Ministry of high education& scientific Research ‫وزارة التعليم العالي و البحث العلمي‬

University of Technology
‫الجامعت التكنولوجيت‬
Materials engineering department
‫قسم هندست المواد‬

Class: Second Year Final Examination

Subject: Chemical Metallurgy (2011-2012) Date: 27/05/2012
Examiner: Dr. Mohammed Abdul Hussein Allowed time: 3 hrs

Note: Attempt only Five Questions.

Q1/ (A) Determine two parameters used to predict spontaneity of the process, then determine when each
one from them is useful in dealing with different conditions of the process. State their
relationship with enthalpy change.
(B) Is the reaction spontaneous under standard conditions?

4KClO3 (s) 3KClO4 (s) + KCl (s)

i ∆Hf  (kJ/mol) So
KClO3 -397.7 143.1
KClO4 -432.8 151.0
KCl -436.7 82.6
(20 Marks)

Q2/ (A) Explain in details the Reversible and Irreversible processes, give an example.
(B) Water at 33  C is pumped from storage tank at the rate of 0.1 m3 /sec. The motor for the pump
supplied work at the rate of 60 KJ/Kg. The water passes through heat exchanger of 1000 KJ/Kg,
and is delivered to elevation of 10 m above the first tank at the velocity 5 m/sec. What is the
3
temperature of the water delivered to this elevation? (0.94 Btu = 10 J). Density of water=1000
Kg/m3 . Sketch Flow Diagram.
 
Enthalpy, Btu/kg Temperature C Enthalpy, Btu/kg Temperature C
160 50 201 90
179 70 226 110
(20 Marks)

Q3 / (A) For closed system adiabatic processes for an ideal gas, by beginning from the differential first
law of Thermodynamic prove that:

 1
T2  P2  
 
T1  P1 
(B) One Kilogram of air is heated reversibly at constant pressure from an initial state of 300 K and
1 bar until its volume triple. Calculate Q, W, ∆U and ∆H for the process. Assume that air
obeys the relation PV/T=83.14 bar cm 3 mol 1 K 1 , Cp=29 J mol 1 K 1 , and Molecular
Weight of air=29 Kg/Kmol.

(20 Marks)
Q4/ For the following Figure, calculate for each process ∆U, ∆H, Q & W.
1
Given that: T1 =T2 =1600 K
P1 = 10 bar, P2 = 3 bar, P3 = 2 bar
Cp=3.5R, Cv=2.5R
R=8.418 J/mol. K

Pressure
2
4 3
3
Volume
(20 Marks)
Q5/ Sulfur dioxide gas is oxidized in 90 percent excess air with 80 % conversion to Sulfur
trioxide. The gases enter the reactor at 410 o C and leave at 460 oC. How much heat must be
transfer from the reactor on the basis 1 mole of entering gas?

SO2 + O2 SO3
Given data; Standard heat of formation at 25  C, and Constants.

i ∆H298  J/mole A 10 3 B 106 C 10-5 D

SO 2 -296830 5.699 0.801 --- -1.015
O2 ---- 3.639 0.506 ---- -0.227
SO 3 -395720 8.060 1.056 ---- -2.028
N2 ----- 3.280 0.593 ---- 0.040

(20 Marks)

Q6/ (A) One mole of an ideal gas, Cp= (7/2)R, Cv=(5/2)R, is compressed adiabatically in a
piston/cylinder device from 1 bar and 40  C to 5 bar. The process is irreversible and requires
35 percent more work than a reversible adiabatic compression from the initial state to the
same final pressure. What is the final temperature and entropy change of the gas?
(B) For an ideal gas with constant heat capacities show that:
For a pressure change from P 1 to P2, the sign of ∆S of an isothermal change is opposite that for
a constant volume change.
(20 Marks)

Good Luck
 Question Solutions of the Final Examination (2011-2012)-Chemical Metallurgy
University of Technology,Materials engineering department

Dr. Mohammed Abdul Hussein

Q1/ (A)

The major parameters to predict spontaneity of the process are Entropy

change (∆S) and Free Energy (∆G), the first one is useful in dealing with different
conditions of the process, but usually the second (∆G) be more useful for certain
conditions of temperature and pressure.

