Metallurgical Thermodynamics

and Kinetics
(MT21105)
Standard enthalpy change or standard heat of reaction

If a chemical reaction is carried out in which the reactants as well as

the products are in their respective standard states and at the same
temperature T, the enthalpy change associated with the reaction is
called the standard enthalpy change or standard heat of reaction. It is
denoted by

Denotes all the reactants and products are in

their std. state
H T
o

Temperature at which the reaction is carried out

 Standard enthalpy of formation

CO(g)+2H2(g)  CH3OH(g) reaction between two components

C(g)+2H2(g)+½O2(g)CH3OH(g)reaction between the elements

A reaction in which only one mole of a single compound is formed

from its constituent elements is called a formation reaction. The
enthalpy change associated with a formation reaction, when the
reactants and products are in their standard state, is called
standard enthalpy (or heat) of formation.

• By convention the standard enthalpy of formation of an element is

zero.

• The standard enthalpies of formation of compounds are reported

at 298.15 K and they are represented as
H 298
0
H f , 298
0
or H f 0 or
Standard Molar Heats of Formation and
Molar Entropies at 298 K
Molar Heats of Fusion and Transformations
Find a set of formation reactions to calculate the
standard enthalpy change for the reaction

CO(g) + H2O(g)  CO2(g) +H2(g)

Solution:
Chemical compounds are CO, H2O and CO2

C(S) +1/2 O2(g)  CO(g) -------- 1

H2 (g) +1/2 O2 (g)  H2O (g) ----- 2
C(S) +O2(g)  CO2 (g) ------------ 3

3-2-1 gives
CO (g) +H2O (g)  CO2(g) +H2(g)
 Standard enthalpy change of combustion
The formation reaction for C4H10 (g) is
4C(s)+5H2(g)  C4H10 (g)
A combustion reaction is defined as a reaction between an element
or compound and oxygen to form specified products. The
standard enthalpy change associated with a combustion reaction is
called standard enthalpy change or standard heat of
combustion, usually represented by Hc0. Example:
13
C4 H10 ( g )  O2 ( g )  4CO2 ( g )  5H 2O (l )
2
H 0 f ,298 CO2 ( g )   393.978 kJ
H 0 f ,298 H 2O (l )   285.958 kJ
H 0C ,298  4H 0 f ,298 CO2  g   5 H 0 f ,298  H 2O(l )  H 0 f ,298 C4 H10  g 
 2880.44  4 (393.978)  5(285.958)  H f ,298 C4 H10  g 
H 0 f ,298 C4 H10 ( g )   125.262 kJ
Change in enthalpy without any change in state of
aggregation of the substance

 H  T2
Cp    H T2   H T1    C p dT
 T  p T1

(For a closed system of fixed composition undergoing a change

of temperature from T1 to T2)
Calculate the enthalpy change when 1 kg of silver is heated
from 25C to 500C
 
773


2
 
773
a bT CT dT
H (500+273)-H (25+273) = C dT = 
298
p
298

 21.1 8.5510 
773
3 2 1mol 1000 g
= T 1.50 10 T 5
dT J / mol  
298
107 g 1kg
= 116  103 J/kg
 Enthalpy changes due to changes in state of
aggregation of the substance

Example 1
A(solid) A(liquid) A(gas) A(gas)
At 298 K at Tm at Tb at T

Tm Tb T
HT – H298 = C
298
p ( s)dT + Hm + C
Tm
p (l )dT + Hv + C p ( g )dT
Tb

Hm = enthalpy change of one mol of solid due to melting (i.e.,

latent heat of fusion per mol
Hv = enthalpy change of one mol of liquid due to vaporization
(i.e., latent heat of vaporization per mol)
 Calculate the enthalpy change when iron is heated from 25
to 2000 0C

Phase Structure Temperature range (K)

of stability
a Body-centred cubic (BCC) up to 1033
b Nonmagnetic BCC 1033 – 1186

 Face-centred cubic (FCC) 1186 – 1665

d Body-centred cubic 1665 - 1809

1033 1186

H2000 – H298 =  C p (a )dT + Htr (a  b +  C p (b)dT + Htr (b   +

298 1033
 FOR A CLOSED SYSTEM OR FIXED COMPOSITION
UNDERGOING A CHANGE FROM T1 to T2

Consider a reaction, A + B  C +D
T2
H T2   H T1    C p dT
T1

Example: Pb(S) + ½O2 (g) = PbO(s)

