Analysisi of Calcium Number in Calcium D Redoxon as Complexometry

1. Objectives
Determine the number of Calcium in Calcium D Redoxon as Complexometry
2. Basic Theories
Complexometric titrations have many applications, especially for determination of metal ions.
Ethylenediaminetetraacetic acid (EDTA) is the most widely used complexion agent for
routine analysis of water hardness and other applications. EDTA is a polydentate ligand that
is represented by the formula H4Y . Usually, EDTA titrations are conducted in alkaline
conditions under which EDTA will be present in different forms including H4Y, H3Y-, H2Y2-,
HY3-, and Y4- . Therefore, controlling the pH is one major factor that affects complexion.
The total concentration of EDTA will be the sum of all equilibrium species

CT = [H4Y] + [H3Y-] + [H2Y2-] + [HY3-] + [Y4-]

The fraction of any species can be found if desired where:
ao = [H4Y]/CT
a1 = [H3Y-]/CT
a2 = [H2Y2-]/CT
a3 = [HY3-]/CT
a4 = [Y4-]/CT

Now, assume a divalent metal reacts with EDTA, Y4-, the following equilibrium will be
observed in alkaline medium:

M2+ + Y4- = MY2-

[MY2-]
Kf = ___________
[M2+] [Y4-]

Y4- concentration is dependent on pH and , therefore, should be calculated as follows:

K1K2K3K4
a4 = __________________________________________________________
[H3O+]4+K1[H3O+]3+K1K2[H3O+]2+k1K2K3[H3O+]+K1K2K3K4
 [Y4-] = a4 CT

Titrimetric methods based on EDTA are simple and provide excellent results. Usually,
EDTA is the titrant except in case of a back titration. The sample containing the metal
ion to be determined is placed in a flask together with a suitable indicator. The
relationship
M1 V1 (EDTA) = M2 V2 (metal ion)
It can be used for calculation of the metal ion concentration.
It is a common practice to express the concentration of the metal ion in ppm units where
1 ppm = 1 mg
L
The number of mgs of the metal ion present in 1 L of the solution gives the ppm value.
Indicators for EDTA Titrations
Metal ion indicators form complexes with the metal ions
Mn+ + Inn- = M-In
When EDTA is added, the weak M-In complex is destroyed and the free In is released
giving color at the end piont.
Among the very important indicators that are routinely used, you will encounter two
indicators namely Muroxide and Eriochrome Black T (solochrome Black). However,
there are many other indicators some of them are very important because of their high
selectivity towards specific metal ions.

Preparation of an EDTA Standard Solution

Primary standards of EDTA can not be prepared. EDTA solutions should be standardized
against ZnSO4 or MgSO4 of very high purity. Water used in EDTA solution preparations
should be free from polyvalent metal ions and preferrably distilled through all Pyrex
glass. Calmagite is a suitable indicator. The titration is conducted at a buffered solution
at about pH 1O.

Sharpness of the End Point

The end point is affected by two major factors, the stability constant of the metal ion-
EDTA complex and the concentrations of the metal ion and EDTA. As the value of both
factors is increased, sharper end points are achieved. If either of the two factors has a low
value, end points of less sharpness result. For very low stability constants diffuse end
points are observed and large errors should be expected.

Masking and Demasking Agents

Some metal ions that interfere in EDTA titrations can be masked by addition of a suitable
masking agent. The titration is performed then, if desired, a demasking agent can be
added to free the previously masked metal ions so that they can be determined.

Usually, cadmium and zinc ions can be masked by the addition of cyanide. If desired, Cd
and Zn ions can be demasked by addition of chloral hydrate or a 3:1 formaldehyde :
acetic acid solution.

Back Titration Using EDTA

This is very important because, in some cases, there may not be a suitable indicator or the
MY2- complex is very weak. An excess of standard EDTA is added and the extra EDTA
is back titrated with standard Mg2+ using a suitable indicator like Arsenazo I.

Calculations Involved in EDTA Titrations

As mentioned previously, this type of calculation is very simple. For example:
In an experiment for the determination of Ca2+ in tap water, it was observed that 75.0 mL
of tap water required 15.0 mL of 0.05 M EDTA solution. Calculate the concentration of
Ca2+ expressed as ppm CaCO3 .

mg CaCO3 0.05 mol Y4- 15.0mL Y4- mol CaCO3

______ = _____________ X ______________ X __________
L 1000 mL Y4- 75.0 mL CaCO3 mol Y4-

100.0 g CaCO3 1000 mg CaCO3 1000 mL

X ____________ X _____________ X _______ = 1X103 ppm

mol CaCO3 g CaCO3 L

This is because Ca2+ forms a 1:1 complex with EDTA. In fact, EDTA forms a 1:1
complex with all known divalent metal ions unless otherwise indicated.
Calcium-D-Redoxon (CDR)
Calcium-D-Redoxon (CDR) is one of supplement that
contain calcium, Vitamin of C, D, B6, so, the bone of
adult was healthy and strong. It is also help to full
calcium need on the human body, help growth age,
healing age, recovery from bad nutrient condition, and
disruption of food absorption.
Every tablet of effervescent contain calcium about 250
mg, vitamin of C about 1000 mg, vitamin of D about 300
IU, and vitamin of B6 about 15 mg.

