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www.mtg.in | February 2014 | 30 TAT PAPER Ri (G0) RNER ie FE yk \N) Tae, mcs ae oe * JEE 7 EON ria CHEMI ae iq PRACTICE nar CHAPTERWISE, SERIES-9 For Competitive Exams Class XI e ‘Questions for Medical Henny, Enrance Exams BE Competiti sess §=—- Competitor {You A SKED} oe ‘Trust of more than 1 Crore Read ‘Since 1982 CHEMISTRY Vol. XXill Corporate Office Flot 99, Sector 4 insiutional are, ‘Gurgaon -122 003 (HR), Te: 0124-4951200 email :info@mtgin website: wnwumtg.in Regd, Office 406, To Apartment, Near Safdarjung Hostal, Fing Road, New Delhi - 110078, Managing Editor: Mahabir Singh Editor Anil Ablawat (BE, MBA) Chemistry Musing Problem Set 7 JE Main Practice Paper 2014 BH NCERT Xtract : Biomolecules | Polymers | Chemistry in Everyday Life You Asked, We Answered Learn Fast : Chemical Kinetics 1H _JEE Foundation Series : Biomolecules | Polymers | Chemistry in Everyday Life 1H _NCERT Comer Class XI-XII CBSE Board 2014 Chapterwise (Practice Paper : Series-9) Concept Booster Competition Corner Chemistry Musing Solution Set 6 Essential Reactions for Competitive Exams tQday 2 February 2014 4 8 15 20 au aw n 76 84 86 ‘can ry svi Al ane eos Deas ain er ‘raised ern em eis tt edit Q,rial Alarm Bells are Ringing Drastic Decrease in Students Seeking Science reduced, This could affect our programs for technological advance T: number of students taking science subjects is geting drastically ofthe nation We need scientists, working in basic sciences, medicine and computer technology, taking to fundamental and applied research in increasing numbers. We have made magnificent advances in almost every branch of science, We ate in the closed grou of nuclear science, computer technology and our achievements in the rocket technology are second to none, The achievements reached by our famous laboratories and research establishments should have fired not only the rackets but also the imagination of our students to be part of groups that are working on the frontiers of science ‘Whatever be the cost of boosting science studies, the government has to take the problem by the horns. Barely within a month ofthe success ofthe launching the satelite tothe Mars, now we have another great news from cur rocket scientists at Vikram Sarabhai Space Centre, Liquid Propulsion Systems Centre and ISRO. Under the same leadership of ISRO, they have successfully launched GSLV 0-5 rocket to put the GSAT-14 satellite init orbit, The success of our rocket and satelite program, lke our atomic energy program is something special. Both were in the teeth of opposition by US.A,, Canada and other alles. Both the programs are successful, thanks to the moral and material help of US.SR. (earlier), and now Russia, We congratulate the success of ISRO and other establishments, Tis isthe tue spirit of Gandhian self-reliance Self-Reliance at all costs Anil Ablawat Editor ‘Subscribe otine at wwwLtg. Individual Subscription Rates ‘Combined Subscription Rates tyr. 2yrs yrs tye 2yrs 3yrs. HathematieTody 300 Son” 67S—-PCM 80012001700 Chemisty Today 3000075. PCB 80012001700 Physics forvou 300500675. —~PCMB 90015002100 BologyTodey 300500675. nd D.D/N.O in favour of MTG Learning Media () Ltd. Payments should be made directly to: MTG Learning Media (?) Ltd, Plot No. 99, Sector 44, Gurgaon - 122003 (Haryana) We havo rt appoied any subscation ago CHEMISTRY TODAY | FFSRUIARY'14 3. MUSING hemistry Musing was sirted from August ‘3 issue of Chemistry Today wit the suggestion of Shri Mahabir Singh. The aim of Chemistry Musing is fo augment the chances of bright students preparing for JE (Main and Advanced) / AIPMT / AIMS / Other PMTs & PETS with addtional study material. ‘n every issue of Chemisty Today, 10 challenging problems are proposed in various topics of JEE (Main and Advanced) / AIPMT. The detailed solutions of these problems will be published in next issue of Chemistry Today. The readers who have solved five or more problems may send their soluions, The names of those wiho send atleast five correct solutions wil be published in the next issue We hope that our readers wil enrich their problem solving skils through “Chemistry Musing" and sland in betler stead while facing the competitive exams. eROBLEY Set 7 ] JEE MAIN/PMTs CH 1. To 500 cm’ of water 3.0 « 10 kg of acetic acid @ is added. If 23% of acetic acid is dissociated, ‘CH,COOH OH what will be the depression of freezing point? [Given : Ky = 1.86 K kg/mol and density of ‘water = 0.997 g/cm*] (a) 035K (9 075K (b) 025K (a) 023K 2. p-Cresol reacts with chloroform in alkaline medium to give the compound X which adds hydrogen cyanide to form the compound Y. Y on acidic hydrolysis gives chiral carboxylic acid. The structure of the carboxylic acid is CHy 2CH(OH)COOH (a) on CHy tb) ‘CH(OH)COOH On CH; CH,COOH © On 4 cuemisrny topay | ress 8 3. In context with the industrial preparation of, hydrogen from water gas (CO + H,), which of the following is the correct statement? (a) CO is oxidised to CO; with steam in the presence of a catalyst followed by absorption of COp in alkali. (b) CO and Hy are fractionally separated using differences in their densities. (9) CO is removed by absorption in aqueous CusCl, solution, (d) Hy is removed through occlusion with Pd. Solution Senders of Chemistry Musing 1. Aravinda Krishnan R, Kollam Kerala) ‘Abhishek Kumar, Bhojpu (Bian) Md, Fialudin, aisha (Bihar) CCK Reo Narasaragpe (Andhra Pradesh) an 1. Foram Ravindra Joshi, Thane (Maharashtra) 2. Hit Aggarwal, Rohtak (Haryana) 4. Asolution which is 10M each in Mn®, Fe® Zn and Hg”'is treated with 10 M sulphide ion. If Ky, of MnS, FeS, ZnS and HgS are 107”, 107, 107" and 10° respectively, which one will precipitate first? (a) Fes, (b) MnS (9. Hgs (a) Zns 5. The root mean square velocity of hydrogen is V7 times the root mean square velocity of nitrogen. If 7 is temperature of the gas then (2) T(Hy) = 7(N2) (b) T(t) > TN) (© TH) © (d) SO, 9. An electron is moving with kinetic energy of 4.55 x 10 J, Its wavelength (in 10” m) is [Given : mass of an electron = 9.1 x 10" kg and 6% 10 kgm? st] 10. The total number of cyclic isomers possible for a hydrocarbon with the molecular formula Ci is 7 AVAILABLE Volumes of the following years are available: Physics For You 2013, 2012, 2011, 2010, 2008 PHYSICS foryan Chemistry Today BIOLOGY MATHEMATICS ogy am 2013, 2012, 2011, 2010, 2008 Biology Today 2013, 2012, 2011, 2010, 2008 SEE Be 6 cuemstay opay | sau 2013, 2012, 2011, 2040, 2008 ‘Mathematics Today BOUND VOLUMES of your favourite magazines Price : ¢300 for each volume POSTAGE FREE! How to order : Send money by demand dratmoney ‘order. Demand Draft stould be dravm in favour of MTG Loarning Media P) Ltd. Menton he vam you require alongwith yournameandaddress.. Mail your order to : Circulation Manager, MTG Learring Mecia (P) Ltd. Plot 9, Sector 44 Institutional Area, ‘Gurgaon - 122003(HR) Wactorag osname 1. The correct order of first ionisation potential among the following elements Be, B, C, N, Ois (a) BxBe Mg>Ca> St > Ba. ‘This is due to {a) increase in melting point (b) increasing molecular mass (0) decreasing lattice energy (d) high heat of solvation of smaller ions, ‘The oxidation number of $ in Caro’s acid (H:SO;) is fa) +5 (b) +3 () +2 (d) +6 ‘The ease of dehydration in the following compounds is Ho D OH Son Qa Con CF OH (a) [>> Veit (9 We1> lle (b) I>I>m>1v (@) I> 1>1>1V From 200 mg of CO;, 107 molecules are removed. How many moles of CO> are left? (a) 2.88 «10° (b) 2.88% 107 (9 0.127 (a) 0.075 12, 127 mL of a certain gas X diffuse in the same time as 100 mL of chlorine under the same conditions. The gas X is (a) SO, (b) CHy () CO; (@) HS 13. Identify the incorrect statement (a) Ozone is present in the upper atmosphere, where it is formed by the action of UV radiations on dioxygen. (b) Ozone absorbs infrared protects earth from its harmful effects () Ozone layer in the stratosphere is deflected by nitric oxide, atomic oxygen and reactive hydroxyl radicals. (a) All the statements are correct. radiations and 414, Identify ‘Z’in the sequence : CHsNHp snepete x SS, y WR, (a) GHsCN (b) GH,CONH, (©) CoHsCOOH (d)_ CoH3CH)NH3 15. When MnO), is fused with KOH, a coloured compound is formed, the product and its colour is (a) K:MnO,, purple-green. {b) KMnO, purple (). Mn,O,, brown (a) Mn.0, black. 16. The correct decreasing order of the O—O bond strength present in O;, KO; and O,[AsF,] is (a) 0:>03>0; — (b) OF>05>05 (©) O2>0,>03 (@ 0; >0;>0; 17. Which of the following is a correct decreasing order ‘of boiling points ofthe given isomeric compounds? Ethyldimethylamine (1), N-Butylamine (I), Diethylamine (II) (a) U>i>1 () ous (9 M>>1 (@) M>I> 18. ‘The values of x, y and 2 in the following reaction are respectively MnO, + yH +2NOs —> aMn?+ 7 H,O + 2NO3 (a) 6.25 ) 5.26 (© 25.6 (@) 2.65 19. The hybridisation of atomic orbitals of the transition metals in the following complexes are respectively [FetE10),", [Co(NHL}.)", [NYCN)P> INW{CO),] 10. chemastay ToDaY | remus a 20. 2. 22. 23. 24. 25. 26. fa) Psp, spPt, dsp?, sp? ) Esp’, sp dsp? (0 hb, sp, dsy?, sp? (a) Psp*, sp’, sp’, dsp™ In the reaction HCN + HjO == H,0" + CN’, the conjugate acid-base pair is (a) HCN, H,0" (b) H,0, CN" (9. CN, HO" (a) HCN, CN ‘The rate constant of a reaction is 1.5 * 107 sat 50°C and 4.5 * 107 sat 100°C. The Arthenius parameter A is (a) 542% 108s (9 542% 10! st ‘The element with the highest ionisation energy among the following is (a) [He] 2s°2p" (©) [He] 2s°2p* AsS) is negative precipitate it is highest in (a) K;S0, (b) NaPO, (© AlCls @ CC, ‘The order of stability of the following carbocations (b) [He] 25°2p° (a) [He] 25°2p* Capacity to y charged sol ay oy th oh No, Gy Oct, (a) I> >> 1v (9 Welter (b) Mattel (@) M>M>T> 1 Identify the correct statement. {a) Bond order of NJ is more than Nz whereas in OF itis less than Oy Bond order of Nj is equal to No whereas in O$ itis more than O, (© Bond order of Nj is less than Nz whereas in OF it is more than Oy Bond order of NJ that of No whereas in Of it is equal to that of Os that of (b) that of that of i) is less than A hydrocarbon P of the formula C;Hy on ozonolysis gives a compound Q which undergoes aldol condensation giving 1-acetyleyclopentene The compound P is CH; CH; @ or S w® CY ° cH, cH © aC 27. Amongst TiF;, CoF?", CusCh and NiCd (At. nos. of Ti= 22, Co=27, Cu=29, Ni=28). The colourless species are (a) CoF}- and NiC} (b) TiF? and Core (©) CuCh and NiCH* (4) THF” and CuCl, 28. A sample of wustite contains one Fe (Ill) for every three Fe (II). The amount of oxygen atoms {in moles) is 2 8 @ > ® 5 4 9 © 5 @ 5 29. The bond enthalpy of Hyg is 436 kJ mol” and that of Noy is 941.3 kJ mol. Calculate the average bond enthalpy of an N—H bond in ammonia if AH; (NH3) =~ 46.0 kJ mot!, (a) 443.67 kJ mol! (b) 474.33 KJ mol! (©) 390.2 kJ mor (d) 244.88 kJ mol! 30. Which of the following will not reduce Tollen’s reagent? CH,OH nh H HOHC LO. yy HONOH ° HO/CH,OH OH yy OH H cH.OH HOH ah H yA 4 HONOH HN o NOH HOH HOH 4, HOH (a) (only (©) Q)only (0) Both (X)and (Y) — (@) Neither (X) nor (Y) EO 1. (a):Due to the extra stability of halEfilled protbitals of N, its first ionisation potential is higher than those of O and C. Further because of higher nuclear charge, first ionisation potential of Cis higher than that of Be and B. Amongst Be and B, the first ionisation potential of Be is higher than that of B because in case of Be, an electron is to ‘be removed from 2s* orbital while in case of B, an electron is to removed from 2p! orbital. Thus, the overall order is B CHy—CH—CH: ie i CH,—CH=CH—CH;CN 5 CHy-CH—CH= Hy CN m (d): The solubilities of BeSO, and MgSO, are highest due to high energy of solvation of smaller Be“ and Mg” ions. The value of solubility product decreases which explains decrease in solubility on moving down the group. fi (@): HO-S—0-O-H 0 Cares acd (H3S05) ‘Two oxygen atoms are in peroxo linkage ie., ‘oxidation number =—1 3 (-2)42(-1) +x +241 -8tx42 xar6 (a): Allylic carbocation is more stable and C—H bond is easily broken compared to C—D bond. Hence, the order is I> HII > IV >IL (b): Gram-molecular mass of CO: ‘Mass of 107! molecules of CO; 44 6.02310 Mass of CO, left = (0.2- 0.073) = 0.127 g 0627 998 «107 77 x10”! 073g Number of moles of CO; left (c) If Fis the time taken for diffusion of each gas, then by Graham's law of diffusion, te w7it_ Ma, _ [a fa, 10/1 {My My ‘cuemistay Topay | remus =CH—CH,Cl 6. (b): Number of electrons in NOy =7+(3%8)+1=32 Number of electrons in CO? = 6+ (3 x8) +232 Number of electrons in CIO; = 17+ (28) +1=34 Number of electrons in $0; = 16+ (3 «8 ‘Therefore, NOS and CO} are isoelectronic. on yo CH, CH;—CH=CH—CH} “CN fast (CH;—~CH=CH—CH,—CN rs) a My Hence, the gas X is CO, having molecular mass Mu 2 127) or My=44u (in) 13. (b): Ozone absorbs ultraviolet radiations and protects earth from its harmful effects. NaNO3+HC1 14. (0): CgHsNH) > CgHgN3Cr-2S mx oO “ tao CeHsCOOH 2K;MnO, + 2,0 16. (d): Since bond strength *« bond order, so we calculate the bond order in the given species 2S 0°28 ep nap: ROR 2p 2p 03 (in KO) : 15 61s? 028 0°25 c2p? nap? naV2 2p w2p) 80-7215 2 O} (in OJASF,)) : 1s" ols? 62s? 62s? o2p? n2pz 2p w'2ph po.= 1-35-95 17, 18, 19, 20. 21. The B.O. of three species follows the order O}>0,>0} + Bond strength in decreasing order is, $>O> 03 (a):1° and 2° amines, unlike 3° amines form intermolecular H-bonding. 1° amine with two H’s available for H-bonding has a higher boiling point than 2° amine. (d): 2MnO; + 6H" + SNO, —> 2Mn* + SHO +5NO}; (0): [Fe(HsO)eI" ad 4s niall 4p fexpoxpuo ——— PB hybridisation 3d ds [Co(NFIy I” Vex ex = Pa hybridisation 3 4s 4p INN): 4AM bod bod boxhod a sp? hybridisation 4p 4d bx }xx| 4p INWCO)A: 4] HO + ON Conjugate acid. Conjugatebase (@): HCN + HO = Add Base (a); Using the relation kg [Q-7, og ‘«_|%-7 ky 2303R | 7, x7, we get og 45X10" Ey [2] 75x10" | 2308x8314] 323%373 E,x50 2.303 x8.314x323x373 or £,=2.2«10*J mol" Again, or log: E, 2303 RT ogi (4.5 * 10°) = logy A Iogia E= logio A ~ - x104 23038314973 A=542 x10" st 22. 23, 24, 25. 26. 27. {o):The element with half-flled electronic configuration is most stable and therefore shows highest ionisation energy. (0): AICI has highest capacity to precipitate ‘As)S5 sol because AICI; produces Al" ion which has the maximum valency among the al. (b): Electron releasing group stabilises while clectzon withdrawing group destabilises the benzylium carbocation. (c): Nj is formed by the removal of an electron from the bonding «2p, molecular orbital which causes the reduction in the bond order in Ni, it becomes 2.5 in Nj from3 in Nz. Nj: ls? ols? 2s 0°28 n2p,? n2py? a2p.! Ny-N, 9-4 2 2 25 Bond order of NS But O3 is formed by the removal of an electron from the antibonding (n*2p,) or (x*2p,) molecular orbital which causes an increase in the bond order in O§, it becomes 2.5 from 2 in OQ, Of: ols ots 02 o'2e odp? mp2 n2p2n'2p Bond order of O} Cy “Demy LMethyleyelohexene © fads I H,C—CH; 1-Acetyiyclopentene (a): Oxidation state of ‘Tim TE? = +4 ie. Ti* —> 30° Co in CoP} = +3 ie. Co* —> 3a Nin NiClP = +2 ie, Ni" —> 3° Cu in CusCh +1 ie, Cu! —> 3”? Colour of salts is a property of partially filled orbitals, Since TiF?" has completely empty and CusCh has completely filled ¢-subshells, hence these are colourless salts. CHEMISTRY TODAY | FFSRUIARY'1¢ 13, 28. (d): Let there be 1 mol of iron atom. Amount of Fe (111) =() mot; aout atte (2) a ‘Total moles of positive charge 1 3 9 -( Jo(3 Jo2r=(2 mot Let x be the amount of oxygen atoms. Total moles of negative charge = 2x ‘To satisfy electrical neutrality, ‘Total moles of positive charge = Total moles of negative charge 2 mol=2x + x=2 mol 4 Multiply eqn. (i) by 7 and (ii) by 3 then add, we get 2 1 3 3 Nag + $ Hayy > Net Hey 29413 x1 +4360% 2 AH! = 941.3 «5 + 436.0% 5 = 4701.65 + 654 = 1124.65 kJ mol Now subtract eqn (iii) from eqn. (iv), we get NH, —> Nyy + 3H ol) AH® = 1124.65 ~ (46.0) kJ mot"! = 1170.65 kJ mol” Since there are three N—H bonds in NH, the average bond enthalpy is obtained by dividing the value of AH? of eqn. (v) by 3. 117065 (iv) Hence, AH yy = = 390.2 KJ mol 29. (c): Given Nagy —> 2No AH? Hyg) —> 2H yy 7 AH 30. (a): Structure (X) is of sucrose, a disaccharide which is a non-reducing sugar. Thus, it does not react with Tollen’s reagent whereas (Y) is maltose, a reducing sugar. 1 3 Nag? 3 Hag) —> NH Al CLASSROOM STUDY MATERIAL ATTENTION COACHING INSTITUTES EM ete] offers "Classroom MTGswway Material” for JEE (Main & Advanced), AIPMT and FOUNDATION MATERIAL for Class 8, 9, 10, 11 & 12 with YOUR BRAND NAME & COVER DESIGN. This study material will save you lots of money spent on teachers, typing, proof-reading and printing. Also, you will save enormous time. Normally, a good study material takes 2 years to develop. But you can have the material printed with your logo delivered at your doorstep. Profit from associating with MTG Brand — the most popular name in educational publishing for JEE (Main & Advanced)/AIPMT/PMT Order sample chapters on Phone/Faxle-mail Phone : 0124-4951200, 09312680856 e-mail : sales@mtg.in | www.mtg.in Your logo here 14 ciemistay toDaY FeeRUARY 14 kkk neo elueel] NCERT wk Questions for Medical/ Engineering Entrance Exams “Atract istry, in) Everyday) life |. Lactose is a disaccharide of (a) a-D-galactose and a-D-glucose (b) B-D-galactose and B-D-glucose (6) o-D-galactose and P-D-glucose (@) B-D-galactose and c-D-ghicose. Which of the following is a biodegradable polymer? (a) Nylon-6, 10 (b) Buna-N (9. PHBY (@) Teflon Identify the correct statement. (a) Amylose is insoluble in water while amylopectin is water soluble. (b) Both amylose and amylopectin are insoluble in water. (6) Both amylose and amylopectin are soluble in water. (d)_ Amylose is water soluble while amylopectin is insoluble in water. Which of the following is not used as an artificial sweetening agent? (@) Aspartame (© Alitame (b) Saccharin (d) Novestrol Which of the following statements indicates the cyclic structure of glucose? (a) Glucose gets oxidised to gluconic acid on reaction with bromine water. (b)_ Glucose on heating with HI forms n-hexane, (©) Glucose does not give 2, 4-DNP test. (a) Allof the above. 