Nickel EDTA titration

The nickel ion freed may then be determined by an EDTA titration. Note that two moles of silver are equivalent to one mole of nickel and thus to one mole of EDTA. 

Murexide may be employed for the direct EDTA titration of calcium at pH =11 the colour change at the end-point is from red to blue-violet, but is far from ideal. The colour change in the direct titration of nickel at pH 10-11 is from yellow to blue-violet. 

Nickel may be determined in the presence of a large excess of iron(III) in weakly acidic solution by adding EDTA and triethanolamine the intense brown precipitate dissolves upon the addition of aqueous sodium hydroxide to yield a colourless solution. The iron(III) is present as the triethanolamine complex and only the nickel is complexed by the EDTA. The excess of EDTA is back-titrated with standard calcium chloride solution in the presence of thymolphthalexone indicator. The colour change is from colourless or very pale blue to an intense blue. The nickel-EDTA complex has a faint blue colour the solution should contain less than 35 mg of nickel per 100 mL. 

EXAMPLE 11-4 Calculate the relation between the potential of an indicator electrode of the type (11-28) and pNi near the end point of an EDTA titration of nickel(II). 

Puschel and Stefanac ° use alkaline hydrogen peroxide in the oxygen flask method to oxidize arsenic to arsenate. The arsenate is titrated directly with standard lead nitrate solution with 4-(2-pyridylazo) resorcinol or 8-hydroxy-7-(4-sulpho-l-naphthylazo) quino-line-5-sulphonic acid as indicator. Phosphorus interferes in this method. The precision at the 99% confidence limit is within 0.67% for a 3-mg sample. In another variation, Stefanac used sodium acetate as the absorbing liquid, and arsenite and arsenate are precipitated with silver nitrate. The precipitate is dissolved in potassium nickel cyanide (K2Ni(CN)4) solution and the displaced nickel is titrated with EDTA solution, with murexide as indicator. The average error is within + 0.19% for a 3-mg sample. Halogens and phosphate interfere in the procedure. 

Chromel is an alloy composed of nickel, iron, and chromium. A 0.6472-g sample was dissolved and diluted to 250.0 mL. When a 50.00-mL aliquot of 0.05182 M EDTA was mixed with an equal volume of the diluted sample, all three ions were chelated, and a 5.11-mL back-titration with 0.06241 M copper(II) was required. The chromium in a second 50.0-mL aliquot was masked through the addition of hexamethylenetetramine titration of the Fe and Ni required 36.28 mL of 0.05182 M EDTA. Iron and chromium were masked with pyrophosphate in a third 50.0-mL aliquot, and the nickel was titrated with 25.91 mL of the EDTA solution. Calculate the percentages of nickel, chromium, and iron in the alloy. 

The most sensitive - and perhaps for the radiochemist, the most useful volumetric procedure is complexlmetrlc titration utilizing the lead EDTA complex. A number of Indicators have been used for the direct EDTA titration (W5) The most popular of these are Erlochrome Black T (Cl) (W5)j Eriochrome Red B and X-ylenol orange (W5)- The direct titration with the sodium salt of EDTA is carried out in a pH 10 buffer solution (P5)(p6). Iron, the alkaline earths and the earths interfere but bismuth, aluminum and antimony do not. Cyanide can be used to mask cobalt, nickel, copper, zinc, cadmium, mercury and platinum (Cl),... 

BackTitrations. In the performance of aback titration, a known, but excess quantity of EDTA or other chelon is added, the pH is now properly adjusted, and the excess of the chelon is titrated with a suitable standard metal salt solution. Back titration procedures are especially useful when the metal ion to be determined cannot be kept in solution under the titration conditions or where the reaction of the metal ion with the chelon occurs too slowly to permit a direct titration, as in the titration of chromium(III) with EDTA. Back titration procedures sometimes permit a metal ion to be determined by the use of a metal indicator that is blocked by that ion in a direct titration. Eor example, nickel, cobalt, or aluminum form such stable complexes with Eriochrome Black T that the direct titration would fail. However, if an excess of EDTA is added before the indicator, no blocking occurs in the back titration with a magnesium or zinc salt solution. These metal ion titrants are chosen because they form EDTA complexes of relatively low stability, thereby avoiding the possible titration of EDTA bound by the sample metal ion. 

CrP" -selective and Ni " -selective electrodes have been used to detenuine the copper and nickel ions in aqueous solutions, both by direct potentiometry and by potentiometric titration with EDTA. They have also been used for detenuining the CiT and Ni " ions in indushial waters by direct potentiomehy. 

The method may also be applied to the analysis of silver halides by dissolution in excess of cyanide solution and back-titration with standard silver nitrate. It can also be utilised indirectly for the determination of several metals, notably nickel, cobalt, and zinc, which form stable stoichiometric complexes with cyanide ion. Thus if a Ni(II) salt in ammoniacal solution is heated with excess of cyanide ion, the [Ni(CN)4]2 ion is formed quantitatively since it is more stable than the [Ag(CN)2] ion, the excess of cyanide may be determined by the Liebig-Deniges method. The metal ion determinations are, however, more conveniently made by titration with EDTA see the following sections. 

