Chemistry 185H

Laboratory #1: Complexometric Titration of Divalent Cations in Water: Determination of Water Hardness Introduction This laboratory exercise demonstrates the use of a microscale complexometric titration in the determination of the concentration of metal ions in water. A titration is the gradual addition of a precisely measured volume of a solution containing a known concentration of a reactant to a test solution until the end point of a reaction with an analyte, the substance being analyzed in the solution, is reached. The usual technique involves monitoring the presence of the analyte or a product species with an indicator molecule, which affords the solution an easily detected color. At the end point of the reaction, the color of the solution changes abruptly, allowing determination of the concentration of the analyte in the solution in terms of the quantity of reactant (titrant) required to reach that point. (For a refresher on titrations and the associated calculations, you can consult Fundamentals Section L.3 in Atkins/Jones.) The presence of free divalent cations (Ca2+ or Mg2+) dissolved in water can be detected using indicator dyes, such as calmagite or Eriochrome Black T whose structures are shown in the Appendix. These dyes exist as anions (H2In-, HIn2-, In3-) in solution with the degree of protonation depending on the solution pH. In acidic and neutral solutions H2In- is the predominant form, while under moderately basic conditions HIn2- is the most prevalent species. This experiment will be carried out under basic conditions maintained by an NH3 buffer using calmagite as the indicator dye. Upon addition of the indicator to a solution containing metal dications (M2+) the solution turns a wine-red color owing to the formation of a complex, M-In-: M2++ HIn2- qeM-In- + H+ K1 (1)

When not associated with a metal ion in moderately basic solutions, these indicators exist in their singly protonated form HIn2-, which is blue. We can precisely determine the combined concentration of Ca2+ and Mg2+ in the solution by gradually adding a solution of ethylenediaminetetraacetic acid (EDTA), which forms a more stable complex with metal dications than the indicator does (K2 >> K1): M2+ + EDTA4- qe M-EDTA2K2 (2)

Accordingly, when enough EDTA has been added to the solution to chelate all of the Ca2+ and Mg2+, the solution will abruptly change from the wine-red color that reports the presence of Ca-In- and Mg-In- complexes to the blue color that reports the presence of free HIn2-. The complexes formed by EDTA with the metal ions are colorless. If we accurately determine the amount of EDTA added to the solution in terms of the volume and concentration required to reach the end point, we can accurately determine the total concentration of Ca2+ and Mg2+ that is present. This procedure is commonly used to determine the amount of Ca2+ in hard (Ca2+- or Mg2+-containing) water obtained from wells or underground springs.

Procedure 1. Set up two 2-mL microburets according to your TAs instructions. 2. Prepare a 0.01 M solution of disodium EDTA. Weigh out about 0.4 g of Na2EDTA2H2O and about 0.01 g of MgCl26H2O, and transfer them into a clean 25-mL beaker. Dissolve the solids in 20 mL of water. If the solution is cloudy, add a drop or two of 0.1 M NaOH, with mixing, until a clear solution is obtained. Ask your TA to inspect the solution to see if it is sufciently clear. Transfer the solution to a clean ask or bottle, and dilute with water to obtain a total volume of 100 mL. (You may be wondering about the presence of Mg2+ in the EDTA solution that will be used to determine the total concentration of Ca2+ and Mg2+ in the unknown sample. The Mg2+ present in the EDTA solution is complexed effectively irreversibly with EDTA (K2 > 6 108) before the EDTA solution is standardized. When Mg2+ is present the color change associated with the end point is sharper.) 3. Prepare a 0.01 M solution of calcium chloride. Obtain a thoroughly cleaned and rinsed 100-mL volumetric ask. Weigh accurately (to a thousandth of a gram) approximately 0.100 g of powdered CaCO3 that has been previously dried at 100 C in an oven for at least one hour. Transfer the solid quantitatively to the 100-mL volumetric ask using a funnel. Rinse any residual solid from the funnel and the neck of the volumetric ask using 10 to 20 mL of deionized water added dropwise from a Pasteur pipet. Then, add concentrated HCl dropwise using a Pasteur pipet until the evolution of CO2 gas from the reaction CaCO 3 ( s ) + 2 HCl ( aq ) CaCl 2 ( aq ) + H 2 O ( l ) + CO 2 ( g ) (3)