10. 1. Which of the following is a synthetic rubber? (a) Teflon (b) Natural rubber (©) Chloroprene (@) Neoprene Scurvy is a disease caused by the deficiency of (a) vitamin D (b) vitamin C (6) ascorbic acid (4) both () and (c). Which of the following is an incorrect statement? (a) 0.2% solution of phenol is a disinfectant. (b) 1% solution of phenol is an antiseptic. (©). Penicillin G is a narrow spectrum antibiotic. (4) Both (a) and (b). Glycine (a) exists as a zwitter ion (b) shows optical activity (6) contains two carboxyl groups (d) contains two amino groups. Which of the following is not an antidepressant drug? (a) Iproniazid (b) Phenelzine (9. Meprobamate (qd) Seldane Mark the wrong statement about denaturation of proteins, (a). The primary structure of the protein does not change. (b) Globular proteins are converted into fibrous proteins. (Q) Fibrous proteins are converted into globular proteins. (a) The biological activity of the protein is destroyed. CHEMISTRY TODAY | FFamUARY "Ts 15, 12, What type of polymer is represented by the following segment? ° ° Il Il —C—CH,CH, —C—0CH,CH,O— (b) Polyester (@) Polyethylene (a) Polyamide (©) Polyolefin 1B. All carbohydrates respond to (a) Tollen’s test (b) Molisch’s test (6) Schiff's test (@) allof these. 14, Among the following, the non-narcotic analgesic (a) Codeine (b) Morphine (9) Aspirin (@) Heroin. 15. Bakelite is a product of the reaction between (a) formaldehyde and NaOH (b) aniline and urea (Q)_ phenol and methanal (d)_ phenol and trichloromethane. 16, The pyranose structure of glucose contains, (a) sixmembered ring (b) epoxy linkage (9) hydroxy groups ” (d) all of these. Which of the following enhances lathering property of soap? (a) Sodium carbonate (6) Sodium rosinate () Sodium stearate (d) Trisodium phosphate 17, 18. Which of the following is a polyamide? (a) Teflon (b) Nyion-6,6 (©) Terylene (@) Bakelite 19, Caprolactam is the monomer of (a) Nylon-6 (b) Nylon-6, 10 (©) Nylon-6, 6 (€) Nylon-2,6 20. Reaction of glucose with acetic anhydride Indicates the presence of (a) —CHOgroup —(b) — CH,— group (©) five —OF groups (4) all of these. Thiamine is the chemical name of vitamin @ B&B © Bp @)% 22. Formaldehyde is not used for manufacture of (a) bakelite (b) urea-resin (©) melamine-resin —(d) dacron Which of the following statements is not true vzyme inhibitors? the catalytic activity of the enzyme. Prevent the binding of substrate. (©) Generally a strong covalent bond is formed between an inhibitor and an enzyme. Inhibitors canbe competitive or non- competitive. 21. 16 CHEMISTRY TODAY | Fesnuany ta 24. 25. 26. 27. 28. 29. 30. 3. 32. 33. 35. The tensile strength, elasticity and resistance to abrasion can be increased by a process called (a) diazotisation ——_(b)_ vulcanization (©) isomerization (d) polymerization. Which of the following is the basic amino acid? (a) Lysine (b) Glycine (6) Leucine (d) Alamine Amylose is a long unbranched chain of -D-(+)-glucose units held by glycosidic linkage. (a) Cl—Co (b) Cl-c4 (9 C2-C6 (a) C2-C4 Glyptal is the polymer of (a) ethylene glycol and terephthalic acid (b) phenol and formaldehyde (©) 1, 3-butadiene and acrylonitrile (d) ethylene glycol and phthalic acid. Equanil is a/an (a) artificial sweetener (b) tranquilizer (©) antihistamine (d) antifertility drug Which of the following is addition homopolymer? (a) Teflon (b) Pvc (0) Polystyrene (d) Allof the above, Structurally a biodegradable detergent should contain a (a) normal alkyl chain (b) branched alkyl chain ()_ phenyl side chain (d) cyclohexyl side chain Tincture of iodine is (a) aqueous solution of I; (b) solution of I, in aqueous KI (6) alcoholic solution of I; (d)_ aqueous solution of KI Which of the following is thermosetting, polymer? (a) Polythene (b) Nylon-6,6 (9) Bakelite (@) Buna-S Which of the following is not an antibiotic? (a) Chloramphenicol (b) Streptomycin (©) Penicillin (@) Bithional Among the following, natural polymer is (a) Proteins (b) Starch (9). Buna-S (4) both (a) and (b). Which of the following is not used to preserve food? (a) Sodium benzoate (b) Salts of sorbic acid (6). Salts of propanoic acid (d) Glucose * saat oe 36. Which of the following chemicals is used as painy killer? (a) Phenyl acetate (6) Methyl acetate (6) Acetyl salicylic acid (d) Salicylic acid 37. 1, 3-Butadiene is one of the monomers of (2) Buna-S () Buna-N (©) Natural rubber (d) both (a) and (b). 38, The given structure is CHOW HA 0H 1 OHH HO) H Hoon (2), o-D-(*}-glucopyranose (b) B-D-(+)-glucopyranose (6) &-D-(}glucofuranose (a) B-D-(1)-glucofuranose. 39. Copolymerisation of 3-hydroxybutanoic acid and Shydroxypentanoie acid gives (a) PMMA. (b) PVC (9. PHBV (@) dacron. 40. Which of the following is a reducing sugar? (a) Lactose (b) Maltose (6) Sucrose (4) Both (a) and (by 41, Which among, bacteriostatic? (a) Penicillin (b) Ofloxacin (Q) Aminoglycosiders (4) Erythromycin the following antibiotics is 42, Crosslinking is present in (a) polythene (b) bakelite (9) nylon-6 (@) polyester. 43. Dettol consists of (a) xylenol + terpineol (b) chloroxylenol + terpineol (c)_cresol + ethanol (d)_ None of these. 44, CHOH CHOF HO AO. 1A Q 0K i ot OHH OH H H Hoon HOW Identify the correct statement Ste 4 SKILLS QUESTIONS (HOTS) i (a). Glycosidic linkage is between C-1 of galactose and C-4 of glucose. (b)_ Glycosidic linkage is between C-4 of galactose and C-1 of glucose. () Glycosidic linkage is between C-5 of galactose and C-2 of glucose. (a) Glycosidic linkage is between C-2 of galactose and C-5 of glucose. 45. Gammaxane is (a) DDT (b) hexachlorobenzene (HCB) (6) benzene hexachloride (BHC) (4) chloral. 1. b): HO HOH BD-Galactose P-D-Gucose 2. (©:PHBY is a biodegradable polymer as it undergoes bacterial degradation inthe environment. (a) {d): Novestrol is an antifertility drug, iC) 6 @ (4): The chemical name of vitamin C is ascorbic acid. Its deficiency causes scurvy (bleeding gums) 8. (d): 0.2% solution of phenol is an antiseptic while its 1% solution is used as a disinfectant. 9. (a): Glycine (Hj,N—CH,—COOH) exists asa zwitter ion (HyN’—CH,—COO->). 10. (d);: Seldane is an antihistamine drug. 1. (0) 12. (b):It constitutes condensation polymer having ester linkages 13. (b) 1 CHEMISTRY TODAY | FeamUARY'T8 17 15. (0: ou oH ont one chon eHcHo 25 . ‘benzyl alcohol CHOH oH oon oon oor" CH Qh Dro Dhoay- ba ba SP by 16. (d) 17. (b) 18. (b): Polymers having amide linkages are known as polyamides. NH,—(CH),—NH, + esate = nHOOC —(CH,),—COOH Adipicadd| linkage 'Q—(CH,),—CO4, NIE(CH, Nii 19. (ad: H I oO ne? avo, | , ats tC cuy ent Capraactar| Nolen 20. (e) : Acetylation of glucose with acetic anhydride gives glucose pentaacetate which confirms the presence of five OH groups. CHO HO cn, stats, dococty, dixon CH,OCOCH; 2. (@d 22. (@): Dacron is a polymer of ethylene glycol and terephthalic acid. 23. (o): Weak bonds such as hydrogen bonds, van der Waals’ forces are formed between enzyme and inhibitor. 24, (b): Vuleanization is a process in which natural rubber is treated with 3-5% sulphur. It introduces sulphur bridges between polymer chains thereby 18 CHEMISTRY TODAY | Fesnuany ta 25. 26. 29. 30. 31. 32, 33. 34. 35. 36. 37. 38. 39. 40. a. increasing its tensile strength, elasticity and resistance to abrasion, {a):In lysine, number of amino (—NH) groups is greater than number of carboxyl (—COOH) ltd COOH uy—pn CH,—(CH,)s—-NH, tysine ©) zm. @ 28. (b) {d): Teflon, PVC and polystyrene are the examples of addition homopolymerisation as only single ‘monomer undergoes addition reaction. (a): Biodegradable detergent should contain a normal alkyl chain, {c):2:3% solution of iodine in alcohol-water mixture is known as tincture of iodine. (c): Polythene is thermoplastic. Nylon-6, 6 is a fibre, Bakelite is thermosetting polymer. Buna-S is an elastomer. (d): Bithional is used as an antisepticin medicated soaps. @ {d): Glucose cannot be used as food preservative because bacteria can utilise glucose and grow in food stuff and thereby contaminate it 0 {d); Buna-S is the copolymer of 1, 3-butadiene and styrene, Buna-N is the copolymer of 1, 3-butadiene and acrylonitrile Natural rubber is the homopolymer of isoprene (2-methyl-1, 3-butadiene). tb): CH,OH HA on on HO) iH HOH £:0.(+) Glocopyranose © {d): Both lactose and maltose are reducing sugars while sucrose is a non-reducing sugar. (a) 2. b) 43. (b) (a) 45. (0) 20 is sealed with an expansion bulb, The space above the liquid contains a mixture of nitrogen and the vapours of the liquid. Since the liquid is transparent, it is made more visible by the addition of a red or blue dye. YQU ASKED WE ANSWERED ; . Q3. In countries where temperature is below 0°C, Do you have a question that you just can’t get answered? which chemicals are used to keep water in Use the vast expertise of our mtg team to get to the bottom liquid state? ‘of the question. From the serious tothe silly, the controversial Harsh Panty, Varanasi to the trivial, the team will tackle the questions, easy and | Ans, Antifreeze and de-icers are used for this ‘ough purpose. An antifreeze is a chemical additive The best questions and their solutions willbe printed inthis Which lowers the freezing point of a water-based column each month, liquid. eg, methanol (CH;OH), ethylene glycol . | (CHOH),, propylene glycol (C3H,O3), glycerol QI. What chemicals are used to detect and identify (CoHiO) Antricing i understood tobe the breast cancer? . application of chemicals that not only de-ice, but ~ Suman, Delhi also remain on a surface and continue to delay Ans. Breath analysis, using the volatile organic the reformation of ice for acertain period of time, compounds (VOC) biomarkers of breast cancer, or prevent adhesion of ice to make mechanical and nanowire is an accurate and non-invasive removal easier. e., inorganic salts like NaCl diagnostic method. In this method, palladium, MgCl, CaCl, KCI and organic compounds polypyrrole and zine oxide nanowires, such as calcium magnesium acetate, potassium fabricated using electrochemical deposition acetate, HCOOK, HCOONa, CaHCOO)>. ‘method, periorm quick response and high ito coil sensitivity tothe four VOC biomarkers of breast | t+ RY should not we use mosquito coils at our cancer, including heptanal, 1-phenylethanone ome? , ~ Amit Sharma, Madhya Pradesh {acetophenone}, "isopropyl myristate and : 2propanol - Mosquito coils often contain BCME. [bis- ° (chloromethyl) ether] which is a dangerous, DPrroawroahe lung-cancer causing chemical. 5. What is the chemistry behind disappear Isopropy myristate are "y pearing (tropan2-l tetradecanoate) ° ~ Rohit Bhatia, Hyderabad ‘Ans. Disappearing ink is also known as security ink Q, not N Ly * olypyrroe) Nowadays, thermometers contain which chemicals other than mercury? ~ Pooja Verma, Saharanpur The alcohol thermometer also called spirit thermometer is an alternative to the mercury thermometer, and functions in a similar way. But unlike mercury, the contents of an alcohol thermometer are less toxic and will evaporate away quickly. An organic liquid such as pure ethanol, toluene, Kerosene or isoamyl acetate (isopentyl ° acetate) is filed in a glass bull J A. which is connected to a capillary 0 of the same glass and the end (samy! acetate) 20 cuemistay tooay | eons sa It is a mixture of thymolphthalein indicator, ethyl alcohol, sodium hydroxide, and water at pH 11. Thymolphthalein is a weak organic acid that behaves as an acid-base indicator in the pH range 9.3 (colourless) to 10.5 (blue). It exists in two different forms—an acid form Hind, which is colourless, and a corresponding conjugate base form Ind”, which is blue. When the blue ink is applied to paper, the blue colour quickly vanishes. The disappearance of the blue ink colour in air is due to the effect of CO2, which reacts with moisture in the air to form carbo acid (HyCO,)—the pH change is enough to push the basic form of the indicator (Ind’) back to its colourless acidic form (Hind). Oz + HzO = 1,003 H,CO} + Ind> —> HCO5 + Hind Blue Colourless =ARNZGSi ee Ma es Chemical kinetics deals with 2 study of the rates of chemical reactions. 9 factors affecting the rates of the reactions. 2 mechanism by which the reactions proceed. Classification of Reactions on the basis of Rates Very fast reactions : Some reactions such as ionie reactionsoccurvery fast. Forexample, precipitation of silver chloride occurs instantaneously by mixing of aqueous solutions of silver nitrate and sodium chloride. Very slow reactions : Some reactions are very slow, For example, rusting of iron in the presence of air and moisture. Moderate reactions : Reactions which are neither very slow nor very fast but take place at moderate speeds. Reactions like inversion of cane sugar and hydrolysis of starch, which proceed with a ‘moderate speed. Rate of Reaction Moles of reactants used ___ x “Time required for this change | Change in concentration _ dy at O Rate = O Rate TTime taken for change Its unit is mol Ls U. Fora reaction, A + B, the rate may be expressed in two ways: Decrease in concentration of A 5 Time taken [A] ar where [A}: and [A], are molar concentrations. of A ata time t and t respectively. ss in concentration of B Time taken ALB) oh AE where [B]; and [B], are the molar concen- trations of B at time f and f, respectively. Significance of -ve sign ‘The concentration of reactants decreases during a reaction fc, A(A] = [Ap ~ [Ah =-ve Therefore, a4) will be negative. But the rate of reaction is always positive. So a (-) sign is put before al so that SIA] 55 positive. For the reaction, 2P+3Q—S AR +58 AP] 2 dt Rate = 3 dt 4 de Average rate of reaction : It is the rate measured over a long time interval. AY at Instantaneous rate of reaction : It is the rate at any moment, ie, when time interval is very small. Average rate of reaction Concentration of protucts —> Time—> CHEMISTRY TODAY | FF5mUARY 18 21 Factors Affecting Rate of Reaction Concentration of the reactants : In most cases, rate of a reaction increases by increasing the concentration of reactants. Presence of a catalyst : A catalyst increases the rate of a reaction. Temperature of the reaction : Usually reactions are faster at higher temperatures, O_ Nature of reactants : Rate of reaction depends on nature of reactants ie, the type of bonds which have to be broken for reaction to occur. Exposure to light : Normally reactions proceed faster in presence of light. G. Surfacearea of solid reactant: Reactionsinvolving a solid with liquid or gas occur on surface and are faster when surface area is more Law of Mass Action This law was given by Guldberg and Wage, 1864, According to this law, “Ata given temperature, the rate of a reaction at a particular instant is proportional to the product of the active masses of the reactants at that instant raised to the powers which are numerically equal to thenumbers of their respective molecules in the stoichiometric equation describing the reaction’, (Active mass = Molar concentration of the substance oe vou Q For the reaction, A+B —> mM + nN Rate, re [4] [B}° r= ey (BP where k is the proportionality constant named as rate constant, Rate Constant For the reaction, A Products dy If [4] =1 then & [4] en For the reaction, aA + bB — Products ax _ ari ca nariah dx If[A]=[B]=1, then 2 [4] =[B] a 22 cxemistmy Tooay | eons sa © Thus, at a given temperature, the rate constant or specific reaction rate or velocity constant of a reaction, is equal to the rate of the reaction when the concentration of each of the reactants is uni Units of rate constant : Units of rate constant are different for different order of reactions. For the general reaction, aA+bB—> CdD Rate = KA]* [B]” where, x and y are the active moles of reactants A and B respectively. Hence, x+ det of reaction ye Rate (are Concentration 1 Time “(Concentration)” SI unit of concentration is mol L"! and that of time iss. Factors Affecting Rate Constant 2 Concentration : The value of rate constant for a reaction does not depend upon the concentration of the reactants. 