MATSCI 204

THERMODYNAMICS AND PHASE EQUILIBRIA

Winter 2016
Final Exam

You get no credit for answers that are not clearly justified
Exam strategy: the points given for every problem are related to how important the topic is
not necessarily to how difficult the problem is so look at all the questions first to optimize
your exam time!

Please write neatly and clearly

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Problem 1
(20 points)
2 points each T/F answer. If F, 1 point for the F, 1 points for the correct explanation)

Answer the following questions with True or False and write a 1-line explanation of why you
think the statement is false (you dont need to write anything if the statement is true). Write
the explanation on this sheet and dont forget to turn it in!

T/F The energy of the Universe can never change

T/F The entropy of the Universe can only increase for any spontaneous process

T/F A bigger thermodynamic driving force for a transformation always translates into a faster
process

F: a faster process relates to kinetics, which are not necessarily linked to thermodynamic driving
forces

T/F In a binary system at an arbitrary P, there can never be more than 3 phases in equilibrium

T (NB: arbitrary P means that P is fixed at an arbitrary value so thats a lost degree of freedom)

T/F Diffusion always occurs down a thermodynamic activity gradient

T/F The decomposition pressure of an oxide MO depends only on the strength of the M-O
bonds, i.e. the oxidation enthalpy

F: it also depends on the entropy of the reaction

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T/F The chemical potential of a species depends on the reference state chosen

F: the chemical potential is a physical quantity thats independent of the reference state, its
measure requires a reference state

T/F The activity of a species depends on the reference state chosen

T/F Miscible species at constant (P,T) always display a negative enthalpy of mixing

F: they can have a positive enthalpy of mixing because the entropy of mixing is always positive

T/F Miscible species at constant (P,T) always display a negative Gibbs free-energy of mixing

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Problem 2
(40 points-10 points each)

The Salleo solution is a special type of non-ideal binary solution. It is regular and exhibits a
mixing enthalpy of the form: hmix = X 2 (1 X) . So that we all use the same symbols, we will
assume that the elements forming the solution are A and B and the mole fraction in the equation
above is that of B.

1. What is the entropy of mixing of the Salleo solution?

2. Find an equation relating the activity coefficients of the two components to

composition.

3. We measure Henrys coefficient of A at room temperature and it is equal to 1.8.

What is the heat of mixing at X=0.5?

4. What is Henrys coefficient at 500C (assuming that the mixture still obeys the
Salleo solution model)?

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Answer:
1. Regular solution=mixing enthalpy is ideal:
Smix = R[X ln(X) + (1 X)ln(1 X)]

2. If the solution is regular, the only contribution to non-ideality is the mixing enthalpy. We
have:
RT ln( A ) = H A,mix .
The partial molar enthalpy of mixing is obtained from the hmix using the tangent
construction found in the notes. With our naming convention:
dhmix
H B,mix (X) = hmix (X) + (1 X )
dX
dhmix
H A,mix (X) = hmix (X) X
dX
I obtain:
2
RT ln ( B ) = 2 X (1 X )
RT ln ( A ) = X 2 ( 2X 1)

! $
3. Henrys coefficient K for A is the limit of A when X tends to 1. Hence: K A = exp # &
" RT %
and as a result we extract =1.47 kJ/mol. At X=0.5, the heat of mixing is 183 J/mol.

4. In a regular solution, the heat of mixing cannot depend on T (p. 168 of the notes),
! $
therefore is independent of T: K A = exp # & with T=500C, I get KA=1.26.
" RT %

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Problem 3
(60 points)

Calvin, an eager PhD student in Stanford is itching to create a new startup company, and having
just finished taking Thermodynamics, is now well versed in reading phase diagrams.
When examining the binary phase diagram of Gallium and Arsenic, he notices that GaAs is the
only compound that forms between the two elements, and has a very narrow region of stability.
Calvin realizes that he may have a new way to grow GaAs crystals quickly and at low cost, the
key to commercial success. Calvin realizes that the synthesis kinetics will be much more
favorable if at least one of the precursors is in the liquid phase. Since Ga has a low melting
point, Calvin decides to synthesize a large GaAs boule by taking a large block of arsenic,
immersing it in an excess of molten gallium (to ensure that the entire block of arsenic is reacted),
and waiting long enough for the system to reach equilibrium.

