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T H E PRI N C I PLES O F EN T RO PY

A N D
SPO N T A N EI T Y O F REA C T I O N
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Spontaneity
spontaneous
nonspontaneous
Spontaneous reaction = having the
potential to proceed without assistance
of external agency
Spontaneity of Reaction
Spontaneous or nonspontaneous ???
Reaction : Fe +O
2
Fe
2
O
3
Spontaneous or nonspontaneous???
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Spontaneous or nonspontaneous ???
Spontaneity of Reaction
Duafaktor yang menentukanterpisahnyaatom-atom reaktan
danpenataulangannyamenjadi produk
Kekuatanikatan(Chemical Bond and Enthalpy)
Derajat ketidakteraturanpadakeadaanakhir (Entropy)
Fungsi Termodinamik : Gibbs Energy
Energi yang tersedia untuk melakukan kerja (driving
force for reaction)
Chemical Bond and Enthalpy
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STRONG STRONG
CHEMICAL CHEMICAL
BONDS BONDS
WEAK WEAK
CHEMICAL CHEMICAL
BONDS BONDS
LARGE LARGE
BOND BOND
ENERGY ENERGY
WEAK WEAK
BOND BOND
ENERGY ENERGY
LOW LOW
INTERNAL INTERNAL
ENERGY ENERGY
HIGH HIGH
INTERNAL INTERNAL
ENERGY ENERGY
LOW LOW
ENTHALPY ENTHALPY
HI GH HI GH
ENTHALPY ENTHALPY
~~
~~
~~
~~

Enthalpy
DH
o
=heat released or absorbed during a
chemical reaction at standard conditions.
Exothermic, (-DH), heat is released.
Endothermic, (+DH), heat is absorbed.
Reactions favor products with lowest
enthalpy (strongest bonds).
Entropy
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P, V, T P, V, T P, V, T P, V, T
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MORE ORDRED MORE ORDRED
LESS ORDERED LESS ORDERED
LESS DISORDRED LESS DISORDRED
MORE DISORDERED MORE DISORDERED
LOW ENTROPY LOW ENTROPY
HIGH ENTROPY HIGH ENTROPY

Entropy
DS
o
=change in randomness, disorder,
freedom of movement.
Increasing heat, volume, or number of
particles increases entropy.
Spontaneous reactions maximize disorder
and minimize enthalpy.
Gibbs Free Energy
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G = G = H H -- TTSS
Chemical Bonding Chemical Bonding
System Structure System Structure
Factors Determining DG
Free energy change depends on
enthalpy
entropy
DH =(enthalpy of products) - (enthalpy of
reactants)
DS =(entropy of products) - (entropy of
reactants)
DG =DH - TDS
Principles of Entropy
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Principle Principle--1 : 1 :
Chemical processes tend to proceed spontaneously
in the direction of diminished free energy, i.e. when
the free energy change, DG, is negative.
G = G = H H -- TS TS
DDG G is is the driving force of the driving force of chemical chemical
processes processes
Remember this
Minimized external driving force
Maximized external driving force
So, spontaneous reaction = having the minimum
of Gibbs Energy, DG must be negative
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Chemical processes tends to proceed spontaneously only Chemical processes tends to proceed spontaneously only
under one of the following sets of conditions : 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 TDS
greater than DH; 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 = G = H H -- TTSS
Chemical Bonding Chemical Bonding
System Structure System Structure
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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
G = H - TS
H = (H
P
-H
R
) <0
S = (S
P
-S
R
) >> 0
G < 0 G < 0
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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 TDS
greater than DH
G = H - TS
H = (H
P
-H
R
) <0
S = (S
P
-S
R
) < 0
G < 0 G < 0
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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.
