B.Sc.

III Year
PHYSICAL CHEMISTRY
SEM – V: Paper -V

UNIT- V

THERMODYNAMICS: 12h

The first law of thermodynamics-statement, definition of internal energy and

enthalpy. Heat capacities and their relationship. Joule-Thomson effect-
coefficient. Calculation of w, for the expansion of perfect gas under isothermal
and adiabatic conditions for reversible processes. State function. Temperature
dependence of enthalpy of formation – Kirchhoff’s equation.

Second law of thermodynamics. Different Statements of the law. Carnot cycle

and its efficiency. Carnot theorem. Concept of entropy, entropy as a state
function, entropy changes in reversible and irreversible processes. Entropy
changes in spontaneous and equilibrium processes.
 Thermodynamics
Introduction:
The word “Thermodynamics” is a Greek word which means, Study of flow of
heat. Thermodynamics is a branch of Physical chemistry, which deals with the
energy changes accompanying a chemical reaction. Chemical
thermodynamics is the study of the interrelation
of heat and work with chemical reactions or with physical changes
of state within the limitations of the laws of thermodynamics.
Thermodynamics, describes macroscopic properties of equilibrium systems
and Built on 4 Laws of Thermodynamics,
• 0th Law ⇒ Defines Temperature (T) : Two bodies which are in thermal
equilibrium with a third body are in thermal equilibrium with each other.
• 1st Law ⇒ Defines Energy (U) : The energy of the universe is constant.
• 2nd Law ⇒ Defines Entropy (S) : In any spontaneous process, there is always
an increase in entropy of the universe.
• 3rd Law ⇒ Gives Numerical Value to Entropy: The entropy of a perfect crystal
at 0 Kelvin is zero.
System: The part of the Universe that we choose to study
Surroundings: The rest of the Universe
Boundary: The surface dividing the System from the Surroundings

Systems can be:

• Open: Mass and Energy can transfer between the System and the
Surroundings
• Closed: Energy can transfer between the System and the Surroundings, but
NOT mass
 • Isolated: Neither Mass nor Energy can transfer between the System and the
Surroundings.

Thermodynamic Processes:

The operation by which a thermodynamic system changes from one state to

another is called a thermodynamic process. A thermodynamic process is
always accompanied by change in energy. A thermodynamic process is a
passage of a thermodynamic system from an initial to a
final state of thermodynamic equilibrium.
Depending upon the condition of change, the following types of
thermodynamic processes are defined,

• Isothermal process: A process in which the temperature of the system

remains constant throughout the process, yet heat enters or leaves the system is
called as isothermal process. Isothermal processes are carried out by placing
the system in a thermostat. For isothermal processes, change in temperature is
zero (dT = 0)
• Adiabatic process: A process in which no heat enters or leaves the system
during any step of the process is known as adiabatic process. Such processes
are carried out in closed insulated containers (Thermos bottle). For adiabatic
process, change in heat is zero (dQ = 0).
• Isobaric process: A process during which pressure of the system remains
constant throughout the reaction is known as isobaric process. For isobaric
process, dP = 0
• Isochoric process: A process during which volume of the system remains
constant throughout the reaction is known as isochoric process, for which, dV
= 0.
• Cyclic process: A process during which the system comes to its initial state
through a number of different processes is called a cyclic process, for which,
dE = 0 and dH = 0.
A reversible process can be proceed very slowly through a succession of
infinitesimal steps and its direction can be reversed at any point by making a
small change in temperature or pressure.
An irreversible process is carried out in a single step and cannot be carried
out in reverse order. All spontaneous processes are irreversible.

The First Law of Thermodynamics

It is also known as Law of conservation of energy. The first law of

thermodynamics states that,

1. “The energy can neither be created nor be destroyed, but it can be

transformed from one form to another form “
OR
2. “The total amount of energy of the universe is a constant”
Or
3. The total energy of an isolated system remains constant though it may
change from one form to another.
4. Mathematical form of First law of thermodynamics,
∆E = q + w,
Where,
∆E = Change in internal energy of the system,
q = Amount of heat supplied to the system,
w = Work done on the system
If q amount of heat is supplied to a system, then this heat energy is useful in
two ways,
When a system goes from initial state to the final state, it undergoes a change
in the internal energy from E1 to E2, thus, ∆E = E2 - E1. The second part is used
to do some external work on the system by the surroundings (w),
If the work is done by the system on the surroundings, then the first law
becomes,
∆E = q - w

Sign Conventions:
➢ +q = Heat absorbed by the system,
➢ -q = Heat liberated by the system
➢ +w = Work done on the system,
➢ -w = Work done by the system
Consider a system whose internal energy at initial stage is E1. If the system is
supplied q amount of heat, the internal energy of the system will become,
E1 + q.