a) What is the temperature range in which Calvin could have made his GaAs boules?
(5 points)
Leaning on his newly made boule of GaAs, Calvin proudly tells his colleagues about his new
method of making GaAs wafers when Hobbes walks in sipping from a can of soda, and asks
Calvin what kind of electrical contacts he plans on using. Calvin proudly responds that he will
use Al, since it is earth abundant, and relatively cheap to come by. Hobbes chuckles, putting his
can down on the boule, and says, I thought you just finished studying thermodynamics. Didnt
you learn anything about activity?

b) Using the Ga-As phase diagram below, plot the activity of gallium at 300K as a
function of XGa. Make sure to state explicitly your reference state, as well as the
value of activity and composition at every point where the activity changes.
(10 points)

c) What is activity of Ga in Calvins boule? Justify your answer to get credit.(5 points)
Hobbes asks Calvin to look-up the phase diagram of Ga-Al to try and determine what would
happen if Al contacts were deposited on the boule.

d) In the Ga-Al binary system, plot the activity of gallium at 300K as a function of XGa.
As before, make sure to explicitly state your reference state, as well as the value of
activity and composition at every point where the activity changes. Justify all the
assumptions you make. (10 points)

e) What is the activity of Ga in the aluminum contacts immediately upon deposition

(i.e. before any reaction or equilibration)? What do you conclude should happen
over time? (10 points)
So, whats the problem? asks Calvin. Smiling, Hobbes replies, Ill show you why it matters.
Hobbes reaches out to pick up his soda that had been sitting on the boule, and as his fingers close

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around the can, the aluminum crumbles into pieces. You see, Hobbes explains, Ga can attack
Al and break apart its grain boundaries, totally destroying the contacts that you want to put down
on your new solar cells. Hobbes walks away smugly, while Calvin distraughtly cries out, Hey,
by leaching out Ga you decomposed part of my GaAs boule and now I will have toxic As in my
lab!

f) Is Calvin right, did the boule decompose and he will be poisoned? (10 points)
After Hobbes walks away, Calvin thinks for a while longer, and realizes that Hobbess argument
might not be relevant for him. After all, he was planning on using his high quality wafers in a
solar concentrator, where the temperatures are around 800K. Frantically, he looks around for a
pad and paper to redo his calculations at a higher temperature.
g) Recalculate the activity plots for the higher temperature case. Remember to include
your chosen reference state, as well as the activity and composition values at the
points where the activity changes. Does Calvin get a different answer at high
temperature? (5 points)

h) How could Calvin have changed the synthesis process to avoid having such reactive
Ga in his GaAs? (5 points)
Data:
Assume all solutions are ideal
Enthalpy of fusion of gallium is 5.6 kJ/mol
Phase diagrams on the next page

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Answer:
a) The synthesis Calvin envisions can be done anywhere from 303-1083 K
b) This should be a step function: from x=0 to .5, its in equilibrium with solid arsenic, so
the activity is 0, and from .5 to 1, its in equilibrium with solid gallium so the activity is
1.

c) The circled point is the activity of Gallium in the boule. Because the boule was formed
from an excess of Gallium, you expect the boule to be slightly gallium richer, thus
choosing the upper bound of the steep drop at the line compound.
d) The Ga in Al line is a little more complicated because there is a Eutectic at 299.3 K, and
the melting point of Ga is 303 K. I choose solid Ga as the reference because it makes my
life easier. Thus, you expect a flat line until the transition to liquid at ~.98, then a drop
along the liquid Ga line, (at a slope of exp(5600(3/300)/2494.2) until you hit the
transition to two phases (~.97), where you get a flat line until ~.08. Then, the activity
should drop to zero along a straight line.

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Zooming in near the XGa=1, you are crossing a pure Ga and a narrow Ga-L 2-phase coexistence
because 300K is between the eutectic temperature and the melting point of Ga:

e) The activity of Ga in Al solid is zero, and is thus quite a bit lower than it is in the boule.
The gallium should diffuse from the wafer into the aluminum until the activity of Ga in
both the GaAs boule and the Al1-xGax phase is the same.
f) No, Calvin is wrong. In order to get enough gallium to leave the wafer to begin forming
pure As solid (which is what Calvin is presumably concerned about), the activity of
gallium in GaAs would have to drop to zero, which would be thermodynamically
impossible as the activity of the gallium in Al will be greater than zero for all
compositions.
g) Higher temperature will not affect the result very much. The reference chosen should be
liquid Ga. There should be a barely perceptible drop on the GaAs activity just at x=1
because the liquid gallium phase is stable there for more than just a line compound. The
GaAl diagram should drop linearly for the first 70%, then horizontally until around 6%.
The slope of the activity in the Al1-xGax phase should be the same as it was in part e.
This is checkable by comparing the activity at the point at which the sloped region
begins.

