Textbooks School Textbooks Online Skip to contentHomeNCERT Class 11Biology1. The Living World2.

Biological Classification3: Plant Kingdom4: Animal Kingdom5. Morphology of Flowering Plants6. Anatomy of Flowering Plants7. Structural Organisation in Animals8. The Unit of Life9. BioMolecules10. Cell Cy cle and Cell Division11. Transport in Plants12. Mineral Nutrition13. Photosynthe sis in higher plants14. Respiration in Plants15.Plant Growth and Development16. Digestion And Absorption17. Breathing and Exchange of Gases18. Body fluids and c irculation19. Excretory Products and their Elimination20. Locomotion and Movemen t21. Neural Control and Coordination22. Chemical Coordination and IntegrationLab ManualChemistry1. Some Basic Concepts Of Chemistry2. Structure Of Atom3. Classi fication of Elements and Periodicity in Propertiesproblem4. Chemical Bonding And Molecular Structure5. States Of Matter6 Thermodynamics7. Equilibrium8. Redox Re actions9. Hydrogen10. The s -Block Elements11. The p -Block Elements12. Organic Chemistry- Some Basic Principles And Techniques13. Hydrocarbons14. Environmental ChemistryPhysicsClass 6Science1. Food: Where does it come from?Class 12Biology1 . Reproduction in Organisms2. Sexual Reproduction in Flowering Plants3. Human Re production4. Reproductive Health5. Principles of Inheritance and Variation6. Mol ecular Basis of Inheritance7. Evolution8. Human Health and Disease9. Strategies for Enhancement in Food Production10. Microbes in Human Welfare11. Biotechnology : Principles and Processes12. Biotechnology and its Applications13. Organisms a nd Populations14. Ecosystem15. Biodiversity and Conservation16. Environmental Is suesMODEL QUESTION PAPERLab Manual Part 2Chemistry1. The Solid State2. Solutions 3. Electrochemistry4. Chemical Kinetics5. Surface Chemistry6 General Principles and of Processes of Isolation Elements7. The p-Block Elements8. The d- and f- bl ock Elements9. Coordination Compound10. Haloalkanes and Haloarenes11. Alcohols, Phenols and Ethers12. Aldehydes, Ketones and Carboxylic Acids13. Amines14. Biomo lecules15. Polymers16. Chemistry in Everyday life12. Organic Chemistry- Some Bas ic Principles And Techniques In the previous unit you have learnt that the element carbon has the unique prop erty called catenation due to which it forms covalent bonds with other carbon at oms. It also forms covalent bonds with atoms of other elements like hydrogen, ox ygen, nitrogen, sulphur, phosphorus and halogens. The resulting compounds are st udied under a separate branch of chemistry called organic chemistry. This unit i ncorporates some basic principles and techniques of analysis required for unders tanding the formation and properties of organic compounds. 12.1 GENERAL INTRODUCTION Organic compounds are vital for sustaining life on earth and include complex mol ecules like genetic information bearing deoxyribonucleic acid (DNA) and proteins that constitute essential compounds of our blood, muscles and skin. Organic che micals appear in materials like clothing, fuels, polymers, dyes and medicines. T hese are some of the important areas of application of these compounds. Science of organic chemistry is about two hundred years old. Around the year 178 0, chemists began to distinguish between organic compounds obtained from plants and animals and inorganic compounds prepared from mineral sources. Berzilius, a Swedish chemist proposed that a vital force was responsible for the formation of o rganic compounds. However, this notion was rejected in 1828 when F. Wohler synth esised an organic compound, urea from an inorganic compound, ammonium cyanate.

The pioneering synthesis of acetic acid by Kolbe (1845) and that of methane by B erthelot (1856) showed conclusively that organic compounds could be synthesised from inorganic sources in a laboratory. The development of electronic theory of covalent bonding ushered organic chemist ry into its modern shape.

12.2 TETRAVALENCE OF CARBON:SHAPES OF ORGANIC COMPOUNDS 12.2.1 The Shapes of Carbon Compounds The knowledge of fundamental concepts of molecular structure helps in understand ing and predicting the properties of organic compounds. You have already learnt theories of valency and molecular structure in Unit 4. Also, you already know th at tetravalence of carbon and the formation of covalent bonds by it are explaine d in terms of its electronic configuration and the hybridisation of s and p orbi tals. It may be recalled that formation and the shapes of molecules like methane (CH4), ethene (C2H4), ethyne (C2H2) are explained in terms of the use of sp3, s p2 and sp hybrid orbitals by carbon atoms in the respective molecules. Hybridisation influences the bond length and bond enthalpy (strength) in organic compounds. The sp hybrid orbital contains more s character and hence it is clos er to its nucleus and forms shorter and stronger bonds than the sp3 hybrid orbit al. The sp2 hybrid orbital is intermediate in s character between sp and sp3 and , hence, the length and enthalpy of the bonds it forms, are also intermediate be tween them. The change in hybridisation affects the electronegativity of carbon. The greater the s character of the hybrid orbitals, the greater is the electron egativity. Thus, a carbon atom having an sp hybrid orbital with 50% s character is more electronegative than that possessing sp2 or sp3 hybridised orbitals. Thi s relative electronegativity is reflected in several physical and chemical prope rties of the molecules concerned, about which you will learn in later units. 12.2.2 Some Characteristic Features of Bonds In a ( i) bond formation, arallel orientation of the two orbitals on adjacent atoms is necessary for a ro er sideways overla . Thus, in H2C=CH2 molecule all the atoms must be in the same lane. The orbitals are mutually arallel and b oth the orbitals are er endicular to the lane of the molecule. Rotation of o ne CH2 fragment with res ect to other interferes with maximum overla of orbit als and, therefore, such rotation about carbon-carbon double bond (C=C) is restr icted. The electron charge cloud of the bond is located above and below the lan e of bonding atoms. This results in the electrons being easily available to the attacking reagents. In general, bonds rovide the most reactive centres in the m olecules containing multi le bonds. Problem 12.1 How many and bond are re ent in each of the following molecule ? (a) HCCCH=CHCH3 (b) CH2=C=CHCH3 Solution (a) C-C: 4; C-H:6; C=C:1; CC:2 (b) C-C: 3; C-H:6; C=C:2. Problem 12.2 What i the ty e of hybridi ation of each carbon in the following com ound ? (a) CH3Cl, (b) (CH3)2CO, (c) CH3CN, (d) HCONH2, (e) CH3CH=CHCN Solution (a) 3, (b) 3, 2, (c) 3, , (d) 2, (e) 3, 2, 2, Problem 12.3 Write the tate of hybridi ation of carbon in the following com ound and ha e of each of the molecule . (a) H2C=O, (b) CH3F, (c) HCN. Solution (a) 2 hybridi ed carbon, trigonal lanar; (b) 3 hybridi ed carbon, tetrahedr

12.3 STRUCTURAL REPRESENTATIONS OF ORGANIC COMPOUNDS

Structure of organic com ound are re re ented in everal way . The Lewi truc ture or dot tructure, da h tructure, conden ed tructure and bond line tructu ral formula are ome of the ecific ty e . The Lewi tructure , however, can be im lified by re re enting the two-electron covalent bond by a da h (-). Such a tructural formula focu e on the electron involved in bond formation. A in gle da h re re ent a ingle bond, double da h i u ed for double bond and a tri le da h re re ent tri le bond. Lone air of electron on heteroatom (e.g., ox ygen, nitrogen, ul hur, halogen etc.) may or may not be hown. Thu , ethane (C 2H6), ethene (C2H4), ethyne (C2H2) and methanol (CH3OH) can be re re ented by th e following tructural formula . Such tructural re re entation are called com lete tructural formula .

The e tructural formula can be further abbreviated by omitting ome or all of the da he re re enting covalent bond and by indicating the number of identical grou attached to an atom by a ub cri t. The re ulting ex re ion of the com ound i called a conden ed tructural formula. Thu , ethane, ethene, ethyne and methanol can be written a : Similarly,CH3CH2CH2CH2CH2CH2CH2CH3 can be further conden ed to CH3(CH2)6CH3. For further im lification, organic chemi t u e another way of re re enting the t ructure , in which only line are u ed. In thi bond-line tructural re re entat ion of organic com ound , carbon and hydrogen atom are not hown and the line re re enting carbon-carbon bond are drawn in a zig-zag fa hion. The only atom ecifically written are oxygen, chlorine, nitrogen etc. The terminal denote me thyl (-CH3) grou (unle indicated otherwi e by a functional grou ), while the line junction denote carbon atom bonded to a ro riate number of hydrogen re quired to ati fy the valency of the carbon atom . Some of the exam le are re r e ented a follow : (i) 3-Methyloctane can be re re ented in variou form a :

(ii) Variou way of re re enting 2-bromo butane are: (a) CH3CHBrCH2CH3

Problem 12.4

Ex and each of the following conden ed formula into their com lete

In cyclic com ound , the bond-line formula may be given a

follow :

tructural f

12.3.1 Com lete, Conden ed and Bond-line Structural Formula

al; (c)

hybridi ed carbon, linear.

ormula . (a) CH3CH2COCH2CH3 (b) CH3CH=CH(CH2)3CH3 Problem 12.5 For each of the following com ound , write a conden ed formula and al o their bo nd-line formula.

Problem 12.6 Ex and each of the following bond-line formula to how all the atom including carbon and hydrogen

12.3.2 Three-Dimen ional Re re entation of Organic Molecule The three-dimen ional (3-D) tructure of organic molecule can be re re ented on a er by u ing certain convention . For exam le, by u ing olid and da hed we dge formula, the 3-D image of a molecule from a two-dimen ional icture can be erceived. In the e formula the olid-wedge i u ed to indicate a bond rojectin g out of the lane of a er, toward the ob erver. The da hed-wedge i u ed to d e ict the bond rojecting out of the lane of the a er and away from the ob erv er. Wedge are hown in uch a way that the broad end of the wedge i toward th e ob erver. The bond lying in lane of the a er are de icted by u ing a normal line (-). 3-D re re entation of methane molecule on a er ha been hown in Fig . 12.1.

Molecular model are hy ical device that are u ed for a better vi uali ation and erce tion of three-dimen ional ha e of organic molecule . The e are made of wood, la tic or metal and are commercially available. Commonly three ty e o f molecular model are u ed: (1) Framework model, (2) Ball-and- tick model, and (3) S ace filling model. In the framework model only the bond connecting the at om of a molecule and not the atom them elve are hown. Thi model em ha ize the attern of bond of a molecule while ignoring the ize of atom . In the ball -and- tick model, both the atom and the bond are hown. Ball re re ent atom and the tick denote a bond. Com ound containing C=C (e.g., ethene) canbe t be re re ented by u ing ring in lace of tick . The e model are referred to a balland- ring model. The ace-filling model em ha i e the relative ize of each atom ba ed on it van der Waal radiu . Bond are not hown in thi model. It convey the volume occu ied by each atom in the molecule. In addition to the e model , com uter gra hic can al o be u ed for molecular modelling.

12.4 CLASSIFICATION OF ORGANIC COMPOUNDS

I. Acyclic or o en chain com ound

The exi ting large number of organic com ound and their ever-increa ing number ha made it nece ary to cla ify them on the ba i of their tructure . Organi c com ound are broadly cla ified a follow :

Molecular Model

The e com ound are al o called a ali hatic com ound and con i t of traight o r branched chain com ound , for exam le:

Acyclic (ali hatic cyclic) com ound contain carbon atom joined in the form of a ring homocyclic). Sometime atom other than carbon are al o re ent in the ri ng (heterocylic). Some exam le of thi ty e of com ound are:

Aromatic com ound are ecial ty e of com ound . You will learn about the e co m ound in detail in Unit 13. The e include benzene and other related ring com o und (benzenoid). Like alicyclic com ound , aromatic comound may al o have hete ro atom in the ring. Such com ound are called hetrocyclic aromatic com ound . S ome of the exam le of variou ty e of aromatic com ound are:

Functional Grou

The functional grou may be defined a an atom or grou of atom joined in a e cific manner which i re on ible for the characteri tic chemical ro ertie of the organic com ound . The exam le are hydroxyl grou (-OH), aldehyde grou (-C HO) and carboxylic acid grou (-COOH) etc.

