CHEMICAL BONDING AND MOLECULAR ORBITAL

MOLECULAR STRUCTURE THEORY

CLASSICAL IDEA OF
REDOX REACTIONS REDOX REACTIONS
MOT
MO Theory was developed by F.Hund and R.S Mulliken in 1932
SALIENT FEATURES
The electrons in a molecule are present in various molecular orbitals as the electrons of atoms are
present in various atomic orbitals
The atomic orbitals of comparable energies and proper symmetry combine to form molecular orbitals
While an electron in an atomic orbital is influenced by one nucleus in a molecular orbital it is
influence by two or more nuclei depending upon the number of atoms in the molecule.Thus an
atomic orbital is monocentric while a molecular orbital is polycentric
The number of MO orbital formed is equal to the number of combining atomic orbital
When two atomic orbitals combine,two molecular orbitals are formed.One is bonding molecular
orbital and other is antibonding molecular orbital.
MOT
The bonding molecular orbitl has lower energy and hence greater stability than the
corresponding antibonding molecular orbital
Just as the electron probability distribution around a nucleus in an atom is given by
an atomic orbital ,The electron distribution around a group of nuclei in a molecule is
given by a molecular orbital
The molecular orbitals are filled in accordance with Aufbau,paulis and hunds rule
just like atomic orbital
Recall Aufbau , paulis and hunds rule
HOW MO ARE FORMED?
 LINEAR COMBINATION OF ATOMIC ORBITAL (LCAO)
Consider hydrogen molecule having atoms A and B .Each hydrogen atom has 1
electron in 1s orbital.The atomic orbitals represented as t
The formation of MO may be orbitals described by the linear combination of atomic
orbitals that can take place by addition and by substraction of wavefunction of
individual atomic orbitals asshown below.
𝜓
  𝑀𝑂 =𝜓 𝐴 ±𝜓 𝐵
The two molecular orbitals are formed as

BONDING MOLECULAR ORBITAL and ANTIBONDING MOLECULAR

ORBITAL
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CONSTRUCTIVE AND
DESTRUCTIVE INTERFERENCE
The formation of molecular orbitals can be understood in terms of constructive and destructive
interference of the electron waves of the combining atoms.
In the formation of BMO,the two electron waves of the bonding atoms reinforce each other due to
constructive interference while in the formation of ABMO,the electron wave cancel each other due to
destructive interference .
As a result,Electron density in BMO=>Located btwn the nuclei of bonded atoms=>repulsion btwn nuclei
is very less
ABMO=>Electron density located away from the space btwn the nuclei,there is a nodsl plane btwn the
nuclei
Electron placed in a BMO tend to hold the nuclei together and stabilize a molecule,BMO always posses
lower energy than either of the atomic orbitals that have combined to form it.
In constrast electron placed in ABMO destabilise the molecule=>repulsion of the electrons in tnis orbital
more than attraction btwn electrons and the nuclei =>increase in energy
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CONDITIONS FOR THE
COMBINATION OF ATOMIC
ORBITALS
The combining atomic orbitals must have the same or nearly the same energy
The combing atomic orbitals must have the same symmetry about the molecular axis
The combing atomic orbitals must overlap to the maximum extent
TYPES OF MOLECULAR
ORBITALS
 sigma=>MO are symmetrical around the bond axis
pi=>not symmetrical
delta are the threeMO of diatomic molecules
FORMATION OF BONDING
AND ANTIBONDING
ORBITALS:ILLUSTRATION
FORMATION OF MOLECULAR
ORBITALS:ILLUSTRATION

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ELECTRONIC
CONFIGURATION OF
MOLECULAR ORBITALS
ELECTRONIC
CONFIGURATION
 ELECTRONS MORE THAN 14

ELECTRONS UPTO 14
ELECTRONIC
CONFIGURATION AND
MOLECULAR BEHAVIOUR
The distribution of electrons among various molecular orbitals is called electronic
configuration of the molecule.
From the electronic configuration it is possible to get information about the
following
STABILITY
OF BOND NATURE
MOLECUL ORDER OF BOND
ES
BOND MAGNECTI
LENGTH C NATURE
STABILITY OF MOLECULES
Nb= number of electrons occupying bonding orbitals
Na= number of electrons occupying antibonding molecular orbitals
STABLE MOLECULE Nb>Na
Reason: More bonding orbitals are
occupied and so the bonding influence
stronger and a stable molecule results
UNSTABLE MOLECULE Nb<Na
Reason:Antibonding influence is stronger
,so molecule is unstable
 BOND ORDER
Defined as one half the difference between the number of electrons present in the
bonding and the antibonding orbitals.
HIGHER THE BONDORDER MORE STABLE THE MOLECULE
BOND ½ (Nb-Na)
ORDER

