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THE TRANSITION & CO-ORDINATION COMPOUNDS

Fill in the blanks (In some cases you may have to choose among some given options in
bracket)

1. Mn+2 can be oxidised to MnO4 by ..(SnO2, PbO2 BaO2) (1981-1 Mark)

2. Galvanization of iron denotes coating with . (1983-1 Mark)

3. Silver chloride is sparingly soluble in water because its lattice energy is greater than
.. energy. (1987-1 Mark)

4. The salts .. and .. are isostructural (1988-1 Mark)


(FeSO4.7H2O, CuSO4.5H2O, MnSO4. 4H2O,ZnSO4.7H2O)

5. The type of magnetism exhibited by [Mn(H2O)6]+2 ion is (1994-1 Mark)

6. The IUPAC name of [Co(NH3 )6]Cl3 is.. (1994-1 Mark)

7. On heating, Rb(ICI2) will decompose giving. and.. (1997-1 Mark)

8 When Fe(s) is dissolved in aqueous hydrochloric acid in a closed vessel, the work done
is.. (1997-1 Mark)

9. Silver Jewellery items tarnish slowly in the air due to their reaction with.
(1997-1 Mark)

True/False

1. Copper metal reduces Fe+2 in an acid medium. (1982-1 Mark)

2. Silver fluoride is fairly soluble in water. (1982-1 Mark)

3. Silver chloride is more soluble in very concentrated sodium chloride solution than in pure
water. (1984-1 Mark)

4. Dipositive zinc exhibits paramagnetism due to loss of two electrons from 3d-orbital of neutral
atom. (1987-1 Mark)

5. Both potassium ferrocyanide and potassium ferricyanide are diamagnetic (1989-1 Mark)

6. Cu+ disproportionates to Cu2+ and elemental copper in solution. (1991-1 Mark)

Multiple Choice Questions with ONE correct answer

1. How many unpaired electrons are present in Ni2+


(a) 0 (b) 2
(c) 4 (d) 8 (1981-1 Mark)

2. Sodium thiosulphate is used in photography because of its


(a) reducing behaviour (b) oxidising behaviour
(c) complex forming behaviour (d) reaction with light (1982-1 Mark)

3. Iron is rendered passive by treatment with concentrated


(A) H2SO4 (B) H3PO4
The Transition & Co-ordination Compounds 2

(C) HCl (D) HNO3 (1982-1 Mark)

4. In the metallurgy of iron, when limestone is added to the blast furnace, the calcium ion ends
up in
(A) slag (B) gangue
(C) metallic calcium (D) calcium ion carbonate (1982-1 Mark)

5. Zinc copper couple that can be used as a reducing agent is obtained by


(A) Mixing zinc duet and copper gauze (B) zinc coated with copper
(C) copper coated with zinc (D) zinc and copper wires welde together
(1984-1 Mark)

6. Amongst the following the lowest degree of paramagnetism per mole of the compound at
298 K will be shown by
(A) MnSO4.4H2O (B) CuSO4.5H2O
(C) FeSO4.6H2O (D) NiSO4.6H2O (1988-1 Mark)

7. Read the following statement and explanation and answer as per the options given below:
Statement (S): To a solution of potassium chromate if a strong acid is added it changes its
colour from yellow to orange
Explanation (F) The colour charge is due to the oxidation of potassium chromate.
Code
(A) Both (S) and (E) are correct and (E) is the correct explanation of (S)
(B) Both (S) and (E) are correct but (E) is not the correct explanation of (S)
(C) (S) is correct but (E) is wrong
(D) (S) is wrong but (E) is correct. (1988-2 Marks)