12.5 NOMENCLATURE OF ORGANIC COMPOUNDS Organic chemi try deal with million of com ound . In order to clearly identify them, a y tematic method of naming ha been develo ed and i known a the IUPA C (International Union of Pure and A lied Chemi try) y tem of nomenclature. In thi y tematic nomenclature, the name are correlated with the tructure uch that the reader or li tener can deduce the tructure from the name. Before the IUPAC y tem of nomenclature, however, organic com ound were a igne d name ba ed on their origin or certain ro ertie . For in tance, citric acid i named o becau e it i found in citru fruit and the acid found in red ant i named formic acid ince the Latin word for ant i formica. The e name are trad itional and are con idered a trivial or common name . Some common name are fol lowed even today. For exam le, Buckmin terfullerene i a common name given to th

A grou or a erie of organic com ound each containing a characteri tic functi onal grou form a homologou erie and the member of the erie are called ho mologue . The member of a homologou erie can be re re ented by general molec ular formula and the ucce ive member differ from each other in molecular form ula by a -CH2 unit. There are a number of homologou erie of organic com ound . Some of the e are alkane , alkene , alkyne , haloalkane , alkanol , alkanal , alkanone , alkanoic acid , amine etc.

Homologou

Serie

Organic com ound can al o be cla familie or homologou erie .

ified on the ba i

of functional grou , into

Aromatic com ound

The e exhibit ome of the ro ertie

imilar to tho e of ali hatic com ound .

II Acyclic or clo ed chain or ring com ound

e newly di covered C60 clu ter (a form of carbon) noting it tructural imilari ty to the geode ic dome o ulari ed by the famou architect R. Buckmin ter Full er. Common name are u eful and in many ca e indi en able, articularly when t he alternative y tematic name are lengthy and com licated. Common name of om e organic com ound are given in Table 12.1.

12.5.1 The IUPAC Sy tem of Nomenclature A y tematic name of an organic com ound i generally derived by identifying the arent hydrocarbon and the functional grou ( ) attached to it. See the exam le given below.By further u ing refixe and uffixe , the arent name can be modif ied to obtain the actual name. Com ound containing carbon and hydrogen only are called hydrocarbon . A hydrocarbon i termed aturated if it contain only carb on-carbon ingle bond . The IUPAC name for a homologou erie of uch com ound i alkane. Paraffin (Latin: little affinity) wa the earlier name given to the e com ound . Un aturated hydrocarbon are tho e, which contain at lea t one carb oncarbon double or tri le bond.

Straight chain hydrocarbon : The name of uch com ound are ba ed on their chai n tructure, and end with uffix -ane and carry a refix indicating the number of carbon atom re ent in the chain (exce t from CH4 to C4H10, where the refixe are derived from trivial name ). The IUPAC name of ome traight chain aturate d hydrocarbon are given in Table 12.2. The alkane in Table 12.2 differ from ea ch other by merely the number of -CH2 grou in the chain. They are homologue o f alkane erie .

Branched chain hydrocarbon : In a branched chain com ound mall chain of carbon atom are attached at one or more carbon atom of the arent chain. The mall c arbon chain (branche ) are called alkyl grou . For exam le: In order to name uch com ound , the name of alkyl grou are refixed to the n ame of arent alkane. An alkyl grou i derived from a aturated hydrocarbon by

Table 12.2 IUPAC Name of Some Unbranched Saturated Hydrocarbon Name Molecular formula Name Molecular formula Methane CH4 He tane C2H6 Ethane C2H8 Octane C8H18 Pro ane C3H8 Nonane C9H20 Butane C4H10 Decane C10H22 Pentane C5H12 Ico ane C20H42 Hexane C6H14 Triacontane C30H62

12.5.2 IUPAC Nomenclature of Alkane

Table 12.1 Common or Trivial Name of Some Organic com ound Com ound Common name CH4 Methane H3CCH2CH2CH3 n-Butane (H3C)2CHCH3 I obutane (H3C)4C Neo entane H3CCH2CH2OH n-Pro yl alcohol HCHO Formaldehyde (H3C)2CO Acetone CHCl3 Chloroform CH3COOH Acetic acid C6H6 Benzene C6H5OCH3 Ani ole C6H5NH2 Aniline C6H5COCH3 Aceto henone CH3OCH2CH3 Ethyl methyl ether

removing a hydrogen atom from carbon. Thu , CH4 become -CH3 and i called methy l grou . An alkyl grou i named by ub tituting yl for ane in the corre onding alk ane. Some alkyl grou are li ted in Table 12.3. Table 12.3 Some Alkyl Grou Alkane Alkyl grou Molecular formula Name of alkane Structural formula Name of alkyl grou CH4 Methane CH3 Methyl C2H6 Ethane -CH2CH3 Ethyl C3H8 Pro ane -CH2CH2CH3 Pro yl C4H10 Butane -CH2CH2CH2CH3 Butyl C10H22 Decane -CH2(CH2)8CH3 Decyl

Abbreviation are u ed for ome alkyl grou . For exam le, methyl i abbreviated a Me, ethyl a Et, ro yl a Pr and butyl a Bu. The alkyl grou can be branc hed al o. Thu , ro yl and butyl grou can have branched tructure a hown be low. Common branched grou have ecific trivial name . For exam le, the ro yl grou can either be n- ro yl grou or i o ro yl grou . The branched butyl grou ar e called ec-butyl, i obutyl and tert-butyl grou . We al o encounter the tructu ral unit, -CH2C(CH3)3, which i called neo entyl grou . Nomenclature of branched chain alkane : We encounter a number of branched chain alkane . The rule for naming them are g iven below. 1. Fir t of all, the longe t carbon chain in the molecule i identified. In the exam le (I) given below, the longe t chain ha nine carbon and it i con idered a the arent or root chain. Selection of arent chain a hown in (II) i not correct becau e it ha only eight carbon . 2. The carbon atom of the arent chain are numbered to identify the arent alka ne and to locate the o ition of the carbon atom at which branching take lac e due to the ub titution of alkyl grou in lace of hydrogen atom . The numberi ng i done in uch a way that the branched carbon atom get the lowe t o ible number . Thu , the numbering in the above exam le hould be from left to right ( branching at carbon atom 2 and 6) and not from right to left (giving number 4 and 8 to the carbon atom at which branche are attached). 3. The name of alkyl grou attached a a branch are then refixed to the name of the arent alkane and o ition of the ub tituent i indicated by the a ro riate number . If different alkyl grou are re ent, they are li ted in al habe tical order. Thu , name for the com ound hown above i : 6-ethyl-2- methylnonane . [Note: the number are e arated from the grou by hy hen and there i no br eak between methyl and nonane.] 4. If two or more identical ub tituent grou are re ent then the number are e arated by comma . The name of identical ub tituent are not re eated, in te ad refixe uch a di (for 2), tri (for 3), tetra (for 4), enta (for 5), hexa (for 6) etc. are u ed. While writing the name of the ub tituent in al habetica l order,the e refixe , however, are not con idered. Thu , the following com oun d are named a : 5. If the two ub tituent are found in equivalent o ition , the lower number i given to the one coming fir t in the al habetical li ting. Thu , the following

com ound i 3-ethyl-6-methyloctane and not 6-ethyl-3-methyloctane. 6. The branched alkyl grou can be named by following the above mentioned roce dure . However, the carbon atom of the branch that attache to the root alkane i numbered 1 a exem lified below. The name of uch branched chain alkyl grou i laced in arenthe i while namin g the com ound. While writing the trivial name of ub tituent in al habetical o rder, the refixe i o- and neo- are con idered to be the art of the fundamenta l name of alkyl grou . The refixe ec- and tert- are not con idered to be the art of the fundamental name. The u e of i o and related common refixe for nam ing alkyl grou i al o allowed by the IUPAC nomenclature a long a the e are not further ub tituted. In multi ub tituted com ound , the following rule may a o be remembered: If there ha en to be two chain of equal ize, then that chain i to be elect ed which contain more number of ide chain . After election of the chain, numbering i to be done from the end clo er to the ub tituent. Cyclic Com ound : A aturated monocyclic com ound i named by refixing cyclo to t he corre onding traight chain alkane. If ide chain are re ent, then the rul e given above are a lied. Name of ome cyclic com ound are given below. Problem 12.7

Solution (a) Lowe t locant number, 2,5,6 i lower than 3,5,7, (b) ub tituent are in equ ivalent o ition; lower number i given to the one that come fir t in the name according to al habetical order. 12.5.3 Nomenclature of Organic Com ound having Functional Grou ( ) A functional grou , a defined earlier, i an atom or a grou of atom bonded to gether in a unique manner which i u ually the ite of chemical reactivity in an organic molecule. Com ound having the ame functional grou undergo imilar re action . For exam le, CH3OH, CH3CH2OH, and (CH3)2CHOH- all having -OH functional grou liberate hydrogen on reaction with odium metal. The re ence of function al grou enable y temati ation of organic com ound into different cla e . E xam le of ome functional grou with their refixe and uffixe along with o me exam le of organic com ound o e ing the e are given in Table 12.4.

CH3(CH2)2CH3 Alkene >C=C< - -ene But-1-ene CH2=CHCH2CH3

Table 12.4 Some Functional Grou and Cla e of Organic Com ound Cla of com ound Functional grou tructure IUPAC grou refix IUPAC grou ffix Exam le Alkane - - -ane Butane,

Structure and IUPAC name of ome hydrocarbon name given in the arenthe e are incorrect.

are given below. Ex lain why the

Alkye -CC- - -yne But-1-yne CHCCH2CH3 Arene - - - Benzene, Halide -X (X=F,Cl,Br,I) halo- - 1-Bromobutane, CH3(CH2)2CH2Br

CH3CH2CHOHCH3 Aldehyde -CHO formyl, or oxo -al Butanal, CH3(CH2)2CHO Ketone >C=O oxo- -one Butan-2-one, CH3CH2COCH3

CH3CH2CH2CH2CN Ether -R-O-R- alkoxy- - Ethoxyethane, CH3CH2OCH2CH3

CH3(CH2)2CO2H Carboxylate ion -COO- - -oate Sodium butanoate, CH3(CH2)2CO2-Na+ E ter -COOR alkoxycarbonyl -oate Methyl ro anoate, CH3CH2COOCH3 Acyl halide -COX (X-F,Cl,Br,I) halocarbonyl -oyl halide Butanoyl chloride, CH3(CH2)2COCl Amine -NH2,

Carboxylic acid

Nitrile

Alcohol

-OH hydroxy- -ol Butan-2-ol,

-CN cyano nitrile Pentanenitrile,

-COOH carboxy -oic acid Butanoic acid,

>NH,>Namino- -amide Butan-2-amide, CH3CHNH3CH2CH3 Amide -CINH2, -CONHR, -CONR2 -carbamoyl -amide Butanamide, CH3(CH2)2CONH2 Nitro com ound -NO2 nitro - 1-Nitrobutane, CH3(CH2)3NO2 Sul honic acid -SO3H ul ho CH3SO3H Fir t of all, the functional grou re ent in the molecule i identified which d etermine the choice of a ro riate uffix. The longe t chain of carbon atom co ntaining the functional grou i numbered in uch a way that the functional grou i attached at the carbon atom o e ing lowe t o ible number in the chain. By u ing the uffix a given in Table 12.4, the name of the com ound i arrived at. In the ca e of olyfunctional com ound , one of the functional grou i cho en a the rinci al functional grou and the com ound i then named on that ba i . The remaining functional grou , which are ubordinate functional grou , are na med a ub tituent u ing the a ro riate refixe . The choice of rinci al func tional grou i made on the ba i of order of reference. The order of decrea in g riority for ome functional grou i : -COOH, -SO3H, -COOR (R=alkyl grou ), COCl, -CONH2, -CN,-HC=O, >C=O, -OH, -NH2, > C=C<, -CC- . The -R, C6H5-, halogen (F, Cl, Br, I), -NO2, alkoxy (-OR) etc. are alway refi x ub tituent . Thu , a com ound containing both an alcohol and a keto grou i named a hydroxyalkanone ince the keto grou i referred to the hydroxyl grou . For exam le, HOCH2(CH2) 3CH2COCH3 will be named a 7-hydroxyhe tan-2-one and not a 2-oxohe tan -7-ol. Similarly, BrCH2CH=CH2 i named a 3-bromo ro -1-ene and not 1- bromo ro -2-ene. If more than one functional grou of the ame ty e are re ent, their number i indicated by adding di, tri, etc. before the cla uffix. In uch ca e the ful l name of the arent alkane i written before the cla uffix. For exam le CH2( OH)CH2(OH) i named a ethane-1,2-diol. However, the ending ne of the arent alk ane i dro ed in the ca e of com ound having more than one double or tri le bo nd; for exam le, CH2=CH-CH=CH2 i named a buta-1,3-diene. Problem 12.8 Write the IUPAC name of the com ound i-iv from their given tructure . Solution ul honic acid Methyl u honic acid

In addition, a methyl grou i attached at 6th carb of thi com ound i 6-Methyloctan-3-ol.

