Crystal Gao

IB Chemistry 2013
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Acids and Bases notes
(Topics 8 & 18)

8.1 Theories of acids and bases (SL)
8.1.1 Define acids and bases according to the Bronsted-Lowry and Lewis theories (1)
Bronsted-Lowry:
Acid proton donor; involves transfer of H
+
ion one species to another
e.g. HCl
(g)
+ H
2
O
(l)
H
3
O
+
(aq)
+ Cl
-
(aq)
Base proton acceptor; involves acceptance of H
+
ion from another species
e.g. NH
3(aq)
+ H
2
O
(l)
NH
4
+
(aq)
+ OH
-
(aq)

Lewis:
Hypothesised that acid-base behavior is not tied to water or restricted to protons
Acid electron-pair acceptor
Base electron-pair donor
Donation of an e
-
pair by a Lewis base to a Lewis acid creates a covalent bond b/w species
Covalent bond known as a dative/coordinate bond because the two share e
-
come from the
same species (represented by arrow with a head [] from e
-
donor to e
-
acceptor)
Lewis acids are often electron deficient, hence very reactive towards e
-
pair donor (e.g. BF
3
)

e.g.BF
3
+ NH
3
BF
3
NH
3

Lewis acid + Lewis base Lewis acid-base complex


Arrhenius:
Acidic solution caused by H
+
(aq)
(released into solution via dissociation)

Basic solution caused by OH
-
(aq)

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8.1.2 Deduce whether or not a species could act as a Bronsted-Lowry and/or a Lewis acid/base (3)

Amphiprotic:
Substances that can act both as a base and an acid
E.g. water (H
2
O), hydrogen carbonate ion (HCO
3
-
), hydrogen sulfate ion (HSO
4
-
)
e.g. HCl
(aq)
+ H
2
O
(l)
H
3
O
+
(aq)
+ Cl
-
(aq)

NH
3(aq)
+ H
2
O
(l)
NH
4
+
(aq)
+ OH
-
(aq)

8.1.3 Deduce the formula of the conjugate acid (or base) of any Bronsted-Lowry base/acid (3)
Bronsted Lowry theory states that a base, after receiving a proton, has the potential to react
as an acid (and vice versa)
i.e. acid-base reactions are reversible

e.g. CH
3
COO
-
(aq)
+ H
2
O
(l)
Cl
-
(aq)
+ H
3
O
+
(aq)
Acid + base conjugate base + conjugate acid
acid

base

conjugate base

conjugate acid
H
2
SO
4
+ CH
3
COOH HSO
4
-
+ CH
3
COOH
2
+


CH
3
COOH + NH
3
CH
3
COO- + NH
4
+


HCl + H
2
O Cl- + H
3
O
+


proton donor

proton
acceptor

proton
acceptor
proton donor

Example: Ammonia + hydrogen chloride
In the reaction between ammonia gas and hydrogen chloride the hydrogen chloride transfers a hydrogen ion to
the ammonia making an ammonium ion. In this reaction the ammonia is behaving as a Brnsted Lowry base by
accepting a proton (hydrogen ion). The hydrogen chloride is a Brnsted-Lowry acid for providing (donating) that
proton (hydrogen ion)
HCl + NH
3
NH
4
Cl

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8.2 Properties of acids and bases
8.2.1 Outline the characteristic properties of acids and bases in aqueous solutions (2)
Acids:
Tastes sour (usually
Turns blue litmus red
Corrosive
Molecular in structure
Conducts electricity in aqueous solution
Reactions
1. Acids react with bases to form salt and water (neutralisation). The base may be a
metal oxide or a metal hydroxide.
e.g. HCl
(aq)
+ NH
3(aq)
NH
4
Cl
(aq)
2. Acids react with metal carbonates forming a salt, carbon dioxide and water
(neutralisation)
e.g. 2HCl
(aq)
+ CaCO
3(s)
CaCl
2(aq)
+ CO
2(g)
+ H
2
O
(l)

3. Acids react with active metals to form salt and hydrogen (this is not actually a
neutralisation reaction although the acid does get used up)
e.g. 2HCl
(aq)
+ Mg
(s)
MgCl
2(aq)
+ H
2(g)

