Chapter-4

Thermodynamics
of
solutions

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 Unit Four Contents
✓ Solutions, ideal and non-ideal solutions,
✓ Henry’s law, Gibbs-Duhem equation,
✓ Regular solution, quasi-chemical approach to
solution, statistical treatment,
✓ Change of standard state.
✓ Free energy composition diagrams for binary alloy
systems, determination of liquidus, solidus and
solvus lines.
✓ Effect of pressure on phase transformation and
phase equilibria

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 Solutions
Solution, in chemistry, a homogenous mixture of two or
more substances in relative amounts that can be varied
continuously up to what is called the limit of solubility.
A solution consists of a solute and a solvent. The solute
is the substance that is dissolved in the solvent.
✓ The term solution is commonly applied to the liquid state
of matter, but solutions of gases and solids are possible.
✓ Air, for example, is a solution consisting chiefly
of oxygen and nitrogen with trace amounts of several
other gases, and
✓ brass is a solution composed of copper and zinc.

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The composition of a solution can be described in several
ways. Here are the most common:
1. The molar fraction of the ith component, xi, is the ratio
of the number of moles of component i, ni, to the total
number of moles of all species within the solution, n.
2. The weight fraction of the ith component, [i], is the
ratio of the mass of component i, wi, to the total mass
of all species within the solution, w.
the weight fraction is often written as a weight percent
[wt%] = 100[i].
3. The molarity of the ith component, ci, is the number of
moles of component i, ni per liter of solution, V:

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 Types of solutions

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Extensive properties depend on the mass of a system.
Properties, such as mass m, volume V, internal energy U,
enthalpy H, and entropy S are extensive properties.
Their values change accordingly as the mass of a system
changes.
Intensive properties are independent of the mass of a
system. Pressure P, temperature T, specific volume v,
specific internal energy u, specific enthalpy h, and specific
entropy s are intensive properties.
✓ All specific properties are intensive properties, as they
refer to the corresponding extensive properties per unit
mass, e.g., specific volume v=V/m and specific internal
energy u=U/m

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 Ideal solutions

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 Types of solutions

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On the basis of Raoult’s Law, liquid-liquid solutions are
classified into two types of solutions, they are:
✓Ideal Solutions
✓Non-ideal Solutions
The solutions which obey Raoult’s law at all compositions of
solute in solvent at all temperature are called ideal
solutions.

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✓ Ideal solutions can be obtained by mixing two
components with identical molecular size, structure and
they should have almost same inter molecular attraction
e.g., two liquids A and B form an ideal solution when A –
A and B–B molecular attractions will be same and hence
A–B molecular atrraction will be almost same as A–A and
B–B molecular attraction.
An ideal solution should have following characteristics
✓ It should obey Raoult’s law i.e., PA= XA and PB = XB
✓ ΔHmixing = 0, i.e. no heat should be absorbed or evolved
during mixing
✓ ΔVmixing = 0, i.e. no expansion or contraction on mixing

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Examples of Ideal solutions
✓Ethyl chloride and ethyl bromide
✓n–hexane and n–heptane
✓CCl4 and SiCl
The solution which deviate from ideal behaviour are called
non ideal solution or real solutions and they do not obey
Raoult’s law over entire range of composition.
It has been found that on increasing dilution, a non ideal
solution tend to be ideal
For non ideal solutions,
PA ǂ XA P0A, PB ¹ǂ XBP0B i.e, they do not obey Raoult’s law
ΔHmixing ǂ 0,
ΔVmixing = 0

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Here we may have two cases
Case 1:

Such a solution shows positive deviation from Raoult’s Law and

the observed boiling point of such solutions is found to be less
than the calculated value. e.g. cyclohexane and ethanol.
Examples of solutions showing positive deviation:
✓ Acetone + Ethanol

✓Acetone- Benzene
✓Water + Methanol
✓Water + Ethyanol
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Case 2:

✓ Solutions of above type show negative deviation from

Raoult’s law and their observed boiling point is found to
be higher than the calculated value
Examples of solutions showing negative deviation:
✓Acetone + Aniline
✓ Chloroform + Diethyl ether
✓ Chloroform + Benzene
✓Water + HCl

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Condition for forming non-ideal solution showing positive
deviation
Two liquids A & B on mixing form this type of solutions
when
✓ A-B attractive force should be weaker than A-A and B-B
attractive force.
✓ “A” and “B” have different shape, size and character.
✓ “A” and “B” escape easily showing higher vapour
pressure than the expected value.

