1687
Enthalpies of Formation of Oxygen-Containing Organic Compounds
Revised Group Additivity Parameters for the Enthalpies of Formation of Oxygen-Containing Organic Compounds H. K. Eigenmann,' D. M. Golden," and S. W. Benson Department of Thermochemistry and Chemical Kinetics, Stanford Research Institute, Menio Park, California 94025 (Received December 4, 1972)
Data on AHr", the standard enthalpies of formation, in the gas phase for over 300 oxygen-containing compounds are critically examined. Internal consistencies within this set are scrutinized from the viewpoint of group additivity principles. New values for the contributions of groups to AHf", as well as higher order corrections, are obtained from multilinear regression analyses of the data. For alcohols and ethers observed values and group additivity values agree to within f l . O kcal/mol, which is about the experimental precision. The data on these classes are very self-consistent. Very nearly the same is true of aldehydes and ketones. Major discrepancies exist in the classes of acids and esters and a few key compounds deviate seriously from other members of their class.
1. Introduction In this report we wish to revise some of the group values for enthalpies of formation reported in our general review of group additivity2 in order to take into account the increase in data in the past 4-5 years, and the appearance of two excellent reviews of thermochemical data of organic compounds.3 The report is focused on oxygen-containing groups because lack ,of thermochemical data about esters, acids, and anhydrides in 1968 produced some ambiguities in the related group values. Similar revisions for entropy and heat capacity for this class of compounds4 will hopefully be undertaken in the near future. For a discussion of the basic concept of additivity rules for the estimation of thermochemical properties, the reader is referred to either the previous report or the original paper by Benson and Buss.5 Nomenclature and general presentation are maintained as in ref 2a. 2. General Discussion Sources for enthalpies of formation are the two mentioned reviews of Stull, Westrum, and Sinke3a and Pilcher and COX,^^ and a systematic inspection of the Bulletins of Thermodynamics and Thermochemistry, No. 10-15 (1967-1972). For the search on more recent results (19711972), the appropriate journals have been surveyed. The results found in either source, although sometimes questionable, were included in the first calculation of group values. The procedure used to eliminate inaccurate values is described below. Estimates of enthalpies of vaporization were generally adopted from the original papers and the two reviews mentioned above. In order to facilitate handling of the -300 enthalpies of formation, these were grouped for the calculation: one set containing only alcohols and ethers (Le., no carbonyls), the other covering aldehydes, ketones, acids, anhydrides, and esters. In each set, the most frequently occurring groups were determined by a multilinear regression analysis (MLR). Adopting the group values obtained by MLR, the less common groups could be evaluated. For all calculations, group values for nonoxygen containing groups were taken from the previous report.2a Assuming group additivity to be correct, it was possible to use multilinear regression in the process of eliminating questionable data; all data producing large deviations in
the predicted value after regression were subject to critical examination and were possibly excluded, if either the enthalpy of vaporization is estimated or the measurement dates back before 1940. Then, without the excluded compounds, MLR was used to reevaluate the groups. This procedure was applied several times and resulted in the group values discussed in section 3. In our previous reports2 several groups containing elements other than C, H, and 0 were assigned by analogy CB-0). As long as with oxygen group values ( i e . , CB-S these other classes of compounds are not revised separately, the values given in those reports must stili be used. 3. Results Tables I and I1 present the group values as obtained in this work. Table 111-a-i6 compare measured and estimated values for the compounds used in the first calculation (including compounds eliminated by MLR) . Compounds used in the final MLR are marked by an asterisk, those excluded by a dagger; compounds without a mark have been used for the calculation of the less frequently occurring groups. The original references for the measured data are given with the exception of those found in either review,3 which are marked as either 3a or 3b, respectively. In the following subsections these results are discussed with emphasis on chosen values for the groups and deviations from group additivity. International Fellow supported by Ciba-Geigy AG, Basei, Switzerland. (a) S. W. Benson, F. R. Cruickshank, D. M. Golden, G. R. Haugen, H. E. O'Neal, A. S. Rodgers, R. Shaw, and R. Walsh, Chem. Rev., 69, 279 (1969): (b) S. W. Benson, "Thermochemical Kinetics," Wiley, New York, N. Y., 1968. ( a ) D. R. Stull, E. F. Westrum, Jr., and G . C. Sinke, "The Chemical Thermodynamics of Organic Compounds," Wiiey, New York, N. Y., 1969; (b) J. D. Cox and G. Pilcher. "Thermochemistry of Organic and Organometailic Compounds," Academic Press, London, 1970. The group values of peroxides and related compounds have recently been updated (S.W. Benson and R. Shaw, "Organic Peroxides," Vol. 1, D. Swern, Ed., Wiley, New York, N. Y., 1969, p 106) and are not included In this paper. S. W. Benson and J. H. Buss, J. Chem. Phys., 29, 546 (1958). Tables II I a-i, "Comparison of Measured and Calculated Enthalpies of Formation," for ail species considered, will appear following these pages in the microfilm edition of this volume of the journal. Single copies may be obtained from the Business Operations Office, Books and Journals Division, American Chemical Society, 1155 Sixteenth St., N.W., Washington, D. C. 20036. Remit check or money order for $4.00 for photocopy or $2.00 for microfiche, referring to code number JPC-73-1687. The Journal of Physical Chemistry, VoI. 77, No. 13, 1973
