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T h r m u d y n a r r . i ~ ploprrtics of chosgsnc have been rvoiilatrd r.p lo :!

rem!2ci.elnrc o f EOWlh a n d a piemure of 15.0 atmo$puesrs us!l?g M x t i n an& Llou


e?u2rion o f s t n ; ~ . T h s r e r ~ l t aaa&$&niod
in :stmlnr f ~ r r n2nd r c an entrap?.
l s m p c i i t u r c di2gra.x.

X i t

r. 1

\,f<>!c,p!!:>,"
,~+'gi., ,,.>d <,,!.?St!

.
:,,sra;tllar
., .
i.rvr,iix~r:i

-. --

'?&, %
i C , a:.
- ~ -- - .
--

;319

H:rc>7T;L:ei.6
- ,.
;
.

,320

s:e;rnzno

...

455,16

D ; s ? ~ ~ a s a :?~ieI?l5CU?,
~ce

b:

il\..<.>fr,;stiii:r:.s~ diameter..
- --

- -

~-t;~:,,

- - - - - ~

0.3'.
-

----

.I,
--

- -----.-~

0 52

56.0

;a :

5:: 0

455.16

~-

- - --

---.
i

an&

T', ylnr
%'.'.:!~,os sel-,:::rJ

--

...

'56.31

,h>,.~&.?
925

'1, g,n.!c.c.

<*(

"G:,S!m,ts

of Blsssocne-9S
-- --- --

we:;hi

- - . .--

-.- ..

i-1 :..k*:li!; a n d ;UsihieuE f~.actirrnr,!iydlblillr-d the Ir!dl;striai phosgene ;n


remo: c c.ii;!zi:~inanrs cu;;slstiog of s u i f u r C O ~ ~ I P C I ::lid
~ I ~ r~eSn ~ o w d
chio!iv2
w i t k mcrcziy for 24 hoilrs.
F~~3 ~ ar .i n i ~ ga reiatiwiy pare sample, Gz:.rn:~nn l n 3 Rtyicsr6 riipea!t.di:
Pi.:.~.i.i?i.~!:c i:axincrciai phosgene. However, tbssz iiivcsii&etors couid it.,;
rondrtxs: t h e sampir: compieteiy a t constant pressure. The uz??er?!u:r?. o!
:~isnp,r.:ni~:iiea n d reappearance of the meniscus were foucc? :o be 4% 36%
and 454 7 6 " ~rcspeciively.
Tiie cririca? pressure f o u n d b y rjbservalioa a d
55.3 s t m x p h e r e s whera as b y cx;rapolaiion of vapour pressure curw, ii s::;
f e u n d :j !x 55.6 atxospi-reres. T h o vaize reported by ?hrse invcz?igaior,
i!?rlriy 455.16 "K For !hc c:iticai izrnprra.tarr bas been accepter: for [hi,
.
.

3 v cil,:ra:r

...

rn"z$:ig?ilon.

Va; iur pressure eqa.!ai!on as giver: by ihese ir~vesii~ptor:;"pi-edict .,


y r i s u : ? of 55 0 atmospheres at i!le accepted critical iemperatcrc- Fitnc.: :
p i - s s x a of 56,O arrnos:;l?eres for the crlricai pressure .was accepted for !!A
','.."."<.
,... igation.
Cri;i.xP densiry w a s daternsintd by u s i u g :lie l a w of rrctilineai diarne:crs
rhe density data of Paterno :in? :vrazz;cbc!iiLi, by Gerrnann
EX! T q l o r "
b2 nl:kirg r.a* o f

i.'lr

:hi? inv?st!yatio-,,

beco w J .

t h e critical data of Gcrma:in and ~ ~ ~ l hove


c r ~ '
T3u5 the witlcsl cousi:.,n:!, used for Ibis work. are :
?'< -455.16

P,

a,

- 5G.uJ

->

0 52

"9

u rnin.

~c.c.

:,

E b p o pi-c.,rurs
~
:

~ i v;.pour
z
pressure d a t a of phosgene has beer. axperimenlaiiy deter%lnr,i by h i k ~ n s o n et oi.', Patelno a n d h.lazzuccheih'~ G e r m a m and Taylor4
anii Glituqus aiid Jones5. Vapoor pressure data i s also presented In ifle
:n:erxai?onoL Critical ~ a b l e s ' . Table 3 gives :ha ;:wiiahle thta o!oiig wl:itb
ihc rncgz of availability.
'fbe mothood adopteo by Germmi: a n d Tayior4 for tile puriiication of the
,.Ii,is!r:
. -.
used is m e n t i m e d earlier.
? h e i n p o u r pressure dati; a r e s:ated iu Le
;ixrti!e to 0.1 a t m . T h e snmpie used by Giauque and J o n e s is stared t o he
99 493 noid 7; pure.
However, t h e accuracy of t h e vapour pressure data are
Pa!erno a n d MrzzucchelEil' have not reported t h e accuracy of
: A ! xported.
tiie &<a. tjermann a n d Taylor4 dctermiiied vrrpouir pressure of phcsgeilr
. ; Y z ~wvo :an;prrarure re_eio:~s,i u n i e l y 273 i G -- 301.06 'I< and 42C.26 - 455 16 'h:.
T b e ~ ss u t h c r s fitted their data t o the s q u a t l c n :

1323

log f =4.4hiP -(i20?,9!T)I

+ ( 1 3 2 % 7' T ' )

Pr:erno a n d M ~ z z u c chelli
..... 243.74-29429

0 2.5-1.75

ill

It

--lor:
,
vapolrr presbure data was caleulilted using Equation [I] and was
f o m d t o 'or: i n very good agreement w i t h t h a t presenrcd in Iuterna:ional
Criricnl Tabics.
For t h i s investigation, the vapour pressure data shove 1 aim. h a s been
from t b e Intzrnetiunal Critical Tables. Beiow d atrn., the data of
Giarrque end Ionea5 has been used.
Zskt::

Equation [2] predicts the vapour pressure data with a maximum diviation
of 0.1%.
rn the present work, t h e vapour pressure d a t a above I atm. was filled :,
the equation,
IO~P=A+(B~T)+CIO~T+DT
[JI

This equation predicts vapour pressure data9 with average absolute and
maximum deviations of 0.1% a n d 0.23% respectively.

For thls work Equations [2] a n d [3] have been used.


3.

Soturnled Liquid mrd Yopour Densities :

Saturated Liquid and Vapour Densities of phosgene have been determined


over a temperature range of 163 to 323 OK by Atkinson ef o l ' and over e
temperature range of 258 t o 455 OK by Paterno a n d ~ a z z u c c h e l l i " .
Both the investigators did not mention the purity of the sample used and
the accuracy of the data. Vspour density of phosgene has been determined
by Paterno arid Mazzuccbelli" over a temperature range of 333-455 OK.
Liquid and vapour density data over a temperature range of 281 to
455 O K a r e presented in the International Critical ~ a b l e s ' . For this invesiigation all the available dnta o n the densities o f saturated liquid and vapour
were c m b i n e d and smoothencd.. Smoothened dnta have been used for this
iravcsligatioo. T h e smoothened daia agree with t h e raw data within a
maximum deviation of I?&

Heat capacity of phosgene over a temperature range of 15 'K t o 2 8 0 ' ~


has k e n determined by Gi;nuquc and ones'.
As stated earlier, the sample
uaed ' ~ ythose investigators was very pure.
Later, in a careful study Glaquc
and 0 t t 6 found, that the data of Giauqe a n d Joness below a tempelature of
1 1 8 . 3 was
~ ~ applicable t o pure solid I1 and above this temperature, to solid 1,
These authors have presented heat capacity data for solid I, which js the most
arable state and also for solid 11. The accuracy o f the data are not reported.
The entropy evaluated using the beat capacity data of solid 1 at 280 71
(normal boiling point) is in very good agreement q i t h their entropy c a l i u l a t d
using! spectroscopic data.

Thermodynamic Propertfes of Phosgene


5.

mar

155

Capacity of Ideal Gas :

Heat capacity of phosgene ia the ideal gaseous state have been evaluated
by ~ h o n p o n ' ~Gordon
,
a n d ~ o l a n d ' a n d by Giauque and Ottf
Giauque
and Ott used the constant recommended by Rossini et sl." and Dumond and
cohen3. The data o f Gordon a n d Goland7 deviates by about 5yL with the
data of Giauque and 0 t t 6 .
For this inveszigation, t h e data o f Giauque and OEt has been used. The
hest capacity data of Giauque and Ott was fitted by the method of least
squares to the equation :

Equation [41 predicts heat capacity data with maximum and average
absolute deviations of 0.03% a n d 0.02% respectively. For the calculation of
thermodynamic properties, Equarion [4] has been used.
6.

Heat o f Vaporizotiort :

Heat of vaporization o f phosgene has been experimentally determined


by Giauque a n d Joness. No other data is available o n the hear of vaporization of phosgene.
As already mentioned, Giauque and Jones5 used very pure sample of
phosgene. They claim a n accuracy o f 99.9 7;.

