Thermodynamics

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 Thermodynamics can be define as the study of energy, energy transformations and
its relation to matter. The analysis of thermal systems is achieved through the
application of the governing conservation equations, namely Conservation of Mass,
Conservation of Energy.

❖ System: A thermodynamic system is that portion of the Universe that we have selected for
investigation

❖ Surroundings: The are everything outside the system

❖ The real or imaginary surface that separates the system

from its surroundings is called boundary

Classification of chemical systems

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 Any characteristic of a system is called a property.
Intensive properties: are those that are independent of the size (mass) of a system,
such as temperature, pressure, and density

Extensive properties: values that are dependent on mass of the system such as
mass, volume, and total energy U

Extensive properties per unit mass are called specific properties, e.g. specific
volume (v=V/m)
Processes and Cycles

Any change a system undergoes from one equilibrium state to another is called a
process and the series of states through which a system passes during a process is
called a path

To specify a process, initial and final states and path must be specified

State function
A quantity in thermodynamics, such as internal energy, entropy or enthalpy, that has a unique value
for each given state of a system.
State functions do not depend on the path by which the system arrived at its present state

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 Reversible process: The initial conditions are restored at the end of the cycle.
There should not be any loss of heat due to friction, radiation or conduction.
Heat pump operates reversed cycle and regarded as refrigerator, because it pumps
heat from the cold body to the hot body.
constant volume, constant pressure, constant temperature, adiabatic and polytropic are all
reversible processes.

Irreversible cycle: In it initial conditions are not restored at the end of the cycle.
- There is loss of heat due to friction, radiation or conduction.
- Causes are:- (a) mechanical and fluid friction
(b) unrestricted expansion
(c) heat transfer with temperature difference

Cyclic process: A thermodynamic cycle consists of a linked

sequence of thermodynamic processes that involve
transfer of heat and work into and out of the system,
while varying pressure, temperature, and other state
variables within the system, and that eventually returns
the system to its initial state 4
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 Fig. 1

Let the pressure P on the piston be exactly equal to the pressure of the gas within. The
piston will neither move downward nor upward and, consequently, there will be no change in the
volume of the gas (Fig. 1a)
Now, suppose the pressure on the piston is decreased by an infinitesimally small amount dP.
Hence, the piston will move up and the gas will expand by an infinitesimally small amount. If the
pressure on the piston is kept infinitesimally smaller than the pressure of the gas itself, the
expansion of the gas will continue infinitesimally slowly, i.e., in a thermodynamically reversible
manner (Fig. 1b).
Pressure on the piston (external pressure), is made much smaller than the pressure of the gas
within the cylinder, then the gas will expand rapidly, pushing the piston upward suddenly (Fig.
1c). The expansion of the gas, in this case, is said to place irreversibly.
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Ref: Puri Sharma Pathania Physical Chemistry Book
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Ref: Puri Sharma Pathania Physical Chemistry Book
 Two mole of ideal gas expands reversibly from an initial pressure 10 atm. to a final of
0.4 atm.; the temperature being kept constant at 0οC. How much work is done by the
gas?

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Ref: Atkins' Physical Chemistry - Oxford University Press
 Types of chemical reactions

Chemical reaction

Exothermic Endothermic
Heat is liberated into the surroundings Heat is absorbed from the surroundings

Chemical reaction

Isochoric Isothermal process Adiabatic Process

process Isobaric process ΔT=0 Δq=0
ΔV=0 Δp=0
No change in internal No heat leaves or enters
No change in No change in energy the gas
volume pressure No change in Temperature of the gas
Temperature Temperature and Temperature changes
and pressure volume will
will increase increase
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 Mechanical work description

• Work = force required to move a body x distance that

body is moved

• Because F=PA, force= pressure per unit area

• This describes a piston’s movement and potential

‘energy’

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 Temperature
❑ The concept of temperature springs from the observation that a change in physical state
(for example, a change of volume) can occur when two objects are in contact with one
another as when a red-hot metal is plunged into water.
❑ The change in state can be interpreted as arising from a flow of energy as heat from one
object to another
❑ The temperature, T, is the property that indicates the direction of the flow of energy
through a thermally conducting, rigid wall.
❑ If energy flows from A to B when they are in contact, then we say that A has a higher
temperature than B

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Ref: Atkins' Physical Chemistry - Oxford
▪ The temperature is a property that indicates whether two objects would be in thermal
equilibrium if they were in contact through a diathermic boundary.
▪ Thermal equilibrium is established if no change of state occurs when two objects A to B are
in contact through a diathermic boundary.
Suppose an object A (which we can think of as a block of iron) is in thermal equilibrium with an
object B (a block of copper), and that B is also in thermal equilibrium with another object C (a flask
of water). Then it has been found experimentally that A and C will also be in thermal equilibrium
when they are put in contact
This observation is summarized by the Zeroth Law of thermodynamics:
If A is in thermal equilibrium with B, and B is in thermal equilibrium with C, then C is also in
thermal equilibrium with A.

