School of Engineering

Department of Materials Science and Metallurgical Engineering

Process Thermodynamics
NPT220
3 July 2017

Prof Andrie Garbers-Craig

 TABLE OF CONTENTS

Organisational Component

Page
1. General Premise and Educational Approach ........................................................................ 1
2. Module coordinators and Consulting Hours ......................................................................... 1
3. Rules of Assessment ................................................................................................................ 1
4. Prescribed text & Learning material ..................................................................................... 1

Study Component
1. Module Objectives, Articulation and Learning Outcomes ..................................................... 2
2. Module Structure .................................................................................................................... 2
3. Guidelines For Using The Study Theme Descriptions ........................................................... 3
4. Study Theme Descriptions ...................................................................................................... 3
4.1 Study Theme 1: The First Law of Thermodynamics .......................................................... 3
4.2 Study Theme 2: Second Law of Thermodynamics ............................................................. 4
4.3 Study Theme 3: Presentation of Thermodynamic Information ......................................... 5
4.4 Study Theme 4: Material balances .................................................................................... 6
4.5 Study Theme 5: Energy balances ....................................................................................... 6
5. ECSA Documents ................................................................................................................ 8
 ORGANISATIONAL COMPONENT

1. GENERAL PREMISE AND EDUCATIONAL APPROACH

The main aim of this course is to develop your competency to (a) to apply the basic concepts of classical
thermodynamics to metallurgical systems and (b) perform mass and energy balance calculations for different
metallurgical operations. This will be achieved through a co-operative and student-centred learning approach.
The main ECSA outcomes that are addressed in this course include ELO 1 (problem solving), ELO 2
(application of scientific and engineering knowledge) and ELO 8 (individual and team work).

2. MODULE COORDINATORS AND CONSULTING HOURS

Module coordinator: Prof Andrie Garbers-Craig
Mineral Sciences Building, Room 3-37
Tel: 012-420-3189
e-mail: Andrie.Garbers-Craig@up.ac.za

Lecture times and venues: Monday 14h30 (Eng II: 3-31),

Tuesday 14h30 (Eng II: 3-31),
Wednesday 8h30 (Eng I: 1-2)
Wednesday 12h30 (Eng I: 1-2)

Tutor class: Thursday 14h30 & 15h30 (Eng I: 1-2).

Consulting hours: By appointment at least a day in advance. (This policy also holds before tests and exams.)

3. RULES OF ASSESSMENT
Calculation of the final mark: Weights of the exam & semester mark
Semester mark: 50%
Examination mark: 50%

Calculation of the semester mark:

The semester mark is compiled as follows:
Semester tests: 90% (45% each)
Problem sets, Take-home assignments: 10%

Pass requirements:
Obtain a final mark of at least 50% AND comply with all ECSA ELOs as set out in the assessment sheets (where
applicable) AND attend all tutorial classes AND obtain a grade of at least 40% for both the semester mark and the
examination mark.

Semester tests: Two tests of 90 minutes each will be written during the scheduled test weeks of the School of
Engineering. Dates, times and venues will be announced as soon as the timetables become available.
Exam: The final examination takes three hours.
Sick test: Any absence from semester tests must be supported by an official and valid statement (e.g. a medical
certificate) and must be submitted to the lecturer within three days of the date of the test. A special semester test for all
legitimate absentees can be taken after the second test week. This test will be based on all the work done in the module
thus far.
The semester tests, sick test and exam are all closed book.

4. TEXTBOOK & LEARNING MATERIAL

Price, G. Thermodynamics of Chemical Processes. Oxford University Press, 1998, Oxford.
Additional notes will also be handed out during the lectures.

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 STUDY COMPONENT

1. MODULE OBJECTIVES, ARTICULATION AND LEARNING OUTCOMES

1.1 General objectives
The general objective of this module is to introduce the basic principles of metallurgical thermodynamics as well as the
basic principles of mass and energy balance calculations to the learners, and develop their skills and confidence in
applying these principles to practical metallurgical problems. The skills that are developed will enable the learner to:
- perform mass balance calculations on any metallurgical system or process
- perform energy balance calculations on any metallurgical system or process
- understand the basic structure and laws of classical thermodynamics
- understand the derivation of the fundamental equations that govern classical thermodynamics
- select the relevant equations that should be used to solve a thermodynamic problem which is related to a specific
type of system
- solve metallurgical thermodynamic problems quantitatively and interpret the acquired answers
The above will be pursued by following student-centred and co-operative learning and teaching methods.

