Acid-base 2816 1

ACIDS & BASES - IONIC EQUILIBRIA

Acid-base theories

LEWIS acid electron pair acceptor H+ , AlCl3

base electron pair donor NH3 , H2O , C2H5OH , OH¯

e.g. H3N: —-> BF3 ——> H3N+— BF3¯ see co-ordinate bonding
base acid

BRØNSTED acid proton donor HCl ——> H+(aq) + Cl¯(aq)

- LOWRY
base proton acceptor NH3 (aq) + H+(aq) ——> NH4+(aq)

Q.1 Classify the following according to Lewis theory and Brønsted-Lowry theory.
H3O+ BF3 H2SO4 H2O NH4+ CH3NH2

B-L

Lewis

Conjugate
systems Acids are related to bases ACID PROTON + CONJUGATE BASE

Bases are related to acids BASE + PROTON CONJUGATE ACID

For an acid to behave as an acid, it must have a base present to accept a proton...

HA + B BH+ + A¯
acid base conjugate conjugate
acid base

Q.2 Classify all the species in the following equations as acids or bases.

a) HSO4¯ + H2O H3O+ + SO42-

b) CH3COOH + H2O H3O+ + CH3COO¯

c) CH3COO¯ + H2O CH3COOH + OH¯

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THE STRENGTH OF ACIDS

Strong acids completely dissociate (split up) into ions in aqueous solution

e.g. HCl ——> H+(aq) + Cl¯(aq) MONOPROTIC 1 replaceable H

HNO3 ——> H+(aq) + NO3¯(aq)

H2SO4 ——> 2H+(aq) + SO42-(aq) DIPROTIC 2 replaceable H’s

Weak acids partially dissociate into ions in

aqueous solution e.g. ethanoic acid CH3COOH CH3COO¯(aq) + H+(aq)

Theory When a weak acid dissolves in

water an equilibrium is set up HA(aq) + H2O(l) A¯(aq) + H3O+(aq)

The water is essential as it stabilises

the resulting ions. However to make
calculations easier the dissociation
is usually written in a shorter way HA(aq) A¯(aq) + H+(aq)

The weaker the acid • the less it dissociates

• the more the equilibrium lies to the left.

The relative strengths of acids can be expressed as Ka or pKa values (see later).

The dissociation constant for the weak acid HA is Ka = [H+(aq)] [A¯(aq)] mol dm-3
(see later for a fuller discussion) [HA(aq)]

THE STRENGTH OF BASES

Strong bases completely dissociate into ions in aqueous solution e.g. NaOH ——> Na+ + OH¯

Weak bases partially react to give ions in aqueous solution e.g. ammonia (see below)

When a weak base dissolves in

water an equilibrium is set up NH3 (aq) + H2O(l) NH4+(aq) + OH¯(aq)

as in the case of acids

it is more simply written NH3 (aq) + H+(aq) NH4+(aq)

The weaker the base • the less it dissociates

• the more the equilibrium lies to the left

The relative strengths of bases can be expressed as Kb or pKb values.

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HYDROGEN ION CONCENTRATION

Introduction • hydrogen ion concentration determines the acidity of a solution

• hydroxide ion concentration determines the alkalinity
• for strong acids and bases the concentration of ions is very much
larger than their weaker counterparts which only partially dissociate.

pH hydrogen ion concentration can be converted to pH pH = - log10 [ H+(aq) ]

to convert pH into hydrogen ion concentration [ H+(aq) ] = antilog (-pH)

pOH An equivalent calculation for bases converts

the hydroxide ion concentration to pOH pOH = - log10 [ OH¯(aq) ]

in the above, [ ] represents the concentration in mol dm-3

Ionic Product of Water. . . Kw

Formula Despite being covalent, water conducts electricity to a very small extent.

This is due to the slight ionisation ... H2O(l) + H2O(l) H3O+(aq) + OH¯(aq)

or H2O(l) H+(aq) + OH¯(aq)

Applying the equilibrium law to the second we get Kc = [H+(aq)] [OH¯(aq)]

[H2O(l)]
[ ] is the equilibrium concentration in mol dm - 3

As the dissociation is small, the water concentration

is very large compared with the dissociated ions and
any changes to its value are insignificant;
its concentration can be regarded as constant.

