Selected Valves of Heats of Combustion and Heats of Formation of Oraanic Compounds Containing the Elements C, H, N, O, P, and S* Eugene S. Domateli Chemical Thermodynamics Data Center, National Bureau of Standards, Washington, D.C. 20234 Selected values of the heats of combustion and heats f formation of 719 organ az reported hore. The data tabulated pera to compounds containing the clement er itoen, oxy apd sur (CHINOPS) The informatio s eranged scoring lasres ‘compounds and within eac clans compounds ae aranged by epiieal formula. The general laos i: htontns aol hen oly cher chic, Ltn, ‘ides eaters, stems lactones, eatbotydraien, heterocycle Ufa definite, Guanne Soewatves:Smago eid poplides, aod Reteroeyee ound, porphyrin, ogni ar compounds, and aga phosphors compoxnin, When slot rom among ever investigator, commetry I provided toindieat the chee, and weully ‘ime relevant data. The numberof references sited eS, An alpshtialcompend indeseprvided page number, empirical formula, and the Wisweseer Line Notation (WL), ‘Key words: CHINOPS compounds; heat of combustion; heat of formation; selected values. Contents rae ee 1. Introduction 222 6.16, Aromatio aside and phonylated aliphatio 2 Arrangement of the Data se 2D acids... 237 3 Generalized Combustion Reactions for 6.17, Acid anhydrides. Ca CHNOPS Compounds... 223 GAB.Methel esters of monobasic aliohatic 4. Development of Combustion Calorimetry 23 acids S238 5. Corrections to the Combustion Data 24 6.19.Methyl esters of monobasic aromatic 5.1. Calibration correction. 24 cid, ar) 52 Vacuum correction. . SONI 28 6z0.bimethyt “esters of dibasic aliphatic 5.3. Molecular weight correction 224 acids. 1 239 54. 24 621.Dimethyl esters of dibasic aromatic 3 ' 206 tas : 209 5.6. Temperature correction 2256 20.Glycerpl esters. svvvvnnnnnnns 239 5.7. Caleulation of the standard heat of 628.Ster0ids..ssnsvnennnnnnnnnnnns 240 formation 225 624 Lactones 21 58 Units and constants... 225 6,25. Monosaccharides. 242 5.9. Uncertainty in the data 25 6,26, Dissaccharides 243 5,10. Acknowledgeme 25 6.27-Oligosaccharides....-.-. 2H 6. Classes of compounds and selec 226 6.28 Heterocyclic oxygen compoun cry 6.1. Aliphatic hydrocarbons 26 — 6.29-Aliphatic amines... nee 245, 6.2. Alicyclic hydrocarbons. 226 6,30. Aromatic amines — 216 63. Aromatic hydrocarbons. 221 6.34. Aliphatic amides. 246 64. Aliphatic aleohols.... “| 229 6.32. Aromatic amid: 6 65. Phen0l6nrnrnnn 280 6.38, Urea, guanidine, and their derivatives... 247 66. $316.94, Aliphatic amine acide... 27 61. 21 6.35. Aromatic amino acids, and aliphatig 68. fennneenee 282 amino acids containing a phenyl 69, ses ever. oa 6.96 Amine acid anhydrides (ikea zines). 250 6.37-Peptides. 250 6.38. Alkaloids. 251 6.39. Heterocyclic nitrogen compounds.. 251 - 6.40.Porphyins, 255 0.19, Unsaturaied aiphatie aicarboxyie acids.. 237 6-41. Organ sulfur compounds... 250 reel end enn dg 642.Organie sulfur compounds containing Pe fb err tn al nitrogen and/or oxygen.. 257 6.49. Organic plosplurus compounds. 258 1, References. boot epi © 1909 he US cy Como eal he iS 8 Compound index. Strib sie wind we Anca es eg teen ems & Compound index... 27 zat 1. Phys Chem. Rl, Data,222 EUGENE S. DOMALSKI 1. Introduetion As part of & continuing program of collecting and evaluating date on the thermeriynassic. properties, of ramic compote, scleted. ives are foported Bete for the heats of combustion and heats of formation of “i organic compounds conaiing the elements carton, Iydronem nitogen otygens phosphorus, and sultur (CHING "Cents ses ono such ae tutino acid, curblraretee, slveryl ater” ad. ey les, have been covered exhaustively because of their prime relevance to biological processes, Other elasses of Eompouns, sich as, hydrocarbons, leah, acids Ketones, eer aldchyder, were treated ina more cu sory and limited manner. These latter classes contain Compounds of natural bilogeal occurrence, and have ten tncluded because «lage group of comnion orgie acetone ql the a ms oacveaal Similar to substances occuring in bilogeal systems ‘The later clases are also needed to provide a sufficient amount of combastion date on cream etrutares ve thal tetimates can be made for molctles having related Structine, but for which there are no experimental data ‘Over the course of the CHNOPS roman, the cover aan nf the Lind at maen feof fore Combustion data have been examined has increased from about 6D to the present value of 19, Te iteature hha been searched fom as far back as the 1840 up to'the sary part of 107, The number of rgence som, wins for hich experimental heats of cmbustion Krave been determined has grown from about 600 prior to 1900, t about 150 by 1580, and to about 4000 for 3 current 11070), Companinde containing. the lo: ‘ments C, H, N, ©, P, and S comprise about 3200 of this current’ total. "We have arbitrarily selected 719 substances which’ we felt were of prime interest in biology. Considerable care has been taken in the evalua- tion and selection processes to present as unified a set ‘of data as possible so that meaningful comparisons ean bbe made among the data. We feel that this information ‘on the heats of combustion and heats of formation of the CHNOPS compounds will be of general use to biochem: ists, biophysicists, and biologists as they make thermo- dynamic assessments on vatious life processes, Tuas virtually impossible to provide a eoncise summa: tion of the general state of the combustion data inthis manuscript because of the broad range of substances ‘which js treated. Various comments can be found atthe end of'a given table assessing the data on that class of compounds as were deemed necessary, along with the al commentary on specific compounds. Qu tively speaking. the combustion data on the bydrocar. bons, “alcohols, ketones. n-aliphatic “acids, ethers, ethyl esters, and amines are very good. The data on the ‘amino acids and organte sulfur compounds can be rated se good tn fits those on the hetonneylia niteagmn nom Pounds aa whole are good; those on carbohydrates and elycery) esters are fair to poor, while the data on the Steroids, alkaloids, porphynins and organic phosphorus fcompauinvia can be rated, i gemesaly-an Pont. & aria quantitative method for rating the combustion data ean be obtained by examining the number of decimal places to which value is given explained more fully 2. Arrangement of the Data The classes of compounds are, arranged according to the general sequence: CH, CHO, CHN, CHNO, Cu, CHNOS, CHP, and CHOP, which denotes the Steaua ale for ae of Compounds the empirical formula (column 1) governs the orderin which compounds are fisted. Tiss followed by the name and physteal state (column 2) of the com- rnd: The combustion data, Ail’, mre expressed Kea ‘mot (column 3), and correspond to one of the netalized combustion reactions below. The substances Involved in the combustion process are present in their eeetedamic tenlard sees shes fy the etable fm Uf the substances at 25°C and one atmosphere presstre The fran de ae