SCH 303:

THERMODYNAMICS &
PHASE EQUILIBRIA
Dr. Fredrick M. Mwazighe
Department of Chemistry
University of Nairobi

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Outline
• Review of the First law of thermodynamics and its shortcomings
• Spontaneous processes
• Second law of thermodynamics
• The Clapeyron/Clausius Equation
• Entropy change calculations for various processes
• Gibbs/Helmholtz free energy functions
• The Gibbs/Helmholtz equation
• Calculation of Gibbs free energy and equilibrium constant

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Outline contd..
• Gibbs phase rule
• Phase diagrams for one component systems
• Phase diagrams for two component systems
• Liquid systems
• Eutectics

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Course assessment
• Continuous Assessment Tests 30% (CATs and Practicals)
• Examination 70%
• Total 100%

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Core reading materials
• Atkins, P., de Paula J., Keeler, J., (2018), Physical Chemistry. 11th Edition.
Oxford

• Barrow, G.M., (2008). Physical Chemistry. McGraw Hill Education, New Delhi.

• Sharma K.K. and Sharma L.K., (2016) A textbook of Physical Chemistry 6eth
edition Vikas Publishing

• Seddon J.M., Gale J. D., (2002). Thermodynamics and Statistical mechanics

Royal Society of Chemistry
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Recommended reference materials
• Rankin, W. J. (2019). Chemical Thermodynamics: Theory and
Applications (1 edition). CRC Press.

• Klotz, I. M., & Rosenberg, R. M. (2000). Chemical Thermodynamics:

Basic Theory and Methods, 6th Edition (6th edition). Wiley-
Interscience.

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SYSTEMS AND STATE
• System: object under study at a given moment
• Surroundings: where observations are made. They remain at constant
temperature, volume or pressure regardless of how much energy flows
into or out of them.
There are 3 types of systems:
• Open system: can exchange both energy and matter with its
surroundings, hence can undergo changes of composition e.g flask, cell
• Closed system: can exchange energy but not matter with its surroundings
• Isolated system: can exchange neither matter nor energy with its
surroundings
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The state of a system is the circumstance in which it is found, expressed
by numerical values of a sufficient set of variables

A macroscopic system has two kinds of states: the macroscopic state,

which concerns only variables pertaining to the system as a whole and
the microscopic state , pertaining to the mechanical variables of
individual molecules
The equilibrium macroscopic state of a one-phase fluid system of one
component is specified by the values of three independent state
variables
All other macroscopic state variables are dependent variables, with
values given by mathematical functions of the independent variables

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The study of macroscopic properties involves thermodynamics
Thermodynamics is a branch of natural science that deals with the laws
of energy
There are different branches of thermodynamics:
Classical thermodynamics and Statistical thermodynamics
Classical thermodynamics:
Equilibrium or reversible thermodynamics
Irreversible thermodynamics

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Reversible classical
thermodynamics
Deals with matter in bulk and does not consider the behaviour of
individual particles.
There are two forms of energy which are important in this:
1. Thermal energy
2. Gibbs free energy

It deals with equilibrium conditions and there are two tendencies for
the system to get into equilibrium:
Lowest energy and maximum randomness
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Irreversible thermodynamics
Deals with fluxes/movement of matter

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Statistical thermodynamics
Deals with matter of individual particles
It uses spectroscopic and quantum laws
Classical thermodynamics Statistical thermodynamics

Gets its data from calorimetric Gets its data from spectroscopy
data/work i.e through experiments
specific heat capacities can be
determined under different conditions

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Applications of thermodynamics
To an engineer:

Calculation of the amount of work that can be derived from a given

specific amount of fuel

Determination of the efficiency of the system/machine

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To a manufacturing chemist:
The stability of the product is established
The maximum yield that can be expected from thermodynamic
calculations is obtained
Avoiding undesirable by-products by telling us the optimum conditions
of temperature and pressure expected
The proper choice of solvent for the synthetic chemist as well as the
analytical chemists

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Limitations of thermodynamics
It does not tell us when the reaction starts and how fast it goes or takes
place i.e in case calculations of thermodynamics indicates the
occurrence of the reaction

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Apart from the three major systems i.e. closed, open, and isolated
systems already described, other types of systems are:
Diathermic: where the system permits heating as a mode of transfer of
energy
Adiabatic: where the system does not permit heating even though
there is a difference in temperature
Other processes include:
A process in a system that heats the surroundings is called exothermic

A process in a system that is heated by the surroundings is called

endothermic

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What is a state of a system?
It is the condition of the system when its macroscopic properties have
definite measurable values

