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Section A, Vol. 15
VISCOSITY OF MULTICOMPONENT
GAS M I X T U R E S OF POLAR GASES
b y S. M A T H U R
and S. C. S A X E N A
Summary
The rigorous binary viscosity expression ~mix as transformed to the form
originally suggested by S u t h e r l a n d is studied for mixtures involving
polar gases. Any attempt to simplify the ~o' of the Sutherland viscosity
expression turns out to be only approximately successfui. A relation for
~~j/~ji is however derived, and the procedure suggested for computing
~mix on this basis appears to be very successful. The ~ij to a large extent
are temperature and composition independent and it has been shown that
this fact can be utilised with success for predicting *Tmixvalues at high
temperatures.
1. I n t r o d u c t i o n .
At the first sight the f o r m u l a t i o n of t r a n s p o r t
coefficients for polar gases seems to be a v e r y c o m p l i c a t e d job because of the a n g u l a r dependence of the i n t e r m o l e c u l a r potential.
Mason, Vanderslice
a n d Y o s 1) m a d e a r e m a r k a b l e contribution in this direction b y showing t h a t the results of the f o r m a l
kinetic t h e o r y 2) still r e m a i n uneffected except the collision integrals are n o w e v a l u a t e d differently a n d these now b e c o m e the
averages over all the possible potentials. M o n c h i c k a n d M a s o n 3)
h a v e recently even calculated such collision integrals for a Stockm a y e r t y p e p o t e n t i a l 4) viz.,
q~is(r) :
4 e i j [ ( a i / r ) 12 - - ( a i / r ) 6 + ~J(aij/r) 3 ~ij],
(1)
203
204
(2)
where
(3)
Bs--(~1/~72)(/fl),
b12 =
(~~1 _
Vs~l)/fl +
(4)
(5)
~~1,
(6)
fl --
(7)
and
2RT 5 -- 3A12
Y - - 5pD12 M1 q- M2
(8)
~]1
1 -1- ~I2(X2/X1)
-~-
7]2
1 -~ qO21(Z1/X2) '
(9)
where
B12 _ BXl(X2 2_
~l~
B21Xl)-1
1 4- Bx2(%2 -~ B21Xl)-1
(lO)
(1 1)
B12B~I1 = f12,
(12)
and
B ~--- B21fi12(~]l 4-
7]2) - 1
--
1.
(13)
205
We now look into the possibility of further simplifying the expression for ~~j. following G a m b h i r and S a x e n a 5 ) . For systems
where M1 ~ M2 (we use subscript 1 throughout to characterise
the heavier component) the factors
Bxl(x2 4- B21xl) -1
= X,
and
Bx2(x2 4- B21x1) -1
= Y
482).
(14)
(15a)
(1sb)
Similarly,
B21 ~
B21 =
282
(16)
__~"b12/282
(16a)
_~ 1/~/~
(16b)
B12
B21
~- -8 2 =
(i7)
~12
82(Q + x~)
B21
(Q 4- 82 X2) '
(18)
where
Q=
(19)
206
207
Computed values of the singly approximated 9t3 and a few other faetors
System
H2-NHa
Temp.
oK
Xl
293.16
0.1
0.9
523.16
N2-NH3
293.16
523.16
0.1
0.9
0.1
0.9
0.1
287.66
0.493
0.371
0.493
0.371
0.478
0.046
0.014
0.190
0.071
0.023
0.114
0.005
0.052
0.011
0.001
0.093
0.011
0.004
0.033
1.081
1.054
0.963
1.054
0.963
0.920
0.9
CH4-NHa
0. I
0.9
Y
0.410
0.125
0.021
0,008
0.204
0.013
0.048
0.006
0.096
0.011
0.010
0.001
0.035
0.004
B 2 1 "~ 9 2 1
(16)
2.698
2.029
2.698
2.029
2.093
I
I
0.899
1.038
0.949
1.038
0.949
1.064
Computed values
System
H2-NH3
N2-NH~
. CH4-NH~
of the
Temp.
K
293.16
523,16
293.16
523.16
287.66
(bi22
4/~2)
+ 0.015
0.000
-- 0.133
+ 0.008
-- 0.073
~1~ ~ ~/B2
(15b)
0.427
0.478
1.097
1.007
0.930
2.339
2,093
0912
0,993
1.076
In table Il, we record the values of the factor b~~ -- 4fi2 for all
the three systems at the two extreme temperatures. In almost all
cases it can be regarded as negligibly small. Thus, off-hand the
doubly approximated 9~~ values are likely to be right for these
eases. Computed values of such ~ij are given in this table while
208
S. M A T H U R
AND
S. C. S A X E N A
the /]mix values obtained on the basis of (9) using these ~i;" are
recorded in table IV column 6. The agreement with the experimental values ig now slightly inferior than obtained on the basis
of the calculations using singly approximated ~0i;"values. The difference though is not appreciable in most cases. The average absolute
deviation is 3.5%, while the maximum and minimum deviations
are 10.2 and 1.0 percent respectively.
