A TEXT BOOK OF HEAT

FOR JUNIOR STUDENTS

(INCLUDING KINETIC THEORY OF GASES, THERMODYNAMICS AND RADIATION)

BY

M.. N. SA.HAJ D.S~.~F.R.S.,

LATI! PALrr PROF1!SSOR OF Pr(YSlClS, CALCUTTA UNlVER5'.I"rY

ANn

B. N. SRIVASTAV~ D.Se.., Y.N.I.,

PROFESSOR Of>" G ENEi~AL PHYSICS, bmIAi'lf ASSOCIATION FOR, TH~ CULTlVATlON OF SCIENCE, CALCUTTA

(TIVELFTH EDITION)

SCIENCE BOOK AGENCY

P. ]31m, Lake Terrace, Calcut.ta.29'

,

FmST EDITION I~33
Second hnprfJ.'isi01t 19~ij
Sl\.WNlD EDI'UON 193'9
THllUl EI"Il"fWN 19'~5
F OUR'll"H. ED1TION 1945
F.ilFTH EDITION 1949
Sun~i ih.mUGN 1Y51
Sii.VENTII EOlTION J95~
L1GHTH Em ,'ION 1954
N~N'l·H E~~uo~ 1957
l"!,;~·rH Eorrtox HWJ
EU:\,l'NTII EOITlON 1962
TWELFTH EmHoN 1%7 . Ul Rights reserved

¥UllUSHlib BY S}!.L R.01'.h\ S.UIA, 125, SOL""l~~n"RN AVENUE, C.\LGUTTA 29

PRH'lTED BY l'IoIom:.rtN INOlA PRE~S

7> RAJ·\ Su~mDiH M ULLICK SQ U A" Rll:, CM..c'UTT' A W

Price R u pe,e~ Nine on1}'

PREFACE 'ro THE FIRST EDITION

'I he Text Bookof Heat for Junior Students has been written wltb L view to supplying the needs of ~h.e students 0'£ the pass course t t'ading ror the B,tJ(;:helor's degree. It has grown Out of the lectures which I be senior author has beenglviog to the B.Sc pass ciass of rile' 1\ llahahad Univer~hy forroevera,] years. The plan of tne book rlusdy fo1101iiS th<lt of the larger Text Bonk which is intended f()l" rtSc. honours and. ]",LSc. s tuden ts. Sep«lnr. te chap ters have been d~votcd to Kinetic Theory, Liquefaction of Gases and Heat Engines, rhe principles of Thermcdynamic» and theiirapp1icadons have been

I n:-::ttnl IT t considers ble leng tho Throughou t the book the me thods oE t alculus have been freely employed, The supplementary chapter 0'11 met~or(dogy has been kindly written by Hr. A" :K" Dasef the Ind.~an \of ~l:corolo£,Jcr,rJ Benke and. M r. B. N, S:ri"1K~ tava ,. Meteor-oktgy . i,~ a glowing sdence and IS ex,tremelj' useful to the public at large, It i~, not at present included in the currieulum of <lny Indian Univetsity (exccp~ Agra where it forms aspeclal cm.H'$~ for the M,Sc, degree)', 1111 t th D s seemsto be a cardin a I omi sslon, I t is ho ped til" t in future ; ~ win form <I regular su bject of study by degree st.udcn!:.s.

As th is Is the first ·ed.idon of the. hook, it is feared thar th ere ma y be several omi ssions and ina ccuracics, The au thors w]J1 be gr::ll te Fu I i[ these arc brough t to their notice,

Allehabad : ffUllWry. 1.933.

M. N, S. 13. N- S,

P'REFACE TO THE ELEVENTfI EDITION

Since t:.lle last edition many Indian Unl:\ien:i~it>.~ .hll.'ve introduced ~ he new three-yeti!" Degree Course whUe some others are stIll eourineing the .o]d 1:WQ.year course, The back hall therefore been thoroughly revised to covel" the sy Ilzbus of the new~ht'ee·year course of m 03t Indien universities, A~ this required on]y addition of some m.aner previouslv found in the Intermediate Syllabus and as the old subjectmatter of tbe book has beee "']II1i()st wholly retained, It. is ronfide"rntly 11 oped that the oM,k will prove eqU:i!Jly u~eful both for ~he new th reerear course and the 010 tWt'J-ye;;r:r course.

Calcutta: fuh. 1962.

.B. N. S .

PRE:rACE TO THE TWELFTH EDITTON

Sevemlsuggestl?J1!& for the .lllip.mvem.cnt ?f the book, kindly ~ (,1~ ~. by te~cher8 u~mg the . book, h ave beentnc;orpota ~ed ~n ~his r(JJ non, The s ~an:d'lJ.'d quesnons, art·angtd ch apterwise and g"1Ycnat 1 he tmd 0'£ the book have been bmught uptodate,

Ca leu Lla :'

rM'1Wlry~ 1967.

It N. S.

ACKNOWLEDG1..f.ENTS

\\r'i:: have much pleasure in expressi ng our inde btedness to the following authors, publishers and societies for allowing us to reproduce diagrams w hlch a ppea red in t he works mentioned below :_

MuIlel-.Pouill.et~. L(lhrbud~ der Ph)'sik.

Henning, T empera: af11Mssul:tg.

Nernst, GmndlQgen des nrn.tn Wlirrnesai1.ftS. JelHnek, f_..ehrbuch der physihali:>clam Chemic. Ewing, The Steam Engim: and Otlse« Heat Engine/. Watson, Pmc~ical Physics.

BUl'gt:S~ and Le ChateIicr, The Measurernent of High Temperature,. Proceedings of the Physical Society of Londo.n,.

Ph)'sic:al 11. eview.

Journal of the Ot)Ucal Sodel~' of Ametictl, Vol. 10.

Proceedings of the Royal Sor;;iety, LDudon. Chap. 11, Fig£. 4, 5; Chap. VIT, Fig. ]0.

PhitOSDPhicCl.! Transaction» of lhe R&)'tll Society. Chap. It Fig. 7;

Chap VI1, Fig. 10.

Z~ilschrpfl fiir PhYllih, Chap. V, Fig. ~. Pflysil alische Zt'iHchriflJ Chap. ]J. Fig. 16.

Annfl{el der Phvsik: C!l1P V Fi,.. Itl : Chap. Vll, Fig. :5. Handbucn de" pJq.rik. Chap, 1\. Fjg. 7; Chap. VI. Fig. 10:

Chap, xt, Fig. 23.

Hnndburl: der F:rpcrimellfOl-physik. Ch::tp. V. l'ig. 11; Chap, VI, Fig~_ ~J. 15: Chap, YTH, Fig. 9 ~ Chap. xr. Fig~. 11, 18, 19, 20.

Ezer Griffiths. ~feUl(Jd.~ of Alc(lSIlring Temperature. Chap. I, Figs. 5, 6, 7. 9; Chap, xr, Figs. 11. 15. 21. 22, 23 frorn diagrams on pp .. 112 • .r)2, 34. 71, 84, 84, 90, 90, HS or the work respectively,

Andrade. Engines. Chap, VI, Fig. 5 ; Chap. IX, Figs. 1, 3. 4, 5, 6. 7, S, 13, ] 5, ] 7 respectively from pages 2390, 6 i, GB, 75, 102, 86, 92" rot. 195, 21 I, 213 of the 'I'.·ol'k by the kind permlsston of Messrs. C. Men &; Sons, Ltd. (London).

Partington and Shilling. SPecific Heats Of Gases, Chap. II, Fig"S. HI, 15, 17. respective 1 y from pages ] 27, 76, 84 of the' \1;·otk.

Preston, Theory of Heat. Chap. I, Fig. 3; Chap. II, Figs .. 3, 12; Chap. XI, Fig. ]6. Reproduced by the kind permission of Messrs. Macmillan & COl.

CONTENTS

L

1

11.

THERMOMETRY

Temperature. ¥ercury thcrmcmeter, Special ty[)C5 of Hq~id thermometers. Ga.~ thermometers. Callenoor compensated airthermometer. Sta.ndard gas thermometers. Pedect ga,!; ~l~" S t.andardh:atiou of wcomlary thermometers, Fi xed tcnl!l.erlllttlr~ baths, Platinum thermometers. Measurement of re5Ist~n~t. Thermo-couples. Lt,W temnc . rature tl11!c1"I;I1o~net~i. Illtemahomlil temperature scale. Illustration of the p,dncillies of Thermometry.

CALQR1MEnY

Oll;ttititv of heat. Melllods in calorimotry. MetllOd of mixtures. Radj.;l,U(-)n correction. Specific he-at of solide, Speelfic heat oJ liquids ~f ethod of COQlirl g_ Method.o£ memn,~ ice. . Bl1l1S~I:' 5, icc: c:alanmetef. Joly's steam calorimeter. I'lie differenttal ~tea!l1 calorimeter, Methods b.ilsed on the rise of temperature, The !ll~thod of steady-I'l.ow electric ealorhneter. Specifi,~ heat of W'l(er. ).Tern~t vacuum caloTlln)!(er. Results or ei\rly experiments, Varlarlon of s1J~dji~ heat with rcmperature, 1'WI) ~'peci nc hcu.t~ _ cl a ~r:ls. E~l?e r i ments ~f Gll,'- L\I5~ac and J oukA ~lliaba tic 1 ranarcrmauons. Experimental methods, ),1 ethod of mIX ttl res. Co I ~tllllt-l'Ju\1;' method. N[~Ostlt'L"merlt t~f C.. Explosion method. Detcrmfuatlon of ''1. AJi.llbatic expansion method, Expetim~nts of Clement and Desormes. Expcrhnents of P-;l.Itingto[1. Rucbartlt':; experiment, \ elocit}· CI.t sOlmd method, Kundt's rube, Experiments of Partington end Shilling, Specific heat Ot su lJC rheo.ted vapour, Results. Special calL'l"imctl!!"l;.

III.

KlNI!:1:1C TI'IF.ORY OF MAI"TER _.

The nature of heat, JCltl1e's experiments. First law of thermod vnarn il~~. l1ethuds for det~rminLng I. Rowl!il.tld·~ ~!C['cri r'I1e1ll~. Ii. slmnle laboratory method ()f finding J. Electriea] mcthcds, Heat as motion of molecules. Crowth oJf the kinetic theory. EVLtiellce 01 melecular agltation, Brownian mo ... ement, Pressure ~x Tied by a peric~t gills_ Dcductio-, of gns In W~. Illtl'udllction of temperarurc, Dl~trilmtiOll uf. velocities. ).ofaxw!.'l!'s law. A\'~I'a~ \·clocities. Law of equlpartldon of ki.n.odc eL1ergy. ),fole.::ular aud atnmie energy. .j:lt311 fre~ path phenomena, Calculalion oE the Tlle,ul free fl<i.lth. Trall~]lOTt nhenom !la .• \-i~co~ity, Conduction, Value of CDI~St~lll~.

IV.

E.q r.hWrONS OF STATE FOR GASES

Devia tin!) from the p.crf~~t ga:!i equa tion, Andre ws' ~..xpr.rimcnts. Van cleT ,"VallIs' Clluatirm of Cltate. :Metbods (If finding the values i)f 'a' and 'N" Di9.cussion of van del' \Vaals' equation" E}:JiI~rtl'l1ent~ stlC((Y of the eqlJation 0.1: state, Experimenta] determination of critical constants, ,\\!fntter near the critiad point.

CHANGE OF STATE

FQ1S!On. Latent 'heat. Sublim~t:ion.. Chl!.l'lge m propenies on m~lting. Determination Q{ the meHli\'I poil'lt. Determination. or the [:1Lle:n~ heat of fusioll. Experimental relationsh(ps.

87

v.

VI

vii

I '''Cit

CUA1"J'lo[t

PAGE

CUAPTER

I X. HI""T ENGINES 204

Three dilt erene etas ses of engines. E~d)" history of the steam ~LI6rifLe_ N ewccmen' s atmospberie d'Lgll:L~_ J a II!t 5 "N a t~. _ U se

00: a ~eJJa~ate condenser, The double-acting engrne. Utih~hQttj

of the e:>1pansivc pOWE!" of steam. . The .gQ'i:c.rnor 0100 the tl:rl,"?ttle

1fa[ ve, The crank and the flywheel. Motlern steam engm.e;9. Efficiency at etlg!nes and indicator djag-ram~. The _carllot

I!ngilltL Reversible anr] irrc\'c,~ibl,e ~l"(Jce.s~es. Reversi bl[it:9' of

lhe C<l:mLrt C'ydc. Caract's the.ol·em. Rankine cyd(). Total heat

of ~tcalU. Internal combustion engiaes, The Otto cycle.

Diesd cycle,. Semi-Diesel engines, The 'N atlonal' f,'a~ engine. Diesel tOI1~-stroke cng;in.es. The steam turbine, The

theory of steam jets. The De Laval turbine, Rateau and Zo!l~ turbines. Reactlcn vturblues {Parsons}, Alternative type~ ot ~'11gil1e~. Thermodynamics of refr'igcration, Effie:ierLcy of a

vapou r compression machine,

Eflect of IlTCS511fP. "II melting pOoirlt_ FIlSIO~ of alloys, Supercooling. Evaporntion, lJui!illg and superheating, Saturated and unsaeurated vapour B. VapLlll r 1~~C3b-u:-e Qt_ water, Statical m~thod!!;_ Dynamical method, DlSCU!iSIOIl ot Tr.SU]t!'l, y;Lf)?U~ pressure over curved surfaces, Latent heat of va:p'(lr.l~flbon. Condensation methods, E.",apCl't-ati.On methods, Varw,tl?"ll.of bl~:r.lt beat with temperature, Tr,ol,.lt.on'\ rule, D!!<L-e:L'ltIl~tJ.O'n Or y:a[Rmr density. Accurate determlnanon of t 1113 dCllSlty oJ ~a~urated vapour,

VI. P~QDUG-rlor; OF Low TEl\;:il'E:T{ATt1R£S 125.

PtindllleJ; used in l·efrigeration. Add!ng a salt to .irr. Broil.ittg a liquid under reduced pressure, Vapour eompressron machioe, Refri gerants. E:kctricrdL-ibrei"~tat".. Ammonia a hsorp~~(jn machhle. Adiabatic e"lla:n!;ion of compres.s.OO ~.~e~. C?OIIll~ due to Peltier err eel. Cooling due to desorption, LII:l uelnctinn ot 1,-a~:;. Llquefaction by application of pres.s~tre and low temperatu.~. The prjncipl« Cif ~as~..n.dC'5_ "PrO_dl.lr.t,lon of 10· ... r temperature by lLt[ll~ing the JOllie- Thomson effeet, Eleruenta L"y t.heory Or . tJl~ porous pf ug e:tperill~~" T"~le ]~or{)lls ph!.£{ ~X:~i'lm~nt. U~rftlcl.ple O'f re.generatl'i'e r.'iloling. Linde s machine tor ittlUdYlllg' air. Hamps01l'5 air liquefier, ChLlide's air IlAJ11.eficr. Urillcla~trot! {If helium, Solidlficatlon m bellum, Cooling produced br adlabatic demagnetisation, Properties o£ b-ubst~tlee:s at liquid he!h1J11 temperatures, Low t.eJtipcl"at?r~ tedtnlq~e. U.S~5 .,of liquid air. Prinelples of air L~ondit[Otlillg. The alr-r))udlhll'IUnK machine.

X. T'I:1ERMODYNAMICS 237

Scope O[ 1hermoclJ'n~l:nks. The thef~l1mJ_ ~tat.e. of a body. Mathenlil.tka! nates. Some phys.lCal applL~atl(Jrls. Different forms

of cnctgy. T ransmutation of energy, Conservation uf ~ne(·p. mS5ip"tion of energy _ The fint law of thcrITl[":>Iiyl'lanuC'S .. Apphca tiOl:lB {If the first law. S pecillc neat of a bod V • Work

done in certain processes, Dil;continuous ehanges in etLcrgy-

latent heat, Hess's law of constant heat-summation. Second

Jaw of thermodynamics and L1.Ltropy •. Scope of the second law, Prellmiuary statement of the ~.e~ondlaw. Absolute ~Ul.le of temperature, Defi.nitio.tl 01 elltrO]lY. Entropy of a syste~Th. Enlropy remains constant in reversible processes. Entropy i1L~ creases III irreversible P'OL:C~~CS. EJl.t.rop~' ()f a perfect gaS_ Gener" I statement oi s~~(Jnd law oi therm(]dYll!l.lnics.. SUllPowd violation of the second lll.w. En.trot})'" and unavailable (.:l]eL-gy_ Physical concept of' entr~py,. Ent~{)py-tel11fH;rature .di1lgrams. EnL'l"Dpy of steam, ApphcabCiju of ~ t'W(} laws of thcrllW. d:rnamics·. The thenl:LOdymU1lkaI rela,tial1~hjp8 (Maxwell). First

rela tion, Ajl:pH_c1!. ~ion to ~ 1L~[Ji_d film, See?itd relation, 0 ther relations. V anan Oil of unrmatc energy with volume. J ouleThomson Coffeet. CCI.rr·tdi(J1l of gas thermometer. EX"d.mples, CIapeyn:l"!i's deduction of the Claus,ills-Clapl!yrO'n relation. Sped-

f[c heat of saturated vapour, The t.iple point.

XL R .... DIATION 278

SorIll! simple instruments t()r tnea~:Llrjug radlation. Properties

and na tlJre of rad.iant energy, Id!J;;iltity of radiant energy and lignt~lltinuitf of spectruai, Fundaruenta l radia tiO[l precesses, Theo-ry of exchanges (Prevoot). Laws of coollng, F....missive

power of di fferent sll!b~tulcc~. Refl{!ctingpower _ /l.l:!.sorptl.o,lJ.. Rel:ltiO'Il~ (!.xisting boeh~een the differeld radiation qlf.QnlitLe3. Ft11lAlamel\tal del'Lnitioll,5.. Ki.rt:htlofF's law _ A ppHc~;t[[)rLS O'f Kitchhotl's law. ADpHcatiQn to ..strophy:sks. 1'emperatlJre

radiaf em. Exchall_~e ·of energy between radh.tirul and matter in

;L hollow enclosure, Deduction of Kirclilioft"~ law. The hhtcII:"

bod.:!'. Radiometers_ S~t1siHrene~s of the tht~rmQpHe. Cr{lO'kes" radicml.e~er. Ilo.fomef.er. RacliQmicmmete,_ Pressure of ratii!t-

tiof"!. Tol.al .m()iatic.tl from a bl!lc.k ·!:Jocl)·-tne Stcfan-Boltzmli1'lIl

law. Experimciltal ver.ifil;a;tion o:f Stef~lr's law. Law~ of di&tdbtJtion of enc;:rgy in. Mat:kbCJd}' SP!!.ctrlltll_ Experi[llentaJ study

{If the bfaci(body ~llcclrLIm. p}7ometry_ Gas pyrometer,!;.. 1~i5'

vn, Tm::ru'\fAL Exl'ANsrox 1.;1

Expansion or solids. Linear' cxpanslon. F_arl[~,. measurements

of linear cxpans.ion. Standard methods. Comparntor method. H.~nning's tube method, Fizeau's Interference method. ~1te

frjng~ width dilatometer, Surface and 1,ro!11me expansien,

l1xr~n sion ~I silica ~las~. invar, E.:;qm,T1J~r"L1 flf ;llli5otropic

bodies. Exp.atJ~ion of [i(Jllids. The diTatometer method, The

weight thermotnejar method. Mattll[eSSeU' s method, /\. bSDI~lte exooj]~i(1n M tiqtlid~. Hydrcstatic tala m=13 method. 'EXP~"Sla!l

of- m~rCl.U"l', water. Practical app!k.il.tlrnl~ of expansion. Compensation {)f docks ami \i\latchc~. Thermost:::lts.. Expansion of

Ii1:3.ses. Exp~rim~ntaf determinatlou Qf thcVO!lln:L€ cO'efficlent 0:1' Qx_pall!;hm. EX-[lednlclltal de termiua hun of tnc press II re Cooefficient of exrmn!'<ion.

VIII. COCiDfJCTION OF HEAT 178-

J\f ethods of heal proil~1laHoIL. Caud.udtivitv of different lelnds

of matter, Definitiol:l of cocductivity. Condtlctivitv of metals, Conductivity from caleriruetric measurement, Rectillncar flow

of heat. Ma.thcmaticaJ lnvestigaticn, rll~l-n;l,.ll~;::'S experi-

merit, Experimd1f05 of Desprets, ",ri~d.ert1!ar.11l alld Franz. Forbes' melhori, Angstrom's method, Cruyfrllictivrty of the· Ear t 11' ~ crust, CondudiDll tl1L"()1tgn OJlinpo<Site waUs_ Relatioo. between t~e thee-

rna] ~.nd electrical conductivities O! metals_ Heat conduction in

tht~e dimensIDlls_ CQOOtlctlVit.t of poorly COlldllCtillg soJids. S-~~hcrkil,l ,silell ttldl:iod_ Cylindrical sr~e][ .methoo. Lees' disc me:lhorl. CondtllCtivity of liquids. CO[llmn methud. Film m(!thad. COllductivity O'f !:,-a~C5. rIot wh'e method. Film method.. R~5t1ltS. Fr(')czing of a pond_ C'Arlvectioo Df heat, Natural cOln'«tioll_

viii

r

I

316

327 331 349 351 852

CHAPTER I THERMOMETRY

1. Temperahlre.- The sensarion of. heat or cold is a matter of daily experience- By the mere sense of touch VI'e can say whether a ~ 11 bstance is ho tter or colder than ourselves, The hot body IS sa ~ d

10 po~ses$ a highe1!" temperature than the cold one. .

But the sense of touch is merely qualitative, while scienulic precisiou requires that every physical quantity should be measurable in numerical terms. Fmther, the measurements most be accurate and easily reproducible. This requires that the problem should be ha n dled objective! y and the sense of touch shou ld be dis carded in I a vour of something w b ieh satisfies the above criteri a, Le t us $€C how th is can he dope.

\.vhen two bodies are brought in contact, it is found that, in !;eneraI, there is a change in t.b~ir properties :;;l_l(.h_ as volume, pres.sure etc- due to exchange of heat. Einally an equllfbrium state IS attained :1 h~r which there is no fu,nher change. The two bodies are then said to be in thenn~ equilibrium with each other. In this state of thermal e(Juilibrium the two bodies are said to have the same temperature which ensures their being in thermal equilibrium: A'so it i:. round that if a body A is in thermal equilibrium with two bodies B and C. then II and C will be in therm al equilibrium 'With each other a ad therefore be a ~ the same temperature. These ale the two hmdamental Jaws of thermal equihbrium and it Is on account of these laws that wc arc able to measure the temperature of bodies B and C hy bringiI~f]; them successively _in thenna! equilibrium wi~ the (her~nometer A. 1 he temperature 01' a system is a pmpe:rt)' which determines whether or not a system is in thermal equilibrium with other systems.

Heat mu,~esm.any changes in the -phy~iGtl properties of matter some of which are well known, e.g., expansion; change in electric ... .1 I t ~j~umfe. production of electromotive force at the .function of two ,Ii:.!>imilal" metals, AU these effects have been utiljsed for the nlr.;J~urement of temperature, The earliest and commonest thermoUI('[{'r~ utilise the property of expansion. Mercury-in-glass isunivcrsIlly p.mpJo}'p.d as 11. thermometer for ordinary purpose~, but though i~ I~ ~rrllpJe. convenient to use and direct-reading, It is not sufficiently ur iurate for bigh-d1&~s scientific work,

2. MerC1J.ry Thermomeh~ii'.*-En~r}'body is familiar with the "r! 1111;11, reutigrade cT1ermomet.cr_ It consists of a gl aSS bulb conI Iii I i JIg- mercury to which a gra du ated cap ill a ry stern b a uached. l'llt, II '-1CZlng point of water is marked ooe and the boiling point IOO°C 41 u I I he interval divider] into 100 equal paTts_ 'This scale was first iuu nduced by Celsius] and is called the Celsius or centigradc scale

F'or rI~ta[l~ of construction see Preston, Thc()ry 17/ Heat, Cbaptcr 2_

t '\ntief5 Cdsiu_~ (1701-1744) was ImI"t1 at Upsala where lie studied matheIII _I" ~ und astronomy, In l7J.{l he became ProfeSS01" of A~tra.Il.omy and ten years Jill" III' huilt th~ observatory at Upsala. and became Us -diro::L£II1". H ~ invented tl ~ "(·l]riFtI':>1.ne scale.

I 1 I]

2

[CHAP.

I, I

']'U !UUIWMETR Y

and is now adopted Ior all scientificwork. Other SUlks in ordiuary use tmhy are those inLHJdlLCcd by Fahrenheit and Rcaumur, But Pahrenhei t~ W~lS the first to choose mercury as the thcrmonretric substance on account of i~ many advantages, It does not wet gla~:s, can be easily obtained purej remains li<p::iid oyer a fairly wide nmge. has a low .~ p ecific hea C a 11 d high ccnd uctivi t y; it is opaque 11 mi its expansi 0 n is a p proxi m a wi y u niforra a ~1,(t regu~ar. But we mu st ~1ot £Ol"get its severa r draw backs . The specific gravIty and sur Jacetension of mercury are 1arge, and the angle fl.i contact with glass when mercury ]8 rising is ctiLIerent. Irom that when it is falling. On account of these delects alcohol Is sometimes used in place of mercury,and since ie has a Larger expansion it is more sensitive but is likely to distil over tocolder parts ol the tube,

The range of an ol"dinal'}' mercury thermometer is lim; ted by the fa ct rha t mercurv freezes <I.t - 38.8 DC and boils at !lS6 G C bu t the upper limit can be raised to a bon t .100 °C by filling the ~op o r the tulle with nitrogen under prt!~surc, The thcrmomctrfc gli:l~:!l 11i1USt he of special quality: it should be: stable and. should r.tpidly nauru to its n orrnal -"COl teo a Her 'ex posurc to high tern II era tures, The g-hls5es geaerally employed ~r.e vern; d1~?' and r= .16111 (or better-class ~he r - momercrs and borosilicate glass 511111 for lHgh-tcmpcratlite work,

Mercurv I herrnometcrs arc genen'llly employed fOol' rough work.

If thev arc J L all used Ior .LU::llrare work various coreections must be applied Lo gee the 11 LLI..! H:nqxrature. The important ones among them arc the rolh.m-iug ;-

{I) Corrcctinn due to shilt ul' the zero, This is very irnportan t since glass after exposure to high Lemper~1 LLlt"U returns to iL~ noruia 1 st;w: nul}' ufL('l· a very long rime,

(~) Correction due to change in the fund~.merltal Interval frurn 100 to 100+0 (say) where ~ h~s aTliy value,

{f1) Calihretion Corrert iL1l1. This is due to. want of uulformity in the bore of the capHhry cube,

(4) Correctlon for la.~· of the thermometer. This increases with the size of the bulb.

(5) COl"1'"ectiOll due 10 chnllgf'sin the size (!If the hulb eauscd by variabl Q jn tern al ;;J: n d ex ternal pres...m.rc.

(Ii) Correction fOT the ~ff{:'["ts of capilhlrity.

(7) E.~l103ed stern correction. Part of ~he stem and hence the contained mercury does, not acquire the temperaane of the bath.

For d eta Us co ncer n i ng- l he OJ. p plica t ion of these eorrectl OIlS see Appendix I.

,l. Specfa[ TfP,~s of Liq~:id Thertn:ometer~.- The ordinary merwry therm?meter 1~ not suitable fnr certatn putpo~es; Ior this reason spcrial tYIJC~ 9£ thermometers have been devl&ed. Th,~y are

~. Daniel C :1bdol Fahrunhoit (1(l86·1736) was born in Danzili!" of a l'i(lh f~lIrlj I y .111(] fil1,9,1[y settled in AI'l1~terd~m. U~ m~l(le improvements in the: harOllic'tm' and the ther1nQrr~e'lG'r and devised his tb~Imometrk ~ca.k

SPEC LiH, TYl"E$ OF UQUW TIIERMG.METI1RS,

I I I nc I i rLc.;<t tions of the ord insry thermome ter d-e.'iign~d to scrv ~ ehc p.!I'I it I I lilt' end in view,

For nieteorologicci pmpDse~ rhermcmetees a.te l"~ql~lred. to u u l i ("; L Le the maxim um and minimum temperatures to which they 11;1 \'t' hccn exposed during a certain period, SL", devised a combined m,l}o. imum and minimum thermometer 'which is indicated ill Fig. L I 'II ~ b LL I 11 A and pan of tllC tube is filled w lth alcohcl: l p w th e level

n. then with mercury up to CRbove which again there is alcohol Lip Lr~ D. The glilS~' indexes I. I, have each an iron wire attached (~huwn ~eparatd}'), and placed above B

,II ill C i Tl each ttl he" \Vhel1 the t.tml)en'L-

IIII e rises the alcohol in A expands and

"Lt· expanding· mercury, on account .of its

~"1 r.H"~e WnSlOI1J pushes ·U~J"Watd.s the index .IIHI~ e C to its maximum llmlt. With ,I

I ~Ill illlempe.atul'~ th!s index is un~Hs.- I

[ [I I hl,tl due to the VIsm~Hy of alcohol heuig small while the index abeve B is pulled IIPW:lI'c'ls by the contrac:ting ak-ohol, but is

IcEl bddml ~11 .. hen the temperature rises.

. I hL' iron 'wire attached to the glass index

I ~ I ~ ',"{:11 I. ~ it (1'01",n falliIlg u nder its own. w~·~gh f, and en a btes its position to be

.11 lit L~ r p.(1 Irom ou tslde.

The clinical thermometers in ordinarv me <lfC mercury thermometers 0 E short I ;LlIg;C of the maximum type. Tbe. 5t.cm I LI ~ l a bovc the bulb has a COTIstn chon .l~rOL.L!';JL which the mercull", passes wben i ts L~ III perature rises. 0 n cooling, the utercui y [s unable to force irs 'II~':a}' back. I'he range of temper a tures is usually ,95°F 10 llO~F and t.he bulb is very thin and

I,ll e ru [)i I] arv bore vcry fine, Tile mercary F jg" 1.-Six'smaxhmm:l and

I mLLllrrmmtberml)m~t':;L

thread is rendered easily visible by con-

~ II 'u rUng lens-fran t tneX1Tl01UeWrs.

Fm.· accurate work, such as the deeermination Q-f the boiling and lUI II ing points of organic Sllh.s~an(es,. several short-range thermoII H'! l' r,~ ... re ern ployed. lJetw~e'!l the rang-e 0 and 4,50 C>C. They are , .11 It,d chcmicw therrnnmeters, Benzol and tcluol jhermometers are 111IUJ1Fl~t the m.any that are in use"

TI1(:! lkc1una.nn thermometer, indicated in Fjg. 2. is used to IIH·.ISUlc' small cbangf:!~ of ternptfatu.re wi~h a high degree of accuracy. . i 'he ~I('ILI is here marked from (} to 5 representing approxlmaaelv ~ t'IIIIg'T;,de degrees an.devt;r~ degree is divided inLoWO equal parts. I fll'I'1' i~ a reserveir at the top 01: the imttut')"'IcnC, shown separately

I i (t.). I n ell ahle the range W 'be varied. To set the thermorne e.cr La, III ~ II es i 1'(;11 range the b1.11 b is hea ted to ex 11 el lTH::rCLLl":}'i uto the rcser-

~I I

4

Fig, 2.-BrckllL~llIL thermomete L ..

ot. The VOh1l.LL~ "" t cd a certain ma ss o~m~ rcnrl at allY tem[J.eL<l ture I lying between 0 and IOO"e ." measurod 0.11 the poeriect g[t~ scale i~ given by the PI:la~.oLl Vj - ~(r + l '81112 X 10-·' ~ + (1'78 X lO- 9 l~).

ThLl~ tn~ rei ii:liorlt~ not linear ant] the readLnl<S IJf the mere[j~Jth~Tm{h1l1i;ter :~s t"lllih~@t<!f] ou ).1. 1 wjll nnt agree, even after a.p!)!ying the eorrectlons metltiolrl~d <JLl I~, :2, ,!}llh lhj')9~ or aperfect g;<t~ th~r:rnometer even in 'H~~ rans-e O·-100~C.

I.]

voir and the in~u'umell~ gently lapped ,",'ht'~'Q the nH~rC'lny CQhlm~1 breaks near the reservojr and SOme lTlI,en:uty is translerred llll to it. N ext the Beckrn a nn thermometer is immersed along wi~h an auxiliary thermometer in a hath whose temperawrc i~ varied tHlthe' mercury stands at {I division 01 tb e former, Thetemperarure correspond E Ilg to th e zero of the Beckmann rh ermomc ter is lJ~ II S observed on the auxiliary thermometer. and by vary j '\.~ the amoun t of merClu·y, in the bu 1 LI th L~ is adjusted to he near the desired range. The value of each scale division varies wlth tile q u ant i.~}' or mercury in the bul Land acorrection curve for different settings of the zero is supplied wid} the instrument from which the correction at any poin t uf the scale lUJY he obtaine-d.

4. Gill! Tllermom.eler8.~ The ELl nd~l n ~ ell HI1 disadvantage of liquid thermometers is that two thermometers containing dilferent liquids such :i~ mercury and alcohol, and graduated as 011 P;jge r win agree pr{)ba hi}' '.II]] Y at, (1 ~ C and 1000 C a [] d at II f) other tern ptr ature. 'This is due to the l'act that t1H~ expansion of Ehe two Iiquids is not rejrulnr and simi lar, Thus the mercury thermomet ~J of page I would g lye 0111 ar 11 i trary It sea 1 e of tempera ture. Moreover, the correct tons to be applied to it (p. 2) are uncertain and known

(b) oul y 11 ppll)ximal£l y. Hell r;e" for accura La war k mercury thermometers ate calibrated (~[~~ Sec. 8) by actua 1 cornpari son with a res i stance thermometer thnmg-hOllt the en~ire range. Even then the mercury rhermometer 13 rarely usee] for accurate work, and for all standard work gas theemometcra are employed.

Ga~t:'s p nssess sC'vlN"a 1 ad \,11 n tagc~ as a thcnT!0mctric substance, 'Their "expansiun is large so that gas thermometers will be more sensitive and theexpansiol'l of the containing vessel. will necessitate only a '!,,'ery small WHeeLion. Their expansion ]~ also l'eguhrr, i.e., the 'ex pansion of a volum e of ga~ a~ 0 g C is the same

for everyone degree rise of temperature. Tbey can be ob~ain~d pure arid remain gaseous over wide ranges of te.ulpel'_ature_. Further, the scales furnhhed by different g::Ji.'lfS are neady identical sincetbe volume .1 nd pressure coefficients or <Ill perman~nt gases <Ire nea~l v eq ~aL H~I1CC, gas thermometers ate used as pnmary standards wnh WhICh. :1 H others 1Ire compared and. calibrated,

The theorstic .. l bases lllld!2rlyitl" ~he usc of, g_a.li as LhennOlnetl'i.c suhstance arC the laws u.l: Boyle'" ani Charles ''I>'I1,1(:h are very apl~r,?"Im a tdy dbeyccl by t he so-called perm anen t ga.:ses In. n.a~uH~ but will he ri~orollsry obeyed by a perfect gas, Let a g8:~ be- inItially, .at pressure h. vohnn e 11j_ a nd tem per a ture t 1 °c. 'l[ [ we fil'$1 d~ange Jt;s pressure from .PI to PiJ;. keeping the t(~mperatlu-e' constant, and next change the temperature from h to t2, keeping the r]fe~~ul"e comt;~nt>~·'I'"e have lrom these laws,

vii + O:i1 illlil = P'2u - = ---

[1'2 1 + ,at2'

where t/ is [he intermedlaee volumeand ~ the coefficient of expansion at constant pressure, which is found t'xpe'r~mentarry t? be approxf· lIL:tteTy equal to ] j27ft Combining these twoeqmtuons we have

PI Vl ].L {l'~1 '1}

P2V~ = l+af:c ' ~

wh i ch is the g,lS c:q uatio n.

H t~ = -I;.:., V'll ___; 0, i,e., at the ~€mpet1l,tlnc 1/.:.;;;;;: 27So,C

(I Lt:'ady) befow ~h.e ice point, the volume of IDe g<l~ would be zero provided the p€rfect gas t!q_uat~orJ i~ obeyed UuougluJII1t the l(i!.'llIge. This temperature is, by definition, caned the absobut« zero. It is true the g:..ls wOlLlldliquefy and soliclt~y long- before tbi~ st<l~ is 1~e8i~11e~ and the perfect gas equation wou~d cear.~ to be valid. Further, It ~s inconceivable that matter sbould at <lny nme occupy no ~pacc (v=O)" Nevertheless the idea of such a zero 01 temperatme h very useful.] l I we mea.mre temperatures from. this zero, the ice-point is given Ill' ]/(1', ~he steam point bv (I/Cii)+lOO. and generally any temperature, t~DC h)' (i/o:) +~~=T~"K" The scale so obtained is called the Keluin or A bsotute Scale find will be denoted by, OK. Hence equation (1) becomes

PeV~ Plo.,) +'2 T~ hlJl ='" (1l~) + t:iJ. = T1j

p~~~ = hrJ:i_ =fJ~lJ~ (S;~l)'L

T2 Tl r;

denotes the quantities at ODe.

The quanti ty

(2)

,., Robert Boyle (1627.1691) was born irl I reland btL~ settled in Em:;land in 1M k I-Ie distingu] !ill~rl hi mscU lnthe :!~lL:dy of I'lJysic~, and Chell] lst L"y and was 1)11" r) r the F'Oi)lid.a ball J:lK\IUOerS (If the RO'J"al Sodcty, H LS main OOllHrilli,itiOll is III L· ra \'It of g:i5ei1 which still bears hi,sna.n~~ ..

'P The absolute zero ~hu!5 (1efi:ll~rl is sho'wnfronl the1,J:rtl)dyt!:>lYJic cOI1~Werrltton~ ( ella V X) to _he th¢ lOWoest tcmperaturepossiale, H¢l:l,ce~he idea or this al)sQlute , I "I ~ toerl' LIltlPQl"t~T\t [see fL~rther § '] 1.

t

6

THF.RJl.I()METRY

/-Jo<'o/To is known as the gas constant and varies as the mass of the gas taken, but is approximately the same for equivalent gram-molecules of all gases. 'Fur one gnuu-molccule this quantity is usually denoted by R and is cgll~il to 8.3 X J~)T erg.!l/degree approximately. If the mass ot the gas IS increased n tunes, the volume at the same tcm perature an d pre~s ure will be i ncrea sled n times and he nee the mas constant will also he increased 11> rimes. Hence, the gas equation C-~l be written generilly. in the form pv=nR T where n denotes the nurn-

bet' of gram-rno lecules of the gas. .

Equation (2) furnishes two ways of measuring temperature, The pressure may be kept constant and the volume observed at different temperatures giving us the constant pressure thermometer; Or the \'o~HI~e may. l?e kept constant and the change ill pl'essure noted, a principle utilised Jll the constant volume thermometer,

Ex err.t~e" .-C,alcula te the p:e'l81lre of 20 grams of hvd ro gen .insi de a vessel 0 t 1 CI] bic me tre ca pac! ty at the tern pel'a ture of 27 ~ C,

[pv: nR T where u =20/2, A ns. 0,25 a tlTJ.]

5. ClIl!Iellidar CQll1.pelJsatEd Air- Th,e1'mClltl~r __. A ccu [a re measur emerits with the constant-pressure gas thermometers are difficult as the gas in the connecting tube and the manometer is at a temperature different from that of the bulb, To avoid this Callendar devised the compensated air thermometer, In this instrument (Fig. 3) the pressure of the air in the thermometer bulb B is kepi equal to the pressure of the air in D as indicated by the sulphuric add gauge G, Wben II is heated, the pre~sure of the air in E increases and cq uali tv of pressu re is restored Lv allowing Imercury to now out from the mcrcurv reservoir S. The voiuma of the tube connecting Band S is eliminated Ly attaching to D an exactly similar tube plated dose to it. This wiU be evident from the following consideration t-c-

Let '0, Vl.' v:) be tile volume of the bulb E, the tube connecting Band S, and the ail' in S respectively; e, fJ1, fJ'J;' .their respective temperatures, n the number of gram-molccnles of air contained ill .:8. Sand the conne ctillg . tu be Oil nd p i ls pres-sure, we have from the gas laws,

s

n

Fig.

,l.-Cal k'11U:;Lt· compensated ah - thermometer.

(V r,/1 t'~ ) ,

P - +--+- == nR.

e 191 1f2·

Strniiarly if 1./, vI' be the volumes o.f Lhe air in n and the tube attached, 0', fJ/ their respective temperatures, n' the number of grammolecules and P' the pressu.re, we have

'( v' <'/) ,

P . fi' +- OJ' . = 11 R"

.. (3)

(1)

I I

1

If fJ ;= p', IZ =r:', VI =<'1'; (h -== 01', we have from (:Jj and (4)

,

v . 1.12 V

T+ O;=-~'"

II ~Il addition S and D are immersed III melting ice, fI~ = f)' =OU, r II~ i i i"C.dl1g point of water, ana

Thill> we see: that the inUllence of the connecting tubes is entirely "I LUi il1al.C·d if U) Ule premrre in B is kept equal to that ill I? (p P').; (:!) the total mass of the gas in. B, S, and the conuectmg tube 15 !,!Wll to that in n and the connecting tube ,{n = n'); {3) the volumes 01 I he conuecdng tubes ;II~' ~'CJual (Vj =vl), The I ,) J1 d i 1. i o n (el =81') i ~ a II tom atrcall y satisfied ~illrc LIte two connect- 111~ tubes are placed

ide bv side and arc at I be sa~lIc temperature.

6. Staod1ll'd Ga s Thermooneters. - The IlImtant-preS8ure a i 1"rhermometer 11i1~ been ~ 'i"t'i"1lded b-y Cal1endar- 1111 various grounds; (I) I [1(' apparatus and the ru leu la tions are ~i m P Ie ~ ('.:!) t.h e in ternal prtsSl!l'e no the bulb does not 10- !'I't"::t:o;c as the temperaIII rc riscs ; (3) accuracj; nf the results depends I_pOll the accuracy or ,\,t"]ghing, Nevertheless, I,ll [> 1 n strurnen t does not ~j \'e concordant resulta ;In d 11 ~sbeen repIa.red hy the constant-volume i herrnometcr <IS a standard. The normal thermorneter selected hy the

Hureau Internauonal Fig, 4(a) ,-Col1stallt-voluluc. Hydrogen Thermometer,

til'!'. Poids et Mesures

,1Jl(1 everywhere a.dopr.cd today is the constant volume hydrogen ther-

'.

8

PF~FE.G'l." GAS ~CALE

I.]

meter filled with. g-as at a pressul'e of l metre of mercnrv at the temperature, of md~ng i~, It ccnsists essentially of two parts; the bul fi e ~do~mg the in \I ariablc gaseous mass and the manometer for meaflurm.g the pressure" Fig. 4: (a) represents rhe thermometer diagramm<l tlcallv,

. The bulb C is a, pl~tim~m.itidium tl~be a litre in capacitv, 1 metre U1. length and 36mm. In di arne ter, It 18 <I uached to the manometer by a. capillary tube of platinum "I. metre in length. The manometer consists of two tubes A and B, and the stern of the barometer R dips

into A. The barometer uibe is bent so that the upper sur-face of mercury in it is exactly above Band these levels can be read off bv a cathetoI~eter fllrn~hed with tdescopes. The number of observations to be taken 1~ thus reduced to two" B cortsists of two columns oJ: mercury separat-ed .by the .lited'pi:c..c H and botl~ these ccilUIi~D~ communtcate wlth!},<, By, raising' or lowering th e mercury reserve 11- M. the mercury surface in the lowel: part of B is arranged just to touch a line platinum point P [shown separatdy in FiM:. ,I (b)],. projecting from the steelpiece H, and thus the volume of (he enclosed

g<.l!; is kept constant. '

The thermometer described above 1);, suitable for measutlng temperatures up to 500°C.

Fig_ 4(b) For higher telllp~rature~ n:rtain. modifications

ate ncccssarv WhICh w111 he [hSCLLSSed under 'p~·rornetry' in Chapter XL The range of gas thermometers with pmper uiodi fic<Jtiuns can he extended from - 2000 LO l 600aC.

VVc.: shalT. nOl,"~ deduce a for;mula for converting the observed premI_re Tead~ilg~ U1(Q COfl'".e spondmg temperature.~. H f~~, Pl~~ denote th~ pressure ~nd.icated by the manometer <It the Ice pOInt and steampmnt respectlv~l}', th.en Pov= ·nRTQ, PIBfJP --::::; '1R(To + 100) where To represents the rce-potnt on the perfect gas scale and the hindamental interval is 100°C. Hence

since To = liP, Thus to determine an unknown temperature the corresponding pressure .fil is observed on the thcr~nm:lle.ter an~. the remperamre Ti calculated. either from the above relation or graph1cally.

In an actual mea~urement corrections have to be applied for me folIow'ing :-

(a) ThE gas in the 'dead space' is not raised ~.o~he temper~tute of the bulb. The 'dead space' consists of the space inside the capillary tube and in the manometer between the mercury level and the steelpiece H, Its ioitial and final ~empel'atures are also dltrel:'cnt.

(b) Increase in the volume of the bulb C with rise of tempen.tt.ure. (c) Change in volume of the bulb due to changes in internal

pressnre., . .'

(d) Changes in .density ofmercury on account of temperature

\~hangc.:s,

For a discuSS'ion of tbese, w,e authors' book 'A Treatise on Heal'

ma y be consulted.

THERMODYNAMIC OR ABSOLUTE SCALE OF TEMPERATURE

7. Perfed Gas Scale.- The fQrtnulre developed for the gas thermometer assume that the ga5, in question, accurately obeys the ~as laws Lul experiments show that no real ga~ does so exactly. The coefficient of expansion (l at constant pre.'!Sure IS no~ ,exactly the same (01' real 6r.t$es as may be seen hODl any book. of physltal constants . (s.ce Kaye and Laby : (Ph)~cal Consta~ts'). ~urt~er the .to~o: coefficients '_:':, j3 arc not exactl y eq ual, and (:J. also. vanes with the Inttial pressur~ .. Thus, different gases would IUl"lllsh different scales of tempera:Nre It the thermometer is calibrated as indicated above, and the selection 01' any particular gas win be arbitrary and will gi'\le an arbitrary scale of temperature. To avoid this arbitrariness we must reduce our () bserva tious to tha t s ta te of the gas in which the perfect gas ~ eq u a tion is satisfied.

We shall now indica tc the methods] DE reducing the olrservatjons 011 real gases to the perfect g·as state, This can be done -.: .... -hen we have knowlLJdge of the deviation of uases from Boyle's law, The t"lLlculatiom are rather complicated :;mc{' win not. be given here, It is enough to point out that the equation for anYI real gas can be ·w·rittc.:n in the form

PV = RT·+ Bf) +~Cp!l + D[jfl + .. , .......

whe~t_"i BJ C, D._,are constants v,rhich go on d.ecreOl~ing rapidly. 'Thus it j s ev ideo ttha t at inf n i tel y low pn~8ure ~O) a 11 ga,S1es will obey Hoyle's Iaw accurately and this conclusion i~ borne out by cxperi-

frIoo To+100

«= r=;-

OJ." 1. PliN-P~>l

T~ =100 ~-- =1'"

where /3 is the eoefficlen L or expansion at com tam volume. Th us we k~O"\\\r !3 for tba~ gas from a measl~rernent of Pl@~ and P{I" To find the absolute temperature corresponding to any observed pressure lh, we have,

or

(6)

"A perfect gas is defined as one which will obc; .. Bnyle:\ law and Jot1Ir:'~ law (Chap, II, S~,. 22) rigorcusly.

r For Iuller infofllUltion see A Treatis« 011· Hetlt by the Authl)["s. ~: FllrthlC~ see (hap. lV, Section L

10

FlXEo TEIH'liRATURli. BATHS

pu tpose, COm pariscn ba ths may be co ns rru cted, each suita ble for a particular range. Between 0° and lOOgC awater bath, between 800 and 250 e.C an oil bath, between 250 ~a.nct 600 c C a rni x. ture 0 [ po eassiurn nitrate and sodiumnitrate, andabove ~hat an electrical hen LCT is generally em p] oyeel,

Th e secondary thermometers rna y also be stand ardized hy meant> uf 11. SC'f Ies of r.::ai>i]y rcproduci ble fixed poi nts whose ~,empctatm-'~ have been accurarely determined. A table of standard ~mpentlUre~ .i~ giv-e'n below. (Table].). The values lIre gene:raUy those adopted by the Seventh General 'Conference nf\o\Teights a.nd M~asillres, representing rhirty-one nations which was held in October 1927, but some amendmelds made by the NInth General Conference in HI4S have also been incorporated. II

9. Pix.ed Te.nwp.eirallilre Ralbs.-It is frequently convenlen ~ to cali brate the second afY '~ermo me eers by. means of the fn::C'ld.poin t seale gi'~(m in Table l. The ice-point may be most conveniently obtained by dl ppio,g the thermometer In purG rae Iting icc con ta j ned in a dc-war flask. This IS a double-walled glasl'i or metal vessel whose :idC'~. ate .;ilwre~.i" For the s~earn.poil1l.t the hypso~etC1' inclf,cated m Flg, 5, p, 12 1.5 employed, "I he dIagram exp]flll').~ theIr, Co l~ the

Temperature Ci!n~j!l'rade

menta 1 observa lion, Now it IS experi rn en !.ally .Em] n d t.h a t the tern perature scales, obtained by l,I~ing the dilferent gases and extrapolariug the ohservutions to zero pressure, ate actually identical for all r.he g,H~S" 'This isthe perfect gas sc a Ie, The coefficient of expansion cl;" [or ;J: perfect gas can. be calculated in [hi" manner from the data given by Heme and Otto. The mean n.E several results g[ves(l;! = O.003flflO& [or a perfect gas. Thus 'Til the melting point or Ice on the perfect gas scale = 1/a.= 273.10oK. CQn~]dering aU the available data Birge' adepts the value 273.16--Hl.Ol. We shall use the value 273 or 2n,~ or 273.lG depending upon she degree of accur<lcy n~quil'lI!d, AW:l.in r rom 50mC .ICCU ra te ex red men tal da ta on oxygen we have

Lim (PV} 0:; 22.4 H litre X atmosphere. p.-+O

T empcratnre C.etltigrade

-25,2,73C!" l'--;-;- of Hydrogen 419'~ t-'_ p, of Zinc
-195 ·81 B_ P _ oi ~Lt~Clg~1l 444-60 It P. of Sulphur
-1i!2·W I It P. Qf O~ygen f1-.)0·3 1-. p, f)f Antimony
- 78'5 Sub~ lmatlon of CO. 9MJ.8 M. 1"_ of Silllr.t
~ 3ll,S7 F_ p, o~ Merrury ] ou.:~ 1I,r_ p- oi Gold
0·00 M. P. of rce I0-8S F p- of C~pper
+ 32·38 Traasition t~:rnPtJra.t1JN H)] M. p, QE Nkk~l
M N~SO.lOHD r .~~ F. P . of Palb.diuO"l
.,.~.{
reo-coo B_ p" o~ Wate'l' pa9 'F', p, of PI~Lti11ll111
2113-0 R P. of I\ aph Ll-u: 1 ~[It 241:~ F. P. of Id,dillm,
231·9 F_ p- ocr Tin 2620±JO M, p" elf MC'liyb·
MIS'9 I B_ ]?, of nC'll~oflh~non~ de!Ut[~1
320·9 F. P. flf Cm:lmllum 3.380±50 ).L "P. of T~11!l:5tefl
327·3 F,. p, of Lead 3500±50 M, p, qf CIL~bM\ '~See "The InternrLNormi TC!l1p~1"'ilture Scale of 19~8"J Natioaal I'l':.'cskal L~b01·a.tory, 'readington (1949),

t For a ~()m1l1et~ [lescripieLo[l see Cbap. VI.

Hence

R = Lim (jill) n!T~ p ).0

22,4 11 X lOa x 76 X 13,:)95 X 931

-----'---""''l.7;::;;S'.''''m;;:-. - ergs/d.egrce

I

I

J ~

f.I_314 X ]01'" etf,'1> pEr (lcgree .

• ')i]]("C' calor ie = 1.1 8:1 X 10' ergs (Chapter Ill), hence R = 1.9WT caIol't{'$ peT llcgteu, This is the value of the gas constant. For real ga«~ the value or the quantlty PnV~n'o Jiffers only ~light[y [rom this.

"\Ve mav poln L out here an iruportaru result arrived at jn Chapter X fheu: i l is showu how Lord Kelvin, from eonsiderution of heat('r\;L;ine~ has developed an ahsolu te scale i1~depl:nde:n~ of tire i.,.r(Jp~Nty 1')1 flny prm icuto r substance. This is the standard scale or ~emperillt'tne and is known as the rhermodynamic scale, Further it is ~hown there that this sea 1(2 is quite identical with the perfect gas scale. 'Me thus see rh::rt rhe p:r[C~L ga8 scale which W<L~ hitherto show'l1, to depend on the prop,enH:~ of ga!ses now bccom.e~ .indcpe:rldent 0'£ the pf(}perti~& 01 rilly particular substance. Hence ie 15 called absolute seale and is the standard seals i1Lcloptecl in scientiftc work.

Another method of obtail'ljng the correction to he applied to the real gas scale consists in perfotl''I.ling the ]ou]e.Thol'llson experiment (Chap. VI). But unlortunatelv the exi~~iog data on Joule.Thom:ol()Jl effect are .not i~.dlkier1C to enable us to apply this method. and the method gn'en above is afmost tmivcl:'sally emplG)'ect

S. St!!lodardizafjoll of Soecondary l'be.mHlmete"!"B.- GOlS the" mOrn e· ters are very cumbersome to use and require several corrr ctions, Hence in Iaborntnries they arc l"epra(;t~d by secondary ~cal1d<trd~, such ;)8 she resistance thermometer, the thermocoupte, etc., which have been carefu Ify atandardized by ccmparlson with a standard hra,~ thermomet~ in ~talldtlrdi~lng laboratories like the National Physical Laboratory 1n Eng-land nr the "Bm"L'[l1i.1 of Standards in ,,\ra$hing~Qn. For this

~I

12

THF.J1MO M l"'1"R Y

C?ndera~[" e]~pJ.oyed Co pl'e\"ent the water [rom being lost by evapora~]o.n, ~[ IS th~ manometer and T the thermometer. The path or steam )~ indicated by arrows: The bomng point" of , ... iter at the pressure p (lU mm, of mercury) 1:> found to be given by the relation

t = lOilOOO+3.67 X 10--.2 (P - 7GO} - 2,3 ,y( lO~'~ U' - 760)2.

For other ~fix,e~ poin_t~ a number of vapour baths in which sulphur, uaphehalene, aniline etc, are used, serves the purpu!>e.

;,' F~r determining the boiling- point uf sulphur Callendar and GI,iffichs fO~ll1tl ~~Ult t~1C:: standard Meyer-tube apparatus was verv suitable, It consists oE a hard glass evlinder A 'J' d - ~' a 'i' r ' '~' . . It 0" .,,~o; '. ., J.CI ~... 0, rameter jr em.

t;: b~:~~tll a.~u t . 2:1 em. to w lu~h a ~:ph er_H.:a 1 bu] b B is attached 11 t C r'l m (1Ig. 5). The. whole lS surrounded by an asbestos chamber

'. I le thermometer T IS fitted WIth an asbestos or aluminium COlle

T

M

Fig. 5·.,-Hypsometel-.

Fig,. 6,-Suirhtlr':boillllg apparatus

D, _This cone serves in LWei ways: (1) it pn:~vent5 the condensed sulphur from TlInning down over th~ bulb and cooling it below the terupc:at.ute of sulphur V1I pour ;. {2) It preven t8 the bul b from dircc tl Y' radlating to the cooler parts of the tube. Sulphur is placed in the bulb and he~ted aver a flame. A side tube rnay be provided in the u P p'~l' paL t, ot the ch 11 m ber _ a n~ serves to condense sul ph ur va pour, Th e burling pnmt of sulphur 18 given hy the formula

t = 444,6cO+9,09 X 1('1-';1 (p -760) - 4,8 X 10· ,5 (1' -760)2.

I. ]

l'LA TINL'M THERlIiOME'I'EIl.S

Baths for naphthalene and aniline may h~ constructed by ~light1y modifving the above apparatus,

RE$ISTANCE THERMOMETRY

10. PlaDnum TherIDGDleten.- The necessity ot serondarv standards has been dearly indicated above. I'wo types of such instruments based on two electrical properties of matter wiIl be describcdin this chapter. These proper tier. al~-(l) variation of. elt:(u~ca~ resisranee of metals l!{lth tempera tum; (2) varrauon nl thermal electrO-IIloti,;e force with temperature. ll'irst ! e t us consi der the fanner.

Sir WiUiam Siemens was t:heftnt to construct thermometer in ] 871 based on this principle but the constructional details were unsatisfactory. Later :impron~merits by Call~ndar" and Griffiths have given the instru-

ment its Illodern form. FrS', 7 represents an b~l:l~tic-

ally-sealed thermometer designed by Dr, E. H. Cnffiths

for laboratory work of high precision. Pure platirmm

wire frof:.'e from silicon. carhorl,. tin and other impurities is

selected. It is doubled on itself to avoid induction effects

and then wound on a thin plate of insulating mica fn.

The ends or this wire are attached to ph tinum 1 e<l,ds

which pass through boles in mica sheets d()se~y fitting

f h e upper par t of the tube. and. the other ends of rh ese

leads are joinec~ 1;0 t:[minal~ P. P at the w.p ol::th~ instru-

ment, The nnca sheets grve the best insulation and

prevent convection current or air UfJ and down the tube.

The ceil is sealed for, otherwi se, moisture would dep osi t

Oil the mica and break. down the insulation. To com-

pcnsate for the resistance of the leads, an exactly similar p:'lir of leads, with their low ends joined together, is placed close to the platinum thermometer leads, and is connected to terminals marked C, C. on the instrument. These are culled oornpcnsating leads anti are joined ill the third ann of the 1Nhcats,toue hritlg'e a~ shown in Fig. 8 (po I fl.).. Then since the ratio arms are kept equal uud the compemOielng and platinum [cads have equal resistance at all tempera tu res, it. is the resistance o( the I .larinum coil alone which Is determined. For work up III 7UO°C copper leads may he used arid the whole may; lx: enclosed i~ a tube or hard glass. But for high tern- Pig, 7.-PlatijJlT:l1 ures platmum leads must he 'used and the whole num thermo-

I n ust he en dosed in a tube of gLuc d porcelai n, mete r,

The precision and reHability of lUodern resistance thermometers are entirely due to the work of Callendar and Griffiths. They deter-

4< H, L, Callendar (186J-19JO) \'~.d.S educated at Cambridac and worked in Ute t 'av~ll£ll~h Laboratory from I BBS to 1890 QIl r~sista.tlce thermometry, His gre.atc~t II ')rk~ are the develepment .~ the plaLimltll rcsi ~tatl~~ thermometer and t~e in".c~tjgati{l1J m the Il~opertj~ S (If stearn,

m

14

J I 11".R.;),{OMI11~ Y

[elI'l.p.

mined the re~i~lance of pllre platinum from 0° to 500°C a d I d

linn iE W<lS vel- , l 1 . " . n. oun

) ::ICC Irate y grven by a parabolic formula of the type

n, = ": (I -L at _I- R~2\. l~)

11 ~ tJ J~ • ~ I • ,,1

w ere 1~, and Re, are Lhe resistances aL tOe and O"G a tl R

constants. For pure platjnum a = ~.9'1' 1O_J:j jQ _ l:: o· n ~,!:' are tullcndar Iurtl ,- "I I l' .;, , P - - :J.O X HI '. l1ul

.. . ,leI snowe; t iat It 1"'<1$ llnneces5ary to 01" l' ,

"h aur equauou to fiLiti t from the \'.dlJe £ it s 1 C t IJS Y.l:'-'L" Conn to 'Lhi) relation ,UlU introd d 0 J' He g_=lve it spt"Clal in to general lise. TIl, - uce nome~c1aLLlr(; which hOi~ rnme ueaus of the .'~pIA J:Us we .(~eti:ne the plarlnun, Lt:mpel'a 1111'1: '» L)

, ~"U ,_ U1Car relation.

. R, =Rcl(] + a )J'

where c· ts the Ill.ean temperature 0::, " P - •

~ nd 'OO"C J' hus ei COC1l.It:1ent 01 resrsiauce I ctwrru 0

. , fum is t us enu a ~ to (R R ) I' 00' .

If'IHpe"l'ature I whi.dl i 'J .. 1 1~1 - n ! R(I. fhl' plat.lulIH

J.. I)' !; near y equa to the true te·· '

t 'Jer'eJon:, gi\'l'jl l.J~' the relatiun . mpCJ.1l111 (' t, I~,

t R~ - Rn

f1 "'" Rl00-RO . 100, (8)

where R R R . ivcl . .

HJO"(_' ~.h II' Wil~e~pCctL\IC y dcnoLe the n:~jstaL1ce~ at i 0° and

- .le quannry R)om -RD is called the hi 1 rol' - '

F, L) of the thennullleLer c- H d: l1C amenrn JI1IJ.:n al Ilel IJNwe~n rbc true tc • ...11 en ar further showed tb;"lt the lliITc~-

,I : IIrat.d}, 1.11 en b, 'Jt"IIP.cratUTbc f] ,aUtd I he pla tlnunr reml'rr;lllln~ I.,

M ".c para 0 a: orrn ula r:

S { C ~o) ~

I 1

100 j ,- r!')

·1 "f I ant f_or the purticuhu- specimen of wi\"(: anrl il~ V-I] LI(,

I [1 pUHL'" of the speci T ~ 1 '

~ imen, o '4('( UCC (!-l) W~]II urecd

1. ]

r t

-&- J OOa + (lOO)~.e X 100 Crom 0)

_ ~(WO)2 [( t ) 2 r J

- - 1:1+ 100fj lOD I - Too'

Thus 8 in equation (9) is equal to

,6p (0):1

- a-=+- 100~·

, The value of 8' ro.l' the specimens, 1, d .

IJ Ighcr the fnn-ity the lareer is . and the emp ]ol)e ~ ts ab~ul 1.5. :rhe

e O! .. sma er rs o. 8 IS determ wed

... (' i~ s tigMly di ff creut frorrn 1'1. The oC'~ct rel atio.rt

II = c(1 +T~J); B - - (J~)i-

may b~ tkduceJ to be

b:- finding the platinum temperature t p for the boiling ~ai~t uf ~ulphur whose LL"lH~ remperamre ts known, <Inti. then suL~uLULul£' in (hi), Knowing B tor a specimen, we COLH use it to jnuasure imy unknown remperaurre The resistance lt~ of the thermcroeter at the unknown tt:1lLpel'::tture is found out and tben using V~) tp is detcflUlllt:d, Fronl this, uu L1g the value ot 8, rhe true temperamn.: ~ can 1)[: determined l\~it,b L111.: help uf (9). 1 L will ,1)(; observed thut the corrccrlon term gH'Ulg: the l'a1ue 01 l- t p contains the unknown iemperat ui e t, lot' I"OL~g-h work the value at t fr may be ~LLhstit~twd lor ~ on the righl-hJod sick ot (9). For accurate WOl'k, howe .... er, the proce[!un: is as totlows :-

I'he right-hand side of t9) is c::llkulated tor diflerent f1siunu~d values or t ana a table is constructed giviug the value of this correction terlll lUI- dincrcm values o[ t It. 'With the help of thi~ table the true ternJ ierature ~ cmn:spomling to the experimerually cJetemrl.]IlEld platinum tempera Lure t Ii is fomHl.

It 1\'.15 shown tater by Heycock and Neville, and '\'Vaiduer and

Burgess that if the platinum thermometer if> standardized at o~ J. IODc und the boiling pOll1l of sulphur the parabolic formula (9) gives true l'cndin!,'"!i OI.!> far as 61101;lC_

''Vc shall WllstnUethe method by, a lmmel'lt:al example. Let the reslstance of :t given platinum thermometer at UO, 100° and boiling point Llf sulphur (1H.G) be 2.56. 5.1)6 and 6.78 ohms rc~pccuvely, J t j~ required to calculate the true tempcrMul:"'(;! when [he restsranre Ilf the thermometer is •. 56 ohms,

5,5(;-2·56

t" = 3.56- 2.56 X lOG "'" SOO~C.

I p lor the 1Joiling point of su.lphur 6·78-2,56-

= 3.56-2.5~f J(. ]00 so. 42:2°C_

444.6-422 =3 l{H4'5)~ _ 4H.6}

1 lOO 100

whence S::] .47.

From (9) we g,et t = 3()O, t - tp = 8.8, hence ~~ = 291..2;°,

t = 3.20. t - ~ f! = lOA hence t.p = 1:109.0".

[he correction t - i ~ for ~ ~ = 29] .~o Is 8,,8 and {or g09,,!) it is ]O,lt

H~llCC [or t~ = 300 it is 8,B + 30]g~~4-=-:~~'2-X (300 - 291.2) = 9.6, I'hei elore the nue temp(::r3tUl'e t i~ equliIJ to 301J.6QC.

II.. MCaAltI!!'cment of .R.t'&is'bince.- The detarrnmatlon 01 temperahue j,y this thermometer invelves the accurate measurement of the I ('~i~lJnceQ£ the platim~m wire. Various special types 01 resistance til 1~IW are used lor ihts purpos~. In order. to ooll1Jlensalc for the I r sisiancc of the leads, H bridge 'iNtth equnl ratio arms IS used, FLLrLhcr

11 IJrittgc should be capable of measuril1£' chal1~cs in rC~iSLtH1Ca to a hi 'h degree of accuracy for the Iundamental interval is gcnelJlly I ohm and measurement of tsmperature C;cl' hundedths of a degree l'q11ires resistance m asurernent to one ten-thousandth of an ohm.

Hi

[CHAP.

The.C:anel~da~ and Griffitbsbri~ge" is quite suitable for ~his purpmc. FIg. 8 indicates rhe connectlons. Q and S, the pitlO. arms. are kept equal by the makers of the ins~rLIment. ,R consiats oi a set

I . of resisrances or 1, 2, ·4, ~l. 16, 32,

------I r-__""--., 64 units. The usual plug contacts are here replaced hy mercury ell p contacts. 1..1 and L~ are two paralId wires of the sa me ma terial which can be connected to each other by the contact-maker K. This. artan~ment is adopted in order to eliminate thermo-electrumotive forces, P represents tile thermometer and C the compensating leads. The res! stan ce r acts as it. s hunt <In d ma kes the resistan oe of t11 e wire exactly in Fig; 8_C~Hel1dF.lr and Griffit11.~ Bridge. the desired ratio, The bridge is

adj usted for no deflccri On _ of the _gah'<llIJ.ome ~er, G _ Su P pose tile balance point i~ obtained wltl~ the key K, at a d,l~t1t,n~ x f~om .. the centre of the WIre and ale enttre length of the WU'e IS _(I. Then

P+ (a-x) p = R + (a+\)p I

P=R + 2xp.

or where p is the resistance per unit length of Ll:c wire. It is found convenient to select the wire L2 and the shum. r In such a manner that 1 em, of the btillpe wire has a reaist;:!.Occ uf 1/200 ohm ~nd the . total leIlgth of the \1'111: is 20 cm., while the. smallest, resistance 1Il. R marked ] has a resistance equal to the rcsutanoe o[ the whole ware, i.e .. ~0/200 = 0.1 ohm. 'Thus if the Tundamcntal interval of _ the resistance thermometer is J ohm the tClTIpen~tlln~ can .hc determined correct to .01°C provided the balance pomt IS determined rorrect to, 0.1 nun. For accurate wurk, however, various preciiutlOns are necessarv 5.OmC of which are given below+ :-

, (1) The current flowing through the bridge heats the hridge

coils ana changc."s their resistance. The change in ternperature ma}i be observed on a thermometer and the corresponding ~hangein re;<;ls~,nce calcuhlt.ed". The correction can then be easily applied, Or the bndge IIWy he

placed in a thcrmo~tat. . .

