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Cusl, + 2K,S04 + Ip * boa > Pia 212) (b)_ Q.gH20}1 + HzO —> Cp) 205 + CoH1205, (©) NaSO, + BaCl, —> BaSO, + 2NaCl Qis (4) CuSO, + 4NH, —> [Cu(NH,),]SO, 3. An organic compound ‘A’ having vapour Solution Senders of Chemistry Musing density 47, gives characteristic colour with ore FeCl, ‘A’ when treated with CO, and NaOH at 140 °C under pressure gives ‘B’ which on being, Dest Achayoe, Klkata (West Bongal) acidified gives ‘C’. It reacts with acetyl chloride Patil Basu to give ‘Dy, a pain killer. The structure of ‘D'is | | 3. Suojhattvje Kolata (est Benga) ococH, ocock, 1. Arun Nayan, Ghaipu (tar Prades) (a) (b) 2. Shoumorup Mukhopadhyay, Kolkata West Bengal ‘COOH 3. Abhishek Bora, Nagaon (Assam) COOH 8 caemistaY ropay| onset How to choose the right = answer, fast? ATH Si ar vour FINGERTIPS ] The answer is practice... | fess Questions (MCQs) are based on the NCERT syllabus. Largely! 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For more information or for help in placing your order, call 0124-4951200 or emaikinfo@mtg.in JEE ADVANCED 6. Identify the reagent in the given reaction, Oe (a) HCHO, C)H;ONa (b) CH,CHO, OH (©) HCOOC,H; (4) HCOOC2Hs, CyHsONa On the basis of elemental analysis, the empirical formula as also molecular formula of a chromium complex was found to be CrN,H,2ClzBr. This complex could be isolated in two isomeric forms, One of these two forms vas found to produce a white precipitate on reaction with AgNO, solution. ‘The white precipitate was found to be readily soluble in dilute aqueous ammonia, ‘The other isomer forms a yellow precipitate on reaction with AgNO; and this yellow precipitate is only partly soluble in concentrated ammonia solution. py Reagent eGoncl 7. If we measure the conductivity of aqueous solutions of these two isomers, the conductivity of the isomer forming white ppt. with AgNO; and that forming yellow ppt. will be found to be as follows: (a) conductivity of isomer forming white precipitate with AgNO, is more than that of the other 40 cemistaY ropay| one (b) conductivity of isomer forming yellow precipitate with AgNO; will be more than the other (©) conductivity of both the isomers will be same (d) none of the above is correct 8. In the two isomers, (a) the oxidation state of Cris +2 (b) the number of unpaired clectrons is 3 (©) the number of unpaired electrons is 2 (d) In one, there are two unpaired electrons whereas in the other, there are three unpaired electrons. Mase 9. Pure water has reversible reduction potential of -0.413 V under 1.00 atm H; pressure. If 2H" + 2&° —> Hp is considered to be the reduction, then pH of pure water is 10. The value of n in the molecular formula Be, AlySiO rs is . ee sue eee Lee ‘¢ DHYAN PRAKASHAN BOOK, OPP. VAZHUTHACAUD, TRIVANDRUM PH : 9497430065 ‘¢ IDEAL BOOK CENTRE, PULIMOODU, TRIVANDRUM Ph: 9645163611 ‘¢ H &C STORE, MAVOOR ROAD, CALICUT PH : 0495-2720620 ‘¢ H & C STORES-TDM HALL-ERNAKULAM, Ph: 0484-2352133/2351233 ‘¢ VIDYA BOOK HOUSE: KASARAGOD, Mobile : 9447727212 ‘¢ H& C STORE-KOLLAM, PH : 0474-2765421 ‘¢ HAND C STORE - KOTTAYAM, PH : 0481-2304351 ‘¢ TBS PUBLISHERS AND DISTRIBUTORS, KOZHIKODE, PH : 0495-2721025,2720086,2721414 ‘© GIFTALIA BOOK BHAVAN-THRISSURE, PH : 0487-2336918, Visit “MTG IN YOUR CITY” on wwww.mig.in to locate nearest book seller OR write to info@mtg.in OR call 0124-4951200 for further assistance. Presenting India’s No. 1 PMT Guides £550 MTG Complete AIPMT Guides are India’s best selling PMT books! Rich in theoretical knowledge with a vast question bank comprising a wide variety of problems and exercises, these guidebooks ensure students are ready to compete in the toughest of medical entrance tests, both at national and state levels. 100% NCERT based, the guidebooks have been updated to match the syllabus and the exam pattern of all major medical entrance exams. No wonder these guidebooks emerged as bestsellers in a short period of time. PT ped engi ed Teng Available at all leading book shops throughout the country For more information or for help in placing your order: Call 0124-4951200 or email:info@mtg.in oe "Application to ead QR codes required orl eo sped are /AIPMIT/ AlIMS/oth red strictly on the basi MTs have drawn their hes Ti Tierney vily from N yeas Reena ea REE RN nek US eee Le PRINCIPLES AND TECHNIQUES Saas Only One Option Correct Type This section contains 20 multiple choice questions. Each question has four choices (a), (b),(c) and (d), out of which ONLY ONE is comect. 1. When chlorine is passed through molten tin, the product obtained is (a) SnCl, (b) (Snel, (c) [SCL (d) SnCly 2. Select the incorrect statement. (a) CH, is called carbanion. (b) In GH,, carbon is even more electron deficient than that in a radical (In CHy, the vacant p-orbital is perpendicular to the plane of C—H bond. (d) CH,CH, is called carbenium ion. 3. 2g of aluminium is treated separately with excess of dilute H,SO, and excess of NaOH. The ratio of the volumes of hydrogen evolvedis (a) 2:3 (b) ist (©) 2:1 (d) 1:2 4. Which is the incorrect name of CHjNC? (a) Acetoisonitrile (b) Methyl isocyanide (c) Methyl carbylamine (d) Methyl isonitrile 5. Group 13 elements show +1 and +3 oxidation states. Relative stability of +3 oxidation state may be given as 412. cuemisrey ropAy | nove ns 6. 10. (a) TI > In > Gat > APY > BY (b) BY > AP > Ga** > In** > TI* (c) APY > Ga** > TI > Int > BY (d) APY > BY > Gat > TP* > In* ‘The presence of carbon in an organic compound can be shown by (a) heating the compound with sodium (b) heating the compound with cupric oxide (c) heating the compound on bunsen flame (d) heating the compound with magnesium. Orthoboric acid contains (a) pyramidal BO} units (b) linear BO} units (c) T-shaped BO} units (d) triangular BO} units. What is the correct order of decteasing stability of the following cations? CH;-CH—CH, CH,—CH—OCH, 1 u CH,—CH—CH,—OCH, an (a) I>T> 1 (©) I> I> 1 (b) I> T>1 (d) [>> UL Wood charcoal is used in gas masks because it a) ispoisonous _(b) liquefies gas (©) is porous (d) adsorbs gases. ‘The increasing order of stability of the following radicals, (a) (CH,),CH < (CHy)C< (CcH2):CH < (CoH3):C (b) (CgH,),C < (CiH,),CH < (CH,),C< (CH),CH uM. 12. 13. 14, 15. 16. 17. (©) (CoH) :CH < (CiHy)s€ < (CHC <(CH;),CH (d) (CH3),CH < (CH3)3C < (CoHs)3C < (CH,),CH ‘The highest coordination number depends on the availability of vacant orbitals in the central atom, Which of the following elements is not likely to act as central atom in MFZ" ? (a) B (b) Al (c) Ga (d) In Among the following, the least stable resonance structure is @ ww, Z~ Wr, Wa I | ° ° ODA? oN 4 6 CO behaves as (a) Lewis acid (b) Lewis base (c) amphoteric oxide (4) none of these. Can homologues be isomers? (a) Yes (b) No (c) Sometimes (d) None of these. CCl, is used as a fire extinguisher because (a) its melting point is high (b) it forms covalent bond (c) its boiling point is low (d) it gives incombustible vapours. ‘The attacking species in the aromatic sulphonation is (a) SO,H* (b) H,SO} (©) HS0; (a) SO, On passing CO, solution containing AP* ions (a) AL(CO,), is formed (b) Al(OH), is preci (©) [AIOH),} is formed (d) colloidal Al(OH); is formed. into aqueous 18, In the reaction, CH,CHO + HCN —> CH,CH(OH)CN: HO CH CH(OH)COOH an asymmetric centre is generated. The acid obtained would be (a) D-isomer (b) L-isomer (©) 50% D and 50% L-isomer (d) 20% D and 80% L-isomer. 19. Which of the following has the highest calorific value? (a) Coal gas (c) Producer gas (b) Water gas (d) Carbon dioxide gas 20. Which of the following is isomeric with methyl vinyl ether? (a) 1-Propanol (b) Ethyl methyl ether (©) Propanal (d) Ethanol Ean One or More Options Correct Type This section contains 5 multiple choice questions. Each question has four choices (a), (b), (c) and (d), out of which ONE or MORE are correct, 21. Which of the following statement(s) is/are correct? (a) Fullerenes have dangling bonds. (b) Fullerenes are cage-like molecules. (©) Graphite is thermodynamically most stable allotrope of carbon (d) Graphite is slippery and hard and therefore used as a dry lubricant in machines. 22. Lassaigne’s extract is heated with concentrated HINO; before testing for halogen because {a) silver halide are insoluble in HNO, (b) Na, and NaCN are decomposed by HNO, (c) Ag,S is soluble in HNO, (d) AgCN is soluble in HNO. 23. Choose the incorrect order of relative stabilities of the given compounds. (a) TI Inl < Gal (b) GeCl; > SnCl, > PbCl, (c) GaCl; < InCl; < TIC]; (d) PbL, > Snl, > Gel, ‘cHemistrY Topay | voveveeR ‘14 13 24. The correct statement(s) about the compound, given below is (are) ch Heo oct ae Hy (a) the compound is optically active (b) the compound possesses centre of symmetry (c) the compound possesses plane of symmetry (d) the compound possesses axis of symmetry. 25, Diborane is a Lewis acid forming addition compound B,H,2NH, with NH, a Lewis base. ‘This (a) is ionic and exists as [BH,(NH,),]* and [BH,]" ions (b) on heating, is converted into borazine, ByN3H, (called inorganic benzene) (c) both are correct (d) none is correct. Paragraph Type This section contains 2 paragraphs each describing ‘theory, experiment, data, etc. Six questions relate to two paragraphs with three questions on each paragraph. Each question of a paragraph has only one correct answer among the four choices (a), (b), (¢) and (¢). Paragraph for Questions 26 to 28 All the elements of group 14 form tetrahalides of the general formula MX, which are covalent compounds (except SnF, and PbE,) and have tetrahedral structures.’ The stability ofthese tetrahalides decreases as we move from C to Pb. The dihalides MX, of group 14 show the reverse trend. The stability of MX; increases as we move from C to Pb. Tetrahalides are covalent compounds while dihalides are ionic. 26. Which of the following does not exist? (a) CCl, (b) SiF, (c) PbBr, (d) SnCl, 27. SiClyis easily hydrolysed but CCI, is not. This is because (a) bonding in SiCl, is ionic (b) silicon is non-metallic (c) silicon can extend its coordination number beyond four but carbon cannot (4) silicon can form hydrogen bonds but carbon cannot. 414 cuemistmy TopAY | ovens 28, Which of the following is not acidic? (a) PCls (b) SbCly (© BIC, (@ ca, Paragraph for Questions 29 to 31 ‘The resonance effect is defined as ‘the polarity produced in the molecule by the interaction of two n-bonds or between a t-bond and lone pair of electrons present on an adjacent atom: The effect is transmitted through the chain. In positive resonance effect, the transfer of electrons is away from an atom or substituent group attached tothe conjugated system. This electron displacement makes certain positions in the molecule of high electron densities. Innegative resonance effect, the transfer of electrons is towards the atom or substituent group attached to the conjugated system. 29. Whichof the following does not show resonance effect? (a) 1,3-Butadiene (b) Acrylonitrile (c) Nitrobenzene (d) Isopropyl isothiocyanate 30. Which of the following shows +M effect? (a) —N(CH,); (b) So=0 (ce) —CN (d) Both (a) and (c) 31. Which of the following carboxylate ions is the most stable? ° tl (b) CI-CH,—C-0- tl (a) CH,—C-0- ° . ° I RM Soe en Matching List Type This section contains 3 multiple choice questions. Each question has matching lists. The codes for the lists have choices (a), (b), (c) and (d), out of which ONLY one is comrect. 32. Match the List I with List II and select the correct answer using the code given below the lists : JEE (ADVANCED) Dry runs are here! ore J ADVANCED EXPLORER Pac + Pr n detailed solutions Behe aaa Betta Now, create your own pre-JEE. Just like pre-boards. With previous years’ papers and model test papers for JEE (Advanced), complete with detailed solutions, identify your areas of weakness and work on addressing them in time. Multiple test papers ensure you do your dry runs again and again, till such time you feel confident of taking on the best. For it will indeed be the best you compete with in JEE (Advanced). So what are you waiting for? Order MTG's JEE Advanced Explorer today. S Sac, 2 (a) 3. (b) 4. (a) : Acetoisonitrile is the incorrect name while all the remaining names are correct. 5. (b):Stability of +3 oxidation state decreases from Al to Tl. B always shows +3 oxidation state in all of its compounds. 6. (b): Compound when heated with CuO reduces CuO to Cu and oxidises C to CO, which turns lime water milky. 48 cuemstmy TopAY|novensih C# 2Cu0 —> 2Cu + CO, CO, + Ca(OH), —> CaCO, + H,0 (ky) 7. (d):Orthoboric acid (H3BO,) contains triangular BO}> units joined together through H-bonds forming a trigonal planar layer structure. 8. (a):CH,>CH-00n, Destabiled by 1 fect ofthe -OCH, group Thus, the stability of carbocations decreases in the order : IT > I > IIL. 9. (d): Wood charcoal adsorbs large volume of gases from atmosphere. 10. (a) On the basis of hyperconjugation, the order of stability of free radicals is as follows 3° > 2°> 1°, Benzyl free radicals are stabilised by resonance and hence are more stable than alkyl free radicals. More the number of phenyl groups attached to the carbon atom, more is the stability of free radical. 11. (a): Boron has maximum covalency of four due to non-availability of d-orbitals. Boron does not form MEF;" ion but it forms complex fluoride of type BE;. 12, (a) : In (a), due to similar charges (two positive charges) on adjacent atoms, the structure is expected to be least stable. 13. (b) : CO is a Lewis base as it acts as a ligand in complexes. Ni + 4CO —> [Ni(CO),] 14. (b):Homologues have different molecular formula, thus cannot be isomers. 15. (d):CCl, under the name pyrene is, incombustible and is used as.a fire extinguisher. 16, (d): 2,50, == SO, + HS0, + Hy adem Mad about rehearsing? SEE (ADVANI WATHEMATICg Tune, Fine tune. Reach the peak of your readiness for JEE with MTG 37413 Years Chapterwise Solutions. It is ‘undoubtedly the most comprehensive ‘teal question bank, complete with detailed solutions by experts. Studies have shown that successful JEE aspirants begin by familarising themselves with the problems that have appearedin past JEEs as early as 2 yearsin advance. Making It one ofthe key ingredients for their success. How about you then? Get 37+13Years Chapterwise Solutions to start your tehearsals early. Visit wwwmtgin to order online. sit un wee Caren ‘Available at all leading book shops throughout the country and to buy For more information or for help in placing your order: la eae Call 0124-495 1200 or email info@mtg.in ‘cHemistrY Topay | voveveeR ‘14 19 17. (b): CO, + H,O —> HCO, = CO} + 2H" 2AP* + 3CO2+ 3H,0 —> 2A(OH);] + 3CO, 18. (c) : The given reaction results in the formation of racemic mixture due to the absence of any suitable optically active reagent. 19. (a) : Calorific value follows the order : Coal gas > Water gas > Producer gas (H,U9%) — [COUSS) +HGIS)]—_[COGSK) + CH(32%) + CO(S%)] +N,(6585)] 20. (c) : Molecular formula of methyl vinyl ether (CH,O—CH=CH, = C,H,0) is the same as that of propanal (CH,CH,CHO = C,H,0). 21. (b,c) : Fullerenes are cage-like molecules and graphite is the thermodynamically most stable allotrope of carbon. It is slippery and soft and hence, used as a dry lubricant in machines. 22. (b) 23. (a,b, c,d) : +1 oxidation state becomes stable along Ga* < In* < TI* while stability of +3 oxidation state is in the order Ga* > In** > TI? due to inert pair effect. Because of the same reason, tendency to show +2 oxidation state increases down the group 14 elements while stability of +4 oxidation state decreases. 24, (a,d): The compound is optically active as it possesses two chiral centres. a oll . co 1H. HC 15 C1 rotated p80 Dn cH, ‘The compound possesses axis of symmetry perpendicular to the C - C bond. dha 25. (c) : Borazine has a structure like benzene and is ionic in nature. 26. (c) : PPBry, does not exist because of highly oxidising power of Pb" ions and moderate reducing power of Br ions, 27. (0): SiCl, is easily hydrolysed because Si can extend its coordination number beyond four due to the presence of vacant d-orbitals but carbon cannot do so in CCl, and hence is not hydrolysed. 20. cuemistmy TODAY |nvensih 28. (d):CCl, is not acidic, all other compounds give acidic solutions on hydrolysi 29, (d): Resonance effect involves delocalisation of m-electrons of two or more conjugated double bonds or non-bonding electrons and x-electrons of a double bond. nycZon cue, <> 1, Butadiene H,C—CH=CH—CH, <> a cHZor ck: ‘Acrylonitrile Ps “OP 5b Nitrobenzene BN ” Oo (Refiect) HC Isopropyl isothiocyanate does not show resonance effect. 30, (a) : —N(CH,)3 shows +M effect while (C=O and —CN show -M effect. 31, (d): Stability of carboxylate ion depends on two factors : Electronegativity of the halogen atom and number of halogen atoms attached. More the electronegativity of the halogen atom and more the number of halogen atoms more will be the dispersal of negative charge. 32. () 33. (b) : (P) HsPO, + 12(NH,))MoO, + 21HNO,—> Ammonium molybdate (NH,);PO,-12MoO, + 21NH,NO, + 12H,0 Ammonium phosphomolybdate (Q) NaSCN + FeCl, > [Fe(SCN)]Cly + NaCl Blood red (R) Dumas method : C,HN, e+[aee2 Jeo + c0, +2 H,0+ En, + fes2 Je 2 (S) Kjeldahl’s method N (from compound) + conc. H,SO, “> (NH,),S0, 34. (a) : (P) Inductive effect is a permanent effect. (Q) Resonance is the delocalisation of t electrons. (R) No bond resonance or hyperconjugation is delocalisation of sigma electrons with a-bond. (S) Electromeric effect is very strong effect. 35, (b): Silicones are organosilicon polymers which have —R,SiO— as repeating unit. These are water repellant in nature because of the presence of cross-linking in their structure in the presence of moisture. 36, (c) : Steam distillation is based on volatility not on solubility 37. (a) 38. (c) : Orthoboric acid H3BO; is soluble in water and behavesasa weak monobasic acid, Itdoes not donate protons hence, it is not a protic acid. Itis a Lewis acid as it accepts a lone pair of electrons. H,BO, + 2H,O —> [B(OH),] + H,0* (a): Simple distillation is used to separate volatile liquids those are stable at their boiling points and which contain non-volatile impurities having sufficient difference in their boiling points. 39, 40. (d):On going down the group 14, lower oxidation state becomes more stable than higher oxidation state due to inert pair effect. Pb** is less stable than Pb”, therefore, Pb compounds are stronger oxidising agents than Sn*" compounds. 41. (6) : Carbene (:CH,) has 6 valence electrons. Borazine (Inorganic benzene) 43, (6) : Percentage of hydrogen 2x wh of water =e x 100 18x wt. of organic compound _20.112100 180.22 = 5.65% = 6% 44. (5): —CH, is an electron donating group, therefore, shows +1 effect. nts \ crt OF $-OFsi— \CHs /,CH; Silicone 46. (4): Four, ie., n-butyl, isobutyl, sec-butyl and tert-butyl. 47. (3): CF, SiCl, CCl,. 45. OH B BN 48. ():HO-K \y pon » Pee oO oh OH 49, (8): C H ON 9 21:35 27) Ril es a4 3: 4:1 Empirical formula = C,H\N (CHAN), = 108 (12x 341%4+ 14), = 108 54n = 108 = n= 108/54=2 Molecular formula = CsHgN> 50. (2) : Lead monoxide (PbO) = single Lead dioxide or Lead peroxide (PbO,) = single Red Lead or Trilead tetraoxide (PbO, = PbO, 2PbO) = mixed Basic lead carbonate (white lead) (2PbCOsPb(OH),) Lead chloride (PCI) = single Plumbic chloride (Lead tetrachloride) (PbC1,) = single mixed ‘cHemistry Topay | voveveeR 14 21 Dear students!! This is the second issue of the seri CONCEPT BOOSTER af Inorganic Chemisty. n the last article have shown the style to tackle the structural problem whereas in ths issue you will get a snapshot of the process how to remember a chemical reaction in a smarter way. Main focus has been given on Nitric acid. | hope you wil ike it. TTI) ‘There are three oxoacids of nitrogen normally known. ‘They are nitrous acid (HINO), nitric acid (HNO5) and hyponitrous acid (HN20;). © The structure of HNOs can be given as below: The planar resonance hybrid structure looks as below: Pures bond character O In laboratory, reaction between potassium nitrate or sodium nitrate with conc. H;SO, gives nitrie acid. NaNO, +H,SO, —*> NaHSO, + HNO; O Pure nitric acid is colourless but on exposure to light it turns brown or yellowish brown due to the following decomposition. A AHNO (qq) > ANO7(Q) + O¢g) + 240) _ 28), Mainly responsible for the colour © Commercially, HNO; is prepared through Ostwald’ process. Steps are as follows: Step-I : At this step, catalytic oxidation of ammonia leads to the formation of nitric oxide. Arunava Sarkar Platinum or rhodium catalyst ANH3(g) + 50249) “5 atm, 851°C ANOw) + 60.9) Step-II : At this step, nitric oxide combines with the atmospheric oxygen to give NO). INO + Ox —> ZNO) ww () Step-III : Dissolution of NO» in water gives nitric acid (HNOs). Stepwise reactions are as follows: 2NOg4g) + H2O(y —> HNO3(aq) + HNO gag) -» (2) 2HNO2{aq) —> Haw + NOr~) + NOW »» (3) BNO 9) + HO) —> ZNO (a4) + NOG (4) NO produced in (3) and (4) is recycled as in (1). HNO; is first 60% by mass. Distillation is thus important, Even today, a large amount of HNO; is produced through this process. Ostwald was awarded Nobel Prize in the year 1909. Ostwald’s process gives 68% by mass HNO when it is concentrated by distillation, To get 98% conc. HNOs by mass it has to be dehydrated by conc, 2804, Important Reactions of HNO 1, Reaction with non-metals HNO; reacts with a number of non-metals. It acts as an oxidising agent here. The non- metals get converted to their corresponding oxyacids. * Institute of Chemistry (IOC)- Asansol, Durgapur, Dhanbad, Burdwan, Kolkata, Jamshedpur, Bokaro, Patna 09732313208 22 CHEMISTRY TODAY | noveBeR ‘18 2 (a) Reaction with phosphorus Step-1 : HNO} decomposes to give nascent oxygen. 