ACIDS AND BASES
The name "acid" calls to mind vivid sensory images—of tartness, for instance, if the acid in question is meant for human consumption, as with the citric acid in lemons. On the other hand, the thought of laboratory-and industrial-strength substances with scary-sounding names, such as sulfuric acid or hydrofluoric acid, carries with it other ideas—of acids that are capable of destroying materials, including human flesh. The name "base," by contrast, is not widely known in its chemical sense, and even when the older term of "alkali" is used, the sense-impressions produced by the word tend not to be as vivid as those generated by the thought of "acid." In their industrial applications, bases too can be highly powerful. As with acids, they have many household uses, in substances such as baking soda or oven cleaners. From a taste standpoint, (as anyone who has ever brushed his or her teeth with baking soda knows), bases are bitter rather than sour. How do we know when something is an acid or a base? Acid-base indicators, such as litmus paper and other materials for testing pH, offer a means of judging these qualities in various substances. However, there are larger structural definitions of the two concepts, which evolved in three stages during the late nineteenth and early twentieth centuries, that provide a more solid theoretical underpinning to the understanding of acids and bases.
HOW IT WORKS
INTRODUCTION TO ACIDS AND BASES
Prior to the development of atomic and molecular theory in the nineteenth century, followed by the discovery of subatomic structures in the late nineteenth and early twentieth centuries, chemists could not do much more than make measurements and observations. Their definitions of substances were purely phenomenological—that is, the result of experimentation and the collection of data. From these observations, they could form general rules, but they lacked any means of "seeing" into the atomic and molecular structures of the chemical world.
The phenomenological distinctions between acids and bases, gathered by scientists from ancient times onward, worked well enough for many centuries. The word "acid" comes from the Latin term acidus, or "sour," and from an early period, scientists understood that substances such as vinegar and lemon juice shared a common acidic quality. Eventually, the phenomenological definition of acids became relatively sophisticated, encompassing such details as the fact that acids produce characteristic colors in certain vegetable dyes, such as those used in making litmus paper. In addition, chemists realized that acids dissolve some metals, releasing hydrogen in the process.
WHY "BASE" AND NOT "ALKALI"?
The word "alkali" comes from the Arabic al-qili, which refers to the ashes of the seawort plant. The latter, which typically grows in marshy areas, was often burned to produce soda ash, used in making soap. In contrast to acids, bases—caffeine, for example—have a bitter taste, and many of them feel slippery to the touch. They also produce characteristic colors in the vegetable dyes of litmus paper, and can be used to promote certain chemical reactions. Note that today chemists use the word "base" instead of "alkali," Page 311 | Top of Article the reason being that the latter term has a narrower meaning: all alkalies are bases, but not all bases are alkalies.
Originally, "alkali" referred only to the ashes of burned plants, such as seawort, that contained either sodium or potassium, and from which the oxides of sodium and potassium could be obtained. Eventually, alkali came to mean the soluble hydroxides of the alkali and alkaline earth metals. This includes sodium hydroxide, the active ingredient in drain and oven cleaners; magnesium hydroxide, used for instance in milk of magnesia; potassium hydroxide, found in soaps and other substances; and other compounds. Broad as this range of substances is, it fails to encompass the wide array of materials known today as bases—compounds which react with acids to form salts and water.
TOWARD A STRUCTURAL DEFINITION
The reaction to form salts and water is, in fact, one of the ways that acids and bases can be defined. In an aqueous solution, hydrochloric acid and sodium hydroxide react to form sodium chloride—which, though it is suspended in an aqueous solution, is still common table salt—along with water. The equation for this reaction is HCl(aq) + NaOH(aq) →H2O + NaCl(aq). In other words, the sodium (Na) ion in sodium hydroxide switches places with the hydrogen ion in hydrochloric acid, resulting in the creation of NaCl (salt) along with water.
But why does this happen? Useful as this definition regarding the formation of salts and water is, it is still not structural—in other words, it does not delve into the molecular structure and behavior of acids and bases. Credit for the first truly structural definition of the difference goes to the Swedish chemist Svante Arrhenius (1859-1927). It was Arrhenius who, in his doctoral dissertation in 1884, introduced the concept of an ion, an atom possessing an electric charge.
