CHAPTER 6

Thermodynamics

It is the only physical theory of universal content concerning

which I am convinced that, within the framework of
theapplicability of its basic concepts, it will never be overthrow
– Albert Einstein
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 Evidence for a Chemical Reaction

1) Evolution of light or heat.

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 Evidence for a Chemical Reaction

2) Temperature change (increase or decrease) to the surroundings.

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 Evidence for a Chemical Reaction

3) Formation of a gas (bubbling or an odor) other than boiling.

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 Evidence for a Chemical Reaction

4) Color change (due to the formation of a new substance).

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 Evidence for a Chemical Reaction

5) Formation of a precipitate (a new solid forms) from the reaction of two

aqueous solutions.

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Chemical Reactions are accompanied by chemical changes appearing in different forms.

Making & Breaking of the bond causes for the energy changes

During chemical reaction energies are absorbed or released.

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 Questions

What Drives the To what extend the reaction will

chemical reaction? proceed at the given
set of conditionS?
Does the reaction is
feasible at the given
set of conditionS?

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 Thermodynamics =Heat + Work

Branch of science which deals with the quantitative relationship between heat
and other forms of energy.

Based on 3 Generalisation which was purely on the basis of human experience.

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 Scopes of Explains Macroscopic properties of
matter
Thermodynamics
Predict the feasibility of reaction
Predict the extend of reaction

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 Limitation of Thermodynamics

Silent about the rates of reaction

No mechanistic explanations
Quantities and qualities explaining are confined to macroscopic systems

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 Systems and Surroundings

oPart under investigation = System

oPart other than system = Surrounding
oSystem + Surrounding = Universe

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 Boundaries

The boundary is a closed surface surrounding a system through which energy

and mass may leave and enter.
Fixed, Movable , real and imaginary

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 Thermos Flask

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 Types Of System

Open System Closed System Isolated System

(Control Volume) (Control Mass)

DM ≠ 0 DM = 0
DM = 0
DQ ≠ 0 DQ = 0
DQ ≠ 0

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 Macroscopic System

System with large number of chemical species

The properties arise as a result of collective behaviour of large number of

species are Called as MACROSCOPIC PROPERTIES

P, V, T, refractive index, Surface tension, Density etc.

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 Macroscopic Properties

Intensive Property
Eg; T,P, viscosity,Density

a ss/ Volume
M

Extensive Property i ve
= i n t e ns
Eg: m, V, U
o p ert i es
p r
e x t e nsive
a n y t wo p ro p e rty
Rat i o of
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 Any system is characterized by

1. Parameters/variables of the state : Can be measured. Once the minimum

number of properties are fixed, other macroscopic variables changes
accordingly.
(T, m,C, P, no:of moles)

2. Functions of the state : Absolute value cannot be measured

(Internal energy, Enthalpy, Entropy, Gibbs Free energy)

Though state function and state variables are used interchangebly, state
variables are properties which are used to describe the state of the system

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State Functions & Path Functions

State Fuctions: Depends on final and initial state , Eg: G, U, S

Path Function: Depends on path of reaching initial to final, Eg: q, w

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 Internal Energy
Sum total of all the energy a system has

U1
U2 For cyclic process

DU=0

U3
Hence,
U1-U2 = U2-U3= U3-U1=0

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 Heat & Work : Path function

The transfer of heat energy (q) as a result of difference in temperature of

system and surroundings.
q>0 = +ve =Absorption of heat
q<0 = -ve = Release of heat

Heat is the transfer of thermal energy between systems, while work is the
transfer of mechanical (electrical or pressure volume work also) energy.

Work done ON the system = +ve = Compression work

Work done BY the system = -ve = Expansion work

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 Thermodynamic Processes
It is the operation which brings change in the state of the system.
Thermodynamic processes are
1. Isothermal process In which temperature remains constant, i.e., (dT = 0, Δ U = 0).
2. Isochoric process In which volume remains constant, i.e., (Δ V = 0).
3. Isobaric process In which pressure remains constant, i.e., (Δp = 0).
4. Adiabatic process In which heat is not exchanged by system with the surroundings,
i.e., (Δq = 0).
5. Cyclic process It is a process in which system returns to its original state after
undergoing a series of change, i.e., Δ U cyclic = 0; Δ H cyclic = 0
6. Reversible process A process that follows the reversible path, i.e., the process
which occurs in infinite number of steps in this Way that the equilibrium conditions
are maintained at each step, and the process can be reversed by infinitesimal change
in the state of functions.
7. Irreversible process The process which cannot be reversed and amount of energy
increases. All natural processes are Irreversible
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Laws of Thermodynamics

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 Zeroth Law of Thermodynamics

The law states that if the two systems are in thermal equilibrium with a third
system then they are also in thermal equilibrium with each other. Temperature is
used here to know, the system is in thermal equilibrium or not.

