Use of Perchloric Acid

Special consideration will be given to the storage and/or use of perchloric acid. The dangers of working with this chemical are well documented and the literature has many examples of situations where fires, explosions, injuries and even death have occurred because of careless or uneducated use of perchloric acid in the laboratory. Perhaps the most disturbing features regarding accidents involving perchloric acid are: 1. the severity of the incidents and 2. that the persons involved are generally experienced in the use of the acid. Because of this, it is important that no one should attempt to use perchloric acid who is not fully informed of its chemistry and until safe working conditions are assured. Perchloric acid is a powerful oxidizing agent that may react explosively with any organic compound or reducing agent. If you consider how many materials that encompasses, you quickly realize the magnitude of the hazard that this acid presents. It reacts with alcohols and certain organics to form very unstable (to shock or heat) perchlorate esters, which have the same shattering power as nitroglycerin. Anhydrous perchloric acid is exceedingly corrosive to the skin and mucous membranes and explosively unstable. It may explode spontaneously. It should never be prepared except for special needs and not stored unless at very low temperature. The dangerously explosive anhydrous acid may also be formed when a drying agent is inadvertently added to diluted concentrations of perchloric acid. This may happen if a material such as hot, concentrated sulfuric acid or phosphorous pentoxide is added. Aqueous perchloric acid at concentrations of less than 85% is stable under ordinary storage situations. The concentration that is normally supplied commercially is 60-72%. Though stable under ordinary circumstances, it must only be stored on ceramic or glass trays never on wood shelves or in wood cabinets. Grave danger exists where perchloric acid evaporates and condenses on the walls and shelves of the storage area. It must not be stored in contact with other chemicals, especially organic solvents. It should not be stored with other acids, since it is capable of oxidizing and reacting with almost all other chemicals including other acids. Explosive reactions may occur when working with hot and concentrated (60 - 72%) perchloric acid. It is particularly critical to keep organics and combustibles away from hot perchloric since these reactions are particularly explosive. Organic matter (paper, wood, grease, plastic or cloth) that has come in contact with perchloric acid fumes must be regarded as a fire and explosion hazard until it has been thoroughly washed down and tested for flammability. If using perchloric acid in the decomposition of organic material (a common use), first treat the material with nitric acid or a mixture of perchloric and nitric acid. This allows the more reactive materials to be oxidized at a low temperature by the nitric acid, thus decreasing the hazard. Perchloric acid must not be used in fume hoods where other materials (organics, flammables) are used because of its capacity to form explosive perchlorates on the hood walls. This necessitates the use of a specially designed perchloric acid hood constructed throughout of stainless steel and equipped with water wash-down capabilities. The perchloric acid hood is designed specifically for use with materials that can deposit shocksensitive crystalline materials in the hood and duct system. These materials become Pyrophoric or explosive when they dry out. The mixture of a perchlorate and any organic material may result in explosion that may be

touched off by friction such as in simply adjusting the panels and baffles in the hood. The water spray should be used whenever perchloric acid is heated in the hood. The exhaust from perchloric acid hoods should not be manifolded with any other type of hood. If a laboratory hood has been exposed to heated perchloric acid, tests must be conducted to determine if explosive perchlorates have formed on the hood walls and duct system. This must be completed before any inspection, cleaning, maintenance, or any other work is done on any part of the hood interior or exhaust system. Some accidents involving perchloric acid:

A violent explosion took place in an exhaust duct from a laboratory hood in which perchloric acid solution was being fumed over a gas plate. It blew out the windows, bulged the exterior walls, lifted the roof, and extensively damaged equipment and supplies. Some time prior to the explosion, the hood had been used for the analysis of miscellaneous materials. The explosion apparently originated in deposits of perchloric acid and organic material in the hood and duct. A chemist was drying alcohol off a small anode over a Bunsen burner in a hood reserved for tests involving perchloric acid. An explosion tore the exhaust duct from the hood, bent a portion of the ductwork near the fan, and blew out many window panes. A 7-lb bottle of perchloric acid solution broke while an employee was unpacking a case containing three bottles. The spilled acid instantly set the wood floor on fire. A stone table of a fume hood was patched with a glycerin cement and several years later, when the hood was being removed, the table exploded when a worker struck the stone with a chisel. The hood had been used for digestions with perchloric acid and, presumably, acid spills had not been properly cleaned up. During routine maintenance involving partial dismantling of the exhaust blower on a perchloric acid ventilating system, a detonation followed a light blow with a hammer on a chisel held against the fan at or near the seal between the rear cover plate and the fan casing. The intensity of the explosion was such that it was heard 4 miles away. Of the 3 employees in the vicinity, one sustained face lacerations and slight eye injury; the second suffered loss of 4 fingers and possible loss of sight in one eye; the third was fatally injured when the 6 inch chisel entered below his left nostril and embedded in his brain. A 6-lb bottle of perchloric acid broke and ran over a fairly large area of wooden floor. It was cleaned up but some ran down over the joists. Several years later a bottle of sulfuric acid was spilled in the same location and a fire broke out immediately in the floor and joists.

Based on these special needs, which are not provided for in most laboratories, this chemical must not be used or stored in any laboratory that has not been especially equipped to address the associated hazards.

Remember These Things About Oxidizing Agents

the primary hazard is the ability to act as an oxygen source, especially hazardous during fire situation. these materials present a fire and explosion hazard when in contact with organic or combustible materials. All contact with organic or combustible material must be avoided. they are generally corrosive. the hazards associated with use of perchloric acid are particularly severe. PERCHLORIC ACID MAY NOT BE USED IN ANY HOOD EXCEPT THOSE SPECIALLY DESIGNED FOR PERCHLORIC ACID USE strong oxidizing agents, such as chromic acid, should be stored and used in glass or other inert, and preferably unbreakable, containers. corks or rubber stoppers must never be used. reaction vessels containing appreciable amounts of oxidizing materials should never be heated in oil baths, but rather on a heating mantle or sand baths.