His understanding was particularly impressive in light of the fact that it was 13 more years before the discovery of the electron, the subatomic particle responsible for the creation of ions. Atoms have a neutral charge, but when an electron or electrons depart, the atom becomes a positive ion or cation. Similarly, when an electron or electrons join a previously uncharged
atom, the result is a negative ion or anion. Not only did the concept of ions greatly influence the future of chemistry, but it also provided Arrhenius with the key necessary to formulate his distinction between acids and bases.
THE ARRHENIUS DEFINITION
Arrhenius observed that molecules of certain compounds break into charged particles when placed in liquid. This led him to the Arrhenius acid-base theory, which defines an acid as any compound that produces hydrogen ions (H+) when dissolved in water, and a base as any compound that produces hydroxide ions (OH−) when dissolved in water.
This was a good start, but two aspects of Arrhenius's theory suggested the need for a definition that encompassed more substances. First of all, his theory was limited to reactions in aqueous solutions. Though many acid-base reactions do occur when water is the solvent, this is not always the case.
Second, the Arrhenius definition effectively limited acids and bases only to those ionic compounds, such as hydrochloric acid or sodium hydroxide, which produced either hydrogen or
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hydroxide ions. However, ammonia, or NH3, acts like a base in aqueous solutions, even though it does not produce the hydroxide ion. The same is true of other substances, which behave like acids or bases without conforming to the Arrhenius definition.
These shortcomings pointed to the need for a more comprehensive theory, which arrived with the formulation of the Brønsted-Lowry definition by English chemist Thomas Lowry (1874-1936) and Danish chemist J. N. Brønsted (1879-1947). Nonetheless, Arrhenius's theory represented an important first step, and in 1903, he was awarded the Nobel Prize in Chemistry for his work on the dissociation of molecules into ions.
THE BRØNSTED-LOWRY DEFINITION
The Brønsted-Lowry acid-base theory defines an acid as a proton (H+) donor, and a base as a proton acceptor, in a chemical reaction. Protons are represented by the symbol H+, and in representing acids and bases, the symbols HA and A−, respectively, are used. These symbols indicate that an acid has a proton it is ready to give away, while a base, with its negative charge, is ready to receive the positively charged proton.
Though it is used here to represent a proton, it should be pointed out that H+ is also the hydrogen ion—a hydrogen atom that has lost its sole electron and thus acquired a positive charge. Page 313 | Top of Article It is thus really nothing more than a lone proton, but this is the one and only case in which an atom and a proton are exactly the same thing. In an acid-base reaction, a molecule of acid is "donating" a proton, in the form of a hydrogen ion. This should not be confused with a far more complex process, nuclear fusion, in which an atom gives up a proton to another atom.
AN ACID-BASE REACTION IN BRØNSTED-LOWRY THEORY.
The most fundamental type of acid-base reaction in Brønsted-Lowry theory can be symbolized thus HA(aq) + H2O(l) →H3O+(aq) + A−(aq). The first acid shown—which, like three of the four "players" in this equation, is dissolved in an aqueous solution—combines with water, which can serve as either an acid or a base. In the present context, it functions as a base.
Water molecules are polar, meaning that the negative charges tend to congregate on one end of the molecule with the oxygen atom, while the positive charges remain on the other end with the hydrogen atoms. The Brønsted-Lowry model emphasizes the role played by water, which pulls the proton from the acid, resulting in the creation of H3O+, known as the hydronium ion.
The hydronium ion produced here is an example of a conjugate acid, an acid formed when a base accepts a proton. At the same time, the acid has lost its proton, becoming A−, a conjugate base—that is, the base formed when an acid releases a proton. These two products of the reaction are called a conjugate acid-base pair, a term that refers to two substances related to one another by the donating of a proton.
