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Chemistry XI
CHAPTER # 1
INTRODUCTION TO FUNDAMENTAL CHEMISTRY
CHEMISTRY:
Branch of chemistry which deals with the study of substances, their structure, properties And
the reactions that changes them into the substances is called Chemistry.
PHYSICAL CHEMISTRY:
Branch of chemistry which deals with the study of physical properties and the structure of
matter and the laws and theories of chemistry is called Physical Chemistry.
ATOM:
OLD DEFINITION:
About 400 B.C, the Greek Philosopher Democritus defined an atom is extremely small
particle of a matter which cannot be further substances. Modern Definition: According to the
modern ideas an atom is the smallest particle of a matter which takes part of chemical
reaction (except the atom of inert gases). It may or may not have Independent existence.
MOLECULE:
A molecule may be defined as the smallest particle of matter formed by the combination of
two or more like or unlike atoms which have independent existence in nature of H 2O , CO2,
N2, O2 etc.
ELEMENT:
A substance cannot be further simplified into more simple substances by any chemical action
and possesses identical chemical and physical properties is called Element.
OR
A substance is which all of the atoms have the same atomic number i.e. same number of
protons in the nucleus is called Element.
COMPOUND:
A compound is a substance that is composed by two or more different elements united
chemically. E.g. CO2, HCl, NaCl etc.
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MIXTURE:
A material containing two or more components which have not been chemically united and
the components of the mixture retain their original properties is called Mixture.
Mixtures are of two types.
1. HOMOGENEOUS MIXTURE:
Mixture whose composition is uniform throughout is called Homogeneous Mixture.
e.g. salt solution, sugar solution, air etc.
2. HETEROGENEOUS MIXTURE:
Mixture which is not uniform in composition throughout is called heterogeneous
mixture of salt + sand, oil and water etc.
FORMULA:
A chemical formula is the symbolic representation of a molecule of a compound. It consists
of symbols and the number of atoms of each element is a molecule of a compound.
Formulas are of two types.
1: Simple Formula or Empirical Formula
2: Molecular Formula
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MOLECULAR FORMULA:
Formula which gives the total number of each kind of atoms present in the molecule of a
compound is called Molecular formula.
For example: Molecular formula of benzene is C6H6 . This shows that a molecule of benzene
is composed of six atoms of carbon and six atoms of hydrogen. Molecular formula of a
compound may be the same or simple multiple of the empirical formula.
For example: Molecular formula and Empirical formula of water and methane are same is
H2O and CH4 respectively. On the other hand molecular formula of glucose is C 6H 12O6 but
its empirical formula is C H2O.
GRAM ATOM:
Mass of one atom of an element is called Atomic mass v when this mass is expressed in gram
is called Gram Atom.
E.g. The mass of one atom of hydrogen is 1.67 10-24 g.
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FORMULA WEIGHT:
Formula weight is the sum of the atomic (weights) masses of all the atoms present in the
simple formula of the compressed.
Formula weight is expressed in atomic mass unit, when it is expressed in gram, it is called
Gram formula weight (Mass)
Formula mass of H2O = 18.00 a.m.u.
Expressed in gram = 18.00 g
Formula mass of NaCl = 58.5 a.m.u.
Expressed in gram = 58.5 g
MOLE:
When atomic mass of an element expressed in grams is called gram atomic mass, the
molecular mass expressed in gram is called gram molecular mass and when formula weight
g a compound expressed in gram is called gram formula (Weight) mass. Each of these mass
is known as a mole.
Hence a gram atomic mass, gram molecular mass and formula mass is called a mole.
e.g. Atomic mass of H = 1.0 a.m.u.
Expressed in gram = 1.0 a.m.u
= 1 g mole of H-atoms
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MODERN DEFINATION:
A mole is the amount of substances that contains as many number of particles (atoms,
molecules or ions) as there are atoms contained in 12.0 gram of pure carbon-12.
SIGNIFICANCE OF MOLE:
The significance of mole is that the having an atom of an element is, the more will be the
mass of 6.02 1023 atoms of that element be. Also the lights an atom of an element is, the less
will be the mass g 6.02 1023 atoms of that element.
SIGNIFICANT FIGURES:
Significant Figures are the reliable digits in a number that are known with certainly.
The last digit of a number is generally considered uncertain by 1 in the absence of
qualifying information. For example: The weight of an object can be expressed as 0.0112 g or
11.2 mg with changing the uncertainly of the weight or the number of significant figures. The
weight is still uncertain by 1 in the last digit. This can be expressed is 0.0112 0.0001 g or
as 11.2 0.1 mg.
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RANDOM ERRORS:
The errors which are unavailable are called random errors. i.e. the errors which remaining
variations indicate are called random errors.
EXPLANATION:
When all the systematic errors have either been eliminated or corrected, we still do not obtain
exact or true measurements because there is some uncertainly is every physical measurement.
A random error may be positive or negative. This is the only reason that we taken the average
of the several measurements, which is more reliable than any individual measurements.
EXPONENTIAL NOTATION:
The powers to the base 10 are known as exponents. Thus all numbers may be expressed as a
power of 10 and 102, 103, 105, 10-1, 10-2, 10-5 etc are generally called exponential notation in
which the base is 10.
For example: One mole of any element contains 602,300,000,000,000,000,000,000 atoms.
This is a very big value. On the other hand the mass of an electron is
0.0000000000000000000000000000911gram. This is a very small value. Such numbers can
in a better way be written in exponential notation.
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Thus 1 mole of an element will contains 6.02 10 23 atoms and mass of an electron is 9.11
10-28gm.
STOICHIOMETRY:
( Stoichiometry Element )
DEFINITION:
The quantitative study of the relationships between the amount of reactants and products of a
certain reaction as given by a balanced chemical equation is called Stoichiometry.
EXPLANATION:
The concept of mole finds one of its most useful applications in the calculations of masses
and volumes of chemical substances taking part in or produced by chemical reactions.
e.g. the following balanced equation indicates.
2H2S + 3O2 2SO2 + 2H2O
1: H2S gas and O2 gas react in the ratio of 2 molecules to 3 molecules to produce So 2 gas and
H2O vapors in the ratio of 2 molecules to 2 molecules.
2: Two moles (68 grams) of H 2S reacts with 3 moles (96 grams) of oxygen gas to give 2
moles (36 grams) of water vapors.
These amounts of reactants and products are called Stoichiometric amounts.
STOICHIOMETRIC CALCULATIONS:
While considering calculation based on the stoichiometry of chemical reaction. Three
important assumptions are considered.
1: Reactants are completely converted to products.
2: No side reactions to be considered.
3: A balanced chemical equation is provided.
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STOICHIOMETRIC RELATIONSHIP:
There are three relationships involved for the stoichiometric calculations from the balanced
chemical equation.
1: Mass Mass Relationships ( weight-weight relationship)
2: Mass - Volume Relationships
3: Volume Volume Relationships
IMPORTANCE:
The correct result by this relation is obtained if we provided with a complete and balanced
chemical equation.
This balanced chemical equation tell us the relationships of the masses or weights of the
reactants to one another and to the products.
UNITS:
The units of mass (weight) may be gram, kilogram, tons etc.
CONVERSION UNITS:
For converting weight into volume or volume into weight (mass). The Avogadros Law is
applied, according to which
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i.
ii.
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EXPLANATION:
The relation between volumes of the gases in a chemical change is based on Gay-lusses Law
of combining volumes, which states that:
Gases react or are formed in a chemical reaction in the ratio of small whole numbers by
volume measured under the same condition of temperature and pressure.
For Example:
2CO + O2 2CO2
Both reactants and products are gases.
The balanced chemical equation tells us that two volumes of carbon monoxide (CO) react
with one volume of oxygen (O2) to yield two volumes of carbon dioxide (CO 2). Thus
coefficients of the formulas gives us the volume volume relationship.
UNITS:
The units of volume may be liters dm3 etc, but the properties remains the same.
LIMITING REACTANTS:
DEFINITION:
The reactant which is present in limited amount and that after the consumption of which the
chemical reaction is stopped is called Limiting Reactant.
As in irreversible chemical reactants, the reactions go to completion in the direction of the
arrow, until one of the reactant which will be the limiting reactant is consumed entirely and
the reaction stops.
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CHAPTER # 2
THE THREE STATES OF MATTER
(SOLID, LIQUID & GAS)
MATTER:
Anything which has mass and occupies space is called Matter.
Properties / States
Shapes
Volume
Diffusion
Compression
Translational Motion
Kinetic Energy
Force of attraction
Solid
Definite
Definite
Extremely slow
No, cause deformity
No, particles vibrate
at their mean position
Negligible
High
Liquid
Not definite
Definite
Slow
Limited
Yes
Gas
Not Definite
Not Definite
Very fast
High
Yes
Moderate
Moderate
High
Negligible
GASEOUS STATE:
The state of matter in which molecules are present wide apart and can move freely in the
space provided, it neither has definite volume nor definite shape. The density of gaseous state
is less than other states of matter.
3: RANDOM ERROR:
The gas molecules are in a state of continuous random motion, travelling in straight paths
between collisions, but in random directions.
