NIST-JANAF Thermochemical Tables

NIST-JANAF Thermochemical Tables. I.
Ten Organic Molecules Related to Atmospheric Chemistry

Olga Dorofeevaa
Physical and Chemical Properties Division, Chemical Science and Technology Laboratory, National Institute of Standards and Technology, Gaithersburg, Maryland 20899
Vladimir P. Novikov
Department of Chemistry, Moscow State University, Moscow 119899, Russia
David B. Neumannb
Department of Chemistry and Biochemistry, University of Maryland, Baltimore County, Baltimore, Maryland 21250
Received 6 September 2000; accepted 16 January 2001
The structural, spectroscopic, and thermodynamic properties of 10 gas phase organic molecules related to atmospheric chemistry, including three peroxides and four carboxylic acids, are reviewed. The calculation of the thermochemical tables involved the critical evaluation of new spectroscopic data, enthalpy of formation determinations, and the use of recent internal rotation data. Since insufcient information to characterize all 10 molecules exists, estimation schemes were used to provide the missing experimental and theoretical data. 2001 by the U.S. Secretary of Commerce on behalf of the United States. All rights reserved.
Key words: critical evaluation; enthalpy of formation; group additivity method; heat capacity; internal rotation; molecular structure; normal coordinates; spectroscopic properties; thermodynamic properties; transferable force elds.
Contents
1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2. Bromoacetic Acid, CH2BrCOOH. . . . . . . . . . . . 2.1. Enthalpy of Formation. . . . . . . . . . . . . . . . . . . 2.2. Heat Capacity and Entropy. . . . . . . . . . . . . . . . 2.3. References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3. Chloroacetic Acid, CH2ClCOOH. . . . . . . . . . . . 3.1. Enthalpy of Formation. . . . . . . . . . . . . . . . . . . 3.2. Heat Capacity and Entropy. . . . . . . . . . . . . . . . 3.3. References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4. Oxopropanedinitrile, NCCOCN. . . . . . . . . . . . 4.1. Enthaply of Formation. . . . . . . . . . . . . . . . . . . 4.2. Heat Capacity and Entropy. . . . . . . . . . . . . . . . 4.3. References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5. Glycolic Acid, HOCH2COOH. . . . . . . . . . . . . 5.1. Enthalpy of Formation. . . . . . . . . . . . . . . . . . . 5.2. Heat Capacity and Entropy. . . . . . . . . . . . . . . . 5.3. References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6. Glyoxal, OvCHCHvO. . . . . . . . . . . . . . . . . . .
a
477 478 478 479 480 481 482 483 484 485 485 485 486 487 488 489 490 492
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8.
9.
10.
11.
Guest Researcher, currently at the Glushko Thermocenter of the Russian Academy of Sciences, IVTAN Association of the RAS, Izhorskaya St. 13/19, Moscow 127412, Russia; Electronic mail: olga.d@ru.net. b Visiting Professor, currently at TPC Data Associates, Box 190, Washington Grove, MD, 20880-0190; Electronic mail: mneumann@aol.com. 2001 by the U.S. Secretary of Commerce on behalf of the United States. All rights reserved. 0047-2689200130247539$35.00
12. 13. 14. 475
6.1. Enthalpy of Formation. . . . . . . . . . . . . . . . . . . 6.2. Heat Capacity and Entropy. . . . . . . . . . . . . . . . 6.3. References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . CN. . . . . . . . . . . . . . Cyanooxomethyl Radical, OC 7.1. Enthalpy of Formation. . . . . . . . . . . . . . . . . . . 7.2. Heat Capacity and Entropy. . . . . . . . . . . . . . . . 7.3. References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . Oxalic Acid, HOCOCOOH. . . . . . . . . . . . . 8.1. Enthalpy of Formation. . . . . . . . . . . . . . . . . . . 8.2. Heat Capacity and Entropy. . . . . . . . . . . . . . . . 8.3. References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . Methyl Hydroperoxide, CH3OOH. . . . . . . . 9.1. Enthalpy of Formation. . . . . . . . . . . . . . . . . . . 9.2. Heat Capacity and Entropy. . . . . . . . . . . . . . . . 9.3. References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . Dimethyl Peroxide, CH3OOCH3. . . . . . . . . 10.1. Enthalpy of Formation. . . . . . . . . . . . . . . . . . 10.2. Heat Capacity and Entropy. . . . . . . . . . . . . . 10.3. References. . . . . . . . . . . . . . . . . . . . . . . . . . . . Diacetyl Peroxide, CH3COOOCOCH3. . . . . . . . . . . . . . . . 11.1. Enthalpy of Formation. . . . . . . . . . . . . . . . . . 11.2. Heat Capacity and Entropy. . . . . . . . . . . . . . 11.3. References. . . . . . . . . . . . . . . . . . . . . . . . . . . . Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Acknowledgments. . . . . . . . . . . . . . . . . . . . . . . . . . Extended Bibliographies. . . . . . . . . . . . . . . . . . . . .
493 493 495 496 496 496 497 498 498 498 499 500 501 502 502 504 504 505 505 507 508 508 509 510 510 510
J. Phys. Chem. Ref. Data, Vol. 30, No. 2, 2001
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DOROFEEVA, NOVIKOV, AND NEUMANN
14.1. Extended Bibliography for Bromoacetic Acid, C2H3BrO2. . . . . . . . . . . . . . . . . . . . . . . 14.2. Extended Bibliography for Chloroacetic Acid, C2H3ClO2. . . . . . . . . . . . . . . . . . . . . . . 14.3. Extended Bibliography for Oxopropanedinitrile, C3N2O. . . . . . . . . . . . . . 14.4. Extended Bibliography for Glycolic Acid, C2H4O3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14.5. Extended Bibliography for Glyoxal, C2H2O2. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14.6. Extended Bibliography for Cyanooxomethyl Radical, NC2O. . . . . . . . . . 14.7. Extended Bibliography for Oxalic Acid, C2H2O4. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14.8. Extended Bibliography for Methyl Hydroperoxide, CH4O2. . . . . . . . . . . . . . . . . . 14.9. Extended Bibliography for Dimethyl Peroxide, C2H6O2. . . . . . . . . . . . . . . . . . . . . . 14.10. Extended Bibliography for Diacetyl Peroxide, C4H6O4. . . . . . . . . . . . . . . . . . . . .
1. Introduction
510 510 511 511 511 512 513 513 513 513 A large number of biogenic and industrial polutant species play a direct or indirect role in tropospheric smog chemistry. Modeling of the kinetics of tropospheric chemical reaction processes often requires thermodynamic data. In the following, evaluated thermodynamic data for a few smaller organic species including some peroxides relevant to smog chemistry and atmospheric chemistry in general are presented. The ideal gas thermodynamic properties of the polyatomic molecules were calculated by standard statistical mechanical methods in which a rigid-rotor harmonic-oscillator model, modied where appropriate for internal rotations, was assumed for each compound. The statistical formulas for thermodynamic functions are discussed in several textbooks, review articles, and reference books.16 Molecular and spectroscopic constants needed for the calculations were selected from the literature. In a few cases missing data were estimated by analogy to related compounds. For some molecules, the fundamental frequencies were estimated by normal coordinate calculations using force constants transferred from related molecules and the program NCA written by Novikov and Malyshev.7 To evaluate the internal rotational contributions to the thermodynamic functions, the internal rotational partition function was formed by the summation of internal rotational energy levels for each rotor. These energy levels were obtained by the diagonalization of the one dimensional Hamiltonian using a potential function of the form V 487 1 2 V n 1 cos n , n 1
List of Tables 1. Ideal gas thermodynamic properties of bromoacetic acid C2H3BrO2g at the standard state pressure, p 0.1 MPa T r 298.15 K). . . . . 2. Ideal gas thermodynamic properties of chloroacetic acid C2H3ClO2g at the standard state pressure, p 0.1 MPa T r 298.15 K. . . . . . 3. Ideal gas thermodynamic properties of oxopropanedinitrile C3N2Og at the standard state pressure, p 0.1 MPa T r 298.15 K). . . . . . . . . . 4. Ideal gas thermodynamic properties of glycolic acid C2H4O3g at the standard state pressure, p 0.1 MPa T r 298.15 K). . . . . . . . . . . . . . . . . . 5. Ideal gas thermodynamic properties of glyoxal C2H2O2g at the standard state pressure, p 0.1 MPa T r 298.15 K). . . . . . . . . . . . . . . . . . . . 6. Ideal gas thermodynamic properties of the cyanooxomethyl radical C2NOg at the standard state pressure, p 0.1 MPa ( T r 298.15 K). . . . . 7. Ideal gas thermodynamic properties of oxalic acid C2H2O4g at the standard state pressure, p 0.1 MPa ( T r 298.15 K). . . . . . . . . . . . . . . . . 8. Ideal gas thermodynamic properties of methyl hydroperoxide CH4O2g at the standard state pressure, p 0.1 MPa ( T r 298.15 K). . . . . . . . . 9. Ideal gas thermodynamic properties of dimethyl peroxide C2H6O2g at the standard state pressure, p 0.1 MPa ( T r 298.15 K). . . . . . . . . 10. Ideal gas thermodynamic properties of diacetyl peroxide, C4H6O4g at the standard state pressure, p 0.1 MPa ( T r 298.15 K). . . . . . . . . 11. Summary of the thermodynamic properties at 298.15 K and the standard state pressure, p 0.1 MPa. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
481
483
491
494
where is the internal rotational angle. The method of generating the internal rotation energy levels has been described by Lewis et al.8,9 The constant required to generate the internal rotational energy levels for each rotor is the internal rotational constant F or reduced moment of inertia of the rotating group ( I r ). Where available, the V n terms and internal rotational constant were taken from spectroscopic data. If the F value was unavailable, it was calculated from the reduced moment of inertia with the relationship F h /8 2 cI r . 2
497
500
503
506
509
510
The value of I r was calculated using molecular structural parameters with a computer program based on a method of calculating the reduced moments of inertia developed by Pitzer and Gwinn.10,11 A molecular model of an equilibrium mixture of trans and cis isomers was employed for calculating the thermodynamic functions of glyoxal.4,12,13 This method uses the enthalpy difference between the two conformers to calculate the equilibrium mole fraction of each species. From these data and thermodynamic functions of two conformers, values of thermodynamic functions were calculated, allowing for the mixing of two conformers. The sources of uncertainties in the calculated thermodynamic functions arise from uncertainties in the molecular
NIST-JANAF THERMOCHEMICAL TABLES constants used in the calculations as well as deviations from the rigid-rotor harmonic-oscillator model. In this work the uncertainties in the thermodynamic functions were estimated by the procedure developed by Gurvich et al.6 This approach predicts the uncertainties in the thermodynamic functions S ( T ) and C p ( T ) for simple molecules such as C3N2O reasonably well. For molecules with one or more internal rotations, the additional uncertainties due to deviations from the rigid-rotor harmonic-oscillator model are difcult to assess. The largest uncertainty probably arises from the anharmonicity of the asymmetric torsion. This will have little effect at room temperature but may be signicant at the higher temperatures. The total estimated uncertainties in the thermodynamic functions S ( T ) and C p ( T ) in the range between 298.15 and 2000 K are given in the discussions for each molecule. Based on the selected values of the molecular constants, the ideal gas thermodynamic functions, heat capacity, C p ( T ), entropy, S ( T ), enthalpy H ( T ) H (298.15 K) , and the Gibbs energy function G ( T ) H (298.15 K) / T , have been calculated for selected temperatures up to 2000 K at the standard state pressure, p 0.1 MPa. In the tables that follow in a few cases excited electronic states have been factored into the calculations; the energy of an electronic state relative to the ground electronic state is given as ; the degeneracy of electronic states are referred to in these tables as the quantum weight, g .) The enthalpy of formation values f H (298.15 K) were selected by analyzing experimental studies which may result in the enthalpies of formation determination. In the absence of experimental data, the f H (298.15 K) values were estimated by approximate methods accepted as standard for organic molecules and radicals.14,15 The calculated values of the enthalpy difference, H ( T ) H (298.15 K) , and entropy, S ( T ), of the ideal gas were
477
combined with values of the enthalpies and entropies of the elements in their reference states to derive values of enthalpy of formation ( f H ), Gibbs energy of formation ( f G ), and the logarithm of the equilibrium constant of formation (log K f ) of the substances as a function of temperature over the range of 02000 K. Values used here of H ( T )- H (298.15 K) and S ( T ) for the elements in their reference states H2g, Ccr, graphite, O2g, N2g, F2g, Cl2g, and Br2cr,liq, T 332.503 K) and Br2g, T 332.503 K] are those given in the JANAF Thermochemical Tables.5
References
K. S. Pitzer, Quantum Chemistry PrenticeHall, Englewood Cliffs, NJ, 1953. 2 J. G. Aston and J. J. Fritz, Thermodynamics and Statistical Thermodynamics Wiley, New York, 1959. 3 G. N. Lewis, M. Randall, K. S. Pitzer, and L. Brewer, Thermodynamics, 2nd ed. McGrawHill, New York, 1961. 4 S. G. Frankiss and J. H. S. Green, Chemical Thermodynamics The Chemical Society, London, 1973, Vol. 1, Chap. 8, pp. 268316. 5 M. W. Chase, Jr., C. A. Davies, J. R. Downey, Jr., D. J. Frurip, R. A. McDonald, and A. N. Syverud, JANAF Thermochemical Tables, 3rd ed. J. Phys. Chem. Ref. Data 14, Suppl. 1 1985. 6 L. V. Gurvich, I. V. Veyts, and C. B. Alcock, Thermodynamic Properties of Individual Substances, 4th ed. Hemisphere, New York, 1989, Vol. 1, Part 1. 7 V. P. Novikov and A. I. Malyshev, Zh. Prikl. Spektrosk. 33, 545 1980. 8 J. D. Lewis, T. B. Malloy, Jr., T. H. Chao, and J. Laane, J. Mol. Struct. 12, 427 1972. 9 J. D. Lewis and J. Laane, J. Mol. Spectrosc. 65, 147 1977. 10 K. S. Pitzer and W. D. Gwinn, J. Chem. Phys. 10, 428 1942. 11 K. S. Pitzer, J. Chem. Phys. 14, 239 1946. 12 K. S. Pitzer, J. Chem. Phys. 5, 473 1937. 13 J. G. Aston and G. Szasz, J. Chem. Phys. 14, 67 1946. 14 N. Cohen and S. W. Benson, Chem. Rev. 93, 2419 1993. 15 D. R. Stull, E. G. Westrum, Jr., and G. C. Sinke, The Chemical Thermodynamics of Organic Compounds Krieger, Malabar, FL, 1987.
1

478
2. Bromoacetic Acid, CH2BrCOOH

Bromoacetic acid (C2H3BrO2) S (298.15 K) 337.0 5.0 J K1 mol1 Molecular constants Point group: C s Ground electronic state: X 1A Energy: X 0 cm1 Symmetry number: 1 Quantum weight: g X 1 Ideal gas M r 138.9485 f H (0 K) 364.6 3.1 kJ mol1 f H (298.15 K) 383.5 3.1 kJ mol1
Symmetry A
Vibrational frequencies, i , and degeneracies g i i , cm1 gi Symmetry
i , cm1 10 11 12 13 14 15 16 17 18
589 384 180 3076 1243 806 611 489 a
gi 1 1 1 1 1 1 1 1 1
1 2 3 4 5 6 7 8 9
a
3566 3037 1808 1449 1325 1208 1047 908 747
1 1 1 1 1 1 1 1 1
Instead of torsional mode 18 47 cm1, the contributions due to the internal rotation about CC bond were calculated from the potential: 1 . V() 1 2 V 3 (1 cos 3 ), where is the torsional angle, V 3 450 cm CH2Br top: Reduced moment of inertia, I r 2.8300 10 39 g cm2, Symmetry number, m 1. Geometry r (CH1.090.02 r (OH0.970.02 CCO1261 CCO 111 1.5 CCBr 112.5 1.5 CCH 112 2 HCH 109.5 1 COH 106 1 (OvCCBr) 0.0 (OvCOH) 0.0 B 0 0.050 528 B 0 0.050 066 C 0 0.044 536 C 0 0.044 176
r (CC1.510.01 r (CvO1.210.01 r (CO1.360.01 r (CBr1.950.02 Rotational constants in cm1: CH279BrCOOH A 0 0.348 921 CH281BrCOOH A 0 0.348 916
Product of moments of inertia: I A I B I C 28 178 10 117 g3 cm6.
2.1. Enthalpy of Formation The recommended value of enthalpy of formation of gaseous bromoacetic acid, (383.5 3.1) kJ mol1, was obtained by Lagoa et al.1 from experimental measurements. This value is the sum of the enthalpy of formation of bromoacetic acid in the crystalline state, f H (C2H3BrO2,
cr I, 298.15 K466.981.08 kJ mol1, determined from rotating bomb combustion calorimetry, and the enthalpy of sublimation, subH C2H3BrO2 ) (83.50 2.95) kJ mol1, determined from Knudsen effusion experiments. Note that the recommended value is close to the value predicted by the method of group equations:2
NIST-JANAF THERMOCHEMICAL TABLES f H CH2BrCOOH f H CH2ClCOOH f H CH2BrCH3 f H CH2ClCH3 427.6 61.9 112.1 377.4 kJ mol1 the f H values for CH2BrCH3, and CH2ClCH3 were taken from compilation by Pedley,3 for CH2ClCOOHfrom Ref. 1. A somewhat lower estimate of the enthalpy of formation of bromoacetic acid, 3956 kJ mol1 was given by Lias et al.4 2.2. Heat Capacity and Entropy From their microwave study, van Eijck et al.5 determined the rotational constants of three isotopic species (CH2 79BrCOOH, CH2 81BrCOOH, and CH2 79BrCOOD. Although no complete structure could be evaluated from the available data, the substitution coordinates of the Br atom and the carboxyl H atom were consistent only with the trans structure with respect to the atoms BrCCOH. This conformation is identical to lowest-energy form of chloroacetic acid named as cis-syn because of cis conguration for OvCOH and ClCCvO groups. The cis structure with respect to the atoms BrCCOH was obtained by Chen et al.6 from ab initio calculation. However, the geometry of chloroacetic acid calculated by Chen et al.6 was also not consistent with that determined from experimental studies. The trans structure with respect to the atoms BrCCOH C s symmetry is accepted in this work for lowest-energy conformer of bromoacetic acid in accord with the microwave data.5 The isotope-weighted value of the product of the principal moments of inertia of bromoacetic acid is calculated in this work from the rotational constants for CH2 79BrCOOH and CH2 81BrCOOH. 5 Structural parameters given above are those estimated by comparison with structural parameters of CH3COOH, 7 CH2ClCH3, 8
479
CH2ClCOOH, 9 and CH2BrCH3. 10 These structural parameters yield values for the rotational constants which are 1.2%1.6% different from the observed values used in the calculations. The difference has a negligible effect on the thermodynamic functions. There is no information on other stable conformers of bromoacetic acid arising from internal rotation around the CC bond. van Eijck et al.5 could only conclude that the gauche conformation, if present, is not signicantly higher in energy than the trans conformation. Their rough estimate of the torsional frequency, 47 cm1, may be compared with 62 cm1 for chloroacetic acid.11 As in the case of chloroacetic acid, the simple potential, V 1 2 V 3 1 cos 3 , where is the BrCCvO torsional angle, is used in this work to calculate the internal rotational contributions to the thermodynamic functions of bromoacetic acid. The barrier height for the rotation about the CC bond is practically the same in CH2ClCH3 and CH2BrCH3 molecules.12,13 For that reason, the value of V 3 for bromoacetic acid was accepted to be the same as that for chloroacetic acid. The value of the reduced moment of inertia for the CH2Br top was derived from structural parameters adopted in this work see above. Vibrational spectra of bromoacetic acid were investigated only for a solid phase.1417 These vibrational assignments are incomplete and it may be expected that they are much different from a gaseous spectrum as in the case of chloroacetic acid. Fundamental frequencies of gaseous bromoacetic acid were estimated in this work by normal coordinate calculations using the force constants transferred from related compounds. Simplied force elds for CH3COOH, CH2ClCH3, CH2BrCH3, and CH2ClCOOH were determined using experimental vibrational assignments for these molecules.1821 37 force constants were used to calculate the vibrational frequencies of bromoacetic acid:
f OH f CH f CvO f CC f CO f CBr f HCH f CCH f COH f CCO f HCBr f CCBr f OvCC f OvCO
7.092 4.998 14.076 4.101 3.891 3.531 0.274 0.793 0.424 2.465 0.547 1.042 2.312
f wagCvO f torsCO f torsCC f CH,CH f CH,CC f CH,CBr f CC,CBr f CC,CO f CvO,CO f CvO,CC f CvO,CCO f CvO,OvCC f CvO,OvCO
0.310 0.183 0.028 0.061 0.332 0.402 0.377 0.693 2.221 1.660 1.365 0.687
f CC,CCH f CC,CCO f CC,CCBr f CC,OvCC f CC,OvCO f CO,COH f CO,CCO f CO,OvCC f CO,OvCO f CBr,HCBr f CBr,CCBr f CH,HCBr f CH,HCH f CH,CCH
0.199 0.425 0.017 1.250 0.041 0.296 0.605 0.148 0.044 0.533 0.184 0.216