4. Reacts with metal hydroxides to produce salt and water
e.g. 2HCl
(aq)
+ Mg(OH)
2(s)
MgCl
2(aq)
+ 2H
2
O
(l)


5. Reacts with metal oxides to produce a salt and water
e.g. 2HCl
(aq)
+ MgO
(s)
MgCl
2(aq)
+ H
2
O
(l)

6. Reacts with metal hydrogen carbonates to produce a salt, water and carbon dioxide
e.g. 2HCl
(aq)
+ Mg(HCO
3
)
2(s)
MgCl
2(aq)
+ 2H
2
O
(l)
+ 2CO
2(g)
Only H
+
ions reacting; Cl
-
ions remain in solution as spectator ions
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Bases:
Taste bitter
Turn red litmus blue
Feel slippery (strong bases convert skin oil to soap)
Conducts electricity in aqueous solution
Carbonates are basic
Reactions:
Same as list for acids

1. Ammonia reacts with acids to produce an ammonium salt
e.g. NH
3(aq)
+ HCl
(aq)
NH
4
Cl
(aq)

8.3 Strong and weak acids and bases
8.3.1 Distinguish between strong and weak acids and bases in terms of the extent of dissociation,
reaction with water and electrical conductivity (2)
Strong acids Strong acids tend to dissociate fully (or nearly 100%) in water
e.g. HCl
(aq)
+ H
2
O
(l)
H
3
O
+
(aq)
+ Cl
-
(aq)
Weak acids only dissociate partially in water (<1%)
e.g. CH
3
COOH
(aq)
+ H
2
O
(l)
H
3
O
+
(aq)
+ CH
3
COO
-
(aq)

8.3.2 State whether a given acid or base is strong or weak (1)
ACID BASE
Strong Weak Strong Weak
HCl CH
3
OOH Group 1
hydroxides
NH
3

HNO
3
H
2
CO
3
Ba(OH)
2
C
2
H
4
NH
3

H
2
SO
4
- - -




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8.3.3 Distinguish between strong and weak acids and bases, and determine the relative
strengths of acids and bases, using experimental data (2)
Energy of neutralisation (i.e. amount of acid/base required to neutralise it)
Conductivity
Rates of reaction
pH measurement

8.4 The pH scale
8.4.1 Distinguish between aqueous solutions that are acidic, neutral or alkaline using the pH
scale (2)
pH > 7 alkaline

pH = 7 neutral

pH < 7 acidic

8.4.2 Identify which of two or more aqueous solutions is more acidic/alkaline using pH values (2)
The greater the pH, the more alkaline

The smaller the pH, the more acidic

8.4.3 State that each change of one pH units = a 10-fold change in [H
+
(aq)
] (1)
Each change of one pH unit = 10-fold change in [H
+
(aq)
]
E.g. If a beaker of HCl has a [H
+
] of 1.0M and pH of 1, then when the pH = 2, the [H
+
] = 0.1M

8.4.4 Deduce changes in [H
+
(aq)
] when the pH of a solution changes by more than one pH unit (3)
pH = -log
10
[H
+
]

pOH = -log
10
[OH
-
]

pH = 14 pOH (and vice versa)


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18.1 Calculations involving acids and bases (HL)
18.1.1 State the expression for the ionic product constant of water (K
w
) (1)
Equilibrium expression for the self-ionisation of water at 25C
K
w
= [H
3
O
+
][OH
-
] = 1.00 x 10
-14
mol
2
dm
-6
at 25C

18.1.2 Deduce [H
+
(aq)
] and [OH
-
(aq)
] for water at different temperatures given K
w
values (3)

H
2
O
(l)
+ H
2
O
(l)
H
3
O
+
(aq)
+ OH
-
(aq)
H = +57kJ mol
-1

Endothermic, therefore energy is required to break the bonds

According to Le Chateliers principle, increase in temperature favours the forward reaction
i.e. equilibrium shifts towards the right and K
w
value increases

As ratio of [H
+
] must remain equal to [OH
-
] in pure water, then if we know K
w
, we can easily
calculate concentrations of [H
+
] and [OH
-
], and hence values of pH and pOH


1. K
w
= [H
3
O
+
][OH
-
]

2. [H
3
O
+
] = [OH
-
]

