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3/8/13

QUIZ
What

is the molarity of a KSCN solution if 23.15ml was used to backtitrate a solution containing pure 1.1956 g of Barium Chloride (BaCl2; MW=208.23g/mol) dissolved in 52 ml of 0.4489 M Silver Nitrate?

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Complexometric Titration

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HISTORY
Justus Metal Ag

Leigbig (1850) Ligand Complexation

and Hg Ions

Ligands

are Cl and CN ions Monodentate only silver and Hg form stable complex with these Ligands.

However

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HISTORY
Schwarzenbach

(1945) acids multidentate

Aminocarboxylic

ligands
Forming

stable 1:1 complex with metal

ions
Analytical

Purposes was establish when metallochromic dyes were introduced. dyes visual indicators for complexation reactions

Metallochromic

Ethylenediaminetetraacetic acid (EDTA)

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Ethylenediaminetetraacetic acid (EDTA)


Lewis 6

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Acid complex cage like = very

binding sites

Metal-ligand

stable
All

metal Ion complex of EDTA = 1:1

OPTIMUM EDTA Metal Ligand Formation


pKa1 All All

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= 0.0 pKa2 = 1.5 pKa3 = 2.0 pKa4 = 2.68 pKa5 = 6.11 pKa6 = 10.17 carboxylate ions must be ionized ammonium ions should be non ionized only if pH > 10.17

Achieved

CONDITIONAL FORMATION CONSTANTS

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CONDITIONAL FORMATION CONSTANTS

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THE EDTA-Metal Complex


To

ensure stability of ion


add buffers to control pH

We

However

some buffers are also ligands. So be careful

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Standardization of 0.1 M EDTA


Usually

EDTA can be obtained in pure

form
Standardized Procedure:
Weigh

with Metallic Magnesium, Calcium Carbonate or Metallic Bismuth


0.24 g Metallic Mg in 25ml 1 M HCl and Dilute to 1L 25 ml of solution to erlenmeyer

Dissolve Transfer

flask

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Standardization
0.1

M EDTA solution was standardized using Metallic Magnesium. 0.2414 g of Mg Metal was weighed and prepared for standardization. The EDTA solution consumed is 25 ml. What is the exact Concentration of EDTA solution?

Mole of EDTA = Mole of Magnesium M(edta) V(edta) = weight Mg/ MW Mg

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Calcium Determination

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Magnesium Containing Compounds


pH

10 (ammonia buffer) Black T

Erichrome

At

presence of other metals ---- ?

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Calcium Containing Compounds


pH

12-13 (0.1 M NaOH) Indicator


: Violet Color

Murexide
Endpoint

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Zinc Containing Compounds


pH

10 (ammonia Buffer) Black T

Erichrome

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Nickel Containing
pH

8 (10% ammonium Chlorideammonia solution)

Murexide

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Aluminum Picky
pH

5.5 (acetate buffer) *previously neutralized slow reaction Titration as Excess

Too

Residual EDTA Zinc

Sulfate as Backtitrant

Indicator

(Potassium Ferrocyanide + 3,3dimethyl naphthidine)


Potassium

Ferrocyanide -> Formation of

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Water HARDNESS TEST


Measure

of amount of Mg and Ca in

water
High

Ca and Mg content = hard water

procedure
Transfer Acidify Bring

exactly 50 mL of water to 250 mL Erlenmayer flask. the solution with hydrochloric acid. with ammonia. to boil, cool down.

Alkalize

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Quiz: Complete the Table


For pH of Buffer Determination Titration Used of: Titrant/s used Indicator and color of Endpoint

Magnesiu m Calcium Nickel Aluminum

1 5 8 12

2 6 9 13

4 7 11 15

10 EDTA Back

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EXAMPLES
You

are using EDTA with a molarity of . 0080 for the titration. You titrate 50.00 mL of water sample using 10.68 mL of EDTA. is the CONCENTRATION of Ca2+ion?

What

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EXAMPLES
What

is the %w/w Ca ion content of a milf formula if 0.453 g of the powder was titrated with 23.17 ml of 0.1337 M EDTA Solution to a murexide endpoint?

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EXAMPLES
A

200 mg Aluminum Hydroxide tablet was dissolved in acetate buffer. What is the actual concentration of Aluminum Ions in the solution if 50 ml of 0.1 M EDTA solution is used as an excess titrant and is backtitrated with 30ml of 0.0983 M Zinc Sulfate to a pink endpoint?

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Standardization example
A

0.0352 g sample of pure calcium carbonate (100.09 g/mol) was dissolved in acid and titrated to its endpoint with newly made EDTA titrant (~0.010 M) according to the procedure given below. The starting burette volume was 0.10 mL. The ending burette volume was 35.52 mL. Calculate the exact concentration of the EDTA titrant. Show all work.

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SAMPLE PROBLEM
A

0.0456 g sample of an unknown sample was titrated using the EDTA titrant from question 1 and the procedure below. The starting burette volume was 0.05 mL. The ending burette volume was 42.35 mL. Calculate the % calcium oxide (CaO; 56.0774 g/mol) by mass in the sample.
What What

is the indicator? pH should be maitained?

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WATER HARDNESS
100.0

mL of an unknown water sample was titrated using the EDTA from question 1 and the procedure below. The starting volume was 0.25 mL and the ending volume was 20.53 mL. Calculate the concentration of Ca2+in the tap water. Show all work.

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