Chapter 8: Phase Diagrams

Homework
Exercises (a-only): 8.3,4, 6, 13, 15
Problems 8.2 & 8.4
Definitions
 Phase(P) -“State matter which is uniform throughout not only in
chemical composition but also in physical state” J. Willard Gibbs
» Solid
 Various phases [e.g. crystal structures (diamond; graphite) or compositions
(UC;UC2)]
 Alloys (sometimes its difficult to tell this - microscopic examination
may be necessary {dispersions uniform on macroscopic scale})
 Miscible one phase (P=1)
 Immisible multiple phases (P>1)
» Liquid
 Miscible liquids are one phase
 Immiscible liquids are multiple phases (P>1)
» Gas
 Systems consisting of gases can have only one phase
» Shape or degree of subdivision irrelevant
Definitions
 Heterogeneous and homogeneous systems
» Systems with one phase are homogeneous
» Systems with more than one phase are heterogeneous
 Constituent- a chemical species (ion or molecule which is present
 Component (C) - chemically independent constituents of a system
» C = #of independent chemical constituents - # of distinct chemical
reactions
 #of independent chemical constituents = total # of constituents minus
the number of any restrictive conditions (charge neutrality, material
balance etc.)
Counting Components
 Example: CaCO3(s)  CaO(s) + CO2(g)
» Phases: P = 2 solid + 1 gas = 3
» Component: C = 3 consitiuents - 1 reaction = 2
 Example: Consider the system NaCl, KBr and H2O. Suppose you can also isolate
the following from it KCl(s), NaBr(s), NaBr. H2O(s), KBr. H2O(s), and NaCl. H2O(s)
» Phases: P = 5 solid
» Components:
 There are 8 constituents
 You can write the following reactions four:
NaCl + KBr  KCl + NaBr; NaCl + H2O  NaCl. H2O
KBr + H2O  KBr. H2O; NaBr + H2O  NaBr. H2O
 Conditions: 1 -Material balance moles of KCl = moles of NaBr + NaBr. H2O
 Components: C = (8 constituents -1 condition) - 4 reactions = 3
Counting Components (continued)
 Remember you must count reactions which actually occur not those
which could occur
» Consider a system in which we has the following : O2(g), H2(g),
H2O(g)
 If conditions are such O2(g) + H2(g)  H2O(g) does not occur, C=3
 If conditions are such (T, catalyst) O2(g), H2(g)  H2O(g) occurs, then
C=3components -1reaction =2
 If conditions are such (T, catalyst) O2(g), H2(g)  H2O(g) occurs and you impose
the condition that all the hydrogen and oxygen come from dissociation of water, then
C=3 constituents - 1 condition -1 reaction = 1
 Identity of components is a matter of some choice, number isn’t
» Chose components that cannot be converted into one another by reactions
 E.g. CaCO3(s)  CaO(s) + CO2(g)
Phase Rule
 In discussing phase equilbria, you need only consider intensity factors
(temperature, pressure, and concentration)
» Only certain of these can be varied independently
» Some are fixed by the values chosen for the independent variables
and by the requirements of thermodynamic equilibrium
 e.g. if you chose  and T for a system P is fixed
» Number of variables which can be varied independently without
changing the number of phases is called the degrees of freedom of
the system
» The number of degrees of freedom or variance of a system, F, is related to
the number of components(C) and number of phases(P)
» F=C-P+2
Phase Rule Proof
 In any system the number of intensive variables are: pressure,
temperature plus the mole fractions of each component of each phase.
 Only C-1 mole fractions are needed since the xJ = 1
» Thus for P phase, the number of intensive variables = P(C-1) + 2
 At equilibrium the chemical potential of phase must be equal,
i.e. µJP1= µJP2= µJP3= µJP4= µJP5….{there are P-1 such equations}
» Since there are C components, equilibrium requires that there are C(P-1)
equations linking the chemical potentials in all the phases of all the
components
» F = total required variables - total restraining conditions

