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Calculation of Gas Mixture

Viscosities
J. W. BUDDENBERG' AND C. R. WILKE
University of California, Berkeley, Calif.

An empirical correlation has been developed to predict A and B are constants which are determined experimentally
the constants i n the Sutherland-Thiesen equation for for each gas pair. Viscosities are assumed to be essentially inde-
binary gas mixtures leading to the general equation: pendent of pressure in this development.
Schudel (10) has effected a simplification of the Sutherland-
U1 U"
Thiesen equation showing t h a t

Reproduction of available data at moderate pressures over


a temperature range from 11" to 225" C. is obtained with leading t o a general equation containing only one constant
a n average deviation of 3.79'0 between calculated and ob-
served values for 116 mixtures. The following general @n =
1
@'
+c9F
+ 1 + @*c 3 @ (3)
form to include multicomponent systems is proposed: 51 P1 zz P2

Through Equation 3, therefore, i t is possible t o predict the entire


viscosity curve for a binary mixture from a single experimental
determination a t one mixture composition,

j#i 140 1 I

Data for three ternary mixtures and two quaternary mix-


tures are reproduced by the general equation with a n aver-
age deviation of 2.56%.

I K MANY chemical engineering problems, particularly in the


interpretationand design of heat andinass transferprocesses, it
is necessary t o know the viscosity of gas mixtures. Although vis-
cosities for pure gases are fairly readily available, data for mix-
tures are scarce. It is desirable, therefore, to have a means of
calculating necessary data for mixtures from the properties of the
0 Exp
pure components.
Uyehara and Watson (21) have developed a general method for
estimating gas mixture viscosities based on a correlation of re-
% H2
duced viscosities for the single components and the pseudo-
crit,ical concept of K a y (8). T h e present method is proposed as an Figure 1. Fit of Hydrogen-Freon
alternate means of calculation. 12 Data by Schudel's Equation
Unfortunately, gas mixture viscosit,ies or fluidities are not
additive on a simple mole fraction or other concentration basis. A T h e authors have further verified the application of Equation 3
plot of viscosity against mole fraction for binary systems niay in a study of five new binary mixtures ( 3 ) . Figure 1 shows the
show marked curvature with the viscosity of the mixture lying reproduction of the hydrogen-Freon 12 curve a t 25" C., and 1
above or below t h a t indicated for a linear relationship, and in some atmosphere by this equation.
cases rising to a maximum viscosity considerably greater than
that for either pure component,. DEVELOPMENT OF GENERAL EQUATION
A number of general equations expressing binary mixture vis- The constant C in Equation 2 was calculated for available
cosit,ies as a function of concentration and pure component vis- binary mixture viscosity data and compared with various proper-
cosities have been proposed (4,6, 9). These equations are ties of the systems. It was found t h a t C could be expressed as a
generally complex and unwieldy and involve a number of arbi- function of the diffusion coefficient of the gas pair as shown in
trary constants which must be determined from experimental Figure 2. The results are summarized in Table I. The most
satisfactory agreement was obtained with values of C based upon
data. A rather simple equation which has been found to fit a a n experimental point in the central region of the viscosity-mole
wide range of experimental data was first derived by Sutherland fraction curve for each gas pair, and this procedure was followed
(11), and later derived independently by Thiesen ( l a ) . in calculation of the d a t a plotted in Figure 2. Diffusion coef-
ficients not available in the literature v e r e estimated by the
method of Arnold (1). The line through the d a t a in Figure 2 is
based on a least squares treatment of d a t a for 21 gas pairs at room
temperature and atmospheric pressure. The data at higher tem-
peratures were excluded from the least squares treatment because
of uncertainty with respect t o the effect of temperature on the
1 Present address, Union Oil Company of California, Oleum, Calif. diffusion coefficient. However, the data a t higher temperatures
1345
1346 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY 7201. 41, N o ?

