The law of mass action and rate laws describe different aspects of chemical reaction kinetics and equilibria
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Reference materials and literature establish that the law of mass action relates reaction rates to reactant concentrations and characterizes behavior in chemical equilibria.
We have traced the historical link between the Law of Mass Action and clinical pharmacology. The Law evolved from the work of the French chemist Claude Louis Berthollet, was first formulated by Cato Guldberg and Peter Waage in 1864 and later clarified by the Dutch chemist Jacobus van ‘t Hoff in 1877. It has profoundly influenced our qualitative and quantitative understanding of a number of physiological and pharmacological phenomena. According to the Law of Mass Action, the velocity of a chemical reaction depends on the concentrations of the reactants. At equilibrium the concentrations of the chemicals involved bear a constant relation to each other, described by the equilibrium constant, K. The Law of Mass Action is relevant to various physiological and pharmacological concepts, including concentration–effect curves, dose–response curves, and ligand–receptor binding curves, all of which are important in describing the pharmacological actions of medications, the Langmuir adsorption isotherm, which describes the binding of medications to proteins, activation curves for transmembrane ion transport, enzyme inhibition and the Henderson–Hasselbalch equation, which describes the relation between pH, as a measure of acidity and the concentrations of the contributory acids and bases. Guldberg and Waage recognized the importance of dynamic equilibrium, while others failed to do so. Their ideas, over 150 years old, are embedded in and still relevant to clinical pharmacology. Here we explain the ideas and in a subsequent paper show how they are relevant to understanding adverse drug reactions.
chemistry, the law of mass action is the proposition that the rate of a chemical reaction is directly proportional to the product of the activities or
In chemistry, the law of mass action is the proposition that the rate of a 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 pr
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is also applicable to second order reactions that may not be concerted reactions. Guldberg and Waage were fortunate in that reactions such as ester formation and hydrolysis, on which they originally based their theory, do indeed follow this rate expression.
In general many reactions occur with the formation of reactive intermediates, and/or through parallel reaction pathways. However, all reactions can be represented as a series of elementary reactions and, if the mechanism is known in detail, the rate equation for each individual step is given by the
r
f
{\displaystyle r_{f}}
expression so that the overall rate equation can be derived from the individual steps. When this is done the equilibrium constant is obtained correctly from the rate equations for forward and backward reaction rates.
In biochemistry, there has been significant interest in the appropriate mathematical model for chemical reactions occurring in the intracellular medium. This is in contrast to the initial work done on chemical kinetics, which was in simplified systems where reactants were in a relatively dilute, pH-buffered, aqueous solution. In more complex environments, where bound particles may be prevented from disassociation by their surroundings, or diffusion is slow or anomalous, the model of mass action does not always describe the behavior of the reaction kinetics accurately. Several attempts have been made to modify the mass action model, but consensus has yet to be reached. Popular modifications replace the rate constants with functions of time and concentration. As an alternative to these mathematical constructs, one school of thought is that the mass action model can be valid in intracellular environments under certain conditions, but with different rates than would be found in a dilute, simple environment .
The fact that Guldberg and Waage developed their concepts in steps from 1864 to 1867 and 1879 has resulted in much confusion in the literature as to which equation the law of mass action refers. It has been a source of some textbook errors. Thus, today the "law of mass…
Examines the frequently misplaced emphasis on the rate law of mass action, its fallacious use to prove the existence and form of equilibrium constants, and the occasional confusion of the two concepts.
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