www.crackjee.xyz LAKSHYA CHEMISTRY STUDY MATERIAL - CLASS 12JEE Main Revision Materials: www.crackjee.xyz SOLID STATE 2. CLASSIFICATION OF SOLIDS Solid state is a state of matter besides liquid and gaseous, Solids are broadly classified on the basis of following. state. In case of solids the inter molecular forces are very Parameters. strong and empty spaces between the atoms/ions/ * based on various properties molecules is very less. That is why they have a fixed shape . based on bonding present in building blocks. and volume, 2.1 On the basisof various properties 1.1 Characteristic Properties of Solids Based on their rious properties solids can be classified as Solids are characterised by the following properties * High density * Lowcompressibility * Rigidity * Crystalline solids * Amorphous solids. Crystalline sotids have a regular structure over the entire volume and sharp properties whereas amorphous solids have irregular structure over long distances and properties, ‘are not that sharp. Various differences are listed in table * Definite shape and volume, below Shape ‘They have long range order ‘They have short range order. Melting point They have definite melting point They do not have definite melting point Heat of fusion They have a definite heat of fusion They do not have definite heat of fusion Compressibility ‘They are rigid and incompressible ‘These may be compressed to some extent Cutting with a sharp ‘They are given cleavage i.e. they ‘They give irregular cleavage i.e. they break edged tool break into two pieces with plane into two pieces with irregular surface surfaces Isotropy and ‘They are anisotropic ‘They are isotropic Anisotropy ‘Volume change ‘There is a sudden change in volume} There is no sudden change in volume on melting. when they melt. ‘Symmetry They possess symmetry ‘They do not possess any symmetry. Interfacial angles They possess interfacial angles. They do not possess interfacial angles.JEE Main Revision Materials: www.crackjee.xyZ Based on bonding There are various type of solids based on type of bonding present in their building blocks. Various types of solids along with their properties are given in the table below. ‘The different properties of the four types of solids are listed in Different Types of Solids ‘Type of Solid Constituent | Bonding Examples Physical Electrical | Melting (1) Molecular Solids (Non polar Dispersion oF An CCl Soft Insulator Very low London forces Hy. 1, CO, (ii) Polar Dipole-dipote HCI, SO, Soft Insulator Low Interactions (iy Hydrogen Hydrogen H,0 (ice) Hard Insulator Low bonded bonding, 2) lonie solids Tons Coulombic or Hard but Insulators | High electrostatic brittle n solid state but conductors in molten state and in aqueous solutions G) Metallic solids Positive Metallic Fe,CuAg, | Hard but Conductors | Fairly fons ina bonding Mg malleable in solid high seaof and state as Aelocalised ductile well asin electrons molten state (4) Covalent or Atoms Covalent SiO, Hard Insulators | Very network solids bonding (quartz) high SiC,c (diamond) AIN, Cpa Soft Conductor (exception)IIT JEE Reference Materials: www.crackjee.xyz STRUCTURE OF CRYSTALLINE SOLIDS ‘The regular array of the building blocks (atomsfions/ molecules) inside the erystalline solid is called “Crystal Lattice”. ‘The smallest part or crystal lattice which can be repeated in all directions to generate emtire crystal lattice is called “UnitCell”. Tn unit cell the atoms of ions or molecules are represented by small spheres, Various lattices are formed by variation in following parameters: * Theedge length along 3 axes -a, b,c + The interfacial angles - 0 7. * Location of atomfions wr. each other in crystal Inall, there are seven types of unit cells and there can be some sub types of unit cells. These seven unit cells are called Primitive Unit Cells or Crystal Habits. Which are listed in table below Tattice. Crystal System Axial distances Axial angles Examples Cubie a=b Copper, inc blende, KCI Tetragonal a=bee Sn (White tin), SnO,. TiO, Orthorhombic aebec Rhombie sulphur, CaCO, Monoctinic aebec a= y= 90: BeOP Monoclinic sulphur, PbC1O, Hexagonal azbeec Graphite, 210 Rhombohedral CaCO, (Calcite), HgS (Cinnabar) aebec as Beyeor K,Cr,0,,CuSO,SH,O For these 7 types of unit cells, 14 types of Lattices exist in nature, These 14 Lattices are called “Bravais Lattices.”IIT JEE Reference Materials: www.crackjee.xyz Crystal system Space lattice Examples Cubic Simple + Latice Body Centered : Face Centered : | Pb, Hg. Ag, a=b=c Points at the eight Points at the eight Points at the eight | Au, Cu, ZnS, Here a, b and ¢ are corners of the unit, corners and at the corners and at the diamond, KCI, parameters cells body centre, six face centres, | NaCl. Cu,0, (dimensions of a CaF, and unit cell slong three alumns. ete. axes) size of crystals depend on parameters. a=P=7=90 Band y are sizes of three angles between the axes. Tetragonal Simple : Points at Body Centered = SnO,. TiO, a=bec, the eight corners Points at the eight comers and at the Zn0,, NiSO, of the unit cell. body centre 21Si0,. PHwO,, ite Sn etc. Orthorhombic Simple : Points | End Centered: | Body Face Centered: | KNO,. K,SO,. «Rhombic) at the eight Alsoccalledside | Centered: Points at the PbCO,, BaSO, arbec comers of the centered or Points at eight coreners rhombic sulphur, unit cell base centered the eight and at the six MgSO,, 7H1,0 te. Points at the comers and Face centtes. eight comers and at the and at two face body centre centres opposite h other.IIT JEE Reference Materials: www.crackjee.xyz Rhombohedral Simple : Points at the eight or Trigonal corners of the unit cell asb EA Hexagonal Simple : Points at the twelve or Points at the twelve aabee, corners of the unit cell out comers of the haxagonal lined by thick End Centered : Point at the Monoclinic ‘Simple : Points ath the eight asbec, corners of the unit cell eight comers and wo face a= 7290", Pe” centres opposite to the each other. calcite, quartz ZnO. PbS. Cus. 1. prism and at the centres of top and bottom faces. ice, Mg. CaSO,.2H,0, NaNO,.CaSO, As, Sb, Bi ete HgS, graphite, Ca ete. Na,S0,.10H,0. Na,B,0,.10H,0, monoclinic sul hur ete. Triclinie ‘Simple : Points at eight corners of the unit cell. aebec ae pey2 90" CaSO, SH,O. K,Cr,0,, H,BO, We will focus majorly on cubic unit cells and their arrangements.IIT JEE Reference Material: 3.3.1 Types of cubic Unit Cells Thisis the most common unit cell, Ina cubic unit cell there are following locations for the atoms or spheres * Comers * Body Centre * Face Centres Following are the contributions of a sphere kept at various locations. : www.crackjee.xyz Cubie Unit Cell Body Centred] Face Centred Cubic (BCC), Cubic (F ‘Location Contribution These unit cells differ from each other in following factors, * Location of spheres inside the unit cell. Corners Wes * — Rank of the unit cell (effective number of spheres inside aunitcell) Body Centre \ * Relation between edge length and radius of one sphere, _ * Packing fraction (fraction of volume occupied by Face Centre 12 spheres in a unit cell) The following parameters for all the 3 unit cells are listed is the table below : ‘Type of Cublic Crystal | No. of atomsat different locations Structure Rank | Packing | Relation b/watomic Corners | Body Face radius and edge centre centre length (a) Simple Cubic 8 os - I 52% Body Centred 8 1 - Face Centred 8 nt 63.4 Density of cubic crystals Density of cubic crystal is given by the following formula MxZ Density P= xn where, Z— rank of unit cell M— Molar mass of solid a Edge length of unit cell Ny > Avogadro Number. ‘Valume of Z.will depend upon the type of unit cell, 3.5. Close packing in Solids : Origin of unit cells Suppose we have spheres of equal size a arrange them ina single layer with the cor should come in close contact with each other. Two types of layers are possible 1, Square Packing 2, Hexagonal Packing In square packing spheres are placed in such a way that, the rows have a horizontal as well as vertical arrangement. In this case Co-ordination Number is 4. Hexagonal packing is more efficient. Its Co-ordination ‘Numbers 6and voids inthe packing are smaller than square packing. If we place another layer on square packing then there are following possibilities: 1. A similar ayer placed just above foundation layer that is the spheres of the second layer coming just above the spheres of the first layer and layers get repeated. If first layer is termed A the packing in this case ‘AA... type and the unit cell is simple eubic. 2. Onother hand ifspheres of second layer are placed in dopressions of frst layer we get BCC unit cell and ABAB.... type of packing. ‘Arrangements based on hexagonal foundation layer are as follows: Ifwe put2™ layerin depressions of first hexagonal layer A two types of voids are created, X type of voids are those which are hollow and through voids of layer A and layer B. While ¥ type of voids are those voids of layer B which are exactly above spheres of layer A. If we place the spheres of 2nd layer on Y voids then we are repeating layer 1 and ABABAB.... type packing is obtained. In this arrangement hexagonal unit cell is obtained and packing is called Hexagonal Close Packing (HCP), The efficiency of this packingis 74%, If the 3rd layer is placed on X-type of voids then a new layer C is obtained and then the arrangement will be repeated. We will obtain ABCABCABC.....typeof packing, ‘The unit cell for this arrangement is FCC and the packing effeciency is 74%. Packing of second layer (b) on first layer (a) A A B. B A Al (b) (a) ABABA... orhep arrangement of spheres. Metals like ‘magnesium, zine, ete. adopt this type of arrangement.‘ccp arrangement (©) ABCABCA.... or cep arrangement of spheres The empty spaces inside a spheres are called “voids”. The size and shape of voids depends upon the type of unit cell and packing. 4.2 Radius Ratio The size of void is expressed in terms of radius r sphere that can be exactly fit in the void to the radius of surrounding spheres. This expressed as : r Radius ratio = = aus ratio = 4.3 Typesof voids 4.3.1 Trigonal void Iis a void formed of equal radii and touching each other as shown in figure, Key Points Radius Ratio * Smallest void * Co-ordination no. Trigonal Void 4.3.2 Tetrahedral Void It forms by contact of 4 spheres and is positioned at the centre of tetrahedron formed by contact of 4 spheres. Figure Key Points = Radius ratio e 0.225 * No. of voids in FCC crystal] =8 * Position : ata distance a ASF from every comer * Co-ordination no, = 4 Key Points t * Radius ratio —= 0.414 dius ratio Fe * No. of voids in FCC crystal] =4 * Positions : Body centre Edge centres43.4 Cubie Void 5.1 NaCI Type Structure This void forms by close contact of 8 spheres Figure Key Points Key Points * CT occupy corners and face * Radius Ratio: 0.732 centres and Na* occupy R acthedral voids in FCC ‘ crystal * No. of voids in cubic crystal = ners omen * Effective formula =Na,Cl, * Postion : at body centre 08 Ni * Co-ordination No of Cr * Distance b/w nearest neigh Co-ordination number=8 * Ranh Itis clear from above details that Rock Salt Structure ‘Trigonal = 4. into 5 categories which are as follows " 3 Tyg thKey Points These are defects that occur when positions that should contain atoms or ions are vacant * Common in alkali oxides like Na,O.Li,Oete, * OF ions occupy FCC and Li’ | ions occupy the tetrahedral voids AnticFluorite Structure 5 CsCl Type Structure Figure Key Points * CI ions simple cubic Lo- cations (comers) and Cs* ions occupy body centre in BCC lattice + Effective formula=CsCl * Coordination no of Cs*=8 * Co ordination no, of Cl =8 (Cesium Halide Structure Feet Moe Dds cUe ee) ‘Sometimes some defects or imperfections occur in crystal structure. 6.1 Classification of defects Defects mo Stoichiometric Non-Stoichiometric] defects defects Schoniky] [Frenkel Metal Metal defect defect exeess | |deficiency| defect defect 6.3 Interstitial sites These are sites located between regular positions sometimes atoms or ions may occupy these pos eoo000 e@oeeooe (a) Lattice Vacancies (6) Interstitial Atoms 6.4 Stoichiometric Defects These defects do not disturb stoichiometry of solid substance. 6.4.1 Schottky defects Itisa vacancy defect in ionic solids. No. of missing cations and anions is equal so electrical neutrality is maintained. This defect decreases the density of the substance. The defect is shown by ionic substances in which cation and anion are of almost similar sizes. eq. KCI, NaCl, AgBr etc. Anionic Vacancy t e®nu00 © © © OP ees ©®eoeo0 ‘Schottky 6.4.2 Frenkel defect In ionic solids the smaller ion is dislocated from its normal position to an interstitial site, It ereates a vacancy defect at its original site and interstitial defect at new location. Itis also called as dislocation defect. It does not change the density of solid. This type of defect is shown by ionic substances in which there is a large difference in size of ions, cq ZnS, AgCl, AgBr ete. Cation in Cation Vacancy Interstitial Site A Frenkel defect 6.5 Non Stoichiometric Defects ‘The compounds having these defects contain combining elements in a ratio different from required by their stoichiometric formulae, 6.5.1 Metal Excess Defect Due to anionic vacancies: The anion may be missing from its lattice site leaving an e~ behind so that charge remains balanced. The site containing electron is called F centre. They import colour to the crystal, F stands for Farbenzenter meaning colour. This defect is similar to schottky defect and is found is crystals having schottky defect eq. NaCl, KCI ete, An F-centre in a crystal Due to the presence of extra cations in the interstitial sites. ‘An extra cation may be present in interstitial site and an electron is present in another interstitial site so that electrical neutrality is maintained. This i similarto Frenkel defect and if found in crystal having Frenkel defect. Metal excess defect eaused by extra cation in the interstitial site. 6.5.2 Metal Deficiency Defect This defect occurs when metal shows variable valency. ‘eq, FeO is mostly found is varying compostions between Fe, 4,0 to Fe,,,0. In crystals of FeO some Fe* cations are missing and the loss of positive charge is made up by the presence of required number of Fe"? ions.IIT JEE Reference Materials: www.crackjee.xyz SOLUTIONS & COLLIGATIVE PROPERTIES INTRODUCTION In normal life we rarely come across pure substances. Most of these are mixtures containing two or more pure substances. Their utility or importance in life depends on their composition. The air around us is a mixture of gases primarily oxygen and nitrogen; the water we drink contains very small amounts of various salts dissolved init. Our blood is a mixture of different components. Alloys such as brass, stainless steel, ete. are also mixtures. In this Unit, ‘we will consider mostly liquid solutions and their properties. peel} A solution is a homogeneous mixture of two or more than two components. For example, common salt in water. Clas ion Solutions which contain two components in it are called Binary Solutions. Substances which are used to prepare a solution are called as Components. The component that is present in the largest quantity is knownas Solvent. Solvent determines the physical state in which solution exists, The other component present in lesser quantity in the solution is termed as Solute. Each component may be solid, liquid or in gascous state. Type of Solution | Solute Solvent Common Examples Gaseous Solutions | Gas Gas Misture of oxygen and nitrogen gases Liquid Gas Chloroform mixed with nitrogen gas Solid Gas Camphor in nitrogen gas Liquid Solutions | Gas Liquid | Oxygen dissolved in water Liquid Liquid | Ethanol dissolved in water Solid Liquid | Glucose dissolved in water Solid Solutions Gas Solid | Solution of hydrogen in palladium Liquid Solid | Amalgam of mercury with sodium Solid Solid | Copper dissolved in gold 1.3 Strength of Solutions ‘The amount of solute dissolved peru solvent is called Strength of solution, There are various methods of measuring strength of a solution. : Mass Percentage (%w/w): “It represents mass of a component present in 100 g of solution” Mass of component in thesol Total Mass of sol. ‘00 Mass % of a component 2. Volume percentage (Yov/v): “Ttrepresents volume ofa component in 100 mL. of solution” Vol.of component, Total vol. of solution Vol.% of a component = 100JEE Main Revision Materials: 3. Mass by volume percentage (w/v): “It represents mass of solute in grams present in 100 mL. of solution” Mass of solute in g Mass by vol, percent = 100 Vol. of sol.in mL. Parts per Million (ppm) No.of parts of thecomponent os Parts per Million = —N0-0F Paris of the component _ ants Per Million = tal no. of all the componens of sol. Concentration in parts per million can be expressed as mass to mass, volume to volume and mass to volume. Mole Fraction (x) “It represents the moles of a solute present in one mole of solution” No, of moles of the component Mole fraction = er Total no. of moles all the components For example, in a binary mixture, if the number of moles of A and Bare n, and ny respectively, the mole fraction of A will be Da. x, = m+n, Molarity, M “It represents moles of solute present in | L of solution” __ Moles of solute Molarity, M = Moks of solute Vol. of sol. in L Units of Molarity are mol/L also represented by ‘Molar’, “Density of a solution is mass of the solution per unit volume” say, q _Mass.of sol = Massof sol m/v Density, d= Sere = m/ Molality, m “It represents moles of solute present per kg of solvent” Moles of solute Molatity, m= Moles of solute _ Mass of solvent in kg. Units of molality are mol/kg which is also represented by ‘m’ or ‘molal’ www.crackjee.xyz 8. Normality, N Itrepresents no. of equivalents of solute present in I L of solution, Normality, n= Noo Eauivalen of solute Vol of sol.in I Weight No.of equivalents, eq =———_Welght_ 'o-oF equivalents, e¢ =F aivalent weight (W/E) M (ais the valency factor) SOME IMPORTANT RELATIONSHIPS Dilution Law Ifa solution is diluted by adding solvent to it, then the ‘amount of solute remains constant and we can write: M,V,=M,Y, and N,V, = N,V, Molarity and Normality Normality = z Molarity IMPORTAN1 ‘Mass %, ppm, mole fraction and molality are independent of temperature, whereas molarity & normality are a function of temperature, This is because volume depends ‘on temperature and the mass does not 2. VAPOUR PRESSURE Vapour pressure of a liquid/solution is the pressure exerted by the vapours in equilibrium with the Liquid/solution at a particular temperature, Vapour pressure o escaping tendency 2.2 Vapour pressure of liquid solutions and Raoult’s Law (Raoult’s law for volatile solutes) Raoult’s law states that for a solution of volatile liquids, the partial vapour pressure of each component in the solution is directly proportional to its mole fraction. Consider a solution containing two volatile components Iand 2 with mole fractions x, and x, respectively. Supposeata particular temperature, their partial vapour pressures are , and p, and the vapour pressure in pure stateare p? and p$. ‘Thus, according to Raoult’s Law, for component 1 Pe x and py = pt x) Similarly, for component 2 PL=P3 XS According to Dalton’s law of partial pressure, the total pressure (P,,4) over the solution phase in the container will be the sum of the partial pressures of the components of the solution and is given as Pyout = Pr + Pa Substituting the values of p, and p,, we get Prout = % Pr + %3 PS = (x2) Py +2 PD = pi + (PE Pi) xs ‘Yspour pressure —> x= 1 Mole fraction x x:70 a nol ‘The plot of vapour pressure and mole fraction of an ideal solution at constant temperature, The dashed line I and II represent the partial pressure of the components. It can be seen from the plot that p, and p, are direetly proportional to x, and x, respectively ‘The total vapour pressure is given by line marked in the figure. Mole fraction in vapour phase Ify, and y, are the mole fractions of the components | and 2 respectively inthe vapour phase then, using Dalton’s law of partial pressures: PLAY Prat In general PPM Pro 2.3 Vapour pressures of solutions of solids in and Raoult’s Law (Raoult's law for non volatile solutes) If a non-volatile solute is added to a solvent to give a solution, the number of solvent molecules escaping from the surface is correspondingly reduced, thus, the vapour pressure is also reduced. ‘The decrease in the vapour pressure of solvent depends on the quantity of non-volatile solute present in the solution, irrespective of its nature. Raoult’s law in its general form can be stated as, for any solution the partial vapour pressure of each volatile component in the solution is dircetly proportional to its ‘mole fraction. Inabinary solution, let us denote the solvent by I and solute by 2. When the solute is non-volatile, only the solvent molecules are present in vapour phase and contribute to vapour pressure. Let p, be the vapour pressure of the solvent, x, be its mole fraction, p be its vapour pressure in the pure state. Then according to Raoult’s law Pax, and P=, BE = Pat Vapour pressure of pure solvent Vapour pressure. —> 0 © Mole fraction of solvent Xciver —> If a solution obeys Raoult’s law for all its vapour pressure would vary linearly from zero to the vapour pressure of the pure solvent.deal and Ideal solution An ideal solution is the solution in which each component obeys Raoult’s law under all conditions of temperatures and concentrations, Properties of Ideal solutions : 0 0 * AH, Muxina = = AY, + Intermolecular attractive forces between the A-Aand B-B. are nearly equal to those between A-B. Eg. solution of benzene and toluene, lution of n-hexane and n-heptane Non ~ ideal solutions : Whena solution doesnot obey Raoult’s law over the entire range of concentration, then it is called non-ideal solution, Solutions showing positive deviation from Raoult’s Law : © Solvent-Solute(A-B) type of force is weaker than Solute- Solute(B-B) & Solvent-Solvent(A-A) forces. © The vapour pressure is higher than predicted by the law. © AN res? O © AVwing 2 0 Eg. ethanol and acetone, carbon disulphide and acetone Pressure composition curve for solution showing e de Vopour pressure of solution I g Eg 5 & = x70 Mole fraction x aod ao x0 7x, Solutions showing negative deviations fram Raoult’s law : + Solvent-Solute(A-B) type of force is stronger than the other two, ‘©The vapour pressure is lower than predicted by the law © Aine <0 AV exc 0 For example,phenol and aniline, chloroform and acetone ete cue Pressure composition curves for solution showing negative deviation Vapour pressure of solution ‘Vapour pressure —> x,70 Mole traction xr x71 x x70 0), the solubility increases with rise in temperature and If (A,,,H < 0) the solubility decreases with rise in temperature. Effect of pressure : Does not have any significant effect as sol are highly incompressible. 