War. Res. Vol. 28, No. 1, pp. 45-55, 1994 0043-1354/94 $6.00 + 0.

00
Printed in Great Britain. All rights reserved Copyright © 1993 Pergamon Press Ltd

KINETICS OF REACTIONS OF CHLORINE DIOXIDE

(OC10) IN WATER--I. RATE CONSTANTS FOR
INORGANIC AND ORGANIC COMPOUNDS
JURG HOIGNE* and HEINZ BADER
Swiss Federal Institute for Water Resources and Water Pollution Control (EAWAG), CH-8600
Diibendorf, Switzerland

(First received September 1992; accepted in revised form April 1993)

Abstract--The kinetics of chlorine dioxide consumption by a wide range of inorganic and organic
compounds, including a comprehensive series of phenols, have been determined using conventional
batch-type and stopped-flow methods. In all cases, the rate law was first-order in chlorine dioxide and
first-order in substrate. The methods allowed us to determine second-order rate constants over a range
from I0 -s to 105 M-1 s-~. Measured rate constants were high for nitrite, hydrogen peroxide, ozone, iodide,
iron (II), and, whenever the pH was not very low, for phenolic compounds, tertiary amines, and thiols.
Bromide, ammonia, structures containing olefinic C--------Cdouble bonds, aromatic hydrocarbons, primary
and secondary amines, aldehydes, ketones and carbohydrates were unreactive under conditions of water
treatment. For substrates that are weak acids, such as phenols, or weak bases, the effect of pH on the
reaction rate showed that the rate constants for the deprotonated compounds are much higher than those
for the protonated species.

Key words--chlorine dioxide, OCIO, hydrogen peroxide, ozone, iodide, nitrite, amine, phenol, phenoxide,
kinetics, rate constants, water treatment

INTRODUCTION The use of chlorine dioxide is sometimes preferred

Chlorine dioxide (CIO2) considered here is a stable
free radical, O-~CI~------O.t This chemical is applied
as an oxidant in a variety of processes including
cellulose bleaching, waste water treatment, and
drinking water oxidation or disinfection (DVGW,
1986; Hoign6 and Bader, 1982; Masschelein, 1979;
Miller et al., 1978; Overath, 1986; Rav-Acha, 1984).
In France, Belgium and Switzerland it is often ap-
plied to protect the drinking water distribution sys-
tem from microbiological recontaminations and
fouling, or to improve the taste of the water and
to decrease the formation of chloroform. In a
few places it is even used as a preoxidant for raw
water treatment.
When chlorine dioxide reacts with aqueous con-
taminants it is usually reduced to the chlorite anion
(C10£). The corresponding electron transfer reac-
tions have been expected to be comparable to those
occurring when singlet oxygen acts as an oxidant
(Tratnyek and Hoign~, 1991), or to those occurring
at a cathode.
*Author to whom all correspondence should be addressed.
tln aqueous systems, and throughout this work, chlorine
dioxide refers to the relatively stable free radical
O~--~-CI~O. This substance should not be confused with
the chlorine peroxy radical, C 1 - - O - - O ' , which is some-
times also called "chlorine dioxide", and has recently
received considerable attention due to its role as a chain
carrier in the destruction of stratospheric ozone.
to chlorine in water treatment because it produces
fewer chlorinated organic substances and no chloro-
form (see, e.g. Alfassi et al., 1986; Brauch et al., 1981;
Colclough et al., 1983; Rav-Acha and Blits, 1985;
Reinhard et al., 1979); it reacts generally as an
electron acceptor, and H atoms present in activated
organic C - H or N - H structures are thereby not
substituted by C1. In addition, in contrast to aqueous
chlorine ( H O C I / C I O - ) , its efficiency for disinfection
varies neither with pH nor in the presence of ammo-
nia, and it does not oxidize bromide. Its oxidation
reaction by direct electron transfer also differs from
that of ozonation processes which usually proceed
by addition of molecular 0 3 to olefinic double
bonds, or by oxygen atom transfer from 03 to the
substrate.
There are strong limitations for chlorine dioxide
dosage, however, because chlorine dioxide is mostly
reduced to chlorite, which is considered to be a blood
poison (see, e.g. Condie, 1986). To comply with such
restrictions, typical dosages for drinking water treat-
ment are in the 0.04-0.4 mg/l range. At such low
concentrations the lifetime of aqueous chlorine diox-
ide is highly dependent on the quality of the water
(Hoign6 and Bader, 1982). Therefore, for drinking
water treatment chlorine dioxide is generally only
applied following another preoxidation or when
especially good raw waters are available. Considering
the low dosages and subsequently low residual con-
centrations of chlorine dioxide, a good understanding

