THE PRINCIPLES OF

ENTROPY
THE DRIVING FORCE

G = H - TS

The Disorder of
the Structure

The Strength of
Chemical Bonding
CHEMICAL BONDS
 Electrostatic Coulombic
Approach Forces

CHEMICAL + -
BONDING

Covalent Sharing of
Approach electron pair
 Electrostatic Ionic Bond
Approach

CHEMICAL normal
BONDING
Covalent Bond
coordination
Covalent Metalic Bond
Approach
Hydrogen Bond
 BOND STRENGTH

STRONG LOW
CHEMICAL LARGE BOND INTERNAL LOW
BONDS ~ ENERGY ~ ENERGY  ENTHALPY

WEAK HIGH
CHEMICAL
BONDS ~ SMALL BOND
ENERGY ~ INTERNAL
ENERGY
 HIGH
ENTHALPY
ENTROPY
 ENTROPY

P, V, T P, V, T
MORE ORDRED
LESS DISORDRED
LOW ENTROPY


LESS ORDERED
MORE DISORDERED
HIGH ENTROPY
Boltzmann’s Concept of Entropy :

S = ln Ω

The Degree of
Disorder

ENTROPY
Principle-1 :
Chemical processes tend to proceed spontaneously
in the direction of diminished free energy, i.e. when
the free energy change, G, is negative.

∆G = ∆H - T∆S is the driving force of

chemical processes
Chemical processes tends to proceed spontaneously only
under one of the following sets of conditions :

 If the total bonding forces in the products exceed

those in the reactants and the total disorder (entropy)
of the products is higher; or
 If the total bonding forces in the products exceed
those in the reactants and the total disorder in the
products is lower but not enough lower to make TS
greater than H; or
 If the total bonding forces in the products are weaker
than those in the reactants but the entropy increase
(increase in disorder) is more than large enough to
compensate for the heat absorbed.
∆G = ∆H - T∆S

System Structure

Chemical Bonding
1. Chemical processes tends to proceed spontaneously, if the
total bonding forces in the products exceed those in the
reactants and the total disorder (entropy) of the products
is higher

REACTANTS  PRODUCTS

WEAKER STRONGER
BOND  BOND

LOWER HIGHER
ENTROPY  ENTROPY
1. Chemical processes tends to proceed spontaneously, if the
total bonding forces in the products exceed those in the
reactants and the total disorder (entropy) of the products
is higher

∆H < 0

∆G = ∆H - T∆S

∆S > 0 ∆G < 0
2. Chemical processes tends to proceed spontane-ously, If
the total bonding forces in the products exceed those in
the reactants and the total disorder in the products is
lower but not enough lower to make TS greater than H

REACTANTS  PRODUCTS

WEAKER STRONGER
BOND  BOND

HIGHER LOWER
ENTROPY  ENTROPY
2. Chemical processes tends to proceed spontaneously, If the
total bonding forces in the products exceed those in the
reactants and the total disorder in the products is lower
but not enough lower to make TS greater than H

∆H < 0

∆G = ∆H - T∆S

∆S < 0 ∆G < 0
3. Chemical processes tends to proceed spontaneously, If the
total bonding forces in the products are weaker than those
in the reactants but the entropy increase (increase in
disorder) is more than large enough to compensate for
the heat absorbed.

REACTANTS  PRODUCTS

STRONGER WEAKER
BOND  BOND

LOWER HIGER
ENTROPY  ENTROPY
3. Chemical processes tends to proceed spontaneously, If the
total bonding forces in the products are weaker than those
in the reactants but the entropy increase (increase in
disorder) is more than large enough to compensate for
the heat absorbed.

∆H > 0

∆G = ∆H - T∆S

∆S > 0 ∆G < 0
ENTROPY PRINCIPLES
Principle-2 :
The gaseous state is more probable than
the liquid state, which in turn is more
probable than the solid state

SOLID  LIQUID  GAS

 Entropy of Various Substances at 25° (in eu)
Entropy Values at 25° (in eu)
Substance
Solid Liquid Gas
Sodium Na 12.30 13.83 36.71
Phosphorous P 9.82 10.28 38.98
Silicone Si 4.43 11.21 40.12
Lead Pb 15.50 17.14 41.89
Water H2O - 16.72 45.11
Methanol CH3OH - 30.30 56.80
Boron trioxide B2O3 12.91 18.55 64.42
Silicone dioxide SiO2 10.00 11.35 54.62
Lithium oxide Li2O 898 9.86 56.03
Beryllium oxide BeO 3.38 10.50 47.21
Titanium oxide TiO2 12.01 15.43 56.44
Lead oxide PbO 15.59 20.55 57.35
Boron trichloride BCl3 45.30 - 85.30
Silicone tetrachloride SiCl4 - 57.20 79.20
Lead chloride PbCl2 32.50 38.34 76.63
Sodium chloride NaCl 17.33 20.22 54.88
Mercury bromide HgBr2 40.71 46.80 76.51
Principle-3 :
A monatomic gas is more probable
than a polyatomic molecular gas, and
hence tends to have higher entropy

MOLECULAR STATE  ATOMIC STATE

Entropy of Monatomic and Polyatomic Gas
(in eu/g atom)

H 27 .4 H2 15 6 - -
N 36.6 N2 22.9 - -
O 38.5 O2 24.5 O3 19.0
F 37.9 F2 24.4 - -
Si 40.1 Si2 17.5 - -
P 39.0 P2 26.1 P4 16.7
S 40.1 S2 27.3 S8 12.9
Cl 39.5 Cl2 26.6 - -
NO2 57 .5 N2O4 36.4 - -
Principle-4 :
An amorphous solid is more probable
than a crystalline solid, and a simple
crystalline solid is more probable
than a more complex crystalline solid

CRYSTALLYNE  AMORPHOUS
Principle-5 :
A molecular addition compound, or a
coordination complex, is less probable
than its separate components

H3N-BF3  NH3 + BF3

Cu(NH3)4SO4  Cu2++ 4NH3+ SO42-

Principle-6 :
Compounds or elements of higher
atomic weight, or molecule of the free
elements themselves, tend to have
higher entropy
Principle-7 :
At ordinary temperatures, entropy
effects are commonly small enough to
have relatively little effects on the
direction of reaction, unless the
difference in total bonding energy
between reactants and products is
relatively small.
Before the concept of entropy had been clearly
recognized, the heat of a reaction (entalpy) was
the sole factor determining the direction of
spontaneous reaction.

Entropy units are calories per degree per mole,

and the entropy changes accompanying reaction
are often only a few entropy units, whereas heats
of reaction are commonly more than a kilocalorie
per mole.
Comparison on the values of Enthalpies and of Free
Energies of Formation (in kcal mole-1).
Substances Hfo Gfo T Sfo
H2O (l) - 57.80 - 54.64 + 3.16
HCl (g) - 22.00 - 22.77 - 0.77
SO2 (g) - 70.96 - 71.79 - 0.83
H2S (g) - 4.82 - 7.89 - 3.67
H2Te (g) + 36.90 + 33.10 - 3.80
KNO3 (c) - 117.16 - 93.96 + 23.20
Na2CO3 (c) - 270.30 - 250.40 + 19.90
Al2(SO4)3 (c) - 820.98 - 738.99 + 81.99
NH3 (g) - 11.04 - 3.98 + 7.06
N2O4 (g) + 2.31 + 23.49 + 21.18
HNO3 (l) - 41.40 - 19.10 + 22.30
PH3 (g) + 2.21 + 4.36 + 2.15
Principle-8 :
All chemical reactions that increase the
entropy occur spontaneously at high
enough temperatures