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THERMODYNAMIC PROPERTlES OF

CARBON DISULlPWlDE
BY D. N. SESHADRP.D. S. VISWANATH.AND N. R. KUEOOR
(Dfpurrment of Chemlcal Engineering, Indian Insrit~rleof Science. Bangalore-121 India)

(Received : February 6, 1965)

ABSTRACT
Thsrmodynamic properties o f carbon disulphide tkave been evaluated up to
a temnerature of 750K and a prsssure o f 330 atmospheres using Martin and Hou
eqiration o t state. Tables o f thermodynamic properties and a temperature
entropy diagram am presented.

3.

Molecular Wright ord Critiral Duta :


The available critical constants of c a r b o n disuiphide are p:cse!~!cd i n
Tabls L.
The d a t a eorlier t h a n 1880 is n o t considered f o r lhis work. The sample
used by H a n n a y 7 was digested over sodium ar;d distilled from quick line inio
a Snlall flask a n d stored over s ~ l p h u r i cacid undcr n boll jar. Calibration of
t h e thermometer was m a d e daily a n d the mean p r o b a b l e error Was fixed at
0 . ! 6 " ~ . Fsr the measurement o f presaurc, hydrogen was used as a reference
gas. T h e p r o b a b l e e r r o r io t h e measurement of prcssara is slated to be about
0.07 atmospheres.

Molecular weiglrl and criiicol consranis of corbcn di~ebhjde


Xgolocu!ar weight of carSon disulph:de=76.!42

Year

Investigator

T<,"K

---

1821
1874
1878
1880
1882
1890
1890

de la Tour
Avenarius
Sajotschewsky
Hannay a n d Rogarth
Hannay
Battelli
Galitzine

1898

Mathias
......
Fischer and Reichel 552.16

1943
.-

548.16
519. 1 G
544.95
546.12
550.84
546.16
552.76

PC,atm.

77.8

Method

......

......

......

74.7
77.9
78.14
72.87

......
......

_..-

0.377

R6 ference

a
a
1~

a
a
?*
:'*

......
......

0.44L

......

......

---

Values selected
551.16
78.0
0.44
a
disappearance of the meniscus.
b
disappearance of the droplets after the mrniscus has broadened.
c
law of rectilinear diimeter.
?* = Methods unknown.
Fischer and Rciche14 determined t h e critical temperatere by ihz micromelting apparatus. The refractive icdex of t h e sample of carbon disulp1,idc
used is stated t o be 1.6278.
The data of Fischer and Reiche14 for the critical temperature agrees well
with those of & m a y 7 and Galitzines. The data of 13annay7 for the critical
pressure was selected a s the most probable. Critical density was determined
by Mathias by the law of rectilinear diameters. Hence, this value is selected.

---

Thus, the critical constants used for this work are:

To 5 5 2 . 1 6 " ~;
PC 78.0 atmospheres ;
and

do 0 44 gm/cc.

Vapcur pressure of carbon disulphide has been determined by vnricus


investigators, including Henning a n d stockg, Siemensi5, ex", Waddington
er 01." and Hannay7. The available data along with the range of availability
arc presented in Table II. Excepting Waddington el
n o investigator has
reported the extent of purity of sample used.

Pierinodyfiamic Properries of Carbon Disulphirle

297

Waddingtoi et aLzR determined the purity of the sample to be 99.98


mole X by the tune-temperature freezing point method
Vapour pressures
were determined by cbuliiometric method. Their data extend u p t o a pressure
of about 2.7 atmospheres. The data of Siemensz5 extend up to 1 atmosphere
pressure. The zuthor claims an accuracy of 0.1 mm Kg. Vapour pressure
data up to the critical point a r e presented in the International Critical ~ a b l e s " .

TABLE
I1
Vaaour Pressure of carbon disul~hlde

Year

Investigator

1880 Wullner and Grotrian


1852 Hannay
1906 Rex
1913 Siemens

1921 Henniug and Stock


1928 International Critical
Tables
1962 Waddington ei al.

Range of
temperature. OK

Range of
pressure, atm.

