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1 Atoms, molecules and stoichiometry

Relative Atomic mass Ar It is the weighted average mass of an atom of an element compared with 1/12th of
the mass of an atom of carbon-12.

Relative formula mass Mr Average mass of a formula of a compound relative to 1/12th of the mass of carbon
12 atom.

Relative molecular mass Mr Average mass of a molecule of a compound or an element relative to 1/12th
of the mass of an atom of carbon-12. atom.

Empirical formula empirical formula represents the simplest whole number ratio of the atoms of different
elements present in the formula of a compound.

Molecular formula Molecular formula represents the actual number of atoms of each element in one molecule
of a compound.

Relative isotopic mass Mass of an isotope of an element relative to 1/12th of the mass of an atom of carbon-12.

Molecular formula of a compound = n * empirical formula

Mole A mole is the amount of substance contained by 6.02 * 10^23 particles.

6.02 * 10^23 is called Avogadro’s constant

Note It is always important to always refer to what the particle is. For example one mole of oxygen atom is 16g
and one mole of oxygen molecules is 32 g.

Mass of one mole of a substance is called molar mass

Molar mass of hydrogen atom = 1g

Molar mass of water = 18g

Molar mass of CO2 = 44g

Volume of one mole of any gas at rtp = 24dm3

Volume of one mole of any gas at stp = 22.4 dm3

Isotopic abundance
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2 Atomic structure

The ionization energy increases with increase in nuclear attraction

Distance of outermost electrons from the nucleus

The force of attraction between the outermost electron and positively charged nucleus decrease with the increase in
distance between them. Attraction falls rapidly with the increase in distance so this factor is very important and it
has a big effect. The ionization energy therefore decreases with the increase in the distance between nucleus and
outermost electron.

The number of protons in the nucleus (Nuclear charge)

The attraction between the nucleus and outermost electron increases with the increase in nuclear charge. The
ionization energy, therefore increases with the increase in nuclear charge

The shielding effect of inner electrons

The electrons present in the inner shells repel the outermost electron and reduce the effect of the positive nuclear
charge. This is called shielding effect. With increase in shielding effect it becomes easier to remove the outermost
electron. The ionization energy therefore decreases with the increase in shielding effect.

Trends of ionization energies

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In a group
As we move down the group. The ionization energy decreases because,
No of shell of electron increases, this increases the distance of outermost electron from the nucleus.
Nuclear attraction decreases.
Due to increase in no of shells shielding effect increases. The electrons present in the inner shells repel
the outermost electron and reduces the effect of attraction of positively charged nucleus.
These two factors outweigh the effect of increased nuclear charge
(ii) Trend in a period (2nd and 3rd )
The variation in ionization energy provides an evidence for the existence of sub-shells.
Across a period, there is a general increase in ionization energy
The nuclear charge increases across a period due to which nuclear attraction increases.
The atomic radius decreases across a period due to which nuclear attraction increases.
Shielding effect of inner electrons almost remains constant in a period because no of shells are same.
Na and Mg
All above points
Outer electron of both Na and Mg is in 3S orbital(same energy level)
Be and B
Comparing Be to B (Same reason for Mg and Al)
Boron outermost electron is in the 2p sub-shell.
Be outermost electron is in 2S sub-shell
The 2p electron in B experiences lesser nuclear attraction and therefore has more energy because
(i) The distance between the nucleus and outer electron increases slightly
(ii) It is more shielded from nuclear attraction
These two factors outweigh the increased nuclear charge

N and O
Both nitrogen and oxygen have their electrons in the same 2p sub-shell with the same energy level.
Nitrogen has only one electron in each p orbital (singly filled).
Oxygen has one 2p orbital with an electron pair. It is easier to remove one of the paired electrons
from the 2p orbital due to the mutual repulsion between the paired electrons.
The first ionization energy of oxygen is therefore lower than nitrogen.
Ne and Na
There is a rapid decrease in ionization energy between the last element in one period and the first
element in the next period. The first ionization energy of Na is less than first ionization energy of all
elements in the previous period.
• The distance between nucleus and the outer electron increases due to which nuclear attraction decreases.
• The shielding by inner shells increases due to which nuclear attraction decreases.
• These two factors outweigh the increased nuclear charge

The variations of successive ionization energies

The variations of successive ionization energies provide the evidence for existence of shells.

There will be a gradual increase in the successive ionization energy values if the electrons are removed from the
same quantum shell.

There will be a big jump in the successive ionization value if the electron is removed from the inner stable quantum
shell.
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First sharp increase indicates the no of electrons in the valance shell.

Sharp rise in successive ionization energy values between 3rd and 4th value indicates that the 4th electron is in the
next inner shell. The element is in group 13. There is a large decrease in distance of outermost electron from
nucleus and shielding effect also decreases. These two factors result in large increase in nuclear attraction.

When electrons are removed from the same shell there is a gradual increase in ionization energy because the size of
particle decreases due to decrease in repulsion between electrons. This makes removal of electron more difficult
from a positively charged ion due to increase in attraction between positively charged nucleus and outermost
electron

4 States of matter

KINETIC THEORY OF GASES

• Kinetic theory explains the behaviour of an ideal gas. An ideal gas is one which obeys General gas equation
(ideal gas equation) and kinetic theory of gases.
• According to this theory
o The particles are in continuous random motion.
o Volume of gas molecules is negligible compared to the volume of the vessel.
o Different other statements to explain the same concept
▪ molecules have mass but negligible size
▪ or intermolecular distances are much greater than molecular size. Most of the volume of
gas is empty space
▪ The molecules have negligible volume
▪
o There are no intermolecular forces.
o The collisions between the molecules are perfectly elastic

PARTICLES OF MATTER

SOLIDS

 Definite shape
 Definite volume
 The forces of attraction between particles are very strong. The particles vibrate about a fixed position. Particles are closely
packed due to which solids have high densities. Solids can not be compressed. Solids do not flow.

LIQUIDS

 No fixed shape.
 Fixed volume.
 The forces of attraction between particles are strong. The particles can slide over each other and can move about freely
within the volume of liquid in the form of loose clusters.. The particles are further apart than solids. Their density is
therefore lesser than solids. Liquids are slightly compressible.
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Gas

 No fixed shape.
 No fixed volume.
 The forces of attraction between particles are very weak. Particles are in random motion, they move about freely. The
particles are very far apart. They have very low density. Gases are easily compressible.

Diagrammatic representation of the particles in each of the physical state

Change of state

 When a solid is heated the particles vibrate as they gain energy.

 This makes them push their neighbouring particles further away from themselves. This causes expansion.
 Eventually, the particles gain enough energy to overcome forces of attraction between particles and solid melts. There is no
rise in temperature during this process. The heat energy is utilized to bring about a separation of particles at this
temperature. We call this temperature the melting point of the substance. The temperature remains constant until the
whole solid has melted into a liquid.

 The temperature at which this takes place is called melting point.

 Solids having high melting points have strong forces of attraction between particles

Evaporation

• Evaporation is the spontaneous conversion of a liquid into vapour phase below its boiling point.
• At any given temperature, average kinetic energy of the liquid molecules is constant but different molecules possess
different energies. Molecules which have sufficient energy to overcome intermolecular forces escape the liquid surface
and turn into gas.

 Liquids having high boiling points have strong forces of attraction between particles.
 Conversion of gas into liquid is called condensation.
Vapour Pressure

The pressure exerted by the vapours on the surface of liquid at equilibrium state at a given temperature is called vapour
pressure.

In a closed vessel the high energy molecules leave the liquid. After sometimes vapours will saturate space above the liquid
surface. At this stage condensation and evaporation will be taking place at the same rate. At this stage pressure exerted by the
vapours on the surface of the liquid is called its vapour pressure at that temperature. Vapour pressure increases with the
increase in temperature. The liquids which have weaker intermolecular forces have higher vapour pressure.

