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Activities
General form of the chemical potential for a real or ideal solvent is given
by modification of the equation for the chemical potential of a mixture.
For an ideal solution, Raoults law applies
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Chapter 7 Simple Mixtures http://people.cst.cmich.edu/teckl1mm/PChemI/Chm351Ch7-Ch8F01.htm
7.7 The solute activity
The problem with defining activity coefficients and standard states for
solutes is that they approach ideal dilute (Henrys Law) behavior as
Both KB and pB* are characteristic of the solvent, so the second term may
be combined with the first to give a new standard chemical potential
(b) Real solutes
For real deviations from Henrys law we introduce aB into the equation
above.
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at all temperatures and pressures. Deviations of the solute from ideality
disappear as zero concentration is approached.
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According to this definition, the chemical potential of solute has its
standard value m when molality of B is equal to b (at 1 mol/kg). Note
as b goes to 0, m B goes to ; that is the solution becomes diluted, so the
solute becomes increasingly stabilized. The consequence of this result is
that it is very difficult to remove the last traces of solute from a solution.
Now as before we incorporate deviations from ideality by introducing a
dimensionless activity aB and a dimensionless activity coefficient gB.
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8.1 Definitions
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If two phases are in equilibrium (ie - liq and vap) in a one component
system such as H2O(l) and H2O(g) (C = 1, P = 2), the T or p can be
changed at will, but the change in one demands an accompanying change
in the other to preserve the number of phases in equilibrium. The system
variance in this case is one (F = 1) one degree of freedom.
.
8.2 The Phase Rule
In one of the most elegant calculations of the whole of thermodynamics, J.
W. Gibbs deduced the phase rule, which is a general relation between the
variance, F, the number of components, C, and the number of phases at
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a) One-component system
For a one-component system, such as pure water, F = 3 - P. When only
one phase is present, F = 2 and both p and T can be varied independently
without changing the number of phases. In other words, a single phase is
represented by an area on a phase diagram. When two phases are in
equilibrium, F = 1, which implies that pressure is not freely variable if
temperature is set.
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Provided the mixture is ideal, the total pressure can be expressed in terms
of mole fractions in the liquid using Raoults Law for pJ and the equation
above for total vapor pressure p, which gives
The compostion (mole fraction) in. the vapor, yA, is related to the
composition in the liquid, xA. By solving the equation for xA and
substituting into the equation for ptot we relate the total vapor pressure to
composition of the vapor.
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