INORGANIC PRESENTATION TOPIC: THEORITICAL ASPECTS OF ANIONS SUBMITTED BY: NIDHI CHAUDHARY B.

Sc(H) CHEMISTRY VI SEMESTER

QUALITATIVE INORGANIC ANALYSIS

It is the analysis (i.e. detection and identification) of the cations and anions present in given compound or salt mixture.

IDENTIFICATION OF ANIONS AND CATIONS

Identification of anions/cations is done through a series of tests, broadly divided into : Preliminary tests : provide us with the idea of the cation/anion present in the compound. Confirmatory tests : confirm the presence of the cation/anion in a given compound.

ANIONS

Anion is an ion with more electrons than protons, giving it a net negative charge (since electrons are negatively charged and protons are positively charged). Anions are contributed by acids, therefore, they are called as acid radicals. For example, the anion (or acid radical) Clin a water solution of salt sodium chloride (NaCl) comes from the hydrochloric acid (HCl) and the cation (or basic radical) Na+ from the base sodium hydroxide (NaOH).

PREPARING TEST SOLUTIONS

Most of the confirmatory tests of the cations/anions are not carried out with the solid mixture but with their solutions : Water Extract: If the given compound is soluble in water, then 1-2 g of mixture is dissolved in distilled water (10-20 ml). Sodium Carbonate (soda) Extract: If the compound is insoluble in water, then 1 g of mixture is taken along with 2 g Na2CO3 in distilled water (15-20 ml) and heated for 15 minutes. Solution is filtered and the filterate is soda extract.

CLASSIFICATION OF ANIONS
Anions can not be classified into specific groups but their action with sulphuric acid divides them into three categories: Dilute Sulphuric Acid: CO32-, NO2-, CH3COO-, S2-, SO32 Conc. Sulphuric Acid: Cl-, Br-, I-, NO3-, Independent Radicals: SO42-,PO43,BO33-, C2O42-

SNo

EXPERIMENT

OBSERVATIONS

INFERENCE

1.

TEST FOR CARBONATE (CO32-) Pre. Test : To a pinch of mixture add few drops of dilute sulphuric acid.

Colorless gas evolves with brisk effervescence. 2 H+ + CO32H2O + CO2

May be CO32- .

Con. Test : Pass the gas evolved in the above step through lime water.

Lime water turns milky. M(OH)2 + CO2 MCO3 + H2O

CO32confirmed.

SNo. 2.

EXPERIMENT TEST FOR NITRITE (NO2-) Pre. Test : To a pinch of mixture in test tube, add dilute sulfuric acid.

OBSERVATIONS

INFERENCE

Con. Test : (a) To the above solution, add 0.5 ml of potassium iodide solution followed by 0.5 ml of pure starch solution.

Reddish brown vapors observed. May be NO2- . 2MNO2 + H2SO4 M2SO4 + HNO2 3MNO2 H20 + HNO3 + NO NO + O2 NO2 (brown fumes) A deep blue coloration NO2- confirmed. observed. 2KI + 2MNO2 + H2SO4 K2SO4 + I2 + NO + H2O I2 + STARCH BLUE COLORED COMPLEX A dark brown or black coloration obtained. MNO2 + H2SO4 MSO4 + HNO2 HNO2 HNO3 + NO FeSO4 + NO FeSO4.NO NO2- confirmed.

(b) Take water extract or soda extract of the compound and add dilute sulfuric acid followed by freshly prepared ferrous sulphate solution.

SNo. 3.

EXPERIMENT TEST FOR ACETATE (CH3COO-) Pre. Test : A pinch of mixture is treated with dilute sulphuric acid . OR, 1-1.5 g of mixture is taken in watch glass to which a pinch of oxalic acid and a few drops of water were added.

OBSERVATIONS

INFERENCE

Vinegar like smell is obtained. M(CH3COO) + H2SO4 CH3COOH + MSO4

May be CH3COO- .

Vinegar like smell is obtained.

