d-BLOCK ELEMENT

1. An inorganic lewis acid [X] gives gelatinous white precipitate with NH4OH in presence of NH4Cl and its
aqueous solution in water gives white precipitate with AgNO3 solution. [X] will respond to which of the follow-
ing characteristics ?
(A*) X fumes in moist air.
(B*) X on heating with solid K2Cr2O7 and conc. H2SO4 gives deep red fumes.
(C) X on addition of excess NaOH gives white precipitate.
(D*) X on heating with Na2CO3 and cobalt nitrate gives a blue bead in oxidising flame.
Sol. (A, B, D)
(A) AlCl3 + 3H2O  Al(OH)3 + 3HCl  (fumes)
(B) AlCl3 + K2Cr2O7 + H2SO4  Al2(SO4)3 + K2SO4 + CrO2Cl2  (deep red or orange red vapour) + H2O
(D) Gives blue bead of Al2O3 . CoO

2. STATEMENT-1 : NH4Cl is added while analysising the rd group basic radicals to suppress the ionisation of
NH4OH.
STATEMENT-2 : With high concentration of OH– ions, basic radicals of other groups are also get
precipitated with  group cations.
(A*) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2 is True
Sol. (A)
Due to common ion effect the concentrations of OH– ions is just sufficient to precipitate the cations of 
group as their hydroxides. (As they have low Ksp values).

3. To increase significantly the concentration of free Zn2+ ion in a solution of the complex ion [Zn(NH3)4]2+
Zn2+ (aq) + 4NH 3 (aq) [Zn(NH3)4]2+ (aq)
add to the solution some :
(A) H2O (B*) HCl (aq) (C) NH3(aq) (D) NH4Cl (aq)
Sol. (B)
On adding HCl the equilibrium will shift in backward direction.
4. Aqueous solution of Ni2+ first gives green ppt. which then turns black with
(A) NaHCO3 (aq.) only (B) NaHCO3 (s) and Br2 (g)
(C) NaOH (aq.) only (D) NaOH (aq.) and Br2 (water)
Sol. (D)
Sol. NiCl2 + 2NaOH (excess)  Ni(OH)2  (green) + 2NaCl
Br2 + H2O  2HBr + [O]
2Ni(OH)2 + H2O + [O]  2 Ni(OH)3  (black)

5. A coloured precipitate is obtained when H2S gas is passed through an aqueous solution of salt in presence
of ammonium hydroxide. The precipitate dissolves in dilute HCl & reacts with NaOH to give white precipitate.
which on standing turns in to a brown/black mass. The brown/black mass on fusion with KNO3 & Na2CO3
gives green mass. The cation of the salt is :
(A) Co2+ (B) Mg2+ (C) Ni2+ (D) Mn2+
Sol. (D)
NaOH
HCl
Mn2+ + H2S  MnS  (buff coloured)   
 MnO  (Brown/black)
 MnCl2 [O ] 2

fusion
MnO2 + 2KNO3 + Na2CO3 + H2O   Na2MnO4 (green mass) + KNO2 + 2NaOH + CO2

6. In which of the following test(s)/reaction(s) a green precipitate/mass is obtained as one of the reaction
products ?
(A) Reaction of chromium (III) soluble salt with ammonium hydroxide
(B) Reaction of cobalt (II) soluble salt with sodium carbonate and bromine water
(C) On heating zinc salt with cobalt nitrate and sodium carbonate in oxidising flame
(D) On fusing a mixture of manganese dioxide, potassium nitrate and sodium hydroxide

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Sol. (A, C, D)
Sol. (A) Cr3+ + 3NH4OH  Cr(OH)3  (green) + 3NH4+

(C) ZnO + Co(NO3)2  CoO.ZnO (green mass)
fusion
(D) MnO2 + KNO3 + 2NaOH   Na2MnO4 (green mass) + KNO2 + H2O

