Titration Curves, Buffers

and Indicator Theory

Chemistry 12
Read Pages 595-597 (buffers),
608-612 (titration curves), 599-
605 (indicators)
 Titration
 is a technique to determine
the concentration of an
unknown acid or base.
 slow addition of one solution
where the concentration is
known to a known
volume of another
solution where the
concentration is unknown
until the reaction reaches a
desired level.
• Colour change is close to
equivalence point
(hopefully)
 a color change from a pH indicator is reached
or a direct reading using a pH meter.
 This information can be used to calculate the
concentration of the unknown solution.
 Strong acid – strong base
titration
 Equivalence point is
where pH = 7
 Complete
neutralization of H+
(acid) with OH-
(base) to make H2O.
 Ideally, you want an
indicator whose
endpoint is very
close to the titration’s
equivalence point.
(within 2 pH units)
 Indicators
 A substance (often organic) that has
a different colour in acidic and basic
solutions and can be used to detect
end points of titrations.
 It is a weak acid or base
 How indicators work:
example of Litmus used
 HIn(aq) < -- > H+(aq) + In-(aq)
Red Blue
 In presence of acid = shift to left = red

 In presence of a base = shift to right

 Ka = [H+][In-]

[HIn]
Rearrange: [HIn] = [H+]
[In- ] Ka
The colour of the indicator depends on [H+] and
also on Ka value, when pH = pKa indicator is in
the middle of its colour change.
 Useful indicators
 Phenolphthalein used
 In this curve, you
had acid in the flask
(colourless b/c pH is
less than 8.2)
 You are titrating
pH
(adding) base to
raise the pH.
 The colour changes
between 8.2 – 10.
Volume of base added
 Practice Choosing an Indicator
1. What colour will the solution be if its pH
is 5.6 using
a) Methyl Red? Orange
b) Ethyl Red? Almost Red
c) Thymol Blue? Yellow

Note: If the range is 8.2-10 like for

phenolpthalein, then any pH less than
8.2 is colourless, and any pH greater
than 10 is pink and anything in between
is an in between colour, like pale pink
 Types of titration curves:

Polyprotic acid with

strong base
 Why do the curves look
different?
 They are all
examples of acids
with bases BUT
• Strong acids and
bases dissociate
100% in solution
• All [H+] can react
with all [OH-] to
make water and
neutralize at pH =7
• No side reactions
occurring here
 Acids, Bases and Neutral salts
 The reason why a strong acid
[HCl] and a strong base
[NaOH] can make water and
pH = 7 is because a neutral
salt was also made [NaCl]
 Neutral salts are like
spectator ions, they move
around in solution but don’t
affect the pH. They are
neutral.
 Any salt made from the
following ions are neutral
 Neutral salts  pH = 7 for
SA/SB

Because NaCl is the neutral salt made, no hydrolysis

occurs, leaving the pH to be only affected by the H+
from HCl and the OH- from NaOH. Doesn’t matter
which order it is titrated.
Hydrolysis and acidic/basic salts
 When weak acids and bases react, the relative
strength of the conjugated acid-base pair in the
salt determines the pH of its solutions.
 The salt solution formed can be acidic, or
basic.
 A salt formed between a strong acid and a weak
base is an acid salt, for example NH4Cl.
 A salt formed between a weak acid and a strong
base is a basic salt, for example NaCH3COO.
 Hydrolysis of acidic salts
 A salt formed between a strong acid and
a weak base is an acid salt.
 Ammonia is a weak base, and its salt
with any strong acid gives a solution
with a pH lower than 7.
 For example, let us consider the
reaction:
HCl + NH4OH  NH4Cl(aq) + H2O
H+ + Cl-+ NH4+ + OH-  NH4+ +Cl-+ H2O
Strong Acid with weak base
Titrations
 Buffering region
occurs where pH is
changing gradually
 After the buffering
region there is a
drastic drop where
the equivalence
point is found.
 Note that the pH is below 7 at equivalence
point because of the hydrolysis of NH4Cl.
 NH3 reacts completely with HCl to form only
NH4+ and Cl- in solution. The NH4+ will
hydrolyse making NH3 and H3O+
 The hydronium ion created adds to the acidity
therefore lowering pH
 NH4+ + H2O < -- > NH3 + H3O+
 Buffering Regions
 Areas on the
titration curve
where buffering
occurs.
 Buffering: area
that resists change
to pH when a small
amount of acid or
base is added to it.
 Buffers
 They work because they are made of
a weak acid and a conjugate base
mix OR a weak base and a conjugate
acid mix.
 THINK… the weak acid can take up
some base without changing pH and
the conjugate base can take up some
acid without changing pH to a point.
 Buffering in Blood
 Dissolved CO2 in blood reacts with H2O to
form HCO3- ions
CO2 + H2O < -- > HCO3- + H3O+
 HCO3- dissociates in water to make CO32-
HCO3- + H2O < -- > CO32- + H3O+

If excess acid is added HCO3- reacts to make CO2

If excess base is added HCO3- reacts to make CO32-
 Hydrolysis of basic salts
 A basic salt is formed between a
strong base and a weak acid
 The higher pH is due to the hydrolysis
of the conjugate base of the weak acid
used during the neutralization
reaction.
 For example, lets consider the reaction
CH3COOH + NaOH  NaCH3COO + H2O
 NaCH3COO will break up to form Na+
and CH3COO- ions, and the acetate
ion will react with water to produce
hydroxide.
CH3COO- + H2O  CH3COOH + OH-
 Weak acid and strong base titrations

always have a pH greater than 7

Strong base with weak acid titration:
NaOH + CH3COOH  NaCH3COO + H2O
 pH starts low, so
acid was in flask.
 Added base, so pH
raises
 Equivalence point
is greater than 7
because of basic
salt hydrolysis of
NaCH3COO
 Can you explain why CH3COO-
undergoes hydroylsis?
 Remember that the NaOH and the
CH3COOH react and become neutral.
 Then the salts made undergo their
own reaction with water.
• In this case the salt is NaCH3COO.
• We only care about the CH3COO-
• That will react with any H+ in solution,
therefore raising the pH of the overall
solution.
 Polyprotic acid titrations
 For acids with more
than one hydrogen to
be removed, you can
see multiple steps in
the titration curve.
 Each step = a proton
being removed by the
base being added (in
this example)
 Example could be of
H2SO4 with NaOH.
 Diprotic H2SO4 with NaOH
 The first ion will break off
in water by the dissociation
• H2SO4 → H+ + HSO4-
 The second H+ comes from
the dissociation of HSO4- by
• HSO4- < -- > H+ + SO42-
 This is essentially titrating
two acids at once.
 Writing equations for
polyprotic/basic species
 Add up the separate steps, then
cancel out similar species to have the
net ionic equation.
 Ex: Write balanced, net ionic
equations for a solution of
phosphoric acid with sodium
hydroxide, and write the overall
neutralization reaction for the
titration
 Answer:
1. H3PO4 + OH-  H2PO4- + H2O
2. H2PO4 + OH-  HPO42- + H2O
3. HPO42- + OH-  PO43- + H2O
4. H3PO4 + 3OH-  PO43- + 3H2O

Steps 1-3 ionic equations; step 4 is net

ionic equation and only OH- is listed
but NaOH can be substituted in.
 Homework questions:
 Pg 598 # 7-9 Buffers
 Pg 616 # 3-5 titrations of wa,wb
 Pg 611 # 23 polyprotic