If any of the macroscopic properties of a system changes, such as

temperature and pressure, the state of the system also changes

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What is a state variable?
It is the measurable property required to describe the state of a system
i.e. temperature, pressure, volume

For any system, a certain minimum number of variables are sufficient to

define its state as the other variables become automatically fixed

Considering a system consisting of an ideal gas, the state may be

defined by only 3 variables such as temperature, pressure and volume.
PV = nRT

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Other variables such as amount of gas, density etc will be definite and
can easily be calculated

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What is a state function?
This is a property where values depend on only the state of a system
and does not depend on the path by which the change from initial to
final step is brought about. The change in the value of the state
function depends only upon initial and final state of the system

Some common state functions are pressure P, volume V, temperature T,

internal energy E or U, enthalpy H, entropy S, and free energy G.

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What are state properties?
State variables and functions may possess either extensive or intensive
properties

Extensive properties: are those whose values are dependent on

quantity of matter contained in any system or state of a system. E.g.
mass, volume, area, energy, no. of moles, enthalpy, entropy etc.

Intensive properties: depend on the nature of a substance/system but

are independent of its amount or size in the system. E.g. density,
viscosity, surface tension, temperature, pressure etc.
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State processes: is an occurrence that changes the state of a system.
E.g
Isothermal process: is that in which the temperature of the system
remains constant ΔT = 0
Adiabatic process: no exchange of heat between the system and the
surroundings Δq = 0
Isobaric process: where the pressure of the system remains constant
during any operation ΔP = 0
Isochoric process: is that in which the volume of a system does not
change
Cyclic process: is one in which the system returns to its initial state
after undergoing a series of changes

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Reversible change (quasi-equilibrium/ quasi-static):
This is when a process is carried out slowly so that the system and the
surroundings are always in equilibrium

Irreversible process:
This is carried out rapidly so that the system does not return to its
initial state

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First Law of Thermodynamics
States that: energy can be converted from one form to another, but it
cannot be created or destroyed
It expresses the conservation of energy principle where one form of
energy can change into another form but the total energy remains the
same
It helps balance the internal energy, heat released and work done in
the process
However, it does not say whether the process of change we specify
can occur and if so, in which direction
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When a system is changed from state A to state B, it undergoes a
change in the internal energy from to . We can write:

This energy change is brought about by the evolution or absorption of

heat and/or by work done on or by the system.
Because the total energy of the system must remain constant the
mathematical statement of the First law is:
…… Equation 1
q is the heat exchange between the system and the surroundings
w is the work done on or by the system
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For a gas expanding against an applied constant pressure by volume ΔV,
the total mechanical work done is given by:

Combining with equation 1 and 2 we get:

For infinitesimal change in energy we write

dU = dq-pdV
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Case I: For a cyclic process involving isothermal expansion of an ideal
gas

ΔU = 0 and therefore q = -w

Case II: For an isochoric process there is no work of expansion i.e

W = 0, hence

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Case III: for an adiabatic process there is no change in heat gained or
lost i.e

q = 0, hence ΔU = w

Case IV: For an isobaric process there is no change in pressure i.e.

P remains constant, hence ΔU = q + w

ΔU = q - PΔV

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Find ΔU, q, and w if 2 moles of hydrogen at 3 atm expand
isothermally at 50 °C and reversibly to a pressure of 1 atm.

Since the operation is isothermal and the gas is ideal

ΔU = 0

From the 1st law: ΔU = q + w

q + w = 0 when ΔU = 0 or q = -w

For a reversible process: w = -nRT ln

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= -2 × 1.987 × 323 × 2.303 × log 3
= - 1410 cal

Since q = -w

q = 1410 cal

Exercise

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Work and heat are not state functions

Work done does not only depend on the initial and final state, but they
also depend on how the process was carried out i.e the path

Heat and work are not state functions because they not properties of a
system. They manifest themselves only during a process (during a
change)

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 Enthalpy
Enthalpy (H), also known as heat content is defined as:
H = U + PV
Enthalpy is a state function and a change of enthalpy can be measured
from a change in internal energy and change in the product PV
dH = dU + PdV + VdP
We can have two processes: a pressure constant process and a volume
constant process for enthalpy

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 Pressure constant process
dH = dU + PdV + VdP
With pressure constant, dP = 0

From the First Law of Thermodynamics

We know that = ,
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 Constant Volume Process

dU = dq – PdV

But

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Since and
Then

When n = 1,
=R
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Spontaneous Processes
One of the main reasons for studying thermodynamics for chemists is to
be able to predict whether or not a reaction will occur when reactants
are brought together under a specific set of conditions
A reaction that does occur under the given set of conditions is called a
spontaneous reaction
If it does not occur under specified conditions, it is said to be
nonspontaneous

