MATE 510 – Lecture 5

Phase Equilibria in Single

Component Systems. From Gibbs
Energies to Phase Diagrams.

2/6/2014 1
Why changes happen in a thermodynamic system?

Lessons from mechanics: 1st Newton’s law. Formulate?

In mechanical systems changes happen only when forces act on the system.
What is force in mechanics?
=
,
Change is caused by potential energy change or by potentials acting on the system.

Same approach is used in thermodynamics: if thermodynamic system state is changed,

we say that it is caused by potential(s) acting on the system.

Examples of potentials: in thermodynamics: P, T, H, U, – thermodynamic potentials. In

thermodynamics potentials are sometimes called intensive variables to distinguish them
from the variables which they act upon (extensive variables).
Give examples of thermodynamic system state changes caused by thermodynamic
potentials?

To what extend the change occurs? To the extend where there is no difference in the
potential between the parts of a system or between the system and its environment.
Give examples?
In the previous lectures you learned what is Gibbs free energy or G. What is this by the
way? Give definition? Write equation(s) for Gibbs free energy?

Why G is so important in thermodynamics? Because it gives a unique description of

thermodynamic equilibrium in commonly used variables: P and T. Namely, at constant P
and T the equilibrium in a one component system of fixed composition occurs when the
system exists in that state, which has the minimal value of G. This gives a universal
recipe for finding the equilibrium state of a system in terms of P and T: look at G’ as a
function of P and T and find the minimum. Compare this criterion of equilibrium to
commonly used “everything in Nature tends to attend the state with minimal energy”. Is
this “energy criterion” correct? Why?
How to use this recipe in practice? In the next slides we consider some examples. 1-
component 2-phase system: H2O liquid (l) and solid (s)

s
s
s

l
l l

s and l H2O are in s H2O melts at T>0 C, P=1
equilibrium at T=0 C, P=1 atm. The equilibrium state of
atm. The system will stay H2O in these conditions is that
like this forever, no of l. Supply heat and s will
change melt (change in system).
When ice melts it consumes
heat and reduces T (potential
which caused transition).
When T of the system = T of
the environment, new
equilibrium is established.
l H2O freezes at T<0 C, P=1
atm. The equilibrium state of
H2O in these conditions is that
of s. Take heat from the system
and H2O will freeze (change in
system). When liquid
crystallizes, heat is evolved
and increases T (potential
which caused transition). When
T of the system = T of the
environment, new equilibrium
is established.
When the amount of heat supplied to H2O(s) + H2O(l) system in equilibrium is not
enough to melt all ice, only some ice will melt, consuming the heat and reducing the T
back to 0 C, at which point a new equilibrium between the changed amounts of H2O(s)
and H2O(l) will be established.

Suppose we have 10 mol of H2O(s) and 10 mol of H2O(l) in equilibrium. Now, we supply
heat amount enough to melt just 1 mol of H2O(l). The transition we have is:

1 2 1 2 ()

= () =0

(since the system is at equilibrium, i.e. G always stays at min, hence G does not change,
its gradient is 0)

Thus, at the state of equilibrium between ice and liquid () = , where

() are molar Gibbs energies of H2O in l and s phases. Therefore, the
Gibbs free energy of the system containing () can be written as:

= + ( )
Since at the equilibrium () = , = ( )+ () = . This
means that in equilibrium G’ of the system is independent of the proportions of the ice
and liquid phase present.
The molar Gibbs free energies of H2O in liquid and solid phase are called chemical
potentials of H2O in the corresponding phases, i.e.

() = , ( ) = , ( ) = .

In terms of Gibbs free energy of the whole system, chemical potential of i component is
partial derivative of G’ by the number of mole of the i component:

=
( ) , ,

For one component system the chemical potential of the component equals the increase
in the value of G’ which occurs when 1 mole of the component is added to the system at
P, T = const. Then the partial differential becomes full differential, i.e.
= = and if =1 , = = , which is molar
( ) , , ( ) , ,
Gibbs free energy of i.
Let’s now go back to different temperatures and try to understand phase behavior of
water at different T based on the analysis of Gibbs free energy.
At T > 0C ice melts. An
P = 1 atm
equilibrium state of H2O at T >
G
0C is liquid water. And since
this is the equilibrium state,
then at T > 0C minimal G’
corresponds to G(l). Thus G(l) <
G(s) or < . This
(s) means, H2O molecules have
higher potential in (s) than in (l)
and they escape (s) moving
into (l).
(l)
Analyze situation at T < 0C, P =
1atm?

