Acids and Bases - the Three Definitions

1. Measurement of pH - the pH meter 2. Bronsted-Lowry definition of acids and bases - an acid is a proton donor - a base is a proton acceptor conjugate acid/conjugate base pairs - relationship of Ka of a conjugate acid and Kb of a conjugate base 3. Lewis definition of acids and bases - a base is an electron pair donor - an acid is an electron pair acceptor - some examples of Lewis acids and Lewis bases

Ionization Constants (1)

Ionization Constants (2)

Exercise on Acid/Bases Strength

For each conjugate acid/base pair, (1) Write the reactions defining Ka and Kb. (2) Find the values of pKa, pKb, and Kb. (3) Which species is the strongest conjugate acid, which is the strongest conjugate base?

nitrous acid: oxalic acid (2): arsenic acid (2): carbonic acid (1):

HNO2 / NO2HC2O4- / C2O42HAsO42- / AsO43H2CO3 / HCO3-

Hydrolysis Reactions
Which salts undergo hydrolysis? Is the resulting solution acidic, basic, or neutral? Write the hydrolysis reaction (if any). Calculate the pH of a 0.10 M solution. 1. sodium acetate (basic (pH=8.88), acetate (pKb=9.25) hydrolyses to produce OH-) 2. ammonium chloride
(acidic (pH=5.12), ammonium (pKa=9.25) hydrolyses to produce H3O+)

3.

calcium chloride (neutral, no hydrolysis)

4.

sodium monohydrogen phosphate (basic (pH=10.12), HPO42- (pKb2=6.79) hydrolyses to produce OH-) (you need to consider two conjugate acid/base pairs..)

pH and % Dissociation of a Monoprotic Weak Acid

What is the pH of 0.10 M CH3COOH?

CH3COOH 0.1 - x

= CH3COO- + x

H+ x

Ka = 1.75 x 10-5
(We let x = [H+])

Ka =

[CH3COO-] [H+] [CH3COOH]

x2 0.1 - x

= 1.75 x 10-5 (x << 0.1)

Approximation Method:

Since Ka <<1, assume x<<0.1 and x = [H+] = 0.0013 M

x2 = 0.1 * 1.75 * 10-5 = 1.75 x 10-6

Calculating % Dissociation and the pH

CH3COOH = CH3COO- + H+

[H+] = 1.3 x 10-3 M pH = - log10[H+] = 2.88

% dissociation = 100 *

[CH3COO-] [CH3COOH]init

x 0.1

= 1.3%

Measurement of pH: the pH Meter

pH varies linearly with output voltage and can be measured over the range pH 0 to pH 14

Ka and Acid Strength

The stronger the acid, the larger the Ka and the smaller the pKa: HNO2 (aq) = NO2- (aq) + H+ (aq) Ka = 4.6 x 10-4 pKa = 3.34
stronger

CH3COOH (aq)

= CH3COO- (aq) + H+ (aq)

Ka = 1.76 x 10-5 pKa = 4.75

HCN (aq)

= CN- (aq) + H+ (aq)

Ka = 6.17 x 10-10 pKa = 9.21

weaker

Weak Acids
stronger
= =

= = =

weaker

Kb and pKb
Arrhenius bases liberate OH- in solution. Kb is the equilibrium constant for this reaction.

NH4OH (aq)

= NH4+ (aq) + OH- (aq) [NH4+] [OH-] [NH4OH]

Kb =

= 1.76 x 10-5 pKb = - log10 Kb (definition)

pKb = - log10 (1.8 x 10-5) = 4.74

Kb and Base Strength

The stronger the base, the larger the Kb and the smaller the pKb:
stronger

PO43- (aq) + H2O (l) = HPO42- (aq) + OH- (aq)

Kb = 4.5 x 10-2 pKb = 1.34

NH4OH (aq)

= NH4+ (aq) + OH- (aq)

Kb = 1.8 x 10-5 pKb = 4.74

Conclusion: phosphate anion is a stronger base than NH4OH.

weaker

Kb's of weak bases

Strength (Ranked)

3 7 6 1 5 2 4

Acids and Bases - Three Definitions

Arrhenius Definition: Acids: increases [H+] in aqueous solution Bases: increases [OH-] in aqueous solution

Bronsted-Lowry Definition:

(based on proton transfer reactions)

Acids: proton (H+) donor Bases: proton (H+) acceptor Lewis Definition: Acids: electron pair acceptor Bases: electron pair donor

Some Lewis Acids and Bases

Lewis bases are characterized by having an available lone pair. Examples are:

.. :O-H..
hydroxide

.. :.. : I
iodide

H : N-H H
ammonia

.. : O-H H
water

.. 2:S : ..
sulfide

Lewis acids are electron deficient - i.e., electron pair acceptors Examples are:

H+

Zn2+
metal cations

Hg2+

Ag+

BF3
electron deficient compounds

Lewis Acids/Bases - the Most General Definition

The Lewis definition generalizes the acid/base concept: Every Arrhenius acid/base is also a Lewis acid/base. Every Bronsted acid/base is also a Lewis acid/base.
Least general definition Arrhenius Bronsted-Lowry Most general definition Lewis

Example: A strong acid reacts with a strong base:

H+(aq) + :OH-(aq) = H2O(l)

Electron pair acceptor

electron pair donor

The Lewis Acid-Base Reaction

Lewis definition: Acid: electron pair acceptor Base: electron pair donor

HNO2 + ClO2- = HClO2 + NO2Bronsted-Lowry: acid1 base2 acid2 base1

The Lewis acid is H+ (the electron deficient species) There are 2 bases (NO2- and ClO2-), which compete for the acid The lone pairs donated by these bases are on oxygen atoms:

.. .. .. O=N- O : H .. ..

.. .. .. [ O=Cl- O : .. .. .. +

.. .. .. : O-Cl= O ] .. .. .. .. .. .. [ O=N- O : .. .. .. .. .. : O-N= O ] .. ..

.. .. .. O=Cl- O : H .. .. ..

Lewis Acids and Bases

The acid/base concept is further generalized by the Lewis acid/base definition. The driving force is the donation of an electron pair to electron-deficient atom. Lewis acid - an electron pair acceptor Lewis base - an electron pair donor

H+
Lewis acid

.. :O-H..
Lewis base

.. = H-O H
:

F F-B F
Lewis acid

H : N-H H
Lewis base

F H F-B:N-H F H

Complex Ions in Solution

One example of Lewis acid-base neutralization involves the stepwise complexes formed between Hg(II) and I- ion. There are four stepwise reactions, each of which is an acid/base neutralization by the Lewis definition:

Hg2+(aq) + I-(aq) = HgI+(aq) HgI+(aq) + I-(aq) = HgI2(s) HgI2(s) + I-(aq) = HgI3-(aq) HgI3-(aq) + I-(aq) = HgI42-(aq)
Identify the Lewis acid and Lewis base in each reaction.

(red-brown ppt)

Complex Ions and Solubility

Stepwise Lewis acid/base complexes form between Al3+(aq) and OH- ion. charged species are soluble in aqueous solution. uncharged Al(OH)3(s) forms a white precipitate. There are four stepwise reactions, each of which is an acid/base neutralization by the Lewis definition: All Only the

Al3+ + :OH- = AlOH2+ AlOH2+ + :OH- = Al(OH)2+ Al(OH)2+ + :OH- = Al(OH)3 (s) Al(OH)3 + :OH- = Al(OH)4Identify the Lewis acid and Lewis base in each reaction. white precipitate