8. Amongst Ni(CO)4, [Ni(CN)4]-2 and NiCI4-2


(a) Ni(CO)4 and .NiCI4-2 are diamagnetic and [[Ni(CN)4]-2 is paramagnetic
(b) NiCl4-2 and [Ni(CN)4]-2 are diamagnetic and Ni(CO)4 is paramagnetic
(c) Ni(CO)4 and [Ni(CN)4]-2 are diamagnetic and NiCI4-2 is paramagnetic
(d) Ni(CO)4-2 is diamagnetic and NiCI4-2 and [Ni(CN)4]-2 are paramagnetic (1991-1 Mark)

9. Which one is solder?


(a) Cu & Pb (b) Zn & Cu
(C) Pb & Sn (d) Fe & Zn (1995-1 Mark)

10. Which pair gives Cl2 at room temperature?


(a) HCl + KMnO4 (b) NaCI + conc. H2SO4
(c) NaCI + MnO2 (d) NaCI + conc. HNO3 (1995-1 Mark)

11. Which compound is formed when excess of KCN is added to aqueous solution of copper
sulphate?
(a) Cu(CN)2 (b) K2 [Cu(CN)4]
(c) K[Cu(CN)2] (d) K3[Cu(CN)4] (1996-1 Mark)

12. Which compound does not dissolve in hot, dilute HNO3?


(a) HgS (b) PbS
(c) CuS (d) CdS (1996-1 Mark)

13. An aqueous solution of FeSO4. Al2(SO4)3 and chrome alum is heated with excess of Na2O2
and filtered. The materials obtained are:
(a) a colourless filtrate and a green residue (b) a yellow filtrate and a green residue
(c) a yellow filtrate and a brown residue (d) a green filtrate and a brown residue
(1996-1 Mark)

14. Among the following, the compound that is both paramagnetic and coloured is
The Transition & Co-ordination Compounds 3

(a) K2Cr2O7 (b) (NH4)2[TiCl6]


(c) CoSO4 (d) K3[Cu(CN)4] (1997-1 Mark)

15. Ammounium dichromate is used in some fireworks. The green coloured powder blown in the
air is
(a) CrO3 (b) Cr2O3
(c) Cr (d) CrO(O2) (1997-1 Mark)

16. The number of moles of KMnO4 that will be needed to react with one mole of sulphite ion in
acidic solution is
(A) 2/5 (B) 3/5
(C) 4/5 (D) 1 (1997-1 Mark)

17. Which of the following is an organometallic compound?


(a) Lithium methoxide (b) Lithium acetate
(c) Lithium dimethylamide (d) Methyl lithium (1997-1 Mark)

18. Read the following statement and explanation and answer as per the options given below:
Assertion: Zn+2 is diamagnetic.
Reason: The electrons are lost from 4s orbital to form Zn+2
(a) If both assertion and reason are correct, and reason is the correct explanation of the
assertion.
(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)

19. In the dichromate dianion,


(a) 4 Cr O bonds are equivalent (b) 6 Cr O bonds are equivalent
(c) all Cr O bonds are equivalent (d) all Cr O bonds are nonequivalent
(1999-2 Marks)

20. The geometry of Ni(CO)4 and Ni(PPh3)Cl2 are


(a) both square planar (b) tetrahedral and square planar, respectively
(c) both tetrahedral (d) square planar and tetrahedral, respectively
(1999-2 Marks)

21. The chemical processes in the production of steel from haematite ore involve
(a) reduction (b) oxidation
(c) reduction followed by oxidation (d) oxidation followed by reduction
(2000-Scr.)

22. The complex ion which has no d electrons in the central metal atom is
(A) [MnO4] (B) [Co(NH3]6]3+
3
(C) [Fe(CN)6] (D) [Cr(H2O)6]3+ (2001-Scr.)

23. Anhydrous ferric chloride is prepared by


(a) heating hydrated ferric chloride at a high temperature in a stream of air
(b) heating metallic iron in a stream of dry chlorine gas
(c) reaction of metallic iron with hydrochloric acid
(d) reaction of metallic iron with nitric acid (2002-Scr.)

