UNIT 4.

CHEMICAL EQUILIBRIUM AND PHASE

EQUILIBRIUM

By

Hanna Samuel (MSc, in Physical Chemistry)

June, 2022
Salale University Fitche, Ethiopia
 4.1 Chemical Equilibrium

Equilibrium is a state in which there are no observable changes as time goes.

Chemical equilibrium is defined as a chemical system where the concentrations of

reactants and products remain constant over time. On the molecular level, the system is
dynamic: The rate of change is the same in either the forward or reverse directions.

 There are two types of equilibrium: Physical and Chemical equilibrium

Examples: Physical- equilibrium between two phases of the same substance.
Changes that occur are physical which mean has the same chemical composition

Chemical- equilibrium chemists are more interested in this because the progress
of the reaction can be easily monitored.
N2O4 (g) ⇄ 2NO2 (g)
Law of Mass Action- For a reversible reaction at equilibrium and constant temperature, a
certain ratio of reactant and product concentrations has a constant value (K).

The Equilibrium Constant (K)- A number equal to the ratio of the equilibrium
concentrations of products to the equilibrium concentrations of reactants each raised to the
power of its stoichiometric coefficient.
 For a general reaction:

jA + kB ⇄ lC + mD

Therefore;
Example 1. On chemical equilibrium one of the environmentally important reactions involved in acid rain production has the following equilibrium expression. From the expression, what would be the balanced chemical reaction? Note: all components are in the gas phase.

Example 1. On chemical equilibrium one of the environmentally important reactions

involved in acid rain production has the following equilibrium expression. From the
expression, what would be the balanced chemical reaction? Note: all components are in the
gas phase.
 EQUILIBRIUM CONSTANT EXPRESSIONS

Equilibrium constants can be expressed using Kc or Kp.

 Kc uses the concentration of reactants and products to calculate the equilibrium constant.

 Kp uses the pressure of the gaseous reactants and products to calculate the equilibrium
constant.
Example 2
4 NH3(g) + 7 O2(g) 4 NO2(g) + 6 H2O(g) Write the Equilibrium Expression for the
reaction. The expression will have either concentration units of mol/L (M), or units of
pressure (atm) for the reactants and products. What would be the overall unit for K using
Molarity and atm units respectively?
Relationships between chemical equations and the expressions of equilibrium
constant
1). If a reaction is re-written where the reactants become products and products-reactants,
the new Equilibrium Expression is the reciprocal of the old.
2) When the entire equation for a reaction is multiplied by n,
The expression of equilibrium constant depends on how the equilibrium equation is
written.
For example 3, for the following equilibrium
 RELATIONSHIP BETWEEN KC AND KP

 How is KP related to Kc? Through the use of the ideal gas law, for all species i: For a
general reaction
jA + kB ⇄ lC + mD
 Units for Kc are to concentration (1 molar) raised to power Δn, and those
for KP are pressure (1 atm) units raised to power Δn. The Kc and KP may
have unit or unit less depends on the stoichometric coefficient.
 Example
RELATIONSHIPS BETWEEN K AND ∆G O

 The standard Gibbs function change for reaction is ∆Go and represents
the energy available for reaction if 1 mol of reactants reacts until reaching
equilibrium. Figure 4.2 relates ∆G and ξ, and clearly shows how the
amount of energy available for reaction ∆G decreases during reaction (i.e.
in going from left to right as ξ increases).
 Stated another way, the gradient of the curve is always negative before
the position of equilibrium, so any increases in ξ cause the value of ∆G to
become more negative.
Figure 4.2 The value of the Gibbs function ∆G decreases as the extent of reaction ξ until, at
ξ(eq), there is no longer any energy available for reaction, and ∆G = 0. ξ = 0 represents no
reaction and ξ = 1 mol represents complete reaction.
 The amount of energy liberated per incremental increase in reaction is quite
large at the start of reaction, but decreases until, at equilibrium, a tiny increase
in the extent of reaction would not change ∆G(total).
 The graph has reached a minimum, so the gradient at the bottom of the trough
is zero. The minimum in the graph of ∆G against ξ is the reaction’s position of
equilibrium we call it ξ(eq). The maximum amount of energy has already been
expended at equilibrium, so ∆G is zero.
 The relationship between the energy available for reaction ∆G and the extent
of reaction (expressed in terms of the reaction quotient Q) is given by
Where ∆G is the energy available for reaction during chemical changes, and
∆G o representing the change in Gibbs function.

