MATE 152 Lec 2

Spring 2024

Dr Shashi Agarwal
Section 1.2 Single component system
(a pure element or one type of molecule that does not change over temp/pressure of interest)

• Phase representation on P-T diagram (no composition)

• Examples are Water, pure Fe
• Note phases present at a given P,T phase boundaries and triple point
– Gibbs Free Energy Variation with Temperature of each phase determine phase preference (note a
discontinuity at transition temperature)

– Gibbs Free energy variation with pressure (not hugely interesting)

– Concepts Application

• Phase equilibrium change in a single component systems with T, P (Clapeyron Equation)

• Melting and Solidification

Single Component Phase Diagram-- PureIron
Equilibrium Phase Diagram (P,T) for Pure Fe

10 kBar = 1 GPa

Phase Crystal PHASE ΔVm dP/dT

MOLAR VOLUME
structure CHANGE
α BCC 7.099 cm3
γ FCC 6.49 cm3 α-Υ -Ve Slope is -Ve
δ BCC α-δ
ε HCP 6,899 cm3 α-ε -ve Slope is -ve
Melting of a single component system
• A phase transformation from solid to liquid
• Free energy of the liquid decreases faster with temperature than that of solid
• L (latent heat) is defined with the difference in entropy at Tm
• Gibbs Free energy at solidification
at m.pt
ΔG ~= L ΔT/ Tm (1.17) See derivation in book
• Rate of solidification vs phase stability (different concepts)
Thermodynamics determines phase stability
Kinetics requires additional information about phase transformations
ΔT indicates probability of nucleation of new phase
Driving Force increases with ΔT
L (kJ/mole) TK
Water (s to l) 6 273
Al 11 934
Al2O3 107 2324

Element/molecule atomic bonding determines Latent heat

Multi Component: Mixture vs Solution

Mixture: Matter consisting of two or more pure substances that retain their individual
identities and can be separated by physical methods
Oil and water
sand and water
Solutions
homogenous solution: Mixture having a uniform composition and properties
throughout (also called a solution)
Ferritic steel
Au and Ag
doped semiconductors

heterogenous Solution: Mixture not uniform in composition and properties throughout

and more than one phase
Al and Cu

What about mixture of gasses??

Thermodynamics provides a much better answer

Solutions and Alloys
• Key concepts
• We rarely use pure metals.
• Alloys are metallic solutions and are much more of engineering
interest.
• Gibbs Free energy of solutions
• In open systems and multi-component systems, Gibbs free energy
has additional component due to composition (in addition to T and P)
• Mixing effects in multi-component systems
ΔGm = ΔHm - T * ΔSm

Gafter mix = Gbefore mix + ΔGmix

• ΔGmix is calculated for Ideal solution and regular solution (models for
interaction between components)
 1.3.2 Ideal solution

No Mixing

After Mixing
Gafter mix = Gbefore mix + △Gmix
Ideal Solution
Simplest model, no interaction between atoms so random mixing
ΔHmix = 0
ΔSmix = -R (XA lnXA + XB lnXB) Eq1.25
A more detailed look at free energy of mixing in binary systems

Look at fig 1.9 (effect of temp)

>The free energy of solution will depend upon G A, GB, and mixing effects
>Free energy curve will assume greater curvature at higher temperature
(mixing effects are stronger)
.
1.3.3 Chemical Potential
The chemical potential of the species i (symbol is i ) is the rate of increase of G
with ni when specie i is added/generated in the system at constant T, P, and
number of moles of all the other species. (symbol is )
i = (G/ni )P,T,nJ

dG = -SdT+ VdP +i dni i = 1 to n

• Can be applied to both open and closed systems

• Two Key equations (for binary systems)

• G = μA XA + μB XB J/Mole 1.31

μA = GA + RT ln XA

1.32
μB = GB+ RT ln XB
Free Energy Curve and Activity
• Tangent construction relates Free energy of pure component, Chemical Potential
and composition of an alloy

• A more general case is GA-μA = RT ln aA

where aA= activity of element A in solution

• Activity is defined as state of component in solution

1.3.4 Regular Solutions
• Solution which has an ideal entropy of formation and non-zero heat of formation
from its pure components.
• A simple model with key assumptions:
• Heat of mixing (Δ Hmix) is only due to bond energies between adjacent atoms
• No volume or elastic strain energy
• In the case of completely randomized atoms, the number of A-B bonds is PAB
PAB = Na z XA XB
and Δ Hmix = PAB ε = Ω * XA* XB (Ω (Omega) = Na z ε )
ε = εAB – ½(εAA +εBB)
ε (bond energy) is –ve when dissimilar atoms like each other.
Na is Avogadro’s number
z is number of bonds per atom.}
• Free energy change on mixing
Δ Gmix = Ω * XA* XB + RT (XA ln XA + XB ln XB)
• Heat of formation of a regular solution is equal to GXS.
• ΔHM= GXS = RTα XA XB •
Effect of Δ Hmix and T on Δ Gmix (Fig 1.15) in Regular Solutions

• Note two minima

and maxima
• Minima are
compositions of
phase separation
• Similar atom
clustering
Regular solution:
GRS as function of temperature at a fixed value of Ω

HRS as function Ω (Bond energy function)

Regular Solution—Miscibility Gap (ALSO SEE P 302 IN PORTER)
NOTE
• PHASE SEPARATION AT LOWER TEMPERATURE
• CRITICAL TEMPERATURE (DIFFERENTIAL OF ENERGY = 0))
• SPINODAL COMPOSITION (CHANGE IN ENERGY CURVECURVATURE)
α
•

α1 + α2
α
Alloy Thermodynamics
• An important consequence of thermodynamics is that at constant temp and
pressure, a closed system will be in stable equilibrium only if it has lowest
possible value of Gibbs free energy ;
• Materials (metals/alloys/ceramics/glasses) transform to different phases at
different temperatures consistent with free energy and are unstable till G is
minimized

• The phase of maximum entropy dominates at highest temperatures. For most

materials this is a gas of isolated atoms, but at lower temperatures most
materials form solid or liquid phase with continuous solubility

• At low to intermediate temperatures, the equilibrium phases and their chemical

composition depend on the free energy vs composition curve for each phase at
temperature of interest.

• At lowest temperatures, we have very small effect of entropy and will have
precise stoichiometry and a high degree of long range order.
Class Exercise-2
15 g of Au and 25 g of Ag are mixed to form a single phase ideal solid solution.

a. How many moles of solution are there?

b. What are mole fractions of Au and Ag?

c. What is molar entropy of mixing?

d. What is total entropy of mixing?

e. What is molar free energy change at 500 C?

f. What are the chemical potentials of Au and Ag at 500 C taking that free Au atom is added
? Express answer in ev/atom?

g. By how much the free enargy of the solution will change at 500C? If one Au atom is
added?
Homework Prob 1

Key impurities in raw Si are Ag, Cu and Al.. Consider mole fractions of Ag is 0.01, Cu is 0.05, Al
is 0.1 and rest Si. Bulk Si is melted under vacuum and held at 1700K

a. Calculate vapor pressure of each

b. Calculate mole fractions of each element in vapor phase (hint: think of mole fraction in
terms of vapor pressure)
c. What do you conclude about purity of S, if molten Si is kept in vacuum at 177K for a long
time

M Pt Vapor Pressure of pure

element(@1700K)
Ag 1234 3.16 Torr
Cu 1358 0.12
Al 933 0.18
Si 1687 5.12 x 10-4
Homework Prob 2

The boiling point of Li is 1620K

A What is vapor pressure if Liquid Li at 1000K (Hint: think Clapeyron equation)
b. Estimate the melting point of Lithium from the data given (Hint: at m.pt solid and liq
are in equilibrium)

Data Enthalpy of Evaporation is 156kJ/mole

Vapor pressure above solid Li is given by ln(P) = 13.049 – (19314/T)
Homework Prob 3

The properties of mixing for a liquid A-B mixture at a temperature of 1000 K are shown in
below
a. Is the liquid A-B mixture an ideal solution? Briefly justify your answer.

b. What is the vapor pressure if A in a mixture with 95% B? (hint: think of Tangent
construction)

c. 1 mole of pure A liquid at 1000K is added to 1.5 moles of pure B liquid at 1000K? How
much heat needs to be extracted/added to keep the system at 1000 K?

Data:
Vapor pressure of pure A at 1000K = 10-5 atm
Vapor pressure of pure B at 1000K = 10-2 atm
Heat capacity for all compositions of the liquid = 30 J/mol-K
Homework

• Read 1.2, 1.3.1 to 1.3.5

• Homework
class exercises 1 and homework prob 1,2,3
Porter 1-4
Homework due next Tuesday Feb 6 ,2024
• Solid Solutions: The Hume-Rothery Rules
• H. K. D. H. Bhadeshia
• Hume-Rothery (1899-1968) was a metallurgist who studied the alloying of metals. His research was conducted at Oxford University where in
1958, he was appointed to the first chair in metallurgy.
• His research led to some simple and useful rules on the extent to which an element might dissolve in a metal [1-4]. The rules that he derived
are paraphrased here. The rules are still used widely. For example, the miscibility gap in Au-Ni is correlated with the fact that the lattice
parameter of Au is 1.15 times that of Ni, thus acting maximally according to Hume-Rothery [5].
• If a solute differs in its atomic size by more than about 15% from the host, then it is likely to have a low solubility in that metal. The size
factor is said to be unfavourable.
• If a solute has a large difference in electronegativity (or electropositivity) when compared with the host, then it is more likely to form a
compound. Its solibility in the host would therefore be limited.
• A metal with a lower valency is more likely to dissolve in one which has a higher valency, than vice versa.
• A quasicrystal has long-range order but lacks translational periodicity in three dimensions. Such crystals are in fact periodic in higher
dimensions. When these higher dimensions are projected in three, it becomes possible to observe symmetries in diffraction patterns which
are not possible in structures with 3-dimensional translational symmetry. Examples include 5-fold and 10-fold rotation axes. A quasicrystal
can in three dimensions be imagined as the tesslation of two different unit cells.
• Quasicrystals are frequently found in aluminium alloys, and in particular those with electron/atom ratios around 1.75. Hume-Rothery deduced
(for example in Cu-Zn alloys) that compound formation occurs at specific electron/atom ratios and this principle has been used to predict
quasicrystal formation in aluminium based systems [6].
• References
1. W. Hume-Rothery and H. M. Powell, Z. Krist.,, 91 (1935) 23.
2. W. Hume-Rothery, Atomic Theory for Students of Metallurgy, The Institute of Metals, London, 1969 (fifth reprint).
3. W. Hume-Rothery, R. W. Smallman and C. W. Haworth, The Structure of Metals and Alloys, , The Institute of Metals, London, 1969.
4. A. H. Cottrell, An Introduction to Metallurgy, Edward Arnold (publishers), London, 1967, p.192.
5. K. Janghorban, J. S. Kirkaldy and G. C. Weatherly, J. Phys. (Condensed Matter), 13 (2001) 8661.
6. A. P. Tsai, MRS bulletin, November 1997.
Homework solutions
Homework Solutions
Homework Solutions 2