Standard Chemical Thermodynai Groups Robert A. Alberty Deparment of Chemistry, Masachusts Institute of ecology, Cambrides, Masachsets 02139 ‘The chemical thermodynamic properties of alkylbenzene isomer groups from C,H, to ‘CoH in the ideal gas phase have been calculated from 298.15 to 1000 K from tables of| ‘Stull Westrum, and Sink Intheabsence of literature data onall isomers of higher isomer groups, the properties of isomers of CygHly«t0 CH, have been calculated using Benson sroup values. For isomer group properties, increments pr carbon atom have been calet- lated to show the extent to which thermodynamic properties of higher isomer groups may ‘veut ly Inna watcapotation, Dgulibrian nok fractions within isomer groupe bare been calculated fr theideal gas state from 298.15 to 1000K. Values of C,S°, cH" and AG axe given forall species from C,H, 0 C,H, in joulesfora standard state pressureof 1 har Key words alkylbenzene; Benson method; enthalpy f formation; entropy Gibbs energy of forma- tion; heat capacity; isomer group thermodynamic properties isomer mole fraction; thermodynam- fe propa Sontents Properties of Alkylbenzene Isomer |. Introduction. "7 2. Standard Thermodynamic Popertics of Isomer Groups 3. Calealations of Standard Thermodynamic Properties of Alkylbenzenes Using the Benson Method. 178 4. Tables of Standard Thermodynamic Properties of Alkylbenzene Isomer Groups. 5. Equilibrium Mole Fractions Within Alkylben- 170 zene Isomer Groups... 180 6. Standard Thermodynamic Properties of Indi- idan Allbenzne Speci. . 180 7. Discussion 7 192 8. Nomenclature 192 9. Acknowledgments, : 192 10, References - 192 List of Tables 1. Number of structural formulas. chiral centers. isomers, and line in tables for aikylbenzenes... 178, 2. Root-mean-square deviations between alkylben- zene therinodynamic properties from Stull, Wes- trum, and Sinke and from the Benson method... 179 4. Introduction ‘When chemical equilibrium calculations are made on organic systems involving alkylbenzenes larger than to- (© 1985by the U.S. Secretary of Commerce on behalf ofthe Unite Sates ‘This copyright i signed to the American Iasttue of Physics and the (0087-2690/05/010177-16/$05.00 3. Standard heat capacity at constant pressure ox alkylbenzene isomer groups in J/K mol 4. Standard entropy for alkylbenzene 1 groups in J/K mol. 5. Standard enthalpy of formation for alkylbenzene ‘comer groups in KI/mol 6, Standard Gibbs energy of formation for alky- benzene isomer groups in kJ/mol 18h 7. Standard enthalpy for alkylbenzene isomer ‘groups relative to isomer groups at 298.15 K in 1i/mal... 8, Standard enthalpy for alkylbenzene isomer ‘groups elativeto the elements at 298.15 K in k3/ ‘mol as 9. Equilibrium isomer groups. 10, Standard heat capacity at constant pressure for alkylbenzenes in J/K mol 184 11. Standard entropy for alkvIbenzenes in J/K mol 186 12, Standard enthalpy of formation for alkyiben- zenes in k/mol 13. Standard Gibbs energy of formation fr alkyl Denzenes in kJ/mol 180 1st 181 182 182 182 188 190 tena, the mules func peste essence Wocy rapidly ‘with carbon number. It is therefore convenient to calculate chemical thermodynamic properties for alkylbenzene iso- ‘mer groups andl use these properties in equilibrium caleula- tions, as recommended by Smith. The mole fractions of in- dividual species may then be calculated ina second step since their mole fractions in their isomer groups are functions of temperature only for ideal gases. 7 4. Phys. Chem. Ret. Data, Vo. 14, No.1, 1985178 ROBERT A. ALBERTY ‘The preceding article? in this series has presented chemical thermodynamic properties of alkane isomer ‘groups through C, Hz. for the ideal gas state from 200 to 1500 K. These tables provide a basis for extrapolation to higher carbon numbers. ‘The rst suastical-mechantcal correlations or tne chemical thermodynamic properties of the alkylbenzenes ‘were made by Pitzer and Scott.’ Prosen, Johnson, and Ros- sini computed a numberof enthalpies of formation of alkyl bbenzenes and developed an extrapolation formula. Taylor, ‘Wagman, Williams, Pitzer, and Rossini* made statistical ‘mechanical correlations for the four C,H» and the eight C,H: alkylbenzenes. Further work was done by Rossin, itzer, Arnett, Braun, and Pimentel,° who published tables in 1953. Some further small changes were made by Stull, ‘Westrum, and sinke” in publishing their book in 1Y0Y. 1ne enthalpies of formation of alkylbenzenes at 298.15 K have been evaluated by Cox and Pitcher,* and the thermodynamic propertiee of the CiHjs allylbonsonce at 298.15 K have ‘been presented by Somayajulu, 2. Standard Thermodynamic Properties of Isomer Groups ‘When isomers are in chemical equilibrium, it has been uw for sume dase’ chat they ean De aggregated In calculations of equilibrium mole fractions by use ofthe stan- ‘dard Gibbs energy of formation 4 G1) of the isomer group Aefined by —RTIn| ¥ exp —4 or/Ra)), 0 4.60) where ,G ; is the standard Gibbs energy of formation of an individual isomer and Nis the number of isomers in the group, including stereoisomers. The equilibrium mole frac- tioner of vasiows inomersin a group can be calculated using. Fim expe ()— 4G; 1/R7 , a ‘where y; 1s the sum of the mole fractions of the individual isomers. The corresponding equations for the other standard thermodynamic properties C(I), $ (), and 4-H" (0) can be derived by differentiating Bg, (1} with respect W tempers ture." When standard Gibbs energies of formation of isomer ‘groups are used to calculate equilibrium constants for reac- tone of ideal exces, the aqilrivn expression i written in terms of equilibrium mole fractions of isomer groups. For the alkylbenzenes the standard chemical thermo- dynamic properties for an isomer group are interrelated by 4G) =4.r0-TIs = 1S sage — (8 — 3Sin40 Js 8) ‘here nis the number of carbon atoms. To calculate the chemical thermodynamic properties foranisomer group, aterm must be included foreach molee- las spevio, including stctevisumers. The nusnbers of chiral centers and isomers ofthe alkylbenzenes areshown in Table 1. Rather than having a line in a thermodynamic table for each steranieamor, thie article follows the etandard practice of giving properties of racemates. Thus R In 2is added to the 4. Phvs. Chem. Ret. Data, Vol. 14, No. 1.1905: Table 1, Numbers of tsomer of alky benzene. Number Chiral Centers Tota of tines "One “Two” _{somers cone 1 2 8 : cet (et ino! ; canto 4 of 4 conta 8 fone inc 3 cits 22 yo 23 ents 40 eet tno as ciznie 67 23 103 calculated standard entropy and RT'In 2s subtracted from the standard Gibbs energy of formation of one of the chiral Forms at cavl tamprratune. Theseus, the nustbers Uf lites in tables in this article do not correspond to the total numbers of isomers; the numbers of lines and of isomers are ‘compared in Table 1 Stull, Westrum, and Sinke” give data on all the isomers ‘through C,H, and on 7 of the 23 isomers of CygH,. In order to compare the properties expected for the remaining isomers of C,cH,, and to examine the relationship between ‘isomer group properties and carbon number, the Benson ‘group method was used. 3.Calculations of Standard Thermodynamic Propertice of Alkylbonzonoe Ucing tho Benson Method In view of the rapid increase in the number of isomers with carbon number, we are dependent ou various etinsa- tion and extrapolation methods for thermodynamic proper- ties of higher isomers. Calculations using the Benson meth- ‘dl were useful in considerations of the propurtioe of the higher alkanes," and they are needed for the alkylbenzenes because the increments in isomer group thermodynamic properties are still increasing with carbon number at C,H. ‘Therefore the Benson method was sed to estimate Cz, S, AH’ and 4 ¢G* forall the individual isomers ofthe alky- benzenes up to C,H in the ideal gas state using computer programs written in APL.