Chlorine Dioxide: Frequently Asked Questions

1. What is chlorine dioxide (ClO2)?

Chlorine dioxide (O=Cl=O) is a free radical monomer chemical compound of chlorine and oxygen, with chlorine in
the +[IV] oxidation state. As a pure substance, above -59 °C, it exists as a yellow-green to orange gas in equilibrium
with its liquid phase. It is an oxidizing agent with a thermodynamic standard reduction potential (E0) equal to 0.95
(mV). It is used industrially as a disinfectant, bleaching agent and oxidizer. It is highly soluble in water. Typical of
most other gasses, ClO2 is more soluble in colder solutions where its solubility limit is about 20,000 mg/l at 0 °C.
Unlike chlorine, ClO2 does not undergo hydrolysis in water. Aqueous solutions of chlorine dioxide have a yellow-
green color and a characteristic bleach-like odor.

2. Is chlorine dioxide explosive?

Highly concentrated gaseous chlorine dioxide can decompose, explosively in air into chorine, oxygen, and heat.
Most commercially available chlorine dioxide generators do not create the conditions (>10%, by weight in air)
required for this to occur. Rather, they produce ClO2 directly in the aqueous phase. Vapors from generated
aqueous ClO2 solutions cannot normally be concentrated to explosive levels.

3. What is chlorine dioxide used for?

As a chemical oxidant and biocide, chlorine dioxide has many industrial uses that include:
- Large scale applications: bleaching of paper pulp and textile fibers, primary and secondary treatment of
municipal drinking water (removal of disinfectant byproduct precursors, iron and manganese as well as
disinfection), microbiological control in open evaporative and single pass cooling water systems, oxidation
of reduced sulfur compounds in industrial ground water, odor control in rendering plants.
- Smaller scale applications: Secondary disinfection (pathogen control) in potable water, microbiological
control in open and closed cooling water and water reuse systems, sanitizing agent for food and beverage
processing equipment, direct and indirect contact disinfectant for food processing, odor control and
oxidation in air scrubbers, waste water treatment (for example, destruction of cyanide and phenols).

Note: Biocide and food and beverage applications are regulated at the state and local levels. It is a violation of
federal law to apply biocides outside of the stipulations stated on the USEPA Pesticide Label.

4. Why use chlorine dioxide?

The major advantages of using chlorine dioxide include:

- Broad spectrum oxidizing biocide– ClO2 is effective in controlling bacteria, viruses, molds, yeast and fungi
at relatively low concentrations. For example, it deactivates resilient cryptosporidium oocysts at 0.2 mg/l
in 20 minutes. Unlike many other biocides, microbes cannot develop resistance to ClO2.
- Penetrates biofilm – Because ClO2 does not react with the biofilm, it diffuses into it and kills the organisms
that lie protected within it.
- Microbiological efficacy independent of pH – In solution, ClO2 exists as a truly dissolved gas and hence,
does not hydrolyze or contain pH sensitive side groups. It is stable from pH 3-10, the practical operating
conditions of most water treatment applications.

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 - Selective oxidizer – because of its relatively low standard reduction potential (0.95 mV), ClO2 only reacts
with certain oxidizable material. These include reduced sulfur compounds but not ammonia, carbohydrate
and hydrocarbons.
- Low corrosion potential (formulation dependent) – Because of it low dose requirements and compared to
oxidizers of higher ‘reduction potential,’ ClO2 is minimally aggressive toward metals. However, certain
chlorine dioxide generation techniques produce solutions with corrosive byproducts.
- Does not form toxic chlorinated byproducts – A number of toxic byproducts (THM’s, HAA’s, AOX) are
formed by chlorine, bromine and iodine through ‘nucleophilic substitution’ where a halogen atom replaces
a hydrogen atom on the compound being oxidized. ClO2 does not participate in this reaction mechanism.
-
5. Are there any disadvantages to using chlorine dioxide?
- More expensive than chlorine and bromine
- Must be generated on site
- Chlorine dioxide vapors are a health hazard and must be vented
- The precursors, sodium chlorite and sodium chlorate are strong oxidizers and are flammable when dried in
the presence of a heat source.

6. Can chlorine dioxide be shipped?

In its pure form, gaseous chlorine dioxide is unstable so it cannot be compressed and shipped like chlorine gas. In
the United States the shipping of chemicals is regulated by the Department of Transportation (DOT). The DOT
allows for ground transportation of aqueous solutions of up to 3000 mg/l, but only in special, approved containers.
Shipping by air of any aqueous concentration is forbidden. It is a violation of federal law to ship any potentially
hazardous chemical by means that are not spelled out in the DOT regulations and it is the responsibility of the
shipper to prove (to the DOT) that shipping containers are adequate. It is for these reasons the chlorine dioxide is
almost always generated from one or more precursors at the point of use.

7. How is chlorine dioxide made?

Chlorine dioxide is generated from sodium chlorite (NaClO2) or sodium chlorate (NaClO3) through electrochemical
and other chemical methods

From sodium chlorite (NaClO2):

- Electrolysis of sodium chlorite (Nalco Envirox™ Technology):
5NaClO2 + 4H2O + electricity = [4ClO2 + NaCl + O2] + 4NaOH + 2H2

- Electrolysis of sodium chlorite:

NaClO2 + H2O = ClO2 + NaOH + ½ H2
- Acidic disproportionation of sodium chlorite with AccuVator™ and catalyst (Nalco AccuCide™ Technology -
US):
5NaClO2 + 4H+ + catalyst = 4ClO2 + NaCl + 4Na+ + 2H2O + catalyst

- Acidic disproportionation of sodium chlorite with hydrochloric acid:

5NaClO2 + 4HCl = 4ClO2 + 5NaCl + 2H2O

- Oxidation of sodium chlorite with chlorine gas or with bleach and hydrochloric acid:
2NaClO2 + Cl2 = 2ClO2 + NaCl
2NaClO2 + NaOCl + 2HCl = 2ClO2 + 3NaCl + H2O
The amount chlorine dioxide that is produced from sodium chlorite ranges between 5 to 1000 g/h

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From sodium chlorate (NaClO3):
- Reduction of sodium chlorate with sulfuric acid (Nalco PURATE™Technology)
2NaClO3 + H2O2 + H2SO4 = 2ClO2 + O2 + Na2SO4 + 2H2O
The amount chlorine dioxide that is produced from PURATE ranges between 1 to 20 Kg/h

Chlorine dioxide solutions known as ‘acidified sodium chlorite’ and ‘stabilized chlorine dioxide’ are generated by
mixing (batch chemistry) sodium chlorite with weak acids (phosphoric, citric, sulfamic). With this scheme, the
conversion of chlorite to ClO2 is not efficient. Dry (powdered) reagents typically containing sources for acid,
hypochlorite and chlorite are also available.