When vapour pressure becomes equal to atmospheric pressure, the liquid starts boiling.

The liquids which have high vapour pressure boil at a lower temperature.

Volatile liquids have high vapour pressure.

Crystalline lattice structures of solids

1. Giant ionic lattices

• Examples MgO, NaCl
• High melting and boiling points because the alternating oppositely charged ions in 3 dimensions in ionic solids
have strong forces of attraction between them.
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• Non conductors of electricity.

• MgO is used in ceramics which are used as a refractory materiel for lining the furnaces
• In both compounds each positive ion is surrounded by 6 negative ions and vice versa.

Giant metallic solids

Examples Cu, Zn, Al, Fe

High mp, bp

Good conductors of electricity

Used for making wires and making alloys

Giant molecular solids (Macromolecules)

Diamond

• Hard
• High mpts because the carbon atoms are bonded covalently in tetrahedral arrangement in a
continuous 3 dimensional structure (giant structure). A lot of energy is required to break these
strong bonds.
• Non conductor of electricity
• Used for cutting and drilling

SiO2, SiC

• Hard
• High mpts because the atoms are bonded covalently in tetrahedral arrangement in a continuous 3
dimensional structure (giant structure). A lot of energy is required to break these strong bonds.
• Non conductor of electricity
• Used for glass manufacturing and ceramics.
•

Graphite

• Soft
• Sippery to touch
• Bonding extend in two dimensions. Each layer is one molecule. The melting point is high because each atom is
covalently bonded with 3 other carbon atoms. A lot of energy is required to break those strong bonds.
• Good conductor of electricity. Each carbon atom is covalently bonded with 3 other carbon atoms. The 4 th electron of
each carbon atom is free to move between layers. Due to presence of these free electrons, graphite is a good
conductor of electricity.
• Used as electrodes and as lubricant

Simple molecular solids

•Examples iodine, sulphur, phosphorous

•Low mp. These are all non-polar molecules. They have weak intermolecular forces (instantaneous dipole,
induced dipole forces). A small amount of energy is required to overcome these weak intermolecular forces.
• Non conductor of electricity because they don’t have free electrons or mobile ions.
Hydrogen bonded solids
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• ice
• low density

Hydrogen bonding in Ice

• In almost all materials, the solid is denser than liquid. Water is the exception, Solid H2O is less dense than liquid H2O.
In water, each oxygen atom forms two hydrogen bonds and two covalent bonds. In liquid state the water molecules
are moving about due to which weak hydrogen bonds break easily. When water freezes, the water molecules are no
longer free to move and hydrogen bonds form permanently. The resulting 3 dimensional structure resembles the
structure of diamond. Due to this tetrahedral structure, the molecules are less tightly packed than in liquid water.
Thus ice is less dense than water.
• Water has relatively strong intermolecular forces, in addition to weak intermolecular van der Waals forces. This results
in higher melting and boiling points in water than the simple molecules containing only weak van der waals forces.

Advantages of Recycling.

• Reduced demand for new raw materiel

• Reduction in environmental damage
• Lesser demand for landfill sites to dump waste
• Reduced cost of waste disposal
• Reduced energy cost..
8 Reaction kinetics

• The speed of chemical reaction tells us how fast or slow a chemical reaction is taking place.
• Kinetics is the study of the speed or rate of reaction.
• Speed of reaction = amount of reactant used up / time taken
or

= amount of product produced / time taken.

Activation energy

Molecules require a certain minimum energy before they can react. This energy is called Activation Energy.
Only molecules which have energy equal to or greater than activation energy react.

Both exo or endothermic reaction can occur readily if they have low activation energy

Collision Theory
• A chemical reaction involves two processes
• (i) Bond breaking
• (ii) Bond formation
o Reacting particles must collide before they react. Breaking of bonds in the reacting particles
requires energy. The energy required for this purpose is derived from the kinetic energy of the
colliding particles.
o The minimum amount of energy required to start a chemical reaction by breaking bonds of the
reactant molecules is called activation energy.
• For a reaction to take place particles must collide with energy equal or greater than the activation
energy. Such collisions are called successful collisions. They result in the formation of product.
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• If particles collide with energy less than the activation energy than no reaction takes place.

The rate of reaction can be increased by increasing the number of successful collisions. The number of
successful collisions can be increased by

• Increasing the number of collision.

• Decreasing activation energy.
• Increasing energy of collision.

The rate of reaction depends on five factors.

1. Cocentration
2. Pressure
3. Size of particles
4. Catalyst
5. Temperature

Effect of concentration
• This factor is important when we are dealing with solutions or gases..
• Higher concentration means that there are more particles per unit volume.
• Thus the number of collisions per unit time increases.
• The average kinetic energy of the collisions remains same (because temp is constant). Thus the
percentage of successful collisions remains the same.
• The number of successful collisions per unit time will increase in the same proportion. And it results
in increase in rate of reaction If no of collisions is doubled; number of successful collisions will also
double.

• Effect of pressure

Pressure can be increased by :

(i) reducing the volume of the container

(ii) pumping more reactant gas into the container

Either way, the result is same. The concentration of reactant gas molecule will increase.

• Higher concentration means that there are more particles per unit volume.
• Thus the number of collisions per unit time increases.
• The average kinetic energy of the collisions remains same (because temp is constant). Thus the
percentage of successful collisions remains the same.
• The number of successful collisions per unit time will increase in the same proportion. It results in
increase in rate of reaction
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Particle size
• If one of the reactant is a solid then breaking it up into smaller pieces will increase its surface area
• More particles are exposed for the chemical reaction.
o . Thus the number of collisions per unit time increases.
o The average kinetic energy of the collisions remains same (because temp is constant). Thus the
percentage of successful collisions remains the same. The number of successful collisions will increase
o The number of successful collisions per unit time will increase in the same proportion. It results in
increase in rate of reaction
•
• Catalyst
• Definition: A catalyst is a substance, which increases the rate of reaction by lowering activation energy.
The catalyst provide an alternate pathway for the reaction. Catalyst participates in the chemical reaction but
is not chemically changed at the end of the reaction.
• For a reversible reaction, it increases the rate of both forward and backward reaction
• Catalyst alters the mechanism or pathway of reaction.
• Amount of catalyst remains unchanged at the end of the reaction.
• Changing concentration of catalyst changes the rate of reaction.
• Transition metals and their compounds are often used as catalysts.
• It is generally specific in action, i.e. different reactions use different chemicals as catalysts.
• Catalyst only speeds up the reaction; it does not affect the type and amount of products formed (yield) in a
reaction. It also does not affect delta H value of the reaction.
• For a reversible reaction, catalyst lowers the activation energies of both the forward reaction and the
backward reaction by equal amount. Thus, the catalyst speeds up both the forward and backward reactions
and system reaches dynamic equilibrium quickly. Catalyst has no effect on the equilibrium constant of the
reaction. Equilibrium constant only changes by change in temperature.
• Catalysts are used in industry to save time and energy (money)
o Time can be saved by increasing rate of reaction
o Instead of increasing rate of reaction by increasing temp, the rate of reaction can be increased by using
catalyst.

• A common catalyzed reaction is the decomposition of hydrogen per oxide.

•
o Without a catalyst this reaction takes years.
o with manganese (IV) oxide (black powder), the reaction takes only seconds.
o When a piece of liver is added, the reaction takes only seconds.

• Over 90 % of the industrial processes use catalyst. In industries, the catalyst speeds up the reaction and hence
save time and money ( less energy is required ).
Iron is used in the Haber process for the manufacture of ammonia.

Nickel is used in the hydrogenation of unsaturated oils to make margarine

Vanadium (V) oxide is used in the contact process for the manufacture of sulphuric acid.

