Foundations of Nanotechnology I

Phase Equilibria for Nanoscale Systems

CNSE 506
Fall 2013

Professor Kathleen A. Dunn
NanoFab East 4316
437-8761
kdunn1@albany.edu
Overview of Todays Lecture
Course Structure & Expectations
Technical Content
Classification of Systems
Classification of Variables
State Functions
Process Variables
Classification of Relationships
Equilibrium & the Laws of Thermodynamics


Philosophical Statement: Text, Context, Pretext
Text: the material you are here to learn (content)

Context: the relationship of that information to other things
you know & understand -- that which allows you to make
sense of the text

Pretext: the reason you are here to learn it & more generally
the meta-text: what you are here to learn BESIDES the text

There isnt a scientific community. Its a culture. It is a
very undisciplined organization.
-- Francois Rabelais
Course Goals & Objectives
The relationship between the fundamental concepts of
thermodynamics and the development of equilibrium structures in
materials systems
The importance of the chemical potential in describing phase
equilibria in condensed systems equality of the chemical potential
when phases are in equilibrium
Goals:
At the end of this module, you should understand:
Objectives (indicators of goals):
At the end of this module, you should be able to:
Discriminate between equilibrium and non-equilibrium systems
Sketch free energy diagrams to describe phase equilibria
Construct and use complex phase diagrams to predict system stability
Apply the concepts of thermodynamics to nanoscale systems,
including the effect of surfaces and interfaces
Organizational Details
Structure
14 Lectures
Pass/Fail Homework assignments (5%)
5 in-class quizzes (75 % of grade)
Final Exam (20% of grade)

Office Hours Monday & Wednesday 4-5 pm, or by appointment
All handouts available at http://blackboard.albany.edu/
Lecture Date Topic: Corresponding Text
1 8/27 Course Structure & the Language of Thermodynamics Chapters 1,2
2 8/29 The Laws of Thermodynamics Chapter 3
3 9/3 Thermodynamic Relationships Chapter 4.1
4 9/10 Thermodynamic Problem Solving Chapter 4.2
5 9/12 Equilibrium & the Chemical Potential Chapter 5
6 9/17 Single Component Systems (Unary Heterogenous) Chapter 7
7 9/19 Multicomponent Systems (Mixing) Chapter 8.1-8.3
8 9/24 Multicomponent Systems (Activity, Solutions, Chemical Potential) Chapter 8.4-8.8
9 9/26 Mutltiphase, Multicomponent Systems (Gibbs Rule, intro to diags) Chapter 9.1-9.4
10 10/1 Interpreting Phase Diagrams Chapter 9.5-9.7
11 10/3 Thermodynamics of Phase Diagrams Chapter 10
12 10/8 Multicomponent, Multiphase, Reacting (Ellingham, Pourbaix) Chapter 11
13 10/10 NanoThermo: the role of Surfaces & Interfaces (Capillarity) Chapter 12
14 10/15 Review Session
A Different
View
Final Exam
TBA

Note: 10/16-10/17

Source Books
Text: Thermodynamics in Materials Science 2
nd
edition, Robert T.
DeHoff, New York: McGraw-Hill.


Other recommended resource materials:
Phase Transformations in Metals and Alloys, D.A. Porter & K.E. Easterling,
New York: Chapman and Hall.

Introduction to Metallurgical Thermodynamics, David R. Gaskell, New York:
McGraw-Hill; Introduction to the Thermodynamics of Materials, ibid.

Thermodynamics of Solids, R. A. Swalin, New York: Wiley & Sons.

Principles of Phase Diagrams in Materials Systems, Paul Gordon, New York:
McGraw-Hill.

