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    Combustion - Heat of Formation - 1996 - Cohen

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    Revised Group Additivity Values for Enthalpies of Formation (at 298 K) of Carbon-Hydrogen and Carbon—Hydrogen-Oxygen Compounds N. Cohen ‘Thermochemical Kinetic Research, 6507 SE det Avenue, Portland, Oregon 97202 8627 Receive ans 17,19: revised manic ese September 4, 1996 | ‘A program laws bee vunletshen for te evaluation su revision of group advity values (GAVs) necessary for predicting, by means of Benson's group additivity method, thermochemical properties of organic molecules. This review reports on the portion of that program dealing with GAVs for enthalpies of formation at 298.15 K (hereinafter abbrevited as 298 K) for earbonhydrogen and carbon-hydrogen~oxygen compounds, ‘A complete database of experimental data for gas, liquid, and erystal (slid) phase en- thalpies of formation is presented. The GAVS, ring strain corrections, and non-nearest neignbor ineractons defved trom the aatabase are presented in tapular form, togetner with a description of their evaluation and comments on reliability, uncertainties, and missing or questionable data. © 1996 American Instite of Physics and American Chemical Savion Key worden of formation; etinaton; group sidiviy: erie compounis: thrmochemial pores Contents and engineers. It is also accepted that the range of molecules 1. Inoduction.....-.- 1411 of possible itrest will for the foresecable future, exceed by 2 Ress and Pewee 1411 orders of magnitude the number of compounds that can be 2.1. Entalpes of Formation. 411 measured inthe laboratory. Hence, simple bat eile tech 22, Group Additvity: A Brief Description... 1412 niques are desirable for estimating thermochemical prope- 23, Procedure. 1413 ties of species for which experimental data are not available. 2.8, The Database 1413 A number of metiods nave been developed in recent years 2.5, Format of the Tables 1414 while Were is not unanimous agreement regarding the best 216, Questionable and Undetermined Group method, it seems generally agreed that one of the best (not Values 1418 the best) is that of group adits, especialy as developed 2.7. Non-Nearest Neighbor Interactions. 1415 by Benson and co-workers.' Not only is the method fairly 28, Summary and Conclusions, 1417 easy to apply, but it usually can estimate properties with an 3, Tables of C-H-O Compounds 1418 uncertainty no lage than typical experimental uncerintes. 4. Acknowledgments 1481 In adation to containing a description of the method, Ret 1 5. References. 1481 tabulate the best available group adiiiy values (GAVS) for gas phase properties as of 1976 List of Tables Under» contact fom the National Intute of Standards 1. Group adaivty values for enthalpy of formation and Technology (NIST), we have underaken a program for (298 K), C-H-O groups. 1418 the evaluation and revision of GAVs necessary for predict 2 Comparison of group additivity values, Entalpy ing, by means of Benson's method, thermochemical proper- ot formation (298 K. 1482 tes of organie molecules, 41. Carbon-ydrogen compounds: Enhalpy of formation (298 K). 135 2. Results and Procedure 4. Gatton hydrogen compounds (HO ° Enthapy of formation (298 K). 1432 2.1. Enthalpies of Formation Carbon-hydrogen compounds (C, 1,0, ‘merous tabulations of thermochemical properties (i 6 Carbon-hydrogen compounds (C,H1,0,.2): have been published. The starting point for most subsequent Enthalpy of formation (298 K). 1472 tabulations has been “Selected Values of Physical and Ther ‘modynamic Properties of Hydrocsrbons and Related Cont 4. Introduction pounds,”” by Kossint e7 al? However, this compilation com- bined experimental values with calculated and extrapolated ‘The importance of reliable and conveniently accessible ones in a manner that did not always make clear which were hermachemieal data (enthalpies of formation, entropies, and which Stall, Westrim, and Sinke (SWS) perpetuated this ‘heat capacities) is universally accepted among both scientists uncertainty in their tabulations of thermochemictl properties 0047-2699!0625(6/1411/71818.00 141 ‘J. Phys: Chem. Ret. Data, Vol. 25, No.6, 1996 1412 into no-familiar JANA oat Thos impstant tronces have been cited primary sources in more receat ompilstions, ott now one i often hard-pressed to deter: mine to what extent paricalar compilation is dependent on onesperimentl valves, This ise. gains in Apoance enone tiesto develop empire! methods for predicting thermochemical proper, asin the group adiiiy Imcthod ill the Rovrnt ond SWS vals are thrown ino the hoppe, one in effec fing to already ited values Cox and Pilcher! began » program to establish the experi mental databne anew, and 0 laily the qesion of what ‘actly has been measured and what has not That stay ‘ulminatd inthe monograph by Pelee a, Thermochem ‘cal Data of Organic Compounds* (PNK). That compilation it ill the soundest starting point for any compilation of experimental enthalpy of formation data.” Several wotkers have temed to Benson's group ditty method for pedcting thermochemical properties. Ap exem- plary msde! is Stein's computer progam, avaible trgh NIST.’ However, such programs and projects often build on previous evalatons in way that does nt always ensure Auta! cooing of all of te eparte prs of te evar ation, For example, most group values ae derived in stp tise fashion, stating with groups ofthe alkanes. If thea ne aroup values are updated, amos all othe oop values Wl be affected, There is thas a clear need to reestablish a Uniformly derived set of GAV evaluations. Hence, the mot Nation forthe present projet. ‘Out approach was sir io dat Of hers nat we be gon by deriving GAVS forthe alkane groups Using 3a da tabase all the alkanes themselves.* The alkane groups, to- othr with he devin vals fal tne phase. are son inthe fst section of Table L. With these values Bed, we then tumed to al alenesodeive GAVS necessary fr tose compounds. These groups and thee derived GAVS ar listed inte send secton of Table 1 These Were rowed In Steps by alkynes and then aromatics and polyeycie t- tether, Gas, guid and ert phase GAs were derived in pera het porlel_svowisee Afer all the. extn iron groups were evaluate, carbon-hydrogen-oxyeen sroups were addesed The GAVs developed in this report are based solely on experimental deta ton eacuaa values, Whe tee at tmany computational schemes (including soup adv) that are eltely sucessful in predicting enthalpies of fr Iaton:lid mot nem appropriate 0 thom 2 derion GAVs Our enthalpy database therefore, omits some species included in other compilations (1, SWS) because ofthat tigorus consti. The reiblty ofthe GAVs is discussed, together th discussion ofa higher level analysis of GAVS and their expected reltonships to each other. Gaps inthe GAN roster ae cscussed, with suggestions for estimating 2.2. Group Adaitivity: A Brief Description vor singe the efforts of Fajane and. Kharsech in the 1920s. there have been numerous efforts to reduce thermo 4. Phys. Chem, Ret Data, Vol. 25, No. 6, 1986 N. COHEN chemical properties of organic compan to 4 set of hori and group energies. In 1958, Benson and Buss! discussed 2 hierarchy of aditvity schemes, and established a conceptual framework that provided a physical