DEPARTMENT OF CHEMICAL ENGINEERING

181CTDCHA2: CHEMICAL
THERMODYNAMICS 2A

Instructor
Prof Kapil Moothi
Associate Professor
Department of Chemical Engineering,
University of Johannesburg,
Room: 4134
Tel: 011 559 6385
E-mail: kmoothi@uj.ac.za

Consultation Times: Tuesday, 10:00-11:30

Lecture session(s): 3 per week
Tutorial session(s): 2 per week

Recommended Textbook: Smith, J.M.,

Van Ness, H.C., Abbott , M.M. (2005),
Introduction to Chemical Engineering
Thermodynamics. 7th Edition, McGraw-Hill
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 ■ 2016-2017: Postgraduate Diploma in Higher Education
Who am I? (PGDipHE), University of Johannesburg, Johannesburg, SA

■ 2010-2014: Doctorate (PhD) in Chemical Engineering,

(Thesis), University of the Witwatersrand, Johannesburg, SA
– Thesis: Production of Carbon Nanotubes using Direct
Coal-Derived Hydrocarbon Products in a Chemical Vapour
Deposition Reactor
– Supervisors: Prof S.E. Iyuke, Prof R. Falcon, Dr M.
Meyyappan, Dr W. Augustyn

■ 2008-2009: Master of Science (MSc) in Chemical

Engineering, (Dissertation), University of the Witwatersrand,
Johannesburg, SA
– Dissertation: Carbon Nanotube Production from
Greenhouse Gases during Syngas Synthesis
– Supervisor: Prof S.E. Iyuke

■ 2008: International Diploma in Brewing & Distilling, The

Institute of Brewing & Distilling (IBD), UK

■ 2004-2007: Bachelor of Science (BSc) in Chemical

Engineering, University of the Witwatersrand, Johannesburg, SA

2
Course Content
■ Learning Unit 1: Review of Basics Concepts
• Learning Unit 1A: Basic Concepts and Definitions (Chapter 1)
• Learning Unit 1B: First Law of Thermodynamics and Other
Basic Concepts (Chapters 2)
• Learning Unit 1C: The Second and Third Law of
Thermodynamics (Chapter 5)
■ Learning Unit 2 : Properties of Pure Fluids (Chapter 3)
■ Learning Unit 3: Heat Effects (Chapter 4)
■ Learning Unit 4: Thermodynamic Properties of Real Fluids (Chapter
6)
■ Learning Unit 5: Properties of Mixtures (Chapters 10 and 11)

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Blooms’ Taxonomy (Bloom, 1956)

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5
Test Dates
(subject to change)

■ Test 1: 06 March 2018

■ Test 2: 03 April 2018

■ Test 3: 01 May 2018

6
 Grading (subject to change)

Assessment Weight
Test 1 15%
Test 2 20%
Test 3 25%
Assignment 15%
Online Activities 25%
Total 100%

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Who am I? ■ 2012-2017: Doctorate (PhD) in Chemical
Engineering, (Thesis), University of the
Witwatersrand, Johannesburg, SA

■ 2011: Bachelor of Science (BSc) with

Honours in Microbiology and
Biotechnology, University of the
Witwatersrand, Johannesburg, SA

■ 2008-2010: Bachelor of Science (BSc) in

Microbiology/Biotechnology and
Chemistry, University of the Witwatersrand,
Johannesburg, SA

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LEARNING UNIT 1A
Basic Concepts and Definitions

Instructor: Dr Gloria Hlongwane

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Guidelines on How to Use Slides
■ Action buttons:

Directs you to back to a previous slide.

Directs you to forward to the next slide.

Takes you back to the home slide.

Video link (Internet connection required for link

to work).

■ The slides provided are interactive and nonlinear.

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Introduction to Thermodynamics
■ Course Objectives
• Introduce fundamental concepts of Chemical Engineering
Thermodynamics
o Thermodynamic concepts/ properties (energy, entropy,
enthalpy, heat capacity, etc.)
o Laws of Thermodynamics (energy and entropy balance)

■ Course Outcomes
• Impact on your abilities as an engineer in the following ways:
o Understand the importance of providing technical
competence using engineering fundamentals
o To think in order of identification, then formulation and
finally solution
o Reinforce the utilisation of a systems approach to design
and operational performance.

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Why Important to Chemical Engineers?
■ Chemical Engineering = understanding
and using mass transfer in conjunction
with heat transfer.

