Summary
In chemistry, the law of mass action is the proposition that the rate of the chemical reaction is directly proportional to the product of the activities or concentrations of the reactants. It explains and predicts behaviors of solutions in dynamic equilibrium. Specifically, it implies that for a chemical reaction mixture that is in equilibrium, the ratio between the concentration of reactants and products is constant. Two aspects are involved in the initial formulation of the law: 1) the equilibrium aspect, concerning the composition of a reaction mixture at equilibrium and 2) the kinetic aspect concerning the rate equations for elementary reactions. Both aspects stem from the research performed by Cato M. Guldberg and Peter Waage between 1864 and 1879 in which equilibrium constants were derived by using kinetic data and the rate equation which they had proposed. Guldberg and Waage also recognized that chemical equilibrium is a dynamic process in which rates of reaction for the forward and backward reactions must be equal at chemical equilibrium. In order to derive the expression of the equilibrium constant appealing to kinetics, the expression of the rate equation must be used. The expression of the rate equations was rediscovered later independently by Jacobus Henricus van 't Hoff. The law is a statement about equilibrium and gives an expression for the equilibrium constant, a quantity characterizing chemical equilibrium. In modern chemistry this is derived using equilibrium thermodynamics. It can also be derived with the concept of chemical potential. Two chemists generally expressed the composition of a mixture in terms of numerical values relating the amount of the product to describe the equilibrium state. Cato Maximilian Guldberg and Peter Waage, building on Claude Louis Berthollet's ideas about reversible chemical reactions, proposed the law of mass action in 1864. These papers, in Danish, went largely unnoticed, as did the later publication (in French) of 1867 which contained a modified law and the experimental data on which that law was based.
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