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MOD II: ANALYT. METH. & SEP. TECH.

CAPE CHEMISTRY UNIT II

Titrimetric Methods of Analysis


APPADU, Pooran; DEY, Basil
University of Guyana, Turkeyen Campus

Principles of Titrimetric (Volumetric) Analysis 1,2

We volumetrically measure the amount of reagent (usually titrant) required to complete a


chemical reaction with the analyte. A generic chemical reaction for titrimetric analysis is

aA+ tT products

where a moles of analyte A contained in the sample reacts with t moles of the titrant T in the
titrant solution.

The reaction is generally carried out in a flask containing the liquid or dissolved sample.
Titrant solution is volumetrically delivered to the reaction flask using a burette. Delivery of the
titrant is called a titration.
The titration is complete when sufficient titrant has been added to react with all the analyte. This
is called the equivalence point
An indicator is often added to the reaction flask to signal when all of the analyte has reacted.
The titrant volume where the signal is generated is called the end point. The equivalence and
end points are rarely the same.

Differentiate Between End Point vs. Equivalence Point

Equivalence point: theoretical point when amount of titrant = amount of analyte


Equivalence point of a titration cannot be determined experimentally
An estimate is made by observing a physical change (that is associated with the condition of
equivalence).
End point: the change
The difference between the end point and equivalence point is referred to as the titration
error.

Practice Question:

1 http://ion.chem.usu.edu/~sbialkow/Classes/3600/Overheads/Titration/Volumetric.html
2 Skoog, D., et al., (2004). Fundamentals of Analytical Chemistry 8th Edition. USA: Thomson Publishers

MOD II: ANALYT. METH. & SEP. TECH.CAPE CHEMISTRY UNIT II

Indicators & Ranges Revisit Later!

2.1

Acid Base

Many substances, natural and synthetic, display colours that depend on the pH of the solutions in
which they are dissolved in;
Some of these substances, which have been used for centuries to indicate acidity and alkalinity,
are still employed as acid/base indicators;
An acid/base indicator is a weak organic acid or a weak organic base whose undissociated form
differs in colour from its conjugate base or its conjugate acid form
For example, the behavior of an acid-type indicator, HIn, is described by the equilibrium:

+
+ H 3 O
HIn+ H 2 O I n
(acid colour)

The equilibrium for a base type indicator, In, is:

+
+ H 3 O
+ H 2 O I n
(base colour)
2.2

Redox

MOD II: ANALYT. METH. & SEP. TECH.CAPE CHEMISTRY UNIT II

A redox indicator (also called an oxidation-reduction indicator) is an indicator that undergoes


a definite color change at a specific electrode potential.3

The requirement for fast and reversible color change means that the oxidation-reduction
equilibrium for an indicator redox system needs to be established very fast. Therefore only a few
classes of organic redox systems can be used for indicator purposes.
There are two common type of redox indicators:
o metal-organic complexes (Ex. phenanthroline)
o true organic redox systems (Ex. Methylene blue)
Sometimes colored inorganic oxidants or reductants (Ex. Potassium manganate, Potassium
dichromate) are also incorrectly called redox indicators. They cant be classified as true redox
indicators because of their irreversibility.
Almost all redox indicators with true organic redox systems involve a proton as a participant in
their electrochemical reaction. Therefore sometimes redox indicators are also divided into two
general groups: independent or dependent on pH.

2.2.1

pH independent redox indicators


E0, V

Indicator

Color of Oxidized form Color of Reduced form

2,2'-bipyridine (Ru complex)

+1.33 V

colorless

yellow

Nitrophenanthroline (Fe complex)

+1.25 V

cyan

red

N-Phenylanthranilic acid

+1.08 V

violet-red

colorless

1,10-Phenanthroline (Fe complex)

+1.06 V

cyan

red

N-Ethoxychrysoidine

+1.00 V

red

yellow

2,2`-Bipyridine (Fe complex)

+0.97 V

cyan

red

5,6-Dimethylphenanthroline (Fe complex)

+0.97 V

yellow-green

red

o-Dianisidine

+0.85 V

red

colorless

Sodium diphenylamine sulfonate

+0.84 V

red-violet

colorless

Diphenylbenzidine

+0.76 V

violet

colorless

Diphenylamine

+0.76 V

violet

colorless

Viologen

-0.43 V

colorless

blue

2.2.2

pH dependent redox indicators


E0, V
Indicator

E0, V

Color of

Color of

at pH=0 at pH=7 Oxidized form Reduced form

Sodium 2,6-Dibromophenol-indophenol

or Sodium 2,6-Dichlorophenol-indophenol

+0.64 V

+0.22 V

blue

colorless

Sodium o-Cresol indophenol

+0.62 V

+0.19 V

blue

colorless

Thionine (syn. Lauth's violet)

