Chemical Thermodynamics

CH 201

Phase Equilibria & Phase Diagrams

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 Phases and the Phase Diagrams.
Definitions
Component – chemically recognizable species (Fe and C in
carbon steel, H2O and sucrose in sugar solution in water).
A binary alloy contains two components,
a ternary alloy – three, etc.
Phase – a portion of a system that has uniform physical and
chemical characteristics. Two distinct phases in a system
have distinct physical and/or chemical characteristics (e.g.
water and ice, water and oil) and are separated from each
other by definite phase boundaries.
A phase may contain one or more components. A single-
phase system is called homogeneous.
Systems with two or more phases are mixtures or
heterogeneous
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 Definitions…Solubility

Solvent is a host or major component in solution.

Solute is a minor component in solution.
Solubility limit of a component in a phase is the
maximum amount of the component that can be
dissolved in it (e.g. alcohol has unlimited solubility in
water, salt has a limited solubility, oils are insoluble).
The same concepts apply to solid phases:
Cu and Ni are mutually soluble in any amount
(unlimited solid solubility), while C has a limited
solubility in Fe.

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 Definitions… Nucleation

Nucleation is the extremely localized growing of

a separate thermodynamic phase.
E.g.: when sugar is supersaturated in water nucleation
will occur, allowing sugar molecules to stick together
and form large crystal structures.
Nucleation generally occurs with much more difficulty in
the interior of a uniform substance, by a process called
homogeneous nucleation.
The creation of a nucleus implies the formation of
an interface at the boundaries of a new phase.

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 Definitions… Nucleation…
Heterogeneous nucleation occurs much more
often than homogeneous nucleation.
Heterogeneous nucleation forms at preferential sites
such as phase boundaries or impurities like dust or
crystallites and requires less energy than
homogeneous nucleation.
At such preferential sites, the effective surface
energy is lower, thus diminishing the free energy
barrier and facilitating nucleation.

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 Definitions… Phase transition, Phase separation
Phase transition - changes from one state of
matter to another: vaporization, sublimation,
fusion.
Phase separation - the process by which a single
solid (liquid) phase separates into two or more new
phases. E.g. salting out process . Water and
ethanol are made immiscible by the addition of
potassium carbonate.
Salting out (also known as antisolvent crystallization,
precipitation crystallization, or drowning out) is an effect
based on the electrolyte-nonelectrolyte interaction,
in which the non-electrolyte could be less soluble at
high salt concentrations.
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 Microstructure
The properties of an alloy
depend not only on
proportions of the phases
but also on how they are
arranged structurally at the
microscopic level.
Thus, the microstructure is
specified by the number of The long gray regions are
phases, their proportions, flakes of graphite. The matrix
is a fine mixture of BCC
and their arrangement in (body-centered cubic) Fe and
space. Fe3C compound.

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 Equilibrium and Metastable States

A system is at equilibrium if at constant

temperature, pressure and composition, the
system is stable, not changing with time.
➢Equilibrium is the state that is
achieved in given sufficient
time.
➢ The time to achieve
equilibrium may be very long
(the kinetics can be slow) that a
state along the path to the
equilibrium may appear to be
stable. This is called a
metastable
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 Equilibrium and Metastable States…
In thermodynamics the equilibrium is described as
a state of a system that corresponds to the
minimum of thermodynamic function called the free
energy (Helmholtz Free Energy A or F, Gibbs
Free Energy G). Thermodynamics tells us that:

• Under conditions of a constant temperature and

pressure and composition, the direction of any
spontaneous change is toward a lower free energy.
• The state of stable thermodynamic equilibrium is
the one with minimum free energy.
• A system at a metastable state is trapped in a local
minimum of free energy that is not the global one.
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 Phase diagrams
• Phase diagrams are one of the most important
sources of information concerning the behavior of
elements, compounds and solutions.
• They provide us with the knowledge of phase
composition and phase stability as a function of
temperature (T), pressure (p) and composition (C).
• Furthermore, they permit us to study and control
important processes such as phase separation,
solidification, sintering, purification, growth and doping
of single crystals for technological and other
applications.

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 Phase diagrams…
Although phase diagrams provide information about
systems at equilibrium, they can also assist in
predicting phase relations, compositional
changes and structures in systems not at
equilibrium.
Phase diagram is a graphical representation of all
the equilibrium phases as a function of
temperature, pressure, and composition.
For one component systems, the equilibrium state
of the system is defined by two independent
parameters (p and T), (T and V), or (p and V).

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 Phase diagram…

• The simplest phase diagrams are p-T diagrams

of a single simple substance, such as water.
• The axes correspond to the pressure and
temperature.
• The phase diagram shows, in pressure-temperature
space (in this case), the lines of equilibrium or
phase boundaries between the three phases of
solid, liquid, and gas.
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 A typical (single simple substance) phase diagram
The critical point:
Tc = 374 °C,
pc = 218 atm,
ρc = 356 kg/m³.
Supercritical fluid:
distinct liquid and gas
phases do not exist. It can
effuse through solids like a
gas, and dissolve materials
like a liquid. In addition,
close to the critical point,
small changes in pressure
or temperature result in
large changes in density.

