Gibbs Free Energy Change (∆G) in Aqueous Dissociation of Benzoic Acid at Temperature ‘K’: A Thermodynamic Study
Chemical Science International Journal,
In article, we have reported a thermodynamic based study of the Gibbs free energy change (∆G) in aqueous dissociation of benzoic acid at Kelvin temperature range in between of 288 K to 318 K. Thermodynamically, at this Kelvin temperatures range the dissociation constant (Ka) of benzoic acid into aqueous solutions have been determined by applying of titration method against standard basic solution of NaOH at different concentrations or ionic strength of NaCl. In observation, the value of Ka is being inversely proportional with respect to temperature in between 289 K to 303 K, and at higher temperature in between 303 K to 314 K, it being directly proportional. This is reported that, there are no regular correlation in between temperature and Ka of that acid. In graph, the plot has shown the value of Ka of benzoic acid is being 4.176 at 298 K temperature. Thus, in finding of precious results for benzoic acid dissociation into water an applying the Gibbs free energy change relationship (∆G = ∆H - T∆S) for endothermic or exothermic reaction process at standard condition of thermodynamic parameters. These parameters value (in kJ.mol-1) are being as ∆G = 12.507, ∆H = 3.823 and ∆S = -29.14. And, at 298 K, it is show that the acid dissociation into aqueous solvent is an endothermic and non-spontaneous process with ordered entropy (∆S).
- Benzoic acid
- ionic strength
- dissociation constant
- Van’t Hoff equation
- Gibbs free energy change
How to Cite
Mishra SP. Titrimetric study of solubility of benzoic acid and their partition in water and benzene solvents. Chemical Sci. Int. J. 2021;30(3):40-45.
Finar IL. Organic Chemistry, 6th Edition, Dorling Kindersley (India) Pvt. Ltd. 2007.
Sergeeva VF. Salting-out and salting-in of non-electrolytes. Russian Chemical Reviews. 1965;34:309-317.
Kilpatrick M, Eanes RD, Morse JG. The dissociation constants of acids in salt solutions. IV. Cyclohexanecarboxylic acid. Journal of the American Chemical Society. 1953;75(3):588-9.
Kettler RM, Wesolowski DJ, Palmer DA. Dissociation quotient of benzoic acid in aqueous sodium chloride media to 250 C. Journal of solution chemistry. 1995;24(4):385-407.
Mishra SP. Concentration effect of sodium chloride salt on benzoic acid solubility and dissocation into water at 298 K temperature. Int. Res. J. Pure & Appl. Chem. 2021;22(6):47-52.
Mishra SP. Introducing of thermodynamic Van’t Hoff equation in process of dissociation of benzoic acid at ordinary temperature range. Chemical Sci. Int. J. 2022;31(1):8-14.
Berthelot M, Jungfleisch E. Sur les lois qui président au partage d’un corps entre deux dissolvants (expériences). Ann Chim Phys. 1872;26:396-407.
Nernst W. Distribution of a substance between two solvents and between solvent and vapor. Z. phys. Chem. 1891;8:110-39.
Treptow RS. Determination of ΔH for reactions of the born-haber cycle. Journal of chemical education. 1997;74(8):919.
Ruoyu L, Zeitler JA, Tomerini D, Parrott EPJ, Gladden LF, Day GM. Phys. Chem. Chem. Phys. 2010;12(20):5329- 5340.
Ramesh H, Huda N, Hossain M, Bhuyan AK. Food Additives Benzoic Acid and its Methyl and Propyl Parahydroxy Derivatives Aggregate Proteins. ACS Food Science & Technology. 2021;1(11):2162-73.
Bolton PD, Fleming KA, Hall FM. Linear free energy enthalpy entropy relation for the ionization of benzoic acids. Journal of the American Chemical Society. 1972;94(3):1033-4.
Huh Y, Lee JG, McPhail DC, Kim K. Measurement of pH at elevated temperatures using the optical indicator acridine. Journal of solution chemistry. 1993;22(7):651-61.
Wang Z, Deng H, Li X, Ji P, Cheng J-P. Standard and absolute pKa scales of substituted benzoic acids in room temperature ionic liquids. J. Org. Chem. 2013;78(24):12487-493.