■ The laws of thermodynamics, which

govern energy and the direction of
energy flow, are amongst the most
important fundamentals of chemical
engineering.

■ The skills and knowledge learnt in this

subject are crucial to the understanding
of chemical engineering and the
careers of chemical engineers. They
provide the basis for solving problems
of interest in nearly all industries,
including petrochemical, mining and
minerals processing, energy
generation pharmaceuticals etc.
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Why Important to Chemical Engineers?
■ Thermodynamics is:
• the science of heat, work and related
properties

• the basic science that deals with energy

https://networkingtimes.com/blog/wp-
• the study of energy movement between
content/uploads/2015/11/nutshell.gif

different objects.

■ Thermodynamics derived from Greek words i.e. therme (heat) +

dynamis (power).

■ ‘Thermo’ (refers to heat) and ‘dynamics’ (think motion or movement).

■ Thermodynamics = heat movement or heat flow = energy movement or

energy flow.
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Energy Flow in Everyday Life
■ All the fundamental concepts are based on observation of
everyday experience.

http://birgitmummu.vikki.fi/OnnitteluKORTIT/Animaatiot/Retkeily/
http://www.aplusphysics.com/courses/honors/thermo/heat.html

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Energy Flow in Chemical Engineering?
■ Energy movement or energy flow in engineering:

o For engineers, it describes the

conversion of chemical energy
stored in fossil fuel into heat and
useful work.

o Chemical Engineering involves

taking natural raw materials and
transforming them into useful
products.

■ Energy is needed to: transport materials, physically transform materials

(smelting or distillation), chemically transform materials.

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Why is Thermodynamics Useful?
■ The ‘Laws of Thermodynamics’ can
help us investigate:

• How much energy?

"You cannot get something for
nothing“ - conservation of mass
and energy.

• How efficiently does energy

move?
Potential to do work is lost
through disorder - "quality" of
energy tends to decrease
(entropy increases).

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Why is Thermodynamics Useful?
■ Given a mixture of substances in a liquid
solution, it can be used to predict which
substance will prefer to be in the vapour
phase and which will prefer to be in the
liquid phase
- For transfer of chemical species
between phases
- This knowledge is vital in the design
and operation of distillation columns

■ It can tell us whether a process will occur

or not but cannot tell us how fast or how
slow a process will occur
-What area of study is this?

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Thermodynamics is Not Hard

■ If everything is so simple, why does thermodynamics have the

reputation of being ‘hard’/ ‘difficult’?
-‘It is full of hard words and signs and numbers, not very entertaining
or understandable looking ...’ (Levenspiel, 1996)

■ Challenge comes from making accurate descriptions of phenomena

and in developing mathematical framework (understanding of the
thermodynamic laws)

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Dimensions and Units
■ Dimension is a measure of a physical variable (without the numerical
value)

■ Unit is a way to assign numerical values to a dimension.

■ Example:

■ Length, mass and time  meter (m)

■ Mass and time  kilogram (kg)

■ Time  second (s)

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Units of Measurement
■ There are three primary unit systems in use today:
■ the International System of Units (SI units, from Le
Systeme International d’Unites, more commonly simply
called metric units)
■ the English Engineering System of Units (commonly
called English units)
■ the British Gravitational System of Units (BG)

■ Two sets of units are still in common use today: the English system
and SI (International System) [Click to view video]

■ SI units are commonly used for scientific and engineering work in

most of industrialised nations

■ SI is a simple and logical system based on decimal relationship

between various units

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Dimensions
Primary Symbol SI unit BG unit English unit
Dimension
mass m (sometimes M) kg (kilogram) slug lbm (pound-
mass)
length L (sometimes l) m (meter) ft (foot) ft (foot)
time t (sometimes T) s (second) s (second) s (second)
temperature T (sometimes q ) K (Kelvin) oR(degree R (Rankine)
Rankine)
electric current I (sometimes i) A (ampere) A (ampere) A (ampere)
amount of light C (sometimes I) c (candela) c (candela) c (candela)
(luminous
intensity)
amount of matter n or N mol (mole) mol (mole) mol (mole)
(sometimes )

■ There’s 7 primary/fundamental dimensions.

■ All other dimensions are called secondary dimensions (why?).

