Chemistry Revision — Part 1 mo ansSample MCQs 1.What is the mole fraction of a solute in 1 m aqueous solution? {a)1.770 {b) 0.0354 {c) 0.0177 (d) 0.17 2. A solution contains 10 g per litre of urea (molar mass of urea = 60 g mol) is isotonic with a 5% solution of non- volatile solute. The molar mass of the non-volatile solute is 9 apf {2} 350 g mot (b) 300 gmol* —_(¢) 250 gmol sn onihtd 200 g mot ie a 3.The weight of silver displaced by a quar " tri ‘ity which displaces 5600 ml of oxygen at STP will be gana fa) 54g (b) Big (o) 5.48, (d) 10.85 4, Molar conductivities (A,,°) at infinite dilution of NaCI, HCI and CH,COONa are 126.4, 425.9 and 91.0 S cm? mol* respectively. A.,° for CH,COOH will be {a) 390.5 Sem? mol? —(b) 425.5$ em? mol _(¢) 180.5 S em? mol*{d) 290.8 S em? mol?Assertion and Reason Questions (For Practice) Assertion: When NaC! is added to water a depression in freezing point is observed. Reason: The lowering of vapour pressure of a solution causes depression in the freezing point. Assertion: Hydrolysis of cane sugar is a first order reaction. Reason: Water is present in large excess during hydrolysis. gr? Assertion: Ce** is used as an oxidizing agent in volumetric analysisn, eh Reason: Ce" has the tendency of attaining +3 oxidation tagen 7 Assertion: [Ni(CO}4] has square planar ecard te {Ni(CN)4] 4- has tetrahedral geometry Reason: Geometry of any complex dapeftas upon the nature of ligands attached. Assertion: Hydrolysis of (-) 2-bromoctane proceeds with inversion of configuration. Reason: This reaction proceeds through the formation of carbocation. Assertion: All naturally occurring amino acids except glycine are optically active. Reason: Most naturally occurring amino acids have L-configuration,Match the following Column 1 ‘Column 2 fa) CHCl, i) Antiseptic (b) CCl, (ii) Insecticide prd (a. a\ccHtp-cl Hs (i) Fire tf icher (a) cH, ih Refrigerant (2) — (iv); (b) ~Match the following Column 1 Column 2 (2) Catechol ti) (b) Resorcinol Miae™ eo ™ ao {c) Quinol osm iy (d) p-Cresol iv) (a) — (ii); (b) — (iv); Ce) ~ (i); (a) — (ai)Match the following Column 1 Column 2 (a) Benzophenone to Diphenylmethane [ (WAI, (b) Benzaldehyde to 1-Phenylethanol (ii) DIBAL-H ear {c} Cyclohexanone to Cyclohexanol rc) znjaie Al {d) Phenyl benzoate to Benzaldehyde wir CH Meer (=; = (HLF ne otMatch the following Column 1 (Amines) Column 2 (pkb values) (a) Ethyl amine (i) 3.25 {b) Diethyl amine pr? (c) Triethyl amine (d) Aniline (2) ~ Gil; (6) — Civ); (od ~ (i); () (a) anon gain OoMatch the following Column 1 Column 2 {a) [Co(NH,),NO,]Cl, (i) lonisation isomerism (b) [Co(NH,),S0,]8r (ii) Coordination isomsism {) [coftvH)q] Ecr(CNDg] (i SotyageaBBtnerism (d) [Co(H20).]Cl, Wlih) Linkage isomerism (a) — (iv); (b) (id; (e) ~ (iid; (d)Match the following Column 1 Column 2 {2) Ni in the presence of H, “(i) Decomposition of KCIO, (b) Cu,Cl, (ii) Contact process). (avo, “Gi veg Bio ghee {d) Ticl, + AN(CHs)s Wilh Ziegler-Natta catalyst (a) - (6) ~ (is (e)~ (i; (€) ~ (iv) sno oaMatch the following Column 1 ‘Column 2 (a) ac? {i) 0.059/n log K. (b) Een (RF afl a) P- (de {d) An (2) ~ Civ); (b) ~ (i); (2) — (i; (a) or.Match the following Column 1 Column 2 (a) Zero order reaction (i) ty = Y/KIR]y (b) First order reaction (ii) tye = [Rh/2k_ yD (c) Second order reaction Gil) tan (2) (i); (6) — (i); (€)— i) mse oo gaatMatch the following Column 1 Column 2 {a) Smoke (i) Gas in liquid (b) Aerated drinks (ii) Solid in fquid send (c) Water vapour (iii) Gas {d) Amalgam yh) Liquid in gas (b) = (iv); (e) =f); (@) — (a) 1 onto oe (a)Match the following Column 1 Column 2 {2) Amino acid {i) Polysaccharides (b) Fatty acid, Glycerol (ii) DNA, pr? (c) Nucleotides ii) Pot {d) Simple sugars pis (0) =i (6)= fe) (A; 1€)=6) gas Oo aneFormulae — Solutions Chapter Concentration Terms Mass Percentage = (M,x 100)/(M,+Ms) Volume Percentage = (V,x 100)/(V,+Vp) > gh yer Molarity (M)= Roca = Wow ¥ 1000/(Magg 85) pa Molarity(m) = Naun/Vie= OW, a Vi Normality (N) = Gram equivasise/Vig = (Weoute * 1000)/(Eq Masszoute X Vm) Mole fraction (x) = Mojute orsoivens/Total number of molesFormulae — Solutions Chapter Henry’s Law P=Ky * Sotute p = partial pressure of gas is equilibrium with solution X jute(gas) = Mole fraction of the gas ase K,, = Henry law constant esa Note: Effect of Pressure on solubility of gas in liqud: Solubility of a gas in liquid is directly proportional to pressure of gas on surface of the liquidFormulae — Solutions Chapter Colligative Properties Relative lowering of vapour pressure: (P°-P)/P° = W./ M, x M,/W, Molar mass from elevation of boiling point: M, = (W, x 1000 x ae xW,) Molar mass from depression of freezing point: nseant’S 0 ‘1000 x K,)/{AT; x W,) ww Molar mass from osmotic preset WW. SRT/nV M, — molar mass of solvent; W, — weight of solvent; M, — molar mass of solute; W, = weight of solute; K,, — ebullioscopic constant; AT,, - elevation