Early Theories of Acids and Bases

The word acid comes from the Latin word acere which means sour. Vinegar and lemons were long known by the ancients to taste sour. The word base has a more obscure origin. However, the word alkaline (another older word for base) was derived from the Arabic word al-qily meaning roasted in a pan or the ashes of plants. Writings as early as the 900s have shown that mixing the ashes of plants with water, then with slaked lime would produce the alkaline solutions NaOH and KOH. Acids and bases were initially defined based on observable properties, also called operational definitions. In 1661, Robert Boyle (1627-1691) described the properties of acids as:

sour taste. changed the colour of a vegetable dye called litmus red. corrosive become less acidic when mixed with alkalies.

He also described the properties of bases or alkalies as:

have a slippery feel change litmus blue become less alkali when mixed with acids.

Antoinne Lavoisier (1743-1794) created the word oxygen in 1777 after the Greek words oxys for sour and genes for born. He said that oxygen was an acid-maker. He studied several acids, including nitric and sulphuric, and proposed that oxygen was responsible for compounds being acidic. He was wrong, but he was one of the first to chemically identify acids as opposed to observable properties. In 1810 Sir Humphry Davys interest in acids and bases came as a result of questioning Lavoisiers theory. He noticed that reactions of several acids with metals and non-metals never resulted in the production of oxygen. He proposed that hydrogen was gives a compound acidic qualities. Davys theory was not complete since many hydrogen-containing compounds, like ammonia (NH3), are not acidic. In 1838, Justus Liebig (1803-1873), a German chemist, modified Davys theory proposing that acids contain hydrogens that can be replaced by metals to form a salt. This theory held for about 50 years until Svante Arrhenius description of acids and bases.

Svante Arrhenius
In the early 1880's, a Swedish chemist named Svante Arrhenius (1859 - 1927) was studying the conductivity of solutions. At that time, very little was known about the structure of atoms and molecules. He proposed that electrolytes break up into charged particles in water. Scientists of the time did not accept Arrhenius' theory. They believed that atoms and molecules were indestructible and could not break apart. Consequently, in 1894, Arrhenius was given the lowest possible mark for the defence of his Ph. D. thesis. Arrhenius believed in his theory and, with the help of some prominent scientists, continued to press the scientific community to accept his theory. Eventually as the knowledge of atomic structure increased, Arrhenius' theory was accepted. In 1903, Arrhenius received the Nobel Prize for his work. In 1887, Arrhenius discovered that all acidic and basic solutions he tested were electrolytes. He determined that acids and bases must ionize or dissociate in water. According to Arrhenius, an acid is defined as a substance, when dissolved in water, which releases hydrogen ions or increases the hydrogen ion concentration. Example 1. Hydrochloric acid: HCl(aq) H+(aq) + Cl(aq) From a particle view, HCl forms ions in water:

Example 2. Acetic acid (vinegar): HC2H3O2(aq) H+(aq) + C2H3O2(aq) According to Arrhenius, a base is defined as a substance, when dissolved in water, releases hydroxide ions.

Example 3. Sodium hydroxide NaOH(s) Na+(aq) + OH(aq) From a particle level, NaOH dissociates like an ionic compound.

Example 4. Ammonia: Ammonia is a little troublesome to explain with Arrhenius' theory. It must first be shown to react with water then dissociate. NH3(g) + H2O(l) NH4OH(aq) NH4+(aq) + OH(aq) Arrhenius is the standard definition of acids and bases used in your earlier science courses and in Topic 1 of this course. Until Arrhenius there was no satisfactory explanation for why acids and bases neutralize each other. He proposed that hydrogen ions produced by acids react with hydroxide ions released by bases to form water.

Problems with the Arrhenius Theory

The Arrhenius definition says that acids and bases can only occur in water solutions. However, we notice that hydrogen chloride gas and ammonia gas will react together. That is, as a gas hydrogen chloride is an acid and ammonia is a base. The Arrhenius definition does not account for this. There are many substances which are acidic or basic but do not have a hydrogen ion or a hydroxide ion. For example,

baking soda (sodium bicarbonate, NaHCO3) in water turns litmus blue, but has no apparent hydroxide ion. metal ions, such as iron (III) and aluminum, turn litmus red, but have no hydrogen ions. The Arrhenius definition does not account for the acidity and basicity of these examples.

The Arrhenius Theory is not a complete loss, however, since it was important in establishing the concept of dissociation and explaining the process of neutralization. The Arrhenius Theory was also an essential starting point for the further development of our understanding of acids and bases.

