BITS Pilani

Pilani Campus

CHEM F111 General Chemistry

Lecture 19
Dr. Ajay K. Sah
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Thermodynamics
The First Law

Thermochemistry
The Second Law

The Third Law

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Extensive and Intensive Properties

Extensive Property: A property that depends on the
amount of the substance in the sample. e.g., mass,
volume

Intensive property: A property that is independent of

the amount of the substance in the sample; e.g.,
pressure, temperature, molar volume.
Extensive properties are additive but intensive
properties are not.
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Extensive and Intensive Properties

Some intensive properties are ratios of two
extensive properties, e.g., density of a substance.
It is ratio of two extensive properties mass and
volume.
Specific property:
Given any extensive property, one may divide it by
the mass to obtain an intensive property called a
specific property.
For example, Specific Volume = Volume per Unit
Mass.
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System
System: That portion of
the universe set apart for
detailed
study
and
analysis.

Surroundings: Rest of
the universe, with which
the system can interact.
Thermally isolated system is called Adiabatic
system eg: water in vacuum flask.
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Classification of Systems
Open System One that can
exchange matter as well as
energy with its surroundings.
Closed System One which
can exchange energy but not
matter with the surroundings.

Isolated System One

which
is
completely
unaffected
by
the
surroundings.
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Homogeneous/Heterogeneous Systems
System consists of one or more parts, each of
which is spatially uniform in its properties, each
called a phase.
A single phase system is homogeneous, while a
system of two or more phases is heterogeneous

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1st law of thermodynamics

Conservation of energy in mechanical and thermal
processes
Work done on a system changes its internal
energy U, a state function which represents the
sum total of all the kinetic and potential energies of
the atoms/molecules/ions in the system.
U = w + q

Internal energy is an extensive property.

Molar internal energy is an intensive property.

In an adiabatic process, U = w
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Work
From mechanics, Work done w = fdx

Work done against gravity in raising an object of

mass m by a distance h = mgh
Most important in thermodynamics of fluids,
work of expansion/compression,
w = -pextdV
Slow, controlled process with no friction and the
external pressure being almost equal to the system
pressure,
w = -pdV
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Work: Example
1 mole of a perfect gas at 2 bar, and 300 K is in a
piston cylinder arrangement, in thermal contact
with the surroundings at 300 K. The gas is taken to
a final pressure of 1 bar, (a) by suddenly reducing
the external pressure to 1 bar, or (b) by reducing
the external pressure in infinitesimal steps, at each
stage allowing the gas to reach equilibrium. Find q,
w, U and in each case. Note: The molar
internal energy of a perfect gas depends only on
the temperature.
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Work: Solution of Example

(a) w = -Pex dV = - Pex(V2 V1) = -PexR(T2/P2 T1/P1)
= - RT(1 0.5) = -0.5RT = -150R.

For a perfect gas, dU = CVdT, and since here T1 = T2,

U = 0.

Therefore q = -w = 150R
Again, dH = CpdT, and with T1 = T2 here, so = 0.

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Work: Solution of Example

(b) At any stage during the process p = nRT/V
w = -PexdV = -pdV = -RT ln(V2/V1)

= RT ln(P2/P1) = -0.693RT = -208R

Like earlier U = H = 0 and hence, q = -w = 208R

U and are the same as in (a) since the initial

and final states are the same, but w and q are not.
w is greater here than in (a).
Reversible work is maximum work and greater
than irreversible work
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Heat And Enthalpy

The energy supplied as heat to a system or
released by a system at constant pressure is equal
to another thermodynamic property called
ENTHALPY which is defined as H = U + pV
It is a state function and an extensive property
like U and V.
Molar enthalpy Hm is an intensive property like Um,
p and Vm
Hm = Um + pVm = Um + RT for a perfect gas.
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Heat Capacity
Heat capacity at const. volume CV = (U/T)V
Heat capacity at const. pressure CP = (H/T)P
Hm = Um + RT
or
or
or
or

Hm - Um = RT
Hm - Um = R T
Hm/ T - Um/ T = R
CP,m CV,m = R
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Thermochemistry
Thermochemistry is the study of the heat evolved
or absorbed in chemical reactions
And hence it deals with calculations of quantities
like heat capacity, heat of combustion, heat of
formation, etc.
Hess Law- Combination of Reaction Enthalpies
Born-Haber Cycle- Determination of lattice
enthalpy of an ionic crystal
Kirchhoffs Equation- Variation of H with
temperature
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Hess Law: Example

The standard enthalpy of a reaction is the sum of
the standard enthalpies of the reactions into which
the overall reaction may be divided. Example:
C3H6(g) + (9/2) O2(g) 3CO2(g) + 3H2O(l) r= ?

