Kinetics of nopyl acetate synthesis by homogeneously catalyzed esterification of acetic acid with nopol

Aida Luz Villa-Holguín, Eliana Paola Hurtado-Burbano


The esterification of nopol with acetic acid to produce nopyl acetate using sulfuric acid as homogeneous catalyst was studied. The reactions were carried out in a batch reactor, at different temperatures (50, 60, 70 and 80 °C), catalyst concentrations (0.0184, 0.0275, 0.0367 and 0.0480 mol L-1) and molar ratio of acetic acid to nopol (1: 1, 1:2, 1:3 and 1: 4); the chemical equilibrium composition was measured at those reaction conditions. It was found that the equilibrium composition is a weak function of temperature, equilibrium conversion was 63, 68, 71 and 75% at 50, 60, 70 and 80°C, respectively. The reaction was described with a simple power-law model with a second-order kinetic model for both the forward and the backward reaction, using concentration and activities which were predicted by the Universal Functional group Contribution (UNIFAC) method for considering non-ideal behavior of the liquid phase. The forward reaction rate and the equilibrium constants increased with temperature; the relation of the pre-exponential factor with the catalyst amount was evaluated. The activation energy and pre-exponential factor estimated for the forward reaction using the kinetic model based on concentration, were respectively, 28.08 kJ mol-1 and 11126 L mol-1 h-1 with a concentration of catalyst of 0.0275 M. Using the kinetic model based on activities, the forward reaction rate constant was 28.56 kJ·mol-1 and the kfo,act was 33860 L mol-1 h-1. The enthalpy (34.90 kJ mol-1) and the entropy (0.12 kJ mol-1 K-1) of reaction were determined using van’t Hoff equation.


esterification, nopyl acetate; reaction rate; equilibrium constant; kinetics

Full Text:



E. Akbay and M. Altıokka, “Kinetics of esterification of acetic acid with n-amyl alcohol in the presence of amberlyst-36,” Appl. Catal. A: Gen., vol. 396, no. 1-2, pp. 14–19, Apr 2011.

S. Ali, A. Tarakmah, S. Merchant, and T. Al-Sahhaf, “Synthesis of esters: Development of the rate expression for the dowex 50 wx8-400 catalyzed esterification of propionic acid with 1-propanol,” Chem. Eng. Sci., vol. 62, no. 12, pp. 3197–3217, Jun 2007.

H. Pardel, S. Sarron, and C. Roy, “α-terpineol from hydration of crude sulfate turpentine oil,” J. Agric. Food Chem., vol. 49, no. 9, pp. 4337– 4341, Aug 2001.

D. B. T. Chatterjee, “Synthesis of terpene esters by an immobilized lipase in a solvent-free system,” Biotechnol. Lett., vol. 20, no. 9, pp. 865––868, Sep 1998.

P. Mullen, “Fragrance-containing insect repellant compositions,” U.S. Patent 2 005 002 980, Jan. 6, 2005.

D. B. et al, “A toxicologic and dermatologic assessment of cyclic and non-cyclic terpene alcohols when used as fragrance ingredients,” Food Chem. Toxicol., vol. 46, no. 11, pp. S1–S71, Nov 2008.

B. Jerez, Morality of War, 2nd ed. Tonawanda, NY: Broadview Press, 2013.

W. Poucher, Poucher’s Perfumes, Cosmetics and Soaps — Volume 1: The Raw Materials of Perfumery, 1st ed. Netherlands: Springer, 1991.

A. Corma and M. Renz, “Water-resistant lewis-acid sites: carbonylene reactions catalyzed by tin-containing, hydrophobic molecular sieves,” Arkivoc, vol. 8, pp. 40–48, 2007.

D. Opdyke, “Monographs on fragrance raw materials,” vol. 17, no. 5, pp. 509–511, Oct 1979.

P. JagadeeshBabu, K. Sandesh, and M. Saidutta, “Kinetics of esterification of acetic acid with methanol in the presence of ion Exchange resin catalysts,” Ind. Eng. Chem. Res., vol. 50, no. 12, pp. 7155–7160, Apr 2009.

