Phase Transformations Phases, Components and Degrees of Freedom

Chapter 8 of Atkins: Sections 8.1- 8.3 Phase diagrams are extremely useful for systems with multiple
components, and serve to describe physical and chemical equilibria
over a range of different compositions, as well as points where
Phases, Components and Degrees of Freedom substances are mutually miscible, or even when a system has to be
brought to a specific set of conditions for equilibrium to exist (e. g.,
Definitions pressure, temperature, and composition)
The Phase Rule Phase diagrams are very important in the development of:
alloys ceramic materials
Two- Component Systems steel semiconductors
plastics superconductors
Vapor Pressure Diagrams cosmetics petroleum product separations
Composition of the Vapor food products glasses
Interpretation of the Diagrams All phase diagrams are developed around one relationship, the
phase rule, which was derived by J. W. Gibbs - it can be applied
The Lever Rule to a wide variety of systems
Phase diagrams: pictorial way of understanding the properties of a
system

Prof. Mueller Chemistry 451 - Fall 2003 Lecture 18 - 1 Prof. Mueller Chemistry 451 - Fall 2003 Lecture 18 - 2

Some Definitions Some Definitions, 2

Phase : Signifies a form of matter that is uniform throughout, not only
in chemical composition but also in physical state
Number of phases is denoted by P:
P = 1 for gas, gaseous mixture, crystal, two miscible liquids, ice
P = 2 for slurry of ice and water, immiscible metal alloys
Sometimes not easy to decide how many phases there are - for
example, a solution of solid A in solid B - homogeneous on molecular
scale - A atoms are surrounded by B atoms, representative of
composition on the whole (example (a))
Constituent: A chemical species that is present in a system. For
example, a mixture of water and ethanol has 2 constituents
Component: A chemically independent component of the system. The
number of components in a system, C, is the minimum
number of independent species needed to define the
composition of all of the phases present in the system
ƒ When no reaction takes place, Constituents = Components
ƒ When a reaction can occur, the number of components is the minimum
number of species which specifies the composition of all of the phases

CaCO3(s) CaO(s) + CO2(g)

A dispersion (example (b)) is uniform macroscopically, Phase 1 Phase 2 Gas Phase
but not on the microscopic molecular level - for • Number of Phases, P = 3
example, regions of A are embedded within a matrix
• Number of Constituents = 3
of B, still uniform composition - very important in
materials synthesis , especially production of steels, • Number of Components, C = 2*
tailoring materials mechanical and electrical properties
*CaCO can be expressed in terms of 2 components in two different phases
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from the stoichiometry of the reaction
Prof. Mueller Chemistry 451 - Fall 2003 Lecture 18 - 3 Prof. Mueller Chemistry 451 - Fall 2003 Lecture 18 - 4

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 Components Example Variance and Degrees of Freedom
Consider the thermal decomposition of ammonium chloride: The variance , F, is the number of intensive variables in a system that
NH4Cl (s) NH3(g) + HCl (g) can be changed independently without disturbing the number of phases
• Number of Phases, P = 2 in equilibrium
• Number of Constituents = 3
• Number of Components, C =1*
In a single-component, single phase system (C= 1, P= 1) the pressure
*NH and HCl are fixed in stoichoimetric proportions by the reaction, and and temperature may be changed independently without disturbing the
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compositions of both phases can be specified by NH4Cl number of phases in equilibrium

N.B., if additional HCl or NH3 were added to the system, decomposition of the F = 2, system is bivariant , or has two degrees of freedom
NH4Cl would not give the correct gas phase compositions, and either HCl or NH3
would be invoked as a 2nd component
If two phases are in equilibrium in a single- component system (C= 1,
H2O (l) 1/2O2(g) + H2(g) (at room temp) P= 2) (e. g., a liquid and its vapor), the temperature (or pressure) can be
• Number of Phases, P = 2 changed, but there must be an accompanying change in pressure (or
• Number of Constituents = 3 temperature) to preserve the phases in equilibrium (the variance of the
• Number of Components, C = 3* system has fallen to one)
*At room temperature, O2(g) and H2(g) do not react to form water, so they are not
in equilibrium: regarded as independent constituents

