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 :

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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. 6/2/2013 7

THE SCOPE OF CHEMISTRY :

INORGANIC CHEMISTRY ORGANIC CHEMISTRY BIOCHEMISTRY

PHYSICAL CHEMISTRY

ANALYTICAL CHEMISTRY

THEORETICAL DEVICES
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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 CHEMISTRY

ANALYTICAL CHEMISTRY

THEORETICAL DEVICES

EXPERIMENTAL DEVICES

THEORETICAL EXPLANATIONS
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EXPERIMENTAL 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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+
REACTANTS
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ATOMIC GAS SYSTEM

PRODUCTS
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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
r1

F
r2 r1
r2

w : work

w = F x (r2 r1)
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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
v1 v2 v1

P2
v2

w=
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Pex dV
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HYDROGEN ATOMIC MODEL

+ r F 6/2/2013

F=-

q1q2

r2

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F=-

q1q2

r2

U = o F dr = - o U=+

q1q2

r2

dr

q1q2 r q1q2

]o

U=6/2/2013

U=-

q1q2

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SYSTEM

MOLECULES

Atomic Nuclei ATOMS Electrons

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Atomic Nuclei nuclear binding energy

Electrons electronic energy

Vibrations
Rotations Translations

vibration energy
rotation energy 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); is not destroyed but is stored within the system to increase the internal energy U

q
heat
SYSTEM

W
work

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THE INTERNAL ENERGY : The total energy

U = q - w
Unuclear Uelectronic Uvibration Urotation : nuclear binding energy : electronic energy : vibration energy : rotation energy MeV eV cal/mole cal/mole

Utranslation
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: translation energy

cal/mole
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Daltons Atomic Theory

1. All elements are composed of submicroscopic indivisible parts called atoms. Atoms of the same element are identical, those of different atoms are different. 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.

2.

3.

4.

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 pV :

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 + pV

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 energy Correction for useless Energy

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GIBBS FREE ENERGY

G = H - T S
Chemical Bonding System 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

r
Uatt= - Catt/r

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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 Approach

Coulombic Forces

CHEMICAL BONDING Electron sharing Approach

Sharing of electron pair

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Electrostatic Approach

Ionic Bond

CHEMICAL BONDING

normal

Covalent Bond

Electron Sharing Approach

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Metalic Bond
Hydrogen Bond

coordination

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BOND STRENGTH
STRONG CHEMICAL BONDS LOW INTERNAL ENERGY

~ ~

LARGE BOND ENERGY

~ ~

LOW ENTHALPY HIGH

WEAK CHEMICAL BONDS

SMALL BOND ENERGY

HIGH INTERNAL 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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Boltzmanns Concept of Entropy :

S = ln
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 - TS 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 TS 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 - TS
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
WEAKER
BOND

PRODUCTS

STRONGER
BOND

ENTROPY
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LOWER

HIGHER
ENTROPY
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H < 0

G = H - TS
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 TS greater than H

REACTANTS
WEAKER
BOND

PRODUCTS

STRONGER
BOND

HIGHER
ENTROPY
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ENTROPY
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LOWER

H < 0

G = H - TS
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
STRONGER
BOND

PRODUCTS

WEAKER
BOND

ENTROPY
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LOWER

ENTROPY
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HIGER

H > 0

G = H - TS
S > 0

G < 0

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THE PRINCIPLES OF ENTROPY

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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 Sodium Phosphorous Silicone Lead Water Methanol Boron trioxide Na P Si Pb H2O CH3OH B2O3 Solid 12.30 9.82 4.43 15.50 12.91 Liquid 13.83 10.28 11.21 17.14 16.72 30.30 18.55 Gas 36.71 38.98 40.12 41.89 45.11 56.80 64.42

Silicone dioxide
Lithium oxide Beryllium oxide Titanium oxide Lead oxide

SiO2
Li2O BeO TiO2 PbO

10.00
898 3.38 12.01 15.59

11.35
9.86 10.50 15.43 20.55

54.62
56.03 47.21 56.44 57.35

Boron trichloride
Silicone tetrachloride Lead chloride Sodium chloride Mercury bromide
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BCl3
SiCl4 PbCl2 NaCl HgBr2

45.30
32.50 17.33 40.71

57.20 38.34 20.22 46.80

85.30
79.20 76.63 54.88 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

MOLECULAR STATE ATOMIC STATE

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Entropy of Monatomic and Polyatomic Gas (in eu/g atom) H N O F Si 27 .4 36.6 38.5 37.9 40.1 H2 N2 O2 F2 Si2 15 6 22.9 24.5 24.4 17.5 -

O3 19.0 -

P S Cl

39.0 40.1 39.5

P2 S2 Cl2 N2O4

26.1 27.3 26.6 36.4

P4 16.7 S8 12.9 69

NO2 57 .5
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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+ SO426/2/2013 71

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 H2O (l) Hfo - 57.80 Gfo - 54.64 T Sfo + 3.16

HCl (g)
SO2 (g) H2S (g)

- 22.00
- 70.96 - 4.82

- 22.77
- 71.79 - 7.89

- 0.77
- 0.83 - 3.67

H2Te (g)
KNO3 (c) Na2CO3 (c) Al2(SO4)3 (c) NH3 (g) N2O4 (g) HNO3 (l) PH3 (g)
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+ 36.90
- 117.16 - 270.30 - 820.98 - 11.04 + 2.31 - 41.40 + 2.21

+ 33.10
- 93.96 - 250.40 - 738.99 - 3.98 + 23.49 - 19.10 + 4.36

- 3.80
+ 23.20 + 19.90 + 81.99 + 7.06 + 21.18 + 22.30 + 2.15
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Principle-8 :
All chemical reactions that increase the entropy occur spontaneously at high enough temperatures

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H = Ho + Cp dT

C p o S = S + dT T
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Energy

TS = f (T)

H = f (T)

S = f (T) G > 0

TC
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G < 0
G = H - T S

T (K)

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Comparison on the Values of Standard Enthalpies and of Free Energies for Some Chemical Reactions
Hfo Gfo kcal/mol - 61.2 - 75.9 - 31.1 - 191.4 - 31.7 - 4.3 - 4.3
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Reactions
CCl4(g) + 2 H2O(g) CO2 (g) + 4HCl(g) SF4 (g) + 3 H2O (g) SO3 (g) + 6HF(g) CaO(c) + CO2(g) CaCO3(c) CH4(g)+2 O2 (g) CO2 (g)+ 2 H2O (g) AsCl3(l) +3 NaF(c) 3NaCl(c) + AsF3(g) AlBr3 (c) + PCl3 (g) AlCl3(c) + PBr3 (g) CH3OH(l)+NH3(g) CH3NH2(g) + H2O(g)
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kcal/mol - 41.2 - 45.0 - 42.5 - 191.8 - 24.7 - 3.1 + 3.5

CaO(c) + CO2(g) CaCO3(c)

Standard enthalpy at 25oC Standard free energy at 25oC

Ho = - 45.0 kcal/mole

Go = - 31.1 kcal/mole

TS = H - G
TS = - 45.0 - 31.1 kcal/mole
TS = - 13.9 kcal/mole

S = 46.4 cal mole-1 K-1

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