CHM1235

ANALYTICAL CHEMISTRY
♥ It is a general term for a method in quantitative chemical
analysis in which the amount of a substance is
determined by the measurement of the volume that the
substance occupies.

♥ It is commonly used to determine the unknown

concentration of a known reactant.

♥ Volumetric analysis is often referred to as titration, a

laboratory technique in which one substance of known
concentration and volume is used to react with another
substance of unknown concentration.
 Volumetric Analysis
 Involves the preparations, storage, and measurement of
volume of chemicals for analysis

Volumetric Titrimetry
 Quantitative chemical analysis which determines
volume of a solution of accurately known concentration
required to react quantitatively with the analyte (whose
concentration to be determined).
 The volume of titrant required to just completely react
with the analyte is the TITRE.
 Titration
 A process in which a standard reagent is added to a
solution of analyte until the reaction between the two is
judged complete

Primary Standard
A reagent solution of accurately known concentration is
called a standard solution.
Standardization
 A process to determine the concentration of a solution
of known concentration by titrating with a primary
standard
 End point
 The point at which the reaction is observed to be
completed is the end point
 The end point in volumetric method of analysis is the
signal that tells the analyst to stop adding reagent and
make the final reading on the burette.
 Endpoint is observed with the help of indicator

Equivalent point
 The point at which an equivalent or stoichiometric
amount of titrant is added to the analyte based on the
stoichiometric equation
 Volumetric analysis involves a few
pieces of equipment:
Pipette – for measuring accurate and precise
volumes of solutions
Burette – for pouring measured volumes of
solutions
Conical flask – for mixing two solutions
Wash bottles – these contain distilled water for
cleaning equipment
Funnel – for transfer of liquids without
spilling
Volumetric flasks – a flask used to make up
accurate volumes for solutions of known
concentration
 Two solutions are used:
 The solution of unknown concentration;
 The solution of known concentration – this is also known
as the standard solution

 Write a balanced equation for the reaction between

your two chemicals
 Clean all glassware to be used with distilled water. The
pipettes and burettes will be rinsed with the solutions
you are adding to them
 The burette is attached to a clamp
stand above a conical flask
 The burette is filled with one of the
solutions (in this case a yellow
standard solution)
 A pipette is used to measure an
aliquot of the other solution (in this
case a purple solution of unknown
concentration) into the conical flask
 Prepare a number of flasks for
repeat tests
 Last, an indicator is added to the
conical flask
 Read the initial level of liquid in the
burette
 Turn the tap to start pouring out liquid of
the burette into the flask. Swirl the flask
continuously. When the indicator begins
to change colour slow the flow.
 When the colour changes permanently,
stop the flow and read the final volume.
The volume change needs to be calculated
(and written down). This volume is called a
titre
 Repeat the titration with a new flask now
that you know the ‘rough’ volume
required. Repeat until you get precise
results
 Acid-base
titration

Precipitation Complexometric

Reduction-
oxidation
 Titration is a process in which a standard
reagent is added to a solution of an
analyte until the reaction between the
analyte and reagent is judged to be
complete.
 When the reaction involves an acid and a
base, the method is referred to as an
acid-base titration.
 When the reaction involves oxidation
and reduction, the method is referred to
as a redox titration.
Titrations involving acid-base neutralization reactions.
 Equivalence point: The point in the reaction at which both
acid and base have been consumed (equivalent or exactly
stoichiometric amount), i.e. neither acid nor base is present in
excess.
 End point: Actual result obtained by observation of a sudden
change of physical properties, i.e. indicator changes color very
near to the equivalent point.
 Titrant:
The known solution added to the solution of unknown
concentration.
 Titration Curve:
The plot of pH vs. volume.
 END POINT EQUIVALENT POINT
The point at which an equivalent or
The point at which the reaction is
stoichiometric amount of titrant is
observed to be completed
added to the analyte
The end point signal frequently
occurs at some point other than the
The point at which the reaction is
equivalent point.
complete
- tells the analyst to stop adding
TITRANT and record the volume.
Theoritically at the equivalence point
The selected indicator should we can calculate the amount of
change color very near to the titrant that is required to react
equivalent point. EXACTLY with the amount of analyte
present.
What is a titration :
A procedure of carefully controlled
addition of reagent (titrant) to an analyte.

