Lecture 20:

Acids & Bases

Part 2
Textbook: Chapter 17

Dr. Anton Blencowe | Senior Lecturer in Chemistry

School of Pharmacy and Medical Sciences | Division of Health Sciences
University of South Australia | P4-21 | City East Campus
GPO Box 2471, Adelaide, 5001
t +61 8 8302 2493 | email: anton.blencowe@unisa.edu.au
www.unisa.edu.au |people.unisa.edu.au/anton.blencowe
 Recap
When an acid (or base) is dissolved in water we form conjugate pairs
HA(aq) + H2O(l) H3O+(aq) + A-(aq)
Acid: Base: Conjugate Conjugate
H+ donor H+ acceptor acid Base

Can predict which is favored based upon acid and base strength
Autoionisation of water: Kw = [H3O+][OH-] = 1.0 x 10-14
pH scale is used to represent the strength of an acid/base
pH = log10[H3O+]
Acidic: pH < 7
Basic: pH > 7
End of Lecture Questions
Is the following aqueous reaction
product or reactant favored?

NH4+ + F- NH3 + HF

HF is a stronger acid than

NH4+. Wants to donate a
proton

NH3 is a stronger base than

F-. Wants to accept a proton

Reactants Favored (Kc < 1)

 Recap: equilibriums
Many chemical reactions dont go to completion: establish equilibriums
reactants products
Rate of forward reaction = rate of reverse reaction

The equilibrium constant expression: aA+bB cC+dD

Products raised to
stoichiometric powers
Kc >> 1: products favoured
kforward [C]c [D]d Kc << 1: reactants favoured
Kc = =
kreverse [A]a [B]b

divided by reactants raised to

their stoichiometric powers
 Acid Ionization (dissociation) constants
When an acid ionizes in water:
HA(aq) + H2O(l) H3O+(aq) + A-(aq)
or HA(aq) H+(aq) + A-(aq)
The acid ionization constant (Ka) is used to report the degree of
ionization:
[H3O+] [A-] [H+] [A-] (Water omitted,
Ka = or Ka =
[HA] [HA] as usual)

Strong acids have large Ka values (e.g., HCl: 1.3 106)

Weak acids have small Ka values (e.g., HF: 6.8 10-4)
 Base ionization (dissociation) constants
For a base in water (e.g., NH3, NEt3):
B(aq) + H2O() BH+(aq) + OH-(aq)

The base ionization constant, Kb, is:

Strong bases have
[BH+][OH-] large Kb values
Kb = [B]
If the base is an anion (e.g., HS-, ClO-): Weak bases have
small Kb values
A-(aq) + H2O() HA(aq) + OH-(aq) (e.g., NO3-: 5 10-16)
[HA][OH-]
Kb =
[A-]
 Relationship between Ka and Kb values
For an acid-base conjugate pair: HA and A-
[H3O+][A-] [HA][OH-] [H O+][OH-] = K
Ka x Kb = - = 3 w
[HA] [A ]

Phenol, C6H5OH(aq) + H2O() C6H5O-(aq) + H3O+(aq)

C6H5OH, O
H
[H3O+][C6H5O-]
is a weak Ka =
[C6H5OH]
acid,
C6H5O-(aq) + H2O() C6H5OH(aq) + OH-(aq)
O
[C6H5OH][OH-]
Kb =
[C6H5O-]
Relationship between Ka and Kb values
[H3O+][C6H5O-] [C6H5OH][OH-]
Ka Kb = = [H3 O+][OH-] = K
w
[C6H5OH] [C6H5O-]

For phenol, Ka = 1.3 x 10-10 at 25C.

Calculate Kb for the phenolate ion C6H5O-

Ka x Kb = Kw = 1.0 x 10-14

Kw 1.0 x 10-14 -5
= Kb = = 7.7 x 10
Ka 1.3 x 10-10
Acid/Base ionization constants Comprehensive list
100 % ionized
Also see Table 17.5
(as ClO4-)
Acid Name Acid Ka Base Name Base Kb
Perchloric acid HClO4 Large Perchlorate ion ClO4- Very small
Sulfuric acid H2SO4 Large Hydrogen sulfate ion HSO4- Very small
... ... ... ... ... ...
Hydrofluoric acid HF 6.8 x 10-4 Fluoride ion F- 1.4 x 10-11
... ... ... ... ... ...
Acetic acid CH3COOH 1.8 x 10-5 Acetate ion CH3COO- 5.6 x 10-10
... ... ... ... ... ...
Hydrogen sulfide H2S 1 x 10-7 Hydrogen sulfide ion HS- 1 x 10-7
... ... ... ... ... ...
Water H2O 1.0 x 10-14 Hydroxide ion OH- 1.0
... ... ... ... ... ...
Ammonia NH 3 Very small Amide ion NH - 2 Large
Hydrogen H2 Very small Hydride ion H- Large
Methane CH4 Very small Methide ion CH3- Large

