Alkanes Paraffins

chapter

General formula of alkanes is Cn H2n+2
They are also called paraffins (parum = Little + affinis = reactivity).


They may have no bond polarity and does not contain in the molecule so known as saturated hydrocarbons.
Preparation
(i) From Grignard reagent
RMgX alkyl magnesium halide (other examples of RMgX type molecules are RLi and R2Cd)
This reaction is known as Zere wittinoffs method for estimation of active hydrogen in the molecule. Active hydrogen is the one
which is attached to a highly electronegative element. eg., N,O,S etc. Hydrogen attached to alkyl groups like CH3, C2H5 are
never active due to less electronegativity of C atom.



R in Hydrocarbon always comes from grignard reagent. In case of alkynes, only 1-alkynes reacts with G.R because it contains
active Hydrogen atom attached with a sp hybridized carbon atom with maximum electronegativity.


(ii) From HI and red phosphorous












Clemmensen Reduction
(iii) Clemmensen Reduction
The carbonyl groups of aldehydes and ketone (mainly) undergo reduction to methylene groups with amalgamated zinc and
concentrated HCl acid is known as Clemmensen reduction.




Mechanism of reaction


Applications
1. Reduction of aliphatic and mixed aliphatic-aromatic carbonyl compounds.


2. Reduction of keto acids


3. Reduction of phenolic carbonyl compounds




(iv) Kolbes Electrolysis
Kolbes electrolysis is ionic (I
st

) cum free radical mechanism.


Here Na or K salts of acids are taken and solution becomes alkaline due to NaOH. So that pH of solution increases.


















Q. Kolbes electrolysis of Sodium Propionate gives.

1. Hexane 2. Pentane 3. Butane 4. All Ans. Butane.

Reduction of alkyl halides
(v) Reduction of alkyl halides


reduction can also be done by a. LiAlH
4
b. Na/C
2
H
5
OH c. Zn Cu Couple

Zn Cu couple is Zn wetted by Cu. It is prepared by putting CuSO
4
on Zn granules present in flask which leads to Cu deposition on them.











(vi) Wurtz Reaction


Two following mechanism have been suggested for wurtz reaction:



If we take one alkyl and one aryl group, this is known as wurtz fittig reaction (practically possible)


(vii) Sabatier Senderons Reduction (Hydrogenation of alkyne or alkenes)






(viii) Decarboxylation by Sodalime (NaOH + CaO)


























Hydrolysis of metal carbides
(ix) Hydrolysis of metal carbides










Al & Be both gives same alkane due to diagonal
relationship between them.









(x) Wolff Kischner Reduction
WolffKischner reduction
involves the conversion of carbonyl groups of carbonyl compounds in to methylene groups by heating their hydrozones or
semicarbazones in the presence of strong base such as C
2
H
5
ONa or NaOH or KOH.


Earlier method of heating the hydrozones of carbonyl compounds with C
2
H
5
ONa at 180C in an autoclave has since been modified. In the modified procedure, hydrazine hydrate and the carbonyl compound
are heated with KOH or NaOH in ethylene glycol for several hours.
(Hung minlon reaction)
The water formed escapes and the temperature rises to 200C when the hydrazone decomposes with the formation of hydrocarbon
with evolution of nitrogen due to more boiling point of solvent all water easily separate out.


In a further modification, the reduction can be carried out at room temperature by using dimethyl sulphoxide as solvent and
potassium tertiary butoxide as base. The yield is very good for example.


In some ways this is better than clemmensen reduction because it does not fail with acid-sensitive or high molecular weight
reactants.


(xi) Corey house synthesis
The most useful organocopper reagents are the lithium dialkylcuprates, which is generated when a copper (I) halide reacts wit h two
equivalents of an alkyllithium in ether as a solvent like tetrahydrofuran.


In the first phase of the preparation, where one equivalent of alkylithium displaces halide from copper to produce an alkylcopper
(I) species :


The second equivalent of the alkyllithium reacts with the alkylcopper to give a negatively charged dialkyl - substituted derivative of
copper (I) called a
dialkylcuprate anion.
It is formed as its lithium salt.


