ANALYTICAL CHEMISTRY

Fill in the blanks:

1. If metal ions of group III are precipitated by NH4Cl and NH4OH without prior oxidation by
conc. HNO3 is not completely precipitated. (1984-1 Mark)

2. The formula of the deep red liquid formed on warming dichromate with KCI in concentrated
sulphuric acid is. (1993-1 Mark)

True / False:

1. Addition of ammonium chloride to a solution containing ferric and magnesium ions is

essential for selective precipitation of ferric hydroxide by aqueous ammonia.
(1985-1/2 Mark)

2 From the solution containing copper (+2) and zinc(+2) ions, copper can be selectively
precipitated using sodium sulphide. (1987-1 Mark)

Multiple Choice Questions with ONE correct answer:

1. The ion that cannot be precipitated by both HCI and H2S is

(a) Pb2+ (b) Cu+
+
(c) Ag (d) Sn2+ (1982-1 Mark)

2. Which one among the following pairs of ionscannot be separated by H 2S in dilute

hydrochloric acid?
(a) Bi3+, Sn4+ (b) Al3+, Hg2+
2+ 2+
(c) Zn , Cu (d) Ni2+, Cu2+ (1986-1 Mark)

3. Read the following statement and explanation and answer as per the options given below:
Assertion: A very dilute acidic solution of Cd2+ and Ni2+ gives yellow precipitate of CdS
passing hydrogen sulphide.
Statement: Solubility product of CdS is more than that of NiS.
(a) If both assertion and statement are correct and statement is an explanation of assertion.
(b) If assertions correct and statement is wrong, statement is not an explanation of assertion.
(c) If assertion is wrong and statement is correct, statement is not an explanation of
assertion.
(d) If both assertion and statement are wrong and statement is not explanation of assertion.
(1989-2 Marks)

4. An aqueous solution contains Hg 2 , Hg 22 , Pb 2 and Cd 2 . The addition of HCl(6N) will

precipitate
(a) Hg2Cl2 only (b) PbCl2 only
(c) PbCI2 and Hg2Cl2 (d) PbCI2 and Hg2Cl2 (1995-1 Mark)

5. The only cations present in a slightly acidic solution are Fe3+, Zn2+ and Cu2+. The reagent
when added in excess to this solution would identify the separate Fe3+ in one step is
(a) 2 M HCI (b) 6 M NH3
(c) 6 M NaOH (d) H2S gas (1997-1 Mark)

6. Read the following statement and explanation and answer as per the options given below:
Assertion: Sulphate is estimated as BaSO4 and not as MgSO4.
Reason: Ionic radius of Mg2+ is smaller than that of Ba2+.
(a) If both assertion and reason are correct, and reason is the correct explanation of the
assertion.
 Analytical Chemistry 2

(b) If both assertion and reason are correct, but reason is not the correct explanation of the
assertion.
(c) If assertion is correct but reason is incorrect.
(d) If assertion is incorrect but reason is correct (1998-2 Marks)

7. Identify the correct order of solubility of Na2S, CuS and ZnS in aqueous medium
(a) CuS > ZnS > Na2S (b) ZnS > Na2S > CuS
(c) Na2S > CuS > ZnS (d) Na2S > ZnS > CuS (2002-Scr.)

8. An aqueous solution of a substance gives a white precipitate on treatment with dilute

hydrochloric acid, which dissolves on heating. When hydrogen sulfide is passed through the
hot acidic solution, a black precipitate is obtained. The substance is a
(a) Hg 22 salt (b) Cu 2 salt
(c) Ag+ salt (d) Pb 2 salt (2002-Scr.)

9. A gas X is passed through water to form a saturated solution. The aqueous solution on
treatment with silver nitrate gives a white precipitate. The saturated aqueous solution also
dissolves magnesium ribbon with evolution of a colourless gas Y. Identify X and Y.
(A) X = CO2, Y = Cl2 (B) X = Cl2, Y = CO2
(C) X = Cl2, Y = H2 (D) X = H2, Y = Cl2 (2002-Scr.)

10. X H 2SO 4 Y a colourless gas with irritating smell,

Y K 2 Cr2 O7 H 2SO 4 green solution. X and Y is
(A) SO32 ,SO 2 (B) Cl , HCl
(C) S , H 2S (D) CO32 ,CO 2 (2003-Scr.)

11. A solution which is 103 M each in Mn2+, Fe2+, Zn2+ and Hg2+ is treated with 1016 M sulphide
ion. If Ksp of MnS, FeS, ZnS and HgS are 1015, 1023, 1020 and 1054 and respectively, which
one will precipitate first?
(a) FeS (b) MgS
(c) HgS (d) ZnS (2003-Scr.)

12. A metal nitrate reacts with KI to give a black precipitate which on addition of excess of KI is
converted into orange colour solution. The cation of the metal nitrate is
(a) Hg2+ (b) Bi3+
2+
(c) Pb (d) Cu+ (2005-Scr.)