C3H6(g) + H2(g) C3H8(g)

r1 = 124 kJ

C3H8(g)+5O2(g) 3CO2(g)+4H2O(l) r2= 2220 kJ

H2O(l)

H2(g) + O2(g)

r3 = 286 kJ

r= r1 + r2 + r3 = 2058 kJ
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Born-Haber Cycle
Determination of lattice enthalpy of an ionic crystal

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Kirchhoffs Equation
Kirchhoffs Equation- Variation of H with

temperature
HT2 = HT1 + Cp ( T2 - T1)
Cp = is the difference between the weighted
sums of the standard molar heat capacities of
products and the reagents ie.

Cp = n Cp(products)- nCp(reactants)
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Natural / Spontaneous Processes

Spontaneous change: Change that has tendency to
occur without work having to be done to bring it
about.
A spontaneous change has a natural tendency to
occur.
Non-spontaneous change: Change that can be
brought about only by doing work.
A non-spontaneous change has no natural tendency
to occur.
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Natural / Spontaneous Processes

Rigid, Adiabatic Container, Or
Isothermal free expansion of a perfect gas
Spontaneous
GAS

GAS

VAC

Not Spontaneous
Forward process spontaneous; Reverse process
non-spontaneous although consistent with First Law
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Natural / Spontaneous Processes

Flow of energy as heat
Spontaneous

Hot
block

Cold
block

Non-Spontaneous

Blocks
are
adiabatically isolated
from the rest of
universe.

In either direction, the

process is consistent
with the First Law.
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Irreversible and Reversible 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. An irreversible
process is also said to be spontaneous or natural.

A process I F is reversible if the system can be

returned to the initial state I without leaving any
change in the surroundings.

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Irreversible and Reversible Processes

Reversible
Infinitesimal driving force

Irreversible
Finite driving force

System traverses sequence of System traverses nonequilibrium states.

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.
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Disorder / Entropy
Matter tends to become disordered.

Energy tends to become disordered.

The extent of disorderness of a system is
measured by entropy (s).
The entropy S, a state function with dimensions
J/K, is an extensive property, defined by
dS = dqrev /T
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Entropy

For the isothermal process in example 1(b), the

entropy change S = nR ln(V2/V1) = Rln2. Since S is
a state function, the change must be the same for
the free expansion 1(a) also, and Rln2 for the
change in state in the opposite direction

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Entropy: 2nd Law of Thermodynamics

Second Law: The entropy of an isolated system (the
universe) tends to increase.
More generally
The entropy of a closed system in an adiabatic
enclosure can never decrease. It increases in an
irreversible process, and remains constant in a
reversible process.

dS 0 (adiabatic enclosure)
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dS = dqrev /T (why?)
The greater the amount of heat transferred to
the system, 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
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Why reversible heat transfer, dqrev ?

Suppose, we want to determine the entropy change
when a system changes between two specified states.
Consider that, entropy change = dSsys
Actual change occurs reversibly or irreversibly, not
known.

Say, we have found a path that joins the same two

states and which is reversible.
Entropy change = dSsys, as entropy is a state function.
But energy absorbed as heat, dqrev for the reversible
path, might be different.
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Why reversible heat transfer, dqrev ?

Let the system to restore to its initial state
reversibly following the same path.
Its entropy changes by dSsys (since entropy is a state
function) and heat released by system will be dqrev.
Therefore entropy of surroundings changes by
dqrev/T.
The total entropy change of the adibatically isolated
system during this restoration will be zero, since it is
carried out reversibly.

Therefore, - dSsys + dqrev/T = 0, or, dSsys = dqrev/T

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Entropy Change
For a measurable change, the entropy change is the
sum of the infinitesimal changes:
f

S = dqrev/T
i

Therefore in case of reversible isothermal

expansion of a gas, the entropy change of the
system,
f
S = (1/T) dqrev = qrev/T
i

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Fundamental Equation
Combined First and Second laws for a closed
system of fixed composition, only pdV work:
dU = q + w,

qrev = TdS,

wrev = -pdV

Hence, dU = TdS pdV

Since, the equation relates changes in functions of

the state, it may be used to calculate these changes
for irreversible processes also.
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