General Chemistry (CHEM F111)

Lecture-18
27/02/2024
RECAP
Thermodynamics: First law
 First Law – different versions
➢ If a system is enclosed by an adiabatic, impermeable
and rigid wall and no other non-expansion work is
done on it, (in other words the system is isolated) then
U = 0, or
U = Constant (Isolated)
“The internal energy of an isolated system is constant” - A
statement of First law of thermodynamics.
➢ U = wadia (adiabatic process, q = 0, closed system)
What is the significance? Under adiabatic condition,
work done will always be same whatever path it takes !
➢ For a closed system at constant volume and no
non-expansion work, U = qv
 Heat And Enthalpy
Since H = U + PV
Therefore dH = dU + PdV + VdP
dU = dq + dW = dq –PexdV (when work is
expansion and no non-expansion work).
dH = dq –PexdV + PdV + VdP
For a system open to atmosphere or in mechanical
equilibrium with surroundings, P = Pex
Therefore, dH = dq –PexdV + PexdV + VdP
i.e., dH = dq + VdP
 Heat And Enthalpy

If heating occurs at constant pressure, dP = 0

Therefore, dH = dq , at constant pressure

or, H = qp , at constant pressure

Therefore, if ‘q’ kJ of energy is supplied as heat to

a system which is free to change its volume at
constant pressure → the enthalpy increases by ‘q’
kJ regardless of how much energy is used by doing
work.
 Constant pressure heating or cooling
CP = dqp/dT
dqp = dH = CP dT
Tf
For a finite change: H =  CP dT
Ti

or, H = CP T when CP is independent in

this temperature range.
 Constant volume heating or cooling
CV = dqv/dT
Or, dqv = dU = CVdT
Tf
For a finite change, U =  CV dT
Ti

When CV is independent of temperature then,

U = CV(Tf – Ti) i.e. U = CV T
Thermochemistry (Self Study, T1-6th edition:3.1-3.7 )

• Role of Enthalpy in Chemistry

•The Enthalpy of Phase transition

•Enthalpies of combustion

•Standard Enthalpies of formation

•Variation of reaction Enthalpy with temperature:

Kirchhoff’s law
Second law of Thermodynamics

Second law has many forms,

but it originates from the same
principle of

Directional constraint
of natural processes
 Natural / Spontaneous Processes
“proceed towards equilibrium and take place in a
particular direction”
Example:

Fluid always flows from a higher elevation to a

lower elevation spontaneously
Heat always flows from high temperature to low
temperature (spontaneous cooling)
Materials always diffuse from high concentration
to low concentration
Reverse of this never happens, without any external source
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 Natural / Spontaneous Processes

Spontaneous Processes:
Matter tends to become disordered.
Energy tends to become disordered.
Disorder – “Mixing” or “ Spreading”.
More disorder – Greater probability, More
microstates (later)
 Natural / Spontaneous Processes

Rigid, Adiabatic Container

Spontaneous

GAS VAC GAS

.

Not Spontaneous
Can the reverse process be made to occur? Yes, by
introducing the piston and first compressing the gas back
to its original volume. Then return the gas to original state
by causing a heat transfer to some object in the
surroundings. Not adiabatically
 Natural / Spontaneous Processes
Last statement true for all natural processes
occurring in an adiabatic enclosure. The
system can be restored to its original state
only at the expense of a heat transfer to the
surroundings and thus changing the state of
the surroundings. Natural process is
irreversible in this sense.
We can also say, a non-spontaneous change can be
brought about only by doing work and when the
system is not isolated adiabatically.
 Natural / Spontaneous Processes

We have to look for a criterion, in particular

a thermodynamic property, which will decide
whether a process will occur adiabatically or
not.
 Natural / Spontaneous Processes
A process i → f is irreversible if the system cannot
be returned to the initial state i without leaving a
change in the surroundings.

In case of free expansion of a gas mentioned earlier,

reverse process is only possible by doing work and
when there is change in the state of surroundings.
Therefore, the reverse process is non-spontaneous.
In other words, the free expansion is irreversible
process. An irreversible process is also said to be
spontaneous or natural.
Reversible and Irreversible Processes
Example: A perfect gas taken from 2 bar, 300 K to
1 bar, 300 K by two different paths:
(a) Sudden reduction in the external pressure to 1
bar. (Irreversible)
(b) External pressure reduced in infinitesimal steps,
and the gas allowed to expand slowly.
(Reversible).
What are the distinct features of these two
processes?
 Reversible Irreversible

Infinitesimal driving force Finite driving force

System traverses sequence of System traverses

equilibrium states. non-equilibrium
states.
At any stage, an infinitesimal
change in some property can
cause the process to reverse,
and the same sequence of
states followed in reverse.
No dissipative effects such as
friction.
 Mechanical and Thermal Reversibility

Mechanical Reversibility – Expansion/Compression

with only an infinitesimal difference between system
pressure and external pressure. System virtually in
mechanical equilibrium with surroundings.

Thermal Reversibility – Heat Transfer across an

infinitesimal temperature difference. System virtually
in thermal equilibrium with surroundings
 ENTROPY

• The entropy S, with dimensions J/K, is an

extensive property, defined by
dS = (dqrev/T)
for a closed system undergoing an
infinitesimal reversible change.
• The entropy is a measure of the extent of
‘disorder’ of a system.
 ENTROPY
dS = dqrev/T (why?)
The greater the amount of heat transferred to the system, the greater
the thermal motion stimulated in it and hence the greater the
dispersal of energy. This suggests that,
dS  dq
More entropy is generated when a given quantity of energy is
transferred as heat to a cold system than to a hot system. The
simplest way of taking this dependence on temperature into account
is to write, dS = dq/T. It takes into account the disorder that is
already present.
Why reversible heat transfer, dqrev ?