This “constant” is combined with the dissociation Kw = [H+(aq)] [OH¯(aq)] mol2 dm-6
constant (Kc) to get a new constant (Kw).
= 10-14 mol2 dm-6 (at 25°C)

Variation The value of Kw varies with temperature because it is based on an equilibrium.

Temperature / °C 0 20 25 30 60 What does the trend tell you

about the sign of ∆Η for the
Kw / 10-14 mol2 dm-6 0.11 0.68 1.0 1.47 5.6
dissociation of water?
4 2816 Acid-base

The relationship between pH and pOH

Because H+ and OH¯ ions are produced

in equal amounts when water dissociates [H+] = [OH¯] = 10-7 mol dm-3
their concentrations will be the same.

• take the equation for Kw [H+] [OH¯] = 10-14 mol2 dm-6

• take logs of both sides log[H+] + log[OH¯] = -14

• multiply by minus - log[H+] - log[OH¯] = 14

• change to pH and pOH pH + pOH = 14 (at 25°C)

N.B. As they are based on the position of equilibrium and that varies with temperature,
the above values are only true if the temperature is 25°C (298K)

Neutral solutions may be regarded as those where [H+] = [OH¯].

Therefore a neutral solution is pH 7 only at a temperature of 25°C (298K)

The value of Kw is constant for any aqueous solution at the stated temperature

[H+] -1 -2 -3 -4 -5 -6 -7 -8 -9 - 10 - 11 - 12 - 13 - 14
1 10 10 10 10 10 10 10 10 10 10 10 10 10 10

[OH¯] - 14 - 13 - 12 - 11 - 10 -9 -8 -7 -6 -5 -4 -3 -2 -1
10 10 10 10 10 10 10 10 10 10 10 10 10 10 1

pH 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH
strongly weakly neutral weakly strongly
acidic acidic alkaline alkaline

Q.3 Convert the following pH values to [H+] ; 13 7.5 3.21 – 0.6993

Convert the following [H+] values to pH ; 0.01 2.5 x 10-4 1.1 x 10-13

BUFFER SOLUTIONS - Introduction

Definition “Solutions which resist changes in pH when small quantities of acid or alkali are added.”

Types Acidic Buffer (pH < 7) made from a weak acid + its sodium or potassium salt
ethanoic acid sodium ethanoate

Alkaline Buffer (pH > 7) made from a weak base + its chloride
ammonia ammonium chloride

Uses • Standardising pH meters • Buffering biological systems (eg in blood)

• Maintaining the pH of shampoos
Acid-base 2816 5

CALCULATING THE pH AND pOH OF STRONG ACIDS AND BASES

• This is relatively easy because the species have completely dissociated

• Only needs to know the original concentration of the acid or base

Example 1 Calculate the pH of 0.1M hydrochloric acid.

HCl (a strong monoprotic acid) is fully dissociated. HCl ——> H+(aq) + Cl¯(aq)

The [ H+] is therefore the same as the original concentration of HCl i.e. 0.1M.

pH = - log10 [H+] = - log10 (10-1) = 1 ANS. 1

Example 2 Calculate the pH of 0.001M sodium hydroxide.

Sodium hydroxide (a strong base) is fully dissociated. Na+OH¯ ——> Na+(aq) + OH¯(aq)

The [OH¯] is therefore the same as the original concentration of NaOH i.e. 0.001M.

pOH = - log10 [OH¯] = - log10 (10-3) = 3

and pH = 14 - pOH = 14 - 3 = 11 ANS. 11

Q.4 Calculate the pH and pOH of the following solutions.

a) HCl; 0.1M, 0.5M

b) H2SO4; 0.1M, 0.5M

c) KOH; 0.1M

d) NaOH; 2M, 0.0005M

e) The solution remaining when 30 cm3 of 0.100M NaOH

The dissociation constant for a weak3acid (Ka)
has been added to 20 cm of 0.200M HCl
A weak monobasic acid (HA) dissociates in water HA(aq) H+(aq) + A¯(aq)

The dissociation constant Ka is written Ka = [H+(aq)] [A¯(aq)] mol dm-3

[HA(aq)]
f) The solution remaining when 24.9 cm3 of 0.100M NaOH
has been added to 25 cm3 of 0.100M HCl
The weaker the acid • the less it dissociates
• the fewer ions you get
• the smaller Ka
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CALCULATING THE pH AND pOH OF WEAK ACIDS AND BASES

• can’t be calculated by just knowing the concentration

• need to know the extent of the ionisation (from Ka) and the original concentration.

