Materials Thermodynamics

Some Sample Problems

Hasan Bin Awais (PIEAS)

1
Problem # 1

2
 An Enthalpy Problem
Uranium can be produced by reacting a uranium bearing
compound with a more reactive metal, e.g., Mg can be used to
reduce UF4 according to the reaction
UF4 + 2Mg 2MgF2 + U
This reaction is exothermic, and the sensible heat released is
used to increase the temperature of the reaction products. In
order to facilitate a good separation of the U from the MgF 2, it is
desirable to produce them as liquids (which are immiscible). If
the reactants are placed in an adiabatic container in the molar
ratio Mg/UF4=2.0 and are allowed to react completely at 298 K.
1. Is the quantity of sensible heat released by the reaction sufficient
to increase the temperature of the reaction products to 1773 K?
2. What is the actual temperature attained by the adiabatically
contained reaction products? Calculate their state as well.
3. Calculate the amount of preheat which is required for the reaction
products to reach to 1773 K.
4. Draw and Explain the enthalpy-temperature diagram (DIY)

3
 Given Thermodynamic Data

Heats of Formation of MgF2 at 298K & UF4

Cp (as temperature dependent terms) of U, U, U,

Uliq, MgF2(s), MgF2(liq), Mg(s), Mg(liq), UF4

Latent heats & the transformation

temperatures of
UU UUliq
MgF2(s) MgF2(liq)
Mg(s) Mg(liq),
4
The Actual Data

5
Is the quantity of sensible heat released by the
reaction sufficient to increase the temperature of
the reaction products to 1773 K?

UF4 + 2Mg 2MgF2 + U

Strategy
1. Choose a basis
2. Calculate the heat released in the reaction
3. Calculate the heat required to raise the
temperature of one mole of U & 2 moles of
MgF2 from 298 to 1773K. All sensible and
latent heat effects
4. Compare the heat required with the heat
available & provide your answer. NO

6
What is the actual temperature attained by the
adiabatically contained reaction products and in
which state they are?

UF4 + 2Mg 2MgF2 + U

Strategy
1. Place in ascending order (from lowest T to 1773K), the sensible
and latent heating steps
2. Make a combined reaction products equation and add the
coefficients of Cp polynomial of equal powers
3. Determine by integration the heat required for each
successive heating step
4. After reaching 1536K, you would notice that some
insufficient heat is still available, not to take the reaction
products to 1773K, but to melt part MgF2. You would
calculate the state by the Unity formula (No of moles of
MgF2 that can be made liquid = Heat available divided by
the latent heat to melt one mole of MgF2)
5. T = 1536K, U(liq) : State MgF2 (liq) : MgF2 (S) :: 1 : 1.23 :
0.77
7
Calculate the amount of preheat which is required
for the reaction products to reach to 1773 K?

UF4 + 2Mg 2MgF2 + U

Strategy
1. Calculate the required heat from first question
2. Use the following formula to calculate T
T
Required Heat C
298
p, reactants dT

3. Place in ascending order the phase transition temperatures

of the REACTANTS from lowest to higher values
4. Assume T is less than the MP of Mg = 923K (the lowest
possible assumption), Solve
5. T = 859K

8
The Enthalpy-Temperature
Diagram

9
Problem # 2

10
 Excess or Limiting Reactants

A mixture of Fe2O3 and Al, present in the molar

ratio 1:2, is placed in an adiabatic container at
298 K, and the Thermit reaction
2 Al + Fe2O3 2Fe + Al2O3
is allowed to proceed to completion.
1. Calculate the state and the temperature of the
reaction products
2. Suppose, now, it is required that the increase in the
temperature of the products of the Thermit reaction
be limited to 1809 K to produce liquid Fe at its melting
temperature. How can we achieve it? What would be
the final molar ratio of the reactants and products?

