4i, Pressure-Volume-'emperature Relationships of Gases; Virial Coefficients! J. M. H, LEVELT SENGERS, MAX KLEIN, AND JOHN S, GALLAGHER ‘The National Bureau of Standards ——_ . Definition. Virial coefficients are the coefficients in the expansion of the compressibility factor PY of a gas in powers of the density 1/V, py = Rr (i++ o+--) (a) or in powers of the pressure P, PV = RT + BrP + CoP? + ++) (2) ‘The density expansion is the more fundamental of the two. It can be proved that such an expansion existe for gases at moderate densities, and ite consecutive coef cients can be related to interactions between pairs, triplets, ete., of molecules (1]. ‘The pressure expansion is often more practical, the pressure being more readily mea- } Supported in part by the Air Force Systems Command, Arnold Engineering Develop- ment Center, Tullahoma Tenn., on Delivery Order no. (40-600) 66.938.VIRIAL COEFFICIENTS 4-205 sured than the volume, but it usually converges more slowly, and its coefficients are not as simply related to molecular interaction. In what follows, the emphasis will be on the expuisiou (4i-1)- 4i-2. Units, ‘The units of the virials depend on the units of volume (4i-1) or pres- sure (4i-2) chosen, We will express the volume in em*/mot and give the virials in the corresponding units. However, a practical unit of volume frequently uecd ie the famagat unit; the volume in amagat units is the ratio of the actual volume of a gas over the normal volume, i.e. that which it would occupy at 0°C and 1 atm (1.013250 Duis). The uvimal vokume for « mole of a real gae differs clightly from the normal volume Vs = 22,413,6 em#/mol of perfect gas, owing to deviations from ideality at 0°C and 1 atm. ‘The virial expansion used in conjunction with amagat units of volume is At Pt ete is) In Table 4i-1, the virials Bp, Cp; Aa, Ba, Ca are expressed in terms of By, Cy. Tapue 4h1. Revatiuas ssiweex Vouumn axe Prosouns Vinsan Conrriorenze Gas constant Tdeal-gas normal volume per mole R= 8.8143 J K-! mol Vo = 22,413.6 em! mol! (= 82.056 orate A! mol) (Both on unified seale) Preasure virials (4-2) Amagat viriale (4-3) Va = Vora Ay = 1 By (0°C) ~ Ca (0°C) + + Ag = AeT/273.15 Bp = By/RT Ba = ByAa/Vy Crm (Cy = BERT) Ca = CrAa/¥a 4i-D. Thooretica Interoot. Of groat interest ie the fndamontal relationshin of By, Ci, ... to th molecular interaction. If the molecular field is represented by & function git) wher: specifies the relative coordinates of two molecules, then N f* q — e-senny de i. Bt) =F fo "a (it) ‘Tho virial By(7) is aniquely determined through Ea. (4i-4) if the molecular interaction (2) is known but the reverse is not true. Higher virials can be likewise related to interactions betwen triplets, ete., of interacting molecules. These expressions for he higher wiriale re loss naoful in practice, not only because the higher virials are poorly known exp timentally, but also because the influence of potential function nonadditivity {1] ca these virials is poorly known theoretically. We have used the relationship (4i-t) between second virial and potential function for smoothing the experimental B(T values; for obtaining derivatives dB/d7, @°B/aT?; and where reasonable, for ex rapolating the B() tables beyond the temperature range where experimental data are available. "Practical Importance. The virials By and Cy represent the initial deviations of the equation of state from ideality as a gas is compressed (Eqs. (4i-1 and 4i-2)]. Functions of these virials serve to estimate the initial density dependence of thermo- dynamic propertic 5. Thus, the internal energy Us = U(V,T) — U(#,1) isgiven by fr T dev = wen (BE + aie +) Similar expression | are valid for other thermodynamic functions (2).4208 HEAT i-2. Tue Seconn Vint Corsricient or Hexiom 12. i u eon'nn | 10. 9 8 5 s Tue Secon Vinat Corrricient of Neon anv Ins TEMPERATURE DERIVATIVES 7 1, | rapar, E cmt | ema | 30.00 s | 80:00, | 5 se | 110-00 | 120.00 «| 0 140.00 | 8 tan vo 8 200.00 8 | i 240.00 a4 | 273.18 wo | 250.00 | ioe | 320.00 m5 | | 360,00 21 | j ar3.19 2S 400.00 12.6 | | 500.00 | 13.3 | sooo | igs | 700.00 0 | | | sooo | 142 | 4 4 900.00 ws | 1 =3 1000.00 143 o.| = iVIRIAL COEFFICIENTS 4-207 4in6. Determina ion; Errors. Virial coefficients, in the majority of cases, are not, directly measured but are obtained by analysis of PVT data of gases. The most common practice ii a least-squares fit of the PV values along isotherms with cither density or pressurt as an independent variable. Using this procedure, the precision of the virials can tt en be cbtained from linear least-squares estimates of their standard deviations. For a single experimental set in the very best cases, it may be better Tspu 4i . THE SECOND Vintat, CozPriciEN? oF Ancox anp Irs Temperature Derivatives r | a, ranjar,raner,| 7, | a, |ranjar,| rasan: | em*mat ‘mma | emé/mol "|| 1 fem/inel|em#/mol | emé/eol =1,700 180,00 | -00.9 126 318 Tree || 19000 | Tae} te) S300 =1495 |) 200.00 | <48°7 | 107 | 268 Zico |} 1000 | aacr| too | Taso =¥he8 | aanc00 | <302 | "ts | Laas 21355} 2nc00 | 35:2] 88 | Late Zico |} d20%00 | Tans] 2] Liss Taso || 25000 | Tas: | 38 | Tis 100.00 o| =1.074 |] 260.00 3] 7 =176 02:00 | Tioss || frat | Taz) Gb | Ties Ione $ Bins | 8:65 a | ig 106.00 fi Zea |) 30000 | Zis:z| ot | ie tos.o0 | “ie19 Tése |) ano | Tae} fo | Tio 10°00 | 126: | =a |) Sioa | Taiz] os) Sine H2:00 | 11:3 | Zea | & | ie 114.00 4 =788 || 2] 40 = 105 16.00 | “isnt | Ht | a] | Sina Hees 4 = | : 124.00 | — 125.2 = 655 | 34] 36 =82 2.00 Tina =388 oz] 3 | a 136.00 | Zao |} soo:00 | ae} 25 | Tar 140.00 | “09:8 Zon || ooo | asia} 30 | Lae Hascop | Dose | Zast || doco | aes] ie | = 148.00 | —80.8 | 172 =450 | 900,00 | 19.7] 14 ~3t ideo | Mas'3] tet | 2489 | soooceo | att] ie | Ia soot | Cert] ae | ag |niio | ea] on | 140.00 2} as | -a04 | 100.008) 23.8] 5 1es.00 | =735| 145 | “sre | tsoo.c0 | aus] 7 ee-00 rt | \ i Date below the d ehed line in this and succeeding tables are extrapolations than 0.1 em?/mol for B and 50 em*/mol? for C. However, virial data from different experiments usual y differ by rauch more than their combined precision because of the presence of systen atic errors. ‘The main sources of systematic errors are: 1. Experimenta.’ (a) errors in the value of RT because of temperature errors or the use of seales other than the thermodynamic scale, (B) systematic errors in the volume because of calibra: ion problems, and (c) difficulties with extrapolation to zero density, especially with doa obtained by the Burnett method [3].4-208 HEAT 2. Cutoff problems: AA finite polynomial has to be used rather than the thecreticelly correct infinite series [Eqs. (4i-1) and (4i-2)], but errors arise if the powers omitted would have contributed in the density range studied. ‘To minimize systematic errors, if there is evidence that any existed, we have refitted the experimental data when available. The data refitted are indicated by asterisks in the literature reference for the bles. Wherever feasible, we reduced temperatures “Taste 4i |. Tae Secon VimiaL Corrricienr or Krypton, AND Ins TEMPERATURE Dusuv.vrives 1, B, | TaB/aT, | Ted5/a' r. B, |TaByar,|Teaep aT, | em?/inel | ein?/imel | e1?/snol i fem*/mol| em?/mol | emt/mol 106.00 | —304 sor | -2813 || 215.00 198 521 = 379 | 21659} 220.00 191 =H 230.00 240.00 | 425 250°00 | 206 Tus | 8 207 =e |, a 214 =570 | 1300 Ba aT 208 =E15 | 100.00 | 37.0] =e re to the thermodynamic scale, using the known relation between this scale and the IPTS [4]. If a laboratory maintained its own gas scale, this scale was used. In a few cases, notably He at low temperatures, where one of the purposes of the exy.eri- ment was gas thermometry, we had to leave the intercept free. Regarding the cutoff criterion [5], we chose the maximum density range in which the (k + 1)th virial does not contribute beyond experimental error, and fitted this range with a pels nominl of degree & — 1. Depending on the emount of low-density data avail! '°, we took # = 3 or4, In order to do this, on estimate of the size of the (k + 1)-hVIRIAL conrrrorente 4 209 virial was necessary In cases where it could not be obtained from the data, we used the theoretical valu 9s calculated for the Lennard-Jones six-twelve potential. This procedure was justif :d since only order-of-magnitude estimates were needed. After second and third virials had been obtained from each set of experimental data for a given substar ce, and after obviously wrong results had been eliminated, a smoothing or avera sing procedure was established. Use was made of the funda- mental relation (4i-!) between the second virial coefficient and the intermolecular potential. 4i-6, Potential F1 nctions—Determination, Use. Equation (4i-4) applies to sub- stances for which qi antum effects are negligible. For such substances, Eq. (4i-4) is, Tame U4. THE SECOND VintAL CorFricieNT OF XENON anp Ins Tewrenarune Denivanives — :| 3 | | 99.7 | : 7 7 1 exact. Quantum ¢Teets become important for only the lightest gases [6], ex, helium, hydrogen, tc. ‘These latter are generally referred to as quantum gases. For such gases, Eq (4i4) can represent only a first approximation whose quality goes down with d creasing molecular weight. In either case, i., whether Eq. i-4) is exact or ar approximation. the use of it requires a knowledge of the inter- molecular potential function #(r). In principle, such functions ean be obtained by direct quantum-me hanical calculation. In practice, this procedure is not feasible even for the simplett system. This has required, in effect, the partial reversal of the process. Thus, ine.ead of using Eq. (4i-4) with a known function (7) to predict B(T), one uses (4i-l|, in part, to produce information on g(r) and, in part, to predict B(T). This is dor e by assuming a form for (7) (often referred to as a potential ‘model), based on wk stever fundamental knowledge is available, inserting & number of parameters in this { rm (for example, « and o of (4i-6)], and varying the values of these49010 ura