7. STATEMENT-1 : When H2S gas is passed into an aqueous solution of ZnCl2 , Zn2+ ions are completely
precipitated as zinc sulphide
STATEMENT-2 : Zinc sulphide is insoluble in solutions of caustic alkali but dissolves in dilute HCl.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement-1 is True, Statement-2 is False
(D*) Statement-1 is False, Statement-2 is True
Sol. (D)
Ksp of ZnS is large and thus is completely precipitated only in presence of ammonium hydroxide.
8. Column-I Column-II
(A) Zn(OH)2 precipitate dissolves in (P) Potassium cyanide
(B) Cr(OH)3 precipitate dissolves in (Q) Ammonia
(C) AgCl precipitate dissolves in (R) Sodium hydroxide
(D) CuS precipitate dissolves in (S) Sodium peroxidse
Ans. (A– P, Q, R) ; (B– Q, R, S) ; (C– P, Q) ; (D– P, Q, S)
Sol. (A) Zn(OH)2  4KCN  K2[Zn(CN)4] + 2KOH
colourless soluble complex
Zn(OH)2  + 4NH3  [Zn(NH3)4](OH)2
colourless soluble complex
Zn(OH)2  + 2NaOH  Na2[Zn(OH)4] (OH)2
colourless soluble complex
(B) Cr(OH)3 + 6NH3  [Cr(NH3)6]3+ + 3OH–
slightly soluble in cold pink or violet soluble complex
Cr(OH)3  + OH–  [Cr(OH)4] –
green soluble complex
2Cr(OH) 3  + 3Na2O2  2Na2CrO4 + 2NaOH + 2H2O
yellow solution
(C) AgCl + 2NH3  [Ag(NH3)2]Cl
AgCl + 2CN–  [Ag(CN)2]– + Cl–
R,S  NO
(D) 2CuS + 8CN–  2[Cu(CN)4]3– + S22– colourless soluble complex. oxidation reduction reaction.
H2 O
CuS + Na2O2  CuSO4 + NaOH
CuS  + H2O  CuSO4 soluble compound
Cu2+ reacts with KCN but not with CuS, same with NH3 and NaOH

9. Aqueous solution of light greenish crystalline compound reacts with potassium ferricyanide to give a deep
blue coloured solution or precipitate. Its chemical formula is :
(A) Fe Fe[Fe(CN)6]2 (B) Fe4[Fe(CN)6]3 (C) Fe3[Fe(CN)6]2 (D) None of these
Sol. (C)
Fe2+ + K3 [Fe(CN)6]  Fe3 [Fe(CN)6]2 + 3K+

10. Statement - 1 : Potassium hexacyanoferrate(II) solution gives intense blue (prussian blue) precipitate with
Fe3+ ions.
Statement - 2 : When iron(III) chloride is added to an excess of potassium hexacyanoferrate(II), a product
with the composition KFe[Fe(CN)6] is formed.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B*) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement-1 is True, Statement-2 is False

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 (D) Statement-1 is False, Statement-2 is True
Sol. Statement - 1 : 4Fe3+ + 3[Fe(CN)6]4–  Fe4[Fe(CN)6]3 (prussian blue)
Statement - 2 : Colloidal solution with this composition is obtained which is called as 'soluble prussian blue'.

11. Which of the following statment(s) is (are) ture :

(A) Cu2+ salts form soluble complex with excess KCN
(B) Cu2+ salts form soluble complex with aqueous ammonia
(C) Cu2+ salts form soluble complex with K
(D) A piece of iron or zinc when place in Cu2+ salt solution, precipitates copper
Sol. (A, B, D)
Sol. (C) is incorrect as with KI, Cu2+ salts form a white ppt. of Cu22

12. Column-I Column-II

(A) Bi3+ gives black ppt with (P) H2S (saturated solution in water)
(B) Cu2+ gives black ppt with (Q) Potassium thiocyanate solution
(C) Zn2+ gives white ppt with (R) Potassium iodide solution
(D) Ag+ gives white ppt with (S) Potassium ferrocyanide solution

Ans. (A–P, R) ; (B– P, Q) ; (C – P, S) ; (D – Q, S)

Sol. (A) 2Bi3+ + 3H2S  Bi2S3  Black + 6H+
Bi3+ + 3–  Bi3  Black
(B) Cu2+ + H2S  CuS  Black + 2H+
Cu2+ + 2SCN–  Cu(SCN)2  Black
First green colouration is produced which then changes to black ppt.
Cu22 is white ppt and Cu2 [Fe(CN)6] brown ppt
(C) Zn2+ + H2S  ZnS  white + 2H+
2K+ + 2[Fe(CN)6]4– + 3Zn2+  K2Zn3 [Fe(CN)6]2  white
Zn2  soluble
(D) 4Ag+ + [Fe(CN)6]4–  Ag4 [Fe(CN)6]  white
Ag+ + SCN–  AgSCN  white
Ag2S  black ; Ag  yellow

Comprehension # 2
Read the following comprehension carefully and answer the following questions.
In qualitative analysis,  group includes Fe3+, Al3+ and Cr3+ . The group reagent is ammonium hydroxide in
presence of ammonium chloride. NH4Cl is added to suppress the ionisation of NH4OH so that only the 
group radicals are precipitated as their insoluble hydroxide and not the iv th and v th group radicals as the
solubility products of their hydroxides are much higher. Before adding group reagent to the filterate of II group,
one drop of concentrated HNO3 (oxidising agent) is added and the content is boiled for 2-3 minutes and then
cool because the solubility product of Fe(OH)2 is very high as compared to Fe(OH)3.
When a light bluish green crystalline compound containing cations of III group and zero group is analysed, it
responds to following tests /reactions.
(a) Its aqeous solution gives a reddish brown precipitate with alkaline solution of potassium tetraiodomercurate
(II)
(b) Its aqueous solution after boiling with conc. HNO3 gives a reddish brown ppt. with sodium hydroxide.
(c) Solution of reddish brown ppt. in dil. HCl gives blood red colouration with ammonium sulphocyanide and
prussian blue with potassium ferrocyanide.
(d) Its very dilute solution gives white ppt. with (CH3COO)2 Pb solution and white ppt. is only soluble in hot
amonium acetate.
13. Why one ml conc. HNO3 is added to IInd group filterate before proceeding for IIIrd group radicals ?
(A) Because it oxidises the dissolved H2S to colloidal sulphur
(B) Because it oxidises Fe2+ to Fe3+ so that Fe3+ can be completely precipitated as its hydroxide
(C) Because precipitation of cations belonging to IIIrd group by group reagent takes place only in presence of
conc. HNO3
(D) None of these

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Sol. (B)
(B) As complete precipitation of Fe(OH)2 (Ksp very high) does not take place in presence of NH4Cl so it is
oxidised to Fe3+ by HNO3 and Fe(OH)3 has lower ksp which is completely separated as reddish brown ppt.

14. Identifies the correct statement :

(A) NH4Cl is added along with NH4OH so that only IIIrd group cations can be precipitated as their hydroxides
(B) In place of NH4Cl, (NH4)2 SO4 can not be used as barium (v th group radical) will also be precipitated as
BaSO4 along with Al+3 , Fe+3 & Cr+3
(C) Aqueous solution of ammonium sulphate also produces white ppt. with BaCl2 solution which is
insoluble in conc. HCl.
(D) All of these

Sol. (D)
(A) As Ksp of hydroxides of Al3+, Fe3+ & Cr3+ are low and NH4Cl suppresses the ionisation of NH4OH
(B) (NH4)2SO4 + Ba2+  BaSO4  (white) + 2NH4+
(C) SO42– + Ba2+  BaSO4  (white) as it contains SO42– as anion.

15. The reddish brown precipitate formed in (a) is of

(A) Mercury amido iodide (B) Mercury iodide
(C) Oxydimercuric amido iodide (D) Mercury amido iodide and mercury

Sol. 2K2(Hg4) + NH3 + 3KOH  HgOHgNH2 + 7KI + 2H2O.

16. (a) 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). Idenfity the transition metal ion. Write the chemical
reactions involved in the formation of (A) and (B). [JEE - 2000]
(b) Write the chemical reactions associated with the ‘borax bead test’ of copper () salt.

Sol. (a) Metal ion = Cu+2 , A = CuS, B = Cu2I2

Cu2+ (aq) + H2S (aq)  CuS(s) + 2H+ (aq)
2Cu2+ (aq) + 4I¯ (aq)  Cu2I2  + I2 ; I2 + I–  I3–

(b) Na2B4O7.10H2O  Na2B4O7   2NaBO2 + B2O3
In oxidising flame,
CuSO4  Cuo + SO3 ; Cuo + B2O3  Cu(BO2)2 (Blue bead in cold)
In reducing flame,
2Cu(BO2)2 + C  2CuBO2 + B2O3 + CO
2Cu(BO2)2 + 2C  2Cu (Brown red bead in cold) + 2B2O3 + 2CO
17. Which of the following sulphides dissolves only in aquaregia?
(A*) CoS (B*) NiS (C) CuS (D*) HgS
Sol. CuS dissolves in 50% HNO 3 .
18. Which of the following will give the same colour in oxidising flame as well as in the reducing flame in
borax bead test (when cold) :
(A*) Chromium (B) Copper (C*) Cobalt (D) Nickel
Sol. Cr = Green ; Co = Blue.
19. What happens when MnS dissolved in conc. HNO 3 is diluted with water and then a few milligram of
sodium bismuthate (NaBiO 3) is added.
(A) A yellow colour solution is obtained
(B) A buff colour ppt is obtained.
(C) A brown precipitate is obtained
(D*) A violet – red (purple) colour solution is obtained.

Sol. 2Mn+ + 5 NaBiO 3 + 14 H+  2 MnO 4– (violet – red) + 5 Bi 3+ + 5 NaI + H2O.

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20. A metal salt solution forms a yellow precipitate with potassium chromate in acetic acid, a white precipitate
with dilute sulphuric acid, but gives no precipitate with sodium chloride or iodide, it is [AIIMS 1987]
(A) Lead carbonate (B) Calcium carbonate
(C*) Barium carbonate (D) Strontium carbonate
Sol. Ksp of CaCrO 4 and SrCrO 4 are higher in acetic acid. BaCO 3 gives yellow precipitate of BaCrO 4 and
white precipitate of BaSO 4. NO precipitate with NaCl or NaI. Pb2+ gives white precipitate with NaCl and
yellow precipitate with K I.

21. Except which all reagent are used for dissolving the green precipitate of Cr(OH)3 ?
(A) Alkaline sodium perborate (B) Bromine water in alkaline solution
(C) Sodium hydroxide in excess (D*) Ammonium hydroxide
Sol. (A)  Cr ( OH )3
BO3– + 2OH–  BO33– + H2O2  2–
  CrO4
(B) 2Cr3+ + 3OBr– + 10OH–  2CrO42– + 3Br– + 5H2O
(C) Cr(OH)3 + OH–  [Cr(OH)4]–
(D) Only slightly soluble in ammonia solution.

22. A mixture upon adding conc. H2SO4 gives deepred fumes. It may contain the acid radical pair :
(A*) CrO42– + Cl– (B) Br– + Cl– (C) NO3– + Cl– (D) CrO42– + NO3–
Hint : CrO42– + H+  CrO72– ; Chromyl chloride test.

23. Which of the following is/are correct for potassium ferrocyanide ?

(A*) It gives a brown precipitate with Cu2+ ions.
(B*) It gives a white precipitate of mixed salt with Ca2+ ions.
(C*) It in excess gives a bluish white precipitate with Zn2+
(D) It develops a deep red colouration with Fe3+
Sol. (D) Gives prussian blue precipitate of Fe4[Fe(CN)6]3 with Fe3+.

24. Match the following :

Column A Column B
(i) Na + Cl 2 (water) + CCl 4 - shake (a) yellow ppt
(ii) CH3COO¯ + FeCl 3 + H2O - boil (b) green mass
(iii) CoCl 2 + KNO 2 + CH3COOH - warm (c) black ppt
(iv) MnCl 2 + KOH + KClO 3 - fusion (d) purple colour
(v) MnCl 2 + NaOH + Br2 (water) (e) red brown ppt
(vi) FeCl3 + KSCN (f) blood red colour
Sol. (i – d), (ii – e), (iii – a), (iv – b), (v – c), (vi – f)
(i) I¯ + Cl 2  2Cl¯ + 2 (purple colour in CCl 4)
shake
(ii) 2FeCl 3 + CH3COO¯   Fe (CH3COO)3 + 3Cl¯

boil
Fe(CH3 COO)3 + 2H2O  CH3 COO (OH)2 Fe  ( Red brown ppt) + 2CH3COOH
warm
(iii) CoCl 2 + 6KNO 2 + CH3COOH   K3 [Co(NO 2)6]  (yellow) + 2KCl + CH3COOK
(iv) KClO 3  KClO 2 + [O]
MnCl 2 + 4KOH + 2[O]  K2MnO 4 (Green mass) + 2H2O + 2KCl
(v) MnCl2 + 2NaOH  Mn(OH)2 + 2NaCl
Mn(OH)2 + Br2 + 2NaOH  MnO 2  (Black) + 2NaBr + 2H2O
(vi) FeCl 3 + 3HCNS  Fe (CNS)3 (blood red coloration) + 3HCl