,
 The value of ∆G only reaches zero when ∆Go is exactly the same as RT lnQ.
In other words, there is no energy available for reaction when ∆G = 0: we say
the system has ‘reached equilibrium’. In fact, ∆G = 0 is one of the best
definitions of equilibrium.
 This allows us to develop a set of criteria to determine in which direction a
reaction will proceed under non-standard conditions. This is because Q/K
will determine the sign of ∆G:
 In the case of equilibrium, Q = K and ∆G = 0

 This Eq. not only proves the existence of an equilibrium constant, KP , it

also gives us an explicit formula for calculating K P from Go data.
 This allows us to develop a set of criteria to determine in which direction a reaction will
proceed under non-standard conditions. This is because Q/K will determine the sign of
∆G:
 If Q/K < 1, then ∆G is negative, and the reaction is spontaneous as written
 If Q/K = 1, then ∆G = 0 and the system is at equilibrium,
 If Q/K > 1, then ∆G is positive, and the reaction is spontaneous in the opposite direction as
written
 Example: Consider the dissolution of CaCO3 (calcite) in aqueous solution:
CaCO3 → Ca2+ + CO3 2- Does the reaction proceed spontaneously as written?
 Calculate the free energy of reaction at standard state and equilibrium constant
(products and reactants at activity = 1, P = 1 atm, T = 25°C): free energy of CaCO 3,
Ca2+ and CO3 2- are -270,-132, and -126 kcalmol-1 respectively.
Therefore, at standard state, the reaction spontaneously proceeds in the opposite
direction to what is written (i.e., calcite precipitates).

 From Sample Calculation of above, we know: ∆G° = +12 kcal/mole Thus:

 All units cancel out

RELATING CHEMICAL EQUATIONS AND EQUILIBRIUM CONSTANTS

 A large value for the equilibrium constant indicates that the mixture contains more
products than reactants and therefore lies towards the product side of the equation.
 A small value for the equilibrium constant means the mixture contains less products
than reactants and therefore lies toward the reactant side.
HOMOGENEOUS AND HETEROGENEOUS EQUILIBRIUM

 Equilibria for which all substances are in the same phase are called homogeneous
equilibria.
 Equilibria in which 2 or more phases are present are called heterogeneous equilibria.
 The concentrations of pure solids and liquids are left out of the equilibrium constant
expression for a heterogeneous equation
LECHATLIER’S PRINCIPLE

 In 1884, the French Chemist Henri Le Chatelier suggested that equilibrium systems
tend to compensate for the effects of perturbing influences.
 When a system at equilibrium is disturbed, the equilibrium position will shift in the
direction which tends to minimize, or counteract, the effect of the disturbance.
 If the concentration of a solute reactant is increased, the equilibrium position shifts to
use up the added reactants by producing more products.
 If the pressure on an equilibrium system is increased, then the equilibrium position
shifts to reduce the pressure.
VARIATION OF EQUILIBRIUM WITH CHANGE IN FACTORS

1. Changes in concentration
Consider the following system at equilibrium:

 Increasing the concentration of either Fe3+(aq) or SCN- (aq) will result in the
equilibrium position moving to the right, using up the some of the additional reactants
and producing more FeSCN2+(aq). The solution will become a darker red color.
 Increasing the concentration of FeSCN2+(aq) will result in the equilibrium position
moving to the left to use up some of the additional FeSCN2+(aq) and producing more
reactants. The solution will become less red.
 Increasing the concentration of FeSCN2+(aq) will result in the equilibrium position
moving to the left to use up some of the additional FeSCN2+(aq) and producing more
reactants. The solution will become less red.
 Removing some of the FeSCN2+(aq) will result in the equilibrium position moving to
the right to produce more FeSCN2+(aq) which will lead the solution to become a
darker red color.
2.CHANGES IN PRESSURE OF GASEOUS EQUILIBRIUM SYSTEMS

 Gas pressure is related to the number of gas particles in the system, more gas particles
means more gas pressure.
Consider the following gaseous equilibrium system:

 Increasing the pressure on this system results in the equilibrium position moving to
the right, consuming NO2(g) and producing more N2O4(g). The system will become
a lighter red-brown colour.
 Reducing the pressure on this equilibrium system will result in the equilibrium
position moving to the left, that is, to the side that has the most gas particles, in order
to increase the pressure
3. CHANGES IN VOLUME OF GASEOUS EQUILIBRIUM SYSTEMS

 Gas volume is related to gas pressure, a gas at reduced volume has a

higher pressure, a gas at increased volume has a lower pressure. Consider
the following gaseous equilibrium system:

 Increasing the volume of this equilibrium system is equivalent to

reducing the pressure, so the equilibrium position moves to the side of the
reaction that has the most gas particles in order to increase the pressure.
 The equilibrium position shifts to the left producing more NO2(g) by
consuming N2O4(g). The system becomes less red-brown in color.​

 Reducing the volume of this equilibrium system is equivalent to increasing

the pressure, so the equilibrium position moves to the side of the reaction
that has the least gas particles in order to reduce the pressure.
 4. CHANGES IN TEMPERATURE

In an endothermic reaction, energy can be considered as a reactant of the

reaction. In an exothermic reaction, energy can be considered as a product of the
reaction.

1. Endothermic Equilibrium Systems Consider the following reaction at

equilibrium:
Increasing the temperature of the equilibrium system will be consumed to
produce more HI(g) product, since H2(g) and I2(s) will be consumed, there will
be less purple solid in the reaction vessel.
2. EXOTHERMIC EQUILIBRIUM SYSTEMS

Consider the following reaction at equilibrium:

 Increasing the temperature of this equilibrium system shifts the equilibrium

position to the left, consuming some of the energy and products to produce
more reactants. There will be less white AgCl(s) in the reaction vessel.
 Reducing the temperature of this equilibrium system shifts the equilibrium
position to the right, producing more heat and more white AgCl(s
QUANTITATIVE EFFECTS IN TEMPERATURE AND PRESSURE

 The equilibrium constant of a chemical reaction is constant at a given

temperature, but its magnitude varies considerably with changes in
temperature. The Le Chatelier's principle gives only a qualitative idea of
the shift of equilibrium when temperature changes.
 However, Quantitative expression for the variation of equilibrium
constant with temperature can be derived thermodynamically as follows :
PHASE EQUILBRIUM
 Phase equilibrium describes the way phases (such as solid, liquid and/or gas) co-

exist at some temperatures and pressure, but interchange at others.

 Appropriately, the word comes from the Greek phasis, meaning ‘appearance’. Ice,

water and steam are the three simple phases of H2O.

 A phase is a component within a system, existing in a precisely defined physical state,

e.g. gas, liquid, or a solid that has a single crystallographic form.

 Ice is a solid form of water, and is its only stable form below 0 ◦C. The liquid form of

H2O is the only stable form in the temperature range 0 < T < 100 ◦C. Above 100 ◦C,
the normal, stable phase is gaseous water, ‘steam’.

 Water’s normal melting temperature T(melt) is 0 ◦C (273.15 K). The word ‘normal’ in

this context implies ‘at standard pressure p o ’. The pressure p o has a value of 105 Pa
 This temperature T(melt) is often called the melting point because water and ice

coexist indefinitely at this temperature and pressure, but at no other temperature can
they coexist. We say they reside together at equilibrium.

 To melt the ice, an amount of energy equal to ∆Ho (melt) must be added to overcome

those forces that promote the water adopting a solid-state structure. Such forces will
include hydrogen bonds.
 Re-cooling the melted water to re-solidify it back to ice involves the same amount of

energy, but this time energy is liberated, so ∆Ho (melt) =- ∆Ho (freeze) .

 The freezing process is often called fusion. (Strictly, we ought to define the energy by

saying that no pressure– volume work is performed during the melting and freezing
processes, and that the melting and freezing processes occur without any changes in
temperature.)
 THE PHASE RULE

 The phase rule allows us to predict the number of stable phases that may exist in

equilibrium for a particular system.

Defining the State of a System

4.2.2 Independent and Dependent Variables

 Pressure, p and temperature, T as the independent variables. Other parameters such as

volume, density and refractive index are then dependent variables.

 If we wish to define the total amount of substance present, then one of the variables must
 We must therefore define our composition in terms of the amounts of substance of the

independent components ni , nj etc.

Constituents and Components

 It is not always necessary to specify the amount of every constituent in order to define the

chemical composition of a system.

 A component is defined as a chemically independent constituent of a system. The number of

components, C, is the smallest number of independently variable constituents needed to

express the composition of each phase.
Independent chemical reactions act as constraints on the composition of the system, and so
contribute to the value of R.
Other conditions imposed by the chemical stoichiometry or by the need to maintain
electroneutrality should also be counted as constraints.
 When considering phase equilibria it is necessary to determine only the number and not
the identity of the independent components.
How can determining the Number of Independent Components?

Example 9 ;A gaseous mixture of CH4, C2H6, C3H8 and H2 consists of four constituents.
However, the amounts of these substances are related by two independent chemical

equations 2CH4(g) = C2H6(g)+ H2(g)

C2H6(g) + CH4(g) = C3H8(g)+ H2(g) which may be considered as constraints on the

system. We could write other chemical equations but these would not be independent of
the first two. For example, the equation 3CH4(g) = C3H8(g)+ 2H2(g) is actually just the
sum of the first two independent relationships. Thus there must be only two independent
DEGREE OF FREEDOM

 The variance, or number of degrees of freedom of a system, F is the number of

such variables that may be varied independently without changing the number of
phases present at equilibrium.
 Systems for which F = 0 have no degrees of freedom and are said to be invariant
 Systems with one degree of freedom, F = 1, are univariant.
 Systems with two degrees of freedom, F = 2, are bivariant.
We will see later that invariant systems are represented by points on phase diagrams,
univariant systems by lines and bivariant systems by areas
 GIBBS PHASE RULE

F = C + 2 – P may be used to determine the variance of any system at equilibrium.

Determining the Variance of a System Using the Phase Rule
Example 11:For a single-component system, such as a sample of pure water, the composition is, by default, fixed and
C = 1. If the substance is present as only one phase,
e.g. a solid, then P = 1. The phase rule therefore shows that F = C + 2 - P = 1 + 2 - 1 = 2 and the system is therefore
divariant with two degrees of freedom.
 If, however, the system exists as two phases in equilibrium, e.g. as a vapour and a liquid, then P = 2, and F = C + 2
-P=1+2-2=1
 For a system of solid, liquid and vapour, P = 3, and so F = C + 2 - P = 1 + 2 - 3 = 0
 The system is therefore invariant and there are no degrees of freedom. Thus for a one

component system, there is only one set of values of pressure and temperature
where The system is therefore invariant and there are no degrees of freedom.

 Thus for a one component system, there is only one set of values of pressure and

temperature where
4.2.4 PHASE DIAGRAMS FOR SIMPLE SYSTEMS

 The phase diagram for a system shows the regions of composition, pressure, volume
and temperature at which various phases are stable.
 The composition of a one-component system is fixed so that the state of the system
may therefore be defined by specifying the value of any two of the pressure, volume
and temperature.
 The state of the system may therefore be represented as a surface on a three
dimensional pressure, volume and temperature plot.
 Areas on the surface represent regions where only one phase is stable
 The lines drawn between the regions represent the values of these variables at which
two phases coexist in equilibrium. Triple Points at the intersection between two lines
represent the values at which three phases coexist in equilibrium.
PRESSURE-TEMPERATURE PHASE DIAGRAMS
 If pressure and temperature are taken as the independent variables that define the state
of the system, then the volume must be a dependent variable and its value may
therefore be determined for any point on the diagram.
PRESSURE-VOLUME PHASE DIAGRAMS
 Less commonly seen are pressure-volume phase diagrams in which the pressure and
volume are taken as the independent variable and temperature as the dependent
variable.
THE CRITICAL POINT AND SUPERCRITICAL
BEHAVIOUR
 A critical point marks the conditions at which two phases become identical. Single

component systems exhibit a critical point at which liquid and vapor phases become
indistinguishable.

 Consider the behavior of a one-component system in which liquid and vapor are in

equilibrium. As the temperature increases, the pressure also increases, as the system
follows the liquid-vapour equilibrium line on the phase diagram.

 This causes an increase in the density of the vapour phase and a slight decrease in the

density of the liquid phase. Eventually, at the critical point, the densities of the two
phases become equal and the two phases cannot be distinguished.
INVARIANT, UNIVARIANT AND BIVARIANT SYSTEM

 Invariant states are represented by points on phase diagrams.

 Systems with one degree of freedom, F = 1, are univariant and are
represented by lines and those with two degrees of freedom, F = 2, are
bivariant and correspond to areas on phase diagrams.
 For a one-component system, the coexistence of three phases in
equilibrium corresponds to an invariant state since variant
 This state is usually called a triple point. The three phases may only exist
at a particular temperature and particular pressure
 The most obvious triple point corresponds to the coexistence of solid, liquid and
vapor phases.
 For water, this triple point occurs at a temperature of 273.16 K and a pressure of 608
Pa, at a temperature close to the normal freezing point, but at a much lower pressure.
 In contrast, for carbon dioxide, the triple point occurs at a much higher temperature
and pressure than ambient condition
4.2.5 THE CLAPEYRON EQUATION

 The slopes of the lines on a one-component pressure-temperature phase diagram may

be derived from the Clapeyron equation.

 This equation is known as Clausius-Clapeyron equation.

