Thermodynamics

Thermodynamics is the study of the effects of work, heat, and energy on a system
Thermodynamics is only concerned with macroscopic (large-scale) changes and observations

Basic terminologies in Thermodynamics

System and surrounding

System

A thermodynamic system is defined as the quantity of matter or a region in space upon which
attention is concentrated in the analysis of a problem.

Surroundings

Everything external to the system is called the surroundings or environment.

There are three types of system as:

Isolated System – An isolated system cannot exchange both energy and mass with its
surroundings. The universe is considered an isolated system.

Closed System – Across the boundary of the closed system, the transfer of energy takes place
but the transfer of mass doesn’t take place. Refrigerator, compression of gas in the piston-
cylinder assembly are examples of closed systems.

Open System – In an open system, the mass and energy both may be transferred between the
system and surroundings. A steam turbine is an example of an open system.
 System and surroundings

Different types of systems

Intensive and Extensive property : Intensive property is a physical property of a system that
does not depend on the system size or the amount of material in the system. By contrast, an
extensive property of a system does depend on the system size or the amount of material in the
system. According to the definitions, density, pressure and temperature are intensive properties
and volume, internal energy are extensive properties.

State function: A property that depends on the initial (state 1 or i) and final state (2 or f) but is
independent of the path used to reach from. Example: Temperature, pressure, internal energy,
enthalpy.

Path function: A property that depends on the path between the initial (A or i) and final state
(B or f) (example, W i.e. work done, q i.e heat transferred)

Internal energy

• In thermodynamics, the total energy of a system is called its internal energy, U. The
internal energy is the total kinetic and potential energy of the constituents (the atoms,
 ions, or molecules) of the system. It does not include the kinetic energy arising from
the motion of the system as a whole, That is, the internal energy is the energy ‘internal’
to the system.
• The change in internal energy is denoted by ΔU when a system changes from an initial
state i with internal energy 𝑈𝑖 to a final state f of internal energy 𝛥𝑈 = 𝑈𝑓 − 𝑈𝑖

• Internal energy is a state function.

• Internal energy is an extensive property of the system.
• Internal energy of a system changes when energy is transferred into or outside the

t and work system in the form heat or work

The total energy of a system is called its internal energy (U) –

Thermodynamic
it changes when energy processes
is transferred into or out of the system.
• There are a number of different thermodynamic processes that can change the
pressure and/or the volume and/or the temperature of a system.

Adiabatic – no heat transferred

Isothermal – constant temperature
Isobaric – constant pressure
Isochoric – constant volume

Work done on/by the system

• Work is simply a force multiplied by the distance moved in the direction of the force.
A good example of a thermodynamic system that can do work is the gas confined by a
piston in a cylinder, as shown in the diagram below (an example of a closed system).
 • If the gas is heated, it will expand and push the piston up, thereby doing work on the
piston. This is an example of how work is done by a thermodynamic system. The work
done when the system expands by dV against a pressure Pex is dw = −PexdV .
𝑣
Total work done by the system to expand from volume Vi to Vf: W = -∫𝑣 𝑓 𝑃𝑒𝑥 dv
𝑖

This is an example of the system doing the work on the surrounding.

• If the piston is pushed down, on the other hand, the piston does work on the gas. This
is an example of the surrounding doing work on the system.
• If the volume doesn't change, no work is done.

• If the external pressure is constant throughout the expansion, 𝑤 = −𝑝𝑒𝑥𝛥𝑉 (example of

irreversible expansion as discussed later)

Reversible process in thermodynamics

A thermodynamics process is reversible if the process can be turned back such that both the
system and the surroundings return to their original states, with no other change anywhere else
in the universe. In reality, no such processes as reversible processes can exist. Thus, a more
appropriate definition is a reversible change in thermodynamics is a change that can be
reversed by an infinitesimal modification of a variable.

Example 1) thermal equilibrium of two systems with the same temperature : If the
temperature of either system is lowered infinitesimally, then energy flows into the system with
the lower temperature. On the other hand, if the temperature of either system at thermal
equilibrium is raised infinitesimally, then energy flows out of the hotter system.

Example 2) is reversible expansion: Suppose a gas is confined by a piston and that the external
pressure, Pex, is set equal to the pressure, P, of the confined gas. Such a system is in mechanical
equilibrium with its surroundings because an infinitesimal change in the external pressure in
either direction causes changes in volume in the opposite directions.

If Pex becomes infinitesimally smaller than P, then the gas will undergo infinitesimal expansion
If Pex becomes infinitesimally larger than P, then the gas will undergo infinitesimal contraction

If Pext>>> 𝑃, an infintesimally decrease in Pext will not make it smaller than P and thus the
direction of the process will not be changed. Here, the system is not in mechanical equilibrium
with the surrounding.

To achieve reversible expansion Pex is set equal to P at each stage of the expansion.

dw = −𝑝𝑒𝑥𝑑𝑉 = −𝑝𝑑𝑉
𝑣
W = - ∫𝑣 𝑓 𝑝dv
𝑖

Examples of Reversible Process

• extension of springs
• slow adiabatic compression or expansion of gases
• electrolysis (with no resistance in the electrolyte)
• the frictionless motion of solids
• slow isothermal compression or expansion of gases
 Zeroth law of thermodynamics

Thermal equilibrium: Two physical systems are in thermal equilibrium if there is no net
flow of heat (thermal energy) between them when they are connected by a path permeable to
heat.

The zeroth law of thermodynamics defines thermal equilibrium and forms a basis for the
definition of temperature. The Zeroth law says that If two systems are in thermal equilibrium
with a third system, then those two systems are in thermal equilibrium with each other.

First law of thermodynamics

The first law of thermodynamics is an extension of the law of conservation of energy. The
internal energy of a system may be changed either by doing work on the system or by heating
it. Heat and work are equivalent ways of changing the internal energy of a system

Example: if a weight has been raised or lowered in the surroundings, transfer of energy happens
by doing the work.
if ice has melted in the surroundings, it indicated transfer of energy as heat.

If w is the work done on a system, q is the energy transferred as heat to a system, and ΔU is
the resulting change in internal energy, then 𝛥𝑈 = 𝑞 + 𝑤

The sign of w and q are positive if energy is transferred to the system as work or heat and are
negative if energy is lost from the system.

