MSE616: Thermodynamics of Materials

2021-22 – II Semester

Lecture # 2

1
 MSE616: Thermodynamics of Materials
Thermodynamics is the study of the state of the system and its properties,
changes to the state of the system and the relationships that govern these
properties and changes to the properties of the system.
The Laws of Thermodynamics govern these relationships.
The laws of thermodynamics are highly condensed expressions of a broad body
of experimental evidence – The laws are empirical (i.e., derived from
experimental observations).
 There exists a property of the universe, called its energy, which cannot change
no matter what processes occur.
 There exists a property of the universe, called its entropy, which always changes
in the same direction no matter what processes occur.
 There exists a lower limit to the temperature that can be attained by matter,
called the absolute zero of temperature, and entropy of all substances is the
same at that temperature.
 MSE616: Thermodynamics of Materials
The First Law of Thermodynamics: There exists a property of the universe,
called its energy, which cannot change no matter what processes occur. Energy is
conserved.
 Kinetic Energy: motion, translation, rotation etc.
 Potential Energy: position of body or particle in a potential field (gravitational,
electrostatic etc.)
 Internal Energy: associated with the internal condition of the body or system,
does not depend upon its motion or position in space.
Energy can be transported or converted from one form to another but cannot be
created or destroyed.
The only way that the internal energy of a system can change is by transferring
energy across its boundary to surroundings by means of ‘heat’ or ‘work’ or both.
Mathematically, the change in internal energy (U) of a system for a process must be
equal to the sum of all energy transfers across the boundary of the system during the
process.

3
 MSE616: Thermodynamics of Materials

U – a thermodynamic state function called internal energy

Q – the quantity of heat that flows into the system during the process
W – mechanical work done on the system by force exerted by the external pressure
in the surrounding (PV work)
W’ – all other kinds of work done on the system during the process

– differential of the state function, – non-differentiable as Q, W and W’ are not state functions
 MSE616: Thermodynamics of Materials
The Second Law of Thermodynamics: There exists a property of the
universe, called its entropy, which always changes in the same direction no matter
what processes occur.
 Similar to the first law, the second law of thermodynamics is general and
pervasive.
 No step in the process is exempt from its application.
 It applies microscopically to every volume element in a system that is
experiencing change.
 It applies during each infinitesimal increment of time in the process.
Specifically, in every volume element of any system and its surroundings that may be
experiencing change, at every instant of time, the entropy production is positive.
However, this does not imply that the entropy of a system can only increase.
Just like energy, entropy can be transferred across boundary of a system in
association with heat, work or mass transfer. However, unlike energy, the change in
entropy of a system is not restricted to entropy transfer across its boundaries. There is
an additional contribution, namely the production of entropy inside the system.
 MSE616: Thermodynamics of Materials
The first law is a conservation law; the second law is not.
∆ 𝑆𝑠𝑦𝑠 =∆ 𝑆𝑡 +∆ 𝑆𝑝
- the entropy transferred across the boundary
- the entropy production inside the system
The transfer term () may be positive or negative depending upon the nature of the
process and the flows at the boundary of the system. The second law states that for
all processes, for all systems
The entropy of a system may decrease for a given process.
System + Surroundings = Universe

“Entropy is times arrow.” Sir Arthur Eddington, The Nature of the Physical World
 MSE616: Thermodynamics of Materials
Reversible and Irreversible Processes
 MSE616: Thermodynamics of Materials
For a process carried out reversibly, there are no dissipations, no entropy production
and no permanent changes in the universe (system + surroundings). Irreversible
processes are accompanied by dissipation of energy, finite entropy production and
permanent changes in the universe.
Calculation of process variables (heat exchange, work done) is relatively easy for
reversible processes primarily because each intermediate step is described by few
parameters (state functions). On the other hand, calculation of process variables for
an irreversible process is extremely complicated as it requires specification of
variation with time and position for the state functions.
Calculation of changes in state functions can be straight forward for both, reversible
and irreversible processes as the state functions only depend on the end points and
not on the path taken to get there.
Mixing of two gases, spontaneous combustion, transfer of energy as heat from a hot
body to cold body are some of the clear examples of irreversible processes.
 MSE616: Thermodynamics of Materials
Relationship between entropy transfer and heat absorbed: Quantitative treatment
of entropy transfer for reversible processes establishes a connection between the
reversible heat flow across the boundary of the system and change in system’s
entropy.
On a macroscopic level, the increase in entropy due to a quasi-static change in which
an infinitesimal amount of heat () is absorbed by system is given by

Consider two bodies A and B in thermal contact but cannot do work on one another
and are isolated from all other surroundings.

