CHEMISTRY-XII ORGANIC CHEMISTRY COMPLETE NOTES CHAPTER # 7 TOPICS OCCURRENCE, PREPARATIONS, USES, ORBIT? TRUC ‘TURES, CHEMICAL PROPERTIES OF Methane Ethane Ethene Ethyne & Benzene PREPARED BY:CHEMISTRY OF METHANE OCCURRENCE Methane is the Ist member of alkane series. it occurs as (@® MARSHGAS, found bubbling from marshy places, produced by t dead vegetable matter (i) EIREDAMP, in coal mines (i) NATURAL GAS, from petroleum wells. It contain 80-90% CH, in Pakistan Sui gas field is source of natural gas seterial decomposition of PREPARATION OF METHANE and heated, methane is evolved which being insoluble is collected over water help ia the fusion of NaOE) CH\COONa + NaOH —HEAT/ Ca0, 2.By ‘Nascent I reducing agent. It is obtained in sita by action of HCI on Zn oF action of Zn/Cu Za + HCI——znCk + 2 [H] Nascent hydrogen then reduces methyl iodide in cold to give m cit +2 [4] ————> cH +H 3. By the catalvtic reduction of methyl iodide Ly ww CH + Hy —Pd—+ CHi+ HI Q Grignard reagents are fed by action of alkyl halide and Mein presence of ether at OFC R-X+M > RMsX ‘Methane is obtained by acidic h tas{ magnesium iodide (CHsMal_ + H:0 —HCE Mol (OH) = HI 1. Soluble in alcohol ez © Slightly solublein water 3. Lighter han aie 4 Colerese, ders & Se.pqs}noes ans .Nen pear in ature Chece low sluiity i polar water) ae ? 0 USES OF METHANE @mthey azbon black, which is used in printing ink, shoe polishes, rubber tyres ete form of natural gas (Gi) In the manufacture of CHs0H CHEMICAL PROPERTIES Due Page sifference in F.N of C and H. the C-H bond is almost nonpolar, and strong, hence it is not reactive tapilar reagents as acids, bases, oxidizing agents as KMnOq an inary conditions Important reactions are_i HALOGENATION ii NITRATION iii, PYROLYSIS iv. COMBUSTION LHAl ATION OF METHANE HALOGENATION is the process in which one or more H atoms of organic compound is replaced by halogen atom. It is substitution reaction CHLORINATION of methane takes place when itis reacted with chlorine in presence of sunlight as catalyst, Such actions in which sunlight act as catalyst are called PHOTOCHEMICAL REACTIONSAll the four H atoms of CHs are replaced, as follows. CH, + Cl; — Sau >CH:C] +HCl Monochloromethane CHsC1+ Ch Bu __, CIbCh + HCL Dichlorometha CHCl + Ch saucer > CHCl +HCl Trichloromethane CHCl+ Ch —saucat >CCly +HCl Tetra chloromethane a MECHANISM OF HALOGENATION (Free radical mechanism) The mechanisin of cilorination is through FREE RADICAL formation, Free Radicals are the highly energetic and hence reactive atom STEP @ INITIATION By the action of sunlight, Cls moleetie breaks dovm homolytic y4@ radical of ilorine (C1?) Cl — Sabie —___,y free radical STEP Gi) PROPAGATION Chlorine (CI?) free radical attacks methane to produce gf gifal CHy° and HCL cl Cl and regenerating CV” free cr cH + ct CHs°Free radical thea attacks another molecule of radi curl i CP fice radical repeats the above sequence till CO STEP (ii) TERMINATION ‘When sunlight is stopped the abov cach other and combine to ich, >CHCL — iid eas iii. CH + CHS —> CH. CH MBUSTION OF METHANE — busin isthe process in wip & 2yol PPetance eats vigorously with excess oxy amoride a8 CO} and hea-The OF pa amt of Met mikes CH, nd other alkanes a vale MO; > COr* IO. AH -43938)/mle topive 1) Methane is compo 2) C of Cy is sp’ yb fing 4 sp hybrid orbitals. 3) These 4sp? hyjfid dtbills aby arranged in tetrahedral fashion with angle 109. 