Estimation of the Heat Capacities of Organic Liquids as a Function Chemical Kinetic and Thermodynamics Disin, National Instn of Standards and Technology, Goithesburg, MD 20899-0001 of Temperature Using Group Additivity. |. Hydrocarbon Compounds Viastimil Razi¢ka, J *, and Eugene 8. Domalski st June 2, 1003; rvced manutript recived October 26,1002 ‘A second-order group additivity method has been developed for the estimation of the heat capacity of liquid hydrocarbons as a function of temperature in the range from the melting temperature tothe normal boiling temperature. The temperature dependence of group contributions and structural corrections has been represented by a polynomial expression. The adjustable parameters inthe polynomials have been calculated using a weighted least squares minimization procedure. Recommended heat copacities from a large compilation of critically evaluated data that contains ‘over 1300 organic liquids erved as a database both forthe development and testing ‘of the method. Key words estimation; group contribution approach; heat capaciy of igus hydrocarbons; temperature dependence Contents 1. Introduct 5. Parameters for the dependence of group 2. Development of the Method... contribution Aci on temperature, Ac; + 2.1. Additivity Scheme 598 (TOO), + di(TNOOY, TIK ... 22, Temperature Range, 598 6, ‘Parameters tor the dependence ot” struc- 23. Group Notation ...... 599 tural correction Ac, on temperature, Ac; + 2.4, Next-to-Nearest Neighbor Interactions ... 600 (T/100), + di(T/100), T/K .. 23. Determination of Additvity Unit Value 1 7. Deviations between recommended and cat 3. Database of Ligud Heat Capacien..... 601 mated heat capacities of n-alkanes. 4, Results and Discussion. = 604 8 Deviations between recommended and esti 4. n-Alkanes... 605 mated heat capacities of branched alkanes 42. Branched Alkanes . 6079. Deviations between recommended and est 43, Alkenes and Dienes. 609 mated heat capacities of alkenes... 4.4, Allynes {609 10. Deviations between recommended and esti 45 Saturated Cyclic Hydrocarbons -- 609 "mated heat capacities of diemes...........-.- 4.6. Unsaturated Cyclic Hydrocarbons. 609 M1, Deviations between recommended and esti- 4.7. Aromatic Hydrocarbons. 609 mated heat capacities of saturated jlc 5. Gonntusio os lydanaibone. 6 Acknowledgement 615 12, Deviations between recommended and esti- 7. References....... 615 mated heat capacities of unsaturated cyclic Appendix 618 hydrocarbons. 13, Deviations between recommended and esti- List of Tables mated heat capacities of aromatic hydrocar- bons . 1. List of groups 14, Summary deviations between observed and s- 2. List of equivalent groups.....-- timated heat capacities. 3. List of structural corrections... 15, Summary deviations between observed heat ca- 4 List of selectea compounas used paciies and those estimated by the Lee-Kesier lation of adj justable parameters. Department of Physical Chemisty, Incite of ‘Chemical Technology, 16628 Prague 6, Czzchosovakia, (©1990 by the US. Secretary of Commerce on behalf ofthe United — and the American Chemical Society. ‘Reprints avalable from ACS; see Reprints Lis at back of isu. ‘0067-2680 /031090507-221812.00 597 method ... List of Figures ‘The agreement between the recommended and the eine Lgl heat cpaces of pen: tenes... 610 612 612 613 ou or J. Phys. Chom, Ret Data, Vol. 22, No. 3, 1999,Introduction Heat capacity is a basic thermodynamic property. It is used in chemical engineering calculations to obtain the differences in thermodynamic functions between two dif ferent temperatures. Experimental liquid heat capacity data are avallable for only a fraction of the total number of compounds encountered in industrial processes. In ad- ition, for only a small number of compounds does the ‘ontant data cover the temperature interval that ie often, required in applications, ie. from the melting tempera- ture up to the normal boiling temperature, Estimation ‘methods are an obvious choice to provide heat capacities for compounds for which there is a complete lack of data or for which data are available only over a limited tem- perature interval. ‘Additivity schemes that correlate thermophysical and ‘thermodynamic properties with molecular structure have become widely used for data estimation. Because a ‘molecular property is calculated by summing up atomic, ‘bond, or group contributions, the additivity methods are purely empirical. The additivity approach applied to the estimation of thermophysical properties was systemati- cally developed by S.W. Benson and coworkers (58BEN/ BUS, 69BEN/CRU, 70BEN/ONE, 73EIG/GOL, TILURIBEN, TISHA/GOL, 7ISTEGOL, 91BEN/ GAR). From the beginning, attention has been focused primarily towards the estimation of thermodynamic prop- erties for the gas phase. Sevetel ahllivity metlnnls lave ben proposed for the estimation of liquid heat capacities (5SJOH/HUA, 65MIS, 69SHA, 73CHU/SWAI, 73CHU/SWA2, 77LUR/ BEN, 810GVARA. 82CHUINGU. 