The dissociation constant for a weak acid (Ka)

A weak monobasic acid (HA)

dissociates in water thus. HA(aq) + H2O(l) H3O+(aq) + A¯(aq)

Applying the equilibrium law we get Kc = [H3O+(aq)] [A¯(aq)]

[HA(aq)] [H2O(l)]
[ ] is the equilibrium concentration in mol dm-3

For a weak acid (little dissociation) in dilute

solution, the concentration of water is large
compared with the dissociated ions and any [H2O(l)] is “constant”
changes to its value are insignificant so its
concentration can be regarded as constant.

Combine this “constant” with the dissociation

constant (Kc) to get a new one (Ka). Ka = [H3O+(aq)] [A¯(aq)] mol dm-3
where Ka = Kc [H2O(l)] [HA(aq)]

A simpler way to write it all out is HA(aq) H+(aq) + A¯(aq)

The dissociation constant Ka is then Ka = [H+(aq)] [A¯(aq)] mol dm-3

[HA(aq)]

The weaker the acid • the less it dissociates

• the fewer ions you get
• the smaller Ka

The stronger the acid • the more the equilibrium lies to the right
• the larger Ka

pKa • very weak acids have very small Ka values

• it is easier to compare the strength as pKa values

The conversion is carried out thus... pKa = - log10 Ka

- the units of Ka are mol dm-3

to convert pH into hydrogen ion concentration Ka = antilog (-pKa)

Acid-base 2816 7

Q.5 Write out expressions for Ka for the following weak acids . . .

HF HCN

CH3COOH C6H5COOH

Calculating the pH of a weak acid

Theory A weak monobasic acid (HA) dissociates in water HA(aq) H+(aq) + A¯(aq)

the dissociation constant (Ka) is Ka = [H+(aq)] [A¯(aq)] mol dm-3

[HA(aq)]

Assumptions The equation shows that, on dissociation, [H+(aq)] = [A¯(aq)]

ions are formed in equimolar amounts.
∴ Ka = [H+(aq)] [H+(aq)]
The acid is weak, so dissociation is small. [HA(aq)]

The equilibrium concentration of HA can

be approximated to be its original value.

the equation can be re-written ... [H+(aq)]2 = Ka [HA(aq)]

and [H+(aq)] = Ka [HA(aq)]

The pH can then be calculated ... pH = - log10 [ H+(aq) ]

Q.6 Calculate the pH of the following solutions of weak acids . . .

a) 0.1M monobasic (monoprotic) acid (Ka = 2 x 10-4 mol dm-3)

b) 0.01M monobasic (monoprotic) acid (Ka = 7.5 x 10-3 mol dm-3)

8 2816 Acid-base

ACID - BASE INDICATORS

General Many indicators are weak acids and HIn(aq) H+(aq) + In¯(aq)
partially dissociate in aqueous solution red blue

The un-ionised form (HIn) is a

different colour to the anionic form (In¯). and Ka = [H+(aq)] [In¯(aq)]
[HIn(aq)]
Apply Le Chatelier’s Principle
to predict any colour change
[ ] is the equilibrium conc. in mol dm-3

Example In acid - increases [H+] - equilibrium moves to the left to give red undissociated form

In alkali - increases [OH¯] - although OH¯ ions don’t appear in the equation they
remove H+ ions to form water.
- equilibrium will move to the right to produce a blue colour

Choice • Must have an easily observed colour change.

• Must change quickly in the required pH range over the addition of ‘half’ a drop of reagent

examples pH 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Methyl Orange pink change yellow

Litmus red change blue

Phenolphthalein colourless change red

To be useful, an indicator must... change over the “vertical” section of the curve
where there is a large change in pH for the
addition of a very small volume.