5 ‘ $9) These 4 sp eee bry C overlap with 4 IS orbital of H atoms to Sy CHeis tetrahedral with angle 109.5", es Ny om a / Ww, - . H La. &S CHEMISTRY OF ETHANE — — Vy vee OCCURRENCE Scie It is the second member of Alkane Series Ii o¢cun (1) Natural gas (ii) gasas from oil wells (ii) Coal gas Nascent hydrogen Tris obtained in situ by action of HCT on Zn or action of Z2/Cu couple on aleohol Za/Cu + CHSOH + (GH.O)» Zn + Cx Zine ethoxideNascent hytrogen then reduces ethyl iodide to give ethane H+ 2 [H] > CiHy+ HI wv the catalytic yl iodide can also be reduced by Hogas in presence of catalyst Palladiun at 300°C, to give ethane GH Hi Ni/300°C > Grignard reagents are organo-metallic compound obtained by action of alky of ether at °C R-X +Mg: ETHER/ 0°C ——> RMaX, Ethane is obtained by acidic hydrolysis of C3HsMgl ethyl mags CoHsMgl ~ H:0 —EP—> C:Hs + Mel (OH) sium iodide (OK) + HI 4. ByWURTZ_ SYNTHESIS This method was frst used by French chemist WURTZ in 1855 In With Na-motal in ether. This process yields symnmetrical alkanes, with double foras than the alkyl halide used. To prepare ethane, Methyl iodide is heated with Naa 2CHSL + 2Na—DRY ETHER Colle +2) CHEMICAL PROPERNES Thus inthe rst sep chlorination gives I-chlorobpate-7// a) CH)— CH + Cl, SUG, oa But replacement of two isomers 1, 1-dichloroethane b) CHCl: c+ Cl. 1, 2-dichloroethane Juminous flame and releasing mare heat than mueth 2CaHls + 7 6110 + Heat STRUCTURE OF C2Hs JF twoC and 6 H atoms ie.C He 2)Each C of C3Hgis sp° hybridized containing 4 sp’ ese four sp hybrid orbital are arranged in teahedral fashion with angle 109. 5 ‘orbitals, 3 sp° hybrid orbitals of each C aining one sp'hybrid orbital of one C a mma Bond b/w carbon and earbon to a formation of sigma bond with 3H om overlap with one sp hybrid orbital of other C methane C:HeCHEMISTRY OF ETHENE Ethene is the first member of Alkene series, Previously it was known as ETHYL PREPARATION OF ETHENE 1 BY DEHYDRATION OF ALCOHOL ‘Dehydration is the elimination seaction in which a mole compound alcohols are delyirated when 1. Heated with acid catalyst as FSO, (cone.) ot H, 2. Passing vapors of alcohols over solid catalyst AL20s(s) or POs(s). A. Ethene is prepared by heating ethanol with H2SO« (conc.) at abou! a) CH) CH:OH — cone, H:S0/170°C 4 ~ Mechanism: this reaction proceeds in two steps Step (1) in this step ethyl hydrogen sulphate is formed in cold CHy—CH:OH + H-OSO3H CMSPSO.H + 10 Step (11) on heating ethyl hydrogen sulphate decomposes intg Bada Ci-Cr2-0S0;H_ — BOIL »Chs= CH: + FESO: B. Ethene is also prepared by passing vapors of eth HsPOVAL203 L203 or Bs penis te. c Cib= CH + HO SS ca cH HO 2. BY DEHYDROMALOGENATION OF F’ Dehiydrohalogenation is the beta elimination cee nich a Hand a halogen atom are CHs-CH:OH — Ab05/350°C to 30 CHs-CH:OH_ — HsPO,/AL05/250°C) removed! from adjacent C atorns ( Ethene is prepared by treating ethyl iat KOH the Hand CT are eliminated fom adjacent C atoms CH -CH.Cl + KORYALCSHOLIC) — CH.= CH + KCI+H:0 Note: if aqueous KOH is used then ally pated duc to substitution A. BY DEHALOGENATION OF A compound co SROETHANE( VICCINAL DICHLORIDE) cent Catoms is called VICCCINAL DIHALIDE oethane with Zn powder or with Nal powder)» CHy=CHy + ZaC mas in presence of Nito form CH= CH /P>~ rwwstcat. pRorenties 1. Colorless gas ph eed ty 2 Lo eae / CHEMICAL PROPERTIES aiiFafed compound with C=C ont of whids one is sigma other is pi bond. Being to become saturated by adding one molecule of other substance. The weak pi b (pi bond provides electron for attacking molecule which are electrophilic reagents h alled Electrophilic Addition Reaction. Alcenes themselves are Nucleophiles due to Followinaye the addition reactions.6 1 ADDITION REACTIONS OF ETHENE a 1. ADDITION OF HYDROGEN (Hs) (ivdrozenation)in presence of Pt, Pd and Ni pf gait. iene N\ dds wp Ht to form ethane. This is called catalytic