Kendriya Vidyalaya Sangathan Lucknow Region Study Material Subject : CHEMISTRY Class - XII Prepared under supervision of Mrs. NOMITA WILSON PRINCIPAL, KENDRIYA VIDYALAYA IIM,LUCKNOW Astt. Commissioner KVS (LR) RANVIR SINGH Under Guidance of Dr. Satyendra pal Principal Kendriya Vidyalaya No. 1 , AFS, Agra Prepared By S.NO NAME OF THE TEACHER KENDRIYA VIDYALAYA 1 Dr. ABHYAS YADAV BARABANKI 2 SANGITA RANI SINGH GOMTI NAGAR, LUCKNOW 3 R.C.TIWARI B.K.T. , LUCKNOW 4 B.K.SHARMA ALIGANJ , LUCKNOW 5 A.K.DIXIT SITAPUR 6 MANJULA DIXIT I I M, LUCKNOW 7 RAJ SHEKHAR I I M, LUCKNOW CONTENTS ONE PAPER 70 MARKS UNIT NO. TITLE MARKS I SOLID STATE 4 II SOLUTIONS 5 III ELECTROCHEMISTRY 5 IV CHEMICAL KINETICS 5 V SURFACE CHEMISTRY 4 VI GENERAL PRINCIPALES AND PROCESSES OF 3 ISOLATION OF ELEMENTS VII P-BLOCK ELEMENTS 8 VIII D & F BLOCK ELEMENTS 5 IX COORDINATION COMPOUNDS 3 X HALOALKANES & HALORENES 4 XI ALCOHALS, PHENOLS & ETHERS 4 XII ALDEHYDES, KETONES & CARBOXYLIC ACID 6 XIII ORGANIC COMPOUNDS CONTAINING NITROGEN 4 XIV BIOMOLECULES 4 XV POLYMERS 3 XVI CHEMISRY IN EVERDAY LIFE 3 TOTAL 70 Unit-I THE SOLID STATE Density of unit cell = Mass of unit cell = z×M Volume of unit cell Na × a3 z- Number of atoms per unit cell M – Atomic mass or formula mass for ionic solids Na – Avogadro number a – Edge length Radius ratio = r+ = Radius of the cation rRadius of the anion If R is the radius of spheres in the close packed arrangement then I. Radius of octahedral void = r = 0.414 R II. Radius of tetrahedral void = r = 0.225 R Packing fraction = Volume occupied by atoms in unit cell Total volume of the unit cell Different types of solids (table) Unit cell Distance b/w nearest neighbor (d) Simple cubic a Face centered a/ cubic (FCC) Body centered /2a cubic (BCC) Where, a = edge length of unit cell Different Type of Solids s.n. Type of Solids Constituent Particles Radius Constituent Atom Coord Ination no. Packing fraction Number of Constituent Atoms a/2 a/2 6 12 0.52 0.74 8 0.68 1/8×8 = 1 (1/8×8) + (1/2×6) = 4 (1/8×8) + 1 = 2 Bonding/ Attractive Forces /4a Examples Physical Nature Electrical Conductivity Melting Point 1. Molecular Solids (i)Non -polar Soft Molecules Dispersion or London forces (ii)Polar Ar, CCl4 , H2 , I2 , CO2 Insulator Soft Insulator HCl , SO2 Dipoledipole Interactions (iii)Hydrogen bonded 2. Ionic solids Ions 3. Metallic solids 4. Covalent or Network solids Positive ions In a sea of delocalized electrons Atoms Very low Low Hard Insulator H2O(ice) Hydrogen bonding Coulombic NaCl, MgO or Zns, CaF2 electrostatic Metallic bonding Fe, Cu, Ag, Mg Covalent bonding SiO2 (quartz), SiC , C(diamond), AIN, C(graphite) Low Hard but Insulators in brittle solid state but conductors in molten state and in aqueous solutions Hard but Conductors in malleabl solid state as e well as in and molten state ductile Hard Insulators Soft High Fairly high Very high Conductor (exception) Important Questions; 1. Name the non-stoichiometric point defect responsible for colour in alkali halides. Ans: F-centres 2. What happens when a ferromagnetic substance is heated to high temperature? Ans: Ferromagnetic substance changes to paramagnetic substance due to randomization of domains (spins) on heating. 3. A compound is formed by two elements X and Y. Atoms of the element Y (anions) make ccp and those of the element X (cations) occupy all the octahedral voids. What is the formula of the compound? Ans: Suppose no. of atoms Y in ccp = N :. No. of octahedral voids = N :. No. of atoms X = N Ratio of X : Y = N : N =1: 1 Formula of compound is XY 4. Explain the following terms with suitable examples: (i) Schottky defect (ii) F-centres Ans (i) Stoichiometric defect when equal number of cations and anions are missing from the lattice. Cations and anions are of almost same size. It lowers the density of solid e.g. NaCl , KCl etc. (ii)The electrons trapped at the anion vacancies are referred to as F-centres from German word Farbenzenter meaning colour centre e.g. yellow colour imparted to NaCl when heated in an atmosphere of sodium vapour. 5. Iron has a body-centred cubic unit cell with a cell edge of 286.65 pm. The density of iron is 7.87 g cm-3 Use this information to calculate Avogadro’s number. (At. Mass of iron = 56 g mol -1) Ans : d= zxM a3 x N A For bcc lattice , z = 2 7.87 g cm-3 = 2 x 56 g mol-1 NA (286.65 x 10-10 cm)3 x NA = 6.04 x 1023 mol-1 Unit-II SOLUTIONS Mass percent = Mass of component in solution x 100 Total mass of solution Mole fraction of a component = Number of moles of the component Total number of moles of all the components χB = Molarity (M) = Moles of solute Volume of solution in litre = WB x 1000 MB Volume of solution in ml WB – mass of solute MB – molar mass of solute Molality (m) = Moles of solute Mass of solvent in Kg = WB x 1000 MB WA (in grams) WA – mass of solvent Henry’s law P = KH x χ1 P – partial pressure KH – Henry’s constant χ1 - mole fraction Raoult’s law for volatile solute PA = P°A χA PA= partial pressure of component A in solution P°A = vapour pressure of pure component χA = mole fraction P = PA + PB = P°A χA + P°BχB Raoult’s law for non-volatile solute P°A - PA = χB = nB = WB x MA P°A nA + nB MB WA (dilute solution) Elevation in boiling point ΔTb = Kb x m = Kb x WB x 1000 MB WA Depression in freezing point ΔTf = Kf x m = Kf x WB x 1000 An ideal solution should have: ΔVmix = 0 ΔHmix = 0 Obeys Raoult’s law over a wide range of concentration Non-ideal solution i. ΔVmix ≠ 0 ii. ΔHmix ≠ 0 iii. Raoult’s law is not obeyed Two types: a) Positive Deviation : When partial pressure of each liquid and the resultant total pressure is greater than the pressure expected on the basis of the Raoult’s law eg- Ether-acetone, Benzene-acetone , water-ethanol , n-hexane-ethanol etc. ΔHmix = +ve ΔVmix = +ve PA > P°AχA ; PB > P°BχB i. ii. iii. b) Negative deviation :When partial pressure of each liquid is less than the vapour pressure expected on basis of Raoult’s law. Eg- Methanol-acetic acid , water-nitric acid , acetone-chloroform , chloroformbenzene , chloroform-ether etc. ΔHmix = -ve 1. How is the molality of a solution different from its molarity? Ans- Molarity is the number of moles of solute per litre of solution whereas molarity is the number of moles of solute in 1kg of the solvent. 2.State Henry’s law and mention two importants application. Ans- Henry’s law : The pressure of gas over a solution is directly proportional to the mol fraction of the gas dissolve in the mol fraction of the gas dissolve in tje solution. Applications :(i): To make soft drink bottle more rich in CO2 sealing is done at high pressure. (ii):Deep sea divers use He and O2 mixture for respiration He is less soluble in blood as compared to N2 at high pressure and create the pain ful effect on the human body. 3. A 5 % sol (by mass) of Cane sugar in water has freezing point of 271K. Calculate the freezing point of 5% glucose in water if freezing point of pure water is 273.15K. Ans- 5% glucose means 5gm in 100gm of sol f= For sugar 273.15 – 271 = 2.15 = kf × 0.154 For glucose f = = Kf × 0.292 Comparing the two = f Freezing point of solution will be 273.15K – 4.08K = 269.07K UNIT-III - ELECTROCHEMISTRY Important formulae • R=V/I Where R is Resistance, V is Voltage, I is Current. • Conductivity or conductance = 1/R = 1/V The unit of conductance is Ohm-1 = Siemens = S. • Specific Conductance = 1/ Specific resistance K=1/p m = Specific Conductance/ Molarity • ^ K/M • Kohlrausch law - ^m = V+ ^+ + v-^- • Faraday’s First Law of Electrolysis m=ZxQ m=ZxIxt Where is mass of substance deposited, I is current in ampere, t is time in seconds, Q=Ixt Z = Eq. Wt./ 96500 Where z is electrochemical equivalent. Unit of electrochemical equivalent is gram/coulomb Faraday is charge on 1 mole of electrons. Charge on 1 electron = 1.602 x 10 -19 C Charge on 1 mole of electrons = 1.602 x 10 -19 x 6.023 x 10 23 = 96487 C = 96500 C • • Faraday’s Second Law of Electrolysis : W1/E1 = W2/E2 = W3/E3 • Where W1 is mass of substance 1 deposited and E1 is its equivalent weight, • W2 is mass of substance 2 deposited and E2 is its equivalent weight, • W3 is mass of substance 3 deposited and E3 deposited and E3 is its equivalent weight. • Nernst Equation o E oxidation = - Eo reduction Eo cell = Eo cathode – Eo anode Eo cell = Eo anode – Eo cathode Mn+ + neM o E = E – 2.303 RT / nF log [M]/[Mn+] where E = reduction electrode potential, Eo = Standard Reduction electrode Potential, n = No. of electrons T = Temperature in Kelvin, F = 96500 C Change in Gibb,s free energy ( ∆G ) = - n F E0 Cell ∆G0 = - 2.303RTlogKc Important Questions • Why is the equilibrium constant K related to only Eocell and not Ecell ? Ans: It is because Ecell at equilibrium is 0 volt . • Write the nernst Equation for the electrode reaction M n+ + ne- → M(s) Ans : Emn+/m = Eomn+/m +2.303RT/nF log[Mn+] • Predict the product of Electrolysis in each of the Following a) An aq Sol. Of AgNO3 with silver electrodes. b) An aq. Sol. Of AgNO3 with platinum electrodes. Ans : At Cathode : Ag+ (aq) + eAg(s) At anode Ag(s) Ag+ (aq)+ eAgNO3(aq) Ag+(aq) + NO3-(aq); H2O(l) H+(aq) + OH- (aq) b) At cathode 2Ag+(aq) + 2e2Ag(s) At anode 2OH (aq) O2(g) + 2H+(aq) + 4e● Can you store copper sulphate in zinc pot ? Ans: No , because Zn is more reactive than Cu . ●If a current of 0.5 ampere flows through a metallic wire for 2 hours , then how many electrons flow through the wire ? Ans : Q = it = 5 Х 2 Х 60 Х 60 = 3600 C No. of electrons flow = 3600 Х 6.022 Х 1023 9600 = 2.246 Х 1022 UNIT-IV Chemical Kinetics Important formulae • Rate Of reaction : it is defined as the change in concentration of reactant (or product) in a particular time interval. Unit of rate of reaction is mol L-1 s-1. If time is in minutes, then units is mol L-1 min-1 and so on. R = K ﴾ Conc ﴿n • Rate Law or rate equation : It is the expression which relates the rate of reaction with concentration of the reactants. The constant of proportionality ‘k’ is known as rate constant. R = K [ A ]p [ B ]q Where , p and q are not stoichiometric coefficient but they are order of the reaction • Rate constant : when concentration of both reactants are unity, then the rate of reaction is known as rate constant. It is also called specific reaction rate. Unit of K = ﴾ Conc ﴿ 1- n time -1 But in gaseous reaction , unit of K = atm 1-n time-1 • Molecularity : Total number of atoms, ions or molecules of the reactants involved in the reaction is termed as its molecularity. It is always in whole number. It is never more than three. It cannot be zero. Examples: Unimolecular reaction NH4NO2 N2 + 2H2O Bimolecular reaction 2HI(g) H2(g)+I Trimolecular reaction 2NO(g) + O2 (g) 2NO2(g) • • • Order of reaction : The sum of the exponents of the concentration of reactants in the rate law is termed as order of the reaction. It can be in fraction. It can be zero also. Zero order reaction : The rate of reaction does not change with the concentration of the reactants, i.e., rate = k [A]0, where ‘k’ is rate constant Unit of rate constant is mol L-1s-1 Half – life of a reaction : The time taken for a reaction when half of the starting material has reacted is called half-life of a reaction. For first order reaction t1/2 = 0.693/k, where k is rate constant. it is independent of initial concentration for first order reaction. Important formulae ▪ K = 2.303 log a t a–x For First order reaction ▪ t ½ = 0.693 K ▪ Slope = - K / 2.303 ▪ General expression for the time taken for nth fraction of a reaction of 1st order to complete : t 1/n = 2.303 log 1 K 1- 1/ n General expression for half life period of a reaction of nth order : T 1/2 α [ Ao ] 1-n ▪ Amount of substance left after n half lives = [ Ao ] / 2n No. of half lives = t / t ½ ▪ Arrhenius equation : K = A e –Ea / RT Log K2 / K1 = Ea / 2.303 R ( T2 – T1 ) / T1T2 Slope = - Ea / 2.303 R Important questions • A