CHAPTER 9 - HYDROCARBONS PREPARATION from unsaturated hydrocarbons Dihydrogen gas adds to alkenes and alkynes in the presence of finely divided catalysts like platinum, palladium or nickel to form alkanes. This process is called hydrogenation, CH,-CeC-H +21, 21, CH -CH,-CH, Propyne Propane From alkyl halides i) Alkyl halides (except fluorides) on reduction with zine and dilute hydrochloric acid give alkanes. CH, -C) +H," cn, + HCL Chioromethane Methane ii) Alkyl halides on treatment with sodium metal in dry ethereal (free from moisture) solution give higher alkanes. This reaction is known as Wurtz reaction. CH,Br+2Na+BrCH, "01, -CH, +2NaBr Bromomethane Ethane if two different alkyl halides are taken, a mixture of alkanes are produced and their separation is difficult acids Sodium salts of carboxylic acids on heating with soda lime (mixture of sodium hydroxide and calcium oxide) give alkanes containing one carbon atom less than the carboxylic acid. This process is known as decarboxylation, CH,COO Na* +NaOH CH, +Na,Co, Sodium ethanoate Kolbe’s electrolytic method An aqueous solution of sodium or potassium salt of a carboxylic acid on electrolysis gives an alkane containing double the number of carbon atoms as present in the alkyl boxylic acid, group of carboxylic acid. > rh 2CH\COONa’ + 2H,0 ———+ CH,-CH; + 2C0, +H; + 2NaOH Note:- Methane cannot be prepared by this method because it has only one carbon. Page 1of1BDUYSICAL PROPERTHS > Alkaves are mostly Honpolar molecules because bonds and due to very little difference of electronegativily betwee ‘The first four members, Cy to Cre gases.Cs to Care liquidsand those containing Lif gurbon gous or more ate solid jt 298 K we in molecular may There is a steady incrouse in boiling point of alkanes with ined ‘ Hur van dow Waals forces inerease with increase of the of the covalent nature of C-C and C-A. Cand Hatoms. is due to the fact that the intermole« molecular size or the surface area of the molecul When branehiny ses, Surface aren decreases which in turn d «9 the boiling point, CHEMICAL PRO US 1. Substitution reactions CH, +S crcl 4 Chloromethane CHCl + CEs Crier Hel Dichloromethane WS CUCL Hey Prichloromethane CHC, + CL Powe? of 18. “2. Controlled oxidation = Ye gon, 20, Calaat sino 24 ont SS : 4 Methanol (CH, +70, "85 HCHO + 1,0 ~ Methanal (ii)2CH,CH, +30, -GuCOOnw, 2CH,COOH Bthanoie acid + 2130 3. Isomerisation Normal Alkanes on heating in the presence of anhydrous aluminium chloride and hydrogen chloride gas isomerise to branched chain alkanes. hy. AICI ic Gs eer CHICH,),cH, At Ae Mcl, n-Hexane CH,CH-(CH, ), -CH,+CH,CH, ~CH-CH, -CH I | cH, cH MethyIpentane 3-Methylpentane n-(normal) Alkanes having six or more carbon atoms on heating to 773K at 10-20: atmospheric pressure in the presence of oxides of vanadium, molybtenum or chromium supported over alumina gel dehydrogenated and cyclised to benzene and its homologues, CH J at, C40, 0r V0, i? Hs a M00, CH, (CH, 773K » 10-20 atm Hy 5. Reaction with steam CH, + H,0 —i>.co + 8H, Bitte CONFORMATIONS (yews goed Spatial arrangements of atoms which can be converted into one another by rotation around a C single bond are called conformations or conformers or rotamers. Hg 22 Monnaie asitor ia pes At202 /pranOs Cea Etta elie eke He tly Ee wea bees Voluwsene Pages of 18 dCONFORMATIONS OF ETHANE : Pstiihorst prollciont == ey. Mowman projections Sune! " (a eeupsca 7 i) Eeipse (ui) Staggered ® Rotation around a C-C single bond is not completely fiee. It is Kindered by a small energy barrier of 1-20 kJ mol ' due to weak repulsive interaction betwesn the adjacent bonds. Such a type of repulsive interaction is called torsional strain ® Magnitude of torsional strain depends upon the angle of rotation about C-C bond. This angle js also called dihedral angle or torsional angle Any intermediate conformation other than eclipsed and staggered is called a skew conformation, ALKENES Restricted rotation of atoms or groups around the doubly bonded carbor atoms gives riseto different geometries, The stereo isomers of this type are celled geometrical isomers. Eg: eis-But-2-ene. trans-But-2-cne Note:- Dipole moment of cis-but-2-ene is 0.33 Debye, whereas, dipole moment of the frams