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The Van 't Hoff equation relates the change in the equilibrium constant, K eq, of a chemical reaction to the change in temperature, T, given the standard enthalpy change, Δ r H ⊖, for the process. The subscript r {\displaystyle r} means "reaction" and the superscript ⊖ {\displaystyle \ominus } means "standard".
That is, observed temperatures above 60 °F (or the base temperature used) typically correlate with a correction factor below "1", while temperatures below 60 °F correlate with a factor above "1". This concept lies in the basis for the kinetic theory of matter and thermal expansion of matter , which states as the temperature of a substance ...
This dependence on microscopic variables is the central point of statistical mechanics. With a model of the microscopic constituents of a system, one can calculate the microstate energies, and thus the partition function, which will then allow us to calculate all the other thermodynamic properties of the system.
C is an overcounting correction factor, often used for particle systems where identical particles are able to change place with each other. [note 4] F provides a normalizing factor and is also the characteristic state function, the free energy. Again, the value of F is determined by demanding that ρ is a normalized probability density function:
The overall rate equation, Equation 6, is shown below. [8] = (+ +) In addition to the goodness of fit to the model, kinetic information about the overall reaction may further validate the proposed reaction mechanism. For instance, a positive NLE in the ML 2 should result in an overall lower reaction rate. [8]
The overall chemical reaction taking place in a cell is made up of two independent half-reactions, which describe chemical changes at the two electrodes. To focus on the reaction at the working electrode , the reference electrode is standardized with constant (buffered or saturated) concentrations of each participant of the redox reaction.
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The compressibility factor is defined as = where p is the pressure of the gas, T is its temperature, and is its molar volume, all measured independently of one another. In the case of an ideal gas, the compressibility factor Z is equal to unity, and the familiar ideal gas law is recovered: