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 isnt

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

Chose components that cannot be converted into one another by reactions

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. JP1= JP2= JP3= JP4= JP5.{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

Point a: only vapor present Point b: Liquid boils - 1 atm= Tb but vapor and liquid co-exist along line(vapor pressure curve) Point C : Liquid freezes Point D: Only solid Triple point: 3 phases in equilibrium Line Below triple point: Vapor pressure above solid Note: You dont necessarily have to have 3 phases and they dont have to be solid liquid and gas

Cooling Curve

A B 100C Liquid Cooling Temp. Solid f reezing C 0C Solid Coolin g D Gas Cooling Gas Condensing

You can generate a cooling curve @ constant pressure (isobar) from previous phase diagram Halts occur during 1st order phase transitions (e.g. freezing)

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 cant 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 Raoults 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 Raoults law so the mole fraction in the gas phase, yA 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 1 0.8

p*/p*=1000
A B

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

0.6

p*/p*=4
A B A

p*/p*=2
B

p*/p*=1 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 axis is the overall composition, zA (as mole fraction)

In Liquid region zA = xA In vapor Region region zA = yA In between two phases present F=1 so at given pressure compositions are fixed by tie lines

Isopleth Compositions in Each Phase

A vertical line represents a line of constant composition or isopleth Until pressure = p1sample is liquid vapor phase composition is a1 At p1, vapor composition is given by tie line to vapor curve At p2 vapor composition is a2, liquid composition is a2 and overall composition is a At p3 vitually all the liquid is vapor and trace of liquid has composition given by tie line to liquid

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 the tie line

nl = nl or n= nl / l

Temperature-Compositions
Assume A more volatile than B Region between two curves is 2-phase region F=1 (pressure is fixed) At given temperature compositions are fixed by tie lines Region outside lines composition & temperature variable Heat liquid with composition a1 Hits boiling curve, vapor has composition a2, liquid a2 (=a1) vapor is richer in more volatile component Distillation Vapor condensed (a2-a3) New vapor @ concentration a3 (richer still) New condensate @a4 etc until nearly pure liquid obtained

Distillation/Theoretical Plates
A theoretical plate is a vaporization-condensation step Previous example has 3 theortetical plates If the two curves move closer together, more theoretical plates are required to achieve same degree of separation

Curves more together if components have similar vapor pressures

Non-Ideal T-C Diagrams - High Boiling Azeotropes

Maximum in phase diagram occurs when interactions in liquid between A & B stabilize the liquid GE is more negative If such a liquid is boiled, as vapor is removed, composition of liquid is richer in B (less A)

As vapor is removed you move to right up the curve until you reach point b At b liquid boils with constant composition
Called an azeotrope (unchanging Gr.)

Example HCl-water boils @80 wt % water at 108.6C

Non-Ideal T-C Diagrams - Low Boiling Azeotropes

Minimum in phase diagram occurs when interactions in liquid between A & B destabilize the liquid GE is more positive If such a liquid is boiled, & vapor is condensed , composition of vapor is richer in B (less A)

As vapor is removed you move to right down the curve until you reach point b At b liquid boils with constant composition Example ethanol-water boils at constant water content of 4 wt% @ 78C

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 Consider Cooling along isopleth from a1

At a2 pure B starts to come out of solution At a3 solution is mixture of B + Liquid with composition b3 (ratio by lever rule) At a4 liquid has composition e and freezes

In solid region there are two phases pure A and pure B

Composition given by tie line, ratio by lever rule

e is called a eutectic

Examples of Simple Eutectic Systems

Componen t A Picric Acid Sb Cd KCl Si

Tm of A (K) 395 903 594 1063 1685

Componen t B TNT Pb Bi AgCl Al

Tm of B (K) 353 599 444 724 930

Eutectic Mol %B 64 81 55 69 89

Eutectic Tm B (K) 333 519 417 579 851

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 Thats 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 183C NaCl and water (23/77) melting point -21.1C

Liquid-Solid Phase Diagrams - Reacting Systems

Some Binary systems react to produce one (or more) compounds

Definite composition Unique melting point

Congruent melting point, I.e. melts to a liquid of identical composition

Maximum in phase diagram Phase diagram interpreted as before except now there are additional regions

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

He for power applications H2, NH3 for propulsion applications
Superior performance to NERVA system (70s era nuclear propulsion system)

Multiple coolants possible

High power densities (10s MW/liter)

Typical operating temperatures >2500 K for propulsion

PBR - Schematic

Materials Requirements for PBR Hot Components

Hot frit, nozzle, etc. Withstand H2 Environment ~2800 K 70 atmospheres Large Temperature Gradients 12K to Tmax over a few cm Multiple Thermal Cycles Long Exposure Times 10s minutes Launch Stresses Withstand Radiation Fields Not Affect Reactor Criticality

Fuel Same as general components Provide for adequate reactivity Optimize coating thickness and type to maintain criticality Maintain (Keff) No HfC coatings Maintain coolable geometry No large gaps between layers No particle clumping No reaction with other components, e.g. hot frit 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
High cost 11BN required Unacceptable thermal decomposition (3 wt % in 10 min @ 2700 K Reaction with baseline ZrC fuel coating Potential for CTE mismatch between coatings and substrate

Pyrolytic BN

Carbide-Coated Carbon (graphite & carbon-carbon)

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

UC

HTGR - SiC PBR - ZrC Spongy layer Dense layer HTGR - UO2 PBR - UC

Pyrocarbon layer(s)

Inner kernel

UC melting point 2525C UC2 2350-2400C

Carbide Phase Diagrams

Tantalum-Carbon

Zirconium-Carbon

Liquid-Solid Phase Diagrams - Reacting Systems (Incongruent Melting)

If the compound is not stable as a liquid incongruent melting occurs

Compound melts into components Called the peritectic melting point One solid phase melts around the other

Isopleths a

a1-> a2 liquid phase with A + B a2 solid B precipitates a3->a4 Solid B + compound

b2-> b3 liquid phase with A + B b3 B reacts to form compound b3->b4 Solidcompound + liquid b5 solid A precipitates with compound

Zone Refining

Ultra high purity can be obtained by moving a small molten zone across a sample.

Impurities more soluble in liquid than solid so they continually move down the liquid front One end becomes purer while other end is dirtier Multiple passes can be used to achieve high purity

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 Usually temperature

Pressure or temperature add third dimension

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

cm

4.2

4.2
1

cm

5.7 cm
A 100 % Component "A"

4.2 cm

To obtain relative amounts d rop a perpendicular to each axis Ratio of the lengths of lines is the ratio of compone nets Ratio A:B:C "1 " = 1:1:1 or 33% o f each component "2 " = 1.6:1:2.2 or 33 .6%A, 20.8%B, 45 .6%C