wR 28:1-o 45
46 JI.)RG HOIGNf~and HEXNZBADER
of the kinetics of chlorine dioxide reactions with
pollutants is important.
In 1984, R a v - A c h a published an extensive review
of the k n o w n reactions o f aqueous chlorine dioxide
relevant to water t r e a t m e n t a n d water disinfection. In
addition, N e t a et al. (1988) have assembled a compre-
hensive c o m p i l a t i o n o f rate constants. M a n y of these
rate constants were only measured in a preliminary
screening p r o g r a m performed in our laboratory be-
fore 1982 (Hoign6 a n d Bader, 1982). Since then,
R a v - A c h a a n d Blits (1985), R a v - A c h a a n d C h o s h e n
(1987) a n d R a v - A c h a et al. (1990) have reported
additional rate constants for the relatively slow reac-
tions of chlorine dioxide with various u n s a t u r a t e d
h y d r o c a r b o n s , including polyaromatic h y d r o c a r b o n s
a n d substituted styrenes a n d indene.
C o m p l e m e n t a r y to these recent studies we have
n o w m e a s u r e d rate constants of chlorine dioxide
reactions with additional c o m p o u n d s o f direct inter-
est for water t r e a t m e n t a n d bleaching processes,
including a series o f c o m p o u n d s which allow for
direct correlation of the kinetics with those of com-
parable oxidation processes. A further aim has been
to develop a n d test more efficient experimental tech-
niques for measuring rate constants for chlorine
dioxide reactions, which can cover the wide range of
values of interest for water treatment, and which
can be applied in conventional water t r e a t m e n t
laboratories.
In Part I we describe the experimental m e t h o d s
a n d general results. In Part II (Tratnyek a n d H o i g n t ,
1994) we will show h o w the results for substituted
phenols (phenoxide anions) can be correlated by
quantitative structure--activity relationships (QSARs)
for generalizing data a n d for evaluating possible
reaction mechanisms. These examples should help to
further test the usefulness o f Q S A R m e t h o d s for
application o f water t r e a t m e n t processes in general.
EXPERIMENTAL METHODS
Kinetic concepts
In this study, the rate law and its constants for the
following reaction have been determined:
CIO 2 + )7P--*products (1)
where P is the probe molecule (i.e. pollutant) and ~/ the
stoichiometric factor determined from the mole ratio of P
converted per ClO 2 dosed:
)7 = A[P ]/A[C102 ]. (2)
The order of reaction (1) was experimentally proven for
many systems by testing if the power n and m of the
concentrations in equation (3) would not significantly
deviate from 1.0:
-- d[ClO 2]
k[C1OE]"[P]g'. (3)
dt
To test for n and m [(2102]0 and [P]0 were varied over
wide ranges. For all kinetic measurements [P]0 was chosen
to be at least five times higher than [CIO2]0. [P]0 therefore
remained practically constant during the reaction.
The order of reaction in respect to the concentration of
chlorine dioxide, n, never significantly differed from 1.0.
Therefore the rate constant could be determined using the
pseudo-first-order relationship. For the batch-type reactors
used in these measurements, this assumption allows us to
integrate equation (3) to become:
-1n[CIO2]/[C102]0 = ko~. t = k[P]g' • t. (4)
That the value ofm would not significantly deviate from 1.0
was experimentally tested by measuring the slope m in the
relationship:
log kob~= log k + m • log[P]0 (5)
by plotting log ko~ vs log[P]0 using a series of different
probe compounds P, and different concentration ranges
for chlorine dioxide.
If P was a compound such as hydrogen peroxide or a
phenolic compound, which dissociated according to pH
controlled acid-base equilibria, the deprotonated species
(A - ) generally reacted with rate constants which were many
orders of magnitude larger than those of the protonated
species (HA). In all such eases the apparent rate constant,
ktot, which characterizes the sum of the reaction of the
two species HA and A - , was a linear function of the
composition:
kto t = (1 - 0t)kHA + ~t " k A_ = kHA + ~ ( k A_ - - kHA ). (6)
There a is the fraction of the compound occurring in the
deprotonated form ( A - ) :
[A-] l
= (7)
[A-]+[HA] 1 + 10(px'-pH)'
Depending on feasibility, kH^ and k^_ were either deter-
mined from plots of kto t v s Ctconsidering the (extrapolated)
ktot-values for ~t = 0 and 1.0, or only from plateau-values
observed for kto t a t low and high pH values.
Batch method based on u.v. absorbance
Chlorine dioxide solutions were injected using a syringe
into the solutions, present in l0 cm u.v. cells, containing the
substrate P and buffer. Rapid mixing was achieved either
by shortly operating a magnetic stirbar or by inverting the
filled and closed cell. The u.v. absorbance by CIO 2 at 358 nm
was followed as a function of time (¢oo2, 3 5 8 n m =
1200 M - t cm - ~). The absorption spectrum was occasionally
tested by recording its fine structure in the region of
350-400 nm and also by analyzing its derivative (for spectra
and derivatives see Hoign6 and Bader, 1982). To measure
low reaction rate constants ( < 1 0 M - ~ s -~) high solute
concentrations were applied. To avoid artifacts resulting
from traces of impurities, reactions were also tested using
elevated dosages of chlorine dioxide. In such cases short u.v.
cells were used.
Stopped-flow method
A stopped-flow method was used for more recent
measurements on an extended series of compounds: sol-
utions of chlorine dioxide and probes, both containing the
appropriate phosphate buffer solutions (50 mM) to achieve
a uniform pH, were stored in two automated plug-type
burettes. These reactants were mixed by passing them into
a commercial u.v.-through-flow cell (optical path length =
5era, vol = 3ml) through short connecting PVC tubes
(i.d. = 1.5 mm). Flow rates were set for 100 and 150 ml/min,
respectively. After a flushing time of a few seconds, both
pumps were stopped simultaneously and the absorbance
(358 nm) was recorded vs time, until values decreased to
10%, and typically to 1 or 0.5%, of their initial value. Data
were recorded about three times per half-life, or at least
every 20 s, and were transmitted on-line to a computer,
 Chlorine dioxide---I. Rate constants
where the absorbance was converted into decadic log units.
To choose a best baseline absorption-value, or "infinity
level", variations due to light absorption by species other
than chlorine dioxide had to be accounted for. Such absorp-
tions may be due to the substrates or to impurities or even
to some reaction products. Based on earlier experience, we
could assume (zero hypothesis) that all tested kinetics were
pseudo-first-order, in respect to chlorine dioxide residuals,
and a correction for the baseline of the absorbance was
calculated by an iterative process set for optimizing the
linearity of the regression. To avoid negative baseline values
and large corrections, a best estimate for the baseline
adjustment was preset using blanks or results from prelimi-
nary tests on paired solutions in which the reaction was
allowed to progress to near completeness. Unless specified,
the determined slope of the plot of the absorbance vs time
was based on at least 10 data pairs which were equally
spaced and which resulted in a correlation value r > 0.99.
The quality of the regression was also assessed by visual
inspection. Half-life times as short as 0.5 s could still be
determined with errors of less than 10%. For examples see
Fig. 1.
Batch-type method using the indigo reagent
A few compounds, such as nitrophenol, and a few
oxidation products, produced significant interference with
the absorbance of chlorine dioxide at 358 nm. For such
cases the indigo method (Hoign6 and Bader, 1980) was
applied to determine the chlorine dioxide residual. The
overall procedure for the measurements was similar to that
used in ozonation kinetics (Hoign6 and Bader, 1983a): the
chlorine dioxide solution was injected into a series of about
12 open 30 ml flasks which served as batch-type "reactors"
containing the solution of the reactants. After a reaction
time of 12-200 s the reaction occurring in the individual
flasks was quenched in sequence by injecting an appropriate
dose of the indigo reagent. The samples were stirred with
'%,T
1 sulfate with 0.02 M chlorite. The chlorine dioxide formed
0.4
o.2(
0.1
0,04 .3 mM
0.0~ ~ 2 ~ mM
0.01
~[1"120 ~ = 0.3 mM
0.00, I ~ 0.0
0.0021 i I l I i I I A
0 0.8 1.6 2.4
I I I I e, 0
i I i I
o ~o ao I~o 160 2~o 240 " "
seconds
Fig. 1. Examples of results for testing the stopped-flow
method of measuring [C102] vs time. The different time
scales applied demonstrate the dynamic range of the
method.
47
stirbars only during injection of the solutions. Samples of
the reacted solutions were transferred into a spectropho-
tometer cell and the chlorine dioxide residual was deter-
mined from the decoloration of the indigo reagent observed
at 600nm (Hoign~ and Bader, 1980, 1983). Although the
decoloration of the indigo reagent occurs with stoichio-
metric factors varying somewhat with conditions, specific
calibrations allowed for good quantification of the pseudo-
first-order kinetics. Cross-tests for comparing with the direct
u.v. method have given consistent results.
Analytical methods for measuring residual concentration of
substrates
For measuring stoichiometric factors, also the residual
concentrations of the substrates had to be quantified. Hy-
drogen peroxide was thereby determined using the DPD
method (Bader et al., 1988). Nitrite was analyzed using the
classical sulfanilamide method. Concentrations of phenols
were analyzed by HPLC (Tratnyek and Hoign~, 1991) or,
after extraction with t-butylmethyletber, by GC analysis
using a 15 m glass capillary (d = 0.3 mm) coated with 0.8%
OV-1 and connected to a flame ionization detector.
In some samples the chlorine and chloride formations
were measured by ion chromatography using an AS 9
Dionex column and a chemical suppressed conductivity
detection.
Determinations of pH and pK~ values
The pH was measured with a glass micro electrode,
calibrated with standard buffers in the range of pH 4-9
(Titrisol Merk). For a few substituted phenols, no pK,
values were found in the literature which were representa-
tive of the conditions applied in this study. In such cases,
the pKa values were experimentally determined from the
pH dependent shift of the u.v. spectra observed at the
same buffer concentration and temperature as applied for
the determination of rate constants (Hoign~ and Bader,
1983b).
Chemicals
Chlorine dioxide was prepared by reacting 0.1 M peroxo-
within hours, and was transferred with a stream of nitrogen
into a washing bottle containing ice-cooled distilled water,
following a prescription by Degussa, Germany (1980).
These stock solutions thereby formed were kept at 5°C for
to 4 months. The concentration of these solutions was in the
range of 80-100 mM. It was determined before each use by
measuring the u.v. absorption at 358 nm of solutions diluted
to about 0.5 mM. For these determinations an E-value at
358 nm of 1200 M -~ cm -~ was used (Granstrom and Lee,
1958). The analysis was preliminarily tested by iodometric
calibrations. Even after extended storage no chlorite and
chlorine were found. Caution: chlorine dioxide present in the
gas-phase equilibrated with an aqueous solution containing
> g g/I of chlorine dioxide ( > 30°C) is explosive (see, e.g.
DVGW, 1986; Masschelein, 1979).
For kinetic and stoichiometric measurements, the pH
was usually buffered by mixing stock-solutions of 0.5 M
Na2HPO 4 and NaH2PO4, to yield the desired pH upon
10-fold dilution. For some pH adjustments sodium hydrox-
ide or phosphoric acid was added. For experiments at
pH <2.5 the pH was only controlled by phosphoric
acid.
Most other reagents were of the purest grade available
from common commercial suppliers. A few chemicals such
as 3- and 4-methoxyphenol, the dimethylphenols, all cresol
isomers and furfuryl alcohol were only received as purum
grade and had to be vacuum distilled under nitrogen.
4-t-butylphenol and 2,4,6-trichlorophenol were sublimated
using about 12 mm vacuum and 50°C. Dimethylfuran was
48 J()RG HOIGNI~ and HEINZ BADER

