Heat Capacity, Enthalpy, Entropy 187

6.11  QUANTITATIVE EXAMPLE PROBLEMS

Quantitative Problem 1 
A mixture of Fe2 O3  and Al, present in the molar ratio 1/2, is placed in an adiabatic
container at 298 K, and the Thermit reaction

2 Al + Fe 2O3 → 2Fe + Al 2O3

is allowed to proceed to completion. Calculate the state and the temperature of the
reaction products.

Solution to Quantitative Problem 1 

From the thermochemical data

H Al2 O3 ,298 = −1, 675, 700 J mole

and

H Fe2 O3 ,298 = −823, 400 J mole

the heat released by the Thermit reaction at 298 K is calculated as

∆H 298 = −1, 675, 700 + 823, 400 = −852, 300 J

and this heat raises the temperature of the reaction products. Assume, first, that the
sensible heat raises the temperature of the products to the melting temperature of Fe,
1809 K, in which state the reactants occur as 2 moles of liquid Fe and 1 mole of solid
Al2 O3 . The molar heat capacities and molar heats of transformation are
−3 5 −2
• c p, Al2O3 ( s ) = 117.49 + 10.38 × 10 T − 37.11 × 10 T in the range 298 − 2325 K
−3 −0.5
• c p, Fe(α ) = 37.12 + 6.17 × 10 T − 56.92T J/K in the range 298 − 1187 K
−3
• c p,Fe ( γ ) = 24.48 + 8.45 × 10 T in the range 1187 − 1664 K
−3 −0.5
• c p, Fe(δ) = 37.12 + 6.17 × 10 T − 56.92T J/K in the range 1667 − 1809 K

• For Fe(α ) → Fe( γ ) , ∆H trans = 670 J at 1187 K

• For Fe( γ ) → Fe(δ) , ∆H trans = 840 J at 1664 K

• For Fe( δ) → Fe(l ) , ∆H m = 13, 770 J at 1809 K

The heat required to raise the temperature of 1 mole of Al2 O3  from 298 to
1809 K is
188 Introduction to the Thermodynamics of Materials, Sixth Edition

 10.38 
∆H1 = 117.48 × (1809 − 298)  +  × 10 −3 (18092 − 2982 ) 
 2 
 1 1 
+ 37.11 × 105  − 
 1809 298 
= 183, 649 J

and the heat required to raise the temperature of 2 moles of Fe from 298 to 1809 K
and melt the 2 moles at 1809 K is

 2 × 6.17 
∆H 2 = 2 × 37.12 × (1187 − 298)  +  × 10 −3 (11872 − 2982 ) 
 2 
 2 × 56 .92 
+ (11870.5 − 2980.5 )  + (2 × 670)
 0.5 
 2 × 8.45 
+ 2 × 24.28 × (1664 − 1187)  +  × 10 −3 (1664 2 − 11872 ) 
 2 
+ (2 × 840) + [2 × 37.12 × (1809 − 1664)]
 2 × 6.17   2 × 56.92 
+ × 10 −3 (18092 − 16642 )  +  (18090.5 − 16640.5 ) 
 2   0.5 
+ (2 × 13, 770)
= (78, 058 + 1340 + 34, 654 + 1680 + 14, 268 + 27, 540)
= 157, 541 J

The total heat required is thus

∆H1 + ∆H 2 = 183, 649 + 157, 541 = 341,190 J

The remaining available sensible heat is 852,300 –  341,190 = 511,110 J.

Consider that the remaining sensible heat raises the temperature of the system
to the melting temperature of Al2 O3 , 2325 K, and melts the mole of Al2 O3 . The heat
required to increase the temperature of the mole of Al2 O3  is

 10.38 
∆H3 = [117.49 × (2325 − 1809)] +  × 10 −3 (23252 − 18092 ) 
 2 
 1 1 
+ 37.11 × 105  − 
 2325 1809 
= 71, 240 J

and, with c p ,Fe( l )  = 41.84 J/K, the heat required to increase the temperature of the
2 moles of liquid Fe is
Heat Capacity, Enthalpy, Entropy 189

∆H 4 = 2 × 41.84 × ( 2325 − 1809 ) = 43,178 J

The molar latent heat of melting of Al2 O3  at its melting temperature of 2325 K is
107,000 J, and thus, the sensible heat consumed is

71, 240 + 43,178 + 107, 000 = 221, 418 J

which still leaves 511,110 –  221,418 = 289,692 J of sensible heat. Consider that this
is sufficient to raise the temperature of the system to the boiling point of Fe, 3343 K.
The constant-pressure molar heat capacity of liquid Al2 O3  is 184.1 J/K, and thus, the
heat required to increase the temperature of 1 mole of liquid Al2 O3  and 2 moles of
liquid Fe from 2325 to 3343 K is