Bronsted-Lowry Theory
The limitations of the Arrhenius theory prompted a Danish chemist named Johannes Brnsted (1879-1947) and an English chemist Thomas Lowry (1874-1936) to independently developed a more general definition of acids and bases, within months of each other in 1923. This definition accounted for the acidity of metal ions AND the basicity (alkalinity) of baking soda. Since they developed essentially the same theory such a short time apart, we apply both their names to their theory of acids and bases. According to the Brnsted-Lowry definition, an acid is a proton or H+ ion donor. A base is defined as a proton acceptor. For example,

In this example, hydrogen chloride (hydrochloric acid) reacts with water by donating a proton. Water acts as the base, accepting the proton. The result is the H3O+ ion called the hydronium ion. Click on the link below to view an animation of this reaction. HCl In this example, ammonia's properties as a base are better explained by the Brnsted-Lowry definition. Ammonia accepts a proton from water, making ammonia a base and water the acid. The result is the ammonium ion and the hydroxide ion.

Now, when we think about acids donating protons, it isn't usually willingly. You see, the hydrogen atoms involved are usually bonded to the rest of the molecule. It then requires some "convincing" for the molecule to give up or "donate" its proton. We can think of it in terms of the playground bully who "convinces" the children to "donate" their milk money. The base is the playground bully. Bases have a strong affinity or desire for protons. So much so that, if they are strong enough, they will steal the proton from an acid and combine it with itself. The stronger the bond between the hydrogen and the rest of the molecule, the more difficult it is for the base to take the proton. So this accepting and donating business is just a nice way to talk about an acid being "mugged" by a base. In the Brnsted-Lowry definition of acids and bases substances like water can act as BOTH an acid and a base. These types of substances are called amphoteric (the root "amph" is similar to the root of amphibian which means "having two lives", on land and in water). Another example of an amphoteric substance is the hydrogen carbonate ion, HCO3, found in baking soda. The hydrogen carbonate can act as an acid by losing its hydrogen in water: HCO3 + H2O CO32 + H3O+ or as a base by stealing a proton from water: HCO3 + H2O H2CO3 + OH

Advantages and Problems With Bronsted-Lowry

The Arrhenius Theory of acids and bases was limited to aqueous solutions. The Brnsted-Lowry Theory expands the definition of an acid and base to a proton donor or acceptor. However, even though acids and bases can occur without water there is still a requirement for the presence of a solvent. The Brnsted-Lowry Theory is able to explain why substances such as the hydrogen carbonate ion can act as an acid and a base and how substances without hydroxides, like ammonia, can act as bases. They did not explain, however, how substances without protons can act as acids. Brnsted and Lowry explained acids and bases in terms of proton donors and acceptors, when protons are actually taken away or stolen. Bases dont simply accept protons, but take protons away from acids. The Brnsted and Lowry theory is the most useful for us in this course, but we will examone another theory on the next page.

Gilbert Lewis
Aqueous metal ions with charges of 2+ and 3+, except group 2 metals, are acidic in water. Metal ions act as Lewis acids in water: Fe3+ + 6 H2O Fe(H2O)63+ Because of the large positive charge and the polar nature of water, the oxygen side of the water (negative) is attracted to the highly positive metal ion and forms a covalent bond with 6 water molecules. A diagram below shows the reaction between the metal ion and a single water molecule:

When 6 water molecules combine with the ferric ion, the structure looks like this:

Advantages of Lewis
Each successive definition for an acid becomes less restrictive until finally the Lewis definition becomes so general that any reaction in which a pair of electrons are transferred becomes an acid-base reaction. The significance of the Lewis concept is that it is more general than any of the other definitions. Lewis acid-base reactions include many reactions that would not be included with the Brnsted-Lowry definition. The Lewis acid-base theory does not affect the substances we have previously called Brnsted-Lowry bases because any Brnsted-Lowry base must have a pair of non-bonding electrons in order to accept a proton. However, this theory vastly expands the number of compounds we have called acids. Any compound that has one or more valence shell orbitals can now act as an acid! Many Lewis acid-base reactions can be quite complex, so we will focus on Brnsted-Lowry acid-base reactions in this module.

Conjugate Pairs
As mentioned on the previous page, in this course we will focus on the Brnsted-Lowry model of acids and bases. The general form of a Brnsted-Lowry acid-base reaction is Acid + Base Conjugate Acid + Conjugate Base

The conjugate acid is what remains after a base has accepted a proton and the conjugate base is what remains after the acid has donated its proton. Let's take another look at the reaction of ammonia with water. NH3(g) Base The reverse reaction would be NH4+(aq) Acid + OH(aq) Base NH3(g) +H2O(l) + H2O(l) Acid NH4+(aq) + OH(aq)

Notice an acid results form the ammonia accepting a proton from water. The ammonium ion can donate a proton to the hydroxide ion. The hydroxide ion accepts the proton making it a base. In the first reaction, ammonia is the base and the ammonium ion is its conjugate acid. Water is the acid in the first reaction and the hydroxide ion is its conjugate base. NH3(g) and NH4+(aq) are called a conjugate acid-base pair, as are H2O(l) and OH(aq). So, for this reversible reaction:

Click on the link below to view an animation that shows the dissociation of ammonia: Ammonia In general for the acid HA,

Click on the link below to view an animation that shows the dissociation of the weak acid acetic acid: Acetic Acid and for the base B,