COURSE CODE: CHE

212

NAME: MR. OLANREWAJU ALADESUYI

SECOND LAW OF
THERMODYNAMICS
The first law of thermodynamics states that one form of
energy can change into another form but the total
amount of energy remains the same. But the first law
fails to indicate if the process of change we specify, can
occur or if so in what direction. The 1st Law of
thermodynamics does not give any information about
direction of change. Yet experience shows that most
natural processes always tend to occur spontaneously
in a direction which will lead to equilibrium e.g. flow
of heat (ii) electricity (iii) water (iv) gas

What is a Spontaneous process

A process which proceeds of its own accord, without any
outside assistance, is termed a spontaneous process.
The reverse process which does not proceed on its own, is
referred to as a non spontaneous process.
In general, the tedency of a process to occur naturally is called
the spontaneity. Spontaneous changes proceed until the system
reaches an equilibrium state. They are irreversible.
Examples:
Cliff jumping and mountain climbing.
Heat flow from a hot ball to a cold one, never from cold to hot.
When a vessel containing a gas is connected to another
evacuated vesse, the gas spreads throughout spontaneiuoly
unless the pressure is the same in both vessels.

Criteria for Spontaneity

1.
2.

3.

4.

5.

A spontaneous change is one-way or

unidirectional.
For a spontaneous to occur, time is no factor
i.e a spontaneous change may occur slowly or
rapidly.
If the system is not in equilibrium then a
spontaneous is inevitable
Once a system is in equilibrium state, it does
not undergo any further spontaneous change
in state if left undisturbed.
A spontaneous change is accompanied by a
decrease of internal energy or enthalpy (

This implies that only exothermic reactions will proceed

spontaneously due to the fact that exothermic changes
results in a decrease in enthalpy. But it has been observed
that endothermic changes such as melting of Ice and
evaporation of water takes place spontaneously. Clearly
there must be some other factor other than enthalpy
change which governs spontaneity. Its is the second law
which introduces the new factor is entropy factor. . The
two factors are related by the equation
G = H - TS (for constant Pressure Process)
G = Change in Gibbs Free Energy which is the driving
force of any chemical or physical change or process.
S = Change on entropy.

What is a Process?
If a change in the value of the properties of a
system occurs when the system goes from one
state to another, a process is said to have taken
place. The process can either be reversible or
irreversible.
Reversible Process
The process is reversible when the driving force is
only infinitesimally (minutely) greater than the
opposing force, and the process can be reversed by
increasing the force by an infinitesimal amount.
For a reversible process p Pex is slightly greater
than p the gas is compressed. On the other hand of
p is slightly greater than Pex, the gas will undergo
expansion.

A reversible process is a change of state such

that
1. The change occurs in a sequence of steps,
each of which is infinitesimally removed from
the preceding and succeeding steps.
2. The change occurs through a succession of
equilibrium steps, each intermediate state being
an equilibrium state.
A reversible process must be carried out at a
very slow rate for condition 2 above to hold. This
makes true reversible process in practice
unattainable as such a process will require an
infinitely long time to go to completion.

In case B the piston is withdrawn rapidly and

no time is allowed for the pressure and
temperature of the gas to attain uniform
values after each change. The temperature
and pressure vary throughout the gas. Hence
the expansion does not go through a
succession of equilibrium states. Therefore,
the overall process can be considered
irreversible.

Definition of Entropy
Entropy is a thermodynamic state quantity that is
a measure of the randomness or disorder of the
molecules of the system. The symbol of entropy
is S, while the change accompanying entropy
from start to the completion is represented by
S. The entropy of a system is a state function
and depends only on the initial and final states of
the system. The change in entropy, S, for any
process is given by the equation,
S = Sfinal - Sinitial
When Sfinal > Sinitial, S is positive.
It is however observed that a process
accompanied by an increase in entropy always
tends to be spontaneous.


Concept
of Entropy, S
1. It is a state function; unlike work or heat
there is no simple physical analogue.
However it may be pictured as a measure of
disorder or randomness of a system.
2. It has the dimension of energy and
temperature.
For infinitesimal change
ds = Jmol-1K-1
or for a finite change
S = ;
+ve when qr is +ve
-ve when qr is -ve

3. For a given system

STotal = Sconfiguration + SThermal
Unlike enthalpy, the absolute entropy of a
substance can be calculated (from 3rd Law
of Thermodynamics)
4. For any process occurring in an isolated
system (Universe) S 0
For any reversible process S = 0
For any irreversible process S > 0

The second law of thermodynamics states that:

whenever a spontaneous process takes place, it is
accompanied by an increase in the total energy of
the universe.
Suniv = Ssyst + Ssurr
The second law, as stated above, tells us that when
an irreversible spontaneous process occurs, the
entropy of the system and the surroundings
increases.
In other words Suniv > 0. When a reversible process
occurs, the entropy of the system remains constant.
Suniv =0. since the univers is always experiencing a
change the second law can be restated as: the
entropy of the system is constantly changing

