Materi I:

Prinsip-prinsip Reaksi Kimia Reaksi Kimia

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THE PRINCIPLES OF ENTROPY

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P, V, T P, V, T

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MORE ORDRED

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LESS DISORDRED
LOW ENTROPY


LESS ORDERED
MORE
DISORDERED
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HIGH ENTROPY
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STRONG LARGE LOW
LOW
 ENTHALPY
BONDS
~
CHEMICAL BOND
~
ENERGY
INTERNAL
ENERGY

WEAK WEAK HIGH

~
CHEMICAL BOND ~ INTERNAL  HIGH
BONDS ENERGY ENERGY ENTHALPY

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∆G = ∆H - T∆S

System Structure

Chemical Bonding

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Principle-1 :

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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

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

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 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.
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∆G = ∆H - T∆S

System Structure

Chemical Bonding

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Chemical processes tends to proceed
spontaneously, if the total bonding forces in the

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products exceed those in the reactants and the total
disorder (entropy) of the products is higher

∆H = (HP-HR) < 0

∆G = ∆H - T∆S

∆S = (SP-SR) > 0 ∆G < 0

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Chemical processes tends to proceed
spontaneously, If the total bonding forces in the

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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 = (HP-HR) < 0

∆G = ∆H - T∆S

∆S = (SP-SR) < 0 ∆G < 0

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Chemical processes tends to proceed
spontaneously, If the total bonding forces in the

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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 = (HP-HR) > 0

∆G = ∆H - T∆S

∆S = (SP-SR) > 0 ∆G < 0

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 PRINCIPLE-2 :
THE GASEOUS STATE IS MORE

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PROBABLE THAN THE LIQUID STATE,
WHICH IN TURN IS MORE PROBABLE
THAN THE SOLID STATE

SOLID  LIQUID  GAS

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 Entropy of Various Substances at 25° (in eu)
Entropy Values at 25° (in eu)
Substance
Solid Liquid Gas

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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
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Sodium chloride NaCl 17.33 20.22 54.88
Mercury bromide HgBr2 40.71 46.80 76.51
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PRINCIPLE-3 :
A MONATOMIC GAS IS MORE PROBABLE
THAN A POLYATOMIC MOLECULAR GAS,
AND HENCE TENDS TO HAVE HIGHER
ENTROPY

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MOLECULAR STATE  ATOMIC STATE
Entropy of Monatomic and Polyatomic Gas
(in eu/g atom)

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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 - - 16
 PRINCIPLE-4 :

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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
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 PRINCIPLE-5 :
A MOLECULAR ADDITION

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COMPOUND, OR A COORDINATION
COMPLEX, IS LESS PROBABLE THAN
ITS SEPARATE COMPONENTS

H3N-BF3  NH3 + BF3

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Cu(NH3)4SO4  Cu2++ 4NH3+ SO42-
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PRINCIPLE-6 :
COMPOUNDS OR ELEMENTS OF HIGHER
ATOMIC WEIGHT, OR MOLECULE OF
THE FREE ELEMENTS THEMSELVES,
TEND TO HAVE HIGHER ENTROPY

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 PRINCIPLE-7 :
AT ORDINARY TEMPERATURES,

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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.
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Comparison on the values of Enthalpies and of Free
Energies of Formation (in kcal mole-1).
Substances Hfo Gfo T Sfo

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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 + 7.0621
N2O4 (g) + 2.31 + 23.49 + 21.18
Before the concept of entropy had been clearly
recognized, the heat of a reaction (entalpy) was

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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.

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PRINCIPLE-8 :
ALL CHEMICAL REACTIONS THAT
INCREASE THE ENTROPY OCCUR
SPONTANEOUSLY AT HIGH ENOUGH
TEMPERATURES

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Energy T∆S = f (T)

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∆H = f (T)

∆S = f (T)
∆G > 0

∆G < 0 T (K)
TC
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∆G = ∆H - T ∆S
Comparison on the Values of Standard Enthalpies and
of Free Energies for Some Chemical Reactions

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Hfo Gfo
Reactions kcal/mol kcal/mol

CCl4(g) + 2 H2O(g)  CO2 (g) + 4HCl(g) - 41.2 - 61.2

SF4 (g) + 3 H2O (g)  SO3 (g) + 6HF(g) - 45.0 - 75.9
CaO(c) + CO2(g)  CaCO3(c) - 42.5 - 31.1
CH4(g)+2 O2 (g)  CO2 (g)+ 2 H2O (g) - 191.8 - 191.4
AsCl3(l) +3 NaF(c)  3NaCl(c) + AsF3(g) - 24.7 - 31.7
AlBr3 (c) + PCl3 (g)  AlCl3(c) + PBr3 (g) - 3.1 - 4.3
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CH3OH(l)+NH3(g) CH3NH2(g) + H2O(g) + 3.5 - 4.3