The partial molar volume is broadly understood as the contribution that a component of a mixture makes to the overall volume
of the solution. However, there is more to it than this:
When one mole of water is added to a large volume of water at 25 °C, the volume increases by 18 cm3. The molar volume of
pure water would thus be reported as 18 cm3 mol−1. However, addition of one mole of water to a large volume of
pure ethanol results in an increase in volume of only 14 cm3. The reason that the increase is different is that the volume
occupied by a given number of water molecules depends upon the identity of the surrounding molecules. The value 14 cm3 is
said to be the partial molar volume of water in ethanol.
In general, the partial molar volume of a substance X in a mixture is the change in volume per mole of X added to the
mixture.
The partial molar volumes of the components of a mixture vary with the composition of the mixture, because the environment of
the molecules in the mixture changes with the composition. It is the changing molecular environment (and the consequent
alteration of the interactions between molecules) that results in the thermodynamic properties of a mixture changing as its
composition is alteredThe partial molar volume is broadly understood as the contribution that a component of a mixture makes
to the overall volume of the solution. However, there is more to it than this:
When one mole of water is added to a large volume of water at 25 °C, the volume increases by 18 cm3. The molar volume of
pure water would thus be reported as 18 cm3 mol−1. However, addition of one mole of water to a large volume of
pure ethanol results in an increase in volume of only 14 cm3. The reason that the increase is different is that the volume
occupied by a given number of water molecules depends upon the identity of the surrounding molecules. The value 14 cm3 is
said to be the partial molar volume of water in ethanol.
In general, the partial molar volume of a substance X in a mixture is the change in volume per mole of X added to the
mixture.
The partial molar volumes of the components of a mixture vary with the composition of the mixture, because the environment of
the molecules in the mixture changes with the composition. It is the changing molecular environment (and the consequent
alteration of the interactions between molecules) that results in the thermodynamic properties of a mixture changing as its
composition is altered
If, by , one denotes a generic extensive property of a mixture, it will always be true that it depends on the pressure (
), temperature ( ), and the amount of each component of the mixture (measured in moles, n). For a
mixture with q components, this is expressed as
If, by , one denotes a generic extensive property of a mixture, it will always be true that it depends on the pressure (
), temperature ( ), and the amount of each component of the mixture (measured in moles, n). For a
mixture with q components, this is expressed as