Solution The functional grou re ent i ketone (>C=O), hence uffix -one. Pre ence of two keto grou i indicated by di, hence uffix become dione. The two keto grou are at carbon 2 and 4. The longe t chain contain 6 carbon atom , hence, arent hyd rocarbon i hexane. Thu , the y tematic name i Hexane- 2,4-dione. Solution Here, two functional grou namely ketone and carboxylic acid are re ent. The rinci al functional grou i the carboxylic acid grou ; hence the arent chain w ill be uffixed with oicacid. Numbering of the chain tart from carbon of COOH fu nctional grou . The keto grou in the chain at carbon 5 i indicated by oxo. The l onge t chain including the rinci al functional grou ha 6 carbon atom ; hence the arent hydrocarbon i hexane. The com ound i , therefore, named a 5-Oxohexa noic acid. Solution The two C=C functional grou are re ent at carbon atom 1 and 3, while the CC f unctional grou i re ent at carbon 5. The e grou are indicated by uffixe di ene and yne re ectively. The longe t chain containing the functional grou ha 6 carbon atom ; hence the arent hydrocarbon i hexane. The name of com ound, ther efore, i Hexa-1,3- dien-5-yne. Problem 12.9 Derive the tructure of (i) 2-Chlorohexane, (ii) Pent-4-en-2-ol, (iii) 3- Nitroc yclohexene, (iv) Cyclohex-2-en-1-ol, (v) 6-Hydroxyhe tanal. Solution (i) hexaneindicate the re ence of 6 carbon atom in the chain. The functional gr ou chloro i re ent at carbon 2. Hence, the tructure of the com ound i CH3CH 2CH2CH2CH(Cl)CH3. (ii) ent indicate that arent hydrocarbon contain 5 carbon atom in the chain. e n and ol corre ond to the functional grou C=C and -OH at carbon atom 4 and 2 re ectively. Thu , the tructure i CH2=CHCH2CH (OH)CH3. (iii) Six membered ring containing a carbon-carbon double bond i im lied by cyc lohexene, which i numbered a hown in (I). The refix 3-nitro mean that a nit ro grou i re ent on C-3. Thu , com lete tructural formula of the com ound i (II). Double bond i uffixed functional grou wherea NO2 i refixed function al grou therefore double bond get reference over -NO2 grou : (iv) 1-ol mean that a -OH grou i re ent at C-1. OH i uffixed functional grou and get reference over C=C bond. Thu the tructure i a hown in (II): (v) he tanal indicate the com ound to be an aldehyde containing 7 carbon atom in the arent chain. The 6-hydroxy indicate that -OH grou i re ent at carbon 6. Thu , the tructural formula of the com ound i : CH3CH(OH)CH2CH2CH2CH2CHO. Carbon atom of -CHO grou i included while numbering the carbon chain.

The functional grou re ent The longe t chain containing aturated hydrocarbon i octane. The -OH i on carbon atom 3. on. Hence, the y tematic name

i an alcohol (OH). Hence the uffix i -ol. -OH ha eight carbon atom . Hence the corre onding

For IUPAC nomenclature of ub tituted benzene com ound , the ub tituent i lac ed a refix to the word benzene a hown in the following exam le . However, co mmon name (written in bracket below) of many ub tituted benzene com ound are al o univer ally u ed. If benzene ring i di ub tituted, the o ition of ub tituent i defined by num bering the carbon atom of the ring uch that the ub tituent are located at th e lowe t number o ible.For exam le, the com ound(b) i named a 1,3-dibromobe nzene and not a 1,5-dibromobenzene. In the trivial y tem of nomenclature the term ortho (o), meta (m) and ara ( ) are u ed a refixe to indicate the relative o ition 1,2- ;1,3- and 1,4- re ectively. Thu , 1,3-dibromobenzene (b) i named a m-dibromobenzene (meta i ab breviated a m-) and the other i omer of dibromobenzene 1,2-(a) and 1,4-(c), ar e named a ortho (or ju t o-) and ara (or ju t -)-dibromobenzene, re ectively .

For tri or higher ub tituted benzene derivative , the e refixe cannot be u ed and the com ound are named by identifying ub tituent o ition on the ring by following the lowe t locant rule. In ome ca e , common name of benzene derivat ive i taken a the ba e com ound. Sub tituent of the ba e com ound i a igned number1 and then the direction of n umbering i cho en uch that the next ub tituent get the lowe t number. The u b tituent a ear in the name in al habetical order. Some exam le are given bel ow.

Problem 12.10 Write the tructural formula of: (a) o-Ethylani ole, (b) -Nitroaniline, (c) 2,3 Dibromo -1 henyl entane, (d) 4-Ethyl-1-fluoro-2-nitrobenzene. 12.6 ISOMERISM The henomenon of exi tence of two or more com ound o e ing the ame molecul ar formula but different ro ertie i known a i omeri m. Such com ound are ca lled a i omer . The following flow chart how different ty e of i omeri m. 12.6.1 Structural I omeri m Com ound having the ame molecular formula but different tructure (manner in which atom are linked) are cla ified a tructural i omer . Some ty ical exam le of different ty e of tructural i ome ri m are given below. (i) Chain i omeri m: When two or more com ound have imilar molecular formula b ut different carbon keleton , the e are referred to a chain i omer and the h

When a benzene ring i attached to an alkane with a functional grou , it i con idered a ub tituent, in tead of a arent. The name for benzene a ub tituent i henyl (C6H5-, al o abbreviated a Ph).

12.5.4 Nomenclature of Sub tituted Benzene Com ound

(ii) Po ition i omeri m: When two or more com ound differ in the o ition of u b tituent atom or functional grou on the carbon keleton, they are called o it ion i omer and thi henomenon i termed a o ition i omeri m. For exam le, th e molecular formula C3H8O re re ent two alcohol : (iii) Functional grou i omeri m: Two or more com ound having the ame molecula r formula but different functional grou are called functional i omer and thi henomenon i termed a functional grou i omeri m. For exam le, the molecular formula C3H6O re re ent an aldehyde and a ketone: (iv) Metameri m: It ari e due to different alkyl chain on either ide of the f unctional grou in the molecule. For exam le, C4H10O re re ent methoxy ro ane ( CH3OC3H7) and ethoxyethane (C2H5OC2H5) 12.6.2 Stereoi omeri m The com ound that have the ame con titution and equence of covalent bond but differ in relative o ition of their atom or grou in ace are called tereoi omer . Thi ecial ty e of i omeri m i c alled a tereoi omeri m and can be cla ified a geometrical and o tical i omer i m. 12.7 FUNDAMENTAL CONCEPTS IN ORGANIC REACTION MECHANISM In an organic reaction, the organic molecule (al o referred a a ub trate) reac t with an a ro riate attacking reagent and lead to the formation of one or mo re intermediate( ) and finally roduct( ) The general reaction i de icted a follow : Sub trate i that reactant which u lie carbon to the new bond and the other r eactant i called reagent. If both the reactant u ly carbon to the new bond t hen choice i arbitrary and in that ca e the molecule on which attention i focu ed i called ub trate. In uch a reaction a covalent bond between two carbon atom or a carbon and ome other atom i broken and a new bond i formed. A equential account of each te , de cribing detail of electron movement, energetic during bond cleavage and bond formation, and the rate of tran formation of reactant into roduct (kine tic ) i referred to a reaction mechani m. The knowledge of reaction mechani m hel in under tanding the reactivity of organic com ound and in lanning trat egy for their ynthe i .

12.7.1 Fi ion of a Covalent Bond A covalent bond can get cleaved either by : (i) heterolytic cleavage, or by (ii) homolytic cleavage. In heterolytic cleavage, the bond break in uch a fa hion that the hared air of electron remain with one of the fragment .

After heteroly i , one atom ha a

extet electronic

tructure and a o itive cha

In the following ection , we hall learn w the e reaction take lace.

ome of the

rinci le that ex lain ho

enomenon i termed a und :

chain i omeri m. For exam le, C5H12 re re ent

three com o

rge and the other, a valence octet with at lea t one lone air and a negative ch arge. Thu , heterolytic cleavage of bromomethane will give CH+ and Br- a hown below. A ecie having a carbon atom o e ing extext of electron and a o itive ch arge i called a carbocation (earlier called carbonium ion). The C+ H3 ion i kn own a a methyl cation or methyl carbonium ion. Carbocation are cla ified a rimary, econdary or tertiary de ending on whether one, two or three carbon are directly attached to the o itively charged carbon. Some other exam le of carb ocation are: CH3C+H2 (ethyl cation, a rimary carbocation), (CH3)C+H H (i o ro yl cation, a econdary carbocation), and (CH3)3C+ (tert-butyl cation, a tertiary carbocation). Carbocation are highly un table and reactive ecie . Alkyl grou directly attached to the o itively charged carbon tabili e the carbocation due to inductive and hy erconjugation effect , which you will be tudying in th e ection 12.7.5 and 12.7.9. The ob erved order of carbocation tability i : C+H3 < CH3C+H2 < (CH3)2C+H < (CH3)3C+. The e carbocation have trigonal lanar ha e with o itively charged carbon being 2 hybridi ed. Thu , the ha e of C+H 3 may be con idered a being derived from the overla of three equivalent C( 2) hybridi ed orbital with 1 orbital of each of the three hydrogen atom . Each b ond may be re re ented a C( 2)-H(1 ) igma bond. The remaining carbon orbital i er endicular to the molecular lane and contain no electron . (Fig. 12.3). The heterolytic cleavage can al o give a ecie in which carbon get the hared air of electron . For exam le, when grou Z attached to the carbon leave with out electron air, the methyl anion(H3C-) i formed. Such a carbon ecie carry ing a negative charge on carbon atom i called carbanion. Carbanion are al o un table and reactive ecie . The organic reaction which roceed through heterol ytic bond cleavage are called ionic or hetero olar or ju t olar reaction . In homolytic cleavage, one of the electron of the hared air in a covalent bon d goe with each of the bonded atom . Thu , in homolytic cleavage, the movement of a ingle electron take lace in tead of an electron air. The ingle electro n movement i hown by half-headed (fi h hook: curved arrow. Such cleavage re ult in the formation of neutral ecie (atom or grou ) which contain an un aired electron. The e ecie are called free radical . Like carbocation and carbanio n , free radical are al o very reactive. A homolytic cleavage can be hown a : Alkyl radical are cla ified a rimary, econdary, or tertiary. Alkyl radical tability increa e a we roceed from rimary to tertiary: Organic reaction , which roceed by homolytic fi ion are called free radical or homo olar or non olar reaction .

A reagent that bring an electron air i called a nucleo hile (Nu:) i.e., nucle u eeking and the reaction i then called nucleo hilic. A reagent that take aw ay an electron air i called electro hile (E+) i.e., electron eeking and the r eaction i called electro hilic. During a olar organic reaction, a nucleo hile attack an electro hilic centre o f the ub trate which i that ecific atom or art of the electro hile that i electron deficient. Similarly, the electro hile attack at nucleo hilic centre, which i the electron rich centre of the ub trate. Thu , the electro hile rece ive electron air from nucleo hile when the two undergo bonding interaction. A c

12.7.2 Nucleo hile and Electro hile

Problem 12.11 U ing curved-arrow notation, how the formation of reactive intermediate when t he following covalent bond undergo heterolytic cleavage. (a) CH3-SCH3, (b) CH3-CN,(c) CH3-Cu Problem 12.12 Giving ju tification, categori e the following molecule /ion a nucleo hile or electro hile: HS-,BF3,C2H5O-,(CH3)3N:, Cl+,CH3-C+=O,H2N:-,N+O2 Solution Nucleo hile : HS-,C2H5O-,(CH3)3N:,H2N:The e ecie have un hared air of electron , which can be donated and hared w ith an electro hile. Electro hile : BF3,Cl+,CH3-C=O,N+O2. Reactive ite have only ix valence electron ; can acce t electron air from a nucleo hile. Problem 12.13 Identify electro hilic centre in the following: CH3CH=O, CH3CN, CH3I. Solution Among CH3HC*=O, H3CC*N, and H3C*-I, the tarred carbon atom are electro hilic ce nter a they will have artial o itive charge due to olarity of the bond.

The movement of electron in organic reaction can be hown by curved-arrow nota tion. It how how change in bonding occur due to electronic redi tribution dur ing the reaction. To how the change in o ition of a air of electron , curved arrow tart from the oint from where an electron air i hifted and it end a t a location to which the air of electron may move. Pre entation of hifting of electron air i given below : Movement of ingle electron i indicated by a ingle barbed fi h hook (i.e. half headed curved arrow). For exam le, in tran fer of hydroxide ion giving ethanol a nd in the di ociation of chloromethane, the movement of electron u ing curved a rrow can be de icted a follow :

12.7.4 Electron Di lacement Effect

in Covalent Bond

12.7.3 Electron Movement in Organic Reaction

urved-arrow notation i u ed to how the movement of an electron air from the n ucleo hile to the electro hile. Some exam le of nucleo hile are the negatively charged ion with lone air of electron uch a hydroxide (HO- ), cyanide (NC) ion and carbanion (R3C:-). Neutral molecule uch a etc., can al o act a nucleo hile due to the re ence of lone air of electron . Exam le of electro hile include carbocation (C+H3) and neutral molecule having functional grou like carbonyl grou (>C=O) or alkyl halide (R3C-X, where X i a halogen atom). The carbon atom in carbocation ha extet configuration; hence, it i electron deficient and can receive a air of electron from the nucleo hile . In neutral molecule uch a alkyl halide , due to the olarity of the C-X bond a artial o itive charge i generated on the carbon atom and hence the carbon atom become an electro hilic centre at which a nucleo hile can attack.

