NENG 301 Thermodynamics

and Kinetics of Nanomaterials

Prof. Y. Alex Xue
CNSE, SUNY Polytechnic Institute

office: CESTM B230C

phone: 956-7220
e-mail: yxue@sunypoly.edu
office hours: Tuesdays 1:002:30 PM
Course Website: http://www.albany.edu/~yx152122/NENG301-15.html

From the course catalogue

Applications of first, second, and third laws of thermodynamics to
open and closed systems. Thermodynamics of multicomponent,
multiphase chemical and biological systems are reviewed. Applies the
concepts of reaction rate, stoichiometry and equilibrium to the
analysis of materials systems. Rate expressions from reaction
mechanisms and equilibrium or steady state assumptions are used.
Design of reactions via synthesis of kinetics, transport phenomena,
and mass and energy balances are covered. Introduction to
diffusional processes.
Prerequisite(s): satisfactory completion of AMAT 311, NENG 120/122

What is Thermodynamics?
Thermodynamics is a funny subject. The first time you go through
it, you don't understand it at all. The second time you go through
it, you think you understand it, except for one or two small points.
The third time you go through it, you know you don't understand
it, but by that time you are so used to it, it doesn't bother you any
more.
-- Arnold Sommerfeld
The Laws of Thermodynamics, in brief

0th: "You must play the game."

1st: "You can't win."
2nd: "You can't break even, except at absolute zero."
3rd: "You can't get to absolute zero."

Course learning objectives

The overall learning objectives for this course are the following:
The student will demonstrate understanding of the basic structure
of thermodynamics, including state functions and process variables;
extensive and intensive properties; and the First, Second and Third
Laws of Thermodynamics
The student will be able to develop, manipulate, and utilize
relationships between thermodynamic variables and apply these
relations to gases, liquids and solids
The student will demonstrate understanding of how thermodynamic
processes determine the equilibrium structures of materials at the
macroscale, the microscale, and the nanoscale
The student will learn how the kinetics of physical and chemical
processes are dictated by thermodynamic driving forces
The student will learn how to address important scientific and
engineering problems by thermodynamic and kinetic analyses

At the beginning of each book chapter covered I will provide you

with a list of specific learning objectives for that chapter

Subjects to be covered

Background Why Study Thermodynamics

The Structure of Thermodynamics
The Laws of Thermodynamics
Thermodynamic Variables and Relations
Equilibrium in Thermodynamic Systems
Unary Heterogeneous Systems
Multicomponent Homogeneous Non-reacting Systems
Solutions
Multicomponent Heterogeneous Systems
Thermodynamics of Phase Diagrams
Multicomponent Multiphase Reacting Systems
Capillarity Effects in Thermodynamics
Introduction to Kinetic Processes: Diffusion, Oxidation,

Textbook and other readings

Textbook: R. DeHoff, Thermodynamics in Materials Science
(Second Edition, CRC Press, Taylor & Francis Group, 2006)
available at the University Bookstore
I will follow the textbook very closely: make sure you read it!!!

Extra readings on kinetics: D.A. Porter and K.E. Easterling,

Phase Transformations in Metals and Alloys
Other readings may be distributed from time to time
All non-textbook readings will be made available on the
course web site

Group exercises, exams and grading

Group exercises: Six sessions
Administered RANDOMLY
You will be working collaboratively on problems in class
NO MAKE-UP exercise

Group ordered according to last name initial

Group I: B,C,W (7)

Group II: D, E, F, Y (7)

Group III: G,J, T (7)

Group IV: K, M, U (7)

Group V: N, S (6)

Group VI: P, R (6)

There will be one comprehensive final exam

Grades will be based on the final exam (40%), and
participation in group exercise (6 x 10%).

Academic dishonesty
Academic dishonesty refers to plagiarism, cheating, multiple
submission, forgery, sabotage, falsification, unauthorized
collaboration, and bribery
Academic dishonesty will not be tolerated in this course
Any incidence of academic dishonesty will result in an
automatic failure of at least the assignment if not the course
and will be reported in writing to the CNSE Office for Student
Services

Lectures and Slides

Lectures will be MWF 10:25 to 11:20; attendance is

expected and mandatory
corollary: it would be foolish for you to miss lectures!

Lecture slides will be posted on the course website each

week
It is possible/probable that I may prepare too many slides to
fit into a 55 minute class period; in this case, I will halt the
presentation wherever it is and pick up from that spot at
the beginning of the next lecture

Student multitasking activities

Ragan et al (2014)

Justification
Sana and Weston (2013)
Students who multitask in class average 11% lower when quizzed on
material immediately afterword.
Students who are surrounded by laptops scored 17% lower.