ceases. Add water almost to the mark of the volumetric ask, and mix the solution in the ask thoroughly; then add water dropwise with additional mixing to obtain the mark exactly. Calculate the molarity of the solution that you have obtained. 4. Standardize the Disodium EDTA solution. Obtain a clean 10-mL Erlenmeyer ask containing a micro stir bar, a 1-mL pipet, and a magnetic stir plate. Rinse one of the microburets with your CaCl2 solution; rinse the other with the EDTA solution. Then ll the burets with the solutions. Record the initial volumes as accurately as possible. Rinse the Erlenmeyer ask with deionized water several times. From the buret, transfer 2.00 mL of the CaCl2 solution into the ask. Add 0.2 to 0.3 mL (1-2 drops) of the NH3 buffer solution (provided by the TA) followed by 0.2 mL of calmagite solution. (The NH3 buffer solution is used to ensure that the EDTA is present in the EDTA4- form that chelates quantitatively with M2+ rather than the H2EDTA2- or HEDTA3- forms. Stir the contents of the ask using the stir bar and magnetic stirrer to obtain a homogeneous solution. Notice that the solution of calmagite currently exhibits a wine-red color. With constant stirring, titrate the solution by adding EDTA solution just until the wine-red color changes to a distinct blue. No trace of red color should remain in the solution. Record the nal volume of EDTA solution that is now present in the buret, and calculate the amount of EDTA solution that you added to the solution in the ask. Repeat the procedure described above several times (at least twice more) until you get reproducible results. Determine the molarity of the EDTA solution using your results. 5. Determine the hardness of an unknown water sample. Repeat the procedure that you used above using a sample of tap water, mineral water (Perrier, Evian, San Pellegrino,...), or

synthetic sea water provided by your TA. (Note: some of the samples may require dilution to be titrated using the volume of your standardized EDTA solution that can be delivered by the microburet. Dilution of a 5.00 mL sample to 50.00 mL would be a good starting point for samples requiring dilution. Your TA will advise when this is necessary.) Rinse the buret that you used previously to hold the CaCl2 solution several times with some of the hard water, and then ll it with hard water so that you can precisely deliver 2.00 mL of the water into your Erlenmeyer ask. The rest of the procedure is exactly the same as described above; nd the amount of EDTA solution (now of known concentration) required to reach the end point, as detected with the calmagite indicator. Repeat the titration several times in order to obtain a reliable result. Calculate the concentration of Ca2+ plus Mg2+ found in the hard water sample from your results. You should calculate the mean and standard deviation using a set of several (at least three) good titration runs. 6. Compare your results with those obtained by your colleagues for different samples. Are you surprised by the results? 7. Your laboratory report can be brief, a couple of pages. It should be prepared according to the format provided below. Note: This is an abbreviated report format that applies to this particular report only. For subsequent laboratories you will be expected to follow the format given in the General Guidelines for CEM 185H Laboratory Reports, which is posted on the course web site. Introduction: state the objectives of this experiment and provide an overview of the procedure used to determine the total concentration of Ca2+ plus Mg2+, including the relevant reactions. Results: tabulate the results from the individual titration runs for the standardization of the EDTA solution and for the total Ca2+ and Mg2+ concentration in the unknown hard-water sample as well as mean values and standard deviations. Show any calculations that are necessary in an appendix. Text should guide the reader through the results. Sufcient information should be provided in this narrative to make it possible for the reader to understand what has been done without consulting this lab handout. Conclusions: state the nal determination of the total concentration of Ca2+ and Mg2+ in the hard-water sample, and compare your results to those obtained by your peers for different water samples. You can add any comments or suggestions about how the procedure might be improved or about how your analysis might have been awed, whatever seems appropriate. Comment on possible sources of systematic error. Acknowledgments The procedure outlined above is based upon that found in Singh, M. M.; Pike, R. M.; Szafran, Z. Microscale and Selected Macroscale Experiments for General and Advanced General Chemistry: An Innovative Approach; John Wiley and Sons, Inc.: New York, 1995, pp. 275-281. An alternate procedure for determining the concentrations of Ca2+ and Mg2+ ions in aqueous solutions using an EDTA titration (pp. 743-744) as well as further discussion of complexometric titrations of metals using EDTA (chapter 13) can be found in the following text: Harris, D. C. Quantitative Chemical Analysis, 3rd ed.; W. H. Freeman and Co.: New York, 1991.

