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Cations

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Submitted By ernestmagier
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Cations are divided into six groups. A specific reagent for each group is used for their separation from the solution. This separation is done in a particular sequence because some ions of prior groups can also react with the reagent of later groups.

This can be cause of difficulty in their separation. The qualitative analysis of cations depends on the solubility products of the ions. The cations get precipitated on the optimum needed concentration and easily detected.

1st group of cations

The group (I) cations form the insoluble chlorides. The dilute hydrochloric acid (generally 1-2 M concentration) is used as the group reagent. The Concentrated HCl is not used because it forms a soluble complex ion ([PbCl4]2-) with Pb2+ and would not be detected. The most important cations of 1st group are Ag+, Hg22+, and Pb2+. Color detection test is not suitable for their chlorides because all are white solid compounds. The analyzing of group is done by adding the respective salt into water and follow it with dilute HCl. This results in a white precipitate in which NH4OH is added. The insoluble precipitate shows the presence of Plumbous (Pb2+) and if precipitate is soluble, then it shows the presence of Argentous (Ag+).If the white precipitate turns black, it shows the presence of Hg22+.

The obtained filtrate after first group analysis is used for the test of second group. Usually Pb2+ is also included in the 2nd analytical group because the solubility of PbCl2 is more than the chlorides of other two ions.

Confirmation Test

For lead

Pb2+ + 2KI → PbI2 + 2 K+
Pb2+ + K2CrO4 → PbCrO4 + 2K+

For Silver

Ag+ + KI → AgI + K+
2Ag+ + K2CrO4 → Ag2CrO4 + 2K+

For mercury ion

Hg22++ 2KI → Hg2I2 + 2K+
2Hg22+ + 2NaOH → 2Hg2O + 2Na+ + H2O

2nd analytical group of cations

The ions of this group form acid-insoluble sulfides. Cations of the 2nd group are Cd2+, Bi3+, Cu2+, As3+, As5+, Sb3+, Sb5+, Sn2+, Sn4+ and Hg2+. The group reagent is H2S (at 0.2 - 0.3 M) which gives S2− ions in solutions. The tests are conducted in presence of dilute HCl to keep the S2- ion concentration at a minimum level. This round of tests helps only in second 2nd group cations precipitation. The cations precipitation of the 4th group if present in the solution might occur in the absence of dilute HCl which can give wrong results. The use of sulfuric acid and nitric acid can cause to the precipitation of the 4th group cations and formation of colloidal sulfur respectively. This group is determined by the addition of the respective salt in water and then adding dilute HCl and then follow it by adding H2S. The precipitate color and the presence of the respective ions are shown in the table below.

Precipitate color | Presence of cation | Reddish brown or black precipitate | Bi3+, Cu2+, Hg2+ or Pb2+ | Yellow precipitate | Cd2+ or Sn4 | Brown precipitate | Sn2+ | Red orange | Sb3+ |

* If the black or reddish brown precipitate comes, then it is boiled in diluted HNO3. If the precipitate is insoluble in diluted HNO3 then Hg2+ is present. * If it is soluble, then Cu2+, Bi3+ or Pb2+ can be present- I this solution sulfuric acid is then added. A white precipitate shows that Pb2+ may be present; * If no any precipitate forms, then an excess of ammonium hydroxide in the original salt solution is added. A blue color indicates the presence of Cu2+ while a white precipitate indicates bismuth. * For the yellow precipitate, an excess of NaOH is added to form a white precipitate. If the white precipitate dissolves, then Sn4+ is present; if it’s not then Cd2+ is present.

Confirmation Test

For Lead

Pb2+ + 2 KI → PbI2 + 2K+
Pb2+ + K2CrO4 → PbCrO4 + 2K+

For Copper

2Cu2+ + K4[Fe(CN)6] + CH3COOH → Cu2[Fe(CN)6] + 4K+
Cu2+ + 2NaOH → Cu(OH)2 + 2Na+
Cu(OH)2 → CuO + H2O (endothermic)

For Bismuth

Bi3+ + 3KI (in excess) → BiI3 + 3K+
BiI3 + KI → K[BiI4]
Bi3+ + H2O (in excess) → BiO++ 2H+

Confirmation test for Mercury

Hg2+ + 2KI (excess) → HgI2 + 2K+ HgI2 + 2KI → K2[HgI4] (red precipitate)
2Hg2+ + SnCl2 → 2Hg + SnCl4 (gray white precipitate)

3rd analytical group of cations

The ions of this group form insoluble hydroxides. Cations in the 3rd group are Fe2+, Fe3+, Al3+, and Cr3+. The group detection is carried out by preparing a respective salt solution in water and then adding NH4Cl and NH4OH. If a reddish brown precipitate forms then Fe3+ is present, agelatinous white precipitate shows Al3+, and a green precipitate is for Cr3+ or Fe2+. The Cr3+ or Fe2+ is identified by adding excess of sodium hydroxide to the green precipitate. The soluble precipitate indicates Fe2+, otherwise Cr3+ is present.

4th analytical group of cations

This includes Zn2+, Ni2+, Co2+, and Mn2+. For determination of this group, the solution of the salt is mixed with NH4Cl, NH4OH, and H2S gas. A green color of the original solution is for Co2+.

The color and the presence of the other respective ions are shown in the table below.

Precipitate color | Presence of cation | Colored precipitate | Mn2+ | White precipitate | Zn2+ | Black precipitate | Ni2+ |

5th analytical group of cations

Ions of 5th group of cations forms the carbonates which are insoluble in water. The (NH4)2CO3 (Approx 0.2 M concentration) is group reagent with a neutral or slightly basic pH. The ions of the 5th group are Ba2+, Ca2+, and Sr2+. The most common way to detect them is flame test. The color of flame for particular ion is shown in table.

Ions | Color of flame | Barium | Yellow-green flame | Calcium | orange red | Strontium | deep red |

In the flame test, the solutions of ions mixed with concentrated HCl and heated on a nickel/chromium wire in a flame. Due to the presence of particular atom, the flame gives a characteristic color.

6th analytical group of cations

The ions of 6th group are Mg2+, Li+, Na+, K+ and NH4+. The NH4+ ion after reacting with Nessler's reagent gives a brown colored precipitate. The rest of the ions are identified by flame color which is shown in table.

Ions | Color of flame | lithium | Red flame | Sodium | bright yellow | Potassium | Violet | Magnesium | Bright white |

Qualitative Data Analysis
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Qualitative Data Analysis (QDA) is the series of processes and procedures which based on an interpretative philosophy.
In QDA, all the meaningful and symbolic content of collected qualitative data are investigated.

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