Applications

 When we get very hot food, we wait to make it normal. In this case, hot food
exchanges heat with surrounding and bring equilibrium.
We keep things in the fridge, and the things come equilibrium with fridge
temperature.
Temperature measurement with a thermometer or another device.
In the HVAC system, sensors or thermostats are used to indicate the
temperature. It always comes in thermal equilibrium with room temperature

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 Limitations of Zeroth Law

It does not tell us about the direction in which heat flows when they are in contact.

When two bodies come in equilibrium conditions, this law is unable to tell about the final
temperature or the temperature of the equilibrium conditions.

It does not tell about energy conservation.

Zeroth law predicts whether there will be heat transfer between objects or not.

If two objects are not in physical contact, there may also be a heat transfer. For example, if
two objects with different temperatures placed little distance, there may be a heat transfer by
radiation.

In the zeroth law, there will not be any heat transfer, if the systems are in thermal equilibrium.

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 First Law of Thermodynamics

Energy can neither be created nor destroyed although it may be converted from
one form to other. The total energy of the universe remains constant although it
may undergo transformation from one form to other. The energy of an isolated
system remains constant .
∆U= q + W
∆U = change in internal energy
q = heat energy
W = work done
q is positive when the system gains heat and negative when it loses heat.
W is positive when work is done by the system and negative when work is done
on the system.
 Let us do this !

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 Pressure- Volume work

Work = Force x Displacement

w = F x Dh
Force = Pressure external x Area

F= Pext.A

Therefore, w = Pext.A .Dh

w= Pext. DV

Area x length = Volume According to sign convention,

w= -Pext. DV

DV is positive on expansion and negative on compression

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 Reversible isothermal work
If the pressure is not constant but changes during the process such that it
is always infinitesimally greater than the pressure of the gas, then, at
each stage of compression, the volume decreases by an infinitesimal
amount, dV.

In such a case we can calculate the work done on the gas by the relation

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 In chemistry, we face problems that can be solved if we relate the work term to the
internal pressure of the system.
We can relate work to internal pressure of the system under reversible conditions by
writing

Now, the pressure of the gas (pin which we can write as p now) can be expressed in terms of its
volume through gas equation. For n mol of an ideal gas i.e., pV =nRT

Therefore, at constant temperature (isothermal process),

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 Free Expansion

Expansion of a gas in vacuum (pex = 0) is called free expansion. No work is

done during free expansion of an ideal gas whether the process is reversible or
irreversible .
Now, we can write equation in number of ways depending on the type of
processes.
Let us substitute w = – pex∆V in first law
∆U = q - pex∆ V
If a process is carried out at constant volume
(∆V = 0), then
∆U = qv
the subscript V in qV denotes that heat is supplied at constant volume.

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 Nutshell…

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Let’s Do This!!!

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 Enthalpy

Enthalpy or heat content of a system may be defined as the sum of the

internal energy and the product of its pressure and volume
H = E + PV
Where E is the internal energy;
P is pressure;
V is the volume of the system

Change in Enthalpy

It is the difference in the enthalpies of the products and the reactants

∆H = H(products)- H(reactants) = Hp- Hr

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 Various Enthalpy Changes
Enthalpy change is the name given to the amount of heat evolved or absorbed
in a reaction carried out at constant pressure.
It is given the symbol ΔH.

Standard enthalpy changes refer to reactions done under standard conditions,

and with everything present in their standard states.

Standard conditions are:

298 K (25°C)
a pressure of 1 bar (100 kPa). Standard pressure was originally defined as 1
atmosphere (101.325 kPa)
where solutions are involved, a concentration of 1 mol dm-3
The symbol for a standard enthalpy change is ΔH°.
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 Enthalpy and first law of
thermodynamics
Chemical reactions takes place in open vessel at constant Pressure

The new state function to explain change in energy for such a system is called
as enthalpy

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 Mole concept and First Law of
Thermodynamics

Case 1

Case 2 Case 4

Case 3

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 Heat Capacity

Heat Capacity (c) of a system is defined as the amount of heat required to raise
the temperature of a system by 1° C.
1. Molar Heat Capacity
It is the heat capacity 1 mole of substance of the system.
2. Specific Heat Capacity
It is the heat capacity of 1 g of substance of the system
q = mc Δ T.
where, m = mass of substance
c = specific heat or heat capacity

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 Derivation of Mayers Equation

At constant volume, the heat capacity, C is denoted by C V

and at constant pressure, this is denoted by Cp

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MEASUREMENT OF ∆U AND ∆H:
CALORIMETRY
We can measure energy changes associated with chemical or physical
processes by an experimental technique called calorimetry.