293 - 358

0.4 - 3.0

313 - 550
273 - 303
I94 - 319
248 - 284
203 -546

0.8 - 78.1
0.17 - 0.57
0.0 - 1.0
0.04 0 28
0 - 75

277 -353

- 2.7

Reference

30
7
20
25
9
I1
28

In general all the available data are concordant. However, a t higher


temperatures the data of ~ a n n a ~are
' lower than those presented in tbe
International Critlcal Tables. This may be possibly because of some error in
the measurements. Hannay7 reported a value of 78.0 atmospheres, a t 5 5 0 ' ~
and 5 5 0 . 8 4 " ~ . For this work the vapour pressure data of Hannay were not
considered.

All the data were combined aud smoothened taking into account the
selected critical point. More weightage was given to the data o f Waddington
The data
et al., and the data presented in the International Critical rables.
were fitted t o the equation :

Over a pressure range of 1 - 78 atmospheres, the equation predicts vapour


Pbzssures with average absolute and maximum deviations of 0.48 % and 0.9 %
respectively. Below 1 atmosphere, the smoothened data were used.

Densiry of saturated liquid has been d e t r r n l i ~ i r dby Schewer;?', Thorpe76,


Lowry", Seitz et a l Z 4a n d ~ y r e r ? Table 111 gives these data a h n g with the
range of availability. Accuracy of the data is n o t reported.
All t h e data agree very closely, t h e differences n o t i-xcetding 0.2%.
I-lence a11 the data were combined a n d smoothened.
Saturated vapour densities a r e presented in the Hnternaticnd Critical
~ables!'. The data were srnoolhencd and wcrc used for chis invest~gztion.
'X'AiJ1.E

111

Saturated Itniil drmiiies of c o d o n rKwlphidi


I nvesfigator

Year

IF30

Tborpe

1912

Schviers

1914

Tyrer

:914

Lowry

1916

Seitz es aB.

Range of temperature.

OK

Reference

The saturated vagour densities wherever n o t available were evaluated


using h4arlin and Hou equation of state (Equation 5 ) .

Ti~esa!uratcd vxpour "densities availahie a n d calculated - and the saturated liquid densilie' were plotted a r d a smooth curve was drawn. The saturated
liquid densit:es accepted for this worlc w e r e taken from tile sn:ooth curve
taking into consideration the observance of the law of rectilinear diameters.

Eeoi Copocitg of Tdedenl Gas :


Heat capacity of carbon disulphide in the ideal gaseous state have been
determined by CrossJ, Waddington et ul.", and by Gordon6.
Gi:rdonyh data are for a rigid rotator harmonic osci!lator approximaticn,
but includes tha anharmonicity correction.
Waddington er al.7a. Rave taken account of centrifugal stretching,
rotation-vibration interaction, vibrational anharmonicicy and effect of isotopic
were
composiiion. Fundamenla1 constants recommended by Rossixi et el."
used.
Also. their data agree with their experimental heal capacily data.
The data of ~ross', Waddington sf ol.la and Gordon6 all agree within
about & I % ,
4.

The d a t a of Waddinaton eral., was fitted over a temperature range o f


273- 1 5 0 0 " ~t o t h e eyua:ion :

c,: - a

- 1.234 x

c=

and d

PI

+ b T + CT' + d 7 '

- 3.363

x 1 w9.

Equation [2] predicls h e a l capacities with arersge absolute a n d maximum


deviations of 0.21% and 0.6!V/, respectively.

Heat of vaporization o f carbon disulphide has been experimentally


determined a t t h e normal boiling point by ~ i l l s ' ~~, a t h e w s and
' ~ wirtz2'.
LVaddington el 01.'' dcrermined the b r a t o f vaporization over a temperature
ranpe of 252 3 2 0 ' ~ . ~vlills". ~ a t h e w s ' % n d WirtzZgdid n o t give the extent
of purity of t h e sample used.
T h e sample used by Waddington el a
i.'
is
staizd t o be 99 98 m o l e % pure. All these d a t a agree within 17;.
Heat of
vaporization h a s been t a b u l a t e d in t h e International Critical ~ a b l c s "a n d the
Nand Book o f Physics a n d Chemistrym.

All t h e d a t a were combined and smoothened. Nowever more weightage


T h e smoothened data were found t o
zgree with t h e a c t u a l values with a maximum deviation of 1%.
was given t o t h e experimental data.

T h e smoothened d.ita
fitted to the e q u a t i o n :

where, ho

over a temperature range of 2 0 - 4 2 0 K

were

- 27.509

71 =

0 50.

