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Another macroscopic consequence of microscopic reversibility is the symmetry of kinetic coefficients, the so-called reciprocal relations. The reciprocal relations were discovered in the 19th century by Thomson and Helmholtz for some phenomena but the general theory was proposed by Lars Onsager in 1931. [ 6 ]
The conservation of mass is expressed locally by the fact that the flow of mass density satisfies the continuity equation: + =, where is the mass flux vector. The formulation of energy conservation is generally not in the form of a continuity equation because it includes contributions both from the macroscopic mechanical energy of the fluid flow and of the microscopic internal energy.
A Markov process is called a reversible Markov process or reversible Markov chain if there exists a positive stationary distribution π that satisfies the detailed balance equations [13] =, where P ij is the Markov transition probability from state i to state j, i.e. P ij = P(X t = j | X t − 1 = i), and π i and π j are the equilibrium probabilities of being in states i and j, respectively ...
In physics, the cross section is a measure of the probability that a specific process will take place in a collision of two particles. For example, the Rutherford cross-section is a measure of probability that an alpha particle will be deflected by a given angle during an interaction with an atomic nucleus.
Case (c) depicts the potential diagram for an endothermic reaction, in which, according to the postulate, the transition state should more closely resemble that of the intermediate or the product. Another significance of Hammond’s postulate is that it permits us to discuss the structure of the transition state in terms of the reactants ...
A reversible reaction is a reaction in which the conversion of reactants to products and the conversion of products to reactants occur simultaneously. [1]+ + A and B can react to form C and D or, in the reverse reaction, C and D can react to form A and B.
Based on the principle of microscopic reversibility, the inert nature of the neopentyl halides towards the S N 2 reaction indicates that an S N 2 reaction is unlikely to be the mechanism for the synthesis of the neopentyl halides in this reaction.
Having discussed reversible inhibition and irreversible inhibition in the above two headings, it would have to be pointed out that the concept of reversibility (or irreversibility) is a purely theoretical construct exclusively dependent on the time-frame of the assay, i.e., a reversible assay involving association and dissociation of the ...