25. True/False :

(i) In the testing of v group radical NH4OH is added to convert NH4HCO3 to (NH4)2CO3 so that Ba2+, Sr2+ and Ca2+
precipitate completely.
Sol. T - (NH4)2 CO3 contains some qty of NH4HCO3

Page No.# 5
(ii) In the fusion test for Mn2+ ions, purple mass obtained turns green on adding NaOH solution (fusion with
KClO3 + KOH).
Sol. F - (Green mass due to MnO42– ions is obtained which turns pink or purple on adding H2SO4.
MnCl2 + 4 KOH (aq) + 2[O] from KClO3  K2MnO4 + 2H2O + 2KCl.

(iii) The addition of zinc dust during the testing of S2– by dil H2SO4 enhances the evolution of H2S gas.
Sol. T - (Zn + H2SO4  ZnSO4 + 2H; HgS + 2H  Hg + H2S)
(iv) Nonluminous flame is called oxidising flame and luminous flame is called reducing flame.
Sol. T
(v) 
Cr2 (SO4)3 + 3B2O3  2Cr(BO2)3 (blue bead) + 3SO3
Sol. F (Green or deep green)

26. A colourless and transparent crystal of a compound (A) burns with apple green flame. W hen (A) is
treated with some soluble sulphate produced a white ppt (B) which is moderately soluble in conc
H2SO 4 . An aqueous solution of (A) gives yellow ppt with K2CrO 4. When (B) is strongly heated with coke
and CaCl2 followed by lixiration with water gives the compound (A). Identify (A) and explain the reactions.

Sol. Apple green flame Ba2+ salt.

BaCl 2 + Na2SO 4  2NaCl + BaSO 4  (white) ; BaSO 4 + H2SO 4  Ba(HSO 4)2 (soluble)

BaCl 2 + K2CrO4  BaCrO 4  (yellow) + 2KCl ; BaSO 4 + CaCl 2 + 4C  BaCl 2 + 4CO + CaS.

27. If for testing of Ca2+, Ba2+ and Sr2+ by mistake, Na2CO3 is added in place of (NH4)2 CO3, then
(A) CaCO3 formed will be soluble in Na2CO3
(B) 5th group radicals will not be precipitated.
(C*) Along with 5th group radicals Mg2+ will also be precipitated.
(D) Na2CO3 will form soluble and insoluble carbonates.
Sol. Concentration of CO32– will be such high that it will precipitate Ba2+, Sr2+, Ca2+ and Mg2+.

28. The correct statement(s) is /are.

(A) titan yellow solution gives red colouration with a neutral solution containing Mg +2 ions
(B*) solution of nitrite is decomposed by sulphamic acid.
(C) Fe2+ ions give brown colour precipitate with [Fe(CN)6]3– ions solution.
(D*) Green precipitate of Cr(OH)3 is soluble in Na2O2 / NaOH.

29. Magneson I and titan yellow reagents are used for the detection of :
(A) Mn2+ (B*) Mg2+ (C) Ca2+ (D) Cu2+
2+ 2+
Sol. Mg gives deep red colour or precipitate with titan yellow. Mg gives blue precipitate/ lake with magneson I
reagent.
30. A metal nitrate containing NH4Cl and aqueous ammonia gives white crystalline precipitate with disodium
hydrogen phosphate on scratching the wall of test tube with glass rod. The metal cation is : (A) Mn2+
(B*) Mg2+ (C) Sr2+ (D) Zn2+
Sol. Mg(NO3)2 + Na2HPO4 + NH4OH  Mg(NH4)PO4  (white) + 2 NaNO3 + H2O.

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