Estudio teórico de la descomposición térmica del ácido malónico en fase gaseosa y en disolución acuosa
Abstract
En este trabajo se presenta el estudio computacional de la reacción de descomposición térmica del ácido malónico. Se modeló mediante dos mecanismos, a cinco temperaturas, en fase gaseosa y en disolución acuosa. Los cálculos fueron realizados mediante la teoría de los funcionales de la densidad. Para las condiciones estudiadas de la reacción, la constante de velocidad fue calculada con la ecuación de Eyring-Polanyi. Los resultados fueron comparados con los valores experimentales reportados. Otro tipo de cálculo realizado fueron los orbitales naturales de enlace. Los resultados obtenidos permitieron discutir diferentes aspectos acerca de los mecanismos de reacción planteados.
Palabras clave: B3LYP, M05-2X, ácido malónico, descomposición térmica, mecanismo de reacción.
References
GHOSH DASTIDAR, T.; NETRAVALI, A. N. “‘Green’ crosslinking of native starches with malonic acid and their properties”. Carbohydr. Polym. 2012, 90 (4), 1620–1628. ISSN 0144-8617
APELBLAT, A.; MANZUROLA, E. “Volumetric properties of aqueous solutions of malonic acid”. J. Chem. Thermodyn. 2016, 102, 63–67. ISSN 0021-9614
MASENDE, Z.; KUSTER, B.; PTASINSKI, K.; JANSSEN, F.; KATIMA, J.; SCHOUTEN, J. “Kinetics of malonic acid degradation in aqueous phase over Pt/graphite catalyst”. Appl. Catal. B Environ. 2005, 56 (3), 189–199. ISSN 0926-3373
WAKIL, J. S. “A malonic acid derivative as an intermediate in fatty acid synthesis”. J. Am. Chem. Soc. 1958, 80 (23), 6465–6465. ISSN 0002-7863
VELLIS, De J.; SHANNON, L. M.; LEW, J. Y. “Malonic acid biosynthesis in bush bean roots. I. evidence for oxaloacetate as immediate precursor”. Plant Physiol., 1963, 38 (6), 686–690. ISSN 1532-2548
KIM, Y. “Malonate metabolism: biochemistry, molecular biology, physiology, and industrial application”. J. Biochem. Mol. Biol. 2002, 35 (5), 443–451. ISSN 1225-8687
AMBATI, C.; YUAN, F.; ABU ELHEIGA, L.; ZHANG, Y.; SHETTY, V. “Identification and quantitation of malonic acid biomarkers of In-born error metabolism by targeted metabolomics”. J. Am. Soc. Mass Spectrom. 2017, 28 (5), 929–938. ISSN 1044-0305
HINSHELWOOD, C. “XX.-The Rate of Decomposition of Malonic Acid”. J. Chem. Soc. Trans, 1920, 117 (1), 156–165. ISSN 0368-1645
EL AWAD, A.; MAHFOUZ, R. “Kinetic analysis of isothermal, non-isothermal and catalysed termal Decomposition of Malonic Acid”. J. Therm. Anal. 1989, 35, 1413–1414. ISSN 1388-6150
CAO, J. R.; BACK, R. A. “The thermolysis and photolysis of malonic acid in the gas phase”. Can. J. Chem. 1986, 64 (5), 967–968. ISSN 0008-4042
HALL, G. A. “The kinetics of the decomposition of malonic acid in aqueous solution”. J. Am. Chem. Soc. 1949, 71 (8), 2691–2693. ISSN 0002-7863
CRUZ CASTAÑEDA, J.; NEGRÓN MENDOZA, A.; FRÍAS, D.; COLÍN GARCÍA, M.; HEREDIA, A.; RAMOS BERNAL, S.; VILLAFAÑE BARAJAS, S. “Chemical evolution studies: the radiolysis and thermal decomposition of malonic acid”. J. Radioanal. Nucl. Chem. 2015, 304 (1), 219–225. ISSN 0236-5731
