MSE561: Phase Transformations,

Kinetics, and Diffusion in Solids

2. Ideal Solutions --- Your First Model of Binary Alloy

Yang Jiao

Materials Science & Engineering

School for Engineering of Matter, Transport and Energy
Arizona State University
Tempe, AZ 85287-6016

Lecture time T/Th 10:30 – 11:45 AM

https://asu.zoom.us/j/2759304275
 Topics Covered:

• Solid Solutions vs. Phase Separation

• Enthalpy of Mixing & Entropy of Mixing
• Configurational Entropy vs. Vibrational Entropy
• Counting configurational states, Stirling’s Approx.
• Effects of temperature
• Chemical potential
 Solution
Example: If three teaspoons of sugar are added to a cup of hot water
(coffee) it will dissolve initially, but upon cooling it will precipitate out
as a second phase. This occurs because the solubility limit decreases
with temperature, as shown in the Figure below.

Are all solutions in liquid state?

Temperature

Liquid

Liquid with sugar

precipitates

% Sugar

Solubility limits change with temperature.

 Solid Solution
Liquids can dissolve other substances, such as salt in water, forming a
homogeneous single phase. Similarly, some solids are soluble in one another.

Example: most gold jewelry contains some dissolved silver to strengthen it

and improve wear properties.

Solid Solutions: A homogeneous solid mixture of two or more elements

Hi-Temperature – lead soluble Low-Temperature – precipitates form

Cooling

Tin

Lead

Many solid and liquid solutions have solubility limits, which depends on
temperature. If the limit is exceeded, it results in the formation of a
secondary phase.
 Solution vs. Phase Separated State

Which phase (i.e., separated vs. mixing) is

thermodynamically more stable?
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Solution vs. Phase Separated State

Enthalpy of Mixing

Entropy of Mixing

Free Energy of Mixing

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 Ideal Solution

Enthalpy of Mixing

Free Energy of Mixing

Entropy of mixing plays the key role in free

energy of mixing for ideal solutions, and thus,
determines the stability of the phases!

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 Vibrational Entropy vs. Configurational Entropy

vN

xN
A single atomic configuration corresponds to Omega = 1

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 Vibrational Entropy vs. Configurational Entropy

vN

xN
At finite T, thermal vibration around a single atomic
configuration corresponds to Omega = M (~ proportional
to the volume of the region around the red dot) 9
 Vibrational Entropy vs. Configurational Entropy

At T=0, Omega = w, # of distinct atomic configurations

vN

xN

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 Vibrational Entropy vs. Configurational Entropy
At finite T, Omega = w*M, i.e., Total volume of the regions
around distinct atomic configurations

vN

xN

S  k ln   k ln( M )
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 Vibrational Entropy vs. Configurational Entropy

S  k ln   k ln( M )  k ln   k ln M  SC  SV
Configurational Entropy: SC  k ln 
Due to w, i.e., number of distinct atomic configurations

Vibrational Entropy: SV  k ln M
Due to M, i.e., states associated with around a specific
atomic configuration

At same T, vibrational entropy

Sv are the same for different
phases. Therefore, Sc plays a
key role in determining Gmix

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 Entropy of the two systems

1  1
2  ?
Sc1  k ln 1  0
Need to find the total number of
configurations for the solution!

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 Configurational Entropy of Solid Solution

Number of A atoms:
Na – Avogadro’s number
XA – molar fraction of A atoms

Number of B atoms:
Na – Avogadro’s number
XB – molar fraction of B atoms

The number of different ways (combinations) to place NA of

A atoms and NB of B atoms in the crystal lattice!
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Configurational Entropy of Solid Solution

( N A  N B )!
Sc 2  k ln 2  k ln
N A !NB !
Using Stirling’s approximation:

ln( N A  N B )! ln N A ! N B !
 N ln N  N  N A ln N A  N A  N B ln N B  N B
 ( N A  N B ) ln N  N A ln N A  N B ln N B
  N A ln  N A / N   N B ln  N B / N 

  N  X A ln X A  X B ln X B 

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Configurational Entropy of Solid Solution

Sc 2  k ln 2  kN  X A ln X A  X B ln X B 

Introducing the gas constant R:

R  kN a

Entropy of the solid solution:

Sc 2   R  X A ln X A  X B ln X B 

Is this entropy positive or negative?

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 Entropy of mixing

S mix  Sc 2  Sc1   R  X A ln X A  X B ln X B 

1  1
Sc1  k ln 1  0

Maximal entropy of mixing is achieved at

XA=XB = 0.5! --- the most random state!
Sc 2   R  X A ln X A  X B ln X B 
This is the mechanism for High Entropy
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Alloys (HEA)
 Free energy of mixing

S mix  S c 2  Sc1   R  X A ln X A  X B ln X B 

1  1
Sc1  k ln 1  0

Is mixing Favored or Not Favored?

Sc 2   R  X A ln X A  X B ln X B 
Which state (solution vs. phase
separate) is more stable?
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 Free energy of solid solution

1  1
Sc1  k ln 1  0
Free energy of the solution:

What G2 looks like?

Sc 2   R  X A ln X A  X B ln X B 
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 Free energy of solid solution

1  1
Sc1  k ln 1  0

Sc 2   R  X A ln X A  X B ln X B 
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 Free energy of solid solution

1  1
Sc1  k ln 1  0

Sc 2   R  X A ln X A  X B ln X B 
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 Chemical Potential

Free energy of the solution:

1  1 Write in a similar form as G1:

Sc1  k ln 1  0

GA (GB): molar free energy of A (or

B) atoms in the PURE substance!

Chemical Potential: molar free energy of

Sc 2   R  X A ln X A  X B ln X B 
A (or B) atoms in the MIXING state!
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 Tangent Construction for Chemical Potential

Tangent line
corresponds to
the linear G
equation!
1  1
Sc1  k ln 1  0

Mixing always reduces molar free energy of

Sc 2   R  X A ln X A  X B ln X B  A (or B) atoms for ideal solutions!
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 Topics Covered:

• Solid Solutions vs. Phase Separation

• Enthalpy of Mixing & Entropy of Mixing
• Configurational Entropy vs. Vibrational Entropy
• Counting configurational states, Stirling’s Approx.
• Effects of temperature
• Chemical potential
Thank You!

Questions?

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