of boiling point; K;- cryoscopic constant; AT; - depression of freezing point; R— universal gas constant; T— absolute temperature (K); m— osmotic pressure; V — volume in litresFormulae — Electrochemistry Chapter Standard Cell Potential: E04 = Ecathode ~ E°anode Standard Gibbs Free Energy Change: AG®° = -nFE° Limiting Molar Conductance: 4,,° (CH;COOH) = “,,° (CH goanni, ° (HCI) -4,,° (Nacl) en na fen OO Degree of dissociation: a= Sy< gana Dissociation Constant or lonisation Constant: K,=C aor a =v(K,/C)Formulae — Chemical Kinetics Chapter Rate constant for zero order reaction, k = {[R]y - [R]}/t Rate constant for zero order reaction, k = (2.303/t) log ([R]o/{R]) Half life period of a zero order reaction, ty), = ([R]o/2k 10 Half life period of a first order reaction, ty)» = (6035) " fro ast Arrhenius equation k = A e®¥i!¥8fect of temperature on rate constant) Arrhenius equation log k,/k, = E,/(2.303 x 8.314) [1/293 — 1/308] (effect of temperature on rate constant)Data from tables ‘Table 10.2: Carbon-Halogen (C—X) Bond Lengths, Bond Enthalpies and Dipole Moments Se Snes 452 1.847 204 1.696 + Fis highly electronegative ggaioSialiest amongst halogens and hence it forms shortest C-X begabétd hence it is strongest and has the highest bond enthalpy * Though fluorine is more electronegative than chlorine, the dipole moment of C-Cl bond is larger than C-F bond as dipole moment depends on charge and distance, since Cl is larger than F, C-Cl bond is longer than C-F bond resulting in higher dipole momentData from tables Table 10.3: Density of Some Haloalkanes In Pano) Int Para) CHC 0.89 cH.c, 1.336, -GH,Br 1.885, cul, 1.489 aC 1747 cc, 1.595, sen ya * Density increases with atgadetVeight of the halogen (also larger size leads to greater van dergasails force) and with the number of halogen atomsData from tables Broo 0 00 Boiling point increases with increase in atomic 200 weight of halo; gapekD with increase in length of Pe the car, in attached to halogen HX CLHX cHLeHCHX oe ad cxemcwonoe caxcumten me-ten, Among isomeric haloalkanes boiling point be a decreases with increase in branching (or 364 " jr Bea 978 with decrease in chain length)Data from tables cl cl or ‘on cl : Asner 54 Boiling points of isomeric (o-, m- and p- dichlorobenzenes are almost similar but para isomer has higher melting point than ortho and meta isomers due to its molecular symmetryName reactions ° Finkelstein Reaction 2 dry exit “ ws RC1+ Nal Spi RA + NaCl Rae! _ Ikyl chiqujde’®* alkyl iodide mip eh, y* Swarts Reaction D ; con R-Cl+ Agr ee ‘AgCl yo alkyl chloride,sno%" alkyl fluoride° Hunsdiecker Reaction Dd ene RCOOA+ Bry Ch, RBs +. cope silver salt of oti onde carboxylic acid y..s8™* Wurtz, Fittig and Wurtz-Fittig Reactions RX+2Nat+XR _Mryether pz X=-Cl,-Br ye —tiyether, ar-Ar+2NaX Bipheny/Diphenyl X=-CL-Br Aryl halide AUX+2Na+X-R_Adryether pp +2NaX X=-Ch-Br Alkyl benzene Alkyl halide + Aryl halide* Sandmeyer Reaction es oh. wie pri SC 1a! gen cute ot +™ X=-Cl,-Br Halo benzene* Gattermann Reaction . aa “ se} wo™ ate An X=-Cl,-Br Halo benzene* Balz-Schiemann Reaction . ee Axe Foxit. MO 5 ad ga (gah? +N, +BFy ver WA Fluoro benzenejiamson’s Ether Synthesis ren? CHyCH,ONa + CHyCH,Br——*, sCM8CH,0CH,CH, + NaBr sodium ethoxide ethyl Drones ethoxyethane oeUllmann Biaryl Synthesis > (ar me Phony ide ee x3 nan ons DiphenytAllylic substitution with NBS Reactant: Alkene Reagent: N-bromosuccinimide (NBS) Product: allyl substituted product (bromo alkene) cyclopentene Br 3-bromocyclopent-1-eneGABRIEL PTHALIMIDE REACTION (RX aq, NaOH ALIPHATIC! PRIMARY ase I AMINE eo * AROMATIC PRIMARY AMINES CANNOT BE PREPARED BY THIS METHOD,HOFFMANN BROMAMIDE DEGRADATION REACTION RCONH) + Br, +4NaQH ———> RANE + NayCO, +2 NaBr+2 0)CARBYLAMINE REACTION 3KC1+ 34,0DIAZOTISATION RNH,+HNO, ————> _ R-OH+ N, + Hi) ALIPHATIC PRIMARY ALCOHOL AMINE on SAT mo, ef) oerezto AROMATIC [BENZENE DIAZONIUM CHLORIDE PRIMARY AMINESCHOTTEN-BAUMAN FOLLOWED BY FRIES REARRANGEMENT“MUSTARD OL REACTION CoH, + 5 ANILINE ISOTHIOCYANATEGattermann Koch Reaction * Benzene is treated with carbon monoxide in acidic medium in the presence of anhydrous aluminium chloride catalyst to give benzaldehyde (Aromatic Electrophilic SubstitytiorPReaction) pri HV 0 Alc, +CO+HCL aeDecarboxylation Reactant: sodium salt of carboxylic acid Reagent: soda lime (NaOH + CaO) Product: alkane - ond CH,COO Na* +NaOH-S5CH, +Na,CO,Ozonolysis Reactant: alkene oO cH,cH=cH,+0, cH, OH, Reagent: ozone Propens se Prope cade [een cH,cHO + HCHO thanal ‘Methanal Product: carbonyl compoundFriedel Crafts alkylation cx, Reactant: benzene + alkyl halide oO + cnc SAE, CQ ici Reagent: anhydrous AICI, rene Product: alkyl benzene p20? preFriedel Crafts acylation Reactant: benzene + acetyl chloride Reagent: anhydrous AICI, Product: acetophenone pri cH, Co + cre EAE, CO a +lDow’s process Reactant: chloro benzene Reagent: NaOH