Bat. Res. Vol. 31, No. 2, pp.

343-345, 1997
Copyright © 1996 ElsevierScience Ltd
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RESEARCH NOTE

REMOVAL OF CHLORINE RESIDUES IN AQUEOUS

MEDIA BY METALLIC IRON

M U S T A F A O Z D E M i R and M E H M E T T U F E K C I
Department of Chemistry, Karadeniz Technical University, 61080 Trabzon, Turkey

(First received October 1995; accepted in revised form July 1996)

Abstract--In the present research, granular metallic iron was used to reduce the chlorine species into
chloride in chlorine solutions. Optimum conditions were investigated with regard to pH, particle size, and
contact period It was determined that the species of OC1- and HOCI were removed by 100% between
pH 4 and 7 w:ithin 25 min. Copyright © 1996 Elsevier Science Ltd

Key words--CMorine residues, aquatic media, removal of chlorine residues, water treatment

INTRODUCTION analytical reagent grade. Solutions of chlorine were

The problem of chlc,rine residues in aqueous media
arises from wastewater treatment plants, paper mills,
power plants, etc. (Helz and Channing, 1984; Heiz
et al., 1985). To solve this problem, several methods
were used for dechlorination of polluted water with
chlorine residues (White, 1972). Some o f the
materials used for dechlorination were granular
activated carbon, hydrogen peroxide (H202), ammo-
nia (NH3), sodium thiosulphate (Na25203), sodium
sulphite (Na2SO3), and sodium metabisulphite
(Na2S2Os) (Helz and Channing, 1984; Martin and
Shackleton, 1990). In addition, ferrous sulphate
heptahydrate (FeSO47H20) was also proposed for
removal of cMorine residues in aqueous media
(White, 1972; Iatrou and Knocke, 1992).
The methods utilising sulphur(IV) species have
some disadvantages such as p H decrease, handling
difficulties, and economic unattractiveness (Helz et
al., 1985). In the method of ammonia, chloramines
possess harmful effects on aquatic environment
(APHA, 1985). In addition to these nuisances,
methods mentioned above have other unpleasant
properties such as "obnoxious odour", "dechlorina-
tion odour", etc. (Helz and Channing, 1984).
In this study, a method for reduction of chlorine to
chloride was tested I:,y using metallic iron in chlorine
solutions. In principle, we have tried to minimise one
type of contaminant while simultaneously trying not
to increase the risk fi~r another (Montgomery, 1992).
EXPERIMENTAL
A Bausch and Lomla Spectronic 20 Spectrophotometer
(New York, U.S.A.) was used for chlorine determination.
Chemicals were from Merck (Darmsdat, Germany) and
prepared from chlorine which was obtained either by NaCl
electrolysis or commercially. The chlorine solution in
water was stirred on a temperature-controlled magnetic
stirrer at 20°C. These chlorinated water solutions in the
reactor (250 ml beaker) were analysed before and after
treatment.
Chlorine determination was carried out according to
procedure outlined in Standard Methods (APHA, 1985).
First, 0.025 N sodium thiosulphate and 0.025 N silver
nitrate solutions were prepared and standardised. Aliquots
of chlorine solutions were initially analysed by Standard
Iodometric Method I and DPD Colorimetric Method
(APHA, 1985). Then, granular metallic iron was added to
the reactor while the mixture was stirred. Ten millilitre
aliquots were taken from the reactor at various time
intervals (5, 10, 15, 20 and 25 min later) and then, they were
analysed for chlorine and chloride contends. While the
titrimetric method of silver nitrate was used for chloride
determination, both the titrimetric Iodometric Method I
and DPD Colorometric Method were used for determi-
nation of residual chlorine concentrations (APHA, 1985).
pH adjustments of chlorine solutions for Iodometric
Method were made by acetic acid. In order to obtain
working ranges of methods, dilution was made by using
Cl2-free distilled water.
The same experiments were carried out at pH 4, 5, 6, 7,
8, and 9. Temperatures of media for all samples were 20°C.
The size of granular metallic iron used in the experiments
were about 0.2-0.5 diameter. In addition, metallic iron
granules with 0.5-1 mm diameter were also tested.
RESULTS AND DISCUSSION
The possible reactions occurring in removal of
chlorine residues in aqueous media by metallic iron
which were tested in this work are considered below:
2Fe + 2HOCI + 2H20 ~ - 2Fe(OH)2
+ 2 H + + 2C1- (1)

WR 31/2--F 343
344 Research Note

Table 1. Removal of chlorine residues and determination of chloride in the range of pH

4--6. Concentrations are mg/1
[HOC1 + OCI-] CI- % Removal
Contact
time (min) pH 4 5 6 pH 4 5 6 pH 4 5 6
0 210 292 292 203 278 278 0 0 0
5 62 96.6 111 295 411 400 71 67 62
10 2.2 5.8 2.9 336 473 456 99 98 90
15 0 0 0 338 479 473 100 100 99
20 . . . . . 475 -- -- 100

