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ALIPHATIC HYDROCARBONS --Hydrocarbons which do not contain benzene ring.

--Straight Carbon chain

n Alkanes are saturated hydrocarbons so they are linked by single covalent bonds and these bonds are hard to break thus they are stable and so lesser chemical reactivity is there. n They possess no functional groups. Alkanes are quite inert substances with highly stable nature. Their inactiveness has been explained as: (i) In alkanes all the C-C & C-H bonds being stronger sigma bonds and are not influenced by acids, alkalis, oxidants under ordinary conditions. (ii) The C-C (completely non polar) & C-H (weak polar) bonds in alkanes- are practically non polar because of small electronegativity difference in C (2.6) and H (2.1). Thus polar species i.e., electrophiles or nucleophiles are unable to attack these bonds under ordinary conditions. Inspite of less reactive nature, alkanes show some characteristic reactions. (1) Oxidation: Oxidation of alkanes gives different products under different conditions. (a) Complete oxidation or combustion : Alkanes burn readily with non luminous flame in presence of air or oxygen to give CO2 & water along with evolution of heat. Therefore alkanes are used as fuels. CnH2n+2 + [(3n+1)/2]O2 → nCO2 + (n+1)H2O; ΔH = -ve CH3 + 2O2 → CO2 + 2H2O; ΔH = -ve (b) Incomplete oxidation : Incomplete oxidation of alkanes in limited supply of air gives carbon black and carbon monoxide. 2CH4 + 3O2 → 2CO + 4H2O CH4 + O2 → C + 2H2O carbon black (c) Catalytic oxidation : (i) Lower alkanes are easily converted to alcohols and aldehydes under controlled catalytic oxidation.


Higher alkanes on oxidation in presence of manganese acetate give fatty acids. CH3(CH2)nCH3 + 3O2 CH3(CH2)nCOOH Chemical oxidation : Tertiary alkanes are oxidized to tertiary alcohols by KMnO4


> methane (v) The nitration of alkanes follows free-radical mechanism HONO2 HO + NO2 .H. Following substitution reactions in alkanes are noticed.2. (ii) Halogenation of alkane is made on exposure to halogen + alkane mixture to ultraviolet light or at elevated temperature. (iv) The reactivity order for halogens shows the order : F2 > CI2 > Br2 > I2 (v) F2 reacts violently even in dark and reaction may be controlled by diluting fluorine with N2. Nitration of alkane is made by heating vapours of alkanes and HNO3 at about 400oC to nitroalkanes. whereas iodination is very slow and reversible. (iv) The nitration of alkane also shows the order: T. Therefore iodination is made in presence of HgO or HIO3 (oxidants which decompose HI) [CH4 + I2 ↔ CH3I + HI] × 5 5HI + HIO3 → 3I2 + 3H2O 4CH4 + 2I2 + HIO3 → 5CH3I + 3H2O (vi) The reactivity order for H atom in alkane shows the order: tertiary hydrogen>secondary hydrogen>primary hydrogen> CH4 (vii) (b) (i) (ii) give The halogenations is catalysed by dibenzoyl peroxide. R-H + X2 R-X + HX (iii) The extent of halogenations depends upon the amount of halogen used. Nitration : Replacement of H atom of alkane by -NO2 group is known as nitration. C-C bonds of alkanes are also decomposed due to strong oxidant nature of HNO3 to produce all possible nitroalkanes. This is also known as vapour phase nitration.H. (i) (ii) (a) (i) Substitution reactions : Substitution in alkanes shows free radical mechanism. > S.H. CH4(g) + HNO3(g) CH3NO2 + H2O (iii) During nitration. > P. Halogenation : Replacement of H atom of alkane by halogen atom is known as halogenations.

C6H14 + 4H2 5. (ii) Alkanes having six to 10 carbon atoms are converted into benzene and its homologues at high pressure and temperature in presence of catalyst.H. (v) Sulphonation of alkanes also follows free radical mechanism. Straight chain alkanes on heating with AICI3 + HCI at about 200oC and 35 atm pressure converted into branched chain alkanes. 3. (ii) Lower normal alkanes are not suphonated. Thus isobutene is easily sulphonated as it contains tertiary hydrogen atom. C6H14 + H2SO4 → C6H13SO3H + H2O (iii) Lower members are sulphonated in vapour phase sulphonation. (i) (ii) are 4. Aromatization: (i) The process of conversion of aliphatic compound into aromatic compound is known as aromatization. C3H8 C3H6 + H2 6. > P. Pyrolysis : (i) The decomposition of a compound on heating in absence of air is known as pyrolysis. conc. > S.e. The product formed during cracking depends upon (a) nature of alkane (b) temperature and pressure . HOSO3H HO + SO3H C3H13-H + OH → C6H13 + H2O C3H13 + SO2H → C6H13SO3H Isomerization : The process of conversion of one isomer into other is known isomerization. (ii) The phenomenon of pyrolysis of alkane is also known as cracking. H2SO4) at 400oC. (iv) The reactivity order for sulphonation is T.H. (iii) Alkane vapours on passing through red hot metal tube in absence of air decomposes to simpler hydrocarbons.C3H7-H + HO → C3H7 + H2O C3H7 + NO2 → C3H7NO2 (c) Sulphonation : (i) Replacement of H atom of alkane by -SO3H is known as sulphonation.H. but higher normal alkanes show sulphonation (hexane onwards) when heated with oleum (i. Dehydrogenation : Alkanes are dehydrogenated on heating in presence of catalyst to produce corresponding alkenes..