F = P(C-1) + 2 - C(P-1) = PC - P + 2 -CP + C = C- P + 2

One Component Systems
 Phase rule says that you can have at most 3 phases
» F = C- P +2; C=1 so F=3-P
 If P=3, F=0 system is invariant
 Specified by temperature and pressure and occurs at 1 point (called the
triple point)
 If one phase is present, F = 2 that is P and T can be varied
independently
» This defines an area in a P,T diagram which only one phase is
present
 If two phases are present, F = 1 so only P or T can be varied
independently.
» This defines a line in a P, T diagram
 Single Component Phase Diagram
Typical Section of Single Component
Phase Diagram
 Point a: only vapor present
(Water in {})  Point b: Liquid boils - 1 atm= Tb but
vapor and liquid co-exist along
d c b a
1 atm line(vapor pressure curve)
Phase II  Point C : Liquid freezes
{Liquid}
 Point D: Only solid
P
Phase I  Triple point: 3 phases in equilibrium
{Solid}
Triple Point  Line Below triple point: Vapor
{P=4.58 mm; T=0.01°C}

Phase III
pressure above solid
{Vapor}
Note: You don’t necessarily have to have 3
phases and they don’t have to be solid
Temperature Bo ilin g Point
liquid and gas
Cooling Curve
 You can generate a cooling
A Gas Cooling
curve @ constant pressure
B
Gas Condensing (isobar) from previous phase
100°C
diagram
Liquid Cooling

Temp.
 Halts occur during 1st order
Solid freezing
phase transitions (e.g. freezing)
C
0°C
D
Solid Cooling

Time
Experimental Measurements
 Phase changes can be measured by performing DTA
(differential thermal analysis) on samples
» In DTA sample is heated vs. a reference
» 1st order transitions can be measured even when they can’t be
observed
 They will occur as peaks in DTA
 High Pressures can be achieved with diamond anvil cells
» See text descriptions
Two Component Systems
 For two component systems, F = 2-P+2 = 4-P
» If P or T is held constant, F’ = 3-P (’ indicates something is
constant)
 Maximum value for F’ is 2
 If T is constant one degree of freedom is pressure and the other is
mole fraction
 Phase diagram (Constant T) is map of pressure and compositions at
which each phase is stable
 If P is constant one degree of freedom is temperature and the other is
mole fraction
 Phase diagram (Constant P) is map of temperature and compositions at
which each phase is stable
» Both Useful
Vapor Pressure Diagrams
 By Raoult’s law (pA = xApA * & pB = xBpB * ), the total pressure
p is
» p = pA + pB = xApA * + xBpB *
» But xB = (1-xA)so xApA * + xBpB * = xApA * + (1-xA) pB * = pB * + xA(pA * -
pB *)
 @ Constant T, total vapor pressure is proportional to xA (or xB )
» The composition of the vapor is given by Raoult’s law so the mole
fraction in the gas phase, y A and yB is
 yA = pA/p and yB = pB/p {also yA = 1-yA)
 From above yA = xApA * /[pB * + xA(pA * -pA *)]
 If pA * /pB *= pA/B then yA = (xA * pA/B) /(1+ (xA * pA/B) - xA )
 Or yA = (xA * pA/B) /(1+ (xA *( pA/B - 1) )
Effect of Ratio of Vapor Pressure
on Mole Fraction in Vapor
1.2

p*/p*=1000
1 A B

p*/p*=10
0.8 p*/p*=50 A B
A B

0.6 p*/p*=4
A B
p*/p*=2 p*/p*=1
A B
A B
0.4

0.2

0
0 0.2 0.4 0.6 0.8 1

Mole Fraction of A in Liquid

 This shows the vapor is richer in the more volatile component

 If B is non volatile then yB = 0
Pressure Composition Diagrams

 Assume the composition on the x

isopleth a
axis is the overall composition, zA
P
A (as mole fraction)
a1
p1
Liquid
F=2
p2 » In Liquid region zA = xA
a2
F=1
» In vapor Region region zA = yA
p3 a3
Liquid + Vapor
» In between two phases present
Pressure
F’=1 so at given pressure
Vapor compositions are fixed by tie
F=2
P
lines
B

x yA
A
Mole Fraction of A z A
Isopleth Compositions in Each Phase
 A vertical line represents a line of constant
composition or isopleth
isopleth a
P » Until pressure = p1sample is liquid
A

Liquid p1
a1 vapor phase composition is a1
p2
F=2 a2 a'2 » At p1, vapor composition is given by

p3
F=1
a3
tie line to vapor curve
Liquid + Vapor
» At p2 vapor composition is a’2, liquid
Pressure
composition is a2 and overall
Vapor composition is a
F=2
P
» At p3 vitually all the liquid is vapor
B
and trace of liquid has composition
given by tie line to liquid
x yA
A
Mole Fraction of A z A
Determining proportions of Phases
(lever rule)
 The composition of each phase
is given by the each end of the
tie line
 The relative proportion of each
phase is given by the length of
n
n the tie line
l l » nl = nl or n= nl / l
 Temperature-Compositions
Assume A more volatile than B
Region between two curves is 2-phase region
Vapor
» F’=1 (pressure is fixed)
Vapor Composition
» At given temperature compositions are fixed
a'2
by tie lines
a2
T2
Region outside lines composition & temperature
variable
Temp,T Heat liquid with composition a1
» Hits boiling curve, vapor has composition a2’,
liquid a2 (=a1)
a3 a'3
T3  vapor is richer in more volatile
a1
component
T b Distillation
Boiling Temperature of Liquid
a4

Liquid » Vapor condensed (a2’-a3)

» New vapor @ concentration a3’ (richer still)
Mole Fraction, z » New condensate @a4 etc until nearly pure
A
liquid obtained
Distillation/Theoretical Plates
A theoretical plate is a
Vapor vaporization-condensation step
1
a2 a'2
Previous example has 3 theortetical
T2 1
2
plates
Temp,T If the two curves move closer
together, more theoretical plates
a3 3 a'3
are required to achieve same
T3 2
a1
degree of separation
4
3 T » Curves more together if
a4
b
Liquid components have similar vapor
pressures
Mole Fraction, z A
 Non-Ideal T-C Diagrams - High Boiling
Azeotropes
Maximum in phase diagram occurs when
Vapor Vapor interactions in liquid between A & B stabilize
Compositon
a4 a4'
a3'
the liquid
a3

a2
a2
» GE is more negative
Tb(b) Boiling
Temperature
of the Liquid
If such a liquid is boiled, as vapor is removed,
composition of liquid is richer in B (less A)
Temp,T
» As vapor is removed you move to
right up the curve until you reach
point b
a1
Tb(a)
» At b liquid boils with constant
a4 composition
Liquid Called an azeotrope (unchanging Gr.)
b a
» Example HCl-water boils @80 wt
Mole Fraction, z A % water at 108.6°C
Non-Ideal T-C Diagrams - Low Boiling
Azeotropes
Minimum in phase diagram occurs when
Vapor interactions in liquid between A & B
destabilize the liquid
a2
» GE is more positive
a2'

Tb(b)
If such a liquid is boiled, & vapor is
condensed , composition of vapor is
Vapor
Compositon
Temp,T
richer in B (less A)
a3'
a3 » As vapor is removed you move
a4'
a4
to right down the curve until
a1
Tb(a)
Boiling you reach point b
Temperature
of the Liquid
a4 » At b liquid boils with constant
Liquid
b a
composition
» Example ethanol-water boils at
Mole Fraction, z A
constant water content of 4 wt
% @ 78°C
Non-Ideal T-C Diagrams - Immisicble
Liquids
 If two liquids immiscible and in intimate contact then p is
nearly the sum of vapor pressures of pure components (p
= pA* +pB*)
» mixture will boil when p = atmospheric pressure
» intimate contact (& trace level saturation maintained)
 If two liquids immiscible and not in intimate contact then p
for each is the vapor pressures of pure components (p =
pA* and p = pB*)
» Each will boil separately when respective pA* = atmospheric
pressure and/or pB* = atmospheric pressure
Liquid-Solid Phase Diagrams
 Liquids miscible & solids
immiscible
a1

Liquid
 Consider Cooling along isopleth
(P=1) a2
from a1
» At a2 pure B starts to come out of
T(°C) b3 a3
solution
» At a3 solution is mixture of B + Liquid
Liquid + A Liquid + B with composition b3 (ratio by lever
(P=2) (P=2)
a4 rule)
e (Eutectic) » At a4 liquid has composition “e” and
Solid A + Solid B freezes
(p=2)
a5' a5 a5"
 In solid region there are two
1
phases pure A and pure B
0
Mole Fraction B  Composition given by tie
line, ratio by lever rule
 “e” is called a eutectic
Examples of Simple Eutectic Systems

Component Tm of A Component Tm of Eutectic Eutectic

A (K) B B Mol %B Tm B (K)
(K)
Picric Acid 395 TNT 353 64 333
Sb 903 Pb 599 81 519
Cd 594 Bi 444 55 417
KCl 1063 AgCl 724 69 579
Si 1685 Al 930 89 851
Eutectics
 In previous diagram, the eutectic (easily melted, Gr.) point is a
temperature at which a mixture freezes without first depositing pure A
or B
» Like a melting point in that it it is a definite temperature
 That’s because, since C=2 and P=3, by Phase rule, F’=0
» A cooling (or heating) curve will have a halt at the eutectic temperature
 If pure A and pure B are in contact a liquid will form at the eutectic
temperature
 Examples
» solder lead/tin (67/33) melting point 183°C
» NaCl and water (23/77) melting point -21.1°C
Liquid-Solid Phase Diagrams - Reacting
Systems
 Some Binary systems react to
Liquid (P=1)
produce one (or more)
compounds
a1 » Definite composition
a2
» Unique melting point
Solid
 Congruent melting point, I.e.
T(°C)
Solid A
+
Compound
+
a3
Solid
melts to a liquid of identical
Liquid Liquid
Compound
+ Solid B composition
e1 Liquid +
a4 Liquid » Maximum in phase diagram
Solid A
+
e2
Solid B
+
» Phase diagram interpreted as
before except now there are
Solid Compound Solid Compound
a5
a5"
additional regions
0 1
Mole Fraction B
PARTICLE BED REACTORS
(PBRs)
 High Power Density Nuclear Sources for Space Power &
Propulsion
» Performance superior to chemical rockets (H2/O2)
 Enabling technology for Mars mission
» Multiple coolants possible
 He for power applications
 H2, NH3 for propulsion applications
» High power densities (10’s MW/liter)
 Superior performance to NERVA system (70’s era nuclear propulsion system)
 Typical operating temperatures >2500 K for propulsion
PBR - Schematic
Materials Requirements for PBR Hot
Components
Hot frit, nozzle, etc. Fuel
 Withstand H2 Environment  Same as general components
» ~2800 K  Provide for adequate reactivity
» 70 atmospheres » Optimize coating thickness and

