MINIMUM LEARNING MATERIAL(MLM) Instruction:-After learning, take a test (TEST YOURSELF)which is given in the site.

THE SOLID STATE TERMS

Amorphous and Crystalline Solids Molecular solids Covalent or Network solid No of lattice points per unit cell No of atoms per unit cell (z ) Coordination Number Calculation of number of voids

EXPLANATIONS
Amorphous- short range order, Irregular shape eg-glass Crystalline Solids- long range order, regular shape eg : NaCl Ar, CCl4, H2O (ice) SiO2 diamond Simple cubic -4, BCC- 9, FCC 14 , End-Centred- 10 Simple cubic -1, BCC- 2, FCC 4 , End-Centred- 2 FCC- 6:6 BCC- 8:8 Let the number of close packed spheres be N, then: The number of octahedral voids generated = N The number of tetrahedral voids generated = 2N Simple Cubic a = 2r , BCC 4r = a3 FCC 4r = a2 Simple Cubic52.4% , BCC 68% , FCC 74%

Relation between r and a Packing Efficiency Calculations Involving Unit Cell Dimensions

Frenkel Defect:

Schottky Defect Metal excess defect due to anionic vacancies (F-centres )

Doping

n / p -type semiconductors 13 15 compounds &1216 compounds Paramagnetic substances

NA = 6.023 10 Ccation is dislocated to an interstitial site. It does not change the density of the solid. Frenkel defect is shown by ionic substance in which there is a large difference in the size of ions, for example, ZnS, AgCl, AgBr and AgI due to small size of Zn2+ and Ag+ ions. A vacancy defect. The number of missing cations and anions are equal. Density decreases. For example, NaCl, KCl, CsCl and AgBr. When NaCl heated in an atmosphere of Na vapour, the Na atoms deposited on the surface of the crystal. The Cl ions diffuse to the surface of the crystal and combine with Na atoms to give NaCl. The released electrons diffuse into the crystal and occupy anionic sites The anionic sites occupied by unpaired electrons are called F-centres They impart yellow colour to the crystals of NaCl. Similarly, excess of lithium makes LiCl crystals pink and excess of potassium makes KCl crystals violet (or lilac). The conductivity of intrinsic semiconductors is increased by adding an appropriate amount of suitable impurity. This process is called doping n- type : Si + As or Sb or Bi p-type: Si + B or Ga or In or Tl 13 15 compounds: InSb, AlP and GaAs. 12 16 compounds :ZnS, CdS, CdSe and HgTe Weakly attracted by a magnetic field. Examples: O 2, Cu2+, Fe3+, Cr3+

23

M=molar mass (g/mol)

a = edge length in cm ,

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Diamagnetic substances Ferromagnetism: Antiferromagnetism Ferrimagnetism:

Weakly repelled by a magnetic field. Example: H2O, NaCl and C6H6 A few substances like iron, cobalt, nickel, gadolinium and CrO 2 are attracted very strongly by a magnetic field. MnO. Domains oppositely oriented and cancel out magnetic moment domains aligned in parallel and anti-parallel directions in unequal numbers . Example: Fe3O4 (magnetite)

SOLUTIONS
Solid Solutions Temp. Vs Conc. Henrys law. Application of Henrys law. Temp and Solubilty of gas Raoults law for volatile liquids Ideal Solutions Gas in solid Solution of hydrogen in palladium Liquid in solid Amalgam of mercury with sodium Mass %, ppm, mole fraction and molality are independent of temperature, whereas molarity depends on temperature. This is because volume depends on temperature. At a constant temperature, the solubility of a gas in a liquid is directly proportional to the pressure of the gas. p = KH . x KH = Henrys law constant ( greater the KH value means lower the solubility.) 1.To increase the solubility of CO2 in soft drinks, the bottle is sealed under high pressure. 2. To avoid bends, the tanks used by scuba divers are filled with air diluted with helium Solubility of gas increases with decrease of temperature. It is due to this reason that aquatic species are more comfortable in cold waters rather than in warm waters. The partial vapour pressure of each component in the solution is directly proportional to its mole fraction p 1 x1 p1 = p10 x1 The solutions which obey Raoults law over the entire range of concentration are known as ideal solutions. ( For ideal solution mixH = 0, mixV = 0) Example : Solution of n-hexane and n-heptane, Positive deviation : A-B interactions are weaker than those between A-A or B-B, Example - Mixtures of ethanol and acetone Negative deviations : Forces between A-A and B-B are weaker than those between A-B Example- mixture of phenol + aniline. a mixture of chloroform +acetone Mixtures have same composition in liquid and vapour phase and boil at a constant temp. minimum boiling azeotrope(positive deviation) eg- 95% aq ethanol maximum boiling azeotrope(negative deviation) eg- 68% aq nitric acid Depend on the number of solute particles not upon their nature.

Non-ideal Solutions

Azeotropes Colligative properties Relative Lowering of Vapour Pressure

Elevation of Boiling Point

Depression of Freezing Point Osmosis Osmotic pressure Osmotic pressure() Solvent flows through the semi permeable membrane from pure solvent to the solution. The extra pressure applied on the solution that just stops the flow of solvent is called osmotic pressure of the solution

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Isotonic solutions Hypertonic Hypotonic Reverse Osmosis vant Hoff factor ( i ) Value of vant Hoff factor(i)

Two solutions having same osmotic pressure Higher osmotic pressure than a particular soln Lower osmotic pressure than a particular soln 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 Application : Desalination of sea water ratio of normal molar mass to experimentally determined molar mass or as the ratio of observed colligative property to the calculated colligative property. NaCl, KCl = 2 ; BaCl2 CaCl2 = 3 ; Na3PO4 = 4 ; Al2(SO4)3 , K4[Fe(CN)6] = 5 CH3COOH ( in benzene) =

ELECTROCHEMISTRY
Cell Notation Nernst Eqn Store CuSO4 in Zn pot? Electrochemical Series Relation between E0 / Kc & G R, G, , G* No. because the following reaction takes place Zn(s) + CuSO4(aq) ZnSO4 (aq) + Cu(s) ; F2(g) + 2e 2F ; E0 = 2.87 F2(g) is the strongest oxidizing element Li+ + e Li(s) ; E0 = 3.05 Li is the strongest reducing element A negative E0 means that the redox couple is a stronger reducing agent(Itself will be oxidized) :Zn(s) | Zn2+ (aq) || Cu2+(aq)| Cu(s) ; LOAN : Left / Oxidation /Anode / Negative

Molar Conductivity (m) Kohlrausch law & Ka The amount of chemical reaction which occurs at any electrode during electrolysis is proportional to the quantity of electricity passed through the electrolyte (solution or melt). The amounts of different substances liberated by the same quantity of electricity passing through the electrolytic solution are proportional to their chemical equivalent weights (Atomic Mass of Metal Number of electrons required to reduce the cation). Cathode : Na+(l) + e Na(s) Anode : Cl Cl2+e Cathode : H2O (l ) + e H2(g) + OH Anode : Cl Cl2+e + Cathode : H + e H2 Anode: 2H2O(l ) O2(g) + 4H+(aq) + 4e + Cathode : H + e H2 Anode: 2SO4 2 (aq) S2O8 2 (aq) + 2e Cathode : Ag+(aq) + e- Ag(s) Anode: Ag(s) Ag+(aq) + e+ Cathode : Ag (aq) + e Ag(s) Anode: 2H2O(l ) O2(g) + 4H+(aq) + 4e + Cathode : Cu (aq) + e Cu(s) Anode: 2H2O(l ) O2(g) + 4H+(aq) + 4e In the primary batteries, the reaction occurs only once, and cannot be reused again Anode(Zn) : Zn(s) Zn2+ + 2e Cathode(Graphite) : MnO2 + NH4+ + e MnO(OH) + NH3 The emf = 1.5 V. Anode(Zn-Hg) : Zn(Hg) + 2OH ZnO(s) + H2O + 2e Cathode(HgO-C) : HgO + H2O + 2e Hg(l ) + 2OH EMF= 1.35 V and remains constant during its life as the overall reaction does not involve any ion in solution whose concentration can change during its life time. Limiting molar conductivity of an electrolyte can be represented as the sum of the individual contributions of the anion and cation of the electrolyte.

Faradays 1st Laws Faradays 2nd Laws Electrolysis of NaCl (molten) NaCl (aq) H2SO4(dil) H2SO4(conc) AgNO3(aq)-Ag electrodes AgNO3(aq)- Pt electrodes CuCl(aq)- Pt electrodes Pri & Sec Batteries Dry Cell

Mercury Cell

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Lead Storage Battery

Fuel Cells

Corrosion of Iron (Rusting) Prevention of Corrosion

Anode : Pb Cathode : Pb packed with PbO2 Electrolyte : 38% H2SO4 Anode: Pb(s) + SO4 2(aq) PbSO4(s) + 2e Cathode: PbO2(s) + SO4 2(aq) + 4H+(aq) + 2e PbSO4 (s) + 2H2O (l ) On charging the battery the reaction is reversed Anode&Cathode : Porous C Electrolyte : Aq NaOH Cathode: O2(g) + 2H2O(l ) + 4e 4OH(aq) Anode: 2H2 (g) + 4OH(aq) 4H2O(l) + 4e The cell runs continuously as long as the reactants are supplied. Efficiency of about 70 % Pollution free. The water vapours produced during the reaction were condensed and added to the drinking water supply for the astronauts (Apollo space programme) Oxidation: Fe (s) Fe2+ (aq) +2e Reduction: O2 (g) + 4H+(aq) +4e 2H2O(l) Atomospheric oxidation : 2Fe2+(aq) + 2H2O(l) + O2(g) Fe2O3(s) + 4H+(aq) By covering the surface with paint or by some chemicals (e.g. bisphenol). / Cover the surface by other metals (Sn, Zn, etc.) that are inert or react to save the object. An electrochemical method (sacrificial electrode like Mg, Zn, etc.) which corrodes itself but saves the object.

