U.S. AIR FORCE PROJECT RAND RESEARCH MEMORANDUM CALCULATION OF THE VISCOSITY OF GAS MIXTURES by P. J. Krieger RM-649, 13 July 1951 Assigned to This is a working paper. It may be expanded, m: drawn at any time. The views, conclusions, and recommendations expressed herein do not necessarily reflect the off 5 of the United States Air Force. re RAND corseration 1700 MAIN 57 ie + SANTA MONICA » CALIFORNIA ——CONTENTS SURMAEY. ec ceeeeeeeseeeeetateeeetens The (iscosity Equations : i Tabies of Viscosity and Diffusion Coefficients. ..06cccs0 3 iesults and Discussion. we ° Conclusions ve reoenons 0 References......- bos fete TABLES Atomic and Molecular Weights 2. Coefficients of Viscosity in Poises X 10°? for Several Chemical Species at Various Temperatures and at a Nominal Pressure of 1 Am vices : 4 Coefficient of Diffusion in cm? sec”! for Several Pairs of Chemical Species at Various Temperatures and at Atmospheric Pressure a 4. The Quantity (4j/4:)! for Several Pairs of Chemical Species 5. The Quantity (1 + M/Mj)” for Several Pairs of Chemical Species 7 Comparison of Experimental Data with Calculated Values of Viscosity for Some Industrial Gases at Atmospheric Pressure 8 . Typical Ramjet and Rocket Exhaust Gas Compositions and Their Calculated Viscosities at Atmospheric Pressure. 8‘SUMMARY Two semi-empirical general equations are presented for the viscosity of a mixture of n gaseous components. One equation involves the molecular weight, the mole fraction, and the viscosity of each species, and the coef ficient of diffusion for cach pair of components in the mixture. The second equation involves only the first three properties and dispenses with the diffusion coefficients, Tables of viscosities and coefficients of diffusion are presented for several gases connonly found ax products of conbast ion for Lemperatures up to 5000°K and at atmospheric pressure. The mean devi- ation from experimental data of the calculated viscosities for 20 industrial gas mixtures over a range of temperatures is 1.109 per cent for the first equation and 1.717 per cent for the second. The equations are applied to typical ramjet and rocket gas compositions.RM. 649 om THE ¥iSCOSITY EQUATIONS Recently Curtiss and Hirschfelder!) developed, on the basis of © of col the quantitative evaluation of intermolecular forces and che u sion integrals, relations for calculating the viscosity of gas mixtures which reproduce the experimental data for nonpolar gases with high pre- cision but require considerable labor. More recently Buddenberg and Wilke developed the following relatively simple general equation for the coefficient of viscosity n of a mixture of n gaseous components: a In this equation n, is the viscosity of component i at the temperature of the mixture, p, is the density of component # at the temperature and toral pressure of the mixture, Dj, is the diffusion coefficient of com- ponents 1 and j at the temperature and total pressure of the mixture, and x, and x, are the mole fractions of components i and j, respectively, in the mixture. The number 1.385 is an empirical constant From the following considerations Eq.(1) may be cast in a someuhat more convenient form. According to Hirschfelder, Bird, and Spots" the coefficient of diffusion is inversely proportional to the absolute pressure so that (2 where Di, is the coefficient of diffusion at 1 atm and P is the pressure in atmospheres. From the perfect gas law the density p of a gas is given by the relation (3)BM. 649 oh where Mis the molecular weight, R is the gas constant (82.056 cm? atm deg"! mol"), and T is the absolute temperature. On combining Eqs. (1), (2) and (3) there results the relation aM; pet ne wi where M, is the molecular weight of component i, and T is the absolute temperature of the gas mixture. The unit for viscosity is the poise having the dimensions gm cm? sec™!, The dimensions for the coefficient of dif- fusion are em? sec Values derived from Eqs.