480

J. B. Pedley, Thermochemical Data and Structures of Organic Compounds Thermodynamics Research Center, College Station, TX, 1994, Vol. I. 4 S. G. Lias, J. E. Bartmess, J. F. Liebman, J. L. Holmes, R. D. Levin, and W. G. Mallard, J. Phys. Chem. Ref. Data 17, Suppl. 1 1988. 5 B. P. van Eijck, H. A. Dijkerman, and J. Smits, J. Mol. Spectrosc. 73, 305 1978. 6 L.-T. Chen, G.-J. Chen, and X.-Y. Fu, Chin. J. Chem. 13, 10 1995. 7 B. P. van Eijck, J. van Opheusden, M. M. M. van Schaik, and E. van Zoeren, J. Mol. Spectrosc. 86, 465 1981. 8 M. Hayashi and T. Inagusa, J. Mol. Struct. 220, 103 1990. 9 J. L. Derissen, and J. M. J. M. Bijen, J. Mol. Struct. 29, 153 1975. 10 T. Inagusa and M. Hayashi, J. Mol. Spectrosc. 129, 160 1988. 11 B. P. van Eijck, A. A. J. Maagdenberg, and J. Wanrooy, J. Mol. Struct. 22, 61 1974. 12 J. R. Durig, W. E. Bucy, L. A. Carreira, and C. J. Wurrey, J. Chem. Phys. 60, 1754 1974. 13 J. Gripp, H. Dreizler, and R. Schwarz, Z. Naturforsch. A 40, 575 1985. 14 J. E. Katon, T. P. Carll, and F. F. Bentley, Appl. Spectrosc. 25, 229 1971. 15 J. E. Katon and D. Sinha, Appl. Spectrosc. 25, 497 1971. 16 J. E. Katon and R. L. Kleinlein, Spectrochim. Acta A 29, 791 1973. 17 P. F. Krause, J. E. Katon, and R. W. Mason, J. Phys. Chem. 82, 690 1978. 18 nthard, J. Mol. Spectrosc. 84, 457 1980. H. Hollenstein and H. H. Gu 19 S. Suzuki and A. B. Dempster, J. Mol. Struct. 32, 339 1976. 20 S. Suzuki, J. L. Bribes, and R. Gaufres, J. Mol. Spectrosc. 47, 118 1973. 21 sa nen, J. Phys. Chem. 97, 10925 J. Nieminen, M. Pettersson, and M. Ra 1993.
3
stretching and stretchstretch interaction constants are in units of mdyn/; bend, wagging, and torsion constants are in units of mdyn ; stretchbend interaction constants are in units of mdyn. These constants were transferred from CH3COOH and CH2BrCH3 molecules with corrections made by analyzing the trends in force constants of molecules CH3COOH, CH2ClCH3, and CH2ClCOOH. The uncertainties in the calculated thermodynamic functions Table 1 may reach 36 J K1 mol1 for C p ( T ) and 512 J K1 mol1 for S ( T ). They are caused by the uncertainties in the adopted vibrational frequencies and the approximate treatment of internal rotation. Ideal gas thermodynamic properties of bromoacetic acid have not been reported previously. 2.3. References
1
A. L. C. Lagoa, H. P. Diogo, M. Pilar Dias, M. E. Minas da Piedade, L. es, R. C. M. P. F. Amaral, M. A. V. Ribeiro da Silva, J. A. Martinho Simo Guedes, B. J. Costa Cabral, K. Schwarz, and M. Epple, Chem. Eur. J. 7, 483 2001. 2 D. R. Stull, E. F. Westrum, and G. C. Sinke, The Chemical Thermodynamics of Organic Compounds Krieger, Malabar, FL, 1987; see also the difference method, N. Cohen, and S. W. Benson, Chem. Rev. 93, 2419 1993.

NIST-JANAF THERMOCHEMICAL TABLES

TABLE 1. Ideal gas thermodynamic properties of bromoacetic acid C2H3BrO2g at the standard state pressure, p 0.1 MPa T r 298.15 K) T K 0 25 50 75 100 150 180 190 200 210 220 230 240 250 260 270 280 290 298.15 300 350 400 450 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000 C p S G H ( T r ) / T H H ( T r ) fH fG J K1 mol1 J K1 mol1 J K1 mol1 kJ mol1 kJ mol1 kJ mol1 log K f 0.000 36.587 41.371 45.202 48.832 56.415 61.214 62.843 64.482 66.128 67.778 69.431 71.083 72.731 74.374 76.007 77.630 79.240 80.540 80.834 88.515 95.600 102.021 107.785 117.569 125.486 132.017 137.498 142.157 146.150 149.592 152.573 155.164 157.423 159.399 161.134 162.662 164.013 165.210 0.000 211.762 238.698 256.212 269.713 290.927 301.635 304.988 308.253 311.439 314.553 317.602 320.592 323.527 326.412 329.250 332.043 334.795 337.010 337.509 350.553 362.842 374.480 385.532 406.081 424.820 442.016 457.891 472.625 486.366 499.234 511.328 522.732 533.516 543.741 553.457 562.712 571.543 579.987 852.075 539.288 442.164 397.423 358.541 348.180 345.818 343.859 342.239 340.910 339.831 338.967 338.291 337.779 337.411 337.169 337.040 337.010 337.011 338.023 340.365 343.514 347.168 355.302 363.915 372.617 381.222 389.634 397.810 405.732 413.394 420.800 427.958 434.879 441.570 448.045 454.315 460.389 16.862 16.008 15.029 13.946 12.771 10.142 8.378 7.758 7.121 6.468 5.799 5.113 4.410 3.691 2.955 2.204 1.435 0.651 0.000 0.149 4.385 8.991 13.934 19.182 30.468 42.634 55.519 69.002 82.991 97.411 112.203 127.315 142.704 158.336 174.180 190.208 206.400 222.735 239.197 364.616 365.365 366.712 368.184 369.448 371.701 372.997 373.427 373.854 374.281 374.706 375.130 375.553 375.975 376.398 382.140 382.632 383.115 364.616 365.150 364.466 363.016 361.099 762.919 380.746 252.820 188.614
481
356.428 124.116 353.251 102.508 352.142 96.808 351.012 91.672 349.858 348.686 347.493 346.282 345.055 343.809 342.466 340.987 339.491 87.020 82.786 78.916 75.364 72.094 69.070 66.252 63.610 61.147 59.261 58.846 49.164 41.687 35.857 31.182 24.153 19.118 15.334 12.388 10.030 8.101 6.494 5.134 3.971 2.963 2.082 1.307 0.618 0.004 0.549
383.500 338.262 383.587 400.269 401.362 402.305 403.114 404.395 405.305 405.904 406.239 406.354 406.281 406.053 405.702 405.257 404.734 404.160 403.549 402.914 402.270 401.625 337.981 329.432 319.235 308.911 298.489 277.439 256.204 234.859 213.457 192.028 170.598 149.181 127.785 106.425 85.097 63.786 42.535 21.313 0.130 21.019
3. Chloroacetic Acid, CH2ClCOOH

Chloroacetic acid (C2H3ClO2) S (298.15 K) 325.9 5.0 J K1 mol1 Molecular constants Point group: C s Ground electronic state: X 1A Energy: X 0
cm1
Ideal gas
M r 94.4975 f H (0 K) 416.0 1.0 kJ mol1 f H (298.15 K427.61.0 kJ mol1 Symmetry number: 1 Quantum weight: g X 1

482
DOROFEEVA, NOVIKOV, AND NEUMANN Vibrational frequencies, i , and degeneracies g i i , cm1 gi Symmetry 3566 1 10 3019 1 11 1806 1 12 1428 1 A 13 1354 1 14 1274 1 15 1111 1 16 891 1 17 792 1 18
Symmetry A
1 2 3 4 5 6 7 8 9
a
Instead of torsional mode 18 62 cm1, the contributions due to the internal rotation about CC bond were calculated from the potential V() 1 2 V 3 (1 cos 3 ), where is the torsional angle and V 3 450 cm1. Geometry
i , cm1 596 397 216 3076 1193 929 611 492 a
gi 1 1 1 1 1 1 1 1 1
CH2Cl top: Reduced moment of inertia, I r 2.4514 10 39 g cm2, Symmetry number, m 1.
r (CC1.5080.006 r (CvO1.2230.004 r (CO1.3520.005 r (CCl1.7780.005 Rotational constants in cm1: A 0 0.350 738 B 0 0.078 433
r (CH1.090.02 r (OH0.970.015 CCvO126.10.5 CCO 110.6 0.4 CCCl 112.5 0.4 CCH 109.5 assumed HCH 109.5 assumed COH 105.8 1.1 (OvCCCl) 0.0 (OvCOH) 0.0 C 0 0.064 913
3.1. Enthalpy of Formation The recommended value of the enthalpy of formation of gaseous chloroacetic acid at 298.15 K is the sum of the enthalpy of formation of the form of the solid and the enthalpy of sublimation both at 298.15 K. The value of f H (298.15 K, -cr) (509.74 0.49) kJ mol1 is from the work of Lagoa et al.1 who measured the enthalpy of combustion of the form of the solid with a rotating bomb calorimeter. Their result is in agreement with the result f H (298.15 K,cr) (510.5 8.3) kJ mol1 of Smith et al.2 from their re-evaluation of earlier static bomb calorimetry measurements.3 The enthalpy of sublimation, subH (298.15 K) (82.19 0.92) kJ mol1, used here is also from Lagoa et al.,1 and is derived from vapor pressures of the solid obtained from Knudsen effusion experiments. This value is supported by application of Hesss law where the enthalpy of sublimation is the sum of ve processes at the standard pressure of 1 bar. Thus,
subH 298.15 K H cr,334.8 K H cr,298.15 K fusH 334.8 K H 1,462 K H 1,334.8 K vapH 462 K H g,462 K H cr,298.15 K 80.9 2.3 kJ mol 1 . The rst and third terms H ( T 2 ) H ( T 1 ) C p (cr) T are (3.9 0.1) and (21.6 0.5) kJ mol1, respectively, based on C p (cr) (106.7 2.0) J K 1 mol1 from differential scanning calorimetery DSC measurements1 and C p (1) (168.9 4.0) J K 1 mol1 from Pickering.4 This value of C p (cr) differs signicantly from the average value of 144 J K1 mol1 over the range of 288318 K reported in Pickering4 and adopted in NIST Chemistry WebBook5 and Donalski and Hearing.6 The value of C p (1) 179.9 J K 1 mol1 from Urazovskii and Sidorov7 was not used. fusH (334.8 K) 16.3 0.7 kJ mol1 from DSC 1 measurements while vapH (462 K) (54.5 2.0) kJ mol1

TABLE 2. Ideal gas thermodynamic properties of chloroacetic acid C2H3ClO2(g) at the standard state pressure, p 0.1 MPa T r 298.15 K T K 0 25 50 75 100 150 180 190 200 210 220 230 240 250 260 270 280 290 298.15 300 350 400 450 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000 C p S ( G H ( T r ))/ T H H ( T r ) fH fG J K1 mol1 J K1 mol1 J K1 mol1 kJ mol1 kJ mol1 kJ mol1 log K f 0.000 36.170 40.498 44.011 47.641 55.261 59.960 61.543 63.133 64.730 66.332 67.938 69.546 71.155 72.762 74.365 75.962 77.551 78.838 79.129 86.790 93.933 100.456 106.342 116.373 124.509 131.218 136.840 141.610 145.691 149.204 152.241 154.877 157.173 159.180 160.940 162.490 163.858 165.071 0.000 203.287 229.818 246.902 260.056 280.802 291.292 294.576 297.773 300.892 303.940 306.924 309.849 312.721 315.543 318.319 321.053 323.746 325.913 326.402 339.180 351.242 362.689 373.583 393.891 412.462 429.540 445.329 460.000 473.693 486.524 498.590 509.971 520.736 530.946 540.650 549.894 558.716 567.153 829.838 523.832 428.827 385.047 346.988 336.846 334.536 332.618 331.033 329.733 328.676 327.831 327.169 326.668 326.308 326.072 325.945 325.913 325.916 326.908 329.202 332.293 335.881 343.883 352.372 360.965 369.473 377.801 385.903 393.760 401.364 408.719 415.831 422.709 429.364 435.805 442.044 448.090 16.514 15.664 14.701 13.644 12.499 9.928 8.200 7.592 6.969 6.330 5.674 5.003 4.316 3.612 2.892 2.157 1.405 0.638 0.000 0.146 4.296 8.816 13.678 18.851 30.005 42.063 54.859 68.270 82.199 96.569 111.318 126.394 141.753 157.358 173.178 189.186 205.359 221.678 238.125 416.032 417.069 418.460 419.862 420.999 422.890 423.925 424.261 424.594 424.922 425.246 425.565 425.880 426.190 426.493 426.792 427.085 427.372 416.032 414.897 412.226 408.793 404.926 396.468 391.086 389.252 387.401 385.533 383.649 381.752 379.841 377.915 375.978 374.030 372.071 370.101 866.858 430.639 284.702 211.506 138.059 113.487 107.010 101.176 95.894 91.088 86.696 82.668 78.959 75.533 72.359 69.409 66.661 64.556 64.094 53.441 45.429 39.181 34.173 26.641 21.246 17.192 14.035 11.508 9.440 7.717 6.260 5.012 3.932 2.987 2.156 1.417 0.758 0.165
483
427.600 368.487 427.651 428.953 430.094 431.085 431.941 433.310 434.295 434.957 435.342 435.499 435.459 435.259 434.930 434.500 433.991 433.426 432.819 432.185 431.536 430.883 368.121 358.094 347.892 337.556 327.116 306.019 284.721 263.304 241.822 220.311 198.792 177.285 155.797 134.342 112.918 91.512 70.164 48.846 27.566 6.322
is derived from vapor pressure data over a temperature range from 385.45 K to the normal boiling point.9,10 Other values of fusH (334.8 K) are 16.3 kJ mol1 from Pickering4 and 12.3 kJ mol1 from Acree.8 The value H (g,462 K) H (cr,298.15 K) (15.4 0.7) kJ mol1 is interpolated from Table 2 of the present work. This corrects the estimate subH (298.15) (75.3 4.2) kJ mol1 by Cox and Pilcher5,6,11 based on fusH (334 K) 19.4 kJ mol1 from Steiner and Johnson12 and vapH (462 K) 54.5 kJ mol1 mentioned above. Cox and Pilcher also use Hesss law, but assume that the values of C p for the gas, liquid, and solid phases are equal. 3.2. Heat Capacity and Entropy According to the experimental1318 and theoretical15,1719 studies, the lowest-energy conformer of chloroacetic acid
(CH2ClCOOH) has the cis-syn structure C s symmetry with the cis conguration for the carboxylic group and with the chlorine atom lying in the carboxylic plane eclipsed with the carbonyl group. The second more stable form corresponds to the cis-gauche structure with a ClCCvO angle of 130 C 1 symmetry. This form differs from cissyn by internal rotation of the CH2Cl group about the CC bond. Structural parameters of the most stable conformer of chloroacetic acid were determined by gas phase electron diffraction.14 These parameters are in good agreement with results from ab initio18,19 and molecular mechanics15 calculations. In this work, the product of the principal moments of inertia for the most stable cis-syn conformer of chloroacetic acid was calculated using rotational constants determined from the microwave study.13 Structural parameters given above are those obtained from the electron diffraction
484
DOROFEEVA, NOVIKOV, AND NEUMANN cm1 was adopted for calculating the internal rotation contributions of the CH2Cl and OH groups. The difference between the values of C p ( T ) and S ( T ) given here and those by Banerjee23 amounts to 57 and 35 J K1 mol1, respectively. Such a difference could not be due to the discrepancy in molecular constants used. The calculation of Banerjee23 seems to be in error. The rough estimate by the method of group equations, C p CH2ClCOOH C p CH3COOH C p CH2ClCH3 C p CH3CH3 63.4 62.6 52.5 73.5 JK 1 mol 1 , is close to the value obtained in this work 78.8 J K1 mol1 and is very different from the value of Banerjee23 136.0 J K1 mol1. The calculation of Banerjee23 is reproduced in the reference book of Frenkel et al.24
study.14 These parameters reproduce the product of the principal moments of inertia calculated above within 3%. Three conformations with respect to internal rotation around the CC bond were found from an electron diffraction investigation,14 namely, 56% of a cis-syn conformation, 30% of a cis-gauche conformation with the CH2Cl group rotated 131 from the former position, and the remaining 14% of a cis-gauche conformation with 79 rotation of the CH2Cl group. Three conformers of chloroacetic acid were identied by vibrational spectroscopy.1518 Two of them were cis-syn and cis-gauche in agreement with the electron diffraction data. The third stable form was found to have the trans structure, in which the carboxylic hydrogen atom is in the trans position with respect to the CvO bond. Trans conformers arise from rotation of the OH group about the CO bond. Ab initio calculations17,18 and molecular mechanics studies15 strongly suggest that the third stable form should be the trans form. The barrier height for the rotation of the OH group around the CO bond is predicted to be 17003500 cm1.1618 Due to the height of this barrier and the temperature range of the present tabulation, this internal rotation was ignored in this work. Two cis conformers with respect to internal rotation about the CC bond were considered in this work: the cis-syn conformer of C s symmetry and two enantiomeric forms of cis-gauche conformer of C 1 symmetry. The observed data and the calculations14,1618 consistently predict a slight energy preference for the cis-syn form and a small barrier of 400450 cm1 for its interconversion. The simple potential V 1 2 V 3 1 cos 3 , where is the ClCCvO torsional angle, is used here for a very approximate calculation of the internal rotational contributions to the thermodynamic functions of chloroacetic acid. The value of the reduced moment of inertia for the CH2Cl top was derived from the electron diffraction structural parameters.14 Vibrational spectra of chloroacetic acid were studied in the liquid and solid phases,15,20,21 in the vapor22 and matrix.16,18 The fundamental frequencies adopted in this work are those derived by Nieminen et al.18 from matrix isolation infrared spectra ( 1 , 3 5 , 7 , 8 , 9 , 15 17) and ab initio calculation ( 2 , 6 , 10 14). These frequencies are in good agreement with results of normal coordinate analysis,22 molecular mechanics,15 and ab initio17 calculations. The value for the torsional frequency, 18 , was estimated from the microwave spectrum13 and it coincides with the value calculated by the ab initio method.18 The uncertainties in the calculated thermodynamic functions Table 2 may amount to as much as 35 J K1 mol1 for C p ( T ) and 510 J K1 mol1 for S ( T ). They are caused by the uncertainties in the adopted vibrational frequencies and the approximate treatment of the internal rotation. Thermodynamic properties of chloroacetic acid were calculated earlier by Banerjee23 using molecular constants known at that time. A value for the barrier height of 1750
3.3. References
A. L. C. Lagoa, H. P. Diogo, M. Pilar Dias, M. E. Minas da Piedade, L. es, R. C. M. P. F. Amaral, M. A. V. Ribeiro da Silva, J. A. Martinho Simo Guedes, B. J. Costa Cabral, K. Schwarz, and M. Epple, Chem. Eur. J. 7, 483 2001. 2 L. Smith, L. Bjellerup, S. Krook, and H. Westermark, Acta Chem. Scand. 7, 65 1953. 3 nberg, Z. Phys. Chem. Abt. A 172, 197 1935. E. Schja 4 S. U. Pickering, J. Chem. Soc. 67, 664 1895. 5 NIST Chemistry WebBook, NIST Standard Reference Database Number 69, edited by W. G. Mallard and P. J. Lindstrom National Institute of Standards and Technology, Gaithersburg, MD, November 1998 http:// webbook.nist.gov/chemistry. 6 E. S. Domalski and E. D. Hearing, J. Phys. Chem. Ref. Data 25, 1 1996. 7 S. S. Urazovskii and I. A. Sidorov, Dokl. Akad. Nauk SSSR 70, 859 1950. 8 W. E. Acree, Jr., Thermochim. Acta 189, 37 1991. 9 R. R. Dreisbach and S. A. Shrader, Ind. Eng. Chem. 41, 2879 1949. 10 D. R. Stull, Ind. Eng. Chem. 39, 517 1947. 11 J. D. Cox and G. Pilcher, Thermochemistry of Organic and Organometallic Compounds Academic, London, 1970. 12 L. E. Steiner and J. Johnston, J. Phys. Chem. 32, 912 1928. 13 B. P. van Eijck, A. A. J. Maagdenberg, and J. Wanrooy, J. Mol. Struct. 22, 61 1974. 14 J. L. Derissen and J. M. J. M. Bijen, J. Mol. Struct. 29, 153 1975. 15 R. Fausto and J. J. C. Teixeira-Dias, J. Mol. Struct. 144, 225 1986. 16 A. Kulbida and A. Nosov, J. Mol. Struct. 265, 17 1992. 17 R. Fausto, J. J. C. Teixeira-Dias, and F. P. S. C. Gil, J. Chem. Soc., Faraday Trans. 89, 3235 1993. 18 sa nen, J. Phys. Chem. 97, 10925 J. Nieminen, M. Pettersson, and M. Ra 1993. 19 K. E. Edgecombe and R. J. Boyd, Can. J. Chem. 62, 2881 1984. 20 J. R. Barcelo, M. P. Jorge, and C. Otero, J. Chem. Phys. 28, 1230 1958. 21 R. J. Jakobsen and J. E. Katon, Spectrochim. Acta A 29, 1953 1973. 22 L. I. Kozhevina, V. M. Belobrov, V. A. Panichkina, and E. V. Titov, Zh. Strukt. Khim. 20, 405 1979. 23 S. C. Banerjee, Br. Chem. Eng. 14, 671 1969. 24 M. Frenkel, G. J. Kabo, K. N. Marsh, G. N. Roganov, and R. C. Wilhoit, Thermodynamics of Organic Compounds in the Gas State Thermodynamics Research Center, College Station, TX, 1994, Vol. I, p. 341.
1
485
4. Oxopropanedinitrile, NCACOACN
Oxopropanedinitrile (C3N2O) S (298.15 K) 310.0 1.0 J K1 mol1 Molecular constants Point group: C 2 Ground electronic state: X 1A 1 Energy: X 0 cm1 Symmetry number: 2 Quantum weight: g X 1 Ideal gas M r 80.0458 f H (0 K) 246.5 6.4 kJ mol1 f H (298.15 K) 247.5 6.4 kJ mol1
Symmetry A1
Vibrational frequencies, i , and degeneracies g i i , cm1 gi Symmetry
i , cm1
712 208.2 2230 1124 550 245.2
gi 1 1 1 1 1 1
A2
1 2 3 4 5 6
2230 1711 712 553 127.5 307
1 1 1 1 1 1 Geometry
B1 B2
7 8 9 10 11 12
r CvO1.2040.005 r CC1.4610.005 r CwN1.1590.015 CCC114.70.5 CCwN179.20.5
Rotational constants in cm1: A 0 0.225 529 B 0 0.097 556
C 0 0.067 980.
4.1. Enthalpy of Formation The recommended value of enthalpy of formation of oxopropanedinitrile is based on calorimetric measurements by usser1 as evaluated by Cox and Pilcher.2 von Glemser and Ha 4.2. Heat Capacity and Entropy Spectroscopic,310 electron diffraction,11 and 1220 theoretical investigations have shown that oxopropanedinitrile, COCN2, is planar in its ground electronic state X 1 A 1 and belongs to the C 2 symmetry group. In this work, the product of the principal moments of inertia of COCN2 was calculated using the rotational constants determined by microwave spectroscopy.4 In the absence of isotopic data, a unique set of geometrical parameters cannot be obtained from the microwave spectrum. Structural parameters given above are r e parameters determined by combining the results of electron diffraction, microwave spectroscopy, and ab initio calculations.20 These parameters give values for rotational constants which are only 0.3%0.9% different from the observed values. The CCN chain appears to be nearly lin-
ear, the deviation from linearity being 0.8. A small inward bend 0.52 was also found by ab initio calculations12,13,19 but is contradicted by ab initio calculations of Tyrrell15 where the CCN is bent outwards by 1.2. Vibrational spectra of oxopropanedinitrile were studied in the gas, liquid, and solid phase510 but there are still several uncertainties in the assignment of the fundamentals. The vibrational frequencies accepted in this work are those assigned by Miller et al.9 from infrared and Raman spectra of gaseous and liquid oxopropanedinitrile. Their assignment was supported by ab initio calculation.15 According to the semiempirical calculation,21 the excited electronic states of COCN2 lie above 24 000 cm1. They are not taken into account in the calculation of thermodynamic functions. The uncertainties in the calculated thermodynamic functions Table 3are estimated to be 12 J K1 mol1 for C p ( T ) and 12.5 J K1 mol1 for S ( T ). Thermodynamic properties of COCN2 were calculated earlier by Natarajan and Rajendran22 using electron diffracJ. Phys. Chem. Ref. Data, Vol. 30, No. 2, 2001
486