3. K
w
= [H
3
O
+
]
2


4. [H
3
O
+
+ = K
w
= [OH
-
]


18.1.3 Solve problems involving [H
+
(aq)
], [OH
-
(aq)
], pH and pOH (3)
pH:
pH = -log
10
[H
+
(aq)
]

[H
+
(aq)
] = 10
-pH


pOH:
pOH = -log
10
[OH
-
(aq)
]

[OH
-
(aq)
] = K
w
/ [H
+
(aq)
]

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pK
w
:
pK
w
= -log
10
K
w


pK
w
= pH + pOH = 14

Calculation of the pH of a weak base:

1. Find the [OH-] from the pKb value (in the same way as for weak acid type calculations)
2. From the [OH-] find the pOH
3. Find the pH from: pOH + pH = 14
Example:

Stage 1:
pH of 0.5 M phenol (pKa = 9.83)
pKa = 9.83 therefore pKb = 14 9.83
pKb = 4.07
Kb = 10
-4.07
= 8.51 x 10
-5

Kb x [phenol] = [X+][OH-]
[OH-+ = (Kb x *phenol+)
[OH-+ = (8.51 x 10
-5
x 0.5)
[OH-] = 6.52 x 10
-3


Stage 2:
pOH = -log
10
[OH
-
]
pOH = 2.19

Stage 3:
pH = 14 2.19
pH = 11.81

18.1.4 State the equation for the reaction of any weak acid or weak base with water and hence
deduce the expressions for K
a
and K
b
(1)
Weak acid with water:
HA
(aq)
+ H
2
O
(l)
A
-
(aq)
+ H
3
O
+
(aq)
K
a
= [A
-
][H
3
O
+
]
[HA]
Weak base with water:
B
(aq)
+ H
2
O
(l)
HB
+
(aq)
+ OH
-
(aq)
K
b
= [HB
+
][OH
-
]
[B]
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18.1.5 Solve problems involving solution of weak acids and bases using the expressions (3):
Note that for strong acids and bases [H
+
] or [OH
-
] are directly related to the concentration of
the acid/base

Therefore doubling the concentration of the acid will double [H
+
] and halve [OH
-
] (and the
reverse is true for bases).

HA
(aq)
H
+
(aq)
+ A
-
(aq)


B
(aq)
+ H
2
O
(l)
BH
+
+ OH
-
(aq)



1. K
a
= ( [H+][A-] / [HA] )

2. K
b
= ( [BH+][OH-] / [B] )

3. pK
a
= -log(K
a
)

4. pK
b
= -log(K
b
)

5. K
a
x K
b
= K
w
(i.e. they equal 1 x 10
-14
at 25C)

6. pK
a
+ pK
b
= pK
w
(ie 14 at 25C)


For any weak acid and its conjugate base: K
a
x K
b
= K
w



18.1.6 Identify the relative strengths of acids and bases using values of K
w
, K
b,
pK
a
and pK
b
(2)








Summary strong acid weak acid strong base weak base
Ka very large Large very low low
pKa very low 0 - 2 2-7 high 13-14 7-12
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18.2 Buffer solutions
18.2.1 Describe the composition of a buffer solution and explain its action (3)
Buffer solutions resist changes in pH when a small amount of an acid or a base is added
Acidic buffer:
HA
(aq)
+ H
2
O
(l)
A
-
(aq)
+ H
3
O
+
(aq)
Weak acid conjugate base
Equilibrium lies far to the left
Larger proportion of reactants than products

MOH
(aq)
+ HA
(aq)
H
2
O
(l)
+ MA
(aq)

Strong base + weak acid salt
The salt then dissociates completely:
MA
(aq)
M
+
(aq)
+ A
-
(aq)
Addition of salt to weak acid produces a mixture that has equally high proportions of HA
(aq)

and A
-
(aq)

A
-
(aq)
+ H
+
(aq)
HA
(aq)
When a small amount of acid is added to the buffer, the pH initially decreases
Conjugate base ions, A
-
, react with the added H
+
ions, causing pH to increase back to original
OH
-
(aq)
+ H
+
(aq)
H
2
O
(l)
When a small amount of base is added, the pH initially increases as H
+
(aq)
is removed by
reaction with OH
-
(aq)