CHEMICAL KINETICS
Rate of a Chemical Reaction For RP Average & Instantaneous Rate For 2HI(g) H2(g) + I2(g) Change in concentration of a reactant or product in unit time. Unit => mol L-1s1

Rate of reaction = Rate law is the expression in which reaction rate is given in terms of molar concentration of reactants with each term raised to some power, which may or may not be same as the stoichiometric coefficient of the reacting species in a balanced chemical equation. The rate expression for this reaction is : Rate [A]x [B]y => Rate = k [A]x [B]y k is the Rate const. (x , y from expts) The sum of powers of the concentration of the reactants in the rate law expression is called the order of that chemical reaction. If Rate = k [A]x [B]y Order = x + y The reactions taking place in one step are called Elementary Reactions For n th order reaction : mol1-n Ln-1 s-1 The number of reacting species taking part in an elementary reaction, which must collide simultaneously in order to bring about a chemical reaction is called molecularity of a reaction (values are limited from 1 to 3) The overall rate of the reaction is controlled by the slowest step in a reaction called the rate determining step The half-life of a reaction is the time in which the concentration of a reactant is reduced to one half of its initial concentration. It is represented as t 1/2.

Rate law / Rate equation / Rate expression For aA + bB cC + Dd Differential Rate Equation Order of a Reaction Elementary reactions Unit of rate constant Molecularity of a Reaction Rate Determining Step Half-life (t1/2) Zero Order Reactions (Integrated Rate Equation) First Order Reactions (Integrated Rate Equation) Dependence of t1/2 on [R]0 Example of Zero Order Reactions Radioactive decay

For zero order : t1/2 0. For first order reaction t 1/2 is independent of [R]0 The decomposition of gaseous ammonia on a hot platinum surface is a zero order reaction at high pressure. Rate = k [NH3]0 = k All natural and artificial radioactive decay of unstable nuclei take place by first order kinetics

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Pseudo First Order Reaction Activation Energy Arrhenius equation e -Ea /RT If k1 and k2 are rate constants at T1 and T2 Action of catalyst

When one of two reactants is present in large excess. During the hydrolysis of 0.01 mol of ethyl acetate with 10 mol of water The concentration of water does not get altered much during the course of the reaction and the reaction behaves as first order reaction. Such reactions are called pseudo first order reactions. Activation energy is given by the energy difference between activated complex and the reactant molecules k = A e -Ea /RT (exponential form) ln k = Ea/RT + ln A (logarithmic form) A is the Arrhenius factor or the frequency factor or pre-exponential factor The factor e -Ea /RT corresponds to the fraction of molecules that have kinetic energy greater than Ea

Collision frequency (Z)

Catalyst provides an alternate pathway or reaction mechanism by reducing the activation energy between reactants and products and hence lowering the potential energy barrier The number of collisions per second per unit volume of the reaction mixture. For A + B Products Rate = P.ZAB eEa/ RT P is probability or steric factor ZAB is collision frequency of reactants, A and B

SURFACE CHEMISTRY
Adsorption Adsorbate & Adsorbent. Desorption. Adsorption and Absorption Accumulation of molecular species at the surface rather than in the bulk of a solid or liquid. The substance adsorbed is called adsorbate. And the surface provider is called adsorbent. The process of removing an adsorbed substance from a surface. In adsorption, the substance is concentrated only at the surface while in absorption, the substance is uniformly distributed throughout the bulk of the solid. Sorption Both adsorption and absorption can take place simultaneously. Enthalpy of adsorption Adsorption is exothermic H is -ve. There is decrease in entropy, S is -ve. For a process to be spontaneous, G must be negative, so H should have sufficiently high-ve value. Surface area & Adsorption Adsorption increases with the increase of surface area of the adsorbent. Thus, finely divided metals and porous substances having large surface areas are good adsorbents. Physisorption van der Waals forces / not specific /reversible /easily liquefiable gases adsorbed readily./ Enthalpy of adsorption is low/ Low temperature is favourable / Multimolecular layers. Chemisorption chemical bond /highly specific / irreversible/Enthalpy of adsorption high / High temperature is favourable / / unimolecular layer. Adsorption Isotherm Variation of amount of gas adsorbed by the adsorbent with pressure at constant temperature can be expressed by means of a curve termed as adsorption isotherm. Freundlich isotherm X / m = k.P1/n (n > 1) log x/m = log k + 1/n log P Applications of Adsorption High vacuum/masks/Control of humidity/ Removal of colour/ catalysis/ curing diseases/ Promoters and Poisons N2(g) + 3H2(g) 2NH3(g) Homogeneous catalysis Reactants and the catalyst are in the same phase. Heterogeneous catalysis Reactants and the catalyst are in different phases. Activity of a solid catalyst Depends upon strength of chemisorption .Reactants must get adsorbed reasonably strongly. Selectivity of a catalyst The selectivity of a catalyst is its ability to direct a reaction to yield a particular product. Shape- Selective Catalysis Depends upon the pore structure of the catalyst and the size of the reactant and product by Zeolites molecules. Example:- ZSM-5 (a zeolite) converts alcohols directly into gasoline (petrol). Characteristics of enzyme Highly efficient/ Highly specific / active under optimum temperature& pH/ Increasing catalysis activity in presence of activators and co-enzymes/ Influence of inhibitors and poisons Catalysts used in industrial Habers process (NH3) Finely divided Fe, Mo - promoter; Ostwalds process(HNO3) Pt process. Contact process(H2SO4) Pt or vanadium pentoxide (V2O5); Colloids Diameters of the particles is between 1 and 1000 nm.

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Lyophilic colloids Lyophobic colloids Multimolecular colloids Macromolecular colloids Associated colloids (Micelles) Kraft Temperature (Tk) CMC Cleansing action of soaps

Electrical disintegration or Bredigs Arc method Peptization

Dialysis: Tyndall effect Conditions for Tyndall effect Charge on colloidal particles Origin of charge on colloidal particles

Zeta potential Electrophoresis Electroosmosis Coagulation(ppt) Reason of Coagulation Hardy-Schulze rule

Coagulating value Emulsions Demulsification Artificial Rain Formation of Delta

Electrical precipitation of smoke(Cottrellppter)

Liquid-loving/ can be reconstituted/ reversible/easily prepared/stable/ eg- gum, starch. Liquid-hating/ not be reconstituted/ irreversible/ prepared by special methods/ precipitated on addition of electrolytes/heating/shaking/ not stable./ eg metal sols , sulphide sols. Large number of atoms or molecules of a substance aggregate eg- gold sol , sulphur sol. Macromolecules in suitable solvents. Eg-starch, cellulose, proteins and enzymes; polythene. Substances at low conc behave as strong electrolytes, but at high conc exhibit colloidal behaviour due to the formation of aggregates(micelles.) eg- soaps and detergents. Formation of micelles takes place only above a particular temperature. Formation of micelles takes place only above a particular conc. Soap molecules form micelle around the oil droplet in such a way that hydrophobic part of the stearate ions is in the oil droplet and hydrophilic part projects out of the grease droplet like the bristles . Since the polar groups can interact with water, the oil droplet surrounded by stearate ions is now pulled in water and removed from the dirty surface. This process involves dispersion as well as condensation. Colloidal sols of metals such as gold, silver, platinum, etc., can be prepared. Process of converting a ppt into colloid 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. Removal of dissolved substance from colloidal by diffusion through a suitable membrane. Colloidal particles scatter light in all directions. Scattering of light illuminates the path of beam of the light. (i) Diameter of particles is not much smaller than wavelength of the light used; (ii) Refractive indices of the phase and medium differ greatly in magnitude +ve charged sols Hydrated metallic oxides,/methylene blue sol. /Haemoglobin (blood) -ve charged sols Metals,/ sulphides/ eosin, congo red / starch, gum, gelatin, clay,charcoal. Preferential adsorption of ions . The sol particles acquire positive or negative charge by preferential adsorption of +ve or ve ions. When two or more ions are present in the dispersion medium, preferential adsorption of the ion common to the colloidal particle usually takes place. AgI/I Potential difference between the fixed layer and the diffused layer. The movement of colloidal particles under an electric potential is called electrophoresis. If electrophoresis is prevented , it is observed that the dispersion medium begins to move in an electric field. The process of settling of colloidal particles is called coagulation or precipitation of the sol. Electrophoresis/mix oppositely charged sols/boiling/persistent dialysis/addition of electrolytes. The greater the valence of the flocculating ion added, the greater is its power to cause precipitation. For coagulation of a negative sol, : Al3+>Ba2+>Na+ For coagulation of a negative sol :[Fe(CN)6]4 > PO4 3 > SO4 2 > Cl Min. conc of an electrolyte in millimoles/L required to cause precipitation of a sol in 2 hours Liquid-liquid colloida (i) Oil dispersed in water (O/W type) - milk and vanishing cream . (ii) Water dispersed in oil (W/O type).- butter and cream. Emulsions can be broken into constituent liquids by heating, freezing, centrifuging, etc. By throwing electrified sand , spraying a sol of opposite charge to the clouds from aeroplane River water is a colloidal solution of clay. Sea water contains a number of electrolytes. When river water meets the sea water, the electrolytes present in sea water coagulate the colloidal solution of clay resulting in its deposition. The smoke, before it comes out from the chimney, is led through a chamber containing plates having a charge opposite to that carried by smoke particles. The particles on coming in contact with these plates lose their charge and get precipitated.