The indicator used depends on the pH changes around the end point
- the indicator must change during the ‘vertical’ portion of the curve -

14 14

12 12

10 10

8 8

6 6

4 4

2 2

0 5 10 15 20 25 30 35 40 0 5 10 15 20 25 30 35 40
Volume of alkali added / cm 3 Volume of alkali added / cm 3

phenolphthalein methyl orange

Acid-base 2816 9

pH Curves

Types There are four possible types of acid-base titration; each has a characteristic curve.

• strong acid (HCl) v strong base (NaOH) • weak acid (CH3COOH) v strong alkali (NaOH)
• strong acid (HCl) v weak base (NH3) • weak acid (CH3COOH) v weak base (NH3)

In the examples below, alkali (0.1M) is added to 25cm3 of acid (0.1M).

The end points need not be “neutral‘ due to the phenomenon of salt hydrolysis

14 14

12 12

10 10

8 8

6 6

4 4

Draw the shape 2 2

of each pH curve 0 5 10 15 20 25 30 35 40 0 5 10 15 20 25 30 35 40

on the grids Volume of alkali added / cm3 Volume of alkali added / cm3

STRONG ACID - STRONG BASE STRONG ACID - WEAK BASE

You may want to draw
the graphs to a larger
scale on a separate sheet
14 14

12 12

10 10

8 8

6 6

4 4

2 2

0 5 10 15 20 25 30 35 40 0 5 10 15 20 25 30 35 40
Volume of alkali added / cm3 Volume of alkali added / cm3

WEAK ACID - STRONG BASE WEAK ACID - WEAK BASE

Q.7 • Why can’t indicators be used for a weak acid - weak base titration?

• What alternative methods can be used?

Other
curves Some titrations have more than one ‘vertical’ portion • acid v. carbonate
• NaOH v. diprotic acids

Q.8 Sketch and explain the pH curves you get when ...
• 0.1M hydrochloric acid is added to 0.1M sodium carbonate
• 0.1M sodium hydroxide is added to 0.1M ethanedioc acid
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CALCULATING THE pH OF ACID/ALKALI MIXTURES

The method depends on whether there are weak or strong acids and alkalis and which is in excess

1 Calculate initial moles of H+ and OH¯

STRONG ACID 2 Calculate which one is in excess
STRONG BASE 3 Calculate its concentration in the combined solution
4 Convert concentration to pH

Example Calculate the pH after 20cm3 of 0.1M HCl is added to 25cm3 of 0.1M NaOH
1 original moles of H+ = 0.1 x 20/1000 = 2 x 10-3 moles
2 original moles of OH¯ = 0.1 x 25/1000 = 2.5 x 10-3 moles
moles of excess OH¯ = 5 x 10-4
3 final volume (20 + 25) = 45cm3 = 0.045dm3
4 [OH¯] = 5 x 10-4 / 0.045 = 0.0111 mol dm-3
pOH = 1.95
pH = 14 - 1.95 = 12.05

WEAK ACID 1 Calculate initial moles of acid and alkali

2 Calculate the excess moles of OH¯
EXCESS
3 Calculate the OH¯ concentration in the combined solution
STRONG BASE
4 Convert concentration to pH

Example Calculate the pH after 22cm3 of 0.1M CH3COOH is added to 25cm3 of 0.1M NaOH
1 original moles of H+ = 0.1 x 22/1000 = 2.2 x 10-3 moles
2 original moles of OH¯ = 0.1 x 25/1000 = 2.5 x 10-3 moles
moles of excess OH¯ = 3 x 10-4
3 final volume (22 + 25) = 47cm3 = 0.047dm3
4 [OH¯] = 3 x 10-4 / 0.047 = 6.38 x 10-3 mol dm-3
pOH = 2.20
pH = 14 - 2.20 = 11.80

1 Calculate initial moles of acid and alkali

EXCESS 2 Calculate the excess moles of acid
WEAK ACID 3 Calculate the moles of anion formed (same as the alkali used up)
STRONG BASE 4 Use the value of Ka for the weak acid to calculate the value of [H+]
5 Convert concentration to pH