Con. Test: (a) 1 ml of water/soda extract is neutralized with dilute acetic acid followed by addition of ferric chloride solution.

Deep red colored precipitate is observed due to formation of a complex. CH3COO- + Fe3+ + H2O [Fe3(OH)2(CH3COO)6]+ + 2H+ [Fe3(OH)2(CH3COO)6]+ + H2O CH3COOH + [Fe(OH)2(CH3COO)] + H+

CH3COO- confirmed.

SNo.

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OBSERVATIONS

INFERENCE

(b)

To 1 ml of water/soda Blue color is obtained. extract lithium nitrate solution and potassium iodide solution were added. After this, few drops of dilute ammonia solution was added and the resultant solution was heated. Equal volume of soda/water extract and pure calcium hydroxide is taken in a test tube. Heat the solution and pass the evolved vapors into a solution of 2,4 DNP hydrazine.

CH3COOconfirmed.

(c)

Yellow precipitate is obtained. Ca(OH)2 + M(CH3COO) CH3COCH3 CH3COCH3 + H2NHC6H5(NO2) (CH3)2CNNHC6H5(NH2)2

CH3COOconfirmed.

SNo. 4.

EXPERIMENT TEST FOR SULPHIDE (S2-) Pre. Test: Take a pinch of mixture in a test tube and add dilute sulphuric acid.

OBSERVATIONS

INFERENCE

A colorless gas evolves which smells like rotten egg. S2- + H2SO4 H2S + SO42Yellow precipitate is obtained. Cd(CH3COO)2 + H2S + CH3COOH

May be S2- .

Con Test: a) Pass the above gas in cadmium acetate.

S2- confirmed.
CdS

(b)

(c)

Acidify 1-2 ml of soda/water extract with dilute acetic acid and boil the solution to expel carbon dioxide. To this add 1-2 ml of lead acetate solution. Add 1-2 ml of freshly prepared sodium nitroprusside solution to the soda/water extract.

Black precipitate obtained. H2S + Pb(CH3COO)2 PbS + CH3COOH

S2- confirmed.

Violet coloration obtained. S2- + Na2[Fe(CN)5NO] Na4[Fe(CN)5NOS]

S2- confirmed.

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EXPERIMENT

OBSERVATIONS

INFERENCE

5.

TEST FOR SULPHITE (SO32-) Pre. Test: Take a pinch of mixture and add 2-3 ml of dilute sulphuric acid.
Con.Test: (a) Take 1-2 ml of soda/water extract; add 2-3 ml of dilute sulphuric acid and few drops of potassium dichromate solution.

A colorless and pungent smelling gas evolves.

May be SO32-

A green color is obtained. 3Na2SO3 + K2Cr2O7 + 4H2SO4 Cr2(SO4)3 (Green color) + 3Na2SO4 + 4H2O + K2SO4

SO32- confirmed.

(b)

Take a pinch of mixture and add 2-3 ml of dilute hydrochloric acid.

Sulphur dioxide is evolved.

SO32- confirmed.

Pass the gas evolved through lime water.

White precipitate is obtained.

SNo

EXPERIMENT

OBSERVATIONS

INFERENCE

6.

TEST FOR CHLORIDE (Cl-) Pre Test: To a pinch of mixture, add 1-2 ml of conc. sulphuric acid. Bring a glass rod dipped in ammonium hydroxide near the mouth of the above test tube. Con. Test: (a) To the water/soda extract, add dilute nitric acid and few drops of silver nitrate.

Greenish yellow gas having May be Cl- . pungent smell evolves. Dense white fumes observed. NaCl + H2SO4 NaHSO4 + HCl HCl + NH4OH NH4Cl + H2O White precipitate formed which is soluble in excess of ammonium hydroxide. AgNO3 + NaCl AgCl + NaNO3 AgCl + 2NH4OH [Ag(NH3)2Cl] (soluble complex) + 2H2O Cl- confirmed.

