Experiment 5

Title: Complexometric Titration of Zn (II) with EDTA

Name: Chong Zheng Yee ( P1 )

ID No.: 1404800
Subject: UDEC 1224 CHEMISTRY LABORATORY II
Name of Partner: Tan Herh Lim, Sia Ting Wai
Date: 13 JULY 2015
Lecturer: Dr. Ooi Mei Lee

Objective :
To determine the unknown concentration of the Zn (II) solution by titrating it with EDTA.

Introduction:
Titration, also known as titrimetry is a basic and important laboratory method of
quantitative chemical analysis skill in chemistry. It is a technique where a solution of known
concentration is used to determine the concentration of an unknown solution
(chemed.chem.purdue.edu, 2015). The basic apparatus needed in titration are burette and conical
flask. There are few types of titrations which are acid-base titration, precipitation titration,
complexometric titration and redox titration. This experiment is an application of
complexometric titration, involving a metal-ligand complexation reaction. In this experiment,
EDTA (titrant) is used to determine the unknown concentration of zinc solution (analyte).
EDTA, also known as ethylenediaminetetraacetic acid, is an aminopolycarboxylic acid
(https://en.wikipedia.org, 2015). Metal ions such as Zn2+ may form many complexes in solution,
such as Zn(NH3)42+. Such complexation reactions is the basic concept of complexometric
titration. It can be used to find out an unknown concentration of particular ions in a solution.
However, as several complexing molecules must be added one at a time, the equivalence point
became difficult to be determined. Thus, scientist solved this problem by adding a strong
chelating ligand to bind with a molecule. This would ensure that the reaction takes place in a
single step only. For instance, ethylenediaminetetraacetic acid, EDTA is such a ligand. It is also a
hexadentate chelating agent, which can form maximum of 6 bonds to Zn2+ ions. Hence, it is far
more stable compare to monodentate ligand when forming a metal complex with Zn2+ ions. Thus,
EDTA is the most widely used chelating agent in complexometric titration due to this special
property.

The chemical structure of EDTA (left) and metal-EDTA chelate (right) :

Retrieved from : https://en.wikipedia.org/wiki/Ethylenediaminetetraacetic_acid

The reaction between the EDTA ( Y4- ) and the metal ion is a reversible reaction which
the equation is shown below:
M+n + Y4-

MYn-4

Kf = (MYn-4) / (M+n)( Y4-)

The reaction usually switch to right due to have large equilibrium formational constant,
Kf which in the range of 108-1025 (http://chemwiki.ucdavis.edu, 2015). The equilibrium constant
varies with the types of metal used in the reactions and some other conditions.
As a result, EDTA will react with metal ions in 1:1 mol ratio. After knowing the molarity
and volume of EDTA needed to titrate with the zinc solution, the molarity of Zn2+ can be
determined. Since
number of mole of EDTA = number of mole of Zn2+

nEDTA = nzn2+
MEDTAVEDTA = MZn2+VZn2+

Molarity=

moles of solute
volume of solution

Moles= ( Molarity ) (Volum e)

EDTA is a weak acid. The fuly protonated form of EDTA, H6Y2+ is a hexaprotic weak
acid with successive pKa values of :

pKa1 = 0.0, pKa2 = 1.5,

pKa3 = 2.0, pKa4 = 2.68, pKa5

= 6.11, pKa6 = 10.17

Retrived from :
http://chemwiki.ucdavis.edu/Analytical_Chemistry/Quantitative_Analysis/Titration/Complexatio
n_Titration
This indicates that EDTA can be exists as various species by manipulating the pH values.
However, the Y4- or (OOCCH2)2NCH2CH2N(CH2COO)2 is the ligand species needed in this
experiment because both two N atoms and four of the O atoms of Y4- can form bonds with the
metal ions. Thus, ammonium chloride buffer solution is added to manipulate the pH value to 10,
and Y4- species will predominate.

