1.

2 Water and Acid Base System

1.2.2 Acid and Base System

Dr. Ang Geik Yong

Integrative Pharmacogenomics Institute
(iPROMISE),
Level 7, FF3, Universiti Teknologi MARA
(UiTM),
Puncak Alam Campus,
42300 Bandar Puncak Alam,
Selangor, Malaysia.
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 Learning Objectives
Upon completion of this lecture, students
should be able to:
• Understand what are acids and bases
• How to calculate pH
• Titration curves and buffers

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 Acids and Bases
Acid is a molecule that acts as a proton donor (H+)
• Strong acid: an acid that is completely ionized in aqueous
solution
• Hydrochloric acid (HCl), hydrobromic acid (HBr), hydroiodic acid (HI),
nitric acid (HNO3), and sulfuric acid (H2SO4)

Acid Proton Conjugate

base

monoprotic acid
(releases a single proton per molecule)
What about diprotic acid and triprotic acid? 3
 Acids and Bases
Base is a molecule that acts as proton acceptor
• Strong base: a base that is completely ionized in aqueous
solution
• Lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide
(KOH), calcium hydroxide [Ca(OH)2], and barium hydroxide [Ba(OH)2]

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 Acids and Bases
Weak acid or base : an acid or base that is incompletely
ionized in aqueous solution
 carboxylic acids (e.g. acetic acid) are weak acids

conjugate acid-base pair

O O
+
CH3 COH + H2 O CH3 CO - + H3 O
Acid Base Conjugate base Conjugate acid
of acetic acid of water

conjugate acid-base pair

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6
Weak Acids and Bases

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• Acid dissociation constant (Ka) measures the
degree of dissociation of acids in water
• Numerical measure of acid strength
 Complete dissociation – strong acid

 Incomplete to no dissociation – weak acid

• Ka formula
Bracket refer to
molar
Higher Ka concentration =
value = concentration in
stronger acid moles per liter 8
• Acid-base reaction is actually a proton-
transfer reaction in which water acts as
solvent. So more accurately,

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 What is pH?
• The extent of self-dissociation of water to
hydrogen ion and hydroxide ion is small but it
does take place

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 Exercise

• Calculate the molar concentration of 1000 g water

in a total volume of 1 L. (MW H2O = 18 g/mol)
– A) molar concentration = concentration in moles/L
– B) 1000 g of H2O (how many moles of water?)
• How many moles of water = 1000 g/18 g/mol
= 55.5 mol
[H2O] = 55.5 mol/1 L = 55.5 M 11
• The ionization of pure water produces equal
concentrations of H+ and OH-

Kw, the ion product constant for water

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 • This Kw equation is valid for any aqueous solution
whether neutral, acidic or basic
• The range of possible hydrogen ion and hydroxide
ion concentrations in aqueous solution makes it
desirable to define a quantity to expressing these
concentrations more conveniently
• pH is defined as the negative logarithmic measure of
H ion concentration
• pH formula

The symbol "p" means take the negative logarithm of whatever follows in the
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formula
 Exercise
• Calculate the pH of 1 x 10-2 M HCl

pH = -log [H+]
= -log (1 x 10-2)
=2

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 Exercise
 Calculate the pH of 1 x 10-3 M NaOH

In 1 x 10-3 M NaOH, [OH] = 1 x 10-3 M

Because Kw = [H+][OH-]= 1 x 10-14

[H+]=(1 x 10-14)/(1 x 10-3)
= 1 x 10-11
pH = -log[H+] = 11 15
 pKa
• In biochemistry, most of the acids
encountered are weak acids (Ka < 1).
• To avoid having to use numbers with large,
negative exponents, pKa is used
• pKa formula

pKa is a more convenient numerical measure of

acid strength
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 • Relationship between Ka & pKa

If Ka = 5.6 x 10-3 ,
If Ka = 5.6 x 10-13 ,

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 Note that the smaller the Ka, the larger the pKa.
Thus, stronger acids are represented by larger
Kavalues, but smaller pKa values

 Whether an acid is strong of weak, it can be

readily identified by either its Ka or pKa:

Type Ka pKa
 Strong acid >1 < 0 (negative)
 Weak acid <1 > 0 (positive)

 Acidic solutions : [H3O+] > [OH–]

 Basic solutions : [OH–] > [H3O+]
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 Henderson-Hasselbalch

How Henderson-Hasselbalch equation is derived

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 Henderson-Hasselbalch
• Henderson-Hasselbalch equation,