reduction or hydrogenation, ) ~ CTL = H+ Hz —Ni300°C >» CH-CH. c 2. ADDITION OF HALOGENS (X:) i 2) Ethene adds up ane molecule of halogens molecule to form ditalolkat Clb =CHls+ Ch CCl» CCH CH-C (ifthe pave fe agus ela eB, here ge I arpa fas UNSATURATED TST CH= Cot Bip —CCly > Be CHCA) vY | S ee ts with I; in presence of ethanol Clb = Clb Ib — ETHANOL Order of reactivity of halogens is Cis Br: >I: (Ethene 3. ADDITION OF HYDROGEN HALIDES (0 Ethene adds up one molecule of HCl, HBr, HI for Ci: =CH:+HCl > CHs-CH-C Clb = Cl + HBr hc, ty of halogen acids is HI cD 0B eos D 4. ADDITION OF 1280: Ethene adds up one molecule of cold cquc_ FAO yields ethyl alcohol a) Order S04 cone) —> CH-CH:- OSO\H {OsH + HO — BOIL CHs-CH:- OH + H:SO thanol ok water i presence of 60% H:SO« to form ethanol HSCF HO E> CHy-CH- OH i~/ EWATER. ei =a fam Ghotangl a ack" RO | oe) ct - cr + Hoc —> Ho-cH-CH-cL LA cH = & / » HO-CH:—CIh-X F MUSTARD GAS Hy + SClb—> S (CH»-CH:-Cl)p +S e is heated at 200°C and under 100 atmospheric pressure in presence of 0.01% Os it polymatves into polyethylene (CH=CH) 200°C, 100 Atm Pressure, Trace of © —9[-CH>-Cl10. OXIDATION OF ETHENE (Reaction with KMnO) ‘When ethene is; ugh ite alain KMsO, (oxidizing pens) slay ir Twiized 3,2 Ethandiol (ETH OL) KMa04+H;O——+2KOH + 2Mn0: + 3{0] (CH: = CH:+ #20 = (0) »HO-CHs-CH:-OH Fihylette So) USES OF ETHENE ‘Used in manufacture of poisonous MUSTARD GAS. 1. Ettene is composed of two C and 4ELatom Le. Coll. 2 Each oF Cxtteds sp’ hybridized containing 3 id orbitals and one uahybridized (pz) orbital, — /~ Se, 3sp? hybrid orbitals are arranged in trigoral shapedtyjth Mngle{20". 4.Out of 3sp” hybridorbitals, boud with 2H atoms id orbital of other C atom to ‘one pi bond bw C anel C atom, wa e i ™ ey > J Acetylene iypeppa ethane with all 2 with alea) aor vi ss base NaNHE BrCH;- (C4ir+pNOH (ALCOHOLIC) —BOIL—> CH=CH +2KBr+ BrCH, IH (ALC) —Room temp—> CH»= CHB —NaNF—> NH iCaQ+3C——+ Ca: +CO— ii. CaCs +20 ——> CH=CH Ca (OH): « PHYSICAL PROPERTIES tly soluble in water, readily soluble in organic solvents, ble being unsaturated Tass gas, sweet sinell 2 Slight ~Exp) hes on compression, as itis un S USES OF ETH NE1, Used for welding. When mixed with O> forms Oxy-acetylene flame whose temperature is 300°C 2. Used for preparation acetaldehyde, Acetic acid, Ethanol and PVC ¢polyvinyl chloride) (CHEMICAL PROPERTIES oy Acetylene is an unsaturated compound with 2 pi bonds and one sma bond between C andj. ZGPts ) reason its ania feactions are ADDITION REACTIONS CNY) itmosty ads w two molecules of substan and changes to strated sable compowyty "// ADDITION REACTIONS OF EXE it ives addition reaction vith HX: HX, HCN, 140, ADDITION OF HYDROGEN (113) OR HYDROGENATION “ Tn presence of Ni or Pt, elhyne adds up two molecules of Hp, First forming eth Sede ce CS, CCH iCHmcH WHORE —VCaee | te et Hh. 7 2. ADDITION OF HALOGENS (X; 2 EEtiyne reacts with 2 molecules of Cl, r Brseven in dark but in presendagf cathe first forming a dinalide then finally tetrahalide Rae of reaction increnses in sunlighy |) A i) aCit=Cit+ Ch—CATALYST—>C1-CH=CH- Cl 12-1&eniSratiane bed —crr= crc > cL-cH-CH-ct 1.1 chloroethane vy >I-CH=CH-I 1, 2-Diioddyhege is Cla> Brs> Is CO 4. ADDITION oF HYDROGEN HALIDES aS! Ethyne reacts with halogen acids in dark facafe Galysed sunlight. Two molecules of HX are added. Order of reactitity fn acid is HT> H1Br> HCL Aiton of fret mest gives VINYL BROMIDE, am a) CH =CH* HBr —100°C —> H- CH 7 GH—BE—Vinyl bromide a Order of reactivity of haloges Vinyl bromide is an unsymmetrical molesuldss0 wow/itie addition of second molecule of HBr (also uunsyrumetica) follows MARKOWNIKOFF'S RULE: Acoédigg 100 “Negative part of the molecule to We addetr'should go to that carbon, which has least number of H” Thus in this addition, Br, should BagHtachad ty/Casbon No.1, giving 1, 1-Dibromoeth b) H-CH = CH-Br+ HBr < » H-CH-CH—Br 1,1-Dibromoethane | ; ~~ Lt 4.ADDITION OF HCN Ethyne adds up only molgonig OSHUCNn presen CH=CH HCN 5 s.apprrion of xrEK Gxo) ‘When acetylene is Puged Bough dilute sulphuric acid containing HeSO. at 75°C fist unstable VINYL ALCOHOL is forazed Wiel) then rearranges to ACETALDEHYDE CH=CH+HQ py) HSOy—75°C —yH-CH = CH-OH —REARRANGMENT—»CHi - CHO. ~ Note: Adiftiog oP HX: and HX are Electrophilic Addition Reaction Addn ‘and 1:0 are Nucleophilic Addition Reaction wae 1TH KMn0s OR OXIDATION OF ETHYNE ‘treated with hot aqueous KMn0,, two molecules of acid are formed Ba (CN) 20r (CuCl + NHLCD to form (cf >H-CH=CH-CN VINYL CYANIDE XRiCH = CH + Eh0 + 30] — Cold KMn0; ——> 2 HCOOH formic acid iiCH= CH~4[0] ———Hiot KMn0Q;———+ COOH - COOH oxalic acid 7. COMBUSTION OF ETHYNE The compl CH=CH + $20) +2 CO; + 1b 0 ATE is exothermic and release 312KJ/mole heat 31217 mole ‘combustion of etlyn SUBSTITUTION REACTIONS OR ACIDITY 0) In Ethyne or other alkynes, H attachedl to C=C bonds called TERMINAL, weakly acidic in narure end highly /~ ‘C atom in CH = CH is sp penetrate more to nacleus, so the C active. Itis due to following reason, more strongly, hence acg Following are the substitution reactions 1, SUBSTITUTION ‘When acetylene is passed over heated sodiuma metal, both ELatoms abe placed by Na. CH = CH + Na—heat (110°C) —9CH = CNa Sod 2. SUBSTITUTION or REPLACEMENT OF H ORC! AVY METAL Ag AND Cu When ethyne is heated with AgNOs im aqueous ammonixNHs of uprous chloride Cul m acqueots ammonia NFj; its hydrogen are replaced by Ag ayCr—— acetylide (White solid) These metalic compounds of Acetyler xd METALLIDES 1. Ethyme is composed of two C and, 2. Bach C of C3Hzis sp hybridized two unby idized py& pz orbity 3. Thee cwo Hpbi rts ny/pefeges oa tape wit male 190 degre. 4. Out of 2sp hybrid orbital of €adCfa} | Sp hybrid orbital are use in formation oan feo wih ne FOR Hdl ct Eom i fom sigma bead bw C&C 5. Remaining py , pz exbjigl aPeach © show parallel overlapping with one another and formed ne prband by C and C10 Molecular O1 reatment Of aS DATA 1 tructure Of Benzene (.) Six membered ring with alternate doubled and single bond system (b) Regular, flat, planner hexagonal shape IN (©) All bond angle are 120° (C-C-C) and (C-C-1, (@) All bond length 1.4A° which is intermediate to doubled and single bond. (e)Each C bonded to tree other atoms 2. Hybridization (@) in benzene (b)Unhybridized pz orbital is perpendicular at sp” hybrid ort ich C atom is sp? hybridized ble three sp? hybrid wns he at 120! tal 3. Construction Benze STEP-1 6 sp° hybrid orbital of 6 C atom and 6 1s orbital of 6 H atoms a) STEP a.Two sp? hybrid orbitals of each C overlap sigh Wyo'agfacent C ator linearly to forts Sigma bond bi C and C (sp’-sp"bond) b. Third sp” hybfidgrbitdl oheachC overlap with Ito form Sigma bend War & HHoy-sbon, One yd il of cash C pape f plane o benzene oN 8) All pe orbital par pon we of two way [and II form alternate double and single bond figure of ste Bat bond les pat (1 1 mediate bw single and double bond. Huckel suggested that each pz onbital overlag’in pazalleYp both adjacent pz orbital equally forming a single molecular orbital that all e- of pare covers a6 SagbGn atoms Due to above and below averlapping of pz arbitals, ow said Delocalized (not fixed). Dus to delocalization of ¢, bond is strong and benzene ‘much stable and bond of benzene is not single or doubled six picare molecule