JEE Chemistry

Coordination Compounds
ADVCOR -1
 Marked Questions may have for Revision Questions.
PART - I : SUBJECTIVE QUESTIONS

Section (A) : General introduction of complex salts and definitions to be used
A-1. K2SO4 solution mixed with Cr2(SO4)3 solution in 1 : 1 molar ratio gives the test of Cr3+ ion but CuSO4 solution
mixed with aqueous ammonia in 1 : 4 molar ratio does not give the test of Cu2+ ion. Explain why ?
A-2. What is the coordination number and the oxidation state of the metal in each of the following complexes?
(a) [AgCl2]– ; (b) [Cr(H2O)5Cl]2+ ; (c) [Co(NCS)4]2–
(d) [Co(NH3)3(NO2)3] ; (e) [Fe(EDTA)]– (f) [Cu(en)2]SO4 ;
(g) K[Pt(NH3)Cl5]
A-3. Write the name of the following ligands and classify their denticity
(A) CH3NC (B) acac–1 (C) N3– (D) dien (E) edta4–
(F) edta 3–
(G) ox 2–
(H) dmg–1 (I) NC– (J) NO2–
(K) O 2–
(L) O22–
(M) O2 –
A-4. Predict the different ligating sites by drawing structures in the following ligands.
(A) (NO2)– (B) (SCN)– (C) (C2O2S2)2– (D) (OCN)– (E) (NOS)–
A-5.(a) Draw the structure of the complexes [Fe(C2O4)3]3– and [Pt(en)2]2+. Determine the denticity of the ligands and
identify any chelate rings. What are the coordination number and the oxidation number of the central metal ion?
(b) Designate the coordination entities and counter ions in the coordination compounds.
K2[Ni(CN)4] ; [Cr(en)3] Cl3 ; Fe4[Fe(CN)6]3 ; [PtCl2(en)2] (NO3)2.
(c) Identify the Lewis acid and Lewis base components of the following complexes.
(i) [HgBr4]2- (ii) [Ni(H2O)6]2+ (iii) [PdCl2(NH3)2]
(iv) [Al(OH)4]–
(v) [Ag(CN)2]– (vi) [Cr(CO)6]
Section (B) : Nomenclature of coordination compounds

B-1. Name the following compounds
(a) [Co(NH3)6]Cl3, Prepared in 1798 by B.M. Tassaert and considered to be first complex salt prepared.
(b) [Rh(NH3)5I]I2, A yellow colored complex obtained by heating [Rh(NH3)5(H2O)]I3 above 1000C.
(c) [Fe(CO)5], A highly toxic volatile liquid.
(d) [Fe(C2O4)3]3–, The ion formed when Fe2O3 rust is dissolved in oxalic acid, H2C2O4.
(e) [Cu(NH3)4]SO4, A deep blue compound obtained when CuSO4 is treated with excess of NH3.
(f) Na[Cr(OH)4], The compound formed when Cr(OH)3 precipitate is dissolved in excess of NaOH.
(g) [Co(gly)3], A complex that contains the anion of amino acid, glycine.
(h) [Fe(H2O)5(SCN)]2+, The red complex ion formed in the qualitative analysis test of Fe3+ ion.
(i) K2[HgI4], Alkaline solution of this complex is called Nessler’s Reagent.
(j) Co[Hg(SCN)4], Deep blue crystalline precipitate obtained in qualitative detection of Hg2+.
(k) Fe4[Fe(CN)6]3, Prussian blue, deep blue colored complex obtained in detection of Fe2+.
(l) K3[Co(NO2)6], Potassium cobaltinitrite or Fischer salt yellow precipitate obtained in detection of Co2+.
(m) [Ni(dmg)2], Rosy red precipitate obtained in detection of Ni2+ ions.
(n) K2[PtCl6], Yellow precipitate obtained in detection of potassium ions.
(o) Na2[Fe(CN)5NO+], Sodium nitroprusside used for detection of sulphide ions/sulphur.
(p) [Fe(H2O)5(NO+)]SO4, Brown ring complex, obtained in detection of Fe2+ ions.
(q) [Cu(CN)4]3–, Colourless stable soluble complex obtained in detection of Cu2+ on adding excess of KCN
solution.
(r) (NH4)2[PtCl6], Only few compounds of ammonium ions are precipitate this is one of these, a yellow
precipitate.
ADVCOR -2
B-2. Name the following compounds.
(a) [CoBr(en)2(ONO)]+ (b) [Co(NH3)6][Co(ONO)6]
(c) [Co(NH3)5(CO3)]Cl (d) [Pt(NH3)4Cl2][PtCl4]
(e) [Co(en)3]2(SO4)3 ;
(f) [(NH3)5Co-NH2-Co(NH3)4(H2O)]Cl5
(g) [Cr(CO)5(PPh3)] (h) [(CO)5Mn-Mn(CO)5]
(i) Cr(  6–C6H6)2 (j) [Co(NH3)4(OH2)2][BF4]3
(k) Ba[Zr(OH)2(ONO)2(ox)] (l) [Co(NH3)6][Co(C2O4)3]
B-3. Write down the formulae of the following compounds
(a) Tetraamminezinc(II) Nitrate, The compound formed when zinc nitrate is treated with
an excess of ammonia
(b) Tetracarbonylnickel(0), The first metal carbonyl(prepared in 1888) and an important
compound in the industrial refining of nickel metal
(c) Potassium amminetrichloridoplatinate(II) A compound that contains a square planar anion
(d) Dicyanidoaurate(I) ion An ion important in the extraction of gold from its ores
(e) Sodium hexafluoridoaluminate(III) Called cryolite, used in the electrolytic refining of aluminium
(f) Diamminesilver(I) ion Ion formed when AgCl is dissolved in excess of ammonia
B-4. Write down the formulae of the following compounds
(a) diamminetriaquahydroxidochromium (III) nitrate
(b) tetrakis(pyridine)platinum(II) tetraphenylborate(III)
(c) dibromidotetracarbonyliron (II)
(d) ammonium diamminetetrakis(isothiocyanato)chromate(III).
(e) pentaamminedinitrogenruthenium(II) chloride
(f) barium dihydroxidodinitrito-O-oxalatozirconate(IV)
(g) tetrapyridineplatinum(II) tetrachloridonickelate(II)
Section (C) : Werner's Theory

(Initial bonding theories and EAN rule)
C-1. Werner conducted many experiments to establish the formula of complexes, one of these were conductivity
measurements. On the basis of the experiments performed he obtained the following values of conductivity
for different type of complexes.
Type of complex Electrical Conductivity
Nonelectrolyte 0 – 10 (due to impurities)
1:1 Electrolyte 90 – 130
1:2 or 2:1 Electrolyte 230 – 290
1:3 or 3:1 Electrolyte 390 – 450
1:4 Electrolyte 500 – 550
On the basis of above table Match the following two columns.
COLUMN A COLUMN B
Formula of compound Conductivity Correct Werner’s Representation
(a) PtCl4.2NH3 6.99 (i) [Cr(NH3)5Cl]Cl2
(b) PtCl4.NH3.KCl 106.8 (ii) [Co(NH3)5Br]Br2
(c) CrCl3.5NH3 260.2 (iii) [Cr(NH3)6]Cl3
(d) PtCl4.2KCl 256.8 (iv) [Pt(NH3)2Cl4]
(e) CrCl3.6NH3 441.7 (v) [Pt(NH3)6]Cl4
(f) PtCl4.6NH3 522.9 (vi) [Pt(NH3)3Cl3]Cl
(g) CoBr3.5NH3 257.6 (vii) K2[PtCl6]
(h) PtCl4.3NH3 96.8 (viii) K[Pt(NH3)Cl5]
ADVCOR -3
C-2. 1 g of complex [Cr(H2O)5Cl]Cl2.H2O was passed through a cation exchanger to produce HCl. The acid liberated
was diluted to 1 litre. What will be the molarity of acid solution [Molecular weight of complex = 266.5] ?
C-3. Calculate the EAN of central atom in the following complexes
(a) [Cr(CO)6] (b) [Fe(CN)6]4– (c) [Fe(CO)5] (d) [Co(NH3)6]3+
(e) [Ni(CO)4] (f) [Cu(CN)4]3– (g) [Pd(NH3)6]4+ (h) [PtCl6]2–
C-4. Arrange the following compounds in order of increasing molar conductivity.
(i) K[Co(NH3)2(NO2)4] (ii) [Cr(NH3)3(NO2)3] (iii) [Cr(NH3)5(NO2)]3[Co(NO2)6]2 (iv) [Cr(NH3)6]Cl3
Section (D) : Valence Bond Theory + Crystal Field Theory (Part-I)

D-1. A metal complex having composition Cr(NH3)4Cl2Br 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
yellow precipitate soluble in concentrated ammonia.
(i) Write the formulae of A and B.
(ii) State hybridisation of chromium in each.
(iii) Calculate their magnetic moments for each (spin-only value).
(iv) Calculate the EAN for both.
(v) Will they conduct electricity or not.
(vi) Write the formula of the complexes formed when the precipitates dissolve in aqueous ammonia & the
concentrated ammonia respectively.
D-2. Predict the hybridisation and geometry of the following complexes.

(a) [NiBr4]2– (b) [AuCl4]– (c) [Pt(NH3)4]2+
Section (E) : Valence Bond Theory + Crystal Field Theory (Part-II)

E-1. For the complex K2[Cr(NO)(NH3)(CN)4];  = 1.73 BM.
(i) Write IUPAC name.
(ii) What will be structure?
(iii) How many unpaired electrons are present in the central metal ion?
(iv) Is it paramagnetic or diamagnetic?
(v) Calculate the EAN of the complex.
(vi) What will be the hybridisation of the complex ?
E-2. Predict the hybridisation and geometry of the following complexes.

(a) [Fe(CN)6]3– (b) [MnBr4]2– (c) [Fe(H2O)6]2+ (d) [Co(SCN)4]2–
E-3. [Co(NH3)6]3+ & [CoF6]3– both are complexes of Co(III), but [Co(NH3)6]3+ is diamagnetic while [CoF6]3– is
paramagnetic with  = 4.90 B.M. Explain.
E-4. Arrange the following in increasing order as directed.
(a) (i) [CoCl3 (NH3)3], (ii) [CoCl (NH3)5] Cl2, (iii) [Co(NH3)6] Cl3, (iv) [CoCl2 (NH3)4] Cl – Molar conductance
(b) C, N, O, F (halogen) - tendency of  donation.
(c) Br–, S2– , NO2– , CO , H2O, CN– , NH3, NO3– - strength of ligands.
E-5. For each of the following complexes, draw a crystal field energy-level diagram, assign the electrons to
orbitals, and predict the number of unpaired electrons:
(a) [CrF6]3– (b) [V(H2O)6]3+ (c) [Fe(CN)6]3–
(d) [Cu(en)3]2+ (e) [FeF6]3–
Section (F) : Applications of crystal field theory

(Colour of complex, Magnetic moment of complex, Stability of complex)
F-1. Cobalt (II) is stable in aqueous solution but in the presence of complexing reagents(strong field ligands) it is
readily oxidised. why ?
ADVCOR -4
F-2. The value of 0 for [Ti(H2O)6]3+ is found to be 240 kJ mol–1 then predict the colour of the complex using the
following table. (h = 6 × 10–34 J-sec, NA= 6 × 1023, c = 3 × 108 m/sec)
––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
Absorbed light (nm) (absorbed) Colour exhibited
––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
Blue 435 – 480 Yellow
green-blue 480 – 490 orange
blue – green 490 – 500 red
green 500 – 560 purple
yellow – green 560 – 580 violet
Yellow 580 – 595 blue
Red 605 – 700 blue green
––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
F-3.(a) [Ti(H2O)6]3+ absorbs light of wavelength 5000 Å. Name one ligand which would form a titanium(III) complex
absorbing light of lower wavelength than 5000 Å and one ligand which would form a complex absorbing light
of wavelength higher than 5000 Å.
(b) Calculate the magnetic moments (spin only) of the following complexes
(i) [PtCl6]2– (ii) [Cr(CO)6] (iii) [Ir(NH3)6]3+ (iv) [Pd(en)2]2+
Section (G) : Isomerism in Coordination compounds

(Structural Isomerism, Stereoisomerism, Geometrical Isomerism, Optical Isomerism)
G-1. What type of isomers are the following :

(i) [Mn(CO)5SCN] and [Mn(CO)5NCS]
(ii) [Co(en)3] [Cr(CN)6] and [Cr(en)3] [Co(CN)6]
(iii) [Co(NH3)5 NO3]SO4 and [Co(NH3)5SO4]NO3
(iv) [Co(H2O)2Cl2 (py)2]Cl and [Co(H2O)Cl3 (py)2]H2O
G-2. (a) Draw all possible constitutional isomers of the compound Ru(NH3)5(NO2)Cl. Label the isomers as linkage
isomers or ionization isomers.
(b) There are six possible isomers for a square planar palladium(II) complex that contains two Cl– and two
SCN– ligands. Sketch the structures of all six, and label them according to the classification.
G-3. How many geometrical isomers are possible for each of the following complexes?
(a) [Pt(NH3)2(SCN)2] (b) [CoCl2Br2]2– (tetrahedral)
(c) [Co(NH3)3 (NO2)3] (d) [Pt(en)Cl2]
(e) [Cr Br2 (en)2]+ (f) [Rh(en)3]3+
G-4. Which of the following complexes can exist as enantiomers? Draw their structures
(a) cis-[Co(NH3)4Br2]+ (b) cis-[Cr(H2O)2(en)2]3+ (c) [Cr(gly)3]
(d) [Cr(en)3]3+ (e) cis-[Co(NH3)Cl(en)2]2+ (f) trans-[Co(NH3)2(en)2]2+
Section (H) : Organometallic Compounds

H-1. Draw the structures of the following metal carbonyls
(a) [V(CO)6] (b) [Cr(CO)6] (c) [Mn2(CO)10]
(d) [Fe(CO)5] (e) [Ni(CO)4]


H-2. 
M C O



The figure represents the synergic bonding interaction in metal carbonyl complex. On the basis of this
explain the following :
(i) Strength of Metal-ligand bond
(ii) Bond order of CO in carbonyl complex as compared to bond order in carbon monoxide.
ADVCOR -5
PART - II : ONLY ONE OPTION CORRECT TYPE

Section (A) : General introduction of complex salts and definitions to be used
A-1. Ethylene diamine is an example of a .......... ligand :
(A) monodentate (B) bidentate (C) tridentate (D) hexadentate
A-2. The donor sites of (EDTA)4– are ?

(A) O atoms only (B) N atoms only
(C) Two N atoms and four O atoms (D) Three N atoms and three O atoms
A-3. Some salts although containing two different metallic elements give test for one of them in solution. Such
salts are :
(A) complex salt (B) double salt (C) normal salt (D) none
A-4. Ligands are :

(A) Lewis acids (B) Lewis bases (C) neutral (D) none
A-5. The oxidation state of Mo in its oxido-complex species [Mo2O4(C2H4)2(H2O)2]2– is

(A) +2 (B) +3 (C) +4 (D) +5
A-6. Co-ordination number of platinum in [Pt(NH3)4Cl2]2+ ion is:
(A) 4 (B) 2 (C) 8 (D) 6
A-7. Which of the following is copper() compound ?
(A) [Cu(H2O)4]2+ (B) [Cu(CN)4]3– (C) [Cu(NH3)4]2+ (D) All of these
A-8. In the complex [CoCl2(en)2]Br, the co-ordination number and oxidation state of cobalt are :
(A) 6 and +3 (B) 3 and +3 (C) 4 and +2 (D) 6 and +1
A-9. What is the charge on the complex [Cr(C2O4)2(H2O)2] formed by Cr() ?
(A) +3 (B) +1 (C) +2 (D) –1
Section (B) : Nomenclature of coordination compounds

B-1. A complex cation is formed by Pt (in some oxidation state) with ligands (in proper number so that coordination
number of Pt becomes six). Which of the following can be its correct IUPAC name ?
(A) Diammineethylenediaminedithiocyanato-S-platinum (II) ion
(B) Diammineethylenediaminedithiocyanato-S-platinate (IV) ion
(C) Diammineethylenediaminedithiocyanato-S-platinum (IV) ion
(D) Diamminebis (ethylenediamine) dithiocyanate-S- platinum (IV) ion
B-2. Which of the following names is impossible ?
(A) Potassium tetrafluoridooxidochromate (VI) (B) Barium tetrafluoridobromate (III)
(C) Dichlorobis(urea)copper (II) (D) All are impossible.
B-3. The formula of the complex tris(ethylenediamine)cobalt(III) sulphate is :

(A) [Co(en)2SO4] (B) [Co(en)3SO4] (C) [Co(en)3]2SO4 (D) [Co(en)3]2(SO4)3
B-4. The correct IUPAC name for the compound [Co(NH3)4CI(ONO)]Cl is :

(A) Tetraamminechloridonitrito–N–cobalt(III) chloride
(B) Chloridonitrito–O–tetraamminecobalt(II) chloride
(C) Dichloridonitrito–O–tetraamminecobalt(III)
(D) Tetraamminechloridonitrito–O–cobalt(III) chloride
B-5. The hypothetical complex triamminediaquachloridocobalt(III) chloride can be represented as :

(A) [CoCl(NH3)3(H2O)2] (B) [Co(NH3)3(H2O)Cl3]
(C) [Co(NH3)3(H2O)2Cl]Cl2 (D) [Co(NH3)3(H2O)3]Cl3 ]
ADVCOR -6
Section (C) : Werner's Theory
(Initial bonding theories and EAN rule)
C-1. EAN of a metal carbonyl M(CO)x is 36. If atomic number of metal M is 26, what is the value of x ?
(A) 4 (B) 8 (C) 5 (D) 6
C-2. The EAN of platinum in potassium hexachloridoplatinate(IV) is (Atomic number of Pt = 78) :

(A) 90 (B) 86 (C) 76 (D) 88
C-3. A compound is made by mixing cobalt (III) nitrite and potassium nitrite solutions in the ratio of 1 : 3. The
aqueous solution of the compound showed 4 particles per molecule whereas molar conductivity reveals the
presence of six electrical charges. The formula of the compound is :
(A) Co(NO2)3.2KNO2 (B) Co(NO2)3.3KNO2 (C) K3[Co(NO2)6] (D) K[Co(NO2)4]
C-4. Which of the following will exhibit maximum ionic conductivity?

(A) K4 [Fe(CN6] (B) [Co(NH3)6] Cl3 (C) [Cu(NH3)4] Cl2 (D) [Ni (CO)4]
C-5. Which of the following shows maximum molar conductance ?

(A) [Co(NH3)6]Cl3 (B) [Co(NH3)3Cl3] (C) [Co(NH3)4 Cl2] Cl (D) [Co(NH3)5Cl]Cl2
C-6. The complex [Cr(H2O)4Br2]Cl gives the test for :

(A) Br– (B) Cl– (C) Cr3+ (D) Br– and Cl– both
C-7. Which of the following complexes will be dehydraded to relatively minimum extent by conc. H 2SO4 under
identical condition.
(A) [Cr(H2O)5Cl]Cl2.H2O (B) [Cr(H2O)4Cl2]Cl.2H2O
(C) [Cr(H2O)6]Cl3 (D) all of these.
C-8. On adding AgNO3 solution to a solution of [Pt(NH3)3Cl3]Cl, the percentage of total chloride ion precipitated is:
(A) 100 (B) 75 (C) 50 (D) 25
C-9. A complex of platinum, ammonia and chloride produces four ions per molecule in the solution. The structure
consistent with the observation is :
(A) [Pt(NH3)4]Cl4 (B) [Pt(NH3)2Cl4] (C) [Pt(NH3)5Cl]Cl3 (D) [Pt(NH3)4Cl2]Cl2
Section (D) : Valence Bond Theory + Crystal Field Theory (Part-I)

D-1. The complex ion which has no 'd' electrons in the central metal atom is :
(A) [MnO4]– (B) [Co(NH3)6]3+ (C) [Fe(CN)6]3– (D) [Cr(H2O)6]3+
D-2. For the correct assignment of electronic configuration of a complex, the valence bond theory often requires
the measurement of
(A) molar conductance (B) optical activity
(C) magnetic moment (D) dipole moment
D-3. The magnitude of crystal field stabilisation energy (CFSE of 1) in tetrahedral complexes is considerably
less than that in the octahedral field. Because
(A) There are only four ligands instead of six so the ligand fild is only 2/3 in tetradedral complex.
(B) The direction of the orbitals does not coincide with the direction of the ligands. This reduces the crystal
field stabilization energy () by further 2/3.
(C) Both points (A) and (B) are correct.
(D) Both points (A) and (B) are wrong.
D-4. Which of the following factors tends to increase the stability of metal ion complexes ?
(A) Higher ionic radius of the metal ion (B) Higher charge/size ratio of the metal ion
(C) Lower ionisation potential of the metal ion (D) Lower basicity of the ligand
ADVCOR -7
D-5. The crystal field splitting energy for octahedral complex (o) and that for tetrahedral complex (t ) are related as:
4 9
(A) t = 0 (B) t = 0.5 o (C) t = 0.33 o (D) t = 
9 4 0
D-6. All the metal ions contains t2g6 eg0 configurations. Which of the following complex will be paramagnetic ?
(A) [FeCl(CN)4(O2)]4- (B) K4[Fe(CN)6] (C) [Co(NH3)6]Cl3 (D) [Fe(CN)5(O2)]-5
Section (E) : Valence Bond Theory + Crystal Field Theory (Part-II)

E-1. Chromium hexacarbonyl is an octahedral compound involving :
(A) sp3d2 (B) dsp2 (C) d2sp3 (D) dsp3
E-2. Which of the following molecules is not tetrahedral ?

(A) [Pt(en)2]2+ (B) [Ni(CO)4] (C) [Zn(NH3)4]2+ (D) [NiCl4]2–
E-3. The complex [Pt(NH3)4]2+ has ..... structure :

(A) square planar (B) tetrahedral (C) pyramidal (D) pentagonal
E-4. Match Column-I with Column-II and select the correct answer with respect to hybridisation using the codes
given below :
Column-I Column-II
(Complex) (Hybridisation)
(I) [Au F4] – (p) dsp2 hybridisation
(II) [Cu(CN)4]3– (q) sp3 hybridisation
(III) [Co(C2O4)3] 3– (r) sp3d2 hybridisation
(IV) [Fe(H2O)5NO]2+ (s) d2sp3 hybridisation
Codes :
(I) (II) (III) (IV) (I) (II) (III) (IV)
(A) q p r s (B) p q s r
(C) p q r s (D) q p s r
E-5. The hybridisation and unpaired electrons in [Fe(H2O)6]2+] ion are :

(A) sp3d2 ; 4 (B) d2sp3 ; 3 (C) d2sp3 ; 4 (D) sp3 d2 ; 2
E-6. The number of unpaired electrons in d6, low spin, octahedral complex is :
(A) 4 (B) 2 (C) 1 (D) 0
E-7. Which of the following is a high spin complex ?

(A) [Co(NH3)6]3+ (B) [Fe(CN)6]4– (C) [Ni(CN)4]2– (D) [FeF6]3–
E-8. Which has maximum paramagnetic nature ?

(A) [Cu(H2O)4]2+ (B) [Cu(NH3)4]2+ (C) [Mn(H2O)6]2+ (D) [Fe(CN)6]4–
E-9. The number of unpaired electrons present in complex ion [FeF6]3- is :

(A) 5 (B) 4 (C) 6 (D) 0
E-10. Which of the following complexes has a geometry different from others ?
(A) [Ni Cl4]2– (B) Ni (CO)4 (C) [Ni(CN)4]2– (D) [Zn(NH3)4]2+
E-11. Select the correct statement.

(A) Complex ion [MoCl6]3– is paramagnetic. (B) Complex ion [Co(en)3]3+ is diamagnetic.
(C) Both (A) and (B) are correct. (D) None of correct.
E-12. Amongst Ni(CO)4, [Ni(CN)4]2– and NiCI42– :

(A) Ni(CO)4 and NiCI42– are diamagnetic and [Ni(CN)4]2– is paramagnetic.
(B) NiCI42– 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 NiCI42– is paramagnetic.
(D) Ni(CO)4 is diamagnetic and NiCI42– and [Ni(CN)4]2– are paramagnetic.
ADVCOR -8
Section (F) : Applications of crystal field theory
(Colour of complex, Magnetic moment of complex, Stability of complex)
F-1. The compound which does not show paramagnetism ?

(A) [Cu(NH3)4Cl2 ] (B) [Ag(NH3)2]Cl (C) NO (D) NO2
F-2. Among the following ions, which one has the highest paramagnetism ?
(A) [Cr(H2O)6]3+ (B) [Fe(H2O)6]2+ (C) [Cu(H2O)6]2+ (D) [Zn(H2O)6]2+
Section (G) : Isomerism in Coordination compounds

(Structural Isomerism, Stereoisomerism, Geometrical Isomerism, Optical Isomerism)
G-1. The complexes [Pt(NH3)4] [PtCl6] and [Pt(NH3)4Cl2] [PtCl4] are :

(A) linkage isomers (B) optical isomers
(C) co-ordination isomers (D) ionisation isomers
G-2. [Co(NH3)5NO2]Cl2 and [Co(NH3)5ONO]Cl2 are related to each other as :

(A) geometrical isomers (B) linkage isomers
(C) coordination isomers (D) ionisation isomers
G-3. The number of geometrical isomer of [Co(NH3)3(NO3)3] are :

(A) 0 (B) 2 (C) 3 (D) 4
G-4. Geometrical isomerism is found in coordination compounds having coordination number :

(A) 2 (B) 3 (C) 4 (tetrahedral) (D) 6
G-5. Cis-trans isomerism is found in square planar complexes of molecular formula ('a' and 'b' are monodentate
ligands) :
(A) Ma4 (B) Ma3b (C) Ma2b2 (D) Mab3
G-6. Geometrical isomerism can be shown by :

(A) [Ag(NH3)(CN)] (B) Na2[Cd(NO2)4] (C) [PtCl4I2] (D) [Pt(NH3)3Cl][Au(CN)4]
Section (H) : Organometallic Compounds

H-1. Which one is not an organometallic compound ?
(A) RMgX (B) (C2H5)4Pb (C) (CH3)4Sn (D) C2H5ONa
H-2. Formula of ferrocene is:

(A) [Fe(CN)6]4– (B) [Fe(CN)6]3+ (C) [Fe(CO)5] (D) [Fe(C5H5)2]
MATCH THE COLUMN

1. Column-I Column-II
(A) [Fe(en)3]3+ (p) d2sp3 hybridisation of central metal
(B) [Co(ox)3]3– (q) sp3d2 hybridisation of central metal
(C) [Cr(CN)6]3– (r) paramagnetic
(D) [NiCl6]4– (s) diamagnetic
(t) metal ion has +3 oxidation state
2. There are some coordination compounds given in column-I which may exist in different isomeric forms as
given in column-II. Select the correct option(s) for the coordination compounds and their respective isomeric
forms.
Column-I Column-II
(A) [Co(en)2NH3Cl]SO4 (p) Enantiomer
(B) [Co(NH3)4(NO2)2](NO3)2 (q) Geometrical isomer
(C) [Co(en)(pn)(NO2)2]Cl (r) Ionization isomer
(D) [Co(gly)3] (s) Linkage isomer
ADVCOR -9
PART - I : ONLY ONE OPTION CORRECT TYPE

1. A complex anion is formed by Osmium (in some oxidation state) with ligands (in proper number so that
coordination number of osmium becomes six). Which of the following can be its correct IUPAC name?
(A) pentachloridonitridoosmium(VI) (B) pentachloridonitridoosmate(VI)
(C) azidopentachloridoosmate(VI) (D) None of these
2. The EAN of metal atoms in [Fe(CO)2(NO+)2] and Co2(CO)8 respectively are :
(A) 34, 35 (B) 34, 36 (C) 36, 36 (D) 36, 35
3. Which of the following is inner orbital complex as well as diamagnetic in nature ?
(A) [Ir(H2O)6 ]3+ (B) [Ni(NH3)6]2+ (C) [Cr(NH3)6]3+ (D) [Co(NH3)6]2+
4. Which of the following statement is correct ?
(A) The oxidation state of iron in sodium nitro prusside Na2 [Fe(CN)5(NO))] is +3
(B) [Ag(NH3)2]+ is linear in shape
(C) In [Fe(H2O)6]3+ , Fe is d2sp3 hybridized
(D) In Ni (CO)4, the oxidation state of Ni is 1
5. The complex K4[Zn(CN)4(O2)2] is oxidised into K2[Zn(CN)4(O2)2] , then which of the following is correct ?
(A) Zn (II) is oxidised into Zn (IV) (B) Paramagnetic moment decreases
(C) O – O bond length increases (D) Paramagnetic moment increases
6. All the following complexes show decrease in their weights when placed in a magnetic balance then the
group of complexes having tetrahedral geometry is :
I Ni (CO)4 II K [AgF4] III Na2 [Zn (CN)4]
IV K2 [PtCl4] V [RhCl (PPh3)3]
(A) II , III , V (B) I , II , III (C) I , III , IV (D) none of these
7. The complex [Fe(H2O)5NO]2+ is formed in the brown ring test for nitrates when freshly prepared FeSO4
solution is added to aqueous solution of NO3– ions followed by addition of conc. H2SO4. Select correct
statement about this complex.
(A) Hybridisation of iron is sp3d2.
(B) Iron has +1 oxidation state.
(C) It has magnetic moment of 3.87 B. M. confirming three unpaired electrons in Fe.
(D) All the above are correct statements.
8. Which of the following statements is not correct?

(A) TiCl4 is a colourless compound. (B) [Cr(NH3)6)]Cl3 is a coloured compound.
(C) K3[VF6] is a colourless compound. (D) [Cu(NCCH3)4][BF4] is a colourless compound.
9. Among TiF62  , CoF63  , Cu2Cl2 and NiCl 24  the colourless species are:
(A) CoF63 and NiCl24 (B) TiF62 and CoF63 (C) NiCl24 and Cu2Cl2 (D) TiF62 and Cu2Cl2
10. The number of geometrical isomers for octahedral [Co(NH3)2Cl4]–, square planar AuCl2Br2– are :
(A) 4, 2 (B) 2, 2 (C) 3, 2 (D) 2, 3
11. Which of the following statements is not true about the complex ion [Pt(en) 2Cl2]2+ ?
(A) It has two geometrical isomers – cis and trans.
(B) Both the cis and trans isomers display optical activity.
(C) Only the cis isomer displays optical activity.
(D) Only the cis isomer has non–superimposable mirror image.
ADVCOR - 10
12. Both geometrical and optical isomerism are shown by :
(A) [Co(en)2Cl2]+ (B) [Co(NH3)5Cl]2+ (C) [Co(NH3)4Cl2]+ (D) [Cr(OX)3]3–
13. Among the following, metal carbonyls, the C—O bond is strongest :
(A) [Mn(CO)6]+ (B) [Cr(CO)6] (C) [V(CO)6]– (D) [Ti(CO)6]2–
PART - II : SINGLE AND DOUBLE VALUE INTEGER TYPE

1. Sum of denticity of following ligands are
Glycinate ion, Oxalate ion, o-phenathroline, 2,2-bipyridyl, diethylenetriamine, ethylenediamine
2. How many total sodium ions are present in one formula unit of sodium ethane-1,2-diaminetetraacetatochromate
(II) and sodium hexanitrito cobaltate (III) ?
3. A blue colour complex is obtained in the analysis of Fe+3 having formula Fe4[Fe(CN)6]3
Let a = oxidation number of Iron in the coordination sphere
b = no. of secondary valencies of central iron ion.
c = Effective atomic number of Iron in the coordination sphere.
Then find the value of (c + a – 2b)
4. Coordination number of Cr in CrCl3.5H2O as six. The possible volumes of 1 M Ag NO3 needed to precipitate
the chlorine inoutersphere in 200 ml of 0.1 M solution of the complex is/are.
Write your answer as V1 + V2 + V3 + .........
5. Ni+2 form a complex ion in water having the formula [Ni(H2O)6]+2. How many of the following statements are
true for the complex ion ?
(i) The complex is octahedral in shape. (ii) The complex is diamagnetic in nature.
(iii) Ni has incompletely filled 3d subshell.
+2
(iv) Secondary valency of Ni+2 is 6.
(v) All the bonds (metal-ligand) are perpendicular to each other.
(vi) All the 3d orbitals of Ni+2 are degenerate
(vii) Total spin of the complex is 1. (viii) The hybridisation of Ni+2 is d2sp3
(ix) The complex is more stable than [Ni(en)3] +2
(x) Effective atomic number of Ni+2 is 36.
6. How many of the following is correctly matched complex ?

Complex Oxidation no. on central metal Electronic configuration
(1) K3[Co(C2O4)3] +3 t 62g e 0g
(2) (NH4)2[CoF4] +2 t 52g e 2g

(3) Cis-[Cr(en)2Cl2]Cl +3 t 32g e 0g
(4) [Mn(H2O)6]SO4 +2 t 32g e 2g
7. Total number of paramagnetic complexes which are inner orbital complexes :
[Cr(NH3)6]Cl3 , [Co(NH3)6](NO3)2 , [Ni(NH3)6]SO4, K2[PtCl6],
[V(H2O)6]SO4 , [Mn(NH3)6]SO4 , [Fe(H2O)5 (NO)]SO4 , K3[CuCl4] , Na4[Fe(CN)5 (NOS)]
8. The number of coordination isomers possible for [Fe(NH3)6]3+ [Cr(C2O4)3]3– is _______
9. Find the sum of number of geometrical isomers for following complexes.

(a) [CoCl2Br2]2– (b) [Rh(en)3]3+ (c) [Cr(en)2 Br2]+
(d) [Pt en Cl2] (e) [Co(NH3)3(NO2)3]
10. What is the sum of bond order of Fe–C bond and C–O bond in Fe(CO) 5 ?
11. How many isomeric forms are possible for the octahedral complex, [Rh(en)2(NO2)(SCN)]+ ?
ADVCOR - 11
PART - III : ONE OR MORE THAN ONE OPTIONS CORRECT TYPE

1. Which of the following statement(s) are incorrect ?
(A) Those additional compounds which lose their identity in solution are called double salts.
(B) In K3[Fe(CN)6] Fe2+ and CN– ion can give quantitative identification test.
(C) [KAl(SO4)2.12H2O] is a coordination compound.
(D) All acids are lewis acids and  donors.
2. The effective atomic number of Co(CO)4 is 35 and hence is less stable. It attains stability by
(A) oxidation of Co (B) reduction of Co (C) dimerization (D) none
3. Select the correct statements ;

(A) Potassium ferrocyanide and potassium ferricyanide can be differentiated by measuring the solid state
magnetic moment.
(B) The complex [Co(NH3)5Br]SO4 and [Co(NH3)5SO4]Br can be differentiated by adding aqueous solution of
barium chloride
(C) The complex [Co(NH3)5Cl]Br and [Co(NH3)5Br]Cl can be differentiated by adding aqueous solution of silver
nitrate.
(D) the complex [Co(NH3)6Cl3] and [Co(NH3)5Cl]Cl2 can be differentiated by measuring molar conductance
4. Consider the following statements :

S1 : [MnCl6 ]3 – , [FeF6 ]3 – and [CoF6]3 – are paramagnetic having four, five and four unpaired electrons respectively.
S2 : Low value of formation constant of a complex indicates its high thermodynamic stability.
S3 : The crystal field splitting o , depends upon the field produced by the ligand and charge on the metal ion.
and arrange in the order of true/ false.
(A) T T T (B) T F T (C) F T F (D) T F F
5. Which of the following is/are correctly matched ?

(A) [Ni(CO)4] – dsp2 and diamagnetic.
(B) [Ni(en)3](NO2)2 - sp3d2 and two unpaired electrons.
(C) [V (NH3)6]Cl3- sp3d2 and two unpaired electrons.
(D) [Mn (NO+)3(CO)] - sp3 and diamagnetic.
6. Which of the following statement(s) is/are correct with respect to the crystal field theory ?
(A) It considers only the metal ion d–orbitals and gives no consideration at all to other metal orbitals.
(B) It cannot account for the  bonding in complexes.
(C) The ligands are point charges which are either ions or neutral molecules
(D) The magnetic properties can be explained in terms of splitting of d- orbitals in different crystal field.
7. 'Spin only' magnetic moment of Ni in [Ni(dmg)2] is same as that found in :

(A) Ni in [NiCl2 (PPh3)2] (B) Mn in [MnO4]–
(C) Co in [CoBr4]2– (D) Pt in [Pt (H2O)2 Br2]
8. Which complex of the following pairs has the larger value of 0 ?

(i) [Co(CN)6] 3 – and [Co(NH3)6]3+ (ii) [Co(H2O)6]3+ and [Rh(H2O)6]3+
(iii) [Co(H2O)6]3+ and [Co(H2O)3 ] 3+ (iv) [Co(NH3)6]3+ and [CoF6] 3–
Select the correct one
(A) [Co(CN)6]3 – > [Co(H2O)6]3+ (B) [Co(H2O)6]2+ < [Co(H2O)6]3+
(C) [Co(H2O)6]3+ > [Rh(H2O)6 ]3+ (D) [Co(NH3)6]3+ < [CoF6] 3 –
9. Which of the following isomerisms is/are shown by the complex [CoCl2(OH2)2(NH3)2 ]Br ?
(A) Ionization (B) Linkage (C) Geometrical (D) optical
ADVCOR - 12
10. Three arrangements are shown for the complex [Co(en) (NH3)2 Cl2]+. Pick up the wrong statement.
(A) I and II are geometrical isomers (B) II and III are optical isomers
(C) I and III are optical isomers (D) II and III are geometrical isomers
11. Consider the following complexies [V(CO)6]–, [Cr(CO)6] and [Mn(CO)6]+. Then incorrect statement (s) about
metal carbonyls is /are.
(A) ‘C –O’ bond is strongest in the cation and weakest in the anion
(B) ‘C –O’ bond order is less in the cation than in anion.
(C) ‘C –O’ bond longer in the cation than in anion or neutral carbonyl.
(D) ‘M–C’ bond order is higher in the cation than in anionic or neutral carbonyl.
12. Following Sidwick's rule of EAN, Co(CO)x will be :

(A) Co2(CO)4 (B) Co2(CO)3 (C) Co2(CO)8 (D) Co2(CO)10
PART - IV : COMPREHENSION
Read the following passage carefully and answer the questions.
Comprehension # 1
In coordination chemistry there are a variety of methods applied to find out the structure of complexes. One
method involves treating the complex with known reagents and from the nature of reaction, the formula of the
complex can be predicted. An isomer of the complex Co(en)2(H2O)Cl2Br, on reaction with concentrated
H2SO4 (dehydrating agent) it suffers loss in weight and on reaction with AgNO3 solution it gives a white
precipitate which is soluble in NH3 (aq).
1. The correct formula of the complex is :

(A) [CoClBr(en)2] H2O (B) [CoCl(en)2 (H2O)] BrCl
(C) [Co Br(en)2(H2O)]Cl2 (D) [CoBrCl(en)2]Cl . H2O
2. If all the ligands in the coordination sphere of the above complex be replaced by F¯, then the magnetic
moment of the complex ion (due to spin only) wll be :
(A) 2.8 BM (B) 5.9 BM (C) 4.9 BM (D) 1.73 BM
3. Similarly if all the ligands in the coordination sphere be replaced by NO2¯ , then the magnetic moment of the
complex ion (due to spin only) will be :
(A) 1.73 BM (B) 0.0 BM (C) 4.9 BM (D) 5.9 BM
4. If one mole of original complex is treated with excess Pb(NO3)2 solution, then the number of moles of white
precipitate (of PbCl2) formed will be :
(A) 0.5 (B) 1.0 (C) 0.0 (D) 3.0
5. The number of geometrical isomers of the formula of the above original complex are (including the complex):
(A) 2 (B) 3 (C) 4 (D) 1
ADVCOR - 13
EXERCISE - 1
PART - I
A-1. K2SO4.Cr2(SO4)3 2K+(aq) + 2Cr3+ (aq) + 4SO42–
So chrome alum is a double salt. It when dissolved in water gives its constituent ions. Hence it gives the test
of K+, Cr3+ and SO42– ions.
CuSO4.4NH3 [Cu(NH3)4] SO4 [Cu(NH3)4]2+ (aq) + SO42– (aq)
As copper (II) is present in coordination sphere it will not give the test of Cu2+ ion.
A-2. The coordination number of the central atom/ion is determined by the number of sigma bonds between the
ligands and the central atom/ions i.e. the number of ligand donor atoms to which the metal is directly attached.
The oxidation number of the central atom is defined as the charge it would carry if all the ligands are removed
along with the electron pairs that are shared with the central atom.
Complex Coordination Number Oxidation State
(a) [AgCl2]– 2 1
(b) [Cr(H2O)5Cl]2+ 6 3
(c) [Co(NCS)4]2– 4 2
(d) [Co(NH3)3(NO2)3] 6 3
(e) [Fe(EDTA)]– 6 3
(f) [Cu(en)2]SO4 4 2
(g) K[Pt(NH3)Cl5] 6 4
A-3. (A) Methyl isocyanide, monodentate. (B) acetylacetonate, bidentate
(C) azide, monodentate (D) diethylenetriamine, tridentate
(E) ethylenediamine tetraacetate, hexadentate (F) ethylenediamine triacentate, pentadentate
(G) oxalato, bidentate (H) dimethylglyoximato
(I) isocyanido, monodentate (J) nitrito, monodentate (K) Oxido, monodentate
(L) peroxido, bidentate (M) superoxido, monodentate
A-4. (A) nitrito-N M  O—N=O nitrito-O
(B) M  SCN thiocyanato or thiocyanato-S, M  NCS isothiocyanato or thiocyanato-N
(C) or dithioxalate
(D) M  OCN cyanato-O or cyanato-N, M  NCO isothiocyanato or thiocyanato-N

(E) M  NOS thionitrito-N or, M  SON thionitrito-S
O 3–
C O
O C
O O
C O
A-5. (a) Fe
C O O
O
O C
C O
O
[Fe(C2O4)3]3– [Pt(en)2]2+
ADVCOR - 14
The ligands, oxalate and ethylenediamine are bidentate as each ligand has two donor atoms. So in
1st case the number of chelate rings (five membered) are three where as in 2nd case the number of
chelate rings (five membered) are two.
The coordination number and oxidation state of iron are six and +3 respectively and the coordination
number and oxidation state of platinum are four and +2 respectively.
(b) K2[Ni(CN)4] 2K+ (aq) + [Ni(CN)4]2– (aq)
[Cr(en)3] Cl3 [Cr(en)3]3+ (aq) + 3Cl– (aq)
Fe4[Fe(CN)6]3 4Fe3+ (aq) + 3[Fe(CN)6]4– (aq)
[PtCl2(en)2] (NO3)2 [PtCl2(en)2]2+ (aq) + 2(NO3)– (aq)
So, [Ni(CN)4] , [Cr(en)3]3+, 3[Fe(CN)6]4– and [PtCl2(en)2]2+ are coordination entities and K+, Cl–, Fe3+
2–
and NO3– are counter ions.

(c) Coordination compounds are acid-base adduct. Cations are electron deficient, therefore, are called
Lewis acids where as ligands are electrons donors, therefore, are called as Lewis base.
LEWIS ACID LEWIS BASE
(i) [HgBr4]2- Hg2+ 4Br–
(ii) [Ni(H2O)6] 2+
Ni 2+
6H2O
(iii) [PdCl2(NH3)2] Pd2+ 2Cl– & 2NH3
(iv) [Al(OH)4] –
Al 3+
4OH–
(v) [Ag(CN)2] -
Ag +
2CN–
(vi) [Cr(CO)6] Cr 0
6CO
B-1. (a) [Co(NH3)6]Cl3, Hexaamminecobalt(III) chloride
(b) [Rh(NH3)5I]I2, Pentaammineiodidorhodium(III) iodide
(c) [Fe(CO)5], Pentacarbonyliron(0)
(d) [Fe(C2O4)3]3–, Trioxalatoferrate(III) ion OR Tris(oxalato)ferrate(III) ion
(e) [Cu(NH3)4]SO4, Tetraamminecopper(II) sulphate
(f) Na[Cr(OH)4], Sodium tetrahydroxidochromate(III)
(g) [Co(gly)3], Triglycinatocobalt(III) OR Tris(glycinato)cobalt(III)
(h) [Fe(H2O)5(SCN)]2+, Pentaaquathiocyanato–S–iron(III) ion
(i) K2[HgI4], Potassium tetraiodidomercurate(II)
(j) Co[Hg(SCN)4], Cobalt(II) tetrathiocyanato–S–mercurate(II)
(k) Fe4[Fe(CN)6]3, Iron(III) hexacyanidoferrate(II)
(l) K3[Co(NO2)6], Potassium hexanitro–N–cobaltate(III)
(m) [Ni(dmg)2], Bis(dimethylglyoximato)nickel(II)
(n) K2[PtCl6], Potassium hexachloridoplatinate(IV)
(o) Na2[Fe(CN)5NO+], Sodium pentacyanidonitrosoniumferrate(II)
(p) [Fe(H2O)5(NO+)]SO4, Pentaaquanitrosoniumiron(I) sulphate
(q) [Cu(CN)4]3–, Tetracyanidocuperate(I) ion
(r) (NH4)2[PtCl6], Ammonium hexachloridoplatinate(IV)
B-2. (a) [CoBr(en)2(ONO)]+1 Bromidobis(ethylenediamine)nitrito–O–cobalt(III)
(b) [Co(NH3)6][Co(ONO)6] Hexaamminecobalt(III) hexanitrito–O–cobaltate(III)
(c) [Co(NH3)5(CO3)]Cl Pentaamminecarbonatocobalt(III) chloride
(d) [Pt(NH3)4Cl2][PtCl4] Tetraamminedichloridoplatinum(IV) tetrachloridoplatinate(II)
(e) [Co(en)3]2(SO4)3 Tris(ethylenediamine)cobalt(III) sulphate or
Tris(ethane -1, 2-diamine)cobalt(III) sulphate.
(f) [(NH3)5Co-NH2-Co(NH3)4(H2O)]Cl5
Pentaamminecobalt(III)––amidotetraammineaquacobalt(III) chloride
(g) [Cr(CO)5(PPh3)] Pentacarbonyltriphenylphosphinechromium(0)
(h) [(CO)5Mn-Mn(CO)5] Decacarbonyldimanganese(0)
(i) Cr(-C6H6)2 Bis(  6–benzene)chromium(0)
(j) [Co(NH3)4(OH2)2][BF4]3 Tetraamminediaquacobalt(III) tetrafluoridoborate(III)
(l) Ba[Zr(OH)2(ONO)2(ox)] Barium dihydroxidodinitrito–O–oxalatozirconate(IV)
(l) [Co(NH3)6][Co(C2O4)3] Hexaamminecobalt(III) trioxalatocobaltate(III)
ADVCOR - 15
B-3. (a) Tetraamminezinc(II) Nitrate, [Zn(NH3)4](NO3)2
(b) Tetracarbonylnickel(0), [Ni(CO)4]
(c) Potassium amminetrichloridoplatinate(II), K[Pt(NH3)Cl3]
(d) Dicyanidoaurate(I) ion, [Au(CN)2]–
(e) Sodium hexafluoridoaluminate(III), Na3[AlF6]
(f) Diamminesilver(I) ion, [Ag(NH3)2]+
B-4. (a) Diamminetriaquahydroxidochromium(III) nitrate [Cr(NH3)2(H2O)3(OH)](NO3)2
(b) Tetrakis(pyridine)platinum(II) tetraphenylborate(III) [Pt(Py)4][B(ph)4]2
(c) Dibromidotetracarbonyliron(II) [Fe(Br)2(CO)4]
(d) Ammonium diamminetetrakis(isothiocyanato)chromate(III). (NH4)[Cr(NH3)2(NCS)4]
(e) Pentaamminedinitrogenruthenium(II) chloride [Ru(NH3)5N2]Cl2
(f) Barium dihydroxidodinitrito-O-oxalatozirconate(IV) Ba[Zr(OH)2(ONO)2(ox)]
(g) Tetrapyridineplatinum(II) tetrachloridoplatinate(II) [Pt(py)4][PtCl4]
C-1. (a) – iv, (b) – viii, (c) – i, (d) – vii,
(e) – iii, (f) – v, (g) – ii, (h) – vi
C-2. 0.0075.
C-3. (a) 36 (b) 36 (c) 36 (d) 36
(e) 36 (f) 36 (g) 54 (h) 86
C-4. ii < i < iv < iii.
D-1. (i) [Cr(NH3)4Cl Br]Cl [Cr(NH3)4Cl Br]+ + Cl– ; Ag+ + Cl–  AgCl  (white) ; soluble in dilute NH3.
[Cr(NH3)4Cl2]Br [Cr(NH3)4Cl2]+ + Br– ; Ag+ + Br–  AgBr  (yellow) ; soluble in conc. NH3.
So, A = [Cr(NH3)4Cl Br]Cl and B = [Cr(NH3)4Cl2]Br.
(ii) In both complexes chromium is in +3 oxidation state. Chromium with 3d3 configuration has 3 unpaired
electrons with weak field as well as strong field ligand. So, the hybridisation scheme is as follow :
(iii) = n (n  2) =
15 (iv) EAN = 24 – 3 + 12 = 33
(v) Yes, both have two ions per formula unit.
(vi) AgCl + 2NH3 [Ag(NH3)2]Cl ; AgBr + 2NH3 [Ag(NH3)2]Br
D-2. (a) [NiBr4]2– sp3, tetrahedral

(b) [AuCl4]– dsp2, square planar
(c) [Pt(NH3)4]2+ dsp2, square planar
E-1. (i) potasium amminetetracyanidonitrosoniumchromate(I)
(ii) Octahedral
(iii) One unpaired electron (iv) It is paramagnetic with one unpaired electron
(v) EAN = 24 – 1 + 2 × 6 = 35 (vi) d2sp3
E-2. (a) [Fe(CN)6]3– d2sp3, octahedral (b) [MnBr4]2– sp3, tetrahedral
(c) [Fe(H2O)6]2+ sp3d2, octahedral (d) [Co(SCN)4]2– sp3, tetrahedral
E-3. Since ammonia is a strong field ligand so can pair up the electrons of Co(III), so will form an inner d-orbital
complex having zero magnetic moment while fluoride being a weak field ligand can not pair up electrons and
forms outer d-complex with higher magnetic moment equal to four unpaired electrons.
ADVCOR - 16
E-4. (a) i < iv < ii < iii (b) X < O < N < C (c) Br– < S2– < NO3– < H2O < NH3 < NO2– < CN– < CO
E-5. (a) F– is weak field ligand. Cr3+, 3d3
So number of unpaired electrons = 3
eg
bari centre
d-orbitals
in presence
(b) H2O is weak field ligand. V3+, 3d2 of ligand field
t2g
d-orbitals
in absence
of ligand field
So number of unpaired electrons = 2

eg
bari centre
d-orbitals
in presence
(c) CN– is strong field ligand. Fe3+, 3d5 of ligand field
t2g
d-orbitals
in absence
of ligand field
So number of unpaired electron = 1.
ADVCOR - 17
eg
bari centre
d-orbitals
in presence
(d) en is strong field ligand. Cu2+, 3d9 of ligand field
t2g
d-orbitals
in absence
of ligand field
So number of unpaired electron = 1.

eg
bari centre
d-orbitals
in presence
(e) F– is weak field ligand. Fe3+, 3d5 of ligand field
t2g
d-orbitals
in absence
of ligand field
So number of unpaired electrons = 5.

F-1. As 3d6 configuration has higher CFSE as compared to 3d7 so it gets oxidised in presence of complexing
reagent to easily have d2sp3 hybridisation.
F-2. yellow colour
F-3. (a) CN–, F–
(b) (i) 0 (ii) 0 (iii) 0 (iv) 0
G-1. (i) Linkage (ii) Coordination (iii) Ionisation (iv) Hydrate
G-2. (a) There are three constitutional isomers
(i) [Ru(NH3)5(NO2)]Cl
(ii) [Ru(NH3)5Cl](NO2) or [Ru(NH3)5Cl]ONO
(iii) [Ru(NH3)5 ONO]Cl
(i) & (ii) are ionisation isomers
(i) & (iii) are linkage isomers
(b) (i) (ii) (iii)
(iv) (v) (vi)
G-3. (a) Two (b) None (c) Two (d) None (e) Two (f) None
G-4. (a) No ; (b) Yes ; (c) Yes ; (d) Yes ; (e) Yes ; (f) No.
ADVCOR - 18
CO CO
CO CO
OC OC
H-1. (a) V (b) Cr
CO CO
OC OC
CO CO
CO
OC
OC CO CO
OC
(c) OC Mn Mn CO (d) Fe CO
OC
CO CO
CO CO
CO
CO
(e) Ni
OC CO
CO
H-2. (i) Increases (ii) Decreases
PART - II
A-1. (B) A-2. (C) A-3. (A) A-4. (B) A-5. (B)
A-6. (D) A-7. (B) A-8. (A) A-9. (D) B-1. (C)
B-2. (A) B-3. (D) B-4. (D) B-5. (C) C-1. (C)
C-2. (B) C-3. (C) C-4. (A) C-5. (A) C-6. (B)
C-7. (C) C-8. (D) C-9. (C) D-1. (A) D-2. (C)
D-3. (C) D-4. (B) D-5. (A) D-6. (A) E-1. (C)
E-2. (A) E-3. (A) E-4. (B) E-5. (A) E-6. (D)
E-7. (D) E-8. (C) E-9. (A) E-10. (C) E-11. (C)
E-12. (C) F-1. (B) F-2. (B) G-1. (C) G-2. (B)
G-3. (B) G-4. (D) G-5. (C) G-6. (C) H-1. (D)
H-2. (D)
PART - III
1. (A - p,r,t); (B - p,s,t); (C - p,r,t); (D - q,r) 2. (A - p,q,r); (B - q,r,s) ; (C - p,q,r,s) ; (D - p,q)
ADVCOR - 19
EXERCISE - 2
PART - I
1. (B) 2. (C) 3. (A) 4. (B) 5. (D)
6. (D) 7. (D) 8. (C) 9. (D) 10. (B)

11. (B) 12. (A) 13. (A)
PART - II
1. 13 2. 05 3. 26 4. (40 + 20) ml = 60 ml
5. 4 6. 3 7. 3 8. 4 9. 4
10. 4
11. It shows linkage, geometrical and optical isomerism.
(1) cis-NO2 / SCN (5) trans-NO2 / SCN (9)
(2) cis-ONO / SCN (6) trans-ONO / SCN (10)
(3) cis-NO2 / NCS (7) trans-NO2 / NCS (11)
(4) cis-ONO / NCS (8) trans-ONO / NCS (12)
PART - III
1. (BCD) 2. (BC) 3. (ABCD) 4. (B) 5. (BD)
6. (ABCD) 7. (BD) 8. (AB) 9. (ACD) 10. (BCD)

11. (BCD) 12. (C)
PART - IV
1. (D) 2. (C) 3. (B) 4. (A) 5. (A)
6. (B) 7. (A) 8. (C)
ADVCOR - 20
This Section is not meant for classroom discussion. It is being given to promote self-study
and self testing amongst the Resonance students.
PART - I : PRACTICE TEST-1 (IIT-JEE (MAIN Pattern))
Max. Marks : 120 Max. Time : 1 Hr.
Important Instructions
1. The test is of 1 hour duration.
2. The Test Booklet consists of 30 questions. The maximum marks are 120.
3. Each question is allotted 4 (four) marks for correct response.
4. Candidates will be awarded marks as stated above in Instructions No. 3 for correct response of each question.
¼ (one fourth) marks will be deducted for indicating incorrect response of each question. No deduction from the
total score will be made if no response is indicated for an item in the answer sheet.
5. There is only one correct response for each question. Filling up more than one response in any question will be
treated as wrong response and marks for wrong response will be deducted accordingly as per instructions 4
above.
1. In which of the following complexes the nickel metal is in highest oxidation state ?
(1) Ni(CO)4 (2) K2NiF6 (3) [Ni(NH3)6](BF4)2 (4) K4[Ni(CN)6]
2. The EAN of platinum in potassium hexachloroplatinate (IV) is :

(1) 46 (2) 86 (3) 36 (4) 84
3. The IUPAC name of K2[Cr(CN)2O2(O)2(NH3)] is :

(A) Potassium amminedicyanodioxoperoxochromate(VI)
(2) Potassium amminecyanoperoxodioxochromium(VI)
(3) Potassium amminedicyanoperoxooxochromium(VI)
(4) Potassium amminecyanodiperoxodioxochromate(VI)
4. Which one of the following high-spin complexes has the largest CFSE (Crystal field stabilization energy) ?
(1) [Mn(H2O)6]2+ (2) [Cr(H2O6)]2+ (3) [Mn(H2O)6]3+ (4) [Cr(H2O)6]3+
5. Which of the following complex will show optical activity ?

(1) trans-[Co(NH3)4Cl2]+ (2) [Cr(H2O)6]3+
(3) cis-[Co(NH3)2(en)2]3+
(4) trans-[Co(NH3)2(en)2]3+
6. Which kind of isomerism is shown by the complex [Co(NH3)5(ONO)]SO4 ?

1. Ionisation isomerism 2. Linkage isomerism
3. Geometrical isomerism 4. Optical isomerism
(1) 1, 2, 3 and 4 are correct (2) 1, 3 and 4 are correct only
(3) 1 and 2 are correct only (4) 2, 3 and 4 are correct only
7. Which of the following statements is correct for complex [Cr(NH3)(CN)4(NO)]2 – (given that n = 1)?
(1) It is d2sp3 hybridised.
(2) The chromium is in +1 oxidation state
(3) It is heteroleptic complex and its aqueous solution is coloured
(4) All of these.
ADVCOR - 21
8. Consider the following statements
S1 : [ Cr (NH3)6 ]3+ is a inner orbital complex with crystal field stabilization energy equal to – 1.2 o
S2 : The complex formed by joining the CN– ligands to Fe3+ ion has theoretical value of ‘spin only’ magnetic
moment equal to 1.73 B.M.
S3 : Na2S + Na2[Fe(CN)5NO]  Na4[Fe(CN)5NOS], In reactant and product the oxidation states of iron
are same
and arrange in the order of true/false.
(1) F T F (2) T T F (3) T T T (4) F F F
9. Which of the following statements is false ?

(1) Complex of Pt (+II) and Au (+III) are square planar - including those with weak field ligands such as halide
ions.
(2) In tetrahedral complex, the t2g orbitals are nearer to the direction of the ligands.
(3) For do, d5 and d10 arrangements the CFSE is zero in both octahedral and tetrahedral complexes with weak
field ligands.
(4) None.
10. If excess of AgNO3 solution is added to 100 mL of a 0.024 M solution of dichlorobis(ethylenediamine)cobalt

(III) chloride. How many moles of AgCl be precipitated ?
(1) 0.0012 (2) 0.0016 (3) 0.0024 (4) 0.0048
11. A complex of certain metal has the magnetic moment of 4.91 BM whereas another complex of the same
metal with same oxidation state has zero magnetic moment. The metal ion could be :
(1) Co2+ (2) Mn2+ (3) Fe2+ (4) Fe3+
12. Oxidation number of Fe in violet coloured complex Na4[Fe(CN)5(NOS)] is :

(1) 0 (2) 2 (3) 3 (4) 4
13. Aqueous solution of nickel sulphate on treating with pyridine and then adding a solution of sodium nitrite
gives dark blue crystals of :
(1) [Ni(py)4]SO4 (2) [Ni(py)2(NO2)2] (3) [Ni(py)4](NO2)2 (4) [Ni(py)3(NO2)]2SO4
14. The IUPAC name of [Co(NH3)6] [Cr(C2O4)3] is :

(1) Hexaamminecobalt(III) tris(oxalato)chromate(III)
(2) Hexaamminecobalt(III) tris(oxalato)chromium(III)
(3) Hexaamminecobalt(II) tris(oxalato)chromium(III)
(4) Hexaamminecobalt(III) trioxalatechromium(III)
15. In the compound lithiumtetrahydroaluminate, the ligand is :

(1) H+ (2) H (3) H– (4) None of these
16. The oxidation number of Co in the complex ion is :

(1) +2 (2) +3 (3) +4 (4) +6
17. The magnitude of crystal field stabilisation energy (CFSE of t) in tetrahedral complexes is considerably less
than that in the octahedral field. Because
(1) There are only four ligands instead of six so the ligand field is only 2/3 in tetrahedral complex
(2) The direction of the orbitals does not coincide with the direction of the ligands. This reduces the crystal
field stabilization energy () by further 2/3
(3) Both points (1) and (2) are correct
(4) Both points (1) and (2) are wrong
18. Other than the X-ray diffractions, how could be the following pairs of isomers be distinguished from one
another by ;
[Cr(NH3)6] [Cr(NO2)6] and [Cr(NH3)4(NO2)2] [Cr(NH3)2(NO2)4]
(1) cryoscopic method (2) measurement of molar conductance
(3) measuring magnetic moments (4) observing their colours
ADVCOR - 22
19. [Fe(en)2(H2O)2]2+ + en  complex(X). The correct statement about the complex (X) is :
(1) it is a low spin complex. (2) it is diamagnetic.
(3) it shows geometrical isomerism. (4) (1) and (2) both.
20. Which of the following pairs will show the same magnetic moment (‘spin only’)?
(1) [Cr(H2O)6]3+ and [Fe(H2O)5NO]2+ (2) [Mn(CN)6]4– and [Fe(CN)6]3–
(3) [Ni(CO)4] and [Zn(NH3)4]2+
(4) All of these.
21. What will be the theoretical value of ‘spin only’ magnetic moment when Fe(SCN) 3 reacts with a solution
containing F– ions to yield a colourless complex ?
(1) 2.83 B.M. (2) 3.87 B.M. (3) 5.92 B.M. (4) 1.73 B.M.
22. Which of the following statements about Fe(CO)5 is correct?

(1) It is paramagnetic and high spin complex (2) It is diamagnetic and high spin complex
(3) It is diamagnetic and low spin complex (4) It is paramagnetic and low spin complex
23. The crystal field-splitting for Cr3+ ion in octahedral field changes for ligands –, H2O, NH3, CN– and the
increasing order is :
(1) – < H2O < NH3 < CN– (2) CN– < – < H2O < NH3
(3) CN < NH3 < H2O < 
– –
(4) NH3 < H2O < – < CN–
24. Which of the following complex ion is not expected to absorb visible light ?
(1) [Ni(H2O)6]2+ (2) [Zn (NH3)4]2+ (3) [Cr(NH3)6]3+ (4) [Fe(H2O)6]2+
25. Of the following complex ions, the one that probably has the largest overall formation constant, K f, is :
(1) [Co(NH3)6]3+ (2) [Co(H2O)6]3+ (3) [Co(NH3)2(H2O)4]3+ (4) [Co(en)3]3+
26. The correct structure of Fe(CO)5 is :

(1) octahedral (2) tetrahedral (3) square pyramidal (4) trigonal bipyramidal
27. Arrange the following in order of decreasing number of unpaired electrons :

: [Fe(H2O)6]2+ : [Fe(CN)6]3– : [Fe(CN)6]4– V : [Fe(H2O)6]3+
(1) V, ,,  (2) ,, , V (3) ,, , V (4) ,, , V
28. Match List-I (Complexes) with List-II (Hybridization) of central atom and select the correct answer using the
codes given below the lists :
List-I List-II
A Ni(CO)4 1. sp3
B [Ni(CN)4]2–
2. dsp2
C [Fe(CN)6] 4–
3. sp3d2
D [MnF6]4– 4. d2sp3
Code :
A B C D A B C D
(1) 1 3 2 4 (2) 5 2 4 3
(3) 5 3 2 4 (4) 1 2 4 3
29. Which of the following complexes shows ionization isomerism ?

(1) [Cr(NH3)6]Cl3 (2) [Cr(en)2 ]Cl2 (3) [Cr(en)3]Cl3 (4) [Co(NH3)5Br]SO4
30. Coordination number of Ni in [Ni(C2O4)3]4– is :

(1) 3 (2) 6 (3) 4 (4) 2
ADVCOR - 23
Practice Test-1 (IIT-JEE (Main Pattern))
OBJECTIVE RESPONSE SHEET (ORS)
Que. 1 2 3 4 5 6 7 8 9 10
Ans.
Que. 11 12 13 14 15 16 17 18 19 20
Ans.
Que. 21 22 23 24 25 26 27 28 29 30
Ans.
PART - II : NATIONAL STANDARD EXAMINATION IN CHEMISTRY (NSEC) STAGE-I

1. In which of the following compounds, the oxidation number of the stated transition metal
is zero. [NSEC-2000]
(A) [Ni(CO)4] (B) [Pt(C2H4)CI3]
(C) [Co(NH3)6]CI2 (D) [Fe(H2O)3](OH)2
2. Ligands contain : [NSEC-2001]

(A) lone pair of electron (B) incomplete octet (C) unpaired electron (D) shared pair of electron
3. Valency bond theory was proposed by : [NSEC-2001]

(A) Heitler and London (B) Slater and Mullican (C) Pauling (D) Rutherford
4. eg orbitals include [NSEC-2002]

(A) dxy and dyz (B) dyz and dxz (C) dyz and dxz (D) dx2 – y2 and dz2
5. The theory which utilises pure electrostatic bonding between metal and ligand is : [NSEC-2002]
(A) valency bond theory (B) molecular orbital theory
(C) crystal field theory (D) ligand field theory
6. Dimethyl glyoxime forms a square planar complex with Ni2+. This complex should be [NSEC-2003]
(A) diamagnetic (B) paramagnetic having 1 unpaired electron
(C) paramagnetic having 2 unpaired electrons (D) ferromagnetic.
7. A [M(H2O)6]2+ complex typically absorbs at around 600 nm. It is allowed to react with ammonia to form a new
complex [M(NH3)6]2+ that should have absorption at [NSEC-2003]
(A) 800nm (B) 580nm (C) 620nm (D) 320nm.
8. The least stable metal carbonyl as per the bonding considerations should be [NSEC-2003]
(A) Cr(CO)6 (B) Mn(CO)6 (C) Fe(CO)5 (D) Ni(CO)4.
9. A coordination complex of type MX2Y2 [M = metal ion; X,Y = monodentate ligands], can have either a
tetrahedral or a square planar geometry. The maximum number of possible isomers in these two cases are
respectively [NSEC-2003]
(A) 1 and 2 (B) 2 and 1 (C) 1 and 3 (D) 3 and 2
10. The blue pigment prussian blue is an iron complex with formula [NSEC-2003]
(A) K4[Fe(CN)6] (B) K2[Fe(CN)4(NH3)2] (C) Fe4[Fe(CN)6]3 (D) Na2[Fe(CN)5NO].
ADVCOR - 24
11. When H2S is passed through a solution containing Cu2+, Cd2+ and an excess of cyanide ions, cadmium
sulphide precipitates while copper ions remain in solution. This is because [NSEC-2003]
(A) Cu2+ forms a stable complex with cyanide while Cd2+ does not
(B) Cu2+ forms a more stable complex with cyanide than Cd2+
(C) Cu2+ does not form a sulphide
(D) both CdS and CuS are formed, but CuS is soluble.
12. IUPAC name for K3 [A(C2O4)3] is [NSEC-2004]

(A) potassium trioxalatoaluminate (III) (B) potassium aluminiumoxalate
(C) potassium trioxalatealuminium (II) (D) potassium trioxalatealuminium (III)
13. Geometrical isomerism would be expected for which of the following compounds [NSEC-2005]
(A) [Zn(NH3)4]2+ (B) [Pt(NH3)2C12] (C) [Pt(NH3)3Cl]+ (D) K2[CuCI4].
14. Co-ordination compounds [Pt(NH3)3(SCN)] and [Pt(NH3)3(NCS)] are examples of [NSEC-2005]

(A) co-ordination isomerism (B) linkage isomerism
(C) optical isomerism (D) hydrate isomerism.
15. The highest molar conductivity will be exhibited by the complex [NSEC-2005]
(A) [Cr(NH3)6]CI3 (B) [Cr(NH3)6CI]CI2 (C) [Cr(NH3)6CI2]CI (D) [Cr(NH3)6CI3].
16. The number of unpaired electrons in the scandium atom is [NSEC-2006]

(A) 1 (B) 2 (C) 0 (D) 3
17. How many isomers are possible for the complex [Co(en)2CI2] (en = ethylene diamine) [NSEC-2006]
(A) 4 (B) 2 (C) 6 (D) 3
18. In which of the following compounds is the oxidation number of the transition metal zero? [NSEC-2007]
(A) [Ni(CO)4] (B) [Pt(C2H4)Cl3 (C) [Co(NH3)6]Cl2 (D) [Fe(H2O)3](OH)2
19. [NiCl4]2– is paramagnetic and therefore its geometry is : [NSEC-2007]

(A) pyramidal (B) bi-pyramidal (C) tetrahedral (D) square planar
20. dsp2 hybridization represents [NSEC-2007]

(A) octahedral geometry (B) square-planar geometry
(C) trigonal-bipyramidal geometry (D) square-pyramidal geometry
21. Which isomerism is exhibited by[Co(NH3)6][Cr(CN)6] and [Cr(NH3)6][Co(CN)6]? [NSEC-2007]

(A) Ionization (B) Linkage (C) Coordination (D) Polymerization
22. The complex pentaaminecarbonatocobalt (III) chlorides is: [NSEC-2007]

(A) [Co(NH3)5CO3] CI (B) [Co(NH2)5CO3]CI (C) [Co(NH2)5CO2]CI (D) [Co(NH3)5CO2]CI
23. According to the Crystal Field Theory, the energy of dxy orbital is lower than d in an octahedral complex
x2 y2
because [NSEC-2007]
(A) the dxy orbital near the ligands.
(B) the repulsion between the dxy electrons and ligand electrons is less than that between d 2 2 and ligand
x y
electrons.
(C) the repulsion between the dxy electrons and ligand electrons is more than that between d 2 2 and ligand
x y
electrons.
(D) the d orbital is away the ligands.
x2 y2
24. The orbitals of iron involved in the hybrdization in Fe(CO)5 are [NSEC-2007]
(A) s, px, py, pz and d (B) s, px, py, d and d
x2 y2 z2 x2 y2
(C) s, px, py, pz and d (D) s, px, pz, dxy and d

z2 x2 y2
ADVCOR - 25
25. The crystal field stabilization energy (CFSE) in [Co(SCN)6]3– is : [NSEC-2007]
(A) 24 Dq (B) 18 Dq (C) 4 Dq (D) 0 Dq
26. Metal carbonyls have the metal ions in zero or unusually lower oxidation states. This is because :
[NSEC-2007]
(A) carbonyl ligand is reducing in nature. (B) carbonyl is a highly electron rich ligand.
(C) carbonyl is a strongly o –bonding ligand. (D) carbonyl is a strongly p -acidic ligand.
27. In which of the following transition metal ion complexes, the colour in not due to d-d transition ? [NSEC-2008]
(A) [Ti(H2O)6]3+ and [CoF6]3 (B) [Ti(H2O)6]3+ and [MnO4]
(C) (C) [CoF6] and [CrO4]
3 2
(D) [MnO4] and [CrO4]2
28. Among the following, the chiral complex is – [NSEC-2009]

(A) [Cr(OX)3]3– (B) cis-[PtCl2(en)] (C) cis-[RhCl2(NH3)4]+ (D) trans-[PtCl2(en)]
29. The species having tetrahedral shape is : [NSEC-2009]

(A) [PdCl4]2– (B) [Ni(CN)4]2– (C) [Pd(CN)4] 2–
(D) [Ni(Cl)4]
2–
30. The types of isomerism shown by Co(NH3)4Br2Cl are – [NSEC-2009]

(A) Geometrical and ionization (B) Optical and ionization
(C) Geometrical and optical (D) Geometrical only
31. The complex that exhibits Co-ordination isomerism is [NSEC-2010]

(A) [Cr(NCS)(H2O)5]2+ (B) [Cr(NH3)6]Cl3
(C) [Cr(NH3)6][Co(CN)6] (D) [CoCI2(NH3)4]Cl.H2O
32. The strong field ligand is : [NSEC-2010]

(A) SCN– (B) NO2 (C) I– (D) S2–
33. The IUPAC name of complex [Cu(en)2 (H2O)2]+ is [NSEC-2011]

(A) ethylene diamine Cu(II) dihydrate (B) diaquobis (ethylenediamine) Cu(II) ion
(C) diaquobisdiethylamine Cu(II) ion (D) diaquobis(ethylenediamine) cuprate(II)
34. The electronic spectrum of [Ni(H2O)6]++ shows a band at 8500 cm –1 due to d-d transition. [Ph4As]2[NiCl4] will
have such a transition in cm –1 at [NSEC-2011]
(A) 3778 (B) 8500 (C) 4250 (D) 850
35. Dimethyl glyoxime forms a square planar complex with Ni2+. This complex should be : [NSEC-2011]
(A) diamagnetic (B) paramagnetic having 1 unpaired electron
(C) paramagnetic having 2 unpaired electrons (D) ferromagnetic
36. The IUPAC name of [Co(ONO)(NH3)5Cl2] is : [NSEC-2012]

(A) pentamminenitrocobalt(ll)chloride (B) pentamminenitrosocobalt(IIl)chloride
(C) pentamminenitritocobalt(lll)chloride (D) pentammineoxo-nitrocobalt(Ill)chloride
37. In which of the following compounds is the oxidation number of the transition metal, zero ? [NSEC-2013]
(A) [Fe(H2O)3](OH2) (B) [Co(NH3)6]Cl2 (C) [Ni(CO4)] (D) [Pt(C2H4)Cl3]
38. The metal carbonyl which is paramagnetic is [NSEC-2013]

(A) Ni(CO)4 (B) V(CO)6 (C) Cr(CO)6 (D) Fe(CO)5
39. High spin complexes having coordination number ‘6’ are usually formed through [NSEC-2013]
(A) sp d hybridisation (B) d sp hybridisation (C) sp hybridisation
3 2 2 3 3
(D) sp d hybridisation
3
40. The complex having zero crystal field stabilization energy is [NSEC-2014]
(A) [Mn(H2O)6]3+ (B) [Fe(H2O)6]3+ (C) [Co(H2O)6]2+ (D) [Co(H2O)6] 3+
ADVCOR - 26
PART - III : ADDITIONAL PROBLEMS
THEORY
Introduction :
(a) The concept of co-ordination compounds arises from the complex formation tendency of transition
elements.
(b) These compounds play a vital role in our lives, as chlorophyll of plants, vitamin B12 and haemoglobin
of animal blood are the co-ordination compounds of Mg, Co and Fe respectively.
(c) The co-ordination compounds play important role in analytical chemistry , polymerisation reactions,
metallurgy and refining of metals, photography, water purification etc.
(d) Co-ordination compounds also find many applications in electroplating, textile dyeing and medicinal
chemistry.
Addition Compounds :
They are formed by the combination of two or more stable compounds in stoichiometric ratio.
Addition Compounds
|
| |
Double salts Coordination compounds
(Complexes)
Double salts :
Those addition compounds which lose their identity in solutions are called double salts. For example, when
K2SO4 solution is added to Al2(SO4)3 solution, the species formed when dissolved in water gives tests of K+,
Al3+ and SO42– ions.
K2SO4+Al2(SO4)3+24H2O  K2SO4 . Al2(SO4)3 . 24H2O (aq.) 2K+ (aq.) + 2Al+3 (aq.) + 4SO42– (aq.)
Other examples are carnallite (KCl. MgCl2 . 6H2O), Mohr’s salt [FeSO4 . (NH4)2SO4 . 6H2O],
potash alum [KAl(SO4)2.12H2O] or [K2SO4.Al2(SO4)3.24H2O] etc.
Coordination Polyhedron :
The spatial arrangement of the ligand atoms which are directly attached to the central atom/ion gives a
coordination polyhedron about the central atom. Figure below shows the shapes of tetrahedral, square
planar, octahedral, square pyramidal and trigonal bipyramidal coordination polyhedra. [Co(NH 3)6]3+ has an
octahedral geometry, while [PtCl4]2– and Ni(CO)4, are square planar and tetrahedral, respectively.
L L
L L
L L
L
L L
L L
M M M L
M
L L L M L
L
L L L
L Square planar L L L
Tetrahedral Octahedral Square pyramidal Trigonal bipyramidal
entity entity entity
entity entity
Writing the name of Polynuclear Coordination Compounds :

(i) Ist case : The name of a bridge complex is prefixed by –.
If the situation on both sides of the bridge is symmetrical then we can write the name of remaining
complex at one place like
5
(NH3 )5 Cr  OH – Cr (NH3 )5  Cl5
–hydroxidobis(pentaamminechromium(III)) chloride
ADVCOR - 27
OR we could also have written the name of one side of the bridge ligand and then the name of bridge
ligand and then the other side of the bridge, like
5
(NH3 )5 Cr  OH – Cr (NH3 )5  Cl5
pentaamminechromium(III)––hydroxidopentaamminechromium(III) chloride
(ii) IInd case :
If the compound is unsymmetrical on both sides of the bridge then we have to follow the second rule,
i.e. write the name of one side then that of the bridge and then that of the second side, like
tetraaquacobalt(III)––amido––hydroxidotetramminechromium(III) sulphate
SUBJECTIVE QUESTIONS
1. What is the coordination number and the oxidation state of the metal in each of the following complexes?
(a) [ZrF8]4– ;
(b) K3[Cr(C2O4)2Cl2]
2. Write the name of the following ligands and classify their denticity
(a) o-phen (b) NOS–
3. Name the K[PtCl3(  2–C2H4)] compound.
4. Write down the formulae of the following compounds

(a) tetraamminecobalt(III)--amido--hydroxidobis(ethylenediamine)cobalt(III) chloride
(b) bis(5-cyclopentadienyl)iron(II)
(c) tetraammineaquacobalt(III)--cyanidotetraamminebromidocobalt(III)
5. Calculate the EAN of central atom in the following complexes

(a) [Fe(CO)2(NO)2] (b) [Fe(C5H5)2]
6. Complete the following table (using concepts of VBT).

