Dioxidul de clor (ClO2) in apa

La introducerea dioxidului de clor (ClO2) in apa, in functie de pH-ul si compozitia apei, pot avea
loc urmtoarele reactii:

Formarea ionului clorit (ClO2-), conform reaciei:

ClO2 (aq)

e-

ClO2
ion clorit

Formarea ionului clorat si clorit, mai ales in domeniul de pH alcalin (pH>7-8)

2 ClO2

2 OH

= H2O

ClO3-

ion clorat

ClO2-

ion clorit

Formarea clorului liber, mai ales in domeniul de pH acid (pH<6)

.
ClO2 + 2 H2 O + 4 e- = Cl +4 OHIn general, in apa potabila, datorita compozitiei complexe a apei, cu multi compusi organici si
anorganici care influenteaza mediul de reactie, la introducerea dioxidului de clor in apa se
formeaza (Werdehoff and Singer, 1987):
Ca reactie predominanata, se formeaza ionul clorit (ClO2-), circa 50-70%;
Formarea ionului clorat (ClO3-) si clor liber (Cl), circa 30%.

La doze scazute de dioxid de clor utilizate, cantitatea de clor liber care se formeaza este mica,
dar la doze mai mari (peste 1 mg/l) ea poate fi evidentiata.
Dioxidului de clor in apa este un oxidant foarte selectiv. In figura urmatoare este prezentata
selectivitatea ClO2 in comparatie cu clorul, in dezinfectia apei:

Figure 2: chlorine dioxide is more selective as an oxidizer than chlorine.

While dosing the same concentrations, the residual concentration of
chlorine dioxide is much higher with heavy pollution than the residual
concentration of chlorine.
Se observa ca, spre deosebire de clor, ClO2 nu se consuma in alte tipuri de reactii decat cele de
oxidare. Pentru diagrama clorului in apa, in prima portiune ascendenta a curbei se formeaza
cloraminele, care apoi se descompun in partea descendenta a curbei pana la disparitie (breakpoint), de unde incepe formarea clorului rezidual liber, cel eficient in dezinfectie, a doua parte
ascendenta a curbei. Curba clorului este functie de compozitia apei, mai ales de continutul de
amoniu, cu care formaza cloraminele (mono, di si tricloramine). Di si tricloraminele sunt produsi
destul de toxici. Clorul mai poate forma si compusi organici clorurati, destul de toxici, cum sunt
trihalometanii (THM), clor-fenolii etc.
Dioxidul de clor nu formeaza astfel de compusi (www.oxy.com).

Experimente in apa cu 5 mg/l acid

humic
Cloroform (ug/l)

120
100
80
60

Clor

40

dioxid de clor

20
0
0

25
timp (ore)

50

Determinarea analitic a dioxidului de clor

Methods of Detecting Residual ClO2 Content of Circulation Water

There are several kits produced by Lamotte Chemical and the Hach Company which rely
on the DPD method of detection and some of which are calibrated directly in ClO2 content.
The concentrated ClO2 stream from the generator may be analyzed by a
spectrophotometer measuring the absorption of the solution at 390 nm for free ClO2 and
the total ClO2 may be measured by the Potassium Iodide-Thiosulfate method (Standard
Methods of Analysis).
Metoda DPD (cu dietil-p-fenilendiamin) Chlorine Dioxide: A modification of the DPD
colorimetric method, which uses glycine to eliminate free chlorine interference.
ClO2 a fost evidentiat in metoda de determinare a clorului cu ortotoluidin.

Chlorine Dioxide Analysis

Residual chlorine dioxide concentrations should be determined by substantiated
methods, which are specific for chlorine dioxide. Chlorine dioxide solutions can be
analyzed by iodometric and amperometric titrations, and spectrophotometrically,
with the standard DPD (N,Ndiethyl- p-phenylenediamine) method. These methods
are described in detail in Standard Methods for the Examination of Water and
Wastewater.
4500-ClO2 B Iodometric Method
4500-ClO2 D DPD-Glycine Method
4500-ClO2 E Amperometric Method II
References
1. Standard Methods for the Examination of Water and Wastewater, APHA,
AWWA and WEF, Washington, D.C. (20th Ed., l998).