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Titrimetric (Volumetric)
Methods of Analysis

1
Principles of titrimetric
analyses
• Titration is the process of
determining the quantity of

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a substance A by adding
measured increments of
substance B

• Add a reagent, called the

titrant, to a solution
containing another reagent,
called the titrand, and
allow them to react
2
2.1 Principles of titrimetric
analyses (Cont’d)
• Titration is a useful analytical technique to
determine the concentration of a solution

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• There are several types of titrations, depending
on nature of A and B:
 Acid-base titrations
 Back titrations/indirect
 Redox titrations
 Potentiometric titrations
 Conductimetric titrations
 Thermometric Titrations 3
2.1 Principles of titrimetric
analyses (Cont’d)
• Determine the volume of a solution (titre) that is required to
completely react with a fixed volume

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• If a titration is to be accurate we must combine
stoichiometrically equivalent amount of titrant and titrand

Equivalence point – the point at which an added titrant is

stoichiometrically equal to the number of moles of substance
(known as analyte) present in the sample

• The point at which the reaction is complete is determined

experimentally and is known as the endpoint of the titration
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2.1 Principles of titrimetric
analyses
• The end point is determined by a change in the color of a
substance, called an indicator, that we add to the titrand’s

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solution.

• The difference between the end point volume and the

equivalence point volume is a determinate titration error

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2.1 Principles of titrimetric
analyses
Criteria necessary for a titrimetric analysis:
known stoichiometry between the titrant and the

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titrand

the titration reaction must effectively proceed to

completion

titration reaction must occur rapidly

a suitable method for accurately determining the

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end point
Standards Solutions
• A standard solution is a solution whose concentration
is known accurately

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• May be classified as:
Primary standard
Secondary standard

• A primary standard is a pure, stable standard

solution; concentration is accurately known

• A secondary standard is a solution that is not stable in

its own form, and must first be standardized against a 7
primary standard before being used
Standards Solutions
The standard solution should:
 Be sufficiently stable
The concentration needs to be determined only once

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 React rapidly with analyte
Time required between additions is minimized

 React completely with the analyte

End points can be obtained

 Undergo a selective reaction with the analyte

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Few standards meet all these requirements

Standard Solutions
• Two excellent standard solutions
KHP

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HCl

• These are used as standard solutions but have

some instability
Na2S2O3 – light sensitive; susceptible to bacterial
oxidation
AgNO3 – light sensitive
KMnO4 - oxidized
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Standards Solutions
The accuracy of a titration method is dependent on
the accuracy of the concentration of the standard

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solution

Q. How do you prepare a standard solution of

accurate concentration?

How are the concentrations of standard solutions

determined?
1. Direct Method 10
2. Standardization
Standards Solutions –
Direct Method
• Accurately weigh a
quantity of a primary

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standard
• Dissolve weighed
primary standard in
suitable solvent
• Dilute to exactly known
volume in a volumetric
flask
• Solutions of Na2CO3 and
AgNO3 may be prepared 11
in this manner
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12

http://www.chemiasoft.com/chemd/node/41
Standard Solutions -
Standardization
The standard solution reacts quantitatively with a
primary standard

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eg. HCl is not a primary standard because of its
gaseous form at room temperature

However, solutions of HCl may be standardized

against anhydrous Na2CO3 to determine the
concentrations accurately
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Primary Standards
• A substance of high purity that is used prepare the
concentration of the standard solution in

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volumetric analysis

• Serves as a reference to determine unknown

concentrations

Q. Which compounds can we

use as a primary standard? 14
2.1 Criteria used in selecting
Primary Standards
1. High Purity
 Purity of at least 99.98%

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2. Stable towards air
 Not altered on exposure to air
 Not oxidized by air
 Not react with CO2 or absorb moisture from air
3. Absence of Water of Crystallization
 Stable to drying
 Composition should not change when heated or
change due to humidity 15
2.1 Criteria used in selecting
Primary Standards (Cont’d)
4. Relatively large formula weight
 Minimizes relative errors associated with weighing

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5. Reasonable solubility in titration medium

Few primary standards meet all the above requirements.

