COMPLEXOMETRIC CALCIUM TITRATION OF CALCIUM

SUSB-017 A Test Exercise 105 points

Last Update: 2/11/2013 2:41 PM

is the 5th most abundant element on Earth comprising 3.6% of the crust Its compounds are found virtually everywhere, in the form of minerals (like calcite and gypsum) and in the remains of living organisms (seashells, bones, etc.) The element itself itself, however however, was not isolated and identified until 1807, when Humphrey Davy isolated it by electrolysis of its molten chloride.

TECHNIQUE
Formation of Ca+2 complex with EDTA
Metal ions (Lewis acids) react with electron pair donors (Lewis bases) to form coordination compounds or complexes. A chelate is p produced when a metal ion coordinates with two or more donor groups from a single ligand . EDTA has six sites which can donate an electron pair to Ca2+ .
EDTADTA)

H C C H

H H

H2N H
HO C H2C CH2 N H H

NH2 C C
H3C C

Ethylene

Ethylene Diamine

H
OH

Acetic Acid

OH

O C

CH2 N C C CH2 Na OH C H H O
4

NaHO C

O
3

Na2H2EDTA di-sodium salt Ethylene Diamine Tetra-acetic Acid

EFFECT OF pH
Na2H2EDTA dissolves in neutral solutions to give
The first four pKa s of EDTA are: 0.0, 1.5, 2.0, 2.7.

THE pH = 10 BUFFER A pH = 10 buffer can be made from an NH4+ salt and NH3(aq) NH4+ (aq) + H2O H3O+(aq) + NH3(aq) Ka = pKa = 9.25
pK = - log K

Na+ +

H2EDTA

2-

anions

However, the most effective complexing form is

To neutralize last two H+s, HO O O OH we will maintain a moderately C C basic environment for the CH2 H2 C titration by adding a pH = 10 buffer N CH2 N CH2 HO C OH C C C Where are the six electron H H donor sites? H O H O 5

4-

a a [ H3O+] [NH3 (aq)] -------------------- = 10-9.25 = 5.6 X 10-10 [NH4+]

pH = 10 means [ H3O+] = 1.0 X 10-10 [ 1.0 X 10-10 ] [NH3 (aq)] / [NH4+] = 5.6 X 10-10 [NH3 (aq)] / [NH4+] = 5.6 So, a solution which is 1.0 M in NH4Cl and 5.6 M in NH3(aq) will be such a buffer. 6

Not surprisingly: Solutions of aqueous ammona (NH3(aq)) smell like ammonia.

Complex between EDTA and Ca+2 is 1 : 1 i.e., 1 EDTA4reacts with 1 Ca+2

O O O O Ca O

N N

When you dispose of solutions after f titration, please l do d so into the drains

Ca+2 +

EDTA

4-

O EQUIVALENCE (END) POINT = when all Ca+2 has reacted with EDTA
But, neither EDTA4-, nor Ca+2 nor its COMPLEX with Ca+2 IS COLORED How will we know when EQUIVALENCE (End) POINT has been reached?

Ca(EDTA)2- O

in the hoods

Not in the sinks.

USE INDICATOR ERIOCHROME BLACK T (EBT) - a BLUE dye - to detect Ca+2 EBT also forms a 1 : 1 complex with Ca+2 The EBT complex with Ca+2 is RED, but,

EDTA

Ca-EBT complex is MUCH LESS STABLE than Ca-EDTA complex

Therefore, in presence of EBT, the Ca-EBT complex can only exist when there is free Ca+2. If all Ca+2 is tied up as the EDTA complex, the Ca-EBT complex cannot form. Free EBT is BLUE. >> I.e., if given the opportunity to choose, a Ca+2 ion will complex with EDTA rather than with EBT. 9
2CaEDTA CaEBT2+ Buffer EBT

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Begin Titration: Lots of Free Ca+2

End Point: All Ca+2 tied up as EDTA Complex

WHATS IN THE SOLUTION WHEN Suppose we start with 2.00 mmol of Ca+2 to which we add 5 mg (~ 0.01 mmol) of EBT. Ca 2+ + EBT CaEBT
0.01 -0.01 0.00 mmol +0.01 mmol