Product: phenol O ( NaOH, 623K, 300 atm 9 n° ou 0Rosenmund reduction Reactant: benzoyl chloride Reagent: hydrogen/ Pd/BaSO, A . eno Product: benzaldehyde oO so, Co ery cre Bena ph BR anes Se ae aan tooStephen reaction Reactant: alkyl cyanide Reagent: SnCl,/HCI Product: aldehyde can Bn? RCN + SnCl, + HCl >> RCH = NH “2° >RcHO wr R28! garnet”Etard reaction Reactant: toluene Reagent: chromyl chloride Product: benzaldehyde Coo CF ‘Tomene (Chromium comple oe aie" = HD = Benzaldehyae HoClemmensen reduction Reactant: carbonyl compound Reagent: Zinc amalgam + con HCI Product: alkane \n 2a, \ Do=0 Ha YH, + #0 war sn R28 gana can Bn? (Clemmensen reduction)Wolff-Kishner reduction Reactant: carbonyl compound Reagent: hydrazine and KOH (base) Product: alkane Noo NEN, S, KOH/ethylene glycol S o=0 Sip oan, See OCH, +N (Wolff-Kishner rduction) nent” oe.Aldol condensation Reactant: aldehyde or ketone with alpha hydrogen Reagent: NaOH (base) Product: beta hydroxy carbonyl compound or alpha beta unsaturated carbonyl compouindalkane Do anne dil. NaOH, A 2. CH,-CHO =—— CH,-CH-CH,-CHO S75> CH,-CH=CH-CHO Ethanal ‘OH ‘ But-2-enal $-Hydroxybutanal (Aldol condensation (aldo) product)Cannizzaro reaction Reactant: aldehyde or ketone without alpha hydrogen Reagent: Conc alkali Product: alcohol and sodium or potassium salt of carboxylic acid _ cnn Pn? 4 % a ee ee ee G ca 1 Nox ‘Benzaldebyde Sodium benzoateHVZ reaction Reactant: carboxylic acid containing alpha hydrogen Reagent: Red P and halogen Product: alpha halo acid gn? prt. 0 ™ Sol) Ra Ree prespnarss * — on ee, Coot ASUS MERE i SoH write i x xrol or Hendon atHydroboration Reactant: alkene Reagent: borane, hydrogen peroxide, aqueous alkali Product: primary alcohol (anti Markovnikov’s addition) aD CH,-CH=CH, + (H-BH,),—> CH,-CH-CH, H BH, Jenecuecn, CH-CH=CH, (CH,-CH,-CH),B <———— (CH,-CH,-CH)),BH 1,0] s11,0,, O11 3CH,-CH,-CH,-OH + B(OH), Propan-1-olDiazotisation Reactant: aniline (aromatic primary amine) Reagent: nitrous acid (273 - 278 K) Product: benzene diazonium chloride ® NH, Noche NaNO. +HClAcetylation Reactant: salicylic acid Reagent: acetic anhydride (acidic medium) Product: acetyl salicylic acid (aspirin) = COOH coon OH * OCOCH, + (CH,CO),0—> + CH,cooH Salicylic acid Acetylsalicylic acid (Aspirin)Jones oxidation Reactant: primary alcohol Reagent: CrO, Product: aldehyde (with same number of C atoms) Dd ca, 188" RCH,OH —22_5 RCHO rar? osKolbe’s reaction Reactant: phenol Gia tt Reagent: carbon dioxide and alkali Cham or 1909, Product: salicylic acid Sty ecRiemer Tiemann reaction Reactant: phenol Reagent: chloroform and alkali Product: salicylaldehyde ananePh oH ‘Nat Ona ‘OH Suess ma OH, x01, iy Cnn peeSchotten Baumann reaction Reactant: aliphatic primary amine Reagent: benzoyl chloride Product: benzamide grd np: CH,NH, + CgH,COCI > CH,NHCOG,H, + HCl Methanamine Benzoyl chloride N-Methylbenzamide ane” OoCoupling reaction Reactant: benzene diazonium chloride + phenol/aniline Reagent: NaOH Product: p-hydroxyazobenzene or p-aminoazobenzene ond Cpe ’ 6 pons Cpe pos crn Dpiiydrosyaabenaene (range ye) Cris + eK mn ts Cee Deans ero ‘yew iedMendius reaction Reactant: alkyl cyanide Reagent: sodium and ethanol Product: alkyl amine (with same no of carbon atoms) can Bn? CH,C = N+4[H] **** 5 CH,CH,NH, pn anonFries rearrangement Reactant: phenyl benzoate Reagent: aluminium chloride Product: o and p-hydroxyacetophenones Res. CG a0 (e-and p- ang netones)Rules Markovnikov’s Rule * During the addition of unsymmetrical reagent to unsymmetrical alkene, the negative part of the reagent goes to the CaRbORWhich contains least number of hydrogen atoms pit:Rules CH3CH,CH,BrRules Saytzeff’s Rule * During B-elimination, whenever there is a possibility of formation of more than one type of alkene, the most supetitilted alkene is obtained as a major product ase propene 1-bromopropane|Law Statements + Henry's law: The solubility of a gas in a liquid is directly proportional to partial pressure of the gas present above the surface of liquid or solution Raoult’s law I: At constant temperature, the vapour pressare of a solution (P) is directly proportional to mole fraction of solvent {xsh®™ Raoult’s law Il: Relative lowering of vapnasr pessure (P°-P/P®) is equal to mole fraction of solute (x,) [Note: Raouisetaw becomes a special case of Henry’s law in which K, becomes equal, tows)” ai Dalton’s law of part®it‘pressure: The total pressure over the solution phase in the container will be the sum of the partial pressures of the components of the solution (Ptotai = Pa + Pa) * Ohm's law: The potential difference across the conductor is directly proportional to the current flowing through it (V/I = Ror V = IRLaw Statements Kohlrausch’s law: At infinite dilution, when the dissociation of electrolyte is complete, each ion makes a definite contribution towards the molar conductivity of electrolyte, irrespective