Yearbook description
The first, second and third laws of thermodynamics, enthalpy and heat capacity. The criteria for equilibrium, Gibbs free
energy, chemical potential, partial molar Gibbs free energy, activity, activity coefficient and the equilibrium constant.
Solution thermodynamics of ideal and non-ideal solutions, as well as solution models. Ellingham, Kellogg and Pourbaix
diagrams. The thermodynamic principles are applied to metallurgical processes. Applications also include stoichiometry
and mass balance problems, as well as the calculation of energy balances.

1.2 Prerequisite learning and articulation with other modules

Successful completion of chemistry is a prerequisite (CHM 171) or (CHM 172).

1.3 ECSA Outcomes addressed in this module

The following ECSA exit-level outcomes are addressed in this module, i.e. at the conclusion of this module you must be
capable of:
ECSA 1: Problem solving
Solve real world thermodynamic, and mass and energy balance problems creatively and scientifically. This includes the
evaluation of the obtained answers.
ECSA 2: Application of scientific and engineering knowledge
Apply mathematics and fundamental thermodynamic principles and concepts to different types of systems.
Apply knowledge of different thermodynamic processes to solve mass and energy balance calculations.

1.4 ECSA Developmental outcomes

ECSA 8: Individual, team and multidisciplinary working
During the tutorial classes it is required that you work in small groups through which interpersonal skills and your ability to work in a
team will be developed.

2. MODULE STRUCTURE
Study theme and Notional Contact session
Study units hours hours
Study Theme 1:
24 12
The First Law of Thermodynamics
Study Theme 2:
40 20
The Second Law of Thermodynamics
Study Theme 3
The Presentation of Thermodynamic 30 15
Information
Study Theme 4:
30 15
Mass Balances
Study Theme 5:
36 18
Energy Balances
Total 160 80

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Notes:
The notional hours include the contact time and the estimated time to be allocated for self-study and preparation for tests
and the examination. These figures in the table are only an estimate.

The modes of instruction are the same for all the study themes, namely lectures, tutorial classes (completing problem sets
in groups) and self study.

3. GUIDELINES FOR USING THE STUDY THEME DESCRIPTIONS

Detailed information on the study themes which make up this module is given in the rest of the study guide. This information is
intended to guide you in the learning process, ensuring that you acquire and reinforce the skills necessary to master the stated
outcomes of this module. The following items are included under each of the study themes:
3.1 Learning outcomes of the study theme
The stated learning outcomes for each study theme are the essential building blocks for achieving the overall critical learning
outcomes / ECSA exit-level outcomes: these are the engineering skills which you must master in each theme
3.2 Study units
References to the relevant sections of the textbook are given here for each subdivision of the study theme; these are the sections
which you need to study to achieve the learning outcomes. Some additional information will be provided as photocopies.
3.3 Criteria of assessment

The criteria of assessment list the skills which you need to master to achieve the learning outcomes. Assessment (tests and the
examination) will be based on these criteria; the tests and exam paper will simply be a subset of the criteria of assessment stated in
this study guide.

4. STUDY THEME DESCRIPTIONS

4.1 Study Theme 1: The First Law of Thermodynamics

4.1.1 Learning outcomes
At completion of this study unit you should be able to apply the first law of thermodynamics in thermodynamic calculations
of metallurgical unit processes.

4.1.2 Study unit

1. Preamble: energy in chemical systems (Price, Chapter 1)
- Chemical systems
- Energy in chemistry
- Internal energy and the First Law of Thermodynamics

2. Enthalpy and thermochemistry (Price, Chapter 2)

- Enthalpy changes in chemical systems
- Variation of enthalpy with temperature
- Enthalpy changes for certain processes

4.1.3 Tutorial class

One assignment will be completed during each of two tutorial classes.

4.1.4 Criteria of assessment

At the end of this study theme, you must be able to do the following:
Distinguish between classical and statistical thermodynamics.
Define a thermodynamic system, i.e. distinguish between the universe, a system, as well as the surroundings and
boundaries of a system.
Distinguish between isolated, closed and open systems.
Distinguish between unary and multicomponent systems as well as homogeneous and heterogeneous systems.
Write a general expression for a change in any property of a system.
Distinguish between the use of d and in equations where a change in a property is depicted.
Define an ideal gas, give the appropriate equation and identify each variable.
Define energy, and give the appropriate units.
Distinguish between molar and specific heat capacities.
Determine the equation for the mechanical work done on a cylinder due to an external pressure. Distinguish
between expansion and compression of the cylinder.
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 Distinguish between reversible and irreversible processes.
Define the sign convention for work or energy that is transferred to or from a system to the surroundings.
Write down the mathematical equation that describes the first law of thermodynamics. Discuss each term in the
equation.
Write an expression that will illustrate the relation between the enthalpy and heat capacity of a system.
Expand the above expression to include phase transitions that may occur in the system.
Distinguish between state functions and process variables.
Define Hesss law.
Calculate the heat of formation of a compound at 25C and any other temperature, e.g. at 500C.

