CHAPTER I

INRODUCTION

A. Objective

Students are able to:

1. Prepare primary and secondary solution for complexometry titration
2. Perform complexometry titration and observe the change at the end of titration
3. Calculate the total hardness, permanent hardness and temporary hardness in water.

B. Literature Review

B.1 Complexometry Explanation

Complexometry is based on the fact that certain organic compounds form stable complexes with
metal ions in solution[1]. Complexometry involves titrating metal ions with a complexing agent
or chelating agent (Ligand). In this method, a simple ion is transformed into a complex ion and
the equivalence point is determined by using metal indicators. This titration the use of EDTA
(Ethylene diamine tetra acetic acid) and other chilons. These chilons react with metal ions to
form a special type of complex known as chelate.

The molecules or ions which displace the solvent molecules are called Ligands. Ligands or
complexing agents or chelating agents can be any electron donating entity, which has the ability
to bind to the metal ion and produce a complex ion[2]. In the titration of Ca2+ with EDTA4- to
produce CaEDTA2-, all components are colorless so end point won’t be known when the

1
stoichiometric amount of EDTA have been added to the reaction. To recognize the end point,
indicator EBT must be added[3].

B.2 Types of Ligands[2]

1. Unidentate Ligands, ligands which are bound to metal ion only at one place are called
unidentate ligands (one toothed). NH3, for example.

2. Bidentate and Multidentate Ligands, many ligands are known that contain more than one
group, capable of binding with metal ions. It include bidentate ligands (2 donar atoms),
tridentate ligands (3 donar atoms), quadridentate ligands, etc. Thus, ethylene diamine is an
example of bidentate ligand. H2N-CH2-CH2-NH2

B.3 Chelate Compound or Chelate[2]

A chelate or a chelate compound is a complex of a metal ion with 2 or more groups on a

multidentate ligand. Ligands which have more than one electron donating groups are called
chelating agents. Amino and carboxylate ions are the most effective complexing agent in ligands.
The solubility of metal chelates in water are affected by the presence of hydrophilic groups such
as COOH, SO3H, NH2 and OH. When both acidic and basic groups are present, complex will

be soluble over a wide range of pH. The solubilities of both the chelating agent and the metal
chelate will be low, but it will be soluble in organic solvents in the absent of hydrophilic groups.

EDTA forms chelates with nearly all metal ions and this reaction is the basis for general
analytical method for these ions by titration with a standard EDTA solution[2].

2
B.4 Reagent EDTA[2]

Disodium salt of EDTA is a water soluble chelating agent and is always preferred. It is non-
hygroscopic and a very stable sequestering agent (Ligands which form water soluble chelates
are called sequestering agents). EDTA has the widest general application in analyses because
of the following important properties.

B.5 Factors influencing EDTA reactions[2]

1.Nature and stability of metal complexes of Ethylenediaminetetra-acetic acid

Ethylenediaminetetra-acetic acid forms complexes with complexes with most cations in a 1:1
ratio, irrespective of the valence of the ion:

2-
where M is a metal and [H2X] is the anion of the disodium salt (disodium EDTA) which is

most frequently used.

2.Effect of pH on complex formation

Ethylenediamine tetra-acetic acid ionizes in four stages and, since the actual complexing species
4-
is Y , complexes will form more efficiently and be more stable in basic solution. If, however,
the solubility product of the metal hydroxide is low, it may be precipitated if the hydroxyl ion
concentration is increased too much. On the other hand, at lower pH values when the
4-
concentration of Y is lower, the stability constant of the complexes will not be so high.
Complexes of most divalent metals are stable in ammonical solution. Although most complexes

3
are stable over a fair range of pH, solutions are usually buffered at a pH at which the complex
is stable and at which the colour change of the indicator is most distinct.

B.6 Important factors in determining the end point.[2]

1. The stability of complex formed: As the stability constant for complex formed is greater,
the larger the charge in free metal concentration (pM) at equivalent point and more clear would
be the end point.

2. The number of steps involved in complex formation: Fewer the number of steps required
in the formation of complex, greater would be the break in titration curve at equivalent point
and clear would be the end point.