of the nature of the other iop,with which it is associated. [A,,° (NaCl) = Aya? + A%] es Faraday’s laws of electrolysis |: The magss6t'S substance deposited or liberated at any electrode is directly Propogtignsfito the quantity of charge passed 5 ‘ 7 Faraday’s laws of elgewdlfsis Il: The mass of a substance deposited or liberated at any electrode on passing a certain amount of charge is directly proportional to its chemical equivalent weight Rate law: At constant temperature, rate of a chemical reaction is directly proportional to product of molar concentration of reactantsOrders * Boiling point of alkyl halides: RI > RBr > RCI > RF n-butyl chloride > n-propyl chloride > ethyl chloride > methyl chloride n-pentyl chloride > isopentyl chloride > neopenty) ehForide * Order of density of alkyl halides: RI > RBs. aC CCI, > CHCl; > CHCl, > CH;Cl * Order of reactivity of alcohols towards halogen acids: 3° > 2°> 1° % prder of reactivity of byalreigen halides towards alcohols/ethers: HI > HBr > * Order of reactivity of alkyl halides towards Sy: 3° > 2° > 1° * Order of reactivity of alkyl halides towards S,?: 1° > 2° > 3° * Acidic strength of alcohols: 1° > 2° > 3° * Ease of dehydration of alcohols: 3° > 2° > 1°Orders * Order of basic character of amines: Aromatic Amines > Ammonia > Aliphatic Amines * Order of boiling points of isomeric amines: 1° > 2° > 3° * Order of basic character of amines (gas phase): 332% a2 * Order of basic character of aromatic agpipes: SS 29> 19 * Order of basic character in in agueeti'Solution (methanamine series): 2° > 1° > 3° * Order of basic characte 2 aqueous solution (ethanamine series): 2° > 3° > 1° * Order of basic strength: p-toluidine (ERG) > aniline > p-nitro aniline (EWG) * Order of stability of free radicals: Benzylic/Allylic > Tertiary > Secondary > Primary > MethylOrders * Order of boiling point ‘comparable molar mass): Alcohols > Ketones > Aldehydes > Ethers > Alkane * Order of acidic strength of phenols: Phenols with EWG > Phenol > Phenols with ERG > Alcohols * Order of acidic strength of phenols: p-i nioge® SY 0" S aicepiarl >m- nitropheno! * Order of field strength of liga years < SCN < Ch RCHO > C,H;CHO > RCOR > C,H,COR > C,H.COC,H, p-nitrobenzaldehyde > benzaldehyde > p-tolualdehyde * Order of ease of leaving group: CH;COCI > CH,COOCOCH, > CH;COOCH, > CH,CONH, * ° aes 3°Distinguish between the following [ROR RNP ROO nO ONS LAE Sl Pyare od RoNr aU nm On Brinn aee treo yard ‘OveysRaoutr’s aw Papa's P= Pa! Pai= Pa s-hexane & n-neptane etl bromide & ety iodide, ethylene bromide & eliylene chloride, benzene & toluene ‘Disobeys Raoult law. Pat Dal Pat Pas Prat? Pa Pa Poni Pat Pa ats 05 Vn 8 Interactions betweenABA.A/BB Form maximum bolting azeotropes ‘Chloroform & acetone, chloroform & benzene, water and hydrochloric acid, water & nitric acidDistinguish between the following Cerne Green Converts chemical energy to electrical energy Converts electrical energy to chemical energy Involves spontaneous redox reactions Non spontaneous, an reactions are brought about by supplying el ‘Anode is negative and cathode is positive Salt bridge is required senieo a cathode is negative it bridge not requiredDistinguish between the following Eoeetaeentincs a Allow current to flow through them without Allow current to flow through them and undergoing any chemical change simultaneously undergo chemical decomposition 2. Conduction is due to movement of electrons Conduction gu WS movement of ions 4. Ag, Cu, Al are example for metallic conductors Ke etc are examples for electrolytic W\S€onductors l « ari OoDistinguish between the following = Bees eee 1 Completely ionized in aqueous solutions Partially ionized in aqueous solutions a Mineral acids like hydrochloric acid, sulphuric Ammonium hydroxide, acetic acid, ete acid, sodium hydroxide, ammonium chloride, ete nse oon” anDistinguish between the following Primary Secondary 1) Itonly acts as galvanic or voltaic cell. .e., produces electricity 1) Itacts as galvanic or voltaic cell while discharging (produces electricity) and acts as electrolytic cell (consumes electricity) 2) Cell reaction is not reversible. 2) Cell reaction is reversible. 