Acids and Bases!

!
Most processes in the chemical industry involve acids and
bases. Sulfuric acid is the most widely used industrial chemical.!

Many reactions in living cells

are understood in acid-base
terms, !
!
Digesting enzymes!
!
Buffering action of blood!
!
Human blood is stored in a
buffer.!

Some common household substances contain acids and

bases. Vinegar is a dilute solution of acetic acid. Drain cleaners
contain strong bases such as sodium hydroxide.!

Models of Acids and Bases!

!
Arrhenius Model!
Brnsted-Lowry Model!
Lewis Model!

Arrhenius Model!
!
Arrhenius theorised that acids break up in water and increase the
hydrogen ion (H+) concentration and that bases break up in water
and increase the hydroxide ion (OH-) concentration.!
!
!
!
!HCl (g)
H+(aq) + Cl-(aq)!
!
!
!
!NaOH (s)
Na+ (aq) + OH- (aq)!

This definition was only useful for a hydroxide base!

!
!
Consider this reaction with ammonia:!
!
!HCl (aq) + NH3 (aq)
Cl- (aq) + NH4+
!

(aq)!

!
and only applies to reactions in aqueous solution, however the
following reaction is also an acid base reaction:!
!
HCl (g) + NH3 (g)
NH4Cl (s)!
!
!
!
We need another definition.!

Brnsted-Lowry Model !

!
Brnsted-Lowry acids and bases are concerned only with a
transfer of hydrogen ions (protons).!
!
Back to the reaction between aqueous hydrochloric acid and
aqueous ammonia:!
!
!
!
!
! !HCl (aq) + NH3 (aq)
NH4+ (aq) + Cl- (aq)!

Lewis Model!
!
The reaction between an acid and a base can be seen as
donating a pair of electrons to make a coordinate covalent bond,
dative bond.!
!
The NH3 is donating a pair of electrons to the HCl.!
!
!
!
!
..!
!
!NH3 + H-Cl
NH4+ + Cl-!

A Lewis base is an electron

pair donor.!
!
For example: Ammonia,
cyanide, hydroxide,!
water, chloride, carbon
monoxide etc!
!
All of these species are
capable of donating a pair
of electrons.!

A Lewis acid is an electron

pair acceptor.!
!
For example: Metal
ions, aluminium!
trichloride, boron
trifluoride etc.!
!
All of these species are
capable of accepting a pair
of electrons.!

Why are BF3!and Ni2+ capable of accepting electrons?!

!
!
!
!
!
!
The reaction of NH3 and BF3 is a Lewis acid-base reaction, write
the reaction and include the double headed arrow to show the
movement of the electrons.!
!
!
!
!!

We will now concentrate on the Brnsted-Lowry

definition of acids and bases.!

Conjugate acid base pairs!

In this reaction B accepts the proton and is acting as a base

and HA donates the proton and is acting as an acid.!
!
Now consider the reverse reaction.!

Example!
Consider the following species in solution:!

H2S!

HS-!

If H2S acts as an acid then its conjugate base is!

If HS- acts as an acid then its conjugate base is!
If HS- acts as a base then its conjugate acid is!
If S2- acts as a base then its conjugate acid is!

S2-!

Hydronium Ion!
!
The hydrogen ion does not exist as
a "naked proton" in aqueous
solution. It is hydrated by water
molecules. !
!
The ion may exist as H5O2+, H7O3+,
H9O4+ etc.!
!
!
The hydrogen ion is represented as
both H+ and H3O+.!

Amphoteric Species !
!
Consider the following reactions:!
!
!
HNO3 (aq) + H2O (l)
H3O+ (aq) + NO3- (aq)!
!
!
NH3 (aq) + H2O (l)
HO- (aq) + NH4+ (aq)!
!
!
Water can act as both an acid and a base.!

Other amphoteric species include HS-, HSO4-, HCO3- and

H2PO4-.!
!
!
Exercise!
!
Write reactions to show the amphoteric behaviour of the
dihydrogenphosphate ion !

Acid Strength!
!
Acids exhibit a variety of strengths.!
!
Consider the reaction:!
!
!HA (aq) + H2O (l)
H3O+ (aq) + A- (aq)!
!
If the equilibrium lies very strongly to the right hand side then HA
is a strong acid, producing a high concentration of protons.!

