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Reactions I need to know

ALKANES Preparation
a) Fractional distillation of crude petroleum  Crude petroleum consists mainly of hydrocarbons.  Mixtures of hydrocarbons can be separated based on their boiling points. Process called fractional distillation.

Boiling range of fraction (C) Below 20

No. of carbon atoms

Use

C1-C4

Natural gas

20 60 60 100

C5-C6 C6-C7

Solvents Solvents

40 200

C5-C10

Gasoline

175 325 250 400

C12-C18 C12 and higher

Kerosene, jet fuel Gas oil, diesel

Nonvolatile

C20 and higher

Mineral oil, wax

Distillation tower at an oil refinery

Fractional distillation apparatus in the laboratory

b) Reduction of alkenes  Reduction meaning addition of hydrogen atoms.  Alkenes possess C=C double bond.  Upon reduction the C=C bond is converted to a C-C single bond.  The reagent used to carry out this reaction is hydrogen.  Reaction requires a catalyst e.g. Pd/C, Ni, Pt

CH3

CH2

CH
CH3

CH2

H2, Pd/ C

CH3

CH2

CH2
CH3

CH3

CH3

CH2

CH

CH3

H2, Pt

CH3

CH2

CH

CH2

CH3

c) Reduction of carbonyl compounds.  Carbonyl compounds are compounds with a C=O double bond.  They are aldehydes or ketones.  By completely removing the oxygen atom (reduction) an alkane can be formed.

O C H3C R + H2 N NH2 NaOH CH3 heat R= H or Alkyl or phenyl

H2N-NH2 is hydrazine The reaction is known as the Wolff-Kishner reduction

CH2 R

Example:
O C H3C CH2 + H2N CH3 NH2 NaOH CH3 heat CH2 CH2 CH3

ketones
O CH3 CH2 C H + H2N NH2 NaOH heat

CH3

CH2

CH3

aldehydes

 If a ketone is treated with hydrochloric containing amalgamated zinc the C=O is completely removed.  Amalgamated zinc is a zinc-mercury mixture.  Reaction is known as the Clemmensen reduction.

Example:
O C H3 C CH3 HCl reflux

Zn(Hg) CH3 CH2 CH3

O CH3 CH2 C CH2 CH3

Zn(Hg) HCl reflux

CH3

CH2 CH2

CH3

d) From alkyl halides.  Alkyl halides are hydrocarbons containing at least one halogen atom.  Reaction with Grignard reagents  Grignard reagents are : RMgX, X= halogen, Chlorine, Bromine, Iodine

Cl + R'MgBr

R' + MgClBr

H+

H--

H3 C

Cl

CH3MgI

Example:

CH3

CH2

Br

CH 3MgBr

CH3

CH2

CH3

+ MgBr2

CH3

CH CH2 CH3

Cl +

CH3CH2MgCl

CH3

CH CH2 CH3

CH2

CH3

+ MgCl2

Note: there is an extension of the chain at the point of reaction.

ALKANES Reactions
a) Combustion  Alkanes will burn in oxygen to form carbon dioxide and water.  This reaction is used to determine molecular formulae of alkanes.

CxHy (g) + (x + y/4) O2 (g)

Combustion Analysis

x CO2 (g) + y/2 H2O (g)

 Using Avogadro s Law:  Equal volumes of all gases, under the same conditions of temperature and pressure, contain equal numbers of molecules  And Gay-Lussac s Law:  When gases react, they do so in volumes that bear a simple ratio to one another and to the volume of the product. Example: Consider combustion of ethane

C2H6(g) + 7/2 O2(g)

2CO2(g) + 3 H2O(g)

Ratio of reacting volumes:

Ratio of products volumes:

C2H6 : O2 is 1 : 3 CO2 : H2O is 2 : 3

If the relative ratios of volumes of reactants and products can be determined then the Molecular Formula can be found.

 Method:  Fixed volume of hydrocarbon mixed with a fixed volume of oxygen and the mixture ignited.  The change in volume is determined. Note the new volume is due to steam (H2O), CO2 and excess O2.  The mixture cooled to room temperature (H2O).  The mixture passed through sodium hydroxide solution (absorbs CO2).  Remaining volume due to excess O2.

E.g. 30 mL of a hydrocarbon is mixed with 180 mL of O2 and the mixture ignited. The resulting was cooled to room temperature and the new volume determined to be 120 mL. After passing the mixture through sodium hydroxide the volume was reduced by 75%. Determine the molecular formula of this compound. Hint: Solution:      120 mL due to excess O2 and CO2 After treating with NaOH volume reduced to 30 mL. Excess O2 is 120 90 = 30 mL therefore O2 used = 180 30 = 150 mL CO2 produced is 90 mL Ratio- 30 CxHy : 150 O2 : 90 CO2 1 CxHy : 5 O2 : 3 CO2 Determine the volumes of the different reactant and products, and apply Laws.