Usually in
buret
Known Usually in a
concentration – conical flask
called standard
What happened during Titration
 Reaction must be stoichiometric, well defined reaction
between titrant and analyte.
 Reaction should be rapid.
 Reaction should have no side reaction, no interference
from other foreign substances.
 Must have some indication of end of reaction, such as color
change, sudden increase in pH, zero conductivity, etc.
 Known relationship between endpoint and equivalence
point.
 Direct Titration:
Titrant is added to the analyte until the
reaction is complete.

 Back Titration:
Alternative technique to direct titration.
Example 1
A sample weighing 0.8365 g is a diprotic acid was dissolved in
75.0 mL distilled water. Indicator was added and the solution
was titrated with sodium hydroxide solution. 35.35 mL was
needed to reach the end point. Molar mass of acid is 150
g/mol.

1. State whether the equivalence point is greater or less than 7.

2. Name a suitable indicator that can be used in the above
titration.
3. Calculate the molarity of the base.
First write the reaction equation:
Equation: H2A + 2OH-  2H2O + A2-
1 mole acid = 2 mole base

0.835
Mole acid = = 5.5767 x 10-3 mole
150
= 5.5767 mmole
 5.5767
Molarity of acid = = 0.0744 M
75
Ma Va 1
=
Mb Vb 2

2 x 0.0744 x 75
Mb = = 0.3157 M #
35.35
OR
Mmole base = 2 x mmole acid
= 2 x 5.5767 mmole
= 11.1534 mmole NaOH.

Molarity NaOH = mmole NaOH

Volume (mL)

= 11.1534
35.35
= 0.3155 M
Example 2: Calculate the concentration of vinegar in %w/v for
a titration of 25 ml of vinegar which was primarily diluted 10
times (25mL into 250mL), reacted with 22.4 ml of 0.1 M NaOH
standard solution.

Mass of vinegar = (Litersvinegar)(Mvinegar)(Fwgtvinegar)

= (0.25)(
22.4 x 0.1 )(60)
25
= 1.34g

In %w/v, concentration of vinegar is 1.34/25 = 5.4%

In g/mL
Sometime not feasible due to:
 Reaction kinetic or the reaction rate is slow.
 No suitable indicator in the direct titration.
 The color change is slow or delay.
 The end point is far from the equivalent point.
 In a simple acid-base titration, a base (reagent) is added
in a known quantity – greater than the amount required
for acid neutralization.

 Acid and base reacts completely.

 The remaining base is titrated with a standard acid.

 The system has gone from being ACID, past the

equivalent point to the BASIC (excess base), and back to
the equivalent point again. The final titration to the
equivalent point is called BACK TITRATION.
 The titration of insoluble acid organic acid with NaOH is
not practical because the reaction is slow.
 To overcome it add NaOH in excess and allow the
reaction to reach completion and then titrate the excess
NaOH with a standard solution of HCl.
 The system has gone from being ACID , past the
equivalence point to the BASIC side (excess base), and
then back to the equivalence point.
 The final titration to the equivalence point is called a
BACK TITRATION.
 Calculation Examples On Analysis Using
Back Titration Method.

Example 1
150.0 mL of 0.2105 M nitric acid was added in
excess to 1.3415 g calcium carbonate. The
excess acid was back titrated with 0.1055 M
sodium hydroxide. It required 75.5 mL of the
base to reach the end point.

Calculate the percentage (w/w) of calcium

carbonate in the sample.
First write a balance equation for the above
reactions.

2HNO3 + CaCO3  Ca(NO3)2 + CO2 + H2O ------ 1

HNO3 + NaOH  NaNO3 + H2O ------- 2

From Equations above:

1 mole HNO3 = ½ mole CaCO3
1 mole HNO3 = 1 mole NaOH

Initial amount of acid:

mmole of acid = 0.2105 x 150
= 31.575 mmole acid.
Remaining/excess acid during back titration:
Mmole of excess acid = 0.1055 x 75.5
= 7.965 mmole acid.

Mmole of acid reacted with CaCO3 = ( 31.575 – 7.965 )

= 23.61 mmole acid.