justification for the approach." In this hierarchy, atomic additivity i the fist level of approximation; the second and third are bond addi- tivity and group additivity, respectively. Atomic aditivity (Ge, « pativulat molecular property ean be evaluated as the ‘sum of contributions from the constituent atoms) is valid for such simple properties as molecular weights, but cetainly not for thermochemical properties. Bond additivity (Le. a ‘molecular property is the sum of eontibations from each bond in the molecule) thus constitutes the fist nontrivial level in the Benson and Buss hierarchial scheme, and can often provide useful estimations. ‘A group is defined by Benson"? as “a polyvalent atom (liganey 22) in-a molecule together with all ofits ligands.” ‘A group is writen 0s X(A)(B),(C)(D),. where X is the central atom attached to | A atoms, j B atoms, et. Inthe present discussion only C, H, and O aioms are considered, so that X is necessarily a carbon or oxygen atom, Several dif ferent types of C atoms are distinguished and notated dis tincly: sp* (C). sp? (Ca). sp (Ca), aromatic sp? (Cy), fused sing aromatic (C,,) and allenic earbon, =C= (C,). Cyy can ‘be bonded only (0 Cy, oF Cy Cy Is necessarily bonded wo rw C, atoms, Two oxygen-containing group families in which the central “atom” is polyatomic are defined: carbonyl (5C=0) and >CC=0, both of whieh have rao variahle Tigands. Tn addition, there are corrections for nonbonded interac- tions that are required because of spatial interactions that are not defined in terms of a series of chemical bonds: the most common are the 1.4, or gauche, interaction of two methyl groups, and the cis and ortho intecactions. The presence oF absence of these corrections depends on intcractions of parts ‘of a molecule, whose proximity is not implicit in bonding alone. These considerations pose problems for any algorit mic apnenach to additivity schemes, without which the cod fication of computerexecutable procedures for calculating thermochemical properties would be almost trivial. Osher spatial correction terms required are the 1,$ interaction of tio substiuents such as CH, ene—)me interactions, and sterie hindrance comtetions for certain substituted phenan- threnes and naphthalenes. More cumbersome isthe fact that ‘eannot be derived on the basis of groups themselves. Unfor- tunately, this enlarges considerably the table of fundamental values that are needed for predicting enthalpies of arbitrary ‘compounds ‘One significant effort has been made 10 extend additivity to the next higher level beyond groups, namely. that of com Donenss, However, sine ihe nus of Feyuired parameters inereases rapidly with each blerarchieal level, the method of ‘components sufers series drawback relative the group a alitvty in site of ite oneepnal soundness The method bas ben criticized elsewhere." REVISED GROUP ADDITIVITY VALUES FOR ORGANIC COMPOUNDS 2.3, Procedure ‘Once the database was compiled (see Sec. 2.4), GAYS. ‘were taken from earlier publications"! and then succes- sively modified to minimize a weighted average error (de- fined as the experimental value minus the calculated value). “This process cannot be described in purely algorithmic terms (as, for example, an unbinsed mulilineae regression analysis) for several reasons First, some molecules were given greater weight than others by virtue of their smaller size (hence fewer different groups involved and smaller cumulative un- certainties), greater number of reported “measurements (hence, sometimes, greater accuracy and/or precision), ot ab- sence of structural complexities that might invalidate the limpliicativus idiisat ie grow blivty antl De~ cause of their unavoidably large experimental uncertainties, very large molecules (say, Cyq's and larger) are not particu- larly useful for derivine GAVs—unless there are no other sources for a particular GAV. Second, values derived for one phase (gas, liquid, or crystal (generally called ‘solid inthis repor})] were taken into consideration in deriving values for fanotner phase, rnysicaly, one Would expect GAYS 10 In- crease from solid to liquid to gas phase, but the statistical nature ofthe analysis can lead to small deviations from this fonder Large differences in values for different phases— particularly if the gas phase value is larger (i.e, more posi- tive) than liguid, or iguid larger than solid—are taken as sign of some inconsistencies in the database. Additionally, closely related groups are expected to have similar GAVs, as Table 2 shows. Exceptions to this guideline are generally cases where there is considerable uncertainty in the derived GAs, Finally, values sere recalculated after the omission cof a small handful of compounds which, by vite of paticu- lary large rors, seemed to be experimentally unreliable oF else beset with other difficulties. Molecules with ring structures posed special problems. Afr all the group contributions toa ringed compound were taken info account (but nor any corrections for gauche or fouret nou-nearest welghbur MMELACUONS WHR ie Fy Ue self), any remaining disagreement between experimental and calculated enthalpy was assigned to a ring strain correction (RSC) term. To clarify this procedure: if for example. one ‘were using 3.4-dimethyleyclopentadiene to evaluate the RSC for the eyclopentadiene ring, any cis or rans effects of the methyl side groups would be taken into account, but not any cis Contributions trom the ring members themseives. In ‘many cases, there was only & single compound with the aiven ting structure, so that there is considerable uncertainty in the assigned RSC. In the assignment of RSCs for complex structures, one is tempted (0 ty to reduce a ring structure to & sum of its various pans in order to minimize the proliferation of RSC terms, Thus. for example, one might hope to take into ac- ‘count the ring correction in indene by summing the corree- lions for benzene and cyclopentene: or of triquinacine by a sum of thee eyelopentadiene rings. In many eases, such o3 timations are good to 10-15 kJ/mol. which may not be much 1413 larger than experimental uncertainties. However, generally theoretical structure calculations show that the bond angles and lengths inthe more complex structures are different from those of the individual ring elements, so there is ood reason rot {0 succumb 10 the temptations of Occam's razor, not- withstanding the benefits that might result from shortening the tables of parameters. Allin all, the profusion of RSCs snus be egarded, if not as « shortcoming of group dltivity. at least as a limiting boundary to its domain of usefulness, Fortunately, there lie well within that boundary such an abundant number of compounds that there is litle justice in ‘questioning the method's utility, 2.4. The Datab ‘The database was assembled from several sources, bezin- ning with PNK, which we have found to be an excellent Dang pia Deane, whe may wasn conan, Ue authors paid scrupulous attention to which values wer in- deed the results of measurements and which, on the other hand. were deduced by theory or estimation techniques. (Many of these latter methods are not to be exitcized—and ‘certainly have their uses—butin a program aimed at deriving ‘GAN ftom the best experimental evidence availabe, incor pation of values obtained