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Secondary Dimensions

Secondary Symbol SI unit BG unit English unit

Dimension
force F (sometimes f) N (Newton = kg× lbf (pound-force) lbf (pound-force)
m/s2)
acceleration a m/s2 ft/s2 ft/s2
pressure p or P N/m2, i.e. Pa lbf/ft2 (psf) lbf/in2 (psi) (note:
(Pascal) 1 ft = 12 in)

energy E (sometimes e) J (Joule = N× m) ft× lbf (foot pound) ft× lbf (foot pound)

power P W (watt = J/s) ft× lbf/s ft× lbf/s

■ These are secondary dimensions (why?).

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Dimensions and Units
Primary Dimension Symbol SI unit BG unit English unit

mass m (sometimes M) kg (kilogram) slug lbm (pound-mass)

length L (sometimes l) m (meter) ft (foot) ft (foot)
time t (sometimes T) s (second) s (second) s (second)
oR (degree Rankine)
temperature T (sometimes q ) K (Kelvin) R (Rankine)
electric current I (sometimes i) A (ampere) A (ampere) A (ampere)
amount of light C (sometimes I) c (candela) c (candela) c (candela)
(luminous intensity)
amount of matter n or N (sometimes ) mol (mole) mol (mole) mol (mole)

Secondary Dimension Symbol SI unit BG unit English unit

force F (sometimes f) N (Newton = kg× lbf (pound-force) lbf (pound-force)
m/s2)
acceleration a m/s2 ft/s2 ft/s2
pressure p or P N/m2, i.e. Pa (Pascal) lbf/ft2 (psf) lbf/in2 (psi) (note: 1 ft
= 12 in)
energy E (sometimes e) J (Joule = N× m) ft× lbf (foot pound) ft× lbf (foot pound)
power P W (watt = J/s) ft× lbf/s ft× lbf/s

■ Why secondary dimensions and units are called secondary?

■ REASON: Secondary dimensions and units are derived as a combination

of primary dimensions and units.
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 Dimensions and Units
■ Example: Length, mass and time  meter (m), kilogram (kg) and second
(s)

■ Force (secondary dimension): F = mass * acceleration = m * a  Newton

(N) =>>Derived as combinations of primary dimensions and corresponding
units.

■ Secondary dimensions:

– Pressure: P = force/ area = F/ A  Pascal (Pa)

– Work: W = force * distance  ?

– Power: P = energy / time ?

■ Temperature  Kelvin (K) (primary or secondary?)

25
Dimensions and Units
Primary Dimension Symbol SI unit BG unit English unit

mass m (sometimes M) kg (kilogram) slug lbm (pound-mass)

length L (sometimes l) m (meter) ft (foot) ft (foot)
time t (sometimes T) s (second) s (second) s (second)
oR (degree Rankine)
temperature T (sometimes q ) K (Kelvin) R (Rankine)
electric current I (sometimes i) A (ampere) A (ampere) A (ampere)
amount of light C (sometimes I) c (candela) c (candela) c (candela)
(luminous intensity)
amount of matter n or N (sometimes ) mol (mole) mol (mole) mol (mole)

Secondary Dimension Symbol SI unit BG unit English unit

force F (sometimes f) N (Newton = kg× lbf (pound-force) lbf (pound-force)
m/s2)
acceleration a m/s2 ft/s2 ft/s2
pressure p or P N/m2, i.e. Pa (Pascal) lbf/ft2 (psf) lbf/in2 (psi) (note: 1 ft
= 12 in)
energy E (sometimes e) J (Joule = N× m) ft× lbf (foot pound) ft× lbf (foot pound)
power P W (watt = J/s) ft× lbf/s ft× lbf/s

■ See the difference between primary and secondary dimensions and units.

■ When working through the tutorials you may encounter other units e.g. English units
(foot (f)) etc.. Recognise, understand and be comfortable with unit conversions.

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Dimensions and Units (cont.)

[Click to view video]

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 Standard Prefixes for SI Units
Multiple Prefix Symbol Multiple Prefix Symbol
10-15 femto f 1015 peta P
10-12 pico p 1012 tera T
10-9 nano n 109 giga G
10-6 micro µ 106 mega M
10-3 milli m 103 kilo k
10-2 centi c 102 hecto h
10-1 deci d 101 deka da

■ SI prefixes are used to form decimal multiples and submultiples of SI units (avoid
very large or extremely small numerical values of dimensions).

■ How to use these:- Attach directly on the name unit of describing the dimension and
the symbol of the prefix also directly attaches to the symbol of the unit.

