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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 ...
Le Chatelier–Braun principle analyzes the qualitative behaviour of a thermodynamic system when a particular one of its externally controlled state variables, say , changes by an amount , the 'driving change', causing a change , the 'response of prime interest', in its conjugate state variable , all other externally controlled state variables remaining constant.
The expression of the rate equations was rediscovered 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.
The entropy is first viewed as an extensive function of all of the extensive thermodynamic parameters. If we have a thermodynamic system in equilibrium, and we release some of the extensive constraints on the system, there are many equilibrium states that it could move to consistent with the conservation of energy, volume, etc.
For a reversible reaction, the equilibrium constant can be measured at a variety of temperatures. This data can be plotted on a graph with ln K eq on the y -axis and 1 / T on the x axis. The data should have a linear relationship, the equation for which can be found by fitting the data using the linear form of the Van 't Hoff equation
At equilibrium, the rate of transfer of CO 2 from the gas to the liquid phase is equal to the rate from liquid to gas. In this case, the equilibrium concentration of CO 2 in the liquid is given by Henry's law, which states that the solubility of a gas in a liquid is directly proportional to the partial pressure of that gas above the liquid. [1]
For example, if equilibrium is specified by a single chemical equation:, [24] ∑ j = 0 m ν j R j = 0 {\displaystyle \sum _{j=0}^{m}\nu _{j}R_{j}=0} where ν j is the stoichiometric coefficient for the j th molecule (negative for reactants, positive for products) and R j is the symbol for the j th molecule, a properly balanced equation will obey:
For this assumption to be valid, equilibrium constants must be determined in a medium of relatively high ionic strength. Where this is not possible, consideration should be given to possible activity variation. The equilibrium expression above is a function of the concentrations [A], [B] etc. of the chemical species in equilibrium. The ...