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GENERAL PRINCIPLES AND PROCESS OF EXTRACTION OF ELEMENTS

The most abundant elements in the earths crust: Oxygen > Silicon > Aluminum > Iron > Calcium Mineral: It is the combined state in which a metal occurs naturally in the crust of the earth. Ore: The mineral from which a metal can be profitably and conveniently extracted is called ore.i.e. All ores are minerals but all minerals are not ores. Gangue / Matrix: Earthly or undesired materials present in mineral are called gangue. Metallurgy: The entire scientific and technological process used for isolation of the metal from its ores is known as metallurgy.
Concentrated Ore Metal oxide Powdered Ore Pure metal
Reduction

Crushing and grinding

-Hydraulic washing -Magnetic separation -Froth Floatation -Leaching

-Calcination -Roasting

-Reduction with ' C ' -Reduction with ' CO ' -Reduction with ' Al ' -Electolitic Reduction

Crude metal

Concentration of ore

Conversion to oxide

Refining - Liquation -Distillation - Electrolysis - Zone refining - Vapour phase refining - Chromatographic method

Reactivity Series
Li K Ca Ore Electrometallurgy Crude metal Electrometallurgy Pyrometallurgy Thermometallurgy Na Mg Al

Ore

Reactivity

decreases Mn Zn Fe Ni Ore Pyrometallurgy Crude metal Pb Cu Moderately reactive elements Ag Hg Au Least reactive elements Ore Thermometallurgy

Highly reactive elements

Crude metal

Electrolytic reduction (Reducing agent is electron, which is powerful reducing agent ) Thermal reduction (Heating in presence of sutable reducing agent ) Simply heating ( In absence of reducing agent )

Hydraulic washing: This method is used when the ore particles are heavier than the gangue particles. E.g. Oxide ores Magnetic separation This is based on difference in magnetic properties of the ore component. Froth floatation method It is based on the difference in the wetting qualities of the gangue and sulfide ore particles with water and oil. Where as the ore particles are wetted by oil, the gangue particles are wetted by water. Collectors enhance non-wet ability of the mineral particles. e.g. Pine oil, fatty acid, xanthates, etc. Froth stabilizers stabilizes the forth e.g. Cresol, aniline, etc. Depressants are reagents used to suppress or depress the formation of forth. For example, ZnS and PbS can be separated from each other in the forth floatation process by the addition of small amounts of NaCN which act as depresent. NaCn selectively prevents ZnS from coming to the froth by forming soluble complex.

4 NaCN + Depressant

ZnS Ore

Na2 [ Zn ( CN )4 ] Soluble complex

Na 2S

But allows PbS to come with the froth.

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Leaching of alumina from Bauxite This process is followed if ore is soluble in suitable solvent. Bauxite contains SiO2, TiO2 and iron oxide as impurities. When bauxite ore is treated with Concn. NaOH, alumina dissolves as sodium meta aluminate and silica as sodium silicate leaving behind the impurities i.e. Iron oxide.

Al2O3 + 2 NaOH + 3 H 2O Alumia SiO2 + 2 NaOH Silica

2 Na [ Al (OH )4] Sodium meta aluminate

H 2O

Na2SiO3 + Sodium silicate

The solution is filtred and neutralised by passing CO2 gas, when hydrated alumina gets precipitated Al2O3.xH2O + 2 NaHCO3 leaving sodium silicate in the solution. 2 Na [Al (OH)4 ] + CO2
Hydrated alumina Al2O3 +

Hydrated alumina on heating give pure alumina. Leaching of Ag and Au from their ore.

Silver and gold ores are treated with dilute solution of NaCN or KCN in presence of air to form soluble complex. 4 Au + 8 NaCN + 2 H2O + O2 4 Na [ Au (CN)2 ] + 4 NaOH 4 Ag + 8 NaCN + 2 H2O + O2 4 Na [ Ag (CN)2 ] Na 2[ Zn (CN)4 ] + + 4 NaOH After filtration the solution treated with znic, which displace Ag and Au as precipitate. 2 Na [ Au (CN)2 ] 2 Na [ Ag (CN)2 ] + + Zn Zn 2 Au

Al2O3.xH2O

x H 2O

2 Slag : During metallurgy, flux is added which combines with gangue to form slag . FeO + Impurity Slag separates more easily from the ore than the gangue.

Na 2[ Zn (CN)4 ] + 2 Ag ( Precipitate ) ( soluble complex ) Roasting Calcination The process of converting an ore into its oxide by The process of converting an ore into its oxide by heating below its melting point in presence of air. heating below its melting point in absence of air. ZnO + CO2 ZnCO3 2 ZnS + 3O 2 ZnO + 2SO
2

SiO2 Flux

FeSiO3 Slag

Hydrometallurgy
The isolation of a metal present in the soluble complex by more reactive metal is called hydrometallurgy. Zinc is more reactive than copper, So Zn can displace Cu from solution of Cu2+

Zn

(S)

Cu2+

(aq)

Zn
Zn2+

2+ (aq)

Cu

(S)

To displace Zn from solution of ions, we need more reactive elements such as Al, Mg, Ca and K. But all these metals react with water forming their corresponding ions with the evolution of H2 gas. Thus Al, Mg, etc. can not be used to displace Zn from solution of Zn2+ ions. Thus, copper can be extracted by hydrometallurgy but not zinc. Electrometallurgy: [For highly reactive metals] Highly reactive metals can be isolated from their ores by the process of electrometallurgy. The strongest possible reducing agent is an electron; any ionic material can be reduce to their respective metal by electrolysis. For Electrolytic reduction can be performed by applying a potential difference, E G a E ( applied ) which is related to G as follows: nF reaction having G value 100 kj / mol, n= 1 and F = 96487 C Then E (applied ) is nearly 1.03 V But for this type of reduction, in terms of pyrometallurgy, require high temperature, at which the ore become volatile. Pyrometallurgy: ( Pyro means fire )- [For moderately reactive metals]

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The process of converting metal oxide in to metallic form upon strong heating with a suitable reducing agent, is known as pyrometallurgy. Moderately reactive metals can be isolated from their ores by the process of pyrometallurgy. [1] Thermite reaction: Reduction of metal oxide with aluminum. Cr 2O3 Al2O3 2 Cr 2 Al

[2] Smelting : Reduction of metal oxide with help of coke.

Thermo metallurgy ( For least reactive metal )

The metals can be isolated by simply heating the oxide of the metals.
2 HgO 2 Hg

O2

Ag2O

2 Ag

1 O 2 2

Distillation : This method is employed for purification of volatile metals ( Zn, Hg, Cd ) by heating the ore followed by condensation. Liquation : This method is used when the M.P of the metals are lower than those of the impurities. e.g. low melting metal Sn

Electrolytic refining ( Zn, Cu )

Anode : Impure metal ( Cu ) Cathode: Pure metal ( Cu ) Electrolyte : Soluble salt of same metal ( acidified CuSO4 solution )
The more basic metal remains in the solution and the less basic ones goes to the anode mud. Cathode: Cu 2+ + 2e Cu Anode: Cu Cu 2+ + 2e - ; Antimony, Selenium, Tellurium, Silver, Gold and Platinum, which are less basic in nature present as impurities in blister copper, collected as anode mud. Zone refining ( Ge, Si, B, Ga, In ) This method is based upon the principle that the impurities are more soluble in the molten state ( melt ) than in the solid state of the metal. i.e. When a molten solution of the impure metal is allowed to cool, the pure metal crystalises out while the impurities remain in the melt. Vapour phase refining ( Ni, Zr, Ti ) In this method, the impure metal is converted into a volatile compound by suitable method leaving behind the impurities. The volatile compound formed being unstable decomposes at an elevated temperature to give pure metal. 450 - 470 K 330 - 350 K Mond process Ni 4 CO Ni(CO)4 Ni 4 CO Impure Nickel Volatile Pure Nickel ( Nickel tetra carbonyl )

Van Arkel Method Zr 2 I2 Impure Zirconium

+ +

' W ' Filament 2 I2 Zr 1800 K Volatile Pure Zirconium

ZrI 4

Impure Titanium

Ti

2 I2

Volatile

Ti I4

Chromatographic Method # This method is based upon the principle that different components of a mixture are differently adsorbed on an adsorbent # The zone thus formed due to adsorption is called chromatogram. # The process of separation of the different components of the mixture from the adsorbent and their recovery with the help of a suitable solvent ( eluant ), is called elution. # The sample is dissolved in a mobile phase and then forced through the stationary phase, to form chromatogram # The stationary phase is selected in such a way that the impurities are more strongly adsorbed in the stationary phase than element to be purified.

Pure Titanium

Ti

2 I2

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Extraction of Znic
Ore Zinc blende / Sphalerite - ZnS; 673 K ZnO C Calamine - ZnCO3 ; Zincite - ZnO

Coke

Zn

CO

The metal is purified by fractional distillation.