Finally Lithium dialkylcuprates react with alkyl halides to give alkanes by formation of carbon-carbon bond between the alkyl
group of the alkyl halide and the alkyl group of the dialkylcuprate.


In this reaction halide of primary nature, especially iodides, are the best substituted because, elimination reaction becomes a
problem with secondary and tertiary alkyl halides. (Rate of any elimination reaction is 3 > 2 > 1)


Lithium diarylcuprates are prepared in the same way as lithium dialkylcuprates and undergo comparable reactions mainly with
primary alkyl halides only.


Physical Properties
As we have seen methane, ethane, propane, and butane are gases at room temperature. The unbranched alkanes from pentane (C
5
H
12
) to heptedecane (C
17
H












36
) are liquids, while higher homologous are solids. The boiling points of unbranched alkanes increase as the number of carbon
atoms in the chain increases. The boiling points for 2-methyl-branched alkanes are lower than those of the unbranched isomer. By
exploring the molecular level the reasons for the increase in boiling point with the number of carbons and the reasons for the
difference in boiling point between branched and unbranched alkanes, we can begin to develop some insights into the relations hip
between structure and properties.

A substance exists as a liquid rather than a gas because there are cohesive forces between molecules
(intermolecular attractive forces )
that are greater in the liquid state than in the gas phase. Attractive forces between neutral species (atoms or molecules, but not ions)
are referred to as
Vander Waals
forces and they are

1.
London forces
2.
dipole - dipole
3.
ion - dipole
4.
hydrogenbonding.

The intermolecular interactions, which are observed in nonpolar molecules, are known as
London forces.
The electrons are in continuous movement and induce temporary polarization in one molecule, which in turn induces polarization
in an opposite direction in adjacent molecule. This momentary induction of dipole results in attraction between otherwise nonpolar
molecules (induced dipole interaction). The London forces are very weak intermolecular forces.
The attraction among nonpolar molecules of alkanes
is attributed to London forces.



Alkanes Paraffins
Chapter


Thus, the overall increasing order of strength for intermolecular forces of attraction is as follows:


Melting Point and Boiling Point
Melting point.
The temperature at which a solid gets converted to a liquid is defined as the melting point of that solid. In solid state, the particles
are arranged in highly ordered manner (regular and symmetrical). On heating, the particles acquire thermal energy and move to a
random arrangement as in liquid. The temperature at which thermal energy of particle overcomes the forces of attraction holding
them in an orderly arrangement is known as the
melting point.
In general, ionic compounds have much higher melting points compared to covalent compounds. In ionic compounds, the strong
electrostatic forces of attraction hold the
oppositely charged ions in a crystal lattice.
To overcome the strong forces, we have to break the ionic bonds between oppositely charged ions and for that a very high
temperature is required.

In covalent compound,
the molecules are held together in crystal through weak van der Waal forces of attraction (dipole-dipole or induced dipole
interactions).
To overcome these forces, relatively low temperature is required. Unlike ionic compounds, no bonds are broken in covalent
compounds rather weakly held molecules are to be separated from each other. In general, the melting point of organic compounds
increases with an increase in molecular mass.


Melting point depends upon




1. Molecular symmetry 2. Molecular mass

For example in normal pentane and neopentane, higher melting point of neopentane due to more symmetry and compact structure.
Other example is
trans form
which always contains higher melting point than cis form due to more stability and symmetry.

In molecules of alkanes melting point follows saw tooth rule means odd number alkanes does not get much higher melting point
than even number due to less symmetry and more repulsion of carbon edges. So graph comes in zigzag manner.


Boiling point.
The temperature at which vapour pressure of a liquid equals the atmospheric pressure is termed as the
boiling point
of that liquid. In other words, the some what orderly arranged molecules in liquid state escape from the surface of liquid to highly
random gaseous phase. On heating, the thermal energy overcomes the forces of attraction between molecules and they escape to
vapour state. In organic compounds, the boiling point increases with an increase in molecular mass.
The hydrogen bonding in an organic molecule increases the boiling point tremendously as the forces of attraction increase.
For example, ethanol (boiling point 78C) has higher boiling point compared to dimethyl ether due to the presence of
intermolecular hydrogen bonding.
Boiling point depends upon




1. Molecular mass 2. Polarity of molecule

Cis isomer are more polar so higher boiling point than trans isomers.
