For strong acids (Ka is very large)!

!

!HCl (g)

!or

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

H+ (aq) + Cl- (aq)!

Some strong acids:!

H-Cl

HNO3

!!
H2SO4

For a weak acid the equilibrium lies far to the left and the Ka is a
very small number. The stronger the acid the higher the Ka.!
pKa is defined as pKa = -logKa!
Acid Formula!

Acid Name!

Ka!

pKa!

HF!

hydrofluoric acid!

7.2 x 10-4!

3.1!

HCOOH!

formic acid!

1.8 x 10-4!

3.7!

CH3COOH!

acetic acid!

1.8 x 10-5!

4.7!

HCN!

hydrocyanic acid!

4.0 x 10-10!

9.4!

Which is the strongest acid?!

For weak acids we always show the equilibrium equation: !

!

HF (aq) + H2O (l)

H3O+ (aq) + F- (aq)!

!
Write the equation for the reaction of the following acids in water,
and circle the conjugate base:!
!
Formic acid HCOOH!
!
Hydrocyanic acid HCN!

Base Strength!
!
Lets first consider hydroxide bases, they are classified as strong
bases:!
!
NaOH (s) Na+ (aq) + OH- (aq) !
!
!

Ca(OH)2 (s) Ca2+ (aq) + 2OH- (aq)!

!
!
!
According to the Arrhenius concept they will completely dissociate
in water.!

Bases that do not contain hydroxide are considered weak bases.!

!
We consider the equilibrium:!
!
B (aq) + H2O (l)
BH+ (aq) + OH- (aq)!

pKb is defined as pKb = -logKb!

Base Formula!

Base Name!

Kb!

pKb!

NH3!

ammonia!

1.8 x 10-5!

4.7!

CH3NH2!

methylamine!

5.0 x 10-4!

3.3!

(CH3)3N!

trimethylamine!

7.4 x 10-5!

4.1!

C6H5NH2!

aniline!

4.0 x 10-10!

9.4!

Write the equilibrium equation for the reaction of the following

bases with water:!
!
Trimethylamine
Aniline (C6H5NH2)!

Strengths of Conjugate Acids and Bases!

!
Consider the ionisation of a strong acid such as HCl in water.!
!
! !HCl (aq) + H2O (l) Cl- (aq) + H3O+ (aq) !
!
!
The equilibrium lies strongly to the right and we can assume
that all of the HCl exists as hydrogen ions and Cl- ions.!
!
!
!
Therefore the conjugate base of a strong acid is an
extremely weak base; we consider it as a spectator ion.!

However, conjugate bases of weak acids are weak bases.!

!
!
!HCOOH (aq) + H2O (l)
HCOO- (aq) + H3O+ (aq)!
!
!
!
The equilibrium does not lie heavily to the right, the reverse
reaction is significant.!
!
!
!
!
Therefore the conjugate base of a weak acid is a weak base. !

Acid!

Ka!

Conjugate Base!

Kb!

HF!

7.2 x 10-4!

F-!

1.4 x 10-11!

HCOOH!

1.8 x 10-4!

HCOO-!

5.6 x 10-11!

CH3COOH!

1.8 x 10-5!

CH3COO-!

5.6 x 10-10!

HCN!

4.0 x 10-10!

CN-!

2.5 x 10-5!

Weak bases also give rise to weak conjugate acids:!

!
NH3 (aq) + H2O (l)
HO- (aq) + NH4+ (aq)!

Base!

Kb!

Conjugate Acid!

Ka!

NH3!

1.8 x 10-5!

NH4+!

5.6 x 10-10!

CH3NH2!

5.0 x 10-4!

CH3NH3+!

2.0 x 10-11!

(CH3)3N!

7.4 x 10-5!

(CH3)3NH+!

1.4 x 10-10!

C6H5NH2!

4.0 x 10-10!

C6H5NH3+!

2.5 x 10-5!

The relationship of acid

strength and conjugate base
strength.!

Source: McMurray and Fay, Chemistry 4th Ed!