The green lines mark the freezing point and the blue line the boiling point, showing
how 2/4/2024
they vary with pressure. The dotted line
CH 201 gives the anomalous behavior of water.
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 Triple point

https://www.youtube.com/watch?v=XEbMHmDhq2I
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 Phase diagram…
✓ Common components of a phase diagram are
lines of equilibrium or phase boundaries,
which refer to lines that mark conditions under
which multiple phases can coexist at equilibrium.
✓ Phase transitions occur along lines of
equilibrium.
✓ Triple points are points on phase diagrams
where lines of equilibrium intersect.
✓ Triple points mark conditions at which three
different phases can coexist.
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 Phase diagram…
✓ The single combination of pressure and temperature at
which liquid water, solid ice, and water vapour can
coexist in a stable equilibrium occurs at exactly 273.16
K (0.01 °C) and a partial vapour pressure of 611.73 Pa.
✓ At that point, it is possible to change all of the
substance to ice, water, or vapor by making arbitrarily
small changes in pressure and temperature.
✓ The triple point of water is used to define the kelvin,
the base unit of thermodynamic temperature in
the International System of Units (SI).
• The kelvin is defined as the fraction ​1⁄273.16 of the
thermodynamic temperature
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of the triple point of water.
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 Phase diagram of water

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torr = 133 Pa; The critical point:
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c = 374 °C, pc = 218 atm 17
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Phase diagram of water including high-pressure forms of ice

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 3D phase diagrams
• It is possible to envision three-dimensional (3D) graphs
showing three thermodynamic quantities.
• For example for a single component, a 3D Cartesian
coordinate type graph can show temperature (T) on one
axis, pressure (p) on a second axis, and specific volume
(Vm) on a third.
• Such a 3D graph is sometimes called a p-V-T diagram.
The equilibrium conditions would be shown as a 3D
curved surface with areas for solid, liquid, and vapor
phases and areas where solid and liquid, solid and
vapor, or liquid and vapor coexist in equilibrium.

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3D phase diagrams

• p-V-T 3D diagram
for fixed amount of
pure material

A line on the surface

called a triple line is
where solid, liquid
and vapor can all
coexist in
equilibrium.

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 3D phase diagrams…

• The critical point remains a point on the surface

even on a 3D phase diagram.
• An orthographic projection of the 3D p-V-T graph
showing pressure and temperature as the vertical
and horizontal axes effectively collapses the 3D plot
into a 2D pressure-temperature diagram.
• When this is done, the solid-vapor, solid-liquid, and
liquid-vapor surfaces collapse into three
corresponding curved lines meeting at the triple
point, which is the collapsed orthographic projection
of the triple line.

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 Phase Rule
Gibbs developed the phase rule (1875).
It describes the relationship between
✓the number of components and
✓the number of phases for a given system and
✓ the conditions that may be allowed to change
(e.g., temperature and pressure).
The phase rule in the general form is:
2+C=F+P (1)
(when temperature and pressure both can vary).

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 Phase Rule…

C is the number of chemically independent

components, usually elements or compounds, in the
system;
F is the number of degrees of freedom, or the
number of variables (such as temperature, pressure, and
composition), that are allowed to change independently
without changing the number of phases in equilibrium;
P is the number of phases present.
The constant parameter “2” implies that both the
temperature and pressure are allowed to change.

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 Phase Rule…
❑ The term “chemically independent” refers to the
number of different elements or compounds needed to
specify a system.
For example, water H2O is considered as one
component system, since the concentrations of H and
O in H2O can not be independently varied.
❑ A phase can be defined as any portion of a system
which is physically homogeneous within itself and
bounded by a surface so that it is mechanically
separable from any other portions.
For example, water has three phases − liquid water,
solid ice, and steam.

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 Phase Rule…
A phase has the following characteristics:
1. The same structure or atomic arrangement throughout.
2. Roughly similar properties throughout.
3. A definite interface between the phase and any surrounding or
adjoining phases.

Pressure-temperature
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The dotted line shows the 1 atm pressure.
 Phase Rule (continue)

Reminder: phase rule

2+C=F+P
F=2+C–P
describes the relationship between
✓the number of components (C)
✓the number of phases (P) for a given system
✓ the conditions that may be allowed to change
(e.g., when temperature and pressure both can vary – “2”),
and
✓the number of degrees of freedom (F). 27
Unary system. Phase
Rule… Pressure
B
Consider phase diagram for Liquid
magnesium:
A
Point A: magnesium is liquid.
1 atm
The number of phases is one
(liquid). From the equation,
2 + C = F + P: Solid
Vapor
F=2+C–P=2+1–1=2
X
It means that number of degrees
of freedom is 2. We can change
the pressure, the temperature, or
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both, and still be an all-liquid
portion of diagram. Temperature, oC
Put another way: we must fix both the temperature and the
pressure to know precisely where we are in the liquid
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portion of the diagram.
Unary (one-component) system. Phase Rule…
Point B: the boundary between the solid
and liquid portions of the diagram. The Pressure B
number of components C is still one, Liquid
but at the point B, the solid and liquid A
coexist, or the number of phases P is
1 atm
two.
From
2 + C = F + P, F = 2 + C – P = 2 + 1 – 2 Solid
=1 Vapor
or there is only one degree of freedom. X
If we change the temperature, the
pressure must be adjusted if we are to
stay on the boundary where the liquid 500 1000
and solid coexist.
Temperature, oC

On the other hand, if we fix the pressure, the phase diagram

tells us the temperature that we must have if solid and liquid
are to coexist. 29
 Unary system. Phase
Rule…

Point X: solid, liquid, and vapor Pressure

B
coexist. The number of components Liquid

is still one; the number of phases is A

three. 1 atm

Thus,
F = 2 + C – P = 2 + 1 – 3 = 0. Solid
Vapor
It means that all three phases coexist X
only if both the temperature and
pressure are fixed.
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The point X is the triple point.
Temperature, oC

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