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EXPERIMENT

OBSERVATIONS

INFERENCE

(b)

Chromyl Chloride Test Take about 0.2 g of mixture in a test tube and add about 0.3 g of solid potassium dichromate and 2 ml of conc. sulphuric acid. Heat the mixture and pass the gas evolved into a tube containing sodium hydroxide solution. Add 1 ml of lead acetate solution.

Yellow precipitate is formed. Cl- confirmed. K2Cr2O7 + 4NaCl + 6H2SO4 2CrO2Cl2 (chromyl chloride) + 2KHSO4 + 4NaHSO4 + 3H2O
CrO2Cl2 + 4NaOH Na2CrO4 + 2NaCl + 2H2O Na2CrO4 + Pb(CH3COO)2 PbCrO4 (yellow) + 2CH3COONa

SNO 7.

EXPERIMENT TEST FOR BROMIDE (Br-) Pre. Test: To a pinch of mixture, add conc. sulphuric acid.

OBSERVATIONS

INFERENCE

Reddish brown vapors with a pungent smell evolved. KBr + H2SO4 KHSO4 + HBr 2HBr + H2SO4 Br2 + SO2 + 2H2O

May be Br-.

Con Test: (a) Take 0.5 ml of soda/water extract and then add 0.5 ml of dilute nitric acid and few drops of silver nitrate solution.

Yellow precipitate obtained Br confirmed. which is sparingly soluble in ammonium hydroxide. NaBr + AgNO3 AgBr + NaNO3 AgBr + 2NH4OH [Ag(NH3)2]Br + 2H2O

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EXPERIMENT

OBSERVATIONS

INFERENCE

(b)

Take 0.5 ml of soda/water extract of the mixture and add 0.5 ml of carbon tetrachloride or chloroform followed by 1 ml of conc. nitric acid or chlorine water. Warm the mixture and shake the test tube.

Organic solvent layer attains orange color due to dissolution of evolved bromine in it. NaBr + HNO3 NaNO3 + HBr 2HBr + 2HNO3 Br2 + 2NO2 + 2H2O

Br- confirmed.

SNO

EXPERIMENT

OBSERVATIONS

INFERENCE

8.

TEST FOR IODIDE (I-) Pre. Test: To a pinch of mixture, add conc sulphuric acid.

Violet vapors of iodine evolved due to partial decomposition of the formed HI. KI + H2SO4 KHSO4 + HI 2HI + H2SO4 I2 + SO2 + 2H2O

May be I-.

I- confirmed. Con Test: (a) Take 0.5 ml of soda/water extract and then add 0.5 ml of dilute nitric acid followed by 0.5 ml of silver nitrate solution. Yellow precipitate obtained which is insoluble in ammonium hydroxide. NaI + AgNO3 AgI + NaNO3

SNO

EXPERIMENT

OBSERVATIONS

INFERENCE

(b)

Take 0.5 ml of soda/water extract of the mixture and add 0.5 ml of carbon tetrachloride or chloroform followed by 1 ml of conc. Nitric acid or chlorine water. Warm the mixture and shake the test tube vigorously.

Organic solvent layer attains violet color due to dissolution of iodine in it. NaI + HNO3 NaNO3 + HI 4HI + O2 2I2 + 2H2O

I- confirmed.

SNO

EXPERIMENT

OBSERVATIONS

INFERENCE

9.

TEST FOR NITRATE (NO3-) Pre. Test: To a pinch of Light brown fumes mixture, add conc sulphuric observed which intensify acid. on heating the mixture with copper turnings. NaNO3 + H2SO4 NaHSO4 + HNO3 4HNO3 4NO2 + O2 + 2H2O A brown black ring at the junction of two layers is formed. NaNO3 + H2SO4 NaHSO4 + HNO3 2HNO3 + 6FeSO4 + 3H2SO4 3Fe2(SO4)3 + 2NO + 4H2O FeSO4 + NO FeSO4.NO(brown ring)

May be NO3-

NO3- confirmed.

