methylene chloride thermodynamic properties of
TRANSCRIPT
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 entropy- temperature 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
I. Critical Constants; The critical pressure and temperature of methy-
lene chloride as given by Kobe and Lynn6 have been used for the present
The critical volume of methylene chloride was calculated using
Meissner's° method, Vowel's° method, and by extrapolating the rectilinear
diameter to the critical temperature. The critical volume calculated by the
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 :
T, 510.0 °K
Pc r-- 60.0 atmospheres
ala 0.181 litres/mole.
117
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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 : 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.
6. Latent Heat of Vaporization: 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,
RT A2 # B2T + C2e- KT1 Tc As B37 4- C3e -ICTITe P
/1„) (V— + +
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with K= 5.475 has been used.
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
C2 Ca 333.17645
43 a 2.1346826
113 a — 1 . 4 1 263 0 x 10 -3
C3 —I 54.635205
A4 _ 0.11580094
B5 a 7.3944412 x 10 -6
C3 -- 0 1 707260
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•
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,
S i 9= Sg — A Sv [10]
ani 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:
The relation , dif s TdS + Vd P may be used
to check the internal consistency of the entropy and enthalpy values.
At constant pressure, dif a- Td S [12]
Hence di! de d (TS) — Sd T, from which
HI 1 gc T2S2 e TI SI -- 2 54T
(13]
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e4 3H t-9 4 Eiv tH ..., IS •Scr 1S 2 A iik -sun y d Mol,
inodrA pue p!nbri Niuitues jo sap.ndom
HICINU,
TIC& P Atms.-4- 0.1 0.2
280.0 V 228.5 113.6
H -16374 -16386 S 68 43 67.03
300.0 V 245.1 122.1 H -16131 -16141 S 69 27 67.87
320.0 V 261.7 130.4 H - 15880 - 1f 888 S 70 08 68 68
341,0.0 V 278 3 138.8 H - 15621 - 15628 S 70.87 69.47
360.0 V 294.8 147.1 H - 15354 - 15360 S 71.63 70.24
380.0 V 311.3 155.4 H -15080 -15U85 S 72.37 70 98
400.0 V 327 8 163 7 H - 14799 - 14803 S 73.09 71.71
420.0 V 344.2 171.9 1-1 -145U1 -14514 S 73 79 72.41
440.0 V 360 7 180.2 H -14215 -14218 S 74.48 73.10
0.3 05
81.02 48.19 - 16150 - 16170
67.04 65.98 86.67 51.65
-15896 - 15912 67.86 66.81 92.27 55.07
- 15634 - 1564 t)8 65 67.61 97.85 58 46
- 15366 - 15377 69.42 68 38 103.4 61.81
-15090 -1c100 70.17 69.13 108 9 65. 8
-14807 -14815 70 89 69.8S 114.5 68.52
- 14518 - 14525 71 60 70 57 120.0 71.85
-14221 - 14228 72.29 71.26
1.0 2.0 3.0 5.0
25.38 15954 65.33 27 16 13.19
-15683 -15754 66.16 64.62 28.92 14.13 9.197
- 15406 - 15466 - 15528 66 95 65.45 64.51 30.65 15.05 9.841 5 664
- 15124 -15174 -15226 - 15335 67.71 66.24 65.33 64.10 32.36 15.94 10.46 6 075
-14836 -14879 -149;2 -150J4 (8.45 66,99 66.11 64 92 34.06 16.82 11.07 64t8
- 14543 14579 - 14616 - 1404 69.16 67.72 66.86 65.70 35.74 17.69 11.67 649
- 14143 - 14275 - 14307 - 14374 69 86 68.43 67.57 66.45
cta
TABLE IT Properties of Superheated Vapour
(Pressure range 0.1 to 5.0 atms.)
