CHEMISTRY ?

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 CHEMISTRY IS THE SCIENCE OF MATTERS
AND THEIR CHANGES, RELATED TO :

- Structure
- Composition
- Properties
- Energy
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 THE SCOPE OF CHEMISTRY :

INORGANIC CHEMISTRY,
ORGANIC CHEMISTRY,
CHEMISTRY
& BIOCHEMISTRY

PHYSICAL ANALYTICAL
CHEMISTRY CHEMISTRY

THEORETICAL DEVICES
9/9/2015 EXPERIMENTAL DEVICES 3
 Kornhauser (1981
1981)) :

z It is not chemistry if we learn theories

without facts,
facts and it is not science if we
learn only facts without learning theories.
theories.

z Theories must not replace facts in

chemistry,
y, but should explain
p them.
them.

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 CHEMICAL REACTION
is the focal point of any
chemical studies

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 Wh do
Why d chemical
h i l reactions
ti occur?
?
The purpose of this chapter is to examine the
nature of chemical change.

Focusing on the recognizing all setting forth the

basic principles that help us to understand why
chemical reactions occur.

F the
For th very essence off practical
ti l chemistry
h i t iis
the scientific control of chemical change.

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 If it is known why it occurs, then we can know
what conditions are necessary to cause or
prevent its occurrence, and we can direct our
ingenuity
g y toward establishing
g such conditions.

Furthermore, such understanding should be

invaluable to students, who without it are faced
with an almost infinite variety of chemical
equations to be memorized but with 110 basis
for recognizing that they do make sense.

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 Before we can consider "Why
"Why"" reactions occur,
it is necessary to think of what happens during
the occurring of a chemical reaction.
reaction.

Reactants Æ products
In order for this to happen, atoms, which are
initially attached to one another in a certain way
i the
in h reactants, b become separated, d at lleast to
some extent, and rearranged in the products.

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 THE CONCEPT OF ENERGY
Definition

Energy could be defined as the capacity of a system to do

work

q
heat
SYSTEM

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 Th Fi
The Firstt Law
L off Th
Thermodynamics
d i :
In ordinary processes, energy is conserved, it is
neither created nor destroyed

q
heat
SYSTEM
W
work
k

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 If h
heatt q is
i added
dd d to
t a system
t and
d workk w is
i done
d
by the system, the total amount of energy added to
the system,
y , (q - w)
w);
); is not destroyed
y but is stored
within the system to increase the internal energy ∆U U

q
heat
SYSTEM
W
∆U work
k

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 THE INTERNAL ENERGY

∆U
U=q-w

∆Unuclear : nuclear binding energy MeV

∆Uelectronic : electronic energy Kcal/mole

∆Uvibration : vibration energy cal/mole

∆Urotation : rotation energy cal/mole

∆Utranslation : translation energy cal/mole

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 U : How to measure?
∆U
Considering that mechanical work w is equal to p∆V :

∆U
U = q - p ∆V
V

∆U
U = qv
measurable at constant volume
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 Since most chemical processes proceed at
constant pressure rather than at constant volume,
it is more convenient to use other new definition
off iinternall energy called
ll d enthalpy
h l : H = U + pV
V or
∆H = ∆U + p∆V

∆U
U + p ∆V
V = qp

∆H
H = qp
measurable at constant volume
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 ‰ If enthalpy (or internal energy) is the driving
force of chemical processes, it is reasonable to
expect that all chemical processes should be
followed by a heat release (exothermic).
‰ In practice,
practice however
however, although it is true that
most chemical processes are exothermic,
some endothermic (heat absorbed) chemical
processes do
d exist.
i
‰ It may be concluded, therefore, that enthalpy
(or internal energy) is NOT the driving force of
chemical processes

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 Th S
The Second
dLLaw off Th
Thermodynamics
d i :

It is impossible to take heat from a body of uniform

temperature and convert it entirely into work
without causing a change in the thermodynamic
state of some other body.

It is impossible to have chemical processes,

working with a 100 % efficiency. Some waste
energy must also be released.