reaction is 50% complete in 2 hours and 75% complete in 4 hours. What is the order of the reaction ? Ans : First order because t75% = 2 t50% • Express the relation between the half life period of a reactant and its initial concentration for a reaction of nth order. Ans : t1/2 1/[R]on-1 • Show that time required for 99% completion is twice the time required for the completion of 90% reaction. Ans : t99% = 2.303/k log [R]o/([R]o – 99/100[R]0) = 2.303/k log 100 = 2.303 x 2/k = 4.606/k t 90% = 2.303/k log [R]0/([R]0 – 90/100[R]0 ) = 2.303/k x l t99%/t90% = 4.606/k x k/2.303 = 2 t99% = 2t90% UNIT-V- SURFACE CHEMISTRY Adsorption : Phenomenon of attracting and retaining molecules of a substance on the surface of a solid resulting in to a higher conc. On the surface than in the bulk . Difference between Physical and Chemical adsorption : Physical Adsorption │ Chemical Adsorption 1. Arises due to van der waals forces 1.Chemical bond 2. Not specific 2. Highly specific 3. Reversible 3.Irreversible 4. Low enthalpy of adsorption 4.High enthalpy of adsorption Adsorption Isotherm : Frendlich Adsorption Isotherm ( effect of Pressure ) X / m = K P 1/n Where , x = mass of adsorbate m = mass of adsorbent P = pressure K and n = Constants Shape Selective Catalysis by Zeolites : The catalytic reaction that depends upon the pore , structure of the catalyst and the size of the reactant and product molecules . Zeolites are aluminosilicatees with three- dimensional network . ZSM – 5 is used in the petroleum industry for the conversion of hydrocarbons into gasoline Sol = solid in liquid example starch sol Gel = liquid in solid example butter Emulsion = liquid in liquid example milk Types of Colloids : 1.Lyophilic sol : Reversible 2.Lyophobic : Irreversible 3.Multimolecular : smaller to colloidal range 4.Macromolecular : bigger to colloidal range 5. Associated : soap solution Peptisation : ppt + dispersion medium = colloid Dialysis : Purification of colloid Tyndall effect : Scattering of light by colloidal solution Zeta Potential ; Potential diff . between the fixed layer and diffused layer of opposite charges . Electrophoresis : Movement of colloidal particles under the influence of electric field . Coagulation : Colloid + Electrolyte = ppt Hardy Schulze Rule : Coagulation power of an ion α ( valency of the ion ) 4 Demulsification : E mulsions can be broken into the constituent liquids by heating , freezing , centrifuging . Important Questions Q1. What is meant by shape selective catalysis ? Ans. The catalytic reaction yhat depends upon the pore structure and size of the catalyst . Q2. Define the following : i. Peptisation ii. Reversible sols Q3.What is the diff between multimolecular and macromolecular colloids ? Give one example of each . Ans : Multimolecular Colloids -- smaller to colloidal range example gold sol Macromolecular Colloids -- bigger to colloidal range example protein sol UNIT:-VI- General Principles & Process of Isolation of Elements The chemical substances in the earth’s crust obtained by mining are called Minerals. 1. 2. 3. 4. Minerals, which act as source for metal, are called Ore. The unwanted impurities present in ore are called Gangue. The entire process of extraction of metal from its ore is called Metallurgy. Removal of gangue from ore is called Concentration, Dressing or Benefaction of ore. 5. Concentration by Hydraulic washing is based on the difference in gravities of ore and gangue particles. 6. Concentration by Magnetic separation is based on differences in magnetic properties of ore components. If either of ore or gangue is capable of attracted by a magnet field, then such separation is carried out. 7. Concentration by Froth Flotation Process is based on the facts that sulphide ore is wetted by oil & gangue particles are wetted by water. 8. Concentration by Leaching is based on the facts that ore is soluble in some suitable reagent & gangue is insoluble in same reagent. e.g. Bauxite ore contains impurities of silica, iron oxide & TiO2 .The powdered ore is treated with NaOH which dissolve Al & impurities remains insoluble in it. Al2O3 +2NaOH + 3 H2O 2 Na [Al(OH)4]. 10. Calcination involves heating of ore in absence of air below melting point of metal. In this process volatile impurities escapes leaving behind metal oxide. Fe2O3.xH2O Fe2O3 +xH2O ZnCO3 ZnO +CO2 CaCO3.MgCO3 CaO + MgO + 2CO2 11. Roasting involves heating of ore in presence of air below melting point of metal in reverberatory furnace. In this process volatile impurities escapes leaving behind metal oxide and metal sulphide converts to metal oxide. 2 ZnS + 3 O2 2ZnO+2SO2 2PbS + 3 O2 2 PbO +2 SO2 2 Cu2S + 3 O2 2Cu2O + 2 SO2 12. Reduction of metal oxide involves heating of metal in presence of suitable reagent Coke or CO2. 13. Reactions taking place at different zones of blast furnace in extraction of iron:(i) Zone of reduction:- Temperature range 250oC-700oC 3Fe2O3+CO 2Fe3O4+CO2 Fe3O4+CO 3FeO+ CO2 FeO +CO Fe+ CO2 (ii) Zone of slag formation:- Temperature range 800oC-1000oC CaCO3 CaO+CO2 CaO+SiO2 CaSiO3, P4O10+10C 4P+10CO, SiO2+2C Si+2CO, MnO2+2C Mn+2CO o o (iii) Zone of fusion:- Temperature range 1150 C-1350 C CO2 + C 2CO (iv) Zone of fusion:- Temperature range 1450oC-1950oC C +O2 CO2 ELLINGHAN DIAGRAM: For considering the choice of reducing agent in the reduction of oxides ∆G ═ ∆H ─ T ∆S ∆G must be negative, ∆G═ ─ n E F , ∆G ═ ─ RT ln K IMPORTANT QUESTIONS: 1.Is it true that under certain conditions Mg can reduce SiO2 and Si can reduce MgO? what are these conditions ? Ans.: By using Ellinghan Diagram 2. Diffrentiate between mineral and ores? Ans: Mineral is a naturally occurring Chemical substance. ore is a mineral from which we extract metal profitably. 3. How is cast Iron different from Pig Iron ? Ans: Cast Iron = Iron + 3% Carbon Pig Iron = Iron + 4% Carbon 4. Why is the reduction of a metal oxide is easier if the metal formed is in liquidstate at the temperature of reduction/ Ans: Due to more ∆S ═ + ve ∆G become more on negative side. And reduction become easier. 5.What is the role of depressant in froth flotation process? Ans: An ore containing ZnS and PbS , the depressants usedis NaCN . It selectively prevents ZnS from coming to the froth but allows PbS to come with the froth. 6.Describe Mond process and Van Arkel’s method . Ans: Mond Process :refining of Nickel 330-350 K 450-470K Ni + 4CO → Ni( CO)4 → Ni + 4CO Van Arkel Method : refining of Zr Zr + 2I2 → Zr I 4 1800K → Zr + 2 I 2 Unit-VII - p-BLOCK ELEMENTS Nitrogen Family : 1) ns2np3 2) O.S. (N) -3,-2,-1,0,+1,+2,+3,+4,+5 Tendency to show +5 O.S. N>P>As>Sb>Bi Tendency to show +3 O.S. N<P<As<Sb<Bi Disproportionation HNO3 → HNO3+H2O+2NO H3PO3 → H3PO4 +PH3 3) Formation of hydrides angle NH3>PH3>AsH3>SbH3>BiH3 Reducing Power Nh3<PH3………… Boiling Point NH3 SbH3 PH3 4) Anomalous behavior of (Nitrogen, Oxygen,Fluorine) →Small Size, High Electronegativety,Non availability of d-orbitals & High I.E. 5) 4NH3+5O2 → 4NO+6O2 P4+3NAOH+3H2O → PH3+3NaH2PO2(sodium hypophosphite) PCL3+3H2O → H3PO3+3HCl Sulphur Family 1) 2) 3) 4) ns2np4 O.S. -2 Hydrides NO + O3 (+2+4+6) H2E(H2O,H2S,H2Ss……………) NO2+O2(Depleting of oxygen) Halogens 1) 2) 3) 4) ns2np5 O.S. <Fluorine (-1)> (+1,+3,+5,+7) Halogen oxides halide ions of higher atomic number. Hydride : Acidic strength HF<HCl<HBr<HI Dissociation enthalpy HF>HCI>HBr>HI 5) Inter Halogen Compounds :Halogens combine among themselves to form a number of compounds known as interhalogens of the types XX’,XX’3,XX’5,XX’7 6) Cl2 is a powerful bleaching agent 7) Due to high electronegativity and small size. Fluorine forms only one oxoacid(HOF) 8) Acidic strength HClO<HCIO2<HCIO3<HCIO4 GROUP 18 1) ns2np6 2) Nobel gases have low b.p. because being mono atomic they have no inter atomic forces except weak dispersion forces . 3) Neil Bartett prepared a compound (O2PtF6) Ionization enthalpy of Xe (1170 KJ/Mol) O2 (1175 KJ/Mol) + 4) XeF2 + PF5→ [XeF] [PF6] XeF4 + SbF5→ [XeF]+[SbF6]XeF6 + MF→ M+[XeF7]{M=No,K,Rb or Cs) 5) Hydrolysis 6XeF4+12H20 → 4Xe + 2Xe03 + 24HF + 3O2 XeF6+ 3H2O → XeO3 +6HF Questions : 1) How does ammonia reacts with a solution of Cu++? 2) Why does No2 dimerise? 3) Are all five bonds in PCl5 molecule equivalent? 4)Are all five bonds in PCl5 molecule equivalent ?Justify your answer 5) H3PO3 is diprotic and why? 6) Which form of sulphur shows paramagnetic behavior ? 7) Complete the following relations 1. Cl2 + 2X- → 2. Br2 + 2I- → 8) Why is helium used in diving apparatus? 9)What is covalency of nitrogen inN2O5 ? 10) Why does R3P=0 exits but R3N=0 does not exists ? 11) PCl5 Is ionic in nature in the solid state .Give reason? 12) ClF3 exists but FCl3 does not .Why? d-Block Elements 1. The transition metals are very much hard and have low validility, because greater number of electrons form (n-1)d in addition to the ns electrons in the interatomic metallic bonding . 2. High enthalpies of atomization . 3. Variable o.s. – The enthalpies difference b/w (n-1)d orbitals is small. 4. Formation of colored ions : When an electron from the lower energy d-orbital is exited to a higher energy d-orbital the energy of excitation corresponding to the frequency of light absorbed .the color observed corresponding to the complementary color of the light absorbs . 5. Formation of complex compound : Due to the small size of metal ions their high ionic charges and availability of vacant d-orbitals for bond formation . 6. Catalytic Properties : a. Variable O.S. b. Metal surfaces have free vacancies. c. They can form complexes. 7. Alloy Formation : d-block transition metals have similar atomic size due to which one metal ion can be readily replaced by another metal atom. 8. Interstitial state : Transition metals accommodate atoms of small size in the voids of there crystal lattice and form interstitial compounds. Questions : A. Why is highest O.S. of a metal exhibited in its oxide or fluoride only ? B. What is lanthanoid contraction ? what are its consequences ? C. Why La(OH)2 is more basic than Lu(OH)3 D. Write preparation of K2Cr2O7? E. What is meant by disproportionation? Give two examples? F. What are interstitial compounds? Why are such compounds well known for transition metal? G. Explain why transition elements have many irregularities in their electronic configurations? H. Which metal in the first series of transition metals exhibits +1 oxidation state most frequently and why? UNIT IX-- COORDINATION COMPOUNDS 1. A co-ordination compound is a molecular compound in which the central metal atom or metal ion is linked toa number of ions or neutral molecules by coordinate bonds e.g. K4[Fe(CN)6] 2. Central metal atom & ligands are collectively written inside square bracket known as COORDINATION SPHERE. 3. The ligands whose only one donor atom is bonded to metal atom/ion are called mono dentate ligand. CO, NH3 ,H2O. 4. The ligand, which contain two-donor atom through which it is bonded to central atom, is called bidentate ligands. e.g. C2O4-- , NH2-CH2-CH2-NH2 . 5. A complex in which there is a close ring of atoms caused by attachment of ligand to a metal atom at two points is called CHELATES. 6. A molecule or ion that can form close ring with metal atom is called chelating ligand. e. g. C2O4--, NH2-CH2-CH2-NH2. 7. 10. Ethylene Di Amine Tetra Acetate is hexa dentate chelating ligand. 11. Ionization isomerism occurs when there is interchanging of groups between coordination sphere to ionization sphere. e.g. [ Co (NH3)5Br] SO4 and [Co (NH3)5 SO4] Br 13. Linkage isomerism exhibited by that compound in which a ligand can form linkage with metal through different atoms i.e. ambidentate ligand form this isomerism. e.g. [Co (NH3)5ONO]Cl2 and [Co (NH3)5NO2]Cl2 14. Hydrated isomerism occurs due to interchanging of H2O ligand from coordination sphere to ionization sphere. e.g. [Co (H2O)6]Cl3 [Co (H2O)5Cl]Cl2.H2O 15. Tetrahedral complex does not show geometrical isomerism. 