(2) The thermometer coil has Co be very dun (0.1.5 mm, dULme tL"T) since it must ha we a large . resistance and hence Lhe h~ating effect ]s considerable, From. Callendar's observations the heating effect for a orrrent of :(11 aml?~re is 0.016° fit OOC and 0.017° at mo°c. According to rnrn the best, procedure is to pass the same current through

* For further cktails see Flint aile! Worsnop 'PraoGtical Pky:;ic:;'_

't For fLdl details see Methods {Jf Me(1S1lrrng Tfl1t.pe-n:lilwe bj. E. Griffiths, (Chap. 3.)

. (

MEASTJRlCMENT OF RESISTANC.t::

17

the thermometer at all temperatures when the heating effectremains appl'Oximately constant.

(3) '1 he bridge centre must be determined and the bridge wire cali bra ted.

(4) Due to tempet',Hurr; gradlent along the conducting leads and the j unc:ti(m~ tbermo-eI~drornot.i ve forces are develoI;led in the circutt whose magnitude may be found by' dOfOmg the gahl~.mometer eircun when the battery circuit is kept open. To eliminate these the galvanome:ter _circuit should be pcrmanenrty dosed and balance obtained for reversals of the battery current, If induction effects an: perceptible when the. batten' > circuit is made or broken a thermoelectric: key should be employed. This key first breaks the galvanomete1' circuit, then makes the battery .and the galvOlnometer circuits i.n succession.

(5) Tile external leads connecting the terminals PP, CC to the bridge should he exactly similar and simHarly placed.

12. As already mentioned the platinum thermometer is starrdardized by measuring the resis ranee at the melting pain L of ice, boning points of water and sulphur, The last !;rive; 3 and hence t can be determined hum any, subsequent determination of t/l' Eqn. (9) however does not hold much above 630@C and therefore cverv such thermometer is provided ,'with a calibration CUrve drawn by in actual cornparison l .. tith a standard gal> thermometer in standardizing laboratories, The temperature can be directly read from this temperature-resistanee curve.

The great advantage of platinum thermometers lies in their wide range (- 2(}DOC to 120{l°q - It ca.rdulIy prepared, their readings are reliable to (UB 0 up to 500cC and to 0.'0 IIp to 12000C hut genenlly it is no t desirable to' U se them above 1 000 ac O'IlJ.Ting to the danger of eontami 11 ationby the insula Crng materials. They are free from changes of zero for the wire when pure and well-annealed has always the sa me res istance a t the sam e tempera ture. They are y,ery convenient for ordiuary use and, 'when once standardized hy comparison with :J:' gas thermometer, they serve as reliable standards, Tbey are !JELen employed to measure small difJe-tences of temperature very .rccuratelv, sometimes even to one ten-thousandth ,of a degree. There are, however, SOme drawbacks also. The resistance thermometer lias a large thermal capacity and the covering sheath has a. low thermal . »nductivity and £hel'e£ore the thermometer does 110t quickly attain r 1.1 ~ tem perature of the bath in which I t is immersed, F urrher some r i III f! f~ los ~ III balancing the bridge. F Or these reasons the l"Esista Dec rhcrmcmcter is useless £0[- measuring rapidly,dlanging temperanrrcs. I' urther impurities in the platinum t10 not obey the same resistance- 1(' tll pent mre Ia w as the pure metal.

Table 2 gives the variation in resistance of a platinum thermollll'rl'f' over a '(vide range. It is taken from Henning's TempcraturII .~\'Imf!.. The value of the quantity H = R,/Ro is given for various

'} -

'THERMO-GOUI'.LES

H!

1HER.MOME11l..Y

LO 100 n° bu t .01 bove that piatinuln;l!lld an 11 no}" of pla tin um wi ill iridium 0 r rltodium arusr be used. Le Chatelder in [t180' lntrcrlneed the cOU p],e consist] ng oE pure pla dnum ~ nd an al Iny of 90 pel" cent Pt and HI per cent lRh which is now largely employed for: sdentHic 'II'o'(JI."k. The e.m.I, developed by

these noble metals is,however, much less, '

The two elements are taken in the form of a wire and. one end of both ]s, welded together electricall y orr in am o.xyhydrogen flame. l'his end a {FIg. 9} forms the: hot j unction. The portions of the ""rires n€flJr the ho t ju netion are ihsul:ued with (11. pillaTie.$ of fireday {or hard glass lot lower tempel"::Itu!es)Olind are ~htt!lded th:rough~ica discs~ndosed in outer prOtEct. mg tube of porcelain, qUa1-t:;!: {J[' bard glass, depending upon tLu~ n::mper<J:mre for which it ]8. meant. The J Jro teet ing tube prevents the junction from contammat]~lll but ne'cesSllIily Introduces a ]01g. F{'J'rrough use this mlly be further enclosed in OJ: st-eel sheath (~hOWD black in the figure). 1j,'Vher-e there is no risk of contamln~tion. the mk~ d]~cs and the pm'tecting tu bes can be dispensed with. The wires are eenneceed to terminals C1 :top C~ on the instrument, To these terminals arc ct)nne.ctJed _flexfb]~ corn peDlS<L dns- leach leading £0 the cold Jlmcw:m ' (Flg.Wa). These leads are usually of the same material as the elements of the couple itself. Thus the cold junction is transferred to a eonveniem cilst~l1t pl<l<;e ~herc<l consranr tempexatuN~, ~il.y n-c, ran ber mam eam ed, U suall y~he com pen~lIl ting Ieads

~ I re marked so . eh a: r ,therei:. no difficui ty in COP ~ecdng·

UI the pwper terminals

. ~f'h etc . a:r~ two. 'Il'l<L Yf of. making the connections which <Ito indicated in Figs. 10 (0) and (c), The diar;nlms eXf!lal~thenlls[2hlc:s., The cold junction Is H:ll mened ~n _ iee at OQ C. As <I recording in ssrument ~Ith~r [I millivoltmeter or a potentiometer is, employed.

remperarures ,,;Il!el'e lit, Ro are the re~istanC:ils a ~ temperatures t Q C an d (19 C res peetively.

Table 2.-Vallles of R =R~ /R~.

T~mp., R Temp, .R Temp, R
·C ~C ·C
-19() 021607 +40 1.1579'6 ZIlO 2_06661
-1&0 {}.25927 6(1 1,230'.;4 300 2.1.%1.31
~100 (I.:l!l50S S(I U1406 320 221154
-140 0.42986 100 1,39141 340 2.28330
-120 1)_~1347 120: 1 AOO3tl .160 2.35-l<lO
-100 0.59612 140 H44,l :Ul{) .2.42543
- 00 0,67814 100 1,62067 400 2_49580
- 6fI (1,75948 180 1,6%Ui 420 2.$6570-
- 4{1 o.M019 200 L7ilIS 440 z'()3513
-l20 (I,92{l3.3 22(1 U3474 400 2.70410
{) 1.00000 bleD 1.91983 400 2,77261
20 tfl7921 260 1.90045
THERMO-ELECTRIC THERMOMETRY 13. TbcmlO..iCQuples.- Let Wi now return to the seoond electri-

"I pr open, in L llsed forte m pera U!rC ruensuremenr. Starting {rom SC:E:'hf'r:k's discover, ill 1821 n uincrous attempts were made to f'umtrLlct u thermometer based on~llj:s principle, for instance, by Hcnllu:rd. Pcuillet and Regmmlt. At present thermo-eleetrlc therrnornetry has attained a degr~e or pl"CC1~i(J1l inferior only to rrsislaucc thermometry below lOOOgC, but Ior temperatures exceed. ill~ that, it is the only sensitive and eonvendent electrical method ~I tOLL r disposal.

A thermo-electric thermometer installation consists oE the following parts :-

p) The two dements consei tu ting the dl~TmQ·conpk,

{:t) The electrical insu lation olthese wIres and the protectingtubes,

(il) Millivcltmetet or potentiometer for measuringthe thermoelerrramori ve force.

(4) Arrangement for controlling thril eold-joncrion ~mpenltun:~,

Th02 choice 01 the dements oomtiLu!.ing the couple 1S determined by l he !e:mperatme to ~,,'h]ch the couple l~ to be heated and the C:LmJ. developed, For lowternperatures up to 30(l°C couples of base metals such as iron-consaa man an d copp er-cnnsran tan are satis[accory, as they devcl op a large e .m.L of ahou t <1 O~O 6 n microvolts pel' degree. 1: or high temperatures these hase metals cannot be used as rhcyge~ oxidized and melt. Nickel-iron eouple may be used up to 600Q while nickcl-nlchrerue and chromel-alumel thermo-couples can be used up

Fig, 9.ThermoC[}Ur!e,

COM

1111 rlllil~[)l1ple JLIll.(t~01i

aUi'lli'~.n9ati~~

~~I::amlll H6t Cold

j!lllCtroli .jmMWJl

14. ' ~ '0 fi 11 (:1 th e LempI,"'l'a ture t) r the hot [u uction we m use IIW:l~LII t' t he e.m.I. dC\'t'loped hptw('('n Ih£' el1d~ oj' the copper leads ..

20

I Ctl:}ll'.

I.J

'llIE.RMO"'0()Lll'LES

21

This can he done by means of a high resistance millivoltmeter ,o;,hich. may be graduated to read temperatures directly an'~ the temperau.u"1f th us 0 brained can be relied ulxlll to about + vac. For a training higher accmacy a potenuorneter must Le used. This arrangernem essentially conslsu ol a number of resistance coils A (F·Ig. 11) placed in s-eries with. a long wire res is lance r stretched alon ,r a sea 1 c. A em-rent [rom t'6c batterv E flows throughfhese re'. sistances a ad its stren gtb is so adjusted hy 'Varying R that the potential l.1ifferencc across a fixed resistanre K balances against the e.m.L of a standard. cadmium cell C (1.(1183 volts). The e.m.f, developed by the thermo-couple Tb is balanced as indicated, The potentiometer can be made direct reading by kceplngK = lOL~3 ohms. Thus there is a fall of I volt ptl 100 ohms and by con sn:uceing the smallest resistance coil of~.1 ohm resistance and the wire r also of the same resistance, the total c.m.f. across the wire will be 1 rn.v, If the wire is divided into 100 divisions and in addition bas a sliding' vernier having 10 divisions the readings can be taken correct to 1 microvolt.

Various types of potentiometers based on this principle have been devised specially for this pllrpOf.c.lt ''Vith these instruments the c.rn.f can be measured accurately to I microvolt which corresponds to' about J <:OC fur a Pt-Pt·Rh couple, For' a copper-constantan couple this corresponds to about 1/40 def5rce. With it sensitive arrangement it is possible to measure to 0 .. 1 mirrcveltwhen the sensitiveness is increased about ten tim{~s. Eor accurate work the cold junction must he main La in ed at O°C ot herwise corrections+ w iII he require d in tha t respect,

In order to deduce the temperature [FOm an experimental determination of the e.m.f. .. calibration curve is gcneraHy supplied with the instrument. This gives the temperature corresponding to different electromotfve forces developed and has been drill ... n by the makers by an actual comparison with a standard thermo-couple throughout the range. If it is required. to calibrate a thermo-couple in the absence of a standard (Inc, the fixed points (Sec. 8) mmt be utilised. The e.m.f at those points is measured and an empirical interpolation formula employed in order to give the e.m.I, cortf:!~ponding to the

G C r-o'IJ-~

Of--- i K1

'.~

. A_,

Hoi Cold

intermediate temperatures. For <I Pt--Pt·R.h couple three different eq ua t i om must be use d fOT the different range~_ Th us

from W' to 4000C, E = At + .B (I _ er') ,

3000 to 12'DOcC,. E = - AI + R't + C!f-J,

11000 to 1750cC, E = ~An + Fjt + GrF~2~

where A .. B, Care constants whose values are empirically determined .

Thermo-couples are frequent.!], employed for laboratory ·v .. ork since they are r.:heap and canbe easily constructed, They can be used for the measurement of rapidly-changing temperatures since the thermal capacity of the junction i~ small and hence the thermometer has pra.c(icaUy no lag. Another advantage in the us-e of thermo-couples is tha t the y measure the te rn ~eta iurc at: a poin t--:-llie pOI_n t at w hi.dt the two metals make electrical contact, Its chief disadvantage Iies in the fact that there is no theoretical formula which can be extrapolated over a wide range and consequently every thermo-couple requires separate calibratiou.

The usetulrange u[ thermo-electric thermometers is about - 2000 to 1600"C. Readings are leljabl~ only, when t~he compo~ition of the l:o~ple _doe~_ no.t "ltangc even slrghtly. ln actual practice frequent calibration ]~ necessary,

The f()llowing are the chid sources of error in thermo-electric thermometrv :-

(I) Parasi tic elec tromotive forces developed in ehe circu i t, They are due to (a) Peltier effect or e.rn.f, developed due to heating of funct.iou of dissimilar metals at points of. the circuit other than the ho~ and the cold junctions. This occurs often in the measuring <t[)paratllS t {b) Beoquercl effect oOr e.m.f, generated due to inhomo~e.nelties in a si.ngle wire; th~s OCC;Ui"S :m~in.ly in the t.h~rmo-collple wrres, The e.m.f, measured 1$ a sum of' these quant1t.le~ and the Peltier e.m.I. at the two junctions and the 'Thomson e.m.f, along homogeneous wires of the thermo-couple with ends at the two temperatures, The undesirable ,dfcd~ mentioned in ((:I) and (b) rnust he criminated by the, use of materials and methods free from these effects since they are not taken into account in anv thermo-eleetrtc Iormula-,

(2) Leakage from. the light maim or furnace circuit. IE le:ak.agp. curren ts p.J.ss ~~rough the potel1ltiom eter their pn::sence c<I n be de tected by short-clrcuiung the thermo-couple when the galvenometercouelnues to he deflected,

(3) Cold-junction correction if it is not kept at O°c,

For the methods of minimising or eliminating these errors the reader is referred to }I,feasut'errumt Of lligh TemPm-'a·tuTCS bv Le

Cluitclier and Burgess, .,

'Table 3 compiled from. various sources gives the thermo-elactri .. '·.m;f. £'01' varIOUS couples 111 common usc. The cold. junction is rnuintained at O"C. and the hot junction at taG. The e.m.L or: the I hcrrno-couple A"B being positive means that the current ftow~ from \ to B a r. the cold [unction.

Fig, ll.-Illtlstmtian or the pr'Urleiple of potentiometer.

'* A description of tllest) w·m be found trJ. M~lkods oj Mea .. mril1g Tel~tp$rnhjr(!,

by E, (;tiffith •

l' See Ezcr Griffith~, Melliods of Me(r.f~~i"i"g T!:lllflJrahwl!, (947), p.. 74,

/

THERMOIlH.TRY

l.CHAl'.

r, J

23

thermometers of o'Lher gases. These experi ments evident! y led to the eoncl usinn Lh~L ~ a gi~S could be relied. u pon 1II~mo5 t. to it~ boiling poi nt, Th!LIS helium furnishes the scale dow n to i~s boiHng poin ~ (4 .2Q K). The corrections nect:ssary to convert this scale to. the lhermody:n arnic s'1I1e rna y be obtained HOd. have been given by 0 nnes rind Carh. Foil' t'el~:peral:un~~ below ,t2°K we must use the helium gotS thermometer with the pressure well below the vapour pressure of liquid helium at the temperature to be measured, &0 that the g:<lS will 11 at liquefy. a. t t.h at t.em.pera:~ure.Wi.th dlts. de. vice the h.e1iul~? g1!S thermometer glveS us the thermodyn:1mu; scale down to 10K" Now we shaH consider the second ary standards.

Mercury freezes at ~ 38$7 and alcohol at - ] lL89Cfln.d hence t hese thermomerers eauno ~ be used below rh e I·espective It.em pc.:ta. tures, A special liquid thennorneterconeaining fracitiomlUY, distilled p etroleu m ether can be used down to - 190(lC.

But for all accurate work, however, ~'e&i$~(jnce thermometer: are employed. It is absolutely essential that the substance of which the thermometer is made ill perfectly pllDe. Pure metals show R :regular dccrea se in resistance 'I. .. '.lth decrease oftem per", tu re. Dewar and F]emin:~ [-otu'!J.~ t h a e the pre5'ence oiI t~c sligh te.st trace ~t lm p,urhy in a metal ts sufficient, to produce a considerable mcrease in resistance at these low temperatures. It is, therefore, difficult to. trust the plu~ty o[ any sp ecimen .lorver}, ]uw temperattU'f'!l withou e actual comparison. Henning found from a detailed in\ie;s~iga6on that the parabolic formula did 1!1()~ huld below - 40cC. Van Dusen proposed the formula

, R~- R~, . ( ~ ) e (t .... ). f3

~ -= R100 _R}OO+8100 -I [00 +- € 100 -l .. 100~ }

l'e.mp, 9(1Pt,l{IRh A~jNi Ag!l'l Fc/con_~- CU/r:OLl~"
~·C, ~g~rnst Pt t8.L~~~.n tentau
- --- -
-200 -fk2'~ -5,519
-HlO -5.82 3,.'H9
- Sf) -1.6& -O.:W ,.
U (UJOO (HlO a,(~} CWO ilOOO
+100 +{lofi.43 +2,18 +0.72 +5AO +4.276
ZtlO 1.436 +4.% +I .. tJ 10.99 92.&i
300 2 .. m 7 "9. 2.96 16.56 14.8;'59
I~-
400 ,l250 9113 4.47 22~O7 2tl.Sfi5
500 4.,2J9 12'_()4 6.26 27.3.8
COO 5,222 l45{1 8.25 3.127
700 ti,200 17,j(} lOBO 39.:YO
sao 7,330 20.7.l 13,1 i' 45,72
000 3A34 24,19 15,99 .12.29
lOOD 9_569 :,R22
120(1 11.9'24
14r)l) I4)12
l(lOO 16,674
mn ]7.B41 (10)

where e is a constanrand 0 has already been defined on P: ].1. The constants, Rm,. Ul~(I and 3 are determined by calibration <lit oac, HJOoC and the .bomng point ?f sulph ur~s c'Xpbi ned previ.o~L]~ly, n~ d the consran t s IS rhen determined Eiy ,call bration ar the bcnhng pm at of oxmen (- IB2,97°q. Van. Dusen's formula has been found to hold ~atisfilctarHy from 00 C 1:;0 - H10°C, t1Hl errOl: nowhere being grea tel" than +O,QJ)D.

For temperiilh~res lowert.ban .... 1909C, the p111~ij1um ehermometer W8JS u~ed by He:nrung and Otso, and can be used with advantage up to 20~K. There is, however. nosati~facto(y, formula for calculating the ~C'mpenltnre from the observed resistance and acalibration curve bas to be usad, Sometimes lead and gold. thermometers are also e-m ploved, Ormes has used lead down to - 259'oC ami Nernst has given amethnd for cakrdming these tern peratures, Below - 250°C resist ... nee therrnomcters of CU11~tlltHan and phosphor.brome have been cmp~o)'~d, the lauer be] ng much more sengi rive,

]i'm' 10'\'11 temp(lrn.turtl~ copper-constantan :uHI iron-constantan couples are very sensitive as they develop a large e.m.I, They can be used down to - 25.i}cC. They must be calibrated bv direct C0111-

parison with a g<L3 thermometer. S

15. Certain methods of n1ea~urLng temperature u ellise th.e radiation emitted hv the hot hody whose temperarure is to be measured. T1H'M· methods will be d_isfussed in detailIatcr (see Chap, XI)., They can he used for measnrmg temperatures from about tooo-c ttl any upper lim it.

161, Certain other methods of m.ca5Uring t~mp(~r:ature utilise allY

one of the IoUowrng properties of 1111i.ttCT;(1) Expansion of H bar of metal,

(2) Changes in vapour dell"~ity wjtb rise of temperature,

(3) Variation of refractive index of a gas with temperamre in accordance vwith Gladstone and Dale's law.

(1) Calorimetric methodsbased on the measurement of quanti ty

of heat. -,

(5) Change of vapour p'I"e'l~ur~ with. teJ:l'Ipcrature.

17. Low Tsmpe:ratliil'e The~mllmJff1l'Y."'- The standard thermometer in rhis ranae is tbe constant volume hvdrouen {)Or he] ium dH~l'mome ser, The difficul ty in til is ease is . that' gas~s Iiq udy ::m d . even 'SoHdfIy at ~b ose low temperatures. Prof. Dewar, however, showed that the boiJing point of' hydrogen as indicated 1J}' the hydrogen thermometer was - 25j.O·DC and- 2.l}ft4°C" '!i~'hile ;1 helium thermoUleta registered - 253.;oC and - 252, ~ °C_ Similarlv hCLOmpared

~'For PY:t'Ollletry see (:.hap. XL

2.4

rCf,L ..... l'.

TREK y,,'l OM ETR Y

In Older to measure temperatures below the u:mpemtu.re C)f boiling helium (- 26S"C) the vapour·pl'es$ure thermometer of helium can be employed. Its" u~ is b?tlt'd ~n the w~ll-knOl."·n fact that the vapour pressure of a. liquid vanes uniquely WIth the temperature. Thus the method consists in measuring the vapour p.ressure of a liquid at the required tempeniture by means or an appili,raUJ.:ij similar to that shown in "Fig. 4, Chap. V. and obtaining the corresponding temperature by means of a calibration curve or a theoretical formula. The helium gas. thermometer and the v~pour-pressu.re thermometer have been used down to about O;75QK. For measuring stili lower temperatures the panllIl [lgnet ic susceptibili ty of sal ts is u tilised,

18. Inte·fDati.wall T em.pcerature Scaf-e.~ W e have seen th at the thermodynamic centigrade scale Is the standard scale of temperature and is givc'll by the helium gas thermometer, but gas thermometry ~nv{)lve.) many eX[leri~en~al difficulties .. On account. of these <lillic:ultie~ In the practical realisation of the therrnodynamic scale the International Commitee in 192~ found it expedient to adof:1t a practical scale k nown as the Interna nona! T em pera~ure S-cale. This scale agree~ with the thermodynamic scale as closely as our ptescn~ knowledge permits and is at the same lime designed to be easily and accurately reproducible" It is Lased upon a number of reproducible fixed points to which n umeri cal values have been assigned and the intermediate tern peraturcs. have been defined by" ag:ret"m~nt OlS the. values given by the (oUowmg thermometers according Ito the scheme gIven below :-

(1) From 0"(,' to 660QC" The. standard platinum resistOlnC€ thermometer calibrated at 1)['. 100°C and the boiling point of sulphur.

(2) From -1 90<iC to 0"0.- The platinum resistance thermometer whlcli gives temperature by means of the formula

~ = Ro {I + crt + rN~' + l' (t - ]'00) t:;},

the fuur constants Leing determined by calibration at ice. steam. sulphur and oxygen points. It. wiU be seen that th4 formula is equivalent to (lO) where € = (IOO}2 2""11/3.

(3) From 660°C to 1(J63c~.-·T'he platinum Pt·Rh thermocouple w here temperature is defined by

E=tI + bt+ d~ ...

and the three .0011 sta n ts are determined oy ca libra cion at the freezing point of antimony and a t the sit vel' and go] d poi n ts,

(1) Abooe Im:;3°C~An optical IJ}'Tometer (see Chap. Xl) cali-

brared at the gold point (1063<>C).

It should be emphasized that the International Scale docs not replace the thermodynamic scale: It merely serves to represent it ill a practical manner with sufficient accuracy for most purpo~es.

:lOlI'l-:
2'la·[~
WO'e
2IlC·
JijQ
oW@
~(!()
\
~OQ
'lO~ -"
EllO -
~m
1~(;J CHART OF FIXED POINTS

-[
~
- lS"4ES Stlblll1:.3tion ~f CQ-l· e.
~
- Sl'i.ti32 f. P. ~t .Mttl~\lr.' -5
~·o~ Wowf= i1
'"
~·~4 'f:r~I!I$IHQt.l (,tNap:!~lOH~O. .. ~
~ e
.0>
lOO'OO B.l'. ~fWatH ~ ~
a 8
2
';
) i::'
211'96. B. P. ~f N~..:htIJil.~CM !
23l'S~ .E1'. P. of TiD
9aB"'3~ It P. o( BeD80iJIlOoO!Jl.o
ail>il'9 F" p" GI Cadmium F. P. ofZi~~

B.. P. I1If Sull!'lmr

~1~I:o( Radlfltu,n

5l!I.'C" Dl'1I[:€l' r,oont ~.rla;t ViBl~le

,. ~-:li. Gao' I

F. P .. ~f A~tlllW1W Jj', r. o(A~~l:Iii~L~nI

BrLJih.t OllE'l'l'Y

I: ,I 1

[I

26

LaGO'C

.~oo

::W:<l

M. P. o1GoJd

F - P- .:;C C'orolO"

Chart of Fil'liedPoims ~C&ntd}.

1052

r. P. QfN~k~

r. p r.f Palladurm

F. P. or f'ia(ir:lIlTll.

2~'L:i r. p, oIIl'Idium

-+---- !ISS\) M. p, of'rl11lS\l(.elj

White

.,

-, \

\

[CHAP.

I. ]

27

1.9. illu.lb'aUol!i of the Principles. of Thermometry.

Absolute or Thermodvnamic

. I J

0" s Thermome ten (Primary standards) ~

Scale

I

Constant Pressure

I

Gravimetric

Thermometers (Compensa ted Air thermometer)

Constant Volume

S econdf.LYY

Thr.nn,o meters

I

f

Expansion

'['11 ermome Len

-I

Radiatlon Pjrorne ten

I .

Thermoelectric

Therm orneters

Resistance

Th ermometers

Boob Recommended

1. Burgess ilmI Le Chateller, Tbe l1ff:'rlSUTem(ml of High Te~nperatures .

2. Ezer GriJIirhs. iV.fethods of Measuri1tg Temperavure, (Griffin, 194-7).

:I. Henning, Temperat!tTfnes:Iung.

"1- A bictiona:lY of Applied Physic~ (Glazebrook), Vol J, Article on Thermometry,

~. J. A. Han, Fu·ndi1mentals of Ther-fnomt!~ry, Institute of Physics, London (1953).

(), J. A. Hall, Practical Thermomet1 .. y, Institute of Physics, London (l953)_

Other Reiesences.

J. Tempe·ta.ture, its lvleastwement and Controi in Science and 11Ui.u,~try (1941), published by Reinhold Publishing COT'pO-

ration, New York. -

CHAPTER II

CA10RIM.ETRY

I. ijll!lDliy 'lIIf Heat...---"It is a matter of COmmon experience that when a hot body is placed in contact with a cold one, the former becomescolder and the Iatter warmer ; we ~fly that a cer ta i n q w.tntlt}' I of heat bas p<lssed from the hot hody to the cold one, . But a simple experiment shows tha ~ when. dilferen t bodi f!~ ,t..re rais ~d to the same tempera rure and ~n. ~llowed..W exchange heat with a~D~ d body the fi na1 temperature ] s different, H we take eq ual q uanuties of water in three different vessels at the same temperature and plunge equal masses of al umin i urn, lead and copper l?l"eviously heated to ] {I()"'C j n to' these vessels, one in each, the equilibrfum wmperattne is highest for aluminium and least fot lead. This indicates that. of these three metals, aluminium can yield the largest quantity of heat and lead th€ least,

For lIH:;.~~m1ng quantities of ht:.at we require a . unit: The q uan ti ty of hea r reel uired to raise the tempe:m ture of 1 gram of water through 1°C is called ~he 'calm-ie' which is also the thermal uni t f OJ: m eas Dl'ing q uautities ot heat. The 15 "C co. lor ie is deli ned as the quantity of heat which 'would raise the temperature of one gram of water from H.5~C to 15_5°C find has been recommended by the In ternation 111 Union 01 Pure and Applied Physics (193'1) lor adoprion as the standard. In Britain the Rritish therma! t.mil (writttTl R Th, U,) is rH quencly employed- wbith represent~ the quanri t}' of heat required to raise 1 lb. of water through 1°F, The stJer.i/ic hra; of any substance l~ defined M the number of calories tt~'1uired 10 raise 1 gram of the substanee through I "c. This is strictly speak ing not the same at all tempera LU res. Thus if ,l quantity of heat Q raises the temperature of m graIns of a substance from (J to II', s, the mean sped f c heat of the ~u bst ance, U gi ven by Q;[m (8'-8) J ; while if a quantity dQ raises the t:f!mpcrature hy dfJ.

!!l{" sped fJ (' b eat at ttl c temp erature I) is ~~O.

The th~?'1'fWJ. cajmcity or water .equ£ualent of a particular body is e::q u al to the prod net of its mass and specific heat.

2. MelhliHl~ in Ca!ori:m6try.~Tilc Eollowing arethe chief methods ('mpkryed in Calorhnetryt:-

(1) Method of Mixture!;.

(2) Method o~ Cooling,

... Sometimes the Ib, c.alilrie or Cfn:~igrade heat tmit (C H, U.) Q'I" ~elltlgtaclc thermal unit (C Th, n,) is also used which represents tn(.; q<1<1:l'Itity of beat required to rai se 1 ItJ.. of water throoIJgh l"C

t A ~ood aceoum of tll~~(! met:hod9 is given in. G!@zebrook, A Dicti~jl~ry of An/jed N~J!!iif8, Vol. 1, aL"ttc]e on "'CaTorimet:ry';_

29

(H) Methods based on Change of State or Latent Heat Calorimerry,

(1) Electrical Methods.

I n the following pages we shalf discuss these :m ethnda one! by OIl~~, Lindet each. of these we shall consider uhe various form~Clr experimental an"'. ngeme. nt th.at have bee~l adopted. Solids and l.iqui(b w iJl be considered first w h ile gases will [)e~ake[l :up I ater AD the chapter.

1. METHOD OF MIXTURES

3. 'Theory of tbeMe:lbd.- Rcgrm ult 8 about the year ] 840m <Ide .l careful S bud)' of the Method of !l.iI ixtures, and by care and skm obtained results of the highest 1I.OCUT1icy. The principle or the method i~ to impart tile quantity of heat to bemeasured to a certain mass of water contained in a vessel of known thefma]C<lpaclt'y and to memiLlr'€ the r_isc Ot remperatl~n; produced, Thus, if a ~ub~tanQ~ of nHl~ fflh specific heat Si 3JJd lI''Utlal temperature 611, be' plunged uno m~ b'iams of water at tem.perature e~, and if W be the thermal capa('i~f or the calorimeter, 0 the final temrel'atun:: of the mixture, we have, by equating ~he ~e.H lost hy the substance to the heat. g'<lined Ly the water and calonimeter;

Ii1lh (Ol-fl)=(m2+ W) (O-e~}, (ma_!_ W) ({l-8~)

or s -, - ~ --.--

l- m1(t71-@}

'This gives the specific heat of the substance. Vafiou~ oorrect ions are, however. necessary for heat 'is lost by the fiyste:m hy r ouduction, convection and ra.diation. Thus (or & we must put f) + 6 (J wl ie re t:. e is' the correctio n,

4. Ramail:iQD Correctioo.-In most experiments 011 calorime(]I'Y I.h e ~ lcula sion Of chis loss of heat d l)e to radia tion is irnportan t. The radiation correction m.ay be accurately calculated with the help of Newton's Law of Couling (Chap. Xi) w hkh s rates tha t for small diff[!rem::&; of tempctatufril the hea r 10s5 d Lie W rad iation is proportional to the' tem pr!:[".a .• l ure diffcrence be ~wee[!l. the caTotirneter and the surroundings. To illustrate its application let AB (Fig. I) denote the observed rise of temperature during an cxpnrimeut, Be the observed ·cooling at I lip end of it, We have to calculate

. . .. Fig, 1,-fi1l,lstratioll al' RSJdirJ:tioLl

the true lise in temperature. DIvide Correcelon ..

the abscissa into 11: equal interva]s3h,

8/, ..... at~ by means of ordinates P!M1> P~)"f~, ... P ~Mu such tll,at

.. Henri Victar Regtlau1t (I8Hl·1ID'8), born at Aix~!a-Chaplin~, h:ill tOSlipport bhmdf whi]'~ yOUng, He jofn;;;.d tile Et>ole F'olyteclllliqlle .ill Paris and later (Ill ill UNO h~ was ~LG~PO[l1ted P~Qf~59.01" in tn~t Poh'te~b[jjque. H~ dld many cl assie I'l·~~n.rdl~s em llrnt.

30

CALORlME'TR Y

[ CHAP.

the small portions AI\, P1P~", .fI "-lP~, may be treated as .s,traight. lines, L,et us. measure temperatures from the temperature or the ~1,l rroundings, If 81, (J2', , .xlenote the m,e.a n tempera tures during these intervals, 81', (V .. , the temperatures at the ends of these intervals represented by P1M1, P2M2 .•• , then the temperature diminution due to radiation in the Interval 8h. is kB1ot1+ If {)IN, (}~", • , , denote r.T1e tr::mpe.I'ature~. ar jhc ends of these intervals had there been no loss due £0 tad iat:ion, '~hen

(lI" = 81' + i;(jlJt1

f)2" = IN + kOl8t 1 + kel/J.r~ f}n"...=! 8n' + 11,(81 8; + e~M2 + .. '. 8~o.tll) = 0 .. ' + k(area of the curve ABM"A)

= 8 ~' + k J ~ ~ dt.

0) (2)

(3)

We can thus correct any temperature e;/ it we der,ermcne (he area AP nM~A and R ..

Au alternarive method ~.~ to plot the' upper curve from the lower curve: by H;JCTea$mg ~he ordinate M1PI to M1P{. M2P~ to M~P~' etc. where M,l P n~ = 'h':. M2P 2' = fN', etc, The highest ordi 11 ate on tLEc' curve (v.~z"'. DE) grves the true rise of l.et:npetature in the experiment corrected for radiation,

To determine k we ha~'e t~ obseryc the. rate of co_?ling at any temperature. The curve Be (Flg. 1) rs obtained experimentallv [or

thi '.' I' dO. 1 •

l~ pL!TpOS~, rWm r lIS Iii IS (;:I culated for an)' mean value of (),

Kow II - -~ :~ , hence k Is known.~

Another method caIled the adiabatic method is to eliminate the heat hy continuously adjusting- the temperature of the bath cndosiJ)JI ihe calorimeter to be always equal to the temperarure of the [alor]: meter i tse 1£, t

5: Specific Heat of Solids.-For linding toe specific heat of solids by this method the requisites are a GilJorimeter with an enclosure, a thern,}O~ete~ and a hea~r, .Fur wor~ a. t ordinary tern.po.ratures the calorimeter IS made of thin .c;apper, 11ld:,e]r;la!tx! and polished on the. outside, so as to reduce radiation losses. It js supported on pointed preces of wood Or by, means of thread inside: a larger double-walled vessel whkh has water maintained at OJ. fixed temperature in the

, . '" A ~.L,mple b~t l·O'ugh method sometimes ado:pre{l is to add to the oiJ!;>[r,.ed rise half the eoolmg C?bser\md at. the hi.~est lernperatm'e in a th'l1e equal to the dura bon of thf! experiment, Tbl~ rs based On the assl1rnptian tllai the averago {!"'c~ss of temperature of the calorimeter ~ver the .~tl:rrnunding~ may be taken to be 1.1arr the final excess, heme the coo hll&" during the expcrimenf is half the cooImg at the final temperature.

~', For other methods sec Glazebrook, .1. Dj~~fiomiry of AJ'filj.p.d P,~~~'ics, Vol, 1. pp, 61-63.

,

1 "11· 'The heater is 1 steam-jacket ill

,I,III11I..t1 space L(:twe~n t re wa . S. It. '. ", ... ,r T

wllil h the substance 18 heated by steam without be~O~Ui\~ v;e~~ An ( ,i I I m III m::1.y also be used. The tramfer~nce an~ radia non e~:ru ~ rn.us~

d 1... itable : ._1, .- I devices as In RC-.Tnault!; da:,slclU

I H' fCfIlice .,y S~Ut3 e mewaruca u ... > '"~ e

I 'x pel iments. .

For high teUlperature~ the sc:iicl substance is heated ill. <In el~drlc

\Ht •. ' t.- "O.·f at T~lgh •. ~·m·pel"at1Jres employed a fm nace

III I 1I,If I', .. , It.lLc In L1IS W d'::' _. r., ." .... ' . , . r

11.I\'ill~ .. piatiUIUU coil w~llnd on jt.s 8Urfa,Ce. Th,e substauce is supIlqH['d jn~jde the furnace ~n a loop of pi.atmum wrre ,I I Id 18 allowed to drop mto the ca~oruueter by a ~uiLahk ]nechanical device. Change in temperature i-. measured hy a resistance therm~meteL _ For wo:'k .u low temperatures the substance IS cooled d~wn l}l :1 II uartz va<;llUm.;,"f'Sse]. surrounded ~Y 1H1Uld arr hclnre being dropped into the calorimeter.

A W bery and her Grifiith~ hav~, d~ term ined tIl e ~ I )e.:c.i fiC heat of sol ids an,d moite~] liqu ids as wdl as rheir latent heat by 1.1Sll1!5, an. lD1pr~ed. ap'p"ratl1S hascd 011 the me rho ~ of m rx lures. Th is IS discussed

in Chap. V.

The use of water as calorimetric liquid has several draw backs, I ts range is . small and specific . D heat laT~ so that the rise of temperature is small; Iuriher there i~ considerable 1·1S1. of' some water being

lust by evaporatlon. For these reasons several workers [lave replaced it by a block of metal. The copper block calorimeter devised by N ernst, Li ndemann and

Kmef is e.x.ceedlngJ.y convenient for low t.~,mper!tures. ,

it crmsists (]if it he",:,,}, copper brock K (FIg .. 2} ..

cemented with Wood's, metal ·too the inside of a Dewer flask D. It i~ essentially 11 calorimeter based on the method of mixtures in which copper replaces wate.r as tb e standard substance, The heated su bstance IS dropp-ed into the copper block tbr,ough the glass-tube R aud the change in t;mperature of the l~tt.er ;IS read Fi~, 2, _

1) n thermo-couples T, r, w h. ose one end IS. lllS1d. e the CuCPIPer. B ~ock

h tl ~.. h hi k C' a orimeter,

w'pper block K and teo rer eDCl. HI t. c oc..','

The €Oppel: block on account of l,t~ good ,conductIVIty keeps th,t' temperature uniform, [aeger and ]l1S co-workers hava emploved this method to determine tfie specific heat or \0\'", P~,. O~, Rh, Ir, etc .• to. about 16,OV"C wi tlla high degree of accuracy

II I

SPECIFIC HFAT of'" LIQ,t:IlJS

31

c

R,

.D

T·

. 'Ii, Sp>ecilic Heat of Liqu:ids.-Specific heat of liquids which do no rvea cr chemical! y with water or any other 811 bsra nee of 'known specific heat may be obtained by dlr,ecL mixture, For liquids which react in this way Rc-gmmlt used a different form of appar~tus, The liquid. v.~as not aUm~'?d to mix. with water bU~W:'-5 admitted whe·~. desired mtoa vessel immersed In water. 'The Iiquld was first heated

CALoRIMETRY

[CHAI',

and then forced into the vessel. The specific heat could be calculated <Is before.s

. (\.no;her class or c.xper]~ent:l for measuring the, specific heat of Iiquid S Involves the expendi ture _.u some mechanical energy and m easuremen t of the (Jol1seg. uen t rrse of rem perature. To thisclass be~on,g.Che _das.8ical experiments ,of Rowland for :dete~ini11g. the mechanieal equivalent of hest. Theywill be des en bed III detail in Chapter In

2. METHOD OF COOLING

7. This met~od, perfecred by Dulong and Petit .• is found to be fJ:ost convenient Ior liq_lli~s but unsuitable for solids owing to varialions of temperaturewithin the latter, The method is based On the <l.ssl.lml~ti9n that when a body cools in a given enclosure on account of radiation alone, the heat dQ emitted 1 n the time dt is gI ven by the reb lion .

dQ = Af(O) dt~ ..,. ;(4)

w11en; A depends upon t.he. ana and the radia.ting power of the body, frO! IS an unknown functlon of f), t~,e excess o[ the temperature of tile body aver that of the surroundings.

If this produces a cuojing' of the body through - df), 'we have dQ=-msdO,

where til and s denote the mass and the specific heat of the bodv respt:<tiyely.

Efj na ting these'

two expressions for dQ we bTCt - msd(} =::; Af(O} dt,

r I dt = _ ~ J f} ~ dO

J 0 A '. Q11(8)

t - ms r ~l d8

- A j @. f(e}'

wbpre t is the time the hody take-s in cooling hom Ole to O:t.

SimilarlJ' for another substance to cool, lhrough the same interval 'Of temperature

r 0= mJ, J:: J1~ J

If ~ . A~ i.e. the surface area and the radiating power of the rwe bodies be the same we have from (5) and (6)

Or

Or

(5)

(6)

m:l' m':/

T=r'

(7)

~f m.ass.t=s. m, m' of two liquids be contained. S'uccessivcIy in a. calorimeter of thermal capacity Wand the calorimeter suspended

* For detail!; see Preston, Thcorj' of li~at:.

I1.J

33

METHOD OF III[ELTlNoG ICE

inside a vessel kept at O"C by immersion in melting tee and then observations of the rate of cooling taken, we have

W+ mt foV..L, 1ll':/

(8)

. --e - = -t-' --

IF One liquid i ~ water (s = 1) t the speci fie heat of the other .LS thus determined from a knowledge of t, t', m.; 1n'.

The method is sometimes employed for determining the specific heat of liquids but is not capable of any great accunlc..]' and is mainly of historical interest,

3. METHODS RASED ON CHANGE or STATE

8. Thesemechods may he subdivided into two: namely the method of melting ice and the method of condensation of steam, These methods were of real advantage in the last century when accura te m easuremeu ts 01 temperature were ] m possi ble, bu C 'Ii'll th the recen t development of accurate therrnometcra and electri cal hea ters they are now less ;i n use, chiefly on a coount 0.[ their inhere nt defects, Th e second method IS, however, very convenie n t for determining- the specific heat of gases at constant volume. and hence retains its importance.

9. Metb:od of Melting I~.- In this method the heat given out hy a eertain su~s.t<lnoe in cooling is impart:-d to ice and measured by the amount of ice thereby melted, Thus 11 M grams oi a substance of specific heat s and initial tempera Lure () are able to melt m grams of ice when placed in contact. with the latter, the specific heat is gi,,'"ell by th e reb don

Mse _rnL,

(9)

where L is the latent heat 01; fusion, The earllest forms of the app;]. rams as devised by Black, and by LaYQi81er aud Laplace were Iiable 10 cause considerable en-or. An improved form of the r:alnrime~r was later devised hy Bunserr" 'which will now be described.

10. BUDse.nJ!'I Ice CaJofweter.-In chi~ calcrimeter, the li .... ater produced by the melting of ice is not drained oft but IS allowed to remain mixed wi th ice and the resulting change in volume is observed, The calorimeter is illustrated in }·rg. 3, P: 34. The test tube A is fused into the cylindrical: glass bulb II which is provided with the gLm stern C_ R is nearly . filled w.ith boiled air-free water and the remaini rig 8 pace and the i rem is filled wit11 mercury. Th e stem term inatcs in an iron collar D containing mcrcu.ry into which a graduated fapiliary tube E is pushed so that mercury stands at a certain. gr:lJuation in E.

In conducilng an experiment a stream ol alcohol, cooled by a lreezing mixture, Is fir-it p<.m-ed through the test-tube A until a cap

* Hobert \hli[hdm Brmscr; (181 t-1899), born at Gottingetl. studic([ a~ GOttit·lg01l.

Paris, Berlin and Vienna, He was professor of Chemistry at Breslau and neiddb<:r~, His important researches an: 011 spectrum analysis, B_l:!lSen cell, grease-spot photornctcr. gas burner and ice calorimeter,

" ,I

CALORIMETRY

[ cUM>.

of ic.;e F IS formed round it in B.

The "I'bole instrument is EMU kept immersed ill pu.re ice at ijOC fOT several days uIl 0111 the water in B is frozen. It is then ready for usc.

To. calibrate the scale on E, 1 ~'L a mass rn of water at a ternperature {lcChe poured into the test-tube- Some ice in B melts and the resulting contrartion of mercury say n di;,:i.li~o11.S on E is observed. Then il a rec~&51(m of mercury by I division corresponds to q calories of heat

me = nq; or q =mOjrr. /(H"I) Next the su bsta nee under investigation .. pre-viau.sly heated to a temperature 8'! alS dTOl~ped into some water at U oon.tallled in the: test-tube A. Then if lVI,

Fig_ .3~nUl1l;l!il'!< Ice Calorimeter. s denote the mass and the s.pe.-

cific he-at of the substance respectively, and n' the observed reCCSSIOn () [ m e.n::ul'Y thread in E, we have

lr[slY = rr.rq~

n mn'()

s = ~WO' s= MnO'

(11)

'I'his gives the speci fic heat ~f the Suu5ta.llce: . The specific .h~at of rare metals \.\1' hic.h can be had III sma~] qu annues can ~c readilv {()l111d by this method. The appar~tu~ IS, however, ~l~t capable i of great accuracy. A fundamental obJec~lOn to ~bc u~<; of. the . ee calorimeter rests on the fact that a grven specimen of wa~eT can freeze into ice of different densities.

II. Jruy's Steam Ca!lo:rimekr.-In the steam calorimeter devised by Prof. J.ol), in l886 thc!\e~li. necessary to raise the temper~tme of a substance from the ordlnarv tern.perature to the tcmpemtulf~ of steam is measured by the amount of vapour condensed into water at the same temperature. It consists 001; ~. thin metal, enc~05ure A. (Fig. 4) I double-waned and covered with cloth, wJych is placed beneath a sensitive Iral ance, One pOlin of the balance l~ remove~ and from this (TId of the beam hangs freely a 'wire w Stlp',POrtJIlg ~ pbtll~um pan inside the ~ndosure. Th:- substance whose ~pecifi~ heat ~s 1"e~.~rc~ j~ placed on this pan and 'Ii~Telghts added on the ~theI pan .tlll balance IS attained, The temperature of the enclosure is o~served hy me_~u:ls. of a thermometer inserted into the chamber. and In the rueantrme

II,]

IOLY'S SI'l1AM !;ALOltIMETJER

35

steam i~ prepared in the b~ile.r. H. is then admitted suddenly into the chamber through the wide ope:rung 0 at the wp and can escape

Fig, 4,-JQly's Steatn Calurhmter_

through the narrow exit-tube t at ~he bottOm. Steam condenses on the snbstauce and the pan, and w,elghts are added on the other pan to mamtain the equilibrium, VI/hen the pan ceases to increase in weight the readings are ~oled and the ter.n.p~ratun~ 0.1 the s:eam read on a thenuometer. Durjug rhe final we3ghmg .. the. steam IS 31~0\",'ed to en ter the cham bel!" through a narrow escape- tu be $0 as n 0 t to distu» b the pan. The weigh t beco~les practica 11 y con st,u; C . in four or live minutes though a very ~dQV,' ,m':reaSie of at~u~ -1 mllligrams per hour rna v be observed due to radiation, Th e difference between the two

wei'ghings 1:)1 ves the weigh t of. steam cond.emed... ..

U W IS the weight oE the substance, w the increase ill \~gb.t of the pan, Oi the initial (cmpttatur~ of the enclosur~. O~ the tempera. ture or steam, 1{ the thermal capaCity of the pan, L the latent heat of steam, s the required specific heat, then

H1s(82 -(1) -1-k(e2- Od=wL. p 2)

h is determined from a. preliminary experiment without any substance on the pan and t11U;!i the specific heat of the substance IS fcnnd,

For great accuracy various precau.tj~ns an~ oorrect]o~.s <Ire necesH';'Ll'V.. Steam condenses on the suapending WIre where H leaves the chamb er alii d then surfaee tension renders accurate weighing d~.fficuI t, A ihin spiral oE platinum wire in which a curr-entflows. usually snrrou nds t he suspendi ng wire jm ~ a bove the opening. an d is lTHH]~ to glow so that. the heat developed is just sufficient to prevent condensation, A rapid introduction of; steam is necer.sary in the early stages, IOl' steam also condenses on the pan due to radiation to the cold air and the chamber, thus causing error, This is, of course, partially balanced by radiation from the steam to the substance later,

Further w does nut accurately represent the weight of steam condensed since the first weight js taken in air at fh DC and the second in s Learn a t r}I~ ac. AIl the weighings must be reduced tn vacu urn and then the increase in weig~t calculated: Specific heat ?~ rapsu bstances can he Jound b)' ehis methorl sm oe small qunn~lUes Or ~~c .!inb8t~nce are ne~de~ but a. sensitive balance is indispensa~le, 1 he !>p~clfic heat nt liquids and pOW.de:r5 can be j'Ol~nd ,by enclo~lll~ them In glas..~ Or metal spheres whose thermal capacu:y 15 taken mto account. Gases can also be similarly enclosed, but then the modified form of the apparatus-the differential calorimeter-is used.

12. The dilfereotial Steam CaJDmn.eter.- In this form invented

by Prof. .10])' in 1889, both the balance pans are made exactly similar and of equal thermal capacity and hang in (he same s tC,"-lTI- cham her (Fig·, 5). The substance to be tested Is pl~ced on one pan and the excess 0 f steam con.dens.ing_ 011. this .r= over that on the other pan I~ entirely due to the su bs ranee. Thermal ca paci tv of the pans, ra dia tion from them. :l 11d .. (I other sources of en-or commo n to them are eliminated, the substance bearing onlv its own share of the error. The cilief use of this apparatus, however, consists II! the determination of the specific heat of gases at constant volume, The p;] ns arc then rep laced by two equal hollow £pher~s of copper furnished with: "catch-waters" (£hown in the figUl'e). One 8phete is filled with the dri,eu experim~n tal gas at ~ ny desired pressu re while the 0 ther 1S emp t y. The-se spheres aremnnrerpoi.sed b'y adding necc.ssary weights m. which rcprellem the mass of the contained gas. Steam

"-( is admitted and condenses on the pans.

A larger amount of steam condenses on the sphere containin$ the gas, the. excess, say (1.,', giving the 1tJllOUiH. of Flg. 5,-The differential Stearn steam required by the gas. Nnw the

Co'l.lol'l.L[trt~r. specific heat at constant volume c. may be calculated lrom the C{p.Httinn

m(.~ (e~-81}=w4 (1 S)

where O~, 01 arc the final and initial temperatures of the chamber, Prof. J oly used wpper spheres of diameter (i,7 e111. and weighing; 92.2 gm, and employed gases at different pressures, Con-ection s wert: applied for the following :_

L The expansion of the sphere due to increased temperature and the consequent work Llone by the gas in expanding to (his volume,

II. J

37

') The expansion of the sphere due to rhe increased pressure

lit the gl-f:S at the higher tcmpe:r:'Hure. , .,. ..

.'}_ The thermal etlect of this stn~tduHg of the material 01 which

I he ~fiherc is made, .

4. The increased buoyancy 01 the sphere due to its increased \ olurnc ill the hlgber temperature.

.5. Th e II neq II al thermal capacities 0 I' the ~phere$.

U. The reduction of the weight of water condensed to ib weight UI \'aCUlUH.

Dewar has devised calorimeters based ou an analogous principle iu which he employed OJ liquefied gas as the calorimetric substance. The heat to be measured is applied to the Iiquehed gas whereby the liquid C\ aporatcs absorbing Its latent heat and the volume 17 of ga.,~ thus pluduL-ed .is measured. The heat communicated to the liquid is then gL1icn DV V pL where p is the density of the vapour and I: the latent heat of ~aporiza1.ion of the substance. Using' liquid oxygen and liquid h \ J~·ogen the appHratm; can be a dopted for very low t.empe ratu res" III the C;'l~C of hydrogen I Lt.,01 vapour <It N,T.P. corresponds to a v l~l~· srna 1I quart lit y of hea t (abou t 1/100 calorie). This method has iJ!:CIl utiljscd Em: measuring the spe(inc heat down to very low te-mpeI ;~tUIT5, Th€ experimental substance (wEd or liq uid] is first kept in .j constant tt:mpt::mture. hath (say (lDC) and then dropped into the r aloi imcter coruainiug Equid oxygen or liquid bydrogen.

4, ELECTRICAL I\.rETHODS

13. The electrical method was tirst employed by JanIe in his <l!tempts to determine the mechanical e(:i.Ul'I ... alent of heat. The electrical methods at present available may he subdivided into twO':(I) Method based on the observation or rise of tempera Lure. (2) Method em.pl,{)ying the steady-Ilow electric calorimeter,

"\ \. e shall first consider the ap plica tf on of these meth ods to ] jquid~ because historically the method was first app]i{~d to them.

14. IIIlet&ods Based! en the Rise of ·relnperatuff~.-FoUo-.\!ing Joule this method was adopted by many workers the chief among them being Griffiths" Schuster and Gannon, \OV. R. Bousfictd and \IV. E. Bcusfield. Thev employed this method for determining the mechanical cq uivalent of heat and found that it was capable of the highest ,m:LLl<lcy" '!'he same arrangements may be employed {or finding the ~pecific heat of liquids,

The principle of the method is to generate heat by passing a current through. a conducting wire. 1£ i is the current through the w ii c of resis ranee Rand E the pol::tn tial differen ce a cross its ends, the ent;rgy spent in :1 time t seconds is E£t ergs, provided F. and i are -xpressed in electromagnetic units, If this raises the temperature u f .1\1 grams of a: subs ranee by {iO D, the speer he heats 0 r the 81.1 bs tan ce is fl:iven by the relation

Eit = IMs an, . (14)

where] is the mechanical equivalent of heat [see Chap, HI). If E

I

I~

I

I I

u.]

$T£ADY-FLOVI,I };LEGTR1G c;;..LORIME .r ER

39

[CHAP.

current near the thermometer. The leads L, Land p, P :i!-'e attached to this tube of copper, the former for il:tI'O~u,dng the heating current all d the latter for measm:ing the potential difference across the ce[ltr~l tonuuctor in terms 01; a. standard cell by means of an accurately

Fig, 7.-.5tee.dy-llow Electric Calorimeter.

calibrated potenti01:l1ete.l", The potentiometer also ~er:res to measure the heating curre n t i by fi1~asuring the paten !la 1 .dl !Terence . acrossa standard resistance included in the same circuit. In order to d iminls h the external loss of heat the flaw tu be 1 ~ eucl osed in a hermetically sealed glass vacuum jacket surrounded by a constant, tc~perature bath. Neglecting small corrections the general equation IS

Eit=JMs (02-f11)+JIlt, . (H5)

emploYing the same notation as b-etrn:e, where h denotes the heat Joss p~,r second on account of radiation, and 01> tJ~ the temperature.5 of inHowing and outflewing water. The time of How t in ~hese expenments was about 20 minutes and was rec.orded automatically on an electric chronograph reading to 0 . .0 I sec. The alas's of water M lvas measured bycollecting the outflowing water and w; .. s about .1)00 gm. The difference in temperature o~- 611 was from 8" to [we and was accurately read to Jl(n "C, The heat loss h was vel:;t small and regular, and was determined and eliminated by suitably adju_~ting tile electric current w as to secure the same rise of tempera.ttlt€ for different rates of flow of the liquid. Thus for two rates of flow we have

Elilt=JMI·t(f)~-8~) + Jill, E~~'~t=.JM~(e~-81} + ]M, (E/, -E~i~ ) f.

J=M M)O .

( 1-. ~ (.'~-Ods

Since ~he tempera rures at e'Ve11' point of me a ppa.ratu s are the same in both experiments the heal loss h must also be the same, The specific heat s thus determined is the av(!tl'lge sp~c.ific heat for the interval UJ and may bc taken as the specific heat at the middle of the Interval,

The l!l"reat. advantage of this steady-flow electric method j~ that no correction IS necessary lot tile thermal capacity of the calorimeter

is expressed in volts and i in ampere:; the energy spent is g"i\'en in Joules (1 Joule = 107 ergs.) ,

Any two of tbe quan~i~ie.sE.> i ~nd R in~y ~e measured, ll;ll$ gh.ing three meili. ods, Gl'lr.h.~hs). m his dctel'ml~1atI~:m of the sp.~Clfic heat of water, (hose to measure E and R which IS rather difficulr for R must be measured during the heating experiment. G.iffi~hs: work is im porta nt since it fir&t esta blished the fact th 11 t the electrical method can accurately give the value of J in absolute units. Schuster and Gannon. measured E and i .

. Jaea:er and ~tejllwehr have applied this method to de;erID1ue the mechanical equivalent of heat and hence aha the specific heat at different tempeI>a tu res. They eJT1ployed a large mass of water (50 kg.) and consequently the thermal CaP.acily, o~ the, vess~l was only about 17a of that of the contained water. A sectron of their appar'a_tus is shown in Fig. 5. AA is the cylindrical copper calorimeter lying on its side and properly insulated from the surrounding constant-

temper~ture bath EV .Orl the upper SI de a: t 0 there 18 a hola for the introduction or ehe heating coil H> the resistance thermometer and the shaft t 'which (hives the stirrer SS- A current or about 10 ;}mpere5 was allowed to flow [or six.' minutes through the constantan heater II or 8 ohms reS1Sranee and the rise in temperature was about L,l°C_ In these experlments an ac-cunt.cy of 1 in 10;000 was aimed at and hence the results are very reliable.

15. Th.e Melhod of

Steady-flow f:]ectric Ca)orimerer.-Greal accuracv was

Fig, (i-A Section 0.£ jaeger and attained by Callenda~ and

Stcinwchr's Calorimeter_ Barnes h'r~ using the steady-

!lo"w electric ealorimeter shown in Fjg. 1. A stead}' current of the experimental liquid flowing tllTOllgh the narrow glass-tube t, about 2 m.m. in diameter, b heated by an electric current flowing through the central conductor o;F platinum. The steady difference of tempera-

. ture 861' hetweenth.einfi:uwing and Otlt-flowing water is measured by a pair of platinum thermometers Pt~ Pt at each end connected differentially in the opposite arms of a bridge (If Callendaj- and Griffiths' type. The b"']~b of ea~h thermometer is surrounded by a thick to?'J~r tube of neglrWble resrstance auachcd to the central conductor. Jl his on account or its good conductivity keeps the whole bulb at the temperature of the adjacent water, and due to res low resistance pre..-cnts the generation or any appreciable amouar of heat by the

[,

40

NEJlliST VAt:U vI\.:( CALORJ Ml'.TER

iCH.AP,

since there .is no change of temperature in an> part of the Instrument, Care must. howo::::vtl·, be t~ke::n to secure perfect. steadiness, as it is pladrcaUl' impossible to correct for unsteady conditions, Further, since all condi tions are steady, the 0 hservations can be taken with the highest degree or a ccuracy. T here is no question of thermometric lag. It is essential, however, that the current Of water be thoroughly mixed otherwise temperature over <to cress-section of the tube wHI not be uniform, Thb, is secured by havin.~ the central conductor in the [OlTU of a spiral instead of a straight wire.

Callender and .Barnet; used this method [;0 find the specific heat of water at various temper-a mrcs, The! r results arc discussed in the next secti0tl- Callendar found the spe rific heat of mercury bv thh method, The een tral conducting wirewas dispensed with, t.he flowing mercury itself serving as the mndudm\ Gdffiths employed this method to determine the specific heat 01' aniline over the range 15° to 50°C.

Hi. Spoedli~ Heat ·of Wate:r,.-In ordinary GdOrLmo/t:ric expecimears the specific heat ol water is assumed coustanr at all temperatures and. equ:::Il to 1.1 ni ry. Accurate iuvest.igatio11,8 o[ th e last' section, ~how. that it v~ries with temperature. The first accurate experiments in tim OCIm1.ectIOl1 were those of Rowland in connection with his determination of the mechanical equivalent of heat (Chap. 111),. He argued that if the specific heat of water at all temperatures were constant ~his me-chanical equl valent, mu st COmC out a cons tan t quantity even:

If ' ... ·e used wa ter at diflcren t temperatures, The vari ution i u t he value of I was due La the variation in specific heat,

'1 abl» 1_ Specific Heat of W-afer tit different t~npetfdUf"es,

The other accura te experiruen ts on the su b j ect are those of Callendar and Barnes {sec Hi) and of Jaegel.' and Steinwehr (sec. H) . Both 01 them determined ace urately the specific: heat .of wa leriilt various temperatures, Their values are given in Table I togclhe< wi th the_ v~lue. S 0 bta i. ned ~ecemly by 0 sborne, Stimson <I. ud G il1~iny; at, the 1\ ational Bureau of Standards, \.'Il asrlll"lg1;Q]l" 111 eohimn :Jothe spedfir- heat is expressed in international Joule8~ per gl'<nn pe!· 0(;,

J!""~2l--

'$ . -- osBOR~asT+DN, &:: GJN~rr~Gs"T----J

i. <I.21·r\.\ r '.. ---- - )Aoo H ... Fl ... &. Si.-Ell-~ NWl'.NR /t

.rJ, - - --- H RNE;';-- V

'5 -, ~ /

2 ... ,~u' \ ·row·LANO

~. ,.\ •. ·~AEl'l ~~i~R'S /7 ,.... ~ ~

z ',{\ I j / /'

- ~'LQI----+":.-----+---l----+· -- ... - ......f----,,j<::.--:>I--::""_-!---l

~ -" J ~/, .> j I

:r: ,.'t'-.. -'~ ~ ~I

u 4-1er--+-~~:-=:f:::;==-...:j:?";":T--:-i .. -"=--t--+~·

~ ~>+-"-"1-' 1 ~ ,.

~ 4"17 .... '~'l -._ j.-.-'~{

W 1(1' nr ;R' ~b.'--~W'!:-:--·-;!;ro':;--~7:±0':-----:9Il'~.:'""" ~ 1(tJji'

~n1U';~

FLp.;. 8.-.;.';!,)edl1Jc Heat Curve for Water,

The results ot all these three IlTv[!:);tigatioIls. are plotted in Fig, ~, It will .be seen that the values obtained by CaBendar and. Barnes he som ewha t wide of the others and a ppeaT to be less reliable chiefly on account of the uncertainty in the values of th,edectrica} .unils eDlp~oyed. From these curves i~. is evident that w"a~erh~& ~ IOH"llmU11J spe eif c heat a t a bout~4 o c. ItIs 0'0. account of this vanauon tha t 011 p. 28 the calorie was defined with res pee! to 15 "C.

SPEcu'rc HEAT OJ" SOLIDS

17. Rise Di Tempor,abInMetlmd.- TIU;! electrical. method was fLr~t applied to. ~oli(ls by Caede ill, 1902, K II. Griffitb~ and E. Griffiths dete:rJ.'Ilinc:d the specllic befil:t 0[' many metals over t.he :range _ HiO" to + 100" c. The 511 bstance w~s used in the form of a c.alorimeter aud was first cooled below the desired temperature. Electrical energy was utllised in heating the calorimeter and the temperature in dicated by a. resistance thermemeter. 'Thecalorhueter was e nclosed ina constan t temperature bath whose temperaturewas kept cons rant to l jlOOdl of a degrr2!e, 'Corr·ection W1l5 applied for the heat lost by radiation,

.,./18. NerJl;9;I Vae.:llum Cafofim~ooli.- A dHIe:renr form of the apparJiius. known as the va~·%l'!Lm uelon:merer, was used hy Nernst and Li ndernann .for measuring tJ.1LC specific Ilea ~ at very, low temperatures. This differed from Gaede's form essentially in haVlng the calorimeter suspended in Vii ClM;lm _ The results achieved with its. a id ate of great t heoretica 1 importan ee and hence their app:aril W 5 will be considered

~, 1 Jfn~. J<JI1[e = 1,OOM1 X 10' ~~g:;,

Temp. Callender Jaeger ~lld Osborne Specific beat
°C & Tlarnes Skin"'~'dLi" Stlm~on& in int, J~lU 1~3
G[mlin,gs (0, S, & G,)
I·
0 1,(1093 {l.O(l5) 1;0076 , 1,2]69
5 1.0017 } ,002"9 1.0039 4,2014
10 1.0019 },0013 ],00]5 4J914
Ej 1,(1000 1.0000 ,-,moo 1,IB50
2-0 0.9988 O.,99{)O O.Q9'9J 4,1811
25 0.0980 O.~}~l83 o.snes 4 . .1788
BTl 0,9976 0,9979 0,99B2 4,1777
35 0.9973 O.~J978 0,,9982 4.17'74
40 0.9973, 0.9981 0.,9983 4,1778
45 (l,{H}7.i) 0:9987 O.99Kf) 4.1787
50 o.m;l7s ~l99'96 0.9988 4J799
50 0,9987 0.9997 4,J830
70 r,ouoo 1.0001:1 4.1888
80 ],0017 U102.? ,tl%6
90 1,OU36 I JlO46 4_2TNj
100 1.0057 1.00/2 4.2152 in some detail, Tor good conducting solids such as metals .he talorilTIIE::ter shown in Fig. 9 Ca} wa.'j, used, The ~l1Ibstancc. whose specific heat. is to be deter-mined is shaped into a cylinder C, havingaeylindrical hole drilled almost through its enure le.[lgm, and a closely fi tting plug P made fill it from the same material The su l:m~ance here acts as its own calorimeter. The plug is wound over wIth a

Fig, 9,-Nernst VaC1J1Jm CalQrimckr.

sp inti wire of pu:n:-~t r lati J1 urn (shown dot ted in th e figure) which is insulaLe~~ hom. it by me~ns of thin paraffined paper, and finally liquid iJa_udIin ].~ poured over 1 t. The upper fan of the p]ug is somewha t ,t~rckcr th~!l the Iower part, thus a. J;f0()( thcnT'Ial ~co~nact ]s obtained, 1 ht: calorimeter K thus constmeted I~ suspended inside a pear-shaped glass bulb [shown at (b)l w hich can be fill.ed with :l,ny gas or evacuated. The whole can he surrounded by suitable Iow temperarere Laths such as liquid ".it Or liquid bydrogen, The pla~i[illl'll spiral, which serves both as electric heater and rcsi~tance thermometer, i~ connected in series with the battery .B, resistance T and il. precision ammeter A. the vol tm eter .v. indicating tb? potcnti al dlfference across the spiral. In OI:.d~r to. brrng the c~lorJ.,meter to the desired. tem pel attlre of ex.penmel'l r, hydrogen w hIchl ~a good conductor of heat wa S hrst ad.mittecl inro the pear-shaped vessel and the latter surrounded by a suitable bath. Next the vessel was completely evacuated 80 that the heat losses from conduction and radiation we're almost entirely eliruinated, Jnaddicion it was surrounded by liguid air or liquid 1 Lydrogen.

p

c

[CHAP.

it, ]

RESl) i..:f8 OF .EARL Y :CXl' ERI;l.fi::j\.S

43

To c.arTY ou t an exper. imen t .. a curren t was :lI.l~owed t-o f~ow through the heater {or t seconds and. the voltage across u. was ad;lu;s~ed. to be constant hy. V<L11'ing the resistance . L. If R.f'·~ and ~ t» tj. denote rha fina 1 all d ini tis:l values of thefesistance of the hc~ ter "and the CUH~nt tluougb it respectively and E the constant potential dllfen::nce,

E,_ E R) =-_ , R.~- , "

~f ~;

Thus an observation of i r- ~ i~ and E gi,,'es 1{ fand R} t and i.rom ~~ previous determination of I.h~ resistance oI the. platm~rn . spiral at VlI.rlo. us temperatures ~he ns_e .. In, Lempera~~'e s:@callbefouncL.The energy supplied electrically is .Et.t where x rs the avera;~ value or th,e currenr. Now if M is the n.1aSS of the substance forming the calorimeter, sits specific heat" we have,

su = ]Ms 8"0 + h. (15)

T11.is gives the specific heat at a single temperature since SO is U3UalJy I ~ or 2°" The; heat capacity of the p<i.per and paraffin can be found and eHmina.ted by taJ:ing different a.mount~ of the substance and at the same rime arranging that the tem.pe:ratme lise is the same, The heat loss h i~ vet:~ small and is determined and ilc.(-?unted fer b:, observing thil' rate of Cf)O]illf; before and atter the cxp~r;.m~nL

For non.oo-ndt~cting solids the (:alarimetcr shown 10 F~g:- 9 (c) was el.nplo,}'ed. The beating wire w~ w?und o_v-er a .cy~i~drical silver vessel D and the whole coveted wlth silver fori to diminish heat loss, 'This foil was soldered at the bottom .of the cyEllder 01:8 indicated, The ~Qlld w hose specific hea t i ~ l'e_qu:irnd ~<"5 pbce~ inside the roil ver: cvlinder and the latter dosed with the hd'. The silver on account o~ its high com:iuctivfty keeps the temperature. l.miIol:m and thi~ is further secured by filling the cylinJe.r with air thr-oughEhe tube i.I'1 the lid. The tube is then closed WIth a drop o[ solder so that It may he g1i.S"tighE. It IS absolutely necessary that air should DC' present inside the ,",c.ssel to, faeilitateequ~Iis,~[ion of temperature throughout the experimental substanee. Liquids and gil8e,~ can he similarly <tdn~iEM::d into the cylinder and their specific heat determined.