88DOM/HEA). Some methods utilize a second order additivity routine that takes into account the nearest-neighbor interactions in the definition of structural units into which molecules are divided. Guthrie and Taylor (84GUT/TAY) devel- ‘oped an additivity method for the estimation of the heat capacity of vaporization that is defined as the difference between the gas and the liquid heat capacities. All additivity methods developed for the estimation of the liquid heat capacity so far, with the exception of ‘TILURIBEN, provide contributions either at a single temperature, typically near 25°C, or at a few discrete temperatures (65MIS). Luria and Benson (77LUR/BEN) developed group contributions that permit the estimation of the liquid heat capacity in an analytical form that rep- resents the dependence of the heat capacity of a hydro- carbon on temperature. In chemical engineering calculations, an analytical equation for the heat capacity as a function of temperature is preferred to discrete val- ues of heat capacities given at a few temperatures. “The eurrent projoot has been concerned with the revi sion of the existing group contributions and structural corrections developed by Luria and Benson (77LUR/ BEN) and the extension of the method to cover a broad range of organic liquids containing the elements: carbon, hydrogen, oxygen, nitrogen, sulfur, and halogens. The second-order additivity method provides for the es ‘J. Phys. Chem. Ret. Data, Vol. 22, No. 3, 1983 V. ROZICKA, JR. AND E. S, DOMALSKI tion of the heat capacity of organic liquids and yields the heat capacity as a function of temperature in an analyt cal form. Thus, the method can be implemented readily in chemical engineering calculations to establish energy balances or to evaluate the effect of temperature on phase and reaction equilibria. ‘The development of the method has been made possi- ble as a large compilation of experimental calorimetri- cally measured heat capacities has become available (G8ZAB/MRUZ, 932AB/RUZ). The compilation containe critically evaluated data for over 1300 organic com- pounds. The evaluated heat capacities served as the input data in the development of the present estimation ‘method. This paper presents group and structural correc- tion parameters for hydrocarbons. A total of 29 groups and 24 structural corrections are given which include ‘those for families such as alkanes, alkenes, alkynes, aro- ‘matic hydrocarbons, and saturated and unsaturated cyclic hydrocarbons. 2. Development of the Method 2.1. Additivity Scheme We have used the following expression to estimate the heat capacity of organic liquids, C, asa function of tem- perature: Gu Snae @ wie A isthe gos constant (R= 091451 31" S8COH/TAY), mis the number of additivity units of type i, Aer isthe dimensionless value of the additivity unit of type i. and k is the total number of additivity unit in 8 molecule, The additivity units include groups and struc- tural corrections. Several functional forms forthe dependence of Ac,on temperature have been considered and. examined (2RUZIDOM), Finally, a simple expression has been chosen: mot, sararadea(hP where Tis temperature in K and a;,h, d; are adjustable ‘parameters. Other, more complex expressions were re- jected as adjustable parameters are highly correlated. In- sufficient accuracy of the heat capacity data, a narrow interval of available data for some compounds, poor choice of structural units into which molecules are bro- ken, and inadequacy of the model are possible explan tions for the parameter correlation. We believe tat the first two items are the most probable causes that prevent the use of a more extensive functional form for the de- pondence of Ao, with temperature. 2.2, Temperature Range ‘The present estimation method is applicable from the melting temperature to the normal boiling temperature which is the range for the liquid phase most often re-ESTIMATION OF HEAT CAPACITIES OF ORGANIC LIQUIDS quired in chemical engineering calculations. At present, itis not possible to develop an empirical method to es mate heat capacities of organic liquids over a wider tem- perature range as experimental data above the normal boiling temperature are scarce. The method can be ex- trapolated to temperatures above the normal boiling point; however, the predictive accuracy deteriorates as the extent of the temperature extrapolation increases. ‘Near thecitical point deviations between observed and estimated heat capacities become large asthe liquid heat and those estimated using additive contributions reported here we have encountered only few was necessary 10 use temperature outside the range of ‘one or more groups present in the compound. We found thatthe temperature extrapolation up to 80 K outside the range of a group has no considerable effect upon the er- zor of prediction. It was shown by 93RUZ/DOM that ex- ‘rapolated group values calculated outside the temperature limits are reasonable when using the eqn. (2) for the dependence of contributions Ac; with temper- ature. Due to the limited temperature range to which the ‘method applies, no distinction was made between the iso- ‘ari heat capacity, Cp, and the saturation heat capacity, Cav, At low saturation pressures below 0.1 MPa, C, and Cu. are nearly equal in magnitude. The difference be- tween C, and Cu: at the normal boiling temperature lies typically below 0.2 % and only becomes significant far above the normal boiling temperature. Even when the ‘method is applied above the normal boiling temperature the deviations between observed and estimated heat ca- ‘exceed the differences between Cy and Cun 2.3. Group Notation We have followed the group notation developed by Benson and coworkers (S8BEN/BUS, 69BEN/CRU). The group is defined as a central atom together with its nearest-neighbor atoms and ligands. We have adopted the short form of the notation for multiple bonded atoms Ca, Cy Cs, and C, that omits the atom at the other end of the multiple bond. Cs is a double bonded carbon atom attached fo a second double bonded carbon atom and to two other monovalent ligands, C, is a triple bonded car- ‘bon atom attached to a second triple bonded carbon ‘alom and 1 another monovalent ligand, Ce a carbon atom in a benzene ring attached to two other benzene ring carbon atoms and to another monovalent ligand, Cy the dauble bonded carhon atom located in the middle of the allenic group >C=C=C<. Table 1 lists all groups that we have used together with a sample group assign- tment