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Examples of spontaneous physical and chemical processes are:
1. A waterfall runs downhill, but never up, spontaneously
2. A lump of sugar spontaneously dissolves in a cup of coffee, but
dissolved sugar does not spontaneously reappear in its original form
3. Water freezes spontaneously below 0 , and ice melts spontaneously
above 0 °C (at 1 atm)
4. Heat flows from a hotter object to a colder one, but the reverse
never happens spontaneously
5. The expansion of a gas into an evacuated bulb is a spontaneous
process. The reverse, i.e the gathering of all the molecules into one
bulb, is not spontaneous

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6. A piece of sodium metal reacts violently with water to form sodium
hydroxide and hydrogen gas. However, hydrogen gas does not
spontaneously react with sodium hydroxide to form water and
sodium
7. Iron exposed to water and oxygen forms rust, but rust does not
spontaneously change back to iron

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Criteria of Spontaneity
1. A spontaneous change is one way or unidirectional. For reverse
change to occur, work has to be done
2. For a spontaneous change to occur, time is not a factor i.e. a
spontaneous change may take place rapidly or very slowly
3. If the system is not in an equilibrium state (unstable), a spontaneous
change is inevitable. The change will continue until the system
attains the state of equilibrium
4. Once a system is in equilibrium state, it does not undergo any further
spontaneous change in state if left undisturbed. To take the system
away from equilibrium, some external work must be done on system
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Criteria of Spontaneity
5. A spontaneous change is accompanied by decrease of internal
energy or enthalpy ΔH

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If we assume that spontaneous processes occur so as to decrease the
energy of a system, we can explain why a ball rolls down hill and why
springs in a clock unwind. Similarly, a large number of exothermic
reactions are spontaneous. E.g.
CH4(g) + 2O2(g) ⟶CO2(g) + 2H2O(l) ΔH° = −890.4
kJ/mol

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But when you consider a solid-liquid phase transition like:
H2O(s) ⟶H2O(l) ΔH° = 6.01 kJ/mol
The assumption that spontaneous processes always
decrease a system’s energy fails. Ice melts
spontaneously above 0 °C even though the process is
endothermic
We can say: Exothermicity favours the spontaneity
of a reaction but does not guarantee it
We cannot decide whether or not a chemical reaction will
occur spontaneously solely on the basis of energy
changes in the system
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Another thermodynamic quantity is needed: Entropy
 Entropy (S)
Is a measure of the randomness or disorder of a system
The greater the disorder, the greater the entropy
A deck of cards can be used to illustrate entropy:

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 An ordered state has a low probability of
occurring and a small entropy, while a disordered
state has a high probability of occurring and a
large entropy

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 Microstates and Entropy
The probability of
occurrence of a
particular distribution
(state) depends on the
number of ways
(microstates) in which
the distribution can be
achieved
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Boltzmann (1868) showed that the entropy of a system is related to the
natural log of the number of microstates (W):
S = klnW
k is the Boltzmann constant J/K
Entropy is a state function. Thus

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Entropy and Disorder

More
particles lead
to increase in
microstates
hence
increase in
entropy
except in
hydration
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 Heating also increases the entropy of a system

This increase in energy is distributed or dispersed among the quantized

energy levels. Consequently, more microstates become available at a
higher temperature; therefore, the entropy of a system always increases
with increasing temperature
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 Standard Entropy
Is the absolute entropy of a
substance at 1 atm and 25 °C
Entropy is obtained by
calorimetric methods unlike
energy and enthalpy where only
the change can be determined

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 The Second Law of
Thermodynamics
It links entropy and the spontaneity of a reaction
It states:
‘The entropy of the universe increases in a spontaneous process and
remains unchanged in an equilibrium process’
For a spontaneous process:
For an equilibrium process:

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For a spontaneous process, the second law says that must be greater
than zero, but it does not place any restriction on or

For an equilibrium process, is zero. In this case and must be equal in

magnitude, but opposite in sign

For a hypothetical process where is negative, the process is not

spontaneous in the direction described but spontaneous in the
opposite direction

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 Entropy Changes in the System
To calculate we need both and
If the system is represented by the reaction:

The standard entropy of reaction is given by:

In general:
Where m and n are the stoichiometric coefficients in the reaction

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From the above examples:
1. If a reaction produces more gas molecules than it consumes, is
positive

2. If the total number of gas molecules diminishes, is negative

3. If there is no net change in the total number of gas molecules, then

may be positive or negative, but will be relatively small numerically
These make sense because gases have greater entropy than liquids and
solids