Note that ΔG is composite of both ΔH and ΔS: ΔG = ΔH -TΔS

If ΔH < 0 and ΔS > 0….spontaneous at all T
•A reaction is spontaneous if ΔG < 0. Such that:
If ΔH > 0 and ΔS < 0….not spontaneous at any T
If ΔH < 0 and ΔS < 0….spontaneous at low T
If ΔH > 0 and ΔS > 0….spontaneous at high T
Q1/ (B)
ΔH°rxn = ∑ᵧi ΔHi
= 3(−432.8kJ) + (−436.7kJ) − 4(−397.7kJ)
= −144kJ
ΔS°rxn = ∑ᵧi So i
= 3(151.0J/K) + (82.6 J/K) − 4(143.1J/K)
= −36.8J/K
ΔG°rxn = ΔH°rxn − TΔS°rxn
= −144kJ − (298K)(−36.8J/K)(1kJ/1000J)= −133kJ
ΔG°rxn < 0; therefore, reaction is spontaneous under standard conditions.
Q2/ (A)
A process is reversible when its direction can be reversed at any point by an
infinite change in external conditions. Once the process is initiated, no infinite change
in external conditions can reverse its direction; the process is irreversible. The
apparatus is shown in figure (a gas in piston/cylinder). Expansion processes result
when mass is removed from the piston (we assume the piston without friction), then
the piston will rise and new balance of the piston level will be achieved. The
oscillation of the peiton level due to that mass m is suddenly removed to a shelf. If we
change the mass by powder the piston gradually rise and the other hand will return to
initial level in the same path.

Figure : Gas Expasion ∆l

 Question Solutions of the Final Examination (2011-2012)-Chemical Metallurgy
University of Technology,Materials engineering department

Dr. Mohammed Abdul Hussein

Q2/ (B)

∆H + ∆Ep + ∆Ek = Q – Ws

Mass flow rate= Density x Volumetric flow rate= 0.1 m3 /sec X 1000 Kg/m3 =100
Kg/sec.
∆Ep= m ∆Z g= 100 Kg/sec x 10 m x 9.81 m/s 2 = 9810 kJ/sec.
∆Ek =m x ∆u2 /2= 100 Kg/sec (52 -0)/2= 1250 kJ/sec. (u1 could be neglected; tank).
Q = 1000 kJ/Kg x 100 Kg/sec = 100000 kJ/sec. (positive sign assume heat absorbed
by the system).
Ws = 60 kJ/Kg x 100 Kg/sec = 6000 kJ/sec.
Then ∆H= Q – Ws – ∆Ep – ∆Ek = = 100000 kJ/sec – 6000 kJ/sec – 9810 kJ/sec – 1250
kJ/sec = 82940 kJ/sec. = H2 – H1
By extrapolation method H1 (at 33  C) = 144 Btu/Kg x (1 kJ/0.94 Btu) x 100 Kg/sec=
15300 kJ/sec.
Then H2 = ∆H + H1 = 82940 kJ/sec. + 15300 kJ/sec. = 98240 kJ/sec.

H2 = 98240 kJ/sec. x (0.94 Btu/ 1 kJ) / 100 Kg/sec = 171.5 Btu/kg.

By extrapolation method T2 (have H=923.5 Btu/kg ) = 66.8  C.

Q3/ (A)

First law of thermodynamic, ∆U = Q – W (Adaibatic Q =0)

Cv dT = – P dV, P=RT/V
Then Cv dT = – RT(dV/V)
dT/T= – R/Cv (dV/V)
R/Cv = (Cp – Cv)/ Cv = Cp/ Cv – 1 =ᵞ – 1

dT/T = – (ᵞ – 1) dV/V (Integration)

ln(T2 /T1 )=ln(V2 /V1 )-(ᵞ-1)

 (  1)
T2  V2 
 
T1  V1 
P1 V1 /T1 = P2 V2 /T2, then V2 /V1 = (T2 /T1 )(P1 /P2 ) substitute in the last equation
Then:
 1
T2  P2  
 
T1  P1 
 Question Solutions of the Final Examination (2011-2012)-Chemical Metallurgy
University of Technology,Materials engineering department

Dr. Mohammed Abdul Hussein

Q3/ (B)

No. of moles = 1/29 Kg/Kmol =0.0 34 mole

P1 V1 /T1 = P2 V2 /T2 = 83.14 bar cm 3 mol 1 K 1 , constant pressure P1= P2
V1 /T1 = V2 /T2 , and V1 /T1 = 3V1 /T2 , T2 =3T1 =3 x 300= 900
V1 = 300 X 83.14 bar cm 3 mol 1 K 1 = 24942 cm 3 mol 1 and V1 = 848 cm 3
V2 = 3V1 = 2544 cm 3
At constant pressure Q = ∆H=nCp (T2 – T1 )= 0.034 x 29 (900-300) = 600 J
W=P∆V=1 X 105 (2544 cm 3 - 848 cm 3 ) = 1696 x 105 N/m2 . cm3 =169.6 J
∆U = Q – W = 600 J – 169.6 J = 430.4 J.

