He~t of Solution

Mi.xing two substances to forma soluuon gener:i.ily results in the evolution

or absorption of heat. If the mixing process 1s c:mied out :n c onstant
pressure. the heat change is equal to the change rn t!nthalpy:
14-I l

Most commonly. heats of solution are measured with water as the solvent.
Aqueous heats of solution depend not only on the nature of the salute.
but also on the relative amounts of sol u te :md sol ven t. The integral he:n
of solution is defined as the enthalpy change when one mole of sol u te is
dissolved in a definite number of moles of water. far example.

432

Experiments

H:SO~U l -

2 H:( e) = H:SO.d 2 H:O

H:SO~t l -

10 H:( ) = H:S4( 10 H:O

H:SO~t 1 -

50 H:Ot r'l

H:SO~

t' - 200 H:01 C1

= H:SO~( 50 H:O
= H:SO~t

jJ{ = -4 l ,920 J 1~::!1

1
1

j.H

.::..H') = -"73.340 J

t4-41

~JI'; = - -

14-:;,

200 H:O

~H" =

-67.030 J

4.940 J

14-J 1

-:ib. i 90 J , ~-1),

l n Figure..:._;. these dar:i :.ire pioned for suifunc :.ic1ci and sorne orhe;
substances. Ir is evident thar the emhalpy change per mole salute ~ve:i
rually becomes constan t. The integral hear of solution ar infinire dilution
is the value obrained when funher dilution causes no further efec~.
Far sodium chloride rhis occurs :n n H:O < 200: far sulfuric acid. J.t
nH 20 > 800.
Experimentally. rhe integral hear of solurion ar infinite dilution :s
found by measuring the integral heats of sol ution ar progressi vely higher
dilutions u mil the enthalpy change per mole of sol u re no longer changes.
Integral hear of solution data pennir calculauon of the integral heat or'
dilution. In this case. the initial stare is a solution of sorne definite concentration. Far example. if Equation 4-.3 is subtracted from Equauon
4-L the result is

~\) =

-.310 J

This is the he:n evolved when l mole of suifunc acid dissolved in iO

moles of water is diluted with 40 moles of water ta fonn a new solut1on
comaining l mole of sulfuric acid dissol ved in :50 moles of water.

'laOH

--

- 50 ~

Moles Hp!mole soiute

Figure 4-1 Integral heats of soluuon.

433

Calorimetry

Integral Heats of Formation of Individual lons

Ionic reactions involving heats of reaction and heats of fonnation of
individual aqueous ions are important in solution calorimetry. Consider
the net ionic reaction for the heat of neutralization of any strong acid
and strong base:
H-1 aq) - OH-(aq)

= H:Ot ::' :

'.:-.'! i

In tenns of heats of formation:

llitJ

lli'.> ( H 20) ~ [ ~: 1 OH - -

.::.ff'.i;

. ~--,)

H . 'i

Far this or any reaction involving ions. :rn l!quai number ot' opposite~y
charged ions must be present. Consequently. there is no way to separare
the contributions of the individual ions represented in the square-bracketed expression. If the he~lt of formation ofjust one ion-any ion-were
known, the contribution of each member or' the pair could be separa tea.
Consequently, it is necessary to adopt the .::onvention that 1he heat ()!.
formation of the hydrogen ion is zero lt :s"' C:
)

:uf . =

1)

~-10 )

This equation. combined with the heat of r'ormation o! wate:- and

tion 4-8. gives the heat of formation of the hydroxyl ion:
H - ( aq) "' O H- 1:.zq1

H10I e)

H1(g) ..;._ -k :(g)

= H 20( t)
= ,.' H1(g)
= OH-(aq)

H-( aq)

,.
1

H::(g)

+ - :(g)

:::~ua

;\...;

,...._ l

:uf') = -235.34

'r
;\...;

' ~-1::: )

~)

kJ

:uf

-55.39

f)

1,

w~ = -229 .9 5 kJ

.:-(J)

l ~-1~)

Now that the heat of formation of the hydroxyi ion is knbwn. it can be
combined with thermal data far many cations to determine their heats
of formation. Similarly, the heat of formation of H -( aq). zero by convention. can be used with a variety of metals to find the heats of formation
of their cations by rnea.suring heats of solutions o! metals in dilute acid.
for example.
~u=