Now if w works done on the system by the surroundings, then the final internal
energy of the system becomes E2. Thus,
E2 = E1 +q + w
Or E2 - E1 = q + w
Or ∆E = q + w
This is the mathematical statement of the first law of the thermodynamics,
where q is the heat absorbed by the system and w is the work done on the
system.
Applications of first law of thermodynamics:

➢ For Isothermal process. Since temperature remains constant in the isothermal

process so the internal energy of the gas must also remain constant, When a
system undergoes an isothermal change (T = Constant) i.e. ∆E = 0, then the first
law of thermodynamics becomes, q = - w, i.e. Heat absorbed by the system
from the surroundings = work done by the system on the surroundings
➢ For isochoric process (V = Constant), w = 0 then ∆E = q, increase in internal
energy of the system is equal to the heat absorbed by the system
➢ A process in which no heat can enter or leave the system is called an adiabatic
process.” In an adiabatic process, there is no transfer of heat across the
boundary of the system, so Q=0. For adiabatic process, there is no exchange of
heat between the system and the surroundings, q = 0, then ∆E = w, the increase
in internal energy of the system is equal to the work done on the system
➢ Isolated system: It is a system that does not interact with the surroundings. In
this case, there is no heat flow and the work done is zero. It means ΔQ = 0 and
ΔW = 0. Hence ΔE = 0. Therefore the internal energy of an isolated system
remains constant.
➢ Cyclic process: The process in which a system returns to its initial state after
passing through various intermediate states is called a cyclic process. In this
process, the change in internal energy is zero. i.e., ΔU = 0. Hence from the first
law of thermodynamics. ΔW = ΔQ, Hence, in a cyclic process, the amount of
heat given to a system is equal to the net work done by the system. This is the
principle of heat engines whose purpose is to absorb heat and perform work in
a cyclic process.

Limitations to First law of thermodynamics:

➢ The law states that whenever a system undergoes any thermodynamic
process it always holds certain energy balance. However, the first law does
not specify the feasibility of the reaction
➢ It does not tells us about direction in which heat flows when they are in
contact
➢ It does not tell about the final temperature of two bodies when they are in
direct contact.
➢ It does not tell about the entropy of system.
Internal Energy

Every substance possesses a definite amount of energy which depends upon its
chemical nature, temperature, pressure and volume. This energy associated with
every substance is called internal energy or intrinsic energy and is denoted by letter
E or U.

The internal energy of a substance or system is a definite quantity and its exact
value cannot be determined because it involves certain quantities like translational,
vibrational and rotational kinetic energies which cannot be measured.

E = Etr + Erot + Evib + Eele + Ebon + …..

Internal energy is state function; therefore its change can be determined instead of
its absolute value.

The change in internal energy of a system is,

ΔE = E2 – E1
Where, E2 = Internal energy of the system at final stage and
E1 = Internal energy of the system at initial stage
If, E1 > E2 (ER > EP ), then the extra energy possessed by the system in the initial
state would be given out and thus ΔE will be negative.
If, E2 > E1 (EP > ER ), energy will be absorbed in the process and ΔE will be
positive.
 Enthalpy

Heat content of a system at constant pressure is called Enthalpy. It is denoted by

H.
The enthalpy of a substance or a system is the total amount of energy stored
in that substance. Enthalpy of a system is a state function and therefore its change
can be determined instead of its absolute value.
The enthalpy of a thermodynamic system is defined as,
H = E + PV
Where,
H is enthalpy is the internal energy of the system, P is pressure, V is the volume of
the system.
Change in enthalpy:
Let the enthalpy, internal energy and volume of a system in the initial state be H 1,
E1 and V1 at pressure P. Let the system gains dQ amount of heat from the
surroundings at constant pressure P and changes to the final state having
enthalpy, internal energy and volume as H2, E2 and V2 respectively.
The enthalpies of two states can be represented as below,
H1 = E1 + PV1
H2 = E2 + PV2
The change in enthalpy will be given by,
ΔH = H2 – H1
ΔH = (E2 + PV2) – (E1 + PV1)
ΔH = (E2 – E1) + P (V2 - V1)
ΔH = ΔE + P ΔV
ΔH = ΔE + W
Thus, the enthalpy change accompanying a process at constant pressure may be
defined as the sum of the increase in internal energy of the system and the
pressure – volume work (i.e. the work of expansion)

The process where, H2 > H1, in exothermic process ΔH is negative, while the
process where, H2 < H1, in endothermic process ΔH is positive.
 Heat Capacities

Heat Capacity: It is defined as the amount of heat required to rise the temperature
of a substance by one unit temperature change. Heat capacity of a system means
the capacity to absorb and store energy.
We can also write it as q = C ∆T, the coefficient, C is called the heat capacity.

