Chapter 4.

equilibrium
Thermal , mechanical, chemical equilibrium

Thermodynamics
 a system:
Some portion of the universe that you wish to study
 The surroundings:
The adjacent part of the universe outside the system

Changes in a system are associated with the transfer of energy

Natural systems tend toward states of minimum energy

H.S. CHANG 1
Systems
• System – the PART of the universe that is under
consideration. It is separated from the rest of the universe
by it’s boundaries
– Open system  when matter CAN cross the boundary
– Closed system  when matter CANNOT cross the boundary
– Isolated  Boundary seals matter and heat from exchange with
another system

open ↔ matter
heat closed ↔ heat isolated

H.S. CHANG 2
 Energy States

 Unstable: falling or rolling

 Stable: at rest in lowest energy state

 Metastable: intermediate energetic

state within a dynamical system other
than the system's state of least
energy.

H.S. CHANG 3
Gibbs Free Energy
Gibbs free energy is a measure of chemical energy
All chemical systems tend naturally toward states of minimum Gibbs
free energy

G = H - TS
Where:
G = Gibbs Free Energy
H = Enthalpy (heat content)
T = Temperature in Kelvins
S = Entropy (can think of as randomness)

The change in some property, such as G for a reaction of the type:

2A + 3B =C +4D
ΔG = Σ (n G)products – Σ (n G)reactants
= GC + 4GD - 2GA - 3GB

H.S. CHANG 4
1st Law of Thermodynamics
• Gibbs in 1873 stated energy cannot be created or
destroyed, only transferred by any process

• The net change in internal energy of a system is equal

to the heat flow into the system plus the work done on
the system (conservation of energy).

• ΔU = Q + W
– Where Q is heat and w is work
– Some heat flowing into a system is converted to work and therefore
does not augment the internal energy

H.S. CHANG 5
1st Law of Thermodynamics
• We can think about work as a function of pressure and volume
• dw = PdV
• Where PdV is the incremental small change in volume at pressure
associated with force x distance (dimensions of work)
• Restate the first law as:
• dU = dq - PdV

dw

Each point on the curve represents an

equilibrium state of the system.
Our equation of state, the ideal gas law
(PV = nRT), only describes the system
when it is in a state of thermal
equilibrium.

H.S. CHANG 6
1st Law of Thermodynamics
Energy change with volume and heat
• Taking dU = dq – PdV from state 1 to state 2:
2 2 2

∫ dU = ∫ dq − P ∫ dV
1 1 1

• Yields: U2-U1 = (q2-q1) – P(V2-V1)

• Make qp=q2-q1, multiply PV terms and rearrange:
• qp=(E2+PV2)-(E1-PV1)
• qp is MEASURABLE – by measuring temperature changes resulting from
energy changes (i.e. from a chemical reaction)

Enthalpy (H)
• H = U + PV
• Total differential for Enthalpy is:
dH = dU + PdV + VdP
• For our integrated change in state previous:
• H1=U1-PV1 and H2=U2-PV2
DH = H2-H1 = qp (at constant P, V)
H.S. CHANG 7
2nd Law of Thermodynamics
• Heat never flows spontaneously from a colder body to a hotter body.
• 2nd Law introduces entropy, S
dq dq
dS = dS >
T T
(reversible) (irreversible)
• The entropy of the universe never decreases.
- irreversible process increases the total entropy of the universe.
- reversible processes do not increase the total entropy of the universe.

• Combining the 1st and 2nd Laws of Thermodynamics:

dU = dqrev + dw = TdS – PdV
• If a process is at constant volume, V, and entropy, S  dU = 0 
nothing happens, energy does not change in the system
: EQUILIBRIUM
– dU>0  spontaneous rxn products to reactants
– dU<0  spontaneous rxn reactants to products

H.S. CHANG 8
Stability

 −E a 
Nv = N exp  
 kT 
H.S. CHANG 9
Phase equilibrium
We can predict that the slope of
solid-liquid equilibrium should be
positive and that increased
pressure raises the melting point.

High pressure favors low volume,

so which phase should be stable
at high P?

Does liquid or solid have a higher

entropy?
High temperature favors randomness,
Figure. Schematic P-T phase diagram of a melting so which phase should be stable at
reaction.
higher T?

Does the liquid or solid have the

lowest G at point A?
H.S. CHANG 10
Free Energy vs. Temperature
Now consider a reaction, we can then use the equation:
ΔG = ΔVdP - ΔSdT
For a reaction of melting (like ice → water)
 ΔV is the volume change involved in the reaction (Vwater - Vice)
 similarly ΔS and ΔG are the entropy and free energy changes

Slope of GL > Gs
since Ssolid < Sliquid

A: Solid more stable than liquid (low T)

B: Liquid more stable than solid (high T)

Equilibrium at Teq : GL = GS

Figure. Relationship between Gibbs free energy and

∆G = 0 at equilibrium
temperature for the solid and liquid forms of a substance
at constant pressure. Teq is the equilibrium temperature.

