MSE 508 Dept.

of Materials Science & Engineering

Solid State Thermodynamics Spring 2011/Bill Knowlton
Problem Set 6 Solutions

1. In class, we found that Dmk = RT ln ak . Using the toolbox 5 tables, derive Toolbox 5-
4 disregarding the first three and last listings in the tables. That is, derive the
following:
Toolbox 5-4: Relations between the PMPs of
component k and its activity

  ln ak 
S k   R ln ak  RT  
 T  p , nk
  ln ak 
Vk  RT  
 P T , nk
  ln ak 
H k   RT 2  
 T  p , nk
  ln ak    ln ak 
U k   RT 2    PRT  
 T  p ,nk  P T , nk
  ln ak 
Fk  RT ln ak  PRT  
 P T , nk

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MSE 508 Dept. of Materials Science & Engineering
Solid State Thermodynamics Spring 2011/Bill Knowlton

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MSE 508 Dept. of Materials Science & Engineering
Solid State Thermodynamics Spring 2011/Bill Knowlton

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MSE 508 Dept. of Materials Science & Engineering
Solid State Thermodynamics Spring 2011/Bill Knowlton
2. In the system Pandemonium (Pn) – Condominium (Cn), the partial molar heat of
mixing of Condominium (Cn) can be fitted by the expression: .
 J 
 H Cn  aX Pn
2
X Cn   where a  12,500 .
 mole 
Calculate and plot the function that describes the variation of the heat of mixing with
composition for this system. In plotting the function, do so with a mathematical
program that is not Excel. Do comment and provide insight to your plot.

units = J/mol

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MSE 508 Dept. of Materials Science & Engineering
Solid State Thermodynamics Spring 2011/Bill Knowlton

Hmix

800


600

mol
J
Hmix  400

200

0
0.0 0.2 0.4 0.6 0.8 1.0
XCn
Hmix

800


600
mol
J
Hmix 

400

200

0
0.0 0.2 0.4 0.6 0.8 1.0
XPn
It is evident that from the equation describing the enthalpy of mixing, ∆Hmix
=a/2(X2CnXPn), is not of the form aXCnXPn and therefore does not describe a
regular solution. Hence, the solution is non-, sub-, or irregular. This is also
evident due to the lack of symmetry in the plot above. The solution is
skewed toward larger values of Xcn (max. ~ 0.7Cn) since the mixture goes by
XCn2 and only linear in XPn. Notice that ∆Hmix has a positive maximum when
the stoichiometry of the alloy is Cn2Pn. This means that the reaction for the
solution at this stoichiometry is the most endothermic suggesting that this
stoichiometry is the least likely to form. This may be due to a repulsive
behavior between Cn-Cn. The entropy of the solution is not discussed here
and will certainly have an effect on which stoichiometry will form. To
determine whether or not the Cn2Pn alloy is the least likely to form requires
knowledge of ∆Gmix.

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 MSE 508 Dept. of Materials Science & Engineering
Solid State Thermodynamics Spring 2011/Bill Knowlton
3. Below is a thoroughly stated problem with a thoroughly provided solution. Create a a
thoroughly problem and a thoroughly stated solution that parallels the problem and
solution provided below. For the problem, you will either need to create your own
data or find data (the literature: text books, journal articles, etc.). Be as thorough as
the problem and solution is below.

PROBLEM: Data are given below for the Gmixxs

as a function of composition for a liquid
solution of Fe and Mn at 1863 K. Using the data, thoroughly answer the following
questions and comment and provide insight to each of the thoroughly labeled plots that
you generate:
XMn 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
Gmix (J/mol) 395
xs 703 925 1054 1100 1054 925 703 395

a. Prove whether or not the system exhibits regular solution behavior.