 The equation relates the values of any pair of points (p1, T1) and (p2, T2) on the
vaporization or sublimation line. By measuring experimentally the gradient of a
pressure temperature line we may therefore determine an average value for the
enthalpy of vaporization or sublimation over that temperature range.
 HIGHER ORDER SYSTEM

 The composition of systems consisting of more than one component may vary and
phase diagrams of such systems can no longer be represented in three dimensions.
 Since drawing three-dimensional plots is difficult (and four- or more dimensional
plots impossible) it is again usual to represent a phase diagram for a multi-component
system as a series of two-dimensional projections.
 These projections show how the stabilities of the different phases of the system
change for pairs of parameters with the values of other variables held constant.
 Thus the phase diagram for a two-component system may represented by, for
example, a pressure-composition plot at a certain temperature (often T = 298 K) or ( p
= 1 bar).
 TWO-COMPONENT PHASE DIAGRAMS

 At high temperatures the system is all in the liquid phase.

 At the lower temperatures the system is in the solid phase.
 In between these two situations there is a region where there are two phases (liquid and
solid) in equilibrium with each other.
 If we continue to cool the system we will eventually reach a temperature where one or
both of the pure components will freeze.
 EUTECTIC SYSTEM

A binary system consisting of two substances, which are miscible in all proportion in the
liquid phase, but which do not react chemically, is known as the eutectic (easy to melt)
system, e.g. a mixture of lead and silver comprises of such a system
Eutectic Mixture is a solid solution of two or more substances having the lowest
freezing point of all the possible mixture of the components. This is taken advantage of
in alloys of low melting point which are generally eutectic mixtures.
Eutectic point: Two or more solid substances capable of forming solid solutions with
each other the property of lowering each other’s freezing point; and the minimum
freezing point attainable corresponding to the eutectic mixture is termed the eutectic
point (means lowest melting point).
 At temperatures at and below the melting points the phase diagram will look
something like the following hypothetical phase diagram involving a substance "A"
and a substance "B."
 In this diagram we are plotting temperature versus the mole fraction of substance B.
 THE LEVER RULE
 Finding the amounts of phases in a two phase region:
a. Locate composition and temperature in diagram
b. In two phase region draw the tie line or isotherm
c. Fraction of a phase is determined by taking the length of the tie line to the phase
boundary for the other phase, and dividing by the total length of tie line

Fig.4.8 The lever rule

The lever rule is a mechanical analogy to the mass balance calculation. The tie line in
the two-phase region is analogous to a lever balanced on a fulcrum.
Derivation of the lever rule
1). All material must be in one phase or the other:
2). Mass of a component that is present in both phases equal to the mass of the
component in one phase + mass of the component in the second phase:

3). Solution of these equations gives us the lever rule

 THREE –COMPONENT SYSTEMS

 For a three component system having a single homogeneous phase, the degree of
freedom .

 Several schemes have been in use for represented the equilibria in three component

systems but the equilateral triangle method suggested by Gibbs and Roozeboom is
extensively used.

 Ternary phase diagrams are taken at constant T and P.

 GRAPHICAL REPRESENTATION OF A THREE-COMPONENT
SYSTEM
 Line AB represents the compositions of all systems that can be prepared from pure A
and pure B: at point P in both figures the system in 60% B and 40% A.

Fig.4.10 typical three-component liquid system

 In Fig. 4 10a, components A and B are miscible and components A and C are

miscible, but components B and C show a region of miscibility. Three-component

systems consisting of two-liquid phase lie under the curved line. Above the curved
line, only a single phase is present and the system is homogeneous.

 In Fig. 4.10b, only A and C are miscible, and two regions of immiscibility exist.

None of the three components is miscible, then three regions of two liquid phases
may exist, as shown in Fig. 4.10c.
 If the three components are very insoluble in each other, the situation in Fig. 4.10d
may occur. Near the corner, the system is homogeneous.
 In the tie line areas, two liquid phases are in equilibrium, and in the center triangular
area, three liquid phases are in equilibrium. In the latter case, F = 3 – P = 3 – 3 = 0
and the system is invariant.
 This means that anywhere in the center triangle the compositions of the three liquid
phases are fixed and are given by the vertices of the center triangle.
 These can be described as an A–rich phase, a B–rich phase, and a C–rich phase,
depending upon which is the closest vertex.
 PHASE DISTRIBUTION EQUILIBRIA

 It often happens that two immiscible liquid phases are in contact, one of which

contains a solute. How will the solute tend to distribute itself between the two
phases?

 One’s first thought might be that some of the solute will migrate from one phase into the

other until it is distributed equally between the two phases, since this would correspond to
the maximum dispersion (randomness) of the solute.
 For a solute S distributed between two phases a and b the process Sa = Sb is defined by
the distribution law

 In which Ka,b is the distribution ratio (also called the distribution coefficient) and [S]i is
the solubility of the solute in the phase.
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