+0.56 V

+0.06 V

violet

colorless

Methylene blue

+0.53 V

+0.01 V

blue

colorless

Indigotetrasulfonic acid

+0.37 V

-0.05 V

blue

colorless

3 http://en.wikipedia.org/wiki/Redox_indicator

MOD II: ANALYT. METH. & SEP. TECH.CAPE CHEMISTRY UNIT II

Indigotrisulfonic acid

+0.33 V

-0.08 V

blue

colorless

(syn. Indigodisulfonic acid

+0.29 V

-0.13 V

blue

colorless

Indigomono sulfonic acid

+0.26 V

-0.16 V

blue

colorless

Phenosafranin

+0.28 V

-0.25 V

red

colorless

Safranin T

+0.24 V

-0.29 V

red-violet

colorless

Neutral red

+0.24 V

-0.33 V

red

colorless

Indigo carmine

Complexometric4

2.3

A complexometric indicator is an ionochromic dye that undergoes a definite color change in


presence of specific metal ions.[1]
It forms a weak complex with the ions present in the solution, which has a significantly different
color from the form existing outside the complex.
Complexometric indicators are also known as pM indicators. [2]
Complexometric indicators are water-soluble organic molecules. Some examples are:
o Calcein with EDTA for calcium
o Curcumin for boron, although the red color change of curcumin also occurs for pH > 8.4
o Eriochrome Black T for calcium, magnesium and aluminium
o Fast Sulphon Black with EDTA for copper
o Hematoxylin for copper
o Murexide calcium and rare earths
o Xylenol orange for gallium, indium and scandium

Primary Standards

Highly purified compound that serves as a reference material in VOLUMETRIC and MASS
TITRIMETRIC methods
Accuracy of a method is dependent on the properties of the compound
Some primary standards for titration of acids:
o sodium carbonate: Na2CO3, mol wt. = 105.99 g/mol
o Sodium Bicarbonate, NaHCO3
Some primary standards for titration of bases:
o potassium hydrogen phthalate (KHP): KHC8H4O4, mol wt. = 204.23 g/mol
o hydrogen iodate: KH(IO3)2, mol wt. = 389.92 g/mol
o Potassium Iodate, KIO3
o Oxalic acid;
Some primary standards for redox titrations:
o potassium dichromate: K2Cr2O7, mol wt. = 294.19 g/m
o oxalic acid;

What are the criteria for choosing a primary standard?

Property
High purity
Atmospheric Stability

Reason
Impurities may interfere with the reaction

4 http://en.wikipedia.org/wiki/Complexometric_indicator

MOD II: ANALYT. METH. & SEP. TECH.CAPE CHEMISTRY UNIT II

Absence of hydrate water

Modest cost
Reasonable solubility in the titration
medium

Reasonably large molar mass

Composition of the solid does not change with


humidity
So that it is affordable to everyone!

Relative error associated with weighing the


standard is minimized

Notes:

Few compounds exist with these characteristics!


Consequently, less pure compounds are used instead of a primary standard.
The PURITY of such a secondary standard MUST be established by CAREFUL analysis.

KHP is used as a "primary" standard because it is chemically stable, water soluble, inexpensive, and
obtainable in high purity.
4

Standard Solutions

4.1

Introduction
A reagent of known concentration that is used to carry out a titrimetric analysis
Standard solns play a central role in all titrimetric methods of analysis.
Ideal standard solution will:
o Be sufficiently stable so that it is necessary to determine its concentration only once;
o React rapidly with the analyte so that the time required between additions of reagent is
minimized;
o React completely (more or less) with the analyte so that the satisfactory end points are
realized;
o Undergo a selective reaction with the analyze that can be described by a balanced
equation;
The accuracy of a titrimetric method can be no better than the accuracy of the
concentration of the standard solution used in the titration!

4.2

Preparing Standard Solutions

4.2.1

Introduction
Can be done in two ways: (i) direct and (ii) standardization
Direct Method
o Carefully weighed quantity of a primary standard is dissolved in a suitable solvent and
diluted to an exactly known volume in a volumetric flask.
Standardization
o Titrant is used to titrate:
A weighed quantity of a primary standard;
OR a weighed quantity of a secondary standard
OR a measured volume of another standard solution
A titrant that is standardized against a secondary standard or against another standard solution is
sometimes referred to as a secondary standard solution.

