Physical Transformations of

Pure Substances
 Phase
• A phase (P) of a substance is a form of matter that is uniform throughout in
chemical composition and physical state (e.g., Solid, Liquid, and Gas)
– The solid form of matter is most stable at low temperatures
– Most substances can exist in liquid and gaseous phases at higher temperatures

• A phase transition is the spontaneous conversion of one phase into another and
may be studied by techniques that include thermal analysis

• The thermodynamic analysis of phases is based on that fact that, at equilibrium,

the chemical potential of a substance is the same throughout a sample
 Phase
• A phase (P) of a substance is a form of matter that is uniform throughout in
chemical composition and physical state (e.g., Solid, Liquid, and Gas)

The number of phases Dispersion: regions of

one component are
• A gas: P = 1 embedded in a matrix of
a second component –
• A gaseous mixture: P = 1 could be uniform on a
macroscale but not on a
• A crystal of a substance: P = 1
microscale
• A solution of NaCl in water: P = 1
• Ice: P = 1 A single-phase solution: the
composition is uniform on both
• A slurry of ice and water: P = 2
microscopic and macroscopic scales
• Two fully miscible liquids: P = 1
• Two immiscible metals: P = 2
• Two miscible metals forming an alloy: P = 1
• A system in which calcium carbonate
undergoes the thermal decomposition
CaCO3(s)  CaO(s) + CO2(g) : P = 3
 Phase Transition
• A phase transition: spontaneous conversion of one
phase into another phase occurs at a characteristic
temperature for a given pressure (e.g., ice  liquid
water)

• Transition temperature, Ttrs: at which the two

phases are in equilibrium
 Detection of A Phase Transition
freezing

• Thermal analysis: the temperature does not change even

though heat is being supplied or removed from the sample-
Differential scanning calorimetry & X-ray diffraction
 Phase Transition
(Thermodynamics vs. Kinetics)
• Thermodynamics
– Molar Gibbs energy of graphite < molar Gibbs energy of
diamond
– Therefore, there is a thermodynamic tendency for diamond
to change into graphite

• Kinetics
– C atoms in solid must change their location: an immeasurably
slow process in a solid except at high temperatures

• Metastable phases
– thermodynamically unstable phases that persist because the
transition is kinetically hindered. i.e. diamond
 Molar Gibbs Energy,
Chemical Potential
• All considerations will be based on the Gibbs energy of a substance and in particular
on its molar Gibbs energy (Gm)

• For a one-component system, ‘molar Gibbs energy’ and ‘chemical potential’ are
synonyms (µ = Gm)

• Chemical potential is the potential of a substance to undergo physical or chemical

change

• At equilibrium, the chemical potential of a substance is the same throughout a sample,

regardless of how many phases are present
 Phase Diagram
• Phase diagram is a map of the pressures and
temperatures at which each phase of a substance is
the most stable
– How vapor pressure of a substance varies with
temperature
– How melting point varies with pressure

• Chemical potential – molar Gibbs energy

• The phase boundaries are the lines separating the

regions and show the values of p and T at which two
phases coexist in equilibrium and their chemical
potentials are equal

• The tendency of systems at constant temperature

and pressure to minimize their Gibbs energy
 Phase Diagram

• Phase boundaries: two phases coexist • Vapour in equilibrium with the liquid
in equilibrium (or solid)

At equilibrium, the chemical potential of a substance is the same throughout a sample,

regardless of how many phases are present
 Vapor Pressure
• Consider a liquid sample of a pure substance in
a closed vessel. The pressure of a vapor in
equilibrium with the liquid is called the vapor
pressure of the substance

• The liquid-vapor phase boundary in a phase

diagram shows how the vapor pressure of the
liquid varies with temperature

• The vapor pressure of a substance increases

with temperature because at higher
temperatures more molecules have sufficient
energy to escape from their neighbors
 Critical Points & Boiling Points
• In an open vessel
– At boiling temperature: the vapor pressure of a liquid is
equal to the external pressure
• Normal boiling temperature Tb = 100 oC (at 1 atm)
• Standard boiling temperature = 99.6 oC (at 1 bar = 0.987 atm)

• In a closed vessel (no boiling)

– As the temperature increases, the vapor pressure
increases and therefore the density of the vapor increases
– At the same time, the density of the liquid decreases
slightly
– At the critical point: the densities becomes equal and the
interface disappears. (critical temperature Tc and critical
pressure Pc)
– Above the critical temperature, single uniform phase called
supercritical fluid fills the container
 Supercritical Fluids

• CO2: Tc = 304.2 K (31.0 oC), Pc = 72. 9

atm
– Low critical temperature
– H2O: Tc = 374 oC, Pc = 218 atm
 Melting Points & Triple Points
• Melting temperature = Freezing
temperature: liquid and solid phases coexist

• Normal freezing point, Tf (1 atm)

• Standard freezing point (1 bar)

• Triple point: gas, liquid, solid phases coexist

 invariant (out of our control)

• Triple point of water: 273.16 K & 611 Pa 

ice, liquid water, water vapor coexist
 The Phase Rule
• It gives the number of parameters that can be varied while the number
of phases in equilibrium is preserved.