h) Three options that I can think of:

1. Run the synthesis at a higher temperature, where you are able to have two liquids
mixed with a seed crystal to ensure that you can carefully control the
stoichiometry. In that case, you can just put more arsenic than gallium in the

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 melt. Its true that the arsenics activity will be higher, then, but then you wont
have to worry about the aluminum problem, at least.
2. Keep adding solid blocks of arsenic until the entire pool of gallium is used up.
The last one that you add will not be fully converted to GaAs, and will likely be
junk, but the others will not have an excess of gallium.
3. Start at the exact right composition (GaAs) in the liquid and freeze the congruent
solid.

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Problem 4
(60 points)

Consider the Pt-Si phase diagram below.

1. In your blue book, going from left to right, to the best of your knowledge list all
eutectics, peritectics, eutectoids, peritectoids and congruent melting points. For each
reaction write the phases involved and write the reaction that occurs as you cool the
system. If according to this phase diagram, there are reaction that violate the phase
rule, indicate them as well. (10 points)

2. Sketch the activity of Si as a function of Si content at T=1019C and T=974C (for

simplicity assume that the activity is always proportional to XSi). (20 points)

3. Draw a sketch of the g vs. XSi curves at T=974C across the whole compositional
range. (10 points)

4. Sketch a heating curve (i.e. T vs. time when a constant heat flux is applied) at XSi=10
at. %. For simplicity, use only straight lines. Be as quantitative as possible about
relative slopes and the temperatures where the slopes change. (20 points)

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Answer

1. I count 11 horizontal lines, which correspond to 3-phase equilibria or violations of the

phase rule. This is a good way to ensure we dont miss anything. I have:

Congruent melting points:

1769C: Pt(l)->Pt(s)
1105C: Pt2Si(l)-> Pt2Si(s)-HT
1232C: PtSi(l)->PtSi(s)
1414C: Si(l)->Si(s)

Eutectics:
851C: L->Pt3Si-HT+Pt
1008C: L->Pt6Si5+Pt2Si
974C: L->PtSi+Si

Peritectics:
874C: L+Pt12Si5->Pt3Si
1004C: L+Pt2Si-HT->Pt12Si5
1019C: L+PtSi->Pt6Si5

Eutectoids: none that can be distinguished from phase rule violations

Peritectoids:
842C: Pt+Pt3Si-HT->Pt25Si7-RT
870C: Pt3Si-HT+Pt12Si5-HT->Pt5Si2

Violations (4 phases intersecting a line): 440C, 770C, 745C

Including the 4-phase intersecting points, I have 11 special temperatures.

2. At 1019C we have:

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At 974C, we have:

3. Here is a plausible set of g vs. X curves. Important aspects are the common tangents and
ensure that the phase combinations shown in the phase diagram always correspond to the
lower Gibbs free energy section in the g vs. X plot.

4. To obtain the heating curve, we follow the phase behavior along a vertical line at XSi=0.1

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 From RT to 842C, the slope is given by the inverse of the specific heat of the solids.
To cross the peritectoid temperature, all Pt25Si7 must react, this leads to a plateau.
From 842C to 851C, Pt and Pt3Si coexist, the slope is given by the inverse specific
heat of the two solids (no reaction as they are both line compounds).
At 851C, there is a eutectic reaction: all Pt3Si must disappear, which leads to another
plateau.
From 851C and 1640C, Pt and L coexist. The slope is shallower than the previous
segments because to increase the temperature Pt and L must be heated and some Pt
must melt too.
The last solid is found at 1640C, beyond which there is only liquid and the slope is
steeper than the previous segment because no latent heat of melting is involved.

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Problem 5
(50 points)

ZrO2 is a very stable refractory oxide, which means that it has a very negative heat of formation
(i.e. strong Zr-O bonds) and a high melting point. There are no other oxides in the Zr/ZrO2 phase
diagram.
A slab of ZrO2 is put in contact with a slab of Zr. The two materials are then sealed in an
ampoule and heated until equilibrium is reached.
At 1800K, the measured solubility of O2 in the solid Zr equiliubrated with ZrO2 is 15 parts-per-
million. You can certainly consider it a dilute solution of O2 in Zr.
We are initially interested in the properties of this solid solution.