The Structure and Properties of Materials, Volume II: Thermodynamics of
Structure, Jere H. Brophy, Robert M. Rose and John Wulff, New York: Wiley
& Sons.
Rubric for Homeworks & Quizzes
(1) Responds fully to the
assignment (answers each
problem)
(2) Invokes and uses disciplinary
facts correctly

Excellent Very good Adequate Weak Poor
Excellent Very good Adequate Weak Poor
Recall of Facts and Details
(a)
(f)
(k)
(b)
(g)
(l)
(c)
(h)
(m)
(d)
(i)
(n)
(e)
(j)
(o)
(From Nickerson & Adams, 1979)
Rubric for Homeworks & Quizzes
(1) Responds fully to the
assignment (answers each
problem)
(2) Invokes and uses disciplinary
facts correctly
(3) Avoids brain-dump
responses (dont make me
guess which of your
answers you meant)
(4) Identifies correct &
necessary calculations
(5) Performs necessary
calculations correctly
(6) Is written legibly
Excellent Very good Adequate Weak Poor
Excellent Very good Adequate Weak Poor
Excellent Very good Adequate Weak Poor
Excellent Very good Adequate Weak Poor
Excellent Very good Adequate Weak Poor
Excellent Very good Adequate Weak Poor
Anything I cant read,
or have to guess which answer you meant
will always be misinterpreted!
This big and copper isnt good enough!
Course Goal: Phase Equilibria
What do we mean by equilibrium?
Stability: Identifying the Proper Potential
Analogously, we want to determine the thermodynamic
potential that will be minimized at thermodynamic equilibrium

First: what is thermodynamics & why study it?

In solid body mechanics: a
minimum in potential energy
represents the equilibrium
position of a system

E
x
A
B
C
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 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

Thermodynamics for Phase Equilibrium
Based on the interactions between phases
Dont have to count every particle, consider just subsets of the full ensemble
We will allow particles to interact (react, change phase, etc.)
Why Study Thermodynamics?
Predictions of behavior based on known properties
(dont necessarily have to do EVERY experiment!)


What happens at 500C ?
Will the layers stay intact? Or mix?
substrate
Why do Peeps expand when
microwaved?
Thermodynamics applies even to complex
systems
How strong can we make these MRI magnets
before they lose their superconductivity?
What happens to this system when we apply
an electric field (and the transistor heats up)?
Before we can address these
questions, we have to agree
on terminology & rules!
Magic Trick
Language Describing the Behavior of Matter
system
boundary
Universe
(everything else)
We need to be explicit about
the condition of the system

Properties
Temperature (T)
Pressure (P)
Volume (V)
Chemical composition (X
i
)
Phase assembly (o,|,)
What happens to these properties when the
system is subjected to a process?
System in
State A

T
A
, P
A
, V
A

Process
System in
State B

T
B
, P
B
, V
B

AT
AP
AV
A

Classifications will help us organize our understanding of
thermodynamic systems, properties, and relationships
Classification of Systems
Questions to ask:
1. How many reacting components
(unary, binary, ternary)
2. Is it homogeneous or heterogeneous?
Solution vs. Mixture
Sidebar: definition of phases
3. Is this system open or closed (with respect to
interactions with the universe)
4. Is anything reacting? (Big One for us!)
5. Are there other complexities affecting the state of
the system? Electric field, magnetic field,
gravitational fields
Sidebar: What is a phase?
How many phases exist?
a) 3
b) 4
c) 6
d) millions
Phase = State of Aggregation

Phase = Different Composition

Definition of Phase
Phase
a portion of the system whose properties and
composition are homogeneous and which is
physically distinct from other parts of the system
vs. steel salt & pepper
S
o
l
u
t
i
o
n

=

1

p
h
a
s
e

M
i
x
t
u
r
e

=


2

o
r

m
o
r
e

p
h
a
s
e
s

salt water
oil
water vs.
Definition of Phase
Phase
a portion of the system whose and
. are and which is
. from other parts of the system
vs. steel salt & pepper
S
o
l
u
t
i
o
n

=

1

p
h
a
s
e

M
i
x
t
u
r
e

=


2

o
r

m
o
r
e

p
h
a
s
e
s

salt water
oil
water vs.
Back to: Classification of Systems
Questions to ask:
1. How many reacting components
(unary, binary, ternary)
2. Is it homogeneous or heterogeneous?
Solution vs. Mixture
Sidebar: definition of phases
3. Is this system open or closed (with respect to
interactions with the universe)
4. Is anything reacting? (Big One for us!)
5. Are there other complexities affecting the state of
the system? Electric field, magnetic field,
gravitational fields
System
Universe
Fe
O
2
rust
Slightly
less O
2
State Functions vs. Process Variables
Classification of Thermodynamic Variables
System in
State A

