What is Chlorine Dioxide?

It is not Chlorine!

Chlorine dioxide (ClO2) is the premium biocide, with broad spectrum efficacy, and
several significant advantages relative to “chlorine”.

Before exploring these advantages, we should start by examining the material that
chlorine dioxide is most often mistaken for, “chlorine”. This will allow us to make a
meaningful comparison of these two very different materials, and will allow the reader to
gain an appreciation of the significant differences between them.

The “chlorine” that most people are familiar with is a water based (aqueous) solution of
sodium hypochlorite, commonly called bleach. Sodium hypochlorite has the chemical
formula NaOCl. In aqueous solution sodium hypochlorite dissociates, that is to say the
sodium ion (Na+) and the hypochlorite ion (OCl-) exist as separate species. Under pH
neutral or mildly acidic conditions , the hypochlorite ion forms hypochlorous acid
(HOCl), the highly biocidal species responsible for most of the antimicrobial character
commonly associated with bleach. Under alkaline pH conditions the hypochlorite ion
remains dissociated and the biocidal character of the solution is greatly reduced. Under
strongly acidic conditions, the hypochlorous acid exists in equilibrium with chlorine gas,
and the solution becomes very hazardous to handle.

Sodium hypochlorite is a very strong oxidizer and a very reactive compound which
readily reacts with many organic materials. The products of these reactions are
generically referred to as “halogenated organics” or more specifically as “chlorinated
organics”. Halogenated organics, measured as AOX (absorbable organic halogens ), are
of strong environmental concern. Two subsets of halogenated organics of particularly
strong concern are the groups referred to as THMs (trihalomethanes) and HAAs
(haloacetic acids). The THM of greatest concern is trichloromethane, more commonly
known as chloroform. THMs and HAAs in general, and chloroform specifically, are
carcinogens and thus their formation, eve n at low levels, is a concern. In many
applications the potential for THM and HAA formation is tolerated due to the excellent
antimicrobial properties of sodium hypochlorite.

Chlorine dioxide is a gas, typically dissolved in a liquid at relatively low concentrations.

Unlike sodium hypochlorite, chlorine dioxide does not dissociate in aqueous solution,
instead it remains as the charge neutral structure ClO 2 . This neutral charge imparts
significant benefits to chlorine dioxide as a biocide relative to hypochlorite. Most
notably chlorine dioxide has the ability to penetrate an established biofilm and attack the
biofilm from the inside rather than simply attacking the outer layers as most biocides do.

Chlorine dioxide is much less susceptible to changes in solution pH than hypochlorite.

Chlorine dioxide retains its biocidal character from strongly acidic pH up to mildly
alkaline pH. At strongly alkaline pH chlorine dioxide has a relatively short lifetime in
solution, it rapidly reacts with hydroxide ion to form chlorite ion.

Chlorine dioxide, like hypochlorite, is a strong oxidizer and will react with many
oxidizable materials. However, unlike hypochlorite, chlorine dioxide does not chlorinate
organic molecules when it reacts with them. ClO 2 is an oxyge n donor like H2 O2 and
PAA. Accordingly, the formation of halogenated organics and especially THMs and
HAAs is not an issue with chlorine dioxide. Also, while chlorine dioxide is a strong
oxidizer, its redox potential is less than that of hypochlorite and therefore its reactivity is
lower. This lower reactivity imparts a greater selectivity to chlorine dioxide. The
enhanced selectivity of chlorine dioxide means that a lower concentration of chlorine
dioxide is required to deliver comparable kill to a solution of hypochlorite. Typically the
concentration of chlorine dioxide required is approximately 1/10 that of hypochlorite to
achieve the same level of kill.

name Sodium Hypochlorite Chlorine Dioxide

chemical formula
optimal biocidal pH
biofilm susceptibility
redox potential
Selectivity
soil tolerance
halogenation of organics
THM formation
HAA formation
concentration necessary for
hard surface sanitizing (per
US EPA)
typical concentration
necessary for water
disinfection
maximum residual
concentration in potable
water (per US EPA)
* - maximum residual levels in potable water in Europe vary from country to country,
France 0.1 ppm, Germany 0.4 ppm, Switzerland 0.05 ppm, UK 0.5 ppm
NaOCl ClO 2
6-7 2-8
attacks surface layers only attacks from within
1.49 V 0.95 V
poor, reacts with most highly selective, does not
organics react with most organics
poor, consumed by reaction excellent, minimal loss due
with soil in solution or on to reaction with soil in
surface being sanitized solution or on surface
Yes No
Yes No
Yes No
200 ppm 20-30 ppm (depends on
target organism)
5-25 ppm 1-5 ppm
(depends on level of (depends on level of
impurities in water) impurities in water)
4 ppm (measured as Cl2 ) 0.8 ppm*

As illustrated by the information presented, the use of chlorine dioxide as a disinfectant

and sanitizer has several significant advantages relative to the use of “chlorine”. These
advantages have earned chlorine dioxide the reputation as a premium biocide.