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Condition for forming non-ideal solution showing negative
deviation
Two liquids A & B on mixing form this type of solutions
when
✓ A-B attractive force should be greater than A-A and B-B
attractive force.
✓ “A” and “B” have different shape, size and character.
✓ Escaping tendency of both “A” and “B” is lower showing
lower vapour pressure than expected ideally

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 Comparison between Ideal and Non-ideal solution

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Limitations of Raoult’s Law
✓ Raoult’s law is applicable only to very dilute solutions.
✓ It is applicable to solutions containing non-volatile solute
only.
✓ It is not applicable to solutes which dissociate or
associate in a particular solution

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 Henry's law
✓ Henry's Law has to do with the principles involving
dissolved gas and pressure. It states that the amount of
gas dissolved under equilibrium in a certain volume of
liquid is in direct proportion to the pressure of the gas that
makes contact with the liquid's surface.
✓ Henry's law, statement that the weight of a gas dissolved
by a liquid is proportional to the pressure of the gas upon
the liquid. The law, which was first formulated in 1803 by
the English physician and chemist William Henry, holds
only for dilute solutions and low gas pressures.

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 P ∝ C (or) P = kH.C
Where,
‘P’ denotes the partial pressure of the gas in the atmosphere
above the liquid.
‘C’ denotes the concentration of the dissolved gas.
‘kH’ is the Henry’s law constant of the gas.

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Example1 : if the concentration of CO2 dissolved in the
sparkling water in a closed soda can is 0.075 m what is the
parital pressure of CO2 (gas) in the can at 25oC. the Henry
Constant for CO2 at 25 C is 0.34 mol/(kg.bar).
Example 2 : A tank filled with water is pressurized with H2O (g)
and H2 (g). the total pressure in the tank is 5 bar at 0oC. The
parial pressure of H2O (g) is 0.15 bar. Find the concentration of
H2 (g) in the water. The Henry constant for H2 (g) in water at 0
oC is 7.8 × 10−4 mol /Kg.bar.

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✓ For a gas mixture, Henry's law helps to predict the
amount of each gas which will go into solution. When a
gas is in contact with the surface of a liquid, the amount
of the gas which will go into solution is proportional to
the partial pressure of that gas.
✓ An equivalent way of stating the law is that the solubility
of a gas in a liquid is directly proportional to the partial
pressure of the gas above the liquid. the solubility of
gases generally decreases with increasing temperature.

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 Henry’s constant
Except for high soluble gases such as NH3 where Henry’s
law constant varies slightly with concentration level in
solution, the solubility curves for most less soluble gases
are straight lines and obey Henry’s law.

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 Solubility and Henry’s law constant
✓ Solubility: the amount of a substance that will dissolve in
a given amount of solvent, g/L.
✓ A saturated solution is one which is in equilibrium with
undissolved solute – it has reached limit of solubility.
According to Henry’s law, gases are more soluble at
higher pressure.
The solubility

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 Two opposite ends of the composition range

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 Gibbs-Duhem equation/Partial Molar Properties
Gibbs-Duhem equation, thermodynamic relationship
expressing changes in the chemical potential of a substance
(or mixture of substances in a multicomponent system) in
terms of changes in the temperature T and pressure P of
the system.
In order to derive the expression for Gibbs’s-Duhem
equation, consider a system that comprises of n types of
constituents with n1, n2, n3, n4 … moles. So, being an
extensive property, the partial molar free energy depends
upon not only the temperature and pressure but also on
the number of moles of different components.
Mathematically, we can say that

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 𝐺 = 𝑓(𝑇, 𝑃, 𝑛1, 𝑛2, 𝑛3 … )
Now let us assume a small change in the temperature, pressure and
amount of different components, this would impart a variation in
partial molar free energy as given below.