Mmole of CaCO3 = ½ x mmole acid

= ½ x 23.61
= 11.805 mmole CaCO3.
Gram CaCO3 = mole x molar mass
= 11.805 x 10-3 x 100
= 1.1805 g.
weight CaCO3
% CaCO3 = x 100
weight of sample
1.1805
= x 100
1.3415
= 87.99 % (w/w)
Arhenius
Acid HA H+ + A-
 Acid are species that can DONATE PROTON, H+

Base BOH B+ + OH-

 Base are species that can DONATE HYDROXIDE ions, OH-

 Neutralisation is the reaction between an acid and a base :

H+ + OH-  H2O

Bronsted:
Acid  it can donate proton, H+
Base  it can accept proton, H+
In theory, any strong acid or strong base can
be used as titrant.
The reason for this is that most reaction
involving a strong acid or a strong base is
QUANTITATIVE.

Examples of strong acid titrants :

Hydrochloric acid (HCl), Nitric acid (HNO3),
Perchloric acid (HClO4), Phosphoric acid (H3PO4)
Acetic acid ,(CH3COOH)
Ammonium ion, (NH4-)
Hydrogen flouride, (HF)
Carbonic acid, (H2CO3)
Nitrous acid, (HNO2)
Hydrogen sulphide, (H2S)
Hydrogen cynide, (HCN)
 Strong & Weak Base Titrant

Strong base titrant Weak base titrant

Sodium hydroxide, Ammonium hydroxide,
NaOH NH4OH
Potassium hydroxide, Amine acetate.
KOH Carbonate, CO32-
Magnesium hydroxide, Flouride ion, F-
Mg(OH)2 Sodium carbonate,
Barium hydroxide , NaCO3
Ba(OH)2
1. Titration of strong acid with strong base.
2. Titration of strong acid with weak base.
3. Titration of weak acid with strong base.
4. Titration of weak acid with weak base.
 pH – A Measure of Acidity

pH = -log [H+]

Solution Is At 250C
neutral [H+] = [OH-] [H+] = 1 x 10-7 pH = 7
acidic [H+] > [OH-] [H+] > 1 x 10-7 pH < 7
basic [H+] < [OH-] [H+] < 1 x 10-7 pH > 7

pH [H+]

36
  Strong acid with strong Base
 Equivalence at pH 7

7
pH

mL of Base added
  Titration of a strong acid by a strong base

Sudden sharp
changes of pH

Slow change of pH

Titration curve for the titration of 25.00 mL of 0.2000 M HCl (a strong acid) with the 0.2000
M NaOH (a strong base).
Titration curve for the titration of 50.00 mL of 0.2000 M HCl (a strong
acid) with the 0.2000 M NaOH (a strong base).

Indicator
color
 l Weak acid with strong Base
l Equivalence at pH >7
l When the acid is neutralized it makes a weak base

>7

7
pH

mL of Base added
 l Strong base with strong acid
l Equivalence at pH 7

7
pH

mL of acid added
 l Weak base with strong acid
l Equivalence at pH <7
l When the base is neutralized it makes a weak acid

<7
pH

mL of acid added
pH change is very gradual
 Do the stoichiometry.
 mL x M = mmol
 There is no equilibrium .
 They both dissociate completely.
 The reaction is H+ + OH-  HOH
 Use [H+] or [OH-] to figure pH or pOH
 The titration of 50.0 mL of 0.200 M HNO3
with 0.100 M NaOH
 There is an equilibrium.
 Do stoichiometry.
 Use moles
 Determine major species
 Then do equilibrium.
 Titrate 50.0 mL of 0.10 M HF (Ka = 7.2 x 10-4)
with 0.10 M NaOH
 Strong acid and base just stoichiometry.
 Weak acid with zero ml of base - Ka
 Weak acid before equivalence point
–Stoichiometry first
–Then Henderson-Hasselbach
 Weak acid at equivalence point- Kb
- Calculate concentration
 Weak acid after equivalence - leftover
strong base.
- Calculate concentration
 Weak base before equivalence point.
–Stoichiometry first
–Then Henderson-Hasselbach
 Weak base at equivalence point Ka.
-Calculate concentration
 Weak base after equivalence – left over
strong acid.
-Calculate concentration
Acid –Base Indicators
The acid-base indicator function by changing
colour just after the equivalence point of a
titration; this colour change is called the
end point.
The end point is most often detected
VISUALLY. Most acid-base indicators are
organic dye molecules which are either
acids or bases.
Indicators can be monoprotic (HIn) or diprotic
(H2In) acids.
The acid form of an indicator is usually
coloured; when it loses a proton resulting in
anion (In-) , or base form of the indicator,
exhibiting different colour.
The two forms exist in equilibrium with one another
as follows:
Hin H+ + In-
(colour A) (colour B)
A diprotic acid indicator, H2In, ionizes in TWO steps
as follows:
H2In HIn- + H+ H+ + In-