3.2 Henry Henry’s law states that at a constant temperature, the solubility of a gas in a liquid is directly proportional to the pressure of the gas. ‘The most commonly used form of Henry's law states that “the partial pressure of the gas in vapour phase (p) is proportional to the mole fraction of the gas (x) in the solution”. This is expressed as: Here XK, is the Henry's law constant. sofKy, + is a function of the nature of the gas, Charaeteri © K © Higher the value of K,, ata given pressure, the lower is the solubility of the gas in the liquid. ‘© K,, values increase with increase of temperature indicating that the solubility of gases increases with decrease of temperature.Appl 1 2 x ions of Henry's In the production of carbonated beverages. In the deep sea diving, For climbers or people at high altitudes Raoult’s Law as a special case of Henry's Law According to Raoult’s law, PAX PL In the solution of a gas in a liquid, one of the components is so volatile that it exists as a gas. Its solubility according to Henry's law, PHKyx Thus, Raoult’s law becomes a special case of Henry's law in which K,, becomes equal top? Pee Ua ela) ‘Ther 1 2: 3, 4 “The properties that depend on the number of solute particles, inrespective of their nature relative to the total number of Particles present in the solution are called colligative Properties. are four colligative properties: Relative Lowering of vapour Pressure Elevation in Boiling Point Depression in freezing point ‘Osmotic pressure 4.1 Rel Lower ig of vapour Pressure Whena non-volatile solute is added to a solvent, the vapour pressure decreases, ‘The lowering of vapour pressure w.rt. the vapour pressure of the pure solvent is called “Relative lowering in vapour pressure”. According to Raoult’s Law : PL=X Pr ‘The reduction in the vapour pressure of solvent (p,) is given as: 4p, =P! —Pi=PL~Pi Xs = Pi (l-x,) Knowing that x, = I —x,, equation reduces to OP, =X PL Equation can be wirtte Pi PB . ‘The expression on the left hand side of the equation as ‘mentioned earlier is called relative lowring of vapour Pressure and is equal to the mole fraction of the solute. The above equation can be written as : Ay nth Here n, and n, are the number of moles of solvent and solute respectively present in the solution, For dilute solutions n, ‘Temperature/K ——> ‘The vapour pressure curve for solution lies below the curve for pure water. The m shows that AT, denotes the elevation of boiling point of a solvent in solution, 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. When a non-volatile solid is added to the solvent its vapour Pressure decreases and now it would become equal to thal of solid solvent at lower temperature. Thus, the freezing point of the solvent decreases. AT, = T? =T, where T? and T; is its freezing point when non-volatile solute is dissolved is known as depression in freezing point. the freezing point of pure solvent Expression : AT,= Kym K, is known as Freezing Point Depression Constant o1 Molal Depression Constant or Cryoscopic Constant. Calculation of molar mass of solute : _¥2!My ww, /1000 Substituting this value of molality in equation we get: at -Ka/M, p oankeewrg My vw, /1000 Itis defined as the depression in freezing point when the molality of the solution is unity, The unit of K, is K kg mot Determination of K,: x -REME (000% Ay, where : R = gas constant (8.314 JK/mol), 1,= freezing temperature in K,IIT JEE Reference Materials: www.crackjee.xyz M, = Molar mass of solvent in Ke/mol, 4, enthalpy of fusion of solvent in J/kg Vapour pressure —> ‘Temperature/K —> im showing AT,, depression of the fre point of a solvent in a solution. When a pure solvent and solution are kept with a semi= permeable membrane between them then the solvent particles pass through the membrane from the solvent side to the solution side. This phenomenon is called “Osmosis”. ‘The semi-permeable membrane isa membrane that allows only small molecules to pass through and blocks the larger solute molecules. Selectively Permeable © super Membrane igh Wate Concentration Low Water Concentration Osmotic pressure : ‘The osmotic pressure of a solution is the excess pressure that must be applied to a solution to prevent osmosis, ic, to stop the passage of solvent molecules through a semipermeable membrane into the solution. Solution Solvent ‘The excess pressure equal to osmotic pressure must be applied on the solution to prevent osmosis. Expression : For dilute solutions, osmotic pressure is proportional to the molarity, C of the solution at a given temperature 7. Thus: n=CRT Here m is the osmotic pressure and R is the gas constant. Calculation of molar mass : r=(n,/V)RT Here V is volume of a solution in litres containing n, moles ofsolute. Ifw, grams of solute, of molar mass, M, is present in the solution, then n, = w, / M, and we can write, or Isotonic solutions : ‘Two solutions having same osmotic pressure at a given temperature are called isotonic solutions. The solution with lower concentration or lower osmotic pressure is known as “Hypotonie” with respect to more concentrated solution. The solution with higher concentration or higher osmotic pressure is known as “Hypertonic” with respect to dilute solution.Reverse osmosis : Ifa pressure larger than the osmotic pressure is applied to the solution side, the solvent will flow from the solution into the pure solvent through the semi permeable membrane. This phenomenon is called reverse osmosis, Application : Desalination of sea water : ‘When pressure more than osmotic pressure is applied, pure water is squeezed out of the sea water through the ‘membrane. Abnormal Molar Masses When the molecular mass of a substance determined by studying any of the colligative properties comes out to be different than the theoretically expected value, the substance is said to show abnormal molar mass. Abnormal Molar Masses are observed: 1. When the solute undergoes association in the solution. 2. When the solute undergoes dissociation in the solution. van't Hoff Factor : To calculate extent of association or dissociation, van't Hoff introduced a factor é, known as the van't Hoff Factor, Normal molar mass ‘Abnormal molar mass Observed colligative property Calculated colligative property Ino, of moles of particles after association (diss ‘No.of moles of particles before association (dissociation) Association : Number of particles will always decrease due to association therefore i< 1. nA>A, Let initial particles (n) Final number( n,)= 1 - a+ a/n van't Hoff factor, i= n/n,= 1 a+ ain Dissociation : The number of particles will always increase duc to dissociation and hence i > 1 A, nA Initial particle = | Final particles = 1 - a+ na -atna i Modified Expressions : Relative lowering of vapour pressure of solvent, Elevation of Boiling point AT, Depression of Freezing point, AT, Osmotic pressure of solution, AAT Gt On increasing the temperature of the liquid the escaping tendency of the molecules increases and the vapour pressure increases, moving molecules have ie energy to supe Irom the lqutd and enter the vapour, temperature “The higher the temperature the larger the number of Kinetic energy —> The distribution of molecular kinetic energies in a liquid Claussius-Clapeyron Equation In p/p, = (AH y/R) (1/7, ~ 1/7) where Alyy, represents the enthalpy of vaporisation of the liquid. BEC ekee ese (el) Ifthe interactions grow stronger the process is exothermic and if they go weaker during the formation of solution the process becomes endothermic. In general AS is positive in dissolution process. If the mixing process is spontaneous/natural then AG has to be negative. Number of moleculesJEE Main Revision Materials: www.crackjee.xyZ oa Teaeave a ‘rome Si senepane vette sila pone adnan Ty AM /A8 yp The non-volatile solute increases the randomness of the solution phase and the entropy of the vapours remains the same, Due to this, AS,,, decreases thus giving rise to the boiling point. Bose te ohn na woah heer ei 8. [S.9L ‘sition, ‘Asa reul e potlng oi of Solaon Thigh tun at the ‘ceause the solvent ina afution has 8 Higher ney evel bein wi, Sy in larger forthe anton than forthe “> 7 [9S pean ‘As a rent, the een pout af he ekitlon 7a lower thas that of the pure ealent. Ith in soe {ba tre saver ad the elation Sim then thi ie ‘aller fr the ‘The lower freezing point of a solution relative to that of a pure solvent is due to a difference in their entropies of fusion, AS, 7. OSTWALD WALKER METHOD ‘alton mi) wa) Wal cetwald Walker Method pure solvent eying war The higher boiling point of a solution relative to that of a pure solvent is due to a difference in their entropies of vapourization, AS,,,- 6.2 Freezing Point Depression AG, is T= AH yy AS ius ‘The entropy difference will increase in this case due to the increase in the entropy of solution, This increase in entropy will result in decrease of the freezing point according to the above relation. This isa typical method to measure the relative lowering in vapour pressure of a solution. Dry air is passed successively through three systems: solution, pure solvent and then a drying agent 1w, and w, represent the decrease in weight of the vessels and w, represents the inerease in weight ofthe third vessel due to absorption, 1, % Poouurion , (as the air was already saturated) In W & Poowvent — Psouution Wa © Poouvent Using the above relations the relative lowering in vapour pressure can be calculated.IMPORTANT FORMULAE 2 4. In the formulae given below A represents solvent and B represents solute, also M, = Molar mass of solvent M, = Molar mass of solute W, = Mass of solvent V,,= volume of solute Volume of soluti d= density of solution. ass of percentage (win) = W, gw, <0 Vo Volume percentage (viv) = yy, y_*!00 w)_ Wy x100 Mass by volume percentage | )="V (mip Ww, Parts per million (ppm) = wewr” nm +M, Mole fraction of A, x, a mole fraction of B, x, = Xt Xp, W, By Wa Volume of solution in litre Vj, MaxVay Moles of solute Molarity (M) = Moles of solute ny Ww, 1000 ‘Molality (m) = Mass of solvent in kg Wy 1000 Gram Equivalents of solute Ws Normality (N) = “Volume of solution in litre GEM of solute x V,,, GEM = Gram Eq Relationship between Molarity and Normality alent Mass The normality (N) and molarity (M) of a solution are related as follows : Normality x Equivalent. mass (solute) = Molarity x Molar mass (solute) JEE Main Revision Materials: www.crackjee.xyZ10. i 12, 13, Relationship between Molarity and Mass percentage (p) Ifp is the mass percentage and d is the density of the solution then pxdx10 Molarity =_Pxdx10__ Mol. mass (solute) 7 pxdxl0 Normality = mass (solute) Dilution formula : Ifthe solution of some substance is diluted by adding solvent from volume V, to volume V,, then M,V,= MV, Similarly, NV, =N,V, Mi V, and molarity M,, then molarity of the resulting mixture of solution (M) can be obtained as : ity of a mixture : If V, mL of a solution of molarity M, is mixed with another solution of same substance with volume Vi+M, VAN; joult’s Inw for volatile solute. p= pAx, and Py PhXy where p, and p, are partial vapour pressures of component ‘A’ and component ‘Bin the solution. p’ and p), are vapour pressures of pure components ‘A’ and ‘B' respectively. Total vapour pressure = p =P, + Py = PAXa + PIXn- Raoult's law for non-volatile solute. (For a dilute solution n, < 1, solute undergoes dissociation. i <1, solute undergoes association. |, neither association nor dissociation. l J" solute is dimer, JEE Main Revision Materials: www.crackjee.xyzELECTROCHEMISTRY Peele aL Electrochemistry is the study of production of electricity from the energy released during a spontaneous chemical reaction and the use of electrical energy to bring about non-spontaneous chemical transformations. PR eler aoe} ‘A spontaneous chemical process is the one which can take place on its own and in such a process the Gibb’s, energy of the system decreases. It is this energy that gets converted to electrical energy: The reverse process is also possible in which we can make non-spontaneous processes occur by supplying external energy in the form of electrical energy. These inter conversions are carried ‘out in equipments called Electrochemical Cells. Bias Electrochemical Cells are of two types: 1 Galvanic Cel Converts chemical energy into electrical energy 3.2 Electrolytic Cells Converts electrical energy into chemical energy. CRN Cell energy is extracted from a spontaneous chemical process or reaction and itis converted to electric current. ‘or example, Daniell Cell isa Galvanic Cell in which Zine and Copper are used for the redox reaction to take place. Zn (s) + Cu** (aq) —» Zn** (aq) + Cus) Zn(s) —> Zn** (aq)+2e~ Reduction Half: Cu?*(aq) +2e° —+ Cu(s) Zn is the reducing agent and Cu* is the oxidising agent. The half cells are also known as Electrodes. The oxidation halfis known as Anode and the reduction halfiis called Cathode. Electrons flow from anode to cathode in the external circuit. Anode is assigned negative polarity and cathode is assigned pasitive polarity. In Daniell Cell, Zn acts as the anode and Cu acts as the cathode. Eira t reheat These electrodes are dipped in and electrolytic solution containing cations and anions. On supplying current the ions move towards electrodes of opposite polarity and simultaneous reduction and oxidation takes place. Preferential Discharge of ions Where there are more than one cation or anion the process of discharge becomes competitive in nature. Discharge of any ion requires energy and in case of several ions being present the discharge of that ion will take place first which requires the energy. Stra eee It may be defined as the tendency of an element, when itis placed in contact with its own ions to either lose or gain clectrons andin tum become positively or negatively charged. The electrode potential will be named as oxidation or reduction potential depending upon whether oxidation or reduction has taken place. Ms) SEEM" (aq) +e” i * (oq) ne" M(s) (a) Both oxidation and reduction potentials are equal in ‘magnitude but opposite in sign (b) It is not a thermodynamic property, so values of E are not additive. DCR ssa el ae im( Itmay be defined asthe electrode potential ofan electrode determined relative to standard hydrogen electrode under standard conditions. The standard conditions taken are = IIT JEE Reference Materials: www.crackjee.xyz(i) IM concentration of each ion in the solution. (ii) A temperature of 298 K. (iii) | bar pressure for each gas. 8. ELECTROCHEMICAL SERIES The half cell potential values are standard values and are represented as the standard reduction potential values as shown in the table at the end which is also called Electrochemical Series. EMSS eee wae The difference between the electrode potentials of two half cells is called cell potential, tisknown as electromotive force (EMF) of the cell ifno current is drawn from the cell, Bsa Coste + Ems For this equation we take oxidation potential of anode and reduction potential of cathode. ‘Since anode is put on left and cathode on right, it follows therefore, +E, Fora Daniel cell, therefore 10. CELL DIAGRAM OR REPRESENTATION lene The following conventions or notations are applied for writing the cell diagram in accordance with IUPAC recommendations, ‘The Daniel cell is represented as follows : Zn(s)|Zn°* (C,)I1Cu** (C,)| Cu(s) (a) Anode half cell is written on the left hand side while cathode half cell on right hand side, mgs =0.344(0,76)=1.10V (b) Asingle vertical line separates the metal from aqueous solution of its own ions. Zn(s)| Zn" (aq); Cu" (aq)|Cu(s) Cato canter (c) Adouble vertical line represents salt bridge (d) The molar concentration (C) is placed in brackets after, the formula of the corresponding ion. (c) The value of e.m4f. of the cell is written on the extreme right of the cell. For example, IIT JEE Reference Material Za(s)|Zn** (1 M)|| Cu® (1 M)| Cu EMF=+1.1V (f) Ifan inert electrode like platinum is involved in the construction of the cell, it may be written along with the ‘working electrode in bracket say for example, when azine anode is connected to a hydrogen electrode, Zn(s)| Zn" (C,)|H" (C3)| MH, |(Pt)(s) PEM tees Salt bridge is used to maintain the charge balance and to complete the circuit by facilitating the flow of ions through it Itcontains a gel in which an inen electrolyte ike Na,SO, or KNO, etc are mixed. Negative ions flow to the anode and positive ions flow to the cathode through the salt bridge and charge balance is maintained and cell keeps on funct Voltmeter/Ammeter Sal bridge Cong: 80, zs0, cuso, Sol. al ‘Anode MoemenofCaony Cathode Zn-HZn° 426 Movement of Aone Cus 2e > Cu tecrochemical ell hasedom the rox reaction, Za + CuSO, > 7480, Co pro eae Witz Xoo} AGE PFE can: For a spontaneous cell reaction AG should be neg: and cell potential should be positive. If we take standard value of cell potential in the above equation we will obtain standard value of AG as well 0 ca. SEMA a dey sy A metal rod/plate is dipped in an electrolyte solution containing metal ions. There is a potential difference between these two phases and this electrode can act as a cathode or anode both AG*= www.crackjee.xyzAnode: M—» M™ + ne~ Cathode: M" +e —> M. Electrodes Electrode gases like H,, Cl, etc are used with their respective ions. For example,H, gasis used with a dilute solution of HCL (UF ions). The metal should be inert so that it does not react with the acid, Aytrogen Platinum electro coated win finely ‘divided platinum A solution of acid (platinum bine ‘containing un fective hydrogen fom concentration of molar Standard Hydrogen Electrode Anode: Hl, —» 21" + 2° Cathode: 211° +26" —» Hh, ‘The hydrogen electrode is also used as the standard to ‘measure other electrode potentials. Its own potential is set to 0 Vas a reference, When itis used as a reference the concentration of dil HCI is taken as 1 M and the electrode is called "Standard Hydrogen Electrode (SHE)”. 13.3 Metal-Insoluble salt electrode We use salts of some metals which are sparingly soluble with the metal itselfas electrodes. For example, if we use ‘AgCl with Ag there is a potential gap between these two phases which can be identified in the following reaction AgCI(s) + 0° > Ag(s) +r This electrode is made by dippinga silver rod ina solution containing AgCK(s) and CI" ions. ‘Calomel E trode Mercury is used with two other phases, one is a calomel paste (Hlg,Cl,) and electrolyte containing Cl" ions, mae vee smut Mec nd oy cateeteterete Cathode = Hg,Cl(s) +20" —+ 2Hg()+2CH(aq) Anode : 2g) + 2CH(aq) —y Hg,Ch(s) + 2e- This electrode is also used as another standard to measur other potentials. Its standard form is also called Standarc mel Electrode (SCE), 13.5 Redox Electrode In these electrodes two different oxidation states of th same metal are used in the same half cell, For example Fe® and inert electrode of platinum is used for the electron transfer Following reactions can take place: Anode: Fe —» Fe'"+e- are dissolved in the same container and ar Cathode: Fe" +e 5 Fett Be NERNST EQUATION Itrelates electrode potential with the concentration of ions Thus, the reduction potential increases with the increas in the concentration of ions. For a general electrochemica reaction of the type. aA +bB— eC +dD Nemst equation can be given as ar, [cI of fay tey Egy =(@ Nature of electrolyte or interionic attractions : Lesser the solute-solute interactions, greater will be the freedom ‘of movement of ions and higher will be the conductance. Gi) Solvation of fons : Larger the magnituele of solute-solvent interactions, greater is the extent of solvation and lower will be the electrical conductance. “The nature of solvent and its viscosity : Larger the solvent- solvent interactions, larger will be viscosity and more will be the resistance offered by the solvent to flow of ions and hence lesser will be the electrical conductance. (v) Temperature : Asthe temperature of electrolytic solution rises solute-solute, solute-solvent and solvent-solvent interactions decreases, this results in the increase of electrolytic conductance. 24, MEASUREMENT OF CONDUCTANCE 1 R iff we measure /, Aand R. The value of the resistance of the solution R between two parallel electrodes is determined by using ‘Wheatstones’ bridge method c Asiwe know, iq The value of could be known, (Fig) Conductivity cet Ry w if Detector ® e Whestatone Bridge It consists of two fixed resistance R, and R,, a variable resistance R, and the conductivity cell having the unknown resistance R,. The bridge is balanced when no current passes through the detector, Under these conditions, RR 25. MOLAR CONDUCTIVITY (A, It may be defined as the conducting power of all the ions produced by dissolving one mole of an electrolyte placed between two large electrodes at one centimeter apart. Mathematically, 1000 AL =KxV, A, ‘ c where, V is the volume of solution in em? containing 1 mole of electrolyte and C is the molar concentration. = ohn! em? mol or S cm? mol 26. EQUIVALENT CONDUCTIVITY (A,.) It is conducting power of one equivalent of electrolyte placed between two large electrodes at one centimeter apart. ‘Mathematically: Kxve «1000 N Where, v is the volume of solution in em? containing 1 equivalent of electrolyte and N is normality. Units: 1000 _ Ohm"! cm? equivalent” equivalent cm” or Sem* equivalent 27. VARIATION OF CONDUCTIVITY AND MOLAR (eee LAA DL euco mntration, Sem* Conductivity decreases with decrease in con this is because the number of ions per unit volume that carry the current in the solution decreases on dilution. Molar conductivity (A,, = «x V) increases with decrease in concentration. This is because the total volume V of solution containing one mole of electrolyte also increases.Ithas been found that the decrease in x on dilution of a Here, 2 and 2. are the limiting molar conductivities of miles is more than compensated by increases in its aia a ac eps volume. EU Leone aeT aNd Graphic representation of the variation of A,, vs ve | 20_APPUCATIONS OF KOHLRAUSCHS LAW] 400 o |CH;COOH For example, molar conductivity of acetic acid at infinite t dilution can be obtained from the knowledge of molar & conductivities at infinite dilution of strong electrolyte like oon. HG, CH,COONa and NaClas illustrated below. = Ke! Aecer-coony = Men -cooP yy Sw te tLe te JL + J 0. 4 Fa ni (mony? ° ie. Anse, coon cone) + Angier) ~ Amnacr 28, LIMITING MOLAR CONDUCTIVITY (A, ] ‘The value of molar conductivity when the concentration ‘approaches zero is knownas limiting molar conductivity or molar conductivity at infinite dilution. It is possible to tion (A°,)in Degree of dissociation («) of Weak Electrolytes determine the molar conductivity at infin case of strong electrolyte by extrapolation of curve of ‘A,, vsVe. On contrary, the value of molar conductivity of weak electrolyte at infinite dilution cannot be determined by extapolation of the curve as the curve becomes almost parallel to y-axis when concentration approaches to zero. ‘Determination of Disso (K) of Weak Electralyt Constant ‘The mathematical relationship between A,, and A‘, for strong electrolyte was developed by Debye, Huckel and x Onsagar. In simplified form the equation ean be given as also ae AS abe” : ise Raga ofan laa) C(AS where A* is the molar conductivity at infinite dilution T=ARTAZ An (AS = As) and b is a constant which depends on the nature of the solvent and temperature. TPN nse eee HALF Ri CE Rae elu CELL REACTIONS ‘When we have two half cell reactions such that on adding them we obtain another half cell reaction then their ems ‘cannot be added directly, But in any case thermodynamic functions like AG can be added and emf values can be related through them, Consider the following three halfcell reactions: Itstates that the limiting molar conductivity ofan electrolyte canbe represented as the sum of the individual contributions of the anion and cation of the electrolyte. In general, if an electrolyte on dissociation gives v, cations and v_ anions then its limiting molar conductivity is given by 2 42e Fe E, Abe watevat Fe? +20 Fe EyFe" +3e—+Fe E, Fe?" +e" > Fe Ey We can easily observe that the reaction can be obtained by subtracting the first reaction from the second. But the same relation does not apply on the emf values ‘That is, E, # E, — E,. But the AG values can be related, according to the reactions. That is, AG,=AG,-AG, n,FE, +n,FE, +26, We should always remember that emf values areadditive only when two half cell reactions are added to give a complete balanced cell reaction, In any other case we will be using AG values to obtain relations between emf values. 4, £ R=p{]}=px Cell constant of <)=» ll cons where, R= Resistance A p= Resist rea of cross-section of the electrodes. l =<» cell constant R where, x= Conductivity or specific conductance «1000 where, A,,= Molar conduct M-= Molarity of the solution. AMA, B=xAL(A)+ YAS (BY) where, AZ, are the number of cations and anions produced by one formula unit of the electrolyte on complete dissociation. Molar conductivity at infinite dilution x and y 5 # 10. a= Degree of dissociation Ag= Molar conductivity at a given concentration Fora weak binary electrolyte AB where, K = Dissociation constant Bea = Eh + Ele Right +E*Iett Nernst equation for a general electrochemical reaction aA+bB "5 cC+eD Rt, [cl (Oy aF fat (ef 2303RT, [CT [P]! oo ATF 2.059 og AT 8). 