•
• Catalyst increases the reaction rate by lowering the activation energy.
• Number of collisions per unit time remains the same.
• The average kinetic energy of the collisions remain same (because temperature is constant)
• More particles will have energy greater than or equal to the activation energy. Thus the percentage of
successful collisions will increase which increases rate of reaction.
•
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Effect of temperature
• When the temperature is increased, the average kinetic energy of the particles is increased.
o Due to faster motion the number of collisions per unit time increases.
o Due to higher kinetic energy, the percentage of successful collisions per unit time increases.
o Thus the number of successful collisions per unit time will increase. This increases the rate
of reaction.
o The number of successful collisions per unit time will increase in the same proportion. It
results in increase in rate of reaction
• .it is true that when the temp increases, kinetic energy increases and the no of collision increases but
the main reason which increases rate of reaction is the increase in no of molecules having energy more
than activation energy

Note: Concentration and particle size increases the rate of reaction by increasing the no of collisions. Temperature
increases the rate of reaction by increasing the no of collisions as well as %age of successful collisions. Catalyst does
not increase the no of collisions, it only increases the %age of successful collisions.

Manufacture of ammonia
The manufacture of ammonia by Haber’s process is represented by the equation

Nitrogen is obtained by the liquefaction of liquid air.

Hydrogen gas is produced by reacting methane with steam

The purpose of heat exchanger is to warm the incoming gas mixture and speed up the reaction.

The equation provides the following information.

(i) The reaction is exothermic in the forward direction.
(ii) When ammonia forms pressure decreases.

On the basis of Le Chatelier’s principle, there are three ways to maximize the yield of ammonia

1. Continual removal of ammonia By continual removal of ammonia after intervals, the reaction
will be favoured in the forward direction and yield of ammonia will increase.

2. Low temperature Lower temperature will favour the reaction in the forward direction. But it will
decrease the rate of reaction ( both forward and backward)

3. High pressure Higher pressure will favour the reaction in the forward direction. It also
increases the rate of reaction ( both forward and backward) by increasing frequency of collision.
High pressure increases manufacturing cost. ( both operational and manufacturing cost of plant)

Following conditions are used in the manufacture of ammonia

• Temperature is maintained at 450 ᵒC. This is a compromise temperature. At this temperature
rate of reaction is fast enough to give a reasonable yield of ammonia. The heat exchanger is used
to warm the incoming gas mixture.
• A pressure of 200 atm (atleast 150 atm) is used. A higher pressure would have high energy costs,
and thicker walled pipes and strong vessel to withstand high pressure would make the
construction of the plant more expensive.
• Finely divided iron is used at catalyst. This helps to reach dynamic equilibrium sooner.

Manufacture of sulphuric acid

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• Sulphuric acid is manufactured by using contact process.

• The raw materials for the manufacturing of sulphuric acid are sulphur, air and water.

1. Sulphur is burnt in air to form sulphur dioxide. The air is passed so fast that only half of the oxygen
is used. The remaining hot oxygen is used in the next process for the production of SO3. This hot
air increases rate of reaction. If air is passed slowly, very hot air will decrease yield of sulphur
trioxide. The air used to burn Sulphur must be as clean as possible because impurities may poison
the catalyst

2. sulphur dioxide is reacted with oxygen to give sulphur trioxide. The reaction is exothermic in the
forward direction.

The system is similar to manufacture of ammonia. Hence similar conditions favour the formation of
SO3 which are
(i) Low temperature
(ii) High pressure
(iii) Excess oxygen
(iv) Catalyst V2O5

But the actual condition used in the industry are

Temperature is kept at 450 ᵒC which is a compromise between yield and rate of reaction. The catalyst is
ineffective below this temperature.
Pressure is kept at 2-3 atm. Under these conditions about 98% yield is obtained. A higher pressure
would the only increase the cost of establishing and maintaining the plant.
Higher yields of sulphur trioxide are obtained by using excess of air in the reversible reaction. Thus
according to Le Chatelier’s principle equilibrium is favoured in the forward direction.
The conversion of SO2 to SO3 is an exothermic reaction. The temperature of the catalyst increases
during the reaction. Higher temperature favours the reaction in the backward direction. The catalyst
must be cooled to 450 ᵒC by using heat exchanger to improve yield.
The air used in the reaction must be clean from dust and other impurities.. Impurities in air may poison
the catalyst.
3. Sulphur trioxide is not directly dissolved in water because the reaction is highly exothermic . the
heat evolved is so large the sulphuric acid vaporizes forming a dangerous mist. This constitutes a
serious safety hazard.
To overcome this problem. SO3 is dissolved in concentrated sulphuric acid to produce oleum H2S2O7.
Oleum is than dissolved in water to obtain 98 % sulphuric acid.

SO3 + H2SO4 → H2S2O7

H2S2O7 + H2O → H2SO4
Similarities between Haber and Contact process
1 A higher yield is favoured by higher pressure.
2 The reaction is a redox reaction.
3 The forward reaction is exothermic.

Types of catalytic reactions

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Catalysts can be divided into two main types - heterogeneous and homogeneous. In a
heterogeneous reaction, the catalyst is in a different phase from the reactants. In a
homogeneous reaction, the catalyst is in the same phase as the reactants.

What is a phase?

If you look at a mixture and can see a boundary between two of the components, those
substances are in different phases. A mixture containing a solid and a liquid consists of
two phases. A mixture of various chemicals in a single solution consists of only one
phase, because you can't see any boundary between them.

You might wonder why phase differs from the term physical state (solid, liquid or gas). It
includes solids, liquids and gases, but is actually a bit more general. It can also apply to
two liquids (oil and water, for example) which don't dissolve in each other. You could
see the boundary between the two liquids.

Enzymes
Enzymes are biological catalysts. Enzymes are proteins. They are specific in their action. Enzyme
specificity refers to the tendency for enzymes to catalyze a specific set of chemical reactions.

state the variation in the solubilities of the hydroxides and sulfates

solubilities of group II hydroxides increases down the group and solubilities of sulfates decreases down the group

3 Chemical bonding

Ionic or Electrovalent bond.

• ionic compounds form giant structures in which ions are arranged due to strong forces of attraction
between oppositely charged ion. A lot of energy is required to overcome these forces of attractions
• An ionic bond is formed when electrons are transferred from a metal atom to a non-metal atom.
• Metal atom loose their electrons and form positive ions.
• Non-metal atoms gain electrons and form negative ions.
• An ionic bonding is the electrostatic forces of attractions between oppositely charged ions.
• Ionic bonding is formed between metals and non-metals but all metals and non-metals do not form ionic
bonding. Ionic bonding is formed between metals and non-metals of significantly different
electronegativities.
• An ionic compound as a whole is neutral. Number of positive charges is equal to no of negative charges.
•
Properties of ionic compounds

• The ionic compound consist of three dimensional arrangement of oppositely charged ions forming
crystalline lattice structure.
• Ionic compounds do not consist of discrete molecules. They form giant structures.
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• Ionic compounds have high melting and boiling points (.> 450 C). due strong electrostatic forces of
attractions between oppositely charged ions. A lot of energy is required to overcome these strong
forces of attractions. All ionic compounds are solids at room temperature.
• Ionic compounds do not conduct electricity in solid state because in solid state ions are at their fixed
position. Ionic compounds can only conduct electricity if they have mobile ions.
• Ionic compounds conduct electricity in molten and aqueous state because in these states ions are free to
move (mobile ions).
• Ionic compounds are usually soluble in polar solvent like water but they are insoluble in organic solvents
which arenon- polar.

Don’t use the terms molecules and intermolecular forces while describing ionic compounds and their properties.

Note ionic bond is the attraction between the ions-not their formation.