middle one (C3 to C17) are liquids and higher are solids. is probably due to the fact that alkanes with odd carbon atoms have their end carbon atom on the same side of the molecule and in even carbon atom alkane. B. (iii) The boiling point of alkanes increases with increase in molecular weight due to increase in van der waals forces with increase in molecular weight i.0oC) (-182. (ii) Lower alkanes (C1 to C4) are gases. Thus all alkanes are lighter than M. order : propane < ethane < methane (-187. of isomeric alkanes who the order : pentane > isopentane > neopentane (v) The melting points of alkanes do not show a regular trend.5oC) (vi) The abnormal trend in m. PHYSICAL PROPERTIES a) State: (i) All are colourless & possess no characteristic odour. Thus alkanes with even carbon atoms are packed closely in crystal lattice to permit greater intermolecular attractions.76 g/ml.e.7oC) (-172. V2O2. (b) Density : The density of alkanes increases with increase in molecular weight and becomes constant at 0. MoO3 catalyses C-H bond fission and presence of That is why b.(c) presence or absence of catalyst (iv) The ease of cracking in alkanes increases with increase in molecular weight and branching in alkane. (vi) Presence of Cr2O3. ZnO catalyses C-C bond fission. (v) Fission of C-C bonds produces alkane and alkenes whereas fission of C-H bonds produces alkene and hydrogen. Alkanes with even number of carbon atoms have higher m. order : pentane < hexane < heptanes (iv) Also the branching in alkanes gives a decrease in surface area (as the shape approaches to spherical) which results in decrease in van der Waals Higher alkanes are converted into lower one (petrol C6 to C11) by (vii) The no. (c) Solubility : . the end carbon atom on opposite side. of products obtained during cracking increases with increase in molecular weight of alkane undergoing cracking. than their adjacent of odd number of carbon atoms. (viii) (ix) Cracking has an important role in petroleum industry.

PREPARATION (i) Decarboxylation : (a) Decarboxylation means removal of CO2 from molecules having . (c) Two different alkyl halides. (f) The decarboxylation of sodium formate yields H2. Its reaction is milder than caustic soda. (e) Soda lime is prepared by soaking quick lime CaO in caustic soda solution and then drying the products. Also CaO used alongwith NaOH keeps it dry (NaOH is hygroscopic) to aid fusion. CCI4. Otherwise the reaction will occur violently.COOH gp. the reaction is named as Frankland method. (ii) The solubility of alkanes decreases with increase in molecular weight. RCOONa R-H or RCOONa + NaOH R-H + Na2CO3 (c) The alkane formed always contains one carbon atom less than the original acid. (b) Saturated monocarboxylic acid salt of sodium potassium on dry distillation with soda lime gives alkane. on Wurtz reaction give all possible alkanes. (iii) Liquid alkanes are themselves good. (d) The yield is good in case of lower members but poor for higher members. (e) If Zn is used in place of Na. R-X + 2Na + X-R R-R + 2NaX (b) An alkyl halide on Wurtz reaction leads to the formation of symmetrical alkane having an even number of carbon atoms.. It is generally written as NaOH + CaO. . non polar solvents. C6H6. CH3X + Na + C2H5X → CH3CH2CH3 + CH3CH3 + CH3CH2CH2CH3 The different steps are: CH3X + 2Na + C2H5X → CH3CH2CH3 + 2NaX CH3X + 2Na + C2H5X →CH3CH3 + 2NaX C2H5X + 2Na + C2H5X → C2H5C2H5 + 2NaX (d) The separation of mixture into individual members is not easy because their boiling points are near to each other and thus Wurtz reaction is not suitable for the synthesis of alkanes containing odd number of carbon atoms. ether etc.g. HCOONa + NaOH H2 + Na2CO3 CH3COONa + NaOH CH4 + Na2CO3 methane (ii) Wurtz reaction: (a) A solution of alkyl halide in ether on heating with sodium gives alkane.(i) Alkanes being non polar and thus insoluble in water but soluble in non polar solvents e.

