The Thermal Conductivity of Fluid Air K. Stephan and A. Laesecke® Instat fr Technische Thermodynamik und Thermische Verfahrenstechnik, Universitat Stuttgart, P.O. Bax 80 1140, D 7000 Stuttgart-0, ‘Federal Republic of Germany Based on available experimental data, the thermal conductivity of uid air has been critically evaluated. A new set of recommended values is presented covering a pressure range from 1 to 1000 bar anda temperature range from 7010 1000 K. Using the concept of ‘residual thermal conductivity the commended values are described by a 13-parameter ‘equation of state in terms of temperature and density which may be applied up to density 0f 900 kg/m’, From comparisons of all data sources, the uncertainty ofthe recommended ‘values was extimated tobetelow + 496. Additional experiment are needed, especialy in ‘the subcritical region of liquid air. Key words: ir; fui region; interpolating equation; recommended values; thermal conductivity. Contents 1. trodueton DAY 6 Reference. ‘Thermodynami Key Vacs 3 Themal Conduct mt List of Tables Bie Dilete as Thal Condi 2281, Skelton table ofthe recommended data st 32, Residual Thermal Conductivity 231 Thermal ondustiviy (mW 7K ofaenee 230 4, Boimaton of Uncertainty BL 2. Compre rommened dt ih 3. Adlaowltpments ern 234” rence complains a 1. Introduotion Air is one ofthe technologically most important sub- stances. Reliable values of its thermophysical properties are therefore very often needed. There exists a vas literature on the thermal and caloric properties of air. Based on a collection ofthese data, Bachr sod Schwiee! established a set of equations of state. How ever, Bachr and Schwier did not treat the transport proper- ties of air, which had been measured only ina very limited range prior to 1961. The first compilation of thermal con- ductivity datain the fuid region of air was given inthe books of Vassermann.*? Touloukian* restricted his compilation to the thermal conductivity at atmospheric pressure. In 1975, ‘Vargaftik® published a data set covering a broad range of fluid states. Unfortunately this set contained inconsistencies ‘because, in some cases, two different thermal conductivity ‘aluee wren given far the came paint af tate These ambign- ities were eliminated in a revised version which was pub- lished in 1978.° However, after the first appearance of Var- gafti’s work in 1971 many new experiments were pub- lished, which were not considered in the revised edition. Recent experiments on the thermal conductivity of air siverise 0a reexamination ofthe available data. Asa result ‘pata ir Fleid- und Thermodyramik, Universi. GH Sige, P.O. ‘Box 21020, D S800 Siegen 21, FRG. © 1985 bythe US. Secretary of Commerce on bch fhe United States ‘This copyright i assigned to the American Taste of Physics and the ‘American Chemical Sosy ‘Reis availble from ACS; se Reprints List at back five (0047-2680/85/010227-06/805.00 227 of thie analyse, now eot of recommended valuet hae boon ‘compiled which was used to establish an equation of state for the thermal conductivity of fluid air. The new data set is consistent with thermal and caloric properties with regard to the phase equilibrium curve. Its accuracy has been assessed bby comparisons with all data sources. 2, Thermoaynamic Key Values Ar sa mixture and not a pure Sid. Hence its vapor pressure curve consist of bubble anda dew line (Fig. 1) In the critical region, one has to distinguish between a point of ‘maximum pressure Pq. and a point of maximum tempera- {re Tm. The point Py Separates the bubble line from the dew Tne, whereas the put Tae i teferred to as the ctcal point. It coordinates were taken from thetbook of Bachr and Sehwier! Pe 97.663 ba, 1, = 13252 K, Pe =313 ke/m 0 ‘The dew and bubble points were also calculated from the correlations established by Bachr and Schwier. The equation ofthe dew line reads og py = Ay + Aa/Tx + Agll — YT Tye 7, 2 with the couficionts Ay= 253293, Ay= — 253901, As= 0.00609, A,= 271.6. ‘J. Phys. Chem. Ft. Data, Vol.14,No 1, 1985,228 K, STEPHAN AND A. LAESECKE A similar relationship holds for the bubble line: log py, = By + By/Ty + 10-? XB+B BF T Mr, G3) = 1.00053, By= 41.503, By= — 1.000755. In both equations pressure and temperature are ex- pressed in reduced form, py = p/p, and T, = T/T... There is good agreement between these data and the corresponding values given by Vassetmau” 3. Thermal Conductivity ‘A total ot 59 publications was found in the literature devoted to the thermal conductivity of air, but 15 of them hhad to be omitted from the analysis because they contain ‘ther lees than three data points ur Lacause day 1opuit dat only in small diagrams that cannot be evaluated with suffi- cient accuracy. Among the remaining papers which are rel- ‘evant for an evaluation procedure. 