Thermochemistry

Thermodynamics

Road map to understanding

Basic terms in TD
internal energy, heat and temp
work and heat
First law of thermodynamics,
Second law of thermodynamics,
pressure-volume work;
Entropy;
Free energy; Criterion of spontaneity.

Enthalpy and FLTD

Relation between Int energy and

enthalpy

Hess law

Spontanei
ty
what is the driving force of spontaneously occurring
changes ?
What determines the direction of a spontaneous

Criterion for spontaneity

having the potential to proceed without
the assistance of external help
A spontaneous process is an irreversible
process and may only be reversed by
some external agency.
Is enthalpy a criteria
Entropy and spontaneity
Free energy
in an isolated system, there is always a
tendency for the systems energy to become
more disordered or chaotic and this could be
a criterion for spontaneous change !

Entropy S
Measurement of randomness of the system
Whenever heat is added to the system, it increases
molecular motions causing increased randomness in e
system. Thus heat (q) has randomising influence on the
system.
temperature is the measure of average chaotic motion
of particles in the system = qrev/T

Second law of thermodynamics

Thesecond law of thermodynamicssays that the entropy

of the universe always increases for a spontaneous process
system Suniverse=Ssystem+Ssurroundings>0

In all spontaneous processes the entropy of the universe

increases

The free energy of the system in all the spontaneous process

decreases

Gibbs free
energy
Gibbs energy change =
enthalpy change temperature
entropy change
units of energy

G is an extensive
property
and a state function.

What is free energy

Effect of temperature on
spontaneity of reaction Criterion of spontaneity
H

-ive

+iv
e

-ive

Spontaneous reaction at all

temperature

+iv
e

-ive

+ive

Non spontaneous at all temperature

-ive

-ive

-ive
at low T

Reaction spontaneous at low temp

-ive

-ive

-ive at high
T

Reaction spontaneous at low temp

+iv
e

+iv
e

+ive at low
T ive at
high T

NS at low temp
Spontaneous at high temp

+iv
e

-ive

+ive at all
T

NS at high T

Third law of
thermodynamics
Limitation of SLTD it is not able to give information
about rate of chemical reaction
TLTD- value of entropy of a completely pure crystalline
substance is zero at absolute zero temperature .