Examples of primary standards

 KHC8H4O4 (potassium hydrogen phthalate)
 NaHCO3
 Na2CO3
 KIO3
 (COOH)2 (oxalic acid) 16
 Borax
Suitable Primary Standards
for Acid-Base Titrations
Standardization of Acids

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Na2CO3 106 g mol-1

Standardization of Bases
KHC8H4O4 204.2 g mol-1

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Secondary Standards
• Compound whose purity is established by
chemical analysis

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• Solutions of unknown concentrations that are
standardized in the laboratory against primary
standards

• Serves as a reference material for titrimetric

method of analysis

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• Examples include KMnO4, NaOH
Indicators
• A weak acid or a weak base

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• The undissociated form of the indicator (HInd) is a
different colour than the isogenic form of the indicator
(Ind-)

HInd + H2O ⇌ H3O+ + Ind-

• Colour change occurs over a range of hydrogen ion

concentrations (i.e. the colour change from pure acid
to pure alkaline does not occur at specific hydrogen
ion concentration) 19
Indicators
The choice of indicators depend on the pH range of
the solution

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2.3 Titrimetric Analysis without
Indicators
Some titrimetric analyses do not require an
indicator

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For eg. conductimetric and potentiometric titrations in
which the end point is detected by electrical
measurements

For eg. some redox titrations such as permanganate

redox titrations

Thermometric uses the change in temperature to 22

indicate the end point
Thermometric titration
Acid-base reactions are
exothermic; heat generated by
the reaction

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Heat is absorbed by the titrand,
increasing its temperature

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Thermometric titration
Endpoint found by:
measuring

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temperature change
reaction

extrapolating the
titration branch and
the excess titration
branch
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Potentiometric Titration
• pH of reaction is
monitored using a pH
electrode

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• measure the potential
difference between two
electrodes of a suitable
cell
• Advantages:
possible in turbid,
coloured and very dilute
solutions
very sharp end points 25
ease of automation
Conductimetric Titration
• Electrical
conductance or
resistance of the

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solution being
titrated is monitored

• Plot Conductance vs
volume titrant added

• Can you explain the

shape of the graph?

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Back Titration
Back (or indirect) titration used if:
the titration’s reaction is too slow
a suitable indicator is not available

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there is no useful direct titration reaction

• For eg. if you wish to determine the concentration of

formaldehyde, H2CO, in an aqueous solution, the
oxidation of H2CO by I3– proceeds by the following
reaction:

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• The reaction above is too slow for a direct titration
Back Titration (Cont’d)
Indirect approach:
1. Pipette a fixed volume of H2CO into a conical flask

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2. Add a known excess of I3– and allow its reaction with
H2CO to go to completion

3. Determine the amount of unreacted I3– by titrating the

unreacted I3– with thiosulfate, S2O32–

The difference between the initial amount of I3– and the 28

amount in excess gives us the amount of I3– reacting with
the formaldehyde
Acid-Base Titrations

Review choosing suitable

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indicators for acid-base titrations
(Chemistry for CAPE)

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2.4 Experiments based on
titrimetric analysis
• Acid-base titrations

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• Redox titrations

• Back titrations

• Preparation of standards
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2.5 Calculations
Q1. Acid-Base Titration

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A 50.00 mL sample of a sodium hydroxide
solution is titrated with a 1.605 M solution
of sulfuric acid. The titration requires 24.09
mL of the acid solution to reach the
equivalence point. What is the molarity of
the base solution?
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A 50.00 mL sample of a sodium hydroxide solution is titrated with a 1.605 M solution of sulfuric acid. The titration
requires 24.09 mL of the acid solution to reach the equivalence point. What is the molarity of the base solution?

• n H2SO4 = 1.605 mol/L X 0.02409 = 0.039 mol

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• @ equivalence pt nNaOH = nH2SO4 ;

nNaOH = 2 X 0.039 mol = 0.770 mol

CM NaOH = 0.0770 mol/0.050 L = 1.54 mol/L

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Q2. Acid-Base Titration
Potassium hydrogen phthalate, KHC8H4O4, is a solid
acidic substance that reacts in a 1:1 mole ratio with

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bases that have one hydroxide ion. Suppose that
0.7025 g of potassium hydrogen phthalate (KHP) is
titrated to the equivalence point by 20.18 mL of a
KOH solution. What is the molarity of the KOH
solution?

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Potassium hydrogen phthalate, KHC8H4O4, is a solid acidic substance that reacts in a 1:1 mole ratio
with bases that have one hydroxide ion. Suppose that 0.7025 g of potassium hydrogen phthalate
(KHP) is titrated to the equivalence point by 20.18 mL of a KOH solution. What is the molarity of
the KOH solution?

• Vol of KOH = 0.02018 L

• Conc KOH = ?