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 THE CONCEPT OF FREE ENERGY

∆ G = ∆ H - T∆ S

Free energy Enthalpy Waste

Energy

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 ∆ G = ∆ H - T∆ S

Chemical System
B di
Bonding S
Structure

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 CHEMICAL BONDING :
A Thermodynamic Interpretation

A B A B

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 ATRACTIVE ENERGY :
• Between nucleus A and electron B
• Between electron A and nucleus B

Uatt= - Catt/r
REPULSIVE ENERGY :
• Between nucleus A and nucleus B
• Between electron A and electron B

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Urep= + Crep/r 21
 U

Urep= + Crep//r

Uatttt= - Catttt/r

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 BOND ENERGY :
The energy required to break down
chemical bond into separate atoms

BOND LENGTH :
The equilibrium distance between two
atoms
t involving
i l i chemical
h i l bond.
b d

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 BOND ENERGY vs INTERAL ENERGY

INTERNAL ENERGY U :
The most stable chemical bond would be
f
formed
d at the
h lowest
l internall energy

BOND ENERGY :
The stronger chemical bond would be
formed with bigger
gg bond energygy
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 Chemical processes tend to proceed
spontaneously in the direction of diminished
free energy, i.e. when the free energy
change, ΔG, is negative.

∆G is the driving force of

chemical
h i l processes

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 Chemical pprocesses tends to p 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)
off th
the products
d t iis hi
higher;
h 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 TΔS
greater than ΔH; or
‰ the total bonding forces in the products are weaker
than those in the reactants but the entropy increase
(i
(increase in
i disorder)
di d ) isi more than
th large
l enoughh to
t
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 A → B

GA > GB ΔG < 0 Spontaneous

p g :A→B
change

GA = GB ΔG = 0 A → B is at the equilibrium state

GA < GB ΔG > 0 Spontaneous change : B → A

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 CHEMICAL EQUILIBRIUM :
A Thermodynamic Interpretation

Gi = Gio + RT ln [[i]]

A → B ∆G = GB – GA

GA GB

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 A → B
GB = GBo + RT ln
l [B]
GA = GAo + RT ln [[A]]

∆G = ∆Go+ RT ln [B]/[A]

∆G = ∆Go+ RT ln Q
Q : reaction quotient
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 A → B
At equilibrium state (∆G = 0) :

- ΔGo = RT ln K THEORETICAL
CONCEPT

K = [B]eq/[A]eq PRACTICAL
APPLICATION

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 A general chemical process
:

aA+bB cC +dD

K = [C]c[D]d/[A]a[B]b

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A El
A. Electrolytic
t l ti Dissociation
Di i ti off Water
W t

H2O → H+ + OH-

Kw = [H+] [OH-]

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 Ion Product of Water Kw :

T, ºC Kw pKw

0 0.12 x 10-14 14.93

15 0.45 x 10-14 14. 35
20 0.68 x 10-14 14.17
25 1.01 x 10-14 14.00
30 1.47 x 10-14 13.83
50 5.48 x 10-14 13.26
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B. Equilibrium of Acids and Bases :

HA → H3O+ + A-
Ka = [H+] x [A-]/[A]

B + H+ → BH+ + OH-
Kb = [BH+] x [OH-]/[B]

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 Acidity and Bacisity Constant :
Acid pKa Base pKb

HClO4 -7 ClO4- 21
HCl -3 Cl- 17
HNO3 -1 NO3- 15
H30+ 0 H20 14
H2S 7.1 HS- 6.9
NH4+ 9.3 NH3 4.7
H2O 14 OH- 0
NH3 23 NH2 -9
OH- 24 O2- -10
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 Ka is the experimental measure of
acid strength

Kb is the experimental measure of

base strength

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 THE PRINCIPLES OF
ENTROPY

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 P, V, T P, V, T

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 MORE ORDRED
LESS DISORDRED
LOW ENTROPY

Æ
LESS ORDERED
MORE
DISORDERED
HIGH ENTROPY

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

WEAK WEAK HIGH

CHEMICAL ~ BOND ~ INTERNAL Æ HIGH
BONDS ENERGY ENERGY ENTHALPY

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 ∆G = ∆H - T∆S

System Structure

Chemical Bonding

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Principle--1 :
Principle
Chemical processes tend to proceed spontaneously
in the direction of diminished free energy, i.e. when
th ffree energy change,
the h ΔG is
ΔG, i negative.
ti

∆G = ∆H - T∆S is
i the
h ddriving
i i fforce off
chemical processes

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

‰ If the total bonding

g forces in the p
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
p g lower to make TΔS
greater than ΔH; 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.
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
products exceed those in the reactants and the total
p
disorder (entropy) of the products is higher

∆H = (HP-HR) < 0

∆G = ∆H - T∆S

∆S = (SP-S
SR) > 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
p
disorder in the products is lower but not enough
lower to make TΔS greater than ΔH