T<0C 0C T>0C Let’s do similar analysis in

FactSage. Explain differences?
This graph is a simple example of phase diagram in a simple system (1 component, 2
phases). Phase diagram tells us which phase is thermodynamically favored in given
conditions.
We can also plot G for s into l and l into s transitions.

P = 1 atm P = 1 atm
G G G
s->l l->s

0 0 (s)

(l)

T<0C 0C T>0C T<0C 0C T>0C

Calculate slope of the lines?

Calculate curvature of the lines?

The analysis of G as a function of an argument to determine the most stable phase (or
structure) is very powerful and is employed very widely in materials science.

One example: stability of nanodiamond clusters as a function of hydrogen chemical

potential in the system.

J. Y. Raty, G. Galli, Nature Materials, 2, 792-795 (2003)

The only criterion for equilibrium is the minimum of G’ of the system (not minimum of
energy or maximum of entropy). However, sometimes it is easier to measure and
analyze other functions, for example, heat (H). How H is related to heat BTW?

Can we relate other thermodynamic functions to G’ and analyze how they behave at
equilibrium? Yes. Let’s do it on the blackboard.
P = 1 atm P = 1 atm
H S (l)
(l)

Hm Sm

(s) (s)

T<0C 0C T>0C T<0C 0C T>0C

Plot these graphs in FactSage?
Equilibrium between 2 phases in 1 component system occurs when the separation
between the (l) and (s) lines in the left graph = separation between the (l) and (s) lines
times T in the right graph ( G = 0 means H = T S). The equilibrium is a compromise
between entropy considerations and enthalpy considerations.
So far we’ve done analysis of phase behavior of water at different temperatures. Similar
analysis can be done at different pressures. The idea is very similar: analyze how G
changes at different P and then identify the ranges of stability of different phases. Let’s
do it on the blackboard.
T=0C
G
Calculate slopes of the lines?

Plot this diagram for water in FactSage?

(l)
Does water behave normal or rather
anomalous?

(s) Skating: an example of G(P) from real

life?
P<1atm 1atm P>1atm

All previous discussion thus shows that it is possible to maintain the equilibrium between
(s) and (l) H2O not only at 0 C and 1 atm, but also at different T and P. For example,
increase of P favors liquid H2O but decrease of T favors solid H2O. Thus if we
simultaneously reduce T and increase P, we may expect that at some P and T, different
from 1 atm and 0 C, both (l) and (s) H2O will be at the equilibrium again.
Plot G as a function of both T and
P in one graph.

The sides of this 3D cube graph

represent G(T) at fixed P and
G(P) at fixed T, which we have
just analyzed in the previous
slides.

The line mo (thick black line

formed by the intersection of the
solid and liquid planes) is the line
of solid-liquid equilibrium of water
at different T and P.

Let’s provide a more rigorous

mathematical description of this
equilibrium on the blackboard.
 A Part of the phase diagram of H2O. This is a
projection of 3 surfaces (liquid, solid, gas) in
the G-P-T coordinates (look at the cube from
the previous slide) onto the P-T plane.
B Normal melting temperature of the material
(m) is the melting temperature at a pressure
m b of 1 atm.

Normal boiling temperature of the material (b)

is the boiling temperature at a pressure of 1
atm.

O Triple point of the material (O) at which the

gas, liquid, and solid phases are at the
equilibrium with each other.
C
OA – liquid-solid equilibrium line, OB – liquid-
gas equilibrium line,
OC – solid-gas equilibrium line.

Plot this diagram for water in FactSage?

What is anomalous about water in this diagram compared to majority of other
substances?
Plot similar phase diagrams for CO2 and Fe?

http://cft.fis.uc.pt/eef/FisicaI01/fluids/thermo20.htm
 Phase diagrams of Binary Systems

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 Phase diagrams
• Phase diagrams may come in different “flavors”

• Unary: P vs. T
• Binary: chemistry vs. T OR P
• Ternary: composition (T + P fix!)