Heat of vaporization was calculated using Clausius-Clapeyron equation,


viz.,

A K - ( ~ P / ~ T )(VsT . VI)

[-"I

making use of the experimental specific volumes. The heat of vaporization


:alculated a t t h e normal boiling point agrees within 2:& wirh the experimen:al
of Giauque and ones'.

3Y

C.&LCULATIONOF ~ N X M ~ ~ U Y N A M I PROPERTIES
C

~~r the calculation of therm~.dy.ilac~ic


properties Martin and
equation of state :

Nc u (biH,

with R= 5.475 has bem used.


The copstants in Equation (6), evaliraled foilowing the pr.?c.d~l.s
outlined by t h e authors'' are :
FQ = O,O45S6972
-41

--

I B.O5OY(37

&.- i.2038681

u. 10."

C; 3.849143 :.: 10".


Using the available experimental specific volumes of saturated vapour in
Equation [6]. pressures were computed. For 21 points tested, the average
absolute and msximum deviations wera found to be 1.23% and 3.08%
respectively. Such a comparison is sbown in Table 3. Comparison could
nut be made in the superheated vapour region because of lack of data.

Specific volumes of saturated and superheated vapour were calculated


using Eqwtivn
by making use of Newton-Raphsoo iterative method on
ISM 1610 digital computer, for varioos temperatures and pressures.

Es]

Efrrropy und Enthalpy of the Superheated Yopour :


Considering t h e entropy and enthalpy to he
temperatwe, we have,

function

of

volunx

TABLE3
Comparlsoo of Calculated Pressures
-

T, "K

P, atms

PCOM, alms.

--

sing Maxwell's reiations, we obtain,

sing d B - TdS + VdP in Equation I83 we obtain

---

96 Deviation

Using Eqmiiozs [83 and [9jPi,

s = J ' t C / T ) ~ T S+ ( r P/? T ) " ~ v

[ill

H-](c:)~T+./7'0.F / 3 T ) ~ ~ " Y P- :J: ~ L P V

[I:]

and

Uring Equations 141 and 1101 in the above tquetions and carrying out the
inragrac~on,\re obtain expressions for entrory a n d enthalpy a s :

S = ( * - i : > In T ~ ~ T + ( C / ~ ) T ' + ( ~ / In~ ()v -TE o~) + X

a h e r e G and Cn ere the oonstonis of integration.

The reference stale chosen depends upon the available data. The
reference state chosen should f iciliraie easy camparison and utilization of
the t a b ~ L z e c ! & l a . The rrfe,ence state H - 0 and S - R In P - 0 for
*kmkn~6' is appiicable for pure substances and also for pure substances
that undergo a chemical reaction.

1. the presen: work the rererencc s t a t e a s given above itas been used.

Entropy vaEue a t the n o r m a l boilirrg point was evsluated using the


ilea:gas thermodynamic properties a n d t h e Berthclot correction. Enthajpy
st the normal boiling point was evaluated by making use of t h e heat e f
fcrmnrion at O'N; the ideal gas thermodynamic properties and the Berihelot
corr&on for enthalpy
T h e iniegration constants Cs a n d CH ware evaluated
the values of entropy and enthalpy a t the normal boiling point.
Entropy and enthalpy o f saturated vapour were evaluated by using
Wherever
t i b txperimentaP data were not nvailnble these were calcuEated using Equation
[t] :nd were used.
the experimental specific volumes in Equations [13]: a n d [id].

fitropy and Enihelpy of the Saitrrufrd Liquid.

The entropy of vaporization is d a t e d to t h e heal of vaporization


'.y ihe relation

AH,.=?-AS,.

[!53

The entropy and e r t ~ h a l p y of t h e saturated liquid were calculated

using

rile equations

S, =. Ss

in

- A S:.

The properties of saturated and superheated phosgene a r c ~ r f s w t e d


the gra?hical form 3s Fig. 1.

The relamin dHI-6--Td.y+T>P may be used


consistency of the entropy and inrhaipy values.

Sencc, d H = d ( T S ) - SdT from which


2

Ef -- T?S2 - TaSt - J' S d r

to

heck the m t e l n d

10 00
50.00
100.00
-.