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• m KHP = 0.7025g/204.22 g/mol = 3.44 x 10-3
• mole ratio is 1:1
CM KOH = 3.44 x 10-3 / 0.02018 L = 0.1705 mol/L KOH

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Q3. Redox Titration
A 25.00-mL sample of a liquid bleach was diluted to 1000 mL in
a volumetric flask. A 25-mL portion of the diluted sample was

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transferred by pipette into an Erlenmeyer flask containing an
excess of KI, reducing the OCl– to Cl–, and producing aqueous
I3–. The liberated I3– was determined by titrating with 0.09892 M
Na2S2O3, requiring 8.96 mL to reach the starch indicator end
point. Calculate the % w/v NaOCl in the sample of bleach.

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A 25.00-mL sample of a liquid bleach was diluted to 1000 mL in a volumetric flask. A 25-mL portion
of the diluted sample was transferred by pipette into an Erlenmeyer flask containing an excess of
KI, reducing the OCl– to Cl–, and producing aqueous I3–. The liberated I3– was determined by
titrating with 0.09892 M Na2S2O3, requiring 8.96 mL to reach the starch indicator end point.
Calculate the % w/v NaOCl in the sample of bleach.

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Q4. Redox Titration
A solution of permanganate is standardized by titration with
oxalic acid (H2C2O4). It requires 28.19 mL of the

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permanganate solution to react completely with 0.1103 g of
oxalic acid. The unbalanced equation for the reaction is
shown below. This reaction in occurring in an acidic
medium.
MnO4− + H2C2O4 + ⟶ Mn2++ CO2
What is the molarity of the permanganate solution?

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A solution of permanganate is standardized by titration with oxalic acid (H2C2O4). It requires
28.19 mL of the permanganate solution to react completely with 0.1103 g of oxalic acid. The
unbalanced equation for the reaction is shown below. This reaction in occurring in an acidic
medium.
MnO4− + H2C2O4 + ⟶ Mn2++ CO2
What is the molarity of the permanganate solution?

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A solution of permanganate is standardized by titration with oxalic acid (H2C2O4). It requires
28.19 mL of the permanganate solution to react completely with 0.1103 g of oxalic acid. The
unbalanced equation for the reaction is shown below. This reaction in occurring in an acidic
medium.
MnO4− + H2C2O4 + ⟶ Mn2++ CO2
What is the molarity of the permanganate solution?

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Q5. Back Titration
2.75 g sample of dolomite containing CaCO3 and
MgCO3 is dissolved in 80 cm3 of 1 M HCl solution.

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The solution is then diluted to 250 cm3. 25 cm3 of
this solution requires 20 cm3 of 0.1M NaOH
solution for complete neutralisation. Calculate the
% composition of the sample.

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Q6. Back Titration
The amount of ascorbic acid, C6H8O6, in orange juice was
determined by oxidizing the ascorbic acid to dehydroascorbic

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acid, C6H6O6, with a known amount of I3–, and back titrating the
excess I3– with Na2S2O3. A 5.00-mL sample of filtered orange
juice was treated with 50.00 mL of 0.01023 M I3–. After the
oxidation was complete, 13.82 mL of 0.07203 M Na2S2O3 was
needed to reach the starch indicator end point. Calculate the
concentration of ascorbic acid in mg/100 mL.

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2.6 Use of titrimetric analysis
in quantification
Acetic acid (ethanoic acid) content in
vinegar

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Sodium chlorate in commercial bleach
Vitamin C content in tablets or orange
juice
Purity of Aspirin
Analysis of neutralizing ability of antacid
tablets 42
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MORE QUESTIONS

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Q7.

Explain how you would

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prepare 2.000 L of 0.1374 M
silver nitrate.

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Q8.
A variety of systematic and random errors are possible
when standardizing a solution of NaOH against the primary

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weak acid standard potassium hydrogen phthalate (KHP).
Identify, with justification, whether the following are
systematic or random sources of error, or if they have no
effect. If the error is systematic, then indicate whether the
experimentally determined molarity for NaOH is too high
or too low. The standardization reaction is:

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Q8. Continued…
a) The balance used to weigh KHP is not properly calibrated
and always reads 0.15 g too low.
b) The indicator for the titration changes color between a pH of

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3–4.
c) An air bubble, which is lodged in the buret’s tip at the
beginning of the analysis, dislodges during the titration.
d) Samples of KHP are weighed into separate Erlenmeyer
flasks, but the balance is only tarred with the first flask.
e) The KHP is not dried before it was used.
f) The NaOH is not dried before it was used.
g) The procedure states that the sample of KHP should be
dissolved in 25 mL of water, but it is accidentally dissolved
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in 35 mL of water