ANIONS I-V NOTES
Bunsen- early attempt towards systematic analysis in 1878, he divided the “acid radicals” into
related groups for the purpose of identification
 Ions are negatively charged due to ionization of acids and salts
 With the exception of fluoride, chloride, bromide, iodide and sulfide ions, the anions
are composed of two or more elements bound in chemical combination
 Oxidizing anions tend to react with reducing anions, and in the reactions, the ions
lose their identities as a result of the oxidation-reduction reaction. Reactions of this
type are avoided by maintaining a pH above 7 through the first three group of the
anion scheme.
 Acetates of calcium, barium, cadmium and silver are used. Solutions of these
acetates are slightly basic due to hydrolysis.
ANIONS I
 Calcium salts are insoluble in slightly basic solution.
 Anions of Group 1 are divided in two subgroups by the action of dilute acetic acid.
 Addition of KClO2 will oxidize the sulphite, sulfide, and thiosulfate ions, in an acid
solution, to the sulfate ion or free sulfur. These produces gases in acid solution
which might be mistaken for carbon dioxide in the test for the carbonate.
 Presence of cations other than sodium, potassium, or ammonium may interfere with
anion analysis. These cations are removed by adding an excess of sodium
carbonate solution. The cations are precipitated as insoluble carbonates, basic
carbonates, or hydroxides.
 Prepared solution will contain excess carbonate ions (white, gelatinous calcium
carbonate)
Advantage: Carbonate ion maintains an alkalinity sufficient to prevent
unwanted redox reactions between anions.
Disadvantage: Carbonate causes a precipitation in Group 1 (of CaCO 3).
 The heavy metals cations are removed by the sodium carbonate treatment.
 Sodium carbonate treatment may be omitted if it is known that only sodium,
potassium and ammonium salts are present.
 Presence of SO4- may cause precipitation of CaSO4 with Group 1 anions. This
precipitate is insoluble in strong acids.
 Sample/solution is yellow=presence of CrO4- is indicated. Contamination of the
Group 1 precipitates with this ion will interfere with the anion analysis. Residue must
be washed until the color is revoved.
 Add more than 15 drops of acetic acid (Procedure 2).
 Hydrogen peroxide oxidizes the sulphite ion to sulfate. Sulfate ion is precipitated as
BaSO4.
 If yellow precipitate does not form, the arsenite ion is absent.
Arsenic pentasulfide- the precipitate of arsenate ion
 If sulfate ion is present, destroy by heating in an acid solution, otherwise, this ion will
react with free iodine liberated in the arsenate test.
 Iodine may be extracted from the brown-colored water solution by shaking of iodine
in CCL4.
 A solution of iodine in CCl4 produces a pink color.
 The excess tartaric acid, in strongly acid solution, forms a complex with arsenic,
otherwise, the arsenate ion will precipitate with ammonium molybdate in the
confirmatory test for the phosphate.
 Do not boil, possibility of soluble complex between tartaric acid and arsenic may be
broken down with heat.
 In absence of phosphate ion, a white precipitate often results due to decomposition
of the ammonium molybdate regent.
 Sulphite and arsenite interfere with the test for oxalate ion.
 The pink colored MnO4- ion is reduced by oxalic acid to (produced by calcium
oxalate in acid solution) to manganous ion which is colorless in this dilution.
 Presence of water interfere with the etching test for the fluoride ion by forming
insoluble silicic acid with volatile silicon tetrafluoride.
 Concentrated H2SO4 reacts with CaF2 to form hydrogen fluoride, and the latter
etches glass produces gaseous SiF4.
 Sulfite ion is oxidized by hydrogen peroxide to sulfte.
ANIONS II
 Calcium salts are soluble; barium salts are insoluble in slightly basic solution.
 Contains chromate and sulfate ions.
 Precipitated by the group reagent, barium acetate, as BrCrO4 and BaSO4 in a
slightly basic solution.
 Chromate is indicated by a yellow color.
 If the precipitate is white, the absence of chromate is confirmed.
 Sodium acetate buffers the hydronium-ion concentration of the solution sufficiently
to permit precipitation of BaCrO4.
 Precipitated from slightly basic solution by addition of barium acetate solution.
ANIONS III
 Calcium and barium salts are soluble; cadmium salts are insoluble in slightly basic
solution.
 The precipitation of the sulfide, ferrocyanide, ferricyanide ions by cadmium ions is
fairly complete.
  The fericyanide will oxidize sulfide ion to free sulfur, being reduced to the  Nitrite ion, in acid solution, oxidizes the iodide ion to free iodine.
ferrocyanide in the course of the reaction.
 The sulfide is converted to H2S. ANIONS V
 This solution is slightly alkaline, some precipitation of cadmium hydroxide usually  Calcium, barium, cadmium, and silver salts are soluble in water and acids.
takes place.  There is no satisfactory inorganic test for borate ion, it is necessary to resort to the
 Of the cadmium salts, sulfide is bright yellow, the ferrocyanide is pale yellow (almost use of an organic reagent: hydroxyanthraquinones a family of organic dyes,
white), and the ferricyanide is orange. specifically carminic acid dissolved in sulphuric acid).
 Dilute HCl should be added until the precipitate is dissolved and barely acid. If made  Appearance of a slight cloudiness for this test should be disregarded.
too acid, the identifying blue precipitate may not be obtained because of its solubility  The chlorate and nitrate ions interfere with the test for borate ion, these are
in HCl. destroyed by evaporating the solution with concentrated sulphuric acid.
 Green solution is obtained upon the addition of ferric chloride solution, the  The a-napthylamine os oxidized by the nitrate ion, in sulphuric acid solution, to a
ferricyanide is confirmed. compound fugitive color.
 Precipitated as cadmium salts.  The presence of chromate, bromide, iodide, ferrocyanide, ferricyanide thiocyanate,
 Cadmium sulfide dissolves in dilute hydrochloric acid. chlorate and nitrite ions interferes with the brown-ring test for the nitrate ion. All
these ions except nitraite and chlorate are precipitated in the anion scheme.
ANIONS IV
 Calcium, barium and cadmium salts are soluble; silver salts are insoluble in a
soluble slightly acid with nitric acid.
 Silver thiosulfate is unstable in this acid solution and undergoes a series of
characteristic of color change.
 Silver chloride has the largest solubility product of any of the precipitating anions of
Group IV.
 AgCl is soluble in ammoniacal silver nitrate.
 Silver thiocyante will react with a solution of ferric chloride.
 The bromide and iodide ions are converted from insoluble silver salts to soluble zinc
salts in the reaction.there
 The iodide and bromide ions are oxidized to the free elements and identified by the
characteristic color of their carbon tetrachloride solutions.
 In the preliminary test, solution must be acid.
 Silver acetate, the group reagent, precipitates Ag2S2O3 which is a white precipitate
when first formed. It rapidly undergoes hydrolysis, with possible color changes to
black Ag2S.
 Silver acetate is not very soluble.
 Black precipitate of Ag2S, white precipitate of AgCl or AgCNS, AgBr is craem-
colored, AgI is yellow.
 AgCl is readily soluble in ammoniacal silver nitrate.
 AgCNS is only slightly soluble in ammonia water.
 Zinc reduces Ag+ in AgBr and AgI, depositing Ag and brining Br- and I- into solution.
 The centrifugate should be acid from the previous treatment.