DETERMINATION OF ALUMINIUM BY BACK TITRATION

Name: Eghan Kojo

Index N o : 6138811
Experiment N 0 : A 2.2.1
Graduate Assistant: Judith Odei
Date: 2 n d April, 2013

AIMS
1. To determine the quantity of aluminium present in a sample using back-titration.
2. To know how aluminium form complexes with ligands.
3. To determine the concentration of an unknown sample.

INTRODUCTION
Back titration is an analytical chemistry technique that allows the user to find the concentration of a
reactant of unknown concentration by reacting it with an excess volume of another reactant of known
concentration. The resulting mixture is then titrated back, taking into account the molarity of the excess that was
added.
Complexometric titration also known as chelatometry is a form of volumetric analysis in which the formation of
a colored complex is used to indicate the end point of a titration. Complexometric titrations are particularly
useful for the determination of a mixture of different metal ions in solution. An indicator capable of producing
an unambiguous color change is usually used to detect the end-point of the titration.
EDTA, ethylenediaminetetraacetic acid, has four carboxyl groups and two amine groups that can act as electron
pair donors, or Lewis bases. The ability of EDTA to potentially donate its six lone pairs of electrons for the
formation of coordinate covalent bonds to metal cations makes EDTA a hexadentate ligand. However, in
practice EDTA is usually only partially ionized, and thus forms fewer than six coordinate covalent bonds with
metal cations.
A ligand, such as ethylenediaminetetraacetic acid (EDTA) will react with a metal in a 1:1 ratio (the oxidation
state of the metal does not change the ratio) to form a hexadentate (six bonds between the ligand and the metal)
chelate. A pair of unshared electrons capable of complexing with a metal ion is contained on each of the two
nitrogens and each of the four carboxyl groups, thus forming six complexing groups. EDTA can be represented
by the symbol H4Y which means it is a tetraportic acid and the hydrogens in H4Y refers to the four ionizable
hydrogens. It is the unprotonated ligand Y4- that forms the complexes with the metal ions, that is the protons
are displaced by the metal ions upon complexation. Chelates are very stable and most are soluble. The
formation of chelates due to complexometry is used in the determination of many substances.

The structure of EDTA is drawn below

Disodium EDTA is commonly used to standardize aqueous solutions of transition metal cations. Disodium
EDTA (often written as Na2H2Y) only forms four coordinate covalent bonds to metal cations at pH values 12.
In this pH range, the amine groups remain protonated and thus unable to donate electrons to the formation of
coordinate covalent bonds. Note that the shorthand formNa4-xHxY can be used to represent any species of
EDTA, with x designating the number of acidic protons bonded to the EDTA molecule.
EDTA forms an octahedral complex with most 2+ metal cations, M2+, in aqueous solution. The main reason that
EDTA is used so extensively in the standardization of metal cation solutions is that the formation constant for
most metal cation-EDTA complexes is very high, meaning that the equilibrium for the reaction:
M2+ + H4Y MH2Y + 2H+
lies far to the right. Carrying out the reaction in a basic buffer solution removes H+ as it is formed, which also
favors the formation of the EDTA-metal cation complex reaction product. For most purposes it can be
considered that the formation of the metal cation-EDTA complex goes to completion, and this is chiefly why
EDTA is used in titrations / standardizations of this type.
Aluminium ranks third among the elements in order of abundance. The estimated abundance in percent in the
igneous rocks is 8.13. It is the most abundant of the metallic elements. The most common minerals are the
aluminosilicates, which include the feldspars, the micas etc. The metal was first prepared commercially about
1850 by the reduction of the chloride by sodium at high temperature. Shortly thereafter methods were
developed for the electrolysis of mixtures of molten aluminium, sodium fluorides, and chlorides. The metal is
extremely light, density 2.7, and possesses relatively high tensile strength. Its electrical conductivity is less than
copper, but weight for weight it is twice as good a conductor. It is easily malleable and may be rolled into thin
foil.
Aluminium has some analytical properties; aluminium ion is colorless, and has a slightly bitter astringent taste.
It forms an insoluble amphoteric hydroxide. Aluminium is generally determined in quantitative analysis by
precipitation as the hydroxide and weighing as the oxide.
To carry out metal cation titrations using EDTA, it is almost always necessary to use a complexometric indicator
to determine when the end point has been reached. Common indicators are organic dyes such as Fast Sulphon
Black, Eriochrome Black T, Eriochrome Red B, Patton Reeder, or Murexide. Color change shows that the
indicator has been displaced (usually by EDTA) from the metal cations in solution when the endpoint has been
reached. Thus, the free indicator (rather than the metal complex) serves as the endpoint indicator.
Direct determination of aluminum with EDTA is impossible - complexation reaction is too slow, making
titration impractical. However, there are not many simple methods of aluminum determination, and complex
stability constant for Al3+ is so high, that EDTA titration is tempting. Of several possible solutions back titration
proves to be the best approach. EDTA and aluminum are allowed to react in the hot solution for several minutes,
and then excess EDTA can be fast and easily titrated with Zn2+.