For this problem, much insight to the regular solution model can be gained
from:
[1] Joel H. Hildebrand, Solubility. XII. Regular Solutions, Journal of the American Chemical
Society, 51 (1929) p. 66-80. You can ask Bill for a copy.
Let: X1=XMn and X2=XFe
Note: The regular solution model is defined in Toolbox 5-2 at the bottom of
column 1. Using this information, we can prove whether or not the data in the
above table exhibits Regular Solution Behavior.

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MSE 508 Dept. of Materials Science & Engineering
Solid State Thermodynamics Spring 2011/Bill Knowlton

Note that ao should be J/mole and the same is true for Gmix
xs
.

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MSE 508 Dept. of Materials Science & Engineering
Solid State Thermodynamics Spring 2011/Bill Knowlton

For the remainder of the problem, let: XS = regular solution XS

b. Derive an equation for Gmix xs

and plot it as a function of XMn. Explain
whether or not the plot exhibits endothermic or exothermic behavior and
provide insight as to why this behavior is observed.
Since the solution is regular, we know that the regular solution model is
defined in Toolbox 5-2 at the bottom of column 1 such that:
xs xs
G1  ao X 22 & G 2  ao X 12
xs xs
[1].
G Mn  ao X 2
Fe & G Fe  ao X 2
Mn

where X1=XMn and X2=XFe. In general, we know from toolbox 5-1 that:
xs xs
Gmix
xs
 X 1G1  X 2 G 2 [2]
And substituting [1] into [2], we find that:
Gmix
xs
 X 1ao X 22  X 2 ao X 12
 ao X 1 X 2  X 2  X 1 
 ao X 1 X 2
 ao X Mn X Fe
The answer above is no surprise since it is of the same form as shown
for the regular solution model in Toolbox 5-2 at the bottom of column 1.
We know ao is 4395 J/mole and we can now plot Gmixxs
.
Gxs
mix
1200

1000
  

800
mol
Gxmsix   J

600

400

200

0 0.2 0.4 0.6 0.8 1

XMn
Since Gmix
xs
 H mix
xs
 H mix and we see that the curve is positive in energy,
then we can say that the curve exhibits endothermic behavior.

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MSE 508 Dept. of Materials Science & Engineering
Solid State Thermodynamics Spring 2011/Bill Knowlton
xs xs
c. Derive equations for G Fe and G Mn and plot them as a function of XMn.
Comment and provide insight for your plot.
From part a, we know that:
xs xs
G Mn  ao X Fe
2
& G Fe  ao X Mn
2
[1].

We know ao is 4395 J/mole and we can now plot G Fe and G Mn .

xs xs

Blue : 
Gxs xs
1 ; Red: G2

4000
 l 
3000
xs    J
mo

2000
G k

1000

0
0 0.2 0.4 0.6 0.8 1
XMn
xs
What we see is that as X Mn  0, G Mn  ao and becomes very active and does
not act ideal at all. This makes sense since there is very little Mn in solution
and is probably being solvated by Fe and vice versa. We also observe that as
xs ID
X Mn  1, G Mn  0 & G Mn  G Mn . So pure Mn or pure Fe acts as an ideal
solution in this regime.

d. Derive an equation for S mix and plot as a function of XMn. Comment on

and provide sight to your plot.
Since the solution is regular, we know that:
S mix
Reg
 S mix
ID
  R  X 1 ln X 1  X 2 ln X 2    R  X Mn ln X Mn  X Fe ln X Fe 
SReg
mix
6

5
 l 

4
SRmeigx  m o
J

0 0.2 0.4 0.6 0.8 1

XMn
We observe that at maximum mixing where XMn = XFe = 0.5 that the
solution is at its greatest disorder thereby maximizing entropy.