11 report ariginal ‘measurements while six references were previous data com pilations. Naturally, these were not used for the generation ‘of the new set of recommended values but served to estimate its tolerances by comparing it with them, ‘The distribution ofthe experimental points over thep, planeis shown in Fig. 1. It should be noted that no data exist in the subcritical region, with the exception of gaseous air at atmospheric pressure. Most of these data lie in the pressure ‘range from 100 o 500 ar and in the temperature range from 20010470.K. The only experiments heyond these limite were carried out by Tarzimanoy,"* up to 1000 bar and 1200 K. Except for Carmichael and Sage," who used a spherical cell apparatus, all other investigators preferred either coaxial cylinder or hot wire devices under steady-state conditions. w The transient hot wire method, which is considered to be very reliable, was applied to air only by Fleter, Kestin, and Wakeham’? and by Scott et a? To evaluate the experimental data, we employed the residual concept which, despite its obvious drawbacks, is still an appropriate method to represent transport coef cients over a wide range of fluid states" The concept con- siders the thermal conductivity ata given temperature and density as the sum ofa dilute gas contribution and a residual or excess part according to ApeT) =AdT) +42 (9 @ ‘The dilute gas contribution depends only on the tempera- ture, whereas the residual part s assumed to be only a func- tion of density. In the case of air we found this concept to be applicable up to three times the critical density. The density dala were obiained from the equations of Bachr and Schwier! and from Vassermann? in the range 714 kg/m?

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Phys. Chom. Ret. Data, Vol. 14, No. 1, 1985,‘THE THERMAL CONDUCTIVITY OF FLUID AIR 231 3.2. Residual Thermal Conductivity ‘The pressure dependence ofthe thermal conductivity of airhas not ben investigated as muchas the thermal onduc- tivity ofthe dilute gas repion. As the distribution of exper- rental data in Fig. 1 reveals, in certain pressure and tem- perature ranges data do not exis. However, in many cases the residual concept offers a useful tol to obiain the missing data by extrapolation, provided the concept can be applied and no splitting of the isotherms occurs at higher densities. This can easily be checked when the residual part of all data points plotted verous density. In cases wherea large satter ‘observe, especially at igh densities, one may deduce that the residual part is not function of density alone. In such cases the concept is not applicable in its simple form but requires additional temperature functions. ‘After oars onalynin of the experimental date, the measurements of Tsederberg and Ivanova,"*Fleeter, Kestn, and Wakeham,” and Scott etal were selected. For the representation ofthe residual thermal conductivity ofthese data, polynomial of 4th degree turned out to be suficent, Ady =D, pp + Dap, + Dap + DaPi> (8) swith tho sosisionte Listed below: D,=3.12013125, D; Dy = 1.65049430, Dy = 2.307 624 00-10, 1.911 481 75.10-, Again, the residual thermal conductivity is reduced by the factor A from Eq. (6). We have Aly, = A2 /A, whereas the density was reduced by its critical valuep, = p/p,..Figure3 presents the residual thermal conductivity according to Eq, (8) and compares calculated values with the selected experi- ‘mental data ‘By means of Eqs. (3) and (8) representing the new set of recommended values, we calculated a skeleton table for the thermal conductivity of air for given pressures and tempera- turee (Table 1), The epacing of temperatures and presturwe ‘was chosen in different steps in order to permit a safe inter- polation ofthe values. However, in process design systems, nox hema Conducts Tempera TE the use of Eqs. (5) nd (8) is recommended for easier compu- tation. Jn order to give an illustrative representation and & lear view of the influence of pressure and temperature on ‘the thermal conductivity, we plotted a perspective view of the