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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Introduction

Lecture 3
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.
Problem 1
The molecules of diatomic gases tend to dissociate into atoms and the degree of dissociation increases with rising
temperature. Thus, at any given temperature the gas consists of a mixture of diatomic and monatomic particles. For
simplicity, let us assume that the diatomic and monatomic portions of the gas obey the ideal gas law. However, the
gas mixture will not behave ideally, because the number of moles increases with increasing temperature. For the
purpose of this analysis, let us define the degree of dissociation designated , as the ratio of the mass m1 of the
monatomic portion to the total mass m of the gas mixture. That is,  = m1/m.
Prove that the equation of state of the gas is PV = (1+) (m/M2) RT.
Where M2 is the molecular weight of the diatomic component. Assume that the gas obeys Dalton’s law.
Solution
Let us suppose that the total pressure ,volume and temperature are P, V, and T, respectively. Let n1 and n2 denote
the number of moles of monatomic and diatomic gaseous species, respectively. Let m1 and m2 be their masses and
M1 and M2 be their molecular weight.
Therefore, n1 = m1/M1 and n2 = m2/M2
Let P1 and P2 denote the partial pressures of monatomic and diatomic species, respectively. Because, individual
components obey the ideal-gas law.
P1V = n1RT = (m1/M1) RT ……… (1) and P2V = n2RT = (m2/M2) RT ……… (2)

The total pressure P, according to Dalton’s law, is given by P = P1 + P2

Add equation (1) and (2)
V(P1 + P2) = RT (m1/M1 + m2/M2) PV= RT (m1/M1 + m2/M2) ……… (3)

m is total mass of gas mixture m = m1 + m2

As the molecules of diatomic gases tend to dissociate into atoms, so M2 = 2M1. Substitution yeilds
PV= RT (2m1/M2 + m2/M2) PV= (RT/M2) (m1+m1 + m2) and  = m1/m

PV= (RT/M2) (m + m1) PV= (RT/M2) (m +  m ) PV= (RTm/M2) (1+  )

Problem 2
An iron ore sample contains iron, silicon and oxygen, its analysis shows that the iron present amount to 68% by
weight. Assuming that all the iron is present as Fe2O3 and the silicon as SiO2 (a) calculate the weight percent of
SiO2 in the ore and (b) expressed the composition of the ore an a mole-percent basis. Molecular weight of Fe =
55.845, O =16 and silicon=28.085.
Solution
consider 100 g of iron ore sample of this 68 g is iron and the reminder is silicon and oxygen.
111.69 g Fe is combined with 48 g O2 to from Fe2O3.
68 g Fe is combined with (48/111.69) × 68 = 29.22 g O2 to from Fe2O3.
So mass of oxygen present as Fe2O3 = 29.22 g
 Mass of SiO2 = 100 – 68 – 29.22 = 2.78 g.
weight percent of SiO2 = 2.78%

(b) The molecular weight of Fe2O3 and SiO2 are 159.69 and 60.085

Mass of Fe2O3 = 68 + 29.22 = 97.22 g.

Mass of SiO2 = 2.78 g.

Moles of Fe2O3 = 97.22/159.69 = 0.6088

Moles of SiO2 = 2.78/60.085 = 0.0463

Total mole = 0.6088 + 0.0463 = 0.6551

Mole-percentage of Fe2O3 = 0.6088/0.6551 ×100 = 92.93

Mole-percentage of Fe2O3 = 0.6088/0.6551 ×100 = 92.93%

Mole-percentage of SiO2 = 0.0463/0.6551 ×100 = 7.07%

Problem 3
The moist blast used in an iron blast furnace containing 7.2 grains of water vapour per cubic foot at 77F. Determine the
temperature to which the blast must be preheated in order that its relative saturation will become 0.12. Molecular weight of
hydrogen =1.008, oxygen =16 and R =1545.45 ft.lb/lb.mole.R.
Solution: Basis: 1 ft3 is the moist blast
Mass of water vapour = 7.2 grains = 7.2 × 0.000143 lb = 1.0296 × 103 lb (as 1 grains = 0.000143 lb)
PH2O V = nH2O RT
Where,
V = 1 ft3, PH2O = (nH2O RT)/V
T(R) = t (F) + 459.67 (R) = 77 + 459.67 = 536.67 C = (5.7149 × 105 × 1545.45 × 536.67)/1
Molar pounds of water vapour = 1.0296 × 103 /18.016 = 5.7149 × 105 = 47.4 lb/ft2
nH2O = 5.7149 × 105 pound mole of water vapour = 17 mmHg = 0.67 in.Hg
R =1545.45 ft.lb/lb.mole.R