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4: ELASTIC COLLISIONS:
The gas particles continuously collide with one another and with the walls of container their
collision are perfectly elastic (i.e. no loss or gain of energy take place).
5: GAS PRESSURE:
The collision of gas molecules with the walls of container produces gas pressure.
7: K.Eave K:
The average kinetic energy of gas molecules is directly proportional to the absolute
temperature.
K.Eave K
and at any given temperature the molecules of all gases possess some average kinetic energy.
BEHAVIOUR OF GASES:
DIFFUSIBILITY:
The distribution or spreading of gas molecules throughout the vessels is known as diffusion.
IN TERMS OF KMT:
The molecules of gas are widely separated and there is large empty space between them due
to which they are free to move. Due to this free movement, molecules of gases intermix and
spread out easily throughout the vessel.
EFFUSION:
The escape of gas molecules from a very small whole of the vessel is called Effusion.
OR
Gas is forced out through a pore or tiny holes in vessels by applying little pressure.
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COMPRESSIBILITY:
The ability of matter by which they can squeeze their volume due to empty space between
molecules by an external pressure.
OR
When external pressure is applied the volume of gas decreases that is known as compression.
IN TERMS OF KMT:
Due to large empty spaces between their molecules gases are easily compressed. When
pressure is applied, molecules come closer to each other and hence gas is compressed.
EXPANSIBILITY:
The increase in temperature causes increase in average kinetic energy resulting in expansion
and gas occupies greater volume.
OR
When pressure on a compressed gas is reduced, the gas molecules rush out the gas expands.
This property of a gas is called expansibility.
Expansibility is the reverse of compressibility.
PRESSURE:
The force exerted by gas molecules on a unit area is called pressure of a gas.
Pressure = Force / Area
At 0C at Sea level 1 atom = 760 mm of Hg
= 76 cm of Hg
= 760 torr
= 14.7 Psi (Pound per square inch)
= 101300 Nm-2 or Pa
IN TERMS OF KMT:
According to KMT gas molecules are in continuous random motion due to which they collide
with one another and with the walls of container. So, gas pressure is the result of collision of
gas molecules with walls of container.
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GAS LAWS
BOYLES LAW:
The volume of a given mass of a gas is inversely proportional to the pressure exerted on it at
a given temperature.
Mathematically;
V 1/P (at constant temperature)
V = K 1/P
K = VP
PV = K
On the basis of this relation, Boyles law can also be stated as,
The product of pressure and volume of a given mass of gas is always constant at constant
temperature.
Hence,
For initial state of a gas P1V1 = K ----------- (i)
For final state of a gas P2V2 = K ------------ (ii)
Comparing equation (i) and (ii)
P1V1 = P2V2
IN TERMS OF KMT:
If the volume of a gas is decreased at constant temperature, the average velocity of the gas
molecules remains constant, so in collide more frequently with the walls of smaller vessel.
The most frequent collision cause higher pressure.
GRAPHICAL REPRESENTATION:
(i)
(ii)
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CHARLES LAW:
The volume of a given mass of gas is directly proportional to absolute temperature at given
pressure.
Mathematically;
V T (Pressure is constant)
V = KT
K=V/T
On the basis of this relation, Charles law can also be stated as,
Under constant pressure, the ratio of volume of a given gas to its absolute temperature is
always constant.
Hence,
For initial state of a gas V1 / T1 = K -------------- (i)
For Final state of a gas V2 / T2 = K -------------- (ii)
Comparing equation (i) and (ii)
V1 / T1 = V2 / T2
IN TERMS OF KMT:
A decrease in temperature, decrease the kinetic energy of the gas molecules, that is average
molecular velocity decreases. At constant pressure the decreased velocity causes the gas to
shrink and occupy a smaller volume.
GRAPHICAL REPRESENTATION:
A graph between temperature and volume give straight line.
ABSOLUTE ZERO:
The hypothetical temperature at which the volume of all gases reduced to zero and all the
motion cease to exist is called Absolute Zero.
It is -273.16C or 0 K.
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The volume of a gas decrease by decrease in temperature and theoretically it becomes zero at
-273C or 0 K.
But practically this temperature has never been achieved because gases condense to liquids at
temperature above this point.
AVOGADROS LAW:
Volume of a gas is directly proportional to the number of moles of gas at constant
temperature and pressure.
OR
Equal volume of all the gases contains same number of moles at constant temperature and
pressure.
Mathematically;
V n (temperature and pressure are constant)
V = Kn
K=V/n
On the basis of this relation, Avogadros law can also be stated as,
At constant temperature and pressure the ratio of volume of gas and its number of moles is
constant.
For two different sample of gas at same temperature and pressure a relation can be
represented as,
V1 / n1 = V2 / n2
DERIVATION:
According to Boyles Law
V 1 / P ( T and n constant )
According to Charles Law
V T ( P and n constant )
According to Avogadros Law
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V n ( T and P constant )
Combining all three laws:
V 1 / P .T.n
V = R.1/P.T.n
V = RTn/P
PV = nRT ---- General Gas Equation
Here R is constant of proportionally called General Gas constant.
For 1 mole of gas (n=1)
PV = nRT
OR
R = PV/T
If P1, V1 and T1 are the initial pressure, volume and temperature of gas, then
R = P1V1 / T1
And similarly P2, V2 and T2 are final pressure, volume and temperature, then
R = P2V2 / T2
Hence,
P1V1 / T1 = P2V2 / T2
It is another form of general gas equation.
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Since,
1 Nm = 1 Joule
Therefore,
R = 8.3143 J.mol-1.K-1
IN TERMS OF KMT:
According to KMT there are large empty spaces present among gas molecules so of another
gas is introduced the molecules of the gas will occupy the empty spaces. Hence gases can
diffuse easily.
And according to KMT two gases at equal conditions of temperature and pressure have same
kinetic energy.
(K.E) = (K.E)2
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m1v12 = m2v22
m1 = v22
m2 v12
v2 = m1
This is Grahams law.
v1
m2
As the rate of diffusion is directly proportional to velocity of molecules and density of gas is
directly proportional to mass of molecules.
PARTIAL PRESSURE:
When two or more gases which do not react chemically, are mix in the same container each
gas will exert the same pressure as it would exert if its alone occupied the volume containing
the mixed gases. This portion of total pressure of mixture is known as its partial pressure.
OR
The pressure exerted by an individual gas in a gaseous mixture is called its partial partial
pressure.
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Pt = PA + PB + Pc
As we know the general gas equation PV= nRT.
If PT is the total pressure and nT is the total number of moles.
Then,
PTV = nTRT
PT = nTRT/ V -------------(i)
Similarly, PA is the partial pressure of gas A and nA is the number of moles of gas A.
PA = nART/ V -------------(ii)
Comparing equation (i) and (ii)
PA / PT = nA / nT
PA = nAPT / nT This equation can be used to find out partial pressure.
IN TERMS OF KMT:
In a non reactive mixture of gases each gas exerts a separate on the container because of
collision of its molecules with the walls of container. Thus, the total pressure in the container
is caused by the sum of all the collision.
APPLICATION:
A gas is collected over water also contain some of water vapor. Thus, the pressure exerted by
gas would be pressure of pure gas plus the pressure of water vapors.
Pmoist = Pdry + Pwater vapors
Pdry = Pmoist Pwater vapors
Thus, partial pressure of dry gas can be obtained and its volume at S.T.P can be calculated by
following formula.
V2 = P1T2V1 / T1P2
IDEAL GAS:
An ideal gas is one whose behavior can be predicted precisely on the basis of kinetic
molecular theory and which obeys gas laws at all temperature and pressure.
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LIQUID STATE:
This state of matter is intermediate between gaseous and solid state. It has definite volume
but no definite shape.
BEHAVIOR OF LIQUID:
1: DIFFUSIBILITY:
The distribution of liquid molecules throughout the container is called diffusion of liquids
and this property is called Diffusibility.
IN TERMS OF KMT:
The freedom of liquid molecules permits diffusion to take place but the cohesive forces
among the molecules cause diffusion to be slow.
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2: COMPRESSIBILITY:
The squeezing of liquid molecules under the influence of external pressure is called
Compressibility.
Liquids are not absolutely incompressible but they may be compressed to a little extend by
high pressure.
IN TERMS OF KMT:
The liquid molecules due to their closeness roll over one another. Owing to very little space
the liquid molecules cannot be pushed close by pressure. Very high pressure is required for
squeezing a liquid.
IN TERMS OF KMT:
On heating the K.E and velocity of molecules increase, it results in expansion.
On cooling the K.E is lowered and negative forces overcome so molecule take less volume
and contraction occurs.
VISCOSITY:
The internal resistance between the molecules of a liquid to flow due to intermolecular
attraction is called Viscosity.
OR
It is the property by virtue of which it tends to oppose the relative motion between two
adjacent layers.
It is represented by (eta).
UNITS:
It is measured in poise, centipoises and millipoise and S.I unit is Newton second per meter
square (Nsm-2).
1 poise = 1 Nsm-2
1.C.poise = 10-2 Nsm-2
1 millipoise = 10-3 Nsm-2
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2: MOLECULAR SHAPE:
The irregular shaped molecules offer more resistance to flow than regular shaped molecules.