𝑑𝑄
A B
T T’
T’ > T
 MSE616: Thermodynamics of Materials
Heat absorbed by body A =
Heat absorbed by body B =
Change in entropy of body A:

Change in entropy of body B:

Overall:

Spontaneous flow of heat between bodies at different temperatures is always an

irreversible process that increases the entropy of the universe.
 MSE616: Thermodynamics of Materials
Example
P1, V1, T1 vacuum P2, V2, T2

Free Expansion
Isolated System:
To restore the original state, you can compress the gas isothermally in quasi-static
manner

In the restoring process, work is done on the system by surrounding and heat is
dissipated to the surrounding and hence free expansion of gas is an irreversible
process.
 MSE616: Thermodynamics of Materials

vacuum

vacuum

P1, V1, T1 P2, V2, T2 P3, V3, T3

Reversible Expansion: no permanent change in surroundings or universe

 MSE616: Thermodynamics of Materials
Entropy Change for reversible and irreversible processes: For a reversible
process that changes the state of a system from A to A’, the change in entropy is
completely due to transfer of heat across the boundary ().
For an irreversible process that changes the state of a system, the changes in entropy
for the process will be same as . However, it must also include another term reflecting
the production of entropy and hence the entropy transfer for irreversible process will
be smaller compared to reversible process.
 MSE616: Thermodynamics of Materials
Combined statement of First and Second Laws of Thermodynamics

For reversible process, only if at each infinitesimal step in the process

and

This is combined statement of the first and second laws of thermodynamics.

 MSE616: Thermodynamics of Materials
The Third Law of Thermodynamics: There exists a lower limit to the
temperature that can be attained by matter, called the absolute zero of temperature,
and entropy of all substances is the same at that temperature. and at .
Example: Consider a cyclic process

∆ 𝑆𝑐𝑦𝑐 = ∆ 𝑆 𝐼 + ∆ 𝑆 𝐼𝐼 + ∆ 𝑆 𝐼𝐼𝐼 +∆ 𝑆𝐼𝑉 =0

 MSE616: Thermodynamics of Materials
However, , , and calculated from the experimental measurements (with in the
experimental error limit) show that

Hence,

This suggests that at 0K, the entropy of the compound is same as for and at 0K
and can be assigned an arbitrary value of 0.
The change in entropy for can be evaluated by measuring heat capacity during the
process III which is not equal to the change in entropy measured for or .
 MSE616: Thermodynamics of Materials
Thermodynamic Variables and Relations
Q – heat absorbed by the system (joules)
W – mechanical work done on the system (joules)
W’ – all other types of work done on the system other than mechanical work (joules)
T – absolute temperature (K)
P – pressure (atm)
V – volume (cubic meter, m3)
U – internal energy of the system (K)
S – entropy (joules/K)

The relationships presented here are the definitions of some important

thermodynamic variables which can be classified into two categories: energy
function and experimental variables
 MSE616: Thermodynamics of Materials
Energy Functions

Enthalpy (H):
is a state function as it is defined in terms of other state functions.

This is an alternate form of combined 1st and 2nd law. If and for isobaric processes

For isobaric processes with no non-mechanical work, change in state function,

enthalpy () is direct measure of reversible heat transfer during the process.
 MSE616: Thermodynamics of Materials

Helmholtz Free Energy (F):

is a state function

For an isothermal process,

For an isothermal process the change in Helmholtz free energy () reports the
total work done on the system.
 MSE616: Thermodynamics of Materials

Gibbs Free Energy (G):

is a state function

For an isothermal and isobaric process, and

For an isothermal and isobaric processes such as frequently encountered in

laboratories the change in Gibbs free energy () reports the total non-mechanical
work done on the system such as during the process of phase transformation,
chemical reactions etc.
 MSE616: Thermodynamics of Materials
Experimental variables:
Volume thermal expansion coefficient:

Isothermal compressibility or coefficient of compressibility:

Heat Capacity:
constant pressure heat capacity,

for a reversible process

 MSE616: Thermodynamics of Materials
Empirically, is described by four parameters, a, b, c and d which are tabulated for
various materials

constant volume heat capacity,

and

For a system at constant pressure, the heat absorbed by system is used in raising
temperature as well as increasing the volume. Hence, it can be surmised (and is
generally observed) that the heat required to raise temperature by one degree would
be larger at constant pressure compared to constant volume process ().
 MSE616: Thermodynamics of Materials
Coefficient Relations: A variety of relationships exist between different
thermodynamic functions and variables and under certain conditions (such as
constant pressure, temperature etc.), these can be used to extract valuable
information from experimentally recorded parameters.

These relationships are a consequence of some basic mathematical relationships.

Suppose , and are state functions and there exists a relationship between them and
given any two values the third can be evaluated (e.g for ideal gas).

The differential form of is given by

 MSE616: Thermodynamics of Materials
Thermodynamic Relations and Thermodynamic Square:
Thermodynamic square as shown in the figure on the right can
be used to define relationships between various parameters.
The functions in “red” are thermodynamic potentials or energy.
General scheme:
1. Identify one thermodynamic potential.
2. The two corners on the opposite side represent the
coefficients of the overall result.
3. In the opposite corner from the coefficients, we have the
associated differential.
4. An additional term may be added where denotes chemical
potential and is number of moles.

Ref: https://en.wikipedia.org/wiki/Thermodynamic_square
 MSE616: Thermodynamics of Materials
Maxwell Relations: A category of thermodynamic relations that define the
relationships between various first order derivatives of thermodynamic variables.
Consider a state variable which is a function of two other variables, and . A property
of state functions is that the order of differentiation does not matter and hence we have

Which can be re-written as

If state functions and are defined as

Then