298K ner Py ae los = 90557 where, K,= Equilibrium constant, A,G" =-nFE%, (Creterion of spontaneity) A,G" =-2.303RT log K, where, 4,G’= Standard Gibbs energy of the reaction. Qalxt where Q= Quantity of charge in coulombs 1 = Current in amperes t= Time in seconds m=Zx1xt where m= mass of the substance liberated at the electrodes = Electrochemical equivalent. where E= Equivalent weight = E/96500CHEMICAL KINETICS INTRODUCTION Chemical Kinetics (Kinesis : Movement) ‘The branch of chemistry which deals with the study of the rates of chemical reactions, the factors affecting the rates of the reactions and the mechanism by which the reactions proceed is called Chemical Kinetics. Classification of reactions (On the basis of rates : © Very fast reactions 4, precipitation of AgCl © Very slow reactions © Reactions taking place at moderate speeds eg. hydrolysis of starch 1. RATE OF A CHEMICAL REACTION The rate of a reaction can be defined as the change in concentration of a reactant or a product in unit time, The rate of reaction measured over a def time interval is called average rate ofa reaction. Consider a hypothetical reaction, RP Average rate of reaction = (Decrease in concentration of R) (Time taken) = -{AR]/ At Or = (Increase in concentration of P) / (Time taken) =[AP]/At 1.2 Instantaneous rate Rate of change of concentration of any one of the reactants or products at that particular instant of time is called instantaneous rate. As At+0 or IMPORTANT: Rate of a reaction is always positive, Since, A[R] is a negative quantity (as concentration of reactants is decreasing), itis multiplied with -1 to make the rate of the reaction a positive quantity, 1.3 Units of rate ofa reaction Units of rate are concentration time ¢.g. mol L's !; atm s“'(for gaseous reactions) 1.4 Overall rate ofa reaction When there are several reactants and products the individual rates of the various components may differ as they would depend on the stoichiometric coefficients. Fora reaction, A+2B —>3C+4D Rate of disappearance of B = 2 Rate of disappearance of AGI) Rate of formation of C=3 * Rate of disappearance of A en Rate of formation of D =4 = Rate of disappearance of A a To define a unique value for the overall rate of the reaction ‘we divide the individual rates by the respective coefficients and equate their signs. Overall Rate=— AA/At = =(+1/4) aD/ at 1/2) AB/At =(+1/3) AC/AtRemember!!! 2.2 Order ofa Reaction aA+bB —> cC+dD aA+bB—*cC+dD Overall Rate=(-I/a) AA/At =(-1/b) AB/At Rate=k [AP [B} = (#M/e) AC/At= (+14) AD/At Sum of these exponents, c.,x+y gives the overall order of W/o) dB/dt areaction where x and y represent the order with respect to 0 Instantaneous Rate = (—I/a)dA/dt = =(41/e) dCidt= (41/4) aD/at the reactants A and B respectively, Hence, the sum of powers of the concentration of the acai eine reactants in the rate law expression is called the order of that chemical reaction. Factors Influencing Rate of a Reaction Order ofa reaction can be 0, 1,2, 3 and evena fraction, * concentration of reactants (pressure in ease of gases), 2.3 Units of rate constant © temperature and + catalyst Rate=k [AT [BP Dependence on Concentration : Consider a general reaction aA+bB—>cC+eD Rate _ concentra 1 [AT (BP ~~ time (concentration)" Reaction Order | Units of rate constant The rate expression for this reaction is Raea (A) [B)’ where exponents x and y may or may not be equal to the stoichiometric coefficients (a and b) of the reactants. Rate=k [A [B} =d[R] /dt=k [AP [BY Above equation is known as differential rate equation, Zero order reaction First order reaction isa proportionality constant called rate constant. Rate law is the expression in which reaction rateis given in terms of molar concentration of reactants with each term raised to some power, which may or may not besame as the stoichiometric coefficient of the rea: abalanced chemical equation. ing speciesin IMPORTANT Rate law for any reaction cannot be predicted by merely looking at the balanced chemical equation, theoretically but must be determined experimentally. eg 2NO(g)+0,g) > 2NO,(g)Rate=k[NO}[O,] RoP ‘The rate of the rea tion is proportional to zero power of the concentration of reactants. CHCI,+Cl, > CCI,+HCI Rate=k [CHCI,] [Cl]? Rate=-[dR] /dt=kR°When of the reactant, chere [R], is the initial concentration ‘Therefore, equation can be written as In[R],=-kx 0+ In[R] Substituting the value of fin equation In[R]=-kt+In{R], 0) Rearranging this equation 3) Attime , from equation (2) In[R},=—kt,+In[R],, Attime t, Inf}. + In[R], where, [R], and [R], are the concentrations of the reactants at time t, and t, respectively. Subtracting In [R], —In[R], =—kt, —(-Kt) RI, in fRETR(=t) Comparing equation (2) with y= mx + ¢, if we plot In [R] against (, we get a straight line with slope =-kand intercept qual toIn (RJ, In[R] —+ eg ‘The first order rate equation (3) can also be written in the form 2.303 1 [Rlo ve tR IRL __kt tog Ph “8 TR] 2303 2 Z| ‘Slope = k/2.303 9 2 0 Time —+ ‘Hydrogenation of ethane, CoH, (8) + H,(g) > CH, (8) Rate=k [CH] Decomposition of N,O, and NO 33 fe of a Reaction 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. Represented as : 5 Fora zero order reaction, rate constant is given by equation. ey FIR, ‘The rate constant att, becomes [Rb-1/21RL,For the first order reaction, 2303, (Rb, eR) at ths ry=Bb 2 So, the above equation becomes 2.308 jog LRle ha IRV? 4 Pseudo First Order React Reactions which are not truly of the first order but under certain conditions become reactions of the first order. CH,COOC,H, + H,0—"+CH,COOH +C,11,0H Rate=k (CH,COOCH,] [11,0] ‘The concentration of water does not get altered much during the course of the reaction. So, in the rate equation the term [11,0] can be taken as constant. Rate= k’ (CH,COOC,H,] where k” =k[I,0] Cat04 + 1 0+ G11,,0, +C,11,,0,, Rate=k [C,,H,,0,,] Case- 1: In gaseous phase reactions we prefer to measure the pressure of the gases or volume. For example the following reactions : For a first order gas phase reaction of the type : A(g) —+ B(g)+ Cie) Let p, be the initial pressure of Aand p, the total pressure at time't Integrated rate equation for such a reaction can be derived as: Total pressure p, =P, + Py * Pe (Pressure units) p,, Py and Pc are the partial pressures of A, B and C, respectively. Ix atm be the decrease in pressure of A at time t. and one mole each of B and C is being formed, the increase in pressure of B and C will also be x atm each. Alg) > Big) + Cig) Att=0 pam = Oatm — Oatm Attimet (p,-x)atm xatm —xatm where, p, is the initial pressure at time t x)txt X=p,-(0,-P) ee bea) t Pa 2303 =230i, 5 —B 1 2p,-P,) Fora first order gas phase reaction of the type : Au) > Bay + CerThe data given to us is: Time | Pressure of gas C/Total Pressure 0 0 t P, eo P, If-we have to find the expression for k or verify that its a first order reaction then we will use the expression for k But we don’t know the values for a or a~x but we ean find the above ratio by relating the givendata with concentration values. For gases, P oc number of moles Ay 7 BGG, PL-P, oan aa-x) = P, (P, -P) Now we can substitute this into the expression for k. k= (In [P_(P_-P)] The above expression can be used to evaluate the value of k from the pressure data and also verify that the reaction is, of first order by checking 2-3 data points. In the above the expression would have been same for the following reactionsas well as the constants will cancel out, Ay > BY+2C,, Ay, > 2B,,+C,, (iftotal pressure is given) ‘And the results will be same if the similar data is given in terms of volume. (Case 2 : [fone of reactants is titrated with a red/ox reagent: Suppose we have a reaction of the type: A>BtC ‘And suppose we detect the amount of A left by titrating it with some reagent and volume of that reagent reacting with the left over A is given at different time interval Volume of the reagent Now the volume of the reagent will be proportional to the moles of A present. Therefore: Viaa V, « a-x We can evaluate kz kt = In(vyV) If the same reagent reacts with all the reactants and produets: V,«a V, 2 atx 2V,-V, « a-x kt=In(V2V,-V)Reaction N,0, +2NO, +40. NH, NO, (aq)-» 211,0 +N, 11,0, +11,0+40, CH,COOC,H, +H,0—"+cH,cooH +C,H,OH CH 04+ HO GH),0,+ CHO, (After the reaction is complete the equimolar mixture of glucose and fructose oblained is lacvorotatory) Initial Rate Data Method: ‘We take different set of initial concentration and measure the initial rate. Then by keeping the concentration of one of the reactants constant and varying the other one we can study the effect on the rate and hence find out the order. Logarithmic data method: Forany order, be it fractional or integral, if we plot log (rate) vs log (concentration) graph it will always bea straight line for the reactions of the type: A - products Rate, r= KAT log r=logk + nog [A] We can take various data points and convert them to log. values and plot them. We will obtain a straight line after curve-fitting with slope n and intercept log k. And hence we can find out the order and rate constant from the graph. Expression for rate constant 2303, V. «= 72383), 1 VV, Here V, = volume of O, after time t and V., volume of, after infinite time. Same asabove, here V,and V, are volumes Of, at time tand at infinite time respectively. Here V, and V, are the volumes of KMnO, solution used for titration of sam of reaction mixture at zero time (ii and after time t. Here V,,V, and V, are the volumes of NaOH solution used for titration of same volume of reaction mixture after time, 0, ¢ and infinite time respectively. r, are the polarimetric readings after time 0,1 and infinity respectively. log (Rate) —> log (conc) ——> iti, lalf Life Method: If'we take various concentrations of reactant and measure half life forall of them then we can find out the order ofthe reaction by mere observation or with the help of some calculations. «= [Al,!If'simple observation is not possible then we can calculate the order of the reaction by taking two data points and using log for calculating n. By integrated rate Equations: If we have simple data of concentration and time we can use the integrated rate equations to find out the order. For this we will have to try and fit the data into the equation at various intervals and calculate the value of rate constants. If the values come out to be the same in all intervals then the data fits into the equation taken and we will know the order, For example, we have the following data: And if we assume that it can be of first order then we will calculate the values of k at minimum three data points by using the equation for first order: (i) In(AJA)=k Let these values be k,, k,and k, If k, = k,=k, then it means that this data fits into the above equation hence the order is LI it doesn’t we will have to try other equations as well. Isolation method: Inthis method we try and eliminate one of the two reactants fromthe rate equation by taking it in excess. What happens is when the amount of a reactant is in excess its effect on the rate becomes marginal or negligible and then we can vary the concentration of the other reactant and observe its effect on rate and find out the order. Welk aU aOR eu IE 1 Molecu ‘The number of reacting species (atoms, ions or molecules) taking part in an elementary reaction, which must collide simultaneously in order to bring about a chemical reaction is called molecularity of a reaction, Class ation of reactions on the basis of Molecularity : Unimolecular renetions : when one reacting species is involved, for example, decomposition of ammoniumnitrite NH,NO, > N,+2H,0 ‘Step- Bimolecular reactions : involve simultaneous colli between two species, for example, dissociation of hydrogen iodide. 2M > +1, ion Trimolecular or termolecular reactions : involve simultaneous collision between three reacting species, for example, 2NO+0, ~ 2NO, Reactions with molecularity greater than three are very rare. The reactions taking place in one step are called elementary reactions, When a sequence of elementary reactions (called mechanism) gives us the products, the reactions are called complex reactions. ‘The different steps in which the complex reaction takes Place is called the mechanism of the reaction. Rate determining step: ‘The overall rate of the reaction is controlled by the slowest. step in a reaction called the rate determining step. A complex reaction can be represented as a series of clementary steps. Forexample 2NO(g)+F(g) > 2NO,F(g) Experimentally, Rate of reaction = k{NO,][F,] Probable mechanism: NO,+NO,— NO+NO, (slow) Step-2: NO,+CO > NO,+CO, (fast) Slow step : bimolecular Hence, abimolecular reaction,Reaction intermediates : ‘There are some species which are formed during the course fof the reaction but do not appear in the overall reaction. They are called reaction intermediates. eg. NO, in the above example. Distintion between Order and Molecularity of a reaction Order 1. Order is the sum of the powers of the concentration of the reactants in the rate law expression, 2 Iean be zero and even a fraction. 3. Iisapplicable to elementary as well as complex reactions. 4, It-can be determined experimentally only and cannot be calculated 5. For complex reaction, order is given by the slowest step. Molecularity 1. Molecularity is the number of reacting species taking part in an elementary reaction, which must collide simultaneously in order to bring about a chemical reaction, n It cannot be zero or a non integer. Itis applicable only for elementary reactions. For complex reaction molecularity has no meaning. 4, Itcan be calculated by simply adding the molecules of the slowest step. Generally, molecularity of the slowest step is same as the order of the overall reaction. Pm aa asaya According to collision theory, a reaction takes place because the reactant molecules collide with each other, ‘The minimum energy which the colliding molecules must, have in order that the collision between them may be cffcetive is called threshold energy. The minimum extra amount of energy absorbed by the reactant molecules so that their energy becomes equal to threshold value is called activation energy. eg ‘Threshold energy =Activation energy + Energy possessed by thereactants Less is the activation energy, faster is the reaction. In order that the reactants may change into produets, they have to cross an energy barrier (corresponding to threshold energy), Reactant molecules absorb energy and form an intermediate called activated complex which immediately dissociates to form the products. H I l+| HOI Intermediate Reaction profile of an exothermic reaction Activated complex Progress of the reaction ——+ (Exothermie) Reaction profile of an endothermic reaction Activated complex Reactants A+B Progress of the reaction ——» (Exothermic)2 Temperature Dependence of the Rate of Reaction Fora chemical reaction with rise in temperature by 10°, the rate constant is nearly doubled. ‘Temperature coefficient = (Rate constant at T + 10°) / (Rate constant at T°) Explanation : Ata particular temperature, if fractions of molecules are plotted versus corresponding kinetic energies, a graph of the type shown is obtained, The peak of the curve represents the kinetic energy possessed by the maximum fraction of molecules and is called most probable kinetic energy. Fraction of molecules —» ‘Most probable kinetic ener Kinetic energy —> Distribution curve showing energies among gaseous molecules s g i Eng of z femfon —_ Thisarea shows = fraction of ana & Thi area ‘molecules which ' hows Facto react at(¢ 10), & Siete Kinetic energy ——> ution curve showing temperature dependence of rate of areaction With increasein temperature : (maximum of the curve moves to the higher energy value i.e., most probable kinetic energy increases (the curve spreads to the right ic., there is a greater proportion of molecules with much higher energies. ‘The area under the curve remains constant since total probability must be one at all times. At (t+ 10), the area showing the fraction of molecules having energy equal to oo greater than activation energy gets doubled leading to doubling the rate of a reaction Arrhenius equation Quantatively, the temperature dependence of the rate ofa chemical reaction can be explained by Arthenius equation keAcfe where A is the Arrhenius factor or the frequency factor or pre-exponential factor. R is gas constant and E; isaetivation energy measured in joules‘mole. ‘The factor ¢°*s/* corresponds o the fraction of molecules that have kinetic energy greater than E, Thus, it has been found from Arthenius equation that increasing the temperature or decreasing the activation ‘energy will result in an inerease in the rate of the reaction and an exponential increase in the rate constant ‘Taking natural logarithm of both sides of equation The plot of In k vs 1/1 gives a straight line with slope E, = and intercept = In. At temperature T,, equation E, Ink, = E+ in A RT, At temperature T,, equation is Fe eina Ink, (since A is constant for a given reaction) k, and k, are the values of rate constants at temperatures T, and T, respectively. Substracting equation form, we obtain Ink, -Ink, = 2-2Csi isa eel ce he eg. ‘Action of the c: A+B+C—> & A catalyst is a substance which alters the rate ofa reaction without itself undergoing any permanent chemical change. May 2KCIO, 2-42 KCI+30, According to intermediate complex theory, reactants first combine with catalyst to form intermediate complex which then decomposes to form the products and regenerating, the catalyst Bm ABiC Catalyst i Product Catalyst Reactants \d (Regenerated) Intermediate complex Effect of catalyst on activation energy Reaction path ~4 Potential eneray without catalyst go | Energy of Energy of |_| activation »\ activation |} without Reaction with catalyst path with catalyst $f catalyst = Reaction coordinate Catalyst provides an alternate pathway by reducing the activation energy between reactants and products and hence lowering the potential energy barrier. Important characteristics of catalyst : © _ Asmall amount of the catalyst can catalyse a large amount of reactants, © Acatalyst does not alter Gibbs energy, AG of a reaction © It catalyses the spontaneous reactions but docs not catalyse non-spontaneous reactions. O A catalyst does not change the equilibrium constant of a reaction rather, ithelps in attaining the equilibrium faster. 7. COLLISION THEORY OF CHEMICAL REACTIO! According to this theory, the reactant molecules are assumed to be hard spheres and reaction is postulated to occur when molecules collide with each other. Rate of reaction depends on the number of effective collisions which in turn depends on : (Energy factor: colliding molecules must have energy more than threshold energy. (i) Steric or probability factor (P) : colliding molecules must have proper orientations at the time of collision ‘Thus, the Arrhenius equation is modified to k= PZy oot Pa eae Ue 8.1 Rate of Reactions 14B_1de_1 aD a@ ba ca aaJEE Main Revision Materials: : Www.crackjee.xyz ‘Zero-Oriler First Order Second Order _aAl, _aal, _4 A wap Rate Law HA =k EM =A] TAL = {ay Integrated [A]=14],-kt [AI=[Aje* ae te tape ” . [A] [Alo far [Alo Rate Law (Except first Order) Units of Rate : : Ms Constant (k) Linear Plot t. [Alyse Inf) vs.t dust 1st inear Plot to. vs n({ AD) vs. = Tv S. (fA) [Al far determine k (Except first Order) l Maltlife {Alo ue 2k “TALK (Except first Order)CBSE Class 12 Chemistry Quick Revision Notes Chapter 5 Surface Chemistry « Adsorption: (i) The accumulation of molecular species at the surface rather than in the bulk ofa solid or liquid is termed as adsorption. (ii) It is a surface phenomenon. (iii) The concentration of adsorbate increases only at the surface of the adsorbent. « Adsorbate: It is the substance which is being adsorbed on the surface of another substance. ¢ Adsorbent: It is the substance present in bulk, on the surface of which adsorption is taking place. © Desorption: It is the process of removing an adsorbed substance from a surface on which it is adsorbed. ° Absorption: (i) It is the phenomenon in which a substance is uniformly distributed throughout the bulk of the solid. (ii) It is a bulk phenomenon. (iii) The concentration is uniform throughout the bulk of solid. © Sorption: When adsorption and absorption take place simultaneously, it is called sorption. e Enthalpy or heat of adsorption: Since, adsorption 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: There are different types of adsorption namely, 1. Physical adsorption 2. Chemical adsorption ¢ Physical adsorption (i) If the adsorbate is held on a surface of adsorbent by weak van der Waals’ forces,the adsorption is called physical adsorption or physisorption. Gi) It is non-specific. Gii) It is reversible. (iv) The amount of gas depends upon nature of gas, i.e., easily liquefiable gases like NH3, CO2, gas adsorbed to greater extent than Hz and He. Higher the critical temperature of gas, more will be the extent of adsorption. (v) The extent of adsorption increases with increase in surface area, e.g. porous and finely divided metals are good adsorbents. (vi) There are weak van der Waals’ forces of attraction between adsorbate and adsorbent. (vii) It has low enthalpy of adsorption (20 - 40 kj mol-1). (viii) Low temperature is favourable. (ix) No appreciable activation energy is needed. (x) It forms multimolecular layers. © 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. Gi) It is highly specific. ii) It is irreversible. (iv) The amount of gas adsorbed is not related to critical temperature of the gas. (y) It also increases with increase in surface area. (vi) There is strong force of attraction similar to chemical bond, (vii) It has enthalpy heat of adsorption (180 - 240 kJ mol-1). (viii) High temperature is favourable. (ix) High activation energy is sometimes needed. (x) It forms unimolecular layers. « Factors affecting adsorption of gases on solids: a. Nature of adsorbate: Physical adsorption is non-specific in nature and therefore every &as gets adsorbed on the surface of any solid to a lesser or greater extent. However, easily liquefiable gases like NH3,HCl, COz, etc. which have higher critical temperatures areabsorbed to greater extent whereas Hz, Oz, 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 ga at constant temperature is called adsorption isotherm and is given by x = = kp/"(n > 1) m 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 © The solid z= first increases with increase in pressure at low pressure but becomes independent of pressure at high pressure. Bix + P—+ ‘Taking logarithm on both sides, we get, L log slonk+—togpTaking logarithm on both sides, we get, log Z = logk+ Llogp « Ifwe plot a graph between log = and log P, we get a straight line. Log k (Intercept) Log P —> ‘The slope of the line is+ and intercept will be equal to log k. © Catalyst: These are substances which alter the rate of a chemical reaction and themselves remain chemically and quantitatively unchanged after the reactionand the phenomenon is known as catalysis. © Promoters: These are the substances which increase the activity of catalyst. Example. Mo is promoter whereas Fe is catalyst in Haber’s Process. Fe(s)/Mo(s) No(g) + 3Ho(g) ———— 2N Hai) © Catalytic poisons (Inhibitors): These are the substances which decrease the activity of catalyst. Example -Arsenic acts as catalytic poison in the manufacture of sulphuric acid by ‘contact process.’ © Types of catalysis: There are two types of catalysis namely, 1, Homogeneous catalysis: When the catalyst and the reactants are in the same phase, this kind of catalytic process is known as homogeneous catalysis. 2, Heterogeneous catalysis: When the catalyst and the reactants are in different phases, the catalytic process is said to be heterogeneous catalysis. 