CHEMICALS
1.
2.
3.
4.
5.
6.

Unknown sample
Standard 0.01M Ethylenediamminetetraacetic acid( EDTA)
Standard 0.01M zinc sulphate solution
0.5% (wt/vol.) Eriochrome Black T
Dilute ammonia solution
Distilled water

APPARATUS
1.
2.
3.
4.

Heating plate
Funnel
50ml Burette
25ml pipette

PROCEDURE
1.
2.
3.
4.
5.

25ml of the unknown sample was measured into a beaker and 35ml of 0.01M EDTA added.
2ml of ammonia solution were added to adjust the pH between 7 and 8
The solution was allowed to boil on a heating plate and cooled to room temperature.
5 drops of Eriochrome Black T was added to the resultant solution. A blue black solution was formed.
The solution was immediately titrated against a solution of 0.01M zinc sulphate. The color changed from
blue black to purple.

TABLE OF RESULTS
Colour change: Blue black to purple
Indicator used: Eriochrome black T

Burette reading/ml
Final reading/ml
Initial reading/ml
Titre value/ml

1
29.00
0.00
29.00

Titre = 29.00ml
CALCULATIONS
The reaction that occurred between the zinc sulphate and the excess EDTA is

ZnSO4 + H2Y2ZnY2- + 2H+

from the reaction the mole ratio of EDTA and the ZnSO4 is 1:1
Mole of (ZnSO4) = C(ZnSO4) V(ZnSO4) = 0.01 29/1000ml= 2.910-4mol
hence moles of excess EDTA= 2.910-4mol
since the concentration of EDTA= concentration of ZnSO4
volume of excess EDTA= 29ml
thus volume of EDTA that reacted with the aluminium in the sample = (35- 29)
= 6ml
hence the amount of EDTA that reacted with Al in the sample = (6 0.01)/1000
= 6.010-5mol
therefore the concentration of Al in the sample = (6.010-51000)/25= 2.410-3M
mass concentration = CM = 2.410-3mol/dm3 26.982g/mol= 0.0647568g/dm3

DISCUSSION
In this experiment the concentration of aluminium in the sample was determined by back titration. In
this experiment a known excess of EDTA is added to the analyte, the excess EDTA is then titrated with a
standard solution of ZnSO4. The solution of aluminium and the excess EDTA was buffered with ammonia
solution to a pH of 7.30 to maintain the pH of the solution and boiled to ensure complete complexation of the
ion. The Al3+ (EDTA) complex is stable in solution at this pH. The solution is then cooled to room temperature
and Eriochrome black T indicator is added and back titrated with the standard zinc sulphate solution. The color
change that occurs at this pH was from purple to blue black and the mass concentration of aluminium in the
sample was 0.0647568g/dm3 and the concentration is 2.410-3M.
PRECAUTIONS
1. It was ensured that the burette reading was taken from the bottom of the meniscus.
2. The pH range at which the complex would form was determined and the solution adjusted and kept at
that pH range.
3. The buffered solution was heated to increase the buffer formation and the complex formation. This was
to ensure that the entire Al has been complexed and only excess EDTA existed in solution.

SOURCES OF ERROR
1. Too much of the indicator might have affected the result of the reading.

CONCLUSION
From the experiment and the result obtained the mass concentration of aluminium in the sample was
0.0647568g/dm3 and the concentration is 2.410-3M. Therefore it can conclude that the experiment was feasible.

REFERENCES
1. Vogel, A.I.; J. Mendham (2000). Vogel's textbook of quantitative chemical analysis (6 ed.). Prentice
Hall. p. 423
2. Harris, D.C. (2003). Quantitative Chemical Analysis (6 ed.). Macmillan. p. 129
3. Patnaik, P. (2004). Dean's Analytical Chemistry Handbook (2 ed.). McGraw-Hill Prof Med/Tech. pp.
2.112.16
4. Holler, F. James; Skoog, Douglas A.; West, Donald M. (1996). Fundamentals of analytical chemistry.
Philadelphia: Saunders College Pub.