2 Temperature : For every 10°C rise in temperature, the rate constant becomes almost double Energy of Thisarea shows activation — fraction of adaitional molecules whieh react at (10°C) Fraction of Kinetic nergy —> “This area shows fraction of molecules which react at! Molecularity of Reaction 2 Itis the number of reacting species (atoms, ions or molecules) taking part in an elementary reaction, which must collide simultaneously in order to bring about a chemical reaction. Depending on the number of reacting molecules, reaction can be unimolecular, bimolecular or srimolectdar. © The reaction can be unimolecular when one reacting species is involved, for example, decomposition of ammonium nitrite. NH,NO, —> Nz + 2H,0 © Bimolecular reactions involve simultaneous collision between two species, for example, dissociation of hydrogen iodide, 2H > Hp + Is © Trimolecular or termolecular reactions involve simultaneous collision between three reacting species, for example, 2NO +0, —> 2NO; Molecularity above three is not usually seen. The overall molecularity of a complex reaction is equal to the molecularity of the slowest (rate determining) step. 2 Forexample, Decomposition of H,Os: 2H,0; > 21,0 +0, Mechanism: H,0; “> 1,0 +0 H,0, +0 > 1,0 +0, Rate = k{H;03], Molecularity = 1 Order of Reaction @ This defined as, the number of molecules of reactants whose concentration determines the rate Jaw expression or it is the sum of the exponents Comparison between Molecularity and Order of React Molecularity of reaction It is the total number of species taking part in a chemical reaction. to which the concentration terms must be raised to express the rate of reaction from experimental data, For the reaction, aA + bB —> Products According to rate law, Rate = KAJ’ [BP Order of reaction =x +y For examples, NOs) > 2NOa,) + 3 Orgs r=K(N,O5] Order =1 2 2NOye) —> INOp) + Ox r=K{NO,P Order =2 2 2NOg) + Or) —> 2NOxey r=K{NO}[O2] Order =3 © CHCHO—> CH, +CO; r=k{CHsCHOP? Order = 3/2 O 2NH; —> N,+3Hy;r=k{NHg]” Order =0 tion Order of reaction It is the sum of the powers of the concentration terms of the reacting species in rate law. Itis a theoretical concept. It isan experimental quantity. Itis derived from the mechanism of reaction. It can neither be zero nor fractional. Its always a whole number. Itis independent of pressure and temperature. It is derived from the rate expression. Tt may be zero, fractional or an integer (may range from 0 to 3). It depends upon pressure and temperature. ‘Types of Order of Reactions Zero order reaction : In a zero order reaction, rate is independent of the concentration of reactant. For the reaction, A —> Products a 0 Attime! (@-x) x oe ap. 0 Rate= [P= KA]? =K(a—ayf On integration, tab k= slope ai 2 Examples of zero order reaction © The photochemical combination of Hy and Ch © Decomposition of ammonia on ahot platinum surface at high pressure. First order reaction : In the first order reaction, rate is determined by the change of one concentration term only. For the reaction, A — Products dy (a-a) apt (a-x) Rate=# (2-2) or kilt On integration, ig. -Infa—x)=K+e where c is an integration constant, when f=0,.=0 then -Ina=c CHEMISTRY TODAY | FFaRUARY "TS 23 -Ina-x)=kt~Ina or kt=Ina—In(a-x) or t= a 2303, a t 8G x) O T=n*ti where T= total time and n=number of halflives. Fora first order reaction Ty = 2 * Tya; T375=3 * Ts; T999 = 10 * T59 Examples of frst order reaction O CypHOy + HOS CH:0, + CHO, 2 $0,ClL —> SO, +Cl, 2 Allradioactive decays © NHNO, —> N; +210 Second order reaction : reactions, rate is determined by the variation fof two concentration terms or second power of concentration © When both the reactants are th For the reaction, 2A —> Products dx dt On integration, In the second order ka-x?? x wax) © When two different reactants having initial concentration @ and react with each other as given below A+B — Products as Fab) so On integration, «= 1.2503 jog Ma=¥) F (@-b) Pe ab—x) i 24 eHeMistRY TODAY | Fesauaav 1a 2 Examples of second order reaction © The hydrolysis of ester in presence of alkali 2 20;—>30, © 2N,0 —> 2N2+ Oz Q. Third order reaction : A reaction is said to be of the third order if the rate of reaction depends upon three concentration terms. A4+B+C —> Products 2A +B —> Products 3A —> Products ‘The simplest case in the reaction of last type. The expression for the rate constant of such a reaction may be: For the reaction, 3A —> Products, a gw? ae hla~ay “a Onin te} 2 © 2b @ (a-x)P ee iAP = 2 Examples of third order reaction 2 2FeCh, + SC —> SnCl, + 2FeCh, © 2NO+ Br, —> 2NOBr a! order reaction : In general, a reaction of the a order, where all the initial concentrations are the same, has a reaction rate ax ‘yt okies 1 1 1 (@tL@=xn"t ay 1 5 ata hyp op oF yp alt 2 1a oe Oa Or a ay Half-life of Reaction (fy:) It is the time in which the concentration of a reactant is reduced to one half of its initial concentration. 1 a a where, 1 is the order of the reaction. fe a Fractional order reaction ; There are some reactions for which order of reaction is not an integer. eg. Decomposition of CH;CHO CH,CHO —> CH, +CO Rate = k[CHsCHO}? Negative order reaction : There are some reactions for which rate of reaction decreases as the concentration of one of the constituent increases. ‘A negative reaction order just means that if we increase the concentration of the reactant, the reaction rate will decrease. Summary of rate law, integrated rate law, half-Ii different orders: eg, 20; > 302 Rate = K{Os}*{O.}" Therefore, the order of reaction with respect to oxygen is, Pseudounimolecular Reaction CH,COOCH, + HO CH,COOH + CH,OH According to law of mass action, given reaction should be bimolecular, but as water is present in large excess, its concentration remains practically constant, so, does not affect the rate of reaction. Hence reactions showing such a behaviour are called psewdounimolecilar reactions and also known as pseudo first order reactions fe, unit of rate constant and graph for the reactions of (ose Rss sna a Haltlife [Unit of al Gaph] constant | 0 Rate=#A]? [A] =-kt + [Alo mol L's! [A] vs t; slope = 1 [Rate= fa]? tna, = H+ in [Ap al Tinta] os rope =| 2 Rate=s(4)? —WlAje= t+ VLAlp tya= UkIAlp Lmot's' Ufa} est:slope=x ee ee tA molt oe eee 2 Rate= ANB Ea api] (ta Welle Lmot [A] 2st; slope=k nm Rate=s{ap | (kt — Rate= Fay" (#1). lar Methods of Determining Order of Reaction a Method of integration (Hit and Trial method): It involves the substitution of experimental values of @ and x at a given time, in different rate ‘equations, The equation which gives constant value of k will suggest the order, © Hall the reactants are at the same molar concentrations, the kinetic equations are: ~ For zero onder reaction, k= Hay -0) = Forssk b= 22g (a-x) - Ferssondonersacton k= tf 1 | il@-» @ - Ferntree | a (asp Graphical method : It involves determining the zate for a given change at different concentrations of reactants. ©. Graphs are then plotted between rates and concentrations, the nature of which suggest the order, en thtst | yet BE e=piagt OE AT Nae ote t | BArenter EL AAtenser | /itrorter Conc—> — Cone— (Conc F— (Cone > —> Rate os Concentration Plots 2 Fractional change method (Half-life method): It involves conducting the reaction at different concentrations and determining time required to complete a definite fraction. It involves the use of the general expression for the halflife and plotting the half-life (tya) 0% concentration (a"-") 1 ies tye © For zero order reaction, tia a © For first order reaction, iy is independent of ie. typ = constant © For second order reaction, ty. 1/4, i = constant. ta © Forthird order reaction, ty) i. typ @ = constant CHEMISTRY TODAY | FFaRUARY'T8 25 eh 7 2 In general, for n! order reaction, t= ie typ a"? = constant. ‘Thus, the nature of dependence of fy on the concentration of the reactant will give the order of the reaction. t t a2 4 rs Tender ft ord rs => = Effect of Temperature a ‘The rates of many reactions are approximately doubled ot tripled for every 10°C rise in temperature. Keei0 ‘Temperature coefficient (u) =" = 2 or 5 Arrhenius equation : k= Ae-'/S" E, 2303 RT where k= rate constant, A= pre-exponential factor (frequency factor) E, = activation energy, T= temperature loggk = logy A~ logiy2 = —E_| 2 "8104, 2303R| TT, (C= Intercept = logy A is Effect of Catalyst a 26 A catalyst is a substance which alters the rate of a reaction without itself undergoing any permanent chemical change. It participates in a chemical reaction by forming temporary bonds with the reactants resulting in an intermediate complex which decomposes to yield products and the catalyst Tt provides an alternate pathway or reaction mechanism by reducing the activation energy between reactants and’ products and hence lowering the potential energy barrier. Positive catalyst : Substances that increase the reaction rate by changing the path of reaction and Towering the activation energy. Catalystinhibitors/Negativecatalyst:Substances that reduce the action of catalysts reversibly. east tooat | con nt Catalyst poisons ; Substances that reduce the action of catalysts irreversibly. Catalyst promotors : Substances that increase the catalytic activity, even though they are not catalysts by themselves Reaction path Thoetecrofa \\ sister Potential energy —> Collision name> Collision Theory of Chemical Reaction 2 According to this theory © Molecules must collide to react. © When colliding molecules possess a certain minimum energy only then products are formed, such collisions are called effective collisions. © For effective collision, molecules must have a minimum (threshold) energy, molecules having lesser energy have to be given this additional energy, called activation energy. © Activation energy = Threshold energy — Energy of colliding molecules © Apart from possessing threshold energy, the molecules should be properly oriented to result in the formation of new bonds k= pze AT where Z is collision frequency and P is steric factor. Activated Complex Theory According to this theory © Breaking of old bonds in reactant molecules and formation of new bonds occur simultaneously. © Atsome stage an activated complex or transition state, is formed with old bonds partially broken and new ones partially formed. © Energy of the activated complex is higher than that of reactants and products. © The reactants do not directly yield the products, They have to cross the activated complex state, called energy barrier. © Height of energy barrier determines the threshold energy. . Foundati Qn Series JEE Maximi eRe =X CCE ce LST a ecm MMe te mocee oe Le Ma eae Reaune tel Ses ee y Tecan eM CUCM mee Cconal oe CTR eum OM Miura ieee a UNIT-8 BUCS CI a a Ee © Introduction ‘¢ Classification, structure, importance © Catbohydrates © Proteins * Vitamins © Nucleic acids Deane Carbohydrates (Sugars or Saccharides) Carbohydrates are primarily produced by plants and forma very large group of naturally occurring organic compounds. eg, cane sugar, glucose, starch, etc, Most of them have a general formula, CHO), and were considered as hydrates of carbon. Sunlight Ghlowophyi © Chemically, they may be defined as optically active polyhydroxy aldehydes or ketones or CO, + yO (HO), + 20 the compounds which produce such units on hydrolysis. Classification G Reducing sugars : Contain free aldehydic or ketonic group and reduce Fehling’s solution and Tollens’ reagent. 9 All monosaccharides and disaccharides having free aldehydic or ketonic group are reducing sugars. ¢.g., maltose and lactose. Q Non-reducing sugars: Do not have free aldiehydic or ketonic group and do not reduce Fehling’s solution and Tollens’ reagent. © In disaccharides, if the reducing groups of monosaccharides, ie, aldehydic or ketonic groups are bonded, they are non-reducing, in nature. eg, sucrose, 2 On the basis of their behaviour on hydrolysis: Carbohydrates ce] Po ‘Monosaccharides ‘Oligosaccharides Polysaccharides 1 ‘+ Cannothydrolyse further. + General formula: (CHO), where n=3-7 + eg.glucose, fructose. ¥ onhydrolysis. where m=2-10 * Yield 2-10 monosaccharides © General formula: (CoH j,Os),, + eg.suctose, maltose. t + Yield large number of monosaccharides on hydrolysis. + General formula :(CgHigOs), ‘where n= 100-3000 + eg.starch, cellulose. CHEMISTRY TODAY | FFaRUARY "TS 27 Nomenclature The names of the simpler carbohydrates end in ase, Carbohydrates with an aldehydic structure are known as aldoses and those with ketonic structure as ketoses. The number of carbon atoms in the molecule is indicated by a Greek prefix. MONOSACCHARIDES Glucose Glucose is an aldoses monosaccharide with formula CgH1O,. As it has six carbon atoms so categorized as aldohexose also known as dextrose. It occurs in ripe grapes, honey and most of the sweet fruits and also known as grape sugar. NumberofC | Aldose | Ketose | | Q It is the monomer of many of the large atoms in the carbohydrates, namely starch, cellulose ete. molecule 2 Preparation 5 TAldauese "| Keres ° Laboratory method + From sucrose (cane | a 4 Aldotetrose — Ketotetrose CoH: 0), +H,0 25S €,H),0, + CHO, Aldopentose | Ketopentose Sucrose Glucose Fructose = : © Commercial method : From starch 6 Aldohexose | Ketohexose Hay ac (Cally Og) + HO E> ne 0, 7 Aldoheptoxe | Ketoheptose Starch of Celuose K 268 Ghuone 2 Structure coon CH, CH, 4,CH,< nw ac SOS StS errs Gatiamrsadyae (GON Uke in assign) group) cH,OH Giuconic acid CH=NOH CHO a NHLOH SICH,CO,0 (CHOH), (CHO), > (CHOCOCHS), I Sie | an CH,OH ‘carbonyl group) CH,OH five —OH groups) (CH,OCOCH, Glucose oxime Glucose Glucose pentaacetale a coon re HNOyOxidation 1 Son HEN : (CHOH), | [indicates the presence ofa (CECE Sarre cee primary alecholic(-OH) COOH don casbonyl group) 2r00p] Gcaticaid or Saccharic acid Glucose eyanohydrin The exact spatial arrangement of different —OH groups was given by Fischer. D4}-Glucose 28 CHEMISTRY TODAY | Fesauaav 1a ‘ Glycarie act © Despite having the aldehyde group, it does not give 24DNP test, Schiff’s test and it does not form the hydrogensulphite addition product with NaHSOs, © The pentaacetate of it does not react with hydroxylamine indicating the absence of free = CHO group in glucose pentaacetate. © The above behaviour could not be explained by the open chain structure, CH,OH weD-(4>Glucopyranose The cyclic structure of glucose is represented by Haworth structure, ‘cH,OH Hf —0, 0H H Kon wy! HOY OH HO) H st H OH HOH W-D-4+Glucopyranose G_ Other reactions of glucose BD-(}.Glucopyranose d CH,OH D-ey-Chucose Reduction CHLOH (CHOH), < STE CH,OH Dueto Duet. Sorbitol jee {Glucose} s+ Oxidation Lew iad Cu,0! + Gluconice a8 ad Red Ppt acid Gren, src Tallens 2Agl + Gluconice Se I Se Sit acid ed Pentachioroghicose rior {Glucose pentachorice) O Tests Reagents With little cone. H2S0, CH,OH B-D-}-Glucopyranese © & and PrD-glucose have different confi- guration at anomeric (C1) carbon atom, and the C-1 carbon atom is called anomeric carbon (glycosidic carbon), © The six membered cyclic structure of glucose is called pyranose structure, hence are called anomers GHO scujcoct ies Cae cH,OCocH, Glucose penaactate (a mistureofa-and f+) oct Saeaee cron. I Tastee CHOM, G4 (FHOH), wn CH,OH cH,0H @:DMethylghicaside PD Methylghacaside Observations Charred residue of carbon. With dilute NaQH Molisciy’s test : Two drops of alcoholic solution of o-naphthol +2 drops of carbohydrate + cone. H:50, along the sides of tes tube. First yellow and then brown. Violet ring at the junction of two liquids. Silver mirror test : With Tollens’ reagent Silver mirror appears With Fehling’s solution Red ppt. of CuO. Fructose Fructose is a keto hexoses as it contains six carbon, and ketonic group. It has general formula CH). Its present in abundance in fruits and hence is called fruit sugar. a a Naturally occuring fructose is laevorotatory so also known as laevulose. In the combined state, it is present in disaccharide as sucrose and polysaccharide as inulin. CHEMISTRY TODAY | FFaRUARY "Ts 29 Q Preparation © From sucrose (cane sugar) i. 80, CigH2011 + Hy ——F*> CoH1206 + CoHi205 Cane sugar Glucose D-Frictose (Dextrorotatory) (Dextrorotatory) (Laevortatory The solution contains equimolar mixture of D-(Hy-ghucose and D-(-)-fructose is called invert sugar and the process is known as inversion, ©} From inulin BIH SO, (CyHjgO5), + 2HO $5 nH ,0,, Trlin Fructose Structure © On the basis of its reactions, it was found to contain a ketonic functional group at C2 atom and six carbon atoms in straight chain as in the case of glucose. It belongs to D-series and is a laevorotatory compound. It is appropriately written as D--)-fructose. Its open chain structure is as shown: (HoH c=0 HO=}— Ht H-}— on H3}— on ‘CH,OH DrFrucese © Italso exists in two cyclic forms which are obtained by the addition of — OH at C-5 to the (6C =O) group. The ring, thus formed is a five membered ring and is named as furanose. 