HYDROCARBON > Hydrocarbons are composed of Carbon and hydrogen. > The important fuels like Petrol, kerosene, coal gas, CNG, LPG etc. are all hydrocarbons or their mixture. Sources: Petroleum and natural gas are the major sources of aliphatic hydrocarbon while coal is an important source of aromatic hydrocarbons. The oil trapped inside the rocks is known as petroleum. PETRA — ROCK, OLEUM - OIL. The oil in the petroleum field is covered with a gaseous mixture known as natural gas. The main constituents of the natural gas are methane, ethane, propane and butane. CLASSIFICATION OF HYDROCARBONS: HYDROCARBON Acyclic or Aliphatic Carbocyclic or Cyclic ( Open chain) Alicyclic Aromatic Alkanes Alkenes Alkyne Cycloalkanes Cycloalkenes CycloalkynesPreparation:- © Wurtz reaction:- 2CH3CH,Br + 2Na os CHCH,CH,CH, +2NaBr > Follow mainly free radical mechanism > Usefill in preparing an alkane containing even number of carbon atoms > Stepping up reaction ©From unsaturated hydrocarbons:- R-CH=CHy +H, “4 5R- CH, -CHy R-C=CH+H,—“ ,R- CH, -CHy 4. From carboxylic acids- Decarboxylation.- CH,COO Na’ +NaOH-9325CH, +Na,CO,, Sodium ethanoate Kolbe’s electrolytic method- 2CH,COO"Na* + 2H,0 Sodium acetate [Electrolysis CH,-CH,+2CO, +H, +2NaOH + Physical Properties:- (1) Nature:- Non-Polar due to covalent nature of C—C bond and C—H bond. C— C bond enrgy = 83 kj/mole and C—H bond energy = 99 kj/mole. Ci—Cy = gases, Cs—C17 = colourless odourless liquid and > C1y= Solid. (2) Solubility:- Like dissolve Viz, Polar compounds dissolve in polar solvent and Non-Polar compound dissolve in non polar solvent. (3) Boiling point:- Low boiling point due to non polar in nature.> Chemical properties © Combustion:- CH, +202 + CO2 +2H,0 AH = -217.0 K cal/mole @ Oxidation:- CH, +0, St 2CH;0H CH, +O, M0 _, HCHO + H0 © Substitution:- © Halogenation:- CH +Ch , CHC! + HCI Vv cHcl—+ cuch —+ cHch och Noted:- lodination is a reversible reaction. So it is carried out by heating alkane in the presence of some oxidizing agent like iodic acid (HIOs) or nitric acid (HNO3) or mercuric oxide (HgO) which oxidizes HI formed during the reaction. CH, +h ste» = CHI + HI SHI + HIO; ——+ 3H,0 + 3], 2HI + 2HNO; ——> 2H,0 + 1, + 2NO,@Aromatization:- H,C(CH,),CH, SPs oO te y WCHs AK Hexane —-10-20atm_— Benzene This method is also called dehydrogenation or hydroforming Similarly, heptane gives toluene, n-Octane give o-xylene and 2, methy! heptane give m-xylene. @Thermal decomposition or Pyrolysis or cracking or Fragmentation: - when higher alkanes are heated at high temp (about 700-800k) in the presence of alumina or silica catalysts, the alkanes break down to lower alkanes and alkenes. (CH3-CH;-CH; ———* — CH3-CH-CH; + CH;-CH; + C.Hy + CH, @ Action of steam:- catalyst: nickel, alumina Al,O3 1000 °C CH, + H,0(Steam) ———* CO + 3H This reaction is used for the industrial preparation of hydrogen from natural gas. 8. Isomerisation:- CH, (CH, ), cH, Anhy. AICL, /HC1 n-Hexane CH,CH-(CH,}, -CH, +CH,CH, -CH-CH, -CH, i CH, CH, 2-Methylpentane 3-Methylpentane> Preparation:- |. From Alkynes:- Alkynes on partial reduction with Partially deactivated palladised charcoal known as Lindlar’s catalyst give alkynes. CH=CH+H, —P@/C, CH, =CH, Ethyne Ethene 2. From Haloalkanes: - dehydrohalogenation (E2 or 1,2-elimination or Bita-elimination) H [2 1. Ale.KOH CH FH, a Chi CH,* KBr + 4,0 Br3. From Dihaloalkanes: - dehalogenation ZnHoAc HT yH -——> Sok + zr, ( H H ver a. vs +1, +2 NaBr 4. From Alcohols:- Dehydration CHaCHyCH)OH £2", , CH3CH = CHp + HO 160°3. From Dihaloalkanes: - dehalogenation zHoac HH rit -——> So= +z, HoH POR, 720 1 1 H a c—H — | H, H Br Br Nal NAY ee ao Q +heanapr 4. From Alcohols:- Dehydration (E1 - elimination) CH3CH2CH2OH —_SonssH,SO% CORES, 160° CH3CH = CH2+ H20% Chemical Properties:- © Addition Reaction:- Alkene show electrophilic addition reaction. 