POSITIVE BOND ORDER,Stable Nb>Na

molecule
NEGATIVE BOND ORDER or Nb< Na
ZERO,Unstable molecule
NATURE OF BOND
BOND NATURE OF
ORDER BOND
1 SINGLE BOND
2 DOUBLE BOND
3 TRIPLE BOND
BOND LENGTH AND
MAGNETIC NATURE
As the bond order increases bond length decreases
Paired electrons=diamagnetic
Unpaired electrons=paramagnetic
BONDING IN SOME
HOMONUCLEAR DIATOMIC
MOLECULES
1.Hydrogen Molecule (H2)
2.Helium molecule (He2)
3. Lithium molecule (Li2)
4.Carbon molecule (C2)
5.Oxygen molecule.(O2)
QUESTIONS
Compare the relative stability of the following species and indicate their magnectic
properties
O2 , O2+, O2-,O2 2-
What is meant by bond order? Calculate the bondorder of N2,O2,O2+,O2-
HYDROGEN BONDING
N,O,F are the highly electronegative elements.When they are attached to a hydrogen
atom to form covalent bond,the electrons of the covalent bond is shifted towards the
more electronegative atom.This partially positively charged hydrogen atom forms a
bond with the other more electronegative atom.This bond is called hydrogen
bonding.
Weaker than covalent bond