3) Can't be recharged 3) Can be recharged ‘4) Can be used as long as the active materials are present ‘4) Can be used again and again by recharging, ‘eg: Leolanche cell or Dry cell, Lithium cell Uses: In Pace makers watches, Transistors, radios, ect. ‘eg: Lead storage battery, Ni- Cd battery, Lithium ion cell Uses: In electronic ‘equipments, automobile equipments, digital cameras, laptops, flashlight.Distinguish between the following Order Molecularity Sum of powers of concentration terms that appear in the rate equation Experimental Number of molecules taking part in each and every elementary step of a chemical reaction Theoretical er? Can be zero, negative or fractional 8 Cannot be zero, pegs’ fractional.ya™ oe Can be assigned for overall reacti Aad at ined for each and every elementary step Order can change with temperature, pressure and concentration Molecularity does not change with temperature, pressure and concentrationDistinguish between the following Nines Cems Binding energies of 4f electrons are higher _ Binding energies of Sf electrons are lower Maximum oxidation state exhibitedis +4 Exhibit +4, +5 and +6 oxidation states 4f electrons have relatively higher shielding _5f electrons have relatively poor shielding effect effect Most of their ions are colourless Most of their ions are coloured They are paramagneticand their magnetic Theyare also paramagnetic and their property can be easily explained ‘magnetic property cannot be easily explained They do not form complexes easily ‘They form complexes easily Expect, promethium they are non Allof them are radioactive radioactive Their compounds are less basic Their compounds are more basic They do not form oxoanions They form oxoanions (UO,", UO)Distinguish between the following emer’ ee Dissociates completely into simple ions _Dissociates into one simple ion and one when dissolved in water (lose their complex ion when dissolved in water (do identity in aqueous solution) not lose their identity in aqueous solution) Exist in solid state Exist in solid state as well as in aqueous solution Contain two simple salts in equimolar May or may not contain two compounds proportions in equimolar proportions Eg: carnallite, Mohr’s salt, potash alum, —_Eg: potassium ferrocyanide, nickel etc tetracarbonyl, etcDistinguish between the following 1, Molecules with more than one stereocenter which are not mirror images can be diastereomers 2. Have different physical and chemical properties 1. Molecules with one stereocenter which are mirror images can be enantiomers 2. Have identical physical and chemical properties. Only differ in rotation of plans polarised Nahaeano™ ant oesDistinguish between the following Unimolecular nucleophilic substitution reaction Two step process Step 1: heterolytic fission of C-X bond to form. carbocation Step 2: attack of nucleophile on carbocation Tertiary halides are more reactive towards Sy Rate depends only on concentration of subsrate Reaction follows first order kinetics Reaction is favoured in the presence of polar protic solvent because the energy required for cleavage of C-X bond is obtained through solvation of halide ion with proton of protic solvent If chiral substrate is used, it leads to racemic mixture and hence the reaction is called racemisation One step process ie., attack of hydroxide ion to form C-OH bond and cleavage of C-X bond occur simultaneously (concerted reaction/mechanism) Hydroxide ion attacks the carbon from the side opposite to C-X bond (backside attack) No intermediate is formed and there is only a transition state (unstable and cannot be isolated) where carbon is simultaneously bonded to incoming nucleophile (hydroxide ion) and outgoing nucleophile (halide ion) The configuration of carbon is inverted and the process is called inversion Reaction rate depends on concentration of both substrate and nucleophile Bimolecular process Reaction is second orderDistinguish between the following EI 1 Tertiary halides undergo elimination by E1 2. Unimolecular 3. Two step process with intermediate 4, Does not require strong base 5. Rate of the reaction depends only on the concentration of substrate 6. Antiperiplanar conformation is not required 7. Good leaving group, stable carbocations, weak bases favour E1 ve Ez 1. Primary halides undergo elimination by E2 2. Bimolecular 3. One step process, no intermediate, concerted 4, Requires strong base 5, Rate of the season depends qua roncentration substrate and base 6. . Antiperiplanar conformation is required 8, Poor leaving group, strong bases favour E2Distinguish between the following Also known as symmetrical ethers Also known as unsymmetrical ethers Two alkyl groups attached to oxygen Two alkyl groups attached to oxygen are same are different Dimethyl ether, diphenyl ether, THE, _Ethy! methyl ether, anisole, etc eteOrganic Reasoning Questions 1. Why aryl halides cannot be prepared by the reaction of phenol with halogen acids? Carbon oxygen bond in phenol has a partial double bond character (short and strong) and hence itis difficult to break the bond 2. Why alkyl iodides cannot be prepared directly by treating an alkane with iodine? lodination of alkanes sa reversible process as the by product formed Hs fBducing agent and it reduces alkyl iodide back to alkane si em CHe +l, 1 gases 3. Why alkyl fluorides cannot be prepared daar Direct fluorination is highly exot pestle luorine free radicals are extremely reactive. It may lead to explosion as it is difficult to control the reaction 4, Why anti-Markovnikov’s addition or peroxide effect is applicable only for HBr addition and not to the addition of HCI or HI? H-Cl bond is strong and hence chlorine free radicals are not easily formed (bond energy of H-Cl bond is more than that of H-Br bond). In case of H-1, iodine free radicals are formed but they are not reactive enough to attack alkenes, instead they combine with each other to form iodine moleculeOrganic Reasoning Questions 5. Why is sulphuric acid not used during the reaction of alcohols with KI? Because H,S0, oxidises KI to |, and thereby prevents formation of alkyl iodide KI +H,50, > KHSO, + HI BHI+H,SO, 9H,S+4H,0 +41, Hence non oxidizing agent like HPO, is used KI +H,PO, > KH,PO, + Han 2? ¥. ROH + Hpi 6. Explain why alkyl halides though polar, are imraigealeNith water? 