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Atomic structure:
Heisenbergs Uncertainty Principle:
Heisenbergs Uncertainty Principle states that if measuring a variable of a
particle there is inherent uncertainty in the act.
The scientific principle stating that at the same time it is impossible to know
exact position and momentum of a particle.
Heisenbergs state that in act of measuring a variable of particle there is
inherent uncertainty.
It is impossible to determine the position of momentum of a particle at any
given point in time.
German scientist Werners Heisenberg gave a principle about uncertainties
in simultaneous measurement of position and momentum of small particles.
This is known as Heisenbergs uncertainty principle.
Heisenbergs Uncertainty Principle Equations:
The product of the uncertainty in the position (x) and the uncertainty in momentum (p)
is always constant.
This is equal to or greater than h/4p, where h is planks constant.
p = m
v where
m is the mass of the particle and
v shows the uncertainty in velocity.
Thus, the uncertainty equation is
p. x h/4p


Heisenbergs Uncertainty Principle formula
The mathematical expression for the Heisenberg's uncertainty principle
p. x h/4p

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By using the above equation, the calculated value of p is the minimum value of p for any
particular value of x. Similar the calculated value of x also shows the minimum value of x
for any specific value of p.
As p = m. v,
So the equation becomes (m. v). x h/4p
Or
( v)( x) h/4pm


Principle of Heisenbergs Uncertainty Principle:

i) A light phenomenon is used for measuring the position and momentum of electron.
ii) The microscope is used to see the reflected photon.
iii) The position and momentum of electron is disturbed due to hitting with photon.
iv) The e- has wave particle duality and it shows uncertainty position and momentum.

Significance of Heisenberg Uncertainty Principle

Heisenberg Uncertainty Principle is good for all the objects and is more significant for
microscopic particles.
For example,
i) The light on the running rat from the torch cannot change the direction and position of
rat.
Or if mass of particle is 1 mg then by using Heisenbergs uncertainty principle
formula.
(v)(x) = (h/4) m
By putting the value of h = 6.626 x 10-34 kg m
2
s
-1
,
m = 1 mg or 10
-6
kg.
So (v) (x) = (6.626 x 10
-34
/ 4) x 3.1416 x 10
-6
,
Or (v) (x) = 10
-28
m
2
s
-1

ii) If the mass of an electron is 10
-27
kg and the uncertainty in position is equal to 10
-11
m then
find the uncertainty in velocity.
Solution:

(v) (x) = (h4) m,

Put the value of x =10
-11
m,
h = 6.626 x 10
-34
kg m
2
s
-1
and m =10
-27
kg.
So (v) = (h4) m (x),

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Or
v = 6.626x103443.141610271011

v = 5.27 x 10
5
m s
-1






iii) Schrodinger wave equation (time independent
Erwin Schrodinger derived equations that conserve energy using his wave function to explain
the electron. After that he solved the equation for different potentials applied to electron. His
description considered the basis for the modern understanding of the electron.

Time-dependent Schrdinger equation (general)


The Time Independent Schrdinger Equation

Second order differential equations, like the Schrdinger Equation, can be solved by separation
of variables. These separated solutions can then be used to solve the problem in general.
Assume that we can factorize the solution between time and space.



Plug this into the Schrdinger Equation.




Put everything that depends on on the left and everything that depends on on the right.


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Since we have a function of only set equal to a function of only , they both must equal a
constant. In the equation above, we call the constant , (with some knowledge of the
outcome). We now have an equation in set equal to a constant




which has a simple general solution,

and an equation in set equal to a constant




which depends on the problem to be solved (through ).
The equation is often called the Time Independent Schrdinger Equation.

Here, is a constant. The full time dependent solution is.



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Particle in one-dimensional box:
It is a fundamental quantum mechanical approximation describing the translation motion of a
single particle confined inside an infinitely deep well from which it cannot escape.
It is a common application of a quantum mechanics model.
Represents an electron or another particle that is trapped between walls.
In Quantum mechanics the particle in a box model describes a particle free to move in a
small space surrounded by impenetrable barriers.

