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*THERMODYNAMICS OF SOLUTIONS

*A mixture is any multi-component system, i.e. one with several

chemical species. The thermodynamics of mixtures in general

(gaseous, liquid or solid) has been considered under the heading

Mixtures, mainly devoted to ideal mixtures. The term 'solution' is

mostly used for the special case of a mixture between very

dissimilar components, i.e. when a small amount of substance,

called solute (solid, liquid or gas), dissolves to a certain limit in a

liquid or solid substance (pure, or a mixture itself) called the

solvent.

COMPOSITION OF A MIXTURE:

MASS AND MOLE FRACTIONS

To determine the properties of a mixture, we need to know the composition

of the mixture as well as the properties of the individual components. There

are two ways to describe the composition of a mixture: either by specifying

the number of moles of each component, called molar analysis, or by

specifying the mass of each component, called gravimetric analysis.

mixture mm is the sum of the masses of the individual components, and the

mole number of the mixture Nm is the sum of the mole numbers of the

individual components

* The ratio of the mass of a component to the mass of the mixture

is called the mass fraction mf, and the ratio of the mole number

of a component to the mole number of the mixture is called the

mole fraction y:

:

number N and molar mass M of the substance as m = NM. Then

the apparent (or average) molar mass and the gas constant of a

mixture can be expressed as:

The molar mass of a mixture can also be expressed as:

*P-v-T BEHAVIOR OF GAS MIXTURES: IDEAL AND

REAL GASES

* An ideal gas is defined as a gas whose molecules are spaced far apart so

that the behavior of a molecule is not influenced by the presence of other

molecules—a situation encountered at low densities. We also mentioned

that real gases approximate this behavior closely when they are at a low

pressure or high temperature relative to their critical-point values. The P-

v-T behavior of an ideal gas is expressed by the simple relation Pv = RT,

which is called the ideal-gas equation of state. The P-v-T behavior of real

gases is expressed by more complex equations of state or by Pv = ZRT,

where Z is the compressibility factor.

*The prediction of the P-v-T behavior of gas mixtures is usually

based on two models: Dalton’s law of additive pressures and

Amagat’s law of additive volumes. Both models are described and

discussed below.

is equal to the sum of the pressures each gas would exert if it

existed alone at the mixture temperature and volume .

is equal to the sum of the volumes each gas would occupy if it

existed alone at the mixture temperature and pressure .

*Dalton’s and Amagat’s laws hold exactly for ideal-gas mixtures,

but only approximately for real-gas mixtures. This is due to

intermolecular forces that may be significant for real gases at high

densities. For ideal gases, these two laws are identical and give

identical results.

*In these relations, Pi is called the component pressure and Vi is

called the component volume.

*Also, the ratio Pi /Pm is called the pressure fraction and the ratio

Vi /Vm is called the volume fraction of component i.

gas relation for both the components and the gas mixture:

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