(1) and (4) indicate that the empirical constant 1.385 must be modified by a temperature-dependent factor in order to sdequately reproduce experimental data over a range of temperatures fron 293°K to 1300°K. Inspection shows that such a factor @ has the form peat or, (3) where a and 6 are constants having the values 0.873143 and 0.000072375, respectively, and T is the absolute temperature. Eq.(4) then becomes a (6) tr 113.65 nT x aM jen Py More recently Wilke effected a simplification of Eq.(1) thru several approximations in the kinetic theory of diffusion to reach the following alternate expression for viscosity: = ey —— 2 se ‘ : at (n/n Tt 7 Mee 2 art yay oe )RM. 649 This equation eliminates the need of diffusivity and density data, but requires the square-root operation an inordinate number of times. TABLES OF VISCOSITY AND DIFFUSION COEFFICIENTS In order to use Eq.(6) for calculating the viscosity of a gas mixture it is necessary to know not only the molecular weight and the viscosity of each component but also the coefficient of diffusion for each pair of com- ponents at l atm pressure and at the desired temperature. In Table 1 are pre- sented the atomic and molecular weights of the gases generally encoantered in propellant combustion products. In Table 2 are presented values of the coefficients of viscosity for these gases at various temperatures and at a noninal pressure of 1 atm. The values for the viscosity of the species H, 0, NX, and OH were calculated by the method described by Gilbert,'®) those for H,, 0,, N,, and CO, by the method of Hirschfelder, Bird, and Spots, and those for the polar molecules NO, CO, and H,0 by the method of Krieger. The coefficients of diffusion presented in Table 3 were conpated by the method of Hirschfelder, Bird, and Spotz.\® In order to facilitate the use of Eq.(7) there are presented in Tables 4 and 5 the quantities (W,/M,)'™ and (1 + M,/M,)!7, respectively, for several pairs of chemical species. Table | ATOMIC AND MOLECULAR WEIGHTS H ° N ou 4 °. 32.000 |AT VARIOUS TEMPERATURES AND AT A NOMINAL PRESSURE OF 1 ATH Table 2 COEFFICIENTS OF VISCOSITY IN POISES x 10~” FOR SEVERAL CHEMICAL SPECIES Rul-649 ot nk [a fo [x [om [a [io [x | x | @ | co: | 0 20.16] eat | 2409] 1965 | 14sa[ 91] 2060 | 1777 | i909] ar7e | aes | nas sco” | a24| 2a | rota | 1461 | a95 | 2070 | azas | 1919] ives | 1494 | 1099 ‘a0 | 996 | 2967 | 2435 | 1839 | 1081 | asan | 2202 | 2387] 221e | 1923 | x76 seo fais4| 3477] 2665 | 2198 | 1250) 3032] 2571 | 203] 2602} zane | 1724 sco | 1302 | 3957 | 327s | 2544 | 1407 | 3442 | 2908 | S11] 2954] 2039 | 2100 too | x441 | 4415 | 3664 | 2070 | 1555 | 3821 | 3224 | 3532] 200 | 2962 | 2501 fm | 1574 | ass | 4039 | 3202 | 1695 | 4179 | 3523 | 3063 | 3507 | 3295 | 2921 900 | xror | s277 | 4402 | 351n | 1929 | 4520] 3808 | 4176 | sete | 3572 | 3353 roo — | 1824 | 5687 | 4754 | 3820 | 1950} gage | soa2 | 4577] 4156 | 3e42 | ates tno | 1942] 6085 | so96 | 4131 | 2082] $162] 4345 | 47665] 4424 | 4oo8 | 4232 i200 | 2087 | 6473 | 5431 | 4429} 2202 | sass] 4599 | Sosa] 4603 | 4346 | 4605, 1300 | 2169 | 6852 | 57s | 4722 | 2318 | 5761 | ses | 5318] 4934 | a5as | 5095, tao | 2977 | 1222 | sort | souo | 2431 | so4e | soes | 5577} 5177 | 4ai9 | 5513, 1500 | 2383 | 7585] 6391 | 5294 | 2542 | e327 | 317 | seaz] seis | soas | 5920 100 | 2487 | 1940] e700] 5515 | 2550] 6599] S545 | som] Sous | S267 | aie ato | 2509 | 269] 1003 | sas2 | 2756 | sas | stot | 6325 | se71 | sea2 | 6702 100 | 2688 | 8633 | 7301 | 6126 | 2acn | t124 | soa | 6563 | 6092 | soos | 7075 100 | 2786 | 8971 | 7595 | 6397 | 2961] 7379] 6197 | 6796{ 6308] 5900 | 7436 zom | 2aa2 | 9303} 7085 | 6664 | 3061 | 7528 | e408 | t025| 6521 | 6102 | 7744 2100 | 2976 | 9631 | ar7| 6930 | 3159 | 7273 | 6612 | 7250| 6730 | 6301] 9122 2200 | 3069 | 9955 | 45s | 7193 | 3256 | alls | soe | 7471 | 6035 | 6196 | axa 2300 | 3160 |ao27a | 9752 | 7453] 3351 | 351 | 7012 | r689| 7137 | 6688 | e766 2400 | 3250 [10589 | 9007 | 7711 | 3448 | ases | 7208 | 7903 | 1335 | 6876 | 07s 2500 | 3339 |10900 | 9280 | 7967 | 3536 | aais | 7400 | eite| 7535 | 067 | 9371 2600 | 3427 | 11208 | 9549 | 2221 | 3627 | 9040 | 7590 | #322 | 7729 | 7245 | 9660 zroy | 3513 ]115%4 | oie | 8473 | 3716 | 9263 | 7777 | as27 | 7920 | 7425 | 9940 2e09 | 3599 [1iais | 10080 | a732 | 3604 | 9483 | 7961 | 730 | e108 | 7603 | 24 290) | 3682 | 12112 | 10342 | a971 | 3091 | 9701) 14s | av30 | 8294] 7779 | waa 3009 | 3767 | 12406 | 10501 | 9218 | 3977 | 9915 | 2323 | 9120 | 476 | 7952 | 10738 sim | 3849 [12698 | 10ase | 9463 | 4062 | 10127 | 501 | 9329 | 660} 8125 | 10991 3200 | 3930 [12988 | 11113 | 9706 | 4146 | 10337 | 8577 | 9523 | se40 | 6293 | 11239 3300 | ani | 13275 | 11365 | 9948 | 4229 | 10544 | asi | 9716 | 9017 | aaso | ise) 3409 | 4090 | 13560 | 11615 | 10189 | 4312 | 10749 | 9023 | 9905 | 9194 | a626 | 1uT16 3500 | 4169 | 13842 | 11863 | 10428 | 4398 | 10952 | 9193 | 10093 | 9367 | a7es | i947 3600 | 4247 [14122 | 12110 | 10665 | 4475 | 11153 | 9361 | 10278 | 9539 | e951 | asi72 zoo | 4325 [14399 | 12355 | 10902 | 4555 | 11352 | 9528 Jings1 | 9709 | 9111 | 12395, soe | 44oz | 14674 | 12598 | 11136 | s634 | 11549 | 9693 | 10543 | 9n7e | 9269 | 12613 900 | 44te | 14947 | 12039 | Lists | aziz | 11744 | 9957 | 10823 | 10046 | 9426 | 12828 4000 | 4553 | 15218 | 13078 | 11603 | 4790 | 11937 | roo19 | 11001 10212 | 9582 | 13039 sion | 4628 | 15497 | 13316 | 11835 | aasr | 12129 | oreo {11178 | 10376 | 9736 | 13247 4200 | 4702 | 15754 | 13552 | 12065 | 4943 | 12319 | 10339 [11353 | 10539 | 909 | 15451 4300 | 4776 | 16020 | 13787 | 12295 | so1s | 12507 | 10497 | 11527 | wor00 | 10941 | 13652 440 | 4849 | 16284 | 14020 | 12525 | 509s | 126094 | 19654 | 11700 | 10861 | 10191 | 13850 4500 | 4922 | 16546 | 14252 | 12750 | st68 | 12879 | 1oa10 |11872 | 11021 | 10340 | 1404s 460 | 4994 | 16806 | 14483 [12976 | sz42 | 13063 | 19965 | 12043 | 117s | 1oase | 14238 4ro0 | 5064 | 17064 | 14712 | 13201 | 5315 | asz4s | 11117 {12212 | 11335 | 19635 | 14428 se00 | 5135 [17321 | 14940 | 13426 | aaa | 13425 | 11270 |12979 | 11490 | 10781 | 14615 490¢ | 5206 } 17577 | 15167 | 13649 | 5460 | 13605 | 12421 | 12545 | 11645 | 10926 | 14800 sone} 5275 |17e3i |15392 | 13871 | 5532 | 1378s | 11570 |12710 | 11799 | Lio6e | 11982Ru-649 “5 Tree a] UNSS3YE DIVGHASONLY LV ONY S34MLYEBUNIL SNOIYYA LY 219348 WOIMSHD 40 SUIVE THIAIS Yos 935 END MI NOTSM4dIa 40 4N319144309 eoigeLTable 4 THE QUANTITY (U,/¥;)" FOR SEVERAL PAIRS OF CHEMICAL SPECIES a-649 “6 t Ha oO Na co. cor No Hy ~ 1.99602 | 1.93076 | 1.93066 | 2.16155 | 1.96820 0; | 0.0100 a 0.96731 | 0.96725 | 1.08293 | 0.98406 x | o.sit9s. | 1.03380 - 0.99995 | 1.1953 | 1.01732 co | 0.51796 | 1.03385 | 1.00005 - anios9 | Lorrsr co, | 0.46263 | 0.92342 | 0.89323 | 0.50228 - 0.90870 no | 0.90838 | 1.01620 | 0.98297 0.98292 | 1.10047 - uo | o.staaz | .isess | taner0 | 1.1664 | 1.25018 | 1.136¢6 ° 0.59579 | 1.49921 | 1.15033 | 1.18027 | 1.2ete3 | 1.17025, 4 t.aeg21 | 2.37368 | 2.29608 2.29585 | 2.57053 | 2.3350 ow | o.seove | auuie | 1asze9 | 113263 | 1.26832 | 1.15251 Ny o.1sea | 1.2249 | Ltav2r | Ltgsta | 1.89135 | 1.20900 ? 