LECTURE 3

IONIZATION AND pH
BUFFER SYSTEMS
 Definition of Acid-Base
• Arrhenius definition
Acid is a substance that produces H+ in water; a
base is a substance that produces OH– in water.

• Brønsted–Lowry definition
Acid as a proton donor (H+ donor) and a base as a
proton (H+) acceptor.

Lewis definition
Acids act as electron pair acceptors and bases
act as electron pair doners
 Acid-Base Reaction
Brønsted and Lowry’s defination of acid-base:

HA + H2O H3O+ + A–
Acid Base

Conjugate Conjugate
acid of the base of the
base acid
 Autoionization of Water

•When it reacts with acid, water acts as a

base. When it reacts with a base, water acts
as an acid.
•Substances that can act as either an acid or
a base are called amphoteric.
• Water can also undergo an acid–base
reaction with itself, called autoionization.
 Autoionization of Water

H 2O + H 2O H3O+ + OH–
(hydronium ion) (hydroxide ion)

• H2O and H3O+ are an acid-base

conjugate pair

• H2O and OH - are an base-acid conjugate

pair
 Autoionization of Water
• Since water is also the solvent in this reaction
and [H2O] remains rather constant under all
circumstances, the equilibrium constant
expression is:
H2O H+ + OH–

Keq = [H + ][OH–]
[H2O]
• Keq is 1.8 x 10–16 M at 25 °C (room temperature).
• [H + ] = [OH–] = 1.0 X 10-7M
 pH Scale

• pH = -log10[H+]
• Calculate the pH of a 0.0034 M solution of
[H3O+]

• pH = -log(0.0034) = 2.47
• pH values are generally given to two significant
decimal points.
 Calculating Hydrogen Ion
Concentration from pH
• Calculate the hydrogen ion
concentration in a solution that has a
pH of 3.52

• [H+] = 10-pH = 10-3.52

• [H+] = 3.0 x 10-4 M

 The Relationship Between
pH and pOH
• pH = -log10[H3O+];
• pOH = -log10[OH-],
• pKw = –log10Kw
[H3O+][OH-] = Kw
log ([H3O+][OH-]) = log(Kw)
log[H3O+] + log[OH-] = log(Kw)
-log[H3O+] - log[OH-] = -log(Kw)
pH + pOH = pKw
pH + pOH = 14.00

pH of a solution depends on the presence of other
substances (acid/base) that increases or decreases the
concentration of H+.

Acid = substance that releases H+

Base = substance that accepts H+

HA H+ + A–
Acid (conjugate acid) Base(conjugate base)

Ka = [H+] [A–] pKa = -log Ka

[HA]
 Strong acids
100%

HA + H2O H3O+ + A–
0%

There are seven strong acids:

hydrochloric (HCl), hydrobromic (HBr),
hydroiodic (HI), nitric (HNO3), perchloric
(HClO4), chloric (HClO3), and sulfuric
(H2SO4).
 Calculating the pH of a
strong acid solution
Calculate the pH of a 0.050 M HCl solution

• HCl is a strong acid, so it dissociates

completely

• HCl H+ + Cl-

• [H3O+] = 0.050 M
• pH = -log[H3O+] = -log(0.050)
• pH = 1.30
 Strong bases

Strong bases are compounds that

quantitatively produce hydroxide ions in water

NaOH(s) Na+(aq) + OH-(aq)

 Calculating the pH of a
Strong Base Solution
Calculate the pH of a 0.017 M Ba(OH)2 solution

• Ba(OH)2 is a strong base, so

Ba(OH)2(aq) Ba2+(aq) + 2OH-(aq)

• [OH-] = 0.034 M
• pOH = -log[OH-] = -log(0.034)
• pOH = 1.47
• pH = 14 - pOH = 12.53
 Test Your Skill

• What is the concentration of a solution of

HCl if the pH is 3.75?

Answer: 1.8 x 10-4 M

• What is the concentration of a solution of

KOH if the pH is 11.60?

Answer: 4.0 x 10-3 M

 Weak Acids and Bases
Weak acids and weak bases are those that do
not ionize completely in water.

A weak acid exists in equilibrium with its

conjugate base.
HCN(aq) + H2O(l) H3O+(aq) + CN-(aq)

A weak base exists in equilibrium with its

conjugate acid.
CH3NH2 (aq) + H2O(l) CH3NH3+ (aq) + OH- (aq)
 Determining Ka for Weak
Acids

HA + H2O H3O+ + A–

[H3O+] [A-]
Ka =
[HA]
 Henderson-Hasselbalch
Henderson-
equation

 Henderson
Henderson--Hasselbalch equation defines pH of a
solution in terms of pKa

 The greater the concentration of [A-] (proton

acceptor), the higher the pH

The Henderson
Henderson--Hasselbalch equation is used for the
calculation of the pH or composition of a buffer
solution..
solution
 Henderson-Hasselbalch
Henderson-
equation
log10Ka = log10[H+] + log10[A- ] -
[H3 O+] [A-]
log10[HA]
Ka =
[HA] -log10[H+] = -log10Ka + log10[A-] -
log10[HA]

Concentration of
conjugated base

Concentration
-log Ka of acid
Calculate the pH of acetic acid/acetate buffer
solution containing 0.1 M acetic acid and
0.05 M sodium acetate. Ka = 1.8 X 10-5

pH = pKa + log10[conjugate base]

[acid]
= 4.7 + log10(0.05)
(0.1)

= 4.7 + (-0.3) = 4.4

 Buffer System

 Buffer - pH of the solution is "resistant" to small

additions of either a strong acid or strong base.

 Constant pH inside cellular is important to ensure

proper function of cell

 Blood and other biological fluids contain buffer

system

 Most effective at pH = pKa

 Buffer System
 Titration method can be used to determine
the pKa value
 Acid-base conjugate pair is most effective as buffer
system at pH equal to its pKa - buffering
range/capacity
 Effective buffer range (pH)= pKa ± 1
e.g. effective buffer range of :
Acetic acid-acetate : pH 3.76 – 5.76

Monoprotic acids

Polyprotic acids
A titration curve of weak acid
A titration curve of Acetic Acid