11
The Actual Data

12
Calculate the state and the
temperature of the reaction products

Exactly same logic as previous

T = 3343K (BP of Fe)
State liq Al2O3:liq Fe:Vap Fe :: 1 : 1.95 :
0.05

13
 How can we retain/limit the
temperature of the products to 1809K
i.e., the MP of Fe (to produce liq Fe at
its melting temperature)?
Add excess Fe (reactant) in an amount sufficient
to absorb the excess sensible heat.

Remaining heat after attaining 1809K

# of moles of excess Fe
Heat required to raise one mole of Fe from 298
to 1809 & converting it to liquid Fe at 1809K

T = 1809K (MP of Fe)

State molar ratio Fe:Al:Fe2O3 :: 8.49 : 2 : 1

14
Problem # 3

15
A Single Component Phase
Diagram

16
The normal boiling temperature is defined as that temperature
at which the saturated vapor pressure of the liquid is 1 atm.
2600K
The saturated vapor pressures for the solid and liquid phases
intersect at the triple point. 1239K
The triple-point pressure is then calculated from the equation
for the vapor pressure of the solid or from the equation for the
vapor pressure for the liquid by putting T trip. 2.29x10-4 atm

Write the general Clausius-Clapeyron

dlnP H
equation in terms of Liq to
Vapr phase equilibria viz. then differentiate the
dT RT 2

saturated liquid vapor pressure and equate with this term

putting normal boiling point of 2006K. Hliqvap= 216,500J

At any T, , do as above Hsl= 33,150J

See

17
Problem # 4

18
 Activity Problems
The activities of Cu in liquid Fe-Cu alloys at
1550C have been determined as
XCu 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.05
aCu 1 0.935 0.895 0.865 0.850 0.830 0.810 0.780 0.720 0.575 0.04

Calculate the activity of iron with at XFe = 0.4

using the two equations separately so that
we can compare the results

Reference [03GAS]

19
Pl. Use the following 2 Eqs.

Use n =4
in both
cases so
that we
can
compare
the
results of
both eqs

20
 Trapezoidal Rule
One method of Graphical Integration

21
 Calculatea(Fe)atX(Fe)=0.4

X(Cu) a(Cu) X(Fe) X(Cu)/X(Fe) Loga(Cu) NegativeLogaB (Cu) Log(Cu) NegativeLogB

1 1 0 0.000 0 1 0 0

0.9 0.935 0.1 9.00 -0.029 0.029 1.038889 0.02 -0.02

0.8 0.895 0.2 4.00 -0.048 0.048 1.11875 0.05 -0.05

0.7 0.865 0.3 2.33 -0.063 0.063 1.235714 0.09 -0.09

0.6 0.85 0.4 1.50 -0.071 0.071 1.416667 0.15 -0.15

0.5 0.83 0.5 1.00 -0.081 0.081 1.66 0.22 -0.22

0.4 0.81 0.6 0.67 -0.092 0.092 2.025 0.31 -0.31

0.3 0.78 0.7 0.43 -0.108 0.108 2.6 0.41 -0.41

0.2 0.72 0.8 0.25 -0.143 0.143 3.6 0.56 -0.56

0.1 0.575 0.9 0.11 -0.240 0.240 5.75 0.76 -0.76

0.05 0.4 0.95 0.05 -0.398 0.398 8 0.90 -0.90

0 0 1 0.00

9.00 0.03 9.00 -0.02

4.00 0.05 4.00 -0.05

2.33 0.06 2.33 -0.09

1.50 0.07 1.50 -0.15

1.00 0.08 1.00 -0.22

0.67 0.09 0.67 -0.31

0.43 0.11 0.43 -0.41

0.25 0.14 0.25 -0.56

0.11 0.24 0.11

22 -0.76
 Class Assignment # 3
Please solve problems of Upadhyaya Chapter 4
with a physical understanding of each problem
and hand over before the first lecture of the 5 th
week of classes i.e., before 27-02-2013

23