CHEMISTRY 11th Notes PDF
CHEMISTRY 11th Notes PDF
CHEMISTRY 11th Notes PDF
CHAPTER NO 01
Rule # 1:
If the digit to be dropped is greater than 5, then add "1" to the last digit to be retained
and drop all digits farther to the right.
For example:
3.677 is rounded off to 3.68 if we need three significant figures in measurement.
3.677 is rounded off to 3.7 if we need two significant figures in measurement.
Rule # 2:
If the digit to be dropped is less than 5, then simply drop it without adding any number
to the last digit.
For example:
6.632 is rounded off to 6.63 if we need three significant figures in measurement.
6.632 is rounded off to 6.6 if we need two significant figures in measurement.
Rule # 3:
If the digit to be dropped is exactly 5 then:
(A) If the digit to be retained is even, then just drop the "5".
For example:
6.65 is rounded off to 6.6 if we need two significant figures in measurement.
3.4665 is rounded off to 6.466 if we need four significant figures in measurement.
(B) If the digit to be retained is odd, then add "1" to it.
For example:
6.35 is rounded off to 6.4 if we need two significant figures in measurement.
3.4675 is rounded off to 6.468 if we need four significant figures in measurement.
Remember: Zero is an even number
3.05 is rounded off to 3.0 if we need two significant figures in measurement.
Use of significant figures in
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addition and subtraction
In addition and subtraction we consider the significant figures on the right side of
decimal point. This
means that only as many digits are to be retained to the right side of decimal point as
the number with fewest digits to the right of the decimal point.
For example:
4.345 + 23.5 =27.845 (actual answer by using calculator)
Answer after rounding off: 27.8
Use of significant figures in
multiplication and division
In multiplication and division , the number obtained after calculation of two or more
numbers must have
no more significant figure than that number used in multiplication or division.
For example:
4.3458 x 2.7 =11.73366(actual answer by using calculator)
Answer after rounding off: 12(because 2.7 has only two significant figures)
Error
An error is defined as:
"The difference between the measured value and the actual value."
If two persons use the same instrument for measurement for finding the same
measurement, it is not essential that they may get the same results. There may arises a
difference between their measurements. This difference is referred to as an "ERROR".
Types Of Error
Errors can be divided into three categories:
(1) Personal Error
(2) Systematic Error
(3) Random Error
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Empirical formula only indicates atomic ratios but it does not indicate actual number of
atoms of different kinds present in the molecule of a compound.
Two or more compound may have same empirical formula.
Empirical formula is determined by experiment.
Molecular Formula www.citycollegiate.com
The molecular formula of a compound is defined as:
"The formula of a compound which not only expresses the relative number of atoms of each
kind but also expresses the actual number of atoms of each element present in one
molecule".
Molecular formula and empirical formula of a compound are related as:
MOLECULAR FORMULA = (EMPIRICAL FORMULA) n
Where "n" is an integer and is given by:
n = molecular mass of compound / Empirical formula mass of compound
Molecular formula of propane = C3H8.
Molecular formula of sugar = C12H22O11.
Limiting Reactant
The limiting reactant is defined as:
" The substance which produces least amount of products when it is
completely consumed in a chemical reaction".
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Mole www.citycollegiate.com
"The atomic mass or molecular mass of a substance expressed in grams is called mole".
OR
A mole may also be defined as
" the gram atomic mass or gram molecular mass or gram formula mass
of a substance that contains 6.02 x 1023 particles."
OR
"The mass in grams of the atoms or molecules or ions which contains
Avogadro's number of particles i.e. 6.02 x 1023 particles."
For example:
(1) Atomic mass of Carbon = 12 a.m.u.
Therefore 12 gram of carbon = 1 mole of carbon.
(2) molecular mass of nitrogen = 28 a.m.u.
Therefore 28 gram of nitrogen = 1 mole of nitrogen.
(3) Formula mass of NaCl = 58.5 a.m.u.
Therefore 58.5 gram of NaCl = 1 mole of NaCl.
Mole is denoted by "n".
Formula www.citycollegiate.com
Number of moles of substance = mass of substance (in grams) / molecular mass or
atomic mass or formula mass
Avogadro's Number
One mole of any substance contains equal number of particles (atoms or molecules or
ions).Value of this number is 6.02 x 1023. This constant value or number is referred to as
"AVOGADRO'S NUMBER"
For example:
One mole of hydrogen = 6.02 x 1023 molecule of hydrogen.
One mole of sodium = 6.02 x 1023 sodium of hydrogen.
One mole of Ca+2 = 6.02 x 1023 ions of Ca+2.
It is denoted by "NA".
Stoichiometry www.citycollegiate.com
Stoichiometry refers to chemical calculations.
Stoichiometry is defined as:
"The quantitative relationship among the reactants and products in a balanced chemical
equation".
Assumption of Stoichiometric
Calculations
There are two important assumptions for stoichiometric calculations:
(1) Reactants are completely converted into products.
(2) No supplementary or side-reactions occur.
Suppose we want to calculate the mass of CO2 formed when a given mass of carbon
burns in air.
The reaction is:
C + O2 CO2
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In actual practice, it is possible that we get less amount of CO2 than the calculated mass
of CO2.This is because that the given mass of carbon can also form CO in addition to CO
2.
2C + O2 2CO
This means that we have to avoid the formation of carbon monoxide.
Types of stoichiometric calculations
Stoichiometric calculations can be divided into three categories.
(1) Mass - Mass Relationship
(2) Mass - Volume Relationship
(3) Volume - Volume Relationship
Gay-Lussac's Law Of Combining
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Volume
According to Gay-Lussac's Law Of Combining Volume:
"Gases react in the ratio of small whole numbers by volume under
similar conditions of temperature and pressure".
For example:
Nitrogen and hydrogen react to form ammonia gas.
N2 + 3H2 2NH3
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CHAPTER NO 02
CHAPTER # 02
.Three States of Matter
Definitions
Ideal gas
An ideal gas is a hypothetical (imaginary) gas, which has no existence. Ideal gas obeys
all gas laws at all temperatures and pressures. There is no force of attraction or
repulsion between the molecules of an ideal gas. Molecules of ideal gas occupy no
space.
Real gas
Gases that exist are real gases such as Hydrogen, Nitrogen, Oxygen, He, Ne, F 2, CO2,
CO etc. Real gases do not obey gas laws at all temperatures and pressures. Real gases
deviate from ideal behavior at high pressure and low temperature. There exists small
force of attraction between the molecules of real gases.
S.T.P
S.T.P: stands for "STANDARD TEMPERATURE AND PRESSURE"
The volume of a gas changes with temperature and pressure. Therefore it is not
completely defined unless temperature and pressure of the gas are specifically
mentioned.
In order to compare different gases, volume of gases must be at a standard set of
conditions of temperature and pressure.
The melting point of ice i.e. 0 0C or 273 K and the average pressure of atmosphere at
sea level i.e. 1.00 atmosphere or 760 torr are the standard conditions of temperature
and pressure.
Pressure
Force per unit area is called PRESSURE.
P = F/A
UNITS:
· Atmosphere
· cm of Hg
· Torr
· mm of Hg
· N/m2 or Pascal
· Psi or pound per square inch
Conversions of Pressure in different units:
1 atmosphere = 76 cm of Hg
1 atmosphere = 760 torr or mm of Hg
1 atmosphere = 1.01 X 105 N/m2 OR Pascal
1 atmosphere = 14.7 psi
Sublimation
Some solid substances on heating directly converted in gaseous state without passing
through liquid state. This phenomenon is called as SUBLIMATION.
In the light of K.M.T the intermolecular forces in these solids (such as NH4Cl, Camphor,
Naphthalene, Iodine) is less than ordinary solids. Therefore high energy molecules at
solid surface overcome the attraction forces and directly pass into vapours.
Molar Volume
At S.T.P volume of one mole of any gas is 22.4dm3. This volume is referred to as "Molar
Volume".
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Or
A 0 0C & 1 atmosphere volume of one mole of any gas is 22.4dm3. This volume is called
"Molar Volume"
Anisotropy
The crystalline substances which show variable intensity of physical properties in
different directions are known ANISOTROPES and the phenomenon is called
ANISOTROPY. For example:
1) Mica can be cleaved easily parallel to its plane but difficult to cut perpendicular
to its plane.
2) Graphite conduct electricity parallel to its plane but it can not conduct
electricity perpendicular to its plane.
Gas laws
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Boyle’ѕ law
Introduction
Boyle’s law is a quantitative relationship between volume and pressure of a gas at
constant temperature.
Statement
"The volume of a given mass of a gas is inversely proportional to pressure if
temperature remains constant ". Mathematical representation of Boyle’s law
According to Boyle’s law
V 1/P
V= (constant)(1/P)
PV=constant
At P1 pressure
P1V1 = constant ------------------(1)
At P2 pressure
P2V2 = constant ------------------(2)
Comparing (1) & ( 2)
P 1V 1 = P 2V2
.
Second statement
"At constant temperature, the product of pressure and volume of a gas
remains constant "
Graphical representation of Boyle’s law
Graph between P & V at constant temperature is a smooth curve known as "parabola"
Charles law
Introduction
It is quantitative relation between volume and absolute temperature of a gas at
constant pressure.
