U.S. AIR FORCE PROJECT RAND RESEARCH MEMORANDUM CALCULATION OF THE VISCOSITY OF GAS MIXTURES by J. Krieger RMA6L9 13 July 1951 Assigned 10 This is o working paper. It may be expanded, modified, or with- drawn at ony time. The views, conclusions, ond recommendations expressed herein do not necessarily reflect the official views or policies of the United States Air Force. 2 RAND conse 1700 MAIN ST, + SANTA MON M4 cauronia—<—$—CONTENTS: Summary The Viscosity Equations... Gddecoo 1 Tables of Viscosity and Diffusion Coefficients... 3 Results and Discussion 9 Conclusions. . 10 References a TABLES 1. Atomic and Molecular Weights... 2 2. Coefficients of Viscosity in Poises X 107? for Several Chemical Species at Various Temperatures and at a Nominal Pressure of 1 Atm eee 4 5. Coefficient of Diffusion in cm? sec"! for Several Pairs of Chemical Species at Various Temperatures and at Atmospheric Pressure Bqo00 4. The Quantity (ify/iti)" for Several Pairs of Chemical Species 6 5. The Quantity (1 + My/Mj)? for Several Pairs of Chemical Species 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 @RN-649) SUMMARY ‘Two semi-empirical general equations are presented for the viscosity of a mixture of m gaseous components. One equation involves the molecular weight, the mole fraction, and the viscosity of each species, and the coef- ficient of diffusion for each 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 cocfficients of diffusion are presented for several gases commonly found as products of combust ion for temperatures up to 5000°K and at atmospheric pressure. The mean devi- ation from experimental data of the calculated viscosities for 20 industeial 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 ae THE ViSCOSITY EQUATIONS Recently Curtiss and Hirechfelder (> developed, on the basis of che quantitative evaluation of intermolecular forces and the use of col- lision 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 recent ly Buddenberg and Wilke developed the following relatively simple general equation for the coefficient of viscosity 1) of @ mixture of n gaseous components: = it 1.385 7, eee me we In this equation 7, is the viscosity of component i at the temperature of the mixture, 9, is the density of component i at the temperature and Loval pressure of the mixture, Dj, is the diffusion coefficient of com- ponents t 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 somewhat more convenient form. According to Hirschfelder, Bird, and Spotz™ the coefficient of diffusion is inversely proportional to the absolute pressure so that (@ 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 ar, aRM- 649 2. where M is the molecular weight, R is the gas constant (B2.056 em? atm 1 mol!), and T is the absolute temperature. On combining Eqs.(1), deg” (2) and (3) there results the relation ni a ea ce w Te th 1 BEATE eM jet Phy we 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 em™? sec™?. The dimensions for the coefficient of dif- fusion are em? sec™! Values derived from Eqa.