2HNOs —> HO + 2NO) + [0] a) Step-2:P, +1010] > Py. (2) In this step always non-metal undergoes oxidation to give oxide. Step-3 : Oxide dissolves into water to give the oxyacid. PyOjg + 6HO —> 4H3PO4 3) ((1) x 10] + (2) + (3) gives 20HNO3 + Py + 100] + PyOjo + 6H. 10H30 + 20NO} + 10[O] + PyOjo + 4H3PO4 Dy + 20HNO; —> 41;PO0, + 20NO, + 4H,0. Reaction with carbon C+ 4HNO; —> HCO; +H,0 + 4NO, Carbonic acid (©) Reaction with sulphur Sg + 48HNO3 —> 8H,S0, + 48NO + 16H;0 (b) Sulphuric acid (d) Reaction with iodine : I, + 10HINO3 —> 2H103 + 10NO) + 41120 Todie acd (e) Reaction with arsenic : As + SHNO3 —> HAsO, + 10 + SNO} Arsenic acid (f) Reaction with antimony » Sb + SHNO; —> H3SbO4 + H,0 + 5NOz Antimonic acid Reaction with metals HNO; is very good at reaction with metals with the exceptions of few, not so reactive metals like gold, platinum which are into the class of noble metals. Style of reaction depends on the nature of HNO; solution like whether cold or hot and whether dilute or concentrated. Moreover, reactivity of metals also greatly influence the overall reaction. Based on this different categories of reactions are 1. Reaction with active metals which in the electrochemical series are higher in position than hydrogen. Formation of nitrate is a must here, Metals are oxidised and HNO; is reduced. Strategy is as follow: M + xHNO,;—> M(NO;), + x[H] Metal (cis valency of Nascent themetal.) hydrogen Mechanism is strictly electron transfer. xHNO, —> xH* — M(NO,), xH*t + xe” —> x[H] ‘This nascent hydrogen reduces HNO; in the similar manner as in case of organic nitro compounds (a) no, 4 xo Nitro 22 Nitroso. ¥ Tinos. = HON sil, ¥ Hino; _ eo” NHy 2 NH,NO; Now, applying heat on NHgNO3, nitrous oxide is a product but it is only possible by applying heat otherwise not. A NH4NO3 iG? N20 (a) Very dilute HNO ‘Two cases happen here mainly: (i) Less amount of HNO; does not allow nascent hydrogen for any further reduction. (ii) Dilute HNO; undergoes more dissociation to give more amount of nascent hydrogens which on combination give Hp gas. For example, Mg + 2HNO; —> Mg(NO3), + Hy? (b) Cold, moderately dilute (not very dilute) HNO3: Stop the reaction at ammonium nitrate stage. catemistay Fopay | novvees 12 23 For example, Fe + 2HNO; —> Fe(NO3); + 2[H] a HINO + 8[H] —> 3120 +NH3 = Q) NH, + TINO, —> NH,NO, ..Q) (1x4) + (2) + (3) gives 4Fe + 8HNO3 + HINO; + 8[H] + NH + HNO} AFe(NO3)> + 8[H] + 3H; + NH; + NH,NO; 4fe + OHNO, —> 4Fe(NO), Ns + NH4NO; + 3H,0. ‘This is shortcut. 4 : 10 ratio is the key to balance the reaction. Similar strategy for Zn, Sn, etc. (bivalent metals) Exception : Lead is an exception to the above strategy. Here, the reduction of HNO stops at NO stage and hence NO is obtained asa product instead of NHjNO3, Proper explanation has not been obtained. Probably this is due to the large surface area of Pb which hinders the process of reduction, So reaction proceeds as below: Pb + 2HNO3 —> Pb(NO3)3 + 2(H] HNO; + 3[H] —> NO +2H,0 [(1) x 3] + [(2) x 2] gives 3Pb + 6FINO3 + 2HNO3 + 6[H] oe ( w= (2) 3Pb(NOs)) + 6[H] + 2NO + 4H,0 3Pb + 8HNO3 —> 3Pb(NOs)> +2NO + 4H,0 (c) With hot and dilute HNOs ‘The trick ie. heating HNO; will release N30 will be applied here. For example, Zn + 2HNO3 —> Zn(NOs)2 + 2(H] a) HNO; + 8{H] —> 3H,0 + NH =) NH3 + HNO; —> NH4NO3 8) NH,NO, —*> N,O + 2H,0 = (4) [(1) x 4] + (2) + (3) + (4) gives 4Zn + 8HNO} + HNO; + 8[H] + NH3 + HNO} 1 + NHyNO3 4Zn(NO3)2 + 8[H] + 3H,0 + NH3 + NH,NO3 + N30 + 2H,0 4Zn + J0HNOj—> 4Zn(NO,), +5H,0 +N,0 24 cHeMisTRY TODAY | nove9eR 18 (d) uw. fa) ‘This is shortcut. Again same ratio of 4: 10 is the key to balance the reaction. Similar reaction can also be shown by Mg. With cone. HNO3: Two points to be remembered. (i) Heat is not to be applied here. N>O is not an expected product, K, c as C is high here so will be less and hence more nascent hydrogen will not be produced and reduction of HNOs will be stopped at the first stage ie. at NOp stage. So, NO» is an expected product here. For example, Zn + 2HNO3 —> Zn(NO3)2 + 2H] HNO + [H] —> H,0 + NO, (1) + [(2) x 2] gives ‘Zn +. 2HNO3 + 2HNO3 + 2[H] J Zn(NO3)2 + 2(H] + 2H,0 + 2NO> ‘Zn+4HNO;—> Zn(NO3)2-+ 2NO2 +2H,0 Similarly, for magnesium Mg + 4HNO3 —> Mg(NO3)2 + 2NOp + 2H2O Note : Tin under similar condition gives metastannic acid instead of Sn(NO3)> due to the reaction with water. 2HNO;—> H,0 + 2NO) + [0] ~() Sn + 2[O] + 120 —> H2Sn03 2) (1) x2 gives 4HNO3—> 20 + 4NO} + 2[0] (2) x 1 gives $n + 2[0] + HO —> H3Sn03 Sn + 4HNO3 > H2$n03 + 4NO> + HO ‘Metastannic acid (ii) Degree of ionization (a) for acids = (1) = (2) H)SnO3 can also be written as SnO7-H0. HNO as an oxidising agent reacting with other compounds. Same as metals, other compounds are also oxidised by HNO3,Someimportantcompounds are : Hy$, SOp, FeSO. With HS : If dilute HNOs is used, then the reaction will proceed upto NO stage whereas if conc. HNOs is used, reaction will stop at NO» stage. adem Last-minute check on your AIPMT readiness AIPMT EXPLORER MTG's AIPMT Explorer helps students self assess their readiness for success in AIPMT. Attempting the tests put together by MTG’ experienced team of editors and experts strictly on the AIPMT pattern and matching difficulty levels, students can easily measure their preparedness for success Order now! & HIGHLIGHTS: + 10 Model est Papers based on latest AIPMT syllabus + Last 10 years’ solved test papers of AIPMT Prelims + Last3 years’ solved test papers of AIPMT Mains + Includes solved NEET 2013 test paper + Detailed solutions for self-assessment and to practice time management + isi PRT for latest offers ‘Available at all leading book shops throughout the country. wpa For mate information or for help in placing your order: Phas) Call 0124-4951200 or email: info@mtg.in Cour) “Application to read QR codes required catemistay Fopay | Novvees 12 25 (i) With dilute HNO}: 2HNO —> H,0 + 2NO + 3[0] a) (NO; is produced at first which is further reduced to NO.) (©) With FeSO,: 2 FeSO, is the point of discussion because Fe”* can be oxidised to Fe’. ie, FeSO, can be converted to Fe,($O4)s. Approach will be same oe () o w= (2) H,S + [0] —> H,0 +8 (2) if any other metal of same type is taken. Just [G) x 1] + (2) x 3] gives remember one trick that to convert FeSO, into 2HNO; + 3H,8 + 3[0] Fe,(SO4)3,H28O, is needed along with the nascent oxygen. (i) With dilute HNO: HzO + 2NO + 310] + 31,0 + 381 3HNO3 —> H,0 + 2NO + 310) (ellow Sree’ 2FeSOy + HySO, + [0] —> 2HNO3 + 3H2S. —> 4H,0 + 2NO +381 Fe,($04)3 + HO .. (2) ) with HNO (Yellow) (1) + [(2) « 3] gives “ - i) With conc. 3: oe rr HNO, —> H,0 + NO) + [0] w 2HNO3 + 6FeSO, + 3H,S0, + 3[0] HS + [0] > H,0+sl Q) (1) + 2) gives HO + 2NO + 3[0] + 3Fex(SO4)3 + 3H,0 2HNO; + H2$ + [O] 6FeSO4 + 2HNO3 + 3H)SO4 —> 3Fe3(SO4)3 + 2NO + 4HO (ii) With conc. HNO3: 2H20 +2NO) + Sl + [0] 2HNO3 —> H,0 + 2NO; + [0] Yellow) 2FeSO, + HzSO4 + [0] —> Fez(SOq)3 + HO 2HNO; + H2$ —> 2H20 + 2NO) + sl fellow) (1) + 2) gives (b) With SO) : Here an extra strategy has to be added. As SQp is a gas, hence, it will undergo dissolution in HO and thus HyS0j will be an expected product (With dilute HNO5: 2HNO; —> H,0 + 2NO + 310] HO + SO + (0] —> H2S04 (1) + (2) x3] gives 2HINO3 + 31,0 + 3802 + 310] (0) w= (2) HO + 2NO + 3[0] + 3H)SO 3802 + 2HNO3 + 2H,0 —> 3H)SO, + 2NO (ii) With cone. HNOs: 2HNO; —> H,0 + 2NO; + [0] H,0 + SO, + [0] > H2S04 (1) + (2) gives 2HNO3 + H20 + SO, + [0] () o» (2) HO + 2NO> + [0] + HSO4 SQ; +2HNO; —> H,S0, + 2NO} 26 CHEMISTRY TODAY | nove9eR ‘18 mL. 2HINO3 + 2FeSO, + FSO; + [0] Fe2($O4)3 + 2H2O + 2NO, + [O} 2FeSO, + 2HNO3 + H,SO, —> Fe(SO4)3 + 2HO + 2NOz Reaction with metals which are at lower position with respect to hydrogen (except noble metals). An obvious trick is H will not be liberated here. Here, metal is oxidised at first to the corresponding metal oxide which on further reaction with HNOs gives metal nitrate. HNO} in this process can be converted either to NO> or to NO. This is found that when concentrated HNO} is used, NO» is produced and with dilute HNO3, NO is produced. Case (a) : Reaction of Cu, Hg, Ag with cone. HNO: 2HNO3 —> H,0 + 2NO; + [0] Responsible for oxidation of metal Cu + [0] —> CuO CuO + 2HNO3 —> Cu(NOs)> + HO. ( ) Cu + 4HNO3 —> Cu(NOs)> + 2NOp + 2H30 HCI + AuCls — H[AuCl,] Aurochlorie acid PtCly + 2HC1 —> Hy{PtCl] CChloroplatinie acid Higand Ag will give similar reactions. Case (b) : Reaction of Cu, Hg, Ag with dilute HNO;: Here NO will bea product of the decomposition of HNO3. For example, 2HNO3 —> H,0 + 2NO + 3[0] () Cut [0] — Cud0 »@) CuO + 2HNO3 —> Cu(NO3)2 + H,O .. (3) (1) + [2) x 3] + 1G) x3] gives 2HINO3 + 3Cu + 3[0] + 3Cu0 + 6HNOS | H,0 + 2NO + 3[0] + 3CuO + 3Cu(NO3)) +3H,0 3Cu + 8HNO; —> 3Cu(NO3); + 2NO + 41,0, ‘Ag and Hg under similar condition give the similar reaction. Now, here comes the reaction of noble metals with HNO3. Basically, as Au and Pt are very non-reactive therefore, they do not react even with conc. HNO. Rather they react with 3 : 1 ratio of mixture of conc, HCl and cone, HNO3 which is known as aqua regia. Here, at first reaction between HCI and HNO; gives NOCI (nitrosyl chloride) and nascent chlorine. A probable mechanism for this can be: anism fy this cane . Siac, Shag ZA 95 a HO AG0 Se SG Scl-N=0 + 2/Cl) Casta Q) ‘Thus the reaction obtained is 3HCI + HNO; —> NOCI + 2H1,0 + 2{Cl) Au + 3[Cl] —> AuCl; Pt + 4{Cl] —> Pic ‘These chlorides dissolve in excess of HCl giving soluble complexes like H[AuCl,] or H[PtClg] ‘Add to your Knowledge Ring Test It is a test (in fact confirmatory test) for nitrate ions. Flowchart : Aqueous solution of nitrate ‘Add freshly prepared ferrous sulphate solution Anew solution Add pure conc. H1,S0, slowly and carefully dropwise along the walls ofthe test tube A dark brown ring (hence the name ring test) is obtained at the junction of the two layers. Reaction is as follows: It is better to take the reaction in ionic form. BFe{iy) + NOsGaq) + 4H faq) —> Bed) + NO) + 2H2O( [Fe(H,0).]** + NOw —> [Fe(t,0);NO"|SO%iaq) Pentaaquanitrosoniumiron(l} (Dark brown) + HO) Fe"* 5 [Ar] 3d° 4s” 4p” ad 4s ap tii NO imparts the strong field to pair up the electrons along with water molecules which are working as the ligands, Now after pairing it looks as Fe’ — glAr] 34° 3d ds 4p Alt} ye Ft Fat HG HG HG HAD HAE NO Surprised! Due to the presence of single electron dot, NO is in much more need of linking up than that of H,O. So, remember that due to single electron donation, here Fe is not in the Fe** form rather than in Fe!* form and NO is also present as NO*. .». To be continued on the next issue. or catemistay Topay | novvees 12 27 Entropy In Carnot cycle (perfect gas, reversible process), the following cyclic integral is zero. ee [ae =0, Carnot cyele, Perfect gas Since the above integrals zero around any reversible 2 cycle, it follows that the value of the integral f 1 states | and pes. is independent of the path between the 2 and depends only on the initial and final states. vey Hence is the differential of a state function. ‘This state function is called as the entropy S ds = Sie, Closed system, Reversible process Since internal energy U is a state function, the differential dU is a state function and the value of the integral of dU between two states depends only on the states and not on the path. Tt is done exactly in a reverse way that since the value of the integral 2 J itis. depends only on the states therefore, i the differential d ‘sew. is the differential of a state function and that state function is the entropy. ‘The entropy change in going from the state 1 to state 2 equals the integral: acc, id Closed system, Reversible process 28 CHEMISTRY TODAY |noveete 18 6» “ ADVANCED CHEMISTRY BLOC (ENTROPY AND ENTROPY CHANGE) Mukul C. Ray, Odisha ame for any process that connects the states 1 and 2 as it is a state function. But it is Mey The value of ASi: only for a reversible process the integral J gives the entropy change. Entropy Change Ways to calculate AS for some processes are given Here AS means AS, O Cyclic process: Since entropy is a state function, AS = 0 for every cyclic process, O Reversible adiabatic process: For adiabatic process, djrey = 0 therefore, AS = 0, for a reversible adiabatic process. © Reversible phase change at constant temperature and pressure: At constant T dg, T 1/Tis taken outside as T'is a constant and gree is the latent heat of transition, Since P is constant and qrey = 4, = AH, therefore, asa, for a reversible phase change at constant T and P. © Reversible isothermal process: Here Tisa constant, and = few. 2 Fl Aare: . ™ T 2 ay as [Aes I T for a reversible isothermal process O Heating at constant pressure with no phase change: Consider the heating that is done reversibly at constant pressure provided no phase change occurs, djer= dg = Cy aT. Thus, ty AS= far, at constant P, no phase change. qT, T If C, is essentially a constant over the temperature range, then As=C, in 1 © Reversible state change of a perfect gas: From first law, Grey = AU = dWeey = or AS=C,In2 +nkIn¥2, fora perfect gas. i Y O Mixing of perfect gases: For mixing of perfect gases, ASmix = -REndnx; for a perfect gas, at constant Tand P. where 1, and x represent the number of moles and the mole fraction respectively, of each constituent of the mixture. What is Entropy? Although there is no simple definition that is completely accurate, entropy can be viewed as a measure of molecular randomness or disorder. ‘The natural progression of things is from ordered state to disordered state that is irom lower entropy to higher entropy. Suppose there is a deck of playing cards ordered in some particular way. These cards are thrown into the air and picked up at random. Looking at the new sequence of cards, it would be very surprising to find that it matched the original order. Such an event would be possible but very improbable, “There are billions of ways for the deck of cards to be disordered, but only one way to be ordered. Thus the chances of picking the cards out of order are much greater than the chance of picking them in order. Ithe ordered state is taken as one macrostate and disordered state as another macrostate then one thing is clear there is only one way of getting them ordered or the ordered macrostate has only one microstate and the disordered macrostate has a billions of microstates means a billions of ways to get the disordered state. For any macrostate, the number of microstates is directly proportional to entropy. ‘The process has a tendency to move towards that state which has higher probability of existence or higher entropy. Furthermore, entropy isa thermodynamic function that describes the number of arrangements that are available to a system existing in a given state, Consider two molecules named A and B to be distributed in between two vessels. Both on theleft vessel Both on the right vessel One in each vessel, once A in left vessel then A in right vessel ‘The probability that both will be on the left is thus 1/4, whereas the probability that they are equally. distributed in two vessels is 2/4 or 1/2. This means the macrostate that has one molecule in each vessel is made up of two microstates whereas the macrostate in which both of them are on the left has just one microstate. So naturally, the molecules will have a tendency to remain equally distributed Cieze3 Interested in more tests! Log on to http:/itest.pcmbtoday.com ccemusray Tooay | oveees 12 29 between the two vessels. ‘That is why gases have a tendency to fulfill the container uniformly. ‘The process moves towards that state which has more probability of existence or made up of more microstates. The great Boltzmann gave the relation between the number of microstatesand the absolute entropy. S=kinw where k is the Boltzmann constant and w is the microstates in a macrostate. Positional and Energy Disorderness Suppose there is a sample of gas in a closed container. Now there are few energy levels, which the molecules can access, On increasing the temperature or expanding the volume, more energy levels will be available to the gas sample. On increasing the volume, the total energy remains constant but more energy levels closer to each other would develop. This is called positional disorderness or probability. On increasing the temperature not only the total energy would increase but also there will be more levels too. ‘This is called energy disorderness or probability. Ultimately everything is linked to energy and energy has a tendency to get spread out. So a gas expands into vacuum because the expanded state has the highest positional probability. Entropy, Reversibility and Irreversibility ‘The total entropy change of the process is the sum of the entropy change of the system as well as surrounding. ASoys, + ASsure PMT CAPSULE 30. CHEMISTRY TODAY |noveNsiR 18 Fora reversible process, although entropy of system and surrounding may change but: ASoniv, = 0, Reversible process ASgniy, > 0, lrreversible process ‘The processes are spontaneous when they result in disorderness. Nature always moves towards the most probable state available to it. This is said in terms of entropy. In any spontaneous process there is always an increase in entropy of the universe. This is the second law of thermodynamics. In contrast to first law, which says energy of the universe, is constant. Second law defines entropy and says it is not constant. Entropy can be created but not destroyed. Consider synthesis of ammonia: Nog) + 3H) > INH) Four moles of gaseous substances are consumed and two moles are formed. This means entropy of the system is decreasing or in other words entropy change of the system is negative. ‘Ihis reaction is exothermic and energy is released. ‘This released energy raises the entropy of the surrounding ‘Together entropy change of the system and surrounding makes ASyxix, > 0 and the process a spontaneousone. On increasing temperature, ASwir. decreases and beyond certain temperature that is around 450°C, the process is no more spontaneous. ‘This signifies the importance of temperature in spontaneity. But if thermal decomposition of solid ammonium chloride to gaseous ammonia and HCL is considered the process is endothermic and more and more spontaneous as temperature increases. ‘There are some simple examplesas well; evaporation of water is spontaneous only above 100°C. in increase ery Physics, Chemistry & Biology Learn how to study effectively How to manage time How to improve concentration How to solve MCQ's on Foundati JEE Electronic configuration General Trends in Physical and Chemical Properties Allotropic forms Structure, Preparation, Properties and Uses of Some Important Compounds Pisoni C1 Elements in which the last electron enters any one of the three p-orbitals of their respective outermost shells are called p-block elements. GROUP-15 ELEMENTS (NITROGEN FAMILY) GO General outer electronic configuration is ns'np*, where n= 2 to 6. Pe eae Ce) Coordination Compounds | Environmental Chemistry CO ‘They are collectively called as pnictogens. Element At.| Electronic | Oxidation No.| configuration No. Nitrogen 7 | [He] 2s2p? | -1,-2,-3, «Ny 0, +1, 42, $3.44, 45 Phosphorus D| [Ne] 3°3p> | -3, +3, 45 @) Arsenic 33) [Ar] 3d!"4s"4p> 3.43, 45 (As) ‘Antimony | [Kr] 4d"%5s25p?