parameters to obtain the best agreement between the B(7) values calculated from Eq. (4i-t) and those determined from the analysis of PVT data described above. ‘The predictive power of (4i-4) remains essentially tact, provided the number of experimental points used is far in excess of the number of parameters scught. Fre- quently used in this way to describe the intermolecular potential of simple nonpolar substances is the Lennard Jones twelve-six potential, a member of the more general class of spherically symmetric m — 6 potentials: we (C-O] Tante 4i-7, Tar Sreoxn Vier. Corrricient ov Nrrroces ano Ins Temperature Derivarives : | em*/mol \ 2, p, | rasan, rss K | em*/inol | em*/moi 88 t 4 5] 65 152 7 a} a <7 4 7 | 38 ~134 7 2) 33 = 7 0) 52 =119 3 9 | 49 -13 4 6] 46 = 105, a 2] 44 = 100 218 fof a3 ~97 1 sa} 40, a1 148.00] -73.7 5] 3h -78 152.00 | 697 S| 30 Sos 4156.00 | —65.8 5 300.00 | —62'3 7 166-00 | —57.3 0 172.00 | —52.7 3 178.00 | —48.6 14.00 | , | emi/inol | em*/mol | em'/mol |||’ | em*/mol | em*/mol | em*/mol 300,00 | —167.3) 318 =935 || 210.00} -34.5 | 95 230 102.00 | -161.2} 3 =893 || 220/00 | -30-2 | 80 ~24 404.00 295, =s54 || 230.00 | -26-4 | 84 =200 106.00, 285 =sis_ || 24000 | -22:9 ) 79 List 108.00 275, =785 || 250-00 | -19'8 | 75 =176 310.00 | 266 =754 || 260.00 | -16.9 | 71 = 168 1900 258, =725 || 273.15 | -13:5 | 66 A155 114.00 | —130.4) 249 Zoos |} 280.00 | =11'9 | os =150 116.00 | =126.0| 242 | 673 || 300.00) -7.7 | 58 136 118.00 | —122:0} 235 | —649 || 520,00) 4.1 | 54 124 120.00 | ~118.2 | 228 340.00] 1.0) 60 =u 124.00} 110.8 | 215 346.81] 0.0 | 48 =i 128.00 | 1043 | 204 360.00] 1.7 | 46 = 106 195 avaiis| ga | ae 101 184 380.00] 4.2 | 43 a3 6 400.00] 6.3 | 40 168 450.00 | 10.7 |___ 35 361 500.00 | 14.1 | "30 162.00| 73:8 | 154 550.00 | 16.8 | 97 186.00) 69.9] 148 =378 || e0000| 19.0 | 24 160.00} 66.2} 142 650.00] 20.8 | 2 166.00} 611) 134 700.00 39 172.00} —565 | 127 800.00 16 178.00 | —s2'2| iat 900.00 14 ys4.00| 48.3) 115 100000 2 190.00) -44.7 | 10 =270 |} 1200.00 3 200.00 | —39:3| 102 =248 || 1400/00 7 Equation (di) and the procedures described above were used for the quantum gases He, Hs, and D: as well. In these cases, however, the methods were used only. to facilitate smoothing and interpolation of virial data. For H:0, D.0, and CO: @ potential of the form (4-6) was found to be inadequate. These oubotancee were therefore treated as were the quantum gases; that is, the methods outlined were used only for smoothing and interpolation. ‘The tables prepared for these six substances ‘conciet only of emoothed experimental B(7) values, with no extrapolations attempted, ‘Tables of 7 dB/aT and 7 ¢*B/dT* are not given, nor are potential parameters used in the smoothing process reported since they are without clear meaning. Since the BCT) tables for these six substances aro s0 closely tied to the experimental values, ‘minor departures from smoothness in the tables may be detected.VIRIAL COEFFICIENTS 4213 ‘Third virials in all c ses, were obtained by graphical interpolation of the (refitted) experimental values fo C. They are summarized in Table 4i-16. ‘Table 4i-17 containe values for the Boyle temperature and the inversion tempera- ture. In those cases 1 here the form (4i-5) for the intermolecular potential applies, ‘the potential paramete rs and the value of m are