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MSE 508 Dept. of Materials Science & Engineering
Solid State Thermodynamics Spring 2011/Bill Knowlton

e. Derive an equation for Gmix and plot as a function of XMn over a

temperature range between 1800 – 2000 K (i.e, multiple plots on the same
graph). Use 50 K increments for temperature. Explain and provide insight
on whether Gmix
ID
or Gmix
xs
has a greater effect on your plot.
Since the solution is regular, we know that:
Gmix
Reg
 H mix
xs
 T S mix
ID

Where:
S mix
ID
  R  X 1 ln X 1  X 2 ln X 2  and Gmix
xs
 ao X 1 X 2  H mix
xs
.
Substituting, we have:
Gmix
Reg
 ao X 1 X 2  RT  X 1 ln X 1  X 2 ln X 2 
 ao X Mn X Fe  RT  X Mn ln X Mn  X Fe ln X Fe 
GReg
mix
0

-2000
 l 
J
GRmeigx  m o

-4000
Increasing
-6000 temperature
-8000

-10000
0 0.2 0.4 0.6 0.8 1
XMn
We see that the Gmix
ID
term has a much greater affect on Gmix
Reg
than does
the Gmix
xs
 H mix
xs
term since the Gmix
Reg
is negative (i.e., concave up).

f. Derive equations for the activities of Fe and Mn and plot as a function of

XMn over a temperature range between 1800 – 2000 K (i.e, multiple plots
on the same graph). Use 50 K increments for temperature. Comment on
and provide insight to your plot.
We know in general that:
xs xs
G1  RT ln  1 & G 2  RT ln  2
Since the activity of component k is defined as:
ak   k X k
Then:
xs a1 xs a
G1  RT ln & G 2  RT ln 2
X1 X2
Since the solution is regular, we know that:

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MSE 508 Dept. of Materials Science & Engineering
Solid State Thermodynamics Spring 2011/Bill Knowlton
xs xs
G1  ao X 22 & G 2  ao X 12
Equating the last two sets of equations, we have:
a a
RT ln 1  ao X 22 & RT ln 2  ao X 12
X1 X2
Solving for the activities, we have:
ao X 22 ao X 22 2
ao X Fe 2
ao X Fe
a1  X 1e RT
 1- X 2  e RT
so aMn  X Mn e RT
 1- X Fe  e RT

ao 1- X 2  ao 1- X Fe 
2 2

a2  X 2 e RT
so aFe  X Fe e RT

aFeGreen & aMnMagenta

1

0.8

0.6
ak

0.4

0.2

0
0 0.2 0.4 0.6 0.8 1
XMn
We see that the activity does not vary greatly as a function of
xs
temperature. Since G k for regular solution is not, to first order, a
function of temperature (see [1]), this result is not too surprising.

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MSE 508 Dept. of Materials Science & Engineering
Solid State Thermodynamics Spring 2011/Bill Knowlton
g. Derive equations for the activity coefficients of Fe and Mn and plot as a
function of XMn over a temperature range between 1800 – 2000 K (i.e,
multiple plots on the same graph). Use 50 K increments for temperature.
Comment on and provide insight to your plot.
We know in general that:
xs xs
G1  RT ln  1 & G 2  RT ln  2
Since the solution is regular, we know that:
xs xs
G1  ao X 22 & G 2  ao X 12
Equating the last two sets of equations, we have:
RT ln  1  ao X 22 & RT ln  2  ao X 12
Solving for the activities, we have:
ao X 22 2
ao X Fe
1  e RT
so  Mn  e RT

ao 1- X 2  ao 1- X Fe 
2 2

2  e RT
so  Fe  e RT

FeOrange & MnPurple

1.3 Increasing
1.25 temperature
1.2
k

1.15
1.1
1.05
1
0 0.2 0.4 0.6 0.8 1
XMn
We observe that for a solution of near purity, the  for the solute
approaches 1 with little effect by temperature. This signifies a near ideal
solution case. As the solute concentration becomes very dilute, the 
increases but less so with increasing temperature. However, temperature
has little effect as we would expect since S mix
xs
must be zero for a regular
xs xs  G kxsxs 
solution. Thus,  S and  S must be zero. That is,  S      0 . As
 T 
1 2 k

  P ,nk
mentioned in part f, since G k for regular solution is not, to first order, a
xs

function of temperature (see [1]), this result is not too surprising.

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