LECTURE PHYSICAL CHEMISTRY 3rd EDITION ROBERT G. MORTIMER

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The partial derivative (∂U/∂V) T ,n is an important
measure of the deviation of a system from ideal gas
behavior. It has the same units as pressure and is
known as the internal pressure. If the internal
pressure is positive, the energy increases as the
volume increases and work is done against the
attractive intermolecular forces. The internal
pressure is a measure of the net cohesive forces of
the system and can have a large positive value for
liquids. To derive a useful equation for the internal
pressure, we begin with Eq. (4.3-2) and apply the
cycle rule to the partial derivative on the right-hand
side of the equation:
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