CHAPTER 3

ACID-BASE EQUILIBRIUM
 THE ARRHENIUS THEORY

Acids  substances that produce H+ ions in water

H2O
HCl (g) H+ (aq) + Cl- (ag)

Arrhenius acid is a substance that produces hydronium ion

(H3O+) in water
 Bases  substances that produce OH- ions in water.

H2O
NaOH (s) Na+ (aq) + OH- (aq)

Arrhenius base is a substance that produces OH- in water.

 Apply only to aqueous solutions  limited

 NEW CONCEPT: ARRHENIUS ACIDS-BASES

Acids  substances that , when dissolved in water, increase

the concentration of H+ ions

Bases  substances that, when dissolved in water, increase

the concentration of OH- ions

Apply only to aqueous solutions  limited

 BRøNSTED-LOWRY THEORY OF ACIDS-BASES

Acid is a proton donor

Base is a proton acceptor
Not necessarily to be in aqueous solution

+
H H
Cl H + •• N H Cl - + H N H
H H

acid base
 Conjugate
acid base

NH3 + H2O NH4+ + OH-

base Conjugate acid

 NH4+ is the conjugate acid for NH3

 OH- is the conjugate base for H2O

Exercise: Identify the conjugate acid-base pairs.

H2PO4 + CO32- HCO3 + HPO42-

 The Lewis Theory of acids and bases

 An acid is an electron pair acceptor.

 A base is an electron pair donor.
 The advantage of this theory is that many more reactions can
be considered acid-base reactions because they do not have
to occur in solution.

 BF3 is acting as the Lewis acid by accepting the nitrogen's lone pair.
 NH3 is acting as the Lewis base by donating the lone pair
 HCl molecule is acting as a Lewis acid.
 It is accepting a pair of electrons from the ammonia, and
in the process it breaks up to form Cl- ion.
 GENERAL PROPERTIES OF ACID

 Sour taste
 Change litmus paper  blue to red
 React with metals (Zn, Mg, Fe) to produce hydrogen gas

2HCl (aq) + Mg (s)  MgCl2 (aq) + H2 (g)

 React with carbonates and bicarbonates (Na2CO3,

CaCO3, NaHCO3) to produce CO2

2HCl (aq) + CaCO3 (s)  CaCl2 (aq) + H2O (l) + CO2 (g)
 Aqueous solutions conduct electricity
 Neutralize bases
 GENERAL PROPERTIES OF BASE

 Bitter taste
 Feel slippery (e.g. : soap)
 Change litmus paper  red to blue
 Aqueous solutions conduct electricity
 Neutralize acids
 The Acid-Base Properties of Water
 Water is a unique solvent
 It can act either as an acid or a base.
 Water is a very weak electrolyte and therefore a poor
conductor of electricity
 The ionization of water is:
H2O(l) H+(aq) + OH-(aq)

acid-base conjugate pair

H2O(l) + H2O(l) H3O+(aq) + OH-(aq)

base2 acid1 acid2 base1

acid-base conjugate pair

 Ion-product of Water

 Ion-product of water refers to autoionization of water

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

 The equilibrium constant for the autoionization of water is:

Kw = [H+] [OH-]

 Kw is called the ion-product constant, which is the product

of the molar concentration of H+ and OH- ions at a particular
temperature.
  In pure water at 25 oC, [H+] = [OH-] = 1.0 x 10-7
Kw = [H+] [OH-]
Kw = (1.0 x 10-7) (1.0 x 10-7)
= 1.0 x 10-14

 Since Kw is small, the reactant, H2O, is favoured,

 so very few H+ and OH- ions are present at equilibrium

Solution Is
[H+] = [OH-] neutral
[H+] > [OH-] acidic
[H+] < [OH-] basic
Example:
The concentration of OH- ion in a solution is 0.0025M.
Calculate the concentration of H+ ions.