Equation [3] predicts the: smoothened d a t a


maximum deviations of 0.69% e n d 1.74% respectively.
C!ausiias-Clapcyron equation, namely,

A H,.

- ( J P / ~ T ) T(. vZ- F',)

average absoiute and


0 1 e r this ranpe the

14

For the ediculati+n of thermodynamic properlies


equation of state, namely,

Martin asd H~~

with K- 5.475 has been used.


The constants evaluated by the method outlined by the authors'' are:
Bo
4.57371 x lo-'
Az
112.362592
B2
6.5174545 x
C2 = - 424.13465

-- -

AS

--

1.3361083
6.3478989 x lo-'
C3 r. 58.190466
A& a - 7.198832 x lo-'
3;
3.5879031 x
C3 = - 6.801570 x
B3

I n the region of available data Martin a n d Hou Equation was found


to predict pressures with average absolute and maximum deviations of 1.93%
and 17; respectively. These are shown in Table IV.

Entropy and E n t h ~ l p yof the Superheated Vopour :


Considering the entropy and enthalpy t o be functions of volume and
temperature. we have,
d S - ( a s!a T ) " da"+ ( a sja

v ) ,d Y

id

Using Maxwell's relations, we obtain,

Using dH

dS=(C: / ~ ) d T + ( b . P / a T ) ~ d v

TdS + VdP in Equation [7] we obtain,

d H - C : d ~ + ~ ( b T~) /~ a~ V + Y ~ P

C ~ ~ T + ~ ( P V ) - P ~ Y + T ( ~ P / ~ T ) , ~ Y

Dl

Th'irmodyriamic Properties

of Carbon Disulpkide

TABLBIV
Comparison of calculated pressures

TzEP'

"

P'&.
(This work)

%
Deviation

PC+.

fO'Br%m)

Alford's)

--

Average absolute
deviation$

Deviation (P - P,,,,)/P
*Smoothened experimental data

%
Deviation

From Equation 153 we have.

Using Equations [2] and @I in the nbov-? aqu:rtions and carryiog out tha
integration, we obtain cxpressmns for entropy and enthalpy a s :

where Cs and CE are the consinnts o f intepCion.

In the present work the reference state choscn is W 0 and S -i.R h P - 0


for olepwnts.
Entropy value at the normal boiling point was n valuated using the ideal
gas thermodynamic properties and the Bertbelot correction. Entimlpy a t the
normal boiling point was eva!uakd by makjng use of rho heat of T c m a t i @ n at
O'K, the ideal gas rhermodgnrmic proporties and t h o Gerthelot correction for
anthalpy. The integration constants Cs and CN YIWO evaluated usil:gtbQ
values of earropy and en?ho:py at the nornlai boiling poiilr.

Th~lizi.~modyna?nic
Properties of Carbon Disulphide

303

Entropy and enthalpy of the superheated vnpour were evaluated by


making cse of the calculated specific volume in Equations 1121 a n d [13].
Entropy a n d enthalpy of saturated vapour were evaluated by using the
experimental specific volumes in Equations [I?] and [13]. Wherever the
experimental data were not available these were calculated using Equaticn [ 5 ]
and were used.
Entropy and Enrholpy of :he Saturated

Liquid:

The entropy o f vaporization is related to the heat o f vaporization by the


relation

AK=TAS,

1141

The entropy and enthalpy or t h e saturated liquid were calculated using the
equations

sl=szAsv

it51

HIHz- A H ,

[I6]

The relation d H - TdS + VdP may be used to check the internal consistency
of the entropy a c d enthalpy values.
At constant pressure,
d x=T ~ S
1173
Hence, dH

d ( T s ) - SdT from which,


I$:

- T. 5 -

I , s.- J S ~ T

Internal consistency checks were made for superheated region by using


Equation [IS] The definilc integral in Equation [18] was evaluated by
Sinlpson's rule. T a b l e V gives the comparison of calculated and tabulated
values of changes of enthalpy A N for 5 isobzrs.

TABLEV
Comparison of the values of l- H
Isobar

am.

1.0

10 0

100.0
203.0
150.0

Range of temp.
OK

350 - 750
450 - 750
570 - 750
670 - 750
690 - 750

AI.I,Ic.