16. In square planar complex cis (when same group are on same side) and trans (when same group on are opposite side) isomers are possible. 17. In octahedral complex cis –trans isomers are as following:- 18. According to crystal field theory as ligands approaches to metal atom then splitting of dorbitals of metal atoms takes place. These d-orbitals splits into two categories:(i) t2g orbital contains dxy, dyz, dzx (ii) eg orbital contains d X2- Y2 , d Z2. 21. For octahedral complex energy of eg is more than that of t2g orbitals. 22. For tetrahedral complex energy of eg is less than that of t2g orbitals. 23. Coordination compounds find use in followings field:(i) In qualitative analysis K4[Fe(CN)6] gives blue and brown colour with Fe3+ &Cu2+ respectively. (ii) In quantitative analysis EDTA is used to remove hardness of water. (iii) In extraction of metals like gold silver complex is formed. (iv) In biological system Chlorophyll & Haemoglobin is a complex of Mg2+ &Fe3+ respectively. Important Questions: Q.1- Write the IUPAC name of linkage isomer of [Cr (en)2(ONO)2]Cl. A.1-Linkage isomer is [Cr (en)2 (NO2)2] Br. IUPAC name- bis(ethane-1,2-diamine)dinitrito-N-chromium(iii) bromide Q.2- What is meant by the chelate effect? Give an example. A.2- A complex in which there is a close ring of atoms caused by attachment of ligand to a metal atom at two points is called chelate effect. e.g. Q.3- Which complex is used in the treatment of cancer? A.3- cis-platin or cis- [Pt (NH3)2 Cl2] Q.4-Draw optical isomers of [Co(en)3]2+ A.4- Q.5- Draw a sketch to show the splitting of d-orbitals in an octahedral crystal field. A.5- Unit-X HALOALKANES & HALOARENES POINTS TO BE REMEMBERED A Haloalkane:1. Halogen derivative of alkanes are called as Haloalkanes & of aromatic hydrocarbon are called Haloarenes. 2. In Haloalkane C-atom of C-X bond is sp3 Hybridized while in Haloarene it is sp2 hybridized. 3. Alcohols can be converted into Haloalkanes by reacting with HalogenAcids, +H-X PCl5 R-OH SOCl2 R-X+H2O R-Cl+POCl3+HCl R-Cl+SO2+HCl Phosphorous halide &Thionyl chloride (SOCl2). 4. Haloalkanes can also be prepared by electrophilic addition of Halogen Acids (HX) to the alkanes. R2O2 R-CH=CH2 + HBr R-CH2-CH2Br Markownikoff’s Rule R-CH=CH2+HBr R-CHBr-CH3 5. The Physical Properties of Haloalkanes are attributed to dipole-dipole and dipole-induced –dipole interaction. 6. Haloalkanes undergo Nucleophilic Substitution reaction (SN) due to polar character of Cδ+—Xδ- bond. 7. There are two types of SN reaction – (a). SN1-Unimolecular Nucleophilic Substitution reaction proceeds in two steps (slow and fast). (b) SN2-Bimolecular Nucleophilic substitution reaction proceeds in a single steps and its rate depends on the concentration of both Haloalkane & Nucleophile. 8. The reactivity of Haloalkane in SN1reaction follows the order ; Tertiary > Secondary > Primary. While reactivity of Haloalkane in SN2 reaction follows the order ; Primary > Secondary > Tertiary. 9. Optically Active compounds have the capacity to rotate the plane of polarized light either to Right (Dextorotatory) or to the left (Laevorotatory). 10. Optical Isomerism in compounds is due to the presence of Chiral carbon Atom as well as Dissymetry. 11. SN1 Mechanism in optically active alkyl Halide leads to Racemisation . 12. SN2 Mechanism in optically active alkyl halide leads to inversion of configuration . 13. Alkyl Halide on reaction with metals form Organometallic compounds such as Grignard Reagent (a useful compound) . B. HALOARENES:- 1. Haloarenes are prepared from their parent arenes and from diazonium salts. C6H6+X2 FeCl3,Dark C6H5X + HX Cu2X2 / HX C6H5N2+X- C6H5X + N2 +HX 2. Haloarenes are more stable & hence less reactive than Haloalkane due to (a) Sp2- hybridized C atom of C-X bond . (b) delocalization of Π- electron cloud. 3. Halogen present on the benzene is Ortho and Para directing but deactivating in nature. 4. Halogenation of benzene proceeds by Electrophilic substitution Mechanism. 5. m.p.of p-dichlorobenzene is higher than that of O & m isomers. C. polyhalogen compound :1. Organic compound having two or more than two halogen atom are called as polyhalogen compounds. 2. polyhalogen compounds such as dichloromethane(CH2Cl2), trichloromethane(CHI3), tetrachloromethane(CCl4),p-dichlorobenzen, Freons(CFC,CCl2F2)BHC,(Benzene hexachloride C6H6Cl6), DDT&PFC have many industrial application. 3. chloroform is no longer used as aneasthatic due to it’s poisionous nature &tendency to form phosgen gas(COCl2)when exposed to air . 4. BHC is a better insecticide as well as pesticide than DDT as DDT is non-biodegradable. γ-Isomers of BHC is called Gammexane or lindane or 666. 5. Freon used as a refrigerants but cause depletion of ozone layer. VERY SHORT ANSWER TYPE QUESTIONS (1MARK) Q.1. Write the structural isomers of C3H6Cl2 which can exihibit enantiomerism ? H Ans. CH3— C—CH2Cl Can exihibit enantiomerism Cl (i.e optical isomerism). Q.2 which compound (CH3)3 –C-Cl or ;CH3Cl Will react faster in SN2 Reaction with –OH? Ans.CH3Cl is more reactive than (CH3)3-C-Cl because of steric Hinderance of three bulky group in (CH3)3CCl. Q.3. Why is vinyl chloride less reactive than ethyl chloride? Ans. Conjugation of electron pair with π-electron pair of double bond in vinyl chloride results to a partial double bond character in C-Cl &it’s bond strength increases. CH2=CH-Cl — CH2-CH=Cl+ Q.4.Write the formula & chemical name of DDT? Ans. DDT is 2 , 2-bis(p-chlorophenyl)-1,1,1-trichioroethane Cl CH Cl C.Cl3 Q.5.Write down the structure of the following compounds; (a) 1-chloro-4-ethyl cyclohexane (b) 1, 4-dibromo but-2-ene (c) 4-tert.butyl-3-iodoheptane (d) 1-bromo-4-secbutyl-2-methylbenzene (e) perfluorobenzene Cl Ans. (a) (b) Br-CH2-CH=CH-CH2-Br Cl s C2H5 (c) H3C-CH2-CH-CH-CH2-CH2-CH3 I F (d) CH3 C-(CH3)3 F (e) Br H3C-CH-C2H5 F F F F Q.6. An alkyl halide having molecular formula C4H9Cl is optically active. What is its structure ? Ans. CH3 *CH CH2 CH3 Cl Q.7. Out of C6H5CH2Cl & C6H5CHCl C6H5 which is more easily hydrolysed with aq. KOH & why? Ans. C6H5 CH C6H5 will get hydrolysed easily because Cl Carbocation formed will be stabilized by resonance effect of two phenyl group. Q.8. Why is sulphuric acid not used during the reaction of alchohols with KI? Ans. Because HI formed will get oxidized to I2 by conc. H2SO4 which is an oxidizing agent. Q.9. A hydrocarbon C5H10 does not react with chlorine in dark but it gives a single monobromo compound in bright sunlight. Identify the compound. Cl Ans. sun + Cl2 light + HCl Cyclopentane Chlorocyclopentane Q.10.Chloroform is stored in dark coloured & sealed bottle. Why ? Ans. As Chloroform reacts with O2 of air in presence of sunlight & forms Phosgene gas which is poisonous . light 2 CHCl3 + O2 2COCl2 + 2HCl Phosgene gas SHORT ANSWER TYPE QUESTIONS (2MARK) Q.1. Give the IUPAC names of the following compounds ? a) ClCH2C CCH2Br b) (CCl3)3CCl c) CH3CH(Cl)CH(Br)CH3 d) Br Cl Ans. (a)1-Bromo-4-chlorobut-2-yne (b) 2-(Trichloromethyl)-1,1,1,2,3,3,3-heptachloropropane (c) 3-bromo-3-chlorobutane (4) p-bromo chlorobenzene Q.2. Predict the product of the following reactions; (a) CH3 CH C(CH3)2 + HCl (b) CH3 CH I CH3 (c) u.v.light + Cl2 (d) CH3 Na/Dry ether CH CH2 Br KOH(alc) CH3 (e) CH3 Markonikoff’s rule + Ans. (a) CH3 HI CH3 CH C CH3 Cl (b) CH3 H CH 2-chloro-3-methylbutane I + 2Na + I CH CH3 CH3 ether CH3 CH3-CH-CH-CH3+2NaF (c) Cl Cl Cl CH3 CH3 (2,3-dimethylbutane) Cl Cl Cl Benzene Hexachloride (BHC) CH CH3 (d). CH3 CH CH2 Br CH3 C CH2 +KB r+H2O 2-methyl propene CH3 + HI Markonikoff’s rule (e). I CH3 1-Iodo-1-methyl Cyclohexane Q.3. Starting from Methyl Iodide, how will you prepare : (a) Nitromethane. (b) Methyl Nitrite. O Ans. (a) CH3I + AgNO2 (b) CH3I + K O CH3----N=O CH3 N + AgI O O N O KI Q.4. How can Iodoform be prepared from ethanol ? Ans. C2H5OH + 6NaOH +4I2 CHI3 + HCOONa + 5NaI + 5H2O Q.5.Write the reactions involved in : (a). The Isocyanide test. (b). Iodoform test . Ans.(a). R-NH2 + CHCl3 + 3KOH(alc.) RN=C + 3KCl+3H2O o 1 -Amine chloroform O (b) CH3-C-CH3+3I2 +4NaOH CHI3 +CH3COONa +3NaI+3H2O Q.6.How will you distinguish between (i) CH3NH2 and (CH3)2NH (ii) Ethanol & 1-propanol Ans. (i) CH3NH2 (Methyl amine) gives Isocyanide test while (CH3)2NH do not. CH3-NH2 + CHCl3 + 3KOH CH3-N=C +3KCl +3H2O (ii) Add I2 & NaOH, ethanol will gives yellow ppt. of Iodoform whereas 1-propanol will not . Q.7. Propose the Mechanism of the following reaction ; CH3-CH2 –Br +CH3OCH3-CH2-OCH3 + BrAns. CH3 H H3C H CH3 CH3-O +C-Br [ CH3O C Br ] CH3O C H +BrH H (Nucleophile) H Q.8.Give the uses of (a) CCl4 (b) Iodoform . Ans. (a). Ccl4 is used as a solvent and also in fire Extinguisher. (b). Iodoform is used as Antiseptic. Q.9.Which will have a higher boiling point 1-chloropentane or 2-chloro-2-methylbutane ? Ans. CH3 CH2 CH2 CH2 CH2 Cl has higher boiling point 1-chloropentane than CH3 CH3 C CH2 CH3 (2-chloro-2-methyl butane).Because branc- Cl -hing of C-atom chain decreases the molecular size and vander waal’s force of attraction leading to decrease in boiling point. Q.10. Rearranging the following in order of increasing ease of dehydro -halogenation CH3CH2CH2Cl , CH3CHClCH3 , CH3 C Cl(CH3)2. Ans. CH3CH2CH2Cl < CH3CHClCH3 < CH3 C Cl(CH3)2. As per saytzeff’s rule more alkylated alkene is more stable and hence is formed. SHORT ANSWER TYPE QUESTIONS (3MARK) Q.1. How will you bring the following conversion? (a) Propene to Propyne (b) Toluene to Benzyl Alcohol (c) Aniline to Phenylisocyanide Ans. Br2 / CCl4 KOH(alc) (a) CH3-CH=CH2 CH3-CH—CH2 CH3-C=CH (Propyne) Br Br (b) CH2OH CH3 CH2Cl Cl / hν aq.KOH 2 -HCl -KCl N≡C → NH2 (c) + CHCl3 + 3KOH(alc.) +3KCl + 3H2O Q.2. What happen when; (a) n-butyl chloride is treated with alc. KOH. (b)ethyl chloride is treated with aq.KOH. (c)methyl chloride is treated with KCN. Ans. +KOH(alc.) (a) CH3-CH2-CH2-CH2-Cl CH3CH2CH=CH2 + KCl + H2O (b) CH3-CH2-Cl+KOH(aq.) CH3CH2OH+KCl+H2O (c) CH3-Cl +KCN CH3CN+KCl Q.3. Complete the following reaction; (a) Cl2CH-CH-Cl2+Zn ∆ (b)(CH3)2-CH-CH-CH2-CH3 C2H5ONa Ethanol Br (c) C6H5ONa +C2H5Cl Ans. (a). Cl2CH-CHCl2+Zn (b). (CH3)2-CH-CH-CH2-CH3 Br (C). C6H5O-Na+ + C2H5Cl Sodium Phenoxide ∆ Cl-CH=CHCl+ZnCl2 C2H5ONa Ethanol (CH3)2-CH-CH-CH2-CH3 OC2H5 C6H5OCH2CH3+NaCl (Phenetole) Unit-XI Alcohols, Phenols and Ethers Points to be remembered:Alcohols: Compounds containing one or more -OH group directly attached to C- atom of an aliphatic system. Phenol: Compounds containing – OH group directly attached to C-atom of an aromatic system. Ethers: Compounds obtained by substitution of a H-atom in a hydrocarbon by an alkoxy or aryloxy group. Structure of functional group: H 142 pm sp3 sp3 O C 108.9 96 pm H H H Alcohol sp2 C H O 136 pm Phenol C-O bond length (136pm) is less than that in alcohol due to – 1. Partial double bound character on account of the conjugation of unshared e pair of oxygen with aromatic ring. 2. sp2 state of C to which O-atom is attached 141pm sp2 H H O C 111.7 H H C H H Ether The C-O-C bound angle is slightly greater than angle due to repulsion interaction between two bulky (-R)gps Preparation of Alcohols: 8. Prom Alkene: (i) By Acid Catalysed hydration: H+ >C = C + H2 O > C -C< H OH (ii) By hydroboration – oxidation: H2O2, OH3CH3 - CH = CH2 + BH3 → (CH3-CH2-CH2)3B 3CH3-CH2-CH2-OH Propan -1-ol + B (OH) 3 (b) From Carbonyl Compounds: (i) By reduction of aldehydes and ketones Pd/Pt/Hi RCHO + H2 RCH2OH (Primary alcohols) NaBH4 RCOR1- R-CH-R1 (Sec. Alcohols) 1 LiACH4 OH (ii) By reduction of Carboxylic acids and esters – (i) LiAl H4 RCOOH R CH2 OH (Pri alcohol) (ii) H2O Or R1OH H2 1 RCOOH RCOOR RCH2OH + R1OH. + H Catalyst (c) From Grignard Regards H2O (i) HCHO + RMg X RCH2OMgX RCH2OH + Mg(OH)X Formaldehyde Pri. Alcohol 1 H2O R (ii) RCHO + R1MgX R-CH – OMgX R-CH-OH+Mg(OH)X Other aldelydc R1 R1 H2 O (iii) RCOR + R1MgX R– C – OMgX R – C – OH + Mg (OH) X Ketone R1 R Test alcohol Sec. Alcohol Preparation of phenols – (a) From Haloarenes Cl | 623k OH ONa+ HCl +NaOH 9. From Benzene 300atm Sulphoric acid – SO3H Oleum OH NaOH H+ 10. From diazonium Salts – NH2 | N2+Cl 273278K NaNo2 +HCl 300atm Aniline OH H2O warm N2 +HCl Benzene diazonium Chloride (d) From Cumene (Manufacture) CH3 CH3 H3C-CH CH3---C-OO-H O2 OH H+ + CH3COCH3 Cumene H2O Cumene Hydro peroxide Physical Properties: Boiling Point – The B.P. of alcohols and phenols increase with increase in the no. of C-alones (increase in Vander waal forces). In alcohols B.P. decrease with increase in branching (decrease in vander waals forces with decrease in surface area). (iii) Due to intermolecular H-bonding, B.P. of alcohols & phenols are higher than hydrocarbons, ethane, haloalkanes and haloarenes of comparable messes. Solubility: Solubility of alcohols and phenols in water due to them ability to form H-bond with water molecules. Solubility decrease with increase in size of alkyl / aryl group. Na C2H5ONa + H2 NaH C2H5 ONa + H2 PCl5 C2H5CL PX3 C2H5X Alcohol C2 H5 OH (X=Cl, Br, 1) SOCl2 O C2 H5 Cl CH3 – C – OH / H+ O CH3 – C OC2H5 CH3 – C – Cl Ch3 – C – OC2H5 O K2 Cr2 O7 / H+ CH3 – C – OH O Cu / 575 K CH3 – C – H ONa OH NaOH COOH CO2 Kolbe’s reaction H+ OH OH NO2 Dil.HNO3 + Nitration OH OH NO2 OH O2N NO2 Conc.HNO3 OH OH Br2 CHCl3 + aq.NaOH OH CS2 Br + 273 OH Reimer Tiemrnn Reaction Br Br Br aq. Br2 ONa Br ONa CHCl2 [ ] OH CHO H+ NaOH O Na2Cr2O7 H2SO4 O O Acidity of Phenols: Phenol is acidic due to resonance stabilized phenoxide ion. CHO Acidity – Phenol Vs Alcohol: Phenols are stronger acid than alcohol and water because – (i) In phenol –OH gp is attached to sp2 C-atom which being more electronegative decreases c-dually on o-atom and increase of ionisation of phenols than that of alcohols. (ii) In alkoxide in, the negative charge is localized on O-atom while in phenoxide ion, change is delocalized as phenoxide in is resonance stabilized. Hence phenoxide ion is more stabilized than alkoxide ion. Distinction between primary, secondary and tertiary alcohols – Lucas test – Alcohols are soluble in Lucas reagent (conc. HCland ZnCl2) while than halides are insoluble and produce turbidity in solution. If turbidity is produced immediately it is test alcohol, if after 5 min. it is sec alcohol and if turbidity is not produced at roar keep. It is pri. Alcohol. Test for phenol: (i) FeCl3 test :- Phenol gives purple color with FeCl3 solution. (ii) Br2 test :- Phenol decolorizes Br2 water forming tribromphenol as while ppt. Preparation of Ethane:(i) By dehydration of alcohols. H2SO4 CH2 = CH2 443K CH3 CH2 OH H2 SO4 C2 H5O C2H5 413K (ii) Williamson Syntheses – (lab method) RX + R1O Na R OR1 + NaX Physical Properties of Ethane: (i) Boling point – C-O bond in ethane polar and ethers have a net dipole moment. But in weak and not affect then B.P. which they have lower B.P. than alcohol due to absence of intermolecular H – bonding in ethers. (ii) Solubility – The miscibility of ethers with reasonable those of alcohols of same molecular ware as O-atom of ether can form H-bond with water. Chemical Properties of ethers: (a) Cleavage of C-O bond in ethers R – O – R + HX R – OH + HX R O + HX RX + R – OH RX + H2O OH + RX (b) Electrophonic Substitution In Anisole –OCH3 group attached to benzene group is ortho para directing and ring activating and thus it gives ortho and para substituted products. Very Short Answer type Questions (1mark) (i) How do you account for themiscibility of ethoxyethane with water? Ans:- Due to intermolecular hydrogen bonding between ether and water molecule. (ii) Write the I.U.P.A.C. name of the following compound : H3C – CH – CH2 – CH – CH – CH2OH I I I CH3 OH CH3 Ans:- 2,5 – dimethylhexane – 1,3 – diol (iii)Give the I.U.P.A.C. name of the following compound : H3C – C = C – CH2OH I I CH3 Br Ans:- 2 – bromo – 3 – methylbut – 2eu – 1ol (iv) Among HI, HBr, HCl, HI is most reactive towards alcohols. Why ? Ans:- HI has lowest bond dissociation enthalpy due to longer bond lengh, that is why it is most reactive. (v) Give the I.U.P.A.C. name of the following compound : H2C = CH – CH – CH2 – CH2 – CH3 I OH Ans:- Hex – 1 – en- 3 – ol (vi) C2H5ONa + CH3Br C2H5OCH3 + NaBr, What is the name of the reaction? Ans:- Williamson’s synthesis of ethers. (vii) Convert ethyl alcohol to diethyl ether. Ans:- 2C2H5OH C2H5OC2H5 + H2O (viii) Give chemical test to distinguish between phenol and ethanol in seemingly similar conditions. Ans:Test Phenol Ehtnaol Lucas Test: No positive test Cloudiness appear on heating. Comp. + Lucas Reagent (conc. HCl + Anhyd. ZnCl2) (ix) Ortho nitrophenol is more acidic than ortho – methoxy phenol. Why? Ans:- Because nitro group being electron withdrawing, increases acidic character whereas methoxy group ( - OCH3) being electron releasing group decreases acidic character. (x) Complete the following reaction – CH3 – CH – CH3 – PCl5 I OH Ans:- CH3 – CH – CH3 – PCl5 CH3 – CH – CH3 – POCl3 – HCl I OH | Cl Short Answer type Questions (3mark) Give a chemical test to distinguish between the following pairs of compounds. (b) CH3 – CH – CH3 And I OH (i) Why is phenol more acidic than ethanol? Ans:- (i) (a) Test 1. Bromine Water test. 2. Ferric Chloride Test Phenol Cyclohexanol Pale yellow ppt. of 2,4,6 Does not give this test Tri bromo phenol is formed Give Red to purple color. Do not give any color (b) Test 2 – Propanol (Sec. alcohol) Lucas Test : produces lubridity within 5 min. No turbidity Comp. + Lucas Reagent Cl (HCl + ZnCl2) I (ii) CH3 – CH – CH3 + HCl ----- CH3 – CH – CH3 + H2O I OH (1) O – H group in this group is much more polar than that in alcohol. (2) O – H group in phenol is directly attached to the sp2 – C of benzene which acts as an electron withdrawing group. So, in resonance structure of phenol the oxygen of – OH is +ve, which increases the polarity of O – H bond. (3) In alkoxide ion the –ve change is localized on oxygen while in phenoxide ion, the charge is delocalized. So, phenoxide ion is more stable (resonance establised) (2) Write the reaction of Williamson’s synthesis of 2-ethoxy-3methylpentane starting from ethanol and 3-methylpentan-2-ol. Ans:- (i) H3C – CH2 – CH – CH – CH3 ----Na--- H3C – CH2 – CH - ONa I I I I CH3 OH CH3 CH3 3 methylpentan-2ol (ii) (iii) C2H5OH ------------P,Br2------- C2H5Br H3C – CH2 – CH – ONa + C2H5Br ---------- H3C – CH2 – CH – CH – OC2H5 I I I I CH3 CH3 CH3 CH3 Chapter 12 ALDEHYDES, KETONES AND CARBOXYLIC ACID ALDEHYDES: Compounds in which the carbonyl group (>C=O) is bonded to a carbon & hydrogen atom. (R-CHO) KETONES: Compounds in which the carbonyl group (>C=O) is bonded to 2 C-atoms. CARBOXYLIC ACID: Compounds in which the carbonyl group (>C=O) is bonded to O-atom. COOH) (R- STRUCTURE OF CARBONYL GROUP:The carbonyl C-atom is sp2 hybridised forming 3 sigma bonds & remaining electron in p-orbital forms pie bond with O-atom. The O-atom has 2 L.p. The bond angle is 120 degree (trigonal coplaner). The C O double bond is polar with net dipole moment & are more polar than ethers. PREPARATION OF ALDEHYDE:11. From acyl chloride (acid chloride) or Rosenmind reaction. O CHO H2 C Cl Pd / BaSO4 12. From nitrile or Stephen reaction. RCN + SnCl2 + HCl RCH=NH RCHO H3O+/H2O 13. From esters. 1. DIBAL-H CH3(CH2)9 --- C --- OC2H5 CH3(CH2)9 --- C --- H +C2H5OH 2. H2O 14. From hydrocarbons. 1. By oxidation of methylbenzene := [i] use of chromyl chloride (CrO2Cl2) or Etard reaction :::) CH3 CH (OCrOHCl2)2 + CrO2Cl2 CHO [ii] Use of chromic oxide (CrO3) :::) CH3 + CrO3 + (CH3CO)2O 273278K CHO CH(OCOCH)2 H3O+ 2. By side chain chlorination followed by hydrolysis := CH3 CHCl2 Cl2 / hv CHO H2O 373K 3. By Gatterman – Koch reaction := CHO CO\HCl Anh. AlCl3 / CuCl3 PREPARATION OF KETONES: From acyl chlorides . 2R –C – Cl + R2Cd 2R – C – R + CdCl2 From nitriles. NMgBr CH3—CH2— C-- N + C6H5MgBr CH3—CH2— C C6H5 H30+/H2O C6H5 -- C C6H5 From benzene or substituted benzene or Friedal crafts acylation reaction. C – Ar / R + Ar/R— CO—Cl PHYSICAL PROPERTIES OF ALDEHYDE & KETONES:(ii) Boiling point:: B.P of aldehyde & ketones are higher than hydrocarbons & ethers of comparable masses due to weak molecular association in aldehydes & ketones arising due to dipole-dipole interaction . But the B.P are lower than alcohols of similar molecular masses due to absence of intermolecular H-bonding. (iii) Solubility:: Lower members are soluble in water due to intermolecular H-bonding but solubility decreases with increasing molecular mass. 3. Test To Distinguish Aldehydes And Ketones (i) Tollens test: Aldehydes give this test but ketones do not. + RCHO + 2[Ag(NH3)2] + 3OH RCOO + 2H2O +4NH3 +2Ag Tollens reagent : Tollens reagent is Ammonical Silver nitrate solution (ii) Fehlings Test: Aldehydes give this test but aromatic aldehydes and ketones do not. Fehlings reagent- Fehling solution A(aq. Copper sulphate solution) and Fehling solution B(alkaline sodium potassium tartarate or Rochelle salt) +2. RCHO + 2Cu + 5OH RCOO + 3H2O + Cu2O (Red brown ppt.) Haloform (Indoform) test: Aldehydes and ketones having methyl ketones CH3CO group give this test. Compounds containing CH3CH(OH) group give this test of ethanol. X2/NaOH R CO CH3 R COONa + CHX3 (X=Cl, Br,I) (Haloform) Reaction due to α hydrogen Aldol condensation : Given by aldehydes and ketones containing atleast one α – H- atom 2CH3CHO CH3-CH-CH2-CHO H20 CH3- CH - CHDil.NaO - aldol condensation product OH H H2O Aldol CHO CH3 Ba(OH)2 2CH3COCH3 CH3-C-CH2-COCH3 OH -H2O (CH3)2- C= CH-COCH3 Cross Aldol condensation: Aldol condensation is carried out between two different or ketenes 2CH3CH0+CH3CH2CHO CH3CH =CHCHO+CH3-CH2-CH = CH(CH3)CHO +CH3CH=CH(CH3)CHO +CH3CH2CH= CHCHO Other reactions: 1. Cannizzaro’s reaction: this is a disproportion reaction given by only aldehydes having no α-H atom. Ketones do not give this reaction 2. Electtrophilic substitution reaction: Given by both Aldehydes and ketones . in this C O group acts as a deactivating and meta-directing group. CARBOXYLIC ACID 1. Structure of carboxylic group: carboxyl C-atom is less electrophilic than carbonyl C-atom because of resonance. Preparation of carboxylic acid: 1. From primary Aldehydes and alcohols: Alk. KMnO4 RCH2OH RCOOH H3O 2. + From alkyl benzene: aromatic carboxylic acid are prepares by this method. Entire side chain is oxidized to the carboxyl group irrespective to the of its length. Test group is not affected. CH2CH2CH3 CHO KMnO4KOH 3. From nitriles and amides: H2O/dil RCN H20 R-CO-NH2 HCL H20/dil HCL CH3CONH2 CH3COOH + NH3 RCOOH H3O + COOH 4. From Grignard reagent: RMgX + O 5. C O R-COOMgX RCOOH + Mg(OH)X From alkyl halides and hydrides: H20 RCOOH + Cl - RCOCl H 20 (C6H5CO) 2O 6. RCOOH + HCl - RCOOH 2C6H5COOH From esters: COOC2H5 COOH + C2H5OH NaOH CH3CH2CH2COOC2H5 CH3CH2CH2COONa + C2H5OH Basic hydrolysis Physical properties: Boiling point: have higher boiling point than Aldehydes and ketones and even 7. 1. alcohols of comparable molecular mass due to more extensive association of carboxylic acid molecules through intermolecular H-bonding, which is not broken completely even in vapour phase as most of them exist as dimer in the vapour phase and in aprotic solvents. 