■ Example: Given: Dimension – Length (L), SI Unit -Meters (m), SI prefix – Nano (n)

■ Which is correct ? Nanolength (nL) or nanometers (nm)?

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Measurement of Amount/ Size

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Measurement of Force
 Force (secondary dimension):

 Derived as combinations of primary dimensions and corresponding units.

 When the numerical values of secondary dimension are known,

numerical values of primary dimensions can be easily found.

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Example (Force)

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Temperature
■ System based on melting and boiling points of water
■ The four temperature scales:

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Temperature
■ Temperature scale in SI units is Celsius (°C)

■ Thermodynamic temperature scale in SI units is Kelvin (K)

■ Temperature scale in English units is Fahrenheit (°F)

■ Thermodynamic temperature scale in English units is Rankine (R)

■ Thermodynamic temperature scale is independent of the properties of any

substance (s)
Conversion of Units: Temperature Differences (ΔT):

33
Temperature (Example 1)
■ During a heating process, the temperature of a system
rises by 10°C. Express this rise in temperature in K, °F,
and R

What is the correct answer (Click on chosen answer):

(a) 10 K, 18°F, and 18 R
(b) 10 K, 18°F, and 10 R
(c) 18 K, 10°F, and 10 R

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Temperature (Example 1)

Problem: During a heating process, the temperature of a system rises by 10°C.

Express this rise in temperature in K, °F, and R

Solution:
The temperature rise of a system is to be expressed in different units
Analysis:
This problem deals with temperature changes, which are identical in Kelvin and
Celsius scales:
T(K) = T(oC)=10 K
The temperature changes in Fahrenheit and Rankine scales are also identical
and are related to the changes in Celsius and Kelvin scales:
 T(oF) = 1.8  T(oC) = 1.8 x 10= 18oF
 T(R) =  T(oF) =10 R
[Click for conversion units and temperature differences reminder]

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Example 2 (Temperature)
■ Convert the following:

i. 25oC into K
ii. 54oF into R
iii. 35K into R
iv. Temperature change of 10oC into K
v. Temperature change of 5oF into R
vi. Temperature change of 25K into F

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Example 2 (Temperature)

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Pressure

40
 Pressure (Absolute and Gauge)

Zero-referenced against
atmospheric pressure

Difference between absolute

and atmospheric pressure

Actual pressure at Indicated in most pressure

a given position measuring device (devices
calibrated to zero in the
Zero-referenced atmosphere)
against perfect
vacuum

https://steemit.com/steemstem/@akeelsingh/pressure-sensor-testing-report-self-done

41
Pressure (Absolute and Gauge) (cont.)
■ Pressure in a fluid at rest does not change in the
horizontal direction

■ Pressure in a fluid changes in the vertical direction

in a gravity field

■ Pressure in a fluid increases with depth because

more fluid rests on deeper layers, and the effect of
this extra weight on the deeper layer is balanced
by an increase in pressure.

■ So to calculate pressure in a fluid this variation is

considered:

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Pressure (Example 1)

True or false?
The pressure at point a
and b are not equal.
[Click on answer]
(a) True
(b) False

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Pressure (Example 2: homework)

Pressures up to 3000 bar are measured with a

dead-weight gauge. The piston diameter is 4
mm. What is the approximate mass in kg of the
weights required?
When done click here to reveal solution

47
 Pressure (Example 3)

The reading on a mercury manometer at 25°C (open to the

atmosphere at one end) is 56.38 cm. Atmospheric
pressure is 101.78 kPa. What is the absolute pressure in
kPa being measured? The density of mercury at 298.15 K
(25°C) is g cm-3. Take g as 9.832 m s-2.

When done click here to reveal solution

49
Systems and Their Behavior
■ A system contains a substance with a large amount of molecules or atoms
and may be taken through a complete cycle of states, in which its final
state is the same as its original state.

■ As engineers we are interested in studying systems and how they interact

with their surroundings

Remember: Chemical
engineering is the all
about understanding
and using mass transfer
in conjunction with heat
(energy) transfer.

■ ‘Universe’ refers to a system and its surroundings.

■ To describe a system and predict its behaviour requires knowledge of its

properties [click for definitions ] and how those properties are related.