Ott" SVE11 ZO-01 Z9' 1 L 86911 — 089 6 Colt 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
05
CCU LO*PL 9PTL, ti 9L 98'LL LTSL I co 08 S
61E11 — 90E11 — tall — 981 — E8Z11 — NM — , 15111— H
1891 81'SZ ZL'OS 9101 17'691 VVSZ 94805 A 00Z9
L9'Zis WEL 6817L LZ*9L 6Z4LL 01'8L Li7.6L S
0L911" 9S911 — Z179 1 1 — VE911 — ZE911 — 0E911 — 6Z911 — H
gr91 StIVZ LOt6t7 01.86 601 0'9VZ ZsZ6P A 0 009
80*ZL 16•L OE'VL 695L It9L I 5'LL 2 68 8L S 1 910Z1' 100ZI — 98611 — 8L611'" . 5L611 — tL611 — - ZL611 — H
8951 Z91EZ It LV 1056 S'851 8.LEZ 1 8' 5Lt A 0.08C
817' IL I E*ZL IL'il 60.5L I I 9L Z6'9L i. 0E.8L S
85EZI — ItEr.1 — 5ZEZI — 911Z1 — CHU — ZIEZ1 — . WEN — H
Z I *SI 8L'IZ 5C5t IL'I6 WES! 96t i Cat A 0'095
LS OL OL; IL 01.EL 6VVL 155L ZE'9L I OL'LL S
g69Z1 — 9L911 — 8S9Z1 — 6179Z 1 — 9t9Z 1 - tV9Z 1 - Zt911 - H
C5 PI tOs a 6041' 1188 5'LV1 Ell ZZ ; 6.ZVP A 0.0t5
5rOL SOIL 8IZL LWEL 68.VL OCCL 1 80' LL s . LZO€1 a 900 .:I — L86Z1 — LL6 : 1 — L6Z1 — IL6Z1 — 696Z1 - H
66'El 01'1Z EV'ZV 01.C8 O'ZVI I'C1Z i 519Zir A 0.0Z g
09'69 WOG S8' I L VVEL 91*I'L LO'CL I St '9L S
VSEEI — ZEEE I — 60EE I — 861E1 — 176ZEI — Z6IC I — 06ZE1 — H
WEI SZ*OZ LCOP 02,18 c9E 1 6.170Z . 001P A 000C
S689 6L'69 01' IL 091L Z9' IL Wirt 18.5L S 9L9€!' 159E1 a LZ9E1 — i719EI — 609E1 — L09C1 — tO9E1 — H
VWZI 017'61 01'6C 6V. 8L 01E1 9961 9' E6C A 0.08t
LZ*89 Z1'69 tg'OL V61 L 96'ZL WEL cyst 'Si. S V66E1 — 996E1 — 816E1 — tZ6E 1 - 816E1' 916fl - 116c1" H 9Z'ZI SS'81 EV.LE LUSL SuSt I t'88I FLU A 0'0917 givi
t Not WE 0'1 01 co Ct Z'O 160 4-.sti2v-d
- _ ".1
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inocitA paingiocins jo sapiodom ('pluo3)-11 ativj