Complex Geometry Hybridisation Number of unpaired electrons(n) Mag. moment
CN =2
(a) [Ag(NH3)2]+ ---------------------- ----------------------
0 ----------------------
(b) [Cu(CN)2]– Linear ---------------------- ---------------------- ----------------------
(c) [AuCl2]– ---------------------- ---------------------- ----------------------

0
CN = 4
(d) [PtCl2(NH3)2] ---------------------- ----------------------
0 ----------------------
(e) [Zn(CN)4]2– ---------------------- ----------------------

0 ----------------------
(f) [Cu(CN)4]3– ---------------------- ----------------------

0 ----------------------
(g) [MnBr4]2– ---------------------- ----------------------

5 ----------------------
(h) [Cu(NH3)4]2+ Square Planar ---------------------- ---------------------- ----------------------
(i) [CoI4]2– ---------------------- ----------------------

3 ----------------------
CN = 6
(j) [Mn(CN)6]3– ---------------------- ----------------------
2 ----------------------
(k) [Cr(NH3)6]3+ ---------------------- ----------------------

3 ----------------------
(l) [Fe(CN)6]3– ---------------------- ----------------------

1 ----------------------
(m) [Ir(NH3)6]3+ ---------------------- ----------------------

0 ----------------------
ADVCOR - 28
(n) [V(CO)6] ---------------------- ----------------------
1 ----------------------
(o) [Fe(H2O)6]2+ ---------------------- ----------------------

4 ----------------------
(p) [MnCl6]3– ---------------------- ----------------------

4 ----------------------
7. Draw the structures of the following metal carbonyls

(a) [Co2(CO)8] (b) [Fe2(CO)9]
ONLY ONE OPTION CORRECT TYPE

8. The correct IUPAC name of the complex is :
H3C OH
C = N• •
CoCl2
••
C=N
H3C OH
(A) Dichloridodimethylglyoximecobalt(II) (B) Bis(dimethyglyoxime)dichloridocobalt(II)

(C) Dimethylglyoximecobalt(II) chloride (D) Dichlorido(dimethylglyoximato)cobalt(II)
9. A co-ordination complex has the formula PtCl4.2KCl. Electrical conductance measurements indicate the
presence of three ion in one formula unit. Treatment with AgNO3 produces no precipitate of AgCl. What is the
co-ordination number of Pt in this complex ?
(A) 5 (B) 6 (C) 4 (D) 3
10. Which of the following complexes produces three moles of silver chloride when its one mole is treated with
excess of silver nitrate ?
(A) [Cr(H2O)3Cl3] (B) [Cr(H2O)4Cl2]Cl (C) [Cr(H2O)5Cl]Cl2 (D) [Cr(H2O)6]Cl3
11. The number of chloride ions which would be precipitated when one mole of the complex PtCl4.4NH3 is treated
with silver nitrate is:(here coordination number of platinum is 6).
(A) four (B) one (C) three (D) two
12. A coordination compound of cobalt has the molecular formula containing five ammonia molecules, one nitro
group and two chlorine atoms for one cobalt atom. One mole of this compound produces three moles of ions
in an aqueous solution. The aqueous solution on treatment with an excess of AgNO3 gives two moles of AgCl
as a precipitate. The formula of this complex would be
(A) [Co(NH3)4(NO2)Cl] [(NH3)Cl] (B) [Co(NH3)5Cl] [Cl NO2]
(C) [Co(NH3)5(NO2)]Cl2 (D) [Co (NH3)5] [(NO2)2Cl2]
13. From the stability constant (hypothetical values), given below, predict which is the most stable complex ?
(A) Cu2+ + 4NH3  [Cu(NH3)4]2+ , K = 4.5 × 1011
(B) Cu2+ 4CN–  [Cu(CN)4]3–, K = 2.0 × 1027
(C) Cu + 2en  [Cu(en)2] ,
2+ 2+ K = 3.0 × 1015
(D) Cu2+ + 4H2O  [Cu(H2O)4]2+, K = 9.5 × 108
14. In Ziesses salt C = C bond length is :
C  C bond length in ethane is 1.54Å 

 
Note : C  C bond length in ethene is 1.34Å 
C  C bond length in ethyne is 1.20Å 
(A) 1.37Å (B) 1.19Å (C) 1.87Å (D) 1.34 Å
ADVCOR - 29
15. Which is not a -bonded complex ?
(A) Zeise's salt (B) Ferrocene
(C) bis(benzene) chromium (D) Tetraethyl lead
16. What is wrong about the compound K [Pt (2 – C2H4) Cl3] ?
(A) It is called Zeise's salt. (B) It is  bonded complex.
(C) Oxidation number of Pt is +4. (D) Four ligands surround the platinum atom.
17. Which of the following are bidentate monoanion ligands ?

(a) Dimethylglyoximato
(b) Oxalato ion
(c) Bis(ethane-1,2-diamine)
Select the correct answer using the codes given below :
(A) a only (B) a and c only (C) c only (D) b and c only
18. Diethylenetriamine is:

(A) chelating agent (B) tridentate neutral molecule
(C) tridentatemonoanion (D) (A) and (B) both
19. In K4[Fe(CN)6], Fe is in the form of

(A) An atom (B) Neutral complex (C) Cationic complex (D) Anionic complex
20. Complex ion [ FeN3(O2)(SCN)4]4 – is named as : (coordination number of central metal ion in complex is six)
(A) azidosuperoxidotetrathiocyanato-S-ferrate(II) (B) azidodioxygentetrathiocyanatoferrate(III)
(C) azidoperoxidotetrathiocyanato-S-ferrate(II) (D) azidodioxidotetrathiocyanato-S-ferrate(III)
21. The IUPAC name of K2[Cr(CN)2O2(O)2(NH3)] is :

(A) potassium amminecyanoperoxodioxochromatic(VI).
(B) potassium amminedicyanoperoxodioxochromium(VI).
(C) potassium amminecyanoperoxodioxochromium(VI).
(D) potassium amminedicyanodioxoperoxochromate(VI).
22. Consider the following statements:

According the Werner's theory.
(1) Ligands are connected to the metal ions by ionic bonds.
(2) Secondary valencies have directional properties
(3) Secondary valencies are non-ionisable
Of these statements:
(A) 1, 2 and 3 are correct (B) 2 and 3 are correct
(C) 1 and 3 are correct (D) 1 and 2 are correct
23. Which of the following is correct for both the following coordination compounds ?
(I) CoCl3.6NH3 and (II) PtCl4.5NH3
(A) They give white precipitate with AgNO3 solution.
(B) They have different primary valencies for the central metal ions.
(C) Both (A) and (B)
(D) None of these
24. In the complex [SbF5]2–, sp3d hybridisation is present. Geometry of the complex is :
(A) Square pyramidal (B) Square bipyramidal (C) Tetrahedral (D) Square planar
25. Crystal field stabilization energy for high spin d4 octahedral complex is :
(A) – 0.6 0 (B) – 1.8 0 (C) – 1.6 0 + P (D) – 1.2 0
2–
[S2 O8 ]
26. [(NH3)5Co–O–O–Co(NH3)5 ]+4 
oxidise
 [(NH3)5Co–O–O–Co(NH3)5 ]+5
Brown Green
The magnetic moment of green complex is 1.7 BM & for brown complexes magnetic moment is zero. (O–O)
is same in all respect in both the complexes.
ADVCOR - 30
The O.S. of Co in brown complex & green complex respectively are-
(A) III III & IV III (B) III II & III III
brown green brown green
(C) III III & III II (D) III IV & III III
brown green brown green
27. Which one of the following will be able to show cis-trans isomerism ?
(A) Ma3b (B) M(AA)2 (C) M(AB)(CD) (D) Ma4
28. Which of the following compounds show optical isomerism ?

1. cis - [Co(NH3)4 Cl2]+ 2. trans - [Co(en)2Cl2]+
3. cis - [Co(en)2Cl2] +
4. [Co(en)3]3+
Select the correct answer using the codes given below :
(A) 1 and 2 (B) 2 and 3 (C) 3 and 4 (D) 1, 3 and 4
MATCH THE COLUMN

29. Match the complexes listed in column-I with characteristic(s) / type of hybridisation listed in column-II.
Column – I Column – II
(A) [Co (en)3]3 + (p) sp3d2 hybridisaion
(B) [Co (ox)3] 3–
(q) Diamagnetic
(C) [Co (H2O)6]2+ (r) d2sp3 hybridisation
(D) [Co (NO2)6] 3–
(s) Paramagnetic
(t) Chelate ligand
SINGLE AND DOUBLE VALUE INTEGER TYPE

30. What is the coordination number of metal in [M(trien) (dipy)]±n ?
31. Out of the following. How many have correct IUPAC naming :
(1) [Ni(CN)4]2– - Tetracyanonickel (II) ion
(2) [Pt(Py)4] [PtCl4] - Tetrapyridine platinum (II) tetrachloride platinate (II)
(3) [Ni(dmg)2] - Bis(dimethylglyoximato) nickel (II)
(4) K3[Fe(CN)5NO] - Potassium pentacyanonitrosylferrate (II)
(5) [Fe(CO)5] - Pentacyanocarbonyl Ferrate (O)
(6) K2[HgI4] - Potassium tetraiodidomercurate (II)
(7) [Pt(NH3)4] [CuCl4] - Tetraammineplatinum (IV) tetrachlorido cuprate (II)
(8) [Cu(gly)2] - Diglycinate copper (II)
(9) K4[Fe(CN)6] - Potassium hexacyanidoferrate (II)
(10) [Pt(NH3)6] Cl4 - Hexaammine platinum (IV) chloride.
32. How many of the given complexes follow E.A.N. rule ?

(a) Fe(CO)5 (b) Co2(CO)8 (c) Fe(C5H5)2 (d) [K3Fe(CN)6]
(e) Fe(NO)2(CO)2 (f) [CoF6]4–
33. A name of neutral complex is :

Bis(acetyl acetanato) methylcyanidethiocyanato-s-iron (Y)
The ‘Y’ is O.N. of metal then calculate sum of primary and secondary valency ?
34. Na2[Cr(NO) (NH3) (C2O4)2], u = 3 B.M., Then total no. of electrons in d x 2  y 2 and d z 2 orbitals of metal :
35. If CFSE increases by 30% and 40% respectively for Co3+ to Rh3+ to Ir 3+ , then the total increase in
CFSE for Ir3+ with respect to Co3+ is .................
36. For the [Cr(H2O)6]2+ ion, the mean pairing energy P is found to be 23500 cm–1. The magnitude of 0 is 13900
ADVCOR - 31
cm–1. Calculate the C.F.S.E (cm –1)for this complex ion corresponding to high spin state (x) and low spin
state (y).
yx
Write your answer as  
 100 
37. The possible number of stereoisomers for the formula [Ma2b2cd]±n.
38. A complex is prepared by mixing CoCl3 & NH3 0.1 M solution of the complex was found to freeze at
–0.372ºC. Total geometrical isomers of complex are x. (Molar depression constant of water = 1.86ºC/m)
Report your answer by multiplying x with 6.
39. Calculate total number of geometrical, optical and structural isomers in the compound.
[Rh(en)2 (NO2)2]NO3
40. What is the EAN value of W(CO)6 carbonyl compounds ?
ONE OR MORE THAN ONE OPTIONS CORRECT TYPE

41. Which of the following pairs of name and formula of complexes, is correct ?
(A) Tetramminecopper(II) sulphate............. [Cu(NH3)4]SO4
(B) Diamminesilver(I) chloride ................ [Ag(NH3)2]Cl
(C) Potassium hexacyanidoferrate (III) ............... K4[Fe(CN)6]
(D) Potassium amminepentachloridoplatinate (IV) ................. K[Pt(NH3)Cl5]
42. In which of the following pairs of complexes the central metals/ions do have same effective atomic number ?
(A) [ Cr (CO)6 ] and [ Fe (CO)5 ] (B) [ Co (NH3)6 ]2+ and [Ni (NH3)6]2+
(C) [Cu (CN)4] and [ Ni (CO)4 ]
3–
(D) [V(CO)6]– and [Co(NO2)6]3–
43. Which of the following statements is/are correct ?

(A) Ni(CO)4 _____ Tetrahedral, paramagnetic (B) Ni(CN)4 ]2– _____ Square planar, diamagnetic
(C) Ni(dmg)2 _____
Square planar, diamagnetic (D) [NiCl4]2– _____ Tetrahedral, paramagnetic
44. Which of the following statement(s) is /are correct ?

(A) [Co(NH3)6]3+, [Co(CN)6]3– and [Co(NO2)6]3 – are diamagnetic involving d2sp3 hybridisation.
(B) [Zn(NH3)4]2+, [FeCl4] – and [Ni (CO)4] are diamagnetic involving sp3 hybridisation.
(C) The magnetic moment of [Fe(H2O)6]3+ is 5.92 B.M and that of [Fe(CN)6 ]3– is 1.73.
(D) The magnetic moment of K4[MnF6] and K3[FeF6] are same.
45. Consider the following statements :

S1 : Generally square planar complexes show geometrical isomerism but do not exhibit optical isomerism
because they do not possess plane of symmetry.
4
S2 : t = 
9 o
S3 : In octahedral complexes each electron entering the t2g orbitals stabilizes the complex ion by 0.4 o and
each electron entering the eg orbital destabilizes the complex by an amount of 0.6 o.
Select the correct statement from the codes given below.
(A) S1 and S3 are correct (B) S2 and S3 are correct
(C) S1 is incorrect (D) S2 and S3 are incorrect
46. Select the correct statement (s) .

(A) [Co(EDTA)] – has two optical isomers.
(B) [Co(NH3)5(NO2) ]2+ show linkage isomerism.
(C) For [ Pt (NH3)BrCl(NO2)py ], theoretically fifteen different geometrical isomers are possible.
(D) [Cr(H2O)4Cl2]Cl2.2H2O is an example of hydrate as well as ionisation isomerism.
47. Which of the following are -bonded organometallic compounds ?

(A) Ferrocene (B) Diethyl zinc
(C) Ethylmagnesium iodide (D) Bis(benzene) chromium(0)
ADVCOR - 32
COMPREHENSION
Comprehension #
Double salts are addition compounds which lose their identity in aqueous solution whereas complexes
which are also addition compounds do not lose their identity in aqueous solution. The coordination compounds
show isomerism and find applications in photography, qualitative analysis, metallurgy, water purification and
in the treatment of various diseases.
48. Which of the following statements is incorrect ?

(A) Alum is a double salt.
(B) EDTA salt of calcium is used in the treatment of lead poisoning.
(C) Effective atomic number of the metals in complexes [Ni(CO)4] and [Fe(CN)6]4– is same.
(D) Chloridotris (triphenylphosphine) rhodium(I) is effective heterogeneous catalyst for hydrogenation of alkenes.
49. Which of the following statements is true for the complex, [Co(NH3)4Br2]NO2 ?
(A) It shows ionisation, linkage and geometrical isomerism.
(B) It does not show optical isomerism because its cis and trans forms each have at least one plane of
symmetry.
(C) Its ionisation isomers cannot be differentiated by silver nitrate solution.
(D) (A) and (B) both.
50. Choose the correct option for the complex [PtCI2(en)2]2+.

(A) Platinum is in +2 oxidation state
(B) Racemic mixture is obtained on mixing mirror images of its trans form in 1 : 1 molar ratio.
(C) It has two five membered chelating rings
(D) (B) and (C) both
PART - IV : PRACTICE TEST-2 (IIT-JEE (ADVANCED Pattern))

Max. Time : 1 Hr. Max. Marks : 63
A. General %
B. Question Paper Format
3. Each part consists of five sections.
4. Section 1 contains 7 multiple choice questions. Each question has four choices (A), (B), (C) and (D) out
of which ONE is correct.
of which ONE OR MORE THAN ONE are correct.
6. Section 3 contains 5 questions. The answer to each of the questions is a single-digit integer, ranging from
0 to 9 (both inclusive).
7. Section 4 contains 1 paragraphs each describing theory, experiment and data etc. 3 questions relate to
paragraph. Each question pertaining to a partcular passage should have only one correct answer among
the four given choices (A), (B), (C) and (D).
8. Section 5 contains 1 multiple choice questions. Question has two lists (list-1 : P, Q, R and S; List-2 : 1,
2, 3 and 4). The options for the correct match are provided as (A), (B), (C) and (D) out of which ONLY ONE
is correct.
C. Marking Scheme
9. For each question in Section 1, 4 and 5 you will be awarded 3 marks if you darken the bubble corresponding
to the correct answer and zero mark if no bubble is darkened. In all other cases, minus one (– 1) mark will
be awarded.
ADVCOR - 33
10. For each question in Section 2, you will be awarded 3 marks. If you darken all the bubble(s) corresponding
to the correct answer(s) and zero mark. If no bubbles are darkened. No negative marks will be answered
for incorrect answer in this section.
11. For each question in Section 3, you will be awarded 3 marks if you darken only the bubble corresponding
to the correct answer and zero mark if no bubble is darkened. No negative marks will be awarded for
incorrect answer in this section.
SECTION-1 : (Only One option correct Type)

This section contains 7 multiple choice questions. Each questions has four choices (A), (B), (C) and
(D) out of which Only ONE option is correct.
1. Given that the energy of the photons of different colours decreases in the order of V I B G Y O R
(Violet > Indigo > Blue > Green > Yellow > Orange > Red) and that if complex absorbs a photon of low energy
then it shows colour of high energy photon. If an ion, M2+ , forms the complexes [M(H2O)6]2+, [MBr6]4– , and
[M(en)3]2+ . The colours of the complexes, though not necessarily in order, are green, red, and blue. Match
the complexes with the appropriate colour. (do not use the table of complementary colours for this
question)
(A) [MBr6]4– blue , [M(H2O)6]2+ green , [M(en)3]2+ red
(B) [MBr6]4– green , [M(H2O)6]2+ blue , [M(en)3]2+ red
(C) [MBr6]4– green , [M(H2O)6]2+ red , [M(en)3]2+ blue
(D) [MBr6]4– red , [M(H2O)6]2+ green , [M(en)3]2+ blue
2. Which of the following pairs of structures shows geometrical isomerism ?
(A) I with III (B) II with IV (C) I with II (D) none of these
3. 50 ml of 0.2 M solution of a compound with empirical formula CoCl3.4NH3 on treatment with excess of
AgNO3(aq) yields 1.435 g of AgCl. Ammonia is not removed by treatment with concentrated H 2SO4. The
formula of the compound is:
(A) Co(NH3)4Cl3 (B) [Co(NH3)4Cl2]Cl (C) [Co(NH3)4Cl3 (D) [CoCl3(NH3)]NH3
4. Which of the following statements is incorrect ?

(A) Potassium amminetetracyanidonitrosoniumchromate(I) having  = 1.73 B.M has d2sp3 hybridisation.
(B) K3[AlF6] + BF3  AlF3 + 3K[BF4]

(C) [Cr(NH3)6]Cl3 and [Cu(NCCH3)4] [BF4] both are coloured .
(D) [Cr(NH3)4Cl2]Br can show ionisation isomerism with [Cr(NH3)4ClBr]Cl
5. Which of the following statements is not true?


(A) MnCl 4 ion has tetrahedral geometry and is paramagnetic.
(B) [Mn(CN)6]2– ion has octahedral geometry and is paramagnetic.
(C) [Cu(CN)4]3– has square planar geometry and is diamagnetic.
(D) [Ni(Ph3P)2Br3] has trigonal bipyramidal geometry and is paramagnetic.
ADVCOR - 34
6. The complexes given below show :
and
(A) optical isomerism (B) co-ordination isomerism

(C) geometrical isomerism (D) bridged isomerism
7. Which of the following statements is correct with respect to the metal carbonyls of Ist transition series?
(A) As M – C bonding increases, the C – O bond length increases.
(B) As positive charge on the central metal atom increases, the C – O bond length increases.
(C) As electron density on the central metal atom increases, the C – O bond length increases.
(D) (A) and (C) both.
Section-2 : (One or More than one options correct Type)

This section contains 5 multipole choice questions. Each questions has four choices (A), (B), (C) and
(D) out of which ONE or MORE THAN ONE are correct.
8. Which of the following statement(s) is/are correct ?

(A) cis-[Pt(NH3)2Cl2] is used as an anticancer species.
(B) Carboxypeptidase- A is an enzyme and contains zinc.
(C) In the silver electroplating of copper, K[Ag(CN)2] is used in place of AgNO3.
(D) CN– ions show the reducing as well as complexing properties towards metal species.
9. Which of the following is true for the complex Co(NO2)(Cl)2.5NH3 (Co is in + III oxidation state) ?
(A) It shows linkage isomerism. (B) It show ionisation isomerism.
(C) It is inner orbital complex. (D) It is diamagnetic.
10. Which of the following complexes can exist as diastereoisomers ?

(A) [Cr(NH3)2Cl4]– (B) [Co(NH3)5Br]2+ (C) [FeCl2(NCS)2]2– (D) [PtCl2Br2]2–
11. Tetrahedral complexes are generally favoured :

(A) where the ligands are bulky
(B) when the ligands are stronger
(C) where the electronic configuration of the central metal is d0 d5 or d10 (with weak field ligands) as there is
no CFSE.
(D) when the central metal ion has pseudo noble gas electron configuration, i.e. (n-1) d 10ns0np0.
12. Which of the following statements is/are incorrect for the complex [Cr(H2O)6]Cl3 ?
(A) It has a magnetic moment of 3.83 BM.
(B) The distribution of 3d electrons is 3dxy1, 3dyz1, 3dzx1
(C) The ligand has satisfied both primary and secondary valencies of chromium.
(D) It shows ionization as well as hydrate isomerism.
Section-3 : (One Integer Value Correct Type.)

This section contains 5 questions. Each question, when worked out will result in one integer from
0 to 9 (both inclusive)
13. In the complex Fe(CO)x, the value of x is :
14. Count the no. of ions which can form both low spin & high spin complexes when co-ordination no. 6
Co+3, Ni+2 , Cr+3 , Fe+2, Fe+3 , Cu+2 , Ti+3, Co+2
ADVCOR - 35
15. The number of unpaired electrons present in [NiF6]2– is ................. .
16. The sum of stereoisomers of complex-A, complex-B and complex-C in following reaction is ..........
2 (pyridine ) NH 
Br
[PtCl4]2–    
 [Complex-A]  
3

 [Complex-B]   [Complex-C]
– 2Cl – Cl – (Pyridine)
17. The number of d-electrons in [Cr(H2O)6]3+ [atomic number of Cr = 24] is :
SECTION-4 : Comprehension Type (Only One options correct)

This section contains 1 paragraphs, each describing theory, experiments, data etc. 3 questions
relate to the paragraph. Each question has only one correct answer among the four given options
(A), (B), (C) and (D)
Paragraph For Questions 18 to 20

The magnetic moment for two complexes of empirical formula Ni(NH3)4(NO3)2.2H2O is zero and 2.84 BM
respectively. The second complex is not a natural complex.
18. The number of water molecules of crystallization are respectively

(A) zero, two (B) zero, zero (C) two, zero (D) two, two
19. The correct formula and geometry of the first complex is :

(A) [Ni(H2O)2(NO3)2].4NH3 ; tetrahedral. (B) [Ni(NH3)4](NO3)2.2H2O ; tetrahedral.
(C) [Ni(NH3)4](NO3)2.2H2O ; square planar (D) [Ni(NH3)4](H2O)2](NO3)2 ; octahedral
20. Which of the following statements are true for the second complex ?
(A) It has the EAN value of 36. (B) It can show optical isomerism.
(C) It cannot show geometrical isomerism (D) It produces three-fold freezing point depression.
SECTION-5 : Matching List Type (Only One options correct)

This section contains 1 questions, each having two matching lists. Choices for the correct combination
of elements from List-I and List-II are given as options (A), (B), (C) and (D) out of which one is correct
21. Column-I and Column-II contains four entries each. Entries of Column-I are to be matched with some
entries of Column-II. One or more than one entries of Column-I may have the matching with the same
entries of Column-II.
Column-I Column-II
(Coordination compounds) (Type of isomerism)
P. [Co(NH3)4CI2] 1. Optical isomerism
Q. cis-[CO(en)3]CI2 2. Ionization isomerism
R. [Co(en)2(NO2)CI]SCN 3. Coordination isomerism
S. [Co(NH3)6] [Cr(CN)6] 4. Geometrical isomerism
Code :
P Q R S P Q R S
(A) 1 3 2 4 (B) 3 2 4 1
(C) 4 3 1 2 (D) 4 1 2 3
ADVCOR - 36
Practice Test-2 ( (IIT-JEE (ADVANCED Pattern))
Que. 1 2 3 4 5 6 7 8 9 10
Ans.
Que. 11 12 13 14 15 16 17 18 19 20
Ans.
Que. 21
Ans.
PART - V : INDIAN NATIONAL CHEMISTRY OLYMPIAD (INChO) STAGE-II

Problem-1
Cobalt complexes [INChO-2008]
A pink solid compound (A) has the formula CoCl3. 5NH3.H2O. An aqueous solution of this
salt, which is also pink, on titration with AgNO3 gives three moles of AgCl per mole of A. Solid
A on heating above 120º C gives a purple solid (B) with the same ratio of NH3 : Cl. Compound
B on titration with AgNO3 gives two moles of AgCl per mole of B.
1.1 Write the electronic configuration of cobalt in compound A.
1.2 Write the molecular formulae of A and B with their IUPAC names.
1.3 Valence bond theory is useful in predicting shapes of complexes. Show the arrangement of the electrons for
cobalt in the low spin purple complex B. Predict the hybridization and the shape of this complex.
Although valence bond theory is successful in predicting the shapes of complexes, it is unable to explain
magnetic properties of coordination complexes. Crystal field theory (CFT) not only explains the magnetic
properties but also accounts for color and spectra of these complexes. CFT is based on splitting of the
d -orbitals of the central metal in presence of ligands.
1.4 (a) Using CFT draw the d orbital energy level diagram for the purple complex B. Label the energy levels and
show the electron distribution.
(b) Complex B is (Mark ‘X’ in the correct box) :
paramagnetic diamagnetic
1.5 Using CFT, show the arrangement of the electrons on the central metal atom in the complex ion [Co(NH3)6]2+
state with justification, whether [Co(NH3)6]2+ is readily oxidized or not.
1.6 For the complex [Co(NH3)3Cl3], draw the structures of possible stereoisomers and label them with
stereochemical descriptors.
1.7 A set of equivalent protons in a molecule gives one signal in the 1H NMR spectrum. The number of signal/s
for the isomers drawn in 1.6 will be :
1.8 Draw the structures of the following complexes and predict which one will be chiral.
(a) cis [CoCl2(ox)2]3– (b) trans [CoCl2(ox)2]3–
where ox = oxalate ligand (represent the same as in the answer).
ADVCOR - 37
Problem-2 [INChO-2010]
Chemistry of coordination compounds
Developments in the field of coordination chemistry have led to new concepts in chemical bonding and
molecular structure, revolutionized the chemical industry and provided insight into functions and structures
of vital components of biological systems. Coordination compounds find extensive applications in metallurgical
processes, analytical and medicinal chemistry.
2.1 Anhydrous copper sulphate, a white solid, when dissolved in water, gives a blue coloured solution. On
addition of dilute ammonia, a blue precipitate is obtained, which dissolves in excess of concentrated ammonia
giving a deep blue solution. Write the chemical reactions involved in the formation of these coloured species.
2.2 Most copper(I) compounds are found to be colourless. This is due to

(a) presence of low oxidation state of copper. (b) completely filled d-level in Cu(I).
(c) diamagnetic nature of the compound. (d) high polarizability of Cu(I) ion.
2.3 The expected spin-only magnetic moments of complexes of a transition metal like nickel or cobalt depend
on
(a) oxidation state of the metal. (b) nature of the ligand.
(c) geometry of the complex. (d) number of unpaired electrons in free transition metal ion.
2.4 Ni2+ forms a variety of complexes with different ligands. Thus, it gives [Ni(H2O)6]2+ with H2O and [NiCl4]2- with Cl-.
Both the complexes show paramagnetism corresponding to two unpaired electrons. Draw the crystal field splitting
diagrams for the two complexes showing the d-electron distribution to explain the observed magnetic properties.
State the geometries of the two complexes.
2.5 (a) Give IUPAC name of the complex [CoCl2(en)2]+ (en = H2N-CH2-CH2-NH2)
(complex A)
(b) Draw the structures of the geometrical isomers of complex A.
(c) Which of the geometrical isomers of complex A is/are optically active?
(d) Give the structures of the optical isomers.
2.6 Both Ni2+ and Pt2+ are d8 ions. With Cl– ligands, both form [MCl4]2– complex ions. However, while [NiCl4]2- is
paramagnetic, while [PtCl4]2– is diamagnetic. For both these complexes, draw the box diagram indicating the
distribution of electrons and the type of hybridization involved that explains the observed magnetic behaviour.
2.7 The crystal field splitting parameter, O, for some of the chromium complexes is given below. Match the O values
from column B with the corresponding chromium complex from column A.
A B
-1
Complex ion o (cm )
i) [CrF6]3– a) 26,600
3+
ii) [Cr(H2O)6] b) 22,000
2–
iii) [CrF6] c) 17,400
3–
iv) [Cr(CN)6] d) 15,000
2.8 Determine the oxidation state, coordination number and EAN of the central atom/ion in the following compounds:
(a) [Fe(CN)6]3– (b) Ni(CO)4
2.9 In an octahedral complex, whenever degenerate d x 2  y 2 and d z 2 orbitals are unequally occupied (as is the
case with, for example, d9 ion), the octahedron undergoes distortion. The two d-orbitals then have different
energies. This is known as Jahn Teller distortion. This distortion usually occurs by elongation or contraction
along z-axis, and the single electron correspondingly occupies highest energy d x 2  y 2 or d z 2 orbital. In a
crystal lattice structure of CuF2, the Cu2+ is six coordinate with four F– at a distance of 1.93 Å and two F– at
2.27 Å. Draw the relevant crystal field splitting diagram for the distorted octahedral geometry of CuF 2.
ADVCOR - 38
(a) The tetragonal distortion in the above case is
(i) by elongation along z-axis. (ii) by compression along z-axis.
(b) The single electron is in
(i) dz2 orbital. (ii) dx2–y2 orbital.
2.10 The order of trans effect in the series of ligands is :

CN ~ CO ~ C2H4 > PPh3 > NO2– > I– > Br– > Cl– > NH3 ~ Py > OH– > H2O
Draw the structures of the product of the following reactions on the basis of trans effect.
(i) [PtCl3NH3]– + NO2– 
A + NO2– 
(ii) [PtCl (NH3)3]+ + NO2– 
C + NO2– 
Transition Metal Chemistry :
Carbon monoxide (CO) is a colorless, odorless and tasteless gas that is lighter than air and highly toxic to
humans.
3.1 Draw the resonance structures (Lewis strctures) of carbon monoxide (CO) and underline the one which
follows the octet rule.
Carbon monoxide forms many metal carbonyls with transition metals in which there is a Metal - Carbon bond
3.2 Four possibilities of metal carbonyl bondings are given below, in which the metal (M) is in its lower oxidation
state. Select the most favourable bonding type.
(M) *(CO)
(A) (B) M C=0
(C) (D)
3.3 Using the effective atomic number (EAN) rule identify the value of x and y metal carbonyls I and II, draw the
structures of the metal carbonyls.
() Crx (CO)y x= y=
() [Mnx (CO)y] x= y=
ADVCOR - 39
According to the Valence Bond Theory (VBT), the metal atom or ion under the influence of the ligands can
use its (n-1)d, ns, np and nd orbitals for hybridization These hybrid orbitals overlap with ligand orbitals that
can donate electron paris for bonding. The symbol indicates electrons in metal and the symbol xx indicates
electrons from the ligand.(Write appropriate alphabets in the boxes).
3.4 Using VBT match the complexes (1-3) with appropriate hybridization schemes (a-c)
Complex Hybridization scheme
1.[Ni(CO)4] (a) XX XX XX XX
2.[Ni(Cl)4]2- (b) XX XX XX XX
3.[Ni(CN)4]2- (b) XX XX XX XX
(1) (2) (3)
Metal carbonyls can be synthesized by disproportionation reactions wherein one part of the reactant is
oxidised and the other part is reduced.
3.5 Write a balanced chemical equation of the reaction for the synthesis of nickel carbonyI from an appropriate
cyanide.
The infrared stretching frequency in terms of wavenumber  and expressed in units of cm -1 is given as  =
1 / (2c) K /  (where c is the velocity of light, k is force constant and  is reduced mass.)
3.6 Using the value of force constant as 1854 Nm -1, Calculate the stretching frequancy of free CO molecule.
A major consequence of the synergic bonding in metal carbonyls is the reduction in the bond order of the C-
O bond which results in the lowering of the CO stretching frequency. Any effect which decreases C - O bond
order should necessarily increase M-C bond order as the two are complementary to each other.
3.7 Arrange the given metal carbonyls according to the descending order of C-O stretching frequency.
(a) MCO (B) M2CO (C) M3CO
(i) where M stands for metal.
(ii) (a) [Ni(CO)3 PMe3] (b) [Ni (CO)3PF3] (C) [Ni(CO)3 PPh3]
3.8 With respect to the complex Co2 (CO)8 answer following. In the IR spectrum, this complex in the solid form
shows separate bands. above and below 2000 cm -1
(i) Draw the structure of the complex in the solid form.
(ii) When it is dissolved in hexane the bands below 2000 cm -1 disappear. Draw the structure of the
complex in the solution.
Hydroformylation (Oxo process) is the conversion of olefins to aldehydes catalyzed by cobalt and rhodium
carbonyl complexes. A catalytic cycle for the hydroformylation of a terminal olefin is given below and the
steps in this cycle are labeled form 1 to 7.
ADVCOR - 40
3.9 The steps given in the diagram can involve any of the following reactions :
(a) ligand substitution and dissociation (b) reductive elimination (c) -olefin coordination
(d) olefin insertion (e) oxidative addition (f) alkyI migration
Using the given information, complete the following table.
Step No Reaction type (Choose form the Formal oxidation state of metal Number of
above list and write only the in the product obtained at the d electrons
alphabet ) end of the step
3
6
7
APPLICATIONS OF TRANSITION METAL COMPLEXES
The transition metals are widely distributed in earth’s crust. The elements Co, Ir belong to Group IX is the
periodic table. These elements as well as their compounds have several applications in chemistry. Cobalt
and its compounds are used as catalysts and in making alloys, pigments and glasses.
Silica, on doping with an aqua complex of Co(II) shows light pink colour in wet condition and deep blue colour
in dry condition. This colour change is associated with the structural changes in the complex of Co(II) due to
partial loss of water.
4.1 Write the formula of the aqua complex of Co(II) that has pink colour.
4.2 With the above formula, write the balanced chemical equation for the reaction responsible for the observed
colour change.
ADVCOR - 41
Paragraph
A. Mercuric tetrathiocyanatocobaltate (II) is another complex of cobalt, used as a standard for calibrating magnetic
balances. Its spin only magnetic moment is 3.872 Bohr magnetons.
4.3 Write the formula of the complex.
4.4 Based on the magnetic moment alone, can the structure of the complex in 4.3 be predicted correctly to be
tetrahedral or square planar ?
Yes No
Paragraph
B. An oxide of cobalt, Co3O4 can exist either
(a) as a normal spinel CoII(Co2IIIO4) where 1/8th of the tetrahedral holes are occupied by CoII ions and 1/4th of
the octahedral holes are occupied by CoIII ions in a cubic lattice, or
(b) as an inverted spinel where 1/4th of CoII and CoIII exchange their sites.
Pairing energy P(cm –1) o(cm–1) t(cm–1)
Co 3+
20680 20760 9226
Co2+ 20800 9200 4090
(o and t imply the octahedral and tetrahedral splitting parameters respectively for oxygen as the ligand)
4.5 On the basis of the above data, calculate the crystal field stabilization energy (CFSE) in kJ mol –1 for
(i) (a) cobalt (III) in octahedral and (b) cobalt (III) in tetrahedral sites.
(ii) (a) cobalt (II) in octahedral and (b) cobalt (II) in tetrahedral sites.
(In actual calculations of CFSE values neglect the pairing energies)
4.6 Calculate the difference of the CFSE values obtained in 4.5 (i) and 4.5 (ii).
cobalt (III) in octahedral and tetrahedral sites.
cobalt (II) in octahedral and tetrahedral sites.
4.7 Based on your above calculations, predict whether Co3O4 exists as

a normal spinel an inverted spinel
4.8 The number of possible isomers for the complex of the type [CoIIIAX(en)2]2+ (en = ethylene diamine) is
2 3 4
4.9 Draw the possible structure(s) for the cis and the trans isomers of the above complex.
(Represent en by ).
Paragraph
Hydrolysis of the above complex (where X is the leaving group) proceeds through dissociation mechanism.
For the trans complex, the reaction proceeds via square pyramidal intermediate but for the cis complex it
proceeds via trigonal bipyramidal intermediate.
4.10 For the trans form, the hydrolysis will result in

(a) Only cis product (b) only trans product
(c) Mixture of cis and trans product
4.11 For the cis form, the hydrolysis will result in

(a) Only cis product (b) only trans product
(c) Mixture of cis and trans product
ADVCOR - 42
Paragraph
C. The complex [IrI(CO)Cl(PPh3)2] was first synthesized by Lauri Vaska in 1961 and is known as Vaska’s
complex. It is a versatile catalyst for several reactions.
The addition of H2 to [IrI(CO)Cl(PPh3)2] is cis, but the addition of CH3Cl is trans. The structures of the
complex and the products are given below. These reactions go through intermediate states.
H
Ph3P I
Cl Ph3P H
H2
(a) Ir 
 Ir
OC PPh3 OC PPh3
Cl
CH3
Ph3P I
Cl Ph3P Cl
CH3Cl*
(b) Ir  
 Ir
OC PPh3 OC * PPh3
Cl
4.12 (i) Draw the structures of the intermediates for the above addition reactions.
Intermediate for a Intermediate for b
(ii) State the oxidation number of Ir in the products.

(a) (b)
PART - VI : INTERNATIONAL CHEMISTRY OLYMPIAD (IChO) STAGE-V

Problem-1
A transition metal atom or ion may be directly bonded to a number of atoms or
molecules that surround it (ligands), forming a characteristic pattern. This is the
essential structural feature of an important class of so-called coordination or
complex compounds. If two or more atoms from one individual ligand form bonds
to the same central atom then the ligand is said to form a chelate (Greek chele = crab' claw).
The glycinate ion, NH2–CH2–COO–, is a bidentate chelate ligand which can form, for instance, tris-glycinato-
chromium(III) complexes. The figure shows one possible structure of such a complex. Oxygen and nitrogen
are forced to coordinate to adjacent octahedral positions, as the N–C–C–O chain is too short to "embrace"
the chromium ion. [IChO, 1982]
1.1 How many different configurational isomers of the complex are possible, not counting optical isomers?
1.2 Which of these isomers can be further resolved into optical isomers?
ADVCOR - 43
Another coordination compound of chromium was analyzed and found to have the following mass composition:
19.5 % Cr, 40.0 % Cl, 4.5 % H, and 36.0 % O. A 0.533 g sample of the compound was dissolved in 100 cm 3
of water, and 10 cm3 of nitric acid (2 mol dm–3) was added. Excess of silver nitrate solution was then added
and the precipitate formed was then filtered, washed, dried and weighed. Its mass was found to be 0.287 g.
When a 1.06 g sample was gently heated to 100ºC i n a stream of dry air, 0.144 of water was driven off.
The freezing point of a solution prepared from 1.33 g of the compound and 100 cm3 of water, was found to be
–0.18 ºC. (Molar freezing po int depression of water is 1.82 K kg mol–1). Use all the experimental information
to solve the following problems :
1.3 Derive the empirical formula of the compound.
1.4 Deduce formula for the compound showing the ligands of the chromium ion. Give molar ratios to support your
result.
1.5 Sketch all possible steric arrangements of the ligands about the chromium ion.
Problem-2
Ludwig Mond discovered before the turn of this century that finely divided nickel reacts with carbon monoxide
forming tetracarbonylnickel, Ni(CO)4, a colourless, very volatile liquid. The composition of Ni(CO) 4 provides
an example of the noble gas rule ("EAN rule"). [IChO, 1984]
2.1 Use the eighteen-electron rule (noble gas rule) to predict the formula of the binary carbonyls of Fe(0) and
Cr(0).
2.2 What composition would the eighteen-electron rule predict for the most simple binary chromium(0)-nitrosyl
compound?
2.3 Explain why Mn(0) and Co(0) do not form so-called mononuclear carbonyl complexes of the type M(CO)x (M
= metal), but rather compounds with metal-metal bonding.
2.4 Suggest structures of Ni(CO)4, Mn2(CO)10 and Co2(CO)8.
2.5 State whether V(CO)6 and the compounds mentioned in a) and d) are diamagnetic or paramagnetic.
2.6 Why are the carbon monoxide ligands bound to metals much more strongly than to boron in borane adducts
(e.g. R3B-CO; R = alkyl)?
2.7 Determine the composition of the compounds labeled A - F in the following reaction scheme:
Hints: (a) C has the following analysis: C, 14.75 % ; Br, 48.90 % .

(b) D contains 30.70 % Fe; the molecular mass is 363.8 a.m.u.
(c) Excess triethylamine is used for the synthesis of F. F contains 5.782 % C and 10.11 % N.
2.8 Why is the compound F formed in the disproportional reaction (given in g)), and not the compositional isomer
[Fe(CO)f]2+[Fe(NEt3)e]2– ?
2.9 The eighteen-electron rule is also satisfied by a compound prepared from elementary chromium and benzene.
(i) Draw the formula of this complex.
(ii) Which complex with the analogous structure is prepared by the reaction of iron powder with cyclopentadiene?
Write the chemical equation for its formation.
ADVCOR - 44
Problem-3
Compounds containing divalent platinum with the general formula PtX 2(amine)2 (X = Cl2, SO42–, malonate,
etc.) have met a lot of scientific interest because of their biological activity, particularly in view of their
properties in the treatment of tumours. The best known compound used clinically is PtCl2(NH3)2. This compound,
in which platinum is coordinated in a planar square, has two geometrical isomers of which only one shows
the antitumour activity. [IChO-1986]
3.1 Sketch the spatial structures of the two possible isomers.
3.2 How many isomers has PtBrCl(NH3)2? Sketch all of them.
It is possible to replace the amine ligands by one ligand containing two donor atoms (N). Then one obtains
a chelating ligand, such as 1,2-diaminoethane (en).
3.3 Show graphically that PtBrCl(en) has only one stable structure.
The ligand en can be substituted via methylation to form dmen or pn (racemic).
or
3.4 Give spatial structures of all isomers of the following compounds: PtCl2(dmen), PtCl2(pn), PtBrCl(dmen) and
PtBrCl(pn).
These compounds can isomerise in aqueous solution through dissociation of a ligand and transient replacement
of the stronger ligands by the weak ligand water. Cl– and Br– are replaced relatively easily, but it is more
difficult to replace the amine ligands, which usually requires heating.
3.5 Considering each of the isomers in the previous questions a-d, indicate which Isomers can be converted to
another at room temperature. Give both the original molecule and the products.
3.6 PtCl2(en) reacts with Br– in a molar proportion of 1 : 2 at room temperature. Which compound would you
expect to form in what proportion? You can assume that the Pt-Br and Pt-Cl bonds are equally strong and
that there is no perturbing influence from hydrolysis.
3.7 Using the equation to express chemical equilibrium, show that hydrolysis hardly ever occurs in blood but
that it does occur in the cells. Note: PtCl2(NH3)2 hydrolyses to and 2Cl–. In cells the Cl– concentration is low;
in blood it is fairly high.
After hydrolysis in the tumour cell a reactive platinum ion is formed to which two NH3 groups are still bound,
as it was found in the urine of patients treated with this compound. The reactive platinum ion appears to be
bound to cellular DNA, where the bonding occurs via guanine to one of the N-atoms.
As a result of the two reactive sites of platinum and the two unreactive NH3 ligands, it can form additionally
a second bond to DNA. Research has shown that this happens in particular with a second guanine base from
the same strand of DNA.
3.8 Show by calculations which of the two isomers in question a) can form this bond.
(Note : Pt-N distance = 210 pm, DNA base distance = 320 pm).
Problem-4
For preservation of meat, sodium nitrite is usually added and as a result NO is, then, formed. Consequently,
NO reacts with the sulphur and iron atoms from decomposition of proteins, forming [Fe4S3(NO)7]–. The complex
anion is bacteriostatic and antiseptic. X-ray crystallography shows that the complex anion has a structure
as shown below : [ICho, 1995]
ADVCOR - 45
4.1 (i) Blacken all the circles corresponding to iron atoms and add symbols Fe(A), Fe(B), Fe(C) and Fe(D)
beside the circles in the sequence of top  left  right.
(ii) The configuration of 3d electron shell of the iron atoms has been studied with modern structural analysis.
Knowing that the mean oxidation number of the four iron atoms is –0.5, give their configurations of 3d shell,
respectively. Assume that each iron atom adopt sp hybridization.
4.2 [Fe4S3(NO)7]– anion can be reduced and a new complex [Fe2S2(NO)4]2– is formed which contains a cyclic
structure unit of Fe2S2. [ICho, 1995]
(i) Write the structural formula for the anion [Fe2S2(NO)4]2–.
(ii) Give the oxidation state of each iron atom with Arabic numerals.
(iii) [Fe2S2(NO)4]2– can be converted into [Fe2(SCH3)2(NO)4]n, a carcinogen. Which of the following three species
is added to [Fe2S2(NO)4]2– : CH3+,  CH3 or CH3– ? Assign the value of n.
(iii) The species added to S atom is CH3+ ; n = 0.
Problem-5
Much of the world’s supply of platinum group metals is derived from the residues recovered from the electrolytic
refining of copper and nickel. A flow chart for the recovery of platinum and palladium is shown on the following
page. [IChO-1997]
5.1 (i) Clearly draw the shape (geometry) of both the PtCl62– and the PdCl42– anions.
(ii) Clearly draw all possible stereoisomeric structures of monomeric Pd(NH3)2Cl2.
Label the structures that you have drawn with their correct stereochemical descriptors.
Problem-6 [IChO-2012]
Platinum (II) compounds, isomers, and the trans effect.
Platinum and other group 10 metals form square planar complexes and the mechanisms of their reactions
have been studied extensively. For example, it is known that substitution reactions of these comlexes
proceed with retention of stereochemistry.
+ Y  +X
It is also known that the rate of substitution of ligand X by Y depends on the nature of the ligand trans to X,
that is, on ligand T. This is known as the trans effect. When T is one of the molecules or ions in the following
list, the rate of substitution at the trans position decreases from left to right.
CN– > H– > NO2–, I– > Br–, Cl– > pyridine, NH3, OH–, H2O
The preparations of cis- and trans-Pt(NH3)2 Cl2 depend on the trans affect. The preparation of the cis isomer,
a cancer chemostherapy agent commonly called cisplatin, involves the reaction of K 2PtCl4 with ammonia.
NH3 NH3
 
6.1 Draw all possible stereoisomers for square planar platinum (II) compounds with the formula Pt(py) (NH3)
BrCl (where py = pyridine, C5H5N).
6.2 Write reaction schemes including intermediate (s), if any, to show the preparation in aqueous solution for
each of the stereoisomers of [Pt(NH3)(NO2Cl2]– using, as reagents, PtCl42–, NH3, and NO2–. The reactions are
controlled kinetically by the trans effect.
ADVCOR - 46
PART - I
1. (2) 2. (2) 3. (1) 4. (4) 5. (3)
6. (3) 7. (4) 8. (3) 9. (4) 10. (3)
11. (3) 12. (2) 13. (3) 14. (1) 15. (3)
16. (2) 17. (3) 18. (2) 19. (4) 20. (4)
21. (3) 22. (3) 23. (1) 24. (2) 25. (4)
26. (4) 27. (1) 28. (4) 29. (4) 30. (2)
PART - II
1. (A) 2. (A) 3. (A) 4. (D) 5. (C)
6. (A) 7. (D) 8. (B) 9. (A) 10. (C)
11. (B) 12. (A) 13. (B) 14. (B) 15. (A)
16. (A) 17. (D) 18. (A) 19. (C) 20. (B)
21. (C) 22. (A) 23. (B) 24. (C) 25. (A)
26. (D) 27. (D) 28. (A) 29. (D) 30. (A)
31. (C) 32. (B) 33. (B) 34. (A) 35. (A)
36. (Bonus) 37. (C) 38. (B) 39. (A) 40. (B)
PART - III
1. The coordination number of the central atom/ion is determined by the number of sigma bonds between the
ligands and the central atom/ions i.e. the number of ligand donor atoms to which the metal is directly
attached.
The oxidation number of the central atom is defined as the charge it would carry if all the ligands are removed
along with the electron pairs that are shared with the central atom.
Complex Coordination Number Oxidation State
(a) [ZrF8]4– 8 4
(b) K3[Cr(C2O4)2Cl2] 6 3
2. (a) 1, 10-diaminophenanthrene, bidentate (b) thionitrito, monodentate
3. K[PtCl3(C2H4)] Potassium trichlorido(  2–ethylene)platinate(II)
4. (a) Tetraamminecobalt(III)--amido--hydroxidobis(ethylenediamine or ethane-1,2-diamine)cobalt(III) chloride
(b) Bis(5-cyclopentadienyl)iron(II) [Fe(  5–C5H5)2]

(c) Tetraammineaquacobalt(III)--cyanidotetraamminebromidocobalt(III) [(NH3)4(H2O)Co–CN–Co(NH3)4Br]4+
5. (a) 36 (j) 36
6. Complex Geometry Hybridisation Number of unpaired electrons(n) Mag. moment

CN =2
(a) [Ag(NH3)2]+ Linear sp 0 0
(b) [Cu(CN)2]– Linear sp 0 0
(c) [AuCl2]– Linear sp 0 0
CN = 4
(d) [PtCl2(NH3)2] Square Planar dsp2 0 0
ADVCOR - 47
(e) [Zn(CN)4]2– Tetrahedral sp3 0 0
(f) [Cu(CN)4]3– Tetrahedral sp3 0 0
(g) [MnBr4]2– Tetrahedral sp3 5 5.92 BM
(h) [Cu(NH3)4]2+ Square Planar dsp2 1 1.73 BM
(i) [CoI4]2– Tetrahedral sp3 3 3.87 BM
CN = 6
(j) [Mn(CN)6]3– Octahedral d2sp3 2 2.83 BM
(k) [Cr(NH3)6]3+ Octahedral d2sp3 3 3.87 BM
(l) [Fe(CN)6]3– Octahedral d2sp3 1 1.73 BM
(m) [Ir(NH3)6]3+ Octahedral d2sp3 0 0
(n) [V(CO)6] Octahedral d2sp3 1 1.73 BM
(o) [Fe(H2O)6]2+ Octahedral sp3d2 4 4.90 BM
(p) [MnCl6]3– Octahedral sp3d2 4 4.90 BM
CO OC CO CO
OC CO
CO
Co Co
7. (a) OC Co Co CO OR
OC
CO
OC CO
CO
CO CO
OC CO CO
CO
(b) Fe Fe
OC
CO CO
OC CO
8. (A) 9. (B) 10. (D) 11. (D) 12. (C)
13. (B) 14. (A) 15. (D) 16. (C) 17. (A)
18. (D) 19. (D) 20. (A) 21. (D) 22. (B)
23. (C) 24. (A) 25. (A) 26. (A) 27. (C)
28. (C) 29. (A - q, r, t) ; (B - q, r, t) ; (C - p, s) ; (D - q, r). 30. 6
31. 5 32. 4 33. 09 34. Zero 35. 82
36. 96 37. 8 38. 12 39. 15 40. 86
41. (A,B,D) 42. (A,C,D) 43. (B,C,D) 44. (A,C,D) 45. (B,C)
46. (A,B,C) 47. (A,D) 48. (D) 49. (B) 50. (C)
PART - IV
1. (A) 2. (C) 3. (B) 4. (C) 5. (C)
6. (C) 7. (D) 8. (A,B,C,D) 9. (A,B,C,D) 10. (A,D)
11. (A,C) 12. (C,D) 13. 5 14. 4 15. 0
16. 7 17. 3 18. (C) 19. (C) 20. (D)
21. (D)
ADVCOR - 48
PART - V
1.1 Co : 3d 4S
3+ 6 0
1.2 A Pink : [Co(NH3)5.H2O]Cl3 : Pentammine aqua cobalt (III)chloride

B Purple : [CoCl(NH3)5]Cl2 : Pentaamine chlorocobalt (III)chloride.
1.3 Co3+ = 3d6
Octahedral
1.4 a. b. diamagnetic
1.5
1.6
1.7 Facial isomer - one peak due to ammonia (with all similar environments)
Meridional isomer - two peaks
1.8
ADVCOR - 49
2.1 CuSO4 + 6H2O  [Cu(H2O)6]2+ + SO42–
White Blue solution
or balanced equation with [Cu(H2O)6]2+ entity
[Cu(H2O)6]2+ + 2OH–  Cu(OH)2 + 6H2O
From dil. NH3 Blue ppt.
[Cu(OH)2 + 4NH3  [Cu(NH3)4]2+ + 2OH–
deep blue soln
2.2 (b) Completely filled d-level in Cu().
2.3 (a) Oxidation state of the metal. (b) Nature of the ligand. (c) Geometry of the complex.
2.4
[Ni(H2O)6]2+ [NiCl4]2–
[Ni(H2O)6]2+ is octahedral. [NiCl4]2– is tetrahedral.
2.5 (a) IUPAC Name : Dichlorobis(ethylenediamine)cobalt(III)ion.

Dichlorobis(ethane-1,2-diamine)cobalt(III)ion.
Dichloridobis(ethylenediamine)cobalt(III)ion.
Dichloridobis(ethane-1,2-diamine)cobalt(III)ion.
(b) Geometrical isomers :
(c) cis-[CoCl2(en)2]+ is optically active.
(d) Two optical isomers of cis-[CoCl2(en)2]+ :
2.6 Ni2+ [Ar] 3d8
[NiCl4]2–
sp3 hybridization
Tetrahedral
Paramagnetic (2 unpaired electrons)
Pt2+ [Xe] 5d8
[PtCl4]2–
dsp2 hybridization
Square planar
Diamagnetic (no unpaired electrons)
ADVCOR - 50
2.7 A B 0 (cm–1)
(i) [CrF6] 3–
(d) 15,000
(ii) [Cr(H2O)6]3+ (c) 17,400
(iii) [CrF6]2– (b) 22,000
(iv) [Cr(CN)6]2– (a) 26,600
2.8 (a) [Fe(CN)6]3– (b) Ni(CO)4

Oxidation state Fe(IIII) Ni(0)
Coordination number of Fe(III) : 6 of Ni(II) : 4
EAN of central metal ion 35 36
2.9
Tetragonally octahedron Tetragonally

distorted octahedron distorted octahedron
contraction along z-axis elongation along z-axis
(a) (i) by elongation along z-axis
(b) (ii) d x2  y2 orbital.
2.10 (A) (B) (C) (D)
3.1
I follows octet rule
3.2
3.3 (I) Crx(CO)y X=1 y=6

(II) [Mnx(CO)y X=2 y = 10 or 11
ADVCOR - 51
3.4 (1) b (2) c (3) a
3.5 2[Ni(CN) + 4CO  [Ni(CO)4] + [Ni(CN)2]
3.6 (CO) = 2143 cm –1 or 6.424 × 1013 Hz
 = 1.1386 × 10–26 kg
3.7 (i) (a) MCO (b) M2CO (c) M3CO  a>b >c
(ii) (a) [Ni(CO)3PMe3] (b) [Ni(CO)3PF3] (C) [Ni(CO)3PPh3]  b>c >a
3.8 (i) (ii)
3.9 Step No Reaction type (Choose Formal oxidation state Number of

form the above list and of metal in the d electrons
write only the alphabet ) product obtained at
the end of the step
3 d +1 8
6 e +3 6
7 b +1 8
4.1 [Co(H2O)6]2+ 4.2 [Co(H2O)6]2+ 

 [Co(H2O)4] + 2H2O
2+
4.3 Hg[Co(SCN)4] 4.4 Yes [X]

4.5 The CFSE of Co(III) in octahedral sites = 592.90 KJ mol–1
The CFSE of Co(III) in tetrahedral sites = 65.8 KJ mol–1
The CFSE of Co(II) in octahedral sites = 87.58 KJ mol–1
The CFSE of Co(II) in tetahedral sites = 58.40 KJ mol–1
4.6 The difference of CFSE for CO(III) in octahedral and tetrahedral site is = 527.10 kJ mol–1
The difference of CFSE for CO(II) in octahedral and tetrahedral site is = 29.18 kJ mol–1
4.7 A normal spinel [X]
4.8 3 [X]
4.9
4.10 only trans product [X]

4.11 Mixture of cis and trans product. [X]
4.12 (i)
(ii) (a) +3 (b) +3
ADVCOR - 52
PART - VI
1.1 Two geometrical isomers of the complex are possible :
(i) the facial, which is the one illustrating the problem,
(ii) the meridional, with oxygen and nitrogen positions as shown :
1.2 It is clearly seen that any complex with three bidentate ligands attached octahedrally as shown, lacks mirror
symmetry. Hence, both stereoisomers are further resolvable into optical isomers.
1.3 The empirical formula is CrCl3H12O6.
1.4 The reaction with silver ions indicates that
1 mol CrCl3H12O6 = 1 mol Cl–
Gentle heating gives
1 mol CrCl3H12O6 = 2 mol H2O
These results support the coordination [CrCl2(H2O)4]Cl.2H2O.
This formula is supported by the freezing point experiment showing that
1 mol CrCl3H12O6 = 2 mol ions in solution.
1.5 Possible steric arrangements of the ligands about the chromium atom:
2.1 Fe(CO)5, Cr(CO)6

2.2 Cr(NO)4
2.3 Explanation: the odd number of electrons in the Mn(CO)5 and Co(CO)4 fragments.
2.4 Ni(CO)4 : tetrahedral geometry
Mn2(CO)10 : octahedral Mn(CO)5-structure having a Mn-Mn bond, relative orientation (conformation) of the
carbonyl groups.
Co2(CO)10: CO-bridges and Co-Co bond.
2.5 Fe(CO)5, Cr(CO)6, Ni(CO)4, Mn2(CO)10, Co2(CO)10 are diamagnetic, V(CO)6 is paramagnetic.
2.6 Explanation using the so-called "back-bonding concept".
2.7 A = [Fe(CO)5] B = [HOCOFe(CO)4] C = [FeBr2(CO)4]
D = [Fe2(CO)9] E = [(CO)4Fe=C(OLi)CH3] F = [Fe(NEt3)6] [Fe(CO)4]
ADVCOR - 53
2.8 This observation is due to differing back bonding capability of NEt 3 and CO.
2.9 (i) Structural formula of dibenzenechromium
(ii) Structural formula of ferrocene.
3.1 to 3.3
The isomers are :
(a) (b)
(c) since can only attack on one side.
3.4 (d) The following 9 isomers are possible :
3.5 In a-c) there is no change possible; in d) I4 and I5, I6 and I7, I8 and I9 transform one into another. Via this
isomerization also PtCl2(dmen), PtBr2(dmen), PtCl2 (pn) and PtBr2(pn) can be formed, even though they are
not isomers.
3.6 PtCl2(en) : PtBr2(en) : PtBrCl(en) = 1 : 1 : 2
3.7 PtCl2(NH3)2 (PtCl(H2O)(NH3)2)+ Pt(H2O)2(NH3)2)2+
In blood the hydrolysis does not occur, because the concentration of Cl– is rather high and the equilibrium is
shifted to the left side.
ADVCOR - 54
3.8 The bond is formed by the cis-isomer, because in that case the distance between the bases (320 pm) has to
change only to 210 2 = 297 nm, whereas in the case of the trans-compound the distant would be
210 × 2 = 420 nm.
4.1
Fe(A) has 3d7 configuration; Fe(B), Fe(C) , and F(D) have 3d9 configuration.
4.2 (i) (ii) Fe(-1) Fe(-1)
(iii) The species added to S atom is CH3+ ; n = 0.

5.1 (i) The PtCl62– anion consists of a Pt(IV) centred in a regular octahedron of Cl– ions. The PdCl42– anion
consists of a Pt(II) centred in a square of Cl- ions.
(ii) Like PdCl42–, Pd(NH3)2Cl2 is also square planar. However, in this case there are two distinct ways in which
the two different substituent groups (ligands) can be arranged. One places the two Cl– on adjacent corners of
the square (and axiomatically, the two NH3 on the other two adjacent corners). This arrangement is called the
cis isomer. The second arrangement has the pairs of the same ligand placed on diagonally opposite corners
of the square. This arrangement is called the trans isomer. There are only these two stereoisomers possible
for a monomeric form of the complex.
6.1
–
6.2 cis-isomer : 
3NH
 NO
 
2

2 points
–
trans-isomer : NO
 
2

NH3

2 points
ADVCOR - 55
PART - I
1. Let x be the oxidation state of nickel then,
(A) Ni(CO)4 ; x + 4 (0) = 0 or x = 0; (B) [NiF6]2– ; x + 6 (–1) = – 2 or x = +4;
(C) [Ni(NH3)6]2+ ; x + 4 (0) = +2 or x = +2; (D) [Ni(CN)6]4– ; x + 6 ( –1) = –4 or x = + 2.
4. [Mn(H2O)6]2+ = 3 × (–0.4) + 2 × (0.6) = 0 ; [Cr(H 2O)6]2+ = 3 × (–0.4) + 1 × (0.6) = 0.6 0

[Mn(H2O)6]3+ = 3 × (–0.4) + 1 × (0.6) = 0.6 0 ; [Cr(H2O)6]3+ = 3 × (–0.4) + 0 × (0.6) = 1.2 0
5. (A) trans-[Co(NH3)4Cl2]+ has plane of symmetry as well as centre of symmetry. Hence it does not show optical
isomerism.
(B) [Cr(H2O)6]3+ has plane of symmetry as well as centre of symmetry. Hence it does not show optical isomerism.
(C) (C) cis-[Co(NH3)2(en)2]3+ lacks one of the symmetry elements.
(D) trans-[Co(NH3)2(en)2]3+ has plane of symmetry as well as centre of symmetry. Hence it does not show
optical isomerism.
6. NO 2– is an ambidentate ligand and can link to central metal ion either through N or O. Hence it show
linkage isomerism.
There is exchange of NO2– and SO42– occurs between coordination sphere and ionization sphere. Hence
it shows ionisation isomerism.
Ma5b has only one form, therefore, it does not show geometrical isomerism.
Ma5b has mirror plane, therefore, it does not show optical isomerism.
 0 4 1
7. [Cr(NH3 )(CN)4 (NO)]2
Central metal ion has one unpaired electron and thus d-d transition of electron is possible. This attributes to
the colour of the solution. As different types of ligands are attached to central metal ion, the complex is
called heteroleptic complex.
8. S1 : Cr3+ CFSE = 3 × – 0.4 = – 1.2 0, hybridisation is d2sp3 (NH3 is strong field ligand)
S2 : Fe3+, 3d5 - one unpaired electron after pairing (CN– is stronger field ligand)
 = 1 (1  2)  1.73 BM
S3 : and .
In reactant and product, the iron is in same oxidation state i.e. +2.
ADVCOR - 56
9. (A) Pt (+II) and Au (+III) with 5d8 configuration have greater CFSE and thus favours square planar
geometry (i.e. dsp2 hybridisation) with weak as well as strong field ligands.
(B) In tetrahedral complex , the t2g orbitals are nearer to the direction of the ligands. Hence they have higher
energies than that of eg orbitals (for detail refer text).
(C) 3d5 , ; CFSE (weak filed ligands) = –0.6 × 2 + 0.4 × 3 = 0 t
3d5 , ; CFSE (weak filed ligands) = –0.4 × 3 + 0.6 × 2 = 0 0 .
Similarly for d0 and d10 configurations the CFSE is zero in both octahedral and tetrahedral complexes with
weak field ligands.
10. [CoCl2(en) 2]Cl, One mole complex contains, one mole of ionisable Cl–.
One mole of complex = one mole of Cl–.
100  0.024
 One mole of AgCl = One mole of complex = = 0.0024.
1000
11. n=4 and  = 4.91
n=0 and =0
13. [Ni (H2O)4 ] SO4 + Pyridine + NaNO2  [Ni(Py)4](NO2)2

Stronger ligand, pyridine displaces weaker ligand, H2O in aqueous solution.
[Ni(py)4](NO2)2 is formed as dark blue crystals on crystallisation.
6
16. 2X + 1(–2) + 1(–1) = +3 ; x = = + 3.
2
18. (A) [Cr(NH3)6]3+ [Cr(NO2)6]3– and [Cr(NH3)4(NO2)2]+ [Cr(NH3)2(NO2)4]– have same number of ions, so cryoscopic
method can not be used.
(B) Molar conductance depends on the number of ions as well as on the charge on the complexes.
[Cr(NH3)6]3+ [Cr(NO2)6]3– and [Cr(NH3)4(NO2)2]+ [Cr(NH3)2(NO2)4]– have same number of ions but different
electrical charges.
(C) Both complexes have same number of unpaired electrons, so measuring magnetic moments methods
can not be used.
(D) They have similar colour because of the similar conditions.
19. [Fe(en)2(H2O)2]2+ + en  [Fe(en)3]2+ + 2H2O

Complex is [Fe(en)3]2+. 'en' is a strong field ligand and thus it is inner orbital complex (d2 sp3) and diamagnetic.
It is M(AA)3 type which has only one form.
20. (A) Cr3+, 3d3 ; sp3d2 hybridisation with three unpaired electrons (weak field as well as strong field
ligand).
Fe+ , 3d7; sp3d2 hybridisation with three unpaired electron (one 4s electron jumps to 3d orbital
for the pairing)
(B) Mn2+, 3d5; d2sp3 hybridisation with one unpaired electron after pairing (CN– is strong field ligand).
Fe3+, 3d5 ; d2sp3 hybridisation with one unpaired electron after pairing (CN– is strong field ligand).
(C) Ni, 3d8 4s2; sp3 hybridisation and all electrons are paired because CO is strong field ligand (4s-
electrons jumps to 3d-orbitals for the pairing)
Zn2+ , 3d10; sp3 hybridisation and all electrons are paired.
ADVCOR - 57
F 
21. [Fe(SCN)(H2O)5]2+ 
 , F– being weak ligand Fe3+— .
Therefore, five unpaired electrons and so  = 5 (5  2) B.M.  5.92.
22. In Fe(CO)5, Fe in zero oxidation state and CO is stronger field ligand. So,
Fe(CO)5
five dsp3 hybrid orbitals

Hence it is diamagnetic and low spin complex.
23. (A) The crystal field-splitting for Cr3+ ion in octahedral field increases with increasing strength of ligands.
This order given in (A) is according to spectrochemical series.
25. (D) Chelate complex has higher stability than the similar complexes having monodentate ligands and
an higher stability means higher overall formation constant.
26. In Fe(CO)5, Fe is dsp3 hybridised. Hence, its structure is trigonal bipyramidal.
27. (I) [Fe(H2O)6]2+ , 3d6 n = 4 (weak field ligand)
(II) [Fe(CN)6]3– , 3d5 n = 1 (strong field ligand)
(III) [Fe(CN)6]4– , 3d6 n = 0 (strong field ligand)
(IV) [Fe(H2O)6]3– , 3d5 n = 5 (weak field ligand)
28. [Ni(CO)4] = sp3 ; [Ni(CN)4]2– = dsp2 ; [Fe(CN)6]4– = d2sp3 ; [MnF6]4– = sp3d2.
29. (A) No anionic ligand is present in coordination sphere for the exchange with Cl– ions present in ionisation
sphere.
(B) No anionic ligand is present in coordination sphere for the exchange with Cl– ions present in ionisation
sphere.
(C) No anionic ligand is present in coordination sphere for the exchange with Cl– ions present in ionisation
sphere.
(D) Br– and SO 4– can exchange their positions between coordination sphere and ionisation sphere.
Hence it shows ionization isomerism.
30. Coordination number of nickel in [Ni(C2O4)3]4– is 6 because C2O2–4 is a bidentate ligand.
ADVCOR - 58
PART - III
5. (a) Fe(Z = 26) ; EAN = 26 + 2 + 8 = 36. (b) Fe(Z = 26) ; EAN = 26 + 10 = 36.
8. Correct name is dichloridodimethylglyoximatecobalt (II)
9. PtCl4.2KCl  K2[PtCl6] 2K+ + [PtCl6]2–.