ADD EDTA UNTIL

Initial 2.00 Change -0.01 Final

Ca+2-EBT Complex (Red)

Just before end point

Free EBT (Blue)

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1.99 0 0.01 mmol 2.00* 2.00 2.01 Before we have added any EDTA, 0.00 0.00 0.00 0.00 0.01 0.01 there is only CaEBT present in 0.00 0.01 solution. Therefore the solution is * EQUIVALENCE POINT red. Titration is conducted inEDTA moderately How many mmol of are basic solution, pH = 10 to enhance formation required to reach the endpoint?of EDTA 12 4 ion

Before the titration we have 1.99 mmol of Ca 2+ , 0.00 mmol free EBT and 0.01 mmol CaEBT. When we add 1.99 mmol of EDTA
Initial 1.99 Change -1.99 Final 0

When we add 2.00 mmol of EDTA, Ca2+ + EDTA CaEDTA

Initial 1.99 Change -1.99 Final 0.00 2.00 -1.99 0.01

Ca2+

+ EDTA

0.00

1.99 -1.99 0

CaEDTA

2-

0.01

0.00 mmol +1.99 mmol 1.99 mmol*

0 mmol + 1.99 mmol 1.99 mmol

2.01

Titration is conducted in moderately basic solution, pH = 10 to enhance formation of EDTAJust before the end point! 4 ion
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* CaEBT EQUIVALENCE POINT There still is 0.01 mmol of in the solution color is still red!

There is no more free Ca2+ but there is some available in the CaEBT complex. complex Since EDTA forms a stronger complex with Ca 2+ than EBT: 2.00 CaEBT + EDTA CaEDTA + EBT
Initial 0.01 Change -0.01 Final 0.00 0.01 -0.01 0.00 1.99 +0.01 2.00 0 mmol +0.01 mmol 0.01 mmol -0.0

END POINT

14 With free EBT present in the solution, the solution is blue

PROCEDURE When we add 2.01 mmol of EDTA, Ca2+ + EDTA CaEDTA

Initial 1.99 Change -1.99 Final 0.00 2.01 -1.99 0.02

0 mmol +1.99 mmol 1.99 mmol

There is no more free Ca2+ but there is some available in the CaEBT complex. Since EDTA forms 2.00 a stronger complex with Ca 2+ than EBT: CaEBT + EDTA CaEDTA + EBT
Initial 0.01 Change -0.01 Final 0.00 0.02 -0.01 0.01 1.99 +0.01 2.00 0.00 mmol +0.01 mmol 0.01 mmol -0.0

[0. PREPARE SAMPLE (if necessary) 1. WEIGH SAMPLE accurately, by difference 2. DISSOLVE in acid ( 5 mL 6M HCl ) 3. ADJUST pH (to insure basic solution) 25 mL water + 10 mL pH 10 buffer 4. ADD INDICATOR (EBT) spatulaful RED Color 5. TITRATE with EDTA to BLUE end point Hold up to light No trace of RED 6. REPEAT PROCEDURE Once more with pill Trial run + 2 or more times with unknown

The order of addition of reagents is critical. The sample must be completely dissolved by HCl before the ammonia buffer is added.

Just after the end point!

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Concentration of EDTA is ~0.050 M Ca+2 - EDTA complex is 1 to 1

HOW MUCH OF A TABLET SHOULD YOU WEIGH?

The contents of antacid pills and calcium supplements are often given as the weight of CaCO3, not Ca. In order to use less than a buret-full ( 50 mL ) of EDTA, you must weigh out a sample which contains

LESS THAN

Moles of Ca2+ = moles of EDTA at the equivalence point 50 mL L of f th the EDTA solution s l ti contains t i s 50 mL X ~0.050 mmol/mL = ~2.5 mmol of EDTA X (1mmol Ca2+/1mmol EDTA) = 2.5 mmol Ca2+. Since every 1 mol of CaCO3 contains 1 mol of Ca2+ x(1mmol CaCO3/1mmol Ca2+) = 2.5 mmol CaCO3 x 100. mg/mmol = 250 mg CaCO3
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2.5 mmol = 250 mg of Calcium carbonate A tablet or sample that contains 500 mg of CaCO3 would require us to use less than half of the tablet. But, we will actually want to use ~25 mL of EDTA

Whats the magic in 25 mL?