H.S. CHANG 11
Phase Equilibrium
Component: is either pure metal and/or compound of which an alloy is
composed. They refer to the independent chemical species that comprise the
system.
Solid Solution: It consists of atoms of at least two different types where
solute atoms occupy either substitutional or interstitial positions in the solvent
lattice and the crystal structure of the solvent is maintained.
Solubility limit: for almost all alloy systems, at specific temperature, a
maximum of solute atoms can dissolve in solvent phase to form a solid solution.
The limit is known as solubility limit.
Phase: defined as a homogenous portion of a system that has uniform
physical and chemical characteristics i.e. it is a physically distinct from other
phases, chemically homogenous and mechanically separable portion of a
system.
Variable of a system: theses include two external variables namely
temperature and pressure along with internal variable such as composition (C)
and number of phases (P). Number of independent variable( (such as pressure,
temperature, and composition) among these gives the degree of freedom (F).
They are given by Gibbs Phase rule
P+F=C+2
H.S. CHANG 12
Solid-solution phase diagram
Phase diagrams are useful tools to determine:
- the number and types of phases,
- the wt% of each phase,
- and the composition of each phase
for a given T and composition of the system.

H.S. CHANG 13
Equilibrium cooling
• Phase diagram:
Cu-Ni system. T(°C) L (liquid) L: 35wt%Ni

→ Phase No. & types

Cu-Ni
130 0 system
A
• System is: L: 35 wt% Ni
--binary α: 46 wt% Ni
35 B 46
i.e., 2 components: 32 C 43
Cu and Ni. D36 L: 32 wt% Ni
24
--isomorphous α : 43 wt% Ni
i.e., complete 120 0 E L: 24 wt% Ni
solubility of one
component in α
α : 36 wt% Ni
another; a phase
(solid)
field extends from
0 to 100 wt% Ni.
110 0
• Consider 20 30 35 40 50
Co = 35 wt%Ni. Co wt% Ni
H.S. CHANG 14
Phase Diagrams

• composition of each phase :

Cu-Ni
C o = 35 wt% Ni T(°C) system
At T A = 1320°C: TA A
tie line
Only Liquid (L) 1300 L (liquid)
CL = Co ( = 35 wt% Ni)
B
At T D = 1190°C: TB
Only Solid ( α) α
Cα = Co ( = 35 wt% Ni) 1200 D (solid)
TD
At T B = 1250°C:
20 3032 35 4043 50
Both α and L CLCo Cα wt% Ni
C L = C liquidus ( = 32 wt% Ni here)
C α = C solidus ( = 43 wt% Ni here)

H.S. CHANG 15
Phase Diagrams
We know the amount of each phase (given in wt%).

• weight fractions of phases: Cu-Ni

C o = 35 wt% Ni T(°C) system
At T A : Only Liquid (L) TA A
tie line
W L = 100 wt%, W α= 0 1300 L (liquid)
At T D : Only Solid ( α)
B
W L = 0, W α= 100 wt% TB R S
At T B : Both a and L α
1200 D (solid)
WL = S =
43 − 35
= 73 wt %
TD
R +S 43 − 32 20 3032 35 40 43 50
CLCo Cα wt% Ni
= R
Wα = 27 wt%
R +S

H.S. CHANG 16
The Lever Rule
• Tie line – connects the phases in equilibrium with
each other - essentially an isotherm
How much of each phase?
T(°C) Think of it as a lever
tie line
1300 L (liquid) WL Co Wα
𝑊𝑊𝛼𝛼 ⋅ 𝑆𝑆 = 𝑊𝑊𝐿𝐿 ⋅ 𝑅𝑅
B
TB
α 1-Wα
R S
1200 (solid) (sum of weight fractions)
R S
(conservation of mass)
20 30C C 40 C 50
L o α C0=WαCα+(1-Wα)CL
wt% Ni C0-CL=Wα(Cα-CL)

ML S C α − C0 R C0 − C L
WL = = = Wα = =
M L + M α R + S C α − CL R + S C α − CL

H.S. CHANG 17
Free energy & Phase Diagrams

H.S. CHANG 18
Eutectic diagram

Eutectic: name comes from the Greek

word eutektos, meaning “easily melted

H.S. CHANG 19
Reaction in binary alloy

liquid transforms to two solid phase

liquid and one solid phase transform to a second solid phase

one solid phase transforms to two other solid phases

H.S. CHANG 20
Reaction in binary alloy

Phase diagrams are useful tools to determine:

--the number and types of phases,
--the wt% of each phase,
--and the composition of each phase
for a given T and composition of the system.

H.S. CHANG 21