Determination of Calcium-Magnesium by EDTA Titration

Background

The purpose of this experiment is four-fold:

o improve proficiency with quantitative titrimetric determinations.

o introduce complex-formation titrations for determinations of metal ions using a widely applicable chelating agent, EDTA. The skills learned with this experiment will be applied later (sections D.2, D.3) for certification of laboratory metal reagents.

o provide an example of determining each of two analytes in a mixture, implementing a physical separation of analytes by selective precipitation.

o provide one (of three) proficiency test(s) designed to certify each student as qualified to perform instrument and reagent validation operations required by Good Laboratory Practice guidelines, and to conduct more complex analytical studies.

Synopsis of the Analytical Problem

The analytical study conducted here involves the determination of both the "total hardness" and the relative concentrations of Mg and Ca in a brine sample containing only salts of these two ions. This is accomplished by a titration method using the chelating agent, EDTA (ethylenediamine tetraacetic acid). First, the titration is conducted under conditions where both ions react with the EDTA, and the end point is detected after both are titrated. Then, one of the ions (Mg) is precipitated as Mg(OH)2 by increasing the pH. A subsequent titration of the solution determines only the remaining Ca ion, which remains soluble. The Mg content can be determined by difference.

Significance of the Ca-Mg Determination

"Hard" water typically contains high concentrations of Ca, Mg (and other) cations, which interfere with the use of the water for many applications. (For example, these ions diminish the effectiveness of soaps and detergents for cleansing operations; they diminish the drinking quality of water; and they contribute to the accumulation of insoluble salt deposits in storage vessels or plumbing.) The determinations of levels of these ions in untreated (natural) water are very common procedures in commercial laboratories. For some purposes it is only necessary to know the "total hardness"; this is related to the total amount of Mg and Ca in the water, and is usually expressed in terms of "ppm CaCO3". (That is, the total moles/liter of Ca and Mg is converted into the equivalent weight of CaCO3, in ppm units.) Sometimes, however, it is desired to know the relative amounts of each ion, Ca and Mg, as one may be a more serious interference in the planned application for the "hard" water.

Procedures.

Preparation of titrant. See Appendix 2 of Lab Manual to prepare 500 mL of about 0.01M EDTA solution (modify the Appendix procedure specified for one liter of 0.01M EDTA). Do not store EDTA in glass stoppered flasks. (The solution tends to "freeze" stoppers.)

nknown sample. Submit a clean 500 mL volumetric flask to receive the unknown. Dilute to the mark with distilled water, and mix thoroughly.

Procedure for "Hardness in Water". Acidify 50 mL aliquots of unknown with a few drops of dil HCl, and boil gently for a few minutes to expel carbon dioxide. Cool, add two drops of methyl red and 0.3M NaOH dropwise until the indicator changes color (see NOTE 2). Introduce 5 mL of special pH 10 buffer, 2 drops of eriochrome black T indicator (very viscous), and titrate with standard EDTA until the color changes from red to pure blue (see NOTE 3). Calculate total hardness, expressed as ppm CaCO3.

NOTES:

(1) The acidification and boiling step is to remove carbonates, which if present, will precipitate CaCO3 when the solution is made basic. The precipitate obscures the end point.

(2) The excess HCl must be neutralized carefully. If too much NaOH is added, Mg(OH)2 precipitates, giving a poor end point.

(3) As the end point is approached, the color goes from purple to blue. When you think it is blue, read the buret, then add another drop of titrant; if there is a perceptible color change, again read buret and add another drop. Continue until a drop of titrant gives no color change, then record the preceding buret reading. If CaCO3 or Mg(OH)2 is present, the purple color returns; add more titrant until the blue color persists for at least one minute.

(4) Trace amounts of many metals, such as Cu or Cd, react with the indicator and interfere seriously with the end point. If these metals are present, they can be masked with a few drops of 0.1M KCN. When KCN is used, review the hazards and the requirement for disposal.

(5) It is necessary to keep the pH at about 10 for two reasons: (a) all reactions between metal ions and EDTA are pH dependent, and for divalent ions, solutions must be kept basic (and buffered) for the reaction to go to completion; (b) the eriochrome black

T indicator requires a pH of 8 to 10 for the desired color change.

Procedure for Calcium Only. If the pH of the sample solution is raised to about 13, magnesium will precipitate as the very insoluble hydroxide which will not react with EDTA, and calcium alone can be titrated using calcon indicator. Since the total hardness titration gives the sum of both Ca and Mg in the sample, and titration at pH 13 gives Ca only, Mg can be obtained by difference.