3. Activity of catalyst: It is the ability of a catalyst to increase the rate of a chemical reaction 4. Selectivity of catalyst: It is the ability of catalyst to direct a reaction to yield a particularproduct (excluding others). For example: CO and Hz react to form different products in presence of different catalysts as follows: wi 1. CO(g) + 3H2(g) —+ CHa(g) + H20(g) Cu/ZnO-Cr203 2. CO(g) + 2H2 (9) —————> CH30H (9) 3. CO(g) + H2(g) “ HCHO(g) e Shape - selective catalysis: It is the catalysis which depends upon the pore structure of the catalyst and molecular size of reactant and product molecules. Example - Zeolites are shape - selective catalysts due to their honey- comb structure. © Enzymes: These 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: (i) Binding of enzyme to substrate to form an activated complex. (ii) 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. Example - Urease catalysis hydrolysis of urea only. (ii) 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*, Co®* and Cu”* 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. © True solution: (i) It is homogeneous. (ii) The diameter of the particles is less than 1 nm. (ii) It passes through filter paper. (iv) Its particles cannot be seen under a microscope. * Colloids: (i) It appears to be homogeneous but is actually heterogeneous. (ii) The diameter of the particles is 1 nm to 1000 nm. (iii) It passes through ordinary filter paper but not through ultra-filters. (iv) Its particles can be seen by a powerful microscope due to scattering of light. * Suspension: (i) It is heterogeneous. (ii) The diameter of the particles are larger than 1000 nm. (ii) It does not pass through filter paper. (iv) Its particles can be seen even with naked eye. © Dispersed phase: It is the substance which is dispersed as very fine particles. © Dispersion medium: It is the substance present in larger quantity. © Classification of colloids on the basis of the physical state of dispersed phase and dispersion medium: PaintsGas smoke, dust | Gel Liquid Solid Cheese, jellies ¢ Classification of colloids on the basis of nature of interaction between dispersed phase and dispersion medium, the colloids are classified into two types namely, 1. Lyophobic sols 2. Lyophilic sols * Lyophobic sols: (i) These colloids are liquid hating. (ii) In these colloids the particles of dispersed phase have no affinity for the dispersion medium. (iii) They are not stable. (iv) They can be prepared by mixing substances directly. (v) They need stabilizing agents for their preservation. (vi) They are irreversible sols. * Lyophilic sols: (i) These colloids are liquid loving. (ii) In these colloids, the particles of dispersed phase have great affinity for the dispersion medium.(ii) They are stable. (iv) They cannot be prepared by mixing substances directly. They are prepared only by special methods. (v) They do not need stabilizing agents for their preservation. (vi) They are reversible sols. ¢ Classification of colloids on the basis of types of particles of the dispersed phase: There are three types of colloids based on the type of dispersed phase, namely, 1, 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. 2. 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. 3. Associated colloids (Micelles): Those colloids which behave as normal, strong electrolytes at low concentrations, but show colloidal properties at higherconcentrations due to the formation of aggregated particles of colloidal dimensions. Such substances are also referred to as associated colloids. e 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: These are are sodium or potassium salts of higher fatty acids e.g., sodium stearate CH3(CH2);gCOO-Na* ¢ Methods of preparation of colloids: 1. Chemical methods: Colloids can be prepared by chemical reactions leading to the formation of molecules. These molecules aggregate leading to formation of sols. 2. Electrical disintegration or Bredig’s 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. . Peptization: It is 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. © Purification of colloids: . Dialysis: It is a process of removing a dissolved substance from a colloidal solution by means of diffusion through a suitable membrane. . 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. . Ultrafiltration: It 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. . 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: Positively charged colloidal particles: (i) These include hydrated metallic oxides such as Fe203.@H20, Cr203.@H20, Al203. @H,0 (ii) Basic dye stuff like malachite green, methylene blue sols. (iii) Example - Haemoglobin (blood). Negatively charged colloidal particles: (i) Metallic sulphides like As2S3, Sb2$3 sols. (ii) Acid dye stuff like eosin, methyl orange, Congo red sols. (iii) Examples - Starch sol, gum, gelatin, clay, charcoal, egg albumin, etc.1, 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. 2. 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. 3. 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. 4. 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. 5. 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. 6, 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. 7. 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. 8. Electrophoresis: The movement of colloidal particles under an applied electric potential is called electrophoresis. 9, Coagulation or precipitation: The process of settling of colloidal particles as precipitate is called coagulation. © Hardy - Schulze rules: Oppositely charged ions are effective for coagulation. The coagulating power of electrolyte increases with increase in charge on the ions used r coagulation. Examples - Al?*> Ba2*> Na* for negatively charged colloids. Fe (CN)g]*>PO} >SO7- >CI for positively charged colloids. Types of emulsions: 1, Water dispersed in oil: When water is the dispersed phase and oil is the dispersion medium. E.g. butter 2. Oil dispersed in water: When oil is the dispersed phase and water is the dispersion medium. E.g. milk Emulsification: It is the process of stabilizing an emulsion by means of an emulsifier. Emulsifying agent or emulsifier: These are the substances which are added to stabilize the emulsions. Examples - soaps, gum Demulsification: It is the process of breaking an emulsion into its constituent liquidsby freezing, boiling, centrifugation or some chemical methods.JEE Main Revision Materials: www.crackjee.xyZ CBSE Class-12 Chemistry Quick Revision Notes Chapter-06: General Principles and Processes of Isolation of Elements Minerals: The naturally occurring chemical substances in the earth's crust which are obtained by mining are known as minerals. Metals may or may not be extracted profitably from them. Ores: The rocky materials which contain sufficient quantity of mineral so that the metal can be extracted profitably or economically are known as ores. Gangue: The earthy or undesirable materials present in ore are known as gangue. Metallurgy: The entire scientific and technological process used for isolation of the metal from its ores is known as metallurgy. Chief Ores and Methods of Extraction of Some Common Metals: Sodium metal a) Occurrence: Rock salt (NaCl), Feldspar (NazAlSisOx) b) Extraction method: Electrolysis of fused NaCl or NaCl/ CaClz ©) Inference: Sodium is highly reactive and hence, it reacts with water. Copper metal a) Occurrence: Copper pyrites (CuFeSz), Malachite (CuCOs.Cu(OH)2), Cuprite ( Cu20) Copper glance (CuzS) b) Extraction method: Roasting of sulphide partially and reduction. 2 Cu20 + Cu2S > 6 Cu +502 c) Inference: It is self-reduction in a specially designed converter. Sulphuric acid leaching is also employed. ed a) Occurrence: Bauxite:(Al0s(OH)s.2x where 0 < x < 1), Cryolite (NasAlFs), Kaolinite (Ak(OH),Si203) b) Extraction method: Electrolysis of Al203 dissolved in molten cryolite or in Na3AICls ©) Inference: A good source of electricity is needed in the extraction of Al Zinc metal a) Occurrence: Zinc blende or Sphalerite (ZnS), Zincite (ZnO), Calamine (ZnCOs) b) Extraction method: Roasting and then reduction with carbon. ©) Inference: The metal may be purified by fractional distillation. Lead metal a) Occurrence: Galena (PbS) b) Extraction: Roasting of the sulphide ore and then reduction of the oxide. ) Inference: Sulphide ore is concentrated by froth floatation process.Silvermetal a) Occurrence: Argentite (Ag2S) b) Extraction method: Sodium cyanide leaching of the sulphide ore and finally replacement of Ag by Zn. ¢) Inference: It involves complex formation and displacement. Gold metal a) Occurrence: Native, small amounts in many ores such as those of copper and silver b) Extraction method: Cyanide leaching, same as in case of silver c) Inference: Gold reacts with cyanide to form complex Iron metal a) Occurrence: Haematite (Fe203), Magnetite (Fe304), Siderite (FeCO3), Iron pyrites (FeS2) b) Extraction method: Reduction with the help of CO and coke in blast furnace. c) Inference: Limestone is added as flux which removes SiQz as calcium silicate (slag) floats over molten iron and prevents its oxidation. Temperatures approaching 2170 Kis required. Steps of metallurgy: a) Concentration of ore b) Conversion of concentrated ore to oxide c) Reduction of oxide to metal d) Refining of metal Concentration of ore: The process of removal unwanted materials like sand, clay, rocks etc from the ore is known as concentration, ore ~ dressing or benefaction. It involves several steps which depend upon physical properties of metal compound and impurity (gangue). The type of metal, available facilities and environmental factors are also taken into consideration. Hydraulic washing (or gravity separation): It is based on difference in densities of ore and gangue particles. Ore is washed with a ‘stream of water under pressure so that lighter impurities are washed away whereas heavy ores are left behind. Magnetic separation: This method is based on the difference in magnetic and non - magnetic properties of two components of ore (pure and impure). This method is used to remove tungsten ore particles from cassiterite (SnO2z). It is also used to concentrate magnetite (Fe30s), chromite (FeCr20,) and pyrolusite (MnOz) from unwanted gangue. Froth floatation process: It is based on the principle that sulphide ores are preferentially wetted by the pine oil or fatty acids or xanthates etc., whereas the gangue particles are wetted by the water. Collectors are added to enhance the non-wettability of the mineral particles. Froth stabilizers such as cresols, aniline etc., are added to stabilize the froth.If two sulphide ores are present, it is possible to separate the two sulphide ores by adjusting proportion of oil to water or by adding depressants, For example, in the case of an ore containing ZnS and PbS, the depressant used is NaCN. It selectively prevents ZnS from coming to froth but allows PbS to come with the froth. Leaching (Chemical separation): It is a process in which ore is treated with suitable solvent which dissolves the ore but not the impurities, Purification of Bauxite by leaching ( Baeyer’s process): a) Step 1: AI,O,(s) + 2NaOH (aq) +3H,O() > 2Na[ Al(OH), (aq) b) Step 2: 2Nal Al(OH ), (aq) + CO,(g) + Al,O;.XH ,0(s)+ 2NaHCO, (aq) c) Step 3: Al,0,.XH,O(s) "+ ALO, (s) + XH,0(g) d) Concentration of Gold and Silver Ores by Leaching: 4M (s)+8CN~(aq)+2H ,O(aq)+0,(g) > 4[M (CN), ) (aq) +40H “ (aq) 21M (CN), 1 (aq) + Zn(s) > [Zn(CN), T° (aq) + 2M (s) Where [M =Ag or Au] Conversion of ore into oxide: It is easier to reduce oxide than sulphide or carbonate ore. Therefore, the given ore should be converted into oxide by any onc of the following method: a) roasting b) calcination Roasting: a) It is a process in which ore is heated in a regular supply of air at a temperature below melting point of the metal so as to convert the given ore into oxide ore. b) Sulphide ores are converted into oxide by roasting ¢) Itisalso used to remove impurities as volatile oxides d) example - 2ZnS +30, > 22n0 +250, Calcination a) It is a process of heating ore in limited supply of air so as to convert carbonate ores into oxides. b) Carbonate ores are converted into oxide by roasting c) Itisalso used to remove moisture and volatile impurities. Host d) Example - CaCO, —“s Ca +€O, Reduction of oxide to metal:The process of converting metal oxide into metal is called reduction. It needs a suitable reducing agent depending upon the reactivity or reducing power of metal. The common reducing agents used are carbon or carbon monoxide or any other metals like Al, Mg etc. Thermodynamic principles of metallurgy: Some basic concepts of thermodynamics help in understanding the conditions of temperature and selecting suitable reducing agent in metallurgical processes: a) Gibbs free energy change at any temperature is given by AG = AH - TAS where AG is free energy change, AH is enthalpy change and AS is entropy change. b) The relationship between AG’ and K is AG’ = -2.303 RT log K where K is equilibrium constant. R = 8.314 JK-? mol-1, T is temperature in Kelvin. c) A negative AG means +ve value of K ie, products are formed more than the reactants. The reaction will proceed in forward direction. d) If AS is +ve, on increasing temperature the value of TAS increases so that TAS > AH and AG will become negative. Coupled reactions: If reactants and products of two reactions are put together in a system and the net AG of two possible reactions is -ve the overall reaction will take place. These reactions are called coupled reactions. Ellingham diagrams: The plots between A/G’ of formation of oxides of elements vs. temperature are called Ellingham diagrams. It provides a sound idea about selecting a reducing agent in reduction of oxides. Such diagrams help in predicting the feasibility of a thermal reduction of an ore. AG must be negative at a given temperature for a reaction to be feasible. Limitations of Ellingham Diagrams: It does not take kinetics of reduction into consideration, i.e., how fast reduction will take place cannot be determined. Reduction of iron oxide in blast furnace: Reduction of oxides takes place in different zones. a) At 500 - 800 K (iower temperature range in blast furnace) 3Fe,0, + CO -3 2Fe,0,+CO, Fe,0,+4CO + 3Fe+4C0, Fe,0,+CO > 2Fe0+CO, b) At 900 - 1500 K (higher temperature range in blast furnace) C+C0,2CO FeO +CO— Fe+Co, ©) Limestone decomposes to CaO and COz CaCO, “+ Ca0 +€0, e) Silica (impurity) reacts with CaO to form calcium silicate which forms slag. It floats over molten iron and prevents oxidation of iron.Ca0+Si0,—+ CaSiO, Calum Sie ag) Types of iron: a) Pig iron: The iron obtained from blast furnace is called pig iron. It is impure from of iron contains 4% carbon and small amount of S,P, Si and Mn. It can be casted into variety of shapes. b) Cast iron: It is made by melting pig iron with scrap iron and coke using hot air blast, It contains about 3% of carbon content. It is extremely hard and brittle. c) Wrought iron: It is the purest form of commercial iron. It is also called malleable iron. It is prepared by oxidative refining of pig iron in reverberatory furnace lined with haematite which oxidises carbon to carbon monoxide. Fe,0,+3C > 2Fe+3CO The substance which reacts with impurity to form slag is called flux e.g. limestone is flux. S+0, SO, 4P +50, > 2P,0, Si+O, > SiO, CaO + SiO, > CaSiO,(slag) 3Ca0 + P,O, > Ca,(PO,), (slag) The metal is removed and freed from slag by passing through rollers, Electrolytic Reduction (Hall - Heroult Process): Purified bauxite ore is mixed with cryolite (NasAlFs) or CaF2 which lowers its melting point and increases electrical conductivity. Molten mixture is electrolysed using a number of graphite rods as anode and carbon lining as cathode, ‘The graphite anode is useful for reduction of metal oxide to metal. 2Al,0,+3C > 4Al+3C0, AlyO, 2-9 2D +30" Atcathode: Al" (melt)+3e" — Al(1) Atanode: C(s)-+* (melt) > CO(g)+2e" C(s)+20* (melt) + CO,(g)+4e" Graphite rods get burnt forming CO and COz. The aluminium thus obtained is refined electrolytically using impure Al as anode, pure Al as cathode and molten cryolite as electrolyte. Atanode: Al — Al’ +3e7 (ip) At cathode: AI™ +3e” — Al(pure) Electrolysis of molten NaCl: NaCl Na’ +Cr- MoeAtcathode: Na” +e” > Na At anode: 2CI” — Cl, +2e" Thus sodium metal is obtained at cathode and Clz (g) is liberated at anode. Refining: It is the process of converting an impure metal into pure metal depending upon the nature of metal. Distillation: It is the process used to purify those metals which have low boiling points, e.g. zinc, mercury, sodium, potassium. Impure metal is heated so as to convert it into vapours which changes into pure metal on condensation and is obtained as distillate. Liquation: Those metals which have impurities whose melting points are higher than metal can be purified by this method. In this method, Sn metal can be purified. Tin containing iron as impurities heated on the top of sloping furnace. Tin melts and flows down the sloping surface where iron is left behind and pure tin is obtained. 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. Atanode: M 3M” +ne (npure) Atcathode: M"™ +ne" > MY Zone refining: It is based on the principle that impurities are more soluble in the melt than in the solid state of the metal. The impure metal is heated with the help of circular heaters at one end of the rod of impure metal. The molten zone moves forward along with the heater with impurities and reaches the other end and is discarded. Pure metal crystallizes out of the melt. The process is repeated several times and heater is moved in the same direction. It is used for purifying semiconductors like B, Ge, Si, Ga and In. Vapour phase refining: Nickel is purified by Mond’s process. Nickel, when heated in stream of carbon monoxide forms volatile Ni(CO)4 which on further subjecting to higher temperature decomposes to give pure metal. Ni ACORIELs Ni(CO), 25 Nit 4CO Van- Arkel method: It is used to get ultra pure metals. Zr and Ti are purified by this process. Zr or Ti are heated in iodine vapours at about 870 K to form volatile Zrl4 or Til4 which are heated over tungsten filament at 1800K to give pure Zr or Ti.Ti+2l, 9 Til, > Ti+ 2, dite Wee Zr+21, > Zrl, > Zr+21, Moe Fire Chromatographic method: It is based on the principle of separation or purification by chromatography which is based on differential adsorption on an adsorbent. In column chromatography, Al203 is used as adsorbent. The mixture to be separated is taken in suitable solvent and applied on the column. They are then eluted out with suitable solvent (eluent). The weakly adsorbed component is eluted first. This method is suitable for such elements which are available only in minute quantities and the impurities are not very much different in their chemical behaviour from the element to be purified.CBSE Class 12 Chemistry Quick Revision Notes Chapter 7 The P-Block Elements e The p-Block elements: Elements belonging to groups 13 to 18 of the periodic table are called p-block elements. © General electronic configuration of p-block elements: The p-block elements are characterized by the ns2np1-6 valence shell electronic configuration. © Representative elements: Elements belonging to the s and p-blocks in the periodic table are called the representative elements or main group elements. © Inert pair effect: The tendency of ns2 electron pair to participate in bond formation decreases with the increase in atomic size. Within a group the higher oxidation state becomes less stable with respect to the lower oxidation state as the atomic number increases, This trend is called ‘inert pair effect’. In other words, the energy required to unpair the electrons is more than energy released in the formation of two additional bonds. GROUP 15 ELEMENTS e Nitrogen family: The elements of group 15 - nitrogen (N), phosphorus (P), arsenic (As), antimony (Sb) and bismuth (Bi) belong to configuration is ns*np?. Atomic and ionic radii: 1, Covalent and ionic radii increase down the group. 2. There is appreciable increase in covalent radii from N to P. 3, There is small increase from As to Bi due to presence of completely filled d or f orbitals in heavy elements. « Ionisation energy: 1, It goes on decreasing down the group due to increase in atomic size.. Group 15 elements have higher ionisation energy than group 14 elements due to smaller size of group 15 elements. , Group 15 elements have higher ionization energy than group 16 elements because they have stable electronic configuration i.e., half-filled p-orbitals. © Allotropy: All elements of Group 15 except nitrogen show allotropy. © Catenation: . Nitrogen shows catenation to some extent due to triple bond but phosphorus shows catenation to maximum extent. .. The tendency to show catenation decreases down the group. ¢ Oxidation states: |. The common oxidation states are +3, +5 and -3. The tendency to show -3 oxidation state decreases down the group because of decrease in electronegativity by the increase in atomic size. The stability of +5 oxidation state decreases whereas stability of +3 oxidation state increases due to inert pair effect. 4. Nitrogen shows oxidation states from -3 to +5. 5, Nitrogen and phosphorus with oxidation states from +1 to +4 undergo oxidation as well as reduction in acidic medium. This process is called disproportionation. 3HNO2 > HNO3 + H20+2NO « Reactivity towards hydrogen: . All group 15 elements from trihydrides, MM H3. It belongs to sp® hybridisation. The stability of hydrides decreases down the group due to decrease in bond dissociation energy down the group. NH3 > PH3 > AsH3 > SbH3 > BiH © Boiling point: PH3 < AsH3 < NH3 < SbH3 < BiH3 . Boiling point increases with increase in size due to increase in van der Waals forces... Boiling point of NH3 is more because of hydrogen bonding. © Bond angle: NH (107.8°) > PHg(99.5°) > AsHy(91.8°) = SbH3(91.3°) > BiHs (90°) . Electronegativity of N is highest. Therefore, the lone pairs will be towards nitrogen and hence more repulsion between bond pairs. Therefore bond angle is the highest. After nitrogen, the electronegativity decreases down the group. . Basicity decreases as NH3> PH3> AsH3> SbH3< BiH3. This is because the lone pair of electrons are concentrated more on nitrogen and hence the basicity will be maximum in the case of NH3. It will decrease down the group as the electronegativity decreases down the group. The reducing power of hydrides increases down the group due to decrease in bond dissociation energy down the group. ¢ Reactivity towards oxygen: . All group 15 elements from trioxides (M203) and pentoxides (M205). . Acidic character of oxides decreases and basicity increases down the group. This is because the size of nitrogen is very small. 3. It has a strong positive field in a very small area. Therefore, it attracts the electrons of water O-H bond to itself and release H+ ions easily. . As we move down the group, the atomic size increases and so, the acidic character of oxide decreases and basicity increases down the group. ¢ Reactivity towards halogen: Group 15 elements form trihalides and pentahalides. |. Trihalides: These are covalent compounds and become ionic down the group with sp? hybridisation, pyramidal shape. . Pentahalides a). They are lewis acids because of the presence of vacant d - orbitals. b). They possess sp’ d hybridisation and hence possess trigonalbirpyamidal shape. POls + Cl- + [PCle|-JEE Main Revision Materials: www.crackjee.xyZ 3. PCIS is ionic in solid state and exist as [PC14]*[PCls]- 4. In PCIS5, there are three equatorial bonds and two axial bonds. The axial bonds are longer than equatorial bonds because of greater repulsion from equatorial bonds. 5, Nitrogen does not form pentahalides due to absence of d- orbitals. © Reactivity towards metals: All elements react with metals to form binary compounds in -3 oxidation state. e Anomalous behaviour of nitrogen: The behaviour of nitrogen differs from rest of the elements. Reasons: i, Ithas a small size. ii. It does not have d - orbitals iii. It has high electronegativity iv. It has high ionization enthalpy © Dinitrogen: a) Preparation: Heat NH4Cl(aq) + NaNO>(aq) —+ No(9) + 2H20(1) + NaCl(aq) Heat (NHy)2Cr20; —+ No + 4720 + Cr03 Heat Ba(N3)2 —+ Ba + 3N2 b) Physical Properties: i) It is a colourless, odourless, tasteless and non - toxic gas. ii) It is chemically un-reactive at ordinary temperature due to triple bond in N = N which has high bond dissociation energy. ¢ Ammonia: 4. Ammonia molecule is trigonal pyramidal with nitrogen atom at the apex. 2. Ithas 3 bond pairs and 1 lone pair. 3. Nis sp hybridised.4. Preparation: Haber’s process: No(g) + 8H2(g) + 2NHa(9) A;sH?