Acids and Bases HL

Connecting to our previous learning

For every billion water molecules only 1 or 2 are ionized…
And that proportion gets even smaller at lower temperatures
 18.2 Calculations involving
acids and bases
Understandings:
● The expression for the dissociation constant of a weak
acid (Ka) and a weak base (Kb).
● For a conjugate acid base pair, Ka × Kb = Kw.
● The relationship between Ka and pKa is (pKa = -log
Ka), and between Kb and pKb is (pKb = -log Kb).
Applications and skills:
● Solution of problems involving [H+ (aq)], [OH–(aq)], pH,
pOH, Ka, pKa, Kb and pKb.
● Discussion of the relative strengths of acids and bases
using values of Ka, pKa, Kb and pKb.
The Dissociation
of Water
H2O ⇌ H+ + OH-
● The dissociation constant Kc is written as.

KC = [H+][OH-] / [H2O]
● The ion product constant of water, Kw, does not contain the
constant concentration of water:

Kw = [H+][OH-]
● At 25oC, Kw is equal to 1 x 10-14.
● We can find [H+] and [OH-] by finding the square root, which
is 1.0 x 10-7M.
 pH and pOH
pH = -log [H+] so [H+] = 10-pH
● The same relationships exist for [OH-]

pOH = -log [OH-] so  [OH-] = 10-pOH

Kw = [H+][OH-] = 1.0 x 10-14
● pH + pOH = 14 at 25oC. This is called pKw.
● For example, if pH = 2 , then [H+] = 1 x 10-2M
● thus [OH-] = 1 x10-12M and pOH = 12.
 What drives dissociation?
● Is the dissociation of water endothermic or exothermic?  

● So how is Kw affected by temperature and why?

● The reaction is endothermic as bonds are being broken.

● At higher temperatures than 298K, more water molecules
will dissociate.

● This will result in more H+ ions so a lower pH.

● Neutral is pH 7 at 298K but at 373K it is 6.1.

 
 
 What does neutral mean?
● Neutral is when the concentration of H+ and OH- ions are
the same.

● When is pH + pOH not equal to 14?

● Kw of pure water is 5.48 x 10-14 at 50oC.

● Find [H+], pH, [OH-], and pOH.

● [H+] = [OH-] = 2.34 x 10-7 M pH = pOH = 6.63

 Example 1
● Determine the [OH-] in mol dm-3 in an aqueous solution
at 298 K in which [H+]= 2.0 x 10-3 mol dm-3?

● [OH-] = Kw / [H+]

= 1.0 x 10-14 / 2.0 x 10-3

= 5.0 x 10-12 mol dm-3

 Example 2
● Deduce Kw for pure water given that its

[OH-] = 1.25 x 10-7 mol dm-3.

● Is this water at a temperature of greater than, equal to or

less than 25o C?

● Kw = 1.56 x 10-14
● Higher temperature than 25o C
 Example 3
● What is the pH of 0.01 mol dm-3 solution of HCl?

● What is the pH when 10 cm3 of this acid is diluted with 90

cm3 of water?

● a) pH = 2 b) pH = 3
 Weak acids and weak bases
HA(aq) + H2O(l) ⇌ H3O+(aq) + A-(aq)
HA(aq) ⇌H+(aq) + A-(aq)

● Ka is the acid dissociation constant

Kc= Ka = [H3O+][A-]
[HA][H2O]
● Water is constant concentration, so it is not included.
Ka = [H3O+][A-] or [H+][A-]
[HA] [HA]
 Acid and Base
Dissociation Constant
● Ka has a fixed value for a particular acid at a specified
temperature

● The higher the value of Ka the greater the dissociation

● And the stronger the acid
● Why?

B(aq) + H2O(l) ⇌ BH+(aq) + OH-(aq)

● Water must be included in the initial equation for bases.
 Practice
● Write the expression for Ka
● CH3COOH(aq)

● Write the expression for Kb

● C2H5NH2(aq)
 Example 5
● Place the following acids in order of increasing strength
A. H3PO4 Ka=7.1 x 10-3

B. HNO2 Ka=7.1 x 10-4

C. H2SO3 Ka=1.2 x 10-2

● B, A, C
 Derive Kw equations
from Ka and Kb expressions
HA ⇌ H+ + A-
so Ka = [H+] [ A-] / [HA]
And for the conjugate base
A- + H2O ⇌ HA + OH-
and Kb = [HA] [OH-] / [A-]
● Therefore
Ka x Kb = [H+][OH-] = Kw = 1.0 x 10-14 at 298K
pKa + pKb = pKw = 14
 Calculate Ka at equilibrium
●Calculate Ka at 298 K for a 0.010 mol dm–3 solution of
ethanoic acid (CH3COOH). It has a pH of 3.4 at this
temperature.