Polyprotic Acids!
!
An acid which is capable of donating only one proton is a
monoprotic acid.!
!
It is possible for some substances to donate more than one proton they are known as polyprotic acids.!
!
!
!
Diprotic acids include H2SO4 and H2CO3!
!
!
H3PO4 is an example of a triprotic acid. !

Consider the behaviour of H2S as a diprotic acid:!

!!
Write the reactions to represent the stepwise ionisation:!
!
!
H2S(aq) + H2O(l)
!
!Ka1 !!
!
HS- (aq) + H2O(l)
!
!Ka2 !!

Ka1 !> Ka2 !!

ACID!

Ka1!

Ka2!

Ka3!

H3PO4!

7.5 x 10-3!

6.2 x 10-8!

3.6 x 10-13!

H2S!

1 x 10-7!

1 x 10-19!

-!

H2CO3!

4.2 x 10-7!

4.8 x 10-11!

-!

H2SO4!

very large!

1.2 x 10-2!

-!

H2SO3!

1.5 x 10-2!

1.0 x 10-7!

-!

The Ionisation of Water!

!
A pure sample of water undergoes self-ionisation according to the
equation:!
!
2H2O
H3O+ + OH-!
!
!
!
!
!
In this reaction water is behaving as both an acid and a base.!
!
Since water is only a weak acid and a weak base the reaction lies
predominantly to the left.!

The extent of the ionisation can be expressed in terms of an

ionisation constant Kw. !
!
!
Kw = [H+][OH-] = 10-14 at 25 C!
In pure water, [H+] = [OH-] = 10-7 M!
!
When [H+] = [OH-] the solution is said to be neutral.!

The addition of other substances may change [H+] and [OH-] but
the product of their concentrations is always constant (at a given
temperature).!
!
!Thus if [H+] = 10-1 M then the [OH-] = 10-13 M.!

If [H+] > 10-7 M then the solution is said to be acidic!

!
!(high concentration of protons).!
!
If [OH-] > 10-7 M then the solution is said to be basic!
!
!(high concentration of proton acceptors) .!

The pH and pOH Scales!

pH = -log[H+]

pOH = -log[OH-]!

!
pH + pOH = 14!
!
Thus if we know the pH we can calculate the pOH.!

Calculation of pH of Acids and Bases!

!
Strong Acids and Bases!
We assume that ionisation is almost 100% for a strong acid and
the H3O+ concentration at equilibrium is equal to the original acid
concentration.!
!
!
If the HCl concentration was 0.0010 M !
!
!HCl (g) H+ (aq) + Cl- (aq)!
!
!then the [H+] = 0.0010 M and the pH = 3.!
!

Similarly for strong bases such as NaOH, which dissociate

completely in water.!
!
!
NaOH (s)
Na+ (aq) + OH- (aq)!
!
!
If the original concentration of NaOH is 0.010 M !
!
then [OH-] = 0.010M; therefore the pOH = 2 and the pH = 12.!

Weak Acids and Bases!

!
To calculate of the pH of solutions of weak acids or bases treat it
as an equilibrium problem. Use an ICE table.!
!
Steps for calculating the pH for an acid or a base:!
!
1. Write the chemical equation!
2. Write the acidity (or basicity) constant (equilibrium expression)!
!
4. Solve for [H3O+] (or [OH-]) using an ICE table!
!
5. Calculate pH (or pOH and then pH for a base)!

Example!
!
Calculate the pH of a solution in which 0.00200 moles of HCN was
dissolved in 1.0 L of water. HCN has Ka of 4.93 x 10-10.!

Therefore!

Ka = X2 0.00200-X!
!
!

! X2 + KaX - 0.00200 Ka = 0!

Substituting in our value for Ka we can solve our quadratic

equation.!
!
!This results in X = 9.93 x 10-7 M!
!
!
!
!pH = -log 9.93 x 10-7!
!
!
!
= 6.00!
!
Although the calculation is correct it is tedious and time
consuming.!

We can make a simplifying assumption if the acid is weak.!

[HCN] in the solution at equilibrium initial [HCN]!

!
!
!
!
!
You can make the assumption for weak acids and bases in
your calculations, make sure you state the assumption in
your calculations.!

Exercise!
!
Determine the pH of a 0.100 M formic acid solution. Formic acid
has a Ka of 1.76 x10-4.!
!
!
!