12.7.5 Inductive Effect

Let u con ider cholorethane (CH3CH2Cl) in which the C-Cl bond i a olar covale nt bond. It i olari ed in uch a way that the carbon-1 gain ome o itive cha rge (+) an the chlorine some negative charge (-). The fractional electronic charg es on the two atoms in a polar covalent bon are enote by symbol ( elta) an t he shift of electron ensity is shown by an arrow that points from + to - en of t he polar bon . In turn carbon-1, which has evelope partial positive charge (+) raws some elec tron ensity towar s it from the a jacent C-C bon . Consequently, some positive charge (+) evelops on carbon-2 also, where + symbolises relatively smaller positive charge as compare to that on carbon 1. I n other wor s, the polar C Cl bon in uces polarity in the a jacent bon s. Such polarisation of -bond cau ed by the olari ation of adjacent -bond i referred to a the inductive effect. Thi effect i a ed on to the ub equent bond al o b ut the effect decrea e ra idly a the number of intervening bond increa e and become vani hingly mall after three bond . The inductive effect i related to the ability of ub tituent( ) to either withdraw or donate electron den ity to the attached carbon atom. Ba ed on thi ability, the ub titutent can be cla i fied a electron-withdrawing or electron donating grou relative to hydrogen. H alogen and many other grou uch a nitro (- NO2), cyano (- CN), carboxy (- CO OH), e ter (-COOR), aryloxy (-OAr, e.g. OC6H5), etc. are electron-withdrawing gr ou . On the other hand, the alkyl grou like methyl (-CH3) and ethyl (-CH2-CH3 ) are u ually con idered a electron donating grou .

ince Br i more olar electronegetive then H, (b) C-O, (c) C-O ex ected to be the lea

Solution Magnitude of inductive effect dimini he a the number of intervening bond ea e . Hence, the effect i lea t in the bond between carbon-3 and hydrogen.

Problem 12.15 In which C-C bond of CH3CH2CH2Br, the inductive effect i t?

Solution (a)C-Br,

Problem 12.14 Which bond i more olar in the following air (b) H3C-NH2, H3C-OH (c) H3C-OH, H3C-SH

of molecule : (a) H3C-H, H3C-Br

incr

When a covalent bond electron den ity i electronegative atom olar covalent bond. c com ound .

i formed between atom of different electronegativity, the more toward the more of the bond. Such a hift of electron den ity re ult in a Bond olarity lead to variou electronic effect in organi

The electron di lacement in an organic molecule may take lace either in the gr ound tate under the influence of an atom or a ub tituent grou or in the re e nce of an a ro riate attacking reagent. The electron di lacement due to the i nfluence of an atom or a ub tituent grou re ent in the molecule cau e ermane nt olarli ation of the bond. Inductive effect and re onance effect are exam le of thi ty e of electron di lacement . Tem orary electron di lacement effect are een in a moleculewhen a reagent a roache to attack it. Thi ty e of ele ctron di lacement i called electromeric effect or olari ability effect. In th e following ection we will learn about the e ty e of electronic di lacement .

12.7.6 Re onance Structure There are many organic molecule who e behaviour cannot be ex lained by a ingle Lewi tructure. An exam le i that of benzene. It cyclic tructure containing alternating C-C ingle and C=C double b ond hown i inadequate for ex laining it characteri tic ro ertie . A er the above re re entation, benzene hould exhibit two different bond lengt h , due to C-C ingle and C=C double bond . However, a determined ex erimentall y benzene ha a uniform C-C bond di tance of 139 m, a value intermediate betwe en the C=C ingle(154 m) and C=C double (134 m) bond . Thu , the tructure of benzene cannot be re re ented adequately by the above tructure. Further, benzen e can be re re ented equally well by the energetically identical tructure I an d II. Therefore, according to the re onance theory (Unit 4) the actual tructure of be nzene cannot be adequately re re ented by any of the e tructure , rather it i a hybrid of the two tructure (I and II) called re onance tructure . The re on ance tructure (canonical tructure or contributing tructure ) are hy othetic al and individually do not re re ent any real molecule. They contribute to the a ctual tructure in ro ortion to their tability.

However, it i known that the two N-O bond of nitromethane are of the ame leng th (intermediate between a N-O ingle bond and a N=O double bond). The actual t ructure of nitromethane i therefore a re onance hybrid of the two canonical for m I and II. The energy of actual tructure of the molecule (the re onance hybrid) i lower t han that of any of the canonical tructure . The difference in energy between th e actual tructure and the lowe t energy re onance tructure i called the re on ance tabili ation energy or im ly the re onance energy. The more the number of im ortant contributing tructure , the more i the re onance energy. Re onance i articularly im ortant when the contributing tructure are equivalent in ene rgy. The following rule are a lied while writing re onance tructure :

Solution Fir t, write the tructure and ut un hared air of valence electron on a ro riate atom . Then draw the arrow one at a time moving the electron to get the other tructure .

Problem 12.16 Write re onance ed arrow .

tructure of CH3COO- and how the movement of electron by curv

The re onance tructure have (i) the ame o ition of nuclei and (ii) the ame number of un aired electron . Among the re onance tructure , the one which ha more number of covalent bond , all the atom with octet of electron (exce t hy drogen which ha a du let), le e aration of o o ite charge , (a negative cha rge if any on more electronegative atom, a o itive charge if any on more electr o o itive atom) and more di er al of charge, i more table than other .

Another exam le of re onance i rovided by nitromethane (CH3NO2) which can be r e re ented by two Lewi tructure , (I and II). There are two ty e of N-O bond in the e tructure .

Problem 12.17 Write re onance tructure of CH2=CH-CHO. Indicate relative tability of the con tributing tructure . [I: Mo t table, more number of covalent bond , each carbon and oxygen atom ha an octet and no e aration of o o ite charge II: negative charge on more electronegative atom and o itive charge on m ore electro o itive atom; III: doe not contribute a oxygen ha o itive charge and carbon ha negative charge, hence lea t table]. Problem 12.18 Ex lain why the following two tructure , I and II cannot be the major contribut or to the real tructure of CH3COOCH3. Solution The two tructure are le im ortant contributor a they involve charge e ara tion. Additionally, tructure I contain a carbon atom with an incom lete octet. 12.7.7 Re onance Effect The re onance effect i defined a the olarity roduced in the molecule by the i nteraction of two -bond or between a -bond and lone air of electron re ent on an adjacent atom. The effect i tran mitted through the chain. There are two ty e of re onance or me omeric effect de ignated a R or M effect. (i) Po itive Re onance Effect (+R effect) In thi effect, the tran fer of electr on i away from an atom or ub tituent grou attached to the conjugated y tem. Thi electron di lacement make certain o ition in the molecule of high elec tron den itie . Thi effect in aniline i hown a : (ii) Negative Re onance Effect (- R effect) Thi effect i ob erved when the tra n fer of electron i toward the atom or ub tituent grou attached to the conj ugated y tem. For exam le in nitrobenzene thi electron di lacement can be de icted a : The atom or ub tituent grou , which re re ent +R or -R electron di lacement effect are a follow : +R effect: halogen, -OH, -OR, -OCOR, -NH2, -NHR, -NR2, -NHCOR, -R effect: COOH, -CHO, >C=O, CN,-NO2

12.7.8 Electromeric Effect (E effect) It i a tem orary effect. The organic com ound having a multi le bond (a double or tri le bond) how thi effect in the re ence of an attacking reagent only. It i defined a the com lete tran fer of a hared air of -electron to one of t he atom joined by a multi le bond on the demand of an attacking reagent. The ef fect i annulled a oon a the attacking reagent i removed from the domain of the reaction. It i re re ented by E and the hifting of the electron i hown by a curved arrow ( ). There are two di tinct ty e of electromeric effect. (i) Po itive Eelctromeric Effect (+E effect) In thi effect the electrons of the m

The re ence of alternate ingle and double tem i termed a a conjugated y tem. The e r. The exam le are 1,3- butadiene, aniline , the -electron are delocali ed and the

bond in an o en chain or cyclic y y tem often how abnormal behaviou and nitrobenzene etc. In uch y tem y tem develo olarity.

ultiple bond are transferred to that atom to which the reagent gets attached. Fo r example : (ii)Negative Electromeric Effect ( E effect) In this effect the electron of the multi le bond are tran ferred to that atom to which the attacking reagent doe not get attached. For exam le: When inductive and electromeric effect o erate in o o ite direction , the elec tomeric effect redominate . 12.7.9 Hy erconjugation

To under tand hy erconjugation effect, let u take an exam le of CH3C+H2 (ethyl cation) in which the o itively charged carbon atom ha an em ty orbital. One of the C-H bond of the methyl grou can align in the lane of thi em ty orbi tal and the electron con tituting the C-H bond in lane with thi orbital can then be delocali ed into the em ty orbital a de icted in Fig. 12.4 (a). Thi ty e of overla tabili e the carbocation becau e electron den ity from th e adjacent bond hel in di er ing the o itive charge. In general, greater the number of alkyl grou attached to a o itively charged carbon atom, the greater i the h erconjugation interaction and tabili ation of the cation. Thu , we have the following relative tability of carbocation : Hy erconjugation i al o o ible in alkene and alkylarene .

There are variou way of looking at the hy erconjugative effect. One of the way i to regard C-H bond a o e ing artial ionic character due to re onance.

Problem 12.19 Ex lain why (CH3)3C+ i more table than and CH3C+H2 i the lea t table cation. Solution Hy erconjugation interaction in (CH3)3C+ i greater than in CH3C+H2 a the ha n ine C-H bond . In C+H3, vacant orbital i er endicular to the lane in which C-H bond lie; hence cannot overla with it. Thu , C+H3 lack hy erconjugative tability. 12.7.10 Ty e of Organic Reaction and Mechani m Organic reaction can be cla ified into the following categorie : (i) Sub titution reaction

The hy erconjugation may al o be regarded a

no bond re onance.

Delocali ation of electron icted a in Fig. 12.4(b).

by hy erconjugation in the ca e of alkene can be de

Hy erconjugation i a general tabili ing interaction. It involve delocali atio n of electron of C-H bond of an alkyl grou directly attached to an atom of un aturated y tem or to an atom with an un hared orbital. The electron of C-H b ond of the alkyl grou enter into artial conjugation with the attached un atura ted y tem or with the un hared orbital. Hy erconjugation i a ermanent effec t.

12.8 METHODS OF PURIFICATION OF ORGANIC COMPOUNDS Once an organic com ound i extracted from a natural ource or ynthe i ed in th e laboratory, it i e ential to urify it. Variou method u ed for the urific ation of organic com ound are ba ed on the nature of the com ound and the im ur ity re ent in it. The common technique u ed for urification are a follow : (i) Sublimation (ii) Cry talli ation (iii) Di tillation (iv) Differential extraction and (v) Chromatogra hy Finally, the urity of a com ound i a certained by determining it melting or b oiling oint. Mo t of the ure com ound have har melting oint and boiling oint . New method of checking the urity of an organic com ound are ba ed on different ty e of chromatogra hic and ectro co ic technique . 12.8.1 Sublimation You have learnt earlier that on heating, ome olid ub tance change from olid to va our tate without a ing through liquid tate. The urification techniqu e ba ed on the above rinci le i known a ublimation and i u ed to e arate ublimable com ound from non ublimable im uritie . 12.8.2 Cry talli ation Thi i one of the mo t commonly u ed technique for the urification of olid o rganic com ound . It i ba ed on the difference in the olubilitie of the com o und and the im uritie in a uitable olvent. The im ure com ound i di olved i n a olvent in which it i aringly oluble at room tem erature but a reciably oluble at higher tem erature. The olution i concentrated to get a nearly at urated olution. On cooling the olution, ure com ound cry talli e out and i removed by filtration. The filtrate (mother liquor) contain im uritie and mal l quantity of the com ound. If the com ound i highly oluble in one olvent and very little oluble in another olvent, cry talli ation can be ati factorily c arried out in a mixture of the e olvent . Im uritie , which im art colour to th e olution are removed by ad orbing over activated charcoal. Re eated cry talli ation become nece ary for the urification of com ound containing im uritie of com arable olubilitie . 12.8.3 Di tillation Thi im ortant method i u ed to e arate (i) volatile liquid from nonvolatile im uritie and (ii) the liquid having ufficient difference in their boiling o int . Liquid having different boiling oint va ori e at different tem erature . The va our are cooled and the liquid o formed are collected e arately. Chl oroform (b. 334 K) and aniline (b. . 457 K) are ea ily e arated by the techniq ue of di tillation (Fig 12.5). The liquid mixture i taken in a round bottom fla k and heated carefully. On boiling, the va our of lower boiling com onent are formed fir t. The va our are conden ed by u ing a conden er and the liquid i c ollected in a receiver. The va our of higher boiling com onent form later and t he liquid can be collected e arately.