J. Prochorov, A. Tramer, and K. L. Wierzchowski, J. Mol. Spectorsc. 19, 45 1966. 8 J. B. Bates and W. H. Smith, Spectrochim. Acta A 26, 455 1970. 9 F. A. Miller, B. M. Harney, and J. Tyrrell, Spectrochim. Acta A 27, 1003 1971. 10 D. M. Thomas, J. B. Bates, E. R. Lippincott, Indian. J. Pure Appl. Phys. 9, 969 1971. 11 V. Typke, M. Dakkouri, and F. Schlumberger, J. Mol. Struct. 62, 111 1980. 12 W. Kosmus, K. Kalcher, and G. D. Fleming, J. Mol. Struct: THEOCHEM 89, 317 1982. 13 fer, J. Mol. Struct: K. Siam, M. Dakkouri, J. D. Ewbank, and L. Scha THEOCHEM 204, 291 1990. 14 M. Dakkouri, Struct. Chem. 1, 179 1990. 15 J. Tyrrell, J. Mol. Struct.: THEOCHEM 231, 87 1991. 16 M. Dakkouri, J. Mol. Struct.: THEOCHEM 258, 401 1992. 17 J. Tyrrell, J. Mol. Struct.: THEOCHEM 258, 403 1992. 18 J. L. G. De Paz and M. Yanez, J. Mol. Struct.: THEOCHEM 107, 59 1984. 19 M. H. Palmer, J. Mol. Struct.: THEOCHEM 200, 1 1989. 20 ck, K. H. Wiedenmann, and H. D. J. Demaison, G. Wlodarczak, H. Ru Rudolph, J. Mol. Struct.: 376, 399 1996. 21 C. H. Warren and C. Ching, Theor. Chim. Acta 30, 1 1973. 22 A. Natarajan and S. Rajendran, Can. J. Spectorsc. 26, 229 1981.
7
tion structural parameters11 and the vibrational assignment of Bates and Smith.8 The numerical data in the four columns of the table of thermodynamic functions in Natarajan and Rajendran22 are transposed. Moreover, these functions do not correspond to the molecular constants used by the authors. The difference between the C p ( T ) and S ( T ) values given here and those by Natarajan and Rajendran22 amounts to 20 J K1 mol1 and could not be due to the discrepancy in molecular constants used. 4.3. References
usser, Z. Naturforsch. B 3, 159 1948. O. von Glemser and V. Ha J. D. Cox and G. Pilcher, Thermochemistry of Organic and Organometallic Compounds Academic, London, 1970; see also J. B. Pedley, Thermochemical Data and Structures of Organic Compounds Thermodynamics Research Center, College Station, TX, 1994, Vol. I. 3 J. F. Westerkamp, Bol. Acad. Nacl. Cienc. Argen. 42, 191 1961. 4 R. M. Lees, Can, J. Chem. 49, 367 1971. 5 A. Tramer and K. L. Wierzchowski, Bull. Acad. Pol. Sci., Classe III 5, 411 1957. 6 A. Tramer and K. L. Wierzchowski, Bull. Acad. Pol. Sci., Classe III 5, 417 1957.
1 2


TABLE 3. Ideal gas thermodynamic properties of oxopropanedinitrile C3N2O(g) at the standard state pressure, p 0.1 MPa T r 298.15 K) T K 0 25 50 75 100 150 180 190 200 210 220 230 240 250 260 270 280 290 298.15 300 350 400 450 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000 C p J K1 mol1 0.000 33.558 37.466 43.512 49.389 59.439 64.718 66.369 67.965 69.506 70.992 72.425 73.804 75.131 76.408 77.636 78.818 79.956 80.853 81.052 85.979 90.165 93.807 97.037 102.566 107.123 110.898 114.022 116.608 118.754 120.542 122.038 123.297 124.364 125.273 126.052 126.724 127.307 127.815 S J K1 mol1 0.000 186.154 210.389 226.703 240.041 262.030 273.341 276.884 280.329 283.683 286.951 290.138 293.250 296.290 299.262 302.169 305.013 307.799 310.028 310.529 323.404 335.165 346.000 356.054 374.251 390.415 404.974 418.222 430.373 441.591 452.003 461.712 470.804 479.348 487.404 495.022 502.247 509.114 515.658 ( G H ( T r ))/ T J K1 mol1 838.755 519.096 419.028 372.658 332.251 321.506 319.064 317.042 315.374 314.008 312.901 312.018 311.328 310.807 310.434 310.189 310.059 310.028 310.029 311.035 313.327 316.363 319.835 327.420 335.286 343.102 350.724 358.090 365.177 371.984 378.517 384.788 390.810 396.598 402.165 407.526 412.694 417.680 H H ( T r ) kJ mol1 17.147 16.315 15.435 14.424 13.262 10.533 8.670 8.014 7.342 6.655 5.953 5.235 4.504 3.760 3.002 2.232 1.449 0.655 0.000 0.150 4.329 8.735 13.337 18.109 28.099 38.590 49.497 60.748 72.284 84.055 96.023 108.154 120.422 132.807 145.290 157.857 170.497 183.199 195.956 fH kJ mol1 246.525 246.274 246.040 245.902 245.872 246.052 246.268 246.354 246.444 246.539 246.639 246.742 246.848 246.956 247.067 247.179 247.292 247.407 247.500 247.521 248.092 248.634 249.125 249.559 250.253 250.757 251.123 251.390 251.851 251.719 251.810 251.862 251.871 251.846 251.779 251.679 251.541 251.366 251.156 fG kJ mol1 246.525 246.273 246.369 246.567 246.796 247.230 247.447 247.510 247.569 247.623 247.672 247.716 247.756 247.792 247.823 247.851 247.873 247.892 247.905 247.907 247.925 247.864 247.738 247.560 247.090 246.521 245.892 245.219 244.520 243.809 243.084 242.358 241.623 240.895 240.197 239.474 238.765 238.058 237.363
487
log K fs 514.553 257.376 171.722 128.911 86.092 71.806 68.044 64.657 61.592 58.804 56.257 53.922 51.773 49.788 47.949 46.241 44.650 43.431 43.164 37.000 32.367 28.756 25.862 21.511 18.395 16.055 14.232 12.772 11.577 10.581 9.738 9.015 8.389 7.842 7.358 6.929 6.545 6.199
5. Glycolic Acid, HOACH2ACOOH

Glycolic acid (C2H4O3) S (298.15 K) 318.6 5.0 J K1 mol1 Molecular constants Point group: C 1 Ground electronic state: X 1A Symmetry number: 1 Energy: X 0 cm1 Number of optical isomers: n 2 Quantum weight: g X 1 Ideal gas M r 76.0518 f H (0 K) 567.9 10.0 kJ mol1 f H (298.15 K) 583.0 10.0 kJ mol1

488
Symmetry A
1 2 3 4 5 6 7 8 9 10 11
a
Vibrational frequencies, i , and degeneracies g i i , cm1 gi Symmetry 3561 1 12 3561 1 13 2928 1 14 1774 1 A 15 1452 1 16 1439 1 17 1332 1 18 1265 1 19 1143 1 20 1090 1 21 854 1
i , cm1 642 468 270 2919 1231 1019 621 495 281 a
gi 1 1 1 1 1 1 1 1 1 1
Instead of torsional mode 21 152 cm1, the contributions due to the internal rotation round the CC bond were calculated from the potential 8 V() 1 2 n 1 V n (1 cos n), where is the torsional angle, V 1 971.1, V 2 1192.6, V 3 196.0, V 4 244.1, V 5 137.1, V 6 173.5, V 7 118.8, and V 8 48.0 in cm1. COOH top: Reduced moment of inertia, I r 1.9292 10 39 g cm2, Symmetry number, m 1. Geometry r (C1C21.4950.006 r (C1O31.3490.006 r (C1vO41.2100.006 r (C2O51.4060.004 r (O3H90.9890.019 r (O5H80.9560.003 r (C2H6,71.0970.003 Rotational constants in cm1: A 0 0.356 783 B 0 0.135 128 C 0 0.099 891. Product of moments of inertia: I A I B I C 4555 10 117 g3 cm6. Other stable conformers: Point group C1 C1 Symmetry number, 1 1 Number of optical isomers, n 2 2 Energy, cm1 1200 1300 C2C1O3 112.6 0.5 C2C1vO4 124.2 0.4 C1C2O5 111.3 0.4 O5C2H6,7 110.6 0.3 C1C2H6,7 108.8 0.3 C1O3H9 105.5 1.1 C2O5H8 105.2 0.1
5.1. Enthalpy of Formation No experimental or theoretical data on enthalpy of formation of gaseous glycolic acid are known from the literature. The value accepted in this work, f H (298.15 K) (583 10) kJ mol1, is based on two estimates by additivity methods. The rst value was estimated by group additivity using the equation f H HOCH2COOH f H OHC f H CH2COO f H COCO f H OCOH
158.6 33.5 147.3 241.8 581.2 kJ mol 1 with group values generated by Cohen1 except for the missing value for the CH2COO group. The latter was evaluated from values known for related groups: f H CH2COO f H CH2COC f H CHCOCO f H CHCOC2
NIST-JANAF THERMOCHEMICAL TABLES 21.8 18.8 7.1 33.5 kJ mol 1 . The other f H value of glycolic acid may be predicted by the method of group equations2 using f H HOCH2COOH f H CH3COOH f H HOCH2CH3 f H CH3CH3 432.8 235.2 83.8 584.2 kJ mol 1 . Values for f H for CH3COOH, CH3CH2OH, and C2H6 were taken from a compilation by Pedley.3 A value intermediate between the above two estimates was assigned to the enthalpy of formation of glycolic acid. 5.2. Heat Capacity and Entropy From microwave spectroscopic studies,46 the lowestenergy structure of glycolic acid was concluded to be of C s symmetry with the alcoholic hydroxyl group pointing toward the carbonyl oxygen of carboxyl group. This structure involves the intramolecular bonding between the alcohol hydrogen and the carbonyl oxygen. With the exception of the methylene hydrogen all the atoms in the molecule were found to be coplanar. The pathways and energy barriers involved in possible conformational interconversions of glycolic acid were investigated by ab initio calculations.712 Along with rotamers of cis-glycolic acid, where the carbonyl group has the cis conformation with its hydroxyl group, the conformers of trans-glycolic acid were predicted from theoretical studies. Based on electron diffraction data13 the second lowest conformer has been assigned to a cis-glycolic acid with hydrogen bonding between two hydroxyl groups. The energy difference between these conformers was found to be 1470 cm1 based on tting to the diffraction data. However, this result is in conict with theoretical data 8,1012 predicting the energy difference for the two lowest conformers to be 530880 cm1. Moreover, it has been shown by Godfrey et al.11 from ab initio calculations and a microwave study that the two experimentally observed glycolic acid species need not necessarily be the two of lowest energy. The authors in Ref. 11 have assigned the second conformer detected by microwave spectroscopy as the trans-glycolic acid with relative energy of 1200 cm1. This conformer was structurally quite similar to the trans-glycolic acid conformer detected earlier in an infrared matrix isolation study.9 The symmetries and relative stabilities of the conformers of glycolic acid adopted in this work are based on the detailed ab initio calculations of Godfrey et al.11 who tested some of their predictions experimentally. The lowest energy
489
conformer identied by ab initio calculation11 was found to be the C 1 conformer which is a slightly twisted version of the C s from detected by microwave spectroscopy.46 A conformer of C 1 symmetry exists in two enantiomeric forms, and there is a small barrier 1.5 cm1 between this conformer and its mirror image where the saddle point is of C s symmetry. The ground vibrational state energy in these symmetric double wells may be greater than the height of the saddle point, in which case the effective structure of the observed conformer would closely match the C s conformer of the saddle point. It should be noted that the decision between assigning C s or C 1 symmetry is of great importance for the calculation of the thermodynamic functions. For C 1 symmetry the term R ln 2 must be added to both the entropy and Gibbs energy function because two optically isomeric forms are present. C 1 symmetry was accepted in this work as the point group of the lowest-energy form of glycolic acid. The product of the principal moments of inertia for the most stable conformer of glycolic acid was calculated using the rotational constants determined from microwave spectrum investigation.4 Structural parameters given above were determined from the microwave spectra of normal and isotopically substituted species of glycolic acid.5 In general, these geometric molecular parameters are close to those determined from electron diffraction analysis13 and ab initio calculations.7,8,10 According to the ab initio calculation of Godfrey et al.11 the C 1 conformer, a twisted version of cis-form with hydrogen bonding between the hydroxyl groups, is expected to be the second lowest conformer with relative energy of 693 cm1. In this work, the energy prole between two lowestenergy C 1 conformers11 was approximated by a potential energy function for internal rotation around the CC bond,
8
1 V 1 cos n , V 2 n1 n
where is the O4C1C2C5 torsional angle. The eight coefcients ( V n ) in the expansion for this moderately complex potential energy function were determined using data from the ab initio calculation by Godfrey et al.11 The at minimum at 0 corresponds to the lowest-energy C 1 conformer of glycolic acid. Because of the small barrier height between its enantiomeric forms 1.5 cm1, they are not represented by the above potential and their contribution was taken into account by adding the R ln 2 to the entropy and Gibbs energy function. The barrier of 1658 cm1 at 110 separates the lowest-energy conformer from the second C 1 stable conformer with an energy minimum of 693 cm1 at 155. There is a barrier of 338 cm1 at 180 between this conformer and its mirror image. The value of the reduced moment of inertia I r was calculated using the molecular structural parameters of Blom and Bauder.5 The next most abundant C 1 conformers with relative energies of 1200 and 1300 cm1 Goldfrey et al.11 were taken into account in this work ignoring their internal
490
DOROFEEVA, NOVIKOV, AND NEUMANN 5.3. References

N. Cohen, J. Phys. Chem. Ref. Data 25, 1411 1996. D. R. Stull, E. F. Westrum, and G. C. Sinke, The Chemical Thermodynamics of Organic Compounds Krieger, Malabar, FL, 1987; see also the difference method, N. Cohen and S. W. Benson, Chem. Rev. 93, 2419 1993. 3 J. B. Pedley, Thermochemical Data and Structures of Organic Compounds Thermodynamics Research Center, College Station, TX, 1994, Vol. I. 4 C. E. Blom and A. Bauder, Chem. Phys. Lett. 82, 492 1981. 5 C. E. Blom and A. Bauder, J. Am. Chem. Soc. 104, 2993 1982. 6 H. Hasegawa, O. Ohashi, and I. Yamaguchi, J. Mol. Struct. 82, 205 1982. 7 M. D. Newton and G. A. Jeffrey, J. Am. Chem. Soc. 99, 2413 1977. 8 nthard, J. Mol. Struct.; THEOCHEM T.-K. Ha, C. E. Blom, and H. H. Gu 85, 285 1981. 9 nthard, J. Mol. Struct. 146, 289 H. Hollenstein, T.-K. Ha, and H. H. Gu 1986. 10 M. Flock and M. Ramek, Int. J. Quant. Chem. 26, 505 1992. 11 P. D. Godfrey, F. M. Rodgers, and R. D. Brown, J. Am. Chem. Soc. 119, 2232 1997. 12 F. Jensen, Acta Chem. Scand. 51, 439 1997. 13 K. Iijima, M. Kato, and B. Beagley, J. Mol. Struct. 295, 289 1993. 14 r, N. Schwizgebel, G. Grassi, and H. H. H. Hollenstein, R. W. Scha nthard, Spectrochim. Acta A 39, 193 1983. Gu
1 2
rotation and adopting their molecular constants to be the same as those of the basic conformer. The conformers with energies of about 2000 cm1 and higher were ignored because of their negligible contribution to the thermodynamic functions. Hollenstein et al.14 have measured the infrared spectra of 11 isotopic modications of glycolic acid isolated in an argon matrix and have evaluated the transferable valence force eld that reproduced the observed frequencies and isotopic shifts very satisfactorily. The vibrational assignment by Hollenstein et al.14 for C s symmetry is adopted in this work. Fundamentals of glycolic acid calculated by an ab initio method10 are close to experimental values except for the low-frequency torsional mode. The uncertainties in the calculated thermodynamic functions Table 4 may reach 35 J K1 mol1 for C p ( T ) and 510 J K1 mol1 for S ( T ). They are essentially due to the approximate treatment of internal rotation in glycolic acid. Ideal gas thermodynamic properties of glycolic acid have not been reported previously.