( k i t s alone, so t h a t better agreement rnight, be expectled with


TABLE
1. SCHUDEII'S CONSTliNTS AND DIFFVSIOK
COEFFICIEXU'TSa more accurate diffusion data.
Temperature, Din C To illustrate further the utilit,? of the general eyua1,ion in the
Gas Pairb 0 C. Rq. Cm.'/sec. ~ e c . / ~ dCm.
.
reproduction of viscosity curves having a wide variety of shapes
Hz-He (14, 17) 20 1.331A 0.9266
Nz-SO (16) 20 0.2001A 6.4646 seven binary systems were selreted as shown in Table IT. The
COz-CaHs (18) 26.9 0.0802.4 15.915
Hz-SHI ( I # ) 20 0.6831A 1.8382 average deviation betwvprn ca81culatetland observed values for the
Hz-CHa ($0) 20 0.6998E 1,9749 35pointslistedis 2.15%.
Hz-Nz (23) 19 0.7413.1 2.0313
Hn-CO ( I S ) 19 0.7153E 2.0572
IIe-Ar (14, 17) 20 0.676GA 2,0328 Awucmiox TO MULHCOWPONE\ r SY wmis
Hd-CaHa (18) 26.9 0.4748.4 3.3262
CzHeAir ( 7 ) 12-13 0.1433.4 9.0547
NHa-CzHa ( 7 ) 12-13 0.1359.1. 8.097 T h e form of the Sutherland-Thiesen type of equation for mulu-
Hz-CnH4 (7) 12-13 0 . A13CE 2.6112 component systems (9) suggeit- t h e following general extension of
COz-Freon 12 ( 3 ) 25 0.0638A 20.876
Hn-Freon 12 ( 3 ) 25 0.45179 3.6002 Equation 6.
Ha-C0z (3') 25 0 . 6158E 2.4504
Nz-Freon (3; 25 O.0965A 14.205
Hz-Ne ( 3 ) 25 1.. 093A 1.3743
Hs-NO (7) 11.1 0.7326A 1.9518
Hz-SO2 ( 7 ) 17 0,5308E 2,7614
Nn-Oz ( 1 9 ) 26.8 0.2067E 0.6281
Hz-On ( 1 9 ) 20 0.7704E 1.9117 u?
Air-CnHa ( 7 ) 99.8 0.2022.1 7.72
Hz-COz ( 7 ) 99,2 0.800E 1.705
Hz-802 ( 7 ) 199 1.10E 1,21Y
Hz-He ( 7 ) 100 1, 9 15.4 0.6552
CHa-CxHa (% 22.5 0.252.k 4.2825
CHi-CrHs 225 0.00926.A- 117.2
where U,,,, U,,, et(:., are the avemge diffusion coefficients of aom-
a A = diffusion coefficients calculated h) Ainald'8 method; E = diffusion
coefficients based on experimental data. ponents 1, 2, etc., with respect to the total ga.s mixture.
D h-umbers in parentheses indicate d a t a source. .4n expression for the diffusion coefficient of one gas into a mix-
e A t 27.2 atmospheres' pressure.
ture of two or more other gases has been derived by Wilke (29) on
the basis of hIaxv-ell's equations for diffusion. This relat,ion may
fit the correlation satisfactorily using diffusion coeffieicnts calcu- he expressed as follows:
lated 011 t,he basis of the usual assumption that D is proportional
t,o Tap.
The equation for the !inc in Figure 2 g i v e the relation

Uirnerisioiial conbidel ations, howwer, require tlial tlie Suther-


land-Thiesen coristanls be dimensionless. so that an exponent
of unity is probably corrcct in I3quation 4 lrading to the relation 3101e T.:~peri:uentaI Calculated
Fraction Vixosity, Viacosiw, Deviation,
Gas Pair I'irsl Gas Iliorogoises Micropoises %
COz-Freon 0.0000 121.0 ..I

0 2900 130. 1 11k:3 -1.4


whaie 1.385 IS n diniensioiiless constant !\-itti nnplovenlent in 0 6000 185.3 133.6: - 1.5
qunntity and accuracy of diffusivitr data it is poqsible that this 0 7500 142.0 140.0 -1.4
1.. 0000 147.8 , . . . , .
constant mar be sonieTrhat chang a d . By combining Equations 3
and 5 a single geneial rc.latiorr niav br written for thc T - i w m t v of xi. xi,
~~ ~.' n nnnn
"-";
on;
-"-I.
7
biniiri ~ H mixtiirw'
S
0.1864 200.8 1b1:4 -1.5
0.2408 199.5 197, 2 -2.1
0,5893 189.4 184. 4 --2.6
0.5920 189.3 185 9 -1.6
0.7822 184.3 180.6 - 2.c
1 ,0000 178.1 ...
where H2-Fre011 0.0000 124.0
111:0
. . I