Covalent Bonding

• A covalent bond is formed by the overlap of two atomic orbitals, each containing a single unpaired
electron. The shared electrons in the molecular orbital attract the 2 nuclei and hold the two atoms
together. This electrostatic attraction between electrons in the molecular orbital and the two nuclei are
covalent bonding.
• covalent bonding is due to electrostatic force of attraction between bonding electrons and the nuclei
• Covalent bonding is usually formed between non-metals but there are few exceptions such as AlCl3,
BeCl2,SnCl2,, SnCl4.
• Dot and cross diagram H2, O2, Cl2, HCl, CO2, CH4, C2H6, NH3,H2O, CCl4, C2H4,H2S, N2H4.
• Properties of Simple covalent compounds
o They have low melting and boiling points because the forces of attraction between molecules
(intermolecular forces) are weak. A small amount of energy is required to overcome these
forces of attraction. Simple covalent compounds are therefore gases. Low boiling point liquids
(volatile liquids) or low melting point solids.
o Simple covalent compounds do not conduct electricity in any state because they don’t have free
electrons or mobile ions. Acids are exceptions. They are covalent compounds but they conduct
electricity only in aqueous state due to presence of mobile ions.
o Simple covalent compounds are usually insoluble in water and soluble in organic solvents.
Metallic Bonding

Metallic bonding is the electrostatic force of attraction between positively charged metal ions and the sea of
electrons. The electrons present in the outermost shell contribute to the sea of electrons.

Metallic structure metallic structure is lattice of positive ions surrounded by sea of electrons.

Factors affecting metallic bonding

Strength of metallic bonding increases with the decrease in atomic radius and increase in no of electrons present in
the outermost shell. The melting point of metals depend upon the strength of the metallic bonding.

The melting point therefore increases as we move from left to right in a period and decreases as we move down a
group.
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Properties of metals

• Metals have generally high melting point.

• Metals are good conductors of heat and electricity due to presence of free electrons.
• Metals are malleable and ductile. When a force is applied layers of ions slide over each other and metal
takes a new shape. Free electrons hold the structure in the new position.

• A covalent bond is formed by the overlap of two atomic orbitals each containing a single
unpaired electron. These shared electrons are now present in a molecular orbital. The covalent
bonding is electrostatic attraction between electrons in the molecular orbital and the two nuclei.

• Definition Hybridization is mixing of different orbitals to form same energy orbitals

• Only central atom hybridizes.

• Orbitals of the same shell hybridize. (Only use valence shell electrons

• The number of hybrid orbitals formed = number of atomic orbitals used

One s + one p ⇒ two sp hybrid orbitals

One s + two p ⇒ three sp2 hybrid orbitals

One s + three p ⇒ four sp3 hybrid orbitals

One s + three p + one d ⇒ five sp3 d hybrid orbitals

One s + three p + two d ⇒ six sp3 d 2 hybrid orbitals

No of s No of p No of d No of hybrid Shape Angle of

orbital orbitals orbitals orbitals molecule

1 1 0 2 sp Linear 180

1 2 0 3 sp2 Trigonal planar 120, 117

Non-linear

1 3 0 4 sp3 Tetrahedral 109.5, 107,

104.5
Trigonal
pyramidal

Non-linear

1 3 1 5 sp3d Trigonal 90, 120 in

bipyramidal same
molecule

1 3 2 6 sp3d2 octahederal 90
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• No of electrons that go into unhybridized p orbitals = π bonds

• Number of bonds formed by an atom is equal to number of unpaired electrons it has. Like
oxygen and nitrogen make two and three bonds because they have these many unpaired
electrons in their valence shell. But, in its ground state, carbon got only two unpaired electrons,
so it should make two bonds. But in reality carbon make four bonds. Two satisfy four bonds we
need four unpaired electrons. This process is called excitation. Excitation increases no of
unpaired electrons.

• Orbitals hybridize because doing so allows the resultant molecule to be lower in energy — and
therefore more stable — than if the orbitals did not hybridize.

• CH4
• The electronic configuration of a carbon atom is 1s22s22p2

•
• If you provide a bit of energy you can promote (lift) one of the s electrons into a p orbital.It is excitation. The
excitation will result in four unpaired electrons. Now methane can form four bonds instead of two bonds.
The configuration is now 1s22s12p3

•
• The four orbitals (an s and three p’s) combine or HYBRIDISE to give four new orbitals. All four orbitals are
equivalent.

•
• sp3 HYBRIDISATION

• The angle between these sp3 orbitals is 109.5

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• H2O
• In water no excitation is required because O has already 2 unpaired electrons. There is also no
empty orbital to unpair 2s electrons. O therefore cannot form more than 2 bonds. Based on
this configuration, you would expect oxygen to form two covalent bonds — one with each
hydrogen atom — and that is what happens. However, you would expect the resulting molecule
to have an H-O-H bond angle of about 90 degrees (angle between p orbitals is 90 degrees), and
that is decidedly not the case.

• Because the oxygen atom does not form bonds with its two half-filled 2p orbitals. Instead, as the
oxygen atom is bonding with two hydrogen atoms, its orbitals hybridize into four equivalent sp3
orbitals (it is sp3 hybridization because one s and three p orbitals mix to form four new
orbitals). In doing so, the regions of electron density are able to spread apart, which lowers the
electrostatic repulsion between them and increases stability.

NH3

In ammonia no excitation is required because N has already 3 unpaired electrons. There is also no
empty orbital to unpair 2s electrons. N therefore cannot form more than three bonds

C2H4
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Only three orbitals (an s and two p’s) combine or HYBRIDISE to give three new orbitals. All three orbitals are
equivalent. The remaining 2p orbital is unchanged. This 2p orbital sideways overlap with the 2p orbital of other C
atom to form pi bond

In ALKENES, the three sp2 orbitals repel each other into a planar arrangement and the 2p orbital lies at right angles
to them

Covalent bonds are formed by overlap of orbitals

An sp2 orbital from each carbon overlaps to form a single C-C bond. The resulting bond is called a SIGMA (δ) bond.

The orbitals involved in π bond don’t hybridize. The two 2p orbitals sideways overlap. This forms a second bond.
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s orbitals in hydrogen overlap with the sp2 orbitals in carbon to form C-H bonds

Be Cl2
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BCl3
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Organic

Chlorofluorocarbons

• Chlorofluorocarbons (CFC's for shorthand) are organic molecules containing carbon,

fluorine and chlorine e.g. dichlorodifluoromethane has the formula CCl2F2
• CFCs are used in refrigerators and air conditioners because they are gases at room
temperature which can be easily liquefied by compression and because they are stable and
non-toxic
• CFCs are used as foaming agents in the production of polystyrene and polyurethane foam
plastics used for insulation and packing materials
• CFCs are used as a propellant in spray cans for paint, insect repellants, deodorants
• CFCs are used in fire extinguishers because they are dense, non-flammable
liquids. Bromochlorodifluoromethane, CF2ClBr, is commonly used in fire extinguishers.

• They are very useful low boiling organic liquids or gases,.

23

• They are relatively unreactive ( due to strong C-F bond) , non–toxic and non-
flammable, so in many ways they are 'ideal' for the job they do.

However it is their chemical stability in the environment that eventually causes the ozone problem

CFC’s have been blamed for damage to the environment by thinning the ozone layer

Ozone absorbs a lot of harmful UV radiation

However ozone breaks down more easily in the presence of CFC's

CFC’s break up in the atmosphere to form radicals. Chlorine free radicals are formed
because C-Cl bond is weaker than C-F bond.

CF2Cl2 ——> CF2Cl• + Cl•

Free radicals catalyse the breaking up of ozone 2O3 ——> 3O2

Compounds containing Br also destroy ozone layer.

o Chemists are developing less environmentally harmful alternatives.