TABLE 4. Ideal gas thermodynamic properties of glycolic acid C2H4O3(g) at the standard state pressure, p 0.1 MPa T r 298.15 K) T K 0 25 50 75 100 150 180 190 200 210 220 230 240 250 260 270 280 290 298.15 300 350 400 450 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000 C p S ( G H ( T r ))/ T H H ( T r ) fH fG J K1 mol1 J K1 mol1 J K1 mol1 kJ mol1 kJ mol1 kJ mol1 0.000 37.880 39.654 42.201 46.011 55.327 61.435 63.524 65.636 67.769 69.920 72.089 74.272 76.467 78.669 80.876 83.082 85.285 87.074 87.480 98.188 108.146 117.092 124.943 137.622 147.128 154.453 160.307 165.136 169.214 172.712 175.742 178.385 180.703 182.744 184.547 186.144 187.564 188.830 0.000 194.730 221.605 238.111 250.752 271.119 281.742 285.120 288.431 291.685 294.888 298.043 301.158 304.234 307.276 310.286 313.267 316.221 318.610 319.150 333.446 347.217 360.482 373.235 397.192 419.154 439.298 457.840 474.988 490.923 505.800 519.747 532.870 545.258 556.987 568.121 578.716 588.818 598.472 839.900 524.756 426.614 381.121 341.183 330.402 327.931 325.873 324.168 322.764 321.621 320.704 319.983 319.436 319.042 318.782 318.643 318.610 318.611 319.716 322.298 325.809 329.918 339.162 349.044 359.085 369.041 378.789 388.267 397.449 406.326 414.900 423.182 431.181 438.912 446.387 453.620 460.623 17.007 16.129 15.158 14.138 13.037 10.510 8.759 8.134 7.488 6.821 6.133 5.423 4.691 3.937 3.162 2.364 1.544 0.702 0.000 0.161 4.806 9.968 15.603 21.658 34.818 49.077 64.171 79.919 96.198 112.921 130.022 147.448 165.157 183.114 201.289 219.655 238.191 256.878 275.699 567.940 569.214 571.011 572.893 574.448 577.040 578.430 578.873 579.308 579.732 580.147 580.551 580.945 581.327 581.698 582.057 582.403 582.737
491
log K f
567.940 566.334 1183.274 562.818 587.964 558.300 388.829 553.193 288.955 541.987 534.844 532.410 529.953 527.475 524.977 522.460 519.926 517.376 514.811 512.231 509.639 507.034 188.734 155.206 146.368 138.408 131.200 124.644 118.653 113.157 108.098 103.425 99.096 95.073 91.325 88.456 87.826 73.306 62.392 53.890 47.080 36.855 29.547 24.067 19.809 16.406 13.627 11.315 9.362 7.692 6.248 4.987 3.878 2.893 2.015 1.226
583.000 504.902 583.059 584.470 585.568 586.386 586.965 587.557 587.601 587.259 586.638 585.808 584.815 583.696 582.482 581.200 579.868 504.418 491.195 477.792 464.267 450.666 423.343 395.964 368.606 341.310 314.095 286.970 259.942 233.008 206.174 179.431
578.508 152.761 577.132 126.198 575.750 99.707 574.375 73.299 573.016 46.960

492
6. Glyoxal, OBCHACHBO
Glyoxal (C2H2O2) S (298.15 K) 272.5 1.0 J K1 mol1 Molecular constants trans-Glyoxal Ideal gas M r 58.0366 f H (0 K) 206.4 0.5 kJ mol1 f H (298.15 K) 212.0 0.8 kJ mol1
cis-Glyoxal
Point group: Symmetry number, : Ground electronic state: Quantum weight, g x : Relative energy, X , cm1: Vibrational frequencies, i , and degeneracies, g i Symmetry
C 2h 2 X 1A g 1 0
C 2 2 X 1A 1 1 1555
i , cm1
2843.27 1744.12 1352.60 1065.81 550.53 801.36 ...a 1047.81 2835.07 1732.10 1312.38 338.55 1.525 0.003 1.207 0.002 1.116 0.008 121.2 0.2 126.6 1.7 1.844 319 0.160 021 0.147 351 504.42 0.8199 1
gi 1 1 1 1 1 1 1 1 1 1 1 1
Symmetry A1
i , cm1
2841 1746 1369 827 284.5 1050 ...a 750 2810 1761 1360 825 1.522 1.208 1.109 123.1 122.8 0.891 062 0.206 503 0.167 864 710.17 0.4807 1
gi 1 1 1 1 1 1 1 1 1 1 1 1
1 2 3 4 5 6 7 8 9 10 11 12
Geometry: r CC r CvO r CH CCvO OvCH
Ag
Au Bg Bu
A2 B1 B2
Rotational constants, cm1: A0 B0 C0 Product of moments of inertia, I A I B I C 10117 g3 cm6: Reduced moment of inertia for CHO top, I r 1039 g cm2: Symmetry number for CHO top, m :
a
Instead of torsional mode 7 126.7 cm1 for trans - and 89.6 cm1 for cis -glyoxal, the contributions due 1 6 n 1 V n (1 cos n), where is the to the internal rotation were calculated from the potential V ( ) 2 torsional angle, V 1 1587.6, V 2 1139.5, V 3 59.0, V 4 110.9, V 5 40.0, and V 6 0.0 in cm1. For 6 the internal rotational constant B , the Fourier expansion coefcients were used B B 0 n 1 B n cos n where B 0 4.213, B 1 1.117, B 2 0.421, B 3 0.126, B 4 0.040, B 5 0.015, and B 6 0 in cm1.
NIST-JANAF THERMOCHEMICAL TABLES 6.1. Enthalpy of Formation The value of f H 298.15 K for glyoxal accepted in this work was determined by Fletcher and Pilcher1 from measurements of heat of combustion by ame calorimetry. A lower value of 224.3 kJ mol1 was obtained by Curtiss et al.2 from ab initio calculation. 6.2. Heat Capacity and Entropy It has been shown both spectroscopically318 and theoretically1935 that glyoxal (OvCHCHvO) undergoes rotational isomerization and exists in two planar, trans and cis, forms. The structure of the more stable trans conformer has been determined by a combination of electron diffraction and rotational data.36 As trans-glyoxal has no dipole moment, there is no microwave spectrum, and accurate rotational constants for the ground state can only be obtained by rotational analysis of infrared or electronic absorption bands. The values obtained for the rotational constants of trans-glyoxal4,5,13,14,37 are in good agreement with each other. Using the rotational constants for the ve isotopic species, Birss et al.11 have evaluated the structural parameters for trans-glyoxal. These parameters are in excellent agreement with electron diffraction results.36 In general, these experimental geometries are in good agreement with theoretical results.24,26,28,3335,3843 The product of the principal moments of inertia for the planar structure of trans-glyoxal of C 2 h symmetry was calculated here using the rotational constants determined from a high-resolution Fourier-transform study of trans-glyoxal.15 Structural parameters of transglyoxal given above are those obtained from an electron diffraction investigation.36 These parameters reproduce the spectroscopic moments of inertia with in an accuracy of 0.2%0.3%. Rotational constants for the ground state of cis-glyoxal were obtained from rotational analysis of the 00 band6,8 and by microwave spectroscopy.7,10,12,17,18 The product of the principal moments of inertia for the planar structure of cisglyoxal of C 2 symmetry was calculated in this work using the rotational constants determined from microwave studies.17,18 Sets of possible structural parameters of cisglyoxal were evaluated using the rotational constants for its isotopomers combined with assumptions of the values of some parameters.7,8,10,28,44 The geometry of cis-glyoxal was also calculated by ab initio22,24,2629,3133,35,38,39,41,42 and molecular mechanics43 methods. Structural parameters of cisglyoxal shown above were proposed by Tyulin et al.44 from analysis of microwave data.17 Vibrational spectra of glyoxal were studied in the gas and with matrix isolation phase48,10,13,15,16,4555 techniques.5658 The experimental assignments have been conrmed by normal coordinate analyses44,5964 and theoretical calculations.26,28,29,31,34,35,40,43,6570 The adopted values for vibrational frequencies of trans-glyoxal were taken from the investigation of dispersed uorescence spectra53 ( 1 5 , 8 ), high-resolution infrared spectra48 ( 6 , 7 , 11 , 12), a rotational ne structure of the CH
493
stretching band5 ( 9 ) and a high-resolution infrared Fouriertransform study15 ( 10). The uncertainties in these values are within 0.5 cm1. The adopted values of 1 7 and 10 fundamental frequencies of cis-glyoxal are those observed from gas and Ar-matrix spectra.13,18,55,58 For unobserved frequencies ( 8 , 9 , 11 , 12), the values were selected on the basis of ab initio calculations;28,31,35,68 and their uncertainties are estimated to be 2550 cm1. The torsional potential function for glyoxal has been investigated experimentally3,6,7,9,13,16,18,71 and 1934,70,72 theoretically by many authors. An early infrared study3 suggested a very high trans-cis rotation barrier ( V rot) of 4810 cm1 based on a torsional frequency of 128 cm1. Currie and Ramsay6 provided the rst estimate for cis-trans enthalpy difference, H (1125 100) cm1, from the temperature dependence of cis and trans absorption bands in the visible spectrum. Durig et al.9 obtained the torsional potential function for glyoxal that ts the infrared data of the trans conformer and the microwave intensity data of the cis conformer and yields the H (1180 150) cm1 with a barrier height V rot 1770 cm1. The energy difference between the cis and trans conformers has been revised upwards twice by Butz et al., rst to (1350 200) cm1 derived from a spectroscopic temperature study13 and then to (1688 100) cm1 by tting spectroscopic data to a torsional potential.16 The potential function obtained by Butz et al.16 has a barrier to bner et al.18 trans-cis rotation of 2077 cm1. Recently Hu have determined the cis-trans enthalpy difference, H (1555 48) cm1, from absorption intensities of glyoxal by microwave spectroscopy. This value is intermediate between the values reported by Butz et al.13,16 Based on this bner et al.18 have recalculated the potential value for H , Hu curve for internal rotation in glyoxal ( V rot 2003 cm1). Numerous ab initio calculations yield different results for H depending on the basis sets and levels of calculation 1050,20 13201970,34 1490,29 15001990,31 1504,72 1600,26,27,32 17002200,23 2000,22,24,25,28,30 and 2422 cm1.70 Due to this wide range they are not of help in deciding among the available experimental data. bner The torsional potential function determined by Hu et al.18 is accepted in this work in order to account for the internal rotation in glyoxal. The Fourier expansion coefcients for the internal rotation constant B were adopted to be the same as those used by Durig et al.9 and later by other authors.16,18 The values of the reduced moment of inertia, I r , were calculated from accepted structural parameters see above. Experimentally observed absorption spectra of glyoxal have been identied with transitions to the excited elecA 1A u ( T 0 tronic states a 3 A u ( T 0 19 199 cm1) and 1 45,73,74 21 973 cm ). These assignments agree with other experimental7579 and theoretical35,80,81 studies. Dykstra and Schaefer82 have predicted two low-lying 15 000 cm1 unobserved triplet states from ab initio calculation. Because of high energies of excited electronic states of glyoxal, they are not considered in this work. These electronic states would only make an appreciable contribution to the thermoJ. Phys. Chem. Ref. Data, Vol. 30, No. 2, 2001
494

TABLE 5. Ideal gas thermodynamic properties of glyoxal C2H2O2(g) at the standard state pressure, p 0.1 MPa T r 298.15 K) T K 0 25 50 75 100 150 180 190 200 210 220 230 240 250 260 270 280 290 298.15 300 350 400 450 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000 C p S ( G H ( T r ))/ T H H ( T r ) fH fG J K1 mol1 J K1 mol1 J K1 mol1 kJ mol1 kJ mol1 kJ mol1 log K f 0.000 33.558 36.353 39.053 41.428 45.964 48.675 49.594 50.525 51.471 52.433 53.414 54.414 55.434 56.473 57.533 58.611 59.707 60.612 60.819 66.557 72.398 78.086 83.427 92.680 99.929 105.446 109.622 112.807 115.270 117.204 118.749 120.001 121.030 121.887 122.609 123.223 123.749 124.204 0.000 168.135 192.179 207.448 219.011 236.671 245.290 247.947 250.514 253.002 255.419 257.771 260.066 262.307 264.502 266.653 268.765 270.841 272.508 272.883 282.686 291.956 300.814 309.321 325.380 340.236 353.957 366.629 378.351 389.223 399.339 408.784 417.631 425.947 433.786 441.198 448.224 454.900 461.260 682.424 431.899 354.677 319.370 289.008 281.018 279.209 277.710 276.474 275.463 274.643 273.987 273.476 273.089 272.810 272.628 272.531 272.508 272.509 273.270 275.031 277.407 280.176 286.389 293.034 299.803 306.534 313.137 319.566 325.797 331.821 337.638 343.251 348.667 353.894 358.941 363.817 368.531 13.690 12.857 11.986 11.042 10.306 7.851 6.431 5.940 5.439 4.929 4.410 3.880 3.341 2.792 2.233 1.663 1.082 0.490 0.000 0.112 3.296 6.770 10.533 14.572 23.395 33.041 43.323 54.086 65.214 76.623 88.251 100.051 111.991 124.044 136.191 148.417 160.709 173.058 185.457 206.432 206.857 207.559 208.268 208.805 209.665 210.146 210.306 210.467 210.627 210.788 210.948 211.107 211.265 211.422 211.576 211.729 211.880 206.432 206.353 205.605 204.466 203.114 200.077 198.114 197.441 196.761 196.071 195.374 194.670 193.959 193.241 192.517 191.787 191.051 190.310 431.146 214.791 142.401 106.095 69.672 57.490 54.280 51.388 48.769 46.387 44.210 42.213 40.375 38.677 37.103 35.641 34.278 33.235 33.005 27.723 23.750 20.652 18.168 14.436 11.767 9.766 8.211 6.969 5.955 5.112 4.400 3.791 3.265 2.805 2.400 2.041 1.720 1.432
212.000 189.702 212.027 212.711 213.294 213.765 214.126 214.547 214.638 214.488 214.174 213.761 213.288 212.789 212.289 211.806 211.349 210.932 210.556 210.227 209.948 209.719 189.563 185.765 181.874 177.917 173.913 165.827 157.696 149.568 141.471 133.416 125.404 117.436 109.508 101.621 93.765 85.921 78.122 70.337 62.575 54.823
dynamic functions at temperatures above 3000 K. The uncertainties in the calculated thermodynamic functions Table 5 are estimated to be 0.53.0 J K1 mol1 for C p ( T ) and 1.03.0 J K1 mol1 for S ( T ). The thermodynamic functions of glyoxal as an equilibrium mixture of trans and cis conformers were calculated by Compton.83 The discrepancies between C p ( T ) and S ( T ) values calculated in this work and in Compton83 increase with temperature and reach 3.1 and 2.2 J K1 mol1, respectively, at 1000 K. These discrepancies are due to different
molecular constants used in the calculations and the noninclusion of internal rotation in glyoxal by Compton.83 Values of H ( T ) H (0) given by Compton appear to be in error. Hollenstein et al.84 derived the thermodynamic functions of glyoxal using the semiclassical approximation for the sumover-states calculation for nonrigid molecules. The difference between their C p ( T ) and S ( T ) values and those calculated in this work range from 0.1 to 8.8 J K1 mol1 depending on the level of approximation used. The discrepancies with the results of statistical calculations by Natarajan
NIST-JANAF THERMOCHEMICAL TABLES et al.85 amount to 5060 J K1 mol1 and cannot be due to differences in the molecular constants used. 6.3. References
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1 2 42
495
fer, K. Siam, V. J. Klimkowski, and C. Van AlseN. L. Allinger, L. Scha noy, J. Comput. Chem. 6, 331 1985. 43 N. L. Allinger and Y. Fan, J. Comput. Chem. 15, 251 1994. 44 V. I. Tyulin, G. M. Kuramshina, Y. A. Pentin, and L. H. Ho, Zh. Strukt. Khim. 38, 287 1997. 45 J. C. D. Brand, Trans. Faraday Soc. 50, 431 1954. 46 R. K. Harris, Spectrochim. Acta 20, 1129 1964. 47 W. Holzer and D. A. Ramsay, Can. J. Phys. 48, 1759 1970. 48 A. R. H. Cole and G. A. Osborne, Spectrochim. Acta A 27, 2461 1971. 49 R. Y. Dong and D. A. Ramsay, Can. J. Phys. 51, 1491 1973. 50 A. B. Duval, D. A. King, R. Haines, N. R. Isenor, and B. J. Orr, J. Raman Spectrosc. 17, 177 1986. 51 G. A. Bickel and K. K. Innes, J. Chem. Phys. 86, 1752 1987. 52 D. Frye, L. Dai, and H.-L. Lapierre, J. Chem. Phys. 89, 2609 1988. 53 E. Pebay Peyroula, A. Delon, and R. Jost, J. Mol. Spectrosc. 132, 123 1988. 54 W. G. Wickun and K. K. Innes, J. Mol. Spectrosc. 127, 277 1988. 55 R. Y. Dong, R. Nanes, and D. A. Ramsay, Can. J. Chem. 71, 1595 1993. 56 M. Diem, B. G. MacDonald, and E. K. C. Lee, J. Phys. Chem. 85, 2227 1981. 57 rnig, and J. M. L. J. Van IJzendoorn, L. J. Allamandola, F. Baas, S. Ko Greenberg, J. Chem. Phys. 85, 1812 1986. 58 A. Engdahl and B. Nelander, Chem. Phys. Lett. 148, 264 1988. 59 T. Fukuyama, K. Kuchitsu, and Y. Morino, Bull. Chem. Soc. Jpn. 41, 3019 1968. 60 C. Cossart-Magos, Spectrochim. Acta A 34, 415 1978. 61 H. J. Oelichmann, D. Bougeard, and B. Schrader, J. Mol. Struct. 77, 149 1981. 62 L. O. Pietila, K. Palmo, and B. Mannfors, J. Mol. Spectrosc. 112, 104 1985. 63 L. O. Pietila, K. Palmo, and B. Mannfors, J. Mol. Spectrosc. 116, 1 1986. 64 R. Sander and H. Bettermann, J. Mol. Struct. 263, 123 1991. 65 Y. N. Panchenko, P. Pulay, and F. Torok, J. Mol. Struct. 34, 283 1976. 66 H. Kato, K. Yamashita, and S. Kato, J. Phys. Chem. 82, 2115 1978. 67 C. W. Bock, P. George, and M. Trachtman, J. Mol. Spectrosc. 78, 248 1979. 68 Y. N. Panchenko, G. R. De Mare, and V. I. Pupyshev, J. Phys. Chem. 99, 17544 1995. 69 X. Zhou, C. J. M. Wheeless, and R. Liu, Vib. Spectrosc. 12, 53 1996. 70 M. L. Senent, J. Mol. Struct. 406, 51 1997. 71 H. H. Le and V. I. Tyulin, Zh. Strukt. Khim. 16, 63 1975. 72 E. L. Coitino and J. Tomasi, Chem. Phys. 204, 391 1996. 73 G. W. King, J. Chem. Soc. 5054 1957. 74 D. A. Ramsay, M. Verloet, F. Vanhorenbeke, M. Godefroid, and M. Herman, J. Mol. Spectrosc. 149, 348 1991. 75 W. Goetz, A. J. McHugh, and D. A. Ramsay, Can. J. Phys. 48, 1 1970. 76 L. G. Anderson, C. S. Parmenter, H. M. Poland, and J. D. Rau, Chem. Phys. Lett. 8, 232 1971. 77 L. G. Anderson, C. S. Parmenter, and H. M. Poland, Chem. Phys. 1, 401 1973. 78 J. Kelder, H. Cerfontain, J. K. Eweg, and R. P. H. Rettschnick, Chem. Phys. Lett. 26, 491 1974. 79 J. M. Leclercq, C. Mijoule, and F. Yvan, J. Chem. Phys. 64, 1464 1976. 80 C. E. Dykstra, R. R. Lucchese, and H. F. Schaefer III, J. Chem. Phys. 67, 2422 1977. 81 W. B. Mueller, J. F. Harrison, and P. J. Wagner, J. Am. Chem. Soc. 100, 33 1978. 82 C. E. Dykstra and H. F. Schaefer III, J. Am. Chem. Soc. 98, 401 1976. 83 D. A. C. Compton, J. Chem. Soc., Perkin Trans. 2, 1307 1977. 84 nthard, Chem. Phys. 47, 269 H. Hollenstein, A. Bauder, and H. H. Gu 1980. 85 A. Natarajan, P. Kolandaivelu, and A. Savarianandam, J. Indian Chem. Soc. 59, 1155 1982.