Thus, the change in internal energy of a system is equal to the heat added to the system minus
the work done by the system
𝛥𝑈 = 𝑞 − 𝑤

For an isolated system, internal energy is constant in an isolated system (for which q = 0 and
w = 0).

Enthalpy
Suppose, the change of a system is brought about at constant pressure, So, there will be change
in volume.
Vi = volume of the initial state, Vf = volume of the final state.
Work done by the system = 𝑤 = −𝑃 (𝑉𝑓 − 𝑉𝑖 )
ΔU = q + W= q - P (𝑉𝑓 − 𝑉𝑖 ) or 𝑈𝑓 − 𝑈𝑖 = q – P (𝑉𝑓 − 𝑉𝑖 ) or (𝑈𝑓 + 𝑃𝑉𝑓 ) − (𝑈𝑖 + 𝑃𝑉𝑖 ) = 𝑞
The quantity U+PV is called the enthalpy of the system and is denoted by H.
ΔH = ΔU + P ΔV

Heat Capacity (An extensive property)

Heat capacity of a system between any two temperatures is defined as the quantity of heat (q)
required to raise the temperature of the system from the lower temperature to the higher
temperature divided by the temperature difference.

If mass of the system is 1 g, the heat capacity is called the specific heat of the system
For 1 mol of substance, the heat capacity is termed as ‘molar heat capacity’.

Molar heat capacity of a system between temperatures T 1 and T2 are:

𝑞
𝐶=
𝑇2 − 𝑇1
𝑑𝑞
Molar heat capacity varies with temperature: C= 𝑑𝑇

Molar heat capacity at constant volume is denoted as Cv

𝝏𝑼
At constant volume w = 0, so, ΔU = q, 𝑪𝒗 = ( 𝝏𝑻 )
𝒗

Molar heat capacity at constant pressure is denoted as Cp

At constant pressure, there is change in volume and some work is done,

 q = ΔU -w = ΔU –(-PΔV)

𝝏𝑯
𝑪𝒑 = ( )
𝝏𝑻 𝒑

Thus, molar heat capacity of a gaseous system of mass one mole at constant volume is defined
as the increase in internal energy of the system per degree rise of temperature and at constant
pressure, it is defined as the increase in enthalpy of the system per degree rise of temperature.

Heat capacity of Ideal gas

When a gas is heated at constant volume, no work is done by the gas i.e. all heat supplied to
the gas is used to increase its internal energy. If the temperature of 1 mole of gas is raised
through 1C, the increase in internal energy gives the molar heat capacity at constant volume.

When the gas is heated at constant pressure there will be increase in volume i.e the gas will
expand and will do some external work. Therefor some extra heat in addition to what is
required to increase its internal energy will be required to enable the gas to perform external
work.

𝑪𝒑 > 𝑪𝒗
CV = 3/2 R (For monoatomic ideal gas)
CP = 5/2 R (For monoatomic ideal gas)

𝑪𝒑 − 𝑪𝒗 = 𝑹 (for 1 mole, For all gases)

𝑪𝒑
𝜸= = 5/3 for a monoatomic ideal gas
𝑪𝒗

Application of first law to the expansion work

Pressure-volume graph

As an aid in calculating the work done, it's a good idea to draw a pressure-volume (P-V) graph
(with pressure on the y axis and volume on the x-axis). If a system moves from one point on
the graph to another and a line is drawn to connect the points, the work done is the area
underneath this line. We'll go through some different thermodynamic processes and see how
this works.

Thermodynamic processes

Isothermal – constant temperature process

An isothermal process is a constant temperature process. Any heat flow into or out of the
system must be slow enough to maintain thermal equilibrium. In an isothermal process, the
temperature stays constant, so the pressure and volume are inversely proportional to one
another. The P-V graph for an isothermal reversible process looks like this:

The internal energy of an ideal gas is proportional to the temperature, so if the temperature is
kept fixed the internal energy does not change. The first law, which deals with changes in the
internal energy, thus becomes 0 = 𝑞 − 𝑊, so 𝑞 = 𝑊.

If the system does work, the energy comes from heat flowing into the system from the
surrounding; if work is done on the system, heat flows out of the system to the surrounding.

ΔU = 0
ΔH = ΔU + ΔPV = ΔU + ΔnRT =0
ΔU = q + w or q = -W i.e. work done by the system occurs at the expense of the heat
absorbed.

Magnitude of W depends on whether the expansion is reversible or irreversible.

Reversible isothermal expansion:

𝑣
W = ∫𝑣 𝑓 𝑃dv (throughout the expansion, Pex =P as the expansion is reversible)
𝑖

Work done by the n moles of gas is evaluated as:

𝑉𝑓 𝑃
W = −𝑛𝑅𝑇 ln 𝑉 = −𝑛𝑅𝑇 ln 𝑃 𝑖
𝑖 𝑓
The work done by a perfect gas when it expands reversibly and isothermally is equal to the
area under the isotherm p = nRT/V. The work done during the irreversible expansion against
the same final pressure is equal to the rectangular area shown slightly darker. Note that the
reversible work done is greater than the irreversible work done. (From Peter Atkins)

Relations for Irreversible Isothermal expansion

Two kinds of irreversible isothermal expansion

a) Free expansion (expansion in vacuum)

𝑣
W = -∫𝑣 𝑓 𝑃𝑒𝑥 dv =0
𝑖
b) Volume of the gas expands against a constant pressure.
𝑣
W = -∫𝑣 𝑓 𝑃𝑒𝑥 dv = -Pex (Vf-Vi)
𝑖

Adiabatic process (constant heat process)

In an adiabatic process, no heat is added or removed from a system. The first law of
thermodynamics is thus reduced to saying that the change in the internal energy of a system
undergoing an adiabatic change is equal to -W.

An example of an adiabatic process is a gas expanding so quickly that no heat can be

transferred. The expansion does work, and the temperature drops. This is exactly what happens
with a carbon dioxide fire extinguisher, with the gas coming out at high pressure and cooling
as it expands at atmospheric pressure.
No heat is allowed to enter or leave the system, q = 0.

∆𝑈 = 0 + 𝑊 𝑜𝑟 𝑊 = ∆𝑈

Expansion: W is negative. So, ∆𝑈 is negative. So, temperature of the system falls during
expansion. In this case, work is done by the system at the expense of its internal energy.