Kw = [H+] [OH-]
14
K 1.0 x 10
[H ]  w


[OH ] 0.0025

= 4.0 x 10-12 M
 pH SCALE

• Use to measure the concentration of H+ (H3O+) in a solution

• Measuring the acidity of the solution
• pH: negative base-10 logarithm (log) of the molarity of
hydrogen ion, [H+]

pH = - log [ H+ ]

• pH decreases as [ H+ ] increases
• Acidic solution pH < 7
• Neutral solution pH = 7
• Basic solution pH > 7
 pOH: negative base-10 logarithm (log) of the
hydroxide ion concentration

pOH = - log [ OH- ]

pH + pOH = 14.00
 STRENGTH OF ACIDS & BASES

Strong acid: - complete ionization (100%)

 dissociated (ionized) in water completely
- examples: HCl, HBr, HI, HClO4, HNO3, H2SO4

HCl (aq) + H2O (l)  H3O+ (aq) + Cl- (aq)

Hydronium
ion

H 2O
HCl (aq) H+ (aq) + Cl- (aq)
Strong base:
- complete ionization (100%)
 dissociated (ionized) in water completely
- examples: NaOH, KOH, Ba(OH)2, Ca(OH)2

H2O
NaOH (s) Na+ (aq) + OH- (aq)

H2O
Ba(OH)2 (s) Ba2+ (aq) + 2OH- (aq)
Determination of the pH of the strong acid and base
EXAMPLE
Calculate pH for the following solutions
i. 0.0010 M HCl
ii. 0.0010 M NaOH
iii. 0.0010 M Calcium hydoxide

i. 0.0010 M HCl
H2O
Step 1: HCl  H+ + Cl-
0.0010 M 0.0010 M

Step 2: pH = - log [ H+ ]

= - log 0.0010
= 3.0
ii. 0.0010 M NaOH

H2O
Step 1: NaOH  Na+ + OH-
0.0010 M 0.0010 M

Step 2: pOH = - log [ OH- ] = - log 0.001

= 3.0
Step 3: pH + pOH = 14.00

pH = 14.0 – 3.0 = 11.0

iii) 0.001 M calcium hydoxide
 Weak Acid
 incomplete ionization (< 100%)
 do not dissociate in water completely
 examples: HF, HNO2, CH3COOH, HCOOH

Acid Ionization Constant, Ka

HA(aq) + H2O (l) H3O+ (aq) + A- (aq)

HA(aq) H+ (aq) + A- (aq)


[H3O ] [ A ] 
[H ] [ A  ]
Ka  or Ka 
[HA] [HA]
 For an acid, the magnitude of its dissociation constant, k a will
give a direct indication of its strength.
 If the acid dissociates extensively by donating most of its
protons, it will have a large value of Ka and be considered as a
strong acid.
 As the value of Ka becomes smaller, the acid becomes weaker.
A smaller Ka value meaning the degree of the dissociation of the
acid is low

CH3COOH (aq) + H2O (l) H3O+ (aq) + CH3COO- (aq)

[H3O ] [CH3COO ]
Ka 
[CH3COOH]
 Weak Base

 incomplete ionization (< 100%)

 do not dissociate in water completely
 examples: NH3, C5H5N, C2H5NH2 (C2H5)2NH

Base Ionization Constant, Kb

NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)


[NH4 ] [OH ]
Kb 
[NH3 ]
 Determination of the pH of the weak acid and base

EXAMPLE

Determine the pH of 0.30 M acetic acid with the Ka of 1.8x10-5.

CH3COOH (aq) H3O+ (aq) + CH3COO- (aq)

Initial [ ] 0.30 0 0

change –x +x +x

Eq [ ] 0.30 – x x x

[H ] [CH3COO ] ( x) ( x)
Ka    1.8 x 105
[CH3COOH] 0.30  x

Ka << 1 0.30 – x  0.30 x = [H+] = 2.3x10-3

pH = -log[H+] = 2.64
 When can we use the approximation?

Ka << 1
0.30 – x  0.30

 When x is less than 5% of the value from which it is subtracted.

If x is more than 5% of the value from which it is substracted, you must

solve for x exactly using quadratic equation
 Exercise 1
What is the pH of a 0.10 M solution of NH3, Kb = 1.8 x 10-5?