Example: Honey is very viscous due to irregular shape of its molecules.
3: INTERMOLECULAR FORCES:
The liquids having strong intermolecular forces are more viscous as their molecules are less
easily moved about.
Example: C2H5-OH is more viscous than C2H5-O-C2H5 as alcohol molecules have hydrogen
bond.
4: TEMPERATURE:
With rise in temperature, the K.E increases and intermolecular forces become less effective
and hence viscosity decreases.
Example:
Viscosity of ethyl alcohol is 1.78 poise at 0C and 0.7 poise at 50C.
Viscosity of water is 1.005 poise at 20C while 0.55 at 50C.
5: DENSITY:
The greater the density of liquid, the more viscous will be the liquid and vice versa.
SURFACE TENSION:
The force per unit length acting at right angles of the surface of liquids at a given
temperature is called Surface tension.
OR
Energy per unit area at the surface of liquid>
It is represented by (gamma).
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UNITS:
It is measured in two units dynes/cm and ergs/cm.
2: TEMPERATURE:
If temperature increases the surface tension decreases and Vice Versa.
2: CAPILLARY ACTION:
The fall or rise of a liquid in capillary tube is called Capillary action.
EXPLANATION:
If a capillary tube is placed in liquid which wets the wall of container the surface area of
liquid is decreased by raising the tube because of surface tension. Such liquid (as water) will
rise in capillary tube until the upward force due to surface tension is just balanced by
downward gravitational pull.
The level of non-wetting liquid in capillary tube will fall below the level of liquid in
surrounding space.
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While liquids which have stronger cohesive force and do not wet the glass will form convex
meniscus/surface e.g. Hg.
VAPOR PRESSURE:
The vapor pressure of liquid is a measure of tendency of that liquid to evaporate and is
defined as:
The pressure exerted by its vapors when they are in equilibrium with the liquid phase at a
given temperature
It is constant at constant temperature and is independent of the amount of liquid present.
UNITS:
It is measured in following units, mm Hg, atmosphere, N/m2, pascal etc.
2: TEMPERATURE:
Vapor pressure increase with the rise of temperature. This is because average K.E of
molecules increase with the increase of temperature and result in escape of vapors from the
surface.
Example:
Vapor pressure of H2O is 18 torr at 20C while 760 torr at 100C.
3: INTERMOLECULAR FORCES:
Liquids having low intermolecular forces have high vapor pressure, while liquids
With strong force have low vapor pressure.
BOILING POINT:
The temperature at which vapor pressure becomes equal to the atmosphere pressure is called
Boiling Point.
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2: INTERMOLECULAR FORCES:
The stronger the intermolecular forces the higher the B.P and Vice Versa.
VACCUME DISTILLATION:
Certain liquid tends to decompose at their boiling point. Such liquids are distilled under
reduced pressure at low temperature. This process is called Vacuumed Distillation.
By lowering the pressure, boiling point of liquid is reduced and their decomposition is
prevented.
PRESSURE COOKER:
Pressure Cooker helps to cook food rapidly even at higher altitude.
EVAPORATION:
The spontaneous escape of liquid molecules from its surface without boiling is called
Evaporation.
(i)
(ii)
BOILING
Boiling takes place only a
particular temperature at which
the vapor pressure of a liquid is
equal to the pressure of the
atmosphere.
Boiling involves the formation of
bubbles of the vapor throughout
the bulk of liquid.
(i)
(ii)
EVAPORATION
Evaporation occurs spontaneously
at all temperature.
Evaporation takes place only at
the surface of liquid.
COHESIVE FORCES:
The forces of attraction between similar particles of liquid are called Cohesive Force.
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ADHESIVE FORCES:
The forces of attraction between a liquid and another surface such as glass are called
Adhesive Force.
SOLID STATE:
The state of matter in which atoms, molecules or ions are held together by strong attractive
forces and cannot move freely. However, they possess vibration energy. It has definite
volume as well as definite shape.
BEHAVIOR OF SOLIDS:
Solids have highest degree of order which accounts different behaviors.
1: COMPRESSIBILITY:
The effect of pressure is negligible on solid and they cannot be compressed instead the mass
is deformed.
IN TERMS OF KMT:
Particles of solids are so tightly bound together that only slight unfilled space is left so cannot
be compressed.
2: DEFORMITY:
Solids are deformed by high pressure.
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IN TERMS OF KMT:
When some particles are dislocated under high pressure their force of attraction are enough
strong that they rearrange well with their new neighbors.
3: DIFFUSIBILITY:
Diffusion in solid is very slow or almost negligible.
IN TERMS OF KMT:
There is no translational movement of molecules in solid but nevertheless particles are
vibrating at their mean position and this vibration motion is responsible for diffusion in solid.
4: MELTINA:
When Solid is heated at certain temperature it starts changing into liquid this phenomenon is
called melting and this temperature is called melting point of solid.
IN TERMS OF KMT:
When solid is heated, the kinetic energy of molecules increases which increases their
vibration, energy and when it overcome the forces of attraction between molecules the solid
starts melting.
5: SUBLIMATION:
The process by which solids directly change to vapor without passing through liquid phase,
process is called Sublimation.
Such solid is known as Sublime.
Example: Nepthelene, Camphor, NH4Cl etc.
IN TERMS OF KMT:
The molecular forces of such solid are so weak that when they get energy the molecules get
free and change into vapor.
CLASSIFICATION OF SOLIDS:
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CRYSTALLINE SOLIDS:
Solids which have definite geometrical shape due to highly ordered three dimensional
arrangements of particles are called Crystalline Solids.
Example: Sugar, Alum, Metals and Diamonds.
AMORPHOUS SOLIDS:
Solids which do not have definite shape and non-repetitive three dimensional
arrangements.
Example: Glass, Plastic and Rubber.
CRYSTALLINE SOLIDS
Particles have definite three
dimensional arrangements.
(ii)
They have sharp melting points.
(iii)
Regular intermolecular forces
throughout crystal.
(iv)
Possess repeating unit cell.
(v)
Breakdown in a fixed cleavage
plane.
(vi)
They are anisotropy.
(vii) They are three solids.
(viii) Examples:
NaCl,
Graphite,
Diamond etc.
(i)
AMORPHOUS SOLIDS
Particles are randomly arranged.
They do not have sharp melting
point.
(iii)
Intermolecular force very form
place to place.
(iv)
They do not possess unit cell.
(v)
Do not break in a fixed cleavage
plane.
(vi)
They are isotropy.
(vii) They are pseudo solid and super
cooled liquids.
(viii) Examples: Glass, Plastic Rubber
etc.
(i)
(ii)
CLEAVAGE:
The breakage of big crystals into smaller crystals of identical shape is called Cleavage.
CLEAVAGE PLANE:
The crystals split up along particular directions. The plane which contains the direction of
cleavage is called Cleavage Plane.
ANISOTROPY:
The behavior of crystals showing variation in property in different direction is known as
Anisotropy.
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Example: Graphite can conduct electricity parallel to its plane of layers but not perpendicular
to plane.
ISOTROPY:
The behavior of crystals showing similar property in all directions is known as isotropy.
Example:
Electrical conductance, thermal conduction etc.
TYPES OF CRYSTALS:
Crystals are classified into four classes.
ATOMIC CRYSTALS:
The crystals in which atoms are packed or held together by metallic bond,l hence also known
as metallic crystals.
Example: All metals from ionic crystals.
They have following properties.
Luster
High melting point
Good conductor
Malleability
Ductility
IONIC CRYSTALS:
The crystals which consist of positively and negatively charged ions held together by
electrostatic forces of attraction are called Ionic Crystals.
Example: NaCl, CaCl2, CuSO4
They have following properties.
High melting point
Conduct electricity in fused state or in solution form
Brittleness and hardness.
3: COVALENT CRYSTALS:
Many non-metals consist of polyatomic molecules and exist in solid and their atoms are held
together by covalent bond, hence known as Covalent Crystal.
They require large amount of energy to break up.
Example: Diamond, Graphite, Silica.
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MOLECULAR CRYSTALS:
The crystals which consist of molecules held together by hydrogen bonding or vander waals
forces are called molecular crystals.
Example: Ice, Solid CO2, Solid I2
They have following properties.
Low melting point
Bad conductor
ISOMORPHISM:
When two different substances have same crystal structure, they said to be isomorphous and
the phenomenon is called Isomorphism.
Examples:
NaF & MgO Cubic
CaCO3 & NaNO3 Trigonal
ZnSO4 & NiSO4 Orthorhombic
They have following properties.
Th ey have different physical and chemical properties.
They have same empirical formula.
When their solution are mixed, they form mixed crystal.
They show property of over growth.
Length of its edges denoted by a, b and c.
Angle between its edges by , and .
SYMMETRY:
Repetition of similar edges, corners or faces at a fixed distances along definite directions is
called Symmetry.
CRYSTAL SYSTEM:
There are seven types of crystal system on the basis of cell dimensions and shapes.