When comparing acids (or bases):

Larger Ka = stronger acid. Larger Kb = stronger base.
Problem Solving Using Ka and Kb
A 0.2 M solution of acetic acid has a [H3O+] of 1.90 10-3 M,
what is the Ka?
CH3COOH(aq) + H2O(l) H3O+(aq) + CH3COO-(aq)
[ ]initial 0.2
0.2 MM 00 00
change -1.910-3 M
-x 1.910-3 M +x
+x 1.910-3 M
[ ]equil (0.2 x)
(0.2 1.910-3 M) 1.910-3-3MM x1.910-3 M
1.910

[H3O+] [CH3COO-] (x)(x) (1.9 10-3 M)2

Ka = = =
[CH3COOH] (0.2 M x) (0.2 M 1.9 10-3 M)

Ka = 1.8 10-5
Problem Solving Using Ka and Kb
A 0.1 M solution of benzoic acid has a pH of 2.59, what is the Ka?

C6H5COOH(aq) + H2O(l) H3O+(aq) + C6H5COO-(aq)

pH = log10[H3O+] = 2.59
10-2.59 = [H3O+] = 2.57 10-3 M

[H3O+] [C6H5COO-] (x)(x) (2.57 10-3 M)2

Ka = = =
[C6H5COOH] (0.1 M x) (0.1 M 2.57 10-3 M)

Ka = 6.5 10-5
Problem Solving Using Ka and Kb
The pH values of 1 M and 0.1 M formic acid solutions are 1.87 and
2.37 respectively; what would be the Ka for these solution?

HCOOH(aq) + H2O(l) H3O+(aq) + HCOO-(aq)

For 1 M solution: pH = log10[H3O+] = 1.87;

10-1.87 = [H3O+] = 1.34 10-2 M

[H3O+] [HCOO-] (x)(x) = (1.34 10-2 M)2

Ka = =
[HCOOH] (1 M x) (1 M 1.34 10-2 M)
Ka = 1.8 10-4
Problem Solving Using Ka and Kb

For 0.1 M solution: pH = log10[H3O+] = 2.37;

10-2.37 = [H3O+] = 4.24 10-3 M

[H3O+] [HCOO-] (x)(x) (4.24 10-3 M)2

Ka = = =
[HCOOH] (0.1 M x) (0.1 M 4.24 10-3 M)
Ka = 1.8 10-4 (same as with 1 M solution)

Le Chateliers principle: if we change the concentration of a reactant (or

product) the system will react to re-establish the equilibrium (Kc (i.e.,
Ka) remains constant)
Problem Solving Using Ka and Kb
Determine [OH-] and pH of a 0.060 M dimethylamine solution at 25C:
Kb = 5.9 x 10-4.

(CH3)2NH + H2O(l) (CH3)2NH2+(aq) + OH-(aq)

Or B + H2O BH+ + OH-

So:
[(CH3)2NH2+][OH-]
Kb = = 5.9 x 10-4
[(CH3)2NH ]
 Problem Solving Using Ka and Kb
Find [OH-] and pH of a 0.060 M dimethylamine solution at 25C:
Kb = 5.9 x 10-4.

(CH3)2NH + H2O(l) (CH3)2NH2+(aq) + OH-(aq)

[ ]initial 0.060 0 0
change -x +x +x
[ ]equil (0.060 x) x x

[(CH ) NH +][OH-]
Kb = 5.9 x 10-4 = 3 2 2
[(CH3)2NH ]
Quadratic
(x)(x) x 2
equation Kb = (0.060 x) = = 5.9 x 10-4
(0.060 x)
Problem Solving Using Ka and Kb
For weak bases (or acids) the Kb (or Ka) is generally very small
Therefore, equilibrium lies far to the left and x will be very small:
assume x << [(CH3)2NH ]
2 2 x is small and
x x
Kb = 5.9 x 10 = -4 negligible
(0.060 x) 0.060 compared to the
initial concentration
x = (5.9 x 10-4 )(0.060) = 0.0059 M = [OH-]

pOH = -log [OH-] = -log (0.0059 M) = 2.23

pH = 14.00 2.23 = 11.77

**Solve quadratic equation, pOH = 2.25**

Ka values for polyprotic acids
Some acids can donate more than one H+:
Formula Name Acidic Hs
H2S Hydrosulfuric Acid 2
H3PO4 Phosphoric Acid 3
H2CO3 Carbonic Acid 2
HOOC-COOH Oxalic acid 2
C3H5O(COOH)3 Citric acid 3

Each H+ ionization has a different Ka.