Statement
"The volume of a given mass of a gas at constant pressure is directly
proportional to absolute temperature"
Second statement
Mathematical representation
V/T = constant
At T1 k
V1/T1 = k ---------------(1)
At T2 k
V2/T2 = k ---------------(2)
Thus
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V1/T1 = V2/T2
Third statement
By using above equation ,Charles’s law can also be stated as:
Graphical representation
But practically volume of a gas can never become zero. Actually no gas can achieve the
lowest possible temperature and before -273.16 0C all gases are condensed to liquid.
This temperature is referred to as absolute scale or absolute zero. At -273.16 0C all
molecular motions are ceased.
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According to Boyle’s Law :
Volume of a given mass of a gas is inversely proportional to
pressure if temperature remains constant
. V 1/P -------------------(1)
According to Charles’s law:
Volume of a given mass of a gas is directly proportional to
absolute temperature if pressure remains constant.
V T ----------------------(2)
According to Avogadro’s law:
Volume of a gas is directly proportional to no of moles.
V n -----------------------(3)
Combining 1,2,and 3
V T.n1/P. V nT/P
V= (constant) nT/P
PV/nT = constant
Here constant is R
PV/nT = R
Or
PV= n RT
This is the equation of state of a gas (Ideal Gas Equation)
R= Universal gas constant
Value of R is equal to 0.0821 dm3.atmosphere/mole.k
R has different values in different systems of unit
ANOTHER FORM:
As PV/nT = constant
For initial conditions:
When temperature is T1 and pressure is P1:
P1V1/T1 = constant -----------------(a)
Similarly for final conditions:
P2V2/T2 = constant -----------------(b)
From equation (a) & (b)
P1V1/T1 = P2V2/T2
VALUE OF R
In atmp.dm3/mole.k
Consider one mole of an ideal gas at S.T.P.
As we know that at S.T.P. one mole of any gas occupies 22.4dm3 volume.
DATA
T = 0 0C + 273 = 273K P=1 atmp n =1 mole V =22.4 dm3
R=?
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In J/mole.k
Consider onemole of an ideal gas at S.T.P.
P=1.01 x 105 N/m2
T = 0 0C + 273 = 273K
n =1 mole
V =22.4 dm3 = 22.4/1000=0.0224 m3
R =?
Using ideal gas equation
PV = nRT
R=PV/nT
R = 1.01 x 105 x 0.0224/ 1x 273
R = 8.31 J/mole K
According to K.M.T, there are very strong forces of attraction between the molecules of a
solid and there is no space between two molecules. Due to this reason solids are completely
incompressible. If we apply high pressure on a solid it will not compress but it will deform.
Q) Explain diffusibility of solids in terms of K.M.T.
In terms of K.M.T, there are very strong force of attraction between the molecules of a solid
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and there is no space among molecules. But there exists vibratory motion in the molecules
of solid. This vibratory motion of molecules is responsible for the diffusion of solids. Since
force of attraction are very large therefore diffusion in solids takes place with very negligible
speed
Scientific Reasons
Q1) Steam produces severe burns, then boiling water, although both have same
temperature.
Both steam and boiling water have the same temperature i.e. 100 oC. But heat content of
steam is greater than the boiling water because latent heat of steam is 2.26 x 10 5 J/kg
.That’s why steam produces severe burn as compared to boiling water.
Boiling point of a liquid depends on the outer atmospheric pressure.At normal atmospheric
pressure boiling point of water is 100 0C. on mountain areas such as Quetta and Swat,
atmospheric pressure is below 760 torr. Due to this reason B.P of water decreases and food
takes longer time to cook.
Q4) Glycerin distilled at 290 0C but it decompose at this temperature, how would
you distilled it?
At 760 torr, B.P of glycerin is 290 0C but at 290 0C temperature glycerine evaporates and it
become difficult to distill it. In order to overcome this difficulty it is distilled at 50 torr . At
50 torr it’s B.P decreases to 210 0C. At 210 0C it does not decompose and distiledl easily.
Rate of evaporation increases with the increase in temperature because on heating kinetic
energy of molecules becomes high enough to overcome intermolecular forces of attraction.
Thus number of molecules leaving the liquid surface is increased. So the rate of evaporation
increases on heating
Q6) Falling drop of liquid is spherical.
Falling drop of a liquid is always spherical in shape due to surface tension. The inward forces
on the surface molecules of the liquid droplet tend to cause the surface to volume ratio as
small as possible. Since surface to volume ratio is minimum for the spherical shape that’s
why falling drop of a liquid is spherical.
Q7) Under similar conditions surface tension of water is higher than the surface
tension of ether.
Surface tension depends upon the strength of intermolecular forces of attraction. Water has
higher surface tension due to polar nature of its molecules. In water there exist hydrogen
bond as compared to ether, which is non-polar and has no hydrogen bond. We know that
hydrogen bond increases intermolecular attraction. Consequently water has high surface
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tension.
Difference between Amprphous Solids and Crystalline Solids
VAPOUR PRESSURE........
OR
Pressure exerted by the vapours of a liquid when rate of evaporation is and the
rate of condensation becomes equal is called "Vapour Pressure".
Boiling point of liquid varies with atmospheric pressure. If atmospheric pressure is less
then 760 torr then the boiling point of a liquid will decrease from its standard boiling
point.
Boiling point of a liquid decreases with the decrease in pressure and vice versa
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SURFACE TENSION
Surface tension is a characteristic property of a liquid.
Definition:
"Perpendicular force acting on the unit length of the surace of a liquid is called
SURFACE TENSION".
Surface tension = force/length
g = F/L
2nd definition:
"Energy per unit area on the surface of a liquid is called SURFACE TENSION"
s = energy /area
Unit of surface tension
· N/m (in S.I system)
· Dyne/cm (in C.G.S system)
· Joule/m2 (in S.I system)
· Erg/cm2 (in C.G.S system)
FACTORS AFFECTING SURFACE TENSION
Inter molecular forces
If force of attraction between molecules is high then surface tension will also be
high.
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Hydrogen bonding
Liquids that have H-bond such as water, have high values of surface tension.
Temperature
Surface tension of a liquid decreases with the increase in temperature because
an increase in temperature, reduces force of attraction between molecules.
Properties of Solid..........
LATENT HEAT OF FUSION
Latent heat of fusion is defined as:
The amount of heat required to melt unit mass of solid substance at its melting point.
It is denoted by Hf.
Unit:
Its unit is
J/Kg ,
erg/gm
Formula: Q=m x Hf
Where
m= mass of solid
Q= amount of heat
UNIT CELL Crystals made of very small basic patterns or arrangements of atoms or
molecules or
ions.These basic patterns are joined together to form a crystal.Theses basic patterns are
known
as "UNIT CELL". All the unit cell of a crystal are identical.
Cell parameters
Length of edges (axes) and the angle between the edges are collectively known as "Cell
Parameters".
CRYSTAL SYSTEM
a=b=c
angle between the edges are equal i.e. 90
= =
Examples:
3. Diamond
a = b c
= =
Examples:
1. SnO2
2. BaSO4.4H2O
a bc
= =
Example:
1. FeSO4.7H2O
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2. ZnSO4.7H2O
3. KNO3
a=b=c
· angles are equal but not equal to 90o. angles are
between 90 and 120
= = 90
Examples:
1. KNO3
2. AgNO3
In this system, two sides are equal but third side is different.
a = b c
Two angles between the edges are equal to 90o but third angle is equal to 120.
= = 90, = 120
Examples:
Graphite
abc
= = 90
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90
Examples:
1. CuSO4. 5H2O
2. Sugar
abc
90
Examples:
1. CuSO4. 5H2O
2. K2Cr2O7
POLYMORPHISM-ALLOTROPY-ISOMORPHISM
POLYMORPHISM
Existence of substance into more than one crystalline forms is known as
"POLYMORPHISM".
In other words: Under different conditions of temperature and pressure, a substance
can form more than one type of crystals. This phenomenon is called Polymorphism
and different crystalline forms are known as ‘POLYMORPHICS’
Example:
a. Orthorhombic
b. Trigonal
a. Orthorhombic (Aragonite)
b. Trigonal
properties.
ALLOTROPY
"Existence of an element into more than one physical forms is known as ALLOTROPY "
Under different conditions of temperature and pressure an element can exist in more
than one
physical forms. This phenomenon is known as Allotropy and different forms are known
as "Allotropes"
Example:
Coal, lamp black, coke, Diamond, graphite etc. are all allotropic forms of carbon.
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ISOMORPHISM
Or
Different substances may exist in identical crystalline forms. This phenomenon is called
as
Isomorphism and these substances are known as ‘Isomorphous’.
Examples:
For example
CaCO3 NaNO3
1:1:3 1:1:3
NaF MgO
1:1 1:1
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4) When their solutions are mixed, they form mixed type of crystals.
TYPES OF SOLIDS
TYPES OF SOLIDS
1) Crystalline solids
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2) Amorphous solids
CRYSTALLINE SOLIDS
Examples:
AMORPHOUS SOLIDS
Solids that don’t have a definite geometrical shape are known as Amorphous Solids.