summarized in Table 4i-18. ‘We note that the op! imum value of m is much eloser to 18 than to the popular value of 12, : 45-8. Accuracy of the Tables. From a computational point of view, in all cases, the temperature spaci ie is sufficiently fine to allow for an interpolation to be made Tanup 4i1(, Tar Szconp Vinrat Corrricienr or HyproaEn 1, B, | BR K Jemima} KE fem'yimot 24.00 | -112.8 |) 74.00 | -12.9 dean | —1ne'2 || 28-00 9 26.00 | 100.8 || 82.00 | “—8.9 27.00 | 9418 || 86.00] -7.2 28.00 | —80.6 | 90.00] —8.7 30.00 | =80.7 || 110.00 | -0.0 31.00 | 76.7 || 110.04] 0.0 sziu0 | X1310 || 120.00 | 2.0 33.00 | 69.5 || 130.00 | 3.7 34.00 140.00] 5.1 35.00 au.00| 6.4 36.00 160.00) 7-6 38.00 170.00] 8.6 440.00 180.00 | 9.6 42.00 190,00 } 10.2 44.00 200.00 | 10.8 48100 8000 | 13.0 48.00 273.15 | 18.7 50.00 300.00 | 144 54.00 260.00] 15.2 58.00 313.15 | 15.6 62.00 400,00 | 15.9 66.00 420.00 | 16.1 10.00 ‘using a quadratic fc mula without the introduction of errors. Furthermore, linear interpolation can be used without introducing an error of more than 0.3 em#/mol in DT) oming. Wo the seglect of quadratic torme Tt should he noted that where B, 7 dB/aT, and T!d!3/dT? are available, a Taylor series expansion can be used for interpolation. Te is much harder to aseece the absolute accuracy of the tables in any general way. Where data from m any sources are available for one substance, as is the case for most of the noble gases a: d for nitrogen, one usually finds discrepancies up to 1.5 em*/mol in B and up to 20 ercent in C hetween data from different laboratories. Discrep- ancies in B may bee me much larger at temperatures below critical. ‘The main source4-214 BRAT Tapie 4i-l1, Tae Seconp Vintat, Cozrricrent or Devrerium 84 85 92 100 110 410. 00 00 00 00 00 00 120.00 130.00 140.00 150.00 160.00 20‘ 180.00 190.00 373.15 420.00 2 3 12.2 3 na Tamir 4i-19, Tue Sreawn Ventas ‘onerreresn or W. wen Vavon (H.O) 7, 432, 434. 400. 438, aaa. 446. 448, 400. 482. 454 456. 458. 460. 462. 464. 466. 470. 475. 480 485. 00 700 490. 495. > B, em?/mel | 1K 500.00 505.00 310.00 515.00 520.00 20.00 B, em?/mol ~176.2 =170.4 =100°0 = 160.0 = 155.8 ~148, = 139. A122 = 135 =119 =u, =107. 102, = 97. 93, ~88. are =50. 78 -72.9 60.4 00:1 = 82.9 = 59.9 =57.0VIRIAL COEFFICIENTS 4215 of oxygen data (L. A. Weber) is particularly precise, ~0.1 em#/mol in B, and agrees swith the others withiz combined precision. For hydrogen and deuterium, problems With the temperature cale between 100 and 274 1 muy cause ervors fu D ws laige ao 0.5 em?/mol. For HO and D,0, there is only one source for which the precision ranges from several c11/mol at the lower temperatures to 0.2 em*/mol at the higher ones. For COs, disen pancies of several emi*/nol iu B eaist between data of different sources, and for CH,, of 0.7 em*/mol in B and of 10 percent in C. ‘Tapue 4113. Tae Si conn Vintat Corrriciesr or Heavy Water Varor (D:0) ri |aemymall 2% |, oms/met -177.6 Sis. = 166.3 = 1611 = 156-4 un = 140.0 = 1328, =126.1 =119.6 soz.00 | —250.8 na.e 454.00 | 251-4 = 10811 456.00 | —247.0 = 103.0 458.00 | 242.8 98.0 ‘ou. | 238.8 98.3 462.00 88.8 464.00 ~84.6 4360.00 =80.0 488.00 -76.7 470.00 -73.1 475.00 09.5 480.00 66.2 485.00 03.0 4490.00 | = 39.9 495.00 | =37.0 |, Use of the 7 ables. ‘The averaged virials presented here can be used for ealeu- lations of precise PT products at low pressures. However, in the process of separately averaging and oun ing the second and third virials, correlations ia their experimental errors have been of iterated; thus, they cannot be used to represent the PVT data from which they w re derived within experimental precision over the entire density range, If precise 7 VI values are needed at higher densities, 3 ie woually proforablo to interpolate in th original data. ‘The tables of vir als and their temperature derivatives can be used to ealculate the initial density depe sdence of other thermodynamic prepertios [24216 npaT Taper 4i 4. THe Seconn Virta Cozrricrent or Cannon Dioxin (CO;) 25.00 | 181.8 || 420.00 | 02.0 255.00 | 174.1 |} 430.00 | 49.1 260.00 | 166.8 || 440.00 | —45.9 265.00 | —160-0 || 450.00 | 42.8 27000 | 153.5 | 460.00 | —40.0 273.15 | —149:7 || 480.00 7 275.00 | 147.4 |} 500.00 0 280.00 | —141:7 || 520.00 8 285.00 | =136:2 || 540.00 1.9 290.00 | 181.1 |} 560.00 4 205.00 .2 || seo.00 | 15.9 300.00 5 |} 600.00 | 12-4 310.00 8 |} 620.00 | -9:8 320.00 8 | 640.00 | 7.4 340.00 8 =3.1 350.00 7 =13 1360.00 0 | 7481 0.0 370.00 || za0.00 27 373.15 2 || s00.00 6.0 380.00 9 | s50.0] 8.8 300.00 | 644 | 90:00 | ana 400.00 | =60.2 | 950.00} 13.0 410.00 | =56.8 |! 1000.00 | 14.6VIRIAL COEFFICIENTS 4217 . THe Seconp Vintat Corrricient or Meriane xp Irs Temperature Derivatives ‘Tair died 1&8 (aT, em?/mol Te aB/aT, em?/mol er 2,044 ~ 505, 643 = 2,132 6 = 463, 114.00 ols 2028 3 459, 116.00 25 | 594 = 1,934 0 ~307 118.00 5] sm = 11846 8 309 120-00 1) 550 = 1764 2 — 346 122.00 2] 331 = 1688 2 324 124,00 7] 512 =1617 6 =318, 128.00 6 | 495 1,551 5 306 438"00 o| 479 =11400 ea 289 130,00 | 240.7 | 404 = 1,492 3 ~213 132/00 | —233.7 | 449 = 1,378 4 = 247 304.00 | a77-0| 135 =107 4 136.00 | -220'7 | 422 1,280 2 =207 140.00 | =208-8 | 308 = 1,193 2 =196 14.00 | 197-9] 377 -15 7 =191 148.00 | —1s7.8 | 357 = 1040 7 =17 152.00 | -178.5 | 340 984 4 = 150 156.00 | —169.9] 323 = 928 4 = 130 160.00} —161.9| 309 | -877 0 =126 164,00 | 154.5 | 205 —831 0 -14 168.00 | —147.5 | 282 = 789 . az2loo | =141"0 | 371 =751 8 176.00 | —134.9| 200 =716 3 | 233 180.00 | 129.2) 250 =683 || s00.00] 18.8) 31 -70 164,00 | 193.8 | 241 =853 |} 900.00) 22.1] 25 = is8.00 | [110'7 | 993 son || ro0000 | 947 | 98 =a 192.00 | —113.9| 224 =600 | 1100-00} 26.8} 20 =a7 196.00 | 109.4) 216 =576 |) 1300.00] 29-8] 16 = 39 200.00 | -103.1 | 209 =554 |] 1500100 | 31.9] 13 32as urat ‘Tarte 4i-16. Tar Tarp Vintat Cozrricinnts or Vantous Sunstances (C in units of 10%em*/mol?) 7,K| He | Ne | ar | Kr | Xe | Ne Air| Hz | Ds| H:0| D.0 | Cos | CH 110 320 180 140 150 100 180 200 220 240 260 273 280, 28 26 23 | 24 90) 21 17} 19 s as | a8 a3 | 17 {| 12] 16 1 | as |] 18 | 10} a5 Ww a si | 29 36 | 28 s2| 26 49 | 24 45) 22 42| 21 20) 41| 13 19} 36 | 13 38 | 19 as| as} 1s eee | se) ae ae | 92)) 10) eee 3 7 a2 | 17 7] 30} 12 a 16 18 | 8 16 | 26 15 | 24 35 | 22 as] 90 u| is ele : : ag]... | 20 SEY of os) 0) as ee wt al foo ||P | aa 0 Mt oy S f= 00) 180) 22] 15: = sal— 6a] 2 | oa = 17/20] 1VIRIAL COBFFICI TS 4-219 Tasve 4i-17, Tae Bove Tearenatere ano tHe Inversion Temperature or Vartots SunstaNces fo Boyle Inversion a ‘temperature, K | temperature, Helium... ey Neon eco p21 231.42 Argon. VINE) aileg tis Krypton : 375.00 1089.72 enon... aoe 708.03, 1455.79 Nitrogen. 