Industrial Applications of Perchloric Acid

A Deep Dive into the Multifaceted Industrial Applications and Chemistry of Perchloric Acid.
10 min read

Perchloric acid (HClO4) is a highly reactive, strong acid often utilized in various industrial applications. Discovered in the early 19th century, perchloric acid holds unique physicochemical properties, notably its oxidizing capabilities and its role as a strong acid. However, its widespread usage also presents specific hazards, given its potential for volatility. This article will discuss the industrial applications of perchloric acid, highlighting its importance and outlining the associated challenges.

What is Perchloric Acid?

Perchloric acid, also known as hyperchloric acid or hydroxidotrioxidochlorine, is a strong mineral acid with the chemical formula HClO4. It comprises hydrogen, chlorine, and oxygen atoms and is a highly corrosive and reactive liquid. As a clear, colorless, hygroscopic liquid, it readily absorbs moisture from the air. It has a strong, pungent odor and is soluble in water, alcohol, and ether. Perchloric acid is commonly classified as a superacid because it is more potent than sulfuric and nitric acids. This potency is due to the high electronegativity of the chlorine atom, which makes the hydrogen atom in perchloric acid more acidic than the hydrogen atoms in other mineral acids.

Chemical structure of Perchloric Acid

Source: Wikipedia

How is Perchloric Acid Produced?

Perchloric acid (HClO4) is not naturally occurring in significant amounts. It is primarily a laboratory chemical produced through synthetic methods. Due to its potent acidity and oxidizing properties, perchloric acid is not commonly found in natural environments.

There are several methods of perchloric acid  production, some of which include:

  1. Reacting hydrochloric acid with sodium perchlorate solution

When hydrochloric acid (HCl) is added to a high-concentration aqueous solution of sodium perchlorate (NaClO4), a reaction occurs in which sodium chloride (NaCl) is precipitated out of the solution, and perchloric acid (HClO4) is formed:

NaClO4 + HCl → NaCl + HClO4

This reaction is an example of a double displacement reaction, where the chloride ion (Cl) in hydrochloric acid replaces the perchlorate ion (ClO4) in sodium perchlorate, forming sodium chloride and perchloric acid as the products. The sodium chloride precipitates out of solution because it is insoluble in concentrated perchloric acid. It is important to note that this reaction must be carried out cautiously, as perchloric acid is a potent oxidizing agent and can react violently with certain organic materials or reducing agents.

  1. The anodic oxidation of aqueous chlorine

The anodic oxidation of aqueous chlorine at a platinum electrode is a direct method for producing perchloric acid without using sodium perchlorate or other salts as starting materials. In this method, an aqueous solution of chlorine is electrolyzed using a platinum anode, which promotes the oxidation of chlorine to form perchloric acid at the anode:

2Cl2 + 2H2O → HClO4 + 4H+ + 4Cl-

The perchloric acid formed at the anode can then be collected and purified by distillation, ion exchange, or crystallization methods. This method can result in higher purity perchloric acid than the traditional method, which involves the reaction of hydrochloric acid with sodium perchlorate.

  1. Treatment of barium perchlorate with sulfuric acid

In this reaction, the barium ion (Ba2+) from barium perchlorate combines with the sulfate ion (SO42-) from sulfuric acid to form solid barium sulfate (BaSO4), which precipitates out of the solution. As a double displacement reaction, the cations and anions exchange partners.

Ba(ClO4)2 + H2SO4 → BaSO4 + 2HClO4

At the same time, the hydrogen ion (H+) from sulfuric acid reacts with two perchlorate ions (ClO4-) from barium perchlorate, resulting in the formation of two molecules of perchloric acid (HClO4). The perchloric acid remains in the solution. Overall, the reaction between barium perchlorate and sulfuric acid yields barium sulfate as a precipitate and produces perchloric acid.

