Acids and

Bases
Chemistry of Materials
TMS1122

Mr. Chanaka Weerarathne

Department of
Engineering Technology
References
• Raymond Chang., Chemistry, (10th edition). McGraw-Hill Education.

• Chemistry – The Central Science, (14 th edition). Pearson.

2
Outline
• What are acids and bases (General idea)?
• What are acids (a deeper look)
• Arhenious theory
• Brønstead Lowry’s theory
• Lewis acids and bases

• Acid Base properties of water

• pH
• Strength of acids and bases
• Strong acids
• Strong bases
• Weak Acids and Acid Ionization Constants
• Weak Bases and Base Ionization Constants
• Buffer Solutions
• Indicators
• Acid-base titrations
3
Introduction

4
 Introduction
Acids Bases
• Sour in taste –Lemons, Oranges, Vinegar etc. • Bitter in taste – Baking Soda, Milk of Magnesia etc.
• Blue litmus Red • Feel slippery when touched – Soap
• Red litmus Blue
• React with active metals such as Mg, Zn & Fe to
evolve Hydrogen gas (H2 ) • Aqueous solutions conduct electricity (Electrolytes)

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

• Aqueous solutions conduct electricity (Electrolytes)

• React with carbonates/bicarbonates such as
Na2CO3, CaCO3 , and NaHCO3, to form CO2

CaCO3 (s) + 2HCl (aq) CaCl2 (aq) + H2O (l) + CO2 (g)
NaHCO3 (s) + 2HCl (aq) NaCl (aq) + H2O (l) + CO2 (g)
5
Strong HClO4 Perchloric acid NaOH Sodium hydroxide Strong
acid H2SO4 Sulfuric acid KOH Potassium hydroxide base
HBr Hydrobromic acid Ba(OH)2 Barium hydroxide
HCl Hydrochloric acid Ca(OH)2 Calcium hydroxide
HNO3 Nitric acid
H3PO4 Phophoric acid
Weak HF Hydrofluoric acid NH3 Ammonia Weak
acid CH3COOH Acetic acid base

Acid + Base Neutralization

6
Acids and Bases – A deeper look
Arrhenius’s definitions

Definitions of
Acids and Brønsted-Lowry
Bases

Lewis
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Arrhenius definition
• Proposed by Svante August Arrhenius (1859–1927), a Swedish
chemist.

• Acids dissociate in water to produce H+ ions

HCl (aq) H+ (aq) + Cl- (aq)

• Bases dissociate in water to produce OH- ions

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

8
Limitations of Arrhenius definition
• Solvent effects are not considered.
• Applies only to compounds with the formula HA (acids) and BOH (bases)
• Applies only to aqueous solutions and not to non-aqueous solutions and gaseous
reactions.

In reality….
o H+ ions cannot exist free in solution. Hence it attaches itself readily to an H2O molecule:

Hydronium ion / H3O+

o Hydronium ions interact with additional water molecules via the formation of hydrogen
bonds
o H+(aq) and H3O+ (aq) can be used interchangeably.
9
Brønsted-Lowry theory
• Proposed by the Danish chemist Johannes Brønsted and Thomas Martin Lowry, independently in 1923
• Their concept is based on the fact that acid-base reactions involve the transfer of ions from one substance
to another
• An acid is a substance (molecule or ion) that donates a proton to another
substance.
HCl (g) + H2O(l) Cl - (aq) + H3O+ (aq)

• A base is a substance that accepts a proton.

NH3 (aq) + H2O(l) ⇋ NH4 + (aq) + OH- (aq)
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• This concept can be applied to reactions that do not occur in an aqueous solution

Q1. Consider the following equilibrium, which substance acts as the Brønsted – Lowry
acid/base?
H2 S (aq) + CH3 NH2 (aq) ⇋ HS-(aq) + CH3 NH3 + (aq)

A substance can function as an acid only if another

substance simultaneously behaves as a base.

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Conjugate Acid-Base Pairs
Remove H +

HNO2 (aq) + H2 O (l) ⇋ NO-2 (aq) + H3 O + (aq)

Acid Conjugate Conjugate
Base
Base Acid

add H +

add H +

NH3 (aq) + H2 O (l) ⇋ NH4+ (aq) + OH - (aq)

Base Conjugate Conjugate
Acid
acid base

remove H +

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Conjugate Acid-Base Pairs-Contd.
• The conjugate base of a Brønsted acid is the species that remains when one proton has
been removed from the acid. A conjugate acid results from the addition of a proton to a
Brønsted base.