Specific heat, also called specific heat capacity is the quantity of heat required to
raise the temperature of one unit mass or 1 gram of a substance by one degree
Celsius.
The molar heat capacity of a substance is the heat capacity for one mole of the
substance and is the quantity of heat required to raise the temperature of one mole
of a substance by one degree Celsius.
𝑪
Cm = ( )
𝒏
For finding out the heat, q, required to raise the temperatures of a sample, we
multiply the specific heat of the substance, c, by the mass m, and temperatures
change, ∆T as
q = C x m x ∆T = C ∆T

Relation between molar heat capacities:

CV: Molar heat capacity at constant volume: It is defined as the amount of heat
required to rise the temperature of one mole of substance by 1 oC at constant
volume.
According to first law of thermodynamics,
Q = ΔE + W
Q = ΔE + P ΔV
Q = ΔE (since at constant volume, ΔV = 0)
From the definition of heat capacity of a substance at constant volume,
Cv = [Q / (T2-T1)] v
Cv = [ΔE / (T2-T1)] v
Cv = [dE / dT] v
Cv = dE / dT
Thus, heat capacity of a system at constant volume is defined as the increase in
internal energy of the system per degree rise of temperature at constant volume. Or
it is the rate of change of internal energy with temperature at constant volume.
CP: Molar heat capacity at constant pressure: It is defined as the amount of heat
required to rise the temperature of one mole of a substance by 1 oC at constant
pressure.
According to first law of thermodynamics,
Q = ΔE + W
Q = ΔE + P ΔV
From the definition of heat capacity of a substance at constant pressure,
Cp = [Q / (T2-T1)] p
Cp = [(ΔE + P ΔV) / (T2-T1)] p
Cp = [ΔH / (T2-T1)] p
Cp = [dH / dT]p
Cp = dH / dT
Thus, heat capacity of a system at constant pressure is defined as the increase in
enthalpy of the system per degree rise of temperature at constant pressure. Or it is
the rate of change of enthalpy with temperature at constant pressure.
The relation between Cp and Cv :
The molar heat capacity of a substance at constant pressure is always greater than
the molar heat capacity at constant pressure i.e.
CP > CV
Whenever a substance is heated at constant volume, no work is done by the
substance and thus the heat absorbed by the system is used completely to increase
the internal energy of the substance. However, when a substance is heated at
constant pressure, do some external work in addition to increase in the internal
energy of the substance. Hence Cp is always greater then Cv.
The relation between CP and CV for an ideal gas is given by,

CP - CV = R
Or
Cp = Cv + R
Where R is the universal gas constant.
Derivation:

When heat is absorbed by a body, the temperature of the body increases. And when
heat is lost, the temperature decreases. The temperature of an object is the measure
of the total kinetic energy of the particles that make up that object. So when heat
is absorbed by an object this heat gets translated into the kinetic energy of the
particles and as a result the temperature increases. Thus, the change in temperature
is proportional to the heat transfer.

q = n C ∆T ……… 1

This equation represents the heat q required to bring about a ∆T difference in

temperature of n mole of any matter. The constant C here is called the molar heat
capacity of the body.

Thus, the molar heat capacity of any substance is defined as the amount of heat
energy required to change the temperature of 1 mole of that substance by 1 unit. It
depends on the nature, size, and composition of the system.

From equation 1,

The molar heat capacity at constant volume CV, is given by

qv = CV ∆T = ∆E ………….. 2.

I.e. the amount of heat supplied to a substance at constant volume is used to

increase the internal energy of the substance (rise in temperature),

The molar heat capacity at constant pressure CP is given by,

qp = Cp ∆T = ∆H ………….. 3.

We know that for one mole of an ideal gas,

∆H = ∆E + ∆ (PV) = ∆E + ∆ (RT) = ∆E + R ∆T

Thus,

∆H = ∆E + R ∆T ………….. 4.