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Ref: Atkins' Physical Chemistry - Oxford
 Internal energy of system (U)

The internal energy U of a system is the total of all kinds of energy possessed by
the particles that make up the system.
In thermodynamics, the internal energy of a system is the energy contained
within the system.
It is the energy necessary to create or prepare the system in any given state, but
does not include the kinetic energy of motion of the system as a whole, nor the
potential energy of the system

✔ Internal energy is extensive property

✔ Internal energy is state function

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 First Law of Thermodynamics

dq = dU + dw and w = PdV

If V is constant, then ΔV = 0, and PdV = 0.

This leaves ∆U = qv
Measure ΔU by measuring heat released or taken up at constant volume

The energy cannot be created nor destroyed

The total energy of the universe is a constant

Energy can, however, be converted from one form to another or transferred from

a system to the surroundings: q = ΔU+ W (Where q is an amount of heat

ΔU is changes in internal energy; W is work done

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 Enthalpy

dq = dU + dw

U2-U1 = (q2-q1) – P(V2-V1)

= q2-q1-PV2+PV1
(U2+ PV2)-(U1+PV1 )= q2-q1
Make qp=q2-q1, qp = (U2+PV2)-(U1+PV1)
= H 2- H 1
= Δ H (H = U + PV)
qp is measurable – by measuring temperature changes resulting from energy changes (i.e. from
a chemical reaction Total differential for Enthalpy is:
dH = dU + PdV + VdP

If the change occurs at constant pressure dP = 0 so VdP = 0

dH = dU + PdV

From the first law of thermodynamics dq = dU + PdV (only mechanical work involved)

So dH = dqp
So qp = ΔH This is the physical significance of qp
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So change in enthalpy is nothing but heat of the process of constant pressure
Heat capacity

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C p− C v = R
dq = dU + dW
dU = Cv dT and dq = Cp dT
Therefore CP dT = CV dT + PdV
For ideal gas PdV = nRdT
So, CP dT = CV dT + nRdT
So, (CP − CV) dT = nRdT
CP − CV = nR

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 Kirchhoff's equation

Kirchhoff's Law describes the enthalpy of a reaction's (heat of reaction) variation with
temperature changes.
Uf − Ui = ΔU f = final state
Hf − Hi = ΔH i = initial state

Differentiate with respect to temperature at constant volume for the former and at
constant pressure for the latter

Or you can write

Integrating between the limits TοK and 0οK we have

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 Thermochemistry
❑ The study of the energy transferred as heat during the course of chemical reactions is called
thermochemistry.
❑ Calorimetry is used to measure the energy supplied or discarded as heat by a reaction, and can
identify q with a change in internal energy (if the reaction occurs at constant volume) or a
change in enthalpy (if the reaction occurs at constant pressure).
❑ Conversely, if we know ΔU or ΔI for a reaction, we can predict the energy (transferred as heat)
the reaction can produce.
❑ A process that releases energy by beating the surroundings is classified as exothermic and one
that absorbs energy by cooling the surroundings is classified as endothermic.

Hess's law

Standard enthalpies of individual reactions can be combined to obtain the enthalpy of another
reaction. This application of the First law is called Hess's law:
The standard enthalpy of an overall reaction is the sum of the standard enthalpies of the
individual reactions into which a reaction may be divided.

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 20
Ref: Atkins' Physical Chemistry - Oxford University Press
 Joule–Thomson effect
In thermodynamics, the Joule-Thomson effect describes the temperature change of a real gas when it
is forced through a valve or porous plug while keeping it insulated so that no heat is exchanged with
the environment. This procedure is called Joule-Thomson process.

If P1 and V1 are the pressure and volume of the

gas before passage through the plug and
P2 and V2 are the corresponding quantities after
passing through the porous plug the work of
expansion is given by;

w = P2V2 – P1V1 … … … (1)

We know the equation, ∆U = q – w
or, ∆U = q – (P2V2 – P1V1) … …. ….. (2)
But, ∆U = U2 – U1 and q = 0, so, equation (2) becomes,
U2 – U1 = 0 – (P2V2 – P1V1) = – (P2V2 – P1V1)
or, U2 + P2V2 = U1 + P1V1
and, H2 = H1 … … … (3) 21
 Carnot's theorem, developed in 1824 by Nicolas Léonard Sadi Carnot, also called Carnot's rule, is a
principle that specifies limits on the maximum efficiency any heat engine can obtain

CARNOT CYCLE
The Carnot cycle is an ideal reversible cyclic process involving the expansion and
compression of an ideal gas, which enables us to evaluate the efficiency of an engine
utilizing this cycle

For the ideal case of the Carnot cycle,

efficiency can be written

where TC and TH are the absolute

temperatures of the cold and hot reservoirs

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 Entropy
Entropy is the quantity that tells weather a chemical reaction or physical change can
occur spontaneously in an isolated system or not