• Every Brønsted acid has a conjugate base, and every Brønsted base has a conjugate acid

Q2

Identify the conjugate acid-base pairs in the reaction between ammonia and hydrofluoric
acid in aqueous solution

NH3 (aq) + HF (aq) ⇋ NH4+ (aq) + F –(aq)

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Lewis Acids and Bases
• Lewis acid is a substance that can accept a pair of electrons
• Lewis base as a substance that can donate a pair of electrons
• Much broader definition compared to other two.
• Lewis acid-base reactions include many reactions that do not involve
Brønsted acids
EXAMPLES

Ag+ (aq) + 2NH3 (l) ⇋ Ag(NH3)2+ (aq)

acid base

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The Acid-Base properties of water
• Water is a very weak electrolyte and therefore a poor conductor of
electricity, but it does undergo ionization to a small extent
• Water has the ability to act as either a Brønsted–Lowry acid or a Brønsted–
Lowry base

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

• This process known as the autoionization of water.

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Ion product of water
• Writing equilibrium constant expressions
For a reversible reaction at equilibrium and a constant temperature, a
certain ratio of reactant and product concentrations has a constant value, K
(the equilibrium constant)

aA + bB ⇋ cC + dD

𝑐 𝑑
[𝐶] [𝐷]
𝐾=
[𝐴]𝑎 [𝐵]𝑏

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Ion product of water
• The equilibrium-constant expression for the autoionization of water is
+
𝐻3𝑂 [𝑂𝐻−] 2H2O (l) ⇋ H3O+ (aq) + OH- (aq)
• 𝐾c =
[𝐻2𝑂]

• Concentration of pure solids/liquids is a constant

𝐾𝑤 = [H3O+] [OH-] 𝐾𝑤 = [H+] [OH-]

Kw called the equilibrium constant, which we call the ion-product constant for water.

𝐾𝑤 = [H3O+] [OH-] = [H+] [OH-] = 1.0 × 10 -14 (at 25 o C )

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Q3.
The concentration of OH- ions in a certain household ammonia cleaning
solution is 0.0025 M. Calculate the concentration of H+ ions.

+ 𝐾𝑤 1.0 × 10−14 −12

𝐻 = − = = 4.0 × 10 𝑀
[𝑂𝐻 ] 0.0025

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• Determine the concentration of H+ and OH- ions in a neutral solution at 25 0C

[H+] [OH-] = (x) (x) = 1.0 x 10 -14 Acidic solutions : [H+] > 1.0 × 10 – 7 M
x 2 = 1.0 x 10 -14 Basic solutions : [H+] < 1.0 x 10 -7 M
x = 1.0 x 10 -7 M = [H+] = [OH-] Neutral solutions : [H+] = 1.0 × 10 – 7 M

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The pH Scale
• The molar concentration of H+ in an aqueous solution is usually very small

pH = - log [H3O +] pH = - log [H +]

EXAMPLE
pH of a neutral solution at 25 0 C

pH = - log (1.0 X 10 -7 ) = - (- 7.00) = 7.00

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 Acidic solutions : [H+] > 1.0 × 10 – 7 M, pH < 7.00
Basic solutions : [H+] < 1.0 x 10 -7 M. pH > 7.00
Neutral solutions : [H+] = 1.0 × 10 – 7 M, pH = 7.00

+
[H ] , pH
Calculating the H+ concentration when pH is given

[H+] = 10 -pH

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Q4
The pH of rainwater collected in Anuradhapura region on a particular day was 4.82.
Calculate the H+ ion concentration of the rainwater.

Solution
pH = - log [H+] = 4.82
Therefore,

log [H+] = -4.82

To calculate [H+], take the antilog of -4.82

[H+] = 10 -4.82 = 1.5 x 10-5 M

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Practice Problems
A solution at 25 0 C has [OH-] = 6.7 X 10 -3 . What is the pH of the solution?
(a) 0.83 (b) 2.2 (c) 2.17 (d) 11.83 (e) 12

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pOH scale
• A pOH scale analogous to the pH scale

• The negative logarithm is a convenient way of expressing the

magnitudes of other small quantities.