_ | -3, +3, 45 (Sb) Bismuth 83 | [Xe] 4f"'sd\6s76p*| +3, +5 (Bi) Qn Series Teel eget tees ey Pane =O Ee LST Ue CM oR UT aN] Cee Reo ecco h Cacia Ae URC acc mC Cu) Prue nthe RRM ura aad eee Wea up 15 to 18) | d- and f-Block Elements Atomic size N Density [ictal character a Boiling point as | glo] | LBtectonegativity 2] 8] g| a] _[tonisston eeray sb] 2] 8 5) a) 2\¢ “) Ala) 8) 2] ¢ Bi )2] 2/8 Ng a N,P, , As,Sb, , (Bi Nom-metals Metalloids Metal C1 Alllotropy : All the elements except Bi show allotropy. Element Allotropic Forms | Nitrogen ce-nitrogen, B-nitrogen Phosphorus | white, red, scarlet, violet, | at-black, B-black Arsenic grey, yellow, black Antimony | metallic, yellow, explosive | CQ Catenation : They exhibit the property of catenation to less extent than group 14 elements due to weak M—M bond. Bond C—C N—N P-—P As—As Bondenergy : 347 159-213, M74 (kJ/mol) ‘cHemistry Topay | voveveeR 14 31 (Q) KEY PO! © Melting point first increases from N to As and then decreases to Sb and Bi * -30S. isexhibited by other elements also eg., CaP, NayAs, Zn,Sb>, © On moving down the group, the stability of +5 oxidation state decreases while that of +3 oxidation state increases due to inert pair effect. * Nitrogen shows disproportionation in acidic medium whereas phosphorus shows disproportionation in both acidic as well as basic medium. “3 as 42 3HNO,—> HNO, +2NO +11,0 45 = 4H,PO, —*> 3H,PO, + PH, (Hydrides : Form MH, type hydrides. O Melting point : Hydrides of group 15 elements follow the sequence : PH; < ASH; < SbH)< NH, 195K 1S67K SK 952K O Boiling point : BiH, > SbH, > NH, > AsH; > PH; ‘The unusual order is probably due to the reason that the increase in the boiling points of SbH and BiH; (because of higher van der Waals’ forces of attraction) more than compensates the increase in boiling point of NH (because of H-bonding). Stability, Basic character, Bond angle, Strength of M—H bond decreases. Bond NH; , PH, , AsH; , SbH , BiH, angle : (I (936%) (91.8%) (91.3) (900°) Reducing character, Acidic character, Poisonous character increases, » C1 Oxides : All these elements form oxides of the type X,0;, X,0, and X,0, N,O3 P03 A8;03 Sb,03 BizO, || rcidic N04 PO, AsOy $bj04 BigOq |) nature NiO; PO; 8,05 Sb,05 BiyO5 increases ‘Acidic nature decreas 32 CHEMISTRY TODAY |noveNsih 1 As the clectronegativity increases, acidic character of the oxide also increases. Among the oxides of same element, higher the oxidation state, greater the acidic character. Oxoacids : The strength and stability of oxoacids having the element in the same oxidation state decrease gradually with decrease in electronegativity of the central atom. HNO; H3PO, HyAsO, — HySbO, Stability decreases O Oxoacids of nitrogen : OH N= A” H-O-N=0 HO ypontaous aid Nitrous aid Gino) UNO) oO 0 Ho nz HO-0-N=o Nitric ac Femitic acd {HINO ‘TINO, © Oxoacids of phosphorus: Oxoacid Structure Phosphinic acid ° (Hypophosphorous U acid), H;PO, HO“ | ~H Basicity OS. of P Phosphonic acid ° (Orthophosphorous 1 acid or phosphorous Ho~ | ~H 5 OH acid), H,PO; Basieity=2 OS. of P= +3 Phosphoric acid ° (Orthophosphoric W |, HjPO, HO~ | ~OH OH Basicity = Metaphosphoric acid oO (Glacial phosphoric I acid), (HPO;),, 07 | Sjo7 Basicity OS. of P Pyrophosphorous acid o 9 (diphosphorous acid), y Mt H,P0s HJ ~O7 WH ou OH Basicity = 2 OS. of P= +3 Pyrophosphoric acid e @ diphosphoric acid), Hoar » 077 ~o~ Son OH OH Basicity = 4 OS. of P= 45 Hypophosphoric acid, °° ll OGM * Phosphorus pentoxide, P,Ojg due to its appearance as a snowy powder is called “Flowers of Phosphorus”. © Mixture of calcium cyanamide (CaCN,) and graphite is called nitrolim which is used as a fertilizer. * Tartar emetic (C,HyKO;Sb) is potassium antimonyl tartarate which contains antimony and is used in medicine as anti-poison. © Thomas Slag : Mixture of Ca;(PO,), Sse H,P,0, PP and CaSiO, which is a by-product of HOTZ, yet steel industry. It contains 14-18% of Basicity =4 PO, and 40% lime. It is used as a fertilizer. OS. of P= +4 Important Compounds of Nitrogen Family Structure Preparation Properties Uses ‘Ammonia (NH3) Nog) + 3Hyy) = 2 yy, 44,0 Infeftigerators, manu- 2NH. facturing of rayon, HNO, 9 te a, PPNH,CL+N, ats proces x AH; =~ 92.4 kJ/mol [SE te (Ostwalds process), DX (Habersproces) NHS NCI, + HCL NaHCO (olay proces), Hon oye, Eras) altrogenous erties cao : [A825 [Ag(NH,),ICl Phosphine (PH,) Ca3P, + 6H,0 —> S501, cy,p, «11,50, For production of smoke 3Ca(OH), + 2PHy? Hot 327 24 screens. Phosphine [> PHC cea PH, 0, in combination with aA lana! acetylene is used in HHH SN, +H:PO, preparing Holme's signals. Nitric acid (HNO ) NaNO, + H,SO, —4> 80 44,50, As fertilizers, explosives, oO a fumes, dyes and No yt NaHSO,+HNOs yg | 30 perfumes, dyes an H one a HNO,~-— => H35n03 medicines. As oxidiser in ° > H,0 + NOCI rocket fuels. +{cll Phosphorus Py + 10Cl, —> PsOr0 As chlorinating and Ipentachloride white) 4PCl, eae (dehydrating agent. (Pcl) pel. f oa P80, + POC, ¢ nl SLE8w, psc, on ro, a 1 ‘cHemistrY Topay | voveveeR ‘14 33 OGM ‘© Moist NH, gas is dried over quick lime, CaO. However, it cannot be dried over conc. H,SO4, P05, because being basic it forms salts with them. Anhydrous CaCl also cannot be used because it forms a complex CaCl, 8NH, with it, © Fe, Cr, Ni and Al become passive in conc, HNO (ie, lose their normal activity) due to the formation of a thin protective layer of the oxide on the surface of the metal which prevents further action. © Nitric acid has no action on noble metals (Au, Pt) but these metals dissolve in aqua-regia (3vol. cone, HCI+ 1 vol. cone. HNO,) forming their respective chlorides. Persons working with white P (very poisonous) develop a disease known as Phossy jaw in which jaw bones decay. © In solid state, PCI; exists as [PCL]*[PCl] in which the cation, [PCl\]* is tetrahedral while the anion, [PCl,]” is octahedral. General outer electroni nsnp', where n= 2to 6. configuration is Element | At. Electronic ‘Oxidation No. configuration No. Oxygen | 8 [He] 2s°2p* | -2,-1, +1, (0) 42 Sulphur | 16 [Ne]3s°3p'—_|-2, 42, +4, () +6 Selenium 34 [Ar]3d4stap*|-2, 42, +4, (Se) +6 Tellurium) 52 | [Kr] 4d!95<5p!_|-2, +2, +4, (Te) +6 Polonium 84 [Xe] 4f'*Sd'°6s*6p*) +2, +4, +6 (Po) O ‘they are collectively called as chalcogens, i. ore forming elements since a large number of metal ores are either oxides or sulphides. 34. cHEMistRY TODAY |nvensih 1 QQ he first four elements of this group are non- metallic in character( ©, $ , Se, Te ). Non-metals. Metafloids C2 The last element of the family, polonium has metallic character and is a radioactive element with very short half life. © Oxygen shows ~2 oxidation state in general, except in O3F> (+1) and OF, (+2). Tonisation energy ° [Electron affinity Se Te Po OD Atomicity : Oxygen is diatomic, sulphur, selenium and tellurium are octaatomic with puckered ring structure. S. Ss\c es ss -SNg 2 Allotropy : All the elements exhibit allotropy. Element Allotropic Forms Oxygen _|O, (dioxygen) and O, (ozone) Sulphur /Rhombic (or @) sulphur Sy, monoclinic (or B) sulphur Syy plastic sulphur open chain. Selenium Red (non-metallic) and grey (metallic) Tellurium | Crystalline, amorphous Polonium | o. and B (both are metallic) C2 Catenation : Maximum in $ due to highest bond strength of SS bond. Order is S>Se>O>Te O Hydrides: All the elements form stable hydrides of the type HM where M is sp* hybt ised. Stability decreases. > HO, HS , HSe , HyTe Poisonous nature, acidic character, reducing © ‘The weakening of M—H bond with the increase in the size of M explains the acid character of hydrides. O Volatile character first increases from H,O. to H,S and then decreases from H,S to character increases HyTe. O Halides: Element Fluorine Chlorine Bromine Iodine Oxygen F,0, 0.F C10, C10,CL0, __Br,O 1,0; Sulphur | Sy, SEs SpFjgS2F_| SCly, SCly, $,Clp S:Bry - Selenium | SeFg, SeFy,Se,Fe, _| SeCly, SeCl,, Se SeBr,, SeBry*, SeyBry— — Tellurium | TeF,, TeFg TesFjy | TeCh*, TeCl, TeBry, TeBry Tel, Polonium | PoF. PoClj, PoCl, PoBry, PoBr; Poly * Unstable Ozone (03) O Uses O Discovered by Van Marum. It is an allotropic form of oxygen. It is present in small quantity in the upper layer of the atmosphere, where it is formed due to the action of ultraviolet rays on the oxygen of the air. Q. Preparation On passing silent electric discharge through dry oxygen, in an ozoniser, ozone is formed. We always obtain a mixture of oxygen and ozone. This mixture is called ozonised oxygen. Silent electric discharge 30, 203, AH(298K) = +142 kJ mol! CO Properties Pale blue gas with characteristic strong smell, slightly soluble in water but more soluble in turpentine oil, glacial acetic acid and CCly. p22 0, + No, HS > H,0 +5 +0, +S» ppso, Kot x0, CH=CH, 11,078 > HCHO (CL SeCl,) 2 > sacl, © Bleaching ivory, oils, flour. O Asgermicideand disinfectant for sterilising water. O For purifying air in crowded places. O Manufacture of KMnO, and artificial silk Oxoacids of Sulphur (A large number of oxoacids are known in the case of sulphur either in the free state or in the form of salts or both, @ Key ON) * Electron affinity of O is lower than that of $ due to electron-clectron repulsions in the small 2p-orbitals of O. * Sthombic changes to Spronodinie above 954°C. * Grey hexagonal selenium is thermodyna- mically most stable allotropic form of Se consisting of polymeric helical chains. * Sulphur is also called as ‘brimstone. ‘© H,Sis called sulphuretted hydrogen. cemusray Tooay | ovees 12 35 Oxoacid Oxidation state, Structure Properties basicity and salt type Sulphurous acid, S$ = +4, dibasic, and 9 ~ acts as reducing agent H,SO, forms two series of salts, as well as oxidising sulphites (S03) and ° agent. bisulphites (HSO;) 10] 5 — exists only in solution, Sulphuric acid (oil of $ = +6, dibasic and ° = highly corrosive acts vitriol), H,SO, forms two series of salts, i] as oxidising agent and sulphates (SO) and no] No dehydrating agent. bisulphates (HSO; ) OH Peroxomonosulphuric $= +6, monobasic and ° ~ white, crystalline and acid (Cards acid), forms single type of salt, I hygroscopic solid, H,SO,, peroxymonosulphates VAN Oo —~ Powerful oxidising (HS05) oO bn O- agent. Peroxodisulphuricacid $= +6 and formssingle) ~ colourless, erystalline (Marshall's acid), type of salt, peroxydi-/ I iy and hygroscopic solid. H,S,0, sulphates (S,05") = stron, oxidisin, 28,0 phates (S03 Hos if iB OH OH agent. Sulphuric acid (H,S0,) Q Preparation It is also known as oil of vitriol and king of chemicals. O Contact process: S ramen 502,[ Dust eetee Arsenic Testing Chamber Drying Purifier Box Impure SO, Pure SO. Cone. H,SO, Yo? 0 Absorption], SO; _[ Catalytic |, Pre- ES So Tower Converter: Heater Oleum Structure Properties Uses ia wae His used as 2804S Na.50,521,0 oXdisng, 7080, Hy dehydrating [Si > 120 + 11H,0 agent and H,S0,- for the | _> s0,4H,0 Sulphuric acid Sulphate ion |__Nas sa 'so, + Hg _| Preparation of Bac 204% FES dyes, drugs, Toran? rec BaSO, + HCl eploees, slFe(CN) 6] sives, K,SO, + FeSO, + | volatile acids, (NH,),80, + COT ete, 36. CHEMISTRY TODAY |noveNsih 1 O General outer electronic configuration is nsinp®, where n = 2to 6, coloured solutions, ‘Thus, Cl, gives yellow, Br, gives brown and I, gives violet solution, QQ Properties of halide ions (X-) : Some properties of halide ions follow the following Element At. Electronic Oxidation, order No. | configuration No. Fern 9 | [del2e3p° 4 ‘Reducing nature inereases. > Chlorine) 17 [Ne]3s*3p> 1, +1, +3, Fo, ce, Bro (ch) #547 Bromine] 35 | [Arlad™aap™ -1, 11, +3 Hydration energy, Basic character decreas (Br) 45, +7 O Hydride 7 fi Weta lydrides (HX) : All halogens directly combine Todine | 53 | [Krl4d!5s’5p°-1, +1, +3, with hydrogen to form HX known as hydracids @) a or halogen acids. Astatine | 85. [Xel4f“5d!os6p> — Hy +X,—32HX (At) Chey are collectively known as halogens (sea salt forming elements). Astatine is radioactive artificially prepared element. Atomie radi F [[lonisation enthalpy | Electronegativity [| Oxidising power | Reactivity cl Br Tiicreases Decreases Decreases Decreases Decreases At CO Bond energy and bond length : The bond length increases from fluorine to iodine. F-F |C-Cl Br-Br| I-I 1.99 1588 242.6 1928 151.1 Bond length (A) Bond energy (kJ/mol) Due to small size the interelectronic repulsions between non-bonding electrons are high in case of fluorine which results in weakening of F-F bond. O Solubi falogens are soluble in water. ‘The solubility of iodine in water is enhanced in presence of KI. KI+1, —> Kh, (ie, KT) In organic solvents like CS;, CHCl, and CCly, the Cl, Br, and I, are more soluble and give O Preparation: - “HE and HCl can be obtained by heating fluorides and chlorides with conc. H,80. CaF, +H,S0, —* >CaSO, +2HF — HBr and HI are strongly reducing in nature and reduce conc. H,SO, and thus, cannot be prepared by this method. 2HBr (or 2HI) +[0] 2 HSOe_, Br, (or 1) +H,0 Hence, they are prepared by hydrolysis of phosphorus halides, PX, +3H)O—>H3PO, +3HX (X=Br, I) O Properties : - HF is a liquid with boiling point 293 K due to intermolecular hydrogen bonding, while HCI, HBr, HI are gases. = The boiling point follows the trend HE > HI > HBr > HCL Q. Oxides : All form oxides of different types. O Halogens do not combine directly with oxygen hence, they are prepared by indirect, methods, They are : OF, c,O BO 1,0, OLF, clo, BrO, 1,05 clo; BO, 404 1,0, 1,0, ‘cHemistrY Topay | voveveeR ‘14 37 O Structures of some oxides Of, Clg On ok Be Ain OSA RNS De cl ao" o oF ae 0 oO ‘oO O Alloxides are powerful oxidising agents and decompose with explosion when heated. C1 Oxoacids: All form oxoacids of the type HOX, HXO,, HXO; and HXO, as shown below Name |ON. Fo Cl) Br I ofX | Hypohalous | +1 HOF HOC! HOBr HOT acid, HXO Halousacid,| +3 - HCIO,| - — - HXO, Halicacid, | +5 - HClO; HBrO, HIO, HXO, Perhalic acid, +7 - HClO, HBrO, HIO, HXO, ‘Thermal stability, acidic strength decreases. HXO, , HXO;, HXO, , HXO' Oxidising nature increases. > Interhalogen Compounds CQ Halogens combine among themselves to form compounds known as interhalogens or interhalogen compounds of the type AX, AX, AXzand AX;. Their structure and hybridisation is as follows sation Square x pyramidal Xp ‘eet 38 CHEMISTRY TODAY |noveNsih 1 AX, | sp'd®Pentagonal bipyramidal ed Examples : Br, BrCl, CIF, BrE, ICI, CIF3, BrF;, IChy BrP, IF, IF, O Properties: They are covalent, more reactive, strongly oxidising and diamagnetic in nature. Preparation : They axe prepared by direct combination of halogens cl, +8, 22%, 2c By the action of halogens on lower interhalogen clk +8, 225 cr, 2 Polyhalide ions : ‘the ions containing more than twohalogen atoms are known as polyhalide ions. For example, KI+1, —3KI, ==K* +15 Other examples are Br;, Cl, ICly, ICly, BrFy [Fes Ip. (2 Pseudohalogens and pseudohalides : The substances behaving like halogens are known as pseudohalides. Some examples are : Pseudohalogens Pseudohalides (CN)>, Cyanogen CN Cyanide (OCN);, Oxycyanogen _OCN™, Cyanate SCN),, Thiocyano, eCN , Selenocyanate (SeGN),, Selenocyanogen SCN”, Thiocyanate NCN?’, Cyanamide Nj, Azide ORG ¢ Iodine also forms I* and I** cations due to less ionisation energy as (CH,COO),I, 1(C10,); and IPO, have been isolated. © Because of the tendency to form hydrogen bond, metal fluoridesare solvated by HF giving species of the type HF,” etc. KHE,(KF-HF), KH, (KF-2HF) and KHF, (KF-3HF) are known examples. O General outer electronic configuration is nsinp®, where n = 2 to 6. Element Atomic Electronic no. configuration Helium (He) 21s? Neon (Ne) 10 1s? 2s? 2p* Argon (Ar) 18 _ 1s? 2s? 2p 3s? 3p® Krypton 36 1s? 2s? 2p 3s? 3p% 3a (Kr) 4s? 4p® Xenon (Xe) 54 1s* 2s? 2p°3s? 3p 3d! 4s? ap® 4d! 557 5p> Radon (Rn) 86 1s? 2s? 2p° 3s? 3p°3q"” 4s" 4p 4d" af'*5s? 5p° 5d"° 657 6p* OQ. Occurrence: The relativeabundance of different noble gases in the atmosphere are given below: Element ‘Abundance in air (% by volume) Helium (He) 5.24 x 10-4 Neon (Ne) 1.82 x 10% Argon (Ar) 0.934 OQ Compounds of Xenon : Krypton (Kr) | 114x104 Xenon (Xe) 87x 10° Radon (Rn) Trace Except radon which is a radioactive element, all other noble gases occur in the elemental state in the atmosphere. Melting point [Boiling point stone rad | [Critical temperature | Heat of vaporisation Solubility in HO rizabilty He focret Taerentes eae ma ea acre] Thereases 1Z Liquefaction : It is extremely difficult to liquefy inert gases due to weak van der Waals’ forces of attraction among their molecules. Hence, they possess low value of critical temperature als all are adsorbed by coconut charcoal at low temperatures. The extent of adsorption increases down the group, Compound | Structure Preparation Properties XeF. Nitube th 2 Xe Fy Wo Xehy [2 > Xe +2HF (Xenon en ae who 1 difluoride) Xe +0,F, BX xe Xe+2HF + >On Xek,+0,, LP 2F xe 2H LESS Xe +2HF + Cly = Acts as fluorinating agent. XeFy, P Xesp, M5 Xer, | Colourless, crystalline solid with (Xenon Gs ore melting point, 117.1°C. tetralluoride) - Xe +2H, —> Xe + 4H = Undergoes disproportionation in water. 6XeF, + 12H,O —> 4Xe + 2Xe0, + 24HF + 30, = Gives adduct. XeF, + SbF; —> [XeFs]* [SbF] — Acts as fluorinating agent. = Dissolves in anhydrous HF. cciemusray Tooar | oven 12 39 XeO5, A) Complete hydrolysis of |- Colourless, highly explosive and (Xenon 0) XeF, and XeF,: powerful oxidising agent. twioxide) Xe 6XeE, +12H,O—> 4Xe — With water forms xenic acid. of \ — 2XeO;+ +30) +24HF/ XeO, + HO —> H,XeO, ° XeF,+3H,0 —> XeO, - Undergoes disproportionation when (46) + 6HE| dissolved in alkali Pyramidal, sp? 2XeO, + 40H” —> Xe +0, + XeOP +2H,0 XeOF,, F Partial hydrolysis of — Unstable tenon | Q\ ae oe Xe—=O XeF,+H,O—> “yt Hy J| XeOF, + 2HF F (+4) T-shaped, sp3d XeO,F, F Partial hydrolysis of — Colourless solid. (Xenon dioxy. | JP XeORsorXeF: = Undergoes hydrolysis readily. sitloord) SF XO, + HO > XeOF;+H,0 —> XeO, +2HF | So XeO,F, + 2HF F XeFig +210 > Distorted trigonal bipyramidal, p34 2XeOF, + SiO, U1 Uses of Noble Gases O Helium — Since its lifting power is 92% that of hydrogen, therefore it is used to lift weather balloons and airships. It is used as breathing mixture (or oxygen dilutant) for divers. Mixture of O, and He is used in the treatment of asthma, Used for inflating aeroplanes. Neon Neon lighting is used for advertising. It is used for filling sodium vapour lamps Itis also used in beacon light as safety signal for air navigators. O Argon Primarily used to create an inert atmosphere in light bulbs, welding and fluorescent bulbs. the tyres of ° 40. cueMstmy TODAY |novensih 1 XeO,F, + 4HF Action of SiO, on XeOF,: > 2XeO,F, + SIF, Used in geiger counters, as it becomes ionised in the presence of radiation. ‘The ratio of “K to Ar can be used to date the age of rocks since Ar is obtained by radioactive decay of an isotope of potassium. Krypton ‘The light emitted by Kr in an electric discharge tube is used for runway and approach lights in airports. Xenon It is used in electrical flash bulbs for Radon is used in radiotherapy of cancer. ORG * Noble gases have high ionisation enthalpies and almost zero electron affinity values © He and Ne do not form clathrate compounds while other noble gases form. ay eee ‘= Introduction Properties ‘= Some important compounds psec _ d@- BLOCK (TRANSITION ELEMENTS) Q Elements in which the last electron enters any one of the five d-orbitals of their respective penultimate shells are known as transition elements, CO ‘their general electronic configuration is (n= 1d" "ns? where mis the outermost shell. When electrons are filled, ns-orbital is filled first then (n~1)d-orbital and during oxidation, ns electrons are lost first. then (n= 1)d-electrons. C2 Thepresence of unpaired and unfilled d-orbitals, favours covalent bonding. Q. Electronic Configuration of Transition Elements 3d-Series 4d-Series 5d-Series Atomic Element Electronic Atomic Element Electronic Atomic Element Electronic No. Configuration No. Configuration, No. Configuration 21 Se [Ar]3d"4s* 39 Yy [Kr]4d'5s? 57 La [Xe]5d'6s? 22 Ti [Ar]3d’4s?_ 40 Zr [Kr]4d"! 2 He — [Xel4f*5d? 6s” 23 Vv [Ard'4s? 41 Nb [Kr}4d*ss! 73 Ta [Xe}4fi4sa? 6s? 24 cr [Ar]3d°4s" 42 Mo [Kr]4d°5s! 74 Ws [Xe]4ftsd* 25 Mn [Ar}3d°4s 4B Te [Kr]4d°5s? 75 Re [Xe]4f4sd? 6s? 26 Fe [ar)3d°4s? 44 Ru [Kr]}4a’5s! 76 Os [Xel4f'*5d* 6s? 27 Co [ar]3d’4s?_ 45 Rh | [kridd*5s!_ | 77 Ir [Xe]af‘'5d 65° 28 Ni [Ar]3d°4s? 46 Pd [Kr]ad'5° | 78 Pt [Xe]4f4sd? 6s! 29 Cu [Ar]3d'4s! 7 Ag [Kr]4a'°5s! 79 Au [Xe]4f*sd'? 6st 30 Zn [Ar]3d"4s? 48 Cd | [Kr]ad'%5s? | 80 Hg — [Xe]4f45d"° 6s? Metallic Character © Transition metals can lose valence electrons, and form cations M—> M"*+ ne’ O They have hep, cep and bec lattices, characteristic of true metals. O Except Hg, they are solids at room temperature and are dense (density of osmium 22.6 g/cm’), lustrous, malleable, ductile, thermal and electrical conductors. ‘There is gradual decrease in electropositive character from left to right. U Tonisation energies : The ionisation energy increases with the increase in the atomic number but not in regular manner, The LE. of 5d-elements are higher than those of the 4d- and 3d-clements due to greater effective nuclear charge which in turn is due to poor shielding of nucleus by 4f electrons. @EGMNM © Formation of Ni! requires 11.29 kJ mol and formation of Pt** requires 9.36 kJ mol! of energy. ‘Thus, K;PtCl, is well known whereas the corresponding nickel compound is not known, O Electrode Potential (E°) E°(M""/M) is governed by three factors : O Heat of sublimation O Heat of ionisation O Heat of hydration For the 3d-transition metals the E%(M°*/M) values are Cr Mn Fe Co Ni Gu 1.18 -0.91 -1.18 -0.44 -0.28 -0.25 0.34 (Volts) cemustay Tooay |noveven 1s 41 ‘The irregular trend is due to variation in ionisation energies and sublimation energies. Except copper 3d-elements are good reducing agents but weaker than s-block elements, CQ Magnetic properties : They are Paramagnetic : Paramagnetic substances are weakly attracted by an applied magnetic field. Thisis due to the presence of unpaired dLorbitals. Paramagnetic character increases with the number of unpaired electrons. O Diamagnetic : Diamagnetic substances are repelled by an applied magnetic field. O Ferromagnetic : In this case permanent ‘magnetic moment is acquired by substance. eg, Fe. O Magnetic moment is given by n(n+2) BM where » = number of unpaired electrons and BM = Bobr ‘Magneton (unit of magnetic moment). electrons in Q Catalytic properties : The transition metals and their compounds behave as catalyst due to O ‘The presence of partially filled d-orbitals and various oxidation states. © ‘The formation of intermediate complex with reactants and thus lowering the energy of activation. © Their rough surface area which provides active sites for adsorption of reactant molecules. e.