W =∆𝑈 = 𝑪𝒗 𝚫𝑻 (for 1 mole of gas)

∆𝐻 = 𝑪𝒑 𝚫𝑻 (for 1 mole of gas)

Reversible adiabatic expansion

Relation between temperature, volume and pressure

𝑇𝑖 𝑉𝑓 𝛾−1
( )= ( )
𝑇𝑓 𝑉𝑖
𝛾
𝑇𝑖 𝑉𝑓 1−𝛾
( ) = ( )
𝑇𝑓 𝑉𝑖

𝑇𝑓 𝑉𝑖
𝐶𝑣 ln = 𝑅 ln
𝑇𝑖 𝑉𝑓

Irreversible adiabatic expansion

Free expansion (external pressure is zero) : ∆𝑇 = 0, 𝑊 = 0, ∆𝐻 = 0

𝑇𝑖 𝑃𝑓 −𝑇𝑓 𝑃𝑖
Expansion against a constant pressure: 𝐶𝑣 (𝑇𝑓 − 𝑇𝑖 ) = 𝑅 𝑃𝑒𝑥 ( )
𝑃𝑖 𝑃𝑓
Isobaric process (constant pressure)

Isobaric - the pressure is kept constant. An example of an isobaric system is a gas, being slowly
heated or cooled, confined by a piston in a cylinder. The work done by the system in an isobaric
process is simply the pressure multiplied by the change in volume, and the P-V graph looks
like:

Isochoric – constant volume process

Isochoric - the volume is kept constant. An example of this system is a gas in a box with fixed
walls. The work done is zero in an isochoric process, and the P-V graph looks like

Numericals from the First law of thermodynamics

Example 1: Calculate w and ∆𝑈 for the conversion of 1 mole of water at 100℃ to steam at 1
atm pressure. Heat of vaporisation of water at 100℃ is 40670 Jmol-1

P = 1 atm = 101325 Nm-2

Vi = volume of 1 mole of liquid water at 1 atm pressure = 18 ml = 18 × 10-6 m3
Vf = volume of 1 mole of steam at 100℃ at 1 atm pressure = (22.4 dm3 × 373)/273 = 30.60
dm3 = 0.0306 m3
W = P (Vf - Vi) = 101325 Nm-2 (0.0306 m3-(18 × 10-6 )m3) = 101325 Nm-2 × 0.0306 m3 = 3100
Jmol-1

Since, conversion of water to steam is accompanied by increase in volume, work is done by

the system on the surroundings. Hence, w = -3100 Jmol-1

Example 2: 1 mole of an ideal gas expands against a constant external pressure of 1 atm from
a volume of 10 dm3 to a volume of 30 dm3. Calculate the work done by the gas in Joules.

𝑤 = −𝑝𝑒𝑥𝛥𝑉, 𝑊 = −(1 𝑎𝑡𝑚) (30 𝑑𝑚3 − 10𝑑𝑚3 ) = −20 𝑑𝑚3 𝑎𝑡𝑚

R = 8.314 Jmol-1K-1 = 0.08206 dm3 atm K-1 mol-1

8.314 𝐽 𝑚𝑜𝑙−1 𝐾−1

1 atm = 0.08206 𝑑𝑚3 𝑚𝑜𝑙−1 𝐾−1

−1
8.314 𝐽 𝑚𝑜𝑙 𝐾−1
𝑤 = −20 𝑑𝑚3 𝑎𝑡𝑚 = −20 𝑑𝑚3 × −1 = -2026 J
0.08206 𝑑𝑚 3 𝑚𝑜𝑙 𝐾−1

Example 3: 1 mole of an ideal monoatomic gas at 27 C expands reversibly and adiabatically

from a volume of 10 dm3 to a volume of 20 dm3. Calculate q, ∆U, W and ∆H. Given
𝐶𝑣 3
=
𝑅 2

Solution: Since the process is adiabatic, q = 0

𝑇𝑓 𝑉
𝐶𝑣 ln 𝑇 = 𝑅 ln 𝑉 𝑖
𝑖 𝑓

3 𝑇𝑓 10 𝑑𝑚3
or 2 ln 300 = ln 20 𝑑𝑚3

or Tf = 189K

𝜕𝑈
𝐶𝑣 = ( 𝜕𝑇 ) or 𝑑𝑈 = 𝐶𝑣 𝑑𝑇
𝑣

For a finite change in n moles, ∆𝑈 = 𝑛𝐶𝑣 ∆𝑇

3
or ∆𝑼 = (1 mol)(2 × 8.314 𝐽 𝑚𝑜𝑙 −1 𝐾 −1 ) (189 − 300)𝐾 = -1384 J
Since for an adiabatic process, q =0, hence ΔU = w, w=-1384 J
ΔH = ΔU + ΔPV = ΔU + ΔnRT = ΔU + nR(Tf- Ti)

𝑛𝑅(𝑇𝑓 − 𝑇𝑖 ) = (1 mol)( 8.314 𝐽 𝑚𝑜𝑙 −1 𝐾 −1 ) (189 − 300) = −923 𝐽

ΔH = -1384 J -923 J = -2307 J

Note: ΔH can also be calculated by using the relation 𝒅𝑯 = 𝑪𝒑 𝒅𝑻

Example 4: 10 moles of an ideal gas expands reversibly and isothermally from a pressure of
10 atm to 2 atm at 300 K. Calculate the work done.
𝑃 10 𝑎𝑡𝑚
W = −𝑛𝑅𝑇 ln 𝑃 𝑖 = -(10 mol)(8.314 𝐽 𝑚𝑜𝑙 −1 𝐾 −1 )(300 𝐾 ) ln = -40.15 × 103J
𝑓 2 𝑎𝑡𝑚

Second law of thermodynamics

Need for the 2nd law of thermodynamics:

The first law of thermodynamics does not tell us anything about the direction of change. The
direction of spontaneous change of a process is defined by the 2nd law of thermodynamics.

2nd law of thermodynamics

Heat does not flow spontaneously from a cool body to a hotter body.