Remember: Delivering 20 25 mL of titrant from a buret optimizes its precision!

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Suppose a tablet contains 500 mg of CaCO3 ( 200 mg Ca ) and the tablet weighs 1.30 g To use ~25 mL of 0.050 M EDTA, we need to have 25 mL x 0.050 mmol/mL =~1.25 mmol Ca+2 or ~ 1.25 mmol CaCO3 x 100 mg/mmol = 125 mg CaCO3 What fraction of the tablet do we need?= 125 mg CaCO3 x ( 1 tablet/ 500 mg CaCO3) = about of the tablet which will weigh: The tablet is 1/4 x 1.30 = .325 = ~325 mg
NOT pure CaCO3

Having established that we need about of a pill, how do we proceed?

Pills are rarely homogeneous (i.e., of uniform composition throughout). They may have special coatings which prevent them from beginning to dissolve in the mouth, or often, more complex outer coatings. Soooooooo, In assaying pills (or other inhomogeneous materials), one must take samples from the entire material. In this case, that means grinding an entire pill to a uniform composition and taking 1/4 of the result rather than trying to break the pill into the required sample size and then grinding that.

You must repeat this calculation with the actual data on the container in the laboratory. 19

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ITS NEVER TOO LATE BURETS - SOME DOS AND DONTS DONT set buret to initial value of 0.00 Burets are made to be READ, not SET. DO let initial reading be arbitrary DO read and record buret to nearest 0.02 0 02 ml (i.e., to 2 decimal places) always! DO rinse buret ( including tip ) with the reagent that will be delivered DO make sure there are no bubbles in the tip

Since the unknowns have a wide range of percent CaCO3, the q to use 25 mL amount required of EDTA will range similarly. So, we do a preliminary run

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From SUSB-017 Data Sheet - 1 Concentration of EDTA solution: 0.04653 M container Init. Mass of vial + sample 14.5432 g Mass of vial + sample left over 14.4112 g Mass of sample to be titrated 0.1320 g Final buret reading 25.67 mL Weight mL is OK Initial buret reading 3.54
Net volume EDTA solution 22.13 mL mmol EDTA (0.04653 mmol/mL X 22.13 mL) 1.030 mmol Ca2+ in weighed sample 1.030 1.030 mmol CaCO3 in weighed sample Mass of CaCO3 in weighed sample 1.030 mmol X 100.1 mg/mmol 0.1031 g 78.08 % Mass percent CaCO3 100(0.1031g / 0.1320g)

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SUSB-017 Data Sheet - 2 Weight of tablet (g) 0.7710 Init. mass of container + sample (g) 14.5432 Mass of container + sample left over (g) 14.4112 Mass of sample to be titrated (g) 0.1320 Final buret reading (mL) 25.67 Initial buret reading (mL) 3.54 Net volume EDTA solution (mL) 22 13 22.13 mmol EDTA (0.04653 mmol/ml)(22.13 mL) 1.030 1.030 mmol Ca2+ in weighed sample 1.030 mmol CaCO3 in weighed sample Mass of CaCO3 in weighed sample (g) 1.030 mmol x100. mg/mmol = 0.1031 Mass percent of CaCO3 (0.1031g/ 0.1320g ) X 100 = 78.11 %

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REVIEW:

3 Results: 5.38, 5.50, 5.41 = 5.43

NEXT WEEK Kinetics of a Bleaching Reaction SUSB - 023 Do pre-lab Check out supplemental information related to this hi exercise i on the h WEB

AVERAGE: M1 + M2 + M3 = 5.38 + 5.50 + 5.41 3 3 AVERAGE DEVIATION: |M1 AVG| + |M2 AVG| + |M3 AVG| 3

(|5.38 - 5.43| + | 5.50 - 5.43| + |5.41- 5.43|) = 0.047 3 PERCENT DEVIATION: 100 X AVG DEV = 100 x 0.047 AVG 5.43 = 0.87%
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