4.2 Study Theme 2: The Second Law of Thermodynamics

4.2.1 Learning outcomes
At the end of this study theme, you should able to apply the Second Law of Thermodynamics to chemical processes
involving standard as well as non-standard conditions. You should be able to evaluate the results of your calculation and
to explain the meaning of it.

4.2.2 Study unit

1. Entropy in chemistry (Price, Chapter 3)
- The second law of thermodynamics
- The measurement of entropy
- The third law of thermodynamics
- Entropy changes in chemical reactions

2. Free energy and equilibrium (Price, Chapter 4)

- Free energy and reactivity; Gibbs free energy of formation; variation of Gibbs free energy with temperature, pressure
and concentration
- Free energy and equilibrium, and the equilibrium constant
- Chemical potential
- Effect of pressure and temperature on the equilibrium constant

3. Phase equilibrium and solutions (Price, Chapter 5)

- Phase behaviour of single component systems (P-T diagrams)
- Quantitative treatment of phase transitions; the Clapeyron and Clausius-Clapeyron equations
- Phase behaviour in two (or more) component systems
- Raoults law
- Henrys law
- Activity constant
- Interaction coefficients (notes)
- The regular solution model (notes)

4. Thermodynamics of electrochemical cells (Price, Chapter 4 & notes)

- Standard electrode potentials
- Concentration dependence of electrode potentials

4.2.3 Tutorial class

One assignment will be completed during each of four tutorial classes.

4.2.4 Criteria of assessment

At the end of this study theme, you must be able to do the following:
Define the concept of entropy.
Write down the mathematical equation that describes the second law of thermodynamics.
Describe the criterion for equilibrium, based on the 2nd law of thermodynamics.
Distinguish between entropy changes in reversible and irreversible processes.
Define the third law of thermodynamics.
Calculate entropy changes in chemical reactions.
Write down the mathematical equation for the combined first and second laws of thermodynamics.
Define the Gibbs free energy, and give appropriate equations.

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 Write down an equation which describes the Gibbs free energy change for a reaction aA+bB=cC+dD in terms of the
quotient of activities (Q) and the standard Gibbs free energy change of the reaction.
Explain what it means when:
(a) G=0
(b) G>0
(c) G<0
(d) Q = K (the equilibrium constant)
Indicate how the Gibbs free energy varies with:
(a) Pressure
(b) Concentration
Define the concept of an activity of a component i in solution.
Define the chemical potential, and give the appropriate equations.
Indicate how the equilibrium constant is dependant on:
(a) Pressure
(b) Temperature
Perform calculations related to single component systems, using the Clapeyron or Clausius-Clapeyron equations.
Define the Gibbs free energy of mixing, enthalpy of mixing and entropy of mixing for a binary solution A-B. Give the
appropriate equations.
Define Raoults law, and the concept of an ideal solution.
Define Henrys law, and the concept of a dilute solution.
Define the activity coefficient of component i in terms of the activity and mole fraction of component i. What does it
mean when:
(a) i=1
(b) i>1
(c) i<1?
Define interaction coefficients and show how they are used to calculate the activity coefficients of components in dilute
solutions.
Define a regular binary solution. Write down the appropriate equation and explain how the constants in this equation
can be determined from experimental data.
Calculate the free energy changes for reactions taking place in electrochemical processes.
Distinguish between electrochemical reactions that take place at the cathode vs. at the anode.
Calculate cell potentials from standard reduction potentials.

4.3 Study Theme 3: The Presentation of Thermodynamic Information

4.3.1 Learning outcomes
At the end of this study theme you should be able to calculate thermodynamic data and present it in a form that provides
useful information about the system.

4.3.2 Study unit

Notes will be handed out on:
1. The Ellingham diagram
2. Predominance / Kellogg diagrams
3. Pourbaix diagrams

4.3.3 Tutorial class

One assignment will be completed during one tutorial classes.