G = H - TS
H = (H
P
-H
R
) > 0
S = (S
P
-S
R
) > 0
G < 0 G < 0
Principle-2 :
The gaseous state is more probable than the The gaseous state is more probable than the
liquid state, which in turn is more probable liquid state, which in turn is more probable
than the solid state than the solid state
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SOLID SOLID LIQUID LIQUID GAS GAS
Substance Substance
Entropy Val ues at 25 Entropy Val ues at 25 (in eu) (in eu)
Solid Solid Liquid Liquid Gas Gas
Sodium Sodium Na Na 12.30 12.30 13.83 13.83 36.71 36.71
Phosphorous Phosphorous PP 9.82 9.82 10.28 10.28 38.98 38.98
Silicone Silicone Si Si 4.43 4.43 11.21 11.21 40.12 40.12
Lead Lead Pb Pb 15.50 15.50 17.14 17.14 41.89 41.89
Water Water HH
22
OO -- 16.72 16.72 45.11 45.11
Methanol Methanol CH CH
33
OH OH -- 30.30 30.30 56.80 56.80
Boron Boron trioxide trioxide BB
22
OO
33
12.91 12.91 18.55 18.55 64.42 64.42
Silicone Silicone dioxide dioxide SiO SiO
22
10.00 10.00 11.35 11.35 54.62 54.62
Lithium Lithium oxide oxide Li Li
22
OO 898 898 9.86 9.86 56.03 56.03
Beryllium Beryllium oxide oxide BeO BeO 3.38 3.38 10.50 10.50 47.21 47.21
Titanium Titanium oxide oxide TiO TiO
22
12.01 12.01 15.43 15.43 56.44 56.44
Lead Lead oxide oxide PbO PbO 15.59 15.59 20.55 20.55 57.35 57.35
Boron Boron trichloride trichloride BCl BCl
33
45.30 45.30 -- 85.30 85.30
Silicone Silicone tetrachloride tetrachloride SiCl SiCl
44
-- 57.20 57.20 79.20 79.20
Lead Lead chloride chloride PbCl PbCl
22
32.50 32.50 38.34 38.34 76.63 76.63
Sodium Sodium chloride chloride NaCl NaCl 17.33 17.33 20.22 20.22 54.88 54.88
Mercury Mercury bromide bromide HgBr HgBr
22
40.71 40.71 46.80 46.80 76.51 76.51
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Entropy of Various Substances at 25 (in eu)
Principle-3 :
A A monoatomic monoatomicgas is more probable than a gas is more probable than a
polyatomic molecular gas, and hence tends to polyatomic molecular gas, and hence tends to
have higher entropy have higher entropy
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MOLECULAR STATE MOLECULAR STATE ATOMIC STATE ATOMIC STATE
HH 27 27 ..44 HH
22
15 15 66 -- --
NN 36 36..66 NN
22
22 22..99 -- --
OO 38 38..55 OO
22
24 24..55 OO
33
19 19..00
FF 37 37..99 FF
22
24 24..44 -- --
Si Si 40 40..11 Si Si
22
17 17..55 -- --
P P 39 39..00 PP
22
26 26..11 PP
44
16 16..77
SS 40 40..11 SS
22
27 27..33 SS
88
12 12..99
Cl Cl 39 39..55 Cl Cl
22
26 26..66 -- --
NO NO
22
57 57 ..55 NN
22
OO
44
36.4 36.4 -- --
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Entropy of Monoatomic and Polyatomic
Gas (in eu/ g atom)
Principle-4 :
An amorphous solid is more probable than a An amorphous solid is more probable than a
crystalline solid, and a simple crystalline solid crystalline solid, and a simple crystalline solid
is more probable than a more complex is more probable than a more complex
crystalline solid crystalline solid
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CRYSTALLYNE CRYSTALLYNE AMORPHOUS AMORPHOUS
Principle-5 :
A molecular addition compound, or a A molecular addition compound, or a
coordination complex, is less probable coordination complex, is less probable
than its separate components than its separate components
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Cu(NH Cu(NH
33
))
44
SO SO
44
Cu Cu
2+ 2+
+ 4NH + 4NH
33
+ SO + SO
44
22--
HH
33
NN--BF BF
3 3
NH NH
33
+ BF + BF
33
Principle-6 :
Compounds or elements of higher atomic Compounds or elements of higher atomic
weight, or molecule of the free elements weight, or molecule of the free elements
themselves, tend to have higher entropy themselves, tend to have higher entropy
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Effect of Mass on entropy of Gases at 25C :
X F Cl Br I
HX 41,51 44,65 - -
NaX 51,70 54,88 - -
PbX
2
69,35 76,63 82,43 85,91
ZrX
4
76,95 87,37 98,78 108,42
Principle-7 :
At ordinary temperatures, entropy effects At ordinary temperatures, entropy effects
are commonly small enough to have are commonly small enough to have
relatively little effects on the direction of relatively little effects on the direction of
reaction, unless the difference in total reaction, unless the difference in total
bonding energy between reactants and bonding energy between reactants and
products is relatively small. products is relatively small.
