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Modern Thermodynamics for Chemists and Biochemists$
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Dennis Sherwood and Paul Dalby

Print publication date: 2018

Print ISBN-13: 9780198782957

Published to Oxford Scholarship Online: August 2018

DOI: 10.1093/oso/9780198782957.001.0001

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Chemical equilibrium and chemical kinetics

Chemical equilibrium and chemical kinetics

(p.413) 14 Chemical equilibrium and chemical kinetics
Modern Thermodynamics for Chemists and Biochemists

Dennis Sherwood

Paul Dalby

Oxford University Press

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.

Keywords:   chemical reaction, spontaneous change, exergonic, endergonic, non-conservative function, Gibbs-Helmholtz equation, life, standard Gibbs free energy, extent-of-reaction, chemical equilibrium, equilibrium constant, mass action ratio, Le Chatelier’s principle, chemical kinetics, Arrhenius equation

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