purified by preparative chromatography. The purified prod-

ucts were colorless. The quality of the purification was tested (s-1) 1
by determinations of the u.v. spectra and, whenever feasible, phenolate
by melting points. From all reactants the visible-u.v, spec- 0.4 pH= 3,-7/~ /
trum was run also to explore possible interactions with the
chlorine dioxide determination.
All solutions were made using either double distilled
water or distilled water additionally treated with a Nano-
pure Sybron System from Barnstead (Boston, U.S.A.), 0.1 J N O ~ "
where deionized water passes through a granular activated
carbon filter. Cross-tests showed no variations of kinetic
0.04
results due to different types of waters used.

Instrumentation
The absorbances were measured in thermostated 1-10 cm 00,
cells or using a 5 cm flow-through cell thermostated at 23°C
in an Uvikon UV 810 spectrophotometer (Kontron AG). 0~( I I I I '
The spectrophotometer was set for a bandwidth of 2 nm and O. -10 4.10-10 10-9 4.10-9 10.8 4-10-6 M
the time constant for absorption measurement of 0.2 s. For [phenolate]
I I I I I I
fast stop-flow conditions the temperature remained that of 10-8 4.10-8 10-7 4.10-7 10-6 4.10-6 I~1
the reagents stored at room temperatures (22-24°C). For [HO~I
experiments in which temperature effects were measured, the I I I I I I I~