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1: CUBIC SYSTEM:
A crystal system in which all axis of equal length and all angles of 90C called Cubic System.
a=b=c
= = = 90C
Example: Nacl, ZnCl and diamond.
2: TETRAGONAL SYSTEM:
It has two axis of equal length and is different, while all angles are of 90.
a=bc
= = = 90C
Example: SnO2, BaSO4, 4H2O
POLYMORPHISM:
The substance which can exist in more than one crystalline form is called polymorphous and
phenomenon is called Polymorphism.
Example: CaCo3 occurs in two crystalline forms.
(i)
Calcite Trigonal
(ii)
Argonite Orthorhombic
(i)
(ii)
(iii)
ISOMORPHISM
The phenomenon is which two
different substance have same
crystal structure.
They have different chemical
properties.
Example: NaF & MgO bith have
cubic structure.
(i)
(ii)
(iii)
POLYMORPHISM
The phenomenon in which one
substance exists in more than one
crystalline from.
They have similar chemical
properties.
Example: CaCO3 exist in Calcite
and Argonite crystalline from.
UNIT CELL:
The basic structural unit which when repeated in three dimensional produces the crystal
structure is called a Unit Cell.
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3: ORTHORHOMBIC SYSTEM:
It has all three axis of different length but all angles are of 90.
abc
= = > 90
Example: FeSO4.7H2O , ZnSO4.7H2O
4: TRIGONAL SYSTEM:
It has all three axis of equal length and all three angles are equal but more than 90 and less
than 120.
a=b=c
= = > 90
Example: Ice, Calcite, NaNO3, AgNO3, KNO3.
5: HEXAGONAL SYSTEM:
It has two axis of equal length but third is different, while two angles are of 90 and one is
120
Example: Graphite, SiO2
6: MONOCLINIC SYSTEM:
It has all three axis of unequal length one of the axis is at right angle to the other two while
two angles are of 90 and one is greater than 90.
abc
= = 90
B > 90
Example: NaCO3, 10H2O
7: TRICLINIC:
It has all axis of different length and all angles are also different.
abc
90
Example: K2Cr2O, CuSO4.5H2O
MELTING POINT:
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Melting point is the temperature at which equilibrium is established between solid and liquid
phase.
2: PRESSURE:
There are two types of effect of melting point.
(a) Those substance which expand on melting have a rise in melting point when pressure
is increased.
(b) Those substance which contract on melting have a fall in melting point when pressure
is increased.
CHAPTER # 3
CROOKS TUBE OR DISCHARGE TUBE EXPERIMENT
PASSAGE OF ELECTRICITY THROUGH GASES UNDER LOW
PRESSURE:
INTRODUCTION:
The first of the subatomic particles to be discovered was electron. The knowledge about the
electron was derived as a result of the study of the electric discharge in the discharge tube by
J.J.Thomson in 1896. This work later extended by W.Crooke.
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This discharge tube consists of a glass tube with metal electrodes fused in the walls as shown
in the figure.
Through a glass sidearm air can be drawn with a pump. The electrodes are connected to a
source of high voltage.
POSITIVE RAYS:
In 1896, Goldstein used a discharge tube with a hole in cathode. He observed that while
cathode rays were emitting away from cathode, there was colored rays produced
simultaneously which passed through the perforated cathode and caused a glow on the wall
opposite to anode. Thomson studied these rays and observed and showed that they consisted
of particles carrying a positive charge. He called them Positive Rays.
Chemistry XI
These are deflected by electric as well as magnetic field in the way indicating that
they are positively charged.
The charge to mass ratio (e/m) of positive particles varies with the nature of the gas
placed in discharge tube.
Positive rays are produced from the ionization of gas and not from anode electrodes.
Positive rays are deflected in electric field. This deflection shows that these are
positively charged so these are named as protons.
THE INFORMATION
EXPERIMENT:
OBTAINED
FROM
DISCHARGE
TUBE
The negatively charged particles electrons and positively charge particles are the fundamental
part of every atom.
RADIOACTIVITY:
In 1895, Henry Beequeral observed that uranium and its compounds spontaneously emitted
certain type of radiation which affected a photographic plate in dark and were able to
penetrate solid matter. He called these rays as radioactive rays and a substance which
possessed the property of emitting these radioactive rays and a substance which possessed the
property of emitting these radioactive rays was said to be radioactive element and the
phenomenon was called Radioactivity.
On further investigation by Mark Curie, It was found that the radiation emitted from the
element uranium as well as its salts is independent of temperature and source of mineral but
depend upon the quantity of uranium present e.g. pitchblende U3O8 was found to be about
four times more radioactive than uranium.
RADIOACTIVE RAYS:
Soon after the discovery of radium, it was suspected that these rays given out by radium and
other radioactive substances were not of one kind. Rutherford in 1902 devised an ingenious
method for separating these rays from each other by passing them between two oppositely
charged plates. It was observed that the radioactive rays were of three kinds, the one bending
toward negative plate obviously carrying positive charge were called -rays and those
deflected to the positive plate and carrying negative charge were named -rays. The third type
gamma rays pass unaffected and carry no charge.
PROPERTIES OF -RAYS:
These rays consist of positively charge.
These particles are fast moving helium nuclei.
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PROPERTIES OF -RAYS:
PROPERTIES OF -RAYS:
With the help of artificial radioactivity, the particle neutron was discovered.
SPECTROSCOPIC EXPERIMENT:
After the discovery of fundamental particles which are electron, proton, neutron, the next
question concerned with electronic structure of atom.
The electronic structure of atom was explained by the spectroscopic studies. In this
connection Plancks Quantum theory has great impact on development of theory of structure
of atom.
Chemistry XI
In 1900, Max Planck studied the spectral lines obtained from hot body radiations at different
temperatures. According to him:
When atoms or molecules absorb or emit radiant energy, they do so in separate unit of waves
called Quanta or Protons.
Thus light radiation obtained from excited atoms consists of a stream of protons and not
continuous waves.
The energy E of a quantum or proton is given by relation.
E = hv
Where v is the frequency of emitted radiation and h the Plancks constant. The value of h =
6.62 10-27 erg.sec
The main point of this theory is that the amount of energy gained or lost is quantized which
means that energy change occurs in small packets or multiple of those packets, hv, 2hv, 3hv
and so on.
SPECTRA:
A spectrum is an array of waves or particles spread out according to the increasing or
decreasing of some property. E.g. when a beam of light is allowed to pass through a prism, it
splits into seven colors. This phenomenon is called dispersion and the bend of colors is called
spectrum. The spectrum is also known as emission spectrum. Emission spectra are of two
types.
Continuous Spectrum
Line Spectrum
CONTINUOUS SPECTRUM:
When a beam of white light is passed through a prism, different wave length is refracted
through different angles. When received on a screen these form a continuous series of color
bands, violet, indigo, blue, green, yellow and red (VIBGYOR). The colors of this spectrum
are so mixed up that there is no line of between different colors. This series of bands that
form a continuous rainbow of colors is called Continuous Spectrum.
LINE SPECTRUM:
When light emitted from a gas source passes through a prism a different kind of spectrum
may be obtained.
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If the light emitted from the discharge tube is allowed to pass through a prism some discrete
sharp lines on a completely dark background are obtained. Such spectrum is known as line
spectrum. In this spectrum, each line corresponds to a definite wave length.
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EXPLANATION:
When an electron coming from the cathode strike with anode in the crooks tube. It can
remove an electron from the inner shell of the atom. Due to removal of this electron, the
electronic configuration of this ion is unstable and an electron from orbital of higher energy
drops into inner orbital by emitting energy in form of photon. This photon corresponds to
electromagnetic radiation in x-rays region.
BOHRS THEORY:
Rutherfords model of atom fails to explain the stability of atom and appearance of the line
spectra. Bohr in 1913 was first to present a simple model of atom which explained the
appearance of line spectra.
Some of the postulates of the Bohrs theory are given below:
1: An atom has a number of stable orbits or stationary states in which an electron can reside
without emission or absorption of energy.
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2: An electron may pass from one of these non-radiating states to another of lower energy
with the emission of radiations whose energy equals the energy difference between the initial
and final states.
3: In any of these states the electrons move in a circular path about the nucleus.
4: the motion of electron in these states is governed by the ordinary laws of mechanics and
electrostatic provided its angular momentum is an integral multiple of h/2.
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LYMAN SERIES:
Lyman series is obtained when the electron returns to ground. State i.e. n = 1 from higher
energy level n2 = 2, 3, 4, 5, 6 etc. This series of lines belongs to the ultraviolet region of
spectrum. It is represented by the following equation.
V = RH (1 / 12 1 / n22)
Where n2 = 2, 3, 4, 5 etc.
PASCHEN SERIES:
Paschen series is obtained when the electron returns to the 3 rd shell i.e. n = 3 from higher
energy levels n2 = 4, 5, 6 etc. This series belongs to Infrared region. The equation for paschen
series may be written as:
V = RH (1 / 32 1 / n22)
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BRACKETT SERIES:
This series is obtained when an electron jumps from higher energy levels to 4 th+ energy level.