8. How do I choose the right generation technology?

The generation techniques outlined in Question 7 vary greatly by capacity (mass per unit time), precursor
conversion efficiency and in-solution byproducts. These differences impact cost of equipment and operation,
maintenance/service requirements, corrosion potential and even regulatory allowances. It is important to study
the impact of these parameters on the water system under consideration as applications are prone to sensitivity
around: pH depression, TDS, added water volume, product purity, safety interlocks, price, availability of
precursors, customer preference, vendor expertise and support, etc.

9. How do I size a chlorine dioxide generator?

ClO2 generators are designated by mass of product ‘as ClO2’ per unit time. Because application demands vary with
time (cooling loads, production schedules, types of contamination), one must consider the Chlorine Dioxide:

appropriate generation rate as well as total amount generated per day, week or month. The generator must be
sized to meet peak demand by generation rate, bulk storage or a combination of the two.
Variables include volume to be treated, oxidant demand of the water, degree of system fouling, target residual,
regulatory limits and water system design. Sizing determination can be as simple as in ‘secondary disinfection’
where ClO2 is added to demand free municipal water in a healthcare facility and as complicated as a high
temperature, high flow heavily contaminated cooling tower.

10. Is there a site survey form?

A generator is properly sized through data collected in a Site Survey Form. The information contained provides
customer’s expectation, treatment objective, and water and system details. Together, this information will
determine the amount of chlorine dioxide required, size of a generator and all ancillary equipment required for
the intended application.

11. What are chlorine dioxide demand, residual and dose?

- Demand is the amount of chlorine dioxide that is consumed before a measurable residual is established.
Demand stems from chemicals in the system which readily react with ClO2. These can be dissolved or
suspended compounds in the water and sessile materials bound up in the biofilm and debris.
- Residual is the measured concentration of ClO2 in the water after the demand is met. It is typically a target
required for achieving a given treatment objective or regulatory limit.
- Dose is the total amount of ClO2 added. It is the sum of demand and residual.

(ClO2 residual) = (ClO2 dose) - (ClO2 Demand)

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12. What is a demand test?

Demand tests estimate the amount of ClO2 consumed by certain reducing agents in aqueous samples and
represent how much ClO2 needs to be added to an application before a residual can be established. Accurate
results are critical when sizing equipment.
In summary, ultrapure ClO2 standards of known concentration are added (‘spiked’), volumetrically, to
representative samples in an iterative process. Spiked samples are held in the dark at room temperature for 20-30
minutes and then analyzed for chlorine dioxide. A pure water ‘control’ sample is also spiked with the ClO2
standard. The difference in concentration between the spiked sample and the control is the demand of the
sample. Samples may require dilution to correct for color, turbidity or very high demand. Results are corrected for
the dilution factor.
This is a laboratory based procedure and is very sensitive to procedural protocol because errors are multiplicative
toward the final sizing calculations. It is not recommended to perform this in the field. It must be performed in a
controlled setting by a qualified technician.

13. Are there OSHA exposure limits around chlorine dioxide?

The Occupational Exposure Limit (OEL) for 15 minutes is 0.3 ppm chlorine dioxide (in air). For 8 hour exposure, the
OEL is 0.1 mg/L.

14. Why is ClO2 a superior biocide?

- Broad spectrum: ClO2 is effective in controlling bacteria, viruses, molds, yeast, algae and fungi at relatively
low concentrations.
- Kill mechanism and resistance: ClO2 disrupts cell membrane functions and protein synthesis which
prevents microbes from building resistance like they do with most other biocides, including chlorine and
‘non-oxidizers.’
- pH independence: ClO2 maintains efficacy from pH 3-10 because, unlike other halogens (chlorine, bromine,
iodine), it doesn’t react with water (hydrolyze) to form hypo-halous salts.
- Efficacy with protozoan parasites: ClO2 deactivates resilient, cyst forming and pathogenic Giardia Lamblia
and Cryptosporidium parasites, often found in drinking water.
- Control of biofilm dwelling (sessile) microorganisms: Up to 99% of a water systems’ microbial population
exist in the biofilm, a sticky protective, polysaccharide mass that blocks pipes and diminishes heat transfer
rates. Biofilms shield microbes from non-oxidizing biocides and are quickly reestablished after treatment
with oxidizers (chlorine, peroxide, ozone). ClO2 does not react with the polysaccharide, so it migrates into
it and kills the microbes therein. Eventually, this bio-fouling sloughs off into the bulk water (filtration is
needed) and regrowth rates are minimized.

15. How do I test for (measure) ClO2 residual?

There are several analytical procedures for determining ClO2 concentration in aqueous solution. Most are meant
for laboratory environment and are discussed in Standard Methods for the Examination of Water and Wastewater
(AWWA).
The most practical field method utilizes the ‘red-ox’ sensitive dye N,N-diethyl-p-phenylenediamine (DPD) and a
hand-held spectrometer. Oxidized DPD displays a pink color that is linear with ClO2 concentration from approxi-
mately 0.06 – 5.5 mg/l. Glycine is added to the sample to mask background ‘free chlorine.’ Accuracy and precision
are greatly affected by sampling technique, handling and storage because ClO2 is reactive, UV sensitive and
volatile.

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16. How do I test for the disinfection byproducts (chlorite and chlorate ions) of ClO2?

The following laboratory based methods are used; listed from greatest to least degree of accuracy:
- Ion chromatography – See EPA Method 300.1
- Amperometric titration – Red-ox titration with potentiametric endpoint determination
- N,N-diethyl-p-phenylenediamine (DPD) method (modified)

A full discussion is available in Standard Methods for the Examination of Water and Wastewater (AWWA).

17. Is chlorine dioxide corrosive?

The corrosion potential of ClO2 depends on its concentration and generation byproducts. Generated solutions,
ranging from hundreds to thousands of ppm, are very aggressive toward all common metallurgy. Additionally,
these solutions may contain corrosive levels of chloride and hypochlorite along with aggressively low pH.
However, typical use concentrations are very low (0.1 – 5 mg/l) and by virtue of its low thermodynamic ‘standard
reduction potential,’ it is much less corrosive than other common oxidizing agents such as bleach, hypobromate,
ozone, hydrogen peroxide, etc. Nonetheless, corrosion monitoring is recommended.

18. Does chlorine dioxide affect cooling water treatment chemicals?

Chlorine dioxide is compatible with all common dispersants and corrosion inhibitors (except nitrite). These include
polyphosphates, organic phosphates (PBTC, HEDP, and AMP) and azoles (TTA and BZT). Laboratory tests with
TRASAR2™, Tagged polymer and PSO suggest a slight reaction with ClO2 but these results were within
experimental error. Real world experience has shown that some corrosion inhibitors require supplemental dosing
after a ClO2 ‘slug’ dose. This may be due to change in pipe surface morphology resulting from biofilm disruption.

19. How does ClO2 control biofilm?

Biofilm is a sticky protective layer secreted by a variety of microbes. After adhering to a surface (pipe wall, heat
exchanger, floating particle) microbes generate a porous polysaccharide matrix where bulk water flow supplies
nutrients and carries away waste products. Suspended solids (corrosion products, debris, other microbes) stick
to/inside of the matrix, building mass and thickness. Higher organisms graze the biofilm consuming smaller
microbes. Biofilm fouling blocks pipes and heat exchangers significantly increasing pumping costs and diminishing
heat transfer efficiency. Studies indicate that up to 99% of a plumbing systems’ microbial population exists within
the biofilm, so control strategies must be focused on the biofilm. Biofilm blocks (sequesters) non-oxidizing biocides
and although oxidizers (chlorine, peroxide, ozone) react with it, it is regrown very quickly. ClO2, the ‘selective
oxidizer’ (low reduction potential), does not react with the polysaccharide. It migrates by molecular diffusion into
the biofilm to kill the microbes that sustain it. Eventually, this bio-fouling sloughs off into the bulk water (filtration
is needed) and regrowth rates are minimized.
A prevailing theory predicts that this process reduces chlorine dioxide to chlorite ions that remain trapped within
the biofilm where acidic conditions regenerate the ClO2 from the chlorite ions. Thus, recycling the chlorite ion to a
biocidal form.

20. Can a surfactant or bio-dispersant be used with chlorine dioxide?

ClO2 can penetrate biofilm and kill the organisms that produce the biofilm. Eventually, the biofilm sloughs off into
the bulk water. Experience has shown that pre-dosing with bio-detergents can accelerate this process.

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21. Can chlorine dioxide dosing be controlled by ORP?

Oxidation-reduction potential (ORP) is a measure of the net tendency of all chemical compounds in aqueous
solution to form an oxidizing or reducing environment. Combination ORP probes consist of a platinum or gold
‘working electrode’ (anode) and a silver reference electrode. The voltage generated at the anode, with oxidants in
the water, is compared to the constant voltage produced at the reference electrode. This voltage difference is
expressed as ‘millivolts ORP.’ Because ORP represents a net oxidizing environment, it cannot be used to determine
contributions by individual oxidants in a mixture. The reading is also significantly affected by temperature, pH,
alkalinity and total dissolved solids (TDS).
Chlorine dioxide control can be achieved using ORP by correlating actual concentration to ORP millivolt (mV)
readings. This is possible if it is the only oxidant being used and temperature, pH, alkalinity and TDS are fairly
constant. This correlation must be established each time a new water source is treated. Also, the ClO2
concentration cannot exceed approximately 1.0 mg/l when making these correlations.
When water composition varies with time (such as in cooling towers), crude correlations can be established to
adequately control biocide additions using chlorine dioxide.

22. How much chloride ion is contributed by chlorine dioxide versus chlorine?

Relative chloride additions depend greatly on how the chlorine dioxide is generated. This includes generation
chemistry and reactor efficiency. As for chlorine, commodity bleach (sodium hypochlorite, 12.5% (w/w)) supplies
approximately two pounds of salt (as NaCl) per gallon. Chlorine dioxide solutions almost always supply significantly
less chloride. For example, when ClO2 is generated using bleach and/or hydrochloric acid approximately 60% less
chloride ion is added, while electrochemical (Envirox) add 80 to 90 % less chloride ion as compared to chlorine
bleach.

23. Can the amount of chlorine dioxide required be estimated by the amount of chlorine used?

A general Rule of Thumb states: “One pound of chorine ‘as Cl2’ is roughly equivalent to one pound of chlorine
dioxide”. This correlation always, overestimates the actual amount of ClO2 needed because oxidant demand for
ClO2 is generally much lower than for free chlorine. System pH also plays a major role in making a correlation since
the biocide efficacy of chlorine diminishes rapidly with increasing pH whereas ClO2 is unaffected by pH under
normal conditions. As with any oxidizing biocide, sizing estimates should be based on demand testing and
material balances to identify where oxidants are most likely consumed or lost in other ways (for example, blow-
down and volatilization).

24. How does chlorine dioxide affect BOD, COD and TOC?

These parameters may be included in discharge permits. They indicate levels of mass loading of carbon
compounds which may adversely affect the quality of receiving waters. Chlorine dioxide is typically a poor choice
for lowering these parameters. Chlorine dioxide is a relatively weak oxidizing agent making it less reactive toward
compounds amenable to COD and TOC methods. Further, ClO2 may oxidize certain organic material into forms that
are more easily metabolized by microbes; in effect raising the BOD.
Biochemical oxygen demand (BOD), expressed as ‘mg O2/L,’ is a measure of how much oxygen is consumed by
microorganisms, under the test conditions, as they metabolize organic and inorganic material in water. Sample
water is saturated with oxygen, a standardized bacterial ‘seed’ is added, the sample is incubated, and the
remaining (unconsumed) oxygen is measured after 5 or 30 days (BOD5 and BOD30, respectively). The difference
between the saturated and depleted oxygen levels is the BOD.

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Chemical oxygen demand (COD), expressed as ‘mg O2/L,’ is a measure of the oxygen equivalent of the organic
matter in water that is oxidizable by a strong oxidant. The sample is heated with a strong oxidizer (potassium
dichromate) and the COD is calculated from the amount of unreacted dichromate.
Total organic carbon (TOC): expressed as ‘mg C/L,’ is a measure of organically bound carbon associated with
organic material in water. TOC can be further partitioned into Particulate and Dissolved Organic Carbon (POC and
DOC, respectively). The sample is heated with infrared radiation and the organic carbon is converted to CO2
(mineralization) which is directly measured by a non-dispersive infrared analyzer.

25. Can chlorine dioxide control algae in cooling towers?

Chlorine dioxide is effective for controlling algae, by attacking the pyrrole ring of the chlorophyll and cleaving the
ring such that the chlorophyll becomes inactive. Since algae cannot function without chlorophyll metabolism, they
are destroyed. Chlorine dioxide may be applied to cooling towers continuously or intermittently. The typical
chlorine dioxide residual concentration range is 0.1 to 1.0 mg/L for continuous doses, and 0.1 to 5.0 mg/L for
intermittent doses. The minimum acceptable residual concentration of chlorine dioxide is 0.1 mg/L for a minimum
one-minute contact time. A shock-dose of chlorine dioxide to the basin (nightly) is another effective treatment
method. This prevents photo-degradation of chlorine dioxide by sunlight. Algal control has been observed in
poorly wetted areas of the tower fill, presumably due to volatilization of ClO2 in the fill.

26. Is ClO2 effective against nitrifying bacteria?

Nitrification, a step in the nitrogen cycle, is the process by which nitrifying bacteria oxidize ammonia to nitrite
(Nitrosomonas) and then to nitrate (Nitrobacter). The other steps in the nitrogen cycle are fixation (bacteria
convert nitrogen gas to ammonia) and denitrification (conversion of nitrate to N2). These processes can be
troublesome where bacteria thrive in cooling water contaminated with ammonia and where nitrite is used as a
corrosion inhibitor.
Chlorine dioxide is a broad spectrum biocide and effective against these bacteria. Further, chlorine dioxide does
not react with ammonia so it does not have to overcome ammonia-related demand. Note that ClO2 is not
compatible with nitrite inhibitors.

27. Does ClO2 oxidize Fe or Mn?

Chlorine dioxide oxidizes soluble Fe2+ and Mn2+ faster than chlorine, at neutral to alkaline pH. Manganese and iron
precipitate as manganese dioxide (MnO2) and iron hydroxide (Fe(OH)3), respectively. Reaction stoichiometry
requires 2.45 ppm of chlorine dioxide per ppm of Mn2+ and 1.20 ppm of chlorine dioxide per ppm of (Fe2+). Both
MnO2 and Fe(OH)3 are insoluble in water and can be settled or filtered out prior to exiting the treatment plant. In
both cases, approximately 99 % of the MnO2 and Fe(OH)3 can be removed through a 0.45 micron filter after five
minutes of contact time.

28. How much sodium bisulfate or sodium meta-bisulfite is required to neutralize chlorine dioxide?

Sodium thiosulfate (Na2S2O3), sodium bisulfite (NaHSO3), or sodium sulfite (Na2SO3) can effectively neutralize a
chlorine dioxide solution at neutral conditions; 1.5 mg/L of Na2S2O3 or 3.9 mg/L NaHSO3 or 4.7 mg/L of Na2SO3 is
required to reduce 1.0 mg/L of chlorine dioxide.

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29. Is there automated control for chlorine dioxide residuals?

Ideally, chlorine dioxide is monitored and controlled via red-ox ion selective electrodes (chlorine dioxide probes).
Where water quality excludes this approach, control is by ORP or on-line free chlorine analyzers1. These require
frequent validation because the correlation between these techniques and actual ClO2 concentration can change
with time. Automated methods are validated using a standard colorimetric ‘DPD test’ where glycine is added to
the sample prior to the DPD to remove any chlorine present.

1 There is discrepancy in the literature around the true conversion factor when ClO2 is measured with a free chlorine test kit or
analyzer. This is due to calibration issues and the number of electrons transferred from the DPD to the oxidant. The value
displayed ‘as Cl2’ is multiplied by 1.90 to 2.65 to convert it to chlorine dioxide concentration. It is best to determine a
correlation coefficient for each specific water matrix.

30. What plastics are compatible with chlorine dioxide?

Chlorinated polyvinylchloride (CPVC) and most fluoropolymers, such as polytetrafluoroethylene (PTFE), fluorinated
ethylene propylene copolymer (FEP), and polyvinylidene fluoride (PVDF), are recommended for chlorine dioxide
solutions. Avoid all other plastics.

31. What metals are compatible with chlorine dioxide?

Titanium and Hastelloy C-22 are acceptable for chlorine dioxide solutions. Avoid stainless steel 306 and 316.

32. What o-ring materials are compatible with chlorine dioxide?

There is no o-ring material that is truly compatible with chlorine dioxide. The following o-ring materials are
considered satisfactory: Viton ETP, Viton FKM, perfluoroelastomer (KALREZ), and fluorosilicone.

