CHAPTER 1: THE SOLID STATE Solid: is a state of matter in which the constituent particles (atoms, molecules or ions) are

arranged very closely. Characteristics of solids: Definite mass, volume and shape Short Intermolecular distances & Strong Intermolecular forces Incompressible and Rigid Constituent particles have only vibrational motion Classification of on the basis of the arrangement of constituent particles: Crystalline (True solids) Amorphous (Pseudo solids or super cooled liquids) Definite characteristic geometrical shape Irregular arrangement of constituent particles Flat Faces, Sharp edges, Sharp melting point. Gradually soften over a range of temperature Definite and characteristic heat of fusion(Hfusion) Do not have definite heat of fusion(Hfusion) Anisotropic(some physical properties are different in Isotropic(same physical properties in all directions) different directions) Long range order(basic unit repeats itself infinitely) Short range order(basic unit not fixed) Ex: NaCl and quartz Ex: Glass, rubber and plastics Classification of Crystalline Solids: Type of Solid Constituent Bonding/ Physical Electrical M.P. Examples Particles Attractive Forces nature Conductivity
Molecular solids Non polar Polar H-bonded Metallic solids Molecules Dispersion/London forces Dipole-Dipole H-bonding Metallic Bonding Soft Soft Hard Hard but malleable& ductile Hard but brittle Hard Soft Insulator Insulator Insulator Conductors Very low Low Low Fairly High High Very High Ar, H2, I2, CO2, CCl4 HCl, SO2(s) H2O (ice) Fe, Cu, Ag, Mg NaCl, MgO, ZnS, CaF2 SiO2, SiC, C(diamond)

Ionic solids Covalent or Network solids

Positive metal ions(kernels) & delocalized e-s Ions Atoms

Close packed structures: Close packing in one dimension: Each atom is in contact with two of its neighbours. Coordination number is 2. Close packing in two dimensions: Obtained by stacking rows of close packed atoms. Square close packing: Horizontal as well as vertical alignment. The arrangement is AAA type. Coordination number is 4. Hexagonal close packing: The particles of the second row are placed in the depression between the particles of the first row. The arrangement is ABAB type. Coordination number is 6. There is lesser free space than square close packing hence packing is more efficient. Close packing in three dimensions: Obtained by stacking two dimensional layers one above another. Simple Cubic/Square Based Packing: The spheres of the upper layer are placed exactly over the first layer such that spheres of the layers are perfectly aligned horizontally and vertically. It has AAAA type pattern. Coordination number is 6 Ex: Pd Hexagonal Close Packing: Here, tetrahedral voids of the second layer may be covered by the spheres of the third layer. It gives rise to ABABAB type pattern. Coordination number is 12. Ex: Mg, Zn, Cd Cubic Close Packing/Face Centred Cubic Packing: Here, octahedral voids of the second layer may be covered by the spheres of the third layer. It gives rise to ABCABC type pattern. Coordination number is 12. Ex: Cu, Ag, Au, Al Types of voids: Tetrahedral voids (4 triangular faces): This type of void is formed at the center when four spheres are joined in the form of a tetrahedron. Coordination Number = 4. Smaller in size than octahedral voids. For an atom to occupy a tetrahedral void, its radius must be 0.225 times the radius of the sphere. Can be located along body diagonal. Each body diagonal will have two tetrahedral voids. Octahedral voids (8 triangular faces): This type of void is surrounded by six spheres. Coordination Number = 6. Larger in size than tetrahedral voids. For an atom to occupy an octahedral void, its radius must be 0.414 times the radius of the sphere. Can be located at the centre of each edge plus one at the centre of the cube. Number of particles in ccp arrangement = Number of particles present in octahedral voids = n Number of particles present in tetrahedral voids = 2n Density of unit cell =
zM 3 . NA
-7

Coulombic or electrostatic Covalent Bonding

Insulator in solid state Insulator

,z = No. of atoms in a unit cell M = Molar Mass a3 = Volume NA = 6.0221023-

Conductor (exception) C(graphite) Crystal lattice: is a regular three dimensional arrangement of constituent particles (called lattice points) in space. There are 14 possible three dimensional lattices. These are called Bravais Lattices. Lattice points or lattice sites: are the fixed positions on which the constituent particles are present. A group of lattice points which when repeated over and over again in 3 dimensions give the complete crystal lattice. Unit cell: is defined as the smallest repeating unit in space lattice which when repeated over and over again generates the complete crystal lattice. Type of Unit Cell Relation between a & r Number of atoms in a unit cell (z) Packing Efficiency() 100 Simple cubic/Primitive a= 2r 8 (1/8) = 1 atom [ +% = 52.4% Body Centred (bcc) Face Centred (fcc) 3a = 4r 2a = 4r 8 (1/8) + 1 = 2 atoms 8 (1/8) + 6 (1/2) = 4 atoms [
6 1003 8 100 32

Conversions: - 1 nm = 10 cm 1 = 10-8 cm 1 pm = 10-10 cm Packing efficiency is the percentage of total space occupied by constituent particles (atoms, molecules or ions)
3 Packing efficiency () = 3 Imperfections in Solids: refers to any deviation from an ordered arrangement of atoms/ions in a crystal. Point defects - are the irregularities or deviations from ideal arrangement around a point or an atom Line defects - are the irregularities or deviations from ideal arrangement in entire rows of lattice points. Types of Stoichiometric defects for ionic solids: Schottky/Vacancy defect Frenkel/Dislocation defect Equal number of cations and anions are missing. The smaller ion (usually cation) is dislocated from its normal site to an interstitial site. Lattice remains electrically neutral but Conduction Lattice remains electrically neutral but Conduction Density of a solid Density of the solid remains same Observed in highly ionic substances with high co-ordination Observed in less ionic substance with low cono. Also the cation and anion should be of similar sizes. ordination no. Also there should be a large difference in the size of the cation and anion.

43

]% = 68%

]% = 74%

Seven crystal systems: Crystal System Cell Edge Axial angles Cubic a=b=c = = = 90 Tetragonal a=bc = = = 90 Orthorhombic a b c = = = 90 Hexagonal a=b c = = 90 = 120 Rhombohedral or Trigonal a=b=c = = 90 Monoclinic a b c = = 90 90 Triclinic a b c 90 Coordination number is the number of nearest neighbours of a particle.

Examples NaCl, Zinc blende, Cu Sn(White tin), SnO2 TiO2, CaSO4 Rhombic sulphur, , KNO3, BaSO4 Graphite, ZnO,CdS, Calcite (CaCO3), HgS(Cinnabar) Monoclinic sulphur, Na2SO4.10H2O K2Cr2O7, CuSO4. 5H2O, H3BO3

For Ex: NaCl, KCl, CsCl and AgBr

For Ex: ZnS, AgCl, AgBr and AgI

Types of Non-stoichiometric defects: (:) 1. Metal excess * > 1+: This type of defect is due to excess of metal cations.
(;)

Metal excess defect due to anionic vacancies: One anion is absent from its lattice site. This empty lattice site is called a hole. To maintain electrical neutrality this site is occupied by an e . Density . The Anion vacancy which is occupied by an unpaired e is called f-centre or Farbenzenter centre. Solids with F-Centre are coloured and paramagnetic. Alkali metal/Alkali metal halide show this type of defect. Na/NaCl Golden Yellow K/KCl Violet Li/LiCl Red Colour Metal excess defect due to the presence of extra cations at interstitial sites: One cation is present in the interstitial site. An eis present in the interstitial site to maintain the electrical neutrality. Density . Solids with this defect are coloured and paramagnetic (due to the presence of unpaired es) Ex: - At low temp, ZnO is a stoichiometric compound. It gives a non-stoichiometric defect at high temperature because 1 it loses oxygen according to the reaction: Zn2+O2- Zn2+ + O2 + 2e- . The excess Zn2+ ions move to interstitial sites and 2 the es to neighbouring interstitial sites. Thus the presence of the extra es in the interstitial sites is responsible for yellow colour of ZnO at high temp. (:) 2. Metal deficiency * < 1+: This defect arises because of absence of metal ions from its lattice sites.
(;)

The electrical neutrality is maintained as we oxidise adjacent cation to its next valency state. This type of defect is observed in solids containing metals which show variable oxidation state or variable valency (i.e. transition elements). Ex: - FeO, NiO Ferrous Oxide (FeO) Non-Stoichiometric Solid exists as Fe0.93O1.00 1 missing Fe2+ Gives 2Fe3+ions. 2 0.07 % Fe3+ = 100 = 15.05% 0.93 % Fe2+ = (100 15.05) % = 84.95% Nickel Oxide (NiO) Non-Stoichiometric Solid exists as Ni0.98O1.00 1 missing NI2+ Gives 2Ni3+ions. 2 0.02 % Ni3+ = 100 = 4.08% 0.98 % Ni2+ = (100 4.08) % = 95.92% 3. Impurity Defects: The process of adding impurity is called doping. When MCl2(where M is a divalent cation, M2+) is added to NaCl defect is formed, Addition of one M2+ results in the loss of two Na+ ions (to maintain electrical neutrality), two vacancies are formed but one is filled by M2+ and the other remains empty (called cation vacancy). On addition of M2+ to NaCl: Density , Melting Point , Electrical Conduction Number of cation vacancies Formed = Number of M2+ (Divalent cation) Added Electrical Properties: Conductors: High conductivity - 104 to 107 ohm-1 m-1. Ex: - Metals Insulators: Very low conductivity - 10-20 to 10-10 ohm-1 m-1. Ex: - sulfur, phosphorus etc. Semiconductors: Conductivity in between conductor and insulator - 10-6 to 104 ohm-1 m-1.Ex: Si, GeBand theory If the

number of atoms involved in the formation of MO is very large, then the energy difference between the various MO decreases. Valence band: is the band formed by lower energy valence orbitals. Conduction band: is the band formed by slightly higher energy orbitals. Band Gap/Forbidden Gap: is the energy gap between the top of the VB and the bottom of CB. Effect of Temperature on Conductivity: Electrical conductivity of metals 1/ Temp Electrical conductivity of semiconductors Temp Types of semiconductors: Intrinsic Semiconductors: are those conduction is due to the movement of es and holes. The forbidden gap is small. Only some es may jump to CB and hence they have very low electrical conductivity. Ex: Si, Ge Extrinsic Semiconductor: obtained by adding impurities (process is called doping) Types of extrinsic semi-conductors: n-type semiconductors p type semiconductors Formed when a group 14 element (Si or Ge) is doped Formed when a group 14 element (Si or Ge) is doped with with e rich impurity like group 15 elements (P, As, Sb). e deficient impurity like group 13 elements (Al, Ga, In) Conductivity due to the negatively charged e s. Conductivity due to the positively charged holes. Compounds which can behave as Semi-Conductors: 12- 16 compounds These compounds are formed by the combination of group 12 and group 16 compounds. They possess an average valency of 4. Ex: ZnS, CdS, CdSe and HgTe 13- 15 compounds These compounds are formed by the combination of group 13 and group 15 compounds. They possess an average valency of 4. Ex: InSb, AlP and GaAs Magnetic Properties: Every substance has some magnetic properties associated with it. The origin of these properties lies in the es. Each e in an atom behaves like a tiny magnet. Its magnetic moment originates from two types of motions: Its orbital motion around the nucleus and its spin around its own axis. Classification of substances on the basis of their magnetic properties: Paramagnetic Weakly attracted by a magnetic field. Unpaired e-s O2, Cu2+, Fe3+, Cr3+, TiO, Ti2O3, Permanent magnetism. VO, VO2, CuO Diamagnetic Weakly repelled by a magnetic field. All e-s paired NaCl, MgSO4, TiO2, V2O5, C6H6(benzene) Ferromagnetic Strongly attracted by a magnetic field. Fe, Ni, Co, CrO2 Permanent magnetism. Antiferromagnetic Net dipole moment = 0 MnO, MnO2, FeO, Fe2O3, CoO, Cr2O3, Ferrimagnetic Net dipole moment 0 Fe3O4, ferrites like MgFe2O4 and ZnFe2O4

CHAPTER 2: SOLUTIONS A Solvent (present in large quantity) B Solute (components present other than solvent) Methods of Expressing Concentration: Mass of component Mass percent (w/w) = 100
Volume percent (v/v) =
Total mass of solution Volume of component

Mass by volume percent (w/v) = Mole fraction (xi) = Molarity (M) = *V T

Total volume of solution Mass of component

100

Total volume of solution

100 =
ni ni

*Wsolvent = Wsoln Wsolute = (Vsoln dsoln) Wsolute+

Number of moles of component Total number of moles of all components Number of moles of solute n 10 x d

Volume of solution (in litre) 1 V 1 T

V(in L)

MB

*M is an intensive quantity it varies inversely with Temperature+ M M Hence M with in Temp+ =

n WA (in Kg)

For any dilution problem: Mconc Vconc = Mdil Vdil Solutions: are the homogeneous mixtures of two or more than two components. Molality (m) =
Number of moles of solute Mass of solvent (in kilograms)

*m is an intensive quantity it does not depend on Temperature+ Parts per million (ppm) =
d M Number of parts of the component Total number of parts of all components of the solution

106 = (% w/w) 104

n-butyl chloride + n-butyl bromide

Relation between various methods of expressing concentration: =

1 m

MB 1000

CCl4 + CHCl3 ; Acetone + benzene; CCl4 + CH3OH; Cyclohexane + ethanol

ether; Water + HCl; Acetic acid + pyridine; Chloroform + benzene

Solubility: of a solute is its max. amt. that can be dissolved in a specified amt. of solvent at a specified temp. Solubility of a Solid in a Liquid: Solubility of a Gas in a Liquid: Vapour Pressure of Liquid Solution: Henrys Law: states at a constant temperature the solubility of gas in a liquid is directly proportional to the pressure of gas. Henrys law can also be stated as the partial pressure of gas in vapour phase is proportional to the mole fraction of the gas in the solution. pi xi pi = KH xi *KH Henrys Law Constant. It depends on Nature of gas, temperature+ Applications of Henrys law: To increase the solubility of CO2 in soft drinks and soda water, the bottle is sealed under high pressure. Scuba divers must cope with high concentrations of dissolved gases while breathing air at high pressure underwater. Increased pressure increases the solubility of atmospheric gases in blood. When the divers come towards surface, the pressure gradually decreases. This releases the dissolved gases and leads to the formation of bubbles of nitrogen in the blood. This blocks capillaries and creates a medical condition known as bends, which are painful and dangerous to life. To avoid bends, as well as, the toxic effects of high concentrations of nitrogen in the blood, the tanks used by scuba divers are filled with air diluted with helium (11.7% helium, 56.2% nitrogen and 32.1% oxygen). At high altitudes the partial pressure of oxygen is less than that at the ground level. This leads to low concentrations of oxygen in the blood and tissues of people living at high altitudes or climbers. Low blood oxygen causes climbers to become weak and unable to think clearly, symptoms of a condition known as anoxia. Raoults law: According to Raoults law for a solution of volatile liquids the partial vapour pressure of each component in the solution is directly proportional to its mole fraction. pi xi pi = poi xi *pi V.P. of ith component poi V.P. of pure component xi Mole Fraction of ith component+ Using Daltons law of partial pressure the total pressure of solution is calculated. ptotal = pA + pB = pA0 xA + pB0 xB = pA0 (1 xB) + pB0 xB = pA0 + (pB0 pA0) xB Classification of Liquid Liquid solutions on basis of Raoults Law. Ideal solutions Non- ideal solutions Positive deviation Negative deviation Obey Raoult's law at every range of Do not obey Raoult's law. Do not obey Raoult's law. concentration. Hmix = 0; neither heat is evolved nor Hmix > 0. Hmix < 0. absorbed during dissolution. Endothermic dissolution Exothermic dissolution Vmix = 0; No change in volume after Vmix > 0. Volume is Vmix < 0. Volume is dissolution. decreased during dissolution. decreased during dissolution. A-A, A-B, B-B interactions are nearly same, A-B attractive force should be A-B attractive force should be i.e., 'A' and 'B' are identical in shape, size weaker than A-A and B-B greater than A-A and B-B and character. attractive forces. 'A' and 'B' attractive forces. 'A' and 'B' { A-A A B B-B } have different shape, size and have different shape, size and character. character. { A-B < A-A B-B } { A-B > A-A B-B } The vapour pressure of a The vapour pressure of a solution is higher than that solution is lower than that predicted by Raoults Law. predicted by Raoults Law. Examples: Examples: Examples: n-hexane + n-heptane; Acetone +ethanol Acetone + aniline; bromoethane+chloroethane; Acetone + CS2: Acetone + chloroform; benzene + toluene; Water + methanol; CH3OH + CH3COOH ; chlorobenzene+bromobenzene; Water + ethanol; H2O + HNO3 ethyl bromide + ethyl iodide; CCl4 + toluene; Chloroform + diethyl

Azeotropes: are binary mixtures having same composition in liquid and vapour phase and boil at constant temperature. Liquids forming azeotrope cannot be separated by fractional distillation. There are two types of azeotropes called minimum boiling azeotrope and maximum boiling azeotrope. The solutions which show a large positive deviation from Raoults law form minimum boiling azeotrope at a specific composition. The solutions that show large negative deviation from Raoults law form maximum boiling azeotrope at a specific composition. Colligative properties: are the properties of solution which depend only on the number of solute particles (amount of solute) and not on the nature of solute. Relative lowering of vapour pressure: is directly proportional to mole fraction of solute. Hence it is a colligative property. p1/p1 = (p1 p1)/p1 = xB WB MA MB =
WA (RLVP)

Elevation of boiling point: We have learnt in Unit 5, Class XI, that the vapour pressure of a liquid increases with increase of temperature. It boils at the temperature at which its vapour pressure is equal to the atmospheric pressure. For example, water boils at 373.15 K (100 C) because at this temperature the vapour pressure of water is 1.013 bar (1 atmosphere). We have also learnt in the last section that vapour pressure of the solvent decreases in the presence of non-volatile solute. Fig. 2.7 depicts the variation of vapour pressure of the pure solvent and solution as a function of temperature. For example, the vapour pressure of an aqueous solution of sucrose is less than 1.013 bar at 373.15 K. In order to make this solution boil, its vapour pressure must be increased to 1.013 bar by raising the temperature above the boiling temperature of the pure solvent (water). Thus, the boilingpoint of a solution is always higher than that of the boiling point of the pure solvent in which the solution is prepared as shown in Fig. 2.7. Similar to lowering of vapour pressure, the elevation of boiling point also depends on the number of solute molecules rather than their nature. A solution of 1 mol of sucrose in 1000 g of water boils at 373.52 K at one atmospheric pressure. Let T0b be the boiling point of pure solvent and Tb be the boiling point of solution. The increase in the boiling point Tb = Tb Tb is known as elevation of boiling point. Experiments have shown that for dilute solutions the elevation of boiling point (Tb) is directly proportional to the molal concentration of the solute in a solution. Thus Tb m..(2.29) or Tb = Kbm.(2.30) Here m (molality) is the number of moles of solute dissolved in 1 kg of solvent and the constant of proportionality, Kb is called Boiling Point. Elevation Constant or Molal Elevation Constant (Ebullioscopic Constant). The unit of Kb is K kg mol-1. Values of Kb for some common solvents are given in Table 2.3. If w2 gram of solute of molar mass M2 is dissolved in w1 gram of solvent, then molality, m of the solution is given by the expression: m = w2/M2/1000 w2 = 1000 w2 M2 w1(2.31) Substituting the value of molality in equation (2.30) we get Tb = Kb 1000 w2/M2 w1.(2.32) M2 = 1000 w2 Kb/Tb w1 (2.33) Thus, in order to determine M2, molar mass of the solute, known mass of solute in a known mass of the solvent is taken and Tb is determined experimentally for a known solvent whose Kb value is known.

Depression of freezing point: The lowering of vapour pressure of a solution causes a lowering of the of Freezing freezing point compared to that of the pure solvent (Fig. 2 8). We know that at the freezing point of a substance, the solid phase is in dynamic equilibrium with the liquid phase. Thus, the freezing point of a substance may be defined as the temperature at which the vapour pressure of the substance in its liquid phase is equal to its vapour pressure in the solid phase. A

solution will freeze when its vapour pressure equals the vapour pressure of the pure solid solvent as is clear from Fig. 2.8. According to Raoults law, when a non-volatile solid is added to the solvent its vapour pressure decreases and now it would become equal to that of solid solvent at lower temperature. Thus, the freezing point of the solvent decreases. Let Tf be the freezing point of pure solvent and Tf be its freezing point when non-volatile solute is dissolved in it. The decrease in freezing point. Tf = Tf Tf is known as depression in freezing point. Similar to elevation of boiling point, depression of freezing point (Tf) for dilute solution (ideal solution) is directly proportional to molality, m of the solution. Thus, Tf m or Tf = Kfm.(2.34) The proportionality constant, Kf, which depends on the nature of the solvent is known as Freezing Point Depression Constant or Molal Depression Constant or Cryoscopic Constant. The unit of Kf is K kg mol-1. Values of Kf for some common solvents are listed in Table 2.3. If w2gram of the solute having molar mass as M2, present in w1 gram of solvent, produces the depression in freezing point Tf of the solvent then molality of the solute is given by the equation (2.31). m = w2 / M2/w1/1000(2.31) Substituting this value of molality in equation (2.34) we get: Tf = K f w2 / M2/w1/1000 Tf = Kf w2 1000. (2.35) M2 /w1 M2 = Kf w2 1000/Tf w1 (2.36) Thus for determining the molar mass of the solute we should know the quantities w1, w2, Tf, along with the molal freezing point depression constant. The values of Kf and Kb, which depend upon the nature of the solvent, can be ascertained from the following relations. Kf= R M1 Tf2/ 1000 fus H. (2.37) Kb= R M1 Tb2/1000 vap H (2.38) Here the symbols R and M1 stand for the gas constant and molar mass of the solvent, respectively and Tf and Tb denote the freezing point and the boiling point of the pure solvent respectively in kelvin. Further, fusH and vapH represent the enthalpies for the fusion and vapourisation of the solvent, respectively. Osmotic pressure: There are many phenomena which we observe in nature or at home. For example, raw mangoes shrivel when pickled in brine (salt water); wilted flowers revive when placed in fresh water, blood cells collapse when suspended in saline water, etc. If we look into these processes we find one thing common in all, that is, all these substances are bound by membranes. These membranes can be of animal or vegetable origin and these occur naturally such as pigs bladder or parchment or can be synthetic such as cellophane. These membranes appear to be continuous sheets or films, yet they contain a network of submicroscopic holes or pores. Small solvent molecules, like water, can pass through these holes but the passage of bigger molecules like solute is hindered. Membranes having this kind of properties are known as semipermeable membranes (SPM). Assume that only solvent molecules can pass through these semi- permeable membranes. If this membrane is placed between the solvent and solution as shown in Fig. 2.9, the solvent molecules will flow through the membrane from pure solvent to the solution. This process of flow of the solvent is called osmosis. The flow will continue till the equilibrium is attained. The flow of the solvent from its side to solution side across a semipermeable membrane can be stopped if some extra pressure is applied on the solution. This pressure that just stops the flow of solvent is called osmotic pressure of the solution. The flow of solvent from dilute solution to the concentrated solution across a semipermeable membrane is due to osmosis. The important point to be kept in mind is that solvent molecules always flow from lower concentration to higher concentration of solution. The osmotic pressure has been found to depend on the concentration of the solution. The osmotic pressure of a solution is the excess pressure that must be applied to a solution to prevent osmosis, i.e., to stop the passage of solvent molecules through a semipermeable membrane into the solution. This is illustrated in Fig. 2.10. Osmotic pressure is a colligative property as it depends on the number of solute molecules

and not on their identity. For dilute solutions, it has been found experimentally that osmotic pressure is proportional to the molarity, C of the solution at a given temperature T. Thus: =CRT(2.39) Here is the osmotic pressure and R is the gas constant. = (n2 /V) R T..(2.40) Here V is volume of a solution in litres containing n2 moles of solute. If w2 grams of solute, of molar mass, M2 is present in the solution, then n2 = w2 / M2 and we can write, V= w2R T/M2.(2.41) or M2 = w2R T/ V.(2.42) Thus, knowing the quantities w2, T, and V we can calculate the molar mass of the solute. Measurement of osmotic pressure provides a other method of determining molar masses of solutes. This method is widely used to determine molar masses of proteins, polymers and othermacromolecules. The osmotic pressure method has the advantage over other methods as pressure measurement is around the room temperature and the molarity of the solution is used instead of molality. As compared to other colligative properties, its magnitude is large even for very dilute solutions. The technique of osmotic pressure for determination of molar mass of solutes is particularly useful for biomolecules as they are generally not stable at higher temperatures and polymers have poor solubility. Two solutions having same osmotic pressure at a given temperature are called isotonic solutions. When such solutions are separated by semipermeable membrane no osmosis occurs between them. For example, the osmotic pressure associated with the fluid inside the blood cell is equivalent to that of 0.9% (mass/ volume) sodium chloride solution, called normal saline solution and it is safe to inject intravenously. On the other hand, if we place the cells in a solution containing more than 0.9% (mass/volume) sodium chloride, water will flow out of the cells and they would shrink. Such a solution is called hypertonic. If the salt concentration is less than 0.9% (mass/volume), the solution is said to be hypotonic. In this case, water will flow into the cells if placed in this solution and they would swell. The phenomena mentioned in the beginning of this section can be explained on the basis of osmosis. A raw mango placed in concentrated salt solution loses water via osmosis and shrivel into pickle. Wilted flowers revive when placed in fresh water. A carrot that has become limp because of water loss into the atmosphere can be placed into the water making it firm once again. Water will move into them through osmosis. When placed in water containing less than 0.9% (mass/volume) salt, blood cells collapse due to loss of water by osmosis. People taking a lot of salt or salty food experience water retention in tissue cells and intercellular spaces because of osmosis. The resulting puffiness or swelling is called edema. Water movement from soil into plant roots and subsequently into upper portion of the plant is partly due to osmosis. The preservation of meat by salting and of fruits by adding sugar protects against bacterial action. Through the process of osmosis, a bacterium on salted meat or candid fruit loses water, shrivels and dies. Reverse Osmosis and Water Purification The direction of osmosis can be reversed if a pressure larger than the osmotic pressure is applied to the solution side. That is, now the pure solvent flows out of the solution through the semi permeable membrane. This phenomenon is called reverse osmosis and is of great practical utility. Reverse osmosis is used in desalination of sea water. A schematic set up for the process is shown in Fig. 2.11. When pressure more than osmotic pressure is applied, pure water is squeezed out of the sea water through the membrane. A variety of polymer membranes are available for this purpose. The pressure required for the reverse osmosis is quite high. A workable porous membrane is a film of cellulose acetate placed over a suitable support. Cellulose acetate is permeable to water but impermeable to impurities and ions present in sea water. These days many countries use desalination plants to meet their potable water requirements. Abnormal Molar Masses We know that ionic compounds when dissolved in water dissociate into cations and anions. For example, if we dissolve one mole of KCl (74.5 g) in water, we expect one mole each of K+ and Cl ions to be released in the solution. If this happens, there would be two moles of particles in the solution. If we ignore interionic attractions, one mole of KCl in one kg of water would be expected to increase the boiling point by 2 0.52 K = 1.04 K. Now if we did not know about the degree of dissociation, we could be led to conclude that the mass of 2 mol particles is 74.5 g and the mass of one mole of KCl would be 37.25 g. This brings into light the rule that, when there is dissociation of solute into ions, the experimentally determined molar mass is always lower than the true value.

Molecules of ethanoic acid (acetic acid) dimerise in benzene due to hydrogen bonding. This normally happens in solvents of low dielectric constant. In this case the number of particles is reduced due to dimerisation. Association of molecules is depicted as follows: It can be undoubtedly stated here that if all the molecules of ethanoic acid associate in benzene, then Tb or Tf for ethanoic acid will be half of the normal value. The molar mass calculated on the basis of this Tb or Tf will, therefore, be twice the expected value. Such a molar mass that is either lower or higher than the expected or normal value is called as abnormal molar mass. In 1880 vant Hoff introduced a factor i, known as the vant Hoff factor, to account for the extent of dissociation or association. This factor i is defined as: i = Normal molar mass/ Abnormal molar mass = Observed colligative property / Calculated colligative property i =(Total number of moles of particles after association/dissociation)/(Number of moles of particles before association/dissociation) Here abnormal molar mass is the experimentally determined molar mass and calculated colligative properties are obtained by assuming that the non-volatile solute is neither associated nor dissociated. In case of association, value of i is less than unity while for dissociation it is greater than unity. For example, the value of i for aqueous KCl solution is close to 2, while the value for ethanoic acid in benzene is nearly 0.5. Inclusion of vant Hoff factor modifies the equations for colligative properties as follows: Relative lowering of vapour pressure of solvent, (p1 p1)/p1 = i.(n2)/n1 Elevation of Boiling point, Tb = i Kb m Depression of Freezing point, Tf = i Kf m Osmotic pressure of solution, = i n2 R T / V Table 2.4 depicts values of the factor, i for several strong electrolytes. For KCl, NaCl and MgSO4, i approach 2 as the solution becomes very dilute. As expected, the value of i gets close to 3 for K2SO4.

CHAPTER 4: CHEMICAL KINETICS Chemical Kinetics: is the branch of chemistry that deals with the study of reaction rates and their mechanisms. Rate of Reaction: is defined as the change in concentration of reactant (or product) in unit time. Unit of rate of reaction is molL-1s-1

Rate = k*A+x*B+y FACTORS AFFECTING RATE OF REACTION1. Concentration of reactant 2. Surface area 3. Temperature 4. Nature of reactant 5. Presence of catalyst 6. Radiation Molecularity of a reaction: Total number of atoms, ions or molecules of the reactants involved in the reaction is termed as its molecularity. It is always in whole number. It is never more than three. It cannot be zero. Order of a reaction: The sum of the exponents (power) of the concentration of reactants in the rate law is termed as order of the reaction. It can be in fraction. It can be zero also. Half- life of a reaction: The time taken for a reaction, when half of the starting material has reacted is called half- life of a reaction. For first order reaction t1/2 = ln2/k , where k is rate constant. It is independent of initial concentration for first order reaction. Pseudo first order reaction: The reaction which is bimolecular but order is one is called pseudo first order reaction. This happens when one of the reactants is in large excess. E.g., acidic hydrolysis of ester (ethyl acetate). CH3COOC2H5 + H2O CH3COOH + C2H5OH Activation energy (Ea): It is extra energy which must be possessed by reactant molecules so that collision between reactant molecules is effective and leads to the formation of product molecules. Arrhenius equation of reaction rate: It gives the relation between rate of reaction and temperature. K = Ae -Ea/RT ,where k = rate constant, A = frequency factor, Ea = energy of activation R = gas constant, T = temperature in Kelvin, ln k = ln A - Ea/RT log k = log A - Ea/2.303RTMechanism of reaction: The sequence of elementary processes leading to the overall stoichiometry of a chemical reaction is known as mechanism of a reaction. Activated complex: It is defined as unstable intermediate formed between reacting molecules. It is highly unstable and readily changes into product. Rate determining step: The slowest step in the reaction mechanism is called rate determining step. The number of collisions per second per unit volume of the reaction mixture is known as collision frequency (Z).

CHAPTER 5: SURFACE CHEMISTRY Adsorption: is a surface phenomenon in which the conc. of molecules of a given substance is more at the surface than in the bulk. Adsorbate: is the substance which gets adsorbed on the surface of another substance. Adsorbent: is the substance present in bulk, on whose surface adsorption takes place. Desorption: The process of removing an adsorbed substance from a surface on which it is adsorbed is called desorption. Absorption: It is the phenomenon in which a substance is uniformly distributed all over the surface. Absorption Adsorption It is the phenomenon in which a substance is uniformly The accumulation of molecular species at the surface distributed throughout the bulk of the solid. rather than in the bulk of a solid or liquid is termed as adsorption. It is a bulk phenomenon. It is a surface phenomenon.
The concentration is uniform throughout the bulk of The concentration of adsorbate increases only at the solid. surface of the adsorbent. Sorption: When adsorption and absorption take place simultaneously, it is called sorption. Enthalpy or heat of adsorption: Adsorption generally occurs with release in energy, i.e., it is exothermic in nature. The enthalpy change for the adsorption of one mole of an adsorbate on the surface of adsorbent is called enthalpy or heat of adsorption. Types of adsorption: Physical adsorption or physisorption: If the adsorbate is held on a surface of adsorbent by weak van der Waals forces, the adsorption is called physical adsorption or physisorption. Chemical adsorption or chemisorption: If the forces holding the adsorbate are as strong as in chemical bonds, the adsorption process is known as chemical adsorption of chemisorption. Physical adsorption (Physisorption) Chemical adsorption (Chemisorption)

For a reaction R P, the behaviour of the concentration of the reactant and product, as the reaction proceeds, is shown graphically. Average rate: is the rate of reaction measured over a long period of time. ;[] :[] Avg rate = = Instantaneous rate: is the rate of reaction when the average rate is taken over a particular moment of time. ;d[R] :d[P] Instantaneous rate = = dt dt Rate Law/Equation: is the expression which relates the rate of reaction with concentration of the reactants. The constant of proportionality k is known as rate constant. For a reaction: aA + bB cC + dD

It is reversible The amount of gas depends upon nature of gas, i.e., easily liquefiable gases like NH3, CO2, gas adsorbed to greater extent than H2 and He. Higher the critical temperature of gas, more will be the extent of adsorption. The extent of adsorption increases with increase in surface area, e.g. porous and finely divided metals are good adsorbents. There are weak van der Waals forces of attraction between adsorbate and adsorbent. It has low enthalpy of adsorption (20 40 kJ mol-1)

It is irreversible The amount of gas adsorbed is not related to critical temperature of the gas.

It also increases with increase in surface area.

Low temperature is favourable. No appreciable activation energy is needed. It forms multimolecular layers. Factors affecting adsorption of gases on solids: a. Nature of adsorbate: Physical adsorption is non-specific in nature and therefore every gas gets adsorbed on the surface of any solid to a lesser or greater extent. However, easily liquefiable gases like NH3. HCl, CO2, etc. which have higher critical temperatures are absorbed to greater extent whereas H2, O2, N2 etc. are adsorbed to lesser extent. The chemical adsorption being highly specific, therefore, a gas gets adsorbed on specific solid only if it enters into chemical combination with it. b. Nature of adsorbent: Activated carbon, metal oxides like aluminum oxide, silica gel and clay are commonly used adsorbents. They have their specific adsorption properties depending upon pores. c. Specific area of the adsorbent: The greater the specific area, more will be the extent of adsorption. That is why porous or finely divided forms of adsorbents adsorb larger quantities of adsorbate. The pores should be large enough to allow the gas molecules to enter. d. Pressure of the gas: Physical adsorption increases with increase in pressure. Adsorption isotherm: The variation in the amount of gas adsorbed by the adsorbent with pressure at constant temperature can be expressed by means of a curve is termed as adsorption isotherm. Freundlich Adsorption isotherm: The relationship between and pressure of the gas at constant temperature is called adsorption isotherm and is given by x/m x/m = kP 1/n (n > 1) Where x- mass of the gas adsorbed on mass m of the adsorbent and the gas at a particular temperature k and n depends upon the nature of gas and the solid x/m first increases with increase in pressure at low pressure but becomes independent of pressure at high pressure.

There is strong force of attraction similar to chemical bond. It has enthalpy heat of adsorption (180 240 kJ mol1) High temperature is favourable. High activation energy is sometimes needed. It forms unimolecuar layers.

N2 + 3H2 2NH3 , Here Fe(s) is catalyst but Mo(s) is promoter Catalytic poisons (Inhibitors): The substances which decrease the activity of catalyst are called catalytic poisons or inhibitors e.g., arsenic acts as catalytic poison in the manufacture of sulphuric acid by contact process. Types of catalysis: a. Homogeneous catalysis: When the catalyst and the reactants are in the same phase, this kind of catalytic process is known as homogeneous catalysis. b. Heterogeneous catalysis: When the catalyst and the reactants are in different phases, the catalytic process is said to be heterogeneous catalysis. Activity of catalyst: The ability of a catalyst to increase the rate of a chemical reaction is called activity of a catalyst. Selectivity of catalyst: It is the ability of catalyst to direct a reaction to yield a particular product (excluding others). For example: CO and H2 react to form different products in presence of different catalysts as follows: Shape selective catalysis: The catalysis which depends upon the pore structure of the catalyst and molecular size of reactant and product molecules is called shape- selective catalysis. E.g. Zeolites are shape selective catalysts due to their honey- comb structure. Enzymes: Enzymes are complex nitrogenous organic compounds which are produced by living plants and animals. They are actually protein molecules of high molecular mass. They are biochemical catalysts Steps of enzyme catalysis: Binding of enzyme to substrate to form an activated complex Decomposition of the activated complex to form product Characteristics of enzyme catalysis: i) They are highly efficient. One molecule of an enzyme can transform 106 molecules of reactants per minute. ii) They are highly specific in nature, e.g., urease catalysis hydrolysis of urea only. iii) They are active at optimum temperature (298 310 K). The rate of enzyme catalysed reaction becomes maximum at a definite temperature called the optimum temperature. iv) They are highly active at a specific pH called optimum pH. v) Enzymatic activity can be increased in presence of coenzymes which can be called as promoters. vi) Activators are generally metal ions Na+, Co2+ and Cu2+ etc. They weakly bind to enzyme and increase its activity. vii) Influence of inhibitors (poison): Enzymes can also be inhibited or poisoned by the presence of certain substances. Distinction between true solution, colloids and Suspension True solution Colloids Suspension It is homogeneous It appears to be homogeneous but is It is heterogeneous actually heterogeneous The diameter of the particles is less The diameter of the particles is 1 nm The diameter of the particles are than 1 nm to 1000 nm larger than 1000 nm It passes through filter paper It passes through ordinary filter It does not pass through filter paper paper but not through ultra-filters

Taking logarithm on both sides, we get, 1 log(x/m) = log k + log()

If we plot a graph between log(x/m) and log P, we get a straight line. The slope of the line is 1/n and intercept will be equal to log k.

Catalyst: Substances which alter the rate of a chemical reaction and themselves remain chemically and quantitatively unchanged after the reaction are known as catalysts and the phenomenon is known as catalysis. Promoters: Those substances which increase the activity of catalyst are called promoters. Example: Mo is promoter whereas Fe is catalyst in Habers Process.

Its particles cannot be seen under a microscope

Its particles can be seen by a powerful microscope due to scattering of light

Its particles can be seen even with naked eye

Colloids: A colloid is a heterogeneous system in which one substance is dispersed as very fine particles in another substance called dispersed medium. Dispersed phase: The substance which is dispersed as very fine particles is called dispersed phase. Dispersion medium: The substance present in larger quantity is called dispersion medium. Classification of colloids on the basis of the physical state of dispersed phase and dispersion medium: Dispersed phase Dispersion medium Name Examples

Classification of colloids on the basis of nature of interaction between dispersed phase and dispersion medium: Lyophobic sols Lyophilic sols These colloids are liquid hating. These colloids are liquid loving. In these colloids the particles of dispersed phase have no In these colloids, the particles of dispersed phase have affinity for the dispersion medium. great affinity for the dispersion medium. They are not stable. They are stable. They can be prepared by mixing substances directly. They cannot be prepared by mixing substances directly. They are prepared only by special methods They need stabilizing agents for their preservation. They do not need stabilizing agents for their preservation. They are irreversible sols. They are reversible sols. Classification of colloids on the basis of types of particles of the dispersed phase: a. Multimolecular colloids: The colloids in which the colloidal particles consist of aggregates of atoms or small molecules. The diameter of the colloidal particle formed is less than 1 nm. b. Macromolecular colloids: These are the colloids in which the dispersed particles are themselves large molecules (usually polymers). Since these molecules have dimensions comparable to those of colloids particles, their dispersions are called macromolecular colloids, e.g., proteins, starch and cellulose form macromolecular colloids. c. Associated colloids (Micelles): Those colloids which behave as normal, strong electrolytes at low concentrations, but show colloidal properties at higher concentrations due to the formation of aggregated particles of colloidal dimensions. Such substances are also referred to as associated colloids. Kraft Temperature (Tk): Micelles are formed only above a certain temperature called Kraft temperature. Critical Micelle Concentration (CMC): Micelles are formed only above a particular concentration called critical micelle concentration. Soaps: Soaps are sodium or potassium salts of higher fatty acids e.g., sodium stearate CH3(CH2)16COO-Na+ Methods of preparation of colloids: a. Chemical methods: Colloids can be prepared by chemical reactions leading to the formation of molecules. These molecules aggregate leading to formation of sols. b. Electrical disintegration or Bredigs Arc method: In this method, electric arc is struck between electrodes of the metal immersed in the dispersion medium. The intense heat produced vaporizes the metal which then condenses to form particles of colloidal size. c. Peptization: Peptization may be defined as the process of converting a precipitate into colloidal sol by shaking it with dispersion medium in the presence of a small amount of electrolyte. The electrolyte used for this purpose is called peptizing agent. 35.Purification of colloids: a. Dialysis: It is a process of removing a dissolved substance from a colloidal solution by means of diffusion through a suitable membrane. b. Electro dialysis. The process of dialysis is quite slow. It can be made faster by applying an electric field if the dissolved substance in the impure colloidal solution is only an electrolyte. c. Ultrafiltration: Ultrafiltration is the process of separating the colloidal particles from the solvent and soluble solutes present in the colloidal solution by specially prepared filters, which are permeable to all substances except the colloidal particles.

d. Ultracentrifugation: In this process, the colloidal solution is taken in a tube which is placed in ultracentrifuge. On rotating the tube at very high speed, the colloidal particles settle down at the bottom of the tube and the impurities remain in solution. The settled particles are mixed with dispersion medium to regenerate the sol. Properties of colloids: a. Colour: The colour of colloidal solution depends upon the wavelength of light scattered by the colloidal particles which in turn depends upon the nature and size of particles. The colour also depends upon the manner in which light is received by the observer. b. Brownian movement: Colloidal particles move in zig zag path. This type of motion is due to colliding molecules of dispersion medium constantly with colloidal particles. c. Colligative properties: The values of colligative properties (osmotic pressure, lowering in vapour pressure, depression in freezing point and elevation in boiling point) are of small order as compared to values shown by true solutions at the same concentrations. d. Tyndall effect: The scattering of a beam of light by colloidal particles is called Tyndall effect. The bright cone of light is called the Tyndall cone. e. Charge on colloidal particles: Colloidal particles always carry an electric charge. The nature of this charge is the same on all the particles in a given colloidal solution and may be either positive or negative. Positively charged colloids Negatively charged colloids Hydrated metallic oxides such as Fe2O3.xH2O, Metallic sulphides like As2S3, Sb2S3 sols Cr2O3.xH2O, Al2O3.xH2O Basic dye stuff like malachite green, methylene blue sols Acid dye stuff like eosin, methyl orange, Congo red sols Haemoglobin (blood) Starch sol, gum, gelatin, clay, charcoal, egg albumin, etc. f. Helmholtz electrical double layer: When the colloidal particles acquire negative or positive charge by selective adsorption of one of the ions, it attracts counter ions from the medium forming a second layer. The combination of these two layers of opposite charges around colloidal particles is called Helmholtz electrical double layer. g. Electrokinetic potential or zeta potential: The potential difference between the fixed layer and the diffused layer of opposite charges is called electrokinetic potential or zeta potential. h. Electrophoresis: The movement of colloidal particles under an applied electric potential is called electrophoresis. i. Coagulation or precipitation: The process of settling of colloidal particles as precipitate is called coagulation. Hardy Schulze rules: i) Oppositely charged ions are effective for coagulation. ii) The coagulating power of electrolyte increases with increase in charge on the ions used for coagulation, e.g. Al3+ > Ba2+ > Na+ for negatively charged colloids. *Fe (CN)6+4- > PO43- > SO42- > Cl- for positively charged colloids Types of emulsions: a. Water dispersed in oil: When water is the dispersed phase and oil is the dispersion medium. E.g. butter b. Oil dispersed in water: When oil is the dispersed phase and water is the dispersion medium. E.g. milk Emulsification: The process of stabilizing an emulsion by means of an emulsifier. Emulsifying agent: The substances which are added to stabilize the emulsions are called emulsifying agents or emulsifiers. E.g. soaps, gum Demulsification: The process of breaking an emulsion into its constituent liquids is called demulsification by freezing, boiling, centrifugation or some chemical methods.

CHAPTER 6: METALLURGY Metallurgy: is the entire scientific and technological process used for isolation of the metal from its ores. Minerals: are naturally occurring substances present in the earths crust which are obtained by mining. Ores: are those minerals from which metal can be extracted profitably and conveniently. Gangue: is the earthy or undesirable material present in ore. Flux: is a substance which combines with gangue to form an easily fusible material called slag. Slag: is an easily fusible material which is formed when gangue combines with flux. Types of Ores:Oxide Ores MnO2(Pyrolusite), ZnO(Zincite), SnO2(Cassiterite or Tin Stone), Cu2O(Cuprite), Al2O3(Corundum), Al2O3.2H2O(Bauxite), Fe2O3(Haematite), Fe3O4(Magnetite) Carbonate Ores MgCO3(Magnesite), CaCO3(Lime Stone), FeCO3(Siderite), ZnCO3(Calamine), PbCO3(Cerussite), MgCO3.CaCO3(Dolomite) Sulphide Ores ZnS(Zinc Blende), HgS(Cinnabar), PbS(Galena), Cu2S(Copper Glance or Chalcocite), Ag2S(Silver Glance or Argentite), FeS2(Iron Pyrite),CuFeS2(Copper Pyrite) Halide Ores NaCl(Common/Rock Salt), AgCl(Horn Silver), CaF2(Fluorspar), Na3AlF6(Cryolite), KCl.MgCl2.6H2O(Carnalite) I. Concentration/Enrichment/Benefaction of Ore: is the process of removal of unwanted impurities from the ore.