(1) and (4) indicate that the empirical constant 1.385 must be modified by @ temperature-dependent factor in order to adequately reproduce experimental data over « range of temperatures from 293°K to 1300°K. Inspection shows that such a factor @ has the form peat or, ) 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 z, 113.65, 7 ri . (9) eee ia'slainms HS65 ont Ey Tm & ot wi 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: ay 14 (n/a J) WH + 07H, ‘ )RM. 649 ns 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 encountered in propellant combustion products. In Table 2 are presented values of the coefficients of viscosity for these gases at various temperatures and at a nominal pressure of 1 atm. The values for the viscosity of the species H, 0, N, and OH were calculated by the method described by Gilbert, %) those for Hy, 0,, Ny, and CO, by the method of Hirschfelder, Bird, and Spotz,‘® and those for the polar molecules NO, CO, and H,O by the method of Krieger. The coefficients of diffusion presented in Table 3 were computed by the method of Hirschfelder, Bird, and Spotz.‘®) In order to facilitate the use of Bq.(7) there are presented in Tables 4 and 5 the quantities (i)/M,)! and (1 + M/Ml))'7, respectively, for several pairs of chemical species. Table | ATOMIC AND MOLECULAR WEIGHTS 8 32.000 |AT VARIOUS TEMPERATURES AND AT A NOMINAL PRESSURE OF 1 ATH Table 2 GOEFFICIENTS OF VISCOSITY IN POISES x 10"? FOR SEVERAL CHEMICAL SPECIES RM-649 ee ne [a | o | s | om | im | or | x2 | x0 | @ | co | m0 298,16] 82 | 2409 | 1965 | 1454] 991 | 2060 | 1777 | 109 [ r776 | sae | oss soo’ | sag] 2ei9 | tora | 1461 | 95 | 2070 | 735 } 1919] 1785 | 1494 | 1099 800 | 996 | 2967 | 2435 | 1839 | 1081 | 25a0 | 2202 | 2307 | 2218 | 1923 | 1376 500 | 1184] 3477] 2666 | 2198 | 1250 | 3032] 2571 | 2803] 2602] 2308 | 1724 600 | 1302 | 3957 | 327s | sas | i407 | 3442 | 2908 | sia] 2954] 2639 | 2100 too | 14ai | 4415 | 3666 | 207 | 1555 | 3621 | 3224 | 3532) 3200 | 2983 | 2501 goof ista | esa] 4039 | 3202 | 695 | 4179 | 3523 | 3803] 3507 | 3285 | 2021 900 | ator | arr | 4402] 3518 | 1829 | 4520 | 3800 | 4176 | 3878] 3572 | 3355 roo | 1824 | 687] 4754 | 3628 | 1958 | saan | 4002 | 4477] 4156 | 3042 | a709 tioo | 1942 | sows | S096 | 4131 | 2082 | 5162} 4345 | 4766] 4424 | soon | 4232 sz00 | 2057 | 6473] 5431 | 4429 | 2202| 5466 | 4599 | Sosa] 4603 | 4346 | 4605 1300 | 2169 | 352 | s7s7 | 4722 | 2318 | sto1 | 4845 | 5314 | 4934] 4506 | S095 1400 | 2277 | 1222 | 6077 | soio | 2431 | cose | soas | ssz7] siz | aeu | 5513 asoa | 2383} 7505] 6301 | 5204 | 2542] 6327 | 5317 | 5832] 5413 | so4s | 5920 scoo | 24a7 | 1940] e700 | 5575 | 2650] 6599 | 5545 | soi | S645 | 5267) 6218 1700 | 2589 | 8269 | 7003 | 5852 | 2756 sass | 5767 | 6328] sa7l | s4e2| 6702 100 | 2688 | 8633] 7301 | 6126 | 2560 | T1246 | S984 | 6563 | 6092 | 5693 | 7075 1900 | 2786 | 8971 | 7595 | 6307 | 2961] t379| 6197 | 6796] 6308 | 5900 | 7436 2000 | 2aa2 | 9303} 7085 | 6664 | 061] 7528 | sans | 7025 | 6321 | e102] 7784 2100 | 2976 | 9631 | siti | 6930 | 3159] 7373 | 6612 | 7250] 6730 | 6301] e122 2200 | 3069 | 9955 | e4sa | r193 | 3256] atis | sols | 7471] 6935 | 6496 | 8449 2300 | s160 } oats | e732 | 1453] 3351] 9351 | t012 | 7689 | 7137 | 6608 | 8765 2400 | 3250 | 10589 | 9007 | 7711} 3444] saa | 7208 | 7903 | 7336 | 6875 | 9073, 2500 | 3339 | 10900 | 9200} 7967] 3536 | gaia | 7400] s1is| 7535 | to67 | 9971 2600 | 3427 | 11208 | 9549 | 221] 3627] 900 | 7590 | 8322] 71729 | 1245) 9660 zro0 | 3513 | 1is1e | sie | 47s | 3716 | 9263 | 7777 | 9527 | 7920 | 1425 | 9940 2eo0 | 3598 |11sts | so0go | a73z | 3804} 9483 | 7961 | e730 | 108 | 7603 | 1214 2900 | 3682 | 12112 | 10342 | 971} 3891 | 9701 | 143 | 930 | 8294 | 7779 | 10479 000 | 3767 | 12406 | 10601 | 9218} 3977] 9915 | 9323 | 9129] sata | 1952 | 10730 3100 | 3849 | 12698 | 1o8se | 9453 | 4052 | 10127 | e501 | 9329 | 660 | 8123 | 10901 3200 | 3930 | 1z9ae | 11113 | 9706 | 4146 | 10337 | 8577 | 9523 | 440 | 6293 | 11239 3300 | 4011 ]13275 |11365 | 9948 | 4229 | 10544 | asi | 9716 | 9017 | 8460 | 11401 3400 | 4090 | 13560 | 11615 | 10189 | 4312 | 10749 | 9023 | 9906 | 9194 9626 | 11716, 3500} 4169 | 13842 | 11863 } 10428 | 4394 | 10952 | 9193 | 10093 | 9367 | 8769 | 11947 3600 | 4247 }14122 | 12110 | 1086s | 4475 | 11153 | 9361 | 10278 | 9539 | e951 | 13173 a7o0 | 4325 | 14399 | 12355 | 10902 | 4555 | 11352 | 9528 | 10461 | 97a | oni | 12395, 3800 | 4402 | 14074 | 12598 | 11136 | 4634 | 11549 | 9693 | 1063 | 9872 | 9269 | 12613 3900 | 447e | 14947 | 12839 | 1isti | 4742 | 11744 | 9457 | 10823 | 10046 | 9426 | 12825, 4000 | 4553 | 15218 | 13078 | 11603 | 4790 | 11937 | 10019 | 11001 | 10212 | 9582 | 12039 4100 | 4620 | 15487 | 13316 | 11835 | 4867 | 12229 | 1o1a0 | inate | 10376 | 9736 | 13247 4200 4ro2 | 15754 | 13552 | 12065 | 4943 | 12319 | 10339 | 11353 | 10539 | 98eo | 13451 4300 | 4776 | 16020 | 13787 | 12295 | Sois | 12507 | 10497 [11527 | 10700 | 10041 | 13652 4400] 4849 | 16284 | 14020 | 12528 | 5094 | 12694 | 10654 | 11700 | inne | 10191 | 13850 450 | 4922 | 16546 | 14252 | 12750 | 5168 | 12879 | loe1o [11872 | 14021 | 10340 | 14046 4500 | 4994 | 16806 | 144ea | 12976 | 5242 | 13063 | 10968 } 12049 | 11178 | 1osee | 14238 4700} S064 | 17064 | 14712 | 13201 | 5345 | 13245 | 1117 [12212 | a4aas | 10635 | 14428 4noo | 5135 | 17321 | 14940 | 13426 | s3a8 | 1345 | 11270 J12379 | 1490 | 10781 | 14635 4900 | 5206 } 17577 | 15167 | 13649 | 5460 | 13605 | 11421 | 12545 | 11645 | 10926 | 14800 5000 | 5275 | 17eai | 15392 |13871 | 5532 } 13794 | 11870 }12710 | 11799 | Lines | 14982RM 649 -5- JUNSS3Ud O1YIHISOKLY LY ONY S3UMLYHIUNL SMOIUYA LY $3193dS TWOINIHO JO SYI¥d THAIS ¥OI ,938 yHO NI NOISMIsIO 40 4N3191I4909 eoige,Table & TwE QUANTITY (¥,/t)™ FOR SEVERAL PAIRS OF ‘CHEMICAL SPECIES N-649 26 Ne on m co to | ~ Wa - 1.99602 1.93076 1.93066 2.16155 1.96420 o, | oso | | e-serar | o.ssras | 1.08293 | ses | avsirea | soon | = | 0.99995 ) nanos | rae co | assis | asses | 0000s | - | anes | aorer este |gotacted 4 |(otoeses |p ofesesse |e tcoersp | geet str wo | e.sosss | rotsto | o.ssee7 | o.serse | aan | tore |eterenn 4 patasrta |p amriog [terest geteeora| erases oO | 0.59879 1.18921 1.15033 1.15027 1.28783 1.17025, a | aaeser | aatsce | 2-200 | 220505 | z-stosa | 2.20ses eu | essere | varne | sisees | aiszes | a.z60st | sas et sterens estes tap hoor [tress