This document discusses complex-formation titrations, which involve reactions that form complex ions or coordination compounds. It describes how coordination compounds are widely used for titrating cations, including forming colored substances for identification and chemical masking. It provides details on common ligands, titrants like EDTA, and indicators used in complexometric titrations. Examples are given for applications like determining water hardness and analytes like metals.
This document discusses complex-formation titrations, which involve reactions that form complex ions or coordination compounds. It describes how coordination compounds are widely used for titrating cations, including forming colored substances for identification and chemical masking. It provides details on common ligands, titrants like EDTA, and indicators used in complexometric titrations. Examples are given for applications like determining water hardness and analytes like metals.
This document discusses complex-formation titrations, which involve reactions that form complex ions or coordination compounds. It describes how coordination compounds are widely used for titrating cations, including forming colored substances for identification and chemical masking. It provides details on common ligands, titrants like EDTA, and indicators used in complexometric titrations. Examples are given for applications like determining water hardness and analytes like metals.
This document discusses complex-formation titrations, which involve reactions that form complex ions or coordination compounds. It describes how coordination compounds are widely used for titrating cations, including forming colored substances for identification and chemical masking. It provides details on common ligands, titrants like EDTA, and indicators used in complexometric titrations. Examples are given for applications like determining water hardness and analytes like metals.
coordination compounds a A + b T --In c Product Polyvalent Ligand Complex Ion / Coordination Compound Cation or Complexing Agent
remarkable growth in their analytical application is
based upon a particular class of coordination compound called chelates widely used for titrating cations Complex-Formation Titrations
Uses of Coordination Compounds
1. Formation of Colored Substances can be used to indicate the presence of a specific metal ion and/or determine its concentration in the sample
2. Chemical Masking masking agent decreases the concentration of a free metal ion to a level where a particular interfering reaction will not occur 3. Titration of Metal Ions A.Nature
Ligand 1. Inorganic 2. Organic
H2O, NH3, Cl1- EDTA, NTA donor species B. Number of Electron Pair Donors must have at least one pair 1. Unidentate 2. Polydentate or of Multidentate unshared H2O, NH3, Cl1- EDTA, NTA electrons available for bond formation Complex-Formation Titrations
Coordination Number number of covalent
bonds that a cation tends to form with electron donors e.g. two, four, six
Chelate - produced when a metal ion coordinates
with two (or more) donor groups of a single ligand to form a five or six- membered heterocyclic ring Cu 2+ + 2 GLYCINE Titrants : Complexing Agents
polydentate / multidentate NTA generally react Nitrilotriacetic acid more completely second most with cations and common thus provide complexing agent sharper end points used for titrimetry ordinarily react tetradentate with metal ions in a ligand single-step process Titrants : Complexing Agents
EDTA Ethylenediaminetetraacetic acid
free acid, H4Y and the dihydrate of the sodium salt, Na2H2Y . 2 H2O, are the commercially available in reagent quality forms very stable, 1:1complexes with most metal ions its dilute solutions are very stable it is sensitive to pH of the solution, thus it is somewhat selective in its reactivity with different metal ions hexadentate ligand Indicators
1. Xylenol Orange
weak complexing one of the few agents indicators that can be used in acidic exhibit different solutions colors in their complexed and uncomplexed form Indicators
2. Eriochrome Black T oldest and most widely used oxidized slowly by complexation dissolved oxygen, indicator ascorbic acid is sometimes added to used exclusively in retard this reaction or the pH range 7 to 11 solid EBT is added directly to the sample prior to titration Indicators
3. Calmagite 4. Arsenazo I excellent indicator for EDTA titrations of the structure is very rare earths similar to EBT unlike EBT and Calmagite, not more stable than blocked by small EBT in aqueous amounts of copper or solution iron (III) during calcium and magnesium titrations Analytes
virtually every determinations
metal cation of analyte or with the mixture of analytes involve exception of one or a the alkali combination of metal ions the titration methods Applications
1. Direct Titration Method
Determination of Water Hardness expressed in terms of the concentration of calcium carbonate that is equivalent to the total concentration of all the multivalent cations in the sample hard water precipitates calcium carbonate upon being heated, which then clog boilers and pipes calculated as ppm CaCO3 Applications
2. Back-Titration Method cations that cannot be titrated directly but form very stable EDTA complexes are good candidates for back-titration
3. Indirect / Replacement Titration Method
unavailability of a suitable indicator may also be overcome by replacing the analyte with an acceptable substitute Exercise 14
An antacid tablet weighing 15.476-g was dissolved in
acid and diluted to 500.0-mL. A 25.00-mL aliquot of the solution was made sufficiently basic to precipitate the Al as Al(OH)3. The remaining Mg required 16.49-mL of 1.043 x 10 -2 M EDTA for titration. A second 25.00-mL aliquot was withdrawn from the 500-mL flask and treated with 50.00-mL of the EDTA. This solution was made basic and the excess EDTA back titrated with 11.73-mL of 5.594 x 10 -3 M MgCl2. Calculate the percentage of both Mg and Al in the sample. Molar Masses: Al = 26.98 Mg = 24.31 Exercise 14
An antacid tablet weighing 15.476-g was dissolved in
acid and diluted to 500.0-mL. A 10.00-mL aliquot of the solution was made sufficiently basic to precipitate the Al as Al(OH)3. The remaining Mg required 6.596-mL of 1.043 x 10 -2 M EDTA for titration. A second 25.00-mL aliquot was withdrawn from the 500-mL flask and treated with 50.00-mL of the EDTA. This solution was made basic and the excess EDTA back titrated with 11.73-mL of 5.594 x 10 -3 M MgCl2. Calculate the percentage of both Mg and Al in the sample. Molar Masses: Al = 26.98 Mg = 24.31 Exercise 14 A 0.4085-g sample containing lead, magnesium and zinc was dissolved and treated with cyanide to complex and mask the zinc: Zn 2+ + 4 CN 1- Zn(CN)4 2- Titration of the lead and magnesium required 42.22-mL of 0.02064-M EDTA. The lead was next mask with BAL (2,3-dimercaptopropanol), and the released EDTA was titrated with 19.35-mL of a 0.007657-M magnesium solution. Finally, formaldehyde was introduced to demask the zinc: Zn(CN)4 2- + 4 HCHO + 4 H2O Zn 2+ + 4 HOCH2CN + 4 OH 1- which was titrated with 28.63-mL of 0.02064-M EDTA. Calculate the percentages of the three metals in the sample. Molar Masses: Zn = 65.37 Pb = 207.2 Mg = 24.31