Industrial Uses of Perchloric Acid

As an inorganic acid, perchloric acid is known for its potent acidity and excellent oxidizing characteristics. It can become dangerously explosive in a dehydrated state, making its use somewhat of a double-edged sword. Though occasionally hazardous, these distinctive properties have made perchloric acid an invaluable resource across various industrial sectors. From laboratories to chemical synthesis processes, metal processing industries, and even the electronics sector, this potent acid has found many uses, underpinning many critical industrial processes and contributing to advancements in technology and science.

Here are some of the most common uses and functions of Perchloric acid: 

  1. Analytical Chemistry: Perchloric acid is commonly used as a reagent in analytical chemistry for sample preparation, particularly for the digestion of organic and inorganic samples. It helps in breaking down organic compounds and dissolving metal oxides.
  2. Etching and Cleaning: Perchloric acid can be used as an etchant for specific metals, including aluminum & molybdenum. Its strong oxidizing properties allow it to dissolve and remove thin layers of these metals during the etching process. In addition to its etching capabilities, perchloric acid is commonly employed as a cleaning agent for laboratory glassware and equipment. Its strong oxidizing nature helps in effectively removing organic residues, such as oils, greases, and other contaminants that can accumulate on surfaces. Perchloric acid is beneficial for cleaning glassware used in organic synthesis where organic compounds are involved.
  3. Treatment of Amiodarone-induced Thyrotoxicosis: Perchloric acid has been used alone or in combination with other antithyroid drugs to treat amiodarone-induced thyrotoxicosis. This condition occurs when excessive iodine levels result from using amiodarone, a medication commonly prescribed to control cardiac arrhythmias. Amiodarone contains a high concentration of iodine, which can lead to thyroid dysfunction in susceptible individuals. The excess iodine can trigger the production of excessive thyroid hormones, leading to hyperthyroidism or thyrotoxicosis. Perchloric acid, along with other antithyroid drugs, is utilized to reduce thyroid hormone production and alleviate the symptoms of amiodarone-induced thyrotoxicosis. These medications work by inhibiting the synthesis of thyroid hormones and blocking the release of stored thyroid hormones.
  4. Electroplating: Perchloric acid can be used in electroplating processes to deposit certain metals, such as platinum, palladium, and iridium. It is typically used with other chemicals to create an appropriate plating solution. In these cases, perchloric acid is often utilized as an oxidizing agent to enhance the deposition of the desired metal onto the substrate. It helps to maintain the necessary electrochemical conditions for the plating process and improve the quality and efficiency of the plating.
  5. Aerospace & Explosives: Perchloric acid is primarily produced as a precursor for synthesizing ammonium perchlorate (NH4ClO4). Ammonium perchlorate is a crucial component in manufacturing solid rocket propellants and pyrotechnics. The production of ammonium perchlorate involves the reaction of perchloric acid with ammonium salts, typically ammonium chlorate or ammonium hydroxide. The resulting ammonium perchlorate is a powerful oxidizer and provides the oxygen necessary for the combustion of the rocket fuel. Perchloric acid’s role in producing ammonium perchlorate highlights its importance in the aerospace industry and its application in solid rocket propulsion systems.

Perchloric acid can also be used in fireworks formulations, flash powders, explosives, smokeless jets, and rocket propellants. Perchloric acid’s oxidizing properties make it a potential component in energetic materials.

Properties of Perchloric Acid

Chemical FormulaHClO4
Appearance Colorless & Oily Liquid
Molecular Weight (g/mol)100.46
Melting Point (°C)-112
Boiling Point (°C)203
Vapor Pressure(mm Hg at 25 °C)6.8 
Density (g/cm³)1.768
SolubilityHighly soluble in water
Storage ConditionsKeep in a cool, dry location away from direct sunlight or heat sources. Excessive heat can lead to decomposition or increased volatility.
Ensure proper ventilation in the storage area to minimize the accumulation of vapors and fumes. The storage area should have exhaust systems to remove released gasses or vapors.