temperature was also controlled in the stock solutions using
thermostated water baths.
For on-line data evaluation, the u.v. spectrophotometer
was connected to a Hewlett-Packard computer HP-9816 by
a serial interface RS 232-C.
RESULTS
Order o f reaction
Figure 1 shows a few examples of typical declines
of the log of the absorbance at 2 = 358 nm vs time
when the reactant P was present in excess of added
chlorine dioxide [cf. reaction (4)]. The evaluated
measurements covered half-life values for chlorine
dioxide ranging from 0.6 to 60 s. Additional results
using the manual method have been given before
(Hoign6 and Bader, 1982). No substrates gave a
significant deviation from linear first-order plots. In
addition, the plots of the kobs vs [P]0, in a log-log
diagram always resulted in straight lines [cf. equation
(5)]. Four examples covering two orders of magni-
tude with respect to pseudo-first-order rate constants
and six orders of magnitude considering the concen-
tration of the reacting species are presented in Fig. 2.
The slopes m of such plots never deviated signifi-
cantly from 1.0. The variances between series have
been used for estimating error ranges of the rate
constants. Such errors seem generally low when
relating to the wide range of orders of magnitude
covered by the considered rate constants. The vari-
ances about the regression for the measurements
using phenols or hydrogen peroxide were primarily
due to uncertainties in pH values: variances became
significantly lower for cases where speciation did not
vary with pH.
Temperature dependence o f reaction-rate constant
Because some of the measurements were made at
ambient laboratory temperatures, the sensitivity of
the rate constants with respect to changes in tem-
perature was determined for a couple of substrates.
Arrhenius plots for nitrite and 4-cresol determined
10.5 4.10-5 10.4 4.10-4 10-3 4.10-3
INO,2]
().01 0.=04 0.'1 0.4 1 4 ~1
IFFA]
Fig. 2. Examples of tests for the determination of the order
of reaction (m) with respect to [P]0 given by equation (5).
The concentrations of phenolate and HO 2 varied by chang-
ing both the concentration and the pH. For phenolate the
pH was varied from 3 to 7 and for HO2- from 5 to II.
Phenols have also been measured by the manual method
(A) for comparison.
from 2 to 30°C gave good linear relationships.
The apparent rate constants increased 4 and 7% per
°C, respectively. Apparent activation energies,
not corrected for the temperature dependence of
the pK a values, are 37 + 4 k J / m o l for nitrite and
52 + 5 kJ/mol for 4-cresol.
Dependency o f reaction rate constants on p H and
presence o f chlorite
Rate constants for substrates not changing specia-
tion with pH (e.g. furfuryl alcohol, or 2,4,-hexadiene-
1-ol or nitrite above pH 4) only showed a small
increase with pH ( < 3%/pH). However, the k~ot-val-
ues of all those compounds exhibiting a pH depen-
dent speciation (phenols, amines, hydrogen peroxide)
showed a pH effect which reflected the speciations
such as predicted by equation (6). Examples for
hydrogen peroxide, phenol, 2-methylphenol and 2-
hydroxy benzoic acid are presented in Figs 3 A ~ . In
Fig. 4 the corresponding total second-order rate
constants, ktot, have been plotted vs ~, the degree of
dissociation [see equation (6)]. For all series of
measurements linear relationships were found in
agreement with those predicted by equations (6)
and (7).
Measurements of reaction rate constants for phe-
nol and 4-cresol have been repeated in solutions
containing chlorite concentration corresponding to
the initial concentration of chlorine dioxide. No
significant effect of this addition has been found.
 Chlorine dioxide--I. Rate constants 49

(M-l,rl)
® ,,.".':-',I® ,:',T ®
(M'I.s-I)
104 io o

lO2
m
1oe

lO4
__

r,,/am~n p . r o x ~ /
i

'il
106

1
I ~

0.01
1

6 8 I0 12 14 I~H
:f .I /Zf

i! , i J i
® ,0- ,0- ,0-2

(M-l.rl) .:_.7:.:-_- - -
Fig. 4. Examples of determinations of second-order rate
constants for the deprotonated species made by extrapolat-
ing the ktot values vs a---,1.00.

2 ~ 1 ,;:,~,/
~4'=C~ ..s./I
/r/
(Co= 50/~M) at pH 4.7 and 9 chlorine dioxide was
consumed about 2.1 + 0.1 times faster than the con-
centration of phenols was depleted. Correspondingly,
I mol of hydrogen peroxide (pH = 6) consumed
2.5 mol chlorine dioxide (Co = 0--300/zM) and 1 mol
,i,.../r , , , , , nitrite (Co = I mM, pH = 6) reduced 2.1 mol chlorine
2 4 6 8 10 12 ;H dioxide. All of these ~/values vary somewhat with the
ratio of chlorine dioxide to substrate.
ktot
(M'L4-1)
©
Kinetic data
The determined rate constants including exper-
J
imental parameters are compiled in Table 1 for
104 2-hydroxybenzoica c ~ j ~
inorganic compounds, in Table 2 for substituted
, z phenols, in Table 3 for a few organic nitrogen
lo 2 _ ~ . , , - - -
and sulfur compounds and in Table 4 for further
TpK1
I I I I I I I I i I - miscellaneous organic compounds. For an easier
4 6 8 I0 12 pH
comparison of the rate data, also an interpolated
Fig. 3. Examples of the measurement of second-order or extrapolated ktot-value has been included for
reaction-rate constants, ktot. A--Hydrogen peroxide; B--
2-methyl phenol; C--2-hydroxybenzoic acid. pH 8. This entry might be of interest for water
treatment.