0.2500 128.1 -0.73


,ul and I.(.: = viscosities of pure compolit~iits1 and 2 at thcl tem- 0.5000 131.9 135.7 f2.B
perature of the mixture 0.7500 135.1 143.1 6 .0
-i-
p i and p2 = densities of pure components 1 and 2 a t the tem-
1.0000 88.4 ...
perature and total pressure of the mixture. 0~0000 81.7 ...
DL2= diffusion coefficient a t t,hc temperature and total pressure 0.1821 8 3 . ii 85.3 +2.'!
of t h r inixture 0 3704 87.4 89 8 f2.d
0,5818 92.4 96.3 +4.2
rl and x2 = mole fractions of conipoiicnts 1 and 2 in the mixture 0.7882 98.5 103.1 $4.7
Any consistent selection of units may be made so t h a t thc 0,8750 U8.7 104.1 -4.7
denominators of Equation 6 are dimensionless. For ideal gases the 0,9225 97.0 102.4 -5.4
1.0000 89.1 ...
denominators are nearly indepcndcnt of temperature or pressure.
For components a t temperatures below their boiling points Hz-C'C) 0~0000 174.5
hypothetical vapor densities may be estimated on the basis of 0,1927 171.7 511'9
0.4096 165.1 166.3
the gas laws. 0,4755 161 . o 163 9
Some theoretical basis for the relation between viscosity and the 0,4755 161 0 163.9
diffusion cocfficient is offered by the treatment of Chapman and 0.6947 144.9 149. G
1 . 0000 87.4
Cowling ( 5 ) . Attempts t o develop Equation G from the kinetic
theory %-ere not successful, howevkr. He-A 0.0000 221.1 " 1.
0.8405 227.8 211:0 -0.34
0.3660 228.6 227.4 -0.52
APPLIC9TIOS TO BPA 4 R Y SYSTEMS 0,3820 229.1 227.7 -0.61
0.4906 229.6 229.2 -0. sa
0.5966 230.4 230.0 -0.17
To test the accuracy of Equation 6 viscosities weie calculated 0.7565 227.0 227.8 $0.35
and compared with experimental data for the systems listed in 1.0000 197.3 ... . ,

Table I. The average deviation from experiment v a s 3.02y0 for


88 binary mixtures a t approximately room temperature. For 23
other mixtures at various temperatures ranging from 99 to
225" C. the average deviation was 6.9s0. These deviations are of 176.8 ... . L .

the order of magnitude which might be expected to result from e h l l d a t a obtained at 25' C. a n d atinospheric p r e m n e .
uncertainty in the estimated and experimental diffusion ooeffi-
M y 1949 INDUSTRIAL AND ENGINEERING CHEMISTRY 1347
DISCUSSION

Equation 10 is believed to be generally applicable t o the ealcula-


tion of gas viscosities under conditions such that pressure has no
appreciable effect on the viscosities of the pure components. No
extension of the method to include behavior which is nonideal
with respect t o pressure has been attempted in view of the limited
amount of data available. Good reproduction of nearly all the
available data has been obtained for mixtures at atmospheric
pressure over a range of temperatures from 11 O to 225 O C. and for
one system a t 27 atmospheres.
A comparison of the present method with that of Uyehara and
Watson was made on the data given in Tables I1 and 111. The
average percentage deviation between calculated and observed
data by the present method for the thirty-five mixtures was 2.15%
coniparpd t o 5.GGy0by the Uyehara-Watson method. However,
such a comparison must be interpreted with caution in view of the
limited data considered and possible error in reading the published
curves in using the latter method.
The general application of the method requires only a knowl-
edge of the viscosities and densities of the pure components and
the diffusion coefficients of the various components with respect
to each other a t the temperature and total pressure of the mix-
ture. Diffusion coefficients may be readily estimated by the
Figure 2. Correlation of C with Diffusion Coefficient for equations of Arnold ( 1 ) or Gilliland (6). It is believed t h a t this
Binary Mixtures method will be useful in the interpretation and design of processes
involving gas mixtures.

with similar equations for the other components. Combining NOMEN<:LATIIRE


relations such as 8 with Equation 7
d arid B = roristants in thp Hutherland-Thieseri equation, di-
lum =
M1 - __ mensionless
.) +
~

C = constant in Schudels modification of Sutherland-


. Thiesen equation, sec./sq em.
I) = diffusion coefficient, sq. cm./sec.