(ii) Addition reaction (iii) Elimination reaction (iv) Rearrangement reaction You will be tudying the e reaction in Unit 13 and later in cla

XII.

One of the technological a lication of fractional di tillation i to e arate different fraction of crude oil in etroleum indu try. Di tillation under reduc ed re ure: Thi method i u ed to urify liquid having very high boiling oin t and tho e, which decom o e at or below their boiling oint . Such liquid are made to boil at a tem erature lower than their normal boiling oint by reducin g the re ure on their urface. A liquid boil at a tem erature at which it va our re ure i equal to the external re ure. The re ure i reduced with th e hel of a water um or vacuum um (Fig.12.8). Glycerol can be e arated from ent-lye in oa indu try by u ing thi technique.

Thu , if one of the ub tance in the mixture i water and the other, a water in oluble ub tance, then the mixture will boil clo e to but below, 373K. A mixtur e of water and the ub tance i obtained which can be e arated by u ing a e ar ating funnel. Aniline i e arated by thi technique from aniline water mixture (Fig.12.9). 12.8.4 Differential Extraction When an organic com ound i re ent i n an aqueou medium, it i e arated by haking it with an organic olvent in wh ich it i more oluble than in water. The organic olvent and the aqueou oluti on hould be immi cible with each other o that they form two di tinct layer wh ich can be e arated by e aratory funnel. The organic olvent i later removed

Steam Di tillation: Thi technique i a lied to e arate ub tance which are team volatile and are immi cible with water. In team di tillation, team from a team generator i a ed through a heated fla k containing the liquid to be di tilled. The mixture of team and the volatile organic com ound i conden ed and collected. The com ound i later e arated from water u ing a e arating funnel . In team di tillation, the liquid boil when the um of va our re ure due t o the organic liquid ( 1) and that due to water ( 2) become equal to the atmo heric re ure ( ), i.e. = 1+ 2. Since 1 i lower than , the organic liquid va ori e at lower tem erature than it boiling oint.

Va our of the liquid with higher boiling oint conden e before the va our of t he liquid with lower boiling oint. The va our ri ing u in the fractionating c olumn become richer in more volatile com onent. By the time the va our reach to the to of the fractionating column, the e are rich in the more volatile com on ent. Fractionating column are available in variou ize and de ign a hown i n Fig.12.7. A fractionating column rovide many urface for heat exchange betw een the a cending va our and the de cending conden ed liquid. Some of the conde n ing liquid in the fractionating column obtain heat from the a cending va our and reva ori e . The va our thu become richer in low boiling com onent. The v a our of low boiling com onent a cend to the to of the column. On reaching the to , the va our become ure in low boiling com onent and a through the cond en er and the ure liquid i collected in a receiver. After a erie of ucce i ve di tillation , the remaining liquid in the di tillation fla k get enriched i n high boiling com onent. Each ucce ive conden ation and va ori ation unit in the fractionating column i called a theoretical late. Commercially, column wi th hundred of late are available.

Fractional Di tillation: If the difference in boiling oint of two liquid i n ot much, im le di tillation cannot be u ed to e arate them. The va our of uc h liquid are formed within the ame tem erature range and are conden ed imulta neou ly. The technique of fractional di tillation i u ed in uch ca e . In thi technique, va our of a liquid mixture are a ed through a fractionating colum n before conden ation. The fractionating column i fitted over the mouth of the round bottom fla k (Fig.12.6).

by di tillation or by eva oration to get back the com ound. Differential extract ion i carried out in a e aratory funnel a hown in Fig. 12.10. If the organic com ound i le oluble in the organic olvent, a very large end (Fig. 12.11). The mixture ad orbed on quantity of olvent would be required to extract even a very mall quantity of the com ound. The technique of continuou extraction i em loyed in uch ca e . In thi technique ame olvent i re eatedly u ed for ex traction of the com ound. 12.8.5 Chromatogra hy Chromatogra hy i an im ortant technique exten ively u ed to e arate mixture i nto their com onent , urify com ound and al o to te t the urity of com ound . The name chromatogra hy i ba ed on the Greek word chroma, for colour ince the method wa fir t u ed for the e aration of coloured ub tance found in lant . In thi technique, the mixture of ub tance i a lied onto a tationary ha e, which may be a olid or a liquid. A ure olvent, a mixture of olvent , or a ga i allowed to move lowly over the tationary ha e. The com onent of the mixture get gradually e arated from one another. The moving ha e i called the mobile ha e. Ba ed on the rinci le involved, chromatogra hy i cla ified into different cat egorie . Two of the e are: (a) Ad or tion chromatogra hy, and (b) Partition chromatogra hy. a) Ad or tion Chromatogra hy: Ad or tion chromatogra hy i ba ed on the fact tha t different com ound are ad orbed on an ad orbent to different degree . Commonl y u ed ad orbent are ilica gel and alumina. When a mobile ha e i allowed to move over a tationary ha e (ad orbent), the com onent of the mixture move by varying di tance over the tationary ha e. Following are two main ty e of chr omatogra hic technique ba ed on the rinci le of differential ad or tion. (a) Column chromatogra hy, and (b) Thin layer chromatogra hy. Column Chromatogra hy: Column chromatogra hy involve e aration of a mixture ov er a column of ad orbent ( tationary ha e) acked in a gla tube. The column i fitted with a to cock at it lower end (Fig. 12.11). The mixture ad orbed on ad orbent i laced on the to of the ad orbent column acked in a gla tube. A n a ro riate eluant which i a liquid or a mixture of liquid i allowed to flo w down the column lowly. De ending u on the degree to which the com ound are a d orbed, com lete e aration take lace. The mo t readily ad orbed ub tance a re retained near the to and other come down to variou di tance in the column (Fig.12.11). Thin Layer Chromatogra hy: Thin layer chromatogra hy (TLC) i another ty e of ad or tion chromatogra hy, which involve e aration of ub tance of a mixture ov er a thin layer of an ad orbent coated on gla late. A thin layer (about 0.2mm thick) of an ad orbent ( ilica gel or alumina) i read over a gla late of uitable ize. The late i known a thin layer chromatogra hy late or chroma l ate. The olution of the mixture to be e arated i a lied a a mall ot abou t 2 cm above one end of the TLC late. The gla late i then laced in a clo e d jar containing the eluant (Fig. 12.12a). A the eluant ri e u the late, the com onent of the mixture move u along with the eluant to different di tance de ending on their degree of ad or tion and e aration take lace. The relative ad or tion of each com onent of the mixture i ex re ed in term of it retard ation factor i.e. Rf value (Fig.12.12 b).

[Rf = Di tance moved by the olvent from ba e line (y)]

ub tance from ba e line (x)/ Di tance moved by the

The ot of coloured com ound are vi ible on TLC late due to their original c olour. The ot of colourle com ound , which are invi ible to the eye but flu ore ce, can be detected by utting the late under ultraviolet light. Another de tection technique i to lace the late in a covered jar containing a few cry ta l of iodine. S ot of com ound , which ad orb iodine, will how u a brown o t . Sometime an a ro riate reagent may al o be rayed on the late. For exam le, amino acid may be detected by raying the late with ninhydrin olution (F ig.12.12b). Partition Chromatogra hy: Partition chromatogra hy i ba ed on continuou differ ential artitioning of com onent of a mixture between tationary and mobile ha e . Pa er chromatogra hy i a ty e of artition chromatogra hy. In a er chroma togra hy, a ecial quality a er known a chromatogra hy a er i u ed. chromat ogra hy a er contain water tra ed in it, which act a the tationary ha e. A tri of chromatogra hy a er otted at the ba e with the olution of the mix ture i u ended in a uitable olvent or a mixture of olvent (Fig. 12.13). T hi olvent act a the mobile ha e. The olvent ri e u the a er by ca illar y action and flow over the ot. The a er electively retain different com on ent according to their differing artition in the two ha e . The a er tri o develo ed i known a a chromatogram. The ot of the e arated coloured com ound are vi ible at different height from the o ition of initial ot on the chromatogram. The ot of the e arated coloured com ound are vi ible at diffe rent height from the o ition of initial ot on the chromatogram. The ot of the e arated colourle com ound may be ob erved either under ultraviolet lig ht or by the u e of an a ro riate ray reagent a di cu ed under thin layer c hromatogra hy.

12.9 QUALITATIVE ANALYSIS OF ORGANIC COMPOUNDS The element re ent in organic com ound are carbon and hydrogen. In addition t o the e, they may al o contain oxygen, nitrogen, ul hur, halogen and ho horu . 12.9.1 Detection of Carbon and Hydrogen Carbon and hydrogen are detected by heating the com ound with co er(II) oxide. Carbon re ent in the com ound i oxidi ed to carbon dioxide (te ted with lime-w ater, which develo turbidity) and hydrogen to water (te ted with anhydrou co er ul hate, which turn blue).

Nitrogen, ul hur, halogen and ho horu re ent in an organic com ound are de tected by La aigne te t. The elements present in the compound are converted from covalent form into the ionic form by fusing the compound with sodium metal. Foll owing reactions take place: C, N, S and X come from organic compound. Cyanide, sulphide and halide of sodium so formed on sodium fusion are extracted from the fused mass by boiling it with distilled water. This extract is known as sodium fusion extract. (A) Test for Nitrogen

12.9.2 Detection of Other Element

The sodium fusion extract is boiled with iron(II) sulphate and then acidified wi th concentrated sulphuric acid. The formation of Prussian blue colour confirms t he presence of nitrogen. Sodium cyanide first reacts with iron(II) sulphate and forms sodium hexacyanoferrate(II). On heating with concentrated sulphuric acid s ome iron(II) ions are oxidised to iron(III) ions which react with sodium hexacya noferrate(II) to produce iron(III) hexacyanoferrate(II) (ferriferrocyanide) whic h is Prussian blue in colour. (B) Test for Sulphur (a) The sodium fusion extract is acidified with acetic acid and lead acetate is added to it. A black precipitate of lead sulphide indicates the presence of sulp hur. S2 +Pb2+PbS Black (b) On treating sodium fusion extract with sodium nitroprusside, appearance of a violet colour further indicates the presence of sulphur. S2 +[Fe(CN)5NO]2 [Fe(CN)5NOS]4 Violet In case, nitrogen and sulphur both are present in an organic compound, sodium th iocyanate is formed. It gives blood red colour and no Prussian blue since there are no free cyanide ions. Na+C+N+SNaSCN Fe3++SCN [Fe(SCN)]2+ Blood red If sodium fusion is carried out with excess of sodium, the thiocyanate decompose s to yield cyanide and sulphide. These ions give their usual tests. NaSCN + 2Na NaCN+Na2S (C) Test for Halogens The sodium fusion extract is acidified with nitric acid and then treated with si lver nitrate. A white precipitate, soluble in ammonium hydroxide shows the prese nce of chlorine, a yellowish precipitate, sparingly soluble in ammonium hydroxid e shows the presence of bromine and a yellow precipitate, insoluble in ammonium hydroxide shows the presence of iodine. X +Ag+AgX X represents a halogen Cl, Br or I If nitrogen or sulphur is also present in the compound, the sodium fusion extrac t is first boiled with concentrated nitric acid to decompose cyanide or sulphide of sodium formed during Lassaignes test. These ions would otherwise interfere wi th silver nitrate test for halogens. (D) Test for Phosphorus The compound is heated with an oxidising agent (sodium peroxide). The phosphorus present in the compound is oxidised to to phosphate. The solution is boiled wit h nitric acid and then treated with ammonium molybdate. A yellow colouration or precipitate indicates the presence of phosphorus. Na3PO4+3HNO3H3PO4+3NaNO3 H3PO4+12(NH4) Ammonium molybdate 2MoO4+21HNO3(NH4) 33PO4.12MoO3+21NH4NO3+12H2O Ammonium phosphomolybdate