Stoichiometric factors Error-ranges of kinetic data and accuracy

In a few cases, corresponding stoichiometric fac- The error-ranges listed in Tables 1-4 are larger
tors have been determined. In the case of 2,4,6- than those calculated by conventional statistics
trimethylphenol (Co = 4/~M) or in case of phenol based on means or regressions within series. The

Table 1. Reaction-rate constants for consumption of chlorine dioxide by P = inorganic compounds (AH + A ) [CIO2]0 = 6-250 g M
( < 0 . 2 x [Pl0)
[P]0 pH k8^ kA k,o, for pH = 8
Solute: H A or A - pK a (mM) range Method* (M Is k) (M Is t) Nt ( M t s i)
Water ( H 2 0 / O H - ) 14 3-10 <<0.05 <<0.05
Hydrogen peroxide (H202/HO f ) 11.7 00.3-20 5-11 Auto <0.1 (1.3 + 0.2)- l05 40 30 _+ 3
Bromide (Br ) 800 7 Manual and < 10 -4 8 <0.05
deriv.
Iodide (I - ) 0.03 9/10 Manual 1400 + 200 2 1400 _+ 200
Ammonia ( N H f / N H 3 ) 9.3 1000 9 Manual < 10 -6 < 10 -6 4 < 10 6
Cyanide (HCN/CN ) 9.3 0.3-1 2/6.3-7.5 Manual < 10 -s 8000 _+ 2000 10 400 _ 100
Nitric acid/nitrite ( H N O 2 / N O : ) 3.1 3 2-10 Auto 113 _+ 3 II 113
lron(II) (Fe2+/FeOH + ) 0.03-0.1 2-3 Manual 3000 _+ 5005 16
(300 nm)
Manganese (Mn2+/MnOH ÷ ) 10.6 20 2 Manual <0.1 ~2.107§ 2 5. 104§
Ozone (03) -- 0.0.%0.2 2~ Manual 1370 + 50 9 1400
*Method used in most extended series: auto--automated stopped-flow method; m a n u a l ~ e s c r i b e d in text *'as batch-type method; deriv--u.v.
absorhance quantified relatively by detecting the derivative of the absorbance.
i N - - n u m b e r of measured rate curves.
$Second-order rate-constant also tested for oxidation of Fe(ll) to Fe(Ill) based on A;. = 330 nm = f (time).
§Both extrapolation of the value from Benschoten et al. (1992) for pH 6-8 and regression including the value for pH 2 from our study give
the k ( M n O H +) = 2- 107M - ~ - s - L
50 JI]RG HOIGNI~ a n d HEINZ BADER

Table 2. Reaction-rate constants for consumption of chlorine dioxide by P = phenolic compounds (P = A r O H + ArO ) [CIO2]0 = 6-250/~M
( < 0.2 x [P]0)
ktot for
[ArOH]tot pH k^~o. k^,o- pH = 8
Solute: A r O H pK, (raM) range Method:~ ( M - i s t) ( M - i s i) N§ ( M - i s i)
Phenol 10.0 0.03-50 1.2-6.7 Auto 0.4 + 0.1 ( 4 . 9 + 0 . 5 ) . 107 120¶1 0.5.106
4-acetylphenol 8.1 0.03-10 2-6.5 Auto <0.5 (8 + 2)" 105 40 1.4- l03
4-tert butylphenol 10.2 0.3-1.5 2 7 Auto I I -+ 3 (1.5+0.1).108 60 0.9- 106
2-hydroxybenzoic acid (salicylic acid) 3.0? 3 1.5-6 Auto < I (46 _+ 3) 38 46
2-hydroxybenzoate (salicylate) 13.6 0.3 3 7-10.5 Auto <46 (6 _+ 1)" I 07 34 1.5- 103
4-hydroxybenzoate 9.2 0.2-40 2 6 Manual <40 ( 6 + 2 ) . I06 38 3.106
2-chlorophenol 8.5 0.07-0.17 2-5 Manual 1.5 (3.5 + 0.5)" 107 I1 11 - 106
4-chlorophenol 9.4 0.08-17 2-5 Manual <2 (3.5 -+ 0.7)" 107 20 1.4.106
2,4-dichlorophenol 7.8* 0.03-0.3 2-5 Auto ~<0.6 (2.2 + 0.3)' 107 14 10. 106
2,4,6-trichlorophenol 6.2* 0.03-0.3 2.2-4 Auto < 800 (5.3 -+ 0.5)" I& 32 5.3.106
Pentachlorophenol 4.7 0.03 2-2.5 Auto -- ( 1 . 4 + 0 . 2 ) ' 103 18 1.4- 103
4-ethylphenol 10.3" 0.054).2 2-5.5 Auto 50 + 10 (8.0 -+ 0.4)" l0 s 8 4.0.106
2-hydroxyphenol (catechol) 9.1 0.03-0.3 2-4.5 Auto <5000 (2 + l)" 109 46 158. 106
3-hydroxyphenol (resorcinol) 9.2 0.03-0.6 2.5-6 Auto 40 -+ 10 (4.8 -+ 0.5)" 107 46 3.0 106
2-methoxyphenol 9.9 0.03-0.3 3 5.5 Auto 1000 + 100 ( I . 2 + 0 . 1 ) ' 109 28 1.5 106
4-methoxyphenol 10.2 0.03 3-5.5 Auto (2.5 + 0.2) .104 ( 1 . 7 + 0 . 6 ) " 109 28 I.I 106
2-methoxy-4-formyl (vanilline) 7.7* 0.03 2 2.6 Manual -- (1.8 + 0.3)" l0 s 4 5.0 103
2-methylphenol (o-cresol) 10.3 0.03-1.5 2.5-6 Auto 16 + 4 (4.4 _+ 0.4)" l0 s 52 2.2 106
3-methylphenol (m-cresol) 10.1 0.03-1.5 2.5-6 Auto <4 (I.0 _+ 1.0)' 108 52 0.8 106
4-methylphenol (p-cresol) 10.3 0.03-1.5 2.5-6 Auto 50 + 10 (5.2 -+ 0.3)" 108 42 2.6 106
2,4-dimethylphenol 10.6 0.03-0.3 2-6 Manual 900 -+ 200 (2.1 + 0.1)' 109 22 5.3 106
2,5-dimethylphenol 10.2 0.03~).3 2-6 Manual 100 -+ 10 (6.8 + 0.6)" l0 s 33 4.3 106
2,4,6-trimethylphenol (mesitol) 10.9 0.03 2-6 Auto 3900 -+ 200 (4 + 1) • 109 37 5.0 106
4-nitrophenol 7.2 0.2-1.5 2.5-8 Indigo 0.14 _+ 0.04 (4 + 1)' 103 12 1.4 l0 s
4-sulfonatophenol 8.8 0.03-5 3-7 Auto < 1 (I.0 + 0.1)" 106 42 0.15' 106
*Own determination; ?value for the carboxyl group; +method used: see Table 1; §N = number of measured rate curves; ¶lincluding
measurements in presence of 2 m M chlorite.