• Alternatives to CFCs i.e. HFCs and HCFCs)
o The idea is to use replacement compounds that are less harmful to the ozone layer.
o The molecules listed below contain C–H bonds and are broken down in the lower
troposphere before they reach the ozone layer in the stratosphere.
▪ Hydrochlorofluorohydrocarbons (a HCFC is composed of hydrogen,
chlorine, fluorine and carbon atoms) e.g. CH3CFCl2 1,1–dichloro–1–
fluoroethane
o Hydrofluorocarbons (a HFC is composed of hydrogen, fluorine and carbon atoms)
▪ e.g. CH2FCF3 1,1,1,4–tetrafluoroethane
o Alkanes (composed of hydrogen and carbon atoms)
▪ e.g. butane CH3CH2CH2CH3 but they are flammable!
o However, all of these molecules are greenhouse gases and will contribute to
global warming!

Inorganic Chemistry

Periodicity
24

Pattern of properties as we move from left to right across a period is called periodicity

Properties of period 3 elements:

25

- Atomic radius

Atomic radius decreases across the period because :

The number of protons increases which pulls electrons closer to the nucleus.

No of shells remain same.

Shielding effect remains same.

Attraction increases.
26

- Covalent radius always gives smaller values due to overlap between orbitals- Argon does
not form any bonds or compounds. It exists as mono atomic (single atom)

Ionic radius
27

Positively charged ions are smaller than the original atoms and the anions of the same
period.

From Na+ to Si4+ the ionic radius decreases

No of electrons is same.

Nuclear charge is increasing.

No of shells is same.

Ionic radius of anions (negatively charged ions) is larger than the parent atom and cations
of the same period.

From P3- to Cl- ionic radius decreases because:

No of electrons is same.

Nuclear charge is increasing.

No of shells is same.
28

Melting points

Giant structures (found on the left) have high melting and boiling point.

Simple molecular structures have low melting and boiling point.

From Na to Al, melting point increases due to increase in strength of metallic bonding.

Strength of metallic bonding increases due to

Increase in nuclear charge

Increase in no of delocalized electrons,

Decrease in ionic radius.

Silicon has very high melting point because it has many strong covalent bonds. A lot of
energy is required to break these strong covalent bonds.

The elements to the right of silicon are all non-metallic elements. They have simple
molecular structure. Ar has atomic structure.

They have low melting and boiling points. They have weak intermolecular forces (van der
Waal forces). The strength of intermolecular forces depends on number of electrons.

P4 has 60 electrons.

S8 has 128 electrons

Cl2 has 34 electrons.

Ar has 18 electrons
29

Electrical conductivity

Na, Mg and Al metals are good conductors of electricity due to presence of delocalized
electrons.

Electrical conductivity increases from Na to Al due to increase in number of delocalized

electrons.

Si is a semi-conductor which conducts electricity only under certain conditions.

P, S, Cl and Ar do not conduct electricity because they do not have free moving electrons.

Ionization energy
30

First ionization energy is the energy required to convert a mole of gaseous atoms into a
mole of singly positively charged gaseous ions.

One electron is removed from each gaseous atom.

There is a general increase in ionization energy across a period.

Nuclear charge increases, this factor increases ionization energy.

Shielding effect remains same.

Atomic radius decreases across a period. This factor also increases ionization energy.
31

Reason of drop in first ionization energy between group 5 and 6

This is due to pairing of electrons.

An electron in pair is easy to remove.

P has no paired electrons, because each p electron is in a different sub-shell.

S has two of its p-electrons paired, and one of these will be easier to remove than an
unpaired one.
32

Reaction(s) of period 3 elements with Oxygen

Na

Sodium reacts vigorously when heated and placed in a gas jar of O2. it burns with a yellow
flame and a white solid is formed. Freshly cut Na tarnishes rapidly due to formation of
sodium oxide.

4Na(s) + O2(g) → 2Na2O(s)

Mg

Magnesium burns with a bright white flame. Reaction is vigorous. White (powder/ash type)
solid is formed.

2Mg(s) + O2(g) → 2MgO(s)

33

Al

Al2O3 forms easily at room temperature and is a useful protection for the metal
underneath. Aluminium is protected by a tough layer of its oxide Al2O3 so it does not react.
But powdered Al reacts with O2. it burns with a bright white flame. White solid is formed.

(note: all gpI, gp2, Al and Zn compounds are white)

4Al(s) + 3O2(g) → 2Al2O3(s)

Si

Silicon (macro molecule) reacts very slowly with oxygen to form a white solid.

Si(s) + O2(g) → SiO2(s)

Phosphorous has two allotropes: white phosphorous P4 is very is very reactive and is stored
under water.

Red P is less reactive and is polymeric form.

White P4 is very reactive. Red P is less reactive.

White P4 reacts vigorously with O2. It burns with a white flame and cloud of white
phosphorous (IV) oxide are formed.

P4(s) + 5O2(g) → P4O10(s)

Yellow solid Sulfur burns gently with a blue flame in air or in a gas jar of O2. Yellow solid
melts turn red and then disappears. Pungent smelling, choking gas is released (SO2).

S(s) + O2(g) → SO2(g)

Sulfur cannot form sulfur trioxide by direct reaction with O2 (even when O2 is in excess). The
reaction takes place in the presence of a catalyst V2O5 at 450C. Pressure is kept at 2 to 3
atm.

Contact process

2SO2(g) + O2(g) → 2SO3(g)

34

Element Na Mg Al P4 S
Flame color Yellow white white white blue

Oxides of period 3 elements

Properties of oxides of period three elements

Properties Na2O MgO Al2O3 SiO2 P4O10/ SO2 SO3

P4O6
structure Giant Giant Giant Giant Simple Simple Simple
ionic ionic ionic covalent molecular molecular molecular
Acid base Basic Basic Ampho Acidic Acidic Acidic Acidic
nature teric
Melting High High High High Low Low Low
point
Oxidation +1 +2 +3 +4 +5/+3 +4 +6
state
Color of White White White White White Colorless Colorless
oxide gas gas
Color of yellow White White yellow blue
flame
vigorous vigorous vigorous

Reaction(s) of oxides of with water

Na2O

Sodium oxide reacts with water to form a strong alkaline solution.

Na2O(s) + H2O(l) → 2NaOH(aq)

MgO

Magnesium oxide reacts with water to form a weak alkaline solution.

MgO(s) + H2O(l) → Mg(OH)2(aq)

35

Al2O3 (amphoteric) and SiO2 (macro molecule) do not react with water.

P4O10

Phosphorous (V) oxide reacts vigorously with water to form an acidic solution.

P4O10(s) + 6H2O(l) → 4H3PO4(aq)

SO2/SO3

Sulfur dioxide and sulfur trioxide reacts with water to form an acidic solution.

Sulfurous acid or sulfuric (IV) acid

SO2(g) + H2O(l) → H2SO3(aq)

Sulfuric acid or sulfuric (VI) acid

SO3(g) + H2O(l) → H2SO4(aq)

Propertie Na2O MgO Al2O3 SiO2 P4O10 SO2 SO3
s
product NaOH Mg(OH)2 H3PO4 H2SO3 H2SO4
pH 14 11 2 2 2
vigorous vigorous vigorous

Acid-base reaction(s) of period 3 Oxides

Na2O/ MgO

Sodium oxide and magnesium oxide are basic oxides that react with acids to form salt and
water.

Na2O(s) + H2SO4(aq) → Na2SO4(aq) + H2O(l)

MgO(s) + 2HCl(aq) → MgCl2(aq) + H2O(l)Al

Al2O3

Aluminium oxide is an amphoteric oxide that reacts with both acids and alkali to form salts.

Al2O3(s) + 3H2SO4(aq) → Al2(SO4)3(aq) + 3H2O(l)

36

Al2O3(s) + 2NaOH(aq) + 3H2O(l) → 2NaAl(OH)4(aq)

SiO2

Silicon dioxide is an acidic oxide that dissolves and reacts with hot concentrated alkali.