Uy theory ox eatin ss the Fisk of circularity of argument) A numberof the most com- plex polyeyelic compounds listed in PNK (generally tricyelo- and tetracelo- species) were omitied because their ‘complex ring. geometry, which gave them unique RSC, rade them unlikely to be useful in generatized estimation program, To the data taken from PNK were added exper ‘mental data recorded in several oxher useful compilations by Stein etal,” Lias etal," Domalski and Hearing.” and Pedley-* References 7 and 14, limited to gas-phase data only, were used selectively, because of the heavy reliance in both on estimated data, SWS includes a tabulation (their Chap. 14) of data forall phases that is annotated as 1 reliability data that seemed sufficiently reliable (their category ““A" of "B'") were incorporated info ths database. AN. important early thermochemical compilation by Kharasch, tabulating experimental heat of combustion data from the 1880s fmugh 1076, included» pioneering effort to develop simple empirical rules for estimating enthalpies of combus- tion, Because the reliability ofthe sources has not been vet fied (most of them are designated category “C” by SWS), these data (unless they appeared in PNK) have not been in corporated into the database. However, this compendium has been searched to extract afew ational GAVS (highly ten- tative at present), which are noted in Sac. 2.5 below. A few other sources were also consulted as they became available.” but the present database should not be consid- ered asa thorough review of all the published literature. Tn general, it has not been possible in this project o evalu ate independently the reliability of individual experimental data, Except in a few cases where errors were readily appar- cnt, the expsrimental data hove been eccepted ay recorded previously."**" One of the best flags to possible exper 4. Phy. Chom. ef. Data, Vo. 25, No. 6, 1986 1414 mental errors is a large discrepancy between experimental and calculated values—especially if other, closely related ‘compounds show no such discrepancy. ‘The database given in tis ance is partitioned, for con vemence oF nanaiing, imo Tour Lables. Ine hist, Laie 3, lists all C,H, compounds; Table 4 lists all C,11,0 com: Pounds; Table 5 lists C,H,0; compounds, and Table 6, ‘though subsite CHO, ince all compounds with thee ‘or more O atoms. The order of listing follows that of PNK: among the C-H compounds, the C subscript isthe fist de- ‘erminan, followed by the H subscript, with listings in as- ‘ending numerical order. Among the C-H-O compounds, the O subscript isthe frst determinant, the C subscript isthe second, and the H subscript isthe lat. Following the chemi- al formula i the parnthotoal index secigned by PNK. wa bookkeeping convenience. Compounds taken from sources ‘other than PNK (or its successor, Ref. 6) lack such an index. Data for gases, liquids, and solids are tabulated in successive sets of columns. Following the column labeled “Expt” is ‘one labeled “Ref,” which is lank if the source was PNK. Other sources are identified by initials or alphabetic refer- ences that are cit a the end ofeach table, The next column lists the enthalpy of formation as calculated by group addi- tivity, using the values of Table 1, The column headed “A ives the discrepancy between experimental and calculated Value (4=Expt-Cale). It should be noted that we are make ing no prejudgments whether the difference is a result of ‘experimental inaccuracy, inaccurate GAVs, or breakdown of total of 992 compounds inthe gas phase, 935 in the liquid phase, and 590 in the solid phase, 2.8, Format of the Tables The evaluated GAVs, RSCs, and non-nearest neighbor teractions (NN) ae listed in Table - The fist column lists the group, defined in the manner inaugurated by Benson.! (Some practitioners have advocated revising this nomencla- ture, but UecaUSe Me majorly OF user ae fama wi Me terminology of Re. 1, we have chosen not to revise it at this time.) The terms for C-H compounds are listed first, fo: Towed by those for C-H-O compounds. For each of the three sts of terms, a column headed "#” lists the number of ifferent compounds in the database in which the pertinent GAY. RSC. or NNI appears. (Multiple occurrences of one GAY ina single compouna count as only One appearance.) A +" sign indicates more than nine compounds. Since GAVS that are derived from only 1. 2, or 3 compounds may be cuhjact to pailarly large sorartaintins, Fomine tthe ‘able identify the compounds used in the evaluation in such cases. These may well signal instances where experimental data ought 10 be reevaluated or supplemented by measure- ‘ments on other compounds with the group in question. As explained in a previous report and noted above. one would expect each liquid phase GAV to be on average about 1 Limal 1 kealimal) emaller (ox laze pocitve) then tho corresponding gas phase GAV. and the corresponding solid 4 Phys. Chem. Ret, Dat, Vol. 25, No.6, 1996 N. COHEN phase GAV smaller than the quid GAV by less than 4 ki! mol Table 1 shows that these expectations are often bore cut, but by no means invariably. We ave no ventured t fill Jn the lacunae inthe able by applying this prediton, bain the event at estimations are needed for phases OF Which some GAVS ae lacking, such a procedure would provide & 00d fist gues. 1h one special cat, a group valve has been derived ind recy, rather than from experimental data eating to a mole cule that contains the group. This isthe case ofthe O-(0), sr0up, derived in detail fr the gas phase by Nangia and Benson,” but revised in accordance with more recent expt rental data.*| In most cases, GAVs and RSCs are listed 10 one signif. sat gute pot inal pt (Oo Od eau). Tn Should not be taken as implying a precision or accuracy of that magnitude: in most cases the uncenainty is considerably seater 2-6 kmol or 0-15 kealmoll. Ina few cases. paricularly with GAVs or RSCs derived from a single ex perimental datum, the values are listed only to the nearest ‘mol or kealmol: this indicates an uncertainty of several ‘mol or Keaimol. In general, ough, the numberof occur renoes of GAV, RSC, or NNI rater than the number of significant figures in tabulated entry, isa bette indicator of the aruracy ofthe asin vale “Ten GAVs in Table {are given in brackets. These have been derived. from data listed. in the compilation by Kharasch.” Because the reliability of these experimental studies has not been ascertained, these valves must be Te garded as temttive at this time, and ceanly subject to con siderable uncertiny. Because no compounds in Tables 3-6 have those groups, these GAVE have sect onthe eal lations im thoe tables “Table | includes numetical values in both keanol and fmol in successive columns. Because the original data ‘were taken from a variety of sours, twas moe convenient to use kcal/mol asthe units in which the data manipulations were actualy cried out Tobie 2 yivrhies « vonpaisun uf he OAVs gain according tO group stuctre. That is ll C-( (Hy aroups where the enpry parentheses canbe filled by either C, Cy. Cy, oF C., are grouped together. The similares in GAVS for many such groupings is stiking, and often refets the ‘ality ofthe bond adtivity approximation, The use of his, table is ciscussed futher in Sec. 2.6 below. Values are given All daa in Tables 