5500.8

5501

41C4

0.02
0.04

4706.0
3584.0
2750.2

3533
2760

6.03
0.01

14C5

0.08

240 GOO
300 -- 630
380 - 600
460 600
540 - 600

0.10
0.00

--

--

1466.7
.-

-- -.-- - - -

--

Consrants in Equatiou [i]


Constants in Equation (4)

Constants in Equation [6]


Heat capacity a t coilstant pressure, ~ a l . / ~ r a rmole
u
'Ii
Hcat capacity a t conslaat volume, c a l . / p , m molc 'K
Constaots of integration in Equations [13] and [Id]
Zutbnlpny, ~ a l . / ~ r a mole
m
Pressure, atmospheres
Gas constant
Entropy, ~ a l . / ~ r a nmi o k 'R
Temperature, OK
Specific volume, litredgram mo!o
Enthalpy of vaporization, ca1s: jgrarn mole
Entropy of vaporization, cals /&ram mole 'K

Properties a t zero pressure or ideal gaseous staie

Critical point
Gas or vapoix
Liq aid
Pressure
Temperature
Volume

--

OWr-45h

?*9<

C W W C 1
N N N N

295.1

103.1

754.7

440.0

460.0

H
5

80.07

377.2
-46710
78.69

360.8
- 47026
77.99

721.8
-49025
79.37

420.0

H
S

- 46709

114.6
-47341
75.08

172.1
- 47340
75.88

344.4
-47338
77.26

V
689.0
1% -47338
S
78.64

400.0

77.31

188.5

- 46'911

180.3
- 47027
76.61

109.1
- 47649
74.32

163.8
-47648
75.13

328.0
- 47646
76.51

656.2
- 47646
77.89

76.51

125.6

75.49

75.27

71.97
-47031
74.78

'68.68
- 47344
74.06

65.38
- 43652
73.31

62.08
-47955
72.53

58.79
-45252
71.72

0.90

--

36.63

0.80

74.55

46.96

4489
- 47035
93.85

42.83
47348
93.12

40.76
-49656
72.37

71.59

38.70

- 47958

70.78

- 48256

(contd.)

74.10

37.52

--

73.29

24.94

17.82
-47052
72.00

23.83
87045
72.58
35.87
- 47038
73.40

16.98
- 47364
71.28
22.73
- 47359
71.86

34.21
- 43350
72.67

~,--

18.65
-46735
72.71

16.15
-4762
70.3
21.62
- 47665
71.11

3 2 56
47658
7192

69.75

.- 47974

15.31

14.48
-48271
65.95

--

70.33

20.51

- 47968

69.53

- 48264

19.40

--

2.00

D 0 5 to 3.50

71.64

30.90

- 47961

70.34

29.25

- 482%

.-

1.SO

Pre?=ure Ranse:

-- . --

1.00

- 46712 - $6715 - 46719 - 46122 - 46728

120.1
- 47029
75.50

73.55

74'35

380 0

75.73

- 47952

!55.6

- 47951

311.5

- 47950

92.74

98.18

73.35

147.4

- 48249 - 48250

0.30

74.93

- 48248

0.20

77.11

623.3

598.5
-48247
76.30

0.10

0.05

TABLE5-

- 47949

PAtms.

-.

El

360.0

TCK

s'

12.36
-46749
71.88

11.80
- 47065
71.15

V1

'S

u$

11.24c
- 47378 2
70.45 2

$
69.70

?
,

3
?

-- 44bS5

I0.6i

68.9!

-- 47987

1O.ii

68.13

- 48283

9.551

3.00

aim.

...

Piaswre Range: 5.0 to:lSO


. .. -. -

-. . . . ..
~

.-

0 atrns.

1. Atkinson. R . R.. H'ycock,


Pope, W. J.

C. T. a n d . .

2. Canjar, L. N. and Manning, F. S.


3. Dumond, J W. M. and Cohen, E. R.

..
..

4. Germann, A. F. 0. and Taylor, Q. M.


5. Giauque, W. F and Jones, W. M.
6.

---,and

Dtt, J . 5.

7. Gordon, J. S. and Colund, D.


8. Hackspill, L. 2nd Mathieu

..
..
..
..

9.

..
..
Rosrini. F.
.Gucker, F. T.Jr.,
..
Johnston,
l'auling. L. and
Vinal, G . W.
Thompson, W. M.
..
..

10. Martin, J.

J. and Hou, Y. C.

Chem Soc (London), 1920, 117, ,410.

H~drocarbonProcessing, 1962, 41, 121.


Phys Rev., 1951, 82, 555.
J . .4m. Chem Sor., 1926, 48, 1 1 54.
ibid, 1948, 70, 120
Ibid. 1960, 82, 2689.
J . Chem. Plrys.. 1958, 27, 1223.

BUN de la Societe ~l&nique dc Fmnce, 1919.25,


482.

Internwional Critical Tahie., 1928. 3 and 5,


(Now York. Mcriraw H111)

A . I. C/I E Journal, 1955, I, 142.

11. Patemo, E. and Maz:ucchelii, A-

Garr. Chim Ifai., 1920, 50,43.

12.

J. Am. C b . Soc., 1952, 74, 2699.

D.,

H . L.,

E3.

Trans. Faradaj Soc.. 1941, 37,251.

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