The entropy of an isolated system increases in the course of a spontaneous change: ΔStot > 0

Stot = S + Ssur , S is the entropy of the system of interest, and Ssur the entropy of the surroundings.
it is vitally important when considering applications of the Second Law to remember that it is
a statement about the total entropy of the overall isolated system (the ‘universe’), not just about
the entropy of the system of interest.

the First Law uses the internal energy to identify permissible changes; the Second Law uses
the entropy to identify which of these permissible changes are spontaneous. A spontaneous
process points towards the direction in which the total entropy increases.

Entropy is a state function.

 Notice the increasing disorder in above processes.

Thermodynamic definition of entropy

The thermodynamic definition of entropy concentrates on the change in entropy, dS, that occurs
as the result of a physical or chemical process. dqrev is the energy transferred as heat reversibly
to the system at the absolute temperature T.

𝑑𝑞𝑟𝑒𝑣⁄ 𝑓 𝑑𝑞𝑟𝑒𝑣
𝑑𝑆 = 𝑇, Δ𝑆 = ∫𝑖 𝑇

Entropy change for the system of an isothermal expansion of a perfect gas

ΔU = 0, q = -w, 𝑞𝑟𝑒𝑣 = −𝑤𝑟𝑒𝑣

wrev =- nRT ln (𝑉𝑓 /𝑉𝑖) (from the expression of work done in a reversible isothermal expression)

𝑞𝑟𝑒𝑣 = 𝑛𝑅𝑇𝑙𝑛(𝑉𝑓 /𝑉𝑖 )

Δ𝑆 = 𝑛𝑅𝑙𝑛(𝑉𝑓 /𝑉𝑖 )

Δ𝑆𝑚 = 𝑅𝑙𝑛(𝑉𝑓 /𝑉𝑖 )

Total Entropy change in Reversible and the Irreversible (spontaneous) of a
perfect gas:

Irreversible process (example: Isothermal expansion of an ideal gas at constant temperature

into vacuum, this process is spontaneous and irreversible)

w = 0, 𝛥𝑈 = 0 Hence, from the first law, 𝑞 = 0 i.e. no heat is absorbed by or removed

from the surrounding. Hence, the entropy of the surrounding remains unchanged.

Δ𝑆𝑚 = 𝑅𝑙𝑛(𝑉𝑓 /𝑉𝑖 ).

𝑆𝑡𝑜𝑡𝑎𝑙 = 𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + 𝑆𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔

𝑆𝑡𝑜𝑡𝑎𝑙 = 𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + 𝑆𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔 = 𝑅𝑙𝑛(𝑉𝑓 /𝑉𝑖 )+ 0 = 𝑅𝑙𝑛(𝑉𝑓 /𝑉𝑖) (As Vf > 𝑉𝑖, this
spontaneous (irreversible) isothermal expansion of a gas is accompanied by the increase in
entropy.)

Isothermal Reversible expansion

w = −𝑝Δ𝑉
qrev =𝑝Δ𝑉

𝑞𝑟𝑒𝑣 𝑞𝑟𝑒𝑣
𝑆𝑡𝑜𝑡𝑎𝑙 = 𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + 𝑆𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔 = ( 𝑇
) + (− 𝑇
) =0

Entropy change during reversible and irreversible process and the spontaneity

Thus, a thermodynamically irreversible process is always accompanied by the increase in total

(entropy of the system and surrounding taken together) entropy whereas in a thermodynamic
reversible process, total entropy remains unchanged. This is expressed by Clausius inequality

𝑑𝑞
dS ≥ 𝑇

Physical significance of Clausius inequality: In an isolated system, there is no heat transfer

and = 0 , thus dS ≥ 0 implying that all natural processes are spontaneous and irreversible.

Reversible process: 𝑑𝑆𝑡𝑜𝑡𝑎𝑙 = 𝑑𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + 𝑑𝑠𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔 = 0, spontaneous in neither

direction and is at equilibrium

Irreversible process: 𝑑𝑆𝑡𝑜𝑡𝑎𝑙 > 𝑑𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + 𝑑𝑠𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔 > 0,

The above understanding is of paramount importance. As all spontaneous process occurring in
nature is irreversible, entropy of the universe is increasing continuously.

The first law and the 2nd law of thermodynamics were thus summed up by the German Physicist
Rudolf Clausius as below:

The energy of the universe remains constant; the entropy of the universe tends towards a
maximum’

Entropy change during different processes

Entropy change of an ideal gas (1 mole) when T and V are the two variables:
𝑇𝑓 𝑉𝑓
∆𝑆 = 𝐶𝑣 ln 𝑇 + 𝑅 ln 𝑉
𝑖 𝑖
𝑇𝑓 𝑃𝑓
Entropy change of an ideal gas when T and P are the two variables: ∆𝑆 = 𝐶𝑝 ln 𝑇 − 𝑅 ln 𝑃
𝑖 𝑖

𝑉𝑓 𝑃𝑓
Entropy change of an ideal gas in an isothermal process: ∆𝑆𝑇 = 𝑅 ln 𝑉 = -𝑅 ln 𝑃
𝑖 𝑖
𝑇𝑓
Entropy change of an ideal gas in an isobaric process: ∆𝑆𝑃 = 𝐶𝑝 ln 𝑇
𝑖
𝑇𝑓
Enyropy change of an ideal gas isochoric process: ∆𝑆𝑣 = 𝐶𝑣 ln 𝑇
𝑖

Heat engine

• A device which transforms heat into work is called a heat engine.

• This happens in a cyclic process
• Heat engines require a hot reservoir to supply energy (QH) and a cold reservoir to take
in the excess energy (QC)
– QH is defined as positive, QC is negative

Carnot Cycle

A Carnot cycle, which is named after the French engineer Sadi Carnot, consists of four
reversible stages in which a gas (the working substance) is either expanded or compressed in
various ways.
Four stages of Carnot Cycle:

Carnot employed a reversible cycle to demonstrate the maximum convertibility of heat into
work. The system consists of 1 mole of an ideal gas which is subjected to four strokes.

1. 1st stroke: Curve AB: A→B: Isothermal expansion at Th, Work done by the gas

Explanation: The gas is placed in thermal contact with a hot source (which is at
temperature Th) and undergoes reversible isothermal expansion from A to B; the
entropy change is qh/Th, where qh is the energy supplied to the system as heat from the
hot source.