Example Calculate the pH after 20cm3 of 0.1M KOH is added to 25cm3 of 0.1M CH3COOH
1 original moles of CH3COOH = 0.1 x 25/1000 = 2.5 x 10-3 moles
original moles of KOH = 0.1 x 20/1000 = 2.0 x 10-3 moles
2 excess moles CH3COOH = 5.0 x 10-4
3 moles of CH3COO¯ formed = moles of H+ used = 2.0 x 10-3
4 Ka for CH3COOH = [H+][CH3COO¯] = 1.7 x 10-5 at 25°C
[CH3COOH]
YOU ONLY NEED TO PUT IN THE MOLAR RATIO
(NOT THE CONCENTRATIONS) BECAUSE THE [H+] = 1.7 x 10-5 x 5 x 10-4 = 4.25 x 10-6 mol dm-3
VOLUME IS THE SAME FOR BOTH SPECIES
2.0 x 10-3
5 pH = -log [H+] = 5.37
Acid-base 2816 11

Calculating the pKa of a weak acid by titration

Method • titrate a weak acid with sodium hydroxide solution

• record the pH after every addition - 1cm3 at first; smaller amounts near the end point
• carry on beyond the end point until the pH evens out
• plot a graph of pH (y axis) against volume of alkali added (x axis)
• calculate the pH and volume added at the end point
• calculate the pH at ‘half neutralisation’

14
Calculation Ka = [H+(aq)] [A¯(aq)] mol dm-3
[HA(aq)] 12

10
At ‘half neutralisation’, half the acid
has been converted to its anion and 8
their concentrations are equal
6

[HA(aq)] = [A¯(aq)] 4

Substituting in the equation gives 2

Ka = [H+] and pKa = pH

0 5 10 15 20 25 30
Volume of alkali added

BUFFER SOLUTIONS - INTRODUCTION AND USES

Definition “Solutions which resist changes in pH when small quantities of acid or alkali are added.”

Biological
Uses In biological systems (saliva, stomach, and blood) it is essential that the pH stays
‘constant’ in order for any processes to work properly. Most enzymes work best at
particular pH values.

Blood If the pH of blood varies by 0.5 it can lead to unconsciousness and coma

Other
Uses Many household and cosmetic products need to control their pH values.

Shampoo Buffer solutions counteract the alkalinity of the soap and prevent irritation

Baby lotion Buffer solutions maintain a pH of about 6 to prevent bacteria multiplying

Others Washing powder, eye drops, fizzy lemonade

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BUFFER SOLUTIONS - ACTION

Acid buffer It is essential to have a weak acid for an equilibrium to be present so that ions can be
removed and produced. The dissociation is small and there are few ions.

CH3COOH(aq) CH3COO¯(aq) + H+(aq)

relative concs. HIGH LOW LOW

NB A strong acid can’t be used as it is fully dissociated and cannot remove H+(aq)

HCl(aq) ——> Cl¯(aq) + H+(aq)

Adding acid Any H+ is removed by reacting with CH3COO¯ ions to form CH3COOH via the
equilibrium. Unfortunately, the concentration of CH3COO¯ is small and only a few H+
can be “mopped up”. A much larger concentration of CH3COO¯ is required.

To build up the concentration of CH3COO¯ ions, sodium ethanoate is added.

Adding alkali This adds OH¯ ions. Although they do not appear in the equation, they react with H+ ions
H+(aq) + OH¯(aq) H2O(l)

Removal of H+ from the weak acid equilibrium means that, according to Le Chatelier’s
Principle, more CH3COOH will dissociate to form ions to replace those being removed.

CH3COOH(aq) CH3COO¯(aq) + H+(aq)

As the added OH¯ ions remove the H+ from the weak acid system, the equilibrium moves
to the right to produce more H+ ions. Obviously, there must be a large concentration of
undissociated acid molecules to be available.

Other The concentration of a buffer solution is also important

If the concentration is too low, there won’t be enough CH3COOH and CH3COO¯
to cope with the ions added.

Summary For an acidic buffer solution one needs ...

large [CH3COOH(aq)] - for dissociating into H+(aq) when alkali is added

large [CH3COO¯(aq)] - for removing H+(aq) as it is added

This situation can’t exist if only acid is present so a mixture of the acid and salt is used.