These reactions take place with sparingly soluble silver salts, and hence provide a method for the determination of the halide ions Cl", Br, I-, and the thiocyanate ion SCN ". The anion is first precipitated as the silver salt, the latter dissolved in a solution of [Ni(CN)4]2", and the equivalent amount of nickel thereby set free is determined by rapid titration with EDTA using an appropriate indicator (murexide, bromopyrogallol red). 

Thymolphthalein complexone (thymolphthalexone). This is thymolphthalein di(methyliminediacetic acid) it contains a stable lactone ring and reacts only in an alkaline medium. The indicator may be used for the titration of calcium the colour change is from blue to colourless (or a slight pink). Manganese and also nickel may be determined by adding an excess of standard EDTA solution,... 

Pipette 25 mL nickel solution (0.01 M) into a conical flask and dilute to 100mL with de-ionised water. Add the solid indicator mixture (50mg) and 10 mL of the 1M ammonium chloride solution, and then add concentrated ammonia solution dropwise until the pH is about 7 as shown by the yellow colour of the solution. Titrate with standard (0.01 M) EDTA solution until the end point is approached, then render the solution strongly alkaline by the addition of 10 mL of concentrated ammonia solution, and continue the titration until the colour changes from yellow to violet. The pH of the final solution must be 10 at lower pH values an orange-yellow colour develops and more ammonia solution must be added until the colour is clear yellow. Nickel complexes rather slowly with EDTA, and consequently the EDTA solution must be added dropwise near the end point. 

Silver halides can be dissolved in a solution of potassium tetracyanonickelate(II) in the presence of an ammonia-ammonium chloride buffer, and the nickel ion set free may be titrated with standard EDTA using murexide as indicator. 

Iron (and nickel, if present) can be determined by adding an excess of standard EDTA to the cold solution, and then back-titrating the solution with lead nitrate solution using xylenol orange as indicator provided the solution is kept cold, chromium does not react. The solution from the back-titration is then acidified, excess of standard EDTA solution added and the solution boiled for 15 minutes when the red-violet Cr(III)-EDTA complex is produced. After cooling and buffering to pH 6, the excess EDTA is then titrated with the lead nitrate solution. 

The procedure involved in the determination of these anions is virtually that discussed in Section 10.58 for the indirect determination of silver. The anion to be determined is precipitated as the silver salt the precipitate is collected and dissolved in a solution of potassium tetracyanonickelate(II) in the presence of an ammonia/ammonium chloride buffer. Nickel ions are liberated and titrated with standard EDTA solution using murexide as indicator ... 

For example, EDTA can be used to determine the percentage of nickel present in a nickel salt by complexometric titration. EDTA is a hexadentate ligand that binds in a 1 1 ratio with most metal ions, such as Ni +, forming a stable octahedral complex as shown in the diagram. 

In an experiment to determine the percentage of nickel In hydrated nlckel(ll) sulfate, 2-63 g of the nlckel(ll) sulfate were weighed accurately, dissolved In water and diluted to 100 cm in a standard flask. A 20-0 cm volume of this solution was pipetted Into a conical flask along with an indicator solution. This solution was titrated against a 0-100 mol fi EDTA solution until the end-point was observed. The titrations were repeated until concordant results were obtained. 

A solution of NP (25.00mL) was titrated with 0.1036molL EDTA at pH 5 and required 20.25 mL for the metal-indicator to change colour. What is the concentration (gL ) of Ni The atomic weight of nickel is 58.71 gmoC. ... 

The liberated nickel ion required 26.73 mL of 0.02089 M EDTA. The bromate in a 10.00-mL aliquot was reduced to bromide with arsenic(III) prior to the addition of silver nitrate. The same procedure was followed, and the released nickel ion was titrated with 21.94 mL of the EDTA solution. Calculate the percentages of NaBr and NaBr03 in the sample. 

Some divalent metal ions can interfere including bariiun, cadmium, lead, manganese, strontium and zinc. These are titrated as hardness. In addition aluminum, cobalt, iron and nickel can interfere with the end point. This interference becomes more severe when phosphates are present above 10 mg k. If these metals are present at significant levels, non-EDTA methods for hardness are preferred. 

The second approach is much like the preceding method. The precipitate in which the anion to be determined is engaged is treated with a reagent that stoichiometri-cally liberates a cation that is titrated with a standard solution of EDTA. Hence, a halide (except the fluoride) or the thiocyanate ion is precipitated as the corresponding silver salt. The latter is treated with a solution of potassium tetracyanonickelate K2 [Ni(CN)4]. The silver salt dissolves into this solution with liberation of one nickel ion Ni + for two ions X . Ni + is titrated with EDTA in the presence of murexide. The reaction constituting the basis of the process is... 

Since a suitable indicator is not always available for the direct titration against EDTA, a back titration is recommended (Sec.2.2.4) where a known excess of standard EDTA solution is added to an aliquot of the nickel solution, back titrating the excess against standard ZnS04 solution. To 25.00 cm of 0.1 M Ni(ll) solution, add a known excess (50.00 cm ) of the standardised O.l.M. EDTA solution in a 400 cm conical flask. Dilute the solution to about 200 cm and add 4 cm of the buffer solution (pH = 10) and 1-2 drops of Eriochrome Black T indicator. Titrate the excess of EDTA with standard 0.1 M zinc sulphate solution until the colour changes sharply from blue to greenish red. Repeat to obtain concordant results. Calculate, from the average titre, the concentration of nickel(II) in g dm ... 

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