CLARK, L. W. “A systematic study of the kinetics of the decomposition of malonic acid in non-aqueous solvents”. J. Phys. Chem. 1958, 62 (1), 79–81. ISSN 0022-3654
MIDYANA, G. G.; MAKITRA, R. G.; PAL’CHIKOVA, E. Y. “Solvent effect on the reaction of decarboxylation of malonic acid. Correlation analysis”. Russ. J. Gen. Chem. 2010, 80 (5), 944–947. ISSN 1070-3632
CAIRES, F. J.; GOMES, D. J. C.; GIGANTE, A. C.; LIMA, L. S.; CARVALHO, C. T.; IONASHIRO, M. “Thermal behavior of malonic acid, sodium malonate and its compounds with some bivalent transition metal ions in dynamic N2 and CO2 atmospheres”. Braz. J. Therm. Anal. 2013, 2 (1), 12–16. ISSN 2316-9842
STANFORD, V. L.;VYAZOVKIN, S. “Thermal decomposition kinetics of malonicacid in the condensed phase”. Ind. Eng. Chem. Res. 2017, 56 (28), 7964–7970. ISSN 0888-5885
LOUDON, A. G.; MACCOLL, A.; SMITH, D. “Heavy atom kinetic isotope effects. Part 1 .-liquid phase decarboxylation of malonic acid”. J. Chem. Soc. Faraday Trans. 1. 1972, 69.(1), 894–898. ISSN0956-5000
HUANG, C. L.; WU, C. C.;LIEN, M. H. “Ab initio studies of decarboxylations of the β-keto carboxylic acids XCOCH2COOH (X = H, OH, and CH3)”. J. Phys. Chem. A. 1997, 101 (42), 7867–7873. ISSN 1089-5639
DMITRIEVA, N.; GRIDCHIN, S.; ROMODANOVSKII, P.; MAIOROV, A. “Standard enthalpies of formation of D,L-α-alanyl-glycine and the products of its dissociation in aqueous solutions”. Russ. J. Phys. Chem. A. 2010, 84 (11), 1997–1999. ISSN 0036-0244
FRISCH, M. J. et. al. “Gaussian 09, Revision B.01.”. Gaussian, Inc., Wallingford CT, 2010.
LEE, C.; YANG, W.; PARR, R. G. “Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density” Phys. Rev. B, 1988, 37 (2), 785–789.ISSN 1098-0121
BECKE, A. D. “Density-functional thermochemistry. III. The role of exact exchange,” J. Chem. Phys., 1993, 98, (7), 5648–5652. ISSN 0021-9606
STEPHENS, P. J.; DEVLIN, F. J.; CHABALOWSKI, C. F.; FRISCH, M. J. “Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields,” J. Phys. Chem., 1994, 98, (45), 11623–11627. ISSN 0022-3654
ZHAO, Y.; SCHULTZ, N. E.; TRUHLAR, D. G. “Design of density functionals by combining the method of constraint satisfaction with parametrization for thermochemistry, thermochemical kinetics, and noncovalent interactions,” J. Chem. Theory Comp., 2006, 2, (2), 364–382.ISSN 1549-9618
DITCHFIELD, R.; HEHRE, W. J.; POPLE, J. “Self-Consistent Molecular-Orbital Methods. IX. An Extended Gaussian-Type Basis for Molecular-Orbital Studies of Organic Molecules,” J. Chem. Phys., 1971, 54, 724–728. ISSN 0021-9606
MERRICK, J. P.; MORAN, D.; RADOM, L. “An evaluation of harmonic vibrational frequency scale factors,” J. Phys. Chem. A, 2007, 111, (45), 11683–11700. ISSN 1089-5639
MCQUARRIE, D.; SIMON, J.Molecular Thermodynamics. Sausalito: University Science Books, 1999.ISBN 1-891389-05-X
