Chemical Engineering Dept.

- NED University

M.Engg. Fall 2013

CH-501 “Chemical Thermodynamics-III”

By
Dr.-Ing. Syed Mushahid Hussain Hashmi
Prof. / Chairman
Dept of Automotive & Marine Engineering
Ext: 2539 email: mushahid@neduet.edu.pk

Ph.D- Mechanical (Institute of Thermodynamics, HSU, Hamburg, Germany)-2010

M.Sc-Energy Systems (NED)-2002
B.E -Mechanical ( NED)-1997

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (lecture 1-Introduction) 1

 Introduction to Thermodynamics

Thermodynamics thermo=heat dynamics=motion

19th century idea of conversion of heat into motion.

Guggenheim called thermodynamics a misnomer. In dynamics or

motion time is always a parameter, but classical thermodynamics is
based on the concept of equilibrium. He suggested thermostatic or
thermo-physics.

Thermodynamics is a tool concerned with Energy and its

transformations.

More specifically it deals with relative energy levels and transfers of

energy between systems and between different states of matter.

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (lecture 1-Introduction) 2

 Introduction to Thermodynamics

“Thermodynamics is the only science about which I am firmly

convinced that, within the framework of the applicability of its
basic principles, it will never be overthrown.”
Albert Einstein

• Describe macroscopic properties of equilibrium systems

• Entirely empirical
[concept of atoms and molecules developed later]

• Built on 4 laws and simple mathematics

• These laws are Universally Valid, they cannot be circumvented

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (lecture 1-Introduction) 3

 Why thermodynamics is challenging?

Scope- large number of relations and diverse applicability

Abstract nature- comprises of abstract properties e.g entropy, chemical

potential, fugacity

Modeling abstraction - Real=ideal + correction OR Real=Ideal ×

correction

Thermodynamics is powerful tool providing a framework for solving a

myriad of real life engineering problems.

Thermodynamics ↔ economy of thought

Engineering ↔ economy of resources

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (lecture 1-Introduction) 4

 Chemical Thermodynamics

• Maximum work obtainable from any physical and chemical process or

minimum work required to drive a process

• Maximum possible yield of industrial processes [e.g yield of ammonia

from nitrogen and hydrogen]

• Establishment of relationship among variables [fewer experimental data]

• Study of mixtures [liquid mixture boiling-distillation-crystallization]

• Composition of phases

• Establish a criterion for determining the feasibility or spontaneity of

physical or chemical transformation

• Energy changes associated with physical or energy transformation.

• Establish a criterion for determining the feasibility of mass transport.

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (lecture 1-Introduction) 5

 Recommended books
1. Chemical Thermodynamics: Principles and Applications by J. Bevan Bevan
Ott, Juliana Boerio-Goates, ELSEVIER

2. Introduction to Chemical Engineering Thermodynamics by J.M. Smith,

Hendrick Van Ness , Michael Abbott, 7 e/d, MCGRAW HILL

3. Chemical Thermodynamics-Basic Concepts and Methods by I. M. Klotz, R

M. Rosenberg, WILEY.

4. Engineering and Chemical Thermodynamics by Milo D Koretsky WILEY

5. Thermodynamics – A Core Course 3 e/d by Srivastava, Saha, Jain

PRENTICE HALL INDIA

6. Introduction to Chemical Engineering Thermodynamics by Gopinath Halder,

PHI Learning Pvt Ltd, India

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (lecture 1-Introduction) 6

 Language of Thermodynamics

“Beginning is the most important part of the work.”

Plato (427-347 BC)

System- The part of the universe that is at the center of attention.

Surroundings- the rest of the universe.

Universe =system + surroundings

Boundary- system is always defined by its boundaries

Open system- both mass and energy can flow across the boundary
[control volume]

Closed system- no mass flow across the boundary [control mass]

Isolated system- neither mass nor energy crosses the boundary

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (lecture 1-Introduction) 7

 Language of Thermodynamics

Properties-parameter or variables characterizing the system [e.g P,V, T ]

Intensive properties- independent of the quantity of matter in a system

[e.g T, P,density]

Extensive properties- dependent of the quantity of matter in a system

[Energy, Volume]

Homogeneous system- Properties are same throughout the system or vary

continuously from point to point with no discontinuities

Heterogeneous system- A system consist of two or more homogeneous

systems separated by a physical boundary or surfaces of discontinuities
[atmosphere with clouds, ice water mixture]

Phase- uniform physical structure and uniform composition e.g solid,

liquid, gas

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (lecture 1-Introduction) 8

 Equilibrium- Example of water in beaker

Take water in a beaker at 80 ºC while the room temperature is 30 ºC.