3-6 ae in k/mo. These tables provide data for C-H, C-H-O, C-H-03, and C-H-0,=» com True, repetvely The format i the cae “Th fe tin fists compound name, often in more than one form {IUPAC and common names) forthe user's convenience “The second column gives the empirical formula, followed by 4: parenthetical index number that is used by PNK an their compilation. The thed column gives the Chem. Abstacts Regisry Number, if one hasbeen found. The nxt fou cl- perimental value, reference, group addivity calculated REVISED GROUP ADDITIVITY VALUES FOR ORGANIC COMPOUNDS value, and the difference between experimental and caleu- lated (experimental-calculated). If there 18 no entry in the “reference column, the datum is taken from PNK. In most, cases, we accept their evaluation of the best experimental ‘alsin afew eases where we have sccepted another valne 4 footnote indicates the reason. If there is an entry in the references column, itis identified by footnotes atthe end of the table. The same set of four entries then follows for liquid and solid (crystal) phases. thas frequently been the practice to refer to original pa- pets by the Keyname used by PNK (or by one of the other Secondary compilations upon which we have drawn). Any critical user ofthese tables will want to have PNK available for reference; therefore we have not felt obliged to repeat their complete journal citations. The extent to which this present work relies on PNK should not be underestimated, though in some instances it has not aceepted their recom: ‘mended evaluations for reasons given in notes. 2.6. Questionable and Undetermined Group Values ‘As Table L shows, in large number of easoa (paioutaly among the RSCs) there is but a single compound upon ‘whose enthalpy of formation the evaluation ests. There are also many with only two of three sources, often with signifi- cant discrepancies among the reported measurements. These instances are footnoted in Table 1. These are all cases for ‘hich additional measurements seem essential “The available GAVs do not exhaust al the possible groups that might occur in organic C-H-O compounds; the ar rangement of Table 2 is useful for identifying the 100 or so ‘groups for which experimental data are completely lacking in all three phases. Table 2 also demonstrates that groups ‘with similar structures may have nearly equal GAVs For example, although, a5 noted above, C,. C,, Cand © ase eated as distinct species, itis interesting to compare GAVs for groups that differ only in the nature of the C ligands. In Table 2 there aze ten diferent possible groups of the elass C-(C.).(H,. where the 2. ligands are anv com- bination of C, Cy, C,, and C, For thre of these, no GAYS, are shown, However, for mest of the others the gas phase value is approximately ~21-5 kimol: we would therefore {expect the MISsng GAS to be sulle. Ths rules tue Dy convention for groups with three H atom ligands (the frst group in Table 2): its quite reliable for groups with two H ligands. anv gers progressively poorer for grouns with one oF ‘no H ligands, This i parly because the number of com- pounds used to derive the groups with fewer H ligands is smaller. so in general their uncertintes are progressively Farge. In fact. the rule doesnot look very useful fo the large umber of missing groups ofthe form CACY (CCC Iy-.-y---earbon atoms with no HL stom ligands. The absonre af any data foe sich groupe i Plies their ait: one isnot very likely to equite thie values in estimating the enthalpy for an unmeasured compound. “Ths. if enthalpy estimates are required. it may be possible to estimate an appeoximate GAV based on the values of 1415 similar groups, but this recourse is by no means problem- ite. ‘Can we, feom Tables | and 2, point to important groups ‘whose values are as yet undetermined in some phase? In a eneral sense, the answer is nor any gen that is relatively important should have already occurred somewhere in the database its complete absence so far suggests there are not ‘many important compounds that contain it. However. Table 2 does suggest several GAYS that, based on values for other ‘hases or fr other similar groups seem to be in errr. No- table among these are: C-(C, x) (soi probaly in eror by 25-30 kdimol); (CC), (H) (gas and lg 5 Kol; CO)Colp Ciguid and’ solid: 25-40 Kimo): CHONG MENO) (liquids 80 ka/mods CACO) (sold: 25-40 kllmok: C-(C)(C,)-(0) (gas: 60, Kol); and CAC\HAICO) Golid; 60100 kafmo). Additionally, the various values for C-(C,)H)O) forall (C,) ate rather is- cordant is a lage difference in the GAVs for a single group in df- ferent phases. These include C-(Cy), C-(CHG))s. Ce{CaHO}, C-(CVC/NHNO), and C-(C}{CyN(O). The values reported inthis tudy for the GAVs ofthese two para- graphs should be regarded as tentative, subject to redetermi- ‘One group of investigators has proposed redefining some of the groups in fused ring molecules" ‘They define four types of carbon atoms in phenanthrene: (Cy CoND €=Cay—(Cy Cao uy =(Cyy){C,). In Benson's original treatment, the fist two were considered the same [C,~(H)]}. We see no need to dis- Linguish b from a for the following reason: b groups will always voeut in de presence of € wioups;detefixe ote ea ‘only determine 6+ experimentally. Thus we ar free to set by definition. However, this does raise the question Whether one should treat the nine and ten earbons in anthre- ene (call them for now) as differen from ordinary Cy atoms, inasmuch as they are bonded 1 two c-type C atoms. ‘This possible, and the fact that the calculated enthalpy for sntnracene auters tom in experimental by 1> Kimo! On the assumption that ¢=b=a suggests that perhaps ¢ has adi ferent value, The objection to this argument is that the rercent GAVe da ft nanhthacene quite wll (ie. sngonsting € does equal & and a). Hence, there is no cutent basis for defining e groups differently until the discrepancy between anthracene and napithacene enthalpies can be resolved 2.7. Non-Nearest Neighbor Interactions Another area in which data are insuicient to draw defini tive conclusions is tht of non-nearest neighbor interactions: Pee, artha, and gauche effects, which involve atoms separated by atleast two other ators (normal group adit ity relations take into account interactions between atoms with at most one atom between them), Table I lists 21 such correction terms, but in many eases they est on inconclusive 4 Phys. Chom, Ret, Data, Vo. 25, No. 6, 1996 1416 ‘or even contradictory data, For example, consider the enthal- pies of formation Tor the following compounds with 1,2- substitutions on a five-carbon ring in the solid phase (all enthalpies are in kJ/mol): Trans Compound Cis(Z)__ 1B) (E)-@) { 2endanylene diacetate 7ras 7598 153 [L2eeyclopentytene dibenzoate -6673 -6749 -76 12indanylene dibenzoate — -5552 ~$468 5.4 It these data are reliable, the wo adjacent ~C(O)O~ groups inthe (2) configuration are less stable in one pair, but more stable in two pais, though one would in general expect less bility. (Tv dffevcuce ia de nlaytene ings owing to the presence of an attached aromatic ring should have slight ef- fect on this comparison) ‘Or consider the following trimethyl benzoic acids in slid phase, all measured in the same study: [Number of adjacent groups Enthalpy Compound —_klimol___CHy-CHy__CHy-COOH 34TMB 887 2 v 23.STMB 