Electrochemical determination of the dissociation constants of glycine in mixed solvents.

number: 
133
إنجليزية
department: 
Degree: 
Imprint: 
Chemistry
Author: 
Abeer Khazal Shames
Supervisor: 
Dr. Jalal Mohammed Saleh
year: 
1996

Abstract:

The subject of this thesis involved the following two main lines: [ 1 ] Studies of the thermodynamics of HC1 reaction as well as of its transfer from water to sodium carboxymethylcellulose (CMC)-Water mixtures. Four different compositions of the CMC-Water mixtures have been tested, containing 0.03, 0.06, 0.1, and 0.31 weight percentages of CMC at five temperatures in the range 293.15-313.15 K. [2] Determination of the first and second dissociation constants and the related thermodynamic quantities of grycine dissociation in CMC-Water mixtures; the study also covered the thermodynamic quantities of the transfer of glycine from water to CMC-Water mixtures. Electromotive force measurements using the cell(C) Pţ H2 (g. latm | HCI(m),solvent mixture | AgCI (s), Ag have been used to evaluate the standard potentials of the Ag | AgCI electrode in CMCWater mixtures at five temperatures in the range 293.15-313.15 K. The standard thermodynamic functions for the cell reaction and the standard thermodynamic quantities for the transfer of HCI from water to CMC-Water mixtures have also been determined. The standard free energy for the cell reaction were negative for all the four it compositions indicating the thermodynamic feasibility of the cell reaction. The exothermic behavior of the reaction over such solvent mixtures compositions was in the negative ΔH° values for the reaction. The results also showed that the transfer free energies Δ4G° of HCI from water CMC-Water mixtures at a constant value of X decreased with increasing from 293.15-308.15, increasing thereafter on raising temperature to K particularly for X values ranging from 0.03 to 0.1. The transfer of HCI from to CMC-Water mixtures was thermodynamically feasible at the higher temperatures. Values of ΔtH° were generally positive at a given value of X particularly at 293.15 and 298.15 K becoming negative on increasing the towards 313.15 K. At a constant temperature (298.15 K), values of ΔtH° over X values from 0.03 to 0.1, decreasing thereafter when X increased to variation of TΔ ,S° values for HCI with the variation of X occurred in a similar manner to that of Δ,H° . The Δ,Cp° values remained almost constant and negative at all the five experimental temperatures and solvent compositions. The dissociation constants pK, and pK2 for glycine in CMC-Water mixtures were determined from the e.m.f. measurements of cells without liquid junction consisting of hydrogen and silver-silver chloride electrodes at five temperatures in the range 293.15-313.15 K. The values of me pK and pK 2 of glycine were utilized for the determination of the thermodynamic quantities (ΔG° AH0 ΔS0 and ΔCp0) of the two dissociation reactions of glycine. The data were also used to determine the thermodynamic quantities for the transfer of the acid from the solvent mixtures to the water and of the dissociation products from water to the solvent mixtures. The results of pK and pK 2 indicated that the variation of second dissociation constants pK2 with increasing values of X at a constant temperature (298.15 K) occurred in a reverse manner to those of pK The values of pK 2 decreased generally with increasing temperature, the manner in which such variation occurred did not differ significantly for all the solvent compositions excluding mat at X = 0.03. Variation of pK values with temperatures differed considerably as the composition (X) of the solvent mixtures changed. pK values generally decreased with increasing temperature for all solvent compositions except at X = 0.06. The ΔG° values for the both dissociation stages did not alter significantly with the variation of the solvent compositions and the alteration was confined to X values < 0.1. Both dissociation processes became less feasible on thermodynamic grounds as reflected in the increasing behaviour of ΔG° values with increasing temperature. The ΔH° values for both dissociation stages decreased over X values 0 to 0.06, increasing thereafter over the variation of X from 0.06 to 0.1, beyond which no further significant changes in ΔH° were observed The results of thermodynamic quantities of transfer of glycine from water to CMC-Water mixtures showed that the Δ G° values for the first dissociation stage were slightly negative at two compositions of CMC-Water mixtures (X = 0.03 and 0.10) and positive at the remaining two compositions (X = 0.06 and 0.31), over the entire range of the experimental temperatures. Values of Δ G° for the second dissociation stage were negative at X = 0.06 for all the five experimental temperatures, but only at 308.15 and 313.15 K at X = 0.10 and 0.31. The positive and negative values of Δ G° for this dissociation stage did not exceed + 0.5 kJ.mol-1.The variation of Δ H° and T Δ,S° value to both dissociation stages at constant temperature occurred in a similar pattern. involving an initial decrease of the values of these thermodynamic functions to some negative value increasing thereafter, beyond X - 0,06 lo attain some positive values, The variation of the Δ S°, Δ H° and Δ Cp° with X and temperature showed that the extend of stabilization of the charged species of the dissociation processes a;; well as of the Zwitter ions and also of their degrees of freedom did not vary significantly in CMC-Water mixtures than in water.