3. Effect of pH: During a complexometric titration, the pH must be constant by using buffer
+
solution. Control of pH is important since the H ion plays an important role in chelation. Most
+ +
ligands are basic and bind to H ions throughout a wide range of pH. Some of these H ions are
frequently displaced from the ligands (chelating agents) by the metal during chelate formation.

+
Equation below shows complexation between metal ion and H ion for ligand:

Thus, stability of metal complex is pH dependent. Lower the pH of the solution, lesser would
+
be the stability of complex (because more H ions are available to compete with the metal ions
for ligand). Only metals that form very stable complexes can be titrated in acidic solution, and
metals forming weak complexes can only be effectively titrated in basic solution.

B.7 Mechanism of action of indicator[2]

Let the metal be denoted by M, indicator by I and chelate by EDTA. At the onset of the titration,
the reaction medium contains the metal-indicator complex (MI) and excess of metal ion. When
EDTA titrant is added to the system, a competitive reaction takes place between the free metal
ions and EDTA. Since the metal-indicator complex (MI) is weaker than the metal-EDTA chelate,
the EDTA which is being added during the course of the titration is chelating the free metal ions
in solution at the expense of the MI complex. Finally, at the end point, EDTA removes the last
4
traces of the metal from the indicator and the indicator changes from its complexed colour to its
metal free colour. The overall reaction is given by:

B.8 EBT Indicator and Buffer Salmiac[2]

Erio - T indicator or Eriochrome Black-T indicator is used in this titration. When it is chealted
or acidifies, it produces a pink-red solution. When it is not chelated and under basic conditions
it is blue. This color change from wine red to violet to blue is due tothe compact nature of the
complex. The statement "the compact nature of the complex" means when the indicator is added
to the hard water, the indicator Erio-T forms a complex with the Ca2+ ions that is pink in color.
As EDTA is added to the solution, the EDTA forms a complex with the Ca2+leaving the indicator
Erio-T uncomplexed, which is blue in color. Eriochrome has pH range between 6 and 7, and it
can be used to determine Ca, Ba, Mg, Zn, Cd, Mn, Pb, Hg . Before the titration started, buffer
salmiac was added. It was meant to control the pH at a certain pH according to the indicator.

B.9 Types of Water Hardness[4]

1. Temporary hardness is due to the bicarbonate ion, HCO3-, being present in the water. This
type of hardness can be removed by boiling the water to expel the CO2, as indicated by the
following equation:

2. Permanent hardness is due to the presence of the ions Ca2+, Mg+2, Fe3+ and SO4-. This
type of hardness cannot be eliminated by boiling. The water with this type of hardness is said to
be permanently hard

3.Total hardness is the sum of permanent hardness and temporary hardness.

5
 CHAPTER II

EXPERIMENTAL METHOD

A.Materials and Apparatus

A.I. Materials
1. ZnSO4
2. EDTA (Ethylene Diamine Tetra Acetate)
3. NH4Cl
4. NH4OH
5. EBT (Eriochrome Black T) indicator
6. NaCl
7. Filter Paper
8. Water Sample

A.2. Apparatus

1. Weighing Bottle
2. Beaker glass
3. Mixing rod
4. Funnel
5. Volumetric flask
6. Watch Glass
7. Measuring cup
8. Volumetric pipette
9. Erlenmeyer
10. Burette
11. Burette stand & clamp
12. Spray bottle

6
B.Solution Preparation

B.1.1. Standard solutions of ZnSO4 ± 0,01 M, 100 mL

Molecular Weight = 287,54 gr/mol

Volume 100 mL = 0,1 L

The formula equation Tolerance ± 10 %

𝑚𝑜𝑙𝑒
M= 0,28754 𝑥 10% = 0,028754 𝑔𝑟𝑎𝑚
𝑣𝑜𝑙𝑢𝑚𝑒

mol = M x Volume 0,028754 + 0,028754 = 0,3169294 gram

mole= 0,01 x 0,1 0,028754 – 0,028754 = 0,258786 gram

mole = 0,001 Mole

mass= mole x MW

mass=0,001 x 287,54

mass= 0,28754 gram

B.1.2. Preparing ZnSO4 ± 0,01 M solution :