eapreseed in Kel mo am 4), and were calelated by combining the appr (rite dats or the bent of formation of COste HO a) HyPOu(e), and TSO. 11510tiq) with the’ com- hrustion date. ‘The literature sources are-given in the last column (column 5). When several references are Mica" forna, Compounds hose seterences which were sed to obtain the selected heat of combust formation are underlined. If only one reference avallable, itis underlined. If two or more references ate undefined, and no comments are provided for that Compound. at the end of the listing, one may assime that the data appearing in the underlined references fre either identical or stem from the same investigation 4 Phy. Cham Ref, Dot, Vol. 1, No.2, 1972 with only minor changes due to recalibration or recal ‘ulation by the eited authors. If two or more references are underlined and cach represent different investiga: tions, then a comment is made regarding that compound land how the references were used as the basis of the selected values. We have also provided an alphabetical Compound index which gives" the empirical formula, i Notation (WLN) for each com Pound, in addition to the page number where the Combustion data appear. Al of the selected values of heat tion ves deve oom serine, which is based upon an estimated val ‘Avfew of the compounds have their values based upon heats of reaction in solution, or have data on the heat of solution, fusion, ‘vaporization, or sublimation com. bined ‘with the combustion data. Discussion is provided for these compounds explaining what has been done ‘The combustion values. cited. by Kharasch [233] were not Used in any way. However, the references in his paper were a valuable means of obtaining the orignal combustion results s0 that the necessary corrections could be applied to them. "The selection process is based upon the personal and professional opinion of an evaluator after examining all fuHEATS OF COMBUSTION AND FORMATION OF ORGANIC COMPOUNDS of the available data on a compound and after applying the appropriate corrections to the data. Factors which are often taken into consideration are: (1) sample purity. @) number of experiments performed, (3) awareness of the investigators of the appropriate procedures, corree- tions, and constants, (4) agreement of the data with other investigations and (S) exposition of random and 223 systematic errors. Cursory presentation of data, or lack of adequate discussion, often leaves. persistent doubts as to the quality of the study. A well-documented presentation answers questions about the sample, the procedures, or the treatment of the results which most ‘thermochemists would raise, 3. Generalized Combustion Reactions for CHNOPS Compounds 1n order to calculate the heats of formation of organic compounds ofthe ‘type: Call, CaHNe, GHNOs, bor GaHsOg from their vores 3 of combus: ttn, any the heats of formation of Os) and HO are needed, Organic nitrogen compounds form Nu(g) as a product in the combustion reaction which, by defni- ‘om, has a heat of formation of zero. CoH + (a+ b/4) Ox(@)—- aC0s(2)+ (012)H20(ig) CaHLNe+ (0+ 6/4) 0s(@)—raCOx(e) SU ONO (2)N CHIN Oat ((4a+6—20/4) 0260 aCOxiR+ (0/2) HOU) (cf2) Net) CoH Oa+ ((4a+b—2d)/8) Oxf) —> “aCO,(g)+ (0/2) H.OUig). To calculate the heats of formation or organic eom- pounds of the type: CaHsS;, CaHOuSy, CoHyNeSy, and C.HLN.O,S; from their corresponding heats of com tion, the eats of formation of CU,(@), Ha0(q) H,S0, 115H.Oflig) are needed. Care must be taken to account for the ((8/2)—f) HeOlliq) formed as a product in these combustions, which is not written as a discrete product, but becomes ineorporated into’ the aqueous sulfurie acid solution. CaHbS+ (4+ 6+6/)/4)02(0) + (I16f—6/2) HeOtliq) > «CO 4+/{H80, 1151.0] (iq) CoHiO0S + ((Sa+ b—2a+6F)/4) 02(@) + A16F— 6/2) HO (igh C044) 4/{HeSO, 1151.0] (lig) CAHINS + ((Sa+b+6/)/4) 0310) + (116/612) HO (ig aCQ4( a) + (12) Na() FUHSO,- 1ISHLO} a) CoHANO4S + ((4a+b~ 2d-+ 6f)/4) O48) + (116f— 6/2)H20 (liqh> aCOu (+ (€/2)NeC@) 4/[H4S0, 1151.0} li). To calculate the heats of formation of organic com pounds of the type: GrEhP» and C-HaO4P. from their Corresponding heats of combustion, the hests of forma: tion of COs(g), HaO (i), and HsPO (0) are required. CuHyPe + ((4a-+5-+5e)/4) Ox(@)—> aCOx(@) + ((b=3e)/2) HO (ligh+ eHsPO,(6) CaHsO4P. + ((4a-+8~2d+5e)/4)0(-> aCO.(g)+ ((6~3e)/2) H2O(lig) + eHePO,(0). 4, Development of Combustion Calorimetry ‘The combustion studies of Andrews [10} and Favre and Silbermann (150, published around the middle of the 19th century, represent some of the very early ‘works Shordlythereater, Thomsen began tis lassie Combustion experiments’ using. a. flame calorimeter. His methods, and the resus of his studies were pub- lished na four volume compilation during the 1860's entitied” “Ihermochemishe "Untersuchungen [531 Berthelot began hie research in thermochemistry shortly besa th eatin by Bese Vee 112 n with a publication lot and Vieille 731i they ‘describe the combustion of substances in nub with oxygen under pressure. Prior to 1900, the sual method of determining the eneegy (wnt) equivalent waa rade by atmaming the products of the masses and epecife heats of the vanous aris of the calorimeter, In 1903, Jacger and. von Brcinwehr [203] reported the determination of the energy tanivalent af their hamh ealorimeter hy means of clectrical_ measurements. As a further improvement, they described the measurement of the temperature rise of their calorimeter using « platinum resistance ther ter [203] in conjunction with the electrical calbra~ is brought the level of impr calibration experiments to about 2.5 parts in 10,000. Internation: ‘neahbrating bomb calorimeters came during the 1920's. The substance chosen was benzoic acid, and still, today remains as the only chemical primary standard for this tvoe of calibration, Improvements in calorimetric procedures, ‘measuring’ instruments, and.calculative methods reduced the inaccuracy of the energy of com- bustion of benzoic acid to 0.07 percent in the 1930's and led Washburn (5591 to auggest the need far another refinement in bomb calorimetric calculations. The latter refinement dea it the eduction of combustion data rom bomb conditions (certain mass of sample, pressure of oxvgen. bomh volte and temperature to sandiions 4 Phy: Cham. Ref: Det, Vek 1, Ne. 2, 1972228 in which both the reactants and products of the iso- thermal combustion reaction are at one. atmosphere Bresgure. Subsequent development and improvement af the Washburn ‘corrections. were. made. by. Hubbard, Scott, and Waddington (chapt. 5 in ref. [393]), and Prosen (chapt. 