• Thus, we can express the concentration of OH- as pOH

pOH = - log [OH -] [OH-] = 10 -pOH

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• Now consider again the ion-product constant for water at 25°C:

[H+] [OH-] = Kw = 1.0 × 10-14

• Taking the negative logarithm of both sides, we obtain

- (log [H +] + log [OH -]) = - log (1.0 x 10-14)

- log [H +] - log [OH -] = 14.00

pH + pOH = 14.00 (at 25 0 C)

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Q5
In a NaOH solution [OH-] is 2.9 x 10-4 M. Calculate the pH of the solution.

pOH = - log [OH-]

= - log (2.9 x 10-4)
= 3.54

pH + pOH = 14.00
pH = 14.00 - pOH
= 14.00 – 3.54
= 10.46
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Measuring pH
• The pH of a solution can be measured with a pH meter

• In brief, a pH meter consists of a pair of electrodes connected to a meter

capable of measuring small voltages, on the order of millivolts.

• A voltage, which varies with pH, is generated when the electrodes are
placed in a solution.

• This voltage is read by the meter, which is calibrated to give pH.

Using a pH Meter - YouTube

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28
29
Strength of Acids & Bases
Strong Acids & Bases
Weak Acids & Bases
Strong Acids and Bases
• Strong electrolytes that ionize completely in water.

Strong Acids Strong Bases

HNO3 (aq) H+(aq) + NO3 - (aq) KOH (aq) K +(aq) + OH - (aq)

HCl (Hydrochloric acid) NaOH (Sodium hydroxide)

HNO3 (Nitric acid) KOH (Potassium hydroxide)
HClO4 (Perchloric acid) Ba(OH)2 (Barium hydroxide)
H2SO4 (Sulfuric acid)
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Weak Acids and Acid Ionization Constants
• Weak acids partially ionized in aqueous solution. We can use the equilibrium
constant for the ionization reaction to express the extent to which a weak
acid ionizes.
HA (aq) + H2O (l) ⇋ H3O +(aq) + A- (aq)
or
HA (aq) ⇋ H +(aq) + A - (aq) (1)

Writing equilibrium reaction for equation 1

+ − + −
𝐻3𝑂 [𝐴 ] 𝐻 [𝐴 ]
Ka = or Ka = Ka : acid-dissociation constant
[𝐻𝐴] [𝐻𝐴]
• The magnitude of Ka
indicates the tendency of
the acid to ionize in water

• The larger the value of Ka,

the stronger the acid

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Calculating pH from Ka
EXAMPLE
Calculate the pH of a 0.50 M HF solution at 25°C.
The ionization of HF is given by
Writing the equilibrium
+ −
expression 𝐻 [𝐹 ]
HF (aq) ⇋ H +
(aq) + F- (aq) Ka =
[𝐻𝐹]
= 7.1 × 10 -4

Let x be the equilibrium concentration of H+

HF (aq) ⇋ H +(aq) + F - (aq)

Initial (M): 0.50 0.00 0.00 (𝑥)(𝑥)
-x +x +x
Ka = = 7.1 × 10 -4
Change (M): (0.50−𝑥)

Equilibrium (M): (0.50 – x) x x

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 x 2 = 7.1 x 10 -4 × (0.50 – x )
x 2 + 7.1 x 10 -4 x – 3.6 × 10 -4 = 0
Because HF is a weak acid and weak acids ionize only to a slight extent, we reason that x
must be small compared to 0.50
𝑥2 𝑥2
0.50 - x ≈ 0.50 ≈ = 7.1 × 10 -4
(0.50−𝑥) 0.50
Rearranging,
𝑥 2 = (0.50)(7.1 x 10-4) = 3.55 x 10-4

𝑥 = 3.55 × 10−4 = 0.019 M

[HF] = (0.50 – 0.019) M = 0.48 M

pH = -log (0.019) = 1.72
[F-] = 0.019 M
[H+] = 0.019 M
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If the approximation is 0.50 - x ≈ 0.50 is not valid; use the quadratic equation

−𝑏± 𝑏2 −4𝑎𝑐
X=
2𝑎

−7.1×10−4 ± ( 7.1×10−4 2 −4(1)(−3.6×10−5 )

X=
2(1)