Retrieved from : http://www.chem.purdue.edu/gchelp/cchem/polys.html

In this experiment, the dark blue colour eriochrome black T is used as an indicator. When
the indicator is added to Zn2+ ion or Ca2+ion, it will form complex metal with them and produces
a pink colour solution. After that, EDTA will be added to the solution. Since EDTA will form a
more stable metal complex with the metals ions, it will bind to the metal ions and displaces out
the eriochrome black T to form new metal complex which gives back the blue colour of
indicator. Thus, the end point of titration is achieved when all the pink colour changes to sky blue
colour. The reaction is shown below (where In = indicator) :
MIn- + Y4pink

HIn2- + MY2blue

Chemicals :
0.01 M EDTA, ammonium chloride buffer stock solution (pH 10), calcium standard solution,
eriochrome black T indicator, zinc unknown sample, deionized water
Apparatus :
50 mL burette, white tile, beaker, pipette 25.0 mL, 250 mL Erlenmeyer flask, measuring cylinder,
250 mL volumetric flask
Procedure:
Standardization of the EDTA Solution
1. 25.00-mL aliquots of 0.003M Ca2+ solution was pipetted into each of three 250-mL
Erlenmeyer flasks.
2. 7-8 mL of pH 10 buffer, 15 mL of deionized water, and 3 drops of Eriochrome Black T
indicator were added, immediately prior to titrating a sample.
3. The solution was titrated immediately with EDTA against a white background until the light
pink solution turned to a light sky blue. The final volume was read at least twice.
4. Near the endpoint, the sides of the flask and the burette tip was periodically squirted and the
flask was swirled to ensure all the titrant had gotten into the solution in the flask.
5. The molarity of the EDTA solution was calculated from the volume of EDTA used in the
titration of each aliquot.
Analysis of the Zinc Unknown
1. 25.00-mL Zinc unknown solution was pipetted into each of three 250-mL erlenmeyer flasks.
15 mL of deionized water, 9-10 mL of pH 10 buffer, and 3 drops of Eriochrome Black T were
added immediately prior to titrating a sample.

2. The solution was titrated with standardized EDTA until the pink solution turned light blue.
3. The concentration of Zinc solution was calculated.

Results :
(a) Standardization of EDTA
Titration Number
Initial volume of burette (cm3)
Final volume of burette (cm3)
Total volume of EDTA used

1
2.50
11.20
8.70

2
11.20
20.40
9.20

(cm3)

Average volume of EDTA used =

8.70+9.20+8.90
3

= 8.93 cm3

Standard deviation =

( 8.708.93 ) + ( 9.208.93 ) + ( 8.908.93 )

3

= 0.2055
Calculating molarity of EDTA :
Number of mole of EDTA = Number of mole of Ca2+

nEDTA = nCa2+
MEDTAVEDTA = MCa2+VCa2+
MEDTA 8.93 mL= 0.003 M 25.00 mL
MEDTA = 0.008399 M
Molarity of standardized EDTA is 0.008399 M.

3
20.50
29.40
8.90

(b) Titration of unknown molarity of zinc solution with EDTA

Titration Number
Initial volume of burette (cm3)
Final volume of burette (cm3)
Total volume of EDTA used

1
0.90
25.60
24.70

2
1.20
26.10
24.90

(cm3)

Average volume of EDTA used =

24.70+ 24.90
2

= 24.80 cm3

Standard deviation =

= 0.141

Calculating molarity of unknown zinc solution :

Number of mole of EDTA = Number of mole of Zn2+

nEDTA = nZn2+
MEDTAVEDTA = MZn2+VZn2+
0.008399 M 24.80 mL = MZn2+ 25 mL
MZn2+ = 0.00833 M
Molarity of zinc solution is 0.00833 M.

Discussion :