19. Re&1iIlts (If Early Experiltlenb.~ In 1819 Dul<::mg!liand Petit from rheirinvcstig.ations concluded that the product of atomic wcigl'tt ond JjJacific heat ~·as constant 101· many ,w.bs.tance;p, or in other words, flWm$ of all .~tlb.l'tances have t:he 8t~1'ne capacity .for h~at. Regnault from his own researches Iou ud that for orai nary su bstances the mean value of the ron .. stant was 6.38 with extremes of 6 .. 75 and!).? A more accurate value of theconstan C can be obtained from. the kinetic Eheory (Cha:p, In}, The atomic heat at constant volume is, shown there to he e-q ual to 3.R = J. %5. Acoord.i ng to Rieharz, the val lie ot the ratio. ct>lc~ for mall" substances lies l)enveen l.OI and l.(}4, hence the atomic heat at (Jonst-am pressure, the quantity oammonlv determined should Iie between 6.01 and 6.1 g, This law is of great

(16)

K

*' PiUTG T ,our s DulQng (1(80-18.;;8), a. distinguished French :;.delltL~t who lost au eye and anllge!' o\'i'ing to the explos LOn of some nitrogen chloride which he ([j~erete(L

[rnAP.

u.]

me in determilling atomic weights" In iUl1~tratioll of the raw table*

~ is added, .. -

TaMe 2.-llht$tration of Dulong an d Petit's law,

Neumann's law can be considered as a particular case of the folIrn,'I:'ing la w _: The molecu lar heat ~f a oolITl2f.1uncl ma~ be c?[I.-liiJeted as the. sum 01. the atonuc 11 eat s of its constrtuents. 'I hus 1£ a compound hal; the composition A •. BhC~ Dd its molecular heat C!J is given b'Ene rula t io n

c, =aC[';!_ +bCl'B -!-cC I'O+dC'!'D' (17)

where A, "B. C. 0 stand for~he different types ol' atoms composing; the compound and C ~A.> C~n~ etc., Lh,eiratou:t!c .bc-ats gi",'c:n hy Dulong fl:ndreL]t'~ Iaw. The law is of mIlch USe IJ1 ~va1uanllg lI1e mot ecu ia r h eats 01 certain sn bs tOln ces,

21). Vari!luull of Spedlfic HMl with r~eratIlN,~-The s:pedtic hea t as determined by the foregoing methods is not found to be a COl18t~nt quantity. Far solids and liquids the effect of pre~sul"e on specific heal. ~s rather smal]. The effect of temperature is how-ever very uiarked, Increase of temperature invariably -increases the specific heat, while the decrease of temperature lowers it. In -race the atomic heat of a ~QHd almost vanishes at the absolute zero and gradually increases with rise or temperature reaching <lsymptotk",rly the Dulong and Petit's value of 3R at a suffi.cien~]}" high temperature which i~ different for different substances, This variation for silver IS iUU8- rrated in Table 4.

Tnb!« 1~A iomic heal of silver a~ difj(Nem u:mperlllwrt!s_

AW11Ll.lC 1. Veight Mean sr(~ci fir Atoaric
Element 0) hcar (2) heat
rl r (1) X (.2)
--- ----
Sodium ~;:l.OO 0.307 7.06
l\-f agncsium 24}12 0,2'I7 :D,OO
Aluminium 27,1 0,2175 J),83
Iron J5JN O.1.W 6.H
Nickel .58.68 O,lOW~ 6.41
Copper ti.'LIj7 0,,0930 5,92
Zinc 6,~,37 O.cI9;~9 6.r4
Siher W7,9 O.05.1J9 6 . .'03
Cadmium 112,4 0.0557 0.26
Tin 1] 8. '7 O.W)[j6 6.,6[J
Anrimouy izr.s OJ1IJ02 6.10
Platinum I ~J.I),2 o.oms 6.21
Gold ~~n2 OJ)H09 6,W
Lead :::'07_2 o.osro hAn
Bismuth zos.n 0.0299 6.22 Temp, in DJ{ Atomic. heat Temp. in oK Atomic heat
1.35 0,000254 55_Sa 3.186
:') 0,00509 1'4.56 4,039
10 0.,0475 ]OjJ4 4,797
20 O,,39!11l 144.38 5.373
36.16 Ujl9i 20i'Ui ,1)_00.1) _\-lean \ alue ::;:;; 6.24

In Jdtll Nellln"Hln ellunciOi~e_d :J ~imn:iLr law concerning l'n ole cular lu-ats : the p-md1u:t of the spe~1!n' l!.r~ar m'ul the moteculnr tueig;h-t of rmt!)Olmm of s"~l!h~1- t'OmjJos~twl1- tS nearly constant, The value of ~ be constant \·aflC~. hum One ser~es of oolllpound~ to armthcr. in illustration nt the law taukt .~ is added.

Table ;,-Molecuhw Heat of Oxides"

The asymptotic value of 3R C,L!l be accounted {,or hy the Kinerlc Theory (Cb ap. nI), The variatien wi th tern perature ha s bee n .mccess~uU)' explained hy the quantum theory of. specific heats and in particular hv the Debye's thenry of specific heat which is however

b !::):ond the soope of ~his bonk. __

21. Tw@ Speci6c Heats 0'£ a Gas.- The spectfie heat of a gas, as of solids and liquids, mOlY be defined as the ratio of the heat absorbed to the rise in temperature, taking aL unit mass of the gJi~, A little consideration will sho.-w that this definicion requires t.o be restricted. Imagine a quantity of gas to be suddenlycompressecl, The temperature nl the gas 'will he found to nisc, £holt1!{h no heat has b.::c:n added. The ratio, hel1~ addedlinaefl--Sf't in teml)el'tl.tm-e i.e. ~ peel f c hea t, van i shes. Ag-ai n ret this CIlmpro(!~ ed :l i If" ex pand ~lIdlknl) : a CTIoHng WOl.1Id take place. This is _just prevented h~· applj'jj'g some heat to ~he gas. III this case the ratio, he« t add~d/

COnLIJOllm]

SpC'ci A c hear (l)

;"'lolecuhtr I Mn1ecu.lar

wei <rb t ht:a ~

(2) (I) X (~)

II!

2'/.2 27.'1 25_3;

2!L9 28.1

0.1700 0.1795 0_ ]277 ()-0901 fU1605

159.8 rsz.o 191.8 287,8 464,8

Mean value = 26.8 ~ T~kefl ~rom f1fJ;JfJ/llrcil d~;- l!,#cri1J~~j!h;r{-Pflji'~jk. \Tnl. &. 1). 19'1

T Taken rrom l!{mdbjjeh d~r Elrprrimell/-a'-Fh~·sik. VoE, !':, p, 20(1.

CALoRIMETRY

[CHAP.

F.Xl'El.UME~n OF G,\'y-LU.5SAC &: JOULE

n.]

chml~e in tempcTfJtv.:'re becomes infinite, Thus we see that the original definition gives an infinite range of values for the specific heat. Hence external conditions are of pai'ar.n(mnt importance in determining' the specific heat of ga!les. It has become customary to sF eak of two sp ecifi c hea rs of a ga.~: tho specific heat at consta 11 t volume d,enOI/d hy C" and the specific heat at ~on;sta~tl2res~ul,'e denoted by C tr In the former proce,~~ the gas 1~ rnamtained at constant volume so that the whok heat applied § es ki increase the internal energy of the gas. In the. latter case the gas is allowed to expand a~irlst a c:>nstant, pressure ~[ld in 50 do, ing it does external work_. TIns work IS obtained by u~~ng up part of the heat ener-g), apphed.w< rill! gas. Hence d1e sJ.~ecdic heat at constant pressure IS necessarily ~reat~ than the specific heat at constant .volu.me by an amount which as simply equal to the thermal equivalent of thel work done by the ga,""

. Let us assume that. the ga~ ~ perfect, i.e., its molecules exert no influence on one another. ThIS 1.~ approximately true for the pen:l1anent :@l'se~ as Joule's experiment {Sec. 2:2') shows, Hence III this expansion no i nternal work.' aga.ii'J st molecular a trractions is done by the gas and tbe ,ex~s of heat supplied in the second case i.-; simply the thermal CY_ uivalen t of the ex ternal work. Consider the gas enclosed ina vessel ot any shape and suppose the "ralls of the vessel can expand outwards, Let 8A denote an element of area of the walls and 8x the distance traversed by, it measured along its outward drawn normal. Then the work dune by the gas f n this expansion against a CODSrant external pressure p is NAi!i.-: and for the expansion of the entire ~ur£~cc the work . is equal to :$ pM.S;'\: = p1.iM .. 8x= /Jl;V where o l B the increase in the volume ol the gas. Suppose a grammemolecule of the gas, ()~C1Jpy1l1g a volume VI at temperature TOK and pr,esslI re 11. ex'p~ I' ds to a vol urne V ~al: tern peril cure (T + 1) o K, the pressure H~mall1InS' cnrutant. Let l'ricp = C p, A1c ~ = Cv .. vherc M i~ the ILl ole en 1 at" wt:lgh L of. the gll S. C ~ and C ~ may he called gram. molecular or molar specific heats. The work done bv the 1;1;as in

expanding fl'QID VI to V:~ is ' .

P(V~ - Vi) = It [ (T + T) - T] = R~ (18)

hy the ga .... laws" The thermal equiva.lem" of this work is J(Cp - Co.). Hence

tic, -CD) = Rt·, (l9)

Or, if either R :i.~ expressed in cll.lo:;rjes, Or C f1 and C ~ measured in f"rgs we gel.

--: .11 /1 ~
,;-;~ I r \
'\ I I I. ,
I I I.
! : ~' ~ ~ • ,
·
r , ... _1... 4"-'" ·
, i._}:[J l._J · ,
t B ,
A C ,
! ,
,
~ ,
t ~. , ,
· ,
· ·
'! • ! ,
!
. ..... ,.,) \ <
. -, ~~ '''- .,,-
.... ,... _, A

c

G~-C~=.R.

This relation was firs; deduced by K Mayer.

. '" This assum es tIle First Ta W lrl Thel'lIu)tlvnamlcs w hicEl w m be cliscil.~sed

III aU;,p~l'~ HI !\i1d X. -

t This i~ true Ior !\ f.lCl·rect gas ofJIJ', For real gases it call be shown thai

C~ -C. = T( !~ ) "( ;;.. ) p where the dlffe;rentiaJ.s mustbe evaluated from the a dual crlll::1tion of. state (Chapter 1\1') fo[, the gas,

..... ~ -- ....

Jo~rlc'3 I;!xilerlment with Joule's ex:p;erEmmlt with

one calorimeter. two calorimeters.

Fifo. 10 Fig. 11

is indicated in Fiss, 10 and l l , The two vessels A lind :B W111.m U nlca ted with ea ~h o ther thruugh a tu be fum i sl~l.'!d wi th a s to pocock G A 1,V'a5 tined with Jl'Y air at 22 atrncsphercs while ~ was exh~mted. First the .wholtl a.pparatllS was placed HI a .slDgle calonmetc~ (FIg. 10) and the stop-cock C opened. t:Jo cl:~.anS'e U1~emperHure at the water was observed showing that ~o HlIternaI. work ~gaJ;nst l.T~olec[lIar attr~clions was done by the gas 111 expandHlf?' "I 00 JIlV~5uga~e: the~ pOint further, the parts A, H, C were placed in separate vessels (FIg .. ll ), containing ~,vater whose temperature could he _read by S1e~~ltn'e thermometers. On opening the stop-cock C. the an'expal:ded mto n and the temperature of the vessel sun:oundU'lg" A fell wllll.e the ternperatures ofB and Cruse" H was found that ~he heat lost by.~ 'was eX::J.Gtlyequal t~ the .~lIITl of . the heats gamed l?y B. ,md, C, thus the total change In the interual energy of the gas during expanswn

is .l<.'''.TO, i.e., ,( ~~) .. = {I where U is the internal energy and fI the volume, This is called Joule's law or Maye.r's hyp(J~hesis, This shows dearly rhat no internal work is done by a. gas in expanding, Joule's law holds only.for the perfect gas to Wh.lcb. the perm~lnent gases of Nature like helium, hydrogen, etc, apprO;;am<lLC" For further

:j: L()llh J OSE'[)h G.i>Y- J.US!>aC ,(t 773-1850) was a distinguished Frtmch scientist who im~til' .. ted Of! the expansion of gases, He \,ra;; .'Iltere.ste.d, 111 avianon and ill 181M made a balloon 2!;.L:Cnt for the purpose of making expernncnts. He was created a peer of France.

4H

CAWRll'"H.TRY

II I

1',\'( ),risc.-Dry air enclosed at 25°C and at atmosphertc pIC~&ure 's ~1H!dl nlv C()fnprcs!>ed to half its volume- Find (it) the resulting , 1111('1 ;Ilm'c" (ll) the re5ult.ing pressure. Assume "f = 1.40.

(II) l,'l'1111\ (24) Tl = T(V/Vi) ,..-1=(273 + 25) (2)1-4-1 =393°K.

(/') Fi om (23) , PI =p(v{vdl' P X 2M =2·(}4· atm.

24. Experimenlal Metbods*.-L.et us nDW consider the experiIllt'IUOII me thuds of finding the sped fie beat of ga~e:'i. Since {m I't'II(~( 1 gases Cp - Cp = RJ a kno,.,Tledge of One of the specific heats ).li\'l'S the other. Again, if we determine "'I> i.e., G~ IC~ the above H!I'I,·ion will give both C~ and Cu' Hence the experrmeutal methods uru Y 11 e eli "idee! 11'1 to tl1rec d asses :

(a) The measurement of C~ (0) Thc measurement of C •• (I:') The determination of l'

(a) MEASUREMENT OF c,

25.. The !pecific: heat at constant ])re~sllre has heen found either by the Method of Mixtures or by the Constant-Flow Method. The pr]ncipk.s of these methods have already been ei plained,

26. :MetLo~ of Mixru1"4l$-Relrllau:lt's AppaTahu. The. method was fint applied to g,tl!lt;:s by Lavoisier and Laplace, Improvements were

d!SCllssion s~e Chap, _VI, sec. ] fi and Chap, X, sec, 3, As a matter of fact, a shg~lt Ian In celll:perOilture should be observable in Joule's expenmcnt with one calorimeter but on account of the larue hen t

capacity of thp. ealorlmerer it escaped detection, 0

23. 'yja~ati.c lrllllll~ormaHulu,- Whelll the pressure and volume nf a IIU bs ranee chan ge but no hen r is allowed to en ter or ls 1\ ve j t, the transformations arc said to he arliabatic (3. = not, dia = thrcuah. ' bales = heat, i.e., heat not passing' through), In an iso tlcrmal chal~ .. e t~e temperature is, kept, l:Ot~stant by adding la;:it to or Laking it aw~y flO~ the sLLbsta~lc~, Cousl.ller ~1: amount or heat 8Q applied to a rerfe-c,t g.t~ .. Til_IS IS spent l,tl r.usmg. the temperature of the gas and In domg external work. ]I we consider a gramme molecule DE the gas, the .former i~, equal to C ~ dl' and. the ];),1 tel' equal [,0 pdV IJ, both III cal orres , Hence

8Q = CpdT + pdf'll, or, if SQ and C ~ are measured in ergs.

8Q ;;;;;;: C. err + l~dV. (20)

Thls llq nation combined with j;V = R.T .wiH gille the' solution nf an problems on perfect gases." In an adiabatic transformatiuu s Q = 0.. Thereforo

C .dT + pdV = 0_ (.';lJ)

, In order to fmd a rclauon between p and V we must eliminate T from (21) by means of the gas equation pF = RT. Dirlerentiating the la Her, we have.

pdf! + fldj) = BelT. (22)

Sulmitutillg {OI' liT [rom (22) In (21), we ger

C pdV+ Vdp I dV 0

~~ R --p =.

ami replacing R l:Jy GI, - C.,

C .Tldf) + C~ 1){111 _ o. nenoting C pIC ~ by 'I we obtain

dp dV

T+1" V=O,

which on integration yields

log jJ + 'Y log V = consranr,

or . .. .., .. f'P''J! = constant, ... (~?,)

ThlS ~~ t~l(;~ lulHlbat;lc re~at]O~l ~etween p and II for 01 perfect ga5_

To hnd the adiabatic relation between T and VOl' between T and j} we must rcs_pectiv;]y eIlJ!linatu p or j? hetv .. een equal ion (23) ;J1]d the gas equanon jJf --= RT. The results nre

TV'I-l = COfISml1t, (2.1)

Tp(1-~\"l' = coustant. , (2,5)

" ~ F or rc~1 gaB_e~ ins ~td of P V ;;:;; RT, and C~ - C" = R W~ rnll.!lt ~ ubstit ute the ,letm,:] ~~jtllltH'I1l ot state nud (he true value 01 C.- C.\Ve shall th 'n rr 'j the n:b,tlon between p, V and 'l' for n:al ga~es. • , ".~~ ~

Fig. 12,-R~Lia.lJJlt'~ AllP,;unlus 10L' C,.

~j T he r~Hd~r W Lll finrl 11 V~ I)' good aecount {Ii! these met hod ~ ill P .ll't in !,!ll.l1l am! Shi l]il'br::; S ".'effie H 6'Q I oj U:(I.s~s.

-1

50

made later by Delaroche and Berard, HlIyttOft and. R~gnaulL Rernau 1 t wi th h 18 great experimental sk i U ob rained results of high aOC~ml(x. His applltatu.!I is indicated in Fig. ] 2_ Pure dry gas was compressed in the reservoir A " ... hich was immersed in a thermoetat. TI~Je.>;,( .. voir W[lg provided with a manometer. (not slHr~rn), Cas could he allowed to flow through the slop-cock V at a Uniform 101te. This li~'as effected oy conrinuously adjusting the stop-cock V (shown SeprlEu.el y) so chat the pressunil_ jnd! cated t)}' t.hem:iU~om et t lit, was eonstam. The gas then Ilowed th:rough a spiral S immersed 1.1.1 a hot oil-bath and then into the calocimerer C fif'l;Jilly escapIng uuo rhe air, The gas acquired rhe temperatl1rc T of the bn th and raised

the temperature of the calorimeter, ~ay, fi'?rn 0, tf) O~, .. ..

Tfrn b l h,~ m1M of the gas t ha t f1uws uito the ca I (DoJ: an eter, (" ~ Its specific heat, i~ given by

t'l'u:p (7 _ 0] ~ (J~) =W(I9~-Bl)' (26)

where (I) is tilt: thermal capacity or the caiorimctc[" and its cenrenrs. The ]"mISS m of the gasw<!,li determined by Regnault as foHows:f<'ilr any rl'e~~ure 1) he assumed that the wof':ight lV of the ga5 contained in rhe 1'(~ser'V{)ir at tern p~ra LUre () was gi yen by til e rela tion

W (1 + all) =Ap + BP: + Cp3

w here A, B J C were deterrni n cd [rom a series of prel i IU i nary ex perimerits. Hence I he wdghrW' of 11:'15 wnespumJing tu the observed pH'~mn: If ~I t tile end 01 the ex pc ri men r h give n by

TV' (1 + ",0) ;- :ip' + B112 + Gp'a

.L hm fiV - rv', i.e .. , Lht· \\'I>ight of the ga.s that Ilowcd uut was found,,· In pI uctice, corrcctiruts arc ne('~~~ar)' [or the loss 01" i'!:ain of heat h~' eundurticu, convection and nuTiarion which. have co he fonnd out hy flu.erving the change r fI lempcnHme of the ealcrimeterbefore and. a r. I,! 1 l he ex P erimen t, and raki ng the a verrtge"

27. O~her Experimell't&. The experiments of 'Wiedem,ann were e~s(!TltiaUy similar to Lhose of Reguault. Lussana devised a highpressure appft1"1I.lm -in which the same amount of gas enclosed at a high pn~~sure.: can be n::p~atetTly heated and passed through the C'alorimeter. The principle employed lsthe ~111nc as in Re.~l]ilul~'s ex peri III ell t, This a pprrratus can be u~ed. to find the speci fie heat o [ gase~~ at very high pr(};s:me an tl po~~e~:ses ~ he ad\"anLa~ that th e g:u i~ not W:iI sted.

For determining the spedfic heat a~ high temperaturesthe experiment ol' Holborn and Henning rna]' be mentioned. :Imploying- suitable electric heaters. resistance thermometers and weU·J~~lgI!led calori-

~ H th-e: pect.ie-tt ga~ ~e]:ltiOll !n1 = RT 1M (p" .Ii), where 'V LS the 5pecilie vehnne fJ£ the g~_~ alid .M its mnlccular WG.lght, i~ a:S~llmed to hold, a ~im]l],t' '~xpr~s~.iD.TI fOr W - W' C1Ln be msily o~t:dneJ, Let V dcaote the \'01\1 me of Til e reservoir and I' == l/v. the density of the gas, Then

W Vl'= ~~, and W-W'=:~ (p-p'),

wlllet~ j~ L~ e:xll1"¢~.~ed in tl}'lle~ and R i'lergs.

II I

MEASUREIIUl:NT OF' C.'

51

I U I r I I II (' Y were able to find the spedfi c heats of nitrogen, carbon II I" .u It, and steam up to HOWe. The calorimeter correcaions are d I j I I L d I .11 h I uncer min" The same method has beenussd b)' N ernst

trill ~ I i III ~ L he specific heat of ammonia up to (j,{HY'C.

2M. Coru:hmt·e!ow Mdhml. For finding the variaticn of ~pcdfic tit I r \\' I! h rc rnperatnre the constant-Howmethod is most suitable, and i ill I u~t'd by SWOIn. The mast recent Iorm of the apparatus is

t II (I [f~~11 b~ Scheel and Hense in finding the. 8pedtic beat down to I~ II" t~'H11 -eratureand is in principle slmilllf to that shown in 7.

J 11[· ga~ under test, prevl{lLLs]y brought to. 11. ~~eady temperatnre pd ~ ill, l hro ugh III suitable ba th. Rows through the calori meter in I! It J Y ~l ream, [115id.c rho calorimeter it is heat.etl~lec[:ricaUy hy hr II i II'-i Loil or canstantan and thus the enetgy supplied can he

~ .11 11:·1 r n I. The temperatures 0 rthe incOl,1"]lng and outgOi:r;lg gases. .1 I,I'~~'I \'cd by' resistance thermometers. The ~ped['jc heat cat) be lit u 1;'11 I'd by an equation similar to (15).

I ut Wlll L:. at low rernperarures the gas 'Ii~TOJ:S initially passedthrough • I (, \\ r I' III p~ r;t nrre bath in which the calorimeter was also i mmersed, III 11II [) i liM helium and other rare gases Scheel and Heuse modified It I ,I PI" I. n m sn as to employ a cl osed eireuft, These ex: pe rimen ten

II I I ~'j I [) II[ measurements on various gases in the range!(J,o to - 180°C"

I fl. IIIL';I~L[rCment or specific heat at high pressure ~h~ constant"

fi,l 1111'. hud 11:j~ been employed Ly Holbom and Jakob and gi",e~

I II II'I)~I n-huhle results.

U,' II.~ rruons :£lASED ON THE MEASUREMENT OF C.

29. Sbmm Calorimeter.. The direct dctermlnauon of (;. is best III I I, 11\' means of §o]y's steam calorimeter (sec. 12). The method ,I It I I ~ III ~ u LIt the experiment and the necess<lry details will be Ion nd I I t L I I ~t t l ion,

I~tI~~~

r

52

[ CHA!'.

30. Explosioo M.elh.Qd. Following the work of Bunsen. Vieille an d OtllffS, PIer im pmve:d. the expl osion method and. deyi~f:!dLbe modern "explosionborob ind:i,caced in F~. 1 ~L Immersed in the. waterbath B I~ a steel-bomb A WblCh has a side tube M through which (he bomb can be evacu 11 ee ('[ a nd various gases introduced at the desired rart~aJ. pressures. S Isa co~tuga ted. steel ~em !)T(lne dosiu~ an ope nmg 10 me bomb and c8Jrr}"mg anll.llifor S. 1.1ght nJlectetl. from the mirro:rfaU~ on the photographic firm t which revolves on it drun£ ~y apr lying variousknown sra tic pressures and noting the deflection of the light spOt, the preS!3ure attained in any experiment can be found simply frnmthe record on the film. Any explosion mixture, say, a mixture of hydr'()gcn and. oxygen together with the i nert gas wh 08C speciflc beat IR requirer], is introduced in the bomb, lly 'inert' IS mean t any gas whichwi11 not take part in the T eacti on either' from want of chemical 1I.ffinity or due to its pr~e.1lce in excess, The p<l rria I pressures nf the various gases arc known, 'Th e ex pl osiou IS starred by means 0 f eh:~r.t.ric ~parks and the final pl'\'::8sure reached (p» is observed. 'Thistakes ahout /OI sec,

The c.alculatIon maybe ellliUy made. If the vessel were allowed to cool to the initial temperature T a (absolute), suppose it would record the pressure 7'2.. The maximum temperature: T, 'reached during the explosion ;.5 calcu lafe(l from the value ot Pl, for, Irom-the gas laws, since the volume remains constant,

Th =-lft.~ . 71 = b T~.

1 a P2

Or if j}, denote the initial prer.sure and. ~ the ratio of the final La the initial number of molecules (owi[)g to she explo .. sion the total number of molecules ch::tnge~),

h= ~j)i [,: volume and temperature a re the Sm1.1e]

Pt p

Tl = -, T~ = - - 7 ~j (28)

~Pi ~

where P i~ the ratio . of ex pl osion pressure to initial pressure, Th e relation connecting the specific h~'HS and. the heat of reaction is

'mQ~ = (T1- T~) rrnCv.+ nC .d, (29)

wh~re m i .. s the number- of gramme-molecules of the reaction products i n the number of gramme-molecule~ of the inert bras: C • ., C ~i} respertively their mean molar specific heats over the range (Tr - T2), and Q~ the heat of reaction Ior the explosionmixture at '1'26• {JJ is generally known from thermo·chemic.al data, We can determine C •• by exploding either with diftt:rcut amounts of a gas whose varIation of speci riC heat with temperature is known, or with. different quantuies of argou, a substance ,""hose specific heat IS constant. Then the same reacting gases may be exploded with <I fly inert gas, and knowing C v.' we ca n find CD; for the Inert g;'l~.

The method is very suitable [or measurements of ~peci6c hear a thigh tem per-aL uresand hOI S bee 11 used to 11 bout 30000 C but suffers lmrn the di..~advantage that directly it gives only the average values

u.]

DETERM tx j\HON OF Y

." er OJ wide rang-e and not the specific heat at any ternperatuTe_ 1'111 UH::t', corrections are neOC&.5alLY for loss 01 heat, effects or dissociat,j I ~ 11, in com pl ete oom bUkitlOU, etc. For argon, Pier fo und that the II. J Il'f d U.: h ea t does no t vary with tem pen ture,

31. Nernst's varunm-calorimcrer method is. employed to find L ~., :n low temperatL.l;eS_ _ The ga~ isendo:;.ed_ in the c.1I1orimet~r 11' j~. U ([) J, Eucken m ~h]sway found the specilic heat of hj'dfoge-Il III 1 \\' I:'_:U .'},5 o and 27!P K 01; n d 0 bta i ned in tercsti ug resu Its.

(c) METHODS BASED ON DETERMiNATION OJ' "i

32. ill dread Y 'pointed out thi~ is an ijJ}d.i:rc.:(:~ method of finding ill(' specific heats of gases. ThQughindirect it is capable of the hlghe~t If r tn'OIe]' so that the modern accepted values of ~pecillc heats aye I',m:tl on the values ofy thus obtained.

The methods for measuring r- the ratio of the rwo specific heats, 1I1~ > be classified under two heads: (1) those depending on the adiei.ulic expansion 01" cf.nnpression of a gas, (2) chose depending on j rll' velocity of seund In the gas. "\Ie shall first consider the former,

(1) ADIABATIC LxP_O\N&W:-f M.f.THO~

33. £Xperlllumt& ·of Clel!llefit and Des~T:nuls+- Clement an d D esormes w(~r~ the first to find I' by the adiabatic expansion method. Their 111'Lg[llitl apparatus has been considerably improved and us indicated I u 'Fig. H. A large flask A of about 28 Iitres capacity is closed I i)' :l stop-cock M about IA em, in diameter. The flask is 1'0 rt nected to the manometer P i f' A hv means of a side-urhe and il< 1)1 !!gged with cotton wool to avold 1068 of heat, Ftrs: the fht8k is I ~:t!'tiaIJy evacuated and the pre5sur~ Pi recorded by the manometer, is n bserved, The ~tOfHDCk

!\ r is then opened

an d. q uicHy dosed" Air

1'1l sb es into tli e flask till

I he ptoCiS;sure inside and

nu tsidc becom es eq 1,1)1 L

Tho proc~s8 is adiabatic

~[nn~ i:hc!o~ bf heat In

• h~ short in terval fur rt.

w h j rh the 8 tori-cock hi is .... i

ope11 may be neglected,

The tempera Lure of the

:l ir in the Ilask rises on aCc.ount of the inru;.<;ll {J.l..

! 11 e external air and. th e pressure Iiecomes atmospher lc, The. fla.,o;k is next allowed ro cool to the (em pcra tore 0 f the surr-ouiHIings when the water i n tlH:~ 11111 n ornerer 1'1 ses ['Ilid fiually indicates the

pl'c~nne Pt. Fig, 14 .. "O,e[J'I~11t aml De~Ol'm~s' apparatus.

Cl"LORIMETR Y

Let the atmospheric pressure be p~ and the specific volumes of air ~t tl~ pres~ures. Pi. /?A. PI> be respectively !'jj VA, l'f. The ilrs.t proC!~8~

IS adiabatic anti hence we have, assuming the gas to be perfect. .

P,vt~PA lJ..tF• (30)

- Since the final temperature is ~he same as the initial, we have. considering 1 gram of the ga.~,

;'fijl1j=P fVf·

Agai n, ~'AI ;=; vI

because the volume of the manometer tube j~ negligible cOn1J;_I.8!Ted with that of the flask and hence there will be no appreciable change in the specific volume o] the ~ ... as due to rise of liquid in the manometer,

Combining (30), (:.11), and (32), we have,

~: = (:~):

log Pt-·]og PA '}' =TOg F;- jog Pt .

II, as usual. the changes in pressure arc sma ll,

Y =-Pi Poi.

P,-PJ

or

t

From the measurements of Clement and Desormes, L<lpTan~ deduced

uie value o~ i' to be 1.3£1 L

In this experiment there is a source of serious error, 'Ve have

< ~~UIlH!t1 tha t (he pre&mre inside has become atmospheric when (he stop-cock M lS closed, Actuall 'I, however, oscillations set in; on account of the kinetic energy more air first rushes in than would make the pressure just ~tmo~phedc, and hence the pressnre.fuside becomes g1"~a tcr th an tJ A' N ext some ai r rtrshes out till the rre~sutc imid~, i ~ 1c5~ than l~ A and 80 on. After several such overshoo rings ehe prc5~un: p A is a uaincd. This t akes consi dent blc time and, as a m a tter ~)f fact, this to-and-fro motion has not subsided when the stop-cock JS closed, It must be closed at the instant when during an oscillation the pre;ssurc just becomes atmospheric. This is very difllcult to secure and hence later investigators tried to. avoid it by measuring the change in temperature rc-su,lting, from adiabatic ex.pa,nslon. The scop-co~ has not to be closed In this .ca~e: ~e shall ,-?rl5Ide,r .sh.orLly the ~p~n. inents of L~III1:n~t: ~.nd Pnng.sbeun and of Partington aud Shlllu.1g based 'On this principle,

We: have assn med above dlat the in oami rig air has the same temperature as the all' in the fla~kinitiaU]'. To avoid correction in case it is nor. 50, it is better to stan with oompressed gas in the flask, when a D-tube manometer must be used in place of p~ PA• Further c~re must be l~ke~ to use perfectly dry air [or y is ~pp{-eci,ably different for motst all'. Consequently sulphuric acid is generally used

01& the Iiquid in the manometer. .

34. Experiments of JOllie, Lu.mmer <l[ld Pr-ingsbeim, and Pamligf.IlIi1.Joule was the first to study the change in temperature by

II I

.E,xPERtM·F.NTS OF PARTINGTON

1,l1:abnlic expa.ns.ion or compression. Various investigit_t.oxs later , 1111 .1,,) cd this method to determine 1" Air was tOll1pTeSsed in a vessel lilt! i ts tcmperatore and prc5S~Jre observed. It was then. allowed. to , 1',LI1LI suddenly to atmospheric pIes~ure .and the char,ige In temperaIII ~ [' n oted, The calcu la tions can be casil y made. If P1, T 1 denote lilt, ]Jr~~~u.re and temperature before cxpansiuu, P2> T 2 the same II I ,I L H i l i es after tl ie ex parniOfl, we have, from (25)

1 -~ I::2:_

TtPI ~ =T2P~ ~

Pi 1 T~

III (I-i') log. =)" og '-T'

P2 1

log PI -logp~ (33) *

'Y (log Pi -log I)~ - (log 'fi -log '12)

r II us "I can be calculated.

Lurnmer and Pri_n~shejm ma(~.c. considerable improvements in .tbe I! 'paratus for d.etermnufig y by, this mech_od. They employed a g.[l.litre , IIpper sphere and III e;'iJi~terl the cha?ge ,HI te_rnperature by the chang.e III resistance of a thin bolometer Wire hangm,g at the centre of this .,phcre. A Thomson galvanometer having a period of ,4 sec.w~~ LI sed :J,~ a nil U instrnmcn c. Certain errors arc, however, inherent In

lilt· appar.<ltus. . , .

In order to eliminate these el'Tm~ Partington has further unproved

III« apparatus. He used a 1_arge expansiol} v essel . (1~O .Iitres cal?acilY) Illd a bolometer of 'very thin platinum IInrc (.001 to ,002 nun. m dia-

Fig, 15.-PartjjjgWfi'~ Appam.ttls.

meter) with compent;ating leads; thus there was no lag. Further all '" Thj~ is true fur a j,lerfe.c"t gas OIlly- For real gases it requires mrH:iifica"tiun.

11·1

VEWGlT'l OF roUND l\offiTIiOD

56

[CHAP"

If the ball now moves a distance x downwards, it col!lpt~s&es ~he .11 r adiabatically increasing the pres~lH:c to jJ -I-- dp, hence Us equauon

"I marion is

d~x

!1\il~- = Force of restitution

= -Ad'fJ.

J\"OW srnre jJv"J' = constant, we have

dv Ax

dp = -yp~= yp-.

v ~

for d» = - A.'>:.

J2_'t YP~:

m tll- "'" v (36)

from which the period of oscillation comes ~ flit to be.

T "" 211'i1' t/ nW V ypA~

4'1'1'~mV' Y == piPp·

(35)

(37)

CALORIMETR Y

Einthovcn string galvanomctr::r capable of recording ~emperatun: in .01 sec. is used so that a detailed record of changes In temperatm:e of tl:le gas during and aftR.T expansion is obtained, His apparatm is indica Led in Fig. 15. The vessel A is provided wi th the expansion val~ C which can be manipulated by means of the spring l' and wbos ~ Stz(O! can also be varied. Ais connected to ~ b e sulphuric acid manometer M, the mercury manometer m,al1d the drying tubes F. Thus careful ly purified air enters A. Further the vessel A is k~ '1t immersed in a water-bath which is kept stirred by S. 13 is the boiometer wire (shown sepa~at_eIYI in t_he tigur(2~ and is connected in one arm of a 'wheatstone bridge, G IS the ~tnng galvanometer.

The initial temperature was read on a carefully standardised mercury thermometer T immersed in (be bath and was given correct to .01. o. Then the resistance in one arm of the \Vheat~tone bridge was lowered to give some deflection in the ga!vanomdcr. It was so arranged l)y tJ;iab that immediately after expansion this detlection was redu ced to zero. After the expansion exper imeu t some j ce was. continuously lId.ded to thc bath to keep it.s temperature constant and equal to that immediately after expansion, . This was ascertained by keeping the galvanometer deflection steadily at zero, and the remperOlture of. the bath was again re-ad on the same mercury' thermometer.

If the aplc"Iture is too large, oscillations of the gas tale place and the galvanomet<:=r deflection is not quite steady, the initial deflection h~iIlg somewhat grcat<.:r thun the true value. If the apertmc is .tOO narrow prolonged expansion results and the pruccs~ i~ not adiabatic. Tn practice, the aperture was gradually diminished and when over~hootiHg was eliminated the deflection W;;JS instautaneous and pedenIy steady. The atmospheric pressure V1.~S read on a Fortin's barometer and r calculated [rom the foregoing' formula, "I WOiS found to be ]:40J'~'" _::Jt_ ] 7<:>C '. This 111etho~ cannot be used arhigh ttl11per~Wlr~s 81r1C(! It IS impossible to determine accurately the cooling correcuon,

35. Ruchardt's Exp.erment.-A simple method [or determining y, which is suitable (01' class-room demonstrarion, has been described hy, E. Ri.ic}mrrit,. ~he apparatus consists of a large gbs~ bottle V" (FIg. Hi) fitted an-t.lght with a glass-tube at the. top and a stop-cock H at the bounm, The glass-cube has a verv uniform bore in which a steel hall of mass m firs ~'ery arcurarely. If the hall is dropped into the tuh:-, it. .begins _to oscillate up and down and cernes to rest after a few oscillations, 1£ the period ill cscillation be determined with a stop-watch, 'Y am be easily calculated.

Let A be the cross-section of the gh~s tube, v the volume of the bot dc,. h the ba rome tric pressure, all d p fLhe pressure in the Husk,

T'hcn 111, the equilibrlum position "

(!l1)

v p

~'LSi.Jlg this, the veracity of sound in clt" air at 0·( was c;alClJlat~d fmm equation (38) to be 331.38 me:tn:s which is in 'close agr[!i!!ITle-nt with Hello's mean yalu€ 331.41 m./se~, (Sec_ J7).

Fig, ·16.-1Hkhardt'~ Apparatus.

apparatus, "f can be

'1 11m, knowing TJ' p and-the constants of the , \ :1 !mLtt"d ,

(2) VnOf"~nY OF SOUND METHO!)

36. This method also depends upon the adiabatic e.1{pamsi?n and t umpre~ion of a gas but differs fro~ the foregoing meth.od~m that; no direct measurement of changes III temperature or p[e3~Ul e need to be observed. " The method has given us the mod accurate daca reg::trding specifichcats for both ~igh and 10;..- t.emperatures and so' we shall consider it in some. detail. .:. _ '.. . +

The velocity of sound m any fluid 1S glvp.n by the equatlon

[' -= VEJ- where EsP is the adiabatic dasticity of the fluid and its dp.nsi~~: For adiabatic changes in perfect gases+ jn/J' = constant (p. 1P,) , hence

(OP)

EE= -~, --'. =r~1J from (35).

;h. s

U"",\/Yi .

p

Thus, i.f '/lie deterrnlne the vdocity of sound In the gas· we can

find ~ .!

~J1'. We may adopt either of the ~11.!() fol!owmg_ methods. TIle

absolute vcloclty or sound in the gas may be determined, Or we may

(38)

'1< Se-~ Rartoll. SOfIHa. ,

l' F or 1'Ca 1 g:a·~es. we must tab: into account the true. eqna tion. (J{ state t Coap_ TV) ~;ld substitute the value o!i (tJ.l.>/iJv). from that 't~luat10!ll. In all accurate w(}rk this is dfme.

59

C.~ LOlUMJLTRY

compare the velocitywith shat in another gas {~<ty, air) which has been determined accuratel y by other methods.

F or our purpCl~e we discard the large·sea le determinations of the velocity of sound in air on account t:lf the various defects inherent in them. The most. accurate dlrect determination cf the 'Velocity of sound in ah::.-wi!.s made by Hebb in 1905 bya method. depending fin the reflection oJ: sound Or known frequency from parabolic minors" His mean value after employing ail cerreceions giv·es 331.41 mctrtsj .see, as the vek.tcity of sound in air at W'C and 760mm. pressure" l

Not ... we .lllmttemember that practically all determinations of the velocity of sound in gases have been made in taibes, but the velocity in a" tube is not tIH~. Same ~~ in free-. spac~. Corrections have 1;0 be applied to re~uce this 1,'el0e,ny to that In ope~ "'p.ace as explained in the next. section. ,,"11 eq uatw:n (37) the v~locuy m open ap ace must ~e ~:rLJstltllted. DIxon has directly determined the velocity 0.£ sound In different gases from ] BOC to IOOO°C in a very satisfactory manner, His result may be employed to give "I'

Method based on the. Measuyeme.ut oj Wavelenga~.

. 3~ KUiJlidl'~ Tu:~e.:-KHnrtt I~nt devised 8.~1 apparatus by means o.f whu:h he could fwd the velOCIty of sound in a ga;s. TJns consists simplv of a glas,s tube about I metre in length and J em. in diameter .. One end of the tube W;l5 fitted with a movable stopper, whii~ turough

\ :ll il Ill'. prucautlons ate, howev·er .. necessary .. , Tht:. tube and. the II~ I W I r~· t mus t be perfectl y ~lty. . CaTe~up y purified ::3.U must he used n r ~ ~ll'ln·lion~. for the vartous lmpuntlts rnus~ b~ ?,a.de_ Too .}1l~lch d m [ ~ II (IL L tel not he used for excess of d USt~Ul~l~1~he.s the ~e1oc~ t~. 1\ (h'r'n:nsc in the diameter of the tube d1?lln.l.shes the velocitj . I'" i 11 a! I y, from the veloci ty In the t"? be the Ve~()Cl ty Ip.open spat:e n.n~~t Ilc' deduced. Though matbematll;al equatwns 7~VJng. the reqm$j~fl ~'ir'J~:ction have been developed by Helmholtz, l"'_lrc~hoff and other s, I tit)' are not quite adequ a te a nd the best method is to ex.pl:'e~s the

\ clodty U" in the tube as

, U' = U (1 - kG) , (40)

wh ere U -= velodty in open 8pace,

II, = a oonstant depending 011 the tube (its radius, . thickness, the the1TG,al conductivity, surface, heql1cncy of the sound,

etc.)

C _~ a factor dependin:g on the glls (its. v15c.o:sity, demit,y. ratio of ,~p eci (1 c hears, etc.)

Kirchhuff sh~red that

C == V·;' {l+V-;(r;~)J

where. ~ = 'ri8(O~Ety, o = density, '1= j[a~i~ of spcdf~c. he8:.ts., a~~ e -= Kh1c~" K being the thermal ronJuc~l'>'Jty. For an: tton~ Hebb s fxperiments we know U, and by obse.rvlllg U~ and cak.ulatu~g. C. h for the tube' i~ determined. ThIS value of It IS (~mployed to give U the velocl ty ]n o}?enspace for any 0 ther gas.

Kundt and Warburg later employed this roe-thud to determine the velocity of sound in. mercury vapour. One of the tubes cont.amecl mercury vapour and was heated in ;tn air-bath to about 3GO"C. The distance bets .... een two nodes was measured when jhe tube cooled. They fouml y _: 1.666. Rarnsay~11lployed this 'method to find y {or argon but 011 a croll nt (~E certain difficul tW-li.hc go.. a I~~ v:aIlH~: . neb n and Geiger improved theapparatu.~ eonsidcrahly. I hey ?'~pemed wi th the sounding rod and em played 11 sealed rehe co III a mi ng t~ e experimental gas as the source of . sou nd , This tube was dalTIpcJ In its middle .1IDd was excited like the sounding.rod. The tube should be chosen pro-perlJ' and itol~el1gth be adjustab:le so tb:<lt t~e UHl rained gas may gnrc resonance WI th the sound erm ~ ted by t1'1l:~ rod, Th.e apparatus was eminently suited [?r gases .at lu~h tempet:lt~nes, Tohl~ method was later~lDp1o}'ed by dlll(~n:nt Investlg~tors p:nlIcularly by, Parting-tcm and Shill ing.

Eig. 17.-T(1l11.dt:'~ DDLihl~-t1Jbe Apnararus,

IL~ ut!:tL"l" end pll;5s~d a lO?.sdy'fitting· disc carried by a glass or metal sounding-rod which was itself damped at Its centre, Later KL~ndr employ ed rhc double-tube app.aratm indicated in Fig. 17. Two tubes A and.. n an:: connected Ly means of the ~ourlding-Tod. S which i:~ damped at distances on~-ql1a:rte:r of its length from either end. The tl:'O rubber.curb, d, ~. 1.11 tlle tubes A anti _B provide the damping .ll rangeme~lt. The. p~sw~s P, P r:an be moved to and fro to brhlg the . LUbes \[1 resonance Wlt~ . the . rod S. Throug.bout ehe lemrth of e~l~h tube IS spread S~H1C :hght ,dust. such as 1ycopodiumpowder or silica dust. One tube IS filled wrth an and the other with the experimental gas. The souuding-rod S is excited by rubbing- it at the centre when t~]e dust IS thrown into violent agit.aIia.n at the antinodes and mU~CC8 fit the nodes. The di~«;!n(e bet.ween SUCGeS.!:ii\'~ nodes equals ~alf-l~a~'elcn.g~h, and knowing the frequency of the sound !he. velOCIty IS. e8s1iy. obtamed., ThE double £01"In of the <lprftr~lm l~. ~.'(~ly. co!l;vem"enc for mmpm'1l1g the velocity of sound in iln'" g"<l5

"iII'uh that m air for ] .

U -. _1r.'.~~-,,-

Vatr -A.l .:

_!_.O= h + ~ . 1'-1 )'1-1 l'2-1

where PI,P~ [l~~h~. partial pre:s!;lJres. of these gas.e£, P th~ tola.l pressure and. r stl!n~i~ fDr the ratio C1!/C.. l[)l" the mixture.

*' It call b~ t~as;Ll)' shown from very siln[)lc considerations that £Q1' <I. f11b::ture of perfect gases,

(39)

[CHAP.

SPECIFIC H.E.AT or SUI'ERl-lEATII:) VAPOUR

61

5U

CALORIMETRY

39.. Experiments ~f Partington and Shilling-.- These investigators

determined the velocity of sound in various gases up to lOOUDC bv ~ n~~(juance method, Tile apparatu~ is diagrannnutically represented JU FIg. I8 ..

F~ is a. silica t It be 230 em. long and wound over almost a]o~g ] ts en tii"~-....lcn,g~ wi th heating coils, T 0 thls tube ]$ 1:1 uachcd at X J,g:1ass tl.l~. MM, ]50 em. long. Inside the Iormer is the piston ~ "ot ailiea carried by the rod A, 11.180 of silica. Bll is a steel tube joined to A by rneans of a cork, The tube Bll carries a saddle 1

Cas O·rJUi!:t

11813a=t;=jP.i·f§L ~rI'I~F.;. £;1::~~

<I.F==='"

40. Speeilic: h~at of superheated o-r lIoD.-15atul'ated vapou.l'.-RegI rnult determined the specific heat. of superheated or non-saturated _.1 C<lITI nud other vapours with an apparaLUs whICh. was essentia'lly .,illlilar to that shown in Fig. 12 (r. 49). Steam is superheated to p l)}' passing it through the spiral S in the oil-b~th kept at. a temperature above WO'='C. The superheated steam. is :next passed .I t com taut pr't5,sure in to the condenser kept immersed In the wa rer {<Jlorimetcl', and the rise in the temperature of the latter from 81 '1:.0 f)':i! Ilnl ed.

H m is the mass of steam condensed, c; its mean specific J.1eat :11 constant pressure between the. t.emperaturf: T and i~ condensing point G" at constant pn.:ssure, and L the latent heat 01: steam at 81}, the quautity 01 beat given by the steam is

k ,,(T -0) +mL+m(O-82}.

This must equal w ((j~ - OJ) where w is the thermal capacity of the calorimeter and its contents. Hence

melJ (T - 9) +mL+m(e-O~) =W(e~-Ol).. (41) The experiment is then repeated with another value of T and a second equation similar to the above obtained. Solving- the two "_'lluM.tOllti,.· the two unknowns (;p and L ate determined. Regriauh thus found cp for steam between 225<;)C to 125°C to be 0-18-

In case of ':apour-s of O(l~el Iiquids, the specific heat of the liquid must he taken Into account H1 WfJi.mg out the above equal;Ions.

41: Reslllts.~ In the £or~g:Qing pages we have considered the various methods of finding specific heats. In table+ [:; (p. 62) we give the values which best represent the experimen~"il data. 'Ne reserve our comments on these values for the nex ~ chap ter.

Fig_ I8.-Partinglc>!l and ShiHing's Apil~ratu~.

~

rno V j ng Oll a m ill imetre sc_aJe, thus die displacemen ~ 0 f the pisto fI ca n bt. found. Through th is tube pa!!.S the th CJ:II1O·cou ple Ie ads to the po ten nome t[~r_ .~ ystem E, The other end or (be ~iIica tube is closedbv a te1e!)~on~ dI;]pnragm T 'which can he moved by means uf the screw Y: . ThlS .t:u~, can be closed ~aHight hy means .clf the bell-jar 1- ,The tdt:J?ounc d~aphl agrn IS. ~xc!~.ed by a valve oS~lJlator V givjng a noteof Jrequencj .3000. D IB a side-tube from which a rubber tulle leads to ~h~ ear C?f the experimenter. X is au asbestos plug to I?l"ev,enii

radiation of heat io M.. e

. The a . illea tube is filled with t,be experimental ga~ and maintained at., d~c ~e~n'ed temperature. T~e centt.a~ tube AB IS gr a dually moved a,,! a~ from D and the ~UCCe38we positrons of the saddle 1 on the ~.r~tlhmetn:: ~C.lre _ooue~ponding to a maximum sound in D are noted. l b [~ sUCC~SSl ~·edi.stanc~s correspond. tel 0./2 and kn'owing the frequcnc' t~e ~ vdocity IS d~tenrll~,ed. 'The p~(ll uon o;f T I"l as CO be adjusted :<II cli_£fc.:rent temp.eratuIeS m order to glve maximum sound in D when it will L('. a t a dL5 tance "II /2 from the latter.

Cook emplo}'ed this metho I .. (". d f ..

o .' 0 > ." •. ~ ,.. l 'LO om r or au' and oxygen fro an

90 ~o 293 R. HIS apparatus rnay be visualized if '1,~Te imagine toe hot~alr h~t~l :of K:.m~Tt a~ld Vthu:bLll"g' (0 he replaced by a long Dewar flask cont'llnmg liquid all'.

..

t Tabor. irom Irmu]buch o'er E.1;p~:rimel!talphysi.~, V(]l. 8, p .• );).

62

II I

HEAT J!ALANCE IN l-aE HllMANJlODY

. d {or the method of mixtures.

III dill,ll Y Cf.l,l()rirn~ter su?h as 1.S use

lid, cJiorimcicr is provided with a tlilTI :in(l accurate mercury thermo- 11111'1, '1 he whole h surrounded by

• I oml ~11 L temperature jacket.

To find the heat capacity of the I 1111 I II ami its accessories a known llllnll 11 t of electrica] eneJ'gy may be 1'1'111 in the ~ystelTI or OJ. fuel Q1

I II" W n 1;11 1 orifi c value burnt. The a.

1(J1·1lI~r method is adopte:d in ~ I: I'll d ~ rd ising htborato~ies and ~.c L, r ter in actual pTaCj;lCIt. Benzoic It id is most Sl,itable" for this callIllal Loll. The hw1.,:if solid, is formed. 11110 <L small briquette; if liquid, it ~

".I1.l.:r1 i11 pure cellulose and. pt:l m I lit:" platinum dish F and ignited, j \ l,n1l1 three times the amount {If I):'; y~(' n :i us t necessary lor com plete r.uuibustlon is admitted through B, t l, The oxvgen is generaUy employI'tt :H a pressure of about 20' atmos- 1 d u.rcs and at this high pr-essu1:'~ tit c , 11 m bustion is almos t iTlsta n tanetms. \ ~ a result of these ex per i men ts it

h:is been found that the ealorific value or anthracite coal, wooJ. (pine),

II['Lwl and methylated spirit are 8.:-1. Fig. i?~Tne Ca[Drimettic 13oml","

,I. I, 11.3 and 6.4 kilocalories per gram rr.::Rpe(.uveiy,

43. Heat balanee in the bllDliriD '!.ody.-The temperature of th~ human body remains almost constant in health. Th~ chief loss ?I 11c.;~1 L is [rom tile skin and from the excretory functions, the skin

un rracting in winter to diminish this 1~s8 .. Heat js. s:uppl~ed to ,the I ~udv by the food we eat and by the O).::1daLlOl1 of llving ussues and Ilms~les. The blood stream serves to keep the temper a mre of the body uniform. Due to the larger heat loss £rom, che LoCl}1 in :"intcr' 1\'(' have to take more food and cover ourselves with heavier clothes,

[CKM' ..

Ta Ole 5.-M {J tar Heats ha C alorics at 200 C and Atmospheric Pressure.

42. Special Calomneten.- Various typf'S of calorimetefs have been devised for special purposes e.g., fo[' the measurement of the heat. of combustion, heat of chemical reaction, heat of dilution, etc., but t.hey Invclve no new priuc:iples. Particular interest, however, auachcs to the deterrnina tlon of hea t of eombuation in indnstries, for the \.d ue of fuel r,~ ju d~ main] y from Its calorific value. This hea t can be easily determined with the .help of the calorimetric 'bomb',

Fig. 19 indicates the calorimetric 'bomb', It consists of a stout steel-cylinder A fitted with a cover herd down tighc]y by suitable means, The cover has a milled-head screw valve which varies the cavity kl and thereby ttgubtes the admission or: oxygen through sho til bes B a n d C i 1:HO toe bo m b. Through t he centre of the cove r bu t insulated from it passes the wire i which :i~ connected to the platinum wire ru, the other end of the latter being connected to e. There 1S another similar screw valve varying the cavity k~ through which. gas com go out of the bomb. To enable the bomb to wjtb.~umd the corrosive action 0.( the p!'ocluc~, of combustion it is plated inside with gold. though platinum would be better. The bomb is enclosed in an

-

Books Recommended

l. Glazebrook, A. Dictionary Of AppUed Physics, Vol. I. article- 1111 'Calortmerry',

2. Partington and Shining. Spe(·ific Heats Of Gases,

3. R(mdbu.rh det· E\perimentolph'Y~il" VoL 8, Put I,

I,

CHAPTER Ul KINETIC THEORY OF MATTER

\

THE NATURE OF HEA. T

1. Hi.storical.-Iu the legend.s of some ancient nations, it is said that fire w~s first ma~l~ (orr.~~m by some friendly .s?i~it ~.Y rubbil:g wgether two [)leces of ~t.lCk .. 1 he .leger:d plObably relet S to. Oil prehisroric discovery of the art ()~ IIDJ.kmg fire. BUL though this way of prm.illcing h~at by irictiOll clearly indical~s the real .nature 01 h~at, the early pllllmophers had no correct notion about It. They phIlosophized from the ubservation that heat could pas.s spontaneously from a hot. bod}' to a cold one. Heat was, thereto> ....... supposed LO be a

kind of tluid-the ca.loric ftu..id.

Various fictitious properties were as~igned to this hvpothetical fluid. It was supposed to-possess no weight, since bodies did not -incl'ea:;e in wejghr on mere heatmg. Further. it was sup:l?o~~d to he highly elastic, aU-pen,ar1[n_g, indestructible and uncreatable hy an y proce~~. The particles of this fluid were su pposed to re pel one ancther strongly :wl_rich explained tl.le expansion. of b~t~ies when heated .. md also the en11S~lOn of beat durmg r.omhu:SLlOl1. 1 ernperature. was Iikeried to pot.ential or levd.'·Vben the body was heated the ealor ic fluid was supposed to stand at a higher level than when cold .. Production of heat by friction 'was compared to the oozing out or water[rom a 5ponge when 5quet.:zed. The caloric fluid when thus squeezed

out, ruani lested itself as heat.

Doubts on the caloric theory of heat began to be thrown towards the end of the eighteenth century, Theearlie.st philosopher to have a LOW:.:ct notion or the physical nature of hear was Count Rum[ord.il In those days gullS were made by cas.ting solid cylindrical pieces and scooping out the: insid(!. by a Loring machine. Rumford in J 798 observed that apparently an incshaustible amount o] heat could be produced by the rl"tction of the spindle of the boring machine against ~hc body of the gun. though the ~:mount of iron scraped was very small. He undertook protracted experiments and found that the amount of heat produccd (measured by the raising of water to a high tcmperature) hore no relation to the amount of iron scraped, but. was J,roponional to the amount of motion lust. He henceforth Tejp-cted the caloric theory and asserted that Heat is only a kind Of Motion. If·hene'uet. Motion diffappea1-s it -reappea.rs as Heat and a~e·re. is tin exact prop01,timta.lity hf1hveen the tW·G. Fie even made an estim(r,te' of what we now call t.he Mecha_nical Equivalent u{ Heat, His value is not much different from the value now adopted as standard.

*' Count Rumford (17.').1-l814) was born in North .huucril..--a.. Bci]lP; loyal to Great rkita;n Ott,ill!!; the AITl~~katl \~iar of Indep£m!~l1ceJ he, had to flee from Ili~ country. He entered LL1tO the service uf tile Prince of Bavaria and [atcr W<lS plaloed In charge of the arsenal at M unich when be perT[)rmed the celebrated expel-irIl€l1B ClI1 the b!lrinp'; of guns. In 1799 be went 1.0 London and \,'a.s one o::.d the 'itmnders of the Royal Iii.~tituti>OI!.

(p. 65)

BI}J-n near Manchester, JOllie was 'f:dli!;ated at home. The majn work \\lhich eceupied the greater part of his life was 011 the relati<1llship between work and heat. He estahli~hed the principle

0:1 the mechanical equivalent 01 heat.

I.

JAMES CLEJlK MJ.,xwELr. (1831-11379)

(p, 7S)

ur.]

In ] 799, Davy showed that when two pieces of icc were rubbed together water is produced. It was admitted b.y, all that Wa.tL'T has grea ter quanti l y of hea t than ice, t Now supporters 0 f the _ caloric theory 11~ serted that hell! t is genera ted in friction becau se the su bsta n ce produced by friction has less capacity for heat ,than the original subslance. But the substance produced In Davy s experiment (water) has gr'eater heat capacity _ than I(.e. hence the caloric theo.ry became untenable. Davy's experrrnent proved the gTe'ate:'l~ stumbling block {or the caloric theory.

Buc the valuable work of Rumfordand Davy was soon forgotten and it was ~tlly about forty years later that the first law of Thermodynamics gained general publicity through the re-searches or _JOl,lle in England, Mayer and Helmholtz in Gennany, and CoMing in nenmark,

z. Jollie's bperimeols.-In 1840 J. JODIe o] Manchester began his classical expcrfrnents for deE.eTmining the relation between the work done and heat genera ted. We do no t wi sh to describe these ex pel' irnents here in detail as they, <Ire at present only of historical interest. The h ~ot 1 was produced by ch urn in g water contained in a cy lin der hy means f)r brass paddles, This ootll(~ be k,ept revolving hy means n ~ a doub I c thread wound over a solid -cy liridcr and pas.m1S ever rLllJ('\~. .irul carrying weights at either end, The amount 01 work (lone \\',{S rulculated by observing the height through which the weights fdl. 'Lhe rise in temperature was measured by. a mercury thermomcur and hence the heat generated could be found. After applying Vii' illm cru-rections Joule ronnd that 772 Ft.Tbs, of work at Manchester c.rn 1 ;li~l' the temperature of I pound of water 1°F. In 1878 Jou1e m~'d :1 modified [a,rm ol the app::J.ratus in which the work done was 1 ,w.mll t'" hy the applica don of au external couple as in Rowland's , "10[", illt'-n1 s LI:) be descrlbcd later (§ 5_)

3. First Law ,of Th,enn!lldylllamk&,- The conversion of wor k into ilr ,,1 wns thus established hy the experiments of Rumford and ]oultJ_ J\. iw, l.etween the times of Rumford and louie, the steam-enginehad In-i-n \'\'ideIy applied for various industria pur-poses. As we shall see LII~T, this is simply" contrivance for the conversion of heat il:1to wmk rims it is established that heat and work are mutually convertible.

;>.r:ly, we may go even further and say. that when some work is spent in generating heat, a definite relation exists between the work spenr .unl heat generated. 'These two facts, vix., the possibility of cnnve:rdng wlllk inln heat and vh,t? Vf:'l~,~a and the existence of a definite relation bd W(-("11 the two arc ~pre5~,c:d by the First Law of Thermodynamics, Marln-mntieallv, the Jaw may be stated thus:-

H ~V IS the work done in genErating an amount of heat H, we ha ve,

W=JH,

( l)

+ Thls 'was proved b}' Black'$ ri'i&;wc.y of Latent Heat of Fusion, He. h~ml-': equal masses of ico arlO ice-cold water alternately inside a room and observed tiJat the water W;;IS raised 4·C ill half-an-hour, ":bile the lee luok 300Ut, ten hours to Iller t 111to wa tel", the temperatura f(!])l<!:i ning con s taut,

5

66

KIK£TIC T.HEOl1. 't' OF MA TIl'lt

[ CHAP.

where J is a constant, 'pm~ided all the w(?rk. done is, spent in pr~duc. 111"· heat and. no portlon is wasted b~1 fnctIOn,. rac'ha non, etc. If H is ~x pressed in COl. lories and W _ in .ergs, J _ 4} 85 X 101" The tru, ili of the second statement embodied m the law IS amply. proved by the bel: t~at the various melh()d~ for fiulling J (sees. 1-7) yield almost identical values.

4. Met'h.tI(ls for determining J.- Various me thods have been devised for finding the value. of the mechanical equivalent of heat hut the method 01 fluid friction and the electrical method are the only ones capable of yielding accura~ T{:~:nlts. and h~nJCe ?l1Iy these will be considered In detail There 18, however, an mgcmol,ls method of calculating we value of J which was first given by J. R. Maycr in HH2. }~l"'Om the theoretical relation J (C p - C.) =.R (p, 46), he calculated lhev~lue o{ l. Thil,ls., Jor hydl'ogen R = !JflVfiJo!T.r, = SJ1l4 X 10' ergs per molper tiC (!'Jr, 6, 10) and C p - G. = 1..985 cal. per rnal pet· QC (p. (2) .

3"314x 10? ~ .

J=-. -Hl85-= 4.18 X lOr ergs per (alone.

Certain other methods" that have been employed areenumerated

bclow i-»-

{I} Me<l~l,lTement of hear produced by cumprc&~lng a gas-Joule. (~) Heat produced Ly percussion-s-Hirrr.

(3) Work done by a s(eam-engine.

This was used bv Him in 1 flG2. He measured th.e amount of steam entering' rhe cylinder of the steam-~:ngine in <l. given time at a known temperature and pressure, The lOL.'I.l hear rejected by the engine was found by eonducting the waste steam into a calorimeter, and the heat loss due to cooling and other causes was estimat-ed. Thus the net amount of heat which is converted into work is obtained" Th e work don e by the engine was fou 11 d from an indica tor niagram (Chap. 'IX_)_ Equating these two Him go( it value of J= 4, IS X 10" crg~ per calorie.

(4) H ca t de vel oped in ;'I cylinder kep t sta t.! on ary, in a rota Ling rnagm:tic field produced by means of polyphase <llt.enmting electric curre::nt-Ik:tiUe and Ferry"

5. Row1andJs EII.p,e~im~Dls.- JouTe's thermometers were not standardised and thin en-on of 1 011" 20/(.0 may arise from thia Cause. The rate ol rise of temperature in his experiment was rat.her slow {about fj,52"C per bour) and hence the radiatianootrectiOD was iarge" R Ow land min imised this ~OIlIT.e of unecrtal n cy by designing a sped al apparacus with the object of securing a rapid rate of rise of temperature: {40<>C per hour) , the principle of £hr; method bring identical wi th that of Joule.

~ FIll- ~ cfi'l7[-.:)kt.~ list (If the methcils see Gli1l2:cbrol}k, A Dk~~~tHl1'"U 0/ AppUed

Ph3.'sic.s. Vol. 1, p. 4RO. " . -

III,!

61

'J he calorimeter was firmly attached to a vertical shaft ab [Fig. r (fI) I tl) ~,l/ h [ell i 5 fixed a wheel ld wound. rou nd wi th a str Ing carrying wr 112.11 [~. 0, p at either end, the whore being suspended by a torsion

wire, The axis of the paddle fF.ig. I (h)] passed through the bottom ~lf the calorimeter and was attached to the shaft ef, The lereer could be rotated :unifor~y by, the wheel $" driven by a ~team"e::ugine_ The number of rev'olut1ol1.;~.Jfa.~ automacically rewtde,d on.a chronograph worked by a screw On the ~haft ef." The revolunon of the paddle at an cnorrnous tate tended to t'Otatethe calorhneter in the same directlon on acC01U n t of fluid friction, TIl j s was prevented by the external I:otlple produced by the. Wt~l,ghts 0; P and. the torsion wire" For th(:: lmrpose of accurutely determining the radiation correction a water ji!d1(~t tss surrcnnded the calorimeter,

. _ Th;e padd.le Is ind~caltd separately in }l'ig, 1 (c). To a hollow {'),lwdncal aXH fourtmgswere attached, each having eight vanes,

I.

I

68

KINE1i'IC 'rHEORY OF MATTER

[CHAP.

Ill, ]

69

Around these were tile fixed vanes, consisting of five rows of ten each, which were fixed to the calorimeter, Thus the liquid could

!

non-condtH:ting ebonite pieces attached to a brass cylinder_C. which can be made to revolve by means ol a motor. .Inside A js another I )l'fJ.% cone B httfng smoothly into it and attached rigidly to a wooden

disc D. The latter has a gro·ove .

runnina round its circumfer-

en ce aI~d carry,iag a cord VI' hich

passes 0 vel" the pulley Pan d

su pport~ a weight mg. W'h en

the outer Mne rotates rapldly

the inner one tends to move in the same direction on1iccount of the friction betv ... -een the two cones, but is held in position by pro per 1 y ~uspen ding a sui table weight mg:u the end 'of the cord, The inner cone R contains . some wa ter, a thermo· meter and a stirrer: (no t shown) .