In calorimetry, the process is carried out in a vessel called calorimeter,

which is immersed in a known volume of a liquid.

Knowing the heat capacity of the liquid in which calorimeter is immersed

and the heat capacity of calorimeter, it is possible to determine the heat
evolved in the process by measuring temperature changes.

Measurements are made under two different conditions:

 Problem

1g of graphite is burnt in a bomb calorimeter in excess of oxygen at 298 K

and 1 atmospheric pressure according to the equation
C (graphite) + O2(g) → CO2 (g)
During the reaction, temperature rises from 298 K to 299 K. If the heat capacity
of the bomb calorimeter is 20.7kJ/K,what is the enthalpy change for the above
reaction at 298 K and 1 atm?

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 Thermochemical Equation

A Thermochemical Equation is a balanced stoichiometric chemical equation

that includes the enthalpy change, ΔH.

1.The coefficients in a balanced thermo-chemical equation refer to the number of moles

(never molecules) of reactants and products involved in the reaction.
2. The numerical value of ∆rH0 refers to the number of moles of substances specified by an

equation. Standard enthalpy change ∆r H 0 will have units as kJ mol–1

3.When a chemical equation is reversed, the value of ∆ rH0 is reversed in sign.

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Laws of Thermochemistry

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 1. Hess’s Law

The heat of any reaction ΔH∘f for a specific reaction is equal to the sum of the
heats of reaction for any set of reactions which in sum are equivalent to the
overall reaction:
According to Hess’s law
ΔH = ΔH1 + ΔH2 + ΔH3

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 Try this!!

The combustion of one mole of benzene takes place at 298 K and 1 atm. After
combustion, CO2 (g) and H2O (1) are produced and 3267.0 kJ of heat is
liberated. Calculate the standard enthalpy of formation, ∆f H0 of benzene.
Standard enthalpies of formation of CO2(g) and H 2O(l) are –393.5 kJ mol–1
and – 285.83 kJ mol–1 respectively.
 Applications of Hess’s Law

(a) In determination of heat of formation.

(b) In determination of heat of transition.
(c) In determination of heat of hydration.
(d) To calculate bond energies.

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 Lattice enthalpy and Born Haber Cycle

•For an ionic compound the lattice enthalpy is the enthalpy change when one mole of
solid in its standard state is formed from its ions in the gaseous state.

• The lattice enthalpy cannot be measured directly and so we make use of other known
enthalpies and link them together with an enthalpy cycle.

•Born-Haber Cycle: a series of hypothetical steps and their enthalpy changes needed
to convert elements to an ionic compound and devised to calculate the lattice energy.

Elements (standard state) converted into gaseous atoms

Losing or gaining electrons to form cations and anions

Combining gaseous anions and cations to form a solid ionic compound

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 Extra Knowledge…
Lavoisier Laplace Law
The enthalpy change during a reaction is equal in magnitude to
the enthalpy change in the reverse process but it is opposite in
sign.
Trouton’s Rule
According to this law, “The ratio of enthalpy of vaporization
and normal boiling point of a liquid IS approximately equal to
88 J per mol per kelvin. i.e.,
ΔHvap / T = 88 J / mol / K
Dulong and Petit Law
This law states “The product of specific heat and molar mass of
any metallic element is equal to 6.4 cal/ mol/ °C. i.e.,
Kirchhoff’s Equation
ΔCp = ΔH2 – ΔH1 / T2 – T1
and ΔCv = ΔE2 – ΔE1 / T2 – T1
Clausius – Clapeyron Equation
– 2.303 log p2 / p1 = ΔHv / R (T2 – T1 / T1 T2)
where, ΔHv = molar heat of vaporisation.
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 Do you know ??

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Limitation of First Law of
Thermodynamics
 Second Law of Thermodynamics
The Second Law of Thermodynamics states that the state of entropy of the
entire universe, as an isolated system, will always increase over time. The
second law also states that the changes in the entropy in the universe can never
be negative.

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 Entropy
It is the measurement of randomness or disorder of the molecules.

It is a state function and extensive property.

