ALKANESOrganic compounds having only two elements, carbon and hydrogen are called hydrocarbons. They are divided into two main classes, aliphatic and aromatic. The Alkane family General formula: CnH2n+2 First member is Methane (CH4) Also known as “Marsh gas”, chief constituent of natural gas (~97%) Hybridisation sp3 Structure: tetrahederal Bond angle: 109.5o Intermolecular force of attraction: van der waal type Preperation of alkanes
When only one alkyl halide is taken When two different types of alkyl halides are taken then we get a mixture of products. This is because the two alky halides not only react with each other but with themselves as well. So, we cannot prepare an alkane with odd no. of carbon atoms by this method.
That’s why Grignard reagent is always protected from moisture because it is very reactive and immediately gets converted to alkane. In Place of RMgX, RLi can also be used.
A molecule of CO2 is removed from carboxylic acid. That’s why this reaction is called decarboxylation reaction. CaO keeps NaOH dry because NaOH is hygroscopic (absorbs moisture).
Physical properties of alkanes
Chemical properties of alkanes As they are saturated hydrocarbons, they are very less reactive and inert but they undergo some substitution reactions.
Bromination is less rapid than chlorination. Iodination requires the presence of an oxidizing agent because HI reverses this reaction. In more complex alkanes, the abstraction of each different kind of H atom gives a different isomeric product 1o, 2o, 3o. Three factors determine the relative yields of the isomeric product: (1) Probability factor. This factor is based on the number of each kind of H atom in the molecule. For example, in CH3CH2CH2CH3, there are six equivalent 1º H’s and four equivalent 2º H’s. The odds on abstracting a 1º H are thus 6 to 4, or 3 to 2. (2) Reactivity of H.: The order of reactivity of H is 3º > 2º > 1º. (3) Reactivity of X.: The more reactive Cl. is less selective and more influenced by the probability factor. The less reactive Br. is more selective and less influenced by the probability factor. According to the reactivity-selectivity principle, if the attacking species is more reactive, it will be less selective, and the yields will be closer to those expected from the probability factor. In absence of air, they undergo pyrolytic cracking. In presence of air, alkanes are oxidized to carbon dioxide and water with evolution of large amount of heat. That is why they are used as fuels.
Tertiary alkanes can be oxidised to corresponding alcohols using KMnO4.
Unsaturated hydrocarbons containing C=C having general formula CnH2n. They are also known as Olefins. Nomenclature
Isomerism Alkanes show chain and position isomerism.
Preperation of alkenes
This reaction is β−elimination reaction. Ease of dehydrohalogenetion Iodine > bromine > chlorine Tertiary > Secondary > Primary Saytzeff rule: In case of dehydrohalogenation, that alkene is the preferred product which has more no. of alkyl groups attached to the double bonded carbon atom.
Problem: Dehydration of: (a) CH3CH2CH2CH2OH yields mainly CH3CH=CHCH3 rather than CH3CH2CH=CH2, (b) (CH3)3CCHOHCH3 yields mainly (CH3)2C=C(CH3)2. Ans: (a) The carbocation (R+) formed in this reaction is 1° and rearranges to a more stable 2° R2CH+ by a hydride shift (indicates as ~H:; the H migrates with its bonding pair of electrons). (b) The 2° R2CH+ formed undergoes a methide shift (~:CH3) to the more stable 3° R3C+.
Physical Properties First 4 members are gases. C5-C18 are liquids and higher members are solids. They are colourless and odourless. Melting points of alkenes are higher than alkanes because p electrons of double bond are polarizable. As a result, intermolecular forces of attraction are stronger. M.P. & B.P. inc. With inc. In the molecular mass but they do not show any regular trend. Trans-alkenes have higher m.p and lower b.p. than Cis-alkenes. Dipole moments: Alkenes are weakly polar because p-electrons of double bomds are easily polarisable. So, their dipole moments are higher compared to alkanes. (More is discussed in geometrical isomerism.) They are soluble in non-polar solvents. Chemical Properties As they have π bond present in them, they are quite reactive compared to alkanes because π electrons are weakly held and more exposed. They have a tendency to undergo electrophilic addition reaction. The electrophilic addition takes place in 2 steps via the formation of carbocation intermediate. Addition of Br2 to alkenes It takes place via two mechanisms, one is given to explain the formation of cis product and other to explain trans. .AlkynesAlkynes are unsaturated hydrocarbons containing carbon-carbon triple bond having general formula as CnH2n-2. First member is Ethyne C2H2. Nomenclature
Just like Alkenes, they show chain and position isomerism. As they are linear molecules (bond angle 180o), they do not show geometrical isomerism. Preperation
Chemical reactions They are more reactive than alkanes and alkynes due to the presence of two π bonds. They undergo addition and oxidation reactions readily. One important property of alkynes is the acidic nature of the hydrogen attached to the triple bonded carbon (because hydrogen is attached to sp hybridised carbon). Reactivity of halogens: Chlorine > Bromine > Iodine Iodination stops after one step resulting in trans product.
Reactivity: HI > HCl > HBr
With dialkylacetylenes, the products of hydrolysis and oxidation are cis-alkenes and ketones, respectively. Acetylene/ethylene produces polyacetylene/polyethylene on polymerisation. On passing through red hot iron tube at 873K, ethylene polymerises to form benzene.
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