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Activities

7.6 The solvent activity

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, Raoult’s law applies
 

The quantity aA is the Activity of A, an “effective mole fraction” just as

fugacity is an effective pressure. Since the chemical potential in terms
of pressures is true for both real and ideal solutions we conclude that
 
 

 
 
A convenient way of expressing this convergence is to introduce the
activity coefficient, g ,

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7.7 The solute activity
The problem with defining activity coefficients and standard states for
solutes is that they approach ideal dilute (Henry’s Law) behavior as

(a) ideal-dilute solutions

For a solute which obeys Henry’s Law, pB = KBxB

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 Henry’s 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.

Example 7.6 Measuring activity

Use the data in example 7.3 to calculate activity and activity coefficient
of chloroform in acetone at 25 0C, treating it first as a solvent then as a
solute.

Method: For the activity of chloroform as a solvent, form a=p/p* and g =

a/x. For activity as a solute, form a = p/K and g = a/x.

Answer: Because p* = 293 Torr and K = 165 Torr (previous problem),

we construct the following table with x the mole fraction of chloroform.

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Notice that g ® 1 as x ® 0 in the Raoult’s Law case;

g ® 0 as x ® 0 in the Henry’s Law case.

(c) Activities in terms of molalities

Another definition of activity. In dilute solutions, to a good
approximation, xB » nB/nA because nB is proportional to molality, b,
we can write

To simplify notation, we interpret b as a relative molality (replace b/b°

by b; in practice, using for b its numerical value in moles per kg). Then
we write

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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.

Chapter 8 Phase Diagrams

We will review a systematic way to describe the physical changes

mixtures undergo when they are heated or cooled and when their
compositions are changed.
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All phase diagrams can be discussed in terms of a relationship, the phase

rule, derived by J. W. Gibbs.

8.1 Definitions

Phase: A state of matter that is uniform throughout in chemical and

physical composition. (solid, liquid, gas, solution of two miscible
liquids, etc.). The number of phases in a system is denoted P. A
solution of water and acetone has one phase, P = 1, since they are
uniformly mixed. A slurry of ice and water is a two-phase system, P =
2. A system in which calcium carbonate undergoes thermal
decomposition consists of two solid phases (calcium carbonate and
calcium oxide are not uniformly mixed) and one gas phase (carbon
dioxide).

An alloy of two metals is a two-phase system (P = 2) if the metals are

immiscible, but a single phase system (P = 1) if the metals are miscible.

A dispersion is uniform on a macroscopic scale but not on a microscopic

scale, for it consists of grains or droplets of one substance in a matrix of
the other. Such dispersions are important in materials where the
microstructure is fixed to tailor important properties.

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By a constituent of a system we mean a chemical species (ion or

molecule) that is present. A mix of water and ethanol has two
constituents. A Component is a chemically independent constituent of
a system. The number of components, C, in a system is the minimum
number of independent species necessary to define the composition of
all phases present in the system.

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When no reaction takes place, the number of components is equal to the

number of constituents, chemical species. The mixture of ethanol and
water is a two-component system (C = 2).

Consider the phase equilibrium

3 Phases - To specify the composition of the gas phase we need the

species CO2, and to specify phase two, we need the species CaO. We
do not need an additional species to specify the composition of phase 3
because its identity can be expressed in terms of the other two
constituents by making use of the stoichiometry of the reaction. Hence
the system has 3 constituents but only two components (C = 2).

In general the number of constituents minus the number of chemical

reactions equal the number of components.

Examples: How many components?

a) aqueous acetic acid – CH3CO2H and H2O; C = 2
b) MgCO3(s) in equilibrium with its decomposition products.
MgCO3(s) ® MgO(s) + CO2(g)
3 constituents - 1 reaction – C = 2
c) water (including its ionization)
H2O(l) ® H+(aq) + OH-(aq) Looks like 3 constituents, 1 reaction.
BUT H and OH are formed in equal molar amounts. Really only
need the concentration of one and the other is the same.
2 constituents - 1 reaction – C = 1
d) NH4Cl(s) ® NH3(g) + HCl(g) in equilibrium
Again 2 constituents – 1 reaction – C=1
e) Reaction above with additional HCl(s) present.
Concentrations are not related by stoiciometry.
3 constituents - 1 reaction – C = 2

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The Variance, F, of a system is the number of intensive variables that

can be changed independently without disturbing the number of phases
in equilibrium.
 
In a single component, single phase system (C = 1, P =1), the pressure
and temperature may be changed independently without changing the
number of phases, so F = 2. This system is bivariant and has two
degrees of freedom.

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 equilibrium, P, for a system of any composition:

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.

At a given temperature, a liquid has a characteristic vapor pressure (F =

1). Thus, the equilibrium of two phases is represented by a line on the
phase diagram.

When the three phase are in equilibrium, F = 0 and the system is

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invariant. This special condition can be established only at a definite

temperature and pressure that is characteristic of the substance and
outside our control. The equilibrium of three phase is represented by a
point (the triple point) on the phase diagram.

8.3 Vapor pressure diagrams

The vapor pressure of the components of an ideal solution of two

volatile liquids are related to composition according to Raoult’s law:
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The total pressure ptot of the mixture is

The total pressure is a linear function of composition of the ideal

solution.

a) The composition of vapor

The partial pressures of the components are given by Raoult’s Law.
From Dalton’s law we write for the mole fractions of the vapor, yA and
yB,

Provided the mixture is ideal, the total pressure can be expressed in

terms of mole fractions in the liquid using Raoult’s 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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