-l52.42 kJ

1~-15 )

The heat of this reaction in terms of heats ar' formation is

TABLE 4-1
Heats of Formation at 2SC (kj/mot)
Compounds

..\gO(s)
H10<l')
KOH{s)
ZnS<s)

~r

Cations

~'

-l27.03
-285.84
-425.85
-189.5

Ag"(aq)
W(aq)
K(aq)
zn~raq

Anions

.::.H'

!05.90

Br-(aq)

- !:0.92

o.o

cnaqJ

-!6 7 .~

OW(aq)
2
- (aq)

-:::.9 .95
. 1.3

-25l.::l
- l 52A2

434

Experiments

-152.42 kJ

= llir(Zn~)

~r(Zn: .. ) =

- O- O- O

(4-16i

-152.42 kJ

(4-1'7\

Combining heats of formation of known c:nions with suitable he:n of

sol ution data and heats of formation of pu re substances results in funher
heat of formation data for anions ....\ few representative data are !isted in
Table -+-l.

Heats of Solution and Reaction from Heats

of Formation of lons
From such data. we can calculate heats of solut1on. For cxample. .ve can
calculate the heat of solution of KOH ( s) :

KOHs, aq = K-(aq) + OH-raq

j,J{sotn = l l i.?.1
j,J{soln

K-) -

= -251.21

.lH? (OH- ) -

- .:::9.95 - .+25 .35

14-18\

:JI~' KOH

-H9)

= -55.31 KJ

From a slightly different point of view. we can calculate the heat or" orecipitation of a very slightly soluble substance . ...\gCl 1s1:

..\g - ( aq J -:- Cl - aq}

llippin

AgCl s 1

lli} ( AgCI)

= -127.03

- .llf~ ( ...\g-) - .~H~ 1C -

' 4-:o l
1

4-:!l i

- 105.90 - i67A4 = -65.-+9 kJ

Measuring Heats of Solution

Experimental heats of solution are me:isured in ordinary Dewar: flasks
open to the atmosphere, equipped with a stirrer, a temperature-sensing
device ( therrnometer or thermistor), and a beater. The heater is used to
calibrate tbe calorirneter by measuring the ternperature rise caused by
the absorption of a detinite amount of electrical energy:

12Rt
C=--~ T cai1b

When the current 1 is in amperes. the resistance R. in ohms. and the time
is in second.s. the heat capacity C has units of joules per kelvin. Measurement of the temperature change caused by a sample of g grams and
.\!/ molecular weight gives the heat of solution in joules per rnoie:
l

l l i = C.\!/ ~Tsom

14--:J)

Apparatus
A heat of solution calorimeter consists of a Dewar flask. stirrer, and heater.
A control unit for passing an accurately measured consrant electric current

through the beater and standard resistor is used for measuring the po-

435

C.:tlorimctry

tential developed and the time. A thermistor and \\.neatstane bridge are
needed. and about 20 g potassium nitrate. 1