1688
H. K.
Eigenmann, D. M. Golden, and S. W. Benson
TABLE I: Group Values for .hNf0298 Noncarbonylic Groups (kcal/mol) a -10.1 -8.1 -6.5 -6.5 -8.1 -7.2 -6.6 8.6 10.3 8.9
4.7
-5.8
0.5
1.2
-0.9 -16.1 -16.3 -18.6
16.6
-37.9 -37.9 -37.9 -37.9 -23.2 -30.5 -33.0 -23.0 -21.1
0.5 7.8
2.0
6.5
2.3
(0 gauche)
6.0
0 0
sn
3.3
26.8 0.2 25.2 6.6
5.9
4Determined by MLR. bC-(H)3(o)'= C-(H)3(C), assigned. 'Cd-(H)(O) =Cd-(H)(C), assigned. dCd-(C)(0) ==Cd-(C)2, assigned. eCd-(Cd)(0) Cd-(Cd) (C), assigned..{ 0-(H) (C) zs 0-(H) (Cd) E O - ( H ) (Ct) = 0-(H) (CB), assigned. g Based on methylallyl ether and allyl alcohol. ti Based on 2-propyn-1-01, rather than methyl 2-propynyl ether. The latter would imply an unexpectedly low group value. Based on ethyl vinyl ether, 2-ethoxyprop-lene, 2-methoxy-n-but-2-ene. J Based on dlvinyl ether. Based on methyl phenyl ether, ethyl phenyl ether, and 3-methoxy-1-methylbenzene. Based on diphenyl ether. m Based on dl-tert-butyl ether, n Based on ethylene oxide and propylene oxide. Based on tetrahydrofuran and tetrahydrofurfuryi alcohol. Based on furan and furfuryl alcohol. Q Based on tetrahydropyran and 2-methoxytetrahydropyran. Based on 1,3-dioxolane and the 2-methyl and 2.4dimethyl derivatives. SSee text. Based on s-trioxane. See text. u N o gauche correction is added for interactions of 0 with alkyl C or 0 along a C-C bond. "NO ortho correction is added for 0 ortho to alkyl C o r 0. Based on dibenzopyran using -7.2 for C - ( H ) ~ ( C B )(from ~ diphenylmethane) .3b
3.1 Alcohols and Ethers. The following parameters (group values) have been subject to multilinear regression: C-(H)z(C)(O), C-(H)(C)z(O), CB-(O), O-(C)(H), O-(C)z, 0-gauche, C-(H)2(0)2, C-(H)(C0)2, C-(C)2(0)2. The remaining groups were determined by inspection from the rest of the available data. Twelve of 78 compounds were excluded from multilinear regression by the principles explained in section 2. In the previous report2b we used a value of $0.8 kcal/ mol as the destabilization due to gauche interaction between 0 and alkyl carbon along C-C bonds in analogy to the value in hydrocarbons for gauche interactions between alkyl carbons. Some of the data on branched alcohols indicate that this value should be lowered. 0.3 kcal/mol would be in fair agreement with the reported conformational free energy of cyclohexanol.7 On the other hand, the differences in conformational free energies of l-methylcyclohexanol, which are reported to be 0.1-0.3 kcal/mol,8 imply a similar, or the same value for either gauche interaction. On the basis of the polyols where this strain often occurs several times in one molecule (as oxygen-carbon or The Journal of Physical Chemistry, Vol. 77, NO.13, 7973
