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Exploring the mechanism of hypochlorous acid

decomposition in aqueous solutions†
Cite this: Phys. Chem. Chem. Phys.,
2019, 21, 19342
Michael Busch, *a Nina Simica and Elisabet Ahlbergb

Hypochlorous acid is an intermediate in important industrial processes such as the production of

Received 18th June 2019,
Accepted 19th August 2019
DOI: 10.1039/c9cp03439k
rsc.li/pccp
chlorate but is also used for water treatment and disinfection. In aqueous solutions hypochlorous acid
may decompose into oxygen or chlorate. Using density functional theory (DFT) modelling we have
for the first time established detailed mechanisms for the respective decomposition pathways.
Our calculations indicate, that both oxygen and chlorate formation proceed through an identical set of
intermediates. At neutral pH the reaction is initiated by a fast equilibrium between HOCl, OCl , Cl2O and
Cl3O2 . The subsequent abstraction of Cl to form Cl2O2 is rate determining for chlorate formation
while it is the decomposition of Cl2O2 in the case of oxygen formation. Under alkaline conditions, OCl
decomposition to chlorate proceeds through chlorite. This reaction path is significantly less active. The
highest rate for chlorate or oxygen formation is found at pH 7.1. These results highlight the need to
consider a complex mixture of different Cl species when addressing the chemistry of hypochlorous acid
containing solutions.

1 Introduction oxygen.4,9 Identical to chlorate formation, the rate dependence

Understanding the chemistry of hypochlorous acid decomposi-
tion in aqueous solutions at different pH is not only interesting
from a fundamental perspective but also central for numerous
applications such as balast water treatment,1 disinfection of
drinking water through chlorination,2 the chlorate process3–5
or medicine.6 The industrial production of chlorate for example
starts with the electrochemical oxidation of chloride to chlorine
which in the pH neutral process electrolyte4,5,7,8 readily dis-
proportionates into Cl and HOCl. The process pH is optimised
for the formation of chlorate in a follow-up chemical reaction,
which takes place homogeneously in solution.4
The uncatalysed5,9–12 chlorate formation path has been
studied in great detail and significant insights on the funda-
mental chemistry of hypochlorous acid decomposition have
been obtained. It is well established that the reaction is third
order with respect to hypochlorous acid. Furthermore, it has
been shown that the maximum rate is obtain at a pH where
hypochlorous acid and hypochlorite have a ratio of 2 to
1.3,4,7–11,13,14 A common byproduct to the chlorate formation is
a
Nouryon, Färjevägen 1, SE-445 80 Bohus, Sweden.
E-mail: michael.busch@nouryon.com, nina.simic@nouryon.com
b
University of Gothenburg, Department of Chemistry and Molecular Biology,
SE-412 96 Gothenburg, Sweden. E-mail: ela@chem.gu.se
† Electronic supplementary information (ESI) available: Summary of thermo-
dynamic calculations of speciation and pH dependence of reaction rates; all
considered reaction paths, molecular structures and reaction energies. See DOI:
10.1039/c9cp03439k
of this reaction is also second order versus [HOCl] and first
order versus [OCl ].
Based on the experimental results a quite detailed mechanism
has been proposed for the HOCl decomposition reaction. The
suggested reaction route proceeds through Cl2O and chlorite to
finally form chlorate.10,11 but also the presence of an asymmetric
Cl2O2 species has been proposed.15 The experiments further
indicate that oxygen and chlorate formation proceed through an
identical set of intermediates.16 For safety and economical reasons
it is crucial to avoid the formation of oxygen during the chlorate
process. At a technical scale this is generally achieved through
addition of sodium dichromate.3–5 But the use of cancerogenous
chromate has been restricted within the European Union and new
catalysts are required. Alternatives to sodium dichromate have
been tested but so far no viable alternative has been found.3,5,9
Despite significant amount of research on the chemistry of
hypochlorous acid in aqueous solutions, detailed mechanistic
studies to confirm the proposed decomposition mechanisms
are still missing. In what follows we will for the first time
evaluate the reaction paths for the decomposition of HOCl or
OCl to O2 or chlorate at different pH using density functional
theory (DFT) calculations. The mechanistic insights serve as a
basis for the thermodynamic modelling of the speciation in
aqueous solutions at different pH. These insights are used
to predict ideal process conditions for chlorate or oxygen
formation. Our results clearly show that a complex mixture of
different species must be considered when addressing the
chemistry of hypochlorous acid containing solutions.