surface (Fig. 4). ‘The fact that air isa mixture requires thatthe shape of ‘the surface difers from that of a pure substance only in the nature of the bubble line and the dew line properics. The diterence isnot visible m Hig. 4 As atypical feature a pre- dominant iniuence of temperature on thermal conductivity is observed, showing two main characteristics. At low te- peratures one notes oteep decreas of thermal conductivity with increasing temperature, asis typical for Hiquids. As can boeseen from Fig, 4 thiseffect is still noteworthy at pressures far above the critical point. where a distinction between the liguid and gascous phase cannot be made. Thus in this re- son, the thermal conductivity exhibits liquidlike behavior ‘At higher temperatures. thermal conductivity passes through a minimum along the isobars and then increases Its ‘behaviors then comparable to that ofa gas. The liquid- and the guslike behavior reflect the different mechanisms of mi- sroncopie energy transfer, The boundary between the gaid- and the gasike behavior is the locus of all minima of the isobars. 4, Estimation of Uncertainty ‘To assess the uncertainty of the recommended values, all the experimental data and also the data from previous compilations were compared with the recommended vals “The results ofthese calculations are summarized in detail in Table 2. The mean departures and their standard deviations suggest moderate discrepancies among the results of the dif. ferent authors. The data of tolyarov,Tpatew, and Tendoro- " and Gaiee and Schifor™ acom to boayetematioaly too ow; this holds also for tables given in the Landolt-Bérnstein series.” The earlier compilation of Tsederberg” and also the Ton 4. Phys. Chem. Ret. Data, Vol 14, No.1, 1985232 K. STEPHAN AND A. LAESECKE ‘rable 2, Comparison of the recommended data set with other sources and compilations Rothor? Tenperature Pressure Wethod Mean departures Number of Ret Year Range K Range bar i Stands dev. Points te o0-200 2 wot vine 1 7aoe ® 1" 7 Stolyarov 293-435 a-su0 Coaxial 5.243.918 1950 eylinger 7 * . Vines se-2173 1 Coaxial 9.0304 1960 ur eylinger nae 5 ° beter 379-1373 a hot wire -2.140.5 © v 10 sel $ Golubev 196-424 1-500 coaxial Lae Gow 426 oma 423.64 ao a Senetleben 273-673 1 Hot wire 1,483.6 8 2 a2 sen wi 33) Sgemichect —gaa-r7 a Egherieat — ovta09 22 566 cali Ghambir 308-363, 1 Hot wire 0,242.2 3 uM 1367 ‘rsederbers 70-360 1 Hot wire -0.981.0 8 we 5 isi 98-490 0,282.0 4 a8 reving arsaee a mot wire -1.980.2 5 ° u 173 Tarimanoy —gup-199 1-500 Hot wire 41,381.34 20 w 107 Fleeter 300, 130 Hot wire “140.5 8 B w i980 scott suu-auo 2 Hot wire 398 312373, 9-528 Yassermann 75-160 1-500 Compilation 0,742.4 8 106 23 Teederberg 273-1279 1-200 compilation 3.5413 4 a 1965 Landoit~ Bornstein 273-473 saw compilation ~2.942.9, 4 51 2 i968 Garroll —— s6u-suu asia compiiation 0,713.04 302 a 08 ‘Touloukian 50-1500 a compilation ~0.820.7 & ry ‘ Vargactik — 95-00u 13-1000 compilation 1,281.6 & 183 6 378 4. Phys. Chem. Ret. Data, Vol. 14, No.1, 1985‘THE THERMAL CONDUCTIVITY OF FLUID AIR 233 retook ta a Pressure p (bar) FFic.5. Comparison of data from ther erature sources with value calev- Ine dreamt fat pcynnadn as meshen T= SDK. wa recent set of Vargafik etal seem to be too high. ‘A more detailed assessment, however, can be read from Aeparture plots slong selected ixatherms, ae given in Figs. 8 forthe widely spaced isotherms 130, 300, 400, and 800 K. nthese diagrams, the deviation of each literature data point denoted by dna, is defined according to 100 snp — Amv anv % with 2ny being the recommended value. The maximum de- ation among difacent anne at temperatures of 200 and 400 K is as high as 12%. It reduces considerably, if those ata were omitted that appear systematically too low; then ‘the maximum uncertainty would be estimated to be at most 4%, and 2.5% at higher temperatures above 400 K. ‘These uncertainties clearly exceed the values claimed by the authors themselves. In order to reduce these uncertainties, Auiber eaperimcuts ate nevessary at suberlcal pressures and temperatures, especialy in the liquid region. Likewise, itis highly desirable to explore by new experi- iments the thermal conductivity of si in the critical epion 130008 ge A) Day) ar Pressure p {bor} ate Fic.7, Comparison of data from ther terturesources with value clon Inte fom theeqation fsa propsedin this work tT = 400K. and to examine a possible critical enhancement. As