TOMASI, J.; MENNUCCI, B.; CAMMI, R. “Quantum mechanical continuum solvation models.,” Chem. Rev., 2005, 105, (8), 2999–3093.ISSN 0009-2665
GLASSTONE, K.; LAIDLER, K.; EYRING, H.The Theory of Rate Processes. New York: McGraw-Hill, 1941.ISBN 0070233608
BENSON, S. The Foundations of Chemical Kinetics. New York: McGraw-Hill, 1960.ISBN 0070047782
FUKUI, K. “A formulation of the reaction coordinate,” J. Phys. Chem., 1970, 74, (23), 4161–4163. ISSN 0022-3654
REED, A. E.; WEINHOLD, F. “Natural bond orbital analysis of nearHartree – Fock water dimer,” J. Chem. Phys., 1983, 78, 4066–4073. ISSN 0021-9606
REED, A. E.; CURTISS, L. A.; WEINHOLD, F. “Intermolecular interactions from a natural bond orbital , donor-acceptor viewpoint,” Chem. Rev., 1988, 88, 899–926. ISSN 0009-2665
GLENDENING, E. D.; BADENHOOP,J. K.;REED, A.E.; CARPENTER, J.E.; MORALES, C.E.; WEINHOLD, F. “NBO 5.0” Theoretical Chemistry Institute, University of Wisconsin, Madison, 2001
WIBERG, K. B. “Application of the Pople-Santry-Segal CNDO method to the ciclopropylcarbinyl and cyclobutyl cation and to bicyclobutane,” Tetrahedron, 1968, 24, 1083–1096.ISSN 0040-4020
GAO, J.“A theoretical investigation of the enol content of acetic acid and the acetate ion in aqueous solution,” J. Mol. Struct. THEOCHEM, 1996, 370, 203–208.ISSN 0166-1280
LAURELLA, S.β-cetoamidas : estudio de equilibrios tautoméricos y reactividad química.Tesis Doctoral, Universidad Nacional de la Plata, La Plata, 2012.
SPENCER, J. N.; HOLMBOE, E.; KIRSHENBAUM, M.; FIRTH, D.; PINTO, P. “Solvent effects on the tautomeric equilibrium of 2,4-pentanedione,” Can. J. Chem., 1982, 60, 1178-1182.ISSN 0008-4042
DUAN,X.; PAGE, M. "Theoretical investigation of competing mechanisms in the thermal unimolecular decomposition of acetic acid and the hydration reaction of ketene," J. Am. Chem. Soc., 1995,117, 5114-5119.ISSN 0002-7863
FREY, J.; RAPPOPORT, Z. “Observation of an amide enol of bis(2,4,6-triisopropylphenyl)acetic acid,” J. Am. Chem. Soc., 1996, 118, (16), 3994–3995.ISSN 0002-7863
NGUYEN, T. L.; XUE, B. C.; ELLISON, G. B.; STANTON, J. F. “Theoretical study of reaction of ketene with water in the gas phase: formation of acetic acid?,” J. Phys. Chem. A, 2013, 117, (43), 10997–11005. ISSN 1089-5639
HEGARTY, A. F.; NGUYEN, M. T. “Molecular orbital study on the hydrolysis of ketene by water dimer: β-carbon vs. oxygen protonation?” J. Am. Chem. Soc., 1984, 106, 1552-1557.ISSN 0002-7863
KRESGE, A. “Ingold Lecture. Reactive intermediates: carboxylic acid enols and other unstable species,” J. Chem. Soc. Rev., 1996, 25, 275-280. ISSN 0306-0012
MOYANO, A.; PERICAS, M.; VALENTÍ, E. “A theoretical study on the mechanism of the thermal and the acid-catalyzed decarboxylation of 2-oxetanones (β-Lactones),” J. Org. Chem., 1989, 54, (3), 573–582.ISSN 0022-3263
HAMMOND, G. “A Correlation of Reaction Rates,” J. Am. Chem. Soc., 1955, 77, (2), 334–338.ISSN 0002-7863
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