TOPIC:

To Bill about the interaction between Chroline dioxide with fluoride


Chlorine Dioxide may readily be converted into Chloryl Fluoride (ClO2F), by elementary fluorine or other fluorinating agents.

Chloryl Fluoride (CLO2F)

Chloryl Fluoride was first obtained in 1942 by Schmitz and Schumacher, by fluorinating Chlorine Dioxide with elementary fluorine. This method is, however, troublesome because of the extraordinary violence of the reaction and, as a result, no further investigation on CLO2F on appeared for 10 years. In recent years the formation of the CLO2F has been studied by several workers. Three routes are available, namely fluorination of KCLO3, CLO2, CL2O6 with elementary fluorine or other fluorinating agents.

Preparation and formation of CLO2F

a. Fluorination of KCLO3. The action of elementary fluorine on KCLO3 represents a method for the formation of the Chloryl Fluoride rather than one for its preparation since it is formed only in small amounts and the main product is perchloryl fluoride. These reactions are carried out between - 40° and + 30°C. Formation of CLO2F is thought to arise from the combination of fluorine witn CLO2 produced by decomposition of the CLO3- anion, and is thus directly related to the formation from CLO2 and fluorine. The course of the reaction when fluorine acts on potassium chlorate is discussed more fully when perchloryl fluoride is considered. Fluorination of KCLO3 may also be effected with other agents and the yields of CLO2F are than better. Thus interaction with CLF3 or BrF3 leads almost exclusively to CLO2F because of the higher reaction temperature needed.

12KCLO3 + 20 BrF3 → 12KBrF4 + 4Br2 + 6O2 + 12CLO2F.

Fluorsulfonic acid may also be used. It may be thought of as HF-SO3, the HF being the actual fluorinating agent, while SO3 serves to combine with water liberated in the reaction. This method gives a 30% yield of CLO2F based on the KCLO3 used, in addition to Chlorine, Chlorine dioxide and oxigen.

b. Fluorination of CLO2. Chlorine dioxide combines directly with fluorine to form CLO2F. As already mentioned chloryl fluoride was first obtained in this way. When the reactants are brought together at room temperature only spontaneous decomposition of CLO2 into chlorine and oxigen is observed. Formation of CLO2F takes place only if the reactants are brought together at suitable partial pressures which are exactly maintained, or if, after condensing them together, they are warmed slowly from - 78°C to + 20°C. Reaction is homogeneous and bimolecular; at low CLO2 concentrations and low pressures the rate controlling step is

CLO2 + F2 → CLO2F + F.

This is followed by the wall reaction 2F - F2. This reaction was developed later by Schumacher into a preparative method. Large quantities of CLO2F may be prepared by leading fluorine into liquid CLO2 at -50°C.
Chloryl fluoride may also be prepared on a larger scale when fluorine is passed into solutions of CLO2 in indifferent solvents; this eliminates the necessity for working with large quantities of condensed CLO2. While in the case of carbon tetrachloride the relatively high crystallization temperature of the solvents limits the working temperature to a minimum of -20°C, at which only low concentrations are possible, it is feasible with CFCL3 at -78°C to reach 3 millimole of CLO2F per ml of solution. Such solutions are execellent for use in studying further reactions of chloryl fluoride. By cooling such solutions to -110°C, CLO2F may be separated and obtained pure after distillation.
The simplest method for preparing chloryl fluoride is certainly to use AgF2 as fluorinating agent. When a slow stream of CLO2 is passed at room temperature through a tube filled with argentic fluoride, quantitative reaction occurs and quite colorless chloryl fluoride may be condensed out in a
trap cooled to -78°C.

AgF2 + CLO2 → AgF + CLO2F.

Consumption of argentic fluoride may readily be followed by observing the movement of boundary between AgF2 (brown) and AgF (yellow), and in this way excess of CLO2 can be avoided. Cobalt trifluoride acts in the same way as AgF2. Chloryl fluoride is also produced when gaseous Chlorine dioxide is passed through liquid BrF3 at +30°C.

6CLO2 + 2BrF3 → 6CLO2F + Br2.

To back up what Bill is getting at...