2. Solubility: decreases with increased mass 1. Acidic nature: cleavage of O-H bond 2RCOOH+2Na 2R-COO-Na+ + H2 R-COOH +NaOH RCOONa+ + H2O RCOOH + NaHCO3 RCOO-Na+ + H2O + CO2 2. Cleavage of C-OH bond: i. Formation of anhydride: 2RCOOH ii. RCOOCOR Esterification : RCOOH +R’OH iii. RCOOR’ + H2O Reaction with PCl5,PCl3 and SOCl2 PCl5 RCOCl + PCl3 + HCl PCl3 RCOOH RCOCl +H3PO4 SOCl2 RCOCl +SO2 +HCl iv. Reaction with ammonia: CH3COOH + NH3 CH3COO-NH4+ CH3CONH2 Substitution reaction in the hydrogen part: 1. Hell – Volhard Zelinsky reactionHalogenations at the α position of carboxylic acid having an α - H atom to give α halogen carboxylic acid Cl2/P(Red) R-CH2-COOH RCH-COOH X 2.Ring substitution- (X=Cl,Br) Electrophilic substitutionin which the – cooh group acts as deactivating and m-directing group COOH COOH Conc. HNO3 + Conc. H2SO4 NO2 ONE MARK QUESTIONS – (i) Write the structural formula of (a) 1-phenylpentan-1-one (b) 3-oxopentanal Ans: - (a) (ii) O O II II (b) H-C-CH2-C-CH2-CH3 Give the I.U.P.A.C names of the following compound – Ans: - 2-ethylcyclopent-3enecarboxylic acid (iii) Give chemical test to distinguish between phenol and benzoic acid. Ans:- Test Phenol Benzoic Acid NaHCO3 Test: No Reaction. With effervescence CO2 Add a few drops of is evolved. aq. sol. (saturated) of C6H5COOH + NaHCO3 -- NaHCO3. C6H5COONa + H2O + CO2 (iv) Why do acryl chlorides have lower boiling point than corresponding acids ? Ans:- Acyl chlorides do not have intermolecular H-bonding while corresponding acids have H-bonding. (v) Complete the following reactions and name the major products (a) CH3CHO ------------ (b) CHCl3 + C2H5NH2 + 3KOH(alc) ------------- OH O . I II Ans:-(a) CH3CHO ------- CH3-CH-CH2-C-H (3-Hydroxy butanal or aldol) (b) CHCl3 + C2H5NH2 + 3KOH (alc.) --------- C2H5NC + 3KCl + 3H2O Ethyl isocyanides (vi) How will you convert Ethanol to Acetaldehyde? O II Ans:- CH3CH2OH --------- CH3-C-H + H2 Ethanol Acetaldehyde (vii) Arrange the following in increasing order of acidic character : HCOOH, CH2ClCOOH , CF3COOH , CCl3COOH Ans:- HCOOH < CH2ClCOOH < CCl3COOH < CF3COOH (viii) Write the IUPAC name of the compound : CH3-CH-CO-CH-CH3 I I CH3 CH3 Ans:- 2,4 – Dimethylpentan-3-one (ix) Name two important uses of formalin Ans:-1. Used as preservative for biological specimens. 2. Used for preparation of Bakelite. (x) Write the structure of phenyl-2-(phenyl) ethanoate. Ans:- 5 – Marks Questions – 1. Identify the unknown organic compounds. (A) to (E) in the following series of chemical reactions – 2. An organic compound (A) having molecular formula C9H10O forms an orange red ppt (B) with 2,4 –DNP reagent. Compound (A) gives a yellow ppt (C) when heated in the presence of Iodine and NaOH along with a colourless compound (D). (A) does not reduce Tollen’s reagent or Fehling’s sol. Nor does it decolourise bromine water. On drastic oxidation of (A) with Chromic acid, a carboxylic acid (E) of molecular formula C7H6O2 is formed. Deduce the structure of the organic compounds (A) to (E). 3. A compound (A) with molecular formula, C5H11O, on oxidation forms compound (B) with molecular formula, C5H10O. The compound B gives iodoform test but does not reduce ammonical silver nitrate. (B) on reduction with amalgamated Zinc & HCl gives compound (C) with molecular formula C5H12. Identify A, B & C. Write down the chemical reaction involved. 5. (a) (i) Ket ones are less reactive towards nucleophiles than aldehydes. (ii) Benzoic acid is stronger acid than ethanoic acid. (iii) Which acid is stronger- Phenol or Cresol? Explain. Ans.(a) (i) (ii) The Alkyl group in Ketones decreases the positive charge on the Carboxyl carbon due to + I effect, makes > C= O less polar than Aldehyde and decreasing the attacking tendency of the nucleophile. (ii) Phenyl group in Benzoic acid has weak +R effect and thus destablises the Carboxylate anion, makes it a stronger base. +I effect of Methyl group in Acetic acid is still greater than +R effect of Phenyl group. This further destabalises the Acetate ion comparatively, makes it a stronger base than Benzoic acid. So, acetic acid is weaker than Benzoic acid. Cresol is a weaker acid than Phenol because +I effect of –R group at the ortho and para position increases electron density on the Benzene nucleus, decreasing stability of ArO- ion making it a stronger base as O-H bond becomes less polar. Hence, substituted Phenol is less acidic than Phenol. Unit-13 Organic Compounds containing nitrogen Points to be remembered:1. Alkyl or Aryl derivatives of ammonia 10 Primary amine R-NH2 0 2 Secondary amine R2—NH 30 Tertiary amine R3-N 2. IUPAC nomenclature Alkane amine in place of ‘e’ of alkane for secondary and tertiaryN-alkyl or N<N-dialkyl alkanamium. 3. Structure is pyramidal 4. Preparation (a)Reduction of nitro compounds H2/ Pd or Ni or Pt Sn + HCl Ar-NO2 Ar-NH2 Ar-NH2 (b)Ammonolysis of alkyl halides R-X + NH3 R-NH2 + NH4X 0 0 If Alkyl halide is in excess 2 and 3 Amines can be prepared (c)Reduction of nitrites H2 /Ni R-C N R-CH2-NH2 (d)Reduction of amides R-CONH2 R-CONH2 LiAlH4 R-CH2-NH2 R-CH2-NH2 (F)Hoffman bromamide degradation reaction R-CONH2 + Br2 + 4NaOH R-NH2 + Na2CO3 + 2NaBr + 2H2O PHYSICAL PROPERTIES: 5.(a)Boiling point increase with the increase in molecule weight. Primary and secondary amines have higher boiling point than the tertiary amines of same molecular weight due to possibility of intermolecular hydrogen bonding in (b)Solubility: - lower members are readily soluble in water due to H-bonding.Solubility in water decreases and in organic solvent increase with increase in molecular weight. As the alkyl group predominates over the amino group thus less tendency of H-bond with water. 6. Basic characters of amines R-NH2 + H2O R-N+H3 + OHLarger value of kb or smaller the value of pkb stronger is the base. In gases phase basis strength is as follows: Tertiary amine > secondary > primary > ammonis Because of the presence of electron release alkyl group which stabilizes ammonium cations and makes nitrogen unshared or lone pair of electron available for sharing. In solution Secondary > tertiary > primary Stabilization due to: electron-releasing effect of alkyl group : salvation trough H-bonding : steric factor/hindrance (C2H5)2NH > (C2H5)3N > C2H5NH2 > NH3 (CH3)2NH > CH3NH3 > (CH3)3N > NH3 Aryl/Aromatic amines are weaker than aliphatic amines and ammonia. Resonance stabilization of aryl amines makes unshared electron pair on nitrogen less available for protonation. In case of substituted aniline electron-releasing groups like -0CH3, -CH3 etc increases basic strength Whereas electron with drawing groups like –NO2,-SO3,-COOH,-X decreases basic strength. E.g. increasing basic strength 7. Alkylation: +R-Br +R-Br R-NH2 8. Acylation: -HBr R2NH -HBr R3N O R-NH2 + R’C-Cl acid chloride R-N-H2 + Cl – C-R’ R-N-C-R’ + HCl R-N-C-R’ + HCl O C6H5-N-H + R-C-O-C-R H O O acid anhydride RNH2 + C6H5COCl BENZOYL CHLORIDE 9. Carbylamines reaction (isocyanide test): HEAT R-NH2 + CHCl3 + 3KOH H O C6H5-N-C-R + RCOOH H O RNHCOC6H5 +HCl R-NC +3KCl +3H2O alkyl carbylamines 10. Reaction with nitrous acid: R-NH2 + `HNO2 C6H5-NH2 NaNO2+H [R-N2+Cl-] ROH +N2 +HCl H2O Cl NaNO2+2HC C6H5N2+Cl- + NaCl + 2H2O l 273-278 K 11. Reaction with arylsulphonyl chloride (Hinsberg’s test): O O Ar-S-Cl + H-N-C2H5 Ar-S-N-C2H5 + HCl O Benzenesuphonylchloride O O(N- ETHYLBENZENE SULPHONAMIDE) O Ar-S-Cl + H-N-C2H5 O Ar-S-N-C2H5 + HCl C2H5 12. Electophilic substitution: a) Bromination NH2 Br O C2H5 (N,N-DIETHYLBENZENESULPHONAMIDE) NH2 Br Br2/H2O + 3HBr + Br (2,4,6-TRIBROMOANILINE) O NH2 H-N-C-CH3 H- O N-C-CH3 OH- OR Br PYRIDI NE NH2 H+ CH3CO OH Br b) Nitration: NH2 NH2 Br NH2 NH2 NO2 HNO3, H2SO4 + NH2 NHCOCH3 NHCOCH3 HNO3, H2SO4 288K + + OH- OR H+ (CH3CO)2O 288K NH2 (D) FRIEDAL CRAFT REACTON Aniline does not undergo this reaction due to salt formation with AlCl3, the Lewis acid : NH2 NH2AlCl3- +AlCl3 DIAZONIUM SALTS ( RN+2X-) Preparation by diazotization. C6H5NH2 + NaNO2 + 2HCl C6H5N2Cl + NaCl + 2H2O 1. Reaction involving displacement of nitrogen. (a) Replacement by halide or cyanide ion Sand Meyer Reaction: ArCl + N2 CuCl/HCl ArN+2XArBr + N2 CuBr/HBr ArCN + N2 Gatterman Reaction: ArN+2X- CuCN/KCN Cu/HCl Cu/HBr (b) Replacement of iodine ion: ArCl + N2 +CuX ArBr + N2 +CuX ArN+2Cl- + KI ArI + KCl + N2 ( c) Replacement by Fluoride ion : ArN+2Cl- +HBF4 ArN+2 BF-4 (d) Replacement By H : H3PO2 + H2O ArN+2ClArH + N2 +H3PO3 +HCl +CH3CH2OH Ar-F + BF3 ArH +N2 +CH3CHO + HCl (e) Replacement by Hydroxyl group: ArN+2Cl- + H2O ArOH + N2 + HCl (f) Replacement by --NO2 group: +N2Cl+N2BF-4 NO2 NaNO2 + HBF4 Cu Flouroboric acid 2. Reaction involving retention of Diazo Group Coupling reaction: OHN+= NCl- + H- -N=N- -OH p-hydroxyozobenzene (Orange dye) -N+=NCl- + H- OH-- -NH2 -N=N-- + N2 + NaBF4 -OH +H2O+Cl- NH2+ P-Amioazobenzene +Cl-+H2O (Yellow dye) Very Short Answer type Questions (1mark) Q.1.How will you convert aniline to benzoic acid? Ans. NH2 N +Cl2 ANILINE CN COOH H2O Q.2.What product is obtained by Hoffman degradation of m-bromobenzamide? Ans. m-bromoaniline is obtained Q.3.What happen when benzonitrite is treated with LiAlH4? Ans. Benzylamine is obtained CN CH2NH2 LiAl H4 Q.4.What for are quaternary ammonia salts widely used? Ans. Quaternary ammonium salts are used as detergents. Q.5.How is aniline converted into flourobenzene ? + N2 Cl NH2 N2BF4 HONO+HQ A 0-5oc F HBF4 LiAl H4 Aniline benzenediazonium chloride Flourobenz Q.4.Arrange in increasing orderof their basic strength (a)C2H5OH, (CH3)2NH, C2H5NH2.(Increasing order of b.p.) (b)C6H5NH2,(C2H5)2NH,C2H5NH2.(INCREASING ORDER OF SOLUBILITY IN WATER) Ans. (a). (CH3)2NH< C2H5NH2< C2H5OH. (b). C6H5NH2<(C2H5)2NH<C2H5NH2. Q.5.Explain (a).coupling reaction. (b). Sandmeyer’s reaction. Ans.(a). Benzene diazonium chloride couples with electron rich aromatic compounds like phenols and amines to give azocompounds. The azo compounds contains –N=N- bond and the reaction coupling reaction. C6H5N2+Cl- + C6H5OH → C6H5-N=N-C6H5-0H (p) p-HYDROXYAZOBENZENE (b)When benzene diazonium salts is treated with cuprous chloride or cuprous bromide at roomtemrature, chlorobenzene or bromobenzene is formed .this reaction is known as sandmeyer’s reaction. C6H5N2+Cl- + CuCl/HCl → C6H6Cl + N2 Short Answer type Questions (3mark) Q1.(a) Give possible explanation for each of the following:(i) the presence of a base is needed in the ammonolysis of alkyl halides. (ii)aromatic primary amines cannot be prepared by Gabriel phtaliminde synthesis (b)Write the IUPAC name of CH3-N-C-CH3 C2H5 (a) (i) To remove the HX produced during the rn. (ii) Aryl halides do not undergo nucleophilic substitutionWITH POTASSIUM PHTHALIMIDE. (b) N-Ethyl-N-methylethanamide. 2.Account for the following :(i) Pkb of aniline is morethan that of methylamine. (ii) Ethylamine is soluble in water whreas aniline is not. (iii) Methylamine in water reacts with ferric chloride to precipitate hydrated ferric oxide. Ans- (i) aniline has an electron withdrawing phenyl group so it is the weaker base than ammonia. Methyl group in methylamine is electron donating group so it is stronger base than ammonia. (ii)ethyl group in ethylamine is comparatively a small group and causes no hindrance in formation of hydrogen bonding and hence it is soluble in water. (iii) methylamine behaves like aqueous ammonia and in similar way it precipitates metal as hydroxides from metal salts CH3NH2 + H2O CH3N+H3OH- 3CH3NH3+OH- + FeCl33(CH3NH3)+Cl- + Fe(OH)3 Ques) arrange the following (i) in decreasing order of the pKb value: C2H5NH2, C6H5NHCH3,(C2H5)2NH AND CH3NH2 (ii) in decreasing order of basic strength: C6H5NH2, C6H5N(CH3)2,(C2H5)2NH and CH3NH2 (iii) in increasing order of basic strength: (a) aniline,p-nitroaniline and p-toylidine (b) C6H5NH2,C6H5NHCH3,C6H5CH2NH2 Ans) (i) C6H5NH2>C6H5NHCH3>C2H5NH2>(C2H5)2NH (ii) (C2H5)2NH>CH3NH2>C6H5NH2>C6H5N(CH3)2 (iv) (a) p-nitroaniline<aniline<p-toulidine (b)C6H5NH2<C6H5NCH3<C6H5CH2NH2 Q-4 Give plausible explanation of each of the following: i) Why are amines less acidic than alcohols of comparable molecular masses? Why primary amines are having higher boiling point than tertiary amines? ii) Why aliphatic amines are having stronger bases than aromatic amines? iii) (i)Amines are less acidic than alcohols of comparable molecular masses because the anion formed is not is not stabilized enough due to presence of unshared electro pair on the nitrogen atom. iv) R-NH2 RNH- + H+ v) (ii) In primary amines , nitrogen bears two hydrogen atoms whereas in tertiary amines nitrogen bears no hydrogen atom hence the hydrogen bonding is more prominent. This is why primary amines have higher boiling point than amines. vi) (iii) In aromatic amines, aryl group has an electron withdrawing Phenyl group on the nitrogen atom. It decreases electron density on nitrogen atom and makes it a weaker base than ammonia. CHAPTER-14 BIO MOLECULES POINTS TO BE REMEMBERED:1. CARBOHYDRATES:-There are optically active poly hydroxyl aldehydes or ketones or the compounds which produce such units on hydrolysis they have general formula Cx(H )y. 2. CLASSIFICATION On the basis of them behaviours on hydrolysis they are classified as: (a).Monosaccharide:- The carbohydrates which cannot hydrolysied further . Eg. Glucose , Fructose. (b).Oligosaccharides:- The carbohydrates which give 2 to10 monosaccharids units on hydrolysis. Eg. Sucrose, maltose. ( c).Polysaccharides:- The carbohydrates which give large number of monosaccharides on hydrolysis. Eg. Starch, cellulose. 