The equation for this series is:
V = RH (1 / 42 1 / n22)
PFUND SERIES:
Pfund series is obtained when an electron jumps from higher energy level to 5th energy level.
Chemistry XI
The number of sub-levels in a given level of energy or shell is equal to its value of n.
e.g. in third shell where n=3 three sublevels s, p, d are possible.
QUANTUM NUMBERS:
There are four quantum numbers which describe the electron in an atom.
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It is represented by s which represents the spin of a moving electron. This spin may be either
clockwise or anticlockwise so the values for s may be +1/2, 0, -1/2.
SHAPES OF ORBITS:
The shape of s orbital is spherical so the probability of finding the electron is maximum
because the electrons are uniformly distributed around the nucleus.
The p orbital are dumbbell shaped. These are oriented in space along the three mutually
perpendicular axis (x, y, z) and are called px, py, pz. these are degenerate orbital of equal
energy. Each p orbital has two lobes. One of which is labeled (+) and other ( - ).
ELECTRONIC CONFIGURATION:
The distribution of electrons in the available orbital is proceeded according to these rules.
1: Pauli exclusion principle
2: Aufbau rule
3: (n+l) rule
4: Hunds rule
AUFBAU PRINICIPLE:
It is stated as:
The orbital are filled up with electrons in the increasing Order of their energy.
It means that the orbital are filled with the electrons according to their energy level. The
orbital of minimum energy are filled up first and after it the orbital of higher energy are filled.
HUNDS RULE:
If orbital of equal are provided to electron then electron will go to different orbital and having
their parallel spin.
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In other words we can say that electrons are distributed among the orbital of a sub-shell in
such a way as to give the maximum number of unpaired electrons and have the same
direction of spin. According to this rule the electronic configuration of some elements are
given below:
N = 1s2, 2s2, 2px1. 2py1, 2pz1
O = 1s2, 2s2, 2px2 . 2py1, 2pz1
(n + 1) RULE:
According to this rule:
The orbital with the lowest value of (n+1) fills first but when two orbital have the same
value of (n+1) the orbital with the lower value of n fills first.
For the electronic configuration the order of the orbital is as follows:
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s etc
ATOMIC RADIUS:
For homonuclear diatomic molecules the atomic radii may be defined as:
The half of the distance between the two nuclei present in a homonuclear diatomic molecule
is called atomic radii.
In case of hetronuclear molecule like AB, the bond length is calculated which is
(rA + rB) and if radii of any one is known the other can be calculated.
For the element present in periodic table the atomic radius decreases from left to right due to
the more attraction on the valence shell but it increases down the group with increases of the
number of shells.
IONIC RADIUS:
Ionic radius is defined as:
The distance between nucleus of an ion and the point up to which nucleus has influence of
its electron cloud.
When an electron is removed from a neutral atom the atom is left with an excess of positive
charge called a cat ion. e.g.
Na Na+ + eBut when an electron is added in a neutral atom a negative ion or onion is formed.
Cl + e- Cl
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as the atomic radius, the atomic radii are3 known from -rays analysis. The value of ionic
radius depends upon the ions that surround it.
Ionic radii if cations have smaller radii then the neutral atom because when an electron is
removed. The effective charge on nucleus increases and pulls the remaining electrons with a
greater force.
Ionic radii of an ions have a larger radii then the neutral atom because an excess of negative
charge results in greater electron repulsion.
Radius of Na- atom = 1.57
Radius of Na+ atom = 0.95 (smaller than neutral atom)
Radius of Cl atom = 0.99
Radius of Cl- atom = 1.81 (larger than neutral atom)
IONIZATION POTENTIAL:
DEFINATION:
The amount of energy required to remove most loosely bounded electron from the outermost
shell of an atom in its gaseous state is called ionization potential energy.
It is represented as:
M(gas) M+(gas) + eThe energy required to remove first electron is called first I.P. The energy required to remove
2nd or 3rd electron is called 2nd I.P or 3rd I.P.
M(gas) M+(gas) + eE = 1st I.P
M+(gas) M++(gas) + eE = 2nd I.P
M++(gas) M+++(gas) + eE = 3rd I.P
SCREENING EFFECT:
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The shell present between the nucleus and valence electrons also decreases the force of
attraction due to which I.P will be low for such elements.
ELECTRON AFFINITY:
DEFINATION:
The amount of energy liberated by an atom when an electron is added in it is called electron
affinity.
It shows that this process is an exothermic change which is represented as:
Cl + e- ClH = =348kj/mole
ELECTRONIC CONFIGURATION:
The atom with stable configuration has no tendency to gain an electron so the E.A of such
elements is zero. The stable configuration may exist in following cases.
Inert gas configuration
Fully filled orbital
Half filled orbital
ELECTRONEGATIVITY:
The force of attraction by which an atom attracts a shared pair of electrons is called electro
negativity.
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CHAPTER # 4
CHEMICAL BOND
INTRODUCTION:
Atom of all the elements exert noble gases have incomplete outermost orbits and tends to
complete them chemical combination with the other atoms.
In 1916, W. Kossel described the ionic bond which is formed by the transfer of electron from
one atom to another and also in 1916 G.N. Lewis described about the formation of covalent
bond which is formed by the mutual sharing between two atoms.
Both these scientists based their ideas on the fact that atoms attain greatest stability when
they acquire an inert gas electronic configuration.
CHEMICAL BOND:
When two or more than two atoms are combined with each other in order to complete their
link between them is produced which is known as Chemical Bond.
OR
The force if attraction which holds atoms together in the molecule of a compound is called
Chemical Bond.
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This energy which is released when one mole of gaseous ions arrange themselves in definite
pattern to form lattice is called Lattice energy.
From this example: We can conclude that it is essential for the formation of ionic bond that
the sum of energies released in the second and third steps must be greater than the energy
required for the first step.
COVALENT BOND:
A link which is formed by the mutual sharing of electrons between two atoms is called
Covalent bond.
Explanation:
In the formation of covalent bond, mutual sharing of electron takes place. This mutual
sharing is possible in non-metals, therefore covalent bond is generally formed between the
atoms of non-metals.
For example:
In Cl2 molecule, two atoms of chlorine are combined with each other to form Cl 2 molecule.
Each atom of chlorine having seven electrons in its valence shell. These atoms are united
with each other by sharing one of its valence electron as shown:
:Cl
In this molecule, one shared pair of electrons forms a single covalent bond between two
chlorine atoms with the formation of a covalent bond the energy of the system is also
decreased.
Cl + Cl Cl Cl H = -242KJ/mole
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This released energy lowered the energy of the stability of the compound is also increased.
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DIPOLE MOMENT:
The product of the charge and the distance present in a polar molecule is called Dipole
Moment and represented by .
OR
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The extent of tendency of a molecule to be oriented under the influence of an electric field is
called Dipole Moment.
Chemistry XI
BOND ENERGY:
The amount of energy required to break a bond between two atoms in a diatomic molecule is
known as Bond Energy.
OR
The energy releasing in forming a bond from the free atoms is also known as Bond Energy.
It is expressed in Kilo Joules per mole or KCl/mole.
EXAMPLES:
1: The bond energy for hydrogen molecule is:
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1: S S ORBITAL OVERLAPPING:
In order to explain S S overlapping consider the example of H2 molecule in this molecule 1s
orbital of one hydrogen overlaps with 1s orbital of other hydrogen to form sigma bonding
orbital. Due to this bonding a single covalent bond is formed between the two hydrogen
atoms. The two molecular orbital formed due to this overlapping are shown below.
2: S P ORBITAL OVERLAPPING:
This type of overlapping takes place in H Cl molecule. 1s orbital of hydrogen overlaps with
1p orbital of chlorine to form a single covalent bond. In this overlapping two molecular
orbital are formed, one of the lower energy while the other orbital is of higher energy. The
shapes of these orbital are as follows:
3: P P ORBITAL OVERLAPPING:
This type of overlapping takes place in fluorine molecule. In this mole 1p orbital of a fluorine
atom is overlapped with 1p orbital of the other fluorine atom. The molecular orbital formed in
this overlapping are given in the figure.
Pi BOND:
When the two atomic orbital involved in a covalent bond are parallel to each other then the
bond formed between them is called Pi bond.
In this overlapping, two molecular orbital are also formed the lower energy molecular orbital
is called bonding orbital while the higher energy molecular orbital is called anti bonding
orbital. The shape of these molecular orbital are as follows:
HYBRIDIZATION:
The process in which atomic orbital of different energy and shape are mixed together to form
new set of equivalent orbital of the same energy and same shape.
There are many different types of orbital hybridization but we will discuss. Here only three
main types.
1: Sp3 HYBRIDIZATION:
The mixing of one S and three p orbital to form four equivalents Sp 3 hybrid orbital is called
Sp3 hybridization. These Sp3 orbital are directed from the center of a regular tetrahedron to its
four corners. The angles between tetrahedrally arranged orbital are 109.5.
Consider the example of CH4 molecule. The electronic configuration of C atom is
1s2, 2s2, 2p1x, 2p1y, 2pz
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It has two partially filled 2p orbital which indicate that it is divalent but carbon behaves as
tetravalent in most of its compounds. It is only possible if one electron from 2s orbital is
promoted to an empty 2pz orbital to get four equivalent Sp3 hybridized orbital.
