THERMODYNAMIC PROPERTIES OF
METHYLENE CHLORIDE
BY SESHADRI, D. N., VISWANATH, D. S. AND KULOOR, N. R.
(Departmeni of Chemical Engineering, Indian Institute of Science, Bangalore-12, India)
!
1
[Received : November 5, 1966]
ABSTRACT
Thermodynamic properties of methylene chloride have been computed upto a
temperature of 750° K and a pressure of 200 atmospheres using Martin and Hou
Equation of State. The results are presented in tabular form and as an entropytemperature diagram.
INTRODUCTION
Methylene chloride is used as a refrigerant and hence a knowledge of its
thermodynamic properties is necessary. A detailed literature survey revealed
that the thermodynamic properties of methylene chloride are available only
upto a temperature of 423 ° K and a pressure of about 2.6 atmospheres.
In the present work, tables and a diagram of thermodynamic properties
of methylene chloride upto a temperature of 750 ° K and a pressure of 200
atmospheres are presented.
SURVEY OF EXISTING DATA
The critical pressure and temperature of methyCritical Constants;
present
lene chloride as given by Kobe and Lynn 6 have been used for the
investigation.
The critical volume of methylene chloride was calculated using
Meissner's ° method, Vowel's ° method, and by extrapolating the rectilinear
by the
diameter to the critical temperature. The critical volume calculated
last method was found to be in good agreement with the critical volumes
calculated by Meissner's and Vowel's method, and hence was accepted for the
present investigation.
Thus, the critical constants used in this work are :
I.
T, 510.0 °K
Pc r-- 60.0 atmospheres
ala 0.181 litres/mole.
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Thermodynamic Properties of Methylene Chloride
119
The maximum and average absolute deviations were found to be 0.46% and
0.15% respectively. Equation [21 has been used for the present investigation.
5.
Heat Capacity of the Saturated Liquid :
6.
Latent Heat of Vaporization:
The heat capacity of saturated
liquid has been presented by Dzung t . These data have been utilized in
checking the internal consistency of the tabulated results.
The heats of vaporization of methylene
chloride have been presented by Dzung 3.
These data were fitted to an
equation of the form :
[3]
with n-r-- 0.41 and AO = 9.062.
The maximum and average absolute deviations of calculated values of
heats of vaporization, in the range of available data were found to be 0.1% and
0.04% respectively.
For this work, Equation [31 has been accepted for the
calculation of latent heats of vaporization.
CALCULATION OF THERMODYNAMIC PROPERTIES
For the calculation of thermodynamic properties, Martin and Hou
Equation of State,
P
A2 # B2T + C2e-
RT
/1„)
KT1 Tc As+B37 4-
(V—
A4
+
C3e -ICTITe
(R- Boy
4- C se – KTITc
( 1 BO) '
B5T
(V B0) 4
£41
with K= 5.475 has been used.
a
The constants in Equation [41 evaluated following
outlined the authors' are :
130 = 3.307556 x 1(1 2
A2— — 16.355163
B2 Pa 1.1851555 x 10 -2
333.17645
C2
43 a 2.1346826
113 a — 1 . 4 1 263 0 x 10 -3
C3 —I 54.635205
A 4 _ 0.11580094
B5 a 7.3944412 x 10 -6
C3 -- 0 1 707260
Ca
the procedures
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1 r+
C.) ici
i
g
.i.
..7
1 as
NI0
(.51
-6i
cl
+
9g1 1
k
IS%
k
1
Ng
I
, ta crl
,
-----
...
es,
-•
N _i
±P
'I
+
......
....
Pci \ifs--
rem
----■
esgi
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111
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+
Esetag
ei--,
I
Nvaleve
I
•
Thrrmodynconic Properties of Methylene Chloride
121
properties, the heats of formation and Berthelot's correction for entropy and
enthalpy. Using the values of entropy and enthalpy at the boiling point, the
constants of integration, Cs and CH were evaluated.
The values of entropy and enthalpy were calculated at various temp&
ratures and pressures using Equations 11 and N.
ENTROPY AND ENTHALPY OF SATURATED VAPOUR
As Martin and Hou Equation of State (Equation 4) holds good for the
saturated vapour region also, the properties of saturated vapour were calculated
in the same manner as in the superheated vapour region.
ENTROPY AND ENTHALPY OF SATURATED LIQUID
The latent heat of vaporization of methylene chloride was calculated
using Equation [31.
