Biotechnology Letters

, Volume 41, Issue 10, pp 1163–1175 | Cite as

Kinetics and thermodynamics of lipase catalysed synthesis of propyl caprate

  • Dhara T. Parikh
  • Kavita J. Lanjekar
  • Virendra K. RathodEmail author
Original Research Paper



To investigate kinetics and thermodynamics of lipase-catalyzed esterification of capric acid with 1-propyl alcohol in a solvent-free system for synthesis of propyl caprate.


The capric acid conversion of 83.82% is achieved at temperature 60 °C, speed of agitation 300 rpm, molar ratio acid:alcohol 1:3, enzyme loading 2% (w/w) and molecular sieves loading 5% (w/w). The activation energy (Ea) for the reaction was determined as 37.79 kJ mol−1. Furthermore, enthalpy (ΔH), entropy (ΔS) and Gibbs free energy (ΔG) values were found out to be + 90.45 kJ mol−1, + 278.99 J mol−1 K−1 and − 2.35 kJ mol−1 respectively.


The results showed that the lipase-catalyzed esterification exhibits an ordered bi–bi mechanism with capric acid inhibiting the reaction and forming the dead-end complex with the lipase. Under the given set of reaction conditions, the lipase catalysed esterification reaction was anticipated to be spontaneous, referring to the value of the Gibbs free energy change (ΔG). Moreover, the esterification process was found to be endothermic, based on the values of enthalpy (ΔH) and entropy (ΔS).