The four Sp3 hybrid orbital of the carbon atom overlap 1s-orbital of four hydrogen atoms to
form a methane CH4 molecule.
2: Sp2 HYBRIDIZATION:
The mixing of one S and two p orbital to form three orbital of equal energy is called Sp 2 or
3Sp2 hybridization. Each Sp2 orbital consists of S and P in the ratio of 1:2. These three orbital
are co-planner and at 120angle as shown.
A typical example of this type of hybridization is of ethylene molecule. In ethylene, two Sp 2
hybrid orbital of each carbon atom share and overlap with 1s orbital of two hydrogen atoms
to form two bonds. While the remaining Sp 2 orbital on each carbon atom overlaps to form a
bond. The remaining two unhybridized p orbital (one of each) are parallel and
perpendicular to the axis joining the two carbon nuclei. These generate a parallel overlap and
results in the formation of 2 orbital. Thus a molecule of ethylene contain five bonds and
one bond.
3: Sp HYBRIDIZATION:
When one S and one p orbital combine to give two hybrids orbital the process is called Sp
hybridization. The Sp hybrid orbital has two lobes one with greater extension in shape than
the other and the lobes are at an angle of 180 from each other. Its means that the axis of the
two orbital form a single straight line as shown.
Now consider the formation of acetylene molecule HC Ch. The two C H bonds are
formed due to Sp S overlap and a triple bond between two carbon atoms consists of an
bond and two bonds. The sigma bond is due to Sp Sp overlap whereas bonds are formed
as a result of parallel overlap between the unhybridized four 2p orbital of the two carbon.
Chemistry XI
The known geometrics of many molecules based upon measurement of bond angles shows
that lone pairs of electrons occupy more space then bonding pairs. The repulsion between
electronic pairs in valence shell decreases in the following order.
Lone pair Lone pair > Lone pair Bond pair > Bond pair Bond pair
When we apply this theory we can see the variation of angle in the molecular structures.
Consider the molecular structures of NH3, CH4 and H2O.
Variations from ideal bond angles are caused by multiple covalent bonds and lone electron
pairs both of which require space than single covalent bonds are therefore cause compression
of surrounding bond angles.
Thus the number if pairs of electrons in the valence shell determine the overall molecular
shape.
STRUCTURE OF BeCl2:
The two bond pairs of electrons is BeCl2 arrange themselves as far apart as possible in order
to minimize the repulsion between them.
The only arrangement which can given to satisfy this condition is linear.
HYDROGEN BOND:
When hydrogen is bonded with a highly electro negative element such as nitrogen oxygen,
fluorine. The molecule will be polarized and dipole is produced. The slightly positive
hydrogen atom is attracted by the slightly negatively charged electro negative atom. An
electrostatic attraction between the neighboring molecules is setup when the positive pole of
one molecule attracts the negative pole of the neighboring molecule. This type of attractive
force which involved hydrogen is known as Hydrogen bonding.
Hydrogen bonding causes the association of molecules with each other.
Example of hydrogen bonding are H2O and HF.
The hydrogen bonding is the strongest of the secondary bond, but it is much weak than a
normal covalent bond.
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The hydrogen bonding greatly affects the physical properties of the molecules. Due to this
bond the melting point, boiling point, density and viscosity the compounds are increased.
CHAPTER # 5
ENERGETICS OF CHEMICAL REACTION
THERMODYNAMICS:
It is a branch of chemistry which deals with the heat energy change during a chemical
reaction.
1: EXOTHERMIC REACTION:
A chemical reaction in which heat energy is evolved with the formation of product is known
as Exothermic reaction.
An exothermic process is generally represented as:
Reactants Products + Heat
2: ENDOTHERMIC REACTION:
A chemical reaction in which heat energy is absorbed during the formation of product is
known as Endothermic reaction.
Endothermic reaction is generally represented as:
Reactants + Heat Products
THERMODYNAMIC TERMS:
1: SYSTEM:
Any real or imaginary portion of the universe which is under consideration is called System.
2: SURROUNDINGS:
All the remaining portion of the universe which is present around a system is called
Surroundings.
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3: STATE:
The state of a system is described by the properties such as temperature pressure and volume
when a system undergoes a change of state, it means that the final description of the system is
different from the initial description of temperature, pressure or volume.
PROPERTIES OF SYSTEM:
The properties of a system may be divided into two main types.
1: INTENSIVE PROPERTIES:
These properties which are independent of the quantity of matter are called intensive
properties.
e.g. melting point, boiling point, viscosity, surface lension, refractive index etc.
2: EXTENSIVE PROPERTIES:
Those properties which depend upon the quantity of matter are called extensive properties.
e.g. mass, volume, enthalpy, entropy etc.
MATHEMATICAL
DERIVATION
THERMODYNAMICS:
OF
FIRST
LAW
OF
Chemistry XI
OR
E = q w
This is the mathematical representation of first law of thermodynamics.
ISOCHORIC PROCESS:
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ISOBORIC PROCESS:
A process in which pressure will remain constant is called Isoboric process.
Let qp is the amount of heat energy provided to system at constant pressure.
Due to this addition of heat the internal energy of the gas is increase from E 1 to E2 and
volume is changed from V1 to V2.
So,
According to first law of thermodynamic.
qp = E + PV
But pressure is constant
P=P
So
qp = E2 E1 + P (V2 V1)
qp = E2 E1 + PV2 PV1
qp = E2 _ PV2 E1 PV1
qp =( E2 + PV2) (E1 + PV1) --------- (2)
Here
H = E + PV
The sum of the product of PV and energy is called Enthalpy and it is denoted by H.
So
H1 = E1 + PV
H2 = E2 + PV2
Put it in equation 2
qp = H2 H1
qp = H
The heat at constant pressure is called Enthalpy.
SIGN OF H:
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All represent the change of enthalpy. It is a characteristic property of a system which depends
upon the initial and final state of the system.
For all exothermic process H is negative and for all endothermic reactions. All is positive.
THERMOCHEMISTRY:
It is a branch of chemistry which deals with the measurement of heat evolved or absorbed
during a chemical reaction.
The unit of heat energy which are generally used are Calorie and Kilo Calorie or Joules and
Kilo Joules.
1Cal = 4.184J OR 1Joule = 0.239 Cal
Na2CO3 + NaOH
H = -49KJ/mole
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CHAPTER # 6
CHEMICAL EQUILIBRIUM
REVERSIBLE REACTIONS:
Those chemical reactions which take place in both the directions and never proceed to
completion are called Reversible reactions.
For these types of reaction both the forward and reverse reaction occurs at the same time so
these reaction are generally represented as:
Reactant Product
The double arrow indicates that the reaction is reversible and that both the forward and
reverse reaction can occur simultaneously.
Some examples of reversible reactions are given below.
1: 2HI H2 + I2
2: N2 + 3H2 2NH3
IRREVERSIBLE REACTIONS:
Those reactions in which reactants are completely converted into product are called
Irreversible reaction.
These reactions proceed only in one direction. Examples of such type of reaction are given
below.
1: NaCl + AgNO3 AgCl + NaNO3
2: Cu + H2SO4 CuSo4 + H2
EQUILIBRIUM STATE:
The state which the rate of forward reaction becomes equal to the rate of reverse reaction is
called Equilibrium State.
EXPLANATION:
Consider the following reaction.
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A+BC+D
It is a reversible reaction. In this reaction both the changes (i.e. forward and backward) occur
simultaneously. At initial stage reactant A and B are separated from each other therefore the
concentration of C and D is zero.
When the reaction is started and the molecules of A and B react with each other. The
concentration of reactant is decreased while the concentration of product is increased with the
formation of product, the reverse process of the reaction starts. Due to the decrease of the
concentration of reactant, the rate of forward reaction decreases with time but the rate of
reverse reaction is increased with the formation of product C and D.
Ultimately a stage reaches when the number of reacting molecules in the forward reaction
equalizes the number of reacting molecules in the reverse direction. So this state at which the
rate of forward reaction becomes equal to the rate of reverse reaction is called Equilibrium
State.
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Kc =
This is the expression for equilibrium constant which is denoted by Kc and defined as:
The ratio of multiplication of active masses of the products to the product of active masses of
reactant is called Equilibrium Constant.
Chemistry XI
Suppose a moles of acetic acid and b moles of alcohol are mixed in this reaction. After
some time when the state of equilibrium is established. Suppose x moles of H 2O and x
moles of ethyl acetate are formed while the number of moles of acetic acid and alcohol are a
x and b z respectively at equilibrium so we can write as:
CH3COOH + C2H5OH CH3COOC2H5 + H2O
Initial moles a b
zero
zero
Moles at a x b x
x
x
Equilibrium
Concentration a x/v b x/v
x/v
x/v
At equilibrium:
According to law of mass action:
Kc = [CH3COOC2H5] [H2O] / [CH3COOH] [C2H5OH]
Kc = [x/v] [x/v] / [a x/v] [b x/v]
Kc = (x) (x) / (a x) (b x)
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CASE 1:
If [Reactant]initial [Product]initial > Kc the reaction will shift towards the reverse direction.