The entropy of vaporization A Sy, is related to the heat of vaporization,
by the relation,
Allv— TASy
191
The entropies and enthalpies of' saturated liquid were calculated using the
equations,
ani
Si 9= Sg — A Sv
[10]
Iii =--- 1-18, — A If v
(I 1]
The properties of saturated and superheated methylene chloride are
presented in Tables I and 11 respectively, and in graphical form as Figure 1.
INTERNAL CONSISTENCY OF THE TABULATED RESULTS
The internal consistency of the results was checked by two methods as
outlined below.
(a) Using dH = Td S + Yd P:
may be used
dif
s
TdS
+
Vd
P
The relation ,
to check the internal consistency of the entropy and enthalpy values.
At constant pressure,
Hence di! de d (TS) — Sd T,
[12]
dif a- Td S
from which
54T
SI
-2
I
S2
e
T
HI 1 gc T2
(13]
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HICINU,
TABLE IT
Properties of Superheated Vapour
P Atms.-4-
0.1
0.2
228.5
-16374
68 43
245.1
-16131
69 27
261.7
- 15880
70 08
278 3
- 15621
70.87
294.8
- 15354
71.63
311.3
-15080
72.37
327 8
- 14799
73.09
344.2
-145U1
73 79
360 7
-14215
74.48
113.6
-16386
67.03
122.1
-16141
67.87
130.4
- 1f 888
68 68
138.8
- 15628
69.47
147.1
- 15360
70.24
155.4
-15U85
70 98
163 7
- 14803
71.71
171.9
-14514
72.41
180.2
-14218
73.10
0.3
05
(Pressure range 0.1 to 5.0 atms.)
1.0
2.0
3.0
5.0
TIC&
280.0
300.0
320.0
341,0.0
360.0
380.0
400.0
420.0
440.0
V
H
S
V
H
S
V
H
S
V
H
S
V
H
S
V
H
S
V
H
S
V
1-1
S
V
H
S
81.02
- 16150
67.04
86.67
-15896
67.86
92.27
- 15634
t)8 65
97.85
- 15366
69.42
103.4
-15090
70.17
108 9
-14807
70 89
114.5
- 14518
71 60
120.0
-14221
72.29
48.19
- 16170
65.98
51.65
- 15912
66.81
55.07
- 1564
67.61
58 46
- 15377
68 38
61.81
-1c100
69.13
65. 8
-14815
69.8S
68.52
- 14525
70 57
71.85
- 14228
71.26
25.38
15954
65.33
27 16
-15683
66.16
28.92
- 15406
66 95
30.65
- 15124
67.71
32.36
-14836
(8.45
34.06
- 14543
69.16
35.74
- 14143
69 86
13.19
-15754
64.62
14.13
- 15466
65.45
15.05
-15174
66.24
15.94
-14879
66,99
16.82
14579
67.72
17.69
- 14275
68.43
9.197
- 15528
64.51
9.841
-15226
65.33
10.46
-149;2
66.11
11.07
- 14616
66.86
11.67
- 14307
67.57
5 664
- 15335
64.10
6 075
-150J4
64 92
64t8
- 1404
65.70
649
- 14374
66.45
cta
".1
Ott"
SVE11
ZO - 01
Z9' 1 L
86911 —
089 6
Col t
Lta I
LEE' 6
EV'OL
16EZ1 —
Z66'8
18 - 69
TEM —
5179 8
81'69
L901.I —
got 8
ES'89
66EE1
Mitt
9819
LZLE1 —
E8CL
91 - L9
'NOVI —
OU'L
tall —
ZL'OS
6817L
Z179 1 1 —
LOt6t7
OE'VL
98611 —
It LV
IL'il
5ZEZI —
5C5t
01 . EL
8S9Z1 —
6041'
8IZL
L86Z1 —
EV'ZV
S8' I L
60EE I —
90E11 —
81'SZ
WEL
9S911 —
StIVZ
16•L
100ZI —
Z9 1 EZ
I E*ZL
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8L'IZ
OL; IL
9L911 —
tOs a
SOIL
900 .:I —
01'1Z
WOG
ZEEE I —
SZ*OZ
6L'69
159E1 a
017'61
Z1'69
996E1 —
SS'81
61E11 —
1891
L9'Zis
0L911"
gr91
80*ZL
910Z1'
8951
817' IL
85EZI —
Z I *SI
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g69Z1 —
C5 PI
5rOL
LZO€1 a
66'El
09'69
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9Z'ZI
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01' IL
LZ9E1 —
01'6C
tg'OL
816E1 —
EV . LE
01
ti 9L
981 —
9101
LZ*9L
VE911 —
01 . 86
695L
8L611'"
1056
60 . 5L
911Z1 —
IL'I6
6VVL
6179Z 1 —
1188
LWEL
LL6 : 1 —
01 .C8
VVEL
861E1 —
02 , 18
091L
i719EI —
6V . 8L
V61 L
tZ6E 1
LUSL
-
98'LL
E8Z11 —
17'691
6Z4LL
ZE911 —
601
It9L
. 5L611 —
S'851
I I 9L
CHU —
WES!