Units : jK-1 mol-1

The change in entropy during a process is mathematically given as:

ΔrS° = Σ S° (products) – Σ S° (reactants) = qrev / T = ΔH / T

Where, qrev heat absorbed by the system in reversible manner

T = temperature

Δ S > 0, Increase in randomness, heat is absorbed

Δ S < 0, Decrease in randomness, heat is evolved.

Entropy of even elementary substances are not zero.

Entropy change of an ideal gas is given by
Δ S = nCV In (T2 / T1) + nR In (V2 / V1)
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 Entropy Change During Phase Transition
The change of matter from one state to another state is called phase transition.
The entropy changes at the time of phase transition:
Spontaneous Process
The physical or chemical process which proceeds by its own in a particular
direction under given set of conditions without outside heir is called spontaneous
process. It cannot be reversed.
All natural processes are spontaneous process.
Spontaneous process where no initiation is needed
(i) Sugar dissolves in water.
(ii) Evaporation of water.
(iii) Nitric oxide (NO) reacts with oxygen.
Spontaneous process where some initiation is required
(i) Coal keeps on burning once initiated.
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Enthalpy Criterion of Spontaneous Process
All the processes which are accompanied by decrease of energy (exothermic reactions,
having negative value of ΔH) occur spontaneously.
It fails when some endothermic reactions occur spontaneously.

Entropy Criterion of Spontaneous Process

A process is a spontaneous if and only if the entropy of the universe increases.
For a process to be Spontaneous
(ΔSuniverse > 0 or ΔSsyst + ΔSsurr > 0)
At equilibrium state, ΔS = 0,

Limitations of ΔS criterion and need for another term

We cannot find entropy change of surroundings during chemical changes. So we need
another parameter for spontaneity viz Gibbs’ energy of system (G).

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 New Parameter!!!
Gibbs Energy or Gibbs Free Energy
It is the energy available for a system at some conditions and by which useful
work can be done. It is a state function and extensive property.
Mathematically,
G = H – TS
Change in Gibbs energy during the process is given by Gibbs Helmholtz
equation.
(ΔG = G2 – G1 = ΔH – TΔS)
where, ΔG = Gibbs free energy
H = enthalpy of system
TS = random energy
ΔGsystem = ΔH – TΔStotal

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 Effect of Temperature on Spontaneity

Now an exothermic reaction which is non-spontaneous at high

The Gibbs energy criterion of spontaneity temperature may become spontaneous at low temperature.
Similarly, endothermic reactions which are non-spontaneous at
ΔG > 0, process is non-spontaneous low temperature may become spontaneous at high temperature.
ΔG < 0, 0, process is spontaneous
ΔG = 0, process is in equilibrium state Standard Free Energy Change (Δ G)

It is the change in free energy which takes places when the

reactants are converted into products at the standard states, i.e.,
(1 atm and 298 K)
where, ΔG°f = standard energy of formation
Standard energy of formation of all free elements is zero.
 Joule-Thomson Effect
The phenomenon of cooling of a gas when it is made to expand adiabatically from a
region of high pressure to a region of extremely. low pressure is known as Joule-
Thomson effect. This effect is zero when an ideal gas expands in vacuum.
[When an ideal gas undergoes expansion under adiabatic condition in vacuum, no
change takes place in its internal energy, i.e., (∂E / ∂V) T = 0 where, (∂E / ∂V)T is
called the Internal pressure.]
Joule-Thomson Coefficient
Extra The number of degrees of temperature change produced per atmospheric drop in
pressure at constant enthalpy when a gas is allowed to expand through a porous plug
Knowledge… is called Joule-Thomson coefficient. It is given as
μ = dT / dp
where, μ = Joule-Thomson coefficient
dT = change in temperature
dp = change in pressure.
Inversion Temperature
The temperature below which a gas becomes cooler on expansion is known as the
inversion temperature. It is given as
Ti = 2a / Rb
where, a and b = van der Waals’ constant
At inversion temperature Ti, the the Joule Thomson coefficient μ = 0, i.e., the gas
neither heated nor cooled.
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Gibbs Energy and Equilibrium Constant
The criterion for equilibrium

Gibbs energy for a reaction in which all reactants and products

are in standard state,∆rG0 is related to the equilibrium constant of
the reaction as follows:

0 = ∆rG0 + RT ln K
or
∆rG0 = – RT ln K
or
∆rG0 = – 2.303 RT log K

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 Criteria for spontaneity

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 Third Law of Thermodynamics

•The entropy of all perfectly crystalline solids may be taken as zero at the
absolute temperature

•At absolute zero a perfectly crystalline solid has a perfect order of its
constituent particles i.e. there is no disorder at all. Hence absolute entropy is
taken as zero
 Thankyou

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