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Partial molar property : ウィキペディア英語版
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 of the extensive property with respect to the amount (number of moles) of the component of interest. Every extensive property of a mixture has a corresponding partial molar property.
==Definition==

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
:Z=Z(T,P,n_1,n_2,\cdots).
Now if temperature ''T'' and pressure ''P'' are held constant, Z=Z(n_1,n_2,\cdots) is a homogeneous function of degree 1, since doubling the quantities of each component in the mixture will double Z. More generally, for any \lambda:
:Z(\lambda n_1,\lambda n_2, \cdots)=\lambda Z(n_1,n_2,\cdots).
By Euler's first theorem for homogeneous functions, this implies〔(Wolfram Mathworld: Euler's homogeneous function theorem )〕
:Z=\sum _^m n_i \bar,
where \bar is the partial molar Z of component i defined as:
:\bar=\left( \frac \right)_ is a homogeneous function of degree 0 which means that for any \lambda :
:\bar(\lambda n_1,\lambda n_2,\cdots )=\bar(n_1,n_2,\cdots ).
In particular, taking \lambda = 1/n_T where n_T=n_1+n_2+ \cdots , one has
:\bar(x_1,x_2, \cdots )=\bar(n_1,n_2,\cdots),
where x_i=\frac is the concentration, or mole fraction of component i.
Since the molar fractions satisfy the relation
:\sum _^m x_i = 1,
the ''xi'' are not independent, and the partial molar property is a function of only m-1 mole fractions:
:\bar=\bar(x_1,x_2, \cdots , x_).
The partial molar property is thus an intensive property - it does not depend on the size of the system.

抄文引用元・出典: フリー百科事典『 ウィキペディア(Wikipedia)
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