So, it has three ions per formula unit. The Cl– is present in coordination sphere so it will not give white
precipitate with silver nitrate solution. So in the compound the coordination number of platinum is 6.
10. (D) [Cr(H2O)6]Cl3 [Cr(H2O)6]3+ (aq) + 3Cl– (aq).

Cl– present in ionisation sphere will give precipitate with AgNO3 .
3Cl– + 3Ag+  3AgCl
So, one mole of complex will give three moles of AgCl precipitate.
11. PtCl4.4NH3  [Pt(NH3)4Cl2]Cl2 [Pt(NH3)4Cl2]2+ (aq) + 2Cl– (aq).

2Ag+ + 2Cl–  2AgCl  (white)
Concentrated H2SO4 will not dehydrate the following complex :
12. (C) [Co(NH3)5(NO2)]Cl2 [Co(NH3)5(NO2)]2+ (aq) + 2Cl–(aq) (no. of ions = 3)
2Ag+ + 2Cl–  2AgCl  (white).
13. K  stability.
14. Relative to free ethylene the C—C bond is lengthened (from 133.77 pm to 137.5 pm). The bonding scheme is
analogous to that in carbon monoxide complexes in which there is a ligand metal  donation and a reciprocal
metal to ligand  bonding.
15. (C2H5)4 Pb is a -bonded complex.
16. X + 3 (–1) = 1 X = +2.
17. (a) (b) (c) NH2CH2CH2NH2
18. Diethylenetriamine is a tridentate neutral molecules with three donor nitrogen atoms. Polydentate ligand
which uses its two or more donor atoms to bind a single metal ion producing a ring is called as chelating
ligand.
1 1 4
20. [Fe(II) N 3 ( O 2 ) (SC N )4 ]4  ; so correct name is azidosuperoxidotetrathiocyanato-S-ferrate(II) according to
IUPAC rules.
ADVCOR - 59
–2 –2 –4 0
21. 2K+ [Cr(CN)2 O2 ( O )2 (NH3 )]2 –
Oxidation state of chromium = x + 2(– 1) + (– 2) + 2(– 2) + (0) = – 2.
 x = + 6.
As per IUPAC name.
Complex is anionic, so metal ion will be named as chromate with +6 oxidation state. So, potassium
amminedicyanodioxoperoxochromate(VI).
22. According to Werner's theory statements (2) and (3) are correct.
(1) Ligands are connected to the metal ion by coordinate covalent bond (dative bond).
(2) Secondary valencies i.e. coordination number give rise to stereochemistry of the complexes because of
their directional properties.
(3) Secondary valencies correspond to coordination number i.e. number of -bonds between metal ion and
lignds.
23. (I) [Co(NH3)6]Cl3 + 3Ag+  3AgCl + [Co(NH3)6]3+

Co3+  Primary valencies i.e. ionisable valency = 3.
(II) [Pt(NH3)5Cl]Cl3 + 3Ag+  3AgCl + [Pt(NH3)5Cl]3+
Pt4+  Primary valencies = 4.
27. Ma3b, Ma4 and M(AA)2 (symmetrical bidentate ligand) have only one form; they does not show geometrical
isomerism. But M(AB)(CD) shows two geometrical isomerism.
28. (1) cis - [Co(NH3)4 Cl2]+ has plane of symmetry as well as centre of symmetry ; so optically inactive.
(2) trans - [Co(en)2Cl2]+ has plane of symmetry as well as centre of symmetry ; so optically inactive.
(3) cis - [Co(en)2Cl2]+ lacks plane of symmetry as well as centre of symmetry ; so optically active.
(4) [Co(en)3]3+ lacks axis of internal rotation ; so optically active.
29. (A) [Co (en)3]3 + ; Co3+ has d6 configuration which has higher CFSE ; so hybridisation is d2sp3 and complex is
diamagnetic. 'en' is a bidentate chelate ligand.
(B) [Co (ox)3]3 – ; Co3+ has d6 configuration which has higher CFSE ; so hybridisation is d2sp3 and complex is
diamagnetic. 'ox' is a bidentate chelate ligand.
(C) [Co (H2O)6]2+ ; Co2+ has d7 configuration ; H2O is a weak field monodentated ligand, so it is paramagnetic
with three unpaired electrons having sp3d2 hybridisation.
(D) [Co (NO2)6]3 – ; Co3+ has d6 configuration which has higher CFSE ; so hybridisation is d2sp3 and complex
is diamagnetic. 'NO2– ' is a monodentate ligand.
30. Trien (triethylene teramine) is a tetradentate Ligand while dipy (2, 2’-dipyridyl) is a Bidentate Ligand.
31. Naming of (1), (2), (5), (7) and (8) are wrong.
32. (d) K3[Fe(CN)6] = 26 - 3 + 2 × 6 = 35 does not follow E.A.N. rule.
33. Complex [Fe(acac)2 (NCCH3) (SCN)]

Y–2+0–1=0
Y = +3
sec. valency = 6
sum = 3 + 6 = 9
ADVCOR - 60
34. In given complex, Cr is in +1 oxidation state.
Cr+  4sº 3d5 (u = 3 B.M.)
36. For a d4 ion in a high spin state.

CFSE = – 0.6 o = – 0.6 × (13,900 cm –1) = – 8340 cm–1
For a d4 ion in a low spin state, the net CFSE is,
= – 1.6 o + P = – 1.6 × (13,900 cm –1) + 23500 cm–1 = + 1,260 cm –1
Since o (= 13,900 cm –1) < P (= 23,500 cm– 1), the high spin configuration would be more stable.
38. Tf = imKf

0.372 = 1.86 × 0.1 × i
i=2
complex is [Co(NH3)4Cl2]Cl octahedral with two geometrical isomers.
39. [Rh(en)2(NO2)2]NO3 Linkage Geo. Optical

NO2 NO2 Cis + trans Cis
NO2 ONO Cis + trans Cis
ONO ONO Cis + trans Cis
[Rh(en)2(NO2)NO3]NO2 NO2 NO3 Cis + trans Cis
ONO NO3 Cis + trans Cis
5 × 3 = 15 isomers.
41. (C) It is not correct formula because the Fe is in +3 oxidation state and as such formula should be [Fe3+(CN)6]3–
or K3[Fe(CN)6].
42. (A) EAN of Cr = 24 + 12 = 36 and EAN of Fe = 26 + 10 = 36.

(B) EAN of Co3+ = 25 + 12 = 37 and EAN of Ni2+ = 26 + 12 = 38.
(C) EAN of Cu+ = 28 + 12 = 36 and EAN of Ni = 28 + 8 = 36.
(D) EAN of V– = 24 + 12 = 36 and EAN of Co3+ = 24 + 12 = 36.
43. In complex nickel is in zero oxidation state. The CO is strong field ligand and therefore compels for the
pairing of electrons. The hybridisation scheme is as shown in figure.
Ni0([Ar] 3d8 4s2)
[Ni(CO)4] Four pairs of electrons from four CO.
sp3 hybrid orbitals

It is tetrahedral and as all electrons are paired so diamagnetic.
44. (A) All are diamagnetic and inner orbital complexes because all ligands are strong field ligands.
(B) Fe3+ n = 5 ;  = 5 (5  2)  5.92 with H2O, so [FeCl4]– is diamagnetic.
(C) Fe3+ n = 5 ;  = 5 (5  2)  5.92 with H2O
Fe3+ n = 1 ;  = 3 = 1.73 with CN–

(D) Mn2+ (3d5) and Fe3+ (3d5) have same number of unpaired electrons i.e. 5 with weak field ligands, F–
45. S1 : Square planar complexes with symmetrical ligands like (en) do not show geometrical isomerism
and they have plane of symmetry, so optically inactive.
S2 and S3 are correct statements.
ADVCOR - 61
46. (A) [Co(EDTA)] – shows optical isomerism.
(B) NO2– being bidentate ligands can attach to central metal ion through N or O.
(C) It is Mabcdef type and thus have fifteen different geometrical isomers.
(D) Ionisation isomerism involves exchange of different ions between coordination sphere and ionisation
sphere. In complex, [Cr(H2O)4Cl2]Cl2.2H2O, same anionic ligands, i.e., Cl– are present in coordination sphere
and ionisation sphere; so no exchange of ions takes place.
47. (A) and (D) are -bonded organometallic compounds as they involve the formation of -bonds between metal
and carbon.
(B) and (C) are -bonded organometallic compounds as they only form  bond by sharing of electrons
between metal and carbon.
48. It is homogeneous catalyst for hydrogenation of alkenes.
49.
cis - trans -
It shows geometrical isomerism but not optical isomerism due to the presence of at least one plane of
symmetry.
[Co(NH3)4Br2]NO2 and [Co(NH3)4BrNO2]Br are ionisation isomers and later complex reacts with AgNO3
solution to give pale yellow precipitate. [Co(NH3)4BrNO2]Br and [Co(NH3)4BrONO] Br are linkage isomers.
50.
trans-form is optically inactive because it is achiral.
PART - IV
1. Order of crystal field splitting en > H2O > Br– so, more stronger ligand will absorb lower wavelength light and
reflect back higher wavelength light.
2. (A) I and III both are identical structures (i.e. trans-isomers).

(B) II and IV are identical structures (i.e. cis - isomers).
(C) I and II are cis - and trans - isomers (i.e. they are geometrical isomers).
1.435
3. mole of complex = 50 × 0.2 = 0.01 and mole of AgCl = = 0.01
143 .5
n Ag+ = n Cl–  1 mole complex = 1 mole AgCl
4. (C) [Cr(NH3)6]Cl3 is coloured as it has three unpaired electrons while [Cu(NCCH3)4] [BF4] is colourless
as Cu(I) i.e. 3d10 electron configuration has all electrons paired, so there is no d-d transition of electron.
5. (C) [Cu(CN)4]3–, [Ar]183d10; As there is no empty d-orbital for dsp 2 hybridization. So it has sp3 hybridization
and is tetrahedral, and diamagnetic.
6. Geometrical isomerism arises in heteroleptic complexes due to different possible geometric arrangements
of the ligands.
When two (C2H5)3P groups are on same side it is cis - and when those are on opposite side it is trans-
ADVCOR - 62
7. Order of C–O bond strength :
[Mn(CO)6]+ > [Cr(CO)6] > [V(CO)6]– > [Ti(CO)6]2– and [Ni(CO)4] > [Co(CO)4]– > [Fe(CO)4]2– .
(A) True statement.
(B) As +ve charge on the central metal atom increases, the less readily the metal can donate electron
density into the * orbitals of CO ligand to weaken the C–O bond.
(C) In the carbonylate anions, the metal has a greater electron density to be dispersed, with the result that
M–C bonding is enhanced and the C–O bond is diminished in strength.
8. All statements are correct.
9. [Co(NH3)5 (NO2)]Cl2 and [Co(NH3)5Cl]Cl (NO2) are ionisation isomers.

[Co(NH3)5 (NO2)]Cl2 and [Co(NH3)5 (ONO)]Cl2 are linkage isomers.
Cobalt in +3 oxidation state has 3d6 configuration which has higher CFSE. So the complex is inner orbital
(i.e. d2sp3 hybridisation) and diamagnetic.
10. (A) Exists as cis and trans form but neither of the forms can have enantiomeric forms on account of
presence of the plane of symmetry as well as centre of symmetry.
(B) Only one form possible
(C) Tetrahedral in which all positions are adjacent to each other.
(D) Exists as cis and trans form but neither of the forms can have enantiomeric forms on account of
presence of the plane of symmetry.
11. Tetrahedral complexes are favoured by steric requirements, either simple electrostatic repulsion of charge
ligands or vander wall's repulsions of large one.
Tetrahedral complexes are thus generally favoured by large ligands like Cl–, Br–, – and PPh3 and metal ions
of three types ;
(1) those with a noble gas configuration such as Be2+ (nsº) ;
(2) those with pseudo noble gas configuration (n–1)d10 ns0np0, such as Zn2+, Cu+ and Ga3+, and
(3) those transition metal ions which do not strongly favour other structure by virtue of the CFSE, such
as Co2+, d7.
12. (A) The 3d3 electron configuration always have three unpaired electrons with weak field as well as strong field
ligands.
(B) 3d3 (C) H2O being neutral molecule satisfies only secondary valencies.
(D) It shows hydrate isomerism and not ionisation isomerism because anionic ligand is not present in
coordination sphere.
13. According to EAN rule
26 – 0 + 2x = 36
x=5
14. Ni+2, Cu+2 only high spin complex.
15. [NiF 6]2– oxidation number = +4

t2g2,2,2 eg0,0 (pairing occur due to high oxidation number of Ni).
16. A [Pt(Py)2Cl2]  Ma2b2 (2 G.I.)

B [Pt(Py) 2(NH3)Cl]  Ma2bc (2 G.I.)
C [Pt(Py) 2(NH3)(Br)Cl]  Mabcd (3 G.I.)
17. 3d3 = t2g1,1,1 eg0,0
ADVCOR - 63
p-block elements (N & O Family)
ADV PNO - 64

Section (A) : General facts about elements
A-1._ Nitrogen forms a simple diatomic molecule but other elements of same group do not form. Explain.
A-2._ White phosphorus is very reactive, but not the red one. Why ?
A-3. Which allotropic form of sulphur is thermodynamically stable at room temperature and pressure ?
A-4._ The important source of phosphorus is phosphorite rocks which is mainly phosphates. The same chemical
compound is also present in bones. What is the formula of the compound(s).
Section (B) : Based on Periodic trends

B-1. Why is Bi (V) a stronger oxidant than Sb (V)?
B-2. Nitrogen shows different oxidation states in the range ______ to _____. It most stable oxidation state
is______ .
B-3._ The tendency to exhibit-3 oxidation state by a group VA element decreases down the group. Why ?
B-4. Why sulphur in vapour state exhibits paramagnetic behaviour at above 800ºC.
Section (C) : Based on Chemical Bonding

C-1._ Write the following for a white phosphorus molecule :
(a) oxidation state of P (b) valency of P (c) total number of bonds
(d) bond order. (e) bond angle (f) geometry
C-2._ Write the structures of the oxides : N2O3, N2O5, P4O6 and P4O10.
C-3._ Write the structure and oxidation numbers of sulphur in tetrathionate ion.
C-4._ The bond angle in PH4+ is higher than that in PH3. Why ?
C-5._ Write the oxyacids of the following :

Oxide Oxyacids
N2 O 3
NO2/N2O
N2 O 5
P4 O 6
P4O10
C-6._ N2, CO, CN– and NO+ are isoelectronic but the former is chemically inert and latter three are very reactive,
why ?
C-7. Why does NO2 dimerise ?
C-8. On moving down the group from H2O to H2Te acidic strength increases, why ?
C-9._ Both PH3 and NH3 are Lewis bases, but basic strength of PH3 is less than that of NH3. Explain
Section (D) : Properties of elements

D-1. What happens when barium azide is heated ?
D-2._ Which stable elements of 15th and 16th group do not react with water under normal conditions ?
ADV PNO - 65
D-3._ Chemiluminescence is a phenomenon in which on element glows in dark when exposed to moisture. Which
element of 15th group shows this phenomenon ?
D-4._ Sulphur flower on reaction with sulphide ion gets reduce to poly sulphide ion. Write the reaction and upto how
many sulphurs atoms the poly sulphide ions are formed significantly.
Section (E) : Oxides, Hydroxides, Peroxides, Oxyacids

E-1._ In the manufacture of sulphuric acid by the contact process, sulphur trioxide is not directly dissolved in
water. Why ?
E-2._ In the preparation of P4O6, a mixture of N2 and O2 is used rather than pure O2, Why ?
E-3._ How are SO2Cl2.SO3 and SO2 obtained from sulphuric acid ?
E-4._ A compound of 15th group element is used as a fast drying agent in the laboratory. It is :
E-5._ Tellurium forms oxides of the formula TeO, TeO2 and TeO3. What is the nature of these tellurium oxides?
E-6. Sulphur on oxidation with hot sulphuric acid gives :
Section (F) : Hydrides

F-1._ Among the hydrides of group 16, water shows unusual boiling point. Why ?
F-2._ Ammonium salts generally resemble those of potassium and rubidium in solubility & structure. Give reason
F-3._ Write balanced equation when NH3 is dissolved in

(a) water (b) HCl (c) aq. CO2
F-4._ What happens when phosphine is absorbed in mercuric chloride solution ?
F-5. On being slowly passed through water, PH3 forms bubbles but NH3 dissolves. Why is it so ?
F-6._ How is hydrazine prepared ?
Section (G) : Halides and Oxyhalides

G-1._ Pentahalides of phosphorus are known, but not pentahydride. Why ?
G-2._ A compound ‘X’ which is a yellowish white powder is prepared by the reactions of white phosphours with
excess of dry Cl2. Identify ‘X’ :
G-3. Which hydride of the oxygen family shows the lowest boiling point?
G-4. What happens when
(A) PCl5 is heated.
(B) PCl5 is reacted with heavy water.
G-5. Why does PCl3 fume in moist air ?
G-6. Complete and balance the following : [JEE 1998, 2]
(i) P4O10 + PCl5  (ii) NH3 + NaOCl 
Section (H) : Miscellaneous

H-1._ NaHSO3 + [X] (excess) + H2O 
 NaHSO4 + HI
[X] + Na2S2O3   NaI + [Y]
Identify X & Y ?
H-2._ Identify the product of the given reaction :
AgBr + 2Na2S2O3  
H2SO4 (dil) + Na2S2O3  
H2SO4 (conc.) + Na2S2O3  
H-3._ A and B are elements with atomic numbers 16 and 17. Write different combinations of binary compounds
known from them.
ADV PNO - 66
Section (A) : General facts about elements
A-1. Which of the following is least reactive ?
(A) White phosphorus (B) Yellow phosphorus
(C) Red phosphorus (D) Black phosphorus
A-2._ Nitrogen is best obtained by the thermal decomposition of which one of the following :
(A) NH4Cl (B) NH4NO3 (C) AgNO3 (D) NH4NO2
A-3. In modern process, white phosphorus is manufactured by :

(A) heating a mixture of phosphorite mineral with sand and coke in an electric furnace
(B) heating calcium phosphate with lime
(C) heating bone ash with coke
(D) heating phosphate mineral with sand.
Section (B) : Based on Periodic trends

B-1. The oxidation state of sulphur in the anions SO32–, S2O42– and S2O62– follows the order :
(A) S2O62– < SO42– < SO32– (B) S2O42– < SO32– < S2O62–
(C) SO3 < S2O4 < S2O6
2– 2– 2–
(D) S2O42– < S2O62– < SO32–
B-2. Correct statement about allotropy of sulphur is :

(A) Monoclinic sulphur is more stable than Rhombic sulphur at room temperature.
(B) Both Monoclinic and Rhombic sulphur have same ring structures and crystalline structure.
(C) Rhombic sulphur exists at room temperature.
(D) None of these

C-1. The nitrogen atom may complete its octet in several ways. Which one is incorrect ?
(A) Electron gain to form the nitride Ion, N3– e.g. Li3N.
(B) Formation of electron pair bonds. e.g. NH3 or NF3 Azo compounds (–N=N–)
(C) Formation of electron - pair bonds with electron gain. e.g. Amide ion NH2– and imide ion NH2–.
(D) Formation of electron pair bonds with electron gain : NH4+ ; N2H5+; (C2H5)4 N+
C-2. NH4 , NH3 , NH2– , NH2– and N3 – are :

Ammonium Ammonia Amide Imide Nitride
(A) Isoelectronic (B) Isostructural
(C) Homologous members (D) Nitrogen has different oxidation state
C-3._ How many P=O bonds are present in (HPO3)3 ?

(A) 0 (B) 6 (C) 3 (D) 9
C-4._ The correct order of sulphur  oxygen bond length in S2O32, SO42, SO3 and S2O62 is
(A) S2O32 < SO42 < SO3 < S2O62 (B) S2O32 < S2O62 < SO42 < SO3
(C) S2O3 < SO4 < S2O6 < SO3
2 2 2
(D) S2O62 < SO42 < SO3 < S2O32
C-5._ Which of the following bonds has the highest bond energy ?
(A) SeSe (B) TeTe (C) SS (D) OO
C-6. The wrong statement about N2O is :

(A) it is nitrous oxide (B) it is a neutral oxide
(C) it is not a linear molecule (D) it is known as laughing gas
C-7. The hydrides of group 15 elements can act as :

(A) lewis acid (B) lewis base (C) both (D) none
ADV PNO - 67
C-8. The basic strength of the hydrides of group 15 elements :
(A) decreases on moving down the group
(B) increases on moving down the group
(C) first decreases upto AsH3 and then increases
(D) first increases upto AsH3 and then decreases

D-1._ Ammonium salts decompose quite readily on heating :
heat
(i) Ammonium salt of weak oxidizing anion (e.g. Cl–, CO32–, SO42–)   Gas X
(ii) Ammonium salt of strong oxidizing anion (e.g. NO2–, NO3–, ClO4–, Cr2O72–) heat
 Gas Y/Z
Identify X, Y, Z
(A) N2, NH3, N2O (B) NH3, N2, N2O (C) N2O, NH3, N2 (D) NO, NH3, N2O
D-2._ Which of the following does not give oxygen on heating ?

(A) (NH4)2Cr2 O7 (B) KClO3 (C) Zn(ClO3)2 (D) K2Cr2O7
D-3. Red and white phosphorus will differ but not in :

(A) smell (B) solubility in CHCl3
(C) exhibiting phosphorescence (D) reaction with concentrated HNO3
D-4._ Which of the following is incorrect ?

(A) Ammonia is prepared in the laboratory by the action of NaOH on Ammonium salt.
(B) All the hydrides of 15th group are colourless, highly volatile and poisonous gases
(C) Metal phosphides upon hydrolysis give phosphine.
(D) Metal phosphides upon hydrolysis give phosphoric acid.
D-5._ Sulphur and Phosphorus do not react with which of the following acids :
(A) Conc. H2SO4 (B) Dil. H2SO4 (C) Conc. HNO3 (D) Dil. HNO3
D-6._ P4 + NaOH  warm

 Products

Products will be :
(A) H3PO4 + PH3 (B) PH3 + NaH2PO2 (C) NaH2PO2 + H3PO4 (D) H3PO4
D-7._ Hydrolysis of Nitride of s-Block elements (for e.g. Ba3N2 , Ca3N2, Li3N) will yield
(A) NH3 + Metal hydroxide (B) only NH3
(C) NH3 + HNO3 (D) NH4OH
Section (E) : Oxides, Hydroxides, Peroxides, Oxyacids

E-1._ Sulphur trioxide can be obtained by which of the following reactions :

(A) S + H2SO4  
(B) H2SO4 + PCl5 

(C) CaSO4 + C  
(D) Fe2(SO4)3 
E-2._ The correct order of decreasing acidic strength of oxy acids of group 15 elements :
(A) HNO3 > H3SbO4 > H3AsO4 > H3PO4 (B) H3PO4 > H3AsO4 > H3SbO4 > HNO3
(C) HNO3 > H3PO4 > H3AsO4 > H3SbO4 (D) HNO3 > H3AsO4 > H3PO4 > H3SbO4
E-3. NO2 can be prepared by heating :

(A) NH4NO3 (B) NaNO3 (C) Pb(NO3)2 (D) KNO3
E-4. HNO3 + P4O10  HPO3 + X

in the above reaction the product X is :
(A) NO2 (B) N2O3 (C) N2O4 (D) N2O5
E-5._ Which of the following oxides of Nitrogen is Neutral

(A) N2O5 (B) N2O3 (C) N2O4 (D) N2O
ADV PNO - 68
E-6._ Industrial preparation of nitric acid by ostwald’s process involves :
(A) oxidation of NH3 (B) Reduction of NH3
(C) Hydrogenation of NH3 (D) Hydrolysis of NH3
E-7. Which of the following oxides is amphoteric in nature ?

(A) N2O3 (B) P4O6 (C) Sb4O6 (D) Bi2O3
E-8. Following are neutral oxides except :

(A) NO (B) N2O (C) CO (D) NO2
E-9._ Which of the following is the most powerful oxidising agent :

(A) H2SO4 (B) HPO3 (C) H3BO3 (D) H3PO4
E-10. When P4O10 is dissolved in water, the acid formed finally is :

(A) H3PO2 (B) H3PO4 (C) H3PO3 (D) H4P2O7
E-11._Aqueous solution of SO2 is a :

(A) weak acid (B) reducing agent (C) bleaching agent (D) All of these
E-12. Which of the following oxides is the most acidic ?

(A) N2O5 (B) P2O5 (C) As2O5 (D) Sb2O5
Section (F) : Hydrides

F-1. The thermal stability of the hydrides of group 15 follows the order :
(A) NH3 < PH3 < AsH3 < SbH3 < BiH3 (B) NH3 > PH3 > AsH3 > SbH3 > BiH3
(C) PH3 > NH3 > AsH3 > SbH3 < BiH3 (D) AsH3 < PH3 > SbH3 > BiH3 > NH3
F-2. One mole of calcium phosphide on reaction with excess water gives : [JEE 1999, 2]
(A) one mole of phosphine (B) two moles of phosphoric acid
(C) two moles of phosphine (D) one mole of phosphorus pentoxide
F-3. H2S burns in O2 to form

(A) H2O + S (B) H2O + SO2 (C) H2O + SO3 (D) H2SO4 + S
F-4._ PH3 (anhydrous) + HBr (anhydrous)  X Identify X ?

(A) H3BrO3 (B) PH4Br (C) Br2 (D) P4
F-5. Calcium phosphide reacts with water or dil. HCl and gives a compound ‘X’, which fails to react with HCl but
produces dense white fumes with HI (g) due to formation of ‘Y’. Compound X and Y respectively.
(A) X = PH3 and Y = PH4I (B) X = NaH2PO2 and Y = H3PO2
(C) X = PH4+ and Y = PH4I (D) X = PH3 and Y = H3PO2
H2 O2
F-6._ N2       X       Y  O2 H2O
Haber 's Pr ocess Ostwald's Pr ocess   Z
Identify X, Y, Z
(A) NH3, NO2, HNO3 (B) NH3, NO, HNO3 (C) NO2, NH3, HNO2 (D) NH3, NO, HNO2
Section (G) : Halides and Oxyhalides

G-1._ The order of stability of halides of sulphur with different halogens is :
(A) I– > Br– > Cl– > F– (B) F– > Cl– > Br– > I– (C) Br– > Cl– > I– > F– (D) F– > Cl– > I– > Br–
G-2._ Ammonia reacts with excess of chlorine to form :

(A) N2 and NH4Cl (B) NCl3 and HCl (C) NH4Cl and NCl3 (D) N2 and HCl
G-3._ A yellow coloured crystalline substance gave a colourless gas X on reaction with flourine, which is thermally
stable and has octahedral geometry. X can be.
(A) SF4 (B) SF6 (C) SF2 (D) S2F6
ADV PNO - 69
G-4._ PCl3 reacts with water to form :
(A) PH3 (B) H3PO3 and HCl (C) POCl3 (D) H3PO4
G-5._ The final product obtained on hydrolysis of PCl5 is :

(A) H3PO4 (B) H3PO3 (C) POCl3 (D) PH3
G-6. Which of the following reactions depict the oxidising behaviour of H2SO4 ?
(A) 2PCl5 + H2SO4  2POCl3 + 2HCl + SO2Cl2
(B) 2NaOH + H2SO4  Na2SO4 + 2H2O
(C) NaCl + H2SO4  NaHSO4 + HCl
(D) 2H + H2SO4  2 + SO2 + 2H2O
G-7._ Which of the following phosphorus halide is the best reducing agent?
(A) PCl3 (B) PF3 (C) PBr3 (D) P3

H-1. When sulphur is boiled with Na2SO3 solution, the compound formed is :
(A) sodium sulphide (B) sodium sulphate
(C) sodium persulphate (D) sodium thiosulphate
H-2. Na2S2O3 is prepared by :

(A) reacting H2S2O3 with NaOH. (B) reacting Na2SO4 with S in alkaline medium.
(C) heating NaOH and S. (D) reducing Na2SO4 with S in acidic medium.
H-3. The products of the chemical reaction between Na2S2O3, Cl2 and H2O are :
(A) HCl + Na2S (B) HCl + NaHSO4 (C) HCl + Na2SO3 (D) NaHClO3 + H2O
H-4. The term 'thio' is used in the names of all of the following compounds except :
(A) Na2S2O3 (B) Na2S2O6 (C) NaSCN (D) Na2SO3
H-5. Which of the following gives H2O2 on hydrolysis ?

(A) H2S2O3 (B) H2SO5 (C) H2S2O7 (D) H2S4O6
H-6._ Which of the following is not formed in the below reaction :

O3 + KI + D2O  
(A) KOH (B) O2 (C) I2 (D) KOD
PART - III : MATCH THE COLUMN

1. Match the reactions listed in column-I with characteristic(s) / type of reactions listed in column-II.
(A) PCl5  
Moist
(p) Hydrolysis
Air
Warm
(B) P4 + NaOH (conc.) + H2O  
 (q) At least one of the products has tetrahedral hybridisation
200 º C
(C) H3PO3   (r) Disproportionation
200 º C
(D) P4O6 + H2O   (s) At least one of the products has p–d bonding.
2. Match the oxy-acids of phosphorus listed in column-I with type of bond(s) listed in column-II.
Column I Column II
(Oxy acids of phosphoros) (Characteristic bonds)
(A) H4P2O7 (p) P—P bond (s)
(B) H4P2O5 (q) P—O—P bond (s)
(C) H3P3O9 (r) P—H bond (s)
(D) (HPO3)n (cyclic) (s) Three or four P—OH bonds
ADV PNO - 70

1. In case of nitrogen, NCl3 is possible but not NCl5 while in case of phosphorous, PCl3 as well as PCl5 are
possible. It is due to
(A) Availability of vacant d-orbital in P but not in N
(B) Lower electronegativity of P than N
(C) Lower tendency of H bond formation in P than N
(D) Occurrence of P in solid while N in gaseous state at room temperature.
2. The P-P-P bond angle in white phosphorus is close to :

(A) 120º (B) 109º28’ (C) 90º (D) 60º
3. Red phosphorus can be prepared from white phosphorus by :

(A) adding red colour to white phosphorus
(B) heating white phosphorus to red heat
(C) heating white phosphorus at high pressure, inert atmosphere to 250ºC or at low temperature in the
presence of sun light.
(D) heating white phosphorus at low pressure to 250ºC or at low temperature in the presence of sun light.
4. As Rhombic sulphur is heated in a test tube :

Process Temperature
(a) Viscosity increases T1
(b) Viscosity decreases T2
(c) Paramagnetic molecules T3
(d) Breakage of S8 rings T4
(Diradical formation in molten phase)
Correct order of temperature is :
(A) T1 < T3 < T4 < T2 (B) T2 < T4 < T3 < T1 (C) T4 < T1 < T2 < T3 (D) T3 < T4 < T1 < T2
5. Dinitrogen gas is evolved when sodium nitrite is heated below 500ºC :

(A) alone (B) with ammonium chloride
(C) with ammonium hydroxide (D) with potassium nitrate
6. Which statement is not correct for nitrogen ?

(A) It is obtained by heating (NH4)2Cr2O7 (B) It does not readily react with O2
(C) It is a typical non-metal (D) d-orbitals are available for bonding
7. Nitrolim is obtained by passing nitrogen over :

(A) heated mixture of Al2O3 and carbon (B) oleum
(C) calcium carbide (D) heated calcium carbide
8. Which of the following have Hºf < 0 :

(A) Ozone (B) O (g) (C) P (red) (D) S8 (monoclinic)
9. CS2 can separate a mixture of :

(A) P4 and S8 (rhombic) (B) P4 and S8 (monoclinic)
(C) S8 (rhombic) and S8 (monoclinic) (D) S8 (rhombic) and S (plastic)
10. Which of the following reactions does not liberate oxygen ?

(A) O3 + KI + H2O  (B) H2O2 + Cl2 
(C) KO2 (s) + CO2 (g)  (D) None
ADV PNO - 71
11. The gas respectively absorbed by alkaline pyrogallol and oil of cinnamon is :
(A) O2, O3 (B) SO2, O2 (C) O3, CH4 (D) N2O, O3
12. Alkaline K is oxidised by ozone to :

(A) potassium iodate (B) potassium periodate
(C) both (A) and (B) (D) None of these
13. NH3 can't be obtained by :

(A) heating of NH4NO3 or NH4NO2 (B) heating of NH4Cl or (NH4)2 CO3
(C) heating of NH4NO3 with NaOH (D) reaction of AIN or Mg3N2 or CaCN2 with H2O
14. When H2S is passed through nitric acid or acidified KMnO4 solution, the product first formed is :
(A) H2SO4 (B) colloidal sulphur (C) SO2 (D) plastic sulphur
15. Ammonia and red hot CuO react to produce :

(A) Cu2O, N2, H2 (B) Cu, H2O, N2 (C) Cu(OH)2, N2 (D) [Cu(NH3)4](OH)2
16. Phosphine is not obtained by the reaction :

(A) White P is heated with NaOH
(B) Red P is heated with NaOH
(C) Ca3P2 reacts with water
(D) Phosphorus trioxide is boiled with water under pressure.
17. When ammonia is oxidsed by oxygen in the presence of platinum at 800ºC, the gas obtained is :
(A) N2O (B) NO (C) NO2 (D) N2O5
18. Substances burn more readily in N2O than in air because N2O :
(A) is reactive at high temperature.
(B) dissociates to give more oxygen than in air.
(C) the activation energy is increased on increasing temperature.
(D) dissociates more readily than O2.
19. Which of the following is a mixed acid anhydride ?

(A) NO (B) NO2 (C) N2O5 (D) N2O
20. When an article is bleached by SO2 it loses its colour. The colour can be restored by :
(A) exposure to air (B) heating (C) dilution (D) none of these
21. The true statement for the acids of phosphorus H3PO2, H3PO3 and H3PO4 is.
(A) H3PO3 on heating does not disproportionate
(B) all of them are reducing in nature
(C) all of them are tribasic acids
(D) H3PO2 is obtained by alkaline hydrolysis of P4 (white)
22. Which of the following does not have S–S linkage but has O—O linkage ?
(A) S2O82– (B) S2O62– (C) S2O52– (D) S2O32–
23. The true statement for the acids of phosphorus H3PO2, H3PO3 and H3PO4 is :
(A) the order of their reducing strength is H3PO2 > H3PO3 > H3PO4.
(B) the hybridisation of phosphorus is sp2 in all these.
(C) all P–H bonds are reinforced by –* back donation between P and H atoms.
(D) all of these.
24. Hydrolysis of one mole of peroxydisulphuric acid produces [JEE 1996, 1]

(A) two moles of sulphuric acid
(B) two moles of peroxymonosulphuric acid.
(C) one mole of sulphuric acid and one mole of peroxy monosulphuric acid.
(D) one mole of sulphuric acid, one mole of hydrogen peroxide.
ADV PNO - 72
25. The reaction of SO2 with PCl5 yield two oxohalides A and B. ‘A’ can also be prepared industrially by reaction
of SO3 and SCl2. Which of the following about A and B is incorrect ?
(A) The structure of B is tetrahedral
(B) The structure of A is trigonal pyramidal
(C) A reacts vigorously with water and is particularly useful for drying or dehydrating readily hydrolysable
inorganic halides
(D) A and B contain their respective central atoms in their highest oxidation states.
26. Which of the following cannot dissociate as PX5 PX3 + X2

(A) PF5 (B) PCl5 (C) PBr5 (D) PI5
O
||
27. Dimethylsulphoxide (DMSO, CH3 – S – CH3 ) can be obtained by :
(A) Bubbling SOCl2 through CH3Cl
(B) Action of CH3MgCl on SO2Cl2
(C) Action of CH3MgCl on SOCl2
(D) Bubbling Cl2 through S2Cl2 followed by action of CH3MgCl and finally H2O
28. The aqueous solution of hydrogen peroxide :

(A) converts blue litmus pink (B) converts blue litumus white
(C) converts red litumus blue (D) None of these
29. Consider the following compounds :

(1) sulphur dioxide (2) hydrogen peroxide (3) ozone
Among these compounds, those which can act as bleaching agents would include :
(A) 1 and 3 (B) 2 and 3 (C) 1 and 2 (D) 1, 2 and 3
30. Bleaching of a fabric cloth is done using A and excess of chlorine is removed using B. A and B are :
(A) CaOCl2 , Na2SO3 (B) Na2S2O3 , CaOCl2 (C) CaCl2 , Na2S2O3 (D) CaOCl2 , Na2S2O3
31. Aqueous hypo solution on reaction with aqueous AgNO 3 gives :

(A) yellow precipitate changing to black (B) white precipitate changing to black
(C) orange precipitate to blue (D) no precipitate
32. Sulphur reacts with hot aq. KOH to form K2S3 , H2O and compound X. Identify X ?
(A) K2S2O3 (B) K2SO4 (C) H2SO4 (D) K2SO3

1. What is the sum of highest and lowest oxidation states for oxygen family.
2. How many of the following is correct order of specified property.

(a) N > P > As > Pb > Sb > Bi (First ionisation enthalpy)
(b) N > P > As > Sb (Electronegativity)
(c) N–N < P–P < As–As (Single bond length)
(d) As3+ > Sb3+ > Bi3+ (Stability of +3 oxidation state)
(e) White > Red > Black (Reactivity of allotropes of phosphorus)
(f) H3PO2 < H3PO3 < H3PO4 (Proticity of acids)
(g) H3PO2 < H3PO3 < H3PO4 (Reducing power of acids)
3. How many of the following properties increase down the group for nitrogen family.
(a) Atomic size (b) Acidic character of oxides (c) Boiling point of hydrides
(d) Reducing power of hydrides (e) Extent of p-p overlap. (f) Metallic character.
(g) Basic character of hydrides
ADV PNO - 73
4. Given below are some properties. How many of these can hold good for phosphorous.
(a) Metal (b) Non-metal (c) Metalloid (d) Exhibits allotropy
(e) Catenation property (f) Solid (g) Good conductor of electricity
(h) Least dense among nitrogen family elements.
5. Below reaction sequence illustrates the various stages of reduction of nitric acid where a, b, c, d are the
number of electrons involved in the reduction of 1 mole N-atoms.
HNO3 
  NO2 
  NO 
  N2O 
  NH3
ae be ce de
Find the value of (2a + b + 3c – d).
6. A yellow coloured crystalline element gives a colourless gas (X) on reaction with fluorine which is thermally
stable & has octahedral geometry. The atomicity of compound (X) would be....
7. Ozone reacts with dry iodine to form an oxide having .... oxygen atoms in one of its molecules.
8. Sulphur can form dihalide, tetrahalide and hexahalide with fluorine. One mole of each of these three compounds
is mixed with water. The total number of moles of product molecules obtained is____. If no reaction occurs,
count zero.
9. Number of halides undergoing complete reaction in presence of water under normal conditions is :
BF3, BCl3, NCl3, AlCl3, CCl4, PCl3, AsCl3
10. In how many of the following reactions N2 gas may be released.

  
(a) NH4NO2   (b)(NH4)2Cr2O7   (c) NH2CONH2 + HNO2  
(d) NH2CONH2 + NaOBr  (e) NH3 + Cl2 (LR)  (f) NH3 + Br2 (LR) 
(g) NH3 + NaOCl  (h) NH3 + CaOCl2  
(i) Ba(N3)2  
11. NH3, N2H4, HN3, PH3, H2S, AsH3, SbH3, H2Se, H2Te
Number of molecules in which lone pair of electrons on the central atom is present in pure s-orbital.
4
gelatin or EDTA
12. NH3 + NaOCl       products
The number of moles of N–H bonds present in one mole of the strongest nucleophile present in the product
is :
13. Number of acidic oxides among the following is :

(a) N2O (b) NO (c) N2O3 (d) N2O4 (e) N2O5 (f) P4O6
(g) P4O10 (h) SO3 (i) B2O3 (j) CO
14. Number of gaseous oxides among the following at room temperature is :

(a) N2O (b) NO (c) N2O3 (d) NO2 (e) N2O5 (f) P4O6
(g) P4O10 (h) SO2 (i) SO3
15. The number of O-atoms having sp2 hybridisation in P4O10 molecule is :
16. N2O4, (HPO3 )3, H2CO3, SO2, SO3, P4O10 H2SO4, N2O3, HNO3, H3PO3.
(a) Among the above compounds, compounds having at least one p-pbond are x.
(b) Among the above compounds, compounds having at least one d-pbond are y.
Give the answer as x + y.
17. Number of acids having central atom in +3 oxidation state among the following is :
(a) HNO2 (b) HNO3 (c) H3PO2 (d) H3PO3 (e) H3PO4 (f) H4P2O5
(g) H4P2O7 (h) H2SO3 (i) H2S2O7 (j) H2S2O8 (k) H2SO4
18. SOCl2 can react with how many of the following species to liberate SO2?
H2O, HCl, C2H5OH, CH3COOH, H2SO4, H3PO4, D2O
19. Cold conc. HNO3 will completely dissolve :

Pb, Pb3O4, Fe, Sn, Mg, MgO, Hg, Au, Ag, Pt.
ADV PNO - 74
20. Cold dil. H2SO4 will completely dissolve :
Pb, Fe3O4, Fe, Cu, Mg, MgO, CoCO3, CuCO3, SrCO3
21. How many are redox reactions -


(i) K4[Fe(CN)6] + conc. H2SO4  (ii) conc. H2SO4 + KCl 
(iii) conc. H2SO4 + KBr  (iv) conc. H2SO4 + NH3 
(v) conc. H2SO4 + KNO3  (vi) conc. H2SO4 + PCl5 
(vii) conc. H2SO4 + COCl2  (viii) conc. H2SO4 + Zn 
(ix) conc. H2SO4 + Cu 
22. x P4 + y SO2Cl2 

then y/x ?
23. Complete hydrolysis product of 1 mole each of following will need how many total number of moles of NaOH
for complete neutralisation?
SOCl2 , SO2Cl2 , PCl3 , PCl5 , NCl3
24. Aqueous solution of how many of the following species turn blue litmus red ?
(i) SF4 (ii) PCl3 (iii) N2O (iv) NO2Cl
(v) SF6 (vi) SeF6 (vii) AsCl3 (viii) POCl3
(ix) SO2 (x) SO2Cl2 (xi) SOCl2 (xii) COCl2
(xiii) CCl4
25. How many of the following compounds are possible products when chlorine is passed through hypo solution.
S, HCl, Na2S, Na2SO4, Na2S4O6, HClO4
26. The difference in oxidation states of sulphur atoms (in different oxidation states) present in Na2S4O6 is :
27. How many compound(s) or ion(s) can be oxidised by H2O2 among the following :
AsO33–, SO42–, Fe2(SO4)3, NH2–NH2, H2S, PbS, O3
NaOH( aq )
28. S(s)    (A) + (B)

CdCl I2
(B) 
2
 Yellow ppt. (C) ; Solid (A)  (D) + (E)
HCl
(E)  White turbidity + Gas (F)
Count total number of sulphur atoms in one molecule each of (A), (B), (C), (D), (E) and (F) :
29. A gas is pale blue in colour on liquifaction, the colour arises from electronic transitions. This transition is
forbidden in gaseous state. The gas does not burn but is a strong supporter of combustion. Give the molar
mass of this gas.

1. As, Sb and Bi show lesser tendency to form negative ions of the type M3–. This is because
(A) these elements are less electronegative
(B) metallic character increases down the group
(C) they are unable to hold the added electrons due to inert pair effect
(D) they do not posses half filled np subshells
2. The correct statement(s) is/are :

(A) The PF6– ion exists
(B) The NF6– ion does not exist
(C) N can form p-p bonds with itself and with other elements having small size and high E.N.
(D) The catenation tendency is weaker in N than P
ADV PNO - 75
3. Dinitrogen gas is evolved when sodium nitrite is heated strongly :
(A) alone (B) with ammonium chloride
(C) with ammonium hydroxide (D) with potassium nitrate
4. Correct statements about allotropy ?

(A) Plastic sulphur exists as zig-zag chains of sulphur.
(B) Monoclinic sulphur is soluble in water and insoluble in CS2.
(C) Milk of sulphur gradually changes to Rhombic sulphur.
(D) Milk of sulphur is used in medicines.

(A) The hydrides of group 15 elements act as oxidising agents
(B) The hydrides of group 15 elements act as reducing agents
(C) The oxidising power increases in going from NH3 to BiH3
(D) The reducting power increases in going from NH3 to BiH3
6. Ammonium dichromate on heating liberates a gas. The same gas will be obtained by :
(A) heating NaNO2 and NH4Cl.
(B) treating H2O2 with NaNO2 .
(C) passing ammonia gas over red hot CuO.
(D) treating ammonia with KMnO4 in neutral medium.
7. Nitrogen differs from rest of the members on the account of various factors. Which of the following properties
can be classified as anomalous properties of nitrogen ?
(A) Bond enthalpy of NN is 941.4 kJ/mol.
(B) Hydride of nitrogen i.e. ammonia has appreciable boiling point as compared to the other members like
P, As.
(C) NH3 can form stable complexes by donating its lone pair.
(D) Molecular nitrogen comprises 78% by volume of the atmosphere.
8.  Which of the following elements react with metals to form their binary compounds exhibiting –3 oxidation
state ?
(A) N (B) P (C) As (D) Bi
9. White phosphorus may be removed from red phosphorus by :

(A) sublimation under reduced pressure (B) dissolving in water
(C) dissolving in CS2 (D) heating with an alkali solution
10. The compound(s) which on strong heating gives oxygen is/are :

(A) AgNO3 (B) BaO2 (C) Pb(NO3)2 (D) CaCO3
11. Which of the following is/are true for oxygen.

(A) KMnO4(s) on strong heating gives oxygen gas
(B) Oxygen mixed with helium is used for artificial respiration.
(C) It has two unpaired electrons in bonding  molecular orbitals.
(D) Fractional distillation of liquefied air is used as an industrial method for the preparation of oxygen gas.
12. The correct statements(s) regarding hydrides (H2E) of group-16 is/are :

(A) The acidic character increases from H2O to H2Te.
(B) The bond (H-E) dissociation enthalpy decreases down the group.
(C) The thermal stability of hydrides decreases down the group
(D) The reducing character of hydrides increases down the group
13. The correct statements regarding ozone is/are

(A) Ozone is thermodynamically less stable with respect to oxygen
(B) It acts as powerful oxidising agent
(C) It rapidly react with NO(g) and form NO2(g) and O2(g)
(D) It is toxic substance
ADV PNO - 76
14. The incorrect statement(s) regarding oxides of group-16 elements is/are
(A) Reducing property of dioxide decreases from SO2 to TeO2
(B) All these elements form oxides of the EO2 and EO4 types
(C) Selenium and tellurium do not form SeO3 and TeO3
(D) SO2 is an oxidising agent while TeO2 is a reducing agent.
15. Which of the following ions dissolve in excess of aq. NH3.

(A) Al3+ (B) Cu2+ (C) Ag+ (D) Zn2+
16. Which of the following is/are incorrect statement(s) for phosphine ?

(A) It is less basic then NH3
(B) It is less poisonous than NH3
(C) The solution of copper sulphate gives no precipitate with PH3.
(D) Phosphine burns in air forming predominantly H3PO4 .
17. Which of the following process(es) can give sulphur ?

(A) H2S gas is passed through nitric acid.
(B) Cl2 gas is passed into water saturated with hydrogen sulphide.
(C) Hydrogen sulphide is passed through sodium bisulphate solution.
(D) H2S gas is passed through acidified KMnO4 solution.
18. How is H2S prepared in laboratory ?

(A) FeS + H2SO4 (B) FeSO4 + H2SO4
(C) FeS + HCl (D) Elemental H2 + elemental S8
19. A gas is obtained on heating ammonium nitrate. Which of the following statements are incorrect about this
gas :
(A) causes laughter (B) brings tears to the eyes
(C) is acidic in nature (D) is basic in nature
20. Which of the following represents correct dissociation of nitrate salts on heating.
1 1
(A) 2LiNO3  Li2O + 2NO2 + O (B) Pb(NO3)2  PbO + 2NO2 + O
2 2 2 2
(C) NH4NO3  N2O + 2H2O (D) NH4NO2  N2 + 2H2O
21. SO2 can reduce :

(A) HClO3 to HCl (B) Cr2O72– / H+ to Cr3+
–
(C) MnO4– / H+ to Mn2+ (D) IO3 to I2
22. A white crystaline oxide (A) having garlic smell reacts with cold water to form a compound (B). On heating,
(B) gives compound (C) & gas (D). Which of the following are correct statements :
(A) Solution of gas (D) does not turn red litmus blue
(B) The gas (D) can also be produced by reaction of NaOH with red phosphorus
(C) Gas (D) exists in dimeric form.
(D) Compound (B) can act as a reducing agent but (C) cannot.
23. Select the correct statement.

(A) Ostwald's method of preparation of HNO3 is based upon catalytic oxidation of NH3 by atmospheric oxygen.
(B) HNO2 can act as both oxidising and reducing agent.
(C) NO2 reacts with O3 to form N2O5.
(D) HNO3 can be used both as oxidising and reducing agent.
24. Which of the following statements is (are) correct ?

(A) Antimony on reaction with conc. HNO3 gives antimonic acid.
(B) Manganese on reaction with cold and dilute HNO3 gives NO2 gas.
(C) HNO2 disproportionate to give HNO3 and NO
(D) HNO3 on reaction with P4O10 gives N2O5
ADV PNO - 77
25. Concentrated sulphuric acid acts as
(A) dehydrating agent (B) sulphonating agent (C) reducing agent (D) oxidising agent.
26. Which among the following is/are peroxo acid (s) ?

(A) H2S2O3 (B) H2SO5 (C) H2 S2 O7 (D) H2S2O8
27. Which of the following reactions are correct.

(A) PCl5  P4O10
 LiPF6
LiF (B) PCl5  POCl3
(C) PCl3 + NaH  PH3 (D) PCl5 + H2O  POCl3
(equimolar amount)
28. Which of the following are used as chlorinating agents in organic synthesis of compounds ? (Like acid
converted to acid chloride).
(A) SOCl2 (B) SO2Cl2 (C) PCl3 (D) PCl5
29. Select the correct statement(s) regarding reaction of SO2 with PCl5.
(A) It is a redox reaction.
(B) One of the product is sulphuryl chloride.
(C) Both the products on addition of water produce strongly acidic solutions.
(D) Both the products have same hybridisation of central atom.
NaH CuSO 4
30. (P)  (Q)    (R)  black precipitate
(P) may be :
(A) SCl2 (B) PCl3 (C) NCl3 (D) HCl
31. What is true for hydrogen peroxide and ozone ?

(A) H2O2 acts as a stronger reducing agent in alkaline medium than in acidic medium
(B) H2O2 and O3 both are oxidising agents as well as bleaching agents
(C) H2O2 forms a hydrate, H2O2.H2O
(D) Ozone is used in the manufacture of potassium permangnate from pyrolusite.
32. Which of the following statement (s) is/are true for sodium thiosulphate ?
(A) it acts as an antichlor
(B) it is used as a reducing agent in iodometric titration.
(C) it reacts with hydrochloric acid to form SO2 and sulphur.
(D) it is used in photography as hypo to dissolve excess of AgBr as a soluble complex.
33. Which of the following statements are correct for H2O2 ?

(A) It is neutral towards litmus, but bleaches litmus white.
(B) It is more acidic than H2O.
(C) Density and dielectric constant are higher than H2O.
(D) H2O2 is produced by auto oxidation of 2-ethyl anthraquinol.
34. A solution of ammonia in water contains which of the following species :

(A) H+ (aq.) (B) OH– (aq.) (C) NH4+ (aq.) (D) NH3 (aq.)
Comprehension # 1
Nitrogen forms the largest number of oxides as it is capable of forming stable multiple bonds with oxygen.
They range from N2O (O.S of nitrogen +1) through NO, N2O3, NO2, N2O4 to N2O5 (O.S of nitrogen +5).
Following points are important regarding the study of oxides of nitrogen.
(a) All oxides of nitrogen except N2O5 are endothermic as a large amount of energy is required to dissociate
the stable molecule of oxygen and nitrogen.
ADV PNO - 78
(b) The small electronegativity difference between oxygen and nitrogen make N–O bond easily breakble to
give oxygen and hence oxides of nitrogen are said to be better oxidising agents.
(c) Except N2O5 , all are gases at ordinary temperature. N2O3 is stable only at lower temperature (253 K).
(d) Except N2O and NO which are neutral oxides, all are acidic oxides which dissolve in water forming
corresponding oxy acids.
(e) They are also good example for illustrating the concept of resonance.
1. The gas which is acidic in nature is :

(A) NO (B) N2O (C) NO2 (D) both (A) and (C)
2. Which of the following statements is correct for the oxides of nitrogen ?
(A) Dinitrogen trioxide dissolves in potassium hydroxide forming potassium nitrate.
(B) Aqueous solution of nitrogen dioxide behaves both as a reducing agent and as an oxidising agent.
(C) Nitrous oxide is fairly soluble in cold water and turns blue litmus red.
(D) Nitrogen dioxide is not acidic oxide.
Comprehension # 2
An inorganic iodide (A) on heating gives gases (B) and (C). (B) is neutral towards litmus while (C) is acidic.(B)
gives back dense white fumes of (A) when cooled with (C). (A) functions as a strong acid in water. (C) is also
obtained by action of (D) on water. (D) can be obtained when (B) reacts with I2 in presence of anhydrous
CaCl2. (B) is poisonous, has smell of rotten fish and it is sparingly soluble in water.
Now answer the following questions :
3. Select the correct statement from the following for the gas (B).
(A) It produces dense white fumes with HCl (B) It produces dense violet fumes on combustion
(C) It produces dense white fumes with BF3 (D) It can act as oxidising agent.
4. The compound (A) :

(A) turns moist red litmus blue (B) reacts completely with water
(C) is used as a dehydrating agent (D) all of these
5. What is true about compound (D) ?

(A) The oxidation number of central atom of (D) is + IV
(B) Compound (D) produces a yellow precipitate with silver nitrate solution.
(C) Compound (D) dissolves in water forming an acid which with sodium hydroxide forms three series of salts.
(D) Both (B) and (C)
Comprehension # 3
Oxygen differs from the other elements of the group. Compounds of oxygen with metals are more ionic in
nature and hydrogen bonding is more important for oxygen compounds. Oxygen is never more than divalent
because when it has formed two covalent bonds, there are no low energy orbitals which can be used to form
further bonds. However, the elements S, Se, Te and Po have empty d-orbitals which may be used for bonding,
and they can form four or six bonds by unpairing electrons. The higher oxidation states become less stable
on descending the group.
The bond between S and O or Se and O are much shorter than might be expected for a single bond owing to
p – d interaction between the p–orbital of oxygen and d-orbital of S or Se.
6. Which of the following statement is incorrect ?

(A) Oxo-anions of sulphur have little tendency to polymerise compared with the phosphates and silicates.
(B) In pyrosulphurous acid (H2S2O5), the oxidation states of both the sulphur atoms are not same, they are
+V and +III
(C) Concentrated HNO3 oxidises both sulphur and selenium to H2SO4 (+VI) and H2SeO4 (+VI) respectively.
(D) Most metal oxides are ionic and basic in nature while non-metallic oxides are usually covalent and acidic
in nature.
ADV PNO - 79
7. Which one of the following orders represents the correct order for the properties indicated against them ?
(A) H2O < H2S < H2Se < H2Te – acidic character (B) H2O < H2S < H2Se < H2Te – thermal stability
(C) H2S > H2Se < H2Te < H2O – reducing character (D) H2S < H2Se < H2O < H2Te – boiling point
Comprehension # 4
The property of hydrides of p–block elements mostly depends on :
(i) electronegativity difference between central atom and hydrogen
(ii) size of central atom
(iii) number of valence electrons in central atom
Some undergo hydrolysis in which central atom is less electronegative, react with OH – to give hydrogen.
While acidic property of hydride in a period depends on electronegativity of central atoms, i.e. more
electronegative is the atom, more acidic is hydride. n a group, acidic property is proportional to size of
central atom. Some electron deficient hydride behaves as Lewis acid while only one hydride of an element in
p–block behaves as Lewis base with lone pair of electrons. Hydrides in which central atom’s electronegativity
is close to hydrogen has no reaction with water.
8. Which one is the weakest acid among the following ?

(A) HF (B) HCl (C) HBr (D) H
9. Which hydride has no reaction with water ?

(A) NH3 (B) CH4 (C) BeH2 (D) NaH
10. Which one is strongest base ?

(A) OH– (B) HS– (C) HSe– (D) HTe–
ADV PNO - 80
EXERCISE - 1
PART - I
A-1. Atomic size of nitrogen is very less. Hence ‘N’ atom can approach close to another ‘N’ atom. This facilitates
the lateral overlap of the p-orbitals forming -bonds.
Due to large size, other atoms of the same group form only single bonds, but not multiple bonds.
A-2. White phosphorus is very reactive, due to the P-P-P bond angle strain at 60º.
Red phosphorus is very stable, due to chain like polymeric structure.
A-3. Rhombic sulphur
A-4. Phosphorite Ca3(PO4)2 and fluoroapatite Ca5(PO4)3F
B-1. Bismuth and antimony both belong to the nitrogen family and exhibit the +5 oxidation state. However, on
moving down the group, i.e., from antimony to bismuth, the stability of the +5 oxidation state decreases.
This is due to the inert pair effect. Thus, Bi (V) is a stronger oxidant than Sb (V).
B-2. – 3 to + 5, 0
B-3. Nitrogen exhibits -3 state in nitride and phosphorus exhibits –3 state in phosphide. Going down the group,
the atomic size increases and metallic character also increases. Hence, the tendency to exhibit negative
oxidation state decreases down the group VA.
B-4. In vapour state, sulphur exists as S2 molecule. S2 molecule, like O2 molecule, has two unpaired electrons in
the anti-bonding n* orbitals. Hence, like O2, it exhibits paramagnetism.
C-1. (a) Oxidation state of phosphorus in P4 molecule is zero.
(b) Valency of P in P4 molecule is three. Each P atom forms 3 bond pairs and possesses on lone pair.
(c) Total number of P-P sigma bonds in a molecule of phosphorus is six.
(d) Phosphorus-Phosphorus bond order in P4 molecule is one.
(e) Bond angle 60º. (f) Tetrahedral.
C-2. P4O6 ; PO
4 10
N2 O 3 ; N2 O 5 :
C-3. Tetrathionate
Tetrathionate has S–S linkage.

The oxidation states of sulphur are : +5, 0, 0 and +5.
The average oxidation state of S is +2.5.
ADV PNO - 81
C-4. In PH4+, phosphoros undergo sp3 hybridization, but in PH3 phosphoros uses pure p-orbitals for bonding.
Hence bond angle in PH3 is nearly 90º.
C-5. Oxide Oxyacids

N2 O 3 HNO2
NO2/N2O HNO2 + HNO3
N2 O 5 HNO3
P4 O 6 H3PO3
P4O10 H3PO4
C-6. Although each of the above has same electronic distribution in bonding orbitals, nitrogen is inert because of
non-polar nature of bond and high NN dissociation energy. Rest all (CO, CN–, NO+) are polar.
C-7. NO2 being odd molecule, on dimerisation is converted to stable N2O4 molecule with even number of electrons.
C-8. Due to the decrease in bond (E – H) dissociation enthalpy down the group acidic character increases.
C-9. ‘N’ atom of NH3 or ‘P’ atom of PH3 has a lone pair of electrons available for donation. Hence NH3 and PH3 are
Lewis bases. The electron pair density on a larger ‘P’ atom is less than that of smaller ‘N’ atom. Hence PH 3
is a weaker base.
D-1. Barium azide on heating undergoes thermal decomposition. Pure dinitrogen gas is obtained on heating
azide.
heat
Ba(N3)2   Ba + 3N2
D-2. All the elements show no reaction with water.
D-3. White phosphorus (P4).
D-4. S2– + S S22– ; S22– + S S32– .......................... S1112– + S S122–
Upto 12 sulphur atoms poly sulphide ions are observed in significant amounts.
E-1. SO3 reacts with water to form H2SO4 which forms a mist that is difficult to condense. It escapes in the
atmosphere. It is, therefore, absorbed in conc. H2SO4 to form oleum which may be diluted to form H2SO4.
E-2. Pure oxygen will oxidise P4O6 to P4O10 despite an excess of P4 is kept at the start of the reaction. Hence,
nitrogen gas is used as a diluent.
E-3. SO2Cl2 is formed from H2SO4 by treating with excess of phosphorus pentachloride.
H2SO4 + 2PCl5  SO2Cl2 + 2HCl + 2POCl3
SO3 is obtained from sulphuric acid by dehydration with phosphorus pentachloride.
2H2SO4 + P4O10  4HPO3 + 2SO3
SO2 is obtained from conc. H2SO4, when heated with copper metal.
2H2SO4 (conc.) + Cu  CUSO4 + 2H2O + 2SO2
E-4. P4O10
E-5. TeO (oxidation number of Te is +2) is basic.
TeO2 (oxidation number of Te is +4) is amphoteric.
TeO3 (oxidation number of Te is +6) is acidic.
As the oxidation number of the element forming oxide increases, the acidic nature also increases.
E-6. SO2
F-1. Due to high electronegativity of O, the O–H in H2O forms strong intermolecular H-Bonds. As a result water
exists as an associated molecule while other hydrides of group 16 do not form H–Bonds and hence exist as
discrete molecules. As a result, water shows unusual physical properties, i.e. high b.p., high thermal stability
and weaker acidic character as compared to other hydrides of group 16.
ADV PNO - 82
F-2. They resemble since the three ions are of comparable radii and same charge :
NH4+ = 1.48 Å, K+ = 1.33 Å, Rb+ = 1.48 Å.
F-3. (a) NH3 + H2O NH3.H2O (Ammonium hydroxide) NH4+ (aq) + OH– (aq)
This reaction occurs to small extent only (1-2 %). Rest of NH3 remains unreacted.
(b) NH3 (aq.) + HCl (aq.) NH4Cl(aq.)
(c) NH3(aq.) + H2O + CO2 (aq.)  NH4HCO3 (solvay ammonia process)
F-4. Mercuric phosphide is formed by the reaction between phosphine and mercuric salt,
2PH3 + 3HgCl2  Hg3P2  + 6HCl
F-5. N–H bond is more polar than P–H bond. Hence, NH3 forms hydrogen bonds with H2O molecules and hence
dissolves in it whereas PH3 does not dissolve and forms bubbles.
Also same electronegativity of P and H.
F-6. NH3 + NaOCl  NH2Cl + NaOH (fast)
NH3 + NH2Cl  NH2NH2 + NH4Cl (slow)
G-1. Phosphorus exhibits pentavalency in excited state. Fluorine, chlorine or bromine is more electronegative and
influences excitation to form PX5. However, hydrogen is not that much electronegative to incluence the
excitation in phosphorus. Hence PH5 is not formed.
G-2. PCl5
G-3. H2S

G-4. (A) PCl5  PCl3 + Cl2
(B) PCl5 + D2O  POCl3 + 2 DCl
POCl3 + 3D2O  D3PO4 + 3DCl
G-5. PCl3 hydrolyses in the presence of moisture giving fumes of HCl
PCl3 + H2O  H3PO3 + 3 HCl
G-6. (i) P4O10 + 6PCl5  10POCl3 (ii) NH3 + NaOCl  NH2Cl + NaOH (fast)
NH3 + NH2Cl  NH2NH2 + NH4Cl (slow)
H-1. X = I2 ; Y = Na2S4O6
H-2. AgBr + 2Na2S2O3  Na3[Ag(S2O3)2] + NaBr
H2SO4 (dil) + Na2S2O3  Na2SO4 + S (white turbidity) + H2O + SO2
3H2SO4 (conc.) + Na2S2O3  Na2SO4 + 4SO2 + 3H2O
H-3. Atomic number of A = 16. It is sulphur. Atomic number of B = 17. It is chlorine.

Excess sulphur reacts with chlorine to give dimeric monochloride. Sulphur reacts with excess chlorine to
give tetrachloride. Molten dimeric monochloride on saturation with chlorine gives dichloride.
2S + Cl2  S2Cl2 ; S2Cl2 + Cl2  2SCl2
PART - II
A-1. (D) A-2. (D) A-3. (A) B-1. (B) B-2. (C)
C-1. (D) C-2. (A) C-3. (C) C-4. (C) C-5. (C)
C-6. (C) C-7. (B) C-8. (A) D-1. (B) D-2. (A)
D-3. (D) D-4. (D) D-5. (B) D-6. (B) D-7. (A)
E-1. (D) E-2. (C) E-3. (C) E-4. (D) E-5. (D)
E-6. (A) E-7. (C) E-8. (D) E-9. (A) E-10. (B)
ADV PNO - 83
E-11. (D) E-12. (A) F-1. (B) F-2. (C) F-3. (B)
F-4. (B) F-5. (A) F-6. (B) G-1. (B) G-2. (B)
G-3. (B) G-4. (B) G-5. (A) G-6. (D) G-7. (D)
H-1. (D) H-2. (C) H-3. (B) H-4. (D) H-5. (B)
H-6. (A)
PART - III
1. (A - p, q, s) ; (B - p, q, r, s) ; (C - q, r, s) ; (D - p, q, r, s)
2. (A - q, s) ; (B - q, r) ; (C - q, s) ; (D - q)
EXERCISE - 2
PART - I
1. (A) 2. (D) 3 . (C) 4. (C) 5. (B)
6. (D) 7. (D) 8 . (C) 9. (D) 10 . (D)
11 . (A) 12 . (C) 13 . (A) 14. (B) 15. (B)
16 . (B) 17 . (B) 18. (D) 19 . (B) 20. (A)
21 . (D) 22 . (A) 23 . (A) 24 . (C) 25 . (D)
26 . (A) 27. (C) 28 . (B) 29. (D) 30 . (D)
31. (B) 32. (A)
PART - II
1. 4 2. 5 3. 3 4. 04 5. 3
6. 7 7. 9 8 . 8 9. 5 10 . 9
11 . 6 12. 4 13 . 7 14. 5 15 . 10
16. 12 17 . 3 18. 6 19 . 6 20. 6
21. 3 (iii, viii, ix) 22. 10 23 . 24 24. 10 25. 3
26. 5 27. 4 28. 9 29 . 32, O2
PART - III
1. (A,B) 2. (A,B,C,D) 3. (A,B) 4. (A,C,D) 5. (B,D)
6. (A,C,D) 7. (A,B) 8 . (A,B,C,D) 9. (A,C,D) 10. (A,B,C)
11 . (A,B,D) 12 . (A,B,C,D) 13 . (A,B,C,D) 14 . (B,C,D) 15 (B,C,D)
.
16 . (B,C,D) 17. (A,B,C,D) 18. (A,C) 19. (B,C,D) 20. (A,B,C,D)

21. (A,B,C,D) 22. (A,D) 23. (A,B,C) 24. (A,C,D) 25. (A,B,D)
26 . (B,D) 27. (A,B,C,D) 28. (A,B,C,D) 29. (C,D) 30. (A,B)
31. (A,B,C,D) 32. (A,B,C,D) 33 . (A,B,C,D) 34. (A,B,C,D)
PART - IV
1. (C) 2. (B) 3 . (C) 4. (B) 5. (B)
6. (C) 7. (A) 8 . (A) 9. (B) 10 . (A)
ADV PNO - 84

above.
1. There is considerable increase in covalent radius from N to P. However, from Sb to Bi only small increase
(of 7 pm) in covalent radius is observed. This is due to:
(1) poor shielding by completely filled d- and f-orbitals in Bi.
(2) similar eletronegativity of Sb and Bi.
(3) the Bi being last element of the group.
(4) similar densities of Sb and Bi.
2. Of the different allotropes of phosphorus, the one which is most reactive is

(1) Violet phosphorus (2) Scarlet phosphorus
(3) Red phosphorus (4) White phosphorus
3. Which of the following elements shows highest number of allotropes :

(1) N (2) P (3) S (4) O
4. Nitrogen gas is prepared :

(1) by heating ammonium nitrate. (2) by reacting excess chlorine with liquor ammonia.
(3) by passing HNO3 vapours on red hot copper. (4) by heating lead nitrate.
5. With respect to protonic acids, which of the following statement is correct ?

(1) PH3 is more basic than NH3 (2) PH3 is less basic than NH3
(3) PH3 is equally basic as NH3 (4) PH3 is amphoteric while NH3 is basic.
6. Phosphorus is manufactured by heating in an electric furnance a mixture of

(1) Bone ash and coke (2) Bone ash and silica
(3) Bone ash, silica and coke (4) None of these
7. Which of the following may ignite spontaneously in air ?

(1) White phosphorus (2) Red phosphorus
(3) Black phosphorus (4) Nitrogen
8. Ozone is obtained from oxygen

(1) By oxidation at high temperature (2) By oxidation using a catalyst
(3) By silent electric discharge (4) By conversion at high pressure
9. Crown shape of S8 molecule is present in :

(1) Rhombic sulphur (2) Monoclinic sulphur (3) Both (1) & (2) (4) None of these
ADV PNO - 85
10. Presence of ozone in a gas sample may be detected by :
(1) H2O2 (2) SO2 (3) Hg (4) KI
11. Amongst H2O, H2S, H2Se and H2Te the one with the highest boiling point is
(1) H2O because of hydrogen bonding (2) H2Te because of higher molecular weight
(3) H2S because of hydrogen bonding (4) H2Se because of lower molecular weight
12. When ammonia is passed over heated copper oxide, the metallic copper is obtained. The reaction shows
that ammonia is
(1) A dehydrating agent (2) An oxidising agent
(3) A reducing agent (4) A nitrating agent
13. Phosphine is generally prepared in the laboratory

(1) By heating phosphorus in a current of hydrogen
(2) By heating white phosphorus with aqueous solution of caustic potash
(3) By decomposition of P2H4 at 110ºC
(4) By heating red phosphorus with an aqueous solution of caustic soda.
14. Cyanamide process is used in the formation of

(1) N2 (2) HNO3 (3) NH3 (4) PH3
15. Ammonium nitrate decomposes on warming into

(1) Ammonia and nitric acid (2) Nitrous oxide and water
(3) Nitrogen, hydrogen and ozone (4) Nitric oxide, nitrogen dioxide and hydrogen
16. Which one of the following combines with Fe() ions to form a brown complex ?
(1) N2O (2) NO (3) CO (4) SO 2
17. Formula for tear gas is :

(1) COCl2 (2) CCl3NO2 (3) N2O (4) None of these
18. In P4O10, the number of oxygen atoms bonded to each phosphorus atom are :
(1) 2 (2) 3 (3) 4 (4) 5

19. In the reaction, conc. H2SO4 + P2O5  (X) + SO3 ; the major product (X) is :
(1) PH3 (2) H3PO4 (3) HPO3 (4) H4 P2 O7
20. Bleaching action of SO2 is due to :

(1) its reducing nature (2) its oxidising nature
(3) its acidic nature (4) its both oxidising as well as reducing nature
21. Ortho phosphoric acid on heating above 300ºC gives :

(1) hypophosphorus acid (2) hypophosphoric acid
(3) metaphosphoric acid (4) phosphorous acid
22. 1 mol each of H3PO2, H3PO3 and H3PO4 will neutralise x mole of NaOH, y mol of Ca(OH)2 and z mol of
Al(OH)3 (assuming all as strong electrolytes) respectively. x, y, z are in the ratio of :
(1) 3 : 1 . 5 : 1 (2) 1 : 2 : 3 (3) 3 : 2 : 1 (4) 1 : 1 : 1
23. Which of the following can convert acidified Cr2O72– to green ?

