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Maxwell Relations By Becky Rameden Physical Chemistry I

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James Clerk Maxwell (1831-1879) Born in Edinburgh, Scotland Physicist well-known for his work in electromagnetism and field theory Also known for his work in thermodynamics and kinetic theory of gases http://en.wikipedia.org/wiki/James_Clerk _Maxwell

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Theory of Heat Written by Maxwell and published first in 1870 Describes his views of the limitations of the Second Law of Thermodynamics Maxwell Relations were first introduced in this book http://store.doverpublications.com/04 86417352.html

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Why Use Maxwell Relations? Certain variables in thermodynamics are hard to measure experimentally such as entropy Maxwell relations provide a way to exchange variables

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What are some examples of Maxwell Relations?

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Deriving Maxwell Relations First, start with a known equation of state such as that of internal energy Next, take the total derivative of with respect to the natural variables. For example, the natural of internal energy are entropy and volume.

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Deriving Maxwell Relations Continued Now that we have the total derivative with respect to its natural variables, we can refer back to the original equation of state and define, in this example, T and P.

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Deriving Maxwell Relations Continued We must now take into account a rule in partial derivatives When taking the partial derivative again, we can set both sides equal and thus, we have derived a Maxwell Relation

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Mnemonic Device for Obtaining Maxwell Relations The partial derivative of two neighboring properties (e.g. V and T) correspond to the partial derivative of the two properties on the opposite side of the square (e.g. S and P). The arrows denote the negative sign; if both are pointed the same way, then the sign is negative.

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Using Maxwell Relations Maxwell Relations can be derived from basic equations of state, and by using Maxwell Relations, working equations can be derived and used when dealing with experimental data.

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References Darin J. Ulness: Course Notes, Chemistry 351 Fall 2004Darin J. Ulness: Course Notes, Chemistry 351 Fall 2004 Physical Chemistry, Laidler, Meiser Sanctuary, 2003.Physical Chemistry, Laidler, Meiser Sanctuary, 2003. http://en.wikipedia.org/wiki/James_Cle rk_Maxwellhttp://en.wikipedia.org/wiki/James_Cle rk_Maxwell http://store.doverpublications.com/048 6417352.htmlhttp://store.doverpublications.com/048 6417352.html

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Entropy Change (at Constant Volume) For an ideal gas, C V (and C P ) are constant with T. But in the general case, C V (and C P ) are functions of T. Then.

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