Appl. sci. Res.
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
Physics Department, Rajasthan University, Jaipur, hldia
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)
where the subscripts i a n d 7" denote the molecular species of the
i n t e r a c t i n g pair, 6ij =/~i#/2(eija~3), # is the dipole m o m e n t a n d the
o t h e r t e r m s are as defined b y t h e m a ) . T h e eij a n d ais are d e t e r m i n e d
fairly a c c u r a t e l y f r o m the corresponding q u a n t i t i e s for the p u r e
gases b y e m p l o y i n g the geometric a n d a r i t h m e t i c m e a n rules respectively.

203
204
S. MATHUR AND S.C. SAXENA
2. Formulae. The first approximation to the viscosity of a
binary mixture ~mix is s) 5)
~]mix =
X12~]1 4 f112XlX s _~_ flSX2~2
2
X~ 4 b12XIX 2 @ fi2X 2
(2)
where
(3)
B12 = (1 4 2T~I @ ~]1~]21)/fl,
Bs(~1/~72)(/fl),
b12 =
(~~1 _
Vs~l)/fl +
(4)
(5)
~~1,
2RT 5M1 + 3A*12M2
5pDls MI(M1 /Ms) '
(6)
fl 
2RT 5M2 + 3A~~M1
5pDl2 M2(Mi 4 M2)
(7)
and
2RT 5  3A12
Y   5pD12 M1 q M2
(8)
Here ~ is in gm cm 1 sec I, p in dyne cm% R the gas constant in
erg mole 1 deg 1, Dl2 the diffusion coefficient in cm 2 sec 1, x the
mole fraction, M the molecular weight, T the temperature in K,
and A12 is the ratio of two collision integrals. The values of A~~
as a funetion of d12 and T;2 = kT/elS are given by M o n c h i c k
and M a s o n 3 ) .
The expression for flmix as given b y (2) can now be easily transformed into the form given b y S u t h e r l a n d 6) viz.,
7]mix :
~]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)
B12 @ B~i1 = bi2,
(1 1)
B12B~I1 = f12,
(12)
and
B ~ B21fi12(~]l 4
7]2)  1

1.
(13)
~021 can be generated from c~12, (l 0), by interchanging the subscripts.
VlSCOSITY OF GAS MIXTURES
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
are usually smaller as compared to B12 and 1 respective]y, and we
can write
B12 ~ B12  1(512 Vb22
482).
(14)
Further as b~2  482 is invariably small
q~12~ b12.
(15a)
If b~2  482 ~___0 is a reasonable assumption, we get
(1sb)
Similarly,
B21 ~
B21 =
b12 ~/b~2  482
282
(16)
__~"b12/282
(16a)
_~ 1/~/~
(16b)
Dividing (15b) by (16b) we get
(5M1 4 3A~~]~jr2) ~]1M2
(5M2 4 3A12M1) ~~2M1
B12
B21
~ 8 2 =
(i7)
Based on relation (10), we can also write
~12
82(Q + x~)
B21
(Q 4 82 X2) '
(18)
where
Q=
B21 x~ 4 (1 @ B12B21) xlxz 4 B12x~
B{Bel   122
1 (~1 / ~2) 1}
(19)
Equation (18) is not inconsistent with (17), because usually both
Xl2 and 82x22 are small compared wJth Q and in such cases both the
expressions are identical. This interesting result establishes the
equivalence of two different sets of approximations. We now proceed to test the appropriateness of different expressions by performing numerical calculations on a few specific gas pairs.
206
S. MATHUR AND S. C. SAXENA
5. Calculations and discussions. In t h e previous section we
have succeeded in writing the ~mix expression as given by (2) in
the form of S u t h e r l a n d ' s expression, (9), with three different sets
of coupled values for 9*J. These m a y be ealled: (a) rigorous set i s
one in whieh no approximation has been made and ~12 is given by
(10) and 921 b y a similar equation in which the subscripts referring
to the molecular species are interchanged; (b) singIy approximated
set as given b y (14) and (16); and lastly (c) doubly approximated set
(15b) and (16b). We do not suggest the set of ~ij values given by
(i5a) and (16a) for computing ~inix, for this requires the knowledge
of force field between the molecules and also the computational
simplification is rather trivial as compared to the set (t 4) and (16).
