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Halogenation
Halogenation
Halogenation is a chemical reaction that incorporates a halogen atom into a molecule. The preparation of organic compounds containing halogens such as Chlorine, fluorine, Iodine, and bromine, can be done by a variety of manners. The conditions and procedures not only differ for each member of halogen family but also with the type and structure and of reacting compound. The chlorine derivatives because of the greater economy in effecting their preparation are most important of the other halogens and for the reasons are given by primary consideration. The bromine derivatives, however sometimes has certain advantages because of the greater ease in effecting the replacement of this halogen in subsequent reaction or because it possesses certain pharmaceutical or dying properties. The fluorine derivatives are as well established in the field of refrigerants and aerosol (a cloud of liquid or solid carried under high pressure and released as a spray) propellants because of their stability and low boiling points. All the halogenation reactions are fairly exothermic reactions. Halogenation may be involved the addition, substitution and replacement reaction. E.g.
FeCl3
Cl2HC
CHCl2
PCl3
ZnCl2
Halgenating Agents
1. 2. 3. 4. Chlorine and derivatives Fluorine and derivatives Iodine and derivatives Bromine and derivatives
Halogenation
Catalyst:
From experiments it becomes clear that each type of reaction may involve not only a specific halogenating agent but also a suitable catalyst or activator. Iron antimony and phosphorus, which are able to exist in low valencies, are less stable at higher valence and give up part of their halogen during process. Iodine, bromine and chlorine which are capable of forming mixed halogens are also frequently used as catalyst in halogenation. Active carbon, clay and other compounds also serves to catalyze halogenation process. Where the halogen is energized to an activated state by means of light, heat, nuclear energy, or free radical, it may then proceed to react by addition or substitution reaction without catalyst.
Chlorination:
Halogenation is almost always chlorination, for the difference in cost between chlorine and the other halogens, particularly on a molar basis, is quite substantial. In some cases, the presence of bromine (Br), iodine (I), or fluorine (F) confers additional properties to warrant manufacture. Chlorination proceeds 1. By addition to an unsaturated bond, 2. By substitution for hydrogen, or 3. By replacement of another group such as hydroxyl (OH) or sulfonic (SO3H). Light catalyzes some chlorination reactions, temperature has a profound effect, and polychlorination almost always occurs to some degree. The most important methods of chlorination are as follows:
+ Cl2
+ HCl
30-100oC
Hydrochloric Acid
HC CH + HCl
HgCl2
H2C
CHCl
2C6H6 + 2HCl + O2
CuCl2 on Al2O3
2C6H5Cl + 2H2O
Halogenation
Sodium Hypochlorite
NaOCL alkaline solution
Cl OH
OH
3RCOCl + H3PO3
Halogenation
Chlorination of Methane
Chlorine and methane (fresh and recycled) are charged in the ratio 0.6/1.0 to a reactor in which the temperature is maintained at 340 to 370oC. The reaction product contains chlorinated hydrocarbons with unreacted methane, hydrogen chloride, chlorine, and heavier chlorinated products. Secondary chlorination reactions take place at ambient temperature in a light-catalyzed reactor that converts methylene chloride to chloroform, and in a reactor that converts chloroform to carbon tetrachloride. By changing reagent ratios, temperatures, and recycling ratio, it is possible to vary the product mix somewhat to satisfy market demands. Ignition is avoided by using narrow channels and high velocities in the reactor. The chlorine conversion is total, and the methane conversion around 65 percent.