439 1 t 236TMB ~476 1 2 24STIMB 496 1 1 246-TMB 478 ° 2 34STMB SOL z 0 Comparing 236 with 24,5, it appears that adding a €11}~COOH swighan ty ve smighbuning Clly pac deat lizes by 20 Klimol: adding it to two neighboring CH, pairs (compare 2.34 with 3.4) decreases stability by 14 kiimol ‘And two compounds with the same apparent number of ortho effects (23,5 and 2.45) differ by 7 kX/mol—vther 3 measure of the imprecision of the data ot ofthe presence of some other, more subtle effects 1s conceptually appealing 0 try 10 resoive tese anc lies by introducing a nonadditive hindrance correction such as utes effect—anadonal stain present when tree or tal data at hand do not provide consistent justification for such an effect. For example, consider the data for the ben zene tris tetra, pemta- and hexacarboxylic acids inthe solid phase. If there are butressing effects, one would expect the fervor. when the calculations take into account only standard sxoups and additive ortho corrections, to increase with in rsasing uinler uf carluay groups, Tle ata on the last page of Table 6 do not support this prediction. Below, the second columa lists foreach ofthese compounds the exper ‘mental eathaloy minus the ordinary sroup contributions. The Uifereace should represent any ortho and butressing correc tions, The thd column is the remainder after subtracting a correction of 25.5 kiimol (from Table 1 for each carboxy farboxy orto snteracuon) 4. Phys. Chom, Ret. Dat Vol 25, No.6, 1996 N. COHEN Expt~GAV~ Compound Expi-Gavs __ontho 1,234riearboxylie acid 46 4 12.4ticarboxylic acid 28 3 [3.Sricarboxylic acid 18 8 1.23 4-etracarboxslic acid B 3 123,S-tetracarborylic acid 9 9 214 S-teracarboxylie acid st 1 Pentacarboxylic acid 106 6 Hexacarboxylic acid 152 1 The one molecule with significant ertor is the LA tricarborylic acid, for which there should be no ortho or butressing effects, Since the GAVs are determined by a ‘much larger database than just these eight compounds, 1s lifcult to argue that changing the GAVs will reveal the presence of buttressing effects. (Note also that the data do ‘ot support the existence of a consistent negative meta com tribution, as has been proposed in other estimation schemes) ‘As a final example, consider the dimethoxy-substituted benzene and benzoi acid in the gas phase. According to Table 1, the ortho correction for methoxy adjacent to COOH is the same as fortwo adjacent methoxy groups, Expt-GAVs— Compound Expt-GAVs Onto 23edimethowybenzoie acid 31 6 26-dimethorybenzoic acid 29 4 3,4-dimethorybenzoie acid 17 5 2d-dimethorybenzoic acid 13. 0 ‘s>-aumetnonybenzoe acid 3 3 1.2-dimethoxybenzene 7 “19 Again, no butessing effect is apparent (it should show up in the 23, and 2,6-dimethoxybenzoic acids and not others). {Nove ale thatthe dimeshoxyhen7ene. unlike the other com: pounds, shows no evidence for ortho destabilization by the ‘methoxy groups) Similar conclusions result from data for the tri: tetra, penta- and hexamethyl benzenes; no unam- biguous non-adsitive corrections were evident. Other steric effects present similar problems resulting from inadequate or inconsistent data. Consider next the ether suche effect (the 1-4 iteration across an O atom bridging two alkyl groups). In Ref. 1, a value of 2.1 kimol (0.5 keal/ mol) was recommended. Reanalysis of the best currently favallae ds suyuess hat 3.9 AIM (0.8 Keatanl) is a better value, though, as the table below comparing the dif ferences between experimental and calculated enthalpies (ith «3.3 Mimal gouche eomestion) shows, thre ie onside ‘erable scatter inthe data, The second column, labeled "6." is the number of gauche interactions. REVISED GROUP ADDITIVITY VALUES FOR ORGANIC COMPOUNDS: Compound G Expt=Cale Methyl isopropyl ether 1 ° ‘Methyl t-butyl ether 2 4 Isopropyl isopropyl ether 2 1 Isopropyl t-butyl ether 3 1 Ethyl sbusyl ether 1 1 s-butyl s-butyl ether 2 1 With the present value of 3.3 klmol destablization for cach gauche:imeraction, the “ether gauche™ effect is no C=C—=0), analogous tothe ear- bonyl groups (C=O), has been defined, Also, some new iteniary Ketone steric correction is similar 0 the dtertiary ether correction. Like the latter, it oscus in a single com pound so far. Some specific cis, gauche, and ortho correc- tions have also been tentatively identified, ‘The group additivity values and ring strain correction terms derived inthis study predict quite well the enthalpies, fF formation of most oF the compounds im tne Gstabase. In the gas phase, for which agreement is best, the average ror for 1028 compounds (17, for which discrepancies were very large—ereate than 4? kl/mol—were excised) was approxi rately 5.5 k/mol (1.32 kcal/mol), For the liquid phase, che average error for the 941 compounds retained out of 971 total was 5.6 klmol (1.34 kealimol). For the solid phase, the average error forthe 538 kept out of S84 total was 9.1 klimol (2.17 kealimol).™ The average error in the gas phase date base is probably no larger than the average experimental un cortaint, and is as good as one could expect, The slid phase database shows some room for improvement, but the defects ‘may well reside in the experimental uncerttintes. Altema- tively, itis possible that intermolecular forces in condensed phases, which often lie outside the conceptual framework of aroup additivity, contibute at least in some cases to the larger diserepancies between calculated and experimental en- thalpies. A comparison of the average discrepancies in the lfferent phases suggests that if intermolecular forces do limit the uility of group additivity in condensed phases, they are sinificantly only inthe soli, and not inthe liquid pase Table 2 shows there are numerous groups as yet com pletely undetermined, bu, as discussed in Se. 2.6, probably fone is greatly important, However, the disrepancy in the enthalpies of anthracene and naphthacene is of some signif cance, because it holds the answer to whether the 9 and 10 catbons of the anthracene molecule (and similar aromatic catbon atoms) need to be ueated as distin fo te tet Cy atoms. The discussion of Sec. 2.7 concludes that many non: nearest neighbor interactions ar subject to great experimen ‘al uncertainty that might henefir from a serie of earefally conducted measurements, Iki possible that afew am neighbor covctious heve bus Mie Tle tes and uncertainties will be clarified if this project continues through other groups of ‘compounds: carbon-ydrogen-oxygen-nitrogen, et, 4. Phys. Chem, Rel. Data, Vol 25, Mo. 6, 1996 1418 N. COHEN 3. Tables of C-H-O Compounds Table 1. Group additivity values for enthalpy of formation (288 K), C-H-0 groups, aap eT “Gas GAT Tao Sond GAV_—— [tee [ean _ksimel_—#_iatiot aol —#_[ieainol _kitnol em “00 ae] oT + lciciaoe ‘0 9: | 4: ass + | 70 23 + lexcren 24 400 + | 22 “e2 + | 40 “te7 + Joxcye a1 04+] 08 a3 +| 45 63 ¢ leavin ss 24+] 49 m5 + | co ait lcocxr as wo + | 77 m2 +) a: mst Joccio 2 27 >| 97 a6 + lcaicayey se ws +| ss m2 -| s2 28 + Bic es 38 6 | 50 m5 6] 77 m2 2] + leaseasa ss me 7] 40 ver 1] 27 13 3] 2 lexcayens soo 8 +| a6 -es + | 01 -23 +] 3 lexexcaxna 48 1 +] 61 a5 + | 50 a 5 Icrciacanw 7 74 +| 26 soo +] 30 426 5 Jere, 7 m+) 2 “e8 s| 43 worl « lcxcarae2 43 180 9] 53 243 5| 133 8 1] 5 Icicneaay 27 ua. 3| 18 75 1 8 lcrciacaa sa ms 1] 52 28 1 7 Jan: v2 wer s| sr 198 3 