1 Ia HOH,C—C—OH | HO—C—CH,OH © The cyclic structures of two anomers of fructose are represented by Haworth structures. ‘ 1 ‘ HOH Jo. Grou HOHE 6 on HHO / “An no wi "S/ou nN /cH0n on oH on H D4 Hctaranse oA. puttucnose Mutarotation 2. Glucose and fructose exists in two isomeric forms, ie, a-D-glucose (specific rotation = + 112°) and B-D-glucose (specific rotation = + 19°). However, when aqueous solution of either of these two forms allowed to stand, it gets converted into the some equilibrium mixture of both the o- and the feforms with a small amount of the open chain form, © Asa result of this equilibrium, the specific rotation of a freshly prepared solution of D-glucose decreases from +112° to +52.7° While that of B-D-glucose increases from 419° 1052.7, e-D-Glucose = Equilibrium = p-D-Glucose mixture [a]p= +527" falp=* 112" [a]o= +19" @ This change in specific rotation of an optically active compound with time to an equilibrium value is called mutarotation. All monosaccharides and reducing disaccharides Ho} og HOH Gg undergo mutarotation. Fructose also undergoes H—4+—oH| H—}— oH mutarotation, Nn HS o-D-Fructose = Equilibrium = B-D-Fructose Tuo ‘HOH mixture edi Fructofuranoe PDC} Fracofuranose alp=-21° [a p=-92°—far]p= 133° Comparison of Glucose and Fructose Property Glucose Fructose Molecular formula Cots eres Nature Polyhydroxy aldehyde Polyhydroxy ketone Optical activity of natural form __ Dextrorotatory Laevorotatory Oxidation (@) |with bromine water Gluconic acid No reaction (©) with conc. nitric acid Saccharic acid (glucaric acid) Mixture of glycollic acid, tartaric acid and trihydroxy glutaric acid 30 cHeMIstRY TODAY | Fesauaav 1a Reduction with NaBH, or Na-Hg/ | D-Sorbitol Mixture of | D-sorbitol and HO D-mannitol Fehling’s solution Gives red precipitate Gives red precipitate Tollens’ reagent Forms silver mirror Forms silver mirror Resorcinol + HCI (dil.) No colouration Gives red or brown colour or Gelivanof’s test) precipitate: Freshly prepared ammonium Light blue colour Bluish green colour on heating molybdate sol. + few drops of acetic acid (Pinoff’s test) Alcoholic a-naphthol + HCI (cone.) (Furfural test) DISACCHARIDES Q Disaccharides are formed when two monosaccharides are joined together by an oxide linkage (glycosidic linkage) formed by the loss of a water molecule. Sucrose (Cane sugar) Preparation Catb:Oiyy + HO Hydrolysis rSicse (seme CHi2Qetag * CoH: tavegae 4pGiucowe [alps #527 and Dacre [aly = 524° Structure + It is a disaccharide in which two ‘monosaccharides are held together by a gly’ linkage between C-l of d-glucose and C-2 of B-fructose. © Since the reducing groups of glucose and fructose are involved in glycosidic bond formation, sucrose is anon reducing linkage OH Ht PD-Fructose HOH eD-Giacose Sucrose © Itis dextrorotatory in nature. Maltose Q Preparation intros 24C Hy) + HHO nC oH 0, Starch Maltose No colouration A purple colour (violet) on boiling Structure + It is a disaccharide in which two D-glucose units are held together by a glycosidic linkage between C-1 of one glucose unit and C-4 of another glucose unit. 6 6 CH,OH CH,OH n Aso, | on HOH HOH eDGhicose — MHeCTVeIIdie gpaGlacose Noneducingunty —HMIARE — Geaducing uni} © It isa reducing sugar and dextrorotatory in nature Lactose (Milk sugar) Q Preparation CaH,:0j 4+ 0 (plane CHO; + CHE a) Dphiase DH). Galacte Structure : It is a disaccharide of f-D-galactose and B-D-glucose which are held together by a slycosidic linkage between C-1 of galactose and C-4 of glucose 6 ‘ CHOH CH,OH ) 0, mh oe H oH Un HOH HOW $Date BD-Glsse (Nonreduing uni) Reducing unt) © It is a reducing sugar and epimeric in nature. CHEMISTRY TODAY | F#5RUARV "18 34 POLYSACCHARIDES GQ Carbohydrates which yield a large number ‘of monosaccharides on hydrolysis are called polysaccharides. ¢g. starch, cellulose, glycogen, gums, ete, G_ They mainly act as the food storage or structural materials. They are non-reducing in nature due to absence of free aldehydic or ketonic group. Starch Starch is the main storage polysaccharide of plants. It is a polymer of ci-D-glucose units and consists of two components—amylose and amylopectin. © Amylose is water soluble component which constitutes about 15-20% of starch Chemically, amylose is a long unbranched chain with 200-1000. a-D-(+)-ghucose ur held by 1,4-tcglycosidic linkage. ‘Amylose © Amylopectin is insoluble in water and constitutes about 80-85% of starch. It is a branched chain polymer of a-D-glucose units in which chain is formed by 14-c-glycosidic linkage whereas branching occurs by 1,6-ceglycosidic linkage. O Structure buon Amylopectin Cellulose Cellulose is present in plants. It is not digestible by human beings. Q Itis the major constituent of cell wall of plant cells 32 qHEMIsTRY TODAY | Fesauaav 1a __Itisastraightchain polysaccharide composed only of B-D-glucose units which are joined together by 14-glycosidie linkages ic, the B-glycosidic linkages between C-1 of one glucose and C- of the next glucose uni 2 Structure 6 CH,OH HOH n Celtulose Glycogen 2 Glycogen is the carbohydrate which is stored in animal body. It is also known as animal starch. When the body needs glucose, enzymes break the glycogen down to glucose. It is a major constituent of liver, muscles and brain. 1 Itisalso found in yeast and fungi Key Points Humans do not contain enzyme, cellulase which hydrolysis cellulose into glucose. Q_ Cellulase is present in the stomach (rumen) of ruminant animals such as cow, buffalo, etc, and hence cellulose is easily digestible by them, 2 Importance © They are storage molecules as starch in plants and glycogen in animals. Cell wall of bacteria and plants is made up of cellulose. © They are used in the form of wood, as furniture and clothe ourselves with cellulose in the form of cotton fibres. © They provide raw materials for many important industries like textiles, paper, lacquers and breweries. © They are the major components of nuc! acids, RNA and DNA, PROTEINS Proteins are the biomolecules of the living system made up of nitrogenous organic compounds by condensation polymerisation of a-amino acids. ing BMV pomtigees LHtelsis Proteins ¥"** > Peptides "> Amino acids © Major sources of proteins are milk, cheese, pulses, fish, meat, peanuts, et. Amino acids Amino acids are the bifunctional molecules with, both acidic carboxylic group (— COOH) and basic amino group (— NH,) Q_ Ina-amino acids, the amino (— NH) group is at, a-position w.rst. carboxylic (— COOH) group. i., both amino and carboxylic groups are attached to the same carbon atom. They are very important as they are the building blocks of proteins. COOH (R= side chain) H cw-Amino acid “Histidine —cH, His Ann n=! Proline H Pro HN: ‘COOH "Essential amino acids Classification of Amino acids J Depending upon the relative number of amino (=NEb) and carboxyl (COOH) groups. Neutral] No. of COOH groups = No. of —NH, groups =e | €g., Glycine, Alanine, Valine symbol ' ' - Acidic thse = ¥ No. of COOH groups > No. of —NH, groups| Alanine CH; Ala €g., Aspartic acid, Asparagine, Glutamic acid *Valine —CH(CH,)2 Val *Leucine ~CH>CH(CH)p Leu Basic : No. of — NH) groups> No. of —COOH groups| Isoleucine =CH-CHSCH, Ih a soleucint T TM) ls eg, Lysine, Arginine, Histidine CH, “Arginine “(GNHLC_NH, Arg | | 2. Onthe basis of their synthesis: 1" Bt “Lysine ~>(CH2)NH2 Lys Glutamicacid|-CH,CH,COOH | Glu ¥ Y 7 a eeneoor 7 Essential Non-essential stint 7 =P amino acids amino acids Glutamine -CH,CH;CONH, Gln v iu Asparagine | ~CH;CONH Asn Cannot be synthesised][Which can be in the body and must bel| synthesised in. the eae ae oo obtained through diet. |} body. Serine —CH,OH Ser E.g. valine, leucine,|fEg. glycine, alanine, lysine, isoleucine|fglutamic acid, Cysteine ~CHLSH Gs arginine et, Ssparticacid ete “Methionine |-CHCH;SCH; Met *Phenylalanine | Glucose + Glucose Lactase Lactose —> Glucose + Galactose Amylase Starch 1 * Glucose Invertase Sucrose -» Glucose + Fructose Pepsin Proteins > @-Amino acids Trypsin _ Proteins + a-Amino acids Urease Urea CO; + NH Nuclease DNA, RNA Nucleotides Emulsin Cellulose — 1 x Glucose Properties Enzymes are needed in very small amount. They reduce magnitude of activation energy. © They are highly specific. They work at specific pH. © They work well at moderate temperature. Mechanism © Bindling of the enzyme (£) to substrate (S) to form a complex called the enzyme-substrate complex. E+S—>ES © Formation of complex product ES—> EP of enzyme and Vitamin name | Chemical name © Release of product from the enzyme-product complex. EP—>E+P 2 Importance © They play a vital role in living organisms as they catalyse many biological processes. © Even its deficiency causes diseases eg., the deficiency of phenylalanine hydroxylase enzyme causes phenyl ketone urea (PKU) and the deficiency of tyrosinase causes albinism. © They are used for the production of beer, wine, syrup and cheese also. VITAMINS. Q These are complex organic molecules which cannot be produced by the body and must be supplied in small amounts in diet to carry out essential metabolic reactions which are required for normal growth and maintenance of the body. 2 Classification Water soluble vitamins * Solublein water. | | J+ Mustbe supplied regularly in dietas they | are regularly excreted in urine (except 2 vitamin B,). Eg,, Vilamin- By, By By, ByyandC Fat soluble vitamins * Solublein fatand oils. = Stored in liverand adipose tissues. Eg, Vitamin-A,D, Eand K Sources Deficiency disease Vitamin A Retinoids (retinol, Milk, butter, eggs, fish, cod | Night-blindness, retinoids and liver oil, green vegetables, etc. | xerophthalmia carotenoids) Vitamin B, | Thiamine Water Pulses, nuts, cereals (rice, | Beri-beri, loss of appetite wheat, etc), rice bran, yeast, egg yolk, fruits and green vegetables, etc Vitamin By | Riboflavin Water Milk, green vegetables, egg | Anaemia, inflammation white, meat, liver, kidney, etc. | of tongue, dermatitis, cheilosis Vitamin Bs | Pyridoxine Water Rice bran, whole cereal (wheat, | Affects central nervous gram), yeast, fish, meat, eggs, ete. 36 CHEMISTRY TODAY | Fesauaav 1a system, causes weakness, convulsions, insomnia, anaemia Vitamin H | Biotin None Milk, yeast, liver, kidney, ete, | Dermatitis | Vitamin Bj | Cyanocobalamin Water Eggs, milk, liver of ox, sheep, | Pernicious anaemia fish, etc. Vitamin | Ascorbic acid Water Citrus fruits, chillies, sprouted | Pyorrhea, scurvy pulses, etc. (bleeding of gums) Vitamin D | Ergocalciferol Fat Butter, milk, eggs, fish liver il, | Rickets (bending of (a mixture of | and liver and meat (Vitamin D3 is | bones) and osteomalacia vitamins Dj | cholecalciferol produced in skin in presence and Ds) of sunlight), Vitamin E | Tocopherol Fat Wheat germ oil, milk, nuts, in males, peanut oil, cotton seed oil, muscle degeneration eggs, fish, etc VitaminK | Phylloquinone Fat Leafy vegetables like cabbage, | Haemorrhages and spinach, etc. lengthens time of blood dlotting Key Points Deficiency of more than one vitamin in the body causes many diseases. This condition Excess intake of vitamins (A and D) may cause hypervitaminoses, GQ Vitamin H (biotin) is neither soluble in water nor in fats. Most of the vitamins cannot be synthesised in our body but plants can synthesise almost all of them. However, the bacteria of the gut can produce some of the vitamins required by us, NUCLEIC ACIDS They are the polynucleotides present in nucleus of all living cells. They play an important role in transmission of the hereditary characteristics and biosynthesis of proteins. Chemical Composition of Nucleic Acids O Nucleicacids are the polymers of nucleotides. Ribonucleic acid (RNA). Deoxyribonucleic acid (DNA) 2 Pentose sugar 2 Deoxyribose : Itis also a carbohydrate (sugar) containing five carbon atoms but one oxygen less than ribose. Itis present in DNA. HOH, OOH HD i H OH H BD2.Deocyribose © Ribose: Itisa carbohydrate (sugar) containing five carbon atoms. Ttis present in RNA. HOH,C 0. oH HH Nucleotide ms 2H SS OH OH Pentose || Nitrogenous |[ Phosphate B-D-Ribose sugar base group (PO})| O Nitrogenous base : ‘These are heterocyclic 7 organic compounds having two or more [Poor ot nitrogen atoms in the ring. Ribose O-P-O NH, i f 9 ne : S wy N HN ‘CH Pyrimidine Purine tL q } 1 Uracil (U) Adenine (A) Sy of n ‘Thymine (1) Guanine (G) N x Cytosine (C) Adenine (A) Toymine (1) CHEMISTRY TODAY | FFaRUARY'T8 37 9 t is Structure A unit formed by attachment of a base to 1’ position of sugar is known as nucleoside. M9 yo wy a Ly J my 4 Ay oy Unciia w(6) Cosine) OQ nciynite ras bond ‘ii Sugar H ] on On Base Sugar Hinkage © The carbon atoms of the sugars are numbered as 1’, 2, 3, etc in order to distinguish from bases © When nucleoside is acid at 5’ po nucleotide. © Nucleotides are joined together _ by phosphodiester linkages between 5’ and 3’ carbon atoms of pentose sugar. linked to phosphoric tion of sugar moiety, we get a On On Phosphate Sugars inkage GQ Nucleic acid Ps eatoreran 38 cuemistmy TooAY | eons sa 2 Two types of nucleic acids, viz, DNA and RNA are distinguished from each other in the following manner: Deoxyribonucleic Components | Ribose nucleic acid (DNA) acid (RNA) 2-deoxy-D-() ribose Sugar D-(ribose Cytosine and Pyrimidine Uracil and thymine base oytosine Adenine and Purine base Adenine and guanine ‘guanine HPO, Phosphoric | HPO; acid Doublestranded Structure Single stranded achelix ochelix Possible Replication | Not possible James Watson and Francis Crick gave a double strand helix structure for DNA. Two nucleic acid chains are wound about each other and held together by hydrogen bonds between pairs of bases, The two strands are complementary to each, other because the hydrogen bonds are formed etween specific pairs of bases. Adenine forms hydrogen bonds with thymine whereas cytosine forms hydrogen bonds with guanine. 2 Insecondary structure of RNA, helices are present which are only single stranded. Sometimes they fold back on themselves to form a double helix structure. ase pair Hydrogen bone Sugar phosphate F badbone Chargatf’s rule Amount of purine bases is always equal to that of pyrimidine bases. Purine base of one strand of DNA molecule pairs with pyrimidine base of the other strand. Adenine (A) pairs with thymine (1) through two H-bonds (A= TD and guanine (G) pairs with cytosine (C) through three H-bonds (G = ©), Incase of RNA, adenine (A) paits with uracil (U), (A=U). RNA Messenger |[ Ribosomal |[ Transfer IRNAGn-RNA)|| RNAG-RNA) | | RNA(-RNA) Importance Replication is the process by which a single DNA molecule produces two identical copies of itself. Protein synthesis occurs in transcription and translation. 2 Transcription is the process of synthesis of RNA Translation : The synthesis of proteins occur in the cytoplasm of the cell. The m-RNA directs, protein synthesis with the help of r-RNA and FRNA. Genetic code : Linear sequences of three nucleotides (triplets) in DNA or RNA. that determines the specific amino acid sequence in the synthesis of proteins is called genetic code. tis the biochemical basis of heredity and nearly universal in all organisms. Mutation : Mutation may be defined as a change in nitrogenous base sequence of DNA molecule which leads to the synthesis of proteins with an altered sequence of amino acids. Mutation may cause genetic disorders or diseases. Es «Intoduction «Types, classification, methods of polymerisation, ‘copalymersation, some important polymers Dison es Polymers are very large molecules having high ‘molecular mass (10°-10"u). two. steps, ie, o o © These are also referred to as macromolecules, which are formed by joining of repeating, structural units monomers on a large scale. © This process of formation of polymers from respective monomers is called polymerisation. © All polymers are macromolecules but all macromolecules are not polymers, Types of Polymers 2 Depending upon the nature of the monomers, 2 Homopolymer : Polymer made up of only one type of monomer. eg., Polythene, Polypropylene, PVG, etc. nCH, = CHly PYMEMHHON SF CHE CHa}, Ethene Polythene © Copolymer: Polymer made up of two or more types of monomers. e., Nylon 6,6, Buna-S, Bakelite, etc. The process of formation of copolymer is called copalymerisation. = Copolymers have better physical and mechanical properties. The properties of copolymers could be changed by varying the amount of each monomer. INH(CH).NH Hexamethylene diamine potymerisation nHOOC(CH,)COOH Aap acid ; re a $N—(CHh),-N—C—(CH) CH, Nylon 6 6 Classification of Polymers Classification based on ->[Source/Origin 1. Natural polymers 2. Syntheticpolymers 3. Semi-synthetic polymers ->| Structure 1. Linearpolymers 2. Branched chain 3._ Crosslinked polymers | >[Molecular forces) T. Elastomers 3. Thermoplastics 2. Fibres 4, Thermosetting >| Synthesis 1. Addition polymers 2. Condensation polymers CHEMISTRY TODAY | FF5mUARY "Ts 39 Thermoplastics «| [Elastomers : Very Neither very strong] | weak intermolecular nor very weak, forces and possess Fibres : intermolecular forces like hydrogenbonds. Used for Quite strong] [Thermosetting] plastics : Extensive cross-links are formed between polymeric! chains on heating, Undergo permanent e.g. polypropylene, polystyrene, etc. ear polymers = Monomers are joined Donothaveany cross-| | elasticcharacters. making fibres, e.g. nylon- links between chains.