[Conjugate base]
pH = pK a + log
[Weak acid]
• Important for calculating pH of buffer
conjugate acid-base pair
O O
+
CH3 COH + H2 O CH3 CO - + H3 O
Acid Base Conjugate base Conjugate acid
of acetic acid of water
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conjugate acid-base pair
 Exercise
Identify the acid, base, conjugate acid and conjugate base
for the following reaction:

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 Exercise
Identify the acid, base, conjugate acid and conjugate base
for the following reaction:

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 Exercise
Calculate the pH of a buffer solution made from 0.50
M HC2H3O2 and 0.50 M C2H3O2. The acid dissociation
constant for HC2H3O2 of 1.8 x 10-5
pH = pKa + log ([A-]/[HA])
pH = pKa + log ([C2H3O2-] / [HC2H3O2])
pH = -log (1.8 x 10-5) + log (0.50 M / 0.50 M)
pH = -log (1.8 x 10-5) + log (1)
pH = 4.7
when the concentrations of weak acid and its
conjugate base are equal, pH = pKa of the weak acid
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 Exercise
Calculate the pH of a buffer solution made from 0.20
M HC2H3O2 and 0.50 M C2H3O2. The acid dissociation
constant for HC2H3O2 of 1.8 x 10-5
pH = pKa + log ([A-]/[HA])
pH = pKa + log ([C2H3O2-] / [HC2H3O2])
pH = -log (1.8 x 10-5) + log (0.50 M / 0.20 M)
pH = -log (1.8 x 10-5) + log (2.5)
pH = 4.7 + 0.40
pH = 5.1
when pH > pKa, the conjugate base predominates24
 Exercise
Calculate the pH of a buffer solution made from 0.50
M HC2H3O2 and 0.20 M C2H3O2. The acid dissociation
constant for HC2H3O2 of 1.8 x 10-5
pH = pKa + log ([A-]/[HA])
pH = pKa + log ([C2H3O2-] / [HC2H3O2])
pH = -log (1.8 x 10-5) + log (0.20 M / 0.50 M)
pH = -log (1.8 x 10-5) + log (0.4)
pH = 4.7 - 0.40
pH = 4.3
when pH < pKa, the weak acid predominates 25
CH3COOH + OH- ↔ CH3COO- + H2O 26
 Exercise
Calculate the pH if you added 6.5 mL of 0.1 M HCl to 93.5
mL of pure water at pH 7.0
pH = -log [H+]
[H+] = concentration of H+ in moles per liter
6.5 mL = 0.0065 L
0.0065 L x 0.1 mol/L = 0.00065 moles H+
There are 0.00065 moles H+ in a final volume of
100 mL or 0.1 L
What is the concentration of H+ in this solution?
[H+] = 0.00065 moles/0.1 L = 0.0065 M H+
pH = - log 0.0065 = 2.19 27
 Exercise
Calculate the pH if you added 6.5 mL of 0.1 M HCl to 93.5
mL of pure water at pH 7.0
pH = -log [H+]

M1V1 = M2V2
M1 and V1 are the molarity and volume of the concentrated stock solution
M2 and V2 are the molarity and volume of the final diluted solution

(0.1 M)(6.5 mL) = M2 (100 mL)

M2 = 0.0065 M

pH = - log 0.0065 = 2.19

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 Exercise
Calculate the pH if you added 6.5 mL of 0.1 M HCl to 93.5
mL of pure water at pH 7.0
pH = -log [H+]

M1V1 = M2V2
M1 and V1 are the molarity and volume of the concentrated stock solution
M2 and V2 are the molarity and volume of the final diluted solution

(0.1 M)(6.5 mL) = M2 (100 mL)

M2 = 0.0065 M

pH = - log 0.0065 = 2.19

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 Exercise
Calculate the pH if you added 1 mL of 0.1 M NaOH to 99
mL of pure water at pH 7.0
pH = -log [H+]
M1V1 = M2V2
(0.1 M)(1 mL) = M2 (100 mL)
M2 = 0.001 M = [OH-]

Because Kw = [H+][OH-]= 1 x 10-14

[H+]=(1 x 10-14)/(1 x 10-3)
= 1 x 10-11

pH = - log (1 x 10-11) = 11 30
 Exercise
• Calculate the pH of a buffer solution made
from 13 mL of 0.8 M chlorous acid (HClO) and
87 mL of 1.1 M potassium hypochlorite KClO.
The acid dissociation constant for chlorous
acid is 1.1 x 10-2
Strong or weak acid? -> which formula to use?

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• Calculate the pH of a buffer solution made
from 13 mL of 0.8 M chlorous acid (HClO2)
and 87 mL of 1.1 M potassium chlorite KClO2.
The acid dissociation constant for chlorous
acid is 1.1 x 10-2

Which is acid? Which is conjugate base?