form is almost zero. > In trans-but-2-ene, the two methyl groups are in opposite directions, Therefore, dipole moments cancel, thus making the trans form non-polar. ‘CH, cH, cH, H Ste 7 Nas cis-But-2-ene trans-But-2-ene (u=0.33D) u=9) Page sof 18PSS) Gana US nga s Cow aleae = SS oS eS = eS i SS ee Fare weusaty oe Quai! Preparation SOX SAes~s Ss casa ~atas Wadsasis PAT eone SMEEAR Can oe pomace Weg Ma in 1. Fromalkynes S302 vy Waskess Se) Qadsos. caketgse Alkynes on partial reduction with calculated amount of dihydrogen in the presence of a mixture of palladium and charcoal partially deactivated with poisons like sulphur compounds or quinoline give alkenes, Partially deactivated palladised charcoal is known as Lindlar’s catalyst. R 4 © ‘ gnasas’s Pa/c eal Se hex RC = CR'+H, x es Alisyne H cis-Alkene (13.30 RC = CR+H, Se/and Nt Alkyne 2, From alkyl halides Alkyl halides (R-X) on heating with potassium hydroxide dissolved in alcohol, eliminate fone molecule of halogen acid to form alkenes. This reaction is known as dehydrohalogenation. Itis also known as f-elimination as hydrogen atom is eliminated from the B- C atom H H Ip le H—c¢—c¢—H neha! HX (&=ClL Br D Note:~ The rate is: 1> Br > Cl, while for alkyl groups i Vicinal dihalides on treatment with zinc metal lose 2 molecule of ZnX; to form an alkene. This reaction is known as dehalogenation. CH.Br—-CH,Br+Zn—>CH, =CH, -ZnBr, Wena defen ZB haregn on te oso Estesne ee ideatan Lege Or Sue SERS cee toon tes ve ety COME OME te = SS % 3 wo a Pape Sof38werses acts an GEES, i a 4. From alcohols by acidic dehydration co~ H H LT Cone. 1,50. , o e sone. HSO. = CH, +H, H— C— C— HS" #8, CH, = CH, + Hy | ASG4 Ethene Ethanol CHEMICAL PROPERTIES eter w ange QL Bee a ae 1. Addition of hydrogen ek, ee CH, CH=CH, +H, "CH, -CH, -CH, Propene Propane 2. Addition of halogens CH=CH, + Br-Br—“ cH,-CH, Ethene | | Br Br 1,2 Dibromoethane ne solution in CCl, is discharged when bromine a on is used as a test for unsaturation [The reddish orange colour of bron ip to an unsaturation site, This reat 3, Addition of hydrogen halides i) Addition reaction of HBr to symmetrical alkenes Addition reaction of HBr to symmetrical alkenes CH, =CH, +H-Br—+CH, -~CH,—Br CH, ~CH=CH-CH, + HBr—>CH, -~CH, —CHCH, Brii) Addition reaction of HBr to asymmetrical alkenes Markovnikoy rule When hydrogen halide is added to an unsaturated asymmetric systems the negative part of hydrogen halide goes fo that carbon atom of double bond haying the lesser number of hydrogen atom. 1 -CH,-CH-CHs i br CH,-CH=CH,+H-Br—| 2-Bromopropane n Ler, CH,-CH,—Br 1- Bromopropane 2-bromopropane is the major product. H,C—CH;—CH, + Br H,C—CH—CH,+ Br (a) less stable (b) more stable primary carbocation secondary carbocation @ The secondary carbocation (b) is more stable than the primary carbocation (a), therefore. the former predominates because it is formed ata faster rate. The carbocation (b) is attacked by Br ion to form the product as follows : zo H,C—CH—CH, —> H,C—¢H—CH, Br 2-Bromopropane (major product)Markovnike ct or Kharash effect When hydrogen halide is added to an unsaturated unsymmetrical San in pe ae peroxide catalyst, the negative part of the addendum goes to that carbon atom bond haying the greater number of hydrogen atom. dition or peroxide et CH,-CH=CH, +HBr “ECOL ,op, CH, ty | CH,Br 1-Bromopropane Mechanism @ - oO CsH,- C-O-O-'C 2C,H,~ C~ O: > 26H, 4 200, @) 6.4, +H prem Gi) CH,—CH= CHC ES CH,—CH—CH,— Br fa) (b) (less stable primary trce radical) (more stable secondary free radical) Gs) CH,~ CH~ CHBr 4 11— Br Homotysis CH, ~ CH,~ CH,Br + Br (major producy) (¥) CH,~ CH- CH, + H- Br Homolysis | Br CH, GH- CH, + Br Br (minor product)be itis ileal by radical, whereas iti is weaker and ‘odie free railed eoniline to fora iodine molecules insteac jot adding to the double bond, 4, Addition of sulphuric acid Cold concentrated H;SO, adds to alkenes in accordance with Markovnikoy rule. CH, ~ CH = CH, + 1OSO,OT CH~ CH- CH, Os0,0H Propyl hydrogen sulphate 5. Addition of water In the presence of a few drops of concentrated sulphuric acid, alkenes react with water to form alcohols, in accordance with the Markovnikoy rule. CH, \ CHy-G=CH, +1130 ait C=C, cH, CHs on lean eres 2 