Brønsted and Lowry's definition represents an improvement over that of Arrhenius, because it includes all Arrhenius acids and bases, as well as other chemical species not encompassed in Arrhenius theory. An example, mentioned earlier, is ammonia. Though it does not produce OH− ions, ammonia does accept a proton from a water molecule, and the reaction between these two (with water this time serving the function of acid) produces the conjugate acid-base pair of NH4+ (an ammonium ion) and OH−. Note that the latter, the hydroxide ion, was not produced by ammonia, but is the conjugate base that resulted when the water molecule lost its H+ atom or proton.
THE LEWIS DEFINITION
Despite the progress offered to chemists by the Brønsted-Lowry model, it was still limited to describing compounds that contain hydrogen. As American chemist Gilbert N. Lewis (1875-1946) recognized, this did not encompass the full range of acids and bases; what was needed, instead, was a definition that did not involve the presence of a hydrogen atom.
Lewis is particularly noted for his work in the realm of chemical bonding. The bonding of atoms is the result of activity on the part of the valence electrons, or the electrons at the "outside" of the atom. Electrons are arranged in different ways, depending on the type of bonding, but they always bond in pairs.
According to the Lewis acid-base theory, an acid is the reactant that accepts an electron pair from another reactant in a chemical reaction, while a base is the reactant that donates an electron pair to another reactant. As with the Brønsted-Lowry definition, the Lewis definition is reaction-dependant, and does not define a compound as an acid or base in its own right. Instead, the manner in which the compound reacts with another serves to identify it as an acid or base.
AN IMPROVEMENT OVER ITS PREDECESSORS.
The beauty of the Lewis definition lies in the fact that it encompasses all the situations covered by the others—and more. Just as Brønsted-Lowry did not disprove Arrhenius, but rather offered a definition that covered more substances, Lewis expanded the range of substances beyond those covered by Brønsted-Lowry. In particular, Lewis theory can be used to differentiate the acid and base in bond-producing chemical reactions where ions are not produced, and in which there is no proton donor or acceptor. Thus it represents an improvement over Arrhenius and Brønsted-Lowry respectively.
An example is the reaction of boron trifluoride (BF3) with ammonia (NH3), both in the gas phases, to produce boron trifluoride ammonia complex (F3BNH3). In this reaction, boron trifluoride accepts an electron pair and is therefore a Lewis acid, while ammonia donates the electron pair and is thus a Lewis base. Though hydrogen is involved in this particular reaction, Lewis theory also addresses reactions involving no hydrogen.
pHAND ACID-BASE INDICATORS
Though chemists apply the sophisticated structural definitions for acids and bases that we have discussed, there are also more "hands-on" methods for identifying a particular substance (including complex mixtures) as an acid or base. Many of these make use of the pH scale, developed by Danish chemist SØren SØrensen (1868-1939) in 1909.
The term pH stands for "potential of hydrogen," and the pH scale is a means of determining the acidity or alkalinity of a substance. (Though, as noted, the term "alkali" has been replaced by "base," alkalinity is still used as an adjectival term to indicate the degree to which a substance displays the properties of a base.) There are theoretically no limits to the range of the pH scale, but figures for acidity and alkalinity are usually given with numerical values between 0 and 14.
THE MEANING OF pH VALUES.
A rating of 0 on the pH scale indicates a substance that is virtually pure acid, while a 14 rating represents a nearly pure base. A rating of 7 indicates a neutral substance. The pH scale is logarithmic, or exponential, meaning that the numbers represent exponents, and thus an increased value of 1 represents not a simple arithmetic addition of 1, but an increase of 1 power. This, however, needs a little further explanation.
The pH scale is actually based on negative logarithms for the values of H3O+ (the hydronium ion) or H+ (protons) in a given substance. The formula is thus pH = −log[H3O+] or −log[H+], and the presence of hydronium ions or protons is measured according to their concentration of moles per liter of solution.
pH VALUES OF VARIOUS SUBSTANCES.
The pH of a virtually pure acid, such as the sulfuric acid in car batteries, is 0, and this represents 1 mole (mol) of hydronium per liter (l) of solution. Lemon juice has a pH of 2, equal to 10−2 mol/l. Note that the pH value of 2 translates to an exponent of −2, which, in this case, results in a figure of 0.01 mol/l.
Distilled water, a neutral substance with a pH of 7, has a hydronium equivalent of 10−7 mol/l. It is interesting to observe that most of the fluids in the human body have pH values in the neutral range blood (venous, 7.35; arterial, 7.45); urine (6.0—note the higher presence of acid); and saliva (6.0 to 7.4).
At the alkaline end of the scale is borax, with a pH of 9, while household ammonia has a pH value of 11, or 10−11 mol/l. Sodium hydroxide, or lye, an extremely alkaline chemical with a pH of 14, has a value equal to 10−14 moles of hydronium per liter of solution.
LITMUS PAPER AND OTHER INDICATORS.
The most precise pH measurements are made with electronic pH meters, which can provide figures accurate to 0.001 pH. However, simpler materials are also used. Best known among these is litmus paper (made from an extract of two lichen species), which turns blue in the presence of bases and red in the presence of acids. The term "litmus test" has become part of everyday language, referring to a make-or-break issue—for example, "views on abortion rights became a litmus test for Supreme Court nominees."
Litmus is just one of many materials used for making pH paper, but in each case, the change of color is the result of the neutralization of the substance on the paper. For instance, paper coated with phenolphthalein changes from colorless to pink in a pH range from 8.2 to 10, so it is useful for testing materials believed to be moderately alkaline. Extracts from various fruits and vegetables, including red cabbages, red onions, and others, are also applied as indicators.
SOME COMMON ACIDS AND BASES
The tables below list a few well-known acids and bases, along with their formulas and a few applications
- Acetic acid (CH3COOH): vinegar, acetate
- Acetylsalicylic acid (HOOCC6H4OOCCH3): aspirin
- Ascorbic acid (H2C6H6O6): vitamin C
- Carbonic acid (H2CO3): soft drinks, seltzer water
- Citric acid (C6H8O7): citrus fruits, artificial flavorings
- Hydrochloric acid (HCl): stomach acid
- Nitric acid (HNO3): fertilizer, explosives
- Sulfuric acid (H2SO4): car batteries
- Aluminum hydroxide (Al[OH]3): antacids, deodorants
- Ammonium hydroxide (NH4OH): glass cleaner
- Calcium hydroxide (Ca[OH]2): caustic lime, mortar, plaster
- Magnesium hydroxide (Mg[OH]2): laxatives, antacids
- Sodium bicarbonate/sodium hydrogen carbonate (NaHCO3): baking soda
- Sodium carbonate (Na2CO3): dish detergent
- Sodium hydroxide (NaOH): lye, oven and drain cleaner
- Sodium hypochlorite (NaClO): bleach
Of course these represent only a few of the many acids and bases that exist. Selected substances listed above are discussed briefly below.
ACIDS IN THE HUMAN BODY AND FOODS.
As its name suggests, citric acid is found in citrus fruits—particularly lemons, limes, and grapefruits. It is also used as a flavoring agent, preservative, and cleaning agent. Produced commercially from the fermentation of sugar by several species of mold, citric acid creates a taste that is both tart and sweet. The tartness, of course, is a function of its acidity, or a manifestation of the fact that it produces hydrogen ions. The sweetness is a more complex biochemical issue relating to the ways that citric acid molecules fit into the tongue's "sweet" receptors.
Citric acid plays a role in one famous stomach remedy, or antacid. This in itself is interesting, since antacids are more generally associated with alkaline substances, used for their ability to neutralize stomach acid. The fizz in Alka-Seltzer, however, comes from the reaction of citric acids (which also provide a more pleasant taste) with sodium bicarbonate or baking soda, a base. This reaction produces carbon dioxide gas. As a preservative, citric acid prevents metal ions from reacting with, and thus hastening the degradation of, fats in foods. It is also used in the production of hair rinses and low-pH shampoos and toothpastes.
The carboxylic acid family of hydrocarbon derivatives includes a wide array of substances—not only citric acids, but amino acids. Amino acids combine to make up proteins, one of the principal components in human muscles, skin, and hair. Carboxylic acids are also applied industrially, particularly in the use of fatty acids for making soaps, detergents, and shampoos.