W hen the weight m.g is kept stationarv the tl.ll'Din~ moment exerted by it just. balanc~,!; the f~ictional c:~mple._If D ]5 the- diameter of the dISC Fig. 2.-A simple laboratory apparaLu~

(be frictional couple is mgD/2 for J.

and tIie work done by it in ?l

revolutions of the cone is 2n.,..mgD/2. U 1',,1 be the water equivalent of the cones and the contcntli.&fl the rise of temperatum pro· dnced by Irietion, then

F!g. 1 (1:»_

Fig_ 1 (d.

n1TmgD = Jmoo,

(4)

be vigorously churned- The rise of temperature was recorded by a therr:omeLer suspended within the central sieve-Iikecylinder in which

water circulated briskly. .

n D denotes the diameter of the torsion wheel and mg, mg, the wei~hts suspended, the work JiV done in 11 revolutions of the p-addle is gln:-n by

W = couple X angle of twist = mgt). 2'lTu.. • (2)

If M denotes the thermal capacity of the calorimeter and i~s contents, M the rise in temperature (Correr.h:d. for radiation) , the heat produced by friction is M go, hence

J = ~~~f'_ (tl)

:H D is in em. and mg in dynes .. J comes out in. erg ... per calorie,

Corrections were applied for the t.01"8101"11l.1 couple, £01' the weight.s in ~i:r which must be reduced to vacuum, for expansion of the torsion wheel, ete, Rowland found J = 4J79 X 107 ergs for the 20-:' calorie: Laby recalculated from Rowland's observations by applying cOrrC'~twns and ohtalned the value J = 4.187 X I'll" ergs for the 150 calorie.

Reynolds and Moorbv obcained by 11 modified apparatus, thevalue of the mean calorie betv.;een ijo and 100°C to be ·4.l833 X l{17 ergs. H crcu sand 1",1. hy employed what j s in prlrici pre a r~ ind u cti on rn otor, to find J, and obtained the value J;:::::::= 4.186 X 107 ergs per caloric.

6. A Simp]Q laboratory Methtu!l of finding J.- For laboratory purpose~ a simple 8!1)paratLu; for finding J due to G. F. C. Searle is shown in Fig_ ~, but the accuracy attained by this apparatus i~ not great. A is <I. brass cone held rigidly in position hy means of

whence .J can be ea Ieulatcd,

. 1. Elec.1rleal M~th.o.ds.~Th~e m~tbod~ 11a ve a]rea~~, been described (pp. ~7"4n m full deunl: It IS easlly seen that lf ~e speofi_c heat of the liquid be known, this method gives the mechanical equI" vulent of heat. There are tv.m ructhods c-« (]) .steady-flow method. (2) Rise in temperature method. The former was employed by Caliendar and Barnes who did their experiments with great care and skill, but the principal source of uncertainty in their work lies in the value of the decttica:l units employed. _AiCcOl'dlng to Laby we molY P II t th e E.M. F. of the Clark ceil used by, Callandar and Barnes as ] .433S volts :3I:t 15"C. Th?y employed the international ohm which is eql101:1 CO LOO()5 X lOD e.m, units. Reducing Callendar's results with the help of these data l..abt gets for the mechanical equivalent of the 20 0 ca Iorie a value of 4.1 f 95 X 101 ergs. This yields 4.1845 X 101 ergs as the equivalent of the 15" calorie, The rnoet, accurate experiments on the subject are those of Ja.eger and Steinwehr by the' rise of temperature met. hod, and of .Lab)' and Hercus by tbe mechanical method, the respective values bemg 4.1863 X 107 and 4.1860 X 101 for the l.~Q calorie. Osborne, Stimson and Ginnings have recently found

.',

"

I

II

I

I,~

'I

70

I

)

the value 4,18.1)8 hy the elecrrtcal method. Hence, we can adopt the value 4.H16 X 10' ergs per calorie.

Exercise,s-: Joule found that 77B ft..lh~. of work. can raise the temperature of 1 pound of water 1"10'. Calculate the mechanical 'e~ ui valent of heat in C.G,S, units,

l 7/8 ft. lbs, = 778 X 3U A8 X 453Jj gm. X em,

= 778;< 30.43 X 4·53Ji X 981 ;:::= L055 X ]()HI ergs.

Heaa produced = 453.6 X t = 252 calories,

J = 1.05.1 X 101<'/252 = ,U87 X 1(11 ergs per calorie,

8. Relit as MIDli.Qllof MI!I!e&1des.-From these experiments it Is dearly established that heat is a kind of modon, the next question l~ -11'wtiort of tvhr;t? The answer was giv~n by Clausdus and 'Kronig in ] 857 :fm the case of gases .. They said that heat consists in the motion oI moleeu les or the smallest panicl es of matter.

The idea th at i ( we go- fm dividi ng matter 1I~'r:: ultima ~el)' rome to small p"rtides whieh Canl1{lthe further subdivided dares from 'very ancient rimes, But it remaineda barren speculation dll Dalton g<Lve to it a definite forrn in the middle of the last ccntur~·. The history of the mclecu Iar th eory is k 11 ow n to all our readers and no accoun L of it need be given here, Suflice it to sa]" that lIocorcling to it a11 mutter is composed of> a large n LImber of molecules, nil molecules of the same substance being exactlv identical· as re~~U'·ds mass, size, etc, but differ in their motion. In the solid and liquid states these mole( I Ii ~ s are cl osely P 8 (' ked while in ga.5C5 Lh~y an: f n:r apart from one nnuther.

X ow accord: n g ro the K i 11 etic Theory of M a tter he at is sn pp osed to eonsist in the motion uf these molecules. The identification 01 heat with motion of molecules is not a mere hypothesis. II. is able to C':.:.piain ~nd, rredicL natural )Jhenomcn.1i and at present there is Tittle dou b t that It rests 1.:1 pon solid founda nom of eru tho

9. Growth of tb.Q Kin.etic: lbeory.- The Kinetic Theory of matter rests upon two fundameneal hypOthe~e.~ ~ (1) the molecular structure or matt.er, (:2) the identifi,cat.ioiU of heat with molceular moticn. The fil'~t of these MIS established early in the 19th CellUl1'Y, wh]~e the ~el(:ond W.1S established. by the experiments of Rumford, Jcmh~, rVfayer uud Colding. VVe nuy, how{'!'ver, consider Daniel Bernouilli (1730) as the founder of the: modem kinetic theory as he was the fiI'~t to 'explain Boyle's law by rnolecttlar motlons, Clausius and Maxwell in the !l1idcile of the [9d1 eentury placed the theory on a firm mathematical ba~i.~. Among the o~hcr prominent contrihutors to the theory are ]~oHzm~nn. Meyer, .Jean~. van del' Waals. Lorentz and Lord Rayleigh,

Up to the beginning ol the prcscnt century, however, the theorv bad been devdoptd endrelv from a mathemarical stand-point. There W:lS no direct experimental proof of rhcactual existence of these molecules or of their motions. Gradm'lJIYJ however, much evidence has

'I I

1 ,

I

I

72

K[NETIC THEORY O'F MATTER

[CHAP.

The Brownian movement never ceases-s-it is eternal and sporJ& tan(:~:H.lSr and is lr,ldepemlem of tl.1C:. cherr~ical nature of, the suspended particles, <111 particles of the same size htJng equally agitated, Smaller partides are, however, much more vjgoromly agitated than bigger ones. The motion becomes 1110re vigorous when the tcmpe:rature h Increased or a less '1,,.j~eOU8 liquid is chosen. It is [ust perceptible in glycerine. and very active in gfl:Sf;!i. No rW(l particles are found to execute the same motion, hence the motion cannot he due to any

con vee tion or eddy currents, .

'The d1s,tovery of such spontaneous motion, and the fact 'ha~ the il1.olion is maintained even 111 viscous liquids without the application of any. force was II. great puzzle to earlier ObSC1'VCJ"S. Gradually, however, rt has been established that the Brownian movement is due to the impact of t.he surrounding molecules of the liquid on the

lJ Brownian particle. It is evident that the M[cr~~ forces du e to moIc:uhl i n;'Pil. ct w ill al~mt com pl etely balance I [ the SIze of the particle is very h:rge(sOly, 11: large body immersed . in the liquid) but then'! can be no balance

.. r....!J:;I::::::;:l;;;;;,=_ .. ==~= ... ~ ~rr--. .if the 8Ize is small, A ny small partkle will,

I ,.~: I ,f hercfore, be a ctcd on bv a res u.J tant u n-

. -- - balanced Iorre 'and will" consequently exeEmUhi.rm cult: motion. As this force varies at

Fig. 4.-()b~ervlng random, so the motion of lh~ panicle Will

Browm"n movement, also be at random and will be somewhat

similar to that: portrayed in Fig 6 (p. 81). Thus the phenomenon I')f ~nlwnian movement .is iii direct proof of the existence of molecular inottun.

'The ~tmJy (1 r the kinetic theory is best a pproachcd tlu'I(mgh a study or gases, The kinetic theory of the liquid anti solid states is compara(;.ively undeveloped and. will not be dlscussed in this book.

12.. PU·Slme Exerted by a Perf.ed G.as.- It has been shown above that a gas consists of molecules in motion. As a cousequcnce, it must EXLTt pressure 011 the walls of its enclosure. To calculate this pressure we first make several simplifying assumptions, These are the fonowing:-

(l) Though the molecules arc incessantly colliding agaimt one another and having their velocities altered in. direction and magnitude at each c.olligiOll, yet In the ~teady state the collisions do not affe[t the molecular density of the gas. The molecules do not collect at one place .in. larger numbers than at another, Further, in evety element of volume of the gas the molecules are moving in all direo~ ion 8 l':Tj{ 11 . all possihle veloci ties" The gas is then SoU i d to be ina ~t1tte of motecuiav chews.

(.2) Between r,WQ collisions a molecule moves in a .~traight line with uniform. velocity. This i:o; because the molecules are material bodies and must obey the laws of motion.

HI.]

.PRESSURE EXERTED BY N:RF"lI.C"r GAS

13

(3) The dimensions= of a mole~ure may be l'H:~Ie:~t;~d in comparison with the distance traversed by It be [ween t.wo collisions. called its free path. The perfect gas theory, treats the molecules as IDe1'(! 111 ass-ooin ts,

(4) The time during which. a. collision lasts. is negligible compared with the time reqw red to traverse the free pa th,

(5) The molecules arc perf.ecl:ly eIa.stiet. spheres. Further, no appredab1e force of attraction orrepu1swt; 18. ex~['t~d ~Y .them o~ one another or on the walls, i.e., all cnerg~1 IS kinetic, TIllS IS pl'ovecl by Joule's experiment (p. 47),

"'\Ie now proceed to calculate the pr~r.~ure exerted by such a ga£. We will employ the method of collisions, because It -is 'Very simple.

Imagine a perfect gas enclosed in a cube of unit sides and consider a molecule moving with the resultant velocity c and component velocities 1..1' s u, w along Ox., OY. OZ axes respectively .. The axes are taken to be parallel to the sides of the. cube, The m.olecul.e collides with the surface of the cube perpendicular to OX w!tb the velociry u. . From the prfndple.8 of conserv~,tioJ1 of energy ~~Ild rnomeutum it follows that it wlill rebound with the same velocity, Hence tIH~ change in momentum s~lffel"ed by l,he. molecule during ('?lh.-sion i~ 2mu... Tl\c. molecule strikes that particular ~lIrbce ill.'l umes p~r second, hcuce the change of momentum per second IS 2mu"uj2 = 1nu2• Since pressure is equal to change ~n mOl_?entum per second, .t.1u~ total pressure .cx.e,rced on that surface rs !1"kttl~ where the su mma tion extends over all tb e molecu leg,

(.1))

,Eu2 ., n ".'.1-.. ~ 2 Il th

N (JW ._ - ="U6 wuera Ur IS me a \ferage or U over a tr e n

n

molecules.

r, =mnu·~

Similarly, (he pressures on the other surfaces ate

(6)

II< Ii we consider the dlmensions of the: niol ecule and the £on~es GP a tt [action .. we get vall der Waals' equation (Chapter IV).

'f Thr :;I,~ sum p¢ion (If perfectly ~l:oI~tlc colllslons, on the avem$~, is wart;1,nteJ by th e fact that we can convert mto work all the heet ~U[)Pll~,d It) a per[ect gas, For otherwise addition of be.i!..t would increase molecular ..,.e[o6tl,~~ am[ ] I ence als (I the f{)rc~ of (;()I'I LSLon, and if dd'U:L1nat lou of molecule results, aH heat til Ii)' not be C("JI"]'l'ert~ci ·l1a.ck to work. The pich1:re here gL ven is essentially tbat of :;I, monatomic molecule: rhen~ wLll occur deformations of pnlyatornie molecules, accompan led b~· B.ttilt(.rca.~e or clecl-eEse of rotational and - vibrational en crzies h III on the average there f s 110 net loss or gain or translational ene~gy dn ring tolJi>.;iOfI, Equation (9), however, ean be deduced wiLhOlRt the assumption 0:[ ]lei'It.'1:tly elastic (;'tillisiol1. For details see the Authors' TrltaJi~c ".1'1 Heat, See, 3.12, foo!note 2,

KINETIC T[-f~()RY OF MKJTER

m.]

75,

[CHAP.

DE.Dl)(:TloN OF GAS LAWS

where v.~, wll d.enot.e the ~1!lea.tl square velocities iu the ocher two perpendieular direccions. Smce experiments= show that j)= P =Jo

we have ~ s r=r e

The Iormula also shows that the molecules of the lightest gas, tnx., hydrogen, would move faster than the molecules of any, other g·RS under the same conditions.

13. DedndilllD of Gat! Laws- From the above re.'jult~ we proceed to dedu.~ the 1:1 ws uf perfect gases.

(1) Avogadnl's!l Law.-U there are rwo gases at the same Ft"cssu re P .~ ~ have Irom (9)

p = :ttn1n1C12 =tm:gnllCi'., (12)

where the subscripts I and 2: refer to the tint and the second gas respectively, Further, H the two gases are .also at the same temper·atUl'e we know there ' ... ·m be no transfer of heat (or energy, since the two are equivalent by the First Law of Th~T1'llod)'naJ1lks) from one to the other when they are mixed l.lp. On mixing. the two types of molecules will collide against one another and there win be a mutual sharing of encrgy.. MaKwcIlt showed purely. Irom dynanrical considera I..iom that the eondl tion fo!:" no resultant transfer of energy from on e type of m olecules to the other is that the mean transla tioual energy of molecules of the one type is equal to that of the other. Hence if t~H:~ two gases arc at the same tem perature it follows tha t

1m1C12 = !mZC22. (13)

Com bining (T 2) and (T 3) we get

1,1.2 if1. = w·2•

T'his is also to be expected from the fact that the molecules do ~en d to OlCCLlm ula te in an}' pan of the vessel, But

- -_ ] ]

tl2+[l'2+W~ =.2:.~(U2+V~+W~) = -1](}~ =c2 (~)

n 1l ~

where c2' is the resultant mean square velocity. Hence froaj (7) and (8)

(7)

not

and fdF.laUy (6) yields

p = jrmnr. (9)

But mn:= r J the dCf.ls.ity of the gas, since n is the number per C.L

P = ~p' c2" (10)

=ij-. ~pc~ -= 2..E {11)

·wh,erc. E is. the kinetic energy .per llnft volU1~e: Thus we see that IJ1C P!ess1oJte of a perfect gal> IS numerically equal to two-thirds of tile b~enc em~rg}'~ of ltans~aLion r= unit volume,

. l\. e have considered a 51l1gIe molecule as if it suffered no collision with others. If a mnlccuje encounters another it ... ives its whole " 11)011 :ll tumt to the other which bv assumption (g) h

cxa t lv th· 10• ' •. • ~ as to traverse

• < : • j e same c l~L~nce as the I.lIst one if there .had been no

collision. By assumption ~'1) no nrne is lost in thi I1• • ;J t . 1 1 • .... . . us to nSI()n ano

tellc~. OUl'. ca curanon hol S true fat a perr~ct "'as.

~y. It.a ti on (1 O) CJJ a b Ies til; to calcula te th e mean sq u a re

velOCity ~.~ of the molecules of any gas, fur c~ = 3:P/ p, The pressure and (~~ mH Y r- ~£ . a gas ca n . be found experimeu tall y all d hen ce r.1]

calculated, . I. hus the densitv of nitrosen at O°C ... d' l-..'

. 00 ' I 0-··' ,,[I acmo:;p!!enc:

pressure IS . ." 0125 gm. per c.c, Hence for nitrogen the root meat;

.square veioc~tj':t .

C = ... /~ • /3x 76x 13-59x981 ..

V e = V--O.00125 - = 1.98 X l04 cm./&ec.

(14)

i.e., two gases ac the same temperature and pno.ssure contain the same number of molecules per e.c, This is Avogadrd's Law.

(2) Buyle's Law.-Equa(ion(lO) states that the pressure of a g·as is directly pro _port ional fo its densi ty or 1 nversel y proportion al to ib volume, Thlli is Boyle's Law. This holds provided OJ remains constant which, as shown above, implies that the 'Lemperacure remains constant,

(3) DaUm'!;':; Law.-Tf a number of ga,~e~ of densities Pl. p~, p~

... and having mean s.quare velocities C12,C2,~' C~2 be mixed'in

the same volume, the resultant pressure p, considerina each SCt of

molecules is given IJ)' o

p = fplCl-H-p~C~~+-}P,aC~t\+" .

""" P1+P2 + Pl+ ... (I5)

*COlmt Amooeo, Avogadro d] Q uarogua (1 i7 5-1856) was born in Turf II where he was Pl'[)irs.sor {II Phygics from 1333 to 1850. Hls chief work ·is Avu1,""-dto's law ..

t Maxwell c(l1l~ldr.r~d the ~.onision of :;la~~t:llU narcieles {If t ~\'o different types and possesslug diff~te.TIt amounts of eTI.eI"HY. By apply[n~ tile dynamical laws of Irnpact\-iz. COtl~er'fation of luome,ntum ami energy, he found that aILer each colllsicn tbc. diffen'rlce in !allergy n'i the h ... o molecules diminisbes by a certain traction, i.e. the molecule possesslng v.re'l1Jel' energy loses it while that possessing less energy gain!;. This process is repeated at each eollisicn, ld.od llltimal:dr the f!nergic~ (~f the two be.eome equal, For details, sec the Authors' Tt,~c,fr.se Ol~ Heat (19"S)JPP. 845..&47.

MA...XWII.LL·S LAW OF mST!lIBUTU)N or VELOc:tTIES

76

tn.,]

77

KIN.lI.TlG T.HEOR Y OF MAT f.r.:R

i .e., the ph'~ssme exerted by the mixture is. eq ual to the sum of the Pl'f:lcS5Ur;S ~xertect sevaratdy by, its several componenl.'l, 'l--m~ is-. Dalton. s law e,. partial pm'::;MII'es"

14. Intoodudion' of T emp.emtllre..- [f we consider a, grammolecule of the gas which occupies a volume V, equation (10) yield!;.

PV = {MC2, {IS)

1~1 being the molecular weight. In order to introduce temperature in the fo~rcgoil1g kinetic consideratious of .<1: perfect gas we ha ve to make use of the experimental law. uiz., jJV = RT. Hence

RT= 'VrlC~,

"".lI_ 3RT \.' - M

pO-!i.Se!i~ the same ~pttd, callisions Ole the next moment win augment the veloci ty of some and. dimi n ish that 0 f the others. As the number Q[ molecules ll; very brge (2.7 X 101~ per c.c, at N,T,P,) and. they are reo small to be visible ,even in the ultra microscope, we do notrmeeest ours . el vcs in the bell a viour of individual molecules" ,"V,e trea t the problem .'ltasiS:~]>CaHy, and apply the theory of probability. We shall illustrate th.l~ by means of an exam pie. I n a big ci ty (here are r:er~o1U of aU ~g~s and "live find the number of persons whose ages he betl'1lt.'C'n definite range~> say between 10 and 15, 15 and 20, and so on. So in au assemblage of molecules where the molecules have all velocities lyi n g bet ween 0 and inn Mty we find the Humber of mole(u]esd11~ PO~!(~&.~.ing velocities lying between c and c + de. In. ~he steady state this number remains eonstant and 1$ not modified. by

·c{}I~ision.s. This number is giy~n hy the distribution. law of Maxwell

which states: /

dt~. = 4'11'nast'~bt2 .c~Jc,. (lS)

where n ist.he number .oJ! molecules pel" c.c, and a = yb/IT" = Vrnj'Z.'1f"kT. But we cannot.s,ay wharthe velocity of arry individual IDOl e~1J le seIe.deC!" at . random is. 'oV e can 0111y say that the pmbabHity til a i. U5 veloci ty Iies between c and c + de i ~

4?J";ol2 rb,;~ ,Pdc .

~nlUS th~' disteihutien law gives a complete knowledge of the gas only ur a statistical sense.

A sliglu; eransformaeion tput,ting bc2 = ;.;:2) wlll show that the

number dn = 41lll,ix~t'-x"dx~ which herptl us to represent the law gTaphir_ally" Let. Us plot the function y = 41l"~f (FX~;(2 against x

or

(17)

Thus C~ is proportional to the absolute temperature whicll may thus be considered proportional to ~lJJ.e mean kinetic energy of translation of the molecules. This is the kinetic interpretation ·of temperature. Hence, acccmding to the kinetic theory, the abr.o]ute zero of aemperamre is the temperature at which the molecules are devoid of all monon. This deduction is, however. not quite justified since the perfect gas state does not hold Q0\\I]1 to the absolute zero. The interpretation given by thermodynamics is somewhat different (Chap. X) and 1S more reasonable, That does not necessarily l't:quire that all motion should cease at the absolute 2leTO.

\Vc can pu.t M = Nm. where '.In ]~ the mass of a :s:ingle molecule and N the IJ umber of molecules in a gnnn-Ulolecule, which is usually called the Avogadro number.

\'1/ c em pu t It / N =- k where k ]s a constan r. k is known liS.

Boltzmann's constant. Hence we get

p = (NjVJkT = nkT~

where n denotes the number of molecules per c.c. Further from (17)

+,Nm.?£ = ~NkT;

or -ll-mc'2,' = t-k T.. (~7a.}

i.e., the mean kinetic c:nergy of translatinn of One molecule is 4 k T, Exercise,-Calculate the molecular kinetic;: energy of 1 gram of helium at N .T,P. What: win be the ene:l~:ry at 100°C?

From (17) the kinetic energy ise(l ual to

" ~ RT B.3y 101 X '273 010... IO'D

tc-- = i M ~ 4- =",,";.) X ergs,

Energy at lOO"C = S,.;5 X 10° X 373/273 = Ll6 X 101(1 ergs,

15. DisUlh(lItinlll of Velocities.. Maxwclrs Law.-In the above we were concerned onl y wi th the mean sq uare velocity and did not cafe to. find the veloci ty, 0 £ every molecule. ::gu t . for st tidying the pmpewe~ of the gas Iurther we: must know the dynamicat state of the whole system, It is easy to see tha~ all the molecules cannot have xhe same speed for even if at any instant all the molecules

(Fig. 5). Then the number dn of molecules whose speed lies bdween

y

, '0 ri'i""Ti"TiilTiTTrT"l--rT'l""T""""'M-f"T'"'lrT"'!"'T'"f'"'T""'I""I-r-L

,-+-++t-+++++++t+;_~+-I + .... +"'-++. C~r.\'e~HIl~trJ~ing m . +1 "~I+t-t-t-+-H"",H ~hn::w(llrs .d;'strdluhon taw", ~

cs ! .~. t. . ~: I . .

j

II I

KiN E'fIC THEORY OF Mil. TT,E.R

[GHAP~

7S

x and x + ds Is proportional to the shaded are~. The ordinate y givcs. the fraction of the number of molecules posse~s;mg 11. speed ?J:rres.p~n~. 11115 to x, and from the curve it :~ n~v~ous th.at the probability t:o~r<.:~:' )onding to .'>I! = 1 is greatesl, li~ThIle It IS {o~lderably les~ .lor x = ;:.. T 01 1. =-:-}. Hen,ce ,we cau appro~rllately t.reat. the wholeg<!'!; as endow ed

with the mOSL pro, hable ve,! ocuy rone~pcmdH:g .co x.~ 1. ,

Hi. A"Ii"€fage V e1odties,- \Ve m ust dLS l:loglml1 b~n~Teen two.

velocities, ~e square ['![~ot. C .0.£ the .mean ~uare ~vel~r.ll_Y" and the mean velocitv c. The former IS such that its :;qll,lre IS the averageof the squares of (he velocities of the I!loler.1.l1e~. Thus

- 1 r I;IJ , :3 3kT

~ = c~ = n J 0 c~dri~ =2b =--;;-'

which we have already obtained in (17).

The mean velo ci 1:)'

- I J~ V3kT.

t = - cdn.= __

ti Ll m-':II"

~- = V~l~ = ·921. (21}

The most probable velocity t}! is that value of c for which, N, the number of molecules with ydncity c is maximum. Hence lor .~uc.h

fiN l··" bstl . f 7!.)

va lues of c, • = o. This re auon gIves Q:', Su stituung or H, we

de

(20)

get

(22)

An interesting consequence of the large molecular velocities ]!i! seen ill the! a 1 most complete absence of an atmosphere Irom thesurface of the mOOI1. Dynauiical investigatlons show that if a particle

is projected horn the F.awh with a velocity exceedfng y2grt! whereg is the gravity at the surFac.e uf the earth and 1"(1 its tadiu~,it will never rerum 1;0 the earth and will he lost in space, This critical vplocity is about II kilometres pel" second for Earth and 2.1 kflomecres Ior the moon, Russian scientists have recently (2nd .J an tr ary > 1959) been a ble to 101 un c11. a cosrni c rocket ,. Much ta' ,Ii' hich overcame the Earth's gravitational barrier and flew past the moun Into space to become the fin;t artificial planet of the sun with an orbital period of lH 7 days.

,Galruhtions show that the avera~ velocit.y or hydrogen at \ ordinary tempera Lures is abcut Lfl kilometres per second and according to ;:"!faxweU's law a large number of molecules have velocities much greater and also much less than this, Thus all molecules having vclocitv gte::tterthall (he critical win escape from the planet. Dueto molecular collisions a certain fraction will alwavs have velocity greater than the critical and will escape, This loss .of the pranetar)~ atmosphere will continue indefinitely. It. is for this reason that there:

111·1

J...1I. W OF EQU lP AlUT]ON OF ~i~t'iiERGY

I~ pta(.timlly no atmosphere on the surface of the moon while the nunosphereof the Man is much rarer than that of the earth,

11. 1.01. W of Equipartitr'luiJ Itf Kili:etk EI:U~fgy.-.W e next. proceed (0 deal with the l~w of equipar.tltion of energ-y. It is better to, introduce here the Idea of degrees of frfledotn of ,I ~ysLem. Suppose we watch OIn ant constrained to move along" straight line; it has.

then only one degree of ll'eedomand its eneJ."b'1' i~ gi'V~n by t~2. If it is aTlowcd-w move in a plane the ·energy is given by imi:2 + !m;12,. An ant cannot have more than two degrees of freedom, but a bee which is capable of flying has three degrees of freedom, all of' trnnslation. Thus a material particle, llupp~s:d to, be a point, can 'lave at most three degrees of freedom. A rIgId body can, however, not only move hut also rotate about "lly, axis passing through itself, The most general Kind of rotatory motion can DC resolved analyticallr into rotations of the body about any three mutually perpendicular axes, thn1ugh a point fixed in itself. Hence the degrees 01: freedom contributed by rotational motion. are three, , 'I/fe may now state the definition of-the term 'degrees of' freedom'. 'The uota] number of independentquantltic$ which must be know:ii'"""'J3€fOi:-e fl1e position arid: configuration or an~' dvnamka system can be fully known is called the number of degrees of freedom of the system.

Now it can be shown from rigo:rOIu dynamical considerations that tile. energy cO'IT(2sr::ondir,lg Co every degree of, freedom 18 the same as for any other, ~.e., the eTWrzy is Gq1~ally distributed. between the' tsirious tlerrri!~'j of freedom, I'his is the raw of equipartjtion of kinetic energy andwas arrived at by Maxwell" in 18.5·9" Boltzmann+ extended it to the energy of rotation and vibrato On also, 11: can further be shown that the energy correspondlIlg to each dezree of freedom pl'..'r molecule is !~T+. TillS law 18 very general, but :e shall not a trem pt h ere to prove :it.

Thua if an", dyn:tmic.al svstcm has n degrees of freedom, the' ene~clat~ri"1rith--it :n-T"'X is-n X -11~T.

- .18: ~to]eC1lI!l.r ud Atomic Energy.- il1.e above theorem is very useful 10 calw1almg molecular energy of substances. Let, us c .. alculace ~he ~pC'cHic .. heat of gases". In a tu01'latomic ga.\the molecules are identical i ... -ith atoms and if, as a first approximarion, we assume the a~Ol.Il to be strucrureless point, theu from the pre'rious w.nsidera, tiona each molecule has got three degrees of freedom and will have the kinetic ener,f:l}1 eqLlal to ['. X ·.v~T. In the stare of perfect gas the

~''\~.axwell, Colle~i:l]d Works" Vol. 1, I), 378.

. t Ll1dwig Bo1t?llla.tLfl P8'l4·IW(6). Born and educated ill Vienna, he wa~ Pr'(>r~S~OT ,of ,Theorr:ti~iiJ Physics at Yictln.a, Graz, Munich and. Leipzig. On account or his fundarnc ural researches he LS regarik!d as (tile of the fOlmrl~l's of the kinetic theory ot gases,

* Eqtlation (I7~) gil'es imC" = ,~kT, Le., the mean killeHc energy of t~an~lalio!1. per l1101ecuJ e l.s ij kT, If w~ assume th!l;t the cTJcrgy :is egua][y dj,str1l.J.ut~d between the three degrees, (jf freedom, tbe energy associated. w ith one degr{~~ n~ freedom per molecule becomes i;k.T. For e. formal prcx]f of the Iaw sec the Authu'rs' Treatise (m IIeat, § 326,

80

KINETIC TH'EOR Y OF M A ITER

[CHAP.

molecules possess a~l}' k.ine~ic energy and no p~ten!i<l~ erle~gy. The total energy E associated with a gTarrl-moJeculc IS N times the above expression. It l~ thus equal to ijN!(T = iRT. The molar specific h eat at consta nr vol umc 1~ therefore

C.' = ~~- =\ R = 2:.98 cal.rdegree,

For all perfect gases we have established the relation Cp-'C~ = R.

Therefore, for 11. monatomic gas

c, = Si- +R= ~ R -= 4·96 cal./degree. and the ratio of the two specific heats

-; = 5jj = 1.6&. (23)

These theoretical conclusion!> :agree with experimental results (see T::J.ble .?!' Cb a p, II) for the monatomic gases like argon, helium, etc,

The specific heat, of poljatcmic ga.~es can. also be o~tailled by ming the equipartition law, The molecule of a dwfomzc ga~ ;'tlay be pictnrcd as a system oE two atoms (a~_sumed to be pOU1t~) JOln~I rigidly to one another like <L dumb-bell. . T.he S)lSlCm pO.s5E5.~e;>.m addition to the three components of the velccity or translarion of me common centre of grflvity, two com pan ents of the velocity o~ rotation about two axes perptnilicLllar to the line of centres of the 1',\,0 a toms, Thus the system has five degrees of freedom and the total f'11ergy E = ~j{ T. Hence

C" =~R) C p =;R, 'Y=-,1.4. {24)

'I his is <JpproximaLe!y the case for hydrogen, nitrogen, etc, (p. G~) _ At low temperatures, however, C~ falls to ~,.n, 808 Eucken's experiments with hvdrogen show, indicating that the rutation has d isa II peared, F o r chlorine. C ~ is greater than ~ R. T_his snows .that the two atoms are not rigidly fixed but can vibrate m a restricted

manuel' alon g t.h~ 1 ine 0 f centres . ,

In a triatomic gas a molecule possesses three rranslationa] and three rotational degrees of freedom and hence

C.=6 XtR=3R, Cf! =4R, y= 1.33. + (25)

For more complex molecules y approaches unit}' but :i.~, always oreaier chan it. It is not possible to calculate in a simple way the ~nergy of internal vibration of such molecules since the vibrations are not freely and fulLy developed.

An expression {Of the. specific IH~~d of solids may also he obtained from the kinetic tbeorv. We (an co:mid~'r molecules of a solid as elastic spheres held in 'po~itiO:!1 by the attrucrion of other molecules and capable or vibrating in a sl!Dple harmonlc manner about _il mean position. The molecule will have three components of velocity, and bence three degrees of freedom, The kinetic energy associatetl with each degree 01 freedom is tkT. On the average the h~monic vibration

III I

81

wi II have equal kinetic and potential energies and hence the total [ III rg~' associated will. each. degree of freedom Is k. T. T jum:::f?te, the Illul energy [or N molecules for the three degrees of Ireedom I~ l'}RT, .Illd 111 mob!' sper.ific heat is!! .~R = 5.955. T'his yields Dulong' and ~'I tit's law,

BtH the kinetic theory of ~p-acific heat is unable to 'explain the \ minrion of specific: heat with tf:mpetatlll'c:! (p, 45). particularly, the II arkl:'lt,· decrease at extremely low t.emp('.tatul'es. Further, the r lcrrr-asc is gradual and cannot be explained Ly the disappearance of ,Ill}' degree or lreedom which would involve discontinuous changes by multiples 00.1' !R. Vile cannot assume fractional degrees of freedom,

ktT the principles of classical dynamics and equipartition law fail «(,mpletely. The quantum theory of specific heat has been developed wlli(h explains tJle existing Jacts satisfacturil.y,

7I.fEAX FREE ~PATH PHENO}',H,XA

19. Need for the A~Slll!-'I,lioiil tbfL't jJjlo!el:l!Ife& ha ve giIl,i afinile Dlarneter.-1;Ve have seen in the previous sections that the molecules Or;] gas are moving at ordluary te.mper~tures with very large velocities: in the case of air it amounts LO about 4,00 metres per sec, There r ~ nn force to res train the roo tion of the molecules, H cnce the (ll,jcC11on was raised that the assnrnptlon of such large rectilinear \ dodties was incompatible with many facts of oliservation. If the Jl:l rucles are, moving with such eaorruous vclocirles, the gaseous mass rmtained in a vessel wouhl disappear in no time. But we are all

.rwarc that the: top of a cloud uf smolcc holds to,l{etht'T [OJ[ hours, hence I here must be SOUle factor which pre':ent~ the free c~cape of pa.rtid~s_

A very simple explanation was offered by Clausius. He showed 111,11'. the: difficulty disappears it we ascribe to the molecules a finirc I hOll['th very smail volume. 'Then MS a partirle moves forward, i r js 'me to collide wiL.h- another partide after a short interval, am'! irs .tlndt'f and direction (If motion ,~Till he complctelv changed_ The fmth traversed between two successive co 11 1 sions wilT he a stmigbt line ,I, '~cribccl with iii rnnstanr vclocitv, Soil] ce the molecules exert no force ovet 011t:_ another PXCf'pt during colIi5ion.. Hence the path of a single 1 ,.nid(~ will consist of a series of short 7.ig-7.a~ ]XI ths as illustrated in Fi!!;_ (),

Some of these paths will he long', others will be short. W'e (all define Q mean free path A _ Add

up the lengths or a l~l"ge number ~

{ff paths and divide it by the total i' 1·· ..

nl1lnb~r; . thiSf' will ~ive II, - Tt~iS~.. .. ,L

quanhty IS 0 great lmpor ance m

~Iudying a class of phenomena, called

tr;lHsport phenomena, such as yj~-FiO!". 6,-TllmtI'aLion of il'C:! prh , f)~i tv, conduction of heat ~ nrl

I Ifh I ~i on.

Zit CalcuJaticm of 'llie Me-lUi Free 'Path.-'Ve shal] give a verv ~ ill.pk method or (,JkulaLing the mean free path apprnxima Lely. 'We

.,

[CHAP.

-·IX ',TI(' TJIJ::ORY OF !!,ilATTER.

82 1>." ....

.. snmotion that an molecules except the o.~e

make the S_lll.ll)h~Yillg aS~l1111~ The moving' molecule will w~!Jde

~ under eonsidcra tron are. at, 1 est, . ..' lie within a distance ('1 from

rhos ·It:cules whose cen ...... cs ,"., 1-

with all u me nI? ". ' ~ the mo:~ecuk~), and. arc tUH. S

( b ina th,~ dlilrne rcr oi - f 1

i ts cc~tre _ IT e tJ '. Ii ! descri bed a bou L 1.J l!' _[t: u tre 0; t 1 e

contained Hl a sphere o~ ~a( '\ s , 1- traverses the gas. wah '\/'el{)n~y t, moving' m()lecul~: As t e mo em1,\ lin in the region traversed, by ~t will collide :w~th an th~T~~I:(';~:BJlusg traversed in a second J~, ~ II'S sphere of influence, " 1 d ].. , of volume 11'0'2",_ If the

, E b ~ and helght u, :11l renee -:lvn

evlinder 0 ase 1T{F" . -, , this evlmder rwill enclose '7Ttr .

1 f molecules 11er c.c. l~ t." " li . _,.,. .ond

t1lll1l )el' , ' , , 1 ' ber v of COlISI011S pf>r Sd':, _

- tres of molecules and hence t ie nu~ 1 ,

[ en ,. The lengt h of the mean Iree path

]5 r.(I'2..,tl.. 1

V' v

~.=-=- ., "

, );' ?'I't1·t'I~, ftrUer

1 .• :1SS111fled the other molecules to be, at r~sL.,

Iu uhe ~ }OVC\\: . : ression h introducing i~to the iore.gol~,g

;\(axwdl ann ected W1S ~p f ll Y 1 les acccrdina to 1h,x, .... eIJ s

, -"derations the motion 0, a 1)10 CUL .',. _ '.-,

lAJil.l _I 1 .: l the result

distril ~lltion law 1I11'll 0 )t[l.ln~t _,. -'

!

A~ -;-

..,/",b.lT1'Cr

]1- . suffered b,,· a molecule Fl:1"

Tilt" <L\'(:I':lg4.:' number of CO rsrnns

second is 8)" , ., . 1 expressed L:;

T' t Phenomena -lhe distrjbutmu a1,'.'

21. riiDsp01 n~ . •

li·n lll~~' also be put m the lorm

( , ~ mi,,'+l,"-l '(~l

( III ) -.f - '1f'j

dlT ..:.... II "'_' I <~

~W~ . M

- .. b, - f ol ecules wi dl veloci L y cum pon e~1I.8 I }'In~

where dn H the 11m" et 0 ~l ,'+ d wand 'W' _ r dw l'espectl'l,o·cly ... 11

b t veen u und H + du, 1.1 ann r~ V, A b ~ then

e .ween u . , -1 tion rcpreseutert- y U'J' Va, .V~.

the git~ i~ endowed wit 1 ruass rno 1 •

~~ ;til. (U~_I P+w.}

( .m. ) - - 2kJ" cHI .u: dW,. (2'9)

dn = n ~nl;T e

-" ¥--I-1J and n/=W-~Lrn'

where U = 1{ - Uil; - , (I , '.' •

, I • - not in a sLcady state anyone of the following cases,

It tlle. g,as rs '." (I) Fin;(j_'" tio, V'I' WI) lila], not have

singly or JOlntl~, ma}OCcul.{ the uas so Ythat there will be a relative

the same value 10 all pa,rt$ 0 S l!iih respect to one auother. We motion of the layers or the '1. . ltv 1 (2) Seeondlv T may not

have then the phenbomen~r 0 y:s~l~'l~~.?\he· Fhellomen~~11'1 of~llc1ncbe the same throug out, ten w. of b' rl ,_ T ~o regions of lower

. . _,' 1· t w:iU llaSS [rom remons 0 If; If.:I. .', •

non, Vl7...., le~ -d" ,; -, t 'h~ _ same everywhere we h:l.ve the case

T (~) Tbl1 y. 1 f! 1.S no l e . l: 1 . 1 ~, ntl'a .. .: ':. ':'. 1 l]e diIfWie from. regions (JllJ~P er c .... nce -

nf dlffuS100._. Le_, filEO elCl -~:en' _ tratloD It IS thus .ob",ioHS that

- t.o l'PG"wns U' owel cone ,. '., ,',

tl011 . .'"7;:> '. 1 dOff' . :epresent l'especnvclv t.he tnmspmt

viscosity. COU,o.uctlOn ,111(, d1 us,lOn;"h's' are colUed r.r~l1SpOl'l pheno-

of momcnn.U:ll, ,energy an mass. e c

IlL 1

83

(~6}

(27)

VffiuQsl'I'Y

uenu, These phencmeua are brough t about by '-!-le thermal agitation uf fLt: molecules, nut the molecules moOvewlth very large velocities, while these processes are comparatively very slow, The 1..11l~e 0.£ this anomaly lies in the Irequent mclecular collisions. Hence I he ~lLTd}' of these phenomena os most ,ooQ1veniently done tLuougb the ruechanisni of mean free pllih., The molecules q:l,rry ,,~Tith lllem ,'('rr ain associated lJlagll[tudt'~ and t~ereby tend to. establish equili. I )] j 11 r~ !'

22.. Vi'sclil'Sity ...... \"rc shall llbt discuss the phenomenon of 'lisr IJ~iL}', Here we shall gi'l'~ an d,emcntary treatment of the phenoIll('IIO]1 based on consideration, of mean free path. Consider a gas i I] morion and choose H honzontal plane -"); such that there is 11, mass ruruion of the gas parallel to J>.)'·plane bu L no mass motion along' rhe z-axis, AS!il1me that the mass-velocity Uo increases upwards a~ z increases. T1IC molecules above the plane z = £.0 pos~es~. On the ,tve.rage, greater momentum than those Lelow it, and hence when molecules from either side cross the t;lll.lle there is greater transport uf mosnennnn d,cl'Ii'\'l1wards, since the number of molecule, moving each wa}' 15 the same, there being no mass mo tion parallel to rh e z-ax is,

\'Fe can CDnsklel.' every molecnle, on the average, to traverse a tl istancc .\ equa.J to the mean free path and then suffer a coltision. If the velocity graciknt ,,~ d~lOldz tho difference ill the mean molecular velocity lIuOSS two planes separated by a. dist,U1ce~ ,\ is ,Ad[~ldz. The 111;11;:; of a IIwI,ecl.1le being m. the dirEer~lh:e in momentum is m'Adu .... /d;" . \gain. due to heat, motion, the number of molect41e.s movinM; along: the v-axls mtrst be; nn the aversge, the same a'l that lDovin,g along the y_ ur the z-axis, Hence one-third of the molecules rna}' be considered .ts ill oving alol1g l he z-axis both up or down, or onl y on e-six th to a Y' be I (1IHidered as mc)'vil1g in theu p-ward di~ction_ COltl'l der tm f t area of the ob.s.ervallQn plane Zo. The number of molecules crossing this area I let second in the upward direction 'win bet ~'1~C where n is the mole~ ular density and c the mean molecular ,.relo[,jty correspondlng to the I ~'11l peril ture of the ga,s. Sill ce all those molecules COn tained in acyl indel' of base unity and height c cross the unit area in One second,

I h::ll(,€ the momentum (,l'ilnsferrerl across the plane in the upward

, . '. -(r< ,dUll) h ,...... I

"''''PClIon IS U1C "-1111\-£ W 'ere '7 is tne momenunu correspond-

illg to the oh~en'aLion plane, Similarly, Em: IlLolecures going- down\\,'Ilr~ rhe momeuuuu trarrsfcrred is fr'Ri!( C+mA~). Hence the

- I ,. - rltlll

~ I II ~II ~ I iorn en CU 111 transferrec dOWnW<lIi([S IS ?, nc .mA - d;: .'

nell. an accL'leraling force On the lower layers, Or the

Tbis win

lower 1 ayers.

(28)

-I' \t:t1lil.ll,_, WI' must lake the al'erage l-esoI.etl part of .:I along the .s-.a:xi~, I III, r"1l1CS iJut t'J be ~A instead at A,

- [{ i HorUU~ ~:;! [culatio{l shows tlmt this wi![ be tll£.

jl

KJXKHC Tlll.ORY OF MATTER.

jUIAJ'.

II I

will retard this Iasrer layer by a Iorcc equal to this, By deli niricn of vism~ity ~ this force ImH;~ equal T}d.l~r,IJz. Hence

11 = i;~ml£"~ = ~r~'\, (3D)

'where p is. tI.lt: tlt:mit}' of the ga~.

23. Di.'SlC~1Ssion Qf trn:we Result.-' Ve ha ve esta L~ i shed til []I t '.1;= ~j p(\

r

but :I =- - lll' 82) J hence

v'l. 1l1!'U:l

me

(31)

llALlW OF CON~TAN"TS

',\ hen c i~ expressed in heat units. Further considerations .~JtO'l:\· that Un ,J hove result must be raodified into I( = "~1(.' where 'iis some IIIJJ':>lan.

'-lilln- f\. = €TIC < and rhe variation of c ; is small, the var iariun 1 d wndLirLil'Lt}' wr~h pn~~~lH'1: and temperature follows in general the ',.1111<' r.!Jlll se as the variation of vlscoslrv, Tlnu conductivirv Jikc \'N o~ity is Indepcuderu of pressure. This' was \'cJrified t:xpel:.imiotany h, 'It;Iuu and others, lNf! shall not consider the phenomenon or II illusion a.~ i~ i~ somewhat more complicated,

~5. V.alllJe of Constanb.- The value of tht! root mean square ',I ["ew,' for a ga~ ".'as calculated numerically for nitrogen on p, 75 . , b I' 11 U::;1Il veloci t} t can he ca I cula ted £'r0]11 (2 I) an el is equal to :12 ''"' '1.!J~1.>:- roil = 4,:) X 101.cm./~ec. Then (30) gives, on substitul- 1Il!'l" 1J- lflh X W-eg1l1. cm "! ~ec-l,

• __ 311 ~_ 3 x 166'" 1O-r. "

" _ = ;1:< I (I-G em.

pc 1·25 / 1O-~:x 4'5 X lOl

1 II r nuin her of mH is i 0 Ill; Soli lIered by a molecu le per $e con d 15

e ,1,,) X W. _

--= .... 5)( 1O~

" 9'·: 10 " .

\~~'l[lli,ng n = 2:7 X lOll' per c.c, we have

~ ~

. ! )~ I . '![

(-- - =- (. ----= _. - -- ) = 3 X 10-6 em,

\/2,m,\ ,l/2x2'7X Wl~X3'14xDx 1O-~

I hcse rulues will gin~ an idea of the numerical lll[lgnitud,es involved ru the kinetic theory of gases. We give below several constants Ior 1111)5[. g;)SCS at (JcC and atlllosphedc pres.sme,.

"

Table r*
}.r~s~ Ot Velocity Vi~l}sity Thermal MC:tLl I .. Molecu-
molecule m '1X 10" COl!UilJ~ti"Vitr free p-ath lar (lill-
r:~~ mXHP metres i~ 11\111. KX 10' .\ X 1(f ll1etel'
gm, pel' sec, em -I in cal. ern."? em. ex lOA
tiCc.-1 !i~C.-l 0(:-1 em.
llT .U 1&39 86 318 18,3 2At
N. ~3 .. 1 4'i'.1 l(i(i, 52 9,44 3 .. ;
Uu 402 %1 187 56 9.95 3.39
1I~ 6.1 1311 1119 339 28,5 2.18
\ 61.3 413 110 38.9 10.0 3.36
el. 5S.S 30"7 129 {57 4.96 Now ~ b ftJmportioD,:l to the. sqll.arc . r~ot of tl:c absolute ternperature, hence the .coelfiC1ent of VIS,WlOlt)' lS mdept:mienl ~}r rhe pre~· . sure or the density of the gas. pmvlded the temperature .I~ ~:omtat1~. This d,eductioll is rather surprising and was first regarc~(_'ft wlth SllSPIdon, ~.faytr and Maxwell subscqnently showed expcnmcntaLly that the law actually held for prcs5Ur("!; lying bc.twe~n 7_00 mm , and 10 mm .. and this was a_ lOtdkirlg" success fur the KU1etLf' "1 hcory, Bu t beyorul both l1mtlS the law fa~h. At higher pressures de'.-ialion from the law i~ exnect~d since the intermolecular forces (:111 not he then i,~l1nl"erl At low pressures t 11 r. mean .free l~a t h A ,g-rad ual I}' i I~ n,:eases ti J lit b ecomes .wrnparabll' with the c .. Iimcnslons of rhe cont::llrl.mg- vessel, and then remn ins constant. .. "-11\, further decrease of pn=~mt'e reduces p and hence 'IJ. Thus at nl"'Y low prc.isurt'!i. the codlicient of viscositv r<lpidly derreases with decrease or pressure,

·\~aill. since c vm-ies .1.5 l!vmJ 'l'j for clilIer~nt ga~es ~11C1111(1 vurv I, /m, T h b I lound to b~ approxirnntelv I rue.

24. ConductioD.-Let us now fiud an expression for the cnndurt~dt) of a ga~ which i~ a ~imtJar problem, In this case the temperature ""d heme the c.;nergy varies from layer La layer and it i~ the energy E wI1 lch is tnmsfet-n·tf Iroiu one laver HI another. COrlsidel'in~ the

dE dlln

energy gradient (I.; instead o[ the momentum gl"adicnt m ti:: ' the

roral transfer of ~nel'fD' [lownward~ per unit area become-

1 _\ dE

:j'oc" (Ii;.

where E denotes the mean molecular energy" pc.;rta:iniIlg to an,' iayer.

I.. ductivi £ h dT

If K be tile con uetivrty 01. t e gas. k the temperature gt<l-

d ien t, the How 0 r energ·y across u ni t area in the duwnward d irec L i o n dT'

IS TK d<:,' where I IS the merhauicel equiulent or heal. Theteforc

rr dE rr

.IlL'd)' = .}1"IC'\ tiT fi.;:_'

iff 1

K 0= }nC1. dT .1 = ?trlf lm.," = 7fC •

(32)

86

[CH.H'-

..

A guod account of [be snhject-rnauer of this ,d!apLer will ue found in ~u~ne Bloch. .Kine~ic Theory of G~jeSj Euglisll lnluslatlon published by I'IfedlUen. and Co,

L Jcan~" .Kine,~i(; Theory III G!l~f!'S (194£1) ,Ci'lLffih. Ui P,

2, K em Hltd, l( inetic T Juxwy of GaSflS (1 9 38), MeG ra:w"HiU.

•

CHAPTER 1\'EQUAUONS OF STATE FOR GASES

1. Dev~8iUol:I foom t~e Periled Gas Eql]ati(]:n~~By the u~~m "£qu:ninn . of Stat~" is meant the mathematical Iornnsla l~hH;:\ exp, r:~i:S the relation between J?1'"C~sllrc,:'tlllml(:: and ter.!JperdtLll e ~f a substance in any state- o~ aggregauon. If any .tWO o] these <juantitks be: known,,~he ~hird .b.as ~ fixed va!u~ dependmg.u111qudy !!pun them, and can be detcrmdned If_ the e1u~uon or st~te ,l~ known, but this isselcicn1] possi ble, According to the laws of Boyle and <'::harl~:;, we have (Dr a Pp.rft>C~ 14<lS,

- pV = RT. (~)

"Jhis ].11 the equation for a pe'rfcct glls.

Em even Bovle himself found that the law held only under ideal conditions, viz., iligh temrf'l":atui·cs and low prl?~511rc. while under -nrdin ary cond! rions i L die. r~ot correct1;{ re present ttl e true sta te'.)f ::JiTa]TS for any actual gas. 'for ever]' tempel'ahH'1t a curve can ot] dra wn w hi ch h as [or il~ abscissa t he vel ume and :Eo1" its ord inatc the {;orrtsPQndin.:r pressure of the enclosed substance. These cun"d are called i~oLhe:;_n<lls, H equat.ion (I) were true the iscrhermals _ ought to he n;clangn]ar hyperbolas parallel to each othe(, but c:>:peI"lmenh "how .that lhil; Is very seldom the case. The moste)(t.enJed earlier im'~s~.i:1;alion~ are due Ito Regnauh. He app1ied presslHcli up to 30 atmospheres while the tcmp(;:rfltul'e was varied £l·om. 0° W 1 OQ~C" He plotted the pruduct pV 1U ordinate agafn~1: /7 as abscissa (~eeFigs. 6, 7 infr(~ this rhapter), 'The rurves nllght LO be ~u·i1ight 1i1H~s p;ll"aI1el to the _\'-ax:i~; actually, however, rht_'"y~~-ere indined to it, He Iound that tor ai~", nihog-en and carbon di.oxide rhe product tV decreases ·with iru:;1""Casing lJl"e'lsute, while ['Or hydrogen i~ inrreascs. He. also f OLl nd. that hldw),,'en show 5 all abnorm ~ 1 10 D le- T hom sen elEect (C hap, VI). Thr!:seff1i.ct~ led. him 10 describe hydrogen as "more than peden". If equation (I) were true t.bepI'()dL1t~ pYi ought to remaln ron s tau t j. thus these pcrm<:Lne rlt gases WCl'P. show 11 to be i In pf:rfect.

La ter work hy N attere r, . \ udrews and Cll i llete ~ using hi g h,('r pressures confirmed the idea that the actual ~ascs sho~ved consider;Clhie deviations from equation (l). Andrews' experlments art: M Itmdnrnental impcnanee as they throw much light on the ad ua] behaviour of gases and form the basis 01' an importan! equarion .,f ~t:llefirst proposed by van de]" 'W:,lals_ Andrews' esperiments are des IT [hed i 11 ~he next se ction .

. , '~'!Jc m~M thcm:mghgoitl"g and exact experiments are due to Amagat ~'IlOllH"e~tlg·a ted t.b e b_ehavlour of, v~rio us gas~sLlp. to a I;ln::s~u re ot ~,OOO atmospheres. HIS results pillhcnlarly with CO:: (Fig. 7) and (,I bylcnc ,showed that their behaviour is very complicated ..

A (.hjJ~Te~lJr ~nethod has been utilized by K. O~H1CS who, invcsti,~t('~l the. behaviour of several ~,~QS at very low lJempCnHurcs awl ( luud L lrat nOllie ofthe numerous equations of state proposf'd rnrrectly t 'Ill '~("rl ts the results of experiments. He finds that at any tcmF~Ul,.

i

II I

I

88

EQI ',\TlUXs OF STATE. FOR {:.\SE~

[CHAP.

Heuce, at this remperature' Boyle's law will be obeyed. up to fairly high pn.:ssurcs, This tern]Jl:l',aLUl"<: is culled the R()'ylf' Point T2.'

2. Andrews' Experimep,h.Whi_le engaged ill th~ attempt to h'Plt·£}, some 0 f the so-ca 11 ed pennauent ga~e:;'--im important pro b I.e m of thoae davs, Andrews," in ]8(19, 'was led 'to ~tl.ldy the i,;;othnmah of carbon dioxide, His appanlfus is indicated in Fig. L ab.is a gla~" tuba whose upper portion consists or capillary tube and IS 11 arrowcr rh an th e rower pan. Carefully dried carbon dioxide was ]XI8~ed (hrough the cu he fur several hours <'I11d then tho tube

Fis-. l.-An(h'lew~' apparatus. sealed at both ends. The lower

end of the tube was immersed under mercury and opened, and SO)1"le of the gas, expelled by heat, !i.() thai, on cooling. a small column ol mercury rose in the tube and cndos~d the experimental g<M,

* Th01U:!S Andrews (181.)-lRS5). nom in Beliast. he: wag Professor of Chemistry at Queon's College, Belfast, from 1845 to lB,7!). lie is remembered chiefly for hls work ill C(Jnm~:,tL" n " .... ith the liqeefscrion of gases,

, I

1Y,j

B9

The tube was surrounded by a stroug cnppc1' tube A [lw~d with b1<L~~ Ii.atl~, at c~thcl' end,. to which brass pieces crml,d b~ attached airtight with the help of rubber wa~hers,A. screw ::i p,tss.e~ through the lower flange. The tube A contained water a,ttcl hy strew, LUg in p"rt:s~Lll'eS, as, bigh a,' S 4,U,O atmu~}Jher~~. c,uuld bu, ~pphed to the carbon dioxide enclosed above 1':. 'To H;gL~tel the pI cssure a similar ~p1:'hary tube cootainiug- air wa~ placed on :he rig~L side, and was enclosed in a tube A', exactly similar to A, wlth wl~lch It cummunicated through the tube cd and thu s th~ pr~.5SUre5 m both the tubes wen~ always kept equal. The rr<:ssure In ~l£hel' tube could be varied by means of the screws S or S', The caplliarytuhc ae could be surrocmded by a.ay suitable constant temperature bath (nut shown},

3. Disms:don of Re!ll,dts.- The curves obtained by Andrews are

shown in }I'jg.? Let us consider the lsothermal cor.responJinK to

}3, 1 -c. StOlrting from the l'i;g;ht we see . (portion A'S) that- as we increase the pre~ sure, the volume di m inis hes considerably and Ii null y 1 L(l u efaction of the gas begin.~ at <l pressure or abou t .19 atrnospheres (p(]int D). As long 3.S li~-l uefaetion con tinucs the pre~~Llre 'remains constant and the volume rontiuuallv diminishes, more and more of t!LI: ~~S beiI~g pre,cip,itated as Iiquid. 'This 1~ indicated by the nearly horizon tal line Be. (Th e slight incli n arion i nrli ca ti Il~' an increase of pressu rc towards the end is due to the presence of air as irnpurity) ~ At C a.n the gas has condensed into liquid and the almost verticn l rise of the curve iudicatedhv CD correspond~ 10 the fact ·'rh<tl. liquids are only ~lightly compressible,

The isothermal oorresponding' to 2l..'lcC is of the same gene~·<tl form but the hcrixontal portion R'C' is shorter, In this case the specific volume of the, vapomv,rhen cou:densa.ticm begl ns is smalll:r while that uf Lhe liquid when eondcnsation has completed i.S <-rre:ltcr than, the cprrespondiog vohimcs {Of the previous curve. As ~he (e..:mperaturc is raised these changes proceed in the same direction us above. till a~ 31.~·Qc, the horizontal plirt bas just disa.ppcmed and the two volumes have become Identical, This is called the critical isolh('n~llli lui' carbon dioxide. Above this temperature, the horizontal. I,;lrt is absent Irom all the isothermals and as we increase thf',:_ rres.s!:!.l'~

lure the results arc best represented by an empirical equation of the typu

pV = Ii + Bp + Ct:P+ DP~ + ... , . (2)

where A, R, C"" are constants for a fixed temperature, but vary with u~mpera.ture[n a complicated manner. As maIl)' as rweuty-five constants are used ; they are called vhial coefjkicrHs. A is siruplv t::gual to RT while the vnlues of the coefficients of higher terms diminish l'apid1r. Holborn and. Otto, folloVl'ing Ormes' method,

. st udied ~e\ era] ga5e~ up to roo atmospheres and between the te1T11Jer.L· tures of - ] 83"C and +. {(}O"C, and found that they need take only four conscants, They gIve the values of these constants tor various ga~t.:~ at different tCrnpenLLlln:'s.

The coefficient B is of particular importance. For all gasl'!S it varies in a similar wav ' at low terupcrallH'C~ It has a negative value, then iL hradllally increases LO zero and becomes

l'X)SUHL·. .Nuw if at any reinpetawrt.: n = 0, and C, n are neg1igiLle a-s usual, then

d(pV) = B -= o, ap

b

so· D

., , .

~C

O,L-~---C~--'$----4--'~~~~'--~ Specin~ \'(lIi,t,,~ in ~L

90

1\-', J

\'AN DER WAALS' EQUATION

ill

EQUATIONS OF STATE FOR GASE.S

l cnrti'.

l;hel:e is ,no, visihle_fon~ation of liquid, _E_ut the 'i.31111l!!!.e diminishes ;:GPlrl1v ~1I H b~coIt!.e~ ~,<ll'll}:.q~,& to ~e :volume .nf .th~ liquid at a ~t1y l<!wer t;m,peratlue, I !lIS peculiarity of the isothermal also": disappears ,'lit higher temperatures as is evident from the isothermal fUl' 18.1 o.C wbich is much like tile isol.hermab for air shown separately on the u!TbC-hand top", '

We thus see that the: whole d,iagram for (arbon dioxide is divided by the crirical isolhcrm.al, in!o two ,essentially different legions, Above this isothermal no Iiqnld state lS at all possible even under the gTeates~ pressure, wbile below it there are three separate regions. 111. the /egmn en,dose:~, by th~ do!ted curve ll!1~PC'S: whose highest rOl1~l J:, called the t;ntu:al i)Qlilt lies on the critical Isothermal, both Iiquid and gaseous states coexist. To the left of the line PC and h,elow the critical. isothermal there is the liquid region whiIe! to the nght of PB there 1.5 the gaseous region .. Now it, by means or gradual changes, we want to cOl1v~r~ ga>rou;s CO~ at, 25~C 1'iud 60 atm. pressure (represented by the iKllnt R) mto liquid CO~ at the same ~mperatm:-c (~epresenteri by th.e point S) withou t any dlscontinuitv ,1ppear:[Dg, U1., the mass is not to separate in to a Iiquid and. a gaseous part With 11 layer between them, we must avoid reachins t1H~ inside of the dotted curve BR'PC'C. Thus "~T h~a( the s[lbstan~e above 31,4° <I_nd . then comprt:'E~ it tHI the volume becomes equal to that of the hrj1nd at that temperature. Next cool it to :!.I)°C and then n~duce the P~Tssu~e ', Thus s~:lrtillg ftu1Tl the point R which undouhtedly represents ,.t g:lSeOll~ State r,~'e are able to reach, by means of gradual .hanges. the pomt .s wll1d~ undoubtedly represents liquid state, while ,tt no 'l:g!~ of t~lt: 01~e_ra.l.lUn dny, her.erogeneit}, or meniscus appears III tl:e \\,hole rnass, I'his result l~ e~ptus~ed by the statement that the» e . «xtsts t! conUnmf.~ uf the hqtad and ga,uwm states and W~]S established by the experiments uf Andrews,

, . }Ve h,tl::c. ~:-(~n thal jf g~suous carbon difl~d[!e i~ compressed above ,~l "r- ~ no Jrqmd C<1n make 1i:.S appearance, however gruat rhe pressure may he. :\iun~ accurat c experunents show that thi~ 'Lemr~!'a ture i~ :I UP and not 3 T.-P. The temperature at, :3 LODC is called 'the rrdi(.'(,'( tcmberatur« (T.) [01' carbon dioxide. 'We lTlay define critical tf'lIlp,erature as the h[g'he~~, ~e.:,"?peraLUre, at which a gas can he Iiquefied by pressmt alone. Tl;IS IS " .. hy the earlier attempts to liquefy th(. p_ermane~t g~ncs failed, though el1Ol'11U?m pressures aniounting to as much as ;),000, atmospheres were sometimes employed, The pressure n~c.:-~ ~ ~ ry to liqu ef y gases a L th e criti ca l' LeU! P Era rure is railed the (~n tr ca I ptes~m:- .. (P ~) a nd the vol u mew h irh toe g a ~ ~ then orcupi es, 1.~:" at the critical temperature and. critical pressure is called the ('t l trr.a.l uo lu me. ( V ~). Th ese three q u antities aTe ca TIed the critical cOl'Ul.a'~H.'; ~oF a gas. A table ~iving' the critica~ conslants for ,.'

~'~sc~ IS . ,. 10'iJ - ". \arwus

'<. glV<:O .or~ p. ""'. It ObVH1Usly foUows Lhat in trying fO

h~~:e[y 11 _f~a~; It l~ mde~_ to apply pressun.,' alone if the inhial tem,~:.r~.-l~1l"e l~ ~WOVf' (he crltlcal PO,tnt and 110 pressure g-l'eater than ,hc c. ltir,l] ne~d he cl1lplo\'F.d,

~ or cQnl';'le th.f' vohll;'!;,~ r)C':lI'f'}ied 1 1

tLmperat[ITe arc the ~al11f', l}- t le gills m:tl rb(' liq1Ji'd at thl' criticJ.l

.,

4. Van tier Waals' EquaiWn of State.-The cqua,tion, of state for

.erlect gases was deduced theoretically hom the kinetic theory uf ~asc;li (Chap, Ill). There we assumed ~hat the mo.lecules. hay; no ~{)llH}.1e: and do not exert forces of anracnon on one another. ,1: here assumptions are correct only~o:!: the ideal o~ FJoCde.c.r glls ~n which ~,~ actual ga~es of nature appl'OxJ.ma~e at low l:lesslL~~ and IH?h te,~pef:e lure. Rigorou~Iy ~peOlk~flg:, ho~ev~r> «u g-'.l.S ~OI4.:_Cllles .. h~,efimte s, . whose 1l11por'tapce wa~ Iirst pointed uut by Clamms., 1 ot our pres~nt pUfjJOSe we shall treat the molecules as hard elasttc. spheres .• U 1: dear that at verv high }lres~ure-.!i the total volume of all the molecules win not be a negligible Iraction of the VOIUHle .of the gas ~nd further even at the highest possible pressure the volu!'ltC occupied by t~l~ subszance cannot be less than the volume oCC1:~pled hy the molecules when they an: most closely packed. It follows, therefore, th~t the free volume of the gas to ,,.r..ich the Boy le-Cher lcs' la w Tef~n; is not the .;-as volume V but is less than V by a factor b where b 1~ rel a ted

to t~e rota l volu me of the gas molecules, .

. Another simple way 0,1 arriving at this ~csult i$~pom COllSIC{.erR: tions of collisions, Cumlder four balls lymg separated from pn~, another on a line perpendicular to the. waU and Jet the [arthest one start to move towards the waU with a fixed velociry. if the balls aye hi', the distance to be traversed is less and hence th~ last b,,1LLl. WIll stl~kC the wall earlier than when the balls are mere pOIntS. Similarly for molecules o£f.inlte size the number oE collisions ''''it!) the walls find hence the prcssul"~ ""HI be greater than for pomt l:nole~les. Thus the effect of nlOlecular size is equ ivalent to a reduction 111 the total volume of the ga~ by b.

Him, in J 86,:1, pcin ted 0 IH. that the molecules must exert forcc~

of attraction on one another, hence the energy, cannot Le wboUy kine~i.c, and potential energy du_e to forces of ~olleslo~ must also be taken into account, 1_"he corn~cho:n for rorces of cohesion can be ... ~ry simply obtained, Thcst' forees are of tile 8~me ~lat~re !lS those wh_Lch gi ve rise to the pheIloUleno~ or surface te1.:sLOI1l" l~ Lt(lmd~. T~e rnole~ cules attract one another WJ(h a force which '«lHE:!S inversely as some power ~f the distan rx; b~tween them.. Tl1U~ ~lte Iorce "will be a ppr:' ctable only for small distances and IS negllgtble 10, larger ones, A molecule i(1 the interior i.~ acted 011 by forces in all directions and hence these wjlI balance : but this is not so with a molecule On the surface Or dose to it" The' components or the forces acting On it res,01ved parallel t.o the surface win balance but not t.~lOse in a p~'Tpendicular direction. There "'lill he 11 resultant force acting perpendicular to (he boundary layer and directed inwards. It i~ obvious that this force _on a single molendc will he prnponiOluil to d~e uumher of auract~ng p<trtiCIes in the fluid, i.e., to tthe numhcr 11 ot mo]e?Ule5 per c,[. . '1 he (oIce actin:", p~r unit area ,of the g.bWUS boundary Will be pl'opo~LlOnal to the product of £he above force and th~ 1H111l~Wr 0'£ molecu1cs in thai; -area. Hen<.e the cohesive force p, acting- per unit area of the l:lUu:,{bry layer of the ga~ i.s proportional to 112, Now n = N./V where ~rlS the totf.lJ numbcr of molecules and. JI the total volume, Thel"eforu III 0: 1/172, This force opposes the outward motion oE .he roolecuks

EQUA'I:lONS OF STA'J.'F. 110& GA.5.Et;,

[ CHA!'.