CASE 2:
If [Reactant]initial [Product]initial < Kc the reaction will shift towards the forward direction.
CASE 3:
If [Reactant]initial [Product]initial = Kc this is equilibrium state for the reaction.
LE CHATELIERS PRINCIPLE:
STATEMENT:
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EFFECT OF CONCENTRATION:
By changing the concentration of any substance present in the equilibrium mixture. The
balance of chemical equilibrium is distributed. For the reaction,
A+BC+D
Kc =
If the concentration of a reactant A or B is increased the equilibrium state shifts to right and
yield of products increases.
But if the concentration of C or D is increased then the reactions proceed in the backward
direction with a greater rate or more A and B are formed.
EFFECT OF TEMPERATURE:
The effect of temperature is different for different type of reaction.
For an endothermic reaction heat is absorbed for the conversion of reactant into product so if
temperature during the reaction is increased then the reaction will proceed with a greater rate
in forward reaction.
Temperature increase More products are formed
ENDOTHERMIC REACTION
Temperature decrease More reactants are formed
Temperature increase More reactants are formed
EXOTHERMIC REACTION
Temperature decrease More products are formed
EFFECT OF PRESSURE:
The state of equilibrium of gaseous reaction is disturbed by the change of pressure. There are
three types of reactions which show the effect of pressure change.
Chemistry XI
1: EFFECT OF CONCENTRATION:
The value of Kc for this reaction is:
Kc = [NH3]2 / [N2] [H2]3
Increase in concentration of reactants which are nitrogen and hydrogen, the equilibrium of the
process shifts towards the right so as to keep the value of K c= constant. Hence the formation
of NH3 increases with the increase of the concentration of N2 or hydrogen.
2: EFFECT OF TEMPERATURE:
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3: EFFECT OF PRESSURE:
The formation of NH3 proceeds with the decrease in volume. Therefore, the reaction is
carried out under high pressure or in other words high pressure is favourable for the
production of NH3.
CONTACT PROCESS:
The process is used to manufacture H2SO4 on large scale. In this process the most important
step is the oxidation of SO2 to SO3 in presence of a catalyst Vanadium pentoxide.
2So2 + O2 2SO3
H = -395KJ/mole
1: EFFECT OF CONCENTRATION:
The value of Kc for this reaction is:
Kc = [SO3]2 / [SO2]2 [O2]
Increase in concentration of SO2 or O2 shifts the equilibrium towards the right and more SO 3
is formed.
2: EFFECT OF TEMPERATURE:
Since the process is exothermic, so low temperature will favour the formation SO 3. The
optimum temperature for this reaction is 400 to 450C.
3: EFFECT OF PRESSURE:
In this reaction decrease in volume takes place so high pressure is favourable for the
formation of SO3.
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SOLUBILITY PRODUCT:
When a slightly soluble ionic solid such as silver chloride is dissolved in water. It
decomposition into its ions.
AgCL Ag+ + ClThese Ag+ and Cl- ions from solid phase pass into solution till the solution becomes saturated.
Now there exists an equilibrium between the ions present in the saturated solution and the
ions present in the solid phase, thus:
AgCL Ag+ + ClUndissolved
dissolved
Applying the law of mass action:
Kc = [Ag+] [Cl-] / K
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Or Kc K = [Ag+] [Cl-]
Or Ks.p = [Ag+] [Cl-]
Where Ks.p is known as solubility product and defined as:
The product of the concentration of ions in the saturated solution of a sparingly soluble salt
is called Solubility product.
The value of solubility product is constant for a given temperature.
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CHAPTER # 7
HYDRATION
SOLUTIONS AND ELECTROLYTES
SOLUTION:
A homogeneous mixture or a single phase mixture of two or more substances is
called solution.
SOLUTE:
The component of solution present in smaller amount is called solute.
SOLVENT:
The component of solution present in larger amount is called solvent
CONCENTRATION OF SOLUTION:
The amount (No. of Moles, No. of Atoms or No. of Molecules) of a solute
present in a given amount of solvent or solution is called concentration of
solution.
The number of moles of solute present per dm3 of solution is called molar
concentration or morality of the solution.
The morality is denoted by M and is calculated as:
M
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EXAMPLE:
When 1 mole of HCl (i.e. 36.5 gm HCl) is present in 1 dm 3 solution the morality of solution
is 1M similarly if 0.5 moles of HCl (i.e. 18.25 gm HCl) is present in 1 dm 3 of solution the
morality of solution is 0.5 M
EXAMPLE:
When one mole of glucose (180 gm glucose) is dissolved in 1 kg of H 2O the molality of
solution is 1m similarly if 2 moles of glucose (360 gm glucose) is dissolved in 1 kg H 2O the
solution is said to be 2 molal.
HYDRATION:
Addition of water or association of water molecules with a substance without dissociation is
called Hydration.
Water is a good solvent and its polar nature plays very important part in dissolving
substances. It dissolves ionic compounds readily.
When an ionic compound is dissolved in water, the partial negatively charged oxygen of
water molecule is attracted towards the cation ion similarly the partial positively charged
hydrogen of water molecule is attracted towards the anions so hydrated ions are formed as
shown in figure.
In solution, the number of water molecules which surround the ions is indefinite, but when an
aqueous solution of a salt is evaporated, the salt crystallizes with a definite number of water
molecules which is called as water of Crystallization. E.g. when CuSO 4 recrystallized from
its solution the crystallized salt has the composition CuSo4.5H2O. Similarly when magnesium
chloride is re-crystallized from the solution, it has the composition MgCl 2.6H2O. This
composition indicates that each magnesium ion in the crystal is surrounded by size water
molecules. This type of salts is called hydrated salts.
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It is observed experimentally that the oxygen atom of water molecule is attached with the
cation of salt through co-ordinate covalent bond so it is more better to write the molecular
formulas of the hydrated salts as given below.
[Cu(H2O)5]SO4 [Mg(H2O)6]Cl2
It is also observed that these compound exist with a definite geometrical structure e.g. the
structure of [Mg(H2O6)Cl2 is octahedral and [Cu(H2O)4]+2 is a square planar as shown.
HYDROLYSIS:
DEFINITION:
The reaction of cation or anion (or both) of a salt with water so as to change its pH is known
Hydrolysis.
SALIENT FEATURES:
1234-
EXAMPLES:
1- When NH4Cl is added in water it forms a strong acid and a weak base. So the
resultant solution becomes acidic.
NH4Cl + H OH NH4OH + HCl
2- When Na2CO3 id dissolved in water it forms a strong base and a weak acid so the
solution has higher conc. of OH- and the pH becomes basic.
Na2CO3 + H OH NaOH + H2CO3
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THEORY OF IONIZATION:
INTRODUCTION:
This theory was put forward by a Swedish chemist Arrbenius in 1887. It accounts for
electrical conductivity of electrolyte solution and it also describes the effect of ionization on
colligative properties of a substance.
POSTULATES OF THEORY:
1: ELECTROLYTES:
Electrolytes are substances that contain charged particles called ions except H +, all positive
ions are derived from metals and negative ions are derived from non-metals.
2: DISSOCIATION OF ELECTROLYTES:
Particles of electrolytes (acid, base, salt) dissociate into opposite charged ions on dissolution
in water.
e.g.
H2SO4 2H+ + SO4-HCl H+ + ClNaOH Na+ + OH-
3: EQUILIBRIUM
MOLECULE:
BETWEEN
IONIZED
AND
UNIONIZED
The ionization is a reversible process. Ions recombine to form unionized molecules. So the
solution contains ions of electrolyte together with unionized molecules.
H2SO4 2H+ + SO4--
DEGREE OF IONIZATION:
The external of dissociation of an electrolyte is called degree of ionization or dissociation.
Greater the dissociation, greater will be conduction of electricity through solution.
Degree of dissociation =
It depends upon
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i.
ii.
iii.
Chemistry XI
Nature of electrolyte
Degree of dilution
Temperature
i: NATURE OF ELECTROLYTE:
Strong electrolytes (HCl, NaCl) ionize almost completely, whereas weak electrolytes
(CH3COOh, NH4OH) ionize partially.
iii: TEMPERATURE:
Ionization increases with increase in dilution.
DRAW BACKS:
This theory cannot explain.
i)
Conductance of electrolytes in fused state.
ii)
Why conductance of strong electrolytes does not increase with dilution.
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ELECTRODE POTENTIAL:
DEFINATION:
The potential difference between a metal and solution of its salt is called electrode
potential.
OR
It is the measure of tendency of an electrode to loose e- (oxidation) or gain e- (reduction),
when it is dipped in its salt solution.
UNIT:
The unit of electrode potential is volt.
REPRESENTATION:
It is represented by E.
i: OXIDATION POTENTIAL:
DEFINATION:
It is the measure of tendency of an electrode to loose e- or get oxidized when dipped in the
solution of its salt.
It is denoted by Eox
Chemistry XI
EXAMPLE:
Eox Zn / Zn++ = + 0.76
ERED Zn++ / Z = - 0.76
SYMBOL:
It is represented by E.
STANDARD ELECTRODE:
Defination:
A half cell used for measuring electrode potential of another half cell is called standard
electrode.
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CONSTRUCTION OF S.H.E:
A hydrogen electrode consists of a platinum plate immersed in 1 molar solution of H+. A
current pure H2 is passed continuously through the solution under 1 atm. The platinum
absorbs the gas on its surface and this hydrogen coated platinum acts as the hydrogen
electrode.
POTENTIAL OF S.H.E:
Potential of S.H.E udner 1 atm, 25C and 1 molar H+ solution is assumed to be zero i.e.
i: FOR OXIDATION:
H2 2H+ + 2e-
i.e.
We can say that,
E H2 / H+ = E H+ / H2 = 0.00 volt
CONSTRUCTION OF CELL:
The cell is constructed as follow:
i.
One half cells is made of Zn plate immersed in 1M Zn++ solution at 25C.
ii.
The other half cell is S.H.E.
iii.
Electrodes of both half cells are externally connected by a wire, thorugh a volt
meter.
iv.
Solutions of both half cells are joined by KCl salt bridge.
OBSERVATION:
Spontaneous flow of electrons (e-) is observed from Zn electrode to hydrogen electrode. As a
result voltmeter shows a reading of 0.76 volt.
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CONCLUSION:
It is concluded that:
i.
Zn is losing e-, i.e. it oxidized or it is ANODE.
ii.
As e- are accumulated on zinc so its negatively charged.
iii.
Standard potential of hydrogen electrode is 0.00 volt hence the meter reading i.e.
0.76 volt is standard potential of Zn.
Standard Ox. Potential of Zn
OR
E Zn / Zn++ = 0.76 volt
CELL REACTIONS:
(i): AT ANODE (OXIDATION)
Zn(s) Zn(aq)++ + 2e-
And
Ecell = Eox + ERED
= 0.76v + 0.00v
= 0.76v
CELL NOTATION:
Zn(s) ; Zn++
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OXIDATION NUMBER:
The formal charge (i.e. not real) on the atom in the compound or ion under consideration is
known as Oxidation number or state.
OXIDATION:
Oxidation is a chemical change in which electrons are lost by an atom or group of atoms.
EXAMPLE:
Fe Fe2+ + 2eIn this reaction neutral iron atom has lost 2 electrons and has changed to ferrous ion so it is
oxidation.
OR
Oxidation is a process in which oxidation number if an element is increased.
EXAMPLE:
C + O2 C+4O2(-2)
Is an oxidation of carbon, since its oxidation number increases from zero to +4.
REDUCTION:
Reduction is a chemical change in which electrons are gained by an atom or group of atoms.
Consider the following examples:
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EXAMPLE:
Cl2 + 2e- 2ClIn this reaction, Cl2 gains two electrons and changes to Cl- ions it is therefore reduction.
OR
Reduction is a process in which oxidation number of an element is decreased.
EXAMPLE:
H2 + Br2 2H+BrIn the reduction of bromine as its oxidation number decreases from 0 to 1.
INDICATES:
Organic substance that change color in solution as the PH of the solution change are called
Indicates.
OR
Indicates are complex molecules that are themselves weak acids (Phenolphthalein) or weak
base (methyl orange).
USE:
Indicates are used to find the end point of an acid base titration.
Color in Acid
Color in Base
Color
Litmus
Methyl Orange
Phenolphthalein
Universal indicator
Red
Red
Colorless
Red
Blue
Yellow
Pink
Purple
Purple
Orange
Colorless
Green
Phenolphthalein
Methyl Orange
Any one
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TYPES OF INDICATORS:
There are three types of Indicators.
1. Acid base indicator
2. Redox indicator
3. Precipitation indicator
2: REDOX INDICATOR:
Indicators used in redox reaction are called redox indicators
EXAMPLE:
Potassium Permanganate
3: PRECIPITATION INDICATOR:
An indicator, which reacts with reactant at the end point and form a precipitate is called
Precipitation indicator.
EXAMPLE:
Potassium Chromate
pH:
Logarithm of the reciprocal of hydrogen ion concentration is called pH.
OR
Negative logarithm of hydrogen ion concentration is called pH.
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MATHEMATICAL REPRESENTATION:
pH = log
pH = -log [H+]
EXPLANATION:
Pure water ionizes very slightly and is therefore a weak electrolyte.
H2O H+ + OH
Thus equilibrium expression on the above reaction is given by:
Kc =
Kc [H2O] = [H+] [OH-]
Kc [H2O] = Kw
Where Kw is called the ionic product of water which is equal to 1.0 10-14 moles/dm3.
Thus
[H+] [OH-] = 1.0 10-14
[H+] = 10-7
[OH-] = 10-7
pH = - log [H+]
pH = - log 10-7
pH = 7 log 10
pH = 7(1)
pH = 7
pH = 7 for neutral solution
ORANGE
3
YELLOW
6
GREEN
7
BLUE
8
PURPLE
14
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2: BY USING pH METER:
A pH meter has a glass electrode which when dipped into solution, will give direct reading of
the pH value on the meter.
pOH:
Logarithm of the reciprocal of hydroxyl [OH-] ion concentration is called pOH.
OR
Negative logarithm of hydroxyl ion concentration is called pOH.
MATHEMATICAL REPRESENTATION:
pOH = log
pOH = - log [OH-]
BUFFER SOLUTION:
A solution in which tends to resist change in pH is called a Buffer Solution.
Chemistry XI
Such solution can be prepared by mixing weak bases and their salts with strong acids.
APPLICATION OF BUFFER:
The use of buffer is an important part of many industrial processes. Examples are
electroplating and the manufacture of leather, photographic materials & dyes.
The biological research culture media are generally buffered to maintain a constant
pH is required for the growth of the bacteria being studied.
Buffers are used extensively in analytical chemistry and are used to calibrate pH.
Human blood is buffered to pH of 7.4 by means of bicarbonates, phosphates and
complex protein systems.
BUFFER ACTION:
The property of a solution due to which it tends to maintain its pH when an acid or an alkali
is added to it is called buffer action.
BUFFER CAPACITY:
The capacity of a solution to maintain definite pH is called buffer capacity.
NEUTRALIZATION:
Reaction in which are cid reacts with a base to form salt and water is called Neutralization.
EXAMPLE:
Acid + Base Water + Salt
HCl + NaOH H2O + NaCl
OR
Reaction of cation of an acid with anion of base to form water is called Neutralization.
EXAMPLE:
H+ + OH- H2O.
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CHAPTER # 8
CHEMICAL KINETICS
INTRODUCTION:
The branch of physical chemistry which deals with the speed or rate at which a reaction
occurs is called chemical kinetics.
The study of chemical kinetics therefore includes the rate of a chemical reaction and also the
rate of a chemical reaction and also the factors which influence its rate.
The determination of the rate of a reaction is not so simple because the rate of a given
reaction is never uniform it falls of gradually with time as the reactants are used up hence we
cannot get the velocity or rate of reaction simply by dividing the amount of substance
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transformed by the time taken for such transformation for this reason we take a very small
interval of time dt during which it is assumed that velocity of reaction remains constant if
dx is the amount of substance transformed that small interval of time dt then the velocity
of reaction is expressed as.
Velocity of a reaction
dx / dt
Thus with the velocity of a chemical reaction use mean the velocity at the given moment or
given instant.
P
(Product)
[R]
=K [R]
Chemistry XI
K = V/[So3]2 [O2]
ENERGY OF ACTIVATION:
DEFINITION:
The minimum energy required for a reactant to reach to an excited state or activated state is
called energy of activation
OR
The minimum energy required for a collusion to be effective is known as energy of activation
For a chemical reaction the reacting molecules are collided with each other and after
collusion if their energy is increased such that they can reach to the activated state then they
are able to from product every reaction has its own energy of activation energy takes place at
low temperature and a reaction with higher energy of activation will take place at high
temperature similarly those reactions which are required low energy of activation are
proceeded with a greater rate but those reaction in which high energy of activation is required
are generally slow.
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The rate of a chemical reaction is usually increased by adding a catalyst which is actually
decreased the energy at activation due to which rate of reaction is increased
AFFECT OF CONCENTRATION:
As we know that the rate of chemical reaction is directly proportional to the concentration of
the reactants are evil able for the reaction the rate of reaction will be greater by increasing the
concentration of reactants the collusion frequency increases so the number of effective
collusion increases so more product is formed.
TEMPERATURE:
With the increase of temperature the average kinetic energy of the molecules is increased
therefore the chance of effective collusion is greater at high temperature so with the increase
of temperature the rate of a chemical reaction is generally increased. It is observed that a rise
of 10oC in temperature approximately doubles the rate of reaction.
CATALYST:
DEFINITION:
A substance which alters the rate of a chemical reaction its self remaining chemically
unchanged at the end of the reaction is called Catalyst.
A catalyst which increases the rate of a chemical reaction by lowering energy of activation is
called positive catalyst where as a catalyst which decreases the rate of a chemical reaction by
increasing energy of activation is called negative catalyst or inhibitor the effect of a positive
catalyst is shown in the figure.
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