2. They don’t have sharp melting points.
5. Examples:
Types of Crystals
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Types of Crystals
1) Metallic crystals
2) Ionic crystals
3) Covalent crystals
4) Molecular crystals
1) Metallic Crystals
2) Ionic Crystals
3) Covalent Crystals
For example:
Diamond
Graphite
4) Molecular Crystals:
In molecular crystals, molecules are joined together by weak Vander Wall forces.
PARTIAL PRESSURE
In a mixture of different gases which do not react chemically each gas behaves
independently of the other gases and exerts its own pressure. This individual pressure
that a gas exerts in a mixture of gases is called it's partial pressure.
DALTON'S LAW OF PARTIAL
PRESSURE
Based on this behaviour of gases, JOHN DALTON formulated a basic law which is known
as "The Dalton's law of partial pressure" .
---------(a)
Adding equation (i) , (ii) and (iii), we get,
Pt = naRT/V + nbRT/V + ncRT/V
Pt = (na + nb + nc)RT/V
OR
But nt = na + nb + nc
Pt = nt RT/V
This expression indicates that the pressure of a gas is proportional to number of moles if
confined under similar conditions.
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DIFFUSION OF GASES
Inter mixing of two or more gases to form a homogeneous mixture without any chemical
change is called "DIFFUSION OF GASES" . Diffusion is purely a physical phenomenon.
Gases diffuse very quickly due to large empty spaces among molecules. Different gases
diffuse with different rates (velocities).
GRAHAM'S LAW OF
DIFFUSION
Graham's law is a quantitative relation between the density and rate of diffusion of
gases.
STATEMENT
The rate of diffusion of a gas is inversely proportional to the square root of its density.
The comparative rates of diffusion of two gases are inversely proportional to the
square root of their densities.
MATHEMATICAL
REPRESENTATION OF THE
LAW
Consider two gases A and B having mass densities d1 and d2 and their rates of
diffusions are r1 and r2 respectively.
According to Graham's law of diffusion:
For gas A:
OR
..................(i)
For gas B:
OR
..................(ii)
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Since density molecular mass, therefore, we can replace density d by Molecular mass
M.
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CHAPTER NO 03
ATOMIC STRUCTURE
ATOM
Smallest particle of an element which shows all properties of element is
called atom.
Some characteristics of "atoms" are as follows:
Atom takes part in chemical reactions independently.
Atom can be divided into a number of sub-atomic particles.
Fundamental particles of atom are electron, proton and neutron.
CHARACTERISTICS OF ELECTRON
Charge: It is a negatively charged particle.
Magnitutide of charge: Charge of electron is 1.6022 x 10-19 Coulomb.
Mass of electron: Mass of electron is 0.000548597 a.m.u. or 9.1 x 10
-31
kg.
Symbol of electron: Electron is represented by "e".
Location in the atom: Electrons revolve around the nucleus of atom in
different circular orbits.
CHARACTERISTICS OF PROTON
Charge: Proton is a positively charged particle.
Magnitude of charge: Charge of proton is 1.6022 x 10-19 coulomb.
Mass of proton: Mass of proton is 1.0072766 a.m.u. or 1.6726 x 10-
27
kg.
Comparative mass: Proton is 1837 times heavier than an electron.
Position in atom: Protons are present in the nucleus of atom.
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CHARACTERISTICS OF NEUTRON
charge: It is a neutral particle because it has no charge.
Mass of neutron: . Mass of neutron is 1.0086654 a.m.u. or 1.6749 x
10-27 kg.
Compartive mass: Neutron is 1842 times heavier than an electron.
Location in the atom: Neutrons are present in the nucleus of an atom.
ATOMIC NUMBER
Total number of protons present in the nucleus of an atom is called
"Atomic number" or "Charge number"
Since the total number of protons and the total number of electrons in an
atom are equal therefore atomic number may also be defined as:
"Total number of electron in an atom is called Atomic number"
SYMBOL: It is denoted by "z".
MASS NUMBER
Total number of protons and neutrons present in the nucleus of an
atom is called "Mass number".
SYMBOL: It is denoted by "A".
A=p+n
SYMBOL OF NUCLEUS
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INTRODUCTION
Gases are bad conductors of electricity. However under reduced
pressure and at high potential difference gases conduct electric current.
DISCHARGE TUBE
Discharge tube is a glass tube fitted with two electrodes placed opposite
to each other. The tube is sealed and contains a vacuum pump. The
function of vacuum pump is to reduced or change the pressure inside
the tube. The two electrodes are connected to a high voltage battery.
THE EXPERIMENT
In discharge tube experiment, at low pressure and at very high potential
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DISCOVERY OF NEUTRON
CHADWICK
EXPERIMENT
Chadwick in an experiment bombarded Be with a-particles. In his
experiment he observe that some very penetrating radiations coming
out from Be. These radiations consist of material particles. Mass of these
particles was nearly equal to the mass of one hydrogen atom. Since
these particles were not deflected by magnetic or electric field ,therefore
they are named as Neutrons.
Be9 + 2H4 6C12 + 0n1
4
DISCOVERY OF PROTON
DISCOVERY OF
PROTON
Passage of electricity through the gases at low pressure also resulted in
the discovery of proton.During the discharge tube experiments, a
famous scientist Gold Stein observed that if a perforated cathode is
used, some radiations appear behind the cathode. Since radiations are
coming from anode, therefore, it was assumed that they must carry a
positive charge. These rays are known as Anode Rays.
PROPERTIES OF
ANODE RAYS
Anode rays travel in straight line.
They consist of material particles.
These rays contain positive charge.
These rays actually consist of positive ions of various gases used in
the experiment.
Their positive charge is either equal to electronic charge (e) or some
multiple of it.
These particles which have a mass 1836 times that of the electron
are known as protons.
RADIOACTIVITY
RADIOACTIVITY
All the elements having atomic number greater than 82 emit invisible
radiation all the time. The phenomenon of emission of these powerful
rays is called "Natural Radioactivity" and the element that emits such
rays is called "Radio Active Elements".
TYPES OF RADIO ACTIVE
RAYS
There are three types of radioactive rays:
-Rays
-RAYS
-RAYS
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PROPERTIES OF -RAYS
NATURE: rays consist of α particle. Each α particle consists of 2He
4
nucleus.
CHARGE: particle carry positive charge.
MASS: Mass of each - particle is 4 times that of a proton or H-
atom.
PROPERTIES OF -RAYS
NATURE: rays consist of fast moving electrons.
CHARGE: rays have negative charge.
VELOCITY: Velocity of rays is from 9 x 107 m/sec to 27 x 107
m/sec.
EFFECT ON PHOTO GRAPHIC PLATE:rays affect the photo
graphic plate.
IONIZTION POWER: Ionization power of rays is very small.
KINETIC ENERGY: Kinetic energy of rays is less than that of -
rays.
FLUORESCENCE: rays produce fluorescence in different
substance.
PROPERTIES OF -RAYS
NATURE: rays are electromagnetic radiations.
CHARGE: - rays are no charge.
VELOCITY: - rays travel with the velocity of light that is 3 x 108
m/sec.
PENETRATION POWER: Penetration power of - rays is very large.
It is about hundred times larger than that of rays.
FLUORESCENCE: - rays produce feeble fluorescence When incident
on screen coated with barium platino cyanide.
QUANTUM NUMBERS
QUANTUM NUMBERS
For complete description of an orbital in an atom, few constant numbers
are necessary. These constant numbers are necessary to describe the
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AZIMUTHAL OR
SUBSIDIARY QUANTUM
NUMBER
Azimuthal quantum number describes the shape of orbital. It is denoted
by . Values of are from zero to n-1.
For s-orbital =0
For p-orbita =1
For d-orbital =2
For f-orbital =3
With the help of the value of azimuthal quantum number we can
determine the total number of energy sub levels in a given energy level.
MAGNETIC QUANTUM
NUMBER
Magnetic quantum number indicates the orientation of an orbital in
space in an applied magnetic field . It is denoted by ‘m’.
Values of ‘m’ are from ( ) to (+ l) through zero.
Orbital l m
s 0 0
p 1 -1, 0, +1
d 2 -2, -1, 0, +1, +2
-3, -2, -1, 0, +1,
f 3
+2, +3.
It is denoted by ‘s’.
s = +1/2 , S = -1/2
ATOMIC RADIUS
Half of the bond length between two homonuclear atoms is called atomic
radius.
OR
The distance from the centre of the nucleus upto which it's outer most
electron is extended.
For example:
C-C bond length in diamond is 1.54Ao.
Therefore, atomic radius of C = 1.54 Ao/2
R = 0.77 Ao.
ATOMIC RADIUS IN A GROUP:
Atomic radius increases from top to bottom in a group.
Reason:
Due to addition of an energy level.
ATOMIC RADIUS IN A GROUP:
Atomic radius decreases from left to right in a period.
Reason:
Due to increase in nuclear charge.
Question: I.P. of Li is 5.4 and of K is 4.3 ev. What would you predict for
the I.P. of Na?
Answer: We know that I.P. decreases down the group, since Atomic size
of these three atoms are in the order of Li < Na < K, therefore, I.P. of
Na will lie between 5.4 ev and 4.3 ev.It will be less than 5.4 but greater
than 4.3 ev.
