BCHEM259: Physical Chemistry I

Solutions I & II

Dr. Elliot Sarpong Menkah

Faculty of Physical and Computational Sciences

Chemistry Department

February 24, 2024

Elliot S. Menkah, Ph.D. (KNUST) Solutions I January, 2024 1 / 10

 Phase Equilibria

Phase Equilibria
- Phase diagrams
- Melting and freezing points
- Boiling point
- Phase diagrams of One-Component systems
- Phase diagrams of Multi-Component systems

Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 2 / 10

 Phase Diagrams

A phase diagram is a diagram that

shows the state of a system under
varying conditions.
The state of a system under varying
T and P is termed the P-T diagram.
In a one-component system’s p − T
phase diagram, volume and the
molar amount n are kept constant.
line shows two(2) phases coexist
thermodynamically (phase
boundaries).

Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 3 / 10

 Phase Diagrams

A phase diagram is a diagram that

shows the state of a system under
varying conditions.
The state of a system under varying
T and P is termed the P-T diagram.
In a one-component system’s p − T
phase diagram, volume and the
molar amount n are kept constant.
line shows two(2) phases coexist
thermodynamically (phase
boundaries).

Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 3 / 10

 Phase Diagrams

A phase diagram is a diagram that

shows the state of a system under
varying conditions.
The state of a system under varying
T and P is termed the P-T diagram.
In a one-component system’s p − T
phase diagram, volume and the
molar amount n are kept constant.
line shows two(2) phases coexist
thermodynamically (phase
boundaries).

Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 3 / 10

 Phase Diagrams

A phase diagram is a diagram that

shows the state of a system under
varying conditions.
The state of a system under varying
T and P is termed the P-T diagram.
In a one-component system’s p − T
phase diagram, volume and the
molar amount n are kept constant.
line shows two(2) phases coexist
thermodynamically (phase
boundaries).

Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 3 / 10

 Phase Diagrams

The boiling equilibrium condition is most easily represented as a line on a

plot of the pressure, p against the temperature, T
A line of positive gradient, so any point on this line corresponds to the
situation where liquid and vapor are at equilibrium.
Away from the line, the equilibrium condition no longer applies; above the
line (at increased pressure and/or decreased temperature), only liquid exists,
whereas below the line (at increased temperature and/or decreased pressure)
there is only vapor.
The line terminates at c, the critical point where liquid and gas are
indistinguishable.
Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 3 / 10
 Phase Diagrams

The boiling equilibrium condition is most easily represented as a line on a

plot of the pressure, p against the temperature, T
A line of positive gradient, so any point on this line corresponds to the
situation where liquid and vapor are at equilibrium.
Away from the line, the equilibrium condition no longer applies; above the
line (at increased pressure and/or decreased temperature), only liquid exists,
whereas below the line (at increased temperature and/or decreased pressure)
there is only vapor.
The line terminates at c, the critical point where liquid and gas are
indistinguishable.
Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 3 / 10
 Phase Diagrams

The boiling equilibrium condition is most easily represented as a line on a

plot of the pressure, p against the temperature, T
A line of positive gradient, so any point on this line corresponds to the
situation where liquid and vapor are at equilibrium.
Away from the line, the equilibrium condition no longer applies; above the
line (at increased pressure and/or decreased temperature), only liquid exists,
whereas below the line (at increased temperature and/or decreased pressure)
there is only vapor.
The line terminates at c, the critical point where liquid and gas are
indistinguishable.
Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 3 / 10
 Phase Diagrams

The boiling equilibrium condition is most easily represented as a line on a

plot of the pressure, p against the temperature, T
A line of positive gradient, so any point on this line corresponds to the
situation where liquid and vapor are at equilibrium.
Away from the line, the equilibrium condition no longer applies; above the
line (at increased pressure and/or decreased temperature), only liquid exists,
whereas below the line (at increased temperature and/or decreased pressure)
there is only vapor.
The line terminates at c, the critical point where liquid and gas are
indistinguishable.
Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 3 / 10
 Phase Diagram

Line shows two(2) phases coexist thermodynamically (phase boundaries).