¢., Iron in the preparation of NH, (Haber's Process). — Finely divided nickel for hydrogenation. = Ptor V,0; in the preparation of H,SO,. Complex formation : They are well known to form a large number of complex compounds mainly due to O Small atomic size and higher nuclear charge. O Presence of partly filled or vacant orbitals eg, Ky[Fe(CN)g]. C1 Oxidation States © Indifferent types of compounds, transition metals exhibit different oxidation states. 42 cuemstmy TopAY|novensin i © ‘The highest oxidation state is exhibited in fluorides and oxides. © In lower oxidation state, the compounds formed are ionic and in higher oxidation state, they are covalent in nature. © ‘The highest oxidation state shown by any transition metal is +8, Ru (4d series) and Os (5d series) show +8 oxidation state. Element Oxidation states Se 3 Ti (12), 43,44 v 12,43,44, 45, cr 42,43, H, 45,46 Mn 42,43, HL, (45), 46,47 Fe 12,43, (+4), (+6) co 42,43, 4 Ni 42, (43), 4) cu 41,42 zn 2 Very rare oxidation states are given in brackets. @EGG0Mm * Transition metals show zero oxidation state in some complexes e.g.,in Ni(CO), and Fe(CO);; Niand Fe have zero oxidation state. O Interstitial compounds : present in a.crystal lattice is known as interstitial space. The non metal atoms due to their small size (e.g, H, B, N, C etc.) when occupy such place, the resulting compound is known as interstitial compound. Such compounds are hard and rigid e.g, cast iron and steel. ‘The empty space Coloured Ions O ‘The colour exhibited by transition metal ions is due to the presence of unpaired electrons in d-orbitals which permits the d-d excitation of electrons. O Colour of a complex depends on the metal, its oxidation state and its ligands. ¢g. [Cu(H,0),]”" is pale blue, [Cu(NH,),|?* is dark blue. Some Important Compounds of Transition Elements Compounds Preparation Physical properties Uses Potassium From sodium dichromate Orange red, crystalline In dyeing, photography oxidising agent, and leather industry. infectant, germicide, oxidising agent, Baeyer’s reagent (alkaline dichromate (obtained from chromite ore). solid, (K,Cr0;) NayCr,0, + 2KCI—> K,Cr,0; melting point, 398°C + 2NaCl Potassium From potassium manganate Deep purple, crystalline As permanganate (obtained from pyrolusite). solid, (KMnO,) —_-2K,MnO, + Cl, —> 2KMnO, | melting point, 240° C +2KCL f BLOCK (INNER-TRANSITION ELEMENTS) CO The block consists of two series of elements known as lanthanides and actinides. CO “The general outer electronic configuration of the ‘Fblock elements is (nm ~ 2)! Mn — 1d ns?. C2 For lanthanides, n is 6 while its value is 7 for actinide series Lanthanides General outer electronic configuration is af 45d“! 66? The fifteen elements from lanthanum, (At. no, 57) to lutetium (At, no, 71) are known as lanthanides or rare earths (because they were obtained as earths (oxides) from relatively rare minerals) “Element Atomic | Electronic Oxidation number | configuration states la 57 | [Xe]5d6s* +3 Ce 58 [Xe]4f"5d' 43,44 Pr 59 [Xelaf%es? 43, (+4) Nd 60 | [Xelaf tos? (42), 43, 44 Pm 61 [Xe]4f%s? +3 Sm 62 | [Xe]4f%s? (42), +3 Eu 63 [Xe]af"6s* 42,43 Gd 64 [Kelaf’Sdles* +3 Tb 65 (Xel4f%6s? +344 Dy 66 | (Xel4fl6s* +3, (+4) KMn0,). Ho 67 [Xe]af"'6s” +3 Er 68 [Xe]4f"76s* +3 ‘Tm 69 [Xe]4f!*6s” (42), +3, ‘Yb 70 | [Xe]4f"*6s* 42,43 Lu 71 [Xel4fM*5a'6s? +3 ‘Very tare oxidation states are given in brackets Oxidation state : The common oxidation state of lanthanides is +3 but some elements also exhibit +2 and +4 oxidation states in which they leave behind stable ions. e.g. Eu: [Xe]4f’, Yb**: [Xe]af™ Cel: [Ke]4f’, Th**: [Xe]4f? Magnetic properties : have spin and orbit contributions (contrast to “spin only” of transition metals). Hence, magnetic moment is given by the formula w= V4s(S41)+LE+1, where L = orbital quantum number, $ = spin quantum number. Trend in magnetic moment is shown by graph: 10 Magnetic. properties Ho bie eee #2, Yass ao @ ah oO be ‘Atomic number —> cemusray Tooay |noveven 12 43 OGM © An aqueous solution of Ce" is a good oxidising agent. © Eu** and Yb** can exist in aqueous solution and are good reducing agents © Alllanthanide ions with the exception of La®, Lu** and Ce** are paramagnetic in nature. O Lanthanide contraction : It is the decrease in size of atoms and ions with increase in atomic number in lanthanide series. Consequences of lanthanide contraction — There is decrease in basic strength of oxides and hydroxides with decrease in the size from La to Lu. - Similar chemical properties. — The electronegativity of trivalent ions increases slightly from La to Lu — There is small increase in standard electrode potential values from La to Lu Colour : The species containing unpaired electrons are coloured and so is the case with lanthanide ions. The f-f transitions are possible ue to absorption of light from the visible region, O Reactivity : Due to their low values of ionisation energies, the lanthanides are very reactive. O Alloys : They form alloy especially with iron eg., MISCH METAL (rare earths 94-95%, iron 5% and S, C, Ca, Alin traces). ides OQ General outer electronic configuration is of Mod 2s, Am 98 | [Rn]5f7,7s" Rn] 5f"6d',7s* [Rn]3f",75° Rn]sf'°,7s" Rn]sf'7s" Rn]5f!2,737 Rn]5f' 37s" Rn)sf'4,7s7 [Rn]5f"4,6d!,75? +3 QQ Actinide contraction is similar to lanthanide contraction due to poor shielding by 3f electrons. 5 s The ions having 2 to 6 electrons in 5f-orbitals are coloured, both in crystalline and in aqueous solution, due to ff transition. Ions with 5/°, 5/7 and 5f" configurations are colourless. O They have higher tendency to form complex compounds. 1 Oxidation state : The common oxidation state is +3 but other oxidation states are also exhibited by actinides, the maximum being +7. COORDINATION COMPOUNDS: Introduction ‘© Wemer's coordination theory © Isomerism ‘Bonding in coordination compounds ‘© Importance of coordination compounds PSone Element Atomic| Electronic Oxidation! no. configuration states_| | 1 Difference between a double salt and Ac 89 [Rn|6d', 7s? 43 coordination compound Th | 90 |[Rn]6d?,75* 43,44 Coordination Double Pa 91 [Rn]5f?,6d',7s7 43, +4, +5. compound salt U 92 [Rn]5f%,6d',75" +3, +4, +5, A coordination A double salt is ionic +6 compound may or compound and does not Np 93 [Rn]5f',6d',7s* +3, +4, +5, may not be ionic contain any coordinate, +647 but the complex part bond. Pu o4 |[Rn}5/5,7% +3, +4, +5) always contains 46,47 coordinate bonds. 44 caemusray TopAy | ovate A coordination|A double salt loses its compound — (com identity in the solution. plex) retains its /eg., Mobr’s salt identity in the FeSO,(NH,),S0,-6H,0 solution. eg, KylFe(CN)g] Important Terms _ooxdinationsphese > Counter ions CCenffal metal ion Ligands Coordination number C2 Ligand : An ion or a molecule that can have an independent existence and can donate a pair of electrons. It can be negative ion, neutral molecule or positive cation (though rare in nature). C1 Denticity : It is the number of such ligating groups. © Unidentate : Which binds to a metal through a single point of attachment. eg., NHy, Br’, ete. © Bidentate: Which binds to a metal through two points. e.g, Ethylenediamine (en), oxalate (ox), etc. O Polydentate + Several donor atoms are present in one molecule. eg, EDTA is hexadentate ie., 6 donor atoms are present init, OQ Chelate complex : It is formed when a bi or polydentate ligand uses two or more donor atoms to bind to one metal atom. O Most common elements to act as donor atoms are N, P, O, §, halides and (in organometallic compounds). CQ Ambidentate ligands : Can ligate through two different atoms. e.g., NO3, SCN’, ete. M<—NO; =M<—ONO Mé«—SCN, -M<—NCS Q Coordination number : It is the number of ligand donor atoms to which the metal is directly bonded. Q Effective atomic number (EAN) : It can be obtained from the following simple expression EAN = Z- ON. +2(C.N.) where Z = Atomic number, O.N. = Oxidation number, C.N. = Coordination number of central metal atom, 1 Homoleptic complexes : Metal bound to only one type of donor groups. e.¢., [Co(NH),]**. Q Heteroleptic complexes : Metal bound to more than one type of donor groups. eg, [Co(NH,),Cl,]* Rules for 'UPAC Nomenclature 1 Name the cation, then anion. Non ionic compounds are given one-word name, C1 Naming of ligands : © Ligands are named first and central atom last. O Ligands are named in alphabetical order. O Neutral ligands are named the same as the molecule (except aqua and amine). © Anionic ligands are named by adding -o to the stem of the name (chloride becomes chlorido). © The ligand name is proceeded by a Latin or a Greek prefix to indicate how many are present, di-, tri-, fetra-, penta-, hexa-. QQ Inaneutralor cationic complex, the name of the central metal atom is followed by its oxidation. number in roman numerals in parentheses, Incase of bridging ligand the prefix pis written before the name of the ligand. Werner’s Coordination Theory Werner was able to explain the nature of bonding in complexes. According to Werner's theory metals have two types of linkages (valen C1 Primary linkages : Which are satisfied by the negative ions, ionisable and their number is equal to the ON, of central metal atom. They are always represented by dotted lines, C1 Secondary linkages : Which are satisfied by the negative, neutral or a positive species (ligands) and their number is equal to the coordination number of the central metal atom, These are non-ionisable and represented by complete lines. cemusray ropa |novevees 12 45 Isomerism Isomers are the compounds with the same molecular formula but different arrangements of atoms. ‘They have different properties. Structural isomerism. | Coordination compounds having different ligands within their coordination spheres. rt Tonisation isomerism || Hydrate/Sotvate isomerism || Linkage isomerism Complexes that give ||Complexes that differ in||Complexes that differ i different ions in||number of water molecules||the atom of a ligand solution, resent as ligands (inside the|| directly bonded to the Coordination isomerism Occurs when both positive and negative ions are| complex ions and two| ege[Co(NH,);Br]80, |lcoordination. sphere) and as}|metal atom, shown by| | isomers differ in ligands} [Co(NH,),S0,|Br |]free molecules (outside the||complexes containing| | distribution in two comples| coordination sphere). ambidentate ligands, ions. eg. [CHH;O),1Cly, eg,[Co(NH,),(NO,)ICl; | | eg.[Co(NH,)gIICr(CN)g] [Cr(#4,0),CI}CLH1,0 [Co(NH,),(ONO)ICI, [CxONH)g][CO(CN)g] Stereoisomerism| | Coordination compounds having different positions and arragements of ligands in space. eee Geometrical isomerism rises in heteroleptic complexes due to different possible geometric arrangementof the ligand, lS ae Optical isomerism Occurs when complex is represented by two different structures which are non-superimposable_mirror| {mages ofeach other called enantiomers x In octahedral complex [May?s] Facial (fac) :3 donor atoms of the same ligands occupy a f | adjacent positions atthe “SS va corners of an Zp ‘octahedral face. ye Meridional (mer) : When, the positions are around We the meridian of the FS octahedron. b In octahedral complex [Mab] b b Me wh a In octahedral complex [Mt(aa)3b,) oF (Maa) be] ° b eee Ox at In square planar complex Optical isomerism in [M(aa)2b3] [Mab] cis : 2 same ligands are @x---yb arranged adjacent to each other frans 2 same ligands are arranged opposite to each other. In square planar complex [Mabe] In square planar complex (Mabed] ‘These isomers are obtained by selecting 1 ligand, (a) and then | | dextro (d): Rotates plane of placing the remaining 3 ligands | | polarised light to right. (b, ¢ and d), one by one, trans to | | laevo (I) : Rotates plane of polarised. ligand (a), lightto left 46 cHEMsTRY TODAY |noveNsih 1 Bonding in Coordination Compounds Valence bond theory (VBT) : Features of this dsp? ‘Trigonal —Fe(CO)s, bipyramidal [Cucl,]* theory are = spd Square [SbF3]*" Uses hybrid orbitals to hold the donated Perit electron pairs for the formation of the op? lOctahedral | [CHINHs)g)"" coordinate bonds. (inner [Fe(CN)™ © Can explain the structure and magnetic orbital) ° Properties, © pi? lOctahedral (Fer), Coordi-. Type of (Outer [Fe(H,0),)°* nation hybri- Geometry Examples orbital) (NWNE,),?" number disation - 2 ” [Ag(NH3)9]". Inner orbital Outer orbital [Ag(CN) 3] complexes complexes 3 gt Tigo Involvesinnerd-orbitals. Involves outer d-orbitals. planar 7 ie, (n—1)d-orbitals. — ie., nd-orbitals. > 2 sp’ Tetrahedral moe oe Low spin complexes | High spin complexes 4 where X-CI'.Br,1| | Havelessorno unpaired Have large number of, a Square INKEN),F, electrons. | Umpaired electrons, ria (cucwt) e.g. [Co(NH)6P eg, (Mn), [CoF¢]* NONE) )** [co(CN),* Applications of VBT to Some Complexes S$. Atom/ion Configuration Oxidation No.of | Magnetic no. complex state of unpaired) behaviour metal electrons LN (a) ad 4s ap 42 2 | Paramagnetic NINN # Lt [Nich ANN) &] ee] Pr 2 Paramagnetic ‘Tetrahedral 2 [Ni(CN), | RENT Fax] ep] 42 dsp’, 0 Diamagnetic Rearrangement gap Square planar 20 Mn’) FF ‘nr sap 42 5 | Paramagnetic IMnCN))" | AT] ee) 2 spinner), 1 Paramagnetic Rearrangement ¢2sp3 Octahedral [Mach]? | TATA 4) 4] eefo] +2 p> 5 | Paramagnetic ‘Tetrahedral ‘cHemistry Topay | voveveen 14 47 3 Cw) Wal i a 4 ay 42 1 | Paramagnetic Icuc, >| FNINTNINTA) fe) bebodo 42 sp’, 1 Paramagnetic - ‘Tetrahedral (Cu(NH,),?*) NNN) ) BT 42, dsp’, 1 | Paramagnetic aa Square planar One electron is shifted from 3d to 4p-orbital 4 FES) TRTRTATS FA 0 4 | Paramagnetic [Fe(CO)s} | (NTNTNTNES) Ee) Eeb=P] 0 asp, 0 Diamagnetic Rearrangement gap ‘Trigonal “ bipyramidal U Limitations of VBT © It does not offer an explanation for the existence of inner-orbital and outer-orbital complexes. © It cannot explain colour and spectra. © ‘The thermodynamic or kinetic stabilities of coordination compounds are not quantitatively interpreted. Crystal Field Theory O Crystal field theory (CFT) was proposed by Bethe and Ven Vleck. It gives satisfactory explanation for the properties and bonding in coordination compounds. ‘The main points of this theory are : O The attraction between the central metal and ligands in the complexes is considered to be purely electrostatic. Thus bonding in the complex may be ion-ion attraction or ion dipole attraction. © Ligands are treated as points of negative charges O There is no interaction between metal orbitals and ligand orbitals, O The d-orbitals present in metal have the same energy in the free state. This is called degenerate state of d-orbitals. But, when a complex is formed the ligands destroy the degeneracy of these orbitals. ‘This effect is known as Crystal field splitting of d-orbitals, 48 cHEMistRY TODAY | noveNsih 1 Itaccounts for both the colour and the magnetic properties of complexes. It is based on d-orbital energy level splitting. State LZ rverapelens Bankentre aN, : eengeeasey # ctotisine . a [spherical crystal field * ovis Telos Splitting of d-orbitals ia an octahedral erystal field Spectrochemical Series QQ When the ligands are arranged in order of the magnitude of crystal field splitting, the arrangement, thus, obtained is called spectrochemical series I vient) 2% i [Ni(H,O) FP > [Ni(en)sF*, iG © For complexes in a ligand field, d-orbital occupancy depends on A, and_ pairing energy, P. = If A, > P (strong field ligand), electron pair-up in lower energy d-subshell first and forms low spin complex. — If A, < P (weak field ligand), electrons spread out among all d-orbitals before pairing up and forms high spin complex. ‘The polarising power x 108 x10" Importance of Coordination Compounds Biological Processes O Haemoglobin : Oxygen carrier is a complex ofiron (ID). © Chlorophyll : Green colouring matter of plants is a complex of Mg O Vitamin B,, : Isa complex of cobalt. O Analytical chemistry : Many metal ions are quantitatively estimated by complex formation eg, Cu, Ni*, APY. Red precipitate of nickel with dimethyl glyoxime cemusray Tooar |novevees 12 49 Hea MAP Core bel Net ene ae ee Mu “our Prieur] y ren erst eee Oe eee ea ste nth AlkanesparainsC,ay3] «# Isomeris~ Chain, Conformational «# Pybriisation sp Preparation 2CH,C00Ns + 241,0 foe ecb CH,CHO + 4H) (Creme esa) ich (Stereo) Dey at (CHB + 2Nas CH,be (we ain) 1 Special method or CH, AljG, + 12H,0 —> 4A110H), + 368,7 CH+Zn + ICH, (Craknd resco) Alkenes/olefins [C,H,,] © Tomeriam ~ Chain Position, Geometrical, Ring-chain. © Hybridisation sp? © Preparation CHOW ‘pinane (CH,cOoNs), (CH,b4),+20 Aromatic (Bowe: oll 9 Benenden Cy (here w=no.fG soma tote fds) ponies 3 partion: seeee Bath Padu een) “Ole on obese ate} Properties Alkanes Physical Boiling point + For straight chain alkanes bbpt = molecularsize Inisomeric alkanes, bptl/branching. {© Melting point : Even no. of C-atoms + Higher ‘mplsOddno.of atoms Lowerm pt. «© Density molecularmas. Chemical © Least reactive becasse of strong Cand CH. bonds. © Undergo only substitution reactions. 4 Salphonation and halogenation occur by free radical mechanism, Alkenes Physical ‘© B p.m. pt-andspecifc gravityoc molecular ‘6 Less volatile than alkanes. pt. and mp areigher thanalkanes Chemical '© Undergo electrophilic adlition easton 48 Tes for unsaturation and Bacyertests ‘© Adltion of unsymmetrical reagents (HN 0, HOX, ete) + Markovnikov'srule ‘¢ In presence of peroxides, addivon is ant Markovnikov'sor Peroxide cr Kharasch effect. ies bromine water Benzenoids Physical ‘© Meltingand oiling pointsocmolecular size © Solubilis organicsalvents, Chemical © Reactvi Insoluble fm wate but soluble in + Alkenes>alkynes>arenes> alkanes. ‘© Undergo electrophilic substitution reactions. 1# DomotgiveBacyer'test, Non benzenoids: ‘© Donotcontainbenzenering €Azulene, ropolone pyrtle,etc Alkynes{C,Hy al? Tomer” Chain, Position, Functional, Ring-chain, Hybridisation sp © Preparation Cac F2H0" (CHB), 20H,» 6g a 20+, ofCH=SCH}(CHCOOK), ‘Aromat verte eer) (tates ect ‘© Containa ringofthreeormoreC atoms. €Cyelopropane,cyelobutene et: (ropa } ae ‘© Anaromaticmolecule = Planar, cyclicand completelyconjugated, ~ Contains (an 2) electrons, an integer). Ion ring closure, the x-clectron energy of an ‘openchain polyene decreases. ‘go [6] anmulene (Benzene) ‘© Ananti-aromaticmolecule- = Planar, cyclicand completelyconjugated, = Contains 4nm-clectrons, (here (where n= an integer) =f, on ring closure, the a-electron energy ‘ego (A annutene (Cyciobutadiene) «¢ Anon-aromaticmolecule- = Non-planar, non-cyclic and not completely sonjugated. =f, on ing closure, the electron energy remainsthe same. ‘egeAlkanesalkenesand 1,3, Sylohepratriene © The first three members of alkanes do not chibi isomerism. # Alkanescontaining odd no, of atomscannot| beprepared by Kolbe electrolysis ‘© Methane cannot be prepared by Sabatier and] ‘Sendoreisreaction. © Method- ~ toascendthe C-chain-Wortzreaction, ~ todescend the C-chain -Decarboxyiation, avid 22 > substitution reaction © Benzene’ X, Lt > «ition reaction. © Octanena.-Knocking quality ofan automobile fick YY ageane Ine fo knocking] [Knocks oy) esses Regula gasoline # asotnes|*SIED <7hy Third grade gusotine (Resrere > Premium gasoline Alkynes Physical © Meltingandboiling points: Alkynes> alkanes andalkenes. 4 Solubility : Insoluble in water but soluble in ‘organic solvenss, [Chemical # Acidity + Alkyncs > alkenes > alkanes (ass-character «acidity, "Test for unsaturation-Gives bromine water and Boeyertest Undergo eletrop f Degeee of unsaturation or index of hydrogen Aeficiency = (21 +2 1,)/2. where m, = number ofearbon atoms, n= number ofhydrogen atoms. le and nucleophilic addition ‘© Tetraethyl lead (an antiknock compound) is used as a misture of TEL (63%), ethylene bromide (25%), ethylene chloride (9%) and methyleneblie(2), + Cetane no. = Sale to desde quality of dese fia 6 CHYCH) CH co Mawleane, Tenge ere oer Tver) iby CO Metallurgical Processes O Nickel is purified by Mond’ process forming volatile nickel carbonyl Ni +4CO —> Ni(CO), 4 Ni + 4€O. © Extraction of silver and gold by cyanide process involves complex formation. Aglagy + 2N@CNiagy —> NalAg(CN)a] ap + Najag) Auayy + INACN (ag) —> Nal Au(CN) 2] ag) + Naog) VGC TT ‘© Introduction ‘© Classification of pollutants © Types of pollution : Air, water and soil pollution Dian CO Environmental chemistry is the branch of chemistry that deals with the study of various chemical processes taking place in the various segments of the environment. O Hydrosphere : Water bodies (sea, oceans, rivers, lakes, etc.) cover about 75% of earths surface. O Lithosphere : Solid part consisting of soil, rocks, mountains, etc. Q Biosphere : Part where living organisms interact with lithosphere, hydrosphere and atmosphere. U Abiotic components(non-living):Lithosphere, hydrosphere, atmosphere. CQ) Tropospheric Pollution Pollutants co Major sources C2 Biotic components (living) : Plants, animals, human beings. 