Quantum numbers:
Quantum Number describes values of conserved quantities in the dynamics of a
quantum system. In case of quantum numbers of electrons, they can be defined
as "The sets of numerical values which give acceptable solutions to the
Schrdinger wave equation for the Hydrogen atom".
Each e
-
(electron) has a total of 4 numbers called quantum numbers.
In an atom each electron has distinctive set of quantum numbers.
Quantum number determine the electron configurations of an atom
There are four quantum numbers:
n - Describes the energy level
- describes the sub shell
m - describes the orbital of the subshell
ms - Describes the spin
Each quantum numbers indicates an electrons trait within an atom which
satisfies to explain the movement of electron as a wave function.

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In an atom each electron has a unique set of quantum numbers. Quantum
numbers can help determine other characteristics of atoms such as ionization
energy and the atomic radius.

Hydrogen Atom Wave Functions
It is an atom of the chemical element Hydrogen.
The wave function of the hydrogenic atom depends on 3 quantum numbers.
The principle quantum numbers: n=1,2,3,4,..
Angular momentum quantum numbers : l= 0,1,2,3,n-1
Magnetic quantum numbers : m
l
=l,l-1,1-2,.,-1

Structure of s orbitals:




Structure of p orbitals


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Chemical bonding:
Types of chemical bonding: Ionic bonds and Covalent bonds.
Ionic Bond:
Ionic bonds are strong bonds. These are formed when opposite charged ions are attract
to each other.
Ionic bond are Non directional.
Example; Atomic radius: Na (r=0.192nm) Cl(r=0.099nm)
Ionic Radius: Na(r=0.095nm) Cl(r=0.181nm)
Ionic compound conduct electricity in molten or in solution.
It involves a metal and a non metal ion through electrostatic attraction.
Complete transfer of valence electron between atoms. It generates 2 oppositely
charged ions.
Require an electron donor, metal and an electron acceptor, non metal.
Characteristics of Ionic Compound:
Hard and rigid due to strong forces of attractions between opposite charged ions
High melting point and High boiling point.
Dissolve easily in water
Solid ionic compounds do not conduct electricity
Crystalline.

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Lattice energy:
It is a type of Potential energy and also called as lattice enthalpy.
It is the energy required to break apart an ionic solid. Then convert its components
atoms into gaseous ions.
It is used to explain the stability of ionic solids.
Symbol of lattice energy U
Depends on 2 factors:-
Charged on the ions and the distance between the centers of neighboring +ve and ve
ions.
Greater magnitude of ion charge, greater is lattice energy.
Born-Haber cycle
It is an approach to analyze reaction energies. Born Haber Cycle developed by 2 German
scientists Max Born and Fritz Haber.
The Born Haber cycle is concerned with formation of an ionic bond from the reaction of
a metal with a halogen.
Simply energy that shows how ionic compounds are formed from their constituents
elements.
They allow lattice energy to be calculated theoretically using empirical data.
BH Cycle is a simplified method. It was developed by Max Born and Fritz Haber in 1919.
To understand the Born-Haber cycle fully we can define the meaning of lattice energy
first. It is the energy released when a metal ion in its gaseous state combines with a non
metal anion in its gaseous state to form an ionic solid.
The energy released in the following processes is called lattice energy.
Li
+
(g) + F
-
(g) -> LiF(s) LE = -1047kJ
Mg
+
(g) + O
2-
(g) -> MgO(s)LE = -3916kJ


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For example, the formation of sodium chloride(NaCl) from sodium and chloride ion involves
788 kj/mol of energy and dissociation of sodium chloride into it constituent ions requires same
amount of energy.