| Jeg. natural rubber,| 6,6, polyacrylonitrile Canbe easily moulded] | buna-S,etc (orlon),et. onheating, change. e.g. bakelite, resin, et. Natural polymers = Substances of natural origin, i.e., found polymers having ‘branched chains. ‘e.g. amylopectin, glycogen, starchete. [Cross linked polymers : Initially formed linear together to form Pee mainly in plants and straight chains. eg./] sialesalbn ene animals. PYC, polystyrene, eg.silkenzymes, nylons, etc. natural rubber, based upon. based upon source | | haemoglobin, starch, Sranched hale siructure —( Polymers cellulose, proteinsete [polymers : Monomers : : lare joined to form tase upon Semisynthetic ‘i nici polymers : Derived irregularly packed mess by using natural polymers e.g. vulcanised rubber, nitrocellulose, cellulose xanthate, ete. Condensation polymers : Formed by combination of monomers with ‘polymer chains are joined together to form a three dimensional network e.g. bakelite, melamine formaldehyde resin (melmac), ete. ‘Addition polymers: Formed by addition of monomers without elimination of by-products eg. PVC, polythene, ete. structure Synthetic polymers Prepared in laboratory. Completely man-made. polymers. eg. teflon, dacron, synthetic rubber, nylon-66, ete. elimination of simple molecules like water, alcohol, ammonia, etc. eg. dacron —nylon-6,6, ate, Methods of Polymerisation Addition or chain growth polymerisation © In this type of polymerisation reactions, monomers are unsaturated compounds. Leads to an increase in chain growth through the formation of either free radical or ionic species (cation or anion). Depending upon the reactive particles formed. in this method of polymerisation, itis further divided into three types. (i) Free radical polymerisation (ii) Cationic polymerisation ii) Anionic polymerisation ° 40 caemistay tooat | ess sa (i) Free radical polymerisation: It takes place in three steps: © Chain initiating step + This step requires initiators which are free radicals produced on heating. eg. benzoyl peroxide, acetyl peroxide, dioxygen, ete ° Th nes RCM, a Etna». 9 tl No —C—R4> 2R-C—S—> 2K +20, CH, © Chain propagating step: The free radical thus formed adds to the double bond of the monomer to form larger free radical. cih=cH, R—CH,—CH, — 7 FT BCH CHa Cy R£CH,—CHy3,CH)—CHy © Chain terminating step : The growing, free radical chain consumes free radicals either by combination or by disproportionation to get polymer. = Combination . 2R-€CHy—CH,3,CH2—CH—, R-£CHyCHy CH CHCH;CHy-+CH;CH 3 R = Disproportionation ECA CCH Ot — R4CH;—CHy};CH=CHy Alene R4CH;—CHy}CHy Alkane —CHy (ii) Mechanism of cationic addition polymerisation: Initiated by the use of strong Lewis acids such as HE, AICls, HyS04, etc H3S0,—> H+ SO; H’ + CHa = CH; —> CHs~ CH3 ¢g. polyvinyl ether, polyisobutylene, polystyrene, ele (iii) Mechanism of anionic addition polymerisation: Initiated by strong bases such as NaNHy, CyHsLi and Grignard reagent, ete. B-cH,-CH corbanin eg. polyacrylonitrile, polyvinyl chloride and polymethyl methacrylate, etc. 2 Condensation or step growth polymerisation: In this type of polymerisation reactions, monomers are bifunctional and form bond with the loss of simple molecule of water, alcohol, ammonia, ete The dimer formed, also contain two functional groups , thus undergo a series of condensations ina stepwise manner and results in the formation of a high molecular mass condensation polymer. oO, Bt +CH, Preparation of Some Important Addition Homopolymers OQ Polyolefins Polymer Structure of monomer Structure of polymer | Polythene CH; = CH, 4CH;—CHy}, Ethylene Polypropylene CH;—CH = CH, lypropy! — Hts CH-CHyj, Polytetrafluoroethene C=C ¢CF—CPr}, (Teflon) (PTFE) Tetraforoethene Polyacryionitrile (CH; =CHCN CN (Orlon) (PAN) ‘Acrylonitrile I (Winyl cyanide) CHy-CH Polyvinyl chloride (PVC) CH, =CHCL a Chioroethene I (iy ehovide) CH, CHE Polystyrene (CH)—CH (Styron) 4 Polymethylmethacrylate CH (PMMa) CHy=C—COOcH, ¢ HC =C- I coche CHC Fy COOCH, CHEMISTRY TODAY | F5RUARY'T8 41 Polymonochlorotrifluoroethylene | Cl-C=CF (ectFe) } CHiorotefivoroethyiene Q Polydienes Polymer Natural rubber leoprene @Methyl-4, 3 butadiene) cl {f “} Foo Structure of polymer i CH, —C=CH— CH, cio, 4Polyisoprene Neoprene (synthetic rubber) a CH)=C—CH=CH, Chloroprene Chore, Sbutadiene) Gutta-percha Cs CHy=C-CH=CH, Tsoprene (2 Methyl, 3 butadiene) a CH; —C=CH— CHa: ee CH,—C=CH-CHy trans Polyfsoprene Preparation of Some Important Addition Copolymers O Polydienes Polymer Structure of monomer Buna-S CH; = CH—CH = CHa (Gtyrene Butadiene Rubber) 1, 3Butadione (SBR) cH Styrene Buna-N CH,=CH—CH=CH (Nitrile rubber) 1 -Butadiene (CH,=CH—CN ‘Acrylonitrile Preparation of Some Important Condensation Homopolymers G Polyamides Structure of polymer 4¢CH,—CH=CH—CH)—CH—CHy}; My (CH) ~ CH=CH ~CH,~CH)—CH3, Caprolactam 42 cHeMistRY TODAY | Fesauaav 1a Polymer |__ Structure of monomer Structure of polymer Nylon-6 (Perlon-t) see nd CH, a Who— ch NOH : C=0 ag. I — M Oecd sah (sae C5 2 soso Nylons © Cyeehanone Caprolatam (Gearon atom in epeting uit) Polyesters Polymer | Structure of monomer Structure of polymer Polyhydroxy butyrate on 01 (PHB) | il CH;—CH—CH,—CooH 0-CH CH, —Cj, “lydrowybutaoic acd &y Preparation of Some Important Condensation Copolymer @ Polyamides Polymer Structure of monomer Structure of polymer Nylon-6,6 HOOC—(CH,),—COOH M1 HO O Asipicaid A (crty,-n—-lcH il HNC) NF ~(CH,),-N—C—(CH).— Hexamethylenediamine Nylon-6 10 HOOC—(CH,)—COOH M1 ear ft (CH), -N—C—(CH)y—C een —(CH),—N—C—(CH)y—Cf. Hexamethylenediamine Nylon-2, 6 H)N—CH,—COOH {t OH fh | Md N=CH,—C—N—(CHy)5—C HN —(CH3);—COOH ‘-Aminoheranoie acid G. Polyesters Polymer Structure of monomer Structure of polymer Terylene HOCH,—CH;0H ° ° (acron) Eylene eyo) i il nooc~/_\-coon Terephthalic aia (enzenest, éliarboxyic aid) Glyptal HOCH,—CH,OH °e oO (Alkyd resin) Ethylene glyeol fl ol ome OCH,CH)—O-Cy_/CHe ‘COOH Phthalic ai (enzene-1,2-diarboxyic acid) CHEMISTRY TODAY | FFaRUARY'T8 43 Poly hydroxy on ° ° buatyeate-coh hyd buratecod hydroxy | cr, CH—CH,—COOH CuCl; C-0-C1-cay-E voles Prins te tren 1 (CH3—CH)—CH—CH)—COOH yen a Poly(glycolic acid) | HO—CH,—COOH eee ee poly(lactic acid) Glycolic acid TT y Ul (Dextron) CH, OCH; Of, i HO-CH—COOH Lactic acd Formaldehyde resins Phenol-formaldehyde resin (Bakelite) on OH ~ CHOH + HCHO) = —OF_, ae Formaldehyde Phenol vttydroxybenzy aeotol CH,OH SE eee Ls Morons rHiydroxybenzy! alcohol OH ow polymerisation oye se Linear polymer (Novolac) on On on CHy CHy CH) on on" . ee Gh sno-{O)-anoH o sore OW OH ” Bakelite (crosslinked polymer) “Melamine-formaldehyde resin (Melmac) 1 N nt H Bayern HN, WY NH—CH), c=0 fe Polymerisaton SNK NR me N < SO So NH NH NH " Melamine | Resin intermediate (monomer) Melamine-formaldehyde polymer 44 cHeMistRY TODAY | Fesauaav 1a Urea-formaldehyde resin NH,CONH, + HCHO —> +NH-CO—NH-CHs}, Formaldehyde Urea formaldehyde resin es “Monomers QO Polysulphide Thiokol Cl-CH,CH,—Cl IECH,CH,—S—S—S—S+ Ethylene dichloride NaS; Sodium tetrsulphide —— ‘Low density polyethylene (LDPE) ¥v ‘High density polyethylene (HDPE) ¥ ¢ Additionor chain growth homopolymer. ‘# Low density (0.92 g/cm) , low melting By heating ethylene under high pressure (1000-2000 atm) at temperature of 350-570 K in presence of traces of oxygen orperoxide. Free radical addition polymerisation Highly branched polymer. point (384K) ‘Transparent, moderate tensile strength. Chemically inert, tough but flexible. Used. for packaging, insulation and manufacturing squeeze bottles, pipes, toys,ete, Linearadidition or chain growth homopolymer. By heating ethylene at 333-343 K and 6-7 atm in presence of Ziegler-Natta catalyst Coordination polymerisation Linear molecules, closely packed. High density (0.97 g/em?), high melting point (403K). ‘Translucent Chemically inert, quite harder, greater tensile strength Used for manufacturing containers, housewares and pipes, ete. RUBBER Q Itis an example of elastomer. Natural rubber ° ° wnCH, CH) ° ° It is obtained from latex of rubber tree. It is also known as. cis-1,4-polyisoprene (about 5,000 units). cH, H H. cH, H Itisa linear 1, 4-addition polymer. It is elastic as the intermolecular forces present are weak van der waals’ forces. The cis configuration gives the polymeric chain of natural rubber a coiled structure, it can be stretched by the application of forces and returns back to original coiled shape when forces are removed © Gutia-percha ; All irans configuration occurs naturally as Gutta-percha, nas trans-polyisoprene, © Itisnon-elastic and non-crystalline. Synthetic rubber © Ttis obtained by polymerizing certain orgai compounds which may have properties similar to rubber and some additional desirable properties. Most of these polymers are derived from butadiene derivatives. These are also vulcanized. For example, neoprene, styrene butadiene rubber (SBR), thiokol, silicones, polyurethane rubber. CHEMISTRY TODAY | FFaRUARY "Ts 45, Cea Wels GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS Sn ¥ 2 Mined form) Oc: al Be ie angen gee sepa iar es Flementswhichare very reactive oceurinthe form oftheir com pouralselled mineral (metalsewstin oxidise form, non-metalsexstinreduced Bes The mires En hack cals en be Gorvesierily ec conn erate ee tale ones Fox Example Brat (AUO, S750) Heretic (Fo,0,, Magnesite Fe, Malachite (CuCO, C¢OH)s-Sphalert 225), Cuprite (CuO) Siderite(FeCO), ron pyres FeSyCopper pits (CUES). from ores \ rushing and Grinding (Pulverisation) of the Ore 2 tamps aoe SE sat pts 22> Fine poder oe oa Scns oma ara eee eee Brearacaee cerebral] eared Sele eae ree cH Fe0,3H,0 > FeO, +340 CuCO,CuOH), > 2Cu0 + CO,T+H,0 0 Reming «Suite co argh Pied a xt a prea A, ee ee ace ale ree eee See ee eee er eels mom Soe Boe a eee Fee res Eee Laan nee eee ees CN = moo Removal of unwranted materia, ganguecoe matrix rom the ore ialled ‘ore-dresingorlnefaction ofore. Theimportantmethods are o Hand picking, > Gravity separation or levigation or hydraulic washing : For oxide ove, based on dillerence in densities of ore (heavier) and gangue particles. eg hacmatittnstne, 2 Magnetic separation : Based on difference in magnetic properties. 2g, chuomite (FeOCr,03), magnetite (FeO) and pyroluste (Mas) being magmetcave separate from non-magnetic slices gong, Froth floatation : This method is based on preferential welling of ore (by oi) and gangue (oy wate) eg sulphide ones such as zinc blende (@s},copporpynits(CuFeS), galena(PbS).ct (Chemical method - Leaching: When ores soluble inasitablesolvents aye spaces For Al» fom baste. ‘Mas Ardhur-Frest cyan proces: For Ag and Au + from thelr native Ponte Extracted metliscontsminated with someimpuriy. © Distillation: The impure metal i evaporated to obtain pure metal 35 dlsilate For ow boiling points metas. Zn Hg, Cd 2 Liguation : Low melting metal gots separated from high melting Impusitiesby making it flow ona sloping surface For low melting points inelals.e Sa, Pb, Diet 9 Blectolyticrefinis + Impuremetal anode + Puremetal-»cathode + Solution of 2 soluble salt of metal + eeerlyte solution ‘+ On passing electricity insoluble impurities sate down below anode asorodemuton ate studge e4-Cu. Ag, Au, Ph.NLCE Zn Alot © Zone refining. Ta obiain ver high purity mele SiGe, B, Ga In As, fete, based on principle of fractional crystallization fe, difference in solubltesofimpurites in molten and in oli state of me © Vapour phase refining : Metal is converted to it volatile compound ‘whichisthen decomposed to give puromet + Mant rae for fing Nitsco 24> nico, Ni(CO), E> nivsco + nel ctl rr 22 0rTe 214, 2% 2a, 24, 22*> 20428 > Chvomatogrphy Base one prncipe hat diferent components ofa snistureareaterenty adhosbedenan adsorb o Paling: When impurities of own metal present og. CujO tn biter copperandS00, increta, © Cupelation: When impurites of ther metals present form volatile oxide eg Potracesin Ag Neoprene rubber : It is prepared by polymerization of chloroprene. Neoprene is superior to natural rubber in its stability to aerial oxidation and. its resistance to solvents. Styrene Butadiene Rubber (SBR) or Buna-S: Polymer of buta-l, 3-diene and styrene. It is very tough and is a good substitute for natural rubber. O Nitrile rubber (Buna-N) : Polymer of 1S-butadiene and acrylonitrile. Resistant to the action of petrol, lubricating oils and organic solvents, etc. Thiokol : Copolymer of ethylene dichloride and sodium polysulphide. Tt has slightly less tensile strength than natural rubber but is exceptionally resistant to chemicals. ‘Vulcanisation of rubber : It is heated with sulphur at a temperature of 373-415 K. Process of heating natural rubber with sulphur to improve its properties is called vulcanisation. Cross-links make rubber hard, tough with greater absorption tendency, resistant to oxidation and organic solvents. Sulphur forms cross-links at reactive sites. The extent of stiffness of vuleanised rubber depends upon the amount of sulphur added. Key Points _ PHBY, poly(glycolic acid) poly(lactic acid) and nylon-2-nylon6 are biodegradable polymers. 2 Biodegradable polymers are useful for medical goods, for controlled drug release and in agriculture materials EMail Introduction . Chemicals in food . Chemicals in mecicines Cleansing agents Dianne a In various areas, chemicals are used as 2 medicines for the treatment of diseases. © food materials © cleansing agents like soaps, detergents, household bleaches, tooth pastes, ete © synthetic fibres made up of chemicals only. CHEMICALS IN MEDICINES a Drugs are the chemicals of low molecular masses (- 100-500 u) which interact with macromolecular targets and produce a therapeutic and useful biological response. These chemicals are called Use of chemicals for therapeutic effect is called chemotherapy. Classification of drugs : Drugs are classified on the basis of, Drugaction + Itis based on the action of a drug on a particular biochemical process, + Antihistamines Pharmacological effect Analgesics (painkiller) ‘+ Antiseptics (kill or arrest the growth of microorganisms) + Antipyretics (reciuce fever) DRUGS, Chemical structure + Ttis based on the chemical structure of thedrug. * Sulphonamides YS ‘Moleculartargets It is based on the interaction with biomolecules such as carbohydrates, lipids, proteinsand nucleicacids. Therapeutic Action of Drugs a Antacids : Drugs which reduce or neutralise acidity. These drugs raise the pH of stomach to some appropriate level. Baking soda, metal hydroxides like AKOH)x, Mg(OH)s, cimetidine, ranitidine, lansoprazole, omeprazole are few ‘examples of antacids. 48 caemistmy tooay | cows sa Antihistamines (anti-allergic drugs) : Drugs which interfere with the natural action of histamine by competing with histamine for binding sites of receptor and therefore diminish its effect. © Histamines are the chemicals released by most cells during on allergic reaction. © Diphenylhydramine (Benadryl), pheniramine maleate (avil), chlorpheniramine (zeet) are few examples of antihistamines. Neurologically active drugs : Tranquilizers and analgesics are neurologically active drugs. These affect the message transfer mechanism from nerve to receptor. Tranquilizer : Its a class of chemical compounds used for the treatment of stress, mild and severe mental diseases. These are commonly called psychotherapeutic drugs. These are the essential component of sleeping pills. Some examples according to the action of drugs are: Narcotics: It reduces anxiety and tension. heroin, pethidine, etc. © Sedatives: It reduces the action of central nervous system. eg. valium, barbiturates. © Antidepressants (mood boosters) depression, e.., iproniazid, phenelzine, etc. © Chlordiazepoxide — and meprobamate, are relatively mild tranquilizers suitable for relieving tension. Equanil is used in controlling depression and hypertension. reduce © Hypnotics (sleep producing drugs): Barbiturates such as seconal, luminal, veronal. © Non-hypnotic drugs : Valium and serotonin. Analgesics : Drugs which relieve pain without causing impairment of consciousness, mental confusion, paralysis, © Now-narcotic : Drugs which do not cause addiction. eg, aspirin, paracetamol are analgesics as well as antipyretics. Aspirin is also used in prevention of heart attack due to ils anticlotting property. Narcotics: Their chronic use leads to addiction, eg. morphine, codeine, ete, Antimicrobial : Human beings and animals are prone to diseases caused by action of microorganisms such as bacteria, fungi, virus and other pathogens. Drugs which inhibit the action or growth of these microbes are antimicrobial Antibiotics, antiseptics and disinfectants are antimicrobial drugs. Antibiotics: These are the chemicals synthesised from microbes and have either cidal (killing) [Bactericidal] effect or a. static (inhibitory) [Bacteriostatic] effect on microbes. © Depending upon the range of microorganisms affected; antibiotics are classified as broad spectrum antibiotics and narrow spectrum antibiotics = Antibiotics which kill or inhibit a wide range of Gram-positive and Gram- negative bacteria are said to be broad spectrumantibiotics, Those effective mainly against Gram-positive or Gram-negative bacteria are narrow spectrum antibiotics. = eg. penicillin (a bactericidal and narrow spectrum antibiotic), ampicillin and amoxicillin (semisynthetic modifications of penicillin), ofloxacin (broad spectrum), ete. ~_ egerythromycin tetracydine, chloramphenicol (@ bacteriostatic and broad. spectrum antibiotic), ete. GQ Antiseptics : These are applied to the living tissues such as wounds, cuts, ulcers and diseased skin surfaces, © Examples are furacine, soframicine, dettol (a mixture of chloroxylenol and terpineol), 0.2% solution of phenol © Bithionol (also called bithional) is added to soaps, iodine, iodoform, etc, 2 Disinfectants : These substances kill or stop the growth of micro-organisms, but are harmful to living cells as well. So used on non-living objects like clothes, floors, utensils, etc. e.g. phenol, bleaching, powder, HO2 etc. © 1% solution of phenol is used as disinfectant. Q Antifertility drugs : These drugs are used to reduce birth