Calcium
Calcium is a chemical element with symbol Ca and atomic number 20. Calcium is a soft gray
alkaline earth metal, fifth-most-abundant element by mass in the Earth's crust. The ion Ca2+ is
also the fifth-most-abundant dissolved ion in seawater by both molarity and mass, after
sodium, chloride, magnesium, and sulfate.[3] Free calcium metal is too reactive to occur in
nature. Calcium is produced in the explosions at the end of the life of massive stars

Calcium is essential for living organisms, in particular in cell physiology, where movement
of the calcium ion into and out of the cytoplasm functions as a signal for many cellular
processes. As a major material used in mineralization of bone, teeth and shells, calcium is the
most abundant metal by mass in many animals.

3. Equipment and Materials

1. Equipments
- Buret and statif
- Volumetric pipette
- Beaker glass
- Erlenmeyer
- Volumetric flask
- Drop pipette
2. Materials
- Indicator Erio-T solution
 - EDTA Solution
- Buffer salmiac
- Aquades
- CDR (Calcium D Redoxon)
4. Work Procedure and Result
No Procedure Result
Make a Erio T indicator
1 About 0,2gram Erio T pellet are dissolved
in the 15 mL methanol amine and added
about 5 mL of absolute ethanol or about
0,4 gram of Erio T pellet are dissolve in
100 mL of ethanol
Make Salmiac buffer solution pH 10
1 About ……gram NH4Cl are dissolved in
……. mL concentrated ammonia (bj =
0,88 -0,90 kg/L). Next dilute the solution
into the volume …… mL with aquades.
Make EDTA solution 0,01 M
1 Powder or crystal of Na2H2Y is heated in
oven until the temperature is 80oC.
2 The powder is cooled in the desiccator
until the hydrate salt is formed with Mr =
372,25.
3 About 7,4458 gram this salt is measured
carefully and dissolved in 1 liter aquades.
Determine the number of calcium
1 About 1,002 gram sample CDR is dissolve in
100 mL aquades.
2 Dilute the solution about 100 times in 100 ml
aquades.
4 Insert 5 mL of the solution into three
Erlenmeyer after that add 0,1 mL Mg2+ into
the Erlenmeyer.
5 Add buffer salmiac, erio T indicator to the
 Erlenmeyer and titrate the sample by using
EDTA.
6 Do this titration in three trials
5. Data Collection
Determine the number of calcium in CDR
Trial Number of CDR solution Number of EDTA
1 10 mL 1,20 mL
2 10 mL 1,19 mL
3 10 mL 1,27 mL
Analysis:
- The Normality of EDTA
𝑚𝑎𝑠𝑠 𝐸𝐷𝑇𝐴 1000
𝑀 𝐸𝐷𝑇𝐴 = ∙
𝑀𝑟 𝐸𝐷𝑇𝐴 𝑚𝐿 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
7,4458 𝑔𝑟𝑎𝑚 1000
𝑀 𝐸𝐷𝑇𝐴 = ∙ = 0,2 𝑀𝑜𝑙𝑎𝑟
372,24 𝑔𝑟𝑎𝑚 /𝑚𝑜𝑙𝑒 100 𝑚𝐿
0,2 𝑀
𝑁 𝐸𝐷𝑇𝐴 = = 0,1 𝑁
2
Dilute to 0,05 N by dissolving 50 mL EDTA 0,1 N in 100 mL aquades.

- The Number of calcium in CDR

The average of volume EDTA used determine in the follows.
𝑉1 + 𝑉2 + 𝑉3
𝑉̅ =
3
1,20 𝑚𝐿 + 1,19 𝑚𝐿 + 1,27 𝑚𝐿
𝑉̅ = = 1,22 𝑚𝐿
3
The normality of CDR

𝑁𝐶𝑎2+ ∙ 𝑉𝐶𝑎2+ = 𝑁𝐸𝐷𝑇𝐴 ∙ 𝑉𝐸𝐷𝑇𝐴

𝑁𝐶𝑎2+ ∙ 10 𝑚𝐿 = 0,05 𝑁 ∙ 1,22 𝑚𝐿
0,061 𝑁 ∙ 𝑚𝐿
𝑁𝐶𝑎2+ = = 0,0061 𝑁
10 𝑚𝐿
Molarity of Ca2+
𝑀 = 2 𝑥 𝑁 = 2 𝑥 0,0061 𝑁 = 0,0122 𝑀
Dilute in 20 mL CDR in 100 mL aquades

M1 x V1 = M2 x V2
M1 x 20 mL = 0,0122 M x 100 mL
 M1 = 0,061 Molar
Mass Ca in CDR
𝑀 𝐶𝑎 ∙ 𝑀𝑟 𝐶𝑎 ∙ 𝑚𝑙 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑚𝑎𝑠𝑠 𝐶𝑎 =
1000
𝑔
0,061 𝑀𝑜𝑙𝑎𝑟 ∙ 40 ∙ 100 𝑚𝐿
𝑚𝑎𝑠𝑠 𝐶𝑎 = 𝑚𝑜𝑙𝑒 = 0,244 𝑔𝑟𝑎𝑚 = 244 𝑚𝑔
1000
The mass of Ca in CDR is 250 mg, so only 6 mg of calcium is lose in titration process.
Or the percentage of calcium in CDR is as follows:
𝑚𝑎𝑠𝑠 𝐶𝑎
% 𝐶𝑎 = 𝑥 100%
𝑚𝑎𝑠𝑠 𝑠𝑎𝑚𝑝𝑙𝑒
244 𝑚𝑔
% 𝐶𝑎 = 𝑥 100% = 24,35%
1002 𝑚𝑔
6. Discussion

7. Conclusion
Based on the data analysis and discussion, the number of calcium in calcium D redoxon is
244 mg or about 24,35 %. The number of calcium lose in experiment are 6 mg.

8. References