8 The new force of attraction between stifles and water is weaker than the force of attraction already existing alkyl halide-alkyl halide mol@éules (dipole-dipole interaction) and water-water molecules (intermolecular hydrogen bonding) 7. The dipole moment of chloro benzene is lower than that of cyclohexyl chloride? In chloro benzene, the electron withdrawing —1 effect of ~C| is opposed by +R effect of —Cl and hence it possesses lower dipole moment whereas in case of cyclohexyl chloride, there is only -1 effect of —Cl and hence it possesses higher dipole momentOrganic Reasoning Questions 8. Why allylic and benzylic halides undergo substitution by Sy1 Allyl and benzyl carbocations are stabilised by resonance. 9. The order of reactivity of haloalkanes is RI> RBr > RCL Larger the halogen, longer and weaker is the R-X bond and hence the more reactive is the alkyl halide. 10. Why Neopentyl chloride does not follow S,? mechanism. Because of steric factor. eh pn? 11. Why iodoform has antiseptic properties? nen se When iodoform comes into contact with topical ca skinot erates iodine which has antiseptic properties. 12. Why even traces of moisture sigue Sized during synthesis or use of Grignard reagent? Grignard reagent is moisture senfive and it decomposes to alkane. 13. Why allyl chloride is more readily hydrolysed than n-propyl chloride? Allyl carbocation is resonance stabilised whereas propyl carbocation is not stabilised by resonance, 14. Why chloroform is kept in dark-coloured sealed bottles? Chloroform is slowly oxidized by air in the presence of light to form phosgene or carbonyl chloride (COCI,) which is highly toxicOrganic Reasoning Questions 15. Why thionyl chloride is preferred for converting alcohol to alky! halide? SO, and HCI are gaseous byproducts (volatile). 16. Why alkyl halides are better solvents than aryl halides? Because alkyl halides are more polar than aryl halides. 17. A small amount of ethyl alcohol is added to chloroform stored for use as an anaesthetic. Alcohol acts as an inhibitor for oxidation of chloroform. Also, ethyl alegpals@adts with phosgene or carbonyl chloride (COCI,) to form harmless diethyl carbonate. gril 18, After using CCl, asa fre extinguisher in a closed spqul, fie area should be thoroughly ventilated, CCl, reacts with water vapour at high temagrS¥#RE to form phosgene (CoCl,) which is toxic. 19. Why even traces of moisture pactftS be avoided during synthesis or use of Grignard reagent? Grignard reagent is moisture sensitive and it decomposes to alkane. 20. Vinyl chloride is unreactive in nucleophilic substitution reaction. Vinyl carbocation is not stabilised by resonance. 21. p- Methoxybenzyl bromide reacts faster than p - nitrobenzyl bromide with ethanol to form an ether product Methoxy group is an electron releasing group which stabilizes the carbocation whereas nitro group is an electron withdrawing group which destabilizes the carbocation.Organic Reasoning Questions 22. Wurtz reaction fails in the case of tertiary alkyl halides. Due to steric hinderance, elimination (side reaction) takes place. 23. Organic halogen compounds used as solvents in industries are chlorides rather than bromides or iodides. Because chlorides are more volatile, stable and lighter. 24, Why anaesthetic ether is preferred over chloroform? Because chloroform slowly decomposes to toxic phosgene and also leads to hepgtotoxicity and cardiac arthythmias. 25. Treatment of alkyl halide with aqueous KOH form aeohos whegqaa ren of alkyl halide with alcoholic KOH forms alkenes. ge In aqueous KOH, OH functions as a nucleophile anaatvelaces x Whereas in alcoholic KOH, C,H.0 "is produced which isa strong base and t leads to B-aliina 26. Why even traces of moisture sui be avoided during synthesis or use of Grignard reagent? Grignard reagent is moisture sensitive and it decomposes to alkane. 27. Vinyl chloride is unreactive in nucleophilic substitution reaction. Vinyl carbocation is not stabilised by resonance. 