Chemical Thermodynamics

2021 ◽  
pp. 344-364
Author(s):  
Christopher O. Oriakhi

Chemical Thermodynamics discusses the fundamental laws of thermodynamics along with their relationships to heat, work, enthalpy, entropy, and temperature. Predicting the direction of a spontaneous change and calculating the change in entropy of a reaction are core concepts. The relationship between entropy, free energy and work is covered. The Gibbs free energy is used quantitatively to predict if reactions or processes are going to be exothermic and spontaneous or endothermic under the stated conditions. Also explored are the enthalpy and entropy changes during a phase change. Finally the Gibbs free energy of a chemical reaction is related to its equilibrium constant and the temperature.

Author(s):  

The possibility of extraction of iron cations Fe2+ from the wash plant electroplating wastewater by carbon sorbents IPI-T synthesized in ISTU has been stated in this work. In this paper we studied the regularities of sorption in static and dynamic conditions, the numerical values defined limiting sorption of iron cations Fe2+ in the interval of temperatures 293-313 K. Such thermodynamic parameters of sorption as Gibbs free energy and enthalpy and entropy changes have been calculated.


Author(s):  
A. M. Savchenko ◽  
Yu. V. Konovalov ◽  
A. V. Laushkin

The relationship of the first and second laws of thermodynamics based on their energy nature is considered. It is noted that the processes described by the second law of thermodynamics often take place hidden within the system, which makes it difficult to detect them. Nevertheless, even with ideal mixing, an increase in the internal energy of the system occurs, numerically equal to an increase in free energy. The largest contribution to the change in the value of free energy is made by the entropy of mixing, which has energy significance. The entropy of mixing can do the job, which is confirmed in particular by osmotic processes.


Author(s):  
Dennis Sherwood ◽  
Paul Dalby

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.


2003 ◽  
Vol 17 (4) ◽  
pp. 753-762
Author(s):  
Christopher J. Rhodes ◽  
Thuy T. Tran ◽  
Philip Denton ◽  
Harry Morris

Using Transition-State Theory, experimental rate constants, determined over a range of temperatures, for reactions of vitamin E type antioxidants are analysed in terms of their enthalpies and entropies of activation. It is further shown that computational methods may be employed to calculate enthalpies and entropies, and hence Gibbs Free Energies, for the overall reactions. Within the Linear Free Energy Relationship (LFER) assumption, that the Gibbs Free Energy of activation is proportional to the overall Gibbs Free Energy change for the reaction, it is possible to rationalise, and even to predict, the relative contributions of enthalpy and entropy for reactions of interest, involving potential antioxidants.


2012 ◽  
Vol 550-553 ◽  
pp. 2607-2611
Author(s):  
Chun Hua Yang ◽  
Gang Chen ◽  
Long Zhang

Seven systems of one-step synthesis of aniline were designed, and it was determined which one could occur spontaneously through the calculation of Gibbs free energy of it. Among the seven systems, the Gibbs free energy of the one with ammonia as the aminating agent and hydrogen peroxide as the oxidant was the lowest, thus its process driving force was the largest, that is, .For this system just mentioned above, the standard Gibbs free energies, the equilibrium constant and the equilibrium conversions of benzene under different conditions were discussed ,which was expected to provide a theoretical basis for further development and application of the system.


NANO ◽  
2016 ◽  
Vol 11 (09) ◽  
pp. 1650100 ◽  
Author(s):  
Zhi-Qiang Wang ◽  
Yong-Qiang Xue ◽  
Zi-Xiang Cui ◽  
Hui-Juan Duan ◽  
Xiao-Yan Xia

Dissolution of nanoparticles is involved in the preparation, research and application of nanomaterials, but there is a surprising difference in dissolution thermodynamics between nanoparticles and the corresponding bulk materials. In the paper, the relations of dissolution thermodynamic properties, equilibrium constant of nanoparticles, respectively, and particle size were derived by introducing interface variables and the surface chemical potential. Experimentally, the solubility of nano-barium sulfate with different average particle sizes at different temperatures were determined by the method of electrical conductivity, obtaining the influencing regularities of particle size on the dissolution thermodynamic properties and the equilibrium constant. The regularities are in accordance with the theory. The results show that there are remarkable effects of particle size of nanoparticles on the dissolution thermodynamic properties and the equilibrium constant; with the decreasing of the size of nanoparticles, the dissolution equilibrium constant increases, while the standard dissolution Gibbs free energy, the standard dissolution enthalpy and the standard dissolution entropy decrease; and the logarithm of the dissolution equilibrium constant, the standard dissolution Gibbs free energy, the standard dissolution enthalpy and the standard dissolution entropy are linearly associated with the reciprocal of particle size, respectively. This new theory provides a quantitative description of nanoparticles dissolution behavior, and has important scientific significance for understanding and predicting of thermodynamic regularity of dissolution concerned in the preparation, researches and applications of nanomaterials.


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