Freid (2008)
Students who used laptops spent considerable time multitasking and
the laptop use posed a significant distraction to both users and fellow
students.
The level of laptop use was negatively related to self-reported
understanding of course material and overall course performance.

Mueller and Oppenheimer (2014)

Student who take notes on laptops tend to transcribe lectures
verbatim rather than processing information and reframing it in their
own words. Laptop notetakers performed worse on conceptual
questions.

Some comments on subject matter

Classes on thermodynamics have a certain reputation for
being difficult
If you have never seen this stuff before, it can be somewhat
challenging
However, it is not rocket science or advanced quantum
mechanics: thermodynamics and kinetics are founded in
real-life experiences
Also: thermodynamics and kinetics are important foundations
for a wide variety of scientific and technical subjects

If you are in nanotechnology, you will see this stuff for the
rest of your career you must know this!!

Some other thoughts

You will find the sequence of NENG 301, 302 and 303 to be difficult
please study accordingly and hard!
Lectures will start at 10:25 sharp dont be late
Dont hesitate to ask questions (if something is puzzling you, it is just as
likely to be puzzling to someone else)
Group exercise if you do not actually and actively participate in the
problem solving yourself, you will not be able to solve them on the exams

Need extra help? Check out a Physical Chemistry textbook from the
Science Library
Or the famous Feymann Lectures in Physics for the more adventurous

NENG 301
Lecture 1 Basic concepts of
thermodynamics (DeHoff, Chap. 1)
Look to the north. Keep looking. There's nothing coming from the south.

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Learning objectives for Chapter 1

At the end of this chapter you will be able to:
Understand the breadth of thermodynamics as an essential
subject in science and engineering
Understand the concept of equilibrium as it pertains to
thermodynamics
Understand the meaning of terms such as system, surroundings,
boundary, and properties from a thermodynamics viewpoint
Understand the concept of phase in a thermodynamics sense
Understand the concept of a unary phase diagram and how it
can be used to predict structure as a function of the state of a
system
Appreciate the concept of equilibrium maps as products of
thermodynamic analyses
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What is Thermodynamics?
The study of energy transformations and the relationships among
physical properties of substances which are affected by these
transformations.
-- K. Wark, Thermodynamics, 5th Edition (1988)
Classical (phenomenological) thermodynamics
Deals with macroscopic systems, without recourse to the nature
of the individual particles and their interactions
Requires no hypothesis about detailed structure of matter on the
atomic scale, thus laws are not subject to change as knowledge
concerning nature of matter is discovered
Statistical thermodynamics
Based on statistical behavior of large groups (ensembles) of
individual particles, and postulates that values of macroscopic
properties merely reflect some sort of statistical behavior of
enormous ensembles
Quantum thermodynamics: properties and interactions depend on the
distribution of electrons and their energies

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Why is the study of thermodynamics

important?
1.
2.
3.
4.

Thermodynamics is pervasive
Thermodynamics is comprehensive
Thermodynamics is established
Thermodynamics provides the basis for organizing
information about how matter behaves
5. Thermodynamics enables the generation of maps in
equilibrium states that can be used to answer a prodigious
range of questions of practical importance in science and
industry

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How is thermodynamics pervasive?

Thermodynamics applies to every volume element of all
systems at all times

How is thermodynamics comprehensive?

Systems: metals, ceramics polymers, composites, solids,
liquids, gases, solutions, crystals with defects
Applications: structural materials, electronic materials,
corrosion-resistant materials, nuclear materials, biomaterials,
nanomaterials
Influences: thermal, mechanical, chemical, interfacial,
electrical, magnetic
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How is thermodynamics established?

J. Willard Gibbs: On the Equilibrium of
Heterogeneous Substances was a
300-page paper published between
1875 and 1878
You flip through the pages and it reads,
more or less, like a modern physical
chemistry textbook
Just about everything that we are covering
in this course can be traced to Gibbs
A theory is the more impressive the greater the simplicity of its
premises, the more different kinds of things it relates, and the more
extended its area of applicability. Therefore the deep impression that
classical thermodynamics made upon me. It is the only physical theory
of universal content which I am convinced will never be overthrown,
within the framework of applicability of its basic concepts. (A. Einstein)
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How does thermodynamics provide a basis for

organizing information on how matter behaves?
Thermodynamics provides a mechanism for describing the
properties of scientifically and technologically important
systems
It allows you to take database information and apply it to an
even wider collection of real-life problems
A huge amount of information has been collected, is stored in
databases, and is available for use

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What are maps of equilibrium states and

why are they important?
Thermodynamics permits the generation and understanding of
maps that describe the structure and properties of matter at
equilibrium in terms of important variables
These maps present relatively simple pictures of equilibrium
structure, even though the quantitative calculation of the steps
leading to those structures may be exceedingly complex
Numerous real-life scientific and technological problems can
thus be studied and performance predicted through the
examination of one or two relatively simple equilibrium maps