SPECTROSCOPY
SPECTROSCOPY
The branch of chemistry which deals with the study of absorption or
emission of radiation is called Spectroscopy.
SPECTRUM
When a ray of light consists of different wave lengths is passed through
a spectrometer or a prism, it is dispersed into component wave lengths
and a band of different colors is obtained which is known as spectrum.
SPECTROMETER
Spectrometer is an instrument used for spectroscopic studies. When
radiation are passed through the prism of spectrometer, they are
separated in to component wavelengths. In this way an image of
different colors is formed which is known as spectrum.
TYPES OF SPECTRA
Emission Spectra.
Absorption Spectra.
EMISSION SPECTRUM
When an element absorbs sufficient amount of energy from an electric
arc or by heating, it emits radiation. These radiation when passed
through spectrometer, spectrum so obtained is called Emission
Spectrum.
There are two types of emission spectra.
Continuous Spectrum.
Line Spectrum.
CONTINUOUS
SPECTRUM
When white light from sun or any incandescent body or lamp is passed
through a prism, it disperses into its component colors and a spectrum
is obtained known as Continuous Spectrum.A continuous spectrum is
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one in which colors are diffused in one another without any line of
demorcation.
CHARACTERISTICS
Continuous Spectrum consists of seven colors.
The colors are so mixed that there is no boundary or line of demarcation
between two colors.
Examples:
Spectrum of sunlight, incandescent solids and liquids, bulb light, tube
light.
LINE SPECTRUM
When electric current is passed through a gas at low pressure, the
atoms of gas are excited and radiate light. When this light is passed
through the prism, a spectrum is obtained known as Line Spectrum.
CHARACTERISTICS
In line spectrum, every two colors are separated by a line of
demarcation.
Each spectral line has a definite wavelength.
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ION
If an electron or more than one electrons are added to or removed from an
atom then it becomes a negative or a positive charged particles which is
known as "ION".
CATION
If an electron or more than one electrons are removed from an atom,
it becomes a positive ion which is also known as "cation".
for example: Na+1, K+1, Ca+2, Mg+2, Al+3.
ANION
If an electron or more than one electrons are added to an atom
it becomes a negative ion which is also known as "anion".
for example: Cl-1, Br-1, O-2, N-3, F-1
IONIZATION POTENTIAL
"Amount of energy required to remove an electron from
an isolated gaseous atom is called ionization potential."
ATOM + ENERGY CATION + ELECTRON
A + Energy A+ + e-
UNIT:
kJ / mole
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FACTORS AFFECTING IONIZATION POTENTIAL:
(i) ATOMIC SIZE (ii) NUCLEAR CHARGE (iii) SHIELDING EFFECT OF INNER
ELECTRONS
1. Big atoms have small I.P. values
2. Small atoms have high values of I.P.
3. Greater the nuclear charge , higher is the I.P. of atom.
I.P. IN A GROUP
I.P. decreases in a group from top to bottom due to increase in atomic size
from top to bottom in a group.
I.P. IN A PERIOD
I.P. increases in a period from left to right.
This increase in I.P. is due to increase in nuclear charge.
DALTON ‘S ATOMIC THEORY
DEFECTS IN DALTON’S THEORY:
Postulate number 2, 3, 4 and 6 are not correct as described below:
DEFECT NO: 1
Atom can be divided into a number of sub-atomic particles such as
electron, proton and neutron etc.
DEFECT NO: 2
Atoms of an element may be different in their masses.
for example:
1H1, 1H2, 1H3
17Cl35, 17Cl37
DEFECT NO: 3
All compounds do not have small number of atoms.
for example:
Decane C10H22.
Sugar C12H22O11.
DEFECT NO: 4
Atom can be destroyed by fission process in
Atom bomb.
Nuclear reactor.
On the basis of above defects, Dalton's atomic theory has failed now.
RUTHERFORD’S ATOMIC THEORYELECTRONEGATIVITY
.
RUTHERFORD’S ATOMIC MODEL
Rutherford's atomic model shows the existence of nucleus in the atom,
nature of charge on the nucleus and the magnitude of charge on the
nucleus.
APPARATUS FOR EXPERIMENT
Alpha particles.
Electron Gun.
EXPERIMENT
In his experiments, Rutherford bombarded alpha particles on very thin
metallic foils such as gold foil.In order to record experimental
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OBSERVATIONS
He observed that most of the alpha particles were pass through the foil
undeflected.
Very few particles were deflected when passed through the foil.
One particle out of 8000 particles was deflected at 90o.
Few particles were deflected at different angles.
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MAIN POINTS OF RUTHERFORD’S THEORY
1. Since most of the alpha particles were passed through the foil
undeflected, therefore, it was concluded that most of the atom is empty.
2. Small angles of deflection indicate that positively charged alpha particles
were attracted by electrons.
3. Large angles of deflection indicate that there is a massive positively
charged body present in the atom and due to repulsion alpha particles
were deflected at large angles.
DEFECT OF
RUTHERFORD’S THEORY
electron when accelerated must emit energy. We know that the motion of
electron around the nucleus is an accelerated motion, therefore, it must
radiate energy. But in actual practice this does not happen. Suppose if it
happens then due to continuous loss of energy orbit of electron must
decrease continuously. Consequently electron will fall into the nucleus. But
this is against the actual situation and this shows that atom is unstable.
BOHR’S ATOMIC THEORY
Main postulates of Bohr’s atomic theory are:
CONSTANT ENERGY CONCEPT
Energy of an electron is constant in one of its allowed orbits. As long
as an electron remains in its orbit, it neither absorbs nor radiates
energy.
CONCEPT OF ENERGY LEVELS
Electrons revolve around the nucleus of atom in circular orbits in
which energy of electrons is constant. These circular paths are
known as "energy levels" or "stationary states".
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RADIATION OF ENERGY
If an electron jumps form higher energy level to a lower energy
level, it radiates a definite amount of energy.
...
ABSORPTION OF ENERGY
If an electron jumps from lower energy level to a higher energy
level, it absorbs a definite amount of energy.
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..
AMOUNT OF ENERGY
Energy released or absorbed by an electron is equal to the difference
of energy of two energy levels.
Let an electron jumps from a higher energy level E2 to a lower
energy level E1.The energy is emitted in the form of light . Amount of
energy released is given by:
E = E2 - E 1
E2 - E 1 = h
Where
h = Planck's consrant ( 6.6256 x 10-34 j.s)
m v r = nh /2
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Where n =1, 2, 3, ………..
m = mass of electron
V = velocity of electron
r = radius of orbit
OR
Only those energy levels or orbits are possible for which angular
momentum of electron is an integral multiple of h /2 .
UNCERTAINTY PRINCIPLE
INTRODUCTION
In classical physics it is generally assumed that position and momentum
of a moving object can be simultaneously measured exactly i.e. no
uncertainties are involved in its description. But in microscopic world it is
not possible. It is found that however refined our instruments there is a
fundamental limitation to the accuracy with which the position and
velocity of microscopic particle can be known simultaneously. This
limitation was expressed by a German physicist Werner Heisenberg in
1927 and known as 'Heisenberg's uncertainty principle'.
STATEMENT
According to Heisenberg's uncertainty principle:
It is impossible to determine both position and momentum of an
electron simultaneously.
If one quantity is known then the determination of the other quantity
will become impossible.
MATHEMATICAL
REPRESENTATION
Let
x = uncertainty in position
P = uncertainty in momentum
According to Heisenberg's uncertainty principle:
The product of the uncertainty in position and the uncertainty in
momentum is in
the order of an amount involving h, which is Planck’s constant.
P x x h
RESULTS OF
UNCERTAINTY
PRINCIPLE
It is impossible to chase an electron around the nucleus.
The principle describes the incompleteness of Bohr's atomic theory.
According to Heisenberg's uncertainty principle there is no circular
orbit around the nucleus.
Exact position of an electron can not be determined precisely.
LIMITATIONS OF
PRINCIPLE
Heisenberg's uncertainty principle is not applicable in our daily life. It is
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AUFBAU
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PRINCIPLE
According to AUFBAU PRINCIPLE:
"The electrons are filled to the orbitals of lowest energy in
sequence, two electrons to each orbital."
In other words:
(n+l) RULE
According to (n+l) rule:
1. Orbital which has the least value of (n+l) will be filled first to
the electrons.
EXPLNATION
EXAMPLE # 01:
3s-orbital will be filled prior to 3p-orbital.
ORBITAL n l (n+l)
3s 3 0 3+0 = 3
3p 3 1 3+1 = 4
COMMENTS: Since 4s-orbital has least value of (n+l), therefore ,it will
occupy electrons before
3d-orbital.
EXAMPLE # 03:
4d-orbital will be filled prior to 4f-orbital.
ORBITAL n l (n+l)
4d 4 2 4+2 = 6
4f 4 3 4+3 =7
HUND'S RULE OF
MAXIMUM MULTIPLICITY
According to Hund's rule of maximum multiplicity:
1. The electrons tend to avoid being in the same orbital.Thus as
the electrons are successively added, a maximum number of
electrons will try occupy orbitals singly.
.
2. When all the orbitals are singly occupied only then the pairing
of electrons commences.
.