1.385~2
PZ
+ x = mole fraction
P = viscosity, gram/cm.-sec. or micropoises
p = density, gram/ml.
Subscripts
P.3 I,2,3, etc. = referring t o component 1, 2, 3, etc.
(9) 2, 3 = referring to i and j components
m = referring t o mixture
= referring t o n component
Equation 9 may be written in more general form for rb coni-
ponents: LITERATURE CITED
II
Arnold, J. H., IND. ENG.CHEN.,22, 1091 (1930).

22
PLm = P%
(10) Bicher, L. B., Jr., and Kats, D. L., Ihid., 35, 754 (1943).
Buddenberg, J. W., M.S. thesis, Unlverslty of Califoinia, 1948.
2=1 1+-
1385u2 Chapman, S., Phil. Trans. Roy.SOC.(London),217A, 115 (1918).
X*Pa
j=1
Chapman, S., and Cowling, T. G., Mathematical Theory of
j#i Non-Uniform Gases, p. 230, Cambridge, University Press,
1939.
Equation 10 was tested by coinparison of calculated with ex- Gilliland, E. R., IND.ENG.CHEM.,26, 681 (1934).
International Critical Tables, 5701. V , New York, McGraw-Hill
perimental data obtained by the authors ( 3 ) for three ternary Book Co., 1929.
mixtures and two quaternary mixtures. These data are given in Kay, W. B., IND. ENG.CHERI.,28, 1014 (1936).
Table 111. The average deviation between the calculated and Kennard, E. H., Kinetic Theory of Gases, pp. 160-2, New
observed data for these mixtures is 2.57y0 which supports both York, McGraw-Hill Book Co., 1938.
Schudel, W., Schweiz. Ver. Gas-u Wasserfach. Monats-Bull., 22,
the validity of Equation 10 for the gas viscosities and the validity 112, 131 (1942).
of Equation 8 for diffusion coefficients in gas mixtures. Sutherland, W., Phil. Mag., 40, 421 (1895).
Thiesen, M., Verhandl. deut. physik. Ges., 4, 348 (1902).
Trautz, M., and Baumann, P. B., Ann. P h y s i k , [5] 2, 733 (1929).
Trauts, M., and Binkele, H. E., Ibid., [ 5 ] 5,561 (1930).
T A B L111.
~ COMPARISONOF CALCULATED
WITH OBSERVED Trautz, M., and Gabriel, E., Ibid., 11, 606 (1931).
DATAFOR COMPLEXMIXTURES~ Trautz, M., and Heberling, R., Ibid., 10, 155 (1931).
Trauts, M., and Kipphan, K. F., I b i d . , [ 5 ]2, 743 (1929).
Experi- Calcu- Trautz, M., and Kurs, F., Ihid., 9, 992 (1931).
mental lated
Vis- Vis- Trauts, M., and Melster, A,, I h i d . , [5] 7, 409 (1930).
oosity, oosity, Devia- Trauts, M., and Sorg, K. G., Ibid., 10, 81 (1931).
Propor- Mipro- Mipro- tion, Uyehara, 0. A., and Watson, K. M., Natl. Petroleum News,
Gasea tions poises poises % 36,R764 (1944).
Ne-Hz-COz (9) l/aeach 185.7 195.3 +5.1 Wilke, C. R., presented before the Am. Inst. Chem. Engrs.,
At-Nz-Freon 12 (8) 1/3each 146.9 151.0 +2.8
Nl-COe-Freon 12 ( 5 ) 1/seach 145.8 144.6 -0.8 Los Angeles, Calif., March 7, 1949.
Ne-H%-COeFreon 12 (3) I/aeach 168.1 162.3 -3.4
He-Nz-COe-Freon 12 (3) 1/4each 147.1 148.2 +0.75
RECEIVEDDecember 13, 1948. Presented before the Division of Physical
All data obtained a t 25 C. and atmospheric pressure. a n d Inorganic Chemistry a t the 114th Meeting of t h e AMERICAN
CHEMICAL
SOCIRTY, Portland, Ore.