T
A
, P
A
, V
A

Process
System in
State B

T
B
, P
B
, V
B

State Function/ State Variable
State variable = property of the system which has a fixed value in a
given equilibrium state regardless of how the system arrives at that state
Example: PV = nRT
X = P
Y = V
Z = T
State Function/ State Variable
State variable = property of the system which has a fixed value in a
given equilibrium state regardless of how the system arrives at that state
Example: PV = nRT
X = P
Y = V
Z = T
State variable = of the system which has a in a
given state regardless of at that state
In other words, the change in the value of
the state variable will be _________ no
matter what path you take between the
two states.
Another view of State Variables
The change in the value of the state variable will be the same no matter what
path you take between the two states.

If a system is carried through a cycle to its
original state, the variable Z is a state
variable iff it returns to its original value.
}
=
cycle
dZ 0
State variable = of the system which has a in a
given state regardless of at that state
Subdivide State Variables into
Extensive vs. Intensive Properties
Extensive vs. Intensive
Extensive properties if the
value for the whole
system is the sum of its
values for the parts

Intensive properties do
not depend on the total
mass or amount of
material, and have the
same value in all parts of
the system at equilibrium
Think, Pair, Share
Extensive or intensive?
Mass, temperature,
density, surface area,
pressure, volume
Extensive vs. Intensive Properties
Mass is an ________ property, because its value _________ depend
on the sum of parts

Temperature is an ________ property, because its value _________
depend on the sum of parts

Density is an ________ property, because its value _________
depend on the sum of parts

Surface area is an ________ property, because its value _________
depend on the sum of parts

Pressure is an ________ property, because its value _________
depend on the sum of parts

Volume is an ________ property, because its value _________
depend on the sum of parts

State Variables & Degrees of Freedom
Any state variable (property) has a fixed
value in a given equilibrium state
regardless of how the system arrives at
that state

All systems are describable by specifying
an ensemble of state variables.

For most systems, it is not necessary to
specify them ALL.

The smallest number that must be
specified to completely describe the
entire thermodynamic state of the
system is called the variance or the
degrees of freedom of the system.

The State Postulate
The state of a simple compressible system can be uniquely
specified by two independent intensive properties

A quantity of gas contained in a cylinder by a piston
Microscopic state:
position & momentum vector of each
gas molecule (10
23
??)

Macroscopic state:
Fix 2 independent intensive properties
& the rest follows

Choices for intensive properties?

What shall we choose?
weight
State Function: PV = nRT
Changing one of the State Variables
weight
What happens if the force on the piston is increased?
Intuitively you know the answer: the piston will sink.
But how far?


Explicitly: (lets assume T is constant)
the pressure exerted by the weight increases to P
2
resulting imbalance between the pressure exerted on
the gas and the pressure exerted by the gas, forces
the piston into the cylinder
the volume of the gas must therefore decrease to V
2

which increases the pressure inside the cylinder until
it equalizes with the external pressure exerted by the
piston


State Function: PV = nRT
weight
In Thermodynamic Terms
The change in pressure takes the system from the
Initial state described by (P
1
,T
1
), to the
Final state described by (P
2
, T
1
)

and the volume, as a dependent variable, changes from V
1
to V
2
.
(P
1
, T
1
)

P

T

V

V = V(P,T)

V
2
V
1
(P
2
, T
1
)
State Functions vs. Process Variables
Classification of Thermodynamic Variables
System in
State A

T
A
, P
A
, V
A

Process
System in
State B

T
B
, P
B
, V
B

State variable = property of the system which has a fixed value in a
given equilibrium state regardless of how the system arrives at that state
Process variable = _____ of the system which depends on __________
How Does that Process Occur?
Process variable = property that only has meaning for a changing system
(explicitly path-dependent!)
Process vs. Path
A process is any transformation
of the system from one
equilibrium state to another

The path of a process refers to
the specification of the series of
states through which the system
passes
State variable example:
PV = nRT
X = P
Y = V
Z = T
But each path has a different
WORK done & HEAT added
Process Variable: Work
F
ds
}
= ds F W
Forces may be due to:
Applied pressure
Gravity
Rotation
Electric fields
Magnetic fields
Surface tension
Any force that causes a displacement of the point of application can do work

