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Use
C1-C4
Natural gas
20 60 60 100
C5-C6 C6-C7
Solvents Solvents
40 200
C5-C10
Gasoline
Nonvolatile
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.
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
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
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.
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
2CO2(g) + 3 H2O(g)
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.
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
10
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
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.
11
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
CH 3CCl 3 CH 2ClCCl 3
2.
2 CH3CH2
C4H10
3.
2 Cl
Cl 2
12
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
H C H
H C H H
1o alkyl halide
X C H
H C H H
13
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
Answer:
H3C
CH2
CH3
2o alkyl halide
1o alkyl halide