Sulfur and potassium chlorate

Various sulfides of the halogens are formed by direct combination of sulfur with fluorine, bromine, and chlorine. No evident reaction occurs with iodine instead, the elements remain as components of a mixture. Mixtures of sulfur and potassium chlorate, or sulfur and powdered zinc, are highly explosive. 

Amazingly, no such protocol existed in the UK before 1988, when it was difficult to prevent dangerous, imported fireworks from reaching the shop shelves. Thus, unsuspecting consumers could, in theory at least, purchase items containing prohibited mixtures of, say, sulfur and potassium chlorate and drop them onto the back seat of the family saloon where they could ignite without warning. 

Brock describes some spectacular firework factory explosions that have occurred since the introduction of chlorates into fireworks. Consequently, the combined use of sulfur and potassium chlorate, an especially sensitive mixture, was forbidden in England in 187S. 

The first large-scale use of chlorine was for bleaching paper and cotton textiles it also is widely used as a germicide for public water supplies. Presently it is used principally in production of the chemical compounds sulfur chloride, thionyl chloride, phosgene, aluminum chloride, iron(ni) chloride, titaniura(IV) chloride, tin(IV) chloride, and potassium chlorate. 

MRH Barium chlorate 5.06/83, calcium chlorate 5.61/77, potassium chlorate 6.07/76, sodium bromate 4.98/80, sodium chlorate 7.32/75, zinc chlorate 6.11/76 Dry finely divided mixtures of red (or white) phosphorus with chlorates, bromates or iodates of barium, calcium, magnesium, potassium, sodium or zinc will readily explode on initiation by friction, impact or heat. Fires have been caused by accidental contact in the pocket between the red phosphorus in the friction strip on safety-match boxes and potassium chlorate tablets. Addition of a little water to a mixture of white or red phosphorus and potassium iodate causes a violent or explosive reaction. Addition of a little of a solution of phosphorus in carbon disulfide to potassium chlorate causes an explosion when the solvent evaporates. The extreme danger of mixtures of red phosphorus (or sulfur) with chlorates was recognised in the UK some 50 years ago when unlicenced preparation of such mixtures was prohibited by Orders in Council. 

The self-ignition of sulfur with potassium chlorate or iodine(V) oxide at 145-160°C, and with potassium perchlorate at 385°C was studied using DTA [1], and combustion characterisitics of the mixtures were determined [2],... 

The second German edition of Ruggieri s book (we have not seen the first) contains a Nachtrag or supplement which lists nine compositions,10 of which four contain Kali oxym. or potassium chlorate. These are (1) for red fire, strontium nitrate 24 parts, sulfur 3, fine charcoal 1, and potassium chlorate 5 (2) for green fire, barium carbonate 20 parts, sulfur 5, and potassium chlorate 8 parts (3) for green stars, barium carbonate 20 parts, sulfur 5, and potassium chlorate 9 parts and (4) for red lances, strontium carbonate 24 parts, sulfur 4, charcoal 1, and potassium chlorate 4 parts. Ruggieri says ... 

Similar test results for intimate mixtures of potassium nitrate and red phosphorus 2 31, potassium chlorate and red phosphorus 3 2 and potassium chlorate and sulfur 3 2 are... 

Chemical delay igniters have always been popular with the more versatile Militants. The most common such igniter, but a perverse one, is the sulfuric acid-potassium chlorate and sugar goody. 

V. Braun reaction Cyanogen bromide. Phosphorus tribromide. Piperidine. Thionyl chloride. Bromination Aluminum bromide. Aluminum chloride. Boron tribromide. Bromine chloride. N-Bromocaprolactam. N-Bromosuccinimide. Bromotrichloromethane. Cupric bromide. Dibenzoyl peroxide. l,3-Dibromo-5,5-diraethylhydantoin. 1,2-Dibromotetrachloromethane. HBr-scavengers acetamide and potassium chlorate. Iodine. Iodine monobromide. Iron. Mercuric acetate. Phenyl trimethylammonium perbromide. Phosphorus trichloride. Pyridine. Pyridine perbromide. Pyridinium hydrobromide perbromide. Silver sulfate. Sodium acetate. Sodium hypobromite. Sulfur. Sulfur monochloride. Tetramethylaramonium tribromide. M-Tribromoacetophenone. Trichloromethane sulfonyl bromide. Trilluoroacetyl hypobromite. Triphenylphosphine dibromide. 

This item consists of a glass bottle containing gasoline and concentrated sulfuric acid. The exterior of the bottle is wrapped with a rag or absorbent paper. Just before use, the rag is soaked with a saturated solution of granulated sugar and potassium chlorate. Thrown against hard-surfaced targets such as tanka, automotive vehicles or railroad boxcars, this fire bottle is a very effective incendiary. 

CHEMICAL PROPERTIES Red AT (500°F) ignites at boiling point reacts only at high temperatures less reaetive than white phosphorus White AT (86°F) spontaneously ignites in air reaets with sulfur, halogens, metals, nitrie acid, alkali hydroxides ineompatible with iodine, oil or turpentine and potassium chlorate. 

Low density polyethylene film (PE), known under the commercial name "Polyane" and produced by "La Cellophane" was used in this work. Its thickness was 100 ym and its density was 0.929 g/cm. It melts between 109-112°C. The PE samples were extracted with acetone, dried under reduced pressure and oxidized by immersion in the mixture of sulfuric acid (sq.gr. 1.84 pure grade) and potassium chlorate (reagent grade). The oxidation was performed at room temperature and the percentage of potassium chlorate in the mixture for each set of experiments was varied. Thus, different degrees of oxidation could be obtained. After oxidation PE samples are rinsed several times with triple distilled water and dried in a desicator under reduced pressure. 

Other early match-like devices were based on the property of various combustible substances mixed with potassium chlorate to ignite when moistened with strong acid. More important was the property of chlorates to form mixtures with combustibles of low ignition point which were ignited by friction (John Walker, 1827). However, such matches containing essentially potassium chlorate, antimony sulfide, and later sulfur (lucifers), mbbed within a fold of glass powder-coated paper, were hard to initiate and unreHable. 

Plants can also be pests that need to be controlled, particulady noxious weeds infesting food crops. Prior to 1900, inorganic compounds such as sulfuric acid, copper nitrate, sodium nitrate, ammonium sulfate, and potassium salts were used to selectively control mustards and other broadleaved weeds in cereal grains. By the early 1900s, Kainite and calcium cyanamid were also used in monocotyledenous crops, as well as iron sulfate, copper sulfate, and sodium arsenate. Prom 1915 to 1925, acid arsenical sprays, carbon bisulfate, sodium chlorate, and others were introduced for weed control use. Total or nonselective herbicides kill all vegetation, whereas selective compounds control weeds without adversely affecting the growth of the crop (see Herbicides). 

Quantitatively, sulfur in a free or combined state is generally determined by oxidizing it to a soluble sulfate, by fusion with an alkaH carbonate if necessary, and precipitating it as insoluble barium sulfate. Oxidation can be effected with such agents as concentrated or fuming nitric acid, bromine, sodium peroxide, potassium nitrate, or potassium chlorate. Free sulfur is normally determined by solution in carbon disulfide, the latter being distilled from the extract. This method is not useful if the sample contains polymeric sulfur. 

Several common acid treatments for sample decomposition include the use of concentrated nitric acid, aqua regia, nitric—sulfuric acids, and nitric perchloric acids. Perchloric acid is an effective oxidant, but its use is ha2ardous and requkes great care. Addition of potassium chlorate with nitric acid also assists in dissolving any carbonaceous matter. 

Chlorates are useful oxidizing agents. Potassium chlorate is used as an oxidant in fireworks and in matches. The heads of safety matches consist of a paste of potassium chlorate, antimony sulfide, and sulfur, with powdered glass to create friction when the match is struck as mentioned in Section 15.1, the striking strip contains red phosphorus, which ignites the match head. 

Write the balanced chemical equation for (a) the thermal decomposition of potassium chlorate without a catalyst (b) the reaction of bromine with water (c) the reaction between sodium chloride and concentrated sulfuric acid, (d) Identify each reaction as a Bronsted acid—base, Lewis acid—base, or redox reaction. 

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