Appendix 1. Calmagite, 2-hydroxy-1-(2-hydroxy-5-methylphenylazo)-4-naphthalenesulfonic acid, has the following structure: H+

CH3 N N OH HO

O3S

A suitable calmagite solution for the procedure described above is 0.1% (w/v) in deionized water. 2. An alternative divalent metal ion indicator, Eriochrome Black T (EBT), 3-hydroxy-4-[(1hydroxy-2-naphthalenyl)azo]-7-nitro-1-naphthalenesulfonic acid, monosodium salt, has the following structure: OH

OH N N

O3S

Na+ O2 N Stock solutions of EBT that are suitable for this analysis are 0.1% (w/v) in methanol; alternatively, solid EBT (usually supplied as 0.1% (w/w) solid mixture in NaCl) can be added to test mixtures. Notice the structural similarities between calmagite and EBT. Consequently, calmagite and EBT complex with metal ions in similar fashions. Like calmagite, EBT is red when complexed with metal ions and blue when free. Calmagite stock solutions are more stable than those of EBT, so calmagite is favored for use in this laboratory exercise. 3. Water hardness is reported as ppm (by weight) CaCO3 based on the often incorrect assumption that Ca2+ is the only divalent metal ion present and CO32- is the only counterion, an oversimplication of the actual situation. Hard water often contains Mg2+, Fe2+, HCO3-, Cl-, and SO42- as well. The compounds CaCO3 and MgCO3 precipitate out of solution and form the scale in water heaters, coffee makers, etc. associated with hard water. 4. In this experiment, the total concentration of Ca2+ plus Mg2+ is determined. EDTA has very large equilibrium constants (K2 > 107) for complexation with metal ions having +2 and higher charge states, which results in quantitative, nonselective complexation with any of these metal ions present. To determine the concentration of a single ion when several ions are present, it is necessary to use masking agents that can sequester one or more of the metal ions present by binding more tightly than EDTA. For example, when Ca2+ and Mg2+ are present, the concentration of Ca2+ can be measured independently by rst adding NaOH to remove
4

Mg2+ through precipitation of Mg(OH)2 and then performing the EDTA titration using the indicator hydroxynaphthol blue, which is a better indicator at higher pH than calmagite or EBT. The equilibrium constants for complexation of EDTA with alkali metal ions are at least 4 orders of magnitude smaller than those for metal ions with +2 and higher charge states; consequently, the presence of alkali metal ions will not appreciably affect the titration results. 5. Two types of error, random and systematic, are encountered in experimental measurements. When multiple measurements of a quantity are made, random error causes the results to be scattered around the actual or true value, while systematic error or bias causes all of the measured values to differ by the same sign and magnitude from the true value. The origin of systematic error can be instrumental, procedural, or operator-related. The results of replicate experimental measurements are reported as a mean standard deviation, with the standard deviation representing the error in the measurement. In the absence of systematic error, the mean value will asymptotically approach the actual value as the number of measurements increases because random error scatters the measured values about the actual value. The mean value of N experimental measurements is given by 1 1 x = --- ( x + x2 + + xN ) - x i = --N 1 N
i=1 N

(4)

The standard deviation for a nite number of measurements

( xi x )
s =

i=1 ----------------------------N1

(5)

provides a measure of the reproducibility or precision of a measurement. Additional information on error in experimental measurements can be found in Appendix 1 of the following text, which is on reserve in the Biomedical and Physical Sciences Library: Skoog, D. A.; Leary, J. J. Principles of Instrumental Analysis, 4th ed.; Saunders College Publishing: Fort Worth, 1992.

Revised 8/05