for some typical molecules. “Tague 1 List of groupe Group on Sample group assignment HHO r 3 propane: | C-FH}), 1 CAC SO 1 3 naterne: 3 CHC), 4 CDA, CDOs 1 4 2-metyipentane: 3 ©(H{C), 2 C-C ACs 1 C-CH\Os HO. 1 0 2.2-dimetybtane: 4 CH) (C), 1 (HAC), 1 CXC coti fe iene: 2 C(t ano) so Fpropenes 1 E-GDO), 1 C-GDu 1 CABIN) COs te 2-mthy-I-propene:2 CHC), 1 C(t, 1 Ce{Cht HH) 14 13 bade 2 Ges 26.1) CHK) 1 0 butadiene 1 C-(H(C), 2 Gr 1 CoB Ca, 1 Ce{CHC) Sandy ae DAC Gat & GHC) © CHANG COOK) 14 chutes: 2 (HO), 1 Cea, 1 eH), 1 CHOC) OMG) 1 0 33+-dimethl-butene: 3 C-H)NC).1 Cea 1 Ge(H)(O), 1 CHONG) CHG 12 A-pemadiene: 2 Cr(H)a 2 Ce(HC), 1 C-DACDe can) a Touts 1 CWC), 1 COD ACHED, 1 EH), 1 C(O) co) 1 0 bute: 2 C-(H)IC), 2 C(O) CXC) 1 0 ethylbenzene: § Cai), 1 Ce(Ca), 1 Ca-(Ca, 1 CoH) q 1 oo 1 a-buadine: 1 C-H)(C)y 1 Ge» 1 Ce(HVO, 1G, ean sod teneene: & Ge G6) 1 0 toluene: § Cai), 1 Gr{C), 1 C-(HXC) CHC) + 0 ethenybenene: 5 Cr(H), 1 CrCal 1 Cefn 1 CHC CoC) 1 0 1,'-biphey: 10 Gar, 2 CrCs) Sapexen 58 givens, 3 Cer) 4 Catt EIMACKED), 1 CED KS) CHONG) a ‘metiyctybenaene: 5 Cr(H), 1 Cr), 1 CH)(C)Cs), 2 (HCY C4CHxCs) ne a (t-aimetyltiy benzene 5 Gi-(H), 1 Car{C), 1 C-{C)Ca), 3 C-CDIC) CHD AC) 12 1,{'-methylnebsbenzen: 10 Ca-{H), 2 Gr{O), 1 CH) ACe) CN j 4 1 -metnldenenrsbenzee: 13 Car) 3 Ce, 1 C-CHCADs Cor{CurCa 1 0 phthalene: 8 Ca-{H), 2 Car{Car)(C)s Car{Cow)xCa) 1 0 phenanthrene: 10 Cri), 2 (Cu )(Ca 2 Cr-{Carb4Ce) artCar)s 10 fuoranthen: 10 CaF), 1 Car-{Car\(Cal # Cur-{Car4Ca, 1 Cur{Cars ‘The approximation C-(H)x(CN(G) = C-(H)(CXGH) was wed ‘The approximation Cy-(C) © Cyr(Cy) was used, ‘J. Phys. Chem. Ref. Data, Vol. 22, No.3, 199600 Benson et al. (69BEN/CRU) and many other authors who have developed a second-order additivity method for the estimation of thermophysical properties arbitrarily signed values to some groups either when groups exist in conjugate pairs or when data for the calculation of a group are unavailable, We have utilized some of the assignments mainly as it reduced the colinearity of adjustable parameters (93RUZ/DOM). The list of equiv- alent groups is given in Table 2 “Tame 2. List of equivalent groups CUDA) = CAHDACD = CLIC) = CMC) CHIACLC) = CHEDKOC) Gr{C) = Ceca) Ca) = Cre{C) CANE # CHOKCD, Gr{OMCa) Car) = Co-{C) Go{GNCa)2 = CotCaNCo)e We have adopted the approach proposed by Benson and coworkers (69BEN/CRU, 76BEN) to estimate the heat capacity of saturated and unsaturated eyelic hydro- carbons. The heat capacity ofa cyclic hydrocarbon is esti- mated by summing up group contributions developed for acyclic compounds and then adding a structural correc- tion that is specific forthe particular cyclic compound. AS the corrections reflect the internal ring strain imposed on molecule, they are denoted as ring strain corrections, or 1c, Table 3 lists all structural corrections that we have used together with typical sample group assignments. V. ROZICKA, JR. AND E. S. DOMALSKI Next-to-Nearest Neighbor Interactions ‘The second-order additivity method makes no al Jowance for next-to-nearest neighbor interactions. Some authors have found that such interactions have consid able influence on molecular properties and therefore in- cluded. corrections to account for next-to-nearest neighbor interactions, The gauche, cis, and ortho correc- tions developed by Benson et al. (69BEN/CRU) or the methyl repulsion correction suggested by Domalski and Hearing (88DOM/HEA) are some examples of the ap- proach, It is worthwhile to include a correction for a nest-to- nearest neighbor interaction if it accounts for a differ- ence between observed and estimated molecular property that is almost equal in magnitude or larger than the uncertainty in the estimated values. When examining the recommended heat capacities taken from the comy lation 93ZAB/RUZ, we have found that the largest di ferences in heat capacities of cis and tans isomers of alkenes and of saturated cyclic hydrocarbons and of or- tho, meta, and para isomers of substituted benzene are approximately as large as the uncertainty of the present estimation method. For some compounds the differences in heat capacities of two isomers change in magnitude or even change from a positive to a negative value in the temperature interval where the data for both isomers are available. This is most probably due to an experimental error of the original data, Thus, we have not developed corrections for next-o-nearest neighbor interactions due to the lack of sufficiently accurate data. ‘Tague 3, List of structural corrections Structural correction Sample group asigament ‘elopropane ne ‘etopropane: 3 -(H(Oh, 1 aelopropane me ‘Galobutane ne ‘elobutine: 4 C-H)(C)e 1 getobutane tse ‘elopentane (uns) ric ejelopentan: $ C-(H)(C)p 1 glopentane (une) rc ‘elopentne (sub) ree ‘etheylopentane: 1 C-(H)(C), ¢ UHs(C)y 1 EHX 1 eopentane (sud) 1s eoherane re ‘cloherane: 6 C-(H):(O), Fewlahenane re eoheptane re ‘qeloheptane: 7 C-(H)(Chy 1 otoheptane ac ‘eoodtane ne clooctane: 8 C-(HD AQ 1 oeloctane se Spiopentane re Spropentane: 4 {HG EC) 1 spropentane eeopentene 6 ‘oelopentene: 1 CHC, 2 Co H\C), 2 C-H) (CVC), 1 elopentene ese yeoberene ne ‘lohexene: 2 C-H)(C), 2 CH{C), 2 CAC KGS), 1 obesene ne cohepere nc Soctne ne johnnie eoocadne ne lepine ne Soocatsee ne inden ee looratetraene: 8 Ce tetrahydronaphhalene tse ‘eloheptene: 3 0-(H) {Op 2 Ca-{HY(O), 2 C-H){CVCd), 1 osloheptene re ‘elooetene: 4 C-CFy{C)y 2 CeGFNC), 2 C-CA(CVCy), | qeooctene re gbejloheradene: 2 Ce-GAY(O), 2 Ce{HVC.), 2 CCH {C) Ca), 1 qeloheradiene re 15.elooeadiene: 4 Ge (HO), 4 CH {CKC), 1 eloetadiene re peta: 2 CrlHNO) 4 Ce (HYG, 1 CDA indan: 1C-(H){C)s 4 Ce-(H, 2 C(O), 2 C-C{ONCa), indene: 1 Ce(H)(C), 1 Ce (HNC) 1 CH) ACa 4 Cu 1,23,4etrahydronaphalene: 2 C-(H)(Chs, 