Statement of Second Law

The second law of thermodynamics can be stated in
different ways, all of which are equivalent to one
another. This equivalence is not immediately
obvious.
1. Clausius Statement
It is impossible for a cyclic process to transfer heat
from a body at a lower temperature to one at a
higher temperature without simultaneous
conversion of work into heat.
This implies that when work is used for the
continuous transfer of heat from a lower
temperature to one at a higher temperature, some
work must be wasted by direct conversion into heat


According
to Clausius,entropy of a system
(not undergoing chemical or physical
changes) is a constant quantity when there is
no communication of heat. When heat(q)
flows into a system, the entropy increases
by . Heat flowing out of a system produces a
corresponding decrease. Thus entropy could
be expresses as S = .
If heat is absorbed, then S is positive and
there will be increase in entropy. If heat is
evolved, S is negative and there is a
decrease in entropy.

Kelvins Statement
It is impossible for a cyclic process to convert heat into work without
simultaneous transfer of heat from a body at higher temperature to one at
lower temperature.
This implies that in the conversion of heat into work, some of the heat in
a body at higher temperature must be wasted by direct transfer to a body at a
lower temperature.
Heat cannot flow spontaneously from a colder to a hotter body.
Heat cannot be extracted from a hot source and turned entirely into work.
However, the most general law of the second law of thermodynamics states
that any process which occurs in Nature is accompanied by an increase in
total entropy i.e.
STotal = (SSystem + SSur) increase
Statistical definition of entropy supposes that it is possible to calculate the
degree of disorder in a system using the Boltzmann formula (1896):
S = KlnW
Where k is the Boltzmanns constant (k = 1.381 x 10 -23JK-1) and W = the
number of different ways in which the energy of the system can be achieved
by rearranging the atoms or molecules among their available states.

Calculation

of Entropy Change for an Ideal

gas
Entropy is a state function and its value depends
on two of the three variables T, P and V.
a) T and V as variables
For one mole of an ideal gas,
S = 2.303Cv log +2.303 R log
For n moles, S = 2.303nCv log +2.303n R log
b. P and T as variables
For one mole of an ideal gas
S = 2.303Cp log +2.303 R log
For n moles, S = 2.303nCp log +2.303 nR log
From these equations entropy change can be
calculated.

 At

constant temperature for an

isothermal process.
In this case T1 = T2, the equation (1) and (2)
reduced to ST = 2.303 n R log
and

ST = 2.303 n R log

In an isothermal expansion ST is positive,

while in isothermal contraction ST is
negative
At constant pressure ( Isobaric
process) where p1 = p2 the equation (1)
reduces to
Sp = 2.303 n CP log

At constant volume for an Isochoric

process in this case v1 = v2,
The equation (1) reduces to
Sv = 2.303 n Cv log .
Exercise
1.
Calculate the change in entropy accompanying the
heating of one mole of helium gas, assumed ideal, from
a temperature of to a temperature of 82 at constant
pressure given that
2. 2mol of an ideal monoatomic gas expand reversibly from
a volume of 2litres and temperature of 289K to a volume of
20litres and temperature of 240K. Assuming , calculate the
entropy change for the process

Entropy change Accompanying change of phase

When
there is a change of state from solid to
liquid or liquid to vapours or solid to vapours,
there is always an entropy change. This
change may be carried out reversibly at
constant temperature as two phases are in
equilibrium during the change.
Considering the process of melting of 1 mole
of the substance reversibly. It absorb molar
heat of fusion at temperature equal to its
melting point. The entropy change then
becomes Sf =


Similarly
we have Sv = as the value for
entropy change when one mole of liquid is
boiled reversibly.
and also St = when one mole of a solid
changes reversibly from one allotropic form
to another at its transition temperature.
Exercise
Calculate the entropy increase in the
evaporation of 2mol of water at 100 degree
centigrade in S. I. units given that the heat of
vaporization of water at 100 degree
centigrade is 540cal/g.

Free Energy (G)

The free energy (G) is defined as

G = H TS
where H is the heat content or enthalpy
of the system, T is its temperature and S its
entropy. It is a single valued function of
thermodynamic state of the system and is
an extensive property.
Let us consider a system which
undergoes a change of state from (1) to (2)
at constant temperature.
We have
G2 G1 =(H2 H1) T(S2 S1)

or G = H - TS
Recall H = E + PV
Substituting for H
G =E + PV - TS
Also we know that A = E - TS
Therefore, G = A + PV
PV is the work done as a result of expansion against a constant external
pressure P. Therefore, it is clear that the decrease in free energy (- G )
accompanying a process taking place at constant temperature and pressure is
equal to the maximum work done obtainable from the system other than the
work of expansion. This quantity is referred to as the network.
Total work/ network = w - PV = - G
This quantity is of great importance in thermodynamics because the change
in free energy is a measure of network which may be electrical, chemical or
surface work.

