Chemistry Honors Project

Perchloric Acid

Laura S. Arana

Colegio Bolvar

May 2017
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Table of Contents

Acids and Bases: An Overview 2

Arrhenius Acids 2

Bronsted-Lowry Acids 2

Lewis Acids 3

Amphoteric and Amphotropic Acids. 4

Concentration and Strength of Acids 4

pH and pOH 5

Basic Physical and Chemical Properties of Perchloric Acid 8

Production and Sources of Perchloric Acid 9

Uses of Perchloric Acid 10

Hazards of Perchloric Acid 11

Conclusion 12

References 13

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Acids and Bases: An Overview

Most liquids have a pH. PH is a measure of acidity or alkalinity in a substance. The

characteristics of each are different; acids taste sour, are corrosive to metals, and change litmus

(a dye extracted from a lichen plant used to indicate pH) to red, while bases taste bitter, feel

slippery, and change litmus blue (Carpi, 2003).

Arrhenius Acids

Arrhenius acids come from the Swedish scientist Svante Arrhenius, who in 1884 stated

that when acids and bases dissolve in water, parts of the substance being dissolved dissociate, or

separate into oppositely charged ions (Acids and bases., 2017). He said that acid-base reactions

are characterized by acids, and from this, Arrhenius suggested that acids contain hydrogen,

which allows them to dissolve in water by releasing hydrogen ions to the solution (Carpi, 2003).

An arrhenius acid is an acid that increases the proton concentration of hydrogen ions. Therefore,

according to Arrhenius an acid is defined as a substance that is ionized when dissolved in water

to give off hydrogen ions (H+), and a base is a substance that gives off hydroxide OH+ ions

when dissolved in water (Definitions of Acids and Bases, and the Role of Water, n.d.).

Bronsted-Lowry Acids

The Bronsted-Lowry theory comes from two independent chemists, the Danish Johannes

Bronsted and British Thomas Lowry, who proposed that an acid is a proton (hydrogen ions H+)

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donor and a base is a proton acceptor (Acids and Bases, 2016). This theory is not based on

water being the solvent, since it states that some substances behave as an acid or base based on

the solvent theyre placed as it can be another liquid, such as ammonia, but acids still need to

have hydrogen. Acid-base reactions are viewed as a competition for protons, which explains why

a strong acid can displace a weak acid from its compounds. Conjugate acid-base pairs are terms

used to refer to the proton donors and acceptors in the proton exchange. A conjugate pair refers

to acids and bases that... have an equal loss or gain of protons between the pairs. Conjugate acids

and conjugate bases are characterized as the acids and bases that gain or lose protons,

respectively. In an acid-base reaction, an acid plus a base reacts to form a conjugate base plus a

conjugate acid (Conjugate Acid-Base Pairs, 2016). Below is an example of an acid-base

reaction labelling the conjugate acid-base pairs.

Figure 1: Conjugate acid base pairs, image courtesy of Google Images.

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Lewis Acids

The Lewis Acids theory comes from the American chemist Gilbert Lewis, who in 1923

defined an acid as a compound that can accept a pair of electrons, and a base as a compound

that can donate a pair of electrons (Acids and bases., 2017). Since this theory uses electrons

instead of protons, it can be more widely used in acid-base reactions, based on structure and

bonding of compounds. A Lewis acid is an electrophile because it accepts an electron pair and

will have vacant orbitals, and a Lewis base is a nucleophile because it donates an electron pair

and will have a lone pair of electrons (Lewis Concept of Acids and Bases, 2016).

Amphoteric and Amphotropic Acids.

The terms amphoteric and amphotropic are similar, and are used to describe substances and

how they behave in an acid-base reaction. Amphoteric substances are those that can act as either

an acid or base. Amphotropic substances are those that can donate protons (H+ ions) and also

accept them, meaning these substances need to have at least one hydrogen atom that can be

donated to another molecule, and also have a lone pair of electrons to receive a proton

(Difference Between Amphiprotic and Amphoteric, 2014). An example of an amphoteric and

an amphotropic substance is water, which acts as both. Water can accept a proton (H3O+) or lose

a proton (OH-), acting based on the Bronsted Lowry theory. This makes water amphotropic, and

since donating or accepting the proton will determine if its an acid or a base its amphoteric

(Clark, 2002).