oxygen-oxygen interaction), a stabilization, rather than a strain, would improve the agreement considerably. From a theoretical point of view, some hydrogen bonding may be responsible for this behavior. In this questionable situation we assigned 0 kcal/mol to this interaction. Although this is a compromise, it improves the general agreement, mainly with respect to the polyols. Similar arguments apply to the aromatic ortho interaction. The already fair agreement may even be improved by again assuming 0 kcal/mol as strain in the cases of 0 and C, or 0 and 0, ortho to each other. The value of the ether oxygen gauche correction, where the alkyl carbons are gauche along a C-0 bond, has been determined to be 0.5 kcal/mol from the MLR. In Tables I and 11, the best group values are summarized, and Tables 111-a, 111-b, and 111-c cover alcohols, ethers, and cyclic ethers and present measured and calculated values for these compounds. E. L. Eliel and S. H. Schroeter, J. Amer. Chem. Soc., 87, 5031 (1965). (8) J. J. Uebel and H. W. Goodwin, J. Org. Chem., 33, 3317 (1968).
(7)
Enthalpies of Formation of Oxygen-Containing Organic Compounds
1689
-7.6 -5.4
4.4
-58.1 -43.1 -45.2 -36.7 -46.5
3.0
-29.1 -29.1 -29.1 -29.1 -31.4 -30.9 -25.8 -26.0 -32.1 -35.1 -32.0 -36.6 -25.3 -29.2 -26.8 -29.3 -29.9
22.6
2.1 1 .l 5.4 11.0
Jk
4.5
0
6"
3.6
0
0.8 0
(y+Dtm
10.3
0
5.2
4k+tm 0
21.1
0
2.2
23.9 22.0
aSeefootnotea to Table I. bC-(H)3(CO) =C-(H)s(C), assigned. 'CO-(H)(C) =CO-(H)(Cd) ==CO-(H)(Ct) =CO-(H)(CB), assigned. dBasedon ethyl-, n- and isopropyl-, and n-butyl-3-pentenoate. e Based on benzyl methyl, benzyl phenyl, and dibenzyl ketone. f Based on furfuraldehyde and furoic acid. g Based on acetophenone, ethyl, n-propyl, and isopropyl phenyl ketone (see text). Based on methyl glyoxal and diacetyl. &Basedon acetic, propionic, and benzoic anhydride. Based on oxalic acid, diethyl oxalate, and diphenyl oxalate. Based on succinic anhydride (see text). Based on maleic anhydride (see text). mThe strain of pyromeiiitic anhydride is twice the strain of phthalic anhydride, as expected. Based on formic acid and methyl formate.
'
a. Alcohols. Most of the calculated heats of formation are within 1.0 kcal/mol of the measured values. The aliphatic alcohols are in even better agreement (*0.5 kcal/ mol). Big discrepancies occur with 2-naphthol (A), thymol (B), 1,3-propanediol (C), 1,3-butanediol (D), 2,3-butanediol (E), glycerol (F), diethylene glycol (G), l-erythritol (H), pentaerythritol (I), and triethylene glycol (K). For compounds A, E, G, and K, either AHf" or AHVap298 were measured before 1940. Furthermore, most vicinal diols (E,F,H) show a stabilization of 2-5 kcal/mol, which might be due to hydrogen bonding. The estimated enthalpy of
formation of thymol (B) is almost within the reported error limits. In the report on 1,3-propanediol ( C ) 9 the authors discuss the unexpectedly low value they have measured, but do not indicate any final arguments. The enthalpy of formation reported by the same authors for 1,3butanediol (D) shows the same behavior. No obvious explanation of the discrepancy with 1-erythritol could be found. (9) P. T. Gardner and (1972).