Multiple Choice Questions with ONE MORE THAN ONE correct answer:

1. The reagents, NH4Cl and aqueous NH3 will precipitate

(a) Ca2+ (b) AI3+
3+
(c) Bi (d) Mg2+
2+
(e) Zn (1991-1 Mark)

2. Which of the following statement(s) is (are) correct when a mixture of NaCl and K 2Cr2O7 is
gently warmed with conc. H2SO4?
(a) A deep red vapour is evolved
(b) The vapours when passed into NaOH solution gives a yellow solution of Na2CrO4
(c) Chlorine gas is evolved
d) Chromyl chloride is formed (1998-2 Marks)

3. Which of the following statement(s) is (are) correct with reference to the ferrous and ferric
ions?
(a) Fe3+ gives brown colour with potassium ferricyanide.
 Analytical Chemistry 3

(b) Fe2+ gives blue precipitate with potassium ferricyanide.

(c) Fe3+ gives red colour with potassium thiocyanate.
(d) Fe2+ gives brown colour with ammonium thiocyanate. (1998-2 Marks)

Subjective Problems: students are advised to attempt the questions, marked with in second
round

1. When 16.8 g of white solid X were heated, 4.4 g of acid gas A that turned lime water milky
driven off together with 1.8 g of a gas B which condensed to a colourless liquid. The solid
that remained, Y, dissolved in water to give an alkaline solution, which with excess barium
chloride solution gave a white precipitate Z. The precipitate effervesced with acid giving off
carbon dioxide Identify A, B and Y and write down the equation for the thermal
decomposition of X. (1984-4 Marks)
2. A mixture of two salts was treated as follows:
(i) The mixture was heated with manganese dioxide and concentrated su.lphuric acid when
yellowish green gas was liberated.
(ii) The mixture on heating with sodium hydroxide solution gave a gas which turned red
litmus blue.
(iii) Its solution in water gave blue precipitate with potassium ferricyanide and red colouration
with ammonium thiocyanate.
(iv) The mixture was boiled with potassium hydroxide and the liberated gas was bubbled
through an alkaline solution of K2HgI4 to give brown precipitate. Identify the two salts.
Give ionic equations for reactions involved in the tests (i), (ii) and (iii). (1987-5 Marks)

3. A hydrated metallic salt A, light green in colour, on careful heating gives a white anhydrous
residue B. B is soluble in water and its aqueous solution reacts with NO to give a dark
brown compound C. B on strong heating gives a brown residue D and a mixture of two
gases E and F. The gases mixture when passed through acidified permanganate, discharges
the pink colour and when passed through acidified BaCI2 solution gave a white precipitate.
Identify A, B, C, D, E and F. (1988-3 Marks)

4. When 20.02 g of a white solid X is heated 4.4 g of an acid gas A and 1.8 g of a neutral gas B
evolved, leaving behind a solid residue Y of weight 13.8 g. A turns lime water milky and B
condenses into a liquid which changes anhydrous copper sulphate blue. The aqueous
solution of Y is alkaline to litmus and gives 19.7 g of white precipitate Z with barium chloride
solution. Z gives carbon dioxide with an acid. Identify A, B, X, Y and Z. (1989-5 Marks)

5. The gas liberated on heating a mixture of two salts with NaOH, gives a reddish brown
precipitate with an alkaline solution of K2HgI4. The aqueous solution of the mixture on
treatment with BaCl2 gives a white precipitate which is sparingly soluble in conc. HCI. On
heating the K2Cr2O7 and conc. H2SO4 red vapours A are produced. The aqueous solution of
the mixture given a deep blue colouration B with potassium ferricyanide solution. Identify the
radicals in the gives mixture and write the balanced equations for the formation of A and B.
(1991-4 Marks)

6. A light bluish green crystalline compound responds to the following tests:

(i) Its aqueous solution gives a brown precipitate or colour with alkaline K2[HgI4] solution.
(ii) Its aqueous solution gives a blue colour with K3[Fe(CN)6] solution.
(iii) Its solution in hydrochloric acid gives a white precipitate with BaCI2 solution. Identify the
ions present and suggest the formula of the compound. (1992-4 Marks)

7. An orange solid (A) on heating gave a green residue (B), a colourless gas (C) and water
vapour. The dry gas (C) on passing over heated Mg gave a white solid (D). (D) on reaction
with water, a gas (E) which formed dense white fumes with HCI. Identify (A) to (E) and give
reactions involved. (1993-3 Marks)
 Analytical Chemistry 4

8. A is a binary compound of a univalent metal 1.422 g of A reacts completely with 0.321 g of

sulphur in an evacuated and sealed tube to give 1.743 g of a white crystalline solid B, that
for hydrated double salt, C with Al2(SO4)3 Identify A, B and C. (1994-5 Marks)

9. A scarlet compound A is treated with conc. HNO 3 to give a chocolate brown precipitate B.
The precipitate is filtered and the filtrate is neutralized with NaOH. Addition of KI to the
resulting solution gives a yellow precipitate C. The precipitate B on warming with conc. HNO 3
in the presence of Mn(NO3)2 produces a pink-coloured solution due to the formation of D.
Identify A, B, C and D. Write the reaction sequence. (1995-4 Marks)

