Inorganic Reactions Slide-01

INTRODUCTION

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 What is Chemistry ?

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

• Structure
• Composition
• Properties
• Energy
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 INORGANIC CHEMISTRY :
is the study of the structure, properties,
composition, mechanisms, and reactions
of inorganic compounds

CHEMISTRY

ORGANIC CHEMISTRY :
is the study of the structure, properties,
composition, mechanisms, and reactions
of organic compounds
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• Inorganic compounds may be classified by the
elements or groups they contain (e.g., oxides,
sulfates).
• The major classes of inorganic polymers are silicones,
silanes, silicates, and borates.
• Coordination compounds (or complexes), an important
subclass of inorganic compounds, consist of molecules
with a central metal atom (usually a transition
element) bonded to one or more nonmetallic ligands
(inorganic, organic, or both) and are often intensely
coloured.
• Until 1828, scientists believed that organic compounds
could be formed only by life processes.
• Since carbon has a far greater tendency to form
molecular chains and rings than do other elements, its
compounds are vastly more numerous (many millions
have been described) than all others known.
• Living organisms consist mostly of water and organic
compounds : proteins, carbohydrates, fats, nucleic acids,
hormones, vitamins, and a host of others.
• Natural and synthetic fibres and most fuels, drugs, and
plastics are organic.
• Hydrocarbons contain only carbon and hydrogen;
organic compounds with other functional groups include
carboxylic acids, alcohols, aldehydes, ketones, phenols,
ethers, esters, and other, more complex, molecules,
including heterocyclic compounds, isoprenoids, and
amino acids.
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 THE SCOPE OF CHEMISTRY :

INORGANIC CHEMISTRY
ORGANIC CHEMISTRY
BIOCHEMISTRY

PHYSICAL ANALYTICAL
CHEMISTRY CHEMISTRY

THEORETICAL DEVICES EXPERIMENTAL DEVICES

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 Physical Chemistry
• Physical chemistry is the study of macroscopic, atomic,
subatomic, and particulate phenomena in chemical
systems in terms of physical laws and concepts.
• It applies the principles, practices and concepts of physics
such as motion, energy, force, time, thermodynamics,
quantum chemistry, statistical mechanics and dynamics.
• Physical chemistry, is predominantly (but not always) a
macroscopic or supra-molecular science, as the majority
of the principles on which physical chemistry was
founded are concepts related to the bulk rather than on
molecular/atomic structure alone; for example, chemical
equilibrium, colloids.
 Analytical Chemistry
• Analytical chemistry is the study of the separation,
identification, and quantification of the chemical
components of natural and artificial materials.
• Qualitative analysis gives an indication of the identity of
the chemical species in the sample and
• Quantitative analysis determines the amount of one or
more of these components. The separation of
components is often performed prior to analysis.
• Analytical chemistry is also focused on improvements in
experimental design, chemometrics, and the creation of
new measurement tools to provide better chemical
information.
 PHYSICAL ANALYTICAL
CHEMISTRY CHEMISTRY

THEORETICAL DEVICES EXPERIMENTAL DEVICES

THEORETICAL EXPERIMENTAL
EXPLANATIONS OBSERVED FACTS

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 Scientific Method

http://www.sciencebuddies.org/science-fair-projects/project_scientific_method.shtml
  It is not chemistry if we learn theories
without facts, and it is not science if we
learn only facts without learning theories.

 Theories must not replace facts in

chemistry, but should explain them.

Kornhauser (1981)

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 CHEMICAL REACTION
the focal point of any chemical studies

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 Why do chemical reactions
occur?
For the very essence of practical chemistry
is the scientific control of chemical change.

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

Reactants  products
In order for this to happen, atoms, which are initially
attached to one another in a certain way in the
reactants, become separated, at least to some extent,
and rearranged in the products.

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 +

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 +

REACTANT ATOMIC GAS PRODUCTS

S
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 Falling Ball : An Example

E1 = mgh1

E2 = mgh2
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 THE CONCEPT OF ENERGY

Definition

Energy could be defined as the capacity of

a system to do work

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 Work

Work = Force x Distance

F F

r2 – r1
r1 r2
w : work

w = F x (r2 – r1) F : force

r2 – r1 : distance
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 w = F x (r2 – r1)
F
w = x A (r2 – r1)
A
w = P x (V2 – V1)

w = P x ∆V
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 Pex

Pex

P1
P2
v1 v2 v1 v2

w= ∫P
ex dV
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 HYDROGEN ATOMIC MODEL

F q1q2
- v
F=- —
r 2

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 q1q2
F=- —
r 2

∞ ∞
q1q2
U = ∫o F dr = - ∫o — dr
r2
q1q2 ∞
U=+ — ]o
r
q1q2 q1q2
U=- — → U=- —
r r
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 MOLECULES

Atomic Nuclei

ATOMS

Electrons
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 Atomic Nuclei  nuclear binding energy

Electrons  electronic energy

Vibrations  vibration energy
Rotations  rotation energy
Translations  translation energy

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 The First Law of Thermodynamics :
In ordinary processes, energy is conserved, it is
neither created nor destroyed

q
heat
SYSTEM
W
work

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 If heat q is added to a system and work w is done by
the system, the total amount of energy added to the
system, (q - w);
w) is not destroyed but is stored within
the system to increase the internal energy ∆U

q
heat
SYSTEM
W
∆U work

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THE INTERNAL ENERGY : The total energy