(colour A) (colour B) (colour C)

Choose an indicator that undergoes a distinct colour
change at the equivalence point (true end point) of
an acid-base titration .
Choose an indicator whose middle half of the pH
transition range (greatest colour change)
encompasses/overlap the pH at the equivalence
point or the pH at the steepest part of the titration
curve.
For indicator color change to be detectable by normal
eyesight, a rough tenfold excess of one or the other
form of the indicator must be present. This
corresponds to a pH range of  1 pH unit about the
pK of the indicator
Common Name Transition range Colour Change
ACID BASE
Crystal violet 0.1 – 1.5 Yellow Blue
Thymol blue 1.2 – 2.8 Red Yellow
Mrthyl yellow 2.4 – 4.0 Red Yellow
Methyl orange 3.1 – 4.4 Red Yellow
Bromocresol green 3.8 – 5.4 Yellow Blue
Methyl red 4.2 – 6.3 Red Yellow
Chlorophenyl red 4.5 – 6.4 Yellow Red
Bromothymol blue 6.0 – 7.6 Yellow Blue
Phenol red 6.4 – 8.0 Yellow Red
Thymol blue 8.0 – 9.6 Yellow Blue
Phenolpthalein 8.0 – 9.7 Colourless Red
 WEAK ACID / STRONG BES

1 5
3

2 6
1. A solution of sodium hydroxide contained 0.250 mol dm-3.
Using phenolphthalein indicator, titration of 25.0 cm3 of this
solution required 22.5 cm3 of a hydrochloric acid solution for
complete neutralization.
(a) write the equation for the titration reaction.
(b) calculate the moles of sodium hydroxide neutralized.
(c) calculate the moles of hydrochloric acid neutralized.
(d) calculate the concentration of the hydrochloric acid in
mol/dm3 (molarity).
(a) NaOH(aq) + HCl(aq) ==> NaCl(aq) + H2O(l)
(b) moles sodium hydroxide neutralized:
0.250 x 25.0/1000 = 0.00625 mol NaOH
(remember: moles = molarity x volume in dm3 and its two
rearrangements and 1 dm3 = 1000 cm3)
(c) moles HCl = moles NaOH (equation) = 0.00625 mol HCl (in
22.5 cm3)
(d) concentration hydrochloric acid =
0.00625 x 1000 ÷ 22.5 = 0.278 mol dm-3 (3sf)
(scaling up to 1 dm3 = 1000 cm3 to get the molarity)
Another way to work it out is 22.5 cm3 = 22.5 ÷ 1000 = 0.0225 dm3
Therefore molarity = 0.00625 ÷ 0.0225 = 0.278 mol dm-3
2. A solution made from pure barium hydroxide contained 2.74 g
in exactly 100 cm3 of water. Using phenolphthalein indicator,
titration of 20.0 cm3 of this solution required 18.7 cm3 of a
hydrochloric acid solution for complete neutralisation.
[atomic masses: Ba = 137, O = 16, H = 1)
(a) write the equation for the titration reaction.
(b) calculate the molarity of the barium hydroxide solution.
(c) calculate the moles of barium hydroxide neutralised.
(d) calculate the moles of hydrochloric acid neutralised.
(e) calculate the molarity of the hydrochloric acid.
(a) Ba(OH)2(aq) + 2HCl(aq) ==> BaCl2(aq) + 2H2O(l)

(b) formula mass of Ba(OH)2 = 171, moles = 2.74 ÷ 171 = 0.016 mol
in 100 cm3, (scaling up x 10) therefore 0.16 mol in 1000 cm3,
so molarity of Ba(OH)2 = 0.16 mol dm-3