3. SUGARS: - The carbohydrates which are sweets in taste are called sugar .eg. Sucrose, lactose. 4. NON SUGARS: - The carbohydrates which are not sweets in taste.eg. Starch, celloluse. 5. REDUCING SUGAR:- Sugars which reduse fehling solution and tollens regent. Eg. Glucose, fructose. 6. NON REDUCING SUGER:-which do not reduce Fehling or tollen’s reagent. Eg;-sucrose. Structure of Glucose 7. CYCLIC STRUCTURE OF GLUCOSE:The straight chain structure of glucose is unable to explain the following reaction. (a) It does not give the2, 4-DNP test, Schiff test and doesn’t form hydrogensulphide addition product with NaHSO3. (b) The pentaactate of glucose does not react with NH2OH indicating the absence of CHO-group. (c) It exits in two different crystalline ά and β forms .They are called anomers.They differ in optical rotation .They have different melting point. HAWORTH STRUCTURE ά- D Glucose β- D Glucose 8. STARCH:- Main storage polysaccharide of plants has two components amylase and amylopectin. 9. PROTIENS: - Protiens are long polymers of amino acids linked by peptide bands. They are essential for proper growth and maintaince of body. 10. AMMINOACIDS:- It contain amino and carboxylicacid functional group. R-CH-COOH | NH2 11. ESSENTIAL AMMINO ACID:-Amino acid which cannot be synthesized in the body and are obtained from diet.eg.Valine, Lysine. 12. NON-ESSENTIAL AMINO ACID:- The amino acid which can be synthesized in the body are called non essential amminoacid.eg.Glysine, serine, proline. 13. ZWITTER ION: - In aqueous solution the carboxyl group can lose a proton and amino group can accept a proton, giving rise a dipoler ion called as zwitter ion. 14. CLASSIFICATION:(A) FIBROUS PROTEIN:1. Polypeptide chains run parallel or antiparllel & held together by hydrogen and disulphide bonds. 2. Generally in soluble in water. Eg-collagen, myorin, fibroin. (B) GLOBULAR PROTIEN:1. Chains of polypeptide coil around to give spherical shape. 2. Usually soluble in water. E.g. Insulin, hemoglobin. 15. DENATURATION OF PROTEIN: - The proteins in its native form, when subjected to physical change like temperature, PH etc undergoes uncoiling and loses its biological activity. This is called denaturation of proteins. The secondary and tertiary structures are destroyed, only primary structure retained. eg: coagulation of egg while on heating. 16. VITAMINS:The organic compound required in the diet in small amounts to perform specific biological function and is not synthesized by our body. 17. CLASIFICATION: - ON THE BASIS OF THEIR SOULIBLITY IN WATER OR FAT. (a)FAT SOLUBLE VITAMIN: - They are insoluble in water but soluble in fat.eg vitaminA, B, E, K. (b)WATER SOLUBLE VITAMIN: - Vitamin B & C Vitamin Source A CARROT, BUTTER & MILK B YEAST, LIVER, GREEN VEGETABLE deficiency disease XEROPHTHAL MIA, NIGHT BLIDNESS BERI-BERI C CITRUS FRUIT.AMLA SCURVY D SUNLIGHT ,FISH EGG YALK RICKETS 18. NUCLEIC ACIDS: - These are bimolecules which are long chain polymers of nucleotides. They are DNA& RNA. 19. COMPOSITION O F NUCLEIC ACID: - They are made-up of a pentane sugar (B-D-2 dexoyribose in DNA d B-D-ribose in RNA), phosphoric acid and nitrogen containing heterocyclic compound. (BASE) (a) DNA: - Base adenine (A), Thymine (t), guanine (g) and cytosine(C). (b)RNA:- Contain adenine(A),guanine(G),cytosine(C)and Uralic(U). 20. ENZYMES: - Enzyme are bio-catalyst and are generally globular protein e.g. zymase, maltase. VERY SHORT ANSWER TYPE QUESTION (1 marks) Q.1 what are reducing sugar? A.1 The sugar which reduces Fehling solution and tollen’s regent .eg.glucose. Q.2 Name the deficiency diseases resulting from lack of vitamin A and C? A.2 Xerophthalmia & scurvy. Q.3 What is name given to the linkage which hold together to monomeric units in polysaccharide? A.3 Glycosidie linkage. Q.4 Name the enzyme which convert sucrose into glucose and fructose? A.4 Invertase. Q.5What are the components of starch? A.5 Amylase and amylopectin.. Q.6 Why is cellulose in our diet not nourishing? A.6 Our body does not have enzyme which help in digestion of cellulose. Q.7 Name the purines present in DNA? A.7Adenine and guanine. Q.8Why vitamin C cannot be stored in our body? A.8 It is water soluble & readily excreted in urine. Q.9Give two examples of non- essential amminoacid? A.9 Glycine and alamine. Q.10 What are different types of RNA found in the cell? A.10 1.m. RNA 2. t. RNA 3.r. RNA SHORT ANSWER TYPE QUESTION (2 marks) Q.1STATE two difference between globular protein and fibrous protein? A.1.(a)They are α-helix structure. While they have β-pleated structures. (b)They are soluble in water while they are insoluble in water. Q.2What are essential amino acids? Give two examples. A.2 The amino acid which cannot be synthesized in the body we get from our Diet e.g. Valine and leuline. Q.3 What is glycogen? How is it different from starch? A.3 It is a polysaccharide found in all animal cells mainly in muscles and liver. Carbohydrates are stored in animal body as glycogen where in plant body as starch. Q.4How are vitamins are classified? Name the vitamin responsible for the cogulation of blood. A.4Vitamins are classified on the basis of their solubility as fat soluble and water soluble. Vitamin K Q.5 What are nucleic acids? Mention their two important function. A.5 They are polymers of nucleotides having ribose or deoxyribose sugar, hetrocyclic base like A,G,C,T and U and phosphoric acid. Q.6 What is difference between DNA &RNA on the basis of bases they contain? A.6 Both have two bases derived from purine, adenine and guanine and two bases from pyramidine, thymine and cytocine but in RNA there is Uralic in place of thymine of DNA. Q.7 (a). Which forces are responsible for the stability of x-helix? (b). What is denaturation of protein? A.7 a. Hydrogen bonding b. When 2 &3 degree structure are ruptured then the proteins are said to be denatured. It is done by heating or change in pH. Q.8 Where does the water present in the egg go after boiling the egg? A.8 When egg is boiled the water present in the egg is used in denaturation of protein through H-bounding.In this the globular protein in the egg changes to rubber like insoluble mass Q.9What are the enzymes? Give two examples. A.9 The enzymes are biocatalyst . Eg maltose and urease. Q.10 What is difference between nucleoside and a nucleotide? A.10 A nucleotide contain only two basic components of nucleic acid pentose sugar and nitrogenous base .But nucleotide contain all three components phosphoric acid group,pentosesugar and nitrogenous base. SHORT ANSWER TYPE QUESTION (3 marks) Q.1Define the following as related to proteins A.Peptide linkage B. Primary structure C.Denaturation A.1A. Peptide linkage: - The bond formed by condensation reaction between amminoacid in protein and polypeptide is called peptide linkage. B. Primary structure:- The sequence in which amminoacid are linked with each other in polypeptide chain forms primary structure . C. Denaturation:- The process in which 2&3 degree structure of protein are destroyed but 1 degree structure remain as the same is called denaturation. Q.2 What are essential and non-essential amminoacid? Give two examples of each type. A.2 Essential amminoacid: - Those amminoacid which are not synthesized in the body. Eg. Valine, leucine. Non-essential amminoacid: - those amminoacid which are produced in our body. Eg.glycine,alaine. Q.3 Enumerate the reaction of D-glucose which can not be explained by it open chain structure? A.3 Open chain structure can not be explained by following reasons:a. Despite having the aldehydegroup, glucose does not give suhiffs test . 2, 4-DNA test b. Glucose does not react with NaHSO3 to form addition product. c. The pent acetate of glucose does not react with NH2OH showing the absence of –CHO group. Q.4 Define the following and give one example of each? (a) ISOELECTRIC POINT (b) MUTAROTATION (c) ENZYMES (a) ISOELECTRIC POINT:- The PH at which no net migration of amminoacid take place under the influence of an applied electric field is called isoelectric point. Ex-Amminoacid exits as zwitter ion at PH 5.5 to 6.3 (b) MUTAROTATION:- Spontaneous change in optical rotation when an optical active substance is dissolved in water. e.g. ά-D-glucose when dissolved in water, its optical rotation changes from 111 to 52.5 degree. (C) ENZYMES: - They are biological catalyst which catalises specific biochemical reaction. ----------------------------------------------------------------------------------------------- UNIT 15 POLYMERS Points to be remembered:Polymers – Polymer is a very large molecule having high molecular mass 103 to 107 g/mol. They are formed by joining together repeating simple unit. Polymerizations- The process of formation of polymers from respective monomers is called polymerization. CLASSIFICATION OF POLYMERS 1) Based on source – a) Natural – found in plants and animals e.g proteins, cellulose, starch, rubber. b) Semi-synthetic – Derived from naturally occurring polymers by chemical modifications e.g cellulose acetate, cellulose nitrate. c) Synthetic – These are prepared in laboratories .They are also called man made polymers. e.g Nylon, polythene, PVC , Buna-S. 2) Base on structure – a) Linear polymers – They consists of long and straight chain of repeating units e.g polythen,PVC. b) Branched chain – They contain linear chain having some branches. e.g. amylopectin, glycogen. c) Cross linked polymers – They have strong covalent bond between various linear polymer chains e.g Bakelite, melamine. c) Based on mode of Polymerization:(i) Addition Polymers: - These are formed by the repeated addition of monomer molecules having multiple bonds. e.g. polythenes, polypropene, polystyrene. (ii) Condensation Polymers: - These are formed by repeated condensation reaction of different bi-functional or tri-functional monomers with the elimination of small molecules like water, HCl, NH3, etc. e.g.: Polythene, Bakelite, nylon. (d) Based on molecular forces:(i) Elastomers: - Forces of interaction between polymer, chain is weakest. e.g.: Natural rubber, neoprene. (ii) Fibres: - Strong hydrogen bonds are present between the polymers chain .e.g.: Nylon, Bakelite. (iii) Thermoplastics: - They are linear or slightly branched chain molecule capable of repeated softening of heating and hardening on cooling. E.g.: Polythene, PVC, polypropene. (iv) Thermosetting Polymers: - They are cross linked or heavily branched molecules which on heating undergo extensive cross linking and become infusible. e.g.: Bakelite. (e) Based on growth of polymerization:- Depending upon the mechanism of polymerization polymers are classified as… (i) Addition Polymer OR Chain Polymer:- They follow mostly free radical mechanism. The process starts with phenyl free radical formed by peroxide which adds with the double bond of ethene to form