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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.
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
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)
+
+ H 3 O
+ H 2 O I n
(base colour)
2.2
Redox
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
Indicator
+1.33 V
colorless
yellow
+1.25 V
cyan
red
N-Phenylanthranilic acid
+1.08 V
violet-red
colorless
+1.06 V
cyan
red
N-Ethoxychrysoidine
+1.00 V
red
yellow
+0.97 V
cyan
red
+0.97 V
yellow-green
red
o-Dianisidine
+0.85 V
red
colorless
+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
E0, V
Color of
Color of
Sodium 2,6-Dibromophenol-indophenol
or Sodium 2,6-Dichlorophenol-indophenol
+0.64 V
+0.22 V
blue
colorless
+0.62 V
+0.19 V
blue
colorless
+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
Indigotrisulfonic acid
+0.33 V
-0.08 V
blue
colorless
+0.29 V
-0.13 V
blue
colorless
+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
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;
Property
High purity
Atmospheric Stability
Reason
Impurities may interfere with the reaction
4 http://en.wikipedia.org/wiki/Complexometric_indicator
Modest cost
Reasonable solubility in the titration
medium
Notes:
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
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.
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
c=n /V n=cV
n= 0.10
mol
250
L =0.025 mol
L
1000
)(
g
=2.650 g
mol
Procedure
4.2.3
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
5 http://homepages.ius.edu/DSPURLOC/c121/week11.htm
6
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;
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:
Formula 2
c=
n
n=cV
V
Where:
Problem 1
Problem 2
Problem 3
5.1
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
Problem 4
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
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:
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.
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
Problem 4
Problem 5
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.
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
14
13 Skoog, D., et al., (2004). Fundamentals of Analytical Chemistry 8th Edition. USA: Thomson Publishers
14
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
6.2
Household Cleaners
6.3
Aspirin 16
16
http://academics.smcvt.edu/chemistry/CHEM_103/CHEM_103/CHEM_103_Labs/Aspirin/Analyzing_Aspiri
n_by_titration_with_Standardized_NaOH.doc
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