155L
9t9Z 1
5'LV1
68 . VL
L6Z1 —
O'ZVI
91*I'L
176ZEI —
c9E 1
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609E1 —
01E1
96'ZL
816E1'
SuSt I
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LTSL I co 08
15111 —
NM — ,
9 4 805
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01'8L
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0E911 —
S
H
A
S
H
A
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H
A
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H
A
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H
A
H
A
S
H
A
S
H
A
S
H
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696Z1
IL6Z1 —
5 1 9Zir
i
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LO'CL I St '9L
06ZE1 —
Z6IC I —
. 001P
6.170Z
18 . 5L
Wirt
tO9E1 —
L09C1 —
9' E6C
9961
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WEL
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916fl
F LU
t'88I
s
ZsZ6P
0'9VZ
68 8L
21
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ZL611 —
tL611 — 8' 5Lt
8 . LEZ 1
0E . 8L
i.
Z6'9L
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96t i Cat
OL'LL
ZE'9L I
Zt911
tV9Z 1
6 .ZVP
;
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1 80' LL
OCCL
-
-
-
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givi
4-.sti2v-d
160
Z'O
Ct
co
00Z9
0 009
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0 .0t5
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000C
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inocitA paingiocins jo sapiodom
romil
('pluo3)-11 ativj
TABLE 11
Properties of Superheated Vapour
____
_
_
__
P. Atms.-+
0.3
0.2
0.1
0.5
10
TIC 4
640.0
660.0
680.0
7G0.0
720.0
750.0
_
( Pressure range 0.1 to 5.0 atms.)
2.0
_
525.0
V
-10928
H
80.61
S
V
541.4
-10570
H
81.16
S •
V
557.9
-10207
H
81.70
S
V
574.3
H
-9841
S
82.23
V
590.7
11
-9470
S
82.75
V
615.3
11
-8906
S
83.52
262.4
- 10929
79.23
270.7
-10571
79.78
:78.9
-1O08
80.32
287.1
- 9842
80.85
295.3
- 947 I.
81.37
307.6
-8906
82.14
-
174 9
- 10930
78 42
180.3
-10572
78.97
185.9
-10210
79.51
191.4
- 9843
80 04
196.8
-9472
80 57
205.1
-8907
81.33
__
104.9
- 10932
77.40
108.2
-10574
77.95
111.5
-10212
78 50
114.8
-9845
79.03
118.1
-9474
79_55
123.0
-8909
80.32
52.38
- 10939
76.02
54 03
-10580
76.57
55.68
-10217
77.11
57.33
-9850
77.65
58.98
-9478
78.17
61.45
-8914
78.94
26.12
- 10951
74 63
26.95
-10592
75.18
27.78
-10228
75.72
28.61
-9860
76.26
29.44
-9488
76.78
30.68
-8923
77.55
3.0
_ _
17.36
- 10963
73.81
17.92
-10603
74 37
18.48
-10239
74 91
19.04
- 9870
75,44
19.59
-9498
75.97
20.42
. - 8932
76.74
5.0
'
10.36
-10988
72.77
10.70
-10626
73.33
11.04
-10261
73.87
11.38
- 9891
74.41
11.71
-9517
74.93
12.22
- 8950
75.71
fr.
o
ta:i
i
:IP
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tE3:I
tl:
et
.
81'09
91c1 —
Z691 0
d'
a
S
n
z
a
Cl;
1949
601(1 —
1169'0
VCE9
S6LEI —
S9Z9*0
ICZ9
OEN —
19175'0
ZZ19
101SI —
99Z17 .0
d
I.