(1) SO2 / H2SO3 / H2SO4 (2) SO3 / H2SO3 / H2S
(3) SO32– / H2S / Fe2+ (4) S2O32– / SO3 / Fe3+
24. Which of the following statements is true for HNO2 ?

(1) It can be prepared by acidifying an aqueous solution of nitrite.
(2) It is unstable weak acid which is known only in aqueous solution.
(3) N2O3 is an anhydride of HNO2.
(4) All of these
ADV PNO - 86
25. The compound which has ionic nature in solid state is :
(1) PCl5 (2) POCl3 (3) P4O10 (4) PCl3
26. Phosphorus trichloride, PCl3 undergoes, hydrolysis at room temperature to produce an oxoacid. It has the
formula :
(1) HPO3 (2) H3PO3 (3) H3PO4 (4) H3PO2
27. Which of the following dissolves in water but does not give any oxyacid solution ?
(1) SO2 (2) OF2 (3) SCI4 (4) SO3
28. Hypo is used in photography to:

(1) Reduce AgBr grains to metallic silver
(2) Convert the metallic silver to silver salt
(3) Remove undecomposed silver bromide as a soluble complex
(4) Remove reduced silver
29. Sulphur on boiling with NaOH solution gives

(1) Na2S2O3 + NaHSO3 (2) Na2S2O3 + Na2S
(3) Na2SO3 + H2S (4) Na2SO3 + SO2
30. Sodium thiosulphate is prepared by [JEE 1996, 1]

(1) reducing Na2 SO3 solution with H2S (2) Boiling Na2SO3 with S in alkaline medium.
(3) Neutralising H2S2O3 solution with NaOH (4) Boiling Na2SO3 with S in an acidic medium

Que. 1 2 3 4 5 6 7 8 9 10
Ans.
Que. 11 12 13 14 15 16 17 18 19 20
Ans.
Que. 21 22 23 24 25 26 27 28 29 30
Ans.

1. In the following reaction, SO2 + 2H2S  3S + 2H2O [NSEC-2000]
(A) sulphur is oxidised and reduced (B) sulphur is oxidised and hydrogen is reduced
(C) sulphur is reduced and there is no oxidation (D) hydrogen is oxidised and sulphur is reduced
2. One gas bleaches the colour of flowers by reduction while the other by oxidation. The gases are
[NSEC-2002]
(A) SO2, CI2 (B) CO, CI2 (C) H2S, Br2 (D) NH3, SO3.
3. In nature, ammonia is synthesisd by nitrifying bacteria using enzymes while in industry it is manufactured
from N2 and H2 using iron oxide catalyst at 550oC. Under the same industrial conditions, enzymes cannot be
used because [NSEC-2003]
(A) enzymes get deactivated at high temperature
(B) enzymes catalyze reactions only in living systems
(C) the reaction becomes vigorous and uncontrollable
(D) the enzymes use nitrates in place of N2.
ADV PNO - 87
4. The anhydride of nitric acid is [NSEC-2003]
(A) nitric oxide (B) nitrous oxide
(C) dinitrogen trioxide (D) dinitrogen pentoxide.
5. Bones glow in the dark. This is due to [NSEC-2005]

(A) the presence of red phosphorus. (B) conversion of white phosphorus into red phosphorus.
(C) the presence of calcium carbonate (D) the presence of calcium phosphate.
6. Which of the following compounds of phosphorus does not have resonating structures ? [NSEC-2006]
(A) H3PO2 (B) H3PO3 (C) H3PO4 (D) (CH3)2HPO3.
7. In thiosulphuric acid H2S2O3, the oxidation states of sulphur atoms are [NSEC-2006]
(A) +  ,+  (B) 0, + V (C) +  , +  (D) – , + V.
8. The ozone hole in the upper atmosphere of the earth is due to the breakdown of ozone to oxygen. The
reaction is catalyzed by – [NSEC-2009]
(A) chlorofluorocarbons
(B) oxygen generated during the reaction
(C) carbon dioxide present in the atmosphere
(D) chlorine formed by the decomposition of chlorofluorocarbons
9. P4 (s) + 3OH– (aq) + 3H2O (l)  PH3 (g) + 3H2PO2– (aq) [NSEC-2009]
In the above equation, the species getting oxidized and reduced respectively are :
(A) P4 and OH– (B) OH– and P4 (C) P4 and H2O (D) P4 and P4
10. The bond having the highest bond energy is [NSEC-2010]

(A) C = C (B) C = S (C) C = O (D) P = N
11. The nitrogen compound formed when Ca(CN)2 reacts with steam or hot water is [NSEC-2011]
(A) N2O (B) NO (C) NO2 (D) NH3
12. The most abundant element in the earth's crust is : [NSEC-2011]

(A) aluminium (B) oxygen (C) silicon (D) iron
13. The element that has the highest tendency to catenate is : [NSEC-2011]
(A) silicon (B) germanium (C) sulphur (D) boron
14. The chemical formula of 'laughing gas' is [NSEC-2012]

(A) NO (B) N2O (C) N2O4 (D) N2O5
15. Phosphine is prepared by the reaction of [NSEC-2012]

(A) P and HNO3 (B) P and H2SO4 (C) P and NaOH (D) P and H2S
16. The oxidation of SO2 by O2 is an exothermic reaction. The yield of SO3 can be maximized if :
(A) temperature is increased and pressure is kept constant [NSEC-2012]
(B) temperature is decreased and pressure is increased
(C) both temperature and pressure are increased
(D) both temperature and pressure are decreased
17. Which of the following salt/s of H3PO3 exists ? [NSEC-2013]

(I) NaH2PO3 (II) Na2HPO3 (III) Na3PO3
(A) I and II only (B) I, II and IIII (C) II and III only (D) III only
ADV PNO - 88
PART - III : PRACTICE TEST-2 (IIT-JEE (ADVANCED Pattern))
A. General :
B. Question Paper Format :
is correct.
C. Marking Scheme :
be awarded.

1. An unknown substance (P) functions as weak base in water. It produces silver mirror test. It reacts with dilute
HCl to produce (Q) which turns blue litmus red. (P) may be :
(A) NH3 (B) PH3 (C) NH2OH (D) HPO3
2. The compound which gives off oxygen on moderate heating is :
(A) Cupric oxide (B) Mercuric oxide (C) Zinc oxide (D) Aluminium oxide
3. Which of the following compounds does give N2 on heating ?
(A) NH4NO2 (B) NH4NO3 (C) NaN3 (D) Both (A) and (C)
4. Which of the following cannot result in the formation of NO ?
(A) N2 + O2 (Electric arc) (B) NH3 + O2 ; (Pt / Rh catalyst / 1200 K)
(C) NaNO3 / HCl (D) None of these
5. A substance dissolves in water giving a pale blue solution which decolourises KMnO 4 and oxidises KI to I2 in
acidic medium :
(A) N2O5 (B) NH3 (C) N2O3 (D) HNO3
6. Which of the following will not decolourise acidified KMnO4 ?
(A) S2O42– (B) S2O52– (C) S2O32– (D) S2O72–
ADV PNO - 89
7. Which of the following statements is not true about ozone ?
(A) It is a pale blue gas at room temperature.
(B) It oxidises sulphur and phosphorus evolving oxygen gas.
(C) It is odourless.
(D) It turns dry KOH red.
8. Sulphuric acid reacts with PCl5 to give

(A) Thionyl chloride (B) Sulphur monochloride
(C) Sulphuryl chloride (D) Sulphur tetrachloride

9. Which is greater for P4 (white) than P4 (red) -

(A) Molar entropy (B) Melting point (C) Solubility in CS2 (D) Ignition temperature
10. What is/are not true about phosphine (PH3) ?

(A) It turns red litmus blue.
(B) It reacts with HCl (aq.) to give PH4Cl.
(C) Phosphonium compounds are obtained when anhydrous phosphine reacts with anhydrous HBr or HI.
(D) It is prepared by hydrolysis of metal phosphides with acids.
11. Which of the following is/are correct regarding nitrogen family.

(A) Nitrogen is restricted to a maximum covalency of 4 as only four orbitals are available for bonding.
(B) The single N–N bond is weaker than the single P–P bond.
(C) The catenation tendency is weaker in nitrogen as compared to phosphorous.
(D) Nitrogen forms p-p bond as well as p-d bonds.
12. P2O5 can dehydrate.

(A) H2SO4 (B) HNO3 (C) HClO4 (D) HPO3
13. The products formed when H3PO2 is heated at 415 K and at 435 K are :
(A) H3PO3 (B) H3PO4 (C) HPO3 (D) PH3
boil
14. 4AgNO3 + 2H2O + H3PO2   4Ag + 'X' + 'Y'
If X is oxyacid of nitrogen and Y is oxyacid of phosphorous then correct statement(s) is/are :
(A) X is HNO2 (B) Y is H3PO4
(C) H3PO2 act as good reducing agent (D) The oxidation number of 'P' changed from +1 to +5
Section-3 : (Single/ Double Integer Value Correct Type.)

15. Cold dilute nitric acid would dissolve how many of the following without significant evolution of any gas :
Pb, Mg, Sb, Au, Ag, Fe, Mn, Sn, P4
16. Which of the following on heating will produce an oxide of nitrogen.
(NH4)2 SO4 , (NH4)2Cr2O7 , NH4NO3 , KNO3 , Pb(NO3)2, (NH4)2HPO4, NH4Cl, NH4NO2
17. NaPO3 can significantly react with how many of the following ?
CaCl2, MgSO4, CaO, Na2CO3, dry HCl, Ca(HCO3)2, Na3PO4
18. One mole of PCl3 is dissolved in excess of water. No. of moles of NaOH required to neutralise this solution
completely is :
19. When hypo solution react with CuCl2 and produce soluble complex, then how many no. of moles of atoms
present in one mole of soluble complex in co-ordination sphere.
ADV PNO - 90
20. How many of the following reactions yield POCl3?
(i) PCl3 + O2  (ii) PCl5 + CO2  (iii) PCl5 + CH3COOH 
(iv) PCl5 + H3BO3  (v) PCl3 + SO2Cl2  (vi) P4O10 + NaCl 
(vii) PCl5 + H2O  (viii) PCl5 + SO2  (ix) PCl3 + SO3 

(A), (B), (C) and (D)

An orange solid (A) on heating gives a green residue (B), a colourless gas (C) and water vapours. The dry gas
(C) on passing over heated Mg gave a white solid (D). (D) on reaction with water gave a gas (E) which formed
black precipitate with mercurous nitrate solution.
21. Select the incorrect statement.
(A) The central atom (s) of the anion of solid (A) has sp3 hybridisation.
(B) The orange solid (A) is diamagnetic in nature.
(C) The anion of orange solid (A) is oxidising in nature.
(D) All metal oxygen bond lengths are equal in anion of solid (A).
22. Which of the following is false for the gas (E) ?
(A) It gives a deep blue colouration with CuSO4 solution.
(B) It is oxidised to a colourless gas (neutral oxide) at 1200 K in presence of a catalyst Pt/Rh in air.
(C) It gives the same gas (C) with potassium permanganate solution.
(D) It gives black precipitate with HgCl2.

23. Match the reactions listed in column-I with characteristic(s) listed in column-II.
Column I Column II
Cool
(1) 2NO2  (p) One of the products is a mixed anhydride.

H
(2) ClO2 + O3   (q) One of the products is an acidic oxide.

(3) K4 [Fe(CN)6] + H2SO4(conc.) + H2O  (r) The oxidation state of the central atom of one of the
products is + 6.
(4) KOH + O3  (s) One of the products is a colourless paramagnetic gas.
Code :
(A) 1 - p, q ; 2 - p, q, s ; 3 - r ; 4 - s (B) 1 - p, q ; 2 - p, q, r, s ; 3 - r ; 4 - s
(C) 1 - p ; 2 - p, q, r, s ; 3 - r ; 4 - s (D) 1 - p, q ; 2 - q, r, s ; 3 - s ; 4 - r

Que. 1 2 3 4 5 6 7 8 9 10
Ans.
Que. 11 12 13 14 15 16 17 18 19 20
Ans.
Que. 21 22 23
Ans.
ADV PNO - 91
PART - IV : INDIAN NATIONAL CHEMISTRY OLYMPIAD (INChO) STAGE-II
Problem # 1 [INChO-2008]
Chemistry of Phosphorus and its compounds
Elemental phosphorus is recovered from the minerals fluorapatite and hydroxyapatite by carbon arc reduction.
The resulting white phosphorus is a solid consisting of P4 molecules.
1.1 Draw the geometrical and Lewis structures of P4.
1.2 White phosphorus reacts vigorously with aqueous sodium hydroxide resulting in the evolution of a gas and
formation of sodium hypophosphite. Write the balanced equation for this reaction.
1.3 Sodium hypophophite and sodium phosphite contain oxoanions of phosphorus.
(a) Draw structures of these oxoaniohs
(b) State whether these oxoanions will act as an oxidizing agent or reducing agent.
Oxidising agent Reducing agent

hypophosphite
phosphite
(c) Give appropriate reasons for your answers.
1.4 H3PO4 can be synthesized by the reaction of hydroxyapatite (Ca5(PO4)3 with H2SO4. Write balanced equation
for this reaction.
Complete combustion of phosphorus yields phosphorus (V) oxide P4O10. that has a cage structure.
1.5 Draw the structure of P4O10.
1.6 Write balanced equation/s for the formation of triethyl phosphate from phosphorus trichloride.
1.7 Show the electronic configurations of P atom in (i) ground and (ii) excited states. State the hybridization of
orbitals of P atom in PCl3 and PCl5 molecules. Predict the geometry of PCl5.
1.8 PCl5 can react with NH4Cl to form cyclophosphazine (NPCl2)n where n  3. Write the balanced equation for
the formation of cyclophosphazine with n = 3 and draw the structure of this product.
PART - V : INTERNATIONAL CHEMISTRY OLYMPIAD (IChO) STAGE-V

Problem # 1 [IChO-1977]
Compare three salts of a composition M2S2Ox where x are three different small integers and M is an alkali
metal. To each of the three salts apply some of the following assertions:
a) The O–O bond is characteristic for the anion.
b) The S–S bond is characteristic for the anion.
c) The S–O–S bond is characteristic for the anion.
d) It is formed by thermal decomposition of hydrogen sulphate.
e) It is formed by anodic oxidation of hydrogen sulphate.
f) It is formed by the reaction of an aqueous solution of sulphite with sulphur.
g) Its aqueous solution dissolves silver bromide.
h) Neutralisation of its aqueous solution with hydroxide MOH yields sulphate M2SO4.
i) In aqueous solution, it is able to oxidise Mn(II) salt to permanganate.
1.1 Fill in the correct x values in the formulas given in the table and indicate in the corresponding square by
appropriate letters those assertions that may be applied to each of the given salts:
M2S2O
M2S2O
M2S2O
ADV PNO - 92
1.2 Write structural formulas of the anions of the above three salts and assign -bonds and -bonds in them.
1.3 Write the chemical equations expressing the processes involved in the assertions under the letters d, e, f, g,
h, i.
The apparatus shown in the figures is intended for preparing ammonia under laboratory conditions.
The test tube being heated contains a mixture of NH4Cl and Ca(OH)2. Which of the figures is correct?
A
B
C D E
32
P labelled phosphorus pentachloride (half-life t1/2 = 14.3 days) is used to study the electrophilic attack of a
PCl4+ cation on nitrogen or on oxygen.
3.1 Write the balanced equations for the reaction of red phosphorus forming PCl5.
3.2 Write the reaction equations for complete hydrolysis of the compounds II and III using sodium hydroxide.
4. Give the oxidation states of N in the following series:
(i) NH3 (ii) NO2– (iii) NO3–
 
5. 
The synthesis of [N ][AsF ] , a white ionic solid, was achieved by reacting [N2F ] [AsF ] with hydrazoic
5
–
6 6
acid, HN3, in liquid HF at –78 °C. Write the balanced chemical equation for this reaction.
ADV PNO - 93
PART - I
1. (1) 2. (4) 3. (3) 4. (3) 5. (2)
6. (3) 7. (1) 8. (3) 9. (3) 10. (3)
11. (1) 12. (3) 13. (2) 14. (3) 15. (2)
16. (2) 17. (2) 18. (3) 19. (3) 20. (1)
21. (3) 22. (4) 23. (3) 24. (4) 25. (1)
26. (2) 27. (2) 28. (3) 29. (2) 30. (2)
PART - II
1. (A) 2. (A) 3. (A) 4. (D) 5. (D)
6. (C) 7. (D) 8. (D) 9. (D) 10. (C)
11. (D) 12. (B) 13. (C) 14. (B) 15. (C)
16. (B) 17. (A)
PART - III
1. (C) 2. (B) 3. (D) 4. (C) 5. (C)
6. (D) 7. (C) 8. (C) 9. (A,C) 10. (A,B)
11. (A,B,C) 12. (A,B,C) 13. (A,B,D) 14. (B,C,D) 15. 4
16. 2 17. 6 18. 5 19. 31 20. 7
21. (D) 22. (D) 23. (B)
PART - IV
1.1
1.2 P4 (s) + 3NaOH + 3H2O  PH3(g) + 3H2PO2– Na+
1.3 (a) or or
(b) hypophosphite-reducing agent

phosphate - reducing agent
(c) They are reducing agents due to presence of P–H bond and lower oxidation state of P.
1.4 Ca5(PO4)3F + 5H2SO4  3H3PO4 + 5CaSO4 + HF
ADV PNO - 94
1.5 or
1.6 PCl3 + O2  2Cl3PO

POCl3 + 3EtOH  O=P(OEt)3 + 3HCl
1.7
1.8
PART - V
M2 S2 O 3 b f g
1.1 M2 S2 O 7 c d h
M2 S2 O 8 a e i
1.2
ADV PNO - 95
1.3 d) 2 HSO4–  H2O + S2O72–
2 MHSO4  H2O + M2S2O7
e) 2 HSO4– 2e  2 H+ + S2O82–
2 MHSO4 – 2e  2 H+ + M2S2O8
f) SO32– + S  S2O32–
M2SO3 + S  M2S2O3
g) AgBr + 2 S2O32–  [Ag(S2O3)2]3– + Br –
AgBr + 2 M2S2O3  M3 [Ag(S2O3)2] + MBr
h) S2O72– + 2 OH–  2 SO42– + H2O
M2S2O7 + 2 MOH  2 M2SO4 + H2O
i) 2 Mn2+ + 5 S2O82– + 8 H2O  2 MnO–4 + 10 SO42– + 16 H+
2 MnSO4 + 5 M2S2O8 + 8 H2O  2 MMnO4 + 4 M2SO4 + 8 H2SO4
2. (C) Nitrogen is collected by downward displacement of air.
3.1 2 32P + 5 Cl2  2 32PCl5
3.2 PCl5 + 2 OH–  POCl3 + 2 Cl– + H2O

POCl3 + 6 OH–  PO43- + 3 Cl– + 3 H2O
PCl5 + 8 OH–  PO43- + 5 Cl– + 4 H2O
Cl3PNPOCl2 + 11 OH–  2 PO43- + NH3 + 5 Cl– + 4 H2O
4. NH3: –III (–3) NO2– : III (3) NO3– : V (5)
5. [N2F  ] [AsF6 ] + HN3 

–78 C
inHF(l)
 [N5 ][AsF6– ] + HF
PART - I
1. Poor shielding by f-and d- electrons enhences the effective nuclear charge in Bi. This causes contraction in
size.
4. (1) (NH4)NO3 gives N2O, (2) chlorine (excess) with liquor NH3 forms NCl3 and (4) Pb(NO3)2 gives NO2 not N2 on
heating.
(3) 5Cu (red hot) + 2HNO3  5CuO + N2  + H2O
5. PH3 is less basic than NH3 due to lesser availability of lone pair of electrons. The lone pair of electron is
present in spherical s-orbital as compared to directional sp3 hybrid orbital in NH3.

6. 2Ca3(PO4)2 (from bone-ash) + 10C + 6SiO2  6CaSiO3 + 10CO + P4(s) white phosphorus
8. 3O2 2O3
9. Both rhombic & monoclinic sulphur has crown shape.
10. Tailing of mercury.
11. The order of boiling point of hydride of oxygen family is H2O > H2Te > H2Se > H2S.
12. The oxidation state of copper changes from +2 to 0 i.e. it gets reduced. So, NH3 works as a reducing agent.

13. P4 + 3NaOH + 3H2O  PH3 + 3NaH2PO2
ADV PNO - 96
2000 º C
14. CaO + 2C + N2   CaCN2 + CO; CaCN2 + 3H2O  CaCO3 + 2NH3
(calcium cynamide)

15. NH4NO3  N2O + 2H2O
16. Fe2+ + NO + 5H2O  [Fe(H 2O)5NO]2+ (brown complex).
17. CHCl3 (chloroform) react with conc. HNO3 on heating to form chloropicrin (CCl3NO2)
CHCl3 + HONO2  CCl3. NO2 + H2O
Chloropicrin
Chloropicrin is used as an insecticide and also war gas. It is also known as nitrochloroform or tear gas.
P
O O
O
18. O P P O
O
O O
P
O
19. 2H2SO4 + P2O5 (dehydrating agent)  2SO3 + 2HPO3 + H2O
20. SO2 + 2H2O  H2SO4 + 2H
coloured matter colourless matter..
220 º C 320 º C
21. H3PO4   H4P2O7   (HPO3)n.
22.
H3PO2 = monobasic ; H3PO3 = dibasic ; H3PO4 = tribasic.

one ionisable H+ two ionisable H+ three ionisable H+
23. (3) Reducing agents can reduce Cr2O72– to Cr3+ (green solution).
24. (1) Ba(NO3)2 + H2SO4  2HNO2 + BaSO4

(2) It is an unstable, weak acid which is known only in aqueous solution.
(3) 2HNO2  N2O3 + H2O
25. PCl5 remains covalent in gas as well as in liquid phase but in solid exists as [PCl4]+ and [PCl6]–.
very slowly
27. H2O + OF2    2HF + O2 (OF2 is neutral towards litmus)
29. 3S + 6NaOH  3H2O + 2Na2S + Na2SO3
Boiling
30. Na2SO3 + S   
–
 Na2S2O3
OH
ADV PNO - 97
PART - III
450 C
2. 2HgO    2Hg + O2
  
3. (A) NH4NO2  N2 + 2H2O, (B) NH4NO3  N2O + 2H2O, (C) 2NaN3  3N2 + 2Na.
4. The reaction of NaNO3 and HCl do not give NO.

NaNO3 + HCl  NaCl + HNO3 ; 4HNO3  H2O + NO2 + O2
5. N2O3 + H2O  HNO 2 ; 2KMnO4 + 5 KNO2 + 6HCl  2MnCl2 + 5KNO3 + 3H2O + 2KCl
2KI + 2HNO2 + 2HCl  2H 2O + 2NO + 3KCl + I 2
6. (A), (B) and (C) are reducing agents while (D) is not.
8. 2PCl5 + H2SO4  SO2Cl2 + 2POCl3 + 2HCl
10. (A) PH3 is a lewis base but is neutral towards red litmus.
(B) It does not react with HCl(aq) or HI(aq). This is because water decomposes PH 4X formed to give back
PH3.
(C) It reacts only with anhydrous HI or HBr.
(D) 2Na3P + 3H2SO4  3Na2SO4 + 2PH3  ; Ca3P2 + 6HCl  3CaCl2 + 2PH3
11. Nitrogen can not form p-d bond because nitrogen has no d-orbitals.
12. P2O5 reacts with H2SO4, HNO3, HClO4.
13. At 415 K ; 3H3PO2  2H3PO3 + PH3 
14. 4AgNO3 + 2H2O + H3PO2  4Ag + 4HNO3 (X) + H3PO4 (Y)
15. NO is evolved with Pb, Sb, Ag, P4.
NH4NO3 is formed and no gas is evolved with Mg, Fe, Mn, Sn.
No reaction with Au.
 
16. NH4NO3  N2O + 2H2O ; Pb(NO3)2  PbO + NO2 + O2
17. CaCl2 + NaPO3  Forms chelate complex with Ca2+, [Ca(P3O9)2]4–, used in softening of hard water..
MgSO4 + NaPO3  Forms chelate complex with Mg2+, [Mg(P3O9)2]4–, used in softening of hard water..
CaO + NaPO3  NaCaPO4
Na2CO3 + NaPO3  Na3PO4 + CO2
dry HCl + NaPO3  No reaction
Ca(HCO3)2 + NaPO3  Forms chelate complex with Ca2+, [Ca(P3O9)2]4– used in softening of hard water..
Na3PO4 + NaPO3  Na4P2O7
18. PCl3 + 3H2O  H



PO 3 + 3HCl
3
  Total 5 moles of NaOH required.
( dibasic )
19. Na2S2O3.5H2O + CuCl2  Na4[Cu6(S2O3)5]

soluable complex
Number of atom in Co-ordination sphere = 6 + 2 × 5 + 3 × 5 = 6 + 10 + 15 = 6 + 25 = 31 Ans.
20. (i) PCl3 + O2  POCl3 (ii) PCl5 + CO2  No reaction.
(iii) PCl5 + CH3COOH  CH3COCl + POCl3 + HCl (iv) PCl5 + H3BO3  POCl3 + B2O3
(v) PCl3 + SO2Cl2  PCl5 + SO2 (vi) P4O10 + NaCl  POCl3 + NaPO3
(vii) PCl5 + H2O  POCl3 + 2HCl (viii) PCl5 + SO2  SOCl2 + POCl3
(ix) PCl3 + SO3  POCl3 + SO2
ADV PNO - 98
21. A = (NH4)2 Cr2O7 , all electrons are paired. So diamagnetic (3d0 4s0)
Cr2O72– acts as strong oxidising agent in acidic medium.
22. (E) = NH3

(A) Cu2+ + 4NH3  [Cu(NH3)4]2+ (deep blue colouration).
(D) HgCl2 + NH3 + H2O  HgO.Hg(NH2)Cl  (white)
23. (1) Cool

2NO2   N2O4 colourless solid / liquid, acidic, mixed anhydride of HNO2 and HNO3

H
(2) 2ClO2 + 2O3 
 Cl2O6 (yellow solid) + 2O2 ; acidic, mixed anhydride of HClO3 and HClO4.

(3) K4 [Fe(CN)6] + 6H2O + 6H2SO4  2K2SO4 + FeSO4 + 3(NH4)2SO4 + 6CO
(4) 2KOH + 5O3  2KO3 (orange solid) + 5O2 + H2O
ADV PNO - 99
p-Block Elements (Halogen & Noble Gases)
ADV PHN - 100


Section (A) : Elements: Occurance & Isolation
A-1. Name the compound which is used to obtain fluorine gas on electrolysis. At which electrode does F2 appears?
A-2._ Name the valuable halogen impurities present in chile salt petre (NaNO 3).
A-3._ What idea lead to the discovery of Xenon fluorides?
Section (B) : Based on Periodic Trends

B-1. Considering the parameters such as bond dissociation enthalpy, electron gain enthalpy and hydration enthalpy,
compare the oxidizing power of F2 and Cl2.
B-2._ Write all the common oxidation states of halogens.
B-3. Write and explain the order of X–X bond energy for halogen down the group.

C-1._ Draw the Lewis dot structures of the following compounds :
HClO3, XeOF4, XeO2F2, ICl2–, ICl4–.
C-2._ Draw the Lewis dot structures of the following multicentred compounds:
I2O5, Cl2O7.
C-3. Give the formula and describe the structure of a noble gas species which is isostructural with:
(i) Cl4– (ii) Br2– (iii) BrO3–
C-4._ Arrange the XeF2, XeF4 in decreasing order of Xe–F bond length, give reason also.

D-1. Answer the following with relevant reason.
(i) The boiling points of noble gases increase with increase in atomic number.
(ii) Why helium and neon do not form clathrate compounds with quinol ?
D-2. Why are halogens coloured ?
D-3. Write the reactions of F2 and Cl2 with water.
D-4._ State what happens when halogens react with a cold dilute solution of NaOH ?
D-5._ State what happens when halogens (X = Cl / Br / I) react with hot and conc. solution of NaOH ?
D-6._ Which halogen is oxidised by conc. HNO3? Give reaction.
D-7. Explain the following with proper reason :

(i) Fluorine cannot be prepared from fluorides by chemical oxidation.
(ii) Fluorine does not form F3– (polyhalide) ion.
Section (E) : Oxides, Hydroxides & Oxyacids

E-1._ Write chemical reactions involved in preparation of HClO3 & HClO4 by displacement from their salts.
E-2. When a blue litmus is dipped into a solution of hypochlorous acid, it turns red and then gets decolourised.
Explain.
E-3. Explain why fluorine forms only one oxyacid, HOF.
ADV PHN - 101

E-4. Predict the products when the following reactions are carried out :
(i) In acidic medium when SO2 is passed through NaClO3.
(ii) HCl + KIO3 + KI 
E-5._ What happen when ClO2 dissolves in NaOH?
Section (F) : Hydracids

F-1._ Arrange the following in the order of : (i) Acidic strength (ii) Reducing behaviour (HI, HBr, HCl & HF)
F-2. How can you prepare Cl2 from HCl and HCl from Cl2? Write reactions only.
F-3. HI can not be prepared by heating NaI with concentrated H2SO4. Give the method which is preferred for the
preparation of HI.
F-4._ What is aqua regia? Write its reaction product with gold and platinum.
F-5. Explain the following with proper reason :

(i) Anhydrous HCl is a bad conductor of electricity while aqueous HCl is a good conductor.
(ii) HF is not stored in glass bottles but kept in wax lined bottles.
(iii) HF has a greater electronegativity difference and more ionic character than HCl, HBr and HI but it is the
weakest acid.
F-6. Fill in the blanks :

(i) Among halogen acids (hydrogen halides) .............. is the strongest reducing agent.
(ii) H2SO4 + H  ________ + ___________ + ________
F-7. Predict the products when the following reactions are carried out :
(i) Red lead is boiled with concentrated HCl.
(ii) SiO2 + HF 
Section (G) : Halides & Oxyhalides :

G-1._ Write the method of preparation of XeF2, XeF4 & XeF6.
G-2._ How is XeOF4 prepared ?
G-3._ Does the hydrolysis of XeF4 lead to a redox reaction ?
G-4._ Write the complete and the partial hydrolysis product of XeF6.
G-5. Complete the following reactions :

(i) XeF2 + H2 
(ii) XeF6 + SiO2 
(iii) XeF6 + SbF5 
Section (H) : Other compounds (Inter halogens, Bleaching powder, Pseudo halides &
Poly halides) :
H-1. Complete the following reactions :
(a) Cl2  F2 473 K


 (b) I2 + 3Cl 2 
(Equal volume ) (Excess )
(c) Br2 + 3F2  (d) Br2 + 5F2 

(Excess )
H-2. Why ICl is more reactive than I2.
H-3._ (a) Name two interhalogens of AB3 type.

(b) Write the hydrolysis product of ICl ?
H-4. Explain the following with proper reason :

(i) Bleaching of flowers by chlorine is permanent while after bleaching with SO 2, the colour returns.
(ii) Iodine dissolves more in K solution than in water.
ADV PHN - 102

H-5. What happens when ? (Give balanced equations)
(i) Sodium iodate is treated with sodium bisulphite solution.
(ii) Chlorine is passed over slaked lime.

Section (A) : Elements : Occurance and Isolation
A-1. Which of the following gaseous molecules is monoatomic ?
(A) chlorine (B) helium (C) oxygen (D) nitrogen
A-2. Which one of the following noble gases is not found in atmosphere ?
(A) Rn (B) Kr (C) Ne (D) Ar
A-3. The inert gas abundantly found in atmosphere is :

(A) Ar (B) Kr (C) He (D) Xe
A-4. Electrolysis of aqueous solution of Brine (NaCl) will give:

(A) Cl2 (B) H2 (C) NaOH (D) all of these
A-5. The catalyst used in the Deacon’s process for the manufacture of chlorine is :
(A) Cu (B) An alloy of copper (C) CuCl2 (D) CuS
Section (B) : Based on Periodic Trends

B-1. Which one of the following configuration represents a noble gas ?
(A) 1s2 2s2 p6, 3s2 (B) 1s2 2s2 p6, 3s1 (C) 1s2 2s2 p6 (D) 1s2 2s2 p6, 3s2 p6 , 4s2
B-2. Astatine is the element below iodine in the group VIIA of the periodic table. Which of the following statements
is not true for astatine ?
(A) It is less electronegative than iodine.
(B) It will exhibit only –1 oxidation state.
(C) Intermolecular forces between the astatine molecules will be larger than that between iodine molecules.
(D) None of these.
B-3._ Which is wrong statement ?

(A) Basic nature of X– is in order F– > Cl– > Br– > I–
(B) Electron gain enthalpy in order F > Cl > Br > I.
(C) The ionic character of M—X bond decreases in the order M—F > M—Cl > M—Br > M—I
(D) Among F–, Cl–, Br– and I–, F– has the highest enthalpy of hydration.

C-1._ Which of the following structure is correct for BrF3 ?
(A) (B) (C) (D) none of these
C-2. Among the following molecules, (i) XeO3 (ii) XeOF4 (iii) XeF6
those having same number of lone pairs on Xe are :
(A) (i) and (ii) only (B) (i) and (iii) only (C) (ii) and (iii) only (D) (i) , (ii) and (iii)
C-3. Select the incorrect match.

(A) XeF2 : Linear (B) XeF4 : square planar
(C) XeF6 : distorted octahedral (D) XeO3 : Trigonal planar
C-4. Which of the following hydrogen halide is most volatile.

(A) HCl (B) HF (C) HI (D) HBr
ADV PHN - 103

C-5. Which of the following has maximum bond strength :
(A) HI (B) HCl (C) HF (D) HBr
C-6. Which of the following is the strongest acid ?

(A) HBr (B) HF (C) H2S (D) PH3
C-7. The strongest acid amongst the following is :

(A) HClO4 (B) HClO3 (C) HClO2 (D) HClO
Section (D) : Properties of elements :

D-1._ Correct order of boiling point of halogens is
(A) F2 < Cl2 < Br2 < I2 (B) Cl2 > F2 > Br2 > I2 (C) F2 > Cl2 > Br2 > I2 (D) Cl2 < F2 < Br2 < I2
D-2. Which of the following statement is correct ?

(A) Helium has abnormal behaviour on liquefication
(B) Iodine is readily soluble in CS2 and the solution is purple in colour
(C) Helium do not form any clathrate
(D) All of these
D-3. Chlorine gas is dried over :

(A) CaO (B) NaOH (C) conc. H2SO4 (D) dil. H2SO4
D-4._ F2 reacts with H2O as follows :

F2 + H2O  H+ + F– + O2
Which of the following halogens shows same reaction but in opposite direction ?
(A) Br2 (B) Cl2 (C) I2 (D) All
D-5. Chlorine acts as a bleaching agent only in presence of :

(A) dry air (B) moisture (C) sunlight (D) pure oxygen
Section (E) : Oxides, Hydroxides & Oxyacids :

E-1. Select the incorrect statement :
(A) Perchloric acid is a stronger acid than sulphuric acid
(B) Only one oxyacid [HOF] is formed by fluorine
(C) The most stable oxy-acid of chlorine is perchloric acid
(D) None of these
E-2. Cl2O6 reacts with water and alkali to give :

(A) Only sodium chlorate (B) Only sodium perchlorate
(C) Both sodium chlorate and sodium perchlorate (D) None of these
E-3. On heating KClO3 we get :

(A) KClO2 + O2 (B) KCl + O2 (C) KCl + O3 (D) KCl + O2 + O3
E-4. The following acids have been arranged in order of decreasing acid strength. Identify the correct order.
ClOH (), BrOH (), IOH () [JEE 1996, 1]
(A) > >  (B) > >  (C) > >  (D) > > 
E-5. ClO3– ion leads with I2 to form :

(A) ClO4– (B) IO3– and Cl2 (C) lCl and O2 (D) ICl and O3
Section (F) : Hydracids :

F-1. Which of the following halogen hydrides will have the weakest conjugate base ?
(A) HF (B) HCl (C) HBr (D) HI
F-2. Concentrated H2SO4 cannot be used to prepare HBr from NaBr, because it ; [JEE 1995, 1]
(A) reduces HBr (B) oxidises HBr
(C) disproportionates HBr (D) reacts slowly with NaBr
ADV PHN - 104

F-3. Hydrogen bromide is dried by passing the gas through :
(A) quick line (B) anhydrous calcium chloride
(C) potassium hydroxide pellet (D) con. H2SO4
F-4. Which one of the hydracid does not form any precipitate with AgNO 3 ?
(A) HF (B) HCl (C) HBr (D) HI
F-5 Which can do glass etching ?

(A) HIO4 (B) HF (C) HNO3 (D) SiF4
F-6. Identify A and B in following reaction,

H2SO4 + HBr  A + B + H2O
(A) Br2 , SO3 (B) Br2 , S (C) BrO3– , SO3 (D) Br2 , SO2
F-7._ Which of the following is obtained when gold is treated with aquaregia.
(A) AuCl4 (B) AuCl3 (C) [AuCl4]– (D) [AuCl4]+
Section (G) : Halides and oxyhalides :

G-1._ The number of lone pairs on central atom in XeF2 , XeF4 and XeF6 are :
(A) 1,2,3 (B) 3,2,1 (C) 2,2,1 (D) 1,3,2
G-2. Of the following species, one which is non-existent :

(A) XeF6 (B) XeF5 (C) XeF4 (D) XeF2
G-3._ XeF2 on complete hydrolysis gives :

(A) Xe (B) XeO2 (C) XeO2F2 (D) XeO4
G-4. Hydrolysis of XeF4 and CaCN2 gives respectively :

(A) XeO3 and CaCO3 (B) XeO2 and Ca(OH)2
(C) XeOF3 and Ca(OH)2 (D) XeOF2 and CaCO3
G-5._ Xenon hexafluoride undergoes hydrolysis in strong alkaline medium:

2 XeF6 + 16 OH–  8H2O + 12F– + A + B + C
then reaction product may be:
(A) perxenate ion (B) O2 (C) Xenon (D) All of the above
Section (H) : Other compounds (Inter halogens, Bleaching powder, Pseudo halides &
Poly halides) :
H-1._ In the inter halogen compounds of AB3/AB5 form which is correct :
(A) A is large size halogen (B) B is large size halogen
(C) B is small size halogen (D) Both (A) & (C)
H-2. Which one of the following is not a pseudohalide ? [JEE 1997, 1]

(A) CNO– (B) RCOO– (C) OCN– (D) NNN–
H-3._ Which of the following behaves like pseudohalogen compound:

(A) NCCN (B) CN– (C) N3– (D) I3–
H-4. Which of the following statement is correct.

(A) All interhalogen compounds are gas at room temperature.
(B) Interhalogen are either gas or liquid at room temperature.
(C) Interhalogens can be solid or liquid or gas at room temperature.
(D) All interhalogen compounds are liquid at room temperature.
ADV PHN - 105


1. Match the reactions listed in column-I with the product(s) listed in column-II.
Column - I Column - II (X = Halogen)
(A) NH3 + F2  (p) N2
(B) NH3 (excess.) + Cl2  (q) HX
(C) NH3 + Br2 (excess.)  (r) NH4X
(D) NH3 (aq.) + I2  (s) Explosive
2. Match the reactions listed in column-I with the product(s) listed in column-II.
Column - I Column - II
(A) Cl2O6 + H2O  (p) ClO2
(B) NaClO4(s) + HCl(conc.)  (q) HClO3
(C) KClO3 + (COOH)2  (r) Cl2O
(D) HgO + Cl2 
573K
 (s) HClO4
3. Match the compounds listed in column-I with characteristic(s) / type of reaction(s) listed in column-II.
Column –I Column –II
(A) XeF2 (p) Undergoes hydrolysis with water.
(B) XeF4 (q) Acts as oxidising agent.
(C) XeF6 (r) Undergoes addition reaction.
(D) XeO3 (s) Has lone pair(s) of electrons.
(t) Gives disproportionation reaction with H2O or OH– .

1. The X – X bond dissociation energy is minimum in :
(A) F2 (B) Cl2 (C) Br2 (D) I2
2. Iodine is liberated from KI solution when treated with :

(A) ZnSO4 (B) CuSO4 (C) NiSO4 (D) FeSO4
3. Which of the following is not oxidised by MnO2 ?

(A) F– (B) Cl– (C) Br– (D) I–
4. F2 + dil NaOH  A + NaF + H2O

F2 + conc. NaOH  B + NaF + H2O
A and B respectively are :
(A) OF2 and O2 (B) O2 and OF2 (C) Both O2 (D) Both OF2
5. When thiosulphate ion is oxidised by iodine, the new product formed is :

(A) SO32– (B) SO42– (C) S4O62– (D) S2O62–
6. NH3(excess) + Cl2  NH4Cl + A(gas)

NH3 + Cl2(excess)  B + HCl
Incorrect statement regarding A and B.
(A) A is highly reactive gas at room temperature.
(B) Bond order of gas ‘A’ is same as C22–.
(C) Compound ‘B’ is explosive.
(D) Bond angle of compound B is greater than bond angle of NF 3.
ADV PHN - 106

7. Which amongst the following reactions cannot be used for the respective preparation ?
(A) 2KBr + H2SO4 (conc.)  K2SO4 + 2HBr (B) NaCl + H2SO4 (conc.)  NaHSO4 + HCl
(C) NaHSO4 + NaCl  Na2SO4 + HCl (D) CaF2 + H2SO4(conc.)  CaSO4 + 2HF
8. Hvaporisation (KJ/mol) are given for the hydrides of halogens in the following graph.
The hydride HF will correspond to

(A) P (B) Q (C) R (D) S
9. Alkali metal hydrogen fluorides have a formula M[HF2]. They are found to contain a linear symmetrical anion
having an overall F–H–F distance of 2.26 Å which may be compared with the H–F bond length of 0.92 Å in
the moment. Which of the following is false for the anion ?
(A) Hydrogen bonding plays a significant role in the existence of the anion
(B) Average bond length (H–F) is 1.13 Å in the anion HF2–
(C) The stretching of the H–F bond in the anion is 0.21 Å
(D) H-atom is bonded to two F-atoms through two T bonds in the anion.
10. A certain hypohalite on treating with hot and conc. NaOH forms anions P and Q. More stable anion among
P and Q can be obtained by neutralizing its conjugate acid X.
Upon heating X to very high temperature, a compound Y is formed, which is used in estimation of a toxic gas
which have 300 times stronger affinity for haemoglobin than dioxygen. Then which of the following statements
are true.
(A) X is HI.
(B) Y is Cl2O5
(C) Final product Y, has total no. of bonds 5.
(D) Y on reacting with toxic gas produces a gas which is used in fire extinguisher.
11. _ When F2 is passed into a solution of mineral acid X, a greenish yellow gas Y is formed. Which on treating
with slaked lime forms “Z”. When Red litmus is kept in contact with Z, it changes into :
(A) Blue colour (B) No change in colour
(C) White in colour (D) None of these
12. Which statement regarding iodine trichloride is incorrect.

(A) It forms dimer in gaseous state.
(B) In dimer I2Cl6, the bridge bonds are longer than the terminal bonds.
(C) In solid state, it exist as planar molecule.
(D) On hydrolysis, it gives a mixture of iodous acid and hydrochloric acid.
13. The order of solubility of noble gases in water is :

(A) He > Ar > Kr > Ne > Xe (B) He > Ne > Ar > Kr > Xe
(C) Xe > Ar > Kr > He > Ne (D) Xe > Kr > Ar > Ne > He
14. Consider following properties of the noble gases.

I : They readily form compounds which are colourless.
II : They generally do not form ionic compounds.
III : Xenon has variable oxidation states in its compounds.
IV : the smaller He and Ne do not form clathrate compounds.
Select correct properties.
(A) I, II , III (B) II , III, IV (C) I, III, IV (D) All
ADV PHN - 107

15. The formation of O2+ [PtF6]– is the basis for the formation of xenon fluorides. This is because :
(A) O2 and Xe have comparable sizes.
(B) both O2 and Xe are gases.
(C) O2 and Xe have comparable ionisation energies.
(D) O2 and Xe have comparable electronegativities.
16. [HXeO4]– + OH–  [X] + [Y] + O2 + H2O

The products [X] and [Y] in unbalanced reaction are :
(A) [XeO6]4– & Xe (B) [XeO6]4– & XeO3 (C) XeO3 & Xe (D) H2XeO4 & Xe

1. The total number of electrons present in 4th shell of Astatatine (85At) are :
2. How many of the following properties of halogen increases with increase in atomic number.
(a) Number of valence electron (b) Metallic nature (c) Boiling points
(d) Atomic radii (e) Density (f) Inoisation enthalpies
(g) Electronegativities (h) Reactivity
(i) Oxidising nature. (j) egH (magnitude wise)
3. A gas P is obtained at anode during the electrolysis of brine. The gas P when treated with excess of NH 3
released a diatomic gas Q. Find the value of (x – y) where x & y are the molar mass of P and Q.
4. How many orders are correct :

(a) H–F < H–Cl < H–Br < H–I (Bond length)
(b) H–F < H–I < H–Br < H–I (Acidic strength)
(c) H–I < H–Br < H–Cl < H–F (Bond strength)
(d) H–F > H–Cl > H–Br > H–I (Thermodynamic stability)
(e) H–F < H–Cl < H–Br < H–I (Reducing power)
(f) H–F > H–I > H–Br > H–Cl (Boiling point)
5. HCl  HNO3 

( Conc.) ( Conc.)
In this reaction change in oxidation number of N is ______
6. How many of the following reactions would have HCl as one of the products ?
(a) CH4 + Cl2 
(b) FeSO4 + H2SO4 + Cl2 
(c) I2 + Cl2 + H2O 
(d) Cl2 + H2O 
(e) H2O + SO2 + Cl2 
(f) SO3 + Cl2 
Electrolysis
(g) NaCl(aq) 

(h) Cl2O7 + H2O 
(i) Cl2 + NaOH(conc.) 
7. The number of mixed anhydride among the following are

Cl2O ; ClO2 ; Cl2O6 ; Cl2O7 ; N2O5 ; NO2 ; N2O
Hydrolysis
8. Br2 + F2 (excess)  A     B + C
The summation of atomicities of compound A, B and C is :
9. The number of lone pairs of electrons present in central atom of ClF3 is :
10. Which of the following interhalogens exist at room temperature and have central atom hybridization sp 3d2
(a) ClF3 (b) ClF5 (c) BrCl3 (d) IF3
(e) IF5 (f) BrF5 (g) IF7 (h) ICl5
(i) IBr5 (j) BrF3 (k) ClBr5
ADV PHN - 108

11. How many of the following properties of noble gases would increase from Helium to Radon ?
Boiling point, First Ionisation enthalpy, Atomic volume, Abundance in atmosphere, Density at STP, Valence
electrons, Critical temperature.
12. The number of compounds/elements oxidised by XeF2 among following is:

HF, HBr, HCl, HI, NH3, CrF2, Pt, S8
13. The oxidation state of xenon in perxenate ion is +n. Give the value of ‘n’.
14._
The summation of total no. of lone pairs and  bonds in in species (A, B and C) is.
15. How many of the given compounds can produce XeO3.

XeF6, XeF4, XeO2F2, XeOF4

1. Which of the following salts will evolve halogen on treatment with conc. H2SO4 ?
(A) NaCl (B) KI (C) NaBr (D) none of these
2. Which of the following reactions are correct ?

(A) NaIO3 + 5NaI + 6H2SO4  6NaHSO4 3H2O + I2
(B) 2KBr + MnO2 + 3H2SO4  2KHSO4 + MnSO4 + 2H2O + Br2 
(C) K2Cr2O7 + 14HCl  2 KCl + 2CrCl3 + 7H2O + 3Cl2
(D) 2K2MnF6 + 4SbF5  4KSbF6 + MnF3 + F2
3. Which of the following will not displace the halogen from the solution of the halide ?
(A) Br2 added to NaI (B) Br2 added to NaCl (C) F2 added to KCl (D) Cl2 added to NaF
4. Iodine reacts with hypo to give :

(A) NaI (B) Na2SO3 (C) Na2S4O6 (D) Na2SO4
5. Cl2 + NH3(excess)  A + B

(A) One of the product is also obtained by decomposition of (NH4)2Cr2O7.
(B) Bond order in one of the product is 3
(C) Both products contain chlorine.
(D) If Br2 is used instead of Cl2, one of product remain same
6. In which of the following case disproportionation reaction take place.

(A) F2 + Hot water  products (B) Cl2 + Cold and dilute NaOH  products
(C) Cl2 + Hot and conc. NaOH  products (D) Cl2 + NH3(excess)  products
7. In which following statement are correct.

(a) Anhydrous hydrogen fluroide is a liquid at ordianry temperature while other halogen acid are gases.
(b) Lead acetate does not form any precipitate with HF acid but other halogen acid from precipitates.
(c) HF is heated with a mixture of MnO2 and H2SO4 , no gas is evloved but in case of HCl, HBr and HI acids
evolved gases.
(d) HF is not oxidised by strong oxidising agent but other halogen acid are oxidised.
(A) a (B) b (C) c (D) d
ADV PHN - 109

8. A pungent smelling gas X after being dried by concentrated H2SO4 was dissolved in water to give strongly
acidic solution. The gas also gives dense white fumes with NH3. X is also a constituent of aqua-regia. Which
of the following is/are true for X ?
(A) X is HCl
(B) X is Cl2
(C) X is the most volatile among the hydrides of halogens
(D) Solution of X in water can liberate CO2 from the solution of sodium hydrogencarbonates.
9. Among the following which reactions are possible

(A) F2 + H2O  HF + O2 (B) Cl2 + H2O  HCl + HClO
(C) Br2 + H2O  HBr + HBrO (D) I2 + H2O  HI + HIO
10. Which of the following statements are true :

(A) Strength of oxyacids : HClO4 > HClO3 > HClO2 > HClO
(B) Strength of oxyacids : HClO4 > HBrO4 > HIO4
(C) Number of p-p bonds : HClO4 > HClO3 > HClO2 > HClO
(D) Percentage s-character of central atom : HClO4 > HClO3 > HClO2 > HClO.
11. Which of the following interhalogen compounds is/are possible :

(A) ClF3 (B) IF5 (C) FCl3 (D) BrF5
12. Which of the following statement are true regareding interhalogens :

(A) Thermal stability order IF > BrF > ClF
(B) Hydrolysis of IF7 produces H5IO6 and HF as products.
(C) Interhalogen compounds are diamagnetic in nature.
(D) IF7 have pentagonal bipyramidal structure.
13. Which of the following inert gas(es) form(s) clathrate compoud(s) with quinol ?
(A) Helium (B) Xenon (C) Krypton (D) Neon
14. Consider the following reactions :
Xe + F2 Ni A
2 : 1
Xe + F2  B
1 : 20
Xe + F2  C
1 : 5
Select incorrect statements :
(A) A, B and C all are non-polar and planner molecule (B) B has no lone pair of electrons
(C) The order of Xe-F bond length is A > C > B (D) A, B and C are act as lewis base.
15. Which of the following statements(s) is /are true for XeF6 ?
(A) Its partial hydrolysis gives XeOF4. (B) Its reaction with silica gives XeOF4
(C) It is prepared by the reaction of XeF4 and O2F2 (D) Its reaction with XeO3 gives XeOF4.
Comprehension # 1
A red liquid (A) when treated with sodium carbonate gives a mixture of two salts (B) and (C) in the solution in
which (C) contains oxygen. The mixture then on acidification with sulphuric acid and distillation produces the
red liquid (A) again.
1. Select the correct statement for the liquid (A).

(A) It acts as an oxidising agent,
(B) It is sparingly soluble in water
(C) It converts the yellow-dye stuff fluorescein (I) into red colour compound
(D) All of these
ADV PHN - 110

2. Which of the following statement is false for salt (B) ?
(A) Its solution in water gives pale yellow precipitate with silver nitrate solution
(B) Its solution in water gives white precipitate with lead nitrate solution
(C) Its acidified solution (with conc. H2SO4) liberates a coloured gas which produces orange red spots on
starch paper
(D) None

(A) Liquid (A) undergoes disproportionation reaction in aqueous solution of sodium carbonate
(B) The anion of compound (C) has sp3 hybridisation and is trigonal pyramidal in shape
(C) (A) and (B) both
(D) None of these
Comprehension # 2
Pseudo halides are anions having resemblance with halide ions. Group I metals can form salts with pseudo
halides. Pseudo halogens can acts as ligands and form coordinate complexes. Their hydrides are weakly
acidic and can be prepared in analogous way as halogen hydrides are prepared. Azides, cyanides,
selonocyanides are example of pseudo halides.
4. Cyanide, CN– is a pseudo halide. When cyanogen is heated with alkali solution, the products are :
(A) HCN, H2O (B) NH3, (NH4)2CO3 (C) NaCN, NaOCN (D) HCOONa, NH3
5. When NaCN reacts with H2SO4, the products are :

(A) HCN and Na2SO4 (B) HCN and NaHSO4
(C) (CN)2 and Na2SO4.H2O (D) None of these
6. When sodium pseudo halides are dissolved in water, it resembles with :

(A) NaCl (B) NaBr (C) NaF (D) NaI
7. (CN)2 when react with Na metal, the product is :

(A) NaCN (B) Na2C2 and N2 (C) NaN3 and C black (D) Na(CN)2–
Comprehension # 3
The ionisation energy of dioxygen (O2) is very close to that of Xenon. Also F and O have the highest
electronegativity and consequently can oxidise Xe among rare gases. So Xe forms a large number of
compounds with F and O. Xe and F2 are mixed and reacted at different temperatures to give XeF2, XeF4 and
XeF6. Xe also forms an unstable gaseous XeO4 and solid XeO3 which is a very powerful explosive at higher
temperatures. Some of the rare gases form clathrates or cage compounds by being entrapped in the cages
of cystals laiitice of water, phenol of quinols. helium can form intersitital compoudns with transition metals.
bigger members of rare gases do not form such compounds because of their large size.
8. Xenon forms the larges number of compounds only with oxygen and fluorine because :
(i) oxygen and fluorine have very high electronegativity.
(ii) ionisation energy of Xe is the largest among rare gases.
(iii) ionisation energy of Xe is low compared to those of other rare gases.
(iv) low dissociation energy of fluorine molecule compared to those of Cl2 and Br2
(A) (i), (ii), (iii) (B) (i), (iii), (iv) (C) (iii), (iv) (D) (i), (iv)
9. XeF6 cannot be prepared by the method :
475 532 K 500 K
(A) Xe + 3F2  XeF6 (B) XeF2 + 2F2   XeF6
50 atm
475 K
475 K
(C) XeF4 + F2   XeF6 (D) XeO3 + 6HF 
 XeF6 + 3H2O

10. He and Ne do not form any clathrates because :

(A) He and Ne are very large in size.
(B) being neutral they cannot form any polar bonds with the host molecules.
(C) being too small, they cannot be entrapped in the cages of water, phenol or quinol.
(D) clathrated with He and Ne are highly explosive.
ADV PHN - 111

EXERCISE - 1
PART - I
A-1._ A solution of potassium hydrogen fluoride (KHF2) in anhydrous HF.
electrolysis
KF + HF  K [HF2]  H2 + F2
On Electrolysis :
Anode : HF2–  F2  H  2e–
 – –
Cathode : 2HF + H  2e  H2 + HF2
Overall reaction: 2HF  H2 + F2
A-2._ It contains trace amounts of NaIO3 and NaIO4. An important property of chile salt petre is that it is soluble in
water while its impurities are not.
A-3._ Neil Bartlett obtained an orange yellow solid from the reaction of xenon with PtF 6to have Xe+[PtF6]–. He
noticed earlier that O2 with PtF6 reacts to give O2+[PtF6]– and since ionisation enthalpies of O2 and Xe were
close to each other (Xe = 1170, O2 = 1175 kJ mol–1), he could succeed to prepare Xe+[PtF6]– from Xe and PtF6.
B-1. The electrode potential of F2 (+2.87 V) is much higher than that of Cl2 (+1.36 V).
1 – H –
x2(g) + e (aq.) x (aq.)
2
1 1
Ex-x H°Hy H = E – |E.A| – |H°Hy|
2 2 x-x
E.A. –
(X(g) x (g)
F2 Cl2 Order
–1 158.8 F2 < Cl2
Bond dissociation enthalpy/kJmol 242.6
Magnitude of E.A/kJmol–1 333 349 F2 < Cl2
Magnitude of H°Hyd./kJmol–1 515 381 F2 > Cl2
Oxidizing power F2 > Cl2

Therefore F2 is much stronger oxidising agent than Cl2.
B-2._ F : –1, 0
Cl : –1, 0, +3, +5, +7
Br : –1, 0, +3, +5, +7
I : –1, 0, +3, +5, +7
B-3._ Enthalpy of dissociation (x-x)/kJ mol–1
Cl – Cl > Br – Br > F – F > I – I, Smaller enthalpy of dissociation of F2 is due to relatively large electrons-
electrons repulsion among the lone pairs in F2 molecule.
C-1._ ; ; ; ;
ADV PHN - 112

C-2._ ; Cl Cl
C-3. (i) Structure of Cl4– –

Cl Cl
No. of electrons in the valence shell of the central I atom = 7.
No. of electrons provided by four Cl atoms = 4×1 = 4
I
Charge on the central atom = 1
 Total no. of electrons around the central atom
Cl Cl
= 7 + 4 + 1 = 12
Total no. of electron pairs around the central atom
Square planar
= 12 /2 = 6
But the no. of bond pairs = 4
( there are four I-Cl bonds)
 No. of lone pairs = 6 – 4 = 2
Thus, I in Cl4– has 4 bond pairs and 2 lone pairs. Therefore, according to VSEPR theory, it should be square
planar.
Now a noble gas compound having 12 electrons in the valence shell of the central atom is XeF 4 (8 + 1 × 4 =
12). Like Cl4– , it also has 4 bond pairs and 2 lone pairs. Therefore, like Cl4– , XeF4 is also square planar..
(ii) Structure of Br2– . Br
No. of electrons in the valence shell of the central I atom = 7 –
No. of electrons provided by two Br atoms = 2 × 1 = 2
Charge on the central I atom is = 1 I
 Total no. of electrons around the central I atom = 7 + 2 + 1 = 10
But the no. of bond pairs = 2 ( there are two I – Br bonds)
Br
 No. of lone pairs = 5 – 2 = 3 LINEAR
Thus, I in Br2– has two bond pairs and three lone pairs, Therefore, according to VSEPR theory, it should be
linear.
Now a noble gas compound having 10 electrons in the valence shell of the central atom is XeF 2 (8 + 1 × 2
=10). Like IBr–, it also has 2 bond pairs and 3 lone pairs.
(iii) Structure of BrO3– .
In BrO3– , since O is more electronegative than Br, therefore, –ve charge stays on the O atom.
Br
-
O O
O
PYRAMIDAL
Therefore, in BrO3– , there are two Br = O bonds and one bond Br – O– bond.
Now according to VSEPR theory, double bonds do not contribute any electron while single bonds contribute
one electron towards the total number of the central atom. However, both double and single bonds contribute
one bond pair. Thus, total number of electrons is the valence shell of the central Br atom = 7 + 2 × 0 + 1 × 1
=8
 No. of electron pairs around Br atom = 8/2 = 4
But total number of bond pairs = 2 × 1 (Br = 0) + 1 × 1 (Br – O –) = 3 and lone pairs = 4 – 3 = 1.
Thus, BrO3– has 3 bond pairs and one lone pair. Therefore, according to VSEPR theory, it should be pyramidal.
Now a noble gas compound having 8 electrons in the valence shell of the central atom is XeO 3 (8 × 1 + 3 ×
0 = 8). Like BrO3– , it also has 3 bond pairs and one lone pair. Therefore, like BrO3– , XeO3 is also pyramidal.
ADV PHN - 113

C-4._ XeF2 > XeF4
2.00 Å 1.94 Å (Order of Xe–F bond length)
XeF2 : SP3d, axial bonds are long & weak
XeF4 : sp3d2 square planar : all bonds identical.
D-1. (i) Van der Waal’s forces of attraction among molecules increase with the increase of atomic masses. Thus,
higher energy is required to separate these molecules as to get gaseous state. Hence, the boiling points
increase with increase of atomic masses.
(ii) The size of cavities formed during crystallisation of quinol is more than the size of helium and neon atoms.
D-2. All the halogens are coloured. The colour is due to the allowed   molecular orbital transitions. The
colour of halogen is actually the colour of transmitted light.
D-3. F2 being a strong oxidizing agent H2O to O2 or O3.

2F2 (g) + 2H2O(l)  4H+ (aq.) + 4F–(aq.) + O2(g)
3F2(g) + 3H2O(l)  6 H+(aq.) + 6F–(aq.) + O3(g)
Cl2, on the other hand, reacts with H2O to form hydrochloric acid and hypochlorous acid to a small extent.
Cl2(g) + H2O(l) HCl(aq.) + HOCl (aq.)
Hydrochloric Hydrochlorous
acid acid
D-4._ 2F2 + 2NaOH  OF2 + 2NaF + H2O

Other halogens (X = Cl / Br / I) disproportionate : X2 + 2NaOH 
Cold
 NaX + NaOX + H2O
D-5._ X2 + 2NaOH  
Hot
 NaX + NaXO3 + H2O
D-6._ I2
I2 + HNO3 (conc.)  HIO3 + NO2 + H2O
D-7. (i) The standard reduction potential of fluorine is maximum.
+ e– 
Thus, it cannot be oxidised by any other reagent. F– ion is very stable due to small size and high
electronegativity of fluorine atom.
(ii) F-does not have empty d-orbital liked other halogen. The formation of X3– ions involves sp3d-hybridizaion.
E-1._ Ba (ClO3)2 + H2SO4  BaSO4+ 2HClO3
KCIO4 + H2SO4  KHSO4 + HCIO4
E-2. HOCl acts as an acid, HOCl  H+ + OCl–, and thus turns blue litmus to red. It also work as bleaching
agent, HOCl  HCl + [O], and the red litmus is decolorized by nascent oxygen.
E-3. Chlorine, bromine and iodine form four series of oxyacids of the general formula HOX , HOXO, HOXO 2 and
HOXO3 in which the oxidation states of halogen (X = Cl, Br or I) is + 1, + 3 , and + 5 and + 7 respectively.
However, due to high electronegativity, small size and absence of d-orbitals, F cannot act as central atom in
higher oxacids such as HOFO. HOFO2 and HOFO3 In which the oxidation state of F would be + 3, + 5 and
+ 7. It just forms one oxoacid. i.e., HOF in which the oxidation state of F is –1 and oxygen is in +1.
E-4. (i) 2NaClO3 + SO2 + H2SO4  2NaHSO4 + 2ClO2
(ii) 5– + IO3– + 6H+  3I2 + 3 H2O
E-5._ ClO2(s) is a mixed anhydride of HClO2 and HClO3 because on dissolving in water it gives a mixture of these
two acids.
2ClO2 + 2NaOH  NaClO2 + NaClO3 + H2O
ADV PHN - 114

F-1._ (i) HI > HBr > HCl > HF
Due to decrease in bond energy
(ii) HI is the strongest reducing agent.
F-2. Conc. HCl can be oxidized to Cl2 by heating with a number of oxidizing agents such as MnO2, KMnO4,
K2Cr2O7, etc.
MnO2 + 4 HCl  MnCl2 + Cl2 + 2 H2O
Cl2 can reduced to HCl by its reaction with H2 in presence of diffused sunlight.
Diffused sunlight
H2 + Cl2       2 HCl
F-3. HI is a strong reducing agent and, therefore, reduces H2SO4 to SO2 and itself get oxidised to 2.

3Na + conc. H3PO4   K3PO4 + H
F-4._ Aqua regia is three parts of concentrated HCl and one part of concentrated HNO 3.
2Au + 11HCl + 3HNO3  2H[AuCl4] + 3NOCl + 6H2O
8HCl + 2HNO3 + Pt  H2[PtCl6] + 2NOCl + 4H2O
F-5. (i) In anhydrous state, HCl is a covalent molecule. In aqueous solution, HCl combines with water molecule to
form H3O+ and Cl– ions.
HCl (g) + H2O ()  H3O+ (aq) + Cl– (aq)
(ii) HF attacks glass bottles. The sodium and potassium silicates are converted into flurosilicates
Na2 SiO3 + 6HF  Na2 SiF6 + 3H2O
(iii) The weakest acidic nature of HF is due to :
High bond dissociation enthalpy of HF bond.
HF has conjugate base F–. Small size and concentrated charge make F– a Lewis base. Hence, it can
accept back H+.
F-6. (i) H (hydrogen iodide) (ii) 2 + SO2 + H2O
F-7. (i) Pb3O4 + 8HCl  3PbCl2 + 4H2O + Cl2
(ii) 3 [SiO2 + 4HF  SiF4 + 2H2O]
3SiF4 + 3H2O  2H2SiF6 + H2SiO3
_____________________________________
Overall :3SiO2 + 12HF  2H2SiF6  H2 SiO3 +3H2O

White waxy
deposit
G-1._ 673 K, 1 bar

Xe(g) + F2(g)    XeF2(s)
(Xenon in excess)
873 K, 7 bar
Xe(g) + 2F2(g)   XeF4(s)
(1 : 5 ratio)
573 K, 6070 bar
Xe(g) + 3F2(g)       XeF6(s)
(1 : 20 ratio)
G-2._ Partial hydrolysis of XeF6 gives XeOF4.
XeF6 + H2O  XeOF4 + 2 HF
G-3._ Yes, hydrolysis of XeF4 leads to a redox reaction (disproportination)
6XeF4 + 12 H2O  4 Xe + 2XeO3 + 24 HF + 3O2
G-4._ XeF6 + 3 H2O  XeO3 + 6 HF

XeF6 + H2O  XeOF4 + 2 HF
XeF6 + 2H2O  XeO2F2 + 4 HF
ADV PHN - 115

G-5. (i) XeF2 + H2 Xe + 2HF
(ii) 2XeF6 + SiO2  2XeOF4 + SiF4 ;
2XeOF4 + SiO2  2XeO2F2 + SiF4
2XeO2F2 + SiO2  2XeO3 (Explosive) + SiF4
(iii) XeF6 + SbF5  [XeF5]+ [SbF6]– [Addition ionic product is formed]
H-1. (a) Cl2  F2 473 K

  2ClF (b) I2 + 3Cl2  2ICl3
(Equal volume ) (Excess )
(c) Br2 + 3F2  2BrF3 (d) Br2 + 5F2  2BrF5
(Excess )
H-2. ICl is more reactive than I2 because I-Cl bond is weaker than I-I bond. Consequently, ICl breaks easily to form
halogen atoms which readily bring about the reactions.
H-3._ (a) Chlorine trifluoride (ClF3); iodine trichloride (Cl3 or 2Cl6)
(b) ICl + H2O  HCl + HOI
H-4. (i) Chlorine bleaching action is due to oxidation while that of sulphur dioxide is due to reduction. Hence, the
substance bleached by SO2 is reoxidised by the oxygen of the air to its original state.
Cl2 bleaches coloured material by oxidation and thus bleaching is permanent.
Cl2 + H2O  2HCl + [O]
Coloured material + [O]  Colourless
On the other hand beaching by SO2 is by reduction and thus temporary because colourless articles
are further oxidised by air.
SO2 + 2H2O  2H2SO4 + 2[H]
[O]
Coloured material + [H]  Colourless   coloured
(ii) 2 is a covalent molecule. Thus, its solubility is less in polar solvent, i.e., water. Potassium iodide combines
with iodine and forms a polyhalide which is an ionic compound. Being ionic, K3 is more soluble.
K + 2  K3 (K+ 3–) brown solution
H-5. (i) 2NaO3 + 5NaHSO3  3 NaHSO4 + 2Na2SO4 + H2O + 2

(ii) Ca(OH)2 + Cl2  Ca(OCl)Cl + H2O
PART - II
A-1. (B) A-2. (A) A-3. (A) A-4. (D) A-5. (C)
B-1. (C) B-2. (B) B-3._ (B) C-1._ (C) C-2. (D)
C-3. (D) C-4. (A) C-5. (C) C-6. (A) C-7. (A)
D-1._ (A) D-2. (D) D-3. (C) D-4._ (C) D-5. (B)
E-1. (D) E-2. (C) E-3. (B) E-4. (A) E-5. (B)
F-1. (D) F-2. (B) F-3. (B) F-4. (A) F-5 (B)
F-6. (D) F-7._ (C) G-1._ (B) G-2. (B) G-3._ (A)
G-4. (A) G-5._ (D) H-1._ (D) H-2. (B) H-3._ (A)
H-4. (C)
PART - III
1. (A - p,q) ; (B - p,r) ; (C - q,s) ; (D - p,q,r,s)
2. (A - q,s) ; (B - s) ; (C - p) ; (D - r)
3. (A - p,q,r,s) ; (B - p,q,r,s,t); (C - p,q,r,s) ; (D - q,s,t)
ADV PHN - 116

EXERCISE - 2
PART - I
1. (D) 2. (B) 3. (A) 4. (A) 5. (C)
6. (A) 7. (A) 8. (A) 9. (D) 10. (D)
11. _ (C) 12. (A) 13. (D) 14. (B) 15. (C)
16. (A)
PART - II
1. 32 2. 4 3. 43 4. 6 5. 2
6. 5 7. 3 8. 13 9. 2 10. 3
11. 4 12. 7 13. 8 14._ 20 15. 4
PART - III
1. (B,C) 2. (A,B,C,D) 3. (B,D) 4. (A,C) 5. (A,B,D)
6. (B,C) 7. (A,C,D) 8. (A,C,D) 9. (A,B,C) 10. (A,B,C)
11. (A,B,D) 12. (A,B,C,D) 13. (B,C) 14. (A,B) 15. (A,B,C,D)
PART - IV
1. (D) 2. (D) 3. (C) 4. (C) 5. (A)
6. (C) 7. (A) 8. (B) 9. (D) 10. (C)
ADV PHN - 117


above.
1. The manufacture of fluorine is done by :

(1) heating anhydrous HF and MnO2. (2) electrolysis of aqueous HF.
(3) electrolysis of anhydrous HF mixed with KHF2. (4) heating a mixture of KF, MnO2 and conc. H2SO4.
2. The catalyst used in Decons process is :

(1) CuCl2 (2) Cu (3) CuSO4 (4) CuS
3. Which electrolyte is used in Dennis method for the preparation of fluorine ?

(1) KHF2 in anhydrous HF (2) molten cryolite
(3) pure dry molten KHF2 (4) none of these
4. Chlorine is liberated when we heat :

(1) KMnO4 + NaCl (2) K2Cr2O7 + MnO2 (3) Pb(NO3)2 + MnO2 (4) K2Cr2O7 + HCl
5. An easy way of obtaining Cl2 gas in the laboratory is :

(1) by heating NaCl and concentrated H2SO4. (2) by heating NaCl and concentrated MnO2.
(3) by mixing HCl and KMnO4. (4) by passing F2 through NaCl solution.
6. When chlorine reacts with turpentine oil, the product formed is :

(1) carbon (2) carbon and HCl (3) turpentine chloride (4) none of these
7. Which of the following does not decolourise iodine ?

(1) Na2SO3 (2) Na2S2O3 (3) NaCl (4) NaOH
 
8. In the reaction, 3Br2 + 6CO 32 + 3H2O  5Br– + BrO 3 + 6HCO 3 :
(1) bromine is oxidised and carbonate is reduced (2) bromine is both oxidised and reduced
(3) bromine is reduced and water is oxidised (4) bromine is neither oxidised nor reduced
9. A greenish yellow gas reacts with an alkali metal hydroxide to form a halate which can be used in fire works
and safety matches. The gas and halate respectively are :
(1) Br2 , KBrO3 (2) Cl2 , KClO3 (3) I2 , NaIO3 (4) none
10. Two gases X & Y bring about bleaching of flowers, X bleaches by reducing the colouring matter. While Y
bleaches due to oxidation of dye. X and Y are respectively
(1) SO2, Cl2 (2) Cl2, SO2 (3) SO2, O2 (4) None of these
11. Which of the following gases can be dried by concentrated H 2SO4 ?

