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Question

The gas liberated on heating a mixture of two salts with NaOH, give a reddish brown precipitate with an alkaline solution of K2Hgl4. The aqueous solution of the mixture on treatment with BaCl2 gives a white precipitate which is sparingly soluble in concentrated HCl. On heating the mixture with K2Cr2O7 and concentrated H2SO4, red vapour (A) are produced. The aqueous solution of the mixture gives a deep blue ppt. (B) with Potassium ferricyanide solution. Identify the radicals.

A
(A)CrO2Cl2, (B)Fe3[Fe(CN)6]2
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B
(A)CrO2Cl2, (B)Fe2[Fe(CN)6]2
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C
(A)CrO2Cl, (B)Fe3[Fe(CN)6]2
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D
(A)CrO2Cl, (B)Fe2[Fe(CN)6]2
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Solution

The correct option is A (A)CrO2Cl2, (B)Fe3[Fe(CN)6]2
Option (A) is correct.
(A) and (B) are CrO2Cl2 and Fe3[Fe(CN)6]2.
Mix a little amount of salt and an equal amount of solid potassium dichromate (K2Cr2O7 ) in a test tube and add conc.H2SO4 to it. Heat the test tube and pass the evolved gas through sodium hydroxide solution. If a yellow solution is obtained, divide the solution into two parts. Acidify the first part with acetic acid and then add lead acetate solution. Formation of a yellow precipitate of lead chromate confirms the presence of chloride ions in the salt. This test is called chromyl chloride test.
4NaCl+K2Cr2O7+6H2SO42KHSO4+2CrO2Cl2+4NaHSO4+3H2O
CrO2Cl2+4NaOHNa2CrO4+2NaCl+2H2O
Another cation is Fe3+.
Fe3++K3[Fe(CN)6]Fe3[Fe(CN)6]2+KCl

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