𝑉𝐵
𝑞ℎ = −𝑤1 = 𝑅𝑇ℎ ln
𝑉𝐴

2. 2nd stroke: Curve BC (B → C): Adiabatic expansion, Work done by the gas

Explanation: Contact with the hot source is broken and the gas then undergoes
reversible adiabatic expansion from B to C. No energy leaves the system as heat, so the
change in entropy is zero. The expansion is carried on until the temperature of the gas
falls from Th to Tc, the temperature of the cold sink.

−𝑤2 = −𝐶𝑣 (𝑇ℎ − 𝑇𝑐 )

3. 3rd stroke: Curve CD (C → D): Isothermal compression at TC, Work done on the gas.

Explanation: The gas is placed in contact with the cold sink and then undergoes a
reversible isothermal compression from C to D at Tc. Energy is released as heat to the
cold sink; the change in entropy of the system is qc/Tc; in this expression qc is negative.
 𝑉𝐷
−𝑞𝑐 = 𝑤3 = 𝑅𝑇𝑐 ln
𝑉𝐶

4. 4th stroke: Curve DA (D → A): Adiabatic compression, Work done on the gas

Explanation: Finally, contact with the cold sink is broken and the gas then undergoes
reversible adiabatic compression from D to A such that the final temperature is Th. No
energy enters the system as heat, so the change in entropy is zero.

𝑤4 = 𝐶𝑣 (𝑇ℎ − 𝑇𝑐 )

The area enclosed by the four curves represents the net work done by the engine in one cycle

The total change in entropy around the cycle is the sum of the changes in each of these four
steps:
𝑞ℎ 𝑞𝑐
∮ 𝑑𝑆 = 𝑇ℎ
+
𝑇𝑐

For an ideal gas, ∮ 𝑑𝑆 = 0

𝑞ℎ 𝑇
Also, = − 𝑇ℎ
𝑞𝑐 𝑐

Efficiency of a heat engine

• The thermal efficiency of a heat engine is

𝑤𝑜𝑟𝑘 𝑝𝑒𝑟𝑓𝑜𝑟𝑚𝑒𝑑 𝑊
𝜂=
ℎ𝑒𝑎𝑡 𝑎𝑏𝑜𝑠𝑟𝑏𝑒𝑑 𝑓𝑟𝑜𝑚 𝑡ℎ𝑒 ℎ𝑜𝑡 𝑠𝑜𝑢𝑟𝑐𝑒
=
𝑞ℎ
= 1 − 𝑞𝑐 /𝑞ℎ = 1 − 𝑇𝑐 /𝑇ℎ

• The “engine” statement of the 2nd Law:

– it is impossible for any system to have an efficiency of 100% (𝜂 = 1) [Kelvin’s
statement]
• Another statement of the 2nd Law:
– It is impossible for any process to have as its sole result the transfer of heat
from a cooler object to a warmer object [Clausius’s statement]

Applications of the Carnot Cycle

• Energy efficiency of the Carnot cycle is independent of its working substance.

• Any cyclic process that absorbs heat at one temperature and rejects heat at another
temperature and is reversible has the energy efficiency of a Carnot cycle.
 • Thermal devices or thermal machines are one of the applications of this cycle. The
heat pumps to produce heating, the refrigerators to produce cooling, the steam
turbines used in the ships, the combustion engines of the combustion vehicles and the
reaction turbines of the aircraft are some of the examples.

Refrigeration, Air conditioners and Heat pumps

REFRIGERATORS, AIR
These appliances CONDITIONERS,
are heat AND HEAT PUMPS
engines operating in reverse.

ese appliances
Bycan bework,
doing thought ofextracted
heat is as heatfrom the cold reservoir and exhausted to the hot reservoir.
REFRIGERATORS, AIR CONDITIONERS, AND HEAT PUMPS
gines operating in reverse.
doing work, heat isThese appliances
extracted fromcanthe
be thought
cold of as heat
engines operating in reverse.
ervoir and exhausted to the hot reservoir.
By doing work, heat is extracted from the cold
reservoir and exhausted to the hot reservoir.

Thermodynamic Temperature

Suppose an engine works reversibly between a hot source at a temperature Th and a cold sink
at a temperature T, then it follows that

T = (1 − η)Th

This expression enabled Kelvin to define the thermodynamic temperature scale in terms of
the efficiency of a heat engine

construct an engine in which the hot source is at a known tem- perature and the cold sink is
the object of interest. The temperature of the latter can then be inferred from the measured
efficiency of the engine.

The Kelvin scale (which is a special case of the thermodynamic temperature scale) is currently
defined by using water at its triple point as the notional hot source and defining that temperature
as 273.16 K exactly.
 Free energy and the spontaneity

As we have seen that the sum total of the entropy change for the system and surrounding is a
criterion for the spontaneity or feasibility of a process. Since, it is not always easy to know
the entropy change of both system and the surrounding, we can express this in terms of the
free energy function G and thus can device a criterion of spontaneity in terms of the state
function of the system.

First we will discuss the assumptions to introduce the Gibbs free energy G and Helmholtz free
energy A

Assumption no 1) the system in thermal equilibrium with its surroundings at a temperature T.

Assumption no 2) Heat transfer between the system and the surrounding happens at constant
volume.

Under the above conditions (conditions 1 and 2) Clausius inequality becomes:

𝑑𝑈
dS − 𝑇 ≥ 0 (we get this by applying the first law and the 𝑑 (𝑞𝑣 ) = 𝑑𝑈)
TdS ≥ dU

dA=dU−TdS or A=U−TS

or
Assumption no 1) the system in thermal equilibrium with its surroundings at a temperature T.

Assumption no 3) Heat transfer between the system and the surrounding happens at constant
pressure.

Under the above conditions (conditions 1 and 3) Clausius inequality becomes:

𝑑𝐻
dS − ≥ 0 (constant P, no additional work)
𝑇

TdS ≥ dH

dG=dH−TdS or G = H-TS

The criterion of spontaneity in terms of Gibbs Free energy change (dG) and Helmholtz energy
(dA)

𝒅𝑮 ≤ 𝟎 and 𝑑𝐴 ≤ 0

These criteria, especially the First, are central to chemical thermodynamics.

For instance, in an endothermic reaction H increases, dH > 0, but if such a reaction is to be

spontaneous at constant temperature and pressure, G must decrease. Because dG = dH − TdS,
it is possible for dG to be negative provided that the entropy of the system increases so much
that TdS outweighs dH. Endothermic reactions are therefore driven by the increase of
entropy of the system

Exothermic reactions are commonly spontaneous because dH < 0 and then dG < 0 provided
TdS is not so negative that it outweighs the decrease in enthalpy.