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Substances Substances DDHH
ff
oo
DDGG
ff
oo
T T DDSS
ff
oo
HH
22
OO(l) (l) -- 57.80 57.80 -- 54.64 54.64 + 3.16 + 3.16
HCl HCl (g) (g) -- 22.00 22.00 -- 22.77 22.77 -- 0.77 0.77
SO SO
22
(g) (g) -- 70.96 70.96 -- 71.79 71.79 -- 0.83 0.83
HH
22
SS (g) (g) -- 4.82 4.82 -- 7.89 7.89 -- 3.67 3.67
HH
22
Te Te (g) (g) + 36.90 + 36.90 + 33.10 + 33.10 -- 3.80 3.80
KNO KNO
33
(c) (c) -- 117.16 117.16 -- 93.96 93.96 + 23.20 + 23.20
Na Na
22
CO CO
33
(c) (c) -- 270.30 270.30 -- 250.40 250.40 + 19.90 + 19.90
Al Al
22
(SO (SO
44
))
33
(c) (c) -- 820.98 820.98 -- 738.99 738.99 + 81.99 + 81.99
NH NH
33
(g) (g) -- 11.04 11.04 -- 3.98 3.98 + 7.06 + 7.06
NN
22
OO
44
(g) (g) + 2.31 + 2.31 + 23.49 + 23.49 + 21.18 + 21.18
HNO HNO
33
(l) (l) -- 41.40 41.40 -- 19.10 19.10 + 22.30 + 22.30
PH PH
33
(g) (g) + 2.21 + 2.21 + 4.36 + 4.36 + 2.15 + 2.15
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Comparison on the values of Enthalpies and of Free
Energies of Formation (in kcal mole
-1
).
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 Entropy units are calories calories per degree per mole, per degree per mole,
and the entropy changes accompanying reaction and the entropy changes accompanying reaction
are often only a few entropy units, whereas heats are often only a few entropy units, whereas heats
of reaction are commonly more than a kilocalorie of reaction are commonly more than a kilocalorie
per mole. per mole.
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Principle-8 :
All chemical reactions that increase the All chemical reactions that increase the
entropy occur spontaneously at high entropy occur spontaneously at high
enough temperatures enough temperatures
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Entropy and Temperature Entropy and Temperature
S increases S increases
slightly with T slightly with T
S increases a S increases a
large amount large amount
with phase with phase
changes changes
Principles 9 :
In general, the more atoms in its molecules, the
greater is the entropy of a substance
Entropy is a function of temperature
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T (K)
Energy
H = f (T)
S = f (T)
TS = f (T)
TT
CC
G > 0 G > 0
G < 0 G < 0
G = G = H H -- T S T S
Reactions Reactions
DDHH
ff
oo
DDGG
ff
oo
kcal/mol kcal/mol kcal/mol kcal/mol
CCl CCl
44
(g) (g) ++22 HH
22
O(g) O(g) CO CO
22
(g) (g) ++44HCl(g) HCl(g) -- 41.2 41.2 -- 61.2 61.2
SF SF
44
(g) (g) ++33 HH
22
OO(g) (g) SO SO
33
(g) (g) ++66HF(g) HF(g) -- 45.0 45.0 -- 75.9 75.9
CaO CaO(c) (c) ++CO CO
22
(g) (g) CaCO CaCO
33
(c) (c) -- 42.5 42.5 -- 31.1 31.1
CH CH
44
(g)+ (g)+22 OO
22
(g) (g) CO CO
22
(g)+ (g)+22 HH
22
OO(g) (g) -- 191.8 191.8 -- 191.4 191.4
AsCl AsCl
33
(l) (l) ++33 NaF NaF(c) (c) 33NaCl(c) NaCl(c) ++AsF AsF
33
(g) (g) -- 24.7 24.7 -- 31.7 31.7
AlBr AlBr
33
(c) (c) ++PCl PCl
33
(g) (g) AlCl AlCl
33
(c) (c) ++PBr PBr
33
(g) (g) -- 3.1 3.1 -- 4.3 4.3
CH CH
33
OH(l)+NH OH(l)+NH
33
(g) (g) CH CH
33
NH NH
22
(g) (g) ++HH
22
O(g) O(g) + 3.5 + 3.5 -- 4.3 4.3
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Comparison on the Values of Standard Enthalpies
and of Free Energies for Some Chemical Reactions
Criterion for Spontaneous Change
EOS