cannot be the rate-determining step for the formation of
chloroform. Moreover, since the formation of chloroform
was quenched when the excess of chlorine was reduced
by sodium sulfite, both ring cleavage and hydrolysis of
trichloromethyl compounds into chloroform cannot be rate
determining either. Hence, chlorination of the chlorinated
ketones resulting from the ring cleavage can be responsible
for the rate-determining step for the chloroform formation.
This was postulated before for chloroform formation from
resorcinol (6). As a consequence, the differences for phenols
and resorcinols with respect to chloroform formation cannot
be only explained by the higher reactivity of resorcinol
compounds with chlorine. For resorcinols, ring cleavage leads
to chlorinated keto-carboxylic acids (8), whereas for mono-
hydroxybenzenes ring cleavage leads to chlorinated ketones
only. Keto-carboxylic acids, whose enol can be stabilized by
the carboxylate groups, show a high reactivity with chlorine
and high yields of chloroform formation (29). In case of
chlorinated ketones produced from monohydroxybenzenes
such stabilization is not possible. Therefore, their rate of
chlorination would be slower than the corresponding rate of
chlorination of keto-acids. This hypothesis may explain the
slower formation of chloroform from monohydroxybenzenes
compared to meta-dihydroxybenzenes and their respective
contribution to long-term (secondary phase) and short-term
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(
primary) effects. However, it does not explain the initial fast
formation of chloroform from meta chlorinated phenols.
In literature, meta-dihydroxybenzenes have been con-
sidered as THM precursors of NOM because of their high
yield of chloroform. However, their kinetics of initial chlo-
rination and THM formation are too fast to explain the
results observed when drinking waters are chlorinated.
Monohydroxybenzenes, that show much slower initial
chlorination and chloroform formation, can be responsible
for the slow formation of THM during chlorination.
(
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The authors gratefully thank Wasserversorgung Z u¨ rich for
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in the laboratory. The authors also thank Silvio Canonica for
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