NaCl(s) Na+(g) + Cl- (g) LH= 788 kj/mol
Na+(g) + Cl-(g) NaCl(s) LH = -788 kj/mol

When oppositely charged ions interact to form ionic solid, a large amount of energy is
released and dissociation of crystal also require a lot of energy which makes melting
point and boiling points of crystal very high.
Born Haber cycle is used to determine this lattice energy by using other energy values
like ionization energy, electron affinity, dissociation energy, sublimation energy and
heat of formation.
Covalent Bonds:
It is a chemical bond.
It involves the sharing of electron pairs between atoms.
Covalent bonds are polar or non polar.
It holds atoms together in molecules. It allows molecules to share electron with other
molecules.
It occurs at unpaired valence electron on outer shell for each atom. In covalent bon ve
charge of e- pair attracts +ve charge nuclei of atom
Eg: H
2
O has two bonds.
Characteristics of covalent bond:
Low melting and boiling point.
Poor conductor of electricity


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Dipole moments: When there is separation of charge dipole moments occur between 2 ions in
an ionic bond or between atoms in covalent bond.
Cause of dipole moments:
1. Differences in electro negativity.
2. Larger the differences in electro negativity larger the dipole moments.
3. Dipole moment is measure of polarity of molecule.
Dipole moments
= q r

Dipole moment, q Magnitude of the charger, distance between charges.
Valence Bond Theory:
It assumes that all bonds are localized bonds.
It formed between 2 atoms by the donation of an electron from each atom.
This theory describes covalent bonds formation as well as the electronic structure of
molecules.
Heitler and London proposed Valence Bond theory to explain the formation of covalent
bonds.
Main postulates of valence bond theory:
i) A covalent bond is formed by overlapping of 2 and half filled valence atomic orbitals.
ii) The e- (electron) in the overlapping orbitals gets paired. It confined between the nuclei
of 2 atoms.
iii) Due to overlapping the e- density between 2 bonded atoms increases.
iv) Greater the extent of overlapping stronger is the bond formed.

Molecular Orbital theory:

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It is a method for determining molecular structure in which electrons are not assigned
to individual bonds between atoms.
It is a function that describes the wave like behavior of a single electron in a molecule.

Using LCAO method some basic rules for making MOs:-
n atomic orbitals must produce n molecular orbitals.
To combine the atomic orbitals must be appropriate symmetry.
Each MO must be normal and must be orthogonal to every other MO.

Comparison of valence bond and molecular orbital theories
VALENCE BOND THEORY
According to valence Bond theory:
Bonds are localized formed between 2 atoms by donation of an electron from each
atom. First proposed by W.Heitler and F.London in 1927
A covalent bond is formed by the overlapping of partially filled orbitals of 2 atoms.
Overlapping orbitals must have electrons with opposite spin.
Atoms involved in bond formation should have unpaired electrons.
Resonance play important role.
Calculations are simpler
MOLECULAR ORBITAL THEORY
It is a chemical bonding theory. It explains the bonding between 2 atoms caused by the
overlap of half filled atomic orbitals.
Bonds are localized to 2 atoms as well as molecule.
Proposed by F.Hund and R.S. Mulliken in 1932.
There is no place of resonance.

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A covalent bond is formed by the overlapping of atomic orbitals which form molecular
orbitals.
2 kinds of molecular orbitals:-
Bonding Molecular orbital theory
Anti bonding molecular theory.

Bonding e- occupies molecular orbital.
Calculations are very tedious.

BOND ORDER: It is the number of bonding pairs of e- between 2 atoms.
o Single bond- bond order 1
o Double bond bond order 2
o Triple bond- bond order 3

Bond order and Bond length
Bond order and Bond length indicates the type and strength of covalent bond between
atoms. Bond order and length are inversely proportional to each other.

Bond order:
It is the number of bonding pairs of electrons between 2 atoms.
In a covalent between 2 atoms a single bond has a bond order of one, a double
bond has a bond order of two, a triple bond has a bond order of 3 and so on.