( 2 × 41.84 + 184.1) × ( 3343 − 2325) = 272, 600 J

which leaves 289,692 –  272,600 = 17,092 J. The molar heat of boiling of Fe at its
boiling temperature of 3343 K is 340,159 J, and thus, the remaining 17,092 J of sen-
sible heat is used to convert

17, 092
= 0.05
340,159

moles of liquid iron to iron vapor. The final state of the system is thus 1 mole of liq-
uid Al2 O3 , 1.95 moles of liquid Fe, and 0.05 moles of iron vapor at 3343 K.
Suppose, now, that it is required that the increase in the temperature of the prod-
ucts of the Thermit reaction be limited to 1809 K to produce liquid Fe at its melting
temperature. This could be achieved by including Fe in the reactants in an amount
sufficient to absorb the excess sensible heat. The sensible heat remaining after the
temperature of the mole of Al2 O3  and the 2 moles of Fe has been increased to 1809 K
has been calculated as 511,110 J, and the heat required to raise the temperature of
2 moles of Fe from 298 to 1809 K and melt the Fe has been calculated as Δ H 2  =
157,541 J. The number of moles of Fe which must be added to the reacting mole of
Fe2 O3  and 2 moles of Al2 O3  is thus

511,110
= 6.49
0.5 × 157, 541

The required final state is thus achieved by starting with Fe, Al, and Fe2 O3  at 298 K,
occurring in the ratio 6.49/2/1. The Thermit reaction is used to weld steel in locations
which are not amenable to conventional welding equipment.

Quantitative Problem 2
A quantity of supercooled liquid tin is adiabatically contained at 495 K. Calculate
the fraction of the tin which spontaneously freezes, given
190 Introduction to the Thermodynamics of Materials, Sixth Edition

∆H m,(Sn ) = 7070 J at Tm = 505 K

c p,Sn (l ) = 34.7 − 9.2 × 10 −2 T J/K
c p,Sn ( s ) = 18.5 + 26 × 10 −3 T J/K

Solution to Quantitative Problem 2

The equilibrium state of the adiabatically contained system is that in which the solid,
which has formed spontaneously, and the remaining liquid coexist at 505 K. Thus,
the fraction of the liquid which freezes is that which releases just enough heat to
increase the temperature of the system from 495 to 505 K.
Consider 1 mole of tin and let the molar fraction which freezes be x . In Figure  6.16,
the process is represented by a change of state from a  to c , and, as the process is
adiabatic, the enthalpy of the system remains constant; that is,

∆H = H c − H a = 0

Either of two paths can be considered.

Path 1 : a  →  b  →  c , during which the temperature of the 1 mole of liquid is
increased from 495 to 505 K and then x  moles freeze. In this case,

∆H( a →b ) = −∆H( b →c )
505
9.2
∆H( a →b ) =
∫
495
c p,Sn(l )dT = 34.7 × (505 − 495) −
2
× 10 −3 (5052 − 4952 )

= 301 J
∆H( b →c ) = −7070 x J

505 K
b c

a d
495 K

1 mole of liquid X mole of solid

(1 – X) moles of liquid

Figure 6.16  Changes in the state of Sn, considered in Quantitative Example 2.

Heat Capacity, Enthalpy, Entropy 191

and thus,

301
x= = 0.0426
7070
That is, 4.26 mol% of the tin freezes.
Path 2 : a  → d  → c ; that is, the fraction x  freezes at 495 K, and then, the tempera-
ture of the solid and the remaining liquid is increased from 495 to 505 K. In this case,

∆H( a → d ) = −∆H( d →c )
n at 495 K
∆H( a → d ) = the head of freezing x moles of tin
= −x ∆H m (495 K )

But,
495
∆H m (495K ) = ∆H m (505 K ) +
∫505
∆c p( s →l )dT

35.2
= 7070 + 16.2(495 − 505) − × 10 −3 (4952 − 5052 )
2
= 7084 J

Thus,

∆H( a → d ) = −7084 x J
505 505
∆H( d →c ) = − x
∫
495
c p( s )dT + (1 − x )
∫495
c p(l )dT

 26 
= x 18.5(505 − 495) + × 10 −3 (5052 − 4952 ) 
 2 
 9.2 
+ (1 − x ) 34.7(505 − 495) − × 10 −3 (5052 − 4952 ) 
 2 
= 301 + 14x

Thus,

−7084x = −14x − 301

which gives

301
x= = 0.0426
7070

The actual path the process follows is intermediate between paths 1 and 2; that is, the
process of freezing and increase in temperature occur simultaneously.
192 Introduction to the Thermodynamics of Materials, Sixth Edition

