1.

6 Thermodynamics Processes
A process means:
change in the condition or state of the system

A path represents a sequence of situations a

system passes through during a change in the state

of the system

 Thus the transformation from A B the system can

go through various parts

1.6.1 Adiabatic Process

No heat transfer occurs across the boundary

between the system and its surroundings i.e. the

temperature gradient, T = 0
If T 0, heat will transfer (which is a rate process)

How adiabatic processes are achieved?

Process is carried out quickly
Well insulated boundary

1.6.2 Isothermal Process

Temperature is uniform at every point throughout the

system and remains constant during the entire process

If T = 0, Transfer of heat = 0.
If T 0, Transfer of heat/work will occur until T = 0.

If the process produces heat

Transfer of heat and/or work across the boundary is

mandatory
How to achieve isothermal process?
Process is carried out very slowly (close to infinity)
Permeable boundary

1.6.3 Isobaric Process

Pressure remains constant throughout the system

during the process

1.6.4 Isochoric Process

Volume remains constant throughout the process.

Achieved by Impermeable and rigid

container/boundary

1.6.5 Cyclic Process

The initial and final states of the system are the same
The overall changes in all state variables are = zero.

i.e.
In the process of going through this cycle, the system

may perform work on its surroundings

repeating nature of the process path allows for
continuous operation, making the cycle an important
concept in thermodynamics (heat engines, heat
pumps)

1.6.6 Polytropic process

process that obeys the relation:
where p is the pressure, V is volume, n, the

polytropic index, is any real number, and C is a

constant

1.6.7 Isentropic process

Occurs at constant values of the systems entropy.

Such processes must be adiabatic, and must also

occur without dissipative effects, or irreversibitities.

Sometimes called the reversible adiabatic process
(2nd Law)

1.6.8 Summary
Process
Isobaric

Constraints imposed
Pressure remains constant
(P=0)
Isothermal Temperature remains
constant (T=0)
Isochoric Volume remains constant
(V=0)
Adiabatic System remains insulated
(Q=0)
Cyclic
All variables return to
original value (Z=0)

Quantity exchanged
Heat and work may be
exchanged
Heat and work may be
exchanged
no work done. Only
heat is exchanged
Only work is
exchanged
Heat and work may be
exchanged

1.7 Thermodynamic Equilibrium

The state of a thermodynamic system can be

characterised by its variable only if the system is in

equilibrium with these variable.
Thus a system is in thermodynamic equilibrium only if
it is satisfied all of the conditions;
Mechanical equilibrium: mainly P (in the absence of

electric, magnetic forces).

pressure of the system must be uniform and there must
be no changes in pressure if other variables are not
changed.

 Thermal equilibrium: Temperature must be uniform

throughout the system. Thus there will be no tendency

of heat to flow from one part of the system to the other.
For purely physical processes such as

expansion/compression of a substance e.g. H2O

vapour, thermodynamic equilibrium = mech
equilibrium + thermal equilibrium.
However, for physico-chemical processes and
reactive systems, such as those encountered in
extractive metallurgy, there is need for attainment of
chemical equilibrium in addition to the above 2

 Chemical equilibrium: Chemical potential of the system

must be uniform i.e. No change in free energy.

Partial/pseudo equilibrium
occurs when a system is not in complete

thermodynamic equilibrium.
There will be very small (undetectable) changes in the
system as it tries to attain equilibrium.
E.g. cementite (Fe3C) in iron-carbon system is
metastable (not completely stable). But it will remain
so for ever for as long as the steel is kept at room
temperature

1.8 The equation of state of an ideal

gas
Any equation that relates the pressure (P),

temperature (T), and specific volume (v) of a

substance is called an equation of state.
Property relations that involve other properties of a
substance at equilibrium states are also referred to as
equations of state.
There are several equations of state, some simple
and others very complex

 The simplest and best-known equation of state for

substances in the gas phase is the ideal-gas

equation of state.
Predicts the P-v-T behaviour of a gas quite
accurately within some properly selected region
is derived from the following laws;
Boyles Law: For a gas at constant temperature

 Charless Law: For a gas at constant

pressure
These relationships can be plotted on a P-v-T surface

(at constant T we get rectangular hyperbola while at

constant pressure we get straight lines)

 Guy Lussacs Law: the pressure of a

fixed amount of gas at fixed volume is

directly proportional to its temperature in
kelvins
i.e.

Combining the 3 laws gives

That constant can be calculated at STP (1 atm, 273K

and 22.4L) to give 8.314 J/mol.K (or kJ/kmol.K), which

is the universal gas constant (i.e. it is for all gases)
and is denoted by Ru

 Thus

equation of state for 1 mole of ideal gas.

It is called the ideal gas law or the ideal-gas

equation of state and a gas that obeys this

relation is called an ideal gas.
In this equation, P is the absolute pressure, T is
the absolute temperature, and v is the specific
volume.
The gas constant R is different for each gas and
is determined from

 The gas constant R is different for each gas and

is determined from
Where M is the molar mass of the gas.
And since mass = molar mass x number of

moles i.e. m = MN
Then the ideal-gas equation of state can be
written in several different forms:

1.9 Zeroth Law

If two systems (say A and B) are in thermal

equilibrium with a third system (say C) separately

(that is A and C are in thermal equilibrium; B and
C are in thermal equilibrium) then they are in
thermal equilibrium themselves (that is A and B
will be in thermal equilibrium

 It is the basis of temperature measurement

Thus in order to know if two bodies are at the

same temperature there is no need to bring

them together and observe changes in their
properties
It is necessary only to check if they are
individually in equilibrium with a third body and
this third body is practically a thermometer
In metallurgical thermodynamics the Law may
be applies in studying phases for example

1.10 Work
It is energy transfer across the boundary of a

system that is equivalent to a force acting through

a distance
2

W F .ds
1

W>0 : work is done by the system

W<0 : work is done on the system

W=0 : no work done

 For a gas, work is the product of the pressure p and

the change in volume V during a process

v2

work pdV
v1

the pressure will be constant.

1.11 Energy
it is the capacity to bring about changes in a

system
Microscopic forms of energy are those related to
the energy possessed by the individual
molecules and to the interaction between them
Macroscopic forms of energy on the other hand
are related to the gross characteristics of the
substance on a large scale.

Total energy, Etotal = Emacroscopic + Emicroscopic

 Kinetic energy,

1 2
Ek mv
2

It is associated with mass of whole body, thus it

is an extensive property
Potential energy E p mgh
Dependent on mass of object; thus extensive
Mechanical: Kinetic, potential and
configurational.
Thermal: Heat exchanged.
Electrical: Electrical energy = current x time x
potential difference.
Chemical: Chemical energy = no. of chemical
bonds x bond strength

 Internal energy, U : sum of all molecular or

microscopic energies of a substance and is an

extensive property
Internal energy per unit mass, u is an intensive property.

Absolute value of the energy is not known. All we

can determine is change in internal energy.

Internal energy will depend on temperature for a
material of fixed mass, composition and structure.
i.e. U is function of Temperature only.