Determine the bond order for nitrate: NO3.


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SOLUTION

1) Draw the Lewis Structure.1 nitrate.JPG

2) Count the total number of bonds 2 nitrate.The total number of bonds is 4.

3) Count the number of bonds between individual atoms. The number of bonds
between individual atoms is 3.

4) Divide the number of bonds between individual atoms by the total number of bonds.

4/3= 1.33 the bond order is 1.33

Solid state:
Crystal systems: It is a class of point groups. Crystal is a solid composed of atoms, ions and
molecules that verify long range periodic order in 3 dimensions.
Unit cells: The simplest repeating unit in a crystal. Opposite faces of a unit cell are
parallel
Lattice points: the points in space about which the particles are free to vibrate in a
crystal.

Bragg's law:
It explains the relationships between an X-Ray light shooting into and its
reflection off from crystal surface. This law was introduced by Sir W.L. Bragg.
This law states that:-

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When the X-Ray is incident onto a crystal surface its angle of incidence will
reflect back with a same angle of scattering.
The structures of crystal and molecules are often being identified using X-Ray
diffraction studies which are explained by Braggs Law.
The law states that when the x-ray is incident onto a crystal surface, its angle of incidence,
, will reflect back with a same angle of scattering, . And, when the path difference, d is
equal to a whole number, n, of wavelength, a constructive interference will occur. Consider
a single crystal with aligned planes of lattice points separated by a distance d.
Monochromatic X-rays A, B, and C are incident upon the crystal at an angle . They reflect
off atoms X, Y, or Z.
The path difference between the ray reflected at atom X and the ray reflected at atom Y can be
seen to be 2YX. From the Law of Sines we can express this distance YX in terms of the lattice
distance and the X-ray incident angle:
If the path difference is equal to an integer multiple of the wavelength, then X-rays A and B (and
by extension C) will arrive at atom X in the same phase. In other words, given the following
conditions:
then the scattered radiation will undergo constructive interference and thus the crystal will
appear to have reflected the X-radiation. If, however, this condition is not satisfied, then
destructive interference will occur. Braggs Law
n=2dsin
Where,
= the wavelength of the x-ray
d = the spacing of the crystal layers (path difference)
= the incident angle (the angle between incident ray and the scatter plane)

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n = an integer
The principle of Braggs law is applied in the construction of instruments such as Bragg
spectrometer, which is often used to study the structure of crystals and molecules.

X-Ray Diffraction:
It measures the average spacings between layers of rows of atoms.
It determines the orientation of a single crystal .
It finds the crystal structure of an unknown material.
It measures the size, shape and internal stress of small crystalline regions.

The atomic planes of a crystal cause an incident beam of X-rays to
Interfere with one another as they leave the crystal. The phenomenon is
called X-ray diffraction.
Closed packing in solid state:
Matter exists in solid state. There are 2 types of close packing found in solids.
These are Cubic Closed Packed and Hexagonal closed Packed lattice.


Radius Ratio rules:
i) Coordination numbers are determined largely by electrostatic considerations in
ideal Ionic crystals.
ii) Cations surround themselves with as many anions as possible. This can be
related to the relative sizes of the ions----------Radius ratio rule.
Calculation of some limiting radius ratio values

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The rotatable structure opposite shows the CsCl structure in which
the Cs
+
ion is surrounded by 8 Cl
-
ions.
To get as close to the cation as possible, the anions must touch along
the edge of the cube, as shown in the figure below. Click the
'Directions in Which Anions Touch' button to see this view.

The side of the cube has a length, a, where:
a = 2r
-

Along the body diagonal, the Cs
+
is touching the two Cl
-
ions on either end so its length, d,
is:
d = r
-
+ 2r
+
+ r
-
= 2r
+
+ 2r
-




Two dimensional view of packing around Cs+ in CsCl showing two opposite edges
of the unit cell.








