ABSTRACT:
The acid catalyzed hydrolysis of butyl formate in presence of 0.1N-HCI in water and the presence of water-DMSO mixture containing up to 30-70% (v/v) was studied over the temperature ranging from 20-400C. The rate of reaction decreases with decrease of water content of the solvent mixture and reached minima at about 70% of organic solvent. The number of water molecule associated with activated complex was showing decrease in trend with increase of temperature, is an indication of change in mechanism from unimolecular to bimolecular in reaction media. The parameters of thermodynamic activation were also calculated and discussed in terms of solvent effect with help of plots of ?H* versus ?S*, the isokinetic temperature was calculated and found to be greater than 300.
Cite this article:
A. K. Singh. Water-DMSO Co–Solvent effect and kinetics of acid catalyzed Hydrolysis of butyl formate and Influence on Activation Parameters. Asian Journal of Research in Chemistry 2023; 16(2):159-2. doi: 10.52711/0974-4150.2023.00026
Cite(Electronic):
A. K. Singh. Water-DMSO Co–Solvent effect and kinetics of acid catalyzed Hydrolysis of butyl formate and Influence on Activation Parameters. Asian Journal of Research in Chemistry 2023; 16(2):159-2. doi: 10.52711/0974-4150.2023.00026 Available on: https://www.ajrconline.org/AbstractView.aspx?PID=2023-16-2-10
REFERENCES:
1. Sharma Sangita et al. Kinetic study of specific base catalyzed hydrolysis of Ethyl Acrylate in water-Ethanol binary system. Russian Journal of Physical Chemistry A. Vol. 87, No. 5, Pp730-736. (2013)
2. Nisha Chhetri., S. A. Bhoite. Study of Solvent Effects on Hydrolysis of Mono-m-toluidine Phosphate. International Journal of Chem Tech Research, Vol.9, No.02 pp 106-109, (2016)
3. DK Varma, Prahalad Kumar, RK Lal, Study of solvent effect on kinetics of alkaline hydrolysis of ethyl picolinate in water acetone medium. International Journal of Advance Engineering and Managements. (IJAEM),Vol-2 Issue-9 pp5-6, 2020.
4. F. Y. Khalil and M.T. Hanna, kinetic, activation parameters and mechanism of acid hydrolysis of ter-Butyl acetate in aqueous DMSO. Croatica Chemica Acta, vol-52(4)pp329-338,(1979).
5. Metwally M. S.: Kinetic study of resin catalised hydrolysis of Ethyl Propionate in aqueous solvent system. Reaction kinetic catalysis and Letters vol-47. No-2 pp319-336. (1992)
6. Singh AK. A kinetics study of solvent effect on alkali catalyzed solvolysis of methyl salicylate in water-DMF media. İnternational journal of advance research and innovation. Vol-3(3);547-549. 6.F. Y. Khalil and M.T. Hanna, kinetic, activation parameters and mechanism of acid hydrolysis of ter-Butyl acetate in aqueous DMSO. Croatica Chemica Acta, vol-52(4)pp329-338,(1979).
7. Metwally M. S.: Kinetic study of resin catalyzed hydrolysis of Ethyl Propionate in aqueous solvent system. Reaction kinetic catalysis and Letters vol-47. No-2 pp319-336. (1992)
8. AK. Singh, Activation parameters and solvent effect on solvolysis of ethyl benzoate in aqueous organic solvent system. Asian J. of Research in Chemistry, Vol-12(2),pp99-102, 2019.
9. Ingold C K. Structure and mechanism of organic chemistry. Cornell University press Ithyca (1967
10. Laidler K.J and Landskroener P A,: Trans Faraday Soc. 52, 200( 1956)
11. E. Tommilla, M Tiilikainen, A. Viapio, Effect of solvent on reaction velocity(X). Solvolysis of alkyl halide in acetone-water mixture. Ann. Acta Sci. Fenn. A2, 91. 1959.
12. C. A. Lane, The possibility of cyclic mechanism for thr acid catalysed ester hydrolysis. J. Amm. Chem. Soc. 86,12,pp2521-2523, 1964.
13. R.E. Robertson,: A survey of thermodynamic parameter for solvolysis in water”, Prog. Phy.Org. chem. 4, pp213 (1967)
14. Robertson. R E., Heppolitite. R L, Scott J.M.W.: A survey of thermodynamic parameter for the solvolysis of water. Canad. Journal of Chemistry. 37(4) pp803-824.(1959)
15. AK. Singh, Activation parameters and solvent effect on solvolysis of ethyl benzoate in aqueous organic solvent system. Asian J. of Research in Chemistry, Vol-12(2),pp99-102, 2019
16. Arjuman Bano, AK. Singh, A kinetics study of dipolar protic solvent in alkaline hydrolysis of ethyl nicotinate in water-ethanol media-A solvent effect. J. of Ultra Chemistry, Vol-13(6)pp145-150,2017.
17. AK. Singh, Solven effect and kinetics on solvolysis of propyl formate in water propanol solvent mixture. International J. of Chemical Science, Vol-3,Issue-4, pp82-84, 2019.
18. Wynne-jones W F K and Eyring H.: The Absolute rate of reaction in condense phases” Journal of Chemical Physics 3; 492-502 (1953).
19. RF Hund and Salive B. Solvent participation in nucleophilic displacement reaction part-II. The reaction between ethanol and acid chloride. Journal of Chem. Soc.1955,pp41-4129.
20. E Tommila, E Mirikallo. Effect of solvent on reaction velocity (VI). Hydrolysis of alkyl ester of benzenesolfonic acid in dioxane-water mixture. Suom. Kemistil. 26B: 1953. Pp79-80.
21. AK Singh, kinetic and solvent effect on activation parameter of aquo-propanol solvent for acid catalyzed solvolysis of propyl format. International J. of Chemical Science, Vol-3, Issue-4,pp85-88, 2019.
22. AK Singhand LK. Tiwari, Study of solvent effect of protic solvent on solvolysis of Hexanoate ester and activation parameter, Asian J. of Research in Chemistry, Vol-13(3),pp216-218, 2020.
23. Barclay I M. and Butlar IAV. The Entropy of solution. Trans Farad Soc. 1938. 34. Pp1445-1454.
24. Laffler J E. The enthalpy entropy relationship and its implication for organic chemistry. The Journal of Organic Chemistry. 20(9):1955. pp1220-1231
25. AK. Singh. Solvent effect and Activation Parameters: A Kinetic Reaction of Ethyl Caprylate in Water-Acetone Media. Asian J. of Research in Chemistry, Vol-14(6),pp441-446, 2021.