III
TABLE
I
System
Temp.
H2-NH
xl
~12
(I0)
293.16
0.1
0.9
0.1
0.9
0.1
0.9
0.1
0.9
0.1
0.9
0.317
0.297
0.378
0.359
1.027
1.024
0.952
0.951
0.885
0.884
523.16
N2-NHs
293,16
523.16
CH4-NHa
287.66
~~~
modified
(I0)
1.653
1.755
1.591
1.669
0.851
0.854
0.937
0.938
1.022
1.024
In table III we list the rigorous qq2 values for these systems as
a function of composition and temperature obtained according to
(10). ~021 values are also given in all cases and are based on the
modified equation obtained from (10) by interchanging the subscripts 1 and 2. The calculated ~mix values using these rigorous ~ij
values are also recorded in table IV column 7. The agreement with
TABLE
IV
Temp.
oK
293.16
523.16
N~-NHa
293.16
523. I6
CH4-NHa
287.66
~mix X 10 v
xl
0.1
0.9
0.1
0.9
0.1
0.9
0.1
0.9
0.1
0.9
Exptl.
1004
1004
1505
1825
1081
1696
1927
Calc.
(9), (14), (16)
2584
945
989
1399
1788
1057
1878
1925
2665
1099
1008
1065
984
Calc.
(9),(15b), (16b)
( % (10)
902
978
1399
1788
1054
1673
I907
2647
1062
983
999
1003
1519
1826
1068
1691
1929
2670
1072
991
Calc.
V I S C O S I T Y OF G A S M I X T U R E S
209
210
S. M A T H U R A N D S. C. S A X E N A
values
System
Temp.
xl 2
H2-N[H~
293.16
0.01
0.25
0.81
0.Ol
0.25
0.81
0.01
0.25
0.81
0.01
0.25
0.8I
0,01
0.25
0,81
oi~
523,16
N2-NH8
293.16
523.16
CH4-NI-ta
287.66
i n (18)
32xP
(Q + x12)(Q +/hx22) -1
--2.895
--6.282
-- 10.923
- - 4.446
-- 8.643
--14.222
--272.571
--240.346
--235.153
-- 793.844
--789.450
- - 784.561
--370.080
--392.674
- - 415.922
0.148
0.046
0.002
0.185
0.057
0.002
0.974
0.301
0.012
O. 822
0.254
0.010
0.700
0.216
0.009
1.050
0.967
0.926
1.041
0.977
0.943
1.003
1.000
0.997
1.001
1.000
0.999
1.002
1.000
0,998
only inappreciably departs from unity. Its average absolute deviation for all the systems given in table V is 1.9% only. Thus, the
simplified version of (18) as given by (17) may be regarded as
fairly accurate and reliable. One further simplification is possible
in (17) without impairing the aecuracy. This is because of the
circumstance that the quantity A~2 which is the ratio of the two
collision integrals is very insensitive to the nature of molecular
interactions and the temperature. This factor has been tabulated
by M o n c h i e k and M a s o n a) and we suggest a value of 1.10 for
A~2 in conformity with its characteristic value even for nonpolar
gases. The form of (17) therefore becomes as
~1~_
B21
(20)
Thus, if pure viscosities are known the ratio ~v12/~21 can be accura~ely calculated from the above relation. We further suggest to
VISCOSITY
211
OF GAS MIXTURES
Computed values of
System
H2-NH3
Temp.
oK
XI
293.16
523.16
N2-NH8
293.16
523. I6
I
CH4-NHa
287.66
Vl
X1
0.1
0.5
0.9
0.1
0.5
0.9
0.1
0.5
0.9
. 1
0.5
0.9
0.1
0.5
0.9
0.183
0.228
0.228
1.202
1.203
1.015
1.014
0.865
0.864
(18)
0.192
0.177
0.169
0.238
0.223
0.215
1.207
1.203
1.199
1.016
1.015
1.014
0.866
0.864
0. 863
all the three cases i.e. when one uses singly approximated, doubly
approximated and rigorous 9,j values. For the first two approximate cases this is independent of composition but does depend on
temperature, while in the rigorous case it is dependent both on
temperature and composition. In the latter case, if we take the
average of the values at the two extreme values of xl, we get very
approximately the same value whieh is obtained at the middle
composition and further this value is in excellent agreement with
the first two sets of approximate values which can also be regarded
as identical to a very great degree of accuracy. The sum total result
is that in the rigorous method if we try to ascfibe a sort of weighted
212
S. M A T H U R A N D S. C. S A X E N A
T A B L E VII
Comparison of the calculated and experimental ~/mix values
Gas
pair
NH~-H2
T~o~p
293.16
373.16
473,16
523.16
NHa-N~
293.16
373.16
473.16
523.16
Xpolar [
10 v X ~mix
(gin/cm-see)
I Exptl I
Cale.
