Properties of Alkanes

Physical Properties of Alkanes

(a) Physical State:

All are colourless & possess no characteristic odour.Lower alkanes (C₁ to C₄) are gases, middle one (C₃ to C₁₇) are liquids and higher are solids.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.e.,B.pt. order : pentane < hexane < heptanes.  

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 forces. That is why b.pt. of isomeric alkanes who the order : pentane > isopentane > neopentane

The melting points of alkanes do not show a regular trend. Alkanes with even number of carbon atoms have higher m.pt. than their adjacent of odd number of carbon atoms.

    M.pt. order :     propane             <    ethane             <        methane

                         (-187.7^oC)            (-172.0^oC)                   (-182.5^oC)

The abnormal trend in m.pt. 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, the end carbon atom on opposite side. Thus alkanes with even carbon atoms are packed closely in crystal lattice to permit greater intermolecular attractions.

(b) Density : The density of alkanes increases with increase in molecular weight and becomes constant at 0.76 g/ml. Thus all alkanes are lighter than water.

(c) Solubility :

Alkanes being non polar and thus insoluble in water but soluble in non polar solvents e.g., C₆H₆, CCI₄, ether etc. The solubility of alkanes decreases with increase in molecular weight.Liquid alkanes are themselves good, non polar solvents.

Refer following Video for Properties of Alkane

Chemical Properties of Alkanes

Alkanes are quite inert substances with highly stable nature. Their inactiveness has been explained as:

1. In alkanes all the C-C & C-H bonds being stonger sigma bonds and are not influenced by acids, alkalies, oxidants under ordinary conditions.

2. 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.

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Inspite of less reactive nature, alkanes show some characteristic reactions.

Oxidation Reactions of Alkane

Oxidation of alkanes gives different products under different conditions.

1. 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. 

C_nH_2n+2 + [(3n+1)/2]O₂ → nCO₂ + (n+1)H₂O;     ΔH = -ve

 CH₃ + 2O₂ → CO₂ + 2H₂O;             ΔH = -ve

2. 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

3. Catalytic oxidation :

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

4. Chemical oxidation : Tertiary alkanes are oxidized to tertiary alcohols by KMnO₄

Substitution Reactions of Alkanes

Substitution in alkanes shows free radical mechanism. For mechanism see free radical substitution.Following substitution reactions in alkanes are noticed.

 1. Halogenation of Alkanes :

Chlorination may be brought about by photo irradiation, heat or catalysts, and the extent of chlorination depends largely on the amount of chlorine used. A mixture of all possible isomeric monochlorides is obtained, but the isomers are formed in unequal amounts, due to difference in reactivity of primary, secondary and tertiary hydrogen atoms.

The order of ease of substitution is

Tertiary Hydrogen > Secondary Hydrogen > Primary Hydrogen

Chlorination of isobutane at 300 ^oC gives a mixture of two isomeric monochlorides

The tertiary hydrogen is replaced about 4.5 times as fast as primary hydrogen. Bromination is similar to chlorination, but not so vigorous. Iodination is reversible, but it may be carried out in the presence of an oxidising agent such as HIO₃, HNO₃ etc., which destroys the hydrogen iodide as it is formed and so drives the reaction to the right, e.g.

CH₄ + I₂  CH₃I + HI

5HI + HIO₃  3I₂ + H₂O

Iodides are more conveniently prepared by treating the chloro or bromo derivative with sodium iodide in methanol or acetone solution. e.g

RCl + NaI  RI + NaCl

This reaction is possible because sodium iodide is soluble in methanol or acetone, whereas sodium chloride and sodium bromide are not. This reaction is known as Conant Finkelstein reaction.

Direct fluorination is usually explosive; special conditions are necessary for the preparation of the fluorine derivatives of the alkanes.

RH + X₂ RX + HX

(Reactivity of X₂: F₂ > Cl₂ > Br₂; I₂ does not react)

The mechanism of methane chlorination is:

Initiation Step

Cl : Cl   2Cl^·      DH = + 243 KJ mol^-1

The required enthalpy comes from ultraviolet (uv) light or heat.

Propagation Step

i). H₃C : H + Cl^·  → H₃C^· + H : Cl           H = - 4KJ mol^-1 (rate determining)

ii). H₃C^·   + Cl : Cl  →  H₃C : Cl  + Cl^·     H = - 96 KJ mol^-1

The sum of the two propagation steps in the overall reaction,

CH₄ + Cl₂   →  CH₃Cl  + HCl              H= - 100 KJ mol^-1

In propagation steps, the same free radical intermediates, here Cl^· and H₃C^·,  being formed and consumed. Chains terminate on those rare occasions when two free-radical intermediates form a covalent bond.

Cl^·  + Cl^·    → Cl₂ ;   H₃C^·  + Cl^·   → CH₃ : Cl

H₃C^·  + ^·CH₃  → H₃C : CH₃

Inhibitors stop chain propagation by reacting with free radical intermediates, e.g.

In more complex alkanes, the abstraction of each different kind of H atom gives a different isomeric product. Three factors determine the relatives yields of isomeric product.

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 1^o H’s  and four equivalent 2^o H’s. The ratio of abstracting a 1^oH are thus 6 to 4, or 3 to 2.

Reactivity of H^· :  The order of reactivity of H is 3^o > 2^o > 1^o.

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, as summarized by 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 the chlorination of isobutane abstraction of one of the nine primary hydrogens leads to the formation of isobutyl chlorides, whereas abstraction of a single tertiary hydrogen leads to the formation of tert-butyl chloride. The probability favour formation of isobutyl chloride by the ratio of 9:1. But the experimental results show the ratio roughly to be 2:1 or 9:4.5. Evidently, about 4.5 times as many collisions with the tertiary hydrogen are successful as collisions with the primary hydrogens. The E_act is less for abstraction of a tertiary hydrogen than for abstraction of a primary hydrogen.

The rate of abstraction of hydrogen atoms is always found to follow the sequence 3^o > 2^o > 1^o. At room temperature, for example, the relative rate per hydrogen atom are 5.0:3.8:1.0. Using these values we can predict quite well the ratio of isomeric chlorination products from a given alkane. For example:

Inspite of these differences in reactivity, chlorination rarely yields a great excess of any single isomer.

The same sequence of reactivity, 3^o > 2^o > 1^o, is found in bromination, but with enormously larger reactivity ratios. At 127^oC, for example, the relative rates per hydrogen atom are 1600:82:1. Here, differences in reactivity are so marked as vastly to outweigh probability factors. Hence bromination gives selective product.

In bromination of isobutane at 127^oC,

Hence, tert-butyl bromide happens to be the exclusive product (over 99%).

2. Nitration :

Replacement of H atom of alkane by -NO₂ group is known as nitration.Nitration of alkane is made by heating vapours of alkanes and HNO₃ at about 400^oC to give nitroalkanes. This is also known as vapour phase nitration.

 CH_4(g) + HNO_3(g)  CH₃NO₂ + H₂O

During nitration, C-C bonds of alkanes are also decomposed due to strong oxidant nature of HNO₃ to produce all possible nitroalkanes.

The nitration of alkane also shows the order:T.H. > S.H. > P.H. > methane

The nitration of alkanes follows free-radical mechanism

 HONO₂  HO + NO₂

 C₃H₇-H + HO → C₃H₇ + H₂O

C₃H₇ + NO₂ → C₃H₇NO₂

3. Sulphonation :

Replacement of H atom of alkane by -SO₃H is known as sulphonation. Lower normal alkanes are not suphonated, but higher normal alkanes show sulphonation (hexane onwards) when heated with oleum (i.e., conc. H₂SO₄) at 400^oC.

C₆H₁₄ + H₂SO₄ → C₆H₁₃SO₃H + H₂O

Lower members are sulphonated in vapour phase sulphonation.The reactivity order for sulphonation is T.H. > S.H. > P.H. Thus isobutene is easily sulphonated as it contains tertiary hydrogen atom.

Sulphonation of alkanes also follows free radical mechanism.

 HOSO₃H   HO + SO₃H

C₃H₁₃-H + OH → C₆H₁₃ + H₂O

C₃H₁₃ + SO₂H → C₆H₁₃SO₃H

4.  Isomerization  :

The process of conversion of one isomer into other is known isomerization.Straight chain alkanes on heating with AICI₃ + HCI at about 200^oC and 35 atm pressure are converted into branched chain alkanes.

 5. Aromatization  :

The process of conversion of aliphatic compound into aromatic compound is known as aromatization. Alkanes having six to 10 carbon atoms are converted into benzene and its homologues at high pressure and temperature in presence of catalyst.

C₆H₁₄      + 4H₂

6. Dehydrogenation : Alkanes are dehydrogenated on heating in presence of catalyst to produce corresponding alkenes.

 C₃H₈   C₃H₆ + H₂

7. Pyrolysis :

The decomposition of a compound on heating in absence of air is known as pyrolysis. The phenomenon of pyrolysis of alkane is also known as cracking. Alkane vapours on passing through red hot metal tube in absence of air decomposes to simpler hydrocarbons. The product formed during cracking depends upon

     (a) nature of alkane

     (b) temperature and pressure

     (c) presence or absence of catalyst

The ease of cracking in alkanes increases with increase in molecular weight and branching in alkane.Fission of C-C bonds produces alkane and alkenes whereas fission of C-H bonds produces alkene and hydrogen.

Presence of Cr₂O₃, V₂O₂, MoO₃ catalyses C-H bond fission and presence of SiO₂, AI₂O₃, ZnO catalyses C-C bond fission.The no. of products obtained during cracking increases with increase in molecular weight of alkane undergoing cracking.   

Cracking has an important role in petroleum industry. Higher alkanes are converted into lower one (petrol C₆ to C₁₁) by cracking.

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