T2 = 2000C = 473 K T1 = 250C = 298 K

H (T1) = H (298 K) = 219 kJ. mol1

Cp = Cp, PbO (S)  Cp, Pb (S)  ½ Cp, O2 (g)

Cp, Pb (S) = 23.6 + 9.75 103 T J. K1 mol1, in the range 298-600 K
Cp, PbO (S) = 37.9 + 27  103 J. K1 mol1, in the range 298-1000 K
Cp, O2 (g) = 30 + 4.18  103 T  1.7  105 T2 J. K1 mol1 in the range
298-
3000 K
 In the range 298-600 K

Cp = Cp, PbO (S)  Cp, Pb (S) 1/2 Cp, O2 (g)

=  0.7 + 15.16  103 T + 0.85  105 T 2 JK1

H473 = 21900 +  0.7 15.16 10 3 T  0.85 10 5 T 2 dT

473

 298

=  219000  (0.7) (473  298) +

15.16 10 3
4732  298 2   0.85  10 5 
 1

1 

2  473 298 

= J mol1
 Adiabatic flame temperature

The highest possible temperature of combustion obtained under the

conditions that the burning occurs in an adiabatic vessel, that it is
complete, and that dissociation does not occur.

Example:
Consider a burner in which a fuel gas at 298 K is burned with the
stoichiometric amount of dry air (21 % oxygen and 79% nitrogen),
also at 298 K. The reaction takes place at one atmosphere pressure.
The composition of the fuel gas (by volume)
20 % CO
30 % CO2
50 % N2
Ans. N2 and CO2 do not react. The combustion reaction for the
carbon monoxide is: CO + ½ O2  CO2
Gas Moles in Moles out Exit gas
Composition (%)

CO 0.20 0 36
CO2 0.30 0.50 64
O2 (0.5  0.20) = 0.10 0
N2 [i.e., 0.5 mol per 0.88
mole of O]
0.50 + 79/21  0.10

Because we want to find the highest temperature that can be

reached, we assume that the burner loses no heat to the
surroundings; that is, it is adiabatic (Q = 0). Hence,
Enthalpies of the products leaving the burner = enthalpies of
the reactants
Reactants at 298.15 K
Products at 298.15 K Products at T
0.20 mol CO(g)
0.50 mol CO2(g) 0.50 mol CO2(g)
0.30 mol CO2(g)
Step 1 0.88 mol N2(g) Step 2 0.88 mol N2(g)
0.1 mol O2(g)
0.88 mol N2(g)

H = Q = 0
Actual Process
 T T
0.5 H f ,CO 2,298  0.5 
298
CP , CO 2 dT  0.88H N 2,298  0.88  CP , N 2, dT
298

 0.2 H f , CO , 298  0.3 H f ,CO 2, 298  0.88H N 2,298  0.1H O 2,298

CP , N 2 dT  0.2  H f , CO , 298  H f , CO 2, 298 

T T
0.5  CP , CO 2 dT  0.88 
298 298

CP , N 2  34.3 J /  mol. K 
CP , CO 2  57.3 J /  mol. K 
H f , CO ,298  110,500 J T = 1260 K
H f , CO 2, 298   393,500 J
 Hess’s Law
The overall reaction enthalpy is the sum of the reaction enthalpies
of the individual reactions into which a reaction may be divided.

W(s)+O2 (g) = WO2 (s) ------------- (1) H298= -134 kcal

3 WO2(s) +O2 (g) =W3O8 (s) ------- (2) H298 = -131.5kcal
W3O8 (s) + ½ O2 (g) =3 WO3 (s) ----- (3) H298 = -66.5 kcal

Calculate the heat of formation of solid WO3 from solid W and O2

gas at 25C & 1 atm.

(1)x3 + (2) + (3)

3 W(s) +9/2 O2 (g) =3 WO3 (s)

H298 = ( 3-134)+ (-131.5)+ (-66.5) = -600 kcal

H298 = -200 kCal