MOD II: ANALYT. METH. & SEP. TECH.CAPE CHEMISTRY UNIT II

4.2.2

IF THERE IS A CHOICE, always choose primary standards over secondary standards! This is
because there are larger uncertainties associated with secondary standards.
MANY reagents lack the properties required for a primary standard, however, and therefore
require standardization!
Experimental: Direct Method

Make up 250 mL of 0.100 M Sodium Carbonate


Initial Calculation

c=n /V n=cV

n= 0.10

mol
250

L =0.025 mol
L
1000

)(

m=nM =0.025 105.978

g
=2.650 g
mol

Procedure

4.2.3

Half fill a 250 mL volumetric flask with distilled water;


After which, weight and dissolve 2.650 g of sodium carbonate into the flask;
Then, make up to mark by adding distilled water;
Stopper, and equilibrate;
Standardization

Consider NaOH5,6

Firstly, solid NaOH has the property of absorbing water from the air so it is not possible to
accurately weigh NaOH.
Secondly, a solution of NaOH tends to absorb atmospheric carbon dioxide, which is weakly
acidic. The reaction between the CO2 and NaOH partially neutralizes the NaOH solution
Therefore, it is unsuitable as a primary standard;
Consequently, another method for preparing a standard solution is needed. A possible choice
would be using oxalic acid dihydrate, H2C2O4

2 H2O

Procedure

2 NaOH ( aq ) + H 2 C 2 O4 2 H 2 O ( aq ) 4 H 2 O( aq)+ Na 2 C2 O4 ( aq)

Prepare a known concentration, ca, of a standard solution of oxalic acid dihydrate;

5 http://homepages.ius.edu/DSPURLOC/c121/week11.htm
6

MOD II: ANALYT. METH. & SEP. TECH.CAPE CHEMISTRY UNIT II

Titrate using phenolphthalein as indicator, a fixed volume, V b, of solution of NaOH against oxalic
acid;
The end point has been reached when the pale pink color of the phenolphthalein persists
for 30 seconds.
Volume of oxalic acid, Va = average titres;
Calculate the number of moles of oxalic acid, n = caVa;

Using the mole ratio between NaOH and Oxalic Acid,

Therefore, concn of NaOH, cb = (n of moles of NaOH)/(volume of N

The equation of NaOH +

n of NaOH = 2 n of Oxalic Acid

H 2 C 2 O 4 is given as follows:

Problem

4.3

Describe how you would standardize a solution of HCl using potassium hydrogen phthalate, KHP!
Practice Questions

Review:

Formula 1

n=

m
M

Where:

n = number of moles (mol);


m = mass of some chemical species (g);
M = molas mass of some chemical species (g/mol);

MOD II: ANALYT. METH. & SEP. TECH.CAPE CHEMISTRY UNIT II

Formula 2

c=

n
n=cV
V

Where:

c = concentration of some species (mol/L)


n = number of moles (mol);
V = volume of some chemical species (L)

Problem 1

Problem 2

Problem 3

5.1

Acid Base Titrations

An acid-base titration is the determination of the concentration of an acid or base by exactly neutralizing
the acid or base with an acid or base of known concentration. 7
Problem 1

Problem 2

7 http://en.wikipedia.org/wiki/Acid%E2%80%93base_titration

MOD II: ANALYT. METH. & SEP. TECH.CAPE CHEMISTRY UNIT II

Problem 4

MOD II: ANALYT. METH. & SEP. TECH.CAPE CHEMISTRY UNIT II

5.2

Back Titrations
It is sometimes necessary to add an excess of the standard titrant and then determine the excess
amount
The excess is determined using a second titrant
This is called a Back Titration
Example:
o
o

3
PO4 can be determined using an excess of standard silver nitrate solution

This leads to the formation of a insoluble silver phosphate:

3 A g3 P O4 ( s)
++ P O 4
3 A g
o

The excess silver nitrate is then back-titrated with a standard solution of potassium
thiocyanate, KSCN:

MOD II: ANALYT. METH. & SEP. TECH.CAPE CHEMISTRY UNIT II

AgSCN ( s )
+ +SC N
A g
o

Problem 1

Problem 2

Problem 3

Here, the amount of silver nitrate is chemical equivalent to the amount of phosphate ion +
the amount of thiocyanate used for the back-titration.

MOD II: ANALYT. METH. & SEP. TECH.CAPE CHEMISTRY UNIT II

Problem 4

Problem 5

5.3

Redox Titrations

Redox titration (also called oxidation-reduction titration) is a type of titration based on a redox
reaction between the analyte and titrant. 8
Problem 1

Problem 2

\
Problem 3

8 http://en.wikipedia.org/wiki/Redox_titration

MOD II: ANALYT. METH. & SEP. TECH.CAPE CHEMISTRY UNIT II

Problem 4

Problem 5

MOD II: ANALYT. METH. & SEP. TECH.CAPE CHEMISTRY UNIT II

5.4

Thermometric Titrations 9

Thermometric titration is one of a number of instrumental titration techniques where endpoints can be
located accurately and precisely without a subjective interpretation (such as qualitatively determining end
points using indicators) on the part of the analyst as to their location. 10
Enthalpy change is arguably the most fundamental and universal property of chemical reactions, so the
observation of temperature change is a natural choice in monitoring their progress. 11
Each chemical reaction is associated with a change in enthalpy that causes a temperature change which,
when plotted versus volume of titrant, can be used to monitor the course of the reaction and thus to detect
the titration endpoint. For a simple reaction this means that the increase (exothermic reaction) or
reduction (endothermic reaction) in temperature depends on the amount of substance converted.