Using Pythagoras theorem, the length of the side and the body diagonal of a cube are related:
d
2
= a
2
+ a
2
+ a
2
= 3a
2
= 3 4r
-
2
= 12r
-
2


d = 2(3)
1/2
r
-

So,
2r
-
+ 2r
+
= 2r(3)
1/2
r
-


r
+
/ r
-
= (3)
1/2
1 = 0.732
As long as the radius of the cation is no smaller than 73% that of the anion, the CsCl structure,
with its high Madelung constant, is possible. If the cation is larger than this, the structure is

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stable as the anions do not need to touch. If the cation is smaller than this, the cation and anion
will not be in contact. A lower coordination number is then needed.
Kinetic molecular theory
Properties of Maxwell's distribution of speeds
o The Maxwell distribution describes the distribution of particle speeds in an ideal gas.
Average speed: The average speed is the sum of the speeds of all of the particles divided by the
number of particles.
Most probable speed is the speed associated with the highest point in the Maxwell distribution.
Liquid state:
Kelvin equation: The vapor pressure of a liquid to the effect of surface curvature. It describes
the changes in vapor pressure.
Kelvin equation:
p
s
(r)/ p
s
() = exp ({2
w
}/{
w
R
v
Tr}) = exp (a/r)
r = droplet radius
p
s
(r) = the actual vapour pressure of droplet of radius r
p
s
()= the saturation vapour pressure over bulk water

w
= surface tension

w
= water density
R
v
- the universal gas constant, T - temperature
Example:
Saturation ratio Critical radius
1 0.12 m
1.1 0.0126 m
2 1.73 nm


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Surface Tension: It is the energy or work to increase the surface area of a liquid due to
Intermolecular forces.
Wetting: It is the ability of a liquid to maintain contact with a solid surface. The degree of
wetting is determined by a force balance between adhesive and cohesive forces.
It deals with 3 phrases of materials: GAS, LIQUID AND SOLID.
Contact angle is one of the common ways to measure the wettability of a surface or material.
Wetting: It is the study of how a liquid deposited on a solid substrate spreads out.

Thermodynamics: It is a branch of physics concerned with heat and temperature and their
relation to energy and work. It refers to descriptions of bodies and processes.
4 laws of thermodynamics:
Zeroth law of thermodynamics
First law of thermodynamics
Second law of thermodynamics
Third law of thermodynamics.
: Work, Heat and internal energy
Work W: useful Energy transferred across the systems Boundaries, capable of producing
Macroscopic-Mechanical Motion of a systems center of Mass.
Work done by a Gas :




Constant Volume Process


Constant Pressure Process


Constant Temperature Process

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First law of thermodynamics: This law is also known as Law of conservation of energy. It states
that energy cannot be created or destroyed. It can only be distributed or changed from one
form to another.
Second law of thermodynamics:
It states that entropy of an isolated system never increases due isolated systems always
evolve toward thermodynamic equilibrium.
It identifies the direction of a process.
It used to determine the Quality of energy and introduce concepts of reversible
processes and irreversibilities.
Third Law of thermodynamics: It states that the entropy of any isolated system approaches a
constant value as the temperature approaches zero.

Clausius-Clapeyron equation:
The Clausius-clapeyron relation named after Rudolf Clausius and Benoit
The relationship between the temperature of a liquid and its vapors pressure is not a
straight line. This behavior can be explained with the Clausius-
Clapeyron equation.
It is a way of characterizing a discontinuous phase transition between 2
phases of matter of a single constituent.
Debye-Huckel theory of strong electrolytes
Peter Debye and Erich Huckel was proposed the Debye-Huckel
theory.It is a linearilized Poisson Boltzman model. This model assumes
an extremely simplified model of the electrolyte solution.
This theory based on 3 assumptions of how ions act in solution:-

I. Electrolytes completely dissociate into ions in solution.
II. Solutions of Electrolytes are very dilute, on the order of 0.01 M.

