scholarly journals Enzymatic Kinetic Issues and Controversies Surrounding Gibbs Free Energy of Activation and Arrhenius Activation Energy

2020 ◽  
pp. 1-13
Author(s):  
Ikechukwu I. Udema ◽  
Abraham Olalere Onigbinde
Keyword(s):  
Activation Energy ◽  
Free Energy ◽  
Equilibrium Constant ◽  
Gibbs Free Energy ◽  
Theoretical Research ◽  
Energy Of Activation ◽  
Arrhenius Activation Energy ◽  
Free Energy Of Activation ◽  
Different Temperatures ◽  
The Difference

Background: The equation of the difference between reverse and forward Gibbs free energy of activation (ΔΔGES#) reflects Michaelis-Menten constant (KM) in both directions; this may not be applicable to all enzymes even if the reverse reaction is speculatively Michaelian. Arrhenius activation energy, Ea and (Ea - ΔGES#)/RT) are considered = ΔGES# and KM respectively. The equations are considered unlikely. Objectives: The objectives of this research are: 1) To derive what is considered as an appropriate equation for the determination of the difference in ΔGES# between the reverse and forward directions, 2) calculate the difference between the reverse and total forward ΔGES#, and 3) show reasons why Ea ≠ ΔGES#  in all cases. Methods: A major theoretical research and experimentation using Bernfeld method. Results and Discussion: A dimensionless equilibrium constant KES is given. Expectedly, the rate constants were higher at higher temperatures and the free energy of activation with salt was < the Arrhenius activation energy, Ea; ΔΔGES#ranges between 67 - 68 kJ/mol. Conclusion: The equations for the calculation of the difference in free energy of activation (ΔΔGES#) between the forward and reverse directions and a dimensionless equilibrium constant for the formation of enzyme-substrate (ES) were derivable. The large positive value of the ΔΔGES# shows that the forward reaction is not substantially spontaneous; this is due perhaps, to the nature of substrate. The equality of Arrhenius activation energy (Ea) and ΔGES# may not be ruled out completely but it must not always be the case; the presence of additive like salt can increase the magnitude of Ea well above the values of the ΔGES#. A dimensionless equilibrium constant for the net yield of ES seems to be a better alternative than KM. The Ea unlike ΔGES#  requires at least two different temperatures for its calculation.

scholarly journals Kinetics and thermodynamic properties related to the drying of 'Cabacinha' pepper fruits

2016 ◽  
Vol 20 (2) ◽  
pp. 174-180 ◽  
Author(s):  
Hellismar W. da Silva ◽  
Renato S. Rodovalho ◽  
Marya F. Velasco ◽  
Camila F. Silva ◽  
Luís S. R. Vale
Keyword(s):  
Experimental Data ◽  
Activation Energy ◽  
Free Energy ◽  
Thermodynamic Properties ◽  
Gibbs Free Energy ◽  
Removal Rate ◽  
Effective Diffusion ◽  
Drying Time ◽  
Three Samples ◽  
Different Temperatures

ABSTRACT The objective of this study was to determine and model the drying kinetics of 'Cabacinha' pepper fruits at different temperatures of the drying air, as well as obtain the thermodynamic properties involved in the drying process of the product. Drying was carried out under controlled conductions of temperature (60, 70, 80, 90 and 100 °C) using three samples of 130 g of fruit, which were weighed periodically until constant mass. The experimental data were adjusted to different mathematical models often used in the representation of fruit drying. Effective diffusion coefficients, calculated from the mathematical model of liquid diffusion, were used to obtain activation energy, enthalpy, entropy and Gibbs free energy. The Midilli model showed the best fit to the experimental data of drying of 'Cabacinha' pepper fruits. The increase in drying temperature promoted an increase in water removal rate, effective diffusion coefficient and Gibbs free energy, besides a reduction in fruit drying time and in the values of entropy and enthalpy. The activation energy for the drying of pepper fruits was 36.09 kJ mol-1.

scholarly journals Some Thermodynamic Properties of White Yam (Dioscorea rotundata) Slices Dehydrated in a Refractance WindowTM Dryer

2020 ◽  
Vol 5 (1) ◽  
Author(s):  
Akinjide A Akinola ◽  
Stanley N Ezeorah
Keyword(s):  
Activation Energy ◽  
Free Energy ◽  
Moisture Content ◽  
Gibbs Free Energy ◽  
Moisture Diffusivity ◽  
Process Conditions ◽  
Dioscorea Rotundata ◽  
History Data ◽  
White Yam ◽  
Different Temperatures

The objective of this study is to estimate the changes in Enthalpy, Entropy and Gibbs Free Energy of yam slices dehydrated at different temperatures using a Refractance WindowTM dryer. Dehydration of 1.5, 3.0 and 4.5 mm thick yam slices, was performed with water temperatures of 65, 75, 85 and 95oC in the flume of a Refractance WindowTM dryer. During the dehydration operations, the moisture-content history data were recorded. For the process conditions considered, the moisture content history data was used to calculate the moisture diffusivity and the activation energy of dehydration of the samples. Subsequently, changes in Enthalpy, , Entropy, , and Gibbs Free Energy, ), were calculated. For the process conditions studied, the changes in, , , and, varied from 20,381.33 to 25,217.05 J.mol-1., -140.69 to -122.29 J.mol-1.K-1.and 67,934.80 to 70,220.15 J.mol-1, respectively. This study is essential as knowledge of these thermodynamic parameters are useful for the optimal design and sizing of preservation dryers for argo-products. Keywords— Enthalpy; Entropy; Gibbs Free Energy; Refractance WindowTM Dryer; Yam 

scholarly journals A rheological description of the water vapour sorption kinetics behaviour of wood invoking a model using a canonical assembly of Kelvin-Voigt elements and a possible link with sorption hysteresis