−7.1×10−4 ± 0.012
X=
2

= 5.6 × 10−3 𝑀 𝑜𝑟 − 6.4 × 10−3 𝑀

𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑖𝑜𝑛𝑖𝑧𝑒𝑑 𝐻𝐴
Percent ionization = × 100%
𝑂𝑟𝑖𝑔𝑖𝑛𝑎𝑙 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐻𝐴
* the approximation is valid if the above expression is equal to or less than 5% 35
Ka from pH ??
EXAMPLE
Calculate Ka of a 0.10 M formic acid solution having a pH of 2.38 at 25 °C
+ −
𝐻 [𝐻𝐶𝑂𝑂 ]
HCOOH (aq) ⇋ H +
(aq) + HCOO - (aq)
Ka =
[𝐻𝐶𝑂𝑂𝐻]

pH = -log [H+] = 2.38

-log [H+] = -2.38

[H+] = 10 -2.38
= 4.2 x 10 -3 M
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Let x be the equilibrium concentration of H+

HCOOH (aq) ⇋ H +(aq) + HCOO - (aq)

Initial (M): 0.10 0.00 0.00

Change (M): -4.2 x 10 -3 +4.2 x 10 -3 +4.2 x 10 -3

Equilibrium (M): (0.10 – 4.2 x 10 -3) 4.2 x 10 -3 4.2 x 10 -3

Assume: 0.10 - 4.2 x 10 -3 ≈ 0.10 M

(4.2 x 10 −3)(4.2 x 10 −3)

Ka = = 𝟏. 𝟖 × 𝟏𝟎 - 4
(0.10)

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 Practice problems
1. Calculate the pH of a 0.36 M nitrous acid (HNO2) solution
2. A student prepared a 0.10 M solution of formic acid (HCOOH) and found its pH at 25 °C
to be 2.38. Calculate Ka for formic acid at this temperature

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Weak Bases and Base Ionization Constants
Weak bases, like weak acids, are weak electrolytes. They ionizes to a very
limited extent in water
• Consider Ammonia dissolving in water

NH3 (aq) + H2O (l) ⇋ NH4 +(aq) + OH- (aq) (2)

Writing Equlibrium reaction for equation 2

+ −
𝑁𝐻4 [𝑂𝐻 ]
Kb = Kb : base-dissociation constant
𝑁𝐻3

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40
Calculating pH from K b
In solving problems involving weak bases, we follow the same procedure we used for
weak acids. The main difference is that we calculate [OH-] first, rather than [H+].

EXAMPLE
we ignore the ionization of water
What is the pH of a 0.40 M ammonia solution?
2H2O (l) ⇋ H3O+ (aq) + OH- (aq)
Let x be the equilibrium concentration of NH4+ and OH- ions in M

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

Initial (M): 0.40 0.00 0.00
Change (M): -x +x +x

Equilibrium (M): (0.40 – x) x x

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 + −
𝑁𝐻4 [𝑂𝐻 ]
Kb = At equilibrium [OH-]= 2.7 x 10 -3 M
𝑁𝐻3
pOH = -log (2.7 x 10 -3 )
𝑥2
= 1.8 × 10 -5
0.40 −𝑥 = 2.57

Assuming (0.40 - x) ≈ 0.40

pH = 14.00 – 2.57
𝑥2 𝑥2
≈ = 1.8 × 10 -5 = 11.43
(0.40−𝑥) 0.40

𝑥 2 = 7.2 x 10 -6

𝑥 = 2.7 x 10-3 M

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Practice problem

Calculate the concentration of pH in a 0.15 M solution of NH3.

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The Relationship Between the Ionization Constants of Acids and
their Conjugate Bases
Let us consider CH3COOH & CH3COONa
+ −
𝐻 [𝐶𝐻3𝐶𝑂𝑂 ]
CH3COOH (aq) ⇋ H +(aq) + CH3COO- (aq) Ka =
[𝐶𝐻3𝐶𝑂𝑂𝐻]

−
[𝐶𝐻3𝐶𝑂𝑂𝐻] 𝑂𝐻
CH3COO- (aq) + H O
2 (l) ⇋ CH 3 COOH (aq) + OH -
(aq) Kb = −
[𝐶𝐻3𝐶𝑂𝑂 ]
Taking ion product of the two ionization constants;
+ −
𝐻 𝐶𝐻3𝐶𝑂𝑂 [𝐶𝐻3𝐶𝑂𝑂𝐻] 𝑂𝐻 −
Ka Kb = × −
[𝐶𝐻3𝐶𝑂𝑂𝐻] [𝐶𝐻3𝐶𝑂𝑂 ]
KaKb=Kw
= [H+] [OH-]
= Kw 44
Buffer solutions
• A buffer solution is a solution of
(1) a weak acid or a weak base and
(2) it’s salt

• These are basically conjugate acid/base pairs. The salt supplies the conjugate acid or
base.
e.g., acetic acid/sodium acetate, or ammonium chloride/ammonia

• The solution has the ability to resist changes in pH upon the addition of small amounts of
either acid or base.