4 Car(H), 2 Ge{C), 2 CAH ACKCA), {Co 1 C-Cp{Ca)s 1 qetoheptatrene re indan re (H) 1 Ca(C), 1 Gar{Cy), 1 1Findene rac ecaiydronaphthslene re decahydronaphthalee: 8 C-H)(Ch, 2 C-(H)(C)s 1 deahydronaphthalene rae herabydroindan re bexabyeroindan: 7 C-(Hs(Ch, 2 C-(H)(C)s 1 erahydroindan rs dodecatdrofuorene sc dodecahydro-S-methivorene: 1 -{H)(C), 8 C(H)(Cs,§ C-{HNChs, 1 dodecahydrofiurene re {etradecaiydrophenanthene rc tetradecabydrophenanthrene: 10 C-(H)(C);, 4 C-(H)(C)y 1 tevradecanydrophenanthrene 16 hexadecahydropyrene se Sethyhexadecahylropyrene: 1 C-(H)y(C) 10 C-{H)(C, 7 C-(H)(C)y 1 exadeeahydropyrene se 4. Phys. Chem, Ret Data, Vol. 22, No. 3, 1983ESTIMATION OF HEAT CAPACITIES OF ORGANIC LIQUIDS 601 3. Determination of Additivity Unit Values ‘A multiple linear least squares method has been used for the calculation of adjustable parameters in Eq. (2). ‘The minimized objective function has the following form: s= Sor - oy ® where the subscript j denotes j-th data point, Cj is the recommended liquid heat capacity, C,* is the estimated heat capacity. The weight, m, is equal to the reciprocal of the variance of the j-th data point o*(G)). It is estimated for each j-th value on the basis of the assumed accuracy of the recommended heat capacities. The input informa- tion is the percentage error of the recommended data, ‘oC. Thus, the weight of the j-th data point is expressed = /688) © ‘Ihe agjustabte parameters were caicuiated by simutta- neous minimization of the recommended heat capacities for families of structurally similar compounds in a series of five successive stepe. In the first step, 16 group parameters were determined using selected data on 39 alkanes, alkenes including dienes, and alkynes. In all con- secutive steps of the parameterization scheme, adjustable parameters were calculated for additivity units that occur in another family of compounds while the previously de- termined parameters were fixed. In the second step, 13 ‘group parameters were calculated using selected data on 36 aromatic hydrocarbons including multi-ing hydrocar- ‘bons and biphenyls. In the third step, 8 structural correc- tions were determined using selected data on 24 ‘mono-cycloalkanes, In the fourth step, 11 structural cor- rections were calculated using selected data on 18 unea urated cyclic hydrocarbons. In the last step, 5 structural corrections were determined using selected data on 16 perhydroindans, perhydronaphthalenes, perhydrofluore- nes, pethydrophenanthrenes, and perhydropyrenes. The list of selected compounds is given in Table 4 together with the temperature ranges for the recommended data and literature references fo sources of original data that served for the generation of recommended heat capac- ities. The adjustable parameters for the calculation of group contributions and structural corrections are given in Tables 5 and 6, The appendix gives a sample calcula- tion for n-heptane at 300 K. 3.4. Database of Liquid Heat Capa ‘The recommended heat capacities were obtained from i tion that contains all currently able calorimetrically measured heat capacities for over 1300 liquid organic compounds (88ZAB/RUZ, 93ZAB/ RUZ). The compitation mctuses parameters oF & smoothing equation obtained from a critical assessment of experimental data. Parameters are accompanied by a rating that represents the expected overall accuracy of the data. The rating was expressed as a percentage error and served as the input information for the calculation of weights in the least squares parameterization (see Eq. (4)). ‘A PCversion of the database that provides parameters of a smoothing equation, tables of heat capacities over a specitiea temperature interval, ana enthalpy ana entropy difference between two specified temperatures, will be available from the Standard Reference Data Program of the National Inctitute of Standards and Technology, Gaithersburg, Maryland. ‘TaoLr 4, List of slected compounds usd fr the ealultion of adjustable parameters Referencee 1st sep ofthe parameterization scheme SSKEMIEGA, 6SCUTMOR, 78600 JIMESIGITT. SGRURAS, SSMELIVER SIHUF/PAR, <6DOUMUF2, SICONSAG, 69WILROT, 7SGRIRAS, TOKARIGRO, SOKALJED, SIGROJING, S2WIL/ING, S{BENIDAR, SABRAPIN, 8SBENDAR, SEMELIVER, SSSAUTAN ‘Compound “Temperature range propane sL20 hexane 180-400 octane m0 ‘S6BEN/DAR decane 247-462 22-dimethybutane 17-365 SSOHNFUI 2methyipentane 117-303, 23 -dimethypentane ag385 | T6FINMES 24-dimethypentane 16-307 SIHUFIGRO 33-dimethylpentane MRS TSEINIMES Sethypentane 161-299 6IHUFIGRO 2zs-uimeddytbuiae 2013 SIHUTORO 33-iethyipentane 2365 223;3terramethypentane 268.383 76FINMES STOSBIGIN, S4FINIGRO, 7SGRURAS, SIGROVING, &ROUIGRO, SSLAUGRO, SEFTNIGRO, 7SGRURAS, 84GRO/NG, 4ROUIGRO, 85GATIWOO, 88KUZIKHA 4sDOUATUF2, 4SKIL/PIT, SOAUESAG, SSBEN/DAR, SABEN/DAR, SSBEN/DAR, ASDOUIHUF2, SBENIDAR, SABEN/DAR, S6BEN/DAR 76FINMES, 79FUCPEA 4 Phys. Chem. Ref. Data, Vol 22, No.3, 1988602 V. ROZICKA, JR. AND E. 8, DOMALSKI “TaaLe 4. List of sleted compounds wed for he calculation of adjustable parameters — Continued Eompomnd “Temperate angen Referers TaaAetametiipentane 2338) TEINS {rpropene 53-25) _SIHUFIPAR, 39POWIGIA, SOAUESAG Butadiene 1daoa0ASTR7A 13-butadiene 165-300 SSSCOIMEY huryne 150-215 SOASTIMAS 2 butyne 248-284 41YOSIOSB prenceg 20 290 DETODIDAR, 4EASTIFIS, 4OSCHIEAG. 2Lmety--propene 158.2% 36TODIPAR 2metiy-13 butadiene 130-304 S7BEK/WOO, TOMES/TOD SmetiyL1 2 butadione 1@-315 7OMES/TOD 1 pentedione 42 208 7OMES/TOD SApentaiene 126310 TOMESTOD 23spentadene 151318 TOMESTOD Prmethyt-utene 14028 47TODOLL Phenyl tues Htsot SuRARMUr, «7roD/OLL Semetigt-btene 11128 47TODIOLT pentene 126320 47TODIOLL, 49SCHSAG 33edimetiy--dutene 16629 | 3SKENSHO Yenc 136309 SOMCCIFIN, RSKALAWOY heptene 15700 SIMCCFINI Loctene 195-309 SIMCCIFINE Idecene 211-386 STMOCIINE nd sep ofthe parameterization heme teraene 287-483 ASOLVEAT, SSDUF/EVE, 6SFINIGRU, TIKRASUB, 7SRASIGRI, 7SSAN, 76FOR DDEN2, 77WILGRO, TSGROMWIL, SOROMNG, S2TAN, S2WILAR, SOOAMUR, STAN, S7TAN, SSLAIROD metyensene 162-03 GSCOIGUT, GHW4/ZIE, TIAKWIEKS, 7SHOL/ZIE, SRASIGRL T6FOR/BENI, “ESANMEL, TIWILIGRO, TBANDIGRI, S2GROVING, S2WILIFAR, 8SROUIGRO syepicnceve zie-s90 sania, SLED ‘thenybentene 247-383 46PITIGUT, SOKUR 12dimetibenzene 28-463 ‘{GPITSCO, TSRASIORI, P9FORIBEN 13edimetiibensene 21S GGPITISCO, 7SRASIGRI, 75AN, enetigtbenene 280-573 4TCOROM, SRASORI, TIFORBEN, 79OTTIOOA, SOMESIFIN cliyemaene 178-393 SIGUTSPI, 4SSCOIBRI, 76FOR/BEN2, MANDIORI, TIFORIBEN, SSGROFARL ‘-methyetnenzene 180-413 S2SCHISAG, TIKISSUG, PANDIGRI popylbenzene 181-371 4STSC, eSMESTOD2, SIGROPAR? TB tenecue Bose eravon 12¢crimetyfbenzene 230-480 STPUTIKIL, 79ANDIGRI 113S.rinethyenzene 230-424 SSTAYIKIL, TIFORIBEN, TSANDIGRI, TOWILIFAR uyberzene 194-390 GSMES/TOD2, SSGROIFARS Gutaimetytetny benzene 220-24 SOMUPIPAR Iemethy-4(lmethycthyDhenzene 211-386 S1HUF/PAR, S7KUR, (-methypropy)penzene 294430 BANDIGRE 1,-metylencbisbentene 302-353 SOHUF/PAR, SISMYVAND, SeDUFIEVE Li{hzenyneaysbencene 36583 _SOKUR, G@pUi-(zemenedyeibensene —M15.553_SEFER/THO, SOKUR 1'{12ethanedyDbibensene 324472 _-S3FERTHO, AISCH, SOKUR, SMESIFIN 111 metiientisbene 573.586 325PA/THO, SOKUR {setyiaptiaene 248-382 SIMCCIFIND Zrmetynephtalene 310-367 IHUF/PAR, STMCOFIN? t-bipbent 4380-889 _32SPA/THO, S6MCE, SSWALIBRO, SSOROIMRA {.s-imetynapatalene sos —_77FINMES 23.dimetiyinaphialene 385-415 SSMESFIN 2fsaimethyinaphtatene 360-438 TTFINMES 27 dimetyinaphtatene 373391 TTRINMES phenanthrene sim ASCH, TINMES (nett). biphemt 283-671 SOMCE, GVARIKOR, IVUKIRAS. fuoranthene 386-452 TIWON/WES pene ‘81-479 TIWONMWES fiphe “81-810 TIWONWES S4Q-naphthalenylmethynaphihalene 345-423 T7FINAMES ‘J. Phys. Chem, Ret, Data, Vol. 22, No. 3, 1903ESTIMATION OF HEAT CAPACITIES OF ORGANIC LIQUIDS “TaMLE 4. List of selected compounds sed forthe calculation of austable parameters — Continued — Traps go —— Tenn ae pec ene saa 4nuEroN isos Sariowt Tecan Sure sms Ino-am KDOURUFY, AAMOR, BFORDAR STAN iBee lDouMUr! steoNsnd dean Senor! Hoan Senet! SoctSimeyincepenane ‘eat SSOROOL inept em Renoptt plone loss Meron Tenioconenane lesa GMistoot atone Beam) GRUEMUR SAUESAG, (MOBO, KLE, AWILZET,21OLMOI, 184, TNGROM, A, PHFORDAR, WILZORO, SOROING, RETAN SSHRC ranma shosoae Lies» 4DOUOP caW28, SHOLZIE, PWILGRO, GRONNG, TAN Trea ses Snurmon cis-1,3-dimethyleyclohexane 204-299 49HUF/TOD Saecislocshee ikea» SUTTOD Forpocetne ims Sh oe mess nines Citdmetniaocshcwse ans SGUDICAM ‘apc ioe Sounean Easeicaonse hon GsotRdcoupcan a oan Senmsco, rs, MFORDAR Sacre SeamtSINaCo, RONDA STAN see fest_iscom “i po he orton ee a so aurear Peace howe holuwor tind He NIE WOE oremne ian EMUNEAT, maisue sgeotepaiene mos SNC octane eat fos See ion BURL 1st gemma imum WscooKd 15am Sram unnrsv Secure Som LENED wince Sood SPIN «sie 2baimarnne Yoon stu 12ielenpenphtane esis Scena anemce Hoe hiteen ‘amen Sore LEAN reining dome NLEERIN rap ettmtinn berm NLEERN creas form _ MUREW So t-te dene aes Tune secatetetine Roan Benne ican ices ROOUNEL, eauDKAN Scupdaimayinh nde is @COLBEL UDICAM Saaipseeptee uC} SIMCCING CUBIC, 8S:1008, 9OKNFLD eee at en here ete SSigietacipbopnine Seats ouBea Ciikcienphaie Seat @oUDIeaM Sopa mieinpmpsndew Sra SEOUHEL, cUDCAM Seria siglo SEAR HUDIEAM SGaiyhcghinccplioierne Sita SEUDEAM tceeuacopienstene aba GGUDICAM Sao. ES Soe Saigacaipieree Sim Goounet Sciyheaiaipioprene SISA SGUDICAL 4. Phys. Chem. Ret. Data, Vol. 22, No.8, 1989604 V. ROZIEKA, JR. AND E. S. DOMALSKI “haus 5. Parates forthe dependence of group contbution Seon temperate, ds e+ (FA00)+4(7 OO, 7K “Adjusble parameters Temperature Group “ bm ant "ange CG) 3a ~aeE1 1965-1 90 camo: ayn ~$4967E—2 {ose 1 20 CAN: Kone 3380961 250-3 sos Co. =20383 Lass ~asene—2 145.395 cabs ine ~47928-1 $99288-2 30355 can0 sano ~hanss aiase-1 sosss CHO 1350 ThivaKe—1 Lisie-1 wos cxcy ooae “yest SS022E-1 130-305 Oe? 1069 Sonste—1 3360761 1303s CaDxorcs, 20208 2137-1 Tete cos CAD OAC? —A0Ssee—1 Sa1mE=1 taaise—1 10-300 CHONG =46006 aon ~A6 2 16.293 cetaacn srs ~Aeor7E-1 S286-1 130-300 cay sae rey iss ao tama tom 150-285 c 30800 ~c2oiTE-1 lois Ce) Lares 200 ca 208 imam cH) 13mm ise Cre 5500 20-550 cae 8 295-400 Santee ne 100 CHOU = Loose 1 180-670 CHONG? 12307 pe CHC — Taste om ENCE ate Bs Gor(Ca\Cae Tassr “Sorase~1 20810 Grice) Theses ~78828-1 sosio Gro oleae +1 12186 sesso “Paramcier alc gen in the notation. The fit part ofthe number dente te facial par which flowed by the exponen oe Base 10 g.~33997E~1 means —339974 %, "Adjustable parameters were calculate from heat expacty data ona single compound ony. 4, Results and Discussion ‘An extensive evaluation of the present method was made by comparing recommended heat capacities and those estimated using additive contributions reported here. the recommended heat capacities were taken from the compilation 93ZAB/RUZ. A total of 265 hydrocar- ‘bons and almost 4000 data points were included in these ‘comparizons. Deviationo between recommended and 2 timated values were calculated forthe temperature range. from the lower limit of the recommended data up to the toma! bong temperate or tthe wont init of the recommended data if it lies below the normal boi temperature, Ifthe recommended data extend above the normal boiling temperature, a second set of deviations was determined using data’for the entire temperature range. The standard deviation and average absolute per cent deviation are given for each compound in Tables 7 6 13 where ewmpuuinls were divided according 6 Ut molecular structures into the following