The amount of heat supplied at constant pressure is used to increase the internal
energy of the substance (rise in temperature) and also used to do some external
work
From equation 3,

qp = Cp ∆T = ∆H

Cp ∆T = ∆H

Cp ∆T = ∆E + R ∆T

Cp ∆T = CV ∆T + R ∆T (from eq. 2, CV ∆T = ∆E)

Cp ∆T = CV ∆T + R ∆T

Cp = CV + R
Hence,
Cp - CV = R
Joule – Thomson effect:

Statement: The phenomenon of change of temperature produced when a gas is

made to expand adiabatically from a region of high pressure to a region of low
pressure is known as the Joule – Thomson effect.

Joule and Thomson observed that when a compressed gas is forced through a
porous plug into vacuum or a region of low pressure, under adiabatic conditions, it
gets appreciably cooled. Hydrogen and Helium are exceptional as they get warmed
up under similar conditions.

The temperature below which a gas becomes cooler on expansion is known as the
Inversion temperature.

Joule – Thomson experiment:

A tube thoroughly insulated is fitted with a porous plug in the middle and two
pistons A and B on the sides. The pressures on the left and right sides of the plug
are kept at P1 and P2 respectively, where P1 > P2.

A volume V1 of the gas enclosed between piston A and porous plug C at a higher
pressure P1 is forced very slowly through the porous plug by moving the piston A
inwards and is allowed to expand to volume V 2 at a lower pressure P2 by moving
the piston B outwards. The change in temperature is found by taking readings on
the two thermometers and it was observed that when the experiment is done at
 room temperature, all gases (except H2 and He) show a fall in temperature on
expansion.

Since the process is carried out adiabatically,

Q=0

According to first law of thermodynamics,

Q = ΔE + W
0 = ΔE + W
ΔE = - W
W = - ΔE
Thus, the work done during the expansion of the gas under adiabatic conditions is
at the expense of the internal energy. In other words, when the work of expansion
is done adiabatically, the internal energy and hence temperature of the gas
decreases.
Further on the left side of the plug, the work is done on the system,
Work done on the system = -P1V1
Whereas on the right side of the plug, work is done by the system.
Work done by the system = P2V2
Net work done by the system,
W = P2V2 - P1V1
Then,
ΔE = - W
ΔE = - (P2V2 - P1V1)
ΔE =P1V1 – P2V2
Further, the change in internal energy,
ΔE = E2-E1
E2-E1 = P1V1 – P2V2
E2+ P2V2 = E1+P1V1
 H2 = H1
ΔH = H2-H1 = 0
ΔH = 0.
Thus, when a gas expands adiabatically through porous plug, the enthalpy of the
system remains constant, while internal energy changes. In other words, adiabatic
expansion of a gas takes place at constant enthalpy, such expansion is known as
isoenthalpic.
Joule – Thomson coefficient:
Joule – Thomson coefficient may be defined as the change in the number of degrees
of temperature produced by a drop of one atmospheric pressure when the gas
expands under conditions of constant enthalpy. It is expressed as,

From the above expression, it is obvious that

➢ If µ is positive (i.e., when dT and dP both are negative), the gas cools on
adiabatic expansion. Most of the gases cools on expansion at room
temperature.
➢ If µ is negative (i.e., when dT is positive and dP is negative), the gas warms
up on adiabatic expansion at room temperature. Hydrogen and Helium warms
up on expansion at room temperature.
➢ If µ =0 (i.e., when dT =0 for any value of dP), the gas neither cooled nor
warms up on adiabatic expansion.
➢ The temperature at which the sign of µ changes is called inversion
temperature.
➢ It has been found that at a particular pressure, every gas has a definite
temperature at which µ = 0, below this temperature µ = +ve and above this
temperature µ = -ve.
➢ The inversion temperatures of most of the gases are much higher than the
room temperature and hence these gases undergo cooling on adiabatic
expansion at room temperature.
 Work done in reversible isothermal expansion of ideal gas

An isothermal process is a change of a system, in which

the temperature remains constant: ΔT =0. This typically occurs when a system is
in contact with an outside thermal reservoir (heat bath), and the change in the
system will occur slowly enough to allow the system to continue to adjust to the
temperature of the reservoir through heat exchange. In an isothermal process, the
value ΔT = 0 and therefore the change in internal energy ΔU = 0.
Simply, we can say that in isothermal processes,
T=0
ΔT = 0.
dT = 0.