* In order to make these calculations, the structure of cach alkylbenzene species was divided into the following Denson groups: CIC} CUTyIChy CANO, CICle CLCa CHE, (Cy CHIE, CIC (Cis, Cal, and Cy(C)- In addition the total symmetry number (TSN), number of “ontical isomers OPT). and ortho corrections were identified. In view of some of the uncertainties in some ofthe alkylben- zene group values indicated by Benson, the gauche and I,5- H repulsions, which affect only several of the most highly branched species were omitted. In calculating symmetry numbers areport by Davies, Syverud, and Steiner” was very helpful. The group assignments were checked by matrix Iuuliptiaion w be sue diey aaauuted fo the wast ‘numbers of carbon and hydrogen atoms. ‘The matrix of numbers of contributions was then ma- trix multiptied hy a mativ ofthe Remsom valves ta ahtnin for cach isomer thesum of the contributions to «HY isnot»‘THERMODYNAMIC PROPERTIES OF ALKYLBENZENE ISOMER GROUPS 179 Stancard altos energy of formation In ki/mot C'r300» C 400» C rs00» C pe00s C pa00» C'>ioo0» And C jp 509. In rufther steps in the calculation the neat capacity values Were ft to the equation Cheatprty?, 4) using the least-squares criteria, and the values of, Band y were used to caleulate C},S*, and A -P from 200 t0 1000 K S°=Sj +alnT+8T + (y/\T?—Rin(TSN/OPT), (5) AH =A,Hy +aT+(B/2)T? U1 SL? ~ MULE LF 396 eng — (nS — Hs, 6 ‘Thevalues of4 ,G” at various temperature were then caleu- lated using Fa. (3). Table 2 shows how well the chemical thermodynamic properties calculated using the Benson method agree with the values from Stull, Westrum, and Sinke™ for Ci, through C,H, and for thesevenisomersofCoHy¢for which they give values The difreaces between the iterator ond estimated values at each temperature were squared, divided by the numberof pairs of values, and the square root was taken. For C.H and C-H, thie yields the magnitudes ofthe deviations, and forthe higher homologous seriesit yields the root-mean-square deviations asa function of temperature. [Even for the higher homologs the root-mean-square devia tions in 4G" average less than 2K mol 4. Tables of Standard Thermodynamic Properties of Alkyibenzene Isomer Groups. Since the International Union of Pure and Applied ‘Chemistry has recently recommended that thermodynamic data be given in ST units fora standard state pressure ofl bar (10* Pa, this has been done for the tables in this article. The ‘change in standard state pressure trom 1 atm t0 1 bar does notaffectC;; and ,H”, but thestandard entropy ofan ideal ‘ass increased by A In(.013 25) = 0.109 5 K~* mol™* ‘any temperature and the standard Gibbs energy of forma- tion is reduced by [RT In(.013 25)}, where 5 is the nt in- ‘crease (4~n) in moles of gas in the formation reaction.*° a Table 3 to 8, the Stull, Westrum, and Sinke tables Ihave been used to calculate the isomer group properties for aH, to Cy and the Benson meted hao beon wed to calculate the isomer group properties for CycH,4 to Cy Hy. For each property the increments in going from one carbon. ‘number to thenext are provided, These increments providea basis for a linear extrapolation of standard thermodynamic properties of alkane isomer groups to higher carbon ‘numbers. Ina general way we would expect these increments toapproach constant values asthe carbon number increases at constant temperature. At lower temperatures, constant values are not approached for some properties, and this ndi- Catca that cxtsapolatione ae van cepelngly eaveta