Sometimes you may be given the pH (pOH or [H+] or [OH-]) and

are asked to calculate the Ka (or Kb).!
!
Example!
The pH of a 0.250M acetic acid (CH3COOH) was found to be
2.67. Calculate the Ka of acetic acid.!

Calculation of Percent Ionisation!

!
The percentage dissociation of an acid (HA) !
!
!
!
!= ([H+]equil. /[HA]original) x 100!

Example!
!
Calculate the percentage ionisation of acetic acid in a 0.100
M aqueous solution. Ka = 1.75 x 10-5.!

pH of Ionic Salts!
!
Consider NaCl:!
!
In water NaCl will dissociate to Na+ and Cl-!
!
! !NaCl Na+ + Cl-!
!
!
Cl- is the conjugate base of a very strong acid and is
considered neutral. !
!
The Na+ comes from a strong base and is considered neutral. !
!
Therefore a NaCl solution is neutral.!

Anions as Weak Bases!

!
Now consider CH3COONa. !
!
In water CH3COONa will dissociate to Na+ and CH3COO-!
!
!

!CH3COONa

Na+ + CH3COO-!

CH3COO- is the conjugate base of a weak acid and is therefore

a weak base. !
!
The Na+ comes from a strong base and is considered neutral. !
!
Therefore a CH3COONa solution is basic. !

We can now calculate the pH of the solution if we know the Kb of the

CH3COO-!
!
We can calculate the Kb of CH3COO- from the Ka of CH3COOH
because:!
!
!
!
!Ka x Kb = Kw
for a conjugate acid/base pair!

Exercise!
!
Determine the pH of 0.010 M CH3COONa solution (use the
data tables to look up the Ka of CH3COOH).!

Cations as Weak Acids!

!
Now consider NH4Cl: !
!
In water NH4Cl will dissociate to NH4+ and Cl-!
!
!

!NH4Cl

NH4+ + Cl-!

NH4+ is the conjugate acid of a weak base and is therefore a weak

acid. !
!
Cl- is the conjugate base of a very strong acid and is considered
neutral. !
!
Therefore a NH4Cl solution is acidic. !

NH4+ (aq) + H2O (l)

NH3 (aq) + H3O+ (aq)!

To calculate the pH it is first necessary to calculate the Ka of NH4+

from the Kb of NH3.!

Solutions Containing Acidic Cations and Basic Anions.!

!
In the case where a solution contains an acidic cation and a
basic anion the solution may be acidic or basic.!
!
In order to decide whether an ionic solution is acidic or basic,
compare the Ka of the acid cation with the Kb of the basic anion. !
!
!
!
Example!
!
Would you expect a NH4OOCCH3 solution to be acidic or basic?!
!
NH4OOCCH3 NH4+ + CH3COO-!

Solutions Containing Amphoteric Species!

!
Consider a solution of NaSH:!
!
In water NaSH will dissociate to Na+ + SH-!
!
! !NaSH Na+ + SH-!
!
The Na+ comes from a strong base and is considered neutral.
However, the SH- is amphoteric. !
!
To determine if the salt is acidic or basic we need to compare
the Ka and Kb of SH-.!

Metal Ions in Solution!

Consider a metal ion Mn+ in aqueous solution.!
!
!
!Mn+ + x H2O
[M(H2O)x]n+ !

The higher the charge on the metal (oxidation state) the stronger
the attraction and the more acidic the solution.!

Consider the following equilibrium:!

!
[Fe(H2O)6]3+
! [Fe(H2O)5OH]2+ + H+
Ka = 7.7 x 10-3!
!
(What would happen if you add some strong acid?)!

Type of Salt!

Examples!

Acid/Base
Behaviour!

pH of Solution!

Cation is from a
strong base and anion
is from a strong acid!

KCl and
NaNO3!

Neither act as an
acid or a base!

Neutral!

Cation is from a
strong base and anion
is conjugate base of a
weak acid!

Cation has no
KCN and
effect on pH; anion
CH3COONa!
acts as a base.!

Basic!

Cation is conjugate
acid of a weak base
and anion is from a
strong acid!

NH4NO3 and ! Cation acts as an

acid; anion has no
CH3NH3Cl!
effect on pH.!