0,9005
0.7087
0.5177
0.2975
0.2239
0. I082
1004
1047
1080
1087
1072
1011
lOO5(+o.1)
lO47(o.o)
lO8O(O.O)
lO87(o.o)
lO72(o.o)
lO14(+o.3)
0.9005
0,7087
0.5177
0.2975
0.2239
0.1082
1299
1333
I354
1329
1299
1204
13o2(+o.2)
1341(q 0.6)
1367(+1.o)
135o(+ 1.6)
132o(+1.6)
1227(+1.9)
0.9005
0.7087
0.5177
0.2975
0.2239
0.1082
1660
"1680
1676
1610
1560
1432
1668(+o.5)
17o3(+1.4)
1718(+2.5)
1670(+3.7)
1621(+3.9)
1483(+3.6)
0.9005
0.7087
0.5177
0.2975
0.2239
1825
1837
1823
1737
1678
1836(+0.6)
1869(+ 1.7)
1879(+3.1)
1818(+4.7)
176I(+4.9)
0,8883
0.7147
0.8638
0.2920
0.111I
1092
1254
I383
1585
1690
1093(+0.1)
1254(0.0)
0.8883
0.7147
0.5638
0.2920
0.1111
1398
1569
1710
1920
2031
1406(+0.6)
1591(+1.4)
1739(+1.7)
1963(+2.2)
2084(+2.6)
0.8883
0.7147
0.5638
0.2920
0.1111
1768
1946
2085
1787(+1.1)
1989(+2.2)
2149(+3.1)
2296
2383(+3.8)
2503(+3.9)
0.8883
0.7147
0.5638
0.2920
0. i l l l
2408
1939
2112
2250
2460
2572
Gas
pair
Temp.
K
NHa-02
293.16
Exptl. I
1143(0.0)
1350(0.0)
373.16
0.8755
0.7079
0.4786
0.2986
0.1351
1472(+0.9)
1718(+ 1.7)
2019(+2.4)
2228(+2.7)
2394( + 2.9)
473.16
0.8755
0.7079
0.4786
0.2986
0.1351
1459
1689
1972
2170
2326
1840
0.900
0. I00
1008
1069
I061
1077
1091
1099
1105
1105
1099
0.8220
0.7179
0.5042
0.2031
0.8220
0.7179
0.5042
1461
1469
1471
1342
1457(--0.3)
1467(--0.1)
147l(0.0)
1345( + 0.2)
1626
1632
1625
1472
1848
1855
1831
1621(--0.3)
0.300
0.200
1586(+0.1)
1699(+0.5)
294.16
I.
327.16
0.2031
372.16
1864( + 1.3)
2141(+2.7)
2473( + 3.5)
2700(+3.7)
2878(+3.7)
0.900
0.800
0.700
0.600
0.500
0.400
0.300
0.200
0.100
0.700
0.600
0.500
0.400
287.66
2085
2390
2604
2773
1604(0.0)
1784(+0.1)
1927( + 0.2)
1100
1203
1306
1403
1492
1576
1618
1713
1764
0.800
HCI-H2
Caic.
1143
1350
1604
1783
1924
N H 3-Air !288.66
NHa-CHa
(gm/cm-sec)
0.8758
0.7079
0.4786
0.2986
0.1351
1383(0.0)
1960(+ 1.1)
2168(+2.7)
2332(+3.6)
2568( + 4.4)
2686(+4.4)
10 7 X ~}mix
Xpplar
0.8220
0.7179
0.5042
0.2031
1629
1093(--0.6)
1205(+0.2)
1308(+0.2)
1404(+0.1)
1492(0.0)
I571(--0.3)
1642(+ 1.5)
1704(--0.5)
1755(--0.5)
1006(--0.2)
1037( -- 0.2)
1059(--0.2)
1077(0.0)
1091(0.0)
I099(0.0)
1102( -
0.3)
1098(--0.6)
1089(--0.9)
1630(--0.1)
1628 ( + 0.2)
1474(+0.1)
1849(+0.0)
1856(+0.o)
1845(+0.8)
1653(+ 1.5)
213
Temp.
oK
1HC1-CO2
SO2-H2
107 X ~]mix
(gin/cm-sec)
] ExptI. i
Calc.