SAFETY CONSIDERA TIONS

The calorimeter Dewar flask should be well C!lped :.lJld 5'afery g~gJes
should be worn.

~~~~~~~~~~~

EXPE R1MENTAL PROCEDURE

Preliminary Preparations. Weigh 2 te :.5 ~ _J.01) 1 g ,1 potas
sium ni trate ( K.."i0 3 ) on a tared. g.lossy .veighing ;Japer. \V:th :
graduated cylinder. add 400 0.5 ml water :o the .:aiorimeter !Je'.var
tlask. The temperature of the water should je whin J. ::-ew deg;rees
of room temperature. Assemble the Oewar rlasK v.ith :he stirrer.
heater, and cover. Be sure the stirrer rnoves :Teeiy. v.ithalllt toucaing
the walls of the Oewar flask.

Calibrarion of the Calorimeter . .-\s J.iready ;JClnted out Eq.

4-22), you calibrate a calorimeter by rinding ns >!nerg- ~uivalent.
C ( J /K). This is nearly always accomplished by iirecnng a known
quantity of electrical energy into the system ;Jius w.ior...meter. This
~nergy is dissipated in a heater resistor R;, immerse :n :tie c:i.iorimeter. To calculate the c:ilibration energy, it :s aecessar; :..-:> know tlle
current lowing through the heater resistor. The he!lte:::- curre:n is
usually not measured directly with an ammeter. bec:luse :he current
can be more accurately measured indirectly potenriomecicaily. The
essential circuitry of a calorimeter is shown :n F!gure ..l.-:.
Because the two resistors, Rh and Rr. Jre '..::i series.. the same
current f passes through both. ( The subscripts h 10d s r:Jean nea.Ier
and standard. respectively.) The heater resl.Stor R~ is i coii 0[ :llchrome wire of unknown resistance; the R, ~s a stand.ar resistor oi
accurately known resistance ( :::0.05%) : The elecmc: ~!:::ergy q~ dissipated in the beater resistor is

' ..\ commcrctal unit is availablc: Parr

53rd Strect. Yloiinc. !llinois 61:65.

1 ~51

Soluuon CJ..ionmc=. ?lr. .='.m::.=t

C~m::;inv,

:: :

E.
1

----"V\/V\/',....-----"IVV'/'.i'r-

R..

Figure 4-2 Calorimctcr

calibration cin:u1t.

-~-

436

Experiments

The current flowing through the two resistors is found by measuring

the potential E1 over the standard resistor:
I

E1
R1

(-4-25 )

:-..;ow the resistance of the heater Rn may be found if the poten tia!
E" over the heater resistor is measured :

R ., =E"
/

' -'-:6)

Substitution of Equations 4-25 and 4-2b mto Equation -+-24 gi ves

:rn equation for the calibration energy ! r: te:ms ) i the ~ime :ind
potenuometnc measuremems:

The energy equivalent oi the calorimete; C is

e = 3.!:._

.:::.T

, 4-:s 1

It is not actually necessary to measure the temperature if a thermistor

is used as a temperature-measuring device. Instead. the res1stance
of the thermistor may be balanced against the diai divisions of :i
Wheatstone bridge. and the energy equivalent oi tbe calonmeter
may then be expressed in joules per dial d.ivisions:
C

= -3..!:.._ =
.::JJh

E,,E,:
R,.:tlJn

14-:9 1

where .::JJ>i is the change in Wheatstone bridge dial d.ivisions recorded

upan balancing the bridge befare and after heating the heater resistor
for r seconds. The data for the calibration consist of the points 1ying
on the line segments ABCDEF in Figure .:+-3 . The length of the
segment ED corresponds to .:tlJh.
Measuring the Heat of Solution. In a calorimeter consisting
of a 1-L Dewar flask containing about 800 mi water. a 4- to 5-g
sample of potassium nitra te is about right. Detennining the heat of
solution consists of measuring the change in bridge dial divisions
when the sample of nitrate is added to the Dewar flask. This corresponds to detennining the length of line segment BC in Figure 4-3.
A ?ractical Calorimeter. Solution calorimeters are available
commercially, but the one yo u will use is probabf y not of commerciai
origin. It is likely that it was built locally. Calorimeter designs differ
widely in detaii but ha ve a number offeatures in common. as already
indicated. The design of a simple. inexpensive. and convenient calorimeter is shown in Figure 4-4. It consists of three physically separable components. enclosed within the doned lines of Figure 4-4.

437

Cllorimctry

F
1000.0

;{

) 90.01
1

! .\

:"V
~

....l.L.I

.r o.o !

/
; ~.

.:::. : .!IJ.0

330.0

3:0.0

31 0.0

t)

500

1000

; ~

.:ooo .::soo

.)000

3500

11secl
Fi~ure

4-3 Bridge dial div1sion versus nme.

The tirst componen t. the calorimeter. is :m ord.inary l-L Dewar

tlask fined w1th a 2-cm-thick plastic cover throug.h which four hales
are drilled. Through the hales pass a stirrer. a heater resistor R;,,
anda YSI z therrnistor. The heater is constructed of 20 turns of ~o.
26 nichrome Wire. glued to a plastic rod and contained in a piece
of glass tubing extending out of the calorimeter. The tube is fled
with mineral ol to improve transfer of heat from the heater to the
solution. The fourth opening allows for a sample to be introduced.
The second componem is a commercially available Wheatstone
bridge ( e.g.; Sargent 3 ), of which the thermistor forms one leg. The
variable resistors in the bridge are helicaJ potentiometers with l 000
divisions. The bridge balance point is detected with an electronic
galvanometer ( e.g .. Honeywell 4) . The energy equivalent of the calorimeter is dete~ined in joules per division.
The third component is a control unit. the three mam parts a r"
which are a digital readout timer. a digital potentiometer. and a
small regulated power supply, which supplies power to the heater

: Yellow Spnngs lnsuument Company, lnc .. Box -Ui5. Yellow Springs. Oho -l538i
: SalcntWelch Scientific Company. 9520 Midwcst Ave.. Ganield Heights. Cleveiand. Ohio
Honcywcll. loe.. .WO Bernardo Ave .. '.'li1ountain View. CJ.iifomia 9404 3.

.!.! 125.

438

Experiments
BRIDGE

CALORIMETER

r---------------,1
1
i

CJlorimeter Calorimeter
heater
thermistor

r--~----------------------,
1

:
1

'~!'!:

6K _.

. .
-----------------

Honevwe il

..::

\''

J:.ll \ anoml!!~r

_-,,.

/ :K / ( Jarse
JCIUS!
,...
'
01'.
,,_,- ... - .
,.,..&,

,..

;- : ne
J01us

~---------------------------

CO'-!TROL L'.'IT

,------------------------------------------------::oo

,'"'OK
_
!

'

1
1

~1

6-

- -

o .'.)

1
1

1
1
1

Dummy heater
!- - -

6-.,

o !o

----:=; TB-3 .i..C ? .S.

.;C

~rounu

'/

::>-- ~.Hemal

1
1
1

'

~--------.:i:

l
1

power
Pos .

-o.-.

l-~'.)

--'.)
1

Interna! power

S.ta.n dard

resistor
1.0000 l.1
:::: 0.05%

1
1

TB-3

1
1

1
1

IOK

-1 Rs

'.) TB- i

'

~-~--~-~--------------------------------------

Figure 4-4 Calorimeter control circuit.

resistor. The power to the heater resistor and the timer is switched
on and olf simultaneously with a four-pole. two-throw switch . .--\.
second timer ( not shown) allows measurement of the total run time.
When the power supply is not heating the heater resistor. it is given
a dummy load so that drift is minimized when it is heating the
calorimeter heater resistor. A standard resistor R, is wired in senes
with the heater resistor Ri, . The vo!tage E, over the heater resistor
R,, is reduced to Vh with a voltage divider. and the voitage Es over
the standard resistor Rs is similarly reduced to Vs. The voltages V"
and V5 are measured with a digital potentiometer. which is switched

439

Calorimctry

back and forth between the heater and standard resistors. For the
voltage divider resistor shown in Figure 4-2. the values of E, and
En are calculated from

E =
'

,..

-
.~

11000~-

1000

t:osoor,
500

1 ~-JO

' ~-JI

\'laking a Run. Check the controi unit: ~he heater switch

should be on .. dummy. not on "'heater... Tum the controi unit
and bridge galvanometer On and let them warm up severa! minutes.
Zero the run timer and the heater timer. The potentiometer should
be set to monitor the potential (V,) across the standard l-ohm
( :=0.05%) resistor R,. The val"ue should be around 0.06 volts.
When the Dewar i1ask and water have come to thermai equilibriurtl after being stirred severa! minutes. set the initial dial settings
on the Wheatstone bridge. Set the sensitivity dial on the bridge to