Hydrogen bond act as a bridge between two atoms,represented by dotted line

Defined as the attractive force which binds hydrogen atom of one molecule with
the electronegative atom of another molecule
CAUSE OF FORMATION OF
HYDROGEN BOND
TYPES OF H-BONDS
Two types
INTERMOLECULAR HYDROGEN BOND:Formed between two different
molecule ex: HF,Water or alcohol.
HYDROGEN BONDING
INTRAMOLECULAR H BONDING
It is formed when hydrogen atom is in between the two highly electronegative atoms
within the same molecule.
UNIT 8: REDOX REACTION
CLASSICAL IDEA OF REDOX
REACTIONS-OXIDATION AND
REDUCTION REACTIONS
OXIDATION REDUCTION
ADDITION OF OXYGEN REMOVAL OF OXYGEN
ADDITION OF ELECTRONEGATIVE REMOVAL OF ELECTRONEGATIVE
ELEMENT ELEMENT
REMOVAL OF HYDROGEN ADDITION OF HYDROGEN
REMOVAL OF ELECTROPOSITIVE ELEMENT ADDITION OF ELECTROPOSITIVE
ELEMENT
OXIDATION
ADDITION OF OXYGEN
2Mg + O2 2MgO
S +O2 SO2
ADDITION OF OXYGEN AND REMOVAL OF HYDROGEN
CH4 + 2O2 CO2 + 2H2O
ADDITION OF ELECTRONEGATIVE ELEMENT
Mg + F2 MgF2
Mg +S MgS
REMOVAL OF ELECTROPOSITIVE ELEMENTS
2K4[Fe(CN)6] +H2O2 2K3[Fe(CN)6] + 2KOH
REDUCTION
REMOVAL OF OXYGEN
2HgO 2Hg +O2
REMOVAL OF ELECTRONEGATIVE ELEMENT
2FeCl3+H2 2FeCl2+2HCl
ADDITION OF HYDROGEN
CH2=CH2+H2 CH3 CH3
ADDITION OF ELECTROPOSITIVE ELEMENT
2HgCl2+SnCl2 Hg2Cl2+SnCl4
Simultaneous oxidation of stannous chloride to stannic chloride is also occurring because of the addition of
electronegative element chlorine to it .
OXIDATION AND REDUCTION OCCUR SIMULTANEOUSLY KNOWN AS REDOX REACTION
QUESTION
REDOX REACTION IN TERMS
OF ELECTRON TRANSFER
REACTIONS
OXIDATION: Loss of electron by any species
REDUCTION:Gain of electrons by any species
OXIDISING AGENT:Acceptor of electron
REDUCING AGENT: Donar of electron
EXAMPLES
2Na + Cl2 2NaCl
2Na + O2 Na2O
2Na +S Na2S
QUESTION
COMPETATIVE ELECTRON
TRANSFER REACTIONS
Zn +Cu2+ Zn2+ + Cu
When we place a metallic Zn strip in an aqueous solution of copper
nitrate,the strip becomes coated with reddish metallic copper and the blue
color of the solution disappears.Formation of Zn2+ can be easily judged
when the blue color disappears,When H2S,passed through the colorless soln
containing Zn2+,White ZnS is formed
ELECTRON TRANSFER
REACTION
Metallic copper dipped in aqueous solution of zinc sulphate,no visible reaction occurred.
Reaction between copper metal and silvernitrate.The solution develops blue color due to the
formation of Cu2+
Cu +2Ag2+ Cu2+ + 2Ag
OXIDATION NUMBER
Oxidation number denotes the oxidation state of an element in a compound ascertained according to a set of rules
formulated on the basis that electron pair in a covalent bond belongs to more electronegative element.
The rules for calculating oxidation number:
1.Elements in the free or uncombinedstate, each atom bears an oxidation number of zero.ex:Na,Mg,Al,H 2,O2,Cl2.
2.For ions composed for only one atom, the oxidation number is equal to the charge on the ion. Na+ has an oxidation
number of +1.Mg2+ =+2
Fe3+ion=+3 Cl- =-1 O2- =-2
In their compounds all alkali metals have an oxidation number of +1,all alkaline earth metals of +2.Aluminium is
regarded to have an oxidation number of +3 in all its compounds.
The oxidation number of oxygen in most of its compounds is -2.Exceptions peroxides and superoxides
Peroxide(H2O2,Na2O2) oxygen atom is assigned an oxidation number of -1.
Superoxide(KO2,RbO2) each oxygen atom is assigned an oxidation number -1/2
In OF2 = +2, O2F2 = +1
OXIDATION NUMBER
The oxidation number of hydrogen is +1 except when it is bonded to metals in binary
compounds ex:LiH,NaH,CaH2,Its oxidation number is -1
In all its compounds fluorine has an oxidation number of -1Other halogen also has an
oxidation number of -1,when they occur as halide ions.
Chlorine,bromine,iodine when combined with oxygen have positive oxidation
numbersex:oxoacids,oxoanions
The algebraic sum of the oxidation number of all the atoms in a compound must be zero.
In polyatomic ion,the sum is equal to the charge on the ion
Ex:CO32- must be equal to -2
Oxidation state/oxidation number.
STOCK NOTATION
The oxidation state/number of a metal in a compound is sometimes presented
according to the notation given by German Chemist Alfred Stock.It is popularly
known as Stock notation
Ex Au(111)Cl3
Sn(111)Cl2
APPLICATION
OXIDATION :An increase in the oxidation number of the element in the given
substance
REDUCTION:A decrease in the oxidation number of the element in the given
substance.
OXIDISING AGENT:A reagent which can increase the oxidation number of an
element.Oxidants
REDUCING AGENT:A reagent which lowers the oxidation number of an
element,Reductants
REDOX REACTIONS:Reactions which involve change in oxidation number of the
interacting species.
QUESTIONS
QUESTIONS
QUESTIONS
QUESTIONS
QUESTIONS
QUESTIONS
TYPES OF REDOX REACTION
COMBINATION REACTION
A +B C Either A and B or both must be in elemental form for such a reaction to be redox reaction.
All combination reaction which make use of elemental dioxygen are redox reactions
C +O2 CO2
3Mg + N2 Mg3N2
DECOMPOSITION REACTION
Decomposition reaction leads to the breakdown of a compound into two or more components at least one of
which must be in the elemental form.
2NaH 2Na +3H2
2H2O 2H2 + O2,
All decomposition reaction are not redox, ex:decomposition of calcium carbonate
TYPES OF REDOX REACTIONS
DISPLACEMENT REACTION
An ion in a compound is replaced by an ion of another element
X +YZ XZ +Y
Two categories 1)Metal displacement 2)Nonmetal displacement.
1)METAL DISPLACEMENT:
A metal in a compound can be displaced by another metal in the uncombined state.
Application: Extraction of pure metals
CuSO4+Zn Cu + ZnSO4
V2O5 + 5Ca 2V + 5CaO
TiCl4 + 2Mg Ti + 2MgCl2
TYPES OF REDOX REACTION
NON-METAL DISPLACEMENT
Involves hydrogen displacement and rarely occurring reaction involving oxygen
displacement.
All alkali metals and some alkaline earth metals which are good reductants will displace
hydrogen from cold water
2Na +2H2O 2NaOH + H2
Ca + 2H2O Ca(OH)2 + H2
Less active metals such as magnesium and iron react with steam to produce hydrogen gas
Mg +H2O Mg(OH)2+H2
2Fe + 3H2O Fe2O3+3H2
TYPES OF REDOX REACTIONS
Many metals, including those which do not react with cold water, are capable of displacing hydrogen from
acids. ex: Cadmium and tin
Zn + HCl ZnCl2+H2
Fe + 2HCl FeCl2+H2
Application: preparation of dihydrogen in laboratory.
Fe is most reactive and Mg least reactive
Ag , Au do not even react with hydrochloric acid.
Zn>Cu>Ag Reactivity order
Like metals halogen has also activity series
The power of these elements as oxidizing agent decreases as we move down the group
This means Fluorine is so reactive and it can displace chlorine , bromine and iodine ions in solution.
Fluorine is so reactive that it attacks water and displaces the oxygen of water.
TYPES
2H2O + 2F2 4HF + O2