• F=C–P+2

• Variance, F: the number of intensive variables that can be changed

independently without disturbing the number of phases in equilibrium
• Component, C: a chemically independent constituent of a system
• Phase, P: the number of phases at equilibrium
 Component vs Constituent
• A solution of sodium chloride
• Constituent = 3 (water, Na+ and Cl-)
• Component = 2

A constituent of a system: a chemical species that is present

Component, C: a chemically independent constituent of a system

The number of Na+ and Cl- ions are constrained to be equal by the

requirement of charge neutrality

 The Phase Rule
• In a single-component, single-phase
system (C=1, P=1), the pressure and
temperature may be changed
independently without changing the
number of phases, so F = 2
(bivariant, it has two degrees of
freedom)

• Variance F is the number of

degrees of freedom
 The Phase Rule
• If two phases are in
equilibrium, in a single-
component system, the T (or
p) can be changed at will, but
the change in T (or p)
demands an accompanying
change in P (or T) to preserve
the number of phases in
equilibrium. F = 1
Phase Diagram, CO2
• Positive slope of the solid-liquid boundary  melting

temperature of solid carbon dioxide rises as the

pressure is increased (characteristic of most substances)

• Triple point is above 1 atm – no liquid can exist at normal

atmospheric pressure (at least 5.11 atm is required) 

Solid (dry ice) sublimes

 Phase Diagram, CO2

• A  B: the vapor condenses directly to a solid

• B  C: formation of the liquid phase
• C  D: evaporates to the vapor
Phase Diagram, H2O
• Negative slope of solid-liquid boundary  Tm
fall as the pressure increases

• Steep slope  enormous pressures are needed

to bring about significant changes

• Polymorph of ice may contribute to the advance

of glaciers (ice at the bottom of glaciers
experiences very high pressures)
 Unique Behavior of Water

• Tm falls as p increases
– Melting (s  l): volume reduction
– Favorable for liquid as pressure increases
• Ice has larger volume because of the very open structure
– The hydrogen-bonded structure partially collapses on melting 
liquid is denser than the solid (dice = 0.92 g/cm3 vs dwater = 1 g/cm3)
• Due to the hydrogen bonding, water has anomalously high Tb,Tc
and Pc.
– CO2: Tc = 304.2 K, Pc = 72. 9 atm
– H2O: Tc = 374 oC, Pc = 218 atm
Phase Diagram (4He)
• Solid and gas phases are never in equilibrium
• He-I: normal liquid
• He-II: superfluid (flows without viscosity, when it will
rotate indefinitely upon being stirred )
• The only substance with a liquid-liquid boundary (λ-line)

• The atoms are small and light (weak interaction between

atoms )

• Vibrate with large amplitude motion even at very low

temperatures

• Solid helium exists only at high pressure

 Chemical Potential
• Gibbs Energy (G)

• Molar Gibbs Energy (Gm) = Chemical Potential (µ)

• Measure of potential that a substance has for

undergoing change in a system (physical &
chemical changes)
 Equilibrium
• At equilibrium, the chemical potential of a substance is the same throughout a sample,
regardless of how many phases are present

• Chemical potential at one location (µ1)

• Chemical potential at another location (µ2)

• If the amount of dn is transferred from one location to the other

• dG = - µ1·dn + µ2·dn = (µ2 - µ1)·dn if µ1 > µ2 then transfer spontaneously occurs from
location 1 to location 2 (dG < 0) until µ2 = µ1
 Temperature Dependence of
Phase Stability
 ∂G 
  = −S
 ∂T  p
 ∂µ 
  = − Sm
 ∂T  p

• As the temperature increases, the chemical

potential of a pure substance decreases (Sm > 0 for
all substances)
• Slope of a plot of µ against T is negative
• Sm(s) < Sm (l) < Sm (g)  slope is steeper for a gas
• The phase with the lowest chemical potential is the
most stable one at a specified temperature
Response of Melting to Applied Pressure

 ∂µ 
  = Vm
 ∂p T

• Increase in pressure
raises the chemical
potential of any pure Vm(s) < Vm(l) For water
substance (Vm > 0) Vm(s) > Vm(l)

• Most substances melt at a higher temperature when

subjected to pressure (solid phase favored)
• Application of pressure to ice encourages the
formation of water (liquid phase favored)
 Effect of Applied Pressure on
Vapor Pressure
RTdp
dµ ( g ) =
p
dµ (l ) = Vm(l )dP
p dp p*+ ∆P
RT  = Vm(l )dP
p* p p*

p = p * eVm ( l ) ∆P / RT
p : vapor pressure
p* : normal vapor pressure
P : pressure on the liquid (pressure experienced by the liquid)
∆P = additional pressure on the liquid