Extraction of iron in the blast furnace

Ore Haematite Fe 2O3 , Magnetite Fe 3O 4 Temperature 2170 K Additive Coke (Reducing agent and fuel) and Lime stone (Basic Flux )
CaCO 3 CaO

CO 2

Flux
C

CaO

+ +

Impurity
O2 C CO CO CO

SiO2

Calcium silicate ( Slag )

CO 2 2 CO 2 Fe 3O 4 3 FeO Fe

CaSiO3

Coke
CO 2

= - 393.3 Kj = + 163.2 Kj

Pig iron The iron obtained from Blast furnace contain about 4% carbon is known as pig iron. Cast iron contain about 3% carbon, obtained by melting pig iron with scrap iron and coke using hot air blast. Wrought iron the purest form, is prepared from cast iron by oxidising impurities with haematite. Haematite oxidises carbon to carbon monoxide. Fe 2O3

+ 3 Fe 2O 3 + Fe 3O 4 + FeO +

+ +

CO 2 CO 2

CO 2

3C

2 Fe

3 CO

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Extraction of Copper
Ore
2 CuFeS2 2 FeS

Copper pyrites- CuFeS2 ;

Copper glance - Cu 2S ;
Cu 2S 2 FeO FeSiO3 Slag

Malachite - CuCO3.Cu ( OH )2 ; Cuprite - Cu 2O

O2

Roasting

+ FeO + Impurity
2 Cu2S 2 Cu2O

3 O2 SiO2 Flux 3 O2 Cu 2S
Partial oxidation

+ 2 FeS + + 2 SO2

SO2

Extraction of Aluminium
Ore Cathode -Steel;

The solidified copper obtained has blister copper. Bauxite - Al2O3.x H2O

+ +

+ 2 SO2 6 Cu + SO2 blistered appearance

2 Cu2O

due to the evolution of SO 2 and so it is called

( Hall - Heroult Process )

Cryolite - Na 3AlF6

Anode - Graphite To make alumina a good conductor of electricity. To lowers the melting point of the mix.

Pure Al2O3 mixed with Cryolite ( Na 3AlF6 ) or CaF2

Al2O 3

2 Al

3+

3O

2-

Cathode - Al Anode C

3+

+ 3e O
2-

Al ; CO + 2e
-

C + 2 O 2CO2 + 4 e The role of graphite as anode is to prevent the liberation of O 2 which may other wise oxidise some of the liberated Aluminium back to Al2O3 How is leaching carried out in case of low grade copper ores ? Copper is leached out from the low grade ores by using acid or bacteria in presence of air.
2 Cu

The solution containing Cu2+ is treated with scrap iron / H2 to get pure copper. Cu2+ Cu2+
(aq) (aq)

2 H2SO4

O2

2 CuSO4

2 H2O

+ +

H2 Fe

Cu Cu

+ +

2 H+

2 Fe2+

Ellingham diagram G = G
T S

G = G

Ve ( Less )

Phase change

S T

A reaction that proceeds with decrease of entropy ( S= Ve ) must have + ve slope.

G =
T

Ve ( More )

The slope becomes - ve for those reactions which proceed with increase of entropy ( S = Ve ) and S of a reaction remain nearly constant, so the value of G changes with temperature.

Defn- Ellingham diagrams are the graphs which represent the variation of standard free energy change ( G ) with temperature for the fomation of oxides of various elements. Characteristics [i] The curves always slope upwards because G value for formation of metal oxide increases with the rise in temperature. [ii] The sudden change in the slope indicates the phase change. This happens at the melting point and boiling point. [iii] For the formation of CO the G values gradually becomes more negative with rise in temperature. i.e. the graph slopes downward. [iv] Any metal oxide with lower G is more stable than the metal oxide with higher G . [v] The element involved in the formation of oxides placed lower in the diagram can reduce the oxide of the element placed higher in the diagram i.e. Cr 2O3 Al2 O3 2 Al 2 Cr Al O
O2 4 Cr + 3

2 Cr 2O 3 3

O3 2 Al 2 3

O2 l + G 4 A
3

T
Cr 2O 3

2 Cr

2 Al

www.cpprashanthschemistry.com own and no reducing agents are required to carry their reduction.
Limitation
2 Ag2O 4 Ag

[vi] Ag2O and HgO, placed at the top of Ellingham diagram, are quite unstable and they decompose of their

Page 11

Ellingham diagram give no idea about the kinetics of reaction.

O2

2 HgO

2 Hg

O2

Explain overall reaction for extraction of aluminium by Hall-Heroults process is the carbon 4 Al reduction i.e. 2 Al2O3 + 3 C + 3 CO2 3+ 2Al2O 3 2 Al ---------------[1] + 3O
Anode -(Graphite) O2CO C Cathode - [ Steel ] [Anode reaction X 3 ] C Al
3+ 3+

+ + +

C O
22-

CO CO2 CO2 Al

+ + +

2e 2e
-

2O + 3e

4e

Al
-

3+

[Cathode reaction X 4 ] = CO2 Al + 4e ]X 3 ]X 4 4 Al +

Cell reaction

+ +

2O 3e + 6O

22-

4 Al

3C

3 CO 2 -------------------[2]

Adding eqn(1) with (2) by multiplying suitable integer.

Al2O 3

2 Al3+
4 Al
4 Al

+
+

3 O23 CO 2
3 CO2

] X 2

4 Al

3+

+ 6O

2-

+
3C

3C

Why is the reduction of a metal oxide easier if the metal formed is in liquid state at the temperature of reduction ? The value of entropy change ( S ) of the reduction process is more on +ve side when the metal formed is in liquid state and the metal oxide being reduced is in solid state. Thus the value of G becomes more on negative side and the reduction becomes easier. Pyrometallurgical carbon reduction process is not applicable for the extraction of aluminium from bauxite ore, explain.
4 Al 3
(S)

2 Al2O 3

+ O2

(g)

2 Al2 O3 3

(S)

, G ( S = -ve since gas 1

solid) 2 mol gas)

.

G1 G2
.

2 C (s) + O2 (g) 2 C (s) + O2 (g)

2 Al2O 3 3 2 Al O 2 3 3

2 CO (g), G2 ( S = + ve since 1 mol 2 CO (g),

4 3 Al

For reduction of bauxite by carbon:

G 1

+
4 Al 3

O2

G2 G 1 G = G 2 G 1

G1

G2 G2

--------------

2000 C

2C

+ 2 CO

To get G negative ,

G1

G 2

i.e the reduction of bauxite by carbon will feasible above 2000 C . But at this temperature bauxite becomes O2 volatile. Therefore bauxite can not reduce by carbon. 2C Reducing nature of carbon ( coke ) [1] C
(S)

+ O2 ( g )
R

CO2 ( g ) n
P

S = 0
So G remain same.
.

O+ 2C

O2

C + O2
+ O

CO2

------------------

n [2] 2 C n

=1 + O2 ( g )

=1

2C

(S) R

2 CO ( g ) ; S n
P

0
.

=1

=2

983 K

2C O

So G becomes increasingly negative. [3] 2 CO

(g) R

T
.

+ O2 ( g ) =3

2 CO2 ( g ) ; S n
P

=2

So G becomes positive.

So it is concluded that carbon ( coke ) act as reducing agent by changing to carbon monoxide above 983 k Out of C and CO which is a better reducing agent for ZnO ? Above 1073 K

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.

G(CO,CO ) 2
CO ,

G ( Zn, ZnO )
CO

G ( C, CO )

So, C can reduce ZnO to Zn but not

Page 12

So, out of C and

C is the better reducing agent than CO for ZnO

Reduction of Zinc oxide Zinc boils at 1180 K, so the curve ( Zn, ZnO ) increases rapidly at this temperayure. Above 1270 K G ( Zn, ZnO ) G ( C, CO )
. .

2 + O2

O Zn

--------------------

Zn

Explain the choice of reducing agent in a particular case depends on thermodynamic factors.

CO

Only metal will reduce the oxides of other metal which lie above it in the Ellingham diagram because the standard free energy change ( r G ) of the combined redox reaction will be - ve by an amount equal to difference in f G of the two metal oxides. Thus both Al and Zn can reduce FeO to Fe, but Fe can not reduce Al2O3 to Al and ZnO to Zn. Similarly C can reduce ZnO to Zn, but not CO. Reduction of Haematite [1] Below 1073 K, G ( Fe, Fe 2O3 ) So Haematite is reduce by CO
Fe2O 3
. .

1180 K

G ( CO, CO2 )

2 CO

1270 K

Thus zinc oxide is reduced by coke above 1270 K. ZnO C Above 1270 K.

Zn

2C

+ O

[2] Above 1073 K , G ( Fe, Fe 2O3 ) So Haematite is reduce by coke.

Fe2O 3

G ( C, CO )

1073 K

3 CO

Below 1073 K

2 Fe
.

+ +

3 CO2

CO

O2

---------------------------2C

2C O

4 Fe + O 2 3
+ O
2

O 2 Fe 2 3

2C O

3C

Above 1073 K
.

2 Fe

3 CO

Out of C and CO AT 673 K

, which is a better reducing agent at 673 K ?

.

So 'CO' is the better reducing agent. Why is the extraction of copper from pyrites more difficult than that from its oxide ore through reduction ? CuFeS2 has to be converted into its oxide before reduction.

G ( c, co )

G ( co, co 2 )

G ( Cu ,Cu2S )
.

G ( C, CS2 ) and

G ( H2 ,H2S )
H2

In contrast,
Cu2O

G ( Cu, Cu2O )
.

So Cu2S can not be reduced by C or G ( C , CO ) So Cu2O can be easily reduced by coke.

C
.

2 Cu

Predict conditions under which Al will reduce Below 1350 C, G( Al, Al 2O3 ) So Mg can reduce Al2O3
2 Mg

CO

gO M

MgO
4 Al + 3

G ( Mg, MgO )

O2

2 Al O 3 O2 + 3 2 g M 2

---------------

2 Al O 3 2 3

2 MgO

4 Al 3

G T
4 Al 3

But Mg is much uneconomical.

costlier than Al, hence the process will

.