Consider an ideal gas enclosed in a non-insulated

cylinder fitted with a weightless and frictionless piston. It iss supposed to be in
thermal equilibrium with the surroundings so that the temperature of the gas
remains constant throughout the experiment. Suppose P is the pressure of the gas
contained in the cylinder.
We know that the reversible expansion of the gas takes
place in a infinitesimal small steps. As a result of expansion the pressure of the gas
within the cylinder falls from P to P-dP and is equal to the external pressure on the
piston and the volume increases from V to V+dV. The external pressure is lowered
further by the same infinitesimal amount of dP and the same type of changes take
place again leading to an increase of an infinitesimal amount of volume dV.
The small amount of work done by the gas in each step
of expansion is given by the product off the external pressure and the increase in
volume,
dW = (P – dP) dV
dW = P dV – dP dV
dW = P dV
(Ignore the product dPdV as both quantities are infinitesimal)
 The total work done by the gas in expansion from original volume V 1 to final
volume V2 will be the sum of the series of terms P dV in which the value of P
goes on decreasing while the volume of the gas goes on increasing gradually.
Hence,
𝑉2
𝑊 = ∫ 𝑃 𝑑𝑉
𝑉1
For n moles of an ideal gas,

PV = nRT

P = nRT / V
𝑉2
𝑛𝑅𝑇
𝑊=∫ 𝑑𝑉
𝑉1 𝑉
For an isothermal process, T is constant. Also n, R are constant quantities. Hence,
𝑉2
1
𝑊 = 𝑛𝑅𝑇 ∫ 𝑑𝑉
𝑉1 𝑉
𝑉2
𝑊 = 𝑛𝑅𝑇 ln
𝑉1
𝑉2
𝑊 = 2.303 𝑛𝑅𝑇 log
𝑉1
Therefore, the work done in reversible isothermal expansion of an ideal gas is,
𝑉2
𝑊 = 2.303 𝑛𝑅𝑇 log
𝑉1
Or
𝑃1
𝑊 = 2.303 𝑛𝑅𝑇 log
𝑃2
 Adiabatic reversible expansion of an ideal gas

An adiabatic process is that in which no heat enters or leaves the system at any
stage.

Thus for every infinitesimal change of the process,

dQ = 0

From first law of thermodynamics,

dQ = dE + dW

Then we get,

dE = - dW

We know that the small work of expansion dW is given by P dV, where dV is the
small increase in volume and P is the pressure of the gas,

dW = P dV

Now we get,

dE = - P dV

From molar heat capacity at constant volume, Cv

Cv = dE / dT

dE = Cv dT

Hence,

Cv dT = - P dV

We know that, for 1 mole of an ideal gas,

PV = RT

P = RT / V

Now we can substitute the value of P in above equation,

Cv dT = - RT / V. dV
 Cv .dT /T = - R. dV/ V

Integrating the above equation between the limits T1 & T2 and V1 & V2, we get,
𝑇2 𝑑𝑇 𝑉2 𝑑𝑉
Cv ∫𝑇1 = −𝑅 ∫𝑉1
𝑇 𝑉

𝑇2 𝑉2
𝐶𝑣. 𝐼𝑛 = −𝑅 ln
𝑇1 𝑉1
𝑇2 𝑉1
𝐶𝑣. 𝐼𝑛 = 𝑅 ln
𝑇1 𝑉2
𝑇2 𝑉1
𝐶𝑣. 𝐼𝑛 = ( 𝐶𝑝 − 𝐶𝑣 ) ln
𝑇1 𝑉2
𝑇2 (𝐶𝑝 − 𝐶𝑣) 𝑉1
𝐼𝑛 = ln
𝑇1 𝐶𝑣 𝑉2
𝑇2 𝑉1
𝐼𝑛 =(γ − 1)ln
𝑇1 𝑉2
𝑇2 𝑉1
𝐼𝑛 = ln [ ] γ−1
𝑇1 𝑉2
Taking antilogarithm of both sides, we get
𝑇2 𝑉1
= ( ) γ−1
𝑇1 𝑉2
𝑇1( 𝑉1) γ−1 = 𝑇2( 𝑉2) γ−1

𝑇 𝑉 γ−1 = Constant

According to ideal gas equation,

𝑃1𝑉1 𝑃2𝑉2
=
𝑇1 𝑇2
𝑇2 𝑃2𝑉2
=
𝑇1 𝑃1𝑉1
𝑇2 𝑃2𝑉2 𝑉1 γ−1
= =( )
𝑇1 𝑃1𝑉1 𝑉2

𝑃2 𝑉1 γ
=( )
𝑃1 𝑉2

𝑃1(𝑉1γ ) = 𝑃2(𝑉2γ )
 𝑃𝑉 γ = constant

Work done in an adiabatic reversible expansion of an ideal gas:

We know that, for an adiabatic process,

𝑃𝑉 γ = constant

Differentiating the above equation, we get

P (γ 𝑃𝑉 γ−1 ) dV + 𝑉 γ dP = 0

γ 𝑃𝑉 γ−1 dV + 𝑉 γ dP = 0

On dividing throughout by 𝑉 γ−1 , we get

γ P dV + V dP = 0

V dP = - γ P dV

( For n moles of an ideal gas PV = nRT

On differentiation, we get

P dV + V dP = nR dT

V dP = nR dT - P dV )

Now,

V dP = - γ P dV = nR dT – P dV

P dV - γ P dV = nR dT

(1- γ)P dV = nR dT
P dV = 1/(1- γ) nR dT
The work done during the reversible adiabatic expansion of an ideal gas is,
𝑉2
W = ∫𝑉1 𝑃 𝑑𝑉

𝑇2 𝑛𝑅
W = ∫𝑇1 𝑑𝑇
(1−γ)

𝑛𝑅 𝑇2
W=
(1−γ)
∫𝑇1 𝑑𝑇
 𝑛𝑅
W= (𝑇2 − 𝑇1)
(1−γ)

Variation of Heat off a reaction or Enthalpy of formation with temperature

Kirchoffs equation

Statement: The change in the heat of a reaction t constant pressure for every degree
change of temperature is equal to the change in the heat capacity at constant pressure.
Mathematically it is expressed as follows,

ΔH2 − ΔH1
= ΔCp
𝑇2 − 𝑇1
The amount of heat evolved or absorbed in a process, varies with temperature. The
exact relationship showing the variation of the heat of reaction with temperature
was given by Kirchoff in 1858. It can be derived easily with the help of the first
law of thermodynamics.

Consider the simple process,

A (reactants) ----------→ B (products)

Now, suppose HA & HB are the heat contents or enthalpies of the reactants and
products respectively. Then the heat of reaction accompanying the process will be
given by,

ΔH = HB - HA

Differentiating the equation with respect to temperature at constant pressure, we

get
d(Δ𝐻) dHB d(HA)
[ ]= [ ]− [ ]
dT dT dT
According to the definition of heat capacity at constant pressure,
𝑑𝐻
Cp = [ ]
𝑑𝑇

d(Δ𝐻)
[ dT
] = (Cp)B – (Cp)A
Where, (Cp)B, (Cp)A are the mean molar heat capacities of the products and
reactants respectively at the given pressure.
d(Δ𝐻)
= 𝛥Cp
dT

d (ΔH) = 𝛥Cp . dT

This is only for a small temperature difference, dT. The equation for large
temperature difference (say T1 and T2) can be obtained by integrating the above
equation between the limits.
𝐻2 𝑇2
∫𝐻1 𝑑(𝛥H) = ∫𝑇1 𝛥Cp . dT

𝛥H2 – 𝛥H1 = 𝛥Cp (T2 – T1)

Where, 𝛥Cp has been assumed to be constant within temperature range from T1 to
T2

Then, finally we get the famous Kirchoffs equation as,

𝛥H2 – 𝛥H1
= 𝛥Cp
T2 – T1

The change in the heat of reaction at constant pressure for every degree change of
temperature is equal to the change in the heat capacity at constant pressure.

When the reaction is carried out at constant volume:

We know that,

H = E + PV and

𝛥H = 𝛥E + P 𝛥V

𝛥H = 𝛥E (at constant volume, 𝛥V = 0)

Then,
𝛥E2 – 𝛥E1
= 𝛥Cv
T2 – T1

This is known as the Kirchoffs equation at constant volume and is defined as, the
change in the heat of a reaction at constant volume for every change of temperature
is equal to the change in the heat capacity at constant volume.
 Second law of thermodynamics

The important limitation of first law of thermodynamics is that, it does not state
whether a reaction is spontaneous or not and in which direction it will occur.

Second law of thermodynamics is concerned with the direction and spontaneity of

processes. It can be defined in several ways; the most common statements are as
below,

1. Statement: All spontaneous processes are thermodynamically irreversible.

A process which proceeds of its own accord, without the help of any external
agency is called a spontaneous process. All natural processes are spontaneous.
Further since the spontaneous processes cannot be reversed without the help of an
external agency and these are also said to be irreversible.
2. Clausius statement: Heat cannot itself pass from a colder body (low temperature
region) to a hotter body (High temperature region) without use of any external
agency.
Second law is used to determine the theoretical limits for the performance of many
engineering systems like Heat engines and heat pump.
3. Kelvin – Planck statement: It is impossible to convert heat completely into
equivalent amount of work without producing changes elsewhere.
No heat engine has a 100% thermal efficiency
4. In terms of Entropy: the main outcome of second law is the concept of entropy.
i. Any change in a system which is accompanied by an increase in entropy tends to
be spontaneous.
ii. The energy of the universe is remains constant while the entropy of the universe is
continuously increasing and tends towards a maximum.
The Carnot cycle:

Carnot proposed a hypothetical heat engine to show that the efficiency of a heat
engine is based upon the temperature between which it operates.