Vogel A. Text book of Quantitative Chemical Analysis, 5th Edition, Longman, Harlow; 1989.
Thomas LH, Jones Andrew OF, Kallay AA, Mclntyre GJ, Wilson CC. Cryst. Growth Design. 2016;16(4):2112-2122.
Remmers K, Meerts WL, Ozier I. Proton tunneling in the benzoic acid dimer studied by high resolution ultraviolet spectroscopy. The Journal of Chemical Physics. 2000;112(24):10890-4.
Khouri SJ. Titrimetric study of the solubility and dissociation of benzoic acid in water: effect of ionic strength and temperature. American J. Analytical Chem. 2015;6:429-436.
Steigman J, Sussman D. Acid-base reactions in concentrated aqueous quaternary ammonium salt solutions. I. Strong acids and bases, carboxylic acids, amines, and phenol. Journal of the American Chemical Society. 1967;89(25):6400-6.
Read AJ. Ionization constants of benzoic acid from 25 to 250° C and to 2000 bar. J. Solution Chem. 1981;10:437-450.
Ellis AJ. The ionization of acetic, propionic, n-butyric, and benzoic acid in water, from conductance measurements up to 225°. Journal of the Chemical Society (Resumed). 1963:2299-310.
Matsui T, Ko HC, Hepler LG. Thermodynamics of ionization of benzoic acid and substituted benzoic acids in relation to the Hammett equation. Canadian Journal of Chemistry. 1974;52(16):2906-11.
Bosch E, Bou P, Allemann H, Roses M. Retention of ionizable compounds on HPLC. pH scale in methanol-water and the pK and pH values of buffers. . Analytical Chem. 1996;68(20):3651-3657.
Sarmini K, Kenndler E. Capillary zone electrophoresis in mixed aqueous–organic media: effect of organic solvents on actual ionic mobilities, acidity constants and separation selectivity of substituted aromatic acids.: I. Methanol. Journal of Chromatography A. 1998;806(2):325-35.
Cleveland JA, Benko MH Jr., Gluck SJ, Walbroehl YM. J. Chromatography A. 1993;652:301-308.
Lima EC, Hosseini-Bandegharaei A, Moreno-Piraján JC, Anastopoulos I. A critical review of the estimation of the thermodynamic parameters on adsorption equilibria. Wrong use of equilibrium constant in the Van't Hoof equation for calculation of thermodynamic parameters of adsorption. Journal of molecular liquids. 2019;273:425-34.
Solomons GT, Fryhle CB. Organic Chemistry, 10th Edition, John Wiley & Sons, Hoboken; 2011.
Strong LE, Brummel CL, Ryther R, Radford JR, Pethyridge AD. J. Solution Chem. 1988;17:1145-1167.
Atkins P, de Paula J. Physical Chemistry, 9th Edition, W. H. Freeman and Company, New York; 2010.
Mesmer RE, Marshall WL, Palmer DA, Simonson JM, Holmes HF. Thermodynamics of aqueous association and ionization reactions at high temperatures and pressures. Journal of Solution Chemistry. 1988;17(8):699-718.
Fernandez LP, Hepler LG. Thermodynamics of Aqueous Benzoic Acid and the Entropy of Aqueous Benzoate Ion. The Journal of Physical Chemistry. 1959;63(1):110-2.
Baes CF, Jr, Mesmer RE. The Hydrolysis of Cations, John Wiley, New York; 1976.
Stańczyk M, Boruń A, Jóźwiak M. Conductance studies of aqueous solutions of sodium salts of selected benzoic acid derivatives at temperatures from (288.15 to 318.15) K. Journal of Molecular Liquids. 2019;278:247-52.
Karimova NV, Luo M, Grassian VH, Gerber RB. Absorption spectra of benzoic acid in water at different pH and in the presence of salts: Insights from the integration of experimental data and theoretical cluster models. Physical Chemistry Chemical Physics. 2020;22(9):5046-56.
Berzins A, Semjonova A, Actins A, Salvalaglio M. Speciation of Substituted Benzoic Acids in Solution: Evaluation of Spectroscopic and Computational Methods for the Identification of Associates and Their Role in Crystallization. Crystal Growth & Design. 2021;21(9):4823-36.
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