rates. eg. mifepristone, silphium, ete CHEMICALS IN FOOD 2 Chemicals which are added to food for their preservation or enhancing their appeal, flavour, etc, are known as food additives. Artificial sweetening agents : These are the compounds which give sweetening effect and enhance colour and flavour of food. ¢g. saccharin, aspartame, alitame, etc. Artificial Sweetness value in sweetener __ comparison to cane sugar Sodium cyclamate 30-50 Aspartame 100 Dulcin 250 Saccharin 550 Sucralose 600 Alitame 2000 CHEMISTRY TODAY | FFaRUARY "Ts 49 Food preservatives : These are the chemical substances which are added to the food materials to prevent their spoilage and to retain their nutritive value for long periods, These preservatives prevent the rancidity of food and inhibit the growth or kill the micro-organisms, eg table salt, sugar, citric acid, sodium benzoate, salts of propionic acid, sorbic acid, etc Antioxidants : These are the chemical substances which prevent oxidation and subsequent spoilage of the food, These act as sacrificial materials, 1. they are more reactive towards oxygen than the materials they are protecting. They also reduce the rate of involvement of free radicals in the ageing process. e,, Butylated hydroxy anisole (BHA) and butylated hydroxy toluene (BHT), Key Point Q Artificial sweetening agents are inert and harmless thus excreted from the body in urine unchanged. Use of artificial sweeiners, is of great value to diabetic persons and people who need to control intake of calories. CLEANSING AGENTS Soaps : These are sodium ot potassium salts of higher fatty acids (with 16-18 carbon atoms) eg. Salts of CisHsCOOH (palmitic acid), CizHasCOOH (stearic acid), Ci-Hj;COOH (oleic acid), Ci7Hs}COOH (linoleic acid), et. ©. Soaps containing sodium salts are prepared by heating glyceryl ester of fatty acid with aqueous NaOH solution and the reaction is, known as saponification. © Only Na/K soaps are soluble in water and are used for cleaning purposes, Generally potassium soaps are soft to the skin than sodium soaps, Key Points Soaps do not work in hard water. Hard water contains calcium and magnesium ions. These ions form insoluble calcium and magnesium soaps respectively when sodium or potassium soaps are dissolved in hard water. These insoluble soaps separate as scum in water and are useless as cleansing agent. U_ Synthetic detergents : Also called as soapless soaps, as they have all the properties of soaps, but actually do not contain any soap. 50 cuemistay tooar | sw sa Used with both soft and hard water. © Chemically, these are sodium salts of long chain sulphonates and sulphates. These are classified as = Cationic detergents positively charged. eg. cetyltrimethylammonium bromide CHy(CHp) 5N"(CH3)38 ‘These are used as fabric softner and hair conditioner. = Anionic detergents : nogatively charged. ‘Their polar head is rheir polar head is 9 i £8 CHa (CH) y— CHO 8 “ON ° sodium Inaryl sulphate Such detergents are clothes. = Nonr-ionic detergents: Their polar head is neutral. eg. Polyethylene glycol stearate, (CHy(CH,);,COO(CH,CH,0),CH;CH;OH Such detergents are used in dish washers. used to wash Advantages of Synthetic Detergents over Soaps 2. They can be used in hard water, in acidie medium while soaps get precipitated. They are more soluble in water and thus form lather more easily. Q They are stronger cleansing agents than soaps as they decrease the surface tension to greater extent. Cleansing Action of Soaps and Detergents 2 In the micelles, the carboxylate groups form a negatively-charged spherical surface, with the hydrocarbon chains inside the sphere Because they are negatively charged, soap micelles repel each other and remain dispersed in water, Water nat NT ge = solublehead yyy ae (iiyarephitcy “ge a Not 7 as ae Cyaan Not Micelles Vi 1 Which of the following pairs give positive Tollens’ test? (a) Glucose, Sucrose (b) Glucose, Fructose (9) Hexanal, Acetophenone (d) Fructose, Sucrose A peptide made up of number of amino acids contains how many peptide linkages? (@) mb) HL ©) 20-1 @) maT The pyrimidine base, common in both DNA and RNA is (@) Thymine (b) Cytosine (0 Guanine (a) Uracil HOCH, ou In the structure, «(oy Si an anomeric carbon is HOS on fa) 1 by 2 (©) 3 @a ‘Tocopherol is the chemical name of vitamin fa) K by E (©) H (d) D In DNA, the complementary bases are (a) adenine and guanine; thymine and cytosine (b) uracil and adenine; cytosine and guanine (©) adenine and thymine; guanine and cytosine (d) adenine and thymine; guanine and uracil Which of the following sets contain only addition homopolymers? (a) Polythene, Natural rubber, Cellulose (b) Nylon, Polyester, Melamine resin (6) Teflon, Bakelite, Orlon (d) Neoprene, PVC, Polythene Which of the following is an example of non- biodegradable detergent? 0) crs ter {Oso (b) Cate (cHaicH-{O)-80,Na CH; eo © cert ony-br-(O)-sons (@) CHs—(CH,)g—CH,0SO;Na Questions for Practice 9. 10. ie 12. 1B. 4. 15. Phenacetin is used as a/an (a) antipyretic (b) antiseptic () antimalarial (a) disinfectant. Which of the statements about “Denaturation” given below are correct? (1) Denaturation of proteins causes loss of secondary and tertiary structures of the protein, (2) Denaturation leads to the conversion of double strand of DNA into single strand. (3) Denaturation affects primary structure which gets distorted. (a) Qyand 3) (b) and @) (9 (and @) (@) (1), @and @) Observe the given disaccharide and choose the correct statement. On Hi CHRO OH H Ay (By (a) Ring (B) is furanose with f-glycosidic link (b) Ring (A) is furanose with c-glycosidic link. (©) Ring (A) is pyranose with o-glycosidic link, (d) Both (a) and (c). In nucleic acid, base is linked to ____ of a pentose sugar and phosphoric acid is attached to of a pentose sugar. (a) C-5,C-2 (b) C25 {(Q CLC5 (a) C5, C1 Vitamin which is neither water soluble nor fat soluble is fa) K (b) Bir (@ H (d) D Which of the following sets of polymers contain biodegradable polymers? (a) PHBY, Nylon-2,6, PGA, PLA (b) PHBY, Nylon-6,10, PVC, PLA (0. PMMA, Nylon-6,6, PGA, PVC (4) Both (b) and (c). Match the list I with list IT andl select the correct answer using the cade given below the lists. List I List It P. Neutralaminoacid 1. Arginine Q. Acidicamino acid 2. Aspartic acid R._ Basic amino acid 3. Valine CHEMISTRY TODAY | F5AUARY'T8 51 P QR @1 2 3 2 103 @1 3 2 @3 2 1 16. Which of the following is not correctly matched? (a) Neoprene: fore} a » (b), Nylon-6, 6: se fe st ote ol, ¢ 6 tmyime focu-cry LO) CH; (@) PMMA;-£CH,—C3, boots 17. Asulpha drug used for the treatment of pneumonia (a) sulpha acetamide () sulphanilamide (b) sulphaguanidine (4) sulphapyridine. 18. Among cellulose, polyvinyl chloride, nylon and natural rubber, the polymer in which the intermolecular force of attraction is weakest is, (a) nylon (b) polyvinyl chloride (6) cellulose (a) natural rubber. 19. Match the list I with list Il and select the correct, answer using the code given below the lists List I List II P. Alkylbenzene 1, Antioxidants sulphonate Q Sodium oleate 2._Detergent R. Sodium benzoate 3. Soap S. Butylated hydroxy 4. Food preservatives toluene (BHT) PQRS @12 3 4 43 21 (23 14 @23 41 20. Identify the correct statement. (a) The starting material for the manufacture of PVC is obtained by reacting HCI with acetylene. (b) Natural rubber isa step growth polymer. (6) Dacron is addition polymer. (d) Intermolecular forces present in nylon-6,6 is H-bonding. 52 cuemistay tooar | eons sa 21, Which is the correct statement about birth control pills? (a) Contain estrogen only (b) Contain progesterone only (© Contain a mixture of progesterone derivatives (a) Progesterone enhances ovulation estrogen and 22, Match the list I with list IT and select the correct answer using the code given below the lists. List I List IT P. Phenol+Formaldehyde 1. Saran Q Terephthalic acid 2. Bakelite + Ethylene glycol R. Caprolactam’ 3. Nylon-6 S. Vinyl chloride + Vinylidine 4. Terylene chloride POoRS @ 123 4 4321 (243 1 @2 413 23. Which of the following is added to soaps for transparency? (a) Benzene () Ethanol (b) Ethyl chloride (@) Barbituric acid 24. ‘The chemical name for melamine is (a) 13,5-triamino-2,4,6-triazine (b) 2,4,6-triamino-1,3,5-triazine (9) 2amino-1,3,5+triazine (d) 24-diamino-1,3,5-triazine. 25. Barbituric acid and its derivatives are well known as (a) tranqui (©) analgesics (b) antiseptics (@) antipyretics, 26. The first step in bakelite formation is (a) aromatic nucleophilic substitution (b) aromatic electrophilic substitution ()_ condensation (d) electrophilic addition. oH Lastcadtion 27. CHs=C—CH=CHys oprene trans addition 5 y X and Y are respectively (a) natural rubber, gutta percha (b) gutta percha, natural rubber (©) natural rubber, natural rubber (d)_ gutta percha, guita percha 28. The bactericidal and bacteriostatic antibiotics lin, ofloxacin (b) erythromycin, tetracycline (©)_ penicillin, chloramphenicol (d) tetracycline and penicillin 29. ‘The compound that causes general antidepressant action on the central nervous system belongs to the class of (a) analgesics (b) tranquilizers ()_ narcotic analgesics (d) antihistamines. Adipic acid 30. Hexamethylenediamine fo ia Y Polymers X and Y are respectively (a) nylon-6; nylon-6, 6 (b) nylon-6, 6; nylon-6 (6) nylon-6; nylon-6, 10 (d)_nylon-6, 6; nylon-6, 10 Res Lo 2 @ 3 & 4 @ 5 6. (0 : DNA contains two types of nitrogenous bases. Purine : Adenine (A) and Guanine (G) Pyrimidine : Cytosine (C) and Thymine (1) Adenine pairs with thymine (A = T) by two hydrogen bonds and guanine with cytosine (G=O) by three hydrogen bonds. 7. (d): Neoprene is made from chloroprene, PVC from vinyl chloride and polyethene from ethene ‘monomers. 8. (0) : Greater the branching, greater is the non- biodegradability. 9. a) 10. (©) : Denaturation does not change the primary structure of protein. 1, (@): Ring (A) is_pyranose with a-glycosidie Tinkage while ring (B) is furanose with f-glycosidic linkage. 12. (©) 15. (dd B.@) 14. @) NH 9 een HN NH “NH Arginine asic) OH NE Aspartic add (Acide) +NH; Valine (eatrad) 16. (© 17. (a) 18. (d) : Cellulose and nylon are fibres and thus their intermolecular forces are the strongest. Polyvinyl chloride is a thermoplastic, the intermolecular forces in them are neither strong nor weak. Natural rubber has weak van der Waals forces, which are the weakest forces. 19. (a) 20. (b) 21. (© : Birth control pills contain a mixture of estrogen and progesterone derivatives. 2. (©) 23. (od): 24. (b): : Terylene contains ester linkage, OCH,—CH;—O—CO— For transparency, ethanol is added to soaps. NH, ry nant 26-Triamino 1 3Steiazine 25. (a): The most commonly used tranquilizers are barbituric acid and its 5, S-disubstituted derivatives such as veronal, luminal and seconal. 9 cn oy H Sea acid ee HOH 26. (b): act, on, “Shey palmer to give bake 27. (a) : LAcis addition reaction of isoprene gives natural rubber while 1,4-frans addition reaction of isoprene gives gutta percha, 28. 29. (b) 30. (@) : mMNH)—(CH,),—NH+ nHOOC—(CH;),— COOH. Hexamethylenediamine +€CO—NH~(CH}),—NH—CO—(CH),— CO} Niylon-66 MNHy—(CH3)-—NH3+ nHOOC—(CH,)g— COOH eats |g mse “20H Adipie acid ¢CO(CH;)sCO—NH(CH;),NH—CO(CH)-— CO Nylon-6, 10 = CHEMISTRY TODAY | FFaRUARY "Ts 53 CE CO 7 Sener Pama a Rearrange the following (1 to IV) in the order of increasing masses and choose the correct answer () Latom of oxygen (l) atom of nitrogen (Il) 1 « 10" g molecular mass of oxygen (IV) 1* 107 g atomic mass of copper. (@) U M," +2, the other metal (Mz) being univalent showing reduction takes up electrons to complete redox reaction (a) (1) ®1 @n @2 Which of the following is electron deficient compound? @) CH, & sin, (Q) PH; (A) Bo The TUPAC name of the given compound is ce (a) 2,4,4-trimethylhex-5-ene-3-ol (b) 3,3,4,4-tetramethylbut-1-en-2-ol (©) 33,5+trimethylhex-1-en-2-ol (d) none of the above, 13. Identify the product Z of the following reaction. uv500 K +a, 2 a a a. cl a. a fa) () a cl cr cl a a cl a od 14. The process of ‘eutrophication’ is due to (a) increase in concentration of insecticide in water (b) increase in concentration of fluoride ion in water (6). the reduction in concentration of the oxygen in water due to phosphate pollution in water (@) attack of younger leaves of a plant by peroxyacetyl nitrate solved 15. Potassium has a lice structure with nearest neighbour distance 4.52 A. Its atomic weight is 39 Its density will be (a) 454g m? (©) 852kgm? (b) 804 kg m™ (4) 910 kgm 16. The freezing point of a solution containing 0.2 g of acetic acid in 20.0 g benzene is lowered by 0.45°C. ‘The degree of association of acetic acid in benzene is [Assume acetic acid dimerises in benzene, K,for benzene = 5.12 K kg mol] (a) 94.5% (b) 98.7% (©) 68.4% (d) 33.4% 17. ‘The equilibrium constant K, for the reaction Cuiy * 2ABiay F Cefn) * ZAR (EZ) = 0.46 V) (a) antilog 15.6 (b) antilog 25 (©) antilog 1.5 (@) antilog 12.2 18, Therate constant for the first order decompo: of a certain reaction is described by the equation 1.25 = 10% T ‘At what temperature will its half-life period be 256 minutes? (a) 338K (9 490K log(k) = 14.34 — () 570K (@) 669K 19. Plot of log x/m against log P is a straight line inclined at an angle of 45°. When the pressure is 0.5 atm and Freundlich parameter, k is 10, the amount of solute adsorbed per gram of adsorbent will be (log 5= 0.6990) (@) 1g b) 2g ©) 38 (d) 5g 20. In the extraction of nickel by Mond’s process, the metal is obtained by (a) electrochemical reduction (b) thermal decomposition (c)_ chemical reduction by aluminium (d) reduction by carbon. 21. The number of P-O ~P bridges in the structure of phosphorus pentoxide and phosphorus trioxide are respectively (a) 5,5 (b) 6.5 © 36 @) 66 22. ‘The number of d-electrons in Fe is not equal to that of the {a)_prelectrons in Cr () Selectrons in Mg (b)_s-electrons in Fe (d) p-electrons in Ne 23. When one mole of each of the following complex salts is treated with excess of AgNO;, which of them gives maximum amount of AgCI? fa) [Co(NH),JCls (b) [Co(NH3),CIJCl, (9 [Co(NHY,ChICL (4) Nas{PtCl] BrlFe ZC BLA sca ° zk 24. CH» P. ‘The compound R is {a) o-bromotoluene (b) m-bromotoluene (©) p-bromotoluene (d) $bromo-2, 2, 6-trichlorotoluene 25. Which one among C,HJOH will be optically active? (a) Butan-1-o1 (b) Butan-2-01 (©) 2-Methylpropan-1-ol (d) 2-Methylpropan-2-ol 26. The increasing order of boiling points of the following compounds is ()_ 1, 2dihydroxybenzene (il) 1, 3-dihydroxybenzene (il) 1, 4-dihydroxybenzene (a) I = 2.6610 g, an u -—t {Ml Mass of one N atom = Ss 32x10 ¢ {Il} 1 g-molecule of oxygen = 32 g 110° g-molecule of oxygen = 32 = 10" =3.2x 10g (IY) 1 g-atom of copper = 63 g 110” g-atom of copper = 63 x 107 =63* 10% g ‘Therefore, the increasing order of masses are u x10° =5 g of CaCO, Hardness of given water sample= 5 ppm {(d): BoF Hydration energy =~ 2494 +2 x (457) ~- 3408 Lattice energy =- 2906 AFestim =~ 3408 ~ (2906) 502 kJ mol” Mgr, Hydration energy =~ 1921 +2» (-457) 2835 Lattice energy =-2610 AHgcaauon =~ 2835 ~ (- 2610) ==225 kJ mol eohton CaF: Hydration energy =~ 1577 +2 (457) 2491 Lattice energy =~ 2459 AHgciation ~~ 2491 ~ (- 2459) 32 kJ mol" BaP Hydration energy =~ 1905 + 2 (457) --219 Lattice energy =-2367 AHaoision =~ 2219 = (2367) 148 kJ mol AHgojnjon iS #ve in BaFy, hence BaF, is easily soluble in water, (0): The reaction shows MJ" +1 ie, electrons released at anode oe d@ eee sci j . {b): Under ultraviolet light, three chlorine molecules add to benzene ring to produce benzene hexachloride, CcH,Cly, also known as gammaxane. a ch, cl w Cha Benzene a a a 14, (o): Eutrophicationisthe term given toenrichment ‘of water bodies by plant nutrients. Itis the process by which lakes are enriched naturally or more usually by human activity, The key nutrients responsible for eutrophication are nitrogen and phosphorus, B 2 edd 28452 V3 1732 ZxM @xN, 15. (d): For bec, 35.219 A=522 pm 2x39 ~ any (6.02310) 10™ = 0.91 g/cm? =910 kg m> 16, (a); Given: w= 02g, W=20 g, AT=045°C 1000%K xx MxW 1000%5.120.2 ™Mx20 observed) = 113,78 (acetic acid) 2CH,COOH = (CH,COOH), Before association 1 0 After association 1a a2 (mol. wt acetic acid ~60) Mesos © op Oy ™ 2 378 Applying, AT;= or 0.45= « wr osered) 2 = 0.945 or 94.5% = log K,-1559 K,~ antilog 15.6 18. (d): Since the reaction is of first order, 0.693 256 60 or =451 10°s* Substituting this value in the given expression, ‘we get | log (4.51 10°) 1 4.34 7 1.25 10% or 4346 = 1434-0) 19. (d): According to Freundlich equation =kPM or log =logk+ Hoge Plot of log x/m vs log P is linear with slope = Ln and intercept = log k. 1 Thus + =tan@=tand5°=1 orn 10 ALP =05 atm and k ~ 210x(05) m ax=5g 20. (b): In extraction of nickel by Mond’s process, ‘metal is obtained by thermal decomposition. Ni+4C0 = Nico), aunt NCO} ZS ni 400 21. (dz P P oOo; ay 16 vé \. PYo- = =0 Pee eT ° oto oO nes 22. (a): Cr Fe? = 158,258 ph 3 Sp ah In Fe™, total number of d-electron: which is not equal to p-electrons in CI (ie, 12). 23. (a): When [Co(NHH,),JCl, is treated with excess of AgNO, then 3 moles of AgCl are obtained, as there are 3 ionisable ions in the complex (present outside the coordination sphere). The presence of ionisable CI ions are responsible for the formation of AgCl. Compounds (b) and (c) have two and one ionisable CI” ions respectively, whereas (d) has none. Thus complex (a) gives maximum amount of AgCl. CHy CCl; 24. (b): oO Brafhe ° | CH, ca, 1c for, -CHE 5. Itisa homopolymer and the monomer from which itis obtained is styrene C,H\CH = CH, 6. Ethanol is added to soap to make it transparent 7. (i) Natural polymer - Natural rubber. (ii) Chain growth polymer-PVC (polyvinyl chloride). 