12.10 QUANTITATIVE ANALYSIS The percentage composition of elements present in an organic compound is determi ned by the methods based on the following principles: 12.10.1 Carbon and Hydrogen Both carbon and hydrogen are estimated in one experiment. A known mass of an org anic compound is burnt in the presence of excess of oxygen and copper(II) oxide. Carbon and hydrogen in the compound are oxidised to carbon dioxide and water re spectively. CxHy + (x + y/4) O2 x CO2 + (y/2) H2O The mass of water produced is determined by passing the mixture through a weighe d U tube containing anhydrous calcium chloride. Carbon dioxide is absorbed in an other U tube containing concentrated solution of potassium hydroxide. These tube s are connected in series (Fig.12.14). The increase in masses of calcium chlorid e and potassium hydroxide gives the amounts of water and carbon dioxide from whi ch the percentages of carbon and hydrogen are calculated. Let the mass of organic compound be m g, mass of water and carbon dioxide produc ed be m1 and m2 g respectively; Percentage of carbon=12m2100/44m Percentage of hydrogen=2m1100/18m Problem 12.20 On complete combustion, 0.246 g of an organic compound gave 0.198g of carbon dio xide and 0.1014g of water. Determine the percentage composition of carbon and hy drogen in the compound. Solution Percentage of carbon = 120.198100/440.246 = 21.95% Percentage of hydrogen = 20.1014 100/ 18 0.246 = 4.58% 12.10.2 Nitrogen There are two methods for estimation of nitrogen: (i) Dumas method and (ii) Kjel dahls method. (i) Dumas method: The nitrogen containing organic compound, when heated with cop per oxide in an atmosphere of carbon dioxide, yields free nitrogen in addition t o carbon dioxide and water. CxHyNz + (2x + y/2) CuO x CO2 + y/2 H2O + z/2 N2 + (2x + y/2) Cu Traces of nitrogen oxides formed, if any, are reduced to nitrogen by passing the gaseous mixture over a heated copper gauze. The mixture of gases so produced is collected over an aqueous solution of potassium hydroxide which absorbs carbon dioxide. Nitrogen is collected in the upper part of the graduated tube (Fig.12.1 5). Let the mass of organic compound = m g Volume of nitrogen collected = V1 mL Room temperature = T1K Volume of nitrogen at STP=p1V1273/760T1 (Let it be V mL)

Where p1 and V1are the pressure and volume of nitrogen, p1 is different from the atmospheric pressure at which nitrogen gas is collected. The value of p1is obta ined by the relation: p1= Atmospheric pressure Aqueous tension 22400 mL N2 at STP weighs 28 g. V mL N2 at STP weighs =(28&timesV/22400)g. Percentage of nitrogen = 28V 100/22400m Problem 12.21 In Dumas method for estimation of nitrogen, 0.3g of an organic compound gave 50mL of nitrogen collected at 300K temperature and 715mm pressure.Calculate the perc entage composition of nitrogen in the compound. (Aqueous tension at 300K=15 mm) Solution Volume of nitrogen collected at 300K and 715mm pressure is 50 mL Actual pressure = 715 15 =700 mm Volume of nitrogen at STP =27370050/300760 =41.9mL 22,400 mL of N2 at STP weighs = 28 g 28 41.9 41.9 mL of nitrogen weighs=(2841.9/22400)g Percentage of nitrogen = (28 41.9 100/22400 0.3) =17.46% (ii) Kjeldahls method: The compound containing nitrogen is heated with concentrat ed sulphuric acid. Nitrogen in the compound gets converted to ammonium sulphate (Fig. 12.16). The resulting acid mixture is then heated with excess of sodium hy droxide. The liberated ammonia gas is absorbed in an excess of standard solution of sulphuric acid. The amount of ammonia produced is determined by estimating t he amount of sulphuric acid consumed in the reaction. It is done by estimating u nreacted sulphuric acid left after the absorption of ammonia by titrating it wit h standard alkali solution. The difference between the initial amount of acid ta ken and that left after the reaction gives the amount of acid reacted with ammon ia.

2NH3+H2SO4 (NH4)2SO4 Let the mass of organic compound taken = m g Volume of H2SO4 of molarity, M,taken = V mL Volume of NaOH of molarity, M, used for titration of excess of H2SO4 = V1 mL V1m L of NaOH of molarity M = V1/2 mL of H2SO4 of molarity M Volume of H2SO4 of molarity M unused =(V V1/2) mL (V V1/2) mL of H2SO4 of molarity M = 2(V V1/2) mL of NH3 solution of molarity M. 1000 mL of 1 M NH3 solution contains 17g NH3 or 14 g of N 2(V V1/2) mL of NH3 solution of molarity M contains: (14M2(V V1/2)/1000)gN Percentage of N=(14M2(V V1/2)/1000)100/m =1.4M2(V V1/2)/m Kjeldahl method is not applicable to compounds containing nitrogen in nitro and azo groups and nitrogen present in the ring (e.g. pyridine) as nitrogen of these compounds does not change to ammonium sulphate under these conditions. Problem 12.22

During estimation of nitrogen present in an organic compound by Kjeldahls method, the ammonia evolved from 0.5 g of the compound in Kjeldahls estimation of nitrog en, neutralized 10 mL of 1 M H2SO4. Find out the percentage of nitrogen in the c ompound. Solution 1 M of 10 mL H2SO4=1M of 20 mL NH3 1000 mL of 1M ammonia contains 14 g nitrogen 20 mL of 1M ammonia contains (1420/1000) g nitrogen Percentage of nitrogen = (1420100/10000.5)=56.0% 12.10.3 Halogens Carius method: A known mass of an organic compound is heated with fuming nitric acid in the presence of silver nitrate contained in a hard glass tube known as C arius tube, (Fig.12.17) in a furnace. Carbon and hydrogen present in the compoun d are oxidised to carbon dioxide and water. The halogen present forms the corres ponding silver halide (AgX). It is filtered, washed, dried and weighed. Let the mass of organic compound taken = m g Mass of AgX formed = m1 g 1 mol of AgX contains 1 mol of X Mass of halogen in m1g of AgX =atomic mass of X m1g/molecular mass of AgX Percentage of halogen = atomic mass of X m1100/molecular mass of AGX m Problem 12.23 In Carius method of estimation of halogen, 0.15 g of an organic compound gave 0. 12 g of AgBr. Find out the percentage of bromine in the compound. Solution Molar mass of AgBr = 108 + 80 = 188 g mol 1 188g AgBr contains 80 g bromine 0.12g AgBr contains= 80012/188 g bromine Percentage of bromine=80 0.12 100/188 0.15 = 34.04% 12.10.4 Sulphur A known mass of an organic compound is heated in a Carius tube with sodium perox ide or fuming nitric acid. Sulphur present in the compound is oxidised to sulphu ric acid. It is precipitated as barium sulphate by adding excess of barium chlor ide solution in water. The precipitate is filtered, washed, dried and weighed. T he percentage of sulphur can be calculated from the mass of barium sulphate. Let the mass of organic compound taken = m g and the mass of barium sulphate formed = m1g 1 mol of BaSO4 = 233 g BaSO4 = 32 g sulphur m1 g BaSO4 contains 32m1/233g sulphur percentage of sulphur= 32m1100/233m Problem 12.24 In sulphur estimation, 0.157 g of an organic compound gave 0.4813 g of barium su lphate. What is the percentage of sulphur in the compound? Solution Molecular mass of BaSO4 = 137+32+64

= 233 g 233 g BaSO4 contains 32 g sulphur 0.4813 g BaSO4 contains 32 0.4813/233g sulphur Percentage of sulphur= 320.4813100/233 0.157 = 42.10% 12.10.5 Phosphorus A known mass of an organic compound is heated with fuming nitric acid whereupon phosphorus present in the compound is oxidised to phosphoric acid. It is precipi tated as ammonium phosphomolybdate, (NH4)3 PO4.12MoO3, by adding ammonia and amm onium molybdate. Alternatively, phosphoric acid may be precipitated as MgNH4PO4 by adding magnesia mixture which on ignition yields Mg2P2O7. Let the mass of organic compound taken = m g and mass of ammonium phosphomolydat e = m1g Molar mass of (NH4)3PO4.12MoO3 = 1877 g Percentage of phosphorus =(31100/1877m)% If phosphorus is estimated as Mg2P2O7, Percentage of phosphorus = (62m1 100/222m)% where, 222 u is the molar mass of Mg2P2O7, m, the mass of organic compound taken , m1, the mass of Mg2P2O7 formed and 62, the mass of two phosphorus atoms presen t in the compound Mg2P2O7. 12.10.6 Oxygen The percentage of oxygen in an organic compound is usually found by difference b etween the total percentage composition (100) and the sum of the percentages of all other elements. However, oxygen can also be estimated directly as follows: A definite mass of an organic compound is decomposed by heating in a stream of n itrogen gas. The mixture of gaseous products containing oxygen is passed over re d hot coke when all the oxygen is converted to carbon monoxide. This mixture is passed through warm iodine pentoxide (I2O5) when carbon monoxide is oxidised to carbon dioxide producing iodine. On making the amount of CO produced in equation (A) equal to the amount of CO us ed in equation (B) by multiplying the equations (A) and (B) by 5 and 2 respectiv ely; we find that each mole of oxygen liberated from the compound will produce t wo moles of carbondioxide. Thus 88 g carbon dioxide is obtained if 32 g oxygen is liberated. Let the mass of organic compound taken be m g Mass of carbon dioxide produced be m1 g m1g carbon dioxide is obtained from (32 m1/88) g O2 Percentage of oxygen = (32 m1 100/ 88 m)% The percentage of oxygen can be derived from the amount of iodine produced also. Presently, the estimation of elements in an organic compound is carried out by u sing microquantities of substances and automatic experimental techniques. The el ements, carbon, hydrogen and nitrogen present in a compound are determined by an apparatus known as CHN elemental analyser. The analyser requires only a very sm all amount of the substance (1 3 mg) and displays the values on a screen within a short time. A detailed discussion of such methods is beyond the scope of this book. SUMMARY In this unit, we have learnt some basic concepts in structure and reactivity of organic compounds, which are formed due to covalent bonding. The nature of the c

ovalent bonding in organic compounds can be described in terms of orbitals Hybri disation concept, according to which carbon can have sp3, sp2 and sp hybridised orbitals. The sp3, sp2 and sp hybridised carbons are found in compounds like met hane, ethene and ethyne respectively. The tetrahedral shape of methane, planar s hape of ethene and linear shape of ethyne can be understood on the basis of this concept. A sp3 hybrid orbital can overlap with 1s orbital of hydrogen to give a carbon hydrogen (C H) single bond (sigma, bond). Overla of a 2 orbital of on e carbon with 2 orbital of another re ult in the formation of a carbon-carbon bond. The unhybridi ed orbital on two adjacent carbon can undergo lateral ( ide-by ide) overla to give a i () bond. Organic com ound can be re re ented b y variou tructural formula . The three dimen ional re re entation of organic c om ound on a er can be drawn by wedge and da h formula.Organic com ound can b e cla ified on the ba i of their tructure or the functional grou they conta in. A functional grou i an atom or grou of atom bonded together in a unique fa hion and which determine the hy ical and chemical ro ertie of the com oun d . The naming of the organic com ound i carried out by following a et of rul e laid down by the International Union of Pure and A lied Chemi try (IUPAC). I n IUPAC nomenclature, the name are correlated with the tructure in uch a way that the reader can deduce the tructure from the name. Organic reaction mechani m conce t are ba ed on the tructure of the ub trate molecule, fi ion of a covalent bond, the attacking reagent , the electron di l acement effect and the condition of the reaction. The e organic reaction invo lve breaking and making of covalent bond . A covalent bond may be cleaved in het erolytic or homolytic fa hion. A heterolytic cleavage yield carbocation or car banion , while a homolytic cleavage give free radical a reactive intermediate . Reaction roceeding through heterolytic cleavage involve the com limentary a ir of reactive ecie . The e are electron air donor known a nucleo hile and an electron air acce tor known a electro hile. The inductive, re onance, elect romeric and hy erconjugation effect may hel in the olari ation of a bond maki ng certain carbon atom or other atom o ition a lace of low or high electron den itie . Organic reaction can be broadly cla ified into following ty e ; ub titution, addition, elimination and rearrangement reaction . Purification, qualitative and quantitative analy i of organic com ound are car ried out for determining their tructure . The method of urification namely : ublimation, di tillation and differential extraction are ba ed on the differenc e in one or more hy ical ro ertie .Chromatogra hy i a u eful technique of e aration, identification and urification of com ound . It i cla ified into two categorie : ad or tion and artition chromatogra hy.Ad or tion chromatogra hy i ba ed on differential ad or tion of variou com onent of a mixture on an ad orbent. Partition chromatogra hy involve continuou artitioning of the com one nt of a mixture between tationary and mobile ha e . After getting the com oun d in a ure form, it qualitative analy i i carried out for detection of eleme nt re ent in it. Nitrogen, ul hur, halogen and ho horu are detected by La aigne te t. Carbon and hydrogen are e timated by determining the amount of ca rbon dioxide and water roduced. Nitrogen i e timated by Duma or Kjeldahl meth od and halogen by Cariu method. Sul hur and ho horu are e timated by oxidi ing them to ul huric and ho horic acid re ectively. The ercentage of oxyge n i u ually determined by difference between the total ercentage (100) and the um of ercentage of all other element re ent. EXERCISES 12.1 What are hybridi ation tate of each carbon atom in the following com ound ? CH2=C=O, CH2CH=CH2, (CH3)2CO, CH2=CHCN, C6H6 12.2 Indicate the and bond in the following molecule : C6H6, C6H12, CH2C12, CH2=C=CH2, CH3NO2, HCONHCH3