Halogenation
(i) Halogenation
Depending upon which hydrogen atom is replaced, any of a number of isomeric products can be formed from a single alkane.
Ethane can yield only one halo ethane ; propane, n-butane, and isobutane can yield two isomers each; n-pentane can yield three
isomers, and isopentane, four isomers. Experiment has shown that on halogenation an alkane yields a mixture of all possible
isomeric products, indicating that all hydrogen atoms are susceptible to replacement. For example, for chlorination :



The product obtained when halogenation of alkane occurs in diffused sunlight depends upon the amount of alkane and Cl
2
taken in the process while reactivity of halogens are F2 > Cl2 > Br2>I2


This is a reversible chemical reaction where HI being a strong reducing agent so it produces CH
4
again in reversible reaction. Reaction is carried out in the presence of some oxidising agent such as HIO
3
,HNO
3
or HgO, which absorb HI from the reaction.




Bromination gives the corresponding bromides but in different proportions :


Although both chlorination and bromination yield mixtures of isomers, the results given above show that the relative amounts of
the various isomers differ markedly depending upon the halogen used. Chlorination gives mixtures in which no isomer greatly
predominates ; in bromination, by contrast, one isomer may predominate to such an extent as to be almost the only product, making
up 97-99% of the total mixture. In bromination, there is a high degree of selectivity as to which hydrogen atoms are to be
replaced.



Halogenation of alkanes is not suitable for the laboratory preparation of alkyl halides. In chlorination, any one product is
necessarily formed in low yield, and is difficult to separate from its isomers, whose boiling points are seldom far from its own.
Even bromination of alkanes is seldom used.
Chlorination of many alkanes has prove these typical results. After allowance is made for differences in the probability fact or, 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 rates per hydrogen atom are 5.0 : 3.8 : 1.0. Using these values we can predict quite well the ratio of isomeric chlorinated
products from a given alkane. For example :

















Inspite of these differences in reactivity, chlorination rarely yields a great preponderance of any single isomer. In nearly every
alkane, as in the example we have studied, the less reactive hydrogen are the more numerous; their lower reacti vity is compensated
for by a higher probability factor, with the result that appreciable amount of every isomer is obtained.

The same sequence of reactivity, i.e., 3
o

> 2
o

> 1
o

, is found in bromination, but with enormously large reactivity ratios. At 127
o

C, for example, the relative rates per hydrogen atom are 1600 : 82 : 1. Here, differences in reactivity are marked as vastly to
outweigh the probability factors.







Reactivity and Selectivity
Reactivity and Selectivity
In its attack on alkanes, the bromine atom is much more selective than chlorine atom (with relative rate factors of 1600 : 82 : 1 as
compared to 5.0 : 3.8 : 1). It is also much less reactive than chlorine atom (only 1/375 000 as reactive toward methane) This is just
one example of a general relationship : in a set of similar reactions the less reactive the reagent, the more selective it is in its
attack.
Mechanism of free radical substitution reaction




Puzzle. Show rate of halogenation in following compound.











Inhibitors
Finally, how does the mechanism of chlorination occurs ? In fact, a small amount of oxygen slow down the reaction for a period of
time, which depends upon the amount of oxygen, after which the reaction proceeds normally?
Oxygen is believed to react with a methyl radical to form a new free radical :





The CH3OO radical is much less reactive than the CH3 radical, and can do little to continue the chain. By combining with a
methyl radical, one oxygen molecule breaks a chain, and thus prevents the formation of thousands of molecules of methyl chloride;
this, of course, slows down the reaction tremendously. After all the oxygen molecules present have combined with methyl radicals,
the reaction is free to proceed at its normal rate.
A substance that slow down or stops a reaction even though present in small amount is called inhibitor. The period of time during
which inhibition lasts, and after which the reaction proceeds normally, is called the inhibition period. Inhibition by a relatively
small amount of an added material is quite characteristic of chain reactions of any type, and is often one of the clues that first leads
us to suspect that we are dealing with a chain reaction







(ii) Reeds Reaction or Chlorosulphonation of alkanes
When alkanes reacts with sulphurdioxide and chlorine in ultraviolet medium it forms chlorosulphonated product reaction follows
free radical mechanism by the steps of propogation and termination. If the reaction can undergo expansion by reaction with alkali it
forms synthetic utility products like detergents (RSO3Na).




