5131.0
41 78 5

5438.7
2348.5
1606.1

AH

5129
4180
5444
2350
1608

36 Deviation

0.04
0.04
0.10
0.05
0.12

REC~ULTS
AND DISCUSSION
The properties of slturated liquid a n d vapour a r e presented in Table vf
and of the superheated vapour in Table VII.
Thermodynamic properties of carbon disulphide were evaluated earlier
by WBrien and ~ l f o r d " . These workers used Beattie-Bridgeman equation of
state f o r the cvalution of therinodynamie properties. The Beattie-Bridgeman
equation of stale cons' nts were evaluated by using the generalibed constants
given by Maron a n d ~ u i n b u l l ' ~ .
The critical temperature and pressure used by O'brien and Alfordi9,
namely T, 5 4 6 . i 6 ' ~a n d PC= 75 0 atmospheres correspond to the data prior
$0 1900.
An authoritative I-eview of K o b e a n d ZynnI2 gives the constants as
T, 5 5 7 . 1 6 " ~a n d PC 78.0 atmospheres. Hence, i t can be seen t h a t O'Brieo
and Alford did noL use the correct set of critical constants.

Using the correct s e t of critical constants, t h e constants of the Beattie.


Bridgeman equation were calculated. The constants were round to agree
well with those calculated by O'Brim a n d ford".

A comparison of Martin a n d Hou equation a n d t h e Beattie-Bridgeman


equations with the experimental data are made in T a b l e IV for the saturated
region.
Around t h e critical region Benttie-Bridgeman equation Fails to
predict pressures satisfactorily
However i n the low pressure regions a good
comparison could be s e n .
A comparison o f t h e two equations in the
superheated region is highly desirable, but could not be made owing to lack
of dala. 111 general i t is believed t h a t the d a t a calculated in this work 1s
superior l o the d a t a oT O'Oiien and ~ l f o r d " a s i t can predict properliis
around the critical regiou and also a1 high pressures.
Calculation of thcrrnodynarnic properties of carbon disulphide were
made up t o a temperature of 7 5 0 ' ~a n d a pressure o f 300 atmospheres. The
calculated properties are represented graphically as a n entropy temperature
diagram and is shown as Fig. 1.

d
PCFbFf R l f U R C - E k T R B W
oraeaau FP#

C
VISWAYLIW. D S..

m P I A 1 C P ti?: SLVHAOII, 0.N..


LXD

P-PRESSURE.

KULOOR. N

ITUOSPHERES

H - ENIHALPI. L I L O I I I S ~ G ~ ~ U W L

v=VOLUuE,

R E r I B L N C I STlTi

C IGRAPHliEI
PNO

----

~rrlrr/mr# roir

X = WEIGHT PERCENT

ATO'K

-- -

AN3 S (RHOMBICI
ZERO PRESSURE

H = O , AND s t R L ~ P - o

Praperiics af Satunted Liquid and Vapour

TABLEBrI

CARBON DISULPHIDE

TeK

P atm.

T"K-

P Alms.

0.10

0.20

.-

0.30

0 50

0.80
1.00

Pressure Range:
1.50

2.00

p
p
p
p
-

3.00

~..
~

5.00

0.10 t o 5.00 atmr.

v
H

H
S

H
S

P atms.

750.0

720.0

700.0

680.0

660.0

640.0

-TK

TABLE
VII--(contd.)
Pressure Range : 0.10
to 5.00

atrns.

6~~9.0

BlElE

PE'ES

QJO'I

6081E

FL'PS

SPE'I

L641F

OQ'S5

OLL'I

f9!ZC

11%

ewz

SIcZE

16'9S

S6.LS
SSKC
ots't

YP'8S
S
ROSZE
H
~ 9 8 . ~A

0'00s

TABLEY 11-(conld.)
Pressure Range: 8.0 to 60 0 atrns.

TDK

P Atms.

S.0

10.0
15.0

_.____
. . . .

20.0

_--.
25.0

- --

T A B ~VLIE
(~01$td.)

30.0

40.0
~~-~

50.0
~

--

--

60.0

--

Pressure Rangc: 8.0 to 60.0 stm.

150.0

--

200.0

25U.O

300 0

--

Presstlre Range: 80 0 to 3W.0 e m s .

Therrnodynnmic Properlies of Carbon Disulphide

314

NOMENCLATURE

-Constants in Equation [I].


A, B. C, D.
Constants in Equation [Z].
a, b, c, d,
so, A2, B2, &;.,
A3, B3, C3, Al, -Constants in Equation [s]

- Hant

capacity a t constant pressure, cal Igm. mole 'K.


-Weat capacity at constant volume, cal./gm mole OR.
-Constants
of integration in Equations 1121 and
respectively.
- Enthalpy, cal Jgm. mole.
- Pressure, atmospheres.
- G a s constant, liter atmIgm. mole OK.
-Entropy, cal.Igm. mole O K .
Temperature, OK.
Specific volume, litres/gm. mole.
- Enthaipy o f vsporization, cals./gm mole.
- Entropy of vaporization, cals /gm. mole OK.

- Properties a t zero pressure or ideal gaseous state.


- Critical point.
- G a s or vapour.
- Liquid
- Pressure
- Temperature
- Volume.
REFERENCES

..
..
..

Avenarius, M..
2. Battelli, A.,
3. Cross, P. C..
4. Fi~cher.R. and Rcichel, T.,
5. Galitzine, B..
1.

..

..
..

..
..
..

Pogg. Ann.. 1874,151, 303.


Mem. Torino. 1890.2, 4 1 .

I.chem. Phps., 1935. 3.8 5.

Mikrochemie, 1943.31, 101.


Wied Ann., 1894 41.620.

[I31

--

..
..

..
".

Gordon, A . It.,

Hanny.3. B.,

H e n n h p , F. and Stock, A,

..

Kodgnian, D.. Editor

..

Lowry, T. M.,

e.,

Maron, S. M.and Turnhull, D ,


Marlin, J. J . and Hau, Y. C . ,
Mathias, E..

..
..

Mills. 3. E.,

..

Mathews, J. H..

O'Brkn,

L.3. and Alford. W. J.,

..

Rex, A.,

Kossini, F. D., Gucker,P. T Jr.,


Johnston. M. E., Paulmq. ..I and
Vioal, 6. W..
Sajotschcwsky, W..

..

Schcwcrs, F..

,.

Scitz, W., Altertburn,

Lecher. W. 6..
Sltmens. H. V.,
Thnrpe, T. E.,
Tyrer. D.,

Proc. R. S o t , (London), 18$2,33,214.

Ibid,1880, 30. l i 8 .

and Iioearth, J..

Kobe, K . A . and Lynn, B.

!nd. T~zan?.
Ciwni., 1913, 35,851.

H. and

..
..
..

..
..

..
..
..
..
*.

"lntcrnationnl CritmL Tahlcs", 3 and 5, M ~ G ~ ~ ~ .


Hill, New Work, 192!:.
C h o n . K r r . 195 ., 52, 117.
J d i e m . Soc., 1914. 105. 81.

Ind. E n p g . Chem , 1941. 33, 408


A. I. (%.E Jorrrrtnl. 1955. 1, 142.

J. Am. chem. Soc., 1926, 48, 562.

J . Am. chenr. SGC, 1909,3E, 1099.

..
..
..

I. An?. chem. Sac.; 1952, 74, 2699.

.,
.

J. chela. Soc. (L.oridon), 1912, 101,1889.

Iml. Engng. Ch~rn.,1951, 43, 506.


2. P h y ~Chem.. 1906. 55, 135.

Beibl. Anit/!$ Phys.. 1891. 3 , 741.

..

Annln Phys., 1916, 49,85.

".
..
..

J. ctwm. Soc. (Loncion), 1885, 37, 327.

Waddingron, G.. Smith, 3. C .


Williamson, K. D. and scort.'~.W.,
Wirlz, K . ,
..
Wullner. A. and Grotrian, O.,

H:mk OF Cheinktry and Plijqics" 41,


ed., The Chenircal Rubber Publishing CO.,
Cleveland, Ohio, 1961.

'%xn:l

..

..

A n n h Phys., 1913, 42, 871.

J. chem. Soe. (London) 1911, 99, 1633,.


J . p l ~ y s Chem.
.
1962, 66, 1574.
Annln Phys., 1890, 40, 439.
Annln P h y ~ . .1880, 11, 545.

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