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Chemical Potential:

In thermodynamics, chemical potential, also known as partial molar free energy, is a form
of potential energy that can be absorbed or released during a chemical reaction. It may also
change during a phase transition. The chemical potential of a species in a mixture can be defined
as the slope of the free energy of the system with respect to a change in the number of moles of
just that species. Thus, it is the partial derivative of the free energy with respect to the amount of
the species, all other species' concentrations in the mixture remaining constant, and at constant
temperature. When pressure is constant, chemical potential is the partial molar Gibbs free
energy. At chemical equilibrium or in phase equilibrium the total sum of chemical potentials is
zero, as the free energy is at a minimum

The fundamental equation of chemical thermodynamics for a system containing n constituent

species, with the i-th species having Ni particles is, in terms of Gibbs energy

At constant temperature and pressure this simplifies to

The definition of chemical potential of the i-th species, μi, follows by setting all the
numbers Nj, apart from Ni, to be constant.

When temperature and volume are taken to be constant chemical potential relates to
the Helmholtz free energy, A.

The chemical potential of a species is the slope of the free energy with respect to the number of
particles of that species. It reflects the change in free energy when the number of particles of one
species changes. Each chemical species, be it an atom, ion or molecule, has its own chemical
potential. At equilibrium free energy is at its minimum for the system, that is, dG=0. It follows
that the sum of chemical potentials is also zero.

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Use of this equality provides the means to establish the equilibrium constant for a chemical
reaction..
FUGACITY
In chemical thermodynamics, the fugacity of a real gas is an effective partial pressure which
replaces the mechanical partial pressure in an accurate computation of the chemical equilibrium
constant. It is equal to the pressure of an ideal gas which has the same chemical potential as the
real gas
For example, nitrogen gas (N2) at 0°C and a pressure of has a fugacity of
.
This means that the chemical potential of real nitrogen at a pressure of 100 atm is less than if
nitrogen were an ideal gas; the value of the chemical potential is that which nitrogen as an ideal
gas would have at a pressure of 97.03 atm.
Fugacity’s are determined experimentally or estimated from various models such as a Van der
Waals gas that are closer to reality than an ideal gas. The ideal gas pressure and fugacity are
related through the dimensionless fugacity coefficient .

For nitrogen at 100 atm, the fugacity coefficient is 97.03 atm / 100 atm = 0.9703. For an ideal
gas, fugacity and pressure are equal so is 1.
The contribution of non-ideality to the chemical potential of a real gas is equal to RT ln .
Again for nitrogen at 100 atm,
the chemical potential is
μ = μid + RT ln
μ = 0.9703
which is less than the ideal value μid because of intermolecular attractive forces.
The fugacity is closely related to the thermodynamic activity. For a gas, the activity is simply the
fugacity divided by a reference pressure to give a dimensionless quantity. This reference pressure
is called the standard state and normally chosen as 1 atmosphere or 1 bar, Again using nitrogen
at 100 atm as an example, since the fugacity is 97.03 atm, the activity is just 97.03 without units.

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The fugacity of a real gas is formally defined by an equation analogous to the relation between
the chemical potential and the pressure of an ideal gas.
Relation between Chemical Potential and fugacity
In general, the chemical potential (μ) is defined as the partial molar Gibbs free energy. However,
for any pure substance it is equal to the molar Gibbs free energy, and its variation with
temperature (T) and pressure (P) is given by . At constant
temperature, this expression can be integrated as a function of . We must also set a reference
state. For an ideal gas the reference state depends only on pressure, and we set = 1 bar so that

Now, for an ideal gas

Reordering, we get

This gives the chemical potential for an ideal gas in an isothermal process, with a reference state
is = 1 bar.

For a real gas, the integral cannot be calculated because there isn't a simple
expression for a real gas's molar volume. Even if using an approximate expression such as
the van der Waals equation, the Redlich–Kwong or any other equation of state, it would depend
on the substance being studied and would be therefore of very limited utility.
Additionally, chemical potential is not mathematically well behaved. It approaches negative
infinity as pressure approaches zero and this creates problems in doing real calculations.
It is desirable that the expression for a real gas’ chemical potential to be similar to the one for an
ideal gas. Therefore one can define a quantity, called fugacity, so that the chemical potential for
a real gas becomes

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with a given reference state to be discussed later. This is the usual form of the definition, but it
may be solved for f to obtain the equivalent explicit form