2Fe(OH)2 + HOCI When granular metallic iron having a smaller size

+ H 2 0 ~ 2Fe(OH)3 + H ÷ + Cl-
The addition of these reactions give the following
total equation:
2Fe + 3HOC1 + 3H20 ~ 2Fe(OH)3
+ 3 H + + 3C1-
In higher pHs, the reactions (1) and (2) occur in the
following manner:
2Fe + 2OC1- + 2H20 ~ 2Fe(OH)2 + 2C1-
2Fe(OH)2 + OCI- + H20 ~ 2Fe(OH)3 + CI-
In this case, the addition o f reaction (4) and (5) gives
the following equation:
2Fe + 3OC1- + 3H20 ~ 2Fe(OH)3 + 3C1-
In the reactions (3) and (6), the consumptions of
HOC1 or O C I - and the formation of CI- were
determined by Standard Analytical Methods (APHA,
1985). The existence of ferric hydroxide was
qualitatively determined. The process was carried out
at optimum conditions. It was seen that the ratio of
removed chlorine residues was approximately 100%.
The results obtained are given in Tables 1 and 2. As
seen in Tables 1 and 2, when the pH was lower than
7, the reaction between granular metallic iron and
chlorine residues had a rather high rate. When the p H
was greater than 7, the reaction rate was smaller than
those of lower pHs. The fact that there was a higher
reaction rate at the low pHs arose from increasing
concentration of HOC1. At pH 7, the composition of
hypochloride solution was 75.2% HOC1 and 24.8%
O C I - , whereas the composition was 2.9% HOC1 and
97.1% O C I - at pH 9 (White, 1972).
than 0.5 m m was used, the optimum reaction rate was
(2) obtained. In addition, the ratio of metallic iron to
hypochlorite concentration was approximately 1.1-
fold of stoichiometric ratio. Furthermore, every
analysis was carried out at least three times, and the
average results were taken.
(3) Because of the adjustments of p H values for
Iodometric Method I (APHA, 1985), the accuracy
and precision of the method decreased. Therefore, the
D P D Colorimetric Method was used in parallel with
the iodometric method for the determination of
(4) chlorine residues. Results from those two methods
have rather good consistency.
(5) The contact time of granular metallic iron with
chlorinated water was approximately 25 min (max.).
It means that at pH ~< 7, the chlorine residues were
totally removed in 25 min from the beginning o f the
(6) reaction.
Both the Iodometric Method I and D P D Colori-
metric Methods totally determine species of free
chlorine (C12 + HOC1/OCI-), monochloramine
(NH2CI), dichloramine (NHCI2) and nitrogen tri-
chloride (NCI3) (APHA, 1985). Monochloramine,
dichloramine (NHC12), and nitrogen trichloride can
be separately determined by D P D Colorimetric
Method (APHA, 1988). In this study, since the
experiments were performed in nitrogen-free water,
NH2C1, NHC12, and NCI3 did not exist. Although it
is thought that metallic iron can reduce nitrogen-
combined chlorine species, further studies are
necessary to find out whether metallic iron will reduce
them.
Dechlorination is an important process in the
water treatment (Finger et al., 1985). Therefore, the
proposed economic method can easily be brought
into application as a pretreatment method in
industrial chlorinated wastewater.

Table 2. Removal of chlorine residues and determination of chloride in the range of pH

7-9. Concentrations are mg/I
[HOCI + O(21-] CI- % Removal
Contact
time (min) pH 4 5 6 pH 4 5 6 pH 4 5 6
0 360 234 234 322 225 224 0 0 0
5 175 178 181.4 448 263 266 51 24 22.5
l0 79 152 128 514 282 298 78 35 45
15 35 102 93.6 544 314 322 90 56 60
20 15 58.5 64.4 556 343 346 96 75 72.5
25 3.0 38 46.8 564 355 354 99.5 84 80
 Research Note
Disadvantages created by metallic iron method in
dechlorination were " e a r t h y - o d o u r " and a suspen-
sion from ferric hydroxide. These disadvantages can
be overcome by ]precipitation within 15-20 min
followed by filtration through an ordinary sand filter
to remove the "earthy-odour".
REFERENCES
APHA (1985) Standa.,d Methods for the Examination of
Water and Wastewater, 16th edn. Am. Pub. Health
Assoc., Washington D.C.
Finger R. E., Harringl:on D. and Paxton L. A. (1985) De-
velopment of an on-line zero chlorine residual measure-
ment and control system J. WPCF 57(11), 1068-1073.
345
Helz G. R. and Channing L. K. (1984) Dechlorination of
wastewater and cooling water. Environ. Sci. Technol.
18(2), 48A-55A.
Helz G. R., Uhler A. D. and Sugam R. (1985)
Dechlorination and trihalomethane yields. Bull. Environ.
Contain. Toxicol. 34, 497-503.
Iatrou A. and Knocke W. R. (1992) Removing chlorite
by the addition of ferrous iron. J. A W W A 84(1),
63-68.
Martin R. J. and Shackleton R. C. (1990) Comparison of
two partially activated carbon fabrics for the removal of
chlorine and other impurities from water. War. Res.
24(4), 477-484.
Montgomery J. M. (1992) Trade-offs key to D-DBP rule. J.
A W W A 84(11), 41.
White G. C. (1972) Handbook of Chlorination, pp. 342-408.
Van Nostrand Reinhold Co., New York.