✓ The first term on the right-hand side gives the change in the
free energy with the temperature at constant pressure and
compositions;
✓ while the second term gives the change in the free energy
with pressure at constant temperature and compositions.
✓ The terms afterward represent the variation in free energy
with the amount of one component while the temperature,
pressure and all other compositions are kept constant

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However, if the temperature and pressure of the system are
kept constant, i.e., dT = 0, dP = 0, the equation takes the
form

Every term on the right-hand side of the equation (181) is

partial molar free energy or simply the “chemical potential”
i.e.

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 After putting the values from equations like (182 – 186) in equation (181), we get

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The differentiation of equation (188) at constant
temperature and constant pressure but changing
composition gives the following relation

OR

After comparing the equation (187) and (190), we can

conclude that the content included in the second bracket
must be equal to zero. Mathematically, we can say that

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 OR

Which is the popular Gibbs-Duhem equation, and is

applicable to the systems under constant temperature-
pressure conditions.
The physical significance of the Gibbs-Duhem equation can
be understood by taking the example of binary solutions i.e.
a system of two components only. The Gibbs-Duhem
equation for such systems is

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 OR

OR

Hence, the chemical potential of one constituent is not

independent of another component in binary solutions. In
other words, the chemical potentials or partial molar free
energies of two components of the binary system are
mutually dependent; and if the one increases the other
one decreases.

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It is also worthy to note that if the number of moles of
different constituents remains constant (closed system),
i.e., 𝑑𝑛𝑖 = 0; equation (180) reduces to the following.

Which is the variation of free energy with temperature and

pressure in closed systems. These two relations can further
be used to deduce the variations of chemical potentials with
temperature and volume.

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 Application of Gibbs-Duhem equation
Used to calculate:-
✓ a partial molar quantity of a binary mixture from
measurements of the composition dependence of the
corresponding total molar quantity,
✓ the partial molar quantity of a component, say 1, of a
binary mixture from measurements of the composition
dependence of the corresponding partial molar quantity
of component 2, and
✓ the partial vapor pressures from measurements of the
liquid-phase composition dependence of the total vapor
pressure.

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The significance of the Gibbs-Duhem equation is that the
chemical potential of a component in a mixture cannot
change independently of the chemical potential of the
other components. For example, in a binary mixture we
have: i.e., if one chemical potential increases, the other
must decrease.
✓ The Gibbs-Duhem equation relates the change in one
thermodynamic potential (dμA) to the other (dμB).

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 Quasi-chemical Solution Models
Thermodynamics properties of solutions are consequence of
interaction amongst atoms molecules. Quasi-chemical theory is
the simplest & able to explain the properties approximately from
atomistic point of view.
✓ In a metallic solution, the components are assumed to be
present as atoms & not molecules due to nature of metallic
bonds. So there exit interaction energy between them.
✓ The quasi-chemical theory explained by considering some
important assumptions.
i. Atoms have chemical bonds amongst them.
ii. Bonds get associated with some enthalpy which alone
contributes to enthalpy of solution.
iii. Only bonds amongst nearest neighboring atoms are
energetically significant.

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• The quasi–chemical solution model has a better
treatment of configurational entropy which accounts for
a non–random distribution of atoms.

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 Regular solutions
✓ regular solution is one involving no entropy change
when a small amount of one of its components is
transferred to it from an ideal solution of the same
composition, the total volume remaining unchanged.
✓ The regular solution model gives an enthalpy that is
symmetrical with respect to composition.
✓ The simplest non-ideal solution model that works beyond
the Henry’s Law model is the regular solution model. The
basic assumption of the simplest regular solution model
is that when components A and B mix, they mix
randomly.