Above 1350 C , G ( Mg, MgO ) The value of

G( Al, Al 2O3 )

So 'Al' can reduce MgO

1350 C

2 MgO

2 Al O 3 2 3

+ 2 Mg

G for formation of Cr2O3 is 540 kJ/mol and that of Al2O3 is 827 kJ/mol.Is the
Since
2 Cr O 3 2 3

reduction of Cr2O3 possible with Al ? So 'Al ' Can reduce Cr2O3

4 3Al 4 Al 3

G ( Cr, Cr2O3 )
2 3 Al2O 3 4 Cr 3 4 3 Cr

G ( Al, Al2O3 )

+ O2 2 + 3 Cr2O3

O2

+3

2 Al O 2 3

G = + 540 KJ / mol G = - 827 KJ / mol G = - 287 KJ / mol

Since G of combine reaction is - ve , therefore reduction of Cr2O 3 by Al is possible. Name the process from which Cl 2 is obtained as by-product. What will happen if an aqueous solution of NaCl is subjected to electrolysis? Down's process , for extraction of sodium metal by electrolysis of fused mixture of NaCl and CaCl 2 at 873 K NaCl Na+ + ClCathode: Na+ + eNa
2

Anode :
2

2 Cl -

Cl2

+ NaCl

2 eNa+ Cl2 + + 2 e
-

If aqueous NaCl is electrolysed H and Cl will obtain. www.cpprashanthschemistry.com

Cathode: 2 H2O + 2 e
-

Cl-

Page 13

H2 +

2 OH

Anode :

2 Cl -

NaOH will obtain in the solution

THE P-BLOCK ELEMENTS

N exhibits +5 oxidation state, but not form NCl5 PH3 has lower boiling point than NH3. Why? Pentahalides more covalent than trihalides BiH3 is strongest reducing agent amongst the hydrides Reaction of thermal decomposition of sodium azide. Why is N2 less reactive at room temperature? Why does NH3 act as a Lewis base ? Conditions required to maximise the yield of ammonia. How does ammonia react with a solution of Cu2+? Why does NO2 dimerise ? What is the covalence of nitrogen in N2O5 ? Prove that PH3 is basic in nature? Bond angle in PH4+ is higher than that in PH3. Why? white P is heated with conc NaOH solution in CO2 ? Why does PCl3 fume in moisture ? Are all the five bonds in PCl5 molecule equivalent? What happens when PCl5 is heated? Hydrolytic reaction of PCl5 in heavy water. Account for the reducing behaviour of H3PO2 What is the basicity of H3PO4? What happens when H3PO3 is heated? The HNH angle is higher than HPH, HAsH angles. Why does R3P = O exist but R3N = O does not Why NH3 is basic while BiH3 is only feebly basic. Nitrogen as diatomic molecule and phosphorus as P4. Differences between white P and red P N show catenation properties less than phosphorus? Can PCl5 act as an oxidising & reducing agent? Justify. Elements of Gr- 16 show lower value of first IE compared to the corresponding periods of group 15. Why? H2S is less acidic than H2Te. Why? Order of thermal stability of the hydrides of Group-16 Why is H2O a liquid and H2S a gas ? Why does O3 act as a powerful oxidising agent How is O3 estimated quantitatively
Which form of sulphur shows paramagnetic behaviour ?

What happens when sulphur dioxide is passed through an aqueous solution of Fe(III) salt? Comment on the nature of two SO bonds formed in SO 2 How is the presence of SO2 detected ? Write the conditions to maximise the yield of H2SO4 Why is Ka2 << Ka1 for H2SO4 in water ? Why is dioxygen a gas but sulphur a solid? Knowing the electron gain enthalpy values for O O and O O2 as 141 and 702 kJ mol1 respectively, how

It does not have d orbitals to expand its covalence beyond 4 Due to high electronegativty of N, NH3 forms H-bonding High +ve oxidation state, more polarizing power, so covalent Because BiH3 is the least stable hydrides of Group 15. 2NaN 2Na+3N2 Strong pp overlap resulting into the triple bond, NN. Nitrogen atom in NH3 has one lone pair of electrons P = 200atm, T=700 K catalyst such as iron oxide. Cu2+ (blue) + 4 NH3(aq) [Cu(NH3)4]2+(aq) (deep blue) It has odd electrons. On dimerisation, converted to N2O4 4 Reacts with acids like HI . PH3+HIPH4I in PH3 there is lone pair-bond pair repulsion P4+3NaOH+3H2O PH3+3NaH2PO2 sodium hypophosphite PCl3 +3H2OH3PO3 +3HCl (fumes) Two axial bonds are longer than equatorial bonds due to repulsion PCl5 PCl3 + Cl2 PCl5 + D2O POCl3 + 2DCl Two H are bonded directly to P giving reducing character 3 4H3PO3 3H3PO4 + PH3 (disproportionation) sp3 hybridisation in NH3 Nitrogen cannot form d p bond Small size and hence high electron density on N Due to small size N form pp bond resulting into NN. White P: white waxy/poisonous/ soluble in CS2/ reactive Red P : grey /nonpoisonous/insoluble in CS2/less reactive N-N single bond is weaker than P-P single bond. P is in highest oxidation state +5. So it is only oxidizing agent Due to extra stable half-filled p orbitals electronic configurations of Group 15 elements Due to the decrease in bond (TeH) dissociation enthalpy H2O>H2S>H2Se>H2Te>H2Po Due to intermolecular H-bonding in H2O Due to the ease with which it liberates atoms of nascent oxygen When ozone reacts with an excess of potassium iodide solution. iodine is liberated which can be titrated against a standard solution of sodium thiosulphate In vapour state sulphur partly exists as S2 molecule which has two 2 and, hence, exhibits paramagnetism. 2Fe3+ + SO2 + H2O 2Fe2+ + SO42- + 4H+
Both the SO bonds are covalent and have equal strength It decolourises acidified potassium permanganate(VII) solution Low temperature and high pressure H2SO4 is largely dissociated into H+ and HSO4O can form pi bond,exists as discrete O 2 molecule, so it is gas. Oxides having O2 have high negative lattice enthalpy.

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Page 14

can you account for the formation of a large number of oxides having O2 species and not O? Which aerosols deplete ozone? How is SO2 an air pollutant? Halogens have maximum negative electron gain enthalpy Although electron gain enthalpy of fluorine is less negative as compared to chlorine, fluorine is a stronger oxidising agent than chlorine. Why? Fluorine exhibits only 1 oxidation state whereas other halogens exhibit + 1, + 3, + 5 and + 7 oxidation states also. Explain. Considering the parameters such as bond dissociation enthalpy, electron gain enthalpy and hydration enthalpy, compare the oxidising power of F 2 and Cl2. Two examples to show the anomalous behaviour of F Write the balanced chemical equation for the reaction of Cl2 with hot and concentrated NaOH. Is this reaction a disproportionation reaction? Justify. Give the reason for bleaching action of Cl2. Name two poisonous gases prepared from chlorine gas. When HCl reacts with finely powdered iron, it forms ferrous chloride and not ferric chloride. Why? Deduce the molecular shape of BrF3 on the basis of VSEPR theory. Why is ICl more reactive than I2? Why are halogens strong oxidising agents? Explain why fluorine forms only one oxoacid, HOF. Oxygen forms hydrogen bonding while chlorine does not. Write two uses of ClO2. Why are halogens coloured? What happens when NaCl is heated with sulphuric acid in the presence of MnO 2. Noble gases have very low boiling points. Why? Does the hydrolysis of XeF6 lead to a redox reaction? Why is helium used in diving apparatus? Why has it been difficult to study the chemistry of radon? With what neutral molecule is ClO isoelectronic? Is that molecule a Lewis base? Why do noble gases have large atomic sizes? List the uses of neon and argon gases. F2, Cl2, Br2, I2 - increasing bond dissociation enthalpy. HF, HCl, HBr, HI - increasing acid strength. NH3, PH3, AsH3, SbH3, BiH3 increasing base strength. Which one of the following does not exist? (i) XeOF4 (ii) NeF2 (iii) XeF2 (iv) XeF6

Freons It causes acid rain Halogens have the smallest size in their respective periods It is due to (i) low enthalpy of dissociation of F-F bond (ii) high hydration enthalpy of F Fluorine is the most electronegative element and cannot exhibit any positive oxidation state. Other halogens have d orbitals and therefore, can expand their octets and show + 1, + 3, + 5 and + 7 Electrode potential of F2 is higher than Cl2 so F2 is stronger oxidizing agent than Cl2

F forms only one oxo acid , HF is liquid but others are gas 3Cl2 + 6NaOH 5NaCl + NaClO3 + 3H2O Yes, chlorine from zero oxidation state is changed to 1 and +5 oxidation states. Cl2 + H2O 2HCl +O , Coloured substance + O Colourless Phosgene gas (COCl2) , mustard gas Its reaction with iron produces H2. 2 Fe+2HClFeCl +H2 Liberation of H2 prevents the formation of ferric chloride. There are three bond pairs and two lone pairs. The two lone pairs will occupy the equatorial positions of aTBP The shape would be that of a slightly bent T. I-Cl bond is weaker than I-I bond Due to low bond dissociation energy, high electronegativity and large negative electron gain enthalpy Due to high electronegativity and absence of d-orbitals Due to large size of Cl It is powerful oxidizing agent and chlorinationg agent Their molecules absorb light in visible region 4NaCl +MnO2 + 4H2SO4 MnCl2 + 4NaHSO4 + Cl2 + H2O Noble gases being monoatomic have no interatomic forces except weak dispersion No, the products of hydrolysis are XeOF4 and XeO2F2 where the oxidation states of all the elements remain the same Due to its low solubility in blood Due to its very short half life ClF, Yes it is a Lewis base They have onle van der Waals radii which is longer Neon- in discharge tube. Ar to make an inert atmosphere I2< F2 <Br2 <Cl2, HF<HCl<HBr<HI BiH3 < SbH3< AsH3,< PH3,< NH3, NeF2