6 in ref. [393)). In 1949, the Commission gh, Theresa of the fatomatona, Union ot Pure and. Applied Chemistry hegan a. project for the se of preparing atext which would place before the Scientific community the best knowledge of the members And advisors af the Comniceion relative to experimental 5. Corrections to From reading the preceding section on the develop ment of combustion calorimetry, one can surmise that the eaperimental data have appeared hr te Hie in a variety of forms and with a variety of corrections. Sometimes the treatment ofthe datais presented clearly, sometimes not, and sometimes the reader i left to guess That the tvetivent io We have attempted ty being all Pertinent combustion data on organie compounds of interest to a common base by applying the appropriate corrections. This base is a react fend reactants ave their vet States 296.15, wih curment values ofthe physieal ceurs with organic compounds containing sulfur in which the ‘corresponding combustion product 1s H,S0,-115110 lig). The latter is not a standard state, Duta convenient final concentration. For a pure liquid or crystal, the standard state is the substance in the condensed phase under a pressore of one atmosphere. For a gas, the standard state is the hiypothetical ideal eae. at unit fugacity, in which state the enthalpy is that ofthe real gas atthe same tempera. ture and at zero pressure. Symbolically, the standard sate is designated by a superscript The reference states for the elements C,H, N, O, P. and § are as follows: For C, the reference state is erystalline graphite at 298.15 K and 1 atm pressure. For H. N. and O. the reference state is the ideal diatomic gas at 208.15 K and unit fugacity. In this state, the respective enthalpy is that of the real gas at 298.15 K and zero pressure. Rar P. the referenea ctate i the crystalline white ‘a-modification at 298.15 K and 1 atm. pressure. For S, the reference state is the rhombie modifica tion at 298,15 K and 1 atm pressure. ‘The heats of formation of the above elements in their reference states are defined as equal to zero. The corrections, which have been applied to the experimental combustion data when neceseary are as follows: At, the National Bureau of Standards, standard samples of benzoic acid are purified, the heat of eom- ustion determined, and the combustion value ‘cer Life (579) ‘under the following. conditions: (@) ‘he combustion reaction is referred to 25°C: (b) the sample {fs bummed in'a bomb of constant volume sn pure oxygen at an initial pressure of 30 atm at 25°C; () the number Of grams of sample burned is equal to three times the 4 Phys. Chom. oto, Vo. 1, No.2, 1972 EUGENE S. DOMALSKI thermochemistry and the measurement of heats of chemical reactions, The first volume of “Experimental Thermochemistry.” edited by F. D. Rossini (303) was Published in 1956, A second volume, edited by H. A. ‘Skinner [437], was published in 1962. ‘Two valuable compilations were published during the course of gathering information for this manuscript, namely, the texts by Stull, Westrum, and Sinke (585), and Cox and Pilcher [587]. Both provide a vast amount of data on the thermochemistry and thermodynamics of ‘organic compounds, volume of the bomb in liters; (d) the number of grams of water placed in the bomb before combustion is cuual to divee tines ute volume of the bomb in liters. No unnecessary departure should be made from the above certified conditions. The heat of combustion of the standard sample benzoic acid under, conditions differing by small amounts from the standard conditions specified by (a), (b), (e), and (A) above will be obtained by multiplying’ the certified value by the factor, f, siven below [579]. 10(P 30) +42(mJ¥ —3) + 30(my/V —3) —45(8—25)] pressure in atmospheres of oxygen at the temperature 0, to which the reaction is referred, im, is the mass of the'sample burned in grams, my is the iss of the water placed in the hamb in prams, and V is the internal volume of the bomb in liters. If the value used by an investigator for the energy of combustion of benzoic acid differs simificantly from the currently certified Jet (weighed in vacuum) [579], the combustion value under evaluation is multiplied by a ratio of the appropriate value to that used by the investigator. 5.2. Vacuum Correction Particularly with the earlier literature, such as that Stohmann_ or Berthelot, the combustion di sented were for the samples weighed in mates of the densities of the sample and of air (assuming a roxcomahla tamparatira, haremetric procenre ond rs tive humidity) a buoyaney correction is applied to reduce the weight of the sample to that in vacuum, 5.3. Molecular Weight Uorrection ‘The amount of the combustion reaction is often stated on the basis of the number of moles of substance burned, or of substance collected as a product. A significant correction may be required due to differences in the accepted values of atomic masses. Molecular weights are converted to the 1961 table of atomic masses based "upon the isotope C!*= 12 (580) 5.4. Washburn Correction This correction reduces bomb calori from bomb conditions to conditior ants and products are in their standard states at one ‘atmospheric pressure.HEATS OF COMBUSTION ANN FOPMATION OF ORGANIC COMPOUNDS 5.5. AnRT Correction ‘The conversion of combustion data presented for the process at constant volume to that at constant pressure is made by means of the equation: AH AU°+ AnR7, where Anis the difference between the number of moles Sf znscous ens and wave reactants involved in ‘combustion reaction, . Temperature Correction All combustion data are reduced to the reference temperature of 25°C. (298.15 K). The appropriate Acp for’ the combustion reaction is calculated or ted for the temperature interval under ration. The temperature 298 K is assigned to the ‘AH. and AHy° aata tabulated for the various classes of ‘compounds in section 6, and is implied to be synonymous with 298.15 K. 5.7. Caleulation of the Standard Heat ‘of Formation ‘The standard heat of formation at 298.15 K of an organie compound is calculated from the standard teat’ of combustion ‘and, the, heats of, formation, of ‘eathon dioxide (@), —94051 keal mol-*; water (liq), =68.315 kcal molt; phosphoric acid (c), —305. ‘nd aqueous sulfurie acid, H.SO, 115110, 212.192 ‘keal “mol. The later heatofformation data were obtained from NBS Technical Note 270-3 (seth 5.8, Unite and Constants The evaluated heats of combustion, and heats of formation are expressed in keal_mol-!. The unit of ‘energy int SI unite is the joule, and one calorie i taken fas 4184 J. Values for the heats of combustion in KJ mol-* can be obtained by multiplying the tabulated values in keal mol~! by 4.184. Calculation of the heats Of formation in KJ mol *'should be obtained frou the difference between the heats of combustion and the corresponding sum of the heats of formation of the ‘combustion products, both in kJ mol”, Following this path, rather than the multiplication of the tabulsted heats of formation by 4.184, will avoid rounding varia- tions in the last place which otherwise will occur. ‘The value of the gas constant, R, is 8.3143 J deg: mol", The ice point 1s denned as 213.19 K. 208 3.9. Uncertainty of the Data Although sncertsintics are not cited, the number of significant figures reporting the combustion and formation data is elated to the estimated