24. When MnO2 is fused with KOH, a coloured compound is formed, the product and its colour
is:
(A) K2MnO4, purple green (B) KMnO4, purple
(C) Mn2O3, brown (D) Mn3O4 black (2003-Scr.)
The Transition & Co-ordination Compounds 4

25. In the process of extraction of gold,


Roasted gold ore + CN + H2O [X] + OH
O2

[X] + Zn [Y] + Au
Identify the complexes [X] and [Y]
(A) X = [Au(CN)2], Y = [Zn(CN)4]2 (B) X = [Au(CN)4]3, Y = [Zn(CN)4]2
4
(C) X = [Au(CN)2] , Y = Zn(CN)6] (D) X = [Au(CN)4], Y = [Zn(CN)4]2
(2003-Scr.)

26. The compound having tetrahedral geometry is


(A) [Ni(CN)4]2- (B) [Pd(CN)4]2-
(C) [PdCl4]2- (D) [NiCl4]2- (2004-Scr.)

27. Spin only magnetic moment of the compound Hg[Co(SCN) 4] is


(A) 3 (B) 15
(C) 24 (D) 8 (2004-Scr.)
28. When I- is oxidised by MnO4- in alkaline medium, I- converts into
(A) IO3- (B) I2
(C) IO4- (D) IO- (2004-Scr.)

29. (NH4)2Cr2O7 on heating gives a gas which is also given by


(A) Heating NH4NO2 (B) Heating NH4NO3
(C) Mg3N2 + H2O (D) Na(comp.) + H2O2 (2004-Scr.)

30. Which of the following pair is expected to exhibit same colour in solution?
(A) VOCl2 ; FeCl2 (B) CuCl2; VOCl2
(C) MnCl2 ; FeCl2 (D) FeCl2 ; CuCl2 (2005-Scr.)

31. Which type of isomerism is shown by Co(NH3)4Br2Cl?


(A) Geometrical and Ionisation (B) Optical and Ionisation
(C) Geometrical and Optical (D) Geometrical only (2005-Scr.)

Multiple Choice Questions with ONE MORE THAN ONE correct answer: I

1. Potassium manganate (K2MnO4) is formed when


(a) chloride is passed into aqueous KMnO4 solution
(b) manganese dioxide is fused with potassium hydroxide in air
(c) formaldehyde reacts with potassium permanganate in presence of a strong alkali
(d) potassium permanganate reacts with conc. sulphuric acid (1988-1 Mark)

2. The aqueous solutions of the following salts will be coloured in the case of
(a) Zn(NO3)2 (b) LiNO3
(c) Co(NO3)2 (d) CrCI3
(e) Potash alum (1990-1 Mark)

3. Among the following ions which one has the highest paramagnetism?
(a) Cr(H2O)6]3+ (b) [Fe(H2O)6]+2
+2
(c) [Cu(H2O6)6] (d) [Zn(H2O)6]+2 (1993-1 Mark)

4. Which of the following alloys contains(s) Cu and Zn?


(a) Bronze (b) Brass
(c) Gun metal (d) Type metal (1993-1 Mark)

5. In nitroprusside ion the iron and NO exist as Fe +2 and NO+ rather than Fe+3 and NO. These
forms can be differentiated by .
(a) estimating the concentration of iron
The Transition & Co-ordination Compounds 5

(b) measuring the concentration of. CN


(c) measuring the solid state magnetic moment
(d) thermally decomposing the compound. (1998-2 Marks)

6. Addition of high proportions of manganese makes steel useful in making rails of railroads,
because manganese
(a) gives hardness to steel (b) helps the formation of oxides of iron
(c) can remove oxygen and sulphur (d) can show highest oxidation state of + 7
(1998-2 Marks)

Subjective Problems

1. Complete the following equation (no balancing is needed):


SO2 + MnO4- + SO4-2 + Mn+2 + . (1981-1 Mark)