can be soon from Fig. 3, present data da nat eupport a divergence of the thermal conductivity of air in the critical region. How- ever, it must be expected thatthe overlapping enhancements ‘of the thermal conductivities of the most important constitu- ‘ents of air, nitrogen, and oxygen will result in an enhance- ‘ment in the thermal conductivity of ar, too. It therefore has tobe assumed that values calculated from Eas. (5)and(8) will ‘vecuusiderably wustmall at deusiles vu! 200 1 490 kyu, ‘pressures from 30 to 80-bar, and temperatures from-120 to 100K. Dering preparatinn of thie pape, the authore wore ine formed about a similar evaluation carried out by Kadoye, ‘Matsunaga, and Nagashima.® A comparison to the results reported here revealed almost perfect agreement in the selec- tion of the most reliable data sets. To represent them, Ka- doya et al, adopted an equation of state, with 12 adjustable parameters, which agrees with Eqs. (5) and (8) proposed here sm seven structural terms. Values that were calculaved frou ‘both equations in the range of available experimental data ‘agree well within the tolerances ascribed to the recommend od data ot, = aT ain via) ols) ts 6) im ta) Pressure p [bar] Fic. 6. Comparison of data fom othe itrature source with ales cae Intatrom taequation tsa proposed nts Wore at = 0K. Waa Ta S00 Pressure p Ibar] Fie, 8. Comparison of data from other erature sures with valves cal ‘atedrom teequston oat proposain tte wore! = 20 ‘Phys. Chem, Ret, Data, Vol. 14, No. 1, 1885234 5. Acknowledgments Weowe sincere thanks to the Deutsche Forschungsge- reinschaft (DFG) for financial support. The help of Mr. R. Krauss is gratfilly acknowledged. The work described in this paper was performed in consultation with the Subeom- imittecon Transport Propestis ofthe International Union of ure and Applied Chemistry (TUPAC), The authors are in- debted to Professor J. Kestin for his valuable suggestions. 6. References LD. Boehrand K. Scher, Die ThermodynamischenEigenchafen der Luft (Springer, Ben, 960, 240A. Vanvermana, Ya'Z Kezavchinei and VA Rabinovich, Therma: hysal Properties of ir and ts Component (Nauk, Moscow, 1966 Resin. ALA. Vasserman and V. A. Rabinovich, Thermophys! Properties of [Linu is and ts Comaonons Standar. Moca. 1968 in Rian *¥-8.Touloakian PE tile, and: Saxena, hermoph pial Popertes ef Mater. Vo. 3: Thermal Conductoy. Nonmetallic Liguls ond Gases (Plenum, New York, 1970, SN. B. Vergalk Tables onthe Thrmophyical Properties of Liu and Gases, 2d Hemisphere, Washington, 1973). NCB Vargfl, LP. Flipov, A.A. Tazimanov, and EB. Tol, ‘Thermal Conductvy of Ligue and Gazer Standard, Mocom, 1978 Rian, "MW. faylor and ML. Jonson J. Cem. Pays. 1,219 1940) "ELA. Stlyazoy,V.V-Tpatiey, and V.P-Teodorovch, Zh. Fi Khim. 24, 1651950) RG. Vines, Tans. Am. Soe: Mech. Eng. 82,48 (1960) “H, Gcie and K, Sb, Ally, Waseca 4, 70(1960, LF Golbey,Teplocnrgetia 10, 781963. ‘SE-H, Senfleben, . Angew. Phys. 17, £6 (1964, 4. Phys. Chem. Ret. Data, Vol. 14, No. 1, 1985, K. STEPHAN AND A. LAESECKE LT. Cermichaa and B. H, Sage, AICHE. 3, 5891960, °K Ghambr,J.M. Ghani andS.C Saxena, Ind Pore Appl: Phys 5, 4571967 "=D, L, Caroll H.Y. Lo, and L.1. Ste J. Chem. Eng, ata 13,53 (1968). YON. V. Teederberg and Z. A. Ivanova Therm. Eg. 18,100 (1971) 1). eving, DT Jamieson, and D. 1. Piaget, Trans, Inst. Chem ag. St, 101973, "ALR Tarsmanoy and RS. Saimanov, Teploss. Vox. Temp 5, 912, usm, "R, Flt, J. Ket and W. A. Walsham, Physica (Amsterdam) 103A, 521 1980, ‘Thermophys 2,103 (198) DIN. V. Taadrtry, Thermal Conducity of Gas and Liguids (MIT, Cambridge, MA, 1965) Landolt Béentin, Zahloncert wd Bunrinon Spins, Ben, 196) Yo. Past 5. K. Stephan and K. Lucas, The Vico of Dense Fis (Plenum, New York, 1979, MELT M Hane. RD, MeCart. and E.G. Coben. Phos Utrecht 320973) H1.1.M Hanley, K.E.Gubbins andS. Mord J. Phys. Chem. Ref Data 4 ustus™. HL. M. Hanley, R.D. McCarty, nd W-M. Haynes, Cryogenics 1,413 (0575. RC Reid J.M, Prawn, nd'Th K Sherwood, The Propetsaf Gass and Luis, 3 0, (McGraw-Hil, New Yor, 197 2K Kadosa, N. Matsunaga and A. Nagashia,"Viroity and Thermal ‘Gonguctiiy ot Air 4 Wide Kange or teiperaare and Frese ‘Report tothe TUPAC Subeommites on Transport Properties Lyngby, Denmark, 18-19 August 198, A. Lacscke and R. Krauss, "Comment on the Caleuation ofthe Ther ‘nal Gondotity of Paid Ai” Report of ast hs Technine Thr ‘modynamik und Thermiche Verfahrenstechik, Universi Stutgat, November, 1983.