families: n-alka- nes, branched alkanes, alkenes, dienes, cycloalkanes, un- samrated —eyrlie—hydracarhane, and aromatic hydrocarbons. ‘We have also made comparisons using group contribu- tion parameters developed by Luria and Benson ‘J. Phys. Chom. Ret, Data, Vol. 22, No 3, 1983 (TTLURIBEN). The comparisons involved a smaller set of compounds than that mentioned previously as we de- termined 11 more group contributions and 10 more struc- tural corrections than reported by TILUR/BEN. In addition, we found that there is apparently an error in parameter values for the C-(H)AC)(Ca) group given by ‘TILURIBEN as deviations between recommended and estimated heat capacities are extremely high for hydro- carbons containing the C-(I)XC\(C) group in their ‘molecular structure. Another indication of an erroneous value of parameters for the C-(H);(C)(Cz) group is that, ‘roup values are large and negative in the entire temper- ature range. By contrast none of the group contribution values that we determined is negative, and the same is te forthe group contribution values forthe liu heat capacity at 25°C reported by 88DOM/HEA. The sum- mary deviations between the recommended and esti- mated values using the parameters by 77LUR/BEN given separately fr sliwust all faullles Uf hydrocarbons. are ven in Table 14, In this table, the summary deviations calculated using group values developed in this work are slco presented for identical ate of compounde. Aa we de- termined parameters for more additivity units than pre- sented by TILUR/BEN, Table 14 also inchudes summary = sins “30001 2as-300 Selec ne Bites Row = ss ed inden nam 280-05 ‘earns 267 =1ssme— 250-300 Accaronaptalen setts Shamte2 aees heraysrinda se —29098 TASSIE-2 20-05 (oderioorene ara fans -tat sis incotgieneatene ne Te MBEt on “ioere 1 discs Sciccahyoprene me CEES Tibime + sae seas ‘Parameter values given in the E notation, The fit part ofthe number denotes the Fractional part whichis followed ty the exponent tothe base 10 (eg.~33997E 1 means ~ 3399710 "Adjustable parameters were calculated from heat capacity data on a single compound onl. ‘An additional comparison ot the present methog with, the method developed by Lee and Keser (7SLEE/KES) hhas been made. The Lee-Kesler method is a gener: CSresponding nates aehod that rogues data for thn critical temperature, critical pressure, acentric factor, and the heat capacity of the ideal gas for the estimation of the heat capacity of vapor and liquid phase as a func- tion of temperature. We have included several represen- tative compounds from each family in the comparison. ‘The input data required for the application of the Lee- ‘Kesler method were taken from the following sources. Critical properties and acentric factors were obtained from the database of physico-chemical properties of pure compounds CDATA (92RUZ/LAB) that contains recom ‘mended values based on the critical evaluation of a wid range of literature sources and includes also some est mated values. The heat capacity of the ideal eas was taken from the compilation by Bure8 etal. (87BUR/ HOL) that presents the heat capacity as a function of ‘temperature in an analytical form. Several reliable data tions were used to develop the parameters of cor- relating equations given in 87BUR/HOL. Deviations be- tween the recommended and the estimated heat aparitics fur individual vompuuints ate given is Tables 7 10 13. Table 15 presents a comparison of the summary de- vations calculated for the present group contribution method and the generalized Lee-Kesler method. Devia- tions are compared for identical sets of compounds be- longing to different families. A slightly smaller number of data points that were included in the evaluation of the LLee-Kesier method Is due to convergence problems in me calculation of density in the proximity of the critical point. Generally, in contrast to the present group contri- bution method, deviations for the Lee-Kesler method are significantly larger in the range from the low temperature limit to the normal boiling temperature than in the entire temperature range of data. An example of the agreement between the recommended and the estimated liquid heat capacity is demonstrated in Fig, 1 for 1-pentene. 4.1. n-alkanes ‘The heat capacity data on n-alkanes are the most abundant with regard to the number of members within 1 family, the temperature range that these data cover, and measurements by different authors. The n-alkanes ‘exhibit the most typical denendence of the heat capacity with temperature. For the majority of n-alkanes, the frst derivative of the heat capacity with respect to tempera- ture is positive over the entire liquid region. For some members of this homologous series, in particular Cito Cs, G.to C;, and Gy, a shallow minimum located a few de- ‘grees above the melting temperature is observed in very piovise measucienl, The pieseut metlion docs wot ac Count forthe initial almost flat part of the curve and pre dicts monotonically increasing heat capacity with temperature, ‘The heat capacity of methane cannot be predicted us- ing the proposed method whereas the prediction for J. Phys. Chom, Ret Data, Vol 22, No. 9, 1999V. ROZICKA, JR. AND E. S. DOMALSKI ‘Taste 7. Deviations between recommended and estimated heat capacities of n-alkanes. Numbers of data points and values of standard and average deviations in parentheses apply to data up to the normal boling temperature ony. Temperature and heat capacity ranges correspond to the entre range of available dat. Recommended data are from ZSbranskf eal. (SSZAB/RUZ) ‘Compound No. data Sider. ‘Ave ‘Avg. dev points mol % (Lee Kesler) * 2 aH 359. a) 193 (106) 91-298 oar 33 a) 2 09 45 (2) 28 (4) 31-29 seus 106 (147) 6 