20 ° a ou N nz | 1.72699 | 1.67645 | 0.84090 | 1.70420 | 1.62357 02 0.06622 | 0.84090 | 0.42129 | 0.05384 | 0.81340 Nz | 0.89549 | 0.86932 | 0.43553 | o.ae270 | 0.84090 co o.a9sse | 0.6936 | 0.43555 | 0.88774 | 0.84094 cop | 0.29988 | a.rzeso | 0.38902 | 0.78845 | 0.75111 No | 0.88025 | 0.85452 | 0.4281 | 0.86767 | 0.82658 430 - 0.97077 | 0.48635 | 0.98571 | 0.93003 ° 1.03011 - o.so100 | 1.01539 | 0.96731 8 2.08612 | 1.99602 - 2.02674 | 1.93076 co 1.01450 | o.seae | 0.49340 - 0.95264 N 1.06493 | 1.03320 | 0.51793 | 1.04971 =THE quaxriTy (1 + mjfl,)” FOR SEVERAL PAIRS OF CHENICAL SPECIES Table 5 0 1.05447 1.66619 | 1.59846 1.59835 1.85549 1.63268 oH | 1.08761 1.69789 1.62703 1.62692 1.89410 1.66263 nm 4 Le o a on N co 1.26187 | 1.25348 1.01783 126776 1.22479Table 6 (COMPARISON OF EXPERIMENTAL DATA WITH CALCULATED VALUES OF VISCOSITY FOR SOHE INDUSTRIAL GASES AT ATHOSPHERIC PRESSURE Eq.) Eq. (6) Fa.(7) 1 (Poises = 10°7) Mole Fraction Composition Oba alculated Te | O | Nz | © | OO; 1% [Ref.2] Her? ]eg.(6) Fe | 0.023 | 0.891 0.086] 293 | ans6 | iter | at6o | inst 0.039 | 0.828 o.tsa| 293 | amas | ates | itso | ime 0.107 | 0.831 .062| 293 | 1793 | ze | i299 | i162 9.016 0.595 | 0.265] 0.104] 23, | 1736 | 1798 | rte | aaa 0.022 {0.200 | 0.850 o-108} 300.5} 1627 | i792 | iter | asi sea.s| amis | 2651 | 2t62 | 2632 973 | 4117 | 4008 | 4136 | 995 yar | sasé | atsa | art | ates 0.022 [0.001 | 0.222 | 0,078 | 0.067] 307.5) 1862 | 13s | 1628 | 1191 sis | 2655 | 2653 | 2555 2609 97s | ose | 4019 | 4052 | 4007 yas | sans | ates | 4791 | 4800 0.007 [0.030 | 0.96 | 0.003] 0.068] 314 | 1904 | 1856 | 1857 | 1026 sia | 2705 | 2644 | 2655 | 2628 ota.s| ais | 4017 | aoia | soi reer | 4e95 | arrt | aeie | 4823 9.115 | 0.001 | 0.861 | 0.251 | 0.060} 302 | 1623 | 1829 | 1827 | 770 525 | 2686 | 2606 | 2710 | 2655 ors | 40g1 | aoaz | dose | 4027 izes | art | aezt | art | 505 Mean deviation, percent, 1.371 1.109 1.717 Table 7 ‘TYPICAL RAMJET AND ROCKET EXHAUST GAS COMPOSITIONS AND THEIR CALCULATED VISCOSITIES AT ATHOSPHERIC PRESSURE Ranjet Rocket Temperature, °K 1000] 3400 1900 Composition, mole fraction Na o.ms0 40 0.12465 0.30756 02 ons? 0.10197 oo o-o1s0s 0.38154 te 0.02809 o.asit9 02 0.00874 on | I 0.03502 ° i i 00870 H | o.o3e90 | Viscosity, poizes «107% | i Linear combination || 3958 |eBo 649 -o RESULTS AND DISCUSSION In Table 6 are presented experimental viscosity data for sone three-, fours, and five-component gas mixtures at various temperatures and at atmospheric pressure. For comparison in the last three columns are listed the values of the viscosity calculated by means of the Curtiss and Hirschfelder relation (Eq.(21), Ref.2), Bq.(6), and Eq.(7). The average deviation for the 20 mixtures is 1.371, 1.109, and 1.717 per cent, re- spectively, for the three methods. The corresponding average deviation for values calculated by taking @ linear combination of the individual viscosities is 3.387 per cent. From a purely mechanical point of view £q.