Notice that at chemical equilibrium, dG = 0

𝑃 𝑉
Free energy change with temperature and pressure: ∆𝐺 = 𝑛𝑅𝑇 ln 2 = ∆𝐺 = 𝑛𝑅𝑇 ln 1
𝑃1 𝑉2

Numericals from the 2nd law of thermodynamics

Example 1. Illustration from Atkins

Example 2: Calculate the maximum efficiency of a heat engine operating
between 100∘C and 25∘C

For engines, we have

Tc=25+273=298K

Th=100+273=373K

𝑇ℎ −𝑇𝑐 373−298
𝜂= = =0.20= 20%
𝑇ℎ 373

Example 3: Heat supplied to a Carnot engine is 1897.8 kJ. How much useful work can be
done by the engine which works between 0∘C and 100∘C

Tc=0+273=273K

Th=100+273=373K

qh = 1897.8 kJ

𝑇ℎ −𝑇𝑐 373−273
w = 𝑞ℎ × = 1897.8 kJ × = 508.7 kJ
𝑇ℎ 373
Work done by the engine is 508.7 kJ

Example 4: 5 mole of an ideal gas expands reversibly from a volume of 8 dm3 to 80 dm3 at
a temperature of 27∘C. Calculate the change in entropy.

Δ𝑆 = 𝑛𝑅𝑙𝑛(𝑉𝑓 /𝑉𝑖) = (5 mol) (8.314 J K-1mol-1) ln (80 dm3/8 dm3) = 95.73 JK-1

Example 5: Calculate the change in entropy accompanying the heating of 1 mole of Helium
gas (assumed ideal) from a temperature of 298 K to a temperature of 1000 K at constant
pressure. Assume Cv =3/2 R

As 𝐶𝑝 − 𝐶𝑣 = 𝑅 , So, Cp =𝐶𝑣 + 𝑅 = 2.5 𝑅

𝑇𝑓 1000𝐾
∆𝑆𝑃 = 𝐶𝑝 ln 𝑇 = (2.5 × 8.314 𝐽𝑚𝑜𝑙 −1 𝐾 −1 ) ln ( 298𝐾 ) =25.17 𝐽𝑚𝑜𝑙 −1 𝐾 −1
𝑖

Example 6: 1 mol of an ideal gas expands reversibly from a volume of 10 dm 3 and 298 K to a
volume of 20 dm3 and temperature 250 K. Assuming Cv =3/2 R, calculate the entropy change
for the process.
 𝑇𝑓 𝑉𝑓 250 𝐾
∆𝑆 = 𝐶𝑣 ln + 𝑅 ln = 1.5 (8.314 𝐽𝑚𝑜𝑙 −1 𝐾 −1 ) ln ( ) + (8.314 𝐽𝑚𝑜𝑙 −1 𝐾 −1 ) ln (20
𝑇𝑖 𝑉𝑖 298𝐾
dm3/10 dm3) =3.57 JK-1mol-1

Example 7: Calculate the free energy change (∆𝐺) which occurs when 1 mol of an ideal gas
expands reversibly and isothermally at 37C from an initial volume of 55 dm3 to 1000 dm3
𝑉
∆𝐺 = 𝑛𝑅𝑇 ln 𝑉1 = (8.314 𝐽𝑚𝑜𝑙 −1 𝐾 −1 ) (310𝐾 ) ln (55 dm3/1000 dm3) = -7476.8 Jmol-1
2

3rd law of thermodynamics

At T = 0, all energy of thermal motion has been quenched and in a perfect crystal all the atoms
or ions are in a regular, uniform array. The localization of matter and the absence of thermal
motion suggest that such materials also have zero entropy.

Statistical or microscopic definition of entropy: S = k ln W

S is the entropy, k is Boltzmann constant, W is the number of microstates or the total number of
ways a molecular state can be distributed over the energy states for a specific value of total
energy.

At T = 0, all molecules are in ground state and there is only one way the energy can be
distributed among different levels.

When T = 0, W = 1 and from S = klnW it follows that S = 0.

if the value zero is ascribed to the entropies of elements in their perfect crystalline form at T =
0, then all perfect crystalline compounds also have zero entropy at T = 0 (because the change
in entropy that accompanies the formation of the compounds, like the entropy of all
transformations at that temperature, is zero).
 Third law of thermodynamics: The entropy of all perfect crystalline substances is zero
at T = 0.

Chemical Kinetics

C hemical kinetics is the branch of chemistry which deals with the study of rates (or
fastness) of chemical reactions, the factors affecting it and the mechanism by which the
reactions proceed.
The rate of a chemical reaction might depend on variables such as the pressure, the temperature,
and the presence of a catalyst, and we may be able to optimize the rate by the appropriate choice
of experimental conditions.
The rates of reactions: The change in concentration of reactants or products per unit time.
Here, the instantaneous rate of disappearance of one of the reactants (A or B) at a given time,
t (at constant volume) is −d[R]/dt. Similarly, the rate of formation of one of the products is
d[P]/dt. (Note the change in the sign)
The negative sign indicates that the concentration is decreasing with time.

Time, t
Consider a general reaction, A + B → C
The rate of reaction:
d A d B  d C 
− =− =
dt dt dt
Consider another general reaction:
aA + bB → cC + dD where a, b, c d are stoichiometric coefficients
− 1 d A 1 d B 1 d C  1 d D
Rate: =− = =
a dt b dt c dt d dt
Sample questions:
1. Write rate expressions for the following reactions:
NO2 (g) + CO (g) → NO (g) + CO2 (g)
 d NO2  d CO d NO d CO2 
− =− = =
dt dt dt dt
2HI (g) → H2 (g) + I2 (g)
1 d HI  d H 2  d I 2 
− = =
2 dt dt dt

Rate laws and rate constants:

The rate law is the relationship between the rate and the concentration, which are related by a
proportionality constant k, known as rate constant.
aA + bB → cC + dD
rate = k [A]m[B]n…..where m and n are order of reaction in A and B, respectively k is the rate
constant.
This above equation is called the rate law of the reaction.