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2 Computational details
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All computations have been performed using the M0617 meta-
hybrid functional as implemented into Jaguar (version: 10.2
release 12)18 in combination with a 6-311**++ triple-z basis set
with diffuse and polarisation functions on all atoms. Calcula-
tions were sped up using the pseudo-spectral method.19–21
Water solvation was modelled implicitly with the Poisson–
Boltzman (pbf) solvation model.22 Geometries were converged
until the final structure did not possess any imaginary modes
or, in the case of a transition state, if it displayed only a single
imaginary frequency. In several cases transitions without sizable
activation barriers were found. In these cases, the absence of
activation barriers was confirmed by scans of the potential energy
surface along all relevant reaction modes. Corrections to the
Gibbs free energy were computed from the vibrational analysis
as implemented into Jaguar. In the case of Cl , no Gibbs free
energy contributions could be computed using Jaguar. Instead,
the experimental entropy contribution of 56.60 J mol 1 K 1 was
added to the electronic energy.23 Energetics of deprotonation
reactions are calculated using the experimental energy of solva-
tion for a proton in aqueous solution of 12.10 eV as a
reference.24 Gibbs Free energies and activation barriers are stated
assuming standard conditions (T = 298.15 K; p = 1 bar) while
reaction rates are estimated under chlorate process conditions
(T = 353 K; p = 1 bar)3–5 using transition state theory.
3 Results and discussion
Building on prior experimental insights, potential reaction
routes were constructed and tested by means of DFT calcula-
tions. In Fig. 1, the most likely reaction paths are shown.
A summary of all considered routes can be found in the ESI.†
Fig. 1 Summary of the reaction mechanism leading to either chlorate or O2 under neutral or alkaline conditions. The rate determining steps for oxygen
and chlorate formation are marked in colour: red – chlorate formation; blue – O2 formation.
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3.1 Neutral pH
At neutral pH, both HOCl and OCl are available as reactants.
In the literature10,11 it is suggested that the initial formation of
Cl2O proceeds through the reaction of 2 HOCl molecules.
Indeed, DFT modelling shows that this reaction is approxi-
mately thermoneutral, i.e., the change in Gibbs Free energy is
below 0.1 eV. Accordingly, its formation is unproblematic from
a purely thermodynamic perspective. However, our calculations
show that a highly strained transition state needs to be over-
come when following this reaction route (Reaction 1).
(1)
Accordingly, this reaction is associated with a very high activation
barrier of 2.8 eV which effectively closes this path. This unfavour-
able transition state might be avoided through deprotonation of
HOCl prior or during the formation of Cl2O. Attempts to find
a transition state for this concerted alternative reaction path
(Reaction 2) failed due to the immediate proton transfer from
HOCl to adjacent water molecules prior to Cl–O bond formation.
(2)
Indeed, deprotonation of HOCl to form OCl and a solvated H+ is
only slightly endergonic (Rxn I in Fig. 2).
Thus, only Cl2O formation through a nucleophilic attack of
OCl on HOCl is a viable possibility (Rxn II in Fig. 1a). This
reaction proceeds through two independent steps. In the first
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Fig. 2 Summary of the reaction energetics at neutral pH. Gibbs free energy corrections have been computed assuming standard conditions. Black
path – common reaction steps for O2 and chlorate formation; blue path – chlorate formation; green path – O2 formation.

step, a HOCl


OCl complex is formed. This reaction is with a

change in Gibbs Free energy below 0.1 eV approximately
thermoneutral (Rxn II in Fig. 2). The obtained Cl2O2H species
(intermediate 3 in Fig. 1a) is characterized by a rather long
HOCl