CxHy (g) + (x + y/4) O2 (g)

x CO2 (g) + y/2 H2O (g)

 For liquid and solid hydrocarbons the combustion analysis tends not to be as accurate as you are unable to calculate the ratio with respect to the hydrocarbon.  Methods are in place to determine the percentage composition of carbon by mass.

 Once the percentage composition is known then the empirical formula can be determined.

E.g. % carbon 84.26 : % hydrogen 15.74     Divide by atomic mass: 84.26/12=7.02 ; 15.74/1=15.74 Divide by the smallest value: 7.02/7.02=1 ; 15.74/7.02=2.24 (CH2.24) Multiply by an integer to give M.F. closest an actual value. E.g. x 8 gives C8H17.92 (C8H18) or x 9 gives C9H20.14 (C9H20)

b) Free radical halogenations o Alkanes react with the first three members of the halogen family: fluorine, chlorine and bromine. o Multiproducts are obtained from this reaction. Example: reaction of methane with chlorine
H H H H C H Cl H
+ Cl2 heat or light

Cl Cl
+

C H

C H

Cl

Cl C H
+ HCl

Cl Cl
+

Cl

C Cl

Cl

 The reaction is a substitution reaction.  One group replaces another. This continues until the alkane is fully substituted (CCl4).

Mechanism free radical  Reaction is promoted by light or heat.  Reactivity of halogens increases in the order Br < Cl < F.  As with most free radical mechanisms there are three main steps:  Initiation  Propagation  Termination

Initiation

heat or light Cl Cl 2 Cl

Cl2

heat or light

2 Cl

Propagation
H Cl Step 2 CH4 + Cl + H C H HCl + CH3 H HCl + H C H H

H Step 3 H C H Cl 2 + CH3 + Cl Cl H

H C H CH3Cl + Cl Cl

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Termination (any two radicals come together)

H H C H Cl + CH3 CH3Cl + Cl H

H C H Cl

H H C H +

H C H 2 CH3 H H

H C H C2H6

H C H H

 Multi halogenated products are formed in a similar manner.

Cl Cl Step 2 CH3Cl + Cl + H C H HCl + ClCH2 H HCl + Cl C H H

Cl Step 3 H C H Cl2 + ClCH2 + Cl Cl H

Cl C H Cl + Cl

CH2Cl2 + Cl

Halogenation of higher alkanes (let us consider ethane and propane)  Halogenation of higher alkanes is also a free radical reaction.  Mono halogenation occurs but  Like methane halogenation (especially chlorination) can lead to multiple products.

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Mechanism free radical Initiation: (as before)

heat or light Cl Cl 2 Cl

Cl 2

heat or light

2 Cl

Propagation:
Cl Step 2 C2H6 + Cl HCl + C2H5 + H : CH2CH3 HCl + CH2CH3

Step 3

CH3CH2

Cl

Cl

CH3CH2Cl + Cl

Cl2 + CH3CH2

CH3CH2Cl + Cl

Steps 2 and 3 are repeated giving multiple products such as:

CH 3CH 2Cl CH 3CHCl 2

CH 3CCl 3 CH 2ClCCl 3

CHCl 2CCl 3 CCl 3CCl 3

Termination (any two radicals come together)

CH 3CH 2 1. Cl + CH 3CH 2 CH 3CH 2Cl + Cl CH3CH2 Cl

2.

2 CH3CH2

C4H10

3.

2 Cl

Cl 2

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 Halogenation of alkanes with more than 2 carbon atoms gives a mixture of mono halogenated alkyl halides.  Hydrogen atoms of higher alkanes are not identical. (1, 2, 3)  Order of reactivity -1< 2< 3  The major products can be predicted.

Initiation same as above Propagation: Looking at propane.  A toss up between abstracting a 2 hydrogen and a 1 hydrogen.  The 2 will be abstracted first.  WHY? The radical formed is more stable.  Stability of radicals - 3>2>1 Chain propagation Step
H H C H H C H H C H H + X H C H
o

H C H

H C H H + HX

1 radical

H H C H

H C H

H C H H + X H

H C H
o

H C H C H + HX H

2 radical X = halogen

Expect Two Major Products

H X C H H H C H H C H H C H H H + X2 heat H C H X = halogen
o

H C H

H C H H

1o alkyl halide

X C H

H C H H

2 alkyl halide (major)

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 Due to the high reactivity of chlorine.  There is not much discrimination between 1, 2 and 3 hydrogen.  Different mono chloroalkanes have similar yields.  Bromine is much more selective. Example:
CH3 H3C C Br CH3 H3C C H H3C CH3 + Br2 heat CH3 C H CH2 Br 3o alkyl haide >99% CH3

1o alkyl halide -trace

Exercise: Predict the products of:

CH3 H3C C H CH2 CH3 + Br2 heat

Answer:
H3C

CH3 C Br 3 alkyl halide

o

CH2

CH3

CH3 CH3 H3C C H CH2 CH3 + Br2 heat H3C C H CH Br CH3

2o alkyl halide

CH3 H2C Br C H CH2 CH3 or H3 C

CH3 C H 1o alkyl halide CH2 CH2 Br

1o alkyl halide