11: 327.92 620.63 Oxygen : 405.88, 70443 Air. 346.81 058.79 Hydrogen mat 110.04 | Beuterior 118 30 Carbon d sside.......66-| 714.81 Methane....-200005 509.68, 967.81 Taper 41-18, Pore: TIAL PARAMETERS FoR THE m — 6 PoTENTIAL oF SeLxeren Sunstaxces subst ace | ‘eon 18 404 22.83 ‘Argon. 18 160.87 43.74 Krypton 2100.1] 1g | 224.78. 53.7 Renan 18 uy 29 73192 Nitrogen 2 199.41 ert Onyaen, a1 172.93 44.49 Air a 447.76 50.95 Methaiie vic] BL | airtd Dv References 1, Hirschfelder, J. 0., C.F. Curtiss, and R. B. Bir Liquids,” chap. $, 9h Wiley & Sons, tne., New 2. Appendix 3B of ref 1 3. Burnett, E. S: J. « ppl. Mech., Trans. ASME 68, A136 (1936). Hoover, A. E., F. 3. Canfield, R. Kobayashi, and Th. W. Leland, Jr.i J: Chem. Eng Data 9, 508 (1964) . Thomas, H, Presto 1, and C. G. M, Kirby: Metrologia 4, 30 (1968). Senuers, J. M, Hi. levelt: ASME Proc. 4th Symp. Thermophys. Properties, p. 37, 1968 fe Boor, I: Rent. j roar, Phys. 12, 305 (1048). Klein, Max, and HIME Hanley: NBS Tech, Note Sou; trans, Faraday Soc. @4, 2927 (2968), . Marquardt, D. W.: J. Soc. Ind. Appl. Math, 14,431 (1968). References for Table ti-8 to 4i-16 Experimental PVT di ta from sources marked by an asterisk were fitted. Table 4i-2: Helium 1, Holborn, L., an¢ H. Schultze: Ann. Payrik 47, 1089 (1015). #2, Holborn, L., anc J. Otto: Z. Physik 30, 320 (1924). “Molecular Theory of Gases and4-220 nat 3, Michels, A., and H, Wouters: Physica 8, 923 (1941), 4. Kistemsker, J., and W. H. Keesom: Physica 12, 227 (1940). . 6. ; Sennetder, W. Gand J. A. He DUmie: J. Chem. Phys. 47, 701 (1049). 5. Yntema, J. L., and W. G. Schneider: J. Chem. Phys. 18, 641 (1950). 1 Keller, W. E.: Phys. Rev. 97, 1 (1958) | Silberberg, J. J., K. A. Kobe, and J, J. MeKetta: J. Chem. Eng. Data 4, 314 (1959) Stroud, Lu. J. E. Miller, and L. W. Brandt: J. Chem, tng. Data 8, 91 (1960) White, D., Th. Rubin, P. Camky, and H. L. Johnston: J. Phys. Chem. 64, 1607 (1960). Canfield, F. B., T. W. Leland, and R. Kobayashi: Advances in Cryog: Eng. 8, 146 963) 12, Witonaki, R.J., and J. G. Miller: J. Am. Chem. Soe. 85, 282 (1903). 13. Hoover, A. E., F. B. Canfield, R. Kobayashi, and Th, W. Leland, Je.: J. Chem. Eng. Data 9, 568 (1964) 1d. Boyd, M.E,, 8. ¥. Larsen, and H. Plumb: J- Research NBS 2A, 155 (1988). 15. Cataland, G., and H. Plumb: To be published. Table 4i-8: Neon "1, Holborn, L., and J. Otto: Z. Physit 88, 1 (1925). #2, Holborn, L., and J. Otto: Z. Physik 88, 359 (1920) M4 Michela 4.7. Waseananr, and P. Lonwerse: Physien 96. 539 (1960) Table 4i-4: Argon “1, Holborn, L., and H. Schultze: Ann. Physik 417, 1089 (1915). *2) Holborn, Land J. Otto: Z. Physik 28, 77 (1924). 3, Holborn, L., and J. Otto: Z. Phyeik 30, 320 (1924) 4, Tanner, C. C,, and I, Masson: Proc. Roy. Soc. (London), ser. A, 128, 268 (1930) 5, Michels, A,. H, Wiiker, and H, Witker: Physica 18. 627 (1949) 6, Whalley, E, Y. Lupien, and W, G. Schneider: Can. J. Chem. 31, 722 (1953) ST, Michels, A.’ J. M. H. Levelt and W. de Graaff: Physica 24, 659 (1958) and J. Rech: CNRS 80, 55 (1960). Cand R. FR. Sonntag: Adiancen in Cryag. Rng. 14, 279 (1968. 10. Weir, R. D., 1. Wynn Jones, J. S. Rowlinson, and G. Saville: Trans. Faraday Soc. 68, 1320 (1967) 11. Byme, M. A., M. R. Jones, and L. A. K. Staveley: Trans. Faraday Soe. 64, 1747 (1968). Table 4i-5: Krypton ‘1, Beattie, J. A., J. 8. Brierley, and R. J. Barriault: J. Chem. Phys. 20, 1013 (1952) 2. Whalley Fi. and W. Gi. Schneider: Trang ASMP. 76, 1001 (194) 8, Fender, B. &.'F., and G. D. Halsey: J. Chem. Phye. 38, 1881 (1902). 