Carnot engine has following features,

i. It consists of a cylinder containing one mole of an ideal gas and fitted

with a weightless, frictionless piston so that all the operations in the cycle
are carried out reversibly, hence Carnot engine is also called reversible
heat engine.
ii. The cylinder is assumed to be insulated on all sides except at the bottom
so that heat can flow from or to the system only through the bottom.
iii. The engine has two heat reservoirs, one at a higher temperature T2 called
the source and the other at a lower temperature T1 called the sink.
iv. Operations are carried out in two way: Isothermal and adiabatic
processes.
v. The complete Carnot cycle consists of four operations. These are
represented on P – V diagram or indicator diagram.
1. Isothermal reversible expansion
2. Adiabatic reversible expansion
3. Isothermal reversible compression
4. Adiabatic reversible compression
1. Isothermal expansion: The cylinder containing one mole of the ideal gas,
occupying a volume V1, is placed in contact with the heat reservoir at a temperature
T2 (Source).The gas absorbs heat (say Q2) from the source and expands
isothermally and reversibly to volume V2.
Work done in this process is,
W1 = Q2
W1 = Q2 = RT2 ln(V2/V1)

(dE =0 as it is isothermal, hence heat absorbed is equal to the work done by the
system on the surroundings)

2. Adiabatic expansion: The cylinder is removed from the source and placed in
contact with the perfectly insulating material. Thus, the gas now expands
adiabatically and reversibly from volume V2 to V3. Work is done in the expansion
but since no heat enters or leaves the system, the temperature must fall and suppose
it drops to T1 (Temp of sink).
Work done by the system = W2
Heat absorbed by the system = 0
Now, from first law,

Q = ΔE + W
ΔE = Q – W
ΔE = - W2
But, we know that,
 ΔE = Cv (T2 – T1)
Hence,
- W2 = Cv (T2 – T1)
3. Isothermal compression: The cylinder is now removed from the insulating
material and placed in contact with the second heat reservoir at a lower temperature
T1 (sink). Since the compression takes place isothermally, ΔE = 0. Thus if Q1 is the
heat given to the sink at temperature T1 and W3 is the work done on the system,
then
- Q1 = W3 = RT1 ln (V4/V3)
4. Adiabatic compression: The cylinder is now removed from the sink and placed
again on the insulating material. The gas compressed adiabatically and reversibly
from volume V4 to the original volume V1 while the temperature rises from T1 to
the original temperature T2.

Work done on the system = -W4

ΔE = Q – (-W4)
ΔE = W4 = Cv (T2 – T1)
- W4 = - Cv (T2 – T1)

Net work done in one cycle: the net work done in one cycle is obtained by adding
the work done in the four processes.

W = W1 + W2 + (-W3 ) + (-W4 )

W = RT2 ln(V2/V1) + Cv (T2 – T1) + RT1 ln (V4/V3) - Cv (T2 – T1)

W = RT2 ln(V2/V1) + RT1 ln (V4/V3)

Net heat absorbed in one cycle: The net heat absorbed in the whole cycle is given
by,

Q = Q2 + 0 + (- Q1) + 0

Q = Q2 - Q1
𝑉2 𝑉4
Q = RT2 ln ( ) - [−𝑅𝑇1 ln ]
𝑉1 𝑉3

𝑉2 𝑉4
Q = RT2 ln ( ) + RT1 ln ( )
𝑉1 𝑉3

Since, V1 and V4 lie on the same adiabatic curve and for adiabatic change,

𝑇 𝑉 γ−1 = Constant
 (V4 /V1) (Γ-1) = T2 / T1

Similarly, V2 and V3 lying on the same adiabatic curve, it follows that,

(V3 /V2) (Γ-1) = T2 / T1

Therefore,

(V4 /V1) (Γ-1) = (V3 /V2) (Γ-1

𝑉4 𝑉3
=
𝑉1 𝑉2

V4 / V3 = V1 / V2

Now,

W = W = RT2 ln(V2/V1) + RT1 ln (V4/V3)

W = RT2 ln(V2/V1) + RT1 ln (V1/V2)
W = RT2 ln(V2/V1) - RT1 ln (V2/V1)
W = R(T2 – T1) ln(V2/V1)

Efficiency of a heat engine: The fraction of the heat absorbed by a machine that
it can be transform into work is called efficiency of the engine. It is expressed as,

η=W/Q

Hence,

η = W / Q2

η = (T2 – T1) / T2 = (Q2 – Q1) / Q2

η = 1 – (T1 / T2)

It is concluded that, η < 1 (Efficiency of heat engine is always less than 100%).

