Determination of dissociation constants and thermodynamic parameters of pyrimidine derivatives in organic-water mixed solvents at different temperatures

2014 ◽  
Vol 199 ◽  
pp. 419-425 ◽  
Author(s):  
Kapil Bhesaniya ◽  
Shipra Baluja
Author(s):  
I. Shehatta

The ionization constants of cephradine in 0, 10, 20, 30, 40, 50, 60, 70, 80 and 90% ( v/v ) 1,4-dioxane-water mixed solvents were determined using a potentiometric technique and an automatic titrator. The measurements were performed at four different temperatures and 0.1 M KCl, and thus the thermodynamic parameters of ionization and transfer were evaluated. The ionization of cephradine has been found to be endothermic and entropically unfavourable. A non-linear dependence of the ionization Gibbs energies (Δ


e-xacta ◽  
2017 ◽  
Vol 10 (2) ◽  
pp. 73 ◽  
Author(s):  
Heloísa Righi Pessoa da Silva ◽  
Roberta Pazinato Cuco ◽  
Barbara Daniele Almeida Porciuncula ◽  
Camila Da Silva

<p>Este estudo tem como objetivo a obtenção de dados cinéticos da secagem de cenouras, bem como o ajuste de modelos matemáticos aos dados experimentais e determinação dos parâmetros termodinâmicos do processo. Buscando este propósito, experimentos foram conduzidos em estufa com renovação e circulação de ar, nas temperaturas de 50, 60, 70 e 80 °C. Os modelos matemáticos foram ajustados aos dados das cinéticas de secagem à diferentes temperaturas, e os modelos de Page e de Midilli apresentaram o maior coeficiente de correlação (R<sup>2</sup>) e menor valor de RMSE. Da análise termodinâmica verificou-se que a entalpia e a energia livre de Gibbs diminuíram com o aumento da temperatura, característico de um processo endotérmico. A entropia apresentou valores negativos e diminuiu com a diminuição na temperatura de secagem, isto indica que há um aumento no grau de ordem do sistema, considerado desfavorável entropicamente.</p><p> </p><p>ABSTRACT</p><p>This study aims to obtain kinetic data of carrot drying, as well as the adjustment of mathematical models to the experimental data and determination of the thermodynamic parameters of the process. For this purpose, experiments were conducted in an oven with renovation and circulation of air, at temperatures of 50, 60, 70 and 80 °C. The mathematical models were adjusted to the drying kinetics data at different temperatures, and the Page and de Midilli models presented the highest correlation coefficient (R<sup>2</sup>) and lowest RMSE values. From the thermodynamic analysis it was verified that the enthalpy and the free energy of Gibbs decreased with the increase of the temperature, characteristic of an endothermic process. The entropy presented negative values and decreased with the decrease in the drying temperature, this indicates that there is an increase in the degree of order of the system, considered as entropically unfavorable.</p>


2019 ◽  
Vol 57 (9) ◽  
pp. 778-783
Author(s):  
V E Shiryaeva ◽  
A A Korolev ◽  
T P Popova ◽  
A Y Kanateva ◽  
A A Kurganov

Abstract Chromatographic determination of the thermodynamic parameters of sorption for light hydrocarbons retention on a stationary phase based on poly [trimethylsilyl (propyn-1)] (PTMSP) was performed and the effect of column preheating at temperatures up to 260°C on the retention of analytes was investigated. It was shown that heating the column to 130°C does not affect the retention of the analytes. At temperatures above 130°C, the gradual decrease of the retention of analytes on PTMSP stationary phase is observed. The process is non-selective and proceeds at the same extent for all the studied hydrocarbons, regardless of the size and geometry of the molecule. Values of enthalpy and entropy of sorption of light hydrocarbons are determined for the original column and after its aging at 200°C. The enthalpy of sorption of the analytes at the PTMSP phase is practically independent on the heating temperature of the PTMSP phase, whereas the loss of entropy increases after heating. The increase of the entropy factor after the heating of the PTMSP stationary phase is associated with its aging and is confirmed by the construction of compensation functions for treated and untreated columns.


Author(s):  
G. Bandyopadhyay ◽  
R. Mondal ◽  
Sujit Chandra Lahiri

AbstractThe dissociation constants of p-nitroaniline (B) (A critical assessment of the solvent-sorting equilibrium method using p-nitroaniline as indicator has been made. The method is not suitable to determine the Gibbs energy of transfer of H


1999 ◽  
Vol 77 (7) ◽  
pp. 1305-1309 ◽  
Author(s):  
Ashraf A El-Bindary ◽  
Adel Z El-Sonbati ◽  
Hanan M Kera

Proton-ligand dissociation constants of 4-(4-acetophenyl)hydrazono-3-methyl-2-pyrazolin-5-one (AHMP) and metal-ligand stability constants of its complexes with some transition metal ions were calculated potentiometrically in 0.1 M KCl and 50% (v/v) ethanol-water mixture. The order of stability constants was found to be Th4+ > UO22+ > Ce3+ > La3+ > Mn2+ < Co2+ < Ni2+ < Cu2+ > Zn2+. The dissociation constant, pK1H, of AHMP and the stability constants, log K, of their complexes were determined at different temperatures (298, 308, and 318 K). The corresponding thermodynamic parameters (ΔG, ΔH, and ΔS) were derived and discussed. The dissociation process is nonspontaneous, endothermic, and entropically unfavourable. The formation of the metal complexes has been found to be spontaneous, exothermic, or endothermic (depending the metal), and entropically favourable. The stoichiometries of these complexes were determined conductometrically and indicated the formation of 1:1 and 1:2 (metal:ligand) complexes. Key words: 4-(4-acetophenyl)hydrazono-3-methyl-2-pyrazolin-5-one, dissociation and stability constants, thermodynamic parameters, stoichiometries.


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