 Large Temperature Gradients type to maintain criticality

Maintain (Keff)
» 12K to Tmax over a few cm
» No HfC coatings
 Multiple Thermal Cycles
 Maintain coolable geometry
 Long Exposure Times
» No large gaps between layers
» 10’s minutes
» No particle clumping
 Launch Stresses
 No reaction with other components, e.g.
 Withstand Radiation Fields
hot frit
 Not Affect Reactor Criticality  Minimum F.P. and U release
» Criticality and safety criterion
Hot Component Material Selection
 Reactor Components (Hot Frit)
» Rhenium (monolithic & coatings)
 Large neutronic penalty for monolithic Re
 High radiation heating for monolithic Re
 Extensive alloying of Re with fuel coatings @ T > 2760 K
» Pyrolytic BN
 High cost 11BN required
 Unacceptable thermal decomposition (3 wt % in 10 min @ 2700 K
 Reaction with baseline ZrC fuel coating
» Carbide-Coated Carbon (graphite & carbon-carbon)
 Potential for CTE mismatch between coatings and substrate
 Fuels
» Baseline fuel HTGR-type with ZrC coating

Conclusion: Materials development program focused on carbide

coatings of carbon materials
“HTGR” Type Fuel
 Outer carbide shell
» HTGR - SiC
UC » PBR - ZrC
 Pyrocarbon layer(s)
» “Spongy” layer
» Dense layer
 Inner kernel
» HTGR - UO2
» PBR - UC
 UC melting point 2525°C
 UC2 2350-2400°C
 Carbide Phase Diagrams
4000

3500 3400±50
Ta C 3330±100
2
Tantalum-Carbon
3000 2830±25
T,°C TaC TaC+C
Ta
2500
2180
2000 1930
Ta C
2

3500 3420±20
0 0.4 0.8 1.2 1.6
C/Ta, atom ratio Liquid
3000 2850±50

2500
ZrC Zr+ZrC
T,°C
2000 1810-1835
Zirconium-Carbon
1500
 Zr+ZrC
Zr+ZrC
1000

0.2 0.4 0.6 0.8 1.0

C/Zr, atom ratio
Liquid-Solid Phase Diagrams - Reacting
Systems (Incongruent Melting)
 If the compound is not stable as a liquid
incongruent melting occurs
b1 a1
Liquid (P=1) » Compound melts into components
p =Peritectic point a2 Solid B
» Called the peritectic melting point
+
Liquid  One solid phase “melts around” the
b2
a3 other
b3

b4 a4
 Isopleths
Solid
Compound Solid B » “a”
+ +

T(°C)
Solid A
+
Liquid Solid Compound  a1-> a2 liquid phase with A + B
Liquid b5  a2 solid B precipitates
e1  a3->a4 Solid B + compound

Solid A
» “b”
+
Solid Compound
 b2-> b3 liquid phase with A + B
 b3 B reacts to form compound
Compound Composition
 b3->b4 Solidcompound + liquid
0 1
Mole Fraction B  b5 solid A precipitates with compound
Zone Refining
Liquid
 Ultra high purity can be obtained by moving a
small molten zone across a sample.
Melting Curve » Impurities more soluble in liquid than solid so
a1
they continually move down the liquid front
a2 a2" a2
b2
Liquid
» One end becomes purer while other end is
L+S a3"
Composition
dirtier
Temp,T
» Multiple passes can be used to achieve high
Solid
Composition
purity

Freezing Curve

Solid

Mole Fraction of B, X B
Ternary Phase Diagrams
 Each composition must be defined by two compositions or
mole fractions
» Composition diagrams are therefore two dimensional
 Triangle with each edge one line of binary phase diagram
» Pressure or temperature add third dimension
 Usually temperature
 Phase diagrams are usually given as a succession of
surfaces at constant temperature
 To examine temperature variation you hold composition
constant
Ternary Phase Diagrams
C

2.6 cm
cm 4.2
2
4.2
cm cm
4.2

1
5.7 cm

4.2 cm

A B
100 %
Component "A"
To obtain relative amounts drop a perpendicular to each axis
Ratio of the lengths of lines is the ratio of componenets
Ratio A:B:C
"1" = 1:1:1 or 33% of each component
"2" = 1.6:1:2.2 or 33.6%A, 20.8%B, 45.6%C