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Page 15

The d & f BLOCK ELEMENTS

Scandium (Z = 21) is a transition element but Zinc (Z = 30) is not? Ag (4d10) but it is a transition element? Transition elements exhibit higher enthalpies of atomisation? Enthalpy of atomization of zinc is low Incompletely filled 3d orbitals in case of scandium Zn & Zn2+ have completely filled d orbitals (3d10) Ag has +2 oxidation state having incompletely filled d-orbital Because of large number of unpaired electrons in their atoms they have stronger interatomic interaction In the formation of metallic bonds, no electrons from 3d-orbitals are involved in case of zinc(3d10) Having no variable oxidation states. Scandium (Z = 21) Largest number of oxidation states. Mn(+2 to +7) Because it has largest number of unpaired electrons 2+ 3+ Why is Cr reducing and Mn oxidising Cr2+ changes from d4 to d3(stable).On the other hand, the change when both have d4 configuration. from Mn2+ to Mn3+ results in the half-filled (d5) The E0(M2+/M) value for copper is +ve Due to its high aH0 and low hydH0) + 2 Oxidising power:VO2 < Cr2O7 < MnO4 This is due to the increasing stability of the lower species Account for the irregular variation of IE Due to varying degree of stability of different 3d-configurations 0 2+ The E (M /M) values are not regular Due to the irregular variation of IE , sublimation enthalpies E0 of Mn3+/Mn2+ is more positive than that Much larger third IE of Mn (where the required change for Cr3+/Cr2+ or Fe3+/Fe2+? Explain. is d5 to d4) is mainly responsible for this. Highest oxidation state of a metal exhibited Small size and high electronegativity O or F can oxidise the metal in its oxide or fluoride to its highest oxidation state. Which is a stronger reducing agent Cr2+ or Cr2+ is stronger reducing agent than Fe2+ Fe2+ and why ? Reason: d4 d3 occurs in case of Cr2+ to Cr3+, d3 is stable But d6 d5 occurs in case of Fe2+ to Fe3+ Magnetic moment of a divalent ion in d5 Configuration (five unpaired electrons). The magnetic moment, aqueous solution if its atomic number is 25. is = 5(5+2) = 5.92BM Calculate the spin only magnetic moment M2+ (aq) ion (Z = 27) d7 3 unpaired electrons of M2+ (aq) ion (Z = 27). = 3(3+2) = 3.87BM What is meant by disproportionation of When a particular oxidation state becomes less stable relative to an oxidation state? Give an example. other oxidation states, one lower, one higher, it is said to undergo disproportionation. For example, Mn (VI) becomes unstable relative to Mn(VII) and Mn (IV) in acidic solution. 3 MnO4 2 + 4 H+ 2 MnO4- + MnO2 + 2H2O Explain why Cu+ ion is not stable in Cu+ in aqueous solution undergoes disproportionation, aqueous solutions? 2Cu+(aq) Cu2+(aq) + Cu(s) The E0 is favourable for this Lanthanoids to exhibit +4 oxidation state. Cerium (Z = 58) Actinoid contraction is greater than 5f electrons themselves provide poor shielding from element to lanthanoid contraction. Why? element in the actinoid series. 2+ 2+ Mn more stable than Fe It is because Mn2+ has 3d5 configuration which is stability. 3 5 8 Stable oxidation state for : 3d , 3d , 3d and 3d3 (V): (+2), +3, +4, and +5 ; 3d5 (Cr): +3, +4, +6 3d4? 3d5 (Mn): +2, +4, +6, +7 ; 3d8 (Co): +2, +3 (in complexes) 4 4 3d There is no d configuration in the ground state. Oxometal anions in which the metal Vanadate VO3, Chromate Cr2O4 , Permanganate MnO 4 exhibits the oxidation state equal to its group number. What is lanthanoid contraction? What are Gradual decrease of atomic radii form La to Lu

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Page 16

the consequences of lanthanoid contraction?

Consequences : similar properties of 2nd and 3rd rows transition elements

In what way is the electronic configuration of the transition elements different from that of the non transition elements? Oxidation states of the lanthanoids? Transition metals are paramagnetic Enthalpies of atomisation of the transition metals are high. Transition metal form coloured compounds Transition metals and their many compounds act as good catalyst. How is the variability in oxidation states of transition metals different from that of the non transition metals? Illustrate with examples. Which of the following will be coloured Ti3+,V3+,Cu+,Sc3+,Mn2+, Fe3+ & Co2+. Of the d4 species, Cr2+ is reducing while Mn(III) is strongly oxidising. Co(II) is stable in aq sol but in the presence of complexing reagents it easily oxidised. The d1 configuration is unstable in ions. Which transition metal has +1 oxidation state most frequently and why? Calculate the number of unpaired electrons in the following gaseous ions: Mn3+, Cr3+, V3+ and Ti3+. Which one of these is the most stable in aqueous solution? The lowest oxide of transition metal is basic, the highest is amphoteric/acidic. A transition metal exhibits highest oxidation state in oxides and fluorides. The highest oxidation state is exhibited in oxoanions of a metal. Which is the last element in the series of the actinoids? Write the electronic configuration of this element. Comment on

In transition elements the last electron goes into penultimate shell

+3 is the common oxidation lso +3, oxidation states +2 and +4 For having unpaired electrons Due to strong metallic bonding

Due to incompletely filled d-orbital there is d-d electron transition Because they can adopt variable oxidation states to form different intermediate In transition elements the oxidation states vary by one For example, for Mn it may vary as +2, +3, +4, +5, +6, +7. In the nontransition elements the variation is selective, always differing by 2, e.g. +2, +4, or +3, +5 or +4, +6 etc. Except Sc3+, all others will be coloured due to incompletely filled 3d-orbitals, will give rise to d-d transitions. Cr2+ is reducing as it change from d4 to d3, the latter is more stable Mn(III) to Mn(II) is from 3d4 to 3d5 again 3d5 is stable Due to CFSE, which more than compensates the 3rd IE. The hydration or lattice energy more than compensates the ionisation enthalpy involved in removing electron from d1. Cu, because with +1 oxidation state an stable configuration, 3 d10 Unpaired electrons Mn3+ = 4, Cr3+ = 3, V3+ = 2, Ti3+ = 1. Most stable Cr3+

In lowest oxidation state ionic bond is formed but in highest oxidation state covalent bond is formed

O and F are strong oxidizing agents and can excite electrons

Oxygen is strong oxidizing agent

Lawrencium(103) 5f 146d17s2 Page 17

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the possible oxidation state of this element.

+3

BIOMOLECULES
KEY POINTS
Monosaccharides Disaccharides Polysaccharides Amylose Amylopectin Cellulose Glycogen reducing sugars Non reducing sugars Anomers. Invert sugar

Glycosidic linkage Importance of Carbohydrates essential amino acids Nonessential amino acids zwitter ion. peptide linkage 10- str. of proteins: 20- str. of proteins: Tertiary structure of proteins: Fibrous proteins Globular proteins Stab.forces 2& 3 Denaturation of Proteins

EXPLANATIONS Cannot be hydrolyzed further . eg- glucose, fructose, ribose Sucrose (-D- glucose + -D-fructose) , Maltose(-D- glucose + -D- glucose) Lactose(-D-galactose + -D-glucose ) Starch (two componentsAmylose and Amylopectin) polymer of -D- glucose Water soluble , 15-20% of starch., unbranched chain , C1 C4 glycosidic linkage. Water insoluble , 80-85% of starch., branched chain polymer, C1C4 & C1C6 glycosidic linkage Straight chain polysaccharide of -D-glucose units/ joined by C1-C4glycosidic linkage (-link), not digestible by human / constituent of cell wall of plant cells Highly branched polymer of -D- glucose .found in liver, muscles and brain. Aldehydic/ ketonic groups free so reduce Fehlings/ Tollens solution and. Eg- maltose and lactose Aldehydic/ ketonic groups are bonded so can not reduce Fehlings solution and Tollens reagent. Eg Sucrose The two cyclic hemiacetal forms of glucose differ only in the configuration of the hydroxyl group at C1, called anomeric carbon Such isomers, i.e., form and -form, are called anomers. Sucrose is dextrorotatory but after hydrolysis gives dextrorotatory glucose and laevorotatory fructose. Since the laevorotation of fructose (92.4) is more than dextrorotation of glucose (+ 52.5), the mixture is laevorotatory. Thus, hydrolysis of sucrose brings about a change in the sign of rotation, from dextro (+) to laevo () and the product is named as invert sugar Linkage between two mono saccharide Major portion of our food. / used as storage molecules as starch in plants and glycogen in animals/. Cell wall of bacteria and plants is made up of cellulose./wood and cloth are cellulose / provide raw materials for many important industries like textiles, paper, lacquers and breweries. which cannot be synthesised in the body and must be obtained through diet, eg- Valine, Leucine which can be synthesised in the body, eg - Glycine, Alanine