How Free Energy Varies with Temperature and

Pressure
H TS
G=
and H = E + PV ( first law of thermodynamics)
G = E + PV TS
Differentiating
dG = dE + PdV + VdP TdS SdT.(i)
For an infinitesimal stage of a reversible
process. dq = dE + dw
Recall dS =
dq = dE + PdV ( first law of thermodynamics)
Therefore TdS =dE + PdV(ii)


Substituting
eqn. (ii) into (i) we have
dG= dE + PdV + VdP dE - PdV SdT
= VdP SdT.
(iii)
At constant pressure eqn (iii) becomes
dGp = -SdTp

Or ()p = -S.

(iv)

At constant temperature eqn (iii) becomes

dGT = VdPT
Or ()T = V.

(V)

Eqn (iv) and (v) shows how free energy

varies with temperature and pressure
respectively.


Isothermal
Change in Free energy
For an isothermal process eqn (iii) ,
dG= dE + PdV + VdP dE - PdV SdT
= VdP SdT
is reduced to dG = VdP..
(vi)
Integrating, G = G2 G1 =. (V)
For one mole of a gas PV = RT
Or V = ,
Substitute for V in eqn (v)
dG = RT
= RT In
For n moles of the gas, G =n RT In .. (vi)


From
the general gas equation P1V1 = P2V2

Or =
Substituting into eqn. (vi) gives
G = RT In
And for n number of moles
G =n RT In
Or G =2.303 n RT log

Conditions for Equilibrium and Criteria for a

Spontaneous Change
a. In terms of Entropy change
The entropy of a system remains constant in a
reversible change while it increases in an
irreversible change.
dS = 0 for reversible
dS > 0 for irreversible change
Considering both the system and its surroundings
dSsystem + dS surrounding =0
And dSsystem + dS surrounding > 0.. (Vii)
Combining we have
dSsystem + dS surrounding 0..(viii)


From
first law of thermodynamics
dS =- = - , dE is the change in internal
energy and dw is the wort done by the
system.
From eqn (viii) we get
dSsystem ( ) 0..(ix)

dSsystem - 0..(x)
When E and V are constant
Eqn. (x) reduces to dSE.V 0
dSE.V > 0 for an irreversible process
(spontaneous)
dSE.V = 0 for a reversible process (equilibrium)

When S and V are constant

dS = 0 and dV = 0
Eqn (x) becomes reduced to dE 0
dE >0 for an irreversible change(spontaneous)
dE = 0 for an reversible change (equilibrium)
b) In terms of enthalpy change
H = E + PV
Differentiating,
dH = dE + PdV + VdP
Or dE PdV = -dH + VdP
Putting into eqn (x)
Tds dH +VdP 0
Rearranging we get
dH -Tds VdP 0..(xi)

At constant S and P
dS = 0 and dP = 0
Therefore dH 0..(xii)
So dH < 0 for an irreversible change
(spontaneous)
dH = 0 for a reversible change (equilibrium)
In terms of Free Energy Change
G = H TS
G = E + PV - TS
(H = E + PV)
Differentiating we get
dG = dE + PdV +VdP -TdS -SdT
TdS dE PdV = -dG + VdP - SdT
c.

Substituting in equations (ix) we get

-dG + VdP SdT 0
Or dG - VdP + SdT 0
At constant pressure in an isothermal
process( T is also constant) this equation
becomes
dG 0
dG < 0 for an irreversible change
(spontaneous
dG = 0 for a reversible change (equilibrium)

Summary of Conditions for Spontaneity

and equilibrium
Conditions

Irreversible
process
(spontaneous
)

Reversible
process
(equilibrium)

At constant E, V ds > 0

ds = 0

At constant S, V - dE > 0

-dE = 0

At constant S, P dH < 0

dH = 0

At constant P,T

dG = 0

dG < 0

Practise Questions

1.Two moles of an ideal gas are allowed to expand

reversibly and isothermally at 300K from a pressure
of 1 atm to a pressure of 0.1 atm. What is the change
in Gibbs free energy?
ANS: -11.4882kJ
2. For the reaction
N2 (g) + 3H2(g) = 2NH3
The free energy changes at 25oC and 35oC are
-33.089 and 28.018kJ respectively. Calculate the
heat of reaction at 35oC ANS: -184.176 kJ
3. Calculate the standard entropy of formation,S of of
CO2 (g). Given the standard entropies of CO 2 (g), C(s),
O2(g), which are 213.6, 5.740 and 205.0JK-1 Ans:
2.86JK-1

 Show that Gibbs free energy is given in

4.
terms of the state parameter
dG = VdP SdT,
Hence derive the expression
()p = -S and

()T = V