Boiling point is the temperature at which the vapor pressure of the liquid is
equal to the external pressure. When pressure is kept at 1 atm.
Melting point is the temperature at which the liquid and solid phases
coexist and equals the freezing temperature when pressure is kept at 1 atm.
Critical point is when liquid and vapor merge to form a supercritical fluid
Triple point is where 3 phases coexist.
Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 4 / 10
 Phase Diagram

Why is the phase diagram important?

These diagrams allow prediction of the nature of the phase(s) present for any
condition of p and T (any state point on the diagram).
, p, and T, which are both intensive variables, are all that is required to
specify the state of the system
The state is its molecular disposition or the number and amount of the
phases present and their composition
This is because although the pressure, p, the molar volume, Vm , and the
temperature, T, are the three intensive variables used to define the state of a
single substance system, these are linked by an equation of state
Knowledge of only two of these variables is necessary, as the equation of state
can be used to calculate the third and specify the state.

Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 4 / 10

 Phase Diagram

The solid phase is favored at low

temperatures and high pressures (low
volumes and entropies).
The gas (or vapor) is favored at high
temperatures and low pressures
(increased volumes and entropies).
The liquid is favored at intermediate
conditions, simplifying phase diagram
labeling.

Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 4 / 10

 Phase Diagram

The solid phase is favored at low

temperatures and high pressures (low
volumes and entropies).
The gas (or vapor) is favored at high
temperatures and low pressures
(increased volumes and entropies).
The liquid is favored at intermediate
conditions, simplifying phase diagram
labeling.

Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 4 / 10

 Phase Diagram

The solid phase is favored at low

temperatures and high pressures (low
volumes and entropies).
The gas (or vapor) is favored at high
temperatures and low pressures
(increased volumes and entropies).
The liquid is favored at intermediate
conditions, simplifying phase diagram
labeling.

Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 4 / 10

 Melting and Freezing Points

Melting and Freezing Points

A(s) ⇌ A(l) (⋆)

(1)

When a pure solid species is heated through its melting point (melting
temperature), the solid changes to a liquid. At the melting point, an
equilibrium is established between the solid and liquid phases.
The melting point and the freezing point are identical for a pure
substance, but not necessarily for a mixture.
Thus, a pure substance’s melting and freezing temperatures are identical; in
this case, the terms can be used interchangeably.
dG = Vdp − SdT
Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 5 / 10
 Melting and Freezing Points

Melting and Freezing Points

A(s) ⇌ A(l) (⋆)

(1)
At the melting point, equilibrium for pure species, A :
A(s) ⇌ A(l) (⋆)
∆G = 0... then, (28)
dp ∆S
= (29)
dT ∆V
Entropy and volume changes are positive
This means entropy increases at equilibrium as the solid melts, and volume
increases due to melting.
Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 5 / 10
 Melting and Freezing Points

Melting and Freezing Points

dp
In this case, is positive(+), and increasing the pressure increases the
dT
melting temperature.
A notable exception to this is water, as solid water (ice) has an
open-hydrogen-bonded structure, which occupies more volume than
liquid water.
dp
∆V is negative(-) and dT is positive(+).

Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 5 / 10

 Boiling and Condensation Points

Boiling and Condensation Point

A(l) ⇌ A(g ) (⋆)

dp ∆S
= (30)
dT ∆V

Entropy and volume changes are positive

Volume change, ∆V in a liquid-to-gas transition is larger than from
solid-to-liquid transition.
Volume occupied by 1 mole of gas is much larger than volume occupied by 1
mole of liquid.

Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 6 / 10

 Boiling and Condensation Points

A(l) ⇌ A(g ) (⋆)

dp ∆S
= (30)
dT ∆V

Volume change, ∆V in a liquid-to-gas transition is larger than from

dp
solid-to-liquid transition, this implies that dT has a larger impact on a
Boiling-Condensation process than on a Melting-Freezing process.
dp
A changed/increase in dT whiles attaining equilibrium will the increase
pressure which will compress the vapor volume. A compression of the vapour
volume will increase its density, whilst the increase in temperature tends to
weaken the liquid intermolecular forces, decreasing its density.
Eventually, at the critical point, characterized by a critical pressure and a
critical temperature, the densities of vapor and liquid become equal, the
two phases are indistinguishable and there is no longer any measurable
phase transition.
Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 7 / 10
 Phase Diagram - CO2

Phase Diagram of Carbon dioxide, CO2

CO2 is solid as dry ice and can also

sublime at 5 atm. At this point, the
solid and liquid phases coexists.
To form a liquid, pressure is required
An Increase in Pressure results in
increased melting point.
It can be a supercritical fluid where it
shows the properties of both a liquid
and gas.
A solid CO2 is stable at higher Temp
because it has a higher density.

Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 8 / 10

 Phase Diagram - CO2

Phase Diagram of Carbon dioxide, CO2

CO2 is solid as dry ice and can also

sublime at 5 atm. At this point, the
solid and liquid phases coexists.
To form a liquid, pressure is required
An Increase in Pressure results in
increased melting point.
It can be a supercritical fluid where it
shows the properties of both a liquid
and gas.
A solid CO2 is stable at higher Temp
because it has a higher density.

Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 8 / 10

 Phase Diagram - CO2

Phase Diagram of Carbon dioxide, CO2

CO2 is solid as dry ice and can also

sublime at 5 atm. At this point, the
solid and liquid phases coexists.
To form a liquid, pressure is required
An Increase in Pressure results in
increased melting point.
It can be a supercritical fluid where it
shows the properties of both a liquid
and gas.
A solid CO2 is stable at higher Temp
because it has a higher density.

Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 8 / 10

 Phase Diagram - CO2

Phase Diagram of Carbon dioxide, CO2

CO2 is solid as dry ice and can also

sublime at 5 atm. At this point, the
solid and liquid phases coexists.
To form a liquid, pressure is required
An Increase in Pressure results in
increased melting point.
It can be a supercritical fluid where it
shows the properties of both a liquid
and gas.
A solid CO2 is stable at higher Temp
because it has a higher density.

Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 8 / 10

 Phase Diagram - CO2

Phase Diagram of Carbon dioxide, CO2

CO2 is solid as dry ice and can also

sublime at 5 atm. At this point, the
solid and liquid phases coexists.
To form a liquid, pressure is required
An Increase in Pressure results in
increased melting point.
It can be a supercritical fluid where it
shows the properties of both a liquid
and gas.
A solid CO2 is stable at higher Temp
because it has a higher density.

Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 8 / 10

 Phase Diagram - H2 O

Triple point is formed at 273.15 K (zero

point on the Celsius scale) and 611 Pa.
Water is more stable with a negative
curve because it is denser than ice at
higher temperatures.

Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 9 / 10

 Phase Diagram - H2 O

Triple point is formed at 273.15 K (zero

point on the Celsius scale) and 611 Pa.
Water is more stable with a negative
curve because it is denser than ice at
higher temperatures.

Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 9 / 10

 Gibbs Phase Rule

Gibbs Phase Rule

F=C−P+2 (31)

A useful concept, especially when applied to multi-component

(multi-substance) systems.
The number of degrees of freedom, F , of the system. This is the minimum
number of intensive variables that can be varied without changing the
number of phases in the system.
C = components (compounds or chemical entities)
P = physical states
F = number of independent variables to vary (T , P, V , n)
The Gibbs phase rule allows calculation of the number of intensive parameters
that can be varied independently (F ) without disturbing equilibrium for a
given number of phases (P) and number of component (C ) system
Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 10 / 10
 Gibbs Phase Rule

Gibbs Phase Rule

F=C−P+2 (31)

A useful concept, especially when applied to multi-component

(multi-substance) systems.
The number of degrees of freedom, F , of the system. This is the minimum
number of intensive variables that can be varied without changing the
number of phases in the system.
C = components (compounds or chemical entities)
P = physical states
F = number of independent variables to vary (T , P, V , n)
The Gibbs phase rule allows calculation of the number of intensive parameters
that can be varied independently (F ) without disturbing equilibrium for a
given number of phases (P) and number of component (C ) system
Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 10 / 10
 Gibbs Phase Rule

Gibbs Phase Rule

F=C−P+2 (31)