8 lousy 272 108 +| 260 1088 + Jouc) za iz +| ms 87 + | m9 imo + Jeurcn osa in a | om? swat | a7 ama >| 0 locos “0 18 + | 416 -e5 +| 101 23 +] 10 leonora a7 er + | 53 m2 + | 71 er 1 | on Jociaenty a3 75 6] 20 46 Jeera saa] ts 7a a] os a+] a lexciacya 35140 + 8 Jeacony 87 mo 6| 47 17 5 Joarcxcr 95 27 2 1“ Jorn 33°18 + | 20 82 +[ 15 63 + Jcvic) ss mo +| 48 wi +| 29 11 + Joxcoens so #18 +| 16 s+ | 401 03 + | 15 Jercyewene 4s 402 + | “er ‘so +] “ss ara + levciacne 342 3 | 40 42 +) 40 a2 + icxcyaico) 2a its] aa a2 es] as 17 + coize2 3 m4 4] 52 218 5| 80 21 4 fe tenouae tr ae + | ce as s| ee sa 7] ve lexorenya fo (a es ao 1 | 7 Joico) 442 2 es #0 2] 8 excycys 430 0 1 mo 155 4] 10 looca) 58 23 9] 80 ws +| ‘58 m3 + lcoicy 57 m8 4] 55 m0 1| 55 20 «| 2 Joost) 52 18 8) so wo 4| 46 we + Jesu eo m2 0] 1 ‘02 0] a0 20 leaioxce) s7 me2| so 29 1| 2 lossonia 8 ss 2| 72 wrt] os a2 0| 2 casconcay 13 54a 2 m2 52 4 | 2 Jcxconcanen2 25 05 1 | 47 107 2 2 enearthvene 45 cecton fos 39 6 woo 8 7] 15 Naprnaene 1-8 corecbon s3_ 2 s| 65 22 2| 50 wo s| ns 4 Phys. Chem, Ret Data, Vol. 25, No.6, 1996 REVISED GROUP ADDITIVITY VALUES FOR ORGANIC COMPOUNDS 1421 Table 1. Group additivity values for enthalpy of formation (298 K), C-H.0 groups, 4 [Group Teo) [1 asscar Ligue GAT Said GAY —[Wotes] [atiol_sulmol —#_[iealnol_ ksimol —#_[teaineh_iinel_® zy 7 7 7 Joxcnny ‘ye tee + | 65 04 + | Soo m2 + Joxcoxr ‘es tet + | “es 50 + | 47 cto54 + Joxcon wos m3 + | 51 234 5 | S24 2102 4 Joxcnen 79) 11586) 118 Joico) ‘7a -2a8 + | 62 270 + | 14 269 + Jowcie wae m5 + | 251 050 + | 250 “tone + Joxcxco) ‘me 4 + | 250 a5 9 | 322 “i947 6 Joxexes, os ze + | sto 107 + | 310 “197 1 | 10 Joxcico) Tar aos + | “as “02 + | “440 “iat + loxcoy2 Sao er 4| 04 54 1 | 490 -ms 4 | 120 Joxcoycs) 2 379 4] 286 ina 1 x Joxceyco) 67 ims 7 | S70 ie 5 | 0 “es 9 Joxcayco) “aa era 2 | “0 “1003 3 m Joxcoj2 e213 + | x0 28 +| so a4 + Js ios vez m2 | me oe + | ona toma 2 | ae Joxcyo) "3 mo + | 2 e+ | ‘10 400 5 | ta Joxenyoy i (2 0 45 ten 1 | 15 Joxoxco) sez 761 4| 208 s70 8| 154 a + | 125 lov var as | ag Get ord Jo-310) 10-418 “18-485 sor 0a | sa Jo-waro2 185 200 jes ws + | 495 74 4 Joxcy210) 81 29 91 ets] 50 me + Je vciaaner 32 et 70 ms 2 | to a3 Jexcvrnor2 158 061 +| 190 909 + | m0 a7 + Jexea0) ss 7s +| 5s m4 +| 56 24 9 Jexciaoz 62 78 3 | 188 s61 + 129 Jowsvom see cers | 47 ona i Jowios ae 121 2] 253-059 2 131 Jove es 15 2| 367 “1536 2 12 Joxcayena0» 69 9 5| 90 05 3 18 excayiniore 3 413 1 oa 1 | toe exc32(cay0) 13 4a 2 1s ccxeaytno m2 12 3| so m9 3 | 195 -crzeri0) 1s 63 2 | 197 Jexeonzte) a eo) 7 c-ccorcoy ‘§ m9 1 | 49 205 1 | 152 oo 1 | 1 cxcyo ma tee 1 | 10 c-coye 210), 124 S19 2 30 26 2 | 14 lexconenore er ue tL tae iexcoinx0) a0 421 | 1a iccoxiatcoy $4 mea] a1 4301 | 30 26 7 | 148 Jexcoxnyoxco) 79 wit | ts Jeexcoxrncy 44-4 2 or os 7 | te, Jcrciacoxa), 42076 2] 18 75 1| 179 749 2] tar lcrcoao2 so 259 1 | 108 Jecox0) wo m3 4] 19, ICscxcoxvaxy) ar wey f2 11 | 0 locoycaxry0) 48 mit 181 Joscpiacay0) 2084s | 152 Jcsriaioxco, 45 102 1 | 153 fexcnmacoy szona+| 52 me +| jas ar + lexcrarico) 47 71 «| 44 $9 +| 90 77 + Joxciaicoy 14 30+] 35 us 9| 52 218 + Jo-warcoye 55 276 5| 58 23 5| 30 05 4 | 15 [cvceico, 40586 + 4 Phys. Chem. Ret ata, Vo. 25, No. 6, 196 1422 N. COHEN Table 1. Group additivity values for enthalpy of formation (298 K), C-H-O groups, 5 [Grou eG) cr Icxcacore 18 67 1 os ar: | 16 c-(cyes70Kc0) 45 188 69 29 2 | 157 c-(cayesH0xco) fo a | te Jo ciaroyco) 135 sos 9 | ecm Jcvovaicowe my | te Joxcjcexticoy 10 42 4 Jexcayenaicoy 38 159 7 6| +50 ae 3 | 16 Jc-cemexxoy ve c-uxcos 13 exrixoxco; ros) py | 184 Joey) m4 40 + 7 leon) Sry “ie 3 3 10 ico.tixco) 2 “54 2 1] 0 ams 1 | 168 coy Si7 ame + + | a4 sar + Jooxcyo) “e2 4473 + + | 5 tas + lcovoe “eo 1 9 S| So 81 5 Icoxoxco) “es m4 5 3 | S60 “1508 5 | 10 lcoxcjcs) “24 158 + 4] aro -ns0 4 | 1 Jeoxcaye) zis 1D 8 3| Sr Ses 1 | 0 coxcaie 155 7 + | 20 “032 6 | am Jcoxcayoy 22 1847 + + | m0 m2 + Jcoxcrx0) 25 163 3 3] sar ser 2] im [coco ei as 2 3] fe tar 2] i Jcoxcyce) ‘09 193 7 7 | 9s 163 + Jcoxcey2 27 1130 9 3] ses m2 9 | 174 Jooxceyo) waa tas + + | 08 m7 + Jcocoycoy es 8 2 oa 322 2 | lcoxcnjca) 28 1685 2 S19 ims 3 | 176 lcoxcaycoy 3 cues 1 | 281 i768 1 | 280 4172 4 | a7 coycycy is 1 | ba 117 178 canco) 2 218 +] ‘20 “es +] 60 aa + cexcio) 89 a2 +] 50 29 7] 40 167 2| 17 cextyo) ss x0 +] 70 23+] 09 00 6 cacayoy 25 ~7 6| eo a7 3| 90 77 4| lcaicxco) 7 349] sa a0 4| 73 me 8 caoyco) ns #5 5| 60. 31 3| 80 5 5 | 1 cescpy0) 4 05 4 12 50 1 | 12 icesconcor 8 m5 1 so 335 1 | iss Josicaxco) 03 7 2] 19 191 ea Joswcore m3 8 1 penta | as Josxcrx0) 78 38 1 16 Josoy oo a8 +] 414 se +] 49 42 + lcoico) 37 is + | 42 ie +] 45 tos + Jecowe ana 477 ¢ | 62 678 187 Joco.ccxs 18 28 1 108 Jerome ra 80 Jeco.coyey 8 ion + 190 Joco4cone 152-651 1s Jexccoxts 30 18 2] a6 es o| sox 23 0 | 162 mer) 217 > 12 evo) Big} 385) 194 Jexcoy zea ines 2 | wo a3 3 | 56 1071 + | 15 4 Phys. Chem, Ret. Data, Vol 25, No.6, 1996 REVISED GROUP ADDITIVITY VALUES FOR ORGANIC COMPOUNDS 1423 Table 1. Group additivity values for enthalpy of formation (298 K), C-H-O groups, 6 [Ron-nearect nelghbor ‘Gaz Gorrecion | Uguid Corecion | Sold Gorrection — [Notes] interactions (C40) Reaine_kuinet_¢_Tican|_taol_ #[icalial snot Ter gauche * * Jonaensauene oo a0 +| oo 00 =| 00 oo + terry eter ws go 1] or 23 1 196 tertiary ketone 63 41] 51 23 4 197 Jorgen 0H, oR) ato (eceptto-COOX) fps (21) i||iioo) foolice eee naire [om ertoto-oR 3 16 2 22 06 2 | 10 |-c00x onnoto ay except ou, oF 3 Re + 1042 + |-c00x erno to tbat 7 m3 4 s1 23 1 | 1 {.C00x erie -COOK oi 3| 65 22 3] os: 3s + | ing evan corrections (CO) ‘GaSe Taguig RSC Belg RSC] Wate catinos limo’ —@ [keane iamol —# [kcaliol _tamol cyelpropanone 61 120 1 mae cyelgropenone soy ass 1 os x8 1 | a0 lontane % iis 2| 23 #3 1 mo yetostanone ze we7 i | 1 150 2 205 cjtontanedione i 13 1 var vona 1 | 207 oyetstenone ara nas 1 | m8 [cjeoeneoone wz oe 1 | we oaa | “te lve 1 | ap 2-Oxeanene 24 wos 1 | ja 757 4 210 lonetene zis 2 1| 25 1087 1 an [Teranyrotiran so 27 2] 40 167 2| 53 m2 4| a2 [revanyeratiran zone es met | 22 (a2 4 213 J2s-onyeronsan 42 176 4 aia f2sonyerotian 7 26 4 215 1 3.0)rtne 53 m2 4| 57 28 5 216 senza 43 58 1 | 178 736 1 27 Jruan 8 243 9 | 60 21 7] 60 21 4 |cyiopertanone 62 mo 1| 19 79 2 218 Jascoie acs a5 we 1 | 29 [succne atyarise os ss a] to 42 4] 74 30 + [3s-cyechestatent.one 6 wo 1 z= [2s-Furandione 33 382 | 24 soo 1| 17 71 2| Pett sortie 57 m8 1 7s sa 1 | zm penzotran Ba 258 1 2 Dibencotran 39 163 1 so 421 | 2 3 Dowie 2ene ws 62 2/ 06 «7 2| 80 m5 1 | 2 } 3-00n0-22ne iq sal a) ogee aa 12 Zs 2.4 Trewiane oa ara | Br [revanyere-2 pyran tas 3] 99° 43 3] 5 21 + | os 3 Dcxane Al a2i fel)| tl ae 4 Dexane 35 46 2] 20 84 ¢ m9 35 traxane 31 130 2] 23 961] 56 24 1| 20 Dinyroberzot 4x For, | 0b] 2a ose zi bina 2pran 13 54 3 1 m Eoormaonthaere 0 sts 1 | 2m eenzopran “148 519 1 me enor conn 55 087 2 25 Divenzoyran 14 50 1 so a1 1 | 26 eionexarane 27 32] 97 204 231 Teale a1 oz 1 | 28 ‘@-Antnacenedene ee 10 4 26 27 4 {0-Phenanhrnedane tea 4021 1 242 4013 1 | 20 js 2-Berzantracene. YOone “os asa 1 “os 10 1 | 20 Lrevonyropiean 2-0 woo 66 i] 45 wes 2a 4. Phys. Chem. Re. ata, Vol. 25, No.6, 1996, 1424 N. COHEN Table 1. Group additivity values for enthalpy of formation (298 K), C-H-O groups, 7 [Ring sain correcions (CAO) Jena annie : f .ytoneaaen one 1 }¢nzphinenedone 