Carnot theorem:

Carnot theorem stated that every machine working reversibly between the same
temperatures of source and sink have the same efficiency whatever be the nature
of the substance used.
 T2 – T1
η=
𝑇2

Q2 – Q1
η=
𝑄2

From the above two equations it is clear that the efficiency of an engine working
reversibly depends only on the temperature of the source and sink. It is independent
of the nature of the substances used.

Entropy:

Entropy is regarded as a measure of the disorder or randomness of a system. More

disordered system having higher entropy. All spontaneous processes lead to an
increase in entropy.

Entropy is a definite quantity and its value is independent of the path taken for the
change and depends only upon the initial and final states of the system, hence
entropy is a state function.

The change in entropy of the system is defined as the quantity of heat absorbed
isothermally and reversibly divided by the absolute temperature at which heat is
absorbed.
𝑄
ΔS =
𝑇

Entropy change in a reversible process:

In a thermodynamically reversible process, the entropy of the system and its

surroundings remains constant.

Consider a process occurring completely reversible conditions. If Qrev is the heat

absorbed reversibly by the system and then Q rev will be the heat lost by the
surroundings. Now, if the process takes place isothermally at absolute temperature
T, then

Entropy change of the system is given by,

 𝑄𝑟𝑒𝑣
ΔSsystem =
𝑇

Entropy change of the surroundings is,

𝑄𝑟𝑒𝑣
ΔSsurroundings = -
𝑇

Total entropy change is,

𝑄𝑟𝑒𝑣 𝑄𝑟𝑒𝑣
ΔSsystem + ΔSsurroundings = -
𝑇 𝑇

ΔSsystem + ΔSsurroundings = 0

Thus, in a reversible process, the net entropy change for the combined system and
the surroundings is zero, i.e., in a thermodynamically reversible process, the
entropy of the system and its surroundings remains constant.

Entropy change in an irreversible process: Spontaneous process:

A thermodynamically irreversible process is accompanied by an increase in the

entropy of the system and its surroundings.

If any part of the process is irreversible, the process as a whole is irreversible. If

the total heat lost by the surroundings is Qirrev then the heat absorbed by the system
will also be Qirrev . However, entropy change of the system does not depend upon
the actual heat absorbed but it depends upon the heat absorbed reversibly.
𝑄𝑟𝑒𝑣
ΔSsystem =
𝑇

𝑄𝑖𝑟𝑟𝑒𝑣
ΔSsurroundings = -
𝑇

The total entropy change,

𝑄𝑟𝑒𝑣 𝑄𝑖𝑟𝑟𝑒𝑣
ΔSsystem + ΔSsurroundings = -
𝑇 𝑇

We know that, Wrev > Wirrev and hence

Qrev > Qirrev

𝑄𝑟𝑒𝑣 𝑄𝑖𝑟𝑟𝑒𝑣
>
𝑇 𝑇

𝑄𝑟𝑒𝑣 𝑄𝑖𝑟𝑟𝑒𝑣
- >0
𝑇 𝑇
 ΔSsystem + ΔSsurroundings > 0

Thus, in an irreversible process, the entropy change for the combined system and
the surroundings is greater than zero, i.e., a thermodynamically irreversible process
is accompanied by an increase in the entropy of the system and its surroundings.

All spontaneous processes are thermodynamically irreversible and are

accompanied by a net increase in entropy – 2nd law of thermodynamics.
 Thermodynamics
Question Bank

Essays Questions: 10 M
1. State and explain 1st law of thermodynamics
2. Derive Kirchhoff’s equation and mention its applications
3. Show that PVr = Constant
4. State and explain Second law of thermodynamics.
5. Explain Joule- Thomson effect
6. Explain Carnot cycle.
7. Show that CP-CV=R
8. Write about the concept of entropy. Explain about the entropy change
in a reversible and irreversible processes
Short answer questions: 5 M
1. Prove that Cp - Cv = R
2. Write about Entropy
3. State and explain Joule- Thomson Effect
4. Write briefly about enthalpy and Internal energy
5. State and explain about second law of thermodynamics