uncertainty as shovin below. If AHe® or AHf* | The estimated uncertanty is cited to: "in AH or AHf* ist (kcal mol) kel mol) 0.001 0.05 0.01 0.05 10 0.5 OL 05 w2 1 2" 1020 5.10. Acknowledgements ‘The program under which this work was performed was initiated at the National Bureau of Standards on 1'May 1964 and has continued up to the present time. vance to biologically related problems. The thermod) namic data are to be used by NASA in studying problems such as: (1) theoretical i ‘of the pre Fence of organi compounds Primitive conditions, and (3) nfering ax much as possi Ble of the thermedynamies. and thermochemistry of uctauie earings fom Unive eh te formation. Technical. supervision was. provided. by Dr. George Jacobs of the National Aeronautics and Space Administration, Dr, Charles W. Beckett and BE Seonge Arnmsrou, bust of she Satna Bureat Standards, We also acknowledge the valuable con. fullaive asltance of Dr, Harald Morowit, Deparment Sf Molecular Biology and Biopbysis, Yale Univer. ‘The work at NBS for NASA fs coordinated wits Inted"aak't the Thermodynamics Research Center, ‘Texas AGM University under the supervision af DeMandneh CW, aS more Comprehensive ompllanon of ibe thermodyneme dave prepared il pear in "Handbook of Thermodynamic Date for Bio chemistry” (Academic Press, Inc), G. T, Armstrong fand RC. Wilhoit, editors "The author scknowlcdges tho important role of (Mrs) Iva Halow Day in Une present work. Her effots in collection, evaluation, and selection of a large seme tient of the combustion and formation data presented tere are The author also thanks tis wf, stance in compiling the re. erences; and Mr. Willam J. Wiswesser for proo(read- ing the Wiewesssr LincFermula Notations cled in the eShpoud index: 4. Phys. Cham. Re. Dot, Vol. 1, No.2, 19720c EUcENE s 6. Classes of Compounds and Selected Values 6.1. Aliphatic Hydrocarbons Formula Compound (State) | AHe'298 K | AH/°298K] Reference Keel molt | keal mal! CH, methane (8) 212.79 | -17.89 Colle acetylene () 310.61 | +5419 Cit ethylene (@ 33723 | +1250 35, 301, 981, 578] Gite ethane (@) 372,81 | —20.24] (62, 300, 531, 578) CoH Propane (#) [62, 390, 531, 578) Catt butane (6) F300; 978, 500 CH pentane (8) Cathe pentane (lig) CoH trhexane (liq) values for the aliphaue hydrocarbons are ‘consist with those tabulated by Zwolinski et al. [578]. This tabulation (A.P.1. Project 44) has appeared in an earlier form which may be more familiar; see Rossini (392]. methane (g)—The combustion data of Rossini (387, 388] ‘were used to make the selection. The earlv studies on the heat of combustion of methane by Andrews [10], Mix. ter [319], Favre and Silberman [150}, Thomsen (530,531) and Berthelot [32] are of historical interest only. ‘acetylene (g)—The unpublished calculated data of Brncnn and Rousni cited hy Wasman, Kilpatrick Pitzer. and Rossini (5561 were chosen for the selected value. ‘The actual data source appears to be the hydrogenation studies of Conn, Kistiakowsky, and Smith (590), cor- Footed to 25°C.’Tho early studios of Thomeon [S21], Berthelot [31, 32], Berthelot and Matignon [62], and Mixter (319, 316] are of historical interest only. ethylene (@—The combustion data ot Rossini and Knowlton {391}, and the heat-othydrogenation data of Kistakowsky, Romeyn, Ruhoff, Smith, and Vaughan [235] as corrected by Prosen and Rossini (375] were used to obtain the selected value. The early studies of Dulong 1141}, Grassi (168], Favre and Silbermann (150), Andrews 10}, Berthelot {82}, Berthelot and Matignon (62), Thomsen (581), and Minter (315, 316] are of historical interest only. ethane (g)—The combustion dota of Rossini (890) wen Used’ to make the selection, “The ‘early studies by ‘Thomsen [531), and Berthelot and Matignon [62] are 0 bistorial interest only. propane (@)~The combustion data of Rossini [390] wen Sed to make th selection acetyl of Tse {531}, and Berthelot and Matignon [62] are of historica interest only. n-butane (a) The combuation data of Rocsint [300] an Prosen, Maron, and Rossini [589] were averaged to of tain the selected value. pentane (2)~The combustion data of Rossini (390] wer tied to make the selection, ‘The more recent data ¢ Pilcher and Chadwick [859] are in very good agreemen with the selection. pentane (lig—The combustion data of Prosen an: Kssint [373}"were ‘used tor the selected value, Th recent data of Good [584] are in very good agreemen ith the selection. The earlier work of Roth and Mache ft [d0dlwas not used mhexane (lig)—The combustion data of Prosen an Rossini 873] were used to make the selection. Th data of Jessup [209] and Good and Smith (167) are i ‘very good agreement vith the selection. The early dat of Stohmann and Kleber (466), and the data of Zabo [526] as corrected by Swietoslawaki [516] are of histor ical interest only. 6.2. Alicyelie Hydrocarbons Formula Compound (State) | AME] AH/-2HK | Kelerence keel mol | Keal mol" cat. evelopropene (@ 490.08] 412.75] fa2, 69,62, 228, 67m) cH eyelebutane (ia) 650.22] “+0.26] 113, 2i7, 578) Ce ‘yelopentane (lq) ~73655] 2528) 21 8 6, CH cyclohexane (liq) ~936.e7] —37.33 | (167, 213, 917, 317, ” Ooi ai aii, Ae, 516, 876, 578}. 1 Ph. Chm. a Dat. Vl Ne 2.1972HEATS OF COMBUSTION AND FORMATION OF ORGANIC COMPOUNDS zr Formula ‘Compound (State) AHf208K | Reference eal mol? CH eyeloheptane (iq) “= 1090.00) 37.47 (24 48,516,576, Cathe | eyclooctane dig) ~Hasas] 40.58 It 2,9, 4, ‘The selected values for the heats of combustion and. formation of the alieyclic hydrocarbons are consistent with those tabulated by Zwolinski et al. (578). This latter tabulation (A.P.L. Project 44) has appeared in an earlier form which may be more familiar; see Rossini [392]. 1c (lig) ‘The combustion data of Coops and ct {13} “and” Knarsemaker “and: "Coope [217] appear to be the same. —The combustion data of Johnson, [219] wee uoed in yrclercuve te the data ‘of Kaarsemaker and Coops (217), and Spitzer and Hufiman (448). The work of Zubov [577] as cor- rected by Swietoslawshi (516] is of historical interest only. cyclohexane (liq)—The combustion data of Good and Smith [167] and Johnson, Prosen, and Rossini [213] were used to make the selection. The data of Kaarse- maker and Coops [217], Spitzer and Huffman [48}, ‘and Moore, Renquist and Parks [317] are in good agree: ‘ment with the selection. The works of Stohmann and Leangbein (477, 4761. Zubow [5761 as, corected by Swietoslawski 1516), and of Roth and ‘von Auwers [397] are of historical interest only. cyeloheptane (ligh—The combustion data of Spitzer sand Huffman [448] and Kaarsemaker and Coops (2171 ‘were averaged to obtain the selected value. The of Zabov [576] a8 corected by S were not used. eyclocctane(lig)—Tho combustion data of Kaarsemaker and Coops [217], ‘and Spitzer and' Huffman [448] were averaged to obtain the selected value. The data of Sehlipter [419] and Ruzicka and Schlipfer [412] 6.3. Aromatic Hydrocarbons Formula ‘Compound (Btate) ‘AN*290 eal mol alip-290 keal mol! Reterence Calle benzene (@) Calle benzene (liq) naphthalene (e) Cools naphthalene (e) Culhe anthracene (g) Cute anthracene) Cullo Cube phenanthrene (a) phenanthrene (e) 709.06] + 19.81! (53, 64, 120, 151, 175, 184, 339, 285, 392, 483, 486, 531, 559, 567, 578} [ata 118 tan, 167, 822, 379, 360, 381, 382, 383, 392, 397, 968, 488, 578] (4, 7,03, tas, 311, 428, 430, 481, 567, 569, 573} (22, 26, 57, 69, 5, 86, 106, 156, 158, 197, 219, 228, 276, 313, 871, 37, 380, 385, 897, 410, 420, af 497, 498, 910, 522, 538) 544, 545, 546, 571} {83, 186, 302, 231, 231, 329, 498, 455) [2, 26, 74, 5, 86, +n -101 | +356 —1318 | +180 -im20 | +537 1687.3 | +29.0 1706.7 — 1685.6 +494 +03 [83, 186, 202) 126, 74, 75, 106, 158, 236, 279, 313, 384, 490) 468 4. Phys. Cham. Ra. Dato Vl. 1, No 2, 1972ENAENE © nOMALSKE Aromatic Hydrocarbons— Continued Formula Compound State) | AHe298.K | AH/"298K) Reference eal mol! | eal mol-t Cutty pyrene (©) e738 | $27.44 | (888, 562) Gath fluoranthene (e) 1992.14 +45.25| (#2, $62} Cutt triphenylene (e) ~2136.53] — +38.72 (279, 562] Cote chrysene (@) =21378 | +350 | (279, 460) Call naphihacene () aii | +383 | (279) Calli 12benzanthracene (e) =2c0| +412 | (279) Cutts ‘siebenapnenanenrene ) | —zisrs | rasa | (209) Calla perylene (0) 2838.60] +48.69 | [364, 562] henzene (2) References (120, 151, 175, 184, 239, 285, 392, 552, 567, 578] provided experimental data on the determination of the heat of vaporization of benzene. We have used the ideal heat of vaporization at 25 °C of 10 keal mal! ae in references [202, S78) Ty combi ing the latter value with the Affe*[CeHe(lig)]— = 780.96 kcal molt, we calculate AHe*=~ 789.06 keal mol for gaseous benzene. The early studies on the hast of cambuetion of gases henzena, references (83, 64, 483, 486, 531] were not used and are of his- torical interest only. Benzene (lig)—The combustion data of Good and Stith, {US} and Prong, Glinont and Ronin [272] ware wed to obtain the selected value, The data of Coops, Mulder, Dienske, and Smittenberg (114, 115] were not used. References (31, 140, 379-883, 397, 468, 483, 578) sum: imarize the early studies, and’are of historical interest only. naphthalene (g)~The sublimation pressures of naphtha- Tene were measured by Bradley and Cleashy (83) Sher ‘Sood ond Beyant 480} Niles fli} Zikberrtan- Cramer kaya {373}, Swan and Mack {507}, Winstrom and Kulp {509}, Allen (7 Hoyer and Peperle (186) Ai Sears and Hopi (426), and Shiyarenko, Markin, and eyarea 431) When plotted individually as log P vers Uf, these sets of data show generally poor agreement, but when considered as whole, good agreement re. sults, giving a reasonably straghi line. Using a least. tae treatment af the vapor pressive data, we obta for the heat of sublimation, 176 keal Combining this'‘with our selection, AffeTCyeHs() T2318 keal mol !, we calculate Affe? =— 1249.4 keal Teal! for grocons naphthalene ‘aphuhalene (c)—The heat of combustion of naphtha. Bete (@) was measured: by von Rechenborg, [377], Stolunann” (457,488), Rubner 410}, Richards. and Dani {30}. Rebel! and Louetining (37) Rebelo tnd Recours (6), Berthelot and Vielle (73), Fincher tnd Wrede (152), Mier and Scheteig [385], Roth Sind von Auwers (397), Wrede (511) Dickinson (138), Kuvee and onan [19]. Verende'and nope (S44, SAS], Beckers [22], Bure {66} Kefler [223]. Milone and. Rossignel (313). Sehiipler and. Fiore! (320), Hitnan and Elis [i9t}, Bender and Resber (25), Speror and. Rowtini [4], Prasen” and. Calabi (3717, Mace sua" O'Hare (206), and Coleman and Pilcher [106). The value forthe heat of combustion of naphthalene Telatveto tht of bese aa cee take te inenters a8 18209 to 18208 For a i int ace Verkade (S38), Verkade, Coope and Hartman Fotoys"Swicteclayats [SiS]y and Swicoslano and 4. Phys Chom Ret Date Vl. 1, No.2, 1972 Storerewsle [522], I we take the value 1.5204, and the cently accepted value. for benzoic acid" (~ AU Sokst Je" (vacuum) at 25 °C), and apply the appro priate corrections (for standard states, AT, and cal. Pnlation of AH/*), we obtain for ou’ selected value SHE T2818 bea mol and ‘Bl 8 ead tinthracene (@)~ Sublimation pressures have been ‘measured by Bradley and Cleseby (83), Stevene [885], Klochkov (287), Inokuchi, Shiba, Handa, and Akamatu [202], Sears and Hopke [428]. Nita, Seki, and Momotani (329), Kelly and Rice (231), and Hoyer and Peperle [186]. The experimental date af Bradley find Cleashy [83], and’ Klochkow [237] were used to ‘htain a selected heat of sublimation of 24.7 keal mol-", By combining the later with He" {Cuttfe)] =— 1687 3 eal molt. we caleulate AHe=— "17120 keal mol"! for gascous anthracene. anthracene (¢) ~The heat of combustion of anthracene (0, was measured by von Rechenberg (377), Stohmann [AST Stohmann, Kishor. and [anehein [468], Rerthelt go Ve TAR sh Mcckers 8). Burl (Goh ger. (960), Klaproth (2 and. Rossignol, [S13 ites, Walter and Schilling (158). Shehuksrey and Shehuleireva [429], Richardson and Parks [384]. Parks, West,” Naylor, Fuh Bender and Farber (36), Magnus, Hartmann, Becker [279], Mackle and O'Hare [276], and Coleman and Pacher {Obl An average heat of combustion de- 1¢ data of the fast six investigations (25, Toe 216, 219, MS, 304)" mentioned consis Sut selected” value." ae"{Cullte}= 1087. Kea rnanthrene.(g)—Sublimation Urol by Bradley and Cleaehy Handa, and Akamatu (202), and Hoyer and Pepe [186)-'We derived the heat of sublimation at 25% 2L kal mol" from the data of Bradley and Cleasby [88]. By combining AM (sublimation) with AMfe*{Cix Hule))=—1685.6 Keal mol, we calculate Ae spike ma for ene enantene mnanthrene ()—The heat of combustion of phenan- threne (¢) was. measured by Stohmann, Kleber, and Langbein {468}, Berthelot and Vielle [74,75], Klaproth (236), ‘Miline and Roceignoli (313), ‘ShchaLasey and Shehikareva, [429], “Fries, Walter, and Schiling 158), Richardson and Parks (384), Bender 26], Magnus, Hartmann, and Bocker (279), tranand Pishor [108]. An averse hos Gerived from the data of the last three investigations 26," 105, 279], constitutes our selected value. A/c” {Coe)] = 1685.6 keal mol Fes] inokachi, Shiba,HEATS OF COMBUSTION AND FORMATION OF ORGANIC COMPOUNDS pyrene (c)—The combustion data of Westrum and Wong 228 and Wong (562), were be preferred to those of Richardson and Parks — Hartmann, and Becker 04) in aking the selection chnysene (c) ~The comb uoranthene (c)—The combustion data of Westrum and mann. and Becker [279] were preferred to those of jong [562], and Boyd, Christensen, and Pua [82] jeryiene (c)—The combustion data of Westrum and ‘were averaged in obtaining the selected value, Wome [562] were preferred tw those of Pongrate and triphenylene (€)—The combustion data of Westrum Geng! (364) he selection. 6.4 Aliphatic Alcohols Formola Compound State) | Aie298 K | anr29eK | Reference eal mol” | eal mol" CHO methanol (g) 182.72 —47.96 | 1150, 389, 531) CHO methanol (liq) 173.64 57.04 | (92, 149, 151, 300, 395, 398, 406, 471, 555, 561) catuo ethanol (2 =336.86) —56.19| (10.150, 389. 