SiO2(s) + 2NaOH(aq) → Na2SiO3(aq) + H2O(l)

P4O10

Phosphorous (V) oxide is an acidic oxide that reacts vigorously with sodium hydroxide to
form salt and water.

P4O10(s) + 12NaOH(aq) → 4Na3PO4(aq) + 6H2O(l)

SO2/SO3

Sulfur dioxide and sulfur trioxide are acidic oxides that react with alkali to form salts and
water.

Sulfur dioxide forms sulfites

SO2(g) + 2NaOH(aq) → Na2SO3(aq) + H2O(l)

Sulfur trioxide forms sulfates

SO3(g) + 2NaOH(aq) → Na2SO4(aq) + H2O(l)

Reaction of Na and Mg with water

Sodium reacts with cold water.

It melts into a silvery ball.

The silvery ball moves across the surface of water, giving off colorless and odorless
hydrogen gas. The gas produced burns with a pop sound.

The silvery ball gets smaller and smaller until it disappears (not dissolves), leaving a strongly
alkaline solution (pH = 14).

The reaction is exothermic.

Mg reacts very slowly with cold water.

When a piece of Mg is placed into water it sinks and at first nothing appears to happen.
37

It takes several days to produce a test tube of hydrogen gas.

The solution formed is very weakly alkaline (pH=11), because is slightly soluble in water.

Mg reacts with steam to form MgO and hydrogen gas.

Reaction(s) of period 3 elements with chlorine

All elements except argon react with chlorine. Metals form ionic halides. Non-metals form
molecular halides.

Common observation: metal/greenish yellow gas disappears.

Na

Metal disappears

Greenish yellow gas disappears

When Na is heated and then plunged into a gas jar of chlorine, Na burns with a yellow
flame in the gas. A vigorous reaction takes place forming a white powder.

2Na(s) + Cl2(g) → 2NaCl(s)

Mg

Metal disappears

Greenish yellow gas disappears

Magnesium burns with a white flame. Vigorous reaction takes place

White solid.is formed

Mg(s) + Cl2(g) → MgCl2(s)

Al

Metal disappears

Greenish yellow gas disappears

Al burns with a white flame. Vigorous reaction takes place

White solid.is formed

38

2Al(s) + 3Cl2(g) → 2AlCl3(s)

→ Al2Cl6(s)

Si

Si (s) disappears

Greenish yellow gas disappears

Silicon reacts slowly with chlorine forming a colorless, volatile liquid.

Si(s) + 2Cl2(g) → SiCl4(l)

P4 (s) disappears

Greenish yellow gas disappears

White phosphorous reacts slowly with chlorine to form a colorless, volatile liquid.

P4(s) + 6Cl2(g) → 4PCl3(l)

In excess of Cl2 white solid PCl5 is formed

SiCl4 and PCl3 are colorless liquids. Other chlorides are white solids

Chlorides of period 3 elements

39

Properties NaCl MgCl2 AlCl3 SiCl4 PCl3 PCl5

structure Giant Giant Simple Simple Simple Simple

ionic ionic molecular molecular molecular molecular
Melting High High Low Low Low Low
point
Oxidation +1 +2 +3 +4 +3 +5
state
Color of White White White Colorless Colorless White
chloride solid solid solid liquid liquid solid
Color of yellow White White
flame
vigorous vigorous vigorous
Reaction of Just Hydrolysis Hydrolysis Hydrolysis Hydrolysis Hydrolysis
chloride dissolves Vigorous Vigorous Vigorous
with water
pH of aq 7 6.5 3 2 2 2
solution

Effect of water on chlorides of period 3 elements

NaCl

Sodium chloride simply dissolves in water and the solution is neutral.

NaCl(s) + (aq) → NaCl(aq)

MgCl2

Magnesium chloride dissolves in water to give a slightly acidic solution.

MgCl2(s) + (aq) → MgCl2(aq)

AlCl3

When Al2Cl6 is added in water, positive and negative ions are formed. Hydrolysis reaction
takes place. The reaction is exothermic. Al3+ has very high polarizing power so it polarizes
water molecule. Water molecule loses its H+ and acidic solution results. (OH) will be ligand
so will not make the solution alkaline.

[Al(H2O)6]+3(aq) ↔ [Al(H2O)5(OH)]+2(aq) + H+(aq)

SiCl4

Silicon chloride is hydrolyzed in water forming white steamy fumes of HCl. Reaction is
vigorous and the solution becomes acidic.
40

SiCl4(l) + 2H2O(l) → SiO2(s) + 4HCl(aq)

PCl5

Phosphorous (V) chloride is hydrolyzed in water forming white fumes of HCl. Reaction is
vigorous and the solution becomes acidic.

PCl5(s) + 4H2O(l) → H3PO4(aq) + 5HCl(aq)

Hydrolysis of PCl3 results in the formation of H3PO3.

Structure of period 3 chlorides

- NaCl and MgCl2 have giant ionic structure.

- Al2Cl6, SiCl4, PCl3 and PCl5 have simple molecular structure.

pH of period 3 aq chlorides

- NaCl = 7

- MgCl2 = 6.5

- Al2Cl6 = 3

- SiCl4/PCl3/PCl5 = 2

Only two chlorides are liquids and no oxide is liquid

Al and Si oxides have high mps and chlorides have low mps

Density of Li, Na and K are less than water.

Group II
41

Electronic configuration Ionization energy decreases

Be [He] 2S2 Reactivity increases.

Mg [Ne] 3S2 Reducing power increases.

Ca [Ar] 4S2 m.p and b.p decreases due

Sr [Kr] 5S2 to decrease in strength of metallic bonding.

Ba [Xe]6S2 Thermal stability of nitrates and

carbonates increases

Ra [Rn] 7S2

- In all group two compounds, the oxidation state of group two metals is +2

- Group two metals have low melting and boiling point as compared to other metals but is
higher than group I metal in the same period.

-They have low densities as compared to other metals but is higher than group I metals in
the same period.

Solubility of hydoxides increases down the group. Mg(OH)2 is slightly soluble in water.
Ba(OH)2 is soluble in water.

Solubility of sulfates decreases down the group. MgSO4 is soluble in water. Others are
insoluble in water.
42

Chemical properties

Reaction(s) of gp II metals with water or steam

- Reactions are exothermic.

- H2(g) is produced.

- If these metals react with water, then they definitely react with steam.

When metals react with water hydroxides are formed

When metals react with steam oxides are formed

Metal(s) +2 H2O(l) → M(OH)2(-aq--) + H2(g)

Metal(s) + H2O(g) → MO(-s) + H2(g)

Mg

Reaction with water is very slow. Weak alkaline solution is formed.

Mg reacts vigorously with steam. Mg glows white solid forms.

Mg(s) + 2H2O(l) → Mg(OH)2(aq) + H2(g)

Mg(s) + H2O(g) → MgO(s)+ H2(g)

Ca

Ca(s) + 2H2O(l) → Ca(OH)2(aq) + H2(g) reaction becomes more and more vigorous.

Sr solution becomes more

Sr(s) + 2H2O(l) → Sr(OH)2 (aq)+ H2(g) alkaline due to increase

in solubility of metal

Ba hydroxides.

Ba(s) + 2H2O(l) → Ba(OH)2(aq) + H2(g)

Observation with Ca
43

White cloudy suspension of sparingly soluble Ca(OH)2 forms. Metal disappears.

Temperature of beaker rises. A colorless gas is produced.

Observation with Sr and Ba

Metal disappears. Temperature of beaker rises. A colorless gas is produced.

Reaction(s) of gp II metals with oxygen

- Group II metals react vigorously with oxygen to form their respective (white) oxides.

Mg

2Mg(s) + O2(g) → 2MgO(s) reaction becomes

Ca more vigorous.