J. L. et al, “Kinetics of esterification of propanoic acid with metanol over a fibrous polymer-supported sulphonic acid catalyst,” AppliedCatalysis A: General, vol. 228, no. 1–2, pp. 253–267, Mar 2002.

Y. Liu, E. Lotero, and J. Goodwin, “A comparison of the esterification of acetic acid with methanol using heterogeneous versus homogeneous acid catalysis,” J. Catal., vol. 242, no. 2, pp. 278–286, Sep 2006.

R. R. et al, “Development of a kinetic model for the esterification of acetic acid with methanol in the presence of a homogeneous acid catalyst,” Chem. Eng. Sci., vol. 52, no. 19, pp. 3369–3381, Oct 1997.

S. Geyer, W. Zeiger, and R. Mayer, “Säurekatalysierte umwandlungen in der monoterpenreihe,” Z. Chem., vol. 6, no. 4, pp. 138–146, Apr 1996.

M. Chiplunkar, M. Hong, M. Malone, and M. Doherty, “Experimentalstudy of feasibility in kinetically-controlled reactive distillation,” AIChE J, vol. 51, no. 2, pp. 464–479, Feb 2005.

C. Beula and P. Sai, “Kinetics of esterification of acetic acid and ethanol with a homogeneous acid catalyst,” Ind. Chem. Eng., vol. 57, no. 2, pp. 177–196, 2015.

G. Jyoti, A. Keshav, J. Anandkumar, and S. Bhoi, “Homogeneous and heterogeneous catalyzed esterification of acrylic acid with ethanol: Reaction kinetics and modeling,” Int. J. Chem. Kinet., vol. 50, no. 5, pp. 370–380, Mar 2018.

S. W. L. et al, “Reactions of α-pinene using acidic ionic liquids as catalysts,” J. Mol. Catal. A: Chem, vol. 279, no. 2, pp. 177–181, Jan 2008.

S. Liu, C. Xie, S. Yu, F. Liu, and K. Ji, “Esterification of α-pinene and acetic acid using acidic ionic liquids as catalysts,” Catal. Commun., vol. 9, no. 7, pp. 1634–1638, Apr 2008.

L. L. et al, “Synthesis of terpinyl acetate using octadecylamine ethoxylate ionic liquids as catalysts,” Res. Chem. Intermed., vol. 39, no. 5, pp. 2095––2105, May 2013.

D. J. T. et al, “Tuning the acidity of sulfonic functionalized ionic liquids for highly efficient and selective synthesis of terpene esters,” J. Ind. Eng. Chem., vol. 41, pp. 122–129, Sep 2016.

X. Chen and T. O. Z. Xu, “Liquid phase esterification of acrylic acid with 1-butanol catalyzed by solid acid catalysts,” Appl Catal A: Gen, vol. 180, no. 1-2, pp. 261––269, Apr 1999.

J. L. et al, “Esterification of different acids over heterogeneous and homogeneous catalysts and correlation with the taft equation,” J Mol Catal A: Chem., vol. 182–183, pp. 555–563, May 2002.

J. G. J. Y. Liu, E. Lotero, “Effect of water on sulfuric acid catalyzed esterification,” J Mol Catal A: Chem., vol. 245, no. 1-2, pp. 132–140, Feb 2006.

E. L. et al, “Synthesis of biodiesel via acid catalysis,” Ind. Eng. Chem. Res., vol. 44, no. 14, pp. 5353––5363, Jan 2005.

M. Mekala and V. Goli, “Kinetics of esterification of methanol and acetic acid with mineral homogeneous acid catalyst,” Chin. J. Chem. Eng., vol. 23, no. 1, pp. 100–105, Jan 2015.

Z. Xu and K. Chuang, “Kinetics of acetic acid esterification over ion exchange catalysts,” Can. J. Chem. Eng., vol. 74, pp. 493–500, Mar 1996.

M. de Jong, R. Feijt, E. Zondervan, T. Nijhuis, and A. de Haan, “Reaction kinetics of the esterification of myristic acid with isopropanol and n-propanol using p-toluene sulphonic acid as catalyst,” Appl Catal A: Gen., vol. 365, no. 1, pp. 141–147, Aug 2009.