Important points about rate laws and rate constant:

(1) Rate law is a result of experimental observation. You CANNOT look at the stoichiometry
of the reaction and predict the rate law (unless the reaction is an elementary reaction).
(2) The rate law is not limited to reactants. It can have a product term,
For example: rate = k[A]m[B]n[C]c
(3) The rate constant is independent of the concentrations but depends on the temperature.
(4) The units for k vary. Determine units for k by considering units for rate and for
concentration.

Order of a reaction:
A+B→C
For rate = k[A]m[B]n, m is the order of reaction in A, n is the order of reaction in B. m and n
can be integers, fractions, negative or positive.
The overall reaction order is the sum of the exponents in the rate law.
m = 0 Zero order k[A]0
m = 1 First order k[A]
m = 2 Second order k[A]2

Examples:
H2 + Cl2 → 2HCl. Rate = k[H2]0 [Cl2]0 Zero
order
SO2Cl2(g) → SO2(g) + Cl2(g) Rate = k[SO2Cl2]1 First
order
NO2 → 2 NO + O2 Rate = k[NO2]2 Second
order
2NO(g) + 2H2(g) → 2N2 (g) + 2H2O (g) Rate = k[NO]2 [H2]1 Third
order
CH3COOC2H5 + H2O → CH3COOH + C2H5OH Rate = [CH3COOC2H5]1[H2O]0 pseudo-first-
order

Integrated rate laws:

Since rate laws are in differential form, we must integrate them to find out the concentration as
a function of time.
Integrated first-order rate law
First Order: A → B
d A
Rate = − = k A
dt
Separate concentration and time terms
d A
= −kdt
A
Integrating over the limits [A]0 to [A]t and 0 to t,
d A
 A = −k  dt

d A
[ A ]t t


[ A ]0
A
= −k  dt
0

lnAt − lnA0 = −kt

lnAt = −kt + lnA0 ………………………………………Straight line equation (y = mx+c)
If we plot ln [A]t versus time, then we will get a straight line having negative slope (-k). Rate
constants can be determined from experiment by plotting data in this manner.
Other forms:

ln
At = −kt
A0
At = e − kt
A0
At = A0 e − kt ………………………………………………. Integrated first order rate law

The exponential decay of the reactant in a first-order reaction. The larger the rate constant, the
more rapid the decay.
Sample question:
1. The variation in the partial pressure of azomethane with time was followed at 600 K, with
the results given below. Confirm that the decomposition is first-order in azomethane, and find
the rate constant at 600 K.
CH3N2CH3 (g) → CH3CH3 (g) + N2 (g)

Solution: To confirm that a reaction is first-order, plot ln([A]t/[A]0) against time and expect a
straight line. Because the partial pressure of a gas is proportional to its concentration, an
equivalent procedure is to plot ln(p/p0) against t. First, convert p into ln(p/p0) and draw the
graph. The plot is straight, confirming a first-order reaction, and its slope is -3.610-4.
Therefore, k = 3.6 10-4 s-1.

First-order Half-life
Half-life is the time it takes for the original concentration to be reduced by half.
From above:

ln
At = −kt
A0
 A0 
 
ln  2 
= −ktt / 2
A0
1
ln = −ktt / 2
2
− 0.693 = −ktt / 2
t t / 2 = 0.693 / k

It is clear from the result that the half-life of a reactant is independent of its initial concentration
for a first-order reaction. Therefore, if the concentration of A at some arbitrary stage of the
reaction is [A], then it will have fallen to 1/2[A] after a further interval of (ln 2)/k.

Another important point to note is the time constant, τ (tau), the time required for the
concentration of a reactant to fall to 1/e of its initial value.
 A / e  1
k = − ln  0  = − ln = 1
 A0  e

Thus, the time constant of a first-order reaction is the reciprocal of the rate constant, .
Sample question:
1. The half-life of a first-order reaction was found to be 10 min at a certain temperature. What
is its rate constant?
Solution: k= 0.693/600s = 0.00115s-1
2. If 3.0 g of substance A decomposes for 36 minutes the mass of unreacted A remaining is
found to be 0.375 g. What is the half-life of this reaction if it follows first-order kinetics?

Solution: ln
At = −kt
A0
ln
At / t = −k
A0
0.375g
ln
3g
k =−
36 min
k =0.0578 min-1
 ln 2 0.693
t1 / 2 = = = 12 min
k 0.0578

Integrated second-order rate law

A→B
d A
− = k A
2

dt
d A
= −kdt
A2
1 1
− = kt
At A0

Integrated zero-order rate law

A→B
d A
− = k A
0

dt
At − A0 = −kt

Pseudo First Order Reaction

A pseudo first-order reaction can be defined as a second-order or bimolecular reaction that is
made to behave like a first-order reaction. This reaction occurs when one reacting material is
present in great excess or is maintained at a constant concentration compared with the other
substance.
A+B→C
So, if component B is in large excess and the concentration of B is very high as compared to
that of A, the reaction is considered to be a pseudo-first-order reaction with respect to A and if
component A is in large excess and the concentration of A is very high as compared to that of
B, the reaction is considered to be pseudo-first order with respect to B.

Below is an example to help you understand the concept more clearly:

Consider the hydrolysis of ethyl acetate, during the hydrolysis, the concentration of ethyl
acetate is 0.02 mol/L whereas the amount of water is 20 mol/L as the process of hydrolysis
involves a large amount of water. Let’s say, the process of hydrolysis attains completion in
time t.
The reaction can be represented as
CH3COOC2H5 + H2O → CH3COOH + C2H5OH
For the above-mentioned reaction, the rate equation can be given as,
Rate = k [CH3COOC2H5] [H2O]
Here we see that the concentration of water is very high and thus does not change much during
the course of the reaction. Thus the rate of the reaction can be said to be independent of the
change in the concentration of H2O. Putting the term for change of concentration of water in
the above reaction to being zero we can write the effective rate equation as,
Rate = k [CH3COOC2H5]
Here, the term kt takes into account the value of the constant concentration of water.
Where k = k’ [H2O]
Such reactions are termed as pseudo-first-order reactions.
Integrated rate laws of different order reactions:

Temperature dependence of reaction rates:

The rate constant of most reactions increases with increase in the temperature.
Arrhenius equation
Ea
ln k = ln A − , where, A is the pre-exponential factor and Ea is the activation energy.
RT
If we plot the graph ln k vs 1/T, we will get the value of A from the intercept at infinite T (i.e.
1/T=0) and the value of Ea from the slope (see the figure below).