∆U = q - w

∆Unuclear : nuclear binding energy MeV

∆Uelectronic : electronic energy eV
∆Uvibration : vibration energy cal/mole
∆Urotation : rotation energy cal/mole
∆Utranslation : translation energy cal/mole
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Dalton’s Atomic Theory
1. All elements are composed of sub-
microscopic indivisible parts called
atoms.
2. Atoms of the same element are
identical, those of different atoms are
different.
3. Atoms of different elements combine in
whole number ratios to form
compounds.
4. Chemical reactions involve the
rearrangement of atoms. No new
atoms are created or destroyed.
Chemical Energy :
• Atoms of different elements combine
in whole number ratios to form
compounds.
• Chemical reactions involve the
rearrangement of atoms. No new
atoms are created or destroyed.

The energy involved in chemical

reactions is in the range of several
electron volt (1 eV = 23.06
Kcal/mole)
 ∆U : How to measure?
Considering that mechanical work w is equal to p∆V :

∆U = q - p ∆V
∆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 of internal energy
called enthalpy : H = U + pV or ∆H = ∆U + p∆V

∆U + p ∆V = qp

∆H = qp
measurable at constant pressure
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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, however, although it is true that
most chemical processes are exothermic,
some endothermic (heat absorbed) chemical
processes do exist.
 It may be concluded, therefore, that enthalpy
(or internal energy) is NOT the driving force
of chemical processes

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 The Second Law of Thermodynamics :

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

Net energy Total Correction

energy for useless
Energy

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 GIBBS FREE ENERGY

∆G = ∆H - T∆S

Chemical System
Bonding Structuring

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 CHEMICAL BONDING :
A Thermodynamic Perspective

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

Urep= + Crep/r
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 U

Urep= + Crep/r

Uatt= - Catt/r

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 U

Urep= + Crep/r

Uatt= - Catt/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 involving chemical bond.

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 BOND ENERGY vs INTERAL ENERGY

INTERNAL ENERGY U :
The most stable chemical bond would be
formed at the lowest internal energy

BOND ENERGY :
The stronger chemical bond would be
formed with larger bond energy

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 U

rAB : Bond Length

rAB

EAB EAB : Bond Energy

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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 is the driving force of

chemical processes

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 THE DRIVING FORCE

G = H - TS

The Degree of
Disorder of the
Structure
The Strength of
Chemical Bond

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 CHEMICAL BONDS

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 Electrostatic Coulombic
Approach Forces + -

CHEMICAL
BONDING

Electron sharing Sharing of

Approach electron pair

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 Electrostatic Ionic Bond
Approach

CHEMICAL
BONDING normal

Covalent Bond
Electron coordination
Metalic Bond
Sharing
Approach Hydrogen Bond

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 BOND STRENGTH

STRONG LARGE LOW

CHEMICAL INTERNAL LOW
BONDS ~ BOND
ENERGY ~ ENERGY  ENTHALPY

WEAK SMALL HIGH

CHEMICAL
BONDS ~ BOND ~ INTERNAL
ENERGY
 HIGH
ENERGY ENTHALPY

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 ENTROPY

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 ENTROPY EXPERIMENT

P, V, T P, V, T

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 MORE ORDRED
LESS DISORDRED
LOWER ENTROPY

LESS ORDERED
MORE DISORDERED
HIGHER ENTROPY

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 Boltzmann’s Concept of Entropy :

S = ln Ω

The Degree of
Disorder
Entropy
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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

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 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.

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 ∆G = ∆H - T∆S

System Structure

Chemical Bonding

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 Chemical processes tends to proceed
spontaneously :
1. 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

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 ∆H < 0

∆G = ∆H - T∆S

∆S > 0 ∆G < 0

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2. 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
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 ∆H < 0

∆G = ∆H - T∆S

∆S < 0 ∆G < 0

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3. 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
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 ∆H > 0

∆G = ∆H - T∆S

∆S > 0 ∆G < 0

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 ENTROPY PRINCIPLES

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 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

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 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
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Sodium chloride NaCl 17.33 20.22 54.88 67
 Principle-3 :

A monatomic gas is more probable than a polyatomic

molecular gas, and hence tends to have higher entropy

MOLECULAR STATE  ATOMIC STATE

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 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 - -
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 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

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 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-

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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, 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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 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.

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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
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
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PH3 (g) + 2.21 + 4.36 + 2.15
Principle-8 :

All chemical reactions that increase the entropy

occur spontaneously at high enough temperatures

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∆H = ∆Ho + ∫ Cp dT

Cp
∆S = ∆So + ∫ dT
T

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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 78
Comparison on the Values of Standard Enthalpies
and of Free Energies for Some Chemical Reactions

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
CH3OH(l)+NH3(g) CH3NH2(g) + H2O(g) + 3.5 - 4.3
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 CaO(c) + CO2(g)  CaCO3(c)

Standard enthalpy at 25oC Standard free energy at 25oC

ΔHo = - 45.0 kcal/mole ΔGo = - 31.1 kcal/mole

TΔS = ΔH - ΔG
TΔS = - 45.0 - 31.1 kcal/mole
TΔS = - 13.9 kcal/mole

ΔS = 46.4 cal mole-1 K-1

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