Fat soluble vit Water soluble vit Vitamins sources-

In aqueous solution, amino acids exist as a dipolar ion known as zwitter ion. peptide linkage is an amide formed between COOH group and NH2 group of two successive amino acids in peptide chain. sequence of amino acids that is said to be the primary structure of protein secondary structure of protein refers to the shape in which a long polypeptide chain can exist. They are found to exist in two types of structures viz. -helix and -pleated sheet structure. further folding of the secondary structure. It gives rise to two major molecular shapes viz. fibrous and globular. Polypeptide chains run parallel, held together by hydrogen and disulphide bonds, fibre like structure. Water insoluble . Eg- are keratin(in hair, wool, silk) and myosin (present in muscles). chains of polypeptides coil around to give a spherical shape. water soluble. Eg-Insulin and albumins hydrogen bonds, disulphide linkages, van der Waals and electrostatic forces of attraction. When a protein is subjected to physical change like change in temperature or chemical change like change in pH, the hydrogen bonds are disturbed. Due to this, globules unfold and helix get uncoiled and protein loses its biological activity. This is called denaturation of protein. (During denaturation 2 and 3 structures are destroyed but 1 structure remains intact.) eg- The coagulation of egg white on boiling, curdling of milk These are vitamins A, D, E and K. They are stored in liver and adipose (fat storing) tissues B , C . these vitamins must be supplied regularly in diet because they are readily excreted in urine Vit- A (Fish liver oil, carrots)- Night blindness / Vitamin B1 (Yeast, milk,)- Beri beri

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Page 18

Deficiency diseases DNA RNA Nucleoside / tides Phosphodiester link

Functions of Nucleic Acids

Vit-B2 (Milk, eggwhite)- Cheilosis / Vit- B6 (Yeast, milk,)- Convulsions / Vit- B12 (Meat, fish,)- anaemia Vit C(Citrus fruits)- Scurvy, / Vit D(Exposure to sunlight, fish and egg yolk)- Rickets, osteomalacia Vit E(wheat oil, sunflower oil)- fragility of RBCs / Vit K(leafy vegetables)- Increased blood clotting time pentose sugar (D-2-deoxyribose) + phosphoric acid + nitrogenous bases ( A , G , C, T ) pentose sugar (ribose) + phosphoric acid + nitrogenous bases (A , G , C, U ) Nucleoside sugar + base Nucleotides sugar + base + phosphate Linkage between two nucleotides in polynucleotides DNA reserve genetic information, maintain the identity of different species , is capable of self duplication during cell division, synthesizes protein in the cell.

POLYMERS POLYMER Polythene Teflon

(Poly tetrfluoroethene)

Poly acrylonitrile Buna S Buna N Natural Rubber Synthetic Rubber(Neoprene) Polypropene Polystyrene Polyvinyl chloride (PVC) Terylene(Dacron) Nylon 66 Nylon 6 Bakelite Melamine PHBV (biodegradable) Nylon 2 Nylon 6 (biodegradable) Urea-formaldehyde resin Glyptal Semi-synthetic poly

MONOMER(Name & Structure) USES Addition or Chain Growth Polymer Ethene CH2=CH2 Insulator, ,Packing material, Lubricant, Insulator and making non-stick Tetrfluoroethene CF2=CF2 cooking ware. Acrylonitrile CH2=CH-CN For synthetic fibres and synthetic wool. Buta-1,3-diene + Styrene Automobile tyres and Foot wears CH2=CH-CH=CH2 C6H5CH=CH2 Buta-1,3-diene + Acrylonitrile Oil seals, Tank lining CH2=CH-CH=CH2 CH2=CH-CN 2-Methylbuta-1,3-diene (Isoprene) Used for tyres after vulcanisation Insulator, making conveyor belts and 2-Chlorobuta-1,3-diene (Chloroprene) printing rollers Propene CH3-CH=CH2 Ropes, toys, pipes and fibres Insulator, Wrapping material,toys, Radio Styrene C6H5CH=CH2 and television cabinets. Rain coats, Hand bags, Vinyl flooring and Vinyl Chloride CH2=CH-Cl water pipe. Condensation or Step Growth Polymers Ethane-1,2-diol + Benzene-1,4Used for making fibres, safety belts, tents dicarboxylic acid Hexamethylene diamine + Adipic acid For making brushes,paratutes and ropes NH2(CH2)6NH2 HOOC(CH2)4COOH Caprolactum Tyres cords,fabrics and ropes Combs,electrical switches,handles of Phenol + Methanal utensiles and computer discs Melamine + Methanal Unbreakable crockery 3-Hydroxybutanoic acid + Specialty packaging, orthopedic devices, In 3-Hydroxypentanoic acid controlled drug release Glycine + Amino caproic acid H2N-CH2-COOH H2N (CH2)5-COOH Unbreakable cups , laminated sheet Urea + Formaldehyde Ethane1,2-diol + Benzene-1,2dicarboxylic acid Cellulose Acetate (Rayon) Page 19 Binding material in preparation of mixed plastics and paints

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Thermoplastic polymers Thermosetting polymers Homo-polymer & Co-polymer Initiators Vulcanisation of Rubber.

Linear or slightly branched / capable of repeatedly softening on heating and hardening on cooling. Example : Polythene, Polystyrene, Polyvinyls, etc. Cross linked or heavily branched molecules, / on heating undergo extensive cross linking in moulds and again become infusible. These cannot be reused. Examples : Bakelite, Urea-formaldelyde resins. Homo-polymer Polymer of a single monomeric species. Example : Polythene , PVC Co-polymer Polymer of more than one monomer .Example : Nylon66, Bakelite Benzoyl Peroxide [ C6H5CO-O-O-CO-C6H5 ] (in free radical addition polymerization) Natural rubber is soft at high temp and brittle at low temp and absorbs water. To improve these physical properties, it is heated with sulphur and an appropriate additive at a temperature range between 373 K to 415 K. On vulcanisation, sulphur forms cross links at the reactive sites of double bonds and thus the rubber gets stiffened.

CHEMISTRY IN EVERYDAY LIFE

Drugs Analgesics Analgesics (Narcotic ) Antibiotics THERAPEUTIC ACTION OF DIFFERENT DRUGS Action Example Relieving pain Aspirin Analgin, Seridon, Anacine, Reduce tension and pain. Opium, Heroin , Pethidine , Codeine, produce unconsciouness. Morphine Produced by micro organism, Penicillin G(Narrow Spectrum) that can inhibit the growth or Streptomycin, Ampicillin , Amoxycillin destroy other micro-organism. Chloramphenicol Vancomycin, ofloxacin , Prevent the growth of microorganism or kill them but not harmful to the living tissues. Kills micro-organisms, not safe for living tissues. It is used for toilets, instruments. Reduce or neutralise the acidity. Reduce release of acid. It is also used to treat allergy Tranquilizers Antipyretics Antifertility drugs Sweetening Dettol, Tincture iodine, Bithional(in soap) 0.2% phenol,

Antiseptics

Disinfectants

1% phenol, chlorine (Cl2) , Sulphurdioxide ( SO2)

NaHCO 3 Al(OH)3 gel AlPO4 MgCO3 Mg(OH)2

Antacids Antihistamines

Cimetidine(Tegamet), Ranitidine (Zantac),

Brompheniramine ( Dimetapp) Terfenadine ( Seldane) Reduce the mental anxiety, Valium, Serotonin, Veronal, stress, (sleeping pill) Equanil,Amytal,Nembutal,Luminal, Seconal Reduce body temperature Aspirin, Paracetamol, Analgin, Phenacetin. These are the steroids used to Norethindrone, Ethynylestradiol control the pregnancy (novestrol ) CHEMICALS IN FOOD Saccharine, Aspartme(for cold foods) Alitame Page 20

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Agent

Sucrolose(stable at cooking temp) Food Preservative Salt, sugar, veg. oils, sodium benzoate CLEANSING AGENTS Soap Na / K salt of long chain fatty Not work in hard water becoz with Ca and acids Mg salt soap produce insoluble scum Anaionic detergen Sodium laurylsulphate Used in household work / in tooth paste Cationic Cetyltrimethyl ammonium Hair conditioner / germicidal properties detergent bromide Non ionic Ester of stearic acid and Liquid dishwashing detergent polyethylene glycol Detergents with highly branched hydrocarbon parts are non biodegradable and hence water pollutants so branching is minimized which are degradable and pollution is prevented. NAME REACTIONS
1. Finkelstein 2. Swarts Friedel-Crafts Alkylation 3.
COCH 3

CH3Br + NaI CH3Br + AgF

CH3-I + NaBr CH3F + AgBr

CH3

Anhydrous AlCl3
H3C Cl

Friedel-Crafts Acylation 4. Wurtz 5. Fittig 6.

Cl
H3C
Cl

CH3COCl Anhydrous AlCl3

Cl

+
+

Cl
Cl

CH3

2Na
H3C CH3

Na Cl

2Na Dry ether

Na Cl

Wurtz-Fittig 7.
OH

2Na
Cl CH3

Dry ether
ONa

CH3
OH

Na Cl

Kolbe 8.

Na OH

i) CO2 ii) H+

COOH

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OH

ONa

OH CHO

Reimer-Tiemann 9. 10. Williamson Stephen 11.

CH3Cl + Na OH

H+

CHO

CH3-Br + CH3-ONa
H3C CN

CH3-O- CH3 + NaBr

H3C CH NH

SnCl2 + HCl

H3O+

H3C

CHO

CH3

CHO

Etard 12.

CrO2Cl2 H3O+
CHO

Gatterman Koch
13. Rosenmund reduction 14. Clemmensen reduction Wolff-Kishner reduction
O C H3C
O C H3C
O C H3C CH3
2+

CO / HCl Anhydrous AlCl3

H2
Cl

O C H3C H

Pd / BaSO4
Zn - Hg

15.

