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CARBON DISULlPWlDE
BY D. N. SESHADRP.D. S. VISWANATH.AND N. R. KUEOOR
(Dfpurrment of Chemlcal Engineering, Indian Insrit~rleof Science. Bangalore-121 India)
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.
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.
---
To 5 5 2 . 1 6 " ~;
PC 78.0 atmospheres ;
and
do 0 44 gm/cc.
297
TABLE
I1
Vaaour Pressure of carbon disul~hlde
Year
Investigator
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
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 :
111
Year
IF30
Tborpe
1912
Schviers
1914
Tyrer
:914
Lowry
1916
Seitz es aB.
Range of temperature.
OK
Reference
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.
c,: - a
- 1.234 x
c=
and d
PI
+ b T + CT' + d 7 '
- 3.363
x 1 w9.
T h e smoothened d.ita
fitted to the e q u a t i o n :
where, ho
were
- 27.509
71 =
0 50.
A H,.
14
-- -
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
v ) ,d Y
id
Using dH
dS=(C: / ~ ) d T + ( b . P / a T ) ~ d v
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
Using Equations [2] and @I in the nbov-? aqu:rtions and carryiog out tha
integration, we obtain cxpressmns for entropy and enthalpy a s :
Th~lizi.~modyna?nic
Properties of Carbon Disulphide
303
Liquid:
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
- T. 5 -
I , s.- J S ~ T
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
$0 1900.
An authoritative I-eview of K o b e a n d ZynnI2 gives the constants as
T, 5 5 7 . 1 6 " ~a n d PC 78.0 atmospheres. Hence, i t can be seen t h a t O'Brieo
and Alford did noL use the correct set of critical constants.
d
PCFbFf R l f U R C - E k T R B W
oraeaau FP#
C
VISWAYLIW. D S..
P-PRESSURE.
KULOOR. N
ITUOSPHERES
H - ENIHALPI. L I L O I I I S ~ G ~ ~ U W L
v=VOLUuE,
R E r I B L N C I STlTi
C IGRAPHliEI
PNO
----
~rrlrr/mr# roir
X = WEIGHT PERCENT
ATO'K
-- -
AN3 S (RHOMBICI
ZERO PRESSURE
H = O , AND s t R L ~ P - o
TABLEBrI
CARBON DISULPHIDE
TeK
P atm.
T"K-
P Alms.
0.10
0.20
.-
0.30
0 50
0.80
1.00
Pressure Range:
1.50
2.00
p
p
p
p
-
3.00
~..
~
5.00
v
H
H
S
H
S
P atms.
750.0
720.0
700.0
680.0
660.0
640.0
-TK
TABLE
VII--(contd.)
Pressure Range : 0.10
to 5.00
atrns.
6~~9.0
BlElE
PE'ES
QJO'I
6081E
FL'PS
SPE'I
L641F
OQ'S5
OLL'I
f9!ZC
11%
ewz
SIcZE
16'9S
S6.LS
SSKC
ots't
YP'8S
S
ROSZE
H
~ 9 8 . ~A
0'00s
TABLEY 11-(conld.)
Pressure Range: 8.0 to 60 0 atrns.
TDK
P Atms.
S.0
10.0
15.0
_.____
. . . .
20.0
_--.
25.0
- --
T A B ~VLIE
(~01$td.)
30.0
40.0
~~-~
50.0
~
--
--
60.0
--
150.0
--
200.0
25U.O
300 0
--
314
NOMENCLATURE
- Hant
..
..
..
Avenarius, M..
2. Battelli, A.,
3. Cross, P. C..
4. Fi~cher.R. and Rcichel, T.,
5. Galitzine, B..
1.
..
..
..
..
..
..
[I31
--
..
..
..
".
Gordon, A . It.,
Hanny.3. B.,
H e n n h p , F. and Stock, A,
..
..
Lowry, T. M.,
e.,
..
..
Mills. 3. E.,
..
Mathews, J. H..
O'Brkn,
..
Rex, A.,
..
Schcwcrs, F..
,.
Lecher. W. 6..
Sltmens. H. V.,
Thnrpe, T. E.,
Tyrer. D.,
Ibid,1880, 30. l i 8 .
!nd. T~zan?.
Ciwni., 1913, 35,851.
H. and
..
..
..
..
..
..
..
..
..
*.
..
..
..
.,
.
..
".
..
..
'%xn:l
..
..