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Concentration and Strength of Acids

Acids can be classified as strong and weak acids and have different concentrations. Acids

dissociate and ionize in water, by charging the atoms or molecules when adding or removing

electrons to produce hydrogen ions (H+). Strong acids completely ionize the solution, while

weak acids only partially ionize, and form an equilibrium mixture (Strong and Weak Acids,

2014). The strength of an acid is measured by the proportion of the acid that has reacted with

water to produce ions, also defined as its percentage of dissociation (Strong acids have high

dissociation percentages, i.e 100%, while weak acids often have small percentages) (Clark,

2002). Examples of strong acids include perchloric acid (HClO4), hydrochloric acid (HCl), and

nitric acid (HNO3). Weak acids include ethanoic/acetic acid (CH3COOH) and oxalic acid

(HO2C2O2H). Acids can also be concentrated or dilute, which is determined by the acid

concentration, but they are not determined by, or determine the strength of the acid. A

concentrated acid is an acid that is in its pure form or has a high concentration in a solvent

(SCH4U Acid-Base: Concentrated vs. Dilute; Strong vs. Weak, n.d.). The concentration of the

acid shows how much of it is dissolved in solution, and measures the number of moles of acid in

1dm3 of acid solution, determining the classification of concentrated, or the opposite, dilute, with

a low concentration (Strong and Weak Acids, 2014).

pH and pOH

PH is the measure of the strength of the acid or base in a substance, or its acid potential.

A low pH indicates a great acid potential (acid), and a high pH indicates a low acid potential

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(basic) (Green, 2013). The pH scale can be can be mathematically defined by a base 10

logarithm:

pH=-log[H+]

[H+] means the hydrogen ions concentration, it is moles of H+ per liter of solution. Since this

scale is based on Bronsted Lowry definitions of acids and bases, which essentially relates to the

hydrogen ions H+ present in a substance. Acids increase the H+ concentration in a substance by

donating hydrogen protons, while bases decrease the H+ concentration by accepting the protons

(Carpi, 2003). The concentration of hydroxide ions, to determine the potential of hydroxide in a

solution can also be measured, by using the formula:

pOH=-log[OH+]

When the pH and pOH are calculated for a substance, the sum of the pH and pOH is always 14,

which can be written as:

[H+][OH-]=10-14

Brackets indicating molar concentration (Green, 2013). This constant happens because when an

acid adds hydrogen ions to the solution it removes hydroxides because H+ and OH- tend to

combine and form water, and a base will have the opposite effect, increasing OH- and decreasing

H+ (Campbell et al., 2008). The pH scale is used to classify substances based on acidity or

basicity (alkalinity) and this scale uses the hydrogen H+ ions concentration found in the

solutions to label them as acid or basic. The scale goes from 1 to 14, a pH of 1-6 being acidic

(pH 1 the most acidic), pH of 8-14 being basic (pH 14 the most basic), and pH 7 a neutral pH, so

equal concentration of H+ and OH-. Since H+ and OH- concentrations can vary by a factor of

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100 trillion or more, the logarithm is used and means that each pH unit represents a tenfold

difference ( i.e a pH of 3 is 10 times more acidic than a pH of 4) (Campbell et al., 2008).

Figure 2: The pH scale and pH values of some aqueous solutions (Campbell et al., 2008).

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Basic Physical and Chemical Properties of Perchloric Acid

The following physical and chemical properties for perchloric acid are taken from

PubChem Open Chemistry Database by the National Center for Biotechnology Information.

Figure taken from Pubchem Open Chemistry Database by the National Center for Biotechnology

Information and Wikipedia.

Formula: HClO4

2D Structure:

Figure 3 and 4: 2D structure of perchloric acid, bond lengths and angles (Perchloric Acid, n.d)

3D Structure:

Figure 5: 3D structure of perchloric acid (Perchloric Acid n.d).

Elements: Chlorine (Cl), Hydrogen (H), Oxygen (O)

Molecular weight: 100.454 g/mol

Melting point: -112C (-170 F)

Boiling point: 203C (397.4 F)

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Solubility in water: Miscible

Density: 1.6 g/cm to 1.7 g/cm at 25 C (77 F)

Physical description: colorless liquid with pungent odor.

Production and Sources of Perchloric Acid

Perchloric acid was first synthesized in by Von Stadion in 1816, who used vacuum

distillation of a mixture of sulfuric acid and potassium chlorate, and electrolysis of a saturated

aqueous solution of chlorine dioxide (Schilt, 1979). There are currently two methods used for

commercial purposes of perchloric acid production, which is done inorganically. One is by a

reaction of sodium perchlorate and hydrochloric acid which exploits the high aqueous solubility

of sodium perchlorate by using hydrochloric acid, which produces solid sodium chloride (salt)

and perchloric acid, which is then purified through distillation:

NaClO4 + HCl NaCl + HClO4

The second way of perchloric acid production, as claimed by the inventor and how it was

patented states that, first, sodium chlorate is produced from common salt by electrolysis; and

then the sodium chlorate, after isolation in concentrated solution is oxidized on platinum

electrodes. By reacting the sodium perchlorate with concentrated hydrochloric acid, the

perchlorate is converted into sodium chloride and free perchloric acid. The technical perchloric

acid thus obtained contains, after separation of the sodium chloride, still small residues of

sodium perchlorate in addition to other impurities contained in the starting material. The

perchloric acid can be liberated from the residual sodium perchlorate only by distillation

(Muller, 1958). By using liquid chloride and anodically oxidizing it, its producing an oxide film

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on a metallic substrate, a platinum electrode. This removes electrons from a substance and

oxidizes the anode (Anodic Oxidation, n.d.).

Perchloric acid is also made in laboratories by treating barium perchlorate (Ba(ClO4)2)

with sulfuric acid (H2SO4 ) and producing barium sulfate(BaSO4) and perchloric acid (HClO4) in

a double replacement reaction (PubChem, n.d):

Ba(ClO4)2 +
H2SO4
BaSO4 +
HClO4

Figure 6: Perchloric acid (Perchloric Acid, n.d).

Uses of Perchloric Acid

Perchloric acid is used in industrial and testing laboratories, and it's called a superacid

because its one of the strongest Bronsted Lowry acids. It is used mainly in rocket fuel to form

ammonium perchlorate. Several million kilograms of perchloric acid are produced annually, due

mainly to the growth of rocketry, and GFS Chemicals is its largest producer (Vogt et al., 2002).

Perchloric acid, thanks to its properties has as well a variety of uses in chemical analysis such as

a solvent for metals and alloys, oxidizing agent (specially in determination of chromium in

steel, ferrochrome, chromite, and silicate materials), dehydrating agent (determination of silica in

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iron, steel, and cement), destruction of organic materials (mixed with nitric acid),

deproteinization reagent in food analysis (i.e determination of butterfat in dairy products),

electric polishing/etching of metals such as aluminium and molybdenum, and as a strong acid, or

the strongest when dissolved in anhydrous acetic acid for the titration of bases (Perchloric

Acid, 2013). Titration of bases consists of neutralizing a base to have a quantitative analysis of

the unknown base concentration.

Hazards of Perchloric Acid

Perchloric acid is a strong, corrosive, and highly reactive acid that is highly damaging to

tissue when it comes in contact with it. Perchloric acid is classified under the Workplace

Hazardous Materials Information System (WHMIS) as a powerful oxidizer (Class C) and highly

corrosive (Class E). As per the Globally Harmonized System for Classification and Labelling of

Chemicals (GHS), perchloric acid is generally classified as an oxidizing liquid (Category 1),

corrosive to metals (Category 1), having acute toxicity (oral - Category 4), and causing skin

corrosion/irritation (Sub-category 1A), serious eye damage/eye irritation (Category 1) and

specific organ toxicity (category dependent on supplier) (A Guideline for the Use of Perchloric

Acid and Perchloric Acid Fume Hoods, 2016). Factors such as storage, temperature, and

concentration affect the stability of perchloric acid, which is why it should be stored, with

concentrations below 70% at room temperature, because at higher concentrations or

temperatures, regardless of concentration perchloric acid acts as a strong oxidizer. Anhydrous

perchloric acid, containing no water, is even more unstable, causing it to explode when it comes

in contact with organic material and after days of storage (Perchloric Acid, 2014). Perchloric

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acid should be stored under the right guidelines and in places designated specifically for

hazardous acids, and when handling with the acid done using protective equipment, and under a

perchloric acid hood, which is a local exhaust specifically designed with materials that are

non-reactive with perchloric acid and is washed down after every use.

Figure 7: Perchloric Acid Hood (Perchloric Acid Fume Hoods, n.d)

Conclusion

Perchloric acid is one of the strongest acids, and its inorganic production by two main methods is

used industrially and in laboratories worldwide. Described as a colorless liquid with pungent

odor, has a low melting point but a high boiling point, which makes it always produced and used

as a liquid. Its strong acid properties, like its corrosivity and low pH makes it useful for

chemical purposes such as titration, destruction of organic materials, and electropolishing of

metals, but also presents hazard that should always be addressed properly when handling the

acid.