1. ZnSO4 powder was weighed within the range of 0,2588-0,3169 gram using analytical
balance
2. ZnSO4 powder was dissolved with distilled water in beaker glass below 100 ml, the
solution was stirred until the dilute had completely dissolved.
3. The ZnSO4 solution was poured from the beaker glass into the volumetric flask 100 ml
using funnel.
4. The volumetric flask was shaken until its completely homogenous

B.2.1. Solution of EDTA ±0,01 M, 900 ml

Molecular weight = 372,24gr/mol

Volume = 900 mL = 0,9 L

The Formula equation :

7
 𝑚𝑜𝑙𝑒
M=𝑣𝑜𝑙𝑢𝑚𝑒

mol = M x Volume

mole= 0,01 x 0,9

mole = 0,009 Mole

mass= 0,009 x 372,24

mass=3,3501 gram

B.2.2. Preparing EDTA ±0,01 M solution:

1. EDTA powder was weighed around 3,3501 gram using hard balance
2. EDTA powder was dissolved with distilled water in beaker glass until 900 mL
3. The EDTA solution was poured into the burrete until 50 mL

B.3.1. Buffer Salmiac; 250 mL

250
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑁𝐻4𝐶𝑙 = 100 𝑥6,75

mass of NH4Cl= 16,875 gr

250
Volume of NH4OH=100 𝑥 57

Volume of NH4OH= 142,5 mL

B.3.2. Preparing of buffer salmiac solution

1. NH4Cl was weighed around 16,875 gr by using hard balance

2. 142,5 mL of NH4OH was taken by using measuring cylinder
3. NH4OH and NH4CL were mixed in beaker glass using distilled water until 250 mL

C. Experimental Procedure

C.1. Standardization of EDTA solution with standard solution of ZnSO4

8
1. 10 mL of ZnSO4 solution was taken with volumetric pipette and was moved into the
Erlenmeyer.
2. 30 mL of distilled water, 5 mL of buffer salmiac solution and a little amount of EBT powder
as the indicator were added.
3. ZnSO4 was titrated with EDTA solution until the color changed.
4. The volume of EDTA solution needed for the titration was noted.
5. The procedure was repeated once.

C.2. Determination of permanent hardness in water sample

1. 300 mL of water sample was taken and put into beaker glass
2. The water sample was heated until it boiled.
3. The water sample was cooled and moved into 250 mL of volumetric flask while it was filtered
by using filter paper and funnel.
4. 50 mL of the heated and cooled sample was taken by using burette and moved into the
Erlenmeyer.
5. 1 mL of buffer salmiac and a little amount of EBT indicator were added into the water sample
in the Erlenmeyer.
6. The sample was then titrated with EDTA solution
7. The volume of EDTA solution needed for the titration and the changes of color was noted.
8. The procedure was repeated once.

C.3. Determination of total hardness in water sample

1. 50 mL of water sample was taken by using burette and was moved into the Erlenmeyer
2. 1 mL of buffer salmiac and a little amount of EBT indicator were added into the water sample
in Erlenmeyer.
3. The sample solution was titrated with EDTA solution
4. The volume of EDTA solution needed for titrating the water sample and the changes of color
were noted.
5. The procedure was repeated once.

9
 CHAPTER III
RESULT AND DISCUSSION

A. Results
Experimental Result
A.1. Standardization of EDTA Solution with Standard Solution of ZnSO4
 Standard solution was prepared by weighing 0.2829 g of oxalic acid, the dissolved and
diluted with distilled water until 100 mL
Chemical formula of oxalic acid: ZnSO4
Molecular weight of oxalic acid: 287.54 gr/mol
 Titration Result
Indicator: EBT

Volume of ZnSO4 Volume of EDTA

Color Change
solution(mL) solution(mL)
10 13.6 Purple - blue
10 13.5 Purple - blue
Average = 10 13.55 Purple - blue