A useful concept, especially when applied to multi-component

(multi-substance) systems.
The number of degrees of freedom, F , of the system. This is the minimum
number of intensive variables that can be varied without changing the
number of phases in the system.
C = components (compounds or chemical entities)
P = physical states
F = number of independent variables to vary (T , P, V , n)
The Gibbs phase rule allows calculation of the number of intensive parameters
that can be varied independently (F ) without disturbing equilibrium for a
given number of phases (P) and number of component (C ) system
Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 10 / 10
 Gibbs Phase Rule

Gibbs Phase Rule

F=C−P+2 (31)

A useful concept, especially when applied to multi-component

(multi-substance) systems.
The number of degrees of freedom, F , of the system. This is the minimum
number of intensive variables that can be varied without changing the
number of phases in the system.
C = components (compounds or chemical entities)
P = physical states
F = number of independent variables to vary (T , P, V , n)
The Gibbs phase rule allows calculation of the number of intensive parameters
that can be varied independently (F ) without disturbing equilibrium for a
given number of phases (P) and number of component (C ) system
Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 10 / 10
 Gibbs Phase Rule

Gibbs Phase Rule

F=C−P+2 (31)

A useful concept, especially when applied to multi-component

(multi-substance) systems.
The number of degrees of freedom, F , of the system. This is the minimum
number of intensive variables that can be varied without changing the
number of phases in the system.
C = components (compounds or chemical entities)
P = physical states
F = number of independent variables to vary (T , P, V , n)
The Gibbs phase rule allows calculation of the number of intensive parameters
that can be varied independently (F ) without disturbing equilibrium for a
given number of phases (P) and number of component (C ) system
Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 10 / 10
 Gibbs Phase Rule

Gibbs Phase Rule

F=C−P+2 (31)

A useful concept, especially when applied to multi-component

(multi-substance) systems.
The number of degrees of freedom, F , of the system. This is the minimum
number of intensive variables that can be varied without changing the
number of phases in the system.
C = components (compounds or chemical entities)
P = physical states
F = number of independent variables to vary (T , P, V , n)
The Gibbs phase rule allows calculation of the number of intensive parameters
that can be varied independently (F ) without disturbing equilibrium for a
given number of phases (P) and number of component (C ) system
Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 10 / 10
 Gibbs Phase Rule

Gibbs Phase Rule

F=C−P+2 (31)

A useful concept, especially when applied to multi-component

(multi-substance) systems.
The number of degrees of freedom, F , of the system. This is the minimum
number of intensive variables that can be varied without changing the
number of phases in the system.
C = components (compounds or chemical entities)
P = physical states
F = number of independent variables to vary (T , P, V , n)
The Gibbs phase rule allows calculation of the number of intensive parameters
that can be varied independently (F ) without disturbing equilibrium for a
given number of phases (P) and number of component (C ) system
Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 10 / 10
 Gibbs Phase Rule

F=C−P+2 (31)

For a double phase;

F = 1 - 2 + 2 = 1; only one
variable can be changed. e.g. T or
P (univariant)
For a single phase;
F = 1 - 1 + 2 = 2; two degrees of
freedom
For a triple phase;

F =1−3+2=0 (32)

Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 10 / 10

 Gibbs Phase Rule

F=C−P+2 (31)

For a double phase;

F = 1 - 2 + 2 = 1; only one
variable can be changed. e.g. T or
P (univariant)
For a single phase;
F = 1 - 1 + 2 = 2; two degrees of
freedom
For a triple phase;

F =1−3+2=0 (32)

Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 10 / 10

 Gibbs Phase Rule

F=C−P+2 (31)

For a double phase;

F = 1 - 2 + 2 = 1; only one
variable can be changed. e.g. T or
P (univariant)
For a single phase;
F = 1 - 1 + 2 = 2; two degrees of
freedom
For a triple phase;

F =1−3+2=0 (32)

Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 10 / 10

 Gibbs Phase Rule

F=C−P+2 (31)

For a double phase;

F = 1 - 2 + 2 = 1; only one
variable can be changed. e.g. T or
P (univariant)
For a single phase;
F = 1 - 1 + 2 = 2; two degrees of
freedom
For a triple phase;

F =1−3+2=0 (32)

Elliot S. Menkah, Ph.D. (KNUST) Phase Equilibria January, 2024 10 / 10