Displacement implies change, so work is a process variable and not a state variable
An Aside for the Physicists
Work is only path-independent for conservative forces
gravity in the absence of air resistance
ideal springs, pendula, etc.
}
=
cycle
conserv
ds F 0
RE: work as a path-dependent quantity
}
=

cycle
conserv non
ds F 0
Work is path-dependent for non-conservative forces
friction & other dissipative forces can still do work
m
m
Process Variable: Heat
What is Heat?
(as opposed to Temperature)
Rigid, impermeable box
Can system ever change?
Temperature measures the
state RIGHT NOW

Heat changes the system

Heat content of the
system is meaningless
State Functions vs. Process Variables

Can we describe these mathematically?
Classification of Thermodynamic Variables
System in
State A

T
A
, P
A
, V
A

Process
System in
State B

T
B
, P
B
, V
B

Mathematical Descriptions of Relationships
... + + = NdY MdX dZ
Infinitesimal steps in functions X, Y, result in
infinitesimal change in state function Z:
Where the coefficients M & N are
the partial derivatives:
,... Y
X
Z
M
|
.
|

\
|
c
c
=
,... X
Y
Z
N
|
.
|

\
|
c
c
=
Maxwells relations tell us how
those coefficients are related
,... ,... Y X
X
N
Y
M
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c

What is Equilibrium?
A system in balance

Conditions for 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


A system not in equilibrium with its
environment will change
spontaneously until it has
exhausted its capacity for change
Types of Equilibrium
Thermal: equality of T across the system boundary
Mechanical: equality of P 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
Ice & Water in a closed
system at 1 atm.
Whats the condition
for equilibrium?
Conditions for Equilibrium
Equilibrium
A system is in thermodynamic
equilibrium if it is not capable of a ___,
_________ change to another state
without a _____ _____ in the state of
_________________


A system not in equilibrium with its
environment will change
__________ until it has exhausted
its ______________
Types of Equilibrium
Thermal: equality of T across the system boundary
Mechanical: equality of P 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
Ice & Water in a closed
system at 25C. Whats
the condition for
equilibrium?
Discussion
Ice & Water in a closed, thermally
isolated system.

True/False & why?

Ice and water can never be in phase
equilibrium because they are different states
of aggregation (1 Liquid, 1 Solid)

If we removed the thermally isolated
constraint, the system would absorb heat
from the environment and melt the ice.

The system will never be in phase
equilibrium because molecules are
constantly transferring from ice to water and
back again
Aside: Equilibrium vs. Stead-State
Whats the difference?
Equilibrium: all state variables are
constant and net reaction rate = 0

Example: Pour 80 L of water into a empty tub and let it
settle, the state variables (volume, pressure,
temperature, composition) are constant.

Steady-state: all state variables may
be constant but net reaction rate
may be nonzero

Example: Start with empty tub, pull out the drain plug &
turn on the faucet. After some time, the flow in will
equal the flow out so again the volume will stabilize.
Net reaction rate (in this case, mass flow), is nonzero.
Laws of Thermodynamics
E
x
A
B
C
1st Law: Conservation of Mass & Energy
Mass Conservation:
the ancient Greeks, really
1774: Lavoisier conclusively demonstrated conservation
of mass in chemical reactions
1st Law: Conservation of Mass & Energy
What do we mean by energy?

The capacity to do work ?

vs.

The capacity to induce a change
in that which inherently resists
change

Capacity = Effort & Change
= Driving Force x Displacement
If DF + displacement contained in system, this
results in a change in internal energy, which is as
important to thermodynamics as changes in
position or motion of entire system.
1st Law: Conservation of Mass & Energy


Energy Conservation:
1797: Count Rumford at the cannon factory showed
caloric cannot be depleted
1799: Humphrey Davy melts ice in a vacuum, end of
caloric gas theory of thermal conduction

Equivalence of Work & Heat:
1843-1848: Joule & Kelvin
demonstrated indisputably
the precise equivalence of
mechanical work & total
thermal energy obtainable
from it
E, m treated separately:
What about E = mc
2
?
Equivalence of Work & Heat
Energy conservation: The change in internal energy (U)
of a system is equal to the heat (Q) added to the system
plus the mechanical work (W) and non-mechanical work
(W) done on the system.
dU = oQ + oW + oW
Path independent Path dependent!
P
V
Initial State
Final State
For a cycle, AU=0
But Q, W, W = 0
Mass conservation: material neither created nor destroyed
AU = Q + W + W
Heat in: Q +ve
Heat out: Q ve