Citizens groups frequently target fluoride, which is added to the water supply of most municipalities to help cut down on tooth decay in children, as a possible carcinogen. The Journal of Epidemiology, in 2001, linked fluoride as the genetic cause of cancer. A 1990 National Toxicology Program study determined fluoride could be the cause of cancers affecting the mouth, pharynx, colon and rectum. Another study, with results published in the Journal of Environmental Pathology, Toxicology and Oncology in 2001, linked osteosarcoma, a rare bone cancer, with fluoride.

www.freedrinkingwater.com/water-education/medical-water-cancer.htm

alfernandes wrote:

To Bill about the interaction between Chroline dioxide with fluoride


Chlorine Dioxide may readily be converted into Chloryl Fluoride (ClO2F), by elementary fluorine or other fluorinating agents.

Chloryl Fluoride (CLO2F)

Chloryl Fluoride was first obtained in 1942 by Schmitz and Schumacher, by fluorinating Chlorine Dioxide with elementary fluorine. This method is, however, troublesome because of the extraordinary violence of the reaction and, as a result, no further investigation on CLO2F on appeared for 10 years. In recent years the formation of the CLO2F has been studied by several workers. Three routes are available, namely fluorination of KCLO3, CLO2, CL2O6 with elementary fluorine or other fluorinating agents.

Preparation and formation of CLO2F

a. Fluorination of KCLO3. The action of elementary fluorine on KCLO3 represents a method for the formation of the Chloryl Fluoride rather than one for its preparation since it is formed only in small amounts and the main product is perchloryl fluoride. These reactions are carried out between - 40° and + 30°C. Formation of CLO2F is thought to arise from the combination of fluorine witn CLO2 produced by decomposition of the CLO3- anion, and is thus directly related to the formation from CLO2 and fluorine. The course of the reaction when fluorine acts on potassium chlorate is discussed more fully when perchloryl fluoride is considered. Fluorination of KCLO3 may also be effected with other agents and the yields of CLO2F are than better. Thus interaction with CLF3 or BrF3 leads almost exclusively to CLO2F because of the higher reaction temperature needed.

12KCLO3 + 20 BrF3 → 12KBrF4 + 4Br2 + 6O2 + 12CLO2F.

Fluorsulfonic acid may also be used. It may be thought of as HF-SO3, the HF being the actual fluorinating agent, while SO3 serves to combine with water liberated in the reaction. This method gives a 30% yield of CLO2F based on the KCLO3 used, in addition to Chlorine, Chlorine dioxide and oxigen.

b. Fluorination of CLO2. Chlorine dioxide combines directly with fluorine to form CLO2F. As already mentioned chloryl fluoride was first obtained in this way. When the reactants are brought together at room temperature only spontaneous decomposition of CLO2 into chlorine and oxigen is observed. Formation of CLO2F takes place only if the reactants are brought together at suitable partial pressures which are exactly maintained, or if, after condensing them together, they are warmed slowly from - 78°C to + 20°C. Reaction is homogeneous and bimolecular; at low CLO2 concentrations and low pressures the rate controlling step is

CLO2 + F2 → CLO2F + F.

This is followed by the wall reaction 2F - F2. This reaction was developed later by Schumacher into a preparative method. Large quantities of CLO2F may be prepared by leading fluorine into liquid CLO2 at -50°C.
Chloryl fluoride may also be prepared on a larger scale when fluorine is passed into solutions of CLO2 in indifferent solvents; this eliminates the necessity for working with large quantities of condensed CLO2. While in the case of carbon tetrachloride the relatively high crystallization temperature of the solvents limits the working temperature to a minimum of -20°C, at which only low concentrations are possible, it is feasible with CFCL3 at -78°C to reach 3 millimole of CLO2F per ml of solution. Such solutions are execellent for use in studying further reactions of chloryl fluoride. By cooling such solutions to -110°C, CLO2F may be separated and obtained pure after distillation.
The simplest method for preparing chloryl fluoride is certainly to use AgF2 as fluorinating agent. When a slow stream of CLO2 is passed at room temperature through a tube filled with argentic fluoride, quantitative reaction occurs and quite colorless chloryl fluoride may be condensed out in a
trap cooled to -78°C.

AgF2 + CLO2 → AgF + CLO2F.