Evaluation of fugacity for a real gas

Fugacity is used to better approximate the chemical potential of real gases than estimations made
using the ideal gas law. Yet fugacity allows the use of many of the relationships developed for an
idealized system.
In the real world, gases approach ideal gas behavior at low pressures and high temperatures;
under such conditions the value of fugacity approaches the value of pressure. Yet no substance is
truly ideal. At moderate pressures real gases have attractive interactions and at high pressures
intermolecular repulsions become important. Both interactions result in a deviation from "ideal"
behavior for which interactions between gas atoms or molecules are ignored.
For a given temperature , the fugacity satisfies the following differential relation:

where is the Gibbs free energy, is the gas constant, is the fluid's molar volume, and is
a reference fugacity which is generally taken as 1 bar. For an ideal gas, when , this
equation reduces to the ideal gas law.
Thus, for any two physical states at the same temperature, represented by subscripts 1 and 2, the
ratio of the two fugacities is as follows:

For an ideal gas, this becomes simply or

But for , every gas is an ideal gas. Therefore, fugacity must obey the limit equation

We determine by defining a new function , which is the difference between the actual molar
volume and the ideal-gas molar volume:

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We can obtain values for experimentally easily by measuring , and .

From the expression above we have

(It is more obvious here that is the "extra" molar volume of a non-ideal gas.) We can then
write

Where

Since the expression for an ideal gas was chosen to be ,we must have

Suppose we choose . Since , we obtain

The fugacity coefficient is defined as = f/P (note that for an ideal gas, = 1.0), and it will then
verify

The integral can be evaluated via graphical integration if we experimentally measure values
for while varying .

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We can then find the fugacity coefficient of a gas at a given pressure and calculate

.
The reference state for the expression of a real gas’ chemical potential is taken to be "ideal gas,
at = 1 bar and temperature ". Since in the reference state the gas is considered to be ideal (it
is an hypothetical reference state), we can write that for the real gas

Activity coefficient

An activity coefficient is a factor used in thermodynamics to account for deviations from ideal
behaviour in a mixture of chemical substances. In an ideal mixture, the microscopic interactions
between each pair of chemical species are the same (or macroscopically equivalent, the enthalpy
change of solution and volume variation in mixing is zero) and, as a result, properties of the
mixtures can be expressed directly in terms of simple concentrations or partial pressures of the
substances present e.g. Raoult's law. Deviations from ideality are accommodated by modifying
the concentration by an activity coefficient. Analogously, expressions involving gases can be
adjusted for non-ideality by scaling partial pressures by a fugacity coefficient.

Thermodynamic definition
The chemical potential, , of a substance B in an ideal mixture of liquids or an ideal solution is
given by

where is the chemical potential in the standard state and xB is the mole fraction of the
substance in the mixture.
This is generalised to include non-ideal behavior by writing

when is the activity of the substance in the mixture with

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where is the activity coefficient, which may itself depend on . As approaches 1, the

substance behaves as if it were ideal. For instance, if , then Raoult's law is accurate.

For and , substance B shows positive and negative deviation from Raoult's
law, respectively. A positive deviation implies that substance B is more volatile.
In many cases, as goes to zero, the activity coefficient of substance B approaches a constant;
this relationship is Henry's law for the solvent. These relationships are related to each other
through the Gibbs–Duhem equation. Note that in general activity coefficients are dimensionless.
Modifying mole fractions or concentrations by activity coefficients gives the effective
activities of the components, and hence allows expressions such as Raoult's law and equilibrium
constants to be applied to both ideal and non-ideal mixtures.
Knowledge of activity coefficients is particularly important in the context
of electrochemistry since the behavior of electrolyte solutions is often far from ideal, due to the
effects of the ionic atmosphere. Additionally, they are particularly important in the context
of soil chemistry due to the low volumes of solvent and, consequently, the high concentration of
electrolytes.

Relation of chemical potential to concentration

Because of the simplicity of the system, this is most easily considered for the case of an ideal gas
undergoing a change in state at constant temperature. In this case, the state of the system can be
defined by variables of state P, V, and T, which define the energy content, and can be used to
describe the work performed on or by the system.

For an ideal gas undergoing a reversible change at constant temperature, when no chemical work
is being performed,

dG = VdP ------------- (1)

On going from state 1, with free energy G1, to state 2, with free energy G2, by a reversible path,
the change in free energy (G2-G1) is the sum over the path, or integral, of all the dG values along
the path, as long as the process is reversible.