3. In the ground state, the electrons occupying the orbitals singly
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PAULI'S EXCLUSION
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PRINCIPLE
According to Pauli's exclusion principle:
"In an atom no two electrons can have the same set of four
quantum numbers."
Pauli's exclusion principle indicates that two electrons may have three
same quantum numbers but the fourth quantum number must be
different.
Notice that the fourth quantum number i.e. spin quantum number is
different for both electrons.
Let us suppose that 1s-orbital contains three electrons i.e. 1s 3, in this
situation:
electro
n l m s
n
e1 1 0 0 +1/2
e2 1 0 0 -1/2
e3 1 0 0 ???
Since there are only two possible values of spin quantum number,
therefore, third electron can not be accomodated in 1s-orbital.This
clearly points out that an orbital can not contain more than two
electrons. Hence by Pauli's exclusion principle, 1s2 is correct but 1s3 is
not possible.
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CHAPTER NO 4
CHEMICAL BOND
Chemical bond can be defined as :
" the force of attraction between two atoms or ions that hold
them
together in a unit is called Chemical Bond".
Actually chemical bond is the main factor that makes molecules and
compounds. By the interaction
of outer electrons, great forces of attraction are developed between two
atoms. This force of
attraction is called chemical bond.
TYPES OF CHEMICAL BOND
There are three types of chemical bonds:
Ionic bond or Electrovalent bond
Covalent bond
Coordinate Covalent bond
IONIC BOND OR ELECTROVALENT BOND
Chemical bond formed between two atoms due to transfer of electron(s)
from one atom to the other
atom is called "Ionic bond" or "electrovalent bond".
EXPLANATION
In ionic bond formation one atom looses electron(s) and the other picks it
up. The atom that looses the electron acquires positive charge and the
other atom which gains the electron becomes a negatively charged
particle. Due to opposite charge an electrostatic force of attraction is setup
between them.
This force hold these atoms together in a unit. This force of attraction is
referred to as
"IONIC BOND".
FORMATION OF IONIC BOND BETWEEN Na & Cl
Due to low ionization potential value, Na-atom loses its valence electron
Electronic arrangement after losing an electron is K = 2, L = 8 , M = 0
Electronic configuration after losing an electron is 1s2, 2s2, 2p6 .This shows that its octet
is complete.
In the above two steps we clearly observe that there is a difference of energy i.e.
This shows formation of one mole of NaCl increases the energy of system by 147 KJ
/mole.
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PROPERTIES OF IONIC
COMPOUNDS
NON-MOLECULAR
FORM
Ionic compounds are not in molecular form. Their formula only indicates
the number of atoms. In ionic compounds each ion is surrounded by a
number of oppositely charged ions.
STATE
Due to strong binding forces ionic compounds exist in solid form.
MELTING AND
BOILING POINT
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COVALENT BOND
Chemical bond formed between two atoms by the mutual sharing of
electrons is known as Covalent bond.
In covalent bond formation each atom provides equal number of electrons
for sharing but no transfer of electrons takes place. Each electron pair is
attracted by both the nucleus.
Chemical bond formed between two similar atoms is always a covalent bond.
Shared electrons spend much of the time between the nuclei, resulting in
the attractive forces between negative charge of electron and positive
charge of nuclei.
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COVALENT BOND BETWEEN
H-ATOM AND Cl-ATOM
Due to small difference b/w the values of E.N., electron transfer from H
or Cl is not possible.
H and Cl share one electron.
In this way without any transfer of electron both H & Cl complete their
outer shell and a stable HCl molecule is formed.
There are three types of covalent bond depending upon the number of shared
electron pairs.
SINGLE COVALENT BOND
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F-F
The type of chemical bond in which one atom provides shared pair of
electron for bond formation is called "Coordinate Covalent Bond".
OR
Chemical bond formed between two atoms due to sharing of electron pair in
which only one atom provides shared pair of electron for the formation of
bond, is known as coordinate covalent bond or dative bond.
In the formation of coordinate bond other atom does not provide electron for
sharing. It is one sided sharing.
Formation of coordinate covalent bond is the property of atoms that have
lone pair of electrons.
The atom that provides electron pair is called "Donor".The other which
takes it is called "Acceptor".
Symbol:
Dative bond is represented by an arrow (), pointing from donor atom to
the acceptor.
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Examples:
Ammonium ion
Hydronium ion
Sigma bond
1. Sigma bond is formed by the linear or head to head or end on overlapping of
orbitals.
2. Sigma bonds are the strong bonds due to maximum overlapping of orbitals.
3. Electron density is maximum around the bond axis.
4. Compounds having sigma bonds are stable and hence less reactive.
5. First bond formed between two atoms is always a sigma bond.
6. s-s overlap, s-p overlap and p-p overlap give rise to sigma bond.
Examples of Sigma bond
s-s overlap in H2 molecule
Hydrogen molecule consists of two H-atoms. Each atom contains one electron in 1s
-orbital. E.C = 1s1
According to molecular orbital theory two 1s1 orbitals of two H-atoms overlap
linearly to produce two types of molecular orbitals.
1. Bonding molecular orbital (-orbital)
2. Anti-bonding molecular orbital (*-orbital)
Bonding molecular orbital (-orbital) has lower energy and results in the covalent
bond formation which is a sigma bond between two H-atoms while the anti-bonding
molecular orbital (*-orbital) possess high energy remains unoccupied.
s-p type overlap occurs in HF molecule when one 1s-orbital of hydrogen atom
overlaps 2p-orbital of fluorine to form two types of molecular orbitals.
1. Bonding molecular orbital (-orbital)
2. Anti-bonding molecular orbital (*-orbital)
Bonding molecular orbital (-orbital) has lower energy and results in the covalent
bond formation (sigma bond) between H-atom and F-atom while the anti-bonding
molecular orbital (*-orbital) possess high energy remains unoccupied.
The relative strength of a sigma bond is related to the extent of overlap of the
atomic orbitals. This is known as the 'principle of maximum overlap'.
Due to spherical charge distribution in s-orbital, generally s-s overlapping is not so
effective as s-p and p-p overlapping.
Where p-orbitals have directional charge distribution and longer lobes which cause
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Pi bond
A Pi bond is formed by the lateral or side ways or parallel overlapping of P-orbital of
the atoms which are already bonded by a sigma bond and their axes are coplanar.
This type of overlap generates two types of molecular orbitals:
(a) Pi-bonding molecular orbital (-orbital)
(b) Pi-antibonding molecular orbital ( *-orbital)
A pi-bonding orbital has two regions of electron density below and above the nodal
plane.The electron contained in it are called pi-bonding electrons which form the pi
bond. It is not linearly symmetrical with respect to the bond axis, rather it has a
nodal plane.
Pi-bonds are weaker than sigma bonds.
In Pi-bonds, electron density lies in the regions above and below the nuclei.
Compounds having pi bonds are more reactive.
Pi bond is formed when two atoms already bonded by a sigma bond.
Bonding
molecul
ar orbital
Its energy is less than that of parent atomic orbital.
It is more stable than the parent atomic orbital.
In B.M.O, the probability of finding electrons is maximum.
Contribution of B.M.O is maximum towards the shape of
molecule.
Anti-bonding
molecular orbital
Its energy is greater than that of parent atomic
orbital.
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Atomic orbital
It surrounds only one nucleus.
HYBRIDIZATION
The phenomenon of mixing up of different orbitals of same energy level
of an atom to produce equal number of hybrid-orbitals of same energy
and identical properties is known as hybridization. A hybrid orbital
contains maximum two electrons with opposite spin.
In hybridization, only those orbital take part that have very little
difference of energy.
TYPES OF HYBRIDIZATION
IN CARBON ATOM
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Sp3-hybridization.
Sp2- hybridization.
Sp- hybridization.
Sp3- HYBRIDIZATION
The process of hybridization in which one s-orbital and three p-orbitals
overlap to produce four hybrid-orbital is known as Sp3-hybridization.
These hybrid-orbital are identical in shape and energy. These orbital are
known as Sp3-hybrid orbitals. Sp3-orbitals are at an angle of 109.5o from
each other. Sp3-orbital are arranged in tetrahedral fashion.
Sp3- HYBRIDIZATION
AND METHANE
Methane molecule composed of one carbon atom and four hydrogen atom
i.e. CH4. In methane molecule central atom is carbon. Here carbon atom
is Sp3-hybridized. One s-orbital (2s) and three p-orbital (2px, 2py, 2pz)
overlap to produce four Sp3-hybrid orbitals. These Sp3- hybrid orbital are
at a angle of 109.5o from each other. These Sp3-orbitals are attached at
the corner of a tetrahedron. Each Sp3-orbital of carbon atom overlaps 1s-
orbital of hydrogen atom. In this way four sigma bonds (Sp3-S bonds) are
generated. The final geometry of methane molecule is tetrahedral as
shown.
There are two types of electron pairs surrounding the central atom.
Bond pair.
Lone pair.
These bond pairs are known as active set of electrons.
These electron pairs (bond pairs or lone pairs) repel each other.
Due to repulsion, electron pairs of central atom try to be as far as
possible. Hence, they arrange themselves in space in such a manner
that the force of repulsion between them is minimized.
The force of repulsion between lone pairs and bond pairs is not the
same. The order of repulsion is as follows:
lone pair-lone pair>lone pair-bond pair>bond pair-bond pair.