K. S. Hussain, J. Chem. Thermodyn., 4, 819
The Journal of Physical Chemistry, Vol. 77, No. 73, 1973
1690
H. K. Eigenmann, D. M. Golden, and S. W . Benson
An inconsistency exists between mono- and polyalcohols insofar as the predicted values for the former are mostly too negative, but too positive for the latter. This behavior is additionally accentuated by the fact that the polyalcohols have more statistical weight in the MLR due to the occurrence of more than one set of oxygen-containing groups in their molecules. In order to take into account the fact that enthalpies of formation of monoalcohols are generally much more reliable than those of polyols, we O-(H)(CJ 0have chosen 0-(H)(C) = O-(H)(Cd) (H)(CB), -37.9 kcal/mol, instead of -38.3, as calculated by MLR. b. Ethers. With the exception of a few compounds, deviations no greater than 11.0 kcal/mol were observed. The difference for methoxybenzaldehyde is -2.3 kcal/ mol, compared to a relatively big error of f 1 . 4 kcal/mol for the measured value. Diallyl ether, burned in 1929, shows a deviation of +7.3 kcal/mol, that may only be assigned to the group C-(H)z(Cd)(O). However, this group value is well established by the excellent agreement for methylallyl ether and allyl alcohol. The group C(H)2(Ct)(0) may be calculated from either methyl 2-propynyl ether or 2-propynyl-1-01, leading to -1.9 or -6.5 kcallmol, respectively. Although the enthalpies of formation of both compounds have the same source, we prefer -6.5 kcal/mol as calculated from the alcohol. This value is within the range suggested by the analogous groups C(H)2(C)(O) (-8.11, C-(HMCd)(O) (-6.51, and C(H)~(CB)(O)(-7.7). c. Cyclic Ethers. This class of compounds mainly determines strain parameters for rings. Usually, only a few derivatives of each particular ring system have been measured. Therefore, most of the strain parameters are based on not more than three measured enthalpies of formation. No considerable deviations are observed, except for the families of 1,3-dioxanes and 1,3,5-trioxanes. In the former case, additional strain is observed with tri- and tetramethyl substituted derivatives which have been excluded from the calculation of the 1,3-dioxan strain. However, part of these discrepancies may be explained by taking into account the strain observed in the structurally similar diisopropyl and isopropyl tert-butyl ethers (0.7 and 0.4 kcal/mol, respectively). The enthalpy of formation of 5,5dimethyl-1,3-dioxane should be remeasured in order to clairfy its surprising extra stabilization of 2.5 kcal/mol. In the latter case, enthalpies of formation of s-trioxane have been reported to be -111.32 (Monsson, et al.IO), -116.1 (Busfield and Merigoldll), and - 120.8 kcal/mol (Snelson and S k i n n e P ) . We have adopted -111.3 kcal/ mol, a value that leads to a strain of 6.6 kcal for this compound. Furthermore, - 111.3 kcal/mol is in agreement with the earlier measurement of Busfield and Merigold11 if their value is corrected for the recently redetermined enthalpy of formation of formaldehyde13 (-26.0 instead of -27.7 kcal/mol). More experimental and theoretical knowledge are needed to explain the unexpected stabilization of the trimethyl derivative.14 3.2 Aldehydes, Ketones, Acids, Anhydrides, and Esters. In the calculation of groups of carbonylic compounds, the previously determined groups of alcohols and esters have been adopted as given in Table I. Of the remaining groups, the following were optimized using multilinear regression (MLR): C-(H)2( C)(CO), C-(H)(C)z(CO), C(c),(Co), c~-(co), Cd-(H)(CO), CO-(H)(C) co(H)(CB)E CO-(H)(Cd), co-(o)(c),c o - ( o ) ( c ~ ) ,co(o)(cd), 0-(CO)(H), 0-(CO)(C), O-(CO)(C,). In order N
The Journalof PhysicalChemistry, Vol. 77, No. 13, 7973
to maintain linear independence between the groups, we had to modify some of the optional assignments of values to groups, mentioned in the previous report.2a In analogy to C-(H)dX), all groups, CO-(H)(X) (X = C, CB, cd), were assumed to be equal. Furthermore, the previous assignment, CO-(O)(C,) = CO-(O)(C,), could be avoided. Due to the higher numbers of compounds and parameters, the process of elimination of erroneous enthalpies of formation was more complicated than with alcohols and ethers. Finally, 97 to 123 compounds remained in the final set for mutlilinear regression. Twenty-six compounds were excluded on the basis outlined in section 2, and by some additional criteria that are explained in the context of Tables 111-d-i. The resulting group values differ in part from the values reported earlier. The standard error of estimation, calculated on the basis of the 97 selected compounds, was lowered to 1.4 kcal/mol. On the basis of all 123 compounds, the improvement is 0.9 kcal/mol (4.4 kcal/mol using “old,” 3.5 kcal/mol using “new” groups). The improved group values are listed in Table 11. Those not calculated by MLR have been determined by inspection, using the groups already calculated. Tables 111-d-i compare measured and calculated AHf” values for all compounds used in this compilation. a. Aldehydes. Except for 4-methoxybenzaldehyde and furfural, both measured 1940 or earlier, no severe deviations occur. b. Ketones. Due to its obvious strain, di-tert-butyl ketone had to be excluded from the original data set for MLR. Its strain is surprisingly high (6.5 kcal/mol). By inspection, the enthalpies of formation of three ketones measured by Geiseler, et al.,l5 are too positive by 5-6 kcal/mol. They have been rejected in the final MLR and should be remeasured in the future. Some minor strain is observed with sterically hindered species like methyl tertbutyl ketone (0.8), diisopropyl ketone (0.7), and isopropyl tert-butyl ketone (1.3 kcal/mol). Within the remaining compounds the trimethylacetophenones show large deviations. Their enthalpies of formation are based on measurements in 1941 and an estimate of The group CO-(C)( Cg) has been calculated without these two values. Otherwise, calculated and measured values differ by less than 1.0 kcal/mol. c. Cyclic Ketones. In this class of compounds, each strain parameter is based on one particular enthalpy of formation. Furthermore, the enthalpy of formation of bicyclo[3.3.0]octanone is calculated by the help of an estimated enthalpy of vaporization. Therefore, at present no discussion in terms of group additivity is possible with these compounds. d. Acids. Within the acids more deviations from group additivity seem to occur than elsewhere. Therefore, a relatively high number of compounds had to be rejected before the final MLR. Beginning with tetradecanoic acid, all higher aliphatic acids were excluded in order to avoid influences of non-nearest-neighbor interactions onto the group values, Suberic, sebacic, and dodecandioic acid have not been used in the final fit. Their combustion (10) , . M. Monsson. E. Morawetz, Y , Nakase, and S. Sunner, Acta Chem. Scand., 23,56 (1969). (11) W. K. Busfieldand D.J. Merigold,J. Chem. Soc. A , 2975 (1969). (12) A. Snelson and H. A. Skinner, Trans. Faraday SOC., 57, 2125 11961). (13) k:A. Fletcher and G. Pilcher. Trans. Faraday Soc., 66,794 (1970). (14) K. Pihlaja and M. L. Tuomi, Suom. Kemistilehti E, 43,224 (1970). (15) Methyl phenyl, propyl butyl, and ethyl pentyl ketone [G. Geiseler, N. Ratlevszh, K. Ebster, and I. Ziegel, Ber. Bunserges. Phys. Chem.,
70,221 (1966)l.