Reversible cycle working between temp T1 and T2

We have (q2-q1)/q2 = (T2-T1)/T2
1-q1/q2=1-T1/T2
q1/q2=T1/T2
q2/T2 - q1/T1=0
Thus algebraic sum of entropies sum of entropies (q/T) in a reversible cycle is zero.
If any process is carried out reversibly so that dq is the amount of heat absorbed by the system from
surroundings at temp. T then entropy change dS (JK-1) is
dS=dqrev/T
Change of entropy is defined as

rev

ΔSsys +ΔSsurr = 0 for reversible process

ΔSsys +ΔSsurr > 0 for irreversible process

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Entropy Change for an ideal Gas

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 Case 1: In case of isothermal process dT = 0, So equation (i)and (ii) reduces to
ΔS = 2.303 n R log P1/P2
ΔS = 2.303 n R log P1/P2

Problem 1:
20 moles of ideal gas expands from a volume 2 ml to 6 ml, isothermally.
Find the entropy change accompanying the expansion.

∆S = 2.303 n R logV2/ V1
= 2.303 x 20 x 8.314 x log 6/2 JK-1

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❑ Entropy and disorderliness (661)

❖ Factors responsible for spontaneity of a reaction (662)

I. Tendency for minimum energy
II. Tendency to attain maximum randomness (entropy)

Entropy of universe
1. A system absorb heat from surroundings or release heat to surroundings both system and
surroundings undergo change in entropy
Heat change of surroundings is the negative of the heat change of the system

qsys = − qsurr
ΔSuniverse= ΔSsys+ ΔSsurr = 0
Entropy change in reversible process for universe is zero

2. For an irreversible (spontaneous) process the ΔSsurr= −qirrev/T

ΔSuniverse= ΔSsys − qirrev/T = qrev/T − qirrev/T >0

For an irreversible process for universe the net entropy increases or

Entropy of the universe is increasing since spontaneous reactions are always taking
place in universe

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 Incompleteness in the First Law
First law does not indicate weather a transformation of energy would at all occur
If occur, to what extent or in which direction the transformation would take place

To Illustrate:
(a) Fluid always flows from higher to lower elevation spontaneously

(b) Heat always flows from high to low temperature spontaneously

(c) Material always diffuse from high to low concentration spontaneously

And reverse of these never happen naturally (without aided by any external agency)

The recognition of two classes of process, spontaneous and non-spontaneous, is

summarized by the Second Law of thermodynamics
The second law of thermodynamics is formulated to record our experiences about direction of
change, stated as
All spontaneous processes are irreversible

All spontaneous processes tend to equilibrium

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 The Second Law

This law may be expressed in a variety of equivalent ways

In case of flow of heat: Clausius Statement

It is impossible for an engine, unaided by any external agency to convey heat from a

body at a low, to one at a high temperature

t1

t1
q1

w
Heat
Pump

t2 q2

t1 > t 2 t2

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 t1
Kelvin-Planck Statement:
It is impossible to convert the heat

completely into an equivalent amount of work

without producing some other changes in
some parts of the system

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 Spontaneous Processes
✔ Spontaneous processes are those that can proceed without any outside intervention
✔ The gas in vessel B will spontaneously effuse into vessel A
✔ Processes that are spontaneous in one direction are nonspontaneous in the reverse direction
✔ Processes that are spontaneous at one temperature may be nonspontaneous at other temperatures

Water
Ice

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Free energy : The thermodynamic functions which consider both energy and
randomness together are known as free energy functions
There are two types
i) Gibb’s Free Energy G = H – TS
II) Helmholtz free energy

Gibbs–Helmholtz equation
G = H – TS
= U + PV - TS
dG = dU + PdV + VdP – TdS – SdT
Combining this equation with dU = TdS – PdV
we get dG = VdP – SdT
At constant pressure dP=0 we can write dGP = – SdT
[d(ΔG)/dT]P = −ΔS = (ΔG − ΔH)/T

ΔG = ΔH + T [d(ΔG)/dT]P 32
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The temperature dependence of free energy comes from the entropy term.
By knowing the sign (+ or -) of Δ S and Δ H,
we can get the sign of Δ G and determine if a reaction is spontaneous.

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 Clausius-Clapeyron Equation
The Clausius-Clapeyron equation relates the latent heat (heat of transformation) of vaporization
or condensation to the rate of change of vapor pressure with temperature
Let us imagine a vapor in equilibrium with its liquid held in a cylinder by a piston, at a constant
temperature – namely the temperature at which the liquid and vapor are in equilibrium − that is
to say, the boiling (or condensation) point for that pressure
G1 be the specific Gibbs free energy for the liquid
G2 be the specific Gibbs free energy for the vapor
when we have a liquid in equilibrium with its vapor (i.e. at its boiling point) the specific Gibbs free
energies of liquid and vapor are equal
G1=G2
So dG1 = dG2
G = H – TS
= U + PV - TS
dG = dU + PdV + VdP – TdS – SdT
Combining this equation with dU = TdS – PdV
we get dG = VdP – SdT

dp/dT = L/(RT²/p) pV = RT
and hence
V = RT/p
dp/p = (L/R)(dT/T²)

Integrated form of Clausius-Clapeyron equation

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