(1) HCl (2) HBr (3) HI (4) H2S
ADV PHN - 118

12. H2SO4 cannot be used for obtaining HBr from KBr because :
(1) HBr oxidises H2SO4. (2) HBr reduces H2SO4.
(3) HBr undergoes disproportionation. (4) KBr reacts very slowly.
13. Which of the following is weakest acid ?
(1) HF (2) HCl (3) HBr (4) HI
14. Among the following which reaction is not correct :
(1) NaAlO2 + HCl + H2O  NaCl + Al(OH)3
(2) Ca3N2 + HCl  CaCl2 + NH3
(3) Au + H+ NO3– + Cl–  AuCl3– + NO + H2O
(4) Pt + H+ + NO3– + Cl–  PtCl62– + NO + H2O
15. Order of boiling point is

(1) HF > HI > HBr > HCl (2) HF > HBr > HI > HCl
(3) HCl > HBr > HI > HF (4) HCl > HI > HBr > HF
16. Euchlorine is :
(1) obtained by heating perchlorate with conc. HCl. (2) a chloride of europium
(3) a mixture of Cl2 and Cl2O7 (4) a mixture of Cl2 and Cl2O2
17. Consider the oxy acids HClOn series here value of n is 1 to 4, then incorrect statement regarding these
oxyacids is :
(1) Acidic chloride of oxy acids increases with increasis n.
(2) Oxidising power of oxy acids increases with decreasis n.
(3) Thermal stability oxy acids decreases with increasis n.
(4) Cl–O bond order decreases with decreasis n.
18. How many of the following are correctly match :
(1) Cl2O - (a) yellow-brown gas (b.p. 10ºC).
(2) ClO2 - (b) React with O3 gives Cl2O6 (dark red) it is a mixed anhydride of HClO3 and HClO4.
(3) Cl2O7 - (c) It is anhydride of HClO4 (only).
(4) Cl2O7 - (d) Oily explasive colourless liquid.
(5) Cl2O7 - (e) has 2 type of O–Cl bond length.
(6) I2O5 - (f) Obtained by reaction between I2 and CO.
(1) (1) - (a); (2) - (b); (3) - (c); (4) - (d) (2) (3) - (b); (4) - (e); (5) - (d); (6) - (f)
(3) (1) - (b); (2) - (a); (3) - (c); (4) - (d) (4) (2) - (c); (3) - (b); (4) - (d); (5) - (e)
19. The strongest acid amongst the following is :
(1) HClO4 (2) HClO3 (3) HClO2 (4) HClO
20. Which of the following is not the characteristic of interhalogen compounds ?
(1) They are more reactive than halogens.
(2) They are quite unstable but none of them is explosive.
(3) They are covalent in nature.
(4) They have low boiling points and are highly volatile.
21. Which of the following statement is correct.
(1) All interhalogen compounds are gaseous at room temperature.
(2) Interhalogen are either gaseous or liquid at room temperature.
(3) Interhalogens can solid or liquid or gaseous at room temperature.
(4) Interhalogen compounds are liquid at room temperature.
22. In which following statement are incorrect

(1) Pseudohalogen ions are not spherical
(2) Pseudohalides are generally less electronegative than the lighter halide (F –, Cl–)
(3) OCN–, NNN– pseudohalide are bidentate ligands
(4) Pseudohalogens form dimers and form molecular compound with non metal and Ionic compounds with
alkali metal.
ADV PHN - 119

23.
.
Ionisation energy values are given for Xenon (Xe) and Radon (Rn)
Element IE(KJ/mol)
Xe 1169
Rn 1036
Predict a suitable reason for the fact that the chemistry of Rn has not been studied significantly while that of
Xe has been extensively studied.
(1) Rn appears to be more reactive (2) Xe is less reactive than Rn
(3) Rn isotopes have shorter lifetimes (4) Rn is heavior than Xe.
24. In the clathrates of xenon with water, the nature of bonding between xenon and water molecule is :
(1) covalent (2) hydrogen bonding
(3) co-ordinate (4) dipole-induced dipole interaction
25. Among noble gases (from He to Xe) only xenon reacts with fluorine to form stable fluorides because xenon :
(1) has the largest size. (2) has the lowest ionization enthalpy.
(3) has the highest heat of vaporization. (4) is the most readily available noble gas.
26. What are the products formed in the reaction of xenon hexafluoride with silicon dioxide ?
(1) XeSiO4 + HF (2) XeF2 + SiF4 (3) XeOF4 + SiF4 (4) XeO3 + SiF2
27. Which of the following are partial hydrolysis gives XeOF2.

(1) XeF2 (2) XeF4 (3) XeF6 (4) XeOF4
28. The ratio of total number of lonepairs in XeF2 and XeF4 are :
(1) 3 : 2 (2) 9 : 14 (3) 14 : 19 (4) 9 : 19
29. Xenon reacts with P + F6 to form

(1) XeF2 (2) Xe+ [P + F6]– (3) Xe–[Pt F6]+ (4) XeF4
30. Which among the following statement is incorrect.

(1) XeF4 and SbF5 combine to form salt
(2) XeF6 on complete hydrolysis gives XeO3
(3) XeF6 react with H2 produce XeF2 and HF
(4) Xenon hexaflouride react with silica to form a Xenon compound and this Xenon compound have oxidation
of Xenon is +6.

Que. 1 2 3 4 5 6 7 8 9 10
Ans.
Que. 11 12 13 14 15 16 17 18 19 20
Ans.
Que. 21 22 23 24 25 26 27 28 29 30
Ans.
ADV PHN - 120


1. Bleaching powder is : (NSEC 2000)
(A) CaOCI2 (B) CaCIO (C) CaCIO3 (D) Ca(OCI)2
2. Acid used for making permanent markings on the glass surface is: (NSEC 2001)
(A) HNO3 (B) HF (C) HIO3 (D) H2SO4
3. One gas bleaches the colour of flowers by reduction while the other by oxidation. The gases are
(NSEC 2002)
(A) SO2, CI2 (B) CO, CI2 (C) H2S, Br2 (D) NH3, SO3
4. Fluorine has –1 oxidation state while iodine exhibits oxidation states of –1, +1, +3, +5 and +7. This is due
to (NSEC 2002)
(A) fluorine being a gas (B) availability of d-orbitals in iodine
(C) non-availability of d-orbitals in iodine (D) none of the above
5. Which pseudo-halogen does not have dimeric nature (NSEC 2002)

(A) cyanogen (B) azide (C) thiogene (D) selenothigen.
6. The correct sequence of reducing power of halide ions are (NSEC 2002)
(A) CI– > Br– > I– (B) Br– > I– > CI– (C) I– > Br– > CI– (D) CI > I > Br
– – –
7. Which gas is mixed with oxygen by sea-divers at the high underwater pressure ? (NSEC 2002)
(A) Nitrogen (B) Neon (C) Helium (D) Argon.
8. Which oxyacid of chlorine shows oxidation state of + 5 ? (NSEC 2002)

(A) hypochlorous acid (B) chloric acid (C) chlorous acid (D) perchloric acid
9. The compound that cannot be formed by xenon is (NSEC 2003)

(A) XeO3 (B) XeF4 (C) XeCI4 (D) XeOF4
10. The interhalogen compound that cannot exist is (NSEC 2003)

(A) IBr5 (B) ICI7 (C) IF4 (D) BrF5
11. Bleaching powder is made by passing CI2 into slaked lime. Its formula is (NSEC 2005-06)
(A) Ca(OCI)2 (B) CaO(OCI) (C) CaOCI2 (D) CaCI22H2O.
12. Hydrogen fluoride is a liquid at room temperature due to (NSEC 2005-06)

(A) dimerisation (B) dissociation followed by aggregation.
(C) association (D) polymerisation
13. Concentrated sulphuric acid on reaction with NaCl, NaBr and NaI produces HCl, bromine and iodine
respectively.What order of oxidizing ability of halogens with reference to sulphuric acid can be established on
the basis of this reaction ? (NSEC 2007-08)
(A) H2SO4 > I2 > Br2 > Cl2 (B) Cl2 > H2SO4 > Br2 > I2 (C) H2SO4 > Cl2 > Br2 > I2 (D) Cl2 > Br2 > I2 > H2SO4
14. Which of the following is a ‘‘super acid’’ (NSEC 2008-09)

(A) (HF + SbF5) in SO2 (B) (H2SO4+ SO3) in SO2
(C) (HNO3 + BF3) in SO2 (D) (H3PO4 + PF5) in SO2
15. Of the interhalogen compounds, CIF3 is more reactive than BrF3 has higher conductance in the liquid state.
The reason is that (NSEC 2011-12)
(A) BrF3 has higher molecular weight (B) CIF3 is volatile
(C) BrF3 dissociates into BrF2– more easily (D) CIF3 is most reactive
16. Radioactive inert gas is : (NSEC 2011-12)

(A) technetium (B) radon (C) xenon (D) curium
17. The gas which liberates bromine from a solution of KBr is (NSEC 2013-14)
(A) Cl2 (B) I2 (C) SO2 (D) HI
ADV PHN - 121


A. General %
4. Section 1 contains 7 multiple choice questions. Each question has four choices (A), (B), (C) and (D)
out of which ONE is correct.
out of which ONE OR MORE THAN ONE are correct.
6. Section 3 contains 6 questions. The answer to each of the questions is a single-digit integer, ranging
from 0 to 9 (both inclusive).
7. Section 4 contains 1 paragraphs each describing theory, experiment and data etc. 3 questions relate
to paragraph. Each question pertaining to a partcular passage should have only one correct answer
among the four given choices (A), (B), (C) and (D).
8. Section 5 contains 1 multiple choice question. Question has two lists (list-1 : P, Q, R and S; List-2 : 1,
2, 3 and 4). The options for the correct match are provided as (A), (B), (C) and (D) out of which ONLY
ONE is correct.
C. Marking Scheme
9. For each question in Section 1, 4 and 5 you will be awarded 3 marks if you darken the bubble
corresponding to the correct answer and zero mark if no bubble is darkened. In all other cases, minus
one (– 1) mark will be awarded.

1. Which graph correctly describes a trend found in the halogen group?
(A) (B)
(C) (D)
ADV PHN - 122

2. (i) (r) + (p)  NaClO2 + O2
H
(ii) IO3– + I– 
 (q)
(iii) Acidic solution of ClO2–  (s) + (r).
(disproportionation reaction)
(p) used as air purifier and CO2 absorber.
(q) estimated by hypo and it forms voilet colour vapour (it self).
(r) is yellow colour gas
(s) gives chromylchloride test.
Which option is correct.
(A) (p) = Na2O2, (q) = l2 (B) (q) = I2O5, (r) = Cl–
(C) (p) = Na2O, (r) = Cl2O (D) (r) = Cl2, (s) = Cl2O3
3. [HXeO4]– + OH–  [X] + [Y] + O2 + H2O

The products [X] and [Y] in unbalanced reaction are :
(A) [XeO6]4– & Xe (B) [XeO6]4– & XeO3 (C) XeO3 & Xe (D) H2XeO4 & Xe
4. Consider following properties of the noble gases.

I : They readily form compounds which are colourless.
II : They generally do not form ionic compounds.
III : Xenon has variable oxidation states in its compounds.
IV : the smaller He and Ne do not form clathrate compounds.
Select correct properties.
(A) I, II , III (B) II , III, IV (C) I, III, IV (D) All
5. Which behave like pseudohalide in following

(A) (CN)2 (B) (SCN)2 (C) N3– (D) I3–
6. Cl2 (g) + Ba(OH)2  X (aq) + BaCl2 + H2O

X + H2SO4  Y + BaSO4

Y  Z + H2O + O2
 365 K
Y and Z, are respectively :

(A) HClO4, ClO2 (B) HClO3, ClO2 (C) HClO3, ClO6 (D) HClO4, Cl2O7
7. Which of the following on treatment with XeF6 gives Xe?

(A) H2 (B) HCl (C) OH– (conc) (D) All of these

8. Which of the following have melting points less than 298 K.

(A) Fluorine (B) Bromine (C) Iodine (D) Chlorine
Ha log en excess
9. Aq. solution of salt   A 
acid ( X )
 soluble
Ha log en acid ( X )
Yellow precipitate
The halogen acid (X) is
(A) HF (B) HCl (C) HI (D) Cl2 (aq.)
ADV PHN - 123

10. Select the correct statement(s).
(A) Cl2O and ClO2 are used as bleaching agents and as germicides.
(B) I2O5 is used in the quantitative estimation of CO.
(C) ClO2 is the anhydride of HClO2 and HClO3.
(D) Cl2O is a colouless oily liquid.
11. Which of the following are Pseudo halid.

(A) CN– (B) N3– (C) OCN– (D) NO3–
12. Which of the following can be obtained by hydrolysis of XeF 6

(A) XeO3 (B) HF (C) XeO2F2 (D) Xe

13. What is the sum of group number and period number (according to IUPAC system) of the non-metal which
exist in liquid state at room temperature.
14. How many of the following compounds form HCl on hydrolysis as one of the products (major or minor)
(i) BCl3 (ii) BiCl3 (iii) SO2Cl2 (iv) NCl3 (v) PCl5 (vi) CrO2Cl2
(vii) CH3Cl (viii) NaCl (ix) ZnCl2
15. NH4ClO4 + NHO3  (A) + (B)   (C) (neutral oxide
The summation of number of lone pairs and atomicities of compound B and C is.
16. The oxidation state of iodine in compound which is obtained by heating HIO 3 at 170ºC is +n.
Give value of n
17. Hydrolysis of compound A, two acids P and Q forms, P is used in etching of glass, Q on strongly heating
gives a oxide R. R is used in estimation of carbon monoxide. Calculate total number of lone pairs on
compound A.
18. The simplest ratio x : y of xenon and fluorine when passes through Ni-tube (400ºC) at high pressure gives
XeF6. Here x + y is :

(A), (B), (C) and (D)

White crystalline solid (A) reacts with H2 to form a highly associated liquid (B) and a monoatomic, colorless
gas (C). The liquid (B) is used for etching glass. Compound (A) undergoes hydrolysis slowly to form (C), (B)
and a diatomic gas (D) whose IE is almost similar to that of (C). (B) forms an addition compound with KF to
form (E) which is electrolysed in the molten state to form a most reactive gas (F) which combines with (C) in
2:1 ratio to produce (A).
19. According to Molecular Orbital Theory, which of the following is correct about the molecule D ?
(A) its bond order is 2.0 (B) it has two unpaired electrons in –bonding M.O.
(C) both the above are correct (D) none of these is correct
20. Which of the following is correct for the white crystalline solid (A) ?
(A) It oxidises F– to F2
(B) It on hydrolysis with alkali under goes disproportionation.
(C) It is obtained by the reaction of (C) with O2F2 at 118ºC.
(D) None of these.
ADV PHN - 124

21. The compound 'A' reacts with sulphur to form a compound in which hybridisation state of sulphur atom is
(A) sp3d (B) sp3d2 (C) sp3 (D) sp3d3

22. Match the reaction products listed in column–I with the particulars listed in column-II
Column–I Column–II
(A) XeF2 + H2O  (p) Redox reaction
(B) XeF4 + H2O  (q) Disproportionation
(C) XeF6 + H2O  (r) O2 formation
(D) XeO3 + NaOH  (s) Xe formation
(t) Etching glass

Que. 1 2 3 4 5 6 7 8 9 10
Ans.
Que. 11 12 13 14 15 16 17 18 19 20
Ans.
Que. 21 22
Ans. (A) (B) (C) (D)

Problem = 1 (INCho 2008)
Potential energy curves and molecular orbitals
J.G. Dojahn, E.M.C. Chen and W.E. Wenthworth [J. phys. che. 100, 9649 (1996)] examined
the potential energy diagrams of X2 and X2– where X is a halogen. The diagram for F2 and F2–
is reproduced on the next page.
1.1 From this diagram, the dissociation energies (in eV) of F2 and F2– are
(Mark X in the correct box)
1.2 1.3 1.6 1.8 1.9

F2
[1 mark]
1.1 1.3 1.5 1.6 1.7
F2–
ADV PHN - 125

1.2 Using this diagram, the electron affinities of the fluorine atom and F2 molecule can be calculated. Mark X in
the correct box the values (in eV) given below. [2 mark]
3.2 3.4 3.6 3.7 3.8

F atom
2.8 3 3.2 3.3 3.4

F2 molecule
1.3 What are the appropriate equilibrium internuclear distances for F2 and F2– ?
(Choose from the following values 1.2, 1.4, 1.6, 1.7, 1.9 and 2.1 Å)
[1 mark]
1.4 The vibrational frequencies for F2 and F2– reported by Dojahn et. al. on fitting the potential energy curves were
917 and 450 cm –1. What is the ratio of the corresponding force constants ? [2 mark]
3
1
g +
0
F+F
-1
U (eV)
-2
-3
F + F
2 +
u
-4
-5
-6
1 2 3 4 5 6 7
Internuclear distances, R (Å)

The above observation regarding the force constants canbe qualitatively explained on the basis of MO theory.
Problem = 2 (INCho 2012)

Halogens
The chemistry of halogens is interesting. Halogens belong to the group 17 of the periodic table. The name
“Halogen” was introduced by J.S.C. Schweiggen in 1811 to describe the property of chlorine (at that time
unique among the elements) to combine directly with metals to give salts. Iodine is an essential trace
element for humans and plays an important role in growth regulating hormone thyroxine, which is produced
in the thyroid gland. Deficiency of iodine in diet leads to Goitre. In order to prevent this condition, about
0.01% Nal is added to the table salt. Iodine is a lustrous solid and sublimes at ordinary temperature.
ADV PHN - 126

2.1 (a) The iodine containing species having maximum concentration, present in a 0.5 M KI solution containing
1.5 M I2 is : (1.5 marks)
(b) The solubility of iodine in carbon tetrachloride is due to
(i) ionic solvent-solute interaction (ii) charge-transfer phenomenon
(iii) van der Waals interaction (iv) dissociation of iodine (0.5 mark)
2.2 Write the balanced equations for the two reactions leading to A and B. (2 marks)
Compound B is a liquid at room temperature (b.p.126°C). It is not only a fluorinating agent, but also a
preparative nonaqueous solvent. Antimony (V) fluoride dissolves freely in B to form a complex (C).
2.3 Write the equation for the formation of C. (1 mark)
2.4 Out of the species PO43–, SO42–, IO4– and XeO64–, the most oxidizing one is : (1 mark)

Problem # 1 (IChO_1988)
Upon heating of a mixture of A and fluorine (molar ratio 1 : 9, pressure
approximately 1 MPa) to 900 °C three compounds ( B, C and D) are formed. All
three products are crystalline solids at ambient temperature with melting points
below 150 °C. The fluorine content of C is found to be 36.7 % and that of D 46.5
% (by weight). When B is treated with anhydrous HOSO2F at -75°C a compound
E is formed:
B + HOSO2F  E + HF
E is a solid which is stable for weeks at 0 °C, but decomposes in days at room temperature. The electron
density distribution of E obtained through X-ray diffraction studies is shown on two intersecting, mutually
perpendicular planes (see Fig. 1).
The numbers indicated on the maps relate to the electron density in the neighbourhood of the atoms of E as
a function of the spatial coordinates. The maxima found in these maps coincide with the locations of the
atoms and the values are approximately proportional to the number of electrons in the atom in question.
1.1 Identify A, B, C, D and E.

1.2 Use the valence-shell electron-pair repulsion theory (VSEPR) to propose electron-pair geometries for B and
C. Using the two electron density maps, sketch the molecular geometry of E.
1.3 Write the equations for the three hydrolysis reactions.
ADV PHN - 127

PROBLEM = 2 (IChO_1977)
Note: The International Jury did not choose Task 2a for the competition but the alternative Task 2b.
Attention
Make sure to open only the correct envelopes. You lose points for an incorrectly opened envelope.
Return unopened envelopes together with your solution.
Halogen X reacts with an aqueous solution of another halogen compound KYO 3 according to the equation:
X2 + 2 KYO3  2 KXO3 + Y2
2.1 The atomic number of halogen X is greater than that of halogen Y. (If you find this answer correct open
envelope 1.)
2.2 The atomic number of halogen X is smaller than that of halogen Y. (If you find this
assertion correct open envelope 2.)
Choose the correct answer 1 or 2, open the correct envelope and continue in the solution according to the
text in the opened envelope.
Text in envelope 1:
Your answer is correct. Continue.
Compound KXO3 is oxidised in alkaline solution by halogen Y forming a compound KXVIIO4 whereas halogen
Y is reduced to halide KY:
KXO3 + 2 KOH + Y2  KXO4 + 2 KY + H2O
An aqueous solution of potassium halide KY yields with AgNO3 solution a white precipitate AgY insoluble in
water but readily soluble in aqueous ammonia solution.
2.3 Halogen Y is fluorine (envelope 3).
2.4 Halogen Y is chlorine (envelope 4).
2.5 Halogen Y is bromine (envelope 5).
Choose the correct answer 3, 4 or 5, open the corresponding envelope and carry on according to the instructions
inside.
Text in envelope 2 :
Your answer is incorrect. Choose envelope 1.
Text in envelope 3:
Your answer is incorrect. Choose answers 4 or 5.
Text in envelope 4:
Your answer is correct. Choose the final correct answer by indicating the correct alternative 6 or 7 :
2.6 X = Br ; KXO4 = KBrO4
2.7 X = I ; KXO4 = KIO4
Text in envelope 5:
Your answer is incorrect. Choose answers 3 or 4.
A solution was formed from 0.5284 g of a sample of an alloy containing aluminium. The aluminium was
then precipitated as aluminium 8-hydroxyquinolate. The precipitate was separated, dissolved in hydrochloric
acid and the 8-hydroxyquinoline formed was titrated with a standard solution of potassium bromate containing
potassium bromide. The concentration of the standard potassium bromate solution was 0.0200 M and
17.40 cm3 of it were required. The resultant product is a dibromo derivative of 8-hydroxyquinoline.
The structural formula of 8-hydroxiquinoline is:
The relative atomic mass of aluminium is 26.98.
3. Write the balanced equation for the reaction in which bromine is produced.
ADV PHN - 128

Halogen Chemistry
Halogens in their reactions among themselves and with a variety of other elements give rise to a large
number of compounds with diverse structure, bonding and chemical behaviour. Metal halides, halogen derivatives
and interhalogens represent major types of halogen compounds.
4.1 Write the formulae and 3-dimensional structures of these interhalogen molecules on the basis of VSEPR
theory. Show the disposition of the lone pairs on the central atom, where appropriate.
A mixture of iodine vapour and chlorine gas when fed into a mass spectrometer gave two sets (A and B) of
mass spectral peaks corresponding to molecular ions of two chemical species at m/z:
A: 162, 164
B: 464, 466, 468, 470, 472, 474, 476
4.2 Identify the molecular species corresponding to m/z = 162, 164, 466 and 476. Draw the structure of the
heaviest species (m/z = 476) indicating clearly the lone pairs on atom(s) of I (iodine). Show the isotopic
composition of each species.
In aqueous medium chlorine gas oxidises sodium thiosulphate to an ion containing the highest oxidation
state of sulphur.
4.3 Write down the chemical equation for this reaction.
4.4 Chlorine dioxide reacts with sodium hydroxide as shown below. Identify the products X and Y (both containing
chlorine) and balance the equation.
4.5 Write the oxidation state(s) of chlorine in bleach.
5.1 Which of the following groups contains solid compounds at 10 °C?
(a) H2O, NH3, CH4 (b) F2, Cl2, Br2 (c) SO3, I2, NaCl (d) Si, S8, Hg
5.2 Which of the following salts forms an acidic aqueous solution?

(a) CH3COONa (b) NH4Cl (c) Na2HPO4 (d) Na2CO3
(e) NaHCO3
5.3 Write the electronic formulas for the following compounds so that the nature of the chemical bonds is
evident:
(a) NaClO3, (b) HClO3, (c) SiF4, (d) NH3,
(e) CaF2, (f) H2O
Gold Capital of Asia
Chiufen, the old mining town located within the hills in the northeast Taiwan, is a place where you can really
experience Taiwan’s historical legacy. It was the site of one of the largest gold mines In Asia. Accordingly,
Chiufen is often referred to as the Gold Capital of Asia. The compound KCN is traditionally used to extract
gold from ore. Gold dissolves in cyanide (CN–) solutions in the presence of air to form Au(CN)2– , which is
stable in aqueous solution.
4 Au(s) + 8 CN– (aq) + O2(g) + 2 H2O (l) 4 Au(CN)2– (aq) + 4 OH– (aq)
6. The function of HCl is to provide Cl–. What is the purpose of the Cl– for the above reaction. Select your answer
from the following choices.
(a) Cl– is an oxidizing agent (b) Cl– is a reducing agent
(c) Cl is a complexing agent
–
(d) Cl– is a catalyst
ADV PHN - 129

A mixture of hydrogen and chlorine kept in a closed flask at a constant temperature was irradiated by
scattered light. After a certain time the chlorine content decreased by 20% compared with that of the starting
mixture and the resulting mixture had the composition as follows: 60 volume % of chlorine, 10 volume % of
hydrogen, and 30 volume % of hydrogen chloride.
7. How chlorine, hydrogen, and hydrogen chloride are produced ?
Write down equations for the following reactions:
8. Action of chlorine on lime water (Ca(OH)2) in a cold reaction mixture.
The detection limit is one of the basic parameters in quantitative analysis of trace amounts of elements. The
detection limit is expressed as the least mass of an element which can be determined by a given method
with a given accuracy.
As an example we shall consider the method used for the determination of microscopic amounts of bismuth.
In 1927 German chemist Berg suggested to precipitate bismuth as a practically insoluble salt :
8-hydroxyquinolinium tetraiodobismuthate [C9H6(OH)NH][BiI4] (Mr = 862.7).
9.1 Write a balanced net ionic equation of the reaction occurred on acidification.
Step 5: Iodine is quantitatively extracted by 4 portions of chloroform. Aqueous layer is transferred to a flask, to which
1 cm3 of bromine water is added, and the mixture is mixed for 5 minutes.
9.2 Write the balanced net ionic equations of the reactions occurred upon the addition of bromine water. Note
that an excess of bromine can react with hydrogen cyanide to give BrCN, and iodide is oxidized into IO 3–.
Step 6: To eliminate an excess of molecular bromine 3 cm 3 of 90 % methanoic (formic) acid is added to the mixture.
9.3 Write the balanced net ionic equations of the reactions occurred upon the addition of KI, taking into consideration
that iodide reacts with BrCN in a similar manner as with ICN to form molecular iodine.
Step 7: The resulting solution is titrated by a standard 0.00200 M Na2S2O3 solution. The results thus obtained are
used to calculate the content of bismuth in the sample taken for analysis.
ADV PHN - 130

PART - I
1. (3) 2. (1) 3. (1) 4. (4) 5. (3)
6. (2) 7. (3) 8. (2) 9. (2) 10. (1)
11. (1) 12. (2) 13. (1) 14. (3) 15. (1)
16. (4) 17. (3) 18. (1) 19. (1) 20. (4)
21. (3) 22. (3) .

23. (3) 24. (4) 25. (2)
26. (3) 27. (2) 28. (2) 29. (2) 30. (3)
PART - II
1. (D) 2. (B) 3. (A) 4. (B) 5. (B)
6. (C) 7. (C) 8. (B) 9. (C) 10. (C)
11. (C) 12. (C) 13. (B) 14. (A) 15. (C)
16. (B) 17. (A)
PART - III
1. (B) 2. (A) 3. (A) 4. (B) 5. (C)
6. (B) 7. (D) 8. (ABD) 9. (BC) 10. (ABC)
11. (ABC) 12. (ABC) 13. 21 14. 5 15. 24
16. 5 17. 16. 18. 21 19. (A) 20. (C)
21. (B) 22. (A) – (p,q,r,s,t) ; (B) – (p,q,r,s,t) ; (C) – (t) ; (D) – (p,q,r,s)
PART - IV
1.1 F2-1.6, F2– - 1.1, 1.3 1.2 F atom -3.4, F2 molecule -3.0, 3.2
1.3 F2: - 1.4 F2– : -1.9 1.4 4.15
2.1 (a) KI7 (b) (iii)
2.2 F2 + Br2  2BrF (A)

3BrF  Br2(g) + BrF3 (B) or 5BrF  2Br2(g) + BrF5 (B)
Compound B is a liquid at room temperature (b.p.126°C). It is not only a fluorinating agent, but also a
preparative nonaqueous solvent. Antimony (V) fluoride dissolves freely in B to form a complex (C).
ADV PHN - 131

2.3 BrF3 + SbF5  [BrF2]+[SbF6]–
or BrF5 + SbF5  [BrF4]+[SbF6]–
2.4 because oxidation state Xe is +8 and it is highly unstable compounds.

XeO64– is called perxenate ion.
PART - V
1.1 A: Xe B: XeF2 C: XeF4 D: XeI6 E: XeF(OSO2F)
1.2 (B) (C) (E)
The original mixture was hydrolysed in water. B reacts to A while liberating oxygen and producing aqueous
hydrogen fluoride. Hydrolysis of C leads to A and oxygen (in molar ratio of 4 : 3) and yields an aqueous
solution of AO3 and hydrogen fluoride. D hydrolyses to an aqueous solution of AO3 and hydrogen fluoride.
1.3 XeF2 + H2O  Xe + 2 HF + 0.5 O2

XeF4 + 2 H2O  2/3 Xe + 4 HF + 1/3 XeO3 + 0.5 O2
XeF6 + 3 H2O  XeO3 + 6 HF
2. The correct answers are as follows: 2.1, 2.4, 2.7.
3. BrO3– + 5 Br– 6 H+ 3 Br2 3H2O
4. CIF3 ; BrF5 IF7
4.1
4.2 4 Cl2 + S2O32– + 5 H2O  8 Cl– + 2 SO42– + 10 H+
4.3 2 ClO2 + 2 NaOH NaClO2 + NaClO3 + H2O

X Y
ADV PHN - 132

4.4 Cl2 + Ca(OH)2 Ca(Cl)(OCl) + H2O
or Cl2 + CaO Ca(Cl)(OCl)
or 2 OH– + Cl2 Cl– + OCl– + H2O
4.5 The oxidation state(s) of chlorine in bleach is (are): –I and I
5.1 (c) SO3, I2, NaCl
5.2 (b)
5.3
6. Answer for multiple choice question: (c)
7. Chlorine and hydrogen are produced by electrolysis of aqueous solutions of

NaCl : NaCl (aq) Na+(aq) + Cl– (aq)
anode: 2 Cl– – 2 e Cl2
cathode: 2 Na+ + 2 e 2 Na
2 Na + 2 H2O 2 NaOH + H2
Hydrogen chloride is produced by the reaction of hydrogen with chlorine.
8. Cl2 + Ca(OH)2 CaOCl2 + H2O
9.1 ICN + I– + H+  I2 + HCN

– –
9.2 (a) 3 Br2 + I + 3 H2O  IO3– + 6 Br + 6 H+
–
(b) Br2 + HCN  BrCN + Br + H+
9.3 (a) IO + 5 I– + 6 H+  3 I2 + 3 H2O

–
(b) BrCN + 2I– + H+ I2 + HCN + Br
ADV PHN - 133

PART - I
1. Moissan method
electrolys is
KHF2    KF + HF
K+ + e–  K F–  F + e–
K + HF  KF + H F + F  F2
H + H  H2
CuCl
2. 4HCl + O2 
2
 2Cl2 + 2H2O
400 ºC
3. KHF2 solution in anhydrous HF
4. Only K2Cr2O7 and HCl will give Cl2
K2Cr2O7 + 8 HCl  2KCl + 2CrCl3 + 4H2O + 3O

2HCl + O  H2O + Cl2 × 3
K2Cr2O7 + 14 HCl  2KCl + 2CrCl3 + 7H2O + 3Cl2
5. 2KMnO4 + 16HCl  2KCl + 2MnCl2 + 8H2O + 3Cl2
6. C10H16 + 8Cl2  10C + 16HCl

Terpentine oil
7. NaCl has no reaction with iodine.
 
8. 3Br2 + 6CO 32 + 3H2O  5Br– + BrO 3 + 6HCO 3 (disproportionation reaction)

In this reaction O.S. of Br changes from 0 (in Br2) to –1 (in Br–) and +5 (in BrO 3 ). Thus, in this reaction
bromine is both oxidised (increase in O.S.) and reduced (decrease in O.S.) –disproportionation reaction.
11. HCl is dried over conc. H2SO4. Because HBr, HI and H2S are oxidised by H2SO4.
12. The HBr so formed reduces H2SO4 and itself gets oxidised to evolve Br2.
2HBr + H2SO4  2H2O + SO2 + Br2
ADV PHN - 134

13. Acid strength order : HI > HBr > HCl > HF
Amongs these HI, HBr, HCl are strong acids whereas HF is a weak acid.
14. Au + H+ + NO3– + Cl–  AuCl4– + NO + H2O
15. BP with increase in atomic mass of the hologes. HF has highest BP due to association of HF molecule
through H-bonding.
16. When KClO3 is heated with conc. HCl, a mix. of Cl2 and ClO2 is formeed known as euchlorine.
2KClO3 + 4HCl  2KCl + + 2H2O
17. (1) Acidic chloride : HOCl < HClO2 < HClO3 < HClO4
(2) Oxidising power : HOCl > HClO2 > HClO3 > HClO4
(3) Thermal stability : HOCl < HClO2 < HClO3 < HClO4
(4) Cl–O bond order : HOCl < HClO2 < HClO3 < HClO4
0ºC
18. ClO2 + O3  Cl2O6 (drark red)
Cl2O6 + H2O  HClO3 + HClO4

–H O
2HClO4  
2
 Cl2O7
(1.71Å )
2 : O – Cl bond
Cl2O7  (1.41Å )
6 : O  Al bond
I2O5 + 5CO  I2 + CO2 (this I2 titrated by hopo solution).
19. ClO4– , conjugate base is most stable as charge is dispersed over four oxygen atom and so HClO 4 is the
strongest acid.
20. Interhalogen compounds are mostly liquid or solid at room temperature and are not highly volatile.
21. It is a fact
22. OCN–, NNN– are ambidentate and monodentate ligends both denate only one lone pair. So both are
monodentate ligand.
23.
.
Due to short life-times, Rn has not been studied.
24. In clathrates the bonding between noble gas atom and water is dipole-induced dipole interaction.
25. Out of He, Ne, Ar, Kr and Xe, Xe has the lowest ionisation energy as ionisation energies decreases down a
group.
26. 2XeF6 + SiO2  SiF4 + 2XeOF4
27. (1) XeF2 + H2O  Xe + 2HF + ½O2 (2) XeF4 + H2O  XeOF2 + 2HF
(3) XeF6 + H2O  XeOF4 + 2HF (4) XeOF4 + H2O  XeO2F2 + 2HF
ADV PHN - 135

28.
Total number of lone pair = 9 Total number of lone pair = 14

Ratio = 9 : 14
30. (1) XeF4 + SbF5  [XeF3][SbF5]–

(2) XeF6 + H2O  XeO3 HF
(3) XeF6 + H2  Xe + HF
6
(4) SiO2 + XeF6  X eOF4 [SbF5]–
PART - III
1. With increasing number of electrons in the molecule and hence increasing molecular size and increase in
van der Waal’s forces.
2. ClO2 + Na2O2  NaClO2 + O2

IO3– + I–  I2 + H2O
H
5ClO2– 
 4ClO2 + Cl– + H2O
(+3) (+4) (–1)
A = Na2O2 ; B = I2 ; C = ClO2 ; Cl–
3. 2[HXeO4]– + 2OH–  [XeO6]4– + Xe + O2 + 2H2O
4. (I) They do not form compounds readily as they are chemically inert on account of stable electron configuration.
(II), (III) & (IV) are correct statement.
5. N3– is pseudohalide
(CN)2 and (SCN)2 behave like pseudohalogen
I3– is polyhalide.
6. 6Cl2 (g) + Ba(OH)2  Ba(ClO3)2 (X) + 5BaCl2 + 6H2O
1 
2ClO2 + H2O + O  2HClO3 (Y) + BaSO4
2 2
7. XeF6 + 3H2  Xe + 6HF
XeF6 + 6HCl  Xe + 6HF + 3Cl2
ADV PHN - 136

8. At loom temperature; (298 K = 25ºC)
F2 (g) 

Cl2 (g) These have M.P.s  25º C

Br2 ( ) 
I2(s)
10. 2ClO2 + H2O  HClO2 + HClO3
I2O5 + 5CO  I2 + 5CO2

Cl2O is brownish yellow gas which condenses to an orange coloured liquid in a freezing mixture (b.pt. = 2ºC).
13. Bromine is the only non-metal which exist as liquid at room temperature.
Group no.  17 
 For Bro min e
Period no.  4 
14. (i), (ii), (iii), (v), (vi), (ix)
16. 
HIO3  I2O5
F5
17. (A )
+ H2O  HF  + HIO3
(P ) (Q)
HF is used in etching of glass
HIO3 I2 O 5
(Q) (R )
I2 O 5 + CO  I2 + CO2
(R )
Total number of lone pair in A = 16.
18. 1 : 20 mixture of Xe and F2 will give XeF6.

 x + y = 1 + 20 = 21
Ni / 400ºC
Xe + 3F2  XeF6
10 – 6
19. Compound (D) is O2 and therefore, its bond order = = 2.
2
118 º C
20. Compound (A) is XeF2 ; so, Xe + O2F2    XeF2 + O2
ADV PHN - 137

(19 to 21)
XeF2 + H2  Xe(g) + 2HF( )
(A) (C) (B)
2XeF2 + 2H2O  2Xe(g) + 4HF + O2(g)
(A) (C) (B) (D)
Electrolysis
HF + KF  KHF2 (E)  F2(F)
K+ [F–H......F]–
Xe + F2  XeF2 ; S8 + 24 XeF2  8 SF6 + 24 Xe

1:2
(C) (F) (A)
22. (A) 2XeF2 + 2H2O  2Xe + 4HF + O2
(B) 6XeF4 + 12H2O  4Xe + 2XCO3 + 24HF + 3O2
(C) XeF6 + 3H2O  XeO3 + 6HF
(D) XeO3 + NaOH  Na+ [HXeO4]–
2[HXeO4]– + 2OH–  [XeO6]4– + Xe + O2 + H2O
ADV PHN - 138

d & f-block elements & their important compounds
ADVDBC - 139

Section (A) : Occurrence, Isolation & Allotropy of Elements
A-1._ Write all the noble metals present in the Modern Periodic Table . Also mention the coinage metals out of
those.
A-2._ Name the ores for the chemical formulae mentioned below–
(i) FeCO3 (ii) CuCO3.Cu(OH)2 (iii) HgS
(iv) FeS2 (v) ZnS (vi) AgCl
Section (B) : Periodic trends

B-1._ What are the two most common oxidation states of the first transition series?
B-2. Why are ionization energies of 5d-elements greater then those of 3d-elements ?
Section (C) : Chemical Bonding

C-1._ Draw the structure of H2 TiO4
C-2._ Draw the structures of Cr2O72– ,MnO–4 , MnO2–

4
C-3._ Why Zn has lowest metallic bond strength amongst 3d series elements ?
C-4._ Which oxides decompose on heating to give oxygen to a significant extent (nearly completely) ?
MnO, TiO2, MnO2, CoO, Co2O3, FeO, Fe2O3, HgO, Ag2O, ZnO, Cu2O
C-5._ Write the increasing order of acidic nature of V2O3,V2O4, V2O5
C-6._ Which is more basic Fe(OH)2 or Fe(OH)3?
C-7._ Which is stronger reducing agent Cr or Fe (given: E M2 / M  Cr  –0.91 EM2 / M  Fe  –0.44 )

D-1. Which of the following ions would form (i) coloured and (ii) colourless complexes in water ?
Cu2+, Zn2+, Ti3+, Ti+4, Cd2+, Mn2+
D-2. Copper dissolves in dilute nitric acid but not in dilute HCl. Why?
D-3._ Which of the following element dissolve in hot concentrated NaOH solution? [JEE /80]
Fe, Zn, Cu, Ag
D-4._ Silver jewellery items tarnish slowly in the air due to their reactions with______&______.
D-5. What reaction will take place if a pure silver coin is put in dilute HNO3 ?
Section (E) : Oxides & Hydroxides

E-1._ How many of the following oxides may be entirely converted to their hydroxides by addition of water?
Ag2O, ZnO, CuO, FeO, Fe2O3, CoO, MnO2, Co2O3, NiO
E-2._ Give the reaction for the preparation of ferric oxide from hydrated ferrous sulphate.
E-3._ How do you prepare Ag2O from AgNO3? Explain with the help of chemical reaction.
E-4._ HCl is added to the following oxides, which one would give H2O2?
MnO2, PbO2, BaO,
ADVDBC - 140
E-5._ The precipiate of Zn(OH)2 dissolves in the following reagents- potassium cyanide, ammonia and sodium
hydroxide. Explain with the help of reactions.
E-6. What happens when :

(a) Zinc oxide and cobalt oxide is fused.
(b) Lunar caustic is made to react with sodium hydroxide and then the product is dried.
(c) Cu(OH)2 + NH3·H2O + (NH4)2SO4 
Section (F) : Sulphates and Nitrates

F-1. What happens when :
(a) Green vitriol is strongly heated.
(b) FeSO4 reacts with potassium ferricyanide.
(c) Malachite is made to react with dilute H2SO4 .
(d) Copper sulphate pentahydrate is exposed to air for a longer period.
F-2. Complete and balance the given reaction :

FeSO4 + H2O + O2 
F-3. What happens when silver nitrate solution is added to Na2S2O3 solution and then content is allowed to keep
for a longer period ?
F-4. Why does AgNO3 produce a black stain on the skin ?
F-5. Copper sulphate dissolves in NH3.H2O solution but FeSO4 does not why?
Section (G) : Halides

G-1. The aqueous solution of FeCl3 is acidic. Why?
G-2. Cuprous chloride is insoluble in water and dilute HCl but dissolves in concentrated HCl.
G-3._ The species [CuCl4]2– exists but [CuI4]2– does not. Why?
G-4. Why is AgBr used in photography ?
G-5. What happens when :

(a) Gold is dissolved in aqua regia ?

(b) CuCl2 . 2H2O  

strong
G-6._ Anhydrous FeCl3 cannot be obtained by heating hydrated ferric chloride. Explain
G-7. Although Cu+ does not exist in solution state, but CuCl(s) is formed in presence of Cl– ions in aqueous
solution of Cu(s) and Cu2+.

H-1. Complete and balance the following reactions :
(a) KMnO4 + Na2S2O3 + H2O 
Tempt  70 º C
(b) K2Cr2O7 + H2SO4 + SO2 + H2O     
(c) Fe(III) + 3NH4SCN 
H-2. Which type of reaction MnO42– shows with acid, dilute-alkali or water ?
H-3. Why KMnO4 is stored in dark bottle and what happens to its acidic solution ?
H-4. Why it is not advisable to dissolve KMnO4 in cold and concentrated H2SO4 ?
H-5._ State true or false : Reaction of K2Cr2O7 with cold and concentrated H2SO4 yields bright orange/red precipitate
of CrO3. Write reactions involved.
ADVDBC - 141
H-6._ Write balanced chemical equations for :
i. Mixture of K2Cr2O7 and NaCl is heated with concentrated H2SO4.
ii. Potassium permanganate is added to a hot solution of manganous sulphate.
iii. Potassium dichromate and concentrated HCl are heated together.
iv. Oxidation of cuprous oxide to cupric hydroxide by alkaline KMnO 4.
Section (I) : f-block elements

I-1. What are inner-transition elements ? Decide which of the following atomic numbers are the numbers of the
inner transition elements : 29, 59, 74, 95, 102, 104.
I-2. Actinoid contraction is greater from element to element than lanthanide contraction. Why ?
I-3. The chemistry of the actinoid elements is not so smooth as that of the Lanthanide. Justify this statement by
giving some examples from the oxidation state of these elements.
I-4. Why Sm2+ , Eu2+ and Yb2+ ions in solutions are good reducing agents but an aqueous solution of Ce4+ is a
good oxidizing agent ?

Section (A) : Occurrence, Isolation & Allotropy of Elements
A-1._ Among the following statements, the incorrect is :
(A) Calamine and siderite are carbonate ores (B) Argentite and cuprite are oxide ores
(C) Zinc blende and pyrites are sulphide ores (D) Malachite and azurite are ores of copper.
A-2._ Which ore contains both iron and copper?

(A) Cuprite (B) Chalcocite (C) Chalcopyrite (D) malachite
Section (B) : Periodic trends

B-1._ Amongst which of the following pairs of ions, the lower oxidation state is more stable than the higher oxidation
state in aqueous solution?
(A) Mn2+ , Mn3+ (B) Cu+ , Cu2+ (C) Cr2+ , Cr3+ (D) V2+, VO2+
B-2. First IE of 5d series elements are generally higher than those of 3d and 4d series elements. This is due to :
(A) bigger size of atoms of 5d-series elements than 3d-series elements.
(B) greater effective nuclear charge is experienced by valence electrons because of the weak shielding of the
nucleus by 4ƒ-electrons in 5d series.
(C) (A) and (B) both.
(D) None of these.
Section (C) : Chemical Bonding

C-1._ Which of the following d-block elements has lowest probable interatomic forces ?
(A) Mercury (B) Chromium (C) Iron (D) Zinc
C-2._ Which of the following is stronger base ?

(A) Cu(OH)2 (B) Ni(OH)2 (C) Fe(OH)2 (D) Zn(OH)2
C-3._ Which is the strongest oxidising agent ?

(A) KMnO4 in acidic medium (B) Mn+2 in acidic medium
(C) K2Cr2O7 in acidic medium (D) Cr+3 in acidic medium.

D-1. Which one of the ionic species will impart colour to an aqueous solution ?
(A) Ti4+ (B) Cu+ (C) Zn2+ (D) Cr3+
D-2. When copper is placed in the atmosphere for sufficient time, a green crust is formed on its surface. The
composition of the green crust is :
(A) Cu(OH)2 (B) CuO (C) CuCO3 (D) CuCO3.Cu(OH)2
ADVDBC - 142
D-3._ When same amount of zinc is treated separately with excess of sulphuric acid and excess of sodium
hydroxide, the ratio of volume of hydrogen evolved is.
(A) 1 : 1 (B) 1 : 2 (C) 2 : 1 (D) 9 : 4
D-4._ Dilute HCl will fail to dissolve

(A) Zn and Hg (B) Cd and Hg (C) Hg and Cu (D) Cu and Cd
D-5._ Dilute H2SO4 dissolves Fe to produce :

(A) FeSO4 and H2 (B) Fe2(SO4)3 and H2O (C) SO2 (D) H2
D-6._ Why is metallic iron harder than alkali metals ? Choose the best possible reason.
(A) Iron atoms are small. (B) Iron atoms are more closely packed
(C) Metallic bonds are stronger in alkali metals. (D) Metallic bonds are stronger in iron.
Section (E) : Oxides & Hydroxides

E-1._ Hot copper wire reacts with oxygen to produce :
(A) Cu2O (B) CuO2 (C) Cu2O2 (D) CuO.
E-2._ VO2 is an amphoteric oxide and in acidic medium it forms :

(A) VO2+ (B) VO2+ (C) V3+ (D) VO22+
E-3._ Which of the following hydroxides will not dissolve upon addition of aqueous NH3?
(A) Cu(OH)2 (B) Ni(OH)2 (C) Fe(OH)2 (D) Zn(OH)2
E-4._ Which of the following oxides will not decompose to release oxygen on heating?
(A) CrO3 (B) Cr2O3 (C) MnO2 (D) Mn2O7
Section (F) : Sulphates and Nitrates

F-1._ Aqueous solution of NiSO4 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)
F-2._ To significantly increase 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)
F-3. When AgNO3 (aq) reacts with excess of iodine, we get :

(A) AgO3 (B) HO3 (C) AgO (D) H
F-4._ The colour of light absorbed by an aqueous solution of CuSO 4 is :

(A) orange red (B) blue–green (C) yellow (D) violet
Section (G) : Halides

G-1._ Anhydrous FeCl3 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 dilute hydrochloric acid
(D) Reaction of metallic iron with concentrated hydrochloric acid.
G-2._ VCl5 undergoes hydrolysis with water and forms :

(A) VOCl2 (B) VOCl3 (C) V(OH)2 (D) [V(H2O)6]3+
G-3._ Fe3 is not known whereas FeCl3 and FeBr3 are known. Because -
(A) of larger size of – (B) of greater electronegativity of Cl and Br.
(C) Cl and Br are oxidising (D) – reduces Fe3+ to Fe2+
ADVDBC - 143
G-4._ Highest oxidation state of Mn in fluoride is +4 (i.e. MnF4) but highest oxidation state in oxides is +7 (i.e.
Mn2O7) because :
(A) Fluorine is more electronegative than oxygen
(B) Fluorine does not possess d-orbitals
(C) Fluorine stabilises lower oxidation state
(D) In covalent compounds fluorine can form single bond only, while oxygen forms two single bonds or a
double bond.
G-5._ Auric chloride on reaction with FeSO4 changes to–

(A) Au (B) AuCl (C) Au2SO4 (D) Au3(SO4)2
G-6. FeCl3 dissolves in :

(A) water (B) ether (C) ammonia (D) (A) and (B) both
G-7. The solubility of silver bromide in hypo solution (excess) is due to the formation of :
(A) Ag2SO3 (B) Ag2S2O3 (C) [Ag(S2O3)]– (D) [Ag(S2O3)2]3–
G-8. The developer used in photography is an alkaline solution of :

(A) hydroquinol (B) glycerol (C) phenol (D) picric acid
G-9. Lucas reagent is :

(A) Anhydrous ZnCl2 + HCl (conc.) (B) MnO2 + H2O
(C) H2SO4 + HCl (D) NO + H2O

H-1. KMnO4 is the salt of :
(A) MnO2 (B) Mn2O7 (C) MnO3 (D) Mn2O3
H-2. Which of the following compounds is used as the starting material for the preparation of potassium dichromate?
(A) K2SO4.Cr2(SO4)3.24H2O (chrome alum) (B) PbCrO4 (chrome yellow)
(C) FeCr2O4 (chromite) (D) PbCrO4.PbO (chrome red)
H-3. When acidified solution of K2Cr2O7 is shaken with aqueous solution of FeSO4, then :
(A) Cr2O72– ion is reduced to Cr3+ ions (B) Cr2O72– ion is converted to CrO42– ions
(C) Cr2O72– ion is reduced to Cr (D) Cr2O72– ion is converted to CrO3
H-4. CrO3 dissolves in aqueous NaOH to give :

(A) CrO42– (B) Cr(OH)3 (C) Cr2 O72– (D) Cr(OH)2
H-5. The compound that gets oxidised even on exposure to atmosphere is :

(A) CuSO4 (B) NiSO4 (C) CoSO4 (D) FeSO4
H-6. A compound is yellow when hot and white when cold. The compound is :
(A) Al2O3 (B) PbO (C) CaO (D) ZnO
H-7._ Which pair gives Cl2 at room temp.?

(A) HCl (conc.)+ KMnO4 (B) NaCl + H2SO4 (conc.)
(C) NaCl + MnO2 (D) NaCl + HNO3 (conc.)
H-8._ The product of oxidation of I– with MnO4– in alkaline medium is

(A) IO3– (B) I2 (C) IO– (D) IO4–
x
H-9._ Cr2O72– y
2CrO42–, x and y are respectively..
(A) x = OH–, y = H+ (B) x = H+, y = OH– (C) x = OH–, y = H2O2 (D) x = H2O2, y = OH–
H-10._ Which of the following compounds do not get their colours due to charge transfer spectra?
(A) K2Cr2O7 (B) KMnO4 (C) [Fe(H2O)5NO]SO4 (D) MnO2
ADVDBC - 144
Section (I) : f-block elements
I-1. The f-block of the periodic table contains those elements in which :
(A) only 4f orbitals are progressively filled in 6th period.
(B) only 5f orbitals are progressively filled in 7th period.
(C) 4f and 5f orbitals are progressively filled in 6th and 7th periods respectively.
(D) none
I-2. Among the lanthanide the one obtained by synthetic method is :

(A) Lu (B) Pm (C) Pr (D) Gd
I-3. The most common lanthanide is :

(A) lanthanum (B) cerium (C) samarium (D) plutonium
I-4. Across the lanthanide series, the basicity of the lanthanide hydroxides :
(A) increases (B) decreases
(C) first increases and then decreases (D) does not change
I-5. Actinides :
(A) are all synthetic elements (B) includes element 104
(C) have only short lived isotopes (D) have variable valency
I-6. The +3 ion of which one of the following has half filled 4f subshell ?
(A) La (B) Lu (C) Gd (D) Ac
I-7. The lanthonoide contraction is reponsible for the fact that

(A) Zr and Y have about the same radius (B) Zr and Nb have similar oxidation state
(C) Zr and Hf have about the same radius (D) Zr and Ce have the same oxidation state

1. Match the salts/mixtures listed in column() with their respective name listed in column(II).
(A) K2SO4.Cr2(SO4)3.24H2O (p) Blue vitriol
(B) FeSO4 (NH4)2SO4. 6H2O (q) Green vitriol
(C) CuSO4.5H2O (r) chrome alum
(D) FeSO4.7H2O (s) Mohr's salt
2. Match the reactions listed in column() with the characteristic(s) of the products/type of reactions listed in
column(II).
(A) MnO4 + CO2 
2–
(p) a pungent smelling gas is liberated.
(B) CrO42– + H+  (q) Shows disproportionation reaction.

(C) FeSO4  (r) Dimeric bridged tetrahedral metal ion in the product.

(D) CuCI2.2H2O  (s) One of the products has central atom in its highest possible oxidation state.
3. Match the pairs of complexes/compounds listed in column() with the characteristic(s) of the reaction products
listed in column(II).
(A) Cu(I) and Zn(II) complexes (p) Pair of compounds having similar colour and same but non-zero magnetic
moment.
(B) KMnO4 and K2Cr2O7 (q) Pair of compounds which are diamagnetic but coloured.
(C) Cu2O and HgI2 (r) Pair of compounds having metals in the highest stable oxidation states.
(D) [Cu(NH3)4] and [Ni(NH3)4]
2+ 2+
(s) Pair of compounds which show diamagnetism and are colourless.
ADVDBC - 145

Note : These questions marked as "$" are based on the previous chapters viz. Periodic property, Chemical bonding
& Metallurgy. The students is expected to solve them on their own. No Class Room time is expected to be
devotated by the teacher on these questions.
1.$ Ionisation energies of Ni and Pt in kJ mol–1 are given below.
(IE )1  (IE )2 (IE )3  (IE )4
      
Ni 2.49 8.80
Pt 2.60 6.70
So, (select the correct statement)
(A) nickel (II) compounds tend to be thermodynamically more stable than platinum (II)
(B) platinum (IV) compounds tend to be more stable than nickel (IV)
(C) (A) & (B) both
(D) none is correct
2.$ Atoms of the transition elements are smaller than those of the s-block elements, because :
(A) there is increase in the nuclear charge along the period.
(B) orbital electrons are added to the penultimate d–subshell rather than to the outer shell of the atom.
(C) the shielding effect of d-electrons is small.
(D) All of these
3.$ Match the compounds of column X with oxidation state of central atom in column Y.
Column X Column Y
I [Cr(H2O)6]Cl3 5
II CrO5 8
III HNO3 6
IV OsO4 3
I II III IV I II III IV
(A) 3 6 5 8 (B) 3 8 5 6
(C) 8 5 6 3 (D) 6 5 8 3
4.$ Standard reduction electrode potential of Zn2+ / Zn is – 0.76 V. This means :

(A) ZnO can’t be reduced to Zn by H2 under standard conditions.
(B) Zn can't liberates H2 with concentrated acids
(C) Zn is generally the anode in an electrochemical cell
(D) Zn is generally the cathode in an electrochemical cell
5.$ E values for the couples Cr3+/Cr2+ and Mn3+/Mn2+ are – 0.41 and + 1.51 volts respectively. Considering these
values select the correct option from the following statements.
(A) Cr2+ acts as a reducing agent and Mn3+ acts as an oxidising agent in their aqueous solutions.
(B) Cr2+ (aq.) is more stable than Cr3+ (aq.).
(C) Mn3+ (aq.) is more stable than Mn2+ (aq).
(D) None of these.
6. Of the ions Zn2+, Ni2+ and Cr3+ (atomic number Zn = 30, Ni = 28, Cr = 24) :
(A) only Zn2+ is colourless and Ni2+ and Cr3+ are coloured.
(B) all three are colourless.
(C) all three are coloured.
(D) only Ni2+ is coloured and Zn2+ and Cr3+ are colourless.
ADVDBC - 146
7. Iron is rendered passive by treatment with concentrated :
(A) HCl (B) H2SO4 (C) HNO3 (D) both (B) & (C)
8. Which one of the following dissolves in hot concentrated NaOH ?

(A) Fe (B) Zn (C) Cu (D) Ag
9. Aqueous solution of which of the following ions is green ?

(A) V2+ (B) V3+ (C) VO2+ (D) VO2+
10. Aqueous solutions of (P) and (Q) are violet. (P) turns green on oxidation while (Q) turns green on reduction.
They may respectively be :
(A) VCl2, CrO3 (B) VCl3, KMnO4 (C) VSO4, KMnO4 (D) VOSO4, K2MnO4
11. At 300ºC, FeCl3(s) :

(A) decomposes into FeCl2 and Cl2. (B) decomposes into Fe and Cl2.
(C) sublimes to give liquid FeCl3. (D) sublimes to give gaseous dimer (FeCl3)2.
12. In the reaction, 2CuCl2 + 2H2O + SO2  A + H2SO4 + 2HCl ; A is

(A) CuCl (B) Cu (C) CuSO4 (D) CuS
13. German silver is an alloy of copper and :

(A) Zn + Ni (B) Al + Ag (C) Zn + Ag (D) Sn + Zn
14. When H2O2 is added to an acidified solution of K2Cr2O7 :

(A) solution turns green due to formation of Cr2O3
(B) solution turns yellow due to formation of K2CrO4
(C) a blue coloured compound CrO(O2)2 is formed
(D) solution gives green ppt of Cr(OH)3
15. Sodium thiosulphate is used in photography because of its :

(A) oxidising behaviour (B) reducing behaviour
(C) complexing behaviour (D) photochemical behaviour
16. Lanthanide contraction is due to increase in :

(A) shielding by 4f electrons (B) atomic number
(C) effective nuclear charge (D) size of 4f orbitals
17. Which of the following is not an actinide ?

(A) Curium (B) Californium (C) Uranium (D) Terbium
18. The correct statement(s) from among the following is/are ?

(i) all the d and f-block elements are metals
(ii) all the d and f-block elements form coloured ions
(iii) all the d- and f-block elements form paramagnetic ions
(A) (i) only (B) (i) and (ii) (C) (ii) and (iii) (D) All
19. Which of the following statements is not correct ?

(A) La(OH)3 is less basic than Lu(OH)3.
(B) In lanthanide series ionic radius of Ln3+ ions decreases.
(C) La is actually an element of transition series rather than lanthanide series.
(D) Atomic radii of Zr and Hf are same because of lanthanide contraction.

1.$ Total number of 3d-series transition elements contain either 3d1 or 4s1 orbital in their ground state electronic
configuration.
2.$ How many of the following show variable oxidation states in their compounds ?
Sc, Cr, Cu, Zn, Fe, Hg, La
ADVDBC - 147
3.$ Magnetic moment value for a d-block ion is 4.90 BM determine value of total spin for it (consider clock wise
spin)
4.$ Determine total number of unpaired electrons in following ions

Ti3+, V3+, Cr3+, Cr2+, Mn3+, Mn2+, Fe3+, Fe2+, Co2+, Ni2+, Cu2+
5.$ An element of Ist transition series X+3 have highest magnetic moment in series and X+2 have non magnetic
nature as low spin complex. If Atomic number of X is ‘a’ and number of unpaired e– in free state X+2 and X+3
is ‘b’ and ‘c’ then calculate a + b + 2c.

6. FeC2O4   products
Number of diamagnetic products= x
Number of unpaired electrons in paramagnetic product = y
Report your answer as (x + y).
7. No. of following reagents in which ppt A is soluble is :

AgNO3 + NaCl  A 
(i) aq NH3 (ii) aq. KCN (iii) Na2S2O3
(iv) Conc. HCl (v) aq. NaOH (iv) aq. KI
8._ The number of water molecule(s) directly bonded to the metal centre in CuSO 4.5H2O is–
9. How many of the following statements are correct for green vitriol?
1. It can be used for the preparation of Mohr’s salt.
2. It is a hydrated salt and its anhydrous form is white in colour.
3. The decomposition reaction of its anhydrous form is redox in nature.
4. It is used for making Fenton’s reagent used as a catalyst in organic chemistry
5. It can be used for the preparation of Potassium ferrocyanide.
6. It has same number of molecules of water of crystallization as white vitriol or blue vitriol.
7. It turns brownish-yellow on exposure to atmosphere.
8. Its aqueous solution is acidic in nature due to hydrolysis.
9. Out of the decomposition products of its anhydrous form, only one can turn acidified K2Cr2O7 solution
green.
10. Chromite ore is processed through the following sequence :

Boil 
Na2O2
FeCr2O4 
Fuse
 {(A) + (B)} 
H2 O
 (B)aq. 
excess H
 (C)
H2 O2 NaOH warm H
(H)  (G)   (F)    (E)   (D)
NH3 little
excess –O2
In this sequence how many species (from A to H) show green colour ?

H
11. KMnO4 
R.A.
 Mnx
–
OH
KMnO4 
R.A.
 Mny
–
OH
K2Cr2O7  Crz
x + y + z is %
12. The no. of electrons satisfying n+l = 7 for Lu (Atomic number : 71)
ADVDBC - 148
13. The heavier members of lanthanoid series metal react with following non-metal.
The summation of atomicity of compound X, Y and Z is ?

1.$ Correct statements about transition metals are that they :
(A) form complex (B) show variable oxidation states
(C) show magnetic properties (D) do not form coloured compounds
2.$ Transition elements have greater tendency to form complexes because they have :
(A) vacant d–orbitals (B) small size
(C) higher nuclear charge (D) variable oxidation states
3.$ The less stable oxidation states of Cr are :

(A) Cr2+ (B) Cr 3+ (C) Cr 4+ (D) Cr 5+
4.$ Which of the following statements are correct ?

(A) Transition elements exhibit higher enthalpies of atomization as they have stronger interatomic interaction
(B) E2 of 23V < 24Cr > 25Mn and 28Ni < 29Cu > 30Zn
(C) Ni(II) compounds are more stable than Pt(II) where as Pt(IV) compounds are more stable than nickel (IV)
(D) The elements which gives the greatest number of oxidation states does not occur in or near the middle of
the series.
5._ Which of the following is/are soluble is excess of NaOH

(A) Al(OH)3 (B) Cr(OH)3 (C) Fe(OH)3 (D) Zn(OH)2
6. The melting point of Zn is lower as compared to those of the other elements of 3d series because :
(A) the d-orbitals are completely filled.
(B) the d-orbitals are partially filled.
(C) d-electrons do not participate in metallic bonding.
(D) size of Zn atom is smaller
7. The colour of the transition metal ions is/are due to :

(A) d-d transition of electrons in presence of ligands
(B) charge transfer from ligand to metal ion.
(C) change in the geometry
(D) polarisation of anion by cation
8. Which of the following ions give(s) colourled aqueous solution?

(A) Ni2+ (B) Fe2+ (C) Cu2+ (D) Cu+
9. What are the characteristics of products obtained when green vitriol is strongly heated ?
(A) Basic oxide (B) Neutral oxide (C) acidic oxide (D) Reducing agent
10. Which of the following reaction(s) is/are used for the preparation of anhydrous FeCl3 ?
(A) FeCl3 6H2O + 6SOCl2  FeCl3 + 12HCl + 6SO2
(B) Fe(OH)3  + 3HCl  FeCl3 + 3H2O
(C) 2Fe + 4HCl (aq.) + Cl2  2FeCl3 + 2H2
(D) 2Fe + 3Cl2(dry)  2FeCl3
ADVDBC - 149
11. Cuprous chloride can be prepared :
(A) by passing SO2 through the solution containing CuSO4 and NaCl.
(B) by heating excess of copper with concentrated HCl in presence of a little KCIO 3.
(C) by boiling copper sulphate solution with excess of copper turnings in presence of hydrochloric acid.
(D) by dissolving cupric oxide or copper carbonate in concentrated HCI.
12. Which of the following chemical reaction(s) is/are involved in developing of photographic plate ?
(A) C6H4(OH)2 + 2AgBr  2Ag + C6H4O2 + 2HBr
(B) AgBr + 2Na2S2O3  Na3 [Ag(S2O3)2] + NaBr
(C) 2AgNO3 + Na2S2O3  Ag2S2O3 + 2NaNO3
(D) AgNO3 + KCN  AgCN + KNO3
13. Which of the following statements are correct when a mixture of NaCl and K2Cr2O7 is gently warmed with
conc. H2SO4 ?
(A) Deep red vapours are liberated
(B) Deep red vapours dissolve in NaOH (aq.)forming a yellow solution.
(C) Greenish yellow gas is liberated
(D) Deep red vapours dissolve in water forming yellow solution
14. Which of the following statement (s) is/are correct ?

(A) S2O82– oxidises Mn2+ to give pink colour.
(B) MnO42– disproportionates to yield MnO4– and MnO2 in presence of H+ ions.
(C) In Cr2O72– each Cr is linked to four oxygen atoms.
(D) Ti3+ is purple while Ti4+ is colourless.
15. Pyrolusite is MnO2 used to prepare KMnO4. Steps are :

I II
MnO2 
 MnO42–  MnO4–
Steps I and II are respectively :
(A) fuse with KOH / air, electrolytic oxidation
(B) fuse with KOH / KNO3 , electrolytic oxidation
(C) fuse with concentrated HNO3 / air, electrolytic reduction
(D) dissolve in H2O, oxidation
16. Which of the following statements are correct

(A) Tendency to form complex : Sc+3 > Y+3 > La+3
(B) Most of Ln3+ are coloured.
(C) Ln(II) hydroxides are mainly basic in character
(D) Lanthanoids release H2 on reaction with strong acids
Read the following comprehension carefully and answer the questions :
Comprehension # 1
Transition metals usually form coloured complexes and d–d transitions (t2g eg) are responsible for colour
as the energy difference between t2g and eg lies in visible region. But all the coloured ions are not due to d–d
transition but charge transfer bands also play important roles. Charge transfer bands may be of two types.
(i) ligand to metal (CTLM) (ii) metal to ligand (CTML).
Charge transfer transition always produces intense colour as compared to d-d transition.
1. Select the incorrect statement :

(A) d-block metal ions are usually coloured.
(B) Colour of the most of d-block metal ions is generally due to d-d transition.
(C) All the complexes of Cu+ are colourless on account of diamagnetic nature i.e. d10 configuration.
(D) CrO3 is bright orange due to CTLM.
ADVDBC - 150
2. MnO4– is dark purple coloured although Mn is in (+ VII) oxidation state with 3dº configuration :
(A) due to d-d transition. (B) due to CTML spectra.
(C) due to CTLM spectra (D) none of these.
3. Select the correct statement.

(A) In CTML, no net reduction-oxidation takes place because of the short life time of excited state.
(B) Cu2O is a red coloured salt.
(C) HgO is a red coloured compound.
(D) All of these.
Comprehension # 2
Pyrolusite ore on oxidation with KClO3/KNO3 in basic medium produces dark green coloured compound
(A), which on electrolysis produces a purple coloured compound (B). The purple coloured compound
can be crystallised to deep purple rhombic prisms. It shows different reactions in different mediums.
Excess of compound (B) on heating with concentrated H2SO4 gives an explosive oil (C), which on
heating decomposes to gives another compound (D) along with oxygen.
4. On passing CO2 in the solution of (A), a purple coloured solution along with brown precipitate is observed.
Select the correct statement.
(A) This is a disproportionation reaction where oxidation number changes from +6 to +7, +4.
(B) This is a comproportionation reaction where oxidation number changes from +3 to +2.
(C) both (A) and (B)
(D) none
5. The nature of compound (C) is :

(A) basic (B) acidic (C) neutral (D) amphoteric
6. Identify (D).
(A) Mn2O7 (B) MnO2 (C) MnSO4 (D) Mn2O3
ADVDBC - 151
EXERCISE - 1
PART - I
A-1. Cu, Ag, Au, Hg Pt are noble metals.
Cu, Ag, Au are called coinage metals.
A-2. (i) Siderite (ii) Cinnabar (iii) Malachite
(iv) Iron pyrites (v) Zinc Blende (vi) Horn Silver
B-1. +2&+3
B-2. In the 5d series, after lanthanum (Z = 57), there is lanthanide contraction. As a result, in each group the
atomic size of 5d element is small and its nuclear charge is large. Hence the ionisation energies of 5d
elements are large than 3d elements.
HO O
C-1. Ti
HO O
O O
Mn Mn
C-2. ;
O O– O O–
O O–
C-3. Enough unpaired electrons are not available for effective metallic bonding for zinc.
C-4. MnO2, Co2O3, HgO, Ag2O
C-5. V2O5 > V2O4 > V2O3
C-6. Fe(OH)2 is more basic than Fe(OH)3
C-7. Cr (Its electrode reduction potential value is more negative as compared to Fe.
D-1. (i) Ti3+ (3d1), Cu2+ (3d9) and Mn2+ (3d5) have unpaired electron(s). Thus they are coloured due to d-d transition
of electron according to CFT.
(ii) Zn2+(3d10), Ti+4 (3d0) and Cd2+ (4d10) do not have unpaired electron(s). Thus they do not under go d-d
transition of electron according to CFT and, therefore, are colourless.
D-2. Copper has less standard oxidation potential (Eop° ) than H2 and thus cannot liberate H2 from acids. However,
it dissolves in nitric acid because HNO3 is strong oxidant.
3Cu + 8HNO3 (dilute)  3Cu (NO3)2 + 4H2O + 2NO
D-3. Zn D-4. H2S and O2. D-5. 3Ag + 4HNO3  3AgNO3 + NO+ 2H2O
E-1. Zero E-2. 2FeSO4.H2O  Fe2O3 + SO2 + SO3  + 2H2O

E-3. 2AgNO3 + 2NaOH  Ag2O  + 2NaNO3 + H2O E-4. None
E-5. Zn(OH)2  + 4KCN  K2[Zn(CN)4] + 2KOH

colourless soluble complex
Zn(OH)2  + 4NH3  [Zn(NH3)4](OH)2
Zn(OH)2  + 2NaOH  Na2[Zn(OH)4] (OH)2
ADVDBC - 152
E-6. (a) ZnO + CoO  CoZnO2 (Rinmann's green)
(b) 2AgNO3 + 2NaOH  Ag2O  (black) + 2NaNO3 + H2O
(c) Cu(OH)2 + 2NH3·H2O + (NH4)2SO4  [Cu(NH3)4 ]SO4 (Schitzer reagent) + 4H2O
300 º C high
F-1. (a) FeSO4.7H2O  FeSO4  Fe O + SO + SO
2 3 2 3
– 7H2O tempt
(b) 3FeSO4 + 2K3 [Fe(CN)6]  Fe3[Fe(CN)6]2 + 3K2SO4

(blue)
(c) CuCO3.Cu(OH)2 + 2H2SO4  2CuSO4 + 3H2O + CO2 
air
(d) CuSO4.5H2O (blue)   CuSO4.3H2O (pale blue)
effloresce s
F-2. 4FeSO4 + 2H2O + O2  4Fe (OH).SO4

(yellow brown)
F-3. White precipitate of Ag2S2O3 is obtained which turns yellow, orange, brown and finally black on keeping.
2AgNO3 + Na2S2O3  Ag2S2O3 (white) + 2NaNO3
Ag2S2O3 + H2O  Ag2S (black) H2SO4
F-4. In presence of organic matter (skin) and light, AgNO3 decomposes to produce a black stain of metallic silver.
2AgNO3  2Ag + 2NO2 + O2
F-5. Copper sulphate dissolves in the ammonium hydroxide due to formation of a copper complex. Ferrous
sulphate reacts with NH4OH to form insoluble Fe(OH)2 . It does not form any complex with NH4OH.
CuSO4 + 4NH3·H2O  [Cu(NH3)4]SO4 + 4H2O
Deep blue solution
FeSO4 + 2NH3·H2O  Fe(OH)2 + (NH4)2 SO4
Insoluble
G-1. In aqueous solution, Fe3+ ions undergo hydrolysis as follows :
Fe3+ + H2O Fe(OH)2+ + H+
Fe(OH)2+ + H2O Fe(OH)2 + H+
Fe(OH)2 + H2O Fe(OH)3  + H+
Hence, it forms an acidic solution.
G-2. CuCl dissolves in conc. HCl due to the formation of a chlorido complex.
CuCl + 2HCl  2H[CuCl2]
G-3. Cu+2 is reduced to Cu+ by I–, hence cupric iodide is converted into cuprous iodide. Cl– cannot affect this
change, since it is not a reductant.
G-4. AgBr is sensitive to light and undergoes photo decomposition to metallic silver instantaneously on exposure
to light.
2AgBr  2Ag + Br2
Unexposed AgBr can be dissolved in hypo (Na2S2O3) solution, obtaining a black image on the original paper
where the light rays fall. Thus produces the "negative" photograph.
AgBr + 2Na2S2O3  Na3 [Ag(S2O3)2] + NaBr..
G-5. (a) Au + 5HCl + HNO3  HAuCl4 + NOCl  + 2H2O


(b) 3CuCl2.2H2O  

strong CuO + Cu2Cl2 + 2HCl + Cl2 + H2O
G-6. On heating hydrated ferric chloride, anhydrous ferric chloride is not formed, as water of crystallization reacts
to from Fe2O3 and HCl.
ADVDBC - 153
G-7. In presence of Cl– ion the disproportionation of Cu+ i.e.
2Cu+(aq) — Cu(s) + Cu2+(aq)
is reversed because precipitation of copper (I) chloride drives the disproportionation reaction to the left.
Cu(s) + Cu2+(aq) + 2Cl–(aq) — 2CuCl(s)
H-1. (a) 8MnO4– + 3S2O32– + H2O  8MnO2 + 6SO42– + 2OH–

temp. 70 º C
(b) K2Cr2O7 + H2SO4 + 3SO2 + 23H2O    K2SO4 . Cr2(SO4)3 . 24H2O
crystallise
(c) Fe(III) + 3NH4SCN  [Fe(SCN)3] (blood red colouration) + 3 NH4+

H-2. It is unstable in acidic medium and disproportionates. It is stable only around pH 14. It disproportionates at
lower pHs.
3MnO42– + 4H+  MnO2 + 2MnO4– + 2H2O
3MnO42– + 2H2O  2MnO4– + MnO2 + 4OH–
H-3. MnO4– solutions are intrinsically unstable in acidic solutions and decompose slowly. This decomposition is
catalysed by sun light hence KMnO4 solution is kept in dark bottles.
h
4MnO4– + 4H+ 
 4MnO2 + 3O2 + 2H2O
slow
H-4. Because explosive Mn2O7 is formed.

2KMnO4 + 2H2SO4  Mn2O7 + 2KHSO4 + H2O
On warming, this Mn2O7 can explode.
2Mn2O7  4MnO2 + 3O2
H-5. True
H-6. (i) K2Cr2O7 + 4NaCl + 6H2SO4  2CrO2Cl2  + 4NaHSO4 + 2KHSO4 + 3H2O

orange
(ii) 2KMnO4 + 3MnSO4 + 2H2O  5MnO2 + K2SO4 + 2H2SO4

(iii) K2Cr2O7 + 14HCl 

 2KCl + 2CrCl + 7H O + 3Cl
3 2 2
(iv) KMnO4 + Cu2O + KOH 2Cu(OH)2 + K2MnO4
I-1. The f-block elements, in which the last electron enters into f-subshell are called inner transition elements.
These include lanthanoids (58-71) and actinoids (90-103). Thus elements with atomic numbers 59,95 and
102 are inner transition elements.
I-2. The 5f electrons are more effectively shielded from nuclear charge. In other words the 5f electrons themselves
provide poor shielding from element to element in the series.
I-3. Lanthanide show limited number of oxidation state, viz, +2, +3 and +4 (out of which +3 is most common).
This is because of large energy gap between 4f, 5d and 6s subshells, the dominant oxidation state of
actinoids is also + 3 but they show a number of other oxidation states also, e.g. uranium (Z = 92) and
plutonium (Z = 94), show +3 +4 +5 and +6 neptunium (Z = 94) shows +3 +4 +5 and +7 etc. This is due to
small energy difference between 5f, 6d and 7s subshell of the actinoids
I-4. The most stable oxidation state of lanthanides is +3. Hence, ions in +2 state tend to change to +3 state by
loss of electron and those in +4 state tend to change to +3 state by gain of electron.
PART - II
A-1. (B) A-2. (C) B-1. (A) B-2. (B) C-1. (A)
C-2. (C) C-3. (A) D-1. (D) D-2. (D) D-3. (A)
D-4. (C) D-5. (A) D-6. (D) E-1. (D) E-2. (A)
E-3. (C) E-4. (B) F-1. (D) F-2. (B) F-3. (B)
F-4. (A) G-1. (B) G-2. (B) G-3. (D) G-4. (D)
ADVDBC - 154
G-5. (A) G-6. (D) G-7. (D) G-8. (A) G-9. (A)
H-1. (B) H-2. (C) H-3. (A) H-4. (A) H-5. (D)
H-6. (D) H-7. (A) H-8. (A) H-9. (A) H-10. (D)
I-1. (C) I-2. (B) I-3. (B) I-4. (B) I-5. (D)
I-6. (C) I-7. (C)
PART - III
1. (A) - r ; (B) - s ; (C) - p ; (D) - q.
2. (A) - q, s ; (B) - r, s ; (C) - p, s ; (D) - p
3. (A) - s ; (B) - q, r ; (C) - q ; (D) - q
EXERCISE - 2
PART - I
1. (C) 2. (D) 3. (A) 4. (A) 5. (A)
6. (A) 7. (D) 8. (B) 9. (B) 10. (C)
11. (D) 12. (A) 13. (A) 14. (C) 15. (C)
16. (C) 17. (D) 18. (A) 19. (A)
PART - II
1. 3 2. 4 3.$ 2 4.$ 34 5.$ 39
6. 6 7. 4 ((i), (ii), (iii), (iv)) 8. 4 9. 8
10. 3 11. 12 12. 15 13. 11
PART - III
1.$ (A,B,C) 2.$ (A,B,C) 3.$ (A,C,D) 4.$ (A,B,C) 5. (A,B,D)
6. (A,C) 7. (A,B,D) 8. (A,B,C) 9. (A,B,C,D) 10. (A,D)
11. (A,B,C) 12. (A,B) 13. (A,B,D) 14. (A,B,C,D) 15. (A,B)
16. (A,B,C,D)
PART - IV
1. (C) 2. (C) 3. (D) 4. (A) 5. (B)
6. (B)
ADVDBC - 155
d & f-block elements & their important compound

above.
1. The maximum oxidation state shown by V(Z = 23), Cr(Z = 24), Co(Z = 27), Sc(Z = 21) are respectively :
(1) + 5 , + 6 , + 3 , + 3 (2) + 3 , + 4 , + 5, + 2
(3) + 5, + 3 , + 2 , + 1 (4) + 4 in each case.
2. Which oxide of manganese is most acidic in nature ?

(1) MnO (2) Mn2O7 (3) Mn2O3 (4) MnO2 .
3. The first ionisation energies of the elements of the first transition series :
(1) generally increases as the atomic numbers increase.
(2) decrease as the atomic number increase.
(3) do not show any change as the addition of electrons takes place in the inner (n – 1) d–orbitals.
(4) increase from Ti to Mn and then decrease from Mn to Cu.
4. The ions from among the following which are colourless are :
(i) Ti4+ , (ii) Cu+1 , (iii) Co3+ , (iv) Fe2+ .
(1) (i) and (ii) only (2) (i), (ii) and (iii) (3) (iii) and (iv) (4) (ii) and (iii).
5. Which of the following transition metal ions has least magnetic moment ?
(1) Co3+ (2) Fe3+ (3) Cr2+ (4) V3+
6. If a non metal is added to the interstitial sites of a metal, then the metal becomes :
(1) softer (2) less tensile (3) less malleable (4) more ductile.
7. The pair of the compounds in which both the metals are in the highest possible oxidation state is,
(1) [Fe(CN)6]3– , [Co(CN)6]3– (2) CrO2Cl2 , MnO4– .
(3) TiO2 , MnO2 (4) [Co(CN)6]3–, Mn2O7 .
8. Solution of CuCl in NH3.H2O does not absorb :

(1) N2 (2) SO2 (3) C2H2 (4) CO.
9. A compound of iron exists as a dimer in vapour state. It is hygroscopic in nature and dissolves in water giving
brown acidic solution. The compound is :
(1) Fe3O4 (2) FeSO4 (3) FeCl3 (4) FeCl2.
ADVDBC - 156
10. Select the correct statement(s) regarding oxides of copper:
(1) CuO is black & Cu2O is white in colour.
(2) Commercially, CuO is obtained by calcination of haematite ore.
(3) Hydrated cupric chloride upon strong heating produces CuO as one of the product.
(4) Upon partial roasting of chalcopyrites ore in metallurgy, Cu2O is obtained as one of the product.
11. Select the correct statements :

(1) CuCl2.2H2O is a green crystalline solid.
(2) Blue vitriol is used for making Fehling’s solution & Bordeause mixture.
(3) Anhydrous CuCl2 is dark brown solid.
(4) All of these
12. 2CuSO4 + 2NaCl + SO2 + 2H2O  Compound + Na2SO4 + 2H2SO4

X
Compound X gradually turns green on exposure in air due to oxidation.
Correct statement about compound X is :
(1) Compound X is Cu2Cl2 (2) Compound X forms black ppt with H2S
(3) Compound X is soluble in aq. NH3 solution (4) All of these
13. Which of the following are correct ?

(1) Anhydrous ferric chloide can not be obtained by heating hydrated ferric chloride.
(2) FeSO4 can be used as primary standard.
(3) ZnCl2 solution on treating with H2S gives black precipitate.
(4) CuSO4 and FeSO4 both gets dissolved in NH4OH.
14. Cu2+ can be reduced to Cu+ on addition of :

(1) Hyposolution (2) KCN (aq) (3) KSCN (4) All of these
15. When FeSO4 is strongly heated, the number of acidic gases produced is :
(1) One (2) Two (3) Three (4) Four
Fe(CN)3 + KCN   X 

FeCl3 SCln
16. Y
Y is :
(1) Brown colored complex,Inner orbital complex
(2) White colored complex , Inner orbital complex
(3) Blue colored complex, outer orbital complex
(4) Blue coloured compex, Inner orbital complex
17. On heating KMnO4, one among the following is not formed :

(1) K2MnO4 (2) O2 (3) MnO2 (4) MnO.
18. Reaction of KMnO4 in neutral or very weakly alkaline solution can be represented as :
(1) MnO4– + 2H2O + 3e–  MnO2 + 4OH– . (2) 2MnO4– + 2OH–  2MnO42– + 1/2O2 + H2O.
(3) MnO4– + 8H+ + 5e–  Mn2+ + 4H2O. (4) MnO4– + e–  MnO42–
19. KMnO4 in excess on treatment with concentrated H2SO4 forms a compound (X) which decomposes explosively
on heating forming (Y) . The (X) and (Y) are respectively :
(1) Mn2O7 , MnO2 (2) Mn2O7 , Mn2O3 (3) MnSO4 , Mn2O3 (4) Mn2O3 , MnO2
20. Which of the following statement is wrong ?

(1) An acidified solution of K2Cr2O7 liberates iodine from iodides.
(2) In acidic solution dichromate ions are converted to chromate ions.
(3) Ammonium dichromate on heating undergo exothermic decomposition to give Cr2O3 .
(4) Potassium dichromate is used as a titrant for Fe2+.
21. The image on an exposed and developed photographic film is due to :

(1) AgBr (2) [Ag(C2O3)2]3+ (3) Ag (4) Ag2O.
ADVDBC - 157
22. The yellow colour solution of Na2CrO4 changes to orange red on passing CO2 gas due to the formation of :
(1) CrO5 (2) CrO3 (3) Na2Cr2O7 (4) Na3CrO8.
23. What happens when a molten mixture of K2FeO4 and K2CrO4 is acidified ?
(1) FeO42– is converted to H2FeO4 (2) CrO42– is reduced to Cr3+ liberating O2
(3) CrO4 is converted to Cr
2– 3+
(4) FeO42– is reduced to Fe3+ liberating O2
24. Why silver chloride is used in photochromic spectacles ?

(1) Silver halides darken in light owing to photochemical decomposition
(2) Silver halides produced elemental silver in light.
(3) If the halogen produced is kept in close proximity to finely divided silver chloride, the silver metal is formed.
(4) All of these.
25. In which of the following reactions, reaction of silver with the given acids lead to the formation of compound &
silver, along with liberation of gas ?
(1) Ag + dilute HNO3 (2) Ag + Conc. HNO3 (3) Ag + conc. H2SO4 (4) All of these
26. Which of the following can be used for the conversion of potassium manganate to potassium permanganate?
(1) O3 (2) Cl2 (3) CO2 (4) All.
27. Reaction of potassium chromate and CuSO4 in aqueous solution produces :

(1) CuCrO4 only (2) Cu5[CrO4]2 only (3) CuCr2O7 only (4) both CuCrO4 and Cu2Cr2O7.
28. Pick out the correct statements from the following :

1. Cobalt (III) is more stable in octahedral complexes.
2. Zinc forms coloured ions or complexes
3. Most of the d-block elements and their compounds are ferromagnetic
4. Osmium shows (VIII) oxidation state
5. Cobalt (II) is more stable in octahedral complexes.
(1) 1 and 2 (2) 1 and 3 (3) 2 and 4 (4) 1 and 4
29. Transuranic elements begin with

(1) Np (2) Cm (3) Pu (4) U
30. Lanthanide contraction is observed in :

(1) Gd (2) At (3) Xe (4) Ac

Que. 1 2 3 4 5 6 7 8 9 10
Ans.
Que. 11 12 13 14 15 16 17 18 19 20
Ans.
Que. 21 22 23 24 25 26 27 28 29 30
Ans.

1. When a piece of copper wire is immersed in a silver nitrate solution, the colour of the solution turns blue due
to [NSEC-2000]
(A) oxidation of silver (B) reduction of copper
(C) oxidation of copper (D) formation of soluble complex
ADVDBC - 158
2. The oxidation state of Cr in K2Cr2O7 is : [NSEC-2000]
(A) + 3 (B) + 6 (C) + 4 (D) – 4
3. Oxidation Number of Mn in [MnO4] is : [NSEC-2001]

(A) –7 (B) + 7 (C) + 2 (D) – 2
4. The reduction potentials of Zn, Cu, Fe and Ag are in the order : [NSEC-2001]
(A) Zn > Cu > Fe > Ag (B) Cu > Ag > Fe > Zn (C) Ag >Cu > Fe > Zn (D) Fe > Zn > Cu > Ag
5. The outermost electron configuration of one of the element is 52, 6d1, 7s2. This element belongs to
[NSEC-2002]
(A) s-block (B) transition series (C) lanthanide series (D) actinide series.
6. If H2S gas is passed in a acidified ZnSO4, the precipitation of ZnS does not take place because
(A) Ksp of ZnS is not exceeded (B) Ksp of ZnS is decreases [NSEC-2002]
(C) Ksp of ZnS is increases (D) none of these
7. Platinum metal (Pt) dissolves in aquaregia but not in concentrated HCI or HNO 3 because [NSEC-2003]
(A) HCI oxidises Pt in the presence of HNO3
(B) HNO3 reacts with HCI to form chlorine which attacks Pt
(C) HNO3 oxidises Pt which is followed by formation of a chloro complex
(D) HCI and HNO3 together give O2 that oxidises Pt.
8. The aqueous solution of a salt of a transition metal ion changes colour from pink to blue, when concentrated
hydrochloric acid is added to it. The change in colour is due to [NSEC-2003]
(A) evolution of hydrogen that changes the oxidation state of the metal ion
(B) change in the coordination number of the metal ion from 6 to 4 and formation of new species in solution
(C) formation of a coordination complex of the metal ion with hydrochloric acid
(D) protonation of the metal ion.
9. A solution containing Co2+ , Zn2+ and AI3+ is mixed with an excess of KSCN solution. The resulting solution
besides the unreacted ions, should contain [NSEC-2003]
(A) [Co(SCN)6] 4-
(B) [Zn(NCS)6] 2-
(C) AI(SCN)3 (D) Zn(SCN)2.
(A) K4[Fe(CN)6] (B) K2[Fe(CN)4(NH3)2] (C) Fe4[Fe(CN)6]3 (D) Na2[Fe(CN)5NO].
11. When H2S is passed through a solution containing Cu2+, Cd2+ and an excess of cyanide ions, cadmium
12. Iron articles get rusted on weathering due to the formation of [NSEC-2003]
(A) FeO (B) Fe2O3 (C) Fe3O4 (D) Fe(OH)3
13. Generation of a blue colour which is not due to metal ammonia complex formation is seen when
(A) sodium is dissolved in liquid ammonia [NSEC-2003]
(B) copper (II) sulphate is reacted with ammonium hydroxide
(C) cobalt (II) chloride is reacted with ammonium hydroxide
(D) formaldehyde is reacted with ammonuim hydroxide.
14. Chromium has the lowest oxidation state in [NSEC-2003]

(A) chromium sulphate (B) chromium trioxide
(C) potassium chromate (D) potassium dichromate.
15. Paramagnetism is not exhibited by [NSEC-2004]

(A) CuSO45H2O (B) CuCI25H2O (C) CuI (D) NiSO4.6H2O.
ADVDBC - 159
16. Silver iodide is used to produce artificial rain because. [NSEC-2005]
(A) it is stable at high temperature (B) it is insoluble in rain water
(C) it can be easily spread (D) it has a seeding effect.
17. Articles made of copper or bronze slowly tarnish in air and turn green. The green colour is due to the
formation of [NSEC-2005]
(A) copper sulphide (B) copper oxide
(C) basic copper carbonate (D) copper oxalate.
18. The cation containing maximum number of unpaired electrons is [NSEC-2005]
(A) Fe (II) (B) Fe (III) (C) Co (II) (D) Ni (II)
19. 1000 mL of a gas weighs 1.5 g at NTP. Its gram molecular weight is [NSEC-2005]
(A) 22.4 g (B) 33.6 g (C) 11.2 g (D) 15 g.
20. Rusting of iron is due to the formation of [NSEC-2006]
(A) hydrated ferrous oxide (B) hydrated ferric oxide
(C) only ferric oxide (D) a mixture of ferric oxide and Fe(OH)3.
21. The brown ring test for NO2– and NO3– is due to formation of complex ion with formula [NSEC-2006]
(A) [Fe(H2O)6]2+ (B) [Fe(CN)5(NO)]2– (C) [Fe(H2O)5(NO)]2+ (D) [Fe(H2O)(NO)5]2+
22. In which of the following compounds is the oxidation number of the transition metal zero? [NSEC-2007]
(A) [Ni(CO)4] (B) [Pt(C2H4)Cl3 (C) [Co(NH3)6]Cl2 (D) [Fe(H2O)3](OH)2
23. As the number of electrons in d-orbitals of transition elements increases, the screening effect on the valence
electrons- [NSEC-2007]
(A) increases (B) decreases greatly (C) is not observed (D) decreases slightly
24. The magnetic moment of MnSO4.4H2O is: [NSEC-2007]

(A) 1.73 BM (B) 3.87 BM (C) 4.09 BM (D) 5.92 BM
25. Metal carbonyls have the metal ions in zero or unusually lower oxidation states. This is because
[NSEC-2007]
(A) carbonyl ligand is reducing in nature. (B) carbonyl is a highly electron rich ligand.
(C) carbonyl is a strongly o –bonding ligand. (D) carbonyl is a strongly p -acidic ligand.
26. For the reaction shown below, which statement is true ? [NSEC-2007]
2Fe + 3CdCl2 2FeCl3 + 3Cd
(A) Fe is the oxidizing agent (B) Cd undergoes oxidation
(C) Cd is the reducing agent (D) Fe undergoes oxidation
27. Which of these ion is expected to be colored in aqueous solution ? [NSEC-2008]

[I] Fe3+ [II] Zn2+ [III] Al3+ [IV] Sc3+
(A) [I] only (B) [III] only (C) [I] and [II] only (D) [I], [II] and [III]
28. How many unpaired electrons are in a Fe2+ ion in the ground state ? [NSEC-2008]
(A) 0 (B) 2 (C) 4 (D) 6
29. 1 mL of concentrated aqueous ammonia is added dropwise to 1 mL of a dilute aqueous solution of Cu(II).
What observations can be made during this process ? [NSEC-2008]
(A) The colorless Cu(II) nitrate solution turns blue and yields a dark blue precipitate
(B) The colorless copper (II) nitrate solution yields a white precipitate which turns dark blue upon standing.
(C) The light blue copper (II) nitrate solution yields a white precipitate which redissolves to form a dark blue
solution.
(D) The light blue copper (II) nitrate solution turns dark
30. Two white solids, lead (II) chloride and silver chloride can be distinguished from each other by -
(A) adding cold water to each : the silver chloride will dissolve. [NSEC-2008]
(B) adding hot water to each : the lead (II) chloride will dissolve.
(C) adding sodium chloride solution to each : the lead (II) chloride will become warm and release chlorine gas.
(D) adding zinc chloride solution to each : the silver chloride will change to metallic silver.
ADVDBC - 160
31. CuSO4 reacts with KCN to form water insoluble CuCN. This insoluble precipitate dissolves in excess of KCN,
due to formation of the following complex [NSEC-2008]
(A) K2[Cu(CN)4] (B) K3[Cu(CN)4] (C) Cu(CN)2 (D) Cu[KCu(CN)4]
32. The ion which has 18 electrons in the outermost shell is – [NSEC-2009]
(A) Cu+ (Z = 29) (B) Al3+ (Z = 13) (C) K+ (Z = 19) (D) Th4+ (Z = 90)
33. The compound with the lowest oxidation state of iron is – [NSEC-2009]
(A) Fe2O (B) Fe3O4 (C) K3Fe(CN)6 (D) K4Fe(CN)6
34. The aqua ion which will be almost colorless is – [NSEC-2009]

(A) Cu2+ (B) Cr2+ (C) Ti4+ (D) Mn2+
35. MnO41– is of intense pink colour, though Mn is in +VII oxidation state. This is due – [NSEC-2009]
(A) d-d transition
(B) charge transfer when Mn gives electron to oxygen
(C) charge transfer when oxygen gives its electrons to Mn making it +VI
(D) absorption of IR frequencies
36. The product formed when chlorine gas is passed over hot iron is [NSEC-2010]
(A) lron(II) chloride is formed.
(B) Iron(III) chloride is formed.
(C) A mixture of iron(II)chloride and iron(III) chloride is formed.
(D) No reactions will take place.
37. The group that has the species correctly listed in the order of decreasing radius is [NSEC-2011]
(A) Cu2+, Cu+, Cu (B) V, V2+, V3+ (C) F –, Br–, I (D) B, Be, Li
38. The compound in which Mn has oxidation state of +3 is [NSEC-2011]

(A) KMnO4 (B) K2 [Mn(CN)6] (C) MnSO4 (D) CsMn(SO4)2.12H2O
39. Lanthanide contraction is caused due to [NSEC-2012]

(A) the appreciable shielding on outer electrons by 4f electrons from the nuclear charge
(B) the appreciable shielding on outer electrons by 5d electrons from the nuclear charge
(C) the same effective nuclear charge from Ce to Lu.
(D) the imperfect shielding on outer electrons by 4f electrons from the nuclear charge
40. Which of the following ion is colourless ? [NSEC-2012]

(A) Mn2+ (B) Cu+ (C) Cr3 (D) Fe2+
41. The lanthanide compound which is used as a most powerful liquid laser after dissolving in selenium oxychloride
is : [NSEC-2012]
(A) Cerium oxide (B) Neodynium oxide
(C) Promethium sulphate (D) Cerium sulphate
42. Which of the following weighs less when weighed in magnetic field ? [NSEC-2012]
(A) ScCl3 (B) FeCl3 (C) TiCl3 (D) VCl3
43. In which of the following compounds is the oxidation number of the transition metal, zero ? [NSEC-2013]
(A) [Fe(H2O)3](OH2) (B) [Co(NH3)6]Cl2 (C) [Ni(CO4)] (D) [Pt(C2H4)Cl3]
44. One of the constituents of German silver is [NSEC-2013]

(A) Ag (B) Mg (C) Cu (D) Al
45. A catalyst is a substance that [NSEC-2013]

(A) undergoes chemical change to accelerate the rate of the reaction
(B) decreases the energy of activation of the reaction
(C) increases the kinetic energy of the reaction
(D) lowers the potential energy of the products with respect to that of the reactants.
ADVDBC - 161
46. The number of unpaired electrons in Ni2+ is [NSEC-2013]
(A) 0 (B) 2 (C) 3 (D) 4
47. The colourless ion from among the following is [NSEC-2013]

(A) Mn2+ (B) Cu+ (C) Cr 3+
(D) Fe 2+
48. The metal carbonyl which is paramagnetic is [NSEC-2013]

(A) Ni(CO)4 (B) V(CO)6 (C) Cr(CO)6 (D) Fe(CO)5
49. Bell metal is an alloy of copper and [NSEC-2013]

(A) Tin (B) Aluminium (C) Zinc (D) Nickel
50. Europium (Eu) and Terbium (Tb) attain stable 4f7 configuration by exhibiting oxidation states of
[NSEC-2013]
(A) +2 and +4 (B) +3 and +4 (C) +2 and +3 (D) +1 and +3
51. The number of unpaired electrons in Ni2+ ion is 2,therefore its spin multiplicity is [NSEC-2013]
(A) 2 (B) 1 (C) 3 (D) 4
52. When zinc rod is directly placed in copper sulphate solution [NSEC-2013]
(A) the blue colour of the solution starts intensifying
(B) the solution remains electrically neutral
(C) the temperature of the solution falls
(D) the weight of zinc rod starts increasing
53. The ions which give black precipitates on passing H2S gas in acidic medium are [NSEC-2013]
(A) Al3+ and Ni2+ (B) Ni2+ and Co2+ (C) Cu2+ and Bi3+ (D) Zn2+ and Mn2+

A. General %
is correct.
C. Marking Scheme :
be awarded.
ADVDBC - 162

1. Among the following series of transition metal ions, the one where all metal ions have 3d2 electronic configuration
is ;
(A) Ti3+ , V2+ , Cr3+ , Mn4+ (B) Ti+ , V4+ , Cr6+ , Mn7+
(C) Ti , V , Cr , Mn
2+ 3+ 2+ 3+
(D) Ti2+ , V3+ , Cr4+ , Mn5+
2. The pair of the compounds in which both the metals are in the highest possible oxidation state is,
(A) [Fe(CN)6]3– , [Co(CN)6]3– (B) CrO2Cl2 , MnO4–
(C) TiO2 , MnO2 (D) [Co(CN)6]3–, Mn2O7
3. VO2 is an amphoteric oxide and in acidic medium it forms :

(A) VO2+ (B) VO+2 (C) V3+ (D) VO22+
4. S1 : Mn2+ compounds are more stable than Fe2+ towards oxidation to their +3 state.
S2 : Titanium and copper both in the first series of transition metals exhibits +1 oxidation state most frequently.
S3 : Cu+ ion is stable in aqueous solutions.
S4 : The E value for the Mn3+ / Mn2+ couple is much more positive than that for Cr3+ /Cr2+ or Fe3+/Fe2+.
(A) T T F T (B) T F F T (C) T F T T (D) F F T F
5. Identify the incorrect statement.

(A) CuSO4 reacts with KCl in aqueous solution to give Cu2Cl2 .
(B) CuSO4 reacts with KI in aqueous solution to give Cu2I2 .
(C) CuSO4 reacts with NaOH and glucose in aqueous medium to give Cu2O.
(D) CuSO4 on strong heating gives CuO.

6. CuFeS2 + O2 (excess)  X(s) + Y(s)
Note : Correspondings sulphates of copper and iron are formed respectively.
Which is correct choice for (X) and (Y) ?
(A) (X) liberates iodine from soluble iodides like KI
(B) (Y) on heating liberates SO3 only
(C) (X) forms bluish white precipitate with sodium hydroxide which redissolves in excess of sodium hydroxide.
(D) (Y) on reaction with potassium ferricyanide gives brown precipitate.
 
H H
7.  [X] 
Fusion
FeCr2O4 + Na2CO3 + O2    [Y] 
 [Z]
H2 O H2 O 2
Which of the following statement is true for the compounds [X], [Y] and [Z] ?
(A) In all three compounds, the chromium is in + 6 oxidation state.
(B) [Z] is a deep blue–violet coloured compound which decomposes rapidly in aqueous solution into Cr3+ and
dioxygen.
(C) Saturated solution of [Y] gives bright orange compound, chromic anhydride, with cold and concentrated
H2SO4.
(D) All of these.

ADVDBC - 163
8. Select the correct statement(s) with respect to oxides and oxoanions of transition metals.
(A) Among oxides of chromium, CrO is basic, Cr2O 3 is amphoteric and CrO 3 is acidic.
(B) No higher oxides of iron above Fe2O3 are found.
(C)Ti,V,Cr and Mn form oxides MO and their correct increasing order of acidic character is
MnO<CrO<VO<TiO.
(D) Vandium(V) oxide does not react with acids but reacts with alkalies only.
9. Fenton’s reagent is X + H2O2. X combines readily with Y and H2O to form crystals of Mohr salt. X can be
made in laboratory from Kipp’s waste. When Kipp’s waste is heated in the presence of O 2 and water, Z is
also produced along with X. The reaction of X with KMnO4 in the presence of H2SO4 also gives Z.
Identify the correct match.
(A) X = FeSO4 (B) X = Fe2(SO4)3 (C) Y = (NH4)2SO4 (D) Z = FeSO4
10. Cuprous chloride can be prepared :

(A) by passing SO2 through the solution containing CuSO4 and NaCl.
(B) by heating excess of copper with concentrated HCl in presence of a little KCIO 3.
(C) by boiling copper sulphate solution with excess of copper turnings in presence of hydrochloric acid.
(D) by dissolving cupric oxide or copper carbonate in concentrated HCI.
11. Potassium manganate (K2MnO4) is formed when :

(A) potassium permanganate reacts with formaldehyde in acidic medium.
(B) manganese dioxide is fused with potassium hydroxide in air.
(C) manganese hydroxide reacts with K2O2 in alkaline medium.
(D) potassium permanganate is heated at 750K.
12. Select the incorrect statement(s) :

(A) In K2MnO4 and CrO2Cl2, the central transition metals/ions have same oxidation state.
(B) Both sodium and potassium dichromate can be used as primary standard in volumetric estimations.
(C) Potassium dichromate on strong heating evolves oxygen gas and forms green powder.
(D) Potassium permanganate on heating with solid KOH evolves oxygen gas and forms a black powder.

13. How many of the following are coloured or paramagnetic or coloured and paramagnetic both.
NO2, Cu+1, O2, O3, Hg2+2, Cd+2, Al, C(graphite), Sc+3
14. How many of the following ions have spin maganetic moment more than four B.M.
Ti3+, Cu+, Ni2+, Fe3+, Mn2+, Co2+
15. In how many of the following reactions, colored precipitate is obtained ?

(a) CuSO4 + NaOH(excess) 
(b) CuCl2 + NH3 (excess) 
(c) ZnSO4 + NaOH(excess) 
(d) ZnSO4 + NH3 (excess) 
in
(e) FeSO4 + NaOH(excess) 
air

(f) FeCl3 + NaOH(excess) 
(g) CuSO4 + KI (excess) 
(h) ZnSO4 + NaHCO3 
(i) CuCl2 + NaNO3 
ADVDBC - 164
16.
In the above reaction scheme, MnO2 appears more than once. From (A) – (F), How many of them contain
MnO2 ?
17. How many of the following compounds are diamagnetic and colored ?
K2MnO4 , Cu2Cl2 , Hg2I2 , Ag2S , HgI2 , K2CrO4 , Cr2O3 , AgCl , Ag2O , CuSO4 , HgS , AgF , CrO5 , Mn2O7 ,
MnO2,
18. How many of given statements are true for lanthanums ?

(1) The common oxidation state of all lanthanides is +3.
(2) All lantanides belongs to group III of modern periodic table.
(3) All lanthanides belongs to seventh period of periodic table.
(4) The radius for all lanthanides cations(M+3) decrease from Ce+3 to Lu+3.
(5) The basic character of hydroxide increases on moving from Ce(OH)3 to Lu(OH)3.
(6) All lanthanides are metals.
(7) The reducing power of lanthanides decreases from Ce to Lu.
(8) Lanthanides reacts with cold water to liberate H2.

(A), (B), (C) and (D)

(i) A powdered substance (A) on treatment with fusion mixture gives a green coloured compound (B).
(ii) The solution of (B) in boiling water on acidification with dilute H2SO4 gives a pink coloured
compound (C) and brown colour compound (D).
(iii) The aqueous solution of (A) on treatment with NaOH and Br2–water gives the compound (D).
(iv) A solution of (D) in concentrated HNO3 on treatment with lead peroxide at boiling temperature
produced a compound (E) which was of the same colour at that of (C).
(v) A solution of (A) on treatment with a solution of barium chloride gave a white precipitate of compound (F)
which was insoluble in concentrated HNO3 and concentrated HCl.
19. Which of the following is true for compound (C) ?

(A) It oxidises ammonia to nitrogen dioxide in neutral medium.
(B) It's pink colour is due to d-d transition.
(C) It can be oxidised by ozone.
(D) It is obtained by alkaline fusion of pyrolusite followed by electrolytic oxidation.
ADVDBC - 165
20 The oxidation state of central metal ions of (A), (B) and (C) compounds are respectively :
(A) +II , + VI and + VII (B) +II , + VI and + VI (C) +II , + VII and + VII (D) +VI , + VII and + VII
21. Consider the following statements ;

(I) anions of both (B) and (C) are diamagnetic and have tetrahedral geometry.
(II) anions of both (B) and (C) are paramagnetic and have tetrahedral geometry.
(III) anion of (B) is paramagnetic and that of (C) is diamagnetic but both have tetrahedral geometry.
(IV) green coloured compound (B) in a neutral or acidic medium disproportionates to give (C) and (D).
of these select the correct one from the codes given :
(A) I and III only (B) II and III only (C) II and IV only (D) III and IV only

22. Match the reactions in Column I with the types of products / the use of products in Column II.
(P) HO OH + AgBr(s)  (1) Turn bull’s blue pigment

(Q) BaCl2 + K2Cr2O7 + H2SO4  (2) Rinmann’s green pigment
(R) FeSO4 + K3[Fe(CN)6]  (3) Chromyl chloride test

(S) ZnO + Co(NO3)2  (4) Photography
Code :
P Q R S P Q R S
(A) 1 3 2 4 (B) 3 2 4 1
(C) 4 3 1 2 (D) 4 1 2 3

Que. 1 2 3 4 5 6 7 8 9 10
Ans.
Que. 11 12 13 14 15 16 17 18 19 20
Ans.
Que. 21 22
Ans.

Problem - 1 (INChO_2005)
Transition Metal Chemistry : Different properties of transition elements such as multiple oxidation states,
formation of coloured complexes, paramagnetism etc. are related to the presence of electrons in d orbitals.
In the first transition metal series, that begins with Sc, two elements exhibit electronic configurations different
from the normal expectation.
1.1 Identify these two elements, write their outer electronic configurations and explain the reason for the observed
configurations.
ADVDBC - 166
1.2 Covalent radius of transition metal elements decreases from left to right across a row Explain this trend
briefly.
1.3 Transition element chemistry is dominated by the co-ordination complexes that have specific three- dimensional
structures. The ligands that are involved in complex formation play an important role in determining the
geometry of the complexes. Write the IUPAC name of [Pt(NH3)4CI2 ]2+. Draw the 3D structures of the possible
isomers.
Problem - 2 (INChO_2011)
2.1 Complexes of iron exist with different numbers of unpaired electrons. For the given complexes, write
the number of unpaired electrons and state whether they are high spin or low spin species. (4 marks)
Complex No of unpaired electrons Spin state

[Fe(CN)6] 4–
[Fe(CN)6] 3–
[FeCl4]–
[Fe(H2O)6]2+
2.2 The oxygen taken during respiration in human beings is carried through the blood stream with the help
of haemoglobin. The latter is a tetramer containing four heme (iron-porphyrin) units. The oxidation state
of iron in deoxyhaemoglobin is +2 and it is a high spin paramagnetic species. On binding with oxygen,
the iron in haemoglobin changes its coordination sphere from 5 to 6. This results in the change in
magnetic property. The value of magnetic moment in each unit of oxyhaemoglobin is (0.5 mark)

Problem - 1 [IChO, 1968]
Write down equations for the following reactions:
1.1 Oxidation of chromium(III) chloride with bromine in alkaline solution (KOH).
1.2 Oxidation of potassium nitrite with potassium permanganate in acid solution (H 2SO4).
Problem - 2 [IChO,1979]
Which chemical processes can take place in the interaction of :
2.1 potassium chromate, ferrous chloride and sulphuric acid.
Many streams drain in areas where coal or metallic ores are mined. These streams have become acidic and
contain high concentrations of dissolved iron and sulphate, due to sulphur-containing ores being exposed to
the atmosphere or to oxygenated waters. The most common sulphur-containing mineral is pyrite, FeS 2, in
which the oxidation state of iron is +2. As the iron-rich streams mix with other waters, the dissolved iron
precipitates as goethite, FeO(OH), which coats the stream bottom while the water remains acidic.
3.1 Draw the electron dot structure that illustrates the bonding in the ion S22–, showing all valence electrons.
3.2 Write a balanced chemical equation to show how hydrogen ions (H+) are generated during the oxidation of
pyrite to form a solution of iron(II) and sulphate ions.
3.3 Write a balanced equation to show how many additional moles of hydrogen are generated when iron(II) ions
are oxidized to form the mineral goethite, FeO(OH).
3.4 Calculate how many moles of pyrite would be required to bring 1.0 dm3 of pure water to a pH of 3.0 if the pyrite
was completely converted into FeO(OH) and H+ ions.
Neglect the formation of HSO4–.
ADVDBC - 167
3.5 The concentration of iron as Fe(II) in a stream is 0.00835 M. At a very narrow point in the stream it empties
into a large pond, with a flow rate of 20.0 l each minute. The water in this stream is sufficiently aerated that
75 % of the Fe(II) is oxidized to Fe(III). The pH of the pond is high enough (>7) that the iron(III) precipitates
immediately as Fe(OH)3 which on aging becomes Fe2O3. What mass of Fe2O3 will be deposited on the
bottom of the pond in two years ?
The preparation of platinum(IV) oxide involves boiling of a solution which contains hexachloroplatinate(IV)
ions with sodium carbonate. In this process PtO2 . n H2O is formed and this is in turn converted to platinum(IV)
oxide upon subsequent filtering and heat treatment. In the following we assume n = 4.
PtO2 . 4 H2O or Pt(OH)4 . 2 H2O can be dissolved in acids and strong bases.
4.1 Write the balanced equations for the preparation of platinum(IV) oxide according to the procedure given
above.
4.2 Write the balanced equations for the dissolution of PtO2 . 4H2O in both hydrochloric acid and sodium hydroxide.
Platinum is mainly found in the nature as the metal (in mixture or in alloying with other precious metals).
Platinum is dissolved in aqua regia under the formation of hexachloroplatinate(IV) ions. Aqua regia is a
mixture of concentrated hydrochloric and nitric acids in proportion 3 : 1, and of the nitrosylchloride (NOCl)
and the atomic chlorine which are formed upon the mixing. The latter is believed to be the active dissolving
component.
The hexachloroplatinate(IV) ions can be precipitated as diammonium hexachloroplatinate(IV) and by thermal
decomposition of this compound, finely powdered platinum and gaseous products are formed.
4.3 Write the balanced equations for the formation of aqua regia and its reaction with platinum.
4.4 Write the balanced equation of the thermal decomposition of diammonium hexachloroplatinate(IV) at elevated
temperature.
Excavated Chinese ancient bronze musical instrument, carillon, was covered entirely by rust. Chemical
analysis showed that the rust contains CuCl, Cu2O and Cu2(OH)3Cl. Simulation experiments showed that
CuCl was formed first under the action of both air and Cl containing aqueous solution and then Cu 2(OH)3Cl
produced through the following two different ways :
5.1 Write balanced equations for reactions (a), (b) and (c).
Extraction of gold using sodium cyanide, a very poisonous chemical, causes environmental problems and
gives rise to serious public concern about the use of this so called “cyanide process”. Thiosulfate leaching of
gold has been considered as an alternative. In this process, the main reagent is ammonium thiosulfate,
(NH4)2S2O3, which is relatively non-toxic. Although this process appears to be environmentally benign, the
chemistry involved is very complex and needs to be studied thoroughly. The solution used for leaching gold
contains S2O32–, Cu2+, NH3, and dissolved O2. The solution must have a pH greater than 8.5 to allow free
ammonia to be present.
ADVDBC - 168
According to the proposed mechanism, a local voltaic micro-cell is formed on the surface of gold particles
during the leaching process and operates as follows:
Anode : Au(s) + 2 NH3(aq)  [Au(NH3)2]+(aq) + e–
[Au(NH3)2]+(aq) + 2 S2O32–(aq)  [Au(S2O3)2]3– (aq) + 2 NH3(aq)
Cathode : [Cu(NH3)4]2+(aq) + e–  [Cu(NH3)2]+(aq) + 2 NH3(aq)
[Cu(NH3)2]+(aq) + 3S2O32–(aq)  [Cu(S2O3)3]5–(aq) + 2 NH3(aq)
6.1 Write the overall cell reaction for this voltaic cell.
6.2 In the presence of ammonia [Cu(S2O3)3]5– is oxidized by O2 back to [Cu(NH3)4]2+. Write a balanced equation
for this oxidation-reduction reaction in basic solution.
6.3 In this leaching process, the [Cu(NH3)4]2+ complex ion functions as catalyst and speeds up the dissolution of
gold. Write the net overall oxidation-reduction reaction for dissolution of the gold metal, which is catalyzed by
[Cu(NH3)4]2+ complex ion.
6.4 Draw the coordination geometries of the metal in [Au(NH3)2]+ and [Au(S2O3)2]3– complex ions, indicating the
coordinating atoms.
6.5 Calculate the percentage of gold(I) ion that exists in the form of thiosulfate complex.
When the concentration of O2 is not high enough and pH > 10, S2O32– reduces [Cu(NH3)4]2+ to [Cu(S2O3)3]5–
with the formation of tetrathionate ion S4O62– :
2 [Cu(NH3)4]2+(aq) + 8 S2O32–(aq)  2[Cu(S2O3)3]5– (aq) + S4O62–(aq) + 8 NH3(aq)
In basic solution tetrathionate disproportionates to trithionate, S3O62–, and thiosulfate.
6.6 Write a balanced equation for this disproportionation reaction.
6.7 When the O2 concentration is too high, S2O32– is oxidized by oxygen to yield trithionate and sulfate ions.
Write a balanced equation for this reaction.
ADVDBC - 169
PART - I
1. (1) 2. (2) 3. (1) 4. (1) 5. (4)
6. (3) 7. (2) 8. (1) 9. (3) 10. (3)
11. (4) 12. (4) 13. (1) 14. (4) 15. (2)
16. (1) 17. (4) 18. (1) 19. (1) 20. (2)
21. (3) 22. (3) 23. (4) 24. (4) 25. (4)
26. (4) 27. (4) 28. (4) 29. (1) 30. (1)
PART - II
1. (C) 2. (B) 3. (B) 4. (C) 5. (D)
6. (A) 7. (B) 8. (C) 9. (A) 10. (C)
11. (B) 12. (C) 13. (B) 14. (A) 15. (C)
16. (D) 17. (B) 18. (B) 19. (B) 20. (D)
21. (C) 22. (A) 23. (A) 24. (D) 25. (D)
26. (D) 27. (A) 28. (C) 29. (C) 30. (B)
31. (B) 32. (A) 33. (A) 34. (C) 35. (C)
36. (B) 37. (B) 38. (D) 39. (D) 40. (B)
41. (B) 42. (A) 43. (C) 44. (C) 45. (B)
46. (B) 47. (B) 48. (B) 49. (A) 50. (A)
51. (C) 52. (B) 53. (C)
PART - III
1. (D) 2. (B) 3. (A) 4. (B) 5. (A)
6. (A) 7. (D) 8. (A,B) 9. (A,C) 10. (A,B,C)
11. (B,C,D) 12. (B,D) 13. 4 14. 2 15. 3
16. 3 17. 9 18. 6 19. (D) 20 (A)
21. (D) 22. (C)
PART - IV
2.1 Complex No of unpaired electrons Spin state

4–
[Fe(CN)6] 0 LS
3–
[Fe(CN)6] 1 LS
–
[FeCl4] 5 HS
2+
[Fe(H2O)6] 4 HS
2.2 8
ADVDBC - 170
PART - V
1.1 2 CrCl3 + 3 Br2 + 16 KOH  2 K2CrO4 + 6 KBr + 6 KCl + 8 H2O
1.2 5 KNO2 + 2 KMnO4 + 3 H2SO4  2 MnSO4 + K2SO4 + 5 KNO3 + 3 H2O
2.1 b-1 2 CrO42– + 2H+  Cr2 O72– + H2O

b-2 6 Fe2+ + Cr2O72– + 14 H+  6Fe3+ + 7H2O
b-3 with high concentrations of Cl– and H2SO4 :
Cr2O72– + 4Cl– + 6H+  CrO2Cl2 + 3 H2O
3.1
3.2 FeS2 + 7/2 O2 + H2O  Fe2+ + 2 SO42– + 2 H+
3.3 Fe2+ + 1/4 O2 + 3/2 H2O  FeOOH + 2 H+
3.4 [H+] = 1 × 10–3

n[H+] = 1 × 10–3 mol
from both equations : n(FeS2) = 2.5 × 10–4 mol
3.5 Total flow into pond in 2 years =

2 yr × 365 days yr–1 × 24 h day–1 × 60 min h–1 × 20.0 dm3 min–1 = = 2.10 × 107 dm3 of water
n(Fe2+) into pond = 2.10 × 107 dm3 × 8,35 × 10–3 mol dm–3 = 1.76 ×105 mol
n(Fe3+) produced = 0.75 × 1.76 × 105 mol = 1.32 × 105 mol
mass of deposited Fe2O3 :
m(Fe2O3) = 0.5 × 1.32 × 105 mol × 159.7 g mol–1 = 1.05 × 107 g
4.1 CO32– (aq) + H2O(l) HCO3– (aq) + OH–(aq)

PtCl62– (aq) + 4OH–(aq) + 2H2O(l)  Pt(OH)4.2H2O(s) + 6Cl– (aq)
Alternative I : PtO2 . 4H2O(s) + 6Cl– (aq)
Alternative II : (n – 2) H2O  PtO2 . n H2O(s) + 6 Cl–(aq)
PtO2 : 4 H2O(s)  PtO2(s) + 4H2O (g)
[PtO2 . 4 H2O (s)  Pt(OH)4 . 2H2O (s)]
4.2 In hydrochloric acid: PtO2 . 4 H2O(s) + 4 H+(aq) + 6 Cl–(aq)  PtCl62–(aq) + 6 H2O
In sodium hydroxide: PtO2 . 4 H2O(s) + 2 OH–(aq)  Pt(OH)62–(aq) + 2 H2O
4.3 3 HCl(sol) + HNO3(sol)  NOCl(sol) + 2 Cl(sol) + 2 H2O(sol)

Pt(s) + 4 Cl(sol) + 2 HCl(sol)  PtCl62– (sol) + 2 H+(sol)
4.4 (NH4)2PtCl6(s)  Pt(s) + 2 NH3(g) + 2 HCl(g) + 2 Cl2(g)
5.1 (a) 2 CuCI(s) + H2O(l)  Cu2O(s) + 2 H+(aq) + 2 Cl–(aq)

(b) Cu2O(s) + ½ O2(g) + H2O(l) + H+(aq) + Cl–(aq)  Cu2(OH)3Cl(s)
(c) 2 CuCl(s) + ½ O2 (g) + 2 H2O(l)  Cu2(OH)3Cl (s) + H+(aq) + Cl–(aq)
6.1 Net anode half reaction: Au(s) + 2 S2O32– (aq)  [Au(S2O3)2]3–(aq) + e–
Net cathode half reaction: [Cu(NH3)4]2+(aq) + 3 2 S2O32–(aq) + e–  [Cu(S2O3)3]5–(aq) + 4 NH3(aq)
Overall cell reaction:
Au(s) + [Cu(NH3)4]2+(aq) + 5S2O32– (aq)  [Au(S2O3)2]3–(aq) + [Cu(S2O3)3]5–(aq) + 4 NH3(aq)
ADVDBC - 171
6.2 Oxidation half reaction :
[Cu(S2O3)3]5–(aq) + 4 NH3(aq)  [Cu(NH3)4]2+(aq) + 3 S2O32– (aq) + e–
Reduction half reaction :
O2(g) + 2H2O(l) + 4e–  4 OH– (aq)
Redox reaction :
4 [Cu(S2O3)3]5–(aq) + 16 NH3(aq) + O2(g) + 2 H2O(l)  4 [Cu(NH3)4]2+(aq) + 12 S2O32–(aq) + 4 OH–(aq)
6.3 Au(s) + [Cu(NH3)4]2+(aq) + 5 S2O3)32– (aq)  [Au(S2O3)2]3–(aq) + [Cu(S2O3)3]5–(aq) + 4 NH3(aq)

4 [Cu(S2O3)3]5–(aq) + 16 NH3(aq) + O2(g) + 2 H2O(l)  4 [Cu(NH3)4]2+(aq) + 12 S2O32–(aq) + 4 OH–(aq)
__________
Summarizing the above equations:
4 Au(s) + 8 S2O32– (aq) + O2(g) + 2 H2O(l)  4 [Au(S2O3)2]3–(aq) + 4 OH–(aq)
6.4 [Au(NH3)2]+ [Au(S2O3)2]3–

Coordination geometry: [H3N-Au-NH3]+ [O3S-S-Au-S-SO3 ]3–
The formation constants, Kf, of [Au(NH3)2]+ and [Au(S2O3)2]3– complexes are 1.00 × 1026 and 1.00 × 1028,
respectively. Consider a leaching solution in which the equilibrium concentrations of the species are as
follows:
[S2O32–] = 0.100 ; [NH3] = 0.100 and the total concentration of gold(I) species = 5.50 × 10–5 mol dm–3.
6.5 Au+(aq) + 2 NH3(aq)  [Au(NH3)2]+(aq) Kf,1 = 1.00 . 1026

Au+(aq) + 2 S2O32–(aq)  [Au(S2O3)2]3–(aq) Kf, 2 = 1.00 . 1028
__________
[Au(NH3)2]+ (aq) + 2 S2O32–(aq) [Au(S2O3)2]3–(aq) + 2 NH3(aq)
K f ,2
K eq   1.00.10 2
K f ,1
[Au(NH3)2]+ + [Au(S2O3)2]3– = 5.50 × 10–5 mol dm–3
(0.100)2 x
K eq   1.00.10 2
(5.50.10 5  x )(0.100)2
x = 5.445 . 10–5
5.445 .10 5
 100  99.0%
5.50.10 5
Thus, 99.0 % of Au(I) is in the form of [Au(S2O3)2]3–.
6.6 S4O62– (aq) + 2e–  2 S2O32–

12 OH –(aq) + 3 S4O62–(aq)  4 S3O62–(aq) + 6 H2O(l) + 10 e–
__________
4 S4O62– (aq) + 6 OH–(aq)  5 S2O32– (aq) + 2 S3O62– (aq) + 3H2O(l)
disproportionation
6.7 2 S2O32– (aq) + 2 O2(g)  SO42– (aq) + S3O62–(aq)
ADVDBC - 172
PART - I
1. (1) Electron configuration of V is [Ar] 3d3 4s2 and thus maximum 5 electrons participate in bonding.
(2) Electron configuration of Cr is [Ar] 3d5 4s1 and thus maximum 6 electrons participate in bonding.
(3) Electron configuration of Co is [Ar] 3d7 4s2 . In octahedral splitting in presence of ligands, half filled t 62 g has
higher CFSE and thus +3 oxidation state is most stable.
(4) Electron configuration of Sc is [Ar] 3d1 4s2 and thus maximum 3 electrons participate in bonding.
2. Transition metal oxide with highest oxidation states is most acidic in character because of the very less
difference in the values of electronegativity between Mn7+ and O2– , and the decreasing order of acidic character
7 4 3 2
is Mn 2O 7 > MnO2 > Mn2O3 > > MnO .
3. First ionisation energies of 3d-series (first transition series) increase with increase in atomic number due to
(1) increase in nuclear charge (2) decrease in atomic size.
4. (i) Valence shell electron configuration of Ti4+ is 3d10 4s0. As there is no unpaired electrons for d–d transition,
the solution of ions will be colourless.
(ii) Valence shell electron configuration of Cu+ is 3d10 4s0. As all electrons are paired, there is no d–d
transition, so the solution of ions will be colourless.
(iii) Valence shell electron configuration of Co3+ is 3d6 4s0. As there are 4 unpaired electrons, there is d–d
transition of electron, so the solution of ions will be coloured.
(iv) Valence shell electron configuration of Fe2+ is 3d6 4s0. As there are 4 unpaired electrons, there is d–d
transition of electron, so the solution of ions will be coloured.
5. (1) Valence shell electron configuration of Co3+ is 3d6 4s0. So has 4 unpaired electrons.
(2) Valence shell electron configuration of Fe3+ is 3d5 4s0. So has 5 unpaired electrons.
(3) Valence shell electron configuration of Cr2+ is 3d4 4s0. So has 4 unpaired electrons.
(4) Valence shell electron configuration of V3+ is 3d2 4s0. So has 2 unpaired electrons.
It has least number of unpaired electrons, so it has least magnetic moment.
6. If a non-metal occupies interstitial sites of a metal, the metal becomes less malleable. This is because the
non-metal atom forms covalent bonds with metal atoms and covalent bond is rigid and directional.
7. (1) Oxidation state of iron is +3 but it can exceed to a maximum of +6. Oxidation state of cobalt is +3 but it
can exceed to a maximum of +4.
(2) Highest oxidation state of Cr in CrO2Cl2 is + 6 and highest oxidation state of Mn in MnO4– is + 7.
(3) Oxidation state of titanium is +2 but it can exceed to a maximum of +4. Oxidation state of Mn is +4 but
it can exceed to a maximum of +7.
(4) Oxidation state of cobalt is +3 but it can exceed to a maximum of +4. Oxidation state of Mn is +7 which
is its highest oxidation state.
8. CuCl absorbs CO, SO2, C2H2

CuCl + 2CO  2CuCl.CO.
9. (3) FeCl3 exists as Fe2Cl6 (a dimer) in vapour state.The solution is acidic due to the formation of HCl and
brown due to the formation of Fe(OH)3 .
FeCl3 + 3H2O  Fe(OH)3 (Brown) + 3HCl
10. (1) Cu2O is red white CuO is black.

(2) Obtained on heating malchite ore not heamatite

CuCO3.Cu(OH)2  2 CuO + CO2 + H2O
ADVDBC - 173

(3) 3 CuCl2.2H2O  CuO + 2CuCl + 2HCl + Cl2 + 5H2O
(4) 2CuFeS2 + 4O2  Cu2S + 2FeO + 3SO2
11. All are facts.
12. 2CuSO4 + 2NaCl + SO2 + 2H2O  Cu2Cl2 + Na2SO4 + 2H2SO4

Cu2Cl2 + H2S  Cu2S + 2HCl
(Black ppt.)
Cu2Cl2 + aq. NH3  [Cu(NH3)2]Cl
Soluble complex
Cu2Cl2 + 4 HCl  2 H2CuCl3
Heat
13. (1) True, 2FeCl3.6H2O   Fe2O3 + 6HCl + 9H2O
(2) False, FeSO4 is oxidised to Fe3+ early, so it is not used as primary standard. But Mohr’s salt
[FeSO4.(NH4)2SO4.6H2O] can be used.
(3) False, ZnCl2 + H2S  ZnS + 2HCl
white precipitate
(4) False, CuSO4 + 4NH4OH  [Cu(NH3)4]SO4 + 4H2O
Deep blue solution
FeSO4 + 2NH4OH Fe(OH)2 + (NH4)2SO4
Insoluble
14. S2O32– , CN– , SCN– and I– act as reducing agent

Cu2+ + S2O32–   Cu+ + S4O62–
Cu + CN 
2+ –
 Cu+ + (CN)2
Cu2+ + SCN–   Cu+ + (SCN)2
15. SO2 and SO3


FeSO4   Fe2O3 + SO2+ SO3+ O2 
The acidic gases produced are SO2 and SO3
16. X : [K3 Fe(CN)6) Y : Fe [Fe(CN)6]
750K
17. 2KMnO4   K2MnO4 + MnO2 + O2 .
18. MnO4– + 3e– + 2H2O  MnO2 + 4OH– (neutral / weak alkaline medium)
19. 2KMnO4 + 3H2SO4  2KHSO4 + (MnO3)2SO4 + 2H2O

(MnO3)2SO4 + H2O  Mn2O7 + H2SO4
 3
Mn2O7  2MnO2 + O
2 2
20. (1) Cr2O72– + 14H+ + 6–  2Cr3+ + 32 + 7H2O.

(2) In acidic solution, actually chromate is converted to dichromate.
2CrO42– + 2H+  Cr2O72– + H2O.

(3) (NH4)2Cr2O7  N2 + 4H2O + Cr2O3.
(4) 6Fe2+ + Cr2O72– + 14H+  6Fe3+ + 2Cr3+ + 7H2O.
21. Quinol developer (a reducing agent) reduces AgBr to Ag.

2AgBr*(s) + 2OH– (aq) + C6H5(OH)2 (aq)  2Ag(s) + 2H2O + C6H4O2 (aq) + 2Br– (aq)
Where AgBr* represents a molecules of AgBr exposed to light.
ADVDBC - 174
22. CO2 + H2O  H2CO3 2H+ + CO32– ; CrO42– + 2H+ Cr2O72– (orange red) + H2O
23. In FeO42–, Fe is in very high oxidation state (+6) and hence unstable, so it gets reduced to Fe 3+ liberating O2.
CrO24– in acidic medium converted to Cr2O 27 – .
24. AgCl  h
 Ag + 1/2 Cl2
(black)
If souce of light is removed, we get back Agce and blacknem due to Ag removed.
25. Ag +dilute HNO3  AgNO3 + NO (g)

Ag + conc. HNO3 AgNO3 + NO2 (g)
Ag + conc. H2SO4 Ag2SO4 + SO2 (g)
26. 2K2MnO4 + Cl2  2KMnO4 + 2KCl ; 2K2MnO4 + H2O + O3  2KMnO4 + 2KOH + O2 .

3K2MnO4 + 2CO2  2KMnO4 + MnO2 + 2K2CO3 .
27. Aqueous solution of CuSO4 is acidic in nature, it converts some CuCrO4 to CuCr2O7 .
28. In Co+3 ion, electronic configuration |Ar|18 3d64s0. For octahedral complex 4 unpaired electron get paired and
in configuration become t2g6 eg0 and hybridization d2sp3.
Os has maximam VIII oxidation state.
29. After uranium all elements are transuranic element.
PART - III
1. 22
Ti = 3d 4s , Ti = 3d
2 2 2+ 2
; 23
V = 3d3 4s2 , V3+ = 3d2 .
24
Cr = 3d5 4s1 , Cr4+ = 3d2 ; 25
Mn = 3d5 4s2 , Mn5+ = 3d2.
2. (A) Oxidation state of iron is +3 but it can exceed to a maximum of +6. Oxidation state of cobalt is +3 but it
can exceed to a maximum of +4.
(B) Highest oxidation state of Cr in CrO2Cl2 is + 6 and highest oxidation state of Mn in MnO4– is + 7.
(C) Oxidation state of titanium is +2 but it can exceed to a maximum of +4. Oxidation state of Mn is +4 but
it can exceed to a maximum of +7.
(D) Oxidation state of cobalt is +3 but it can exceed to a maximum of +4. Oxidation state of Mn is +7 which
is its highest oxidation state.
3. It is an amphoteric in nature and it reacts with alkalies as well as with acids to give V4O92– and VO2+
respectively.
4. S1 : It is because Mn2+ has 3d5 configuration which has extra stability.

S2 : Not titanium but Copper, because with +1 oxidation state an extra stable configuration, 3d 10 results.
S3 : It is not stable as it undergoes disproportionation ; 2Cu+(aq)  Cu2+(aq) + Cu(s). The Eº value for this is
favourable.
S4 : Much larger third ionisation energy of Mn (where the required change is d5 to d4) is mainly responsible for
this.
5. (A) CuSO4 reacts with KI to give Cu2I2 (white precipitate) but not with KCl.
(B) 2Cu2+ + 4I–  Cu2I2 + I2  .

(C) Fehling's solution mainly contains CuSO4 and NaOH. When warmed with glucose (with – CHO group)
gives red precipitate of Cu2O. Glucose reduces the Cu2+ to Cu2O (red).
(D) CuSO4 on heating gives CuO.
1000 K 1
CuSO4   CuO + SO2 + O.
2 2
ADVDBC - 175

6. CuFeS2 + 4O2  CuSO4 (s) + FeSO4 (s)
(A) CuSO4 + 4KI  Cu22 + 2 + 2K2SO4

(B) 2FeSO4  Fe2O3 + SO2 + SO3
(C) CuSO4 + 2NaOH  Na2SO4 + Cu(OH)2  (insoluble in excess NaOH)
(D) Fe2+ + 2K3 [Fe(CN)6]  Fe3 [Fe(CN)6]2 (deep blue)
 VI   VI  VI
Fusion H 
7. 4FeCr2O4 + 8Na2CO3 + 7O2   Na 2CrO 4  Na 2Cr2O 7   Cr O(O 2 )2 (deep blue
H / H2O 2

H O 2
H2 O
violet)  O2 + H2O + Cr . 3+
(X) (Y) (Z)
Na2Cr2O7 + H2SO4  2CrO3 (bright orange/red- chromic anhydride) + Na2SO4 + H2O.
8. (A) and (B) statements are correct. These statements are factual.
(C) Along the period, the electronegativity of metals decreases and therefore the difference of
electronegativities between metal and oxygen decreases. Hence, the acidic character increases, so
the correct order is TiO < VO < CrO < MnO.
(D) V2O 5 reacts with alkalies as well as acids to give VO43– and VO 2+ respectively.
9. Fenton’s reagent is FeSO4 + H2O

FeSO4 + (NH4)2 SO4 + 6 H2O  FeSO4.(NH4)2SO4.6 H2O
(Y)
FeS2 + O2 + H2O  FeSO4 + Fe2(SO4)3 + H2SO4
(Z)
FeSO4 + KMnO4 + H2SO4  Fe2(SO4)3 + MnSO4 + K2SO4 + H2O
(X) (Z).
10. (A) 2CuSO4 + 2NaCl + 2H2O + SO2  Cu2Cl2 + Na2SO4 + 2H2SO4

(B) Cu + HCl + [O]  CuCl2 + H2O ; CuCl2 + Cu  Cu2 Cl2
(C) CuSO4 + 2HCl  CuCl2 + H2SO4 ; CuCl2 + Cu  Cu2Cl2
(D) CuO + 2HCl  CuCl2 + H2O ; Cu2Cl2 is not formed.
11. (A) 5HCHO + MnO4– + 6H+  2Mn2+ + 5HCOOH + 3H2O.

(B) 4KOH + 2MnO2 (manganese dioxide) + O2  2K2MnO4 (potassium mangnate) + 2H2O.
(C) Mn(OH)2 + O22–  MnO42– (mangnate) + 2OH– .
750 K
(D) 2KMnO4   K MnO (potassium mangnate) + MnO + O .
2 4 2 2
12. (A) In both compounds central metals have + 6 oxidation states.

MnO42– ; x + 4 (– 2) = – 2, So, x = 6. ; CrO2Cl2 ; x + 2 (– 2) + 2 (–1) = 0, So, x = 6.
(B) Sodium dichromate is Na2Cr2O7.2H2O, so it can not be weighed correctly for the preparation of standard
solution.

(C) 2K2Cr2O7  2K2CrO4 + Cr2O3 (green) + 3/2 O2 .

(D) 4KMnO4 + 4KOH  4K2MnO4 (green) + 2H2O + O2
13. *NO2 Coloured & Paramagnetic

Cu+1 Colourless
*O2 Paramagnetic
O3 Diagmagnetic
Hg2+2 Colourless
Cd+2 Coloureless
*Al Paramagnetic
*C(graphite) Paramagnetic
Sc+3 Colourless or diamagnetic
ADVDBC - 176
14. Ions Outer configuration Number of unpaired electron (s) ms = n(n  2)
Ti3+ 3d1 1 2
Cu+ 3d10 0 0
Ni2+ 3d8 2 8
Fe3+ 3d5 5 35
Mn2+ 3d5 5 35
Co2+ 3d7 3 15
15. (a) Cu(OH)2  (blue) (b) [Cu(NH3)4]2+ (aq.) (c) Na2[Zn(OH)4] (aq.)
(d) [Zn(NH3)4]2+ (aq.) (e) Fe(OH)2  (greenish) (f) Fe(OH)3  (reddish brown)
(g) CuI  (white) (h) ZnCO3  (white) (i) Cu(NO3)2 (aq.)
16.
17. Paramagetic – K2MnO4 , Cr2O3 , AgO , CuSO4 , MnO2

Diamagnetic and Colored –Hg2I2 , Ag2S , HgI2 , K2CrO4 ,
(black) (Red) (yellow)
Ag2O (brown), HgS (black) , AgF (yellow)
CrO5 (deep blue) , Mn2O7 (dark red oil)
18. (1) All lanthanides exhibits +3 O.N. but few also exhibit +2 and +4 O.N.
(2) Correct
(3) Incorrect as all belongs to 6th period.
(4) True due to lanthanide contraction.
(5) Incorrect as basicing decreases from Ce(OH)3 to Lu(OH)3 becomes of fazans rule.
(6) Correct
(7) Correct
(8) All lanthanides have –ve S.R.P. hence all releases hydrogen.
19. (A) 2MnO4– + 2NH3  2MnO2 + N2 + 2OH– + 2H2O

(B) It is due to charge transfer from O2– to empty d-orbital of Mn(VII).
(C) MnO4– is in highest oxidation state i.e. +VII and thus can not be oxidised further.

[e ]
(D) MnO2 + OH  MnO22–  MnO4–
20 (A) In MnSO4, = +II ; (B) MnO42– = +VI ; (C) MnO4– = +VII
ADVDBC - 177
21.
(III) Electron configuration of Mn(VI) in MnO42– is [Ar]18 3d1. So it is paramagnetic and tetrahedral.Electron
configuration of Mn(VII) in MnO4– is [Ar]18 3d0. So it is diamagnetic and tetrahedral.
(IV) 3MnO42– + 4H+  2MnO4– + MnO2 + 2H2O.
(Solution : 19 to 21)
A = MnSO4 , B = K2MnO4 , C = KMnO4 , D = MnO2 , E = HMnO4 , F = BaSO4.
MnSO4(A) + 2KNO3 + K2CO3  K2MnO4(B) + 2KNO2 + 2CO2 + K2SO4
2MnO42– + 4H+  MnO4– (C) + MnO2 + 2H2O.
Mn2+ + 2OH–  Mn(OH)2 ; Mn(OH)2 + Br2 + 2NaOH  MnO2(D) + 2NaBr + 2H2O
MnO2 + 4HNO3  2Mn(NO3)2 + 2H2O + O2
Mn(NO3)2 + 5PbO2 + 6HNO3  2HMnO4(E) + 5Pb(NO3)2 + 2H2O
SO42– + Ba2+  BaSO4 (white) (F)
22. (P) HO OH + 2AgBr(s)  O O + 2HBr + 2Ag(black silver particles)
Hydroquinone acts as developer

(Q) BaCl2 + K2Cr2O7 + 3H2SO4  K2SO4 + 2CrO2Cl2 + 2BaSO4 + 3H2O
(R) FeSO4 + K3[Fe(CN)6]  KFeII [FeIII(CN)6] + K2SO4

(S) Co(NO3)2 + ZnO  CoZnO2 or CoO. ZnO
ADVDBC - 178
Metallurgy
ADVMTL - 179
Metallurgy

Section (A) : ORES & Method of concentration
A-1. Name three ores which are concentrated by froth-floatation process.
A-2. What is meant by a depressant ?
A-3. Which concentration method is used for separating tungsten ore particles from cassiterite ore (SnO 2) ?
A-4. Which metals are obtained by self reduction of their ores ?
A-5. How carnallite ore is made anhydrous ?
A-6. What is the role of a stabiliser in froth-floatation process ?
Section (B) : Thermodynamic Principles of metallurgy

B-1. Out of C and CO, which is a better reducing agent for ZnO ?
B-2. Why the HgO decomposes into its constituent elements on heating ?
B-3. CuO is less reduced by carbon but more reduced by H2. Explain in terms of thermodynamics, given:
Gºƒ for CuO = –129.7 kJ mol–1, CO = –137.2 kJ mole–1, H2O = –237.2 kJ mol–1
Section (C) : Metallurgy of some useful metals

C-1. Cinnabar (HgS) and galena (PbS) on roasting often give their respective metals but zinc blende (ZnS) does
not. explain.
C-2. Magnesium oxide is often used as the lining in steel making furnace, Explain.
C-3. In the extraction of tin from tin stone addition of excess lime stone should be avoided. Why ?
C-4. In the extraction of lead from galena lime stone is added, why ?
C-5. Why excess of carbon is added in the zinc metallurgy ?
C-6. In the extractive metallurgy of iron from haematite ore, lime stone is added during smelting. Explain why.
C-7. State the role of silica in the metallurgy of copper.
Section (D) : electrochemical principles of metallurgy

D-1. Why air is continuously passed through the suspension of the concentrated ore of silver, the argentite during
leaching with the aqueous solution of sodium cyanide ?
D-2. Alkali metals and alkaline earth metals can only be extracted by electrolytic reduction of their fused salts,
why ?
D-3. What is the role of cryolite in the metallurgy of aluminium?
Section (E) : Purification or Refining of Impure Metals

E-1. Name the physical processes which are used for the purification of impure metals ?
E-2. Which impure metals are purified by Poling process ?
E-3. Give the name of the metals which are purified using vapour phase thermal decomposition method.
ADVMTL - 180
Metallurgy

Section (A) : ORES & Method of Concentration
A-1. Calamine is an ore of :
(A) Zn (B) Mg (C) Ca (D) Pb
A-2. Which of the following is not the ore of aluminium ?

(A) Bauxite (B) Corundum (C) Langbeinite (D) Kaolinite
A-3. Which of the following is not an ore ?

(A) Malachite (B) Calamine (C) Salt cake (D) Cerussite
A-4. Which of the following set of metals mostly found as sulphide ores :
(A) Zn, Cu, Mg (B) Zn, Cu, Pb (C) Fe, Al, Ti (D) Cu, Ag, Au
A-5. The formula of carnallite is :

(A) LiAl(Si2O5)2 (B) KCl.MgCl2.6H2O (C) K2O.Al2O3.6SiO2 (D) KCl.MgCl2.2H2O
A-6. Magnetic separation process may be used for the concentration of :

(A) chalcopyrite (B) bauxite (C) haematite (D) calamine
A-7. Which mineral has been named incorrectly ?

(A) Bauxite : Al2O3.2H2O (B) Corundum : Al2O3
(C) Cryolite : 3NaF .AlF3 (D) Feldspar : Be3Al2Si6O18
A-8. Black tin is

(A) an alloy of Sn (B) an allotrope of Sn (C) 60-70 percent SnO2 (D) 100 percent SnO2
A-9. NaCN is sometimes added in the froth flotation process as a depressant when ZnS and PbS minerals are
expected because :
(A) Pb(CN)2 is precipitated while no effect on ZnS.
(B) ZnS forms soluble complex Na2[Zn(CN)4] while PbS forms froth
(C) PbS forms soluble complex Na2[Pb(CN)4] while ZnS forms froth.
(D) NaCN is never added in froth floatation process.
A-10. Which one of the following reactions represents a calcination reaction?

(A) HgS + O2  Hg + SO2 (B) AgNO3 + NaCl  AgCl + NaNO3
(C) CuCO3.Cu(OH)2  CuO + CO2 + H2O (D) Al2O3 + NaOH  NaAlO2 + H2O
Section (B) : Thermodynamic Principles of Metallurgy

B-1. Selection of temperature to carry out a reduction process depends so as to make :
(A) G negative (B) G positive (C) H negative (D) H positive
B-2. Ellingham diagram represents :

(A) change of G with temperature. (B) change of H with temperature.
(C) change of G with pressure. (D) change of (G – TS) with temperature.
B-3. Which of the following represents the thermite reaction?

(A) 3Mn3 O4 + 8Al  9Mn + 4Al2O3 (B) MgCO3 + SiO2  MgSiO3 + CO2
(C) Cu2S + 2Cu2O  6Cu + SO2 (D) Fe2O3 + 3CO  2Fe + 3CO2
Section (C) : Metallurgy of some useful metals
C-1. Self-reduction of Cu2S to Cu can be carried out in.
(A) bessemer convertor (B) blast furnace (C) both (A) and (B) (D) none of these
C-2. Blister copper is :
(A) impure copper.
(B) obtained in self reduction process during bessemerisation.
(C) both (A) and (B) are correct.
(D) none is correct.
ADVMTL - 181
Metallurgy
C-3. Main source of lead is PbS. It is converted to Pb by :
air
(X) : PbS 


PbO  SO 2
|C
Pb  CO 2
air
(Y) : PbS 


PbO  PbS
|
Pb  SO 2
air
(Z) : PbS 


PbO  SO 2
|CO

Pb  CO 2
Self - reduction process is :
(A) X (B) Y (C) Z (D) none
C-4. Identify the metal M whose extraction is based on the following reactions :
MS + 2O2  MSO4
2MS + 3O2  2MO + 2SO2
MS + 2MO  3M + SO2
MS + MSO4  2M + 2SO2
(A) magnesium (B) aluminium (C) lead (D) tin
C-5. Which of the following reactions represents the self-reduction process?

HgS  O 2  HgO  SO 2 Cu 2 S  O 2  Cu 2 O  SO 2
(A) HgO  HgS  Hg  SO (B) Cu S  Cu O  Cu  SO
 2  2 2 2
PbS  O 2  PbO  SO 2
(C) PbO  PbS  Pb  SO (D) All of these
 2
Section (D) : Electrochemical Principles of Metallurgy

D-1. Magnesium is extracted from ore carnallite by :
(A) the self-reduction process
(B) the carbon-reduction process
(C) the electrolytic process
(D) treating the ore with aqueous NaCN and then reducing the mixture
D-2. NaCl and CaCl2 are added to fused MgCl2 in the electrolysis of MgCl2 since :
(A) melting point is decreased and conductivity is increased.
(B) melting point is increased and conductivity is decreased.
(C) melting point and conductivity both are decreased.
(D) melting point and conductivity both are increased.
D-3. Which of the following metals cannot be extracted by the carbon reduction process ?
(A) Zn (B) Fe (C) Al (D) Sn
D-4. In electrolysis of Al2O3 by Hall-Heroult process :

(A) cryolite Na3[AlF6] lowers the melting point of Al2O3 and increases its electrical conductivity.
(B) Al is obtained at cathode and probably CO2 at anode
(C) both (A) and (B) are correct
(D) none of the above is correct
D-5. During the electrolytic reduction of aluminium, the carbon anodes are replaced from time to time because:
(A) the carbon anodes get decayed
(B) the carbon prevents atmospheric oxygen from coming in contact with aluminium
(C) oxygen liberated at the carbon anodes reacts with anodes to form CO and CO 2
(D) carbon converts Al2O3 to Al
ADVMTL - 182
Metallurgy
Section (E) : Purification or Refining of Impure Metals
E-1. Poling process :
(A) reduces SnO2 to Sn (B) oxidises impurities like iron and removes as scum
(C) uses green poles (D) all of the above are correct
E-2. Aluminium metal is purified by :

(A) Hooper's process (B) Hall-Heroult process
(C) Serpeck's process (D) Baeyer's process
E-3. High purity copper metal is obtained by :

(A) carbon reduction (B) hydrogen reduction
(C) electrolytic reduction (D) thermite reduction
E-4. In the electrolytic refining of lead, Sb, Cu, Ag and Au are found :
(A) on anode (B) in electrolyte solution
(C) in anode mud (D) in cathode mud
E-5. The anode mud in the electrolytic refining of silver contains :

(A) Zn, Cu, Ag, Au (B) Zn, Ag, Au (C) Cu, Ag, Au (D) Au only
E-6. Silver can be separated from lead by :

(A) fractional crystallisation (B) liquation
(C) cupellation (D) addition of zinc (Parke's method)
E-7. The method of zone refining of metals is based on the principle of :

(A) greater mobility of the pure metal than that of impurity
(B) higher melting point of the impurity than that of the pure metal
(C) greater noble character of the solid metal than that of the impurity
(D) greater solubility of the impurity in the molten state than in the solid
E-8. Which does not represent correct method ?

(A) TiCl2 + 2Mg  Ti + 2MgCl2 : Kroll
(B) Ni(CO)4  Ni + 4CO : Mond
1
(C) Ag2CO3  2Ag + CO2 + O : Van Arkel
2 2
(D) ZrI4  Zr + 2I2 : Van Arkel

1. Match the reactions listed in column (I) with processes listed in column (II).
(reactions) (processes)
(A) 4 Au + 8 NaCN + 2 H2O + O2 (air)  4 Na[Au(CN)2] + 4 NaOH (p) Leaching
(B) CuFeS2 + 2 H2SO4  CuSO4 + FeSO4 + 2H2S (q) Smelting

(C) CaO + SiO2  CaSiO3 (r) Hydrometallurgy
(D) MgCl2. 6 H2O   MgCl + 6 H O (s) Calcination

Dry HCl ( g ) 2 2
2. Column – I Column – II

(Reaction) (Process)
(A) FeO + SiO2  FeSiO3 (p) Calcination
(B) 3Mn3O4 + 8Al  4Al2O3 + 9Mn (q) Displacement method

(C) Cu2S + 2Cu2O  6 Cu + SO2 (r) Smelting

(D) 2Al(OH)3  Al2O3 + 3H2O (s) Thermite process
(E) 2Na[Ag(CN)2] + Zn  Na2 [Zn(CN)4] + 2Ag (t) Bessemerisation
ADVMTL - 183
Metallurgy
3. Match the purification processes given in Column-I with the metal(s) given in Column-II.
Column-I Column-II
(A) Poling (p) Titanium
(B) Cupellation (q) Copper
(C) Liquation (r) Silver
(D) Van Arkel method (s) Tin
4. Match the ores given in column-I with type(s) of processes given in column-II.
(A) Haematite (p) Slag formation during roasting/smelting and bessemerisation.
(B) Copper pyrites (q) Reduction by carbon monoxide / carbon at different temperatures.
(C) Carnallite (r) Electrolytic reduction.
(D) Bauxite (s) Calcination.

1. Match Column-I with Column-II and select the correct answer using the codes given below :
Column-I (Metals) Column-II (Ores)
(A) Tin (p) Calamine
(B) Zinc (q) Cassiterite
(C) Iron (r) Cerrusite
(D) Lead (s) Siderite
Codes :
(A) (B) (C) (D) (A) (B) (C) (D)
(A) p q r s (B) q p s r
(C) s r q p (D) q p r s
2. Which is not correct statement ?

(A) Cassiterite, chromite and haematite are concentrated by hydraulic washing (Tabling).
(B) Pure Al2O3 is obtained from the bauxite ore by leaching in the Bayer's process.
(C) Sulphide ore is concentrated by calcination method.
(D) Roasting can convert sulphide into oxide or sulphate and part of sulphide may also act as a reducing
agent.
3. Bauxite is leached with :

(A) KCl (B) NaCN (C) NaOH (D) Na2SO4
4. Froth floatation process for the concentration of sulphide ores is an illustration of the practical application of:
(A) adsorption (B) absorption (C) sedimentation (D) coagulation
5. Which one of the following is not a method of concentration of ore ?

(A) electromagnetic separation (B) smelting
(C) gravity separation (D) froth floatation process
6. The metal which mainly occurs as oxide ore in nature is :

(A) gold (B) lead (C) aluminium (D) magnesium
7. The reason, for floating of ore particles in concentration by froth floatation process is that :
(A) they are light (B) they are insoluble
(C) they are charged (D) they are hydrophobic
ADVMTL - 184
Metallurgy
8. Choose the correct option using the code regarding roasting process.
(I) It is the process of heating the ore in air in a reverberatory furnace to obtain the oxide.
(II) It is an exothermic process.
(III) It is used for the concentration of sulphide ore.
(IV) It removes easily oxidisable volatile impurities present in the concentrated ore.
(A) I, II and III (B) I, II and IV (C) I, III and IV (D) I, II, III and IV
9. Select correct statement

(A) In the decomposition of an oxide into oxygen and solid/liquid metal, entropy increases.
(B) Decomposition of an oxide is an endothermic change.
(C) To make G° negative, temperature should be high enough so that T S° > H°.
(D) All are correct statements.
10. A sulphide ore like ZnS is first roasted into its oxide prior to reduction by carbon because :
(A) a sulphide ore cannot be reduced to metal at all
(B) no reducing agent is found suitable for reducing a sulphide ore.
(C) the Gibb’s free energy of formation of most sulphides are less than that for CS2.
(D) a metal oxide is generally less stable than the metal sulphide.
11. Which of the following statements is correct regarding the slag obtained during the extraction of a metal like
copper or iron ?
(A) The slag is lighter and has lower melting point than the metal
(B) The slag is heavier and has lower melting point than the metal
(C) The slag is lighter and has higher melting point than the metal
(D) The slag is heavier and has higher melting point than the metal
12. The slag consists of molten impurities, generally, in the form of :

(A) metal carbonate (B) metal silicate (C) metal oxide (D) metal nitrate
13. In the metallurgy of iron, the upper layer obtained in the bottom of blast furnace mainly contains :
(A) CaSiO3 (B) spongy iron (C) Fe2O3 (D) FeSiO3
14. Which one of the following reactions occurs during smelting in the reduction zone at lower temperature
(in iron metallurgy) ?
(A) CaO + SiO2  CaSiO3 (slag) (B) Fe2O3 + 3C  2Fe + CO
(C) 3Fe2O3 + CO  2Fe3O4 + CO2 (D) CO2 + C  2CO
15. Magnesium is extracted by electrolysing fused magnesium chloride containing NaCl & CaCl2 using :
(A) a nickel cathode and a graphite anode.
(B) the iron container as anode and a nickel cathode.
(C) the iron container as cathode and a graphite rod as anode.
(D) the nickel container as cathode and iron anode.
16. The process of the isolation of a metal by dissolving the ore in a suitable chemical reagent followed by
precipitation of the metal by a more electropositive metal is called :
(A) hydrometallurgy (B) electrometallurgy (C) zone refining (D) electro-refining
17. Which method of purification is represented by the equations ?

500 K 1675 K
Ti  2 2  
 Ti 4   Ti  2 2
(impure ) (Pure)
(A) Cupellation (B) Poling (C) Van Arkel (D) Zone refining
18. Select correct statement regarding silver extraction / purification process.

(A) When the lead-silver alloy is rich in silver, lead is removed by the cupellation process.
(B) Lead is removed from argentiferous lead by Parke’s process.
(C) Zinc forms an alloy with lead, from which lead is separated by distillation.
(D) Zinc forms an alloy with silver, from which zinc is separated by distillation.
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19. Formation of volatile Ni(CO)4 and then its subsequent decomposition into Ni and CO makes basis of Mond’s
process :
T1 T2
Ni + 4CO  Ni(CO)4  Ni + 4CO, T1 and T2 are :
(A) 100ºC, 50ºC (B) 50ºC, 100ºC (C) 50ºC, 200ºC (D) 200ºC, 50ºC
20. Which one of the following processes involves the principle of fractional crystallisation for the refining of
impure metals ?
(A) Parke’s process (B) Mond’s process (C) Van Arkel process (D) Zone refining
21. In Van Arkel method, if I2 is introduced at 1800 K over impure zirconium metal, the product will be :
(A) iodide of the metal (B) pure metal
(C) impurities react with iodine (D) none of these

1. How many of the following are oxides ores.
(i) Carnallite (ii) Cuprite (iii) Cassiterite (iv) Chromite (v) Cinnabar
(vi) Calamine (vii) Cerussite (viii) Chalcopyrite (ix) Chalcocite.
2. In an ore of iron, iron is present in two oxidation state. Fen+ and Fe(n + 1)+
Number of Fe(n + 1)+ is twice the number of Fen+.
If empirical formula of ore is FexO. Calculate value of [x × 100].
3. In extraction of metal how many of the following ores calcination process is involved.
(i) Dolomite (ii) Malachite (iii) Calcite (iv) Copperpyrities (v) Sylvine
(vi) Cryolite (vii) Siderite (viii) Iron pyrite (ix) Argentite
4. How many of the following metallurgies involve leaching?

Al2O3  Al, ; Ag2S  Ag ; Au  Au ; CuFeS2  Cu ; PbS  Pb
MgCl2  Mg ; FeCO3  Fe ; Low grade copper ore  Cu ; HgS  Hg
5. Among the following metals how many metals are extracted by self-reduction method from their respective
ores. Hg, Zn, Cu, Al, Mg, Pb, Fe, Sn.
6. Number of metals among following which are obtained by electrometallurgy in molten state are.
Li, Ba, Na, Al, Fe, Cu, Pb, Sn, Ag, Au, Zn, Ca, Mg
7. The number of reducing agents involved in the extraction of iron (as pig iron) using blast furnace from ore
haematite is(are).
8. How many of following are correctly matched for electrolytic reducing in molten state.
Ore Reagent / Process Remark
(a) Al2O3 AlF3 and CaF2 added Decrease M.P.
(b) MgCl2 KCl, CaCl2 Increase conductivity
(c) NaCl AlCl3 Decrease M.P.
(d) AlF3 Haroult process Al form at cathode
(e) MgBr2 Dow process Br2 from at anode
(f) Al2O3 conc. NaOH Leaching process
(g) Carnellite Dow process Directly applied to Carnellite crystals.
9. How many of the following reduction processes are correct :

 
(1) B2O3 + Al  B. (2) Cr2O3 + 2Al  Cr..
 
(3) TiCl4 + Mg  Ti. (4) PbS + PbO  Pb.
(5) 3Fe2O3 + CO  2Fe3O4 + CO2 (6) Fe3O4 + CO  3FeO + CO2
(7) 2Cu2O + Cu2S  6Cu + SO2 (8) SnO2 + C  SnO + CO 
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10.^ The minimum voltage required to electrolyse of Al2O3 in the Hall-Heroult process is
Given : Gºƒ (Al2O3) = –1520 kJ mol-1 ; Gºƒ (CO2) = -394 kJ mol-1
If net reaction in Hall-Heroult process is : 3C + 2AI2O3  4AI + 3CO2
(Report your answer as voltage × 10)
11. Calculate mass of Zn (at. mass = 65) required to recover Ag from a 500 ml solution of 0.5 M sodium argento
cyanide (Give your answer by multiplying 8).
G º
12. What is the value of required in kJ/mole for prepration of Mg from Dow’s process using 2.02 voltage.
10
13. Oxidation state of Zr in the compound formed by it in Van Arkel process ; ‘  ’

Bond order of the gas involved in Mond’s process = ‘m’
Total number of ions present in one formula unit of Thomas slag obtained during Bassemerisation of iron = ‘n’
Report your answer as (  × m × n).
14. How many of the following process of refining is/are chemical methods.
(i) Liquation process (ii) Fractional distillation process
(iii) Zone refining method (iv) Chromato graphic method
(v) Cupellation (vi) Poling process
(vii) Hoop’s process (viii) Kroll’s process
(ix) Mond’s process

1. Which of the following manufactured by the electrolysis of their fused salts.
(A) Copper (B) Sodium (C) Aluminium (D) Platinum
2. On the basis of ellingham diagram which of the following is/are correct.
(A) Entropy change for all metal oxides is roughly same.
(B) Below the boiling point, 'TS' factor is same irrespective of metal.
(C) Above G = 0 line, oxide decomposes into metal & oxygen.
(D) If randomness increases the slope increases
3. The smelting of iron in a blast furnace involves, which of the following process/(es) ?
(A) Combustion (B) Reduction (C) Slag formation (D) Sublimation
4. Addition of high proportion of manganese makes steel useful in making rails of rail roads, 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
5. Complexes formed in the cynide process are :

(A) [Au(CN)2]– (B) [Ag(CN)2]– (C) [Cu(CN)4]2– (D) [Zn(CN)4]2–
6. In poling process of purification of Cu, O2 oxidises following group of elements :

(A) S, Sb, As (B) Sb, As, Fe (C) S, Sb, As (D) As, Ag, Au
7. Which of the following process(es) occur(s) during the extraction of copper from chalcopyrites ?
(A) Froth floatation (B) Roasting
(C) Bessemerisation (D) calcination
8. Calcium silicate (slag) formed in the slag formation zone in extraction of iron from haematite ore :
(A) does not dissolve in molten iron.
(B) being lighter floats on the molten iron .
(C) is used in cement industry and as building material.
(D) prevents the re-oxidation of molten iron.
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9. Which of the following statement(s) is (are) incorrect ?
(A) In Serpeck’s process silica is removed by heating the bauxite to 1800°C with coke in a current of N 2
(B) In extraction of lead from galena roasting and self reduction takes place in the same furnace but under
different conditions of temperature and supply of air
(C) The tin is obtained by the carbon reduction of black tin.
(D) None
10. Parting of gold may be done with :

(A) Sulphuric acid (B) Sodium hydroxide (C) Borax (D) Chlorine (Cl2)
11. Liquation process may be applied for the purification of :

(A) copper (B) tin (C) iron (D) zinc
12. Of the following reduction processes, the correct process(es) is/are :

(A) Fe2O3 + CO  Fe + CO2 (B) ZnO + C  Zn + CO
(C) Cu2O + Cu2S  Cu + SO2 (D) PbO + C  Pb + CO
13. Roasting of copper pyrites is done :

(A) to remove moisture.
(B) to oxidise free sulphur and antimony.
(C) to convert pyrites completely into Cu2O and FeO.
(D) to remove volatile organic impurities.
14. Select the correct statement(s) with respect to the differences between roasting and calcination.
(A) In roasting at higher temperature sulphide ores of the some metal like Cu, Pb, Hg etc. are reduced
directly to metal but not in calcination.
(B) Partial fusion occurs in calcination but not in roasting.
(C) Calcination is done in limited supply of air or absence of air but in roasting supply of excess air is
required.
(D) Combustion reaction occurs in roasting but not in calcination.
Comprehension # 1
Amongst the various ores of a metal (M) (sulphide, carbonates, oxides, hydrated or hydroxides) two ores [X]
and [Y] show the following reactivity.
(i) [X] on calcination gives a black solid (S), water and a colourless gas which produces milkyness when
passed through lime water. But this colourless gas does not decolourise the acidified KMNO 4.
(ii) [X] dissolved in dilute HCl on reaction with KI gives a white precipitate (P) and iodine gas.
(iii) [Y] on roasting at high temperature gives metal (M) and a gas (G 1) which turns starch iodate solution
blue.
(iv) [Y] on reaction with dilute HCl gives a white precipitate (MS) and another gas (G 2) which turns lead
acetate solution black and also reacts with gas (G1) to precipitate colloidal sulphur in presence of moisture.
The M, S, [X] and [Y] gives greenish blue flame.
1. The metal ores [X] and [Y] are respectively :

(A) Carbonate and sulphide ores (B) Sulphide and carbonate ores
(C) Carbonate and hydroxide ores (D) Carbonate and oxide ores
2. Which of the following statements is correct about [Y] ?

(A) [Y] is converted to metal (M) by self reduction.
(B) Carbonate extract of [Y] gives yellow precipitate with suspension of CdCO 3.
(C) [Y] is copper glance or copper pyrite
(D) All of these
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3. The gas (G1) acts as
(A) oxidising agent (B) reducing agent
(C) oxidising and reducing agent (D) fluxing agent
4. The white precipitate (P) is of :

(A) Cu2I2 (B) CuI2 (C) K2[CuI4] (D) none
5. Identify the correct statement about [X].

(A) It is malachite or azurite ore (B) Its solution in dil. HCl gives white ppt of Cu22 with K
(C) It on calcination gives black cupric oxide (D) All of these
Comprehension # 2
Read the following graph and answer the following questions.
6. At what approximate temperature, zinc and carbon have equal affinity for oxygen.
(A) 1000ºC (B) 1500ºC (C) 500ºC (D) 1200ºC
7. To make the following reduction process spontaneous, temperature should be :

ZnO + C  Zn + CO
(A) < 1000ºC (B) > 1000ºC (C) < 500ºC (D) > 500ºC but < 1000ºC
8. Which of the following statement is true ?

(A) In the extractive metallurgy of iron, the reduction of calcined / roasted haematite ore in blast furnace
takes place in the lower temperature range as well as in the higher temperature range by carbon
monoxide and carbon respectively.
(B) The reduction of zinc oxide by carbon takes place at higher temperature than that in case of copper.
(C) It is quite easy to reduce oxide ores of copper directly to the metal by heating with coke after 500 - 600K.
(D) All of these
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EXERCISE - 1
PART - I
A-1. This method is commonly used for the concentration of low grade sulphide ores like. ZnS, Cu2S, PbS.
A-2. Substances which are used to prevent certain type of particles, from forming the froth with the bubbles by
complexation.
A-3. By magnetic separation as wolframite (FeWO4 + MnWO4) has magnetic property.
A-4. Copper, Lead, Mercury etc.
A-5. By heating in a current of dry hydrogen chloride gas.
A-6. Stabiliser like cresol and aniline tend to stabilise the froth (i.e. the froth last for longer period).
B-1. All three oxidation curves for the carbon system lie above that for oxidation of zinc, until a temperature of
approximately 1000ºC is reached. At this point, C is thermodynamically capable of reducing ZnO to Zn.
Since this temperature is greater than the boiling point of Zn (907ºC), it will be formed as a vapour. The overall
equation for reduction is, ZnO(s) + C (s)  Zn(g) + CO(g).
B-2. When the temperature is raised a point will be reached where the graph crossed the G = 0 line. Below this
temperature the free energy of formation of oxide is negative, so the oxide is stable. Above this temperature
the free energy of formation of the oxide is positive, and the oxide becomes unstable and should decompose
into metal and oxygen. This explains why HgO, for instance, decomposes spontaneously into its elements
when heated.
B-3. CuO + H2  Cu + H2O CuO + C  Cu + CO

Gºƒ = – 237.2 – (– 129.7) Gºƒ = – 137.2 – (– 129.7)
Gºƒ = – 107.9 kJ Gºƒ = – 7.5 kJ
So, reduction of CuO is quite feasible with H2 than C.
C-1. Oxide of Pb and Hg are unstable while that of zinc is stable towards heat, therefore, oxides of mercury and
lead are reduced by their respective sulphides to the corresponding metals but zinc oxide does not.
C-2. MgO acts as a basic flux and removes certain acidic impurities present in steel in the form of slag.
MgO + SiO2  MgSiO3 ; 3MgO + P2O5  Mg3(PO4)2
C-3. It will combine with tin to form calcium stannate.
C-4. CaO + SiO2  CaSiO3 (slag) ; PbO + SiO2  PbSiO3
CaO converts the PbSiO3 to PbO, PbSiO3 + CaO  PbO + CaSiO3 , and also prevents the formation
of PbSO4.
C-5. It reduces ZnO to Zn and also reduces CO2 to CO which is used as a fuel.
C-6. Remove the infusible impurities of silica as slag

CaCO3  CaO + CO2 ; CaO + SiO2  CaSiO3 (slag)
formed CO2 reacts with carbon and form CO which works as reducing agent
CO2 + C  2CO
C-7. Silica removes iron oxide impurity remaining in the matte by forming silicate, FeSiO3.
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D-1. Na2S is oxidised to Na2SO4 in the presence of air and thus equilibrium is shifted in the forward direction
according to the following reactions.
Ag2S + 2NaCN 2AgCN + Na2S ; 4Na2S + 5O2 + 2H2O  2Na2SO4 + 4NaOH + 2S 
Ag2S +4 NaCN 2Na [Ag(CN)2] + Na2S
D-2. As they have low ionisation energies and are more electropositive elements, they themselves act as strong
reducing agent.
D-3. To lower the melting point and increase conductivity of the mixture.
E-1. (A) liquation process, (B) fractional distillation process, (C) zone refining method and (D) chromatographic
methods.
E-2. This method is used for the purification of those impure metals which contain their own oxides as one of the
impurities. This process is used for the purification of copper and tin.
E-3. Ni, Zr, Ti etc.
PART - II
A-1. (A) A-2. (C) A-3. (C) A-4. (B) A-5. (B)
A-6. (C) A-7. (D) A-8. (C) A-9. (B) A-10. (C)
B-1. (A) B-2. (A) B-3. (A) C-1. (A) C-2. (C)
C-3. (B) C-4. (C) C-5. (D) D-1. (C) D-2. (A)
D-3. (C) D-4. (C) D-5. (C) E-1. (D) E-2. (A)
E-3. (C) E-4. (C) E-5. (D) E-6. (D) E-7. (D)
E-8. (C)
PART - III
1. (A  p, r) ; (B  p, r) ; (C  q) ; (D  s) 2. (A  r, t) ; (B  s) ; (C  t) ; (D  p) ; (E  q).
3. (A  q,s) ; (B  r) ; (C  s) ; (D  p) 4. (A  q, s) ; (B  p) ; (C  r, s) ; (D  r, s)
EXERCISE - 2
PART - I
1. (B) 2. (C) 3. (C) 4. (A) 5. (B)
6. (C) 7. (D) 8. (D) 9. (D) 10. (C)
11. (A) 12. (B) 13. (A) 14. (C) 15. (C)
16. (A) 17. (C) 18. (D) 19. (C) 20. (D)
21. (D)
PART - II
1. 3 (ii, iii, iv) 2. 75 3. 4 (i, ii, iii & vii) 4. 4 5. 3
6. 6 7. 2 8. 5 (a, b, d, e, f) 9. 7 10. 16
11. 65 12. 39 13. 60 14. 5
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PART - III
1. (B,C) 2. (B,C,D) 3. (A,B,C) 4. (A,C) 5. (A,B,D)
6. (A,B,C) 7. (A,B,C) 8. (A,B,C,D) 9. (D) 10. (A,D)
11. (B,D) 12. (A,B,C,D) 13. (A,B,D) 14. (A,C)
PART - IV
1. (A) 2. (D) 3. (C) 4. (A) 5. (D)
6. (A) 7. (B) 8. (D)
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above.
1. The rocky and silicious matter associated with an ore is called :

(1) slag (2) mineral (3) matrix or gangue (4) flux
2. The process of removing lighter gangue particles by washing in a current of water is called :
(1) levigation (2) liquation (3) leaching (4) cupellation.
3. Gravity separation method is based upon :

(1) preferential washing of ores and gangue particles.
(2) difference in densities of ore particles and impurities.
(3) difference in chemical properties of ore particles and impurities.
(4) none of these.
4. In the froth floatation process for the purification of minerals the particles float because :
(1) they are light. (2) they are insoluble.
(3) their surface is preferentially wetted by oil. (4) they bear an electrostatic charge.
5. An ore of tin containing FeCr2O4 is concentrated by :

(1) magnetic separation (2) froth floatation
(3) leaching method (4) gravity separation.
6. Process of heating ore in air to remove sulphur is :

(1) calcination (2) roasting (3) smelting (4) none of these.
7. In roasting :
(1) moisture is removed. (2) non–metals as their volatile oxide are removed.
(3) ore becomes porous. (4) all the above.
8. Which one of the following reactions is an example of calcination process ?

(1) 2 Ag + 2HCl + [O]  2 AgCl + H2O (2) 2 Zn + O2  2 ZnO.
(3) 2 ZnS + 3O2  2 ZnO + 2 SO2 (4) MgCO3  MgO + CO2 .
9. Roasting is carried out in case of :

(1) galena (2) iron pyrites (3) copper glance (4) all.
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10. Slag is a product of :
(1) flux and coke. (2) coke and metal oxide.
(3) flux and impurities. (4) metal and flux.
11. An ore after levigation is found to have basic impurities. Which of the following can be used as flux during
smelting ?
(1) H2SO4 (2) CaCO3 (3) SiO2 (4) Both CaO and SiO2 .
12. Among the following statements, the incorrect one is :

(1) calamine and siderite are carbonates (2) argentite and cuprite are oxides
(3) zinc blende and iron pyrites are sulphides (4) malachite and azurite are ores of copper
13. Electrolytic reduction method is used in the extraction of :

(1) highly electronegative elements. (2) highly electropositive elements.
(3) transition metals. (4) noble metals.
14. Which one of the following metals cannot be extracted by carbon reduction ?
(1) Pb (2) Fe (3) Zn (4) Al.
15. Among the following groups of oxides, the group that cannot be reduced by carbon to give the respective
metals.
(1) Cu2O, SnO2 (2) Fe2O3 , ZnO (3) CuO, K2O (4) PbO, FeO.
16. The process of bringing the metal or its ore into solution by the action of a suitable chemical reagent followed
by extraction of the metal either by electrolysis or by a suitable precipitating agent i.e. more electropositive
metal is called :
(1) electrometallurgy (2) hydrometallurgy (3) electro-refining (4) zone refining.
17. Cryolite is :
(1) Na3AlF6 and is used in the electrolysis of alumina for decreasing electrical conductivity.
(2) Na3AlF6 and is used in the electrolysis of alumina for lowering the melting point of alumina.
(3) Na3AlF6 and is used in the electrolytic purification of alumina.
(4) Na3AlF6 and is used in the electrolysis of alumina for increasing the melting point and electrical conductivity.
18. In the extraction of Cu the reaction takes place in Bessemer converter is :

(1) 2Cu2O + Cu2S  6Cu + SO2 . (2) 2CuFeS2 + O2  Cu2S + FeS + SO2 .
(3) 2Cu2S + 3O2  2Cu2O + 2SO2 . (4) 2FeS + 3O2  2FeO + 2SO2 .
19. Which of the following statement is incorrect about the extractive metallurgy of copper ?
(1) Matte chiefly consists of iron sulphide and some ferrous oxide.
(2) The impurity of iron sulphide is removed as fusible slag, FeSiO3 during roasting.
(3) The copper pyrite is concentrated by froth floatation process.
(4) Copper is obtained by self reduction in bessemer converter.
20. Van Arkel method of purification of metals involves converting the metal to :
(1) volatile stable compound. (2) volatile unstable compound.
(3) non-volatile stable compound. (4) none of these.
21. Copper and tin are refined by :

(1) liquation (2) cupellation (3) bessemerisation (4) poling.
22. The process of zone refining is used for :

(1) silicon (2) germanium (3) gallium (4) all the above.
23. Tin and zinc can be refined by :

(1) cupellation (2) liquation (3) poling (4) bessemerisation.
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24. Match column I with column II and select the correct answer using the codes given below the lists :
Column I Column II
I. Cyanide process. (a) Ultra pure Ge
II. Froth floatation process. (b) Pine oil.
III. Electrolytic reduction. (c) Extraction of Al.
IV. Zone refining. (d) Extraction of Au.
(1) I–(c), II–(a), III–(d), IV-(b) (2) I–(d), II–(b), III–(c), IV–(a)
(3) I–(c), II–(b), III–(d), IV-(a) (4) I–(d), II–(a), III–(c), IV-(b)
25. Match the ores listed in column I with the type of ores listed in column II and select the correct. alternate.
Column I Column II
(a) Limonite. (p) Carbonate ore.
(b) Argentite. (q) Halide ore.
(c) Carnallite (r) Sulphide ore.
(d) Calamine. (s) Oxide ore.
(a) (b) (c) (d) (a) (b) (c) (d)
(1) (s) (r) (q) (p) (2) (p) (s) (q) (r)
(3) (p) (q) (r) (s) (4) (s) (r) (p) (q)
26. Match the method of concentration of the ore in column I with the ore in column II and select the correct
alternate.
Column I Column II
(a) Leaching. (p) Copper pyrite.
(b) Calcination. (q) Siderite.
(c) Froth floatation. (r) Bauxite.
(d) Magnetic separation. (s) Chromite.
(a) (b) (c) (d) (a) (b) (c) (d)
(1) (s) (q) (p) (r) (2) (r) (q) (p) (s)
(3) (p) (q) (r) (s) (4) (q) (r) (p) (s).
27. Match the extraction process listed in column I with metals listed in column II and choose the correct option.
Column I Column II
(a) Self reduction. (p) Copper from copper glance
(b) Carbon and carbon monoxide reduction. (q) Silver from argentite.
(c) Electrolytic reduction in fused state. (r) Aluminium from bauxite.
(d) Complex formation and displacement by metal. (s) Iron from haematite.
(a) (b) (c) (d) (a) (b) (c) (d)
(1) (p) (s) (r) (q) (2) (p) (r) (s) (q)
(3) (s) (p) (r) (q) (4) (p) (r) (s) (q)
28. The iron obtained from the blast furnace is called :

(1) pig iron (2) cast iron (3) wrought iron (4) steel
29. The extraction of zinc from zinc blende involves :

(1) the electrolytic reduction.
(2) the roasting followed by reduction with carbon.
(3) the calcination followed by reduction with another metal.
(4) the roasting at molten temperature.
30. Carbon cannot be used in the reduction of Al2O3 because :

(1) it is non-metal (2) the heat of formation of CO2 is more than that of Al2O3
(3) pure carbon is not easily available (4) the heat of formation of Al2O3 is too high
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Metallurgy
Que. 1 2 3 4 5 6 7 8 9 10
Ans.
Que. 11 12 13 14 15 16 17 18 19 20
Ans.
Que. 21 22 23 24 25 26 27 28 29 30
Ans.

1. Select the group of oxides that cannot be reduced by carbon to give the respective metals. [NSEC-2000]
(A) CaO, K2O (B) Fe2O3, ZnO (C) Cu2O, K2O (D) PbO, Fe2O3
2. Which of the following metal is extracted by thermal reduction process : [NSEC-2000]

(A) AI (B) Fe (C) Cu (D) Mg
3. The metal which can not be obtained by electrolysis of its aqueous salt solution is : [NSEC-2001]
(A) Au (B) Al (C) Ag (D) Cu
4. The metal that can be extracted from its oxide by reduction with carbon is [NSEC-2003]
(A) sodium (B) calcium (C) iron (D) aluminium.
5. In the gold plating process, sodium cyanide solution is used as an electrolyte instead of nitric acid because
(A) cyanide forms a complex with gold and thus helps uniform deposition of gold. [NSEC-2003]
(B) sodium cyanide is a better solvent for gold ions.
(C) cyanide binds with impurity ions and keeps the impurities in solution.
(D) deposition of gold from nitric acid bath is slow.
6. White lead is : [NSEC-2004]

(A) PbCO3 (B) PbCO3. PbO (C) 2PbCO3.Pb(OH)2 (D) 2PbSO4.PbO.
7. High purity germanium is obtained by a technique that is based on [NSEC-2004]

(A) fractional distillation (B) recrystallization
(C) fractional crystallisation (D) diffusion.
8. Stainless steel contains iron along with [NSEC-2006]

(A) Cr + Cu + C (B) Ni + Zn + Cr (C) Cr + Ni + C (D) Ni + Cu + Mn.
9. For the reaction shown below, which statement is true ? [NSEC-2007]

2Fe + 3CdCl2 2FeCl3 + 3Cd
(A) Fe is the oxidizing agent (B) Cd undergoes oxidation
(C) Cd is the reducing agent (D) Fe undergoes oxidation [NSEC-2007]
10. Sapphire is a mineral of : [NSEC-2008]

(A) Cu (B) Zn (C) Al (D) Mg
11. Adding powdered Pb and Fe to a solution containing 1 M each of Pb2+ and Fe2+ ions would result in the
0
formation of – ( E0  0.126 V and EFe2 / Fe  0.44 V ) [NSEC-2010]
Pb 2 / Pb
(A) more of Pb and Fe2+ ions (B) more of Fe and Pb2+ ions
(C) more of Pb and Fe (D) more of Pb2+ and Fe2+ ions
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Metallurgy
12. Pure germanium is an example of- [NSEC-2010]
(A) an intrinsic semiconductor (B) a n-type semiconductor
(C) a p-type semiconductor (D) a n-p type semiconductor
13. The most abundant element in the earth's crust is : [NSEC-2011]

(A) aluminium (B) oxygen (C) silicon (D) iron
14. The commercial of calcium hydride is [NSEC-2012]

(A) Lime (B) Hydrolyth (C) Slaked lime (D) Calgon
15. One of the constituents of German silver is [NSEC-2013]

(A) Ag (B) Mg (C) Cu (D) Al
16. Bell metal is an alloy of copper and [NSEC-2013]

(A) Tin (B) Aluminium (C) Zinc (D) Nickel
17. Van Arkel method of purification of metals involves converting the metal to a [NSEC-2013]
(A) Volatile compound (B) Volatile unstable compound
(C) Non-volatile stable compound (D) Non-volatile unstable compound
THEORY
Cr2O3 is mixed with requisite amount of Al-powder (this mixture is called thermite mixture) and is placed in a
large fire-clay crucible. An intimate mixture of Na2O2 or BaO2 and Mg powder (called ignition mixture or
igniter) is placed in a small depression made in the thermite mixture. The crucible is surrounded by sand
which prevents the loss of heat by radiation. A piece of Mg ribbon is struck into the ignition mixture and the
charge is covered by a layer of fluorspar (CaF2) which acts as a heat insulator. Now Mg-ribbon is ignited so
that ignition mixture catches fire and flame is produced, leading to a violent reaction between Mg and BaO 2
with the evolution of large amount of heat.
Mg + BaO2  BaO + MgO + Heat
Heat produced in the above reaction makes Cr2O3 and AI-powder react together.
Cr2O3 + AI  2Cr () + AI2O3
Molten Cr-metal formed settles down at the bottom of the crucible.
An application of aluminothermic process has been used for joining the broken pieces of iron (welding). In
this process thermite mixture consisting of Fe2O3 and Al-powder in 3 : 1 ratio is placed in a funnel shaped
crucible lined internally with magnesite and having a plug hole at its bottom. The thermite mixture is covered
with a mixture of BaO2 plus Mg-powder (ignition mixture) in which a piece of Mg ribbon is inserted. The ends
of the iron pieces to be welded are thoroughly cleaned and surrounded by a fire-clay mould. When Mg ribbon
is ignited, ignition mixture catches fire and Fe2O3 gets reduced to Fe by Al-powder.
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Metallurgy
Leaching pitch blends with H2SO4 or sodium carbonate to dissolve uranium:
1
U3O8 + 3 Na2CO3 + O  3 Na2UO4 + 3 CO2
2 2
1
U3O8 + 3 H2SO4 + O  3 UO2SO4 + 3 H2O
2 2
Precipitation of Mg (OH)2 from sea water using lime solution:
MgCI2 + Ca(OH)2  Mg(OH)2 + CaCI2.
Oxidation Reduction :
Besides reductions, some extractions are based on oxidation particularly for non-metals.
(a) A very common example of extraction based on oxidation is the extraction of chlorine from brine (chlorine
is abundant in sea water as common salt).
2Cl– (aq) + 2H2O(l)  2OH–(aq) + H2(g) + Cl2(g)
The G for this reaction is + 422 kJ. When it is converted to E0 (using G0 = –nE0F), we get E0 = –2.2 V.
0
Naturally, it will require an external e.m.f. that is greater than 2.2 V. But the electrolysis requires an excess
potential to overcome some other hindering reactions. Thus, Cl2 is obtained by electrolysis giving out H2 and
aqueous NaOH as by-products. Electrolysis of molten NaCl is also carried out. But in that case, Na metal is
produced and not NaOH.
(ii) From Magnesite :

The concentrated ore is calcined at higher temperature
Heated
MgCO3 Strongly
  MgO + CO
2
The calcined ore is heated with coke in a current of dry chlorine gas.

MgO + C + Cl2  MgCl2 + CO
The magnesium chloride is fused and then electrolysed.
2000 º C
MgO + C (Other reducing agents like Si, Al can be used)   Mg + CO
Vaccume

A. General %
is correct.
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Metallurgy
C. Marking Scheme
be awarded.

1. Give the correct order of initials T or F for following statements. Use T if statement is true and F if it is false.
(i) In Gold Schmidt thermite process aluminium acts as a reducing agent.
(ii) Mg is extracted by electrolysis of aqueous solution of MgCI2
(iii) Extraction of Pb is possible by carbon reduction of PbO in smelting.
(iv) Red bauxite is purified by Serpeck`s process
(A) T T T F (B) T F F T (C) F T T T (D) T F T F
2. Leaching of Ag2S is carried out by heating it with a dilute solution of :

(A) NaCN only (B) HCI (C) NaOH (D) NaCN in presence of O2
3. In which of the following pair of metals, both are commercially extracted from their respective ores by self
reduction method ?
(A) Zn, Cu (B) Pb, Cu (C) Sn, Zn (D) Al, Ag
4 Consider the following isolation / purification processes.

(I) Heating impure metal with I2 at 150 – 200ºC and passing the resulting volatile iodide on hot tungsten
filament at 1400ºC to get the pure metal.
(II) Heating the sulphide ore in air until a part is converted to oxide and then further heating in the absence of
air to let the oxide react with unchanged metal sulphide to get the metal.
(III) Electrolysis of the molten electrolyte containing metal oxide and cryolite or florspar to obtain the metal.
The processes used for obtaining aluminium, titanium and lead are respectively :
(A) (I), (II) and (III) (B) (II), (III) and (I) (C) (III), (I) and (II) (D) (II), (I) and (III)
5. Consider the following statements :

S1 : In extraction of iron from haematite ore, the reduction reactions take place only in the lower temperature
range in the blast furnace.
S2 : Calamine is an carbonate ore of zinc.
S3 : The principal ore of aluminium, bauxite, usually contains silica, iron oxides and titanium oxide as
impurities.
S4 : Solidified copper obtained from silica lined convertor (Bessemer converter) has blistered appearance due
to the evolution of SO2.
and arrange in the order of true/false.
(A) F T T T (B) F T F F (C) F F T T (D) T F F T
6. In the extraction of aluminium

Process X : employed for red bauxite to remove iron oxide (main impurity)
Process Y : (Serpeck`s process) : used for white bauxite to remove Z (main impurity) then,
Select correct option for the process X and impurity Z.
(A) X = Hall and Heroult`s process and Z = SiO2 (B) X = Bayer`s process and Z = SiO2
(C) X = Serpeck`s process and Y = iron oxide (D) X = Bayer`s process and Y = iron oxide
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Metallurgy
7. Which of the following metals may be present in the anode mud during electrorefining of copper?
. Gold ; . Iron, . Silver ; V Magnesium
(A)  and  (B)  and V (C)  and  (D)  and V

8. Select the correct statement :

(A) Dolomite contains both magnesium and calcium.
(B) Extraction of lead from galena involves roasting in limited supply of air at moderate temperature followed
by self reduction at higher temperature (to melt the charge).
(C) Extraction of zinc from zinc blende involves roasting followed by reduction with carbon.
(D) The chemical composition of ‘slag’ formed during the extraction of iron and copper is FeSiO 3.
9. The reaction(s) which does (do) not occur in the reduction zone in the extraction of iron from haematite ore
is (are) :
(A) Fe2O3 + CO  2 FeO + CO2 (B) FeO + CO  Fe + CO2
(C) Fe2O3 + 3C  2Fe + 3CO (D) CaO + SiO2  CaSiO3
10. Which of the following is a correct statement ?

(A) Calamine is the ore of zinc. (B) Proustite is the ore of silver.
(C) Cassiterite is the ore of tin. (D) Diaspore is the ore of aluminium.
11. Froth floatation :

(A) is a physical method of separating mineral from the gangue
(B) is a method of concentration of ore depending on the difference in wetability of gangue and the ore
particles.
(C) is used for the concentration of sulphide ores
(D) is a method in which impurities sink to the bottom and ore particles pass on to the surface with froth.
12. Which of the following reduction reactions are actually employed in commercial extraction of metals?
(A) Fe2O3 + 2Al  Al2O3 + 2Fe (B) Cr2O3 + 2Al  Al2O3 + 2Cr
(C) 2Na[Au(CN)2] + Zn  Na2[Zn(CN)4] + 2Au (D) Cu2S + 2CuO  6Cu + SO2

13. The minimum potential difference needed to reduce Al2O3 at 500ºC is :

The reaction for decomposition is :
2 4
Al O  Al + O2 G = + 960 kJ at 500ºC.
3 2 3 3
(Report your answer as potential difference × 2)
14. How many of the following minerals are oxides of metals/metalloids.

(i) Bauxite (ii) Corundum (iii) Dolomite
(iv) Malachite (v) Magnetite (vi) Pyrolucite
(vii) Argentite (viii) Horn silver (ix) Quartz
(x) Cryolite (xi) Siderite (xii) Zincite
(xiii) Calamine (xiv) Syline
(xv) Carnellite
15. Calculate number of metals which can be extracted by self reduction method –
Cu, Al, Fe, Mg, Zn, Sb, Sn, Pb
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Metallurgy
16. Poling process is applied when impurity is a compound of a metal and a non-metal. Atomic number of non-
metal is ............ .
17. How many of following metals can be purified by electro refining by using metal as impure anode.
Cu, Al, Pb, Sn, Ag, Zn, Ca, Mg
18. How many of the following refining processes are correctly matched with their element ?
Liquation - Tin, Fractional distillation - Zinc, Zone refining - Germanium, Poling - Tin, Van Arkel - Titanium,
Cupellation - Silver.

(A), (B), (C) and (D)

Metallic gold frequently is found in aluminosilicate rocks and it is finely dispersed among other minerals. It
may be extracted by treating the crushed rock with aerated sodium cyanide solution. During this process
metallic gold is slowly converted to [Au(CN)2]– , which is soluble in water. After equilibrium has been reached,
the aqueous phase is pumped off and the metallic gold is recovered from it by reacting the gold complex with
zinc, which is converted to [Zn(CN)4]2– . Gold in nature is frequently alloyed with silver which is also oxidised
by aerated sodium cyanide solution.
19. The correct ionic reaction for the process are

(A) 4Au + 8CN– + 2H2O + O2 (air)  4[Au(CN)2]– (soluble) + 4OH–
(B) Au + 2CN–  Au[(CN)2]–
(C) Zn + 2CN–  Zn[(CN)2]–
(D) Zn + 4CN–  Zn[(CN)4]2–
20. There have been several efforts to develop alternative gold extraction processes which could replace this one.
Why ?
(A) Sodium cyanide solutions corrode mining machinery
(B) Sodium cyanide escapes into ground water and produces hydrogen cyanide which is toxic to many
animals.
(C) Gold obtained by this process is not pure.
(D) The amount of gold in aluminosilicate rocks is very less.
21. The process described above in the passage is represents :

(A) ore concentration (B) pyrometallurgical extraction
(C) hydrometallurgical extraction (D) purification of metal

22. Match the name of the processes given in column-I with type(s) of metallurgical methods given in column-II.
(P) Hall-Heroult process (1) Molten Al2O3 + Na3AlF6 electrolysis.
(Q) Dow’s sea water process (2) Molten MgCl2 + CaCl2 + NaCl electrolysis.
(R) Hoop’s process (3) Molten impure aluminium + fluorides of Na+, Ba2+ and Al3+ electrolysis.
(S) Mac-Arthur Forrest process (4) Complex formation and displacement method.
Code :
P Q R S P Q R S
(A) 4 2 3 1 (B) 1 2 4 3
(C) 2 1 3 4 (D) 1 2 3 4
ADVMTL - 201
Metallurgy
Que. 1 2 3 4 5 6 7 8 9 10
Ans.
Que. 11 12 13 14 15 16 17 18 19 20
Ans.
Que. 21 22
Ans.
PART - V : INDIAN NATIONAL CHEMISTRY OLYMPIAD (INChO) STAGE-II

Chemistry of silicon : Silicon is the second most abundant element (~27.2 %) in the earth’s crust after
oxygen (45.5 %). Carbon, silicon, germanium, tin and lead constitute the group 14 of the periodic table.
Chemistry of silicon is distinctly different from that of carbon.
For example, under standard conditions CO2 is a gas whereas SiO2 is a covalent solid.
1.1 In zone refining, silicon is purified as [1 Mark]

(a) portions of Si rod are heated and cooled so that impurities are differentially evaporated
(b) impurities are more soluble in liquid phase than in solid
(c) impurities are less soluble in liquid phase than in solid
(d) impurities are insoluble in molten Si and can be separated
PART - VI : INTERNATIONAL CHEMISTRY OLYMPIAD (IChO) STAGE-V

PROBLEM 1
a) A chromium ore which does not contain water, consists of: Fe(CrO2)2, Mg(CrO2)2, MgCO3, and CaSiO3.
b) It was found by analysis the ore contains 45.6 % of Cr2O3, 7.98 % of Fe2O3, and 16.12 % of MgO.
c) When the ore was treated with a concentrated hydrochloric acid, chromium compounds being present in
the ore did not react with the acid.
d) When the reaction was finished, the ore was thoroughly washed with water (till the reaction with Cl – was
negative) and the solid residue was dried to a constant mass. (IChO-1978)
1.1. Write stoichiometric and ionic equations for the reactions taking place when the ore is treated with the
hydrochloric acid as given in c).
Calculate:
– the content of the compounds (in mass %) present in the ore,
– amounts of substances of the compounds present in the ore.
PROBLEM 2
Metallic gold frequently is found in aluminosilicate rocks and it is finely dispersed among other minerals. It
may be extracted by treating the crushed rock with aerated sodium cyanide solution. During this process
metallic gold is slowly converted to [Au(CN)2]–, which is soluble in water (reaction 1).
After equilibrium has been reached, the aqueous phase is pumped off and the metallic gold is recovered from
it by reacting the gold complex with zinc, which is converted to [Zn(CN)4]2– (reaction 2). (IChO-1998)
2.1 Write balanced ionic equations for reactions (1) and (2).
Gold in nature is frequently alloyed with silver which is also oxidized by aerated sodium cyanide solution.
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Metallurgy
2.2 Five hundred litres (500 L) of a solution 0.0100 M in [Au(CN)2]– and 0.0030 M in [Ag(CN)2]– was evaporated to
one third of the original volume and was treated with zinc (40 g). Assuming that deviation from standard
conditions is unimportant and that all these redox reactions go essentially to completion, calculate the
concentrations of [Au(CN)2]– and of [Ag(CN)2]– after reaction has ceased.
[Zn(CN)4]2– + 2 e–  Zn + 4 CN– E° = – 1.26 V
[Au(CN)2]– + e–  Au + 2 CN– E° = – 0.60 V
[Ag(CN)2]– + e–  Ag + 2 CN– E° = – 0.31 V
2.3 [Au(CN)2]– is a very stable complex under certain conditions. What concentration of sodium cyanide is
required to keep 99 mol % of the gold in solution in the form of the cyanide complex?
{[Au(CN)2]– : Kf = 4 x 1028}
2.4 There have been several efforts to develop alternative gold extraction processes which could replace this one.
Why? Choose one of the options on the answer sheet.
PROBLEM 3
One of the largest factories in Greece, located near the ancient city of Delphi, produces alumina (AI2O3) and
aluminum metal using the mineral bauxite mined from the Parnassus mountain. Bauxite is a mixed
aluminium oxide hydroxide - AIOx(OH)3 – 2x where 0 < x < 1. (IChO-2003)
Production of AI metal follows a two-stage process:
(i) Bayer process : Extraction, purification and dehydration of bauxite (typical compositions for industrially
used bauxites are AI2O3 40-60%, H2O 12-30%, SiO2 free and combined 1-15%, Fe2O3 7-30%, TiO2 3-4%, F,
P2O5, V2O5 etc., 0.05-0.2%). This involves dissolution in aqueous NaOH, separation from insoluble impuri-
ties, partial precipitation of the aluminium hydroxide and heating at 1200oC. Complete and balance the
following chemical reactions of stage (i).
AI2O3 + OH– + ...........  [AI(OH)4(H2O)2]–
SiO2 + OH–  SiO2(OH)22-
SiO2(OH)22- + ...........  CaSiO3  + .............
[AI(OH)4(H2O)2]–  ........... OH– + H2O
AI(OH)3  AI2O + ............
(ii) Heroult-Hall process : Electrolysis of pure alumina dissolved in molten cryolite, NaAIF 6. Typical electro-
lyte composition ranges are Na3AIF6(80-85%), CaF2(5-7%), AIF3(5-7%), AI2O3 (2-8% intermittently re-
charged). Electrolysis is carried out at 940oC, under constant pressure of 1 atm, in a carbon-lined steel
cell (cathode) with carbon anodes. Balance the main reaction of the electrolysis.
AI2O3 (I) + C (anode)  AI (I) + CO2 (g)
Since cryolite is a rather rare mineral, it is prepared according to the following reaction. Complete and
balance this reaction.
HF + AI(OH)3 + NaOH  Na3AIF6 + ...........
During the electrolysis process several parallel reactions take place that degrade the graphite (C) anodes
or reduce the yield.
(iii) By using the thermodynamic data given below, which are taken to be independent of temperature,
determine the thermodynamic quantities H, S and G at 940oC for the reaction.
C (graphite) + CO2 (g)  2CO (g)
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Metallurgy
Problem-4 [22 Points]
Gold Nanoparticles [IChO-2005]
The synthesis and characterization of gold nanoparticles is currently an active research area. The Brust-
Schiffrin method for the synthesis of gold nanoparticle (AuNP) allows the facile preparation of thermally
stable and air-stable AuNPs of reduced polydispersity with a controlled size distribution ranging in diameter
between 1.5 and 5.2 nm. The preparative procedure is briefly described as follows. An aqueous solution of
HAuCl4 is mixed with a toluene solution of tetra-n-octylammonium bromide. The solution is mixed with
dodecanethiol and is treated with an excess of NaBH4. Formation of the AuNPs is evidenced by the immediate,
pronounced darkening of the toluene phase. After ca. 24 h, the toluene solvent is removed with a rotary
evaporator and the resulting solid washed on a frit with ethanol and hexane to remove excess thiol. These
AuNPs can be repeatedly isolated and re-dissolved in common organic solvents without irreversible aggregation
or decomposition.
4.1 Is the methodology for this fabrication referred to a top-down or a bottom-up approach? Select your answer
from the following choices. [2 Points]
(a) top-down approach, which entails reducing the size of the smallest structures to the nanoscale
(b) bottom-up approach, which involves manipulating individual atoms and molecules into nanostructures
4.2 The trimethyl-n-octylammonium bromide can also be used as a phase-transfer reagent. It can carry AuCl4–
from an aqueous phase to an organic phase. Which property does trimethyl-n-octylammonium bromide
possess to function as an efficient phase-transfer reagent? Select your answer from the following choices.
(a) one side of the molecule is electropositive, the other side is electronegative. [2 Points]
(b) one side of the molecule is hydrophilic, the other side is hydrophobic.
(c) one side of the molecule is acidic, the other side is basic.
4.3 What is the function of NaBH4 in this preparation? Select your answer from the following choices.
(a) reducing agent (b) oxidizing agent [2 Points]
(c) neutralization agent (d) complexing agent
4.4 If the average diameter of a gold nanoparticle is 3 nm, what is the estimated number of Au atoms in each
nanoparticle? (the atomic radius of Au is 0.144 nm). Select your answer from the following choices and show
your work. [8 Points]
(a) 102 (b) 103 (c) 104 (d) 105
4.5 What is the estimated percentage of Au atoms on the surface of a nanoparticle?

Select your answer from the following choices and show your work. [8 Points]
(a) 20-30% (b) 40-50% (c) 60-70% (d) 80-90%
PROBLEM 5
Extraction of gold using sodium cyanide, a very poisonous chemical, causes environmental problems and
gives rise to serious public concern about the use of this so called “cyanide process”. Thiosulfate leaching of
gold has been considered as an alternative. In this process, the main reagent is ammonium thiosulfate,
(NH4)2S2O3, which is relatively non-toxic. Although this process appears to be environmentally benign, the
chemistry involved is very complex and needs to be studied thoroughly. The solution used for leaching gold
contains S2 O32– , Cu2+, NH3, and dissolved O2. The solution must have a pH greater than 8.5 to allow free
ammonia to be present. (IChO-2011)
According to the proposed mechanism, a local voltaic micro-cell is formed on the surface of gold particles
during the leaching process and operates as follows:
Anode: Au(s) + 2 NH3(aq)  [Au(NH3)2]+(aq) + e–
[Au(NH3)2]+ (aq) + 2 S2 O32– (aq)  [Au(S2O3)2]3– (aq) + 2 NH3(aq)
Cathode: [Cu(NH3)4]2+(aq) + e–  [Cu(NH3)2]+(aq) + 2 NH3(aq)
[Cu(NH3)2]+(aq) + 3 S O2– (aq)  [Cu(S2O3)3]5– (aq) + 2 NH3(aq)
5.1 In this leaching process, the [Cu(NH3)4]2+ complex ion functions as catalyst and speeds up the dissolution of
gold. Write the net overall oxidation-reduction reaction for dissolution of the gold metal, which is catalyzed by
[Cu(NH3)4]2+ complex ion.
ADVMTL - 204
Metallurgy
PART - I
1. (3) 2. (1) 3. (2) 4. (3) 5. (1)
6. (2) 7. (4) 8. (4) 9. (4) 10. (3)
11. (3) 12. (2) 13. (2) 14. (4) 15. (3)
16. (2) 17. (2) 18. (1) 19. (1) 20. (2)
21. (4) 22. (4) 23. (2) 24. (2) 25. (1)
26. (2) 27. (1) 28. (1) 29. (2) 30. (4)
PART - II
1. (A) 2. (B) 3. (B) 4. (C) 5. (A)
6. (C) 7. (A) 8. (C) 9. (D) 10. (C)
11. (A) 12. (A) 13. (B) 14. (B) 15. (C)
16. (A) 17. (B)
PART - IV
1. (D) 2. (D) 3. (B) 4 (C) 5. (A)
6. (B) 7. (C) 8. (A,B,C) 9. (C,D) 10. (A,B,C,D)

11. (A,B,C,D) 12. (B,C,D) 13. 5 14. 06 15. 3
16. 8 17. 08 18. 6 19. (A) 20. (B)
21. (C) 22. (D)
PART - V
1.1 (b)
PART - VI
1.1. MgCO3 + 2 HCl  MgCl2 + CO2 + H2O
MgCO3 + 2 H+  Mg2+ + CO2 + H2O
CaSiO3 + 2 HCl  CaCl2 + SiO2 + H2O
CaSiO3 + 2 H+  Ca2+ + SiO2 + H2O
The total amount of iron is in the form of Fe(CrO2)2:
Since: Fe2O3  2 Fe(CrO2)2
Mr(Fe2O3) = 159.70
Mr(Fe(CrO2)2) = 223.87 % Fe2O3 = 7.98
2  223.87
% Fe(CrO2)2 = ×7.98 = 22.37
159.70
The difference between the total amount of Cr2O3 and that being contained in Fe(CrO2)2 corresponds to the
amount of Cr2O3, having been in the form of Mg(CrO2)2.
% Cr2O3 in Fe(CrO2)2:
Fe(CrO2)2  Cr2O3
Mr: 223.87 152.02
152.02
% Cr2O3 = × 22.37 = 15.19
223.87
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Metallurgy
% Cr2O3 in Mg(CrO2)2 : 45.5  15.19 = 30.41
Content of Mg(CrO2)2:
CrO32O3  Mg(CrO2)2
Mr: 152.02 192.34
192.34
% Mg(CrO2)2 = × 30.41 = 38.47
152.02
The difference between the total amount of MgO in the ore and that corresponding to Mg(CrO2)2, is contained
in MgCO3. % MgO and % MgCO3 can be calculated analogously as it is given above.
Mg(CrO2)2  MgO
Mr: 192.34 40.32
40.32
% MgO = × 38.47 = 8.06
192.34
MgO  MgCO3
Mr: 40.32 84.32
84.32
% MgCO3 = × 8.06 = 16.86
40.32
Content of CaSiO3 is obtained as complementary value to 100 %.
% CaSiO3 = 100 – (22.37 + 38.47 + 16.86) = 22.30 One kilogram of the ore contains:
223.7 g of Fe(CrO2)2  1 mol
384.7 g of Mg(CrO )  2 mol
168.6 g of MgCO3  2 mol
223.0 g of CaSiO3  2 mol
2.1 Reaction 1: 4 Au + 8 CN– + O2 + 2 H2O  4 [Au(CN)2]– + 4 OH–
Reaction 2: Zn + 2 [Au(CN)2]–  [Zn(CN)4]2– + 2 Au
2.2 E0(Ag/Zn) = –0.31 – (–1.26) = 0.95 V
E0(Au/Zn) = –0.60 – (– 1.26) = 0.66 V
E0(Ag/Zn) > E0(Au/Zn)
Therefore the Ag(l) complex will be reduced first.
(i) mol Ag(l) in 500 dm 3 = 500 × 0.0030 = 1.5 mol
(ii) mol Au(l) in 500 dm 3 = 500 × 0.010 = 5.0 mol
(iii) mol Zn in 40 g = 40 / 65.38 = 0.61 mol
1 mol zinc reacts with 2 mol of Ag(l) or Au(l)
Therefore 0.61 mol Zn will consume 1.2 mol [Ag(CN)2]–
[Ag(CN)2] – remaining = 1.5 – 1.2 = 0.3 mol [Au(CN)2]– will not be reduced.
Concentration of [Au(CN)2]– when reaction has ceased = 0.010 × 3 = 0.030 M
Concentration of [Ag(CN)2]– when reaction has ceased = 0.3 × (3 / 500) = 0.002 M
[Zn(CN)4]2– + 2 e–  Zn + 4 CN– E0 = –1.26 V
[Au(CN)2]” + e–  Au + 2CN~ E0 = – 0.60 V
[Ag(CN)2]” + e–  Ag + 2CN- E0 = – 0.31 V
2.3 Au + 2 CN–  [Au(CN)2]– Kf = 4×108
99 mol % [Au(CN)2]–
[Au(CN)2 ]
K =
f [Au  (CN) ]2
[Au(CN)2 ]
[Au ]  [Au(CN)2 ] = 99 /100

Thus: 100 × [Au (CN) –] = 99 × [Au+] + 99 × [Au(CN) –]

2 2
Therefore [Au+] = [Au (CN) –] / 99
2
substituting into K :
f
4 × 1028 = 99 / [CN”]2
[CN–] = 5 × 10–14
ADVMTL - 206
Metallurgy
2.4 Sodium cyanide escapes into ground water and produces hydrogen cyanide which is toxic to many animals.
3. i) Al2O3 + 2 OH– + 7 H2O  2 [Al(OH)4(H2O)2]–
SiO2 + 2 OH–  SiO2 (OH)22–
SiO2(OH)22– + Ca2+  CaSiO3 + H2O
[Al(OH)4(H2O)2]–  Al(OH)3 + 2 OH– + 2 H2O
2 Al(OH)3  Al2O3 + 3 H2O
ii) 2 Al2O3(l) + 3 C(anode)  4 Al(l) + 3 CO2(g)
6 HF + Al(OH)3 + 3 NaOH  Na3AlF6 + 6 H2O
iii)  r H1213
0
 2 f H1213
0
(CO) –  f H1213
0
(CO2 )  2  (–111) – (–394)  172kJ
 r S1213
0
 2S1213
0 0
(CO) – S1213 0
(CO2 ) – S1213 (C)  2  (–198) – 214 – 6)  176kJ–1
 r G1213
0
 r H1213
0
– TS1213
0
 172 – 1213  0.176  41.5 kJ K –1
4.1 (b) 4.2 (b) 4.3 (a) 4.4 (b) 4.5 (b)
5.1 Au(s) + [Cu(NH3)4]2+(aq) + 5 S2O32– (aq )  [Au(S2O3)2]3–(aq) + [Cu(S2O3)3]5–(aq) +
+ 4 NH3(aq)
4 [Cu(S2O3)3]5–(aq) + 16 NH3(aq) + O2(g) + 2 H2O(l) 
 4 [Cu(NH3)4]2+(aq) + 12 S2 O32– (aq )
Summarizing the above equations:
4 Au(s) + 8 S2 O32– (aq ) + O2(g) + 2 H2O(l)  4 [Au(S2O3)2]3–(aq) + 4 OH–(aq)
PART - I
1. The rocky and silicious impurities associated with an ore is called matrix or gangue.
2. Lighter gangue particles are washed in a current of water by a process called levigation. In levigation the
powdered ore is agitated with water or washed with a upward stream of running water, the lighter particles of
sand, clay etc are washed away leaving behind heavier ore particles.
3. Hydraulic washing or Gravity separation or Levigation method is based on the difference in the densities of
the gangue and ore particles.
4. This method is commonly used for the concentration of the low grade sulphide ores like galena, PbS (ore of
Pb) ; copper pyrites CuFeS2 (ore of copper) ; zinc blende, ZnS (ore of zinc) etc., and is based on the fact that
gangue and ore particles have different degree of wettability with water and pine oil; the gangue particles are
preferentially wetted by water while the ore particles are wetted by oil.
5. An ore of tin containing FeCr2O4 is concentrated by magnetic separation as FeCr2O4 is ferromagnetic.
6. Roasting is a process of heating the concentrated ore (generally sulphide ore) strongly in the excess of air or
O2 below its melting point. During roasting impurities of As, Sb, P and S escape as their volatile oxides.
S (s) + O2 (g)  SO2 (g)
7. Roasting removes easily oxidisable volatile impurities like arsenic (as As2O3), sulphur (as SO2), phosphorus
(as P4O10) and antimony (as Sb2O3).
4M (M = As, Sb) + 3O2  2M2O3 
S + O2  SO2  ; P4 + 4O2  P4O10 
Organic matter, moisture if present in the ore, also get expelled and the ore becomes porous.
8. Conversion of a carbonate into oxide is an example of calcination

MgCO3  MgO + CO2  .
absence of air
ADVMTL - 207
Metallurgy
9. Generally the sulphides of Zn, Pb, Fe, Cu etc. are subjected to roasting to convert in to their oxides prior to
reduction by carbon.
10. In many extraction processes, an oxide is added deliberately to combine with other impurities and form a
stable molten phase immiscible with molten metal called a slag. The principle of slag formation is essentially
the following.
Nonmetal oxide (acidic oxide) + Metal oxide (basic oxide)  Fusible (easily melted) slag.
11. Acidic flux is used. It is an acidic oxide (oxide of a non-metal) like SiO2, P2O5, B2O3 (from borax). It is used
to remove the basic impurity like CaO, FeO, MgO etc. The acidic flux combines with the basic impurity and
forms a slag.
12. (1) Calamine is ZnCO3 and siderite is FeCO3
(2) Argentite is Ag2S while cuprite is Cu2O
(3) Zinc blende is ZnS and iron pyrites is FeS2
(4) Malachite is CuCO3 Cu(OH)2 and azurite is 2CuCO3 Cu(OH)2
13. Electrolytic reduction method is used in the extraction of highly electropositive elements as they themselves
are stronger reducing agents. They lie above hydrogen in electrochemical series.
14. Electrolytic reduction method is used in the extraction of highly electropositive elements as they themselves
are stronger reducing agents. They lie above hydrogen in electrochemical series. The heat of formation of
Al2O3 is very high and therefore, at higher temperature there will be the possibility of formation of Al4C3 with
carbon.
 1800 º C
15. (1) Cu2O + C  2Cu + CO ; SnO2 + 2C (anthracite)   Sn + 2CO.
1200 º C
(2) 2Fe2O3 + 3C  4Fe (spongy iron) + 3CO2 ; ZnO + C   Zn + CO.
(3) Oxides of highly reactive metals (like K2O) are not reduced by carbon. K lie above hydrogen in electrochemical
series and so it acts as strong reducing agent. K is obtained by electrolytic reduction of their fused salts.
(4) FeO + C  Fe + CO ; PbO + C  Pb + CO
16. A hydrometallurgical process for the extraction of metals from ores, concentrates, or secondary materials
essentially contains three basic steps—dissolution of the valuable metal in the aqueous solution (leaching)
purification of leach solution and subsequent recovery of metal from the purified solutions either by electrolysis
or by adding some electropositive metal to it.
17. Cryolite is Na3AlF6 and is used in the electrolysis of alumina. It reduces the melting point of alumina and
increase the electrical conductivity of electrolyte.
18.
Bessemer convertor
Reactions involved :
2FeS + 3O2  2FeO + 2SO2 ; FeO + SiO2  FeSiO3
2Cu2S + 3O2  2Cu2O + 2SO2 ; 2Cu2O + Cu2S  6Cu + SO2 (self reduction)
19. In actual process the ore is heated in a reverberatory furnace after mixing with silica. In the furnace, iron
oxide ‘slags off’ as iron silicate and copper is produced in the form of copper matte which contains mostly
Cu2S and some FeS.
ADVMTL - 208
Metallurgy
50 – 250 º C 1400 º C
20. Ti (impure) + 2I2 (g)    TiI4 (g)     Ti (pure) + 2I2 (g)
Tungsten filament
21. This process is used for the purification of copper and tin to remove the impurities of their oxides.
Green wood  Hydrocarbons  CH4 ; 4CuO + CH4  4Cu (pure metal) + CO2 + 2H2O
Green wood  Hydrocarbon  CH4 ; 2SnO2 + CH4  2Sn + CO2 + 2H2O
22. This process is used when metals are required in very high purity, for specific application. For example pure
Si and Ge are used in semiconductors and hence are purified by this method. Zone refining method is based
on the principle that an impure molten metal on gradual cooling will deposit crystals of the pure metal, while
the impurities will be left in the remaining part of the molten metal.
23. This process is used for the purification of the metal, which itself is readily fusible, but the impurities present
in it are not, i.e., the impurities are infusible. This process is used for the purification of Sn and Zn, and for
removing Pb from Zn-Ag alloy, which is obtained at the end of Parke’s process and contains Pb as impurity.
24. (I) 4Au / Ag (s) + 8CN–(aq) + 2H2O(aq) + O2(g)  4[Au / Ag (CN)2]–(aq) + 4OH–(aq)
2[Au / Ag (CN)2]–(aq) + Zn(s)  2Au / Ag (s) + [Zn(CN)4]2– (aq)
(II) This method is based on the fact that gangue and ore particles have different degree of wettability with
water and pine oil; the gangue particles are preferentially wetted by water while the ore particles are wetted
by oil.
(III) Electrolytic reduction (Hall-Heroult process) :
The purified Al2O3 is mixed with Na3AlF6 (cryolite) or CaF2 (fluorspar) ) which lowers the melting point of the
mixture and increases conductivity. The fused matrix is electrolysed. The electrolytic reactions are :
Cathode : Al3+ (melt) + 3e–  Al(l)
Anode : C(s) + O2– (melt)  CO(g) + 2e–
C(s) + 2O2– (melt)  CO2 (g) + 4e–
(IV) This process is used when metals are required in very high purity, for specific application. For example
pure Si and Ge are used in semiconductors and hence are purified by this method. Zone refining method is
based on the principle that an impure molten metal on gradual cooling will deposit crystals of the pure metal,
while the impurities will be left in the remaining part of the molten metal.
25. (a) Limonite is Fe2O3.3H2O. (b) Argentite is Ag2S.
(c) Carnallite is KCl.MgCl2.6H2O. (d) Calamine is ZnCO3 .
26. (a) Bauxite is leached with NaOH (concentrated) to form soluble Na[Al(OH)4] complex and insoluble impurities
are filtered off.
(b) Carbonate and hydroxide ores are heated in absence of air below their melting point to convert in to their
oxides in reverberatory furnace. This is called calcination. So siderite, FeCO 3 is subjected to calcination.
(c) This method is commonly used for the concentration of the low grade sulphide ores like galena, PbS (ore
of Pb) ; copper pyrites CuFeS2 (ore of copper) ; zinc blende, ZnS (ore of zinc) etc., and is based on the fact
that gangue and ore particles have dIfferent degree of wettability with water and pine oil; the gangue particles
are preferentially wetted by water while the ore particles are wetted by oil.
(d) Chromite ore (FeO.Cr2O3) having magnetic properties is separated from non–magnetic silicious impurities
by magnetic separator.
27. (a) Self-reduction method
This method is also called auto-reduction method or air reduction method. If the sulphide ore of some of the
less electropositive metals like Hg, Cu, Pb etc. are heated in air, a part of these is changed into oxide or
sulphate that then reacts with the remaining part of the sulphide ore to give its metal and SO 2.
Cu2S + 3O2  3Cu2O + 2 SO2
2Cu2O + Cu2S  6Cu + SO2
(b) Reduction with carbon / carbon monoxide :
2Fe2O3 + 3C  4Fe (spongy iron) + 3CO2
Fe2O3 + 3CO  2Fe + 3CO2
Fe3O4 + 4CO  3Fe + CO2
ADVMTL - 209
Metallurgy
(c) Electrolytic reduction (Hall-Heroult process) :
mixture and increases conductivity. The fused matrix is electrolysed.
The electolysis of the molten mass is carried out in an electrolytic cell using carbon electrodes. The oxygen
liberated at anode reacts with the carbon of anode producing CO and CO 2.
C(s) + 2O2– (melt)  CO2 (g) + 4e–
(d) Complex formation and displacement by metal :
Extraction of Ag and Au. Metals like Au and Ag can be precipitated for their salt solution by electropositive
metals for example, Zn.
Metallic Ag is dissolved from its ore in dilute NaCN solution, and the solute so obtained is treated with scrap
Zn when Ag is precipitated. Air is blown into the solution oxidize Na2S. Leaching the metals like silver, gold
with CN– is an oxidation reaction (Ag  Ag+ or Au  Au+)
Ag2S (s) + 4CN– (aq)  2 [Ag(CN)2]– (aq) + S2– (aq)
2Ag(CN)2– (aq) + Zn (s)  [Zn (Cn)4]2– (aq) + 2Ag (s)
Here Zn acts as reducing agent.
28. Molten iron from blast furnace is taken in to sand pigs for solidification. Therefore iron obtained from blast
furnace is called pig iron.
roasting 1100 º C
29. 2ZnS + 3O2   2ZnO + 2SO2 ; ZnO + C   Zn + CO.
Therefore, (2) option is correct.
30. In Ellingham diagram, the fGº of Al2O3 lies below that of CO2. If reduction is carried out at very high
temperature, the Al produced will react with carbon forming Al4C3.
PART - IV
3 0 3 0

1. (i) C r2 O3 + 2 A l  A l2 O3 + 2 C r
(ii) Mg is extracted by electrolytic reduction of fused MgCl2. As Mg lies above hydrogen in electrochemical
series.
 