9http://www.metrohm.com.au/Products/Titration/ThermometricTitration.html?
identifier=88595004&language=en&name=%3Cp%3EBrochure%3A+859+Titrotherm++Thermometric+titration%3A+the+ideal+complement+to+potentiometric+titration%3C%2Fp%3E
10 http://en.wikipedia.org/wiki/Thermometric_titration
11 Ibid.

MOD II: ANALYT. METH. & SEP. TECH.CAPE CHEMISTRY UNIT II

Figure 1 Graph for a Typical Thermometric Titration12


5.5

Potentiometric Titration

No indicator is required
Voltage is measured for a reaction against Volume of Titrant
End point is determined at the point of inflexion

12 http://en.wikipedia.org/wiki/File:Aaaathermo_fig2.jpg

MOD II: ANALYT. METH. & SEP. TECH.CAPE CHEMISTRY UNIT II

Figure 2 Apparatus for Potentiometric Titration13

Figure 3 A typical Potentiometric titration curve

14

13 Skoog, D., et al., (2004). Fundamentals of Analytical Chemistry 8th Edition. USA: Thomson Publishers
14

MOD II: ANALYT. METH. & SEP. TECH.CAPE CHEMISTRY UNIT II

MOD II: ANALYT. METH. & SEP. TECH.CAPE CHEMISTRY UNIT II

5.6

6
6.1

Conductometric Titrations

Uses
Vinegar 15

Acetic acid (CH3COOH) is the analyte and sodium hydroxide (NaOH) is the standard. The reaction is:
CH3COOH(aq) + NaOH(aq) --> CH3COONa(aq) + H2O(l)
In a titration procedure, 40.57 mL of 0.493 M NaOH solution was used. How many mols NaOH did this
volume of NaOH solution contain?
Buret reading = 0.76 mL
Determining the Volume of Titrant Delivered in a Titration
Final buret reading:
Initial buret reading:
Volume delivered:

15 http://web.lemoyne.edu/~giunta/chm151L/vinegar.html

49.37 mL
0.74 mL
48.63 mL

MOD II: ANALYT. METH. & SEP. TECH.CAPE CHEMISTRY UNIT II

6.2

Household Cleaners

6.3

Aspirin 16

Aspirin is an acid, and reacts with sodium hydroxide:

Figure 4 Aspirin (2-acetoxybenzoic acid)


Aspirin(aq) + NaOH(aq) Aspirin-(aq) + H2O(l) + Na+ (aq)
As such, 1 mole of aspirin will react with 1 mole of sodium hydroxide. This is an ACID-BASE reaction.
Problem 1

16
http://academics.smcvt.edu/chemistry/CHEM_103/CHEM_103/CHEM_103_Labs/Aspirin/Analyzing_Aspiri
n_by_titration_with_Standardized_NaOH.doc

MOD II: ANALYT. METH. & SEP. TECH.CAPE CHEMISTRY UNIT II

MOD II: ANALYT. METH. & SEP. TECH.CAPE CHEMISTRY UNIT II

MOD II: ANALYT. METH. & SEP. TECH.CAPE CHEMISTRY UNIT II

6.4

Vitamin C 17

Vitamin C (ascorbic acid) deficiency leads to scurvy, a disease characterized by weakness, small
hemorrhages throughout the body that cause gums and skin to bleed, and loosening of the teeth.
The minimum daily requirement is 30 mg, the recommended daily allowance is 60-70 mg.
The formula for ascorbic acid is C 6H8O6 and the structures for the reduced form and for the oxidized form
(dehydroascorbic acid) are shown below:

The amount of ascorbic acid can be determined by a redox titration with a standardized solution of iodine.
The iodine is reduced by the ascorbic acid to form iodide. As shown in the other half of this redox
equation.

The titration end point is reached when a slight excess of iodine is added to the ascorbic acid solution.
Thyodene is used to determine the endpoint, excess iodine reacts with the thyodene indicator and forms
a highly colored complex. Thyodene does not form this complex with iodide.
6.5

Antacids 18

17 http://wwwchem.csustan.edu/chem1112/1112vitc.htm
18 http://wwwchem.uwimona.edu.jm/lab_manuals/c10expt28.html