Acid : chlorous acid (HClO2)
Conjugate base : chlorite ion (ClO2-)

Which formula to use to calculate final molar

concentrations of acid and conjugate base
[ClO2-]
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• Calculate the pH of a buffer solution made
from 13 mL of 0.8 M chlorous acid (HClO2)
and 87 mL of 1.1 M potassium chlorite KClO2.
The acid dissociation constant for chlorous
acid is 1.1 x 10-2

Which formula to use to calculate final molar

concentrations of acid and conjugate base
M1V1 = M2V2

[ClO2-] (1.1 M)(87 mL) = (M2) (100 mL)

M 2 = 0.957 M

[HClO2] (0.8 M)(13 mL) = (M2) (100 mL)

M 2 = 0.104 M 33
• Calculate the pH of a buffer solution made
from 13 mL of 0.8 M chlorous acid (HClO2)
and 87 mL of 1.1 M potassium chlorite KClO2.
The acid dissociation constant for chlorous
acid is 1.1 x 10-2

[ClO2-] (1.1 M)(87 mL) = (M2) (100 mL)

M 2 = 0.957 M

[HClO2] (0.8 M)(13 mL) = (M2) (100 mL)

M 2 = 0.104 M

pH = - log Ka+ log ( [A-]/[HA] )

= -log (1.1 x 10-2 ) + log (0.957 M/ 0.104 M)
= 1.96 + 0.96
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= 2.92
 Titration Curves
• Titration: an experiment in which measured
amounts of acid (or base) are added to measured
amounts of base (or acid)

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 Titration Curves
• Equivalence point: the point in an acid-base titration
at which enough acid has been added to exactly
neutralize the base (or vice versa)

pH ?

Equivalence point
pH
at pH7 is only for
strong acid +
strong base

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Volume of OH- added
 Titration Curves
• Inflection point: a point on the titration curve where
the pH equals to the pKa of the acid. Also known as
half equivalence point

pH

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Volume of OH- added
 Titration Curves
• Buffer: a solution whose pH resists change upon
addition of either more acid more base. Consists of a
weak acid and its conjugate base.

pH

Buffer region

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Volume of OH- added
Titration Curve for acetic acid

CH3COOH + OH- ↔ CH3COO- + H2O 39

 Why are buffers important
• Most biological processes are very sensitive to pH
e.g. enzyme activity

• Buffers are needed to stabilize pH changes in

organism
• Blood plasma is an example of a biological buffer
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• All buffers are mixtures of weak acids and its
salt of conjugate base
• Examples of acid-base buffers are solutions
containing
– CH3COOH and CH3COONa
– H2CO3 and NaHCO3
– NaH2PO4 and Na2HPO4
• We pick buffers by choosing pKa nearest to the
pH that we want

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Buffer range : a buffer is effective in a range of about
+/- 1 pH unit of the pKa of the weak acid

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Buffer Range

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 How does it work?
CH3COOH + OH- ↔ CH3COO- + H2O

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 How does it work?
CH3COOH + OH- ↔ CH3COO- + H2O

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46
 Buffers in the Body
• H2PO4-/HPO42- (phosphate buffer system) is the
principal buffer in cells
• H2CO3/HCO3- (carbonic acid-bicarbonate buffer system)
is an important (but not the only) buffer in blood
• E.g. : hyperventilation can result in increased blood pH
hypoventilation can result in decreased blood pH
(CO2 dissolve  carbonic acids)

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 How does human maintain a blood
pH 7.4 inside the body?
• When there is rapid metabolism, the body
produce excess CO2 and H+
• Carbon dioxide diffuses out of cells and is
transported in blood by dissolving in blood
plasma, binding to hemoglobin and converted
to carbonic acid (H2CO3) by carbonic
anhydrase
• Carbonic acid then dissociates to bicarbonate
ions (HCO3-) and hydrogen ions (H+)
• Lungs and kidney helps to remove CO2, HCO3-
and H+ from the blood 48
 Exercise
• 1. Which has the larger numerical value?
a) The pKa of a strong acid or the pKa of a
weak acid?

b) The Ka of a strong acid or the Ka of a weak

acid?

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 Exercise
• 2. Which is the stronger acid:
a) Benzoic acid with a Ka of 6.5 x 10-5 or
hydrocyanic acid with a Ka of 4.9 x 10-10?

b) Boric acid with a pKa of 9.14 or carbonic

acid with a pKa of 6.37?

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 Exercise
• Ka for benzoic acid is 6.5 x 10-5. What
is the pKa of this acid?

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Thank you

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