496
CN 7. Cyanooxomethyl Radical, OC
Cyanooxomethyl radical (C2NO) S (298.15 K ) 278.2 1.5 J K 1 mol 1 Molecular Constants Point group: C s Ground electronic state: X 2A Excited electronic state: A 2A Energy: X 0 cm1 Energy: A 15 500 cm1 Symmetry number: 1 Quantum weight: g X 2 Quantum weight: g A 2 Ideal gas M r 54.0281 f H (0 K) 207.2 10.0 kJ mol 1 f H (298.15 K) 210.0 10.0 kJ mol 1
Symmetry A 1 2 3
Vibrational frequencies, i , and degeneracies, g i i , cm1 gi Symmetry 2249 1 4 1703 1 5 909 1 A 6 Geometry r (CvO) 1.19 0.02 r (CC) 1.47 0.02 r ( wN) 1.16 0.02 OvCC 128 3 CCwN 170 5
i , cm1 488 174 233
gi 1 1
Product of moments of inertia: I A I B I C 183 10 117 g3 cm6.
7.1. Enthalpy of Formation No experimental data are available for enthalpy of formation of the cyanooxomethyl radical. The value accepted in this work was estimated by Francisco and Liu1 by using the isodesmic reaction approach with the following reaction: O. CNHCNC N HC OC 2 2 The relationship between the enthalpy of formation of CN and the enthalpy change of the above reaction is OC CN H C N H HC O f H OC f 2 2 f f H HCN r H . Based on known experimental enthalpies of formation of O, and the H value predicted by ab iniHCN, C2N2, HC r tio calculations, Francisco and Liu1 have estimated the en CN to be 207.5210.0 kJ mol1. thalpy of formation for OC
values are based on the results of ab initio calculations1,2 and comparison with structural parameters of COCN2, COX2, O (XF, Cl) molecules. and XC CN were calculated in this Vibrational frequencies of OC work using the following force constants: f CvO11.413 mdyn/, f CC7.225 mdyn/, f CwN13.674 mdyn/, f CCvO0.750 mdyn , f CCwN0.110 mdyn , f CC,CO0.513 mdyn/, f CC,CN1.543 mdyn/, f CC,CCO0.585 mdyn.
7.2. Heat Capacity and Entropy There are no experimental data on structure and vibra CN. According to ab initio tional spectra of OC 1,2 calculations, a bent structure of C s symmetry is adopted in CN in the ground electronic state this work for OC X 2A . The product of the principal moments of inertia was calculated using the structural parameters shown above. These
These constants were transferred from the COCN2 molecule except for f CCO and f CCN whose values were reduced by comparison with the bending force constants in O (XF, Cl, Br). Normal coordinate analysis COX2 and XC for COCN2 was carried using the vibrational assignment of Miller et al.3 The uncertainties in the calculated frequencies CN can reach 50 cm1. These frequencies agree overof OC all with those resulting from the ab initio calculation.1 CN was preThe rst excited electronic state A 2 A of OC 1 dicted at an energy of 15 500 cm by an ab initio calculation1 and was included in the calculations in this work. Structural parameters and vibrational frequencies for the A 2 A state were accepted as identical to those of the ground state.
NIST-JANAF THERMOCHEMICAL TABLES The uncertainties in the calculated thermodynamic functions Table 6 are estimated to be 1.52.0 J K1 mol1 for C p ( T ) and 1.53.0 J K1 mol1 for S ( T ). Ideal gas thermodynamic properties of the cyanooxomethyl radical have not been reported previously. 7.3. References
497
J. S. Francisco and R. Liu, J. Chem. Phys. 107, 3840 1997. A. L. Cooksy, J. Am. Chem. Soc. 117, 1098 1995. 3 F. A. Miller, B. M. Harney, and J. Tyrrell, Spectrochim. Acta A 27, 1003 1971.
1 2
TABLE 6. Ideal gas thermodynamic properties of the cyanooxomethyl radical C2NOg at the standard state pressure, p 0.1 MPa ( T r 298.15 K) T K 0 25 50 75 100 150 180 190 200 210 220 230 240 250 260 270 280 290 298.15 300 350 400 450 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000 C p J K1 mol1 0.000 33.297 35.132 38.803 42.195 47.280 49.604 50.296 50.955 51.582 52.182 52.757 53.309 53.839 54.350 54.842 55.318 55.779 56.145 56.226 58.286 60.126 61.811 63.373 66.186 68.609 70.666 72.395 73.839 75.044 76.051 76.896 77.609 78.214 78.731 79.175 79.559 79.894 80.189 S J K1 mol1 0.000 174.512 197.975 212.901 224.543 242.677 251.509 254.210 256.807 259.308 261.721 264.054 266.311 268.498 270.620 272.680 274.683 276.632 278.183 278.531 287.356 295.262 302.442 309.036 320.845 331.235 340.534 348.960 356.665 363.761 370.335 376.457 382.182 387.558 392.622 397.409 401.946 406.257 410.362 ( G H ( T r ))/ T J K1 mol1 685.016 436.251 359.439 324.309 294.223 286.384 284.620 283.165 281.970 280.995 280.208 279.582 279.095 278.729 278.467 278.296 278.205 278.183 278.184 278.877 280.439 282.491 284.820 289.863 295.046 300.161 305.122 309.897 314.475 318.860 323.057 327.078 330.933 334.632 338.185 341.602 344.893 348.064 H H ( T r ) kJ mol1 13.594 12.763 11.914 10.990 9.977 7.732 6.278 5.778 5.272 4.759 4.240 3.715 3.185 2.649 2.108 1.562 1.012 0.456 0.000 0.104 2.968 5.929 8.978 12.108 18.589 25.332 32.299 39.454 46.768 54.214 61.770 69.419 77.145 84.937 92.785 100.681 108.618 116.591 124.596 fH kJ mol1 207.190 207.298 207.405 207.563 207.781 208.327 208.683 208.802 208.921 209.039 209.156 209.271 209.384 209.496 209.605 209.712 209.817 209.919 210.000 210.018 210.473 210.852 211.153 211.379 211.634 211.683 211.585 211.379 211.093 210.748 210.353 209.918 209.441 208.931 208.384 207.808 207.199 206.559 205.890 fG kJ mol1 207.190 206.094 204.851 203.542 202.171 199.251 197.403 196.773 196.137 195.495 194.847 194.194 193.536 192.873 192.206 191.535 190.860 190.181 189.625 189.499 186.041 182.524 178.965 175.376 168.146 160.892 153.643 146.410 139.204 132.033 124.893 117.792 110.720 103.689 96.710 89.746 82.823 75.929 69.071
log K f 430.604 214.003 141.757 105.602 69.384 57.284 54.096 51.225 48.626 46.262 44.102 42.121 40.298 38.614 37.054 35.605 34.255 33.221 32.994 27.765 23.835 20.773 18.321 14.638 12.006 10.032 8.497 7.271 6.270 5.436 4.733 4.131 3.611 3.157 2.758 2.403 2.087 1.804

498
8. Oxalic Acid, HOACOACOAOH

Oxalic acid (C2H2O4) S (298.15 K) 320.6 5.0 J K1 mol1 Molecular constants Point group: C 2 h Ground electronic state: X 1A g Symmetry Ag Energy: X 0 cm1 Symmetry number: 2 Quantum weight: g X 1 Ideal gas M r 90.0354 f H (0 K) 721.2 2.0 kJ mol1 f H (298.15 K) 731.8 2.0 kJ mol1
Au
1 2 3 4 5 6 7 8 9
a
Vibrational frequencies, i , and degeneracies, g i i , cm1 gi Symmetry 3484 1 1800 1 Bg 1423 1 1195 1 Bu 815 1 608 1 405 1 666 1 460 1
10 11 12 13 14 15 16 17 18
i , cm1 a 851 563 3484 1826 1278 1127 651 264
gi 1 1 1 1 1 1 1 1 1
Instead of torsional mode 10 90 cm1, the contributions due to the internal rotation about CC bond were calculated from the potential V() 1 2 V 1 (1 cos ), where is the torsional angle and V 1 700 cm1. COOH top: Reduced moment of inertia, I r 3.6454 10 39 g cm2, Symmetry number, m 1 Geometry r CC1.5480.004 r CvO1.2080.001 r CO1.3390.002 r OH1.0560.014 CCvO123.10.9 OvCO125.00.2 COH104.42.3
8.1. Enthalpy of Formation Wilhoit and Shiao1 have measured the enthalpy of combustion of solid oxalic acid in a rotating platinum bomb calorimeter and have calculated f H C2H2O4 , cr,298.15 K829.91.0) kJ mol1. The enthalpy of formation of gaseous oxalic acid is calculated from this value by adding the enthalpy of sublimation, subH 98.1 kJ mol1, obtained from vapor pressure measurements.2 8.2. Heat Capacity and Entropy Nahlovska et al.3 carried out an electron diffraction and an IR study of oxalic acid indicating that the structure was in a planar trans conformation C 2 h symmetry in which the
hydrogen atom of one COOH group participated in intramolecular hydrogen bonding with the carbonyl oxygen of the other COOH group hydrogen bonded trans conformer. Infrared matrix-isolation spectra of oxalic acid4 were interpreted in terms of the same model and the tentative conclusion was made that a second conformer of oxalic acid exists in the vapor phase. This conformer was suggested to be a trans form C 2 h symmetry with the hydrogen atom of each COOH group oriented towards the carbonyl oxygen of the same COOH group free trans form. Oxalic acid was determined to be in its trans conformation from x-ray crystallographic studies5 and no other conformers were observed. Studies of oxalic acid in solution6 favored almost free rota-
NIST-JANAF THERMOCHEMICAL TABLES tion, which would include a range of possible conformations. Ab initio studies of oxalic acid79 have obtained a most stable hydrogen bonded trans planar structure in agreement with the results of an electron diffraction investigation.3 The hydrogen bonded or free trans form was found to be lowest energy depending on the basis set used in the ab initio calculations.10 The free trans conformer was reported to be most stable by an earlier ab initio study.11 The hydrogen bonded trans form C 2 h symmetry is accepted for oxalic acid in this work. Its product of principal moments of inertia was calculated using the structural parameters determined from the electron diffraction study.3 Following the results of a theoretical calculation by Tyrrell,9 it was assumed that there is a slight energy preference for this conformer and only a small barrier of about 2 kcal mol1 700 cm1 separating it from other stable conformers. The simple approximate potential,
1 V 2 V 1 1 cos ,
499
where is the OCCO torsional angle, was used here for the calculation of internal rotational contributions to the thermodynamic functions of oxalic acid. The value of the reduced moment of inertia for the COOH top was derived from the molecular constants shown above. There are several studies of the vibrational spectra of the free C2H2O4 molecule3,4,1214 but some fundamentals are still unobserved. Stace and Oralratmanee14 have reported the infrared vapor phase measurements and the rst vapor phase Raman spectra. They have proposed a new vibrational frequencies assignment based on their experimental results as well as calculated in-plane frequencies using an Urey Bradley force eld derived from formic and acetic acid. Redington and Redington4 have investigated the infrared spectra of oxalic acid vapor and the infrared spectra of matrixisolated C2H2O4, C2HDO4, and C2D2O4 and have carried out a normal coordinate analysis using a general valence force eld for the in-plane infrared-active modes. None of the above studies, however, gives a complete vibrational assignment for oxalic acid. De Villepin and Novak15 have developed a general valence force eld for both infrared and Raman frequencies using the relatively small number of experimentally observed fundamentals. Their force eld reproduces the experimental vibrational spectra of oxalic and is comparable with force elds already known for other carboxylic acids. The fundamental frequencies 2 5 and 7 adopted here were observed in the Raman spectra of gaseous oxalic acid.14 The 405 cm1 mode was subsequently reassigned to 7 . 4 The values of 8 , 9 , 13 16 , and 18 are those determined from gas-phase infrared spectra.4 The value for 17 was obtained from spectra of neon matrix-isolated oxalic acid.4 The uncertainties in these experimental frequencies are in the range of 510 cm1. Redington and Redington4 have suggested tentative values for 6 ( A g ) 538 cm1, 11( B g ) 590 cm1, and 12( B g ) 512 cm1 fundamentals using possible combination bands.
The adopted values of these frequencies were taken from normal coordinate calculations.15 Calculations for the other frequencies are in good agreement with experimental results. The value of the symmetric OH stretching frequency 1 was accepted to be the same as the value of antisymmetric OH stretching ( 13) and it coincides with the calculated value.15 The uncertainties in these frequencies are estimated to be 2550 cm1. Evidently due to its weak intensity, the CC torsion mode 10( A u ) was not observed in a vapor phase spectra search that extended down to 35 cm1.4 Ab initio calculations8,10 have suggested the value of 160 cm1 for the torsional mode, however, it should be noted that all other calculated values are much greater than those from experiment. Cyvin and Alfheim16 have calculated 10 90 cm1 using force constants transferred from formic and acetic acids. The value of 110 cm1 was obtained from other normal coordinate calculation.15 The corresponding torsional mode for oxalyl uoride FCOCOF was observed in the gas phase at 54 cm1 and in the solid phase at 94 cm1.17 From the ratio of torsC2F2O2 , solid/torsC2F2O2 , gas) 1.74 and the value of 138 cm1 for the torsional mode of solid oxalic acid,15,18 the value of 80 cm1 for the torsional mode of gaseous oxalic acid is expected. The uncertainties in the calculated thermodynamic functions Table 7 may be as much as 57 J K1 mol1 for C p ( T ) and 510 J K1 mol1 for S ( T ). These uncertainties arise from the uncertainties in the adopted values of the vibrational frequencies and the simple and approximate model for internal rotation. Ideal gas thermodynamic properties of oxalic acid have not been reported previously. 8.3. References
R. C. Wilhoit and D. Shiao, J. Chem. Eng. Data 9, 595 1964. R. S. Bradley and S. Cotson, J. Chem. Soc. 1684 1953. 3 Z. Nahlovska, B. Nahlovsky, and T. G. Strand, Acta Chem. Scand. 24, 2617 1970. 4 R. L. Redington and T. E. Redington, J. Mol. Struct. 48, 165 1978. 5 J. L. Derissen and P. H. Smit, Acta Crystallogr. Sect. B: Struct. Crystollgr. Cryst. Chem. 30, 2240 1974. 6 T. A. Shippey, J. Mol. Struct. 65, 71 1980. 7 fer, J. Mol. Struct: C. Van Alsenoy, V. J. Klimkowski, and L. Scha THEOCHEM 109, 321 1984. 8 T. Kakumoto, J. Sci. Hiroshima Univ. A 51, 69 1987. 9 J. Tyrrell, J. Mol. Struct: THEOCHEM 258, 389 1992. 10 T. Kakumoto, K. Saito, and A. Imamura, J. Phys. Chem. 91, 2366 1987. 11 D. Ajo, G. Condorelli, I. Fragala, and G. Granozzi, J. Mol. Struct. 37, 160 1977. 12 M. Pava Bruce and F. E. Stafford, J. Phys. Chem. 72, 4628 1968. 13 L. Bardet, G. Fleury, and V. Tabacik, C. R. Acad. Sci. B 270, 1277 1970. 14 B. C. Stace and C. Oralratmanee, J. Mol. Struct. 18, 339 1973. 15 J. De Villepin, A. Novak, and D. Bougeard, Chem. Phys. 73, 291 1982. 16 S. J. Cyvin and I. Alfheim, Acta Chem. Scand. 24, 2648 1970. 17 J. R. Durig, S. C. Brown, and S. E. Hannum, J. Chem. Phys. 54, 4428 1971. 18 J. De Villepin, A. Novak, and F. Romain, Spectrochim. Acta A 34, 1009 1978.
1 2

500

TABLE 7. Ideal gas thermodynamic properties of oxalic acid C2H2O4g at the standard state pressure, p 0.1 MPa ( T r 298.15 K) T K 0 25 50 75 100 150 180 190 200 210 220 230 240 250 260 270 280 290 298.15 300 350 400 450 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000 C p S ( G H ( T r ))/ T H H ( T r ) fH fG J K1 mol1 J K1 mol1 J K1 mol1 kJ mol1 kJ mol1 kJ mol1 0.000 40.556 41.771 43.565 46.685 56.008 62.509 64.693 66.861 69.005 71.116 73.190 75.223 77.213 79.160 81.061 82.918 84.731 86.176 86.501 94.724 101.995 108.424 114.112 123.628 131.195 137.323 142.375 146.605 150.187 153.247 155.880 158.158 160.137 161.866 163.381 164.714 165.891 166.934 0.000 193.337 221.869 239.102 252.031 272.618 283.401 286.839 290.213 293.527 296.786 299.993 303.151 306.262 309.329 312.352 315.334 318.275 320.644 321.178 335.142 348.276 360.668 372.392 394.073 413.720 431.652 448.127 463.353 477.499 490.701 503.074 514.711 525.692 536.084 545.943 555.320 564.258 572.794 848.905 529.039 429.695 383.721 343.382 332.497 330.004 327.931 326.214 324.802 323.654 322.734 322.013 321.466 321.073 320.815 320.677 320.644 320.645 321.729 324.235 327.601 331.499 340.152 349.281 358.473 367.531 376.362 384.921 393.192 401.173 408.872 416.297 423.462 430.379 437.062 443.523 449.775 17.321 16.389 15.359 14.295 13.169 10.615 8.837 8.201 7.544 6.864 6.164 5.442 4.700 3.938 3.156 2.355 1.535 0.696 0.000 0.160 4.695 9.616 14.880 20.446 32.352 45.107 58.543 72.536 86.991 101.836 117.011 132.471 148.175 164.092 180.195 196.458 212.865 229.396 246.038 721.180 722.227 723.498 724.813 725.959 727.905 728.902 729.209 729.504 729.786 730.057 730.316 730.564 730.801 731.027 731.243 731.450 731.646
log K f
721.180 719.030 1502.311 715.371 747.333 711.016 495.189 706.240 368.897 695.943 689.455 687.255 685.040 682.809 680.566 678.311 676.044 673.768 671.482 669.187 666.886 664.576 242.346 200.072 188.937 178.912 169.837 161.585 154.047 147.135 140.774 134.901 129.460 124.407 119.701 116.099 115.308 97.095 83.422 72.779 64.260 51.473 42.335 35.480 30.149 25.885 22.398 19.495 17.039 14.936 13.115 11.523 10.120 8.874 7.760 6.759
731.800 662.689 731.834 732.644 733.273 733.761 734.137 734.633 734.871 734.902 734.765 734.487 734.087 733.590 733.013 732.379 731.700 730.994 730.273 729.544 728.823 728.113 662.260 650.598 638.832 626.996 615.113 591.258 567.341 543.401 519.472 495.566 471.692 447.859 424.068 400.327 376.632 352.965 329.363 305.796 282.276 258.789
9. Methyl Hydroperoxide, CH3AOAOAH