getesTe ston elena leo 7 = F i Patmm | aera | ooo | atone | iene o, | eves | o.cwse | ori | o.csms | o.sis0 sz | ocasser | ovesss2 | o.sssss | oneenro | 0.0180 co | o.assse | casas | onvsss | o.eezrs | o.ssor co, | o-ro9ee | ovrreso | o.stso2 | o.reo4s | o.r5in1 wo | ovaaeas | ovesase | owen | o.serer | o.szeso wo | = | ocstorr | oceesss | orsesta | 0.0803 | van | | aso | soisss | o.seran ya erosers | resvees |e | ieeere | tees cu | rotso | esosss | oso | - | ovssace x | roses | ness | osita | oon | -THE quANTiTY (1 Table 5 RN-649 + ujfj)"™ FOR SEVERAL PAIRS OF CHEMICAL SPECIES é~ ty o Ne co. C03 No We = ‘1076 | 3.85964 | 3.05926 | 4.77@11 | 3.98559 0, | 10202 - 1.3649 | 1.36042 | 1.54120 | 1.99203 Ny | 103535 | 1.46363 - rans | 1.60340 | 1.43913 co | 103536 | aaeata | a anaze - 1.60350 | 1.43021 Op 1.02265 1.s149 | 1.27929 1.03133 - 1.29686 xo | 1.29299 | 14st49 | 1.39055 | 1.39087 | 1.51084 - Ho | 1.05447 | 1.66619 | 1.5946 | 1.59835 | 1.85549 | 1.63268 ° tosis | 1.73208 1.65861 | 1.65850 | 1.93665 | 1.69573 # 1.ts20s | 5.72261 | 5.36597 | 5.36542 | 6.68287 | 5.54t06 on} 1.08761 | 1.69749, 1.62703 | 1.62692 | 1.a9410 | 1.66263 x | s.o69s4 | t.siz20 | a.7s205 | a.7s193_| 2.o3sig | 1.77263 3 Hg0. o ol on N n, | 3.15222 | 2.90040 | 1.22474 | s.o71a9 | 2.81929 0, | 1.28020 | 1.22674 | tones | 1.23754 | 1.19906 na | tzere2 | 125s | routes | arene | i.zzare co | 1zerer | 1.25888 | roses | 1.26176 | 1.22479 cop | taerit | trem | rouse | args | 1 taait no | 1.26506 | 1.29022 | 10166 | a.2sim1 | 1.2m 0 . ustaon | 1.02759 | 1.39429 | 1.33524 o | tasa08 - rosio2 | 1.43631 | 1.36949 no | sagan) 4.10768 - s.22765 | 3.85068 on | a.4a501 | 2.39310 | 1.02021 . 1.35081 N rsni9s | 1.45363 | 1.03535. | 1. 4a801 :RN-649 Table 6 ‘COMPARISON OF EXPERIMENTAL DATA WITH CALCULATED VALUES OF VISCOSITY FOR SOME INDUSTRIAL GASES AT ATMOSPHERIC PRESSURE ny (Poises x 10-7) Nole Fraction Composition ‘Obs: Calculated 2 | 0 | Nz | CO | Gd, | 7° | Ref.2 | Nef.2 | ea.(6) | fa-(7) | 0.023 | 0.801 0.086| 293 | 1756 | 1761 | 1760 | 1731 0.038 | 0.828 | o.ts3| 293 | nas | ates | ate | amie. 0.107 | 0,831 | 0.062] 293 | 1793 | 1789 | at99 | 1762 0.018 0.595 | 0.285] 0.104] 293 | i738 | 798 | ante | 1723, 0,022 0.200 | 0.as0, 0.108 | 300.5} 1927 | 1792 | ita7 | i751 524.5 | 271s | 2661 | 2762 | 2632 | ons. | aut | atoe | aise | 3996 | 129 | guss | 4753 | 4777 | 4786 0.022 [0.001 [0,892 | 0.078 0.067 | 307.5 1847 | 1835 | 1828 | 1791 sis | 2685 | 2653 | 2655 | 2609 ots | 404s | 4019 | 4052 | 4007 1255 | ss0a | ates | 4191 | 4300 0.007 | 0.030 | 0.896 | 0.003] 0.064} sie | 1904 | ias6 | 1857 | 1828 sie | 2706 | 2644 | 2655 | 2628 ors.s | 41a | 4017 | ao1a | 409 ize? | se95 | 4777 | sae | 4823 0.115 | 0.001 | 0.567 | 0.257 | 0.060] 302 | 1923 | 1929 | 1827 | 1770 526 | 2606 | 2696 | a7ta | 2654 976 | 4041 | 4042 | 4046 | 4027 raes | 4777 | aga | azz? | 4805 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 Ramjet Rocket Temperature, °K 1000 3400 1900 Composition, mole fractio Na 6.11150 40 0. 12465, 0.30754 C02 0.11671 9.10197 co 0.01905, 0.36154 My 0.02809 0.14179 02 0.00574 of 0.03582 0 9.00876 4 9.03890 Viscosity, poises * 10°7: Linear combin Eg.