2Ca(s) + O2(g) → 2CaO(s)

Sr

2Sr(s) + O2(g) → 2SrO(s)

Ba

2Ba(s) + O2(g) → 2BaO(s)

Mg burns with a white flame. Ca and Sr burn with red flame. Ba burns with green flame.

- These group II metal oxides react with water to form their respective hydroxides.

Mg

MgO(s) + H2O(l) → Mg(OH)2(aq) reaction becomes

44

Ca more vigorous. Solution becomes

CaO(s) + H2O(l) → Ca(OH)2(aq) more alkaline due to increase in

solubility

Sr

SrO(s) + H2O(l) → Sr(OH)2(aq)

Ba

BaO(s) + H2O(l) → Ba(OH)2(aq)

CaO = quick lime/lime

Ca(OH)2(s) = slaked lime

Ca(OH)2(aq) = lime water

CaCO3(s) = limestone

Thermal stability of group II carbonates and nitrates

- Compounds which are thermally stable require large amount of heat for decomposition.
Thermal stability of group II carbonates and nitrates increases down the group.

- Down the group, size increases so polarizing power decreases. Therefore, stability
increases.

- Example:

Bond breaking of magnesium carbonate is easiest because magnesium ion has small size,
hence greater polarizing power. It polarizes the carbonate ion and thus magnesium
carbonate decomposes to magnesium oxide (same for nitrates).

Group II metal Carbontes

MgCO3(s) → MgO(s) + CO2(g)

45

CaCO3(s) → CaO(s) + CO2(g)

SrCO3(s) → SrO(s) + CO2(g) thermal stability

BaCO3(s) → BaO(s) + CO2(g) increases down

Group II metal Nitrates the group.

Mg(NO3)2(s) → MgO(s) + 2NO2(g) + 1/2O2(g)

Ca(NO3)2(s) → CaO(s) + 2NO2(g) + 1/2O2(g)

Sr(NO3)2(s) → SrO(s) + 2NO2(g) + 1/2O2(g)

Ba(NO3)2(s) → BaO(s) + 2NO2(g) + 1/2O2(g)

Mg and Ca nitrates and carbonates can even be decomposed by the heat of a Bunsen burner.
Other oxides and carbonates require higher temperature.

Uses of group II compounds

MgO(s)

Magnesium oxide has a very high melting point. Has low thermal conductivity. It will
absorb some acidic impurities in some metallurgical processes. It is therefore used as a
refractory material for lining of the furnace.

CaCO3(s)

Calcium carbonate is used in the manufacture of steel and glass. It is also used to control
the acidity of the soil. It is used to remove acidic flue gases.

CaO(s)

Lime mortar is a mixture of lime, sand and water. It is used for brick laying in construction.
It is also for controlling the acidity of the soil. It is used to remove acidic flue gases.

CaO and Ca(OH)2 react with CO2 to form CaCO3

Group 17
46

Electronic configuration

F [He] 2s2 2p5

Cl [Ne] 3s2 3p5

Br [Ar] 3d10 4s2 4p5

I [Kr] 4d10 5s2 5p5

Physical properties

- Melting and boiling point increases due to increases in strength of van der Waal’s forces
(number of electrons increases from Fluorine to Astatine).

- States at r.t.p:
47

Depth of color increases down the group

- Cl2(g) is a greenish yellow gas.

- Br2(l) is an orange brown liquid (bromine vapors are brown).

- I2(s) is a shiny black solid (iodine vapors are purple).

Chemical properties

Oxidizing ability of Halogens

- All halogens are good oxidizing agents. Halogens and their aqueous solution act as
oxidizing agents. - Their reactivity decreases down the group therefore their oxidizing
ability decreases.

Cl2(g) oxidizing ability decreases

Br2(l) down the group.

I2(s)

Reducing ability of the Halide ions

Cl- reducing ability increases

Br- down the group.

I-

Reaction(s) of Halogens with Hydrogen

- Halogens reacts with Hydrogen to form their respective hydrogen halides.

48

Cl2

Reaction is explosive in the presence of sunlight/UV rays. Reaction takes place at a

moderate rate in the diffused (controlled) sunlight.

Cl2(g) + H2(g) → 2HCl(g)

Br2

Reaction is very slow in the presence of a catalyst. It takes place on heating.

Br2(g) + H2(g) → 2HBr(g)

I2

Iodine combines very slowly with Hydrogen on heating in the presence of a catalyst. The
reaction is reversible.

I2(g) + H2(g) ↔ 2HI(g)

Hydrogen Halides

When HCl, HBr and HI dissolve in water, acidic solutions are formed.

H-Cl bond length is increasing due to which bond

H-Br energy is decreasing. Hence thermal

H-I stability decreases down the group.

HI can be decomposed by a hot glass rod. HCl and HBr require higher temperature

Identification of Hydrogen Halides

Reaction type: ionic precipitation.

Acidify the unknown Halide solution with HNO3(aq)(to remove any carbonate present). Then
add AgNO3(aq).
49

- white precipitates of AgCl(s) are formed if Cl- ions are present.

Cl-(aq) + AgNO3(aq) → AgCl(s) + NO3-(aq)

- cream precipitate of AgBr(s) are formed if Br- ions are present.

Br-(aq) + AgNO3(aq) → AgBr(s) + NO3-(aq)

- yellow precipitate of AgI(s) are formed if I- ions are present.

I-(aq) + AgNO3(aq) → AgI(s) + NO3-(aq)

Identification by color is not completely reliable therefore NH3(aq) is added to the resulting
precipitates.

- white AgCl(s) precipitates dissolve in dilute NH3(aq) solution forming a colorless solution.

AgCl(s) + 2NH3(aq) → [Ag(NH3)2]+1(aq) + Cl-(aq)

- cream AgBr(s) precipitates dissolve in concentrated NH3(aq) solution forming a colorless

solution.

- they partially dissolve in dilute NH3(aq).

AgBr(s) + 2NH3(aq) → [Ag(NH3)2]+1(aq) + Br-(aq)

- yellow AgI(s) precipitates do not dissolve in NH3(aq).

NH3 acts as a ligand . Ligand is an atom, ion or molecule which is datively bonded to central
metal atom or ion in a complex ion.

Concentrated H2SO4 can also be used to identify Halide ions (no need for aqueous
nature).

Lowery-Bronsted Acid base reaction.

NaX(s) + H2SO4(l) → NaHSO4(s) + HX(g) X=Cl,Br,I

Concentrated H2SO4 is a strong oxidizing agent. It can oxidize HBr and HI but not HCl.
50

- Observation with NaCl:

White steamy fumes of HCl(g) are formed.

NaCl(s) + H2SO4(l) → NaHSO4(s) + HCl(g)

- Observation with NaBr:

Brown gas / reddish brown vapors of Br2(g) are formed.

NaBr(s) + H2SO4(l) → NaHSO4(s) + HBr(g)

2HBr(g) + H2SO4(l) → Br2(g) + SO2(g) + 2H2O(l)

- Observation with NaI:

Purple fumes of I2(g) are formed.

NaI(s) + H2SO4(l) → NaHSO4(s) + HI(g)

2HI(g) + H2SO4(l) → I2(g) + SO2(g) + 2H2O(l)

6HI(g) + H2SO4(l) → 3I2(g) + S(s) + 4H2O(l)

8HI(g) + H2SO4(l) → 4I2(g) + H2S + 4H2O(l)

HI is stronger reducing agent than HCl

Reaction of chlorine with alkali

- Reaction with cold, dilute NaOH(aq).

Sodium chlorate (I) is formed.

Cl2(g) + 2NaOH(aq) → NaCl(aq) + NaClO(aq) + H2O(l)

- Reaction with hot, concentrated NaOH(aq).

Sodium chlorate (V) is formed.