427.16
2099
0.8417
2104
0.6989
0.5092 i 2053
1866
0.2409
2115(+0,8)
2121(+0,8)
2101(+2.3)
1921(+2.9)
473.16
0.8417
0.6989
0.5092
0.2409
2311
2304
2261
2024
2315(+0.2)
2319(+0.7)
2292(+1.4)
2087(+3.1)
0.7947
0.6312
0.5178
0.2991
2527
2507
2454
2281
2541(+0.6)
2533(+1.0)
0.900
0.800
0.700
0.600
0.500
0.400
0.300
0.200
0.100
I489
1545
1592
1638
1678
1715
1749
1778
1800
1502(+0.9)
1548(+0.2)
1596(+0.3)
1637(--0.1)
0.900
0.800
0.700
0.600
0.500
0.400
0.300
0.200
0.100
0.8215
0.5075
0.2963
0.2286
0.1676
1293
1350
1370
1272(--1.6)
1350(0.0)
1376(+0.4)
1344
1304
1363(+1.4)
1330(+2.0)
0.8028
0.5075
0.2963
0.2286
0.1676
1425
1475
1494
1453
1410
1416(--0.6)
1489(+0.9)
1508(+0,9)
1490(+2.5)
1449(+2.8)
0.8028 ! 1535
0.6999 I 1557
0.6175 I 1 5 7 4
1558(+o.1)
523.16
HC1-Air
Xpolar
298.66
291.16
290.16
318.16
343.16
l 0 T X 'r/mix
Gas
pair
Temp.
K
365.16
2508(+2.2)
2355(+3.2)
Exptl. ]
Calc.
0.4823
0.2963
0.2306
0.1676
0.1657
1587 I 1609(+1.4)
1596 1619(+1.4)
1551 1598(+3.0)
1500 i I550(+3.3)
1505 1547(+2.8)
0.8028
0.6999
0.6175
0.4823
0.2306
0.1676
0.1657
1648
1675
1682
1640
1573
1577
1633
1627(--0.4)
1654(+0.4)
1675(0.0)
1705(+1.4)
1687(+2.9)
1634(+3.9)
I632(+3.5)
1797
1814
0.6760
0.4698
0.3265
0.1676
0.1512
1942
1960
1942
1803
1748
2004(+3.2)
1894(+5.0)
1867(+6.8)
472.16
0.6760
O.4905
0.3265
0.1512
2118
2121
2098
1953
2125(+0.3)
2166(+2.1)
2165(q 3.2)
2007(+2.8)
SO2-CO2
288.96
0.900
0.800
0.700
0.600
0.500
0.400
0.300
0.200
0. I00
1288 1262(--2,0)
1316 1296(-- 1.5)
1338 1329{--0.7)
1363 1358(--0.4)
1384 1384(0.0)
1407 ! 1406(--0.1)
1429
1424(--0.3)
1447 i 1436(--0.8)
1464 1442(-- 1.5)
H2S-Air
290.36
0.900
0.800
1331
1403
1469
1535
1603
1655
1709
1755
1795 i
432.16
1718(+0.2)
1755(+0.3)
1788(+0.6)
1819(+1,0)
1579(+0.3)
(gin/cm-sec)
0.6760
0.4698
0.3265
0.1636
397.16
1678(0.0)
1527(--0.5)
Xpolar
0.700
0.600
0.500
0.400
0.300
0.200
0.100
1801
1685
1805(+0.4)
1851(+2.0)
1856(+3.1)
1755(+4.2)
1955(+0.7)
2003(+2.2)
1330(--0.1)
1403(0.0)
1474(+0.3)
1541(+0.4)
1603(0.0)
1660(+0.3)
1710(+0.1)
1752(--0.2)
1785(--0.6)
214
S. MATHUR
AND
S. C. SAXENA
Temp.
K
NH~-He
NH3-N2
NHs-02
NH~-Air
NH~-CH4
HC1-H2
HC1-Air
HC1-COe
SO2-H2
SO2-CO2
H~S-Air
293.16
293.16
293.16
288.66
287.66
294.16
298.66
291,16
290.16
288.96
290.36
~1 x 107
~]g x 107
912
9)21
982 ~) ~) k)
1758 a)
2031 d)
881 a)
982 a)
982 a)
975 a) g) k)
1073 a)
884 a)
1845 a)
1415 e)
876 a)
144! a)
1807 a)
0.305
0.973
0.972
0.916
0.811
0.237
0.764
0.857
0.142
0.721
0.676
1.670
0.809
0.779
0.760
0.938
1.829
1.162
0.971
2.185
1.144
1,110
1797 a)
973a) g) k)
1433 e) h)
1455 c) ~1)
1451 a)
1230f) i) j)
1225f) i) j)
1252 b) e)
VISCOSITY OF GAS M I X T U R E S
2t5