(d) The yields are generally high and the hydrocarbons formed are pure. reaction occurs at normal temperature. when AI dissolves leaving Ni in finely divided state. Note : Zn-Cu couple is prepared by adding Zn granules in aqueous CuSO4 solution where copper is deposited on the Zn pieces. (iv) (a) By hydrogenation of alkenes : Sabatier and senderen's method : Alkenes and alkynes on catatlytic hydrogenation give alkanes CH2 = CH2 + H2 CH3-CH3 CH≡CH + 2H2 CH3-CH3 (b) Catalyst Ni is used in finely divided form. R-X R-H + HX (b) The nascent hydrogen may be obtained by any one of the following (i) Zn + HCI (ii) Zn + CH3COOH (iii) Zn-Cu couple in ethanol (iv) Red P + HI (v) Al-Hg + ethanol (c) Alkyl halides can also be reduced catalytically to alkane by H2/Pd or LiAIH4 or by H2/Ni. The filtered. If Pt or Pd are used as catalyst. (a) Involving intermediate formation of an organometallic compound: RX + 2Na → [RNa] + NaX Intermediate RX + [RNa] → R-R + NaX (b) Involving intermediate formation of free radicals: RX + Na → [R] + Nax Free radicals R + R → R-R Alkane (iii) By the reduction of alkyl halides: (a) Alkyl halides on reduction with nascent hydrogen form alkanes. . It is obtained by boiling Ni-AI alloy with NaOH. Also some times Raney nickel is used as catalyst.(f) Limitations of wurtz reaction : (a) Methane can not be obtained by this method (b) The reaction fails in case of tertiary halides (g) Mechanism : The mechanism of Wurtz reaction is although not clear however two mechanisms are proposed for this reaction.

This is Clemmensen reduction. (v) Kolbe's electrolysis method: (i) Alkanes are formed. all probable alkanes are formed. (vi) By Grignard reagents: (i) Organic compounds in which a metal atom is directly linked to carbon atom are known as organometallic compound. e. (vii) By reduction of alcohols. Raney Ni is effective at room temperature and atmospheric pressure. (C2H5)4 Pb. CH3CHO + 2H2 CH3CH3 + H2O CH3COOH + 2H2 CH3CH2CH3 + H2O (ii) Carbonyl compounds may also be reduced to alkanes by Wolf Kishner reaction (ix) By the hydrolysis of AI or Be carbides: (i) Only CH4 can be obtained by the hydrolysis of Be or Al carbides. ketones or fatty acids and their derivatives: (i) The reduction of either of the above in presence of red P & HI gives corresponding alkane. (iii) Grignard reagent on double decomposition with water or with other compounds having active H(the hydrogen attached on O. AI4C3 + 12H2O 4AI(OH)3 + 3CH4 Be2C + 4H2O 2Be(OH)2 + CH4 . HCI also yields alkanes. However. N. (C2H5)2 Zn (ii) Alkyl or aryl magnesium halide (R-MgX) are also called Grignard reagents or organometallic compounds.g. in case of mixture of carboxylic acid salts.washed and died Ni is known as Raney Nickel. (viii) By Reduction of Carbonyl compounds : (i) The reduction of carbonyl compounds by amalgamated zinc and conc. F or triple bonded carbon atom are known as active hydrogen) give alkane. aldehydes. on electrolysis of concentrated aqueous solution of sodium or potassium salt of saturated mono carboxylic acids (ii) Electrolysis of an acid salt gives symmetrical alkane. HC≡CNa. R1COOK + R2COOK R1-R2 + 2CO2 + H2 + 2NaOH (R1-R1 and R2-R2 are also formed).