tF Vapour pressure

Relative saturation =0.12 = at in.Hg
. .
= 0.67/0.12 = 5.5833 in.Hg 110 2.596
120 3.446
130 4.525
From the table temperature corresponding to this vapour pressure 138F.
140 5.881
FIRST LAW OF THERMODYNAMICS
Work
Work(w) can be described as an interaction between a system and its surrounding. The interaction involves
exchange of energy .
Mechanical, Surface tension, Electrical, Magnetic work etc., but we are concerned only with Mechanical work.
Work of expansion: Consider the expansion of hot gases in the cylinder of an automobile engine. The hot gases push
the moving piston outward. Thus, work is done by the gases on the surroundings. This type of
work is known as the work of expansion.
Work of compression: Another example deals with the compression of air by means of an air compressor, or this air
is forced into a given volume with the help of the compressor. In this example, work is done
by the surroundings on the system. This type of work is known as the work of compression.
If system has done work on the surroundings then w is positive, whereas work is done on the system, the W is
negative
Let us, suppose that a gas enclosed in a cylinder (Figure 1) filled with a smoothly
moving frictionless piston is the system under consideration. The system is at a
pressure (P), volume (V) and temperature (T) and there are n moles of gas.
Assumptions:
• At every instant the applied or external pressure Pe is very nearly equal to the
pressure of gas.
• During a reversible process, the pressure, temperature and density of the gas
are uniform throughout the cylinder. Figure 1: Schematic representation
of reversible compression of gas
The mechanical work done (W) = force × displacement = APe (x) =Pe dV
dV = Adx is the volume change during the small displacement.
For a reversible process, Pe  P and W = P dV ……….. (1)

The molar work done (W) = P dV ……….. (1)

Where V is the molar volume of the gas at the particular instant indicated in Figure 1.

Suppose that the reversible compression process was carried out from an
initial thermodynamic state designated 1 to a final state designated 2.The
path of the process is depicted by a curve on the P-V diagram (Figure 2)
that joins the end points 1 and 2.

The small shaded strip under the curve represents the work done W = P dV.
𝑽𝟐
For the entire process stretching from 1 to 2, we have 𝑽
..........(3).
𝟏

W is equal to the total area under the curve 1-2.

A system can change from one state to another in many different
ways. In other words, there are several different paths that the
system can take changing state 1 to state 2, two of which are shown
in figure 3. These two paths are labelled 1 A 2 and 1 B 2.

Path 1 A 2 consists of two distinct parts:

During the first part the system is compressed at constant pressure until
the volume become equal to VA (= V2);
During the second part the gas is heated at constant volume its the
pressure and temperature rises to P2 and T2 , respectively.

Path 1 B 2 also consists of two parts:

In the first part gas is heated at constant volume unit the pressure until the pressure rises to PB (= P2).
In the second part the gas is compressed at constant pressure until the volume becomes equal to V2.
Heat
The amount of heat, Q, involved in a process is an important thermodynamic quantity.

Heat flows from the system to its surroundings, or vice versa, by virtue of a temperature difference, however
small, between the system and the surroundings.

The convention is that the heat is positive when it is absorbed by the system from the surroundings and negative
when heat is lost by the system to do the surroundings.

In adiabatic processes, no heat is exchanged between the system and its surroundings. In other words, Q = 0 for an
adiabatic process.

W is dependent on the path taken by the system between two given thermodynamic States.

Similarly, Q is not a state function either, that is ,it can not be expressed as a function of the thermodynamic
coordinates (P, T, etc).
FIRST LAW OF THERMODYNAMICS
The statement of the law of conservation of energy.

E = Q  W ……………. (1)

Q and W are not state functions, but their difference Q  W = E is a state function.
In other words, E can be expressed as a function of thermodynamic variable such as P,T and so forth.

In this particular cycle, steps 1 and 3 are constant volume steps and 2 and 4 are constant pressure steps.

On applying the first low of each of these operations,

(E)1 = Q1  W1, (E)2 = Q2  W2, (E)3 = Q3  W3 and (E)4 = Q4  W4

For the entire cycle, (E)cycle = Qi  Wi ……. (2)

Where Qi = Q1 + Q2 + Q3 + Q4 and Wi = W1 + W2 + W3 + W4 (E)cycle either  or = or  0

Therefore, (E)cycle = 0

The first law applies whether the process is reversible or not. For an infinitesimal process, the
first law statement can be expressed as follows: dE = Q  W