Methyl hydroperoxide (CH4O2) S (298.15 K) 276.5 3.0 J K1 mol1 Molecular constants Symmetry number: 1 Energy: X 0 cm1 Ideal gas M r 48.0414 f H (0 K) 126.2 5.0 kJ mol1 f H (298.15 K) 139.0 5.0 kJ mol1 Number of optical isomers: n 2 Quantum weight: g X 1
Point group: C 1 Ground electronic state: X 1A
Symmetry A 1 2 3
Vibrational frequencies, i , and degeneracies, g i i , cm1 gi Symmetry 3604 1 9 2957 1 10 2955 1 11
i , cm1 1145 1115 1003
gi 1 1 1

501
4 5 6 7 8
a
2861 1509 1453 1450 1348
1 1 1 1 1
12 13 14 15
800 415 a b
1 1 1 1
Instead of torsional mode 14 240 cm1, the contributions due to the internal rotation of CH3 group around the CO bond were calculated 1 V 3 (1 cos3), where is the HCOO from the potential V ( ) 2 torsional angle and V 3 1120 cm1. b Instead of torsional mode 15 149 cm1, the contributions due to the internal rotation of OH group around the O-O bond were calculated from the potential: V ( ) V 0 V 1 cos V2 cos2V3 cos3, where is the COOH torsional angle, V 0 780.7, V 1 1111.1, V 2 555.6, and V 3 52.6 in cm1. CH3 top: Reduced moment of inertia, I r 0.4282 10 39 g cm2, Symmetry number, m 3. OH top: Reduced moment of inertia, I r 0.138 10 39 g cm2, Symmetry number, m 1.
Geometry r CH1.0900.010 r OH0.9700.005 COO105.30.5 OOH100.02.0 HCO109.54.0 COOH1205 r CO1.4200.005 r OO1.4600.010 Rotational constants in cm1: A 0 1.434 544 B 0 0.350 826 C 0 0.301 985. Product of moments of inertia: I A I B I C 144.3 10 117 g3 cm6.
9.1. Enthalpy of Formation Experimental data on enthalpy of formation are not available for methyl hydroperoxide. Values of f H CH3OOH,g,298.15 K between 122 and 138 kJ mol1 were estimated from semiempirical,13 molecular mechanics,46 ab initio,7 and group additivity810 calculations. Lay et al.11 have estimated f H 298.15 K to be (139.7 5.0) kJ mol1 using the experimentally determined value of f H (CH3OO) with an average bond energy for the OH bond in ROOH compounds. Based on the experimental values of f H (CH3O), f H (OH), 12 and the bond energy of the OO bond in CH3OOH, 13 the value of 134.3 kJ mol1 may be obtained for the enthalpy of formation of methyl hydroperoxide. Benassi et al.5 proposed f H (298.15 K) 138.1 kJ mol1 by employing theoretical and empirical approaches. Similar values of f H are predicted by the method of group equations from
f H CH3OOH f H CH3OOCH3 f H CH3OH f H CH3OCH3 125.5 201.5 184.1 142.9 kJ mol1, f H CH3OOH f H CH3CH2OOH f H CH3OH f H CH3CH2OH 173.6 201.5 235.2 139.9 kJ mol1, the f H values were taken from Pedley14 CH3OH, CH3OCH3, and CH3CH2OH, Baker et al.15 (CH3OOCH3), and Lay et al.11 (CH3CH2OOH). The average of these estiJ. Phys. Chem. Ref. Data, Vol. 30, No. 2, 2001
502
DOROFEEVA, NOVIKOV, AND NEUMANN 172.5 cm 1 ( COOH 180) was taken from the microwave study.16 It should be noted that substantially lower values of V trans from 80 to 126 cm1 were predicted by ab initio5,16,19,20 and molecular mechanics6 calculations, whereas high V trans values of 240590 cm1 were found from other molecular mechanics studies.4,5 No experimental data for the V cis rotational barrier have been published. Its value accepted in this work is based on theoretical results46,16,25 which agree closely with each other. The equilibrium COOH dihedral angle, e 120, was estimated in this work see above. The values of the reduced moments of inertia for CH3 and OH tops were calculated from structural parameters given above. Experimental data on the vibrational spectra of methyl hydroperoxide are unknown. Vibrational frequencies of CH3OOH were predicted from ab initio calculations.16,22 In this work, fundamental frequencies of methyl hydroperoxide were estimated by normal coordinate calculations using force constants transferred from the CH3OOCH3 and H2O2 molecules: 5.000 f OOH 0.940 f CH,HCO 0.056 f OO 5.529 f tors CO 0.094 f CH,HCH 0.090 f CO f CH 4.692 f tors OO 0.011 f CO,HCO 0.240 7.173 f CH,CH 0.041 f CO,COO 1.735 f OH f COO 1.512 f CH,CO 0.250 f OO,COO 0.617 f OO,OOH 0.919 f HCO 0.820 f CO,OO 0.267 f HCH 0.516 f OO,OH 0.317 f OH,OOH 0.925 stretching and stretch-stretch interaction constants are in units of mdyn/; bend and torsion constants are in units of mdyn ; stretch-bend interaction constants are in units of mdyn. The valence force elds for CH3OOCH3 and H2O2 were obtained from normal coordinate calculations using known vibrational assignments.6,26 Comparison of our frequencies with those obtained in ab initio calculations16,22 shows satisfactory agreement taking into account the fact that the ab initio frequencies are unscaled and the anharmonicity contributions are neglected. The uncertainties in the calculated thermodynamic functions Table 8 may reach 24 J K1 mol1 for C p ( T ) and 35 J K1 mol1 for S ( T ). They are caused by the uncertainties in the adopted vibrational frequencies and the approximate model used for internal rotation. Ideal gas thermodynamic properties of methyl hydroperoxide have not been reported previously.
mates, 139 5.0 kJ mol1, is accepted in this work for the enthalpy of formation of methyl hydroperoxide at 298.15 K. 9.2. Heat Capacity and Entropy The microwave spectrum of methyl hydroperoxide, CH3OOH, has been investigated by Tyblewski et al.16 However, the assignment of the spectrum was complicated because of the widespread effects of the internal rotation around the OO bond. The experimental results provide denitive evidence that the minimum of the potential energy relative to internal rotation around the OO bond corresponds to a skew conformation. The adjustment to the observed data resulted in a small trans barrier of 172.5 cm1. This barrier separates two equivalent potential minima associated with two enantiomeric skew forms. From a preliminary interpretation of microwave data, Tyblewski et al.17 reported almost all the structural parameters of the CH3OOH molecule. In a more detailed study, Tyblewski et al.16 gave only one parameter adjusted to the observed data, CCO 105.3. All other structural parameters were adopted by those authors from ab initio calculations. Conformational properties of methyl hydroperoxide have been investigated theoretically.1,2,46,11,16,1822 Ab initio5,16,1922 and molecular mechanics4,6 calculations provide an equilibrium molecular structure and trans barrier in close agreement with the conclusions of experimental study of Tyblewski et al.16 The product of the principal moments of inertia of methyl hydroperoxide was calculated in this work using the rotational constants determined from a microwave study.16 Structural parameters for the skew C 1 symmetry conformation given above are based on the experimental16 and theoretical46,16,1922 data for CH3OOH and from comparison with the structural parameters of CH3OOCH3. 23 These parameters give values for the rotational constants which differ by only 0.4%0.6% from the observed values. Methyl hydroperoxide contains OH and CH3 groups, which rotate around OO and CO bonds. Contributions to the thermodynamic functions from these hindered rotors were evaluated in this work based on available data on rotational barriers in CH3OOH. The value of V 3 1120 cm1 was accepted for the barrier to internal rotation of the methyl group around the CO bond. This value was found from the microwave study16 and agrees closely with values obtained from ab initio calculations.4,16 The double-minimum potential energy function, V V 0 V 1 cos V 2 cos 2 V 3 cos 3 , was used in this work for the OO internal rotation. This function was chosen earlier for the hindered rotation potential function in hydrogen peroxide.24 The expansion coefcients V 0 , V 1 , V 2 , and V 3 can be expressed in terms of the trans barrier height V trans , the cis barrier height V cis , and the COOH dihedral angle e corresponding to a minimum of the potential function.24 The values of V 0 , V 1 , V 2 , and V 3 were calculated in this work assuming V trans 172.5 cm1, V cis 2500 cm1, and e 120. The value of V trans
9.3. References
C. Glidewell, J. Mol. Struct. 67, 35 1980. V. N. Kokorev, N. N. Vyshinskii, V. P. Maslennikov, I. A. Abronin, G. M. Zhidomirov, and Yu. A. Aleksandrov, Zh. Strukt. Khim. 22, 9 1981. 3 M. Jonsson, J. Phys. Chem. 100, 6814 1996. 4 L. Carballeira, R. A. Mosquera, and M. A. Rios, J. Comput. Chem. 9, 851 1988. 5 R. Benassi, U. Folli, S. Sbardellati, and F. Taddei, J. Comput. Chem. 14, 379 1993. 6 K. Chen and N. L. Allinger, J. Comput. Chem. 14, 755 1993. 7 T. P. W. Jungkamp and J. H. Seinfeld, Chem. Phys. Lett. 257, 15 1996.
1 2

S. W. Benson, J. Chem. Phys. 40, 1007 1964. S. W. Benson, J. Am. Chem. Soc. 86, 3922 1964. 10 P. S. Nangia and S. W. Benson, J. Phys. Chem. 83, 1138 1979. 11 T. H. Lay, L. N. Krasnoperov, C. A. Venanzi, J. W. Bozzelli, and N. V. Shokhirev, J. Phys. Chem. 100, 8240 1996. 12 L. V. Gurvich, I. V. Veyts, and C. B. Alcock, Thermodynamic Properties of Individual Substances, 4th ed. Hemisphere, New York, 1991, Vol. 2. 13 R. D. Bach, P. Y. Ayala, and H. B. Schlegel, J. Am. Chem. Soc 118, 12758 1996. 14 J. B. Pedley, Thermochemical Data and Structures of Organic Compounds Thermodynamics Research Center, College Station, TX, 1994, Vol. I. 15 G. Baker, J. H. Littlefair, R. Shaw, and J. C. J. Thynne, J. Chem. Soc. 6970 1965. 16 M. Tyblewski, T. K. Ha, R. Meyer, A. Bauder, and C. E. Blom, J. Chem. Phys. 97, 6168 1992.
8 9 17
503
M. Tyblewski, R. Meyer, and A. Bauder, 8th Colloquium on High Resolution Molecular Spectroscopy, Tours, France, 1983. 18 K. Ohkubo, T. Fujita, and H. Sato, J. Mol. Struct. 36, 101 1977. 19 R. A. Bair and W. A. Goddard III, J. Am. Chem. Soc. 104, 2719 1982. 20 D. Christen, H. G. Mack, and H. Oberhammer, Tetrahedron 44, 7363 1988. 21 J. Koller, M. Hodoscek, and B. Plesnicar, J. Am. Chem. Soc. 112, 2124 1990. 22 R. Benassi and F. Taddei, Tetrahedron 50, 4795 1994. 23 B. Haas and H. Oberhammer, J. Am. Chem. Soc. 106, 6146 1984. 24 R. H. Hunt, R. A. Leacock, C. W. Peters, and K. T. Hecht, J. Chem. Phys. 42, 1931 1965. 25 L. Radom, W. J. Hehre, and J. A. Pople, J. Am. Chem. Soc. 94, 2371 1972. 26 P. G. Giguere and T. K. K. Srinivasan, J. Raman Spectrosc. 2, 125 1974.
TABLE 8. Ideal gas thermodynamic properties of methyl hydroperoxide CH4O2g at the standard state pressure, p 0.1 MPa ( T r 298.15 K) T K 0 25 50 75 100 150 180 190 200 210 220 230 240 250 260 270 280 290 298.15 300 350 400 450 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000 C p S ( G H ( T r ))/ T H H ( T r ) fH fG J K1 mol1 J K1 mol1 J K1 mol1 kJ mol1 kJ mol1 kJ mol1 log K f 0.000 34.489 35.540 38.512 41.627 46.975 49.820 50.758 51.703 52.659 53.627 54.610 55.609 56.624 57.653 58.696 59.751 60.816 61.690 61.889 67.290 72.583 77.604 82.279 90.573 97.633 103.693 108.935 113.485 117.439 120.878 123.871 126.478 128.752 130.741 132.485 134.018 135.369 136.564 0.000 171.468 195.488 210.437 221.948 239.876 248.694 251.413 254.040 256.586 259.058 261.463 263.808 266.099 268.340 270.535 272.689 274.804 276.502 276.884 286.830 296.163 305.005 313.427 329.181 343.688 357.130 369.654 381.372 392.378 402.748 412.544 421.822 430.627 439.001 446.981 454.598 461.881 468.855 692.887 438.841 360.349 324.360 293.352 285.189 283.340 281.810 280.549 279.516 278.679 278.011 277.489 277.094 276.810 276.625 276.526 276.502 276.503 277.276 279.059 281.455 284.234 290.432 297.017 303.701 310.342 316.865 323.235 329.433 335.453 341.294 346.958 352.451 357.779 362.948 367.965 372.836 13.919 13.036 12.168 11.243 10.241 8.021 6.569 6.066 5.554 5.032 4.501 3.960 3.408 2.847 2.276 1.694 1.102 0.499 0.000 0.114 3.344 6.841 10.597 14.596 23.250 32.670 42.743 53.381 64.507 76.058 87.978 100.219 112.739 125.503 138.480 151.643 164.970 178.441 192.039 126.247 127.153 128.683 130.278 131.534 126.247 125.355 261.912 123.025 128.522 119.836 83.460 116.158 60.674 37.613 29.829 27.768 25.909 24.222 22.684 21.276 19.982 18.788 17.683 16.657 15.703 14.811 14.128 13.977 10.499 7.861 5.790 4.118 1.584 0.248 1.634 2.719 3.590 4.305 4.901 5.405 5.837 6.210 6.536 6.823 7.077 7.304 7.507
133.584 108.013 134.723 102.791 135.098 101.007 135.472 99.203 135.845 136.215 136.583 136.949 137.312 137.671 138.026 138.376 138.722 139.000 139.063 140.679 142.143 143.453 144.620 146.559 148.043 149.133 149.884 150.352 150.582 150.618 150.500 150.261 149.928 149.526 149.075 148.588 148.080 147.563 97.380 95.540 93.683 91.810 89.922 88.019 86.103 84.173 82.231 80.640 80.277 70.350 60.202 49.879 39.418 18.190 3.328 25.032 46.850 68.737 90.659 112.593 134.525 156.442 178.338 200.219 222.061 243.882 265.672 287.436

504
10. Dimethyl Peroxide, CH3AOAOACH3

Dimethyl peroxide (C2H6O2) S (298.15 K) 308.4 3.0 J K1 mol1 Molecular constants Point group: C 2 Ground electronic state: Symmetry number: 2 Energy: X 0 cm1 Number of optical isomers: n 2 Quantum weight: g X 1 Ideal gas M r 62.0682 f H (0 K) 106.5 5.0 kJ mol1 f H (298.15 K) 125.5 5.0 kJ mol1
X 1A
Symmetry A 1 2 3 4 5 6 7 8 9 10 11 12
a
Vibrational frequencies, i , and degeneracies, g i i , cm1 gi Symmetry 2945 1 13 2917 1 B 14 2900 1 15 1487 1 16 1474 1 17 1433 1 18 1198 1 19 1165 1 20 1020 1 21 786 1 22 448 1 23 a 1 24
i , cm1 ...b 3000 2965 2818 1483 1433 1430 1119 1112 1032 376 a
gi 1 1 1 1 1 1 1 1 1 1 1 1
Instead of torsional modes 12 218 cm1 and 24 231 cm1, the contributions due to the internal rotation of CH3 groups around CO 1 V 3 (1 cos 3 ), where bonds were calculated from the potential V ( ) 2 is the HCOO torsional angle and V 3 900 cm1. b Instead of torsional mode 13 73 cm1, the contributions due to the internal rotation of OCH3 group around OO bond were calculated from the potential V ( ) V 0 V 1 cos V2 cos 2V3 cos 3, where is the COOC torsional angle, V 0 1341.3, V 1 2081.0, V 2 1052.2, and V 3 225.5 in cm1. CH3 top: OCH3 top: Reduced moment of inertia, I r 0.4910 10 39 g cm2, Symmetry number, m 3. Reduced moment of inertia, I r 1.5928 10 39 g cm2, Symmetry number, m 1. Geometry r (CO) 1.420 0.007 r (OO) 1.457 0.012 r (CH) 1.099 0.004 COO105.20.5 HCH110.10.7 (COOC) 119 4 Product of moments of inertia: I A I B I C 1123 10 117 g3 cm6.
10.1. Enthalpy of Formation The enthalpy of formation of dimethyl peroxide recommended in this work 125.5 kJ mol1 was determined by Baker et al.1 from calorimetric measurements of the enthalpy of combustion. Slightly lower values of
f H 298.15 K from 129.3 kJ mol1 to 133.9 kJ mol1 were estimated by group additivity2,3 and molecular mechanics calculations.4,5A lower value is estimated from the experimental value of f H (CH3O) Gurvich et al.6 and the bond energy for the OO bond in CH3OOCH3:7
NIST-JANAF THERMOCHEMICAL TABLES f H CH3OOCH3 2 f H CH3O D CH3OOCH3 2 13 160 134 kJ mol1. A still more negative value, 138.1 kJ mol1, was proposed by Benassi et al.8 employing theoretical and empirical approaches. Semiempirical MINDO9,10 and molecular mechanics11 calculations provide f H 298.15 K values, 105.1 to 121.6 kJ mol1, which are greater than the experimental value. The available theoretical and empirical evaluations are grounds to believe that the experimental value of f H 298.15 K may be overestimated. Thus, its uncertainty was increased in this work. 10.2. Heat Capacity and Entropy The molecular structure of dimethyl peroxide, CH3OOCH3, was studied by electron diffraction.12 The molecular intensities were analyzed using a model which considered the internal rotation about the OO bond. The equilibrium geometry was determined to be the skew conformation with a COOC dihedral angle of 119. The barrier in the trans conguration ( COOC 180) was found to be 87 87/ 52 cm1. This result agrees with an analysis of infrared and Raman spectra13 and a normal coordinate analysis based on the these data14 as well as with results of semiempirical,9,10,15,16 ab initio1719 and molecular mechanics4,5,8 calculations. Photoelectron spectra investigations20,21 and ab initio calculations8,2224 support an exactly planar or nearly planar trans conguration. However, it should be noted that the value of a dihedral angle depends strongly on the basis set and method used.19 Hamada and Morishita25 have described the Raman and infrared spectra of CH3OOCH3 in terms of planar structure of D 3 h symmetry. In this work, the product of the principal moments of inertia of dimethyl peroxide for skew conformation of C 2 symmetry was calculated using the structural parameters determined from electron diffraction study.12 The dimethyl peroxide molecule undergoes three largeamplitude motions: an internal rotation of the OCH3 groups about the OO bond and internal rotation of the CH3 groups about two CO bonds. Contributions to the thermodynamic properties from these hindered rotors were calculated in this work based on available data on the rotational barriers in CH3OOCH3. The value of V 3 900 cm1 was accepted for the internal rotation barrier of methyl groups around the C-O bonds. This value was used by Koput26 in his theoretical model describing the internal rotation in dimethyl peroxide and it is the average of the results of molecular mechanics calculations.4 The double-minimum potential energy function, V V 0 V 1 cos V 2 cos 2 V 3 cos 3 , was used in this work for the internal rotation around the OO bond. This function was chosen earlier for the hindered rotation potential function in hydrogen peroxide.27 The expansion coefcients V 0 , V 1 , V 2 , and V 3 can be expressed
505
in terms of the trans barrier height V trans , the cis barrier height V cis , and the COOC dihedral angle e corresponding to a minimum of the potential function.27 The values of V 0 , V 1 , V 2 , and V 3 were calculated in this work assuming V trans 87 cm1, V cis 4700 cm1, and e 119. The value of V trans was taken from the electron diffraction study.12 It agrees with results of theoretical calculations4,5,8,19 within the limits of experimental accuracy. The adopted value of V cis is based on results of ab initio8,18 and molecular mechanics4,5 calculations. The values of the reduced moments of inertia for CH3 and OCH3 tops were calculated from structural parameters given above. Christe13 has investigated the infrared spectra of CH3OOCH3 and CD3OOCD3 both in the gas phase and in an Ar matrix and the Raman spectra of these molecules in the liquid phase. The vibrational assignment proposed by Christe13 has considerable uncertainty for a number of the vibrations, and the low-frequency modes were not assigned at all. Bell and Laane14 have carried out a normal coordinate analysis of dimethyl peroxide using the experimental data of Christe.13 Hamada and Morishita25 have described the vibrational spectra of CH3OOCH3 in terms of D 3 h symmetry. However, this assignment is in conict with available information on dimethyl peroxide. There are two ab initio calculations of vibrational frequencies of CH3OOCH3. 23,28 Results of Benassi and Taddei23 show overall agreement with experimental data taking into account the fact that the ab initio frequencies are unscaled and the anharmonicity contributions are neglected. Chen and Allinger5 have carried out the molecular mechanics calculation of vibrational frequencies of dimethyl peroxide. Their results are in agreement with the available, but somewhat tentative and incomplete, experimental data.13 The assignment proposed by Chen and Allinger5 is accepted in this work. The uncertainties in the calculated thermodynamic functions Table 9 may reach 24 J K1 mol1 for C p ( T ) and 35 J K1 mol1 for S ( T ). They are caused by uncertainties in the adopted vibrational frequencies and the approximate treatment of internal rotation. Ideal gas thermodynamic properties of dimethyl peroxide have not been reported previously.
10.3. References
1
G. Baker, J. H. Littlefair, R. Shaw, and J. C. J. Thynne, J. Chem. Soc. 6970 1965. 2 S. W. Benson, J. Chem. Phys. 40, 1007 1964. 3 S. W. Benson, J. Am. Chem. Soc. 86, 3922 1964. 4 L. Carballeira, R. A. Mosquera, and M. A. Rios, J. Comput. Chem. 9, 851 1988. 5 K. Chen and N. L. Allinger, J. Comput. Chem. 14, 755 1993. 6 L. V. Gurvich, I. V. Veyts, and C. B. Alcock, Thermodynamic Properties of Individual Substances, 4th ed. Hemisphere, New York, 1991, Vol. 2. 7 R. D. Bach, P. Y. Ayala, and H. B. Schlegel, J. Am. Chem. Soc. 118, 12758 1996. 8 R. Benassi, U. Folli, S. Sbardellati, and F. Taddei, J. Comput. Chem. 14, 379 1993. 9 C. Glidewell, J. Mol. Struct. 67, 35 1980. J. Phys. Chem. Ref. Data, Vol. 30, No. 2, 2001
506
10

