Besaran molar

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Partial Molar property

A partial molar property is a thermodynamic
quantity which indicates how an extensive
property of a solution or mixture varies with
changes in the molar composition of the
mixture at constant temperature and
pressure. Essentially it is the partial derivative
with respect to the quantity (number of
moles) of the component of interest. Every
extensive property of a mixture has a
corresponding partial molar property.

 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 rather 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 ,Z
one denotes a generic extensive property of a
mixture, it will always be true that it depends
on the pressure (P ), temperature (T), and the
amount of each component of the mixture
(measured in moles, n). For a mixture with m
components, this is expressed as

 Now if temperature T and pressure P are held

constant,
is a homogeneous
function of degree 1, since doubling the
quantities of each component in the mixture
will double Z . More generally, for any lamda :

 By Euler's first theorem for homogeneous

functions, this implies

Where is the partial molar of component

defined as

Applications
Partial molar properties are useful because
chemical mixtures are often maintained at
constant temperature and pressure and under
these conditions, the value of any extensive
property can be obtained from its partial molar
property. They are especially useful when
considering specific properties of pure substances
(that is, properties of one mole of pure
substance) and properties of mixing. By
definition, properties of mixing are related to
those of the pure substance by:

 Here * denotes the pure substance, M the mixing

property, and Z corresponds to the specific
property under consideration. From the
definition of partial molar properties,

substitution yields :

So from knowledge of the partial molar

properties, deviation of properties of mixing from
single components can be calculated.

Relationship to thermodynamic
potentials
Relationship to thermodynamic potentials
Partial molar properties satisfy relations analogous to those
of the extensive properties. For the internal energy U,
enthalpy H, Helmholtz free energy A, and Gibbs free energy
G, the following hold:

Where P is the pressure , V the volume, T the temperature,

and S the entropy.

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