The limiting increments per carbon atom are quite similar t0 those for the alkanes, but there are some differences? The limiting increment in AP) ace abot § KT mt more negative for the alkylbenzenes than for the alkanes above 500 K. The increments in C(1) and S° (I) are remarkably similar forthe two homologous series above 400 K. “Table 7 gives A’ (I, T)— H’ (I, 298.15 K), ‘the olandard enthalpy for an izomer group rel ‘isomer group at 298.15 K. Table 8 gives values for HU, T) — HL, 298.15 K) +4 pH (L 298.15 K), the standard enthalpy for the isomer group relative to the to the Phys. Chem, Ref. Data, Vol. 14,No 1, 1985,180 clements at 298.15 K. This quantity allows the direct caleu- lation of heat effects when the reactants and products are at different temperatures. 5. Equilibrium Mole Fractions Within Alkyibenzene Isomer Groups ‘The equilibrium mole fractions within isomer groups calculated from standard Gibbs energies of formation are given in Table9 for the ideal gasstate. Since the uncertainties, in ,G* (I) and 4 (G7 are about the same, the uncertainty in the difference is nearly independent ofthe relative values of the two parameters, but the absolute uncertainty does in- crease with temperature. Since the nearly constant uncer- tainty iain the exponent in the oaloulation, the equilibeium ‘mole fractions ofthe isomers ata given temperature are un- certain by the same factor, whether they are large or small. ‘The usual equation forthe propagation of variance indicates, that the equilibrium mole fractions are uncertain by about 15% at the lower temperature and 10% at the higher tem- peratures. This makes it dificult to indicate the uncertain- ties inthe table, It could be done by using exponential nota- tion, but this makesit difficult to compare the mole fractions of various isomers. ‘Compounds are named in tables according W the 1U- PAC Revised and Collected Recommendations for the No- rmenclature of Organic Chemistry, 1978.” For example, the two forms of I-methylpropylhenzene are represented by 1R. and 1S, and the racemic mixture is represented by (RS) ‘methylpropylbenzene. In naming species with two or more ring hydrogens substituted, the name ofthe largest substitue ents given fist to clarify the relationships between the var- {ous structural isomers. ‘Table 9 shows that in general the more highly branched Isomers have very tow equilibrium mote fractions at any temperature. The isomers with more methyl groups, and ROBERT A. ALBERTY ‘ore branches have more positive standard Gils energies ‘of formation. At higher temperatures there isin general more even distribution of the male fractions between theless ‘branched isomers, reflecting the fact that entropies are more similar than the enthalpies of formation It sof interest to note that if certain isomers are ex- loded by the catalyst, the equilibrium moe fractions of the remaining isomers may be caleulated from these tables by simply excluding certain isomers and renormalizing the to- tal mole fraction to unty. The caleulation of the standard Gibbs eneray of formation of the restricted isomer group is ‘more complicated. Ite standard Gibbs energy of forma- tion ofthe retrcted isomer group (RIG) that is in equilib’ um is represented by 4G" (RIG) and the standard Gibbs ‘energy of formation of the excluded isomer group (EX- ‘CLIGIis reoresented bv AG" (EXCLIG}. then the standard Gibbs encray of formation ofthe whole isomer group and of the restricted isomer group are given by the following equa- tions: exp — 4 ¢@ (IV/RT] = expl — 4 (RIGYRT] + expl — 4G (EXCLIG/RT}, a 4G (RIG) = — RT infexpl — 4,6" (IV/RT} exp — 4, (EXCLIG/RT}}. ® 6. Standard Thermodynamic Properties of Individual Alkyibenzene Species ThevaluesofC}, 5° A HT, and dG? forall thealky!