●pH 3.4 ⇒ [H+] = 10–3.4 = 4.0 × 10–4 mol dm–3

We know that [H+] = [CH3COO–]

●Consider the dissociation of the acid

● CH3COOH(aq) ⇌ CH3COO- (aq) + H+(aq)

initial 0.010 0.00 0.00

𝚫 – 4.0 × 10–4 +4.0 × 10–4 + 4.0 × 10–4

 Calculate Ka at equilibrium
● CH3COOH(aq) ⇌ CH3COO- (aq) + H+(aq)

initial 0.010 0.00 0.00

𝚫 – 4.0 × 10–4 +4.0 × 10–4 + 4.0 × 10–4

final 0.010 – (4 × 10–4) 4.0 × 10–4 4.0 × 10–4

The approximation 0.010 ≈ 0.010 – (4 × 10–4) is valid within the

precision of this data.

Ka = [CH3COO–][H+] = (4.0 × 10–4)2 = 1.6×10–5

[CH3COOH] 0.010
● A 0.75 mol dm–3 solution of ethanoic acid has a value for
Ka = 1.8 × 10–5 at a specified temperature.
What is its pH at this temperature?

Let the change in concentration of CH3COOH = –x

The change in concentration of CH3COO– and H+ = +x

CH3COOH(aq) ⇌ CH3COO–(aq) + H+(aq)

initial 0.75 0.00 0.00

𝚫 –x +x +x

final 0.75 – x x x

≈ 0.75
 CH3COOH(aq) ⇌ CH3COO–(aq) + H+(aq)

initial 0.75 0.00 0.00

𝚫 –x +x +x

final 0.75 – x x x

≈ 0.75 Valid with small Ka so little dissociation

Ka = [CH3COO–][H+] = x2 = 1.8×10–5

[CH3COOH] 0.75

Therefore x = √ (1.8 × 10 −5 × 0.75) = 3.7 × 10–3

[H+] = 3.7 × 10–3 ⇒ pH = 2.4

 Practice these problems
1. Calculate the Kb for a 0.100 mol dm–3 solution of
methylamine, CH3NH2 at 25 °C . Its pH is 11.80 at this
temperature.

2. A 0.20 mol dm–3 aqueous solution of ammonia has Kb of 1.8

× 10–5 at 298 K . What is its pH?
1. Calculate the Kb for a 0.100 mol dm–3 solution of
methylamine, CH3NH2 at 25 °C . Its pH is 11.80 at this
temperature.

CH3NH2(aq) ⇌ CH3NH3+(aq) + OH-(aq)

initial 0.100 0.00 0.00

𝚫 –0.0063 +0.0063 +0.0063

final 0.0937 +0.0063 +0.0063

Kb = [CH3NH3+][OH-] = (0.0063) 2 = 4.22×10–4

[CH3NH2] 0.0937
2. A 0.20 mol dm–3 aqueous solution of ammonia has Kb of
1.8 × 10–5 at 298 K . What is its pH?
NH3(aq) + H2O(l) ⇌ NH4+(aq) + OH-(aq)

initial 0.20 0.00 0.00

𝚫 –x +x +x

final 0.20 – x x x

≈ 0.20 Valid with small Kb so little dissociation

Kb = [NH4+][ OH-] = x2 = 1.8×10–5

[NH3] 0.720

Therefore x = √ (1.8 × 10 −5 × 0.20) = 1.9 × 10–3

[OH-] = 1.9 × 10–3 ⇒ pOH = 2.72 ⇒ pH = 14 - 2.72 = 11.28

 Gilbert Lewis

Lewis
acids and
bases
 18.1 Lewis acids and bases
Understandings:
● A Lewis acid is a lone pair acceptor and a Lewis base
is a lone pair donor.
● When a Lewis base reacts with a Lewis acid a
coordinate bond is formed.
● A nucleophile is a Lewis base and an electrophile is a
Lewis acid.
 18.1 Lewis acids and bases
Applications and skills:•
● Application of Lewis’ acid–base theory to inorganic and
organic chemistry to identify the role of the reacting
species.
● Define Kw as Ka × Kb.
● Define pKa as -logKa and pKb as -logKb.
● Solve problems involving [H+(aq)], [OH-(aq)], pH, pOH,
Ka, pKa, Kb and pKb.
● Discuss the relative strengths of acids and bases
using values of Ka, pKa, Kb and pKb.
 Lewis acids
● This definition includes substances which don’t have H+
ions.