Con Test: Take around 1 ml of soda/water extract and acidify with dilute sulphuric acid. Add 2-3 ml of freshly prepared ferrous sulphate solution and then pour conc. sulphuric acid slowly in thin stream along the sides of the test tube.

SNO

EXPERIMENT

OBSERVATIONS

INFERENCE

10.

TEST FOR OXALATE (C2O42-) Pre. Test: Add conc sulphuric acid(1-2 ml) to a pinch of given mixture(0.1 g) and heat the solution. Bring the mouth of the test

tube near the flame.

Also pass the gas in the lime water.

Evolved gas burns with a blue flame. (COONa)2 + H2SO4 Na2SO4 + (COOH)2 (COOH)2 CO + CO2 + H2O
Lime water turns milky.

May be C2O42-.

Con Test: (a) Acidify 1 ml of soda/water extract of the mixture with dilute acetic acid and boil the solution. Then add 1 ml of calcium chloride solution and shake the test tube.

White precipitate obtained. (COONa)2 + H2SO4 Na2SO4 + (COOH)2 (COOH)2 + CaCl2 (COO)2Ca + 2HCl

SNO

EXPERIMENT Dissolve the precipitate in

OBSERVATIONS Pink color of potassium permanganate gets discharged. (COO)2Ca + H2SO4 (COOH)2 + CaSO4 2KMnO4 + 3H2SO4 + 5(COOH)2 2MnSO4 + K2SO4 + 10CO2 + 8H2O

INFERENCE C2O42- confirmed.

minimum quantity of dilute sulphuric acid and then add potassium permanganate solution drop wise.

(b)

Acidify soda/water extract with dilute acetic acid and boil the solution. Add ferrous sulphate solution.

Yellow precipitate obtained. C2O42- + Fe2+ [Fe(C2O4)]2-

C2O42- confirmed.

SNO 11.

EXPERIMENT TEST FOR FLUORIDE (F-) Pre. Test: Take 0.1 g of the mixture and add 1 ml of

OBSERVATIONS

INFERENCE

conc. sulphuric acid.

Oily droplets are formed along the sides of the test tube. 2NaF + H2SO4 Na2SO4 + 2HF

May be F-

F- confirmed. Con Test: Add a pinch of sand to the above reaction mixture. Heat it. Bring a glass rod moistened with water near the mouth of the test tube. White gelatinous deposit on the glass rod observed. 4NaF + H2SO4 + SiO2 SiF4 + 2Na2SO4 + 2H2O 3SiF4 + 4H2O H4SiO4 + 2H2SiF6 (hydrofluorosilicic acid; waxy appearance)

SNO 12.

EXPERIMENT TEST FOR SULPHATE (SO42-) To the soda/water extract (1 ml) add dilute hydrochloric acid (1 ml) so as to remove the carbonate (if present). Add 1 ml of barium chloride solution.

OBSERVATIONS

INFERENCE

White precipitate obtained which is insoluble in conc hydrochloric acid. Na2SO4 + BaCl2 BaSO4 + 2NaCl

SO42- confirmed.

13.

TEST FOR PHOSPHATE (PO43-) Take a pinch of the given mixture in a test tube and add about 1 ml of conc nitric acid. Boil the contents and add excess of ammonium molybdate solution.

PO43- confirmed. Yellow precipitate is obtained. PO43- + 12MoO42- + 24H+ PMo12O403- + 12H2O

SNO 14.

EXPERIMENT TEST FOR BORATE (BO33-) In a porcelain dish, take a small amount of the mixture, say 0.2-0.3 g, and add nearly 1 ml of conc sulphuric acid followed by 1 ml of ethyl alcohol. Heat the dish and bring a burning paper over it.

OBSERVATIONS

INFERENCE

Green flame is observed. Na3BO3 + 3H2SO4 Na2SO4 + 2H3BO3 H3BO3 + C2H5OH B(OC2H5)3 + H2O

BO33- confirmed.