Work done on: W +ve
Work done by: W -ve
oW = - P dV
dU = oQ - PdV + oW
Equivalence of Work & Heat
True or False?
Why?
Work and Heat are equivalent because they are both forms of energy.
Work and Heat are equivalent because The Prof just said so.
Work and Heat are equivalent because Joule & Kelvin said so, and theyre
names I recognize from the Nobel Prize list.
If Joule & Kelvin say so
Do you believe Heat & Work are equivalent?
Think, Pair, Share

Do you expect that:
Stones, cooling themselves, could convert their heat
contents into work: roll uphill unaided?
Hot water could spontaneously convert its heat into
kinetic or potential energy?

Not in our experience. So dU = oQ + oW + oW cannot be
the full story on thermodynamics!

Nature does not allow heat to be spontaneously converted
into work without the accompaniment of other changes.
(Kelvins formulation of 2nd law!)
2
nd
Law: Directionality of Processes
Times arrow in classical thermodynamics: Entropy (S)
Changes occur in the direction that increases entropy for the
universe ( system + surroundings)

For any given process, entropy of the system may increase or
decrease: but the total entropy of universe must increase
heat
engine
Hot reservoir Cold reservoir
oW s oQ
h
- oQ
c
Entropy as waste or unavailable energy
Entropy as Disorder
Ordered structures (crystals) vs.
ice, H
2
O
water, H
2
O
graphite, C
amorphous C
quartz, SiO
2

silica, SiO
2

Atomic example:
Molecular examples: let = molecule
As more became known about the nature of matter, the
statistical thermodynamics concept of entropy as disorder
(mixedupness) arose
disordered structures (gasses,
most liquids, amorphous solids)
Configurational Entropy
As more became known about the nature of matter, the
statistical thermodynamics idea of entropy as disorder
(mixedupness) arose
Configurational entropy
A
B
Case 1
Case 3
Case 2
Which has the greatest (configurational) entropy? Which has the least?
Configurational Entropy
Configurational entropy
A
B
Case 1
Case 3
Case 2
Which has the greatest (configurational) entropy? Which has the least?
They all have the same entropy because all microstates are equivalent.

Case 1 has the most entropy because it is the least likely to occur.

Cause 2 has the most entropy because it is the most mixed up.

True/False? Discuss your evidence.
Configurational Entropy vs. Microstates
Each microstate is unique but there are many more essentially random ones
Consider what can be swapped for what
A
B
Case 1
Case 3
Case 2
1 2 3 4 5 6 7 8 9 10
1
2
3
4
5 6
7 8
9
10
1 2 3
4 5 6 7
8 9 10
Neighbor Tally
38 A-B nearest neighbors
9 B-B nearest neighbors
x A-A nearest neighbors



74 A-B nearest neighbors
0 B-B nearest neighbors
y A-A nearest neighbors


22 A-B nearest neighbors
37 B-B nearest neighbors
z A-A nearest neighbors
Try to make an equivalent state with
the same number of interactions
Configurational Entropy vs. Microstates
1 2 3 4 5 6 7 8 9 10
Neighbor Tally
38 A-B nearest neighbors
9 B-B nearest neighbors
x A-A nearest neighbors



42 A-B nearest neighbors
7 B-B nearest neighbors
x-2 A-A nearest neighbors



38 A-B nearest neighbors
9 B-B nearest neighbors
x A-A nearest neighbors
1 2 3 4
5
6 7 8 9 10
1 2 3 4 5 6 7 8 9 10
Can only swap for if I swap the entire row
Case 1 (lowest entropy): limited # of equivalent states
Case 1
Configurational Entropy vs. Microstates
Case 2 (highest entropy): nearly infinite # of equivalent states
Case 2
1
2
3
4
5 6
7 8
9
10
Neighbor Tally
74 A-B nearest neighbors
0 B-B nearest neighbors
y A-A nearest neighbors