Hull thus decreases rheir' mouicntum and hence also the pressure generated by .th.eir impact. Hence the pressure win. be . less than that calculaterl previously by the factor alP':!., where a j.~ some co!lliotan£. In other words, we must replace P III the perfect gas equatwll by

a

tJ + F~ as if the; external pressure jJ on the gas is increased by alP.

Applying both tJ.w..se corrections the g.as equation becomes

(p+ ;2) (V-. b ) = RT. (4)

This Is van dci- Waals' equation *, Detailed consideration, show that b is equal to fouir times tile total vol uine o~ th~ mole .. cul~s .. yan del' \oV::labt was the Iirst to work out a systemanc tncory, taking rnto acooun r. both these Iactors. viz., the finite size uf molecules and the forces of cohesion. Van der \rV1.1ab' equation is found to hold true for smal] deviations from the perfect g<!s equation. A comparison or this with the experirnen tal results is given in sec 0. Various other eq LW ti on s of S tate ha ve b~n pr~.Ipos.ed. S~rne 0.[ til em are more accurate thau van der VVaals, equation In oertarn Tt.'gWJ.1S ; nevertheless, the latter, considering iEs ~impJjdty, gives in gentral, the most ~aLi~facwr}' 111'sL approximtuion to the behaviour of actual gases. 'Wf' ~hall dissuss this equation ill more detail.

5. M,e,thod of IindhJg the VaJqes of 'a' and 'b' - A me tho d 9 f 'l.LJdilfW tile values or <D' [llid 'b' orultr::in~ in van del" \V"aU equation

is ~,L\'~~l Ldo\\ :_ '

n('{r'i"mint~thm or '(I' (1n(t 't)' from Critical Dalf1.-In the next ~{'l tion it will he shown from theoretical ccnsiderations that the ('J I iral t.eIl!peraturC! T <, critical pressure p , and critical volume V, ... fOJ ;1 .IS~s oLey[ng van der Waals' equation are le_~peltlvely given by

T Sa ;, a. V % (!i)

s ==27bR '; r c =·27b~ j < = ..

27 R~ 1". ~ , R T ~

!1- £4. p~' b =-3 'p;- (6)

Thus if 't., P. are experiul!~ntaUy determined <a' and ''// can be ralcula ted with dw help of cqnaucn (G). It may, however, be !-min ted out thiH the method is Ilotvery accurate as the ga~ does nor obey vall del' Waah' law accurately ncar the crt tical, point. Butthis J$ not of much con~eq uence as fa' and 'b' themselves dep€~nd npO!l temperature and volume. The values of <a' and 'b' for a few important gases are given in table L They refer to j (~c.t of Wi" at N.T.P., and art: determined by this method from equation {fi) ..

* F{)r tbe yarlO"llS mdhQd.;: of dodu~illg thls ~"(.jllati(JDl see tile Authors' TrecJtisem~ Hea: n9.::i.~). Out]]. X_

i' _Tohallll()S Diderik van dc~r Waals (1837-1923) was born at Leyden, In 1873: he f(Jrmulated his equation of state and ('"stab!ished the cOJ1l1ntritv of liquid RI1d p:mL;Oll~ states, In 1871 be bl!Cal11e Professor at Amsterdam aud was awarded the' N or~! PL-j;ze in 1910.

:1; 1i we consider a g"J'am-molectl[c we have to IDtlltiply'I.I.' ill the table hy (22.4 X hPj" ~ld 'b' DY' r22A X 1{)"). This is obvious fmm rdation (6) since R for n gTar:(l-mol~r,ule in these unlts (",tnL X ern,") is 22A X 10'/2n.

1\' .1

llIS(;UM;lO;"; OF VAN DEB. WAALS' EQ,L"II.TION

!J3

Substance

a X IO~ 1 b X 10"

in atm. X C111_4 I in C..L

5~-1J06

~68 143

27f.i I 1-13

272 173

48_7 US

in HH

833 IGG

I Ielium

Argon

Oxygen Nitrogen' .• Hydrogen. :. Carbon dioxide

.. I .. I

Ammonia

To:: 3 P '_ ~_25 atrn., ralruE.xeT(:i.I·t'.-U~ing the va,lue~ or • = ;;." .. c

•. ,'. ·1 'I.> [01' helhnu I or a gram-molecule.

iate a anc u

27 R'.l. T~ 2 27 X {8'S X 1 07~ X (5'3}~ dvnes X em_"= 3'5 X 104 ell = fA- ' PI =- f14·X1·25 X 1,,01 X lO~'

~

atm. xcm.

'R T, 5·3 x R'3x 1~=2<l' c.c,

,) = ~r' jJ~ =:2'25 X 8 >< 1·01 X 10£

6. D~ll!sPiion of van dier Wilals.~ Ilqll!anon.- We shall. nm..,. discuss \' a n der "Vaa 1 s' equation

(P+r;-) (l'-b) ~1tT.

This i~ ~11l equation or the

t 11 iro degree in" V, h ence i ~ follows that for every value of i~; V must ~i'lv,e three value'S. Further., from theory of equations, eitl,cr all. the three values are real or .one is real and two imaginary.

Again writing- we. equation in the form

R'F a

J)'--=V-b - Vl!.·

l'hewetirol. C1Jn'g!5 {ijir c:!.ti;Im ·diulI:id1.

(7)

'2 3: Co .E.

Sl!e~ifle volume

7

94

b for then p would be negative which is physinlHy absurd. H in (7) W~ substitute the values of 'a' and '0' fm' carbon dioxide viz., a = 0.00,71'7 a t:m. X ern.", u = {tOO 191 c." and then re ptc.;sen t rhc :resulting etiua tion [;y means of graphs lor every temperature {p = ordinate, V = abscissa), curves of the t)"P(~ shown in Fig. (I ;I1;e obtained. It. is readily seen that the curves resemble, in general, the experimental curves (Fig. 2') obtained by Andrews, but if we look for quantillltive ag,fe<JmemIJj' lIving to make the two sets of curves coincide we .are gl'eatI}' disal~pointed. In fact, theagreement is only approximate andqualitarivc partly became or errors in the assumed values of 'a' and 'b' and pardy, because the equation 1101ds on]y approximately.

T'ilere is, however, a remarkable drvergence between the theorelic;d and the experimental curves in one region.Tbe theorctica] CUl"l"'~S drawn Irom van. der \Vaals' equation give maxima and minima in the region represcn ted hy sn-aight lines in A udrews' carves, Ex pc.:-r]~ ulcmally, this is the region where condensation at vaporisation begjns. ami the pressure remains constant ali long as the process continues.

This dilference is easily explained when the theoretical curve i~ pw red y i nrerpreted. The part b d inside the dortcd cur we.: cfllTespon ds. Lo~he ~itC~ th;:tc the volume ~houI~l decrease _ with decrease of pressurewhich 1$ 'quite cuntrary to experrcnce. 'This would be a collapsible state, for any decrease of volume is accompanied by 11 decrease uf pressure which tends to further decrease thl' volume. (This is. apparent if we imagine the Huhl to be confined in 11. cylinder.) Thus. Lhc state of the fluid Inside the dotted curve represents a statu of uIlSta,hle equ~IiL~inm, and wnsequeI\d}~. can ne\'f;l" he. realised' i.r! pr.iCoI Jet. ThIS !S why the part lh:~ I,~ not obtained m Al}dl'ew~ cxpcriuienrs, L'he portion 17.0 represents supersarurared vapour and is ~U!ll~lim('s obtained experimentally as, for exampk_ when air conrmning water vapour 1~ compressed beyond the rOll1e when condensation would usually occur, without condensation occurring, This happens when the air i~ free from dust or charged ions 'which act as nurlei 1.01' condensation, This state is, however, unstable and is easily disturbed by the introduerlon of parrlcles of dLL5t, etc. Helice thepOl' lion a b 'I,V hich re pl'e.:sun ts su persa L urared vapour in unsta ble equ illbrium does not OCClU' in Andrews' mrvcs which represent only stares of stahle: eC(uiljbrlum: Simi~arlr, the porti?_l1. dt; repre.sen.ts a su.pct. heated Iiquld WhICh ]~ also m uustahle equilibrium and is obtained cxperirneruallj- when g1ts-fn:e Iiquid is carefully heated. Hun(e this also does not. occurun Anl\re,,\·.~' CU1TC'S.. Thus the apparent diverg-cnce is explained.

Van der "\Taals' theory, however. does ncr tell us when condensation begins, i.e., where the strafghtp:ut commences, A lkimpje the~'mod}'t1amic argument * ~bows that the straigb I; portion should be so drawn that the area abce :- area cdec.

1" Let the substance l-epr'es~lltedl)y the point fi form the. wm kil'l~ substance or a heat engine ( Cha,p. IX) and I et it he t'lk-fll through {ht: cvchc operation Telll-~S{':L1t~r[ by th~ pa~h (fJJ'C4~'m. Si[!cc the temperlilbu'~' re Ilia.ill's run"~tra.nt thl"Oughollt the prooess, it foll{l",,'.~ f~01l1 t he theory rri hea t engines (Chap_ IX) that tEJ(~ totar work [lone by the working substance, i . .tr •• the area of the cllcIO'Se,~ curve is zero. Ht::nce the two areas !lLoca and cdee, since the .... are deaerlbed ~tl;;

o]JPfJ<ite senses, must f,)e equal. -

-

95

n:I.';'Cl -S5 EO N OF V", N D,lllt W"'ALS' EQ,U A TWN I I It' Ilia" IWa. and minima points on the theoretical curve can be 11'I,ljllt If hy putting ~~?= O. Hence from (7). by differentiation,

op HI' 2a (H)

. + V-~-= 0,

ar = -(V-b)~ ~

. 2aCr--'-bp

'[ 1 = - lUi'!! (9)

I II I h :IIs.O ;1 cubic. equation, Hence, for _every isoth~nnal theye_ art.' ~.II t 1'1' I fa l or 0 rie real and two iI1I1agi nary POlll ts of maxi m_~ or ).111 ~Li rna. I h 'III W'~ below P in Fig. 3 are seen to PO~~C$S one maxlI.lIa and 0 ne 1IIlU Illn l,oInt while those above it have none at al~. A $hg~,1t... mat.J~e- 111.111' al transfcrruatiort will show that the. other po~nt of lTlmr.ma liea III lin· 1 eg j 0 I) V < b and hence bas no physical lT1(~anmg - Etl uat to n (1) III! I (~)). when combined yield

a(V 2h} (10)

JiJ -::: --Va -.

I II i j~ die curve passing thnmgh~he maxima and m.lnima points and II"" It bv the dotted C11n'e QPR.

1]1 Fig'. 2 aU isnthermals _ Iower tb~n p.c~t the dO:l:R.d ,c~:;v~.

HI','!,! /(, at two pmnts anti, therefore, Iiquefaetion .c~n he obsei :

I,~ 111:mgiL1g the YOIUITiH'. a.1J)1l~ them. _ For. the crlUc.a.l. isothei mal,

• !.lIt' isothermal conespondlUg to the. c~ltlcal t~lTIpel~~U:l"e,. th~s~ l\ .1 [,ulnts have coalesced-into one. Referring to. Fig., 3,It IS I_ea'~_il:

• II Ib;n rhe L.sotherm<ll p a ssmg through the pomt. J, wh_ere liS a .uiut or inflexion for the family of C1H'lieS or a maxima point ,~or d}e-

!1!1.1~'Ll curve is the critical isothermal because below P every Isother-

I 11 h~ls got' maxima and minima points. while ~bove _ P there an:

II' ,II ( , a t a 11. .1\.<;, we .h a ve see n a bo ve, 1£ t~e I sotherma 1. has gut 111.n,: 1111 a an d mi uirna poln ts then: 111Wi t be:. hqu,efa.chon ot, the gas 111I1 '0\'(' can fLnd out the positicn where hqucfanlOll. beg;m.s. For Illjllt·f:lltion there must, be two points ,on th,c C'l.HV~ .hav~ng ~g~al

II , , ~ III e. The hizhest 'iso thermal for which this con d ltl en IS. sa tis lied !, 111<' nne passin; through tIu: point P since at p. th;_ maxrnia an(~. II! III itua points have ~,~[e!>ccd. mtD one. f:IencE P~l!l llg .. ~ 1~USt}1f. 1111'111 j rj('d with the critical POll1t and the lsotberm..tl. th.rou~h H. v.; ith illi nit kit l i!;o thermal. N uw for P to be th e l ~lax.uua pom t 01' th f' .1, 'II ['11 curve 'we have, hy diner~l1tiating (19) With l'tspect 1'0 V and. I ·'pI.11 I ng to zero,

3a(V-2b) V~

i ~1

0,

I' jllllI (10)

Illd l t orn (7)

I I I I

J I

96

ICHAI'.

I XPERIME.r:·.rrAL S7UDY 01." EQUATION OF STAT~

97

. F' 1. T is the measuring vessel 1111 .lpparatus is s_hown ~~ .·t~.

III ,dl f,l,1 nut glasswlucl.l ends :1.11 .-1.

.1( !!" I)' !'aJibrated capllla~y . LuLe~ I h{ 11,\\,('1' part ot the VCSSellS plated III .1 ~uTI cylinder. By weans of a lu.1 ,. l' i!:d t' A and a 5![Y~W ~ the \ '~ t I i~ held in the steel c,yimder. t\ 1 J ~ a tl I C rmostat surrounding :-he II !J I'N. L ra rrow part ofthe t~ he v.: hie h:

I ,11-:.1111 dosed by means o~ a mantle

( . l II~: vessel I' is filled with the g~s unih-r investigatlon <It atmospheric I'n,,,.,mc, the space between T. and 1.111' inner wall B being fined with a ~ II iii r i r-n t q uan Li ty of mercury over ".,11 kl"! a quantity of g~}'cenne <:r p",allln oil is poured. Pres~l]re. JS «uurnunicared from a cOIDpresSJ~n l'll ill P t.in'cmgh gl}'oeri, fie . to. t :1e ul~"i~ud[lg .-ves;'l,el. At I"ll,~h. ~e~,su:es IlItTC'Ury wIll rise IIp to rpe capllla.ry tul.c and the vol ume xan be easil y I j .ul olf from the calfbration. ,.vhen I Ill' prcsmre is high" it is measured II" a compression manometer. If m.e "n'~!Ollrt; is above 3(~() .atm .. and .. IS

, XC] ted only from the 11151de the call1l~ Fig, 4.-Cailkt.ct's apparatus.

I r i es an: generally smashed, hence .... .. " "d

'I' .: ' : ntal tube should be subj eered to press-ure Irom all si CS.

I It' t::xpEIlmen .. '" ... • ,

"i~11 II ::J, pressure tube W:EI,S built hy A~,ag1lt. ' .•

Am,agat carried out an exhaustive slu.dy of the behaviour of sever al g_ases by the above method. In one set of e...xper~m~nts he employ~d pressures up co.4,50 atrn., while in the next series pressmes as 111gh as 3.,000 atmospheres were

r used. . 'pI I

(b) A'l)fmralus based. on the .prmc~' . eo·

tiariable mass.-~lhi.s method wag employed by Holborn and. Schultze, Holborn ~nd Otto and Kamerlingh Ormes The~e inv_e.sUg"tQrs worhd

at high pres;syres al;d obtained nTJportant results, Si nee wi th mcte;as1.l1:g pressure the vel ~me . becomes smaller, greatcr error would occur u~ ~ea~.in'" the volume at high pressurc~. To aVOid It.,

W Lh~se in vestigators kept the vol ume constan t 11[1 d used different quanritles of the gas whose masses

r:jg, i-The were determined, The apparatus Lewme~ some-

prtssur« balance. what complicated by the p1"e~ence of devl.u"S for

II, i mroductiou and removal of the gas both Inside and outside the

7

The critical constanrx may he yety easily deduced Iroui (7)! since for the critical isothermal 1 he point P is a maximum point as well ::IS

op (J2p

a poin r of inflexion, and for it both a v and d Vii ",'e equal ro Z.lTO.

'We have therefore

,Op RT 2d

av == ~ ur-b)~ + p;t = () ~)

&2p 'lRT 6a

o V2={F-b}~ - V1=O. (2)

COl'llhlllfng (8) and (12) we get V c = 3F'~'Ulri I hen with the hel p

F Sa ,.. aRT,. D

of {S). 'I Ii = 27Rb -, Fin;!f]y from (I), jl c =27b2 and ,fl. V, = 3'

1. DefedS in VaD del" Waals~ .Equation.-ln spite o[ general agreement d(~rtuctjons from van del' l:Vaa]s' eq U~ uon sJIOW consider~ ble deviation from ex per] men t..1.1 results. ''\Ie ha vc already shownthat fur carbon dioxk1e the Clll"'VC'~ drawn from van der 'Va 8r~> equation do net ql1i[(~ agree with the exp::rimemfl.l curves of Andrew«, At _particular ] sothermal rna y be made to agl"lfe much 1lJ ore closely with suitably chosen values of 'a' and 'b' hut theH [or the same varue~ the agrecmcnr is not so g-ond for other isor.hennals. This only implies that '(I.' anf! 'b' var}' 1.\'1Lh LemperatUHc a~ hasbeen directly fonnd from cxpenmenis but van del' '\o\/aa18' theory assnnies them to be constant, This is 11 great defect of the Lheor); ..

Another rjisr:repal1("Y llOwc\'er, lies in the value of IJl(~ critiC:Jl cocflicleru RT. /Pc Vc· From equation (J) this should be S!3 lor -n gases, inckpendenc or (heir nature. Ac.tu~.Uy, howe"l.'e.r, it 'imrie,~ Irom gas to gas, the valuf' ranging' from 2.~2i for neon to 4.99 {o-r a(etj,~ acid, IL 1 hus SCCl'l18 to depei1d upon tile molecular Sl:J"l.Icture of the ga~ ..

I~g~in. "an der ,,,,raals: equation gives 17" = 3b., while cxpenrnen.

Lally H IS Iound that V~ IS, more nea.rly equal to 2b.

8. ElQlerimelitai g,tu.dy of the Eqll:atio!] oJ State.- The method, of detennin.ing Isoi:henn;:i.ls for gases and liquids fall into rwo classes; (a) In Lhe one, we observe the change in volume when di.lff'.rent pressures are applied', (b) In the other, vol ume remains ro.l"1Stam. the quanrity of matter being- varied,

(a) Appa~'lltU.!i based on the p1'incip1e Of variab.~e voluu1-r!.~Whel1: the pressure is SlIWU, dle apparatus i~ quite simple and is given in eI~memal"Y text-boob as the Boyle's law ap[J;J:au.lS, For higher pre.s~u1es, up to 100 atm. an apparatus due (0 f":fllHetet is used. This is descnhed here. Tbe same apparattls with cenain modlfica tiOI1~ 11115 been used by Regmmlt, Andr,E?Wif and Amagat in their l'cseal:Che5.

:F.QUAT10NS OF .lIT 1\ TE F'ORGAS£5

[ GH.:'.!'.

a<.perh');lental vessel. An ing~niou8 ptes.snre bahnce shown in Fig, 5 was used. to measure such high preSf,UTC:-5. The metal bleck B was firmly damped in po.sititm al~d, carried the _tube T '1,.rhich was, COll: nected to the apparatus conratnina the experhnental ga~. The block B has also a cylindrical hole in wh'ch the cylindrical rod It accurately fitted. Between R and t~e gas in the, tube T. there was cas LOr, oil ~o that gas prcssur'e, transmitted rhrough the 011, tended tc; raise the piston R. :rh18 was jus~ prevented b,Y the screw ,S prefi,<;m~. em t¥ tOp of R with the oom Lined. \~lght. (J~ the frame F a nd weights \N/. When balance is obtained, i.e., the piston neither rises nor tails, the ga.s pre~mc p=mg/a, where. m i~ the mass .of R. S, J', and W, and (lis tile cross-sec Lion of the plst.on or the cyhnder"

9. D1sell.SS~om 0-1' lte$l'IIb.- Amagar represen te~ his . results by graphs In wlnch p V denotes the ordina w andp the a bscissa, The curves for hydrogen and ninogcn for several tempera rures OJ re shown in Fig. 6, As alrcad y mentioned, for h)'d:mgen t.l.l.C prod.u rt p V 10- creases wuh pre'lSllre, but for nitrogen it first decreases. The curves are stra.igh t lines ill dined to the pTe~sure axis, while if Boyle's law were true, they would be straight lin es parallel to the pres· sure axis. The curves for carbon dioxlde (Fig. 7) arc typical of all gases. The isothermals below about 30" have a portion of them parallel to the IJV-lIXis. Thls Indicates that the pressure remains constant while thevolume varies, and corresponds to the condensation of the Yllpour. Eurther. it is seen that the curvaui re of the isothcrmals dimi u ish es as til e tern perature rises, The mb~hna points on isothermals gradually recede ~wa.y from the origin, and the dotted curve through them is paraholic. At .still high,er temperatures no minima paint IS Iou nd and car bon di oxide behaves like hydrogen.

This general behaviour ofEhe isothermals can he easily explaillcd fror'o van derWaa.l~' t!ll[[ation. -W,e have

(p+ ;2) (V-b}=RT,

01.--------,1-=,1)""00 2.000

II in nmtos..

Fig. 6.-AmllRS-t's curves U'V against p) Ior diff erent gases,

TjV~!l'Jr'_I_ ~--~ =RT ;c ,u V 'V~ "

(IS)

In the fhird ani! fourth terms which are small,we can make the approximate substitution V = .n.·rjp. .E-qn, (IH) then yields

H'I

(14)

/\i Itig-!I remperamres the rerm abP~!112~1'2 can be ueg1ccccd" If we Ihul \)Iot .f'V ~s Y-~()l'chnil!.te and pas x-oo~rclillilte, the plot will =. a M I .Il~' 1 t line Inclined to the pressure axis (e.g. curves for H ~ ~ n

---."'-'_ ..

~ -., -.

...

o ~~=-~~ ~

C ,2~ 1~ ~()Q i~!;' ]1>0 j'f.;!, !lQQ 8E;~, '2~.o

pill aTInoa:

Fig.. 7.---Curves r.oo- eai[xlfi dioxide,

l' i~. G}. Thus for temperatures above the Boyle point T lJ = ajoR r I,~' ~I~lpe will always be ;r08h:ive as Ior H$ in the figure. For temIII r, I til res. be low the Boy Ie point O'! 3 in the case of N ~ and CO2 in I' !p;~. (i }':n~l 7, the s.lope, will be: negative unless the t;res~m~ is too hl'-!Ii. I'his can be readily seen Iromcqn. (H) which holds for the

c IU' I :1] case, since

(IS)

I hi'~lupe is th_ererore negative at l?~ pre'~sL~res but becomes positive •• 1IIIIIe If'll t~y I;l,lgh pre~ures. The mamma pOlnt on the Am.agat curves j j'"lhl' PQmt where the slope changes iES sign" can be obtained by I'PI:lrfug (15) to zero. Th~LS cnuc5ponciing to any singlc value of

I 'I I '1111 ,. there are two tern pe:ratmes given by the relation

a2abp·

b - RT+ R.~Tg =0, (.Hi)

r , III t·, I hlL~ed ell rve d:Il:'(l")u gh the IT! in] rna PO,! n rs is a pproxil'"Jl a tely 1,.1",1 ,ur Jt. Eqn- (16) shows that the dotted curve will meet the axis t' II' .u the RoYl.eteml?erature Tn ._ ajbR. Thus .A.m.agat'~ Cl;n;Ve~ III I,I· llJlIy explained with the help £If van. der Waals' equation.

1\', 1

I::XPER[:\fENTi\L Tl!F,T"ERM[]\ATfON of f:RrTl~:AL CONSTANTS

101

100

EQUATIONS OF stA1."E FOIt GM'ES

I,Hl:_ The curve An is a line passing through the mean of the vapour .Ifld liqnid densities and will consequently pass through the critical Il'lllpl·I;ll1Ln~, It was first observed by Callletet and Mathias that for .111 subsrances this line WOiIS straight or veil' nearly so. The equation I'll III i~ line I;.s )' = {. {Pl +r" } = a + bt where )J 1.5 the ordinate and t Illr' ;i I )~~ issa and PI, l'v denote the densities in the liquid. and the \ II H 1111 'i rates res p ~cti vel y. This law enahres. us to find ;l:c critical lit II ltv or the critical volume, for we determine the (femme" of the

uu ,I I, .~ 1 vn po 1I.r a nd the Iiq ui d as near to the LTI tical temp erat ure , . plj~~ihll:!, then draw the rectilinear diameter. The intersection of IIII~ line with the ordinate at the critical temperature gives the critic .. ] tkll~iI}' Pr or the critical volume.

.,'or substances like water which attack glass at high tempera.

I ~~I'C5 Cailletet uud Colardean empl~y~dtt~e ,apparatus shown in l'It-!., U. The .~~rong steel tube AR, platlnized 1l'1S1([~ to prevent attack, 11~1'lnins the water or the substance to be Investigated, It Is immersed II ~ ;1 Lcrnperature bath :t.L which is heated by a gas n~guLated burner,

10. Experimental Detennm:ation of Critical Constants.- ',Ve have defined the critical constants ill sec. 3. They are constants characteristic. of ~vcry substance, and are of fundamental importance <IS they occur j n certain eqrra tions of sta te. Their im ponan ce in. tile stu dy 01 liq uefacti on i s discussed in C~. ap teT V 1.

The determi nation of rh ese critical values j s often a task of considerable d1fhcuJty. Of these the critical ~emperat1l~>e is. the easiest to measure accurately, 1"01" ordinary substances" a hard gla;lis tube like that of Andrews and connected to a manometer m?l}' be employed. Sufficient quantity of the Equid is introduced and the tube surrounded. b!' a ,thennost<lt which. can be maintained at constant temperatures dllfermg by very small amounts, The temperatures at which the liquid suddenly dis-appears and reappears are observed, the mean of these giving the critical temperature, The~"'1itical p,essw'e is the pre;ssure at the criti C.1 ~ tern perawre and can be re ad easily from the manometer. The critical volume is much more difhlCu]t t.o measure ~H::OC'Llrately, for even a. small variation of temperature by Q·1 °C pto, duces a large change 10 volume, and hence rhe substance has to be kep t. exactl y a t the crit,i~l tcm pera.ture. Tile pres.s.u re rnn st a 1 &0 be ~xattl y eq ~al t~ the .C1'ltI~l pre85Ul"t: since the com pressibi.H ly of the subs tanc: In ChIS reglOll IS very great. The m e thou adopted was to arrange in such a way that a very slight increase (If volume Iowered the te.mper~tU1:e by a small amount and. caused the separation of the ~~iS~ rnto hqUl.d and vapour,. ~e liquid appearing at the top. Thi~ lllltmJ volume IS caned the critical uolume. The amount of substance initially contained in the tube has thus to be adjusted.

O"~ The most accurate method,

o,-g""_ however, is to make use of the

---..._~ Law Of Rectillnea« Viame~er$

~'AL..__-+-_---I __ I--I----""'_-_;::::..o;~_+----1 ·bOT rnCe~lrnl deU:!iitdics,u discovered

~~.-- 'i V . ,u etet .RU mathias. If

,e. u. ie densi tv of 11 liu uid and. of

i A .) .~

~Q/~r~~t=1::::::::::;:+:::4=:ifJ~ Its saturarcd ,'apour be Tepre-

I . B SEn ted by ord ina tc$ and the

'f: .... - -----.,.-. --.-_ ... - ""=, corresponding temperatures by

I)"~ • a bscissae, a curve roughly para-

VaTlOllr _-'_/ i bolic in shape is obtained (Fig.

-- Tci: S), In the figure the vapour

200 ~Iit(t -~S~ ~.~ 70 -1 eo -'L~"Q ...... '.1:1:; -t:-

Tenrperatnre C.·nti ~r;I~~_ density of n r trogenis plotted

Fig. S.-Law of Recrjliuear Diameters, from the observations of Onnes and Crornmelln and is typical of all substances, The densltics in the two Hates <YO on a ppWadlil1g each other till they beco me e.(l ual a~ th.e critical tc:rpera-

'" Somdim~s a simpte ~l'pa.atm. first ~l):Il[~tsted by Cagniard ck 1;1 Tour h r'mpl[)y~d fC11' the purpose. It eonsists cl a glass tube shaped like _T, wit:) its 5h(lrt_e~ arm somewhat broadened ami containing the liquid in question wbich is se~'u;l.,ed fron_:l <L~L m the: larger arm by a column of mercury. The two ends are l:l.o~ed, the arr H1 the longer tum serving as a compression manometer. The [lJ!5aPP=:·.'10ce: of tbe. surface or separation b~hv{:el1l tb,;: Il[pid aad its YS[1OUT [n the slwt"Ler arm was observed,

Fig. 9.-uiUet~t amI Colardoau's aJ;lpaL1:ltus.

mnl thus its te~perature can he kept constant. The tube AS is I nlllHTlt:J. to a similar steel tube FG by means of the flexible steel 1I,i r, 11 CDE. fI.~el'"cury fills pan of the tube AB, the spiral CDE .uu] th!'. tube J'G up to the level S1, above which there is water filliog- 1IIf' ~·:Itln..: tube up to the manometer, Difltrrent presmretl can be ''1:1,1 icd _by t~lC force l?ump a~ indicated. At S1 an insulated platinum WII~· which 13 sealed in the SIde of the wall completes an electric: hen ( II' II i r. ,"Vhel] the tern per-al.u rc of the ba th is raised 1;1.1 e pressure of

,

102 .

[ CHAP.

E.QUATIONS OF STATE l"OR. GASU

the "\'apo~r .I!l on rises, .tue.rcury ~s forced past Sl in FG and sets the ben nngmg. Water IS forced m by the pump to keep the level uf. mercury constantly at ~l and thus ,the volume occupied by the w~ttt an.t! water vapour ~n AiEl re.ma~ns ?,nst,mt" The platinum wrte a t S~ completes ano ther electric circui t and serve'S to sound a warning tha.t thew hole IDt::["cm:y is about to be expelled out of A B.

W c thus get the va pour pressure curve of the snbstan .. -c. The cu nrc i~ perfectl ~' conti n trous and characteristic o[the su bstance. For water this is shown in Fig. 10. If. however, 'we start. ·w1 th dillerent quantities of the liquid we get the same curve a." far :!IS M. but above it we get different curves. The vapou.! pl'c.ssurc thus 1Ii,P pea rs to bTancl~ ?ff at 11.1, a pom t whose P05] tion was found bj COl illetet 'to he praetiG:!I.lly independent or the quan~ity of Iiq uid taken, This tern pcrature is the critical tern per a tu re fOT the substance"

11. We give below a table of critical constants, taken from Landolt and Bomstein's Physikalisch.Chemi"SlChe Tab~kn.

.020 '0

~, 160

•

I

• i I

• I

:Tc

~~--~--~--~~~--~-- 300 32(10 310 360 38.(1 4 0

Temperatnra centigrade.

Fig, 10.-Vapour Pressure C1Jt'i'"C for "Vater.

Gas

Tobie 2.-Critical data.
T. p~ v •. RT~
in -c, in atm. Specific P. V¢
volume
- 267·9 2-25 E'1,4 3·13
- 239·9 12·S 32,2 3·28
- 122·9 4.8·0 1,88 !H3
-188·8 49·7 2,32 3·J~2
-147,1 33·5 .~·21 S ·'1·2
31·0 '72·8 2· I7 3·18
l!l2 ·2 112·3 4·24 4·12
1'93,8 3Edi 3·85 3·8!
157·2 77·6 1·95 3·60
143·1 65·9 2·'71 3·80
D74·2 220 2,6 Helium Hydrogen Argon OxygeTI J\~ i tl'ogen

C;j t bon-dioxi de Ammonia Ether

Sulphur dioxide M et.h yl ch lori de \V"tP._r

12. MaHer near the Criti:cal pmn:t.- There has been much diseussion about the state of matter' near the critical point since the LIme of Andrews. The properties actually observed afe:~ (1) tile

•

IV.]

MATTER NEAR. THL CRITICAL. l'OlNT

103

Jemilies of the liquid and the ,:apour gradually approach each other till they become equal at the eritical point; (2) at the critical temperature the boundary line be tween the Iiqu id and the V:i pour disa ppears. and hence there must be mutual diffusion, and the surface tension must vanish, i.e., the molecular attraction In rhe liquid and vapour states must become equal; (3) the whole mass presents a very flickerLng· appearance which sugge~t!S that [here might be variations ·0£ densii y i uside eh. e mass. Thi5 W:LS e'Xperlmenrully, observed to be $'0 ~"ly .Hein and ?thers. They suspended spheres of" diff.cl'em densities insitle the fluid when each comes to rest ar a horizontal vsurface having. ~ density e9u~1 to. its own.; (1) compressibiliry of ""_pour at the critical pom t IS infinite and 1:; very great near that pomt. As pointed out "by GUCI)" this explains the variation of density. throughout <he mass observed in (3) > for the superincumbent. vapour causes the density OL lower parts to increase.

From these considerations the simplest and probably the most correct view whichwa~ put forward by Andrews appears to be that [ust beyond the Cl'ltLf.lil t,cmperature the 'whole mass is converted inw v::Jpmlt consistlng of a single c;omtltucnt and should behave like a gas near its poirit of liquefaction,

According to thls theory the critical phenomenon; i.e., the disappearance of the boundary between the liquid and the vapour and not its motion, should occur only when the amount. of liquid in the lube is such that it will fill the' whole tube with vapour of critical d.ensIty, If ~o:re liquid is present the meniscus should go on risi;ng Llll at the crirical temperature the whole tube becomes fillet! wIth lifluid, If less liquid is present, the meniscus goes on falling till at the critical temper(iltur~ the whole Sh01l1d become filled with 'It':apour alone, Experimentally, huwever. Hein fo·und that the critical phenomenon is observable when t.he initial density varies from 0 ·135 to T .269 times the critical density. This is probably due to the property (,1) ali [he variarton of density inside the mass allows the excess or deficit amount to he adjusmd. The branching of the vapour pressure rurvc at ]1,,1 observed by Caijletet and. Colardeau mav be explained

in a similar way. . '

Experiments with water by Callendar point to the existence of n critical legion rather than a critical point. He Iound that the t!ensity of the liquid and the vapour did not become equal at the leTIlper~ture at which ~be meniscus disappeared, but that 11 difference of d(·~mmy , .. 'as perceptible even beyond that temperature. The critiral point is that potn; at which the properties in the two phases become equal,

1.

Books Recmum.endecl.

Jeam, Kinetic Them) of Gnus, C. U, P. (1910). Kennard, Kinetic Them)' of (':ra.se.~, (1938), Clazebrook, it. Dictionary of APfili,ed Physics, Vol. 1.

3.

;

CHAPTER V

CHANGE OF S.TATE

I. _ It is a rna ner 01 cornI!-lon experience that on the a p plicatio [I ?,l heat, su_bstanres ~an~~ d~,e1t ,~tate of aggregatioll. Thus when ice 1."_ heated It melts .mro .hqU.Id .\_water) at I..Y'C (t.he melting point). ~.yben flUt~e~ heated .t~e hq~l(1 passes completely into the vapour !>ta~e at 100 ~ (the b.ollrng point) under atmospheric prcssme. Conv"t:l~ely, _on w]thdrRwmg hea.t ftyrn a .g~, it 1.iquefies at ,the lig,uefa. ctlO~ .pom_t and" later .the liquid solidifies at the jree:nng pOUlt or ~()ltdlfi.~ltJ.on p~I~t .. } or a pur8 substance the melting and the freezlUff pmnts are Identical, as are also the boilirnr and the Iiquefaction

poultS_ ~

. The telTIp~ratu~e at ~1!lbicl1 any chang{~ of state takes place is g;en,era~ly fixed provided the external pressure h fixed and the substance 1$ plll·e. 1.--he fusion point usually varies ,,'c1'y liulc with the pr~SSllrc \1 L reqUIre! a pressure of ab?u~ 130 atm. to l~,~'er the_ melcing p01~t of !ce to - 1 C), but the vartauon o( the hoiling pOll1t wuh plC~SU1'"e ts very great. As a mauer of fact, it can he easily shown t.l~a( water ~a_ll be rn~de to_ ~oi) at any temperat.ure up'. to (}'~C.* pro\l(~f'r'l the pI essure is suffici4!uny reduced- Conversely, the boilina JJOl?t can also be :ai~fd comidera.uly if. rhe pTe5~llr~ 'he 5Ufficiently ]~lCle~sed. 'These Iacts can he readily verified 6y considering evapora· non in a closed space.

. 2:. _ Evapora.tion in a. ~ed _Spac:e.- If we fill a glas$ vessel partly with .wal~r and evacuate l!wHh 11.. pump, then water wilI begin to o~0I1 ,c;ven at loom temperature, If the pump he now cut oll, the pI'Cs~ure can be measured by a manometer, Fur a certain definite tC'mpet.aturc of the liquid, there is always a definite vapour pressure. If we. mr:rea:~ tile total space, more liquid will evaporate, and f111 up l~te extra spa~e,. 1£ we reduce the space, some vapOllr WIn condense tl..T! the :remauung va P our exerts the same pressure. If there '-

tit dr.' ith h .. - 15 a _. 11"_ ga;s~ no n::actlng. wit t e vapour, the 'partial pressure of the

liquid ,.~'Il~ be approx.1m::uel y .equal" to the vapour pres~me in the a h~l~CLOl the tlu!u gas. It IS an lmporW,nt experimental task in Physics to determine rhe vapour pressure of a liquid at different tern pera rures,

3. .~~o:t Heat.- BJ ack lOU nd that the dlange from one sta re to another IS nor abrupt, but a brge amount of heat must be absorbed before the entire mass Is converted from. one state to another at the same temperature.f Tlmsto eorrvcrt 1 gram of

~ :M~c rigorously, 1L11l to the triple DCfint

. t We. have already discussed in G.lajL II. pp 33-37 the methods of measur-

mg' quantity of heat hy Change of State, . ' ,

v, J

("lAKGE OF PROP J:.'RTI t>:S ON !>.IEL T[NG

105

i

ice at OQC to 1 gram of water at QQC, about 80 calories of heat are ~'quired, The amoullt of b~al. required to w~,,'erL ] gram of a solid into a liquid without raising the temperature 15 called the latent h~td of fU4icm. Thi.o; amount o{ heat is required for overcoming the forces of attraction bel;>\leen the particles of the solid, so that they ~m.ay become mobile enough to form a liquid. In ~olids the molecules are imagined 1:1;.'1 vibrating about mean ,ectuilibTiurn positions which ~uefixed but in liquids they execute rotational and. translational motions and wander throughout the liquid, though eonsiderably hampered. Similarly. to c~nve:rt one b~am of w::ter at lOO_c~ t~ vapour at IODOy, 53S·7 calOf1i~S are requll·ed. ThIS heat, which IS necessary for pulBng the D101eC'I)I_1es of water 50 far apart _that they become quite independent of each other (vapour state) 1S known as the w.tent heat of V'apo?'l:Suliorr.. It will be seen that the latent heal varies, g1'eatl)' with the temperature of vaporisation.

.. 4. Sub~~aHtllli.- SmIletirnes. a solid ,may ras~ to a vapour state wUh?ut passmg through tile, .mtermedmte h9u1d state., Camphor fl.'lrm~h,e5 a .fl:ood example of tb~ class. On bC"1~g heated It == ~Ol roe It, bu t sim pI y eva para tes, Such a process lS called ,m b r H11{l t wn

and the substance is sa_id. to be volatile.

But we shall see that the ptocess is not peculiar to allY parti-

cular substauce. All sotid subsrances posses~ finite vapour tension at even ordinary t,emperature_ \rVhen this vapour tension i~ too ~mall> we take no notice of it, butwith the aid of d~licate apparatus, it can he measured. A substance ]!i said to be ,wlattle only when the boiJing point at atmospheric.J)le~su.re_.is less than the melting point. Thus under an atmosphere different tram our (.lWH, say at the moon, even ice which we no not consider volatile would have to be treated as sn dl. The moon is su pposed to ha vc a very thin a tm osphere ( < 1 mrn, or ttlerc~O') ,and the tern perature is below OO{:. H we consider om-selves transported to the moon, our studies will show that ic:e is voluHe because on being: heated, it, "",HI e'\,'aporate to the g~seous state withou~ passing through the liquid state. If we want liquid water in the moon we must arti.ficiaUy produce a higb pressure ana apply heat to ice under this pres5l1fe. Similarly, camphor <.'H1 he melted to a. 1icluid form wben it is heated under high pre-5sl.m:.

S. AmorpholJs SQlids.-Impure substances, mixtures, and non-crystalline subSLaI1CeS do not usually have a sharp melting point; in their case fusion and solidification lake place over a short range of temperature. This is due to the pl'{!·st:'n(.1~ of two or more substances which do not solidify at the same t("1llperalme. Eumples Or such amorphous ~ul?S,Hlru:~s !:Ire, W[I_X,. pitch. gbs.~ et,;_ GLass ~adllan}' softens throughout Its bulk as its temperature 1-5 raised- and is usuallv rt:g;ardcd as a supercooled liquid.

6. Cbaflge of Properlie5 I}D Mefting.- Several properti es of su b~t;mcc~ change in a very marked way when a substance melts. This IS due til the regular aJTangcnlent of the molecuies in the Slolkl being IlI'~Lroy~d by the addition of heat. The following are some of these

I .roperucs :-

1

1.'1 ~

-

--

lO6

[ CHAP.

. (I) . Cho.n$8 Of Volmne~Most substances expand on soliditica-

non while 3;. few others contract, To the Iormer class belong ice. iron, bismuth, antimony, ctc.: paraffm wax and IU(}.';.t metals belong to the latter d aSS. Good cas Lings can only be made £1'01'11 su bstances of the former class. Oft:en enormous force is exerted by water when i t freezes in to ice, The burs ting or wa ter pi pes and of plant cells and the ~pJitting of rocks is due to this cause.

(2) Change of I:'apowY.Pressure,-The vapour pressUTe .abruptly changes at the mel ung pOIll t. The vapour pressure curves of the solid and liquid states are dillerent and there is a sharp discontinuity at the melting point (Chap. X, §4l).

(3) Chamge of E.lec(.rical Resistance,:-: The electrical resistance of metals undergoes a sudden change on melting, ·When the substance contracts on melting- the conciuctjvicv increases and when it expand.s on melting: the cor~du{tivit~ decrea5c~. Tab!e P he:lo;w gives the ratio of the resistance of the fl uid metal to tha t of th e so lid form at the melting point for a number of metals,

Tabl~ 1,

Th " 1'," I;" resist nnr::e () f .fi1dd me:ta l j J

~ ~ "-" . or SOme melarot/,

resistance: ()r r.:rystallisf:d metal \

Substance Rcltlu Substance Ratio
Al 1·6._) eu ] ·97
Sb 0,70 l.i 1·96
1-'b 2·0 Ka 1·3+
Cd 1·97 Ag 1 ·'98
Cs 1·65 Bi. 0·45
Get 0,.58 Zn 2·00
Au 2,28 Sil 2·01
K ] ·32 (~) I~ i~ ,:]so found that mohe!_1 metals show 11. diseontinuitv in their dH-.~(llymg pm"'er at the mel un g poin t..

7. .Determination (lji ilbe Me1.till.gPoimt.- The melting point under normal conditions can be determined with very simple apraratus. The substance Inay be heated in a crucible electrically or otherwise. For high temp-:ra,wres, the crucible must be of graphite or some other suitable materia], and the substance heated in a non-oxidizing atmosphere .. 1 [ the substance is rare, it can be employed in rhe form of a wire (Wire-method), As thermometer, the secondary standards are very convenient. [0 use, the thermo-couple or the resistance

~ Taken hom HfJ!l(]IJ·lfctr del' Ph)'~k, Vol, X, p, 37..

v·1

DE1"jillMINATION OF TIlE LATEN'): HEAT OF FUSION

101

thermometer being generally ~husen t. such thenno,~uples or reslstance wires must Dot he thrust du-ecth'lIlto the II'.le. It.]n.~ substance, but should .be protected by a shea ~ h of protect.mg material. say porcelalH, hurd glass or magnesia cubes. N (JW [IS long as the substance is melring the temperarurc remains constant and hence the E.M.F. of the thermo-con fI.1 e . or ih e res~stllnoe of the thermometer IS abo statlonary.

A curve is· plotted with the E.~.F. ':

or the resistance as ordinate and time as abscissa. The horizontal part TC, presents the freezing of tl~e m~ tal and the . corresponding E.M.lt, . g'lves l.t~ melting pomt" Such acuTV.e fDrcopper is sho ..... .n in Fig', 1. where 9UP't-lORh, Pt couple is .. used, The con~tant KM,F .. c-orre5pondlI~g Co the hosizontal Fart IS about 1O· 5 InV, whkh

WfI'l:~ponds to 1084°C.

8. D.elermina.tl.oD of the Lakm Heat of f'u:sion.- For determining the latent heat of fusion, an onlinary calorimetric method (CbaF, U) may be employed, e.g.,-(l} the n1ei.h?d of mix;ul"es, (2). the Bunsen lee calorimeter. (3) the me thud of c~)ohl1g,and Vi). dec-meal methods. Method. (3) is unimportant and will not be conSIdered here.

The method of nlixlurt!".-It is quite simple and has been explained in Chap. n. Most ~f tile early ~e,tCl'r~l;atiom of the ~atent he::lt of ice were made by this method. 1 hus l E M gra.llli of ice at 00C are added to a calorjmeter containing water whose total thermal capacity is W and initial temperature 01 and if ~ll he the final tempera ture, the latent heat L 1 s g-i ven by the rela non

.iHL+M{l~=W(Ol-BJ... (1)

An important source of error in the. ab~ve met~lOd lies i~, ~he: fact t ha t some water a dheres to the crvsta 15 of ice n tOe, T (I elim In ate this, icc below oce is {feq_uentlJ: chosen which n::quir~s a K.ll?wlec'lge of the specific heat,of i.cc. ~n this method we a~e.r:qULrec1 to fi.nd the heat, taken up ~Y ice rn bClIl~ healed, A cot:lie:F.ic m~t~od r~l.ay also. be employe-d, mz., the heat gIVen ou~ by wat~r In solidiflcarion ;nay he found. The most accurate experrments gIve the value I. = {9" 6 cal. (or the latent heat of fusion of ice.

The met hod nf mix trrres has been very cunvc:nien tl y adopted to 1 he simultaneous determination of the melting point and the latent heat of fusion of metals and their salts, Gooclwin and Kalmus 1::111- ployr-d this method for finding the latent hca! of E.usion of "arlo\~s. salts. A known '''leight of the substance contained In a sealed planUlIIO vessel is heated in an et.ectl-lC furnace to a hig-ll accurately measurable temperature, It is then dropped into a (.a~orimeter and ITu' quantity of heat liberated is determined in the usual manner. The'

11')\ -

1~.7
'1~,· 1\
10,5 \ LO~.·C
.........
~ \
. l~,~·, \
•
io.a \ '
~~.2 ~Tim_ n,
~ :61~
, ,to . lci~!llo 0011 l~ 'r=.

Fig. 1.-1~dt.ing point OI copper,

108

CHANCE OF ST,~:rE

r CHAP.

electric furnace 1::; specially designed to secure a uniform tEmperature throughout the platinum cy~lnd.er ;!lh:i.ch is measured by a Pt-Rh thermo-cou ple, As rnlonme tnc Iiq uid, water was ern ploy ed helot .... ' .tIJOo C andanil inc above that Cern perature.

First a blank experjment giy~S the heat capacity of the platinum vessel. The experiment is then

d performed with the substance

]120! I heated to different initial tempera-

I cures extending over a range of

J,-.~, ~ilEf-i}-!r7.;...' _: -I---l----l---...-l about 50"C both above and below ,~ the melting point. and the final

tern pera LU re 0 f the calorimeter noted. From these after correcting

lOO M -c for the heat capacity of the vessel,

the c!uantlty of heat Q nf'Cl.:;SSary to raise 1 gram of the substance from the room tempera ture to its 'i.n[tlal temperature could be calcula ted, Plott.ing Q as ordinate and T the corresponding initial temperature as abscissa curves of the t'Vpe shown in Fig. 2 are obtained, The discontinuity in the value of' Q indicated by the vertical line givc8 the latent heat of fusion, the ternperature at whi • .h this dlscorninulty appears is the melting point T iH' • find the slope of the curve at any tCl1lperature giv:.rthe specific heat

of the substance at that tEmperature. .

This method has been ronsidereblv improved by Awbery and EGriffiths who ha VI: made accurate determination of the latent heat of fusion of several metals, 'I be)' employed a very special type of calorimeter which was so designed that the heated substance couM be kept surrounded vy water imide ~he calorimeter and the lid of the latter closed bcIore an}' water had access to it. so that she loss or liquid 'by evupcration was eliminated.

Electricai M ethod.::« This consists in measuring the amount of electrical en€1"gy r~'l u Ired to hea t a mass of the su bstancc below its melting point to a temperature above it. The me thou was employed by Dickinson, Harper and Osborne [or finding the latent heat of fusion of ice. Electrical energy was supplied to a special calorimeter similar to thac of Nernst in which ice below OCG was, placed, Then

E..,." r :mc~ldT +L+ r~. ~'I>~dT~

J 1 Jm

Cd_r---;r-_"-~-....,...."...:-r___'_'

lOO~-+--I-f-+-

Fig. 2:..-Latel1~ Heat 01 Fuslon ·of Salts.

:,,~~e:~ E denotes the electrical Clle_:l'gy supp~ied p~r grarn, Ti) T~its initial and final temperatures and c 1'1, C ~ ~ the 5pecinc heats of ice and wate.r respectively. From this relation L can be calculated. This method is very convenient for finding the latent heat at, low tern pera tit res,

Methods simi.lar to the foregoing can also be employed fOT finding the heat of transformation of One allotropic modification to. another hut we are not concerned with them here.

(2)

•

vl

l'.Fl'F .. C'1" 01-;" PRESSIJRE ON MEl:rrNG pOIK[,

109

9. Indirect ~letLod.- Another method of finding the latent heat. consists in making me of tile Clausius.-Clapeyron relauon (Chap. X)

I T (jp. ) (3}

.. = . oT ~V2-1l1 ,

where Hz, v~ denote the specific VO]UlTlES of the' liquid and solid respectively, and ~i the ratio 0.1: the change of pressur.e to tlu~ change of the [reezing point. .In this way L can be easily found.

10. Empirica[ Reiatienshil"£,.-It was _ o~served by, Rl~rds ~t. [[ M L denotes the latent heat multi plied by the aionuc weight and T"" the melting point,_ ML/.T,;; is appl"OxirnateTy. constant _for .aU substances and its value lies between ::! and. 3. TIm generahs.atIOll is known as Tvouion's Rule. But the relation is only approximately true, and the value of the constant seems to depend upon ihe nature of the crystalline form in which the. substance solidifies. T'able E" shows how far this generalis a tion hol ds.

TaMe 2.-I11ustratiol1 of Twuton',j: Rule.

Me.l~ing ML
Substance Atomic latent pOInt 1- .. Crj':m!l system
heat in cal. r:
----
Na -630 371 l ·7 }
K I 570 336 1 ·7 Body-centred
Rb 520 .'112 r ,7 tube
c.;~ I 590 ~oo 1·7
eu 2750 1356 2·0~ }
Ag I 26~O r234 2·13- F" ee-centred
Au ~ sioo 1337 2·32
Ph l .1110 @(} 1·96 cube
Al 2500 930 2·70
J\1g 1130 927 ,1·2:2 11
Zn ]800 692 2·60 Hexagonal,
Cd 1500 594 2·53
Hg 560 231 2·'i'O I U. Effect of Pre&ll1ill"e 0'11 Melting Point. Rege]ati,GJI-A~ already mentioned the melting point of a substance is not quite fixed: It (hang-c~. when the ext.ernal pre~5ure is varied. Equation (3) givit;tg 1 1'1 c ch amre in meltin g poiri r due to pressure has been ded u red m l :hap. X f'mm thermodynamtc considerations. This expression clearly ~hows that the melting point of" substances which expand on solidifira[ L on is 1 owered by increase of pressure w h 1 le the con verse Is the case rf)r the other class of subsrances.

>t Largely taken 1r(J;~\ H.;;,ndbtfCh (!~I" EJtPcrjmt'I!!t;lI-Ph:J'si,~, Vol. 8, Part 1, I' ~I)::'.

no

{mAP-

ClilA,NGE OF HATE

v, ]

Ice belongs to the iiP.ltca tegory, ] L is ~lis prnpert y 01 i~ w hicb accounts for the well-known phcnume.ll.o.r; of. Regda:tton, t.e,) the mel ti ng of ice n u d er pressl1 re and il:.~re.!iohdJfica ".lOon when the pl'e~m r.e t~ released, This pl'op~ty cna?lcs us t~ explain the ~legantexp~u. menr of Tyndall" 10 which a plec.e of WlT!~ loaded <H either end 'Wl1h we]ghtB and placed on 11 block of icc finds il~ way through the latter though the fauer remains intact, 'The well-known phenomenon of gl<l!cier motion is tJan1y due to the same cause, Snm~T ~oes. Gil -depC)~it]llg on a mountain and when the mass attains .sufficient hCl;?'ht the ice at the bottom m~h.s under pre!l~.ur~ ~ncl hC'guCis to flow, u.ut a~ soon as the pn::;sure ]05 released It resolidifies. The block of ace t.ll us contin uousl y shifts down the slope and we have tb e phi.enJomenon 'Qf g lacier roo lion,

12. F~jolil (Ii AUey5.-Alloys, c.x .. cept those having composition in the neighbcnrhood of that of the ente<:tk alloy, do not have. a definite melting point. Consider for example an alloy of lead and un, The rneltl.llg point of lead is 32:'i°C and that. of lin is 2;:l2;)C, the euteeric al1o~y l'laving the com.~o~itiou 6;;1% Sn a.nd 37% Pb. ,If. an 1l!lloy of 90~o Su ,Hid HI% Ph IS cooied h'011'1 the molten state It first becomes pasty ott about 2lOQC whr=n .~ol]d,ification commences and till begins to separate out, and this continues t.ill a ~emperature of 18S<>C Is reached and the remaining liquid mass whizh has the composltjon 63% SF! and 37% Pb solidifies completely; Thus [he addition of a liLLle lead to do 01' a little tin tcIead has the eflecc of lowering the mdting point of the plae substance just ills the addition of a little ~Jlt lowers the melting JJuint of ice, .in fact thp..-behav.i,our of the .;J;lloy is jmt Iike that of u.: salt solution depicted in Fig, 1, Chap, VI.

Similarly if we starr. witl1 a mol ten alloy rich in lead. i.e., 80% Ph 201"f, Sn, the mass first becomes pasty at about 275°C when lead b{ ~jllS to ~~par3tlJ out [otHd finally the whole mass solidifies at ] 8Y'C. Thus whenever the alloy is vell' rich in o-ne compone.;ut, the molten TIl a ss w i1l fi rst become pa~ty on roo]ing-,thc J;18.stc cOll5rsdng of crystals of solid held in the liquid, and this will be indicated by a halt in the cooling curve. On further cnoling 11 second bah i~ reached when the ,emire mass solidifies at lMgC, T'he lI110y correspondil1lg wthe composition 6.1- ~4 Sn .n % Ph is called the eureetl C lIUny a rid this t empenl.[un~ of 183QC is called the eutectic temperature, If we start wi~;b the alloy of ~his wm.posidnn it llliH solidH'y or In~b at a de6nHe lem.pera.tl:.:rre-rhe eutectic temperarnre. Similarly if we melt an aHoy of compos i tien nth er than the eutectic. it win rlfst become pasty and du:n at a higher tempera rare melt eomple tel}'. The <lUo'Ys of other metals jn general behave similarly.

Alloys are of considerablepractical importance. 'Thus on:lin:at)' $oft 5>older or thumm's solder is an alloy of le~d and tin hltving about 60~ Sn i,c., a eute.cdc mixture of ]e-ad and tin. It has a me!.dng

1)(1 i Il t I II II l II 1" w~:r th~n ~3;,t of, tin or lead, and ~l<l;ii a sharp a ~Id .II liu i I (~ I nJ1 l" 1 .uure of solidificatien, An alloy of HH and lead {un. rl, letu], I) I!L{'] L!oI at 194"C; Rose's fusib,~c metal (tin, 1; lead, 1; bL'oIllll!II,':'::) 111~'IL~ at 91°C; "\¥ood'g fusibie l11~1.llI1 (tin, 1; leac],.2; i ,HilUllllli. I. hismuth, 4) melts at GO ·5QC though~~f: melting points ~ tj Ili~lmll h. I(';HI and tin arc 2fiD. 327. 232~C respectively.

] 3. ~UII~ICIIQ][ng.~it has been. stated above that when a liquid j I I" III II II. ~U] i tl i hes at i a defL.l1i. teo toe. mpe~a tun~. (i~8 fr.eezing pnf ut). 1'1 j, I I II, fill II q, h u~vCver ,.J ~I owly cooled 111 a, per~c>Ctly dean vessel, I III I" 1'1 I n I Kh t down to Oil t,enlpl..'ratUrL" roll eh bel ow the normal fteez-

.1 "11Il \~lIhout s"l1l1u~i[ring. This is ;knm~n as the phenol".L"lenon of I I' JI r j' ~ fit su 1"£USIOl'l, "Vater c<ln. in this way be cooled dO".~n to

I ~ I l ,n ~I m lower with <I. Iittk- Care. Dufour suspended a minute II IJf ~Ir w,Her in a mixture o.f chlnroform and of sweet almonds l~'hich r I I I l'I'L'irtf'" gnn'i~}' equal to that of~he water drop and managed I I L 11,~l till· latter to ·-20QC without solidification while a drop of II 11011111 I lcne could Le supercooled to 40QC (nonnal melting' pOInt 101 ill' HW'q,

S, I II It'rcot;ll i.ng is, however, essen tii:ll~y an unsta hl.e J?ihel'lo~'lenon" I III inuoelucticn of the smallest quan~lty of the solid 111 which the I.~ I L1!d wouhi h'eezc at Qfil-e starts the solldlfication, Mechanical dls- 1111 h II1I e such a~ ~.~I.a_ki]lg ,the tube, st.:irrinp. ~r rubhing ~h~ sides with • 'I,I.~~ rod; or addition of some o~heT aohd ~l~ often sufficient to start I ,Iii hilI ~ i LO~1. If solidification has once started it wi.ll coneinue with

~ \ 0,1111. ion 01 heat till the normal freezing' point is reached. After lh) I lUll her solidificatiou wlll take pba: only when heat is JUSt by I III tol i LOll, etc. Absence of air favours supercoollng probably because II1I i luvt particles contained in H are rhen absent.

VAPOILUSATION

14. [Yapor.lIt:<lD, BD~iIlg'8!l1.d SlIIperhell.ti.ng.- A substance can pass it LJ:11 l hciiqL~~ d state _t~ the vapO.U.f state In ~wo 'h~1J. ys, viz. (i )evapoj ar ruu and (n)ebt.llnlOU or ])oIlmg,. 11:0. the £On1!ler the Formation ql \'::ipnUf takes place dowly at the surface atall ~emperanHes> while I II I he La uer Iohe 'ilia pour is rco.med in all pfi ttl; of the liq ui d a.C a I 1~II~Lam temperature and f~sciflpe;5 in tIte form of bubbies producing 11. hi~~fnh noise, Inltially these vapour bubblesare funned around sma]! 1IIIIJlJl~~ (If air clinging to ~he bottom and sides 0.1' the vessel which I ,~I i J ~ W te th e proC"e5.ll of boil i ng. If, however, the Ilqu id is carefully II ~·t·il [1"('J<m disselved uir ani! dum heated in a dean vessel, its ternl'l'I.l.llll'l' can be raised several degree-.~ above noo"c without its beginII ~lIg 1.0 b~)il, but when boiling $t.1lrts due to disturbances of rimy kind, u, ~t a rt s with ex plosive vIc.1 ence, US1l3 11}' caned b urn ping, and the II t II] ~('1 ': 1I111't: faU ~ to roo <;>c. Thi~ 51l tiet h ea a 1'1(5 is thc cause of bump .. III~ .lll!] j\ pH~\'ellted hy tbe a.ddition o.f porous objects,

IS. Saturated aDd U:nslI.'lIlr,1Itedi Vapour,s.-]f the varmn esclIping Ii "Ill ;1 li~J11Ltl either by evaporat.ion or by boiJing is collected in a \ i ~sd it will fonn. 1II} unsaturat.ed vapour. In the ca&C of evapora· 1 jnn in a du~ed space as ~[l § 2, the ~p1lce wUl be filled with un~

'I" John l'yn{iall (1820-1.003). Born ill Irellll!ld, he studL~cI at Marbllrg :J:rtd in Berlin. Fr'Olll. ]253 ollward:s hll was Pro;]essor oi Pny~Lcs m the Roy-at 1i'I.~titutioll in L1l11don, H!l wa~ weH.J~[lClwn a.s a. bdlliail,t expetlm~!1kT :md Was f<md of m01JlJhdil,eedng.

IU

I I

112

'ClIA:-fGE OIl" STATE

I CHAP~

saturated vap0I.l1' if atl the liuuid haseva~orated, but if the vapour remains in contact withsoTl1e liquid, it will be saturated. Unsaturated vapour approodmately (lb, eys Bovle's law but for saturated vapou1' the pressure depends only on the temperature and not on the volume. '\Then saturated vapour is heated it becomes u~aturated or surer" heated, ,"Vru::n saiurated vapDur is 'Cooled withou t eondensauon occuni ng it becomes su pers:ltu.t"a ted.

'1/1,[ e shall now describe some nlethoJsf.or dctermini ng the vapourpressure- The range of p[essu~c to be measured varies from W-4 nun. to 400 atmospheres, In oertarn CiI::Se5, pressures ~t8 low at IO~1i mm. have to be measured. It is dear that such wIde range oI values requires various kinds of apparatu.'>.

16. Viilpour Pressure of Waler.-Tlle first accurate determination or the p:ressure of saturated vapol1l' was made by Dalton, A similar bur: improved apparatus was later employed by. Regnau]t I'm finding the v-"pour ple8S111'e at temperatures lying between 00° and. 50°C, Reg. nault's experiments were perf;ormed with the gre.ate~t care and extend over it wide raJlg,e of re:mperacures, Ilts apparatus far the range 00 -50':! is shown in Fig. 3. Two barometer tubes A and B were arranged side by side. fed Irom the same cistern of met<.:1.lt)' M. The spaoc a above the mercury level in the tube B is. ~'acuum, whitewater ]~ ~adl..lal}y introduced at the bottom of A tifl iL Tili-e"S through the mercury column all d eva poraIes 0 II reach Lng b. More water] ~ introd uced t.ill<l small layer rem ai ns fJ.oat~g_ over ttl e me-feu 1.'1' surface in A. A constant temperature bath DD furnished wlth stirrer (not shown), and a rhermcmeter surrounds rI." b, as 'wen as some length of the mercm}, column. The difference in the heights of the two mercury columns-which ;" _ observed through a g-lass :~'indnw with a cathetnmeter, gives the sattu<l!.ed "lipour pre~sme of water ,at the temper~tm:c or the bath, Cor.rcc(~on must be made for the l,,;'elght of water m A. [or effects of capillarity, refrac tio n, etc.

FOl'rempc.:rature~ below w'e Regnault modified his apparatus to rl.ac nf Gav Lussac. The top. of the tube A 11!a~ bent round and terminated 'in a spherical bulb which contained water or ire and was surrounded by a suitable bath, For tt:mperature.~ not much above 50"C the apparatus already described (Fig. 3) could be used. 'when a

Fig_ 3.-RellLlault'~ Y~:_)[)Lli!" pressure il.1JP~ ratus.

H3

GENERAL MlrU-tQOS

I'JIIgt'l lcuh would be necessary, but Regnault preferred the boiling l~wlll. <.Ipparatus (Sec. 18).

17. General Methods.- The methods used tOT measuring saturatd v: If lOU 1 pre:;s me Cit n be broadly divided into two classes ::

~!)~ le l hods ~n wh ieh the ~m perature is kept fixed and the III c ',~~.IJ 1 i .1.' determined either manometri caUl' or by measuring the ~ I!' t m l)' of saturated vapour. Thisis called the direct or static me tbod. (i i) M etl~od~ i n w~li ch the _ptr~3£lH'e is _gh'en and the tern pe.ra ture Ll \\ III til the liquid begins (0 bcil is determined, This is Lh~ d'ynllmic JJlI'lllUll.

IS. Statical Methods.-Regnault's method is Illustrative of class

't: '1"11:- sa:me, mel.h~d ~an be adopted for _fi,nrling the V3I)our pressure I" .~I.}y.b<JUl~ provldnll,t_ does not react wrtn mernn:), an~ the ~'apour jlj , ,~~ u~ e IS Il,~lth er . ~oo lugh nor t.o~ low. A Ilumbt:r 0 f JOvest~gators h.1 \ C ~mpJ(}]e~ this method. Their apparatuses dlffC!I' only In un( ~~"IllHII . details. .A g.tTIerar sch . .cm.e of appara.tus ut:ih.'~ing" this uldhod !s shown l.n li'Ig. 4" A 15 a small grass sph~Te,> a. few C.Co I II ccq.JUO ty, to w luc.h f 8 attached a g,l a:;s ttl b e (, ,1.lId. another glass urbe D with :\I smaller bore,

I his 1:; connected to a bigger glohe G and a II I ( rcary rna nom et_er ~·I abo tt t 90 em, long. The \\ Illlle apparanrs l!; first evacuated through the ~Ifj[l cork S1 and then the latter is closed, Next I he gas under investigation is introduced I II ~"Ough the :s~()p-cock S2 and condensed in A by

~11I j ably cooling the latter; finally S2 il> also (III~L'J_ The sphere A is then surrounded by It'!npenl.cme baths and the vapour p.ressure corI L '~,~ nn ding to til e te!upeta ture of the' ba th is

In L I ra ted by the manometer M" B is a baro-

IIId.er to Indicate Lhe atmospheric pressure, The

.1 PI.);lr.'l.LUS . l_s convenient for measui-ing vapo.~r

pl L S stu es 6, OJU ~ few em. to the a tmospheric

I UU.qu-e. } or hIgher pressures a compressed air 1I1;1l10111eter may be employed when the whole appal".atlls has CO be made of steel,

. A similar apparatus was employed by Hell- 1111lg' and Stock lor firlding the vapour rre8~ure ~ II :'l Humber of gase:;: between + Wand

I H I "C." On the same principle Siemens has ~ I"~ doped v<lronr pressure thermometry at ]ow 'llIl"~'l.ltmC~, :F01: high pre~ur.es we may 1I]I'lif,1II1l the c!;:J:;5sKlJI experiments of Cailletet

III~ I (·III'lrd~au (p. 101 ):with water.. Andrews' q'I''' r ·.Jm (p. 88} may also lie used. Hoiborn .~ lid B.1IJ Ilb~ tUI determined the vapour pressure III \\';!I('I' ahove 200QC by the statical method. III~: nut hrnl has. also bee~. employed by Smith and MeIlzies though 1,lu II' app:uatus IS much different,

r:

D

M

Fig. 4.-Detenni'[L~tioll of vapour pT(~~Sllre hv s ra tical method. -

114

CJL.\.NGE. OF STATE

[ GHAl'.