A.2. Determination of Total Hardness in Water

 Titration Result
Indicator: EBT

Volume of water Volume of EDTA

Color Change
sample(mL) solution(mL)
50 1.2 Purple - blue
50 1.0 Purple - blue
Average = 50 1.1 Purple - blue

A.3. Determination of Permanent Hardness in Water

 Titration Result
Indicator: EBT

10
 Volume of water Volume of EDTA
Color Change
sample(mL) solution(mL)
50 0.5 Purple - blue
50 0.3 Purple - blue
Average = 50 0.4 Purple - blue

B. Calculation
B.1. Concentration of EDTA solution
𝑚𝑜𝑙𝑒 𝑜𝑓 𝑍𝑛𝑆𝑂4
𝑀 𝑍𝑛𝑆𝑂4 =
𝑣𝑜𝑙𝑢𝑚𝑒
𝑀𝑎𝑠𝑠
( 𝑀𝑤 ) 𝑍𝑛𝑆𝑂4
𝑀 𝑍𝑛𝑆𝑂4 =
𝑣𝑜𝑙𝑢𝑚𝑒

0.2824
( ) 𝑚𝑜𝑙
𝑀 𝑍𝑛𝑆𝑂4 = 287.54
0.01 𝐿
𝑀 𝑍𝑛𝑆𝑂4 = 0.0098 𝑀

nEquivalent of ZnSO4 = nEquivalent of EDTA

(M x V) ZnSO4 = (M x V) EDTA
0.0098 x 0.01 = M EDTA x (13.55 x 10^-3)
M EDTA = 0.0072 M

B.2. Determination of Total Hardness of Water sample (ppm CaCO3)

nEquivalent of CaCO3 = nEquivalent of EDTA
(M x V) CaCO3 = (M x V) EDTA
M CaCO3 x 0.05 = 0.0072 x (1.1 x 10^-3)
M CaCO3 = 1.394 x 10^-4 M
Ppm CaCO3 = M CaCO3 x Mw CaCO3 x 1000
Ppm CaCO3 = 1.594 x 10^-4 x 100 x 1000
Ppm CaCO3 = 15.94 mg/L

11
 B.3. Determination of Permanent Hardness of Water sample (ppm CaCO3)
nEquivalent of CaCO3 = nEquivalent of EDTA
(M x V) CaCO3 = (M x V) EDTA
M CaCO3 x 0.05 = 0.0072 x (0.4 x 10^-3)
M CaCO3 = 5.798 x 10^-5 M
Ppm CaCO3 = M CaCO3 x Mw CaCO3 x 1000
Ppm CaCO3 = 5.798 x 10^-5 x 100 x 1000
Ppm CaCO3 = 5.798 mg/L

B.3. Determination of Temporary Hardness of Water sample (ppm CaCO3)

Temporary Hardness = Total Hardness - Permanent Hardness
= (15.94 - 5.798) mg/L
= 10.14 mg/L