For these very two reasons the doubly approximated set should
be most preferable if the calculations could establish its accuracy.
We may now compute ~mix Oll the basis of (9) using these three
sets of 9*J values with a view to assess their relative aecuracy. The
nature of assumptions made in simplifying ~i~ dictate orte general
requirement for choosing the gas pair viz., it should satisfy the
condition M1 >~ M2. However, we consider in this article the
specific binary gas combinations of NH3 with H2, N2 and CH4.
It should be noted that for all these systems the approximation
M1 >~ M2 is rather poor but for the same reason these systems
offer a crucial test to the simplifying proeedure and the resulting
formulae.
To know the degree to which the various speeific approximations
hold for these systems we record in table I the computed values of
the constants X and Y at two limiting compositions, and at the
two extreme temperatures where experimental data are available.
In eertain cases two sets of B12 values are obtained and for all
such cases two values of X and Y are recorded for the same value
of Xl. In such cases we have underlined the particular set for
which the various approximations hold bettet and therefore should
be preferred. Similar calculations were performed for 21 and the
final values only are given in the table for the sake of brevity. It
should be noted that contrary to out expectations the two assumptions viz., X ~ B12 and Y ~ 1, are least valid for the system
H2NH3. For N~NHs and CH4NHs systems these approximations
hold reasonably well and thus these calculations reveal that any
assessment just on the basis of molecular weights m a y not be cor
VISCOSITY OF GAS MIXTURES
TABLE
207
Computed values of the singly approximated 9t3 and a few other faetors
System
H2NHa
Temp.
oK
Xl
293.16
0.1
0.9
523.16
N2NH3
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
CH4NHa
B12 "~ ~o12
(14)
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
rect contrary to our experlence with the mixtures of nonpolar
gases. Finally, to judge the appropriateness of these singly approximated 9ij we compute ~mix and these are listed in table IV
column 5. The agreement with the experimental values, recorded
in column 4, is not as good as obtained with the rigorous theory
and indeed is unsatisfactory for H2NH3. For the remaining two
systems the agreement may be regarded as satisfactory. The average absolute deviation being 2 . 8 , while the maximum and minimum deviations are 7.0 and 0.1 percent respectively. These numbers
refer to all the mixtures considered in table IV.
T A B L E II
Computed values
System
H2NH3
N2NH~
. CH4NH~
of the
doubly approximated ~ij and the faetor (b]2 ~  4~72)
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)
~~1 ~ (1/~//~)
(16b)
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, offhand 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
Computed values of the rigorous q0j
I
System
Temp.
H2NH
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
N2NHs
293,16
523.16
CH4NHa
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
Experimental and calculated ~mix values obtained according to different p~j
System
H2NHa
Temp.
oK
293.16
523.16
N~NHa
293.16
523. I6
CH4NHa
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
the experimental values, as expected, is much improved and the
deviations with the experimental values are not very disappointing.
The average absolute deviation obtained is 1.1%, while the maximum and minimum deviations are 3.3 and 0.1 percent respectively.
From a critical study of the tables I, II and III certain important features regarding ~0i~ are obvious. The rigorous 9~~ are
seen to be temperature dependent though for most of the systems
it is not likely to be pronounced. The composition dependence is
negligible in all cases except for H 2  N H s system, which is also
somewhat unique as regards the composition dependence of ~mi
The singly approximated 9iJ values are dependent on temperature
though the nature of approximation make it composition independent. Similar remarks also hold for doubly approximated 91j
values.
As already stated the three sets of computed ~mix values obtained using the rigorous, singly and doubly approximated ~~~
values are recorded in table IV at a few representative temperatures and compositions along with the experimental values. A few
conclusions are straightforward. The rigorous values are in excellent agreement with the experimental values in almost all cases.
The discrepancies are pronounced in both the other sets of computed values and the difference is larger than the uncertainty
associated with the experimental data. The interesting point to
note is that leaving the H 2  N H s system at the lowest temperature
both the singly and doubly approximated ~ij values lead to very
much the same values. This conclusion is of great practical utility
for it suggests that fairly reliable values of ~mix are obtained using
the doubly approximated ~~j values.
No doubt rigorous ~i3"lead to better ~mix values b u t the associated
handicap of tedious lengthy calculations and the knowledge of the
interatomic potential is a seri6us limitation. E r e n the singly approximated ~vij values suffer appreciably for the same reasons.
Thus, if we could employ these doubly approximated ~0ij values in
such a way that the accuracy of calculated ~mix is increased we
will have a great practical success of an important and useful
nature. We explore this possibility in the ratio ~0~j/%'i obtained
using these doubly approximated ~ij expressions.
Two relations for the ratio of ~12 and ~~1 have been derived in
the previous section viz., (17) and (18). At first sight these look
210
S. M A T H U R A N D S. C. S A X E N A
quite different. The calculations given in table V, however, tend to
clarify the ineIfectiveness of the Iactor (Q + x~) (Q +/%x~)i
and thus the marked and pleasant equivalence of the relations of
(17) and (18). To a reasonable degree the approximations that x~
and 2x~ should be small as compared to Q hold for these three
systems. Consequently, the factor distinguishing the two expressions
TABLE
Calculated
values
System
Temp.
xl 2
H2N[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
N2NH8
293.16
523.16
CH4NIta
287.66
of certain factors occuring
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
filM2 (5M1 + 3.30M2)
~2M1 (5M2 + 3.30M1)
(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
determine the abso]ute 9# values occurring in (9) on the basis of
the above relation between g0ij and ~3"i. and one ~mix value.
Before we discuss the detailed calculations of ~mix aceording to
this procedure let us examine the temperature and composition
dependence of the ratio (~12/g021). One expects this factor to be
only weakly dependent on temperature because of the feeble dependences of (pD12/~T) and (~1/~2) on temperature. These are
relatively better approximations for nonpolar gases but are not
too unreasonable even for polar gases. To actually demonstrate
the limitations of these approximations and their effectiveness we
record in table VI the values of ~12/~21 for these three systems for
TABLE
Computed values of
System
H2NH3
Temp.
oK
~12/~0fll and its likely composition dependence
XI
293.16
523.16
N2NH8
293.16
523. I6
I
CH4NHa
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
(14), (16) I (15b),(16b)
0.183
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
NHaN~
293.16
373.16
473.16
523.16
Xpolar [
10 v X ~mix
(gin/cmsee)
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
NHa02
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
HCIH2
Caic.
1143
1350
1604
1783
1924
N H 3Air !288.66
NHaCHa
(gm/cmsec)
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
VISCOSITY OF GAS MIXTURES
TABLE VII (continued)
Comparison of the calculated and experimental ~/mi~ values
Gas
pair
Temp.
oK
1HC1CO2
SO2H2
107 X ~]mix
(gin/cmsec)
] 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
1459 1444( 1.0)
1472 1466(0.4)
1483 1483(0.0)
1492 1494(+0.1)
1499 1499(0.0)
1502 1499(0.2)
1503 !1494(0.6)
15oo
1485( 1.o)
1495 1470(1.7)
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
HC1Air
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)
SO2CO2
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)
H2SAir
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/cmsec)
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
value for the ratio in reference to composition it will invariably
be the same as that obtained from the two approximate procedures.
This further emphasises that the ratio as given by (20) is to be
associated with a high degree of accuracy. Of course the temperature dependence of this ratio is not negligible and any procedure
based on this assumption will have to counterbalance this inherent
deficiency if reliable and accurate ~mix values are to be evolved.
Computed values of ~]mix for a large number of systems, where
experimental data are available, as a function of composition according to the procedure which exploits (9) and (20) in conjunction
with one experimental ~mix value are recorded in table VII. These
caleulations refer to seventynine mixtures at the lowest temperature for all the systems and the agreement between theory and
experiment is excellent. The average absolute deviation is only
0.4%. This compares very favourably with the rigorous method
where the corresponding deviation is 1.7/o. The various ~v,3. values
along with the pure viscosity data are recorded in table VIII.