2. An unknown solid mixture contains one or two of the following: CaCO 3, BaCl2, AgNO3,
Na2SO4, ZnSO4 and NaOH. The mixture is completely soluble in water and the solution gives
pink colour with phenolphthalein. When dilute hydrochloric acid is gradually added to the
above solution, a precipitate is produced which dissolves with further addition of the acid.
What is/are present in the solid? Give equations to explain the appearance of the precipitate
and its dissolution. (1981-2 Marks)

3. State with balanced equations what happens when:


(i) Sulphur dioxide gas is bubbled through an aqueous solution of copper sulphate in
presence of potassium thiocyanate (1982-1 Mark)
(ii) aqueous solution of ferric sulphate and potassium iodide. (1984-2 Marks)
(iii) aqueous solution of potassium manganate and acid are mixed. (1984-2 Marks)
(iv) aqueous solution of potassium chromate and acid are mixed. (1984-2 Marks)
(v) potassium permanganate interacts with manganese dioxide in presence of potassium
hydroxide; (1985-1 Mark)
(vi) potassium ferrocyanide is heated with concentrated sulphuric acid; (1985-1 Mark)
(vii)Gold is dissolved in aqua regia. (1987-1 Mark)
(viii) Write balanced equations for the extraction of silver from silver glance by cyanide
process. (1988-1 Mark)
(ix) Silver chloride is treated with aqueous sodium cyanide and the product thus formed is
allowed to react with zinc in alkaline medium (1989-1 Mark)
(x) Cobalt (ll) solution reacts with KNO2 in acetic acid medium. (1989-1 Mark)
(xi) Write balanced equations for the extraction of copper from copper pyrites by self-
reduction. (1990-2 Marks)
(xii) A mixture of potassium dichromate and sodium chloride is heated with concentrated
H2SO4. (1990-1 Mark)
(xiii) Iron reacts with cold dilute nitric acid. (1984-1 Mark)
(xiv) Potassium permanganate is added to a hot solution of manganous sulphate.
(1990-1 Mark)
(xv) Copper reacts with HNO3 to give NO and NO2 in molar ratio of 2:1
Cu+ HNO3 .. + NO + NO2 + ......... (1992-1 Mark)
(xvi) Na2CO3 is added to a solution of copper sulphate.
CuSO4 + Na2 + CO3 + H2O ........... Na2SO4 + .. (1992-1 Mark)
(xvii) Potassium dichromate and concentrated hydrochloric acid are heated together.
(1992-1 Mark)
(xviii) AgBr+Na2S2O3 . + .. (1993-1 Mark)
(xix) (NH4)2S2O8 + H2O + MnSO4 .... + . + ..
K2Cr2O7 + HCl KCl + . + + H2O (1993-1 Mark)
(xx) [MnO4]-2 + H+ + [MnO4]- + H2O (1994-1 Mark)
(xxi) SO2(aq) + Cr2O7 + 2H
-2 +
.......... + ........... + ....... (1994-1 Mark)
The Transition & Co-ordination Compounds 6

(xxii) Write a balanced equation for the reaction of argentite with KCN and name the
products in solution. (1996-1 Mark)
(xxiii) Write balanced equations for the oxidation of cuprous oxide to cupric hydroxide by
alkaline KMnO4. (1997-1 Mark)
(xxiv) Write balanced equations for the reaction of alkaline perbromate with zinc giving
tetrahydroxozincate anion. (1997-1 Mark)
(xxv) Write balanced equations for the reaction of zinc with dilute nitric acid.(1997-1 Mark)

4. Give balanced equations for extraction of silver from its suiphide ore. (1982-2 Marks)

5. Give reasons for the following:


(i) Silver bromide is used in photography (1983-1 Mark)
(ii) Most transition metal compounds are coloured. (1986-1 Mark)
(iii) Zinc and not copper is used for the recovery of metallic silver from complex [Ag(CN) 2]
Explain. (1987-1 Mark)
(iv) The colour of mercurous chloride, Hg2Cl2 changes from white to black when treated with
ammonia. (1988-1 Mark)
(v) The species [CuCl4]-2 exists while [Cul4]-2 does not. (1992-1 Mark)
(vi) CrO3 is an acid anhydride. (1999-2 Marks)

