GROUP(26)

SHEET (6-2)
Thermochemistry

Question No. (1)

Calculate the standard heat of formation at 25 C and 1
atmosphere pressure of the following reaction:
3FeO + 2Al Al2O3 + 3Fe ,

per mole of Al2O3 formed, per mole of Fe formed, per mole of FeO
reacted, per mole of Al reacted and per gram of Fe formed. Given
that: Hf(FeO) at 298K = - 63.3 kcal/mole,
Hf(Al2O3) at 298K= - 400 kcal/mole, and
The atomic weight of Fe = 56

The Answer of Question No.(1)

. H(298k)= HAl2O3 - 3HFeO
= - 400000 3 ( -63300 )
H(298k)= - 210100 cal/mole of Al2O3

.H(298k)= 1/3 HAl2O3 - HFeO

= 1/3 (-400,000) + 633,00
H(298k)= - 70033 cal/mole Fe

.H(298k)= 1/3 HAl2O3 - HFeO

H(298k)= - 70033 cal/mole FeO
. H(298k)= o.5 HAl2O3 1.5HFeO
H(298k)= - 210100/2 = - 105 kcal/mole Al
3

. H(298k)= - 70.033 kcal/mole Fe

= - 70.033 * 56
= - 3921.848 kcal/gm

Question No. (2)

Calculate the standard heat of formation of solid WO 3 from solid
W and O2 gas at 25 C and 1 atmosphere pressure from the
following data at

25 C and 1 atm:

O2

WO2Hf at 298K= - 134

3WO2 +

O2

W3O8Hfat 298K = - 131.5 kcal

W3O8 + 0.5 O2 3WO3Hf at 298K = - 66.5

The Answer of Question No. (2)

W

O2

WO2Equation (A)
4

kcal
kcal

3WO2 + O2

W3O8Equation (B)

W3O8 + 0.5 O23WO3Equation (C)

Sequence of solving equations
3 (A) + (B) + (C)
3 W + 4.5 O2

3 WO3Hf= - 600 kcal

Heat of formation per one mole

W + 1.5 O2

WO3

Hf= - 200 kcal

Question No. (3)

Predict the heat of fusion for LiCl at 883K, given the followings:
Li(l) + 0.5 Cl2(g) LiCl(l)

Hf at 883K = - 92.347

kcal/mole
Li(l) + 0.5 Cl2(g) LiCl(s)

Hfat 883K = - 97.105

kcal/mole

The Answer of Question No. (3)

Li(l) + 0.5 Cl2(g) LiCl(l)

Equation (A)

Li(l) + 0.5 Cl2(g) LiCl(s)

Equation (B)

SEQUANCE OF SOLVING
(A) (B)
LiCl(s)LiCl(l)Hf= 4758 kcal

Question No. (4)

Calculate the standard heat of formation of anhydrous aluminum

chloride from the following data:
2Al(s) +6HCl(aq.) Al2Cl6(aq.)+3H2(g)Hf at 298K = - 240 kcal
H2(g)+ Cl2(g) 2HCl(g)
Hf at 298K = - 44 kcal
HCl(g) + aq.

HCl(aq.)

Hf at 298K= - 17.5 kcal

Al2Cl6 + aq.Al2Cl6(aq.)
Hfat 298K= - 153.7 kcal

The Answer of Question No. (4)

2Al(s) +6HCl(aq.) Al2Cl6(aq.)+3H2(g)Equ.(A)
H2(g)+ Cl2(g) 2HCl(g)Equ.(B)
HCl(g) + aq.HCl(aq.)Equ.(C)
Al2Cl6 + aq.Al2Cl6(aq.)

Equ.(D)

Sequence of solving
(A) + 3 (B) + 6 (C) (D)

2Al + 3Cl2Al2Cl6
Hf= - 240000 + 3(- 44000) + 6 (-17500) +153700

Hf = - 323300 cal

Question No. (5)

The enthalpy changes for the following reactions are as follows:
2B+3H2+ 3O2 + aq. 2H3BO3(aq.) Hfat 298K= - 512.8 kcal
B2O3+3H2O(l) + aq. 2H3BO3(aq.) Hfat
298K = - 4.12

kcal

H2 + 0.5 O2H2O(l)

Hfat 298K= - 68.73 kcal

8

Calculate the standard heat of formation of B2O3 per mole of

B2O3, and per gram of B2O3. The atomic weight of B and O are
11 and 16, respectively.

The Answer of Question No. (5)

2 B2O3+3H2O(l) + aq. 2H3BO3(aq.) x (+1)
B2O3+3H2O(l) + aq. 2H3BO3(aq.) x(-1)
H2 + 0.5 O2H2O(l)

x(3)

2B +1.5 O2B2O3
Hf=512.8+4.12+368.73
=302.49 kcal/mole B2O3
Hf=302490[211+316]
=211744300 cal/gm B2O3

10

Question No. (6)

Calcium carbide is considered to be a potential fuel in the basic
oxygen converters and would be expected to burn into CaO and
CO or CO2, depending upon the conditions. If the heat required
to raise the steel scrap to 1600 C is 333 kcal/Kg of scrap,
calculate how many Kg of steel scrap can be charged per 1000 Kg
of CaC2 when
(a) all CaC2 is consumed to form CO
(b) all CaC2 is consumed to form CO2
(c) 60% of CaC2 is utilized to produce CO2 and the rest produces
CO.
Assuming that the reactions take place at 25 C, given that:
Hf(CaC2) at 298K= - 14.1 kcal/mole
Hf(CaO) at 298K = - 151.8 kcal/mole
Hf(CO) at 298K = - 26.42 kcal/mole
Hf(CO2) at 298K = - 94.05 kcal/mole
The atomic weights of Ca and C are 40 and 12, respectively.

11

The Answer of Question No. (6)

a. CaC2+O2CaO+2CO
Hf at 298K=Hf(CaO)+2Hf(CO)Hf(CaC2)=151.8+226.42+14.1
=190.54 kcal/mole
Hf at 298K=190.5464
=12194.6kcal/1000kg
Hf(steel) at 298K=333kcal/kg
N=12194.6333=36.4 kg of steel
b. CaC2+1.5O2CaO+2CO2
Hf at 298K=Hf(CaO)+2Hf(CO2) Hf(CaC2) =151.8294.0514.1
=325.8kcal/mole
Hf at 298K=325.864
=20851.2kcal/1000kg
N=20851.2333=62.6 kg of steel
c. CaC2+1.4O2CaO+0.8CO2+1.2CO
Hf at 298K=Hf(CaO)+1.2Hf(CO)
+0.8Hf(CO2) Hf
12

(CaC2)=151.8+1.226.42+0.894.5+14.1
=244.644kcal/mole
Hf at 298K=244.64464
=15657.16kcal/1000kg
N=15657.16333=47 kg of steel

13

Question No. (7)

Calculate the heat required to raise the temperature of Pb and O 2
to 227 C from 25 C; you may use the following data:
Hf(PbO) at 298K = - 52.4

kcal/mole

Cp (PbO)= 10.6 + 4.00 x 10-3 T cal/(deg-mole)

Cp (Pb) = 5.63+ 2.33 x 10-3 T cal/(deg-gm atom)
Cp (O2) = 7.16 + 1.00 x 10-3 T 0.4 x 105 T-2cal/(deg-mole)
Also calculate Hf(PbO) at 227 C.

The Answer of Question No. (7)

at T=273+227=500 K
Pb

+ 0.5O2

PbO
500

Hf=Hf at 298K+ Cp( R) dT

298

Cp(R)=Cp (PbO)0.5Cp (O2) Cp (Pb)

=[10.60.57.165.63]+[40.512.33]10-3 T
+[0.40.5105 T-2]
=1.39+1.1710-3 T+0.2105 T-2
14

500

Hf (500K)=52400+ ( 1.39+1.1710-3
298

T+0.2105 T-

)dT

=52400+1.39(500298)+(1.172) 10-3(50022982)0.2105(500-1 298-1)=52123.9 cal

15

Question No. (8)

18 gm ice at 0 C is heated to 100 C until vapor is formed against
an external pressure of 1 atm.
(a) Calculate the thermal energy needed for the process
(b) Calculate the work done by the system on the surroundings
(c) The internal energy change throughout the process.
Given that: Hf(H2O) at 0 C = 1.4 kcal/mole
Hvap(H2O) at 100 C = 9.7 kcal/mole
Cp(H2O)= 18 kcal/(deg-mole)

The Answer of Question No. (8)

H2O(l)H2O(v)
373

HT=H1+ Cp( R)
273

dT+H2

H2O

373

=1400+ 18 dT+9700
273

=1400+18(373273)+9700
a.

