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Organic Synthesis (CH-205)

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.

C2H2 + 2Cl2 CH3COOH + Cl2 C2H5OH + HCl

FeCl3

Cl2HC

CHCl2

PCl3

CH2ClCOOH + HCl C2H5Cl + H2O

ZnCl2

Halgenating Agents
1. 2. 3. 4. Chlorine and derivatives Fluorine and derivatives Iodine and derivatives Bromine and derivatives

Organic Synthesis (CH-205)

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:

Direct Action of Chlorine Gas


C2H4 + Cl2 ClH2CCH2Cl
Cl
FeCl3

+ Cl2

+ HCl

30-100oC

Hydrochloric Acid
HC CH + HCl
HgCl2

H2C

CHCl

2C6H6 + 2HCl + O2

CuCl2 on Al2O3

2C6H5Cl + 2H2O

Organic Synthesis (CH-205)

Halogenation

Sodium Hypochlorite
NaOCL alkaline solution

Cl OH

OH

Chlorination with Phosgene (COCl2)


CHO + COCl2 CHCl3 + CO2

Chlorination with sulfuryl chloride


NH3Cl + 3SO2Cl2
C6H6 Solvent

NH3Cl Cl Cl + 3HCl + 3SO2 Cl

Chlorination with Phosphorus Chlorides: 3RCOOH + PCl3

3RCOCl + H3PO3

Design and Construction of Equipment for Halogenation


From the several experiment on pilot scale as well on large scale, it is obvious that no general rules can be formulated for the design and construction of the plant. For non-aqueous media, apparatus constructed of iron and lined plastics, such as Teflon, PVC, polyesters, epoxy resins, or with stoneware, enamels, porcelain, glass, nickel, inconel, stainless steel, hestelloy, can be used. For aqueous media like HCl or hypochloric acid the above mentioned materials are severely limited. Tantalum, zirconium and titanium are usually resistant but expensive. The plastics of variable ranges are limited due to temperature and solvent attacks. In dilute solutions wood is satisfactory. For HCl acid rubber lined steel is excellent at low temperatures even in the absence of organic solvents. It is usually desirable in the pilot laboratory stage to make measurements of potential across propose materials under operating conditions.

Organic Synthesis (CH-205)

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.