Q4/
1 2
T1 = T2 (Isothermal process), ∆H=0, ∆U=0

P   10 
Q=W= RT ln  1  =8.314 x 1600 ln   = 16015 J.
 P2  3
2 3
Constant Volume (W=0)

P2 P3
 , constant volume. T3 = 1600 x 2/3= 1066.6 K
T2 T3

∆H= Cp (T3 – T2 )= 3.5x8.314(1066.6 – 1600)= – 15519.4 J

∆U= Cv (T3 – T2 )= 2.5x8.314(1066.6 – 1600)= – 11085.3 J
Q = ∆U = –11085.3 J
4 1
Adiabatic Process (Q=0), and P4 =P3 = 3 bar

 1  1
T1  P1  
1600  10  
   
T4  P4  ,
T4 3
, and  =1.4

Then
T4 = 1134.3 K
∆H= Cp (T1 – T4 )= 3.5x8.314(1600 – 1134.3)= 13551.4 J
∆U= Cv (T1 – T4 )= 2.5x8.314(1600 – 1134.3)= 9679.6 J
W= - ∆U= – 9679.6 J

3 4
Constant pressure (Isoparic), Q= ∆H
∆H= Cp (T4 – T3 )= 3.5x8.314(1134.3 – 1066.6)= 1970.0 J
∆U= Cv (T4 – T3 )= 2.5x8.314(1134.3 – 1066.6)= 1407.1 J
W = Q – ∆U = 1970.0 – 1407.1= 562.8 J
 Question Solutions of the Final Examination (2011-2012)-Chemical Metallurgy
University of Technology,Materials engineering department

Dr. Mohammed Abdul Hussein

Q5/
Basis: 1 mole of SO 2 entering., T1 =410+273.15= 683.15 K, T2 = 460+273.15= 733.15 K.
O 2 required (computed on base completely conversion)
According reaction equation ( 1 mole SO2 Vs 0.5 mole O2 required)
Excess O 2 = 0.5 x 0.9= 0.45 mole
Total O 2 entering = 0.5 + 0.45= 0.95 mole.
Tout=460 oC
 79  Q=∆H
N 2 entering= 0.95 x   = 3.57 mole. Tin=410 oC SO2 0.2 mol
 21 
Leaving the reactor: SO2 1 mol SO3 0.8 mol
SO2 = 1 x (1 – 80% conversion) = 0.2 mole
O2 reacted = 1 x 80% x 0.5= 0.4 mole. O2 0.95 mol ∆HP O2 0.55 mol
∆HR
O2 output = input-reacted = 0.95 – 0.4 = 0.55 mole.
SO3 produced = No. of mole SO2 reacted = 0.8 mole. N2 3.57 mol N2 3.57 mol

∆H=∆HR + ∆H298 + ∆HP ∆H298

∆H298 = ∑ᵧi ΔHi= - 395720 + (- 1) (- 296830)=- 98890 J

Tam=(T1+T2)/2=708.15 K.

∆HR= ∑niCpm,hi(298.15 – Tin)

∆HP= ∑niCpm,hi(Tout–- 298.15)

∑niCpm,hi=R(∑niAi + (∑niBi)Tam +
n D
i i
)
T1T2

∑niAi= 1 x 5.699 + 0.95 x 3.639 + 3.57 x 3.280= 20.86

∑niBi= 3.4, ∑niDi= - 1.088

1.088
∑niCpm,hi= 8.314(20.86+3.4 x 708.15 + )= 173.5
683x733

The:

∆HR= ∑niCpm,hi(298.15 – 683)= – 66771.5 J

And the same way ∆HP= 78665.3 J

Finally

∆H=– 66771.5 J + (– 98890 J) + 78665.3 J

= – 86996.2 J
 Question Solutions of the Final Examination (2011-2012)-Chemical Metallurgy
University of Technology,Materials engineering department

Dr. Mohammed Abdul Hussein

Q6/ (A) Compressed adiabatically, Q=0

∆U = – W
The first step we find reversible and adiabatic work (i.e ∆S=0)
T  P 
∆S=0=Cp ln  2  – R ln  2 
 T1   P1 
 T2  4
7/2Rln   =Rln   , T2 = 465.3 K
 313.15  1
W=– ∆U= Cv(T2 – T1 )= 5/2R(465.3-313.15)=
Wre v.= 3163.2 J
Wirre v=1.3 x Wrev (More 30 %).= 4112.2 J
= Cv(T2 irrv. –T1 )=5/2R(T2 irrv– 313.15), T2 irrv.= 511 K

 511  4
∆S=7/2R ln   – R ln  
 313.15  1
= 2.7 J/K > 0 spontaneous process.
Q6/ (B)
T  P 
∆S=Cp ln  2  – R ln  2  ,
 T1   P1 
1. Isothermal process T2 =T1
P 
Then (∆S)iso = – R ln  2 
 P1 
2. Constant volume
P1 P2 T P
 , and 2  2
T1 T2 T1 P1
P  P 
And ∆S=Cp ln  2  – R ln  2 
 P1   P1 
P  P 
= (Cp -R)ln  2  = +Cv ln  2 
 P1   P1 
Therefore (∆S)T opposite sign of (∆S)V