1 Medium : Soil or organism affected by the pollutant or contaminate is called a receptor. Sink is a chemical medium or species that retains and interacts with the pollutant. Classification of Pollutants (1 On the Basis of the form in which they Persist O Primary pollutants :‘Those which remain as such after their formation. e.g, nitric oxide (NO), SO,, NO}, CO, hydrocarbons etc. O Secondary pollutants : Formed from the primary pollutants in the atmosphere or hydrosphere. For example, hydrocarbons and oxides of nitrogen react together photochemically to form certain compounds eg, PANs ie. peroxyacetyl nitrates. On the Basis of Disposal O Degradable pollutant : Degrades after some time either automatically ie., by heating or through action of microorganisms (bio-degradable, e.g, sewage). O Non-degradable pollutant : It does not get degraded or broken down into harmless material, e.g., DDT, plastics. ‘Types of Pollution 2 Air pollution : It is the addition of undesirable materials into the atmosphere either due to natural phenomena or due to human activity on the earth which adversely affect the quality of the air and hence, affects the life on the earth. Effects Incomplete combustion of carbonaceous Carbon monoxide is toxic. It binds with matter in automobile engines and haemoglobin in red blood cells and prevents defective furnaces, matter, voleai NO, Combustion of fuel, natural fires, _anthro-stationary forest combustion incomplete them from combining with oxygen. Low combustion of agricultural and_ slash eruptions, forest fires. levels of CO cause headaches and dizziness. Concentrations of ~19% causes death in minutes, Toxic to living tissues, harmful to paints, textiles and metals. sources (factories and power plants), transportation. 52. CHEMISTRY TODAY |noveNsih 1 50, Anthro-stationary combustion sources, ‘They are respiratory tract irritants, low industry found in metal ores, coal, decay concentration causes throatandeyeirritation, products, volcanoes. Hydrocarbons refineries, anaerobic gas. CIC's CFC inert (in the lower atmosphere). were used primarily as a refrigerants, in aerosol sprays and in the plastics industry. Freons are stable (lasts for over 80 years), inflammable, and causes breathlessness, affect larynx. Combustion of fuel in automobiles, At concentration greater than 500-1000 ppm, bacterial decomposition of organic matter, natural they have carcinogenic effect in lungs. They reactwith O, and NO, to form photochemical smog which have a strong damaging effect on human being as well as plants. React with stratospheric ozone. When CFC’s are broken down, chlorine free radicals are produced. ‘These can react with more than 10,000 molecules of ozone. ‘Thus, depleting the ozone layer. Particulates incomplete combustion, crushers and grinders, Volcanic eruptions, fly ash, smelting and mining operations, smoke from dust from Inhalation of metallic particles leads to respiratory disorders like asthma, bronchitis, lung cancer, ete. Greenhouse Effect and Global Warming The retention of heat by the earth and atmosphere from the sun and its prevention to escape into the outer space is known as greenhouse effect. ‘© Greenhouse gases such as CO,, ozone, methane, chlorofluorocarbon compounds and water vapour form a thick cover around the earth which prevents the IR rays emitted by the earth to escape. © Itgradually leads to increase in temperature of atmosphere. OQ. Consequences of Greenhouse Effect © Global warming would result in rise in sea level due to increased rate of melting of glaciers and floods. © Spread of some tropical diseases. O New weather patterns Acid Rain U Ihe oxides of C, N and § present in the atmosphere, dissolve in water and produce acids and lower the pH of water to below 5.6. H,0 + CO, —> H,CO, == H* + HCO; 2H,0 + 280, +O, —> 2H,SO, == 4H" + SOP 2H,0 +4NO, +0, —> 4HNO, == 4H" + 4NO; ‘The acids are toxic to vegetation, react with marble and damage buildings. CaCO; + H,S0, —> CaSO, + H,0 + CO, Acids corrode water pipes and produce salts with heavy metal ions viz., Cu, Pb, Hg and Al toxic in nature. Smog The word smog is derived from smoke and fog Itis the major air pollutant. Smoke + Fog —> — Smog (containing harrnfil gases) Classical smog Photochemical smog Also called as Also. called as Los London smog. Angeles smog. Formed due to Formed due to oxides oxides of sulphur, of nitrogen. Contains primary Contains secondary pollutants pollutants Causes bronchitis Causes irritation in and problems in eyes lungs. It is reducing in It is oxidising in nature. nature. cceausray Tooar | oveves 12 53 C1 Stratospheric Pollution ° Ozone depletion = The ozone layer, existing between 20 to 35 km above the earth's surface, shield the earth from the harmful UV radiations from the sun. The UV radiations cause skin cancer, cataract of eye, and harmful to vegetation. = Depletion of ozone is caused by oxides of nitrogen. N,0 + hv —> NO +N (Reactive) NO +O; —> NO, +0 0, + hv —> 0, +0 NO, +O —> NO +0, 20, + hv —> 30, (Net reaction) = The presence of oxides of nitrogen increase the decomposition of 3. Depletion of ozone by chlorofluoro- carbons. CF,Ch + hw —> CRCI + cr CPC; + vu —>, CEC, + Cl G46, > A640, exe C16 +O > C1 +0. 03 + O > 20, (Net reaction) QO Water Pollution oO Natural wastes Organic chemicals Metals (Hg, As, Pb, C Man-made wastes wastes, oil pollution. Water pollution is defined as, the contamination of water by foreign substances which makes it harmful for health of animals, plants or aquatic life and makes it unfit for domestic, industrial and agricultural use Pollutants Major sources Leaching of minerals, silt rom soil erosion, falling of organic matter from banks, ete Pesticides, surfactants, deter- gents, industrial wastes. ‘Nuclear power plants, mining, metal plating industries. etc.) Sewage, domestic wastes, soaps and detergents, wastes from animal sheds and slaughter houses, run off from agricultural fields, industrial 54. CHEMISTRY TODAY |nveNsih 1 Effects of water pollution : High concentrations of fluoride (over 10 ppm) are poisonous and harmful to bones and teeth. = Excess nitrate in drinking water can lead to ‘blue baby’ syndrome. = Excess sulphate (> 500 ppm) causes laxative effect. Remedial measures : = Degradation of organic content of vaste water by microbial oxidation. = Removal of phosphates, coagulation, filtration and disinfection using chlorine for improving the quality of waste water. — Sewage treatment should be improved. = Settlement of the filtered waste water to remove suspended solids, oily and greasy material which floats on the surface can be skimmed off. Biochemical Oxygen Demand (BOD) : It is defined as, the amount of free oxygen required for biological oxidation of the organic matter by aerobic conditions at 20°C for a period of five days. Its unit is mg/L or ppm. An average sewage has BOD value of 100 to 150 mg/L. Q Chemical Oxygen Demand (COD) : It is measure of all types of oxidisable impurities (biologically oxidisable and biologically inert organic matte such as cellulose) present in the sewage. COD values are her than BOD. values. O Soil Pollution o fe) ‘The addition of substances in an indefinite proportion changing the productivity of the soil is known as soil pollution. Sources of soil pollution : = Agricultural pollutants : Chemicals like pesticides, fertilizers, fumigants, insecticides, herbicides, fungicides. ~ Domestic refuge and industrial wastes. = Radioactive wastes from research centres and hospitals. = Soil conditioners containing toxic metals like Hg, Pb, As, Cd ete = Pollutants present in air from chemical works © Effects of soit polation Pollution runs-off into rivers and kills the fishes, plants and other aquatic life. = Cropsand foddergrownonpollutedsoil may pass on the pollutants to the consumers = Soil structure is damaged (clay ionic structure impaired), = May release vapours and hydrocarbons into buildings and cellars and cause corrosion of foundations and pipelines. = Contaminated — soil soil fertility and hence, there is decrease in the crop yield. ~ When soil pollution modifies the soil structure, death of many beneficial soil organisms (e.g. earthworms) in the soil could take place decreases People living near polluted land tend to have higher incidences of migraines, nausea, fatigue, skin disorders and even miscarriages. © Control of soil pollution - Reuse and recycle unwanted items. The less rubbish we create, the less chance the waste will end up in our soil — Make use of organic fertilizers and organic pesticides, because they are usvally made of natural substances so are biodegradable. ~ Insist on buying natural and organic food, because chemical pesticides and fertilizers are not used in their growing process, = Cut down the usage of paper or use recycled paper. Exam Café QUESTIONS FOR PRACT! 1, The IUPAC name of [Pt(NH,),NO3CI}SO, is (a) tetraamminechloridonitrito-N-platinum(IV) sulphate (b) tetraamminechloridonitrito-O-platinum(IV) sulphate (c) chloridonitrotetraammineplatinum(1V) sulphate (a) platinum(IV)tetraamminenitrochlorido. sulphate. 2. Reagent used to distinguish H,O, and O, is (a) lead sulphide —_(b) starch and iodine (c) potassium permanganate (a) bleaching powder. Which of the following statements is incorrect? (a) All halogens form oxyacids. (b) All halogens show -1, +1, +3, +5 and +7 oxidation states, (©) Hydrofluoric acid forms KHF,, K,F, and attacks glass. (d) Oxidising power of halogens follows the order F; > Cl > Bry > Ip. 4, Inert atmosphere needed for welding of metals is obtained by (a) Ar, He (b) Nz, He (©) 03, Ne (a) Ar, Ne Native silver metal forms a water soluble complex with a dilute aqueous solution of sodium cyanide in the presence of (a) nitrogen (b) oxygen (©) carbon dioxide (@) argon ‘The chemical formula for tartar emetic is CH(OH)COOH FHIOHICOONa ) (a) | CH(OH)COOK CH(OH)COOK CH(OH)COO(SbO) , CH(OH)COOK (©) (@) | CH(OH)COOK CH(OH)COOK Which of the following statements is incorrect? (a) ‘The average residence time of NO is one month (b) Limestone acts as a sink for $O,. cuemistayropay | oreveen a 55 (©) SO, can be removed from flue gases by passing through a solution of citrate ions. (4) Ammonia acts as a sink for NO, Copper sulphate solution decolourises on addition of potassium cyanide due to the formation of a) [Cu(CN),]? (b) [Cu(cN),]° (c) Cu(CN) (d) CuCN, ‘The reaction, 3C1O{44) —> C105 aq) + 2Cliugy is an example of (a) oxidation reaction (b) reduction reaction (c) disproportionation reaction (d) decomposition reaction. ‘The molecular shapes of SF,, CE, and XeF, are (a) the same with 2, 0 and 1 lone pairs of electrons on the central atoms respectively (b) the same with 1, 1 and 1 lone pairs of electrons on the central atoms respectively (c) different with 0, 1 and 2 lone pairs of electrons on the central atoms respectively (a) different with 1, 0 and 2 lone pairs of electrons on the central atoms respectively. 10. 11, When rain is accompanied by a thunderstorm, the collected rainwater will have a pH value (a) slightly lower than that of rainwater without thunderstorm (b) slightly higher than that thunderstorm is not there (©) uninfiuenced by the thunderstorm (a) depends upon the amount of dustin air. when the of, occurrence 12, A bottle completely filled with conc. H,SO, is left unstoppered for several days and we observe spontaneous overflow of acid. It is due to (a) change in temperature (b) hygroscopic nature of H,SO, (0) absorption of air by H,SO, (d) dehydration of H,S0,. Two compounds pentaamminesulphato- cobalt(IL1) bromide and pentamminesulphato- cobalt(III) chloride represent (a) linkage isomerism (b) ionisation isomerism 13, 56. CHEMISTRY TODAY |noveNsih 1 14, 15, 16. 17. 18, 19, 20. (c) coordinatio (d) no isomerism. isomerism. Bordeaux used asa fungicide is a mixture of (a) CuSO, and Ca(OH), (b) CaSO, and Cu(OH), (©) CuCO, and Cu(OH), (d) CuO and Cad Select the correct statement(s) regarding the behaviour of HF as a non-aqueous solvent. (a) HCI behaves as an acid and HF as a base. (b) HCI, behaves as a base and HF as an acid. (©) HNO, and H,SO, behave as base and HF as an acid. (@) Allare correct. Oxidation of hydrogen halide, HX affords a method for the industrial and laboratory preparation of the halogen, Xin the free state in respect of all of the following except (a) fluorine (b) chlorine (©) bromine (d) iodine, Which of the following molecules has planar structure? (a) NFS (b) NH,OH (©) PSCl, (@) PECL Which of the following substances are regulated by the Kyoto Protocal? I. Argon II, Carbon dioxide IIL, Nitrogen IV. Nitrous oxide V. Sulphur hexafluoride (a) I, Hand IL (b) Land III (©) Hand V (d) I, Vand V In which of the following coordination entities the magnitude of A, (CFSE in octahedral field) will be maximum? (At. no. of Co = 27) a) [Co(C,0))3° —(b) [Co(H,0),]*" (©) [Co(NHg)g!** — (@) [Co(CN),]* The colour of CuCr,O, solution in water is green because (a) CrOF ions are green (b) Cu?* ions are green (c) both Cr,07" and Cu”* ions are green (d) Cu?* ions are blue and Cr,0: yellow. What is JEE (MAIN) like? mee A Se EXPLORER Eye [urate iced Rs 285 491 pages Thinking about competing in the JEE? Unsure of what it's like? Get a first-hand feel with MTG's JEE Main Explorer. With solved papers from the past 13 years, glance through the changing pattern of examination. Or attempt the papers to check your chances of success. Either way, at Rs 285, isn't this a steal for JEE aspirants like you? So what are you waiting for? Order MTG's JEE Main Explorer today. Scan now with your smartphone er tobet ‘Applicaton tread Reeder required Se ee een er PoE ee ee te eee ace ad ‘cHemistrY Topay | voveveen ‘14 57 21, Hydrolysis of Pl; yields (a) amonobasic acid and a salt (b) a monobasic acid and a dibasic acid (0) a dibasic acid and a tribasic acid (d) a monobasic acid and a tribasic acid. 22. Antichlor is a compound which (a) absorbs Cl, (b) removes Cl, from a material (0) liberates Cl, from bleaching powder (@) acts as a catalyst in the manufacture of Cly. 23, Which of the following statements about polar stratospheric clouds (PSCs) is not correct? (a) PSCs do not react with chlorine nitrate and HCL. (b) Type I clouds are formed at about -77°C and contain solid HNO,.3H,0. (©) Type II clouds are formed at about -85°C and contain some ice. (d) Due to presence of PSCs a tight whirlpool of wind called Polar Vortex is formed which surrounds Antarctica. 24, ‘The structure of dithionate ion is > (a) ope ‘oy " es © ey © i 7) (c) Som, oy ix ve 7 fe) Z a ops ‘d 25, The compound containing coordinate bond is (a) O; (b) SO5 (©) H,80, (@) Allof these. 26. Ifa non-metal is added to the interstitial sites of a metal, then the metal becomes (a) softer (b) less tensile (c) harder (a) more du 27. In the volumetric estimation of Fe(II) with Cr,0F in acidic medium, K3[Fe(CN),] is used as an external indicator. The end point will be reached when the solution of iron salt 58 CHEMISTRY TODAY |noveNsih 1 (a) starts giving blue colour with indicator (b) ceases to give blue colour with indicator (c) starts giving red colour with indicator (a) ceases to give red colour with indicator 28. The coloured discharge tubes for advertisement mainly contain (a) xenon (b) helium (©) neon (€) argon, 29, Metals of group-12 are softer than other transition metals because (a) group-12 metals have a cage-like structure (b) group-12 metals have high ionization energies (©) sas well as d-electrons take part in metallic bonding (d) delectrons do not take part in metallic bonding. 30. Phosphine is not evolved when (a) white phosphorus is boiled with a strong solution of Ba(OH), (b) phosphorous acid is heated (©) calcium hypophosphite is heated (d) metaphosphoric acid is heated. Ens 1. (a): [Pt(NH,),NO,CI]SO, ‘Tetraamminechloridonitrito-N-platinum(1V) sulphate x (c) : The pink colour of potassium permanganate is decolourised by HO, and not by 0. 2KMnO, + 3H;S0, —> K,SO, +2MnSO, +3H,0 +50 [H,0, —> H,0+0]x5 [0+0 —> 0] x5 2KMn0O, + 3H,SO, + 5H,0, —> K,SO, +2MnSO, + 8H;0 + 50; 3. (b): Fluorine shows only -1 oxidation state. 4. (a) 5. (b): Metallic silver dissolves in sodium cyanide solution in the presence of oxygen to form water soluble complex i¢., sodium argentocyanide. 4Ag + 8NaCN + 2H,0 + Oy44¢) —> 4Na[Ag(CN),] + 4NaQH CH(OH)COO(SbO) 6. (c): Tartar emetic is | CH(OH)COOK 7. (a): 4 days. 8. (b): (CuSO, + 2KCN —> Cu(CN), +K,SO,] x2 2Cu(CN), —> Cu,(CN), + (CN). Cu,(CN) + 6KCN —> 2K,[Cu(CN),] 2CuSO, + 11KCN —> 2K,[Cu(CN),] +2K,S0, + (CN), hhe average residence time of NO is Oxidation iui? Fag * 2Chan Reduction XeF, (Squat planar) to lone pairs 11, (a) : Normal rainwater haspH5.6. Thunderstorm, results in the formation of NO and HNO; which lowers the pH. 12. (b) 13, (d): Pentaamminesulphatocobalt(II1) bromide [Co($04)(NH3) HNO} + F HF + H,S0, —> 1,80 + F 16. (a) 17. (a): (a) Planar (b) Pyramidal at N and bent at O (c) Tetrahedral (@) ‘Trigonal bipyramidal with apical Cl atom. 18, 19, 20. 2. 22. 23. 25. 26. 27. 28. 29. 30. (a) (d): Greater the charge on central metal ion, and stronger the field of ligand, greater is the A, value (CFSE). According to the spectrochemical series, the increasing order of A, is C0, H,PO, + 3HT Dibasic~ Monobasic acid acid (b): Antichlor is a compound which removes unreacted chlorine from a material. For example hypo. (a) : PSCs react with chlorine nitrate and HCL to give HOCI and Cl. . (b) : Dithionate ion ($,0,°) is OX 0} oi I “So oO ' @: 0 s °K, an Z 0” So oo N, e Non Os 05 H,80, (c) : Ifa non-metal is added to the interstitial sites of a metal, then metal becomes even more harder. (b) : Fe(II) gives blue colour with K,[Fe(CN)g] but Fe(III) does not. 3Pe** + 2K3[Fe(CN)g] > Fes[Pe(CN),] + 6K” Blue (c): Neon is used in discharge tubes for advertisement purpose. (d): Metals of group-12 are softer than other transition metals due to comparatively weak metallic bond since their d-electrons do not take part in metallic bonding. (a) ‘cHemistrY Topay | voveveeR 14 59 aE CBSE-B©ARD CHAPTERWISE PRACTICE PAPER Alito Haloalkanes and Haloarenes | Alcohols, Phenols and Ethers Time : 3 hrs. Marks : 70 GENERAL INSTRUCTIONS (All questions are compulsory. ( Git Question numbers I to 5 are very short-answer questions and carry I mark each, Question numbers 6 to 10 are short-answer questions and carry 2 marks each (iv) Question numbers 11 to 22 are also short-answer questions and carry 3 marks each, (v) Question number 23 is value based question and carries 4 marks. (vi). Question numbers 24 to 26 are long-answer questions and carry 5 marks each. (vii) Use Log Tables, if necessary. Use of calculator is not allowed. 1. Why is chloroform stored in brown coloured bottles? 2. Why is ethanol less acidic than water? Why is sulphuric acid not used during the reaction of alcohols with KI? 4. How do you account for the miscibility of ethoxyethane with water? 5. Phenols do not undergo substitution ofthe -OH group like alcohols, why? 6. What are the products of the following reactions? (i) CH3CH)CH =CH, + HBr TE 5 (ii) CH CH = C(CH;), + HBr ———> 7. Give equations of the following reactions : (i) Oxidation of propan-I-ol with alkaline KMn0, solution. (ii) Treating phenol with chloroform in the presence of aqueous NaOH followed by hydrolysis. OR Ilustrate with examples the limitations of Williamson’s synthesis for the preparation of certain types of ethers. 60. cHemisray TopAy | ovesee 8 8. Write the IUPAC names of (i) ethylidene chloride (ii) ethylene dichloride. 9. (i) Convert propan-2-one into tertiary butyl alcohol. (ii) Arrange H)O, ROH and CH = CH in the increasing order of acidity. 10. Which one in the following pairs undergoes Syl substitution reaction faster and why? Kak (i) or a (ii AMA“ 11. Write the equations for the reactions of hydrogen iodide with (i) 1-methoxypropane i) methoxybenzene (iii) benzyl ethyl ether. 12. How can the following conversions be carried out? (i) Propene to propan-1-o1 (ii) Benzene to 4-bromonitrobenzene (iii) Aniline to chlorobenzene 13. Write the mechanism of hydration of ethene to yield ethanol. 14, Illustrate the following name reactions: (i) Warts reaction (ii) Sandmeyer's reaction (iii) Fittig reaction 15. How will you synthesize (i) L-phenylethanol from a suitable alkene (ii) cyclohexylmethanol using an alkyl halide by Sy? reaction. (iii) pentan- 1-ol using a suitable alkyl halide. 16. (i) Give the TUPAC name and structural formula of D.D.T. (ii) Complete the following: UN light 17. Write equations of the following reactions: (i) Nitration of anisole (ii) Bromination of anisole in ethanoic acid medium (iii) Friedel-Crafts acetylation of anisole. 18. Arrange the compounds of each set in order of reactivity towards Sy2 displacement: (i) 2-Bromo-2-methylbutane, 1-Bromopentane, 2-Bromopentane (ii) 1-Bromo-3-methylbutane, 2-Bromo-2-methylbutane, 2-Bromo-3-methylbutane (iii) 1-Bromobutane, 1-Bromo-2, 2-dimethylpropane, 1-Bromo-2-methylbutane, 1-Bromo-3-methylbutane 19. (i) Name the reagents and write the chemical equations for the preparation of the following compounds by Williamson's synthesis: (a) Ethoxybenzene (b) 2-Methyl-2-methoxypropane (ii) Why do phenols not give the protonation reaction readily? 