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Students can Download Chapter 10 The s Block Elements Notes, Plus One Chemistry Notes helps you to revise the complete Kerala State Syllabus and score more marks in your examinations.

Kerala Plus One Chemistry Notes Chapter 10 The s Block Elements

Introduction
Group 1 of the periodic table consists of the elements: Lithium, Sodium, Potassium, Rubidium, Caesium and Francium. They are collectively known as alkali metals.

Group 2 consists of Beryllium, Mgnesium, Calcium, Strontium, Barium and Radium. These elements except of beryllium are known as the alkaline earth metals. The general electronic configuration of s-block elements is [noble gasjns1 for alkali metals and [noble gas] ns² for alkaline earth metals. The first elements of Group 1 and Group 2 respectively exhibit diagonal similarity, which is commonly referred to as diagonal relationship in the periodic table. The diagonal relationship is due to the similarity in ionic sizes and /or charge/radius ratio of the elements.

Group 1 Elements: Alkali Metals

1) Electronic Configuration:
All the alkali metals have one valence electron, ns¹ outside the noble gas core. The loosely held s-electron readily lose electron to give monovalent M⁺ ions.

2) Atomic And Ionic Radii:
The atomic and ionic radii of alkali metals increase on moving down the group. Hence, ionization enthalpies of the alkali metals are considerably low and decrease down the group.

3) Hydration Enthalpy:
The hydration enthalpies of alkali metal ions decrease with increase in ionic sizes. Li⁺ > Na⁺ > K⁺ > Rb⁺ > Cs⁺ Li⁺ has maximum degree of hydration and for this reason lithium salts are mostly hydrated, e.g., LiCl- 2H₂O

Physical Properties
When heat is supplied to alkali metal or its salt the electrons are excited to higher energy levels. As these electrons return to their original level; radiations are emitted which fall in the visible region of electromagnetic spectrum. Thus they appear coloured. Li imparts crimson red colour, K gives violet colour and Na gives golden yellow colour to the flame.

Chemical Properties
The reactivity of these metals increases with their size. They burn vigorously in oxygen forming oxides. Lithium forms monoxide, sodium forms peroxide, the other metals form superoxides. The superoxide O₂ ion is stable only in the presence of large cations such as K, Rb, Cs.
4Li + O₂ → 2LizO(oxide)
2Na + O₂ → Na₂O₂ (peroxide)
M + O₂ → MO₂(superoxide)
(M=K, Rb, Cs)
Because of their high reactivity towards air and water, they are normally kept in kerosene oil.lt may be noted that although lithium has most negative E° value.

They also react with proton donors such as alcohol, gaseous ammonia and alkynes.AII the alkali metal hydrides are ionic solids with high melting points.
2M + H₂ → 2M⁺H^–.

The alkali metals readily react vigorously with halogens to form ionic halides, M⁺X^–. However, lithium halides are somewhat covalent. It is because of the high polarisation capability of lithium-ion. The alkali metals are strong reducing agents, lithium being the most and sodium the least powerful. The alkali metals dissolve in liquid ammonia giving deep blue solutions. The solutions are paramagnetic and on standing slowly liberate hydrogen.

General Characteristics Of The Compounds Of The Alkali Metals

Oxides And Hydroxides
Reactivity of alkali metals with oxygen increases down the group. Lithium, when heated in air, forms the normal oxide (Li₂O) while sodium forms the per-oxide (Na₂O₂). Potassium, Rubidium and caesium form superoxides (MO₂).
4Li + O₂ → 2Li₂O; 2Na+ O₂ → Na₂O₂; K + O₂ → KO₂

The normal oxides dissolve in water to form hydroxides (MOH) which are strong bases. However, LiOH is only slightly soluble in water and it decomposes on heating. The peroxides and superoxides also dis-solve in water to form basic hydroxides. The basic character of alkali metal hydroxides increases down the group.

Halides
Alkali metals react vigorously with halogens to form metal halides of the general formula MX. 2M+X₂ → 2MX X=F, Cl, Br or l and M= alkali metal Reactivity of alkali metal towards halogen increases from Li to Cs. Halides of alkali metals are ionic compounds readily soluble in water. But LiF is almost insoluble due to high lattice energy.

Anomalous Properties Of Lithium
The anomalous behaviour of lithium is due to the :

1. exceptionally small size of its atom and ion, and
2. high polarising power (i.e., charge/ radius ratio).

As a result, there is increased covalent character of lithium compounds which is responsible for their solubility in organic solvents.

Points Of Similarities Between Lithium And Magnesium
The similarity between lithium and magnesium is particularly striking and arises because of their similar sizes: atomic radii, Li = 152 pm, Mg= 160 pm; ionic radii: Li⁺ = 76 pm, Mg²⁺ = 72 pm. The main points of similarity are:

1. Both lithium and magnesium are hander and lighter than other elements in the respective groups.
2. Lithium and magnesium react slowly with water. Their oxides and hydroxides are much less soluble and their hydroxides decompose on heating. Both form a nitride, Li₃N and Mg₃N₂, by direct combination with nitrogen.
3. The oxides, Li₂O and MgO do not combine with excess oxygen to give any superoxide.
4. The carbonates of lithium and magnesium decompose easily on heating to form the oxides and CO₂.

Some Important Compounds Of Sodium Sodium Carbonate (Washing Soda), Na₂CO₃.10H₂O
Sodium carbonate is generally prepared by Solvay Process.
The equations for the complete process may be written as:
2NH₃ + H₂O + CO₂ → (NH₄)₂CO₃
(NH₄)₂CO₃ + H₂O + CO₂ → 2NH₄HCO₃
NH₄HCO₃ +NaCl → NH₄Cl + NaHCO₃
2NaHCO₃ → Na₂CO₃ +CO₂ +H₂O

In this process, NH₃ is recovered when the solution containing NH₄Cl is treated with Ca(OH)₂. On heating washing soda becomes monohydrate and then completely anhydrous i.e., soda ash.

Sodium Chloride, NaCl
The most abundant source of sodium chloride is seawater. Common salt is generally obtained by evaporation of seawater. Crude sodium chloride, generally obtained by crystallisation of brine solution, contains sodium sulphate, calcium sulphate, calcium chloride and magnesium chloride as impurities. Calcium chloride, CaCl₂, and magnesium chloride, MgCl₂ are impurities because they are deliquescent (absorb moisture easily from the atmosphere). To obtain pure sodium chloride, the crude salt is dissolved in minimum amount of water and filtered to remove insoluble impurities. The solution is then saturated with hydrogen chloride gas. Crystals of pure sodium chloride separate out. Calcium and magnesium chloride, being more soluble than sodium chloride, remain in solution.

Uses:

• It is used as a common salt or table salt for domestic purpose.
• It is used for the preparation of Na₂O₂, Na0H and Na₂CO₃.

Sodium Hydroxide (Caustic Soda), NaOH
Sodium hydroxide is generally prepared commercially by the electrolysis of sodium chloride in Castner-Kellner cell. A brine solution is electrolysed using a mercury cathode and a carbon anode.

The amalgam is treated with water to give sodium hydroxide and hydrogen gas.
2 Na – amalgam + 2H₂O → 2NaOH + 2Hg +H₂
The sodium hydroxide solution at the surface reacts with the C02 in the atmosphere to form Na₂CO₃.

Uses:
It is used in (i)the manufacture of soap, paper, artificial silk and a number of chemicals,(ii) in petroleum refining, (iii) in the purification of bauxite, (iv) in the textile industries for mercerising cotton fabrics and (v) for the preparation of pure fats and oils.

Biological Importance Of Sodium And Potassium
Sodium ions participate in the transmission of nerve signals. The concentration gradient of Na₊ and K₊ demonstrates that-a discriminatory mechanism called sodium-potassium pump, operates across the cell membranes.

Group 2 Elements: Alkaline Earth Metals
The group 2 elements (except beryllium) are known as alkaline earth metals. The first element beryllium differs from the rest of the members and shows diagonal relationship to aluminium.
1) Electronic Configuration:
These elements have two electrons in the s-orbital of the valence shell. Their general electronic configuration may be represented as [noble gas] ns².

2) Atomic And Ionic Radii:
Within the group, the atomic and ionic radii increase with increase in atomic number due to the increased nuclear charge in these elements. They have low ionisation enthalpy and it decreases down the group with increase in size.

3) Hydration Enthalpy:
Hydration enthalpies of alkaline earth metal ions decrease with increase in ionic size down the group. Be²⁺ > Mg²⁺ > Ca²⁺ > Sr²⁺ > Ba²⁺ The hydration enthalpies of alkaline earth metal ions are larger than those of alkali metal ions.

Physical Properties
Calcium, Strontium and Barium impart characteristic brick red, crimson and apple green colours respectively to the flame. Inflame the electrons are excited to higher energy levels and when they drop back to the ground state, energy is emitted in the form of visible light. The electrons in Be and Mg are too strongly bound to get excited by flame. Hence, these elements do not impart any colour to the flame.

Chemical Properties
The alkaline earth metals are less reactive than the alkali metals. The reactivity of these elements increases on going down the group.
Reactivity towards air and water Beryllium and Magnesium are kinetically inert to oxygen and water because of the formation of an oxide film on their surface. However, powdered beryllium burns brilliantly on ignition in air to give BeO and Be₃N₂.
Reactivity towards halogen
M + X₂ → MX₂ (X = F, Cl, Br, I)

Reactivity towards hydrogen
All the elements except beryllium form their hydrides, MH₂.BeH₂, however, can be prepared by the reaction of BeCl₂ with LiAlH₄.
2BeCl₂ +LiAlH₄ → 2BeH₂ +LiCl + AlCl₃

Reactivity towards acids:
The alkaline earth metals readily react with acids liberating dihydrogen.

General Characteristics Of Compounds Of The Alkaline Earth Metals
i) Oxides and Hydroxides: Alkaline earth metals burn in air or oxygen to form their oxides. (Oxides are also prepared by the thermal decomposition of their carbonates). Be, Mg and Ca form monoxides (MO). The tendency to form peroxide increases as the size of the metal ion increases. Strontium and barium form peroxides (MO₂)
2M + O₂ → MO (M = Be, Mg or Ca)
M+O₂ → MO₂ (M = Sr or Ba)

BeO is amphoteric in character, while the oxides of the rest of the elements in group 2 are basic. The oxides of Ca, Sr and Ba react with water to form their corresponding hydroxides.