OCl bond of 2.35 Å which indicates a very weak bond
characterized by dispersion interactions between the two fragments.
As expected for such a complex, this reaction is barrierless which
implies that this reaction is controlled by the rate of diffusion of
the two reactants (Rxn II in Fig. 2). Due to this very low barrier
this route is also active under acidic conditions where OCl is
almost completely absent. For example assuming a pH of 3 a rate
Fig. 3 The Mulliken charges (bold fonts) and bond lengths (normal fonts)
of 39 M2 s 1 for Cl2O formation is estimated under diffusion
for intermediates and transition states participating in Rxn III, Rxn V and
control (T = 353 K; [HOCl] = 0.05 M). Rxn VIIa are summarized. Colour-code: green – Cl; red – O; white – H.
Intermediate 3 readily forms Cl2O (intermediate 4 in Fig. 1a)
through release of the terminal OH group. Surprisingly, this
reaction is barrierless and thermodynamically slightly favour-
able by 0.3 eV. The lack of a sizeable activation barrier can be
understood when considering the frontier orbitals and the
changes in the electron distribution. Initially, the negative total
charge of the reactant is almost exclusively distributed on the
two oxygen atoms (see Fig. 3a). Accordingly, only minor
changes in the electron distribution are required to facilitate
the formation of the O–Cl bond between HOCl and OCl and
the release of the OH leaving group. Additionally, the lowest
unoccupied molecular orbital (LUMO), is of s* antibonding
type and delocalized over the entire complex (Fig. 4a). Thus, the
formation of the O–Cl bond also results in the donation of an
Fig. 4 Lowest unoccupied orbitals (LUMO) of the intermediates 3, 6 and 8.
electron into an antibonding orbital which weakens the Cl–OH Colour-code: green – Cl; red – O; white – H.
bond until it eventually breaks. During this reaction the overall
number of bonds is conserved and only minor changes in the
stability must be expected which is indeed also observed. This reaction is, in contrast to the release of OH , subject to an
An alternative reaction to OH elimination would be the activation barrier of 1.2 eV and therefore less likely to occur.
release of the terminal Cl (Reaction 3). The significantly higher barrier can be understood from the
electron distribution in structure 3. Mulliken charges indicate
that the negative charges are almost exclusively localized at the
(3) oxygen atoms while the Cl atoms display a charge close to 0
(Fig. 3a). While this is beneficial for OH elimination, it hinders