CH3

Conc. HCl
i) NH2-NH2 ii) KOH / Ethylene glycol /
+ 5 OH
-

H3C

CH2 CH3

H3C

CH2 CH3

16.

17. Tollens test 18. Fehlings test

R-CHO + 2 [Ag(NH3)2]+ + 3 OHR-CHO + 2 Cu

O C H3C CH3

R-COO- + 2Ag R-COO + Cu2O

+ 2H2O + 4 NH3

+ 3H2O

Iodoform
19.

I2 / NaOH OR, NaOI

CHI3 + CH3COONa
OH

Aldol condensation
20.

dil NaOH 2 H3C

CHO

CHO H3C CH CH

H3C CH CH2

CH

Cannizzaro
21. Hell-VolhardZelinsky (HVZ) 22.

HCHO

+ HCHO
COOH

Conc. NaOH

HCOONa

H3C

OH

H3C

i) Cl2 / Red Phosphorus ii) H2O

H2C Cl COOH

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Hoffmann bromamide 23. degradation

24.

O H3C C NH2

Br2 NaOH
H3C NH2

Carbylamine Diazo

R-NH2 + CHCl3 + 3 KOH

NH2

R-NC + 3 KCl + 3 H2O

N2 Cl
+ -

NaNO2 + dil HCl 273 - 278 K

N2 Cl
+ -

25.

Cl

Sandmeyer.
26.
N2 Cl
+ -

CuCl / HCl

+ N2
Cl

Gatterman
27.

Cu / HCl

+ N2
OH-

Coupling
28.

N2 Cl

OH

OH

DISTINGUISH BY A SINGLE CHEMICAL TEST 1. All aldehydes ( R-CHO) give Tollens Test and produce silver mirror. RCHO + 2 [Ag(NH3)2]+ + 3 OH- RCOO- + 2 Ag
Tollens Reagent silver ppt

+ 2H2O + 4 NH3

Note: HCOOH(methanoic acid ) also gives this test, ketones(RCOR) do not give this test 2. All aldehydes (R-CHO) and ketones(RCOR) give 2,4-DNP test RCOR + 2,4-DNP Orange ppt R-CHO + 2,4-DNP Orange ppt 3. Aldehydes and ketones having CH3CO- (keto methyl) group give Iodoform Test. Alcohols having CH3CH- group also give Iodoform Test. | OH CH3CHO + 3I2 + 4 NaOH CHI3 + HCOONa + 3 NaI + 3H2O
Yellow ppt

The following compounds give Iodoform Test: ethanol (C2H5OH), propan-2-ol (CH3CH(OH)CH3), ethanal(CH3CHO), propanone(CH3COCH3), butanone ( CH3COCH2CH3) , pentan-2-one (CH3COCH2 CH2CH3) , acetophenone ( PhCOCH3 ) 4. All carboxylic acids ( R-COOH) give Bicarbonate Test RCOOH + NaHCO3 RCOONa + CO2 + H2O

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effervescence

5. Phenol gives FeCl3 Test C6H5OH + FeCl3 (C6H5O)3Fe + 3 HCl (neutral) (violet color) 6. All primary amines (R/Ar -NH2) give Carbyl Amine Test R-NH2 + CHCl3 + KOH(alc) R-NC + KCl + H2O
offensive smell

7. Aniline gives Azo Dye Test ( Only for aromatic amines) C6H5NH2 + NaNO2 + HCl C6H5N2+Cl- ; then add -naphthol orange dye 8. All alcohols (ROH) give Na-metal test R-OH + Na R-ONa + H2
bubbles

9. For esters (RCOOR) : Hydrolyses first. Then see the products ( acid & alcohol) and give a test to identify them 10. All alkenes (C=C) and alkynes (CC) decolorizes Br 2 water from red to colorless 11. Lucas Test to distinguish primary, secondary and tertiary alcohols Lucas reagent: ZnCl2/HCl 0 3 -alcohol + Lucas reagent immediate turbidity 20-alcohol + Lucas reagent turbidity after sometime 10-alcohol + Lucas reagent no turbidity

KEY FOR CONVERSIONS

Sl No

Reagent
KMnO4 / H+ LiAlH4 Cu / 573 K or CrO3 PCl5 or SOCl2 Cl2 / or Cl2 / UV Aq NaOH / KOH KCN AgCN Alcoholic KOH Mg / dry ether HBr H2 / Pd-BaSO4 Zn-Hg / HCl NH3 / Br2 / NaOH or NaOBr HNO2 or NaNO2/HCl CHCl3 / alc KOH

Group Out
-CH2OH -COOH -CH2OH -OH -H -X -X -X -HX >=< -COCl >C=O -COOH -CONH2 -NH2 -NH2

Group In
-COOH -CH2OH -CHO -Cl -Cl -OH -CN -NC = Mg H, Br -CHO -CH2-CONH2 -NH2 -OH -NC

Remark
Strong Oxidation (20 alc ketone) Strong Reduction (ketone 2 alc) Dehydrogenation
0

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17

Free radical substitution Nucleophilic substitution Step Up Dehydrohalogenation (Stzf) R-X R-MgX Merkovnikov Rosenmund Reduction Clemmension Reduction -COOH + NH3 -COONH4 Step Down ( Hoffmann) HONO Carbyl amine Page 24

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18 19 20 21 22

P2O5 H3O+ OHLiAlH4 Red P / Cl2

-CONH2 -CN -CN -CN -H of acid

-CN -COOH -CONH2 -CH2NH2 -Cl

Dehydration Hydrolysis Reduction HVZ Reaction

In benzene ring
23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 Fe / X2 /dark CH3Cl / AlCl3(anhyd) CH3COCl / AlCl3(anhyd) Conc.HNO3/con.H2SO4 Conc H2SO4 KMnO4 / H+ CrO2Cl2 / H+ Sn / HCl or Fe/HCl NaOH / 623K / 300 atm Zn dust / NaNO2 / dil HCl / 273-278 K CuCl / HCl or Cu/HCl CuBr / HBr or Cu/HBr CuCN / KCN KI HBF4 / H3PO2 or CH3CH2OH H2O / 283 K HBF4/ NaNO2, Cu / C6H5-OH C6H5-NH2 -H -H -H -H -H -R -CH3 -NO2 -Cl -OH -NH2 -N2+Cl-N2+Cl-N2+Cl-N2+Cl-N2+Cl-N2+Cl-N2+Cl-N2+Cl-N2+Cl-N2+Cl-X -CH3 -COCH3 -NO2 -SO3H -COOH -CHO -NH2 -OH -H -N2+Cl-Cl -Br -CN -I -F -H -OH -NO2 -N=N-C6H5-OH -N=N-C6H5-NH2 Halogination Friedel Craft alkylation Friedel Craft acylation Nitration Sulphonation Oxidation Mild oxidation(Etard Reaction) Reduction

Diazo reaction Sanmeyer or Gattermann Sanmeyer or Gattermann Sanmeyer

Coupling ( p-hydroxy) Coupling ( p-amino)

Reactions of Grignard Reagent

Grignard reagent + Any one below + H2O H2O or ROH or RNH2 H-CHO R-CHO R-CO-R CO2 R-CN HCOOR RCOOR Product R-H R-CH2-OH (10 alc) R-CH(OH)-R (20 alc) R2C(OH)-R (30 alc) R-COOH R-CO-R Aldehyde Ketone

R-MgX

NB: i) During reaction generally changes take place in the functional group only so see the functional group very carefully. ii) Remember structural formula of all the common organic compounds ( with their IUPAC and common names) iii) Wurtz Reaction and Aldol Condensation are not included in the table although they are

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very important for conversions so study them . iv) By taking examples practice all the above cases ( from 1 to 43 and Grignards reaction.) vi) Start practicing NOW !

Directional Properties of groups in benzene ring for electrophilic substitution

Ortho-para directing group: -R , -OH, -NH2, -X, -OR, -NHR, -NR2, -NHCOCH3, -CH2Cl, -SH, - Ph Meta-directing group: -NO2 , -CHO , -COOH , COOR , -CN , -SO3H , -COCH3 , -CCl3 , -NH3+ ,

ELECTRON DISPLACEMENT EFFECTS + I : O- , COO- , (CH3)3C , (CH3)2CH , CH3CH2 , CH3 - I : NR3 ,

+

(electron donating)

SR2+

, NH3 , NO2 , SO2R , CN , COOH , F , Cl , Br , I , OR , OH, NH2 (withdrawing)

+R (+M) : -R (-M)

OH , NH2 , OR , NHR , X

(electron donating) (electron withdrawing)

: NO2 , CN , CHO , COOH , COCH3

DIRECTIVE INFLUENCE OF SUBSTITUENTS IN BENZENE RING (for electrophilic substitution reactions) EFFECT OF THE GROUP DIRECTING ACTIVATING / DEACTIVATING

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+I +I,+R -I< +R -I>+R -I -I, -R Example: -I

Ortho / Para Ortho / Para Ortho / Para Ortho / Para Meta Meta +R

Activating Activating Activating Deactivating Deactivating Deactivating

>

: - X , - CH=CH2 , -CH=CH-COOH , -CH2-Cl

These groups are deactivating but exceptionally o / p directing due to +E effect by the attacking reagents electron density increases at ortho and para position .

If two groups are present initially 1. When both the groups present in benzene ring are o/p directing than the order of influence : O- > NH2 > NR2 > OH > OCH3 > NHCOCH3 > CH3 > X 2. When both the groups present in benzene ring are meta directing than the order of influence : (CH3)3N+ > NO2 > CN > SO3H > CHO > COCH3 > COOH 3. When one group is o/p and another is m directing than o/p directing group takes priority

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