Metallurgical Thermodynamics and

Kinetics (MMC301)

Dr. Manas Kumar Mondal

Associate Professor
Department of Metallurgical and Materials Engineering
National Institute of Technology, Durgapur
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FIRST LAW OF THERMODYNAMICS

Lecture 5
References:
1. Stoichometry and thermodynamics of Metallurgical processes - Y K Rao.
2. Introduction to Metallurgical Thermodynamics – David R Gaskell.
5. Metallurgical Thermochemistry – O. Kubaschewski, E LL Evans and C B Alcock
3. Textbook of Materials and Metallurgical Thermodynamics – Ahindra Ghosh
4. Problems in Metallurgical Thermodynamics and Kinetics – G S Upadhyay and R K Dube.
5. Chemical Kinetics - Keith Laidler.
CALCULATION OF ENTHALPY CHANGES
The enthalpy change associated with change in temperature of a substances can be calculated from the heat capacity data a
follows.
At constant pressure dH = CP dT On integration H = ∫ 𝐶 𝑑𝑇

On the substitution for CP, H = ∫ (𝑎 + 𝑏𝑇 + 𝐶𝑇 )𝑑𝑇 → ∆𝐻 = 𝑎 𝑇2 − 𝑇1 + 𝑇 −𝑇 −𝑐 −

HEAT FORMATION OF SUBSTANCES:

It is impossible to measure the absolute value of a thermodynamic property such as the enthalpy of a substance. In practice
this difficulty is overcome by choosing a reference a standard state and measuring the enthalpy relative to the enthalpy of the
standard state. The heat or the enthalpy of formation of an element or compound will depend on the standard state chosen. For
convenience, the following standard states are defined.
Solids: For solid element or compounds, pure substance at 1 atm pressure and specified temperature is the standard state.
Liquids: For liquid elements or compound, pure liquid at 1 atm pressure and specified temperature is the standard state.

Gases: For gases elements and compounds, pure, ideally behaving gas at 1 atm pressure and specified temperature is the
standard state.

The standard state chosen depends primarily on temperature

The titanium metal has two allotropes: Ti () and Ti ().

Ti () Ti (), absorbs 3350 J

Hess’s law and heat of reaction:
The amount of heat absorbed or liberated during a chemical reaction depends on the conditions under which the reaction is
taking place and also an the quantities of substances partaking in the reaction.
1
2CuFeS 2  6 O2  2CuO  Fe2O3  4 SO2
2
The quantity of heat liberated when 2 moles of chalcopyrite combine with 13/2 moles of oxygen to yield 2 moles cupric
oxide, 1 mole of ferric oxide and 4 moles of sulfur dioxide at constant temperature and pressure is known as the heat of
reaction at constant pressure or simply the heat of reaction.
The enthalpy is a state property. It depends an only the initial and final states.
According to Hess's law, the enthalpy change associated with a given chemical reaction is the same either it takes place in
one or several stages.
The reaction between methane and oxygen to produce carbon dioxide and water vapour can proceed by two distinctly
different paths. Direct oxidation or three stage process:
CH4 + 2O2 = 2CO2 + 2H2O, H1
Indirect oxidation or three stage process
CH4 = C + 2H2, H2
C + O2 = CO2, H3
2H2 + O2 = 2H2O, H4

Involving Hess’s law, we find that H1 = H2 + H3 + H4

Variation of heat of reaction with temperature: Kirchhoff’s law
The heat of reaction varies with temperature. Kirchhoff’s law gives the temperature
dependence of the heat of reaction in quantitative terms.
aA + bB + cC + …………. = lL + mM + nN +……… (endothermic reaction) ….(1)

The standard heat of reaction is ∆𝐻 . ∆𝐻 =?

Enthalpy is a state property. So, there will be no change in the enthalpy of the system in
a cyclic process.
Consider the cycle IJY X I in Figure 10
 H 298
0
 H Y  H J  H T01  H I  H X  0........(2)
T1 T1
For the reactants H Y  H J   aC
298
PA  bC PB  ...dT .......(3) For the products  H I  H X   lC PL  mCPM  .....dT .......( 4)
298

Substitution and rearrangement of items yields

T1 T1

 H   aC  bC PB  ...dT  H   lC  mC PM  ...dT  0

0 0
298 PA T PL
298 298

T1

H  H   lC  mC PM  ...  aC PA  bC PB  ...dT ......( 5)

0 0
T1 298 PL
298

Differential form of Kirchhoff’s law 𝑑∆𝐻 𝑑𝑇 𝑃 = ∆𝐶 …… (6) CP   CP , products   CP ,reac tan ts
Problem
Find the H0 at 1200 K for the following reaction
Fe2O3 (S) + 3 CO (g) = 2 Fe(s) + 3CO2 (g)
Following data are given
Transformation Transformation Heat of transformation (J)
temperature (K)