2 Jovenzocyctneranone 1 3 exenane + yelnepten one 4 yelnepatrin-one os 252] sa 1421] 23 a6 2] 28 cyelnegtanone 20 wii | o5 214 = Doseconrere 3 1o-ethasbenso. a3 98+ wes mer 1 | sr cjloetagecen 21-ene | sereadoxepn a7 mat | ns ast m2 Scare tae io 1 | ze 536 + 23 Hrevacxane 13 Stat er wo 1 | 25 Jyeloocanene 2 842] 08 23 1| 23 «3 2| 26 cyelononanone s3 zz 1] 33 18 1] 26 a3 1 | 27 meena nonce pean ro ta 1 | os ast | go lua t | ae ytascanene 42 ie 1] 21 ea 4 = Penaoxeeane 260 527 1 woo «18 1 | 20 cyeeundecanone s1 231) 27 nat 281 ji 4z7icreraoncycoomdecane zcoma | 9z > 1 | ar mu t 2e2 cyelcodecanone 37 i351] 21 a8 1] 24s 1005 1 | 20 .4.7,10.13 Pertaonacytpertadecane ao sz 1] 64 28 1 24 cyclpertadecanone 3 26 1 sy rary | a cyelnertaocen-2-on8 87 384 t 49 ms 1 | 266 yleptaecaane 288 4 us tata t | 267 JAstracene pero zr so 1 | 28 f-omabeyoe221-reptane wz se 1] 100 a8 1 29 bije-22 thhptan zene 15 28 2 mo ss 2 | 20 ici 2 1pnptan7-ne 2% 62 1 wr 14 1] 27 ico 30poctan-2.0ne 8 m5 2] 40 17 2 2m sieeoge 2 2}octanone 138 69 1 2m f-orabeyio(2.2.2poorane ne 85 1 s2 28 1 | 73 pyano(2 sean. 7ene sso ste8 2 | 774 lpyanot4.s0pyran2Sdene 160 203 2| 25 Pyrola 20pyren28dene 0 mrs 1 | 26 [248,10-Teranxesprof5Sndecane 2 a7 4 s4 31 | a7 [Eponeendurtsanhyteafcinoet}) 44 02 1 | 70 ltaolactone oar 1] 24 104 7 4 Pentanlactone as ei] 22 ‘2 1 a0 |s-Pentaroactone wo 661] 45 198 1 a [Acamantan-2-one 98 tot zr ses 1 | 282 Dimarianone 1 53 1 312 105 1 | 20 ncen2-one m1 7 4] 19 79 3| 20 148 1 | 2 Berzoperachere'S done 38 28681 1 sao -zo7 1 | 24 4 a2a-Tevahyrot methano 26 sod + | 285 ‘acta 5 one do 102 Dingo penecofoozc3 4 2s m3 1 206 ‘cyl 2 coon Jso.0,11-Teranyaro§ 12-mehano 7H we 165 4 ass 150 1 | 287 sartnen 97 96 2 [a7 7-Teranyeo-47methano 27 98 1 265 1051 | 208 ‘scvanafrant Sone fa -Resnney 51.122. rot raprinacene [s12.0nyer 5, s2seproppaenecycopetagene [CBHI (6, WR Is ae any source fr he Ful RSC 3 a,l's: Assigned te same values 0s (CNH 4 © GAV bases on C1OH16 (15) (Camphene) onl 5 & GAV based ony on 1.3.eyeohepatine, whlch alto onl sauce er oylceptations RSC. The GAV is as age ‘as can ce wnnourine ou beromng Neg, BU si seme eo eal compared te ete phase GAVS © GAV based on 2}-S-ethyienebioyce22 1}heptene igunacine, and deyettigunacine, I GAV found ony inthe fist these. Aline ae questonabie expert alin, 7 9.1: GAVe based on naromadane(C7H8 (4) on ©. Alene, 1.20u0tene, >menye buadne, 1.2 and Zperanene; 1. ouadene, Z:}peagane and s-metnet 2-badene 8 9 27-Dietnyeoc-1,7+2) ousuodziuauno 2 avout igioua> | ousuad. ipa 2 suse uae) suorai-esute-2) sunt Ayers! ua cusrphoviuare| aura eesot5-| une tdedoat9 2 1438 “4 962) uoneunos Jo Acjewua :{4HXx9) spuncdwos uaBoipAy-uomeo “¢ aqeL 4 Phys. Chem, Ref, Data, Vo. 25, No, 6, 1998 1439 REVISED GROUP ADDITIVITY VALUES FOR ORGANIC COMPOUNDS z0 Ho! ts sor S001 co oe | cw sw aie pret oat eu 18! ois. ow oie. a te ones 4 giz 4 caw | egezs ew | sero osx | coro e eax | rueree ase | covses sroc- | cs0v% Zioe- | zercos Lice | a0 asi | Cen esx | coves sear | caris eior | rao oer | reries List| Sze a PRS BROT 5) s¥0 $ "04 262) uonewos Jo Adjeunua “{K¥%XO) spunoduies UaboIDKH-UOgED “E OFEL 4. Phys. Cham. Ref. Data, Vol. 28, No.6, 1996 N. COHEN. 1440 aueuodostonineurs-Aurg-1-2) “ot 862) uoneunos Jo AdeuUa :(4HXx0) spunodwoa uaBoIphy-uogeD “t OHEL 4 Phys. Chem. Ret. Data, Va. 25, No.6, 1996 1441 REVISED GROUP ADDITIVITY VALUES FOR ORGANIC COMPOUNDS “01 962) voneUu0s Jo AcjeuUa {KHxXD) spunoduo> usBophH-uOLIED “¢ oqeL 4. Phys. Chem. Re, Dats, Vol. 25, No.8, 1996 N. COHEN eure sz pie Fi oope- se tee oz eer 96 eee so Lo8- et ecez Zar Leer ss SL yee SNS 06s iz SMe so oo ec se > oo oF ou 90% 4 ee ec uu 8 “(O1 862) Uoneunrs Jo Adieu :(444x9) SpuNoduioo UaBOIPAH-UOGED “E aICeL 4. Phy Chem, Rf, Data, Vol. 25, No.6, 1996, 1443 REVISED GROUP ADDITIVITY VALUES FOR ORGANIC COMPOUNDS: “OF 962) uoneUso) Jo AcreyNUS AAHXO) spunoduios uabouphH-uoges “¢ 2qeL, 4. Phys. Chem, Ret. Date, Vol. 25, No.6, 1996, N. COHEN. so ote oo oss! ro ceaL vor se oz 601 om esi bz sie vow | ex sur coor Sk pub eeu re son owe zo ser ezor Fo Zee ober 00 ool oon | zo gor 00 ee Lor 90 ve os = xo | so oe oe gor tse sr ae ei ove st eee wor | ez os oz ee eee sve | oe os vo te | ov ove ve vor | zs see cw soot | eo oe acer zes | io oo a esn ce Lor | Noe zo os ave be 20e ole 60 Oar bee ze cee oe OF osr oe ez cee soe ze om sz st om ser es ew so ze ao ow er om ow errs eer so 9m be oo os zoe ve eee sz (ob ‘(4 862) Uoneusoy Jo AsjeunU :{KHxXD) spunodulo> UaBosPAH-UOGeD “£141 4. Phys. Chem. Re, ata, Vol. 25, No.6, 1996 1445 REVISED GROUP ADDITIVITY VALUES FOR ORGANIC COMPOUNDS zo eer eer ze ewe ale er ss caer to ever oer rd ow a edorootojiou 2 ut sunay-s hipouenas'sz'24a sume Majoueness2 2-2 4. Phys. Chem. Ret Data, Vol 25, No.6, 1998 N. COHEN 1446 zo suquewepeseus $y Tb ‘04 962) UoneUNO) 40 AdyeuUS «| (AHx9) spunodwos UabephH-uaeD “¢ a1qeL 4. Pha. Chem, Ret, Dat, Vol 25, No.6, 1996 1447 REVISED GROUP ADDITIVITY VALUES FOR ORGANIC COMPOUNDS aueayaptoien ‘eh ‘(1 962) Uoneusos Jo AdeyUZ :(6HXO) spunodulos UaBOIPAH-UOGED “Et ‘J. Phys. Chom. Ro. Data, Vol. 25, No.6, 1996, N. COHEN. Seo ha WS oa 862) uonewos yo Acres, {hHx9) spunodwos uabophH-uoged “¢ a4eL 4. Phys. Chem. Ret. Data, Vo. 25, No 8, 1996 1449 REVISED GROUP ADDITIVITY VALUES FOR ORGANIC COMPOUNDS be see zo L5H ze re oo pe oo 110 89 IOS. inbr =o vo enuos punodwoo Sb ‘4 gz) uoneUsoy Jo AdyeuUZ (AHXD) spunodwos uaBoIPAH-UOMeD “¢ ageL 4. Phys. Chom. ot. Data, Vo. 25, No.6, 1996 N. COHEN 1450 TSaS SETS ET TS TTT 91 ‘01 86%) uoneUNos Jo AddeINUZ :IAHXD) spunodwiod UeGomAH-UOGED “f e1TeL 4. Phys. Chem, Ret. Dat, Vol. 25, No.6, 1896, 1451 REVISED GROUP ADDITIVITY VALUES FOR ORGANIC COMPOUNDS sou Bab 24 ‘(0 £62) uontui0) Jo Adreuug :(4H%x9) spunodiioo uebospAH-UeqeD “eeIqeL 4. Phys. Chem. Re. Data, Vol. 25, No.6, 1996, N. COHEN b “(4 962) uoyews0) Jo Adjeuea (OKHxD) spunodutod uaBAxO-L2BOIPAH-UOGIED “y 0192 J. Phys. Chem. Ret. Dat, Vol. 25, No.6, 1996, 1483 REVISED GROUP ADDITIVITY VALUES FOR ORGANIC COMPOUNDS se per Hoes Ts BES 2 ‘(4 962) Uonew0s Jo Adjeya x{OAHXD) spuRodulod uaBAxo-vaBospAH-UOGED “y OIG 4. Phys. Chem. Ret. Data, Vol 25, No.6, 1896, N. COHEN 1454 corinso orine. Boris sur yaw ne rouenaz-Aaares| euenaz-Auaiez| rouenae-faaree| oven -Aenr2| erwece| oeneg avangzsoouan-z-) emunos puredwo9 © 4h4 962) UoneULI0} Jo AdyeyU :(O44Xx9) sptnodutos UaBAxQUDBoIPAHYOReD “y IGE, 4. Phys. Chem, Ret. Dat, Vol. 25, No.6, 1896, 1455 REVISED GROUP ADDITIVITY VALUES FOR ORGANIC COMPOUNDS (ovouaudoeay) aucueuue:t| enyenie| (over fuse) atousue fut roueroyersoayZ-2) \euesjououeroy2ai9 20034 dorosi| ¥ ‘01 262) uNEUNIOS 10 AdJeUNA (OAHXD) spUNodWIOD UEBAXC-UBBOIPAH-UOGES “y aIGEL 4. Phys. Chem, Rf, Data, Vol. 25, No.6, 1996 N. COHEN 1456 se saz | eae: oe re hue eur bre ome oe cme cue Pe aie hee Ty Sea 8 ‘04 962) donewo} 0 Adyeunwa (OkHx9) spurcduio Labhxo-ueBosphH-toqeD “Ie, “4. Phys Cham. Ref, Oats, Vol 25, Mo 6,195 1487 REVISED GROUP ADDITIVITY VALUES FOR ORGANIC COMPOUNDS bee coe Fr zo Lee ate wa eee 5 coe hoe be oe Le ome: ow os oem sez oe ewe gore vee er 6s #0 oz: vo cee bo boc tea zoel | ro em Tea Ts vas "on Kanone wn) PS BRT =o svo enuueg one ou 888 BaSe8 F 9 "1 862) UeneUL0$ 0 AdjeuI43 :(OAHXD) spunodwos 4eBAxO-aBospAH-UOMIED “y 2142, 4. Phys. Chom, ef, Data, Vol. 25, No.6, 1996, N. COHEN 1458 BRETT L oo vo emunes 