larger free radical. This step is called Chain Initiating Step. This reacts with another molecule to form bigger radical. This is Chain Propagation Step. This reacts with another radical to form polymerized product. This is called the Chain Terminating Step. CHAIN INITIATING STEP: C6H5-C-O-O-C-C6H5 2C6H5C-O* 2*C6H5 O O O Phenyl Radical Benzoyl peroxide *C6H5 + CH2=CH2 C6H5-CH2-*CH2 CHAIN PROPAGATION: C6H5CH2-*CH2 + CH2=CH2 C6H5-(CH2-CH2)n-CH2-*CH2 CHAIN TERMINATING: C6H5-(CH2-CH2)n-CH2-*CH2 C6H5-(CH2-CH2)-CH2-CH2 + C6H5-(CH2-CH2)-CH2-*CH2 C6H5-n(CH2-CH2)-CH2 Polythene (ii) Condensation Polymers or Step Growth Polymers:-They are formed by gradual steps. Some Important Polymers: NAME OF POLYMERS MONOMERS STRUCTURE Polythene Ethane -(CH2-CH2)n- Teflon Terylene or Daeron CF2=CF2 CH2OH | CH2OH + HOOC-COOH -(CF2-CF2)n-[O-CH2-CH2-O | -n[C-C=O H2N-(CH2)6-NH2 + HOOC-(CH2)4COOH -[N-(CH2)6-N-C=O | | H O H Nylon-6,6 Nylon-6 O H2C | H2C C H N CH2- CH2 CH2 USES Insulating wire , dustbin, toys Oil seal & gaskets. Ropes, tyre cord ,Safely belts, sarees & dress materials O -n[-C--(CH2)4 O H || | -[C-(CH2)5-N]n- Socks, ropes , bristle for brushes Tyre cord, Fabrics, Ropes Buna-S CH2=CH-CH=CH2 + -CH=CH2 Buna-N Natural Rubber Neoprene Nylon-2-Nylon-6 CH2=CH-CH=CH2 + CN | CH2=CH2 CH2=C-CH=CH2 | CH3 Cl | CH2-C-CH=CH2 H2NCH2COOH Glycine + H2N-(CH2)5-COOH Amino caproic acid Floor tiles, foot wears -[CH2-CH=CH-CH2-CH-CH2]n-[CH2-CH=CH-CH2-CH2-CH]n | CN Oil seal tank lining CH3 | -[CH2-C=CH-CH2]nCl | -[CH2-C=CH-CH2]n- Used for tyres O -[C-CH2-NH-CO(CH2)5-NH]n- Conveyor belts, gasket. Biodegradable Polymer RUBBER:1. Natural Rubber: - It is a linear polymer of isoprene. It is prepared from rubber latex. CH3 CH3 | | CH2=C-CH=CH2 -[CH2-C=CH-CH2]nIsoprene Natural rubber 2. Vulcanization of Rubber:- Natural rubber is soft , soluble in non-polar solvents. To improve its physical properties it is vulcanized. The process of heating raw rubber with sulphur and additive to make it hard, more resistant and elastic is called Vulcanization of rubber. Sulphur form cross- links at the reactive site of double bonds. 3. Synthetic Rubber:- These are obtained by polymerization of butadiene or its derivative are called Synthetic rubber. e.g. Buna-S, Buna-N. 4. Biodegradable Polymers: - The polymers which are decomposed by the microorganism into simple molecule are called Biodegradable Polymers. They do not pollute the environment. e.g. PHBV, Nylon-2-nylon-6. HO-CH-CH2-COOH + HOCH-CH2-COOH CH3 CH2 CH3 3-Hydroxy butanoic acid 3 hydroxy pentanoic acid -[O-CH-CH2-C-O-CH-CH2-C]nCH3 O CH2 O CH3 PHBV Very Short Answer type Questions (1mark) Q1: What is polymerisation? Ans: The process of formation of polymers from respective monomer is called Polymerisation. Q2: Is (-NH-CHR-CO-)n, a homopolymer or a copolymer? Ans: It is a homopolymer because it is obtained from a single monomer. Q3: Write the name and structure of one of the common initiators used in free radical addition polymerisation? Ans: Benzoyl peroxide (C6H5CO-O-O-CO-C6H5). Q4: Write the structures of monomer used in the preparation of i. Teflon ii. PVC. Ans: (i) CF2=CF2 (ii) CH2=CHCl. Q5: What are the monomers of bakelite? Ans: Phenol and formaldehyde HCHO. Q6: Write the equation used for the synthesis of neoprene. Ans: nH2C=CCl-CH=CH2 (H2C-CCl=CH-CH2-)n – Q7: What is mean by vulcanisation of rubber? Ans: The process of heating natural rubber with sulphur to improve its properties. Q8: What are homopolymer? Ans: The polymers formed by the polymerisation of a single monomeric species are called homopolymer. Q9: On the basis of forces between their molecules in a polymer to which class does Nylon 6,6 belong? Ans: It belongs to the class of fibres. Q10: Write the chemical equation for the preparation of terylene. Ans: nHO-CH2-CH2-OH + nHOOC-------_______-COOH -(O-CH2-CH2-O-OC- -COO)n-- Short Answer type Questions Q1: What are natural and synthetic polymers? Give two examples of each type. (2mark) Ans: Polymers of high molecular mass obtained from plants and animals are called natural polymers. Ex. Cellulose, starch. Polymers prepared in laboratories are called synthetic polymers. Ex. Nylon, PVC, Buna-S etc. Q2: Explain the difference between Buna-N and Buna-S. Ans: Buna-N is copolymer of 1,3 butadiene & acrlonitrile. Buna-S is copolymer of 1,3 butadiene & styrene. Q3: What are biodegradable polymers? Give two examples. Ans: Polymers which are decomposed by the micro-organism. eg. PHBV & Nylon-2, Nylon-6. Q4: In which classes, the polymers are classified on the basis of molecular forces? Ans: On the basis of molecular forces they are classified as 1 Elastomers –natural rubber 2 Fibres –nylon-6,6 3 Thermoplastics –Polythene 4 Thermosetting plastics- Bakelite. Short Answer type Questions (3mark) Q1) What are the synthetic and natural polymers? give two examples? Ans:-polymers of high molecular mass obtained from plant and animals are called natural polymers e.g.;-cellulose and starch. Polymers prepared in the laboratories are called synthetic polymers e.g:-Nylon, Buna-S and PVC. q2) Explain the difference between Buna-N and Buna –S. Ans:-Buna –n is copolymers of 1,3 butadiene and acrlonitrile Buna-s is copolymers of 1,3 butadiene and styrene. Q3) what are biodegradable polymers? give two examples. Ans:- polymers which are decomposed by micro-organism dg:- PHBV and nylon -2 and nylon-6. Q4) In which the polymers are classified on the basis of molecular forces? Ans- on the basis of molecular forces they are classified as 1. Elastomers ------ natural rubber Fibres------- nylon-6 and 6 2. Thermoplastics----- polythene 3. Thermosetting plastics-----Bakelite. Q5) write the structural formula for the monomers of the following polymers; (i) Nylon-,6,6 (ii) Natural rubber Ans: (i) Nylon-6,6: Adipic acid HOOC-(CH2)4 –COOH Hexamethylene diamine H2N-(CH2)6NH2 (ii) Natural rubber: isoprene CH2C-CHCH2CH3 Q6) what is the step growth polymerisation give 1 example for it Ans: It is a process in which isomers undergo condensation polymerisation step wise. Ex: Nylon and Terylene are step growth polymers. Q7) Write the chemical equation for the synthesis of glyptal Mention one use of it. Ans: + {-O-CH2-CH2OOC HOCH2-CH2OH HOOC COOH Phthalic acid ethylene glycol Glyptal It is used in the manufacture of paints and lacquers. Q8) Comment on the natural difference b/w thermoplastics and thermosetting polymers Ans: Thermoplastics have less intermolecular forces of attraction because they are not cross linked and become soft on heating and can be moulded. Thermosetting polymers have strong forces of attraction due to cross linkage. They do not become soft on heating. Q9)(a) How does vulcanization change the character of NATURAL RUBBER (b)Why 66 and 6 put in the name NYLON-66AND NYLON -6! Ans:(a) Natural rubber become more hard and elastic on vulcanization due to formation of cross linkage with sulphur. (b) Nylon-6,6 is a polymer of adipic acid and Hexamethylene diamine, both the monomers has 6 carbon atom each Nylon-6 is polymer on caprolactum which contain 6 carbon atom. Q10) write the chemical reaction involved in the synthesis of Bakelite. Ans: OH OH CH2OH + HCHO Phenol Formaldehyde O-hydroxy benzyl alcohol OH + CH2OH -H2O OH -CH2- OH OH -CH2CH2 OH -CH2- Polymerisation -CH2- CH2 -CH2- -CH2 CH2 -CH2- OH OH Bakelite (2) Write the name and structure of the monomers of the following polymers. (a) Buna-S (b) Buna-N (c) Dacron. Ans. Buna-s 1, 3 butadiene CH2=CH-CH=CH2 Styrene C6H5 CH=CH 2 (b)Buna-n 1,3butadiene CH2=CH-CH=CH2 CO }- Acronitrile CH2=CH-CH ethylene glycol HO-CH2-CH2O+ Terephthalic acid HOO---COOH (3) What are biodegradable polymers? Give an example and write its preparation. O Ans. The polymers which get decomposed by micro organisms. e.g: PHBV and Nylon-2, nylon-6. Preparation of Nylon-2-nylon-6:O HOOC-CH2-NH2 + HOOC-(CH2)5NH2 -------→ [-C-CH2-NH-CO-(CH2)5-NH-] Glycerine amino caproic acid nylon-2-nylon-6 (4) How does the presence of double bond in rubber molecules influences their structure and reactivity? Ans. The natural rubber is cis-1,4 polyisoprene. The double bonds located b/w C2 & C3 of isoprene uniprene units. The cis-configuration about double bonds do not allow chains to come closer for effective attraction due to weak intermolecular forces of attraction .That is why the natural rubber has a coiled structure and shows elasticity. (5) How can you differentiate between addition & condensation polymerisation . Give one example of each? Ans. ADDITION POLYMERISATION CONDENSATION POLYMERISATION (c)Dacron = 1.It takes place in unsaturated monomer 2. Loss of small molecules like HCl, H2O, NH3 does not take place . e.g: Formation of polythene & polypropene 1.It takes place in monomer having multi functional groups 2. Loss of small molecules likeH2O,NH3, NaCl takes place. e.g: Formation of nylon-6,6 terylene (6) What are monomers? Write monomers of PHBV, nylon-6, 6. Give there uses. Ans. The simplest molecules which combine to give polymers are called Monomers. PHBV: -3-hydroxybutanoic acid & 3-hydroxy pentatonic acid Nylon-6, 6:- Hexamethylene diamine adipic acid. Uses: 1.PHBV is used in specialty packaging, and in controlled release of drug. 2. Nylon-6, 6 is used in making sheets, bristles for brushes and in textile industry. -------------------------------------------------------------------------------------------------------- Unit-16 CHEMISTRY IN EVERYDAY LIFE POINTS TO BE REMEMBERED 1. DRUGS – Drugs are chemical of low molecular masses, which interact with macromolecular targets and produce a biological response. 2. CHEMOTHERAPY- The use of chemicals for therapeutic effect is called chemotherapy. 3. CLASSIFICATION OF DRUGS – (a) ON THE BASIS OF PHARMACOLOGICAL EFFECT-drugs for a particular type of problem as analgesics-----for pain relieving. (b) ON THE BASIS OF DRUG ACTION-Action of drug on a particular biochemical process. (c) ON THE BASIS OF CHEMICAL ACTION-Drugs having similar structure .egsulpha drugs. (d) ON THE BASIS OF MOLECULAR TARGETS- Drugs interacting with biomolecules as lipids , proteins. 4. ENZYMES AS DRUG TARGETS (i) CATALYTIC ACTION OF EN ZYMES(a) enzymes have active sites which hold the substrate molecule .it can be attracted by reacting molecules. (b) Substrate are bonded to active sites through hydrogen bonds , ionic bonds ,Vander Waal or dipole –dipole interactions. (ii) DRUG- ENZYME INTERACTIONS(a)Drug complete with natural substrate for their attachments on the active sites of enzymes .They are called competitive inhibitors. (b)Some drugs binds to a different site of the enzyme called allosteric sites which changes the shape of active sites. 5. ANTAGONISTS- The drugs that binds to the receptor site and inhibit its natural function. 6. AGONISTS-Drugs mimic the natural messenger by switching on the receptor. 7. ANTACIDS-These are compounds which neutralize excess acid of stomach.egAluminium hydroxide, Magnesium hydroxide. 8. ANTI HISTAMINES-The drugs which interfare with the natural action of histamines and prevent the allergic reaction. eg-rantidine,tegarnet, avil. 9. TRANQULIZERS-The class of chemical compounds used for the treatment of stress,mild or even severe mental diseases. Eg-idardil, iproniagid,luminal,second equaqnil. 10. ANALGESICS-They reduce pain without causing impairment of consciousness, mental confusion or some other disturbance of the nervous system. Eg-aspirin,seridon,phenacetin. 