ii<
z
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9Z°99
SS8ZI —
OZE°1
VS S9
ZSZEI —
OPZ*1
LL V9
60E1 —
SS 1 'I
V619
MP! —
Z901
00 19
SOSV1 —
9SS6°J
9819
LLOSI —
IEZ8*0
5i
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6S9ZI —
Z60
99°99
8Z011 —
L86° t
S6 - S9
0017E1 —•
6L13°I
IZ'S9
9LLE1 —
99L1
ZV V9
V911'1 —
1179°1
LS°19
L95tP1 —
ZIS'I
19°Z9
000SI —
Z91°1
6
72
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cA
L
o ooz
gym
cram
(roc
0 Oi
0'0Z
______
____
V6 4 89
LLVZ1 —
V61 V
11 89
9Z8! —
01Z4
S919
ZLIEI —
EZO 'V
8699
LiCEI —
ZEICE
Lt°99
198E1 —
919E
1750
90M —
Eio°1
LEV9
EMI —
'WE
S619
L0611 —
966•Z
SO 19
ELM —
ISLIZ
0'0i •
_
S
IT
A
S
H
A
S
H
A
S
II
•A
S
H
A
S
1-1
A
S
Ft
A
0°09S
0'0K
0 4 0ZS
o005
0°08V
•
0°0917
0 60117
s
H
A
S
Ft
A
4--.stuily
0'01P
0•0017
t Nei
Csullg 0 . 001 01 01)1 32= itissoid)
anochu panatpacIns Jo sa!liadoid
(ppioa)—II
aThYj
•
(concld.)
TABLE
Properties of Superheated Vapour
20.0
30.0
;. 50.0
2.193
-12290
67.97
2.291
-1192!
68.60
2.388
-1051
1.396
-12466
66.95
1.468
-12080
67.60
1.538
-11695
0.7520
- 12858
65.42
0 8061
-12425
66 15
O861
-12005
70.75
69.21
5.110
2.483
-11050
-11179
71.32
69 80
5. 1 86
2.577
-1O85
-10804
7L88
70.37
5.460
2.670
-10316
- 104728
72.44
70.94
5 634
2.762
-.9943 - 10047
72.98
71.49
5.807
2.853
-9566
-9666
73.51
72.03
6 065
2.988
-8995
-9086
7423
72.81
68.23
1.607
-11312
68.84
1 674
-10928
69.43
1.740
-10542
70 01
1.804
-10155
70.57
1.868
-9766
71.11
1 963
-9179
71.91
66.84
0.9048
-11592
67.49
0.9510
-11185
68.12
0 9957
- 10179
68.73
1.039
_10 1 75
69.31
1.082
-9972
69.88
1.144
-9366
70.71
10.0
P. Anus.
(Pressure range 10.0 to 20( atms.)
100.0
150.0
200 0
T°K
580.0
600.0
620.0
V
4 576
H
S
V
H
S
V
H
S
640.0
V
660.0
H
S
V
H
S
680.0
700.0
720.0
750.0
V
H
S
V
H
S
V
H
S
V
H
S
- 12126
69 56
4.755
-11771
70 16
4.933
-L1412
0.24/3
- 14240
62.10
0.2991
-13518
63.33
0.3407
-12922
64.31
0.3767
-123S8
65 15
0.4C92
-11890
65 92
0.4392
-11515
66 63
0.4674
-10955
67.30
0.4941
-10505
67.93
0.5322
-9842
68 83
'--i
-1714o
t.
`z
,tr.
0.1672
-14059
62.00
0.2015
-13309
63.19
0 2309
-12a68
64.18
0.:566
-12093
65 04
0.2799
-11558
65.81
0.3015
-11049
66 53
0.3316
-10319
67.52
Fi
3
0
0.1488
-13418
62.70
*b
et
4.-./.4
ttea
to
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et i
Zc.c
0 1677
fr
(11
-12786
63 65
0..878
Si
-12172
64 54
0.2e68
-1196
65 35
0.2328
-10789
--..2
t'6 45
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ai
bad • ad
c,; .0
Cl3
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M Ct
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W. Cci
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Thermodynamic Properties of Methylene Chloride
129
TABLE IV
Temp. °K
Ckliterature)
C/(calcuiated)
%deviation
250.0
23.341
22.617
3.10
260.0
23.351
22.941
1.76
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23.667
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300.0
23.898
23.856
0.18
310.0
24.162
24 051
0.46
NOMENCLATURE
Constants in Equation (2)
Constants in Equation (1)
a,b,c,d,
B0 1A21B2,,C2
A 3 , 133,C 3 1
A4 1 .85 C5
C F.
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°K
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°K
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Cv
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Constant in Equation (3)
Ti
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Entropy, calories/gram mole . .K
Temperature, G K
V
Volume, litres/gram mole
Enthalpy of vaporization, calories/gram mole
Entropy of vaporization, calories/gram mole
Heat of vaporization, calories/gram molt
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