2. ‘G1 962) uopewos jo AdjeuUa :(OAHxD) spunodwos UaBAxoUeBoIpA4-UOIeD “y O1aeL, 4 Phys. Chem. Ret. Data, Vol. 25, No.6, 1996 REVISED GROUP ADDITIVITY VALUES FOR ORGANIC COMPOUNDS Tes se BRETT 5 sv emma 9““}4 962) UrpeUt04 jo KdyeuTUA :(OAHXD) spinoduios Usb AKOueBOIPAH-UOGIED “y Ge, 4. Phy Chom. Ret. Dat, Vol. 25, No.6, 1996, N. COHEN 1460 .Spunedueg ausbio Jo uoneauten o sadg, spots 'A Puen Ag >apURUILOR: (Goat) ize oe wou) Slug sabvseurg 09 eta 15 Ta BROT = RO sv ued 6 ‘04 962) UoneUOS Jo AdyeUL!a :(OAHXD) spunoduios HaBAxQ-teBOsph}-UOGIeD “y OIE, 4 Phys. Chem. Ret. Data, Vol 25, No.6, 1996 1461 REVISED GROUP ADDITIVITY VALUES FOR ORGANIC COMPOUNDS (asoo1H0 repevene't “Oa 962) ueneuios 0 Adjeya :(ZOAHKO) spunoduos UOBAxo-uaBosp/H-UOGseD “s a1atL ‘Phys. Chem. Rot. Data, Vol. 25, No.6, 1996, N. COHEN 1462 ewe “04 862) uoneULI0) jo AdjeyL!3 :(ZO/HXO) spunoduio> Us6AKC-UaBospiH-UoGED °S 21q?L 4. Phys. Chem. Ret, Data, Vo. 25, No, 6, 1996 Table 5. Carbon-Hydrogen-Oxygen compounds (CxHy02}: Enthalpy of formation (298 K), 3 REVISED GROUP ADDITIVITY VALUES FOR ORGANIC COMPOUNDS 1483 4: Phys. Chem. Ret Data, Vol 25, No.6, 1998 N. COHEN 1464 4 ‘O1.962) woneUo Jo Adieu +(ZoKHXO) spuNodwo2 Ua6Ax9-UaBOPAH-UogeD °g OREL J. Phys. Chem, Ret, Data, Vol. 25, No.6, 1986 1465, es cm = ite | rae ez gear | euzone — e)zoniHeo 80 om = au | co rol asi | wieesx —(W1zoPIHeD oh cso sms coms Gt tau ims Cour REVISED GROUP ADDITIVITY VALUES FOR ORGANIC COMPOUNDS, 8 "01 86z) vonewo) so Adieuua :{ZoKHXO) spunoduico UOBAxo-UabOIRKH-UOGED °s 21GeL 4. Phys. Chem, Ret. Dat, Vol 25, No.6, 1896 1488 8 ‘(4 962) uoneunioy Jo Adjequa :(z04HXo) spunoduo> UaBAxq-UaBosp/H-UOMED °s GPL 4. Phys. Chem. Rt. Det, Vo. 25, No 6, 1986, 1467 REVISED GROUP ADDITIVITY VALUES FOR ORGANIC COMPOUNDS rerzie oi z01H019 udoropmusas Zonas} ppunodwoo £4 962) Lonewioy 0 Adyeyua :(ZoKHx9) spunodwios uaBAxo-uaBosphH-ogeD °s ele, No.6 1996 4. Phys. Chem. Ret. Data, Vol N. COHEN. 1468 oS Diab 35 90. eimauoy @ ‘G1 862) UoMEUL Jo AdyapUR :(ZOAHXD) spunoduoD UdBAco-UaBOIPAH-UoueD “s AqeL 4. Phys. Chom, Rf, Data, Vol. 28, No.6, 1996 REVISED GROUP ADDITIVITY VALUES FOR ORGANIC COMPOUNDS: 6 ‘G4 962) UoneWUG) jo AdjenUa :(ZOKHXo) spunodwoo UaBAxO-uaBosphH-UoqeD °s OMe, 4. Phys. Chem. Ret, Data, Vol. 25, No 6, 1996 N. COHEN 1470 PIRBET OF "G4 962) oneute Jo Adieu :(ZoKHXD) spunoduios uoBAxo-uaBonAH-UomeD “sg BEL 4. Phys Chom, Rf. Date, Vol. 25, No.6, 1996, 1471 REVISED GROUP ADDITIVITY VALUES FOR ORGANIC COMPOUNDS Tae 1126 woos snoanbe up 4 OFOEHO J UREIDKY oF Wah PSMMAIED “(SN Gey (Us “np spunoduoy auetio jo soweutpout Yeu SUL, 9K (ret) oc vase 57 GOdUS-LSIN wesoig uREunsS pu eseqEES Tonaee w PEIPSY Ur) Tea TRTIET reeetiee )ZORHeD -Yusv-OF G'a-foindomDhe ‘Sropeyceute SN oh PISS aT co vo sais punodiuog n “(01 92) uonewuos Jo KéreuUg {ZOAHXG) spunodwos UatAxO-Ua6OIPAH-UOGED “SaIqeL N. COHEN 1472 cer oem exer ——@e0H0 Zoe sme Sra Zour SMe over bes Gear ee pie abe bse Ouse vice ese fee cme vies eel eae om: es ove = zu | zm se cL so tw gale re vue cee | zee ome ete be cae ves | si ose soc cr ie ae ei cee ts yo 9 = (Oa se sa risa | or one = sae |e nee La Sr 6S Hoe Sa 00 bee vad Fes 96 9US Fee OFor Fe 01s ved Bere 8 PF Fes ONS os Gor ved ere ov om = oom | ave auc "ara se cle tae so sue oe | to ous sais ts eer op oo ess esis | oo om tue vor Fu sie [10 cue ou to pale Ho sei zo tas wares so sax owe J is sue oui a ae to ows sae | oe ou zum ero oe 82 Sie ome se swe ous |sr var ous 96 tes = sexe Joe cme 0 tus ez sue zee | tee vas scar ze oer = pee Jor sus suis 69 rie Mase | ce cus Hoses | 10 Ooms Haazs a ‘vor come v2 ous teaver | ze 98s ves aue ze osm bee to ome sees ou oor oa Sr Sas Sa oo owe ste | ce ves = sus foo ros 9 par zeus __cer | ze per sain Boz moe, Le BIOS mT 25 poetoundon- (fens 26 + ‘01 862) uoneuii0s 30 Adjeupea :(cOKHxD) spanoduios UaBAxc-ueBospAH-YoGleD “9 91atL, 4 Phys. Chem, Ret. Data, Vol 25, No.6, 1996 1473 REVISED GROUP ADDITIVITY VALUES FOR ORGANIC COMPOUNDS (p18 aeuropenavag) poe oxo nsoue00pe| Z 44.962) ueneusios 0 Adjeunsa :(c04HX9) spunoduos uaBAxg-uobOPMH-UOGIED “9 91421 J. Phys. Chem. Ro. Data, Vol. 25, No.8, 1996, N. COHEN 1474 ze ea sms sms (owabeena) ore vo ew = rou | susie et sronet pene susees ow ewe zeus ed owe 086 treat! cos sie ae © “(4 962) Ueneus0§ yo Adjeuua “(CO/HXO) SpuNodWo> U9BAxo-VaBOIPKH-UORIED “9 2101 4. Phys. Chem. Ret. Osta, Vol. 25, No.6, 1996, 1476 REVISED GROUP ADDITIVITY VALUES FOR ORGANIC COMPOUNDS 000° 9960- ze ore BRETT 05 seer reve oueeut 1 ‘(w96z) uonewo}s0 Adieu :(EOKHXD) spunodwo> UaBAx0-UdBOsPKH-UOGRD “9 219EL 4. Phys. Chem, et. Data, Vol. 25, No.6, 1098 N. COHEN 1476 ast en bxs vel ocie | tz pau you es ous 0s sme ea bee sme sue § ‘04 962) uoneW0},0 AdjeuIwa AEO/HXO) sfUNoduIad UabAxo-UaBoIRKH-OGED “9 2ICeL 1477 REVISED GROUP ADDITIVITY VALUES FOR ORGANIC COMPOUNDS sus eu 9 ‘1 862) Loneuo} jo AdyeuUa {OKHXO) spUNodwed UabKxD-UaBOIPAH-UOGUED “9 91961 Data, Vol. 25, No 6, 1896 Phys N. COHEN 1478 ewes ese 00 au: ted 99H: se cae ese | covccur vee sr ous | cova vee | so sou seu | suzonie cae e960 opt sep vo vu sa | careio vec jos sse sae | cereus tie | ov cue = oar | opzis conn eles Soa ose socecen eo vou eau: | ovesesa e905 sore corece a cress ves sms soar sas sms z00r vas sms ove Vem Sms 995m zo ows os Loo sms 7s tees ez risice vex Pusel peers el eu sms cen sus ies L990 ave 898- sm 6m: fo Lv sis eves toe ROP SOS ST PIS ‘BRETT 35 v9 a 2. ‘O4 962) vonewos Jo Adieu :(OKHXD) spanoduios UaBAxc-uaBomphy-UOGED “9 aIeL, 4: Phys. Chem, Ret. Data, Vol. 25, No.6, 1996 1479 REVISED GROUP ADDITIVITY VALUES FOR ORGANIC COMPOUNDS, — ase oe 2 ‘4 962) uspeUOsso AdjeuUA “(COSHXD) spunoduos UaBAxo-voboIFAH-UOGED “9 21¢eL J. Phys. Chem, Rf, Dats, Vol. 25, No.6, 1996 N. COHEN ‘Gest) 072 vor sz ac cas-L9IN wsbo.guojeue pur aseqeie soRadoly FS=ITINND LS (551) 506 22 0 woUD ud 715.662 SpLOdWoD LAfOEH-S-O-H-H-0 1 sandoxg MRUPOULEAL ‘no disci an pue (31. 5/r10¢) 90000] 20 FH frar-sovlaewoen-' pur lgz9-205] e128 Zo aA 1480 seoumejoy pve HN Ts ar eS ON 5 PISS oT eo sv eynauos punodunon 6 ‘01 862) voneuno, Jo Adlequa ={EOKHXO) spunodwos Us6Ax9-UaBopAH-uogteED “9 2aeL 4. Phys. Chom. Rot. Data, Vol. 25, No.6, 1096 REVISED GROUP ADDITIVITY VALUES FOR ORGANIC COMPOUNDS 4, Acknowledgments This work was carried out under Contract No. 43NANB420595 of the National Institute of Standards and ‘Technology, whose support is gratefully acknowledged. The continued interest and advice of Professor S. W. Benson is also deeply appreciated. The painstakingly thorough evalua~ tions of the two anonymous referees proved most helpful their services considerably improved the paper. 5. References "See, W. Benton, Phemochemia! Kits, 2nd e. Wiley, New Yok, 196), and he eterences ened teen, ‘Seed Vales of Pyscal ond Taermotnamie Proper of Hyroe Ins and Related Conpown, Comprising the Tables of te American Peso Inia Research Prot €4 Exot a of December 3, 1952 _{Camegi Ps, Psy 1953) ‘ranicr of Organ Compounds (Keege,Malb PL, 198) 1'D Cox and Pit, Permachomsy of Organic and Organomet “ie Compounds (alec, Lando. 1970). Sk nua. DNase and 8B. Kiby, Phrmochomal Bar of Organic Compounds, ede. (Chspman ad Hal, Loon 986). ‘Petey has weeny sevsd the compton of Pee, Nair, and Kiby in Themechenial Dat aad Sucre of Organi Conpownds (Tet

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