- ‘benzene species through C,H. are given in Tables 10to 13 injoules fora standard state pressure of I bar. The values for ‘CaH through C,H, have been converted from the tables of Stull, Westrum, and Sinke,” and the values for CigHy« trough CiaHys have been calculated using the Benson ‘method.'* The values for chiral forms are for the racemates. ‘J. Phys. Chem. Ref. Data, ol. 14, No. 1, 1985‘THERMODYNAMIC PROPERTIES OF ALKYLBENZENE ISOMER GROUPS. 181 gegeeies beegegeg aeaseeas: 4.Phvs. Chem. Ref. Data, Vol 14, No. 1.1985182 ROBERT A. ALBERTY 3 3 assggzagz © 88888833 anaes BSSa8e882 * pasesessa 4. Pha. Chem. Ref Data. Vol. 14. No. 4. 1985‘THERMODYNAMIC PROPERTIES OF ALKYLBENZENE ISOMER GROUPS 183 Flea Voy Tancene 4. Phys. Chem. Ref. Data, Vol. 14, No. 1, 1985,184 ROBERT A. ALBERTY (idee Rives ‘one “eote ‘9 31RS)-aethy panty ibencone 208 09 Se igs) metry tee: d-aimethy tpropy benzene 009 Soe ‘8 8 A i Stonaard neat copsclty at constant prasture for athytoansenae in WK no 28382 88288: 238 288 8338: 3 4. Phys. Chom. Ref. Data, Vo. 14, No.1, 1985‘THERMODYNAMIC PROPERTIES OF ALKYLBENZENE ISOMER GROUPS 185 Hg) Seavtatny pranyieancone BERUERERRSORESSSE: a08y a 38 (Nite) -neenptastyt)-a-naeny benzene {J.Phys. Chom. Ref. Data, Vol. 14, No.1, 1985186 ROBERT A. ALBERTY S-U1G5) -ainoenyropr')-a-neeny teeneens ISGS} 2-aimctnpterepy!oa-netmyoersens 4Jikeh-setmylpentyisenzene We 0.1 100 400 t00_goo__700_s00 2001000, Sees 4.Phys. Cher, Ret. Data, Vol. 14,No. 1, 1985 SESESSSESz5888 885998.‘THERMODYNAMIC PROPERTIES OF ALKYLBENZENE ISOMER GROUPS. 187 {able 11,_Standara entrooy of sbnylpentnas_ 69/0} “Continue, 82288 g823288 SSEAEISASREISEEE 82888 3 FEErisait4 3! 85155383: 38 Gs} setny reat ites |onetny tout SSEESSiS899908: iiaieieert fia S828: |J.Phys, Chem. Ref. Data, Vol. 14, No 1, 1985188 ROBERT A. ALBERTY Heipevieeterers NUGs) siRe)-ainetnyTeuty benzene SB eeeeeees Heanor ‘eed natnyta:atnethy propy bensene ATP actnyloreayfoersane tathy \propy ibenaare Cetra ty benzene oo las ‘ gclatranethyIeensene aie ‘ 4. Phys. Chem. Ref. Data, Vol. 14, No.1, 1985‘THERMODYNAMIC PROPERTIES OF ALKYLBENZENE ISOMER GROUPS. 9822233880993 9R0280 3841 MSE) ‘s'aveomnyioudyteencera 190 4. Phys. Chem Rel. Data, Vol. 14, No.1, 1965190 ROBERT A. ALBERTY Tabte 19. standard avtbs ergy of formation for stkytwenzenes 18 t/t wm ster s00 0 co__ton soon en etrane ty banzone cereal 4 Phys. Chom. Ref. Data, Vol. 14, No.1, 1985‘THERMODYNAMIC PROPERTIES OF ALKYLBENZENE ISOMER GROUPS: tot Hiibraees ne HSS ie iesmemee ee cen & C fot {ies} empl a Seinesty trop eenzane 4. Phys. Chem, Ret Data, Vol. 14, No.1, 1985192 ROBERT A. ALBERTY 7. Discussion The values of standard thermodynamic properties of isomer groups given here may be used in predicting equilibri- ‘um compositions of organic systems at temperature-catalyst conditions where species in an isomer group ae in equiibri- tum, They also provide a bass for extrapolation to estimate the standard thermodynamics properties of higher isomer groups. As the carbon number increases, the equilibrium tnolatrastioneofindividualmalesular epee Weeome lee interest because there are 30 many of them and because gas chromatographic analytical methods yield mole fractions of isomer groups rather than individual somers,at higher er- ‘bon numbers. ‘The distribution of species within an isomer group is independent of pressure for ideal gases andis only afunction of temperature, and 80 i€18 of fnerest to note that If any alkylbenzene species (or isomer group) i exposed toa cats- Iyst of disproportionation and isomerization reaction, the cquilibrium distributions similarly independent of pressure for ideal gases ands only a function of temperature. Actual 1y this statement applies to any inital mixture of alkylben- ~enes, The reason is that the disproportionation reactions, CyB =1Ce—1Hane H1Cy1Ha- 0) donot involvea changein the numberof moles of gas. Caleu- lations of equilibrium mole fractions of alkylbenzene mix- tres at various H/C ratios for the mixture provide an llos- ‘tration of the usefulness of data on isomer groups. 