Consumption of argentic fluoride may readily be followed by observing the movement of boundary between AgF2 (brown) and AgF (yellow), and in this way excess of CLO2 can be avoided. Cobalt trifluoride acts in the same way as AgF2. Chloryl fluoride is also produced when gaseous Chlorine dioxide is passed through liquid BrF3 at +30°C.

6CLO2 + 2BrF3 → 6CLO2F + Br2.

I see now that there is a reaction but excuse my ignorance -- Is this a dangerous reaction to humans?
Should there be a serious warning applied to the use of chlorine dioxide that it is NOT to be mixed in any way with water that has flouride.

This is basically the purpose of my original question and that is Do we need a serious warning applied to our protocols not to mix these two chemicals together?

Your concern is noted Bill.

Here is a report with the first pages of a study done for Fort Collins, Colorado water treatment works. It shows they directly mix CLO2 and Fluorosilicic acid to gain the treatment advantages for their purpose (whatever that may be) and if this was dangerous to human health as a poisonous outcome, I am sure this practice would not be allowed.

Link: www.healthdistrict.org/fluoridereport/title.tableofcontents.intro.pdf

I am trying to see if i can find an inorganic chemical reaction indication between ClO2 and H2SiF6 to see the effects and indications. Not a chemist, but this is not a mystery also.

Personally I am glad and grateful I can avoid the fluoridation in my own drinking water....

Sky wrote:

Your concern is noted Bill.

Here is a report with the first pages of a study done for Fort Collins, Colorado water treatment works. It shows they directly mix CLO2 and Fluorosilicic acid to gain the treatment advantages for their purpose (whatever that may be) and if this was dangerous to human health as a poisonous outcome, I am sure this practice would not be allowed.

Link: www.healthdistrict.org/fluoridereport/title.tableofcontents.intro.pdf

I am trying to see if i can find an inorganic chemical reaction indication between ClO2 and H2SiF6 to see the effects and indications. Not a chemist, but this is not a mystery also.

Personally I am glad and grateful I can avoid the fluoridation in my own drinking water....

Thanks but I am not really confident your statement "if this was dangerous to human health as a poisonous outcome, I am sure this practice would not be allowed."

Lets keep plugging away for a definete answer.

Thanks everyone for all the imput so far.

To BILL and Others

Chloryl fluoride

Chloryl fluoride is the chemical compound with the formula ClO2F. It is commonly encountered side-product in reactions of chlorine fluorides with oxygen sources.[1] It is the acyl fluoride of chloric acid.

Preparation
ClO2F was first reported by Schmitz and Schumacheb in 1942, who prepared it by the fluorination of ClO2.[2] The compound is more conveniently prepared by treatment of sodium chlorate and chlorine trifluoride and purified by vacuum fractionation, i.e. selectively condensing this species separately from other products. This species is a gas boiling at -6 C:

6 NaClO3 + 4 ClF3 → 6 ClO2F + 2 Cl2 + 3 O2 + 6 NaF

Structure
In contrast to O2F2, ClO2F is a pyramidal molecule. This structure is predicted by VSEPR. The differing structures reflects the greater tendency of chlorine to exist in positive oxidation states with oxygen and fluorine ligands. The related Cl-O-F compound perchloryl fluoride, ClO3F, is tetrahedral.

References

^ Chrisie, K. O.; Wilson, R. D.; Schack, C. J. "Chloryl fluoride" Inorganic Syntheses, 1986, volume 24, pages 3-5. ISBN 0-471-83441-6
^ Schmitz, H.; Schumacheb, H. J. "Über eine neue Reaktion des Chlordioxyds. Die Bildung einer Verbindung der Formel ClO2F" Zeitschrift für anorganische und allgemeine Chemie 1942, Volume 249, Pages 238 - 244. DOI 10.1002/zaac.19422490302

To BILL

IRRITATING OR CORROSIVE GASES AND VAPORS


LUNG IRRITATION AND DAMAGE: intense exposure (prolonged exposure to irritants or brief exposure to corrosives) causes lung tissue to swell and seep fluid, a condition called chemical pneumonitis; lungs may be damaged enough to cause death. Methyl isocyanate caused
chemical pneumonitis in the Bhopol India tragedy. Chemical pneumonitis survivors may have permanent lung damage with symptoms similar to emphysema and a form of asthma in which airways constrict when exposed to quite low levels of irritating chemicals.

EYE IRRITATION AND DAMAGE: irritating and corrosive gases may cause intense pain and temporary eye damage which can take several weeks to heal. During exposure the eyes are usually tightly shut--which opens the victim up to the hazards of temporary blindness. Direct eye contact with irritants and corrosive liquids or powders can cause (at best) short term irritation and swelling to (worst case) permanent blindness. Quick and correct actions can reduce symptoms and prevent blindness. Prevention is the best approach to prevent eye damage; wear goggles and face shields when handling corrosive materials. However, if contact does occur, wash chemical out of eyes immediately and continue rinsing with a gentle stream of water for 15 minutes.

SKIN IRRITATION AND DAMAGE: Corrosive chemicals cause severe burns which will form scars unless treated properly. Wash contaminated skin with soap and water (or special solvent in several notable cases--bromine, phenol, hydrogen fluoride) immediately.

Irritating chemicals cause a wide range of skin effects including burns, blisters, redness, itching, dryness, cracks (i.e., between fingers), roughness and a variety of skin problems termed dermatitis (skin inflammation). In general irritant effects are not severe, but are at least, annoying and at worst, temporarily or permanently debilitating (i.e., when an irritant effect turns into an allergy).

EXAMPLES OF IRRITATING AND CORROSIVE CHEMICALS:

Gases such as ammonia, chlorine, bromine, ozone, cyanogen chloride, phosgene, arsenic trichloride, nitrogen oxides, sulfur oxides, hydrogen chloride, acrolein, formaldehyde, fluorine,

Liquids and solids such as strong acids, bases, chlorinated solvents (dichloroacetone, methylene chloride), organic bases, organic solvents, detergents, metal salts (chromates, nickel sulfate). See list below.


Acids and anhydrides
Acetic acid, acetic anhydride, acid mixtures, battery fluids, chlorosulphonic acid, chromic acid, chloroacetic acid, dichloroacetic acid, fluoroboric acid, fluorsilicic acid, hydrobromic, hydrochloric, hydrofluoric and hydriodic acids, methacrylic acid, nitric acid, nitrohydrochloric acid, perchloric acid, phenolsulphonic acid, phosphorus pentoxide, propionic acid, selenic acid, spent acids, sulphamic acid, sulphuric acid and oleum (fuming sulphuic acid), sulphurous acid, thioglycolic acid, trichloroacetic acid.

Alkalis
Ammonium hydroxide, potassium hydroxide (caustic potash), quaternary ammonium hydroxides, sodium hydroxide (caustic soda).

Halogens and halogen salts
Aluminum bromide and chloride, ammonium bifluoride and other bifluorides, antimony trichloride, pentachloride and pentafluoride, beryllium chloride, boron trichloride, bromine, chlorine, calcium fluoride, chromic fluoride, chromous fluoride, iron chlorides (ferric chloride, ferrous chloride), fluorine, iodine, lithium chloride, phosphorus oxybromide and oxychloride (phosphoryl bromide and chloride), phosphorus trichloride
and pentachloride, phosphorus sulphochloride (thisphosphoryl chloride), potassium fluroide and bifluoride, potassium hypochlorite, pyrosulphuryl chloride, sodium chlorite, sodium fluoride, sodium hypochlorite, stannic chloride, sulphur chloride, sulphuryl chloride, thionyl chloride, titanium tetrachloride, vanadium dichloride, zinc chloride.

Interhalogen compounds
Bromine trifluoride and pentafluoride, chlorine trifluoride, iodine monochloride.

Organic halides, organic acid halides, esters and salts
Acetyl bromide, allyl chloride and allyl iodide, acrylonitrile monomer, allyl chloroformate, allyl iodide, ammonium thiocyanate, anisoyl chloride, benzyl chloride, benzhydryl bromide (diphenyl methyl bromide), benzoyl chloride, benzyl bromide, butyl acid phosphate, benzyl chloroformate (benzyl chlorocarbonate), chloroacetyl chloride, ethyl chloroformate (ethyl chlorocarbonate), dibromoethane (ethylene bromide). 1,2-dichloroethane (ethylene chloride), ethylene oxide, fumaryl chloride, ethyl chloroformate (methyl chlorocarbonate), propionyl chloride, iso-propylchloroformate, diisooctyl acid phosphate, p-chlororbenzyl chloride, chloropropionyl chloride, sodium tluorosilicate.

Chlorosilanes
Allyl trichlorosilane, amyl trichlorosilane, butyl trichlorophenltrichlorosilane, cyclohexyl trichlorosilane, dichlorophenyl trichlorosilane, diethyl trichlorosilane, diphenyl dichlorosilane, dodecyl trichlorosilane, hexadecyl trichlorosilane, hexyl trichlorosilane, methyl trichlorosilane, nonyl trichlorosilane, octadecyl trichlorosilane, octyl trichlorosilane, phenyl trichlorosilane, trimethyl trichlorosilane, vinyl trichlorosilane.

Miscellaneous corrosive substances
The following corrosive substances are widely used but do not fall into any of the above classes: ammonium sulphide, benzene sulphonyl chloride, benzyl dimethylamine, beryllium nitrate, catechol, chlorinated benzenes and toluenes, chlorobenzaldehyde, chlorocresols, cresols, cyclohexylamine, dibenzylamine, dichlorophenol, diethyl sulphate, diketene, dimethyl sulphate, hexamethylenediamine, hydrazine, hydrogen peroxide, organic peroxides, phenols, soda lime, sodium aluminate, sodium amide, sodium bisulphate, sodium bisulphite, sodium chromate and dichromate, sodium pyrosulphate, sodium hydride, triethyltertramine, tritolyl borate, silver nitrate.
Proprietary mixtures, i.e., cleaning, disinfecting, bleaching, degreasing solids or solutions based on these chemicals are corrosive to a degree dependent upon dilution.


SENSITIZERS (ALLERGENS)

Some chemicals cause allergies; an allergy (or sensitivity) is an abnormal response to low exposure levels of chemicals which don't elicit a similar response in the majority of people. The allergic response can be quite serious. Once an allergy develops it usually does not go away. If the symptoms are serious, the person must not be allowed to work where the chemical is used or generated. Allergic responses vary from life threatening (anaphylactic "bee sting" type reactions which can cause death by asphyxiation within minutes of exposure); to moderate (dermatitis, severe headache, head or chest cold or flu symptoms); to slight (rash, dry skin, itching nose or eyes).

Chemicals which cause skin sensitivities (by class and several examples of each): coal tar and its derivatives (cresol, pyridine, acridine);dyes (including auramine, amido-azo-benzene, aniline black);dye intermediates (acridine and compounds; aniline and compounds); benzidine and compounds (naphthalene and compounds);explosives (fulminate of mercury, picric acid, sodium nitrate);insecticides (many);natural resins (i.e., dammar, japanese lacquer, pine rosin, copal);natural oils (cashew, coconut, cutting, linseed, mustard, tung);photographic developers (hydroquinone, bichromates, pyrogallol);plasticizers (stearic acid, butyl cellosolve stearate, etc.); rubber accelerators and antioxidants (p-toluidine, guanidine);synthetic resins (acrylic, alkyd, epoxy, chlorophenyls);enzymes (proteolytic enzymes, B. subtilis)


CENTRAL NERVOUS SYSTEM (CNS) DEPRESSANTS ANESTHETIC AND NARCOTIC GASES, VAPORS AND LIQUIDS (MOSTLY SOLVENTS)

Anesthetic or narcotic materials depress the central nervous system (CNS, the brain and spinal cord) causing sleepiness, dizziness, drunk behavior, headache and often nausea and vomiting. Many organic solvents, alcohols, ethers, ketones, esters, etc. are CNS depressants. CNS effects generally occur within a few minutes of overexposure and may last quite awhile, until the chemical has been detoxified by the liver.
Chlorinated hydrocarbon solvents (methylene chloride, methyl chloroform, carbon tetrachloride, etc.) have a peculiar and dangerous effect at high exposure levels (inhalation or direct skin contact): they cause changes in heart function (similar to a heart attack) which can cause death in
minutes. The exposure situation is usually use of these materials in a confined area, where extremely high exposure levels can rapidly develop. Deaths in "glue sniffing" may also be due to this type of heart effect.

One of the most dangerous symptoms of overexposure to CNS depressants is inebriation (drunk behavior) because victims are more likely to make mistakes, to fall or trip, and are less likely to follow or hear instructions or see imminent danger. They are dangerous to themselves and others. Watch for signs of inebriation due to overexposure to chemicals, both in your co-workers and yourself. Many chemicals (especially solvents) can enter the body through the skin, and entry by this route is often more toxic than by oral or inhalation routes. (Propylamine is ten times as toxic via skin than via mouth). Some areas of skin are more easily penetrated by chemicals than others: the scrotum is very easily penetrated (which makes contaminated slacks particularly hazardous); the scalp and forehead are quite easily penetrated, and the palm of the hand is the least easily penetrated. OSHA and ACGIH workplace standards regulate permissible air levels of chemicals; if chemicals can also get into the body via skin, then these organizations give them an "S" or "skin" notation, which means that skin contact must be controlled as well. Chemicals denoted "skin" by ACGIH and OSHA are listed in the following table.

SYSTEMIC TOXINS

Systemic toxins damage tissues at sites other than the point of contact. They enter the body through the skin, mouth or lungs, spread via blood, and damage one or more internal organs such as the liver, kidneys, blood forming tissue, reproductive system, brain or nerves. Systemic damage is usually caused by long term exposure (years) to relatively low levels of chemicals, an exposure pattern often found in industry. Short term exposure to high levels of chemicals (acute exposure) is less likely to cause systemic toxic effects.

We learn about systemic toxicity from human experience (e.g., occupational overexposure) and animal research. Some chemicals have many target organs, some just one. The target organ depends on the material and route and pattern of exposure. It is best to treat systemic toxins as possibly harmful to all organs, since the complete toxicity profile is usually not known. Examples:

CHEMICALS THAT AFFECT SEVERAL ORGANS: halogenated hydrocarbons (many); benzene, phenols (brain and bone marrow/blood forming tissue); ionizing radiation (skin, gut, bone marrow, reproductive organs); carbon disulfide (nervous system, heart); methanol, n-hexane, methyl n-butyl ketone (nerves, brain); organophosphorus compounds, tetra-alkyl lead (brain); lead (bone marrow, brain, conceptus); manganese (lungs); cadmium (lungs, testes); beryllium (lungs); mercury (kidneys, brain); arsenic (many organs including blood); phosphorous (bones); selenium (liver); fluorides (many organs); dichloromethane (kidney, liver, brain); 2-ethoxyethanol (kidney, liver, brain, reproductive system).

CHEMICALS THAT PRIMARILY AFFECT THE BLOOD: acetonitrile, aniline, antimony, arsenic, benzene, carbon disulfide, carbon tetrachloride, cobalt, DDT, ethyl silicate, EGMME, ethylene oxide, fluorides, lead, manganese, mercury, methylchloride, nitrobenzene (nitrophenol), phenylhydrazine, radium, selenium, tetrachloromethane, thallium, thorium, toluene, toluene diamine, toluidine, trichloroethylene, trinitrotoluene, uranium, vanadium, xylene.

CHEMICALS THAT PRIMARILY AFFECT THE LIVER: acrylonitrile, aflatoxin, allylalcohol, antimony, arsenic, beryllium, bromobenzene, cadmium, carbon disulfide, carbon tetrachloride, cerium, chlorinated diphenyls, chlorinated naphthalenes, chloroform, cobalt, cycloheximide, cycloparaffin, DDT, dioxane, dimethyl formate, dimethyl nitrosamine, dinitrophenol, diphenyl, ethanol, ethylene chlorohydrin, ethylene dichloride, hydrazine, methyl bromide, methyl chloride, methyl formate, methylene chloride, nitrobenzol, phenol, phenylhydrazine, phosphorous, pyrolizidine alkaloids, tannic acid, tetrachloroethane, thioacetamide, trichloroethylene, triflurochloroethylene, trinitrotoluene, uranium, urethane.

Thank you alfernandes for all the time and effort you've spent researching this for us.

Chloryl

In chemistry, chloryl refers to the cation having the chemical formula ClO+2. It is polyatomic ion the structurally identical to chlorite and having the same chemical formula but with chlorine in the +5 oxidation state rather than +3. In chloryl, the two oxygen atoms "borrow" a pair of electrons each from the central chlorine atom, forming chloryl, and another elmement or ion oxidizes the chlorine further, leaving the chlorine with one electron pair, wheareas in chlorite one oxygen "borrows" two electrons from chlorine and the other "borrows" one from chlorine and one from another element, leaving chlorine with two electron pairs. Chloryl is isoelectronic with sulfur dioxide.[1]. Chloryl compounds, Such as FClO2 and [ClO2][RuF6] are all highly reactive, and react violently with water and most organic compounds.[2][3]

Structure
The ClO+2 cation is isoelectronic with SO2,[1] and has a bent structure with a bond angle close to 120°. The bond-stretching force constant for its bonds indicate that the Cl–O bond has double bond character.[4]

The red color of ClO+2 is caused by electron transitions into an antibonding orbital. The analogous transition in SO2 is not in the visible spectrum, so SO2 is colorless. The strength of interaction with the counterion affects the energy of this antibonding orbital; thus, in colorless chloryl compounds, strong interactions with the counterion, corresponding with the higher covalent character of the bonding, shift the transition energy out of the visible spectrum.[1]

Compounds

There are two categories of chloryl compounds. The first category is colorless, and includes chloryl fluoride (FClO2). These are moderately reactive. The second category features red-colored compounds that are highly reactive. These include chloryl fluorosulfate, ClO2SO3F, and dichloryl trisulfate, (ClO2)2(S3O10). Chloryl compounds form red solutions in fluorosulfuric acid, and have been found to contain the red-colored ClO+2 cation. In the solid state, the Raman and infrared spectra indicate strong interactions with the counterion.[1][2] Not all chloryl compounds in the solid state are necessarily ionic. The reaction products of FClO2 with BF3 and PF5 are assumed to be molecular adducts rather than true salts.[1][4]

One notable chloryl compound is dichlorine hexoxide, which exists as an ionic compound more accurately described as chloryl perchlorate, [ClO2]+[ClO4]−.[5]

Chloryl compounds are best prepared by the reaction of FClO2 with a strong Lewis acid. For example:[4]

FClO2 + AsF5 → [ClO2][AsF6]
Other synthesis routes are also possible, including:[4]

5 ClO2 + 3 AsF5 → 2 [ClO2][AsF6] + AsF3O + 4 Cl2
Cl2O4 + 2 SbF5 → [ClO2][SbF6] + SbF3O + FClO3
Metathesis reactions may be carried out with strong Lewis bases. For example, the reaction of the hexafluoroplatinate salt with nitryl fluoride yields the nitronium salt:[4]

[ClO2][PtF6] + FNO2 → [NO2][PtF6] + FClO2

References
↑ 1.0 1.1 1.2 1.3 1.4 H. A. Carter; W. M. Johnson; F. Aubke (1969). "Chloryl compounds. Part II. Chloryl hexafluoroarsenate and chloryl fluoride". Canadian Journal of Chemistry 47 (24): 4619–4625.
↑ 2.0 2.1 Christe, K. O.; Schack, C. J.; Pilipovich, D.; Sawodny, W. (1969). "Chloryl cation, ClO+2". Inorganic Chemistry 8 (11): 2489–2494. doi:10.1021/ic50081a050.
↑ Bougon, R.; Cicha, W. V.; Lance, M.; Meublat, L.; Nierlich, M.; Vigner, J. (1991). "Preparation characterization and crystal structure of chloryl hexafluororuthenate(1-). Crystal structure of [ClF2]+[RuF6]−". Inorganic Chemistry 30 (1): 102–109. doi:10.1021/ic00001a019.
↑ 4.0 4.1 4.2 4.3 4.4 K. O. Christe; C. J. Schack (1976). H. J. Emeléus, A. G. Sharpe. ed. Chlorine Oxyfluorides. Advances in inorganic chemistry and radiochemistry, Volume 18. Academic Press. pp. 356–358. ISBN 0120236184.
↑ Tobias, K. M.; Jansen, M. (1986). "Crystal Structure of Cl2O6". Angewandte Chemie International Edition in English 25 (11): 993–994. doi:10.1002/anie.198609931.