® = —46.1kJ mol} Pressure 200x 10 Pa Temperature 773 K Catalyst is FeO with small amounts of K20 and Al,O3 * Nitric Acid: Ostwald Process: The NO thus formed is recycled and the aqueous H NO3 can be concentrated by distillation upto ~ 68% by mass. Further concentration to 98% can be achieved by dehydration with concentrated Hz SOg . Nitric acid is strong oxidizing agent in the concentrated as well as in the dilute state. Pt/Rh gauge 500k, 9 bar AN H3 + 502 ————————> 4NO + 6420 2NO + Oz + 2NO2 3NO2(g) + H2O(1) + 2HNOs (aq) + NO(g) Phosphorus: a) It shows the property of catenation to maximum extent due to most stable P - P bond. b) It has many allotropes, the important ones are: i) White phosphorus ii) Red phosphorus iii) Black phosphorus White phosphorus: . Discrete tetrahedral P4 molecules . Very reactive . Glows in dark .. Translucent waxy solid . Soluble in C'Spbut insoluble in water ;. It has low ignition temperature, therefore, kept under water PUR wen Ep© Red phosphorus . Polymeric structure consisting of chains of P4 units linked together .. Less reactive than white phosphorus . Does not glow in dark . Has an iron grey lustre . Insoluble in water as well as CS YON e ¢ Black phosphorus 1. Exists in two forms - @ black phosphorus and black phosphorus 2. Very less reactive 3, Has an opaque monoclinic or rhombohedral crystals 573k in an inert atmosphere for several days White phosphorus ——————————————_> Reed phosphorus . High pressure,473K White phosphorus ———————> Black phosphorus Inasealed tube,803K Red phosphorus —-———————-+ Black phosphorus © Phosphine 1. Itis highly poisonous, colourless gas and has a smell of rotten fish. 2. Preparation Ca3P2 + 6H2O - 3Ca(OH),+ 2PH3 Calcium — Water Calcium Phosphine Phosphide Hydrozide Ca3P2+6HCl - 3CaCl, + 2PH3 Phosphine P4+3NaOH +3H2O > 3NaH2PO)+ PH3 Sodium Phosphine Hypophosphite Chlorides of Phosphorous: a) Phosphorus Trichloride i) It is a colourless oily liquid. ii) Preparation Py + 10Clz — 4PClsP4+10S02Clz + 4PCls + 10S02 iii) With water, It gets hydrolysed in the presence of moisture. PCls + 3H2O0 — H3PO3 +3HCl iv) Pyramidal shape, sp3 hybridisation v) With acetic acid 38CH3COOH + PCl3 + CH3COCI+ H3PO3 vi). With alcohol 3C,H;0H + PCl3 > 3C2HsCl+ H3PO3 b) Phosphorus pentachloride C2H;3OH + PCls + CoHsCl + POCI; + HCl . Yellowish white powder. . Trigonalbipyramidal shape, sp3dhybridisation . . Preparation . Py +10Cl2 > 4PCls Ps+10S02Cl, + 4PCls + 10502 . With water 6. PCls + H20 —- POCl3 + 2HC1 POC; +3H,O0 + H3PO4 + 3HCI 7. With acetic acid 8. 3CH3COOH + PCls + CH3COCI+ POC; + HCl 9. With alcohol 10. With metals Penyp ww 2Ag+ PCls -+ 2AgCl + PCls Sn+2PCls + SnCl4 + 2PCls GROUP 16 ELEMENTS © Oxidation states:were aun . They show -2, +2, +4, +6 oxidation states. Oxygen does not show +6 oxidation state due to absence of d- orbitals. . Po does not show +6 oxidation state due to inert pair effect. , The stability of -2 oxidation state decreases down the group due to increase in atomic size and decrease in electronegativity. . Oxygen shows -2 oxidation state in general except in OF2and O2 F2 Thus, the stability of +6 oxidation state decreases and +4 oxidation state increases due to inert pair effect. © Jonisation enthalpy: . Ionisation enthalpy of elements of group 16 is lower than group 15 due to half-filled p- orbitals in group 15 which is more stable. . However, ionization enthalpy decreases down the group. ¢ Electron gain enthalpy: . Oxygen has less negative electron gain enthalpy than S because of small size of O. . From S to Po electron gain enthalpy becomes less negative to Po because of increase in atomic size. © Melting and boiling point: . _Itincreases with increase in atomic number. . Oxygen has much lower melting and boiling points than sulphur because oxygen is diatomic (Q2 ) and sulphur is octatomic (Sg). © Reactivity with hydrogen: . All group 16 elements form hydrides. . They possess bent shape. . Bond angle: HO [373K] > HS [213K] < H2Se [232K] < H2Te [269K] ¢ Acidicnature: #20 < H2S < HoSe < HeTe This is because the H-E bond length increases down the group. Therefore, the bond dissociation enthalpy decreases down the group. © Thermal stability: HO < H2S < HoSe < HoTe < H2PoThis is because the H-E bond length increases down the group. Therefore, the bond dissociation enthalpy decreases down the group. * Reducing character: H20 < H2S < H2Se < HeTe < HoPo This is because the H-E bond length increases down the group. Therefore, the bond dissociation enthalpy decreases down the group. « Reactivity with oxygen: EO. and EO; 1, Reducing character of dioxides decreases down the group because oxygen has a strong positive field which attracts the hydroxyl group and removal of H* becomes easy. 2. Acidity also decreases down the group. 3. SOz is a gas whereas SeO2 is solid. This is because SeO2 has a chain polymeric structure whereas SO2 forms discrete units. * Reactivity with halogens: EX2, EX4 and EX6 . The stability of halides decreases in the order F— > Cl— > Br— > I-. .. This is because E-X bond length increases with increase in size. . Among hexa halides, fluorides are the most stable because of steric reasons. . Dihalides are sp* hybridised and so, are tetrahedral in shape. . Hexafluorides are only stable halides which are gaseous and have sp’ d? hybridisation and octahedral structure. 2 O is a liquid while H2S is a gas. This is because strong hydrogen bonding is present in water. This is due to small size and high electronegativity of O. Pe prp ps 2 Oxygen: The compounds of oxygen and other elements are called oxides. Heat/MnO; 2K C103 ————> 2KCl + 302 Finely divided metals 2.H2O2(aqg) ———————> 2H2. O() + O2(g) Heat 2.Ag20(s) —> 4Ag(s) + O2(g) 2H g0(s) —+ 2H9(l) + O29)2Pb3O4(s) 4 6PbO(s) + O2(9) Red lead 2PbOz(s) > 2PbO(s) + O2(g) Oxides: The compounds of oxygen and other elements are called oxides. © Types of oxides: SO. + HzO -+ Hz SO3(Sulphurous acid) Na,O0 + H20 > 2NaOH K2.0 + H20 > 2KOH CaO + H2O + Ca(OH)otitex) nN » S . Acidic oxides: Non- metallic oxides are usually acidic in nature. Basic oxides: Metallic oxides are mostly basic in nature. Basic oxides dissolve in water forming bases e.g., . Amphoteric oxides: They show characteristics of both acidic as well as basic oxides. AlpOy + 6HCl(aq) -> 2AIC13(ag) + 3120 AlzO3 + 6NaOH (aq) + 3H20(I) -> 2Nas[Al(OH)o](aq) . Neutral oxides: These oxides are neither acidic nor basic. Example: Co, NO and N20 * Ozone: . Preparation: It is prepared by passing silent electric discharge through pure and dry oxygen 10-15 % oxygen is converted to ozone. 302 (9) + 203(9); AH = +142kJ mol“ . Structure of Ozone: Ozone has angular structure. Both 0 = O bonds are of equal bond length due to resonance. * Sulphur: . Sulphur exhibits allotropy: 1, Yellow Rhombic (a - sulphur) 2. Monoclinic (6- sulphur)309K 2. a— sulphur —> 6 — sulphur 3, At 369 K both forms are stable. It is called transition temperature. 4. Both of them have S8 molecules. 5, The ring is puckered and has a crown shape. 6. Another allotrope of sulphur - cyclo Sg ring adopts a chair form. 7. S2is formed at high temperature (~1000 K). 8. It is paramagnetic because of 2 unpaired electrons present in anti bondingz* orbitals like On. ¢ Sulphuric acid: By contact process $58 + Oz > S02 Vs0s /2bar 720k 2502(g) + O2(9) ————> 2503 (g) AH® = -196.6kJ mol~* S03(g9) + H2SO4 — H25207(oleum) Hy S207 + H2O — 2H2SO4 (96-98%) . Preparation: . Exothermic reaction and therefore low temperature and high pressure are favourable. 3. It is dibasic acid or diprotic acid. . It is a strong dehydrating agent. Prone . Itis a moderately strong oxidizing agent. GROUP 17 ELEMENTS © Atomic and ionic radii: Halogens have the smallest atomic radii in their respective periods because of maximum effective nuclear charge. © Ionisation enthalpy: They have very high ionization enthalpy because of small size as compared to other groups.xn b RN one N > ene a « Electron gain enthalpy: Halogens have maximum negative electron gain enthalpy because these elements have only one electron less than stable noble gas configuration. . Electron gain enthalpy becomes less negative down the group because atomic size increases down the group. © Electronegativity: . These elements are highly electronegative and electronegativity decreases down the group. .. They have high effective nuclear charge. © Bond dissociation enthalpy: . Bond dissociation enthalpy follows the order: Cl > Br2> Fy> In This is because as the size increases bond length increases. . Bond dissociation enthalpy of C12 is more than F2 because there are large electronic repulsions of lone pairs present in F2. Colour: All halogens are coloured because of absorption of radiations in visible region which results in the excitation of outer electrons to higher energy levels. © Oxidising power: . All halogens are strong oxidisingagents because they have a strong tendency to accept electrons. . Order of oxidizing power is: Fp > Cl > Bro > In * Reactivity with Hydrogen: . Acidic strength: HF HCl>HBr> HI. This is because of decrease in bond dissociation enthalpy. . Boiling point: HClHCI>HBr> HI Dipole moment: HF >HCI>HBr> HI. Electronegativity decreases down the group. . Reducing power: HF MCI>MBr> MI. The halides in higher oxidation state will be more covalent than the one in the lower oxidation state. ¢ Interhalogen compounds: Reactivity of halogens towards other halogens: 1, Binary compounds of two different halogen atoms of general formula X Xj, are called interhalogen compounds where n = 1, 3, 5, or 7. All these are covalent compounds. 2, Interhalogen compounds are more reactive than halogens because X-X is a more polar bond than X-X bond. 3, All are diamagnetic. 4. Their melting point is little higher than halogens. 5. XX’ (CIF, BrF, BrCl, ICI, IBr, IF) (Linear shape) XX’3 (CIF3, BrF3, IF3, ICl3) (Bent T- shape) XX’s-CIF, BrFs, IF, (square pyramidal shape) XX’; -IF; (Pentagonal bipyramidal shape) * Oxoacids of halogens: HClO, ~ H* + C10; Most Stable 1. Fluorine forms only one oxoacid HOF (Fluoric (D acid or hypofluorous acid) due to high electronegativity. 2. Acid strength: HOCI < HClO) < HClO; < HClO, 3. Reason: 4. Acid strength: HOF >HOCI>HOBr> HOI. This is because Fluorine is most electronegative. GROUP 18 ELEMENTS: * Jonisation enthalpy: 1. They have very high ionization enthalpy because of completely filled orbitals. 2, Tonisation enthalpy decreases down the group because of increase in size.© Atomic radii: Increases down the group because the number of shells increases down the group. « Electron gain enthalpy: They have large electron gain enthalpy because of stable electronic configuration. Melting and boiling point: It has low melting and boiling point due to the presence of only weak dispersion forces. © Shapes: XeFh is linear, XeF is square planar and XeF is distorted octahedral. KrF is known but no true compound of He Ne and Arare known. ¢ Compounds of Xe and F: 673k,1bar « Xe+ Fy ——> Xen 873K/Tbar « Xe+2F, ——+ XeFy 573k/60—70bar o Xe +3F, ————> XeF5 © XeFy + O.F, + XeFs+O2 XeF2, XeFy and XeFs are powerful fluorinating agents. * Compounds of Xe and 0: 6XeFy + 12H2O — 4Xe + 2XeO3 + 24HF + 302 XeFe +3H20 + XeO; + 6HFd & f BLOCK ELEMENTS Pee Definition “The elements in which the last differentiating electron enters into the d-orbitals of the penultimate shell i.e. (n-1) dwheren isthe last shell are called d-block elements ‘A transition element may also be defined as the element which partially filled d-orbital in their ground state or most stable oxidation state, ‘Cu(Z = 29)= Is? 2s? 2p* 3s? 3p" 3d" 4s! 2st2p' 3s? 3p* 3d” (Coprc ion) ‘The properties of these elements are intermediate between the properties of s-block and p-block elements. ‘These elements represent a change or transition in properties from more clectropositive elements (s-block) to less clectropositive elements (p-block). Therefore these elements are called transition elements. Position in the periodic table ‘The position of d-block element has been shown in periodic table as follows : a MA TA VA Via vial 2 1s" oe Ys Yo ar 10) Q QB) 4) 1 ‘tronic configuration Ind-block elements with increase in atomic number, the d- orbitals of penultimate shell ie. (n-1) d are gradually filled by electrons. The general electronic configuration of d- block element is, (n-11) d™", ns™, Depending upon the d-orbitals of which penultimate shell ie.n=4, 5,6, 7 are filled, four rows (called series) os ten elements each obiained, They correspond to 3d, 4d, Sd and 6d subshells. Energy of “(n-1)d” subshell is slightly greater than ‘ns’ subshell, hence orbitals filled first then (n~ 1) d orbitals ‘The general electronic configuration of d-blocl/d-scries elements be shown as follows : First (3d) Transition Series (Sc-Zn) AcNo. [212 2399578 9 3 [Etoment|Se_Tl__V —_cr_Mn__Fe Co Ni Gu Zn EC. |adasTadies' adda Was ad as adasad' essa Es d 409 AT 2, Second (4d) Transition Series (V-Cd) ALNo. [3840 aaa a Etoment|"—Y 2" Nb Mo —Te"_Ru_Rh__Pd Ag Ca EC |aalSsiau'5e'4d'Ss"4e'Ss 40'S ad Ss'ed sd 584d SEC" Se 3 OT (Sd) Transition Series (La-lig) a Etement|—ta_Ht_Ta_W__Ro Ose 17 78 73] t_ Au He (1) deblock elements lie in between's’ and ‘p’ block elements, these elements are located in the middle of the periodic table, d-block elements are present in, 4 period (,,Sc to ,,Zn, 10 elements) + I" Transition series, S*period (,5¥ to Cd, 10 elements) > 2°'Transition series, 6° period (,,La, ,Hf'to Hg, 10 elements) —> 3"' Transition series, T* period (WAC, ,,,Rfto ub, 10 elements) —>4® Transition series. Q junvava viovua ae 7 Ec. [Raes'Sate 5a bs bey bd Gs edu Sd Os SSN US EE Ce Ere aha oh 4. Fourth (6d) Transition Series oe FARA LT afro lee 3 CT feted fe Elomont| Ae KuHa SB} Hs — Muna Infor [oe |orlon {Un (Uns) (Une) (Uno) P ec. [67a 6d Te 6d 7s 6d7e 6472 OSTH6d 7S CATER TSCETS (ex Le Exceptional configuration of Cr and Cu, The exceptions observed in the first series are in case of electronic configurations of chromium (2.= 24) and copper(Z=29). It may be noted that unlike other elements, chromium and copper have a single electron in the 4s-orbital. This is due tothe gain of additonal stability by the atom by cither having half-filled configuration (ic., containing S electrons in the d-sublevel) of completely filled configuration, (i.e. containing 10 electrons in the d-sublevel). The 3d-level in case of chromium gets excatly half-filled with configuration 3a 4s! and that in case of copper, it gets completely filled with configuration 34 4s!. This can be explained on the basis of exchange energy oo‘Thus, the electronic configuration of chromium (Z = 24) and copper (Z.=29) are Is? 2s? 2p* 3s? 3p" 3d 4s! and Is*2s? 2p 3st 3p? 3d! 4s! respectively. (3 Properti 1. Atomic Raddi (Theatomic radi of the transition metals lie in-between those of s- and p-block elements. (Generally the atomic radii of d-block elements in a series decreas with increase in atomic number but the decrease in atomic size is small after midway. Explanation ‘The atomic radius decreases with the increase in atomic number as the nuclear charge inereases whereas the shielding effect of d-clectron is small, After midway, as the eleetrons enter the last butone (penultimate) shell, the added electron shields (screens) the outermost electron. Hence, with the increase in the d-electrons, screening effect increases. This counterbalances the increased nuclear charge due to increase in atomic number, As a result, the atomic radii remain practically same after chromium. For example in Fe, the two opposing tendencies almost no change in the size from Mn (ii) At the end of the period, there is a slight increase in the atomic rai Explanation Near the end of series, the increased electron-electron repulsions between added electrons in the same orbitals, are greater than the attractive forces due to the increased ‘nuclear charge. This results in the expansion of the electron, cloud and thus the atomic radius increases. iv) ‘The atomic radii inerease down the group. This means that the atomic radii of second series are larger than those of first transition series. But the atomic radii of the second and third transition series are almost the same. ‘The atomic radii of the elements of the second and third transition metals are nearly same due to lanthanide contraction (or also called lanthanoid contraction) discussed Iater. @ The trend followed by the ionic radii is the same as that followed by atomic radi Ionic radii of transition metals are different in different oxidation states, (éi)_The ionic radii ofthe transition metals are smaller than those of the representative elements belonging to the same period. 15 Metallic character Except for mercury which is a liquid, all the transition, elements have typical metallic structure. They exhibit all the characteristics of metals. ductile, have high melting and, boiling points, high thermal and electrical conductivity and. high tensile strength. ‘Transition elements have relatively low ionization energies ‘and have one or two electrons in their outermost energy level (ns! orns?). Asaresult, metallic bondsare formed, Hence, they behaveas metals. Greater the number of unpaired d electrons, stronger is the bonding due to the overlapping of unpaired electrons between different metal atoms, 1.6 Melting Point ‘Transition metals have high melting points which is due to their strong metallic bond. The metallic bond. The metalic bonding depends upon the number of unpaired e°. The melting point first increases (Se-C1), reaches amaximum value (CP) and then decreases (Fe-Zn) * Tungsten (\W) has the highest melting point. + Mercury (Ig) has the lowest melting point. + Mn has the lowest melting point in 3d series typicl transition elements 1-7 Tonisation energies or Tonisation enthalpies @ The irstionisation enthalpies of d-block elements lie between s-block and p-block elements. They are higher than those of s- block elements and are lesser than those of p-block elements. ‘The ionisation enthalpy gradually increases with increase in atomic number along a given transition series though some irregularities are observed Explanation ‘The increasing ionization enthalpies are due to increased ‘nuclear charge with increase in atomic number which reduces the size of the atom making the removal of outer electron TH (ad, 45%) 2) Allltransition elements show variable oxidation state except Mn* (3d, 4s") > Mn (3d*, 4s) last element in each series Fe, (3d, 4st)> Fe (3d, 434) ) Minimum oxidation state =Total number ofelectrons in4s | (9) Cu’? is more stable than Cu‘ even when Cu‘! is 3d while Jost. Maximum oxidation state= (Total number of electrons Cu'*is 3d due to high heat of hydration in 4s + number of unpaired electrons in 3d lost). eee < Variable oxidation states shown by 3d-series of d-block elements. Oxidation States ELECTRON! STi v G@ Mn Fe Go N Cu Zn conriguration | i's? @s? a's? a's? ds? dh? ag? ate? dg? as! als! Z 4 4 5 n oR 2 7] 2 2 2 242 2 2 B48 8 8 8 8 8 8B 8 9 44 4 4 MH 4 MOH g 6 +5 +5 +5 +5 +s Ss +6 +6 +6 +wi) Gi) ‘Thermodynamic stability of the compounds of transition elements can be evaluated in terms of the magnitude of ionisation enthalpies of the metals —smaller the ionisation enthalpy of the metal, stabler is its compound. In solution, the stability of the compounds depends upon electrode potentials rather than ionization enthalpies. Electrode potential values depend upon factors such as enthalpy of sublimation (or atomisation) of the metal, the ionisation enthalpy and the hydration enthalpy, i.e., M(s)—***">M(g), (4,,,{ is enthalpy of sublimation’ atornisation) M(s) 4M" (g)-+e°, (A, H is ionisation enthalpy) M*(g)+aq—*" 5M" (aq), (A,,, H is enthalpy of hydration) The total energy, A, H, for the process invol sublimation, ionisation and hydration simultaneously, e, for the process, M(s)—> M’ (aq) +e", will be the sum of the three types of enthalpies, ie., A,;H=AyH+4H+4,JH. ‘Thus, A, H, is the total enthalpy change when solid meal, M is brought in the aqueous medium in the form of ‘monovalent ion, M° (aq) MG) #5 M*(aq) 1 wall M@) > MG) TM) Aye ‘Trends in the M™/M Standard Electrode Potentials ‘There is no regular trend in the E* (M®/M) values. This is because their ionization enthalpies (I, + 1E,) and sublimation enthalpies do not show any regular trend ‘The general trend towards less negative E* values along, the series is due to the general increase in the sum of first and second ionization enthalpies. Copper shows a unique behaviour in the series as itis the only metal having positive value for E°. This explains why is does not liberate I, gas from acids. It reacts only with the oxidizing acids (HNO, and H,SO,) which are reduced. “The reason for positive E* value for copper is that the sum of enthalpies of sublimation and ionization is not balanced by hydration enthalpy. (iv) The values of E* for Mn, Ni and Zn are more negative than expected from the generall trend. This is due to greater stability ofhalf-filled d-subshell (d') inn", and completely filled d-subshell (4") in Zn". The exceptional behaviour of Nitowards E* value from the regular trend is due to its high negative enthalpy of hydration, ‘Trendsin the M/M* Standard Electrode Potentials (A very low value for E* (Sc/Se™) reflects the sta Se ion which has a noble gas configuration, ity of (ii) The highest value for Zn is on account of very high stability of Zn** ion with d'° configuration. It is difficult to remove an electron from it to change it into +3 state. ‘The comparatively high value of E° (Mn**/Mn**) shows that Mn** is very stable which is on account of stable d° configuration of Mn” Gi) (iv) The comparatively low value of E* (Fe™/Fe") is on account of extra stability of Fe (d') ie, low third ionization enthalpy ofFe. (v) The comparatively low value for V is on account of the stability of V™ ion due to its half-filled 13, configuration (discussed in unit 9), Chemical Reactivity and E* Values, The transition metals, ‘vary very widely in their chemical reactivity. Some of them are highly electropositive and dissolve in mineral acids whereas afew of themare ‘noble’, ie., they do not react with simple acids, Some results of chemical reactivity of transition ‘metals as related to their E* values are given belo’ (The metals ofthe first transition series (except copper) are relatively more reactive than the othr series. Thus, they are oxidized by H* ions though the actual rate is slow, ¢.g., Ti and V are passive to dilute non-oxidizing acids at room temperature. (i) As already explained, less negative E* values for M/M along the series indicate a decreasing tendency to form divalent cations Gi) More negative E® values than expected for Mn, Ni and Zn show greater stability for Mn*, Ni** and Zn™ E* values for the redox couple M?'/M"* indicate that Mn" and Co** ions ar the strongest oxidizing agents in aqueous solution whereas Ti", V" and Cr are strongest reducing agents and can liberate hydrogen from a dilute acid, e.g.,2 Cr (ag) +2 H (aq) —+ 2. Cr (aq) +H, (g) (iv) 1.10 Catalytic Property ‘Most transition elements and their compounds have good catalytic properties because (a) They possess variable oxidation state,(b) They provide a large surface area for the reactant to be absorbed. Catalysts Uses TICl,+A1(C,H,) Ziegler-Natta catalyst, used in polymerisation of ethylene V0, Contact process SO, > SO Fe Haber Bosch process PdCl, Wacker’s process for CH CHO manufacturing Pd Hydrogenation of alkene, alkyne ete PuPio ‘Adam's catalyst for selective reduction Pt Catalytic convertor, for cleaning car exhaust fumes PURh Ostwald’s process : NH >NO cu ‘Oxidation of alcohols T-1I Magnetic Behaviour Whena substance is placed in a magnetic field of strength H, the intensity of the magnetic field in the substance may be greater than or less than H. Ifthe field in the substance is greater than H, the substance is a paramagnetic material and attracts line of force. Ifthe field in the substance is less, than H, the substance is diamagnetic. Diamagnetic materials tend to repel lines of force. The magnetic moment of a substance depends on the strength of magnetic field generated due toelectronic spin, there isa change in electric flux which leads to induction of magnetic field. The electron is also under orbital angular momentum or orbital spin. It leads to generation of magnetic moment. In first transition elements series the orbital angular magnetic ‘moment is insignificant the orbital contributions quenched by the electric fields of the surrounding atoms so magnetic, ‘moment is equal to the spin magnetic moment only. Herr = n(n-+2)BM n> no, of unpaired electron, Maximum transition elements and compounds are paramagnetic due to presence of unpaired electrons. sare «it) 0 (i (i) ‘Transition metal ions form a large number of complex compounds. Complex compounds are those which have metal ion linked toa number of negative ions (anions) or neutral molecules having lone pairs of electrons, These ions or molecules are called ligands. They donate lone pairs of electrons o the central transition metal ion forming coordinate bonds ‘A few examplesare given below: [Fe(CN),}*. [Fe(CN),J*. [Cu(NH),F*, [Zn(NH),.F, [Ni(CN),F-and [Ptel Such complex compounds are not formed by s - and p ~ block elements, Explanation, The transition elements form complexes because of the following reasons : ‘Comparatively smaller size of their metal ions. ‘Their high ionic charges. (Because of (i) and (ii), they have large charge/size ratio) Availability of vacant d-orbitals so that these orbitals can accept lone pairs of electrons donated by the ligands. 