Holzforschung ◽  
2012 ◽  
Vol 66 (1) ◽  
Author(s):  
Callum A.S. Hill ◽  
Barbara A. Keating ◽  
Zaihan Jalaludin ◽  
Eike Mahrdt
Keyword(s):  
Cell Wall ◽  
Free Energy ◽  
Gibbs Free Energy ◽  
Sorption Kinetics ◽  
Energy Of Activation ◽  
Relaxation Processes ◽  
Sorption Behaviour ◽  
Vapour Sorption ◽  
Free Energy Of Activation ◽  
Sorption Hysteresis

Abstract The dynamic vapour sorption behaviour of two Malaysian hardwoods, acacia (Acacia mangium Wild) and sesendok (Endospermum malaccense Bent ex Müll. Arg.) was studied over a narrow temperature range (20–40°C). The rate of sorption or desorption of water into or out of the wood cell wall was considered to be limited by the viscoelastic behaviour of the material and the sorption kinetics was accordingly analysed in terms of a canonical series of Kelvin-Voigt elements. A two series and three series model have been applied to the kinetic data and the results are compared. Characteristic times and moisture contents were obtained from the models. The Arrhenius equation was used in conjunction with the reciprocals of the characteristic times to calculate the activation energy and activation entropy of sorption, and the Gibbs free energy of activation for the sorption process was also determined. This is the first time that entropy of activation and Gibbs free energy of activation for sorption processes with wood have been reported. Interpretation of these data invokes a model describing the polymeric relaxation processes occurring within the cell wall during adsorption or desorption. A possible link between sorption kinetics, polymeric relaxation processes, and sorption hysteresis is discussed.

Etude par rmn du proton et du carbone-13 de pyrimidines substituées. IV. Empêchement de rotation dans des N,N-diméthylamino-4 pyrimidines à l'état monoprotoné

1980 ◽  
Vol 58 (5) ◽  
pp. 466-471 ◽  
Author(s):  
Jacques Riand ◽  
Marie-Thérèse Chenon ◽  
Nicole Lumbroso-Bader
Keyword(s):  
Free Energy ◽  
Line Shape ◽  
Pyrimidine Ring ◽  
Energy Of Activation ◽  
Hindered Rotation ◽  
Dimethylamino Group ◽  
Free Energy Of Activation ◽  
The Difference ◽  
C Nmr

The free energy of activation for hindered rotation about the C—N exocyclic bond in some N,N-dimethylaminopyrimidine hydrochlorides has been determined by 1H and 13C nmr line-shape analysis.Monoprotonation of N,N-dimethylaminopyrimidines induces a large increase of the free energy of activation (from 14 to 24 kJ mol−1). This increase is larger for the 4-dimethylamino group than for the 2-dimethylamino group due to the predominance of the monoprotonated (N-1 H) form. Consequently, the difference of conjugation of the 4- and 2-dimethylamino groups with the pyrimidine ring is more pronounced in the monoprotonated species.

Viscosity of Dimethyl Sulfoxide + 1,4 Dimethylbenzene System

2008 ◽  
Vol 59 (1) ◽  
pp. 45-48
Author(s):  
Oana Ciocirlan ◽  
Olga Iulian
Keyword(s):  
Free Energy ◽  
Dimethyl Sulfoxide ◽  
Atmospheric Pressure ◽  
Entire Range ◽  
Polynomial Equation ◽  
Energy Of Activation ◽  
Excess Gibbs Free Energy ◽  
Experimental Measurements ◽  
Gibbs Energy Of Activation ◽  
Free Energy Of Activation

This paper reports the viscosities measurements for the binary system dimethyl sulfoxide + 1,4-dimethylbenzene over the entire range of mole fraction at 298.15, 303.15, 313.15 and 323.15 K and atmospheric pressure. The experimental viscosities were correlated with the equations of Grunberg-Nissan, Katti-Chaudhri, Hind, Soliman and McAllister; the adjustable binary parameters have been obtained. The excess Gibbs energy of activation of viscous flow (G*E) has been calculated from the experimental measurements and the results were fitted to Redlich-Kister polynomial equation. The obtained negative excess Gibbs free energy of activation and negative Grunberg-Nissan interaction parameter are discussed in structural and interactional terms.

Chemical equilibrium and chemical kinetics

2018 ◽  
Author(s):  
Dennis Sherwood ◽  
Paul Dalby
Keyword(s):  
Free Energy ◽  
Equilibrium Constant ◽  
Gibbs Free Energy ◽  
Chemical Kinetics ◽  
Chemical Equilibrium ◽  
First Principles ◽  
Effect Of Temperature ◽  
Total System ◽  
Free Energies

Building on the previous chapter, this chapter examines gas phase chemical equilibrium, and the equilibrium constant. This chapter takes a rigorous, yet very clear, ‘first principles’ approach, expressing the total Gibbs free energy of a reaction mixture at any time as the sum of the instantaneous Gibbs free energies of each component, as expressed in terms of the extent-of-reaction. The equilibrium reaction mixture is then defined as the point at which the total system Gibbs free energy is a minimum, from which concepts such as the equilibrium constant emerge. The chapter also explores the temperature dependence of equilibrium, this being one example of Le Chatelier’s principle. Finally, the chapter links thermodynamics to chemical kinetics by showing how the equilibrium constant is the ratio of the forward and backward rate constants. We also introduce the Arrhenius equation, closing with a discussion of the overall effect of temperature on chemical equilibrium.

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