20. What happens when (i) n-butyl chloride is treated with alcoholic KOH (ii) bromobenzene is treated with Mg in the presence of dry ether (iii) chlorobenzene is subjected to hydrolysis? OR Identify A, B, C, D, E, Rand R’ in the following: ® Oy teeatg dryetber, 4 HO, (i) R—Br+ Mg CPC HGHCH, D (iii) CH, CH; ether pry M CHy cH, Mth px Es p CH, CH, Hof E 21. Write structures ofthe products ofthe following reactions: (@ cH,-cH=cH, > ° cHy-¢—0cH, > (ii) u i ) CH,—CH, “CH CHO CH, 22, Explain the following with an example: (i) Kolbe's reaction (ii) Reimer—Tiemann reaction (iii) Williamson's ether synthesis 23. Raj’ father wanted to go to the hospital to his ailing friend. Raj insisted to accompany h father. On reaching the hospital, Raj noticed a peculiar smell. After reading the passage, answer the following. questions: (i) Name the chemical compound which causes the hospital smell. (ii) What is the use of this chemical and how does it work? (iii) How is this chemical prepared in the laboratory? (iv) Can we use some other chemical which has the desired effect but no smell? 24. (i) Give chemical tests to distinguish between compounds in each of the following pairs: cemusray Tooay |noveven 12 61 25. i) CH) Gi) @ (ii) «i Gi) (a) Phenol and Benzyl alcohol (b) Butan-2-ol and 2-Methylpropan-2-ol How would you synthesize the following alcohols from appropriate alkenes? CH, OH @) Chon ) wy OH (©) OR How would you account for the following: (a) Phenols are much more acidic than alcohols. (b) The boiling points of ethers are much lower than those of the alcohols of comparable molar masses? Give reason for the following: (a) m-Aminophenol is stronger acid than o-aminophenol. (b) Alcohols act as weak base. (c) Propanol has higher boiling point than that of the hydrocarbon butane. Primary alkyl halide (A) C,HgBr reacted with alcoholic KOH to give compound (B). Compound (B) is reacted with HBr to give (C) which is an isomer of (A). When (A) is reacted with sodium metal it gives compound (D), CgHyg which is different from the compound formed when n-butyl bromide was reacted with sodium. Give the structural formula of (A) and write the equations for all the reactions. Write the isomers of the compound having molecular formula C,HoBr. OR Explain why: (a) thedipole moment of chlorobenzene is lower than that of cyclohexyl chloride. (b) alkyl halides, though polar, are immiscible with water. (©) Grignard reagents should be prepared under anhydrous conditions. A hydrocarbon CsHi does not react with chlorine in dark but gives a single 62. cwemistmy TopAY|novensih monochloro compound CsHgCl in bright sunlight. Identify the hydrocarbon. 26. (i) How would you account for the following: (a) Ethers possess a dipole moment even if the alkyl radicals in the molecule are identical. (b) o-Nitrophenol is more acidic than ‘o-methoxyphenol (©) Primary alcohols are more acidic than secondary alcohols? (ii) How are the following conversions carried out? (a) Ethyl magnesium chloride to Propan-1-ol (b) Methyl magnesium bromide to 2-Methylpropan-2-ol OR (i) (@) When 3-methylbutan-2-ol is treated with HBr, the following reaction takes place hr CH,—CH—CH—cH, “>cH,—C—CH,—CH, it i 3 CH, OH cH; Give a mechanism for this reaction. (b) How are the follo carried out? (Ethanol to Propan-2-ol (i) Ethanol to 1,1-Dichloroethane (ii) Complete the following reaction equations: (a) Con + SOCly;—> ing conversions EO 1. In the presence of sunlight and air, chloroform is slowly oxidised to highly poisonous phosgene gas. 2CHCI, + 0, 8s 2COCl, + 2HCl Phosgene 2. ‘The ethyl group in ethanol is electron donating (4Leffect) and increases the electron density in 3. 4, 5. 6. 7. the O — H bond making it difficult to remove HasH ion. CH; O--H HySO, is a strong oxidising agent and hence oxidises HI produced during the reaction to ly. Ethoxyethane is miscible in water because of hydrogen bonding. GHs\ HN 9-H O- CH HO ‘TheC— Obondin phenolshas some doublebond character due to resonance and hence cannot be easily cleaved by nucleophile (i) CH;CH,CH = CH, + HBr Peg CH;CH,CH,CH,Br 1-Bromobutane Anti-Markownikoff’s (Kharasch or peroxide effect) CH; Hs (ii) cn,cis¢ + HBr—>CH,CH;-C—CH, rule Br cH, 2-Beomo-2-methylbutane Markownikoff's rule alk. KMn0, (i) CH,—CH,— CH,OH +> Propan-|-of ° CH,CH,COOH + H,0 Propanoic acid on ONa . CHO (ii) + CHL, 2H Phenol ail Hcl {ins OH CHO Salicyladehyde OR Williamson's synthesiscannot beemployed for tertiary alkyl halides as they yield alkenes instead of ethers. The reaction of CHONa with (CHs)3CBr gives exclusively 2-methylpropene. 8 @ (ii) » W (ii) 10. (i) (ii) a CBr + Na—G-CH, I ca, | CH,—CSCH, + NaBr 1 CH, Aryl halides and vinyl halides cannot be used as substrates because of their low reactivity in nucleophilic substitution, Ethylidene chloride is gem-dichloride in which both Cl-atoms are attached to the same carbon atom. CHy~GH—CL cal 1, 1-Dichloroethane Ethylene dichloride is vic-dihalide in which Cl-atoms are attached to adjacent carbon atoms. eg aoa 1, 2 Dichloroethane a Mga CHA OY cH Mee S CH,—C-CH cn” ° Sy Hs opan-2-0ne GE, Propan-2. find: Gi CH,-¢-On CH, {Butyl alcohol CH < ROH < HO Aeidity Oxygen is more electronegative than sp hybrid carbon and further alkyl group in alcohols increases electron density due to +1 effect hence, ionisation decreases. a Tertiary halide reacts faster than secondary halide in Sy1 reaction because of the greater stability of tertiary carbocation intermediate. 1 Secondary halide reacts faster because of greater stability of secondary carbocation than primary. cemusray Tooay |oveves 12 63 11. (i) CH,CH,CH,—O-—CH, 1-Methoxypropane HI a K ‘OH + CH,—1 I-fodomethane oc, » Gum +CH-I Iodomethane Maethoxybenzene Phenol CH,-O-C)H, CHI HI. 373K + CjH,OH Ethanol Benzyl ethyl ether Benzyl iodide 12. (i) cH, HBr —CHECH, ae CHs—CH,—CH,Br Propene fn Konia CH,—CH,—CH,—OH Propan-l-ol Br NO, 4-Bromonitrobenzene NH, N=nct NaNO, + Hi K Benzenediazonium chloride Jescunct a (i) cone. H,SO, Oun Gas omg Benzene Bromebenzene Aniline Chlorobenzene 13. ‘The acid catalysed hydration of ethene may be represented as: H. H +H Nes=ct B° 8. cH,—ch,-on “H Bihene Ethanol ‘The mechanism followed by the above reaction. may be depicted as: 64. cuemistmy TopAY|novensin 14, 15, Step 1: Generation of carbocation : Protonation of ethene yields a carbocation. cm, H,0: + H*—> H,0° HY Lo", Cy ty wesc PH an CH, +H,0 Carbocation Step 2: Nucleophilic attack of water on carbocation: Thecarbocation polarizesthelone pair ofelectrons of © of water and hydration takes place. ta, Ht CHy~CH, + HO CH CHOC Step 3: Formation of product : Regeneration of the proton takes place. CH,—CH,— OF Fly CH,—OH +H Ethanol (i) Wurtz reaction: cH, F3Nas Br}-cH, eat Methyl bromide CH,—CH, +2NaBr Fuhane Sandmeyer’s reactio NiCI, cl 2 Cuch, +N, Benzenediazonium chloride Chlorobenzene (iii) Fittig reaction: Ox 1) saat a Chiorobenzene +2NaCl Diphenyl (i) When ethenylbenzene is treated with dilute HSO, it gives 1-phenylethanol. Ou CH=CH, Cr +H,0 ? dil. 1,80, cH. ‘cH, 1-Phenylethanol Ethenylbenzene (ii) When cyclohexylmethyl bromide is treated with aq. NaOH, it gives cyclohexyimethanol. CHBt 5.2 reaction CH,OH cy NaOH ug, PES +NaBr Cyclohexylmethyl bromide Cyclohexylmethanol (iii) CH(CH,)3CH Br + NaOH (gg) ——> | Bromopentane CH,(CH);CH OH + NaBr Pentan- 1-ol 16. (i) D.D‘T.(p,p’-dichlorodiphenyltrichloroethane) a{O)-en-ca, a TUPAC name: 2,2-bis(p-chlorophenyl)-1,1,1-trichloroethane. a shay Ch cl i) eG 43, Lilet, a cl Benzene g Benzene hexachloride Br b) Heat (b) OC + Bry Wine +HBr Gystohexene OCH, OCH, OcH, NO, ‘ conc. HNO, 2 Anisole o-Nitroanisole NO, p-Nitroanisble OCH, OCH, oy By Gi) Gi,coon” ,COOH’ Anisole ° os prorat (iii) OCH, OCH, OCH, COcH, oO + excoa CY + Anisole Acetyl chloride o-Methoxy . me eaptane COU = p-Methoxy- acetophenone 18. The reactivity of alkyl halides towards Sy2 displacement follows the order 3° < 2° < 1°. ‘This is because primary alkyl halide has lowest steric hinderance and tertiary alkyl halide has highest steric hinderance. (i) 2-Bromo-2-methylbutane < 2-Bromopentane < 1-Bromopentane (ii) 2-Bromo-2-methylbutane < 2-Bromo-3-methylbutane < L-Bromo-3-methylbutane 1-Bromo-2, 2-dimethylpropane <1-Bromo-2-methylbutane <1-Bromo-3-methylbutane < I-Bromobutane All these are primary alkyl halides but 1-bromobutane has least steric hinderance and I-bromo-2,2-dimethylpropane has most steric hinderance, ONa OCH,CH, 19.) @ + CH,CH,Br-bet| Bromoethane Sod phenonide +NaBr Ethoxybenzene cH, heat (b) CH;—C—ONa + CH, Br | Bromomethane J CH; CH; Sod. -methyl-2-propexide 3 CHy-C-OcH; CH 2-Methyl-2-methoxypropane (ii) In phenols, the lone pairs of electrons on the oxygen atom are delocalised over the benzene ring due to resonance and hence are not easily available for protonation. H,—CH,—CH,—CH,—Cl nfutyl chloride a6: KOHL CH,—CH,—CH=CH, But-l-ene (ii) (Oy: + Mg teeter, (C))—migbr Bromobenzene Phenylmagnesium bromide (ii) (Ora Names, (O-on Chlorobenzene Phenol 20. (i) NaOH, 623K, 300 atm cemusray Tooay | oven 12 65 OR “ Cte Mg aay Qe mn-O 7 B Grignard reagent I (ii) Ris CH;—CH—CH, CHy=CH-CH, + Mg dry ether Br CH CHP CH, CH-CH ] D MgBr Msi en (i) R isu, e— CH, CH, CH, CH, Navether I cH CH HE CHEK CH, CH, cH, fy cH, cH, Ho. ony 2 cH, of oex cH, cu, EO D OH 21. (i) CH; CH=CH, 2°"5cH,—CH—CH, Propan-2- ° ) Onna i ° on Methy-2-(2"-hydroxyeyclohexyi) cthanoate cur —cro ts (ii) CH,—CH,— cH, CH,—CH,—CH—CH,OH 66. cHEMistRY TODAY |novensih Kolbe’s reaction : When sodium phenoxide is heated with carbon dioxide under pressure, it gives salicylic acid. 22. (i) O-Na* OH COO™-Na* Qa CY phenoide t OH on (i) Reimer—Tiemann reaction : This involves the treatment of phenol with chloroform in aqueous sodium hydroxide solution followed by acid hydrolysis. Salicylaldehyde is obtained as the major product along with smal amount of para product. Oa" ys culo A Salicylaldehyde (Major) (iii) Williamson’s ether synthesis : Alkyl halide when treated with sodium alkoxide gives dialkyl ether. Na + C3H3Cl ——> CH; — O— CpHs + NaCl It is the smell of a chemical compound called iodoform (CHI). (ii) It is a mild disinfectant and is used for cleaning the floors. It can also be used as an antiseptic for skin infections, burns, etc. When applied on skin, decomposes to release iodine. It is iodine which acts as the actual antiseptic, killing bacteria and fungi. It is also safer than other antiseptics if it is accidently swallowed. iii) It is prepared in the laboratory by treating ethanol or acetone with iodine in presence of 5% NaOH. (iv) Savion is used as an antiseptic. It kills bacteria, fungi, insect larvae and worms much more effectively than iodoform, It also does not smell at all. CHO cucl, Crete Phenol C2) 23. i) 24. (i) (a) Phenol gives violet coloured complex with neutral FeCl; solution while benzyl alcohol does not. 6CsHsOH + FeCl; Phenol. J [Fe(OCgHs)]* + 3H" + 3HCL Violet complex (b) 2-Methylpropan-2-ol (tertiaryalcohol) will give turbidity immediately when treated with Lucas’ reagent (cone. HCL and anhyd. ZnCl;) while butan-2-ol (secondary alcohol) will give turbidity after 5 minutes. ie CH; C—O +HCl CH, GH CHy-C—Cl+ 1,0 CH, (Forms turbidity immediately) Anhyd. ZnCl, ——> Anya, ZnCl, — CHy CH, CH— CH, + HCL Ou CHy—CH,—CH—CH, + H,0 cl (Forms turbidity ater 5 min) CH, i. CH. Gi) (@) CY Ho on 1 -Methyleydlohiexan-1-01 on (b) +H,0 > 4-Methythept-3-ene 4-Methylheptan-4-ol oO AAN+H oS DA Pent-L-ene Pentan-2-0l OR (i) (a) Phenols are more acidic than alcohols. Itcan be explained on the basis that alcohol on losing H* ions forms alkoxide ion and phenol forms phenoxide ion. OH Oo O-0- ‘The greater acidity of phenol is due to the stability of the phenoxide ion which is resonance stabilized as shown below: aemenens an Th ayy w (b). The boiling points of ethers are much lower than those of alcohols of comparable molar masses because unlike alcohols they cannot form intermolecular hydrogen bonds. (ii) (a) In substituted phenols, the presence of electron releasing group decreases the acidic strength of phenol. This effect is more pronounced when such a group is present at ortho and para-positions. It is due to the increased negative charge in phenoxide ion, Thus m-aminophenol is stronger acid than @-aminophenol. (b) Alcohols act as weak base because of the presence of lone pairs of electrons on ‘oxygen atom. H" ions from an acid adds on to oxygen of © — H bond forming an oxonium ion. (©) The molecules of butane are held together by weak van der Waals forces of attraction while those of propanol are held together by stronger intermolecular hydrogen bonding. HO H-O~ CsH, CH, 25. (i) There can be only two primary alkyl bromides with molecular formula, Cy HBr. ‘These are ‘cHemistry Topay | voveveex ‘14 67 CH,CH,CH,CH,Brs, CHy~CH—CH,Br CH; 1-Bromo-2-methylpropane (iso-Buryl bromide) 1-Bromobutane (n-Butyl bromide) (A) must be iso-butyl bromide as, when treated with sodium it gave a compound different than that produced by n-butyl bromide which reacts with sodium to give n-octane, CH, GH—CH,Br< SSH C=CH, CH. a> iso-Batyl bromide nal CH, tert-Butyl bromide {Tsomer of (4)] CH; GH CH,—CH)— CH-CH, CH. CH. 5 oO ° 2.5-Dimethylhexane (ii) The isomers of the compound having molecular formula CyHyBr along with their common and TUPAC names are given below: CH,CH,CH,CH,Br ; CH,CH,CHBrCH, n-Botyl bromide (1-Bromobutane) sec-Butyl bromide (2-Bromobutane) (Bromide) (2 Bromide) oH oH, CH;~CHTCH)Br 5 CHy~C—Br CH, éso-Buiyl bromide tert-butyl bromide (1-Bromo-2-methylpropane)(2-Bromo-2-methylpropane) (P Bromide) (3° Bromide) OR ‘There are two reasons : (i) In case of chlorobenzene, carbon to which chlorine is attached is sp” hybridised and is more electronegative than the corresponding carbon in cyclohexyl chloride which is sp* hybridised. So @ @ 68 cHemstRY TODAY | novensih 1 (ii) 26. (i) the net dipole moment is lower in chlorobenzene. (ii) In chlorobenzene C= Cl bond has some double bond character so its bond length is smaller. Hence dipole moment is smaller than cyclohexyl chloride which has a longer C— Cl single bond ° cs i ” a ” Chlortbenzene Cyclones chore (b) Alkyl halides are polar but are insoluble in water because energy required to break the intermolecular H — bond among water molecules is much higher than energy released by water halide interaction, (c) Grignard reagents react with water to form alkanes. R—Mg-X + HjO—>R-H + Mg¢* So, they must be prepared under anhydrous conditions. Molecular formula CsHyo indicates that it can be either an alkene or a cycloalkane. Since it does not react with chlorine in dark so it cannot be an alkene. It gives only a single monochloro derivative, which shows that all the hydrogen atoms are identical. It isa cycloalkane, ic, cyclopentane. Due to the bent structure of ethers and polarity of C—O bond, all ethers have a net dipole moment ROKR ‘As we know that the electron withdrawing groups enhance the acidic character of phenols because they help in the stabilisation of phenoxide ion. Nitro group is an clectron withdrawing group whereas methoxy group isan electron releasing stoup, s0 o-nitrophenol is more acidic than o-methoxyphenol, Concerned about your performance in Class XII Boards? Excelx ‘CHEMISTRY a xcelix MATHEMATICS xceln PHYSICS Excel BIOLOGY Rs 450 Rs 375 Well, fear no more, helpis at hand... To excel, studying in right direction is more important than studying hard. Which is why we created the Excel Series. These books ~ for Physics, Chemistry, Biology & Mathematics ~ have been put together totally keeping in mind the prescribed syllabus and the pattern of CBSE’s Board examinations, so that students prepare and practice with Just the right study material to excel in board exams. Did you know nearly all questions in CBSE's 2014 Board Examination were a part of our Excel Books? That too fully solved eect? ‘omprehensive theory strictly based on NCERT, Se eee cat NCERT ques See en ht ce roe Bieter tesa Latest CBSE Board Sample Papers (Solved) Ser kes oe sea adenine Ren fla nai WUEGS | pvaisbteat all ending book shops throughout the country penrane For more information or for help in placing your order: are Call 0124-4951200 or email info@mtg.in a “Application to read QR codes required cemusray Tooar | oven 12 69 YH HH NO, OCH, e-Nivophenol —_o-Methoxyphenol (©) Alkyl groups have +F effect, As the number of alkyl groups increases from primary to tertiary, electron density in the O—H bond is maximum in case of tertiary alcohol and minimum in case of primary alcohol. Thus, the O—H bond in tertiary alcohol is the strongest and in primary alcohol it is weakest. ‘Thus, the acidity of alcohols follows the order primary > secondary > tertiary. 9 (ii) (@) Ethyl magnesium — Formaldehyde chloride I CH,—CH,MgCl + H—C—H Diy “| CH,—CH,—CH,—OMgCL Jno» CH,—CH,—CH,—OH Propan-t-ol e (b) CH,MgBr + CH,—C—CH, J ‘Methyl magnesium Propanone bromide OH OM CHy-C-CH, Screen, cH, cH, 2-Methylpropan-2-o1 oR (i) (a) This reaction proceeds through the rearrangement of the 2° carbocation formedintoamorestable3° carbocation, ‘The mechanism is as follows: CHCH—CH,2=CH,~CH— CH=CH, CH,:QH CH, “QH, 3-Methylbutan-2-ol | CH,—CA—CH—CH, CH, 2° Carbocation 70. cuemistmy TopAY| ovens 18 H Ky Cry -GEH— cng SoH, C—CH,- aN, cH, cH, 3° Carbocation fer Br cue CH,—CH, tu, 2-Bromo-2-methylbutane K,Cr,0, + H,S0, ‘controlled oxidation (b)@) CH,CH,OH: Ethanol OMebr cH, —CH—cH, 8" cHcHO Adltion product Ethanal ou CH, —CH—CH, Propan-2-o1 “| H'/HOH, -Mg(OM)EF (i) CH,CH,OH7ES CHC Fthanol It Bthanal Lu i) @ (-on1+s0c > ya +80) + HCl CHjOH Heat (b) I + HCL HO’ cH, stu HO’ WitG Attempt free online test Log on to http://test.pcmbtoday.com nt as CONSE Tsai eT Only One Option Correct Type This section contains 20 multiple choice questions. Each question has four choices (a), (b),(c) and (di), out of which ONLY ONE is correct. 1. Which of the following compounds is the most basic in aqueous medium? q (a) CHy-C—NH (6) CHy~C—NH, NH CH, (c) CHy-C—NH, (d) CH;~C—NH), 2. Mixture of 1°,2° and 3°amines can be separated by (a) Hinsberg’s method (b) Hofmannis method (o) distillation (@) all of the above. : Zndust, , Cold 3. CgHSNO. a ASone He P A and B respectively are @) (O-NHon. HoXO)-NH (b) (Op-NH-NnXO). =yO). ©) (d) None is correct. ‘Maximum pK; value is of (a) (Oyxncn, (b) (CH;CH,))NH (©) (CHs).NH (a) (Opn) Which is the best leaving group? (a) No (b) OH” (©) NH (@) CH;COO Which one of the following sets of monosaccharides forms sucrose? (a) 0-D-galactopyranose and ot-D-glucopyranose (b) o1-D-glucopyranose and -D-fructofuranose (0) B-D-glucopyranose and o1-D-fructofuranose (d) a-D-glucopyranose and B-D-fructopyranose. ‘The shape of (CHs)3N is pyramidal because (a) nitrogen forms three sp* hybridised sigma bonds with carbon atoms of methyl groups and there is one non-bonding electron pair (b) nitrogen forms three sp” hybridised sigma bonds with carbon atoms of methyl groups .d fourth orbital forms pi bond (©) nitrogen has five valencies which are arranged in pyramidal shape. (d) the unpaired electron present on nitrogen is delocalised. A dextrorotatory sugar present in fruits is (a) glucose (b) fructose (c) cellulose (d) starch. For the nitration of aniline, which of the following steps is followed? cesta ropay | reve 74 (a) Direct nitration using nitrating mixture (conc, HNO, + conc, H,S0,) followed by oxidation. (b) Using fuming HNO, at 273 K followed by hydrolysis (c) Using NaNO, and HCI followed by reaction with conc. HNO, followed by hydrolysis. (a) Acetylation followed by nitration and. hydrolysis 10. Which of the following statements about RNA is not correct? (a) Ithasa single strand. (b) It does not undergo replication. (c) Itdoes not contain any pyrimidine base. (a) It controls the synthesis of proteins. 11. The reaction of benzenesulphonyl chloride with ethylamine yields (a) N-ethylbenzenesulphonamide, insoluble in alkali (b) N, N-diethylbenzenesulphonamide, soluble in alkali (©) N, N-diethylbenzenesulphonamide, insoluble in alkali (@) N-ethylbenzenesulphonamide, soluble in alkali. 12, Five-membered ring structures of fructose are given below. Mark the incorrect statement. GO CHOH CH,OH on HHO H OH H CH,OH OH H OHH (a) The five-membered ring structures are named as furanose structures. (b) The cyclic structures represent two anomers of fructose. (c) Five-membered ring structures are named as pyranose structures. (d) These are also called Haworth structures. 13. Which of the following is not a property of diazonium salts? (a) Diazonium salts are colourless, crystalline solids. (b) Being ionic in nature they are soluble in water. (©) Most of these salts explode when dried, (d) The aqueous solutions of these salts are poor conductors of electricity. 72 cuemstmy TopAY|novensin 14, A tripeptide is composed equally of L-valine, L-tyrosine and L-alanine (one molecule of each). How many isomerie tripeptides of this kind may exist? (a) 3 (4 © 6 8 15. Which of the following compounds cannot be identified by carbylamine test? (a) CH,CH,NH, —_(b) (CH,),CHNH, (©) CoHsNHp (@) CcHsNHCsHs 16. Which of the following acids is a vitamin? (a) Aspartic acid (b) Adipic acid (c) Ascorbicacid —(d) Saccharic acid 17. Which of the following is amphoteric in nature? (a) CH;NH5 (b) CHyNHCH, (©) CH;CONH, —_(@) CHj—-N—CH, CH, 18. Milk changes after digestion into (a) glucose (b) lactose (©) fructose (a) glycogen. 