(4) Fq.(8) Fact) iRM- 649 “oe RESULTS AND DISCUSSION In Table 6 are presented experimental viscosity data for some three-, four-, and five-component gas mixtures at various temperatures and at atmospheric pressure, For conparison in the last three colunns are listed the values of the viscosity calculated by means of the Curtiss and Hirschfelder relation (Eq.(21), Ref.2), Eq.(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 a 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 a hydrocarbon fuel with oxygen in a rocket motor. No experi~ mental data are available for these gas mixtures. The viscosity values were calculated by four methods: by taking linear combinations of individual viscosities and by means of Eqs.(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 corresponding 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- ed in Table 3. Inspection of the results shows that the linear combination valuesRy-649 =10- are, as usual, lover than those obtained by other methods. For the ramjet~ gas composition the results are relatively uniform, the value derived from Eq.(6) being slightly higher than the other two. For the rocket-gas compo- sition che discrepancies are more pronounced, especially at the higher temperature. This may be due to the following reasons. Pirst, the tempera: ture correction factor @ in Eq.(6) is probably not valid above 1750°K since it was derived 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 means of Eqs.(4) or (7) for rocket gases which include dissociation products may not exceed § per cent. No attempt has been made in this report to introduce o pressure- correction factor for viscosity. Experience shows that the effect of pres- sure is slight below 20 atmospheres, but that it becones quite pronounced 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 Eq.(6) overcomes this deficiency. Eq.(1) gives slightly better values at low temperatures than Eq.(4), and, like Eq.(4), gives improved results with increasing temperature. In spite of the fact that it dispenses with the use of diffusion coefficients, fc cumberson: vo handle then +) and (6).RM- 649 sl REFERENCES Curtiss, C.F, ond J.0, Hirschfelder, The Kinetic Theory of Multicosponent Systens of Gases, University of Nisconsin, CF-727, July, 1947 Rirschfelder, J.0., R.B. Bird, and E.L. Spots, "The Transport Properties of Gases and Gaseous Mixtures I." Chem. Rev., Vols44, 1949, pp. 205-231 |. Buddenberg, J.W. and C.R. Wilke, “Calculation of Gas Mixture Viscosities," Ind. Eng. Chea., Vol.41, 1949, pp. 1845-1347 Wilke, C.R., “A Viscosity Equation for Gas Mixtures," J. Chea. Phys., Vol.18, 1950, pp.517-519 Gilbert, M., “Estimation of the Viscosity, Conductivity, and Diffusion Coefficients of 0. HN, and OH," California Inativute of Technology, Jet Propulsion Laboratory, Memorandum No.4-51, July 6, 1949. . Hirschfelder, J.0., R.B, Bird, end E-L. Spote, “The Transport Properties of Not Polar Gases,” J. Chem. Phys, Vol.16, 1948, pp.968-981. Krieger, Fide, The Viseosity of Polar Gases, The RAND Corporation, Research Memo- Fendum, AN-646, July 1, 1951.