3) 31 3) 43 20) 1036s 13178 32 4H) 2 uy, 40 2H 18 13) 145.390 142-200 ua) 3 08) 39 a) 13 07) 180-463, maz 18 @3) 35 Go) 20 67) 15 (19) 19-500 203-408 20 03) n 09 28 (18) 07 ©) m40 233.302 12 a3) 2 a a2 0 msi 265-292 3 25 (2) 63 1) 14 (12) 247-482 2-416 12 (12) 21 Qn) 82 16 252-433 330-424 as 5 @ 46 19 261-317 364-386 27 36) 63 4 m0 serait EY 8 Gs), Ma 23 753-433 ‘82377 18 6 ©) 18 15 285-313 465478 a 49 1s 20 23 S254 22 10 (19) 14 an-384 535-597 22 9 0) 18 3038 ‘567-605 26 7 ap 2s 305-453 395-709 16 9) Be 325-400 653-748 ag 4 30 Siea83 60776 3 16 (15) BS 318-453 res 20 4 0) 207 3244s 1s7 15 (3) 290 324453 mas 6 ©) 49 33373 816-865 1s a5) 252 309-454 47-1005 ‘octacosane 4 (4) 28 334453 912-1072 ‘netiscontane 1a) 337 33 339-339 1008-1008 so ndotracontane? = 14 (4) 80 189 sss CSL ritiacontane 5 (5) 34 07 353383 nus: Bd 266 7 346452 1138-1313 Incheratriacontane 17 (17) wT “a 39-00 1201-1817 fetraontane 2 @ mm sa 338 wai rdotetracontane 12. (12) 24 3 ssr-ase 1aa3-1684 364 26 393-482 16181818, sD = where ny is the numberof datapoints (usualy 10 K apart) "average absolute percent deviation i eaeulated as anv = wos S| “Average absolute percent deviation calulated by the above equation between the recommended heat capacities and those estimated bythe Lee- Kesler method (7SLEEIKES), ‘or all n-alkanes higher than n-decane no experimental bat are uncer, pasty subject to a stem er thane is poor with an average percent deviation of 11% in the range from the melting temperature to the normal boiling temperature. Past experience shows that first ‘members of homologous ceriae often do not conform eae ily toa group additivity in comparison to other members. We have thus not included data on ethane in the basic data set used to calculate parameters despite the fact that there are extensive accurate measurements of the heat capacity of this compound over almost the entire vapor- liquid saturation region. ‘J Phys. Chom, Ret. Data, Vol. 22, No 3, 1903, above the normal boiling temperature ae available Deviations berween observed and estimated heat ca- pacities for all n-alkanes are given in Table 7. Deviations slightly higher than the average, reaching a maximum value of about 6 96, have boon found for almost all alkanes starting with undecane at temperatures above 400 K. The deviations are almost constant for all higher ‘n-alkanes thus indicating that the dependence of a group contribution on the length of the carbon chain would not result in an improved estimation ofthe heat capacity. The use of 4 adjustable parameters in Eq. (2) to describe theESTIMATION OF HEAT CAPACITIES OF ORGANIC LIQUIDS 607 “Tnote 8, Deviations between recommended and estimated heat capacities of branched alkanes. Numbers of datapoints and valves of standard and erage deviations in parentheses apply to data up to the normal boiling temperature only. Temperature ad heat capacity ranges orre- Sond tote entre range of ovale data, Recommended data re from Zsbranst ea. QSZABRUZ) Conpoxnd ‘No. data - ins (Leekeser) ® Zmatnpropane BG) as eH 60 GI) 3 GO 22 dimetyiropane Omen 66 u Zimethybutane 21 @) 12 s Panorpueaee 2 Gn e) 16 an 3 an a8 08) ia a 2 @ aa a 2% Od 10 3 1 a 3 Fa 3 6) us) 59 (6) 16 10 a 4 as 36 te Us) ts at 16 1) a 3a 2 @ 3 as 22 tmethybane 9 (9) os 1s SS.aimemnenane 22) 3 13 25-dimetyterane 6) as oe Zemetyteptane 2 @ 08 04 Smethyhepane 25 G3) 10 109 eemneeae © t9 or oe 22a3etramethybutane 2 (2) i ZaAuimetiypenane— 22 (22) 22 28 233.timetiypentane 2 (2) 3 to Zsacrimemypensne 16 8) ts 5 GS) 10 16 9) 33 1 G9) 0s 3 C3) 0 Zemetyinonane 10 a Ssmetyinoane nay oa 1 ‘tmetylnonane 2 uD 09 22 ‘Seino nay 03 is metyidecane 18 cs) io Ideyhenecosne PO iva ‘Stanaard uevon ano average sosowte perwent devaion Otined mr TAKE T * See footnote eat the bottom of Table 7. dependence of Ac; on temperature does not lead to sub- stantially better predictions at higher temperatures as, well. The most plausible explanation lies in the selection of compounds used for the calculation of adjustable parameters. The set of selected compounds (see Table 4) contains predominantly short-chain hydrocarbons simply because there are no data available for long-chain hydro- Lerbuns utes than r-alhanes. 4.2. Branched Alkanes Deviations in the family of branched alkanes are in general low (Table 8). There are no data for branched alkanes higher than Cio except for 2-methyldecane and ‘N-decytheneicosane. Somewhat larger deviations for two compounds, 2-methylpropane and 2,2-dimethylpropane, can be possibly explained by a methyl repulsion for a recommended ond the estimated ternary and quaternary carbon atoms. The methyl repul- eyo pene Teresommendel 81S on correction was proposed and applied othe estima- tion of enthalpies of formation of substituted alkanes by semper Fig 1. The oprooment berween liguid eat capac from ZSbrancy 4. Phys. Chem, Ret. Dats, Vol 22, No. 3, 1983608 V. ROZIEKA, JR, AND E. S. DOMALSKI ‘TanLe9, Deviations between recommended and estimated heat capacities of alkenes. Numbers of datapoints and values of standard and average 2 00 8 209-236 Sige @metmtedybonene 19 D8 anos soe 8 (Cmetigropbesene BO) 1 391-00 soe 1234tetromethbemene uu) ua 300 pias 1235 tetromethybensene 30 2 255.297 sme 1248 tenn ten HG) 98 @) 38 ao same e308 netyiaphihalene wD oF 238 one 70 2 310367 9.282 wy 26 B09 nie no 3 same Zoe 0) 24 298 25.209 169 us 6s 2eu-i00 30) 89 62) 30589 mas 14 08) Tb-dmetpnaptbalene ©) 37 350-02 moa 25-dmetinnaphialene Siege cise Seas Zea 2é-dmeinnaphialene éO 2 Soot eae 27imetynaptlene 4@ 07 in 296-295 ‘J. Phys. Chom, Ret, Data, Vol. 22, No. 3, 1993,ESTIMATION OF HEAT CAPACITIES OF ORGANIC LIQUIDS 613, {Asus 13, Deviations between recommended and estimated heat capacities of aromatic hydrocarbons. Numbers of