Perform as follows a preliminary titration to find the approximate volume of EDTA solution needed to react with the calcium. To 50 mL of the sample solution, add 3-4 drops of polyvinyl alcohol, 20 drops of 50% NaOH, and heat to 60-70o. Add 2 shots of hydroxy naphthol powder indicator (caution) and titrate with EDTA to a

clear blue. Titrate rapidly without trying to get an exact end point.

To another aliquot of the sample solution, add 3-4 drops of polyvinyl alcohol, 2 shots of hydroxy naphthol powder indicator, and accurately add (carefully measure) ~95% of the volume of EDTA used in the preliminary titration. (See NOTE 1.) Heat to 6070o, add 20 drops of 50% NaOH, mix, and continue the titration to a clear blue end point. Repeat with two additional portions of sample.

NOTES:

(1) The precipitated magnesium hydroxide obscures the end point somewhat. The precipitate also adsorbs and coprecipitates calcium ions, and frequently causes the calcium results to be low. By adding 95% of the volume of EDTA obtained in the preliminary titration, the calcium ion concentration is reduced to a

very low value before precipitating magnesium hydroxide and thus little is adsorbed or coprecipitated. Also polyvinyl alcohol and heating to 70o reduces the adsorption of calcium.

(2) Eriochrome Black T indicator does not give a satisfactory color change at high pH. Hydroxy naphthol indicator is similar to Eriochrome Black T, and functions in the same manner, but at high pH.

Report

For the brine sample, report:

(1) Total hardness, expressed as ppm CaCO3

(2) Calcium, expressed as weight/volume percent

(3) Magnesium, expressed as weight/volume percent

Recommendation

While the EDTA solution is freshly prepared, it is recommended that the student perform one of the reagent certification procedures of the Series D lab studies. (Select one from Series D.2; procedures at end of Lab Manual).

Click here to view and/or print the Table for this section

Click here to view and/or print the Sample Table for this section

Desinfection, sterilisation and cleaning of water and sewage water by UV-light

SenLights offers UV and ozone lamps for the disinfection, sterilisation, sterilization and cleaning of drinking water, potable water and sewage water. Those lamps can be installed above the water, partially in the water and in the

air, and in the water. They can be used to clean the air above the water and to clean the water itself. The oxygen in the air or water is decomposed by a 185 nm wavelength radiation produced by the UV lamp. The decomposed oxygen then combines with other oxygen which forms ozone. This ozone is then decomposed by a 254nm wavelength radiation to compose oxygen and the very high energy "O*" radical which is able to break the bonding of most organic elements. The efficiency depends on the amount of ozone, the exposure span to the ozone, the light energy, the light spectrum and the distance to the light source.

To sterilize the AIR in the tank

As the level of the water decreases, the air gets in and is sterilized by the ozone generated by the UV lamp.

To sterilize the AIR and WATER in the tank

The air aswell as the water, is sterilized by the ozone generated by the UV lamp. This is achieved by installing the lamp in a horizontal position.

To sterilize the WATER in the tank

Only the water inside the tank is sterilized by the ozone generated by UV lamp.

Down Light Type Tank Layer ST-110D-6A

This model is used to sterilize the air with 254nm wavelength radiation. It can be made to produce ozone.

Tank Layer ST-110P

This model is used to sterilize the water inside the tank. The system can be chosen depending on the tank. It can be installed inside the water (side insertion) or partially in the water and in the air (top insertion).

Uzon
SenLights developed a special model for the sewage water cleaning which is called Uzon. Uzon uses the combined power of uv-light and ozone to purify the water. The ozone which is internally created by the same UV-lamp is infused into the sewage water to increase the effect of the UV/ozone power. Uzon is available in sizes from 25W lamp and 300 * 460 * 936mmH dimensions to process 2,000 l/H to a large one with 12 lamps of 95W and 1250 * 650 * 1865mmH to process 90,000 l/H.
.

UZ 1108

This model can be used indoor or out door. It uses eight 95W-lamps to produce 60 m/H. Its 185nm wavelength is efficiently used to produce ozone from Oxygen which is induced into the sewage water to increase the purification ratio.

UT-110 H

This model includes a 95W UV lamp which sealed in a water proof quartz glass Jacket. It should be put in the water to purify the water. Its ozone can not be infused into the water because of its structure. This model also includes a 95W UV lamp which is sealed in a water proof quartz glass Jacket.The difference to the UT-110 H model is in the structure of the unit that permits to inject the air inside the jacket to produce ozone and infuse it into the water to increase

UTZ-110 T

the effect of the UZ/ozone.

SANITRON SS1101SN
The UV lamp is protected inside a quartz jacket and the inner side of the stainless steel tank is precisely polished to reflect the light and increase the purification's effects. It is installed inside the tank.