The 1st proton is easiest to remove.
The 2nd is harder, etc.
Ka values for polyprotic acids
Phosphoric acid (H3PO4) has three acidic protons:

H+ harder to remove
H3PO4(aq) + H2O() H3O+(aq) + H2PO4- (aq)
Ka1 = 7.5 x 10-3

H2PO4-(aq) + H2O() H3O+(aq) + HPO42- (aq)

Ka2 = 6.2 x 10-8

HPO42-(aq) + H2O() H3O+(aq) + PO43- (aq)

Ka3 = 3.6 x 10-13
Trends in binary acids
What makes a strong acid?
A weak HA bond, so H+ can be easily removed!

Consider the binary acids (hydrohalic acids) HF, HCl, HBr, HI.

larger acid strength

smaller bond energy
HX Bond Energy (kJ) Ka
HF weak acid 566 7 x 10-4
strong acids

HCl 431 1 x 107

HBr 366 1 x 108
HI 299 1 x 1010
Weak acids v Strong acids
Strong acids fully dissociate

If we have 0.1 M HCl we will have 0.1 M H3O+

Weak acids do NOT fully dissociate

If we have 0.1 M acetic acid we will

NOT have 0.1 M H3O+

Need to consider the equilibrium

Acid strength and pKa
Often we may wish to compare 2 acids and determine which one
is stronger (compare their proton donating tendencies):

HA + H2O H3O+ + A (conjugate base)

We define the acid equilibrium constant:

If Ka (acid 1) > Ka (acid 2) then acid 1 is stronger (dissociates

more).

Usually compare: pKa = -log10 Ka

Acid strength and pKa
For comparing acids based on pKa,
if pKa (acid 1) < pKa (acid 2) then acid 1 is stronger.

ACID Ka pKa
HCl 2.0 106 -6.3
HCO2H (formic acid) 1.8 10-4 3.7
CH3COOH (acetic acid) 1.8 10-5 4.7
HCN (hydrogen cyanide) 4.9 10-10 9.3
Application to Biochemistry and Pharmaceuticals
Take the example of the local anesthetics:
lignocaine (pKa 7.7) and bupivacaine (pKa 8.3) Note: pKa of
conjugate acid

Lignocaine: Bupivacaine:
66% ionised at pH 7.4 89% ionised at pH 7.4

Bupivacaine causes a much slower anesthetic effect.

Due to the fact more of the molecules are charged ...

Application to Biochemistry and Pharmaceuticals

Charged molecules get stuck in the cell lipid bilayer

The more highly charged bupivacaine takes longer to give

an anesthetic effect (but lasts longer!!)
Application to Biochemistry and Pharmaceuticals
Opioids for pain management
Morphine (pKa 8.1) and diamorphine (pKa 7.6) Diamorphine
60% ionised
Morphine: at pH 7.4
84%
ionised at
pH 7.4

Interacts with receptors in the brain and central nervous system

Cause analgesia (relief from pain), sedation and euphoria
Application to Biochemistry and Pharmaceuticals
What causes differences in Diamorphine
60% ionised at pH 7.4
onset and duration?
Onset (IV): secs
To get to CNS and brain, Duration: 3-5 h
molecules must pass through
the semi-permeable blood brain
barrier (BBB)
Morphine:
Lipid-soluble molecules pass 84% ionised at pH 7.4
through the hydrophobic barrier Onset (IV): 5 min
via diffusion more easily than Duration 3-7 h
lipophilic molecules
Class test 2
Class test: Friday 12th May @ 12.10pm

Location: Main Hall, Brookman Building OR BJ3-56/BJ3-30

(You will be advised of the location to attend)

Topics included (Lectures 9-10, 12-16, Tutorials 4-6):

Eg: chemical thermodynamics/calorimetry
chemical kinetics
states of matter

Materials: Calculator (graphics not allowed)

Something to write with !!
Class test 2

Please bring student ID

(place on top right hand corner of desk)

ENTEXT students may have a bi-lingual dictionary

and have an extra 10 minutes

Reading time of 10 minutes + 50 minute test

Reading time is for reading ONLY

Please review the universitys academic integrity

code: http://www.unisa.edu.au/policies/manual