In the experiment menrioned above the pl'essure wa., me,l~i,l :ed manometrlcally, but the pressure may also he found by determining the density of saturated v·apuuI'. for assuming that the perfect g:as eq nation holds, we have

p =~:. {4}

Thus knowing- M, p we can calculate p, ii. very simple .appara.tus based on this method was employed by ~snanh :iln~ Gans, A portlon of the va pour was isolated an d i ts densi ty determined,

19. Dynamical or BoiIi:ng Point Method.~ This method is based on the fact that when a liquid boils, its vapour pressure equals the external pre~~sure on the surfac~ o,f the liquid. A definite exsernal pre8~Ul'e is, appH~d on the l~qm.d, su~face. by r~eans of a pump and then t~e I~qUld rs heated, The. Iiquid WIU bo.Il at t~]e. teJ:.npe~ature at which rts vapour pressure equals the exter nal pressure, v.i7.., that set up by the P urn P: ~e!'i ["~ the va POUl' pressun.: corres pending to the temperature of ebullition 1S the pressure exerted by the pUlTlp !l.D:1U can be read On a manometer.

Fig. 5.-RegJ'JillL11t's Vapour Pressure Appal'attl~ (Dyuarnical iucthod.) Reguault employed this method for. finding the v,ap?ur. pn:-s;Hl;c of water between 50°C aud 200cC. HIS appnratus IS indicated ill Fig,!5. Tht:' ooppe.r boiler A is p'lrtly~lIed with the. experimental liquid and contains four thcruwl:netrrs he immersed to d~.ffel'ent (~eptl~:;, inaide the vapour and the liquid. The upper part of the boiler 1&

\ . J

U5

..

«mnected by means of H to a pump, the pressure befng indicated by r rlt:' mP-l"cury manometer NM. The reservoir is kept immersed in. a water-bath Wand serves to transmit the pressure from the boiler to I he manometer as well a'!;. to smooth the fluctuations in the pressure II m j ntained by the PUHl p. The-vapour of the Iiq U] d condenses in C alia returns to the boiler, thu;!; the same qmt.ntity of liquid is used II vur and OW~I' again.. First, a definhe pressu re is established by the I,Llfill) and the boiler heated. In a short time the readings indicated

J I ~r the thermometers be hecom e steady. The manonie ter indicates 11If' vapour pressure corresponding ~O this temperature.

The apparatus can be adapted [or all pressures. For high pressure 'ill the parts must be made of copper and the pump must !Jc a force I )1~Illp. The method is capable of great accuracy. By chis method II olborn and Henning have very accunHely determined the vllpour "J"e~$1I1'e of :~:iter .between 50 and 200cC H to 16 atm.) , Ramsay and \ (lung applied elm method to the measurement of very small vapour

jJr~ssure~. 'Their a:pparatLIs (Fig. p

h) consists of a wIde gl.l5<S tube I' tu which is connected a reser-

voir R, the latter being connectt'd to an air pump and a mannureter M. Definite pressure :is ~t t up by the pump and the experirnental Iiquid, stored ][1 F, i: allowed to drop au the COtton WHOJ. surrou nd:i.n.g the bu lb of I 11e thermometer. The t LL be T I ~ k€ pt .~IHTO unded by OJ. su ffi. I it~lHly hot bath so tlutt the exr w rimen ta;l liquid a:~ once eva pontes imide T and the th erm omcter Sri on reaches .. steady ~pcl'lItul'e>thc true boil.

ing; point of the Equid under that pressure.

Smitl_1 an? Me.r!.~ie~ IHll"'~. devisc~ auingeni. ous mcdification ot the hodJng' pmnt method. Their apparatus is irH:licated in Fig .. 7. The sub. stance tinder investig;J:tion is kept in the sphere A dose to the bulb ol the thermornetzi- T, both being immersed in some liquid contained in the t<.:st-tnue B.. The ~e~Huhe is closed ainight all d com ImH1I(3 reswirh a pump and mal] ometcr (not shown). It Is further surrounded by " bath. who~e t~111reratute ~u be varied, A ,defi;nit~ pressure ~~ l:irst t:'stabl!~hed hv the pump and ti:u" tern perature of the bath gradua U Y raised, '.Vheu the vapour pressure of the substance contained in At,ecorn.es (2l1 LIar to the external pressure 011 the surface of the liquid in the tubevanv fu.rt,hel' I' if'. 7.-S1rILth and increase. or t~mpen.Hln·~increalies the pressure of ~11'11'1~:~' Ariparatus. the vapour m A. which c()tlsequQnuy bubbles

F~~. 6.-Rafi15av and Young'~ appar~@tlr~.

, I

I

I

I

QH,\NGE OF STATE '[ CHAP.

,. h

throu ,.11 the liquid in the tube_. When this just happens te press~re

rccorJ'ed by the m:n:,orr.~etel·gn .. es the vapour pre!;~ure c.orrespondl11g

to the temperatun: inrlicated by the thermometer. . .

TheboiIing - point 111 ethod has also h~~n ap~lH'!d to metals hy Braun. Zinc or cadmium was heated electncally III 11 quart.1. or po;!:" edam tube and the temperature ,of the vap our was measm:ed by a

thermo-cou plc.

20. DiscllIssio.n 01 Rentlts.-Experiments show that the :;.atur.atf::l ",;,tpour pressure of every substance incre~ses :'15. th~ .tcmp?,anue l~ raised. IIenl;.e the vapour pressure P must he a function of :he tern

". '.h - f (n where f (T). nrnst be of such form that Its value

pel ature, vJ,7.., r - , ...' 1 lati hi

increases with the tempcrarure T. Vanous. e.mpln.ca n: atrons IpS

'between p and T have beet! proposed from. tml~ [,~. ~une. "T~l~Y 'hold (or limited ranges and are by no means quite ex-an and u ruv er sal,

In 1.820 Young proposed a very simple Earmula B

log p <= A + 'T'

w here T is th e a bso lute iern pera cure and A., I! ~te constants, K irchhoff in 185R and Rankine in ] 866 proposed q LUte Independently

the formula

116

(fi)

Jogp = A + ~ + Clog T.

(6)

\ .J

117

Thi~ formula a~ees with exreri.mental r_<:~uIts. v!:!ry '11<0 be deduced {tom rheorcrical comHI~ratlom.

Chapter X that

closely and can It is shown in

LATENT HE.AT OF \"Al'ORIZATION

di.,nlphiue. (2) In case the liquids are partially miscible the vapuut l'I'~~~~un~ is always less than the sUIIl of the va,rour pr.essures of the constitucnts and Illay even he 1(1;:'; than that of one of rhern. e.g., water ill I d e tl ser, or water and iso bu ty l alcohol, In this case each cons tituen t dissolves a li ale of the other and the va pour p:e~sun: of t~e mixture reuiains constant over a large l'~mge of composmen of the nnxture but [;1IL~ ol] for yay dilute solutions finally attaining the Iimiting value for the pure eonsrituent. Thus if we distil 11. weak solution of isobutyl alcohol, we hnd that the solution in the 5tiU becomes weaker and. ~vcakel' till finally there is o. 11. Iy pure .water in the ?tnI and pure alcohol 11[ the condenser. For <tweak solution of water in alcohol the reverse is the case. (3) 'Vhen the two liqu~ds arew~lOlly miscible. e.g..,. water and methyl alcohol, the prt:ssure ili intermediate between those of the sCl'ar~te constituents. In this case whatever. composition we. start wi~~, alcohol a~ways passes to the condenser Ieaving pure water in the srill.

21. YIlP0lil" PresSllre over Clu·'v·e;d Surlaces.-In the fn'regoing we have eonaidered the valmur pressure over a fiat surface .. The vapour I ~l"Cssure over a curved surface is different on account of surface eensinn. Evapmation from a spherical drop produces a decrease in ~ u rfa ce area and hen ce aho in the surface energy due to surface tension and therefore, it will proceed further than in the C<lSIe o] a flat surface, i,e .• the vapour pressure over a convex. surface will be greater than that over a. II<Jt surface, Detailed considerations yield the result

1 PI) 2SM

og, -p = r -, pRY'

(7)

(8)

Assuming L constant, equation. (8) yiel~~ Young's forl11u~a (5). If. however, we assume L to vaTY h.nBady w1.th temperature, L€ ..

L =Ln - OiT~

equation (8) yields us formula (6). In order to get the exact valtre o r: pressure correspond 1 n g to any tern per-atur.e we lUU ~t me all accurate ex pression giving the l/31 uc of L as a functlOn of T.

The a hove ho ld s for the sa tura ted va pour pressure of a pure linuid: when mixmres o.f two liqufds are investigated Lhf'~Y yield inee;esting results. (1) To case of liquids which do not at all mix the vapour pr~!;sure of the mixture is equal to the sum of the vapour pressure of the constituents, e.g., water and benzene or water and carbon,

(9)

where p~, p d.ttlote the vapour pre~sure over ~at and curved surfaces respect! vcly S the surface tension, r the radius of curvature ot the. surface (oon.sidered positive for concave and negative for CO!fiVf:'.x) and p t!1e density of the liquid. These ccresiderarions have important nmseq uen res in d Lt.· preei pi ta tion of rain and in the phenomencrrof boil ing. Equation (9) r.hITWS that if r is small and negalive, i.e., the surface is convex, p rna)' become very large. Hence, if suitable n II de l for con densa rion are OJ bsen 1, a h 19h degtE:le 0 r: 5U p ersarura tion [1}:l.Y be attained and inspire of it, no drops will be form~ri.

~ATENT H.EAT OF VAPORIZATION

22.. In the measurement or latent heat of vaporization we have to remember two points; first, that its absolute value is relatively h igh; secondly. chat the latent heat Is absorbed or evolved in an i so therma I ell auge of st;t Ceo The wnseguencc ~ that its ex peri men tar ch'i.(;rmination Is very Iittle affected by the usual sources of error which :111: Ii resen tID all calorimetric measurements, The methods can be ~Inu ped under three broad headings:

(1\) Condensation. Meth(J~~.~Tbo.se in which the amount of 11t',lL evolved when a certain amount of vapour condenses is measured.

(R) Evaporation Methods.- Those in which the amount of heas 1('IJllin~d to vaporize 11 glven mass of the liquid is measured directly.

118

CRANGE OF ,\;TATE

[ (::HAl'.

1I9

The heat is generally added in the form ofelectrical energy and can h~ easily determined.

(C)

Indirect Melhods.-ThOM.: in which the latent heat is cal(.,date~ with tl~e help of some ,then;rwdynalltlCal relutionship such as Cla.usms· Clapeyron relation (equation 7). Fr~nl the va po ur pre.~sun~ curve th(~ q uan ti ty dP / d T is deterrni ned a nd hence L eval Hated. [rum (7}. l.N e shall now consider rhe first two methods in greater detail,

gi,'cs the temperatutt: of the condensed liquid as it leaves the apparatus. In this npetimcnt the vapour must be produced at a s read V ra te au d this is achieved by the use of elecu ical heating. The latent heat is 0 blain ed from the formula

M(!=m[L+s U2-lt) 1- (10) where (} is the excess of temperature of the outflow water over the inflow warer,

M' i~ the <Juan~ity. of wat·~r

flowmg- per trmt time, TIl IS

rhe rate at which the liquid

is bclng discilled, t~ i~ the

boiling point or the liquid, tl the tempera tu re of the I j. q uid as it leaves the a ppara· tus,

B. Ev APORATWN METlton~

25. This method was employed by Diererici, Y-Tho measured the heat required to evaporate a given mass of water with the help of a Bunsen ice-calorimeter. The water wa~ contained in the

tube A Of the ice-calorimeter (Fig. 3, P .. 3-4) and the heat was measured by finding: the mass of meremy expelled. Griffiths found theelectrical ener~ry required to vaporize ~ given ma.~~ .of water, WP. shall describe the apparatus used hy HE:'T1mng for precrsion measurement of the heat of vaporisation between 300 and] OO°C.

Fig, 9.-Awbe.ry and GriJIi~bd Lat~t IIeat Apparatus,

26.. HlmDillg~6 ExperimeDls.- TIle apparatus employed by Henning i3 indicated in Fig. 10. C is a copper ;ressel, one Iitre in capacity, in which the liquitl is allowed to evaporate. This is surrounded hy an oil-hath It maintained at 11. constant temperature. The heating lakes place through the spiral D of constantan wire \'Ij'QulJd on a quadrilateral mica frame. E is a platinum resistance thermometer. T'w vapour which is evotved passes through the GeJ:'Tnan ~iJver tuhe T T downwurda through the Corman silver tube RK CO the vessel P in which it is rondcnscd am'! weighed. The end of H is bent downwards so that no Iiquid drops can be carried. The vapour is first led to one o[ the vessels P, and when the conditions become steady [ II e & Lap" cock R is turn cd so tha t stea m is led to tile (J ther vessel P_ \ftcr OJ suffi-cient quantity of steam has been led to P the stop-cock R is rurned to the other side.

A. CONDENSATION METHODS

X3. Berthdot"s Appara'lu:s.-Rcg--

uault's experiments are rather o] hiaw· rical interest. \'Ve describe below the appara tus of, Berthelot (Fig. 8) . In this a pp~~a ~us whi.cb . is 'whorl},. of gla~s :he Iiq uid IS kept m the ve!l.Se 1 D a 11 d heated by the ring burner B. The rest of the apparatus )s protected by an Insulating man de M. The evaporated gas 'pa~ses. through the Lube T into ihe spiral S. placed within the calorimeter C. The spital S is fitted to T by a conical ground piece and can be easily removed,

1 'he ~ a • JOur co n dcnses wi thiu thl.: spiral a 11 d gi ves oIT its laten t hea t of vaporization to the calorimeter which can be easily meas~n~d by observing the Tire of temperat.ul'e on the therruo~neter 1,?laced 1llii11e a w:.Iter jacket, Th€ amount ~~ water conJ~med rs ;?btamed by welghing the spiral S belore and af~er .tbe expenment.. n~e hcac measured rcprestnts the heat ol vaporization ]?l~$ th(2. heat gl'llen. by the condcnscd liquid In cool fnf!; from the boilmg pm~t to the final temperature of the calorhneter, The open end or S 1S connected to a pump to regulate the pressure under which the boiling takes place.

Errors arc likelv to arise owing (1) to superheating of the liquid, (2) to minute drops of water being car,tied over by th.e val~OUT', As the usc of a ring- burner ~uscs the heating to b~ so~eu!lles 11Te~ul.0I.r, K"hl~nL:tg replaced the Img. burrier by a metalllc spiral placed inside the liq U I d and heated. electricall y.

2:4. Awberv and GrHtjths used a slightly modified apparatus ill wh fell th e mtHll' ca lorimcter WH~ re pla o::d boy 11 conrin UOUl; flow calorimeter. The a ppaT.'l tU8 f 8 shown In Fig. 9. The boiling cha ill bet is heated electrically by an inner coil. The vapour pa:;~cs dm'o1H the vertical tuhe which is surrounded by a jad:et of water through 'which 11 stream of water Ilows at 8:. constant tate. The temperatures of the inHoWing and outflowlng water are determined by two thermo-mllp~e~. There is " third thermo-couple at the mouth of the vertical tube which

Fig. H.-BcrthelC1t's Latent Heat t\ppaTil.tus.

12(}

v, 1

CHANGE OF STA T.E

TROLITON'S {tOLE

121

A typical curve 5,howillg the latent: heat of carbon dioxide at various temperatures is gillen in Fig- 1 L "It is drawn ho1'1.1 the results of several investigators and TCpte-sellt~" mean valLles;. The figure shows dearly that the latent. heat vanishes at th~ Lnt~cal te~npera. rure of CO~ which. is about 3] 0c. This result l~4une universal. The exact varca~ion of latent heat livith temperature for all substances is givetL by the thennodynami" formula

d~. __ L_= ct: _.:',_ ~_ L_ ) (~) ._ (O~Tt) }. .

rr T "'2 - [.']_ l 8 T r 8, .~

where (g. Cj denote the specific heat of the substance in the gaseous and liquid states respectively and 1.,'~, 1l1> tb~ respective specific

volumE>li.

28.. Troulon's Ru:lo.- As in the case of latent heat of fusion, we have here also an important generalization known as Trouton's Rule which states rhat the ratio of the mo[cn- latent heat of 'vaDon~f1- don to the boUing point is n: constant tO'l' most suu.~w'nf:tH; or

symbolically. .

The quantity of vapour deposited in the second vessel is now Ionnd by weighiug and the quarrtitv or beat supplied is obtained from observations of the electrical measuring apparaLUS. For determining the heat of evaporation at lower pressure, P is con n ected to a httge vessel of about 5 lures capacity which h maintained by means 0.1: a water pump at the required pressure.

A similar apparatus was employed by Henning for hnding the heat. of vaporization 01' water up La 180QC when uie Fressurc reaches about 10 aH'Twspl:eres. Fogler and Rodebush used thiS method for determiui ng the 1 ateut hea t. of e \'::'1 porati on of m en::m:}' up to 200" c.

For dete:rmining the latent heat of evaporation of substances like nitrogen, hydrogen, helium, etc., w hi ch he come Iiq ukl a t very low temperM.tuH~S, the above principle has been utilized bv Dana. and

F· '0 H . , T t Heat Ormes, Simon and' Lanee and

lJi- . <t1mlll.~· 9 .• [1 eut ~~ u

Appararus, others.

DISCUSSION OF LA. TENT HEAT DATA

J.=T1 (t .. -t)} (II)

where t e is the critical temp~rature and L1 a constant which denotes the val ue of L a ~

t = t. - L This is of course based on. the assumption rhac 1<1 tent he" t vanishes at the critical temperature, Henning showed tha t be L ween flO" .and

1 OO°C the latent heat of vaporization of water Is given bv the formula .

L = 538 ·86 +0· 59c)4-( 100 - t). (12)

(13)

ML

T-;= eonstant, (14)

where M is the molecular weight and T ~ the boiling point. The value of the consraru is about 2L 'The law does not hold for aSSOelated yapours. Table S shows that the law holds approximately for most substances.

Table 3.-1lIw;tralion Df Trottion's Rule.

SuLstJI1Ce

Helium

Hvdrogen Nitrogen

Oxygen Hvdrochloric acid Chlorine

Pentane

Carbon disul ph 1 de Benzene

Aniline

Mc"]"cury

Caesium

Rubiriiurn

Sodium

Zir.c

Lead

27. V a.fra~ioD of the Lat~lIt Heat with T emper.abll!"o.-:B!:x penmen ts show that the latent heat diminishes as the temperature at which ~oiiinl.5 takes place is raised. . This W~5. noticed. b'_'n by early m vcs tlgatots 'W ho pro po sed varro LlS em pa n cal form Jr ae, 0 f these Thiesen's formn 1 a a ppea rs to have been iucst satislactorv and states '

Tern p~r-dtAn~

Fk. U.-Varia.lion -of Latent Heal: of GO, with temperature.

Grf)m-tnolenL1a1t "Boiling Value f MI.
latent hem in point o '1
&
c.aIQrief> Th experimen tall y
ML
22 4·29 5·1
219 2'0·4 10·0
1310 77·3 17·3
1630 90 ·1 18·1
3890 18S·1 20·7
46(10 2Br_)·!) HH:
5100 309·0 19·75-
64g0 ~j]{J. 2 2H)
7350 303 20·8
10000 ·H57·0 21·!}
14200 (i:~O ·0 22·6
15600 R58 18·2
18700 94~ 19·9
~3nOO n5~ 20·2
27730 mm 23·3
46000 1887 24·4 122

nl£NSITY OF ~ATURATEU V.u'O't!R

12:1

(;I'III.NGE OF STAT];:

[ CHAP.

It will be seen, however, that lUI.IT is really not quite constant for all substances. A simple theoretical discussion shows that it can. not be. so~ for ~e boiling point un~ at~ospherlc pressure ~s purely an artificial P0l1ll, and bas no physical slgmfi,cam::{'. It vanes enormOLLsI}' wi tb the external pressure, while the Ia tent heat \' a des neith er in the same direction I'J Or to th e same ex ten t. In the cas e of WOI ter the Trenton q uotient at ct few temlJe.rature~ is given in Table 1_

that of Victor Meyer, wh.ich is of considerable pl'actical importance :md is consequently described below.

The apparaLLls (Fig. 12) consists ot" a cylindrical bulb 13 1.~'hh a long: narr?,w stem, near the top of wInch th ere J.S a Side- tu be'The lower par t or the tu b e is surrci .. mde.d by a suitable tem,peratu~e hatl~ w~llch .IS kept replenished by a. SUI ta ble _ Iiquid boiling at some pre~8Urf:! In A. Alr inside the tube gets heated and is expelledtaz the top; after a time; however, a steady st~te

is attained when 110 mute air escapes" The

su bstan ce whose vapour density is to be

determined is enclosed In a thin-walled stoppered bottle and placed inside the rube. By manipulating s it is allowed to drop ~ml)' in D, The bottle bre~k.s> the liquid vaporizes and thereby displaces an equal volume of air w hich esca pes <H

the side-tube aud is collected in th,e tube t, Knowing the mass of this air.~he del;tShy of the vapour o[ the substan.ce,ls ?I::itamed by divicling the mass of the Iiquid taken

b)' the mass of digpl~ced. air. , . Fi2:. 12_-Vktof }.I[eyer's

N ernst has modified the apparatus a?d Vapour Dttl5ity Apparatus. co uld th ere hy 111 easure the va pOU1' ~cnsl ty

of KCl and KaCl up to 200tPC while ,"Varteuberg Iound the vapoliT density of several metals ~lP .to 20ClO?C. For a descri ption see Arndt Ph'Ys~)~alw'h-dum:sche Tech-

nih" Chap. lX.

3.0. Ac.curalOO ·d,eterminafioZi of the Deosity o.f Salurakd V~O'1U'.-In I 86{) Fairbairn and Tate devised an appamtus by mea.m of which th~ measirrcd. the density of saturaled vapour directly. Fig. 1.3 explains the principle of their appOIratm .. A is a spherical glas;' hu~b whose ml.n:ow stem dip Into mercurycontainedin the outer Wider glass ':nbc-. The latter communicates with the metal reservoir B. Both f\ and B contain some water above the mercury levels, the latter containing a laTger q uantiry than the former. All air is ex p c llcd from the a ppa ratus and then both the vessels are surrounded by a hath whose tempera.ture is gradually raised .. The , levels of the mercu t}' in the two vessels remam constan t,

Fjg. 13.-Fa1.- that, in A bEing always higher than in B due, to th.e h a irn and Tate's excess of wat.er In B~ 'This is so as long- as there I~

apparatus. 1m}' liquid water in~. But as soon ~s the Ihui~

in A disappears, the level. of meTcuty ,In A suddenly rises, 'Thls IS because the saturated vapour pressure mcrcascs much Iaster than the

Pressure B..P. I latent heat Trouton quotient
----
4·0 rum. IY'e. I 606·5 caL 10
760 ., lOO""C. 535·9 " 25·9
'2\ORI}O " ~::W(PC. 4..oj.fj " 16 From the variation in L and the boiling point it is evident that the T'routon quotient will go on decreasing as the temperatute rises becoming zero at the critical teIIlpeJ.'Ia~ure. where the latent heat vanishes. 'Thus till" quotien L can have ally value Irorn 0 to 'iO and it appears to be merely an accident that. for most substances bol'Iing under armosphcric pressure, the value is about 20_

HETERMINA'lJON OF VAPOUR DENSITY

29. B~' vapour demity we mean the specific gl.'wllity of the vapour referred to air Or hydrogen :JS unity. The "-"POUl' density can be easily rOll nd if we finJ the volume occupied by a known wc:ight (If vapour at a certain pre,'iIlurc and tcruperature, Thus ir w gral}l:S- of the l'<Iponr occupy 1,' c.e, at the pressure p and temperature ""-'1', and P,) he the weight of I c,c, of tnt standard substance (air) at 273" awl 7(lO mm. then the V(lPO]]\' density i~ gi v en hy

w T 760

(15)

The density of the unsatusated. val)our em be easily and accu rately found by any one of tile standards methods= vi~_, of Victor Meyer, Dumas, Hofmann and ethers, Rut belore 1860 there was no method for directly determining the density of .~atun~ted ·vapour s. The methods adopted were all indirect in which the density of the unsaturated vapuur was tirst determinerl, and a.~sul'nlng the perfect gas laws to hold up to the saturated state, the d.emity o.f the saturated v.a pom was de term i ned. This assump cion is, hUWeVl'.T, not quite justifiable, hence these n;ethods can never give ;JC':cm<Ltely the density of saturated vapour. Still, however, they are frequently used espceiall-,

'" F\rll !li:ta1h or these methods will be fotmd in any text-hook on Phytieal Chemistry,

IN

[ CHAP.

CHANGE OF STATE

pn:-ssute of. unsat~rated vap~ur obeying :Boyle's law. The tempera· true at ·WlllCh. this sudden rise of me-rcury column. in A appea1".~ is. noted, At th.l1> temperature the vessel A becomes filled with saturated vapmrr whose_pressure may he found by means of a gauge connected to B. Knowing the mass ot water in. A and the volume of the enclosed space, the density of the vapour ar the particular temperarurc smd. pressure can he calculated,

Somewhat later Perot attempted to isolate a portion of the saturated .vapo~t and to weigh it. 'This could be very conveniently ~one. by ,1s~L:lGLng the. yapom l?I me.[t[IS ?.f ~ stop-c{.)ck. and. getting 1L absorbed m dry c.a~C1um chloride and we1ghmg the latter. K.. Onncs e~nplo}'ed another. 81111p~e ~ethod. In. a graduated. vacuous tube different masses 01 the liquid are introduced and the volumes of the vapour and. d~c liquid observed. Th11S if m and ml grams of the s.ubsC,<lI!c,e arc Introduced ,and the volumes occupied by the gas and the liq uid are VI 8 nd v~ m the first case, and v/, 'U2i in I he secon 1 case, and p ~, P 1 represent the densities at the ga~ and the liquid we

have '

(Hi)

Book Recommended.

L Gb~cbrook, A Dsctitmat« . .' of API*I~d Physics, Vol. 1 . J

01 Latent HC1t' ' nrttc e

CHAPTER VI

PRODUC'UON OF LOW 1EMPE,RA,TURES

1. lntr-odudion.- In the early days of the h~Wdy of1·1H;at: dll;rt' seems to have been a wid.espread belief that ~Ol Jng co~ c Ill: co ner dun ice, This point. was, therefore, dlm,en,lU aU .earher 5)'Su_"rn~ ~f temperature mcasorerncnt as the zero (~ta.rtmg pOHn) of the Scale. But.· Fahrenheit showed that if the mercury thermometer was placed in a mixture of ice and common salt the threac~ [It mercury .went. dO"ll-.'ll much lower. Fahrenheit chose the lowest pOInt reach~~ In iJ"11~ "way (-lSCC) as his zero, but w~ no:.' know that Fahrc~heltr ~ lerp· lS ~ot the lowest L€mpera turc ob raina ble. 'The 8;.ud y 0 f the laws 0 ~ perfect gases tells us th at we can, at least th[:l(J~etl can r' pro~ecd o~ :he. ct:'1:~ tigrade scale 273 deg"l'ees below th;e meltrng P?,m,t of ice and LI:at this i.~ the lowest temperature conceiva blc. ,!b IS 18 taken as the" :ze:r~ of the a.b8olute temperature scale. In ~lS c::haptL'T. we shall ~lS;llS:li the princi plcs and cnntri varices hy wlJlch the I'eticm {rom 0 C to a bsol u te zero can be reached.

PRINClPLES USED fN R"F.FRIGER...;<\ TION

2. F or teaching low temperatures we have to utilize processes by which a body can be deprived of iLS t,~)tal he,at content. The following methods may be employed to achieve t.111~ end :-

(i) By add i rig a sal ~ to ice,

(i I:) By boding a Iiquid 1;.1 ndcr reduced pr~ssl1 rc.

(iii) By the adiabatic t;xp.a.lIsion of a ga,~ doing external work. (iv) :By utilizing- tht:- cooling due to JOI.I.le-ThoffifoDn effect. ·(v) .u.y utilizing the cooling due to Pelner e-ffect,

(vi) By utilizing the heat, of ".dsorption, , .

(vii) By the prooes$ of adiabatic uemagnetlsauo-n,

A gell.€tal tl~eol.'Y of ~d:rigeration':Vm. be gi.ven later i~ Chap, IX; here we shan simply dISCUSS the principles and contrrvances for

uti U'ZI.I1g them,

(i) AnDING A SALT TO ICE

3. Low tempenttutes way be attained hyariding ~a .w..lt ~n iu!. This is the same ptoce"iS whicbwas employed by l'ahrenhe~L The came of this lowering of temperature is easily understood, Pieces of ice have generally some water adhering to them, and if salt be added to this ice, it is dissolved bv thee water and more ice melts. The necessary heat for rhls process, lJiz., the heat of solution and the latent heat required to melt the ice, is cxtracteu Irorn the mixture itself whose temperature consequently Ialls down.

12'6

PRODllGTWN OF LOw TEMPltlM .. TURES

This is the principle of jreeziug

20· f
1.5 C
.10 So,luti-Ol1

mixtures. This process, however, C"a11l10t go or:' indefinitely. Fig. I &b~ows the Iree:ung curve-a 0 b. tat n eel 'Wl Lh ammon i um chkmde, the ordinate representing ternpent ture in <.Ie and a bsciss.at'be con..:cnt1'.a lion 0 f the salt, 11\71*n the S1I It j s added to ice the ternperature of the m ixture dlanges as represe I) ted bv th e line Ail un die eutectic t.e-mperat.u1e of -15· ROC is reached, Tempera. tUH::S lower than chis cannot be obtained ill this way for wI1er; more salt is add~d it no longer goes into solution, The curve All represents eqtrilibrium between solu tion and ice while CB re presents cq LI i 1 i bri LIm between

TaMe l~FTe,e.t.ing Mixtures_

-_

(if) UOIT.n..;c ... LIQUID UNDER R.EDUCI!n PRE..';,sI)RE

~. ,Low tempt:ratun.:may also be attained hy allowin a li uid to bo~l under reduced pressure. 1Nben a li uid eva crates ft, ~. . heat lor eonversion from tbe liquid to' the q ase P (1 leqmre$, of V~ poti1.ation·) .. , Thus em e O1"anl' 'u','~ w' 'CM"~L °t uis '" Stlt~1cte .a t~n t afar

.. 1 ., . " _.f",. , J. a c I a u f'ef.pHre~ 5?9

ca on.e~ tOT completeevapor:won, If such. Iiquid be for' db.' ;) .. contrivance to ,evaporate rapidly and J·t the ,- .... id 1.. .ce,l }' some I ., I" d ! ,ll rlqlH ue m) ated this

!l~at_ ts supr ie <I'~ ~hl! cxncnsc of its '0" j h t· .: )

r.ool]l10" t. ... d l • '.'l! ea ron tent and rntense

, h may ne pro'! nee ,

Th~ o~ilest cont.rivance for lItilising this process - th ' phorus indicated in Fi<Y? The bulb f!' . - c ss IS e eryo-

l' ore ' ]. 1" lirruld !:j.~' , - ) conrains water or som~

voia uc .' HIUl and the! rest of the space is filled with the vapour

I

u]

127

Ii'rg-. l.-N l£CJ and water

Sy:.tOLl1.

salt and sclu tion 1In d B denotes the eutectic mixture with a fixed composi tion andfixcrl temperature.

In Table 1 the composition of the eutectic mixture and the cO~Tesponding eutectic or cryohydr] c tempera tures are g lven [or a. nt tuber of commoner salts, Gene. ra U Y ,h I'd rat ed salts are emp 10]'\.: d ~ nd ru tha t case th e correspondmg quantity o~ the hydrated salt .. shou Id be 0 b famed by calc ul a cion. These entecrir temperatures repre~el1L t h~ Iowest tern pcratu re Chat lS po .. ssible to au ... ain with rhar rree-.dng mixture.

",\.POUR CO>l.:H'ru:;SSlON MACHI,NJI.

of the same liquid. 'When A is immersed in ice tbe vapour in it COndenses and the pressure of the vapour in B becomes so much lowered that the liquid' in B bo ils, The latent heat necessary [0'1' thispuryos:e is ~tracted from. the res t of the liq uid ~.v Inch consequen t 11" freezes.

Now-a-days this principle is employed jn ;;I. large number of refrigerating machines both for 'industrial and domestic work. '"Vater, however, i~ not. a suitable liquid to use for though it bas a large Ia lent beat of evapor a tion, the

vapour pressur-e at low tempe-names Fig., 2.--The C:rYOphOil'11s.

is_ sr:1:llL The liquids commonly em~loycd al~e ammonia, sulphur dioxide, etc. Two types of such machines are m use :- (1) Vapour compression machines, (2) Vapour absorption machines, The vapoUl rompressicn machines are more efficient, particularly for large plants, and require less initial cost , consequently, their use is'more common th an tha c of the other. The only essen tial difference be tween these two types (1.£ machines COFJ.si~ (~ in rhe mariner of com pressing the low ptes£ll1'c '1apO~lr_ In the fanner fl. motor r.()~pn!s~ori~ used whil_~ l.n th.e latter it dilute aqw_'"OU5 solution at ordinary temperatures lS employed to dissolve the low prcssure vapour and the concentrated solution is heated in a gcnennor to expel the gas at high prer-sure. "Vc shall now describe these machines in greater detail.

5. Vapour Compression Macltine.- Fig. 3 shows the essential parts o [ aV:lpo'Ul' compression mf;l.(:h.in e _ There are three princi pal parts

.1'=2'5 atmes, ~~'" -1.0""'C,

=,-

v

Fig. 3_- Essential parts OJ a. VapO<l:lr Cornprcssjon Machine,

-t.he COmpressor P, the condenser C and the rdri3ctalur or- evaporater R- The cylinder of the compressor has two valves, Sand D,

I I I

\

I

I I

I'

I,:

II

I

1I,_

128

PROOUGTlON 01-' LOW "l'EMPERATURES

the former for the suction of the low pressure vapour born the evaporator and the lai:t.e~· for the ?'llch,.nge of the compressed V ",POU1' La the condenser. ''''hen the pISton. p moves upwards the pressure.: in the cylinder falls below the pres~ul"e in the evaporator and hence the low pressure vapOul' is sucked ill through S anti the suction pipe, During the dOliynW<lr.d stroke the vapour is. compressed and I:hen deli vered to the condenser C through the discharge vabve D and. the discharge pipe, 'The cond~nstt i5 cooled by cold wate~ circulating in the outer chamber. On account o~ the low tt,mperature and high. pre~urc the vapour Iiqueties in C. This liquid pas~e5 through the expansion valve or the regulating valve V which is simply a throttling valve to rt:duce the pre&sun~ of the liquid from the bigfl pre5sure prevai1in~ in the oondenser to the low prc:;sure in the evaporator. Due to tne low pres.~lITe the liquid boils thereby extracting Its latent heat from the cold storage space SllHollIlding the eval1utator" This space is cousequcntly cooled, In some cases the eV<I.pOT:::Itor is surrounded by brine water kept, in eirradation. The brine water thus becomes cooled and is taken elsewhere for n~fti'5erating pl1l'pO:!les- '1 be row pres;;mevap~ur Is sucked i.n by the earnpressor and the cycle 0'1' operomoOn S con trnues,

In the diagram anll),drous ammonia i~ supposed to be 'utilised as the refrigerant. The pressures and temperatures of ammonia m different pans of the apparatus are approximately :<IS indicated in dle

figure, .

. \ complete vapoUi' compression machine is shown in Fia. 4 which, however, utilises sulphur dioxide as the l'e[riJ:!;eraIlt. Vapou,r WIn )r.e~~ioll iuachines are now extensively employed in ice-makinz, in prescT\"ing- meat and other foodstuffs and for .. arious other indu~. tr; a] pmpu~es.

~. Refrigerallls.- Various liquids have been used as reh'i~rant8, the l mportam ones being' ammonia, sulphur dioxide, ethyl cliloride and methyl chloride. Of these amruonia is 111.05t commonly used in large refrigerating- pllWt~! while sulphur dioxide IS employed in ma.n)' household plants, There are various criteria {or selecting a suitable refrigerant: (1) The latent heat of the refrigerant should be Iarve

so that the minimum amount of liquid may produce the dc~i:rcd r-efrigerat.ing efre~t. (2) The Tefrfgemnt must be a vapour at ordinary L~mreraturc~ and pressures bat should be easily liquefied when co~ pressed and .cooJe~i. . ~ene.:mll'y a :-r::mp€Iature of about ,~'''F (some-what below Ice-point) H required In the ,evaporator- (011$ and about SW'F (~tbou~ room ternperatuF'::) in the condenser coils. (3) The pressure ofthe vapour of ther.e.fng-cm.nt In the eVl;I,po:rawr con must he grea ter than t he a tn~o5 phen~ pressure so that atmos pherf c i m puri ties may not be sucked mSlde and rater block the valves, lNith oooTing water at roor~I remperar.ure. surrounding the condenser the pres~nre l1ec~~sa:}' to lIquefy the gas in the condenser should not be too large otherwise the compressor and the cylinder will have to he made verv stout an.d consequently costly and there will be much le;lk21l{c of the vap(mr Into the atmosphere, (1-) The specific volume of the vapour

of the refrigerant should not b I "th··

'J1 b' e arge u erwrse a very huge compressor

WI., C neu~:;.sary. . ~ """~

The Important properties of f .

in T~L l' . ',.J." •. '. • s?rne ~()mIllOO re :ngeran ts are given

_ .~~, .Fl!?I~l uus table It rs evident that ammoni . 1,

m00C suitable rclrigeraut. One uund (, ., .. a LS tuc the same amount of refrigeration Pas 8.75 0 pO~~IJ:O~lt- ., t\~H PI',Od~lCe whl_le the pressure In the condenser in case of carbon d~~r ·cin .dlOLxlde G nines ~'l'eater than in the case I ' I xi e is a out

, ", ' .. ,_., "'- () . [1m mom D., 10 the t t of

specific volume, .h(nve-vcl', carbon dioxirle ., mil: er 0

Sulphur dioxide req uires a less Hout?:H.~ y1)Ssessc.~ an ad ~'a.rltage.

ammonia but for the same ref.ri;"""'ad~ m;Ert:ssor1. :--nJ. condenser than be made large. ' ~-. g c ect t ie compressor has to

Table 2,-CharaCle1'isti'cs or rei1ig(mmts*

) , .- -c~ "
1\ ) ~
VI.] REF1~HH!.Ri.NTS 129 'i

I

r SIJJrhm

-:-_----: !!_~___ di(tdd~

1. ]~,()iling point in --1---- -- -

OF at atm. presSun:

Carbon dioxide

Methyl chloride

F'reon eel.F.

14.0 I -W.o
1- H18.4 -21.7
175.0 111-,7 178.5 69.5 -28,0

~+ Latent heat of eva potation at 5 "F in .B.t.u. per

pound . . 565.0

~. Refrigeratlng

effect. in lU,u

per lb. 4·74.45

.

141.37 56.69

148.7 5.1.07

95.53 107.9

4. Vapour pressure

at 5°F in lb/in2., 34.27

5. 'Va pour pressure

at B6~F in Ib/in~ IG9,~

6. Speci Iic volume of vapour in

evaporator in'

cu. [to per 1 b, 8,1.'1U

7. Horse-power for a l'drigerachlg-

effect of 200

Kt.u. per mill. 0.99 0.09 l.B7 I 1,06 00.997

.. A l,mnbn of 11cW ~efril('ern1lts bay!'! be ; . . .

t"",enty years, AlT.lol1~ these 'ar~ F~ .' etll. nil ?ducctl dUTlllg; t11£: lr.st

LaTT~ne ( c;H,c,'") , tric h !oro-rlton~fltl~~~~m ~[b3 ~~.hl(o t}.~~lJ)o l'Ojll.le~111a1]e (C C I, F 0), .;thane (eel ro.) cte Of tht.;:Po Freon '" tl . _. n , (I~" oro-tt:tf3fiuonJ-

aecoisnt of the ',," ,{' 1 b. l~ OLLe most C:O<n1ll(111[y used. Fo .

(194.3-~4) publis!r:~fb;'·~.\;!l~:ic<i~!eS~ci~:~I~r~le·l~~l' sec tf~cfJE'iq~'r.atiJ1U DMa Ra~k

9 J • gera II 'f' LJ,gmeen, N {''W York.

11,.81 331,4

20.89 :26,51

6(;.45 1039,0

6.421 0.267

4.529 L-18

]30

PROIJUGI'ION" OF LOW TEMl'ERATtIRES

1'-". ]

AMMONL\. /l.13$(JRl'TION MACIUNE

131

This method may be employed to obtain €x~emdy_ l~ ternperatl"lTeS by ~5ing liquid hydrogen and helium .. ~ best liquIds ~'e allowed to boll under reduced pressure when temperature~ lower than

their normal boiling points are reached.

1. Eloctrl'C R,e-f~lgeriltor . .- Fig. 4 shows a m?dern electric reiri,ge:rrttJJr known as tbeFr:Lgldarre, working auto~H!.t~!cal~y on the vapour compression principle .. Here. liquid slIlp.hur .d101tlde 1S used as the refrigerant. The part above the dotted hoe IS the cold stmage spac;e.

v

it

I

....... ._, .... ~ ........ __ - - ...... _ ............ __ . __ .. ,. _ .. __ - __ - - - - - • - - - • ............ ".. .... "" .... _Ii:

Fig. +_-Frigidai:re,

The rdri~rator con R contains liquid sulphur dioxide which extracts heat Iro~") the surrounding ~pace a.nd evaporates and t!Je low l~Te:ssure VapQUT collects at the top, ThIS va.pQ1u conlmutu("'ltes ,",nth the

suction pipe S and the crank case R to the motor switch W. -\iVhen enough gas has colLected In UlC top of 11 it exert" a ,large prc:;s.llre which is transmitted through Sand. K thereby ope-mung the switch

"V. This starts the motor and the letter works the compressor P, as a result ol which, the low pressure vapour is sucked in through S to UH:: crank case 8 nd compressed by the piston <tlld delivered to the cundcnscr C. The condenser' it; cooled hy a current of air forced across it by the fan mounted on the motor !VI but in some cases the uJoOlin.g is brought about hy the flywheel itself 'livhose spokes are shaped H,Lt..: the blades or <I fan. The 111gh pressure sulphur dioxide vapour on bL"iug thus cooled liquefies and collects in the reservoir T. From Irere {!II account of the higb pr(!5~uu: the liquid is forced. up through the liquid pipe L and enters R through the needle-valve N. \,Vhen oenoLLgh liquid has collected 'in R the. float valve V rises and closes Ilw needle valve. Thus the machine works onlv when the !!;as pressure in R becomes large and liquid is rranslerred from the sturage tank T to R ou,ly when the quantity of llquld In R becomes Iess and the limit valve has sunk so as 10 open the needle valve :N".

8. Am.m.oniaAbs.orption Maclrilte.-I\.!; already stated the ab-

sorption machi ncs Jj ffer from ..

the vapour compression rnach i nes onl v in the manner of con'\o"enil1lg the low pressure vapour into high pressure vapoUl', Ammonia is the most suitable refrigerant for use in absorption rnad~l1es!<lod water is a very suitable absorber, Water at t~1J of absorbs about one thouill,a rid. times its volu me ot ammonia vapour but when Fig, 5_,-AmmollL"- Absorption M~11inc..

the aqua ammonia ~olut]on is heated to 80QF ammonia Yllpour fr~ely escapes rrom the. solution.

The vw~:ing ?f Jan ammonia absorption machine wnI be ,casily u ndeI'stoo(~ from ,F[g'" 5. The w:nerawr A contains a strong solution .,1 ammoma gas m l¢ater and IS heated bv a burner a~ shown in the Ji~m'e or by means of pipes carrying steani, Ammonia rTa5i~ expelled lrunl the solution and passt$ into the coils immer~e~ in the. COIl:.It-''~t:r n through whi~Jl cold water C()~tinLlf!ml" fi01NS,. The ga. .. i ,~ II! I ~eml.:'Ji the~e u n de:~- 1 L& Own pre_~~u re ] n to 1 !qu id s m m on ia. The .III[ ~ rI dam lTl'?ma .thus form ed passes ~hml1gh a 11 arr-ow regu Iarin g ,,::I, Ivc V III lilt: spiral Irn.mer.~ed in the refrigerator C, where on account 01: r he rilW. pre~s:ll:e rt evaporates. The valve is adjusted to maintain I rw dnlf('d riLA'erence of pressure on the two sicks. Through the I ~'I n~~~1 :1 tor ~[Ow.s a stream of brine water which becomes cooled by the I:\'~lpr)r:tf[on 01 ammonia. The cool brine colution mal' be taken

to ,U1Y ,.I[;U'C for. rer:r~gerating purposes .. ,. , .

1 he amrnorna gas formed Inthe coils in C IS absorbed bv water or dilute ammonia solution contained in the absorber 0 and thus i lit: ,~n'&.mre is kept. Iow, The solution in D becomes concentrated .Illtl is transferred by the pump P to the gen€rator at the top. Thus

I"

; J

,

,

II

, II

Ii

I,

I'

132

PR.ODUCrION OF LOW T"M[,EllA"fllRIL.~

the supply of concentrated ammonia solution is kept up. Dilute ammonia from the: bottom o.f the gen~rHor 111ay be runro the absorher and concentrated. TIlU~ the cycle is repeated and the action is quite continuous.

The difficulties of d:I~~ mach.ine arc !h(lt it has a r~w efiic,iency and the pressures are wIdely diffcrem an the condenser and (.he eVi!pOralOr. The low efficiergr.y is due to the circumstance tha t the heat absorbed by the ammonia in the 6TCneratOl" is 11l uch " Jarg~r than the heat absorbed hy it in the evapmator coils. Further the machine has a moving part in the pump needed to transfer 'tl~c liquid to the generator, and is costly. All these ditnmhies are avoided in a clever invention by two Swedish engiIleen, von Platen ami Munters, which is placed in the market under the name Electrclux Refrigerator. In this Dalton's law of partial pressures is used to make the total pre~ure in the condenser and the evaporator equal, maintaining at the same time a difference in partial pres~ures of ammonia in the two chambers; (his [5 accomplisfied h}' using an inert g:a~ like hydrogen at a pres:mJ'c uf 9 atmos., the partial pressure of ammonia being;) atmos, in we evaporator and the absorber, and ammonia Iiquefies in the condenser at the pl"essure of 12 armos .. Con('entrat{:n ammonia solution .is fnrcerl up intu the generator Ly heat and not by a pump.

(iii) t\mt\Ri\TIG f;'.xl'IlNS!OX 01' CO~1l'lU,SSY,:]) GASES

9. Cooling prodll.ced b) the lIudden adiabatic Expansion of compressed gas-es.-If !l highl) compressed gas be sml.denly allowed to expand adiaharicallv, it cools very considerablv on account of the latgt:: external work it docs in expanding, vide § 2!;1, Chap. n wln:l'~ it is shown that T' -= 'J.' Ui /p) '}'- IJ/~. The cooling may be so gr(~al. that the ga.~ may even sclidily .. ,

AI1 example which is easily available In a big town i~ afforded by cylinders containing carbon dioxide. If such a cvlinder be suddenly. ore~ed and a piece o_f doth held belore it, the 1s~nil1g gas is deposited m the form oE solid CO2 (called dry ice commercially) .

_!~js principle was utilised by Cailktet who first liquefied oxygen 111 18'1/. UP. compressed oxygen to a pre~ure or 300 atmospheres in a ~tTong capillary Lube cooled to - 2~lDC by liquid sulph LIt dioxide boiling '~nder l"e.du~ed _pressure and then sudd~~nly ~elea~etl the .pres~Ul"e_ ~ mrst or. liquid ox]'geTi was formed WhICh disappeared In a few seconds. P fete1:. cum pre~se-d. oxygen to a pressure of 500 atrn, an d coo Ted it to abou e - 12(J°C by. Iiqtdd carbon dioxide evaporating under redu ced pH:'S~Uf"e. Then he so dden 1 y relea sed the pressure. OKyge t1 in the form of a white solidwas thereby obtained. In ~ RR4 vVrobJei(\'sk.i. obtained ~ mist _ of hydTOge~ :while in 1~93 Olszewski obtained liquid l~} cTf~ogen III ~Uffi·CH:l1t quan trues. by coollna compressed hydrogen with liquid oxygen and then mt!denly rdeasing the pressure. Simon in 193~ pmdilce.d appreciable quaIl titles of liquid helium by sudden adiabal:1C expansion of the c~)mpreflsed gas which hall been precooled by solid hydrogen cvaporatmg at reduced pressure.

\11.]

LlQ_UEFACI10N OF GASES

The process is, however, essentiallv discontinuous, bcn~e for coinmercial pUTpOSe.~ it was almost dis~:;ll:d.cd; but :'l novel '1.1 ay of utilizing' the prjnciple has been invented by Claude and Hevlandt [or liquefying air {see sec. 22),

"Ve have d escribed above two types of Tefrigerating machines.

Then: j s ;:J 1 hird type also which is som etimes e m ployed, This rna]' be {::;!tied the '-'11' compresslon machine because air is here used :;[8 the refrigeran t. In this air is first compressscd in a cOlnpressor, the beat of cOIIJpression. is thcp removed oy 'pa~singthe gas through coils kept r.oul by' cold CIrculating water. Tins coo] compressed air then sufiers adiabatic expansion in the expansion cylinder and becomes consider:I.bJy cooled. This cold air_ then traverses the cold storage space and !hu$ g~cs heated and JS agarn compressed. Thu~ the cyd.e continues. "rlm IS t.he. pnn~lple of the Bell-Coleman refr~gera~r largely used f.or the rdngerauon of cold storage chambers In ships,

(iv) COOI.J.NG DUE TO PELTIER EFFECT

Ill. I t is well known that when an de ctric curren t f[m~s in a circuit front bismuth to antimony through a juuctiun,chis junction is cooled. This is known as the Peltier effect and may be utilized in p;uduci?g co.oIing. This cooliug is rather 8m.all though semo,-c-ondu.ctor therrno-juncrions have recently produced much more cooling; and have been employed in some refrigerators,

(:0) COOLING BY ] QULI£·THOMs.fJN EXPANSION

This method is of considerable importance and will be con-

in det a il J ater in this cha ptcr. .

i

I

11. sidered

,J

(vi) COOT...JN(~ HUE, TO DESOlU'TION

I? Charcoal adsorbs anum bel' of gases w hi ch are released un ~Ol;"Cl'1ng the pre-~sun.:> and 'when these ga.';e~ 'escape. a cooling results ~11 ~ m~mller 50mewhat~nalogm.~s to the case of evaporation of liquids.

~]1JS IS called the 'Desorption method" and was utilised bv Slrnon. In an experiment charcoal adsorbed helium gas at 5 atm_ and lOOK and subsequent desorption to 0.1 mm .. pre"5t;Lire lowered the wmperaLure to 4°K which is :sufficient to liquefy helium.

LIQUEFACTION OF GASES

13. Liquefaction by :lpplkafiol:l of pressure ao.d low temperature.'iUII~(:jll~'~, whkh. ,u.e g<l8e~ at o.rdinary temperatures may be , "II \'t'111:~ 1 to the liquid state H1bey are sufficiently cooled, and simul~'.'I~[·'lLl~.I~· a Ltrge: pressure be applied to the mass, 'Vhen pressure I~ .tpplit·.d the molecules come closer together and if heat motion he ~IIHII ,H'II~lv small, they may coalesce and form a liquid mass, ~ r. 11](· III I Lilt! so cooled be allowed further to evaporate rapidlv, ~,l Ii I . rOl.\'~·r Il'nD]Ter(l iures m,lI~ be ol~ta~ned.,. The production of ( xtrr rur 'y low temperatures H; thus intimatelv connected wlth the 1'1"1 ,bl{ m of J iq uelacrion of such gases which. ordinarily show themselves to he ",err rdr::JCLOl'Y.

1.1

PRODl:C1'ION O~ LOW T.IlMI'ERl\,TURF.S

The earliest scientist to try this effect of combined cooling and comprelision was Faraday" who, as early as 18~3. employed, the

11. pparatus s h own III Fl ~_ 6 for lique] yl n g eh loan e. One end DE rh'e bent gla~s tu be con tains th~ su bsra 0 ce {rom which chlorine is liberated by heat while the o ther en d is immersed ln a free:dl:1<Y mixture. Ga,~eous

'" • I

dllodne collec[.s. In. tue

other end and finally liqueties under its own ·pres'iure. By applying this proc'es~ Faraday and others ~t1Creeded in liquefying a large number DE ga.sc~ but some uiz., ox.ygen, 11 itrogeu, hrdrogrt-n, carbcn monoxide

Fig_ 6,-Fa!1lday'~ Apparatus £01' Liqcefacticn

. of Chlorine. and methane baffled all at-

temp ts a l liq u efaction,

though sometimes enormous pressures up to 30-0(} atm. were used. They were, therefore, termed permanent ga:>e~,

Discovery or the Csitical l'oint.-'fhe cause of. t,hcse failures' beLame apparent wIth Andrews' discovery of the cnt~cal ~enlpl:ra'LUr(l in 18(HL 'I his suhject has already been treaLe~ in Chapter lV. Andrews' e;li:pfrimenu first clearly showed the unportauce o( the critical p.hcnomena, "!"hcy.estaLlished. clearly that f~~' c\'ej'ysubH.~m[e. which usually ()cUlT"S III the gaS(iOltS Iorm, ih~rc exists a temperature above which i l cann (It be llq uefie_d. however hIgh, rna y b.c the pres5u~,e L.O which it i.s ~ulJlt!~ted Hence, in order to liq Ltd)' 11 gas by this method it must be pre-cooled below its critical temperature-

The determination of the critical point (p. 100) is not, however, easy, The early workers did not i~1 fact, wait [or its deter-' mination. Tbey cooled the gases b)' ordinarymethods as much as they could, and then applied high pr{:s.mres.

14. -.r:h~ pl'incipaI.met,hod~ of liquefying-ail' _and o!.h.er gases~e the foUowln<T:- (1) Pictet s cascade method ,\",Thl~h utilises a series of liquids WftJl successively lower boiHn~ points but the p,rlnciple is the same as explained above; (2) the Lincle and Hampson s methods ew.ploylng. t~1e J o~J~e.Thorns-ol: effect :_ (~) the Claude and Heylar;dt methods which utilise rlre coolmg produced when a gas expands doing

* Michael Faraday (1791-1867), the "prince of experimenters," 1.~S born of httmble par~ts in London. At the :;rge. of thirteen he became er"l"anJ boy to a booksdler bUL later ill un.:) he got employment under Sir Humphrey Dill>'"}" at the Royal ItLslitl.ltiOll where be. carried on hI!> !>cientific work and £i.naIl}" st1.CC"el!ii(:d niH'), in 1$27 "-s Director of the ko)'al Il1Stltlltiol1, His greatest work L~ the discovery o~ eleetrornagn etLC i~duction in 1 &31.

VI·l

135

S,ERIES kl!:FRIGERATION

exte:nal W(Wk. W~ ~hall. DO~ e<?nsitlcr these methods in greater detail. OE tht:se the first IS historically the oldest and them-eti ~allr' the mast efficient hut i~ somewhar cumbersome and is verv little used

at 'pre5e~ It. ' .

15. The Prmdp]e ofClIISca,des 00" Series RefrlgeraHon.- The me thod was ~r~t employed by R. Pictct in 1878. In principle it may be described as a number of compression machines in series, Pictet employed machines containing sulphur dioxide and carbon dioxide aud obtained temporarily a jet of liquid oxygen b)' allowing COI1lpH:~5Cd oxygen to expand adiabatically. Wroblewski. and Olszewski at Cracow obtained sufficient quantities of liquid oxygen, nitrogen and carbon monoxide by the cascade method and determined their proFenie~. _Olszewski used ethylene as another intermediary belO¥\T carbon dioxide and could thereby cool these ga.~e~ below their critical temperature. Kamerliugh Onnes later' employed the eombination of rnttI:y! chloride. al~d .ethylene tOT liquefying oxygen,. The prinel pre 01 the ,method ~li dlwitrawrj in Fig_ 1. Machine {l) urilizes methyl c.h~Hnd!e. This has got a critical temperature olE 113"C and h~'t'ic~ ~t room tem.r~m~ure it GlTI he easily liqttefied by the pr~essur'e of a few lltmosphere5 only, Water at room temperature Ilows In the

F.L~. 7.-rtlllstratio.tt of the Method of Cascades,

j:'1(' kct in (1). Liq u i d C~ ~C1 falls lll!0 the jacket in (2) which 1S (~m'~(~ned to the suction side of the L-ot,ppre5.lioion pump. Thus the Ii q LU d eV;J po~'ates under reduced pressure and its temperature fallstc about i- 9f~Qq_ T~1e compres1>OT l';etums compressed CH~CI gas duough the tube m51de jacket (I}, WhH:b. is shown straight but is really ~H ~ her 0]"01 of spirals.

l nsirle the jacket (2) is placed the condenser coil through which ethvlene passes from ~ll!e compressor 0,[" ~le gas cylinder, h. liquefies and then enters the jacket (3). There It evaporates under reduced

L%

[CHAP,

j' lWDUC nON 01i' LOW 'rE~1:PERA TURES

pressure and lowers the temperature to abo~t - 160"C.. Throy.gb t~lt: tube inside j:H:ket (3) oxygen from a cylinder pa.s~es and Iiqnefics under prcsnllc, Llquiil oxygen f~ collecred ill the Dewar J1:1~k D. The lowest temper,Llure obtained by hoiliIlg oxygen under reduced presmrc is - 213°(; which is higher than the _C1"itiLal temperatures of neon (- 228.7), hydrogen (- 240~C) and. helium, hence the method of cascades failed to liquefy these three gases.

The method of cascades is VeTY useful for laboratory purposes.

The usc of the compressor can be entirely dispensed with by the use of suitable liquids boiling' under atmospheric or redu~ed t:n~ssu~e, 'The auitable liquids can he selected I rom Table 3 Wh,ICh gl!/_t:~ the normal boiling point, the critical remperature and t~~ triple pomt (or the common gases. The interval between the critical temperature and the triple point represents the range in :which th~ Iiquld is av~ilable, Still lower temperatures ran be obtained by further reducing the pressure over the liquid when it solidifies. Tbu.~,. ~sf;rg solid nitrugen and. a good pllmp 11 _temperature ol about - ~24 C can. b.e obt:aim:d 'which i.~ still above the critical temperature of neon and jt h no t possi ble to bri dge t~ c ga:ps be ~ween nitrogen and II can an d between h ydwgp.n and he! rum m this way.

Table i,-Critical temperature, normal boill~ng point alul triple poin.t of gases

Substance

I Critical tern- I Triple point

""?". _1 _

R P_ at 1 atm.

pres..~u:r~

Methyl chloride - 24.0WC 14J:l.3"C - lO2.9"C,
SuI ph ur dioxide -10,1 157
Ammonia -:B$.5 131.9 -77.7
Carbon dioxide - '78,(1 3I.O -56,{}
N i tric oxide . ~9.8 36,50 -102.3
Ethylene - lO3:7i! +9.~O - Hl9
Methane -]51.37 -82,85 -183.15
Carbon monoxide -190-0 -138,7
Oxygen -182.95 -T lR.R2 - 2]8.4
Nitrogen -19.5_78 -147.13 -209.86
Ncou -2-t:t-92 - 228,71 -248,67
Hydrogen -~.'2.7fi - 239.91 - 259,14-
Helium - 258.83 - 267.84 16.Prodt!ldioD of tow Temperatures by utilizing the J~1l1e.ThQ1ll:mtl Effect.- A~ the above method is not capable o] Hquclvine hydrog-e:n and helium. another procer.s beg·;mto he utilired from 1 S98_ l}liS is the Joule-- 'Thomson effect discovered in 18!i2. A fulllll<uhcmat1tal

,"'I. ]

THEORY OF POROUS I'LU(; EXPE.RDu;:Iir

137

"

analysis of the phenomenon is postponed to Chapter X. V\7e shall

describe the pbenomenon here, . _ . .

'"Va have alreadv described [oule's expcnment (p- 4't) which showed, that for pen!ianent g-<lses th~ internal energy does not depend

upon volume, .1. e .. ( ~:) T = o. This is called ] au h:~'s ] aw or Mayer's hypo t hes! S a nd is the characteristic property (l f a perfect gas (Eor pcifect monatomic gases U = iNh T per mol.), But t~lis, is not. li(rict.ly true for the actual gases of nature ; they all show deviations from the state of perfectness and hence Ior them U is not independent of volume. A !di'Thr change ill the temperature of the gas should occur

. iI; J.ouh:'s ~~[Jc~imcllt, but since the capacity f()~ heat of the conl.aj~cJ air is neghglblc as compared to the heat capaCIty oE the surrounding water, no change in tet!lperaturc could be observed. In UI52 Lord. Kelvi~i, in C{!llabo~'ation with Joule, devis.ed a modi[~C<l,1;ion or J(lUle's expenment In which very small changes III temperature produced by expan"sion could be ea~iJy measured,. :.rhis is called the '~,P()rous plu~" experl~.eM and prov!(l~s annn£iulmg test of ~:!ayer ~bYrothe~ts, "llfnll Its help we can t:$l$lIy find how far a ga~ deviates from the state of b~i ng per feet. Before procecdi n~ to describe ih is ex. P erimen t we shal I discuss lh P. theory under! ring 1 L

17. Elementary Theory i!If the PlilrOlJ! Plug Experimenl:.- In th[~ experiment a highly compressed gas is being continuously forced at a constant pressure through a constricted nozzle or porous plug. The plug, as its name implies, consists simply of a porous material, say, cotton·w~ol, silk, etc. having a number of ,fiue ~oles or pore~ and '5 thus eqnivalcnt to a number of narrow orifices in parallel. nH~!0S during in passage through the pores becomes throttled or wire-drawn, viz" molecules of the ga.~ are drawn further apart from one another doing irlt.::rn,aJ ,vork against molecular attractions. This is al\\I,:'ays the case whenever- a fluid has to e~tape through a partly obstructed passage. 00 11 el t11 er side of til e p1 L~g constan t rre~ ute~ are rna in ).ain ell, the pressul'e on the side from wh lch the gas flows helllg much grr::a~eT than on the other side since the plug orters great resistance to the How of the g-as. This expansion is of a character essentially ditferent from Joule's expansion. In Joule expansion, the gas expanded without doing any external work. Here it expands against a constant external pressure and hence it has to do extemal IIJml~ <1.1$0, together with any internal work, while some work is done on the gas as well. The plug is surrounded by a non-conducting jacket so that t.he pl'ocess i~ ad.iaLatic iu the sense: that no"--nqc enters Dr leaves the system. For such 'processes we now proceed to sli'ol;;o that the total heat Iunction h = u + pv remains constant.

To prove this theorem, let us consider a mass of the fluid traversing the porous plug C [rom left to light as indicated in r:;g. S, Le.:t p!'., IJ~, T~. 11.\ and FE) lIB' TEl' Ill! be the pre~~urc, volume, temperamre and internal energy of nne gram of the fluid before and after traversing the orifice respectively, SUPPO$C that One granl of

(1

,~ l

I

138

PROI)(.1GTlON uP Ww T!':MPERATURES

(CHA!.>.

the gas IS contained between {he porous plug and some point M On the left and also between the plug- and some point N on the right- For visualising thepeocess w:- rna}' assum e a bl i t?~ ginar)' piston A 11 r M separa ung this q uan tit)' of th e gas" and that th e How of the gas is caused by the Iorward motion of the piston A. Actually, however, the rest of the gas exerts a pressure PA at M which is maintained by the source of !,upply_ The gas after traversing the plug pushes forward the imaginary piston B whose motion is opposed by th e pressu re t of the gas to the right of B. The in 1 rial it I"! d final stat es arc show u r,e~pectivery at (a) and (b) in the f:i gure, the ini tia 1 \101 ume of the .gas be ing equal to l\.-IL and the final volume equal to 0 N.

The gas during' its Jlassage through the orifices .in the plug has to m:eroome friction, viscosity, erc., and hence loses energy. The E5caping gas issues in the form of eddies and its temperature !alb considerably just at the [ei (and this effect is spurious) because some th~f'mal t:neTg)· is now converted (0 the energy of mass motion. The eddies, hO·WCytT, subside alter traversing a short distance and the temperature- consequently rises, Let us consider only the steady How before and after transmission through the orifice, i.e., at points l'ar removed lrorn the plug where eddies are not present. \Ve assume that the ga~ moves VCTY slowly so that the energy of mass motion is n:ry small and negligihle in comparison to the energy of thermal m ori ons, Now our ini ti al system is ML and the final system is 0 N . But the plug OL is initially and finallv in the same state; hen ce the change simply consists in a chanse 'from MO to I.N. Hin addition, the tube is surrounded by ~i non-conducting mateda!, no heat is supplied LO or withdrawn from the system. Some work Is, however, don: by t.he, external forces on the slowly moving system, The: force actlng- at A IS equal to 7h X ,5: where S is the cross-sectional area. or the cylinder. The work done by this force upon the "as. is PA';-f.. S X M? = P,~1JJI' ~imi11l:dy, the work done hy the gas in forcing the piston B IS PDIJD. Therefore, the network done by the gas is

PB<JB - fiJI., ~J!.! and from the first lllw :oI thermodynamlcs, since (\ C? = 0, We work ~one by the ... ystoem 1$ equal to the decrease in Hs In ternal energy, VIZ,.

'B

Ii'ig. 3,-- 'The PI1l"<J11S Plug Experiment,

V"A -U"l!J-PB7iJP;-PAYA

or uA +PAVA = u·E+PBvn

Hence 1t + tlV remains constant in the t.hlotdilJlg process.

(1) (2)

For pErfect gases Boylc'!; law -(pv) T' _:: ronstant and JOllle's law tel = cT hold true, and iheretore u+pv would depend upon temper,,:

Lure only. 'We have just shown that u,+pv fO: _the porous p]u~ expe:~I; ment i~ constant ~"r he rher the gas IS, per{~ ct or not. Hence, f __ per feet gases the tempera iure on b?th ~ld~ S of the plug .•. "'?li.l; d ,tCm~rU1 the same" In actual e'Xpenrn,ents, however, :l cooling e~cct "I. as observed [or most gases such as air, 002, N~, C~2 and a heating effect 'e of H. T hus nO']C of the g.ase.~ exa mInr2d was perlecr. The

III cas .~. . " . 1'· e.: Boyle's

lack of pedeCLnes" may be due. either to (eVHIUOn~ nom ~ . .

hi. w or from J oulc' s ill:" or ~mh, ~ Hwe. know the ionrner: as from. Amagat's e~"'.rernnents lp. 91)wc can find the .. laue! by performing the pOI'Ous. plug expenm~nt.. !f at, the." tn .. rticular pressure and temperature In A, the gas l~ IDmecompn.:s.slbJe t~1an at lower pressures f cf. curves of N~, ~O_~ before the be~d (p. ~~) ].

