A-Chlorinations

Antimony peniachloride, SbCls. M.p. TC, b.p. 79 C (Sb or SbCIa plus CI2). Readily hydrolysed by water, forms complexes, e.g. [SbClft]". Mixed antimony(III)/(V) complexes occur as salts M2SbCl6. SbCls is used extensively as a chlorinating agent. 

H0S(CI)02. Colourless liquid m.p. -80°C, b.p. 158" C (SO3 plus HCl or H2SO4 plus PCIj or POCI3). Hydrolysed by water. Used as a chlorinating and sulphonating agent. 

This compound, which contains atoms arranged tetrahedrally around the boron atom, can readily be isolated from a mixture of dimethyl ether and boron trichloride. On occasions a chlorine atom, in spite of its high election affinity, will donate an electron pair, an example being found in the dimerisation of gaseous monomeric aluminium chloride to give the more stable Al2Clg in which each aluminium has a tetrahedral configuration ... 

Pure anhydrous aluminium chloride is a white solid at room temperature. It is composed of double molecules in which a chlorine atom attached to one aluminium atom donates a pair of electrons to the neighbouring aluminium atom thus giving each aluminium the electronic configuration of a noble gas. By doing so each aluminium takes up an approximately tetrahedral arrangement (p. 41). It is not surprising that electron pair donors are able to split the dimer to form adducts, and ether, for example, forms the adduct. 

The replacement of the —OH group by a chlorine atom (reaction 9.4) is a very general reaction of phosphorus pentachloride. For example, if concentrated sulphuric acid is written as (H0)2S02 then its reaction with phosphorus pentachloride may be written ... 

Sulphur oxide dichloride is used as a chlorinating agent in organic chemistry, for example in the preparation of acid chlorides ... 

In what way does a solution of hydrogen peroxide react with (a) chlorine water, (b) potassium permanganate solution, (c) potassium dichromate solution, (d) hydrogen sulphide 50 cm of an aqueous solution of hydrogen peroxide were treated with an excess of potassium iodide and dilute sulphuric acid the liberated iodine was titrated with 0.1 M sodium thiosulphate solution and 20.0 cm were required. Calculate the concentration of the hydrogen peroxide solution in g 1" ... 

Copper 1) chloride, bromide and cyanide were used by Sandmeyer to introduce a chlorine, a bromine atom and a cyanide group respectively into a benzene ring by addition to the phenyl diazonium salt. 

Both chloramine-T and dichloramine-T slowly liberate hypochlorous aeid in eontaet with water and are therefore employed as antiseptics the former is employed in the form of a dilute (e.g., 0-2 per eent.) aqueous solution, and the latter (which is insoluble in water) as a solution in an organic solvent, such as a chlorinated paraffin. 

TABLE M4. SUBSITTUTION EFFECTS OUALITATTVE VARIATIONS OF 7T NET CHARGE INDUCED BY THE SUBSTITUTION OF A CHLORINE OR AN AMINO GROUP (123) ... 

Transfer of an electron from a sodium atom to a chlorine atom yields a sodium cation and a chloride anion both of which have a noble gas electron configuration... 

Each chlorine atom formed m the initiation step has seven valence electrons and IS very reactive Once formed a chlorine atom abstracts a hydrogen atom from methane as shown m step 2 m Figure 4 21 Hydrogen chloride one of the isolated products from... 

Step 1 Dissociation of a chlorine molecule into two chlorine atoms... 

Step 2 Hydrogen atom abstraction from methane by a chlorine atom... 

These two products arise because m one of the propagation steps a chlorine atom may abstract a hydrogen atom from either a methyl or a methylene group of butane... 

This behavior stems from the greater stability of secondary compared with primary free radicals The transition state for the step m which a chlorine atom abstracts a hydro gen from carbon has free radical character at carbon... 

A single secondary hydrogen m butane is abstracted by a chlorine atom 3 9 times faster than a single primary hydrogen... 

In summary then the chlorination of alkanes is not very selective The various kinds of hydrogens present m a molecule (tertiary secondary and primary) differ by only a factor of 5 m the relative rate at which each reacts with a chlorine atom... 

In a process similar to that described in the previous item, the stored data can be used to identify not just a series of compounds but specific ones. For example, any compound containing a chlorine atom is obvious from its mass spectrum, since natural chlorine occurs as two isotopes, Cl and Cl, in a ratio of. 3 1. Thus its mass spectrum will have two molecular ions separated by two mass units (35 -i- 2 = 37) in an abundance ratio of 3 1. It becomes a trivial exercise for the computer to print out only those scans in which two ions are found separated by two mass units in the abundance ratio of 3 1 (Figure 36.10). This selection of only certain ion masses is called selected ion recording (SIR) or, sometimes, selected ion monitoring (SIM, an unfortunate... 

This example can be used in reverse to show the usefulness of looking for such isotopes. Suppose there were an unknown sample that had two molecular ion peaks in the ratio of 3 1 that were two mass units apart then it could reasonably be deduced that it was highly likely the unknown contained chlorine. In this case, the isotope ratio has been used to identify a chlorine-containing compound. This use of mass spectrometry is widespread in general analysis of materials, and it... 

Chlorine cannot be stored economically or moved long distances. International movements of bulk chlorine are more or less limited to movements between Canada and the United States. In 1987, chlorine moved in the form of derivatives was 3.3 million metric tons or approximately 10% of total consumption (3). Exports of ethylene dichloride, vinyl chloride monomer, poly(vinyl chloride), propylene oxide, and chlorinated solvents comprise the majority of world chlorine movement. Countries or areas with a chlorine surplus exported in the form of derivatives include Western Europe, Bra2il, USA, Saudi Arabia, and Canada. Countries with a chlorine deficit are Taiwan, Korea, Indonesia, Vene2uela, South Africa, Thailand and Japan (3). 

Zinc Sta.nna.tes, The zinc staimates are also effective synergists for flexible PVC however, as shown in Figure 4a, antimony oxide is more effective. If more chlorine such as in a chlorinated paraffin such as Cereclor is added, then the staimates become more effective and eventually outperform antimony oxide (Fig. 4b). 

---