The hydroxides of alkaline earth metals are bases except Li(OH)₂ which is amphoteric. The basic strength increases from Mg(OH)₂ to Ba(OH)₂. The solubility and thermal stability of hydroxides increase downward in the group. Be(OH)₂ and Mg(OH)₂ are almost insoluble. Ca(OH)₂ is sparingly soluble, while Sr(OH)₂ and Ba(OH)₂ are increasingly more soluble.

ii) Halides: Group 2 metals directly combine with halogen to form divalent halides of the formula

The s-Block Elements
MX₂ where X is the halogen. The metal halides are also formed by the action of halogen acids on metals, their oxides, carbonates and hydroxides. BeCl₂ is, however, prepared by passing Cl₂ over a hot mixture of BeO and coke.
In contrast to the halides of other alkaline earth metals, beryllium halides are covalent. In the solid-state BeCl₂ has a polymeric chain structure involving Be-CI-Be bridges. The anhydrous halides are hygroscopic and form hydrates such as MgCl₂.6H₂O, CaCl₂.6H₂O etc. Due to this reason, anhydrous calcium chloride is widely used as a dehydrating agent. Fluorides are relatively less soluble due to high lattice energies,

iii) Salts of Oxoacids:
The alkaline earth metals also form salts of oxoacids. Some of these are : Carbonates, Sulphates and Nitrates.

Anomalous Behaviour Of Beryllium
Beryllium differs from the rest element in many of its properties. These are

1. Beryllium has high ionisation enthalpy.
2. Small size of Be atom
3. Be does not exhibit coordination number more than four.
4. The oxides and hydroxides of Be are amphoteric in nature.

Diagonal Relationship Between Beryllium And Aluminium
The ionic radius of Be²⁺ is estimated to be same as that of the Al³⁺ ion. Hence Be resembles Al in some ways. Some of the similarities are:

1. Like AI, Be is not readily attacked by acids because of the presence of an oxide film on the surface of the metal.
2. Beryllium hydroxide dissolves in excess of alkali to give a beryllate ion just as aluminium hydroxide gives aluminate ion.
3. The chlorides of both Be and Al have Ch bridged chloride structure in vapour phase. Both the chlorides are soluble in organic solvents and are strong Lewis acids. They are used as Friedel Craft catalysts.
4. Be and Al ions have strong tendency to form complexes, BeF₄^2-, AlF₆^3-.

Some Important Compounds Of Calcium
Important compounds of calcium and their preparations are given below.

Calcium Oxide Or Quick Lime, CaO
It is prepared by the following reaction.
CaCO₃ \(\rightleftharpoons \) Ca0 + CO₂
CO₂ is removed as soon as it is produced to enable the reaction to proceed to completion.
CaO + H₂O → Ca(OH)₂
This process is called slaking of lime. CaO is a basis oxide.

Uses:

• Primary material for manufacturing cement
• It is used in the manufacturing of caustic soda
• Used to purify sugar

Calcium Hydroxide (Slaked Lime), Ca(OH)₂
It is prepared by adding water to CaO. The aqueous solution of Ca(OH)₂ is known as lime water and the suspension of slaked lime is known as milk of lime. When CO₂ is passed through lime water it turns milky due to the formation of CaCO₃
Ca(OH)₂ + CO₂ → CaCO₃ +H₂O

Uses:

• It is used in whitewash due to its disinfectant nature.
• Used in the preparation of bleaching powder.
• Used to purify sugar.

Calcium Carbonate, CaCO₂
It occurs in limestone, chalk, marble etc.
It can be prepared by the following reactions.
Ca(OH)₂ + CO₂ → CaCO₃ + H₂O
CaCl₂ + Na₂CO₃ → CaCO₃ + 2NaCl
CaCO₃ reacts with dilute acids to liberate carbon dioxide.

Uses:

• It is used as a flux in the extraction of metals.
• It is used as the building material of quick lime.

Calcium Sulphate (Plaster Of Paris), CaSO₄.½H₂O
It is obtained by heating gypsum (CaSO₂.2H₂O)

Above 393K anhydrous calcium sulphate is formed. This is known as ‘dead burnt plaster’

Used:

• It is used in building industry as well as plasters.
• Used to make casts of statues.

Cement
Cement is prepared by combining CaO with other materials such as clay with silica, SiO₂ along with Oxides of Al, iron and magnesium. The average composition of portland cement is:
CaO, 50-60%;
SiO₂, 20-25%;
Al₂O₃, 5-10%;
MgO, 2-3%;
Fe₂O₃, 1-2% and
SO₃, 1-2%.
When limestone and clay are heated we get cement clinker. This clinker is mixed with gypsum to form cement.

Setting of Cement:
When mixed with water the setting of cement takes place to give a hard mass. It is due to the rearrangement and hydration of molecules of constituents. Gypsum is added to slow down the setting process so it gets sufficiently hardened.

Uses:

• Used in construction of building.

Biological Importance Of Magnesium And Calcium
Human body contains about 25g of Mg and 1200g of Ca. Mg is a cofactor in enzymes which use ATP in phosphate transfer process in our body. Photosynthesis in plants takes place in presence of chlorophyll which contains Mg. About 99% of body calcium is found in teeth and bones. Calcium concentration in plasma is regulated at 100mg/litre in presence of hormones such as calcitonin and parathyroid hormone.

Students can Download Chapter 9 Hydrogen Notes, Plus One Chemistry Notes helps you to revise the complete Kerala State Syllabus and score more marks in your examinations.

Kerala Plus One Chemistry Notes Chapter 9 Hydrogen

Introduction
Hydrogen has the simplest atomic structure all the elements around us in nature. It consists of only one proton and one electron.

Position Of Hydrogen In The Periodic Table
Hydrogen is the first element in the periodic table. Hydrogen has electronic configuration 1 s1. On one hand, its electronic configuration is similar to the outer electronic configuration (ns¹) of alkali metals. On the other hand, it is short by one electron to the corresponding noble gas configuration, helium (1s²). It has resemblace to both alkali metals and halogens.

Dihydrogen, H₂

Isotopes Of Hydrogen
There are three isotopes of hydrogen with mass numbers 1,2 and 3. They are called protium, deuterium and tritium respectively. Their natural abundances . are in the ratio l:1.56 × 10^-2: 1 × 10^-17 respectively.

1. Protium (ordinary hydrogen)(\(_{ 1 }^{ 1 }{ H }\)): It is the most abundant isotope of hydrogen. Its nucleus contains one proton and no neutron.
2. Deuterium (heavy hydrogen, \(_{ 1 }^{ 2 }{ H }\) or D): Heavy hydrogen is prepared from heavy water (D₂O) which is obtained by electrolysis of ordinary water.
3. Tritium has 2 neutrons in the nucleus.

Preparation Of Dihydrogen, H₂
It is usually prepared by the following reactions:

3. Reaction of steam on hydrocarbons or coke at high temperatures in the presence of catalyst yields hydrogen.

The mixture of CO and H₂ is called water gas. As this mixture of CO and H₂ is used for the synthesis of methanol and a number of hydrocarbons, it is also called synthesis gas or ‘syngas’. Nowadays ‘syngas’ is produced from sewage, sawdust, scrap wood, newspapers etc. The process of producing ‘syngas’ from coal is called ‘coal gasification’.

This reaction is called water-gas shift reaction.

Properties Of Dihydrogen

Physical Properties
Dihydrogen is a colourless, odourless, tasteless, combustible gas. It is lighter than air and insoluble in water.

Chemical Properties
Dihydrogen is not particularly reactive because of its high bond dissociation enthalpy. However, hydrogen forms compounds with almost all elements at high temperature or in presence of catalysts.
Reaction with halogens:
H₂ (g) + X₂(g) → 2HX(g) (X = F, Cl, Br, l)
Reaction with dioxygen:

Uses Of Hydrogen

1. Hydrogen is used in the manufacture of ammonia by Haber process, water gas, fertilisers etc.
2. It is used in the hydrogenation of vegetable oils and as a reducing agent.
3. It is used in the production of methanol and synthetic petrol.
4. Liquid hydrogen is used in as rocket fuel along with liquid oxygen.
5. It is used in oxy-hydrogen torch used for welding.

Hydrides
Hydrogen can form binary compounds with almost all elements. These are known as hydrides.
The hydrides are classified into three categories:

1. Ionic or saline or salt like hydrides
2. Covalent or molecular hydrides
3. Metallic or non-stoichiometric hydrides

Ionic Or Saline Hydrides
These are stoichiometric compounds of dihydrogen formed with most of the s-block elements which are highly electropositive in character. However, significant covalent character is found in the lighter metal hydrides such as LiH, BeH₂ and MgH₂.

Covalent Or Molecular Hydride
Dihydrogen forms molecular compounds with most of the p-block elements. Most familiar examples are CH₄, NH₃, H₂O and HF. For convenience hydrogen compounds of nonmetals have also been considered as hydrides. Molecular hydrides are further classified according to the relative numbers of electrons and bonds in their Lewis structure into :

1. electron-deficient,
2. electron-precise,and
3. electron-rich hydrides.

Group13 elements form electron deficient compounds. They act as Lewis acids i.e., electron acceptors. eg.B₂H₆ Group 14 elements form electron precise compounds. They have required number of electrons. eg.CH₄. Electron-rich hydrides have excess electrons which are present as lone pairs. Elements of group 15-17 form such compounds. (NH₃ has 1 – lone pair, H₂O – 2 and HF -3 lone pairs).They will behave as Lewis bases.

Metallic Or Non-Stoichiometric (Or Interstitial) Hydrides
These are formed by many d-block and f-block elements. However, the metals of group 7, 8 and 9 do not form hydride. Even from group 6, only chromium forms CrH. These hydrides conduct heat and electricity though not as efficiently as their parent metals do. Unlike saline hydrides, they are almost always nonstoichiometric, being deficient in hydrogen. For example, LaH_2.87 & YbH_2.55

Water
Water is a colourless tasteless liquid. A major part of all living organisms is made up of water.The unusual properties of water is due to the presence of extensive hydrogen bonding between water molecules.

Structure Of Water
In the gas phase water is a bent molecule with a bond angle of 104.5°, and O-H bond length of 95.7 pm

(a) The bent structure of water;
(b) the water molecule as a dipole

Structure Of Ice
The crystalline form of water is ice. At atmospheric pressure, ice crystallises in the hexagonal form, but at very low temperatures it condenses to cubic form. Hydrogen bonding gives ice a rather open type structure with wide holes. These holes can hold some other molecules of appropriate size interstitially. Density of ice is less than that of water. Therefore, an ice cube floats on water. In winter season ice formed on the surface of a lake provides thermal insulation which ensures the survival of the aquatic life.

Chemical Properties of Water
1) Amphoteric Nature:
It has the ability to act as an acid as well as a base i.e., it behaves as an amphoteric substance. In the Bronsted sense it acts as an acid with NH₃ and a base with H₂S.

2) Redox Reactions Involving Water
Water can be reduced and oxidised:
2H₂O(l) + 2Na(s) → 2NaOH(aq) + H₂(g): reduction Water is oxidised to O₂ during photosynthesis
6CO₂(g) +12H₂O(I) → C₆H₁₂O₆ (aq) + 6H₂O(I) + 6O₂(g)

3) Hydrolysis Reaction:
Due to high dielectric constant, it has a very strong hydrating tendency.
P₄O₁₀(s) + 6H₂O(l) → 4H₃PO₄(aq)

4) Hydrates Formation:
From aqueous solutions, many salts can be crystallised as hydrated salts. Such an association of water is of different types viz.,
i) Coordinated water e.g.,
[Cr(H₂O)₆]₃+3Cl^–
ii) Interstitial water.g., BaCl₂.2H₂O
iii) hydrogen-bonded water.g.,
[Cu(H₂O)₄]²⁺ SO₄^2-.H₂O in CuSO₄.5H₂O

Hard And Soft Water
Water which produces lather with soap solution readily is called soft water. For example, rainwater, distilled water etc. Water which does not produce lather with soap solution readily is called hard water, eg: Sea water, water from certain rivers.

Hardness of water is due to the presence of bicarbonates, chlorides and sulphates of calcium and magnesium. The calcium and magnesium ions present in hard water form insoluble salts with soap and prevent the formation of lather.

Temporary Hardness
Temporary hardness is due to the presence of mag-nesium and calcium hydrogencarbonates.
It can be removed by boiling.

Permanent Hardness
It is due to the presence of soluble salts of magnesium and calcium in the form of chlorides and sulphates in water. Permanent hardness is not removed by boiling. It can be removed by the following methods:
i) Treatment with washing soda (sodium carbonate):
Washing soda reacts with soluble calcium and magnesium chlorides and sulphates in hard water to form insoluble carbonates.
MCl₂ → MCO₃ ↓ 2NaCl (M=Mg, Ca)
MSO₄ + Na₂CO₃ → MCO₃ ↓ +NaSO₄

ii) Calgon’s method:
Sodium hexametaphosphate (Na₆P₆O₁₈), commercially called ‘calgon’, when added to hard water, the following reactions take place.
Na₆P₆O₁₈ → Na^{+ + Na₄P₆O₁₈2- (M=Mg, Ca)
M2+ + Na₄P₆O₁₈2- → [Na₂MP₆O₁₈]2- + 2Na+}

iii) Ion-exchange method:
This method is also called zeolite/perm utit process. Hydrated sodium aluminium silicate iszeolite/permutit.Forthe sake of simplicity, sodium aluminium silicate (NaAlSiO₄) can be written as NaZ.
2NaZ(s) + M²⁺(aq) → MZ₂(s) + 2Na⁺(aq) (M=Mg, Ca)
MZ₂ (S) + 2NaCl(aq) → 2NaZ(s) + MCl₂(aq)

iv) Synthetic resins method:
Nowadays hard . water is softened by using synthetic cation exchangers. This method is more efficient than zeolite process.Ion exchange resin (RSO₃H) is changed to RNa by treating it with NaCI. Here R is resin anion.
2RNa(s) + M²⁺(aq) → R₂M(s) + 2Na⁺(aq)

The resin exchanges Na+ ions with Ca²⁺ and Mg²⁺ ions present in hard waterto make the water soft.

HYDROGEN PEROXIDE (H₂O₂)
It can be prepared by the following methods.

Structure
Hydrogen peroxide has a non-planar structure.

Chemical Properties
i) Oxidising action in acidic medium
PbS(s) + 4H₂O₂(aq) → PbSO₄(s) + 4H₂O(l)

ii) Reducing action in acidic medium
HOCl + H₂O → H₃O⁺ +Cl^– + O₂

iii) Oxidising action in basic medium
Mn²⁺ +H₂O₂ → Mn⁴⁺ + 2OH^–

iv) Reducing action in basic medium
2MnO₄^– + 3H₂O₂ → MnO₂ + O₂ + 2H₂O + OH^–

Uses

1. As a bleaching agent for textiles, wood and paper pulp
2. In the manufacture of chemicals such as sodium perborate, epoxides etc.
3. A dilute solution of H₂O₂ is used as a disinfectant. This solution is used as an antiseptic for wounds, teeth and ears under the name perhydrol.
4. iv) It is used in pollution control treatment of domestic and industrial effluents.

Heavy water. D₂O
It is extensively used as a moderator in nuclear reactors and in exchange reactions for the study of reaction mechanisms. It can be prepared by exhaustive electrolysis of water or as a by-product in some fertilizer industries.lt is used for the preparation of other deuterium compounds.

Dihydrogen As A Fuel
Due to extensive use, our reserves of fossil fuels are fast depleting. A prospective alternative in this regard is what is known as hydrogen economy. The major idea behind hydrogen economy is the storage and transportation of energy in the form of gaseous and liquid hydrogen. Hydrogen can replace fossil fuels in automobiles, and coal or coke in industrial processes involving reduction. Hydrogen fuel can release more energy per unit weight of the fuel than our conventional fuels. Hydrogen oxygen fuel cells can be used for generating power in automobiles. Liquid hydrogen has already been used as rocket fuel along with liquid oxygen.

The technology involves the production of bulk quantities of hydrogen and its storage in liquid form in vacuum insulated cryogenic tanks. Transport of liquid hydrogen by road or rail, or through pipelines is feasible. Certain metal alloys can be used as smaller storage units for hydrogen.

Students can Download Chapter 8 Redox Reactions Notes, Plus One Chemistry Notes helps you to revise the complete Kerala State Syllabus and score more marks in your examinations.

Kerala Plus One Chemistry Notes Chapter 8 Redox Reactions

Introduction
The reaction which involve both oxidation and reduction reactions is called Redox reaction.

Classical Idea Of Redox Reactions Oxidation And Reduction Reactions
“Oxidation” is defined as the addition of oxygen/electronegative element to a substance or removal of hydrogen/electropositive element from a substance. Examples of oxidation:

1. Addition of oxygen 2Mg + O2 → 2MgO
2. Removal of hydrogen 2H₂S + O₂ → 2S + 2H₂O
3. Addition of electronegative element Mg + Cl₂ → MgCl₂

The term reduction been broadened these days to include removal of oxygen/electronegative element from a substance or addition of hydrogen /electropositive element.

1. Removal of electronegative element FeCl₃ + H₂ → 2FeCl₂ + 2HCl
2. Removal of Oxygen (2H₂O → 2Hg + O₂)
3. Addition of Hydrogen (H₂ + Cl₂ → 2HCl)

Redox Reactions In Terms Of Electron Transfer Reactions
According to electronic concept, the processes which involves loss of electrons are called oxidation reactions. Similarly, processes which involve gain of electrons are called reduction reactions.
The atom which reduced, act as oxidising agent and the atom which oxidised act as reducing agent.For example;
2Na(s) + Cl₂(g) → 2Na⁺Cl^–(s) or 2NaCl(s)
Here Na is oxidised and Cl is redused.

Competitive Electron Transfer Reaction
Place a strip of metallic zinc in an aqueous solution of copper nitrate. You may notice that the strip becomes coated with reddish metallic copper and the blue colour of the solution disappears. Formation of Zn²⁺ ions among the products can easily be judged when the blue colour of the solution due to Cu2+ has disappeared. The reaction is,
Zn(s) + Cu²⁺(aq) → Zn²⁺(aq) + Cu(s) zinc is oxidised, releasing electrons, something must be reduced, accepting the electrons lost by zinc. Copper ion is reduced by gaining electrons from the zinc.

Oxidation Number
Oxidation number of an element may be defined as the charge which an atom of the element has or appears so have when present in the combined state in a compound.

1. Electrons shared between two like atoms are divided equally between the sharing atoms.
2. Electrons shared between two unlike atoms are counted with the more electronegative atom. Atoms can assume positive, zero or negative values of oxidation numbers depending on their state of combination. Oxidation number can be a fraction in some cases.

The rules for calculation of oxidation number are:
1. In elements, in the free or the uncombined state, each atom bears an oxidation number of zero. Evidently each atom in H2 has the oxidation number zero.

2. For ions composed of only one atom, the oxidation number is equal to the charge on the ion. Thus Na+ ion has an oxidation number of +1, Mg²⁺ion, +2, Fe³⁺ ion, +3, Cl^– ion, -1, O^2- ion, -2; and so on. In their compounds all alkali metals have oxidation number of +1, and all alkaline earth metals have an oxidation number of +2. Aluminium is regarded to have an oxidation number of +3 in all its compounds.

3. The oxidation number of oxygen in most compounds is-2. However, we come across two kinds of exceptions here.in peroxides (e.g., H₂O₂, Na₂O₂), each oxygen atom is assigned an oxidation number of—1, in superoxides (e.g., KO₂, RbO₂) each oxygen atom is assigned an oxidation number of -(½). The second exception appears rarely, i.e. when oxygen is bonded to fluorine. In such compounds e.g., oxygen difluoride (OF₂) and dioxygen difluoride (O₂F₂), the oxygen is assigned an oxidation number of +2 and +1, respectively. The number assigned to oxygen will depend upon the bonding state of oxygen but this number would now be a positive figure only.

4. The oxidation number of hydrogen is +1, except when it is bonded to metals in binary compounds (that is compounds containing two elements). For example, in LiH, NaH, and CaH₂, its oxidation number is —1.

5. In all its compounds, fluorine has an oxidation number of-1. Other halogens (Cl, Br, and I) also have an oxidation number of-1, when they occur as halide ions in their compounds. Chlorine, bromine and iodine when combined with oxygen, for example in oxoacids and oxoanions, have positive oxidation numbers.

6. The algebraic sum of the oxidation number of all the atoms in a compound must be zero. In polyatomic ion, the algebraic sum of all the oxidation numbers of atoms of the ion must equal the charge on the ion. Thus, the sum of oxidation number of three oxygen atoms and one carbon atom in the carbonate ion, (CO₃)^2- must equal -2. A term that is often used interchangeably with the oxidation number is the oxidation state. Oxidation state of a metal is a compound is sometimes represented by Stock notation. According to this, the oxidation number is written as Roman numeral in parenthesis after the symbol of the metal in the molecular formula. e.g.,Fe(ll)0, Sn(IV), Cl₄,Mn(IV)O₂.

Problem
Using Stock notation, represent the following compounds HAUCl₄, Ti₂O, FeO, Fe₂O₃, Cul, CuO, MnO and MnO₂.

Solution
By applying various rules of calculating the oxidation number of the desired element in a compound, the oxidation number of each metallic element in its compound is as follows:
HAuCl₄ → Au has 3
Tl₂O → Tl has 1
FeO → Fe has 2
Fe₂O₃ → Fe has 3
Cul → Cu has 1
CuO → Cu has 2
MnO → Mn has 2
MnO₂ → Mn has 4

Therefore, these compounds may be represented as
HAU(III)Cl₄, Tl₂(I)O, Fe(II)O, Fe₂(III)O₃, Cu(I)l, Cu(II)O, Mn(II)O, Mn(IV)O₂.

In terms of oxidation number, oxidation may be defined as a chemical change in which there occurs an increase in the oxidation number of an atom or atoms. Reduction may be defined as a chemical change in which there occurs a decrease in the oxidation number of an atom or atoms. Thus, a redox reaction may be defined as a reaction in which the oxidation number of atoms undergoes a change.

Types Of Redox Reactions
1. Combination Reactions:
A combination reaction may be denoted in the manner
A + B → C

2. Decomposition Reaction:
Decomposition reactions are the opposite of combination reactions.
For example, 2H₂O → 2H₂ + O₂

3. Displacement Reaction:
In a displacement reaction, an ion (or an atom) in a compound is replaced by an ion (or an atom) of another element. It may be denoted as:
X +YZ → XZ + Y
Displacement reactions fit into two categories:
metal displacement and non-metal displacement.

a) Metal displacement:
A metal in a compound can be displaced by another metal in the uncombined state.
CuSO₄(aq) + Zn(s) → Cu(s) + ZnSO₄(aq)

b) Non-metal displacement:
The non-metal displacement redox reactions include hydrogen displacement and a rarely occurring reaction involving oxygen displacement.
2Na(s) + 2H₂O(I) → 2NaOH(aq) + H₂(g)

The power of these elements as oxidising agents decreases as we move down from fluorine to iodine in group 17 of the periodic table.

Note:
fluorine is the strongest oxidising agent; there is no way to convert F^– ions to F₂ by chemical means. The only way to achieve F₂ from F^– is to oxidise electrolytically,

4. Disproportionation Reactions:
In a disproportionation reaction an element in one oxidation state is simultaneously oxidised and reduced.

Balancing Of Redox Reactions
There are two ways to balance a redox equation.
They are oxidation number method and Half Reaction Method.

a) Oxidation Number Method
The various steps involved in this method are:

1. Write the skeletal equation and assign oxidation numbers to each element. Identify the elements undergoing change in oxidation number.
2. Find out the increase or decrease of oxidation number per atom. Multiply the increase or decrease of oxidation number with number of atoms undergoing the change.
3. Multiply the formulae of the oxidising agent and the reducing agent by suitable integers so as to equalize the total increase or decrease in oxidation number as determined in the above step.
4. Balance the equation with respect to all atoms other the term reduction has than oxygen and hydrogen.
5. Balance oxygen atoms by adding equal number of H₂O molecules to the side deficient in oxygen atoms.
6. For reaction taking place in acidic medium, add H⁺ ions to the side of deficient in hydrogen atoms.
7. For reaction taking place in basic medium, add H₂O molecules to the side deficient in hydrogen atoms and simultaneously add equal number of OH ions on the other side of the equation.

Problem
Permanganate ion reacts with bromide ion in basic medium to give manganese dioxide and bromate ion. Write the balanced ionic equation forthe reaction.
Solution:
The skeletal ionic equation is:
MnO₄^–(aq) + Br^–(aq) → MnO₂(s) + BrO₃^–(aq)

Assign oxidation numbers for Mn and Br

this indicates that permanganate ion is the oxidant and bromide ion is the reductant.

Calculate the increase and decrease of oxidation number, and make the increase equal to the decrease.

As the reaction occurs in the basic medium, and the ionic charges are not equal on both sides, add 2 OH^– ions on the right to make ionic charges equal.
2MnO₄^–(aq) + Br^–(aq) → 2MnO₂(s) + BrO₃^–(aq) + 2OH^–(aq)

Finally, count the hydrogen atoms and add appropri- ‘ ate number of water molecules (i.e. one H20 molecule) on the left side to achieve balanced redox change.
2MnO₄^–(aq) + Br^–(aq) → 2MnO₂(s) + Br0₃^–(aq) + 2OH^–(aq)

b) Half Reaction Method
This method involves identifying the oxidation and reduction reactions in the given skeletal equation and then splitting the reaction accordingly as two half reactions. Each half reaction is then balanced systematically in various steps as outlined below.

Step 1.
Write the skeletal equation and identify the oxidant and reductant.

Step 2.
Write the half reactions for oxidation and reduction separately.

Step 3.
Balance the half reaction with respect to atoms that undergo change in oxidation number. Add electron to whichever side is necessary, to make up for difference in ON.

Step 4.
Balance O-atoms by adding proper number of H₂O molecules to the side deficient in oxygen atoms.

Step 5.
For ionic equations in acid medium, add sufficient H⁺ ions to the side deficient in hydrogen. If the reaction occurs in basic medium, add sufficient H₂O molecules to the side deficient in H atoms to balance H atoms and equal number of hydroxyl ions on the opposite side.

Step 6.
Equalise the number of electrons lost or gained by multiplying the half reaction with suitable integer and add the half reactions to get the final balanced equation.

Problem
Permanganate (VII) ion, MnO₄^– in basic solution oxidises iodide ion, l^– to produce molecular iodine (l₂) and manganese (IV) oxide (MnO₂). Write a balanced ionic equation to represent this redox reaction.
Solution:

Redox Reactions As The Basis For Titrations
In redox systems, the titration method can be adopted to determine the strength of a reductant/ oxidant using a redox sensitive indicator. The usage of indicators in redox titration is illustrated below:
1. In one situation, the reagent itself is intensely coloured, e.g., permanganate ion, MnO₄^–. Here MnO₄^– – acts as the self indicator. The visible endpoint, in this case, is achieved after the last of the reductant (Fe²⁺ or C₂O₄^2-) is oxidised and the first lasting tinge of pink colour appears at MnO₄^– concentration as low as 10^-6 mol dm^-3 (10^-6 mol L^-1), This ensures a minimal ‘overshoot’ in colour beyond the equivalence point, the point where the reductant and the oxidant are equal in terms of their mole stoichiometry.

2. If there is no dramatic auto-colour change (as with Mn04 – titration), there are indicators which are oxidised immediately after the last bit of the reactant is consumed, producing a dramatic colour change. The best example is afforded by Cr2072-, which is not a self-indicator, but oxidises the indicator substance diphenylamine just after the equivalence point to produce an intense blue colour, thus signalling the endpoint.

Redox Reactions And Electrode Pro-Cesses
When zinc rod is dipped in copper sulphate solution, zinc gets oxidised to Zn²⁺ while Cu²⁺ ions are reduced to Cu due to direct transfer of electrons. However, if a zinc rod dipped in ZnSO₄ solution taken in a breaker is connected externally by a conducting wire to a copper rod placed in CuSO₄ solution in another beaker, electrons are transferred indirectly from Zn to Cu. Now, each beaker contains both the oxidised and reduced form of the same substance ‘ called a redox coupe. In this experiment the redox couples developed are Zn²⁺/Zn and Cu²⁺/Cu When the solutions in the two beakers (called electrodes) are joined by a salt bridge (a U-tube containing a solution of KCl, solidified in presence of agar-agar), electrons flow from Zn to Cu while current flows in the reverse direction. The salt bridge provides electrical continuity between the solutions without allowing them to mix with each other. The flow of current is due to a potential difference between Cu and Zn electrodes (or half cells). This experimental set up gives an electrochemical cell or galvanic cell.

The potential of an electrode is a measure of its ability to lose (oxidation) or gain (reduction) electrons. When the concentrations of solutions in the half cells are unity and the temperature is 298 K, the potential of each electrode is known as Standard Electrode Potential (E°). By convention, E° of hydrogen electrode is zero volts and the potential of other electrodes will be a measure of the relative tendency of the active species to be in oxidised/reduced form. A negative E°shows that the redox couple is a stronger reducing agent than H⁺/H₂ couple.

A positive E° shows that the redox couple is a weaker reducing agent than H⁺/H₂ couples. The values of standard reduction potentials of various electrodes are given in the increasing order in an electrochemical series (electromotive series)

Students can Download Chapter 7 Chemical Equilibrium Notes, Plus One Chemistry Notes helps you to revise the complete Kerala State Syllabus and score more marks in your examinations.

Kerala Plus One Chemistry Notes Chapter 7 Chemical Equilibrium

Introduction
Chemical equilibria are very important in numerous biological and environmental processes. At equilibrium state, the rate of product formed is equal to the rate of reactants formed. The mixture of reactants and products at equilibrium state is called an equilibrium mixture. A equilibrium mixture involving ions in aqueous solutions which is called as ionic equilibrium

Equilibrium In Physical Processes
Phase transformation processes are the familiar example for equilibrium in Physical process.
They are,
Solid \(\rightleftharpoons \) liquid
Liquid \(\rightleftharpoons \) gas
Solid \(\rightleftharpoons \) gas

Solid Liquid Equilibrium
Consider a perfectly insulated thermos flask containing some ice and water at 273 K and normal atmospheric pressure. Since the flask is insulated, there will be no exchange of heat between its contents and the surroundings. It is seen that as long as the temperature remains constant, there is no change in the mass of ice and water. This represents an equilibrium state between ice and water and maybe represented as

We observe there is no change in mass of both ice and water. Since the rate of both reactions are equal.
rate of melting = rate of freezing For any pure substance at 1 atmospheric pressure the temperature at which the solid and liquid phases are at equilibrium is called the normal melting point or normal freezing point of the substance.

Liquid – Vapour Equilibrium
In order to understand the liquid-vapour equilibrium, let us consider evaporation of water in a closed vessel. Consider a closed vessel connected to a manometer. The water vapour present in the vessel is first removed by placing some drying agent such as anhydrous calcium chloride in it for some time. The drying agent is then removed. Now the level of mercury in both the limbs of the manometer will be same. Introduce some water into the vessel and allow to stay at room temperature. Now water starts evaporating. A Pressure will gradually develop within the vessel due to the formation of water vapours. The change of pressure can be easily measured from the manometer. As evaporation continues, the pressure goes on increasing and the level of mercury in the right limb of the manometer starts rising. After some time it is observed that pressure becomes constant. This shows that the quantity of water vapour is not increasing any more, although liquid water is still present in the vessel. This indicates that a state of dynamic equilibrium has been attained between liquid water and water vapours.

At equilibrium, both reaction take place at the same rate. Thus at equilibrium,
rate of evaporation = rate of condensation

The pressure exerted by the vapours in equilibrium with the liquid at a particular temperature is called
vapour pressure of the liquid.

It may be noted that the equilibrium between the vapours and the liquid is attained only in a closed vessel. If the vessel is open, the vapours leave the vessel and get dispersed. Hence the rate of conden-sation will never become equal to the rate of evapo-ration.

Solid – Vapour Equilibrium
Consider systems where solids sublime to vapour phase, For example,

Equilibrium involving Dissolution of Solid or Gas in Liquids
Solids in liquids: In a saturated solution, a dynamic equilibrium exits between the solute molecules in the solid state and in the solution: the rate of dissolution of sugar = rate of crystallisation of sugar. Gases in liquids: This equilibrium is governed by Henry’s law, which states that the mass of a gas dissolved in a given mass of a solvent at any temperature is proportional to the pressure of the gas above the solvent

General Characteristics of Equilibria involving Physical Processes
For the physical processes discussed above, following characteristics are common to the system at equilibrium:

1. Equilibrium is possible only in a closed system at a given temperature.
2. Both the opposing processes occur at the same rate and there is a dynamic but stable condition.
3. All measurable properties of the system remain constant.
4. When equilibrium is attained for a physical process, it is characterised by constant value of one of its parameters at a given temperature.
5. The magnitude of such quantities at any stage indicates the extent to which the reaction has proceeded before reaching equilibrium.

Equilibrium In Chemical Processes – Dynamic Equilibrium
Consider a general reversible reaction
A+B \(\rightleftharpoons \) C+D

Suppose the reaction is carried out in a closed container. In the beginning, the concentrations of A and B are maximum and the concentrations of C and D are minimum (equal to zero). As the reaction proceeds, the concentrations of A and B will decrease whereas the concentrations of C and D will increase. Hence the rate of the forward reaction will be high in the beginning and it will decrease gradually because of the fall in concentrations of A and B. On the other hand the velocity of the reverse reaction will be minimum at the beginning and it will increase gradually due to the increase in concentrations of C and D. Finally a stage will be reached when the rate of the forward reaction becomes equal to the rate of the reverse reaction. This state of the system is known as the state of chemical equilibrium. At this state the concentrations of the reactants and the products remain constant.

We can also start with C and D and make the reaction to proceed in the reverse direction. The concentration of C and D decreases and A and B increases. Finally, equilibrium is attained. One such example is given.
H_2(g) +l_2(g) \(\rightleftharpoons \) 2Hl_(g)

Law Of Chemical Equilibrium And Equilibrium Constant
The relation between rates of reaction and concentrations was given by Guldberg and Wage in 1864. This relation is known as law of mass action.
The relation is,
\(K_{c}=\frac{[C][D]}{[A][B]}\)
For a general reversible reaction of the type,
aA + bB \(\rightleftharpoons \) cC + dD
the equilibrium constant maybe represented as
\(K_{ c }=\frac { [c]^{ c }[D]^{ d } }{ [A]^{ a }{ \left[ B \right] }^{ b } } \)
The equation is known as the expression for the law of chemical equilibrium.

The law of chemical equilibrium or equilibrium law may thus be stated as :
At a given temperature, the product of concentrations of the reaction products raised to the respective stoichiometric coefficient in the balanced chemical equation divided by the prod-uct of concentrations of the reactants raised to their individual stoichiometric coefficients has a constant value. This is known as the Equilibrium Law or Law of Chemical Equilibrium.
If equilibrium constant for the backward reaction is
K’_c then K’_c = \(\frac{1}{K_{e}}\)

Homogeneous Equilibria
In a homogeneous system, all the reactants and products are in the same phase. For example, in the gaseous reaction,
N_2(g) + 3H_2(g) \(\rightleftharpoons \) 2NH_3(g)

Heterogeneous Equilibria
Equilibrium in a system having more than one phase
is called heterogeneous equilibrium.
For example, H₂O_(l) \(\rightleftharpoons \) H₂O_(g)

Applications Of Equilibrium Constants

Predicting the Extent of a Reaction

• If K_c >10³, products predominate over reactants, i.e., if K_c is very large, the reaction proceeds nearly to completion.
• If K_c < 10^-3, reactants predominate over products, i.e., if K_c is very small, the reaction proceeds rarely.
• If K_c is in the range of 10^-3 to 10³, appreciable concentrations of both reactants and products are present.

Predicting The Direction Of The Reaction
The equilibrium constant is also used to find in which direction the reaction mixture of reactants and products will proceed. For this, we have to calculate the reaction quotient (Q_c) and compare with the equilibrium constant (K_c).

The concentrations of the species in Q_c are not necessarily equilibrium values.
For a general reaction aA + bB → cC + dD
\(Q_{ c }=\frac { [c]^{ c }[D]^{ d } }{ [A]^{ a }{ \left[ B \right] }^{ b } } \)
If Q_c > K_c, the reaction will proceed in the direction of the reactants (i.e., reverse reaction).
If Q_c < K_c, the reaction will proceed in the direction of the products (i.e., forward reaction).
If Q_c = K_c, the reaction mixture is already at equilibrium.

Calculating Equilibrium Concentrations
Step 1.
Write the balanced equation forthe reaction.

Step 2.
Under the balanced equation, make a table that lists foreach substance involved in the reaction:
a) the initial concentration,
b) the change in concentration on going to equilibrium, and
c) the equilibrium concentration.

In constructing the table, define x as the concentration ’ (mol/L) of one of the substances that reacts on going to equilibrium, then use the stoichiometry of the reaction to determine the concentrations of the other substances in terms of x.

Step 3.
Substitute the equilibrium concentrations into the equilibrium equation forthe reaction and solve for x. If you are to solve a quadratic equation choose the mathematical solution that makes chemical sense.

Step 4.
Calculate the equilibrium concentrations from the calculated value of x.

Step 5.
Check your results by substituting them into the equilibrium equation.

Problem
3.00 mol of PCl₅ kept in 1L closed reaction vessel was allowed to attain equilibrium at 380 K. Calculate composition of the mixture at equilibrium. K_c = 1.80

Solution
Let x mol of PCl₅ dissociated, At equilibrium:
(3 – x) x x
K_c = [PCl₃][Cl₂][PCl₅]
1.8 = x²/(3 – x)
x² + 1.8x – 5.4 = 0
x = [-1.8 ± √(1.8)² – 4(-5.4)]/2
x = [-1.8 ± √3.24 + 21.6]/2
x = [-1.8 ± 4.98]/2
x = [-1.8 + 4.98]/2
x = 1.59
[PCl₅] = 3.0 -x = 3 – 1.59 = 1.41 M
[PCl₃] = [Cl₂] = x = 1.59 M

Relationship Between Equilibrium Constant K, Reaction Quotient Q And Gibbs Energy G

• ∆G is negative, then the reaction is spontaneous and proceeds in the forward direction.
• ∆G is positive, then reaction is considered non-spontaneous. Instead, as reverse reaction would have a negative ”G, the products of the forward reaction shall be converted to the reactants.
• ∆G is O, reaction has achieved equilibrium; at this point, there is no longer any free energy left to drive the reaction.

A mathematical expression of this thermodynamic view of equilibrium can be described by the following equation:

∆G = ∆G° + RT InQ
where, G° is standard Gibbs energy.
At equilibrium, when ∆G = 0 and Q=K_c the equation becomes,
∆G = ∆G° +RTIn K = 0
∆G° = -RTInK
InK = -∆G° / RT
Therefore, K = e^∆Gv/RT

Factors Affecting Equilibria
In order to decide what course the reaction adopts and make a qualitative prediction about the effect of a change in conditions on equilibrium we use Le Chatelier’sprinciple. It states that a change in any of the factors that determine the equilibrium conditions of a system will cause the system to change in such a manner so as to reduce or to counteract the effect of the change. This is applicable to both physical and chemical equilibria.

Effect of Concentration Change
When the concentration of any of the reactants or products in a reaction at equilibrium is changed, the composition of the equilibrium mixture changes so as to minimize the effect of concentration changes.

Effect of Pressure Change
A pressure change obtained by changing the volume can affect the yield of products in case of a gaseous reaction where the total number of moles of gaseous reactants and total number of moles of gaseous products are different.

Effect of Inert Gas Addition
If the volume is kept constant and an inert gas such as argon is added which does not take part in the reaction, the equilibrium remains undisturbed. It is because the addition of an inert gas at constant volume does not change the partial pressures orthe molar concentrations of the substance involved in the reaction. So the reaction quotient does not change.

Effect of Temperature Change
Whenever an equilibrium is disturbed by a change in the concentration, pressure or volume, the composition of the equilibrium mixture changes because the reaction quotient, Q_c no longer equals the equilibrium constant, K_c However, when a change in temperature occurs, the value of equilibrium constant, K_c is changed. In general, the temperature dependence of the equilibrium constant depends on the sign of ∆H for the reaction.

• The equilibrium constant for an exothermic reaction (negative ∆H) decreases as the temperature increases.
• The equilibrium constant for an endothermic reaction (positive ∆H) increases as the temperature increases.

Temperature changes affect the equilibrium constant and rates of reactions.

Effect of a Catalyst
A catalyst increases the rate of the chemical reaction by making available a new low energy pathway for the conversion of reactants to products. It increases the rate of forward and reverse reactions that pass through the same transition state and does not affect equilibrium. Catalyst lowers the activation energy for the forward and reverse reactions by exactly ‘ the same amount.

Ionic Equilibrium In Solution
Michael Faraday classified the substances into two categories based on their ability to conduct electricity. One category of substances conduct electricity in their aqueous solutions and are called electrolytes while the other do not and are thus, referred to as non-electrolytes.

Faraday further classified electrolytes into strong and weak electrolytes.

Strong electrolytes on dissolution in water are ionized almost completely, while the weak electrolytes are only partially dissociated.

Acids. Bases And Salts

Arrhenius Concept of Acids and Bases
According to Arrhenius theory, acids are substances that dissociates in water to give hydrogen ions H⁺_(aq) and bases are substances that produce hydroxyl ions OH^–_(aq). The ionization of an acid HX _(aq) can be represented by the following equations:
HX_(aq) → H⁺(aq) + X^–(aq)
or
HX(aq) + H₂O(l) -> H₃O⁺(aq) + X^–(aq)

The Bronsted-Lowry Acids and Bases
The Danish chemist, Johannes Bronsted and the English chemist, Thomas M. Lowry gave a more general definition of acids and bases. According to Bronsted-Lowry theory, acid is a substance that is capable of donating a hydrogen ion l-T and bases are substances capable of accepting a hydrogen ion, H⁺. In short, acids are proton donors and bases are proton acceptors.

The acid-base pair that differs only by one proton is called a conjugate acid-base pair. Therefore, OH^– is called the conjugate base of an acid H₂O and NH₄⁺ is called conjugate acid of the base NH₃. If Bronsted acid is a strong acid then its conjugate base is a weak base and vice versa.
Consider the example of ionization of hydrochloric acid in water.

Ionization Of Acids And Bases

The Ionization constant of water and its ionic product
Water undergoes self ionisation to a small extent as follows.

Since [H₂O] is constant, K[H₂O]² may be taken as a new constant K_w. Thus,
K_w= [H₃O⁺][OH^–]

Where K_w is called ionic product of water. Its value is 1 x10‘14 mol2 L2 at 298 K. In pure water, the concen-tration of hydronium ions and hydroxyl ions are equal. Therefore in pure water,
[H₃O⁺] = [OH^–] = 1 × 10^-7 mol L^-1

Since the ionisation of water increases with increase of temperature, K_w increases with rise of temperature.

The pH Scale
Hydronium ion concentration in molarity is more conveniently expressed on a logarithmic scale known as the pH scale.

The pH of a solution is defined as the negative logarithm to base 10 of the activity (a_H+) of hydrogen ion.
i.e., pH = – log aH^H+ = – log {[H+]/,mol L^-1}
Acidic solution has pH < 7 Basic solution has pH > 7
Neutral solution has pH = 7

Ionization Constants of Weak Acids

Here, c= initial concentration of the undissociated acid, HXat time, t = 0. α = extent up to which HX is ionized into ions.
K_a = c²a² / c(1 – α) = cα²/1 – A
K_a is called the dissociation or ionization constant.

Ionization of Weak Bases
The equilibrium constant for base ionization is called base ionization constant and is represented by K_b.

When equilibrium is reached, the equilibrium constant can be written as:
K_b = (cα)² / c(1 – α) = cα² / (1 – α)
considering the base-dissociation equilibrium reaction:
K_b = [BH⁺][OH^–]/[B]
Then multiplying and dividing the above expression by [H⁺], we get:
K_b = [BH⁺][OH^–][H⁺]/[B][H⁺]
= {[OH^–][H⁺]}{[BH⁺]/[B][H⁺]}
= K_w/K_a
Then we get the following relation;
pK_a + PK_b = pK_q = 14 (at 298 K)

Common ion effect in the ionization of Acids and Bases.
Common ion effect my be defined as the suppression of the dissociation of a weak electrolyte (weak acid or weak base) by the addition of some strong electrolyte containing a common ion.

Factors Affecting Acid Strength
Dissociation of an acid depends on the strength and polarity of the H-A bond.
Electronegativity of A increases CH₄ < NH₃ < H₂O < HF Acid strength increases

Common Ion Effect in the Ionization of Acids and Bases
Ka = [H⁺] [Ac^–] / [HAc] acetate ions to an acetic acid solution results in decreasing the concentration of hydrogen ions, [H⁺], Also, if H⁺ ions are added from an external source then the equilibrium moves in the direction of undissociated acetic acid. This phenomenon is an example of common ion effect.

Hydrolysis of Salts and the pH of their Solutions
Salts formed by the reactions between acids and bases in definite proportions, undergo ionization in water. The cations/anions formed on ionization of salts either exist as hydrated ions in aqueous solutions or interact with water to reform corresponding acids/bases depending upon the nature of salts. The later process of interaction between water and cations/anions or both of salts is called hydrolysis.

Buffer Solutions
The solutions which resist change in pH on dilution or with the addition of small amounts of acid or alkali are called Buffer Solutions.

Solubilityequilibriaof Sparingly Soluble Salts

Solubility Product Constant
The equilibrium between the undisolved solid and the ions in a saturated solution can be represented by the equation:

We call K_sp the solubility product constant or simply solubility product.

Thus, solubility product of a salt is the product of concentration of ions in its saturated solution, raised to a power equal to the number of times the ions occur in the equation representing the dissociation of the salt.

The term K_sp in equation is given by Q_sp when the concentration of one or more species is not the concentration under equilibrium. Obviously under equilibrium conditions K_sp = Q_sp but otherwise it gives the direction of the processes of precipitation or dissolution.

Common Ion Effect on Solubility of Ionic Salts
The solubility of salts of weak acids like phosphates increases at lower pH. This is because at lower pH the concentration of the anion decreases due to its proto-nation. This, in turn, increases the solubility of the salt so that K_sp = Q_sp.

Ncert Supplementary Syllabus

Designing Buffer Solution
Knowledge of pK_a, pK_b and equilibrium constant help us to prepare the buffer solution of known pH. Let us see how we can do this.

Preparation of Acidic Buffer
To prepare a buffer of acidic pH we use weak acid and its salt formed with strong base. We develop the equation relating the pH, the equilibrium constant, K_a of weak acid and ratio of concentration of weak acid and its conjugate
base. For the general case where the weak acid HA ionises in water,

ratio of concentration of conjugate base (anion) of the acid and the acid present in the mixture. Since acid is a weak acid, it ionises to a very little extent ‘and concentration of [HA] is negligibly different from concentration of acid taken to form buffer. Also, most of the conjugate base, [A^–], comes from the ionisation of salt of the acid. Therefore, the concentration of conjugate base will be negligibly different from the concentration of salt. Thus, equation (A-2) takes the form: pH-pK_a + log\(\frac{[\mathrm{Salt}]}{[\mathrm{Acid}]}\)

In the equation (A-1), if the concentration of [A^–] is equal to the concentration of [HA], then pH = pK_a because value of log 1 is zero. Thus if we take molar concentration of acid and salt (conjugate base) same, the pH of the buffer solution will be equal to the pK_a of the acid. So for preparing the buffer solution of the required pH we select that acid whose pK_a is close to the required pH. For acetic acid pK_a value is 4.76, therefore pH of the buffer solution formed by acetic acid and sodium acetate taken in equal molar concentration will be around 4.76.

A similar analysis of a buffer made with a weak base and its conjugate acid leads to the result,

pH of the buffer solution can be calculated by using the equation pH + pOH =14.

We know that pH + pOH = pK_w and pK_a + pK_b = pK_w On putting these values in equation (A-3) it takes the form as follows:

If molar concentration of base and its conjugate acid (cation) is same then pH of the buffer solution will be same as pK_a for the base. pK value for ammonia is 9.25; therefore a buffer of pH close to 9.25 can be obtained by taking ammonia solution and ammonium chloride solution of equal molar concentration. For a buffer solution formed by ammonium chloride and ammonium hydroxide, equation (A-4) becomes:

pH of the buffer solution is not affected by dilution because ratio under the logarithmic term remains unchanged.

Students can Download Chapter 5 States of Matter Notes, Plus One Chemistry Notes helps you to revise the complete Kerala State Syllabus and score more marks in your examinations.

Kerala Plus One Chemistry Notes Chapter 5 States of Matter

Introduction
The observable characteristics of chemical systems represent bulk properties of matter. Chemical properties do not depend the physical state of matter but chemical reactions do.

Inter Molecular Forces
Intermolecular forces are the forces of attraction and repulsion between interacting particles (atoms and molecules). This term does not include the electrostatic forces that exist between the two oppositely charged ions and the forces that hold atoms of a molecule together i.e., covalent bonds.

Dispersion Forces Or London Forces
A nonpolar atom or molecule has a positive centre surrounded by a symmetrical negative electron cloud. The displacement of electron cloud creates an instantaneous dipole temporarily. This instantaneous dipole distorts the electron distribution of other atoms or molecules which are close to it and induces dipole in them also. In this way, a large number of nonpolar molecules become temporarily polar and they mutually attracted by weak attractive forces. These forces are very weak and are known to operate in all types of molecules.

Dipole-Dipole Forces
These type of interactions occur in polar molecules having permanent dipoles such as HCl, HBr, H₂S, etc. Such molecules possess partial charges of opposite sign at their ends. The positive end of one molecule attracts the negative end of the other molecule and vice versa. A simple example is the of H-Cl in which chlorine being more electronegative acquires slight negative charge whereas hydrogen becomes slightly positively charged. The dipole-dipole inter-action then takes place in H-Cl as follows.

Dipole-Induced Dipole Forces
These type of interactions are found in a mixture, containing polar and nonpolar molecules. When a nonpolar molecule is brought neara polar molecule, the positive end of the polar molecule attracts the electron cloud of the nonpolar molecule. Thus a polarity is induced in the nonpolar molecule. Then there will be attractive interacting between the polar molecule and the induced dipole of the nonpolar molecule.

Hydrogen Bond
Hydrogen bond can be defined as the attractive force which binds hydrogen atom of one molecule with the electronegative atom (F, O or N) of another molecule. When hydrogen is bonded to strongly electronegative element ‘X’, the electron pair shared between the two atoms moves far away from hydrogen atom. As a result, the hydrogen atom becomes, highly electropositive with respect to the other atom ‘X’. Since there is displacement of electrons towards X, the hydrogen acquires fractional positive charge (δ⁺) while ‘X’ attain fractional negative charge (δ^–). This results in the formation of a polar molecule having electrostatic force of attraction which can be represented as: H^δ+ – X^δ-

The magnitude of H-bonding depends on the physical state of the compound. It is maximum in the solid state and minimum in the gaseous state. Thus, the hydrogen bonds have strong influence on the structure and properties of the compounds.

Types of Hydrogen Bonds
There are two types of hydrogen bonds

1. Intermolecular hydrogen bond
2. Intramolecular hydrogen bond

1. Intermolecular hydrogen bond:
It is formed between two different molecules of the same or different compounds. For example, H-bond in case of HF molecule, alcohol or water molecules, etc.

2. Intramolecular hydrogen bond:
It is formed when hydrogen atom is in between the two highly electronegative (F, O, N) atoms present within the same molecule. For example, in o-Nitrophenol the hydrogen is in between the two oxygen atoms as shown below:

Thermal Energy
Thermal energy is the energy of a body arising from motion of its atoms or molecules. It is directly proportional to the temperature of the substance. The movement of particles using thermal energy is called thermal motion.

Intermolecular Forces Vs Thermal Interactions
Intermolecular forces tend to keep the molecules together but thermal energy of the molecules tends to keep them apart. Three states of matter are the result of balance between intermolecular forces and the thermal energy of the molecules.

The Gaseous State

• Gases are highly compressible.
• Gases exert pressure equally in all directions.
• Gases have much lower density than the solids and liquids.
• The volume and the shape of gases are not fixed. These assume volume and shape of the container.
• Gases mix evenly and completely in all proportions without any mechanical aid.

The Gas Laws

Boyle’s Law (Pressure – Volume Relationship)
On the basis of his experiments, Robert Boyle reached to the conclusion that at constant temperature, the pressure of a fixed amount of gas
varies inversely with its volume. This is known as Boyle’s law. It can be written as p ∝ \(\frac{1}{V}\)
where temperature(T) and number of moles(n)are constant.

If a fixed amount of gas at constant temperature T occupying volume V₁ at pressure p₁ undergoes expansion, so that volume becomes V₂ and pressure becomes p₂, then according to Boyle’s law :
p₁V₁ = p₂V₂ = constant
\(\Rightarrow \frac{p_{1}}{p_{2}}=\frac{V_{2}}{V_{1}}\)

Here T is constant and the graph is called isotherm

Charles’ Law (Temperature – Volume Relationship)
Charles’ law, which states that pressure remaining constant, the volume of a fixed mass of a gas is directly proportional to its absolute temperature. According to this law

Here we use new temperature scale called the kelvin temperature scale or Absolute temperature scale, t °C in Celsius scaleis equal to (273.15+t) kelvin in kelvin scale.

Each line of the volume vs temperature graph is called isobar. The lowest hypothetical or imaginary temperature at which gases are supposed to occupy zero volume is called Absolute zero.
We can see that the volume of the gas at – 273.15 °C will be zero.

Gay Lussac’s Law (Pressure-Temperature Relationship)
The relationship between pressure and temperature was given by Joseph Gay Lussac and is known as Gay Lussac’s law. It states that at constant volume, pressure of a fixed amount of a gas varies directly with the temperature. Mathematically,
P ∝ T
⇒ \(\frac{p}{T}\) = constant
This relationship can be derived from Boyle’s law and Charles’ Law.Each line of Pressure vs temperature (kelvin) graph at constant molar volume is called isochore.

Avogadro Law (Volume -Amount Relationship)
In 1811 Italian scientist Amedeo Avogadro tried to combine conclusions of Dalton’s atomic theory and Gay Lussac’s law of combining volumes which is now known as Avogadro law. It states that equal volumes of all gases under the same conditions of temperature and pressure contain equal number of molecules.

Mathematically we can write v α n where n is the number of moles.

The number of molecules in one mole of a gas has been determined to be 6.022 *1023and is known as Avogadro constant. A gas that follows Boyle’s law, Charles’ law and Avogadro law strictly is called an ideal gas.

Ideal Gas Equation
The combination of Boyle’s law, Charles’ law, and Avagadro’s law leads to an equation which gives the combined effect of change of temperature and pressure on the volume of a gas.
According to Boyle’s law, V α \(\frac{1}{P}\) ——- (i) (at constant T and n)
According to Charles’ Law, V α T ——- (ii) (at constant P and n)
According to Avogardro’s Law, V α n ——- (iii) (at constant T and P

Where R is a constant known as the universal gas constant. The equation is known as ideal gas equation.

Density and Molar Mass of a Gaseous Substance
Ideal gas equation can be rearranged as follows:

we get \(\frac{d}{M}=\frac{p}{R T}\)
(where d is the density)
On rearranging equation we get the relationship for calculating molar mass of a gas.
\(M=\frac{d R T}{p}\)

Dalton’s Law of Partial Pressures
The law was formulated by John Dalton in 1801. It states that the total pressure exerted by the mix-ture of non-reactive gases is equal to the sum of the partial pressures of individual gases.
P_Total = P₁ + P₂ + P₃ + ………. (at constant T, V)

where p_total is the total pressure exerted by the mixture of gases and p₁, p₂, p₃ etc. are partial pressures of gases.

Partial pressure in terms of mole fraction

Kinetic Molecular Theory Of Gases
Maxwell, Boltzmann, and others put forward a theoretical model of the gas. The theory is known as
Kinetic molecular theory of gases or microscopic
model of gases.
Postulates of kinetic molecular theory.

1.  All gases are made up of a large number of extremely small particles called molecules.
2. The molecules are separated from one another by large distances so that the actual volume of the molecules is negligible as compared to the total volume of gas.
3. The molecules are in a state of continuous rapid motion in all directions. During their motion, they keep on colliding with one another and also with the walls of the container.
4. Molecular collisions are perfectly elastic i.e. there is no net loss or gain of energy in their collisions. However, there may be redistribution of energy during such collisions.
5. There are no attractive forces between the molecules. They move completely independent of each other.
6. The pressure exerted by the gas is due to the bombardment of its molecules on the walls of the container.
7. At any instant, different molecules possess different velocities and hence different energies. However, the average kinetic energy of the molecules is directly proportional to its absolute temperature.

Behaviour Of Real Gases:
Deviation From Ideal Gas Behaviour
There are two types of curves are seen in the graph. In the curves for dihydrogen and helium, as the pressure increases the value of pV also increases. The second type of plot is seen in the case of other gases like carbon monoxide and methane. In these plots first, there is a negative deviation from ideal behaviour, the pV value decreases with increase in pressure and reaches to a minimum value characteristic of a gas. After that pV value starts increasing. The curve then crosses the line for ideal gas and after that shows positive deviation continuously. It is thus, found that real gases do not follow ideal gas equation perfectly under all conditions.

We find that two assumptions of the kinetic theory do not hold good. These are

1. There is no force of attraction between the molecules of a gas.
2. Volume of the molecules of a gas is negligibly small in comparison to the space occupied by the gas.

If assumption (a) is correct, the gas will never liquify. This means that forces of repulsion are powerful enough and prevent squashing of molecules in tiny volume. If assumption (b) is correct, the pressure vs volume graph of experimental data (real gas) and that theoritically calculated from Boyles law (ideal gas) should coincide.

The volume occupied by the molecules also becomes significant because instead of moving in volume V, these are now restricted to volume (V-nb) where nb is approximately the total volume occupied by the molecules themselves. Here, b is a constant. Having taken into account the corrections for pressure and volume, we can rewrite equation as This equation is known as van der Waals’ equation.

Value of ‘a’ is measure of magnitude of intermolecular attractive forces within the gas and is independent of temperature and pressure.
Real gases show ideal behaviour when conditions of temperature and pressure are such that the intermolecular forces are practically negligible. The real gases show ideal behaviour when pressure approaches zero.

The deviation from ideal behaviour can be measured in terms of compressibility factor Z, which is the ratio of product pV and nRT. Mathematically
\(z=\frac{p V}{n R T}\)

For ideal gas Z = 1 at all temperatures and pressures because pV = nRT.
At high pressure, all the gases have Z > 1. These are more difficult to compress. At intermediate pressures, most gases have Z < 1. The temperature at which a real gas obeys ideal gas law over an appreciable. range of pressure is called Boyle temperature or Boyle point.

Liquefaction Of Gases
The highest temperature at which liquefaction of the gas first occurs is called Critical temperature (T_c). Volume of one mole of the gas at critical temperature is called critical volume (V_c) and pressure at this temperature is called critical pressure (P_c).
The critical temperature, pressure, and volume are called critical constants.

Liquid State
Intermolecular forces are stronger in liquid state than in gaseous state.

Vapour Pressure
The pressure exerted by the vapour on the walls of the container is known as vapour pressure.

Surface Tension
Liquids tend to minimize their surface area. The molecules on the surface experience a net downward force and have more energy than the molecules in the bulk, which do not experience any net force. This characteristic property of liquids is known as surface tention. Liquids tend to have minimum number of molecules at their surface due to surface tention.

If surface of the liquid is increased by pulling a molecule from the bulk, attractive forces will have to be overcome. This will require expenditure of energy. The energy required to increase the surface area of the liquid by one unit is defined as surface energy.

Viscosity
It is a common observation that certain liquids flow faster than others. For example, liquid like water, ether, etc. flow rapidly while liquids like glycerine, castor oil, honey, etc. flow slowly. These differences in flow rates result from a property known as viscosity. Every liquid has some internal resistance to flow. This internal resistance to flow possessed by a liquid is called its viscosity. Liquids which flow slowly have high internal resistance and are said to have high viscosity. On the other hand, liquids which flow rapidly have low internal resistance and are said to have low viscosity.

Viscosity is also related to intermolecular forces in liquids. If the intermolecular forces are large, the vis-cosity will be high. Viscosity of a liquid decreases with rise in temperature. This is because at higher temperature the attractive forces between molecules are overcome by the increased kinetic energies of the molecules.

Ncert Supplementary Syllabus

Kinetic Energy And Molecular Speeds
Molecules of gases remain in continuous motion. While moving they collide with each other and with the walls of the container. This results in change of their speed and redistribution of energy. So the speed and energy of all the molecules of the gas at any instant are not the same. Thus, we can obtain only average value of speed of molecules. If there are n number of molecules in a sample
and their individual speeds are u₁, u₂, ……… u_n, then average speed of molecules u_av can be calculated as follows:
\(u_{a v}=\frac{u_{1}+u_{2}+\ldots u_{n}}{n}\)

Maxwell and Boltzmann have shown that actual distribution of molecular speeds depends on temperature and molecular mass of a gas. Maxwell derived a formula for calculating the number of molecules possessing a particular speed. Fig. A(1) shows schematic plot of number of molecules vs. molecular speed at two different temperatures T₁ and T₂ (T₂ is higher than T₁). The distribution of speeds shown in the plot is called Maxwell-Boltzmann distribution of speeds.

The graph shows that number of molecules possessing very high and very low speed is very small. The maximum in the curve represents speed possessed by maximum number of molecules. This speed is called most probable speed, u_mp. This is very close to the average speed of the molecules. On increasing the temperature most probable speed increases. Also, speed distribution curve broadens at higher temperature. Broadening of the curve shows that number of molecules moving at higher speed increases. Speed distribution also depends upon mass of molecules. At the same temperature, gas molecules with heavier mass have slower speed than lighter gas molecules. For example, at the same temperature, lighter nitrogen molecules move faster than heavier chlorine molecules. Hence, at any given temperature, nitrogen molecules have higher value of most probable speed than the chlorine molecules. Though at a particular temperature the individual speed of molecules keeps changing, the distribution of speeds remains same.

The kinetic energy of a particle is given by the expression:
Kinetic Energy = \(\frac{1}{2}\) mu²
Therefore, if we want to know average translational kinetic energy, \(\frac{1}{2} m \overline{u^{2}}\) , for the movement of a gas particle in a straight line, we require the value of mean of square of speeds, \(\overline{u^{2}}\), of all molecules. This is represented as follows:
\(u^{2}=\frac{u_{1}^{2}+u_{2}^{2}+\ldots . u_{n}^{2}}{n}\)

The mean square speed is the direct measure of the average kinetic energy of gas molecules. If we take the square root of the mean of the square of speeds then we get a value of speed which is different from most probable speed and average speed. This speed is called root mean square speed and is given by the expression as follows:
\(u_{m s}=\sqrt{u_{2}}\)

Root mean square speed, average speed and the most probable speed have following relationship:
u_rms u_av u_mp

The ratio between the three speeds is given below:
u_mp : u_av : u_rms :: 1 : 1.128 : 1.224

Students can Download Chapter 3 Classification of Elements and Periodicity in Properties Notes, Plus One Chemistry Notes helps you to revise the complete Kerala State Syllabus and score more marks in your examinations.

Kerala Plus One Chemistry Notes Chapter 3 Classification of Elements and Periodicity in Properties

Introduction
The systematic classification of elements made the study of elements easy. In this unit, we will study the historical development of the periodic table and also learn how elements are classified.

Genesis Of Periodic Classification
While Dobereiner initiated the study of periodic relationship, it was Mendeleev who was responsible for publishing the Periodic Law for the first time. It states as follows:

The properties of the elements are a periodic function of their atomic weights.
Mendeleev arranged elements in horizontal rows and vertical columns of a table in order of their increasing ‘ atomic weights. Elements with similar properties occupied the same vertical column or group. He realized that some of the elements did not fit in with his scheme of classification if the order of atomic weight was strictly followed. He ignored the order of atomic weights, thinking that the atomic measurements might be incorrect, and placed the elements with similar properties together.

At the same time, keeping his primary aim of arranging the elements of similar properties in the same group, he proposed that some of the elements were still undiscovered and, therefore, left several gaps in the table. He left the gap under aluminium and a gap under silicon, and called these elements Eka-Aluminium and Eka-Silicon. Mendeleev predicted the existence of gallium and germanium, and their general physical properties. These elements were discovered later.

Modern Periodic Law And The Present Form Of The Periodic Table
Modem periodic law states that “The physical and chemical properties of the elements are periodic functions of their atomic numbers”. Atomic number is equal to the nuclear charge and the elements are arranged in the increasing order of atomic number.

The period number correspond to the highest principal quantum number (n) of the elements.

Nomenclature Of Elements With Atomic Number Greater Than 100
The names (IUPAC) are derived directly form the atomic number using numerical roots for zero and numbers 1 to 9. The roots are linked together in the order of digits and ‘ium’ is added at the end. The roots for 0,1, 2 9 are nil, un, bi, tri, quad, pent, hex, sept, oct and enn respectively. For example, the element with atomic number 110 will have the name Ununnilium (Un+ un+nil + ium), The element with atomic number 114 has the name Ununquadium (un + un + quad + ium) and the element with atomic number 120 will be Unbinilium (un + bi + nil + ium).

Electronic Configurations And Types Of Elements: s, p, d, f- Blocks

The s-Block Elements
The elements of Group 1 (alkali metals) and Group 2 (alkaline earth metals) which have ns1 and ns2 outermost electronic configuration belong to the s-Block Elements. They are all reactive metals with low ionization enthalpies.

They lose the outermost electron(s) readily to form 1+ ion (in the case of alkali metals) or 2+ ion (in the case of alkaline earth metals). The metallic character and the reactivity increase as we go down the group. Because of high reactivity they are never found pure in nature.

The compounds of the s-block elements, with the exception of those of lithium and beryllium are predominantly ionic.

The p-Block Elements
The p-Block Elements comprise those belonging to group 13 to 18 and these together with the s-Btock Elements are called the Representative Elements or Main Group Elements. The outermost electronic configuration varies from ns2np1 to ns2np6in each period. At the end of each period is a noble gas element with a closed valence shell ns2np6 configuration. All the orbitals in the valence shell of the noble gases are completely filled by electrons and it is very difficult to alter this stable arrangement by the addition or removal of electrons. The noble gases thus exhibit very low chemical reactivity. Preceding the noble gas family are two chemically important groups of non-metals. They are the halogens (Group 17) and the chalcogens (Group 16). These two groups of elements have high negative electron gain enthalpies and readily add one or two electrons respectively to attain the stable noble gas configuration. The non-metallic character increases as we move from left to right across a period and metallic character increases as we go down the group.

The d-Block Elements (Transition Elements)
These are the elements of group 3 to 12 in the centre of the Periodic Table. These are characterised by the filling of inner d orbitals by electrons and are therefore referred to as d-Block Elements. These elements have the general outer electronic configuration (n-1) d1-10ns^2. They are all metals. They mostly form coloured ions, exhibit variable valence (oxidation states), paramagnetism and oftenly used as catalysts. However, Zn, Cd and Hg which have the electronic configuration, (n-1) d10ns2 do not show most of the properties of transition elements. In a way, transition metals form a bridge between the chemically active metals of s-block elements and the less active elements of groups 13 and 14 and thus take their familiar name “Transition Elements”.

The f-Block Elements (Inner-Transition Elements)
The two rows of elements at the bottom of the Periodic Table, called the Lanthanoids, Ce(Z = 58) -Lu(Z = 71) and actinoids, Th(Z = 90)-Lr(Z= 103) are characterised by the outer electronic configuration (n-2)f1-14 (n-1 )d°-1ns2. The last electron added to each element is filled in f- orbital. These two series of ‘ elements are hence called the Inner Transition Elements (f-Block Elements). They are all metals. Within each series, the properties of the elements are quite similar. The elements after Uranium are called Transuranium Elements.

Metals, Non-metals and Metalloids. In addition to displaying the classification of elements into s, p, d and f-blocks, they can be divided into Metals and Non-Metals. Metals usually have high melting and boiling points. They are good conductors of heat and electricity. They are malleable (can be flattened into thin sheets by hammering) and ductile (can be drawn into wires). In contrast, non-metals are located at the top right hand side of the Periodic Table.

In fact, in a horizontal row, the property of elements change from metallic on the left to non-metallic on the right. Non-metals are usually solids or gases at room temperature with low melting and boiling points (boron and carbon are exceptions). They are poor conductors of heat and electricity. Most nonmetallic solids are brittle and are neither malleable nor ductile. The elements become more metallic as we go down a group; the nonmetallic character increases as one goes from left to right across the Periodic Table. The elements (e.g., silicon, germanium, arsenic, antimony and tellurium) running diagonally across the Periodic Table show properties that are characteristic of both metals and nonmetals. These elements are called Semi-metals or Metalloids.

Periodic Trends In Properties Of Elements
Most of the properties such as atomic radius, ionic radius, Ionisation enthalpy, electron gain enthalpy and electron negativity are directly related to electronic configuration of their atoms. They show variation with change in atomic number within a period or a group.

Trends In Physical Properties

1. Atomic Radius :
lt is defined as the distance from the centre of the nucleus of an atom to the outermost shell of electrons. Electron cloud surrounding the atom does not have a sharp boundary since, the determination of the atomic size cannot be precise. Hence it is expressed in terms of different types of radii. Some of these are covalent radius and metallic radius. Covalent radius is defined as one half of the distance between the centres of nuclei of two similar atoms bonded by a single covalent bond. Metallic radius may be defined as half of the internuclear distance between two adjacent atoms in the metallic crystal.

2. Ionic Radius:
The removal of an electron from an atom results in the formation of a cation, whereas gain of an electron leads to an anion. The ionic radii can be estimated by measuring the distances between cations and anions in ionic crystals. When we find some atoms and ions which contain the same number of electrons, we call them isoelectronic species. For example, O2-, F~, Na+ and Mg2+ have the same number of electrons (10). Their radii would be different because of their different nuclear charges.

3. Ionization Enthalpy:
A quantitative measure of the tendency of an element to lose electron is given by its Ionization Enthalpy. It represents the energy required to remove an electron from an isolated gaseous atom (X) in its ground state. To understand the trends in ionization enthalpy, we have to consider two factors: (i) the attraction of electrons towards the nucleus, and (ii) the repulsion of electrons from each other. The effective nuclear charge experienced by a valence electron in an atom will be less than the actual charge on the nucleus because of “shielding” or “screening” of the valence electron from the nucleus by the intervening core electrons.

The first ionization enthalpy of boron (Z = 5) is slightly less than that of beryllium (Z = 4) even though the former has a greater nuclear charge. It is because, s-electron is attracted to the nucleus more than a p-electron. In beryllium, the electron removed during the ionization is an s-electron whereas the electron removed during ionization of boron is a p-electron. The penetration of a 2s-electron to the nucleus is more than that of a 2p-electron; hence the 2p electron of boron is more shielded from the nucleus by the inner core of electrons than the 2s electrons of beryllium. Therefore, it is easier to remove the 2p-electron from boron Compared to the removal of a 2s-electron from beryllium.

Thus, boron has a smaller first ionization enthalpy than beryllium. Another “anomaly” is the smaller first ionization enthalpy of oxygen compared to nitrogen. This arises because in the nitrogen atom, three 2p-electrons reside in different atomic orbitals (Hund’s rule) whereas, in the oxygen atom, two of the four 2p-electrons must occupy the same 2p-orbital resulting in an increased electron-electron repulsion. Consequently, it is easier to remove the fourth 2p-electron from oxygen than it is, to remove one of the three 2p-electrons from nitrogen.

4. Electron Gain Enthalpy :
When an electron is added to a neutral gaseous atom (X) to convert it into a negative ion, the enthalpy change accom-panying the process is defined as the Electron Gain Enthalpy (∆_eg H).

5. Electronegativity:
A qualitative measure of the ability of an atom in a chemical compound to attract shared electrons to itself is called electronegativity. Unlike ionization enthalpy and electron gain enthalpy, it is not a measurable quantity. However, a number of numerical scales of electronegativity of elements viz., Pauling scale, Mulliken-Jaffe scale, Allred-Rochow scale have been developed.

Trends In Chemical Properties
1. Oxidation State :
The atomic property, valency is better explained in terms of oxidation state. It is the charge which an atom of element has or appears to have when present in the combined state. Electronegative elements generally acquire negative oxidation states while electropositive elements acquire positive oxidation states.

2. Anomalous properties of second-period elements:
The first element of each group in s and p block differs in many respects from the remaining members of the respective groups. This is due to their small size, high charge/ radius ratio, high electronegativity and availability of less valence orbitals. The first member has only 4 valence orbitals (2s, 2p) whereas the second member of the same group will have nine valence orbitals (3s, 3p, 3d) for bonding. B can form only (BF₄)^– while Al forms (AlF₆)^3-

In group 1 only Li forms covalent compounds and in many respects, Li resembles Mg of group 2. Similarly, Be resembles Al of group 13. This type of similarity in properties is known as diagonal relationship.

Chemical Reactivity
Across a period ionisation enthalpy increases and electron gain enthalpy becomes more negative. Thus elements at the extreme left show lower ionisation enthalpies (more electropositive nature) and those at the right (excluding nobel gases) show larger negative electron gain enthalpies (more electronegative). Therefore high chemical reactivity is found with elements at the two extremes compared to those at the centre. Electropositivity leads to metallic behaviour and electronegativity leads to non-metallic behaviour.