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Entropy Changes in the
Surroundings

For constant-pressure
processes the heat change
∆ 𝑺 𝒔𝒖𝒓𝒓 𝜶 − ∆ 𝑯 𝒔𝒚𝒔 is equal to enthalpy change
of the system
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The minus (-) is used if the process is exothermic, is negative and is a
positive quantity, indicating an increase in entropy.
For an endothermic process, is positive and the negative sign ensures
that the entropy of the surroundings decreases
The change in entropy for a given amount of heat absorbed also
depends on the temperature.
If the temperature of the surroundings is high, the molecules are
already quite energetic. Absorption of heat from an exothermic process
in the system will have relatively little impact on molecular motion and
the resulting increase in entropy of the surroundings will be small

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However, if the temperature of the surroundings is low, addition of the
same amount of heat will cause a more drastic increase in molecular
motion and hence a larger increase in entropy

For:
Calculate and and determine whether the reaction is spontaneous.

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NOTE: Just because a reaction is spontaneous does not mean that it will
occur at an observable rate. E.g. the synthesis of ammonia is, in fact,
extremely slow at room temperature
Thermodynamics can tell us whether a reaction will occur
spontaneously under specific conditions, but it does not say how fast it
will occur. That is the focus of chemical kinetics

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 The Third Law of
Thermodynamics and Absolute
Entropy
Consider a perfectly crystalline substance at absolute zero (0 K)
Molecular motions are at a minimum and the number of microstates (W)
is one

= k ln 1 = 0
Third law of thermodynamics states:
The entropy of a perfect crystalline substance is zero at the absolute zero
of temperature
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The entropy of any substance at a temperature above 0 K is greater
than zero
If the crystal is impure or if it has defects, its entropy is greater than
zero even at 0 K, because it would not be perfectly ordered and the
number of microstates would be greater than one
The 3rd law of thermodynamics enables us to determine the absolute
entropies of substances
Starting with the knowledge that the entropy of pure crystalline
substances is zero at absolute zero, we can measure the increase in
entropy of the substance when it is heated from 0 K to say 298 K

=
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Because they are determined at 1 atm, absolute entropies are called
standard entropies
The numerical definition of entropy was introduced by Clausius (1850)
According to him the entropy of a system (not undergoing chemical or
physical changes) is a constant quantity when there is no flow of heat
When heat (q) flows into the system, the entropy increases by
Heat flowing out of a system produces a corresponding decrease
For a reversible change taking place at a fixed temperature T, the
change in entropy is equal to the heat absorbed or evolved divided by
the temperature T

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Units of Entropy
Entropy is equal to heat energy divided by the absolute temperature
and therefore it is measured in entropy units (eu) which are calories per
degree per mole i.e. c
The SI units are joules per mole per degree i.e. J

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Definitions
1. Cyclic Process
When a system undergoes a series of changes and in the end returns to
its original state, it is said to have completed a cycle. This whole process
comprising the various changes is called a cyclic process

Since the internal energy of a system depends on its state, it implies

that for a cyclic process the net change of energy is zero. Thus, the
work done by the system during all these changes is equal to the heat
absorbed by the system

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2. Heat engines

The flow of heat from a hot body to a cold body is a spontaneous

process

A machine which can do work by using heat that flows out

spontaneously from a high temperature source to a low temperature
sink is called a heat engine

A heat engine takes heat energy from a high temperature reservoir and
converts some of it into work, returning the unconverted heat to a low
temperature sink

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Principle of a Heat Engine
A steam engine is a typical heat engine. It takes heat from the boiler
(high temperature source), converts some heat to work and returns the
unused heat to the surroundings (low temperature sink)

A heat engine running on a periodic cyclic process can yield work

continuously

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3. Efficiency of a Heat Engine

The ratio of the work obtained in a cyclic process, w, to the heat taken
from the high temperature reservoir, q, is referred to as the efficiency
of a heat engine

No heat engine can convert all the heat from a high temperature
reservoir into work. Such an engine would be 100% efficient

Sadi Carnot was the first scientist to discover this and deduced an
expression showing the limitations of heat engines

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The Carnot Cycle
Carnot proposed a theoretical heat engine to show that the efficiency
was based upon the temperatures between which it operated

The Carnot’s imaginary engine could perform a series of operations

between temperatures , so that at the end of these operations the
system was restored to the original state

This cycle of processes which occurred under reversible conditions is

referred to as the Carnot’s cycle

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The medium employed in operating Carnot’s engine was 1 mole of an
ideal gas which could be imagined to be contained in a cylinder fitted
with a frictionless piston