51

3Cl2(g) + 6NaOH(aq) → 5NaCl(aq) + NaClO3(aq) + 3H2O(l)

These both reactions are Disproportionate reactions. (the simultaneous oxidation and
reduction of the same species in a chemical reaction).

Use of chlorine in water purification

When chlorine is used to purify drinking water, disproportionation occurs to form HCl and HClO

Cl2 + H2O → HCl + HClO

The bacteria in water are killed by reactive oxygen atoms which are produced by a slow decomposition of
HClO.

HClO = Chloric (I) acid

Nitrogen and Sulfur

The triple bond between N2 is very strong. Its bond energy is 944KJ/mol.

Due to this strong bonding, most of the reactions of nitrogen are endothermic. For example
the formation of NO and NO2 is endothermic.
52

Displacement of NH3 from NH4+ salts.

When alkali or bases are heated with ammonium salts, NH3(g), salt and water are formed.

Lowery-Bronsted Acid base reaction.

(NH4)2SO4(aq) + 2NaOH(aq) → 2NH3(g) + Na2SO4(aq) + 2H2O(l)`

Nitrogen and Sulfur compounds as a source of pollutants.

Source of SO2(g):

- combustion of fossil fuel containing sulfur as an impurity.

- volcanic eruptions.

- burning of metal sulfide ores during extraction of metals.

Source of NO(g) and NO2(g):

- when fuel burns in internal combustion engine, N2(g) and O2(g) react to form NO(g).

N2(g) + O2(g) → 2NO(g)

- NO(g) reacts with air to form NO2(g).

2NO(g) + O2(g) → 2NO2(g)

NO2(g) combines with water and air to form HNO3(aq) which causes acid rain.

2NO2(g) + H2O(l) + 1/2O2(g) → 2HNO3(aq)

NO(g) / NO2(g) as catalyst

- NO(g) and NO2(g) act as a catalyst and convert SO2(g) into SO3(g).

- SO3(g) reacts with water to form H2SO4(aq) which causes acid rain.
53

NO(g) as catalyst:

NO(g) + 1/2O2(g) → NO2(g)

NO2(g) + SO2(g) → NO(g) + SO3(g)

SO2(g) + 1/2O2(g) → SO3(g)

NO2(g) as catalyst:

NO2(g) + SO2(g) → NO(g) + SO3(g)

NO(g) + 1/2O2(g) → NO2(g)

SO2(g) + 1/2O2(g) → SO3(g)

Catalytic converter

- alloy of Platinum, Rhodium and Palladium is used as a catalyst.

- Unburnt hydrocarbon and CO(g) oxidize and NO(g)/NO2(g) reduce.

zNO(g) + CxHy → xCO2(g) + y/2H2O(l) + z/2N2(g)

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Uses of ammonia and ammonium compounds

Ammonia reacts with acids to form ammonium salts. These salts are used as fertilizers.

Ammonium sulfate, ammonium nitrate and ammonium phosphate are used as fertilizers.

Nitric acid and ammonium nitrate are used to make explosives.

Nitric acid is used in the manufacture of detergents, paints, pigments, dyes and nylon .

Eutrophication
Eutrophication is a water pollution problem in lakes and rivers caused by nitrates and
phosphates.

Sources of nitrates are

Fertilizers leached from farmland due to high solubility of nitrates.

Sewage

Soruces of phosphates are

Fertilizers leached from farmland

Sewage

Detergents

The unintentional enrichment of lakes and rivers with phosphates and nitrates encourages
the rapid growth of algae. It is called algal bloom. Proliferation of algae on water surface
blocks off sunlight for submerged green plants. Eutrophication causes lack of oxygen due
to following reasons:

Underwater plants stop producing oxygen because their process of photosynthesis stops
due to no-availability of sunlight.

When these plants die, their decomposition by bacteria consumes oxygen.

When algae die, their decomposition by bacteria also consume oxygen.

Eventually when there is little or no oxygen left, fish die due to lack of oxygen and water
becomes murky and smelly
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Halogenoalkanes

Halogenalkanes are used in the industry to prepare:

- polymers such as PVCs.

- pharmaceuticals.

- solvents and lubricants.

- CFCs

- in dry cleaning industry because they can dissolve oi and grease.

Halogenoalkanes are used as a fire retardants. Introducing a halogen atom into alkane
greatly reduces its flammability.

Chlorofluorocarbons (CFCs)

- contain only three elements: Carbon, Fluorine and Chlorine.

Example: CCl3F, CCl2F2, CCl2F, CClF2 e.t.c.

- they have the following properties:

. Non-toxic

. Non-flammable

. Unreactive

. They can easily be evaporated and recondensed (volatile).

- These properties make them useful as:

. Refrigerant

. Aerosol propellants example perfumes and insecticides.

. As foam blowing agent example to make expanded polystyrene packaging material.

. As cleaning agent in electronic industry.

- The CFCs can persist in the atmosphere for about 100 years. They diffuse up in the
stratosphere. The UV light from Sun in the stratosphere breaks the C-Cl bond (it’s weaker
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than C-CF bond) in the CFCs. Chlorine free radicals are formed which react with the ozone
molecule and destroy the Ozone layer.

- HCFCs such as CF3CHFCl which has a C-H bond can be used as an alternative. These are
much less stable in the lower atmosphere. However some HCFCs do persist and reach the
stratosphere and destroy the Ozone layer.

- Compounds such as HFCs are developed which contain Hydrogen, Carbon and Fluorine.

- Hydrocarbons can be used for the same purpose. They do not effect the Ozone layer.

- CHBr3, CCl3CBr3 e.t.c are not CFCs but they also damage the Ozone layer because
bromine free radicals can also react with the Ozone molecule.

Spectroscopies

INFRA-RED SPECTROSCOPY

a) Introduction

All molecules contain covalent bonds and these bonds are constantly rotating,
bending and stretching with characteristic frequencies. When these bonds are
subjected to infra-red radiation with the same frequency, they will bend or stretch
more and the radiation of that frequency will be absorbed. Each bond absorbs one or
two distinct frequencies only, so when infra-red radiation containing a full range of
frequencies is passed through a sample of an organic compound, some frequencies
are absorbed and others pass through unaffected. The resultant radiation can be
detected and converted into a spectrum known as an intra-red spectrum.

INFRA RED SPECTROSCOPY

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Different covalent bonds have different strengths due to the masses of different atoms at either end of
the bond.

As a result, the bonds vibrate at different frequencies

The frequency of vibration can be found by detecting when the molecules absorb electro-magnetic
radiation.
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Various types of vibration are possible.

ALCOHOL

ALDEHYDE

CARBOXYLIC ACID
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a) explain the use of chlorine in water purification

Chlorine is added to water to kill bacteria. Chlorine reacts with water to some extent to
give a mixture of hydrochloric acid and chloric(I) acid.

You will also sometimes find HClO written as HOCl.

The chloric(I) acid is a powerful oxidising agent, and kills bacteria by oxidation.

describe the chemistry of alkenes as exemplified, where relevant, by the following reactions of ethene and propene (including
the Markovnikov addition of asymmetric electrophiles to alkenes using propene as an example):
When a compound HX is added to an unsymmetrical alkene, the hydrogen
becomes attached to the carbon with the most hydrogens attached to it already.
In major product the carocation is more stable due to positive inductive effect of allkyle group. Tertiary carbocation is more
stable than primary carbocation.

Crude oil as a source of both aliphatic and aromatic hydrocarbons. The compounds which contain benzene ring are called
aromatic compounds.
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outline the use of infra-red spectroscopy in monitoring air pollution (see

also Section 22.2)

IR spectroscopy identifies particular bonds in a molecule, and so each pollutant will

show a different pattern of absorptions - and also that it is possible to measure the
concentration of each pollutant

Formation of alcohols by the reduction of carboxylic acid by use of LiAlH4

Esters are used as. solvents, perfumes, and artificial flavourings