12.3 Write bond line formula for : I o ro yl alcohol, 2,3-Dimethylbutanal, He t an-4-one. 12.4 Give the IUPAC name of the following com ound : 12.5 Which of the following re re ent the correct IUPAC name for the com ound concerned ? (a) 2,2-Dimethyl entane or 2-Dimethyl entane (b) 2,4,7- Trimethyloct ane or 2,5,7-Trimethyloctane (c) 2-Chloro-4-methyl entane or 4-Chloro-2-methyl e ntane (d) But-3-yn-1-ol or But-4-ol-1-yne. 12.6 Draw formula for the fir t five member of each homologou erie beginnin g with the following com ound . (a) H-COOH (b) CH3COCH3 (c) H-CH=CH2 12.7 Give conden ed and bond line tructural formula and identify the functiona l grou ( ) re ent, if any, for : (a) 2,2,4-Trimethyl entane (b) 2-Hydroxy-1,2,3- ro anetricarboxylic acid (c) Hexanedial 12.8 Identify the functional grou in the following com ound 12.9 Which of the two: O2NCH2CH2O or CH3CH2O i ex ected to be more table and w hy ? 12.10 Ex lain why alkyl grou act a electron donor when attached to a y tem. 12.11 Draw the re onance tructure for the following com ound . Show the electr on hift u ing curved-arrow notation. (a) C6H5OH (b) C6H5NO2 (c) CH3CH=CHCHO (d) C6H5-CHO (e) C6H6-CHO (f)CH3CH=CHC+H2 12.12 What are electro hile and nucleo hile ? Ex lain with exam le . 12.13 Identify the reagent hown in bold in the following equation a nucleo h ile or electro hile : (a) CH3COOH + HO CH3COO+ H2O (b) CH3COCH3 +C N (CH3)2C(CN)(OH) (c) 6 5 6 5 3 C6H5 +CH3C+O C6H5COCH3 12.14 Classify the following reactions in one of the reaction type studied in th is unit. (a)CH3CH2Br + HS CH3CH2SH + Br (b)(CH3)2C = CH2 + HCl (CH3)2ClC CH3 (c)CH3CH2Br + HO CH2=CH2 +H2O + Br (d)CH3 3C CH2OH HBr CH3 2 CBrCH2CH2CH3 H2O 12.15 What is the relationship between the members of following pairs of structu res ? Are they structural or geometrical isomers or resonance contributors ? 12.16 For the following bond cleavages, use curved arrows to show the electron f low and classify each as homolysis or heterolysis. Identify reactive intermediat e produced as free radical, carbocation and carbanion. 12.17 Explain the terms Inductive and Electromeric effects. Which electron displ acement effect explains the following correct orders of acidity of the carboxyli c acids? (a) Cl3CCOOH > Cl2CHCOOH > ClCH2COOH (b) CH3CH2COOH > (CH3)2CHCOOH >(CH3)3C.COOH 12.18 Give a brief description of the principles of the following techniques tak ing an example in each case. (a) Crystallisation (b) Distillation (c) Chromatography

12.19 Describe the method, which can be used to separate two compounds with diff erent solubilities in a solvent S. 12.20 What is the difference between distillation, distillation under reduced pr essure and steam distillation ? 12.21 Discuss the chemistry of Lassaignes test. 12.22 Differentiate between the principle of estimation of nitrogen in an organi c compound by (i) Dumas method and (ii) Kjeldahls method. 12.23 Discuss the principle of estimation of halogens, sulphur and phosphorus pr esent in an organic compound. 12.24 Explain the principle of paper chromatography. 12.25 Why is nitric acid added to sodium extract before adding silver nitrate fo r testing halogens? 12.26 Explain the reason for the fusion of an organic compound with metallic sod ium for testing nitrogen, sulphur and halogens. 12.27 Name a suitable technique of separation of the components from a mixture o f calcium sulphate and camphor. 12.28 Explain, why an organic liquid vaporises at a temperature below its boilin g point in its steam distillation ? 12.29 Will CCl4 give white precipitate of AgCl on heating it with silver nitrate ? Give reason for your answer. 12.30 Why is a solution of potassium hydroxide used to absorb carbon dioxide evo lved during the estimation of carbon present in an organic compound? 12.31 Why is it necessary to use acetic acid and not sulphuric acid for acidific ation of sodium extract for testing sulphur by lead acetate test? 12.32 An organic compound contains 69% carbon and 4.8% hydrogen, the remainder b eing oxygen. Calculate the masses of carbon dioxide and water produced when 0.20 g of this substance is subjected to complete combustion. 12.33 A sample of 0.50 g of an organic compound was treated according to Kjeldah l s method. The ammonia evolved was absorbed in 50 ml of 0.5 M H2SO4. The residual acid required 60 mL of 0.5 M solution of NaOH for neutralisation. Find the perc entage composition of nitrogen in the compound. 12.34 0.3780 g of an organic chloro compound gave 0.5740 g of silver chloride in Carius estimation. Calculate the percentage of chlorine present in the compound . 12.35 In the estimation of sulphur by Carius method, 0.468 g of an organic sulph ur compound afforded 0.668 g of barium sulphate. Find out the percentage of sulp hur in the given compound. 12.36 In the organic compound CH2 = CH CH2 CH2 C CH, the pair of hy ri ise orb itals involve in the formation of: C2 C3 bon is: (a) sp sp2 (b) sp sp3 (c) sp2 sp3 ( ) sp3 sp3 12.37 In the Lassaignes test for nitrogen in an organic compoun , the Prussian bl

ue colour is obtaine ue to the formation of: (a) Na4[Fe(CN)6] (b) Fe4[Fe(CN)6]3 (c) Fe2[Fe(CN)6] ( ) Fe3[Fe(CN)6]4 12.38 Which of the following carbocation is most stable ? (a) (CH3)3C.C+H2 (b)(CH3)3C+ (c) CH3CH2C+H2( ) CH3C+HCH2CH3 12.39 The best an latest technique for isolation, purification an separation o f organic compoun s is: (a) Crystallisation (b) Distillation (c) Sublimation ( ) Chromatography 12.40 The reaction: CH3CH2I + KOH(aq) CH3CH2OH + KI is classifie as : (a) electrophilic substitution (b) nucleophilic substitution (c) elimination ( ) a ition Answer to Some Selecte Problems 12.32 Mass of carbon ioxi e forme = 0.505 g Mass of water forme = 0.0864 g 12.33 % fo nitrogen = 56 12.34 % of chlorine = 37.57 12.35 % of sulphur = 19.66 I. Multiple Choice Questions (Type-I) 1. Which of the following is the correct IUPAC name? (i) 3-Ethyl-4, 4- imethylheptane (ii) 4,4-Dimethyl-3-ethylheptane (iii) 5-Ethyl-4, 4- imethylheptane (iv) 4,4-Bis(methyl)-3-ethylheptane 2. The IUPAC name for is ________. (i) 1-hy roxypentane-1,4- ione (ii) 1,4- ioxopentanol (iii) 1-carboxybutan-3-one (iv) 4-oxopentanoic aci 3. The IUPAC name for

I. Multiple Choice Questions (Type-I) (i) 1-Chloro-2-nitro-4-methylbenzene (ii) 1-Chloro-4-methyl-2-nitrobenzene (iii) 2-Chloro-1-nitro-5-methylbenzene (iv) m-Nitro-p-chlorotoluene 4. Electronegativity of carbon atoms epen s upon their state of hybri isation. In which of the following compoun s, the carbon marke with asterisk is most ele ctronegative?

(i) CH3 CH2 *CH2 CH3 (ii) CH3 *CH = CH CH3 (iii) CH3 CH2 C *CH (iv) CH3 CH2 CH = *CH2 5. In which of the following, functional group isomerism is not possible? (i) Alcohols (ii) Al ehy es (iii) Alkyl hali es (iv) Cyani es 6. The fragrance of flowers is ue to the presence of some steam volatile organi c compoun s calle essential oils. These are generally insoluble in water at roo m temperature but are miscible with water vapour in vapour phase. A suitable met ho for the extraction of these oils from the flowers is: (i) Distillation (ii) Crystallisation (iii) Distillation un er re uce (iv) Steam istillation

7. During hearing of a court case, the ju ge suspecte that some changes in the ocuments ha been carrie out. He aske the forensic epartment to check the in k use at two ifferent places. Accor ing to you which technique can give the be st results? (i) Column chromatography (ii) Solvent extraction (iii) Distillation (iv) Thin layer chromatography 8. The principle involve in paper chromatography is

(i) A sorption (ii) Partition (iii) Solubility (iv) Volatility 9. What is the correct or er of ecreasing stability of the following cations.

(i) II > I > III (ii) II > III > I (iii) III > I > II (iv) I > II > III 10. Correct IUPAC name for is ___________. (i) 2- ethyl-3-methylpentane (ii) 3,4- imethylhexane (iii) 2-sec-butylbutane (iv) 2, 3- imethylbutane 11. In which of the following compoun s the carbon marke with asterisk is expec te to have greatest positive charge? (i) *CH3CH2Cl

pressure

(ii) *CH3CH2Mg+Cl (iii) *CH3CH2Br (iv) *CH3CH2CH3 12. Ionic species are stabilise by the ispersal of charge. Which of the follow ing carboxylate ion is the most stable?

13. Electrophilic a ition reactions procee in two steps. The first step involv es the a ition of an electrophile. Name the type of interme iate forme in the first step of the following a ition reaction. H3CHC = CH2 + H+ ? (i) 2 Carbanion (ii) 1 Carbocation (iii) 2 Carbocation (iv) 1 Carbanion 14. Covalent bon can un ergo fission in two ifferent ways. The correct represe ntation involving a heterolytic fission of CH3Br is

15. The a ition of HCl to an alkene procee s in two steps. The first step is th e attack of H+ ion to portion which can be shown as (iv) All of these are possible II. Multiple Choice Questions (Type-II) In the following questions two or more options may be correct. 16. Which of the following compoun s contain all the carbon atoms in the same hy bri isation state? (i) HC CC CH (ii) CH3C CCH3 (iii) CH2 = C = CH2 (iv) CH2 = CHCH = CH2 17. In which of the following representations given below spatial arrangement of group/ atom ifferent from that given in structure A?

18. Electrophiles are electron seeking species. Which of the following groups co ntain only electrophiles? (i) BF3 , NH3 , H2O (ii) AlCl3, SO3 , NO2+ Note : Consi er the following four compoun s for answering questions 19 an 20.

19. Which of the following pairs are position isomers? (i) I an II (ii) II an III (iii) II an IV (iv) III an IV 20. Which of the following pairs are not functional group isomers?

21. Nucleophile is a species that shoul have (i) a pair of electrons to onate (ii) positive charge (iii) negative charge (iv) electron eficient species 22. Hyperconjugation involves

elocalisation of ___________.

III. Short An wer Ty e

I. CH3 CH2 CH2 CH2 OH V. CH3 CH2 O CH2 CH3 VI. CH3 O CH2 CH2 CH3

24. Identify the air of com ound which are functional grou i omer .

27. For te ting halogen in an organic com ound with AgNO3 olution, odium extr act (La aigne te t) i acidified with dilute HNO3. What will ha en if a tuden t acidifie the extract with dilute H2SO4 in lace of dilute HNO3? 28. What i the hybridi ation of each carbon in H2C = C = CH2. 29. Ex lain, how i the electronegativity of carbon atom related to their tate of hybridi ation in an organic com ound?

30. Show the

olari ation of carbon-magne ium bond in the following tructure.

26. Identify the

air of com ound that re re ent

chain i omeri m.

25. Identify the

air of com ound that re re ent

o ition i omeri m.

23. Which of the above com ound form air

of metamer ?

Note : Con ider

tructure I to VII and an wer the que tion 2326.