4.3.4 Criteria of assessment

At the end of this study theme, you must be able to do the following:
Explain the principles upon which the Ellingham diagram for oxides / carbides / sulphides etc. are constructed.
Comment on phase changes, and the slopes of the G vs. T lines.
Use G - T data to construct an Ellingham diagram.
Make use of the Ellingham diagram for the formation of oxides to determine the following:
a) The most stable oxide phase.
b) The most stable metallic phase.
c) The positions of the pivot points O, C and H.
d) The equilibrium dissociation pressure (Po2) for a specific M-MO pair at a specific temperature.
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 e) The equilibrium constant K for a specific M-MO pair at a specific temperature.
f) The equilibrium CO/CO2 ratio for a specific M-MO pair at a specific temperature.
g) The equilibrium H2/H2O ratio for a specific M-MO pair at a specific temperature.
h) The equilibrium oxygen potential (Po2) for a gas mixture with a specific CO/CO2 ratio at a specific temperature.
i) The equilibrium oxygen potential (Po2) for a gas mixture with a specific H2/H2O ratio at a specific temperature.
Construct a Kellogg / predominance diagram for a system M-S-O from G-T data. Use either the compositional axes
logPso2 logPo2 or logPs2 logPo2.
Use Eh pH data to cconstruct a Pourbaix diagram.

4.4 Study Theme 4: Material Balances

4.4.1 Learning outcomes
At the end of this study theme, you should be able to perform a material balance for a given metallurgical unit process.

4.4.2 Study units

1. Introduction (Hand-out notes)
What is a material balance calculation all about?

2. Stoichiometry (Refer to 1st year chemistry textbook and notes.)

- Balancing chemical reaction equations
- Stoichiometric calculations

3. Material Balances (Hand-out notes)

- A general strategy for solving material balances.
- Performing a mass balances for a non-reactive process.
- Performing a mass balance for a process involving chemical reaction.
- Solving more complex problems e.g. mass balance of the ironmaking process.

4.4.3 Tutorial classes

One assignment will be completed during each of five tutorial classes.

4.4.4 Criteria of assessment

At the end of this study unit the learner should be able to do the following:
Know of and understand the laws of conservation of matter; definite proportions and multiple proportions.
Express chemical compositions as volume percentage or mass percentage and be able to switch between the
different ways of expressing compositions.
Differentiate between a steady state process and a non-steady state process.
Distinguish between the following: batch process; and continuous process.
Use stoichiometric principles to perform calculations in a mass balance.
Determine the limiting and excess reactant for a given chemical reaction.
Understand and be able to use the gas laws in performing mass balances.
Ideal gas law
Daltons law
Understand why the ideal gas law can be used in most metallurgical processes.
Perform a mass balance calculation on any metallurgical system (or process).
Make use of the concept of a tie component in solving mass balances.

4.5 Study Theme 5: Energy balances for reactive systems

4.5.1 Learning outcomes
At the end of this study theme, you should be able to calculate a combined material and energy balance for a given
metallurgical unit process. You should further be able to evaluate the obtained results and to optimize the operational
parameters in order to improve the efficiency of the process.

4.5.2 Study unit

1. A general strategy for solving energy balance. (Hand-out notes)
- setting up the energy balance equation
- problems concerning relatively simple processes
- problems concerning complex reactive processes

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4.5.3 Tutorial class
One assignment will be completed during each of three tutorial classes.

4.5.4 Criteria of assessment

At the end of this study unit the learner should be able to do the following:
Know of and understand the law of conservation of energy.
Understand what the enthalpy of a system is.
Explain the reasons for making use of standard state conditions in determining enthalpy values, and be able to state
the reference (standard) state.
Explain why the enthalpy of elements in their standard state is zero.
Explain what is the heat capacity of a substance, and be able describe its
relationship with enthalpy (or state it in the form of an equation).
State the different ways in which the enthalpy of a system could be changed (for a metallurgical system). And know
the associated enthalpy equations (where necessary).
Differentiate between heat of reaction; heat of transformation (or latent heat); and sensible heat.
Make use of Hess law to perform energy balance calculations on any metallurgical process.
Know of and understand the significance of adiabatic processes.