6. State the conditions under which the following preparation is carried out. Give the necessary
equations which need not be balanced.
Potassium permanganate from manganese hydroxide (1983-1 Mark)

7. What happens when: (1985-1 Mark each)


(i). aqueous ammonia is added drop wise to a solution of copper sulphate till it is in excess.
(ii) CrCI3 solution is treated with sodium hydroxide and then with hydrogen peroxide.

8. Mention the products formed when Zinc oxide is treated with excess of sodium hydroxide
solution. (1986-1 Mark)

9. What is the actual reducing agent of haematite in blast furnace? (1987-1 Mark)

10. The acidic, aqueous solution of ferrous ion forms a brown complex in the presence of NO3- ,
by the following two steps. Complete and balance the equations:
[Fe(H2O)6]+2 + NO3- + H+ . + [Fe(H2O)6]+3 + H2O
[Fe(H2O)6] + ..........
+2
........ + H2O (1992-2 Marks)

11. Identify the complexes which are expected to be coloured. Explain


(i) [Ti(NO3)4] (ii) [Cu(NOCH3)]+ BF4-
+3 -
(ii) [Cr(NH3)6] 3Cl (iv) K3[VF6] (1994-2 Marks)

12. Write down the IUPAC names of the following compounds:


(i) [Co(NH3)5ONO]Cl2 (1995-1 Mark)
(ii) K3[Cr(CN)6] (1995-1 Mark)
(iii) [Cr(NH3)5CO3]Cl (1996-1 Mark)

13. Compare qualitatively the first and second ionization potentials of copper and zinc. Explain
the observation. (1996-2 Marks)
14. Write the IUPAC name of the compound [Cr(NH3)5(NCS)] [ZnCl4] Is this compound
coloured? (1997-2 Marks)
15. Write equations for the reaction of: (1997-1 Mark each)
(i) silver bromide with hypo in photographic process.
(ii) cobaltous chloride with excess KNO2, in aqueous acidic solution.
16. Write the formulae of the following complexes: (1997-1 Mark each)
The Transition & Co-ordination Compounds 7

(i) Pentamminechlorocobalt(lU) (III)


(ii) Lithium tetrahydroaluminate(Ul) (III)
17. When the ore haematite is burnt in air with coke around 2000C along with lime, the process
not only produces steel but also produces a silicate slag that is useful in making building
materials such as cement. Discuss the same and show through balanced chemical
equations. (1998-4 Marks)

18. Work out the following using chemical equations. In moist air copper corrodes to produce a
green layer on the surface. (1998-2 Marks)

19. A, B, and C are three complexes of chromium (III) with the empirical formula H 12O6Cl3Cr All
the three complexes have water and chloride ion as ligands. Complex A does not react with
concentrated H2SO4 whereas complexes B and C lose 6.75% and 13.5% of their original
mass, respectively, on treatment with concentrated H2SO4 Identify A, B and C.
(1999-6 Marks)

20. Write the chemical reaction associated with the brown ring test. (2000-2 Marks)

21. Draw the structures of [Co(NH3)6]3+ [Ni(CN)4]2 and [Ni(CO)4] Write the hybridization of
atomic orbitals of the transition metal in each case. (2000-4 Marks)

22. (i) Write the chemical reactions involved in the extraction of metallic silver from argentite.
(ii) Write the balanced chemical equation for developing photographic films. (2001-2 Marks)

23. A metal complex having composition Cr(NH 3)4 Cl2Br has been isolated in two forms (A) and
(B). The form (A) reacts with AgNO3 to give a white precipitate readily soluble in dilute
aqueous ammonia, whereas (B) gives a pale yellow precipitate soluble in concentrated
ammonia Write the formula of(A) and (B) and state the hybridization of chromium in each
Calculate their magnetic moments (spinonly value). (2001-5 Marks)

24 Deduce the structure of [NiCl4]2 and [Ni(CN)4]2 considering the hybridization of the metal
Calculate the magnetic moment (spin only) .of the species. (2002-5 Marks)

25. Write the IUPAC nomenclature of the given complex along with its hybridization and
structure K2[Cr(NO)(NH3)(CN)4], = 1.73 BM (2003-4 Marks)

26. Nickel chloride, when treated with dimethylgyloxime in presence of ammonium hydroxide,
a bright red precipitate is obtained Answer the following. (2004-4 Marks)
(a) Draw the structure of the complex showing H-bonds
(b) Give oxidation state of nickel and its hybridization
(c) Predict the magnetic behaviour of the complex

27. A1 & A2 are two ores of metal M. A1 on calcination gives black precipitate, CO2 & water.
n Black solid + CO2 + H2O
atio
l cin
Ca

A1 dil HCl

KI I 2 ppt
A2
roasting Metal gas
K 2 Cr2 O 7 H 2SO 4

green colour (2004-4 Marks)



F (excess)
28. Fe3
SCN (excess)

blood
red(A) colourless (B)
Identify A and B. (2005-4 Marks)
(a) Write IUPAC name of A and B.
(b) Find out spin only magnetic moment of B.
The Transition & Co-ordination Compounds 8

29. Write balanced chemical equation for developing a black and white photographic film. Also
give reason why the solution of sodium thiosulphate on acidification turns milky white and
give balance equation of this reaction. (2005-4 Marks)

Moist air Zn
(B) MCl4 (A)
white fumes having smell (M = transitionelement colourless)(purple color)
Identify the metal M and hence MCl4. Explain the difference in colours of MCl4 and A.
(2005-4Marks)
The Transition & Co-ordination Compounds 9

ANSWERS

A 1. PbO2 2. zinc 3. hydration/solvation


4. FeSO4.7H2O, ZnSO4.7H2O 5. paramagnetism
6. hexamine cobalt (III) chloride 7. RbCl, ICI
8. zero 9. H2S

B 1. F 2. T 3. T 4. F
5. F 6. T

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


5. (b) 6. (b) 7. (c) 8. (b)
9. (c) 10. (a) 11. (d) 12. (a)
13. (c) 14. (c) 15. (b) 16. (a)
17. (d) 18. (b) 19. (b) 20. (c)
21. (c) 22. (a) 23. (b) 24. (a)
25. (a) 26. (b) 27. (c) 28. (a)
29. (a) 30. (b) 31. (a)

D 1. (b, c) 2. (c, d) 3. (b) 4. (b, c)


5. (c) 6. (a & c)

E 2. ZnSO4 NaOH
8. sodium zincate, water 9. CO 11. (iii), (iv)
12. (i) pentamminenitritocobalt (III) chloride
(ii) potassium hexacyanochromate (III)
(iii) pentamminecarbonatochromium (III) chloride
14. pentammine isothiocyanotochromium (III) tetra chlorozincate
16. (i) [CoCl(NH3)5]2+ (ii) LiAlH4
19. [Cr(H2O)6]Cl3, [Cr(H2O)5Cl](H2O)Cl2, [Cr(H2O)4Cl2](H2O)2Cl
23. [Cr(NH3)4BrCl]Cl, (d2sp3), [Cr(NH3)4Cl2]Br, (d2sp3), 3.87 BM, 3.87 BM
25. Potassium aminetetracyanonitrosoniumchromate (I), octahedral shape
26. (b) +2, dsp2, (c) diamagnetic
27. CuCO3, Cu(OH)2, Cu2S, Cu, CuO, Cu2I2, SO2
28. Fe(SCN)3, [FeF6]3; trithiocyanoiron (III); 5.92 BM
30. [Ti(H2O)6]Cl3, HCl, TiCl4