EDTA-metal complexes calcium complexation reactions

By use of releasing agents Considering the reaction M-X-i-R = R- Xh-M, it becomes evident that an excess of the releasing agent (R) will lead to an enhanced concentration of the required gaseous metal atoms (M) which will be of special significance if the product R-X is a stable compormd. Hence in the determination of calcium in presence of phosphate the addition of excess of strontium chloride to the test solution will lead to the formation of strontium phosphate and the calcium can then be determined in an acetylene-air flame without any interference due to phosphate. Also addition of EDTA to a calcium solution before analysis may increase the sensitivity of the subsequent flame spectrophotometric determination which may be due to the formation of an EDTA complex of calcium which is readily dissociated in the flame. 

C. Replacement or substitution titration. Substitution titrations may be used for metal ions that do not react (or react unsatisfactorily) with a metal indicator, or for metal ions which form EDTA complexes that are more stable than those of other metals such as magnesium and calcium. The metal cation M + to be determined may be treated with the magnesium complex of EDTA, when the following reaction occurs ... 

If the analyte metal ion forms a stable EDTA complex rapidly, and an end point can be readily detected, a direct titration procedure may be employed. More than thirty metal ions may be so determined. Where the analyte is partially precipitated under the reaction conditions thereby leading to a slow reaction, or where a suitable indicator cannot be found, back titration procedures are used. A measured excess of EDTA is added and the unreacted EDTA titrated with a standard magnesium or calcium solution. Provided the analyte complex is stronger than the Ca-EDTA or Mg-EDTA complex a satisfactory end point may be obtained with eriochrome black T as indicator. An alternative procedure, where end points are difficult to observe, is to use a displacement reaction. In this case, a measured excess of EDTA is added as its zinc or magnesium complex. Provided the analyte complex is the stronger, the analyte will displace the zinc or magnesium. 

EDTA forms 1 1 complexes with divalent metals such as calcium (reaction (20))... 

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