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Thermodynamics L2

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20 views3 pages

Thermodynamics L2

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purushottamapanda
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Thermodynamics

By

Dr.puspanjali Mishra
Asst.Prof. in Chemistry
PMEC, Berhampur

Module–II: FREE ENERGY IN CHEMICAL EQUILIBRIA (9 Hours)


Concepts of Entropy, Entropy in Physical and Chemical Changes, Free Energy
Concepts, Gibbs Helmholtz Equation, Free Energy Change and Criterion of
Spontaneity of Chemical Equation and Chemical Equilibrium, Van’t Hoff Equation.
L1-Terminology of thermodynamics, First law of thermodynamics, Isothermal & adiabatic
processes,
L2-concept of Entropy, Entropy in Physical and Chemical Changes, entropy changes in
reversible and irreversible processes.
L3-Entropy changes of ideal gases.
L4-Entropy changes in solids and liquids, entropy changes in phase changes.
L5-Entropy of mixing, Entropy of a reaction, Numerical problems.
L6-Free Energy Concepts, Variation of free energy change with temperature and pressure of
an ideal gas, Gibb’s Helmoltz equation.
L7-Free Energy Change and Criterion of Spontaneity of Chemical Equation and Chemical
Equilibrium
L8-Free energy and chemical equilibrium, Numerical problems.
L9-Maxwell’s relations, Van’t Hoff Equation.

Entropy
• It is known that a state with minimum energy is the most stable state of a
system.
• Therefore, in this universe there is a natural tendency of all systems to
stabilise by acquiring minimum energy.
• It was believed that all processes in which energy decreases (exothermic,
having negative value of ΔH) occur spontaneously.
• Hence, decrease in enthalpy is the driving force behind the spontaneous
processes.
• However, there are many endothermic reactions (ΔH positive) that are
spontaneous.
• For example, Water absorbs energy and is evaporated (endothermic
process) but it is spontaneous in nature.
• H2O (l) → H2O (g) ΔH = + 44.0 kJ mol-1
• Melting of ice is endothermic but spontaneous.
• It is definite that this cannot be explained by considering the decrease in enthalpy
alone. There are some additional contributory factors like entropy to the
spontaneity of these reactions.
• Entropy is a property that is used to express the extent of disorder or randomness
of a system and may be defined as the thermodynamic property that is a measure
of the randomness or disorder of the molecules of a system.
• Entropy is expressed by the symbol ‘S’. Like internal energy and enthalpy, entropy is
also a state function and therefore change in entropy depends only on the initial
and final states of the system.
• Change in entropy is given by
ΔS = S (final state)−S (initial state).
For a reversible process at equilibrium, the change in entropy is expressed as
𝑑𝑞
𝑑S = 𝑟𝑒𝑣 , Unit of entropy is Joule per Kelvin (J K -1).
𝑇
• Thus, entropy change may be defined as the amount of heat absorbed by the
system in a reversible manner divided by the absolute temperature at which the
heat is absorbed.

• A process occurs because the randomness or entropy increases.


• For a spontaneous process in an isolated system, entropy change is positive, that is, ΔS > 0.
• However, if the system is not isolated, the entropy changes of both the system and
surroundings have to be taken into account. Then
ΔStotal = ΔSsystem + ΔSsurroundings ≥ 0
For a reversible process, ΔS total must be zero. ΔStotal = ΔSsystem + ΔSsurroundings = 0
For a irreversible (spontaneous) process, ΔS total must be positive, that is,
• ΔStotal = ΔSsystem + ΔSsurroundings > 0.
• The system and the surroundings together constitute the universe.
• Therefore, for a spontaneous change, ΔS universe > 0.
• Hence, according to the second law of thermodynamics ‘in any natural process the energy
of the universe is conserved but the entropy of the universe always increases’.

Entropy is a state function


In the definition of entropy, the quantity qrev is not a state function and depends on
the path of the reaction, whereas the (dqrev /T ) is a perfect differential. This can be
shown as follows:
Suppose 1 mole of an ideal gas is undergoing a reversible expansion.
From the first law, dqrev = dU − dw
For work expansion, − dw = PdV hence dqrev = dU + PdV -----------(1)
𝜕𝑈
As P=RT/V and Cv=( ) or dU= Cv dT,
𝜕𝑇 v

𝑅𝑇
dqrev = Cv dT + dV ------------------(2)
𝑉

𝑅𝑇
dqrev = Cv dT+ dV
𝑉
As dqrev is not an exact differential, it can not be integrated. This is confirmed by
𝑅𝑇
observing the right hand side of Eq. (2) where dV can not be evaluated unless
𝑉
we specify the path or in other words the relation between T and V is known.
The value of V will be different for different values of T. Thus, dqrev depends on the
path by which the gas is expanded.
Dividing Eq. (2) by T on both sides we get
dqrev Cv RT 1 Cv 𝑅
= 𝑑𝑇 + dV = 𝑑𝑇 + dV = Cv ln T+ R ln V+constant.
𝑇 𝑇 𝑉 𝑇 𝑇 𝑉
dqrev
It follows that can be evaluated; hence, dqrev/T is an exact differential.
𝑇
Hence, we may conclude that entropy change dS is a perfect differential and hence
entropy S is a state function.
Thus, if a system changes from the initial state 1 to the final state 2, the entropy
change is expressed by
2 2 dq 2 2 dq
1
𝑑𝑆= 1 rev or 1 𝑑𝑆=S2 – S1= ∆𝑆= 1 rev,
𝑇 𝑇
where S1 and S2 are the entropies of the system in initial and final states
respectively.

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