11.13
Exercise 2
What is the pH of a 0.5 M HF solution (at 25 oC)? Ka = 7.1 x 10-4
4.0 x 10-11

Exercise 3
The pH of a 0.010 M weak monoprotic acid is 6.20.
Determine the Ka of the acid.
4.0 x 10-11
ACID-BASE
REACTION
 Neutralization
• Reaction between acid and a base to produce salt and water
HCl (aq) + NaOH (aq)  NaCl (aq) + H2O (l)
acid base salt

Titration
Procedure of determining the concentration of solution
Standard solution is added gradually to another solution of
unknown concentration until chemical reaction is complete
 calculate the concentration of unknown solution

MaVa = MbVb
a b
 EXAMPLE

Calculate the volume of 0.200 M NaOH needed to neutralize 25.0 ml

of 0.100 M HCl completely

ANSWER

HCl (aq) + NaOH (aq)  NaCl (aq) + H2O (l)

MaVa = MbVb
a b

0.100 M x 25.0 mL = 0.200 M x Vb

Vb = 12.5 mL
 EXAMPLE 2
How many moles of H2O form when 25.0 mL of 0.100 M HNO3
solution is completely neutralized by NaOH?

ANSWER

HNO3 (aq) + NaOH (aq)  NaNO3 (aq) + H2O (l)

1 mol 1 mol
Moles HNO3 = 0.100 mol/L x 0.0250 L

= 2.50 x 10-3 mol

 Exercise 1
A solution is made by dissolving 18.4 g of HCl in 662 mL of water.
Calculate the pH of the solution. (Assume that the volume remains
constant)
 Exercise 2

Calculate the volume of 1.000 M Ca(OH)2 needed to neutralize 20.00

ml of 1.500 M HCl completely
 Exercise 3
210 g of sodium bicarbonate (NaHCO3) was dissolved in water and the
solution made up to 250 mL. 25.0 mL of this solution was pipetted into a
conical flask and some methyl orange indicator was added. This solution
was neutralized by 25.9 mL of dilute hydrochloric acid (HCl) added from
burette.
NaHCO3 + HCl  NaCl + CO2 + H2O
a) Calculate the molarity (concentration) of the NaHCO3 solution.
b) Determine the number of moles of NaHCO3 used in this experiment.
c) Calculate the concentration of the HCl solution.
 Acid-Base Properties of Salts

 Salt is a ionic compound formed by the reaction

between an acid and a base.
 Salts are strong electrolytes that completely dissociate
into ions in water.

Salt Hydrolysis

 Describe the reaction of an anion or a cation of a salt, or

both, with water.
 Salt hydrolysis usually effects the pH of a solution.
 Salts That Produce Neutral Solutions

 Salts containing an alkali metal ion or alkaline earth metal ion

(except Be2+) and the conjugate base of a strong acid DO
NOT undergo hydrolysis
 The salt solutions are neutral
 Example: HNO3 + NaOH  NaNO3 + H2O

H2O
NaNO3(s)  Na+(aq) + NO3-(aq)

 NaNO3 dissociates completely in water.

 The hydrated Na+ ion neither donates nor accepts H+ ions
 The NO3- ion is the conjugate base of the strong acid, and it
has no affinity for H+ ions
 Hence the solution is neutral with pH  7
 Salts That Produce Basic Solutions
 The solution of salts derived from a strong base and a weak
acid is basic.
 Example: reaction between NaOH and acetic acid

CH3COO-(aq) + H2O(l) CH3COOH(aq) + OH-(aq)

CH3COONa(aq)  Na+(aq) + CH3COO-(aq)

 The Na+ ion has no basic or acidic properties

 Acetic ion is the conjugate base of the weak acid, and it
has an affinity for H+ ions.
 The hydrolysis reaction is:

CH3COO-(aq) + H2O(l) CH3COOH(aq) + OH-(aq)

 CH3COO-(aq) + H2O(l) CH3COOH(aq) + OH-(aq)

 This reaction produces OH-, so the salt solution will be basic.

 The equilibrium constant is

[CH3COOH][OH ] 10
Kb   5.6 x 10
[CH3COO ]
 Percent hydrolysis could be calculate as

[CH3COO ]hydrolyzed
% hydrolysis  
x 100%
[CH3COO ]initial

[OH ]eq
 
x 100%
[CH3COO ]initial
Example
Determine the pH of a 0.15 M sodium acetate solution and calculate
the % hydrolysis

CH3COONa (aq)  Na+ (aq) + CH3COO- (aq)

Initial [ ] 0.15 0 0

change –0.15 +0.15 +0.15

Final [ ]

CH3COO-(aq) + H2O CH3COOH(aq) + OH-(aq)

Initial [ ]
change
Eq [ ]
 Salts That Produce Acidic Solutions

 The solution of salts derived from a strong acid and a weak

base is acidic.
 Example: reaction between HCl and ammonia
HCl(aq) + NH3(aq)  NH4Cl(aq)
NH4Cl(aq)  NH4+(aq) + Cl-(aq)

 The Cl- ion is the conjugate base of strong acid. So it has no

affinity for H+ ions
 NH4+ ion is the conjugate acid of the weak base, and ionizes as
follow:

NH4+(aq) + H2O(l) NH3(aq) + H3O+(aq)

 NH4+(aq) NH3(aq) + H+(aq)

 This reaction produces H+, so the salt solution will be
acidic.
 The equilibrium constant is

[NH3 ] [H ]
Ka  
 5.6 x 1010
[NH4 ]
 TITRATION

Equivalence point  the point at which the acid has been

completely reacted / neutralized by the base
Indicator  to determine the equivalent point of titration.
 a substance whose colour depends on the pH of the
solution to which it is added.
 eg: phenolphthalein, methyl orange
End point  occurs when the indicator changes color
Example: phenolphthalein is colourless in acid and pink
colour in base solution
 Method to determine the equivalence point

1) Using the pH meter

 The electrode of the pH meter is dip into the unknown
solution.
 Acid or base from the burette is added to the unknown
solution until equivalence point is reached.
 A graph of pH versus volume added is plotted to
determine the equivalence point.
2) Using an Indicators
 An acid-base indicator is commonly used to determine the
equivalence point of titration.
 Because the indicator has a different colour in acid to
that of base solution.
 The end point of a titration occurs when the indicator
changes colour.
 Normally the equivalence is very closed to the end point.

Indicator Acid colour Alkaline colour pH range

Methyl orange pink yellow 3.1 – 4.4
Bromothymol blue yellow blue 6.0 – 7.6
phenolphthalein colourless red 8.3 – 10.0
thymolphthalein colourless blue 8.5 – 10.5
 Strong Acid-Strong Base Titrations

NaOH (aq) + HCl (aq) H2O (l) + NaCl (aq)

NaCl(aq) Cl-(aq) + Na+(aq)

16.4
 Weak Acid-Strong Base Titrations
CH3COOH (aq) + NaOH (aq)  CH3COONa (aq) + H2O (l)
CH3COONa(aq)  Na+(aq) + CH3COO-(aq)
At equivalence point (pH > 7):

CH3COO-(aq) + H2O(l) CH3COOH(aq) + OH-(aq)

16.4
 Strong Acid-Weak Base Titrations
HCl(aq) + NH3(aq)  NH4Cl(aq)
NH4Cl(aq)  NH4+(aq) + Cl-(aq)
At equivalence point (pH < 7):

NH4+(aq) + H2O(l) NH3(aq) + H3O+(aq)

16.4
Acid (A) – base (B) End point pH : Indicator

Strong A – strong B 7 Methyl blue

(phenolphthalein, Methyl
orange)
Strong A – weak B 5.5 Methyl orange

Weak A – strong B 8.5 Phenolphthalein

(Bromothymol blue)
Weak A – weak B 7 Use pH meter
Example
Calculate the pH in the titration of 25.0 mL of 0.100 M acetic acid
by sodium hydroxide after the addition of
a) 25.0 mL of 0.100 M NaOH a) pH = 8.72
b) pH = 12.22
b) 35.0 mL of 0.100 M NaOH

Answer
a) Moles CH3COOH = 0.100 mol/L x 0.0250 L

= 2.50 x 10-3 mol

Moles NaOH = 0.100 mol/L x 0.0250 L

= 2.50 x 10-3 mol

 Equivalence point
 CH3COOH (aq) + NaOH(aq)  CH3COONa(aq) + H2O(l)
Initial 2.50 x 10-3 mol 2.50 x 10-3 mol 0
(mol)
change -2.50 x 10-3 mol -2.50 x 10-3 mol +2.50 x 10-3 mol
(mol)
Final
0 0 2.50 x 10-3 mol
(mol)

 At the equivalence point, the [ ] of both acid and base are

zero. The total volume is 50.0 mL. So the [ ] of the salt is

2.50 x 10 3 mol
[CH3COONa]   0.0500 M
0.0500 L
 H2O
CH3COONa(aq)  Na+(aq) + CH3COO-(aq)

hydrolysis of salt:
 Buffer Solution

 A solution which resist a change in pH when a small

amount of acid or base is added to the solution.