A plot of ln k against 1/T is a straight line when the reaction follows the behavior described by
the Arrhenius equation.
The higher the activation energy, the stronger the temperature dependence of the rate constant
(i.e., the steeper the slope).
If a reaction has zero activation energy, its rate is independent of temperature.

Sample questions:
1. The rate of the second-order decomposition of acetaldehyde (CH3CHO) was measured over
the temperature range 700–1000 K, and the rate constants are reported below. Find Ea and A.

Solution: First convert T in (103) and k into ln k. Now, plot ln k against 1/T. You will obtained
the following graph having slope = −22.7 and intercept 27.7.

Now, Ea = 22.7 × (8.3145 J K−1 mol−1) × 103 K = 189 kJ mol−1

A = e27.7 dm3 mol−1s−1 = 1.1 × 1012 dm3 mol−1 s−1

2. The values of rate constants for a reaction are 9.51x10 -9 L/mol.s and 1.10x10-5 L/mol.s at
temperatures 500K and 600 K respectively. Calculate the activation energy. [176
kJ/mol]

k2 E 1 1
Solution: ln =− a  − 
k1 R  T2 T1 
−1
k 1 1
Ea = − R ln 2  − 
k1  T2 T1 

Substitute the given values and do the calculation.

Energy barrier: interpretation of Arrhenius parameters

 Ea
ln k = ln A −
RT
One can rewrite the above equation as:
Ea
−
k = Ae RT

To interpret Ea, lets us consider the collision between molecules of reactants A and B.

Collision theory:
1. The rate of a reaction is proportional to the rate of reactant collisions:
2. The reacting species must collide in an orientation that allows contact between the atoms
that will become bonded together in the product.
3. The collision must occur with adequate energy to permit mutual penetration of the reacting
species’ valence shells so that the electrons can rearrange and form new bonds (and new
chemical species).
But all the collision will not lead to the product. Only the molecules which are having sufficient
energy (E  Ea) can cross the energy barrier. As the reaction proceeds, A and B come into
contact, distort, and begin to exchange or discard atoms. The reaction coordinate is the
collection of motions, such as changes in interatomic distances and bond angles which are
directly involved in the formation of products from reactants. The minimum energy necessary
to form a product during a collision between reactants is called the activation energy (Ea). The
kinetic energy of reactant molecules plays an important role in a reaction because the energy
necessary to form a product is provided by a collision of a reactant molecule with another
reactant molecule. (In single-reactant reactions, activation energy may be provided by a
collision of the reactant molecule with the wall of the reaction vessel or with molecules of an
inert contaminant.) If the activation energy is much larger than the average kinetic energy of
the molecules, the reaction will occur slowly: Only a few fast-moving molecules will have
enough energy to react. If the activation energy is much smaller than the average kinetic energy
of the molecules, the fraction of molecules possessing the necessary kinetic energy will be
large; most collisions between molecules will result in reaction, and the reaction will occur
rapidly.
The potential energy rises to a maximum and the cluster of atoms that corresponds to the region
close to the maximum is called the activated complex. After the maximum, the potential
energy falls as the atoms rearrange in the cluster and reaches a value characteristic of the
products. The climax of the reaction is at the peak of the potential energy, which corresponds
to the activation energy Ea. This crucial configuration is called the transition state of the
reaction.
For a reaction involving the collision of two molecules, the activation energy is the minimum
kinetic energy that reactants must have in order to form products. For example, in a gas-phase
reaction there are numerous collisions each second, but only a tiny proportion is sufficiently
energetic to lead to reaction. The fraction of collisions with a kinetic energy in excess of energy
Ea is given by the Boltzmann distribution as e−Ea/RT. Hence, we can interpret the exponential
factor as the fraction of collisions that have enough kinetic energy to lead to reaction.
The pre-exponential factor is a measure of the rate at which collisions occur irrespective of
their energy. Hence, the product of A and the exponential factor, e−Ea/RT, gives the rate of
successful collisions.

A potential energy profile for an exothermic reaction. The height of the barrier between the
reactants and products is the activation energy of the reaction.
Both postulates of the collision theory of reaction rates are accommodated in the Arrhenius
equation. The frequency factor A is related to the rate at which collisions having the correct
orientation occur. The exponential term is related to the fraction of collisions providing
adequate energy to overcome the activation barrier of the reaction.

At one extreme, the system does not contain enough energy for collisions to overcome the
activation barrier. In such cases, no reaction occurs. At the other extreme, the system has so
much energy that every collision with the correct orientation can overcome the activation
barrier, causing the reaction to proceed. In such cases, the reaction is nearly instantaneous.
The Arrhenius equation describes quantitatively much of what we have already discussed about
reaction rates. For two reactions at the same temperature, the reaction with the higher activation
energy has the lower rate constant and the slower rate. The larger value of E a results in a smaller
Ea
−
RT
value for e reflecting the smaller fraction of molecules with enough energy to react.
Alternatively, the reaction with the smaller E a has a larger fraction of molecules with enough
Ea
−
RT
energy to react. This will be reflected as a larger value of e , a larger rate constant, and a
faster rate for the reaction. An increase in temperature has the same effect as a decrease in
activation energy. A larger fraction of molecules has the necessary energy to react (Figure 4),
Ea
−
RT
as indicated by an increase in the value of e . The rate constant is also directly proportional
to the frequency factor, A. Hence a change in conditions or reactants that increases the number
of collisions with a favorable orientation for reaction results in an increase in A and,
consequently, an increase in k.

(a) As the activation energy of a reaction decreases, the number of molecules with at least this
much energy increases, as shown by the shaded areas.
(b) At a higher temperature, T2, more molecules have kinetic energies greater than Ea, as shown
by the yellow shaded area.

Some more solved numericals:

1. Show that in case of first order reaction, the time required for 99.9% completion is nearly
ten times the time required for half completion of the reaction.
Solution:
2. The rate of the reaction x + 2y → product is 4 x 10−3 mol L−1s−1 if [x]=[y]=0.2 M and rate
constant at 400K is 2 x 10-2 s-1 , What is the overall order of the reaction.
Solution: