Chemical Reactivity of ClO2 | Scotmas - Chlorine Dioxide Specialists (2024)

The electrophilic nature of chlorine or hypochlorous acid can lead, through reaction of addition or substitution, to the formation of organic species while the radical reactivity of chlorine dioxide mainly results in oxycarbonyls.

Generally, Chlorine Dioxide (ClO₂) rapidly oxidises phenol-type compounds, secondary and tertiary amines, organic sulphides and certain hydrocarbon polycyclic aromatics such as benzopyrene, anthracene and benzoathracene.

In general, Chlorine Dioxide will not react on double carbon bonds, aromatic cores, quinionic and carboxylic structures, primary amines, and urea.

Commercial applications have shown that Chlorine Dioxide can effectively oxidise many compounds considered waste and water pollutants. The table below lists a selection of pollutants found in various industries from our files and demonstrates the wide range of possible applications for Chlorine Dioxide. Scotmas possesses over 25 years of application expertise in chlorine dioxide technology in challenging applications.

Aldehydes

Amines and Mercaptans

The primary sources of odorous substances such as mercaptans and substituted amines include the chemical and petroleum industries, cooking and sanitary processes, animal feedlots and rendering plants.

Between pH 5 & 9, 4.5 parts by weight of Chlorine Dioxide instantaneously oxidises 1 part by weight of mercaptan (expressed as sulphur) to the respective sulphonic acid or sulphonate compound, thus destroying the mercaptan odour. Similarly, chlorine dioxide reacts with organic sulphides and disulphides, eliminating the original odour.

Secondary and tertiary amines are also present in many waste waters, causing unique odour problems. The oxidation of amines with Chlorine Dioxide depends on the reaction mixture’s pH and the amine’s degree of substitution.

Between pH 5 and 9, an average of 10 parts by weight of Chlorine Dioxide oxidises 1 part by weight of a secondary aliphatic amine (expressed as nitrogen), removing all traces of amine odour. The higher the pH of the reaction mixture (chlorine dioxide and tertiary and/or secondary aliphatic amines), the more rapidly oxidation proceeds.

THM Precursors

The key to understanding why Chlorine Dioxide is so effective can be found in the differences in chlorine dioxide and chlorine reactions with Tri-halomethane (THM) precursors such as humic and fulvic acids.

Chlorine reacts with THM precursors by oxidation and electrophilic substitution to yield volatile and non-volatile chlorinated organic substances (THMs).

Chlorine Dioxide, however, reacts with THM precursors primarily by oxidation to make them non-reactive or unavailable for THM production. This means that pre-treatment with chlorine dioxide inhibits THM formation when chlorine is subsequently used.

Pesticides

Algae/Slime

Chlorine Dioxide is effective in controlling algae growth. In one study, ClO2 was more effective than copper sulphate at comparable treatment costs. Chlorine Dioxide is believed to attach the pyrolle ring of chlorophyll. This leaves the ring and leaves the chlorophyll inactive. Since algae cannot function without chlorophyll metabolism, they are destroyed. The reaction of Chlorine Dioxide with algae and their essential oils forms tasteless, odourless substances.

Algae control is carried out by adding chlorine dioxide to the reservoir at night (To prevent photolytic decomposition of ClO2). The algae-killing action is fast enough to be effective before the sun rises. A 1 mg/litre dosage has been reported to control algae populations.

Sulphides

Between pH 5 and 9, an average of 5.2 parts by weight of Chlorine Dioxide instantaneously oxidises 1 part by weight of hydrogen sulphide (expressed as sulphide ion) to the sulphate ion.

Many industrial processes produce sulphide-containing gases and waste products. These are generated, for example, during petroleum refining, coal co*king, black liquor evaporation in kraft pulping, viscose rayon manufacture and natural gas purification. These gases and wastes are frequently scrubbed with alkaline solutions and require treatment before discharge.

Nitrogen Compounds

Nitrogen oxides are dangerous and corrosive. Nitrous Oxide (NO) and nitrogen dioxide (NO2) are industrial effluents resulting from fuel combustion, nitric acid manufacture and use, and metal finishing operations which use nitrates, nitrites or nitric acid. Other sources include chemical processes in which nitrogen compounds are used as reagents.

Chlorine Dioxide has been used to scrub these contaminants. Nitric Oxide contained in gas discharges from co*ke kilns may be eliminated by oxidation by Chlorine Dioxide. This process is particularly convenient for continuous operation.

Cyanides

Cyanide compounds originate from metal plating, steel case hardening, pickle liquor neutralising, gold and silver ore refining and blast furnace stack gas scrubbing. Chlorine Dioxide oxidises simple cyanide to cyanate (a less toxic substance) and/or carbon dioxide and nitrogen. The end products depend on reaction conditions.

In neutral and alkaline solutions below pH 10, an average of 2.5 parts by weight of chlorine dioxide oxidises 1 part by weight of cyanide ion to cyanate. Above pH 10, an average of 5.5 parts by weight of Chlorine Dioxide oxidises 1 part by weight of cyanide ion to carbon dioxide and nitrogen. Chlorine Dioxide does not react with cyanate ions, nor has it been observed to form cyanogen chloride during the oxidation of cyanide.

Chlorine Dioxide also oxidises thiocyanate to sulphate and cyanate. In neutral solutions, an average of 3.5 parts by weight of chlorine dioxide oxidises 1 part by weight of thiocyanate ion.

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