Since P is related to V by:

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PV = nRT

where n is the amount of gas in moles, and R is the gas constant. From the rules of integration:

We now define our initial state as a standard state in which the gas was at a pressure of 1 atm.
Then

G2 = Go + nRT ln P2 --------------------------- (4)

where Go is the standard state free energy of the gas.

In a mixture of ideal gases, each gas has a partial pressure which is the pressure which the gas
would have if it alone occupied the volume. The partial pressure is thus equivalent to the
concentration of the gas. For gases A, B, C, D the partial free energy due to each gas (G#A, G#B,
G#C, G#D) is related to the partial pressure of the gas by equation 4:

G#A = G#oA + nART ln PA

G#B = G#oB + nBRT ln PB, etc.

Let us now consider an ideal gas in equilibrium with the gas in solution. The concentration of the
gas in solution (assuming an ideal solution) will be proportional to the pressure of the gas, so that
an equivalent set of equations must exist relating the partial free energy of the gas in solution to
its concentration, X.

The partial free energy per mole of a component is its chemical potential, so we may write:

GA#soln = nAµA, GB#soln = nBµB, etc.

and, dividing by nA, nB, etc.

GA#soln = µA = µoA + RT ln XA,

nA

GB#soln = µB = µoB + RT ln XB, etc. --------(5)

nB

where XA, XB, etc., are concentrations of the gases in solution.

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Note that by dividing G# by n, we have changed the units from free energy (measured in joules,
J, or calories,) to free-energy per mole (J.mol-1, or cal.mol-1). This is a more useful parameter for
comparing energy terms for different chemical processes, because we don't have to worry about
the size of the system when comparing the work potential available from different reactions.

For non-ideal solutions, the relation between concentration and pressure of a gas in equilibrium
with the solution is affected by interaction between molecules in the solution. This leads to a
deviation from the constant proportionality between pressure and concentration, so that equations
5 do not apply exactly. This deviation is compensated by considering activities (aA, aB, etc.)
instead of concentrations. The activity is related to concentration by an activity coefficient ( ),
so that

a= X

Then

µA = µoA + RT ln aA -------- (6)

= µoA + RT ln XA A

In dilute solution, the activity coefficient approaches unity so that the behavior of the molecules
approaches the ideal, and activities approximate to concentrations. As we will see below, when
considering the energy changes in reactions, activity terms occur in ratios, and activity
coefficients tend to cancel. (Note that in equation 6, a term of value unity, corresponding to the
activity in the standard state, is ommitted by convention from the logarithmic term.)

Gibbs-Duhem-Equation
The Gibbs free energy can be defined in two different ways once by subtracting off combinations of
entropy S, enthalpy H and temperature T and other as a sum of chemical potentials and amounts of
species. The fact that they are equal gives a new relation known as “Gibbs-Duhem Relation.” The
Gibbs-Duhem relation helps us to calculate relationships between quantities as a system which
remains in equilibrium. One example is the Clausius-Clapeyron equation which states that two
phases at equilibrium with each other having equaled amount of a given substance must have
exactly the same free energy i.e. it relates equilibrium changes in pressure to changes in
temperature as a function of material parameters.
Deriving the Gibbs-Duhem equation from thermodynamics state equations is very easy. The Gibbs
free energy G in equilibrium can be expressed in terms of thermodynamics as:

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dG=μ1 dn1 +n1 dμ1 +μ2 dn2 +n2 dμ2………..μj dnj +nj dμj
dG= (μ1 dn1 + μ2 dn2 + ……… μj dnj) + (n1 dμ1 + n2 dμ2 +……….. nj dμj)
At constant temperature and pressure, the above equation can be written as:
n1 dμ1 +n2 dμ2 +………..nj dμj =0
∑ni dμi =0 ……………………..(1)
Because at constant temperature and pressure, (μ1 dn1 + μ2 dn2 + ……… μj dnj) = dG
The equation (1) is known as the Gibbs-Duhem equation.
Applications-of-Gibbs-Duhem-equation:
(i) Gibbs-duhem equation is helpful in calculating partial molar quantity of a binary mixture by
measuring the composition of the mixture which depends on the total molar quantity.
(ii) Gibbs-duhem equation is helpful in calculating the partial vapor pressures by calculating the total
vapor pressure. All these calculations require a curve-fitting procedure. Using tabulated experimental
data the accuracy of the calculated quantities was found to be comparable to the accuracy of the
original experimental data.

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