Pi-electron pairs are not considered as an active set of electrons.
Introduction:
The degree of polarity of a molecule is expressed in terms of dipole moment.
Definition:
The product of magnitude of charge on a molecule and the distance between
two charges of equal magnitude with opposite sign is equal to dipole moment.
Mathematical representation:
Dipole moment=charge x distance
µ = exd
Symbol:
It is represented by an arrow ()
Unit:
Its unit is debye.(D)
Conversion:
1 debye=3.335 x 10-30 coulomb x meter
OR
1 debye=1 x 10-18 E.S.U x cm
For example:
H2O = 1.84 debye
NH3 = 1.46 debye
BOND ENERGY
Definition:
Amount of energy required to break a bond between two atoms in a di-
atomic molecule is called bond energy.
Or
Bond energy may also be defined as the amount of energy released when two
atoms unite together with a covalent bond.
Example:
Cl-Cl ; B.E. = 2.44 KJ/mole.
H-H ; B.E. = 4.35 KJ/mole.
Unit:
Its unit is KJ/mole and Kcal/mole.
Bond breaking is an endothermic reaction. Bond formation is an exothermic reaction,
FACTORS ON WHICH BOND ENERGY DEPENDS:
BOND LENGTH:
Shorter the bond length, greater is the bond energy.
IONIC CHARACTER:
Greater the ionic character, greater is the bond energy.
MULTIPLE BOND:
Multiple bonds have short length, therefore, they have high bond energy.
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CHAPTER NO 05
THERMODYNAMICS
THERMODYNAMICS
"The branch of science which deals with the interconversion of heat energy
and other forms of energies is called thermodynamics."
OR
"It is the study of the flow of heat or any other form of energy into or out
of a system,as it under goes a physical or chemical change."
In thermodynamics we discuss all those problems which are related to the conversion of
any other form of energy into heat energy. Heat engines or I.C. engines or E.C. engines
are discussed under the field of thermodynamics.
THERMOCHEMICAL
REACTIONS
All those chemical reactions which accompanied with mass change as well as energy
change are known as thermo-chemical reactions.
TYPES OF THERMO-
CHEMICAL REACTIONS
There are two types of thermo chemical reactions:
ENDOTHERMIC REACTIONS
EXOTHERMIC REACTIONS
ENDOTHERMIC REACTION
"All those chemical reaction in which heat is absorbed in going
from reactancts to product are known as "Endothermic reactions. "
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These reactions can not proceed without addition of heat.
For example:
2KClO3 + Heat 2KCl + 3O2
CaCO3 + Heat CaO + CO2
GRAPHICAL
REPRESENTATION
EXOTHERMIC REACTION
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All those chemical in which heat is realeased in going from reactant to product
are known as exothermic reactions.
For example:
3H2 + N2 2NH3 + Heat
2SO2+O2 2SO3 + Heat
GRAPHICAL
REPRESENTATION
INTERNAL ENERGY
Internal energy of a thermodynamic system is defined as the total energy possess by a
system.It is numerically equal to the sum of all microscopic kinetic energies and potential
energies of all the atoms or molecules or ions present within a system.
Internal energy of a thermodynamic system is a state function which strictly depends
upon the initial and final states of the system.
The change in internal energy of a system is the amount of energy exchanged by a
system with its surroundings during a thermodynamic process, chemical or physical.
Change in internal energy of a system is equal to the difference between final internal
energy and initial internal energy.
E = E2 - E1
In the light of the first law of thermodynamics, change in internal energy of a system is
equal to the difference between the heatabsorbed or released by the system and the work
done.
E =Q - W
Internal energy of a system depends upon the temperature of system. If temperature of a
system is constant, then its internal energy will also be constant.
DEFINITIONS
SYSTEM
A thermodynamic system is a collection of matter which has distinct boundaries.
OR
A real or imaginary portion of universe which has distinct boundaries is called
system.
OR
A thermodynamic system is that part of universe which is under thermodynamic
study.
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FOR EXAMPLE:
A BALLOON FILLED WITH AIR
A BEAKER FILLED WITH WATER
TYPES OF SYSTEM
There are three types of thermodynamic systems.
Open system
closed system
Isolated system.
OPEN SYSTEM
An open system is one in which both mass & energy transfer takes place across the
boundaries.
An open tank of water.
CLOSED SYSTEM
A closed system in which there is no transfer of mass takes place across the boundaries
of system but energy transfer is possible.
A gas in a balloon.
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ISOLATED SYSTEM
An isolated system is that in which there is no transfer of mass & energy takes place
across the boundaries of system.
A thermo flask containing hot or cold liquid.
MACROSCOPIC PROPERTIES
all the properties of a system in bulk which are easily measurable are known as
macroscopic properties.
TYPES OF MACROSCOPIC
PROPERTIES
INTENSIVE PROPERTIES
Macroscopic properties of a system which are independent of mass are known as
intensive properties. Whatever is the mass but properties remain unchanged.
FOR EXAMPLE: MELTING POINT, BOILING POINT, DENSITY, TEMPERATURE, PRESSURE,
VISCOSITY.
EXTENSIVE PROPERTIES
Macroscopic properties of a system which are strictly dependent on there mass or
quantity of matter are known as extensive properties.
If mass is halved the property will also be half.
FOR EXAMPLE: volume, mole, mass, enthalpy, internal energy, kinetic energy.
Thermodynamic terms
SURROUNDINGS
The environments that contained the system are known surroundings.
Or
Any thing which is not a part of system is called surroundings.
System and surroundings are separated from each other by a real or imaginary
boundary.
EXAMPLE:
When a reaction is carried out in a flask placed in a thermostat, the content of flask is
the system, flask itself is the real boundary and thermostat is surroundings.
ENTHALPY
The total heat content of a system is called enthalpy.
Or
The total heat content of a system at constant pressure is equivalent to the sum of its
internal energy and PV which is called enthalpy.
Enthalpy = E + PV
It is denoted by H
HEAT OF FORMATION
Heat of formation of a compound is defined as the amount of enthalpy change when
one gram mole of a compound is formed from its elements.
It is represented by H
Unit of heat of formation is :
joule / mole
OR
Kilo joule / mole
OR
calorie / mole
OR
Kilo calorie / mole
STANDARD HEAT OF
FORMATION
Standard heat of formation is the heat of formation when all the substances involved
in the reaction are at unit activity i.e. at 25oC and one atmospheric pressure.
It is represented by Hf
STATE
A thermodynamic system is said to be in a certain state when all its properties are
specified or fixed.
The fundamental properties, which determine the state of a system, are:
Temperature
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Pressure
Volume
Mass
Composition
Any change in the above properties changes the state of system. Due to this reason
they are called 'State Functions'.
There are two states of a system
1. Initial state
2. Final state
INITIAL STATE
The description of the system before it suffers any physical or chemical change is called
'Initial State'
of the system.
FINAL STATE
The description of the system after it undergoes a physical or chemical change is called
'Final State'
of the system.
CHANGE IN STATE
Comparison between the final state and initial state of the system is referred to as
'change in state'.
The change in state of a system is completely defined when its initial and final states
are specified.
Change in state = Value of property in the final state - Value of property in the
initial state
FIRST LAW OF THERMODYNAMICS
INTRODUCTION
First law of thermodynamics is a statement of conversion of energy. It was enunciated
by HELMHOLTZ in 1847.
STATEMENT
In other words
"During any process total energy of system remains constant"
OR
"During any change the total energy of system and its surrounding remains
constant .
MATHEMATICAL
REPRESENTATION
Consider a thermodynamic system initially have internal energy E1 absorbs Q amount
of heat from its surroundings and performs W amount of work and at the same time
its internal energy increases to
hen according to the first law of thermodynamics:
Heat supplied = increase in internal energy +work done
Q = + W
OR
QE2 - E1W
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OR
QE2 - E1P V
Where
= E2 - E1
W = P V
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PRESSURE-VOLUME
WORK
AT CONSTANT
VOLUME
Heat supplied at constant volume is also known as "ISOCHORIC SYSTEM". An isochoric
process is one in which the volume of system during the supply of heat does not
change.This is achieved only when the piston of cylinder is fixed.
In order to supply heat at constant volume piston of cylinder is fixed at a certain
position so that during heat supply volume of system remains constant.
qv = E + W
qv = E
E = E2 – E1
OR
qv= E2 – E1
CONCLUSION
This expression shows that heat supplied at constant volume is used in increasing the
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AT CONSTANT
PREESURE
Heat supplied at constant pressure is also known as "ISOBARIC PROCESS". An isobaric
process is one in which no pressure change takes place during the supply of heat to
system.
Let the internal energy of the system at initial state is E 1, the temperature of system is
T1, volume of gas is V1 and pressure is P.
If qp amount of heat is supplied to the system, its internal energy will increase from E 1
to E2 and the temperature of system also rises from T1 to T2,
At the same time gas exerts some pressure on the piston, since the piston is free to
move, it displaces by "h" the volume of gas increases from V1 to V2 . Due to increase in
volume, pressure again decreases to its original value i.e. P1.