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Properties
If a thermodynamic property is a state function:
- Its change is independent of the path between the initial and final states
- Depends on only the properties of the initial and final states of the
system

Intensive properties Extensive properties

■ Are not additive and do not depend ■ Are additive and depend
upon the mass of the system e.g. upon the mass of the
P, T, refractive index, density, system, e.g. m, n, V, H, U,
thermal conductivity, etc. etc.
■ Intensive properties can be
expressed as derivatives of
extensive properties (mathematics [Click for video ]
will emerge in this course i.e.
differentials, integrals etc).

53
 System and Surroundings
■ Different form of energy:
– Kinetic energy (Ek) is the capacity for
mechanical work related to the motion
of a body.
– Potential energy (Ep) is the capacity
for mechanical work related to the
position of a body.
– Internal energy (U) is associated with
atomic motion and bonding (‘all
chemical energy)’.
– Energy may be transferred in the form
of heat (Q) or work (W) through the
system boundary.

■ Heat (Q) and work (W) always

refer to the system, and the
modern sign convention makes the
numerical values of both quantities
positive for transfer into the system
from the surroundings

54
 ■ An example of a thermodynamic system is
Heat and Work gas confined by a piston in a cylinder..

■ If the gas is heated, it will expand and

push the piston up, thereby doing work on
the piston. If the piston is pushed down,
on the other hand, the piston does work
on the gas and the gas does negative
work on the piston.

■ Work is a force multiplied by the distance

moved in the direction of the force

■ Thermal equilibrium is an important

This is one example
thermodynamic system and of
how a thermodynamic system
can do work.
concept in thermodynamics. When two
systems are in thermal equilibrium, there
is no net heat transfer between them. This
occurs when the systems are at the same
temperature.

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Types of Processes
■ However, what type of system is this? Closed or open?
■ Is it a reversible or an irreversible process?
■ Adiabatic process:
• Any process within the system whereby there is no heat
transfer
■ Steady state process:
• Variables in the system remain constant with time
• System exchanges energy or matter at a constant rate
■ Unsteady state process (transient process):
• Variables in the system change with time

56
 Conversion of Units

Convert the following: 12 N/cm2 to N/m2

(cm) 2
(100) 2
12 N =
cm2 1 m2
12 N/Cm2 = 12x104 N/m2

57
Conversion of Units

58
 Conversion of Units (do this at
home)
Convert the following :7200 psi to N/m2 or Pa

7200 lbf 4.4482216 N 1 in 2

in 2 1 lbf (0.0254)2 m2

7200 psi = (7200)(4.4482216)/(0.0254)2= 49642252 Pa

59
Interpolation

■ Mathematical/Statistical tool used to estimate values between two

points.
■ When a value is required from a table at conditions which lie between
listed values, interpolation is necessary
[click for video]

■ For example, the enthalpy of saturated vapour steam at 413.95K

(140.8oC) is intermediate between the following values:

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Interpolation

61
Next Session(s)
■ We will delve further into this first law of thermodynamics and get
to the mathematics (‘conservation of energy’ or ‘energy
balance’):

■ Understanding the second law of thermodynamics: What is

entropy (S)? Why does it increase?
■ P-V diagrams: Constant V, Constant P processes
■ Enthalpy, specific heat/ heat capacity (of an ideal gas)
■ Homework - read Chapter 1 (in particular, understand the gas
cylinder example) in the textbook:
o Smith, J.M., Van Ness, H.C., Abbott , M.M. (2005),
Introduction to Chemical Engineering Thermodynamics.
7th Edition, McGraw-Hil

62
Other Recommended Textbooks
Sandler, I. (2006), Chemical, Biochemical, and
Engineering Thermodynamics. 4th Edition, John Wiley
and Sons Inc.

Levenspiel, O. (1996), Understanding Engineering

Thermodynamics. Prentice Hall PTR.

Tester, J.W. and Modell, M. (1997), Thermodynamics

and its Applications. 3rd Edition, Prentice Hall.

63
Tips
Need to work in pairs and not stay isolated
from the other students (need to develop
working relationships and get to know each
other) [Click here if you would like to see
quotes about teamwork)

Important to use the tutorial sessions

productively i.e. prepare for the sessions and
discuss issues/ challenges with the tutor/s

64
At the end of this course you should
have attained these outcomes

■ Applying Thermodynamic principles to diagnose and solve

engineering problems.

■ Demonstrate engineering knowledge and skills in the

Thermodynamics field.

■ Engage in Thermodynamics work individually and as part

of a team.

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