∆H = (HP-HR) < 0

∆G = ∆H - T∆S

∆S = (SP-S
SR) < 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
p
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-S
SR) > 0 ∆G < 0
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 Principle--2 :
Principle
The gaseous state is more probable than
the liquid state, which in turn is more
probable than the solid state

SOLID Æ LIQUID Æ GAS

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 Entropy of Various Substances at 25° (in eu)
Entropy Values at 25°
25° (in eu)
S b t
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
9.86 56 03
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
9/9/2015 bromide HgBr2 40.71 46.80 76.51
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 Principle-3 :
Principle-
A monatomic gas is more probable
than a polyatomic molecular gas, and
hence tends to have higher entropy

MOLECULAR STATE Æ ATOMIC STATE

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

H 27 .4 H2 15 6 - -
N 36..6
36 N2 22..9
22 - -
O 38.5
38. O2 24.5
24. O3 19
19..0
F 37..9
37 F2 24..4
24 - -
Si 40..1
40 Si2 17..5
17 - -
P 39.0
39. P2 26.1
26. P4 16.
16.7
S 40..1
40 S2 27..3
27 S8 12
12..9
Cl 39..5
39 Cl2 26..6
26 - -
NO2 57 .5 N2O4 36.4 - -

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 Principle-4 :
Principle-
An amorphous solid is more probable
than a crystalline solid
solid, and a simple
crystalline solid is more probable
than a more complex crystalline solid

CRYSTALLYNE Æ AMORPHOUS

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 Principle-5 :
Principle-
A molecular addition compound, or a
coordination
di ti complex, l iis lless probable
b bl
than its separate components

H3N-BF3 Æ NH3 + BF3

Cu(NH3)4SO4 Æ Cu2++ 4NH3+ SO42-

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 Principle-6 :
Principle-
Compounds
p or elements of higher
g
atomic weight, or molecule of the free
elements themselves, tend to have
higher entropy

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 Principle-7 :
Principle-
At ordinaryy temperatures,
p , entropy
py
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
l ti l small.ll

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 Comparison on the values of Enthalpies and of Free
Energies of Formation (in kcal mole-1).
Substances ΔHfo ΔGfo T ΔSfo
H2O (l) - 57.80 - 54.64 + 3.16
HCl (g)
( ) - 22.00
22 00 - 22.77
22 77 - 0.77
0 77
SO2 (g) - 70.96 - 71.79 - 0.83
H2S (g) - 4.82
4 82 - 7.89
7 89 - 3.67
3 67
H2Te (g) + 36.90 + 33.10 - 3.80
KNO3 (c) - 117.16
117 16 - 93.96
93 96 + 23.20
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)
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- 41.40 - 19.10 + 22.30 56
PH3 (g) + 2.21 + 4.36 + 2.15
 Before the concept of entropy had been clearly
recognized, the heat of a reaction (entalpy) was
the sole factor determining
g 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
units, whereas heats
of reaction are commonly more than a kilocalorie
per mole.

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 Principle-8 :
Principle-
All chemical reactions that increase the
entropy occur spontaneously at high
enough temperatures

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 Energy T∆S = f (T)

∆H = f (T)

∆S = f (T)
∆G > 0

∆G < 0 T (K)
TC
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∆G = ∆H - T ∆S 59
Comparison on the Values of Standard Enthalpies and
of Free Energies for Some Chemical Reactions

ΔHfo ΔGfo

Reactions kcal/mol kcal/mol

CCll4(g)
( ) + 2 H2O(g)
( ) Æ CO2 (g)
( ) + 4HCl(g)
l( ) - 41.2 - 61.2
SF4 (g) + 3 H2O (g) Æ SO3 (g) + 6HF(g) - 45.0 - 75.9
CaO(c)
( ) + CO2(g)
( ) Æ CaCO3(c)
( ) - 42.5 - 31.1

CH4(g)+
(g)+2
2 O2 (g) Æ CO2 (g)+ 2 H2O (g) - 191.8 - 191.4
AsCl3(l) +3 NaF(c) Æ 3NaCl(c) + AsF3(g) - 24.7 - 31.7
AlBr3 (c) + PCl3 (g) Æ AlCl3(c) + PBr3 (g) - 3.1 - 4.3
CH3OH(l)+NH3(g)
(g)Æ
Æ CH3NH2(g) + H2O(g) + 3.5 - 4.3
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