For this reason that the displacement reactions of chlorine ,bromine and iodine using fluorine are not generally
carried out.

On the other hand ,chlorine can displace bromide and iodide ions

Cl2 +2 KBr 2KCl +Br2

Industrial application
TYPES
DISPROPORTIONATION REACTION
Special type
An element in one oxidation state is simultaneously oxidized and reduced.
One of the reacting substances in a dispropotionation reaction always contains an element that can exist in at
least three oxidation state.
2H2O2 2H2O+O2
Phosphorous, Sulphur and chlorine undergo dispropotionation in the alkaline medium.
Cl2+2OH- ClO- + Cl- + H2O
Application: The hyperchlorite ion ClO - formed oxidises the color bearing stains of the substances to colorless
compounds.
Fluorine doesnot undergo dispropotionation tendency,it cannot show positive oxidation number due to high
electronegativity
BALANCING REDOX
REACTIONS
OXIDATION NUMBER METHOD
Write the correct formula for each reactant and product
Identify atoms which undergo change in oxidation number in the reaction by assigning the
oxidation number
Calculate the increase or decrease I the oxidation number per atom and for the entire
molecule/ion in which it occurs.If these are not equal then multiply by suitable number so
that these become equal.
Make the charges equal on both sides add H+ and OH-.If the reaction is carried out in
acidic medium add H+ and basic medium add OH-
Make the number of hydrogen atoms equal in both sides by adding water molecule .Then
check for oxygen atom if they are equal then the equation is balanced.
BALANCING REDOX
REACTIONS
HALF REACTION METHOD
Write down the ionic form of unbalanced chemical equation
Separate I to two half reaction
Balance atoms other than H and O.
Acidic medium,add water to balance O atoms and H+ to balance H atoms.
Basic medium Add equal number of OH- to balance the charges.
Add electrons to balance the charges.
Add two half reactions to achieve the overall reaction
Verify that the equation contains the same charges on both sides of the equation.
HOW TO REMEMBER EASILY?
OXIDATION NUMBER METHOD (ACIDIC)
Balance atom other than H and O
Balance electron
Balance O
Balance H
OXIDATION NUMBER METHOD(BASIC)
Balance atom other than H and O
Balance electron
Balance charge by adding OH-
Balance O
Balance H
HOW TO REMEMBER EASILY?
HALF CELL REACTION (ACIDIC)
Make two half cell reaction
Balance atom other than H and O
Balance O
Balance H
Blance charge using electron
Add
HOW TO REMEMBER EASILY?
HALF CELL REACTION (BASIC)
Make two half cell reaction
Balance O
Balance H
Add equal OH- proportional to H+
Balace by adding electons
Add
 OXIDATION NUMBER
METHOD(ACIDIC MEDIUM)
Cr2O72- +SO3 Cr3++ SO42-

Cr2O72- +SO3 Cr3++ SO42-

Cr2O72- +SO3 Cr3++ SO42-

Cr2O72- +SO3 Cr3++ SO42-

Cr2O72- +SO3 Cr3++ SO42-

OXIDATION NUMBER
METHOD
(BASIC MEDIUM)
MnO4-+Br- MnO2+BrO3-

MnO4-+Br- MnO2+BrO3-

MnO4-+Br- MnO2+BrO3-

MnO4-+Br- MnO2+BrO3-
MnO4-+Br- MnO2+BrO3-
HALF REACTION
METHOD(ACIDIC MEDIUM)
Fe2++Cr2O72- Fe3++Cr3+
Fe2+ Fe3+
Cr2O72- Cr3+

Cr2O72- Cr3+

Cr2O72- Cr3+
Fe2++Cr2O72- Fe3++Cr3+
HALF REACTION
METHOD(BASIC MEDIUM)
MnO4-+ I- MnO2+ I2
I- I2
MnO4- MnO2
I- I2

MnO4- MnO2
MnO4- MnO2
MnO4- MnO2
MnO4- MnO2
MnO4- MnO2
MnO4-+I- MnO2+I2