Table 3. Screening experiments for measuring reaction-rate constants for consumption of chlorine dioxide by P = organic nitrogen and sulfur
compounds (P = HB ÷ + B)
ktot for
[P]0 pH ka, + ka pH = 8
Solute: BH + or B pK a (mM) range Method* (M is i) (M-Is i) Nf (M i s - i )
Urea 2 9 Manual < 10 6 3 < 10 +
Methylamine 10.6 16-70 7.4-10.5 Manual < 10 2 ~< 10 6 <0.1
Dimethylamine 10.7 0.3-5.0 6.8-9.3 Manual ~<0.4 (5 + 2)- 102 6 < 1
Trimethylamine 9.7 0.1-80 5.7-8.4 Manual < 1 (6 _+ 2). 10+:~ 7 102
Glycine 9.9 0.4 8 Manual < 10 -5 < I 3 1 < 10 s
~-L-alanine 2.3/9.9 8-10 Manual <10 5 <10 2 4
L-cysteine 2/8.4/10.3 6.3 Manual < 10 2
lmidazol 7.1 540 5/6 <10 4 <10 4 2 <10 +
2-methyl-I propane thiol 11.2 0.3-3 2-5.5 Manual 1 (7.5 + 0.8). 108 8 ~ 5" 105
D-L-cysteine 1.7/2.3/7.9/9.9 Var. 8.5 Manual -- 7 _+ I 4 6+ 1
*Method used: see Table I; ?N = number of measured rate curves; :~added chlorine (10 # M ) decreased apparent rate constant.

Table 4. Screening experiments for measuring reaction-rate constants for consumption of chlorine dioxide by P = miscellaneous organic
compounds
[P]tot pH kHa kA k,o' for pH = 8
Solute pK, (mM) range Method* (M's ') (M's *) N? (M's ')
Cyclohexene -- 1/3 5/7 Manual ~0.03 2 ~0.03
I-hexene-3-ol -- 2 8 Manual < 10 2 I < l0 2
2,4-hexadiene-l-ol -- 3 2 10 Manual 8.5 10 36 8.5
Acetone -- 5000 6 Manual < l0 5 -- I < l0 s
Methylpropylketone -- 6 6 Manual < 3 " l0 5 __ I <10 ~
Dimedone 5.2 0.2 2-5 Manual ~ 2.104 7 --
2,5-dimethyl furane -- 0.3-3 2-10 Manual ~ 120 6 ~ 120
Furfuryl alcohol -- 300-3000 3-9 Manual 0.37 _+ 0.02 11 0.37
Maleic acid 1.8/6.1 44 7 Manual -- < 10 5 I < 10 5
Fumaric acid 3.0/4.4 44 3/6 Manual < 10 5 < 10 5 2 < 10 5
2-dimethylbenzene (o-xylene) -- 0.4 2 Manual < 10 5 I < 10 5
1,3,5-trimethylbenzene (mesitylene) -- 0.1 8 Manual < 10 5 I < 10 5
Vinyl benzene (styrene) -- 1-2 5 Manual < 5 . 10 5 2 < 5 . 10 5
3-phenyl-l-propene (allyl benzene) -- 0.1-1 2-7 Manual ~ 10 3 3 ~ 10 3
Naphthalene -- 0.2 5 Manual <0.3 5 <0.3
Anisole -- 1.5 5 Manual <2.10 3 5 < 2 - 10
Benzaldehyde -- 30 8 Manual < 3 . 10 4 _ 1 <3.10 4
4-benzoquinone -- 1 7 Manual < 5 . 10 3 __ I < 5 " 10 3
Phthalic acid 3.0/5.4 400 6 Manual < 10 3 3 < 10 3
lndigotrisulfonate 0.004 7 Manual >2.5 • 105 2 > 2 . 5 - 105
*Method used: see Table I; f N = number of measured rate curves.
 Chlorine dioxide-I. Rate constants 51

error-range estimates were based on estimates con-
sidering reproducibility between series of exper-
iments performed with different sets of solutions and
using somewhat varied experimental conditions. In
cases where rate-data for dissociated species had to be
calculated by extrapolating the k,,, value for tl + 1.O,
the k values are based on the pK, value given in the
tables. In such cases the accuracy of the results is
predominantly controlled by the accuracy with which
the exponent of the difference between the pH-scale
and the pK, value is known. If, for example, the
difference between the pH scale and the pK, value
has a variance of 0.1 units, the accuracy of the
extrapolated rate constant is only 25%.
DlSCUSSION
Order of reaction
For all substrates and all over the concentrations
tested, the kinetics were first-order in both the
chlorine dioxide and the substrate concentration.
Therefore the reaction kinetics of chlorine dioxide
can be conveniently characterized by second-order
reaction-rate constants.

hoi
0
A t1n
M-W + P
W-

102

J’
0,
10’
102
N9’
ldl -7d

0
1

6 8 10 6 8 10
PH PH

ktot
M’1.S’1
102
104t .