4, Thomaes, G., and K, Van Steensrinkel: Nature 13, 160 (1962). 5. Trappeniers, N. J, T. Wassenaar, and G. J. Wolkers: Physica $2, 1503 (1906) 6. Weir, RD. 1 Wynn Jonas, J. Rowlinson, and G. Saville: Trans, Faraday Sec. 68, 1320 (1867). 7. Byrne, M. A., M. R, Jones, and L., A. K. Staveley: Trane. Faraday Soc. 64, 1741 (1908) able 466 M1. Beattie, J. M., R. J. Barriault, and J. , Brierley: J. Chem. Phys, 19, 1219 (1951). #2, Michels, A., T, Wassenaar, and P. Louwerse: Physica 20, 99 (1954), 3, Whalley, E., Y. Lupien, and W. G. Schneider: Can. J. Chem. 33, 633 (1955). Table Nitrogen “1. Holborn, L., and J. Otto: 2, Physii: 10, 367 (1922) 23, 77 (1924) ; $0, 320 (1924). 2, Michels” A\, Hl. Wouters, and J. de Boer: Payetea 4y 98/ (1954), 3. Saurel, J., and J. Reoh: CNRS 42, 21. (1958) 4 Canfield, F. BT. W. Leland, and R. Kobayashi: Advances in Cryoo, Eno. 8, 140 1963). 5, Witonsky, 1 Ju, and J. G, Miller: J. Am, Chem, Soc. 85, 282 (1963) #6. Crain, R. W., and K. E, Sonntag: Adeances in Cryog. Eng. 11, 879 (1965). Table 4i 1: Oxygen $1, Holborn, L., and J. Otto: Z. Physik 10, 367 (1922), #2. Michels, A.) H. W, Schamp, and W. de Graaif: Physica 90, 1141 (1954).VIRIAL COEFFICIENTS 4-221 #3, Weber, L. Au: NB, Repl. 9710, 1968. (We acknowledge the help of Dr, Weber in refitting his data fo our purpose.) Table avy: aw 41, Holborn, L., and H Schultze: Ann, Physik 47, 1089 (1915). #2, Michels, A., T. Wa senaar and W. Van Seventer: Appl. Sci. Research Ad, 52 (1953) #9, Michela, A.) T. Wai enaar, J. M. H. Levelt, and W. de Graail: Appt. Sct, Research Ady 881 (1954). Table #i-10: Hydrogen #1, Michels, A., W. de raulf, T. Wassenaar, J. M. H. Levelt, and P. Louwerse: Physica 25, 25 (1959). 2, Goodwin, R.'D., D E. Diller, H. M. Roder, and L. A. Weber: 121 (1084). . Research NBS 68A, Table 4:11: Deuterium .W. de raf, T. Wassenaar. J. M. H. Levelt. and P. Lonwerse: Phusion 2, Knaap, H. F. P., ). Knoester, C. M. Knobler, and J. J. M. Beenakker: Physica 28, 21 (1962) Table 4i-12: Water Vapo: (H:0) 1, Kell, G. 8., G. B. } icLaurin, and E. Whalley: J. Chem. Phys. 48, 3805 (1968). Table 4i-13: Heavy Water Vapor (D:0) 1 Kell, G.S.,G. E. } ‘cLaurin, and E. Whalley: J. Chem. Phys. 49, 2839 (1968) abie 41-18: Varoon Lio2 ae (GU2) 1, Michels, A., and C, Michels: Proe, Roy. Soe. (London), ser. A. 183, 201 (1935). MacCormack, K. E | and W. G. Schneider: J. Chem. Phys. 18, 1269 (1950) Kendall, B. J, and B. H. Sago: Petroleum 14, 184 (1051), Piefferle, W. C..J. 4. Goff, and J. G, Miller: J. Chem. Phys. 23, 500 (1955). Dadson, R. 8. B.J Evans, and J. H, King: Prac. Phys. Soe. 92, 1115 (1967). Vukalovich, MM. P, and V, V. Altunin: “Thermophysieal Properties of Carbon Di- valde," United Bin slum Alviniy Bueigy Authvrity Peaualation, Cullet's Publistiessy London and Wellin ‘borough, England, 1968. pepen Toble 4i- 1. Michels, A. Schamp, H. W., E. A. Mason, 320 (1088), 3. Douslin, D. Rut Poor. Intern. Rescarch Thormedyn. Transport Propertice, p. 135, ASME, Princeton \ niversity, 1962, 4, Byme, M.A, MB Jones, and L. A. K. Staveley: Trans. Faraday Soc. 64, 1747 (1968). Methane and GW. Nederbragt: Physica 8, 569 (1980). C. B. Richardson, and A. Altman: Phys, Fluide 1,