Prof. Mueller Chemistry 451 - Fall 2003 Lecture 18 - 5 Prof. Mueller Chemistry 451 - Fall 2003 Lecture 18 - 6

Phase Rule One Component Systems

J.W. Gibbs, regarded as America’s first theoretical scientist and the father Phase diagrams are extremely useful for systems with multiple
of chemical thermodynamics, wrote that the number of components, C, components, and serve to describe physical and chemical equilibria over a
and the number of phases at equilibrium, P, for a system of any range of different compositions, as well as points where substances are
composition: mutually miscible, or even when a system has to be brought to a specific
F = C – P + 2 set of conditions for equilibrium to exist (e. g., pressure, temperature and
composition)
For a one- component system, F = 3 - P
1. Count the number of intensive variables (p and T count as 2) If 1 phase present, F = 2, and p and T can be
2. Specify composition of the phase by mole fractions of C - 1 varied without changing the number of phases
components (need C - 1, not C, since sum of all mole fractions = 1) (single phase is an area on the phase
3. Since there are P phases, total number of composition variables is diagram)
P(C - 1), and total number of intensive variables is P(C - 1) + 2 If 2 phases in eqb, F = 1, implying the
pressure in not freely variable if the
4. At equilibrium, chemical potential of J must be same in every phase temperature is set
µJ,α = µJ,β = .... for P phases If 3 phases in eqb, F = 0, and the system is
There are P - 1 equations of this kind for each component J. If there invariant - this condition can only be
are C components, total equations is C(P - 1) established at a definite p and T
5. Each equation reduces our freedom to vary P(C - 1) + 2 intensive 4 phases cannot exist in a one component
variables, so the number of degrees of freedom is system, since F cannot be negative
F = P(C - 1) + 2 - C(P - 1) = C – P + 2
Prof. Mueller Chemistry 451 - Fall 2003 Lecture 18 - 7 Prof. Mueller Chemistry 451 - Fall 2003 Lecture 18 - 8

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 Phases, Components, and Degrees of Freedom
Consider pure water:
a In gas phase, cooled at constant p, F = 2
b Liquid appears at the phase transition (the
boiling temperature), and F = 1. We have
specified constant p (single degree of
freedom), so equilibrium T is not under our
control
c Lowering T takes liquid to single phase
liquid region, F = 2, T can be varied at will
d Liquid- solid phase transition at Tf , with
F = 1, and at constant p, T is not under
our control
e Lowering T further results in single solid
phase with F = 2, where p and T can be
varied
Prof. Mueller Chemistry 451 - Fall 2003 Lecture 18 - 9
Experimental Procedures 2
High pressure phase transitions can be observed in the diamond-anvil
cell, in which pressure can be exerted by turning a screw (1 Mbar
pressures) and the pressure is monitored spectroscopically by shift in
lines from small ruby pieces added to the sample.
Prof. Mueller Chemistry 451 - Fall 2003 Lecture 18 - 11
Experimental Procedures 1
Detecting phase transitions is tricky, requiring special techniques
Thermal analysis: technique which takes advantage of the enthalpy
change during a first order phase transition:
• sample is allowed to cool
and the temperature is monitored
• at a 1st-order transition, heat is
evolved and cooling stops until the
transition is complete
• cooling curve for the isobar cde in
the water phase diagram is at right
Prof. Mueller Chemistry 451 - Fall 2003 Lecture 18 - 10
Two-Component Systems
When there are two components in a system, C = 2, and F = 4 - P, so if the
temperature is held constant, remaining variance is F l = 3 - P, which has a
maximum value of 2 for a single phase. The remaining degrees of freedom are
assigned normally to p and the composition (mole fraction).
ƒ Phase diagrams of pressures & compositions for stable phases
ƒ Phase diagrams of temperatures & compositions for stable phases
Vapor pressure diagrams:
Partial pressures of components of an
ideal solution of two volatile liquids are
related to the composition of the mixture
by Raoult’s Law
pA = x A p∗A pB = x B p∗B
where * signifies the vapor pressures of
pure A and B. Total vapor pressure is
p = pA + pB = x A p∗A + x B p∗B = p∗B + (p∗A − p∗B )x A
Linear variation of vapor pressure at fixed
temperature with changed composition
Prof. Mueller Chemistry 451 - Fall 2003 Lecture 18 - 12
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 Composition of the Vapor Interpretations of the Diagrams
Compositions of liquid and vapor in equilibrium For distillations, both vapor and liquid contributions are of interest, so
are not necessarily the same, as vapor should be we combine the two previous diagrams into one
richer in the more volatile component.
For mole fractions of a gas yA and yB p∗A
y A = pA p y B = pB p p∗B
For an ideal mixture, partial pressures may be
expressed in terms of mole fractions in the liquid
(see equations on previous page)
x A p∗A p∗A
yA = y B = 1− y A
p∗B + (p∗A − p∗B )x A p∗B
In all cases, yA > xA (vapor richer in more volatile
component). If B is non-volatile, pB*= 0, yB = 0. The Point a: vapor pressure of mixture of composition xA
total vapor pressure as composition of the vapor: Point b: composition of vapor in equilibrium with liquid at that pressure
p p ∗ ∗ At equilibrium, P = 2, F’ (fixed T) = 1, so if composition specified, pressure at
p= A B
which equilibrium exists is fixed
p∗A + (p − p∗A )y A
∗
B