HT =12900cal/mole
U=q+w
16

H=U+pv
V1 =R T1P1 =0.082273=22.4 lit
V2 =R T2P2 =0.082373=30.6 lit
W=P(V2V1)=1(30.622.4)=8.2 lit .atm
W=8.2101.325(14.18)=198.78 cal
b. Wsys=198.78 cal
H=U+pv
U=Hpv
U=12900198.8=12701 cal
c. U=12701 cal

Question No. (9)

For the reaction:
CO + H2O CO2 +H2

Hf at 298K= - 10 kcal

Calculate the standard change in enthalpy at 1000K knowing that all chemical
species of the reaction are in their gases form.
17

Data: Cp (CO)g = 6.6+1.0x10-3 T cal/(deg-mole)

Cp (H2)g= 6.6+1.0x10-3 T cal/(deg-mole)
Cp (H2O)g= 7.3+2.0x10-3 T cal/(deg-mole)
Cp(CO2)g=7.3+3.0x10-3T

cal/(deg-mole)

The Answer of Question No.(9)

1000

H(1000k)= H(298k) + Cp dT
298

Cp =Cp(H2)+ Cp(CO2)- Cp(CO)- Cp(H2O)

=(6.6+1.0x10-3 T) +(7.3+3.0x10-3T) - (6.6+1.0x10-3 T)-(7.3+2.0x10-3 T)

Cp = 1x10-3 Tcal/(deg-mole)
H (298) =H(CO2)-H(H2O)-H(CO)
=(-94.05 + 68.73 +26.42)x103 =1100 cal

H(1000k)=1100 +

H(1000k)=1556 cal

1
2

x 10-3 x (10002 -2982)

18

Question No.(10)
Calculate the standard heat of formation of solid PbO from liquid Pb and O 2 gas at 527
C. The melting point of lead is 327 C and its latent heat of fusion is 1.15 kcal/mole.
The molar heat capacities at constant pressure are given below:
Hf (PbO)s at 298K = -52,400 cal/mole
Cp (Pb)l= 7.75 0.74 x 10-3 T cal/(deg-gm atom)
Cp (Pb)s= 5.63+ 2.33 x 10-3 T cal/(deg-gm atom)
Cp (PbO)s= 10.6 + 4.00 x 10-3 T cal/(deg-mole)
Cp (O2)g= 7.16 + 1.00 x 10-3 T 0.4 x 105 T-2cal/(deg-mole)

Pb(l) +

1
2

The Answer of Question No.(10)

O2(g)

PbO

T=527 +273 = 800 K

T(m)=327 +273=600
Hf=1150 cal.mole
19

600

H800= H298 + Cp(s)dT

298

H(800k) =-52400 +

800

Cp(l) dT +Hf
600

Cp ( pbo )

600

-Cp (O2)-Cp (pbs))dT

298

Cp ( pbo )

+1150+ -Cp (O2) -Cp (pbl))dT

800

600

H(800k)= -52400 +(-502.97) +1150 +(522754.67)

=471001.7 cal/mole

Question No. (11)

20

Calculate the heat of reaction of chlorination of zirconium oxide at 25 C and 777 C;

the process occurs according to the following reaction:

ZrO 2 + 2Cl2 + C ZrCl4 +

CO2
Given that: Hf(ZrCl4) at 298K= - 234.7 kcal/mole
Hf(CO2) at 298K = - 94.05 kcal/mole
Hf(ZrO2) at 298K= - 259.5 kcal/mole
Cp (ZrCl4)= 31.92 2.91 x 105 T-2cal/deg-mole
Cp (CO2)= 10.55 + 2.16 x 10-3 T 2.05 x 105 T-2cal/(deg-mole)
Cp (ZrO2)= 16.64 + 1.80 x 10-3 T 3.36 x 105 T-2cal/(deg-mole)
Cp (Cl2)= 8.82 - 0.06 x 10-3 T 0.68 x 105 T-2cal/(deg-mole)
Cp (C)= 4.10 + 1.02 x 10-3 T 2.10 x 105 T-2cal/(deg-mole)

The Answer of Question No.(11)

T=777+273 = 1050 k
H(298k)= H(ZrCl4) + H(CO2) - H(ZrO2)
= - 234.7 +(- 94.05 ) (- 259.5 )
H(298k)= -69.25 kcal/mole
1050

H(1050k)=H(298k)+ Cp dT
298

Cp

= Cp (CO2)+Cp (ZrCl4) - Cp (C)-2Cp (Cl2) -Cp (ZrO2)

21

=(10.55 + 2.16 x 10-3 T 2.05 x105 T-2)+(31.922.91 x

105 T-2 ) (4.10 + 1.02 x 10-3 T 2.10 x 105 T-2 ) 2(8.82
- 0.06 x 10-3 T 0.68 x 105 T-2 ) (16.64 + 1.80 x 10-3 T
3.36 x 105 T-2)
Cp
=4.095.4x10-4 T +1.86x105 T-2cal/(deg-mole)

1050

H(1050k)= -69.25 x 103 + 4.09 5.4x10-4 T

298

+1.86x105 T-2 )

H(1050k)= - 66 kcal/mole

22