Weak acid dissociates to increase [H
+
(aq)
] and hence decrease pH to original level

Buffer solution:
B
(aq)
+ H
2
O
(l)
BH
+
(aq)
+ OH
-
(aq)
Weak base conjugate acid

HX
(aq)
+ B
(aq)
BHX
(aq)
Strong acid + weak base salt
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Summary of composition and behaviour of buffer solutions
Buffer
solution
Made up of When small amount of acid
added
When small amount of
base added
Acidic Weak acid, e.g. ethanoic
acid, CH
3
COOH
pH initially decreases
Conjugate base reacts
A
-
(aq)
+ H
+
(aq)
HA
(aq)

pH increases as H
+

reacts
pH initially decreases
H
+
(aq)
+ OH
-
(aq)
H
2
O
(l)

Weak acid dissociates
HA
(aq)
H
+
(aq)
+ A
-
(aq)

pH decreases as HA
dissociates
Basic Weak base, e.g. ammonia,
NH
3
Weak base reacts
B
(aq)
+ H
+
(aq)
BH
+
(aq)
pH increases as H
+

reacts
pH initially increases
Conjugate acid
dissociates
BH
+
(aq)
H
+
(aq)
+ B
(aq)

pH decreases as
conjugate acid
dissociates


18.2.2 Solve problems involving the composition and pH of a specified buffer system (3)

Calculation of buffer pH
The pH of a buffer solution can be found from the expression for Ka
K
a
= [H+][A-] / [HA]
this can be rearranged to
[H
+
] = K
a
x [HA]/[A
-
]
or
pH = pKa - log [HA]/[A
-
]

Due to the presence of salt in the buffer solution, there is a large reservoir of A
-
(aq)
present
that pushes K
w
to the left
HA
(aq)
+ H
2
O
(l)
A
-
(aq)
+ H
3
O
+
(aq)
Can assume that [HA] at equilibrium is essentially equal to the initial concentration of HA i.e.
concentration of weak acid in the buffer solution
[HA]
eq
[HA]
I
= [acid]
Similarly
[A
-
]
eq
[A
-
]
I
= [salt]
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[H
3
O
+
] = K
a
x [acid]
[salt]

pH = pK
a
+ log
10
[salt]
[acid]

pOH = pK
b
+ log
10
[salt]
[base]

Therefore, [H
3
O
+
] = K
a
and pH = pK
a


18.3 Salt hydrolysis
18.3.1 Deduce whether salts form acidic, alkaline or neutral aqueous solutions (3)
Salts involving ions with a high charge density
Solvation
Ionic compounds dissociate 100% into ions in solution. These ions become solvated by the
water molecules (the water molecules bond to the ions - this is one of the driving forces
behind dissolution). The polar water molecules use the lone pairs on the oxygen of the
water to coordinate to the positive metal ion. The ions are then enclosed by a 'cage' of
water molecules usually in an octahedral arrangement.
Octahedral arrangement of water molecules around a
positive ion (in this case a 3+ ion)

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Charge density
This means the charge to size ratio of the ion.
charge density = ionic charge/ionic size
When the ion has a charge of 3+ or when it is very small this charge to size ratio is enough
to polarise the water molecules surrounding the ion in solution. This results in a weakening
of the O-H bonds within the water molecules allowing hydrogen ions to be released into
the solution. Hence the solutions are acidic.
This effect is typified in aluminium salts (the aluminium ion has a charge of 3+) which are
very acidic in solution

The aluminium hexaaqua ion
Aluminium ions are surrounded by six water molecules in an octahedral arrangement. This
is called the aluminium hexaaqua ion. The high charge density of the aluminium ion
polarises the water molecules and hydrogen ions are released into solution. The solution is
so acidic that it releases carbon dioxide from sodium carbonate (this reaction is used in
some fire extinguishers to produce foam in conjunction with detergent)
[Al(H
2
O)
6
]
3+
[Al(OH)(H
2
O)
5
]
2+
+ H
+



[Al(OH)(H
2
O)
5
]
2+
[Al(OH)
2
(H
2
O)
4
]
+
+ H
+


Transition metals
As the transition metals have variable oxidation states the ions that are formed with high
charges (high oxidation state) also produce acidic solutions. A good examle of this is the
Iron III ion. Salts such as iron III sulphate are acidic in solution.