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the release of Cl since a full electron needs to be transferred from
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the negatively charged O atoms to Cl. This reorganisation of the
electronic structure in turn renders the reaction subject to a
comparably high activation barrier.
Once Cl2O is obtained, OCl can attack resulting in the
formation of Cl3O2 , which is one of the key intermediates of
the decomposition mechanism (intermediate 5 in Fig. 1a). This
reaction is exergonic by 0.3 eV and barrierless (Fig. 2). The
bond between the central Cl and the OCl groups is with 1.98 Å
significantly longer than what could be expected for a purely
covalent bond. Additionally, the charge distribution on
both OCl groups is identical (Fig. 3b). Thus, this molecule
may be interpreted as a ‘‘complex’’ where the central Cl atom
‘‘coordinates’’ to two OCl ‘‘ligands’’ which bind in through the
negatively charged O atom. Release of one of the terminal Cl
results in the formation of Cl2O2 (Rxn V in Fig. 1a). This step is
endergonic by 0.5 eV, which implies that a moderate thermo-
dynamic barrier needs to be overcome. Additionally, the reaction
is subject to a significant activation barrier of 0.9 eV (Fig. 2) which
renders this step rate determining for chlorate formation. The
activation barrier corresponds to a rate constant of k = 0.44 s 1.
To allow for the direct comparison with experiment, this needs
to be recalculated to the apparent rate constant by including the
fast equilibrium between intermediate 5, HOCl and OCl prior to
the rate determining step. This is achieved by calculating the
speciation assuming an initial HOCl concentration of 1 M at a
temperature of 353 K. The obtained calculated apparent rate of
0.13 M 2 s 1 is in excellent agreement with the experimental
value of 0.38 M 2 s 1 which has been measured at 353 K in
the absence of any added electrolyte.16 However, it should be
noted that the experimental rate constants vary strongly between
different measurements.4,9,11,12,16 A summary of the experi-
mentally obtained rate constants can be found in the ESI.† The
discrepancies between the experiments can only partly be asso-
ciated to different reaction conditions such as ionic strength and
temperature.
The higher activation barrier required for this reaction step
compared to the release of OH can again be attributed to the
charge distribution in the reactant. Initially, all Cl atoms are
uncharged while the negative excess charge is distributed
almost exclusively between the 2 O atoms (Fig. 3b). During the
Fig. 5 Summary of potential Cl2O2 reactions. Gibbs free energy corrections were computed assuming standard conditions.
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bond breaking electrons are redistributed from the adjacent O
and Cl atoms to the leaving group which displays already in the
transition state a significant negative charge (Fig. 3b).
The obtained Cl2O2 species is finally the bifurcation point
towards either oxygen or chlorate formation. This agrees well
with experiments which suggest that both products are formed
through mechanisms which share equivalent intermediates.16
Horny et al.25 identified 4 possible Cl2O2 isomers which can be
converted into each other. Coming from Cl3O2 (intermediate 5),
the entry point is intermediate 6 (Fig. 5). Direct formation of
chlorate from 6 might occur through nucleophilic attack of
OH at the central Cl atom (Reaction 4)
(4)
which is followed by the release of the terminal Cl (Reaction 5).
(5)
The attack of OH is barrierless and exergonic by 0.3 eV.
Formation of chlorate on the other hand is hindered by a
relatively high barrier of 1.2 eV. The high activation barrier is
again a result of the need to rearrange the electrons such, that
only the slightly positively charged Cl atom can be released as
Cl (see Mulliken charges of 6 in Fig. 3b). Thus, this reaction
path will only contribute to a minor part to the overall chlorate
formation.
Alternative routes towards oxygen or chlorate could also
proceed through one of the other isomers of Cl2O2. Intermediate
6 may react either to 7 or 8 (Fig. 5). The intramolecular rearrange-
ment to 7 is energetically highly favourable by 0.7 eV. Consi-
dering that this reaction is subject to a cost of 0.25 eV for the
changes in solvatisation (DGSolv), this is in semi-quantitative
agreement with high level ab initio gas-phase calculations.25
In agreement with that work25 we find an activation barrier of
0.7 eV for this transition (DGSolv = 0.0 eV). Intermediate 7 in turn
decomposes into Cl2 and O2. This reaction is strongly exergonic by
1.9 eV but subject to a relatively high activation barrier of 1.3 eV
(Rxn VIIb in Fig. 1a and 2). Accordingly, the oxygen formation
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reaction should display a significantly lower rate than the
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corresponding chlorate formation. This is indeed observed
experimentally.9,13 However, since the backward reaction from
7 to 6 has an even higher barrier, 7 likely accumulates over the
course of the reaction and slowly decomposes to oxygen and
chlorine. The formed chlorine immediately dissociates to
HOCl and Cl thus, resulting in the correct overall stoichio-
metry for the formation of oxygen while still obeying a third
order rate law.
Similar to the isomerisation of 6 to 7 also the formation of
the asymmetric intermediate 8 is possible. This structure has
been proposed to play a crucial role in the formation of
chlorate.15 This is in line with our calculations which suggest
that 8 indeed may decompose into chlorate. The M06 DFT
functional used in the present study severely underestimates
the stability of 8, by suggesting that it should be energetically
similar to 6 with a negligible change in the solvatisation energy.
This is in contrast to earlier gas-phase ab initio calculations
which show that the conversion of 6 to 8 is exergonic by 0.5 eV.25
This quantitative discrepancy does, however, not affect the quali-
tative mechanistic conclusions as it only renders the backward
reaction less likely. In contrary, a higher exergonicity would further
strengthen our proposed mechanism. Similar to the reaction of 6
to 7, this reaction also requires a barrier of 0.7 eV to proceed. These
results would, in contrast to experimental evidence,9 indicate that
similar amounts of oxygen and chlorate should form during the
uncatalysed decomposition of hypochlorous acid. However, the
conversion from 6 to 8 could be catalysed by Cl . This alternative
path is characterized by the concerted formation of a Cl–Cl bond
between a Cl from solution and the internal Cl atom combined
with the immediate breaking of a terminal O–Cl bond resulting in
the release of Cl (Reaction 6).
(6)
Our calculations indicate that the bond formation and breaking is
essentially barrierless which implies, that the reaction rate is
controlled by the diffusion of Cl and 6 into the same solvation
cage prior to the reaction to 8. The lack of a sizeable activation
energy can be understood from the analysis of the relevant LUMO
and LUMO+1 frontier orbitals into which the electron pair of the
Cl nucleophile is donated (Fig. 4b). Similar to intermediate 3, the
LUMO and LUMO+1 are of s* antibonding nature. Accordingly,
the Cl–Cl bond formation results in the donation of electrons into
antibonding orbitals which in turn initiates the barrierless breaking
of the O–Cl bond.
Formation of chlorate can then proceed through a concerted
reaction step whereby OH attacks at the central Cl atom while
the terminal Cl leaves as Cl (Reaction 7).
(7)
This reaction is strongly exergonic by 1.5 eV and diffusion
controlled. The concerted nature of the reaction during which
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an electron is donated from the attacking OH into s* anti-
bonding orbitals when forming the HO–Cl bond may again be
responsible for the lack of any sizeable barrier (Fig. 4c).
Furthermore, the terminal Cl, which leaves as Cl displays a
minor negative charge which may aid the bond breaking
further (Fig. 3c).
The equally exergonic competing formation of O2 and Cl2
proceeds through a highly strained transition state comprising
2 condensed 3-membered rings (Reaction 8).
(8)
Not surprisingly, this reaction is hindered by a very high
activation barrier of 2.5 eV. Alternatively, 8 could also rearrange
to 9. This reaction is, however, energetically unfavourable by
1.7 eV. In contrast to the earlier proposed mechanism,10,11 we
could not identify any kinetically favourable reaction path from
Cl2O to chlorite.
In summary the HOCl decomposition in neutral solutions
is characterized by an initial fast equilibrium between HOCl,
OCl , Cl2O and the central Cl3O2 species. Cl elimination from
Cl3O2 finally results in the formation of Cl2O2 which serves as
the bifurcation point for the formation of chlorate or oxygen.
3.2 Alkaline pH
A small but measurable activity for chlorate formation has also
been reported under alkaline conditions.5,10,13,14 Following the
increase of pH from neutral solutions, the activity initially
quickly drops until a minimum is reached between pH 9 and 10.
Moving to even more alkaline pH, the activity starts to increase
again until a plateau is reached.10 In strongly alkaline solutions
the chlorate formation follows, in contrast to the decomposition
in neutral solutions, second order kinetics versus [OCl ].10,13
This change in reaction order in combination with the observed
pH dependence of the rate clearly indicates that a different
reaction mechanism is active. This is not surprising considering
that the reaction route described for neutral pH requires the
presence of HOCl to form the critical Cl3O2 intermediate which
serves as a precursor to the rate determining step (Fig. 1a).
Considering the speciation of HOCl and OCl , (Fig. 6a), only
OCl and OH are available as initial reactants under alkaline
conditions. The formation of Cl2O (intermediate 4), which
serves as precursor for the subsequent reaction steps, can be
ruled out already from a purely thermodynamic perspective as
its formation is endergonic by 0.7 eV. This is in line with the
complete absence of Cl2O in alkaline media (Fig. 6c). Further-
more, no clear reaction path to the formation of Cl2O exists in
strong bases since the protonation of the terminal O atom,
which is required to form a OH or H2O leaving group, is no
longer possible. Formation of chlorite through a concerted
reaction step where OCl performs a nucleophilic attack on
the Cl atom of the second OCl combined with the release of
Cl on the other hand is still possible (Fig. 1b). This reaction
is slightly exergonic by 0.3 eV but hindered by a rather
high activation barrier of 1.0 eV which renders this step rate
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Fig. 7 Reaction energetics for the formation of chlorate at alkaline pH.

Gibbs free energy corrections have been computed assuming standard
conditions.

of the speciation and reaction rates. From a kinetic perspective,

Fig. 6 Speciation of (a) HOCl and OCl , (b) Intermediate 5 and
(c) intermediate 4. The values are calculated using the DFT Gibbs free
energies computed at 353 K in combination with the experimental HOCl/
OCl equilibrium constant pKa = 7.4011 assuming an initial [HOCl] =
0.05 M. The plot is truncated at pH 2 since at lower pH Cl2 dominates.26
Details on the construction of the plots can be found in the ESI.†
determining (Fig. 7). This implies, in line with experimental
evidence,10,13 second order kinetics versus [OCl ]. Furthermore,
experiments indicate the build up of measurable amounts of
chlorite during OCl decomposition above pH 9 which is not
detected at lower pH.10 No reaction paths resulting in the
formation of oxygen were found.
Assuming a rather high pH, chlorite decomposition to
chlorate may only proceed upon reaction with either a second
chlorite27 or with OCl . The former reaction is initialized by the
formation of a chlorite dimer,27 which is followed by chlorate
formation and OCl release (Reaction 9).
both the oxygen and chlorate formation reactions should display
similar pH dependence since the selectivity determining steps
appear too late in the mechanism to be affected. This is in line
with experimental observations.9 Building on the detailed mecha-
nistic insights discussed above, it is possible to evaluate the
contributions of the two main mechanisms to the total hypo-
chlorous acid decomposition rate. pH will mainly affect the
reaction rate by changing the concentrations of OCl and Cl3O2
(intermediate 5 in Fig. 1a), which are the precursors to the
respective rate determining steps. In Fig. 6b the speciation
computed from our DFT data assuming a temperature of 353 K
and an initial HOCl concentration of 0.05 M is shown. Inter-
mediate 5, which is central for the low barrier path, has the
highest concentration at a pH of 7.1. This is not surprising when
considering the fact, that HOCl and OCl , which are both available
at this pH (Fig. 6a), are required for the reaction to proceed. Moving
towards more alkaline or acidic pH, the concentration of 5 quickly
diminishes. The concentration profile of species 5 perfectly aligns
with the highest rate of chlorate formation (Fig. 8a). Accordingly the
highest rate for the first order chlorate formation via Rxn V (Fig. 1a)
from Cl3O2 is found at pH 7.1. Both the position of the maximum

(9)

While this reaction is thermodynamically favourable by 0.7 eV,

it is hindered by an activation barrier of 1.2 eV. Thus, in line with
experimental evidence, high stability of chlorite in the absence of
OCl is expected.28
The reaction of chlorite with OCl on the other hand can
proceed with a significantly lower activation barrier of 0.7 eV
while being strongly exergonic by 1.2 eV (Fig. 7). This renders
the decomposition of chlorite through attack of OCl the most
likely reaction path to chlorate at alkaline pH.
Fig. 8 Rates of chlorate formation via intermediate 5 (a) and chlorite (b).
3.3 pH dependence The data are computed using the DFT Gibbs free energies computed at
353 K in combination with the experimental HOCl/OCl equilibrium
An important aspect in applications involving the chemistry of constant pKa = 7.4011 assuming an initial [HOCl] = 0.05 M. The plot is
hypochlorous acid in aqueous solutions is the pH dependence truncated at pH 2 since at lower pH Cl2 dominates.26

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and the reaction rate of 3  10 3 M s 1 are in very good agreement
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with experiment (compare with Fig. 8a).9,11 Above a pH of 8, the
second mechanism which proceeds through chlorite, starts to
become active and reaches its maximum at a pH of ca. 9
(Fig. 8b). Once the maximum rate is reached, the reaction rate
becomes pH independent. This behaviour is in qualitative agree-
ment with experiment.10 However, the experimentally onset of the
second reaction path is observed at somewhat higher pH. In
agreement with these measurements10 we find the alkaline chlorate
formation route to be significantly less active.
4 Conclusions
Decomposition of hypochlorous acid can proceed through
two distinct mechanisms. At neutral pH chlorate and oxygen
formation proceed through Cl2O (intermediate 4 in Fig. 1a),
Cl3O2 (intermediate 5 in Fig. 1a) and Cl2O2 (intermediate 6 in
Fig. 1a) species. Cl2O2 serves as bifurcation point from which
either oxygen or chlorate are formed. In line with previous
experiments9 we find different rate determining steps for the
two products. In the case of chlorate formation, the abstraction
of Cl from Cl3O2 is rate determining while it is the decom-
position of Cl2O2 in the case of oxygen evolution. The selectivity
between both products is determined by the isomerisation rate
of Cl2O2. The highest reaction rate is found at a pH of 7.1.
Under alkaline conditions a second less active mechanism
proceeding via chlorite to chlorate is identified. These results
highlight the complex equilibrium between very different chlorine
species which, depending on the pH, may be present in hypo-
chlorous acid solutions. Thus, it is crucial to consider a very
diverse set of reactants when addressing the chemistry of
solutions containing hypochlorous acid.
Conflicts of interest
M. B. and N. S. are employed at Nouryon which is a major
producer of chlorate. E. A. has received funding from Nouryon.
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