28. p- Methoxybenzyl bromide reacts faster than p - nitrobenzyl bromide with ethanol to form an ether product Methoxy group is an electron releasing group which stabilizes the carbocation whereas nitro group is an electron withdrawing group which destabilizes the carbocation.Inorganic Chemistry Reasoning Questions 1. Why first ionisation energy of chromium is less than that of zinc? lonisation energy of fully filled orbital (Zn - 4s? 3d") is more than half filled orbital (Cr- 4s* 3d) 2. Why Zn, Cd & Hg are not considered as transition metals? They have completely filled d-orbitals and hence do not show regular properties of transition metals ie., they do not, form coloured salts, they do not exhibit variable oxidation states, etc. 3. Why alkali metals are soft whereas transition metals are hard? er? Alkali metals are soft because of larger size and presence of only one velsitte electron which results in weak inter metallic bonding oe 4. Why silver has highest electrical conductivity? yavo™ /Ag— [kr] 4a#® 5st, Presence of only ong, y@HeiEe electron which can move freely in the crystal structure. In is lower than that of Cr though Mn has more unpaired electrons? 5. Explain why the melting point of Half filled d orbitals ~stable- so ‘d’ electrons do not take part in inter atomic / inter metallic bonding 6. Generally, as we move down the group, atomic radius increases but atomic radius of ‘Sd element is almost the same as ‘4d’ element belonging to the same group. Why? Due to Lanthanide contraction.Inorganic Chemistry Reasoning Questions 7. Why Ni?* compound is more stable than Pt* whereas Pt** are more stable than Ni** compound? Ni?* compounds have the sum of first two ionisation enthalpies to be lower than that of Pt?* compounds. Hence they are thermodynamically more stable. Whereas, the sum of the first four ionisation enthalpies of Pt“* compounds is lower than that of the first four ionisation enthalpies of Ni** and is therefore relatively stable. 8, Why Cu" is more stable than Cut in aqueous solution? It is due to high hydration energy of Cu2* which compensates for ionisation energy and enthalpy of sublimation. 9. Why alkali metals are soft whereas transition metals are hard? nen? Alkali metals are soft because of larger size and presence of onlygnsalence electron which results in weak inter metallic bonding mse 10. Why the highest oxidation state exis inits fluoride or oxide? Due to high electronegativity and geese of fluorine and oxygen 11. Which is a stronger reducing agent: Cr?* or Fe*? Why? Cris a stronger reducing agent because It can lose one of its electron to become Cr" in which the tyg level of d- orbital is half filled and eg level is empty. 12. In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy of atomisation of zinc is the lowest, .e., 126 kJ mol. Why? Zn has no unpaired electrons in outermost orbital and so interatomic covalent bonding is not possible. There is only metallic bonding in solid Zn. The net result is the weaker attractive force and lowest enthalpy of atomisation.Inorganic Chemistry Reasoning Questions 13. Why transition metals form complex compounds? Small size, high charge density and availability of ‘’ orbitals. 14. Why transition metals acts as catalysts? Ability to exhibit variable oxidation states. 15. Why transition metals form interstitial compounds? They are large in size and contain interstitial voids which can be filled with srgellttoms like H, C, O, etc and this leads to formation of interstitial compounds yeh 16. Why transition metals form alloys? ase 0 Transition metals almost have similar size and guetta ‘can easily take up the position of other metal in crystal lattice and hence they readily form alloygon™ 17. Why third ionsation energies oPLa, Gd and Lu are low? Cris a stronger reducing agent because it can lose one of its electron to become Cr°* in which the t, level of d- orbital is half filled and e, level is empty. 18. Actinoid contraction is greater for element to element than lanthanide contraction. Why? This is because of poor shielding of Sf electrons in actinoids than by the 4f electrons in lanthanoid.Inorganic Chemistry Reasoning Questions 19. Why transition metals form coordination compounds or complex compounds? Presence of partially filled d-orbitals, small size, high charge to radius ratio. 20. Why tetrahedral complexes do not show geometrical isomerism? In tetrahedral complexes, all the ligands are equidistant to one another 21. Why transition metals form interstitial compounds? They are large in size and contain interstitial voids which can be filled with srgalfiatoms like H, C, O, etc and this leads to formation of interstitial compounds yeh 22. Actinoids show larger number of oxidation states than est MHoids. Why? Sf, 6d and 7s have comparable energies. ner 3 23. Why transition metals show egg sation states with CO ligand? CO is involved in back bonding (synergistic effect) with transition metal. 