● A Lewis acid is species that can accept a lone pair of

electrons.

● A Lewis acid is an electrophile.

 Lewis bases
● This definition includes substances which don’t have OH-
ions.

● A Lewis base is species that can donate a lone pair of

electrons.

● A Lewis base is an nucleophile.

Lewis acids are electrophiles
 This can
be seen
as proton
donation
or as
electron
pair
accepting
 What species are capable of
accepting a lone pair of electrons?

Molecules that have an incomplete valence shell

or a vacant valence orbital.

Hydrogen ions are not required.

Lewis acid-base complex
Lewis acid-base reactions
result in the formation of a dative covalent bond.
 BF3 has an incomplete octet
So it can accept an electron pair---Lewis acid
NH3 donates lone pair---Lewis base
 Transition metals
The metal ions have a high charge density and attract ions and
molecules with lone pairs (ligands).

These metal ions can form dative covalent bonds with

ligands.
The ligands surround the metal ion in a fixed number ratio, a
complex forms.
 Exercise 4, p. 277
● Identify the Lewis acid and the Lewis base
a) 4NH3 + Zn2+→[Zn(NH3)4]2+
b) 2Cl- + BeCl2→[BeCl4]2-
c) Mg2+ + 6H2O →[Mg(H2O)6]2+
 Exercise 5, p. 277
● Which of the following could not act as a ligand in a
complex ion of a transition metal?

a) Cl-
b) NCl3
c) PCl3
d) CH4
 18.3 pH curves
Understandings:
● The characteristics of the pH curves produced by the
different combinations of strong and weak acids and
bases.
Applications and skills:
● The general shapes of graphs of pH against volume
for titrations involving strong and weak acids and
bases with an explanation of their important features.
 A new idea about salts…
● Salts do not all form neutral aqueous solutions.
● Their pH in solution depends on how much their ions react
with water to hydrolyze it.

● Hydrolyze: cause water to break down into H+ and OH-

 How do we know what
type of salt we have?
● What acids and bases could the salt have been formed
from?
● NaCl could be formed from NaOH and HCl.
● The pH of the salt will be closer to the stronger one e.g. if
the acid is strong and the base is weak it will be an acidic
salt.
● If they are both strong then the salt is neutral.
● There are no generalizations for salts made from weak
acids and weak bases.

● NaCl could be formed from NaOH and HCl. Both are

strong. So NaCl is neutral.
Determining Salt Characteristics
● CH3COONa was formed from CH3COOH and NaOH, a weak
acid and strong base. Why is it alkaline?

CH3COONa → CH3COO- + Na+

H2O ⇌ H+ + OH-
● The ethanoate ions from the salt will combine with the H+
ions from the water.
CH3COO- + H+ → CH3COOH
● They will form ethanoic acid which is a weak acid so stays
undissociated in the solution which leaves an excess of
OH-, thus making the solution alkaline.
 Cation Hydrolysis
● Metal ions that are small and 2+ or 3+ may hydrolyze water
due to a high charge density.
● Al3+ ions attract more than 1 water molecule,
leading to hydrolysis.

● The OH attaches to the Al3+ and the H+ are free in the

solution, making the solution acidic.
 Cation Hydrolysis
● Metal ions which can hydrolyze water are:
Be2+, Al3+ and transition metals, especially Fe3+.
You are required to know these three for IB.

E.g. Relate this to the Periodicity unit

AlCl3 will cause hydrolysis of water, Al3+ acts as a ligand. There
will be excess H+ left in solution making the solution acidic.

MgCl2 is also very slightly acidic for the same reason.