Hydraulic washing (or gravity separation): is based on difference in densities of ore and gangue particles. Impure crushed ore is washed with a stream of water under pressure so that lighter impurities are washed away whereas heavy ores are left behind. It is used for conc. of lead and tin ore like SnO2 and PbCO3 2. Magnetic separation: is based on the difference in magnetic properties of ore and the gangue particles. It is used for conc. of iron, chromium and manganese ores like Fe3O4 and FeCr2O4 3. Froth Floatation Process: is based on the difference in the wettability of the ore and the gangue particles. Collectors are added to enhance the non-wettability of the mineral particles. Ex: pine oil, fatty acids and xanthates. Froth stabilizers are added to stabilize the froth. Ex: cresols, aniline. Depressants are added to speed up the formation of froth by one sulphide ore and depress the formation of froth by the second sulphide ore. Ex: In the case of an ore containing ZnS and PbS, the depressant used is NaCN. It combines with ZnS and forms a soluble complex while PbS forms stable froth. 1 ZnS + 4NaCN + H2O + O2 Na2[Zn(CN)4] + 2NaOH + S 2 4. Leaching (Chemical separation): is a process in which ore is treated with suitable solvent which dissolves the ore but not the impurities. Leaching of Bauxite (Baeyers process): Bauxite contains SiO2 as impurity. Al2O3 + 2NaOH + 3H2O 2Na[Al(OH)4] [Impure] [Sodium tetrahydroxido aluminate (III)] Na[Al(OH)4] + CO2 Al(OH)3 [white ppt.]+ NaHCO3 [soluble] Al(OH)3 Al2O3[pure] + 3H2O Leaching of Gold and Silver Ores (Mac-Arthur Cyanide Process): 4M + 8NaCN + 2H2O + O2 4Na[M(CN)2] + 4NaOH [M = Ag or Au] [Cyano Complex] Oxidation as O.S. changes from 0 to +1 2Na[M(CN)2] + Zn Na2[Zn(CN)4] + 2M Reduction as O.S. changes from +1 to 0 Here NaCN acts as complexing agent and Zn acts as reducing agent. II. Conversion of ore into oxide: It is easier to reduce oxide than sulphide or carbonate ore. Therefore, the given ore is converted into oxide by suitable method. Calcination Roasting Heating the ore strongly in the absence of air Heating the ore in a regular supply of O2 at a temp below M.P. of the metal Used for carbonate ores and hydrate ores Used for sulphide ores CO2(g) or H2O(g) is evolved SO2(g) is evolved Ex:ZnCO3 ZnO + CO2 Ex: 2ZnS + 3O2 2ZnO + 2SO2 CaCO3.MgCO3 CaO + MgO +2CO2 2PbS + 3O2 2PbO + 2SO2 Fe2O3.xH2O Fe2O3 + xH2O 2Cu2S + 3O2 2Cu2O + 2SO2 III. Reduction of metal oxide to metal: usually involves heating with reducing agent (C or CO or even another metal). The reducing agent removes oxygen from the metal oxide. Reduction of metal oxide is an endothermic process, H = +ve. Better reducing agent is decided by G value. 1. Reduction by heat: Metals low in the reactivity series can be obtained by heating their oxides. HgS + O2 Hg + SO2 2. Reduction by carbon or carbon monoxide(Smelting): Metals in the middle of the reactivity series can be obtained by heating their oxides in presence of reducing agents(C,CO) MxOy + yC xM + yCO ZnO + C Zn + CO ; Fe2O3 + 3C 2Fe + 3CO FeO + CO Fe + CO2 ; Fe2O3 + 3C 2Fe + 3CO 3. Reduction by aluminium (Alumino thermic process): Fe2O3 + 2Al 2Fe + Al2O3 (Used for welding broken rails) Cr2O3 + 2Al 2Cr + Al2O3 4. Reduction by hydrogen (Hydrometallurgy): H2 is used to extract Cu from low grade ores. CuO + H2 Cu + H2O The solution containing Cu2+(obtained by treating ore with acid) is treated H2 . Cu2+ (aq) + H2(g) Cu(s) + 2H+ (aq) 5. Auto/Self reduction: can only be used for Pb and Cu. 2Cu2O + Cu2S 6Cu + SO2

1.

6.

IV.

Electrolytic reduction: Metals high in the reactivity series can be obtained from their ores by electrolytic reduction. Extraction of Al from Al2O3 (Hall-Heroult Process): Pure Al2O3 is mixed with Na3AlF6 (Cryolite)and CaF2 (Fluorspar) to lower its M.P. and increase its electrical conductivity. Cathode [Stainless Steel]: Al3+ + 3e Al Anode [Graphite]: C + O2- CO+ 2e C + 2O2- CO2 + 4e Extraction of Na from NaCl (Downs Cell ): CaCl2 is added to lower the M.P. of NaCl by forming impurity defect. Cathode [Steel]: Na+ + e Na Anode [Steel]: 2Cl- Cl2+ 2e Refining: is the process of converting impure metal into pure metal. 1. Distillation: is used when metal and impurities have a difference in their B.P. It is used for purification of low B.P. metals (e.g. Zn and Hg). Impure metal is heated so as to convert it into vapours which change into pure metal on condensation and are obtained as distillate. 2. Liquation: is used when metal and impurities have a difference in their M.P. It is used for purification of Sn and Pb. 3. Electrolytic refining: In this method, impure metal is taken as anode, pure metal is taken as cathode, and a soluble salt of metal is used as electrolyte. When electric current is passed, impure metal forms metal ions which are discharged at cathode forming pure metal. Anode [Impure metal]: M M+ + neCathode [Pure metal]: M+ + ne- M It is for purification of Cu and Zn. 4. Zone refining: is based on the principle that impurities are more soluble in the melt than in the solid state of the metal. This method is used for producing semiconductor and other metals of very high purity, e.g., Ge, Si, Ga and In. 5. Vapour phase refining: The metal is first converted into its volatile compound Then the volatile compound decomposes to give pure metal. Monds process: Ni + 4CO Ni(CO)4 Ni + 4CO [Impure] [Pure] van- Arkel method: It is used to get ultra-pure metals.

M + 2I2 MI4 M + 2I2 {where M = Zr,Ti} [Impure] [Pure] 6. Chromatographic method: is based on the principle that different components of a mixture are adsorbed differently on a adsorbent. The mixture is put in a liquid or gaseous medium which is moved through the adsorbent. Different components are adsorbed at different levels on the column. Later the adsorbed components are removed (eluted) by using suitable solvents (eluant). Thermodynamic Principles of Metallurgy For a spontaneous/thermodynamically feasible reaction G = ve G = H TS *Here G = Gibbs free energy change, H = Enthalpy change, T = Temperature and S = Entropy change+ G = RTlnK = 2.303RTlogK [Here K = Equilibrium constant, R = 8.314 JK- mol-1, T = Temperature] From these facts the following conclusions can be made: As H = +ve for metallurgy, G becomes ve only when TS H, possible only at high temperature Reduction of metal oxide to metal is easier if the metal is obtained in the liquid state because if the metal is in the liquid (or gaseous) state, S > 0 and then TS H and the value of G becomes more ve G = ve means K = +ve and the reaction proceeds towards products Sometimes, a reaction may have G = ve but still it does not take place. This is because the reactant molecules are not able to cross the Ea barrier. The reaction is said to be thermodynamically feasible but kinetically forbidden.

Coupled reactions: If reactants and products of two reactions are put together in a system and the net G of two possible reactions is ve the overall reaction will take place. These reactions are called coupled reactions. Ellingham Diagram: is a plot of fG versus temperature. It helps us in predicting the feasibility of thermal reduction of an ore. These plots are mainly for oxide formation. [ 2xM(s) + O2(g) 2MxO(s) S = ve ] TS becomes ve and G with in temp ( +ve slope) At a given temp metal oxide with more ve G will reduce metal oxide of less ve G. In the Ellingham Diagram, low reduces high.

Limitations of Ellingham Diagram: It is based only on the thermodynamic concept. It does not take kinetics of reduction into consideration, i.e., how fast reduction will take place cannot be determined. The interpretation of G is based on equilibrium constant, K (G = RTlnK). Thus it is presumed that the reactants and products are in equilibrium. Electrochemical principles of Metallurgy: G = nFE [where n = no. of e s and E = Electrode potential of the redox couple] More reactive metals have large ve values of the electrode potential. So their reduction is difficult. If the difference of two E values corresponds to a positive E and consequently negative G, then the less reactive metal will come out of the solution and the more reactive metal will go to the solution. Metallurgy of Iron: Metallurgy of Copper: