Arrhenius Theory: Svante Arrhenius (1884), Sweden

An Arrhenius acid is substances dissociate in water to produce H+ ions An Arrhenius base is substances dissociate in water to produce OH- ions

Example: HCl(aq) > H+(aq) + Cl-(aq) CH3COOH(aq) <-> CH3COO-(aq) + H+(aq)

HCl and CH3COOH are Arrhenius acids

Example: NaOH(aq) > Na+(aq) + OH-(aq) Ba(OH)2(aq) > Ba2+(aq) + 2OH-(aq)

NaOH and Ba(OH)2 are Arrhenius bases

Limitation: Many compound show basic properties but do not contain OHExample: NH3, Na2CO3 and C2H5ONa The Brnsted-Lowry Acid-Base Theory: Johannes Brnsted (1879-1947), Denmark and Thomas Lowry (1874-1936), England

A Brnsted-Lowry acid is a proton (H+) donor A Brnsted-Lowry base is a proton (H+) acceptor In an acid-base reaction, a proton is transferred from an acid to a base

Brnsted-Lowry acid-base reaction: HB(aq) + A-(aq) <-> HA(aq) + B-(aq)

HB and HA act as Brnsted-Lowry acid A- and B- act as Brnsted-Lowry base

Conjugate base is the species formed when a proton is removed from an acid Conjugate acid is the species formed when a proton is added to a base

B- is the conjugate base of HB HA is the conjugate acid of A-

Conjugate acid-base pair differs only in the presence or absence of a proton, H+ Example: Conjugate acid NH4+ HSO4HF Conjugate base NH3 SO42F-

Amphiprotic is a species that can either accept or donate a proton. Example: H2O molecule Hydronium ion (H3O+) H2O molecule gain a proton Hydroxide ion (OH-) H2O molecule lose a proton

Lewis Theory: G.N. Lewis (1938), America

A Lewis acid is a species (an atom, ion or molecule) form a dative covalent bond by accepting an electron-pair from base[electron pair acceptor] A Lewis base is a species form a dative covalent bond by donating an unshared electron-pairwith an atom, ion or molecule[electron pair donor]

Example 1: B(OH)3(aq) + H2O(l) <-> B(OH)4-(aq) + H+(aq)

Lewis acid: Boric acid (H3BO3) Lewis base: Water (H2O)

Example 2: BF3 + NH3 > BF3NH3

Lewis acid: BF3 Lewis base: NH3

Example 3: Cu2+(aq) + 4NH3(aq) > [Cu(NH3)4]2+(aq)

Lewis acid: Cu2+ Lewis base: NH3

Example 4: Ni(s) + 4CO(g) <-> Ni(CO)4(l)

Lewis acid: Ni Lewis base: CO

The Lewis Definitions of Acids and Bases

In 1923 G. N. Lewis suggested another way of looking at the reaction between H+ and OH- ions. In the Brnsted model, the OH- ion is the active species in this reaction accepts an H ion to form a covalent bond. In the Lewis model, the H ion is the active species bond. it accepts a pair of electrons from the OH- ion to form a covalent
+ +

it

In the Lewis theory of acid-base reactions, bases donate pairs of electrons and acids accept pairs of electrons. A Lewis acid is therefore any substance, such as the H+ ion, that can accept a pair of nonbonding electrons. In other words, a Lewis acid is anelectron-pair acceptor. A Lewis base is any substance, such as the OH- ion, that can donate a pair of nonbonding electrons. A Lewis base is therefore an electronpair donor. One advantage of the Lewis theory is the way it complements the model of oxidationreduction reactions. Oxidation-reduction reactions involve a transfer of electrons from one atom to another, with a net change in the oxidation number of one or more atoms.

The Lewis theory suggests that acids react with bases to share a pair of electrons, with no change in the oxidation numbers of any atoms. Many chemical reactions can be sorted into one or the other of these classes. Either electrons are transferred from one atom to another, or the atoms come together to share a pair of electrons.

The principal advantage of the Lewis theory is the way it expands the number of acids and therefore the number of acid-base reactions. In the Lewis theory, an acid is any ion or molecule that can accept a pair of nonbonding valence electrons. In the preceding section, we concluded that Al3+ ions form bonds to six water molecules to give a complex ion.

Al3+(aq) + 6 H2O(l)

Al(H2O)63+(aq)

This is an example of a Lewis acid-base reaction. The Lewis structure of water suggests that this molecule has nonbonding pairs of valence electrons and can therefore act as a Lewis base. The electron configuration of the Al3+ ion suggests that this ion has empty 3s, 3p, and 3d orbitals that can be used to hold pairs of nonbonding electrons donated by neighboring water molecules. Al3+ = [Ne] 3s0 3p0 3d0 Thus, the Al(H2O)63+ ion is formed when an Al3+ ion acting as a Lewis acid picks up six pairs of electrons from neighboring water molecules acting as Lewis bases to give an acid-base complex, or complex ion. The Lewis acid-base theroy explains why BF3 reacts with ammonia. BF3 is a trigonalplanar molecule because electrons can be found in only three places in the valence shell of the boron atom. As a result, the boron atom is sp2 hybridized, which leaves an empty 2pzorbital on the boron atom. BF3 can therefore act as an electron-pair acceptor, or Lewis acid. It can use the empty 2pz orbital to pick up a pair of nonbonding electrons from a Lewis base to form a covalent bond. BF3 therefore reacts with Lewis bases such as NH3 to form acid-base complexes in which all of the atoms have a filled shell of valence electrons, as shown in the figure below.

The Lewis acid-base theory can also be used to explain why nonmetal oxides such as CO2 dissolve in water to form acids, such as carbonic acid H2CO3.

CO2(g) + H2O(l)

H2CO3(aq)

In the course of this reaction, the water molecule acts as an electron-pair donor, or Lewis base. The electron-pair acceptor is the carbon atom in CO2. When the carbon atom picks up a pair of electrons from the water molecule, it no longer needs to form double bonds with both of the other oxygen atoms as shown in the figure below

One of the oxygen atoms in the intermediate formed when water is added to CO2 carries a positive charge; another carries a negative charge. After an H+ ion has

been transferred from one of these oxygen atoms to the other, all of the oxygen atoms in the compound are electrically neutral. The net result of the reaction between CO2 and water is therefore carbonic acid, H2CO3.

There are several ways to define acids and bases, but pH only refers to hydrogen ion concentration and is only meaningful when applied to aqueous (water-based) solutions. When water dissociates it yields a hydrogen ion and a hydroxide. H2O H+ + OHWhen calculating pH, remember that [] refers to molarity, M. Kw = [H+][OH-] = 1x10-14 at 25C for pure water [H+] = [OH-] = 1x10-7 Acidic Solution: [H+] > 1x10-7 Basic Solution: [H+] < 1x10-7 Calculate pH and [H+] pH = -log10[H+] [H+] = 10-pH Example: Calculate the pH for a specific [H+]. Calculate pH given [H+] = 1.4 x 10-5 M pH = -log10[H+] pH = -log10(1.4 x 10-5) pH = 4.85 Example: Calculate [H+] from a known pH. Find [H+] if pH = 8.5 [H+] = 10-pH [H+] = 10-8.5 [H+] = 3.2 x 10-9 M