P . <p v Therefore. due to deviations El"Om Boyle slaw alone

<1,.1)'11. H n- , . .,' if' If 1 "

flB < 11", i.e. the gas would. show a co01111g effect, . .• t 1(: gas is

less comp"f.t:ssible (ct., H2) there "."'ou~d. be a h€atmg e~fe~t. U~on

these cffect~ will he superpnsed, the eile.ct due to deviation h cm~, joule's Jaw. Since i~ actual g:a~e~, _ cohe~ni~ !orces are J)resent,w:Jrr~ will be done in drawing the nioleculcs further apar l d:u.~lng eXpil.ll~lOn and the g<Ui would become cooled- Thus .the Joule-I ~~)ln.~on _ effect due to this cau se WCJ uld ai wa ys be a (."'0 I) 11 Ll!:\" effect. J he 0 b_served effect is the resultant oE these two. effects and m~)' be a heating or cooling effect d.ependi·.og upon the sign and magl1ltude of the former

effect,

18. Tlte Perous Plug El;periment.- "\l,e shall now describe an actual experiment. joukt and T~om~n

were the first to carry ou t these ex perlI~el'l t>

They em. pluyed a cy li n dri cal pl ug, w hi ch 1~

indicated in. J'ig. 9. T'h~ c?[(lpr.e~i;E:d. gas flows through a copper spiral immersed Ul_ a thermos La t and after ha vm.ng seq u ired Jt3 temperawT'c., passes. rlll'oug-~ the porous plu[{ ·""'V. The plug consists ~E SIlk, or ~a()n.:,~'.ool or other porous rnaterial, kept m pOSItIOn between two pieces of wire.gauze fI.Il~ enclosed ill a cvlinder of some llon-condllctlng wood b'~. The p]U& and part ?f th~ tu b~ is st:rrouurled by asbestos contained in a tm cylinder zz so that no heat reaches it Irom the hath. Joule a nd Thomson worked with aJr: '~~' 1\ 2. CO~ between 4cflnd IOOQC, we initial and final pr~SlDre~, being 1..1') atnlo8Rheres and 1

atmosphere respe,ctiveiy- ~,

vr.]

Ttll!. .POROL'S PLUG l'_"U'ER]MENT

l39

, ,

Fig. 9.- ;'couk."- Tilml1- SQl\'S porous plug_

140

PRODUCTION <)l' l .. OW "fEMPER..4,:nm.E~

l QlAl'.

Some of the subsequent workers employed a plug of the "axial flow" type as used hy Joule and Thomson, while some others employed. a plug of the "radial tlow" type, In the: latter the gas flowed from the outer side of a hollow cylindrical plug to the Interior and hence heat insulation was better. Certain others employed only a threttle val ve or a rcstr icted 0'1"1 lice.

From theseexperiments Joule and Thomson foun~ (bat the fall in temperature was proportional to the difference in pl'es.sure on the two sides of the plug, i.e.; 8fJ=k(jJA - P"ll), where k i~ 11 constant, .-;harac,ttristic of the nu~d, They found empirically that k =- AlP where T is the absolute temperature of the gas, while Ross-Innes found It = A + B/T. Hoxton, however, found that his results were best represented by the formula

B Cp k=.4+T+T~

(3)

'Hie com find a value of k from theoretical considerarions (see C 11 a p. X).. If the ga~ be supposed to obey van d er 'Vaals' equ1t lion . of state, It can be shown that the '[oule- Thomson effect

6.8 1 (2a )

!::,_f} =CI'R.T-h appmx. (4)

Exercise [~Using the values of a -=.:: 1· 3(i X 106 atm. c.m4 and b=« ~2' U c.c, for a wa.m-moh~nlk of uxygen at N .T.lt-'. and Cp = 7·03 (";11, per mol., calculate the joule ... Thomson effect from equation (1).

/'. f} T [2 X 1·36x TOGy 1·01 X JOII 1

ll/J =7.03 X 4· W X 107 e·} x 107 x 273 -32·0 j

iJ. (I BY deg,

6.p 7.03 x 4.13 x 107 dyne!crn~ Wix 1·01 x lOt. -7,03 x 4.11j:x 101 = 0·31

dcg;. atrn./cm"2

Exercise 2. Calculate for a van dcr \Vaals' 1fd~ the cooling produced ill rhc joule-Thomson process.

Internal work done bv the gas = r V~ !! dV =~_ "

, .I Vi V2 VI V2 •

., Net work (external + Internalj done by the gas

=h.V2-PIV1+J~- -;-

1 2

R'T 'T '+b{ } 2·t~ 2a

= \.' ~- 11 P~-h +v-:;:---V~'

since [rom va~l der Waals' equation pV = RT + up - {a/f!) approx,

for the .twa. SIdes of the plu1§' '

~hlS WIll produce a coolll1g by -6,0 (since .6.0 =-= O} such (,hat

(see Chap, X .. sec. 10) ~ .

-c, 6.@==R(T"? T,)+')(j)~-Pl)+ 2a _ '2;-

V, f2

VL]

PR.JKCIf'LE OF itF.GENF.RA'fIV.E COOL.INt,

141

or

i::ombining lh:i~ with the relation G ~ - C. = R, 1,..,(.; get equation (4).

19. PriDcipl.e of Reg€oeraliVll COOHiig.-Th.e Joule-'.I. ~omson cooling observ ed lot most ~ases is very small. Thus, Ior a~t at a. te]?~ reraturt: of 2WG when the pl'e%L:r-E::~ on tllc two .• sides arc ~(I a nnospheres and I atrnos phere 1"t3 ~~ct.ivl:l t. J ou le and 1. hOmS01? ,t QUoll (~ that 1 he rernperature fal,ls by 11· ( C ... He~lce the ,method ~:¢dd rIO, be employed lor a. !ong time for producHlq llquefa~t1~n. SL1b.~equ~I.1t~: . however, it was UlscovcTed that the coohu-S" ,e!Iect can he H1te~~IlLd by etJlploying what. is called the re$cnemtnJe pl"oce~ss. A portlOii ~f the gas 1;.,,11ic11 first suffers Joule-") 1l~l1l~on eKpa_nslOfi. and beC~~l1c~ cooled 15 employed. to cool other POl:UOm; ?f the incommg ga..s before the latter reaches (he nozzle. The mcormng g-as becomes ~tlI1 more cooled after traversing the nozzle. In this "'?Y. the cooling err_~c.t can be made cumulative. In actual practJ.ce. thls is secured by usmg either eoncenrric rubes as in binde's process or by means of Har:upson spirals (~ec" 21). T'~:o or more eoncentrlc t.ub~s arc. ~rra,ng:~d 11l ,~.hc form of spirals, the: inner one carrying the high-pi eSSUl e mHov; mg gas while the outer- one the low-pressure outflowing ga~. In the reeeI'lcnLtive method a Iurther advantage is 0 gained by the ~act WHIt .the lower the temperature the greater is the jouleThomson cooling.

The regenerative principle is illustrated diagrammaLically in Fig. 10 where the high-pres~ut~. gas {w~ t11e. compressor enters ihe spirals con tamed in the watercooled jackel~. The gas next ente~~ the 1:"(~genel'ator coils at E and. hy expansmn at th.ey"l ve C h ccomes cooled by a small amoun t, Th i ~ retu rns hy the oil ter tu he abstracting heat' from the high pres~m:c gas, and reaches 1" almost at the sa-tnt: temperature <18 the incoming ~as at ~E. The gas is again compressed and cooled by A and re-enters at E. As time passcs, the gas approa~hi.l1~ C becomes cooled m?n: and mute 1111 !fIC .Joule- Thomson cooling Fig. 10.-JHll~tralioll of the

Regenerative Cowin.c:, at C is sufficient to liquefy jt uiz., its

temperature reaches the value at whIch .. . .

the gaswouI~l liquefy under th~ prcs~;tre. prevailing at F~ A poruon 01" the escaping ga;;; then condenses inside the Dewar llask D. At this stage. the t.emperatm:c throughout me appa~~LUs hecomes steady and may be represented hy the curve Shm.HI 10 I'ig. 11. p. ] +2" The part LM reprcsents the continuous decrease of temperJ.~ure of thS gas as we approach the nozzle through the Inner tube while J<..fN n:preseuts the .Joule-Thomson .cool.in?"·, NL {eprcsents the ~emperat.uTe of the Iow-pressure gas which ]s ress than that of the adjacent high-

it js. th€:1.1 cooled by passage ihrough water-cooled tubes ~nd is deUvel'td to the suction side of the second stage compressor. '1 he compressed gas. th en pa~~.5 lhrough tl?e. ~y l.i n ~ler f. w,bich con t a in s cain tic, so~a. Th]3 absorbs the carbon dioxide (][ this is not done, carbon dioxide -will become solidified. and cho. ke. th. e valves in the liquel:;er proper). The gas then passes to the tubes g which are coo-lea by a beez.ing lDixmre to ~20ac. From here it passes on through the m£taHic tubes p~ to the inner coils of the Iiq uefier pto~er. At awe have got the plug which is a throttle valve operated by the handle T. As the gar> expands (in the first staflC to 20 airn.) , the temperaiure falls [,0 about _7BaC, and the air agam passe~ through the outer coils cooling the incoming g-as; it is then led through the pipe P1 to the secoLld stage coD1pression cylinder, where it is again compressed and allov,red to pass through the refrigerator and the inner coils to a, After the completion of a few cycJe~ the temperature of the incoming gas falls 80 10'1"1 that the second throttle valve is opened. The air is now allowed to expand to 1 atmosphere when it becomes liquid and collects in the Dev .. ar flask. from which it can be removed hy the siphon h, The unliqueficd gas is ~gain led back through the outermost coils to the compressor e as incliG:lted hy the arrows, Fresh charge of aLl' is be'ing continuousky taken in (It .~, compressed and delivered: along witb the ga~ from the midd.le tube to d. The process is cyclic.

21. Hampsan's Airr Liquefier. This liquefier' also utilizes the Joule-Thomson eIft:c.t and the regenerative principle, but differs from Linde's apparatlls in details of construction. The special feature about it is the Hampson ~piraL The high pressure inflowing gas passc~ thrvug'h cappel' tubes coiled in rhe Iorm of concentrlc spirals arr::lngcd in lavers: it. then suffers the throttle expan~ion and becomes coo~ed. This cooled mil' )"lYElS' through the Interstices between the hyen of spiral and thereby cools the incoming high-pressure ga5" After some time the hi.gh-luessurr:: gas becomes sufficiently cooled $(I that onsllD'ering the throttle. expansion, it liquefLe.s, The app:amtus thus differs from tbat of Linde only in the rnanner of cooling- the incoming gas. The appar:atus was later impro\I'ed bv Olszewski. The Hampson construetion has been utilized later Ly Dewar, Ormes and Meissner for li<iuefying hydrogen (see Fig. 14) and helium.

2:2. Claude's:Air Liqueli.€r.-Ahhough the Linde and Hampson li<'.I.t1eflcrs just described are in exLensive use in laboratories and (:0[[1- mere ial i u 5 La 11 a ti ons, the ma chines canna t he said to he saris r actorv, mainly because the efficiency of the machine, i"e.~ heat extractedj €uergy consumed by the machine, is extremely low (about 15%}. The cooling pro,cess ·eruplo}'ing Joule-Thormon expansion is really very inefficient. A more efficIC'Ht machine could be devised if the compressed ga.~ was made to expand adiabaticall'y doinl": ex terria] work and thereby suffered cooling. The technical dilliculties in constructing an apparatus lor cominuous liquelactiorl of gase~ by adiabatic expansion were overcome by Claude. The main difficulty consists in filldiT17: a suitable lubricant for the moving parts of the expansion. qlimIer since the ordinary lubricants become solidified at these

142

l'IWDUCTIONOF LOW TCEMFERATUR.1!S

prCllsure gas, Thus the cooler low-pressure g~ abstracts heat from

the incoming stream. .

1,[&,. 12.-Linae'$ apparatus Im- liquefying air ..

three st..9.ge compreswr the r 1· ,

2~ atmospher~s whiie d co~~~~~s~~~elt ;~~?;3s~~n~()~'c gas fAro~J.. 1 to

of a unosphei-ic ai t· tak ~. ... a tm. Ulargc

. IS '"" en In at e and compressed by c to 20 atm.

* Karl v~ ~itld_~ hom in Hl42. Wl!S P,ofe -. M -

account of his arT-hqud')'itl~' machine ill 1895, ssor at UJ11c;.h, He puulishoo. an

1-1+

PRODL'Gl'Io:>l OF LOW TEMl'ERATURJ!.s

[CHII.P-

Claude utilized petroleum ether as the lubricant, '1 his remains viscous at tempera-

('{lmp:l'eSSOt" tures or - 140°C. 01" even - HiD",?'

r . irnr- and thus acts as all ef.lec.u·ve lubri• t~~ ~ can L ~:lp to. this range.. . 1. Lg. 1 ~ shows diagrammati..." . callv the Claude's air liquefying

rn ach~n e. The gas fmm the cornprcsS61' 1.5 divided I n to 1,'.Ii10 pa rb at A, One part goes to the expansimi I.:vllnder and Si.lffns adiabatic expansion and consequent cooling, 111 this expansion it does external work which is utilized in doing work on the compn:ss,or. The COO leu gas traverses u pwa rds in the pipe D thereby cooling the second p<l rl. of the j n romi ug COIn pres8~d gas in the second heat-exchanger. Fi:g_ 13,-Clamlc-Heyl;mdt system, The h.igh.pressul'e gas thus pilrtL-

all y 1 [q uefies, It thcu suff ers J ou 1,:-ThuIIISOll expansion at the throttle valve. The evaporated gas h taken to the compressor and <Wain L"Omprcs~C'd.

Theorctic;tlLy Claude's mt:3wJ. should be more efficient than the Linde pIOCCS<, but in actual practice IL i!'> only slightly so. This is clue to i hc serious technical difhculties o{ the Claude method, The ljrul(;" method has the great advantage that no movable parr.~ of tI~e app.tI .l1l15 are at low temper;J,tlLTeS and hence the (,_U1l5~.I'UctlO.E1 as simple. Heylaudt slightly modilie~ the Cl~~u(k l lquchcr, .

It is obvious thnt an expansIOn turbine will po,ssess several advantages oyer the reciprocarIng engine. Kapitza in 19lW developed an air Iiqueher in wh ich the compressed air is allowed to expand from a pre~~nTc of about i'i aimos. W a pres.sure of about 1·.5 atmos. and drive a turbine wheel, and thereby suffer cooling on account f)f the work done. The machine 19 about three times as efficient as Linde's Ilquefier and as it utilizes a pressure of about ,I) atmospheres only, all danger due to high pressure is eliminated,

23. LiqlllefactioD of Hydrogen.- The method of cascades {ailedlt. to liquefy hydrogen, 'Vrob]ew$li thereupon studied the isntherrns of hydrogen at low teropeTat.u~5: and fmm that r:alcu.late~~ the v~il,ueij. 0.£ a and b, an d thence the critical eonstanis (p, 95), .I. he en tical temperature 'Was fnund wb~ very low (_21(}OC.) and Olszewski pointed out that this tempeTillture could not bereached bv the evaporation of liquid nitrogen, which was the most intensive cooling' agent then known. The phy.~icbt.s then turned to "he Joule-Thomson method_

This method, however, first appeared to be ioapplicable to !'lydrogcn and helium, £01' Regnault had shown that when hyd1'Ogen

low Urn peraturcs. ~

* Neon can be llItilise(l but it is very rare,

HYDROGEN LlQ.UEFVlNG A 1'1' ARATUS

1'15

is subjected to this process, it gets heated instead of being cooled. That the difficulty is not fundamental and insuperable can be seen from the expression for the Joule-Thomson effect vito.,.

6.(} =1- (2a -0). (4)

6/1 C~RT .'

It is thus proportional to 'lal RT - b hut in hydrogen andhelium a is so srn all ilia Lac ordi nary tern pcrature:s 2a j R T < b, andthe term on the rigbt-hand side becomes negathe. Hence, {or iii negative value of 6P, i.e., expansion of the gas. 60 is positive at, ordinary tempel'alures, and the g'a8 shows a heating effect,

If The suffidently r-educed, the right-hand term in (4) evenfu~tlly becomes pO$itive and the gas shows a cooling- effect, There)8 jmt a temperature where 2a/RT -l~ = 0, i.e., where Jou)e."rhomson effect changes sign; this temperature is called the "tempemture: at inversion' ~. which is thus equal to 2aj bR. This relation gives, a Iter substitutil1g the values of {l;;t.lld b for hydrogen, T, to be -73(>C. Olszewski exp~rinlc:ncally (Jb!jerv~cl the JOUlc-TIlOffi;5on effect fer hydrogen <It various temperatures and found );he~empe:ratuIe of inversion to be - 80.5°C.

Sim I1 ar is the c .. se with all gases. There is iii. tern perature of inversion for an of them which, however, depends upon the initial pressure of the gas. Even the Joule- 'Thomson effect depends ·"c.:ty much upon the initial pressure. It is thus clear that the behaviour of hvdrogen nnd helium i-s not anomalous : they differ from othet gases only in having a low t~mperature of Inversion.

Nuw since T. > the critical ~empeTatJ]IT, is equal to 8aj27bR (p. 95) and T; = 2ajbR, it follows that Ti= (27/4) T ~. This relation is found to hold true approximatety.

Hydrogen must, therefore, be cooled below - ~IODC., for Iiquefaclion. But for practical success it should be pre-cooled to the Boyle

point T B (p. 88) which Is defined as the point at wl;;d.ch o~V} = u. Calculation with the help of van del" \¥aals' equation shows that this temperature T B= a] en. Hence T B = ! T.io ',Ve thus see ihal hydrogen should be pre-cooled to about m;oK (- 177'~q. This remperature is easily attained if we immerse the hydrogen liquefying apparatus in. a ba~J of liquid aIL

u.. H~ro,geD Liquefying APPOlT8Jlus.,- Dewar first, succeeded in liquefying hydrogen in this manner in the Jle a r 189R. Tm.vcrs later improved the apparatus. Hydrogen pl"'epare from zinc and sulphuric add Is compressed to about HiO atm. and then passed th.rough coils immersed in ~ . vater in order to deprive the gas of the hear of coiu pressi on _ :-.fext it passes throu gh cy lindcrs of ca ustic . po-tas h ;HI~ some dehy_dr~ting ag~nc and is d.eprived_ of it5 carbon c~lo_xideand moumre. This 1S essential a~ these Impunnes,,,r()ulJ. sohd~fy mud. hclorc the liquefaction of hydrogen sets in and choke the: tubes. The

JO

146

PRODL"CTlON OF t.ow TEMPERATURES

gas then enters the ] iqu e li er and tra verses the regenera ti ve colls A (Fog. H) 'which are cooled by the outgojng cold hydrogen gas. and in the final steady state, becomes cooled to about - 170 C C. N ex t the gas pliLSses through a ref_Ti~at-. ing coil B immersed in Iiquid air, and th~n ,~tough an~)the_r ~ri~nltil~ coil L immersed In Iiquid all' boiling at a pressure of 100 mill. Ttris is adjusted by allowing Iiq u id air from F to rrickl e Into G and Ly evacn~t[ng G through a pump attached at P. The temperature of the hy. dl'Ogen gas thus falls to about - 2'OO"C. After this it traverses the coil D and s,llffers '[oulc-Thomson expansion at thevafv'C a which is operated by H, The gas~hus becomes cooled and this cold gas. p .. asses lLp round the chambers G and 10', thereby cool ing the coils D and C, to the chamber Rand from there to til e corn pre ss or . r I'hus after a few cycles the temperarure of the incoming gas at a falls to - 250cC, and then Or! suffering the: .Joule-Thomson expansion it Iiquefies

Fi.l{, 14,-I1yilrOg"e-n liquefier. and drops as liquid into the Dew a r vessel V.

Many Iater luvcstigators devised aPEaratus which have <J r.ar~e output. Amol~g~t them Ifl~Y be. men~lOned ~e~nst, Ka.merb~1gh Onnes and Meissner. Ormes apparatus 15 ... 'ery similar to hIS helium liquefier. Meissner's appal.'atllsis sornewhat different. in construction

bu L similar ill pri TI ci ple. . .

Liquid hydrogen boils at - 252.78QC, under atmospheric prei;.!iun~.

By. ca.ush~g it to bon under reduced pressure rt can be frozen tel a '(\IllIte solid.

2.'i. LiqllefactiioB (lfHeliam.~He1inm could not be liquefied fOof If Iong time. The attempts or Dewar and Olszewski to liquefy helium bv the adiabatic expansion method were unsuccessful. Karnerlingh Ormes," however. proceeded in his dforts vcr]' sysremati~"':,dl'i', He studied the isotherms of helium down en 'liquid hydrogen ~emper'atl[l'es (up w- 250"C) and obtained the critical constantsfor helium. He found the following values :-Tc ~ 5.25°1{, jJ, = 2.~5 :.utm. and normal boiling point = 4.2fiQK. The .Joule-Thomson inver-

* Heikc.Kamcrlingh Onn~3 (1 ~J.J.-] 9.3:5), bnm ill Holland, hecarne Professor flf 'P hvsics at Leideu where he established his low temperatura [~OO n:tWI'}' filnd im"'esti"gated the properties uf subsrances at low tcmueratnres.

nJ

117

SOLWIFICATroN OF HELn":M

~i on puin t came out to he a bout 350 K and d.!e BoO}' Ie i?ouin t . 17 Q K. 'l'ui::; tem_peraul1'e could, theref?te, be readied by pte-coo.lmg the ,ga_~ with, l~9.Uld hyd:'ogell. Kam~rhn$h O~nes was thus. convinred of the possibiliry .uf being ab!e to l~que.fy, helium .by ~he Linde process .. He succeeded In actually liquefying It m 1908 in his laboratory at Leiden, Subsequently helium Iiquefiers were conS~1!'uct~d at. Leiden, "Berlin and Toronto. To-day there are scores of helium liquefiers 111 the workl, Since helium is rather costly, the arrangement mould be such that it can work in cycles. in the apparatus used at the cl'yogenic laboratory at Leiden gaseous helium compressed to 35 atm. is passed through spiral S Immersed in liquic! hydrogen b? ili ng under redu Qed pressure and then through au Lg~lng cold helIum. ",!-pour. The. ga~ then suffers Joule- Thomson expamnon and becomes Iiquefied, T'he plant for liquelying helium is, therefore, complicated by arrangements for liqudying air and hydrogen.

"Both. hydrogen and hel1un~ w~r,e liquef.i~d hr Iftapitza. ill 1934 by the Claude-Heylandt method" Helium was Iiquclied by Simon by the adiabatic expansion method alldaho hy the desorption method, Collins in 1947 developed a cormnercial type of helium liquefier based on the Kapitza method. In the Collins expansion engine the piston and cylinder are constructed of nitrided nitralloy steel, the clearance being about 0,0005 inch. es on the diameter and the operation bei.u.g· uJOJpIetery dry, Thus th . e leakage of ~as i~ extremely small and whatever does leak, also 6T(J~3 to the SUcUOl1. side of the compressor.

26. SoUdifu:ation of Helium.-Kame.dingh Onues tried. to solidify helium by boihng it ut;'d~r reduced ~re8surt:. but tl:ou~h he ~aimed to have reached L15QI,- m 1910" helium still remamed a fluid, In 1921 he again tackled the problem and by employing a battery or large diffusion pumps he reduced t .. hevapour pressure to OJH3 mm. and the temperature to O.8IoK,9u.t helium still remained :fJuid. After the death of Ormes, his collaborator and successor. Dr. Keesom suereeded in 1926 in sulidifying helium by subjecting- it to an enormous pr(>.ssute. Helium was compressed in a narrow brass €.Ube under a p:t-es~m;e ~f ] 3.0 atmospheres, the tube itself being im.merse~I ~.n a lUI uid helium bath, It was found that the tube was blocked mchcati LLg that pars of the gas had solidified. IF the pressure was rGducc~I ill' ] or 2 atmospheres, she tube became dear again. Later expenmeutx showed that helium ar 4.2"R solidified at 140 atmospheres willie at 1.1 cK it solidified only under 23 atmospheres .. Solid helium em h;m.lly be distinguished from the' liquid: it is a transparent mass 1i.I~i[lg' almost the same refractive index as the liquid.

21'. Cooling produced. Illy Adia.balk Demagnetisa.tjoitl+~ U pta 1925 11w 011 Iy method available for producing temperature lower than r 'I W;l~ the boiling of liquid helium under reduced pressure .. 1"'1'{'Mllli ill this way reached 0.'72(>:1{ in FH.12. In 1926 Debve and. (:i,HHILIe showed theoretically that Iower temperature's could be prod t If ('( r hy I he adia bottle demaguctisation 0 ( p1.ll'amagne YC substances (i .e, ~ hose s u bs ranees for which the magn eric susce ptibiHty X is !,1II.11 r hut pO~ll.i\ e). The prjnciple of the method ]5 as [oUal'IIS ;-

.14B

PRO.LlliCTION OF row T.EMPERATURES.

[CHAP.

The process of m.agned8ing a su bsrance involves doing 'work on I ~ in align ing the elementary ]TH:lgn~t~ in the direction of the cxterna I field, U a SlI bs ranee already magru;:l i se d • is ~km<lgneti8ed ~ ~Habatically, it has w do work and the energy to do thi~ work. is drawn from within itself, i~ (on~equ>el1ce of ';Illiell it. cools.. This cooling can be made .large If a s~rong magnenc field is employed and the initiOlJl temperature is low because then the magnetisatlen produced in the suhsaanee is large, This follows Irorn Lurie's law which states tlw the paramagnetic su~ceptihiliLy?f a SUb. SWrtCC varies h0ic.r~ulY as the absolute temperature i.e, ;1;:' - C /T. The final temperature attaincd is determined by measuring the nUl.glletlc fimr:cptiiJility 01 the substance and calculating [rom Curie's law. In this way de Haas and '~it:rsma succeeded ion reaching the pre~el1~ low temperature record LIi abut! t 0 J)034 oK ! 11 1935 by adia ba ucally demagnc tisi ng mixed rrystals of chromiul1:-l?oyassi,mn alum and alumlnium-potassiu«, alum at 1 ,,29°K [rom an inltial field of 21000 gauss.

28. Pn!pl'ltPe.s of 'ldl!daD£.e~art Ilquid beJium k!mperBitllm.,_____.

Properttes o.i subsrances undergo veq' interesting dUnges a~ extremel y low temperanrres. lL Onnes round in Elll til a t a t a bou t .16.1;;: m~U1~' metals appe<!Jf' to lose oomp]eteIy their electric a l resistance aut! become superconducting, The resistance do~s not absolutelv vanish Lut falls tu about a rnilliouth of its value so th,at if a current be iuduced. in,a mil uf the metal pl:.1oCU imide ~ucil a Jowrempcramre h~l th b)' ]n:mgmg; a magnet ncar rt, ~h~ CD rreut does not immeclia'tdy die out as 111 ordinary clectromaznetic iurluction, but may continue to. llow for days togt:ther. it has arm been found that near the absolute ~Illll-poin L, the sl-Iecific heat seems to varrish. Besides, liquid helium itself hC'lo\~' about 2cl{ pClS5e:S!>[~~ s~l"ange properties, the 1110~t, imp~ma~t LelIlg the propt:ny ofsuperduiditv when the liquid has no VISCOSit.y.

29. L 41 W 'femperaliq~e

T ~dll!lt{):ue.;----' DeWlt:lT fl~,~k ~ The d i.'<i" __ uvery of .D ewar fl1'l,~k by Sir James Dewar~ in the Royal I nsti tut ion of London provided a very conven ien t ~ppOlraws for ~01i~T temperature stor age, Though y·e~'y low temp era tures had been proch.lH::ed, i t was d ifficu h to maintain the -ljquids a t ~h esc eem pcratures , as e .. en by packing 'lhe bottles with the best heat l 11 SU 1 a ting mat_erial,the le_ahge of heat from ou~idc couJc~ not "be prevented. lBut the problem was solved by Dewar rn a very mg~nmu~ ~v"Y"

Fig, 15.-De~\'ar Fl::LSk,

... James Dewar {l &4 2' -191., L 11(>1'11 at Kincardi ri~, be(:~~Dle Proiessor or N aturn] iPhilosoJl!ly at C ~lrrl hritlg(! in 1 g75~tu:l ~15Q Professor (If a]emi~l ry in tlH' Roval

Institution ill lSJ7, His chLef wDrk\l{a~ in the low tetlIperature - regloll. -

, I

VLl

149

USE.S OF LIQ.l)JD AIR

The Dewar fb~k (shol'm in. Fjg., 15 together with a siphon) consi~t.o; of a double-walled gla51S ve~8e\r, the inside walls being silvered. The "il- is completely evacuated fro111 the intel'spac:e be'tween the walfs w Irich is then sea led. If so~e :~ubsbncc be nOl~ placed inside such a vessel rind the lOp dosed, H IS perfectly heat 1n,~ulatcd. '~x.ocpt fa·!' the small amcu ut of heat. whi ch ma y creep in by conduction alonz the sides. The silver coatings pwtect the inside hum radi.lldon. lloJ the absence of air prevents the passage of heat by conducaion through the walls, If the substance be hung by thin wires inside the flask :,md thc ] attsr evacuated by pump and. sealed, the insula ~1on is compI ete, Such. an arransement was used bey N ernst J n his ]ow ternpel'awre calorimetry !fl. 42). Dewar flash are now sold in the market under the trade name "Thermos flask". They have latelv ~Ct~n; made entirely of met~l with it long ]l£ck of SOilTlC badly CGlfIQUdJng allo!y as Getman silver,

Lnw Tetn.pe-rat!~H1 Si'phon,~.-J'ol' tran~f€'ITing liquid air from one ~'e>5sel to a;noth.er ,special types of S1 phons are U sed, One. such siphon IS shown In Ftg. 15, connected to the Dewar na~k. It i~ formed of a double-walled tube silvered inside, the spOlar between the walls being evacuated. On .the. aFpIlc~do!1 ef gend:~ p.r~s.su.r.e to therubber compressors A 011' B, liquid au: I'H,t;l:; up the siphon and can. he trans-

terred to 011 second vessel, .

Cry ostass ~F Or Jow tempentu reWbt k constant temperature baths are necessary; they are caUed crvosrms, The sebstance to' be investigated is kept h'nnl~n:ed in these b'atl1.s. From Table 3, (p. 136) i~ is easy to find out WhE~h liquids are suItabl€ in a particular range of tem per1l: turcs, Inchl.s "'.'11, y suitable Iiqn id bath s can be easil v constructed down to -218~'C. ,\;Vhen no snltable liquids are ~vaifable, vapoUl's of liquids call be employed-

3D. .~~~ of .Li,l.lIid ~ir ~d Oth~r ~iqll!e~d O"SOI,- The impart. ance of hqmd arr ~,!; bemg lU1::rca~mg.ly felt so much. so that it 1M! nOW become e~,~~nw.~l.]Jor several PIH'pOs.es. Bottles of liquld ulr C:i11 now be obtained rn ~ ny . U11porta n t modern town at a COlnpan'lL~\'el'y ~1~l'lU co.st. We shall gJve some of the import,mt uses to which liquid a H" has been pu t.

(i) PrQd~'ction oj High f!.f.lcMuw.-Hig;h vacuum can be obtained II}' mi]~H liquefied ga&es with or withcmtf'h,atCOaJi., For instance, .. H a \'~'~,'l~' Ii ~ r~rs~ filled with 1i. Le5!> volatile ga~ than 1I.i1",. say sulphurous ~lC-I~[ 111' water VapO~ll':, and 15 then fiur:Hl:undtd by l.iquid ~lr a][ the gas 1 [u~de hl'ool~les s~hdl~led.~nd thus hIgh vacuum. rs produced, if the :"t'~sl:f ~'~Ul8J1h <ur~. Iiquid hyd:~ogen may- he employed to condense II. I 1m process 1~ grea ~]ya5~I~ted by ella rcoal whi ch pcssesaes the I'n 11 ark ~I h h: prorJe'rty of: occlud ll1g gases at very low tem[J era h!:re~ al1 d the hl'\ll/!'I· I~.S te~per:;ttl,lFe the grearer is the adsorption. Further also IJ1(; mhnrpl,lnm is sp.~ee[lve; as ageneral rule it lTIaybe sllid that the mOrf: \,0];11 de the goa3, the less it is adsorbed .

We.: lIhall g-i,'c <J numerical eliilmplc. Dudng a cel"tain expedIIIl'nt ~. \'c~~eI wtltaining ail." at ,t pressure of L7 rom .. at 15<;1C, when

15.1

P~INGIJn.u:s OF lI.IR·CONnHTlO;><ING

VI·l

[ cHAP.

150

l'RODtiGTI'O:>l' OF LOW TEI>fPERATURliS

the specific heat of lead and other rubsuLnces 111<1y be inve~tig"'tcd at low temperatufelj"

(v) use 0/ Liql~id Gases in Scie.raific Research>« The extr~me.l)' low temperatures which are n01;'~' available to ~s by "the use of liquid all' am,1, Iiquid hydrogen h~'I;:e opened Ior tb~ u:ve~t~gator 11 ne~~ a~d vast field lor research, ~ his has made a liq U ld azr plan t eS8~ ntial for every modem la bora tory. Most of the important prapert_IB."l of Blauer have been investigated at low tempe-ran,lres and have Yielded resulta of rat-reaching importance. This has been extended even to biulugical research, where it has been shown that bacteria as w~ll ~s seeds retain (heir activity unimpaired even after exposure to hquld air fcmperatlll'es though a moderately hig'h tempemture is fatal,

(vi) Indusiria! Uses of Liquid Gm·es.-LlquiJ air is used commerclally [or the preparation ~f Iiquid oxygen as ,e.xplained a~ov.c. For submarines and aeroplanes It may be found useful to store !lqm? air or liquid oxygen for l'espimtion but the low lhen:llodynarruc €~. ciency inherent in the Linde machine prevent~ the use of Iiquid air in a heat engine (Chap. IX) all any larjtf'. scale" though mixtures of 119 uid oX}'Qeo 6l~J liqn5d hydrog;i:ll .have been 5uccess:fuU,r u~ed. as _ a highly efficient hght-weight fuel tor Jet-propeU~d aew-en.gmes. Liquid oxygen is., employed on ~ small scale for preparm,g explosives, ~or when mixed wah powdered charcoal and c1eco[lated, It explodes wIth great

violence.

al. rrLndp[es of Air.coDdillo-ning.- The Comfort Charl.-The seasonal variations of temperature, humidity, etc., have marked effect on growth, lOrig-e;,·jty and 'working efficiency of man. The seasonal cban~T€S of the year lead us to change periodically our clothing, food and manner of livill;g_ Bu ~ we Can hardly rope adequately 1h'ith the varia tious UlJJe5B\!,' e can reall y' con trol the w'ealher changes wi dliu our comfortIimits as TC:ga:rds'Leuipcr<t~urc, humidity and other factors, The science of refrigeration; heating and. ventilating devices have rendered it possible to control the weathtt at least within the four walls of our room~ This partlculal' branch ol study is known as the science of. air-conditioning.

Conlplete air.conditioning meaus the control of the foIlrnl>'ing Iactors t

cooled by charcoal immersed in Iiquid air, ga,'c a pre.'jsute of 0.0000+17 mm. in an hour and using liquid hydrogen as the cooler the pressure was reduced to 0.0000058 mm,

(ii) . A~aly·tiCl!l Uses of A~r.~Ll4uid air is ol great use in drying and punfymg gases. ,,\later vapour and the less volatile Irnpuritics ~e ,:asily removed by .sunuuml.inJj ~he gas in question (say H~) with liquid air, and for this purpo5c H is now used as a common laboru-

wry reagent. -,

(iii) Preparation. Of GaSes from Liquid Ail'.-OKygen .~ now pre,pared eormnercially from liquid air by Iractional distillarion, Since the boiling point of nitrogen is - 195.8{lG. and that or oxygen Is _ 182.9<:lG, the fraction to evaporate first will he rich in nitrogen while -that eyap()rating last will be rich in uxygen. A few traenonal distillations will ~uffic.e to separate ~he~e completely. ~c~l!er<l~ Tec:ti~,ers ha vc been devised tel effect this separauon. In Linde s rectifier (1902) Iiqtrid air lJ.ickl es down a rectil yi ng column >;N he re i L mee ~<; an upgomg stream of gas. The ternperature at the wp oI the celumn ~s s}ightly. be10V;T -194ClC .. , (B. P. of U..$luid a_ir) while at the bottom It IS - 183QC- (B. P .. ot m;:_ygen). The ming 15'<15 at the bottom COUles in contact with the down-coming liquid and thereby some oxygen of Lhe. ri~in~' ~s is eondensed, while son:e of the n[trogen in the downcoming liquid evaporates, and the liquid also becomes warmer. The prucess continues till the liquid reaches the bottom when it contains nearly pure oxygen, while nitrogen pas~e~ off as vapour. at the top. 'I'his oxyg-en is almost pure hut the nitrogen 0011- rains about 7% or oxyge-n. More efficient rectifiers have since been devised hy other workers, For details see Separd~ion. of Gases by M. Ruhemann, Chaps. \'1, VII and VIlT.

Again atmospheric air may be utllised few the production ot the rare gases, particnlarly heli U]l1 , neon and arg-Oll. Roughly five volumes of helium are found in million vclumes of air but. this is sufficient for our purpose. Liquid air I)]lIY be separated into twa fractions, the less volatile part consisting of O~, Nj!, A, CO2, Kr, Xe and the more volatile part consisting of He, H!l, Ne. Thus in the rectifier described above the gas going up will contain N~, H~, He and Nc. TIu: nitrogen is removed hy passing the gas through a dcphlcgmaror and hzdwgcn is removed by sparking with oxygen, Neon and helium can be separated by cooling the mixture with liquid hydrogen. Th us, oxygen, nitrogen and fu: Iiurnma y be ob rained from air, For details sec Ruhemarm, Separation of Gases, Chap, IX.

(iv) Calorimetric Applieatio1'!.j.-Dc\\'IHl.i: constructed calorimeters of liquid air. oxygen and hyd.rogen. He e.rnpTo)'ed pLtre lead as the be~tel"j and the volume of the ga_s evaporated bv the application of this heat was measured. T'hesecalo:riDlet~r5 have the advantage that a hrf:?c quantity of gas is formed. which makes it possible (0 c1etcct as httle as 1/300 calories with liquid hydrogen. In this way

Avcuge comfort condition. 75·77°F.

60-65%.

25-7.Fl ft.Jmin.

at least 2.1:', % of total eircol arion,

T em. pt!i'ature

Relative Humidity

Air movement lrHrociuc.iug Fresh Air Puriticatiun of Air

n codorizln ~

rlillilatiofl or Activating

the Air.

i\.lLllOLigll apparently tern pera l lire seems LO be the only guiding I.u.tor in tlu; comlort feeling. the relative hurniditv (r_h.) plays, almost j'jlwllly impm tant role ill the feeling of warmth. 'The same tempera-

]52

PRODUCTION OF LOW TEMPERATURES

LCUAP.

tun: condition, say 75°F. rnay make us feel either a. bit too warm or too chilly according as the r.h, is too hIgh or too low, This is because the humidity condition controls the evaporation from our body and hence the abetracrion of latent hearwhich giye~ rise to the different warmth [<eeIing. It 1S interesting to note that WIDe of the air-conditioning plants in the tropics (CaJ.,utta) do not f;:mp]oy any heat.lug device during winter but only hu.midify the atmosphere by atomised spray of wat~r. This is became the avera . se winter temperature of the place (about 7'0-75"'1' indoors) is not ~reany teo IO~T, but what makes us feel chilly is the lUi .... (4(l%) r.h. Sl,J we fed qune ~omfonable only b), raising the r.h. up to 60-'70%. In cold coul:tnes, h?weveT. rooms are conditioned by electrical or steam-pipe heating devices,

It is interesting to find that the comfort feeling is Iairlv critical, that. is to say. that Individual variation does pot go mUtJI 01£ the average. El ab~ra te experhnen 15 have beenper formed by the H arvard Schou} ~tPubhc Health in collaboration with the American Society of HeaClllg a.nd Ventilatin.g E~gineer.s On the average comfort Jeeting under the different combinations of temperature, humidity. and air

Fi:g-, 16.-Th~ COmf{lIt chart.

velocities. etc, As a result 01 these experiments the comfort chan (Fig. 16) If. drawn in which the co-ordinates are the dry and the wet bulb temperatures and lines of constant r.h, and COIJlfOlt stales [or

VI.J

i'JHNClIt'LES OF A1R-CONDrl'IoN'ING

153

summer and winter are also drawn. The chart shows that gg% ol the eeople during; !ll)mm_er would feel very comfortable ~t 'il OF. effective temperature. We shall gee presently what effective ternp(:rature really means. It relates to. the human feeling of warmth under various cornbmatlons of temperatm-c. r.h. and air velocity. For exam ple, th is 710 F effective tern pera ture, may be obtaiu ed by various combl 11 a tio 1'18 , stich 11£ 4.{1% r.h .• 78°F dl,]' bulb, 62°F wet bulb : or 60910 r.h., 75ClF dry bulb, GODF wet bulb i Or 70% r.h, 74°F dry bulb, 57°F wet bulb (all with air veloeities 15-25 ft.jmin.). So <we '!;BC that the term 'effective temperature' represents ,11:. new scale which enables uS to standardise the comfort feeling due to the various combinations of dry bulh and wet bulb temperatures ("rhich automaticalfv define r.h.) and ail' movemerus, The three combinations (s~ardng with 40'7'0. 60% and 709'0 r .. h.) asexemplified a bove would give rise to a feeling as if the petwn were placed at a temperature of 7 l" F in OJ sa tura ted atmesphere and wi rh still air. This h how we can define eflic:ctivet.emperatute.

The effective temperature sCI!I1e th'tl~re.prc-5cl1~ tile conditions of equal warmth Ieefing with various cornbinatinns o[ temperature,

humidi ty an d <I i r move- \,).<:J

menta, These ale find- no U~

Ings based on experi- ~

ments with men and ~ 100 •

women with normal ~

clothing' and activity ~ 90:

and subjected to conch- tL; -

tioned a tmos pheres of {!!l

the various combina- ~

tQ

tions of temperature, ..J

1'.:1:1 ,., and air movemen ts. 5:

~~j. 17 shows the

effucllYf:l tempera ture

chart. Let us see howe:!' . to read the chart to find .-0 Z

.... - 1'00

the effective tempera- i!>.. ~ •

turc, . Suppose that we :.: ~ -~

have rn the room an l'..; ~ 'J,r;/iJ

atmosphere with dry _~t"i.r$l

bulb temperature 75°F, fj}.!i'~ 00

and wet burt 62 C F and hl I ~ En .

win d vclnci t}' -30 ft. I ig. .I ,- < echveiemper-atii;lre ehart,

min, (0-30 ft./1TIin. may be taken 018 good as still air.) Now puc the str-aight edge or a seale across the twO temperatures (the dotted 1ine) , and it intersects the effective temperature lines at about 70~F. If the sametemperature or 76cF dry bulb and 62°F wet bulb an: found to exist with a wind velocity of 200 ft.jmill. our feeling would be correspomling to 67tOF effective temperature and so on,

'We have seen that temperature and humidity are the most important factors for comfort ke1ing, wlrile movement of air give!>

!

!M

l'R01JL'{:nON OF LOW ·Yl£i\'(J'l':R.. .. TlJRES

[GHAP,

a. f<:eling of ~~.s~ if it has velocities within 25-75 {t./min. If the air IS dead still, It becomes uncomfortable and stuffy. On the other band~ if .it has too high a velocity ;it becomes b1ast'y and we would !lot. Iike y~ The hig"11er" the wind velocity, the colder is OUf feeling. as H facilitates evaporation from our body,

. 'VVe- next consider fresh air. A room-cooler (or iii room-heater HI the coJ;d. s,easoq~) ,must meke provision for Introducing sufficient amount of fresh '11.r Into the room, Of the total circulatien a minimum ot- 2.5 % fresh; air is, recommended, the re.mail1il1lg pan is the ~~)om an'. It~eTf. recirrulating through the machine, It IS true that if more air i~ drawn from outside and cooled in the air-eondiuouing machine for distribution in the room i~ would be better, but it bec.ome's too expensive since much more work hall ~rot to he done in order to cool the large bulk of outside bot air. e

. In 11. complet~ air-con~icionin& outfit, devices ate included ro pun] 'i and deodorize the air by suitable means,

In spite of the oompl,ete lIir.wnciitlouio;g arrangements it TS found ihat :w.e can never fee~ like t.henatural atmosphere under the same conditions, Recently it h.1S been found that the amount ofelectri. cally dl~rge ions. pre,8ent in fresh atmosphere is higher than that presel1t l.l1 r.he ~ll' of .an occupied worn. Experiments have been made to ionise all" by X-rays and introduce the tons into the room ill n_atural pr?portions to activate the atmosphere of the room, Thls bas grven posItive effect

32. The Air.Coolilitiob£ng Mac:hme.- "Ve ha veso far seen w hat "air-conditioning' actually means, Vile shall now consider bow it is achieved.

Fig. 18.- Th~ E v a~)Ct["at[)r.

The air-conditioning machine or the room-cooler is fundamentally a !·efr.ige,atjn~ m~chine which has been described hi section 7, P: nu WIth the main difference in tile design of its evaporators. 'This js

VI.]

THE AIR-GONoITJONl:'lfG MA(.1·n:r-.E

just the question o~ how we ~"aDt ~ ~Hi~ile tile, cold produced by the refrigerating machine- In alr-conrll.tlOnmg umt the .evapora~.or cO~l· sisrs or a series of zigzagcopper.tul";IlTJgs thoroughly inured with th~r! copper sheets in order to get a large area o( cold surface (Fig. i~), As the Ii quef ed rcfrigeran t (SO~" Freon, etc.) ev~ pO~Ol tes lIT the tu bing at low pres.sun~> it. becomes cooled and a fan put tJel:l?d ,the L"YaEo,rator dri ves the war rn all' in the room. A comple te £ngld an'"e~c.omIl tio 11 er is shown in Fig. HI with tbe fan, cooling and heating (oils, humidiIler, etc., clearly shown,

It iJ;. important to note that the summer air Is laden with much moisture and it is dcsiralila that humldity should he lowered. As the air is Iarmed through the cold fins of the evaporator the moisture condenses on them into droplets which are ultimately drained off. Thus cooling and dehumidificatlon are simultaneousLy btonght about in the same pro(:css.

156

l'RODUC'l10N OF LOW 'l·F.;.\IP"ERATURES

[CHAL

T~e size and capacity of an air-conditioning machine is 110t ~etermin.C"(1 on~y by the size of a room, H depend s upon the followJog considerations ot heat roads ~

(i) Sun's rays f:lllil1g on walls or roof.

(i i) COl~ _ducti on t~1~ugh walls a nd ro,_rs due to the difference of O1l tside and Ulsxele ECm peraturcs,

(ii~) Hum.a.n ol['cypanc)t.~For small private installations thii'heat load IS not more than 5% of t.he total load but incinemi<ol" theatre halls, it is 55 to' 65% and in restaurant 40 tG60%: (Average heat dissipation is taken to be 400 n.t.u .. per hour by each person).

(i'l..') Infiltr~tio~, i.e., ou~sid~ un~01~ditioned air entering t.hTOllgh (TInchtlolUn~ ma"hme itself (Its motor) • cooking .'>tOVC, etc. (rJ} Heat-'p.rod.Llcmg 1te~:ns ion the room, e.g., electric ramps, airCOndlW)l,1mg machine ) tself (its motor}, cooking stove, etc.

,In or-der to minfmi~~ the heat load which mostly enters from outside, the walls and ceiling must be covered with insulatlng boards such as celotcx, masonue, etc. and matting- for the floor should

be used. .

It should: however, be noted that the comIort feeling vanes to some extent for people of different counu-ies. The comfort chart show~ in Fig. lfi, is suitable for people of temperate climates, like Amen~a a~J mGS_t of the "European countrfes. nut for tropical CU~l1t:'le~ .l!~t: India, the chart. would differ comidera~Iy_ People in ,till; ti 0J~l~~ a~e aCCU8tomcx~ to I1~llr[! 't~T~r~nt~ and 11"1.1.1":1Id atmosphere, and th!; IS ,dl}' the l~lIIenr.aJ1 air-conditioning machines have got to be readjusted according t.(J our comfort conditions.

Books Recommended.

i. Andrade, 2. J._ C.

M ethucn F.: Co.

3 .. M. an(.~ B. ~uhelnann! Low Temperature Physics (1931), Oamhndgc University Press.

4_ C. [0' .. Squire, Lom 'Tem-perature Pkysiu (1953), McGraw-Hill nook Co.

l!nginr:s. j<!.chon,

Tow

Physics

(1950) ,

5. . M. Ruhcmann, The Separation of Gases (J 940), Clarendon Press, Oxford ..

,6: ~~la~eb.r0o.k, A D~d.ionCl.ry .of Applied .Ph"j'$i.C.~, VoL 1, articles on Relrigeration and LIquefaction'.

7. Moyer a 11 d I" I ttz, Re/rigerativ.n.

8. Hull, Hou.sdwld Re{1'igenttion. pubri~hed by Nickerson &;

Collins Co., Chicago. -'

9. K.Mendehsohn, Cf)'oph)'s£t;s, (1960), Intersclencc Publishers, Iuc., New York.

CHAPTER VII

TH~RMAL EXP AN SION

1. The size of all material bodies changes ott being heated. In the majority of cases, the size increases with rise in temperature, the important exceptions being water and some aqueous solutions in the ranse 0 to 4~C, and the iodide dI silver (resolidiJied) below

14.2cC. o\,Ve shall fine consider the expansion of solids. .

EXPANSION OF SOLIDS

Z. The cubical expansion at: solids is somewhat difficult to measure directly (a method is given in section 17)! and is generally calculated from the linear expansion. Hence, experilTl!ellt~ on the expansion of solids gener a ny conaistin measuring tbe Iinear expansion of bars or rods of the solid. Ffjirisotrnpi~ bodies whose properties are the same in all directions, the expansion is also the same in all directions. To this class belong- amorphous solids (e.g., gla1ls) and regular ~'t'stems of crystals (e.g.) rock sale). Metals may a180 be illeluded because though they are composed of a verv large number of small crystals, these crystals are oriented. at random and the ouerag« properties are independent of direction. In anisotropic bodies such as many crystals, the expansion is different in different directions ami may be even of different sign. We shall first consider isotro pic La-dies ..

lSOT1,OPIC SOLIDS

3. Lillea!!'" Ibpal1!S"ion.- If 11 bar o f length l~ 1.1 t DOG. (J,LU pies a length II when raised to tec,. l~ can always he expressed by a relatlon of the form

lj=.le(1 +.\.e)~ (1)

where A is calle.d the mean coefficient of linear expansion between o and t"'G., and is a very small quantity. This differs very little from the true coefficient. of linear expansion (~ at the Lemperature

L· h . 1· 1 dl. . _1

f W ic . IS equa Co T dt ' The true coefficient 1:1. may also he defined

by ,11e relation CI = JB ~~",,1iidl on integration will yield (1) if 1 i),!d I - At. The mean eoefficien t rna y be pur equal to the: coefficient of expansion at, t/2°C it the range of temperature is small. Often the initial length is measured not at OQC hut at h QC- Then if t2 denotes the other temperature at which the lengh is l:!, WP. have

19 1 +At2 _ l' ) ( ,

lJ """ I +At1 - + .. t~-tl) applOx.

(

158

THERMAL l::~'ANSI()N'

[CHAP.

by the binomial expansion, Hence

. [,,-II

A = .:» --appl'ox. (2)

ll(t~-~J

The mean eocfficien t l\. itself is fou nd to "Ii at]' wi th temper 11 ture.

This implies that the relation connecting length andtemperamre is Hot a linear one and equation (I) must be modified into

l; = IB {l +;\It+Azt2+ ... }, "t (3)

"'Where the successive wefficiellts go on decreasing rapidly.' An equation of thh type is entirely empirical, The molecular theory 'of matter has not yet been developed sufficiently to yield an exact theoretical formula. Cenerally it is sufficient, to include terms up to the square or t; the relation then becomes parabolic, In most cases both the coefficients Al and J\~ are positive, the body becoming more expansible as the tempera LUre rises.

4. Hadier Meulb'elnents (If Linear ExplIl!!smn.- The linear eXPQnS1011 of solids is very small t a bar of iron one metre long: when heated [Torn 0 to looac., mcreases in length by about ~ ,2 rom. To measure su cn ~mall cb~ngt."'1l i nIengtb acrur~tel y , ,special devic~s are .nec.css,n:y. The increase 111 length may be obtained from the readings of a spherometer, .Dr directly oh~~tv~d ~Y means of ~ lUicro.s,~op(l. Af5 ra in, the expansion rna>' be multiplied III a known ratio by uhl.ismg tile principle of the lever. The most satisfactory method. howev'eI", consists in utilising the interference fringes, which is considered in detail later. In this section, we shall consider the earlier experiment);"

The spherometer 01' a m!aometer sere» was generally employed to measure the expansion and is suitable tor ordinarv work. The ~xrerimelltal b~l~> about a. metre ~Ol!lg. has its one end pressed agaimt a fixed screw while the other end 15 free to expand. There i.:9. 11. micrometer screw or :J spherometer which com be brought into contact with this end, ily nnting the micrometer readings when the Screw is in contact ~t GOG, and at anv other temperature t°c" the expansion ol the rod 18 Iotmd, whence the mean coefficient of Iinearcxpansion can he calculated from equation (1).

" Roy and Ramsden ~m~lo}'ed microscopes to measure the expan. sron ~nd wp.re able to obtain results of considerable accuracy. The experimentul bar was pluccd horizontally in a ~rough between two standard bars, and parallel to them, One standard bar carries a cross-mark a t each ell dwh ile th e 0 ther ca rries at either end an eyepie.oCe pro,·ided WILh cross-wires. The experimental bar carries an "Object g-l~.~.s, at Doth ends so that the eye-piece on the standard rod a ~d the ob leet glass on "the experirnen tal bar together formed a mlcl"OSoopC focussed. on the cross-marl: on the second standard bar, The standard bars Were ,always kept ira ice, One end 0J the experlmental bar W;:I,S fixed while the other end was free to move when the bar . ,~I!as ilea ted. The 0 bj ect g lass was brongh t back to its initial positron by a fine micrometer screw, whose initial and final readinss

gave the expansion, 0

'I'll. ]

159

GOM1'AitATffit METHOD

Laplace and Lavoisier employed t~e lever principl: to magnify the expansion (rnedumical lever method}. The change 10 length was converted into a change in angle by mean s of a ] ever arra I1gemen t and the a ngul<JT change was measu red by a scale a nd a mirror or telescope. The principle of their appara." HIs is indicated in FIg. I, One end A or the experjmcnt a .l bar AB is fixed while the other end B pushes against a vertical

lever on attached at Fig, l,-Apparatus 01 Laplace and

righl angles to the a.xis Lavolskr,

of a telescope J~L; whu:]t .. '.. 'r

is itself pivoted at 0 and is ,focus.se~ on. a distant veru.c<"lI~~:-a}~ CC :

The bar AB is first placed 111 meltmg ice and the ~C<Ji.l~ d rVlslO~l t; seen through the telescope is noted. N ext the bar IS enclosed in a hot-water bath. The rod AD expands toB' thereby tilting the telesc . .up~ LOL to th~ position :r-/OU and. the sca}~ division C' IS null>' seen through the telescope. 1. he exparmon BB IS equal to OR tan L llOD'= OBtan l .. CDC' = 0.B X ee' JOC. .

Paschen employed 011 combination of the micrometer screw and the lever, The expansion was multiplied in the ratio 1 :!) oy the lever and this magnified dl1l:nge in length was ~easured by. the micrometer screw. An optical Iever arrang~tnem 1S "aho s()metm~es used when the expansion causes a plane rmirror to tllt and thereby def ect a ray reflected from the minor.

s. Standard Metlw~At the present time the SEa!J dard me thods

employed for measuring ex pa nsian,are :. , .. ...

(l) Comparator Method, (2) Hennmg s Tube Meth()~, (3) I\,.~I:thod of Interference Fi'jng~s. Methods (1) and (3) are direct while {2) is dndircct,

,G. C>omparatoT Method.- This is a standard. precision method for -determining the expansion of materials in the form of 11:. bar of tube, Th.e bar, abont a me,!e long, is mounted horizontally in ,a ~oublewalled trough so that It call expand freely at both ends (Flg"~} an~ h as rwo fine marks L, 1. made near the ends" A s tandard rn etre l~ abo mounted horizontally in another double-walled trough, both these trou ghs. being arranged parallel to each 0 ther and mounted on rails so that e:itller the experimental bar or the standard metre OUl be bwul;fht into the field of view of two vertical microscopes II.:[, M" The microscopt:~ are provided with an eyepiece micrometer or can be moved parallel to the direction of expansion Ly means of a micro" meter screw, and are fixed vertically in rigid horizontal supports projecting out from two massive pillars, the disrance between the micro" scupe.s heing about one metre.

HiO

[CHAP.

First the two troughs ate filled with water surrounded by melting ~cc in the space .he~·wee[l. ~he double walls, The exp:nment;a! bar l~ then wheeled into posltlOn and the fine marks on 11: a.t~ viewed

Fig. 2,r- The Compara tor method ..

through the t.wo microscopes and their positions are noted in the micrometer. The standard metre is thC'n brought below the microscopes and the two extreme nUIl:k.:s of .g1'aduati~n are viewed~rrough the rui rroscopes, From the change In the micrometer rtaciUlg the lencth of the bar at QDe i .. obtained. The experimental har is then

o heated by replacing the melting ice in the. doublewalled space of rhe trough by water which 13 heated

~ under thermostatic coutrol. The fine marks ... re ag-diu viewed through the micrometer eyepiece. The increase in length is determined from the change in micrometer rear!ing-, For measure-

:l',,",", men ts at low tern peratu.res th e'-' ex perimental rod is placed in a tube which is immersed in a suitable liquid bath (e,g. liquid air) ,

7. He.nning'.s Tube Method o·f rr;'Iea&nrill~ Relative Expalliion.-In this method the experimental and the- comparison bodies are together brought to the same temperature and the difrerefltial change of their lengths is measured. The comparison Llody is so chosen that its expansion in the temperaLure region is accurately known and, if possible, is also verv small. Fused silica

sq_ 1. J

I serves this purpoll-C well. Inside a Iong vertical

tube made of some well-defined glass ([used silica, jeea glass) , there i,~ a ground point, molten and dra w n ou t of the same glass ;:t t res lower end. Upon this point rests the experimental rod R (F 115'· ~) • a bon t 50 em. Itmg and having both of its end faces ground plane, Upon che upper surface Flg', 3.-Hel[l1ing's ur R rests. a pointed end of another glas~ rod S

apparatus. made of the same glass as the outer wider tube.

To the upper end of this rod as well ar, of the outer tube are attached end-pieces carrying scales. The whole tube

s

vn.]

:FIZF.AU'S lNTERFERE.NCE METHOD

151

up to half of the height of the rod S is immersed in a hot or cold b~th and the relative shilt of the end-pieces is measured with a ml.cl'?soope pTo~·i ded wi til a miCf"?met.tt eyer.iece .. The shift gi~g, the relative expansIOn. o~ the experimental ~od a,gamst a grass tube oE equal length. Th15 1$ so on r,h~ assumption that the temperature of t1?-if: rod and of the ou tel' tu be ts fllC same a t the same height. For high and low temperatures suitable baths, may be employed .

. 8. Fjze.au~s. JDtorf(!HJlCe M.ethQd.-FiZitall devised an optical me iJlod ~~peJ}(hng U p,on the observation o.f interference U:ingc..:..s, This method rs capab!e 01 very great ac~urat:y. and ]S specially suitable wh.en small ~p!lc;lmens of the experimental substance are available, as in the case of crystals. , '

, In h:is ori,gina' experiment, Fizeau used the substance B {Fig. 4) m the form of a slab ahout l em. thick wit.h 1:1;;"0 of its opposite plane

Fig. 4.-FJzcau'5 interference method,

fa(~~ parallel and polished, It was plawed with one of these faces h:)] izontal on a metal plate A supported by three levelling screws S, S. l h,l'~(l screws pf[lvct~d upward through the .. metal plate a, little be .. yo. nd 1 he. 11 P !1c-r surface of th~ slab B. A con vex lens L haVing the lower SUI' r a ~e of. ".ery large r~ chus. ~f curva tur~ was placed on these screws so that a thin fL1m of aer lay between this surface of the Iens and the u Pjlcr 1 to I i.~ hed Sl~r£a{:e of the slab. Wi ththe help of a rna rror M au d ~ 1"l~ht-:lll~~l{'d. pn:;m ~ placed above the le-:as, horh:~ntaI ~a]'8 of Ught i.rom a socli 11m flame} were sent down verricallv toi'lluminate the air film and tile r.l}:s reflected repeatedly at the surface of the Slab and the Iower surface of the lens proceeded verticallv upwards and were asain l'd!cded by ~hc .pri~m P and received by a 'horizontal telescope f so that Newton s nngs could he seen through the telescope.

11

162

[CHAl:'.

TlfF.RMAL EX[> ANHON

"~Ye know that in the case of Newton's rings the condition [or fl bright ring is

0. = 2,~e cos r;:::::::: (2n + 1)A.j2,

where S is the path difference, e the eorrespcnding t.llickne.ss of tht; ail" film and # its refra.ctive index; l' the angle of refraction ot d1C: ray inro the film, n the order of rings and 1\ the wavdengdt of the hgb r used.

In the present case fJ. = 1, '.I' = O. 'liVe have therefore \.

8 = .28 = (2n + 1) Aj2. C~)

The difference In the thickness of the film at two successive bright rings is A/2. Hence when the thickness of the film .challoae~ due to expansion 'Of the slab and of the t~ree screws su~por:tmg th~ lens the rings appear to pas.. s acr~ss a ~lark l.n the lens. Slll~ o:le-tenth _of th: distance between successrve bnght rmgs could be measured, the chan~e in length of the order of 'A/2 i,e. about O.OO(}U2944 mm. could be determined.

Wllen the above arrangernen t prod uci ng' the air film Willi enclosed in a ella m ber which. was heated, the t/bjc.kness 0'1' the film ch.anged d ue to' the differential expansion O[ the screws and the substance Fl. ~l'ld tile shift of bright rings across the mark was ol~erved, U x ,bn~h~ rings are thus shifted, the difference in the expa~mon of ~be p~o.jectm.g portion of the suppOTling :;OCTeW and of the slab B along us thickness IS equal to xAj2. In order to fin~ the expanston 01 (he ~cre"w.s, the slab was removed and interference rings were produced by rellectlons at the lower surface of the lens and the polished surface of the metal pl me through which the SCTeW5 prnjeCl ed,

Abbe and Pulfrich Impl'ovc.:d l'ueau's appa.ratm hr rt:pJacing the screws by y'uarLz. rrn..~~ as :;lwwn in. Fig: .5, p. _ ] 50_ G and Dare tv>'O' (1 UM tz pla tes and lit IS a hollow r.y Iindri ca ~ trt p.od, also of q uartz, cut with its g~nerating ?-xis p,arallel to. the OptiC axts, aJ1~ placed between G and D. The specm1Cn rs pla{:ed inside R and the fringes an: formed by the "Nedg:e-shap~d air film encl~serl between the lowe r surface u~ D ana the uppCr SL~r£~ce of the}~eCimen, the ~ng~c of ch<=: l~l'etIge being very small. The ~ight lrom a Geissler tube (l'lg. ti) wnt~lfimg mercu"y and hydrogen a used. It enters the telescope at tight .angle~, JS deviated through a right. angle-by means of the prisms P, P and then falls upon the system as a parallel beam. The brjnge systems for different 'wavelengths are formed at different heights. in the focal plane of the O'l?jective. 'By l~u.rning 11 strey.,. any of Che?eSj's~c"lT1~ can bebrou.,.,ht 111 the field of view of the rrucrometcr evqnece. 1 he lower ~m:fa;e 0'1' the upper quartz plate n is prO'v1ded with rt mal' k of reference and the UUJ.I1 her o{ fringes crossing this reference mark due to rise of temperature can he measured with thp-bclp o[ the micrometer eyepiece_ If ;1,1~ r.~} 1\~,.".,."deuoLe the various wavelengths of ligh t employed and Xl + gl' .1;~+e~, Xa +~~ _ ... .rhc numberof iuterfereuce bands displaced across a fixed line (x representing a 'whole number and ~ a fraction), the increase 6. in the thickness ol; the au' film is given by

\CU_]

1M

~I~_.:._,,,:;_J"'~ ~--~--":~ ::::~O;U. _. _ .. :; 'j£J~~

P\'ff, ~ :

· , , ,

, . , .

· .

: 1

! I

I'j ~

.1 ~.

~'l ! . .'

..

· .