19. Which of the following is correct method to convert p-toluidine to p-toluic acid? (a) Diazotisation, CuCN, H,/Pd. (b) CHCI,/NaOH, KCN, $n/HCL (c) Diazotisation, CuCN/KCN, H,O/H* (d) Diazotisation, NaCN, NaOH 20. Keratin, a structural protein is present in (a) hair (b) wool (© silk (@) all of these. Bourn One or More Options Correct Type This section contains 5 multiple choice questions. Each question has four choices (a), (b),(c) and (d), out of which ONE or MORE are correct. 21. Select the correct statement). (a) Most alkylamines are more basic than ammonia in aqueous solution. (b) pK, of MesNH is higher than that of NH, (c) Aniline is more stable than anilinium ion. (d) pK, of CH3NHy is higher than that of NH3. 22. Which of the following carbohydrates are D-isomers? 23. 25. . In the following reaction, OMe (a) O\OH H/H HOH CHO (b) H4-OH CH,OH Which of the following statement(s) is/are correct. cH) ug )-cH, N-Methylpiperidine 4-Methylpiperidine “) (B) (a) A has higher boiling point than B. (b) B has higher boiling point than A. (c) A and B have same boiling point being isomeric amines. (@) B reacts with benzenesulphonyl chloride while A does not. (ae OHA HC Hy the product(s) is/are omy (©) (b) ff N(CH3)9. @ N(CH); N(CH) D-(+)-Ghucose X69} 5 p.(+)-Glucose pentaacetate Which statement(s) is/are true about glucose pentaacetate? (a) It will react with phenylhydrazine but not with Tollens’ reagent, (b) It will react with Tollens’ reagent but not with phenylhydrazine. (©) It will react with both of the above mentioned reagents. (a) It will react neither with phenylhydrazine nor with Tollens reagent. Aeon Paragraph Type This section contains 2 paragraphs each describing theory, experiment, data, etc, Six questions relate to two paragraphs with three questions on each paragraph. Each question of a paragraph has only one correct answer among the four choices (a), (b),(¢) and (¢). Paragraph for Questions 26 to 28 Proteins are the polymers of about twenty different amino acids which are linked by peptide bonds ‘Ten amino acids are called essential amino acids because they cannot be synthesised by our body, hence must be provided through diet. Proteins perform various structural and dynamic functions in the organisms. Proteins which contain only o-amino acids are called simple proteins. ‘The secondary or tertiary structure of proteins get disturbed on change of pH or temperature and they are not able to perform their functions. This is called denaturation of proteins. 26. Which of the following ot-amino acids does not form optical isomers? (a) NHjCH(CH;)COO™ (b) NH,CH;COO (0) NICH(CH,Ph)COO™ (d) NH,CH(CH(CH;),)COO™ 27. Which of the following amino acids contain sulphur and is an essential amino acid? (a) Isoleucine (b) Methionine (©) Proline (d) Glutamine 28. Which of the following statements is incorrect regarding digestion of proteins? (a) Proteins are hydrolysed to peptones in mouth by amylase (b) Proteins are hydrolysed to peptones in stomach by pepsin. ccieausray Tooay | ovees 12 73 (c) ‘The peptones are broken to peptides in the intestine by trypsin. (d) The peptides are further broken to amino acids in the intestine by peptidase Paragraph for Questions 29 to 31 All amines are basic in nature due to the presence of lone pair on nitrogen atom. Aliphatic amines are more basic than ammonia and aromatic amines but aromatic amines are less basic than ammonia. ‘This is due to (+1) effect of alkyl group and resonance effect of benzene ring, In aromatic amines, presence of electron withdrawing group decreases basic character and electron donating group increases basic character. 29. Which of the following is least basic? (a) 0-Toluidine (b) N-Methylani (©) m-Toluidine (4) p-Toluidine 30, Which of the following is most acidic? H-N-CH, NH /NH, (a) (b) HN= ney NH, yee @ unc () Hy v CH, (4) HN. Hen, L f 31, The most basic amine among the following is, NH) NH, NO, (a) (b) NO, NH), NH, (©) (d) Hy F Ee Matching List Type This section contains 3 multiple choice questions. Each question has matching lists. The codes for the ists have choices (2), (b), (¢) and (d), out of which ONLY ONE is correct. 32. Match the List] with List II and select the correct answer using the code given below the lists: 74 cuemistmy TopAY | ovens List I List I P. Benzenesulphonyl 1. Zwitter ion chloride Q Sulphanilic acid 2. Hinsberg’s reagent R. Alkyldiazonium salts 3. Dyes S. Aryldiazonium salts 4. Conversion to alcohols P QR s (a) 4 203 (b)3 2 4 21 (2 1 4 3 @4 2 3 1 33. Match the List I with List I] and select the correct answer using the code given below the lists: List 1 List IT P._ Peptide linkage 1. Inversion Q Nucleic acid 2. Polysaccharide R. Hydrolysisofcane 3. Proteins sugar S. Starch, 4, Nucleotides PQeRs @2 13 4 (b)4 1 2 3 3 4 1 2 @il 3 4 2 34. Match the List I with List II and select the correct answer using the code given below the lists : List I List IL P. Reaction of benzene- 1. Gattermann diazonium chloride with reaction cuprous salts dissolved in the halogen acid. Q. Reaction of benzenedi- 2. Sandmeyer azonium chloride with reaction halogen acid in the pres- ence of copper powder. R. Reaction of amines with 3. Hinsberg’s chloroform reaction S. Reaction of amines 4. Carbylamine with benzenesulphonyl reaction chloride. Assertion-Reason Type In the following questions, a statement of assertion is followed by a statement of reason, Mark the correct choice as : (@) If both assertion and reason are true and reason is ‘the correct explanation of assertion (0) If both assertion and reason are true but reason is not the correct explanation of assertion. (c)_ If assertion is true but reason is false. (d) If both assertion and reason are false. 35, : Proteins are made up of camino Reason : During denaturation, secondary and tertiary structures of proteins are destroyed. 36. Assertion : Gabriel phthalimide synthesis can be used to convert alkyl chlorides into primary amines Reason : With proper choice of reagent Gabriel synthesis can be used to prepare primary, secondary and tertiary amines. 37. Assertion : All enzymes are proteins but all proteins are not enzymes. Reason : Enzymes defend the body against the invasion of foreign organisms. 38. Assertion : The amino group of aniline being completely protonated in strongly acidic solution, the lone pair of electrons on the nitrogen is no longer available for resonance. Reason : In strongly acidic solutions, aniline becomes more reactive towards electrophilic reagents. 39. Assertion : All enzymes found in cells are invariably proteins which catalyse biological reactions. Reason : Enzymes act efficiently at a moderate temperature and pH. 40. Assertion : p-Methoxyaniline (p-anisidine) is a stronger base than m-Methoxyaniline (m-anisidine). Reason : At m-position, methoxy group can exert only -I effect but not + R effect. Soe Integer Value Correct Type This section contains 10 questions. The answer to each question is a single digit integer, ranging from 0 to 9 {both inclusive). 41. Number of amines out of the following which will react with CS, is om NH, Ay, ANN . AL 42. Glucose reacts with v moles of phenylhydrazine to yield osazone. The value of x is 43. CjHy\N_ on reaction with HNO, forms 3° alcohol. Thus, amine is x°. xis NHPh. NCH) 44, In sucrose, two monosaccharides are held together by a glycosidic linkage between C-1 of G-glucose and C, of B-fructose. Here x is 45. Liebermann’s nitroso reaction is given by 2? amines only. The value of x is SHO NaBH 46. (CHOH), ~~ Product | CH,OH Glucose Number of possible racemic forms of the product is 47. Number of compounds out of the following which will react with HNO, by formation of CN bond is NH, Oo" *oo™ 48. u- and B-D-glucose differ in configuration at anomeric carbon at carbon position number Ww NH, N cemusray Tooay | oveees 12 75 49. In carbylamine reaction, number of molecules of alcoholic KOH used is 50, Fructose is subjected to bond cleavages by HIO,. The number of HCHO unit(s) formed per unit of fructose is 1 ©: it i (a) CH,—C—NH, +H CH,—C—NH, ‘itde tendency to accept a proton) s $ (b) CH,—C—NH, + H+—>CH,—C—NH, Tht tendency to accep a proton) NHL NH (© CHy—C—NH, + H*—>CH,—¢-NH, wo NH, NH, La ==CH,—C—NH,==CH,—C=NH, Carbocation (1) is more stable since it has two equivalent resonance structures. oh, CH, |S I (&) CH;-C—NH, + H*\—>CH,—C—NH, m CH, ==CH,—C=NH, Carbocation II is less stable than I since it has only one resonating structure. ‘Thus, compound (c) is most basic. 2 (d) Zn dust 3. (a) CoHsNO, BEES Cols sNHOH Cold, cone. HCL angen? HO-{O)-Nt @ @ 5. (@) 6. (b): Sucrose is formed by the condensation of -D-glucopyranose and B-D-fructofuranose. q JN cH, 7 (ads ‘CH, 76 cuemstmy TODAY |novensih 8. (a) : Glucose is dextrorotatory. 9. (d):-NH} group is first oxidised on direct nitration hence ~NH) group is first blocked by acetylation and then nitration is carried out. NH, Om NHCOCH, cH,coc, BNO TAS0, | 101K" NO, 10. (¢) : Itcontains uracil and cytosine as pyrimidine bases. Therefore, statement (c) is wrong, t LL (d): (Op fea ricn-c, Benzenesulphonyl Ethylamine chloride i ire HCl OH N-Fthylbenzenesulphonamide {soluble in alkali) 12. (c) :Five-membered rings are named as furanose while six-membered rings are named as pyranose rings. 13. (d): The aqueous solutions of diazonium salts, are good conductors of electricity. 14, (¢) :Val. Tyr. Ala Tyr. Ala. Val Val. Ala. Tyr Ala. Tyr. Val Tyr. Val. Ala Ala. Val. Tyr EMD fal get on orders above Rs. 999/- Apply coupon code - Va COUPON25 MTG Books are also 2 on wernt ppeme cores Cee Crash Course for Peak Performance rapid PHYSICS © HIGH YIELD FACTS © EASY TO GRASP @ ESSENTIAL FOR COMPETITIVE EXAMS PHYSICS, CHEMISTRY, MATHEMATICS & BIOLOGY vA PR ed es ‘ailabe tal leading book shops throughout the country. aed For more information or fr help in placing your order lars Call 0124-4951200 or email: info@mtg.in GHemisTRY Topay | NoveweeR ‘14 77 15, (d) : Secondary amines do not give carbylamine test. 16. (c) : Ascorbic acid is vitamin C. Its structure is H HO- 0. HO’ H ‘OH 17. (c) : Amines are basic in nature while amides are amphoteric in nature 18. (a) : Milk contains lactose which on hydrolysis gives glucose and galactose. 19. (c) 5 CH, NINO, , DY CuCNIKEN, “aa? ose) NH, Njcl- peToluidine [row CH, COOH peToluic acid 20. (d) : Keratin is a fibrous protein present in hair, wool, silk and muscles. 21. (a,b, ¢) 22. (a,b, ¢,d) : The compound whose numerically largest numbered (as per IUPAC convention) asymmetric carbon has configuration similar to D-glyceraldehyde has D-configuration. 23. (b, d) 4. (c) oF OHA, 7 ~* 0” HN N(CH), uc” CH, 25, (d) : During acetylation of (+)-glucose, itis the C; — OF of the hemiacetal that is acetylated and not the C; — OH that forms the ring (eyelie structure). Since equilibrium with the open- chain aldehyde is prevented, the pentaacetate does not respond to the aldehydic reactions. 78 cuemstmy TopAY|novensih 27. 32. I CHOH | 6 CHOAc H OH H OAc HO--H O AcOH 9% H-+on H-+0ac H H CH,OH CH,OAc D-()-Glucose aor -Glucose pentaaceate (b) (b): Methionine is an essential amino acid which contains sulphur, 9 cu Kou NH, . Pepsin + HCL (a) : Proteins aahy > Peptones Trypsin Peptidase “Tintestiney > Peptides Tintestiney > Amino acids Hence choices (b), (c) and (d) are correct. (a) is incorrect because in mouth by amylase only polysaccharides are hydrolysed to disaccharides. (a) :Due to ortho-effect, o-toluidine is the weakest base, even weaker than aniline, (b) (c):Only -CH, group is electron donating group hence it increases the electron density on nitrogen making it most basic. oO (c) :(P) Hinsberg’s reagent ©>;-a Benzenesulphonyl chloride (Q) Sulphanilic acid NI, SO5H so; Sulphanilig acid Zwviter ion (B) Alkyldiazonium salts NaNO, FHC HO RONH, OES (RN, CH 0 R—OH +N,7 + HCl (S) Aryldiazonium salts ©- N=NCI+ n{O)-0n a (Op-y=s{O)-0n +c +H,0 (p Hydroxyazobenzene (Orange dye) 33. (2) 34. (d) 35. (b) : During hydrolysis of proteins we get only a-amino acids. 36, (c) : Gabriel synthesis can be used only for the preparation of primary amines. 37. (c) : Antibodies are proteins which defend the body against the invasion of foreign organisms. 38. (c) 39. (b) 40. (a) 41. (4): Primary and secondary amines react with CS, Ho 22.0): HoH + 3CjH.NHNH ear (Guo, Phenylhydrazine CH,OH CH=NNHC,H, Glocose C=nwnicgtts (cHiom), cHon 43. (1) Glucosarone 44. (2) u,0H Gijociie Hoon *“* On Ht wD (ID ceD-Ghicose B-DFructose 45, (2): Both aliphatic and aromatic secondary amines undergo Liebermann’ nitroso reaction. ‘Thus, this test is used to separate secondary amines from primary and tertiary amines, CHO CH,OH | nap, | 46, (4): (CHOH), ——*> (CHOH), | i CH,OH CH,OH Sorbitol No. of chiral carbon atoms (7) in sorbitol = 4 No. of optical active isomers(«) 48. (1) 49. (3) 50. (2) = SOLUTIONS TO OCTOBER 2014 CROSSWORD psyefef i ulalit fela falulofat>l=folul i fot {sf fafa fo Epa te tala tol Winners of October 2014 Crossword Anurag Bera (West Bengal): MTG magazine plays a role of a proper guide in my study. I was totally influenced by this Crossword: It helps to increase anyone’ thinking ability and check their subject depth. So, itis a ‘fabulous booster for me as well as all MTG readers. Aditi Rastogi (Bhopal): The concept of Crossword’ is very good. Ithelps to revise my concept in chemistry. Sender of September 2014 Crossword Shubham Panwar (Rajasthan) ccemusray Tooar | oveees 12 79 SSA MUSING (b): Optically active alcohol (CgHyoO) is an unsaturated alcohol containing C=C bond, since it absorbs two moles of hydrogen Compound (Q) being optically inactive must be a tertiary alcohol, since it is resistant to oxidation by CrO,. Therefore, its structure should be Hs CH;CH,— ¢ OH CH @ and thus (P) is Hs Hc=c—C—on CH; Hence, the reaction is OH; Hs 2g HC=C~C—OH —> CH,CH,—C-OH CH CH (P) Q) 2. (c) : Perhydrol is 30% H,0;, Using the relation, Volume strength = 5.6 x Normality <5, Percentage strength 5 Eq. wt. of HO, =5.6x 2x10 = 98.82 =99 7 (d): Aspirin being a weak acid remains unio- nised in the stomach (acidic medium) but completely ionised in small intestine (alkaline medium) due to the common ion effect. 4. PY _2Px2V 7 f Ty =4T; P and V remain constant, when air is taken in. 80. cHEMstRY TODAY |nvensih ‘Thus, nAT,= nT where 1 and ir’ are the number of moles at temperatures 47, and T’ respectively. rd nsntons2n 5 6. oon crag “This wos Due to resonance C-Br__ takes part in bond is shorter and strong the reaction therefoce this halogen cannot takepart in the reaction, 9° N- CHK) Be << (Major) 7. (d): Any metal placed below hydrogen in electrochemical series will not give its sulphate with dil. H,SO, 8. (d): With the exception of Li,SO,, other alkali metal sulphates are water soluble. 9. (6): 50 mL of 1 M oxalic acid [(COOH),-2H,0] 50 mL of 0.5 M oxalic acid = 6.3 x 0.5 = ~. Oxalic acid adsorbed on 0.5 g wood charcoal = 63-315 =3.15¢ % Amount of pal acid adsorbed per gram of charcoal 05 Og=6.0g 10. (8): BrF; is square pyramidal in shape. ‘The observed bond angles are F 87%, which is close to the , E theoretical 90°, This slight distortion is caused due to presence of one lone pair of P electrons on Br-atom. PRACTICE PROBLEMS 2 1 > Chemistry Olympiad When threo-3-bromo-2-butanol is hydrolysed with NaOH gp the product obtained is (a) erythro-3-bromo-2-butanol (b) threo-2,3-dihydroxybutane (c) optically active 2,3-dihydroxybutane (@) meso-2,3-butanediol ‘The pH of D,O and H,O at 298 K is (a) 7.43 and 7.0 (b) 7.0 and 7.0 (c) 7.0 and 6.85 (d) 6.85 and 7.35 During the adsorption of krypton on activated charcoal at low temperature (a) AHOandAs<0 (c) AH>OandAS>0 (d@) AH o Oil spreads on water surface because (a) oil is denser than water (b) surface tension of oil is more than water (©) surface tension of oil is less than water (d) none of the above. Which one undergoes facile decarboxylation? 000GrHs COOC,Hs, OH (b) Ph A COOH OH o cat (d) C,H,COCH,COOH If two compounds have the same empirical formula but different molecular formula, they must have (a) HAC 10. (a) different percentage composition (b) different molecular weights (©) same viscosity (@) same vapour pressure. In Ramsay and Rayleigh’s isolation of noble gases from air, the nitrogen of the air is finally converted into (a) NaNO, only (b) NO and NO, (©) NaNO, only (4) NaNO, and NaNO, ‘Two oxides of an clement contain 57.1% and 72.7% of oxygen. If the first oxide is MO then second oxide is (a) MO (b) M0 (c) MO; (@) MO, ‘The inversion of table sugar (sucrose) in acidic medium proceeds with a half-life 450 minute at pH = 5 for any concentration of table sugar. ‘The half-life changes to 45 minutes if pH = 6, the inversion of table sugar follows the rate law expression (a) 7=k{sugar}'[H" (b) r= kisugar}'[e"]! (©) r=K{(sugar]’[H"|) (d) r= kisugar]*[H"]" ‘The position of equil each of these reactions. N3H? + NH; = NH} + NjHy NH, + HBr == NH} + Br NjH, + HBr ==NjH! + Br rium lies to the right in Based on this information, what is the order of acidic strength? (a) HBr > N,H; > NH} (b) NJHE > N,H, > NH} (c) NH, >N,H,> Br (@) N,H! > HBr > NH} caemusray Tooay |noveven 12 81 11. When a Cu-Zn galvanic cell operates under standard conditions, (a) the concentration of Zn®* ions in the zine half-cell gradually decreases (b) the concentration of Cu** ions in the copper half-cell gradually increases (c) negative ions migrate from the zinc half- cell to the copper half-cell (d) the intensity of the colour of the electrolyte in the copper half-cell gradually decreases. 12. According to Charles’ law, volume of a gas can be plotted against temperature in celsius as shown in the graph, If Vp is the volume of a gas at 0*Cand V; is the volume at °C then slope of the straight line is equal to S : (yc ay Yo a 273 ©) a wf ve @% 273 13. Which of the following reactions gives non- resolvable prguct? @ oO 050 pride, cu, OMS, ‘CH,CH, (b) POS (i) Os0y pyridine. NaS, > ray "oe Bry, HjO 14, Which one of the following is a covalent crystal? (a) Rock salt (b) Toe (c) Quartz (d) Dry ice 15, The expected product in the reaction, cold, dilute KMnOy 70 is &) CD wl HO 1 Q oh, HO by 82. cHeMstmY TODAY | novensin HO i H ou OH 16. An alloy of Cu, Au and Ag is found to have Cu constituting the cep lattice. If Ag atoms occupy the edge centres and Au is present at body centre, the alloy has formula (a) Cu,AgyAu (b) Cu,Ag.Au (©) Cu,AgsAu (a) CuAgau 80-110°C. CQ nn state in this transformation is (a) chair (b) boat (0) half chair (@) no transition state due to fast rupture of bonds. 17. 18. The critical micelle concentration (CMC) is (a) the concentration at which micellization starts () the concentration at which the true solution is formed (c) the concentration at which one molar electrolyte is present per 1000 g of the solution (d) the concentration at which AH = 0 19, Least energetic conformation of cyclohexane is (a) chair conformation (b) boat conformation (0) half-chair conformation (d) twist-boat conformation. 20. Nylon is used in many things in our today’s life, like umbrellas, tyre cords and brushes, ete. Which of the following has the same linkage as nylon? (a) Vitamins (c) Proteins (b) Fats (a) Carbohydrates 21. ‘Ihe reaction of benzene with iso-butene in the presence of sulphuric acid gives (a) iso-butylbenzene (b) tert-butylbenzene (©) wbutylbenzene (A) no reaction The most comprehensive question bank books that you cannot afford to ignore Cea aaees CAPTERWISE, MOREA 27 Years Physics, Chemistry & Biology contain not only chapter-wise questions that have appeared over the last 27 years in CBSE PMT, but also full solutions, that too by experts. Needless to say, these question banks are essential for any student to compete successfully in AIPMT. More so since almost ‘50% of questions in AIPMT are from previous years. HIGHLIGHTS: Chapterwise questions of last 27 years’ (2014-1988) of CBSE-PMT Chapterwise segregation of questions to help you assess the level of effort required to succeed ‘An unmatched question bank series with close to 1,000 pages having detailed solutions by experts Avallable atall leading book shops throughout the country. For mate information or for help in placing your order: Call 0124-4951200 or email info@mtg.in “Application to read OR codes required Scan now wih smartphone oat” Oa cceausray Tooay | ovees 12 83 22. The molar enthalpy of fusion of water is (a) AH=0 (b) AH=AG =AS=0 6.01 kJ mol"', The entropy change of 1 mole of (c) AS=0 (d) AG=0 ice at its melting point will be , js G2] imal (b) 109)! mol! 27. seal of KI increases the rate of the 44}K ‘mol! (d) 1K mol! tone (©) 44) K" mo (@) 11K" mo CHCH,CI + H,0 ——> CHjCH,OH + HCI 23. Which of the following is most likely steuctuze ‘This is because [is of CrCl;.6H,O, if 1/3 of total chlorine of the (@) a good nucleophile and a good leaving group compound is precipitated by adding AgNO; to . (b) a poor nucleophile and a poor leaving group its aqueous solution? ile and a good leavi (@ crcetno (6) a poor nucleophile and a good leaving group (6) [Cr(H,0),C1ICH,0), (6) mone ofthe above (©) [Cr€1,(4,0),]C12H,0 28. ‘Temperature coefficient of a reaction is ‘2. (d) [CrC1(,0)s}C1, 0 When temperature is increased from 30°C to 24, NaCl shows Schottky defects and AgCl Frenkel 90°C, the rate of reaction is increased by defects. Their electrical conductivity is due to the (a) 60 times (b) 64 times (a) motion of ions and not the motion of (c) 150 times (d) 400 times. electrons 29. Rice is deficient in (b) motion of electrons and not the motion of | (a) alanine (b) glycine bee (6) lysine (4) leucine. (0) lower coordination number of NaCl (d) higher coordination number of AgCl 30. ‘The ozonolysis of benzene produces 25. The concentration of B at ° (a) glyoxal (b) ethylglyoxal the point of intersection of (c) dimethylglyoxal (d) methylglyoxal. the two curves as shown in the figure for, A—> nB is ( % () 27 L@2@ 3@ 40 5 @ 2 ne 6. (b) 7. (a) 8 (d) 9 (a) 10. (a) nGy nol 1 @) 12 @) 13.