Class Announcements

• Assignment:
– Reading: Callister, edition 2: 10.1-10.11, 10.14-10.17
– Reading: Callister, edition 3, 4, or 5: 10.1-10.12, 10.15-10.18
– Homework set 4 due Tuesday, Oct. 29
 Quick Review
• The chemical bonding and molecular shape dictates what
type of material is formed and the molecular structure
• The molecular structure of the material dictates the
material properties
• Many molecules can exist as different structures (and we
call these different structures: phases), for example:
– Iron can form BCC or FCC crystal structures
– Carbon can form graphite, diamond, fullerenes, and nanotubes
– Polymers can be completely amorphous or semi-crystalline

• What dictates which structure (i.e., phase) will be formed?

 Thermodynamics
• The study of how energy in all its
forms is related to one another

• First developed in 1820’s to describe

steam engines

• What are some different forms of energy?

 Thermodynamics
• The study of how energy in all its
forms is related to one another

• First developed in 1820’s to describe

steam engines

• Forms of energy:
– Kinetic: electrical, mechanical, light
– Potential: chemical, magnetic, nuclear, gravitational
– Internal energy: caused by microscopic kinetic and
potential energies of molecules, often considered to be
potential energy
– Work: a process that transfers energy
– Heat: a macroscopic measurement of work (atomic
collisions) that results in energy being transferred
 Thermodynamics
• Classical thermodynamics: macroscopic observations,
“engineering” thermodynamics
• Statistical thermodynamics: microscopic observations,
mathematical description of the statistics of moving
molecules

• Equilibrium: no change in the system

 Equilibrium
• Equilibrium is when a system is at rest or balance
• In thermodynamics, the system will be at equilibrium when it is in
the lowest possible energy state

• We can use thermodynamics and the concept of equilibrium to

predict chemical changes (like reactions) and physical changes
(like ice melting to water, coffee becoming diluted, and a BCC
lattice changing to an FCC lattice)

State 1: solid ice + State 2: diluted, room

concentrated, hot coffee temperature coffee
 Equilibrium
• Equilibrium is when a system is at rest or balance
No further change in free energy of the system
Change in free energy: DG = 0
• In thermodynamics, the system will be at equilibrium when it is in
the lowest possible energy state
If DG < 0, then the system is moving to a lower energy state, so the
process will spontaneously occur.
If DG > 0, then the system is moving to a higher energy state, so
the process will not spontaneously occur.

DG < 0

State 1: solid ice + State 2: diluted coffee

concentrated coffee
 What is the free energy of a system?
• Gibbs Free Energy, G
G = H - TS
where H is enthalpy
T is temperature
S is entropy

– Enthalpy, H: a convenient term to describe internal energy (U) and

work (PV)
H = U + PV
Enthalpy values are tabulated for many materials

– Entropy, S: amount of disorder or randomness in a sample

But what we want to know is the change in energy: DG

 What predicts equilibrium?
• Gibbs Free Energy, G
G = H - TS dG = dH - (dT)(S) - (T)(dS)
for the systems we’ll describe in this class: dT = 0

– Enthalpy, H: a convenient term to describe internal energy (U)

and work (PV)
H = U + PV dH = dU + (dP)V + (P)(dV)
For most solids, dP~0 and dV~0, so dH = dU

– Change in entropy, dS: the change (increase or decrease) in the

amount of disorder or randomness in a sample
 What predicts equilibrium?
DG = DH – T DS
DG < 0, process is spontaneous
DG = 0, process is at equilibrium
DG > 0, process is not spontaneous

DH < 0: Exothermic, heat flows from system to

surroundings
DH > 0: Endothermic, heat flows from
surroundings to system

DS < 0: Process results in more order; for

example, crystallization
DS > 0: Process results in more disorder; for
example, melting
Example: Predicting Spontaneous Solubility
• Will urea spontaneously dissolve in water?

DGmix= DHmix -T DSmix

DGmix > 0

H2O State 2: solid urea + water?

DGmix < 0

State 1: solid urea +

pure water

State 2: dissolved urea?

 Predicting Solubility
• Will urea spontaneously dissolve in water? DGmix= DHmix -T DSmix

• Solid urea is crystalline; how will this affect DSmix?

DSmix < 0 or DSmix > 0

 Predicting Solubility
• Will urea spontaneously dissolve in water? DGmix= DHmix -T DSmix
DSmix = 69.4 J/K mol
• Solid urea can form unusually strong hydrogen bonds with itself; how will
this affect DHmix?
DH = [energy used to break reactant bonds] – [energy released to form product bonds]

DHmix < 0 or DHmix > 0

 Predicting Solubility
• Will urea spontaneously dissolve in water?

DGmix= DHmix -T DSmix

T = 65 F = 18.3 C = 291.5 K
DHmix = 13.8 kJ/mol
DSmix = 69.4 J/K mol
DGmix = -6.43 kJ/mol

• Because DHmix is positive, this is an endothermic process.

• Because DSmix is positive, the solution is more disordered.
• Because DGmix is negative, urea will spontaneously dissolve in water at
room temperature and atmospheric pressure.