Reversible transfer of heat is smooth, careful, restrained. No hot

spots generated in the object.
 Entropy and Second Law
Second Law:
The entropy of the universe tends to increase
Or
the entropy of an isolated system tends to increase
for a spontaneous change.
Global Isolated
Here isolated System of
system, energy
system in the interest
is conserved
sense of a little
universe
Surroundings
Entropy and Second Law
For a measurable change, the entropy change
is the sum of the infinitesimal changes:
f
S=i  dqrev/T

Therefore in case of reversible isothermal

expansion of a gas, the entropy change of the
system,
f
S = (1/T)  dqrev = qrev/T
i
 Entropy Change with Volume
Consider the reversible, isothermal expansion of n
moles of a perfect gas in which the volume doubles.
Isothermal process, so Ti = Tf = T
For this process, q = nRT ln(Vf/Vi) = nRT ln2, and
since the process is isothermal and reversible,
S = (dqrev /T) = q/T = nR ln2
This entropy change has come about due to the
heat transfer from the surroundings, ie., heat
transfer is accompanied by entropy transfer. 24
Entropy Change with Volume

25
 Entropy Change with Temperature
Reversible Heat Transfer at Constant Volume:
S = (dqrev /T) =  (CVdT /T)
If CV taken to be independent of temperature,
S = CV ln(Tf /Ti)
Ti and Tf are initial and final temperatures
respectively.

The higher the heat capacity of the substance, the

greater is S for a given rise in temperature.
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Entropy Change with Temperature

Assumption:
heat capacity is
constant Over
the temperature
range

27
Heat capacity varies with temperature
S = area under the
graph of CV/T plotted
against T, between Ti
and Tf

28
 Entropy change for Phase Transitions
•When a solid melts at its melting temperature
or, a liquid boils at its boiling temperature, the two
phases are in equilibrium.

•Transfer of energy as heat occurs reversibly when

a solid is at its melting temperature or a liquid is at
its boiling temperature.
•Therefore the transformation can be driven in
either direction by causing an infinitesimal heat
transfer into or out of the system reversibly.
 Entropy change for Phase Transitions
The transition occurs at constant pressure,
therefore, qrev = H.

At constant pressure, heat transferred per mole of

the substance melts = enthalpy of fusion = fusH

At the melting temperature Tf ,

fusS = fusH/Tf
At the boiling temperature Tb ,
vapS = vapH/Tb
 Trouton’s Rule
Substance vapS(JK-1mole-1)
Benzene 87.2
Cyclohexane 85.1
Bromine 88.6
Carbon Tetrachloride 85.9
Water 109.1
vapS approximately constant at about
85 JK 1mole-1 for all liquids at their
boiling points
 Trouton’s Rule

vapS = vapH/Tb
Liquid vapourises into widely dispersed
gaseous form, that will occupy the same
volume. Identity doesn’t matter!

Exceptions : liquids with specific interactions

Water (hydrogen bonding), mercury

(metallic bonding) etc.
 Application
The enthalpy of vapourisation vapH, for a
liquid can be found if we know it’s boiling
point
Estimate the enthalpy of vaporization of liquid
bromine from its boiling temperature 59.20C.

vapS = 85 JK-1mol-1 vapS = vapH/Tb

vapH = 332.4 K  85 J/K/mol

= 28 kJ/mol
Experimental value = 29 kJ/mol
 Entropy Changes in Surroundings
For the reversible, isothermal expansion:
Surroundings → a large reservoir remains almost at
constant temperature and pressure regardless any events
taking place in the system.
Therefore, qsur,rev = Hsur
Enthalpy is state function, so Hsur is path independent.
Therefore, Ssur = qsur/T.
Applicable for surroundings regardless of whether the
change in the system is reversible or not.
If energy supplied to the system as heat is q,
then qsur = − q = - nRT ln(Vf/Vi) [perfect gas]
Therefore, Ssur = − q /T
In the previous example of reversible, isothermal
expansion of n moles of a perfect gas,
Ssurr = qsurr/T = − q/T = - nR ln(Vf/Vi) = − nR ln2
Stotal = Ssys + Ssurr = 0
(The total entropy change of the universe in a
reversible process is zero. There is only a transfer of
entropy.)
 Entropy Change in Surroundings:
Adiabatic Free Expansion
In adiabatic free expansion of a perfect gas:
considering volume doubles
S = nR ln2 (initial and final states being same).

Since U = 0 and w = 0; q = 0.
Since there is no change in the surroundings,

Ssur = − q/T = 0, and Stot = nR ln2.

Total entropy increased, irreversible process

Entropy of the universe is constantly increasing
Entropy Change in Surroundings: Phase transition
For a process such as a phase transition or
chemical reaction taking place in system at
constant pressure,
q =  = −qsur
 = change in enthalpy of the system.
If exothermic ( < 0), Ssurr > 0 ;
Ssurr increases for exothermic reactions, because heat is
released into the surrounding
If endothermic  > 0, Ssurr < 0 ; Ssurr decreases,
because heat is absorbed from the surrounding
 Molecular Interpretation of Entropy
• Ludwig Boltzmann described the concept of entropy
from the molecular (microscopic) point of view.
• Temperature is a zeroth law quantity. Temperature is a
measure of the average energy of the molecules in a
sample. It is molecular interpretation of temperature.
• Internal energy is a first law quantity. Internal energy is
interpreted as total molecular energy.
• We have to look for molecular interpretation of entropy.
• Molecules exhibit several types of motion:
 Molecular Interpretation of Entropy

• Boltzmann envisioned the motions of a sample

of molecules at a particular instant in time.
– This would be akin to taking a snapshot of all
the molecules.
• He referred to this sampling as a microstate of
the thermodynamic system.