21 Inter [Compounds ‘The transition metals form a large number of interstitial compounds in which small atoms such as hydrogen, carbon, boron and nitrogen occupy the empty spaces (interstitial sites) in their lattices (Fig.). They are represented by formulae like TiC, TiHl,, Mn,N, Fe,H, Fe,C etc. However, actually they are non- stoichiometric materials, eg., TiHl,,, VH,.,, etc. and the bonds present in them are neither typically ionic nor covalent, Some of their important characteristics are as follows: They are very hard and rigid, e.g., steel which is an interstitial compound of Fe and Cis quite hard. Similarly, some borides are as hard as diamond. ‘They have high melting points which are higher than those of the pure metals. ‘They show conductivity like that of the pure metal ‘They acquire chemical inertness. 2.2 Alloy format Alloys are homogeneous solid solutions of two or more metals obtained by melting the components and then cooling the melt. These are formed by metals whose atomic radii differ by not more than 15% so that the atoms of one ‘metal can easily take up the positions inthe erystal lattice ofthe other (Fig,) Now, as transition metals have similar atomic radii andee other characteristics, hence they form alloys very readily. Alloys are generally harder, have higher melting points ‘and more resistant to corrosion than the individual metals. ‘The most commonly used are the ferrous alloys the metals chromium, vanadium, molybdenum, tungsten and manganese are used in the formation of alloy steels and stainless steels. Some alloys of transition metals with non- transition metals are also very common. ¢.g., brass (Cu+ Zn) and bronze (Cu + Sn) TRAPPED ATOMS, “> INTERSTITIAL voIDs Formation of Interstitial compounds. ATOMS OF METAL M. ‘ATOMS OF METAL M" Formation of alloys. 3, COMPOUNDS OF TRANSITION ELEMENTS (iv) ) “The metals ofthe first transition series form oxides with oxygen at high temperature. ‘The oxidesare formed in the oxidation, states +1 t0-+7 (as givenin Table 8.10, page 8/14), ‘The highest oxidation state in the oxides of any transition ‘metal is equal to its group number, ¢.g., 7 in Mn,O,, Beyond group 7, no higher oxides of iron abov Fe,O are known, Some metals in higher oxidation state stabilize by forming oxocations, ¢g., V¥as VO}, Vas VO" and Ti as TiO*, All the metals except scandium form the oxides with the formula MO which are ionic in nature. As the oxidation number of the metal increases, ionic character decreases, .g., Mn,0, is a covalent green oil. Even CrO, and VO, have low melting points. 2 mos ‘ MnO Mn,O, Mn,O, MnO, Mn,O, In general, the oxides in the lower oxidation states of the metals are basic and in their higher oxidation states, they are acidie whereas in the intermediate oxidation state, the @ 4Fe0.Cr,0, + 8Na,CO,+ 70, —> 8Na,CrO, + 2F i ‘oxides are amphoteric. For example, the behaviour of the oxides of manganese may be represented as follows : MnO MnO, Mn,O, MnO, Mn,O, ae Amt Amp! Ang Ae ‘Thus, Mn,O, dissolves in water to give the acid HMnO,, SZKMnO, Potassium permanganate Itis prepared from the ore called chromite or ferrochrome ‘or chrome iron, FeO.Cr,0,. The various steps involved areas follows = Preparation of sodium chromate. The ore is finely powdered, mixed with sodium carbonate and quick lime and then roasted, ic., heated to redness in areverberatory furnace with free exposure to air when sodium chromate (yellow in colour) is formed and carbon dioxideis evolved. Quick lime keeps the mass porous and thus facilitates oxidation. , + 8CO, Chromite ore Sod, chromate Feri oxide ‘After the reaction, the roasted mass is extracted with water shen sodiumchromate is completely dissolved while ferric oxide is left behind. Ferric oxide is separated out by filtration, Conversion of sodium chromate into sodium dichromate, “The filtrate containing sodium chromate solution is treated with concentrated sulphuric acid when sodium chromate is converted into sodium dichromate. 2Na,CrO,+H1,S0, —+ Na,Ch,0,+Na,SO, + H,0 Salchomic! (Cane) Sol dime Sodium sulphate being less soluble crystallizes out as decahydrate, Na,$O,. 10H, and is removed. The clear solution is then evaporated in iron pans to a specific gravity of 1.7 when a further erop of sodium sulphate is formed. It is removed and the solution is cooled when ‘orange crystals of sodium dichromate, Na,Cr,0,, 2H,0 separate on standing, ) Conversion sodium dichromate into potassium dichromate. Hot concentrated solution of sodium dichromate is treated with calculated amount of potassium chloride when potassium dichromate, being much less soluble than sodium salt, erystallizes out on cooling as orange crystals, Na,C1,0, +2KCl —+ K,Cr,0, +2NaCl Sau dctemse ‘Reni dcromte3.3 Properties Colour and Melting point. It forms orange crystals which melt at 669K. Solubility. It is moderately soluble in cold water but freely soluble in hot water. Action of heat. When heated to a white heat, it decomposes with the evolution of oxygen. 4K,C,0, —>4K ,C10, +2C5,0, +30; Action of alkalies. When an alkali is added to an orange red solution of dichromate, a yellow solution results due tothe formation of chromate. K,Cr,0, + KOH 2K, Cr0,+ 1,0 a ra Pacha or Cr,0} +20H” —+2Cr0} +H1,0 On acidifying, the colour again changes to orange red due to the reformation of dichromate, 2K,C10, + 11,80, —>K,Ch0, +K,S0, +H,0 or 2CrO} +2 1’ —4C,0F +11,0 This interconversion is explained by the fact that in dichromate solution, the Cr,0}" ions are invariably in equilibrium with CrO}* ions at pH=4, Cr,03" +H,O 8 2107" +211" (ieee) irra) ‘Onadding an alkali (ic, increasing the pH of the solution), the I* ions are used up and according to the law of chemical equilibrium, the reaction proceeds inthe forward direction producing yellow chromate solution. On the other hand, when an when an acid is added (ie., pH ofthe solution is decreased), the concentration of H° ions is increased and the reaction proceeds in the backward direction producing an orange red dichromate solution. id Action of concentrated sulphuri (a) Incold, red crystals of chromic anhydride (chromium, trioxide) are formed. , +211,80, 210, + 2KHSO, +H,0 (b) On heating the mixture, oxygen is evolved. 2K,Cr,0, +81,S0, —+2K,SO, +2Cr, (SO, ), +8H,0+30, @ ro) 0) w) wi) (wii) (iii) sy) Oxidising properties. It isa powerful oxidising agent. In the presence of dilute sulphuric acid, one molecule of potassium dichromate furnishes 3 atoms of available ‘oxygen as indicated by the equation : K,CK0, + 4H,S0, —+K,SO, +Cr, (SO,),+ 4H,0+30 or CxO} +1411" +6" —92Cr* +7110 Mol. wt, 24 og Eq. wt. of K,Cr,0, = z It liberates 1, from KI K,Cr,0, +7H,S0, + 6KI—+4K,S0, +Cr, (SO,), +31, +7H1,0 Itoxidises ferrous salts to ferric salts K,C1,0, +7H,S0, + 6FeSO, —>K,SO, +Cr, (SO,), +3Fe, (SO,), +2H,0 Itoxidises H,S to sulphur K,Cr,0, +4H,S0, +3H,S—+K,S0, +Cr, (SO,), +7H,0+38 It oxidises sulphites to sulphates and thiosulphates to sulphates and sulphur K,C;0, +4H,S0, + 3Na,SO, —>K,SO, +Cr,(SO,), +41,0+3Na,S0, Itoxidises nitrites to nitrates K,C1,0, +4 11,80, +3NaNO, —>K,SO, +Cr,(SO,), +3NaNO,+411,0 Ito ises halogen acids to halogen K,Cr,0, +14 HCI 2KCI+ 2CrCl, + 7H,0+3C1, Itoxidises SO, to sulphuric acid K,C,0, + 11,80, +380, —+K,S0, +Cr, (S0,), +31,0 It oxidises stannous salts to stannic salts CeOF +14 11 435n!* —42.Cr" 43 Sat +350" +7 11.0 It oxidises ethyl alcohol to acetaldehyde and acetic acid. K,Ci,0, +4H,S0, rk, SO, +Cr, (SO, ), +4H,0+30 CH,CH,OH+O—+CH,CHO+H,0 aldozs Uses. o Note CH,CHO+ O—+CH,COOH ‘eee ‘este aid Test for a drunken driver. The above reaction helps ti test whether a driver has consumed alcohol or not, he is asked to breathe into the acidified K,Cr,O, solution taken inatest tube. Ifthe orange colour of the solution changes into green colour (due to Cr,(SO,), formed in the reaction), the driver is drunk, otherwise not Horide test (Reaction witha chloride and conc. acid). When heated with concentrated hydrochloric acid or with a chloride and strong sulphuric acid, reddish brown vapours of chromyl chloride are obtained. K,Cr,0, +4KC1+ 611,50, —>+ 2C10, Cl, + 6KHSO, +311,0 Reaction with hydrogen peroxide. Acidified K,Cr,0, solution reacts with H,O, to give a deep blue solution due to the formation of peroxo compound, CrO (O,),. Cr,OF +2 H" +4 1,0, —92 CrO, +5 The blue colour fades away gradually due to the decomposition of CrO, into Cr ions and oxygen ~ a The structure of CrO, is | Ai 2KMnO, +MnO, | 42K,CO, 2K,MnO, +Cl; —+2KMnO, +2KCI 2K,MnO, +1,0 +0, —+2KMn0, +2KOH+0, ‘The carbon dioxide process is uneconomical as one third of the original manganate is reconverted to manganesedioxide. However, this process has the advantage that the potassium carbonate formed as a by-product can be used for the oxidative fusion of manganese dioxide. In the chlorine process, potassium chloride obtained as a by-product is lost, PROPERTIES 3. 4. 5. @ @ Colour, Potassium permanganate exists as deep purple black prisms with a greenish lustre which become dull in air due to superficial reduction, Solubility. 11 is moderately soluble in water at room temperature and it is more soluble in hot water, . When heated to $13 K, it readily ing oxygen. Action of he decomposes 2KMnO, —+K,MnO,+Mn0, +0, et mena At red heat, potassium manganate formed decomposes into potassium manganite (K,MnO,) and oxygen, 2K,MnO, —+2K,MnO, +0, Action of heat in current of hydrogen. When heated in a current of H,, solid KMnO, gives KOH, MnO and water vapours, 2KMnO, +SH, —>2KOH +2Mn0+4H,0 ing property. Potassium permanganate is powerful oxidising agent. The actual course of reaction depends oon the use of the permanganate in (a) neutral (b) alkaline or (c) acidic solution, In neutral solution, Potassium permanganate acts as a moderate oxidising agent in neutral aqueous solution, because of the reaction 2KMnO, +H,0—>+2KOH +2Mn0, +30 or MnO; +2H,0+3 ¢ —>MnO, +401” ‘Thus, MnO, ion gains 3 electrons, Also, according to the above equation, in neutral medium, from two moles of permanganate, three oxygen atoms are available, In fact, during the course of reaction, the alkali generated renders the medium alkaline even when we start with neutral solutions. Hence, Eq. wt. of KMnO, in neutral or weakly alkaline medium _ Mol wt. _ 158 “3 q Some oxidizing properties of KMnO, inthe neutral medium. These are given below : 2.67 Itoxidises hot manganous sulphate to manganese dioxide. 2KMnO, +3MnSO, +2H,0—+K,SO, +2H,S0, +5Mn0, Presence of ZnSO, or ZnO catalyses the oxidation. @ (ii) ©) It oxidises sodium thiosulphate to sodium sulphate, 8KMn0, +3N: ), + 11,0 —+3K,S0, +8Mn0, + 3Na,SO,+2KOH It oxidises hydrogen sulphide to sulphur. 2KMnO, +411,S—+2MnS+S+K,SO, +4H,0 In alkaline solution, Instrongly alkaline solution, MnO} (manganate) ion is produced 2KMnO, +2KOH—+2K,MnO, +H,0+0. or MnO! +e" —>Mn0;- Mol wt. _ 158 1 1 2 Eq. wt, of KMn0, Potassium manganate is also further reduced to MnO, when a reducing agent is present K,MnO, +H,0—+ MnO, +2KOH +0 or MnO} +2H,0+2 e" —9Mn0, +40H" So the complete reaction is : 2KMn0, + H,0—+2Mn0, +2KOH +30 or MnO; +2H,0+3 e° —+MnO, +401 which is the same as that for neutral medium, Hence, equivalent weight of KMnO, in weakly alkaline mediumis same as that in the neutral medium, viz.,52.67 ‘Some oxidizing properties of KMaO, in the alkaline medium. o @ ‘These are given below Itoxidises potassium iodide to potassium iodate. 2KMn0, + H,0 +KI—+2Mn0, +2KOH + KIO, or 1 +601" —410; +311,0+6 In this case, iodine is not liberated unlike the case of acidic ‘medium, Si reaction takes place with KBr. It oxidises olefinic compounds to glycols, i, when an olefinic compound is shaken with alkaline KMnO,, pink colour of KMn0, is discharged CH, CH,OH || +H,0 + ©) —faae> | CH, CH,OH Ethylene Ethylene glycol Alkaline KMnO, used for this test is known as Baeyer's reagent. Itis used for oxidation of a number of organic compounds.© Some oxi o Co) ™ (wi) (wii) In acidic medium. Potassium permanganate in the presence of dil. sulphuric acid, ie, inacidic medium, acts as a strong oxidising agent because of the reaction 2KMnO, +311,S0, —+K,SO, +2MnSO, +311,0+50 or MnO; +81’ + ¢° —>Mn™* +41, Since in the above reaction, MnO; ion gains 5 electrons of fiveatoms of oxygen are available from two molecules of KMnO,, Hence, baw or pte a MOL, ‘These are given below : loxidises H,S 10S. 2KMn0, +3H,80, +5HS—+K,S0, +2MnSO, +2H1,0+50 Itoxidises sulphur dioxide to sulphuric acid. 2KMnO, +5 SO, +211,0—>+K,SO, +2MnSO, +2H,S0, It oxidises nitrites (NO) to nitrates (NO; ), arsenites (As0}") to arsentates (AsO{") and sulphites and thiosulphates to sulphates. 2KMn0, +3H1,SO, +5KNO, —+K,SO, +2MnSO, + 31,0+5KNO, Itoxidises oxalates or oxalic acid to CO, 2KMaO, +3H,S0, +5C,H,0, —>K,$0, +2MnSO, + 8H,0+10 CO, Itoxidises ferrous sulphate to ferric sulphat salt to ferrie salt) , ferrous 2KMnO, +8H,SO, +10FeSO, —>K,SO, +2MnSO, + 5Fe, (SO,), +8H,0 Itoxidises H,O, to H,O and O, This is because acidified KMnO, is a stronger oxidising agent than H,O,, 2KMnO, +3H,S0, +5H,0, —+K,SO, +2MnSO, + 8H,0+50, It oxidises potassium iodide to iodine 2KMnO, +3H,SO, +10KI—> K,SO, +2MnSO, + 8H,0+51, (viii) (os) Uses, 0 (i), (vy) Itoxidises HX (where X= Cl, Br, 1) 0X, 2KMnO, +3H,SO, +10 IX—+K,SO, +2MnSO, + 8H,0+5x, 1oxidises ethyl alcohol to acetaldehyde 2KMnO, + 311,80, + SCH,CH,01 —+K,S0, +2MnSO, + SCH,CHO+8H,0. Itis often used in volumetric analysis forthe estimation of ferrous salts, oxalates, iodides and hydrogen peroxide. However, it isnot primary standard because itis difficult to obtain it in the pure state and free from traces of MnO, Itis, therefore, always first standardised with a standard solution of oxalic acid. ‘Remember that volumetric titrations inolving KMnO, are carried out only in presence of dilute 1,SO, but not in the presene of HCl or HNO, This is because oxygen produced from KMnQ, + dill. H,SO, is used only for oxidizing the reducing agent. Moreover, 11,SO, does not give any oxygen of ts own to oxidiize the reducign agent. In case HCL is used, the oxygen produced from KMnO, + HCl is partly used up to oxidize Hel to chlorine and in case HNO, is used, it itselfacts as oxidizing agent and partly oxidizes the reducing agent. Itis used as a strong oxidising agent in the laboratory as ‘well as in industry. It is a favouriteand effective oxidising agent used in organic synthesis Alkaline potassium permanganate is used for testing unsaturation in organic chemistry and is known as Bacyer’s reagent. Potassium permanganate is also widely used as a disinfectant and germicide. A very dilute solution of permanganate is used for washing wounds and gargling for mouth sore. It is also used for purifying water of stinking wells. ‘Because of its strong oxidizing power, it is also used for bleaching of wool, cottong, silk and other textile fibres, and also for decolourisation of www.telegram.dog/jeemainrkPMD rae) These elements are classified by the filling up of the THE LANTHANIDE SERIES antipenultimate 4f energy levels. oe aa Electronic Configuration and oxidation states anenr Electronic Electronic ‘Oxidation States Configuration ‘Configuration of M* Lanthanum la [Xe] Sd! 63 [Xe] +3 Cerium ce [Xe] 4# Sa! 6s? [Xe] 4f! +3 (+4) Praseodymium Pr [Xe] 4f? 6s? [Xe] 4f? +3 (4) Neodymium Na [xe]4t 6s? [Xe] 48? 2) +3 Promethium Pn [xe]4r 6s? [Xe] art 2) +3 Samarium, Sn [Xe]4f® 6s? [Xe] 41° 2) +3 Europium Eu [Xe]4f? 6s? [Xe] 4f* (#2) +3 Gadolinium Gd [Xe] 4f7 Sd! 6s? [Xe] 4f7 +3 erbium: Th [Xe] 4f? 6s [Xe] 4f* +3 (+4) Dysprosium Dy [Xe]4f"? 6s? [Xe] 4f° +3 (+4) ‘Holmium Ho [Xe]4f" 6s? [Xe] 4f!* +3 Erbium: Ee [Xe]}4f? 6s? [Xe] af!" +3 ‘Thulium: Tm [Xe] af? 6s? [Xe] 4f? (+2) +3 ‘Yiterbium_ Yo [Xe]4r" 6s? [Xe] 4£9 (+2) +3 Lutetium Lu [Xe] 4 Sa! 6s? [Xe] ae! +3 2.1 Oxidation state The sum of the frst three ionization energies for each element state (HI) is ionic and Ln’* are low. Thus the oxidat dominates the che ry of these elements, The Ln?* and Ln** ons that do occur are always less stable than Ln. Oxidation numbers (+11) and (+1V) do occur, particularly when they lead to : 1. anoble gas configuration e.g. Ce** (f°) 2.ahalffilled f shell, e.g. Eu? and Tb** (f°) 3. acompletely filled level, eg. Yb™ (f"). JEE Main Revision Materials: www.crackjee.xyZThe 4f electrons in the antipenultimate shell are very effectively shielded from their chemical environment ‘outside the atomby the Ss and Sp electrons. Consequently the 4f electrons do not take part in bonding, They are neither removed to produce ions nor do they take any significant part in crystal field stabilization or complexes. Crystal field stabilization is very important with the d= block dements Theactahedra splitting of forbitdsa, is ‘only about 1k3 mol"!. Whether the f orbitals are filled or ‘empty has little effect on the normal chemical properties. However, it does affect their spectra and their magnetic properties. 22 Atomic radius Inlanthanide series, with increasing atomie number, there is a progressive decrease in the atomic as well as ionic radii of trivalent ions from La** to Lu’. This regular decrease in the ‘atomic and ionic radii with increasing atomic number is known as lanthanide contraction. ‘As we move along the lanthanide series, the nuclear charge increases by one unit at each successive element. The new electron is added into the same subshell (viz.,4f). Asa result, the attraction on the electrons by the nucleus increases and this tends to decrease the size. Further, as the new electron is added into the f-subshell, there is imperfect shielding of ‘one electron by another in this subshell due to the shapes of these Forbitals. This imperfect shielding is unable to counterbalance the effect of the increased nuclear charge. Hence, the net result is a contraction in the size though the decrease is very small. It is interesting to note that in lanthanides, the decrease in the atomic radius for 14 elements [Ce (58) to Lu (71)] is only 11pm (from 183 to 172 pm). Similarly, decrease in ionic radii from Ce** to Lu’* is only. 17pm (103 1086 pm) ‘The contraction is similar to that observed in any transition series. The cause is also similar, just as in the transition series where the contraction is due to imperfect shielding of ‘oned electron by another. Butthe shielding of one 4felectron by another is less than one d electron by another with increase in nuclear charge along the series. Atomic and Ionic radii (pm) of lanthanum and lanthanoids. Element la | Ce | Pr | Nd | Pm | Sm Eu ct | 15 | py Ho | & | tm} vb | Lu Atomic Radii(Ln) | 187 we [oe ig | 181 | 180 19 10 [1 [ 176} 175 | 174 | 173 | 172 lonicRadii(Ln™*) | 106 fo 9 | ® | % 95 | 94 aa |» |» |» fo |» 72.3 Magnetic behaviour Paramagnetism is shown by the positive ions of lanthanides except La** (lanthanum ion, !°) and Lu” (lutetium ion, £4). ‘This property of the lanthanides is due to presence of unpaired electrons in the incomplete 4f'subshell. lanthanides differ from transition elements in the fact that their magnetic moments do not obey ‘spin only" formula, viz. Hen = fn (n+2) BM. where n is the number of ion unpaired electrons, This because in case of trans clements, the orbital contribution is quenched by the electric ficld ofthe environment but incase of lanthanides, f orbitals lie to deep to be quenched. Hence, their magnetic moment is calculated by considering spinas well as orbital contribution, ie, Her = V4SG4 +L (C40 BM, where $ number, spin quantum number and L is orbital quantum Separation of the Lanthanide Elements ‘Since the change in ionic radiusis very small, the chemical properties are similar. This makes the separation of the ‘element in pure state difficult, Separation is done by lon Exchange methods which is based on the ionic size, JEE Main Revision Materials: www.crackjee.xyz2.4 Colour ‘The Lanthanides are silvery white metals. However, most of the trivalent metal ions are coloured, both in the solid state and in aqueous solution. This is due to the partly filled-f- orbitals which permit F- transition Lanthanides ions with x f electrons have a similar colour to those with (14-x) f electrons e.g., La®* and Lu’* are m?* and Dy** are yellow and Eu™* and Tb** colourless, are pink The hydroxides Ln(OH), are precipitated as gelationous precipitates by the addition of NI1,OH to aqueous solutions. ‘These hydroxides are ionic and basic. They are less basic than Ca(OH), but more basic than Al(OH), which is amphoteric. The metals, oxides and hydroxides all dissolve indilute acids, forming salts. Ln(OH), are sufficiently basic toabsorb CO, from theair and formearbonates. The basicity decreases as the ionic radius decreases from Ce to Lu. Thus Ce(OH), is the most basic, and Lu(OH,), which is the least basic, is intermediate between Scandium and Yttrium in basic strength. The decrease in basic properties is illustrated by the hydroxides of the later elements dissolving in hot concentrated NaOl!, forming complexes. Yb(OH), + 3NaOH — 3Na* + [Y(OH),]* Lu(OH), + 3NaQH - 3Na*+[Lu(OH), > ACTINIDES SERIES ‘The clements and their Oxidation States Atomic} Element |Symbol | Outer | Oxidation electronic states* structure 9 Actinium Ac 6d'7s? a ” Thorium: Th 6d? 7s? 43,44 91 | Protactinium) Pa | St? 6d! 75? | +3,+4,45 2 Uranium, Us [st 6d! 7s? | +3,+4,+5,+6 B ‘Neptunium Np | 5f*6d' 7s? |+3,+4,+5,+6,+7 94 | Plutonium =| Pu [Sf 75? |+3,+4,+5,+6,+7 % Americium =| Am |5f7 7s? |+2,43,+4,+5,+6 % Curium, Cm | S£7 6d! 7s? |+3, +4 ” Berkelium Bk [Sf 7s? [+3,+4 98 | Califorium | cr | stl? 7s |42,43 9 Einsteinium | Bs |Sf'! 7s? |+2,+3 100 | Fermium Fm |5f'? 7s 142,43 101 | Mendelevium | Md | 5¢!? 73? }+2,+3 102 | Nobelium No |st'* 7s? }+2,+3 103 | Lawrencium | Lr | Sf'* 6d! 7s* ]+3 104 | Rutherfordium] RE | 4f** 6d? 7s? eau Unlike Lanthanides, Actinides show a large number of oxidation states. This is because of very small energy gap between Sf, 6d and 7s subshells. Hence, all their electrons can take part in bond formation. The dominant oxidation state of these element is+3 (similar to Lanthanides). Besides, +43 state, Actinides also exhibit an oxidation state of +4. Some Actinides show still higher oxidation states. The maximum oxidation state first inereases upto the middle of the series, and then decreases, .g,, it increases from +4 from Th to +5, +6, and +7 for Pa, U and Np but decreases in the succeeding elements. ‘The Actinides resemble Lanthanides in having more compounds in +3 state than in the +4 state. However, the compounds in the +3 and +4 state tend to undergo hydrolysis. Further, itmay be noted that in case of Actnides, the distribution of oxidation states is so uneven that itis of no use to discuss their chemistry in terms of their oxidation states. ree ‘The Actinides show Actinide contraction (very much like Lanthanide contraction) due to poor shielding effect of the Sfelectrons. As a result, the radii of the atoms or ions of these metals decrease regularly across the series. The contraction is greater from element to element in this series, due to poorer shielding by 5f electrons. This is because Sf orbitals extend in space beyond 6s and 6p orbitals whereas 4forbitals are buried deep inside the atomDae Like Lanthanides, the Actinides elements are strongly paramagnetic, The variation in magnetic susceptibility of ‘Actinides with the increasing number of unpaired electrons, is similar to that of Lanthanides but the values are higher for the Actinides than the Lanthanides. 