2 4 6 8 10
PH
Fig. 5. Summary of reaction-rate constants and halftime values of different compounds in presence of
chlorine dioxide vs pH. Assumptions for t,/? scale: [ClO,] = 1p M ( = 67 y g/l); [p] <<[CIO,],,,,,,, q = I .O;
A-Inorganic compounds; B-phenols; C-organic compounds except N- and S-compounds; D-organic
N- and S-compounds.
52 JORG HOIGNI~and HEINZBADER
p H dependency of reactivity
In cases where the substrate's speciation does not
vary, the reactivity of chlorine dioxide does not
significantly change from pH 2 to 10.5. This is
in agreement with the chemical structure of the
aqueous chlorine dioxide which does not change
with pH.
Comparison of rate constants and half-time values for
different substrates
For easier instruction and comparison, second-
order reaction-rate constants for representative
inorganic and organic compounds selected from
Tables 1~, are visualized in Figs 5A-D as a func-
tion of pH (left-hand scale). On the right-hand of
the figures a time scale informs about the corre-
sponding half-time values within which substrates
P become oxidized when in the presence of a typical
concentration of chlorine dioxide. This scale has
been adjusted to the scale of rate constants by
considering that:
t~,2 = 0.69/(~/ • ktot • [CIO~])
and assuming a constant chlorine dioxide concen-
tration of 1 # M (67/~g/1). A concentration in this
order would be typically applied for protecting drink-
ing water distribution systems (range of typical
dosages: 30-400 pg/1). For accounting for higher or
lower concentrations of chlorine dioxide, such as used
for other process-aims, the logarithmic right-hand
scale would have to be shifted upwards or downwards
correspondingly to equation (8). For simplicity all
data are based on the rate of chlorine dioxide con-
sumption, i.e. all r/ values were assumed to be 1.0.
This would typically deviate from real values by a
factor of two. However, a corresponding correction
would not significantly show up on the highly com-
pressed logarithmic scales applied for these graphical
overviews.
Hydrogen peroxide reacts with chlorine dioxide
predominantly when dissociated to HO:-. Extrapol-
ation, as performed in Figs 3A and 4A, shows that the
second-order reaction rate constant for the depletion
of chlorine dioxide by HO:- is 1.3 x 105 M -~ s -I and
the low lying plateau value at low pH values reflects
the unreactive nature of non-dissociated H202
(k < 0. I M - J s- ~). The rate constant determined here
for HO:- is twice as high as that quoted in the
compilation of Neta et al. (1988) which was deduced
from a graph given by Eriksen et al. (1981). However,
the value by Eriksen et al. was based on measurements
of the rate of C10: depletion observed upon pulse
radiolysis and following the kinetics by spectroscopy in
the millisecond range. During this short time period
only the primary oxidation leading from HO2- to
HO2/O2- was detected. This reaction would have an r/
value of 1.0. In contrast, our measurements performed
in the time range of seconds also included subsequent
reactions of HO~/O2- with further C102. Including
this, the apparent r/ value of the overall reaction
becomes 0.5 (cf. Table l).
Accounting for this difference in measurements, the
agreement between our value and that given by
Eriksen et al. is therefore excellent.
Inserting the determined rate constants and the
proper pKa value for hydrogen peroxide in equations
(6) and (7), we calculate a ktot value of 400 M-1 s -
for hydrogen peroxide in water at pH 8 (see Table l).
This means that a steady-state concentration of
hydrogen peroxide of only l0/~M (0.34 mg/l) would
reduce small concentrations of chlorine dioxide
within a half-life of 170s. Correspondingly, long-
lasting consumption of residual chlorine dioxide has
been reported by waterworks, which for disinfection,
flushed some distribution lines with hydrogen per-
oxide solutions. Similar problems must be expected
when drinking water is pretreated using combinations
of ozone with hydrogen peroxide or u.v.: both pro-
cesses may result in a hydrogen peroxide residual
(Hoignr, 1988).
Bromide is not oxidized by chlorine dioxide (cf.
(8) entry in Table 1). Therefore, water treatment with
chlorine dioxide will not transform bromide into
hypobromite, and it neither gives rise to the for-
mation of bromoform nor bromate. This is an
important difference to the case where chlorine or
ozone are used as oxidants (von Gunten and Hoign&
1992).
Iodide, in contrast to bromide, is easily oxidized by
chlorine dioxide. The rate constant, as measured in a
screening experiment was 1400 M-~ s-~ (see Table 1).
This value only approximates the value determined in
an extended and critical study by Fukutomi and
Gordon (1967) of 2950M I s-~ (25°C), for the for-
mation of an intermediate (C1021 ), which slowly
decomposes. Despite this, both results indicate that
the oxidation of iodide requires a few hundred sec-
onds when chlorine dioxide concentration is in the
micromolar range (also cf. Fig. 5A).
Ammonia, often present in raw waters, does not
consume chlorine dioxide. In contrast to chlorine,
chlorine dioxide can therefore also be considered as
a virucide when ammonia is present. This might be
one of the historical reasons why chlorine dioxide has
been adopted as a disinfectant by some treatment
plants using well oxidized waters but which contain
changing ammonia concentrations.
Nitrite is easily oxidized by chlorine dioxide.
Nitrite may occur in waters as a metabolite pro-
duced by microbiological denitrification, and by
other processes occurring during water treatment
or transport. Its presence at a concentration of
2 # M , a limit given by some drinking water
ordinances (Trinkwasserverordnung FRG, 1990;
Schweizerisches Lebensmittelbuch, 1986) would
deplete most of the typically dosed chlorine diox-
ide within a few minutes (cf. Fig. 5A). It must be
kept in mind that chlorite formed in this reaction
is considered of comparable toxicity to nitrite.
 Chlorine dioxide---I. Rate constants
Iron (II) and manganese (II) ions, such as present
in reduced groundwaters and in the hypolimnion of
stratified lakes and reservoirs, also consume chlor-
ine dioxide. Kinetic values measured for iron (II) at
low pH values could not be extrapolated to pH 8;
oxidation of free iron (II) by oxygen leads to the
formation of a colloidal iron (IlI)-oxide which would
interfere with the solution-phase oxidation. In case
of manganese (II) van Benschoten et al. (1992) have
been able to distinguish between the different reac-
tion pathways and they have determined a rate
constant of 50,000 M -~ s -t for the solution-phase
reaction at pH 8. This constant increased consider-
ably as a function of pH when measured between
pH 6 and 8. We therefore assume that MnOH ÷
rather than Mn 2÷ controls the total rate of reaction.
Using this assumption, the values listed in Table 1
for pH 2 are in good agreement with the pH-depen-
dent fraction of the reactive species. In addition,
van Benschoten et aL have also accounted for
interferences by colloidal manganeous phase. The
data for the free ions do not however provide