[Fe(H
2
O)
6
]
3+
[Fe(OH)(H
2
O)
5
]
2+
+ H
+



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IB Chemistry 2013
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Summary of salt hydrolysis
pH of solution Neutral Acidic Basic Depends on K
a
and
K
b

Combination of
acid and base to
make salt
Strong acid +
strong base
Strong acid + weak
base
OR
Strong acid anion +
highly charged
metal cation
Weak acid + strong
base
Weak acid + weak
base
Examples NaCl
KNO
3

NH
4
NO
3
CH
3
NHCl
Al(NO
3
)
3

FeCl
3

CH
3
COOK
HCOONa
CH
3
COONH
4

NH
4
CN


18.5 Indicators
18.5.1 Describe qualitatively the action of an acid-base indicator (2)
Indicators show when a neutralisation reaction is complete in most acid-base titrations
Acid-base indicators are usually weak acids, the dissociation of which can be represented as
HIn
(aq)
H
+
(aq)
+ In
-
(aq)
Colour 1 colour 2
When [H
+
] increases, equilibrium shifts to the left
When [H
+
] decreases, equilibrium shifts to the right
Point at which colour change occurs is called the endpoint

18.5.2 State and explain how the pH range of an acid-base indicator relates to its pK
a
value (3)
pH at which indicator will change colour can be calculated using the pK
a
of the indicator,
otherwise known as pK
in

KIn
(aq)
H
+
(aq)
+ In
-
(aq)


K
in
= [H
+
][In
-
]
[HIn]

-log
10
K
in
= -log
10
[H
+
][In
-
]
[HIn]
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pK
a
= pH log
10
[In
-
]
[HIn]
OR

pH = pK
in
+ log
10
[In]
[HIn]

The pH at the endpoint of the indicator is equal to the pK
a
of the indicator, pK
in


18.5.3 Identify an appropriate indicator for a titration, given the equivalence point of the
titration and the pH range of the indicator (3)


Indicator pKa Useful range
Methyl orange 3.7 3.1 - 4.4
Bromophenol blue 4.0 3.0 - 4.6
Methyl red 5.1 4.2 - 6.3
Bromothymol blue 7.0 6.0 - 7.6
Phenol red 7.9 6.8 - 8.4
Phenolphthlein 9.3 8.2 - 10.0

No indicators suitable for indicating the equivalence point for a titration of a weak acid with
a weak base

Equivalence point is where the ratio of moles of acid to moles of base is equal to the
stoichiometric ratio neither reactant is in excess

Endpoint is point where indicator changes colour very close to the equivalence point,
usually 1 or 2 drops after


.
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18.4 Acid-base titrations
18.4.1 Sketch the general shapes of graphs of pH against volume for titrations involving strong
and weak acids and bases, and explain their important features (3)
General
Type
Example
Typical Titration
Curve
Features of Curve
Strong acid
& Strong
Base
HCl added to NaOH

Curve begins at high pH typical of strong base
and ends at low pH typical of strong acid.
There is a large rapid change in pH near the
equivalence point (pH =7).
Strong
base &
strong acid
NaOH added to HCl

Curve begins at low pH typical of strong acid,
and ends at high pH typical of strong base.
There is a large rapid change in pH near the
equivalence point (pH=7).
Weak acid
& Strong
base
NaOH added to
ethanoic acid
(CH
3
COOH)

Curve begins at a higher acidic pH and ends at
high basic pH. The pH change at the
equivalence point (pH > 7) is not so great.
Strong acid
& Weak
base
Ammonia (NH
3
)
added to HCl

Curve begins at low pH and ends at a less
high basic pH. The pH change at the
equivalence point (pH < 7) is similar to that
for Strong base & Weak acid.
Weak acid
& Weak
base
Ammonia (NH
3
)
added to ethanoic
acid (CH
3
COOH)

Curve begins at higher acidic pH and ends at
low basic pH. There is not a great pH change
at the equivalence point (pH ~ 7) making this
a very difficult titration to perform.