4. COLOUR ‘These metals are silvery white, However, Actinide cations are generally coloured, The colour of the cation depends ‘upon the number of Sf-electrons. The cations containing no Sf-electron or having seven Sf-electrons (i.e., exactly half-flled fsubshel!) are colourless, The cations containing subshell are coloured both in the crystalline state as well as in aqueous solution, The colour arises due to f-f transition e.g. Ac** (5°) = colourless, U* (Sf?) = Red, Np** (Sf) = Blue, Pu** (55) = Voilet, Am** (Sf®)=Pink, Cm** (Sf7)=Colourless, Th (5f°) =Colourless as s0 on COMPARISON OF LANTHANIDES AND ACTINIDES Similarities : As both Lanthanides and actinides involve filling of orbitals, they show similarities in many respects as follows : (@ Both show mainly an oxidation state of +3. Gi) Both are electropositive and very reactive. (ii) Both exhibit magnetic and spectral properties. Actinides exhibit Actinide contraction like Lanthanide contraction shown by Lanthanides. Differences: The show differences in some of their characteristics as follows : Lantha Actinides Mi iii) Iv) I(v) (vii) Besides + 3 oxidation state| they show +2 and-+4 oxi- dation states only in few cases. Most of their ions are colourless ‘They have less tendency towards complex formation Lanthanides compounds are less basic. Donot formoxocation -ept promethium, they are non-radioactive ‘Their magnetic properties ccan be explained easily. |() Besides +3 oxidation state, they show higher oxidation| states of +4,#5,+6,+7also. |(i) Most of their ions are| coloured ‘They have greater tendency) towards complex formation, (iv) Actinides compounds are more basie (v) From oxocationse.g U03*,PuO}* and UO* (vi) They are radioactive. (vii) Their magnetic properties ‘cannot be explained easily, asthey are more complex. JEE Main Revision Materials: www.crackjee.xyzBP en N # xn N JEE Main Revision Materials: www.crackjee.xyz CBSE Class 12 Chemistry Quick Revision Notes Chapter 9 Co-ordination Compounds * Co-ordination compounds: A coordination compound contains a central metal atom or ion surrounded by number of oppositely charged ions or neutral molecules. These ions or molecules re bonded to the metal atom or ion by a coordinate bond. Example: K4[Fe(CN)g] They do not dissociate into simple ions when dissolved in water. * Double salt . When two salts in stoichiometric ratio are crystallised together from their saturated solution they are called double salts Example: F'eSOq . (Hy) 2504 .6H2O (Mohr’s salt) ‘They dissociate into simple ions when dissolved in water. * Coordination entity: A coordination entity constitutes a central metal atom or ion bonded to a fixed number of ions or molecules. . Example: In K4[Fe(C'N)g] , [Fe(C.N)_]*~- represents coordination entity. © Central atom or ion: . In a coordination entity, the atomvion to which a fixed number of ions/groups are bound ina definite geometrical arrangement around it, is called the central atom or ion. Example: In K4[Fe(CN),, Fe is the central metal ion. * Ligands: . Amolecule, ion or group that is bonded to the metal atom or ion in a complex or coordination compound by a coordinate hond is called ligand.er ne e nN » nS ne e » IIT JEE Reference Materials: www.crackjee.xyz . It may be neutral, positively or negatively charged. . Examples: H20, CN~, NO* etc. © Donor atom: . Anatom of the ligand attached directly to the metal is called the donor atom. . Example: In the complex J¢4 [F'e(C'N)g],CN is a donor atom. © Coordination number: . The coordination number (CN) of a metal ion in a complex can be defined as the number of ligand donor atoms to which the metal is directly bonded. . Example: In the complex J¢4 [F'e(C'N),], the coordination number of Fe is 6. © Coordination sphere: . The central atom/ion and the ligands attached to it are enclosed in square bracket and are collectively termed as the coordination sphere. . Example: In the complex K4[Fe(CN)g], [Fe(CN)q]*"is the coordination sphere. * Counter ions: . The ions present outside the coordination sphere are called counter ions. . Example: In the complex K4[F'e(CN),, K+ is the counter ion. * Coordination polyhedron: . The spatial arrangement of the ligand atoms which are directly attached to the central atom/ ion defines a coordination polyhedron about the central atom. . The most common coordination polyhedra are octahedral, square planar and tetrahedral. . Examples: [P£Cl4}*~ is square planar, Ni(CO), is tetrahedral while [Cu(NH3)6]3+ is octahedral. « Charge on the complex ion: The charge on the complex ion is equal to the algebraic sum of the charges on all the ligands coordinated to the central metal ion. © Denticity: The number of ligating (linking) atoms present in ligand is called denticity.np Rp IIT JEE Reference Materials: www.crackjee.xyz * Unidentate ligands: . The ligands whose only one donor atom is bonded to metal atom are called unidentate ligands. . Examples: #20, NH3, CO, CN~ * Didentate ligands: |. The ligands which contain two donor atoms or ions through which they are bonded to the metal ion. . Examples: Ethylene diamine (Hz NC H2C HN Ho) has two nitrogen atoms, oxalate ion « oo- coo- has two oxygen atoms which can bind with the metal atom. * Polydentate ligand: . When several donor atoms are present in a single ligand, the ligand is called polydentate ligand. . Examples: In N(C H2C H2N Hp),, the ligand is said ta be polydentate and Ethylenediaminetetraacetate ion (EDT A*—~) is an important hexadentate ligand. It can bind through two nitrogen and four oxygen atoms to a central metal ion. © Chelate: . An inorganic metal complex in which there is a close ring of atoms caused by attachment ofa ligand to a metal atom at two points, . An example is the complex ion formed between ethylene diamine and cupric ion, [Cu(NH2 CH: NEp),|**. © Ambidentate ligand: Ligands which can ligate (ink) through two different atoms present in it are called ambidentate ligand. . Example: NO?- and SC'N~ . Here, NO?~ can link through N as well as 0 while SCN- can link through $ as well as N atom. * Werner's coordination theory:IIT JEE Reference Materials: www.crackjee.xyz 1, Werner was able to explain the nature of bonding in complexes, 2. The postulates of Werner’s theory are: a), Metal shows two different kinds of valencies: primary valence and secondary valence. b). The ions/ groups bound by secondary linkages to the metal have characteristic spatial arrangements corresponding to different coordination numbers. ). The most common geometrical shapes in coordination compounds are octahedral, square planar and tetrahedral. Primary valence . This valence is normally ionisable. . It is equal to positive charge on central metal atom. . These valencies are satisfied by negatively charged ions. . Example: In CrClg, the primary valency is three. It is equal to oxidation state of central Bene metal ion. Secondary valence . This valence is non -ionisable. nN .. The secondary valency equals the number of ligand atoms coordinated to the metal. It is also called coordination number of the metal. 3. Itis commonly satisfied by neutral and negatively charged, sometimes by positively charged ligands. * Oxidation number of central atom: The oxidation number of the central atom ina complex is defined as the charge it would carry if all the ligands are removed along with the electron pairs that are shared with the central atom. © Homoleptic complexes: Those complexes in which metal or ion is coordinate bonded to only one kind of donor atoms. For example: [Co(NH3)4|°" * Heteroleptic complexes: Those complexes in which metal or ion is coordinate bonded to more than one kind of donor atoms. For example: )2- [CoCh, (NFs),]*, [Co(NH3),Br] +IIT JEE Reference Materials: www.crackjee.xyz © Isomers: Two or more compounds which have same chemical formula but different arrangement of atoms are called isomers. © Types of isomerism: a). Linkage isomerism b). Solvate isomerism or hydrate isomerism c). Ionisation isomerism d). Coordination isomerism . Structural isomerism np . Stereoisomerism Geometrical isomerism ‘). Optical isomerism © Structural isomerism: p . It arises due to the difference in structures of coordination compounds. n . Structural isomerism, or constitutional isomerism, is a form of isomerism in which molecules with the same molecular formula have atoms bonded together in different orders. ¢ Tonisation isomerism: . It arises when the counter ion in a complex salt is itself a potential ligand and can displace a ligand which can then become the counter ion. . Example: (Co(NH3);,Br] SOyand [Co(NH3);SO4] Br nN * Solvate isomerism: . Itis isomerism in which solvent is involved as ligand. . If solvent is water it is called hydrate isomerism, e.g., (Cr(H20)g] Cls and [CrCl(H20),] Cle. 2H 0. nN « Linkage isomerism:IIT JEE Reference Materials: www.crackjee.xyz 1. It arises in a coordination compound containing ambidentate ligand. 2. In the isomerism, a ligand can form linkage with metal through different atoms. 3, Example: (Co(N'H3);ONO] Cl; and [Co(NH3);NO2] Ch. * Coordination isomerism: 1. This type of isomerism arises from the interchange of ligands between cationic and anionic entities of different metal ions present in a complex. 2. Example: [Co(N'H3)g] [Cr(C204)3] and [Cr(N'H3)¢] [Co(C204)s] © Stereoisomerism: This type of isomerism arises because of different spatial arrangement. * Geometrical isomerism: It arises in heteroleptic complexes due to different possible geometrical arrangements of ligands. © Optical isomerism: Optical isomers are those isomers which are non-superimposable mirror images. © Valence bond theory: 1. According to this theory, the metal atom or ion under the influence of ligands can use its (n-1)d, ns, np or ns, np, nd orbitals for hybridisation to yield a set of equivalent orbitals of definite geometry such as octahedral, tetrahedral, and square planar. 2. These hybridised orbitals are allowed to overlap with ligand orbitals that can donate electron pairs for bonding. Coordination ‘Type of hybridisation Shape of hybrid Number Square planar5 spd Trigonalbipyramidal spd? (nd orbitals are involved - outer orbital Octahedral complex or high spin or spin free complex) 6 d?sp? (n — 1) d orbitals are involved -inner orbital Octahedral or low spin or spin paired complex) © Magnetic properties of coordination compounds: A coordination compound is paramagnetic in nature if it has unpaired electrons and diamagnetic if all the electrons in the coordination compound are paired. Magnetic moment j1= a2) where n is number of unpaired electrons. © Crystal Field Theory: 1, It assumes the ligands to be point charges and there is electrostatic force of attraction between ligands and metal atom or ion. 2. It is theoretical assumption. © Crystal field splitting in octahedral coordination complexes: de ds» Energy oe dey % 3/54 inayentre rsa) CO fora : 2/5, 1,d.d, de. dy d, d,4,, Average energy — Splitting of d orbitals of the d orbitals in in octahedral Free metal ion spherical crystal field crystal fieldlIT JEE Reference Materials: www.crackjee.xyz © Crystal field splitting in tetrahedral coordination complexes: dd, Energy CO t a 2 24 soul? at : ao : de dy. & Me 01 dy.» dp d, dd, Average energy — Splitting of d orbitals of the d orbitals in in tetrahedral Free metal ion spherical crystal field crystal field « For the same metal, the same ligands and metal-ligand distances, the difference in 4 A, =-—A, 90 energy between eg and t2g level is Metal carbonyls: 1. Metal carbonyls are homoleptic complexes in which carbon monoxide (CO) acts as the ligand. 2. Example: Ni(CO), 3. The metal-carbon bond in metal carbonyls possess both s and p character. 4. The M-C bond is formed by the donation of lone pair of electrons from the carbonyl carbon into a vacant orbital of the metal. 5. The M-C mbond is formed by the donation of a pair of electrons from a filled d orbital of metal into the vacant antibonding7* orbital of carbon monoxide. 6. The metal to ligand bonding creates a synergic effect which strengthens the bond between CO and the metal.JEE Main Revision Materials: www.crackjee.xyz ALKYL HALIDE The alkyl halides or haloalkanes are a group of chemical compounds, derived from alkanes containing one or more This reaction involves the loss of atoms or groups of atoms t¢ halogens. They are used commonly as flame retardants, fire form an unsaturated compound. extinguishers, refrigerants, propellants, solvents and I '''ay pharmaceuticals. The alkyl halides are clasified broadly into three r | categories based on type of carbon atom to which the halogen reagent \ J ee ape co SE. acl +x-Y atom is attached. 1 aN x ¥ ERrc nce mca LER Men bie een eee) —C—x+Nu® —+ —C—Nu +x? 2° Secondary I ‘The replacement of halogen atom (leaving group) by the attacking nucleophile is called nucleophilic substitution reaction at sp carbon. This reaction was studied in great detail and two extrem mechanisms have been outlined to explain the course of the reaction 3.1 Substitution Nucleophilic Bimolecular —S,2 3° Tertiary Xmay be F, Cl, Brorl. Hy CTIONS IN ORGANIC CHEMISTRY p There are various types of reactions possible in organic 107 SH Be compounds depending on reaction conditions and attacking cit, agent. Reactions in organic chemistry are classified into three ategories Transition State A tet Mean jon involves addition of groups to a x bond. ie rt 2 Rate=kIRX] {No} NeacS + xy —ec 3. Nointermediateis formed, Reaction goes through a transition “> I state. x Y 2.2 Substitution Reaction 4, Rearrangement is not observed. 7 - 5, Inversion of configuration is observed. This reaction involves the replacement of an atom or a group of . atoms by another atom or group of atoms. 6, Order of reactivity of alky! halides: ‘This can be attributed to the steric hinderance to back side attack of nucleophile. Favoured by aprotic solvents.—cHc— BE acl +HX | | Hx “The removal of halogen from the carbon to which it is attached along with the removal of hydrogen from adjacent carbon iscalled ©, Brelimination or simply elimination. Three mechanisms have been outlined for elimination reactions.R, Rs R,. Ry ye sa RY Ry RY \ Ry\s a nucleophile. To understand how elimination and substitution compete with each other, we compare the nucleophilic behaviour with the basic behaviour, Nucleophilic nature LN pe — nature 5.1 Nucleophilicity vs Basicity (a) Nucleophilicity & basicity will be parallel if the comparing nucleophile have same attacking atom e.g. I CHO > On®> CHy;—C—O (b) Negatively charged nucleophiles are stronger than neutral nucleophiles. e.g. OH°>H,0 or NHS >NH, (©) Electrons on larger atoms are less tightly bound by the nucleus and are more polarisable and more readily available to carbon & will be better nucleophile. But they will be weaker base as their bond with smaller H-atom will be weaker & theirconjugate acids will be more reactive. Ifthe attacking ‘atoms are of same size, the stronger bases are better nucleophile. (In a period basicity of anions decreases) e.g Acidic Strength : CH,< NH,< H,0< HF Basie Strength and Nucleophilicty : CH, >°NH, > SoH > FF (@) Ifthe attacking atoms are different in size, the nucleophilicit depends on the solvents. However, in gaseous phase nucleophilicity parallels basicity. (©) Nucleophilicity is inversely proportional to stability of anion, 9 ee is a weaker nucleophile as it is resonance stabilized. (O Steric factor limits nucleophilicity CH, CH,CH,-0P> cae Nucleophilicity CH, Hy HP > CH,CH,—O? Basicity CHy(g) A strong base can be made a good leaving agent e.g. Oxygen containing group like OH® can be made a weak base in lic medium by protonation & become a better leav’ & agent OH). (ty Protic solvent : These solvents have a hydrogen atom attached to an atom of a strongly electronegative element (eg. oxygen). Molecules of protic solvent can, therefore form hydrogen bonds to nucleophiles as : A small nucleophile which is having high charge density than the larger nucleophile is strongly solvated and this solvation hinders the direct approach to the nucleophilic centre. Hence the smaller nucleophile doesn’t act as a good nucleophile as the larger one. Hence in protic solvent nucleophilicity is reverse of basicity. Fc? BP 1o inereasing basicity increasing mucleophilicity Aprotic solvents : These are the polar solvents that don't have H atom, capable of forming H-bonds e.g. oO 1 Aw ° H—C—N_ I ‘CH, CH;—S—CH, N, N-Dimethyl formamide Dimethyl sulphoxide (DMF) (DMSO) CH, CH, Dimethyl acetamide (DMA) These solvents dissolve i ic compounds and solvate the cations Now the naked anions are highly reactive as nucleophile and nov nucleophilicity follows the basicity e.g. Fc? B® 12 increasing basicity increasing nucleophilicity in aprotic solvents 5.2 Saytzeff vs. Hofmann Rule When alkene is formed by elimination of alkyl halides, th orientation of the double bond formed is governed by two rule: 5.2.1 Saytzeff’s Rule/Zaitsev Rule This rule suggests the formation of more stable alkene an therefore more substituted double bond. Reactions following thi rule are said to be thermodynamically controlled. 5.2.2 Hofmann Rule This rule suggests the formation of less stable alkene and therefor less substituted double bond. In such cases, the more acidic f hydrogen is abstracted to produce alkene. Such reactions a said to be kinetically controlled. High temperature favours elimination while low temperatui favours substitution reaction, cs Le TNS tis the preference of one direction of chemical bond making breaking over all other possible directions.mo Hy PH CHO Br | KOH —CH, + CH;—CH=CH—CH, But-2ene Stereoselective reactions give one predominant product because the reaction pathway has a choice. Either the pathway of lower vation energy (kinetic control) is preferred or the more stable product (thermodynamic control), ta ened on Pi | ea pr St nd Major Minor Stereospecific reuctions lead to the production of a single isomer as a direct result of the mechanism of the reaction and the stereochemistry of the starting material. There is no choice. The reaction gives a different diastereomer of the product from each stereoisomer of the starting materi ee He on IT Br ,C H 6.4 Chemosele When there are two or more functional groups in a molecule, given reagent may react preferentially with one rather than th other. Such reactions are called chemoselective. Reeves 1 Preparation of ty “Alkane Free radi Halogenatioa} [Alkenes ‘Alcohol 1. Addition of X (AX, PX, PX, 2. Addition of HX SOCI,) 3. a-Ialogenation) RX [Aligynes Eaxtany! Compownd 1. Audition of X (PCI) 2. Addition of ‘Alkyl Halides Halide Exchange 1. Finkelstein Reaction 2. Swartz Reaction 1. Alkanes ch RH—*RCI+HCI ‘This method gives a mixture of mono, di & trihalides.. 2. Alkenes () R—CH=CH, +X, + R—CH—CH, x CH, + HX —+ R—CH—CH, x I = x ae (ii) (a) R-CHy— CH=CH, > R—-CH—CH CH, (b) R—CH,—CH=CH, 85> p—cH—cH=CH, Br 3. Alkynes: xX xX )R-C=sC— Ht | G car RE xX xX JEE Main Revision Materials: www.crackjee.xyZi i) R—C=c— HX, R-e-cH x 4. Alkyl Halides () Finkelstein Reaction R—Br+Nal S22") R—1+NaBr R—Cl+ Nal 22%» R—1+ NaCl Swartz Reaction RoI Agl R—Br +AgF ee R—F + AgBr R-Cl sprotic AgCl 5. Alcohol +H,0 +H,PO; R—OH RX + POX, +X SOCIySOBr, +50,-+ 1X (SOC, Pyridine | +0, +11C1 6. Carbonyl Compound a r—C—i Sy R—C—H + Pocl, a 7.2 Reactions of Alkyl Halide (Coupling Reaction 1. Wurtz Reaction 2. Through Grignard Reagent Williamson's 3. Corey House Synthesis Synthesis LAI, Je RX (NaNO, (i With KCN (ii) Agno, (1) With AgCN 1, Coupling Reaction (@) Wurtz Reuction 2RX + 2Na 22s R—R + 2NaX (6) Grignard Reagent R—X+R—MgX —* R—R + MeX; (©) Corey-House Synthesis R—X +2Li ——* R—Li+Lix 2R—Li + Cul —* R,CuLi+ Lit R,CuLi+ R'—=-X—*RR'+R—CutLix 2. Ammonia Hon R—X + NH, —3—* R—NH, + HX WeAmine 3 KCN R—X + KCN——>R—CN + KX 4. AgCN R—X + AgCN—*R— 5. NaNO, RX + NaNO, —> R—O—N=0 + NaX 6. AgNO, RX + AgNO, —*R—NO, + AgX 7. Lisl, ROX + LiAI RH 8. Williamson's Synthesis R—X + R'—O—Na—+ R—O—R' 9, Aq. KOH& Al. KOH Rox 8, pon R=X AEKOMY Atkene JEE Main Revision Materials: www.crackjee.xyz10. Reactions of R-MgX HCHO. 1° alcohol 2° aleahol R—Mgx 3° aleohol # Wee ROH OH Halogenation of arenes Schiemann’ [Sandmeyer Aryl Halide| Reaction Reaction Diazotization (a) Halogenation of Arenes x ch + C1, eee QO (b) Sandmeyer Reaction NH, x (NaNO, 10? (Gu (©) Diazotization a © cuct NH, Nesnc? 7 = Br Car” (@) Schiemann Reaction NH, F N, + BFy 82 Reactions ofA jefMtaloarenes Electrophilic Aromatic Substitution + Benzyne Formation of Aryl [Mechanism [*—LHaloarenes | Grignard reagent t ‘Nucleophilic Aromatic Substitution (a) Electrophilic Aromatic Substitution Reaction : Halogens are ‘weakly deactivating and ortho/para directing,(6) Formation of Aryl Grignard Reugent: (4) PCY, withDicis& Carhony! Compounds cHon cHcl |" +pc,— |” Vicinal cHoH cuci — Dihalide x Mex Reactivity order: Ar-I > Ar-Br> Ar-Cl>Ar-F CH,CHO + PC, ——* CH,CHCI, Gem Dihalide 9.1.2 Properties (©) SyAr—Aromatic Nucleophilic Substitution Reaction (a) Alcoholic KOH : (Dehydrohalogenation) OCH e Alcohols Cyan XCH,CH,X SEM4> CHmmCH CHCHX, AEE CHCl () Zine Dust : (Dehalogenation) No, XCH,CH,X 4 CH=CH, zn (@)_Benzyne Mechanism (Elimination Addition Mechanism) CHCHX: nar CH=CH, Strong bases such as Na, K and amide react readily with (©) Actionofaq. KOH: (Alkaline Hydrolysis) (i) Vicinal Dihalides XCH,CH,X od a tooth OH OH Ethylene Glycol CH;CHXCH,X “ES + cHy—cH— CH, Alkylidene Dihalides or (i) Gem Dihalides Geminal Dihalides ous -H.0 a CH,CHX, “85 CH,CH(OH), + CH,CHO a fe yylene Dihalides or (unstable) x x Vicinal (1,2) Dihalides: CHCX,CH, “25> CH—C(OH),—CH, Prepar: > (unstable) [vs (a) Alkenes and Alkynes Halogenation of Alkenes & Alkynes CH,=CH, + X,—*CH;X—CH,X _Vicinal Dihalide cH,—C—CH, CH=CH + 2HX—> CH,CHX, Geminal Dihalide ‘Acetone9.2 TRI-HALIDES & TETRA-HALIDES. CHCl, CHB, Chloroform Bromoform li liquid) CHCl, cc, fodoform Carbon Tetrachloride (yellow solid) liquid) 9.2.1 CuLooroum: CHCI, (A) Preparation (i) Ethyl Alcohol : (using NOH/CI, or CaOC1,) NaOH + Cl>— NaOCl + HCl ; NaOCI—>(0] oy ch CHOH-S+ cH,CHO—-+ cCI,CHO + 3HCI 10) Cora cao, CCI,CHO + CuOH, —* 2CHICI, 1 Ca(liCOO), Slakel Lime Chloroform ‘NaOH u,clio + 3cl, —+ ccl,crio PASS ccl,cH(on), 4+ crcl, + HCOONa + 1,0 Chloralaydrate (ii) Methyl Ketones CHCOCH, +3Cl, ——> CCI,COCH, hoes abe jeson, CHECI, + (CH,COO),Ca (il) Carbon Tetrachloride Fe to CCI, + 2[H] aq —> CHC, + HCI Gv) Chlorination of Methane at 370°C ame + 3Ch: “Died Suaiabe (B) Reactions (@ Oxidation CH, CHCI, + 3HCI Chloroform in presence of light and air (O,) forms a highly posionous gas, Phosgene. 2CHCI, +0, + 2cocl, + 211C1 Phosgene (i) Carbylamine Reaction RNH, + CHC, + 3KOH > RNC +3H,0+3 KCI C,H.NH, + CHCI,+ 3KOH C,H,NC+3H,0+3KCI Isocyanides (carbylamines) have a very disagreable smell, so the above reaction is used as a test of chtororom and test of 1° (aliphatic and aromatic) amines. Gil) Hydrolysis, OH CHC, + 3KOH(aq) —+ HC—OH ou 11,0 HCOOK + H,0 4% HcooH (iv) Formation of Acetylene 2CHCI, + 6Ag ——> CH=CH + 6AgCI ‘Acetylene () Formation of Chloropicrin CHC, + HNO, ——* CCI,NO, Chloropicrin (an insecticide) (vi) Formation of Chloretone CHCl, + CH,COCH, ——> (CHye—cel on Chloretone (ahhypnotic medicine) JEE Main Revision Materials: www.crackjee.xyz‘9.2.2 IODOFORM: CHI. (A) Preparation: CyHOU +31; + 3Na,CO, | CHI, 4 + 311COONa + 3Nal + 2CO, T yellow ‘solid CH,COCH, + 31; + 2Na;CO, CHI, | +2Nal + CH,COONa+#,0 +2C0,t by @ CH, +4C, SES CCl, AHCI Gi) CS, +3Cl, aaa CCL, +S, SCI, is separated by fractional ‘obtain pure CCI, 28,Cl; + CS; —* CCL, + 68 CH,CH,CH, + Cl, = APE col, +HC1+ CCl, @B) Reactions: (@ Oxidation cci,+H,0 C+ coci, +2Hc1 steam lation. Itis then treated with more CS, to give CCI,. C washed with NaQH and distilled to (li) Reduction Fe/H, CCI, + 2[H] ——— CHCl, + HCI Gi) Hydrolysis CCl, + 4KOH(aq) ——> C(OH), 24,0 2KOH K,CO, +H,0 co; (iv) Action of HF SbF, CCl, + 4HF ——*> CIF, + 2HCI Freon (i) CH=CH + HCI———> CH, =CHC1 diy cH,cicr,c. $V. cH,=cHcl + KCI+H,0 Visi ital 600°C Gil) CH=CH, + C1, 27S cH=Scnel + HI (B) Reaction @ CH,=CHCI+ ale. KOH ——> CH=CH + HCI ‘Aceiyleae Halogen atom is vinyl chloride is quite stable and does not respond to nucleophilic substitution reactions easily. It is due to resonance stabilisation of vinyl chloride. @ H,c=cucn, + c1, 2S, cy —=cucn,cr Propene (ii) H,C=CHCH,OH + PCL, —+H,C=CHCH,CI Allyl Alcohol + Pocl, + HCI(B) Reactions (i) Addition Reactions @ cH,cr Se, CH,OH CH—CH,C1 + Cl, —> CH,CICHCICH,CI : NaCl CH,=CH—CH,Br + HBr—* CH,CHBrCH,Br 1, 2:Dibromopropane ‘The addition follows Markonikov's rule, However in presence of ; Kew peroxides, |, Sdibromopropane is formed. w Hcl SSS CHACN + Kel (ii) Nucleophilic Substitution Reactions Since in allyl chloride, there is no resonance (unlike in vinyl chloride), nucleophilic substitution reactions take place with ease, cr cnjc1 EM > CH=CHCH,OH + cH=ci—cn,cl CH=CHCH,OH + KCI m (Crone Nth ©O-~ Nii CHj=CH—CH,Cl + CH=ClI—CH,NH; + HCL + Hcl CH= CHCH,ClSX+ CH;=CH—CH,CN + KCl (iv) Wurtz Reaction CH CHCH,CL+ Mp + cH HCH,MgCl ign Reagent CH,CI + Na 9.2.6 Benzyl Chloride : C,H,CH,Cl: PhCH,CI [eo (A) Preparation oO v04%(C)-< H1,Cl+ HCL () Oxidation ZnCl, o(C)-104-O)-ene ©-= SNe” Orem + Mee enn ee + HCI ret ih 10.1 Preparation aii) ‘CH,OH—+++ CH,CL , RX +Mg aha R—Mg—X eI Ally Magnosam Halide + In Grignard re POCI; - H ue (B) Reactions ‘The main reactions are like those of Alkyl Halides (since there is [ 10.2 Reactions noresonance in benzyl chloride and intermediate benzyl carbonium ion is stable supporting S.1 subst substitution reactions occur with ease unlike in case of ary! halides (due to resonance in aryl halides). (A) Grignard reagent as a base reacts with compounds containing active H to give alkanes, R—Mgl + HOH ——> RH + Mg(OH) 1R—Mgl + RO—H—> RH + Mg(OR})1 (© Acid Chloride R—Mgl + R'NH—H—* RH + Mg(NHR)) I (B) Grignard reagent acts as a strong nucleophile and shows nucleophillic additions to give various products. Alkyl oMel ‘group being electron rich (carbonian) acts as nucleophile i Grignard Reagent. cH4cocl+ CH4Mel —* cH —E—Cl cH ee r ia | ‘ ROMEK + Go Maton CHLE=0 + Mal (Ch ew oun R Asals cH, Ketone Ketones (acetone) formed further reacts with Grignard reagent to oMel form3* alcohols (tert butyl ulcohol), However, with 1: moleratioof i cid halide and Grignard Reagent, one can prepare ketones. HCH + CH)Mgl—+ HCH ) Eaters [pem0 cu,Cu,oH OMel ("Atco HCOOCH, + CHyMgl —+H—C—0CyH, Format Ester " ll i OMel CH,CH + Mg (OCH) CH —C—H+ CHMgl —* CH,—C—H1 Aldehyde CH, . ‘The aldehydes react further with CH,Mgl to give 2° alcohol, if 11,0 a8! to Bt 7 Present in excess, But | : | mole ratio of reactants will certainly cHi—sH0H tive aldehydes, by €@ Alohot OMel CH,COOC,H, + CH|Mgl —* CH,—C—OC,I, Acetate Ester (CHy,C=0 + CH,Mgl —— (CH),C—OMgl cH, [veo | (CH,),C—OH i "Alcohol CHCCH, + Mg (OCH) 1 Ketone ‘The ketones react further with CH Mgl to give 3° alcohol, if present inexcess. But |; | mole ratio of reactants will certainly give ketones.