There are plenty of acids found in the human body, including hydrochloric acid or stomach acid—which, in large quantities, causes indigestion, and the need for neutralization with a base. Nature also produces acids that are toxic to humans, such as sulfuric acid.
Though direct exposure to sulfuric acid is extremely dangerous, the substance has numerous applications. Not only is it used in car batteries, but sulfuric acid is also a significant component in the production of fertilizers. On the other hand, sulfuric acid is damaging to the environment when it appears in the form of acid rain. Among the impurities in coal is sulfur, and this results in the production of sulfur dioxide and sulfur trioxide when the coal is burned. Sulfur trioxide reacts with water in the air, creating sulfuric acid and thus acid rain, which can endanger plant and animal life, as well as corrode metals and building materials.
The alkali metal and alkaline earth metal families of elements are, as their name suggests, bases. A number of substances created by the reaction of these metals with nonmetallic elements are taken internally for the purpose of settling gastric trouble or clearing intestinal blockage. For instance, there is magnesium sulfate, better known as Epsom salts, which provide a powerful laxative also used for ridding the body of poisons.
Aluminum hydroxide is an interesting base, because it has a wide number of applications, including its use in antacids. As such, it reacts with and neutralizes stomach acid, and for that reason is found in commercial antacids such as Di-Gel™, Gelusil™, and Maalox™. Aluminum hydroxide is also used in water purification, in dyeing garments, and in the production of certain kinds of glass. A close relative, aluminum hydroxychloride or Al2(OH)5Cl, appears in many commercial antiperspirants, and helps to close pores, thus stopping the flow of perspiration.
SODIUM HYDROGEN CARBONATE (BAKING SODA).
Baking soda, known by chemists both as sodium bicarbonate Page 316 | Top of Article and sodium hydrogen carbonate, is another example of a base with multiple purposes. As noted earlier, it is used in Alka-Seltzer™, with the addition of citric acid to improve the flavor; in fact, baking soda alone can perform the function of an antacid, but the taste is rather unpleasant.
Baking soda is also used in fighting fires, because at high temperatures it turns into carbon dioxide, which smothers flames by obstructing Page 317 | Top of Article the flow of oxygen to the fire. Of course, baking soda is also used in baking, when it is combined with a weak acid to make baking powder. The reaction of the acid and the baking soda produces carbon dioxide, which causes dough and batters to rise. In a refrigerator or cabinet, baking soda can absorb unpleasant odors, and additionally, it can be applied as a cleaning product.
SODIUM HYDROXIDE (LYE).
Another base used for cleaning is sodium Page 318 | Top of Article hydroxide, known commonly as lye or caustic soda. Unlike baking soda, however, it is not to be taken internally, because it is highly damaging to human tissue—particularly the eyes. Lye appears in drain cleaners, such as Drano™, and oven cleaners, such as Easy-Off™, which make use of its ability to convert fats to water-soluble soap.
In the process of doing so, however, relatively large amounts of lye may generate enough heat to boil the water in a drain, causing the water to shoot upward. For this reason, it is not advisable to stand near a drain being treated with lye. In a closed oven, this is not a danger, of course; and after the cleaning process is complete, the converted fats (now in the form of soap) can be dissolved and wiped off with a sponge.
WHERE TO LEARN MORE
ChemLab. Danbury, CT: Grolier Educational, 1998.
Ebbing, Darrell D.; R. A. D. Wentworth; and James P. Birk. Introductory Chemistry. Boston: Houghton Mifflin, 1995.
Haines, Gail Kay. What Makes a Lemon Sour? Illustratedby Janet McCaffery. New York: Morrow, 1977.
Oxlade, Chris. Acids and Bases. Chicago: Heinemann Library, 2001.
Patten, J.M. Acids and Bases. Vero Beach, FL: Rourke Book Company, 1995.
Walters, Derek. Chemistry. Illustrated by Denis Bishopand Jim Robins. New York: F. Watts, 1982.
Zumdahl, Steven S. Introductory Chemistry A Foundation, 4th ed. Boston: Houghton Mifflin, 2000.