Prof. Mueller Chemistry 451 - Fall 2003 Lecture 18 - 13 Prof. Mueller Chemistry 451 - Fall 2003 Lecture 18 - 14

Interpretations of the Diagrams, 2 Interpretations of the Diagrams, 3

The horizontal axis shows the overall composition, zA, of the system:
All points down to the solid diagonal
correspond to a system under high
pressure where there is only a liquid
phase (zA = xA, composition of liquid)
All points below lower curve correspond to a
system with low pressure where only the
vapor phase exists (applied pressure is
less than the vapor pressure, so zA = yA)
Points between lines are systems where
two phases exist: 1 liquid & 1 vapor
Lowering the pressure on a liquid by drawing out a piston, start at point a:
a: Here, F’ = 2 and P = 1; changes to system do not effect overall composition, so
system moves down vertical line that passes through a (vertical line called an
isopleth), until point a1is reached (pressure reduced to p1)
a1: Liquid is in equilibrium with its vapor
(composition of vapor phase given by a1’,
horizontal line is called a tie line)
Composition (of liquid) same at the lower
pressure, so at this pressure (p1), virtually
no vapor pressure
a2": Pressure is lowered to p2, new
pressure is below the vapor pressure of the
liquid, so it vaporizes until the vapor
pressure of the remaining liquid falls to p2
Two phases are at equilibrium here, so F’ =
1 for a given pressure p2, variance is zero
and vapor and liquid phases have fixed
compositions, at a2 and a2’
a3’ : Pressure is further dropped to p3, and now the composition of the vapor is the
same as the overall composition, so the tiny amount of liquid present must be
negligible, with composition a3
a4: Pressure drops to p4, and now only the vapor phase exists, same composition
as the overall composition of the system

Prof. Mueller Chemistry 451 - Fall 2003 Lecture 18 - 15 Prof. Mueller Chemistry 451 - Fall 2003 Lecture 18 - 16

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 Interpretations of the Diagrams, 4 The Lever Rule
The previous diagram can be viewed more generally below, considering The point in a two-phase region of a phase diagram indicates not only
pressure reduction via a piston qualitatively if both liquid and vapor are present, but also quantitatively
tells us the relative amounts of each.
In (a), the liquid and To find the relative amounts of phases
vapor phase are in α and β in equilibrium, measure
equilibrium, the distances lα and lβ along the tie lines,
compositions and and use the lever rule:
abundances of the nα lα = n β lβ
two phases can be
predicted. Proof: If n = nα+ nβ and the overall
In (b) compositions amount of A is nzA, then the overall
of phases are amount of A is the sum of its two
determined from the phases: nz = n x + n y
A α A β A
tie lines.
In (c), the applied pressure is much less than the vapor pressure, so nz A = nα z A + n β z A
all of the liquid has vaporized, and we are in a one phase region Then equating the sides:
Above, lβ ≈ 2lα , the amount of
nα (x A − zA ) = n β (zA − y A )
phase α is 2x that of phase β
Prof. Mueller Chemistry 451 - Fall 2003 Lecture 18 - 17 Prof. Mueller Chemistry 451 - Fall 2003 Lecture 18 - 18