( 24.7024.80 ) + ( 24.9024.80 )
21

3
3.60
29.10
25.5

Normally, solid dihydrate Na2H2Y. 2H2O is used to prepare EDTA solution. Under normal
atmospheric condition, the EDTA solution will contain 0.3 % moisture in excess of
stoichiometric water of hydration. This is because the mass of the Na2H2Y. 2H2O crystals
measured might contain excess water of hydration. Hence, standardization of EDTA solution
with Ca2+ solution was carried out to determine the exact molarity of EDTA solution. The
molarity of EDTA identified in the standardization process would be used to calculate the
unknown molarity of the zinc solution (Skoog. D, 2014).
Next, sometimes when eriochrome black T indicator is added into the solution, a light
purple colour solution is formed instead of light pink solution. This is because the amount of
indicator added was different in each conical flask. It was observed that a single drop of indicator
is just enough to give a light pink colour. When about 3 drops of indicator were added to the
conical flask, it will form purple colour because the light pink solution will mix with the excess
blue Eriochrome Black T indicator to form a purple solution. If a purple colour solution is used
to carry out the complexometric titration, a dark blue colour solution would be observed at the
end point instead of light sky blue colour. Thus, the detection of end point would become much
more difficult if excess of eriochrome black T indicator was added.
In addition, eriochrome black T indicator would reacts immediately with the Zn2+ ions to
form complex Zn-eriochrome black T, which gives a pink colour to the solution (Jean-Louis
Burgot. 2012). The reaction is as below ( where In = eriochrome black T indicator) :
Zn2+ + In ZnIn
Moreover, ammonium chloride buffer stock solution was added to the mixture in conical
flask to provide a pH value of 10. By doing so, more Y4- species would be yield. In turns, the Y4will take place in the complexometric titration later. Furthermore, another uses of buffer is to
resist any pH changes because it is crucial to maintain the pH value at 10 throughout the titration
process ( Clark. J, 2013). At such, the buffer solution works by removing H+ ions when they are
formed. The changes of the amount of Y4- with respective to the pH value is shown below :

Fraction of EDTA species as a function of pH

Retrived from : http://www.escritoscientificos.es/trab21a40/durezagua/pagina05.htm

When Y4- species is present in the conical flask, it immediately formed metal complex
with Zn2+ and displaces out eriochrome black T indicator. This is because the hexadentate Y4species of EDTA would have produces a stronger chelate effect with the Zn2+ ions. Thus, the new
metal complex formed is much more stable. As a result, the solution turns from pink colour to
sky blue colour. The reaction can be summarized as follows :
MIn- + Y4pink

HIn2- + MY2blue

In this experiment, deionised water is used instead of distilled water. This is because
deionised water does not contain any ions. It is important because distilled water may contains
others ions may bind to Zn2+ ions or EDTA, affecting the accuracy of the result. Thus, this
problem can be reduced with the usage of deionised water.
In this experiment, the average volume of EDTA used in the standardization is 8.93 mL.
The molarity of the EDTA determined is 0.008399 M with standard deviation of 0.2055. The
result is has a large standard deviation and it is not precise enough. This is because the
standardization is conduct by different person. Next, the sky blue colour is difficult to be
detected as the amount of indicator added is different.
On the other hand, for the titration of the zinc unknown sample, the average volume of
EDTA used is 24.80 mL. The molarity of Zn (II) ions determined by the titration is 0.00833 M

with standard deviation of 0.141. When calculating the average volume and the standard
deviation, only two reading is consider which is 24.70 and 24.90 mL and another reading which
is 25.5 mL is elimated as it is a outlier. The error may be due to the difficulty in determining the
sky blue colour as excess indicator has been added.
There are some precaution steps that had been taken in this experiment. First of all,
EDTA solution must be prepared one day earlier before the experiment to ensure all the EDTA
solid is completely dissolved. Secondly, the burette was filled up with tap water first before
conducting experiment to detect presence of any leakage. Thirdly, the burette must be rinsed with
EDTA solution first before the titration to improve the accuracy of the result. Moreover, the
burette must not be clamped at a slanting way, instead it should be clamped vertically upward to
avoid parallax error. Furthermore, we should swirl the conical flask continuously during the
titration process to ensure the rate of reaction fast enough. Apart from that, we should not blow
through the nozzle of burette to expel the last drop of solution from it. Instead, deionized water
should be used to rinse the nozzle of the burette to expel the last drop of EDTA solution. Besides
that, deionized water can also be used to wash down the tiny droplets of sodium hydroxide into
the solution of the conical flask. Gloves should be wore during the experiment to prevent
injuries.

Conclusion :
(a) The molarity of the EDTA determined by the standardization with Ca2+ solution is
0.008399 M with standard deviation of 0.2055. The result was has low precision.
(b) The molarity of Zn (II) ions determined by the complexometric titration with EDTA is
0.00833 M with standard deviation which is 0.141. The result was quite precise.

References :

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at:http://chemed.chem.purdue.edu/genchem/lab/techniques/titration/what.html. [Accessed
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