The weak acid provides the equilibrium and the large CH3COOH(aq) concentration.
The sodium salt provides the large CH3COO¯(aq) concentration.

∴ One uses a WEAK ACID + its SODIUM OR POTASSIUM SALT

Acid-base 2816 13

CALCULATING THE pH OF AN ACIDIC BUFFER SOLUTION

Example 1 Calculate the pH of a buffer solution whose [HA] is 0.1 mol dm-3 and [A¯] of 0.1 mol dm-3.
Assume the Ka of the weak acid HA is 2 x 10-4 mol dm-3.

Ka = [H+(aq)] [A¯(aq)]
[HA(aq)]

re-arranging [H+(aq)] = [HA(aq)] Ka = 0.1 x 2 x 10-4 = 2 x 10-4 mol dm-3

[A¯(aq)] 0.1

∴ pH = - log10 [H+(aq)] = 3.699

Example 2 Calculate the pH of the solution formed when 500cm3 of 0.1 mol dm-3 of weak acid HX is
mixed with 500cm3 of a 0.2 mol dm-3 solution of its salt NaX. Ka = 4 x 10-5 mol dm-3.

Ka = [H+(aq)] [X¯(aq)]
[HX(aq)]

re-arranging [H+(aq)] = [HX(aq)] Ka

[X¯(aq)]

The solutions have been mixed; volume is now 1 dm3 [HX] = 0.05 mol dm-3
[X¯] = 0.10 mol dm-3

∴ [H+(aq)] = 0.05 x 4 x 10-5 = 2 x 10-5 mol dm-3

0.1

∴ pH = - log10 [H+(aq)] = 4.699

Alkaline buffer Very similar but is based on the equilibrium surrounding a weak base e.g. ammonia

NH3(aq) + H2O(l) OH¯(aq) + NH4+(aq)

relative concs. HIGH LOW LOW

but one needs ; a large conc. of OH¯(aq) to react with any H+(aq) added
a large conc of NH4+(aq) to react with any OH¯(aq) added

There is enough NH3 to act as a source of OH¯ but one needs to increase the
concentration of ammonium ions by adding an ammonium salt.

One uses AMMONIA (a weak base) + AMMONIUM CHLORIDE (one of its salts)
14 2816 Acid-base

SALT HYDROLYSIS

Introduction Many salts dissolve in water to produce solutions which are not neutral. This is because
the ions formed react with the hydroxide and hydrogen ions formed when water
dissociates. There are four distinct systems. All dissociated ions are aqueous ions.
When mixed, the ions of strong acids and bases remain apart. Ions of weak acids
and bases associate.

Salts of strong acids and strong bases

Sodium chloride completely dissociates Na+ Cl¯ ——> Na+ + Cl¯

Water partially dissociates H2O H+ + OH¯

Pairs of ions stay apart as they are

from strong acids and bases. [H+] = [OH¯] NEUTRAL

Salts of strong acids and weak bases

Ammonium chloride completely dissociates NH4+ Cl¯ ——> Cl¯ + NH4+

Water partially dissociates H2O H+ + OH¯

Some ammonium and hydroxide ions associate

to form ammonia (a weak base) and water.
NH3 + H2O

[H+] > [OH¯] ACIDIC

Salts of weak acids and strong bases

Sodium ethanoate completely dissociates CH3COO¯ Na+ ——> CH3COO¯ + Na+

Water partially dissociates H2O H+ + OH¯

Some ethanoate and hydrogen ions associate
to form ethanoic acid (a weak acid).
CH3COOH

[OH¯] > [H+] ALKALINE

Salts of weak acids and weak bases

Ammonium ethanoate completely dissociates CH3COO¯ NH4+ ——> CH3COO¯ + NH4+

Water partially dissociates H 2O H+ + OH¯

Some ethanoate and some hydrogen ions associate to

form ethanoic acid and some ammonium ions combine
with some hydroxide ions to produce ammonia. The pH CH3COOH NH3 + H2O
depends on the relative values of the two dissociation
constants but the solution will be . . .
APPROXIMATELY NEUTRAL