Monitor the temperature of water with time.

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (lecture 1-Introduction) 9

 Steady State- Seral’s Experiment

Take Seral’s experiment, thermal conductivity of metallic rod. By

continuously supplying energy we can maintain temperature invariant of
time, even though the temperatures are different at different positions.

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (lecture 1-Introduction) 10

 Equilibrium and Steady State

Both are steady state situations, but beaker example is of equilibrium.

A healthy human body maintains a constant temperature of 37 ºC, which

does not depend on ambient temperature.

Equilibrium state is only a subset of steady state. In both equilibrium and

steady state the system shows no further tendency to change its properties
with time.

dφ
=0 where φ is any property
dt

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (lecture 1-Introduction) 11

 Equilibrium- Example

Consider a solid block resting on the table:

A and C are in equilibrium, while B is unstable equilibrium. C is the

most stable equilibrium position. A criterion for this mechanical system
in equilibrium is the potential energy should be minimum.

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (lecture 1-Introduction) 12

 Equilibrium State

Consider a ball rolling in a valley:

The ball will spontaneously roll
downhill, losing potential energy as it
goes, to the lowest point it can reach.

Equilibrium states in systems have two attributes:

1. A system at equilibrium has none of its properties changing with

time, no matter how long it is observed.

2. A system at equilibrium will return to that state after being disturbed,

that is, after having one or more of its parameters slightly changed,
then changed back to the original values.
CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (lecture 1-Introduction) 13
 Equilibrium-Stable, Unstable, Meta-stable

Stable and meta-stable are the terms used to describe the system in its
lowest equilibrium energy state and any other equilibrium energy state,
respectively.

Four positions of a ball on a surface, to illustrate the concept of

equilibrium.
Position a – meta-stable equilibrium. Position b – unstable.
Position c – unstable. Position d – stable equilibrium.
CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (lecture 1-Introduction) 14
 Equilibrium-Ice water Example

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (lecture 1-Introduction) 15

 Equilibrium-Diamond Graphite Example

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (lecture 1-Introduction) 16

 Equilibrium- Mechanical

If the gases in these two containers are at different pressures, when

the pins holding the pistons are released, the pistons move one way
or the other until the two pressures are the same. The two systems
are then in mechanical equilibrium. If the pressures are the same to
begin with, there is no movement of the pistons when the pins are
withdrawn, for the two systems are already in mechanical
equilibrium.
CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (lecture 1-Introduction) 17
 Zeroth Law of Thermodynamics

if A is in thermal equilibrium with B, and B

is in thermal equilibrium with C, then C will
be in thermal equilibrium with A.

Consequence of
Zeroth Law of
Thermodynamics

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (lecture 1-Introduction) 18

 Concept of Continuum

Problem: It is required to count the number of molecules present in 1

mm3 of gas at STP. If there is a hypothetical counter which can count 1
million molecules in 1 second.

Knudsen number (Kn) is a dimensionless number defined as the ratio of the

molecular mean free path length (λ) to a representative physical length scale (L).

If Kn <<1 then continuum assumption is valid.

In contnuum regime neigbouring atoms are

indistinguishable

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (lecture 1-Introduction) 19

 Concept of Temperature

Statistical thermodynamics account for the bulk properties of matter

in terms of its constituent atoms. Bulk properties we don’t need to
think about the behavior of individual atoms but we do need to think
about the average behavior of myriad atoms.

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (lecture 1-Introduction) 20

 Concept of Temperature

Atom can exist with only certain energies- At a given

temperature—in the bulk sense—a collection of atoms consists of
some in their lowest energy state (their ‘ground state’), some in
the next higher energy state, and so on, with populations that
diminish in progressively higher energy states. When the
populations of the states have settled down into their
‘equilibrium’ populations, and although atoms continue to jump
between energy levels there is no net change in the populations, it
turns out that these populations can be calculated from
knowledge of the energies of the states and a single parameter β

Temperature is just a parameter that summarizes the relative

populations of energy levels in a system at equilibrium.
CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (lecture 1-Introduction) 21
 Temperature- Boltzmann distribution

The Boltzmann distribution is

an exponentially decaying
function of the energy. As the
temperature is increased, the
populations migrate from lower
energy levels to higher energy
levels. At absolute zero, only the
lowest state is occupied; at
infinite temperature, all states are
equally populated.

The Maxwell–Boltzmann distribution of molecular speeds for molecules of

various masses and at different temperatures. Note that light molecules
have higher average speeds than heavy molecules. The distribution has
consequences for the composition of planetary atmospheres, as light
molecules (such as hydrogen and helium) may be able to escape into space.
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