(c) moles Ba(OH)2 used in titration = 0.16 x 20/1000 = 0.0032 mol

(d) moles HCl titrated = 2 x moles of Ba(OH)2 used (2 : 1 in

equation) 2 x .0032
= 2 x 0.0032 = 0.0064 mol HCl in 18.7 cm3 of the acid solution,
18.7 cm3 = 0.0187 dm3

(e) therefore molarity of HCl(aq) = 0.0064/0.0187 = 0.342 mol dm-3

3. 4.90g of pure sulphuric acid was dissolved in water, the
resulting total volume was 200 cm3. 20.7 cm3of this solution was
found on titration, to completely neutralise 10.0 cm3 of a sodium
hydroxide solution. [atomic masses: S = 32, O = 16, H = 1)
(a) write the equation for the titration reaction.
(b) calculate the molarity of the sulphuric acid solution.
(c) calculate the moles of sulphuric acid neutralised.
(d) calculate the moles of sodium hydroxide neutralised.
(e) calculate the concentration of the sodium hydroxide in mol
dm-3 (molarity).
(a) 2NaOH(aq) + H2SO4(aq) ==> Na2SO4(aq) + 2H2O(l)

(b) moles H2SO4 = 4.90 ÷ 98 = 0.050 mol in 200cm3

scaling up to get molarity of the sulphuric acid solution,
0.050 x 1000 ÷ 200 = 0.25 mol dm-3

(c) moles of sulphuric acid neutralised =

0.250 x 20.7/1000 = 0.005175 mol

(d) moles of sodium hydroxide neutralised =

2 x 0.005175 = 0.01035 mol (2 : 1 in equation)

(e) concentration of the sodium hydroxide =

0.01035 x 1000 ÷ 10 = 1.035 mol dm-3 (molarity 1.04, 3sf)
4. 0.12 g of rock salt was dissolved in water and titrated with
0.100 mol dm-3 silver nitrate until the first permanent brown
precipitate of silver chromate is seen.
19.7 cm3 was required to titrate all the chloride ion.
[Atomic masses: Na = 23, Cl = 35.5]
(a) How many moles of chloride ion was titrated?
(b) What mass of sodium chloride was titrated?
(b) What was the % purity of the rock salt in terms of sodium
chloride?
(a) moles = molarity AgNO3 x volume in dm3 =
0.100 x 19.7/1000 = 1.97 x 10-3 mol Cl-ion

[AgNO3:NaCl or Ag+:Cl- is 1:1]; f. mass NaCl = 23 + 35.5 = 58.5

(b) mass = mol x formula mass = 1.97 x 10-3 x 58.5 = 0.1152 g NaCl

(c) % purity = 0.1152/0.12 x 100 = 96.0 % in terms of NaCl (3sf)

5. A 50.0 cm3 sample of sulphuric acid was diluted to 1.00 dm3. A
sample of the diluted sulphuric acid was analysed by titrating
with aqueous sodium hydroxide. In the titration, 25.0 cm3 of 1.00
mol dm-3aqueous sodium hydroxide required 20.0 cm3 of the
diluted sulphuric acid for neutralisation.
(a) give the equation for the full neutralisation of sulphuric acid
by sodium hydroxide.
(b) calculate how many moles of sodium hydroxide were used in
the titration?
(c) calculate the concentration of the diluted acid.
(d) calculate the concentration of the original concentrated
sulphuric acid solution.
(a) 2NaOH(aq) + H2SO4(aq) ==> Na2SO4(aq) + 2H2O(l)

(b) moles of sodium hydroxide used in the titration =

25.0 x 1/1000 = 0.025 mol NaOH

(c) mol H2SO4 = mol NaOH ÷ 2 = 0.0125 mol in 20.0 cm3,

so scaling up to 1000 cm3 to get molarity of diluted acid =
0.0125 x 1000 ÷ 20 = 0.625 mol dm-3
(or molarity = 0.0125 mol/0.02 dm3 = 0.625 mol dm-3)

(d) scaling up from 50 to 1000 cm3, gives the concentration of the

original concentrated sulphuric acid solution,
= 0.625 x 1000 ÷ 50 = 12.5 mol dm-3