K. Kimura and K. Osafune, Bull. Chem. Soc. Jpn. 48, 2421 1975. P. Rademacher and W. Elling, Liebigs Ann. Chem. 1473 1979. 22 R. A. Bair and W. A. Goddard III, J. Am. Chem. Soc. 104, 2719 1982. 23 R. Benassi and F. Taddei, Tetrahedron 50, 4795 1994. 24 M.-B. Huang and H. U. Suter, J. Mol. Struct: THEOCHEM 337, 173 1995. 25 K. Hamada and H. Morishita, Spectrosc. Lett. 13, 185 1980. 26 J. Koput, J. Mol. Spectrosc. 141, 118 1990. 27 R. H. Hunt, R. A. Leacock, C. W. Peters, and K. T. Hecht, J. Chem. Phys. 42, 1931 1965. 28 G. A. Pitsevich, V. I. Gogolinskii, and I. P. Zyatkov, Zh. Prikl. Spektrosk. 56, 643 1992.
20 21
V. N. Kokorev, N. N. Vyshinskii, V. P. Maslennikov, I. A. Abronin, G. M. Zhidomirov, and Yu. A. Aleksandrov, Zh. Strukt. Khim. 22, 9 1981. 11 W. H. Richardson, J. Org. Chem. 54, 4677 1989. 12 B. Haas and H. Oberhammer, J. Am. Chem. Soc. 106, 6146 1984. 13 K. O. Christe, Spectrochim. Acta A 27, 463 1971. 14 M. E. B. Bell and J. Laane, Spectrochim. Acta A 28, 2239 1972. 15 R. M. Minyaev, V. I. Minkin, I. I. Zakharov, and I. D. Sadekov, Teor. Eksp. Khim. 9, 816 1973. 16 K. Ohkubo, T. Fujita, and H. Sato, J. Mol. Struct. 36, 101 1977. 17 B. Plesnicar, D. Kocjan, S. Murovec, and A. Azman, J. Am. Chem. Soc. 98, 3143 1976. 18 W. Gase and J. E. Boggs, J. Mol. Struct. 116, 207 1984. 19 D. Christen, H. G. Mack, and H. Oberhammer, Tetrahedron 44, 7363 1988.
TABLE 9. Ideal gas thermodynamic properties of dimethyl peroxide C2H6O2g at the standard state pressure, p 0.1 MPa ( T r 298.15 K) T K 0 25 50 75 100 150 180 190 200 210 220 230 240 250 260 270 280 290 298.15 300 350 400 450 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000 C p S ( G H ( T r ))/ T H H ( T r ) fH fG J K1 mol1 J K1 mol1 J K1 mol1 kJ mol1 kJ mol1 kJ mol1 0.000 38.665 42.071 45.713 49.953 58.133 62.664 64.145 65.624 67.105 68.594 70.095 71.609 73.139 74.685 76.247 77.823 79.413 80.717 81.014 89.107 97.131 104.858 112.164 125.390 136.887 146.892 155.605 163.187 169.774 175.490 180.449 184.752 188.491 191.746 194.585 197.069 199.247 201.164 0.000 180.406 208.414 226.123 239.851 261.681 272.683 276.111 279.439 282.676 285.832 288.915 291.930 294.884 297.783 300.630 303.432 306.190 308.409 308.910 322.005 334.429 346.320 357.750 379.396 399.609 418.557 436.373 453.169 469.039 484.062 498.309 511.843 524.721 536.992 548.703 559.898 570.612 580.882 831.484 513.657 415.019 369.568 330.120 319.647 317.266 315.292 313.662 312.325 311.241 310.374 309.695 309.181 308.812 308.570 308.441 308.409 308.411 309.427 311.782 314.963 318.674 327.012 335.955 345.108 354.269 363.327 372.223 380.922 389.409 397.673 405.719 413.543 421.152 428.551 435.748 442.750 17.153 16.277 15.262 14.167 12.972 10.266 8.453 7.819 7.171 6.507 5.828 5.135 4.426 3.703 2.964 2.209 1.439 0.652 0.000 0.150 4.402 9.059 14.110 19.538 31.431 44.558 58.759 73.893 89.842 106.498 123.768 141.570 159.536 178.502 197.518 216.838 236.423 256.241 276.264 106.460 106.460 107.908 104.953 110.130 101.224 112.460 96.245 114.304 90.552 117.336 119.030 119.590 120.149 120.707 121.264 121.818 122.370 122.919 123.465 124.006 124.542 125.072 125.500 125.597 128.110 130.424 132.528 134.426 137.633 140.119 141.956 143.219 143.993 144.351 144.366 144.105 143.625 142.971 142.187 141.305 140.351 139.347 138.314 78.000 69.973 67.232 64.462 61.664 58.840 55.990 53.116 50.219 47.301 44.360 41.401 38.422 35.981 35.425 20.196 4.619 11.235 27.313
log K f 219.284 105.747 67.030 47.299 27.162 20.305 18.483 16.836 15.338 13.970 12.716 11.560 10.493 9.503 8.582 7.723 6.921 6.304 6.168 3.014 0.603 1.304 2.853
59.970 5.221 93.110 6.948 126.561 8.263 160.207 9.298 193.966 10.132 227.782 261.615 295.441 329.235 362.990 396.716 430.365 463.971 497.516 531.010 10.816 11.388 11.871 12.284 12.640 12.951 13.223 13.464 13.677 13.868

507
11. Diacetyl Peroxide, CH3ACOAOAOACOCH3

Diacetyl peroxide (C4H6O4) S (298.15 K) (390.7 6.0) J K1 mol1 Molecular constants Point group: C 2 Ground electronic state: X 1A Symmetry number: 2 Energy: X 0 cm1 Number of optical isomers: n 2 Quantum weight: g X 1 Ideal gas M r 118.089 f H (0 K) (477.0 10.0) kJ mol1 f H (298.15 K) (500.0 10.0) kJ mol1
Symmetry A 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
a
Vibrational frequencies, i , and degeneracies g i i , cm1 gi Symmetry 3001 1 19 2998 1 B 20 2934 1 21 1762 1 22 1466 1 23 1428 1 24 1426 1 25 1290 1 26 1087 1 27 927 1 28 875 1 29 850 1 30 648 1 31 631 1 32 392 1 33 285 1 34 151 1 35 a 1 36
i , cm1 b 3001 2998 2934 1749 1457 1427 1426 1285 962 922 808 639 619 545 328 140 b
gi 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
Instead of torsional mode 18 70 cm1, the contributions due to the internal rotation of OCOCH3 group around OO bond were calculated from the potential V ( ) V 0 V 1 cos V2 cos2V3 cos3, where is the COOC torsional angle, V 0 1433.9, V 1 2222.2, V 2 1111.1, and V 3 232.8 in cm1. b Instead of torsional modes 19 and 36 60 cm1, the contributions due to the internal rotation of CH3 groups around CC bonds were calcu1 lated from the potential V ( ) 2 V 3 (1 cos 3), where is the HCCO torsional angle and V 3 80 cm1. OCOCH3 top: Reduced moment of inertia, I r 4.5200 10 39 g cm2, Symmetry number, m 1. CH3 top: Reduced moment of inertia, I r 0.5182 10 39 g cm2, Symmetry number, m 3.
Geometry r CC1.4950.01 r CvO1.210.02 r CO1.340.02 r OO1.460.02 r CH1.090.01 CCvO1283 Product of moments of inertia: I A I B I C 96075 10 117 g3 cm6.
OvCO1223 COO1133 HCH109.52.0 COOC12010 OvCOO0

508
DOROFEEVA, NOVIKOV, AND NEUMANN 11.1. Enthalpy of Formation from structural parameters estimated by comparison with structural parameters of CH3COOOH, 7 9 8 CH3COOCOCH3, and CH3OOCH3. The diacetyl peroxide molecule undergoes ve largeamplitude motions: an internal rotation about a central OO bond and about two CC and two CO bonds. Contributions to the thermodynamic functions due to internal rotation of CH3 groups were calculated in this work assuming the V 3 barrier height to be the same as that in peroxyacetic acid.7 The double-minimum potential energy function, V V 0 V 1 cos V 2 cos 2 V 3 cos 3 , was used for the internal rotation about the OO bond. This function was chosen earlier for the hindered rotation potential function in hydrogen peroxide.10 The expansion coefcients V 0 , V 1 , V 2 , and V 3 can be expressed in terms of the trans barrier height V trans , the cis barrier height V cis , and the COOC dihedral angle e corresponding to a minimum of the potential function.10 The values of V 0 , V 1 , V 2 , and V 3 were calculated in this work assuming V trans 90 cm1, V cis 5000 cm1, and e 120. The values of V trans and V cis are derived from the results of a MINDO calculation5 taking into account that the same calculation overestimated the V trans and underestimated the V cis barriers for the CH3OOH and CH3OOCH3 molecules. The values of the reduced moments of inertia for CH3 and CH3COO tops were calculated from structural parameters given above. There are no data on barriers hindering the internal rotation of CH3CO groups about the C-O bonds. Frequencies 17 151 and 35 140 cm1 were accepted in this work for the torsional motion about the C-O bonds. Zyatkov et al.11 have calculated vibrational frequencies of diacetyl peroxide using a theoretical simulation of the force eld. In this work, vibrational frequencies of CH3COOOCOCH3 were calculated using force constants transferred from the CH3COOOH molecule. The simplied valence force eld for that molecule was obtained by normal coordinate calculations for the vibrational assignment of Cugley et al.12 The calculated force constants reproduce the observed vibrational wave numbers of CH3COOOH with a root mean square deviation of 0.6 cm1. The following 18 force constants were used for calculating the vibrational frequencies of diacetyl peroxide:
Jaffe et al.1 determined the enthalpy of formation for liquid diacetyl peroxide (CH3COOOCOCH3) from calorimetric measurements. Assuming the enthalpy of vaporization of diacetyl peroxide to be equal to the enthalpy of vaporization of acetic anhydride (CH3COOCOCH3), the authors obtained the value of 498 kJ mol1 for the enthalpy of formation of gaseous diacetyl peroxide. A similar value of f H (298.15 K) 502 kJ mol1 may be derived from the group additivity contributions for peroxyacids and peroxyesters obtained by Benassi and Taddei2 using empirical approaches and ab initio calculations. The value predicted by the method of group equations, f H CH3COOOCOCH3 f H CH3COOCOCH3 f H CH3OOCH3 f H CH3OCH3 572.5 125.5 184.1 513.9 the f H values for the related compounds were taken from the compilation by Pedley3, agrees with the two above estimates within the limits of the combined errors of those determinations. Considerably lower values of f H for diacetyl peroxide were estimated from a group additivity approximation 540 kJ mol14 and a semiempirical calculation 585 kJ mol1.5,6 The value recommended in this work, (500 10) kJ mol1, is based on the estimates.1,2 11.2. Heat Capacity and Entropy Experimental data on molecular structure and vibrational frequencies of diacetyl peroxide, CH3COOOCOCH3, are unknown. Semiempirical MINDO calculations5 predict that the skew conformation of C 2 symmetry with a COOC dihedral angle of 108 is the most stable. Although a planar structure was suggested for the peroxy acid group in peroxyacetic acid from a microwave study,7 the skew conformation of C 2 symmetry is accepted in this work for diacetyl peroxide in accord with a semiempirical calculation5 and by analogy with dimethyl peroxide.8 The product of the principal moments of inertia was calculated
f OO f CO f CvO f CC f CH f COO
3.821 3.827 11.382 3.480 4.836 1.659
f CCO f OvCO f OvCC f CCH f HCH f wagCvO f torsCC
2.363 1.972 0.497 0.523 0.515 0.006
f torsCO f torsOO f CvO,CC f CvO,CO f CC,CO f CH,CCH f CO,OvCO
0.430 0.104 1.679 0.356 0.415 0.232

NIST-JANAF THERMOCHEMICAL TABLES stretching and stretch-stretch interaction constants are in units of mdyn/; bending, wagging, and torsion constants are in units of mdyn ; stretch-bend interaction constants are in units of mdyn. The uncertainties in the calculated thermodynamic functions Table 10 may reach 812 J K1 mol1 for C p ( T ) and 610 J K1 mol1 for S ( T ). They are caused by the uncertainties in the adopted vibrational frequencies and the approximate treatment of internal rotation. Ideal gas thermodynamic properties of diacetyl peroxide have not been reported previously. 11.3. References
1 2 3
509
L. Jaffe, E. L. Prosen, and M. Szware, J. Chem. Phys. 27, 416 1957. R. Benassi and F. Taddei, J. Mol. Struct.: THEOCHEM 303, 101 1994.
J. B. Pedley, Thermochemical Data and Structures of Organic Compounds Thermodynamics Research Center, College Station, TX, 1994, Vol. I. 4 S. W. Benson, F. R. Cruickshank, D. M. Golden, G. R. Haugen, H. E. ONeal, A. S. Rodgers, R. Shaw, and R. Walsh, Chem. Rev. 69, 279 1969. 5 C. Glidewell, J. Mol. Struct. 67, 35 1980. 6 V. N. Kokorev, N. N. Vyshinskii, V. P. Maslennikov, I. A. Abronin, G. M. Zhidomirov, and Yu. A. Aleksandrov, Zh. Strukt. Khim. 22, 9 1981. 7 nthard, Chem. Phys. J. A. Cugley, W. Bossert, A. Bauder, and H. H. Gu 16, 229 1976. 8 B. Haas and H. Oberhammer, J. Am. Chem. Soc. 106, 6146 1984. 9 H. J. Vledder, F. C. Mijlhoff, J. C. Leyte, and C. Romers, J. Mol. Struct. 7, 421 1971. 10 R. H. Hunt, R. A. Leacock, C. W. Peters, and K. T. Hecht, J. Chem. Phys. 42, 1931 1965. 11 I. P. Zyatkov, V. I. Gogolinskii, V. V. Sivchik, and D. I. Sagaidak, Zh. Prikl. Spektrosk. 29, 652 1978. 12 nthard, Chem. Phys. 18, 281 1976. J. A. Cugley, R. Meyer, and H. H. Gu
TABLE 10. Ideal gas thermodynamic properties of diacetyl peroxide, C4H6O4g at the standard state pressure, p 0.1 MPa ( T r 298.15 K) T K 0 25 50 75 100 150 180 190 200 210 220 230 240 250 260 270 280 290 298.15 300 350 400 450 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000 C p S ( G H ( T r ))/ T H H ( T r ) fH fG J K1 mol1 J K1 mol1 J K1 mol1 kJ mol1 kJ mol1 kJ mol1 0.000 50.640 58.035 62.084 66.834 78.569 86.766 89.636 92.559 95.524 98.523 101.547 104.588 107.640 110.696 113.750 116.796 119.830 122.291 122.848 137.551 151.377 164.144 175.813 196.085 212.888 226.936 238.778 248.823 257.379 264.693 270.965 276.360 281.017 285.051 288.556 291.613 294.288 296.638 0.000 213.740 251.723 276.009 294.500 323.725 338.764 343.532 348.204 352.791 357.304 361.750 366.136 370.468 374.749 378.984 383.176 387.327 390.682 391.441 411.491 430.772 449.350 467.258 501.163 532.691 562.062 589.495 615.187 639.314 662.031 683.471 703.754 722.984 741.252 758.641 775.223 791.063 806.219 1130.731 682.615 543.259 478.840 422.461 407.276 403.796 400.900 398.500 396.525 394.917 393.626 392.614 391.844 391.290 390.925 390.730 390.682 390.685 392.235 395.855 400.773 406.531 419.512 433.456 447.717 461.963 476.014 489.774 503.192 516.243 528.919 541.221 553.157 564.737 575.973 586.880 597.471 23.944 22.925 21.545 20.044 18.434 14.810 12.332 11.450 10.539 9.599 8.629 7.628 6.598 5.536 4.445 3.323 2.170 0.987 0.000 0.227 6.740 13.967 21.860 30.363 48.990 69.465 91.476 114.778 139.172 164.493 190.606 217.397 244.770 272.645 300.953 329.637 358.649 387.947 417.496 476.961 478.990 481.588 484.278 486.503 490.316 492.443 493.135 493.820 494.496 495.163 476.961 473.540 467.166 459.352 450.697 431.949 420.074 416.035 411.959 407.849 403.707
log K f 989.395 488.038 319.917 235.417 150.416 121.901 114.374 107.591 101.446 95.851 90.736 86.041 81.717 77.720 74.014 70.569 67.357 64.896 64.356 51.885 42.484 35.141 29.244 20.359 13.983 9.186 5.449 2.457 0.010 2.027 3.747 5.218 6.490
495.821 399.536 496.468 395.336 497.104 391.109 497.729 498.342 498.943 499.530 386.857 382.581 378.283 373.963
500.000 370.427 500.105 502.777 505.120 507.157 508.918 369.622 347.661 325.337 302.738 279.929
511.704 233.859 513.643 187.388 514.847 140.688 515.418 93.879 515.458 47.036 515.048 514.271 513.201 511.906 510.431 508.834 507.144 505.392 503.606 501.807 0.210 46.561 93.260 139.862 186.370
232.810 7.600 279.105 8.576 325.314 9.440 371.413 10.211 417.423 10.902