1691
Enthalpies of Formation of Oxygen-Containing Organic Compounds dates back to 1926, and all of them show an apparent high strain. Finally, the enthalpies of formation of maleic and fumaric acid cannot reasonably be fitted within the rest of carbonylic compounds. Their calculated enthalpies of formation are +7 t o i-9 kcal off the measured value. Both have been discarded. Within the remaining set of compounds, most discrepancies occur in aromatic acids. They find their counterpart in aromatic anhydrides and esters, but benzoic acid is the most prominent disagreement. Excluding benzoic acid would considerably improve the consistency of the rest of the data. A redetermination of its heat of sublimation should be undertaken in order to establish a more reliable value for the important group, CO-(O)(C,). e. Anhydrides and Related Compounds. No MLR was carried out on these strained species. First, by using acetic, propionic, and benzoic anhydride, the group 0-(C 0 ) z was determined. The consistency of O-(CO)z within these three compounds is as bad as f.3 kcal/mol. Nevertheless, the averaged value of this group has been used to calculate strains of the intramolecular anhydrides. In the case of succinic and maleic anhydride, the methylated homologs have been neglected for the calculation of the respective strains. The available data indicate, for both molecules, extra stabilization of the methylated derivatives, although the enthalpies of formation are based on measurements earlier than 1942. f. Esters. Although a considerable number of enthalpies of formation are reported, many enthalpies of vaporization are estimated and a lot of measurements date back before 1940. Therefore, we had to exclude from MLR a high number of compounds by the procedure described in section 2. Within the remaining major discrepancies, we eliminated all data leading to deviations too large to be corrected by a reasonable change of group values (ie., glycerol triacetate, A = -10.2; alkyl esters of phthalic acid, A = -10 to -15 kcal/mol). Although a critical review of these data is beyond the scope of this paper, some additional comments seem to be in order. The group CO(H)(O) has been determined on the basis of the recently measured enthalpies of formation of formic acid and methyl formate, neglecting ethyl and allyl formate, both burned in 1929. The enthalpy of formation of ethyl propionate reported by Pilcher and COX^^ should be corrected to -112.2 kcal/mol due to an-arithmetical error. All isomeric butyl pentanoates show extra stabilization, probably due to a systematic error. The data reported by Hancock, et a1.,I6 (esters of a-methylbutyric, isovaleric, and
pivalic acid) lead to predictions positive by -3-5 kcal/ mol, again possibly a systematic error. (For methyl pivalate, a more recent value is in better agreement with group additivity.17) All enthalpies of formation of esters of the isomeric pentenoic and pentynoic acids are based on estimated enthalpies of vaporization. For methyl cis-9octadecenoate and the diesters of phtalic acid, the reported error limits already account for *3 kcal/mol. All enthalpies of formation reported by Carson, et produce deviations of the order of 3 kcal/mol (benzoic anhydride, diphenyl oxalate, and phenyl benzoate). However, for two of these compounds there exist previously reported values which are in better agreement with group additivity (benzoic anhydride = -79.9,19 and phenyl benzoate = -37.5 kcal/molZO). Part of these discrepancies may furthermore be due to the general inconsistency of data on aromatic acids, anhydrides, and esters. Nevertheless, except for the compounds mentioned above, deviations generally remain within f1.5 kcal/mol, nearly as accurate as in the other classes of organic oxygen compounds. 4. Conclusions
The group values presented in this report are based on a considerably increased number of experimental data and predictions are mostly within k l . 0 kcal/mol. We feel, therefore, that data leading to discrepancies of more than 2 kcal/mol should be reexamined carefully in each case. Either unexpected strain or stabilization may be the reason for this behavior, or the reported values are less accurate than is indicated by the precision listed by the authors. Typical examples are the aromatic acids, where the heats of formation of the alkyl esters are not compatible with that of the unsubstituted acid. A similar situation exists in the case of trioxane. The trimethyl derivative is far from the prediction based on trioxane itself. It is our experience from dealing with a large amount of thermochemical data that the method of group additivity is not only useful for the prediction of thermochemical values, but also as a tool in estimating the internal consistency of data for homologous families of compounds. (16) c. K. Hancock, G. M. Watson, and R. F. Gilby, J. Phys. Chem., 58, 127 (1954). (17) H. K. Hail, Jr.. and 2. H. Baldt. J. Amer. Chem. SOL-., 93, 140 (1971). (18) A. S . Carson, D. H. Fine, P. Gray, and P. G. Laye, J. Chem. SOC. 8,1611 (1971). (19) J. W. Breitenbach and J. Derkosch, Monatsh. Chem., 81, 689 11950). ---* (20) G. P. Adams, D. H. Fine, P. Gray, and P. G. Laye, J. Chem. SOC. 6, 7 , 720 (1967). ~I
\
The Journal of Physical Chemistry, Vo/. 77, No, 13, 1973