maximum and lock it. Set the sensitivity dial on the Honeywell null
galvanometer about a half-tum less than maximum. Do not disturb
these settings for the duration of the experiment.
Set the fme-adjust dial of the Wheatstone bridge near the high
end of the scale. around 950. With this initial setting on the fineadjust dial. null the Honeywell galvanometer by adjusting the coarseadjust dial of the bridge. Because of the extreme sensitivity of the
galvanometer. it may be necessary to finish the actual nulling with
the fine adjust of the bridge: when nulled. the fine adjust should
have a reading over 900.
Figure 4-3 shows that making a run consists of five parts. indicated by the five line segments. ploned over the data in the gure.

1. Start the run timer and null the galvanorneter every 50 seconds until enough data are gathered to determine the slope of line
AB.
:!. Open the calorimeter cover. quickly durnp in the sarnple
of K.."O,. and record the run time at the moment of dumping the
sample. Line BC is a nearly vertical line: its ordinate value is the
run time of dumping the sarnple.
3. >f ull the galvanometer again with the bridge fine adjust.
Continue to null every 50 seconds until enough data are gathered
to establish the slope of iine CD.
-1 . Switch the heater switch froin "dummy"' to heater'' and

record the run time at the moment of switching. The heater timer
automatically begins to run as a constant potential is applied to the
calorimeter heater. Heat for l 00 to 200 seconds. While heating,
switch the potentiometer back and forth between the potential over
the standard resistor and the calorimeter heater. They should be

..

440

Experments

constant within about 0.05%. Record the reading of V, and V,.

The digital readout potentiometer gives values around 60 and 70
m V, respectively. Line DE is a vertical line: it is drawn exactly at
the halfway time ofheating ( run time + heating time/ 2). Note that
heating more than about 200 seconds may result in exceeding the
number of dial divisions on the fine-adjust dial.
-' '.'iull the galvanometer with the fine Jdjust. Continue to
the galvanometer every 50 seconds unril enough data are gathered to establish the slope of line EF.
'.1 ull

Results and Calculations

The electrical heating energy qeiect in jouies 1s given by Equauon ...1-:-.
When Equations 4-30 and 4-31 are combined with Equation 4-29. the
energy equivalent of the calorimeter C (joules/ bridge dial division J is

C = 265 l V,!;, l /

:>J),,

where jJ)1i is the change in bridge fine-adjUst dial divisions occumng

when the system is heated far t seconds with R, set ta l .000 ohm ( line
segment DE in Fig. 4-3 ). and Vi, and V, are the potentials in volts across
i:he voltage divjders in Figure 4-1.
The heat of solution is given by
::,.]{ = .'vfC jJ)so1n/ g

(4-331

where :'vf is the formula weight. gis the mass of the sample in grams. and
~soin is the change in bridge fme-adjust dial divisions occurring during
the solution process ( line segment BC in Fig. -+~).
Calculate the heat of solution ( kJ /mol) for four samples of pot.assium nitrate. Compare the average with literature values. Determine the
propagated errors.

Other Systems Suitable for Calorimetric lnvestigation

A: wide variety of processes lend themselves to. calorimetric study. In

addition to the solution process. enthalpies of formation. mixing, neutralization, ionization. reaction. displacement. and complex ion formation
have been studied ( Table4-2).
The reaction between silver ion and zinc ( Hill et al .. l 965) is interesting beca use the heat of reaction can also be.measured potentiometrically as described in Experiment 22. The potentiornetric heat of reaction
can then be compared. with the direct calorimetric heat of reaction.
To measure the heat of the reaction between silver ion an :::.inc
with a calorimeter with the sensitivity of the apparatus described in this