(Fe2O3) (Fe2O3) 953 670

(Fe2O3) (Fe2O3) 1053 -

(Fe) (Fe) 1033 5105
(Fe) (Fe) 1187 670
Heat of formation and heat capacities
∆𝑯𝟎𝒇 𝒂𝒕 𝟐𝟗𝟖K (kJ) 𝑪𝑷 (J/mole.K)
Fe2O3 ()  821.3  = 98.28 + (77.28 × 103T)  14.85 × 105 𝑇2
 = 150.62
 = 132.63 + (7.36 × 103T)
Fe () 0.0  = 17.49 + (24.77 × 103T)
 = 37.66
 = 7.70 + (19.5 × 103T)
CO (g) 110.5 28.41 + (4.10 × 103T)  0.46 × 105 𝑇2
CO2 (g) 393.5 44.14 + (9.04 × 103T)  8.54 × 105 𝑇2
Solution: The heat of reaction at 298K for the reaction Fe2O3 (S) + 3 CO (g) = 2 Fe(s) + 3CO2 (g)
H 298
0
 2  0  3   393.3   821.3  3   110.5  27.7 KJ  27700 J

Fe2O3  ,298  3Co g ,298  2 Fe ,298  3Co2 g ,298 : H1

Fe 2 O3  ,298  Fe2 O3  ,953 : H 2 Fe2 O3  ,953  Fe2 O3  ,953 : H 3 Fe2 O3  ,953  Fe2 O3  ,1053 : H 4

Fe2 O3  ,1053  Fe2 O3  ,1053 : H 5 Fe2 O3  ,1053  Fe2 O3  ,1200  : H 6 2 Fe ,298  2 Fe ,1033 : H 7

2 Fe ,1033  2 Fe ,1033 : H 8 2 Fe ,1033  2 Fe ,1187 : H 9 2 Fe ,1187   2 Fe ,1187  : H 10

2 Fe ,1187  2 Fe ,1200 : H 11 3Co g ,298  3Co g ,1200 : H 12 3Co 2  g ,298  3Co 2  g ,1200 : H 13

For the reaction at 1200K, Fe2 O3  ,1200  3Cog ,1200  2 Fe ,1200  3Co 2  g ,1200

The heat of reaction 𝐻 is given by H 1200  H 1  H 2  ...  H 6   H 7  ...  H 11   H 12  H 13

0

H 1  H 298
0
 27700 J

 98.28  77.28  10 T   14.85  10 T dT  92831J

953 953

C 
3 2
H 2  P  Fe2 O3 dT  5

298 298

H 3  670 J  H 4  15062 J H 5  0 H 6  20716 J H 7  49942 J H 8  10210 J H 9  11600 J

H 10  1340 J H 11  1340 J H 12  84,840 J H 13  131300 J

Substitutions gives
 H 1200
0
  27700  129274  73898  84840  131300   36621 J
REVERSIBLE ADIABATIC PROCESS
For an infinitesimal reversible process undergone by an ideal gas, the first law is Q = dE + P dV
and heat capacity at constant volume is given by: 𝐶 = (𝜕𝐸/𝜕𝑇) … … … . (1)

For the ideal gas, E is a function of T only. Therefore, the partial deviation of E with respect to T can be replaced by the
total deviation . 𝐶 = 𝑉= → 𝑑𝐸 = 𝐶 dT for ideal gas

On combining this result with the first law, we have Q  CV dT  PdV

In an adiabatic process, Q = 0 and P dV =  CV dT ……………. (2)

Furthermore, for 1 mole of substance: PV = RT  P = RT/V

Substitute into equation (2) gives RT  dV 

dV  CV dT  RT    CV dT
V  V 
 dV  dT
 R   CV .
V  T
 R.d ln V  CV .d ln T
R

 d ln V CV
 d ln T
R

 d ln V CV
 d ln T  0
 CR 
 d lnV V .T   0
 
 
On integration: 𝑉 𝑅 𝐶 𝑇 = 𝑘 … … . . (3)
R CP R
 1     1.......(4) as CP –CV = R
CV CV CV
R

Combining equation (3) and equation (4) V CV

.T  K  TV  1  k ...........(5)
Equation (5) gives the relationship between temperature and volume for adiabatic process.
A pressure-volume relationship can be deduced as follows.
T= , 𝑇𝑉 ( ) = 𝑉( )= = 𝑘 → 𝑃𝑉 = C

WORK DONE IN AN ADIABATIC PROCESS FOR AN IDEAL GAS:

For an infinitesimal change, work done is given by W = P dV

Eliminating P in favour of V, we can write 𝛿𝑊 = 𝐶 … … … … 6 [𝑎𝑠 𝑃𝑉 = C]

Let us suppose, that the initial and final states of the system are (P1, V1, T1) and (P2, V2, T2) respectively. An integrating
equation (6).
𝑊 = 𝐶⁄ 1 − 𝛾 𝑉 −𝑉 … … . . (7)
𝐴𝑔𝑎𝑖𝑛, 𝐶 = 𝑃2𝑉2 = P1𝑉 =P𝑉 … … … … … … … … . (8)

On combining equation (7) and (8) we obtain W = (P1V1 – P2V2)/( - 1) …………. (9)

For a ideal gas P1V1 = RT1 and P2V2 = RT2

𝑇ℎ𝑖𝑠 𝑙𝑒𝑎𝑑𝑠 𝑡𝑜 𝑊 = 𝑅⁄  − 1 𝑇 −𝑇 = 𝐶 (𝑇 − 𝑇 )
 POLYTROPIC PROCESS
Polytropic process as a general process , this process is a thermodynamic process that obey the reaction for polytrophic
process: 𝑃𝑉 = 𝐶, 𝑤ℎ𝑒𝑟𝑒 𝑛 = 𝑝𝑜𝑙𝑦𝑡𝑟𝑜𝑝𝑖𝑐 𝑖𝑛𝑑𝑒𝑥 𝑎𝑛𝑑 𝑛

1. if n = 0 then PV 0  C  P  C  Constant pressure process or isobaric process.

2. if n =1 then PV 1  C  PV  C  Constant temperature process or isothermal process.

3. if n =  then PV  C if multiply both side power 1/

1  1

P V 
C 

 V  CONSTANT  Constant volume process or isochoric process

4. if n =1.4=  𝑡ℎ𝑒𝑛 𝑃𝑉 = 𝐶𝑜𝑛𝑐𝑡𝑎𝑛𝑡  Reversible adiabatic process or Isentropic process.
For an infinitesimal change, work done is given by W = P dV
Eliminating P in favour of V, we can write 𝛿𝑊 = 𝐶 … … … … 1 [𝐹𝑜𝑟 𝑝𝑜𝑙𝑦𝑡𝑟𝑜𝑝𝑖𝑐 𝑝𝑟𝑜𝑐𝑒𝑠𝑠 𝑃𝑉 = C]
Let us suppose, that the initial and final states of the system are (P1, V1, T1) and (P2, V2, T2) respectively. An integrating
equation (1).
𝑊 = 𝐶⁄ 1 − 𝑛 𝑉 −𝑉 … … . . (2)

𝑀𝑜𝑟𝑒𝑜𝑣𝑒𝑟, 𝐶 = 𝑃2𝑉2 = P1𝑉 =P𝑉 … … … … … … … … . (3)

On combining equation (2) and (3) we obtain W = (P1V1 – P2V2)/(n- 1) …………. (4)
 For a ideal gas P1V1 = RT1 and P2V2 = RT2
𝑇ℎ𝑖𝑠 𝑙𝑒𝑎𝑑𝑠 𝑡𝑜 𝑊 = 𝑅⁄ 𝑛 − 1 𝑇 −𝑇

Again change in internal energy E2 – E1 = CV (T2 – T1)

From first law of thermodynamic

P1V1  P2V2 
E 2  E1  Q  W  E 2  E1  Q 
n 1

 CV T2  T1   Q 
P1V1  P2V2 
n 1
We know that CP – CV = R  CP/CV – 1 = R/CV  CV = R/( - 1) [As CP/CV = ]

Heat exchanged R
Q T2  T1   R .T1  T2 
 1 n 1
 1 1 
 Q  R T1  T2   
 n  1   1

Q
R
T1  T2    n   W .   n
n 1   1   1
Problem
Air (ideal gas with  = 1.4 ) at 1 bar and 300K is compressed till the final volume is one-sixteenth of the original volume,
following a polytrophic process PV1.25 = constant.
Calculate (a) The final pressure and temperature of the air, (b) Work done and (c) The energy transferred as heat per mole of air.
Solution:
(a) Initial volume V1, and final volume V2

According to polytropic process P1V11.25 = P2V21.25 = c

1.25
V 
P2  P1  1   1  16   32bar P1V1  P2V2  T  P2V2 .T  32  V1  300  600K
1.25

 V2
2 1
 T1 T2 P1V1 1 16  V1

R 8.314  300  600 

(b) W  .T1  T2    9976.8 J mole  9.977 KJ mole
n 1 1.25  1

 n 1.4  1.25
(c) Q W   9.977   3.741 KJ mole
 1 1.4  1