_________________________________________________________________________________________

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5. ECSA DOCUMENTS

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 EXTERNAL EXAMINERS ACCEPTANCE REPORT
Module NPT 220: Process Thermodynamics
Question paper set by Prof AM Garbers-Craig, PhD
Andrie.Garbers-Craig@up.ac.za
Examination type Final exam: Yes
Re-exam/Sickness Exam
Date of examination Nov 2017
External Examiner(s) Prof Johan de Villiers
Compliance with ECSA Exit Level Outcomes (ELOs)/Development Level Outcomes (DLOs). Yes/No
Are the expected ECSA ELOs or DLOs for this course reflected in the examination paper and are they
adequately assessed?
ECSA ELO ELO Description Where is the ELO How is the ELO assessed?
assessed?
ELO 1 Solve real world In 15 problem Semester tests and exam consist
Problem solving: thermodynamic, and sets, in two mostly of the execution of
Identify, formulate, analyse mass and energy semester tests thermodynamic, mass and energy
and solve complex balance problems and one exam. balance calculations. Theory
engineering problems
creatively and innovatively. creatively and questions comprise less than 10% of
scientifically. This the final mark. Problem sets 10% of
includes the evaluation semester mark, semester tests 90% of
of the obtained semester mark. Sub-minimum of 40%
answers. for exam entrance and a final mark of
50% for pass.
ELO 2 Apply fundamental In 15 problem Semester test and exam in which
Application of thermodynamic sets, in two students can apply given data to
scientific and principles and semester tests different types of materials and
engineering concepts to different and one exam. process routes associated with
knowledge: types of metallurgical existing metallurgical systems (e.g.
Apply knowledge of systems. Perform alloys, slags, mattes, ceramics).
mathematics, natural mass and energy
sciences, engineering
fundamentals and an balance calculations to
engineering speciality to metallurgical
solve complex engineering processes.
problems.
DLO 8 (not accessed in this paper): Individual, team and multidisciplinary working (Demonstrate competence to
work effectively as an indivi-dual, in teams and in multi-disciplinary environments.)
It is required that the students work in small groups during the tutorial classes that cover the thermodynamic
work. This DLO is assessed through the submission of one problem set per group, at the end of a tutorial class.

Comments on any ELO or DLO of the question paper:

External examiners acceptance of Accept as is

question paper Accept with comments or changes
Reject with comments:
Signature Date
(External Examiner)
Signature Date
(Department Head)
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 REPORT ON QUALITY OF ASSESSMENT
(updated October 2012)
Please Tick Exam Re-exam Special Exam
DEPARTMENT OF MATERIALS SCIENCE AND METALLURGICAL ENGINEERING
UNIVERSITY OF PRETORIA
General remarks: Since the University of Pretoria strives for excellence; external examination of the quality of assessment is of the utmost importance. The external examiner is to
evaluate the standard of answering and the quality of assessment by means of random sampled answer sheets (undergraduate: at least 10). After evaluation of the examination
paper, the external examiner is to document his/her findings by means of this report form, which must please be returned to the Head of Department via the internal examiner.
MODULE CODE: COURSE: EXAMINATION PERIOD:
NPT220 Process Thermodynamics Nov 2017
NAME OF INTERNAL EXAMINER: NAME OF EXTERNAL EXAMINER:
Prof Andrie Garbers-Craig Prof Johan de Villiers
INTERNAL EXAMINER (COMPLETE AND SEND TO EXTERNAL EXAMINER)
Original marks % class average: % passes: % distinctions: Histogram attached? Yes No

Comments by internal examiner on the quality of the examination paper, assessment process and results:

Was it necessary to adjust marks? Yes No

If yes, provide justification:

Adjusted marks % class average: % passes % distinctions: Histogram attached? Yes No

TO BE COMPLETED BY THE EXTERNAL EXAMINER
Did you assess, in detail, at least 10 answer books/sets (4 failures, 3 average and 3 good ones) Yes No
Were the papers graded consistently? Yes No
Is there good agreement between the marks awarded and the students demonstrated ability? Yes No
Judging from the sample papers and histogram, are the students that pass competent in the required outcomes? Yes No
Were the results satisfactory? Yes No
Does it appear that components of the examination process (e.g. time allotted for paper, degree of complexity, comprehensibility) were unsuccessful? If so, please make
recommendations for rectifying the problem:

If adjustments were made to the marks, do you agree that these adjustments were justified and appropriate? Yes No
Any other comments?

Signature Signature
External Examiner Date Internal Examiner Date

TO BE COMPLETED BY INTERNAL EXAMINER, SECTION HEAD AND HEAD OF DEPARTMENT

The internal examiner must submit this evaluation report and the following documents and discuss these with the Research Group Leader and the Head of Department
Study guide Memorandum Marks electronic media Answer books
Exam paper Histogram Marks spreadsheet printout
Evaluation of results/examiners comments by the Internal Examiner, Section Head and Head of Department:

Minutes of remedial steps that were decided upon (if necessary):

Signature Signature Signature

Internal Examiner Date Research Group Leader Date Head of Department Date

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