10. Calcium burns in nitrogen to produce a white powder which dissolves in sufficient water to
produce a gas (A) and an alkaline solution. The solution on exposure to air produces a thin
solid layer of (B) on the surface. Identify the compounds A and B. (1996-2 Marks)

11. A colourless inorganic salt (A) decomposes completely at about 250C to give only two
products, (B) and (C), leaving no residue. The oxide (C) is a liquid at room temperature and
neutral to moist litmus paper while the gas (B) is a neutral oxide. White phosphorus burns in
excess of (B) to produce a strong white dehydrating agent. Write balanced equations for the
reactions involved in the above process. (1996-3 Marks)

12. During the qualitative analysis of a mixture containing Cu 2+ and Zn2+ ions, H2S gas is passed
through an acidified solution containing these ions in order to test Cu2+ alone. Explain briefly.
(1998-2 Marks)

13. A white solid is either Na2O or Na2O2. A piece of red litmus paper turns white when it is
dipped into a freshly made aqueous solution of the white solid.
(i) Identify the substance and explain with balanced equation.
(ii) Explain what would happen to the red litmus if the white solid were the other compound.
(1999-4 Marks)

14. An aqueous solution containing one mole of HgI2 and two moles of NaI is orange in colour.
On addition of excess NaI the solution becomes colours. The orange colour reappears on
subsequent addition of NaOCl. Explain with equations. (1999-3 Marks)

15. An aqueous blue coloured solution of a transition metal sulphate reacts with H 2S in acidic
medium to give a black precipitate A, which is insoluble in warm aqueous solution of KOH.
The blue solution on treatment with KI in weakly acidic medium, turns yellow and produces a
white precipitate B. Identify the transition metal ion. Write the chemical reactions involved in
the formation of A and B. (2003-4 Marks)

16. Write the chemical reactions associated with the borax bead test of cobalt (II) oxide.
(2003-3 Marks)

17. A white substance (A) reacts with dilute H2SO4 to produce a colourless gas (B) and a
colourless solution (C). The reaction between (B) and acidified K 2Cr2O7 solution produces a
green solution and a slightly coloured precipitate (D). The substance (D) burns in air to
produce a gas (E) which reacts with (B) to yield (D) and a colourless liquid. Anhydrous
copper sulphate is turned blue on addition of this colourless liquid. Addition of aqueous NH 3
or NaOH to (C) produces first a precipitate, which dissolves in the excess of the respective
reagent to produce a clear solution in each case. Identify (A), (B), (C), (D) and (E). Write the
equations of the reactions involved. (2001-10 Marks)
 Analytical Chemistry 5

18. When a white crystalline compound X is heated with K 2Cr2O7 and concentrated H2SO4 a
reddish brown gas A is evolved. On passing A into caustic soda solution, a yellow coloured
solution of B is obtained. Neutralizing the solution B with acetic acid and on subsequent
addition of lead acetate, a yellow precipitate C is obtained. When X is heated with NaOH
solution, a colourless gas is evolved and on passing this gas into K 2HgI4 solution, a reddish
brown precipitate D is formed. Identify A, B, C, D and X. Write the equations of reactions
involved. (2002-5 Marks)

19. A mixture consists of A (yellow solid) and B (colourless solid) which gives lilac colour in
flame.
(a) Mixture gives black precipitate C on passing H2S(g) through its aqueous solution.
(b) C is soluble in aqua-regia and on evaporation of aqua-regia and adding SnCl 2 gives
greyish black precipitate D.
The salt solution with NH3 gives a brown precipitate.
(i) The sodium extract of the salt with CCI4/FeCl3 gives a violet layer.
(ii) The sodium extract gives yellow precipitate with AgNO 3 solution which is insoluble in NH3
identify A and B, and the precipitates C and D. (2003-4 Marks)
 Analytical Chemistry 6

ANSWERS

A 1. Fe3+ 2. CrO2Cl2

B 1. T 2. T

C 1. (d) 2. (a) 3. (b) 4. (c)

5. (b) 6. (b) 7. (d) 8. (d)
9. (c) 10. (a) 11. (c) 12. (b)

D 1. (a, b) 2. (a, b, d) 3. (b, c)

E 1. CO2, H2O, Na2CO3 2. FeCl2, NH4Cl

3. FeSO4.7H2O, FeSO4.NO, Fe2O3, SO2, SO3
4. CO2, H2O, KHCO3, K2CO3, BaCO3
5. NH4+, Fe2+, SO42, Cl
6. NH4+, Fe2+, SO42, FeSO4. (NH4)2SO4.6H2O
7. (NH4)2Cr2O7, Cr2O3, N2, Mg3N2, NH3
8. KO2, K2SO4, Al2(SO4)3
9. Pb3O4, PbO2, PbI2
10. NH3, CaCO3
13. (i) Na2O2, (ii) turns blue
15. Cu2+
17. ZnS, H2S, ZnSo4, S, SO2
18. CrO2Cl2, Na2CrO4, PbCrO4, iodide of Millons base NH4Cl
19. HgI2, KI, HgS, Hg