T. Pöpken, L. Götze, and J. Gmehling, “Reaction kinetics and chemical equilibrium of homogeneously and heterogeneously catalyzed acetic acid esterification with methanol and methyl acetate hydrolysis,” Ind. Eng. Chem. Res., vol. 39, no. 7, pp. 2601––2611, Jun 2000.

D. J. T. et al, “Kinetics for the esterification reaction of n-butanol with acetic acid catalyzed by noncorrosive brønsted acidic ionic liquids,” Ind. Eng. Chem. Res., vol. 50, no. 4, pp. 1989–1996, Jan 2011.

O. Levenspiel, Chemical Reaction Engineering, 3rd ed. New York, USA: John Wiley Sons, 1999.

D. Othmer and S. Rao, “n-butyl oleate from n-butyl alcohol and oleic acid,” Ind. Eng. Chem., vol. 42, no. 9, pp. 1912––1919, Sep 1950.

M. Altiokka and A. Citak, “Kinetics study of esterification of acetic acid with isobutanol in the presence of amberlite catalyst,” Appl. Catal. A: Gen., vol. 239, no. 1-2, pp. 141–148, Jan 2003.

G. Yadav and P. Mehta, “Heterogeneous catalysis in esterification reactions: Preparation of phenethyl acetate and cyclohexyl acetate by using a variety of solid acidic catalysts,” Ind. Eng. Chem. Res., vol. 33, no. 9, pp. 2198––2208, Sep 1994.

R. Aafaqi, A. Mohamed, and S. Bhatia, “Kinetics of esterification of palmitic acid with isopropanol using ptoluene sulfonic acid and zinc ethanoate supported over silica gel as catalysts,” J Chem Technol Biotechnol, vol. 79, pp. 1127––1134, Sep 2004.

T. Komón, P. Niewiadomski, P. Oracz, and M. E. Jamróz, “Esterification of acrylic acid with 2-ethylhexan-1-ol: Thermodynamic and kinetic study,” Applied Catalysis A: General, vol. 451, pp. 127–136, Jan 2013.

S. Chandane, A. Rathod, K. Wasewar, and S. Sonawane, “Process optimization and kinetic modeling for esterification of propionic acid with benzyl alcohol on ion-exchange resin catalyst,” Korean J Chem Eng., vol. 34, no. 4, pp. 987––996, Apr 2017.

A. Kouzekonani and M. Mahdavian, “Modeling of esterification in a batch reactor coupled with pervaporation for production of ethyl acetate catalyzed by ion- exchange resins,” Adv Environ Technol, vol. 2, pp. 69–75, 2015.

A. Fredenslund, R. Jones, and J. Prausnitz, “Group contribution estimation of activity coefficients in nonideal liquid mixtures,” AIChE J., vol. 21, no. 6, pp. 1086–1099, Nov 1975.

B. E. Polling, J. M. Prausnitz, and J. P. O’Connell, The properties of gases and liquids, 5th ed. NY, USA: McGraw-Hill, 2013.

B. Erdem and M. Cebe, “Kinetics of esterification of propionic acid with n-amyl alcohol in the presence of cation exchange resins,” Korean J. Chem. Eng., vol. 23, no. 6, pp. 896–901, Nov 2006.

L. Ma, Y. Han, K. Sun, J. Lu, and J. Ding, “Kinetic and thermodynamic studies of the esterification of acidified oil catalyzed by sulfonated cation exchange resin,” J. Energy Chem., vol. 24, no. 4, pp. 456–462, Jul 2015.

S. Schwarzer and U. Hoffmann, “Experimental reaction equilibrium and kinetics of the liquid phase butyl acrylate synthesis applied to reactive distillation simulations,” Chem Eng Technol., vol. 25, no. 10, pp. 975–980, Oct 2002.

J. E. House, Principles of chemical kinetics, 2nd ed. New York, USA: Elsevier Inc., 1997.

DOI: Abstract : 156 PDF : 148

Article Metrics

Metrics Loading ...

Metrics powered by PLOS ALM

Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International License.

Esta publicación hace parte del Sistema de Revistas de la Universidad de Antioquia
¿Quieres aprender a usar el Open Journal system? Ingresa al Curso virtual
Este sistema es administrado por el Programa Integración de Tecnologías a la Docencia
Universidad de Antioquia
Powered by Public Knowledge Project