74 A-B nearest neighbors
0 B-B nearest neighbors
y A-A nearest neighbors



74 A-B nearest neighbors
0 B-B nearest neighbors
y A-A nearest neighbors

1
2
3
4
5 6
7 8
9
10
1
2
3
4
5 6
7
8
9
10
In fact I can swap any for any
Configurational Entropy vs. Microstates
Case 3 (moderate entropy): Moderate # of equivalent arrangements
Case 3
1 2 3
4 5 6 7
8 9 10
Neighbor Tally
22 A-B nearest neighbors
37 B-B nearest neighbors
z A-A nearest neighbors



22 A-B nearest neighbors
37 B-B nearest neighbors
z A-A nearest neighbors



22 A-B nearest neighbors
37 B-B nearest neighbors
z A-A nearest neighbors

1 2 3
4 5 6 7
8 9 10
1 2 3
4 5 6
7 8 9 10
Have to swap several for
Can have many microstates with same S
Entropy
A measure of disorder or
randomness
C
o
n
f
i
g
u
r
a
t
i
o
n
a
l

e
n
t
r
o
p
y




6 equivalent microstates




Nearly equivalent microstates





~45 equivalent microstates

8

A
B
Case 1
Case 3
Case 2
Entropy and Randomness
Consider it atomistically: in any conglomeration of atoms, each atom has
thermal kinetic energy & an associated velocity which continually change both
in magnitude and direction by chance collisions with other atoms

From a strictly statistical point of view, an essentially random positional
arrangement (Case 2, on previous slides) has by far the highest probability of
occurring at any given moment.

BUT it doesnt win because it is opposed by (and at least partially
counterbalanced by) the forces derived from the potential energy of the atoms.

HOWEVER:
The tendency towards randomness is always present and is stronger when
atomic kinetic energies are higher (i.e., at higher temperatures)

Described mathematically as:
T
Q
dS
rev
o
=
change in heat, applied reversibly
(i.e. without losses) to achieve the event
temperature at which the event occurs
incremental change in entropy
for a particular event
The 2nd Law, Mathematically
The entropy of an isolated system not at equilibrium will tend
to increase over time, approaching a maximum value.









For a process taking place for a system at equilibrium
(reversible), the entropy of a system + surroundings, the
entropy of system + surroundings is constant:



In a spontaneous (irreversible) process:



0 = +
rev
surr
rev
sys
dS dS
0 > +
irrev
surr
irrev
sys
dS dS
Combined Statement of 1
st
& 2
nd
Laws
dU = oQ - P dV + oW
1
st
Law:
2
nd
Law:
T
Q
dS
rev
o
=
dU = T dS - P dV + oW
A centerpiece of the mathematical
framework of thermodynamics!
3
rd
Law: Absolute Zero
As a system approaches absolute zero of temperature all
processes cease and the entropy of the system approaches
a minimum value which is the same for all substances.
For conveniences sake, choose this minimum value to be 0
Handy for calculating the change in entropy for chemical
reactions without having to actually measure every case
experimentally.
AS (Reaction) = Products - Reactants
To simplify the calculations of AS for chemical reactions, the
values of S are tabulated for elements & many compounds at
a standard state, taken to be 298K and 1 atm pressure:
o
S
298

Substance S
298
(J/mol K)
C (graphite) 5.69
O
2
205.03
CO 197.9
CO
2
213.64

First write a stoichiometrically
balanced equation for the reaction
C + O
2
= CO
(

+ = A ) (
2
1
) ( ) ( ) (
2 298 298 298 298
O S C S CO S rxn S
o o o o
(

+ = A ) 3 . 205 (
2
1
69 . 5 9 . 197 ) (
298
rxn S
o
56 . 89 ) (
298
= A rxn S
o
J/mol K
Summary

Thermodynamics describes the quest for equilibrium
Classification of Systems
Classification of Variables
State Functions
Process Variables
Classification of Relationships
Equilibrium & the Laws of Thermodynamics
0: You have to play the game.
1: You cannot win.
2: You cannot break even, except at absolute zero.
3: You cannot reach absolute zero.
The Minute Paper (Anonymous!)
Take an index card

On the front of the card
What do you think was the most important point of todays
lecture?

On the back of the card
What was the muddiest point in this lecture? That is, what
was least clear to you?

Turn in the index card when you leave, please!