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References

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Office of the Chief Inspector of Mines. Retrieved from

http://www2.gov.bc.ca/assets/gov/farming-natural-resources-and-industry/mineral-explorati

on-mining/documents/health-and-safety/perchloric_acid_guideline2016.pdf

Acids and Bases. (2016). Funk & Wagnalls New World Encyclopedia, 1p. 1.

Acids and bases. (2017). Columbia Electronic Encyclopedia, 6th Edition, 11.

Bronsted Lowry Concepts of Acids and Bases. (2016, May 28). Retrieved from

https://chem.libretexts.org/Core/Physical_and_Theoretical_Chemistry/Acids_and_Bases/Aci

d/Bronsted_Concept_of_Acids_and_Bases

Campbell, N. A., Reece, J. B., Urry, L. A., Cain, M. L., Wasserman, S. A., Minorsky, P. V., &

Jackson, R. B. (2008). Acidic and basic conditions affecting living organisms. In Campbell

Biology (8th ed., pp. 5254). Pearson Benjamin Cummings.

Carpi, A. (2003). Acids and Bases: An Introduction.

Clark, J. (2002a). Strong and Weak Acids. Retrieved from

http://www.chemguide.co.uk/physical/acidbaseeqia/acids.html

Clark, J. (2002b). Theories of Acids and Bases. Retrieved from

http://www.chemguide.co.uk/physical/acidbaseeqia/theories.html

Conjugate Acid-Base Pairs. (2016). Retrieved from

https://chem.libretexts.org/Core/Physical_and_Theoretical_Chemistry/Acids_and_Bases/Aci

d%2F%2FBase_Reactions/Conjugate_Acids-base_Pairs

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Definitions of Acids and Bases, and the Role of Water. (n.d.). Retrieved from

http://chemed.chem.purdue.edu/genchem/topicreview/bp/ch11/acidbase.php

Difference Between Amphiprotic and Amphoteric. (2014, December 9). Retrieved from

http://www.differencebetween.com/difference-between-amphiprotic-and-vs-amphoteric/

Fact Sheet: Perchloric Acid Use. (n.d.). Retrieved from http://ehs.uky.edu/ohs/perchloric.htm

Lewis Concept of Acids and Bases. (2016, December 14). Retrieved from

https://chem.libretexts.org/Core/Physical_and_Theoretical_Chemistry/Acids_and_Bases/Aci

d/Lewis_Concept_of_Acids_and_Bases

Muller, W. (1958, August 5). Process of manufacturing perchloric acid by anodic oxidation of

chlorine. Retrieved from https://www.google.com/patents/US2846383#backward-citations

Pearson, R. G. (1963). Hard and Soft Acids and Bases. Journal of The American Chemical

Society, 85(22). https://doi.org/10.1021/ja00905a001

Perchloric Acid. (2013). Retrieved from

https://www.gfschemicals.com/statics/coreproducts/Perchloric_acid.html

Perchloric Acid. (2014, April 24). Retrieved from

https://www.drs.illinois.edu/SafetyLibrary/PerchloricAcid

Perchloric Acid. (n.d.). Retrieved from

https://pubchem.ncbi.nlm.nih.gov/compound/perchloric_acid#section=Top

Perchloric Acid Safety. (n.d.). North Carolina State University.

Sarpong, R. (2013). Standard Operating Procedures: Perchloric Acid. Retrieved from

http://www.cchem.berkeley.edu/rsgrp/SOPs2013/PerchloricAcid_Sarpong.pdf

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SCH4U Acid-Base: Concentrated vs. Dilute; Strong vs. Weak. (n.d.). Retrieved from

http://www2.ucdsb.on.ca/tiss/stretton/chem2/acid02.html

Schilt, A. A. (1979). Perchloric Acid and Perchlorate. The G. Frederick Smith Chemical

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http://www.bbc.co.uk/schools/gcsebitesize/science/triple_ocr_gateway/how_much/strong_w

eak_acids/revision/1/

Vogt, H., Balej, J., Bennett, J. E., Wintzer, P., Sheikh, S. A., & Gallone, P. (2002). Chlorine

Oxides and Chlorine Oxygen Acids. In Ullmanns Encyclopedia of Industrial Chemistry.

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