C. Discussion
Titration of complexometry (chilometric titration)[2] involves metal ion and a
complexing agent (ligand) to form a complex compound (a chelate).[6] In the experiment,
complexometry principal is utilized in the standardization of EDTA solution and the
determination of water hardness.[2]
In standardization process, ZnSO4 was used as primary solution, which consists of ion
of Zn2+; the reason is that the it has reasonably large molar mass, high in purity, and stable.[9]
The metal ion (Zn2+) functions as lewis acid (electron acceptor) while EDTA, which is the
secondary standard, functions as lewis base (electron donator); both combines together to
form a complex ion. [6]
The basic requirement in such titrations is that the complex involved should be highly
soluble and stable. EDTA is a non- hygroscopic and a very stable sequestering agent to
solubilize metal ions.[8] It has a special structure of its anion which has 6 ligand atoms
(hexadentale ligand) that includes: two donor of nitrogen atoms and four donor oxygen
atoms; thus forming hybrid coordinate bonds with the metal ion Zn2+. The complex ion
formed is ZnEDTA2- which has a stern 5-membered ring. However, EDTA is a very
unselective reagent.
12
 Before the titration, buffer salmiac, an alkaline buffer consisting of NH4Cl and NH4OH,
was added into ZnSO4 solution.
Mn+ + H2Y2- → MY(n-4)+ 2H+
This addition is due to the reaction between metal ion and EDTA is reversible, so buffer
salmiac is used to shift reaction between EDTA and metal forward, to prevent the
reversibility of the reaction. It carries out the reaction in a basic buffer solution removes H+
as it is formed, which also yields the formation of the EDTA-metal cation complex reaction
product. Furthermore, as the effectiveness of the complexing agent (EDTA) is strongly
affected by pH, buffer salmiac functions to keep the pH at the optimum of 6 to 10 and to
prevent the formation of metal hydride precipitate. This condition also allows the indicator
EBT which (Eriochrome Black T) to indicate end point. [6]
The indicator used in the titration was EBT which has the pH range of 6-7 from red to
blue. EBT has the formula HIn2- with the color blue when it is dissociated. [7]
Zn2+ + HIn2- ↔ ZnIn- + H+
A red color will appear after the addition of EBT in ZnSO4 solution due to the bond with
Zn2+. When EDTA is titrated completely with Zn2+(end point), the solution will become blue
leaving the HIn2- as its original color. [7]
In the determination of water hardness, the steps of titration is almost the same, except
there is a procedure to boil the water sample in determining the permanent water hardness.
Based on the reaction: [10]
Ca(HCO3)2(aq) → CaCO3(s) + H2O(l) + CO2(g).
There is a precipitate of CaCO3 in which after cooling down will be decreased in solubility.
The procedure involving determination of total hardness follows the same principle as
complexometric titrtation with exception that the metal ion is a Ca2+ ion. The temporary
hardnes can be determined by substracting total hardness with permanent hardness obtained
from the titration. [10]

13
 CHAPTER IV

CONCLUSION AND SUGGESTION

A. Conclusion

The concentration of EDTA solution was 0.0072 M (after standardization). The water
sample has the of total hardness of 15.94mg/L whereas the permanent hardness was 5.798mg/L.
So, the temporary hardness is 10.14 mg/L

B. Suggestion
1. Remember to be precise at expelling the titrant to the sample. Any indirect contact
between two fluid will reduce the accuracy of the result.
2. After reaching the end point, please wait for a moment until the color stop changing.

14
 REFERENCES

1. Complexometric titration @ www.federica.unina.it. (n.d.). Retrieved from

http://www.federica.unina.it/agraria/analytical-chemistry/complexometric-titration/
2. Husain, A. (2014). Theoretical Basis of Analysis: Complexometric Titrations, (May).
3. EDTAeq @ genchem.rutgers.edu. (n.d.). Retrieved from
http://genchem.rutgers.edu/EDTAeq.html
4. Determination-of-Water-Hardness-by-Complexometric-Titration-Class-Notes @
www.scribd.com. (n.d.). Retrieved from
https://www.scribd.com/document/333769726/Determination-of-Water-Hardness-by-
Complexometric-Titration-Class-Notes
5. Masking, I. T. O., Spectrophotometry, I. T. O., To, I., & Inhibition, C. (n.d.).
CHAPTER 1 INTRODUCTION TO COMPLEXOMETRY,
SPECTROPHOTOMETRY AND CORROSION INHIBITION STUDIES.
6. Bellucci, G., Chiappe, C., Bianchini, R., Lenoir, D., Jl, R. H., & Doria, V. A. (1995).
Complex Formation, (10), 12001–12002.
7. Titration, C. (n.d.). Complexometric titration Reactions for Complexometric Titration.
Retrieved from
http://www.srmuniv.ac.in/sites/default/files/downloads/Complexometric_Titration.pdf
8. Harris, D. C. (2015). Quantitative chemical analysis, 9th ed. Analytical and
Bioanalytical Chemistry (Vol. 407). https://doi.org/10.1007/s00216-015-9059-6
9. Nahlé, Ayssar (2018). Chapter 13: Titrations in Analytical Chemistry. Lecture.
10. calcium @ www5.csudh.edu. (n.d.). Retrieved from
http://www5.csudh.edu/oliver/che230/labmanual/calcium.htm

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