 Basic oxides
Na2O(s) + H2O(l)→ 2NaOH(aq)
MgO(s) + H2O(l)→ 2Mg(OH)2(aq)
Li2O(s) + 2HCl(aq) → 2LiCl(aq) + H2O(l)
MgO(s) + 2HCl(aq) → MgCl2(aq) + H2O(l)
 Acidic Oxides
P4O10(s) + 6H2O(l)→4H3PO4(aq)
P4O6(s) + 6H2O(l)→4H3PO3(aq)
SO3(l) + H2O(l)→H2SO4(aq)
SO2(g) + H2O(l)→H2SO3(aq)
Cl2O7(l) + H2O(l)→2HClO4(aq)
Cl2O(l) + H2O(l)→2HClO(aq)
Insoluble in water but will react with hot, concentrated alkalis

SiO2(s) + 2OH-→SiO32-(aq) + H2O(l)

We Are Here 18.3
 Adding acid to base
● Your graphs for
adding base to
acid will have the
same shape but
start at pH 0
instead.
 Strong acid vs Strong Base
Pearsons page 387

● .
 Weak acid vs. Strong base
Pearsons page 388

● ,
 Half Equivalence
● At the half-equivalence point [acid] = [salt], we can
substitute these values into the equilibrium expression of
the acid:

● Ka =[H+][A–]/ [HA]
● so if we assume that [acid] = [HA] and [salt] = [A–], then
[HA] = [A–] and so we can cancel these terms in the
equilibrium expression:

● ∴ Ka = [H+] and pKa = pH

 Strong acid and Weak base
http://www.chemguide.co.uk/physical/acidbaseeqia/phcurves.html

● .
 Weak acid and Weak base
Pearsons page 389
● .
 Key Points
● Acid-base titration curves have a characteristic shape

● The shape depends on the combination of strong/weak

acid-strong/weak base used

● The pH changes very fast at the point of equivalence due to

the logarithmic nature of the pH scale

● The ‘flatter’ parts of the weak acid/base curves are due to

equilibrium effects
We Are Here
 18.3 Indicators
Understandings:
● An acid–base indicator is a weak acid or a weak base
where the components of the conjugate acid–base pair
have different colours.
● The relationship between the pH range of an
acid–base indicator, which is a weak acid, and its pKa
value.
Applications and skills:
● Selection of an appropriate indicator for a titration,
given the equivalence point of the titration and the end
point of the indicator.
 Indicators
Are usually weak acids but can be weak bases

Dissociated and undissociated forms have different colors

HIn(aq) ⇌ H+(aq) + In-(aq)

Color A ⇌ Color B

BOH(aq) ⇌ B+(aq) + OH-(aq)

What happens to the color when acid is added? Alkali added?

Explain why.
Indicators change color when…
Ka = [H+][In-] Ka = [H+][In-]
[HIn] [HIn]
● When [In-]=[HIn] we get a color change and...
Ka = [H+] and pKa = pH
● This is the end point of an indicator.

● Knowing the equivalence point of a titration and the pKa

of the indicators ⇒ choose a suitable indicator.
 Indicators
● At this point, the addition of a very small volume of acid or
base will shift the equilibrium as described above, and so
cause the indicator to change colour – this is its end-point.

● The colour change can be considered to take place over a

range of pKa ± 1.
 Choosing an indicator

● Check out the simulation here:

● http://introchem.chem.okstate.edu/DCICLA/acid_base.html

● From the simulation you can see the indicator should be

chosen such that the colour change happens as close as
possible to the equivalence point of the titration.
 18.3 Buffers
Understandings:
● The buffer region on the pH curve represents the
region where small additions of acid or base result in
little or no change in pH.
● The composition and action of a buffer solution.
 18.3 Buffers
Applications and skills:
● While the nature of the acid–base buffer always
remains the same, buffer solutions can be prepared by
either mixing a weak acid/base with a solution of a salt
containing its conjugate, or by partial neutralization of
a weak acid/base with a strong acid/base.
● Prediction of the relative pH of aqueous salt solutions
formed by the different combinations of strong and
weak acid and base
 Buffers
Something that acts to reduce the impact of one thing on
another
 Buffer Solutions
● A buffer solution is resistant to changes in pH on the
addition of small amounts of acid or alkali.

● Made up of a weak acid and its salt

OR a weak base and its salt.

HCOONa → HCOO- + Na+

HCOOH ⇌ HCOO- + H+ 

 What is the effect of adding
acid or base to water?