1. Using your intuition and the information above: do you expect Henrys
coefficient for O2 in Zr to be large or small? (10 points)

2. Calculate Henrys coefficient at 1800K. (10 points)

3. The measurement is repeated at 1850K and it is found that Henrys

coefficient doubled. Calculate the molar heat of mixing of O2 in Zr (i.e. the
enthalpy of mixing 1 mole of O2 in Zr, not that of making 1 mole of Zr/O2
solid solution). (10 points)

4. The slab of ZrO2 is replaced by a film epitaxially grown on an inert substrate

that puts ZrO2 in a state of compression. For simplicity, the mechanical state
is considered equivalent to a hydrostatic pressure of 200 MPa:
a. Using your intuition, do you predict that the maximum solubility of
O2 in Zr will increase or decrease and why? (5 points)
b. Calculate the equlibrium solubility of O2 in Zr under these new
conditions (T=1800K). (10 points)

5. Explain in a short paragraph why chips of equilibrated Zr/ZrO2 are excellent

oxygen getters when dropped in molten metal. (5 points)

Data:
At 298K:
hF (ZrO2)=-1080 kJ/mol
S(ZrO2)=50.3 J/K.mol
S(Zr)=39.2 J/K.mol
S(O2)=205 J/K.mol
Assume that Cp for the formation reaction of ZrO2 is ~0
VZrO2=2.16x10-5 m3/mol (assume the compressibility is negligible)

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Answer
1. Considering that ZrO2 is a very stable oxide, this means that Zr has a very strong affinity
for O. As a result, I would expect that Henrys coefficient would be very small.

2. To calculate Henrys coefficient of O2 in Zr, we need to calculate its activity and compare
it to the expected activity for an ideal solution. Because the solid solution of Zr and O2 is
equilibrated with ZrO2, the oxygen pressure over the solid solution must be the same as
the decomposition pressure of ZrO2. With the data given, we can calculate h0298 and
S0298. I get h0298=-1080 kJ/mol and S0298=-194 J/K.mol.
We need to calculate g01800 in order to obtain the equilibrium oxygen pressure. If the Cp
of the formation reaction is ~0, we can assume that h0T and S0T are independent of
temperature. As a result, g0T= h0298-T S0298. For T=1800K, I get g0T=-731 kJ/mol.
!P $ ! g 0 $
The decomposition pressure is given by: # O20 & = exp # T & , which gives PO2~6.2x10-22
" P %eq " RT %
atm. (I told you it was a very stable oxide!). Using pure oxygen at 1 atm as the reference
state, the activity of O2 in the oxide and in the metal is 6.2x10-22.
If the solution of O2 in Zr was ideal, its activity would be equal to 15x10-6 using the same
reference state of pure O2 at 1 atm (the pressure of O2 at equilibrium would be equal to
the mole fraction times the pressure of pure oxygen in its chosen reference state). As a
result, Henrys coefficient K is 6.2x10-22/15x10-6=4x10-17, a very small number indeed!

3. In the dilute solution limit, Henrys coefficient is the activity coefficient. The dependence
ln ( ) H mix
of the activity coefficient on temperature is given by: = . In the dilute
(1 / T ) R
solution limit, the total molar enthalpy of mixing is only equal to the partial molar
enthalpy of mixing of the solute because the solvent is ideal. Hence we obtain
ln ( )
H mix = R , which is the molar heat of mixing we are looking for. Using the data
(1 / T )
ln ( )
provided ( is Henrys coefficient), we have =-46164 and H O2 , mix =-384 kJ/mol.
(1 / T )
You can also use the equation H O2 , mix = RT ln ( K ) where K is Henrys coefficient since a
dilute solution is also regular. You get a different result (my fault, I did not run this check
when I set-up the problem) and you get full credit.