(i) electrons of carbon-hy rogen bond of an alkyl grou directly attached to an atom of un aturated y tem. (ii) electron of carbon-hydrogen bond of alkyl grou directly attached to the o itively charged carbon atom. (iii) -electron of carbon-carbon bond (iv) lone air of electron

(i) II an (ii) II an (iii) I an (iv) I an

III IV IV II

CH3 CH2 CH2 CH2 Mg X 31. Com ound with ame molecular formula but differing in their tructure are aid to be tructural i omer . What ty e of tructural i omeri m i hown by

32. Which of the following elected chain i correct to name the given com ound according to IUPAC y tem.

33. In DNA and RNA, nitrogen atom i re ent in the ring y tem. Can Kjeldahl me thod be u ed for the e timation of nitrogen re ent in the e? Give rea on . 34. If a liquid com ound decom o e at it boiling oint, which method ( ) can y ou choo e for it urification. It i known that the com ound i table at low re ure, team volatile and in oluble in water. Note : An wer the que tion 35 to 38 on the ba i of information given below: Stability of carbocation de end u on the electron relea ing inductive effect of grou adjacent to o itively charged carbon atom involvement of neighbouring g rou in hy erconjugation and re onance. 35. Draw the possible resonance structures for and predict which of the structur es is more stable. Give reason for your answer. 36. Which of the following ions is more stable? Use resonance to explain your an swer. 37. The structure of triphenylmethyl cation is given below. This is very stable and some of its salts can be stored for months. Explain the cause of high stabil ity of this cation. 38. Write structures of various carbocations that can be obtained from 2 methylb utane. Arrange these carbocations in order of increasing stability. 39. Three students, Manish, Ramesh and Rajni were determining the extra elements present in an organic compound given by their teacher. They prepared the Lassai gnes extract (L.E.) independently by the fusion of the compound with sodium metal . Then they added solid FeSO4 and dilute sulphuric acid to a part of Lassaignes e xtract. Manish and Rajni obtained prussian blue colour but Ramesh got red colour . Ramesh repeated the test with the same Lassaignes extract, but again got red co lour only. They were surprised and went to their teacher and told him about thei r observation. Teacher asked them to think over the reason for this. Can you hel p them by giving the reason for this observation. Also, write the chemical equat ions to explain the formation of compounds of different colours. 40. Name the compounds whose line formulae are given below :

42. Draw the resonance structures of the following compounds;

41. Write structural formulae for compounds named as (a) 1 Bromoheptane (b) 5 Bromoheptanoic acid

43. Identify the most stable species in the following set of ions giving reasons :

44. Give three points of differences between inductive effect and resonance effe ct. 45. Which of the following compounds will not exist as resonance hybrid. Give re ason for your answer : (i) CH3OH (ii) RCONH2 (iii) CH3CH = CHCH2NH2 46. Why does SO3 act as an electrophile? 47. Resonance structures of propenal are given below. Which of these resonating structures is more stable? Give reason for your answer.

48. By mistake, an alcohol (boiling point 97C) was mixed with a hydrocarbon (boil ing point 68C). Suggest a suitable method to separate the two compounds. Explain the reason for your choice. 49. Which of the two structures (A) and (B) given below is more stabilised by re sonance? Explain.

IV. Matching Type In the following questions more than one correlation is possible between options of Column I and Column II. Make as many correlations as you can. 50. Match the type of mixture of compounds in Column I with the technique of sep aration/purification given in Column II. Column I Column II (i) Two solids which have different solubilities in a solvent and which do not u ndergo reaction when dissolved in it. (a) Steam distillation (ii) Liquid that decomposes at its boiling point (b) Fractional distillation (iii) Steam volatile liquid (c) Simple distillation (iv) Two liquids which have boiling points close to each other (d) Distillation under reduced pressure (v) Two liquids with large difference in boiling points. (e) Crystallisation 51. Match the terms mentioned in Column I with the terms in Column II. Column I Column II (i) Carbocation (a) Cyclohexane and 1 hexene (ii) Nucleophile (b) Conjugation of electrons of CH bond with em ty -orbital ent at adjacent o itively charged carbon. (iii) Hy erconjugation (c) 2 hybridi ed carbon with em ty -orbital (iv) I omer (d) Ethyne (v) hybridi ation (e) S ecie that can receive a air of electron (vi) Electro hile (f) S ecie that can u ly a air of electron 52. Match Column I with Column II. Column I Column II

re

53. Match the intermediate given in Column I with their robable tructure in C olumn II. Column I Column II (i) Free radical (a) Trigonal lanar (ii) Carbocation (b) Pyramidal (iii) Carbanion (c) Linear

V. A ertion and Rea on Ty e In the following que tion a tatement of A ertion (A) followed by a tatement of Rea on (R) i given. Choo e the correct o tion out of the choice given below each que tion. 55. A ertion (A) : Sim le di tillation can hel in e arating a mixture of ro an-1-ol (boiling oint 97C) and ro anone (boiling oint 56C). Rea on (R) : Liquid with a difference of more than 20C in their boiling oint c an be e arated by im le di tillation. (i) Both A and R are correct and R i the correct ex lanation of A. (ii) Both A and R are correct but R i not the correct ex lanation of A. (iii) Both A and R are not correct. (iv) A i not correct but R i correct. 56. A ertion (A) : Energy of re onance hybrid i equal to the average of energi e of all canonical form . Rea on (R) : Re onance hybrid cannot be re ented by a ingle tructure. (i) Both A and R are correct and R i the correct ex lanation of A. (ii) Both A and R are correct but R i not the correct ex lanation of A. (iii) Both A and R are not correct. (iv) A i not correct but R i correct. 57. A ertion (A) : Pent- 1- ene and ent- 2- ene are o ition i omer . Rea on (R) : Po ition i omer differ in the o ition of functional grou or a u b tituent. (i) Both A and R are correct and R i the correct ex lanation of A. (ii) Both A and R are correct but R i not the correct ex lanation of A. (iii) Both A and R are not correct. (iv) A i not correct but R i correct. 58. A ertion (A) : All the carbon atom in H2C = C = CH2 are 2 hybridi ed Rea on (R) : In thi molecule all the carbon atom are attached to each other by double bond . (i) Both A and R are correct and R i the correct ex lanation of A. (ii) Both A and R are correct but R i not the correct ex lanation of A. (iii) Both A and R are not correct. (iv) A i not correct but R i correct.

54. Match the ion

given in Column I with their nature given in Column II.

(i) Duma method (a) AgNO3 (ii) Kjeldahl method (b) Silica gel (iii) Cariu method (c) Nitrogen ga (iv) Chromatogra hy (d) Free radical (v) Homoly i (e) Ammonium ul hate

59. A ertion (A) : Sul hur re ent in an organic com ound can be e timated quan titatively by Cariu method. Rea on (R) : Sul hur i e arated ea ily from other atom in the molecule and ge t reci itated a light yellow olid. (i) Both A and R are correct and R i the correct ex lanation of A. (ii) Both A and R are correct but R i not the correct ex lanation of A. (iii) Both A and R are not correct. (iv) A i not correct but R i correct. 60. A ertion (A): Com onent of a mixture of red and blue ink can be e arated by di tributing the com onent between tationary and mobile ha e in a er ch romatogra hy. Rea on (R) : The coloured com onent of ink migrate at different rate becau e a er electively retain different com onent according to the difference in th eir artition between the two ha e .

(i) Both A and R are correct and R i the correct ex lanation of A. (ii) Both A and R are correct but R i not the correct ex lanation of A. (iii) Both A and R are not correct. (iv) A i not correct but R i correct. VI. Long An wer Ty e 61. What i meant by hybridi ation? Com ound CH2 = C = CH2 contain bridi ed carbon atom . Will it be a lanar molecule? or

2 hy

63. Two liquid (A) and (B) can be e arated by the method of fractional di till ation. The boiling oint of liquid (A) i le than boiling oint of liquid (B). Which of the liquid do you ex ect to come out fir t in the di tillate? Ex lain . 64. You have a mixture of three liquid A, B and C. There i a large difference in the boiling oint of A and re t of the two liquid i.e., B and C. Boiling o int of liquid B and C are quite clo e. Liquid A boil at a higher tem erature t han B and C and boiling oint of B i lower than C. How will you e arate the co m onent of the mixture. Draw a diagram howing et u of the a aratu for the roce . a diagram of bubble late ty e fractionating column. When do we require e of a column for e arating two liquid . Ex lain the rinci le involve e aration of com onent of a mixture of liquid by u ing fractionating What indu trial a lication doe thi roce have?

66. A liquid with high boiling oint decom o e on im le di tillation but it ca n be team di tilled for it urification. Ex lain how i it o ible? ANSWERS I. Multi le Choice Que tion (Ty e-I) 1. (ii) 7. (iv) 3. (iii) 2. (iv) 8. (ii) 14. (ii) 3. (ii) 4. (iii) 9. (i) 10. (ii) 15. (ii)

5. (iii) 11. (i)

6. (iv) 12. (iv)

65. Draw uch ty d in the column.

62. Benzoic acid i a organic com ound. It crude am le can be urified by cry talli ation from hot water. What characteri tic difference in the ro ertie of benzoic acid and the im urity make thi roce of urification uitable?

II. Multi le Choice Que tion (Ty e-II) 16. (i), (iv) 20. (i), (iii) 17. (i), (iii), (iv) 18. (ii), (iii) 21. (i), (iii) 22. (i), (ii)

III. Short An wer Ty e 27. White t. of Ag2SO4 will be formed. with increa ing character.

31. Metameri m. 32. The four carbon chain. Selected chain hould have maximum number of function al grou . 33. DNA and RNA have nitrogen in the heterocyclic ring . Nitrogen re ent in rin g , azo grou and nitro grou cannot be removed a ammonia. 35. . Structure II i more table becau e every atom ha com lete octet.

38. Four o ible carbocation are

Order of increa ing tability I < IV < II < III 39. In La aigne te t SCN ion are formed due to the re ence of ul hur and nitr ogen both. The e give red colour with Fe3+ ion . Thi ha en when fu ion i not carried out in the exce of odium. With exce of odium th e thiocyanate ion, if formed, i decom o ed a follow : NaSCN + 2Na NaCN + Na2S 40. (i) 3-Ethyl-4-methylhe tan-5-en-2-one (ii) 3-Nitrocyclohex-1-ene. 41. (a) CH3 CH2CH2CH2CH2CH2CH2Br

42. 43. (i) , The re lacement of hydrogen by bromine increa e

o itive charge on carbon at

37. Stabili ed due to nine o ible canonical

tructure .

36. Structure I i more table due to re onance. (See re onance No re onance i o ible in tructure II.

tructure A and B).

30. . Since electronegativity of carbon i more than magne ium it will behave a

29. Electronegativity increa e 3 < 2 <

19. (ii)

44. Inductive effect Re onance effect (i) U e -electron (a) U e - electron or lone air of electron (ii) Move u to 3-carbon atom (b) All along the length of conjugated y tem (iii) Slightly di laced electron (c) Com lete tran fer of electron 45. CH3OH; Any o ible contributing tructure will have charge e aration and i ncom lete octet of electron on atom . So the tructure will be un table due to high energy. e.g., 46.

47. I > II 48. Sim le di tillation can be u ed becau e the two com ound have a difference of more than 20 in their boiling oint and both the liquid can be di tilled wit hout any decom o ition. 49. Re onating tructure are a follow :

IV. Matching Ty e 50. 51. 52. 53. 54. (i) (i) (i) (i) (i) (e) (ii) (d) (iii) (a) (iv) (b) (v) (c) (ii) (f) (iii) (b) (iv) (a) (v) (c) (ii) (e) (iii) (a) (iv) (b) (v) (a), (ii) (a) (iii) (b) (a), (b), (d) (ii) (b) (iii) (b) (iv) (c) (d) (vi) (e) (d) (c), (d)

V. A ertion and Rea on Ty e 55. (i) 56. (iv) 57. (i) 58. (iv) 59. (iii) 60. (i) VI. Long An wer Ty e 61. No. It i not a

lanar molecule.

Central carbon atom i hybridi ed and it two unhybridi ed -orbital are er endicular to each other. The -orbital in one lane overla with one of the orbital of left terminal carbon atom and the -orbital in other lane overla w ith -orbital of right ide terminal carbon atom. Thi fixe the o ition of two terminal carbon atom and the hydrogen atom attached to them in lane er end icular to each other. Due to thi the air of hydrogen atom attached to termina

Structure B i

more tabili ed a it doe

not involve charge e aration.

Three highly electronegative oxygen atom are attached to ul hur atom. It make ul hur atom electron deficient. Due to re onance al o, ul hur acquire o iti ve charge. Both the e factor make SO3 an electro hile.

(ii) i mo t table becau e electronegativity of chlorine i more than hydrogen. On re lacing hydrogen by chlorine, negative charge on carbon i reduced and ecie i tabili ed.

om and de tabili e the

ecie .

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