11. ANTIMICROBIALS-They tend to prevent/destroy or inhibit the pathogenic action of microbes as bacteria,virus,fungi etc.They are classified as (i)ANTIBIOTICS-Those are the chemicals substances which are produced by microorganisms. Eg-Pencillin, ofloxacin. NARROW SPECTRUM ANTI-BIOTICS-These are effective mainly against gram positive or gram negative bacteria. Eg-Penicillin,streptomycin. BROAD SPECTRUM ANTI-BIOTICS-They kill or inhibit a wide range of microorganisms. eg- chloramphenicol,tetracydine (ii)ANTISEPTICS OR DISINFECTANT-These are which either kill/inhibit the growth of micro-organisms Antiseptics are applied to the living tissuses such as wounds,cuts,ulcers etc. egfuracine,chloroxylenol & terpinol(dettol).Disinfectant are applied to inanimate objects such as floors , drainage , system. Eg- 0.2% solution of phenol is an antiseptics while 1% solution is an disinfectant. 12. ANTIFERTILITY DRUGS- These are the chemical substances used to control the pregnancy.They are also called oral contraceptives or birth control pills. Eg-Mifepristone, norethindrone. 13. ARTIFICIAL SWEETNING AGENTS-These are the chemical compounds which give sweetening effect to the food without adding calorie. They are good for diabatic people eg- aspartame, saccharin,alitame,sucrolose. 14. FOOD PRESERVATIVES- They prevent spoilage of food to microbial growth.eg-salt, sugar, sodium benzoate. 15. CLEANSING AGENTS(i) SOAPS- They are sodium or potassium salts of long chain fatty acids.They are obtained by the soapnification reaction , when fatty acids are heated with aqueous sodium hydroxide. They do not work well in hard water. (iii) TOILETS SOAP-That are prepared by using better grade of fatty acids and excess of alkali needs to be removed .colour & perfumes are added to make them attractive. (iv) MEDICATED SOAPS- Substances of medicinal value are added.egButhional,dettol. 16. SYNTHETIC DETERGENTS-They are cleaning agents having properties of soaps ,but actually contain no soap.They can used in both soft and hard water .They are(i)ANIONIC DETERGENTS-They are sodium salts of sulphonated long chain alcohols or hydrocarbons.eg-sodium lauryl sulphonate. They are effective in acidic solution. CH3(CH2)CH2OH → CH3(CH2)10CH2OSO3H (lauryl alchol) + →CH3(CH2)10CH2SO3 Na (sodium lauryl sulphonate) (ii)CATIONIC DETERGENTS- They are quarternary ammonium salts of amines with acetates , chlorides, or bromides.They are expensive used to limited extent.egcytyltrimethylammoniumbromide (iii)NON-IONIC DETERGENTS- They do not contain any ions. Some liquid dishwashing detergents which are of non-ionic type . 17. BIODEGREDABLE DETERGENTS-The detergents which are linear and can be attacked by micro-organisms are biodegradable. Eg-sodium 4-(1-dodecyl)benzene\ sulphonate. 18. NON-BIODEGREDABLE DETERGENTS-The detergents which are branched and cannot be decomposed by micro-organisms are called non-biodegdradable.eg-sodium 4(1,3,5,7 tetramethyloctl)-benzene sulphonate.It creates water pollution. VERY SHORT ANSWER TYPE QUESTION (1 marks) Q-1 Define the term chemotherapy? Ans-1 Treatment of diseases using chemicals is called chemotherapy. Q-2 Why do we require artificial sweetening agents? Ans-2 To reduce calorie intake. Q-3 What are main constiuent of dettol? Ans-3 Choloroxylenol & Terpinol. Q-4 What type drug phenaticinis? Ans-4 It is an antipyretics. Q-5 Name the drug that are used to control allergy? Ans-5 Antihistamines. Q-6Why is the use of aspartame limited to cold food and drinks? Ans-6 It is unstable at cooking temperature and decompose. Q-7What are tranquilizers? Give an example? Ans-7 They are the drug used in stress , mild severe mental disease. Q-8 What type of drug chloramphenicol? Ans-8 It is broad spectrum antibiotic. Q-9Why is biothional is added to the toilet soap? Ans-9It acts as antiseptics. Q-10 What are food preservatives? Ans-10 The substances that prevent spoilage of food due to microbial growth. eg- sodium benzonate. SHORT ANSWER TYPE QUESTION (2 marks) Q-1 Mention one important use of the following(i) Equanil (ii)Sucrolose Ans-1 (i) Equanil- It is a tranquilizer. (ii) Sucrolose-It is an artificial sweetener. Q-2 Define the following and give one example(i)Antipyretics (ii)Antibiotics Ans-2 (i) Antipyretics- Those drugs which reduce the temperature of feveral body are called Antipyretics. Eg - Paracetamol (ii) Antibiotics-The drugs which prevent the growth of other micro-organisms. Eg- Pencillin. Q-3 Name the medicines used for the treatment of the following(i) Tuberculosis (ii) Typhoid Tuberculosis- Sterptomycin Typhoid- Cholororophenicol Q-4 What are tincture of iodine? Ans-4 2-3% iodine solution of alcohol water is called tincture of Iodine. It is a powerful antiseptics and is applied on wounds. Q- 5 What are artificial sweetening agent? Give two examples? Ans-5 The substances which give sweetening to food but don’t add calorie to our body . Eg- Saccharin , alitame. Q-6 How are synthetic detergents better than soaps? Ans- 6 (i)Detergents can be used in hard water but soaps cannot be used. (ii) Detergents have a stronger cleansing action than soaps. Q-7 What are sulpha drugs? Give two examples? Ans-7 A group of drugs which are derivatives of sulphanilamide and are used in place of antibiotics are called sulpha drugs. Eg- sulphadizine, sulphanilamide. Q-8 What forces are involved in holding the active sites of the enzymes? Ans-8 The forces are involved in holding the active sites of the enzymes are hydrogen bonding , ionic bonding , dipole-dipole attractions or Vander waals force of attractions. Q-9 Describe the following giving an example in each case- (i) Edible colours (ii) Antifertility drugs (i) Edible colours- They are used for dying food. Eg- saffron is used to colour rice. (ii) Antifertility drugs- Those drugs which control the birth of the child are called Antifertility drugs. Q-10 Give two examples of organic compounds used as antiseptics? Ans-10 Phenol(0.2%) , iodoform SHORT ANSWER TYPE QUESTION (3 marks) Q-1 What are Biodegredable and non-biodegdredable detergents? Give one example of each. Ans-1 Detergents having straight hydrocarbon chain and are easily decomposed by microorganisms are called Biodegredable detergents.The detergents having branched hydrocarbon chain and are not easily decomposed by micro-organisms are called Non-Biodegredable detergents. Q-2 What are barbiturates? To which class of drugs do they belong? Give two examples. Ans-2 Derivatives of barbituric acid are called barbiturates.They are tranquilizers . They also act as hypnotics. eg- luminal , seconal. Q-3 What is the use of – (i) Benadryl (ii) sodium benzoate (iii) Progesterone Ans-3 (i) Antihistamines (ii) Preservatives (iii) Antifertility drug Q-4 Identify the type of drug(i) Ofloxacin (ii) Aspirin (iii) Cimetidine Ans- 4 (i) Antibiotic (ii) Analgesics & Antipyretics (iii) Antihistamines & antacid Q-5 Describe the following with suitable example(i) Disinfectant (ii) Analgesics (iii) Broad spectrum antibiotics (i) Disinfectant- chemicals used to kill the micro-organisms can applied on non living articles. (ii) Analgesics- They are the drugs which are used to relieve pain . eg – Aspirin , Ibuprofen. (iii) Broad spectrum antibiotics- They kill the wide range of gram positive and gram negative bacteria. Eg- Chloramphenicol , ofloxacin. ----------------------------------------------------------------------------------------------------------------------- BIOMOLECULES Carbohydrates: These are optically active poly hydroxyle or ketones or molecule which provide such unit on hydrolysis. Classification of Carbohydrates Carbohydrates are classified into three classes depending on well behaviour towards hydrolysis: Monosaccharide:-The carbohydrates which cannot hydrolysied futher. Eg: glucose, fructose. Oligosaccharides: The carbohydrates which have 2 to 10 monosaccharides units on hydrolysis. Eg: sucrose,cellulose. Polysaccharides: the carbohydrates which give large no. of monosaccharides on hydrolysis. Eg: starch,cellose Sugar: The carbohydrates which are sweet in taste are called sugar. Eg: sucrose ,lactose Non-Sugars:The carbohydrates which are not sweet in taste.Eg:starch,cellose. Reducing Sugar: Sugars which reduce fehling solution and tollens reagent. Eg: glucose, fructose. NON Reducing Sugar: which do not reduce Fehling or tollen’s reagent. Eg: sucrose. CHO H OH OH H H OH H OH CH2COOH Structure Of Glucose Cyclic Structure Of Glucose: The straight chain structure of glucose is unable to explain the following reaction. 1. It does not give the 2,4-DNP test, Schiff test and dosen’t form hydrogensulphide addition product with NaHSO3. 2. The penta acetate of glucose does not react with NH2Oh indicating the absence of CHO group. 3. It exist in two different crystline α and β forms. They are called anomers. They differ in optical rotation. They have different melting point. CH2OH Starch: Main storage polysaccharide of plants has two components amylase and amylopectin. Protiens: Protiens are long polymers of amino acids linked by peptide bands.they are essential for proper growth and maintaince of body. Amino Acids: It contains amino and carboxylicacid functional group R-CH-COOH NH2 Essential Amino Acids: Amino acid which cannot be synthesized in the body and are obtained from diet.eg:Valine,Lysine. Non-Essential Amino Acid: The amino acid which can be synthesized in the body are called non essential amino acid.eg:glysine,serine,praline. Zwitter Ion:In aqueous solution the carboxyl group can lose a protone and amino group can accept a protone,giving rise a dipoler ion called as zwitter ion. NH3+----CH----COOR Classification: 1. Fibrous Protein: Polypeptide chains run parallel or antiparalle and held together by hydrogen and disulphide bonds. Generally in soluble in water.eg:collagen,myorin,fibroin. 2. Globular Protien: Chains of polypeptide coil around to give spheical shape. Usually soluble in water.eg:insulin,haemoglobin. Denaturation Of Protein: The proteins in its native form, when subjected to physical change like temperature,PH etc undergoes uncoiling and loses its biological activity. This is called denaturation of proteins. The secondary and tertiary structure are destroyed, only primary structure retained.eg:coagulation of eggs while on heating. Vitamins:The organic compound required in the diet in small amounts to perform specific biological functions and its not synthezised by our body. Classification: On the basis of their souliblity in water or fat. (a) Fat Soluble Vitamin: They are insoluble in water but soluble in fat.eg: vitamin A,B,E,R. (b) Water Soluble Vitamin: Vitamin B & C. VITAMINS A B C D SOURCE DEFICIENCY DISEASE CARROT,BUTTER & XEROPHTHAL MILK MLA,NIGHT BLINDNESS YEAST,LIVER,GREEN BERI-BERI VEGETABLE CITRUS FRUIT,AMLA SCURVY SUNLIGHT,FISH,EGG RICKETS YALK Nucleic Acids:These are bimolecules which are long chain polymers of nucleotides.They are DNA & RNA. Composition Of Nucleic Acid: they are made-up of a pentane sgar (BD-2 dexoyribose in DNA d B-D-ribose in RNA), phosphoric acid and nitrogen containing (a) DNA: Base adenine (A),Thymine(t),guanine(g),and cytosine(C). (b) RNA: Contain adenine(A), guanine(g), cytosine(C)and Uralic(U). Enzymes:enzyme are bio-catalyst and are generally lobular potein eg: zymase,maltase. VERY SHORT ANSWER TYPE QUESTIONS Q1 What are carbohydrates? ans- These are optically active poly hydroxyle or ketones or molecule which provide such unit on hydrolysis. Q2 Name the deficiency disease resulting from lack of vitamin C and D? ans- SCURVY and RICKETS. Q3 what are the name given to the linkage which hold together to monomeric units in polysaccharide? Ans-Glycosidie linkage. Q4 Name the enzyme which convert sucrose into glucose and fructose? Ans-Invertase Q5 What are the components of starch? Ans-Amylase and amylopectin. Q6 Why is cellulose in our dite not nourishing? Ans-Our body does not have enzyme which help in digestion of cellulose. Q7 Name the purines present in DNA? Ans-Adenine and Guanine. Q8 Why vitamine C cannot be stored in our body? Ans-It is water soluble and readily excreated in urine. Q9 Give two examples of non-essential ammino acid? Ans-Glycine and alamine Q10 What are different types of RNA found in the cell? Ans-1.m.RNA 2.t.RNA 3.r.RNA.