Chapter 6

EDTA TITRATIONS Complexometric titrations have many applications, especially for determination of metal ions. Ethylenediaminetetraacetic acid (EDTA) is the most widely used complexing 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 complexation. 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: o = [H4Y]/CT 1 = [H3Y-]/CT 2 = [H2Y2-]/CT [HY3-]/CT 4 = [Y4-]/CT Now, assume a divalent metal reacts with EDTA, Y4-, the following equilibrium will be observed in alkaline medium: M2+ + Y4- = MY2Kf = [MY2-] ___________ [M2+] [Y4-]

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

K1K2K3K4 4 = __________________________________________________________ [H3O+]4+K1[H3O+]3+K1K2[H3O+]2+k1K2K3[H3O+]+K1K2K3K4

[Y4-] = 4 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) 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 Y415.0mL Y4mol CaCO3 ?_________ = _____________ X ______________ X __________ L 1000 mL Y475.0 mL CaCO3 mol Y4100.0 g CaCO3 1000 mg CaCO3 1000 mL X ____________ X _____________ X _______ = 1X10 3 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.

Applications
Experiment 14. Complexometric Determination of Total Hardness of Water Background Water hardness is attributed to the presence of Ca2+ and Mg2+ and usually their total concentration is a measure of water hardness. EDTA form complexes with both ions and the end point can be detected using Eriochrome Black T or calmagite indicator. Results are reported as ppm CaCO3. Reactions Ca2+ + H2Y2- = CaY2- + 2 H+ Mg2+ + H2Y2- = MgY2- + 2 H+ The titration is conducted at about pH 10, which can be achieved by addition of ammonium buffer to the titration flask. Reagents and Chemicals a. Provided 1. Approximately 0.01 M EDTA solution containing about 0.1 % NaOH and 0.01% MgCl2. 6H2O. 2. Eriochrome Black T indicator that is 0.5% (W/V) in ethanol. 3. Ammonium buffer at pH 10. 4. Primary standard CaCO3 (solid, Predried and desiccated). 5. 1 : 1 HCl solution. b. Need Preparation 1. Standard Ca2+ solution, 0.01 M. This can be prepared by weighing out about 0.1 - 0.15 g of CaCO3, transfer to conical flask and add about 15 mL of HCl provided. Dilute with 50 mL of distilled water and heat the solution to boiling in order to remove CO2. Transfer to 500 mL measuring flask and dilute to volume. Procedure a. Standardization of EDTA Solution 1. Transfer exactly 25.00 mL of the Ca2+ standard solution into a 250 mL conical flask.

2. Add about 10 mL of the ammonium buffer, followed by 5 drops of the Eriochrome Black T indicator. 3. Titrate against the EDTA solution and record the volume to two significant figures after the decimal point. 4. Repeat steps 1-3 two more times. 5. Calculate the molarity of EDTA. b. Determination of Water Hardness 1. Pipet exactly 50 mL of tap water into a 250 mL conical flask. 2. Add 10 mL of the ammonium buffer and 5 drops of the Eriochrome Black T indicator. 3. Titrate against standard EDTA solution and record the volume. 4. Repeat steps 1-3 two more times. 5. Calculate the total hardness of water and report your results as ppm CaCO3. Report of Results a. Standardization of EDTA Solution
Vol of EDTA Vol of Ca2+ Molarity of EDTA

X= =

b. Determination of Total Hardness of Water

Vol of Water Sample Vol of EDTA ppm CaCO3

X= = It should be observed that this method gives the total Mg2+ and Ca2+ present in the solution. However, results should be reported as ppm CaCO3 since this is the unit, which is used by analytical laboratories for comparative purposes. Another important note concerns storage of standardized EDTA solutions where these solutions should never be stored in soda based glass. Preferrably, polyethlene bottles should always be used.

Remarks and Observations

Experiment 15. Indirect Complexometric Determination of Cobalt Background Co2+ reacts with EDTA to form a complex at low pH. If an alkaline pH is used, Co2+ precipitates as Co(OH)2 . However, Eriochrome Black T indicator is not suilable at low pH values. Therefore, Co2+ is allowed to form a complex with excess EDTA at low pH. The pH is then increased to alkaline pH where the excess EDTA can be back-titrated with standard Mg2+. Reactions Co2+ + H2Y2- (excess) = CoY2- + 2 H+ (excess) H2Y2- + Mg2+ = MgY2- + 2 H+

Reagents and Chemicals a. Provided 1. 2. 3. 4. 5. Approximately 0.01 M EDTA solution. Predried and desiccated MgCl2 . 6H2O Eriochrome Black T indicator 0.5% (w/v) in ethanol. Ammonium buffer, pH 10. Co2+ solution of unknown concentration.