Methylpropan 2 ol Yzonolysis pean CH,CH=CH,+0,—%CH,-Cil CH, Propene 1 I o— oO Propene ozonide Za 11,0 CH,CHO + HCHO Ethanal — Methanal 5 pO = Mat Oy —+ We 2-Methylpropene ne |» “iho pe=0+ HCHO7. Polymerisation ‘n(CH,—CH=CH, ) Hish temp/pressure, Lemp pest, + CH-CH, 4 cH, Polypropene ALKYNES (Onti24-2 ) PREPARATION & |. From ealeium carbide Ethyne is prepared by treating calcium carbide (CaC,) with water. Calcium carbide is prepared by heating quick lime with coke. Quick lime can be obtained by heating limestone. Caco, > CaO + CO, CaO+3C —> CaC, + CO Calcium carbide Ca(OH), + C,H . From vicinal dihalides Vicinal dihalides on treatment with alcoholic KOH undergo dehydrohalogenation, The resulting alkenyl halide on treatment with sodamide gives alkyne. (utuudy 1 i H,C-C-H+KOH —2l¢ohol, I I Ung Br Br H 7 PHYSICAL PROPERTIES * First three members are gases, the next eight are liquids and the higher ones are solids. * Alkynes are weakly polar in nature. They are lighter than water and immiscible with water but soluble in organic solvents like ethers, carbon tetrachloride and benzene. % Melting point, boiling point and density increase with increase in molar mass, Page 10 of 181 kaytitisad, saat sans ihe PA < giucn wh 1 wArhie we wee aivashed Wo the > Hydrogen some in © are attacksed to off Ins rica cation on carbons i oh sige 7> Due tw the per casbon atoms in etayne mvke Eg:2 . iets ie eases sAlcnass oad coiee = Addition of dikydropen ropesNOTE: Reddish oran i 1 colour of the solution of bromine in eartem tetrnchlaride be ecolourised. ‘This in used wn w test for unsaturation: (il) Addition of hydrogen halides Clipe @ CH + 1 9 ICMy © = GH) Ne 2 Asrenenprepene Hy OH 4 AGT Addition of water one molecule of water adds tn alkyne dilute sulphuric seid at 394 K to reurie sulphate ind CHy- Can + H-on MEe Propyne : i (iv) Polymerination (a) Lineur polymerisation > Under suitable conditions, linear polymerisation of ethyne takes place te produce polyethyne which is 4 high molecular weight polyene and ean be represented as (CH= CH CH © CH), > Thin film of polyethyne can be wed us electrode in butteri A (Wy Cyetle polymerization Pihyne on paying through red hot iron tube at 873K undergoe polymerization, Three molecules polyme to form benzene. cH A, cit eu Reed fio I inte, cH ACH ATK ICHe cy RMT a13 a CJAROMATIC HYDROCARBON Aromatic compounds containing benzene ri a benzene ring are known as non-benzenoids. Methylbensene 1 Toluene) (oNylene Resonance and stability of benzene * (i¥} Presence of (47 This is referred to as Hiickel Rule. ] ‘vckpeniaent SN Naphthalene (n= 2, 10 = electrons) Anthracene (y=3, 14x electrons)oo CO +ACE Toh oe (Y) Jrledet-Craphy eqplanine reaction Tiexachy tts ARB DOOS REACTIONS Alchigh trenporstarn ama! cr prettarare: i thee pramsirwe: uf abckal catalys’ Rydregonation of Cpcahe nines ra-vialel Bhd, thie elilorine mmotecwlcy see edited to beramee ni pertace 43 tector yetohexwn:, CHK wists bs also cated pamimanaine. COMESa sername hae Nethae g ees : Cie FO, 900, mg ee a Directive influesice af a unetinngt Afoup iy menncobstituted theme rs Wbce Mheineubtited benzene je nubj ected rther usbattuion feo Fie a behaviours are ctiverveal, Hisher rhe aral para Brducts br amete peodboct exe. y farmed. ‘This botunvieae dtgienchs ols Give martise si thee wattinneed aireadly present itn the benorene cing anni! nett Wee nacucn ef ther ensoring grote The bs AryiWvnt ei dinectie imfbaesiee off ssbutiments Orthis ane pare ivevtisie props The. groups wich dinecs th AIDING Tap bo oct kal pawn peouitineey Ste called Orth anil pia directing exiyaps, Freer g ik mee no nd peace maby ie theses posit ‘group sho operates chu: vibe becroncnc rica PovitiO OF tbe ring dee te resonance ring. Activating grep ares OH, NE SHR, NROOCT, OOH. SCH, Ay ete rt thee conan off aayl babies, tbubojpesns ary moleranchy Scactivatiog, Weccie' pf shir rome —Ledlect, overall vlvcron density on beneces ristg drcteasen: by stakes Merthes eur lie diffecule. However, due to:reeununice the siecao hemalty on seid onisinen fs greater than thet ai the m-positien, Heats, they ate elie o~ aed Sinreting groggy. ‘The growpi whieh deccn the Encuaming group ia ir pein ine called maa ddieeeting groups.