~xperiment, use 400.00 mi ! four l 00.00-ml aliquots) of a standard so1ution of silver sulfate about 0.00625 M. Because silver sulfate is the
limiting reagent. the volume of its solution must be accurately known.
but the calorimeter Dewar flask need not be perfectly dry. The optimum
concentration and amount of zinc to be added depend on the apparatus

441

Calorimetry

TABLE 4-2

Some Suitable CaJorimetric Systems

Enthalpy of fonnation: \11g0(s) 1Mahan. 1960). LiOH 1 \lauhc:ws. ! %31
Enthalpy oi mixing: chlorofonn-acetone. carbon tetr:ichionde-acc:wnc:. c::iiuro
fonn-carbon tetr:ichloride ! Z:islow. l 960I
.. EnthaJpy of neutralizationtioniz:iuon: rnifam1c . .ic:::1c. :noncc:iioroace::c. ' ';:: :;.:.
and tartanc acids IMiller <!t :il.. !94-:"\
~ . EnthaJpy of pn:cipitation: \11gtOH\:1 s1 . ..\l!OH ).1 s 1 1 P:imson : : :Ji. . ' ci..3 1: .\ 4(:1 .
AgBtis). Pbl1(.S) (Clever. 1961 l
Enthalpy of reaction ! Pattison c:t li. . i <l4 _; 1:
'
'

H~o~

MnO~ =

C:i.C: - HC =
K.Br0 3 + HCI =
!CH 3C0h0 1- NaOH =
6. Enthalpy of comJ>lex ion lonn:iuon: HgC:i- . Cul ~ H:1i P:iu1son c:t
- EnthaJpy of displacemc:nt:
Cu:~ ZnlsJ = Zn~.,.. Cursi 1Charieswonh :ind P::itc:i. ' 1::
Ag..,... Znis\ = Ag(sl ~ zn:" IHill c:t ll.. 1%5)

:l .. : ' ).:

used and are chosen to give ::m adequate temperature change ...\llow :he
solution to come to thermal equilibrium and add about l O g zmc dust.
Ten grams of zinc is a large excess ::md does not need to be accurately
measured. With a large excess of zinc the reaction takes place rapidly
and to completion. Silver nitrate is not a suitable substitute for silver
sulfate. because zinc reacts too s!owly with the silver nitrate. resi.llting in
an inconveniently slow temperature rise ( Hill et al.. l 96 5). However.
silver sulfate d.issolves in water very slowly. so the solution should be
prepared in advance.
Since the reaction is exothermic. it may be necessary to cool the
solution to approx.imately the original temperature befare calibrating the
talorimeter electrically. This is conveniently accomplished by add.ing three
or four pea-sized pieces of solid dry ice to the reaction mixture. When
the original temperature is reached. !et the calorimeter stand several minutes to come to thennal equilibrium before the electricaJ calibration.
Calibrate the calorimeter: calculate the heat of reaction as described
above and compare it with the heat of reaction measured potentiometrically in Experiment 22.

REFERENCES
! . Char!esworth. Y. E .. :.md E. \1. P:nch. '"He:i.t or' Re:i.cuons. Scnooi Sc:ence
Review 13:256. 1932.
:. Oever. H. L.. "Heat of Precipitation. I Chem: Educ. 38:470, 196 l.
3. Hill. O. L.. S. J. H. Moss. and R. L. Strong, 'Heat of Reaction in A.queous
Solution by Potenriometry and CJ.lorimetry," J. Chem. Educ. 42:541. 1965.
4. Lewis. G. ~ . and M. Randall. revised by K. Pitzer and L. Brewer. Thermadynamics. 2nd ed., McGraw-Hill, New York. 1961.
S. Mahan. B. H .. "A Simple Ice Calorimeter: J. Chem. Educ. 37:634. t 960.

442

Expcriments

6. Matthews, P. G., "A Simple Experimental Test ofHess's Law," School Science Review 45: 194, 1963.
7. Miller, J. G., A. l. Lowell, and W. W. Lucasse, "Calorimetric Studies of
'.'ieutralization Reactions," J. Chem. Educ. 24: 121. l 94i.
3. Neidig, H. A .. H. Schneider. and T. G. Teates. "Thermochemical Investigations far ;:i First-Year College Chemistry Course. J Chem. Educ. 42:26-3 l.
1965.
9. P:mison. D. B.. J. G. Miller, and W. W. Lucasse. "Simplified Calorimetric
Studies of Yarious Types."' J. Chem. Educ. 20:319. 1943.
iO. Rossini. F. D .. ed .. Experimental Thermochemzstry. Interscience. >iew York.
1956.
l l. Stunevant. J. M .. in A. Weissberger. ed .. Tt!chnwue o(Orf?antc Chemzsrry
vol. l. pt. l. Interscience. New York. 1959.
l :. Stunevant. J. \i1.. in A. Weissberger. c:d .. Tecnnzques q( Chemisir'.'. voi. '..
pt. 5. Wiley-lnterscience. New York. 197 l.
l 3. Zaslow. B.. "The Heat of Mixing of Organic Liquids.'" J Czem. Educ. 37:
578. 1960.