ACCORDING TO THE FIRST LAWOFTHERMODYNAMICS
Qp = E + work
Qp = E + P V
Q p = E + P V but (E = E2- E1
)
Qp = E2-E1 + P (V2 – V1)
Qp = E2-E1 + PV2- PV1
Qp = E2+ PV2 – E1 – PV1
Qp = (E2+ PV2) – (E1+ PV1)
but
(E + PV =H)
(H= enthalpy)
therefore,
qP = H
OR
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q p E + P V = H
CONCLUSION
This expression indicates that heat supplied at constant pressure is equal to increase in
enthalpy of system.
HESS'S LAW OF CONSTANT HEAT SUMMATION
INTRODUCTION
Heat absorbed or evolved in a certain reaction is equal to the difference of intrinsic
energies of reactants and products, no matter in what manner the reaction is carried out.
In the light of this fact, the Hess's law stated as:
STATEMENT
"The amount of heat evolved or absorbed in any chemical reaction is
constant and is independent of the method followed"
In other words:
"The change in enthalpy in any chemical reaction is constant and is
independent whether the reaction takes place in one step or in many steps"
EXPLANATION
Consider a system chemical whose initial and final states are represented by "A" and "E"
respectively. The change from A to E may take place in single step.
CHAPTER NO 6
At initial stage the reaction proceeds in the forward direction only because no
product is formed.
As the reaction starts A and B reacts to form C and D . Now C and D react
each other to reproduce A and B and the reaction now proceeds in both forward
and backward directions but the rate of forward reaction and the rate of backward
reaction are different.
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Finally a state is established at which the rate of backward reaction becomes
equal to the rate of forward reaction. This state is called 'chemical equilibrium'.
At equilibrium state, the reaction does not stop. Reactants form products and
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products again converted into reactants. This process is always continue but with
the passage of time, there is no change in the concentration of reactants and
products due to same rate of reaction. At this point, it apparantely appears as the
reaction has stopped because we don't see any change in the concentration of
reactants and products with time.
Since chemical equilibrium continues and never go to stop, therefore, chemical
equilibrium is a dynamic equilibrium.
CHEMICAL EQUILIBRIUM
There are three possible values of this ratio when it is compared with the value of
Kc.
When ratio=Kc
According to the law of mass action, there is no shifting of reaction and there will
be no change in the concentration of reactants and products and the system is
already at equilibrium.
When ratio> Kc www.citycollegiate.com
In this condition the reaction will shift in the backward direction to achieve
equilibrium state. At equilibrium quantity of product will decrease and the quantity
of reactants will increase.
When ratio<Kc
In this condition the reaction will shift in forward direction to achieve equilibrium
state. At equilibrium quantity of product will increase and the quantity of reactants
will decrease.
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To predict the extent of a reaction :
From the magnitude of equilibrium constant, we can predict not only the direction
of a reaction but also the extent to which a reaction proceeds.
There may be three values of equilibrium constant:
A very high value of equilibrium constant
A very small value of equilibrium constant
A moderate value of equilibrium constant
When the value of equilibrium constant is very high:
A very high value of equilibrium constant indicates that the forward is almost
complete and in other words we can say that the reactants are very unstable and
they react spontaneously.
For example the equilibrium constant for the reaction 2O3 3O2 is very
large i.e. 1 x 1055.
This indicates that the forward is almost complete and ozone (O3) is very unstable.
When the value of equilibrium constant is very small:
A very small value of equilibrium constant indicates that there is very little
tendency for the reaction to occur in the forward direction and in other words we
can say that the reactants are very stable.
For example the equilibrium constant for the reaction 2HF H2 + F2 is
very small i.e.
1 x 10-13.
This indicates that the forward occurs with negligible speed and hydrogen fluoride
(HF) is very stable.
When the value of equilibrium constant moderate:
When the value of equilibrium constant is neither very high nor very small, we
conclude that the reaction occurs both in forward and backward direction and
equilibrium will be attained after certain period of time.
For example the equilibrium constant for the reaction N2 +3H2 NH3 is
10, which is a moderate value.
Define KP
KP www.citycollegiate.com
For gaseous equilibrium systems we can use partial pressure of gases instead of
concentration. Therefore,
"Equilibrium constant determined by using partial pressure
of gases in a gaseous chemical equilibrium is denoted by Kp"
Consider a general reversible reaction :
Kp = Kc[RT]n
From above relation we conclude three results as follows.
1. If Kp=Kc
In this case there is no change in volume
For example:
H2 + I 2 2HI
In this example volumes of products are equal to the volumes reactants.
2. If Kp>Kc
In this case reaction occur with the increase in volume.
For example:
2NH3 N2 + 3H2
In this example volumes of products are greater than the volumes reactants.
3.If Kp<Kc
In this case reaction occur with the decrease in volume.
For example:
2SO2(g) + O2(g) 2SO3(g)
In this example volumes of products are less than the volumes reactants.
LE-CHATELIER'S PRINCIPLE
INTROUCTION citycollegiate.com
The equilibrium state of a chemical equilibrium system is changed by change in
concentration, pressure temperature etc. The effect of change in any one of the
above factors changes the equilibrium system. The effect of change of these factors
is explained by Le-chatelier's principle.
STATEMENT
If a stress or constraint is applied to an equilibrium system, the equilibrium
will shift in such a direction so that the effect of stress is cancelled or
minimzed.
For endothermic
reaction
Increase in temperature:
In an endothermic reaction, an increase in temperature favours the reaction to
occur in the forward direction. At equilibrium, the concentration of A and B will
decrease and the concentration of C and D will increase.
Decrease in temperature:
In an endothermic reaction, a decrease in temperature favours the reaction to occur
in the backward direction. At equilibrium, the concentration of C and D will decrease
and the concentration of A and B will increase.
EXAMPLE
H2 + I2 + HEAT 2HI
Above example is an endothermic reaction. If we increase the temperature of
system, then the equilibrium will shift in the forward direction where more amounts
of HI will be obtained and the concentration of H2 and I2 will decrease at
equilibrium.
EXAMPLE
H2 + I2 + HEAT 2HI
In this example a decrease in temperature favours the reaction to occur in the
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backward direction where more amounts of H2 and I2 will be obtained and the
concentration of HI will decrease at equilibrium.
For exothermic
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reaction
Increase in temperature:
In an exothermic reaction, an increase in temperature favours the reaction to occur
in the backward direction. At equilibrium, the concentration of C and D will decrease
and the concentration of A and B will increase.
Decrease in temperature:
In an exothermic reaction, a decrease in temperature favours the reaction to occur
in the forward direction. At equilibrium, the concentration of A and B will decrease
and the concentration of C and D will increase.
EXAMPLE
N2 + 3H2 2NH3 + HEAT
In this example an increase in temperature favours the reaction to occur in the
backward direction where more amounts of N2 and H2 will be obtained and the
concentration of NH3 will decrease at equilibrium.
EXAMPLE
N2 + 3H2 2NH3 + HEAT
In this example a decrease in temperature favours the reaction to occur in the
forward direction where more amounts of ammonia will be obtained and the
concentration of N2 and H2 will decrease at equilibrium.
The
effect
of
change
in
pressure
2 volumes 2 volumes
In the equilibrium of H2 + I2 2HI an increase or decrease of pressure
will not change the equilibrium state because equal volumes will change equally
and no change in equilibrium state will be observed.
In this condition there is no effect of change in pressure on the equilibrium system
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When volumes of reactants are greater than the volumes of products:
In this situation two conditions are applicable:
An increase in pressure
A decrease in pressure
Effect of increase in
pressure
An increase in pressure favours the equilibrium to shift in forward direction. At
equilibrium, the concentration of reactants will decrease and the concentration of
products will increase.
Effect of decrease in
pressure
A decrease in pressure favours the equilibrium to shift in backward direction. At
equilibrium, the concentration of products will decrease and the concentration of
reactants will increase.
For example: N2 + 3H2 2NH3
1 volume + 3 volumes 2 volumes
4 volumes 2 volumes
In the equilibrium of ammonia, an increase in pressure will shift the equilibrium to
forward direction i.e at high pressure the formation of ammonia is favoured.
When volumes of products are greater than the volumes of reactants:
Effect of increase in
pressure
An increase in pressure favours the equilibrium to shift in the backward direction.
At equilibrium, the concentration of products will decrease and the concentration
of reactants will increase.
Effect of decrease in
pressure
A decrease in pressure favours the equilibrium to shift in forward direction. At
equilibrium, the concentration of reactants will decrease and the concentration of
products will increase.
For example: 2O3 3O2
2 volumes 3 volumes
In this equilibrium system , a decrease in pressure will shift the equilibrium to
backward direction i.e at low pressure the formation of oxygen is favoured.
Solubility - Solubility product
Solubility:
Definition:
Solubility of a solute in a solvent is the number of grams of solute necessary to
saturate 100 grams of solvent at a particular temperature.
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Kc x K'= [Ag+][Cl-]
Let Kc x K' = solubility product or Ksp , Therefore,
Ksp = [Ag+][Cl-]
Ionic product:
Product of ionic concentration other than equilibrium is called ionic product.
Applications of solubility product:
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Knowledge of solubility product is very useful to determine whether precipitates will be
obtained or not by the addition of more amount of solute to the solution. There are
three conditions:
When Ksp > ionic product:
If solubility product is greater than the ionic product then, the solution is unsaturated
and no precipitate will form by the addition of more solute.