Propane. into gasoline and fuel oil. USES Some of the common uses of alkanes are: -heating -electricity generation -Cooking -production of polymers . coal. The first four alkanes(Methane. Magnesium carbide. Butane) are used for heating. They are used as fuel sand as good solvents for nonpolar substances. Propane and Butane are used as LPG(liquefied petroleum gas). It is also a potential source of natural gas. Mg2C2 reacts with water to give propyne. Alkane having carbon number 5-8 are volatile liquids. Propane is also used in the propane gas burner. The main components of natural gas are methane and ethane. 3. The other fossil fuel. pesticides and other chemicals .components of gasoline (pentane and octane) . 2R . . is a potential second source of alkanes. This trialkyl borane on treatment with acetic acid or propanoic acid yields alkane. 2.paraffin wax The uses of alkanes can be determined according to the number of carbon atoms present in it. They are also used as propellants in Aerosol sprays. This lithium dialkyl cuprate now again reacts with alkyl chloride to given alkane. Calcium carbide reacts with water to give acetylene. cooking and electricity generation. Processes are being developed to convert coal. CH3CH2CI + 2Li CH3CH2Li + LiCl 2CH3CH2Li + CuI → Li(CH3CH2)2 Cu + LiL Li(CH3CH2)2Cu + CH3CH2CI → CH3CH2CH2CH3 + CH3CH2Cu + LiCl SOURCES The alkanes are isolated from natural gas and petroleum. through hydrogenation.serve as intermediate in the synthesis of drugs. Ethane. CH4 can be obtained by passing a mixture of H2S and CS2 through red and Cu tube CS2 + 2H2S CH4 + 4Cu2S (x) By hydroboration of alkenes : Alkenes on hydroboration give trialkyl borane as a result of addition of diborane on olefinic bond.1. butane in disposable cigarette lighters.CH=CH2 2(RCH2CH2)3B 2RCH2CH3 (xi) ByCorey-House synthesis : Alkyl chloride say chloroethane reacts with lithium in presence of ether to give lithium alkyl then reacts with CuI to give lithium dialkyl cuprate.

b) Addition reactions : (i) Cyclopropane being the most strained ring and more reactive undergoes addition reactions like alkenes. (ii) Cyclobutane is relatively less reactive as it does not undergo addition reactions under normal conditions. Physical properties (i) Cyclopropane and cyclobutane are gases. (ii) These are insoluble in water but soluble in alcohol or acetone. a) Free radical substitution : Cycloalkanes are halogenated in presence of sun light or UV light like alkane. It is therefore cyclohexane floats over water. Alkanes from 17 carbon upwards form the most important components ofFuel oil and lubricating oilalso used as anti-corrosive agents. Synthetic Polymers such aspolyehtylene are alkanes with chains containing hundreds of thousands of carbon atoms. However it undergoes these reactions under special conditions. next three members are liquid and higher members are solid. It is therefore higher cycloalkanes are not attacked by acids. CYCLIC HYDROCARBONS --Closed carbon chain CYCLOALKANES Chemical properties Cyclopropane and cyclobutane are comparatively less stable due to more strain in ring (Follow Baeyer's strain theory) and thus tend to breakup and open the ring to act like a double bond species to give addition reactions. Many solid alkanes find use as paraffin wax also. Alkanes with 35 or more carbon atoms are used for road surfacing. The cycloalkanes from cyclopentane and onwards show remarkable similaries with alkanes due to their stability. . as their hydrophobic nature means that water cannot reach the metal surface. The stability of higher cycloalkanes is due to less strained ring as well as each carbon atom being sp3 hybridized like alkanes. (c) Oxidation : Cycloalkanes are oxidized by alkaline potassium permanganate to dicarboxylic acids involving ring fusion. (iii) Their density increases with increase in molecular weight. alkalis and common oxidizing under normal conditions.Alkanes from having carbon 9-16 form the major part ofDiesel and aviation fuel. Lower members are lighter than water and floats over it.

The method can be regarded as intramolecular Wurtz reaction and is called Freund reaction.(iv) The boiling points increase with increase in molecular weight. SOURCE/S Natural gas and petroleum USES 1) used as a nonpolar solvent for the chemical industry and 2) raw material for the industrial production of adipic acid and caprolactam. These βketo esters on hydrolysis and subsequent heating gives cyclic ketones which are reduced by ZnHg/HCI to give cycloalkanes. both of which are intermediates used in the production of nylon. .V. light gives derivatives of cycloalkanes. The boiling point are also higher than their corresponding alkenes and alkanes PREPARATION (a) From dihalogen compounds : α-ω elimination from dihalides having halogen atoms on two ends of carbon chain (α-ω dihalides) with Na or Zn dust gives rise to the formation of cycloalkanes. (d) By Dieckmann cylisation : Esters of dicarboxylic acids on heating in presence of sodium ethoxide undergo intramolecular Claisen condensation to gives cyclic β-keto esters. This can be used to prepare cycloalkanes from three to six carbon atoms. (b) By Clemmensen reduction : The reduction of cyclic ketones by Zn-Hg/HCI gives cycloalkanes. (e) From aromatic compounds: Six membered cyclo compounds can be easily obtained by the catalytic reduction of benzene and its derivatives. (c) From alkenes : Alkenes on treating with CH2I2 in presence of Zn-Cu couple or by diazomethane (CH2N2) in presence of U.