direct information on the rate constants that should
be used for real drinking waters, where part of
the manganese is masked by dissolved organic
material.
Ozone easily oxidizes chlorite and chlorine dioxide
to chlorate. The results agree with those measured by
Klaning et al. (1985) for solutions containing a large
stoichoimetric excess of chlorine dioxide. Because
health officers consider chlorate to be of similar
toxicity as chlorite or chlorine dioxide, ozonation
should not be considered for eliminating an excess of
chlorite and chlorine dioxide.
Phenolic compounds, as shown in Table 2, react
quickly with chlorine dioxide when present as phe-
noxide anions (i.e. as the deprotonated species).
Because these dissociated forms often react a million
times faster than the non-dissociated species, their
fraction already begins to control the total reaction
rate constant [see equation (6)], when pH values are
less than 6 units below the pKa of the corresponding
phenol. Correspondingly, over the entire pH range of
interest for water treatment, the apparent total reac-
tion-rate constant increases for most types of phenols
by a factor of 10 per pH increment (also compare
entries in Figs 3B and 5B). The fact that the specific
rate constants of the non-dissociated phenols are a
million times smaller than those of the dissociated
species causes their values to be obscured, except at
very low pH values where the fraction of dissociated
species becomes negligible. But at such low pH values
(pH < 2) interferences by changing ionic strength and
other irregularities may occur.
The effects of substituents on the reaction-rate
constants of the phenols are large. Only a more
sophisticated analysis of the rate data, such as pre-
sented in Part II (Tratnyek and Hoignr, 1993), has
allowed for interpretation and generalization of the
results and comparison with literature values.
53
Because chlorine dioxide reacts highly selectively
with phenols, it has become an accepted oxidant
for polishing drinking waters where a risk for pol-
lutions with phenols has to be accounted for, and
where consumers reject waters that contain a taste
of chlorophenols. However, reaction products are
known to have quinoid structures, and it has been
reported that retarded recoloration may occur when
waters colored by humic substances are being
bleached by chlorine dioxide.
Organic nitrogen and sulfur compounds have only
been tested here with an exploratory series to learn
how to interpret for water treatment the data
presented in the literature (Neta et al., 1988). The
results compiled in Table 3 show, that even non-
protonated mono- and dialkylamines exhibit only
low reaction-rate constants. Even trimethylamine
has at pH 8 a kto t value of only 100 M -~ s -~. In
presence of 1/~M chlorine dioxide its lifetime
would therefore be in the order of 3 h (also com-
pare Fig. 5C). These rate constants would sig-
nificantly increase when the amino group was sub-
stituted with more extended alkyl groups (for
comparisons see compilations by Neta et al., 1988)
and the comprehensive series of publications by
Rosenblatt's group, which has studied reaction
mechanisms (for a later publication of this large
series see, e.g. Davis et al., 1972). In contrast to
amino groups, thiol groups are much more easily
oxidized by chlorine dioxide. The observations on
the reactivities of proteins generally reflect the pat-
terns of rates measured for the amines and thio
compounds (Noss et al., 1986).
Miscellaneous organic olefinic and aromatic hydro-
carbons, aldehydes, ketones and carboxylic acids.
Screening experiments have been performed includ-
ing many further organic compounds to: (i) select
reference compounds suitable for testing rate laws in
respect to orders of reactions, (ii) quantify effects of
variations in conditions, and (iii) to provide examples
which allow for an easier interpretation of literature
values considering water treatment processes.
Methyl-, vinyl and allyl substituted aryl com-
pounds, or naphthalenes and phthalate ions have
reaction-rate constants well below 10 -3 M-~ s-~, and
those of substituted styrenes are below I M -~ s -~
(Choshen et al., 1986). Also carboxylic substituents
do not significantly enhance the reactivity of aliphatic
compo'mds. These reactions with chlorine dioxide
have therefore no relevance for water treatment
processes. In contrast, polynuclear aromatic hydro-
carbons, such as pyrene, have rate constants in the
range of a few M -j s-~ (Rav-Acha and Choshen,
1987).
For some of the experimental methods applied
here, it is important to note that indigotrisulfonate
was decolorized at pH 7 with a rate constant of
> 2 . 1 0 S M -j s -~. Its discolored reaction products,
which were formed when using stoichiometric
amounts of chlorine dioxide, consumed further
54 J/]RG HOIGNEand HEINZ BADER
chlorine dioxide only with a rate constant of
20 M - I s -,"
Humic acids have shown reaction rates that
increased by a factor of three per pH (pH region 4-8).
These rates depended on chlorine dioxide concen-
trations and aging by preoxidation. They therefore
cannot be expressed by second-order reaction-rate
constants (also compare Hoign6 and Bader, 1982).
CONCLUSIONS
Comprehensive measurements of second-order rate
constants for chlorine dioxide reactions with various
types of substrates have been made using conven-
tional laboratory methods, which can be reproduced
in standard drinking water laboratories. The exper-
imental data provide information about compounds
which react with chlorine dioxide during water treat-
ment processes, and those which can be considered as
non-reactive.
All reaction rates were first order in both chlorine
dioxide and substrate concentrations. They can there-
fore be characterized by second-order reaction-rate
constants. Chlorine dioxide is a very highly selective
oxidant. It is apparent that it reacts at nearly diffu-
sion controlled rate constants with compounds such
as deprotonated hydrogen peroxide or phenoxide
anions or amines which can easily donate an elec-
tron. Correspondingly, in the case of the reaction of
chlorine dioxide with hydrogen peroxide, phenols or
amines, the total rate constant is generally controlled
by its reaction with the fraction of the deprotonated
compounds present at a given pH. For drinking water
conditions, reaction rates therefore often increase by
an order of magnitude per pH increment.
Under conditions of water treatment, chlorine
dioxide is not consumed by ammonia, or bromide or
hydrocarbon compounds.
Acknowledgements--We thank Raoul Schaffner and
Tamara Wehrli who devoted much skill in measuring many
of the series reported here during their apprenticeships. We
would also like to recognize the valuable discussions we
have had with various members of the Working Groups
for "Oxidants in Water Treatment" and "Chlorine Dioxide
Application" of the German Association for Gas and Water
(DVGW). We thank Paul Tratnyek, David Sedlak and
Urs yon Gunten for discussions and for reviewing the
manuscript.
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