8. Chloramphenicol. It is antibiotic while all other three are used as antiseptic. CH: 64 cuemistay tooaY | sw sa 9. Growth of the polymer chain depends on the availability of the monomers in the reaction mixture during their synthesis. Thus, the polymer sample contains chains of varying lengths and hence its molecular mass is always expressed as an average. 10. (i) Tincture of iodine is 2-3% solution of iodine in ethanol. It is used as an antiseptic. (ii) There are two components in dettol. Their names are chloroxylenol and terpineol. 11. Gi) HyN(CH,),NH, - Hexamethylenediamine HOOC(CH;),COOH ~ NY ww C3 i) CF. Adipic acid 0 ~ Caprotactam OR cr, = Tetrafluoroethene (ii) CH, =CH— Cl ~ Vinyl chloride 12, Aspirin is 2-acetoxybenzoic acid. It is used as an analgesic as well a5 antipyretic. It should not be taken empty stomach because it gets hydrolysed to form salicylic acid which causes bleeding, in the stomach as well as ulcer formation. 13. Homopolymer ; Polymers whose repeating structural units are derived from only one type of monomer units are called homopolymers. For example, polythene, PVC, PAN, teflon, polystyrene, nylon 6, ete, Copolymer: Polymers whose repeating structural units are derived from two or more types of monomermolecules are copolymers. For example, Bune-S, Buna-N, nylon 6, 6, polyester, bakelite, ete. 14. Receptor proteins are embedded in the cell membrane in such a way that their small part possessing active site projects out of the surface of the membrane and opens on the outside region of the cell membrane, Outer surface of Binding site of receptor cell membrane Receptor, +CH,— CH, Ethene i Polythene The polymer consists of branched chains and therefore has low density. () High density polyethene ; It is manufactured by passing ethene under pressure into an inert solvent (aromatic hydrocarbon) containing (C,Hs);Al and TiCl, called Ziegler-Natta catalyst After polymerisation, the catalyst is decomposed by adding dilute acid and the crystalline polymer is filtered off. This polymer consists of almost linear chains and therefore has higher density (ii) Bakelite is prepared by condensation reaction of phenol and formaldehyde. It is used in making electrical switches and switch boards. Itis thermosetting polymer because it does not become soft on heating due to cross-linkages. (iii) Linear polymers are well packed and have high densities, high tensile strength and also have high melting point, eg; high density polythene. Branched chain polymers are irregularly packed and have lower tensile strength and lower melting point than linear polymers, e.g; low density polythene, These are different from cross-linked polymers because cross-linked polymers are hard, rigid and brittle, eg.; bakelite OR (Chain initiating step ° ° pC EUS > 2R-C-d > 28 +2€0, bier,» RCH, CH Chain propagating step CH=CH, RCH CH FRG rch R4CH,—CHy3,CH)—CHy Chain terminating step ~ Combination 2R-¢CHy—CHy},CHp—CH; —> R-(CH,CH;)-CH:CH,CH,CH;+CHsCH:R = Disproportionation RCH, —CH2},CH)—CH —> R-CH,—CHy}, CH=CH + R-¢ CH. CH,),CH) —CH Allene Alkane Gi) On the basis of magnitude of intermolecular forces present in the polymers, they are classified into four categories: | S.No. Type _ Forces between Polymers Examples (@) Elastomers _Polymerchainsareheld togetherby | Buna-S, Buna-N, Neoprene, the weakest intermolecular forces; | CH;—C=CH— CH}, being elastic in nature polymer | can be stretched. Few crosslinks a exist between chains due to which polymer regains its original form after force is released ©) Fibres ‘They are thread forming, solids | Nylon 6,6, Polyesters (terylene) with high tensile strength and high | H. 9° ° modulus, Strong intermolecular _ | itl 1 forces are due to H-bonding and | tN (CH) N= C—(CH,),Ch; ‘impart close packing of chains with ‘crystalline structure. () Thermoplastic These are the linear or slightly PVC polymers branched long chain molecules. + CH,—CH-}, ‘They have the properties of 1° softening on heating and hardening a on cooling, Intermolecular forces of Polythene attraction arein between elastomers and fibres. TCH CHeh (@) Thermosetting Intermolecular forces are cross | Bakelite, urea-formaldehyde resin (iii) Polythene, polyvinyl and polystyrene soften on heating and harden on cooling. Such polymers are polymers linked or heavily branched molecules. When heated there occurs extensive cross-linking. in moulds and polymer becomes infusible. called thermoplastic polymers, Structural Similarity : They possess intermolecular forces whose strength lies between strength of intermolecular forces of elastomers and fibres, P Tere Eri ee ed CAPSULE oo ee OH OH ang Bakelite 20 CHEMISTRY TODAY | FF5RUARY "Ts 69 CONCEPT BOOSTER Dear students!! Substitution reaction is an integral part while discussing the reaction mechanism of organic chemistry. ‘After going through the theory salve the previous engineering/medical questions on this topic, This will help you to apply your concept correctly. This topic and its application will be continued in the next issue. Take care Chemistry of substitution reactions is quite vast because it has many aspects to study. In general, the first level classification of substitution reactions can be done as follows: Substitution Reactions ¥ Aromatic nucleophilic Aliphatic nucleophilic Aromatic electrophilic Aliphatic electrophilic Free radical In this issue, main focus will be on aliphatic nucleophilic substitution reactions as other topics will also be discussed in the subsequent chapters In general, a nucleophilic substitution reaction can be shown as below: R—X + Nu orNui—> R—Nu + X Nuceophite Here, Nu or Nut is thenucleophile, Nucleophile may either be neutral or may be negatively charged. But the nucleophile must have unshared pair of electrons. This is why all nucleophiles are bases ie. Lewii bases. Ifthe nucleophile is a solvent then the reaction may be termed as solvolysis (‘lysis’ means to ‘break down’ and here we are breaking the bond between =R and -X by this solvent, if H,O is used then it is called hydrolysis) The group which is leaving ie. X is termed as the leaving group (LG) or nucleofuge (the term “fuge’ refers to Something that is ‘outward’ like ‘centrifugal *Arunava Sarkar force’ is a force which is acting outward from the centre). Overall, aliphatic nucleophilic substitution canbe classified into six categories: @ 2 (i) St (iii) Sy (iv) Sy” Ww) Sz (wi) Sr Among these S,2 and Syl mechanisms are common. The above classification has been made based on the substrate, attacking agent, ie. the nucleophile, nucleofuge (the leaving group) and of course a very important factor i, the reaction conditions. The best example to understand $x2 mechanism may be the following: CH,Br + OH” —> CH,OH (Substrate) (Nucleophiley (Product) $\2 stands for substitution nucleophilic bimolecular. The whole meaning will be cleared gradually. In the above reaction, the nucleophile ie, OH” attacks the carbon atom of methyl bromide from the backside of the leaving group i. Br; so this is a backside attack, There are two reasons for which backside attack takes + Br (Leaving group) place here. Reason 1: Sterically backside attack is favourable, HA larger electron cloud favourable larger electron cloud Hct Be 22 ogbromine som HO : Incoming OH’ carries negative charge cloud; outgoing Br also carries negative charge cloud, If OH will attack from the same side of the outgoing Br there will be severe electrostatic repulsion which will destabilise the system, ™ Institute of Chemistry (JOC)- Asansol, Durgapur, Dhanbad, Burdwan, Kolkata, 09732313208 CHEMISTRY TODAY | #5AUARY TS 71 Ekctrostatic repulsion The process is purely concerted i. one step process (breaking of =C—Br bond and formation of N S€-0 bond takes place simultaneously). There is intermediate (as obvious in case of a concerted, process) but there is a single transition state where carbon atom is partially bonded to Br atom and oxygen atom and completely bonded with the three hydrogen atoms (there are very few exceptions where intermediates can be isolated in $y2 mechanism; to be discussed shortly). At this stage, hydroxyl group has a decreasing ve charge and the bromine atom has an increasing -ve charge (because, OH” gives its -ve charge to the carbon atom and the bromine atom starts departing with the shared pair of electrons with carbon). Here, NS the energy required to break the C—Br bond is XN supplied by the formation of C—O bond. At the transition state, carbon atom with its three hydrogen atoms become almost coplanar with the bond angle of 120° (it will be exactly coplanar if the incoming group and the outgoing group will be same, but that is of no practical use). Useful Concept When the transition state appears, the central carbon atom changes its ‘hybridisation’ state from 5" to 5p? [or tends to a sp* hybridisation state]. This, is why the bond angles between the central atom carbon and non-interacting atom ie. hydrogens are 120°. At this stage, one p-orbital becomes almost perpendicular with the plane of the central atom and the non-interacting atoms. One lobe of the p-orbital overlaps with the nucleophile and the other lobe of the p-orbital overlaps with the leaving group. This arrangement ensures the maximum overlap and ‘hence low energy transition state. This is why for ‘x2 mechanism it is always the backside attack that takes place; front side attack is not permitted in this case. The credit of the formulation of $x2 parts goes to Hughes and Ingold. 72. eaemistmytooat | eons sa Energy profile diagram of 5,2 As per the informations given under the point, ‘useful concept, the reaction between the hydroxyl ion and the methyl bromide can be shown as below: HOH NZ 7 > -Br— HO Cc (el J no OE Transition state t A HOCH + Br H ‘As per the RDS, rate k{CHBr] [OH] The mechanism is termed as Sx2 as both the nucleophile (OH) and the substrate are involved in the rate determining step (RDS). The energy profile diagram can be drawn as below: CHsBr+ OH a (Reactant) Seas (CH,-OH +B (Products) Reaction coordinate —> (Progress ofthe reation) (Eqer~ activation encrgy and 4H ~ change in enthalpy) Stereochemistry involved in $2 mechanism The nucleophile attacks the carbon atom from the backside of the leaving group. Therefore, initially, if the I then the product obtained will have an inversion of configuration. For example: substrate 1 i oa. | 5 & C= Br fs |riGitw Cont Br | SN, s(n Cy ‘CH, Transition stale oromabutane | i CoH HOW CH, 540)2butanal Seybutan201 The approach may be shown using the FMO approach (Frontier Molecular Orbitals refer to ‘pericyclic reactions’) A best bonding is offered when there is an overlap between an empty and a filled molecular orbital. The empty orbital may be considered as LUMO. (Lowest Unoccupied Molecular Orbital) whereas the filled molecular orbital is considered as the HOMO, (Highest Occupied Molecular Orbital). Owe) + COX ic) Filled orbital of — Empty p-orbit Departing, hnucleophile which of eatbon atom, group is not bonded to Thisempty orbital any atom so fas, is antibonding in So,itisnon-bonding nature. This is in nature, This is LUMO. HOMO. Racemisation - an outcome of $,2 reaction Take the last example of the stereochemistry of $2 mechanism. H | womens CH, (5-6-22butanol (84) 7bromobutane For each attack one molecule of R-(-)-2-bromobutane is converted into one molecule of 5-(4-2-butanol which is having opposite configuration as well as optical activity with the starting substrate. In a single word, there is an inversion of the configuration which is better known as Walden inversion or Umbrella effect (when you keep your umbrella in the direction of a strong windflow, the face of the umbrella gets inverted). Now, see that when one molecule of R4{-}2-bromobutane is converted into one $-)2-butanol then you must observe the following two things: Due to inversion, already optical activity of one molecule of R-(-)2-bromobutane is gone. O From this R-(-}2-bromobutane what S-(#)-2-butanol we are getting, will cancel the optical activity of another R-C)-2-bromobutane. In this way racemisation is taking place and the most important thing is for inversion of one molecule, there is a cancellation of two molecules. So, rate of racemisation will be twice the rate of inversion. Now, if the optical activity of R4-}-2-bromobutane and $-(+)-2-butanol are not same then? Therefore, tobetter understand wecan take radioactive evidence. There is a very common example for it. In acetone or DMF solvent, when optically active 2iodooctane reacts with (1), then the final alkyl halide is found to contain '2N] and the optical activity of this alkyl halide is zero, So, there is 100% racemisation and a 50% backside attack can generate this racemisation. radioactive iodide ion (asalready explained that rate of racemisation is twice the rate of inversion). ‘The reaction is found to follow second order kinetics, CHy(CH),CHI + 787—> CH(CH) CHE +1 CH; cH, Rate ‘pucuga] fa] tu, (CH,)sCHy (CH)),CH, eB aft gt Non, wt %, [Opti ey sat "| Optical activity of (CHy);CH3 iynnetane type ssh f This will cancel another (R-(}-2iodooetane’sy optical activity (SH) 2igdeoetanet128) CHEMISTRY TODAY | FFaRUARY'T8 73 Sy stands for substitution nucleophilic unimolecular. Here, the rate of the reaction depends on the substrate only (say alkyl halide). In general, we can show it as: where, rate =k [R — G] The rate of the reaction does not depend on the fact that how much concentration of the nucleophile is involved in the reaction, Basically, the reaction follows a two-step path slow, pt Step: R- GSR +E Step-2 wfs As the first step is slow ionization of the substrate, the presence of high dielectric constant containing solvent (e.g. HO) isquite necessary. Solvent, preferably should be polar protic as it will help to ease the release of the leaving group and this will promote the ionization of, the substrate. Basically, it has been found that a polar protic solvent forms hydrogen bonding (evidences say that two solvent molecules are involved in it) with the partially negative charge containing leaving group and smoothes its departure from the front side. 0. aoa Intermediate carbocation us Nu R ; G: x H4 Breaking becomes Now, a8 “ionization requires energy; so Sy1 should be anendothermic process (AH >0) and thus unfavourable = then how does it take place"? Basically, the amount of energy required to ionise R—G is more than compensated by solvation of Rand Take the following example to understand and analyse the different aspects of S<1 mechanism: c-Br On MS ie $b OH + HOW Gomer CH. CH rducts with opposite configuration Theabove reaction, as depicted in the general equation, will occur in two steps: 74 eaemistmytooay | eons sa Step-l: CH, HC iti @— Bp ‘ionization (RDS) cH, sp hybridsed empty perbitel sy? nybridised At this step, the tetrahedral substrate ie. the fert-butyl bromide undergoes slow ionization to generate a trigonal planar carbocation where the carbon atom bearing the positive charge is sp* hybridised, This carbon atom and the atoms connected to it lie on the same plane and the empty pure p-orbital becomes perpendicular to it, Step-2: At this stage, the nucleophile (ie. OH) attacks the carbocation to generate the final product ie. the alcohol. But from which side the nucleophile will attack the carbocation? As the intermediate (i. the carbocation) is planar hence its both sides are available to the approaching nucleophile - one is the front side and the another one is backside. Both the attacks are stereochemically feasible and it generates the mixture of two products where the 50% of the products is with the retention of configuration and another 50% is with the inversion of configuration to the original substrate. Retention is the outcome of front side attack and inversion is the outcome of backside attack. cH Cs Hye Non, CH, 2G ICH, HAC Cs HO’ \ d OH CH, cH, 57% inversion (when overall products concemed.) An optically active substrate will finally give a racemic mixture 50% retention (when overall product is concerned.) i" HC C— pr Siow Ta cy, (CHy)s He tO OH BLO emael v0) by exeion) — | apie < Su CAs sat) C soil GH, HO \ ars C{CHg)3, dlovenion) a Organic Chemistry In the last article, we had discussed the oxidation- reduction reactions with special reference to aldehydes and ketones, In continuation to our effort to differentiate between conceptual and informative part of organic chemistry. We present carboxylic acids and their derivatives this time. © Starting with acidity of carboxylic acids, you can see some comparisons, as the followings are purely conceptual ° ° 9 I Il il — C= OH > Chg C—O > CH, C— OH NO, F a © The electronegativity of —NO, group is higher than the electronegativity of —F group. But when it comes to a trend of the type shown below, then acidity of carboxylic acids follows the order: GG, cetrichloroacetic acid > 6, o-dichloroacetic acid > o-nitroacetic acid > 2-chlorobutanoic acid > aviodoacetic acid > 4-chlorobutanoic acid > acetic acid The rich chemistry of carboxylic acids is because ‘of so many possible sites for reaction, f Lewis basicity (greater) cehydrogen 202 chemist Levis basicity (lesser) Tews acidity Bronsted acidity Besides the usual reactions of carboxylic acids with bases like (CjH.)sN, NaOH and reagents like PCly, PCl;, SOCI; take close look at the following two reactions, which are generally asked. mi r con > cco Labeled rappers ‘oth postone 76. enemsrey Tooay | snus Mukul C, Carboxylates are good nucleophiles. O° Can becasiy generated wing a base. moto AtianL6) g a —> R-C—0 —CH,-¢- Also, R—C—OH + CH Ny —> I R—C—0 —CH, ‘One well-known yet important concept may be revisited i SN o a CA Without going detailsinto the mechanism justnote alcohol is showing acidity in such esterification. Important usages. Formic acid is used in the leather industry to remove hair from hides and as an ingredient in tanning formulations. It is used as latex coagulant in natural rubber production. Formic acid reduces clostridia bacteria that helps preserving protein and suigar content and is thus "used as food preservative oo ° Formic acid is used as a miticide by beekeepers. Sodium formate and potassium formate are used as deicing agent for airport runways and roads. Formatesare used as brightening agentsiin textiles. Formates are also used in wood preservatives, resins, plasticizers, perfume fragrances, ete. ‘Acetic acd is used in the manufacture ofa wide variety of products including adhesives, polyester fibres, plastics, paints. A large percentage of acetic acid is used in the manufacture of vinyl acetate troncmer for the plastics indastey. Vinepat Gist luce ot ose aaa rete has ae vital ingredient of foodstuffs. Decarboxylation of B-keto acidsis easier that takes place at even 25°C. oO Oo i of wo, LABS BC LN, HC ‘OH Hye CH; Brdiacids also undergo decarboxylation but at a igher temperature. COOH 35:6 Ho sc, CxeR coon? 0,N—CH,—COOH, NC—CH;—COOH, R-CH=CH—CH;—COOH = also_undergo decarboxylation. Acid derivatives like acyl chloride and ester preparation methods involve very simple reactions, like treating a carboxylic acid with PCls, PCls, SOC, alcohol, ete, Let’s note few other important reactions. t a cH,—C—cH, 59 cn, O+CH, Hy— C—OH ~Rns CH, =C= 0+ H,0 Ketene is now treated with acetic acid to get acid anhydride or alcohol to get ester. On treatment ‘with ammonia it gives amide. o Cl 011 Z ~ CH CO ‘O-CH, While preparing acid derivatives starting from another acid derivative using simple nucleophiles like Cl, ROH, NHy RCOOH noie that the conversion is possible only downhill of the given arrangement, Acyl chloride Acid anhydride Ester Amide I “1 R—C-OR—* > No acyl chloride i I R-C—cl 5 R-C-NH, oO 0 oO i I ROH, I RoC-O— CR Ss pCR All the derivatives of acids can be forced to react with water to regenerate the parent acid. The reactivity towards water decreases as oO I I I >R—C—Cl >R—C—O—C—R > \ Do=e i i R-C—OR >R-C—NH, The famous Arndt—Eistert synthesis involves a ketene. ° 1.80C1y ROCH, i] 2.CHN2 2 3.Ag:018 4.120 q R—CH;—CHy—C—OH Just after heating with Ag,O, we were having, R—CH, —CH= C=O, which is attacked by H,O, a nucleophile. I > R=CH CH C—O — HM OCH R-cH,- CHS Hydrolysis of acyl chlorides and anhydrides do ‘not require even catalysis. Both esters and amides are hydrolysed in aci as well as alkaline medium. Remember basic hydrolysis of amide is even easier than acidic hydrolysis. Here comes reduction reactions oO th R-C—OR’ 1. LAIN, Tinonr? R-CH,OH + ROH CHEMISTRY TODAY | FFaRUARY'T8 77 78 cHEMistRY TODAY Alternatively, Na/aleohol or Hz in presence of CuCr,O, at 175°C under high pressure may be used, oo TL Namettintheabeence TT r-c—oR SS R-C=C-R proton sours OH O #0 ill R—-CH—C-R a aeloiny tam 2HOH R-CH-OH Ze it RC R-C-H rd Na PaBeSO, Again, I 1 LiATH, ROCNH: S55 > ROCHyTNH Reactions with organic metallic reagents are always important 1. PM @ moe), ao" n t Yo ewe, RO NH, RK The above reaction is an acid-base Grignard reagent sees amide as an acid! Slight modification gives different result. ONgx Dw —MgX—> R—EoNC NHMgX + R'H reaction. CH; CH, ke Stable until acidified See another interesting reaction, pbc 8 Tyat (Carhosylate is seldom attacked by nucleophile) FeeRUARY'4 gui gu aut =HQ, 1 4S P>—c—on > Dc D4 CHy CH; i C—CH; Dialkyl cadmium is a soft nucleophile. Acyl chloride reacts with dialkyl cadmium to give ketone, which is not further attacked by nucleophile dialkyl cadmium. I Rice I R-c—cl > RR’ Hunsdiecker reaction is another decarboxylation reaction. Itinvolves heating a Ag-salt of carboxylic acid with Br, in dry CCL, cay ol Rr + Cope Alternatively, the same reaction can be affected by heating the acid and bromine with HgO. The reaction involves free radical COOAg Br I 9° R—C—OAg’ + Br, 22> ee Br Suitable salvent” Reactivity of carboxylic acids at the a-position is illustrated by HVZ reaction. Zo ye ROCH CO Se RCHCe > Son *? l Br Br 9 2 Rogie 1H Bb No need to check the mechanism. Another way to illustrate the reactivity of a-position is to use LDA (Lithium Di-isopropyl Amide) o oO zg n 2 Rec Ce As cH cA OH nion) SO oO = 29 bn A R-CH-CH RoGH-Ce ° (Agianion) | Sor Br oO 0 a RoGH= co Reeall that LDA i. Lithium Di-isopropyl Amide is a strong and bulky base. (CHyCHy Nii (CHy),CH7 (pay Claisen and Dieckmann condensation reactions are observed on esters. Ihe I R-CH)—CLOR + HCH C—OR R L.RONG (excess) I Il in RCH C— CHC OR RK Without analysing the mechanism based ‘explanation just remember: © The alkoxy group of ester and the alkoxide must carry the same alkyl group. Alkoxide should be sed in excess. There must be at least two c-hydrogens in ester. The intramolecular Claisen condensation is °° known as Dieckmann condensation. Active methylene compounds like diethyl malonate can be used to synthesise many compounds. Consider an example diethyl malonate. ° ° I il _—-OGHs y Nat 7S OCH cH, — SH Se =0CaHs FOC 3 ° a Se? R-CH,—COOH 80 CHEMISTRY TODAY | Fesauaay 1a cH=cH—cZ Now its time to see some conjugate addition, In such reactions the C=C bond in conjugation to —COOH or — COOR give nucleophilic addition, OH 1 ; Sf cr=cH—C—on“> cu Ser Con cr OH Scnp-cistoncn-c-Lon & & Some more examples are o ANH, Z > RN-CHy—CHy— CO OR 29 _ HoH, Zo So CH CH Ce ‘OR [ ‘OR OH 0 \ ee on en Great NEC CHC +y Seunsaturated acids react with strong acids to give lactones. i i CH,=CH—CH,—CH,-C—OH = e HC CH;-CH-CH,-CH,-C—OH > Se © Important usages. ° Acetic anhydride is used in the manufacture of cellulose acetate for photographic films A little percentage of the entire production is used for aspirin. synthesis, include the manufacture of industrial chemicals, pharmaceuticals, perfumes, weed killers. It is also a restricted chemical in many countries as it is used clandestinely for the purification of banned drugs. Other usages Acetyl chloride is largely used as an acetylating agent i.e. as a means of introducing the acetyl group, into. compounds containing hydrogen atoms. It is also used to detect the presence of hydroxyl groups in organic compounds. Before we close see some important reactions from examination point of view. active Coming to boiling points ° ° ° es i I Il oN eS 2 AN Hy Ney Hy© NH—CHy HSC” “NC i bpLmee pt 208C CH OO bp tsar ° ioral 9° ° 9° ° i I Tl i é ° nore’ ay Ko? Hye Ship Narn Hé “on f Typha bpt. 6 bpeni79%¢ 2R-CH—COOH an a 6 ° oH oA I I i GR aN Nog a ON U HAC “OCH; Hx® “CH; HAC Cd uptorc bpLses bp src 98% FSO) Finally, see why formic acid is called as polar C— CCH; +HCooH Ey 7 ° Pp solvent but not acetic acid I Ih CH; CH, CH;—C—OH H-C-OH Tt eeticac Formic acid CHy-C— C—COOH + 1,0 weds-17D be L6-L8D Cis CH Dielectric constant Dielectric constant <6 -» CH=CH, > cHy-CH-C=0 > Did you check, it is not the dipole moment but 2 Co ‘ta? the dielectric constant that gives the name ‘polar ‘CH C=0 toa solvent. oH . Ney Tee Tee Now, no need to wait for the shipping to arrive! You can read all the four digita magazines on iPAD, iPhone, iPod tou and Android running devices anywl anytime. Flexible subscription offer for each Single issue: Rs 30/- 6 months subscription: Rs 1 Vist the link to subscribe your Digital magazines |http:/werwmagzter com/publishers/MIG-Learning-Media-Put-Ltd 82 CHEMISTRY TODAY | Fesauaav 1a HEMISTRY WSN) Pa 1. (b) : According to the Arthenius equation ke Ae Fel Let the activation energy (E,) in the absence of catalyst =. kJ mol"! ‘Then the activation energy in the presence of catalyst will be (x= 20) kJ mot AL 580 K; k= Ae ® (i) AL420 K; k= Act 2N420 & sil) Divide (i by Gi), we get 1/5808 et we AIDS pws FoR =(x-20)__-¥ OR 580K By solving above equation we get, 725 kJ molt 2. (a) : ALO, +3C +N, —> 2AIN+3CO mole of AlO3 requires 3 moles of carbon ie,, 102 g of AlOy requires 5 « 12 g of carbon So, 23g of Al;0; requires 3%]? x93 =8.12g of carbon 3. (0 +: Claisen condensation C110 2CH3CO,C,H3— Ca on? CHsCOCH,COOC; Hs ih le} ee. heated in CHLARC C=O resence of Ncuy nn), o 4. (0: The compound is said to be chiral if the central atom is attached to four different groups and the molecule has no plane of symmetry. 5. (d) : 38Cl, + 4NaF "Ss sr, + $,Cl + 4NaCl 6. (@): 1, 4-Pentadiene reacts with HCI, in presence of peroxide, in accordance with Markovnikov’s rule, 88 caemistay tooaY | cows sa 10. Grignard’s reagent on reaction with ethyl acetate forms ketone or tert. alcohol if we use excess of Grignard’s reagent. Reactions: Bol H,C=CH— CH,—CH= CH, Sane] OT Mg dey ether * 2 Pesos H,C— GH CH, —CH— CH ay a cujCOOEIH5 CHs— CH HO — CHS Tite acc MgCl MgCl % oa CHCA CH; Coch, — COcH, (a): AG =-nEF @) As M -27 —> M™ Thus, 1 AG =-2 « 0.059 96500 = =11,387 Jmol =—11.4 kJ/mol {b) : For concentration cell, cy Fagy = 2b og CEH nm’ Cys) Eggi ~ 0.059 V, Cyypqis) = 0.001 M 01059 = 20591 jg 2001 _, 20.059 _j,, 0.001 2 Gq 0.0591 G 0.001 0.001 _ 5 tilog2 =P" ¢, = 0% Fe 100 C= Concentration or solubility of M?* = 10 MX, > MP + 2x" S28 Ky= S25) = 457 Ky=4 (10) = 4% 10° mol dm? (4): SE, XeO,F,, BrF; and IF; have sp'd? hybridisation in their geometrical structures. (6) : Fe" is oxidised to Fe and C07 is oxidised to CO) by MnOj in acidic medium. SFe + MnO; + 8H! —> 5Fe + Mn? + 4H 5C,O} + 2MnOj + 16H’ —> 10CO, + 2Mn?* +8H,0 5FeC,0, + 3MnO; + 24H" —> 5Fe™ + 10CO, +3Mn* + 12H,0 Thus, 5 moles of FeC,O, are oxidised by 3 moles of MnO; 144 g tie, EY -0.01 mol) FeC,0, is oxidised by 3 0.01 = 0.006 mol of MnO; 5 If V mL of 0.01 M KMnO, are required then ESSENTIAL REACTIONS Nt frees © Redox reaction (Oxidation-reduction) Reduction Sn + 2Fet = —— > 2Fe®+Snt Reducing Oxiis agent ent ‘Oxidation © Types of redox reactions: ~~ Combination reaction 0 0 y 2 3 3Mg + Np -*> MgsNo - Decomposition reaction see rao 2KCIO, > 2KC1+30, = Displacement reaction (a) Metal displacement 1216-2 0 0 3246-2 CuSO, + Zn —> Cu + ZnSO, () Non-metal displacement 0 12 4 32 0 2Fe + 3H_O A> Fez03 +37, - _ Disproportionation reaction Ht Hoo 2H,0, —> 2H,0+0, In C,O,, oxidation number of carbon is 4/3. In Br,O,, oxidation number of bromine is 16/3. Tn Na,5,0, oxidation number of sulphur is 25. ‘The element having fractional oxidation stat realised to present in different oxidation states. 20 2 O=C=C=C=0 0, (carbon suboxide) oO oO Os spall p79 Ths 9 O77 Br—Er—Br=O One Sos 4 x bd o °° ° BO, sor (tibromoactaonide) (Getrathionate ion) ¢ In redox systems, the titration method can be adopted to determine the strength of a reductant/ ‘oxidant using a redox sensitive indicator. 86 cuemistmyTooaY | ess sa MnOj acts as the self-indicator. Cr02 which is not a self-indicator but oxidises the indicator substance diphenylamine just after the equivalence point to produce an intense blue colour thus signalling the end point. Iodine itself gives an intense blue colour with starch and hasa very specific reaction with thiosulphate ions (8,07), which is a redox reaction. 2Cu™ + 4 > Cush + 1p 1, + 25,0% > 2 + 5,02 Mona ‘The first element in the periodic table. Electronic configuration: 15! ‘Three isotopes : protium, |H, deuterium, 7H or D and tritium, }H or T. Laboratory preparation Zn + HSO,(dil.) + ZnSO, + Hy}; Zn+2NaOH — Na,ZnO, + H:T Commercial production Electrolysis 2HLO Tres ofandinane” f+ O2 2Na’ + 2Cl + 2H,O — Cl, + H, + 2Na’ + 20H- At anode : 2c Cl, + 2° At cathode : 2H,O + 2e—> H, + 20H” 1270, CyHagag ? NH ZO > nCO + Qn + 1)H ‘The process of producing ‘syngas’ from coal is called ‘coal gasification’, Lak, coro “scorn, 1,0 2° *5co, +H, CO+ 1,0 Ty PCO Hh ‘This is called water-gas shift reaction. Chemical properties Hi, + X; —> 2HX; (X cotalystfheating 2H, + 0, NONE 5 2H 673 K200 atm 3H, + Ny ON, "Cl, Br or 1) Hy + 2M > 2MH; where M is an alkali metal Hy + Pd® > Pd +20 yHy + M,O, > xM+ yHO H, + CO + RCH = CH, RCH,CH;CHO H, + RCH,CH,CHO ~ RCH,CH,CH,OH Chemical properties of water H,O + H,0 = H,0" + OH” (Gelf-ionization of water) H,O + NHy = NH, + OH" acid base base (Amphoteric character) Reduction 2Na+2H,O —> 2NaOH + Fly eT Oxidation acid (As an oxidizing agent) 2F; + 2H,0 + 4H + 4F- +0, Sunlight nCO, + nH,O- Pee Slocophylt (CHO), + 20, Carbohydrate (Asa reducing agent) Water is said to be soft if it produces sufficient lather with soap while itis said to be hard if it forms an insoluble scum before it forms lather with soap. 2CyHyCOONA + ME (CisHCOO), ML + 2Na'; (M is Ca/Mg) Removal of temporary hardness: (a) Boiling CaCO), 8% CaCOsb + H,0 + Cost Mg(HCO,), “> Mg(OH)sl + 2CO.t (b) Clark's process: Ca(HCO,): + Ca(OH), —> 2CaC0,L +2H,0 Mg(HCO,)s + 2Ca(OH); —> 2CaCO| + Mg(OH)2| + 2H0 Removal of permanent hardness MCI, + Na,CO;-> MCOs! + 2NaCl (M = Mg, Ca) MSO, + Na;CO,—+ MCOpL + NasSO, ‘Na,P,Ojs—+ 2Na* + Na,P,Oj, (M = Mg, Ca) M+ NayP,O3s > [NazMP,OysP + 2Nat 2NaZ + M2 MZ, + 2Na* (M= Mg, Ca) MZ, + 2NaCl —> 2NaZ + MC, 2RNa + M* > RM + 2Nat 2RH + M® = MR; + 2H! NH} + H,0 = RNH!.OH RNH;.OH: + X= RNH;.X-+ OH Hydrogen peroxide Preparation BaQ;.8H,O + H,SO, > BaSO, + HO, + 8H,O Electrolysis Hydrolysis 1H0,80080,H 2HSO;+ 2H" + HO; KS,0,+ 2D,0 > 2KDSO, + D,0; aie 2ethylantaraguinol ==? 11,0. + © oxidised product 2HSO, Chemical properties Oxidising action in acidic medium 2Fe* + 2H + H,0, > 2Fe” + 21,0 PbS + 4H,O, > POSO, + 4H,0 Reducing action in acidic medium 2MnO, + 6H + 5H,O, > 2Mn** + 8H,0 + 50, HOCI+H,O, > H,0'+ Cl +0, Oxidising action in basic medium 2Fe2' +H,O, + 2Fe" + 20H- Mn? + HQ; Mn‘*+ 20H Reducing action in basic medium 1, +H,O,+20H- > 21 +2H,0+0, 2MnO, +3H,O, — 2MnO, + 30, + 2H,0 + 20H" Heavy water, D;0 CaC;+2D,0 + C:D, + CaOD); $0,+D,0 DSO, AljC;+ 12D,0 + 3CD, + 4AOD), oe Alkali metals : [noble gas}is! Alkaline earth metals : (noble gas}ns* Chemical properties of alkali metals ALi + 0; 215.0 (Oxide) 2Na + O; > Na,O, (Peroxide) M+0;-+MO; (Superoxide) (where, M=K, Rb, C3) 2M+2H,0 > 2M" +20H: +H, [M=an alkali metal] 2M + Hy —S> 2M 2M + X,—9 2M'X- M+ (x+y)NH3—>[M(NH,),]° + [e(NH3),F° ammoniated cation ammoniated clectzon responsible for blue colowr and paramagnetism, causes conductivity MO + HO — 2M" + 20H M;0;+ 2H; > 2M’ + 20H + H,O, 2MO, + 2H,0 > 2M* + 20H'+ H,02 +O; ALINO, — 2Li,0 + 4NO, +O; 2NaNO, ~> 2NaNO, + O Some important reactions 2NH, + H,0 + CO, > (NH)):CO, (NH,),CO, + H,0 + CO, 2NH,HCO, NH,HCO, + NaCl > NH,CI + NaHCO, CHEMISTRY TODAY | FFaRUARY'T8 87 2NaFICO; > Na,CO, + CO; + HO 2NHLCI + Ca(OH); > 2NH3+ CaCl: + 2H,0 375K Na,COy10H,0 “> Na,CO,H,0 + 94,0. Na,COyH,0 =2*5Nia,CO, + H,0 Na,CO; + H,O + CO; + 2NaHCO; Chemical properties of alkaline earth metals M+ X > MX (X= F, C1 Br, 1) 00-800K BeO + C + Cl, ——= Bel, +CO 2BeCl; + LIAIH, > 2BeH, + LICI + AICI, M+2HCI—> MCh +H, M + (w+ yNHy — [M(NH,),}* + 2fe(NEb),] MO +H,0 + MOH), Be(OH); + 20H” > [Be(OH),]> Beryllate ion Be(OH): + 2HCl > BeCh + 2H0 2M(NO,); > 2MO + 4NO, +O, IM = Be, Mg, Ca, Sr, Ba) Important reactions CaCO, = a0 + CO; CaO + HO > Ca(OH), CaO + CO, > CaCO, CaO + SiO; Ca8iO, 6CaO + POyy > 2Cay(POY), Ca(OH), + CO; > CaCOs + HO CaCO; + CO, + H,O + Ca(HICOs)s 2Ca(OH), + 2Cl; CaCl, + Ca(OCl); + 2H,0 Bleaching powder CaCl, + Na,CO, > CaCO, 2NaCl aco, E*S cao +c CaCO, + HCI CaCl, + H,0 + CO, CaCO, + HaSO, > CaSO, + HO + COs 2(CaS0,2H,0) + 2(CaSO,)-H,0 + 3,0 oe Flectronic configuratior Chemical properties 4E + 30, —» 2£,0, 2E +N; 3» 2EN 2AL + 6HCI > 240" + 6Cl + 3H, 2Al +2NaOH + 6H,O > 2Na'[AI(OH),]- + 3H Sodium tetrahydroxoaluminate(t) 2E+3X,32EX, (X= F, CL Br, 1) EB + NH; —> F,B — NH, NayB,O, + 7H,0 + 2NaOH + 4H,BO, ‘Onhoboric acid 'np (except for He) Na,B,O;10H,0 ~*> NayB,0; > 2NaBO,, Sodium + BOs metaborate Borie, anhydride Na,B,O, + 2HICI + 5H,O — 2NaCl + 4B(OH), B(OH); + 2HOH — (B(OH),] + HjO" HBO; ~*> HBO, ~*> B,O; ABF, + SLiAIH, + 2B,H, + 3LIF + 3AIF, 2NaBH, + I, > BH, + 2Nal + Hs 450K 2BF,+ 6NaH ——> BH, + 6NaF BiH,+ 30; —> B,O, + 3H,0 BiH, + 6H,0 > 2B(OH), + 6H BH, + 2NMes > 2BHyNMey BiH, + 2CO — 2BHyCO 3B,H, + 6NH, — 3[BH,(NH,),1BH,)- E82 5. 2B,NGH, + 12H Borazine (lsorganie benzene) 2MH + BH, > 2M"BH,-— (M=Li or Na) Sn + 2H,O -4> SnO, + 2H, SiCl, + 41,0 HC sor, Silicie add Important reactions 2C +0, “>2c0 373K HCOOH "> H,0 + CO 4731273 K c+Ho > corn, Water gas 173k 2C +O, + AN, "> 2C0 + 4N, Producer gas 3CO + Fe,O, “> 2Fe + 3CO, CO + ZnO 4s Zn + CO; |; + 2NaOH — Na,SiO, + H,0 SiO, + 4HF — SiF, + 2H.0 Cu powder, 2CHCI + 5i SES (CH,SiCly (CH):Si(0H), 222. Hs He Hs HO —$i—OH + HO 5 - OH + HO—Si—OH CH; cH, ay + 10 | mesatin te -olfrot he Silicone 20 CHEMISTRY TODAY | FF5RUARY "TS 89