Hydrothermal reactions of formaldehyde and formic acid: Free-energy analysis of equilibrium

Journal of Chemical Physics

Volumn 122, Issue 7, 2005, Pages

  Matubayasi, Nobuyuki ^a   Nakahara, Masaru ^a  

^a KYOTO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL EQUILIBRIA; ELECTRONIC CONTRIBUTION; EQUILIBRIUM WEIGHTS; NONPOLAR SPECIES;

CARBONYLATION; CARBOXYLIC ACIDS; FORMALDEHYDE; FREE ENERGY; HYDROTHERMAL SYNTHESIS; PHASE EQUILIBRIA; SOLVENTS;

REACTION KINETICS;

EID: 22944437769     PISSN: 00219606     EISSN: None     Source Type: Journal    
DOI: 10.1063/1.1849165     Document Type: Article

References (76)

1. Organic Synthesis in Water, edited by, P. A. Grieco, (Thomson Science, London, 1998).
2. R. Breslow, Acc. Chem. Res. 24, 159 (1991).
3. Water, A Comprehensive Treatise, edited by, F. Franks, (Plenum, New York, 1972), Vols. 1-7.
4. R. W. Shaw, T. B. Brill, A. A. Clifford, C. A. Eckert, and E. U. Franck, Chem. Eng. News 69 (51), 26 (1991).
5. M. Siskin and A. R. Katritzky, Science 254, 231 (1991).
6. P. E. Savage, Chem. Rev. (Washington, D.C.) 99, 603 (1999).
7. N. Matubayasi and M. Nakahara, J. Chem. Phys. 112, 8089 (2000).
8. N. Akiya and P. E. Savage, Chem. Rev. (Washington, D.C.) 102, 2725 (2002).
9. R.T. Morrison and R.N. Boyd, Organic Chemistry (Allyn & Bacon, Boston, 2000).
10. Y. Tsujino, C. Wakai, N. Matubayasi, and M. Nakahara, Chem. Lett. 1999, 287 (1999).
11. D. Bröll, C. Kaul, A. Krämer, P. Krammer, T. Richter, M. Jung, H. Vogel, and P. Zehner, Angew. Chem., Int. Ed. 38, 2998 (1999).
12. C. Wakai, S. Morooka, N. Matubayasi, and M. Nakahara, Chem. Lett. 33, 302 (2004).
13. M. Osada, M. Watanabe, K. Sue, T. Adschiri, and K. Arai, J. Supercrit. Fluids 28, 219 (2004).
14. Y. Nagai, C. Wakai, N. Matubayasi, and M. Nakahara, Chem. Lett. 32, 310 (2003).
15. Y. Nagai, N. Matubayasi, and M. Nakahara, Chem. Lett. 33, 622 (2004).
16. A. B. Bjerre and E. Sørensen, Ind. Eng. Chem. Res. 31, 1574 (1992).
17. J. Yu and P. E. Savage, Ind. Eng. Chem. Res. 37, 2 (1998).
18. P. G. Maiella and T. B. Brill, J. Phys. Chem. A 102, 5886 (1998).
19. C. Wakai, K. Yoshida, Y. Tsujino, N. Matubayasi, and M. Nakahara, Chem. Lett. 33, 572 (2004).
20. K. Yoshida, C. Wakai, N. Matubayasi, and M. Nakahara, J. Phys. Chem. A 108, 7479 (2004).
21. Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed., edited by, J. I. Kroschwitz, and, M. Howe-Grant, (Wiley, New York, 1991).
22. W. M. Graven and F. J. Long, J. Am. Chem. Soc. 76, 2602 (1954).
23. H. R. Holgate, P. A. Webley, J. W. Tester, and R. K. Helling, Energy Fuels 6, 586 (1992).
24. Th. Hirth and E. U. Franck, Ber. Bunsenges. Phys. Chem. 97, 1091 (1993).
25. S. F. Rice, R. R. Steeper, and J. D. Aiken, J. Phys. Chem. A 102, 2673 (1998).
26. T. Sato, S. Kurosawa, R. L. Smith, Jr., T. Adschiri, and K. Arai, J. Supercrit. Fluids 29, 113 (2004).
27. Since the backward reaction of Eq. (4) is called "hydration," we avoid the phrase hydration to denote the effect of intermolecular interaction between the solute and the solvent water. Instead, we use the phrase "solvation" to refer to the intermolecular interaction effects.
28. N. Matubayasi and M. Nakahara, J. Chem. Phys. 117, 3605 (2002);
29. 118, 2446 (2003).
30. N. Matubayasi and M. Nakahara, J. Chem. Phys. 113, 6070 (2000).
31. N. Matubayasi and M. Nakahara, J. Chem. Phys. 119, 9686 (2003).
32. H. Takahashi, N. Matubayasi, M. Nakahara, and T. Nitta, J. Chem. Phys. 121, 3989 (2004).
33. M.P. Allen and D.J. Tildesley, Computer Simulation of Liquids (Oxford University Press, Oxford, 1987).
34. BT for the molecules treated in the present work and does not affect our arguments even if it is neglected.
35. 0+ΔW) in Eq. (10). Since K is not a dimensionless quantity, it is always necessary to specify the unit of K when the corresponding standard free-energy change is to be mentioned.
36. 0i) are functions also of the solute concentration. In this case, although Eq. (10) is a valid expression, K depends on the solute concentration and cannot serve as an "equilibrium constant." When one of the reactive species is the solvent itself and is present in excess, on the other hand, its concentration (density) does not change in the course of reaction and the ρ value in Eq. (10) is simply equal to the input density. Equation (10) is thus assured to be valid as an expression for the equilibrium constant when one of the reactive species is the solvent and the others are at infinite dilution.