8. Nomenclature Cy standard heat capacity at constant pressure of isomer i, J K~' mol co) standard heat capacity at constant pressure ‘of isomer group I, JK" mot AG; standard Gibbs energy of formation of 180- ‘mer KJ mol™ 4;G'(l)__=standard Gibbs energy of formation of iso- ‘mer group I,K mol? ELT) — HL, 298.15 K) tandard enthalpy for isomer groups rela tive toisomer groups at 298.15 K, KI mol HLT) —H(, 298.15 K) +4 Af (L,298.15 K) = standard enthalpy for isomer groups rela- tive to elements at 298.15 K, KJ mol”! A;H} = standard enthalpy for isomer i, kJ mol~* 4;H° (I) =standard enthalpy of formation of isomer group I, KI mol! » number of earbou alouss in a molecule y ‘= number of isomers in an isomer group orr = number of optical isomers 5 equilibriom male fraction af epacins fin an, isomer group 4: Phys. Chem. Ret. Data, Vol. 14,No. 1, 1985, Si standard entropy of isomer, K~! mol? so tandard entropy of isomer group I, JK mol! TSN total symmetry number v1 = mole fraction of isomer {within the isomer sroup a ‘mole fraction ofisomer group Tin amixture 9. Acknowledgments. 1 am indebted to Catherine Gehrig for checking the ‘Benson group assignments, to Lillian Alberty for assistance with programming, and to Frederick D. Greene for advice ‘on organic nomenclature. The calculations in this paper were made using a terminal connected to the IBM 370/ 3033Nin the MIT Computer Center. Programs were written im APL ana tables were printea on a Xerox 6700 Printer in the Computer Center. This research was supported by a ‘grant from the National Bureau of Standards. 10. References "B.D. Smith, AICRE. 5, 26(1959, ARCA. Alery and. A. Geb J Phys. Chem, Ref Dat 1, 11731984) KS Pitzer and DW, Soot, J. Am. Chem. Soc 68, 03 (1943, “EJ Prosen, W-H. Johnson, and FD. Rosin J. Res. Nall. Bur Stand 36,485 0946) 5.1 Taylor, DD: Wagman, M, G. Wiliams K:S. Pitzer, nd F.D, Ronin. Res Nat Bur. Stan 37,95 (1940. FD Rossin K.S Pater, RL. Arma, RM. Brau, and. O. Pimente ‘etcee ree of tac and herp Pog of Hs tons and Related Compounds Carne, Pitsbargh 1933). %D_R. Sal EF, Westram, and GC. Sink, The Chemical Thermody- namics of Organic Compounds Wiley, New York, 1969 AED. Con and Plc, Thermochoriy of gone and Orgomamea- ie Compounds Academic, New York, 197, 9G, R. Somaya, Thermodynaries Research Center Hydrvearboa Pro- jst, Texas ARM Universit, College Sato, Texas, 1983. ey teneig at 1 tara Chom Ph 36 2620 (1962, "RE, Daf end 8. H. Baur, J. Chem. Phys 36, 1758(1962) !8W.R. Smith and R.W. Mun, Can J. Cher. Eng. $2 280 (1974, ‘WR. Sith Theoretical Chetry, Advances ond Pept, ited bbyD. Henderson and H. Eyring Academic, New York, 1980, VoL 5 W-R Smith and Re W. Mien, Chemical Reaction guiorium Anal: Theory and Algortoms Wie, New York, 1982) "RL, Montgomery, Extimation of Thermcbemical Properties of Unde- fined Hydrocarbon Mixtres: Heats of Combustion of Peto Frac tions American Chena! Society Meting, Kansas Ct, MISOUr 13 September 1982. "A Alberts, REC Fundamentals 22, 3181983, SW. Benoa, F-R. Cruickshank, D. M, Golden, G. R Haugen 1H. GrNeae A'S. Koper Canam, ARG: Wah, Chem Revo, 279 (190, 'W. Bensoa, Thermochemical Kina (Wey, New York, 1976. MC. A. Davie, A.N.Syvere, and EC. Steiner, fart of he documestaion {in preparation for Program CHETAH 6.x of ASTM Commitee 27 DID. Wapinan, WB Eva, VD. Parker, RH. Sebo, 1 alow 5. Malley K.L- Charney, nd RL. Nuttall J Phys. Cher. Rec Data, Soppl 211982, Namencloture of Organic Choy, prepared for pabliation by J. Ri pncy nd Petar Dengan, Moe ort 08) ICA’ Albers, IEC Fundamentals ubmitd for publication