Enzyme kinetics Lipase Ordered bi–bi mechanism Propyl caprate Thermodynamics 



  1. Al-zuhair S (2005) Production of biodiesel by lipase-catalyzed transesterification of vegetable oils: a kinetics study. Biotechnol Prog 21:1442–1448CrossRefGoogle Scholar
  2. Arsan J, Parkin KL (2000) Selectivity of Candida antarctica B lipase toward fatty acid and (Iso) propanol substrates in esterification reactions in organic media. J Agric Food Chem 48:3738–3743CrossRefGoogle Scholar
  3. Awang R, Basri M, Ahmad S, Salleh A (2004) Lipase-catalyzed esterification of palm-based 9,10-dihydroxystearic acid and 1-octanol in hexane—a kinetic study. Biotechnol Lett 26:11–14CrossRefGoogle Scholar
  4. Badgujar KC, Bhanage BM (2014) Application of lipase immobilized on the biocompatible ternary blend polymer matrix for synthesis of citronellyl acetate in non-aqueous media: kinetic modelling study. Enzyme Microb Technol 57:16–25CrossRefGoogle Scholar
  5. Bansode SR, Hardikar MA, Rathod VK (2017) Evaluation of reaction parameters and kinetic modelling for Novozym 435 catalysed synthesis of isoamyl butyrate. J Chem Technol Biotechnol 92(6):1306–1314CrossRefGoogle Scholar
  6. Chulalaksananukul W, Condort JS, Delorme P, Willemot RM (1990) Kinetic study of esterification by immobilized lipase in n-hexane. FEBS Lett 276:181–184CrossRefGoogle Scholar
  7. De Barros DPC, Pinto F, Fonseca LP et al (2014) Enzymatic kinetic model for the esterification of ethyl caproate for reaction optimization. J Mol Catal B 101:16–22CrossRefGoogle Scholar
  8. De Castro HF, De Oliveira PC, Pereira EB, Brazil LÐSPÐ (1997) Evaluation of different approaches for lipase catalysed synthesis of citronellyl acetate. Biotechnol Lett 19:229–232CrossRefGoogle Scholar
  9. Garcia T, Sanchez N, Martinez M, Aracil J (1999) Enzymatic synthesis of fatty esters part I. Kinetic approach☆. Enzyme Microb Technol 25:584–590CrossRefGoogle Scholar
  10. Gawas SD, Jadhav SV, Rathod VK (2016) Solvent free lipase catalysed synthesis of ethyl laurate: optimization and kinetic studies. Appl Biochem Biotechnol 180:1428–1445CrossRefGoogle Scholar
  11. Gharat N, Rathod VK (2013) Enzyme catalyzed transesterification of waste cooking oil with dimethyl carbonate. J Mol Catal B 88:36–40CrossRefGoogle Scholar
  12. Guvenc Afife, Kapucu NMU (2002) The production of isoamyl acetate using immobilized lipases in a solvent-free system. Process Biochem 38:379–386CrossRefGoogle Scholar
  13. Higuchi WI, Patel FA (2018) Composition comprising bioreversible derivatives of Hydroxy n-substituted-2-aminotetralins, dosage forms and related methods.pdf. US9956201 B2Google Scholar
  14. Ho J, Bong S, Woo S et al (2011) Biodiesel production by a mixture of Candida rugosa and Rhizopus oryzae lipases using a supercritical carbon dioxide process. Bioresour Technol 102:2105–2108CrossRefGoogle Scholar
  15. Jaiswal KS, Rathod VK (2018) Acoustic cavitation promoted lipase catalysed synthesis of isobutyl propionate in solvent free system: optimization and kinetic studies. Ultrason Sonochem 40:727–735CrossRefGoogle Scholar
  16. Jensen RG, Galluzzo DR, Bush VJ (1990) Selectivity is an important characteristic of lipases (Acylglycerol hydrolases). Biocatalysis 3:307–316CrossRefGoogle Scholar
  17. Karabulut I, Durmaz G, Hayaloglu AA (2009) Fatty acid selectivity of lipases during acidolysis reaction between oleic acid and monoacid triacylglycerols. J Agric Food Chem 57:10466–10470CrossRefGoogle Scholar
  18. Lanjekar K, Rathod VK (2013) Utilization of glycerol for the production of glycerol carbonate through greener route. J Environ Chem Eng 1:1231–1236CrossRefGoogle Scholar
  19. Marangoni AG (2003) Enzyme kinetics a modern approach. Wiley, New JerseyGoogle Scholar
  20. Matsunaga S, Takahashi A, Hayakawa H (2018) Curing accelerator for oxidative polymerization-type unsaturated resin, printing ink and coating material.pdf. US2016/0152867 A1Google Scholar
  21. Melo LLMM, Pastore GM, Macedo GA (2005) Optimized synthesis of citronellyl flavour esters using free and immobilized lipase from Rhizopus sp. Process Biochem 40:3181–3185CrossRefGoogle Scholar
  22. Mestri SD, Pai JS (1995) Effect of moisture on lipase catalysed esterification of Geraniol of palmarosa oil in non-aqueous system. Biotechnol Lett 17:459–460CrossRefGoogle Scholar
  23. Paiva AL, Balca VM, Malcata FX (2000) Kinetics and mechanisms of reactions catalyzed by immobilized lipases. Enzyme Microb Technol 27:187–204CrossRefGoogle Scholar
  24. Paludo N, Alves JS, Altmann C et al (2015) The combined use of ultrasound and molecular sieves improves the synthesis of ethyl butyrate catalyzed by immobilized Thermomyces lanuginosus lipase. Ultrason Sonochem 22:89–94CrossRefGoogle Scholar
  25. Pellis A, Comerford JW, Mane AJ et al (2018) Elucidating enzymatic polymerisations: chain-length selectivity of Candida antarctica lipase B towards various aliphatic diols and dicarboxylic acid diesters. Eur Polym J 106:79–84CrossRefGoogle Scholar
  26. Raza S, Fransson L, Hult K (2001) Enantioselectivity in Candida antarctica lipase B: a molecular dynamics study. Protein Sci 10:329–338CrossRefGoogle Scholar
  27. Ribeiro SS, Oliveira JRD, Porto AL (2012) Lipase-catalyzed kinetic resolution of (±)- mandelonitrile under conventional condition and microwave irradiation. J Braz Chem Soc 23:1395–1399CrossRefGoogle Scholar
  28. Segel IH (1993) Enzyme kinetics: behavior and analysis of rapid equilibrium and steady-state enzyme systems. Wiley, New YorkGoogle Scholar
  29. Sheldon RA (2007) Enzyme immobilization: the quest for optimum performance. Adv Synth Catal 349:1289–1307CrossRefGoogle Scholar
  30. Shimotori Yasutaka, Hoshi MMT (2015) Combination of novozym 435-catalyzed enantioselective hydrolysis and amidation for the preparation of optically active δ-hexadecalactone. J Oleo Sci 64:561–575CrossRefGoogle Scholar
  31. Srivastava S, Modak J, Madras G (2002) Enzymatic synthesis of flavors in supercritical carbon dioxide. Ind Eng Chem Res 41:1940–1945CrossRefGoogle Scholar
  32. Tewari YB, Bunk DM (2001) Thermodynamics of the lipase-catalyzed esterification of glycerol and n -octanoic acid in organic solvents and in the neat reaction mixture. J Mol Catal B 15:135–145CrossRefGoogle Scholar
  33. Yahya ARM, Anderson WA, Moo-young M et al (1998) Ester synthesis in lipase- catalyzed reactions. Enzyme Microb Technol 23:438–450CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  • Dhara T. Parikh
    • 1
  • Kavita J. Lanjekar
    • 1
  • Virendra K. Rathod
    • 1
    Email author
  1. 1.Department of Chemical EngineeringInstitute of Chemical TechnologyMumbaiIndia

Personalised recommendations