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The Generic Question Addressed by

Thermodynamics

We will want to consider the following process:

System A is in equilibrium with its surroundings (Surroundings I)
The surroundings are changed (Surroundings II)
Will System A transform to System B, and what will be its
properties?
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What do we mean by equilibrium

Thermodynamic equilibrium a condition in which the
thermal (temperature), mechanical (pressure), and chemical
(concentration) characteristics do not change with time
No net flows of matter, no phase changes, no unbalanced
potentials (a.k.a. driving forces) within a system
Characteristics of a system at thermodynamic equilibrium
no changes with respect to time: dX/dt = 0
when a system is in thermodynamic equilibrium it will not
change when it is isolated from its surroundings ?

Note the distinction with steady state

no changes with respect to time,
but the system changes when it
is isolated from its surroundings

Thigh

Tlow

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Kinds of Equilibrium
Equilibrium
A system is in thermodynamic equilibrium if it is not capable
of a finite spontaneous change to another state without a
finite change in the state of the environment
Thermal: equality of temperature across the system boundary
Mechanical: equality of pressure across the system boundary
Phase Equilibrium: no tendency for net transfer of one or
more species from one phase to another
Chemical: no tendency for chemical reaction

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Some important (if obvious) concepts

System: any region of the universe, large or small,
that is being considered in our analysis
Boundary: the interface between the system and
its surroundings
Surroundings: regions outside the boundaries of
the system but can alter the system by interacting
with it
Properties: Physical characteristics that define the
condition of the system and its surroundings
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What is a phase (a really important concept)

A phase is a physically distinctive form of matter, such as a
solid, liquid, gas or plasma
A phase of matter ( a region of materials) is characterized by
having relatively uniform chemical and physical properties
Phases are separated from each other by a (usually) distinct
boundary or interface
A single phase may or may not have regions separated by
surfaces or interfaces, but two phases are always separated by a
surface or interface

The phases that develop due to materials synthesis or

processing can have a huge impact on the properties and/or
performance of those materials
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Unary phase diagrams

These simple unary (single component) phase diagrams show the

stability of a particular phase under different conditions (P and T)
Water (left) can exist in at least three phases depending on
temperature and pressure -- thermodynamics can predict behavior
when conditions change
Molybdenum (right, atomic number 42) shows qualitative behavior
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that is similar, but there are major quantitative differences

Thermodynamic Basis for Equilibrium

Maps
In phenomenological thermodynamics each system is a
structureless glop that is endowed with properties.

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Equilibrium Map #1a: Phase Diagram

(Ge/Si)

Liquid (L)

L+S

Solid (S)

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Equilibrium Map #1b: Phase Diagram

(Al/Si)

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Aluminum-rich side of the Al-Si phase

diagram

A simple binary eutectic with limited solubility

of aluminum in silicon and limited solubility of
silicon in aluminum. Eutectic point indicates
The chemical composition and temperature
corresponding to the lowest melting point
Of the solid mixture.

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Equilibrium Map #1c: Phase Diagram

(Ag/Mg)

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Equilibrium Map #2: Gas Phase Equilibria

This equilibrium gas
composition map shows
the equilibrium partial
pressure of oxygen (PO2)
as a function of the
chemical composition
(carbon, hydrogen and
oxygen) of the system

Dashed lines = oxygen

isobars that give a
specific oxygen partial
pressure as a function of
C, H and O composition

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The equilibrium partial pressure of oxygen and the boundary of carbon deposition
region in gas mixtures for the C-H-O diagram at temperatures ranging from 400 to
1000 C. Broken lines show the boundary of carbon deposition region; therefore,
carbon deposition is expected in carbon-rich composition beyond the lines.

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Equilibrium Map #3: Predominance Diagram

This predominance diagram shows the effects of oxygen and sulfur

partial pressure on the equilibrium phase that forms on copper
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Equilibrium Map #4: Defect Diagram

This type of diagram shows the dependence of a variety of mobile

charges (electrons/holes) and crystal defects (vacancies/interstitials,
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neutral/ionized) on O2 partial pressure

Equilibrium Map #5: Pourbaix Diagram

corrosion

passivation

immune to
corrosion

A Pourbaix diagram is the potential/pH (hydrogen ion concentration)

diagram that maps out possible stable phases of an aqueous
electrochemical system. Example here shows the chemical equilibria
that exist in an electrochemical system as a function of electrode
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potential and pH value

So how do we get there?

All of these useful equilibrium maps are developed from
relationships developed from the principles and strategies of
thermodynamic
In order to understand them, we first need to understand the
scientific basis of thermodynamics (laws + definitions)
Next we will have to learn how to compute properties from these
laws/definitions

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