Pearsons page 379

 How buffers work
● Acidic buffers: maintain a pH value of less than 7.

● Basic buffers: maintain a pH value of more than 7.

● If methanoic acid and sodium methanoate form a buffer,

what happens when I add a small amount of acid to the
mixture?

● A small amount of OH-?

 Action of Buffer
HCOONa → HCOO- + Na+
HCOOH ⇌ HCOO- + H+
● If H+ is added, it will shift the dissociation equilibrium to
the left, removing the excess H+ ions and producing more
methanoic acid.

● If OH- is added, the H+ ions react to neutralize the OH- and

produce water.
More methanoic acid will dissociate to replace the H+ ions.

● Blood : Water + CO2 ⇌ H2CO3 ⇌ H+ + HCO3-.

Determining the pH of a buffer solution
HA(aq)<->H+(aq)+ A-(aq) eg. HF<-> H+(aq)+ F-(aq)

MA(aq) ->M+(aq)+ A-(aq) eg. NaF(aq) ->Na+(aq)+ F-(aq)

2 assumptions to make calculations easier

1. [HA]initial=[HA]equilibrium

(Weak acid so very little dissociation takes place)

1. [MA]initial=[A-]equilibrium

(Salt is totally dissociated so [ion] = [original salt]

 Ka and Kb
Ka is Kc for acids and Kb is Kc for bases.

pKa = - log Ka

pKb = - log Kb

pKw = - log Kw

pKw = pH + pOH

pKw = pKa + pKb

● What concentration of ethanoic acid will make a buffer
of: volume 140.ml using 15.0g of sodium ethanoate and
having a pH of 5.2?
CH3COOH↔CH3COO- + H+, CH3COONa → CH3COO- + Na+

The acid is at equilibrium so Ka = [CH3COO-][H+]/[CH3COOH]

pka= 4.76 for the acid (data bk), thus Ka = 10-4.76

pH = 5.2 so can find [H+], this is = 10-5.2

Moles of CH3COO- = mass /Mr, [CH3COO-] = moles/ volume

Plug all this in and [CH3COOH] = 0.47M

 What is the pH of a buffer containing: 1.00M
NH4OH and 0.40M NH4Cl?

● Kb = [NH4+][OH-]/[NH4OH]
Find pkb from data booklet which is 4.75 so Kb = 10-4.75

● [NH4OH] = 1.00M, [NH4+]= 0.40M

● Solve to find [OH-].

● [OH-] is 4.4 x 10-5M

● pOH = - log 4.4 x 10-5M = 4.4

● So pH = 14 - 4.4 = 9.6
 Henderson-Hasselbalch Equation
● Ka = [H+][A-]/[HA],
● Therefore [H+] = Ka [HA]/[A-]
● [HA] = acid, [A-] = salt
Taking logs, the equation becomes
● pH = pka + log [salt]/ [acid]
● pOH = pkb + log [salt]/ [base]
These equations can be used for buffers only, not to find the pH of a
weak acid or base.
● What is the pH of a buffer containing: 1.00M
NH4OH and 0.40M NH4Cl? (pKw = 14.00)

● pOH = pkb + log [salt]/ [base]

● pOH= 4.75 + log [0.40M]/ [1.00M] = 4.35

● pH =14.00 – 4.35 = 9.65

 What can influence buffers?

● Dilution???
● Ka and Kb are not changed by dilution
● Ratio of acid (or base) and salt concentration is not
changed

● Diluting a buffer does not change its pH

 What can influence buffers?

● Dilution???
● Ka and Kb are not changed by dilution
● Ratio of acid (or base) and salt concentration is not
changed

● Diluting a buffer does not change its pH

 What can influence buffers?
● Temperature???

● Temperature affects Ka and Kb

● Temperature affects buffer pH

● Constant temperature should be maintained when working

with buffers
Calculate the pH of a buffer solution made by reacting 20 cm3 of
0.10 mol dm-3 HCl(aq) with 40cm3 of 0.10 mol dm-3 NH3(aq) at
298 K. The pKb for ammonia is 4.75. (pKw = 14.00)

pOH = pkb + log [salt]/ [base]

[salt] = [base] as HCl used up and 20ml of the salt and base are left.

pOH = 4.75

pH = 14.00- 4.75 = 9.25