531) CxHeO ‘ethanol (liq) 326.68, 66.37 | [11, 12, 59, 60, 92, TOL, 144, 151, 380, 406, 555] CIO 1L-propanol (iq) 402.75 | —72.06 (92, 261, 380, 445, 516, 575] CHO 2:propanal dig) —s79.44| —1597| (92, Bot, 382, 344, 516, 575) Cattw0 butane —659.53| —78.25 Cato | 2a ad —ess.90| —a1.08 CHO 2-methyl-1-propanol (liq) 637.93 79.85 516, 575] C400 | 2methst2n0nane ad ono} —as.a6) ath CHO 2-methyl-2-propanol (c) 630.3 —87.5_ | (263, 376,516,575} HO L-pentanol (liq) 795.88 | —84.27| (92, 171, 261, 516, Sia, 575] Caw texan iy =951.86| —9n.65 | (92,548) methanal (2) —The combnstion data of Rossini (3801 fn gaseous methanol were chosen in preference to the ‘early work of Thomsen [531]. A correction for dimer fand tetramer formation amounting to—0.13 keal mol swar mede to, the combustion dats of Roesint [20] Using the study of Weltner and Pitzer [561]. The data of Favre and Siermann [160] are of historical intrest only. al 134) —Oun chested alu forthe bea of comm instion of CHiOlitig) is obtained by combining the Yalue for the heat of combustion of CLLOH() with the Heat of vaporiation of the liquid to. the qascous towers Phe ew of veyed ve tel 25°°C""was taken from the measurements of Fook, Ginnings, and Holton [151], AHvap at 25 °C=8.95 kcal mol", Recent vaporization data by Wadsé [555] Edlarery food aprecmont By sppinne the dimers tion data of Weltner and Pitzer (361] to the vaporiza- tion data, we obtain AHvap at 25' 08 keal mol? for the process: CH,OH(liq) = CHsOH(g, monomer). pelt, gza comin mewurene! of Chao and sini [22] on the liquid is in good agreement wil our selection. The earlier works of Stohmann, Kleber, se eee, Teh fnickteds and Davie (200), enk Laas} Bete a Banc (OR) Bath nd Millon (AD and L. G""Fatbenfabriken [149] have not been use ethanol (g)~The combustion data of Rossini [389] ‘on gaseous ethanol were chosen in preference to the trier date of Thomewn [S21]. Avaorastion for the presence of dimeric ethanol (g) was introduced into the Combustion data from the data of Coburn and Grunwald 01) amounting t0 ~0.06 keal molt. The data ot An- drow (10) and Favre and Silberman [160] are wuly of ethanol (lig)~Out selection forthe heat of combustion tras obtained by combining the value forthe heat of Simnbusin of CHCHZOKG) whi the hear of vapors tion of the liquid tothe gaseous monomer, The heat of vaporiation of ethanol at 25°C was taken from the Incasurements of Fiock, Cinningsy and Holton {191}, nape Hecate ta sb (555] “ae in very good agreement. By applying the dimerization data of Coburn and Gran wald [101] to the vaporiation data, we obtain forthe Brocess: CHLCHsOillig= CHLCHLON tg, monomer), Ava at 25 °C=10.18 keal mol The recent combustion measurement of Chao and Roteint POS] an the eg arin Good upeeomeae it 4. Phys. Cham. Rt, Dot, Vol 1, No.2, 1972230 ‘our selection. The earlier data of Berthelot and Matignon 59, 60] Emery and Benedict [144], Atwater and Rosa 1, Atwater and Swell (2), Roth and Miller (106) and itichards and Davis (380 were not propanol (ig)The combustion data of Chao and Rossini [92] and Snelson and Skinner [445] were averaged to obtain the selected value. The earlier data were not used, ton de of hg and Beropanl lg)—the combustion da of Chae ap Rossini [92], Snelson and Skinner [445], and Parks, Mosley snd Petergon Cad] were, averaand to abiain the selected value. The earlier data were not used. butanol (lig)—The combustion data of Mosselman and Dekker [320], and Gundry, Head, and Lewis [172] were averaged to obttin the selected value, The carly ddata of Zabov {575} and the correction of the latter by Swietoslawaki (516] were not used. The combus data of Tjebbes appeared to be not negative nowgh by at least ane keal mol-", and once ware hot used. ‘The combustion data of Chao and Rossini {92] appeared too negative by about 0.4 kcal mol-*, EUGENE S. DOMALSKI The, combustion data of Richards and Davis (380), Verkade and Coops [543], and Skinner and Snelson [438] were not used. butanol (ig)—The, combustion data of Chao and Rossini [92], and Skinner and Snelson [438] were averaged to obtain the selection, 2.methvl-L-propanol (lig) The combustion data of Chae dnd Rossini [92] and Skinner and Snelson (488) were averaged to obtain the selected value. ‘The earlier date wwere not used, DemethstI-prapanol fe)—The cambuesion data Skinner and Snelson [438] on the liquid, and the heat offusion dats of Raley, et al. [376] were combined to obtain the selected value, I-pentanol (lig)—The combuetion data of Gundry, Harrop, Head, and Lewis [171] were used to obtair the selected value. The earlier daia were not used. Fhexanol(lig)—The combustion data of Chao and iat (22) mee wacal wy vbtaia the sclevied. value. which trees withthe. data af Verkade and Coupe 543] by about 0.3 keal mol 6.5. Phenols Formula Compound (State) | AHe-298.K | AH/298 K] Reference eal molt | “keal mol? Cals0 phenol (¢) —np.80] 39.45] (9, 16, 57, 75, 118, 119, 218, 280, 341, 371, 457, 460, 476, ‘1 Cates pyrocatechol (¢) 083.0 | 86.3 Gatleos senencinel (2) eor.so| 02.96 CHO: isdroquinone (e) =oei-t8| —arar| (29-5r, 277, 3m, 363, 460, 476, - 484, 525, 537] Gano o-eresol{e) ~ws2.72| —48.90| 19, 118, 119, 485) CHO meeresol (6) 885.25] —46.37| [9, 118, 119, 485, Cato peresdl ) 19.00) — 762] poo tte Hb, 495) CHO 2-ethyiphenol (c) 1407} son) CoH 3-ethylphenol (c) 1082.77} -51.21 | [7] Cath ‘ethylphenol (c) = 1040.35 | —53.68 | [7] phenol (c)—The heat of combustion of phenol was measured by von Rechonberg (377), Stohmann. [15 460), Berthelot and Louguinine v7], Berthelot anc Vieille [75], Andon, emir Cox, Handley, 3, Hevington, and. Martin 2}, Cox, 118, 19h Kare Sieh steadier (200, Maaksy Maetoaters and Vaug [341], Stohmann, Rodatz, and Herzbers [484], Stohmann and Langbein [476], and Badoche [16] ‘We have used the data of Andon et al. [9] and Cox {018, 119] for our selected val Ppyrocatechol (c)—The combustion data of Stohmann [460], and Stohmann and Langbein [476] were obtained using an oxygen bomb calorimeter, and are preferred to the data of Stohmann [407] in which the potassium thiorse-tidative mixture technique. was used. The data in references [460] and {476} are the same. The heat of combustion calculated from the latter was found tobe GHL9 Leal mol" afer all correcdons, were applied, This was adjusted to —683.0 kcal mol-! ijecause the value for the heat of combustion of phenol found ‘by Stohmann and Lanabein (876) was 2 10 8 4 Phys Chom. Rt, Dot, Vol 1, No 2, 1972 kcal mol! more negative than our presently selected value for phenol. resorcinol (c)—The combustion data of Dessi, Wilhoit, and Zwolinski [137] were chosen in preference to the earlier combustion data, hydroquinone (c)— The combustion data of Pilcher and Sutton [363] were chosen in preference to any other combustion data, ‘o-cresol (€)~ The combustion data of Andon, Biddis- combe, Cox, Handley, Harrop, Herington, and Martin {9}, and Cox [118, 119] were chosen in preference to the’ data of Stohmann, Rodatz, and Herzberg. [485]. meeresot (¢)~ The combustion data of Andon, Biddis- combe, Cox, Handley, Harrop, Herington, and Martin [9], and Cox [118, 