• Spontaneous cold packs commonly use this change in phase.

 Phase Diagrams
• Instead of calculating DG for each phase change that might occur, we can put
all of this information into a phase diagram

• Phase diagram: graph that depicts the relationship between variables (like
temperature and pressure) and which phases are present for given components

• Component: the distinct chemical molecules that make up the system; for
example:
– copper, water, NaCl, CaF2, polyethylene, and gold are all components

• Phases: matter with different atomic levels of structure, for example:

– Liquid, gas, solid
– Different types of crystal lattices like FCC, BCC, HCP
– Amorphous, crystalline, semi-crystalline
– Crystalline sodium nitrate and dissolved sodium nitrate
 Single Component Phase Diagram
• Equilibrium phase diagrams:
– Can have many different axis labels (free energy, temperature, concentration, pressure)
– Depict the phase with the lowest free energy at the given conditions
– Solid lines represent conditions where phases can co-exist in equilibrium

Note that the axes are

not drawn to scale in
order to show the most
information possible.
 Independent Variables
• Independent variables are also known as “degrees of freedom”
• Example 1: If you want to do an experiment with water molecules co-existing in
the liquid, solid, and gas phases, can you choose your temperature to be 50ºC?

Yes? No?

Note that the axes are

not drawn to scale in
order to show the most
information possible.
 Independent Variables
• Independent variables are also known as “degrees of freedom”
• Example 2: If you want to do an experiment with water molecules co-existing in
the liquid and gas phases, can you choose your temperature to be 50ºC?

Yes? No?

Note that the axes are

not drawn to scale in
order to show the most
information possible.
 Independent Variables
• Degrees of freedom, F = C - f + N
C is the number of components
f is the number of phases
N is the number of non-compositional intensive variables (e.g., temperature, pressure)

Example 1:
At the triple point,
F=C-f+N
F=1–3+2=0
The experimenter cannot select any
independent variables, i.e. the
experimenter cannot choose a pressure or
a temperature.

Example 2:
Along the water-steam equilibrium,
F=C-f+N
F=1–2+2=1
The experimenter can select only 1
independent variable, i.e. the experimenter
can choose the temperature OR the
pressure, but not both.
 Independent Variables
• Degrees of freedom, F = C - f + N
C is the number of components
f is the number of phases
N is the number of non-compositional intensive variables (e.g., temperature, pressure)

Example 3:
Inside the ice region,
F=C-f+N
F=?
 Cooling Rates and Equilibrium
• If you cool very slowly without external perturbations, the
system will sometimes become super-cooled

• Is a super-cooled system at equilibrium?

Yes? No?

• Examples:
– Two phases: Liquid to solid phase transition
One component: water
– https://www.youtube.com/shorts/0z05d4PK6pA
 Two Component (Binary) Phase Diagram
• Water-Sugar System

• Solubility Limit:
Maximum concentration at
which only a solution
occurs. Above this limit, there
is a mixture of a liquid solution
with insoluble solid.

Diagram variables: Temperature and composition

Non-compositional intensive variables: Temperature

If a variable is not shown on the phase diagram, we assume it is constant.

 Two Component (Binary) Phase Diagram
• Water-Sugar System

pure
water
solid
Example: sugar

What is the solubility limit at 20ºC?

At 80 wt% sugar, how high must you heat it to solubilize the sugar into syrup?

How many degrees of freedom are there in the liquid solution region?
F=C-f+N=?

How many degrees of freedom are there in the liquid solution + solid sugar region?

How could you use this phase diagram to make candy?

 Two Component (Binary) Phase Diagram
• Water-Sugar System

F=2
What is the solubility limit at 20ºC?
63 wt% sugar
If Co < 63 wt% sugar: syrup
If Co > 63 wt% sugar: syrup + sugar F=1

At 80 wt% sugar, how high must you heat it to solubilize the sugar into syrup?
Solubility limit increases with T:
e.g., if T = 100ºC, solubility limit = 80 wt% sugar

How many degrees of freedom are there in the liquid solution region?
F=C-f+N=?=2–1+1=2

How many degrees of freedom are there in the liquid solution + solid sugar region?
F=C-f+N=?=2–2+1=1
 Solubility Phase Diagram
• If you are making “rock candy”, how can you control at which
temperature the candy will begin to crystallize?
- One degree of freedom
- You can only specify one experimental variable

• How to make rock candy video:

https://www.youtube.com/watch?v=HYRbtnqvteQ

A (70 wt% syrup)

B
(70 wt% syrup + small bit solid sugar)

C
(62 wt% syrup + more solid sugar)
 One Component (Unary) Phase Diagram
• Now let’s translate what we’ve
learned about water and water-sugar
phase diagrams to metal materials
F=1
• One component: Gold
(T or P)

• Two phases: FCC solid and liquid, F=2

solid line shows the melting (T & P)
F=2
temperature at different pressures
(T & P)

• At atmospheric pressure (~1 bar), the

melting temperature is 1337 K F=C-f+N
• How is gold used in medicine?
 Gold in Modern Medicine
• Eyelid weights – use gravity to assist with closing the eye

• Dentistry (usually a gold alloy to improve durability)

• How do we describe mixtures of metals (alloys)?

