Experiment 4: EDTA Titration of Ca2+ and Mg2+ in Natural Waters Motivation and Objectives

Motivation: The quality of a water sample can be described in terms of its hardnesstotal Ca2+ and Mg2+ content. Hard water is normally undesirable, both in practical (ie. formation of soap scum) and industrial (ie. formation of clogs industrial broilers due to CaCO3 deposits) sense. Essentially, analysis and determination of total hardness of water allows for the selection of suitable methods to reduce ion content. Objective: 1. Determine total hardness of water (ie. total ion concentration of Ca2+ and Mg2+) by complexometrix EDTA titration. 2. Determine absolute concentrations of Ca2+(aq) and Mg2+(aq) by EDTA titration fractional precipitation of Mg(OH)2.

EDTA Titration
EDTA forms colored, stable complexes with most divalent metal ions such as Ca2+(aq) and Mg2+(aq): Ca2+(aq) + EDTA4-(aq) [Ca-EDTA]2-(aq) Kf = 5.0 x 1010

Mg2+(aq) + EDTA4-(aq)

[Mg-EDTA]2-(aq) Kf = 4.9 x 108

Ethylenediaminetetraacetic acid (EDTA) Forms stable complexes with Ca2+(aq) and Mg2+(aq) Can be used as a good reagent for standardization as it is non-hygroscopic and can be obtained in very high purity Inexpensive

Fractional Precipitation of Mg(OH)2

Ca2+(aq) and Mg2+(aq) can be precipitated out from solution by using an appropriate precipitating agent such as OH-(aq). In the experiment, 50 wt% NaOH shall be used as the hydroxide source. Ca2+(aq) + 2OH-(aq) Ca(OH)2(s)

Mg2+(aq) + 2OH-(aq) Mg(OH)2(s)

However, Mg(OH)2 and Ca(OH)2 are slightly soluble salts; we can consider their respective equilibria in solution and solubility product constants: Mg(OH)2 Mg2+(aq) + 2OH-(aq) Ksp = 6 x 10-10

Ca(OH)2(s)

Ca2+(aq) + 2OH-(aq)

Ksp = 5.19 x 10-6

EDTA Titration
What happens during titration? Note: Na2H2EDTA = H2Y2- (at pH = 10, H3Y-) Eriochrome Black T = HIn2- (at pH = 10, HIn2-) Ca2+(aq) + HY3-(aq) [Ca-Y]2-(aq) + H+(aq) Complexation
reactions

Mg2+(aq) + HY3-(aq) [Mg-Y]2-(aq) + Ca2+(aq) Mg2+(aq) + HIn2-(aq)

[Mg-Y]2-(aq) + H+(aq)

Release of Mg2+

[Ca-Y]2-(aq) + Mg2+(aq) Mg-In-(aq) + H+(aq) Mg-Y2-(aq) + HIn2-(aq)

M-Indicator complex formation

metal-indicator complex

EDTA displaces indicator

Mg-In-(aq) + H+(aq) + Y4-(aq)

EDTA Titration
What happens during titration? Precipitation Mg2+(aq) + 2OH-(aq) of Mg(OH)
2

Mg(OH)2(s) Ca-In-(aq) Ca-Y2-(aq) + In3-(aq)

M-Indicator complex formation

Ca2+(aq) + In3-(aq)

metal-indicator complex

EDTA displaces indicator

Ca-In-(aq) + Y4-(aq)

Both Eriochrome Black T and hydroxynaphthol blue bind the metal ions (in the metal-ion -indicator complex) less strongly than EDTA does. (Why is it important?)

Part 1: Determination of Total Hardness

Sample + pH = 10 buffer + EBT Titrate with prepared EDTA primary standard until the blue endpoint Perform blank titration

Part II: Determination of [Ca2+]

Sample + 50 wt% NaOH + hydroxynaphtol Titrate with prepared EDTA primary standard until the blue endpoint Allow to stand for 5 mins with occasional swirling Resume titration until the blue endpoint

Calculations
Data to be calculated: 1. Total ion concentrations of Ca2+ and Mg2+ in the unknown solution in ppm and molarity Statistical analysis: 1. Report average values of all obtained data 2. Standard deviation 3. Relative standard deviation

Other Stuff
Waste disposal: 1. Dispose off titrates and excess analyte on the sink while ushing with running water. Some guide questions: 1. Why is EDTA used in this particular analysis? 2. In carrying out the titration, why must the solution be buffered to pH 10? 3. What makes Eriochrome Black T (or hydroxynaphtol blue) a suitable indicator for EDTA titrations? 4. Why is titration with EDTA insufcient to determine absolute concentrations of Ca2+ and Mg2+? (ie. a second titration is necessary) 5. Describe the separation of Mg2+(aq) and Ca2+(aq) in the second titration.