@ 14 15. @) Om @ (2) 16. (©) 17. (b) 18. (a) 19%. (a) 20. (© . 21. (b) 22. (a) 23. (©) 24. (a) 25. (C) 26. A reaction having equal energies of activation for forward and reverse reactions has 26. (a) 27. (6) 28 (b) 29. (c) 30. (a) 00 Do you want TO ETC RS Nee aE eed Secce htt eeu Cui Sue Ucar a rd TU CSU cureu Tn ecu Sa ROC Acre sri ear en from science world, and much more co) Like us on Facebook https:/www.facebook.com/pembtoday 84 cuemusray Topay | oveste 8 ACROSS Glass used for making lenses. (6) 6. Effect develops between a m-bond and a lone pair. (9) 7. Bffect, due to scattering of light but iT not observed in sugar solution. (7) 10.Name of the CaH303.(7) i . A catalyst used for i contact process (metal in+505).(13) |. Pure substance 5 containing only one type of atoms. (7) 5. Doebner modification of aldol condensation, ay pr 7. BH, exists as (5) Common name for Ca(OH). (9) The no, of C-atoms in dibromomethane. (3) A. chemical used in cleaning products, unfriendly. (9) 2. He gave the frst insight into the structure of benzene. (6) which is environmentally Sugar, which gives B-D-glucose and -D-galactose on hydrolysis. (7) DOWN 1. If the carbonyl group is not at the end of a carbon, ©) A pyrimidine base present in DNA. (8) 3, Reaction intermediate formed in Reimer reaction. (7) chain, the substance is 9 U1. 13, 16, Analloy, sed in aircraft industry for its light weight. (9) ‘The reaction in which the final product obtained is B-amino-carbonyl compound. (7) The flame colour for potassium, a bit like lilac too. (6) A torch to caramelize sugar in cooking, (6) Change from a liquid to a gas. (11) Blectrolytes are conductors. (12) Electrons float around the atom in distinct shell: arrangements called. (8) Highly vulcanized rubber containing 20-30% sulphur. (7) 30% HO. (9) - ‘cHemistry Topay | voveveeR 14. 85 YQU ASKED WE ANSWERED Do you have a question that you just can’t get answered? Use the vast expertise of our mtg team to get to the bottom of the question, From the serious to the silly, ‘the controversial to the trivial, the team will tackle the questions, easy and tough. The best questions and their solutions will be printed in this column each month. QU. In organic chemistry, what is the actual difference between aqueous KOH and alcoholic KOH as reagent? ~ Ratnadeep Das, Silchar, Assam OR ‘What is the use of aqueous KOH in organic reactions? ~ Sachin Diman . Type of reaction, depends upon the nature of reagent used. 1. The solvent ‘The proportion of water to ethanol in the solvent matters. = Water 85 sy bstitution reaction. ~ Ethanol “°""8"> Elimination reaction. 2. The temperature ~ Higher temperature Encourages, OEE Elimination reaction. [he concentration of KOH solution ~ Higher concentration #°"> Elimination reaction. Example : Subsitaton CHsCHCH, + KOHap) “en | Br CH CHCH, + KBr 2-Bromopropane (A haloalkane) + OH KOH atc) Propan2-o Flimination |, (An alcohol) CH,=CHCH; + KBr + H,0 analkene) 86. cHEMIsTRY TODAY |nvensih 1 2. Why chemical formula of water represented as HO not OH; and ammonia as NH, not HN? “Mohd. T: Khan and Arun Nayar, Ghasipur, U.P. Ans. Covalent compounds (oy molecular compounds) are formed between non-metals only. Somecompoundsare identified with their unique names and formulae. For compounds, water and ammonia, the empirical formula is same as the molecular formula, Compound | Proper | Empirical | Molecular name | formula | formula ‘Water Dihydrogen | HO. H,0 oxide Ammonia | Nitrogen | NH ‘NH; trihydride Hence, they can be represented as HO and Hs, Q3. Why the elements having d'° configuration are not considered as ‘transition clements? = Chirag Thakar The modern, IUPAC definition states that a transition metal is “an clement whose atom has an incomplete d-subshell, or which can give rise to cations with an incomplete d-subshell” = Theelements of group 12(Zn, Cd and Hg) have a completely filled (1 ~ 1)d-subshell in their elementary form as well as in the combined state (M’* ions). These elements do not show much resemblance with other d-block elements except for their ability to form complexes ~ Apart from this, elements of group 3 (Sc, ¥, La and Ac) form ions by losing three outer electrons and end up with noble gas configuration, Hence, these elements also do not meet the definition. However, they are d-block elements. Ans. Master Resource Books in Chemistry Pe we NL Parton PUN Nose NUS NIC EMISTRY JEE (Main & Advanced), PET, <= ‘AIPM, AIMS and ll other Engineering /Medical Entrance Exams. HIGHLIGHTS: + Concise theory for competitive exams + Practice assignments with pinch of hints + Illustrations with detailed solutions + Solved MCQs single and multiple option correct + Twists and turns to learn important formulae type, Assertion & Reason, Fill in the blanks, True or False, Comprehension, Integer & Matching + Elaborate solutions to mysterious NCERT problems {V2 vith aecellaneous Questions Success in CET 2015 Now Made Easy Pn ‘nalable tall leading book shops throughout the county For more information ofr help in placing your order Call 0124-4951200 or email:info@mtgin cemusray Tooay |noveves 12 87 SUPER-ZOOM MICROSCOPE : WON THE CHEMISTRY NOBEL PRIZE 2014 Vi 2014 is remarkable for Chemistry. Three scientists Eric Betzig, William Moerner (Americans) and Stefan Hell (German) won the Nobel Prize in Chemistry on 8th October for developing new methods that let microscopes see finer details than they could before Dr. Betzig, a group leader at the Janelia Research Campus works to develop novel optical imaging tools to open new windows into molecular, cellular and neurobiology. Dr. Moerner, a professor at Stanford University works in the field of single ~ molecule spectroscopy, super resolution imaging, and trapping of single biomolecules and photosynthetic proteins. Dr. Hell, one of the directors at the Max Planck Institute for Biophysical Chemistry in Goettingen works in the field of Far-ield Optical Nanoscopy. Importance of Optical Microscopy Optical microscopy has always played a prominent role in many scientific fields, especially in life sciences. This is based on rather exclusive advantages such as noninvasive access to the interior of (living) cells and specific and highly sensitive detection of cellular constituents through fluorescent tagging. These advantages always remained the major drawback for electron and scanning probe microscopy - although providing nanoscale resolution down to the atomic level they cannot make up with the inherent incompatibility with living matter. Until the mid of the 1990s, obtaining a resolution on the nanometer scale with focused visible light was considered unfeasible because due to diffraction a focal spot is limited in its width to about half the wavelength of the used light. Only n recent years methods to surpass the diffraction barrier have been invented making the major disadvantage of optical microscopy obsolete. Optical imaging with subdiffraction resolution has an impact on numerous fields of research including cell biology, medicine or material science. WE. Moermer Stefan W. Hell Eric Betzig Success Journey : Research to Nobel > Their breakthroughs, starting in the 1990s, shattered previous limits on the resolution of optical microscopes, giving scientists improved tools to study diseases such as Parkinson's, Alzheimer’s and Huntington's at a molecular level. Hell has peered inside living nerve cells in order to better understand brain. synapses. Moerner studied proteins in relation to Huntington's disease. Betzig's work is the study of cel division inside the embryos. v v Prof, Hell developed the stimulated emission depletion (sted) microscopy in 2000. The other method, single molecule microscopy was developed separately by Prof. Betzig and Prof. Moerner. Significance — The Nobel committee says the work “has brought optical microscopy into the nano-dimension.” — The path of the individual molecules inside the living cells gave different colours after irradiation, characteristic of the molecules which has led to a reyolution in the field of microscopy all over the world. - ° ° ° =ARNZGi In physical equilibrium, opposing processes involve physical changes. In chemical equilibrium, opposing processes involve chemical changes. Chemical equilibrium may be defined as the state of a reversible reaction when the two opposing reactions occur at the same rate and the concentrations of reactants and products do not change with time. At equilibrium, both reactions i.e. forward and backward continue to perform and such a state of equilibrium where both opposing forces balance each other and molecular activity still continues is known as dynamic equil At equilibrium, the Gibb’s free energy (G) is minimum and and change taking place at equilibrium proceeds without change in free energy i.e. AG=0. According to law of mass action, the rate of a chemical reaction is proportional to the product of the active masses of the reactants. Chemical equilibrium at a given temperature is characterised by constancy of certain observable properties such as pressure, concentration, density or colour. ‘A catalyst can hasten the approach of equilibrium but does not alter the state of equilibrium. Fora reaction, A ag) + Bag) = Cag + APagy _tcrwrt lartsr where K, is known as the equilibrium constant, ‘This is called law of chemical equilibrium. Equilibrium constant K, is simply the ratio of the rate constants of two opposing reactions and it is constant as a given temperature. m. Qo ° ° ° Q For a general gaseous reaction: aA + Be Sly + mM the equilibrium constant K,, is given by _(pLl ps (pal Leal’ ie. partial pressure is taken in place of molar concentration, Equilibrium constants K, and K, are related as K, = K (RDS where An, is the difference of the sum of the coefficients for the gaseous products and reactants. If An, = 0, K, = K, If An, = +ve, K,> Ky Wan, = ve, K,< K, If reaction is reversed, equilibrium constant is inversed. i.e., K’ = 1/K. If equation for a reaction is divided by a factor of ‘rf, the new equilibrium constant becomes nt root of the previous equilibrium constant. ie, K'=YK If equation for a reaction is multiplied by a factor ‘n’ then the new equilibrium constant (K) becomes equal to K". ie, K’= K" Ifequation is written in a number of steps, then its equilibrium constant will be multiple of equilibrium constants of each step. ie K=K, XK, x Ky Xs Ky In homogeneous equilibrium, all the reactants and products are in the same phase. Nog + 3Hyjg) =? 2NHyy, \" Kp In heterogeneous equ and products are present in two or more phases. Cy + HOw = CO + Fay Predicting the extent of reaction: - _K_> 10° [Forward reaction is favoured.] jum, the reactants cemusray Tooay |noveees 12 89 90 = _K,<10™ [Reverse reaction is favoured.] = 10° K, [Reverse reaction is favoured,] - Q.1 [Borward reaction is favoured] — IFAG?>0 then K<1 (Reversed reaction is favoured.] ~ IAG =0, then K=1 [Reaction is in equilibrium.} SOIT aInKp _AH® i. known as vant Hoff’ a RT equation. where AH? is the standard enthalpy change for the reaction at constant pressure when the reactants as well as the products are in their standard states. Kp AH q Ky, 2.303R| 42, where K”, is the equilibrium constant at temperature T,, K’, is the equilibrium constant at temperature T\and AH is heat of reaction (enthalpy change). According to Le-Chatelier’s principle, if a system in equilibrium is subjected to a change of concentration, pressure or temperature, the equilibrium shifts in the direction that tends to undo the effects of the change imposed. Change in concentration : Increasing the concentrations of the reactants resultsin shifting the equilibrium in favour of the products while increasing the concentration of the products results in shifting the equilibrium in favour of the reactants. log: cuemisray ToDaY | ioveste 1 ° ° ° ° ° Change in pressure : ‘The increase of pressure on a chemical equilibrium shifis it in that direction in which the number of molecules decreases and vice-versa, Change in temperature : The increase of temperature favours the reverse change in an exothermic reaction and the forward change in an endothermic reaction. Effect of adding inert gas : Addition of inert gas at constant volume does not affect the equilibrium and addition of inert gasat constant pressure favours the direction in which larger number of moles of the gas are produced. Effect of adding catalyst : The addition of catalyst does not affect the equilibrium, Tonic equilibrium is the study of equilibrium in the reactions where formation of ions take place in aqueous solution, Tonisation of acids: HA Cag) = Hig + Aiag) _(HtAT] (H4] pK, = -logk, As K, increases, pK, decreases and acidity increases. Tonisation of bases: BOH (ag) = Bligy + OMGag) [B07] As K,, increases, pK, decreases and basicity increases. istage ionisation of acids and bases For a polybasic ac K,, > K,,> Ky, and so on For a polyacidic base, K,, > Ky, > Kj, and so on. According to Arrhenius theory, an acid is a compound that releases H” ions in water and base is a compound that releases OH ions in water. According to Bronsted-Lowry concept, an acid is any molecule or ion that can donate a proton (H*) and base is any molecule or ion that can accept a proton ie Master NTSE (National Talent Search Examination) with the most Up-to-Date and Authentic Study Books This book will help students to master the NTSE curriculum and to excel in highly prestigious examinations as well as enrich their knowledge. ate NTSE EXPLORER Fr Pa: MrkaT | Lea le Ee —MADE EASY rn Detailed Solutions of 2013-2014 NTSE Papers | Comprehensive Theory ‘Scholastic Aptitude Test (SAT) Solved Examples to Understand Concepts Mental Ability Test (MAT) 2500+ Questions of Verbal and Non Verbal Reasoning English Language Test Sample Papers (Stage |& Stage Il) See ee ete em ee Fe a a ee meee Cen eu ccemusray Tooa |noveven 12 91 ° 92 ‘The strength of a Bronsted acid depends upon its tendency to donate a proton, ‘The strength of a Bronsted base depends upon its ability to accept a proton, Some common acids have been arranged in the following order of their acid strengths HCIO, > HBr > H,SO, > HCl > HNO, The acid (HA) and its conjugate base (A”) that are related to each other by donating and accepting a single proton are said to constitute a conjugate acid-base pait A weak base has strong conjugate acid and a weak acid has a strong conjugate base. A strong acid has a weak conjugate base and a strong base has a weak conjugate acid. Monoprotic acids are capable of donating one proton and monoprotic bases can accept one proton. Polyprotic acids are capable of donating two or more protons are polyprotic bases can accept two or more protons, Molecules or ions that can behave both as Bronsted acid and base are called amphiprotic substances. According to Lewis concept, an acid is an electron pair acceptor and base is an electron pair donor. According to Ostwald’ dilution law for weak electrolytes the degree of dissociation is inversely proportional to the square root of concentration. 1 ae oro ve For two weak acids of dissociation constant K, and K,, at the same concentration, where G1, and Gy are the respective degrees of dissociation of the two acids, Degree of dissociation of an acid is a measure of its capacity to furnish hydrogen ions and hence a measure of its strength. K, K, [K, Strength of one acid, HAy Strength of another acid, HA, cuemisray ToDaY | ioveste 1 ‘Thus, relative strengths of any two weak acids at the same concentration are given by the ratio of the square roots of their dissociation constants. ‘The hydrogen ion concentration in a solution ofa weak acid in water at a given concentration is directly proportional to the square root of the dissociation constant of the acid. =f = CK, ‘The dissociation constant K;, of the base is given. Ionic product of water: 2H,0() = H30{q) + OH Gag) K, = [H,O*][OH] =1 «10M? [OH] = [H*] = 1.0 x 107 Mat 298K The pH of a solution is the negative logarithm of the concentration (in moles per litre) of hydrogen ions which it contains. pH = -log[H"] or pH = -log[H,O") Similarly, negative logarithm of hydroxyl ion concentration is called pOH. pOH = -loglOH |] Relationship between pH and pOH pH + pOH=14 pH + pOH = pK, pK, + pK, =pK,, ‘The scale on which pH values are computed is called the pH scale. ‘The lower the pH, higher is the [H"] or acidity. IfpH value of a solution is , it is neutral, if pH value is less than 7, the solution is acidic and if it is more than 7, the solution is alkaline ‘The solubility (S) of a substance in a solvent is the concentration in the saturated solution, Molar solubility is defined as the number of moles of the substance per litre of the solution. Solubility product : AyyBy = mA" +nB"™ y=") ~ Kiy> Ky, Precipitation occurs. ~ Kip< Key Precipitation does not occur. = Ki, = Ky solution is saturated. Relation between solubility and solubility produ K op =[n]"[nS]" = mS" -ni"s" =m" ni" -(S)"** [where $ is solubility.] ‘The suppression of the dissociation of a weak acid or a weak base on the addition of an electrolyte containing its own ion is called common ion effect. A buffer solution is one which can resist change in its pH value on the addition of an acid or base. ‘The capacity of a solution to resist alternation in its pH value is known as its buffer capacity. Solutions of salt of weak acid and weak base are called simple buffers. ¢.¢., CH,;COONH, A weak acid together with a salt of the same acid with a strong base are called acid buffers. eg. CH,COOH + CH,COONa A weak base and its salt with a strong acid are called basic buffers. e.g. NH,OH + NH,Cl {Salt} [Base] pOH = pK; +log is known as Henderson's equation and enables the calculation of pH values of bufier solutions made by mixing known concentrations of a weak acid and its salt, ‘The phenomenon of the interaction of anions and cations of the salt with the H" and OH ions furnished by water yielding acidic or alkaline or sometimes even neutral solution is known as salt hydrolysis. Salts of strong acids and bases do not undergo hydrolysis e.g, KCI. A buffer solution is assumed to be destroyed if an addition of strong acid or base, changes ° ° ° ° Q its pH by 1 unit ie. pH (new) = pK, + 1. This means the ratio Sa, [Salt] 19 4, 4. [Acid] [Base] 10 The aqueous solution of the salt of a weak acid and a strong base is alkaline because of hydrolysis. ‘The aqueous solution of the salt of weak base and strong acid is acidic because of hydrolysis. ‘The reaction of an anion or cation with water accompanied by cleavage of O—H bond is called hydrolysis. Degree of hydrolysis is defined as the fraction of the total salt that has undergone hydrolysis on the attainment of the equilibrium. ‘The hydrolysis constant K;, of the salt varies inversely with the dissociation constant K, of the weak acid. Kj, = K,/K, Weaker the acid, the greater is the hydrolysis constant of the salt. ‘The pH of asalt ofa strong acid and strong base is 7 and the solution is neutral e.g., NaCl, KCL ‘The pH of a salt of a weak acid and strong base can be calculated using the relation: pH= 7+3IDK, +logC] eg, CH,COONa, Na,PO, ‘The pH of salt of weak bases and strong acids can be calculated by using the relation: pH 1 5 IPR) log] e,gs NHCl. CuSO, ‘The pH of a salt of a weak acid and weak base is given by 1 At25°C, PH=74+5[pKy—PKy] eg, CH,COONH,, AlPO, For salts of weak bases and strong acids, degree of hydrolysis is given as For salts of weak acids and weak bases, the degree of hydrolysis is given as " ‘cHemistrY Topay | yoveveeR ‘14 93 Seine TE eases PHYSICS | [SstaNiiung open t day = Conerten Cane abe Ganka & Advanced), AIPMT, = PMTs, All State E LevelEngg. & IG Medical Exams YB e ‘Trust of over 1 Crore readers, Since 1982. + Practice steadily, paced month by comprising experts and members _confidence-building exercises, month, with very'similar & model from MTG's well-experienced new studying techniques, time test papers Editorial Board management, even advice from + Selfassessment testsforyouto + Stay up-to-date withimportant past IT/PMT toppers evaluate your readiness and information such as examination «Bonus: exposure to competition confidence for the big exams dates, vends& changesin sylabl__at aglobal level, with questions + Content puttogetherbya team —« Alkround skill enhancement from Inti, Olympiads & Contests Please accept my subscription to: (Confirm your hoe by icking the appropriate boxes) Name: ______ Ctyee 900 Jayrsce 1s00 Jaye 2100 scone Dityne soo [Fayee 1.200 Ja yesiz roo miata Re OT eee OO Ftyres00 Jayme r200 Jayne 700 | omerrronealol TY TT TIT eames Individual magazines Ea _____________i___.____ Ftyee300 = Jayrsesoo = —Jayse6s | OD 4 es - cuemisray ToDay | ovate 18