b. Need Preparation 1. Standard EDTA solution, 0.01 M. The standardization of EDTA can be achieved simply by titration against MgCl2. 6 H2O standard solution at pH 10 as follows: Exactly 25.00 mL of Mg2+ (0.0l M) are transferred into a conical flask (250 mL) and 10 mL of ammonium buffer are added, followed by 5 drops of the indicator. The solution is titrated against standard Mg2+ and the experiment is repeated so that precise results are obtaind. 2. Standard Mg2+ solution. This solution can be prepared by weighing an appropriate amount of the magnesium salt provided, transferring to a 250 mL measuring flask and dissolution of the sample followed by adjustment of the volume to the mark. The required concentration is approximately 0.0l M, which should be exactly determined. Procedure

1. Transfer exactly 25.00 mL of the Co2+ solution into a 250 mL conical flask. 2. Add 10 mL of the ammonium buffer, pH 10. 3. Add 5 drops of the Eriochrome Black T indicator. 4. Titrate against standard Mg2+ and record the volume to two significant figures after the decimal point. 5. Repeat steps 1- 4 two more times. 6. Calculate the concentration of Co2+ in the solution and report your results as ppm Co2+.

Report of Results 1. Standardization of EDTA Solution

Vol of Mg2+ Vol of EDTA Molarity of EDTA

X= = 2. Determination of Co2+
Vol of EDTA Vol of Mg2+ Molarity of Co2+

X= = Calculations Assume that 50 mL of 0.01 M EDTA solution were added to 25 mL of Co2+ solution and the excess EDTA required 20 mL of 0.005 M Mg2+ solution. Calculate ppm Co2+ present. First, find the Volume of EDTA present in excess, which reacted with the Mg2+ added.
1000 mL EDTA mol EDTA 0.005 mol Mg 2+ ? mL EDTA =_______________X___________ X ______________ X 20 mL Mg 2+ = 10 mL 0.01 mol EDTA mol Mg2+ 1000 mL Mg2+

Vol of EDTA which reacted with Co2+ = 50 - 10 = 40 mL

mg Co2+ 0.01 mmol EDTA 40 mL EDTA mmol Co 2+ ? ________ = ______________ X _____________ X ___________ X L mL EDTA 25 mL Co2+ mmol EDTA 58.9 mg Co2+ 1000 mL ___________ X _______ = 942 ppm mmol Co2+ L

Remarks and Observations

Experiment 16. Complexometric Determination of Zinc and Magnesium in a Mixture Background EDTA form complexes with both Mg2+ and Zn2+ in solution. First, a titration of the mixture will result in the determination of the total amounts of the two cations. Zn2+ can be selectively masked with the addition of CN- and Mg2+ can be determined by direct titration against EDTA. Zn2+ concentration can be determined by difference. Reactions Zn2+ + H2Y2- = ZnY2- + 2 H+ Mg2+ + H2Y2- = MgY2- + 2 H+ Reagents and Chemicals a. Provided 1. A solution of Zn2+ and Mg2+ mixture of unknown concentration. 2. Stock EDTA solution (0.01 M). 3. Eriochrome Black T indicator. 4. Predried and desiccated MgCl2 . 6H2O. 5. Solid KCN (HIGHLY TOXIC!!). 6. Ammonium buffer at pH 10. 1 L of the buffer is composed of 6.4 g of NH4Cl plus 57 mL of concentrated ammonia diluted with distilled water.

b. Need Preparation 1. Standard EDTA solution. If you do not have enough from previous experiments, follow procedure mentioned in experiment 15 to standardize the EDTA stock solution. 2. Standard MgCl2. 6H2O solution. Same procedure as in experiment 15 if you do not have enough solution from previous experiments. Procedure a. Total Zn2+ and Mg2+ 1. Pipet exactly 25.00 mL of the mixture into a 250 mL conical flask. 2. Add 10 mL of the buffer solution and 5 drops of the indicator. 3. Add 50 mL of standard EDTA solution. This is an excess of EDTA.

4. Perform a back titration of excess EDTA against standard MgCl2. 6H2O. This should enable you to calculate total amounts of Mg2+ and Zn2+ present in the mixture. 5. Repeat steps 1-4 two more times and always record your volumes. b. Mg2+ Determination 1. 2. 3. 4. Pipet exactly 25.00 mL of the mixture into a 250 mL conical flask. Add 10 mL of the buffer solution provided. Add about 0.3 g of KCN and dissolve well. Add 5 drops of the Eriochrome Black T indicator and titrate against standard EDTA solution. 5. Repeat steps 1-4 two more times and record the volume of EDTA solution consumed. 6. Calculate the amount of Zn2+ present in ppm units.

Report of Results a. Total Zn2+ and Mg2+ in the mixture

Vol of EDTA Added X= Vol of MgCl2 Vol EDTA Eq to Total ppm (Zn2++Mg+)

b. Zn2+ Determination
ppm Zn2+ ppm Mg+

Vol of EDTA X=

Vol of Mixture

Remarks and Observations