33. Do ClO2 byproducts include AOX, THM and HAA?

Trihalomethane (THM) and haloacetic acids (HAA) belong to large class of compounds known as adsorbable
organic halides (AOX). These disinfection byproducts, formed through chlorination / bromination of surface and
industrial waters, are toxic. Drinking water regulations limit THM and HAA and many water discharge permits
include them, as well.
Chlorine dioxide does not form these compounds2 because its reaction mechanism with organic compounds is
different from halogens like hypochlorous and hypobromous acids (so called bleach and bromine). When
chlorine / bromine oxidizes organic material, it involves nucleophilic substitution where a halogen atom replaces a
hydrogen atom in the organic compound. For example, methane becomes chloro-methane and multiple
substitutions result in trichloromethane, a THM. HAA and AOX are analogues that are created when chlorine
reacts with organic acids and a variety of other organic materials. ClO2 does not participate in nucleophilic
substitution reactions. Rather, it directly oxidizes (if it reacts at all) organic material to it corresponding organic
acid. ClO2 is also used to control disinfectant byproduct precursors in drinking water that is subsequently
chlorinated.
2 Some studies have suggested the formation of extremely low level AOX with ClO2.

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34. Why is ClO2 recommended for control of Legionella?

Legionella bacteria are protozonoic, meaning that their life cycle includes proliferation inside protozoa that graze
on them in the biofilm. This survival strategy offers two forms of protection: 1) the biofilm protects
microorganisms from environmental stress (for example, biocides and heat), and 2) many protozoa form
impenetrable cysts when stressed. Chlorine dioxide, a relatively small non-polar molecule migrates into and
penetrates both the biofilm and the cyst at concentrations as low as 0.20 mg/L, thus deactivating the legionella
bacteria and destroying their habitat.

35. Can I use ClO2 when the makeup-water is grey water?

Chlorine dioxide can be used and is preferred over chlorine with grey water. The reason is that chlorine is
unselective and easily consumed by all types of materials present in the grey water. As a result, large quantities of
chlorine must be used to ensure there is a sufficient residue to act as a biocide. Chlorine dioxide is selective and
only reacts with some sulfur compounds, selected amines and other reduced organic compounds. As a result, low
levels of chlorine dioxide can be used to eliminate micro-organisms, as it is not consumed attacking non-target
compounds.

36. What is the impact of chlorine dioxide on marine life?

The following is an excerpt from US EPA Document EPA 738-R-06-007: “For freshwater aquatic animals, the results
of studies examining the toxicity of chlorine dioxide / sodium chlorite to freshwater fish indicate these chemicals
range from slightly toxic to practically non-toxic on an acute basis. For aquatic invertebrates, the studies indicate
that chlorine dioxide and sodium chlorite range from very highly toxic for technical grade sodium chlorite to
practically non-toxic for the formulated product on an acute basis. Results of toxicity studies indicate that chlorine
dioxide / sodium chlorite are slightly toxic to estuarine / marine fish on an acute basis and range from highly toxic
to slightly toxic to estuarine / marine invertebrates on an acute basis.”

37. What is the pH range for ClO2 effectiveness?

Unlike chlorine, the effectiveness of chlorine dioxide is not controlled by pH. It does not dissociate and remains as
a molecule in an active form from pH range of 4 to 10.

38. Does chlorine dioxide ‘gas off’?

Yes, chlorine dioxide is a highly soluble dissolved gas and as such, partitions between the aqueous and vapour
phase as a function of temperature and pressure. It is more soluble at low temperatures and high pressure.
Mathematically, the equilibrium relationship is described by Henry’s Law.
where x is the chlorine dioxide concentration in the liquid phase, y the chlorine dioxide concentration in the vapor
phase, P the total pressure, and HClO2 Henry’s law constant (2.24 x 10-3 kPa-L/mg at 104 °F and 101.32 kPa). This
relationship describes partitioning in a closed vessel, not in a dynamic system.
Due to its extremely high solubility, ClO2 deviates from Henry’s Law at lower concentrations (< 10 ppm) which
means that it is less likely to ‘gas off’ at concentrations typical of most water treatment applications. However,
ClO2 volatilization must be considered for safety and application planning.

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39. How much chlorine dioxide is lost over a cooling tower?

Loss of chlorine dioxide across the tower is a function of return water temperature, type of packing, air to liquid
ratios and exposure to sunlight. Typical losses are 45 to 65 %. Therefore, ClO2 is almost always dosed to the basin
distribution header. However, the stripping effect associated with the volatility of chlorine dioxide can help keep
packing free from excessive algal and microbiological growth, even in the ‘damp’ areas that do not normally have
direct contact with circulated water. ClO2 is a very effective biocide for open evaporative cooling systems and
becomes economically competitive with commodity bleach in large systems where Nalco’s PURATE technology is
used.

40. Can I use ClO2 in closed loops systems?

Chlorine dioxide is a highly effective ‘best practice’ biocide in closed loop cooling systems, especially where
microbes have developed resistance to traditional non-oxidizing biocides (i.e. isothiazoline and gluteraldehyde)
and where biofilm has accumulated. Typical dosing levels for closed loops are monthly or quarterly at a 10 ppm
slug dose level. The target is to achieve a 1.0 to 2.0 ppm residual after the slug dose. For process chilled water
(where a continuous disinfectant residual is required), residuals of 0.1 to 0.2 ppm can be controlled by ORP or ClO2
probe/controllers. Corrosion monitoring and filtration are highly recommended. If solution volumes are added
later, this added volume must be accounted for to avoid over-pressurization.

41. What is the ‘half-life’ of ClO2?

In water treatment, the concept of ‘half-life’ is used to determine the time it takes for a dissolved compound to
reach one half of its original concentration. This is important where minimum or ‘threshold’ concentrations are
needed for given chemicals to be effective (e.g. corrosion inhibitors and non-oxidizing biocides). It is desirable to
know how long before the chemical residual reaches a concentration where it is no longer effective. In cooling
towers, Holding Time Index (HTI) is used for this purpose. This term is not particularly applicable to chlorine
dioxide because its degradation rate is dependent on a number of variables including volatilization, UV
degradation and, of course, consumption with system contaminants. ClO2 does not have a practical threshold as it
is effective at very low concentrations. ClO2 demand testing is the best predictor of its consumption through
chemical reaction.

42. Can I use non-oxidizing biocides with ClO2 microbial treatment?

Yes, optimal biocide control programs may include intermittent use of chlorine dioxide with non-oxidizing
biocides, such as isothiazoline, gluteraldehyde, DBNPA and quaternary amines. The non-oxidizing biocides have
specific functionalities (type of organism targeted), holding time indices and other dosing considerations to be
evaluated on a case by case basis.

43. What are the breakdown products of chlorine dioxide?

The reaction products of chlorine dioxide depend on what it reacts with and other variables, such as pH. For
example, when reacting with relatively weak reducing agents, ClO2 becomes predominantly chlorite ion (one
electron transfer) while with strong reducing agents, chloride is formed (five electrons transferred). At high pH,
ClO2 undergoes base hydrolysis to form chlorate and chlorite and at low pH, ClO2 decomposes to form chlorate and
chloride.
Chlorine dioxide is photo sensitive and decomposes upon exposure to UV light. In the vapor phase, ClO2 forms
chlorine trioxide which subsequently breaks down to chlorine and oxygen. In the aqueous phase, ClO2
disproportionates to chlorate and chloride.
In typical potable and other water treatment applications, a mixture of the above oxy-chloro species is formed.

FAQ Chlorine Dioxide – European version – April 2017 Page 10

44. What is the ‘kill mechanism’ of chlorine dioxide as a microbicide?

At high concentrations, chlorine dioxide directly oxidizes the cell wall or disrupts its permeability. More
importantly, at low concentrations, because ClO2 is neutral free radical, it can bypass the cell’s active transport
system (the mechanism by which the cell allows materials in and out), migrate into the cell and react directly with
intercellular components. “Chlorine dioxide most likely inactivates microorganisms through direct oxidation of
tyrosine-, methionyl-, or cysteine-containing portions of their proteins, interfering with key structural regions of
sensitive metabolic enzymes or membrane components .”3
3 Alvarez, M.E. 1982. The Mechanisms of Poliovirus inactivation by Chlorine Dioxide and Iodine and the Effects and the Effects of Cations on Halogen Inactivation. PhD
thesis. Las Cruces, N.M.: New Mexico State University

Viruses are inactivated through oxidation of peptone, a water-soluble substance that originates from hydrolysis of
proteins which form amino acids.

45. Can chlorine dioxide be used in conjunction with 3D TRASAR™?

Yes, chlorine dioxide is compatible with the TRASAR, while tagged polymers are minimally affected (less than 4%
degradation) at ClO2 concentrations as high as 1 mg/L chlorine dioxide ‘as free chlorine’ (about Chlorine Dioxide: 2
ppm ‘as ClO2’). In cooling towers with continuous dosing (0.1-0.2 mg/L ClO2 ‘as free chlorine’), no interference was
observed with the studied cooling water treatment chemicals. Likewise, with 3D TRASAR Bio-Control, limited
studies have indicated that chlorine dioxide (as controlled by the 3D Bio-Control) exhibits a typical oxidant
response to the 3D Bio-Reporter control mechanism; even with slug dosing, chlorine dioxide had a minimal impact
on 3D Bio-Control operation and recovery was fast. Good results were observed with the appropriate Ratio Values
assigned in the controller.

46. Can microorganisms develop resistance to chlorine dioxide?

Bacterial resistance to inactivation by antibacterial agents is associated with heterogeneity of the microbial
population. Given fractions are more or less resistant to inactivation. As the susceptible cells are inactivated, they
are replaced by phenotypically resistant ones and the entire population eventually becomes more resistant. Then,
higher biocide levels or different biocides are required for control. Studies have shown that populations are slower
to resist deactivation by ClO2 than for other biocides, if they develop resistance at all. For example,
Cryptosporidium parvum and Giardia lambia are known to develop strong resistance to free chlorine while ClO2
has relatively low C×T values even after prolonged exposure. This is attributed to chlorine dioxide’s unique
reaction characteristics as a high energy, selective oxidant – free radical that can penetrate cell walls.

47. How much chlorine dioxide should be used in potable water applications?

Applications for chlorine dioxide in drinking water include oxidation of metals and organic material for subsequent
coagulation and flocculation, reduction of organic disinfection byproduct precursors (precursors to THM and HAA
formation), organoleptic (taste and odor) control, remediation of algae and bacterial spores in holding ponds and,
of course, final disinfection. ClO2 is also used for secondary disinfection of municipal water for pathogen control in
buildings.
Specific source water quality parameters determine case by case dosing rates and contact times, but neither the
ClO2 nor the chlorite ion residual may exceed 0.8 mg/l in the distribution system.
As an EPA approved potable water additive, federal guidelines must be followed in accordance with the EPA
Pesticide Label for the sodium chlorite or sodium chlorate precursor.

FAQ Chlorine Dioxide – European version – April 2017 Page 11

48. Can chlorine dioxide be used to disinfect swimming pools?

Yes, it can be used alone or in combination with chlorine (Cl2) present as hypochlorous acid (HOCl) and
hypochlorite ion (OCl-). Chlorine dioxide may be added to a side stream of the recirculating water. Chlorine dioxide
breaks down substances, such as phenols and may help to minimize other odorous compounds, such as
chloramines. The advantages of chlorine dioxide are that it can be used at low concentrations for disinfection, is
relatively non-reactive with organic matter, and that few disinfection byproducts are formed. The downsides
include UV sensitivity and a slight yellow color imparted to the water. It is best used for episodic disinfection of
contaminated pool water.

49. Can chlorine dioxide be used to disinfect cooling towers?

Yes, chlorine dioxide is highly effective for microbiological control in open recirculating systems. It is especially
useful for systems with high oxidant demand from outside contamination or process leaks, uncontrolled
biofilm/bio-fouling, water savings requirements, corrosion issues with other oxidizing biocides, discharge
limitations on halogenated byproducts and Legionella contamination. Because it penetrates and strips away
biofilm, ClO2 can vastly decrease operating costs of cooling systems due to increased heat transfer efficiency and
energy savings from pumping water through unobstructed pipes and heat exchangers. It also decreases liability
around water borne pathogens when applied and monitored correctly. In most small to medium sized systems
where chlorite based ClO2 is the right fit, it is not always economically competitive with traditional oxidizers such
as chlorine and bromine unless there is a driving force, as discussed above. Then, huge benefits may be realized.
However, in larger and once-through cooling systems, where chlorate based ClO2 is appropriate, it can be
competitive with chlorine gas or commodity bleach, especially where there is an existing driving force.
Chlorine dioxide can be dosed continuously or semi-continuously or added as a ‘shock dose.’ In consideration of
volatilization losses in the tower, ClO2 is almost always dosed into the distribution header drawing from the sump.

50. What is Envirox SRE 1000/2000?

Envirox is Nalco’s patented NSF-61 certified chlorine dioxide generation and dosing system for control of
microbiological fouling in domestic or other water services. This method uses a three-compartment electrolytic
module where sodium chlorite is converted to chlorine dioxide. The ideal system for control of Legionella in
healthcare facilities domestic water, at chlorine dioxide production of 5 to 100 g/h. Treatment is rendered safe
and simple by the use of a single sodium chlorite precursor, low voltages to the electrochemical cells and a dilute
(540 mg/l) generated ClO2 solution.

51. What is NALDIOX™?

NALDIOX is Nalco based chlorine dioxide generation and dosing system for control of microbiological fouling in
industrial environments. This generator utilizes chemical reaction between sodium chlorite and an sulfuric acid in
an in line reactor. NALDIOX generates chlorine dioxide from 8 to 1000 g/h.

52. What is PURATE?

PURATE is Nalco’s trade name for a blend of sodium chlorate and hydrogen peroxide. The PURATE solution is
reacted with sulfuric acid in a SVP-PURE chlorine dioxide generator. This technology is used in large applications
for bleaching, oxidation and microbiological control for open evaporative and once-through cooling water, odor
control, pulp bleaching and primary disinfection of municipal water, among others. PURATE/SVP-PURE is capable
of producing chlorine dioxide at rate from 1.9 to 90 kg/hr.

FAQ Chlorine Dioxide – European version – April 2017 Page 12

53. What is the best feed point for chlorine dioxide in an open recirculating cooling system?

As a highly soluble dissolved gas, ClO2 should be injected into the distribution header on the outflow of the sump.
This ensures that the chemical travels through the entire system before the water cascades over the packing/fill
where some of it is lost. Typically, the target residual in the return water is 0.1-0.2 mg/l. In some cases, the
chlorine dioxide is injected just upstream of a trouble spot (e.g. condenser or heat exchanger) to solve a particular
microbiological fouling issue. Similarly, ClO2 can be dosed directly into the return water to help clear the tower of
algae and slime.

54. What is the best feed point for chlorine dioxide in a closed loop cooling system?

Although for many chemical treatment programs closed loops are considered well-mixed batch systems, there are
certain guidelines that apply chlorine dioxide which dissipates as it moves through the system. Inject ClO2
upstream of major heat exchangers or trouble spots in order to deliver ‘fresh’ solution to the most critical
operations in the system. In very large loops, two or more injection points may be a strategic advantage because it
is desirable to produce a consistent residual throughout the system. ClO2 may also be injected directly into
seasonal dead-legs (e.g. buildings that are isolated from the main loop during the winter) to minimize
contamination from the dead-leg entering the main loop. Plan on monthly 10 ppm slug doses and a target residual
(after the slug dose is complete) of 1-2 ppm. It is best to deliver the entire slug dose over 24 hours. To avoid
corrosion, do not over-dose. Heavily contaminated systems may require several monthly slug doses before a
residual is observed. Filtration is essential because biofilm bound debris is released into the bulk water. Also,
consider the added volume of solution. Blow down or pressure relief valves may be indicated.

55. What is the best feed point for chlorine dioxide in a thermal energy storage (TES) system?

TES systems present challenges to microbiological control. Fouling may occur in the large cold water reservoirs as
well as in heat exchangers and up to miles of distribution pipework. It is best to install two injection points for
injecting both during the charge and the discharge of the reservoir (in some cases, this is a single point). Chlorine
dioxide dissipates as it moves through the system, so it may be necessary to inject additional ClO2 at distal points
of the system. Inject ClO2 upstream of major heat exchangers or trouble spots in order to deliver ‘fresh’ solution to
the most critical operations in the system. ClO2 may also be injected directly into seasonal dead-legs (e.g. buildings
that are isolated from the main loop during the winter) to minimize contamination from the dead-leg entering the
main loop. Plan on monthly 10 ppm slug doses and a target residual (after the slug dose is complete) of 1-2 ppm. It
is best to deliver the entire slug dose over 24 hours. To avoid corrosion, do not over-dose. Heavily contaminated
systems may require several monthly slug doses before a residual is observed. Filtration is essential because
biofilm bound debris is released into the bulk water. Also, consider the added volume of solution. Blow down may
be indicated.

56. What are the costs of using chlorine dioxide?

Chlorite based chlorine dioxide is about 5 to 10 times more expensive than chlorine in demand-free systems.
Typically the higher the oxidant demand of a system, the more cost-effective chlorine dioxide becomes (provided
the contaminant is non-reactive with ClO2). Chlorine dioxide is usually generated on site from up to three
precursors. The cost of chlorine dioxide depends upon precursor pricing and degree of maintenance required.
Larger, chlorate based ClO2 systems may be cost competitive with commodity chlorine and bleach, especially
where there is a compelling pretext. Note that where a biocide program is ineffective, comparing costs with a
system that does work may be counterproductive.

FAQ Chlorine Dioxide – European version – April 2017 Page 13

57. Is chlorine dioxide safe to work with?

Chlorine dioxide is safe when handled properly. It is vitally important that best practices are followed. The main
safety concern is exposure to airborne ClO2 vapors which can cause severe respiratory damage. Topics for concern
include use of suitably compatible materials in contact with ClO2, avoidance of leaks and spills, mixing of
precursors outside of the reactor, and provision of adequate ventilation where it is in use. Information on the
Safety Data Sheet (SDS) must be understood and practiced.

58. Can chlorine dioxide be used combined with other disinfectants?

Yes, chlorine dioxide can be used in combination with other disinfectants, such as chlorine, bromine, ozone, and
chloramines.

59. Is chlorine dioxide compatible with other cooling water treatment chemicals?

Chlorine dioxide does not react with copper corrosion inhibitors (benzotriazole, tolyltriazole). The polymer,
TRASAR #2, and tagged polymer are not affected at chlorine dioxide concentrations of less than 2.0 mg/L. Polymer
consumption may be significantly reduced when switching from chlorine or bromine to chlorine dioxide.

60. Can chlorine dioxide oxidize phenols?

Yes, below pH 10, a minimum of 1.5 mg/L of chlorine dioxide oxidizes 1 mg/L of phenol to benzoquinone. Above
pH 10, 3.3 mg/L of chlorine dioxide oxidizes 1 mg/L of phenol to a mixture of low molecular weight, nonaromatic,
carboxylic acids (such as oxalic and maleic acids).

61. How can I determine the chlorine dioxide dosage for reused or recycled water with high demand?

Demand tests on representative samples are used to quantify the demand and chlorine dioxide requirement.
Presently, there is no accurate field demand test. Please contact the TEC to arrange for a demand test.

62. Does chlorine dioxide react with ethylene glycol?

Chlorine dioxide does not react with ethylene glycol making it a good biocide for glycol chilled loops and where
cooling water is contaminated with ethylene glycol. Glycol contaminated cooling water is a concern as it serves as
a nutrient for microbes.

63. Since chlorine dioxide does not react with ammonia (unlike chlorine/bleach which form chloramines), what
is the fate of ammonia when a cooling water system is treated with chlorine dioxide?

There is a trend in cooling towers where municipal reclaimed/recycled/reuse, lake, or river water is used in place
of fresh water due to its lower cost. This water can contain up to 10 ppm of ammonia. Ammonia combines with
chlorine, lowering its disinfection effectiveness. Chlorine dioxide does not combine with ammonia and is a good
alternate. Ammonia is very corrosive on yellow metals but has little effect if any on ferrous metals. Therefore,
when using chlorine dioxide with ammonia containing waters, a copper corrosion inhibitor (for example, chemical
treatment programs containing benzotriazole and/or tolyltriazole) must be used. Chlorine dioxide exhibits low
reactivity to dispersant polymers, PSO and azole based corrosion inhibitors, particularly under high pH conditions.

FAQ Chlorine Dioxide – European version – April 2017 Page 14

64. Is chlorine dioxide used in drinking water applications?

- Chlorine dioxide is used with potable water for:

- Primary oxidation for dissolved iron and manganese, as well as disinfection byproduct (for example, THM)
precursor reduction.
- Disinfectant residual for potable water distribution systems.
- Secondary disinfection of municipally treated water to provide additional disinfection properties to the
water (for example, risk reduction of water borne pathogens like legionella).

65. Does chlorine dioxide react with hydrogen sulfide (H2S)?

Between a pH of 5 to 9, chlorine dioxide oxidation of H2S predominantly yields sulfur, as follows:

2 H2S + 2 ClO2
H2SO4 + HCl + S
An average of 2.0 mg/l of ClO2 can be used to instantly oxidize 1.0 mg/l of H2S. In practice, ClO2:H2S weight ratios
usually vary from 2:1 to as much as 4:1.

66. Does chlorine dioxide react with SynGas (carbon monoxide and hydrogen gas)?

At 77 °F, the solubility of hydrogen gas and carbon dioxide in water is approximately 1.5 and 25.0 mg/L,
respectively. Carbon monoxide is not known to react with chlorine dioxide, while hydrogen gas can react according
to:
H2 + ClO2
2 HOCl K = 0.090
The small equilibrium constant indicates very low conversion rates.

67. Can I send the blow-down of the cooling water to my membrane bioreactor or waste water treatment plant
(WWTP) or Publicly Owned Treatment Works (POTW)?

Chlorine dioxide is a biocide and, hence, can deactivate beneficial microbial populations that make up bioreactors.
However, due to the low concentrations used in cooling systems, it rarely persists to create a problem. ClO2 levels
should be closely monitored before discharge to a biological reactor, waste water treatment plant (WWTP) or
Publicly Owned Treatment Works (POTW).

68. How much ClO2 is needed to control the microbial ‘total viable counts’ (TVC) level below 104 CFU/mL?

Follow the best practice dosing guidelines and perform frequent dip-slide and differential microbial analysis (DMA)
to optimize the biocide program.

69. Where free available chlorine (FAC) or total chlorine levels are stipulated in a discharge permit, how is the
permit affected when changing to chlorine dioxide?

In many cases the permit does not change and chlorine dioxide levels in the discharge are analyzed ‘as FAC’ or ‘as
total chlorine.’ This means that the same test is used as before and not a specific test for chlorine dioxide.
However, permit conditions are decided on a case by case basis. Consult with the local regulating authority.

70. Is ClO2 compatible with UF/MF membranes?

Literature reviews indicate limited compatibility of these membranes with chlorine dioxide. As a rule of thumb,
where free chlorine is approved for a membrane, so is chlorine dioxide, at the same levels. Always consult the
membrane manufacturer.

FAQ Chlorine Dioxide – European version – April 2017 Page 15

71. Does chlorine dioxide react with hydrocarbons?
- Alkanes, alkenes, alkynes, and unsaturated aromatics are not readily oxidized by chlorine dioxide in the pH
range of 5 to 9 with five minutes of contact time at ambient temperature.
- Unsaturated hydrocarbons

FAQ Chlorine Dioxide – European version – April 2017 Page 16