510

TABLE 11. Summary of the thermodynamic properties at 298.15 K and the standard state pressure, p 0.1 MPa S 298.15 K J K1 mol1 337.0 325.9 310.0 318.6 272.5 278.2 320.6 276.5 308.4 390.7 5.0 5.0 1.0 5.0 1.0 1.5 5.0 3.0 3.0 6.0 C p 298.15 K J K1 mol1 80.5 78.8 80.8 87.1 60.6 56.1 86.2 61.7 80.7 122.3 3.0 3.0 1.0 3.0 0.5 1.5 5.0 2.0 2.0 8.0 f H 298.15 K kJ mol1 383.5 427.6 247.5 583.0 212.0 210.0 731.8 139.0 125.5 500.0 3.1 1.0 6.4 10.0 0.8 10.0 2.0 5.0 5.0 10.0
Molecule Bromoacetic acid Chloroacetic acid Oxopropanedinitrile Glycolic acid Glyoxal Cyanooxomethyl radical Oxalic acid Methyl hydroperoxide Dimethyl peroxide Diacetyl peroxide
12. Conclusions
The thermodynamic properties of 10 organic molecules have been calculated, based on the critical evaluation of available thermodynamic and spectroscopic information. Where no data were available, estimation techniques were used. Recommended values for the entropy, heat capacity, and the enthalpy of formation at 298.15 K are summarized in Table 11. For a rst round of new experimental studies, substantially improved formation properties could be obtained with new or conrming measurements for the enthalpy of formation for bromoacetic acid, glycolic acid, the cyanooxomethyl radical, and the three peroxidesmethyl hydroperoxide, dimethyl peroxide, and diacetyl peroxide. In order to calculate signicantly more reliable thermal functions, the structure and the vibrational frequencies are needed for the cyanooxomethyl radical and diacetyl peroxide, since these data were estimated for these two compounds.
13. Acknowledgments
The authors wish to acknowledge the support of this work by the Upper Atmospheric Research Program of the National Aeronautics and Space Administration NASA and the Standard Reference Data SRD Program of the National Institute of Standards and Technology NIST. The authors thank Professor Joel Liebman of the University of Maryland, Baltimore County, for bringing to their attention the justpublished work, so relevant to this article, of the 10 scientists of Portugal and Germany working with Professor Manuel E. mica Estrutural, ComMinas da Piedade of the Centro de Qu cnico, Lisplexo Interdisciplinar, at the Institutio Superior Te bon, Portugal. The authors are also grateful to Professor Vladimir Yungman of the Institute for High Temperatures IVTAN of the Russian Academy of Sciences, Dr. Malcolm W. Chase of SRD, and Dr. Eugene S. Domalski of NIST whose expert advice, support, and encouragement were essential to the completion of this project.
14. Extended Bibliographies

The following bibliography lists articles that were found in the literature pertaining to the molecules discussed above but were not used as sources of information in the evaluations. 14.1. Extended Bibliography for Bromoacetic Acid, C2H3BrO2 71KIN/GOL 78VAN/BRA 93CAR/LAY King, K. D., Golden, D. M., and Benson, S. W., Thermochemistry of the gas-phase equilibrium CH3COCH3Br2CH3COCH2HBr, J. Chem. Thermodyn. 3, 129134 1971. Van Eijck, B. P., Brandts, P., Maas, J. P. M., Microwave spectra and molecular structures of rotational isomers of uoroacetic acid and uoroacetyl uoride, J. Mol. Struct. 44, 113 1978. Carson, A. S., Laye, P. G., Pedley, J. B., Welsby, A. M., The enthalpies of formation of iodomethane, diiodomethane, triiodomethane, and tetraiodomethane by rotating combustion calorimetry, J. Chem. Thermodyn. 25, 261269 1993. 14.2. Extended Bibliography for Chloroacetic Acid, C2H3ClO2 64JOH 75CHA/DEV 75SIN/KAT Johansen, H., Normal coordinate analysis of polyatomic molecules and statistical thermodynamics of isotopic molecules, Z. Phys. Chem. 227, 305328 1964. Chandramani, R., Devaraj, N., Torsional-vibration frequency in -CH2ClCOOH and its temperature dependence from pure quadrupole resonance measurements, Indian J. Pure Appl. Phys. 13, 637638 1975. Sinha, D., Katon, J. E., Jakobsen, R. J., The vibrational spectra and structure of - and -chloroacetic acid, J. Mol. Struct. 24, 279291 1975.

NIST-JANAF THERMOCHEMICAL TABLES 86FAU/TEI2 93KUL/FAU 96NYQ/CLA
511
Fausto, R., Teixeira-Dias, J. J. C., Conformational and vibrational spectroscopic analysis of CHCl2COX and CCl3COX XCl, OH, OCH3, J. Mol. Struct. 144, 241263 1986. Kulbida, A., Fausto, R., Conformers, vibrational spectra and infrared-induced rotamerization of dichloroacetic acid in argon and krypton matrixes, J. Chem. Soc., Faraday Trans. 89, 42574266 1993. Nyquist, R. A., Clark, T. D., Infrared study of -haloacetic acids in solution, Vib. Spectrosc. 10, 203228 1996. 14.3. Extended Bibliography for Oxopropanedinitrile, C3N2O
53KEM/TRA 70NAY/ARU 71DUN/WHI 72NAY/ARU 97LER/DEW
97MED/BHA
Kemula, W., Tramer, A., Vibrational specrum of carbonyl cyanide, Roczniki Chem. 27, 522523 1953. Nayar, V. U., Aruldhas, G., Force eld and Coriolis coupling coefcients of carbonyl cyanide, Indian J. Pure Appl. Phys. 8, 840841 1970. Duncan, A. B. F., Whitlock, R. F., Vacuum ultraviolet absorption spectrum of carbonyl cyanide, Spectrochim. Acta A 27, 25392541 1971. Nayar, V. U., Aruldhas, G., Joseph, K. B., Cyvin, S. J., Vibrational analyses and mean amplitudes for some simple molecules. III. Carbonyl cyanide, Mol. Struct. Vib. 237242 1972. Leroy, G., Dewispelaere, J. P., Wilante, C., Benkadour, H., A theoretical approach to the thermochemistry of the polymerization of some derivatives of the monomers CH2X XCH2, NH, O, Macromol. Theory Simul. 6, 729739 1997. Medhi, C., Bhattacharyya, S. P., Transcription of the results of quantum calculations in terms of the classical notion of molecular structures: The cases of some small carbonyls in the ground and excited states, Proc. Indian Acad. Sci., Chem. Sci. 109, 6170 1997. 14.4. Extended Bibliography for Glycolic Acid, C2H4O3
87KAK 93DOM/HEA
Kakumoto, T., A theoretical study on the unimolecular decomposition of some -dicarbonyl compounds: glyoxal, oxalic acid and glycolic acid, J. Sci. Hiroshima Univ. A 51, 69111 1987. Domalski, E. S., Hearing, E. D., Estimation of the thermodynamic properties of C-H-N-O-S-halogen compounds at 298.15 K, J. Phys. Chem. Ref. Data 22, 8051159 1993. 14.5. Extended Bibliography for Glyoxal, C2H2O2
39LUV/SCH 49COL/THO 54BRA/MIN 64COL/OSB 69JEN/HAG 71AGA/BAI
73DON/RAM 73GLE/MCC 73LE/TYU 75COL/DUR 75GUT/BAU 75PAN 76COL/CRO
LuValle, J. E., Schomaker, V., The molecular structures of glyoxal and dimethyl glyoxal by the electron diffraction method, J. Am. Chem. Soc. 61, 35203525 1939. Cole, A. R. H., Thompson, H. W., Vibration-rotation bands of some polyatomic molecules, Proc. R. Soc. London, Ser. A, 200, 1020 1949. Brand, J. C. D., Minkoff, G. J., The infrared spectrum of dideuteroglyoxal, J. Chem. Soc. 29702971 1954. Cole, A. R. H., Osborne, G. A., Fundamental 12 of glyoxal, J. Chem. Soc. 1532 1964. Jensen, H. H., Hagen, G., Cyvin, S. J., Mean amplitudes of vibration for some conjugated carbonyl compounds: glyoxal, acrolein, and p-benzoquinone, J. Mol. Struct. 4, 5158 1969. Agar, D. M., Bair, E. J., Birss, F. W., Borrell, P., Chen, P. C., Currie, G. N., McHugh, A. J., Orr, B. J., Ramsay, D. A., Roncin, J. Y.,The 4550 band system of glyoxal. III. Vibration-rotational analyses for 11 bands of C2D2O2, Can. J. Phys. 49, 323327 1971. Dong, R. Y., Ramsay, D. A., A band system of glyoxal-d 1 and glyoxal-d 2 , Can. J. Phys. 51, 14631465 1973. Gleghorn, J. T., McConkey, F. W., The structure and properties of carbonyl compounds, J. Mol. Struct. 18, 219225 1973. Le, H. H., Tyulin, V. I., Raman spectrum of liquid glyoxal (C2O2H2), Opt. Spektrosk. 35, 770772 1973. Cole, A. R. H., Durig, J. R., Raman and infrared spectra of solid glyoxal-d 1 and glyoxal-d 2 , J. Raman Spectrosc. 4, 3139 1975. nthard H. H., Solution of the rotation-internal rotation problem of glyoxal type Gut, M., Bauder, A., Gu molecules by innite matrix technique, Chem. Phys. 8, 252271 1975. Pancir, J., Cis-trans isomerization of glyoxal. A contribution to the rehabilitation of semiempirical methods, Theor. Chim. Acta 40, 8183 1975. Cole, A. R. H., Cross, K. J., Ramsay, D. A., Rotational structure of the 00 visible band of glyoxal-d 1 . A reanalysis, J. Phys. Chem. 80, 12211223 1976.
512 76DEV/TOW 77VON 78COS/FRA 78LUC/SCH 78PAR/ROR 79MOR/MAK 81NGU/TRO
DOROFEEVA, NOVIKOV, AND NEUMANN Devaquet, A. J. P., Townshend, R. E., Hehre, W. J., Conformational studies of 1,3-dienes, J. Am. Chem. Soc. 98, 40684076 1976. Von Niessen, W., Trans- and cis-glyoxal: A Greens function calculation on their photoelectron spectra, J. Am. Chem. Soc. 99, 71517153 1977. Cossart-Magos, C., Frad, A., Tramer, A., Fluorescence and phosphorescence spectra of glyoxal-h 2 and -d 2 from single vibronic levels of 1 A u and 3 A u states, Spectrochim. Acta A 34, 195 1978 Lucchese, R. R., Schaefer, H. F., III, Formulation of the direct conguration interaction method for triplet spin states. Application to glyoxal, J. Chem. Phys. 68, 769774 1978. Parmenter, C. S., Rordorf, B. F., Fluorescence from selected rotational levels of S 1 glyoxal, Chem. Phys. 27, 19 1978. Morozov, A. A., Makhnev, A. S., Panchenko, Y. N., Stepanov, N. F., Calculation of some molecular parameters of glyoxal, Vestn. Mosk. Univ., Ser. 2: Khim. 20, 326331 1979. Nguyen-Xuan, T., Tronchet, J. M. J., Bill, H., Conformational equilibriums of carbohydrates on the level of C( s p 2 ),C( s p 3 ) bonding. IX. Study of the factors affecting the conformational equilibrium of E-1,3disubstituted propenes using energy partitioning techniques, Helv. Chim. Acta 64, 19491958 1981. Osamura, Y., Shaefer, H. F. III, Dupuis, M., Lester, W. A., Jr., A unimolecular reaction ABCABC involving three product molecules and a single transition state. Photodissociation of glyoxal: HCOHCOH2COCO, J. Chem. Phys. 75, 58285836 1981. Bock, C. W., Trachtman, M., George, P., An ab initio study of the geometry of the CCHvO group, the f CC2 stretching force constant, and the f CvO,CC coupling constant in conjugated monosubstituted carbonyl compounds, Chem. Phys. 68, 143154 1982. Panchenko, Y. N., Mochalov, V. I., Pentin, Y. A., Calculation of potential curves of the internal rotation of glyoxal and its uoro derivatives in the CNDO/2 approximation taking into account a change in geometry, Vestn. Mosk. Univ., Ser. 2: Khim. 24, 357360 1983. Musso, G. F., Figari, G., Magnasco, V., Improved bond-orbital calculations of rotation barriers in molecules containing conjugated double bonds and/or lone pairs, J. Chem. Soc., Faraday Trans. 2 81, 12431258 1985. Duval, A. B., King, D. A., Haines, R., Isenor, N. R., Orr, B. J., Coherent Raman spectroscopy of glyoxal vapor, J. Raman Spectrosc. 17, 177182 1986. Spangler, L. H., Pratt, D. W., Birss, F. W., Rotational analysis of some vibronic bands in the 3 A u 1 A g transition of glyoxal. Spin splittings in the lowest triplet state of the isolated molecule, J. Chem. Phys. 85, 32293236 1986. Yamanouchi, K., Yamada, H., Tsuchiya, S., Rotationally resolved stimulated emission pumping spectra of glyoxal cooled in supersonic free jet, Chem. Phys. Lett. 132, 361364 1986. Pebay Peyroula, E., Jost, R., S 1 S 0 laser excitation spectra of glyoxal in a supersonic jet: Vibrational analysis, J. Mol. Spectrosc. 121, 177188 1987. Rodler, M., Oldani, M., Grassi, G., Bauder, A., Rotational spectra of s-trans and s-cis glyoxal-d1 (CHOCDO) observed by microwave Fourier transform spectroscopy, J. Chem. Phys. 87, 53655369 1987. Fabian, W. M. F., AM1 calculations of rotation around essential single bonds and preferred conformations in conjugated molecules, J. Comput. Chem. 9, 369377 1988. Brinn, I. M., Fundamental vibrational frequency correlation. IV. C 2 v C 2 h in-plane trends, Spectrochim. Acta A 45, 653659 1989. Mohan, S., Payami, F., Kuttiappan, P., Laser Raman spectrum of glyoxal and its vibrational analysis, Proc. Indian Natl. Sci. Acad. A 55, 598601 1989. Wiberg, K. B., Rablen, P. R., Marquez, M., Resonance interactions in acyclic systems. 5. Structures, charge distributions, and energies of some hetrobutadiene rotamers, J. Am. Chem. Soc. 114, 86548668 1992. Mo, Y., Zhang, Q., Why N2O2 is cis while (CHO) 2 is trans: MO and VB studies, Int. J. Quantum Chem. 56, 1926 1995. Promyslov, V. M., Shorygin, P. P., Quantum-chemical study of conjugation in molecules containing conjugated CvC and CvO bonds, Izv. Akad. Nauk, Ser. Khim. 16481652 1996. Rempe, S. B., Watts, R. O., The convergence properties of hindered rotor energy levels, Chem. Phys. Lett. 269, 455463 1997. 14.6. Extended Bibliography for Cyanooxomethyl Radical, NC2O
81OSA/SHA
82BOC/TRA
83PAN/MOC
85MUS/FIG
86DUV/KIN 86SPA/PRA
86YAM/YAM 87PEB/JOS 87ROD/OLD
88FAB 89BRI 89MOH/PAY 92WIB/RAB 95MO/ZHA 96PRO/SHO 97REM/WAT
91GUR/VEY
Gurvich, L. V., Veyts, I. V., Alcock, C. B., Thermodynamic Properties of Individual Substances, 4th ed. Hemisphere, New York, 1991, Vol. 2.

NIST-JANAF THERMOCHEMICAL TABLES 92DOR/GUR
513
94PED
Dorofeeva, O. V., Gurvich, L. V., Thermodynamic properties of linear carbon chain molecules with conjugated triple bonds. Part 2. Free radicals Cn H ( n 2 12) and Cn N ( n 2 11), Thermochim. Acta 197, 5368 1992. Pedley, J. B., Thermochemical Data and Structures of Organic Compounds Thermodynamics Research Center, College Station, TX, 1994, Vol. I.
14.7. Extended Bibliography for Oxalic Acid, C2H2O4 26VER/HAR Verkade, P. E., Hartman, H., Coops, J., Calorimetric researches. X. Heats of combustion of successive terms of homologous series: Dicarboxylic acids of the oxalic acid series, Recl. Trav. Chim. 45, 373393 1926. De Villepin, J., Novak, A., Romain, F., Vibrational spectra of oxalic acids. II. IR and Raman spectra of the -phase of oxalic acid, and its deuterium and oxygen-18 derivatives, Spectrochim. Acta A 34, 10191024 1978. Shippey, T. A., Vibrational studies in aqueous solutions. Part I. The oxalate ion, J. Mol. Struct. 65, 6170 1980. Chen, L.-T., Chen, G.-J., Fu, X.-Y., Theoretical studies on the mechanism of the thermal decarboxylation and decarbonylation of a number of -ketoacids, Chin. J. Chem. 13, 487492 1995.
78DEV/NOV
80SHI 95CHE/CHE
14.8. Extended Bibliography for Methyl Hydroperoxide, CH4O2 79MOL/ARG 96GRE/COL 96JUR/MAR 97JAC/WEH Molina, M. J., Arguello, G., Ultraviolet absorption spectrum of methyl hydroperoxide vapor, Geophys. Res. Lett. 6, 953955 1979. Grela, M. A., Colussi, A. J., Quantitative structure-stability relationships for oxides and peroxides of potential atmospheric signicance, J. Phys. Chem. 100, 1015010158 1996. Jursic, B. S., Martin, R. M., Calculation of bond dissociation energies for oxygen containing molecules by ab initio and density functional theory methods, Int. J. Quantum Chem. 59, 495501 1996. Jacob, P., Wehling, B., Hill, W., Klockow, D., Feasibility study of Raman spectroscopy as a tool to investigate the liquid-phase chemistry of aliphatic organic peroxides, Appl. Spectrosc. 51, 7480 1997.
14.9. Extended Bibliography for Dimethyl Peroxide, C2H6O2 82BAT/WAL 92ZYA/KNY Batt, L., Walsh, R., A reexamination of the pyrolysis of bis triuoromethyl peroxide, Int. J. Chem. Kinet. 14, 933944 1982. Zyatkov, I. P., Knyazhevich, N. D., Gogolinskii, V. I., Pitsevich, G. A., Quantum-chemical calculations on structure and conformations of organosilicon peroxides, Vestn. Beloruss. Gos. Univ., Ser. 1, No. 2, 3337 1992. Lee, S.-Y., Shin, Y.-J., Estimation of thermodynamic properties in the pyrolysis of dialkyl peroxides in helium gas, Hwahak Konghak 34, 592596 1996.
96LEE/SHI
14.10. Extended Bibliography for Diacetyl Peroxide, C4H6O4 71VLE/MIJ 80HOL/GUN 81VAN/VAN 93CHE/ALL 94BEN/TAD 96JON Vledder, H. J., Mijlhoff, F. C., Leyte, J. C., Romers, C., Electron diffraction investigation of the molecular structure of gaseous acetic anhydride, J. Mol. Struct. 7, 421429 1971. nthard, H. H., A transferable valence force eld for polyatomic molecules. A scheme Hollenstein, H., Gu for a series of molecules containing carbon:oxygen groups, J. Mol. Spectrosc. 84, 457477 1980. Van Eijck, B. P., van Opheusden, J., van Schaik, M. M. M., van Zoeren, E., Acetic acid: Microwave spectra, internal rotation and substitution structure, J. Mol. Spectrosc. 86, 465479 1981. Chen, K., Allinger, N. L., A molecular mechanics study of alkyl peroxides, J. Comput. Chem. 14, 755768 1993. Benassi, R., Taddei, F., Conformational properties of peroxyacids, peroxyesters and structurally related radicals: A theoretical ab initio MO approach, J. Mol. Struct.: THEOCHEM 303, 83100 1994. Jonsson, M., Thermochemical properties of peroxides and peroxyl radicals, J. Phys. Chem. 100, 6814 6818 1996.

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NIST-JANAF Thermochemical Tables. I.

Ten Organic Molecules Related to Atmospheric Chemistry

12. 13. 14. 475

J. Phys. Chem. Ref. Data, Vol. 30, No. 2, 2001

DOROFEEVA, NOVIKOV, AND NEUMANN

J. Phys. Chem. Ref. Data, Vol. 30, No. 2, 2001

DOROFEEVA, NOVIKOV, AND NEUMANN

2. Bromoacetic Acid, CH2BrCOOH

Vibrational frequencies, i , and degeneracies g i i , cm1 gi Symmetry

3566 3037 1808 1449 1325 1208 1047 908 747

Product of moments of inertia: I A I B I C 28 178 10 117 g3 cm6.

J. Phys. Chem. Ref. Data, Vol. 30, No. 2, 2001

DOROFEEVA, NOVIKOV, AND NEUMANN

J. Phys. Chem. Ref. Data, Vol. 30, No. 2, 2001