24. Why HCI cannot be used to acidify KMnO, solution? Because KMnO, oxi 25. Why KMnO, is coloured? Due to charge transfer transition (CTT). ses HCI to Cl,.Organic Problems ‘An organic compound with molecular formula C,H;NO, exists in three isomeric forms, the isomer ‘A’ has the highest melting point of the three. ‘A’ on reduction gives compound ‘B’ with molecular formula C;HaN. ‘B’ on treatment with NaNO,/HCI at 0-5°C to form compound ‘C’. On treating C with HPO, ,it gets converted to D with formula C7Hg, which on further reaction with CrO,Cl, followed by hydrolysis forms ‘E’ C,HgO . Write the structure of compounds A to E . Write the chemical equations involved. aChemical tests to distinguish between pairs of compounds Cees io Primary, secondary & tertiary alcohols Lucas test, Victor Meyers test (RBC) Alcohols vs phenols Neutral ferric chloride Aldehydes vs ketones Tollens, Fehlings, Benedicts, Schiffs Aliphatic aldehyde vs aromatic aldehyde Fehlings path? 2-pentanone vs 3-pentanone lodafo Aliphatic amines vs aromatic amines oon tte dye test Primary vs secondary/tertiany. git Carbylamine test Primary vs secondary vs tertiary amines Hinsberg test Haloalkane vs haloarene Alcoholic KOH Acid Vs Neutral NaHCO,IUPAC Nomenclature (Organic) ‘Whether the compound Isapen chain (acyelle) oF ‘losed chain (eyelte) | areof ‘substituent Number of carbon atoms in the ye 1. Find out the longest chain on Rai 2: Numbering is done in such aywafifhat carbon which is attached to substituent gets the lowest possible number or lowe: le sum in case if more than one substituent is present. 3. If functional group is present, it gets priority over substituent 4. If more than one substituent of the same type is present, prefixes such as di, tri and tetra are used. 5. If substituents are different, they are listed in alphabetical order and lower number is given to one which comes first in the alphabetical order 6. For aromatic compounds substituent name followed by benzene is used and in case of di or tri substituted, substituents are numbered in such a way so as to get the lowest sum 7. Priority rules: Functional groups > unsaturation > substituents > alkyl side chain 8. Order of priority of functional groups: COOH > -SO,H > -COOCO- > -COOR >-CO-X > -CONH, > - CN > -NC> -CHO > -CO- > -OH >-NH,> -IUPAC Nomenclature (Inorganic — Coordination Compounds) Positive ion is named first followed by negative ion 2. In naming the complex, names of ligands are written in alphabetical order followed by name of central metal atom . The oxidation state of the central metal atom is expressed by a Roman numeral in paranthesis after name of CM atom a 3. For naming ligands, a suffix ‘ois added ifthe ligand is negagygus€lphato, nitrito-N, etc) and ‘ium’ is added if the ligand is positive (hydrazinium, im, etc) and neutral ligands have unique names (aqua, ammine, carbonyl, ete), WS™ 4. Ligands are named in alphabetical qxaet4¥respective of whether neutral or negative 5. The number of each kind gf {sare specified by the prefixes di, tri, tetra. If the ligand is complex, such as ethyl®{ediamine and is repeated two, three or four times then the word bis, tris, tetrakis are used 6. Anionic complexes end with ‘ate’ suffix whereas cationic and neutral complexes do not have any distinguishing termination 7. Incase of ambidentate ligands, point of attachment is indicated by putting the symbol of an atom through which it coordinatesWhich of the following statements in correct/incorrect? Which of the following statement is true? (a) molecularity of reaction can be zero or a fraction. (b) molecularity has no meaning for complex reactions. 2 (c) molecularity of a reaction is an experimental quantity ener (@) reactions with the molecularity three are very rare ya fast. wer ww grat” Which of the following is 1% 2orrect? (a) In haloarenes, the electron pairs on halogen atom are in conjugation with n-electrons of the ring. (b) The carbon-magnesium bond is covalent and non-polar in nature. (c) During 5, reaction, the carbocation formed in the slow step being sp? hybridised is planar. (d) Out of CH,= CH-Cl and C,HCH,CI, C,H,CH,CI is more reactive towards $,¢ reactionPreparation of alcohols Alkene Grignard Reagent \ RCHO! | ava.o es RCOR i nen? Pt Hrd ° oe Ea, Carboxylic acids Aldehyde or Ketone—_yyastCoho anit ov SP MINaBH, H,/Pd EstersPreparation of phenols } som | SA BCL agi ~ a oe. echo,Methods of preparation of ethers Intermolecular dehydration Wlllamson’s ether synthesis con. H»SO, sodium pees Ikoxids Alcohol —————— _ Ether a halide 413K ge ern ws Intermolecular dehydration aya" works well for prima algenae (Sx2) only secondary(tersiatPaicohols undergo elimination to form alkenes (reaction mechanism changes to Sy")METHODS OF PREPARATION ALIPHATIC ALDEHYDES ‘ACID CHLORIDE RCOCI ROSENMUND REDUCTION] Hy panaso, PRIMARY ALKENE, RCHOT=4R-CH=CH, ALCOHOL DEHYDROGENATION mY ALDI BRE 7! Wo aw Rae" (or pe salifttion —/romatios er CyHn 2 R-CN ALKYNE. NITRILES 100