• This buffer action is very important to chemical/biological systems.

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Let’s see how a buffer works CH3COOH / CH3COONa

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

• If an acid is added, the H+ ions will be consumed by CH3COO-

CH3COO- (aq) + H+
(aq) ⇌ CH3COOH (aq)

• If a base added, the OH- ions will be neutralized by the acid in the buffer

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

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Calculating pH of a buffer
The acid-dissociation equilibrium in this buffered solution involves both the acid and its
conjugate base
HA (aq) ⇌ H+ (aq) + A- (aq)
Acid-dissociation-constant expression:
+ − −
𝐻 [𝐴 ] + [𝐻𝐴 ]
Ka = 𝐻 = Ka −
[𝐻𝐴] [𝐴 ]

+ 𝐻𝐴 [𝐻𝐴]
− log 𝐻 = − log 𝐾𝑎 − = −𝑙𝑜𝑔𝐾𝑎 − 𝑙𝑜𝑔 −
𝐴 [𝐴 ]

+
𝒃𝒂𝒔𝒆
𝐵𝑢𝑡 − log 𝐻 = 𝑝𝐻 𝑎𝑛𝑑 − 𝑙𝑜𝑔𝐾𝑎 = 𝑝𝐾𝑎, 𝒑𝑯 = 𝒑𝑲𝒂 + 𝒍𝒐𝒈
𝒂𝒄𝒊𝒅
𝐻𝐴 𝐴−
p𝐻 = 𝑝𝐾𝑎 − 𝑙𝑜𝑔 − = 𝑝𝐾𝑎 + 𝑙𝑜𝑔
𝐴 𝐻𝐴
47
 Practice problem
(i) Calculate the pH of a buffer system containing 1.0 M CH3COOH and 1.0 M
CH3COONa

(ii)What is the pH of the buffer system after addition of 0.10 mole of gaseous
HCl to 1.0 L of the solution? (Assume that the volume of the solution
doesn’t change when HCl is added.

Ka of CH3COOH is 1.8 x 10 -5

48
 pH indicators
• Acid–base indicators can be
used to measure pH
• An acid–base indicator is a
colored substance that can
exist in either weakly acidic or
a base form.
• Indicator has one color at
lower pH and another at
higher pH

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 Color
Indicator pH Range
In Acid In Base
Thymol blue Red Yellow 1.2 – 2.8
Bromophenol blue Yellow Bluish purple 3.0 – 4.6
Methyl orange Orange Yellow 3.1 – 4.4
Methyl red Red Yellow 4.2 – 6.3
Chlorophenol blue Yellow Red 4.8 – 6.4
Bromothymol blue Yellow Blue 6.0 – 7.6
Cresol red Yellow Red 7.2 – 8.8
Phenolphthalein Colorless Reddish pink 8.3 – 10.0

50
 Let us consider a monoprotic weak acid that we will call HIn

HIn (aq) ⇌ H+ (aq) + In- (aq)

Color A Color B

• If the indicator is in an acidic medium

According to Le-Châtelier’s principle, equilibrium shifts to the left, and the color of the
indicator is to color A

• If the indicator is in a basic medium

According to Le-Châtelier’s principle, equilibrium shifts to the right, and the color of the
indicator change to color B

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Acid-Base titrations
• Titrations are procedures in which one reactant is
slowly added into a solution of another reactant
Burette containing
NaOH of known • Why do titrations?
concentration 1. To find the concentration of one of the reactants
2. To find the equilibrium constant for the reaction

• In an acid-base titration, a solution containing a

known concentration of base is slowly added to
acid (or the acid is added to the base)
Beaker containing
HCl of unknown • Indicators can be used to signal the equivalence
concentration point of a titration (the point at which equal
amounts of acid and base have reacted. pH of the
solution will be around 7.00)
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• The endpoint of a titration occurs when the indicator changes color

Homework
Find the difference between the endpoint and the equivalence point

Different types of acid-base

titrations

• Strong acid-Strong base

titrations
• Weak acid-Strong base
titrations
• Strong acid-weak base
titrations

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