 A buffer solution is an aqueous solution consisting of a

mixture of
1. A weak acid and its salt (containing the weak
conjugate base)
2. A weak base and its salt (containing the weak
conjugate acid)

 Two types of buffer solution:

1. Acidic type – to maintain pH < 7
2. Basic type – to maintain pH > 7
Exercise: Which of the following are buffer systems?
(a) KF/HF
(b) KBr/HBr,
(c) Na2CO3/NaHCO3
 How Buffers work?
 Buffers work by removing H3O+ or OH- ions from solution as
they are added.
 Using LeChatelier's principle
 Example: the buffer solution of the acetic acid and sodium
acetate
CH3COO-(aq) + H3O+(aq) CH3COOH(aq) + H2O(l)

 If an acid is added (H3O+), it combines with CH3COO - to form

CH3COOH and water. The pH will not therefore change dramatically.

 If a base is added, the OH- ions combine with the H3O+ ion in the
equilibrium and form water. Once more the pH does not change
dramatically
Example

Calculate the pH of a buffer solution containing 0.40 M CH3COOH

and 0.20 M CH3COONa. Given Ka = 1.8 x 10-5
Solution
Dissolving 0.20 M sodium acetate (salt) initially produces 0.20 M
CH3COO- and 0.2 M Na+

CH3COONa(aq)  Na+(aq) + CH3COO-(aq)

0.20 M 0.20 M

CH3COOH (aq) H+ (aq) + CH3COO- (aq)

Initial [ ] 0.40 0 0.20

change –x +x +x
Eq [ ] 0.40 – x x 0.20 + x

x = [H+] = 3.6 x 10-5 pH = -log[H+] = 4.44

Alternate way to calculate the pH of a buffer solution

Henderson – Hasselbalch Equation

[conjugate base]
pH  pK a  log
[acid]

[conjugate acid]
pOH  pK b  log
[base]
Equation for Buffer Solution

The Henderson-Haselbalch
Equation

pH = pKa + log [salt]

[acid]

pOH = pKb + log[salt]

[base]
Example:
Calculate the pH of a buffer solution containing 0.40 M CH3COOH
and 0.20 M CH3COONa.

CH3COOH (aq) H+ (aq) + CH3COO- (aq)

0.40 M 0 0.20 M

[conjugate base ]
pH  pK a  log
[acid]

0.2 M
pH   (log1.8 x 10 5 )  log  4.44
0.4 M
Exercise 1:
Calculate the pH of a solution containing 0.20 M NH3 and 0.30 M
NH4Cl
pH = 9.08
Exercise 2

1.00 L buffer solution was prepared by mixing 0.100 M CH3COOH

and 0.100 M CH3COONa.
i. Determine the pH of the buffer solution.
ii. Determine the pH of the buffer after the addition of 0.020
mol HCl.
iii. Determine the pH of the buffer after the addition of 0.030
mol NaOH.
Assume there is no change in volume.

i. 4.74
ii. 4.57
iii. 5.01
 Exercise
1) Calculate the pH at the equivalence point when 100 mL of
0.10 M HNO2 is titrated by a 100 mL of 0.10 M NaOH
solution.

2) Calculate the pH of the 0.20 M NH3/0.20 M NH4Cl buffer.

What is the pH of the buffer after the addition of 10.0 mL of
0.10 M HCl to 65.0 mL of the buffer?

3) Aminah is asked to prepare a buffer solution at pH = 8.60,

using one of the following weak acids:
HA (Ka = 2.7 x 10-3)
HB (Ka = 4.4 x 10-6)
HC (Ka = 2.6 x 10-9)
Which acid should she choose? Why?