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 A regular solution is non-ideal but the interactions
between molecules are weak, and all molecules are about
the same size.
✓ To construct a regular solution model we recall an ideal
solution which is a solution where all interactions
between solution components are equal.
✓ In a solution composed of two components A and B, call
the interaction between two A molecules, εAA, between
2 B molecules εBB, and between an A and a B εAB. If
these three interaction energies are equal, the solution is
ideal. If they are not the same, the solution’s
thermodynamic behavior is non-ideal.

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How we weather a solution is regular solutions?
✓ Only the enthalpy of mixing is non-zero, unlike for an
ideal solution, while the volume of the solution equals
the sum of volumes of components.
✓ For a regular solution the entropy of mixing is the same
as for the ideal solution but the enthalpy now depends
on composition,

where Β is the interaction parameter. The Gibbs free energy

of mixing is therefore

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✓ For a regular solution the entropy of mixing is the same
as for the ideal solution

Since mole fractions are always less than unity, the ln terms
are always negative, and the entropy of mixing is always
positive. The Gibbs free energy is always negative and
becomes more negative as the temperature is increased.

The Gibbs free energy of mixing for ideal solutions is

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✓ Suppose we imagine mixing NA molecules A with NB
molecules B to form a solution. The solution can be
imagined as NA A molecules and NB B molecules
arranged on a lattice:

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 Ideal Gas Mixture
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.
✓ 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.
✓ In a ideal gas mixture, partial molar properties of a
species (except volume) is equal to its molar properties
of the species as a pure ideal gas when the temperature
is the mixture temperature and the pressure equal to its
partial pressure in the mixture.
M ig (T , P ) = M iig (T , pi )
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 Equation of state: pv = nℜT, for an ideal gas.

partial pressure: Pi V = ni ℜT, Pi = Xi P (all components

occupy same total volume V)

Hence, for enthalpy

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• For entropy

• For Gibbs energy

G ig = 
i
yi i (T ) + RT 
i
yi ln ( yi P )

Integration constant

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 Fugacity, Activity, and Standard States
Fugacity and Fugacity Coefficient:
fugacity, a measure of the tendency of a component of a
liquid mixture to escape, or vaporize, from the mixture and
has the units of pressure (atmosphere or Pa) and is identical
to the partial pressure of ideal gases.
Fugacity is a property used to show differences between
chemical potentials at standard states.
Or is a convenient measure of chemical potential
Example
A high fugacity of water or oxygen means a high chemical
potential of water or oxygen, respectively.
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Additionally,
✓ Fugacity is a measure of chemical potential in the form of
'adjusted pressure.' It directly relates to the tendency of
a substance to prefer one phase (liquid, solid, gas) over
another.
✓ At a fixed temperature and pressure, water will have a
different fugacity for each phase. The phase with the
lowest fugacity will be the most favorable; the substance
minimizes Gibbs free energy.

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✓ The fugacity coefficient is defined as the ratio
fugacity/pressure. For gases at low pressures (where the
ideal gas law is a good approximation), fugacity is roughly
equal to pressure. Thus, for an ideal gas, the ratio ϕ = f/P
between fugacity f and pressure P (the fugacity
coefficient) is equal to 1.
What does fugacity coefficient greater than 1 mean?
✓ A real gas is defined as a gas that at all standard pressure
and temperature conditions does not obey gas laws. It
deviates from its ideal behaviour as the gas becomes
huge and voluminous.

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✓ For pure species in ideal-gas state;
Giig = i (T ) + RT ln P

For pure species in real-gas state;

Gi  i (T ) + RT ln f i

fi
Gi − Gi ig
= RT ln = GiR
P
fi
i =
P
is called fugacity coefficient of pure species.
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✓ For species i in a mixture of real gases or in a solution of
liquids, in equilibrium;
fˆi  = fˆi  = .... = fˆi 
The fugacity of each species is the same in all phases.
✓ For vapor-liquid equilibrium
fˆi v = fˆi l

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✓ For species in gas mixture or solution of liquids,
Fugacity coefficient of species i in gas mixture;
ˆi
f
ˆi =
yi P
Fugacity coefficient of species i in solution;
fˆi
ˆi =
xi P
For species i in ideal-gas mixture,

ˆ
i = 1
ig

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In vapor-liquid equilibrium, vapor is assumed ideal gas,
hence,
ˆ
i = 1
ig

fˆi l = fˆi v = yi P

✓ Thus, fugacity of species i (in both the liquid and vapor

phases) is equal to the partial pressure of species i in the
vapor phase.

fˆ1 = y1 P fˆ2 = y2 P

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In an ideal solution
ˆf i id = xi f i
By introducing a activity coefficient
fˆ i fˆ i
i = = id
xi f i fˆi

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 Standard States
The standard state is the reference state for thermodynamic
state parameters such as enthalpy, entropy, Gibbs free
energy, and many other material standards for a certain
substance. The standard enthalpy change of formation for a
material in its standard state is zero.
It is used to calculate the material's properties under
different conditions.
A superscript circle ° (degree symbol) or a Plimsoll
(⦵) character is used to designate a thermodynamic quantity
in the standard state, such as change in enthalpy (ΔH°),
change in entropy (ΔS°), or change in Gibbs free energy (ΔG°)

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 Standard Enthalpy of Formation
✓ The standard enthalpy of formation, or standard heat of
formation, of a compound is the change in enthalpy that
accompanies the formation of one mole of the compound
from its elements in their standard states. For example, the
standard enthalpy of formation for carbon dioxide would
be the change in enthalpy for the following reaction:

✓ Note that standard enthalpies of formation are always

given in units of kJ/mol of the compound formed.

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Standard enthalpy change of formation is equal to the sum
of the standard enthalpies of formation of the products
minus the sum of the standard enthalpies of formation of
the reactants.

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 Change in entropy (ΔS°),
✓ Entropy Change is the phenomenon which is the
measure of change of disorder or randomness in a
thermodynamic system. It is related to the conversion of
heat or enthalpy done in work. A thermodynamic system
which has more randomness means it has high entropy.
✓ For any chemical reaction, the standard entropy change
is the sum of the standard molar entropies of the
products minus the sum of the standard molar entropies
of the reactants.

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 The standard Gibbs free energy change, ΔG°,
indicates the thermodynamic favorability of a physical or
chemical process. When ΔG° < 0, the process is
thermodynamically favored. For a given process, the value of
ΔG° can be calculated directly from the values of ΔH° and ΔS°
using the following equation: ΔG° = ΔH° - TΔS°.
✓ in other words, ΔG is the change in free energy of a system
as it goes from some initial state, such as all reactants, to
some other, final state, such as all products. This value tells
us the maximum usable energy released (or absorbed) in
going from the initial to the final state

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 Alternative Standard States
The concept of standard states arises from the definition of
the activity function.
The choice of a standard state is arbitrary, and the activity is
always unity at the standard state chosen
The activity of a component in a solution is essentially a
relative quantity. From the definition of activity it follows
that the numerical value of the activity of a particular
component is dependent on the choice of the standard
state. There is no fundamental reason for preferring one
standard state over another. Convenience dictates the
choice of the standard state.

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✓ The activity of a component, aij, is related to the mole
fraction of that component in a solid phase, Xij. Activity
increases as mole fraction increases. This relationship
applies to solids and also to components in aqueous
solution or gaseous mixture.
✓ The activity of pure substances in condensed phases
(solid or liquids) is normally taken as unity (the number
1). Activity depends on temperature, pressure and
composition of the mixture, among other things. For
gases, the activity is the effective partial pressure, and is
usually referred to as fugacity.

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✓ The particular choice is known as the Raultian standard
state.

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• The Henrian standard state is a hypothetical, non-physical
state for component j. suppose that we are interest in the
composition marked x in the following figure:

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