4.
a- Applying pressure increases the chemical potential of ZrO2 solid and as a result I
expect the partial pressure of oxygen (and therefore the equilibrium solubility of O2 in Zr)
to increase.

b- Hydrostatic pressure changes the activity of ZrO2 according to the following equation:
200 MPa
RT ln ( aZrO2 ) = vZrO2 dP ~vZrO2 ( P ) . Plugging in the numbers, I get aZrO2~1.33.
0.1MPa

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 " PO2 %
$ 0'
#P &
Since gT0 = RT ln , we get as a new equilibrium pressure
aZrO2
! PO2 $ !P $
# 0& = aZrO2 # O20 & ~8.2x10-22 atm. Henrys coefficient in Zr does not depend
" P %200 MPa " P %0.1MPa
on the pressure condition in ZrO2, therefore the same multiplication factor applies to the
equilibrium solubility of O2 in Zr: XO2~20 ppm.

5. Because the activity of O2 is so low in these chips, every oxygen molecule that
encounters them will be captures and used to transform Zr into ZrO2 and maintain the
low oxygen activity mandated by the 2-phase equilibrium. They cease to work as getters
when all the Zr is consumed and only ZrO2 is left because in this case there is no 2-phase
equilibrium anymore.

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Problem 6
(50 points)

Id like to protect Fe from oxidation at 1000C with a sacrificial amount of Cr dissolved into it,
so that Cr oxidizes first leaving Fe intact. Henrys coefficient of Cr in Fe is 0.1.

1. What is the minimum mole fraction of Cr I need to dissolve in Fe? (10 points)

Use the Ellingham diagram to answer the following questions (briefly justify each one to get full
credit):

2. 1 mole of Cr2O3 and 1 mole of Al2O3 are sealed in a closed, evacuated container at
1200C?
a. What is the equilibrium state of the system (name phases present and oxygen
pressure)? (10 points)
b. Explain why it is unphysical to not observe any Cr2O3 at equilibrium. (5
points)

3. What CO/CO2 ratio oxidizes Ni at 800C? (10 points)

4. Will Ti reduce water to H2 at 500C? Calculate the ratio of H2 to H2O pressures at

equilibrium. (10 points)

5. What is the equilibrium pressure of oxygen at the melting point of Mn? (5 points)

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Answers

1. Pure Cr is below all the Fe lines, which means it oxidizes more easily. Diluting it in Cr
reduces its activity and makes it less reactive. The minimum amount of Cr is the mole
fraction that provides an activity such that the equilibrium pressure of Cr is equal to that of
Fe. Any more Cr will oxidize preferentially compared to Fe.
For the Cr oxidation at 1000C, g0=~-530 kJ/mol.
2/3
aCr ! 530, 000 $
So we have for the Cr oxidation equilibrium: K Cr = 2O3
= exp # &
! PO2 $ 4/3 " R 1273 %
# 0 & aCr
"P %
We need to plug in the lowest O2 pressure that would oxidize Fe in order to find the Cr
activity that would make Cr oxidize at that pressure rather than Fe. From the Ellingham
diagram, thats oxidation to FeO, which occurs at PO2~10-15 atm. Assuming that the activity
of Cr2O3 is 1 (pure oxide), I get aCr=8.7x10-6. Since aCr=K.XCr, We get XCr=87 ppm.

2. The oxides will start decomposing in the vacuum. The decomposition pressure of Cr2O3 is
higher than Al2O3 therefore the final state will be Al2O3, Cr2O3 in equilibrium with Cr at the
Cr2O3 decomposition pressure (~10-18 atm.). The reason why the pressure is not fixed below
the Cr2O3 decomposition pressure is that for this happen, all the Cr2O3 would have to
decompose entirely: you can calculate the volume necessary to have 1.5 moles of O2 at
pressures below 10-18 atm

3. Reading from the scale in the Ellingham diagram, I have a CO/CO2 ratio of ~0.02.

4. If we look at the H2 to H2O ratio in equilibrium with Ti at 500C, we get something between
1012 and 1013, so yes, Ti certainly reduces H2O!
The ratio of pressures is obtained by calculating g0 from the Ellingham diagram since the
scale does not allow to read it exactly.
The reaction Ti+2H2O->TiO2+2H2 can be split as Ti oxidation (g0500=~-775 kJ/mol) and
water splitting ((g0500=+400 kJ/mol), so for the reaction above we have (g0TOT=-375
2
! PH 2 $
# 0& ! gTOT
0 $
"P % 12
kJ/mol). Using the equation 2
= exp # & , we obtain PH2/PH2O~4.7x10 .
! PH 2O $ " RT %
# 0 &
" P %

5 Reading from the diagram I get ~10-19 atm.

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