The Carnot cycle comprises four operations or processes

1. Isothermal reversible expansion

2. Adiabatic reversible expansion

3. Isothermal reversible compression

4. Adiabatic reversible compression

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First operation-Isothermal
Operation
Let be the temperature, pressure, and volume respectively of the gas
enclosed in the cylinder initially

The cylinder is placed in the heat reservoir at the higher temperature

The gas is allowed to expand isothermally and reversibly so that the

volume increases from to . AB represents the path of the process in the
diagram

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Work done:
Since the process in operation 1 is isothermal,
If is the heat absorbed by the system and the work done by it,
according to the first law equation ()

But
Therefore

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Second Operation- Adiabatic
Reversible Expansion
The gas at B is at a temperature and has a volume under the new
pressure
The gas is allowed to expand reversibly from volume to when the
temperature drops from to (along BC)
Work done:
Since this step is adiabatic, q = 0
If is the work done, according to the first law equation (ΔU = q + W)

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Third Operation- Isothermal
Reversible Compression
The cylinder is now placed in contact with a heat reservoir at a lower
temperature,

The volume of the gas is then compressed isothermally and reversibly

from (represented by CD in the diagram).

Work done:

During compression, the gas produces heat which is transferred to the

low temperature reservoir

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Since the process takes place isothermally, ΔU = 0

If is the heat given to the reservoir and the work done on the gas,
using proper signs for q and W, we have

(-)

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Fourth operation – Adiabatic
Reversible Compression
The gas with volume and temperature at D is compressed adiabatically
(along DA) until it regains the original state i.e. the volume of the
system becomes and the temperature

Work done:
In this step work is done on the system
If it is denoted by , therefore

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Net Work Done in One Cycle
Adding up the work done in all the four operations of the cycle

Net heat absorbed in one cycle:

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Therefore the efficiency of a Carnot engine, the most ideal of all
engines is limited by the operating temperatures of the engine

The larger the temperature difference between the high and low
temperature reservoirs, the more the heat converted to work by the
heat engine

For a given temperature of the high temperature reservoir, the lower

the temperature of the sink, the greater will be the efficiency of the
machine. Similarly, for a given temperature of the sink, the efficiency
will be increased by using a high temperature of the source reservoir

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 Carnot Theorem
We have seen that

For a perfect gas, this result depends on the temperature limits

between which the cycle operates and is independent of all other
factors

This relation is known as the CARNOT THEOREM which states that:

every perfect engine working reversibly between the same temperature
limits have the same efficiency, whatever the working substance

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More Statements of the Second
Law
From
It is evident that is less than 1 or is greater than W. This means that
heat transferred by a spontaneous process is never completely
converted into work (if so would be 1)

This leads to another statement of the second law (by Lord Kelvin)
which states that it is impossible to take heat from a hotter reservoir
and convert it completely into work by a cyclic process without
transferring a part of the heat to a cooler reservoir

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The statement recognizes the fact that heat engines can never be 100%
efficient since some heat must be returned to a low temperature
reservoir

Another statement of the second law is given by Clausius which states:

it is impossible to transfer heat from a body at a lower temperature to
one at a higher temperature without at the same time converting
some work to heat

This statement recognizes that heat flows spontaneously from hot

objects to cold objects and for it to flow in the opposite direction work
has to be expended

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Example 1
An engine operating between 150 and 25 takes 500 J heat from a high
temperature reservoir. Assuming there are no frictional losses, calculate
the work that can be done by this engine.

From

Substituting the values

; W= 147.75 J
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Example 2
The boiling point of water at a pressure of 50 atmospheres is 265 .
Compare the theoretical efficiencies of a steam engine operating
between the boiling point of water at :
i. 1 atmosphere
ii. 50 atmospheres, assuming the temperature of the sink to be 35 in
each case

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At 1 atmosphere:

Efficiency =

At 50 atmospheres:

Efficiency =

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Example 3
If a Carnot engine operating between two heat reservoirs at 227
absorbs 1000 calories from 227 reservoir per cycle, how much heat is
discharged into the 27 reservoir and how much work is done per cycle?
What is the efficiency of the cycle?

(a) We know that

W = 400 calories (work done per cycle)

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(b) The heat from the higher temperature reservoir minus the heat
discharged into the low temperature reservoir , is converted into work,
W. Thus

1000

(c) Efficiency:

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PHYSICAL SIGNIFICANCE OF ENTROPY

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Example 2

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Determination of Entropies of Substances
(Third Law of Thermodynamics

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