© Cyanides H I HC==N + CH,MgI—+ CH, —C=NMgl [vs 1,0 CH,CHO +4.N, + MgI(OH) CH,C==N + CHjMgl—+(CH,),C=N—Megl ors 1,0 (CH,)C=0 +4 Ny +Mgl(OH) ——> R—C—OMgI fora0 —C—OH + Mgl (OH) Carboxylic Acid (G)_ Oxygen RMgl +0, 4S» R—O—OMgI ar er r R—O—O—Hl + Mgi(OH) Alkyl Peroxides (H)_ Ethylene Oxide (Oxiranes) CH Mgl + CH,— ‘0 + CH,—CH,—CH—OMel 11,0 CH,CH,CHOH + Mg(OH)I @® Alkynes CHyC=SC—H + CHMgl —> CH;C=C—Mel + CH, CH,C=C—Mgl + CHyI—* CH,C=C—CH, + Mel; (D Alkyl Halides R—Mgl + CH,CH;Br —>CH,CHR + Mg(Bnl CHyMgBr + CH HCH,Br—> CH,CH,R + MgBr, Alkyl Bromide (K)_ Inorganic Halides ACyIIMgBr +2PbCl, —> (CyH9) Pb ‘Tetracthy! Lead Pb + 4MgBr(Cl)ALCOHOLS, ETHERS AND PHENOLS PR ‘The compounds in which hydroxyl group (-OH) is attached to a sturated carbon atom are called as Alcohols, The compounds in which a hydroxyl group is attached to an unsaturated carbon atom of a double bond are called as Enols, The saturated carbon may be that of an alkyl, alkenyl, alkynyl, cycloalkyl or benzyl group. However, ia hydroxyl group is attached toa benzene ring, the compounds are called as Phenols. ‘The alcohols are further classified as : Monohydrie (containing one -OH group), Dibydrie (containing two -OH groups) and ‘Trihydrie (containing three -OH groups). Alcohols find usage in industry as well as day to dt example, ordinary spirit used for polishing wooden fu chiefly ethanol. Sugar, cotton, paperare all mace up of compounds containing ~OH groups. Phenols are used in several important polymers such as Bakelite and in several drugs such as Aspirin, Ethers are commonly used as solvents and anaesthetics. pare CH,—OH Methanol R—CH,—OH 1° Alcohol Primary Secondary 3°Alcohol Tertiary Symmetrical Ether Unsymmetrical Ether 3. STRUCTURES OF FUNCTIONAL GROUPS In alcohols, the oxygen of the -OH group is attached to carbon by a sigma (0) bond formed by the overlap of a sp" hybridised orbital of carbon with a sp’ hybridised orbital of oxygen. The following figure depict and methoxymethane. structural aspects of methanol, phenol Bond angle is slightly HL less due to LP-LP repulsion. OR eH H Methanol Lone pair of oxygen is delocalised on_ ring c—0 due to which bond lengthis less. Bond angle in methoxymethane is more than tetrahedral angle due to repulsive interaction between the two bulky (R) groups. The C—O bond length issameas inaleohols, Methoxymethane Ae Gans Boiling Point ‘The boiling points of alcohols and phenols increase with increase in the number of carbon ators (increase in van der Waals forces In alcohols, the boiling point decreases with increase in branching (decrease in Van der Waals forces due to decrease in surface area). ‘The -OH group in alcohols and phenols contains a hycdrogen, bonded to an electronegative oxygen atom. Therefore, itis capable of forming intermolecular hydrogen bond, strength of which is even greater than amine. [—O--H}-0-—~ 4 R H—9——-H—0-—-H—9-— It is due to the presence of strong intermolecular hydrogen bonding that alcohols and phenols have higher boiling points corresponding to other classes of compounds, namely, hydrocarbons, ethers and haloalkanes/haloarenes, amines of comparable molecular masses. Their boiling points are lower than carboxylic acid which have even more strong H-bond. For isomeric alcohols boiling points decreases with increase in branching due to decrease in van der ‘Waals forces with decrease in size. The order of boiling point is 1° alcohol > 2° alcohol > 3° alcohol. JEE Main Revision Materials: www.crackjee.xyZIn ethers, boil very less, and comparable to those of alkane of comparable molecular mass due to less dipole moment and absence of H-bonding. of alcohols and phenols in water is due to t ability to form hydrogen bonds with water molecules. The solubility decreases with increase in the size of hydrophobic group (R). Higher alcohol are insoluble. Branching increases solubility, due to decrease in surtace area of non-polar hydrocarbon part -butylalcohol 5.2.1 Acid Catalyzed Hydration > Markovnikov addi with carbocation rearrangements Ll 0 28 ee | HOH Markovnikoy orientation ‘5.2.2 Oxymercuration-Demercuration > Markovnikov addition without carbocation rearrangements. CH, CH; (1yHe(OAey, HO = H,C=C oye ani ‘CH; os oO om 5.2.3 Hydroboration-Oxidation Anti-Markovnikov ad CH, CH; (1) BH THF Hc, HO, Non” FH—E—CH, ‘CH, 5.2.4 SYNHydroxylation Reagents : Cold dil. KMnO,/NaOH or 0s0,/H,0, y CJ aor, 0H eKMRO AO” 1OH A H Cyclopentene cis-Cyclopentane-1, 2-diol5.25 ANTI Hydroxylation 5.33 Grignard Reagent/Organolithium Reagent Reagents : Peroxy Acids followed by Acidic Hydrolysis Nucleophilic addition to the carbony! group Le oO OMgx OH amex, | ne | C C— ——+—c— AN Dry ether” Ty i ~ 7 OH RCo. (a) Addition to Formaldehyde- 1°Alcohol IH on Cyclopentene trans-Cyclopentane-, 2-diol CH;CH.MgBr_ + HxC=0 vee one? CH,CH,—CH,—OH Primary (and some Secondary) Halides (CH)),CHCH,CH,—Br $914+ (CH,),CHCH,CH;—OH 5.3.2 First-order Substitution > (\- MgBr ‘Tertiary (and some Secondary) Halides ( Enantiomer) (b) Addition toan Aldehyde-2° Alcohol Phenyl Magnesium Bromide Acctaldchyde (Bier HF CH, | H CH;—C—CH 1 I con cl | {Bury Chloride cn, AcctonenWater 1-Phenylethanol Heat CHy CH; (Addition toa Ketone-3°Alcakol cup ets + H,C=C—CH, a oH 9 on Buyl Acohol Isoburylene 0) Ether 1 (CH,CH,MgCl + oe ‘CH,CH, one Cyclohexanone 1-Finyleyelohexanol JEE Main Revision Materials: www.crackjee.xyZ(@)Addition to: Acid Halide oran Ester-3°Alcohol yh € Senos Bensaldchyd Benzyl Aleoho! CH;—-C—Cl_ or ‘Acetyl Chloride Methyl Aeciate 2. Reduction of a ketone gives a secondary alcohol CyetohexsTmagnesiam Bromide o nan ae =a pa Cyclohexanone cyclohexanol i 1, LsDicyelohexylethanot CHj—(CH,,—C—OH or CHy—(CH,)—C—OCH, Decanoic Acid Methyl Decanoote (e) Addition to Ethylene Oxide 1° Alcohol (with wo carbon mua atoms added) and CH;—(CH,)—CH,—OH Deano MgBr CH,CH,O Reactions of LIAIH, and NaBH, nian, nda, NaBH, m7 ‘Cyetohexy! Magnesium Bromide 2.Cyclohexylethanol 0 Aldehyde pen R—CH,—OH]R—CH,—On 5.4 Carbonyl Compounds > 9 HH OW 5.4.1 Catalytic Hydrogenation > Ketone }R—C—R' |R—CH—R' | R—CH—R OH N\ f ay ame, athens | Yom | NoResetin | No Reston This method is usually not as selective oras effective as the use of hydride reagents. Acid Anion|R—C—C? | No Reaction |R—CH;—OH 5.4.2 Reduction with Metal Hydrides > aioe yin |. Reduction of an aldehyde gives a primary alcohol R—CH,OH Baer fa ogy NoReaeton ftGaal renee Oxidation 6.3 Ester ° I IL ROI + HO—C—R'—> RO—C—R' + H,0 Reactions as Acid 1. Alkoxide Formation] 2. Esterification Reactions as Base} }4)1. Dehydration 2. Substitution Fruity Smell Esterification is catalyzed by an acid or base. 3. Tosylation L. Pinacol-Pinacolone Rearrangement | 2. Periodic Cleavage of Glycols 1 Dehydration > R—CHy—CH,;—OH gone. HS, Saytzeffalkene easy ‘oF cone, HyPO,” (With rearrangement) Al;O3 Saytzeff alkene Rw 400°-S00°C (No rearrangement) . ThO, Hoffmann alkene -_ (No rearrangement) P,0,.4 ‘aytzetl a 20s Saytzeff alkene BD (No rearrangement) f Reactions with Aly Aee.. gaseous phase. 6.2 Substitution HX. RX+H,0 Syl/Sy2 RX +H,PO, Sy2 R—OH RX+POX,+HX — Sy2 RX+SO,T+HCIT Syi SOCI Pyridine RX+S0,T+HICIT §,2 Reaction of alcohol with SOCI, in the presence Nove. of Pyridine is known as Darzen’s Process. 6.4 Tosylation > ‘Tosylation is used to convert poor leaving group OH into good leaving group OTS. mp t ROH + oOo © Foyt Chtoride |) oC) +HCI 0 ‘Alkyl Tosylate iG mp (city cron BoPaitine Isopropyl Aleoho! 65 Oxidation (CH,),CH—OTs Isopropy!Tosylate (a)Primary Alcohols R—CH,OH Alk. KMn0, = RCOOH + Mn0,t + H,0 Pa Bow Acidic K,Cr,0,, . Sa RCOOH + Cry$0,), + K,S0, + H,0 Green 10, + H,0 + RCOOH Acetone PCC/PDC RCHO L_cu_, RCHO A (350°-400°C) JEE Main Revision Materials: www.crackjee.xyZ- Oxidation of Alcohols : Points to Remember ANoee. 1, Jones Reagent —Cr0, + H,O/Acetone PCC-—Pyridinium Chlorochromate PDC-—Pyridinium Dichromate CrO Pyridine in CH,Cl,-Collins Reagent. Cr (VI) oxidizes primary alcohol to aldehyde in anhydrous! non-aqueous state and to carboxylic acid otherwise. as ep (b) Secondary Alcohols H Secondary alcohol in the presence of any oxidising agent is oxidised to ketone. (c) Tertiary Alcohols 0,01 No reaction KMn0, or Kc 0 711,50, ‘far hours Smaller Acids cua opour Phase Dehydration Alkene MnO, is an oxidising agent which oxidises only allylic, benzylic & propargylic alcohols. R—CH=CH—CH;—OH ©- 1,—On Benzylic Alcohol Propargylic Alcohol Allylic Alcohol R—C=C—C—OH 9 OH H Common Phenolsand Aromatic Ethers OCH, OCH, CHy Oo O “ Arisole Phenctale 0-Cresol on coon NO, on NO; Pieri Acid Salicylic Acid ou ou OH “ ol ‘oH ou Catechol Resocinol Nydroguinone enue kamen ‘Cumene Process Distillation of Dow Phenolic A‘ Phenol #— proves with Sodalime = Hydrolysis of Diazonium Salts This is industrial method for preparation of phenol, It occur through Benzyne Mechanism.00re Ggll,Cl + 2NaOH Sgn H,O + NaCl + C,H OPNe . 202 a C,H,OH ‘Acid Cl (6 Grignard Reagent - Oo Be rhe Spe, On ©» + Mg(OH)Br 9. REACTIONS OF PHENOLS 1 Form cH, n of er AIC, CoH + CH, —=> CgHs—C—H (a) Williamson Synthesis cH, cumene aro Rx® f ey cn cH, Aron 2s Are?” hs, \ ue | : - —t-0—0-1 (CH),S0) CHsOH + Jo 0<—— CH 7 ‘O—O—H ‘Ar—O—CH, + CHy cHy ny Cumene Hydroperoxide (b) Nucleophilic Aromatic Substitution 83 Hydrolysis of Diazonium Salts > es AiNSHSO? + HO — ArOH +N, +H,S0, el PCs NO, NO, 8.4 Distillation of Phenolic Acids with Sodalime +N, P8cH, — +cP NO, NO, One +Na,CO,9.2 Formation of Esters 9.4.2 Oxidation to Quinor (CH,CO),0 + C,H,OH + NaOH ou ° CH,COOG,H, + CH;COP NP + 11,0 oy Phenyl Acetate mr Y Ouinone CyH,COCI + CyH,OH + NaOH | 9.43 Electrophilic Subst ion C\H,COOC,H, + NaCl +H, Phenyl Renzoate (a) Halogenation ou on Br, Br f.1,0 OH C—CH, Br 2.4.6 Taibromophenol o-Hydrosyacetonhenone iiider tayo eure C—CH, oO P-Hlydroxyacctophenone ‘OH OH Kinetic Control versus Thermodynamic Control Soto 4 cs, +B, +Br |. Para isomer is the major product at 25°C. It has lower AH and is formed more rapidly (rate controlled product). 2 Ontho isomer is the chief product at 165°C (equilibrium Br p-Dromophcnol controlled product). (major) ‘9.4 Reactions of Benzene Ring 9.4.1 Hydrogenation Monobromination is achieved with non-polar Example-26 Note. solvents such as CS, to decrease the clectrophilicity oH oH of Br, and alsoto minimize phenol ionization. In polar solvents ‘such as water, phenol ionizes to phenoxide ion whichis strongly Ni 175°, 15 atm activated and therefore, bromination takes place at all the +3, ‘activated positions. Cyclohexano! JEE Main Revision Materials: www.crackjee.xyz(b) Nitrosation to ou oH ° Toutomerize HONO N=0 N—OH ‘Quinone-Menoxime (©)Sulphonation Example -31 on SO,H (rate controlled) 1480, Bare 1H0PCI,S0, C,H,OH oH TOO (equilibrium controlled) SOjH (d)Diazonium Salt Coupling - Azophenols ArN® + CHG —> P-G—C,H,—N=N—Ar G is an electron releasing groups such as OH, -OR, -NR,.-NHR,-NHy, (e) Ring Alkylation: .H,OH + ‘CHyCH=CH, or (CH,),CHOH 1180, or HF Ou o- and p= CH +H,0 Ncryciy), RX andl AICI, give poor yields be lone pair of oxygen. (Ring acylation This is achieved using Fries Rearrangement, (g) Kolbe's Synthesis, oes CHPNP + o=c=0 LEC, ise AICI, co-ordinates with OH asc, 7 arm > O- Golly ‘COONa Sovlium Salicylate [ne OH 0-cH, coon Salieylie Acid (h) Riemer-Tiemann Synthesis of Phenolic Aldehydes OH OH CHO + CHCI, + OH? —> Salieylaldchyde ‘This reaction involves formation of carbene, CCl,. (Formation of Aspirin Ose (C0, KO one Il O—C—CH, COOH Acetylslicylic Acid (Aspiriny(j) Formation of Oil of Wintergreen on OH COOH cHon Tso,” coocH, Methyl Salicylate (Gil oF Winergroen) BOOM aity Substrate and Leaving Group in Williamson Aoie.. FA Synthesis L. Leaving group X= Cl, Br, 1, OTs, etc. 2. Substrate - Alkyl group R’ must be primary. 10.2 Alkoxymercuration-Demercuration \ ORE), I cmec/ Htononon, fd cv oN AcOHg OR tsa, H OR This reaction follows Markovnikov orientation. (0.3 Bimolecular Dehydration of Alcohols This reaction is an industrial method for synthesis of ethers. ar—on #s p-o—R+ 11,0 1 BRM cn ke sie TI Cleavage by Hi HI + xces HX py Rs ROR! BESET ROX ERIK Excess UX Ar OTR kB ‘Ar Aromatic Ring Ar—OH + R—X JEE Main Revision Material: Excess Hl CH,CH,—0—cH, =" CH,CH,I+ CHI thy! Methyl Ether Ethyl fodide Methyl Iodide excess 0 (slow OOH I R—O—CH—R' + R—O—O—CH,—R' Hydroperoxide Dial! Peroxide 12. PREPARATION OF EPOXIDES \ cc” + R—C—OOH DAK + ROE 0, 9° /\ | C0 + ton | 12.2 Base-promoted cyclization of halohydrins x ll on Il OH X=CI,Br,1,OTs,cte. N01, 11,0, rag 1c aoe oH 2-Chlore-1-Phenylethanol 2-Phenyloxirine www.crackjee.xyz13. REACTIONS OF EPOXIDES (a) Inwater I —c—c— te fe 4 t 9 OH Anti stereochemistry is followed. (b) Inalcohots on LL ue. tS WY LT o OR ‘The alkoxy group bonds to the more highly substituted carbon, 0 nph H. ‘c—cn, tee cry—ci—ci,—on A fie corr” iy HC ‘0 OcH, Methyl Oxirane 2-Methowy-propan--ot (Propylene Oxide) (€) Hydrohalic Acids (X= Cl, Br, I) OH {ows fb ex, | x I o_o \of I 2 Base-catalyzed Opening (a) With Alkoxides | ri? —C—Ch, qa peor o oH ‘The alkoxy group bonds to the less highly substituted carbon, ne 329 CHP Ox Rp Sion > CHs—CH—CH,—OCH, HC No OH Propylene Oxide 1-Mathoxy-2-Propanol (b) With Organometallics orem _ | —cocH, “+ cm \ FF ene yk ° oH M-=LiorMgx R bonds to the less substituted carbon mple- 41 "\ RS uc! Sof Propylene Oxide ane cmpra{ On L-cyclohexyl2-Propanol ‘Opening of Epoxide Rit Soe A ores ee 1. Inacid catalyzed opening, nucleophile attacks on that epoxide ‘carbon from which more stable carbocation can be made. 2. In base catalyzed opening, nucleophile attacks on the less hindered carbon. Brora (Alcohols are weaker acids than thiols even though oxygen is more electronegative than sulphur. Conjugate base of alcohol ite. RO” is more basic than RS" asin RO negative charge is placed onsialleroxyzen atom soit will have more charge density. Butin RST negative charge is dispersed on bigger sulphur so it isa poor base and its conjugate acid will be more acidic. Order of acidic strength of some of the compound are given as : RSO,H>RCOOH > Phenol > H,O> ROH > HC=CH>NH,>CH,=CH, >CH,-CH, (i) Allalcohols (except CH,OH) are weaker acids than H,O due to +H effect of alkyl group. CH, OH is slightly stronger than HO. Phenols are stronger than alcohol due to electron withdrawing benzene ring & resonance stabilized phenoxide ion, Alkoxideions, the conjugate base of aleohol have no resonance so they are less stable and more basic. Phenol is weaker than carboxylic acid which have strong electron withdrawing carbonyl group and more stable resonating structures.TESTS FOR ALCOHOLS, PHENOLS & ETHERS aracterization (a) Alcohols dissolve in cold concentrated sulfuric acid. This property they share with alkenes, amines, practically all compounds ining oxygen, und easily sulfonated compounds. (Alcohols, like other oxygen-containing compounds, form oxonium salts w dissolve in the highly polar sulfuric acid) (b) _ Alcoholsare not oxidized by cold dilute, neutral permanganate (although primary and secondary alcohols are oxidized by permanganate uneler more vigorous conditons.) However, as we have seen, alcohols often contain impurities that are oxidized under these conditions, and so the permanganate test must be interpreted with caution. cont (0) Alcohols do not decolorize bromine in carbon tetrachloride. ‘This property serves to distinguish them from alkenes and alkynes. Alcohols are further distinguished from alkenes and alkynes and from nearly every other kind of compound by their oxidation by chromic anhydride (CrO,) in aqueous sulfuric acids. Within two seconds, the clear orange solution tums blue-green and becomes opaque. ROH + HCrO, —* Opaque, blue-green Wer2” Clear Tertiary alcohols do not give this test. Akichydes do, but are eas lifferentiated in other ways. (a) Reactions of aleohols with sodium metal with the evolution of hydrogen gas is of some use in characterization, A wet compound! of any kind, of course, will do the same thing, until the water is used up. (©) Thepresence of the -OH group in a molecule is often indicated by the formation of an ester upon treatment with an acid chloride oF anhydride, Some esters are sweet-smelling: others are solids and harp melting points, and can be derivatives in identifications, I the molecular formulas of starting material and product are determined it is possible to calculate how many -OH groups are present. (9) Whetheran alcohol is primary, secondary or tertiary is shown by the Lucas test, which is based! upon the difference in reactivity of the three classes toward hydrogen halides. Alcohols (of not ‘more than six carbons) are soluble in the Lucas reagent, a mixture of concentrated hydrochloric acid and zine chloride, The corresponding alkyl chlorides are insoluble. Formation of achloride from an alcohol is indicated by the cloudiness that appears when the chloride separates from the solution. Hence, the time required for cloudiness toappearis a measure of the reactivity of the alcohol. ‘A tertiary alcohol reacts immediately with the Lucas reagent, and asccondary alcohol reacts within five minutes. A primary alcohol does not react appreciably at room temperature. Benzyl alcohol and allyl alcohol react as rapidly as teritary alcohols with the Lucas reagent. Allyl chloride, however, is soluble in the reagent. (g) Whether or not an alcohol contains one particular structural unit is shown by the fodoform test. The alcohol is treated with iodine and sodium hydroxide (sodium hypoiodite, NaOl). An alcohol of the structure yields a yellow precipitate of iodoform (CHI, mp. 119%), u R—-C—CH, — R=H/R/Ar on H CH, to ‘Any other primary aleohol ou " H cu-t—cn, cit—cu, bu ou " u on}—en.cx.cn cucy4—cH,cH, ou ou C\Hj;—CH,—CH,OH ‘The reaction involves oxidation, halogenation and cleavage. I R—C—CH, + Nol FRE CH +Nal + H,0 on nec + 3NsO1—+ RFC, +3Na0H 0 oO R—C—Cl, + NIOH—*RCOCNE + CHI, Yellow As would be expected from the equations, a compound of structure also gives a positive test R—C— I CHs R= WAyAnylTn certain special cases this reaction is used not as a test, but to synthesize the carboxylic acid, RCOOH. Here, hypobromite or the cheaper hypochlorite would probably be used. 15.2 Analysis of Glycols, Periodic Acid Oxidation Upon treatment with period HIO,, compounds containing two or more ~OH or C=O groups attached to adjacent carbon atoms undergo oxidation with cleavage of carbon-carbon bonds. R—CH—CH—R' + HIO, —> RCHO + R'CHO (+HIO,) OH OH RE G—R'+ 110, —+ RCOOIL+ REOOH oO ° 3 Miscellaneous Tests (@) eric Ammonium Nitrate Test - Alcohols give red colour with this reagent. Co(NH,),(NO, ), + CH, OH Co(NH,),(NO,), + RCOOH+HNO, ©) Potassium Dichromate Test = Alcohols turn orange dichromate to green. Tertiary Alcohol do not give this test. (© EsterTest- Alcohol gives fruity smell ofester with carboxylicacid. (@__ Mcthanal forms oil of winter green with salicylic acid. 154 Victor Meyer's Test 1° Alcohol 2° Alcohol 3° Alcohol R, R, S SS RCH,OH ‘cHOH | R=C—OH n4 F rvs pet, | RO [er RCH,L R,C—I oss, Aan RCH;—NO, R,C—NO, [10% vtono C—NO, [No Reaetion toon sow Nitrolic acid Colourless [son Blood Red Colour |} | Bluc Colour} 155 Differentiat 15.5.1 Alcohols and Phenols 1, Litmus Test : Phenol tums blue litmus red but not alcohols. 2. FeCl Neutral FeCly 3. Coupling reaction: ts henol Blue-Violet aronium Sat X2kWbasic, Yellow or Phenol + Diazonium Salt “SEES Toe Diazonium Salt + Alcohol “S282 8 No Reaction 4, Bromine Water Test : OH Br Br Phenol + Br, 2°» Br (white ppt.) Alcohol + Br, 2°, No Reaction 15.5.2 Alcohols and Ethers (a) Alcohols react with Na to give H but not ethers, (b) Alcohols give fumes of HCI with PCI, but not ethers. 15.5.3 Sodium Bicarbonate Test Phenol, ROH and H,0 do not displace CO, from carbonate & bicarbonates but RCOOH & RSO,H gives brisk effervescence of CO, which proves that RCOOH & RSO,Harestrongeracicls HCO, but phenol is weaker acid than H,CO,. Nitrophenols also give effervescence of CO, with Na,CO,, Trinitrophenol (Picric Acid) is highly acidic due to strong electron withdrawing effect of three groups its acidic strength is comparable to that of carboxylic acids, Its anion is highly resonance stabilised, on RCOOH + NaHCO, — RCOONa + CO, + H,0 Ph—OH + NaHCO; —* No Reaction.oH 1554 FeCl, Test ON, NO, Phenol gives characteristic purple colour with FeCl, but alcohols +NaHICO, do not react with FeCl, Carboxylic acids also form buff coloured precipitate with FeCl,. Only acetic acid forms red coloured NO, precipitate with FeCl, so it can be used as a test for acetate salts. ° ne Open (Os Fe+ 3HCI ON. No, f + Cost +10 rue [ssssermm NO, [Fe(PhO),) Purple SolutionINTRODUCTI Amines are organi derivatives of ammonia with one or more alkyl or ry| groups bonded to the nitrogen atom, Amines serve many functions n living organisms, such as bioregulation, neurotransmission, and lefense against predators. Because of their high degree of iological activity, many amines are uscd as drugs and medicines. Phe alkitloids are an important group of biologically active amines, nostly synthesized by plants to protect them from being eaten by nals, Although some alkaloids are used fy as painkillers) all alkaloids are toxic and cause ath if taken in Large quantities. Creu Amines are classified as primary (1°), secondary (2°),or tertiary 3°), corresponding to one, two or three alkyl or aryl groups onded to nitrogen. qe Primary (1°) (>it. » HyC—C—NH, RNH; | CH, Cyeloherytamine (1°) Tert-Buty amine (1°) CH,CH, Secondary (2°) R,NH 1 t H H NeEthylaitine (2°) Pipeidine (2°) CH,CH, | CH,CH, N.N-Diethylaniline (8°) Quinvetidine (3°) Quaternary ammonium salts have four alkyl or aryl bonds to a trogen atom. The nitrogen atom bears a positive charge. just as ( does in simple ammonium salts such as ammonium chloride. Phe fallowing are examples of quatemary (4°) ammonium salts. cncn, 1° 1,CH,C—N—CH,CH, CH,CH, ‘Tetraethylammanium fodide EM es Ammonia has a slightly distorted tetrahedral shape. A lone pair of nonbonding clectrons occupies one of the tetrahedral positions, This geometry is represented by sp* hybridization of nitrogen, with the bulky lone g the H—N—H bond angles 10 107° from the “ideal” sp* bond angle of 109.5°, Trimethylamine shows less angle compression because the bulky methyl groups open the angle slightly. 0 Now ARN HNN oe air compress Ammonia A tetrahedral amine with three different substituents (and a lone pair) is non-superimposable on its mirrorimage. In mostcases, we cannot resolve such an amine into two enantiomers, however, because the enantiomers interconvert rapidly. This interconversion takes place by nitrogen inversion, in which the lone pair moves from one face of the molecule to the other. sp orbital porbital (R)-cthylmethylamine (Transition State] (S)-cthylmethylamine In case of quaternary ammonium salts with asymmetic nitrogen atoms, inversion of configuration is not possible because there is no lone pair to undergo nitrogen inversion. 2 oo Nee CHC (CH,),CH "7 ScHch, HCH,C7™ \y CH(CHy)2 HC CH, (R) (Ss) Amines that cannot attain the sp-hybrid transition state for nitrogen inversion also show chirality. If the nitrogen atom is contained ina small ring, for example, itis prevented from attaining the 120° bond angles that facilitate inversion