datapoints and values of stan- ‘dard and average deviations in parentheses apply to data up tothe normal bolig temperature only. Temperature and heat capacity ranges correspond tothe entire range of availble data, Recommended data are fom Zabranskj eal. 9SZAB/RUZ) — Continued ‘Std. de Compound ‘Avg dev BK! molt 9 ‘elobebenzene Da A 09 Deramethlbenzene 3) (124 32 1 -methylenbisbemzene 70 65 19 diGtetanetiindan nay 09 02 1447etramettyndan BG) 18 os anthracene 70) 6s 13 (.2-ethyneibisbenzene 2 @h aL 3a henantrene nu 96 28 (EpL-(idethenediypoibenzene 17 (15) 38 G3) 08 (08) Li2ethanedyDbibenzene 17 (17) 130 27 11 -tilidenedisbenzene 7 38 31 ‘Simcuytpnenamrene BG) 33 0 (C-metylethy)11 biphenyl ©) 4 GIs) 22 @3) fvoranthene 9 @) 13 03 pyrene 6 @ 06 01 Erpnenytene =o By 0s 112 terphenyl 2 hy ‘to 24 LYS" 1terpheny 20D 89 18 114" 1terpheny nay 4s 28 meny-7-(emetylethyDphenanthrenei3 (13) 140 28 srar'bisI-methylethy!)-11'-biphenyl 18 (18) 11 16 At" methylidenetisbenzene” 24) 00 1@Lnaphehalenyimethyaphhalene 10 (10) 09. on 2 Spaenys's 1 serpaeny 3) 30 on 14'S 1°3%A"-quaterphemyt ny BT 37 1Ut-diphenyldodecane 6 33 03 (eydoheryldodecl)benzene 2@ 23 on Trahsoctenzeneery) ‘wisnaphthalene 10 aa “a "Temp, Heat expaciy Avg. devs range, K range, FK-! mol! (Lee-Kesler) % 230-470 258-370 43.473 377-398 302-353 266-287 236.378 22309 170-396, 240-350 497-541 a39 5-553 sing 03-583 351-422 sma 313-382 260-299 23.295 oer 345-638 380-452 336373 ‘1479 353-380 330-356 390-407 ersu ss3512 487-580 285.500 20-487 521-687 581-640 440-503 597-60 586-595 603-606 370-967 ‘Standard deviation and average absolute percent deviation defined in Table 7. ‘ne neat capac values forthe compound were teed 3 = sige source of data w determine te aut parameters ‘See footnote « a the botom of Table 7 ‘TaBte 14. Summary deviations between observed and esi temperature only Family No. No. data ‘Avg. dev? Temp. Heat capacity emp points % ge, K ange, Jat ivallanes C; 10 Ca 85405) ms (88) 28 9) «ISO esis ‘Lris-Benson 485 (405) 137 G71) 26 (14) ‘branched alkanes Py 518 497) 45 3) 14.2) 85.383 100-938 ‘Benson x 518497) 51 G8) 16 (3) alkenes C; 10 Cie B 38964) 8 66 24 1.) 90366 67-488 alkenes C: to Cy 5 wa (11a) 86 43) 3823) 93-366 erst lie Remo & ut ang), 67 ay 2 Oo dienes C. 10 Cy 0 166 (157) 25 es) 09 (09) = asi6 108180 Bianee C0 Ce 2 we 2 eo 1G) eae mst ‘Tris-Beneon 7 ns (117) 42 42) 28 Qa) saturated eylic hydrocarbons ‘J. Phys. Chem. Ret. Data, Vol 22, No,14 V. ROZIGKA, JR. AND E. S. DOMALSKI ‘Tame 14. Summary deviations between observed and estimated heat capacities. Values in parentheses apply to data up to the normal boling temperature only — Continued Family Ne. No. dat ‘Avgde? ‘Temp. Heat capacity mpd points % ange, K ‘ange, ak"? Saturated epic hydrocarbons C10 Co 60 (1838) 20 210) 29 16.803 m9 sturated eee hydrocarbons 10 Gr 7% 81 0) LA I) 30 GH 36.523 1590. Lavia-Benson 20 G35) 34 G3) ‘enstarated acti hydrocarbons GIG » 132 (132) 23 @3) 09 (09) 141-328 2m aromatic hydrocarbons Gio Ce a 528 (os) 28 as) 1345) aon 4970 aromatic hydrocarbons G0 Ca as a7 G54) 90 (A) 18) 9 to Carle Denson 427 G59) m4 Gs 37 3) “Standard deviation i ealulated (c= — cmp where es the numberof compounds andy i the numberof datapoints foreach compound (usualy 10 K apt. Santana ae ano = 10-22 xf wie {Amu 19, summary aevatons netween ooserved nest capacities and tose estimated by the Lee-Kes parentheses apply to data up to the normal boing temperature ony. rmetnod (/9LEKIKES). Values in Family Ne. Ne. data “Temp. Heat eapaciy mpd, points range, K range Kot alkanes C10 Go Z 38 2 m1 a9) ‘srs 1008 tee Kesler B 386.250) m3 27) tranched alkanes C10 Ce 2s 406. (383) 47 an 1s an sss seo. Tee Kadler 8 403. G83) 136 (40) 50 (52) alkenes C; t0 Cis B 236 (191) 80 Ga) 3309) 90-366 67-365 Lee Kesler 8 23 49h na G4) 62 dienes C, 10 C5 2 35 @) 02 (02) 01 @) eee ass Lee Kesler 2 35 Go) 22 (20) 51 (58) saturated etic hydrocarbons 10. B st G18) 67 @a) 16 0) 136-505 1-300 Tee-Kedler B 336. G18) 187 (194-65 (69) ‘unsaturated ejetic hydrocarbons GIG 2 3 @) 24 @4) 1303) os at30r LeeKeler 2 Be 136 (36) 78 7a) aromatic hydrocarbons C10 1s 5 (54) 43 63) 13 GD) 162-5893 Lee Kesler 321 54) no GH $2 (62) ‘Standard don nd eae ass pa even dete a Te LPs, Chom. Ret. Dt, Vl 2, No. 3,880ESTIMATION OF HEAT CAPACITIES OF ORGANIC LIQUIDS 6. 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Ret, Data, Vo. 22, No. 8 1983618 ‘Appendix Sample calculation for the estimation of the heat capacity of n-heptane at 300 K (1)_ Kind and number of additive groups. "The structural formula for n-heptane is: (CHy-CH-CH-CH,-CHr-CH-CH, ‘The following groups are needed for the calculation of adjustable parameters necessary to estimate the heat ca- pacity of n-heptane in the liquid phase at an arbitrary temperature in the range from the melting to the boiling Temperature; let us choose 300 K. Molecular Group (No.of groupe Tragment oe CHES 2 eee IMO s 2) Group additivity representation for n-heptane. @ x CHIC) + x C-ODIC}) 4. Phys. Chem, Ret Data, Vol 22, No. 3, 1993, V. ROZIGKA, JR. AND E. S. DOMALSKI (3) Equations (1) and (2) are used to perform the calculation, CIR = X nebo and Bo; = a) + b(TNOO) + d(T/100), respectively, where R = 8.31451 Fmol“K"' and Tis in kelvin (4) Selection of groups and adjustable parameters, Adjustable parameters for C-(H)x(C) and C-(H)C): ate obtained from Table 5. Group cs a ‘Tem. range, K CHO 38652-39971 E-1 80400 CEC), 2797 = S496TE-2L06VE-1 80-450, (5) Calculation of the estimated value and comparison with the recommended value. CIR = 27.126 and C = 2255 Jmol Ko This result may be compared with the recom- mended value for the heat capacity of liquid incheptane at 300 K given in SIRUZ/ZAD equal to 225.40 Jmol~'K"!. The estimated value differs by