When Ksp< ionic product:
If solubility product is less than the ionic product then the solution is super saturated
and the excess of solute will precipitate immediately.
When Ksp= ionic product:
In this condition solution is saturated and further addition of solute will cause
precipitates.
COMMON ION EFFECT
DEFINITION
The degree of ionization of an electrolyte is suppressed by the addition of a strong
electrolyte containing common ion. This effect is known common ion effect.
In other words:
The phenomenon of lowering the degree of ionization of a weak electrolyte by adding
a solution of a strong electrolyte having a common ion is called common ion effect.
APPLICATION OF COMMON ION EFFECT
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H2O.
H2S 2H+ + S-2 : H+ + OH- H 2O
Removal of H+ ions from product side shifts the equilibrium to right and the
concentration of S-2 increases which is enough to exceed the KSP of the sulphides of
group IV. In this way CoS, NiS or ZnS can easily be precipitated.
PRECIPITATION OF THE CATIONS OF
GROUP IV
Cations of groups III are precipitated as hydroxides by passing NH4OH in the presence
of NH4Cl. Here
NH4Cl provides common ion NH4+ which suppresses the ionization of NH4OH.
NH4OH NH4+ + OH- : NH4Cl NH4+ + Cl-
Common ion NH4 shifts the equilibrium to left side and the concentration of OH- ions
+
decreases. Under these circumstances, the KSP of the hydroxides of Al, Fe and Cr is
only exceeded and they are precipitated as Al (OH)3, Fe (OH)3 and Cr (OH)3 but the
hydroxides of Zn, Ni and Co are not precipitated as they have high values of KSP.
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CHAPTER NO 7
MOLARITY
When NaCl is dissolved in water hydrolysis does not take place because by the addition of
NaCl in water, pH of water does not affected.
HYDRATION-HYDRATES
HYDRATION
When an ionic compound is dissolved in water it splits into positive and negative
ions. These ions are surrounded by water molecules. The phenomenon in which
water molecules surround a positive or negative ion is called 'HYDRATION'.
Hydration occurs either by the interaction of lone pairs of electrons in water with a
cation or by hydrogen bonding with anions.
HYDRATES
Many compounds have crystallized water molecules additional to that required for a
simple stoichiometry. Water can be bonded to cations by coordinate bonds from
oxygen or to anions by hydrogen bonds. These compounds are generally termed as
'HYDRATES'.
EXAMPLES
CuSO4.5H2O
Na2CO3.10H2O
ZnSO4.7H2O
BaCl2.2H2O
FeSO4.7H2O
MgCl2.6H2O
K2SO4.Al2(SO4)3.24H2O (potash
alum)
FeSO4.(NH4)2SO4..6H2O (Mohr's
salt)
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DEFINITION .www.citycollegiate.com
When a metal (electrode) is immersed in a solution containing the ions of that metal, a
potential difference is set up between the metal and its ions in the solution. This
potential difference is referred to as "ELECTRODE POTENTIAL".
EXPLANATION .
If a copper plate is dipped in a solution of copper sulphate (CuSO4) a potential
difference is set up between copper and Cu+ -ions which is known as electrode
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potential.
Electrode potential may be positive or negative depending upon the nature of electrode.
STANDARD
ELECTRODE POTENTIAL
When concentration of solution in which electrode is immersed is 1.00M, temperature is
25oC and pressure is 1.00 atmosphere, then the electrode potential is called standard
electrode potential. It is denoted by Eo.
CHARACTERISTICS OF
ELECTRODE POTENTIAL
Electrode potential is the measure of the tendency of an electrode to loose or gain
electron (s).
In other words electrode potential describes the tendency of an element to oxidize or
reduce.
Electrode potential also determines the chemical activity of an element.
OXIDATION POTENTIAL
It is the measure of tendency of an element to oxidize.
REDUCTION POTENTIAL
It is the measure of tendency of an element to reduce.
UNIT OF ELECTRODE
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POTENTIAL
Unit of electrode potential is "VOLT".
HYDROGEN ELECTRODE
Hydrogen electrode is the reference electrode used to compare electrode potential of
different electrode because absolute electrode potential can not be measured.
"A hydrogen electrode consists of a platinum bar immersed in 1.00M solution
of H2SO4. A current of pure hydrogen gas is passed through the solution
under 1.00 atmosphere. The platinum plate adsorbs hydrogen at its surface
and platinum plate is coated with hydrogen. The plate now behaves as if it
were made of hydrogen. The electrode potential of hydrogen electrode is
assumed to be 0.00V at all temperatures.".
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The potentiometer reading gives the E.M.F. of the cell which is 0.76 Volt. Since hydrogen
electrode has the potential of 0.00 Volt, hence potential of Zn electrode is 0.76 Volt.
Thus it concludes that the electrons must have originated from Zn i.e. it is oxidized and
it is anode and it is negative with respect to hydrogen electrode. Thus standard
reduction potential of zinc is - 0.76V.
CELL REACTION
Adding two equations:
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CHAPTER NO 8
CHEMICAL KINETICS
CHEMICAL KINETICS www.citycollegiate.com
The branch of chemistry, which deals with the "RATE" and the SPEED at which a
chemical reaction occurs, is called "CHEMICAL KINETICS". The study of chemical
kinetics, therefore, includes the rate of a chemical reaction and also the factors that
influence or alter or control the rate of chemical reactions. In chemical kinetics we
study how molecules react, bond breaking and new bond formation.
RATE OF A CHEMICAL
REACTION
"It is defined as the quantity of a reactant consumed or the
quantity of a product formed in unit time."
In other words:
The conversion of the number of moles of reactants into products in unit time. The
rate of reaction is not constant through out the activity but decreases with time due to
decrease in the concentration of reactants.
MATHEMATICALLY:
According to the law of mass action, rate of reaction is directly proportional to active
mass, hence for the above reaction:
This expression is called rate expression and K is called rate constant or velocity
constant.
CHARACTERISTICS OF RATE
CONSTANT
(i) It has a fixed value at a particular temperature.
(ii) Value of K varies with temperature.
(iii) Value of K remains unaltered with the change in concentration of reactants.
ORDER OF REACTION www.citycollegiate.com
"The order of reaction is defined as the sum of all the exponents
of the reactants involved in the rate equation."
It should be noted down that all the molecules shown in a chemical equation do not
determine the value of order of reaction but only those molecules whose
concentrations are changed are included in the determination the order of a reaction.
In other words:
For example:
2NO + O2 2NO2
dx/dt = k[NO]2[O2] , the reaction is of third order as 2 + 1 = 3
For a reaction maximum order is three and the minimum is zero.
FIRST ORDER REACTIONS
The reaction in which only one molecule undergoes a chemical change is called first
order reactions. Example:
N2O5 2NO2 + ½ O2
SECOND ORDER REACTIONS
The reaction in which two molecules undergo a chemical change is called second order
reactions. Example:
2CH3CHO 2CH4 + 2 CO
THIRD ORDER REACTIONS www.citycollegiate.com
The reaction in which only three molecules undergo a chemical change is called third
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Activation energy = Threshold energy – Average internal energy
ACTIVATION ENERGY AND RATE OF
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REACTION
The reactions having low activation energies take place with high speed.
The reactions having high activation energies take place with slow speed.
Following are the main factors that influence the rate of a chemical reaction.
NATURE OF REACTANTS www.citycollegiate.com
Different reactants have different energies of activation. Reaction between polar or
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ionic molecules is very fast. Oxidation-Reduction reactions are slower than ionic
reactions because they involve transfer of electrons and bond rearrangement. The
physical state of reacting substances are important in determining their reactivities.
The reaction in which ionic solutions are involved also take place at high speed
CONCENTRATION OF
REACTANTS
The concentration of reactants plays an important role in chemical kinetics. It is
usually true that by increasing the amount of reactants, the rate of reaction is
increased. As we know that an increase in concentration of reactants increases the
number of molecules. According to collision theory, the greater the number of
molecules the higher is the collision ratio, consequently faster is the rate of reaction.
SURFACE AREA OF
REACTANTS
In heterogeneous reactions, the rate of reaction depends upon the surface area of
solid reactant. Greater the surface area, higher is the rate of reaction. For example
finely divided calcium carbonate (marble) reacts more quickly with hydrochloric acid
than calcium carbonate chips. It is due to the fact that powered calcium carbonate
offers larger surface area to the reacting acid. In other words, by increasing the
surface area of reactant, rate of reaction increases due to greater contact between
individual particles and also due to the fact that the surface molecules reacts more
quickly.
TEMPERATURE www.citycollegiate.com
The rate of reaction increases with the rise of temperature. It can be explain by the
fact that at higher temperature, a greater fraction of colliding molecules posse the
necessary energy of activation
Generally an increase of every 10oK in temperature doubles the rate.
As the temperature increases the velocity of molecules also increases which results in
the increase in the frequency of collision.
The rise in temperature rises the kinetic energy of each molecule. It has been found
that by raising the temperature by 10k,the fraction of molecule possessing threshold
or activation energy becomes double. As a result the no of effective collision is also
double,hence rate is doubled
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H2 + Cl 22HCl