• With several variables, 2D representation can

only show a part of the whole problem!
Gibbs Phase Rule
F = # of Variables - # of Equations

F + P' = C' + 2

2/6/2014 16
 Phase diagrams
As simple as it gets: unary phase diagrams

• Both solid phases can both melt

Pressure

and sublimate
• Phase boundaries that involve
Solid 1
melting or phase transitions of
Liquid solid phases are usually very
steep because there is only a
very small change of the volume
Vapor • The slopes (in this case: all
positive) are a result of the
Temperature
change of volume and latent
heat

2/6/2014 17
 Phase diagrams
Clausius-Clapeyron & Le Chatelier's principle:
If a chemical system at equilibrium experiences
dT T a change in concentration, temperature,
= volume, or partial pressure, then the
dP equilibrium shifts to counteract the imposed
change and a new equilibrium is established
Pressure

Meaning: by increasing the

Solid 1 pressure, we solidify the vapor
Liquid to solid 2 and later on to solid
1. Note, the density increases
as we go from vapor to solid 2
Vapor and later on to solid 1

Temperature
2/6/2014 18
L. W. Diamond, Lithos, 55, 69-99 (2001) http://www.geopetro.ethz.ch/research/orefluids/simulati
on/nacl3d?hires
The complete diagram of a two-component system is 3-D with the coordinates: T, P, composition.
In most cases it is sufficient to present a binary phase diagram as a constant pressure section
(isobaric section) of the 3-D diagram. The constant pressure is normally chosen at 1 atm, and the
coordinates are T and composition.

The easiest example of such binary phase diagram is an isomorphous phase diagram.
Isomorphous phase diagram is a phase diagram in which components display both unlimited liquid
and unlimited solid solubility.
In these systems only a single type of crystal structure exists for all compositions of the
components (alloy) and the system is therefore called isomorphous system.

Liquidus line: the line of temperatures and

compositions at which the first solid begins to form
Liquid solution (1 phase) during solidification. At any given composition
MA there is no solid phase present in the system
above the temperature on liquidus line.

Solidus line: the line of temperatures and

T

compositions below which all liquid has completely

Solid solution (1 phase)
0 10 20 30 40 50 60 70 80 90 100
A wt% OR mol% B
solidified. At any given composition there is no
liquid phase present in the system below the
MB temperature on solidus line.
At any given composition, the range of
temperatures between the liquidus and solidus
B lines is called freezing range.
Which quantitative information can be extracted from binary phase diagrams and how it can be
done?
Many parameters can be extracted, including melting points of pure components, freezing range of
liquid+solid system, liquidus and solidus temperatures, which phases are present at any given T
and composition, as well as the relative amount and composition of each phase.
Phases present and their relative amounts

Point 1: System composition 40 wt. % B and 60 wt.

% A. Only one phase is present: solid solution (
Liquid solution (1 phase) phase). The composition of this phase is same as
MA the system composition.
2
Point 2: System composition 20 % wt. A and 80 wt.
% B. Only one phase is present: liquid solution.
3
T

The composition of this phase is same as the

1
Solid solution (1 phase)
0 10 20 30 40 50 60 70 80 90 100
A wt% OR mol% B
system composition.
MB
Point 3: System composition 40 % wt. A and 60 wt.
% B. Two phases are present in equilibrium: liquid
and phase. How much of each phase is present?
What is the composition of each phase? Is it same
B
as system composition?
 To determine composition of the liquid and solid phases in
Two-phase region equilibrium in the two-phase region we draw a tie-line, which
goes across the two-phase region to intersection with the phase
equilibrium lines.

Point 3: Composition of liquid phase is 70 wt. % B and 30 wt. %

A. Composition of solid ( phase) is 38 wt. % B and 62 wt. % A.
How to determine the relative amounts of each phase?

Lever rule (inversed)

Construct a system of 2 mass balance equations.
1) All material must be in one phase or another:

+ =1

2) Mass of the component that is present in both phases is equal

to the mass of the component in one phase + mass of the
component in the second phase:

+ =
C C0 Cl
Solution of this system gives us the lever rule:

= =

In Point 3 C0 = 60 wt. % B, C = 38 % wt. B, Cl = 70 wt. % B,

then W = 31.3 wt.%, Wl = 68.7 wt.%, i.e. the system is mostly
liquid in these conditions.
 Example of real isomorphous phase diagram in FactSage:

Cu and Ni are mutually soluble in solid state (complete solubility) because they both
have same fcc structures, nearly identical atomic radii and electronegativities, and
similar valences. With these many similarities elements usually form isomorphous
systems.
 Phase Diagrams with Eutecticum
The simplest kind of system with two solid phases is called a eutectic system.
A eutectic system contains two solid phases at low temperature. These phases may have different
crystal structures or same crystal structure with different lattice parameters. Examples: Pb(fcc) and
Sn(tetragonal) – solders, Fe(bcc) and C(hexagonal) – cast irons, Al(fcc) and Si(cubic) – cast
aluminum alloys
MA • MA, MB: melting point of phases A
and B, respectivly.
Liquid
MB • Liquidus line: at temperatues
Temperature

higher than this threshold, we

A + Liquid only have a liquid phase
B+
Liquid • Solidus line: below that line, we
only have solid phases
Solidus line
E
A+B • E = eutecticum: L A + B
• Only at this point is the liquid
0 10 20 30 40 50 60 70 80 90 100 phase (melt) in equilibrium
A B with two solid phases
wt% OR mol% B
2/6/2014
• Also: lowest melting point 24
 Phase diagrams
Tie lines

X • In equilibrium crystallization or
T1 L1 melting in a closed system, the
Liquid final composition of the system
T2
L2 will be identical to the initial
composition of the system.
B+
T3 L3 Liquid
“congruent melting”
A + Liquid
• Tie lines connect conjugated
A+B
phases, that is, phases that are
in equilibrium with each other
A 10 20 30 40 50 60 70 80 90 B (e.g., T1: A + L1; T3: A + L3)
%B
2/6/2014 25
 Phase diagrams
Cooling history
• T > T1: liquid phase with
chemistry X
X
• T = T1: the first infinitesimal
L1
T1 small amount of A forms; A is
Liquid
depleted in the remaining
T2
L2 liquid phase
B+ • T = T2 (T3): the fraction of A
T3 L3 Liquid crystals increases while the
A + Liquid
T4 liquid phase becomes B
LE enriched and shifts to L2 (L3)
A+B
• T = T4: solid A is in equilibrium
A 10 20 30 40 50 60 70 80 90 B with a liquid phase of chemistry
LE. Note: starting from X, LE is
%B the B-richest liquid possible! 26
2/6/2014
 Phase diagrams
Quantification: the lever rule

X
T1 L1
Liquid

a b B+
T3 L3 Liquid
A + Liquid

A+B

A 10 20 30 40 50 60 70 80 90 B
%B
2/6/2014 27
Example of a simple diagram with eutecticum in FactSage:
 Phase diagrams
SiO2-CaO phase diagram via FactSage

Remember: select the right

solution database or you will
never get a reasonable result!

2/6/2014 29
 Phase diagrams
SiO2-CaO phase diagram via FactSage

First try:
+ = single phase

2/6/2014 30
 Phase diagrams
SiO2-CaO phase diagram via FactSage

?!

We need to consider possible 2-

phase immiscibility (liquid phase)!

2/6/2014 31
 Phase diagrams
SiO2-CaO phase diagram via FactSage
Right mouse
button

2/6/2014 32
 Phase diagrams
SiO2-CaO phase diagram via FactSage

2/6/2014 33
 Phase diagrams of systems forming
chemical compounds
• If components A and B react
according to A + B = AB, the
MA third component (equimolar
Liquid MAB
compound AB) is formed in the
Liquid M system
Temperature

B
• Combine two phase diagrams
A+ AB + for A + AB and AB + B
Liquid Liquid AB + B+
E Liquid Liquid • Two eutectica: A + AB and AB +
Solidus line
B
E
• Two solidus lines, two liquidus
A + AB Solidus
line
AB + B lines, etc.
0 10 20 30 40 50 60 70 80 90 100 • Examples: Intermetallic
A B compounds (Mg2Pb, etc.)
wt% OR mol% B
2/6/2014 34
 Phase diagrams
Peritectic reaction
Peritectic line