Perchloric Acid Derivatives

PerchloratesPerchlorates are salts or esters of perchloric acid. They are formed by replacing the hydrogen atoms in perchloric acid with a metal or organic group. For example, sodium perchlorate (NaClO4) and ammonium perchlorate (NH4ClO4) are commonly used perchlorate salts.
Perchloric Acid SaltsPerchloric acid salts neutralize perchloric acid with a metal hydroxide, metal oxide, or metal carbonate. The resulting compounds are typically stable and less hazardous than perchloric acid itself. Examples include potassium perchlorate (KClO4) and magnesium perchlorate (Mg(ClO4)2).
Perchloric Acid EstersPerchloric acid esters, organic perchlorates, are compounds formed by reacting perchloric acid (HClO4) with alcohol or phenols. In this reaction, the hydrogen atoms in perchloric acid are replaced by an organic group, forming ester compounds. Perchloric acid esters are highly reactive and can exhibit powerful oxidizing properties. They are commonly used as potent oxidizing agents in various chemical reactions and as components in rocket propellants. Some examples of perchloric acid esters include methyl perchlorate (CH3ClO4) and ethyl perchlorate (C2H5ClO4).
Perchloric Acid ComplexesPerchloric acid can form complexes with various metals like platinum, cobalt, etc., resulting in unique properties and applications. These complexes can be used as catalysts, reagents in chemical processes, or as supporting electrolytes in electrochemical applications.

Safety & Regulatory Considerations

Despite the widespread usage of perchloric acid, its volatility and corrosive properties pose substantial challenges. Contact with organic material can result in explosive reactions, making safe storage and handling vital. Furthermore, its environmental impact is significant, with perchlorate contamination presenting potential risks to human health and ecosystems. Thus, strict regulations govern its manufacture, use, and disposal, requiring industries to incorporate robust safety measures and waste management procedures.

Health Effects of Perchloric Acid

As a strong acid that can cause severe burns upon contact with the skin, eyes, or mucous membranes, it can also corrode metals and other materials, including organic compounds. Perchloric acid is a powerful oxidizer, meaning it can promote combustion or react violently with reducing agents. Its contact with flammable or combustible materials, such as organic solvents or reactive metals, can lead to fires or explosions. When perchloric acid is heated or comes into contact with certain organic compounds, it can release highly toxic and potentially explosive fumes, such as chlorine dioxide and perchlorates. Inhalation of these fumes can cause severe respiratory distress and other health problems. Laboratories working with perchloric acid should have established protocols for its safe handling, storage, and disposal. 

Toxicity of Perchloric Acid

Inhalation of perchloric acid fumes or mist can cause severe respiratory irritation, coughing, and difficulty breathing. Perchloric acid is corrosive to the skin and eyes. Direct contact can cause burns, skin irritation, and eye damage. Immediate flushing with water and seeking medical attention is crucial in case of contact. Ingesting perchloric acid can result in severe mouth, throat, and gastrointestinal burns. It can cause abdominal pain, nausea, vomiting and potentially lead to systemic toxicity. When heated or in contact with certain organic compounds, perchloric acid can release toxic fumes, including chlorine dioxide. Inhalation of these fumes can cause severe respiratory distress, lung injury, and other health complications.

Environmental Concerns

The potential dangers associated with perchloric acid are not to be underestimated. These risks are not just limited to their explosive nature but also environmental concerns. For instance, improper disposal of perchloric acid can lead to perchlorate contamination, which presents significant ecological risks and potential adverse impacts on human health.

Identification Numbers

Chemical NamePerchloric Acid
CAS Number7601-90-3
EC Number231-512-4
ICSC Number1006

Fun Facts About Perchloric Acid 

  • Friedrich von Stadion synthesized perchloric acid in the mid-1810s. It was called “Oxygenated chloric acid” at the time of discovery & later identified as perchloric acid.
  • Perchlorates, the salts derived from perchloric acid, have been discovered on Mars by NASA’s Phoenix Mars Lander. The existence of perchlorates on Mars raises exciting possibilities for the presence of liquid water in the past and its potential use as a resource for future human missions to the Red Planet.
  • It has been suggested that perchloric acid or its derivatives could be formed in the atmosphere during lightning strikes due to the high energy and electrical activity involved.
  • Perchloric acid is one of the most potent acids known and can even dissolve some metals.

Additional Sources & Resources