37. H. J. C. Berendsen, J. R. Grigera, and T. P. Straatsma, J. Phys. Chem. 91, 6269 (1987).
38. The International Association for the Properties of Water and Steam, IAPWS Formulation 1995, Fredericia, Denmark, 1996.
39. J. D. Madura and W. L. Jorgensen, J. Am. Chem. Soc. 108, 2517 (1986).
40. P. Jedlovszky and L. Turi, J. Phys. Chem. B 101, 5429 (1997).
41. P. Mináry, P. Jedlovszky, M. Mezei, and L. Turi, J. Phys. Chem. B 104, 8287 (2000).
42. C.F. Melius, N.E. Bergan, and J.E. Shepherd, Proceedings of the Twenty-Third Symposium (International) on Combustion (The Combustion Institute, Pittsburgh, PA, 1990), p. 217.
43. N. Akiya and P. E. Savage, AIChE J. 44, 405 (1998).
44. T. Yagasaki, S. Saito, and I. Ohmine, J. Chem. Phys. 117, 7631 (2002).
45. W. L. Jorgensen, J. Phys. Chem. 90, 1276 (1986).
46. T. A. Bruce, Phys. Rev. B 5, 4170 (1972).
47. Kagaku Binran (Dictionary of Chemistry), 5th ed., edited by Chemical Society of Japan (Maruzen, Tokyo, 2004) (in Japanese) (revised edition).
48. J. G. Harris and K. H. Yung, J. Phys. Chem. 99, 12021 (1995).
49. A. D. Buckingham and R. L. Disch, Proc. R. Soc. London, Ser. A 273, 275 (1963).
50. J.P. Hansen and I.R. McDonald, Theory of Simple Liquids, 2nd ed. (Academic, London, 1986).
51. Since the dipole moment is small, CO is categorized as nonpolar.
52. When the solvent density is low enough, the density derivative of βΔμ at constant temperature has the same sign as ∫d x {1-exp[-βv (x)] }, where x is the solvent configuration relative to the solute and v (x) is the solute-solvent interaction. The excluded volume region, where v (x) is very large, always makes a positive contribution to the density derivative of βΔμ. The density derivative is reduced by the attractive (negative) portion of v (x), and is not necessarily positive at low temperatures. In Table I and Fig. 2, the density derivative of βΔμ of a polar solute is negative at 400°C in the low-density region. In other words, 400°C is not high enough in the sense that the contribution from the attractive part of the solute-solvent interaction is not overwhelmed by that from the repulsive part. It should be noted that the attractive contribution is more sensitive to the temperature variation than the repulsive contribution and that the repulsive contribution dominates at a high enough temperature.
53. It is a rather rough statement that the density corresponding to the minimum βΔμ is larger when the solute-water interaction is stronger. Indeed, the interaction strength is not a uniquely definable concept, but expresses the "intuitive feeling" about the molecule.
54. H. Sato, N. Matubayasi, M. Nakahara, and F. Hirata, Chem. Phys. Lett. 323, 257 (2000).
55. R. Crovetto, R. Fernández-Prini, and M. L. Japas, J. Chem. Phys. 76, 1077 (1982).
56. R. Fernandez-Prini, R. Crovetto, M. L. Japas, and D. Laria, Acc. Chem. Res. 18, 207 (1985).
57. R. Fernández Prini and R. Crovetto, J. Phys. Chem. Ref. Data 18, 1231 (1989).
58. R. Fernández-Prini, J. L. Alvarez, and A. H. Harvey, J. Phys. Chem. Ref. Data 32, 903 (2003).
59. B. Guillot and Y. Guissani, J. Chem. Phys. 99, 8075 (1993).
60. BTexp(βΔμ), where ρ is the density of the solvent water.
61. 2.
62. NASA Glenn thermodynamic database, URL: http://cea.grc.nasa.gov
63. BT) in the dilute gas condition.
64. 3 when the extrapolation to 400°C is performed. In this view, the extrapolated βΔW at 400°C is in good agreement with the corresponding βΔW value given by Figs. 5 and 8.
65. 2 through the quartz vessel used.
66. T. Minowa and Z. Fang, J. Chem. Eng. Jpn. 31, 488 (1998).
67. I. Wender, Fuel Process. Technol. 48, 189 (1996).
68. C. B. Roberts and N. O. Elbashir, Fuel Process. Technol. 83, 1 (2003).
69. M. Stelmachowski and L. Nowicki, Appl. Energy 74, 85 (2003).
70. J. G. Kirkwood and F. P. Buff, J. Chem. Phys. 19, 774 (1951).
71. N. Matubayasi and R. M. Levy, J. Phys. Chem. 100, 2681 (1996).
72. N. Matubayasi, E. Gallicchio, and R. M. Levy, J. Chem. Phys. 109, 4864 (1998).
73. T. Imai, M. Kinoshita, and F. Hirata, J. Chem. Phys. 112, 9469 (2000).
74. T. Imai, H. Nomura, M. Kinoshita, and F. Hirata, J. Phys. Chem. B 106, 7308 (2002).
75. T. Imai and F. Hirata, J. Chem. Phys. 119, 5623 (2003).
76. N. Matubayasi, L. H. Reed, and R. M. Levy, J. Phys. Chem. 98, 10640 (1994).