When pressure is applied, the vapour

pressure of the condensed phase increases
Locations of Phase Boundary

µα ( p, T ) = µβ ( p, T )
dµα = dµβ
dG = Vdp − SdT
− Sα , mdT + Vα , mdp = − Sβ , mdT + Vβ , mdp
(Vβ , m − Vα , m)dp = ( Sβ , m − Sα , m)dT
dp ∆trsS ∆trsH
= =
dT ∆trsV T∆trsV
Clapeyron Equation

Since ∆trsG = ∆trsH – T∆trsS = 0

at equilibrium, ∆trsS = ∆trsH/T
 Solid-Liquid Boundary
dp ∆fusH
=
dT T∆fusV
p ∆fusH T dT
p* dp = ∆fusV T * T
T  T −T * T −T *
ln = ln1 + ≈
T*  T*  T*
∆fusH
p ≈ p*+ (T − T *)
T * ∆fusV
ln(1+x) = x - x2/2 + x3/3 ··· if x <<1

T* is melting temperature when the pressure is p*

The equation of a steep straight line
 Liquid-Vapor Boundary
dp ∆vapH ∆vapH
= =
dT T∆vapV T ( RT / p)
d ln p ∆vapH
=
dT RT 2
ln p ∆vapH T dT ∆vapH 1 1 
ln p* d ln p =
R T * T 2
= −
R
 −
 T T *


∆vapH 1 1 
p ≈ p * e−χ , χ =  − 
R  T T * 

The line does not extend beyond the critical temperature Tc,
because above this temperature the liquid does not exist
 Solid-Vapor Boundary
∆subH = ∆fusH + ∆vapH

A steeper slope for the sublimation curve than for the

vaporization curve at similar temperatures ∵∆subH > ∆vapH
 Types of Phase Transitions
• Fusion & Vaporization
• Solid-Solid, Conducting-
Superconducting, Fluid-Superfluid
 Thermodynamic Basis
 ∂µ ( β )   ∂µ (α ) 
  −   = Vm ( β ) − Vm (α ) = ∆ trsV
 ∂ p T  ∂p T
 ∂µ ( β )   ∂µ (α )  ∆ H
  −  = − S m ( β ) + S m (α ) = −∆ trs S = − trs
 ∂T  p  ∂T  p Ttrs

• Phase transitions (e.g., fus. & vap.) are accompanied by changes of enthalpy
and volume  Slope of chemical potentials at either side of the transition
• H changes by a finite amount for a transition temperature (constant). There

for the heat capacity, =( ) , is infinitely at the transition.

First vs. Second Order Phase Transition

Ehrenfest Classification
First order phase transition: First derivative of the chemical potential
with respect to temperature is discontinuous
Second order phase transition: First derivative of the chemical potential
with respect to temperature is continuous but second derivative is
discontinuous
 Second Order Phase Transition

• A continuous slope of µ implies that the volume, entropy, and

enthalpy do not change at the transition
• The heat capacity is discontinuous at the transition but does
not become infinite there

 ∂µ ( β )   ∂µ (α ) 
  −   = Vm ( β ) − Vm (α ) = ∆ trsV
 ∂p T  ∂p T
 ∂µ ( β )   ∂µ (α )  ∆ H
  −  = − S m ( β ) + S m (α ) = − ∆ trs S = − trs
 ∂T  p  ∂T  p Ttrs
 λ-Transition
• A phase transition that is not first-order yet the heat capacity becomes infinite
at the transition temperature
• The shape of the heat capacity curve resembles the Greek letter lambda
• Examples: the order-disorder transitions in alloys, the onset of ferromagnetism,
and the fluid-superfluid transition of liquid helium
 Molecular Interpretation
(1st Order)
• First-order transitions typically involve the relocation of
atoms, molecules, or ions with a consequent change in the
energies of their interactions.
• Vaporization eliminates the attractions between molecules
Molecular Interpretation
(2nd Order)
Tetragonal to cubic phase
transition does not
involve a discontinuity in
the interaction energy
between the atoms or the
volume they occupy
 Molecular Interpretation
(λ-Transition)
• The order-disorder transition in β-brass (CuZn) is an example of a λ-transition
• The low-T phase is an orderly array of alternating Cu and Zn atoms
• at T = 0 order is perfect
• at T increases, islands of disorder appear based on the exchange of atomic locations
• Once two atoms have exchanged locations, it is easier for their neighbors to exchange their locations

• The heat capacity increases as the transition temperature is approached because it is increasingly easy for
the heat supplied to drive the phase transition rather than to be stored in thermal motion

• High-T phase is a random array of the atoms