(6) is much easier to use than either of the other equations. For the set of gas mixtures given, it yields slightly more accurate results than the others. In Table 7 are presented two theoretical gas mixtures. One is typical of the composition resulting from the combustion of a hydrocarbon fuel in a ramjet engine. The other is a typical composition resulting from the combustion of @ hydrocarbon fuel with oxygen in a rocket motor. No experi- mental data are available for these gas mixtures. The vise ty values ere calculated by four methods: by taking Linear combinations of individual viscosities and by means of Bys.(4), (6), and (7). For the ramjet gas composition the calculations were made at 1000°K, while for the rocket gas composition the viscosity was calculated at two temperatures correspending to the chamber and the exhaust conditions, respectively. In the Latter case the minor components OH, 0, and H were included. The diffusion coef ficients required for these species were estimated from the values pre- sented in Table 3 Inspection of the results shows thst the linear combination valuesRM-649 =i0 are, as usual, lower than those obtained by other methods. For the ranjet~ gas composition the results are relatively uniform, the value derived from Eq. (6) being slightly higher than the other two. For the rocket-gas conpo- sition the discrepancies are more pronounced, especially at the higher temperature. This may be due to the following reasons. First, the vempera- ture correction factor @ in Eq.(6) is probably not valid above 1759°K since it wns devived from empirical values covering the range of temperatures from 293° to 1300°K, Secondly, the diffusion coefficients estimated for the species 0, H, and OH may have been too conservative. Little can be said with certainty about the accuracy of the high- temperature rocket-gas viscosity values because of the nonexistence of observed data. The probable error, however, in results obtained by neans of Eys-(4) or (7) for rocket gases which include dissociation products may not exceed 5 per cent. No attempt has been made in this report to introduce » pressure- correction factor for viscosity. Experience shows that the effect of pres- sure is slight below 20 atmospheres, but that it becomes quite prorounced at extremely high pressures. The magnitude of the pressure effect varies also with the chemical species. CONCLUSIONS In general, Eq.(4) gives abnormally low values of viscosity at low temperatures. By incorporating a temperature-correction factor Ey.(6) overcomes this deficiency. Bq.(T) gives slightly better values at low temperatures than Eq.(4), and, Like Bq.(4), gives improved reaulta with increasing temperature. In spite of the fact that it dispenses with the use of diffusion coefficients, By.(7) is auch more cumbercon: se handle chan Eqs.(4) and (6).RM. 649 le REFERENCES Curtias, C.F, and J.0, Hirschfelder, The Kinetic Theory of Mal ticomponent Systeas of Gases, University of Nisconsin, CF-127, July, 1947, Hirschfelder, J.0., R.B. Bird, and E.L. Spotz, “The Transport Properties of Gases and Gaseous Mixtures IT." Chen, Rev., Vol:44, 1949, pp. 205-231 Buddenberg, J.¥. and C.R. Wilke, “Calculation of Gas Mixture Viscosities," Ind. Eng. Chea, Vol.41, 1949, pp-1345-1347. Phys., Vol.18, 1950, Wilke, Cu, “A Viscosity Equation for Gaz Mixtures," J. Chet >p- 517-519) Gilbert, M., “Estimation of the Viscosity, Conductivity, and Diffusion Coefficients 3f 0, HN, and OH," California Institute of Technology, Jet Propulsion Laboratory, Yemorandum No.4-S1, duly 6, 1949 Wirschfelder, J.0., R.B. Bird, and E.L. Spote, "The Transport Properties of Non Polar Gases,” J. Chem: Phys, Vol-16, 1948, pp.968-981 Krieger, FoJ., The Viscosity of Polar Gages, The RAND Corporation, Research Meno randum, RN-646, July 1, 1951.