1, Addition of Hydrogen:- RCH=CH, HM, RcHocHy 2. Addition of Halogens:- CHR CHa =CHp + Br, Sh, Pad bod CHa = CHa +Brg a Br—CH —CH, —OH+ HBr (Brown colour) (Colourless) 3. Addition of hydrogen halides- Addition reaction of HBr to symmetrical alkenes CH, =CH, +H-Br—-CH, -CH, - Br Addition reaction of HBr to unsymmetrical alkenes takes place according to Markovnikov Rule Markownikov rule:- negative part of the addendum (adding molecule) gets attached to that carbon atom which possesses lesser number of hydrogen atoms. ¢ g cH, ———- P be be ‘At Position ‘ch, —— con, cH?! ay cH cH Lo= — 2° r =CH, more stable cation ® a Major Product r a) " a, cH— cit, =e Lo. ge b ‘CH—CH, Br At Position ve oH ° 2 ee less stable cation Minor Product Peroxide effect or Kharasch (Anti Markownikoff’s addition): In 1933 Kharasch and Mayo observed that when HBr is added to an unsymmetrical double bond in the presence of organic peroxide, the reaction take places opposite to the Markovnikov rule, Her CH;—-CH=cH, CHS-CH;-CH,Br Peroxide Propyl bromide4. Addition of water (Hydration):- Acid catalyzed addition of water 70% H:50. on cu— CH— CH = cH, +H, 8° 70° MSO. ony ge oH CH, Hot cH. — cH, cH CH, cn fs(i) Alk.KMnO, CH;—CH =CH, ————— cH, COOH + CO, + H,0 (il) Ha © )xidation with Ozone:- Ozonolysis — give carbonyls compounds. crich.crmccn, 2 en ref mer t- crite I\ Zot, cocryCH+ crybon, +2104, cH, cH, OzonideAlkynes © Unsaturated hydrocarbon which have triple bond. © General molecular formula CyH2y.2 = sp hybridization & Shows chain, positional and functional isomerism > Preparation: From vicinal dihalides: - dehalogenation 2KOH (alc) CHy—PH— pH, —— > CH, —C == CH + 2KBr + 2H,0 A Br Br By the action of water on calcium carbide:- CaCy + Hg0 > HC =CH + Ca(OH), + Chemical Properties: @ Addition Reaction:- Alkyne show electrophilic addition reaction. ® Addition of Hydrogen:- Hydrogenation. CH,C= CH + 2H, AN CH,CH,CH, Propyne@Addition of Halogens:- @ Addition of hydrogen halides: H+ QHBr ——> CHSCH Bry @ Addition of water oe Acid catalyzed addition of water HC= CH + H0 [ex=chou] == ci,cHo Unstable aoAromaticity:- The compounds that follow the following features are to be considered aromatic. (i) Planarity (ii) Complete delocalisation of the x electrons in the ring (iii) Presence of (4m + 2) x electrons in the ring where n is an integer (n = 0, 1, 2,...). This is often referred to as Hiickel Rule. Preparation of Benzene: (i) Cyclic polymerisation of ethyne: (ii) Decarboxylation of aromatic acids, COONa CaO + NaOH x’ + Na,CO, (iii) Reduction of phenol: Phenol is reduced to benzene by passing its vapours over heated zinc dust A + ZZ —> + ZnO Physical properties: 1, Aromatic hydrocarbons are non- polar molecules and are usually colourless liquids or solids with a characteristic aroma. 2. Aromatic hydrocarbons are immiscible with water but are readily miscible with organic solvents. 3. They burn with sooty flame, OHNO, Nitration Conc.HNO,+Conc.H,SO, +#,0 Nitrobenzene Halogenation +Cl, Anhyd. AICI; + HCl Chloro benzene SO,H Sulphonation Fuming sulphuric acid + H,O H,S0,(SO: pSOEOS) Benzene sulphonic acid Anhyd. AICI; Ethyl benzene COCH, Friedel-Crafts acylation +CH;COCI +HCl Anhyd. AICI; Fri. CH, iedel-C\ Ukylatic atts jedel-Crafis alkylation ior . | +O2HsCl acetphenonecl Anby AICL 7 +6Cl, Anti a + 6HCI cr Cl cl Hexachlorobenzene (C.Cl) Addition reactions of benzene- uv cl O + 3Ccl, ———> 500 K cl cl Benzene hexachloride, (BHC) Directive influence of a functional group in monosubstituted benzene:- 1. Ortho and para directing groups and activating--OH, NH, NHR, — NHCOCHs, -OCH3, -CHs, -CoH,, etc. :OH +0-H +6-H G (3 CD 2 Meta directing group and deactivating--NO2, CN, -CHO, ~COR, ~COOH, — COOR, ~SO3H, etc. 62, 72 O40 Sad