Liquid • In a peritectic reaction, a liquid

phase and a solid phase are consumed
Temperature

+ Liquid by the formation of another solid

phase
P + Liquid

peritectic reaction
Liquid +
+

• P = peritectic point: here, + + L

A 10 20 30 40 50 60 70 80 90 B
are in equilibrium

%B
2/6/2014 35
 Phase diagrams
Calculated vs. experimental phase diagram

Ideal case: small (or no) deviation

2/6/2014 Gaskell 2008 Fellner & Gabcova, 1992 36

 Phase diagrams
Calculated vs. experimental phase diagram
“Usual” case: significant differences (esp. between different studies!)

o
2627
2800

Both calculated – no
Liquid

2400 Liquid

(25.2%)
o
experimental data 2400
2145
o
2068

2000 (27.3%)

Two different
T, C

T, C
o
2057
o

o
2000
2 Liquids

databases for the

-Ca2 SiO4
o 2 Liq.
1723
Ca3 SiO5

o
(43.8%) 1679

different software
Crs + Liq.
1600 o 1600
1544 Trd + Liq.
o

Hat
o 1471 o
1438 1444

packages (Zaitsev:
Psw
(63.5%)
Ca3 Si2 O7
Ca2 SiO4

CaSiO3

o (44.5%)
1258

IVTANTERMO; Ball:
o 1200 Wo + Trd
1450

Ra
'-Ca2 SiO4

Wo
1200

BINGSS)
0 20 40 60 80 100 0 20 40 60 80 100
CaO Mol % CaO Mol %
SiO2 SiO2

Zaitsev et al. 1993 Ball et al. 1993

2/6/2014 37
 Phase diagrams
Calculated vs. experimental phase diagram
“Usual” case: significant differences (esp. between different studies!)

2800
Some complex systems fill a
scientists lifetime to get studied
2400 in detail!

Phase diagram plotting via

T, C
o

2000

FactSage cannot replace

1600
experimental work!
Experimental work can be used
to refine calculation method
and calculated values help to
1200

0
CaO
20 40
Mol %
60 80 100
S iO 2
guide the experiments to
Zaitsev et al. 1993 Ball et al. 1993 concentrate on interesting x-T-
2/6/2014 P windows 38
 Phase diagrams
Free energy
BeO
2700 K
• Liquid = liquid UO2 + liquid BeO
• UO2: (Gs – Gl) = -3530 cal/mol
UO2
• BeO: (Gs – Gl) = -799 cal/mol
• “Mixture of solids” = mechanical!
• Step-by-step construction of the phase
diagram
• 1 UO2 0.5: lowest G for UO2 + L
• 0.5 UO2 0.1: lowest G for L
• 0.1 UO2 0.0: lowest G for BeO + L

Comparison: calculated and

2/6/2014 experimental phase diagram 39
 Phase diagrams
Free energy
2900 K
UO2 • Liquid = liquid UO2 + liquid BeO
• 1 UO2 0.2: lowest G for UO2 + L
• 0.2 UO2 0.0: lowest G for L
• There is no composition for which only
solid BeO would be stable!

2/6/2014 40
 Phase diagrams
Free energy
2500 K
BeO • Liquid = liquid UO2 + liquid BeO
• UO2 + BeO solid mixture energetically
most advantageous
• Only at UO2 ~0.6: lowest G for eutectic
UO2 phase equilibrium (BeO + UO2 + L)
• There is no composition for which only
the liquid phase would be stable!

90° difference for the eutectic point

between calculation and experiment

2/6/2014 41
Homework:

1. Build a phase diagram of Pb-Sn in FactSage. On the phase diagram indicate melting points of
both components, liquidus line, solidus line, phases in equilibrium, eutecticum. Using the phase
diagram calculate the composition and temperature of eutecticum. For T=498 K and mole
fraction of Pb in the system 0.67 calculate the composition and the relative amounts of phases
in equilibrium.

2. Plot one-component phase diagrams of water, CO2 and iron in the vicinity of their triple points.
What is anomalous about phase diagram of water compared to other two substances? Support
your reasoning by equations.

On each of these on-component phase diagram indicate:

a) Triple points and all phases in equilibrium;
b) Number of degrees of freedom at triple points, areas between the lines, and on the
equilibrium lines.

Using these one-component phase diagrams for each substance find:

a) Temperatures ad pressures at triple points;
b) Normal boiling temperatures;
c) Saturated vapor pressures in equilibrium with liquid at temperatures in the middle between
the triple points and normal boiling points;
d) Saturated vapor pressure at normal melting temperature.