119} were chosen in preference tothe earlier data. preresol (c)— ‘The combustion data of Andon, Biddis- ‘combe, Cox, Handley, Harrop, Herington, and Martin 9], and Cox [118, 119] were ehosen in preference to the data of Stohmann, Rodatz and Herbers [485],MEATS OF COMBUSTION AND FORMATION OF ORGANIC COMPOUNDS at 6.6. Aliphatic Di- and Polyols Formula ‘Compound State ‘AHe208 K leference een) [estat | tearm | 1 2ethanediol (ig (ethylene | 284.28 | —108.70 | (216, 260, 222, 245, elycol) 476] 12:propanediol (iq) 435.8 | 119.6 | [259,322] 1,3-propanediol (liq) 431.0 | —124.4 | [259] 123-propanetsol (tq) =395.65 | —159.76 | (144, 260, 345, 457, Glycerol) 481] meso-1,2.3A-butanetetrol —500.22 | —217.56 | [58, 270, 345, 457, (© daesreryuliwod 360, 476) | pentaerythritol (€) 660.1 | —220.0 | {305, 476) aolitol(¢) —612.88 | —267.32 | [330] L-arabitol(o) -ons | -268.7 | (476) acetone glycerol (tig) ail 16 | (17) Cathe D.maneutol (¢) —72.97 | —319.54 | [17, 76, 162, 345, 877, 457, 476, 481) Gitte dulitol(e) 720,08 | —sz1.85 | (70, 345, $17, 497, 476, 481) Coty Dperseitol (c) 835.2 | -309.7 | (476) D glvoo-a heptite (6) ems | —364's | (256) 1,10-decanediol (©) = 1526.20 | — 165.78 | [343] dipentaerythritol (0) =1315.1 | —376.9 | [307] 1.256-diacetone-mannitol ) | ~1530 | —350 | 171 1 2ethanediol, (ethylene glycol) (ig)—The combustion data of Parks, ‘West, Naylor, Fujii, and MeClaine [Fist wor prefrontal va L2.propaneaiol (tig) The combustion data of Mourew a be {322) ere preferred to those of Louguinine 123 propanctriol, (glycerol) (liq) The combustion dite Bark Wea Neo, Fujiand MeCisine 8} ‘were choten in preference to the earlier combustion daa, imeso-b2ehA-butanctetrol, (mesoerythritel) (c) ~The Combustion data of Parks, West, Naylor, Fuji, and McClaine [345] were chosen in preference to the earlier combustion dat pentan ytheted (e)—Fre wanubuston date of Meda and ‘Them 1s [305] were preferred to the data of Stoh- U7] sive isomers, but because of their seant description of calorimetric procedures and results, we have assigned a single value to all D mannitol (c) "The combustion data of Parks, West, Naylor, Fujii, and McClaine [345] were preferred to any data published before 1900 (references (76, 162, 377, 457, 460, 476, 481)). The recent combustion dat ‘of Bace and lehmig [17] are im poor agrecment vith four selected value, deviating by 6 to 7 keal mol Details of their calorimetric procedures and data are scant, and the 6 to 7 keal mol eould be the overall ‘uncertainty in their experiments, dulcitol (c)—The combustion data of Parks, West, Naylor, Fujii, and MeClaine [345] ‘were chosen in preference to the earlier combustion data. 12,2,0-dacelone-mannitol " (¢)~Baer "and Klehmig [i7)'give combustion data for D-, and Leisomers, but because of their scant description of calorimetric pro- cedures and results, we have assigned a single value to 6.7._ Ethers Formule Compound State) | ate2ve x | anr298 | Reference Z eal mol | Keal mol cath0 dimes ether(@) — 9.06 | —43.99| (32,300,581) Gio methyl ethyl ether(@) = 503.69 | —51.72 | (360,581) itv | debe there 65752 | e026 | fas. 458.5301 Citw0, | 12:dimethonyethanedi) | —627-76 | —90.02 | (286) dimeihyt ether (x) ~The combustion data of Pitches, Pell and Coleman [360] were prefered to the earlier methyl ethyl ether (g) ~The combustion data of Pilcher, data of Thomsen (531 J. diethyl ether (g)—The combustion data of Pilcher, Skinner, Vell, tnd Pope [361] were prefened to the Fal and Golem, [360] were preferred tothe carer 4. Phy. Chom, Ref ote, Vo. Ne 2, 1972232 EUGENE $. DOMALSKI 6.8. Aldehydes Formula Camponnd State) ‘ane2o8 K [AHP IORK| Reference eal mol? | keal mo pt et CHO formaldehyde (g) (methanal) | —186.42 | ~25.95 | 1558,591) CHO. elyoxal () =205.76 | —50.66| {591} GaHLO acetaldehyde (g) (ethanel) —285.01 | —39,72| [65, 139) CHO acetaldehyde (i) (ethanal) | —278.77 | —45.96] [49, 50, 105, 406] CHO ‘propionaldehyde (liq) (1- ase | —53.0 | (49,50, 534) propanal) CHO, slyeeraldehyde (lia) 4 =143 | (17) C0 mebutyraldehyde (lig) + ~se22 | —s7.0 | [326,594] Dutanal) GHW revaeralchyde Gg) —m2 —10 | [262] pentanal) CaHiOs S-hydroxy-1-pentanal (liq) oa | -1s7 | [4429 Colts acetone glyceraldehyde =76 | —180 | [17] ig) Gals pataldelyde (iy) 210.0 | —168.2 | [90, 155, 265] GHO benzaldehyde (ia) —e43.2 | —20.1 | [246, 487) GO: salieylaldehyde (ig) = 7964 | 66.9 | [71, 134, 386] CHAO mheptaldehyde (ig) 10622 | —74.4 | [261, 326] Hic noctaldehyde (lia) =12189 | 80.0 | [161 formaldehyde (methunal)(3)—The cobras Fletcher and Pilcher {591} were prefered von Wartenberg and Lemer Steinberg (558 acetaldehyde (ethanal) (g)—The heat-of-hydrogenation data of Boller, Gresham, Kistakowsky, Smithy and Vaughan [139] were used as the basis of our selected vale rather than the early combustion data of Berthelot and Ogier [65]. acetaldehyde (ethanal) (lig)—'The heat of vaporization of ethanal as determined by Coleman and DeVries [105], 6.24 heal mol”! at 25°C, was combined with the heat of formation of gaseous acetaldehyde. The combustion dita of Berthelot and Delepine (09.50), and Toth and Miiller [406] were not use¢ ‘propionaldehyde (Ipropanal) (liq)—he. combustion data of Thee [34] wore veed to obtain the selection ‘The data of Berthelot and Delepine [49, 50] were not used. yceraldehyde (liq)—Baer and Flehmig [17] give Foe Ley ae tanner hat tine rebut ade tata (lg) ~The eombuston data of Tjebbes [534] and Nicholson [326] were averaged to take the selection. ‘acetone slyceraldehyde (liq)—Baer and Flehmig [17] ive combustion data for Dand Isomers, but bee ative oftheir soam description of eslormeni procedure and results, we have assigned a single value to both isomers. fralchoe (lig)-—The ramtunston data Flschee Mortimer, and Springall (155] were used to obtain the selected value. The same data are given earlier by Cass, Springall, and White [90], but show AHc oaater by 02 heat out? The emt Louguinine [265] were not used. benzaldehyde (liq)—The combustion data of Landrieu, Baylocq, and Johnson [246] were chosen in preference to reer ant etna Rein and Heeeeee salicylaldehyde (liq)—The combustion data of Delepine and Rivals (134) were chosen in preference to the dats of Berthelot and Rivals (711 and Rivals (3861, Gf their scant description of calorimetric procedures n-heptaldehyde (liq)—The combustion data of Nichol- ae ral" tre have ansigned a single aelus to ail on [326] were cllosen in preference to the data of oo Eeueuinine (261) 6.9. Ketones Formula Compound (State) ‘AHc°298 K | AHf°298 K Reference eal mot | Keal mot cio propanone i) (acetone) =asosz) once] (anv, 99) CHO Propanone ig) (acetone) — | 427,92) 59:18 (49,50, 144, 351, 528 Ho Ihntanane (¢) (methyl ethyl sono] — —saoe| aS! ‘etore) cao botanone Gig) methyl ety! | —se4.7] —65.29| (217,344, 378,436 Ketone) 316] 4. Phys. Char. Ref. Dato, Vl. No 2, 1972HEATS OF COMBUSTION AND FORMATION OF ORGANIC COMPOUNDS Keton a Continued Formula Compound State) | AHe298 K | AH/298.K] Reference eal mot" | eal molt 23+butanedione (lig) 493.71] — 87.44) [245, 327, 381, 449] (iaceryd) 2pentanone (ig) (methyl n- | 740.78] — ~71.05 | [278, 516, 575) ropy! ketone) S-pentanone (liq) (diethy! = 740.96] —70.87| (178, 264, 406, 516, ketone) 575] acetophenone (ia) 991.60] —34.07 | 1109, 110. 