TABLE VIII
D a t a used for calculation of b i n a r y viscosity
Gas pair
Temp.
K
NH~He
NH3N2
NHs02
NH~Air
NH~CH4
HC1H2
HC1Air
HC1COe
SO2H2
SO2CO2
H~SAir
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)
The subscript 1 refers to the heavier component.
Though, as shown earlier the ratio ~12/~v21 is still dependent on
temperature if we use this value at a higher temperature in conjunction with a ~mix value at that temperature, it is likely that
the absolute ~v~j values so obtained m a y successfully explain the
viscosity results. This approach demands for its success the cancellation of the consequence of assuming the ~0ij. ratio to be temperature independent in the use of ~]mix at that temperature while
VISCOSITY OF GAS M I X T U R E S
2t5
fixing the absolute values of ~%.. This optimism is likely to be
successful for it has been known that there is an inherent large
flexibility in the ~%. values in (9) to repersent ~mix. As a check we
calculate the viscosity for all these systems at higher temperatures
as a Iunction of composition where experimental data are available.
In table VII, we report for such ninetyfive mixtures and the
absolute deviation on the average is only 2.0 percent. This, however, is not bad when one recalls the simplicity of the calculation
procedure.
An interesting point which still remains to be investigated is the
degree of the success that can be achieved if the whole procedure
is directly performed at the higher temperature i.e. calculation of
the ratio ~12/~v2 Indirectly this will check the assumption of the
invariance of the ratio ~v12/~21 with temperature. We choose the
systems H2NH3 and N2NHa for this purpose. Our results are,
for the H2NH3 system at 523.16K, ~012 = 0.371, ~021 = 1.625, the
maximum and average absolute deviations became Irom 4.9 and
3 to 0.2 and 0.08 percent respectively. In the same way for N2NHa system at 523.16K, ~12 = 0.977, ~21 : 0.963, the maximum
and average absolute deviations became from 4.4 and 3.2 to 3.0
and 1.0 percent respectively. In general, by adopting this procedure an improvement is expected though its degree seems to
depend on the particular system in a somewhat unique fashion.
Received 15th January, 1956.
REFERENCES
1) M a s o n , E. A., J. T. V a n d e r s l i c e and J. M. Yos, Phys. Fluids "~ (1959) 688.
2) C h a p m a n , S. and T. G. C o w l i n g , The Mathematieal Theory of NonUniform
Gases, Second Edition, Cambridge University Press, New York, 1952.
3) M o n c h i c k , L. and E. A. M a s o n , J. Chem. Phys. 85 (1961) 1676.
4) S t o e k m a y e r , W. H., J. Chem. Phys, 9 (1941) 863.
5) G a m b h i r , R. S. and S. C. S a x e n a , Trans. Faraday Soc. 60 (1964) 38.
6) S u t h e r l a n d , W,, Phil. Mag. 40 (1895) 421.
a) B r a u n e , H. and R. LiIlke, Z. Phys. Chem. A 1 4 8 (1930) 195.
b) G r a h a m , Phil. Trans., (1846) 573.
c) H a r l e , H., Proc. Roy. Soc. A 100 (1922) 429.
d) H i r s e h f e l d e r , J. O., R. B. B i r d and E. L. S p o t z , J. Chem. Phys. 16 (1948) 968.
e) R a n k i n e , A. O. and C. J. S m i t h , Phih Mag. 42 (1921) 615.
I) S t e w a r t , W. W. and O. M a a s s , Canadian J. Res. A G (1932) 453.
g) T r a u t z , M. and R. H e b e r l i n g , Ann. Physik 10 (1931) 155.
h) T r a u t z , M. and A. N a r a t h , Anrl. Physik 79 (1926) 637.
i) T r a u t z , M. and W. W e i z e l , Ann. Physik 78 (1925) 305.
j) T r a u t z , M. and R. Zink, Arm. P h y s i k 7 (1930) 427.
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