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Each ion is surrounded by ions of the opposite charge, on average.

Debye and Hckel developed the following equation to calculate the mean ionic activity
coefficient :
log=1.824106(T)3/2z+zI
where
is the dielectric constant,
z+ and z are the charges of the cation and anion, respectively, and
I is a quantity called the ionic strength of the solution.
The above equation is known as the Debye-Hckel Limiting Law. The ionic strength is
calculated by the following relation:
I=12imiz2i
where mi and zi are the molality and the charge of the ith ion in the electrolyte. Since
most of the electrolyte solutions we study are aqueous (=78.54) and have a
temperature of 298 K, the Limiting Law reduces to
log=0.509z+zI.

Galvanic cells:
It is also known as voltaic cell.
It was named after Luigi Galvani or Alessandro Volta
respectively.
Galvanic cell is an electrochemical cell that releases
energy.
It consists of 2 half cells joined by two salt bridge.

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These are the devices in which electron transfer occurs via
an external circuit.
If a strip of Zn is placed in a solution of CuSO
4
, Cu is deposited on the
Zn and the Zn dissolves by forming Zn
2+
.
Zn is spontaneously oxidized to Zn
2+
by Cu
2+
.
The Cu
2+
is spontaneously reduced to Cu
0
by Zn.
Galvanic cells consist of :
Anode: Zn
2+
(aq) + 2e
2

Cathode: Cu
2+
(aq) + 2e
-
Cu(s)
Salt bridge: cations move from anode to cathode, anions move from cathode
to anode.

Below is a galvanic cell in which the reaction between A
+
and B is exothermic, with a G of -10
kJ/mol under standard conditions and a value of E
0
of 0.10 V.







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Concentration Cells :
It is an electrolyte cell.
It is comprised of two half cells with the same electrodes but differing
in concentration.
It acts to dilute the more concentrations solutions.
Uses of concentration cells
A pH meter is a specific type of concentration cell that uses the basic setup
of a concentration cell to determine the Ph or the acidity/basicity of a
specific solution.

Electrochemical series:
The electrochemical series is built up by arranging various redox
equilibria in order of their standard electrode potential.
Most negative E values are placed at the top of the electrochemical
series. Most positive at the bottom.

equilibrium E(volts)

-3.03

-2.92

-2.87

-2.71

-2.37

-1.66

-0.76

-0.44

-0.13

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0

+0.34

+0.80

+1.50
EMF: It is the maximum potential difference between 2 electrodes of a
galvanic cells.

Chemical Kinetics: Differential and integral rate equations for Zeroth, first,
second and fractional order reactions
Differential rate law: It relates the rate of reaction to the concentration of the various species
in the system.

Zero-Order Reaction: The rate of reaction is a constant. When the limiting reactant is
completely consumed, the reaction abrupts stops.

Differential Rate Law: r = k

The rate constant, k, has units of mole L
-1
sec
-1
.

First-Order Reaction: The rate of reaction is directly proportional to the concentration
of one of the reactants.

Differential Rate Law: r = k [A]

The rate constant, k, has units of sec
-1
.

Second-Order Reaction: The rate of reaction is directly proportional to the square of the
concentration of one of the reactants.

Differential Rate Law: r = k [A]
2


The rate constant, k, has units of L mole
-1
sec
-1
.

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Photochemistry:
It is a sub-discipline of chemistry.
It is the study of chemical reactions that proceed with the absorption of light by atoms
and molecules.
Examples:
Photosynthesis,
degradations of plastics,
Formation of vitamin D with sunlight.

Photosynthesis involves the absorption of light by the chlorophyll in plants to produce
carbohydrates from CO
2
and H
2
O.

Photochemical reactions are the reactions that takes place in the presence of light only
or some other radiations.
These reactions do not take place in the dark.
Temperature has very little effect on the rate of a photochemical reactions.
Light is a form of energy. Hence it provides the necessary activation energy for the
reaction to take place.