462. 4881 Jbenzophenone (¢) =1556.2 | 8.0 | (22, 86, 108, 247, 402, 488] propanone (aceton)(@)—The combustion data of Miles {hd Hunt [310] were chosen in preference to the early dita of Thomsen I581L ‘ropanene (acetone) (ig) The heat of vaporization was taken fom the data of Pennington and Kobe (351) Srhap” 25-0570 eal a The ater ae was ‘omboed with the heat of combustion of eascous pro Parone. The combustion data of Berthelot and Deleping {39,50}, Emery and Benedict [144 and Taylor, Halland Ietonont (tial esto! eione) (ia)~'The comb jtanone (methyl ethyl felons) (ig)~The combustion data of Sinke and Octting [436] were chosen in prefer fence to any previous work. 2-butancdion (diarety (ig)~'The combustion data of ean Si ner EV Pa Mae eters and Vaughan [94i] were averaged to make the Selection, The data of Springall and: White (149) and 2pentanone (methyl npropyt ketone) (lig)—The com- inition data of Harrop Head, and Lewis [178] were pre- ferved to thone of Zabow (3251 ax corrected by Swietox: laws 316} S:pentanone (diethyl ketone) (ig) The combustion data of Harrop, Head, and Lewis 17H] were preferred 1 those of Roth and Miller [406]. Louguinine [268]. and Zubov {S75}as corrected by Swictoslawski [516]. ‘acetophenone (lig)—The combustion data of Colomina, Tatorre, and Perez Ossorio [109, 110] were chosen in jar 1g the early eombantion dats af Stohmagn 462], ‘and Stohmann, Rodatz, and Herzberg [488] enzophenone (c)—The combustion data of Colom Cambeiro, Perez-Ossorio, and Latorte [108], and Parks, Mosley. and Peterson {Uld] worn svnraend forthe selection. ‘The data of Beckers [22], Burriel [86], Landrieu, and Blatt [247], Stohmann, Rodatz, and Landrieu [245] were not used. Herzberg [488], and Stohmann [462] were not used, 6.10. Aliphatic Acids Formula ‘Compound Stato) | AMeR9EK | AH/29BK | Reference eal mol | Keal mol? CHO: form acd (a) methanic | —60.86 | —10181 | (4,89, 60, 208, 218, CHO: acetic acid (liq) (ethanoie 200.02 | —115.71 | [59, 60, 146, 248, i) 395, 416. 417] cH, propionic acid (ia) (propancie} ~365.08 | 122.07 }f2an, 96s, 417, 479, id) 43] Cath: butyric acid (ig) (butanoie | | 521.87 | —127.59 | (248, 472, 473) acid) Catt Ws volere acid (ig) (nemtancic | —67a.a2 | —199.71 | 2, 176, 249, 472, acid) 473) CaHla0s ceaproie acid (lig) (hexanoic | 934.49 | —139.71 |(3, 152, 248, 263] ty Cat.0, | ent acd ay (heptane | —yn.a1 | 148.75 | 13,248) ‘acid) CaO caprylic acid (lig) (octanoic | ~1187.00 | —151.98 | (3, 248, 266, 267] acid) Calle pelargonic acid (lig)(nonanoic| | —1303.62 61 | (3, 288, 266, 267, acid) 472,473) Coots acid (iqy(decanoic | 14601 | —163.6 | 2.3 ) CulOe | eapric acid (@) —1453.07 | 170.59 ][3, 457, 472, 473, (decanoie acid) 481) 4 Phys Cham. Rt: Dot, Vol. 1, No.2, 19726.10. n-Aliphatic Acids—Cor Compound (State) laurie acid (iq) Cull: (dodecancie acid) CitlsOs | lure aide (dndecanaic =n) Cutts | myratie acid (lig) (tetrade- anole se) Cua, | myrntic acd 0) (tetrad ancieaci), Citic: | palmitic acid (ig) (hexade- ic ai) Cds tilly esade- cance acid) CabtnOs | wees hy oo Cue cai ace) (otadecanvie Cote Jc aid (ia) hen ‘apole eck) Calas | arachitc ci () ctomanoie Ctl, formic acid, (methanoie acid) (lig—The combustion ‘tata of Sinloe [iB4] grove ased\te cbaein the selested value. The data of Lebedeva [248] are in excellent ‘agreement with the selection. ‘The data of Berthelot {58}, Berthelot and Matgnon {59, 60, and John [20] ‘acetic acid, ethanoic acid) liq)—The combustion data ff Evans and Skinner (146) ‘were used to obtain the Selected value. The data of Lebedeva (248) are in fxcollent ereement with the aeleetion, ‘The data of Berthelot ‘and’ Matignon [59, 60), oi [595], and Schjinberg [416, 417} were not used, although oniy the data of Roth [395] appeared to deviate from the selec- ton bv more than 0.3 keal mol" propionic acid, (propanoie acid) (lig)—The combustion ata of Lebedeva (248) were chosen in preference t0 the previous data matyrn acid, (cutangie ari) (iq)—The eombnation. ‘dana of Lebedeva (248) were chosen in preference t0 the early data valerie acid, (n-pentanoic acid) (lig)—The combustion Anta nf Lehedowa [248], and Adviaanse. Dekker. and Coops [31 were averaged to obtain the selected value. ‘The data of Hancock, Watson, and Gilby [176] agree well withthe early work of Stohmann, Kleber, Langhein, 2nd Oren (572.4731. Data fromthe later thece references were not Us meaproie acid, (-hexangic acid) (tig)—The combustion data of Lebedeva (248), and Adriaanse, Dekker, and Goons [31 were averaged to obtain the selected value. ‘Thevdata of Fischer and Wrede [152], and Louguinine [268) were not used, ‘enanthic acid, (wheptanoie acid) (iq)—The combustion data of Lebedeva (248], and Adriaanse, Dekker, and ‘Coops 3] were averaged to obtan ie selection eaprylic acid, (n-octanoic acid) (ig)—The 2 thy Chem Bek ate Mal A 9, re AHe298 K Keeal molt EUGENE S. DOMALSKI AH p28 K eal mol-? (8, 176, 266, 267, “109, 474, 362} [3, 266, 267, 377, 451.414, 881, 542, 506) [2, 3,176, 298) (3, 144, 266, 267, ‘457, 472, 473, 506) (3, 248) (3, 144, 248, 266, 308, 377, 410, 457, 472) 473, 481; 506) 2.37 [3, 472, 433) faa] data of Lebedeva (248] and Adviaanse, Dekker, end Goops [B)-vere averegrd to-obtain the cslostod valu. ‘The data of Louguinine [266,267] were not used. pelargonic acid, (n-nonanoic, acid) (lig)—The com- brstion data of Lebedeva [248], and Adrisanse, Dekker, tnd Coops [2] sero averaged te nbtsin the caloction ‘The early data were not used caprie acid. (redecanoie acid) (e)—The combustion data of Adriaanse, Dekker, and Coops [3] were chosen in tretarenra sath onrilr ata loarie acid. ( oie acid) (c)—The combustion data of Adriaanse, Dekker, and Coops [3] were chosen inpreferenee tothe earlier data. maristic acid (ntetradecanaie acid) (c)—The combus- tion data of Advaanse, Dekker, and Coops {3} were used to obtain the selected value, The data of Swain, Sitbert, and Miler [506], although not as precise, are in sood aareement with the selection. The early combus- palmitic acid, (n-hexadecanoic acid) (lig) —The heat ‘as determined by Adriaanse, Dekker, and ‘S| was selected in preference t0 that of sand’ combined ‘with the. combustion data onthe exysta palmitic acid, (n-hexadecanoie acid) (c)—The com: bustin data of Adriaanse, Dekker, and Coops [3] were Used to obtain the selected value in preference 10 the data of Lebedeva [248]. The data of Swain, Silbert, and Miller (506), although not es precise as either of the above data are in good agreement with the data of ‘Adriaanse, Dekker, and Loops 13). Data prot 10 the shove were not used. stearic acid, (n-octadecanote acid) (lig)—The fasion data of Lebedeva [248], and Adriaanse, Dekker, and Woops. [2S] were averaied to obtain the selected value, Ai(fusion) at 25°°C=140 Keal mol” and