 Mixtures of Metals (i.e. Alloys)
• Components:
The elements or compounds which are mixed initially (e.g., Al and Cu)
• Solubility:
If the two metals are “soluble,” then only a single phase is formed
• Phases:
The physically and chemically distinct material regions
that can result. Metallic mixtures often include more than one solid
phase, often with different lattice structures (e.g., a and b).

Both the a and b phases

Adapted from contain both
Fig. 9.0,
Callister 3e. components, Al and Cu,
but they are present in
Aluminum-Copper Alloy
different ratios!
 Binary Phase Diagrams
• Binary phase diagram example with soluble metals: copper and nickel
• Unlike solid sugar, the composition of the solid metal can change (i.e. the
ratio of copper to nickel within the solid phase can change). This is shown
with the solidus line.

• 2 components:
Copper (Cu)
Nickel (Ni)

Adapted from Fig. 9.2(a), Callister 6e.

Cu-Ni Phase Diagram (Fig. 9.2(a) is adapted from Phase
Diagrams of Binary Nickel Alloys, P.
Nash (Ed.), ASM International,
Materials Park, OH (1991).
 Binary Phase Diagrams
• Binary phase diagram example with soluble metals: copper and nickel
• Unlike solid sugar, the composition of the solid metal can change (i.e. the
ratio of copper to nickel within the solid phase can change)

• 2 components:
Copper (Cu)
Nickel (Ni)

Adapted from Fig. 9.2(a), Callister 6e.

Cu-Ni Phase Diagram (Fig. 9.2(a) is adapted from Phase
Diagrams of Binary Nickel Alloys, P.
Nash (Ed.), ASM International,
Materials Park, OH (1991).
 Two Proofs for the Lever Rule

• Sum of weight fractions:

• Conservation of mass (Ni):
• Combine above equations:

• A geometric interpretation:
 Solidification
Consider:
Co = 35 wt% Ni
Cu-Ni
system
What happens to
the amount of the
solid phase as the
solution is cooled?

What happens to
the composition of the
solid phase as the
solution is cooled?

Adapted from Fig. 9.3,

Callister 6e.
 Cored versus Equilibrium Phases
• The solid phase grows as we lower the temperature
• Ca changes as we lower the temperature
• Cu-Ni case: First a to solidify has Ca = 46 wt% Ni, 54 wt% Cu
Last a to solidify has Ca = 35 wt% Ni, 65 wt% Cu
• Fast rate of cooling:
Cored structure
 Cooling Rates and Equilibrium
• Is a “cored” particle at equilibrium? Yes or No?

• Fast rate of cooling:

Cored structure
 Cooling Rates and Equilibrium
• Is a “cored” particle at equilibrium? Yes or No?

• Fast rate of cooling: • Slow rate of cooling:

Cored structure Equilibrium structure
 Cooling Rates and Equilibrium
• This is another example of super-cooling
• A super-cooled system is not at equilibrium
• In liquid to solid phase transitions for metals, super-
cooling is more common when you cool very quickly

• Super-cooled Examples:
– Liquid to solid phase transition
One component: water
• https://www.youtube.com/shorts/0z05d4PK6pA
– Cored metallic particles
 Lecture 7 Summary
• Things you should now be able to do…
Describe the concepts of free energy, enthalpy, and entropy
Use the Gibbs Phase Rule
Use a binary phase diagram to:
determine which phases are present
determine the composition of each phase
determine the relative abundance of each phase
(an extra example is included at the end of the lecture notes)

• Assignment
– Reading: Callister, edition 2: 10.1-10.11, 10.14-10.17
– Reading: Callister, edition 3, 4, or 5: 10.1-10.12, 10.15-10.18
– Homework set 4 due Tuesday, Oct. 29
 Another Binary Phase Diagram Example
• For point A and point B, determine:
- which phases are present
- the composition of each phase (in same units as the graph)
- the amount of each phase (in same units as the graph)
 Another Binary Phase Diagram Example
• For point A and point B, determine:
- which phases are present
- the composition of each phase (in same units as the graph)
- the amount of each phase (in same units as the graph)

Point A: C0,Ni = 60 wt% Ni

Phases: a solid

Composition:
Ca,Ni = 60 wt% Ni
Ca, Cu = 40 wt% Cu

Amount of each phase:

100% a solid
 Another Binary Phase Diagram Example
• For point A and point B, determine:
- which phases are present
- the composition of each phase (in same units as the graph)
- the amount of each phase (in same units as the graph)

Point B: C0,Ni = 36 wt% Ni

Phases: liquid + a solid

Composition:
CL,Ni = 33 wt% Ni
CL, Cu = 67 wt% Cu

Ca,Ni = 45 wt% Ni
Ca, Cu = 55 wt% Cu

Amount of each phase:

WL = (Ca – C0) = 45 – 36 = 0.75
(Ca – CL) 45 – 33

Wa = 1 – WL = 1 – 0.75 = 0.25