Nitration

(iii) Nitration


Here mixture is obtained due to cleavage of CC and CH Bond.





Mixture of nitroalkanes are formed in different percentages where product amount based on intermediate stability.
(CH3)2CHNO2 is obtained in highest proportion on nitration of propane while nitroethane and nitromethane like compounds in
minimum amount.



(iv) Sulphonation
This process is done by con. H2SO4 or fuming H2SO4 (olium : H2S2O7) which contains SO3 as active species, but in this process by
the mechanistic rule H atom is replaced by SO3H group.
We already know that alkanes are less reactive so lower alkanes do not undergo sulphonation however only higher branched
alkanes undergo sulphonation with fuming H2SO4 (oleum). Alkanes are very less reactive so require reagent with high reactivity at
high temperature so fuming H2SO4 (oleum) which contains dissolved SO3 works as suitable sulphonating agent.





Q: Which of the following does not undergo sulphonation ?







(v) Combustion

















Q: How many litres of air is needed
for complete combustion of 8 lit. of
CH CH ?





Answer = 100 litres
























Catalytic dehydrogenation / Hydroforming / Cyclization / Aromatisation
(vi) Catalytic dehydrogenation / Hydroforming / Cyclization / Aromatisation
When alkanes with at least six carbon atoms are heated in the presence of oxides of d-block elements e.g. Mn,Co, Th, V, Cr (good
catalyst) to form six carbocyclic aromatic compounds with higher stability.





(vii) Pyrolysis: Cracking
Decomposition of a compound by the action of heat alone is known as Pyrolysis. This word is taken from the Greek pyre = fire,
and lysis = loosing and hence to chemists it means cleavage by heat, compare hydro-lysis cleavage by water.The pyrolysis of
alkanes, particularly when petroleum is concerned, is known as cracking. In thermal cracking alkanes are simply passed through a
chamber heated to high temperature. Large alkanes are converted into smaller alkanes, alkenes, and some hydrogen. This process
yields predominantly ethylene (C2H4 ) together with other small molecules. In a modification called steam cracking, the
hydrocarbon is diluted with steam, heated for a fraction of a second to 700 - 900
o
C, and rapidly cooled. Steam cracking is of great
importance in the production of hydrocarbons as chemicals, including ehtylene, propylene, butadiene, isoprene and
cyclopentadiene. Another source of smaller hydrocarbons is hydrocracking, carried out in the presence of catalyst and hydrogen, at
high preasure and at much lower temperatures (250 - 450
o
C).
The low-molecular weight alkenes obtained from these cracking processes can be separated and purified and are the most
important raw materials for the large scale synthesis of aliphatic compounds.
Most cracking, however, are directed toward the production of fuels, not chemicals, and for this catalytic cracking is the major
process. Higher boiling petroleum fractions (typically, gas oil) are brought into contact with a finely divided silica -alumina catalyst
at 450 - 550
o
C and under slight pressure. Catalytic cracking not only increases the yield of gasoline by breaking large molecules
into smaller ones, but also improves the quality of the gasoline; this process involves carbocations and yields alkanes and alkenes
with the highly branched structures desirable in gasoline.
Through the process of alkylation some of the smaller alkanes and alkenes are converted into high-octane synthetic fuels.
Finally, by the process of catalytic reforming enormous quantities of the aliphatic hydrocarbons of petroleum are converted into
aromatic hydrocarbons which are used not only as superior fuels but as the starting materials in the synthesis of most aromat ic
compounds.
Pyrolysis follows free radical mechanism






(viii) Isomerisation :
When straight chain alkanes are heated in the presence of AlCl3 and dry HCl gas they are converted into more symetrical stable
branched chain alkane.






USES OF ALKANES