, I

I: :

"l

I •

~ =

~l!. ;:

., e

., I ., ,

, .

~~~

. . i

G' .',

Fig- 5_-Quartz rings of Abbe,

Fig_ 6. Apparatu» Eor rnea~l~riJlg; expansion of ~rys*als by Fixeau' s method.

6=?(Xl+fl)=~2(X~+e~)=;~ (Xil+t~l' (5)

9. The Fringe Width Dilatomoter.-In the Iast method the change in _length '\'~ilS Iound. from ob:5et~atiom. On dispia'c:cn:ent of the ~nges. Priest devised a dilatorneter In which ,changes in length can be obtained from the change in width of the interference fringes. The apparatus is indicated if 1 Fig. 7, p. Hi4.

The air firm IS enclosed between - the lower surface of the cover plate and the upper surface of the base plate, both of which are ~Pt~cally plane and enclose a w(~dge-shaped" space (0, I .to O.li mm, t.hl~k)_ I'he sample under test ends at_ me top 1~ a fine .pOll?-t X upon whIch res ts the cover pIa te, On looking down In the clued] 01: 00, a system of interference fringes will be seen (a~ shown in the plan) arp~earinf~ to He in ~he plane hb so that the fringes and the ":efe'I'ence Iines ss and .'{x on the mirror can be simultaneously focussed" ,\rVheu the sample expands on hearing, it lilts the cover plate and thercbv chang-es the t.hicTme~s of the air film and consequently the 'WEdtN of the Iringes, The number of fringes between the lines ss and x» arc observed both initlallv and finally, and from this the cxpausion

can be calculated.' ,

\

1(;,1

'l1'1yTtMAL EXPANS10N

[ t:HAI'.

The calculations CaJI be readilv made. \Ve 8~W from equation (4) iI1 the last section that if the him thickness increases by 'ltj2, there is a shift of one fringe across the mars, the fringes actually contracting. Thus if in the presen ~ arrangement the rium bet' of fringes between the mal' jl:,g ss and xs: changes by ...: + t) and d denotes the distance between ss and xx and). the wa'l,'elength of the light employed, then the change .p in the angle between the planes bb and G(; measured in radians is given by

4>"" (J:'H)~. ~. (6)

. Again. if D' is the .perpendicular distance £'1'0111 X ttl knife-edge S5, 6- the relative expansion of the sample with respect to a pi cce of eq II al height made from the ' material compesing

d the base plater then If> is also given by

Fig. 7.-Fdnge width dilatometer, 1>= 2. (7)

Combining (6) and (7) we get

" = )2·D (x + ~).

:;:. 'a·

(8)

Knowing 6" thu coefficient of expansion can be calculated,

10. DisCllssroD of ReiuJu.- Table I gives the mean coeffideni or expansion of several substances between 0 and lOocC. The mean coefficient )( multiplied hy lOfo is given in the table.

Table 1. Coefficient oj Linear Expansion of Substances,

___ S_'l1_l)_sta_n_c_e A_X._1_O_e:_I- __ S_"L_lbstance I __ "_X_]_O_6_

per -c per °C

Platinum Palladium Silver Tungsten Brass Invar lena glass. Pytcx glass Quartz glass

Alumlnium .. I

Copper .. I

Cadmium

Chromium

Lead

Magnesium ManganeSE Molybdenum

Nickel

2:3.8 16.66 31.59

8.4 ~8.0 ~6.0 22.8

.?20 13.0

8.86 11.04 19.68- 4.5

18.1.3 0.9 8.08 5.3 0.510

vn,l

EXi' /l.XSWN Of' AN15ornO;b'IC BOoDlES

165

But as already mentioned in section 3, these values change appreciably if the final terupe:raturrc is different from 100°C. The mean coefficient A 15 a function of the temperature. As the final temperature is lowered the coefficient decreases. GrOnei3en has

. 1 dt [ low temueratun d

found th~ value of the q Ll."'I.nt.ny l;, ,dt (I·rvel'Y 'ow empera uresan

has deduced an important law conlleciing the coellic:ient of expansion and the specific heat, Grlineisen's law states that [or fJ meUtI the ratio of the coeffiden~ of linear eXfJtlnsion ~o its :r.:j)eciji.c hea: a.t Ul-nstant 1n:eSIure is GGnsWnt at all femperatun~$.

11:. Surface and Vo[wne E~ansioD.- The change in area ~nd volume can he easily calculated from a knowledge of t?e coe£fiCl~nt of linear expansion. A rectangle of 5itles ~ and b WIll, OI!" being heated, have sides o[ lengths l (1 +M) and b (I -I- At), and Its area will become Ib (I -I- M) !!. II the inl tial and final areas be A 0 and A we have

A = s; (1 + 2M, approx.. (9)

small, Thus (he coefficient of surface expansion is 2,\. the coeflicienr of volume expansion tan be ~hO'wn to

since " is Simila rl y;

he ::lA.

12. bparuzoD o£ SiJrC9i Glull. Invar.- Silica glass (quartz .which has been Iused and resolidified into the non-crystalline form) 15 now commo,nly eTl1pl()v~d for the (omtTU('~Cion :of ther~l~meters." The expansIOn of sihca is very small (,\= 0.:) ;< ro-» per C,), and l~ \'e~y conveniently determined by Fizeau's method. Vessels made of this material can he heated without any fear of breaking', . The c~rve connecting the coefficient of expansion and temperature is a ~t.t~ug~t line between the mom temperatuw. and 100ooG. but at both Iirnits It bends. The ooefficien! is negative below - 80"C.

Iuvar is another special substance, being an alloy of nicke1(360/0) and steel. Its cllClJ1cient of expansion at ordinary temperatures is extremely small and hence it is .genenJ.lly employed for ma~~ng secon .. dar)' standards of length, and in the manufacture of pl'eo:;,um docks and watches ..

o\NL<;'01'1WPIG 1l0D[F.S

13. It was first observed hy Mltscherlich that the angles between the faces of cleavage of a. crvsral of Iceland spar change whe:n the crl'3t.al is heated, He ga~ve the correct exr).lan~tlOrl of .the _Eheno. menon, viz., that the expansion of the crystal l!; different in different directions and this Is the cause o] the change in angle. Such substances ate called anisotropic or non-isotropic,

For every crystal, however, there GUl be found thl'ee rnutually p~rpe~l dj,c.ul. a r directi ens su ell t h~ t if. 11 eli be is ell t out of the cryst.al with. Its Sides parallel to these directions and heated, the angles wIll remain right anzles though the sides will become unequal. These directions are catYed the principal axes of dilltlation and the coefficients of expansiouIn tJlOSC directions are called the princijml coefficient:;

166

TI"IE-RMA,L EXl'i"NSWN

(mAP.

of ex.pansim'~" Denote these by A-,,~ A), 1\1;- Then a ~~e of sides If! willon being' ,heatc:d to tOC, become a parallcloplped, whose edge~ will

he given uy

l;,: =lo( 1 + .\"t}, l;. =lflj( 1 +:l.""t}. l~ =t~{l +A~t)., (10)

l~lj'l.t =lo~[ 1 + (.l~ +A.f +,l~}tJ •. . . (li)

The yolupile coefficien t c:t cxJ?ansion is rhus ~'" + A) + J_~. Th~ H.~ar exp8Jl.:51C1~1 l~ any oLhey directioncan .he T.eailily ~alculated rn terfDs of the prm Cl pal coefficien ts and the (h.n~CtJ.01l cosines,"

14. Experimeutal Melli0U and R.efilllii:s..~Crys,~aIs are 'best inve~tigated by the interference method. The cq<s tal is cut in the manner d.e'lin::d, into apIa te with parallel faces froln 1 00 10 mill. thick, an"d is flaced betwe~n the, gillii8 plate and the 1Il.eLal disc. The deuuh 0 these ex PCfHUCll ts have already been gIven.

",,\Then the expansion along the various axes of different crystals is investigated, vet)' iDtet'estingr,~ml ts are 0 brained, In the hexagonal S'}'stGm, for optlcallv negative crystals the expansion along the axis is aJway.s grc8.cer than that along an axis at right angles to ito; whi Ie for optically poaiti ve crystals the reverse is the case. T'11O:5, 1:'1" Iceland ~par we have expansion parallel to the axis and contracnon p-erp£udlcu]arto it. The contraction is always much less than the expansion so tb OJ. t the vol ume OJ efllcien ~ remains positive,

EXPANSION OF UQUIDS

IS. In Gi~C: of liquids we have to consider only the cubical (,.'X. pansion. As before. t h<2 volume e<U1 (lgain be expressed as a {U11(,; .. tion of the temperature; thus V = V~ (1+ <lilt I~ a~t~T

) ,

(12) (n)

or approximately.

v -= f'ro (1 + tJd) ,

where tJt is called the mean coelflcient of e;,: panslon between 0" and te,C. Th us if a mass M of the liquid oecu pies the vol umes V, V~ at te- and fI~C, the densities p, Po oJ the liquid :at. the l'e;;pective temperatute~ arc p =MJV, p~= .MjVQ• Using- (13) we get the relation

]V

:0= V(I =1 +M, (H)

The exlh\1.nsion of liq uids 1.8 ]11 uch greater than tha t of soll ch, yet it is more difficult to measure, for it iscemphcated hy tlteex.pan~ion of the contain.in& ves~eL, ~he ex pa:rlS!On . observed is called I, the a ppaTent ex.pansJ:on and 1~ a COm bination of the two effects, mz."expamiofi of the li(1Uid and of the containing vessel, It cau be shown (see sec, 11) that the coefficient 0'£ absolute expansion of the Iiquid i~ approxilll<l!t.e.lyequaI to the sum of, ~le coefficients DIE expa1l81011 of the conraming 'I,i'~sseland the coefficient of apparent expansion efthe liquid" Thus the farmer can be de'tecrminell ifhhe latter two quantities are known.

To Further ~ Glazebroolc, A Dktimt;fW:Y tif AfJPlip.d l'h'Ysks, Vul. 1, p. ar1il,

!

vrr.]

WEIGln- 'f'HEIlMOME",[iI:1l 1¥m:fHOD

There ate three well known methods for determining the app<l-

rent or relative expansion :-, _..-

(0 The Volume Thermumeter Method, (~i) Ule Welght Thenno-

meter Met.hod, and (iii) the H ydros~a tic Method.

16. Tke Di.tarometel' or Volume Thermom.eterM·ethod.-l?he rherroometer consi ses of a bul b to which a. graduatoo seem l~ au,ached. It i5 neady filled with the liquid to beexperi~entE;)d up()n~ , If ~~ liquid stands to the: mark ;<J;~ OIl the stem at 0 C., and; to the m..uk, Xl at tOe", and. if the volume of the bulb at O~~. ~s Vo and. of each divlslon of the stem ViI,l:,hen volumes of the Iiquid at the tWO

cemperatur{';S are

v~+ ~(IV(l ./ heing th€ expansion oV t g C. is also eq ual to

and (Vo + X11JO) (1 + yt) ,

the ccmtaining vessel. 'The volume: at

(Vo + xov~) (1 + c:t'),

where IT is the coefficient of absolute 8x:paruioll of the liquid. Equa-

ting we have, "

(Vo -{- ;oc~v~} (I + at) ==== (1"0 +X1~)O) (1 + yt)

Knowing y L',he true coefficient tJ;: is c_<tkulated, or if "i i~ no~ known, the relative ex pa usion ill -"'I can be eval u ated,

17. The Weight TbermoUleter Mellimd.-A more accurate rneth od, depending- upon ,. Ute detcnnination of w~tght ann not of volume is Iurrrished by the pyknomNe'r or the wel~bt tllB1rmOff'lCLer. ,!h~se are vessels so constructed as to take a. defini tevolurne 0 E the htl uid, The weight therm.orw..::tel' is of the shape shown in, Fig. 8, and is made of gl.a;'lsor, fused ~iH~a. It is fjr_~t weighed and then corn P letel y fined WI t!1 the liquid by alternate hea tjng mdcfJoling wi ttl the open end di p'pi:ng in a ell P of the liquid.

The (~Kpr:dIDCnt consists in. weighing the tbennometerlllkd with the liquid a' t~ilTO temperatures, Let Wi' r,Li:;! represent the weights of the liquid filling' the C~ic:rmo1Uel.er <It, icmpera rurest 1 and t~ respectIvely, If V 1! V 2 are the VO]UITIe:!i of the ve.~sd at the two tempeutnres and Pt, P2 the corresponding densities of the liquid, then

tU1 = V lP1, w~ = V~P:ll. (H)

But n a, 1" denote the: expansion ,coefIkient or the ll(;ll.lid and the vessel respectivel y,

V~_l+yt~. ~ _1+a~I

V;-l+r~' PI -'l+at2

~_h __ ~ 1 +yt1 . I + ai2

w~ 1 +yt2 1-+ 'et.t1 .

==' II' (u-l) {t,"--t1} apprullThe<lppa~'em, expansion a ~iJ.n be obtained [rom (lG) m (17) if

)(~

! :

I !

U1

I

Fig, &_ - Th~ Weight Thl!["m(}l]'Jct-e~- -

157

(Hi)

(17)

/

168

THERMAL EXPANSION

[CHAP.

the expansion of glass is disregarded i.e., "t is put zero. \Ve then obtain from (17)

w W

or a= 1- ~ . appro:;::, .(i8)

W~(l~- ~n)

.l!:qualion (HI) can be I:.reated t-igornusly. A~;u.n1iug t2 to reler to 06C, and dropping the suffix l, equation (I6) \yicIcts

w H"'J,t '

:.._ - . )

Wo l+al

W"-tV+fLI,,

a=.- - -y,

rot rlJ

or

(19}

w

= a. I- ~".. w-

(20)

I t h ch Us seen rha t, rigorous] y speaking, the tru e ex pa [) sion cocfficient is a Iiule rnorc than t.he sum of the apparenL coefficient and the expansion coefficient of glass, though the difference is almost negIig-i blc, and £01" all. pnu:;licat pur pose;;; we can assurn e . CI: = n + y. \'Ve could treat eq nation (If)) more gcneralIy when the result will be more complicated than {2U}. Knowing y the absolute expansion

H can be calculated. .

The thermometer can also be employed to find the cubical expanslon of solids indirectly hy enclosing the specimen inside the thermoTIICler.lI

. .18. Hydrostatic Method (M,atthifsfien's mothod).- 'This consists in fiml1llg the apparent weight of a solid when immersed in the Iiqirirl at two temperatures t1, t~ respectively. The loss in weight. of the solirl_ is ]ly Archimedes' principle equal to the w(,;ight of a volume of the liquid equal 10 that of the solid i denote this quantity by w. Then

Wl = V1Pl' W2 = V ~p~, .

where 1-'t. V2 denote the volumes of the solid at the two ternpcl"atu!"es t1> t~ respecti .... ely. Then

Vl l+ytl V~ =; 1 +yt~' and proceeding- 8:~ before,

W1-%

a-y= W~(t2-tl) appmx. (21)

An equation analogous to (19) can also he deduced.

UI. Abf;olute Expauioo {If Liqll.i.ds.- As a1re8rIy mentioned, the throe foregoing methods rna]' be crnploJed to find the absolute ~xpansion of a liquid provided the cubical cxpanslon 01" the containmg vessel [or of the immersed solid in § 18J he known, One way

II; See Glazebrook, A .Di~·tilmat'J' of AJ-tPJie.d Physic..s Vol. 1, p. 8"13_

of finding the latter is by calculating it from the linear expansion. This is, however, open to objectlon for the linear expansion is determined from bars of the material and it cannot be assumed a priori that the physical properties of the material do not change when it is annealed and worked into a vessel of some sha pe, For r h is rea son it is best to select vessels of fused silica for which the volume coeflldent is extremely srnal] (about 0.0000015 per °C.).

20. Hydros;tatic BaJllII.Ce Method.- There 1S onIy one direct method Q f determining the ahsol ute ex panslou of a liqnidwhich 'was first given by Dulong and Petit. It depends on the hydro. static balancing of two liquid columns at different temperatures, Dulong and pe.tit employed a simple If -tube for the p1,.ll·p()~e. RegnauJt brought the upper ends of the mhe dose together! an improvement which wade h: easi er to 0 bserve the di ffcrence in heigh t of the 1:l;",ToWlumIlS. The diagram {Fig. 9) serves to illustrate the principle ol the method. A glas~ or metal tube, bent as shown in the fig ure, contains mcrcu ry, T'h e vertical columns All, CD. GrD; are 8UI.'rounded by melting ice and are thereby maintained at O°C., while the column NB' is surrounded by an oil bath maintained at any temperar.ure l°e. Suppose that /'1.1\' is horizontal, T .et H, H', h, h' denote the heights of mercury in the various columns ~ shown and p, PB the densities of mercury at ~cC. and O°C. Then since the pl'esmr~;s at D and lY arc equal, we have by equating rhe two expressions for the hyd.tostatic prcssnre at A,

h' Pc. +H'p = llplI + nP\J.

P = hij(l +ct).

VII.]

HymWsl"ATrC BALAXCE METHOD

lb9

But

r

Fig. 9~Hydr()sutk ~a1<Ul!Ce Method.

(22)

where c is the coefficient of absolute expansion of mercury. H~n~E H'

l+ct +h'-.=H+Il, (23)

t

whence: G can be calculated.

If the columns H .• h., hf an not at ooC. hut at temperatures. tt! t~, l@ respectlvel y we shall ge ~

H' h' Ii

- + - . - ._-+,...."..---

I +ct I +cst~. ~. + c1t1 I +C-2~

~hete the quantities .C1, c~, c~ denote t~~ mean 00. efficleu ts of. expansion between the differem ranges, 1 hese can Lc determined bv having the temperature of A'U' to be tj, t~! l~ successively. 1'£ the- height uf A' above A is hi. a corresponding tum can be added to the right-hand side.

Reg-nault's observations, though carried out with great sk ill. must be corrected fur various sources of error and hence cannot, yield

(24)

170

'l'flERMAL EXPAN~ION

[Cli,,:r.

results ,!f ~igh aCGul?cy. Callen dar and Moss repeated the experiments aunmg at a hlgh degree of accuracy. Instead or a single pair of hot: and. mId. columns 1.5 m. long cl1lployEldby Regnault, ihev used srx pam of hot an d col d 001 UmM eac h 2 m. long and connec ted.

in seri es as shown diagrarnma ricall y in Fig. 10. The hot and cold eclumns are

b marked Hand C respec civdy. The difference in heigh e or the firs £ aoo the last column (viz., ab) is six times that due to a singIe parr.

In the actual apparatus .'1f. gil •.. were doubled back so that an the columns marked C 'were one behind the other, and. similar was the case with H columns, All the H columns were placed in one limb of a rectangle and all the C columns in one limb of anoth er rectangle, w hile the 0 eher lim bs ui these rectangles contained electrically heated: oil and ice-cooled baths respe ctivel y. 'These 'were kf'p~ circula ci.ng by means of an electric motor and their temperatures were determined by a. long 'bulb' resistall ex: thermometer. Experimen rs 'Were performed in the rang~ (1 to 300°(;. and an accuracy or I in lO,UOO 'I;\T1(5 aimed at,

c

F~. 1O.-Ar11l.EJgement o£ Cal.l~1'ldar and MO~5' s apparatus.

21. Remlts for MeJ'Clfry.- Their values {OJ· mercury are, however, . 5y~lelllatically different from the mean or earlier investigators such as Regnauli and Chappuis. Harlow has also made accurate determinnrions with the help of a lNeIght thermometer of silica and aimed at an ac.elHJCY of 1 in 18,000. The concordance of results 'with bulbs of diltercnt shapes showed that silica was quite isotropic. The coefficient o( expansion in rhe region 0 to lOOtlC .. is according to Callendar and Mm~ O.O(t0l82 per -c.

The following numerical examples show how [he expansion of mercury is taken into account in (1:1.) the CUITt';di01l Of the banJmetric reading fm temperature, (b) the correction foY' the i'tm·f1'Yge:nt column of a n~eTt-:Uii' thermometer and (c) the compensatior: of the rrlefCitn' Pf!t/ . .duium.

Hxampl:e J ~A barometer having a steel scale reads 750.0 rnm. on a Jay when the temperature is 20°C. H the scale is correctlygraduated at O"C., find the true pl"'e8~(U'e, given that the coefficient of linear ex, pansion of steel = 12 X 1O~ °C-i, and coefficient of expansion [absoJute) of mercury = 182X IO-G per 0c.

Tbe lengtb of scale at IW Q C = 75.00 (I -I- 20 X 12 X 10-11) ern. Density ol mercury at 20°C = ,(1)/ (1 + 20 X 182X W-~)

where p,) Is density of mercury at ODC.

Pres 75.00(1 +20x 12 X HJ-~)Pllg ~

ressurcee, (1 +20 X 182 X 10-1;) dynes/ern •

=75.00(1-0.0034) p~=14.Jtt.5 PGI! dYDesJcm.2

/

vn.]

EXPANS.~ON OF WATER

171

Example 2.-A mercury thermometer, jmmersed up to 30"C. mark in a 'hot liquid reads 230DC. If the exposed stem has a.r:' aver<tg;e temperaLUrc of 50<)C., calculate the true temperature, gwen that mean coefficient or expansion of mercury is, 182 X 10-(> per "C, and coefficien t of linear expansion of glass __:. 8 X 1 O-~ DC-~.

Coclil£:i en 1.. of a ppflrent expansion of mercu ry = (182 - 3 X 8)10-& = 158 X 1O-(l =c-i.

Hence. the exposed stern, if at the true temperature t~c., would occu py a lengt.h (l:3Q - 30) I I + {t- 50) 158 X 1(1-'1.1].

t - 2300 = (2.30 - (0) (t- 50) 158 X H)-il,

when t = 235°C.

Example 3.-fn a mercury pendulum a steel rod of length l em. at ODe -supports a glass cistern ccntaining mercury .. Find the height to which mercury should be filled up in the cistern for perfect compensation of the pendulum, given that the linear coc:ffitient of expansion of M.ee~ a = 12 X 1O-~. linear coefficient of expansion of glass g = 8.5 X W-(f, cu brcal cOt'dfici.en t of ex pansion of mercury m ~ I .82 X 1 0-'1 -c-i,

Let h be the required hcight of mercury in the cistern at O~C, V the volume of that mercury and. A the cross-sectional area or the cistern, both at One. Due to the rise of temperature to t"C, the volume of mercury Increases to V (1 + mt) • the cross-sectional area of the cistern increases to A (1 + 2gt) and therefore the heig-ht of merCoury mcreaacs to

V(l +mt) . ') .'

;'1(l+2gt) = 11(1 +mt-~~n·

Since rhe centre ~r g-~'3.ViL'y of mercury at QOG is <I t a hei~ht h/'2. Irom the bottom, It wlll me to (h Iz) (:1 + m~ - 2gt) at t~C, the mcrease being (h/2) (mt- 2g". "I'he increase in. the length of the steel rod at l QC is led. For pcrfect corupens arion these tWO changes m nsf be eq ual. Hence

~ ·(mt-2gt) = '(l.t.

2« I = ~2.!.2x 10-11 I = 0.1451.

m-2g· (132-17) X 1O-1I

22. JE.:ll:(l<aDsion €If Watel.- It is WEU-known that the expansion of water is anomalous in the xegion 0 to 1·<:lC. Several workers such <I';; Hope, Despretz, Matthicssen, Joul,e and Playfair and others, measured this expansion ca.refuUy. A constant volume dilatomerer (sec, 16} may be employed for this purpose. If the dilatometer is made of ordinary glass some mercury is initially put in it to compensate for the expansion of glass. Since the expansion of mercury is 0.000182 and of gla~ 0-0000255, a volume of mercury equal to one-seventh of the volume of the dilatometerwill he required for compensation. These e}{pe~i.me.nr.s shot .. , th.'i.t when water at. O°C . ill heated it ~oes On ~ot;'rractmg 3[0 long as the temperature IS below 4°C_ AbOVE 4DC It

Or

172

THERMAL JE.XP A:>l'SION

[CHAP.

expands on heating. Accurate experiments by joule and Playfair show that this temperature of maximum density is 3.9SoC. This anomalous behaviour is usuallv explained on the assumption that. there ~ise three t~f(es of molecu.1'e.:s H20! (H~O)2'. (Hj!Oh whi~ have differen t spenti.c; volu \11 B& and are mixed in different pro portlOm at dlffereut temperatures. The total volume occupied 1.5 assumed to be rhe Bum of the specific volumes, though there seems to be little . i usrifica LIOn fOI" such [I n assumpdon,

PRACTICAL APPLICATIONS OF EXP A NSION\

23. The expansion of solids and Iiquids is of gmat importance in OUr daily life and its cvmequellCe$ have often to be borne in mind carefully. The student will be familiar w:i~h most of these from his elemcntarv studies, Thus ie is well-known that allowance must he made for expamion in the layin$ of railway lines and the erecting of steel LtidW~5, the contraction ot metal tyres on cartwheels etc, The expansion of the steel scale must be to) ken j n to account In readi n~ the barometer {sec. 2I., 1£umple l~., Similarly the cxpansinn Of Il1ercul'y must he Iound out fur obtaining the true tamperature from a mercury thermometer (sec, 21, Example 2). Expansion in optic a I and electrical apparatus also rauses difficulties. 'The mirrors of reIkcl.ing telescopes which arc very accurately figured 111l1~t be pw, tccred from distortion of their surface by expansion of different purtions which may be at different temperatures. The inductance of a coil depends upon its dimensions and therefore changes wlrh exp:m. sion of the coil.

In dc:aling with glassware it is particularly important tu remember the consequences of expansion and contraction as the gI<1s~ is likdy to break when subjected to sudden dl<!I1ge~ or temperature. This is because gl a~s Is a poor conductor of heat and the diffe.:re.:nce in tern. per<l t me he tween the di ff cren t parts causes U ncq ual cxpan sian. Hreakage is avoided by either t:houslng thin glassware or choosing g-la~.~ of small co-efficient of expansion and high thermal conductivity. Fused silica vessels can he heated to white heat and plunged safely into rold water, while pyrex glass can be thrust inlo a blowpipe name suddenly without risk of fracture, Platinum wires can be sealed into ordinary glass (lead glass) without anv ri~k of a crack developing because platinum and glass have practically the game coefficient or expansion but a copper wire wm.:dd cause cracks to develop due to tinequ ul expansion,

24. Compensation of Cloc:u Olod Watche:s.- For our present purpose the pendulum of a clock may be treated as a "simple peuduIu_m" with ~ bah of n~gIigible dimensions suspended at the end of a 'tV-Ere of 1U:gl~gib~e mass .. The time kept by the: clock depends upon the nme of uscdh~on of rts pendulum which, i:n the case of a simple pendulum, vanes as the square root of the length of the pendulum. The leugth of the simple pendulum is the distance between the point of S'l.lpporl: and the centre of gravity of the bob. Thus if this length

vrr·l

COMFF.Ni$ATlON OF ct.oGKS AND WATt;IIES

173

increases in summer due to expansion, the time of osciflatinn will increase and the clock win lose time. If the length. decreases due. to rsn of (,('mperature, the pendulum swings faster a.llc~ the dock gams. Therefore unless the pendulum is compensated ag,8:mst the effect ~f expansion the clock. wiU gain in winter and lose in su.mme-r. T.~11:i compensation is bnmghL abo:ut by the ll~e of tw'Oexlnnslbl,: mater:~"'-h so arranged that the e;xpanswn of one 18 oornpensated by the expan . sicn of the other.

In the g;t!:diron pendulNm alternate rods of steel and brass are counoctcd as shown IU Fig. II so that the steel rods expand only downwards, and the brass rods only upwards. It is so arranged that Itat = l~ where II and l:!, arc the total lengths of the steel and brass rods respectively, an~ "':I., '"2 the respective c~. effictents of linear expans1On. Under these condidons the effective length of the pendulum l"emams corn rant a t all ten~ p eratures and the pen d ulum is corn pem:'lte~. It w III be seen that 11!If! = ~/ 0.1 ;::::: 3/2 approximately,

In the mercury pendulum a long steel rod carries, in place of the ordinary bob, a Irame fitted with two gla~s cylinders containing ~ercury_ ,Colnpensatiun i~ obtained by the expanSIon of the rod downwards and tho e l:xpa:mion or mercury upwards, (See sec. 21, Example 3) .

In wat['hes the rate of movement is governed by the osci 11 a tion of a small fl yw heel caned "the bal ance wheel which is itself contrnlled by a hairspring. The time of oscil la lion of the hala~ce lV.heel depends Fi~. n .--GridLfOll

u pon the s ti ~l'n ess of the hair-spri og and tb e penduhem,

moment of inertia of t.h!: wheel about its axis of

oscillation. The moment of Inertia depends on the diameter of the wheel and Is mainly contributed by the three small we~gh~s (Fig. I~) screwed on the rim of the wheel, A rise in tl.:mpe:rature 'weaken~ the hair-spring and Increases t.he diameter of the balance wheel. Both these changes cau se the oscill a nons to become slower, th e former eflecr being more important. Te effect compensation, the rim of the balance wheel is made in three segments of a bimetallic strip with brass on the outside and steel on the inside. and weighting the rim Willi three weigJ1 ts as shown in the figure. Due to the larger expansion of brass the end of each segment curls inwards when the temperature rises thereby reducing the moment of inertia sufficiently to compensate both for radial expansion ami we<lkenillg 'Of the hair-spring. The prc~i5ion watches such as chronometers are u~lJa!ly provided with rmupensated balance wheels. Invar steel is now frequently used in the manufacture

Fig_ 12.- 0:JmllL'Tl:!j~ted balance-wheel.

\

\

174

rCHAP•

of pendulums and halance wheeh on account of its 'Very small eoelfident of expansion.

25. Thet.moshds.-The property of expansion is ofren utillsed lor

l CfJn~ tl'ucting thermostats, In these the

. A tempera ture of any su bstance can be kept consta nt fl)r a long time. For teruperaruees uptn 100'0,(; a toluene thermostat may be used" bu:~\ro!· tetllpera. tures it bove ] 00 °C, a blmeiaii,lc thermoregula tor ]8 ~nenl.U y used. These willi now L{~ described, r

T Toluene Thermostad.~A toluene

thermostat is shown in Fig. 13. In the bulbs T there is toluene, a Icohol or some other liquid having' a l;1!l'geC'(rFig. lJ.,-Toiuene Thennoatar; efficient of expansion, These bulbs

are immersed in the bath whose Icmpe:tatute Is required to be maintainedconstant, In case the temperature of the bath increases the toluene expands and forces the mercury {SJI(JW1:~ black ip thefigu~) up the. tube in C and thereby doses the Opf':nlllg lead mg from A to K The hath. ill heated bv 11. hum~r and the ga~ feeding this burner i~ sUf;lplied through A an? ihi~ opcrnng.. . Th us, on account, ot. the ex panswn tb. ,r= gas. supply IS d·e·· (Teased and the temperature Ialls, If the tempcratW'e of the bath I aH~ too much, toluene conrraets, the opening is increOls.ed and ~[lS ~Llpply increases, By adjusting the amount of mercury in R the tcmpenmrrc em be kept O)lJ1s~aI1t at anv desired value. In case of eh~ .. tri ell 1 hea ti ng sn ita ble electrical contact can be arransed iii bove the m~n:,uTy level Ior switching orr the heating current. 0

Bimetallic Thermo-Regulalor.-The Dekhotirul(y bimcrallic thermo-rcgulator is shown in Fig. 14. it consists of a compcrmd 1;[l'ir R.

which 1S made by welding' to- <1W

ge ihcr brass and invar steel, '

The strip is wound into a small

helix and is connected by R p

means of the rod P to the con- D

tact maker C which makes 01"

breaks ~11e electrical circuit of

the heater l-I. When the tC111- ~" ~

pe1'atmc rises the expansion of ~.'.,-

the brass causes th8 helix to H'

MJ!.lN9~-""""'P--·-~

unwind and there by the con" .:______ __ ~ . .-

tact ate is opened thus break -. ....

rng the electrical circuit, Witb Hg, 14--Tbc Binietalllc T.hermo-R{~!.lli\.toL

fail In temperat.ure the helix contracts and thus. contact is made .;;J t C thereby completing the elecuical circuit. '¥itb this apparatus remp~ratuI'(~s up to 300~C. can be maintained to within -t-J0C, for a long time.

VII,j

:i!:XPANS.~ON OF GNfE8

lifo

EXPANSION OF GAS.ES

26. Expanslofi of Gases.- The expansion of gases torms the very basis of the system of thermometry and the perfect gas scale diliicus.sed in Chap. I. As ~ tated tht:rc the results are best expressed in the form of Charles' law which holds rvery approxhnaeety fur the so-called perm ancn ~ ga:!ics in nature" Here we shall describe the experimental methods of determining the coefficient of expansion,

I~ the case of ~ases it is Deceg.~:ary to dist.inguish beLwe:n t wo coefficiems of e~panslOll: (1) the volume ()()effic:lenc of expamlon t"I: at constant pi'CSSu.re. and (.2) the ptCl;tlut(l coefficient of expansion .(3 ~'H constant volume. The volume coefficient of expansion is defined as the increase in volume of unit volume at O"C for each centigrade degree rise of cernpeJ.'aUl re iii t constan t p.essute. Thug

V-Vii

(L =~. (25)

where V and V ~ denote ~.he volumes 0.[ a I.1xcd mass of gas at to and O°C. Or

(2G)

If U1.e volumes at t.emp£rnwrc~ tl and t!! are ~\ and V2 respcctivelv, we get, wi th th e hel p of (26).

(27)

vVe can thua deterrnine j, by measaring the volume of a fixed mass o r ga~ at two temper·atures.

Similarly the pressmt" coefficient of e. x pansion 0.[ a gas is defined as the in:c:rtl:;)~c in p~e~~Ul-e, cxp-[e.li5e.d as. a fracrion uf the pressure at O°C. Ior onece'llUgrade dcgl"ec rrse of tr::r.ape[atu.re when a fixed mass of the gas 1$ heated at constant volume, 'Thus if p and Po he the pressures at to and w'e we ha\'e

~ = P-Pll . (2~)

p~t

Irom wltich telatious analogous to (26) and (27) can be deduced.

. 21. IlxperilDJe<DJtaldetfl'nlmatioD of [he- Vobnne- wefiicl.eut of Expallc-

Sloo:.- Gay-Lussac was among the earliest to measure the volume coefficient lI!Cl:ur~tcly. RegnauH .us.ed an improved form. ?{ apparatus and correctedhis n~'5'LL]t~ fOT Y[:InOuS sources of error. F~g-, II shows a. laboratory RfnilnbT"Clnent. for determining the volume rnclfic..ient and crnplovs R.egnaulf8 technique in a simplified form,

, T'he bulb A. h connected by 1:1. narrow gla.ss tube to a cafibrated

Iimb R ot a metCUTV manometerwhose other Iimb C can be moved H P an Q do~\'n for ad] usting the mercury level in B. The tap T enables t!:I![~ quanLlty of W1s in A to be adjusted. First the bulb A IS put in it cord water bath at !to, and after it has acquired the temperature of the lJ,'H .. h, the tube C is adjusted until the mercury stands at (he same level in both arms, and the mercury level in G noted, Then the

176

TIi:ERMAL EXPANSION

[ CliA1'.

bath is heated, when the enclosed ail: expands pushillg the mercury down in Rand u'p in C. The bath is maintained at a certain tempeTatun: and the tube C lowered to brine :JH~ mercury J evel at the same heigh t m Rand C, and the volume of gas in .Bread from the gradua rio ns , The prcxe.lis i s repeated for" (:lve.['y 2'(19 rise of tempe.l:'atul"(: up 10 roo-c. and the observed readings ate mHi3ed for cal-

culating (Jri from (~7). \

The results are best treated bv ploHing the observed volumes agains't temperature on a graph. It is found that all the points lie on a $tra'lght line showing that. equal changes in ternperat.ure lead to equ 81 cbauges in volume at constant pressure. Thi~ is Cluu Ies' law which maybe form all y stalled: for a fix.ed mass Of gttS besued. at COr1;l'tant tn'essul'e~ tIle vQlt~m,t::: it~. creases by a constant fradion. of the volume .at Goe for each ct!ntigrade degree rise m ternjJlJrutufe. This also follows from the result that a! comes out to. be the same whatever values of 11 and t2 are utilised in (27). Results further show that IT = 1/273 (nearly) for all the so-called permanent gases,

For accurate work corrections must be applied for the foUovo'irlg sources or error:- (1) the gas, it! the narrow tu be and the ma nome rer i~ at a ditlerent temperature from the bath, (2) the expansion of the gl.a:;s bulb with rise of (em perature. Regnault applied corrections for these and found that. all real gases showed small departures from uniform expansion a~ld t.h at tl:e codl':id eut of cxpan sion dlfiered slightly from One gas .0 another.

28. Ex.perlm~nf.m determiuati.on

of tber,e&SlIn 'Coeffici.enl iii! E~Q" ,~lmn.- The pn's.,~llre coe-fficie-nt can beeasily determined in the Iaboratorv 'with ~he hel p of an a P pllTa tus J.::no~~rn as Jol1"!; apparatus, It OOH515ts of a /!lass h.ulb A. of about

J 00 ct. capaCIly, which is filled with Fig, 10.-Joly's apparatu~

dry air and is connected by a glass :for determining pressure r;(:Jeffieient.

Fig. lS.-Apl,larMLl5 fur rlJe:aSIJT;n,~ '''(Jli;im~ coefflclent.

YIr.)

PRI'$llllE COEFFICIENT OF r.x.pl>N310N'

177

capillary tube to a mercury manometer mounted on a stand (Fig', 16) . _A. fixed reference mark X is made 011 the tube B near the top bv means of a file, and the mercury level is always brought to this mark by adjusting C before a1'1y rea.ding is taken. This ensures that the volume of the enclosed gas i~ Kept constant. A metre scale S is bed to the vertical stand to read the difference h in the levels of mercury in the two, tubes Rand C. The bulb A is immersed in a water bath which is well stirred, and tempt:l"atures are read with a mercury thennome ter,

F,i;,st the cXl?eriment Is do?e with ~ld water in the bath and the difference h In she levels of mercury ill the two columns noted. If the barometric height if; N, the pressure of the gas is J-I +h depending upon whether the level in C is higher or lower than that in B. The bath is then heated through about 20~, headng stopped, and. the bath wen stirred. The mercury is again brought to the reference mark and the level watched carefu lJy. 'When the level b ecomes steady at the reference mark, the reading in C is noted, Heating is then resumed and readings are taken in this way at inte-rvals of 20~. 'The coefficien t of ex pansion {:J is then calcu la ted from the rela ti on

p-" f)~-b_ (29)

A'2-P~t1

FOT accuraic work various corrections are necessary. The most difficult Ion estimate is the "dead space" correction (p, 9') since the exact h_'111peratllre of the gas in the capillary rubeIs not 101(I"",n, The expansion of the bulb introduces all error In f3 of the order of 170 : this can L~ satisfactorily corrected for by adding the coefficient 01 cubical expansion of glass to the observed 'value of 13. Experiments have mown that p is J'airly dose to 1/27,'1 for all the p~tmaf.lent gases w hich means that for a fixed. mass of an y gas heated at constan t volume, the pr-essUI"C increases by 1/273 of the pre5:;ur~ at ODe for each centigrade degree rise in temperature,. Accurate experiments however show chat this expansion is neither uniform for- a ..-as, nor

is i t exactly the same for all gases.. o

As mentioned in § 7, Chap. 1. these observed deviations 'of a: and f3 from the correct value 01 1/273.H:i- are really due to the deviation of actual gases from Boyle's law, Let a fixed mass of perfect gas, whfch fiy definition obeys Boyle's law, have the pressure /Jo and volume t.'o at. OOG, When it i~ heated to tDe, the product ol' pressure an d yo Iu me ca n be wri Hen a, p~v~ (.l + at) or Pov~ (1 + fit) depen J.ing on whether the pressure is kept cunstant or the volume JS kepi constant. Since these pmduCLsmlJ]~t be equ:.tl by Boyle's law, we ge.~ .~ = f3 lor a perfect gas. The expansion coefficient is experjrncnrally found to be 0.00,%608 for aU gll.ses provided they are reduced to the state ot a perfect gas (p-;.O). The equnlity of a.: for all b'<l.s:es is really ... consequence 01 the kinetic. theory.

noah Recommended

A Dictionary of AppUcd Physil:S,. Vol. 1.

L Gla7..ebrook: pp. 872-900,

12

CHAPTER V.U[ CONDUCTION OF HEAT

I. M.et.hods of Heat Pr~pEl&atioI!'- When a bar of: me~al is heated a~; one endand held at the other by the hand wu f~I the sensatinn of heat, Heat travels from the hot end along the bar and pfoduL-e:S this sensation in the hand, The- rowel;" of t.ran~miu:il1g heal ill thi~ manner ~:s possesaed by al ~,8U batances to avll.[Y i ng degree and this p~lenOm~no!t ts called CondudlO1l of [-l(1(1,l, In the pwcess of C~mv~ct~~m~ heat ].iI ~ransferred by the actual motio'l1 of heated partides ol' matter whether liquid or gaseou~. This i~ hest jllu.m::tt.cd bl' p!a:,citlg gen,tly some crjstals of potaR5ium petTn~~nganate :iI.L the bOl.t!H]l of a beaker con~ raining water and h-eabng jt, Heated water risesup and curls down forming a closed path whkb is rendered visible b1' the red CO]Ol1T imparted tothe water. In eenduetion, heat is teanslerred by "contact" and r.bel'e is no apparent transfer 01' mauer.

in boch the :;J. bove PH) cesses the interven i 11,g medi um ta tees an adi\'e part 111 heat prop'1ffation, but in addlnon to these there is anothei'Pl'OCft~~ 111 1,,,hi,'h Lhe intervening medium takes .. no pim. If we ~tHn~r near a coal furnace, we feel the sensatron of heat, If we arc .in the SUl1, we' Jeel W:Unl" Hen: the souree of heal; is the coalflTl'11aC(~ or the sun, and ill the latter case it is at all enormous distance frolll us, There h absolutely no material medium between us and the ,,1111, srill heat from the sun enntinues t.tI reach U~. This phenomenon Is culled Radial ion, The processes of conduction and convection are ucccssarf ly dow due b) the action o] the intervening medium while radiation travnla wit,h the cnnrmnus veiociL}' uI light. In this chapter we shall cr)usi 1 ret the c;t:! 11 duction of heat,

2.. Conductivity (if mlhrenl Kindl! IIfM:aUer.-,COlllllWll observations ~how that different substauces vOIr), enormously in their COn· ducting power, A gla8s rod can be melted in a Hams by holding it at iii. point two Or three in.ehe~ a.way Irom the Game, while a copper rod under ~imiIOlr comlidon.s becomes too hot to touch, Copperi8 thus OJ. better conductor of he~t than glass, Metals, in ge-neral, are good coruluctors or heat., glass, wood and other ncn-meeals a1"£ bad cond u c con. Hold inside a flam e two blocks, one of wood and dl'~ other of ~()pper, each covered ~vil:h paper. The paper covering the cnpper blorl: ]Snot bm nt, for heat is rapidly conducted aWffLY hyooppcr and the temperatuJ"e does not rise to the ignition poiJ],t. The p~lper covering tha w()od i~ hmnt,. Similarly, water rn:ay be boiI~d.b1 a r.l.lp or

p<lper fat the heat ~s taken up by water (oomrectioIlJ. '

Liquids, in £,~nend, <J re worse cond ucters of heat than solids and gfIJsc~ fire dIe WOl __ ~~. A very simple eX[l eriment ShOW5 that "W'" ter is a "!'''Cry bad totldu,etoT of hean, Take some water ira. ;L test-tube and sin\:. in~.o i~ ,a plec~: of ;ice bywefg~ting it: The W.11te:1:' at the top can be boiled by heahng It Io cany w hile the lee at the boUo[llJ does not evert

ViII,]

melt. Ail' and gafiCS in general, are even worse eonductors dum water. \lVoolen clothing protectsu~ from cold on account uf the fact that tt conr .. ains air in the interstices which renders 1 t a very bad conductor of hea to

The good. conductivity 01 metals !,S utilised in. the construe Lion of the D a vysafety Iarn p. The Ilame is enclosed in an iron gauze chamber (Fig. 1) and CHI be taken down a mine. Any combustible gas, if pt(d~cn~, comes In. contact with the naked flame and uurns imide (he chamber, But the irQl'l.gauz~ CDn· ducts away heat so quickly that. the tempe]l"EUUre at .my polnt nl'it does nut rise to the ignition point and the ou tel' gas does nut Ignite.

3. Deiinitron Q{ Corumdi\1i~y.- The Iimto give a precis-e definition of conductivity was Fourier who in his memorable Theori« An~ly~tqtte de fa Chaleur (1822) trf"aCed the subjece of: heutconduction in a Fig.. !~Da.vy masterlyw1ty~ and. placed. it on finn mathematical Safety Lamp. basis. \V'e shall fint d.hcuss the flow of hr?at inside a

bar heated at one end, Consider a thin w:J,n of the material with parallel j'~M~il:S such that heat flows in a direction perpendi,wlar. to the faces. Let fh, 61~ be the: tempentWl"eS of the two £a(es, l the thickness of ~he wall, A th ~ area of ell clI. tace, then ] ~ can be shown ex perimentally that tbe amount of heat Q [towing through the wall in. :l ~f 111 ~ t, W h<::nwe" tc.;mperatn n: at every p()int _ ~:f~he bar is swady, '~,~lr~ctl]' ptaportlOn"l.w ~~) Ot~e2' (~;) t~e area A of the. surf~ce, (~H} tID(' time t find (w) inversely proporuond to r.,~hat IS,

Q. = leA 01 l02l, (1)

The ooeffk1ent K lS a quarnt,itydepending upon the nature 0.£ the substance and is called its ~her1i1'H~~ con au ct t1.l'ity ,. !From this relatioa conductivity mOlY be clqfined as ~h(f qu.tl11Jil;y «: heat {lmving ~7' ..'il'i'COIHl~hrough a tmft mBa (If plate Of Nuit thidmess, when ~he dffjerc'l'w: Qf~emp(J1'att/,re bet1Vt1tm the faces is unity, In ana]pgy' with the electrical resistance, the inverse: of K may be called the Ihennal resistance of a unieeube.

N(l~" imagine the thickness of thl£" pllllteto be dhlllni~hed indeH.

ltel Tl l' .". f til-!\!2. . O~-el " de . .:iI -,1

nite T. ne : UJ:lw.ng Vll,Ue 0 or - --, - 13, _. -. anti uenotes

l I dx

[he temperature gf;icHenJ at "ny point. The minus $ign has been.

used hefnrc ~ ... t1 because the symbol d a]w<tys stands for tile :incI'C'nSf-.

a:~

Tlcn ce, the quan ti ty of heat 'QHow ~ng in the pnsilive direction of x ir~ time df across ~h.~ isothermal surface o,~ area A at 1I0y point x i .. given by

Q .,.. dR,

=-n.A I. cd. ~L\'

(2}

180

CONDuanON OF H;EA'l'

[CHAP.

This equation i.s of fundamental importance in tbe theory of heat conduction. The units in which conductivity is measured In the C.G.s. system are the calorie pet .~eCDnJ. per ~quare centimetre of area tor a temper a ture gradient of 1 "C, per ern, [caL cm.-1 sec-1 "C-I}

CONDUCTIVITY OF METALS

4. . We shall now give the vatious methods oE dete1"mj nin g the thermal conductivity of metals, Methods I to III employ ~tationarv beat-How while in I V a stationary periodic flow of heat is used ..

1. CONDUCTIVITY FROM CAL·(lliIl!.'lIr:nHC MEASUREMENT

S. The definition ol conductivlty from equation (1) provides a simple method of determining the conductivity of a substance. "Ve need have only a slab of the material of 'kuown cress-section heated at one end, and measure the amount of heat that ftow~ out at the other end in a known time, as ~,~'~ll as the temperature. o[ the 1;111'0 faces. Tbus an th e other q uannues except K In eq ua non (1) are known, and hen ce J( can he evalu a ted.

The rnetho (I though simple pres.ant~ considezable experimental dillicultfes. It is difficult to measure :ac~mate1y t.h~ tet~. perature. of the two faces of a slab of metal, This IS best achieved uy kcepulgembedded in the surface the junction of a thermo cou ple, the use ~f mercury thermometer or resistance thermometer beIng inconvenient or impossible. Some early experimenters used steam to heat the :Jllb at one end and icc or water to mol it at the other end, and assumed that the temperdture of the end races or the slab was that ol steam and wale! le!;l;lectivel~·. But i! proper precautions be not taken, the method some LImes gi,'es absurd results, This IS on account or the fact that a thin film or fluid always at rest, is formed in contact with the surface, and this has 8 large temperature gndient. Hence it is essen ti al that we should observe the tem pera ~HrC inside the sla b i (Self by IOean~ of thermometers. There are many apparatus based on this method, anti oue due to Searle is described below,

Fig-. 2 s~ows the ;:t,pparatus diagrammatically, One end B of the rod AB IS enclosed III the steam-chamber S while the other end A I~ro,~ct3 into another chamber C through which enid water circulate .. as I~dIca ted, the te rn pera tures a. t en ~ry and ex! t b ei ng T ~ and T 4 respedlvely ', T~mperf.ltures at. two pornts 3Jong the bar are measured Ly thermorn e ters T I a nd T ~ , let these be T I a nd T ~. The who fe i"od is wrapped T'OlJl1d with some non-conducting material like wood. felt, etc, In rhc stea dy sta te U om grams of wat.eT flow past the cold end ol the bar pet' ~er.ond, the heat conducted by the bar per second is

T.-T

m(T.4 - T~) and thi s equals A K 1 d 2" where d i.& the dist ancc

between the thermometers T., T~" Th.U8, the ccnductivlty [( is detennined.

In the foregoing experiment some heat was lost bv radiation from the sides of the bar, This is a source of error ~l1d is very

\

vrn.]

181

OONDU(. rt 'rvrrv FROM CALORIME"IRlG MEASUREIYfENT

easily eliminated if the bar be surrounded wiLh some material at the same temperature as the adjacent portions of the bar. There will be no now 0 f hea t perpendicular to the length of the bar as no

r; to".

1

~M!TI

'. t i------.....,

- B

ls4

temperature gradient exists in that direction. The surrounding material is caned the 'guard-ring'.

Bel"get, utilised this guard-ring' method [or determining the conductivity uf various substances such as copper, iron, brass and mercury. A vertical cylindrical column of Dle1"Cury is surrounded ~Y ~n annular ring or m.ercnry. In both the upper surface of mercury IS heated by steam while the lower surface r~sts on a metal plate· cooled by H~C. Thus the temperature gradient as well as the tern pe1'1I. tures at the same level in the experimental eolu rnn and the

'surrounding annular ring are identical, Under these coudttions there can be II 0 lateral How of heat and the annular ring' serves <'I S ~t 'guard"rillg·. The lower end of the experimental column projects lOW the bulb of a B unsen Ice-calorimeter and the heat Hawing nul; at the lower end is found from the indicarlons of rhe mercury thread, Tb~ dHreren~e of tempetatu~~ ben~een several points along the ~[)lu.n:n 18 determined by (our .differerrtial thermo-couples. The conductivity J( can be calculated from. formula (1).

This method has been adopted by a number of workers, notably Ly Lees, Donaldson, Honda and Srmidu, and others, Lees used the ~o.d me thod (or rueas'Uring the conductivity of many metals tJuoughout the temperature nmge 18°C to - I7W'C. The experimental rod, about "I ern, IOl1g' and 0.58 ern, in diameter, was hcatedelectrically at the upper end, its lower end being' fixed ~o the base of a hollow, closed, cyLindrical shell of COppE.'l' which completely surrounded the rod. The outer cylinder wag suspended inside a Dewar flask and immersed in liquid air or heated electrically and t!1U8 the desired temperature of Experiment

Fig . .'t-Tlle two-plate system.

182

1't.'1I.S attained, Knov.ring the electricale.nergy spent. in the 11:,eater wire and the temperature at. two rOi,nts on. the rod by plarluum resistance thermometers, the therrna conductiviw can becalculared. Some corrections are however necessary which are difficult to evaluate

accurately, .

Honda and Simidu em ployed the two plate method ~ho",:, II. H1 Fig, 3. P;, P:: are two exactly similar plates made of the expen:m.en~ tal rnatel'ial.Bet.ween these is symmetrically placed. the electrical heater H in which the heat Q is generated, For ,peden symmetry two cold plates, K, K maintained at the same temperature are pl~ca at the other end .. of these plates. Thus the amount of heat HOWl,nr; through each plate is Q/2.

II. Co:r-mUCTIVITY FROM TEMPERATURE MEJ\SUR.l'Jo.fENTINDTRECT METIlO£!

€I. Rectilinear Flow of Rea1. Matllmllatical Investigali;QIlJ.-

Consider a metal rod heated [It. one end,

~ ,~+dO the isothermal surfaces being parallel

Q~=i Ei. Q~ plane;',: pcrp(~ndkular ~o the 1 ength of

il~'hl"'-;:-""'_~ ~~-.I the rod, and '] et the aXI S o[ x be normal

Qa Co these planes. At n distance x hum

of heat ill a rod. the hot end (fig- +) let 0 be the tempera-

dO IO

ture and d." the: temperature brra.c ienr;

.U1d con sider a layer of thickness dx at this point, The amount of J1)

heat QT which enters the layer per second is - KA rf~ (Irom equa-

tion 2), Q2 the heat which leaves the layer at the face x + d.1/: I~

_ KA d (iH- dfJ (D:. ). > (3)

t/x d:t

[]:

,..·0 Heate«

Fig_ 4.-Pluw

since {} + dO. dx is the temperajure of that face. Hence the gain ds:

of hea t by the Ia yer is equal to

to [ d ( se ) l' ..' d~O

-KA~ - -KA- e + -d fix, i=KAJ:i d»,

d.!: dx X "' ax

(4)

Now before the stead]' state is reached this amount of heat raises the tempe.,ratul'e of the layer of thid:._ncss dx, ~et p be the densitv and c the specific heat of the material per untt mass, and let. WI:

b dB f 'h 1_

rate of rise of tempera Lure be denoted .}' d -. The mass 0 r e uytr

t

is {J Adxo Hence, neglecting the heat lost by rsdiation fmjl1 the ~uT'fare. we ge t.

(5)

(6)

vrn, ]

RECT1UNEil.R FLelW OF HEAT

where h = K/pc. Thus h is equ~ to the theml~I conductivlty divided by the thermal capacity per unit volume. ThIS con_stant h has .been caned thermal difrtlsil)it,1 by Kervin and thermometric c01Hl-ua1:.)~ty by Maxwell but the former term i~ more commonly used, It will be seen that the thermal diHos.:ivity h represents the change of .tempera tu re, prod uced in un~ t volu.me. of the sub stan ce_ by the q Ul,lli:tty ~:~ heat which would flow 11'1 urnt ume through umt area unfleJ. umt temperature gradient. 'Thus fBI calculations of the rate ot rtse of temperature the constant h is of greater importance than K as equation (6) shows (as (be rate depends not only on K but also on pc). bur in tile steady state the rate of How of heat depends only on K and not on pc (see equation 8).

If, in addition, the sides of the bar arc allowed to lose beat by radiation, this must be taken. into account. 1£ E is the emissive pOwer of the surface, p its perimeter and () the e~css;l; of. the t~\pe. rature of the surface over that of the 8~rroundlfi~'ll, tim r~(hatlon loss Qs> assuming Newton's Law of Cooling to hold true, 15 equal to F.1VJ d». Hence we should rewrite (.Fi) ,IS

J2() dO

KA d'!"~ 4"1; "'" r A!U.,c fit + EpOdx.

Or

dO d~f) .

dt "-- rl t.b:.".!- - p.f1.

Ep

p. ;= plle-

where

This is the standard Fourier equation For one dimensional flow ot heat and any probl.em in t~l.erm~l oon~ucti(Hl Ol!ong a rod consists simpJy in the solution of this differential cqm:hon.

Stead), State-A state is said to be steady when the tempe:ra-

, df) nWh

hue at e'ic:r~t poi n t of the rod is stationary, U:., dt = ,-". eave

then

where

(8)

If the radiation losses from the sides can be n~g~ecr.ert, this equation further reduces tOo

{1~8

dJf- = O.

The solution of thjs differential equation )'ie:lcis Y=Ax+B,

'" '¥hem the radlatlon IIJ$S term is included as in €qUil.tiun (:7). ~ must ~ measured as exeess over thp. temperature I.If the surroundings. If tll!~ term 1S not included as in equation (6) j (} may denote the actual temperature or the excess over the surroundings,

184

[CHAP

wbere the constants A and B can he determined from Lh~ boundary oonditions, Let these conditions be {I) f) =BD at x = 0, Oil being the temperature of the source; (2) f} = Oi at x = 1, Then we have

O~-(J1. ()= O~ - =r=

whc::rc(} is the remperature at an)l rtrint :I)". . ~

If radia lion losses are not neghgdjlc, the solu ti OD will he rhfferebtt Let us assume tha t in this case {J = eo' is the solu tion, Hence. bv \

&11 hs ti nrtion, '

n2 .= 7n-2; or n = ± m.

Therr:lore, the complete solution IS

e = Ae""" + Be-r= where AJ 11 are constants.

7. Ingeu,.Haa5zts ExperimeDt.-A method of comparing the conductivity of different substances Lased on this solution was employed by Ingen-Hausz ::IS early all l 789 and is generally .<; .. hown as a demonstration experiment, I! .. ars of ditI~rcnt substances are mated

wi th wax and have thei r one end immersed in a hot bath of. oil (Fig. 5) . The wax melts to different lengths along differens bars, Before the steady state is reached the temperature at any point depends on h, l.e., on Loth the thermal capacity and LIla thermal conductivity as Indicated by equation (7). This is why initially the temperature 'Wave is (l bserved to travel faster along bisniu rh 1 han aloIlg ~()pper, for the roW thermal ca p::.t ci ty of the former more than L"Ompensa tes 101' t.he larger conductivi ty of

the latter, \'Vheo the steady state I~ attained, ho,,"'evert the wax is found to melt on the copper over a greater length,

Let ll' l~, .. ,. denote the lengths along which the wax hal. melted on the different bars, (I@ the temperature of the hath measured above that of the surroundings, and (h, the- temperature of melting wax similarly measured, 1£ (he bars are long enough the temperature at their other cuds is the same as that of the surroundings, i.e., (I = O. The complete solution of this problem is represented by equ;]tinn (9)- The boundary conditions far an the bars are (i) () __ 0 at x = 00, (ii) {)=IJB at x=O) Uq 8={ll at :JJ=I.

. , By s.u,bstit,utio~ in equation (Y) wIldi.Lion (t) gives A = 0, Condltlon (H) then gives R = O{l' The solution thenbecomes

f) = 8rf-bli<.

Condition (i!:i) then give~

01 = flue-mI.

8Ll ml = log~e;.

(9}

Fi1;, 5,-Apllar"tu~ of Irlb-e.ll-Hau~sz,

j

(10)

01'

1

.,

,,)II. ]

FOR1!F.~' METHOD

Since log $ (00/ Oi) is the Sallie for aU the bars we have mIl:! = m~l~ = i'nJ;l!l =. +.= constant, which from the definition of m implies that

Kl _K~ _K~ _,' t

_ _ -'-" -= .... _ constan ;

~l ~~~ l..,t

provided _. ~he- dillere~ t .bar~ have fbe same cross-seen on, perimeter and codti.ncnt of enussicn. 'Thus

K P

K~'= 1~· (12)

'Therefore the conductivitie'5 are in the simple ratio of the sqU:lJ'es of the lengt.hs. along which the wax has melte~, _3,ud if the conductivity of one ol the bars be known the conductivity of the others can be calculated, 'This is an indirect method, In order to secure the same coefficient of emis~ion the bats are electroplated and polished.

8.. Experiments Df Degpretz, Wi.e.wD'l<um and Franz.- Desprctz, as e.arly as 1822, compared the oonducrivity of ~wo substances by means of tlm::c rem perarures at cq ual dl st;,mces- '1 he bars wen hea ted al . one end and were provided with a number of e:quidi~tant hol.e~ thro ughout t heir entire length. These holes contained mercury III which the bulbs of mercury thermometers were immersed for recording the temperature, The theory of the method can be worked out

with ~c help of equation (9)" , ,..

"'hedemann and Franz following the l):tIDI:! principle devised a more accurate apparatus. The Lars under test were about half a metre Ionsr and 6 mm. in diameter and were erect.topIa.ted, One end of tlJe bal was heated by steam and the remainder sUl~][~lInded by a constant-temperature jacket. 'The temperatures at equidistant pomt,~ were measured I:l~' a sliding thermo-couple which could he manipulated from outside.

(11)

Fig, 6,-FL)rb~s' apparatus, Statical experhnent,

(The d9Ucd C1;!n'(~ shows fall of temperature alot\.~ the bar and tangent to the curve gives the temperatura gi"a.c'l\ent)_

186

[CHA['.

CONm:c.'fION OF HEAT

III. CONDL1C'fll1l'I'-V 8Y A COMBINATION OF TUE STEJ\DY A~D VARIABLE H&\T FLOW

9. FQJ'oe~' Mdbod.-One of the earliest methods of determininz the absolute conductivity of a substance Is rhat due to ForbE$.~ Though simple 111 principle, it is exceedingly tedious in practice. Forbes used a. bar of wrought iron 8 (e. long and ]1- inch stlu.ire: section. One end of the bar (Fig. 6) W<lS heated by being fixed into an iron crucible containing molten lead or silver. A number of thermometers; with, their bulbs immersed in holes drilled into the bar, were employed to indicate its temperature throughout its entire lcng-th, After about six hours the temperatures at all poin'~s become steady and are read on the thermometers, The temperature disu-ibution is indicated by the dotted Iinc in Fig. 6, and follows the law () ={)!I~-m:<, This is called [he statical expe~·im.er~t since it deals wjth the steadv state of hear

~ow. .

To obtain the heat flowing across a particular cross-section, Forbes determined the amount of heat lost by radiation by the portion of the bar lying between that crO!!8-,~ection and the cold end. Theile two quantlties are obviously equal in the steady state since 110 heat flows out from the cold end, this being at the room temperature. Forbes achieved h. by performing the d·ynamical experiment; 80 caned because the temperature in this case is changing. For this. purpose a bat only 20 inches long but in all respects e..'Cact1y similar to the previous bar was used, First a. high uniform temperature is communicated to this bar which is then allowed to mol ir~ exactly the same surroundings as the statical bar, and a cooling curve plotter fur iL (l~ig. 7). \

I et us now calculate the amount of heal lost Ly the statical liar from the poin t x = Xl! to [he end of the bar (x = l) . The amount of heat lost per second hy radiation from the surface of the bar from x to x + dx 111 til e st.eady state, is

de -AdJi',pc -d ' t

where p is the densIty 01: the material, c its specific heat and _ dO fit

the rate. of ~ooJing of that dement. Hence rhe total heat lost by the purl.l{)U of the bar from X = ;\:1' to ~ = l in a second is

of< Jam~s David Forbes (1&l9·1868) was 1Proie~sDr of I'o.Tatl.lrat PM1~soph:r in the Unlversity 01 Edinburgh from 1833 to 1800.

"JILl

137

CONDt;C rrv ITY BY PERIOple f;'WW MEnIOD

.• -1

jde

-Ape -. ds: dt

'This will also be equal to the heat ,crossing the surIace at x = Xl~ vi.;."

-KA( drJ)

. . dx ~. '·:1

since the bar is long enough so that its other end is at the room temperature and 'hence there is no loss of heal from that end. Equatingthese two quanrities we have

=t

}• de

= ~d dx,

. f,

(13)

F I 1 - dO 1 d 'I ' . I d

. or ca cu <lung tit t re . yllattliLa expenmentis per orrue on an

exacrly similar specimen with the same exposed surface. The observations are plotted in j'jg. 7 which is self-explanatory. The 8, x and e. 1,. curves 1Ire drawn [tom actual observations while the values

f dO..;). • 1 I . h

a· - tit corrtsJ:lonutug to vanous V<I ues oi 0 are computed [rom t e

(J, f. curve and plotted as indicated. Equation (13) yielcb

II

- tan .p=F, pc

where tan .q, <Inc! Fare indicated in the figure, The area F of the shaded portion can be measured by means of a: planimeter and hence ]( calcu la ted.

Tl~ ere a re several sources or error in Forbes' method and hence the method £"118 to give accurate r~81.11t<;. The specific heat does T.W~ re-main constant at different temperatures as assumed oy Forbes, Further the: distribution of temperature inside the hal' in the statical and dynamical experiments are different. Forbes' method bas been rmproved by Callendar, Nicholson, Griffiths and others.

IV. CONDUCTIVITY BY PERIODIC FLOW METHOD

10. Angslrools Metilu:ul.- The conduclivjty of a metallic bar can a]go be [oll~d by pel·jodi.cally heating and cooli~g a portionof the bar and observing the temperature at dilIel"enc times at two points along

the bar. This method was first employed. by ..:\ng8nOm~.

111 his early experiments a small portion of the bar was enclosed in achamhe:~ through which steam and water at any til::mpctature could be a lternau-ly passed, In Ia rer experimen ts the end instead o E the middle was heated. Tile bar was heated For 12 minutes and cooled also for the same rime, the periodic time being 24 minutes. Tempera-

'* Ai,d("Fs Jonas .!'q~gstl'fun (1814-18"74) Was Pn)fesso, of Physics at Upsala, He made Important researches in h(:at, n~aID1(..-tlsm and optics,

188

GONouarrON O~ H~AT

[GHAP.

urreswere observed every minute at two points along the ~ar by means of two rhermocouples, The mathematical analysis of this case is somewhat eomplicatcd and 1i~riU not be given here. IN'e have to solve equation (5) such that the solution is a periodic function ot

time. "

II. CQoiifuclivily of the Eal'il:h's cm6t.- The periodic £IO\'!" method is yery suitable [or hnding the conductivity of tl1e earth's crust, The earth's surface Is heated hy day and cooled by night. 'This :i1temate heating and cooling effect travels into the interior of the earth i'il, the form of a heat wave (diurnal wave) and gives rise to the diut~tal var-iations in temperature at points inside the earth's (;["U5t. Again, the earth receives a larger amount of heat in summer than in wirucr and this causes a. second heat wave having the period cue year (annual w.we) which i~ also propagated :into the interior of the earth. Assuming' the w.aves to be simple harmonic as a first approximation (tbe annual wave, in paruicular, departs considerably from this ideal ~tate). let us find how they travel into the earth, The problem 1.S that of a bar ~eri od icall y heated and cooled at one end and. provided wi dl a g1larCl-Tin_g; ({L = 0.).

A simple harmonic solution of (6) 1$

(J = Vllc"."" sin (wt+,6.x+y), (14)

which gives the LCmperaturc fluctuaticns ill any point x, This is the equation of a damped progressive wave and is graphically represented in :Fig. 8. The wave moves forward with the velocit)·

X- (.IJ /fJ while it;; amplitude go~s on d i minishing exponen ti ally (g:lyen by Ooe-o::.k) which is

Fig·. 8.--Tempe:ratt11'e wave at a particular Instant. shown by the dotted

curve, These fluctua-

ti?n", will ~e ~.uperpo~ed 011 the mean tempera Lure at an}' point which will also diminish as we go farther from the hot end.

r~ can be, ca:si;ly seer~ that the y'?a"(}~-length of the f.e-mperatu'!:"ewave IS Ii. = - 2-n- 1f3· Ag<un, by substituticn Irorn (1·<[.) in (6) we get

l~l A

h=-- =--

2W 41.rT

lIence a==~t~!h~.

)l" Ow if a n urn ber 0 f thermometers are embedded in t 11 e earth .. iet . different depths,. rhe progress of the temperature wave inside tl~e e~l1-.th can he Investigated, find kllOw:ing the wavc-Iength, the dI.ffusmty hcan ~)~ calculated fm~ (l;'i). In the same way we can find .th~ COl1dUCUYlLY of any bar If ,~e heat one end in a simple harmonic manner as was done by Kmg.

y

fJ t

(15)

VIII. ]

CONmlCTI"'ITY OF THE EARTH'S CRUST

189

12. Applica"tio1lS.- . rile a hove rna thematical trea tmen t can be utilised [or solving the !{eulogical problem, oiz., the penetratiOn of the daily and annual c'ilfLU!:,re5 of tcmptn:tture within the earth's crust. It will be easily seen from (14) that the range of arnpHtud-e. R at. any point i~

and velocity of propagarion

v = - ;-=2 V~i

(17) (18)

and wOlve-length

The "lag," i.e .. , the time which any temperature applied at the surface takes to travel to a point x is

t ;;= .!!_ = x. ~ / T

'V 2 V -uk'

Vile shall now apply these results to' the pI'Opag<i~ion of heat Insi{k~ earth's crust. Here for the daily wave

T = 24 hours = 86400 sec.

the

Taking !l = 0.0049, ~he value for ordinary moist soil, we have i\ = 7:3 cm.; 1) = 8.4 X ] O-·l cm.fsec.; 0: = III 1.6.

Suppose the maximum tL";]llperatnre is 15°C. at 2' P.M. aud the minnnum is 25cC. just after sunrise, the amplitude of temperature variation is, therefore. 20"G. This variation win diminish as 1Ii·-~111·6 at a depth x, For x = 10 ern .. , r,,"[l1.e = .42, for x = 30, «: ~,Ill. ~ = Al'lti and for x = ] GOo., 8 - "Ill. ~ = :000 IS. Thus a t a depth 01 ~ 1 metre che temperature variations will be. scarcely noticeable.

The slow velccity.of penetration of the dai~y heat wave must h~ .e been familiar to all observant. minds In a tropical country. Here the roof of the house i~ exposed to the scorching heat 'Of the sun, and at 2 P.M. the temperature may be as great <IS (j.(),oC. But t.hi~ temper~. ture travels inward at the extremely slow rate of 9, T X 10-4 cm.j'sec. or GA em. per hour in a mass of concrete (h = 0,Q058), Hence to penet.rate a wall depth of. 30 to 40 em. a period of 5 or (i hours is necessary, The inSIde of the mom, provided the windows are shut, therefore, rea~hes its maximum temperat.ure at about 7 or 8 P.M. when the ", a Us become Intolerably hot. and beginw radiate. ~\1ost 'People mu~t. ~av~ experienced ,tb.at it js found impossible to sleep mi1001's at this tome. The mJl1U1""lUm at the top or the mom is reached at a bou t sunri se, So the rooms an' Ion nd to he cool f(C)]11 II A.M. to about 2 P.M. when the ou tside is iii ot,

Annual Wav(;'~Be~ide8 the diurnal fluctuations the surface of the e ~.r th Is also su b] ect to a nann ual period of 3 G5± days ow lug to the different amount of sudan: heating In winter and summer. This amount is variable .in differen L countrles, but in desert countries it lTItly amount to as much as 60"C in. the sun in summer and flOC. in winter.