TABLE 11
Properties of Superheated Vapour
____ __ _ _ ( Pressure range 0.1 to 5.0 atms.)
_
P. Atms.-+ 0.1 0.2 0.3 0.5 1 0 2.0 3.0 5.0 TIC 4 _ _ _ '
640.0 V 525.0 262.4 174 9 104.9 52.38 26.12 17.36 10.36 H -10928 - 10929 - 10930 - 10932 - 10939 - 10951 - 10963 -10988 fr.. S 80.61 79.23 78 42 77.40 76.02 74 63 73.81 72.77
o
660.0 V 541.4 270.7 180.3 108.2 54 03 26.95 17.92 10.70 H -10570 -10571 -10572 -10574 -10580 -10592 -10603 -10626 ta:i S • 81.16 79.78 78.97 77.95 76.57 75.18 74 37 73.33 i
680.0 V 557.9 :78.9 185.9 111.5 55.68 27.78 18.48 11.04 :IP H -10207 -1O08 -10210 -10212 -10217 -10228 -10239 -10261
S 81.70 80.32 79.51 78 50 77.11 75.72 74 91 73.87 I
7G0.0 V 574.3 287.1 191.4 114.8 57.33 28.61 19.04 11.38 t H -9841 - 9842 - 9843 -9845 -9850 -9860 - 9870 - 9891 o S 82.23 80.85 80 04 79.03 77.65 76.26 75,44 74.41
720.0 V 590.7 295.3 196.8 118.1 58.98 29.44 19.59 11.71 11 -9470 - 947 I. -9472 -9474 -9478 -9488 -9498 -9517 c;..". S 82.75 81.37 80 57 79_55 78.17 76.78 75.97 74.93 3 et
750.0 V 615.3 307.6 205.1 123.0 61.45 30.68 20.42 12.22 n 11 -8906 -8906 -8907 -8909 -8914 -8923 . - 8932 - 8950 t- E3- S 83.52 82.14 81.33 80.32 78.94 77.55 76.74 75.71 :I tl: et - _ _
d' a S
n z a
Cl; d I. ii- < z <
5-
i 6 72 <
LcA
o ooz
. ______ ____ _
1949 601(1— 1169'0 VCE9 S6LEI — S9Z9*0 ICZ9 OEN — 19175'0 ZZ19 101SI — 99Z17.0
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
0 Oi
E1L9 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
0'0Z
V6489 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
S IT A S H A S H A S II
•A S H A S 1-1 A S Ft A s H A S Ft A
0°09S
0'0K
040ZS
o005
0°08V •
0°0917
060117
0'01P
0•0017
t Nei gym
81'09 91c1— Z691 0
cram (roc 0'0i • 4--.stuily
Csullg 0.001 01 01)1 32= itissoid) anochu panatpacIns Jo sa!liadoid
(ppioa)—II aThYj
•
TABLE (concld.) Properties of Superheated Vapour
(Pressure range 10.0 to 20( atms.)
P. Anus. 10.0 20.0 30.0 ;. 50.0 100.0 150.0 200 0 T°K
580.0
600.0
620.0
640.0
660.0
680.0
700.0
720.0
750.0
V H S V H S V H S V
H S V H S V H S V H S V H S V H S
4 576 - 12126
69 56 4.755
-11771 70 16 4.933
-L1412 70.75 5.110
-11050 71.32 5. 1 86
-1O85 7L88 5.460
-10316 72.44 5 634
-.9943 72.98 5.807
-9566 73.51 6 065
-8995 7423
2.193 -12290
67.97 2.291
-1192! 68.60 2.388
-1051 69.21 2.483
-11179 69 80 2.577
-10804 70.37 2.670
- 104728 70.94 2.762
- 10047 71.49 2.853
-9666 72.03 2.988
-9086 72.81
1.396 -12466
66.95 1.468
-12080 67.60 1.538
-11695 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
0.7520 - 12858
65.42 0 8061
-12425 66 15
O861 -12005
66.84 0.9048
-11592 67.49
0.9510 -11185
68.12 0 9957
- 10179 68.73 1.039
_101 75 69.31 1.082
-9972 69.88 1.144
-9366 70.71
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
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
0.1488 -13418
62.70 0 1677
-12786 63 65
0..878 -12172
64 54 0.2e68
-1196 65 35
0.2328 -10789
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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
270.0 23.476 23.227 1.06
280.0 23.522 23.450 0.31
290.0 23.684 23.667 0.07
300.0 23.898 23.856 0.18
310.0 24.162 24 051 0.46
NOMENCLATURE
a,b,c,d,
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Constants in Equation (2)
Constants in Equation (1)
i Constant in Equation (4)
Heat capacity at constant pressure, calories/gram mole
Heat capacity at constant volume, calories/gram mole
Enthalpy, calories/gram mole
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°K
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Pressure, atmospheres
Entropy, calories/gram mole ..K
G Temperature, K
Volume, litres/gram mole Enthalpy of vaporization, calories/gram mole
Entropy of vaporization, calories/gram mole Q.K
Heat of vaporization, calories/gram molt
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