The entropy produced by the spontaneous freezing is

 505  −3
∆S( a →b ) + ∆S( b →c ) = 34.7 × ln   − [9.2 × 10 (505 − 495)]
 495 
 7070 
−  0.0426 ×
 505 
= 0.602 − 0.596 = 0.006 J K ⋅ mole

Quantitative Problem 3
The adiabatic flame temperature is that temperature reached when all of the sensible
heat released by the combustion of a fuel is used to raise the temperature of the
gaseous products of combustion. Consider the adiabatic flame temperature reached
when acetylene, C2 H2 , is combusted at 298 K with (1) the stoichiometric amount of
oxygen and (2) the number of moles of air containing the stoichiometric number of
moles of oxygen. Air is, by mole or volume percent, 21% O2  and 79% N2 .
The combustion reaction with stoichiometric oxygen is

C2H 2 + 2.5 O2 = 2 CO2 + H 2O (i)

For C2 H2 : Δ H 298  = +226,700 J

For CO2 : Δ H 298  = – 393,500 J
For H2 O: Δ H 298  = – 241,800 J

Solution  to Quantitative Problem 3 

Thus, for the reaction given by Equation  (i):

∆H ( i )298 = ( −2 × 393, 500) − 241, 800 − 226, 700 = −1, 255, 500 J

The constant-pressure molar heat capacities of the products of reaction are

For H 2O: c p , H 2O = 30.00 + 10.71 × 10 −3 T + 0.33 × 105 T 2 J/K ⋅ mole

For CO2 : c p , CO2 = 44.14 + 9.04 × 10 −3 T − 8.54 × 105 T 2 J/K ⋅ mole

The adiabatic flame temperature, T , is then obtained from the requirement
T
∆H (i)298 +
∫
298
(2c p , CO2 + c p , H 2O)dT = 0

or

−1, 255, 500 + 118.28 × (T − 298) + 14.40 × 10 −3 × (T 2 − 2982 )

+ 16.75 × 105 (1 T − 1 298) = 0
Heat Capacity, Enthalpy, Entropy 193

which has the solution T  = 6,236 K.

For combustion with the stoichiometric amount of air, the reaction is written as

C2 H2  + 2.5 O2  + 2.5 × (79/21) N2  = 2CO2  + H2 O + 9.41 N2 

For N 2 : c p , N 2 = 27.87 + 4.27 × 10 −3 T J/mole ⋅ K

and the adiabatic flame temperature, T , is obtained from

T
∆H (i)298 +
∫
298
(2c p , CO2 + c p , H 2O + 9.41c p , N 2 )dT = 0

or

−1, 255, 500 + 380.1 × (T − 298) + 40.16 × 10 −3 × (T 2 − 2982 )

+ 16.75 × 105 (1 T − 1 298) = 0
as T  = 2,797 K.
This high adiabatic flame temperature facilitates the use of acetylene for welding
metals with high melting temperatures.

PROBLEMS *

6.1 Calculate Δ H 1600  and Δ S 1600  for the reaction Zr(β ) + O2  = ZrO2 (β ).
6.2 Which of the following two reactions is the more exothermic?
a. C( graphite ) + 1/ 2 O2( g ) → CO( g ) at 1000 K
b. C( diamond ) + 1/ 2 O2( g ) → CO( g ) at 1000 K
6.3 Calculate the change in enthalpy and the change in entropy at 1000 K for the
reaction CaO( s )  + TiO2( s )  →  CaTiO3( s ) .
6.4 Copper exists in the state T  = 298 K, P  = 1 atm. Calculate the temperature to
which the copper must be raised at 1 atm pressure to cause the same increase
in molar enthalpy as is caused by increasing its pressure to 1000 atm at 298 K.
The molar volume of Cu at 298 K is 7.09 cm3 , and the volumetric coefficient
of thermal expansion is 0.501 ×  10 – 4  K– 1 . These values can be taken as being
independent of pressure in the range 1– 1000 atm.
6.5 Calculate Δ H 298  and Δ S 298  for the following reactions:
a. 2 TiO + 1/ 2 O2 = Ti 2 O3
b. 3 Ti 2 O3 + 1/ 2 O2 = 2Ti3O5
c. Ti3O5 + 1/ 2 O2 = 3TiO2
6.6 An adiabatic vessel contains 1000 g of liquid aluminum at 700° C. Calculate the
mass of Cr2 O3  at room temperature, which, when added to the liquid aluminum
(with which it reacts to form Cr and Al3 O3 ), raises the temperature of the result-
ing mixture of Al2 O3 , Cr2 O3 , and Cr to 1600 K.

* Thermodynamic data required for the solution of the end-of-chapter problems are tabulated in the
appendices of the text.