Acidic!

Type of Salt!

Examples!

Acid/Base
Behaviour!

Cation is conjugate
Cation acts as an
NH4F and!
acid of a weak base
acid; anion acts as
and anion is conjugate CH3COONH4!
a base.!
base of a weak acid!

Cation is from a strong

base anion is an
amphoteric species!
Cation is a highly
charged metal ion and
anion is from a strong
acid!

pH of Solution!
Compare Ka of
cation and Kb of
anion!
Acidic if Ka > Kb
Basic if Ka < Kb
Neutral Ka = Kb!

NaHS and
NaHCO3!

Compare Ka and Kb
Cation has no effect
of anion !
on pH; anion acts
Acidic if Ka > Kb
as a acid or a base.!
Basic if Ka < Kb!

FeCl3 and
Al(NO3)3!

The hydrated cation

acts as an acid;
anion has no effect
on pH.!

Acidic!

Buffer Solutions!
!
A solution which shows only marginal change in pH upon
addition of acid or base (even though they may be strong) is a
buffer solution.!
!
A buffer solution is made up of an acid/conjugate base pair.!
!
!
!CH3COOH/CH3COO-!
!
!!
!
!NH4+/NH3!
!
!Such a pair is known as a buffer pair.!
!
We will consider how a buffer works on a qualitative level.!

Firstly imagine what would happen if we add hydroxide to pure

water. !
!
!
!
Imagine now we have a solution containing 0.1 M CH3COO- and
0.1 M CH3COOH and we add hydroxide to this solution.!
!
!
The following equilibrium exists:!
!
!CH3COOH + H2O!
! CH3COO- + H3O+!

As soon as hydroxide is added to solution it will react with the

acetic acid to generate more acetate. The hydroxide
concentration in solution is only marginally affected and the pH
is not greatly affected. !
!
At some point the amount of hydroxide added will exceed the
amount of acetic acid originally present in solution. At this point
the hydroxide concentration in solution rises dramatically. The
solution has then lost its capacity to behave as a buffer. !
!
The above buffer also protects the pH of the solution from the
addition of acids. Strong acid will react with acetate ions to
form acetic acid. !
!
Since the acetate ion mops up the protons the pH stays
constant.!

Acid-Base Titrations!
!
The technique allows the
determination of the concentration
of the sample solution. !
!
!
The process by which the acid (or
base) is titrated to equivalence
point is called neutralisation. Be
careful with this term!!
!
!
Consider the titration curve of a
strong acid with a strong base.!

NaOH + HNO3 KNO3 + H2O!

The pH curve for the titration

of 50.0 mL of 0.100 M
CH3COOH with 0.100 M
NaOH.!

Comparison of strong and

weak acid titration curves.!

The pH curve for the titration of 100.0 mL of 0.050 M NH3 with

0.10 M HCl.!

Indicators!
!
In a titration, how do we know that the equivalence point has
been reached? We use an indicator.!
!
An indicator is chosen so that it will change colour close to the
equivalence of the titration. !
!
!
!
!HIn + H2O !
!In- + H3O+!
!
The aim is to choose an indicator such that the end point occurs
at the equivalence point of the titration.!

Indicator End Points!

The first indicators were

isolated from plants, Litmus
comes from lichen. Red
cabbage juice can be used
as an indicator.!
!
The acid and base forms of
the indicator
phenolphthalein. In the acid
form (Hln), the molecule is
colorless. When a proton
(plus H2O) is removed to give
the base form (ln-), the color
changes to pink.!

Influence of Structure and Bonding on Acid Strength!

!
The strength of an acid, HA, is influenced by the H-A bond energy. !

A similar trend is exhibited

by group 16 elements.!
!
Acid strength:!
!
H2O < H2S < H2Se < H2Te!

For acids of the type HOX, the more

electronegative (or electron withdrawing)
the halogen, the stronger the acid.!
!
Acid strength:!
!
!HOCl > HOBr >HOI!
!
For oxy-acids the acid strength increases
with the oxidation state (the number of
oxygen atoms) of the central element.!
!
Acid strength:!
!!
!HOCl < HClO2 < HClO3 < HClO4!

Strength of Carboxylic Acids!

Source: Wade, Organic Chemistry!