(iii) PbO + C  Pb + CO ; CaO + SiO2  CaSiO3
(iv) Red bauxite (contains impurity of iron oxide) is purified by Bayer’s / Hall's process.
2. Ag2S (conc. ore) + 2NaCN 2AgCN + Na2S.

Ag2S and AgCN are in equilibrium so Na2S is oxidised by air in to Na2SO4 . Hence equilibrium shifts towards
right side.
4Na2S + 5O2 + 2H2O  2Na2SO4 + 4NaOH + 2S
AgCN + NaCN  Na[Ag(CN)2] (soluble complex)
2Na[Ag(CN)2] + Zn (dust)  2Ag  + Na2[Zn(CN)4].
3. (i) Extraction of tin (carbon reduction) :

SnO2 + C  SnO + CO 
(ii) Extraction of zinc (carbon reduction) :
coke, 673
ZnO + C     Zn + CO
(iii) Extraction of lead (self reduction) :
PbS + 2O2  PbSO4 ; PbS + 3O2  2PbO + 2SO2
PbS + 2PbO  3Pb + SO2 ; PbS + PbSO4  2Pb + 2SO2
(iv) Extraction of copper (self reduction) :
2CuFeS2 + 4O2  Cu2S + 2FeO + 3SO2
ADVMTL - 210
Metallurgy
Cu2S + FeO + SiO2  FeSiO3 (fusible slag) + Cu2S (matte)
2Cu2S + 3O2  2Cu2O + 2SO2 ; 2Cu2O + Cu2S  6Cu + SO2
(v) Extraction of aluminium (electrolytic reduction, Hall-Heroult process) :
mixture and increases conductivity. The fused matrix is electrolysed.
C(s) + 2O2– (melt)  CO2 (g) + 4e–
(vi) Extraction of gold/silver (leaching and displacement method) :
4Au / Ag (s) + 8CN–(aq) + 2H2O(aq) + O2(g)  4[Au / Ag (CN)2]–(aq) + 4OH–(aq)
2[Au / Ag (CN)2]–(aq) + Zn(s)  2Au / Ag (s) + [Zn(CN)4]2– (aq)
150  250 º C 1400 º C

4 (I) Ti (s) (impure) + 22(g)    Ti4 (volatile)   Ti (s) (pure) + 22 (g)
tungsten filament

(II) 2PbS + 3O2  2PbO + 2SO2
high
PbS + 2PbO   3Pb + SO2
temp.
(III) Cathode : Al3+ (melt) + 3e–  Al(l)

C(s) + 2O2– (melt)  CO2 (g) + 4e–
5. S1 : At 500 – 800 K (lower temperature range in the blast furnace)

3 Fe2O3 + CO  2 Fe3O4 + CO2
Fe3O4 + CO  3Fe + 4 CO2
Fe2O3 + CO  2FeO + CO2
At 900 – 1500 K (higher temperature range in the blast furnance) : FeO + CO  Fe + CO2
S2 : calamine is ZnCO3
S3 : It contains Fe2O3, SiO2 and TiO2 as impurities
S4 : The surface of solidified copper has blistered like appearances due to the evolution of SO 2 and so it is
called blister copper.
6. (X) Red bauxite contains the impurities of oxides of iron and silicates. In Bayer process, alumina is
dissolved by reacting sodium hydroxide solution leaving behind the insoluble oxide of iron.
(Y) White bauxite contains the impurity of silica which is removed by Serpeck's method.
1800 º C 1800 º C
Al2O3 + N2 + 3C   2AlN + 3CO ; SiO2 + 2C   Si  + 2CO 

AlN + 3H2O  Al(OH)3  + NH3 ; 2Al(OH)3  Al2O3 + 3H2O.
7. Anode mud contains Ag, Au as impurities.
ADVMTL - 211
Metallurgy
8. (A) dolomite is CaCO3.MgCO3
Roasting Self reduction
(B) 2PbS + 3O2     2PbO + 2SO2 ; PbS + 2PbO      3Pb + SO2
Roasting Carbon reduction
(C) 2ZnS + 3O2     2ZnO + 2SO2 ; ZnO + C        Zn + CO
(D) In extraction of iron the slag obtained is CaSiO 3 where as in copper it is FeSiO3.
9. C + O2  CO2 (combustion zone)
C + CO2  2CO (fusion zone) ; FeO + C  Fe + CO (fusion zone)
CaO + SiO2  CaSiO3 (slag formation zone) ; FeO + CO  Fe + CO2 (slag formation zone)
3Fe2O3 + CO  2Fe3O4 + CO2 (reduction zone) ; Fe3O4 + CO  3FeO + CO2 (reduction zone)
10. (A) Calamine, ZnCO3 is the ore of zinc (B) Proustite, Ag3AsS3 is the ore of silver.
(C) Cassiterite, SnO2 is the ore of tin. (D) Diaspore, Al2O3.H2O is the ore of aluminium.
11. This method is commonly used for the concentration of the low grade sulphide ores like galena, PbS (ore of
Pb) ; copper pyrites CuFeS2 (ore of copper) ; zinc blende, ZnS (ore of zinc) etc., and is based on the fact that
gangue and ore particles have dIfferent degree of wettability with water and pine oil; the gangue particles are
preferentially wetted by water while the ore particles are wetted by oil.
12. (A) 2Al + Fe2O3  AI2O3 + 2Fe (molten) ; H = – 3230 kJ (The reaction is used for thermite welding)
(B) Aluminonthermic process : Cr2O3 + AI  2Cr (molten) + AI2O3
(C) Extraction of gold : 4Au (s) + 8 CN– (aq) + O2 (g) + 2H2O (l)  4 [Au(CN)2]– (aq) + 4OH– (aq)
2[Au(CN)2]– (aq) + Zn (s)  [Zn(CN)4]2– (aq) + 2 Au (s)
(D) Self-reduction method : Cu2S + 3O2  3Cu2O + 2 SO2 ; 2Cu2O + Cu2S  6Cu + SO2
13. Hence, the change in oxidation number of aluminium is 3 per mole. Since 4/3 moles of Al are produced n =
3 × 4/3 = 4
960 000
Eext = 4  96490 = 2.5 V
A potential difference of at least 2.5 V must be applied to the oxide to bring about reduction.
14. (i), (ii), (v), (vi), (ix), (xii)
15. Self reduction method can be used for Cu, Pb, and Sb
16. Impurity is of metal oxide.
17. Cu, Pb, Sn, Zn, Ag : In aqueous medium
Al, Ca, Mg : In molten state
19. Dissolution of gold in NaCN forming soluble complex is reversible, so it is carried out in presence of air
bubbling. Oxygen contained in air oxidises Au to Au+ which then complexes with CN– to form soluble complex.
20. (B) HCN produced with water by NaCN and KCN is poisonous and have carcinogenic activity.
21. The process which involves the dissolution of ore in to a suitable reagent and then extraction of metal from
the solution by more electropositive element is called hydrometallurgy.
22. (A) Hall- Heroult process is the electrolytic reduction of molten Al2O3 dissolved in cryolite or fluorspar.
(B) Dow's sea water process involves the isolation of Mg from sea water as MgCl2 and then electrolytic
reduction of molten MgCl2 dissolved in CaCl2 and NaCl.
(C) Hoop's process is the electrolytic purification of impure aluminium. The cell has three liquid layers upper
most layer containts impure Al, middle one contains fluorides of Na+, Ba2+ and Al3+, lower most layer has
pure Al (obtained by cathodic oxidation).
(D) Mac-Arthur forest cyanide process is the process used for the extraction of gold and silver. Extraction of
gold and silver involves leaching the metal with CN–. The metal is later recovered by displacement method.
ADVMTL - 212
Qualitative Analysis (Anion)
ADVQUA - 213

Section (A) : Heating in dry test tube
A-1. What is importance of dry tests and it is applicable to which kind of substances ?
A-2. Give the observation when each of the following is heated in a dry test tube. Also give balanced equations :
(a) HgCO3 (b) NH4NO2
(c) (NH4Cl + NaNO3) mixture (d) Pb(NO3)2
Section (B) : Flame and borax bead test

B-1. Why compounds shows colours in flame test ?
B-2. Is intensity of colour in flame test, depends upon the concentration of metal present ?
B-3. Why is a green flame not obtained in the case of barium sulphate or barium phosphate ?
B-4. Cu2+ and Ba2+ interfere in the flame test for borate, why ?
2
 Cu ,
B-5. Colourless salt (A) 
740C
 (B) + (C)   blue coloured bead (D)
Identify the compound (A) , (B) ,(C) and (D).
Section (C) : dil. HCl / dil. H2SO4 group

C-1. Why is sodium carbonate extract acidified before performing the confirmatory test for anions ?
C-2. Can sodium carbonate extract be used test for CO32– ions ?
C-3. What will happen if a solution of Ca(HCO3)2, formed by passing the carbon dioxide through a milky solution
of CaCO3 for a longer time if, ammonia solution is added ?
C-4. What will happen if bromine water is added in a white precipitate of BaSO 3 , ?
C-5. Salt (A) + lime water  white precipitate 

white precipitate + prolong passage of gas (B)  it forms soluble salt (C), gas (B) has burning sulphur
smell Identify the anion of salt (A) and (C).
C-6. What will happen ? (Also write the chemical equations) .

(a) When a filter paper moistened with potassium iodate and starch solution is brought in contact with
sulphur dioxide gas.
(b) When H2S gas is made to react with sodium tetrahydroxidoplumbate(II) solution.
(c) When sulphite reacts with dilute H2SO4 in presence of zinc
C-7. A nitrite solution is added to a saturated solution of iron(II) acidified with dilute acetic acid or with dilute
sulphuric acid. If any reactions occurs then write the name and chemical composition of the products
formed. Also write the chemical equations involved.
Section (D) : Concentrated HCl / Conc. H2SO4 group

D-1. Why is it necessary to test for the acid radicals first with dil. H2SO4 and then with conc. H2SO4?
D-2. Why chromyl chloride test is carried out in a dry test tube ?
D-3. Why bromides and iodides do not respond to chromyl chloride test ?
D-4. NaCl on heating with conc. H2SO4 gives HCl where as NaBr and NaI give Br2 and I2 respetively, why?
ADVQUA - 214
D-5. Dilute Hydrochloric acid contains chloride ions but it doesnot give positive chromyl chloride test, why ?
D-6. Salt with X¯ anions

+ conc. H2SO4 + MnO2 /
Green Yellow gas Red Blue gas Violet gas

(A) (B) (C)
Organic layer test Organic layer test Organic layer test
(Not given) Red brown colour Violet colour

excess of Cl2 water excess of Cl2 water
Yellow solution Colourless solution

(D) (E)
Identify the gas A, B and C.
D-7. Why heavy metal chlorides such as Hg2Cl2, AgCl, PbCl2 etc. do not respond to chromyl chloride test.
D-8. Why is a freshly prepared solution of FeSO4 used for the detection of nitrate and nitrite ?
Section (E) : Precipitation Reactions

E-1. In which of the following reagents, the white precipitate of PbSO 4 is soluble ?
dilute HCl, hot concentrated H2SO4, ammonium acetate (6M), ammonium tartrate 6M in the presence of
ammonia, sodium hydroxide solution.
E-2. Mercuric nitrate solution reacts with a soluble sulphate forming a yellow precipitate. If the statement is true
then explain giving the complete balanced equation.
E-3. How will you distinguish between sulphite and sulphate ions ?
Section (A) : Dry test

A-1. When a metal sulphate is heated in dry test tube, the colour changes from blue to white. Then metal
sulphate may be :
(A) BaSO4 (B) CuSO4.5H2O (C) Na2SO4 (D) None of these
A-2. Which of the following can not evolve more than one gas (vapour) if heated in dry test tube.
(A) NaNO3(s) (B) MgCO3(s) (C) FeSO4(s) (D) (NH4)2Cr2O7(s)
A-3. On heating, a white amorphous inorganic compound becomes yellow and on cooling, turns white again.The
salt may be
(A) PbCO3 (B) MgCO3 (C) ZnCO3 (D) K2CO3
A-4. Which of the following metal carbonates liberate. CO2(g) on heating :

(A) Na2CO3 (B) K2CO3 (C) Rb2CO3 (D) Ag2CO3
A-5. In which of the following reactions a brown coloured gas is evolved ?

(A) KBr (s) + dil.H2SO4  
(B) NH4NO2 

(C) NaNO3 800

ºC (D) AgNO3(s) + conc. H2SO4 
A-6. Which of the following will not react with each other when heated together ?
(A) BeO + MgO (B) Li2CO3 + BeO (C) MgO + CaCO3 (D) MgCO3 + Al2O3
ADVQUA - 215
Section (B) : Flame and borax bead test
B-1. Why is concentrated HCl used to dissolve the given metal salt in the flame test ?
(A) strong acids produce better flame test.
(B) HCl is volatile
(C) Volatile metal chloride produce better flame test.
(D) sharper coloured are seen in the flame in presence of Cl– ions.
B-2. The hottest part of the flame of a Bunsen burner is the

(A) Blue Zone (B) Zone of complete combustion
(C) Zone fo partial combustion (D) All parts of the flame are equally hot.
B-3. Metal (M) shows crimson red colour in flame test and its halide is deliquescent then metal (M) could be :
(A) Li (B) Mg (C) Ca (D) Ba
B-4. In Borax bead test, metal oxides react with B2O3 and form a coloured bead. This bead contains.
(A) orthoborate ion (B) metaborate ion (C) double oxide (D) tetraborate ion
B-5. Which one of the following ions does not give borax bead test :
(A) Cr3+ (B) Cu2+ (C) Mn2+ (D) Zn2+
B-6. In the Borax bead test of Co2+, the blue colour of bead is due to the formation of :
(A) B2O3 (B) Co3B2 (C) Co(BO2)2 (D) CoO
B-7. A salt gives white residue in charcoal cavity test but in cobalt nitrate test it gives pink mass. It represents:
(A) Zn+2 (B) Al+3 (C) Mg+2 (D) PO –43
Section (C) : dil. HCl / dil. H2SO4 group

C-1. Which of the following anions are identified by dil. HCl :
(A) NO2–, NO3–, CO32– (B) NO2–, NO3–, SO32– (C) S2–, SO32–, NO2– (D) CH3COO–, I–, CO32–
C-2*.Two inorganic compounds A and B were heated in a dry test tube. A evolved a colourless gas which turned
lead acetate paper black and B evolved a gas which turned lime water milky. The anions in A and B respectively
are :
(A) SO32– , CO32– (B) S2–, CO32– (C) PO34– , HSO3– (D) S2–, NO3–
C-3. If addition of conc. H2SO4 is made to an unknown salt, a colourless and odourless gas is produced then
which of the following can be present ?
(A) CO32– (B) S2– (C) Cl¯ (D) NO3–
C-4. A gas turns lime water milky and acidified K2Cr2O7 solution green then gas is :
(A) HCl (B) H2S (C) SO2 (D) CO2
C-5. A gas has smell like rotten egg and turns lead acetate paper black. The gas is :
(A) NO2 (B) H2S (C) CO2 (D) SO2
C-6. Rotten egg smell

(P)
 dil. H2SO4
CdCO3 suspension –2 (CH3COO)2Pb

Yellow ppt  Salt with X anion Black ppt 
(S) (Q)
Sodium Nitroprusside
Violet
(R)
Anion (X2–) is:

(A) CO32– (B) SO32– (C) S2– (D) S2O32–
ADVQUA - 216
C-7. The acidic solution of a salt produces blue colour with KI starch solution. The reaction indicates the presence
of :
(A) Sulphite (B) Bromide (C) Nitrite (D) Chloride
C-8. Sulphide ion reacts with Na2[Fe(CN)5NO] to form a purple coloured compound (X). In this reaction oxidation
state of iron.
(A) changes from +2 to +3 (B) changes from +3 to +2
(C) changes from +2 to +4 (D) does not change.
Section (D) : Concentrated HCl / Conc. H2SO4 group

D-1. Which of the following pair of anions are identified by conc. H2SO4.
(A) NO3–,CO32– (B) Cl–, NO3– (C) Br–, CO32– (D) CO32–, CH3COO–
D-2. Which of the following anion behaves in a different manner than other on heating with conc. H 2SO4?
(A) Cl¯ (B) I¯
(C) Br¯ (D) All behave in a similar manner
D-3. Which of the following reagents turns white precipitate of AgCl yellow ?
(A) NaNO3 (B) Na3AsO3 (C) Na3AsO4 (D) NaCN
D-4. A Unknown salt (S) when heated with dil. H2SO4 does not evolve brown vapours but with conc. H2SO4 brown
vapours are obtained. The vapours when brought in contact with AgNO 3 solution do not give any precipitate.
The salt (S) contains.
(A) NO2– (B) NO3– (C) – (D) Br–
D-5. When a mixture of solid NaCl and solid K2Cr2O7 is heated with concentrated H2SO4, deep red vapours are
obtained. This is due to the formation of :
(A) chromous chloride (B) chromyl chloride (C) chromic chloride (D) chromic sulphate
D-6. AgCl dissolves in ammonia solution giving :

(A) Ag+, NH4+ and Cl– (B) [Ag(NH3)]+ and Cl– (C) [Ag2(NH3)]2+ and Cl– (D) [Ag(NH3)2]+ and Cl–
D-7. A mixture upon adding conc. H2SO4 gives deep red fumes. Mixture may contain the anions pair :
(A) Cr2O72 – and Cl– (B) Br – and Cr2O72 – (C) NO3– and Cl – (D) CrO42 – and NO32 –
D-8. A solution of a salt in concentrated H2SO4 produced a deep blue colour with starch iodide solution. The salt
may contain :
(A) chloride (B) carbonate (C) acetate (D) bromide
D-9. A colourless solution of a compound gives a precipitate with AgNO3 solution but no precipitate with a solution
of Na2CO3. The action of concentrated H2SO4 on the compound liberates a suffocating reddish brown gas.
The compound is :
(A) Ba(CH3COO)2 (B) CaCl2 (C) NaI (D) NaBr
D-10. An aqueous solution of salt containing an acidic radical X– reacts with sodium hypochlorite in neutral medium.
The gas evolved produces blue black colour spot on the starch paper. The anion X– is :
(A) CH3COO– (B) Br– (C) I– (D) NO2–
D-11. Which of the following gases turn starch iodide paper blue?
(A) CO2 (B) SO2 (C) NO2 (D) H2S
D-12. Nitrate is confirmed by ring test. The brown colour of the ring is due to formation of :
(A) ferrous nitrite (B) nitroso ferrous sulphate
(C) ferrous nitrate (D) FeSO4 .NO2
Section (E) : Precipitation Reactions

E-1. Precipitate of PbSO4 is soluble in :
(A) ammonium acetate (6M) (B) dilute HCl
(C) dilute H2SO4 (D) none of these
ADVQUA - 217
E-2. When a mixture containing phosphate is heated with conc. HNO 3 and ammonium molybdate solution, a
canary yellow precipitate is formed. The formula of the yellow precipitate is :
(A) (NH4)3PO4 (B) (NH4)3PO4.12MoO4
(C) (NH4)3PO4.12MoO3 (D) (NH4)3PO4.(NH4)2MO4
E-3. A metal salt solution gives a yellow precipitate with silver nitrate. The precipitate dissolves in dil. Nitric acid
as well as in ammonium hydroxide. The solution contains.
(A) Br– (B) I– (C) PO43– (D) SO42–

1. Match the anions with the changes observed on qualitative analysis :
Column-I Column-II
(A) SO42– (p) Canary yellow ppt. with ammonium molybdate.
(B) NO3– (q) Brown ring test.
(C) NO2– (r) Yellow ppt. with Hg(NO3)2 solution.
(D) PO43–
(s) Yellow ppt. with AgNO3 solution.
(t) White ppt. with AgNO3 solution.
2. Match the reagent which are used in qualitative analysis of given anions :
Column-I Column-II
(A) AgNO3 solution (p) CO32–
(B) BaCl2 solution (q) Cl–
(C) PbNO3 solution (r) S2–
(D) Acidified KMnO4 solution (s) NO2–
1. Which of the following pair of acidic radical can be distinguished by using dil H 2SO4?
(I) C 2O 24– and NO3– (II) NO3– and NO 2–
(III) Cl– and Br– (IV) HCO 3– and CO32–

(A) I and II (B) II only (C) II and IV (D) III and IV
2. Which of the following salt liberates a colourless gas when acidification with dil. H 2SO4 ?
(A) KNO2 (B) Na2CO2 (C) NaNO2 (D) NaHCO3
3. The compound formed in the borax bead test of Cu2+ ion in oxidising flame is :
(A) Cu (B) CuBO2 (C) Cu(BO2)2 (D) None of these
4. A fire work gave bright crimson red light. It probably contained a salt of :
(A) Ca (B) Sr (C) Ba (D) Mg
5. Alkali metal salt “X” gives a pale violet colour in flame test “X” is :
(A) NaCl (B) LiCl (C) KCl (D) None of these
6. Borax bead is responded generally by :

(A) Alkali metal salt (B) Alkaline earth metals
(C) p-block metal salt (D) d-block metal salt
ADVQUA - 218
d il. H 2SO 4
Colourless gas with brick effervescence
A gNO3 bo il
7. Salt of Anion A White ppt Turns black
Acidic
Green colour
K 2Cr2O7
Shape of anion A will be :

(A) Tetrahedral (B) Trigonal planner (C) Trigonal pyramidal (D) Linear
8. A sodium salt of unknown anion when treated with MgCl2 gives white precipiate only on boiling. The anion of
unknown salt is :
(A) SO42– (B) HCO3– (C) CO3– (D) NO3–
9. Which of the following anions are producing same gas on treatment with (Zn + dil. H 2SO4)
I : SO32– II : HSO3– III : S2– IV : Cl
(A) I and II only (B) I, II and III only (C) I, II, III and IV (D) I, III and IV only
10. Consider the following reaction ; Nitrite + Acetic acid + Thiourea  N2 + HSCN + 2H2O. Formation of
the product in the above reaction can be identified by :
(A) FeCl3 / dilute HCl, when blood red colour appears.
(B) FeCl3 / dilute HCl, when blue colour appears.
(C) K2Cr2O7 / HCl, when green colour appears.
(D) KMnO4 / HCl, when colourless solution is formed.
11.*_ A white sodium salt dissolves readily in water to give a solution which is neutral to litmus. When silver nitrate
solution is added to the solution, a white precipitate is obtained which does not dissolve in dil. HNO 3. The
anion could be :
(A) CO32– (B) Cl– (C) SO32– (D) S2–
12. A salt solution of Cd2+ in dilute HCl, on treatment with a solution of BaCl2 gives a white precipitate, which is
insoluble in concentrated HNO3. Anion in the salt may be –
(A) SO24– (B) CO32– (C) SO32– (D) S2–
13.
The gas ‘G’ will show which of the following property ?

(A) It turns lead acetate filter paper black.
(B) It turns acidified K2Cr2O7 filter paper green.
(C) It produces purple colouration on filter paper moistened with sodium nitroprusside already made alkaline
with sodium hydroxide.
(D) All of these
14. Sodium borate on reaction with conc. H2SO4 and C2H5OH gives a compound (A) which burns with a green
edged flame. The compound (A) is :
(A) H2B4O7 (B) (C2H5)2B4O7 (C) H3BO3 (D) (C2H5)3BO3
15. When a acidic solution of salt (X) is treated with thiourea, N2 is evolved and thiocyanic acid is produced. This
thiocyanic acid give blood red colour with FeCl3 solution. Salt (X) contains the anion :
(A) S2– (B) NO3– (C) NO2– (D) CO32–
ADVQUA - 219
1. How many compounds liberate NH3 on heating from the following?
(NH4)2 SO4, (NH4)2 CO3, NH4Cl, NH4 NO3, (NH4)2 Cr2O7
2. How many of following metals impart a characteristic colour to the Bunsen flame ?
Na, Li, K, Ba, Sr, Mg, Rb, Cs, Be, Ca, Cu
3. Number of ions which are identified by dil. HCl from the following.
SO42–, CO32–, SO32–, HCO3–, S2O32–, NO2–, NO3–, CH3COO–, PO43–
4. Find the total number of acidic radical which produce volatile product with dil HCl
SO24– , I¯, NO2– , NO3– , SO32– , HCO3–
5. Na2S + Na2 [Fe(CN)5NO]  ''X'' (Violet colour)

The total number of possible isomers for complex ''X'' is, provided the ambident behaviour of CN – is not
considered.
6. NaCl + Solid K2Cr2O7 + Conc. H2SO4  ''X'' (reddish brown fumes)
How many axial-d-orbital are involved in hybridization of ''X'' ?
7. Fe2+ + NO3– + H2SO4(conc.)  ‘X’ (Brown ring complex)

The magnetic moment of complex 'X' to its nearest integer is :
8. How many anions evolve brownish gas when treated with dil./conc. HCl. ?
CO32–, SO32–, NO2 , Cl–, Br–, NO3–, CH3COO–
9. Na2CO3, NaCl, NaNO2, Na2SO3, NaBr, CH3COONa are separately treated with AgNO3 solution. In How many
cases white precipitate is/are obtained.
ignite
10. BO33– + conc. H2SO4 + CH3CH2–OH  ‘A’ (green flame)
What is the oxidation number of central atom in Compound 'A' that is responsible for green flame ?
11.
a = difference in the oxidation number of Cl in the product X and product Y, respectively

b = total number of atom in X and Y
c = total number of lone pair in X
then calculate a + b + c = ?
PART - III : ONE OR MORE THAN ONE OPTION CORRECT TYPE
1. Which of the following salts release reddish brown gas when heated in a dry test tube?
(A) LiNO3 (B) KNO3 (C) Pb(NO3)2 (D) AgNO3
2. Which of the following can decompose on heating to give CO2?

(A) Li2CO3 (B) Na2CO3 (C) KHCO3 (D) BaCO3
3. Metals which do not give flame test?

(A) Be (B) Li (C) Mg (D) Ba
ADVQUA - 220
4. In the following diagram bunsen flame the (X) represent
(A) Oxidising zone (B) Reducing zone

(C) Lower temperature zone (D) Hottest portion of flame
5. Metal salts, which respond to Borax bead test?
(A) Nickel salts (B) Copper salts (C) Cobalt salts (D) Aluminium salts
6. Which of the following gases turn lime water milky when passed throught it.
(A) SO2 (B) CO2 (C) HCl (D) H2S
7.
Then A may have :

(A) CO32–, Br– (B) Br–, S2– (C) CH3COO–, S2– (D) CH3COO–, SO32–
8. S2– and SO32– can be distinguished by :
(A) (CH3COO)2Pb (B) Cr2O72– / H+
(C) Na2[Fe(CN)5NO] (D) Zn + dil. H2SO4 followed by (CH3COO)2Pb
9.* Which statements is/ are correct about sodium nitroprusside test?
(A) This test is used for detection of S2– anion.
(B) H2S also gives positive test.
(C) Formation of Na2[Fe(H2O)5NOS] complex confirm the presence of S2– anion.
(D) Iron has +2 oxidation state in sodiumthionitroprusside complex.
10. Which statement(s) is/are correct about Brown ring test ?
(A) This test is given by NO2–, NO3– anions.
(B) Brown ring test depend upon the reduction of NO2– and NO3– to Nitric oxide.
(C) Brown ring is formed due to formation of [Fe(H2O)5NO]2(SO4)3
(D) Charge on NO ligand is +1.
11. Which of the following metal chloride will give chromyl chloride test ?
(A) NaCl (B) KCl (C) AgCl (D) SbCl3
12. Which of the following will be completely or partially dissolved in NH4OH ?
(A) AgCl (B) AgBr (C) AgI (D) BaSO4
13. Reddish-brown gas is obtained when the following are treated with conc. H2SO4?
(A) Br– (B) NO2 (C) NO3 (D) SO32–
14. Each of these are added to a mixture of aqueous solutions of iodide and CHCl3 separately. Which will give a
positive test for iodine when the solutions are vigorously mixed?
(A) NaCl solution (B) NaBr solution (C) Chlorine water (D) Bromine water
Cold filtered boil

15.     white ppt.    (Filtrate)  White ppt  .
excess of BaCl2
Anion of (A) could be :
(A) SO32–, HSO3– (B) CO32–, SO32– (C) SO32–, HCO3– (D) None of these
ADVQUA - 221
Comprehension # 1
Step-I Step-II Step-III
A K 2Cr2O7 passed through acidified with CH3COOH
  B      C      D
chloride salt  conc. H2SO4 dil NaOH solution & Pb(CH3COO) 2 is added
1. ‘A’ can be :
(A) PbCl2 (B) SbCl3 (C) SnCl2 (D) RbCl
2. In step-III if Pb(CH3COO)2 is added without acidifying the solution with CH3COOH then possible product may
be:
(A) PbCrO4 (B) Na2Cr2O7 (C) Na2CrO4 (D) Na2PbO2
Comprehension # 2
3. Gas (B) on passing through cadmium acetate solution will give :

(A) Black ppt (B) Yellow ppt (C) Orange ppt (D) White ppt
4. Gas (B) and (E) are respectively :

(A) H2S, NH3 (B) H2S, SO2 (C) SO2 , H2S (D) H2S, CO2
ADVQUA - 222
EXERCISE - 1
PART - I
A-1. The dry test give information in short time and also provides a clue about the presence or absence of certain
substances so wet analysis may be modified and shortened.
It is applicable to solid substances.
 1
A-2. (a) HgCO3  Hg + CO2 + O
2 2

(b) NH4NO2  N2 + 2H2O (no solid residue)

(c) (NH4Cl + NaNO3) mixture  NaCl + N2O  + 2H2O
 1
(d) Pb(NO3)2  PbO + 2NO2 + O
2 2
B-1. When compound is heated, the electrons gain energy and can jump into the empty orbitals at higher level.
Higher levels are energetically unstable so electrons tend to fall back and transmit the light as characteristic
colour.
B-2. Yes, because intensity of the absorbed light is proportional to the concentration of element in the flame.
B-3. Both barium sulphate and barium phosphate are insoluble and cannot be easily converted into
chlorides.Therefore, the green flame is either indistinct or visible with difficulty.
B-4. Because they also impart green colour to flame.
2
 Cu ,
B-5. Na2B4O7 .10H2O 
740C
 2NaBO2 + B2O3   Cu (BO2)2
(A) (B+C) (Blue bead)
(D)
C-1. Sodium carbonate extract in addition to the sodium salts of anions contain carbonate also. On heating with
the test reagent carbonates of certain metals precipitate which interfere in the detection of acid redicals.
Because of this, Na2CO3 is decomposed by adding HCl, HNO3, H2SO4 , depending upon the nature of test.
C-2. No, because it already contains CO32– ions.
C-3. White precipitate of CaCO3 is formed.
Ca(HCO3)2 + 2 NH3  (NH4)2CO3 + CaCO3 
C-4. Colour of bromine water is discharged according to the following reaction.
BaSO3 + Br2 + H2O  BaSO4  (white) + 2HBr
C-5. (A) = SO3–2 (C) = HSO3– (Lime water test)
C-6. (a) Blue colouration develops due to the formation of iodine gas.
5 SO2 + 2IO3– + 4 H2O  I2 + 5 SO42– + 2 H+
I2 + Starch  Blue (starch iodine adsorption complex)
(b) Black precipitate is formed owing to the formation of PbS.
[Pb(OH)4]|2– + H2S  PbS + 2OH– + 2 H2O
(c) SO3 + 3 Zn + 8 H+  H2S + 3 Zn2+ + 3 H2O
2–
C-7. NO2– + CH3COOH  HNO2 + CH3COO–

3 HNO2  H2O + HNO3 + 2 NO
NO  + Fe2+ + SO42–  [FeNO]SO4 (Nitroso ferrous sulphate)
ADVQUA - 223
D-1. There are some ions like, SO32– , S2– , NO2–, and CH3COO– which can react with dilute/conc. H2SO4 whereas
ions like Cl– , Br–, I– , NO3 , etc. react only with con. H2SO4.
Now if conc. H2SO4 is used first then the anions of both the types will react. Hence, it is desired to test acid
radicals first with dilute H2SO4 and then with conc. H2SO4.
D-2. Because in presence of water, chromyl chloride forms the chromic acid.
CrO2Cl2 + 2H2O  H2CrO4 + 2HCl
D-3. Because chromyl bromide (CrO2Br2) and chromyl iodide. (CrO2I2) compounds are unstable and are not
formed. In such case bromine and iodine are evolved
D-4. HBr and HI are reducing agent where as H2SO4 is oxidizing agent and thus Br2 and I2 are formed.
NaCl + H2SO4  NaHSO4 + HCl
NaBr / NaI + H2SO4  NaHSO4 + HBr/HI
HBr/HI + H2SO4  Br2/I2 + SO2 + 2H2O
D-5. Because in presence of water chromic acid is obtained in place of chromyl chloride.
D-6. A = Cl2
B = Br2
C = I2
D-7. Because heavy metal chlorides are partially dissociated, This test is given generally by Ionic chloride.
D-8. This is because Fe2+ ions on long standing are oxidised to Fe3+ ions which are not used for the detection of
nitrate and nitrite.
E-1. Not in dilute HCl but dissolves in all other reagents.
PbSO4  + H2SO4  Pb2+ + 2 HSO4– ; PbSO4  + 4 CH3COO–  [Pb(CH3COO)4]2– + SO42–
PbSO4  + 2 C6H4O62–  [Pb(C6H4O6)2]2– + SO42–
PbSO4  + 4 OH–  [Pb(OH)4]2– + SO42–
E-2. SO42– + 3 Hg2+ + 2 H2O  HgSO4. 2 HgO  + 4 H+

Yellow precipitate is owing to the formation of basic Hg(II) sulphate.
E-3. BaCl2 gives a white precipitate. with both sulphite and sulphate ions.
BaSO3 is soluble in conc.HCl whereas BaSO4 is insoluble in conc.HCl.
FeCl3 solution gives a red colour with sulphite and no colour is obtained with sulphate.
PART - II
A-1. (B) A-2. (B) A-3. (C) A-4. (D) A-5. (D)
A-6. (C) B-1. (C) B-2. (B) B-3. (A) B-4. (B)
B-5. (D) B-6. (C) B-7. (C) C-1. (C) C-2. (B)
C-3. (A) C-4. (C) C-5. (B) C-6. (C) C-7. (C)
C-8. (D) D-1. (B) D-2. (A) D-3. (B) D-4. (B)
D-5. (B) D-6. (D) D-7. (A) D-8. (D) D-9. (D)
D-10. (C) D-11. (C) D-12. (B) E-1. (A) E-2. (C)
E-3. (C)
PART - III
1. (A) - (r,t) ; (B) - (q) ; (C) - (q, t) ; (D) - (p, s)
2. (A) - (p,q,r,s) ; (B) - (q) ; (C) - (p,q,r) ; (D) - (q,r,s)
ADVQUA - 224
EXERCISE - 2
PART - I
1. (B) 2. (C) 3. (C) 4. (B) 5. (C)
6. (D) 7. (C) 8. (B) 9. (B) 10. (A)
11.*_ (B) 12. (A) 13. (D) 14. (D) 15. (C)
PART - II
1. 3 2. 9 3. 6 4. 3 5. 3
6. 0 7. 4 8. 1 9. 5 10. 3
11. 14
PART - III
1. (A,C,D) 2. (A,C,D) 3. (A,C) 4. (B,C) 5. (A,B,C)
6. (A,B) 7. (C,D) 8. (A,B,C) 9.* (A,D) 10. (A,B,D)
11. (A,B) 12. (A,B) 13. (A,B,C) 14. (C,D) 15. (A,C)
PART - IV
1. (D) 2. (A,D) 3. (B) 4. (B)
ADVQUA - 225

¼ (one fourth) marks will be deducted for indicating incorrect response of each question. No deduction from
the total score will be made if no response is indicated for an item in the answer sheet.
5. There is only one correct response for each question. Filling up more than one response in any question will
be treated as wrong response and marks for wrong response will be deducted accordingly as per instructions
4 above.
1. When a salt is heated with dilute H2SO4 and KMnO4 solution, the pink colour of KMnO4 is discharged, the
salt is :
(1) a sulphite (2) a carbonate (3) a nitrate (4) a bicarbonate
2. Solution of a salt in dilute H2SO4 or acetic acid produces deep blue colour with starch iodide solution. The
salt contains :
(1) Br– (2) I– (3) NO3– (4) NO2–
3. A test tube containing a nitrate and another containing a bromide and MnO 2 are treated with concentrated
H2SO4. The reddish brown fumes evolved are passed through water. The water will be coloured by :
(1) the nitrate (2) the bromide (3) both (4) none of the two
4. Which of the following combines with Fe() ions to form a brown complex?
(1) N2O (2) NO (3) N2 O3 (4) N2O4
5. Colourless salt (A) + dil. H2SO4 or CH3COOH + KI  blue colour with starch. (A) can be
(1) K2SO3 (2) Na2CO3 (3) NH4NO2 (4) NH4Cl
6. There are four test tubes containing dilute HCl, BaCl2, CdCl2 and KNO3 solutions. Which of the following
reagents will help in the identification of BaCl2 ?
(1) NaOH (2) K2CrO4 (3) AgNO3 (4) both (2) and (3)
7. Which one of the following ions does not give borax bead test ?
(1) Cr3+ (2) Cu2+ (3) Mn2+ (4) Zn2+
8. A brick red colour is imparted to Bunsen flame by a :

(1) Ca salt (2) Sr salt (3) Na salt (4) Co salt
9. Which one of the following metal salts produces a blue coloured bead in cobalt nitrate charcoal cavity test ?
(1) Zn2+ (2) Mg2+ (3) Sn2+ (4) Al3+
10. BaCl2 solution gives a white precipitate with a solution of a salt, which dissolves in dilute hydrochloric acid
with the evolution of colourless, pungent smelling gas. The gas as well as the salt both are used as bleaching
agent in the textile industries. The salt contains:
(1) sulphite (2) sulphide (3) acetate (4) carbonate
ADVQUA - 226
11. Pink colour of acidified KMnO4 is decolourised but there is no evolution of any gas. This may happen with the
compound containing the following acid radical.
(1) SO32– (2) NO 2– (3) S2– (4) All of these
12. When KI is added to acidified solution of sodium nitrite :

(1) NO gas is liberated and I2 is set free (2) N2 gas is liberated and HI is produced
(3) N2O gas is liberated and I2 is set free (4) N2 gas is liberated and HOI is produced
13. Zinc pieces are added to acidified solution of SO32 –. Gas liberated can :
(1) turn lead acetate paper black (2) turn lime water milky
(3) give white precipitate with AgNO3 solution (4) None of these
14. A substance on treatment with dilute H2SO4 liberates a colourless gas which produces (i) turbidity with
baryta water and (ii) turns acidified dichromate solution green. The reaction indicates the presence of :
(1) CO32– (2) S2– (3) SO32– (4) NO2–
15. Ammonium molybdate test is used for the estimation of :

(1) PO34– (2) NO3– (3) SO32– (4) SO 24–
16. A colourless gas is dissolved in water and the resulting solution turns red litmus blue ; the gas may have
been which one of the following ?
(1) HCl (2) H2S (3) SO2 (4) NH3
17. When Ag reacts with conc. HCl, then products will be :

(1) AgCl, Cl2 (2) AgCl, H2 (3) AgCl, H2, Cl2 (4) None of these
18. Which of the following salt will evolve sulphur dioxide gas along with formation of yellowish turbidity when
treated with dilute H2SO4 ?
(1) Sodium sulphide (2) Sodium sulphite
(3) Sodium thiosulphate (4) Sodium sulphate
19. Aqueous solution of a salt + MgSO4 solution no precipitate in cold 

Heating
 White precipitate appears.
The salt contains the acidic radical :
(1) CO32– (2) HCO 3– (3) SO32– (4) C 2O 24–
20. In the test for iodine, I2 is treated with sodium thiosulphate (Na2S2O3) :
Na2S2O3 + I2 NaI + ......
(1) Na2S4O6 (2) Na2SO4 (3) Na2S (4) Na3ISO4
21. With Cr2O3, colour of the bead in sodium carbonate bead test is :
(1) red (2) blue (3) yellow (4) green
22. Which metal gives violet colour in oxidising flame when heated with borax ?
(1) Fe (2) Pb (3) Co (4) Mn
23. KBr, on reaction with conc. H2SO4, gives reddish-brown gas :

(1) Bromine (2) Mixture of bromine and HBr
(3) HBr (4) NO2
24. An inorganic salt when heated evolves coloured gas which bleaches moist litmus paper. The evolved gas is :
(1) NO2 (2) SO2 (3) N2O (4) I2
25. Which of the following halide is soluble in water ?

(1) AgF (2) AgCl (3) AgBr (4) AgI
26. Which of the following radical can not be confirmed by using dil.HCl:
(1) S2– (2) S 2O32 – (3) CO32– (4) NO 2–
ADVQUA - 227
27. When K2Cr2O7 is heated with conc. H2SO4 and soluble chloride such as KCl :
(1) red vapours of CrO2Cl2 are evolved
(2) Cl– ion is oxidized to Cl2 gas
(3) CrCl3 is formed
(4) Cr2O72 – ion is reduced to green Cr3+ ion
28. A white solid imparts a violet colour to a Bunsen flame. On being heated with concentrated H 2SO4, the solid
gives violet vapours that turn starch paper blue. The salt may be :
(1) KI (2) NaI (3) MgI2 (4) CaBr2
29. NaCl, NaBr, NaI mixture on adding conc. H2SO4 gives gases, respectively :
(1) HCl, HBr, HI (2) HCl, Br2, I2 (3) Cl2, Br2, I2 (4) None of these
30. Potassium chromate solution is added to an aqueous solution of a metal chloride. The yellow precipitate
thus obtained is insoluble in acetic acid. The precipitate is subjected to flame test, the colour of the flame is:
(1) lilac (2) apple green (3) crimson red (4) brick red

Que. 1 2 3 4 5 6 7 8 9 10
Ans.
Que. 11 12 13 14 15 16 17 18 19 20
Ans.
Que. 21 22 23 24 25 26 27 28 29 30
Ans.

1. Which of the following metal carbonate will decompose on heating ? [NSEC-2000]
(A) K2CO3 (B) Na2CO3 (C) MgCO3 (D) None of these
2. For which element crimson colour is obtained in flame test ? [NSEC-2002]

(A) sodium (B) barium (C) strontium (D) calcium
3. The precipitate of AgCI dissolves in [NSEC-2004]

(A) conc. HNO3 (B) excess of HCI (C) dilute H2SO4 (D) aq. ammonia.
4. Colour of the bead in borax bead test mainly due to the formation of [NSEC-2005]
(A) metal oxides (B) boron oxide (C) metal metaborates (D) elemental boron
5. The brown compound formed in the ring test for nitrates contains the ion [NSEC-2005]
(A) [Fe(H2O)5NO]3+ (B) [Fe(H2O)5NO]2+ (C) [Fe(H2O)5NO]4+ (D) [Fe(H2O)5NO]+.
6. The brown ring test for NO2– and NO3– is due to formation of complex ion with formula : [NSEC-2006]
(A) [Fe(H2O)6]2+
(B) [Fe(CN)5(NO)] 2–
(C) [Fe(H2O)5(NO)]2+
(D) [Fe(H2O)(NO)5]2+
7. MgSO4 on reaction with NH4OH and Na2HPO4 forms a white crystalline precipitate. The formula of the precipitate
is : [NSEC-2009]
(A) Mg(NH4)PO4 (B) Mg3(PO4)2 (C) MgCl2.MgSO4 (D) MgSO4
8. The gas which liberates bromine from a solution of KBr is [NSEC-2013]

(A) Cl2 (B) I2 (C) SO2 (D) HI
ADVQUA - 228

1. What are the products formed when an aqueous solution of magnesium bicarbonate is boiled?
(A) MgCO3, H2O, CO2 (B) Mg(HCO3)2, H2O (C) Mg(OH)2, H2O (D) Mg, CO, H2O
2. NaX (Sodium salt of particular anion ‘X’) gives brisk effervescence of Y with dilute HCl. On heating, NaX
evolves gas Y which can be completely absorbed in conc. KOH solution and is colorless odourless gas.
Hence X and Y respectively are :
(A) HSO3– , SO2 (B) HS¯ & H2S (C) HCO3– , CO2 (D) HC2O –4 & CO2 + CO
3. White precipitate of AgCl turns to greyish or black when :

(A) reacts with Na3AsO3 (B) exposed to sunlight
(C) reacts with K2CrO4 (D) reacts with concentrated HCl
4. A mixture is known to contain NO3– and NO2–. Before performing ring test for NO3–, the aqueous solution
should be made free of NO2–. This is done by heating aqueous extract with :
(A) conc. HNO3 (B) dil HNO3 (C) urea (D) zinc dust
MATCH THE COLUMN

5. CuCO3 was strongly heated to obtain a residue A and gas B. The residue obtained was treated with a salt of
sodium ‘X’ and oxide Y, which produced a blue colored glassy compound C on heating in oxidizing flame.
The same combination of X and Y gave a green colored glassy compound D when Cr2(SO4)3 was heated with
them in oxidizing flame. Match the following accordingly :
(A) A (P) Cu(BO2)2
(B) B (Q) Na2CO3
(C) C (R) CuO
(D) X (S) CO
(T) Cu2O
(U) CO2
(V) NaBO2
(W) Cr(BO2)2

6. A metal salt evolves the dark violet fumes of (X) with MnO2 and this (X) gives the deep blue colouration with
starch solution. Then number of lone pair on central atom in (X).
7. How many of the following will volatilize on heating leaving no solid residue ?
NaNO3, NH4NO3, Ca(H2PO2), NH4HCO3, N2H5HSO3, AlCl3, [Cu(NH3)4]SO4, FeSO4.7H2O
8. Na2S + Na2 [Fe(CN)5NO]  ''A'' (Violet Color)

In Complex ''A'', number of type of ambidentate ligand is/are ''a'' and number of d-orbital involved in hybridisation
is/are ''b'' Then 7a + 8 b will be :

9. Heating which of the following salts in a dry test tube may cause a change in their colour ?
(A) ZnCO3 (white) (B) Co(NO3)2.6H2O (red)
(C) FeSO4.6H2O (green) (D) MnSO4 (faint pink)
10. Which of the following combinations will give yellowish precipitate in an aqueous medium ?
(A) AgNO3 + NaBr (B) (CH3COO)2Pb + Na2CrO4
(C) AgCl + Na3AsO3 (D) AgNO3 + NaNO2
ADVQUA - 229
11. Which of the following produce red coloured flame during flame test?
(A) Li (B) Ca2+ (C) Sr2+ (D) Ba2+
12. When Borax is heated it forms a colourless glassy bead because of formation of :
(A) B2H6 (B) NaBO2 (C) B2O3 (D) Na2B4O7
13. Which of the following anion(s) is/are easily removed from aqueous solution by precipitation?
(A) Cl– (B) SO42– (C) NO3– (D) CO32–
14. H2S and SO2 can be distinguished by :

(A) Litmus paper (B) MnO4–/H+ (C) (CH3COO)2Pb (D) None of these
Comprehension #
When compound (A) is treated with conc. H2SO4, a reddish brown colour gas (B) is evolved. To this solution,
a solution of (C) is added slowly from the side of the test tube, a blue ring is obtained at the junction of two
layers due to formation of (D).
15. Gas (B) may be :

(A) Cl2 (B) Br2 (C) I2 (D) NO2
16. Compound (D) has formula :

(A) C6H5NH–C6H5 (B) (C6H5)2N–N(C6H5)2 (C) C6H5–NH–NH–C6H5 (D) C6H5 – NH – N – C6H5

O
17. Which compound gives same test as compound (A)

(A) NaCl (B) NaBr (C) Na2CrO4 (D) Na2S

A. General%
8. Section 5 contains 1 multiple choice questions. Question has two lists (list-1 : P, Q, R and S; List-2 :
1, 2, 3 and 4). The options for the correct match are provided as (A), (B), (C) and (D) out of which ONLY
ONE is correct.
ADVQUA - 230
C. Marking Scheme

1. An inorganic salt when heated with concentrated H2SO4 evolves a colourless pungent smelling gas but with
concentrated H2SO4 and MnO2, evolves a coloured pungent smelling gas which bleaches moist litmus paper.
The coloured gas is :
(A) NO2 (B) Cl2 (C) Br2 (D) I2
2. Chromyl chloride vapours are dissolved in water and acetic acid and barium acetate solution is added, then:
(A) the solution will remain colourless. (B) the solution will become dark green.
(C) a yellow solution will be obtained. (D) a yellow precipitate will be obtained.
3. When CS2 layer containing both Br2 and I2 (2 : 1) is shaken with excess of chlorine (Cl2) water, the violet
colour due to I2 disappears and a pale yellow colour appears in the solution. The disappearance of violet
colour and appearance of pale yellow colour is due to the formation of :
(A) I3– and Br2 respectively. (B) HIO3 and BrCl respectively.
(C) ICl and BrCl respectively. (D) I– and Br– respectively.
4. A metal salt solution gives a yellow precipitate with silver nitrate. The precipitate dissolves in dilute nitric acid
as well as in dilute ammonia solution. The solution contains :
(A) bromide ions (B) iodide ions (C) phosphate ions (D) chromate ions
5. Which of the following will not give positive chromyl chloride test ?
(A) Copper chloride, CuCl2. (B) Mercuric chloride, HgCl2.
(C) Zinc chloride, ZnCl2. (D) Anilinium chloride C6H5NH3Cl.
6. A white sodium salt dissolves in water to give a solution which is neutral to litmus. When silver nitrate
solution is added to the solution, a white precipitate is obtained which does not dissolve in dilute HNO 3. The
anion is
(A) CO32– (B) Cl– (C) SO32– (D) S2–
7. A one litre flask is full of reddish brown bromine fumes. The intensity of brown colour of vapour will not
decrease appreciably on adding to the flask some :
(A) pieces of marble (B) animal charcoal powder
(C) carbon tetrachloride (D) carbondisulphide

ADVQUA - 231
8. Which of the following statements is/are incorrect ?
(A) A filter paper moistened with cadmium acetate solution turns yellow, when brought in contact with H 2S
gas.
(B) Both carbonate ions as well as bicarbonate ions in the solutions, give reddish-brown precipitate with
mercury(II) chloride.
(C) Sulphites in presence of zinc, reacts with dilute H2SO4 to liberate SO3 gas.
(D) A filter paper moistened with KIO3 and starch turns blue in contact with SO2 vapours.
9. Which of the following reagents can be used for making the distinction between AgCl and AgI ?
(A) Sodium arsenite solution. (B) Dilute ammonia solution.
(C) Potassium cyanide solution. (D) Dilute HNO3.
10. Which of the following statement(s) is/are correct with respect to bromide ions ?
(A) KBr on heating with MnO2 and concentrated H2SO4 liberates Br2 and SO2 gases.
(B) KBr on heating with concentrated H2SO4 liberates Br2 and SO2 gases.
(C) KBr forms HBr with concentrated H3PO4.
(D) KBr(s) liberates Br2 on gentle warming with concentrated H2SO4 and K2Cr2O7(s).
11. Which of the following imparts green/apple green colour to the Bunsen flame ?
(A) Calcium chloride (B) Volatile boron trifluoride
(C) Barium chloride (D) Ethoxy borate
12. What final product(s) is/are formed in the following series of reactions ?
H O
Concentrated borax solution + silver nitrate solution  Precipitate 2 Products (final)
boiling
(A) Ag3BO3 (B) Ag2O (C) H3BO3 (D) AgBO2

13. How many of following metals give Borax bead test

Sc, Ti, V, Cr, Mn, Co, Ni, Cu, Zn
14. How many of the following salts impart characteristic colours to the Bunsen flame ?
NaCl, KCl, CuCl2, BaCl2, CaCl2, SrCl2, ZnCl2, MgCl2, AlCl3
15. How many of the following liberate coloured vapour/gas with concentrated H 2SO4?
KCl (s) + K2Cr2O7 (s), KNO2 (s), KI(s), KBr(s), KCl(s)
KBr (s) + MnO2 (s), KNO3, KCI(s) + MnO2, K2SO3
16. Which of the following statements is/are incorrect

(I) Filter paper moistened with cadmium acetate and lead acetate turn black and yellow respectively,
when brought in contact with H2S gas.
(II) Sulphites in presence of Zinc, reacts with dilute H2SO4 to liberate H2S gas.
(III) Stability of carbonates decrease with increasing metallic character.
(IV) Borax bead test is responded generally by p and d block metal salts.
(V) Sodium chloride on heating with aqueous solution of K2Cr2O7 and concentrated H2SO4 produced
white fumes.
17. How many B–O–B bond(s)(per molecule) is/are present in compound which is used in Borax bead test ?
18. In brown ring complex, if number of ambidentate is/are ''a'' and oxidation state of iron is/are ''b'' then a + b =?

(A), (B), (C) and (D)
ADVQUA - 232
2–
dil. HCl Cr2O7 / H+
(A) (B) + (C) (D)
(Mixture of two salts) (Gas) (Gas) (yellow turbidity)
NO3
–
nd dil. H
MnO4 / H+ Hot a
HgCl2
(E) (F)
(yellow ppt.)
19. Find the anion(s) :

(A) SO32– (B) SO32– , S2– (C) SO32– , CO32– (D) S 2O32 –
20. Find out (E) :

(A) S2– (B) CO32– (C) S 2O32 – (D) SO 24–
21. Find out (F) :

(A) HgSO4.2HgO (B) HgSO4.3HgO (C) HgSO4 (D) Hg2SO4.3HgO

22. Match List-I with List-II and select the correct answer using the codes given below the lists :
List-I List-II
P. White turbidity 1. IO3– + SO2 + starch 
Q. Rotten egg smell 2. SO2 + MnO –4 
R. Colourless solution 3. Zn + NaOH + SO2 
S. Blue colour 4. CO2 + Ca(OH)2 
Code :
P Q R S P Q R S
(A) 1 3 2 4 (B) 3 2 4 1
(C) 4 3 2 1 (D) 4 1 2 3

Que. 1 2 3 4 5 6 7 8 9 10
Ans.
Que. 11 12 13 14 15 16 17 18 19 20
Ans.
Que. 21 22
Ans.
ADVQUA - 233
PART - I
1. (1) 2. (4) 3. (2) 4. (2) 5. (3)
6. (2) 7. (4) 8. (1) 9. (4) 10. (1)
11. (4) 12. (1) 13. (1) 14. (3) 15. (1)
16. (4) 17. (4) 18. (3) 19. (2) 20. (1)
21. (4) 22. (4) 23. (1) 24. (1) 25. (1)
26. (3) 27. (1) 28. (1) 29. (2) 30. (2)
PART - II
1. (C) 2. (C) 3. (D) 4. (B) 5. (B)
6. (C) 7. (A) 8. (A)
PART - III
1. (A) 2. (C) 3. (B) 4. (C)
5. AR, BU, CP, DV 6. 3 7. 4 8. 30
9. (A,B,C,D) 10. (A,B) 11. (A,B,C) 12. (B,C) 13. (A,B,D)
14. (A,B,C) 15. (D) 16. (B) 17. (C)
PART - IV
1. (B) 2. (D) 3. (C) 4. (C) 5. (B)
6. (B) 7. (A) 8. (C) 9. (A,B) 10. (B,C,D)
11. (B,C,D) 12. (B,C) 13. 5 14. 6 15. 7
16. 4 (I), (III), (IV) & (V) 17. 5 18. 1 19. (B)
20. (D) 21. (A) 22. (C)
PART - I
1. SO3 reduces KMnO4 to colourless Mn
2– 2+
5SO32– + 2MnO4– + 6H+  2Mn2+ + 5SO42– + 3H2O
2. Nitrite ion liberates I2 from potassium iodide turning starch blue.

2NO2– + 3I– + 4CH3COOH  I3– + 2NO + 4CH3COO– + 2H2O
I2 + starch  blue colour
3. NO3– gives NO2 with concentrated H2SO4 which on passing through water form colourless HNO3() and
HNO2(). Br– + MnO2 on heating with concentrated H2SO4 gives Br2 gas which on passing through water
imparts it a reddish brown colour.
4. Fe2+ + NO + 5H2O  [Fe(H2O)5NO] 2+ (brown complex)
5. 2NO2– + 3I– + 4CH3COOH  I3– + 2NO  + 4CH3COO– + 2H2O.

I3– + starch  blue colouration.
6. Ba2+ + CrO42–  BaCrO4  (yellow) ; Ag+ + Cl–  AgCl  (white)
ADVQUA - 234
7. Zn2+ is colourless and borax bead test is given by coloured ions such as Cu2+, Mn2+, Fe3+ etc.
8. Ca salts impart brick red colour to the flame.
9. Al2O3.CoO formed in the test is blue in colour. It is called as thenard's blue.
10. Ba2+ + SO32–  BaSO3  (white)

BaSO3 + 2HCl  BaCl2 + SO2(colourless pungent smelling gas) + H2O
SO32– and SO2 both act as bleaching agent.
11. (1) 5SO32– + 2MnO4– + 6H+  2Mn2+ + 5SO42– + 3H2O
(2) 2MnO4– + 5NO2– + 6H+  2Mn2+ + 5NO3– + 3H2O
(3) 2MnO4– + H2S + 6H+  2Mn2+ + 5S  + 8H2O
12. NO2– + 2I– + 4CH3COOH  I2 + 2NO+ 4 CH3COO– + 2H2O
13. SO32– + Zn + 8H+  H2S  + 3Zn2+ + 3H2O

Pb2+ + S2–  PbS  (black)
Ag+ + S2–  Ag2S  (black)
14. SO32– + Ba(OH)2  BaSO3  (white) + 2OH–.
3SO2 + Cr2O72– + 2H+  2Cr3+ (green colour solution) + 3SO42– + H2O.
17. E0SRP of Ag = 0.80 V , E0SRP of Cl– = 1.36 V , E0SRP of H+ = 0.00 V , So Ag can not oxidize Cl– and can not
reduce H+.
18. S2O32– + dil.H2SO4 


 SO2 (Suffocating gas) 2Cl– + S  (yellow turbidity or white turbidity) + H2O
19. HCO3– + Mg2+  Mg (HCO3)2 (No PPt) 


 Mg CO3 
23. KBr + H2SO4  KHSO4 + HBr , 2HBr +9 H2SO4  Br2 + 2H2O + SO2
24. Some nitrates on heating give NO2 which bleaches moist litmus paper due to its oxidizing nature.
25. Solubility order Ag F > AgCl > AgBr > AgI
26. S2– + 2HCl 


 H2S  + 2Cl–
Rotten egg smell (Specific smell)
S2O32– + HCl 

 SO2 (Suffocating gas) + 2Cl + S  (yellow turbidity or white turbidity) + H2O
–

CO32– + 2HCl 
or cold CO2 (Odourless gas)+ H2O + 2Cl–

NO2– + HCl   HNO2 + Cl– NO  (colourless) 
atmospheric air
 NO2 (Brown colour gas)
27. KCl + H2SO4 + K2Cr2O7  CrO2Cl2 (Chromyl Chloride test)

28. K  violet colour in flame test
2I– + conc. H2SO4  HI + SO42– ; HI + H2SO4  I2 + H2O + SO2
I2 + starch  blue colour.
29. HBr and HI are strong reducing agents and are oxidized by H2SO4 to Br2 and I2, respectively.
30. Ba2+ salts gives yellow precipitate with K2CrO4 solution and this precipitate is not soluble in CH3COOH. Ba2+
ions gives apple green colour in the flame test.
PART - III
1. 2Mg(HCO3)2  2MgCO3+CO2+H2O
2. NaHCO3 + HCl  NaCl + H2O + CO2
(NaX) (Y)
ADVQUA - 235
2NaHCO3   Na2CO3 + H2O + CO2 
CO2 + 2KOH  K2CO3 + H2O
CO2 is colourless & odourless gas.
h
3. 2 AgCl 
 2 Ag  (black) + Cl2  .
4. NO2– + H+  HNO2

CO(NH2)2 + HNO2  2N2  + CO2  + 3H2O

5. CuCO3  CuO   CO 2 
( A) (B)
(X)
CuO + NaBO2 + B2O3  Cu(BO2)2 + NaBO2
B orax b ead (C) B lue bea d
Borax
Cr2(SO4)3  

Bead test Green colored metaborate

6. 3I– + MnO2 + H2SO4   3  + Mn2+ + SO42– + H2S
I3– + starch  Blue color due to starch Iodine complex
7. 
NH4NO3  N2O + 2H2O
NH4HCO3 
 NH3 + H2O + CO2
N2H5HSO3 
 N2H4 + H2O + SO2
AlCl3 
 AlCl3(g) (sublimes)
8. A  Na4[Fe(CN)5NOS]
ambidentate ligand [a] = CN , NOS 
a=2
Hybridisation  d2sp3 b =2
7a + 8b = 30
9. ZnCO3 
 ZnO + CO2. ZnO is yellow when hot.
(white)
1
Co(NO3)2.6H2O 
 CoO (black) + 2NO2 + O  + 6H2O
2 2
2FeSO4.6H2O 
 Fe2O3 (brown) + SO2 + SO3 + 6H2O
3MnSO4 
 Mn3O4 + 2SO2 + SO3
(faint pink) (black)
10. AgNO3 + NaBr  AgBr  (Yellow ppt.)
Pb2+ + CrO42–  PbCrO4 (Yellow ppt.)
AgCl + Na3AsO3  Ag3AsO3 (Yellow ppt.)
Ag+ + NO2–  AgNO2 (White ppt.)
ADVQUA - 236
 
12. Na2B4O7.10H2O  Na2B4O7  2NaBO 2  B 2O 3
glassy bead
13. All nitrate are water soluble.

14. H2S, SO2 both are acidic so turns blue litmus red but SO2 is a bleaching agent which turns red litmus
colourless.
MnO4–/H+ oxidising agent, so SO2 is oxidised to SO42– & H2S is oxidized to sulphur
2MnO 4–  5SO2  2H2O  2Mn2  5SO 4 –2  4H

2MnO 4–  5H2S  6H  2Mn2  5 S  8H2 O
(yellow )
Pb + S
2+ 2–
 PbS - (black ppt.), SO2 will not give black precipitate so can be distinguished.
(15-17) NaNO3 + H2SO4 — NaHSO4 + HNO3
(A)
2HNO3 — H2O + 2NO2  + [O]
(B)
2C6H5NHC6H5 + [O] — (C6H5)2N–N (C6H5)5 + H2O
blue ring (D)
This testing also given by various oxidizing agent like CrO42–, Cr2O72– , ClO3– etc.
PART - IV
1. Cl + H2SO4  HCl  (colourless) + HSO4–
–
MnO(OH)2 + 2H2SO4 + 2Cl–  Mn2+ + Cl2  (yellowish green) + 2SO42– + 3H2O
Cl2 + H2O  2HCl + [O]
Litmus + [O]  colourless oxidised form
Cl2 is a yellowish green gas which bleaches litmus paper by oxidation.
2. CrO2Cl2 + 2H2O  H2CrO4 + 2HCl

H2CrO4 + (CH3COO)2Ba  BaCrO4 (Yellow) + 2CH3COOH
3. 5Cl2 + I2 + 6H2O  2HIO3 (colourless) + 10HCl

Br2 + Cl2 2BrCl (pale yellow)
4. Ag3PO4 is yellow precipitate which is soluble in both dilute ammonia solution and dilute HNO 3.
HPO42– + 3Ag+  Ag3PO4 + H+
Ag3PO4 + 2H+  H2PO4– + 3Ag+; Ag3PO4 + 6NH3  3[Ag(NH3)2]+ + PO43–
Pale yellow precipitate of AgBr is not soluble in dilute HNO3; bright yellow precipitate of AgI is not soluble in
both; Ag2CrO4 is obtained as red precipitate.
6. NaCl + AgNO3  AgCl  (white) + NaNO3 ; Ag2S  (black).
Ag2CO3 and Ag2SO3 dissolves in dilute HNO3 liberating CO2 and SO2 respectively.
Both Ag2CO3 and Ag2SO3 are white. AgCl is white but insoluble in dilute HNO 3. NaCl solution is neutral to
litmus as it is a salt of strong acid and strong base.
7. Marble (CaCO3) do not react, adsorb, absorb or dissolve Br2. As such there is no change in colour of Br2.
Remaining dissolves or absorb or adsorb bromine.
8. (A) Cd2+ (aq) + H2S (g)  CdS  (yellow) + 2H+ (aq)
(B) Co32– + 4Hg2+ + 3H2O  HgCO3 . 3HgO  (reddish-brown) + 6H+
HCO3– (aq) does not give precipitate.
(C) SO32– + 3Zn + 8H+  H2S  + 3Zn2+ + 3H2O
(D) 5SO2 + 2IO3– + 4H2O  I2 + 5SO42– + 8H+
ADVQUA - 237
9. (A) 3AgCl  + AsO33–  Ag3AsO3  (yellow) + 3Cl–
AgI is unaffected by this treatment.
(B) AgCl + 2NH3  [Ag(NH3)2]Cl
AgI is not soluble in dilute ammonia solution.
(C) Both soluble in potassium cyanide, forming soluble complexes.
(D) Both insoluble in dilute HNO3.
10. (A) 2KBr + MnO2 + 2H2SO4  Br2 + 2K+ + Mn2+ + 2SO42– + 2H2O
(B) 2KBr + 2H2SO4  Br2 + SO2 + SO42– + 2K+ + 2H2O
(C) KBr + H3PO4  HBr + H2PO4– + K+
(D) 6KBr + K2Cr2O7 + 7H2SO4  3Br2 + 2Cr3+ + 2K+ + 7SO42– + 7H2O
11. BF3 colour the flame green ; B(OC2H5)3 burns with green edged flame ; Barium chloride (volatile) gives apple
green colour to flame.
12. B4O72– + 4Ag+ + H2O  4AgBO2 (white) + 2H+
Hydrolysis
2AgBO2 + 3H2O     Ag2O (brown) + 2H3BO3
 / H2O
13. Cr, Mn, Fe, Co, Ni, Cu give Borax bead test.
14. NaCl-Golden yellow ; KCl-Lilac ; CuCl2-bluish-green, BaCl2-Apple green ; SrCl2-Crimson ; CaCl2-Brick red.
15. (i) 4Cl– + Cr2O72– + 6H+  2CrO2Cl2  (deep red) + 3H2O
(ii) NO2– + H+  HNO2 ; 3HNO2  HNO3 + NO  + H2O
2NO  + O2   NO2  (brown)
(iii) 3I– + 2H2SO4  I3–  (violet) + SO42– + 2H2O + SO2
(iv) 2KBr + 2H2SO4  Br2  (reddish brown) + SO2  + NO42–+ 2K+ + 2H2O
–
(v) Cl– + H2SO4  HCl  (colourless) + HSO4
(vi) 2KBr + MnO2 + 2H2SO4  Br2  (reddish-brown) + 2K+ + Mn2+ + 2SO42– + 2H2O
(vii) 4NO3– + 2H2SO4  Br2  (reddish-brown) + 2K+ + Mn2+ + 2SO42– + 2H2O
(viii) KCl + MnO(OH)2 + 2H2SO4 + 2Cl– (brown)  Mn2+ + Cl2  (yellowish green) + 2SO42– + 3H2O
(ix) SO32– + 2H+  SO2  (colourless) + H2O
16. (I) Pb+2 + H2S  PbS
black
Cd+2 + H2S  CdS
yellow
(II) Zn + H2SO4 + SO3–  H2S + Zn2+
(III) Stability of carbonate  metallic character
(IV) Borax bead test is responded by d-block metal salt.
(V) NaCl + K2Cr2O7 + H2SO4  CrO2Cl2 + Cr3+ + SO 24–
17. Na2B4O7.10H2O contains 5 B–O–B bonds

Borax
18.  a=0 H2O, NO+ are not ambidentate ligand
b=1 Fe+1
a+b=1
ADVQUA - 238
2– 2– dil. HCl
S , SO3 +
(19-21)
(B) (C)
(A) mixture of two salt
– + 2– +
MnO4/H Cr2O7 / H
2– hot and conc.HNO3

SO4 S
(E) (D)
HgCl2
(F) yellow
22. 1 IO3– + SO2  I2 + SO 24–

I2 + Starch  deep blue colour
2 SO2 + MnO –4  MnSO4 + SO 24–
colourless
3 Zn + NaOH + SO2  H2S + Zn2+
rotten egge smell
4 CO2 + Ca(OH)2  CaCO3 (milky)
ADVQUA - 239
Qualitative Analysis (Cations)
ADVQUA - 240

Section (A) : Ist Group
A-1. Name of one chloride which is soluble in hot water as well as in excess of HCl.
A-2. Why do lead salts turn black on keeping for a long time in the laboratory ?
A-3. A metal salt forms a yellow precipitate (P) with potassium iodide solution and black precipitate (Q) with
acidified H2S. Yellow precipitate (P) does not dissolve in excess dilute solution of KI. Then metal salt could
be and also write the chemical equation.
A-4. When calomel reacts with ammonia solution, a black precipitate is formed. Write the chemical equation and
also name the reaction nature.
A-5. What products are formed when precipitate formed by the reaction of Hg22+ ions and excess of sodium
hydroxide solution is boiled ?
A-6. A metal salt forms a green precipitate with KI solutiion and white ppt with KCl. This green precipitate under
goes disproportionation reaction in excess of reagent which results in a soluble compound and black precipitate
then write the chemical equations and identify the cation in the original sample.
A-7. Why bright yellow precipitate of AgI is soluble in KCN and Na2S2O3 solution.
A-8. What happens when diammine argentate (I) reacts with hydrazine sulphate ?
A-9. Solid (A) is used in photographic film, Identify (A) to (E) ?
Section (B) : II A Group

B-1. Why Na2S cannot be used in place of H2S (in presence of HCl) as a reagent for IInd group cations ?
B-2. Does sodium hydroxide solution can be used to differentiate Hg(I) from Hg(II) ?
B-3. What happens when white precipitate of Bi(OH)3 is boiled ?
B-4. Is there any reaction other then cyanide reaction which can be used for the differentiation of Cu2+ and Cd2+
ions?
ADVQUA - 241
B-5. Identify A to F.
(F) K 4 [Fe(CN)6 ]
  (A) BaCl2
  (B)  (C)
Chocolate Blue solution White ppt.
brown
(D) Hypo
  (E)
Brown ppt. Solution White ppt.
Section (C) : IIB Group

C-1. An original solution is prepared in conc. HCl when diluted a white ppt. is formed. What does it indicate ?
C-2. Can we use other reagent in place of yellow ammonium sulphide for separation of group-II (A) and group-II (B)
redicals ?
C-3. Why HNO3 can not be used in place of HCl as a reagent (H2S in presence of HCl) for IInd group cations ?
C-4. Which cation can be detected by "Marsh's test" ? Also write the balanced chemical reaction.
C-5. A metal salt (X) forms yellow precipitate with H2S in acidic medium. This yellow precipitate is soluble in conc.
HNO3 due to formation of compound (Y). Compound (Y) gives ammonium molybdate test then find the metal
salt (X).
C-6. Identify (A) based on the following facts :

(i). (A) reduces HgCl2 solution to white ppt. changing to grey.
(ii). (A) turns FeCl3 yellow coloured solution to green.
(iii). (A) gives white ppt. with NaOH soluble in excess of NaOH.
(iv). (A) gives yellow dirty ppt. on passing H2S gas, soluble in yellow ammonium sulphide (YAS).
(v). (A) gives chromyl chloride test.
Section (D) : IIIrd Group

D-1. Why is the original solution boiled with conc. HNO3 in group  ?
D-2. Why use of excess cobalt nitrate solution should be avoided in the dry test of aluminium compounds ?
D-3. Do Fe(III) salts and Fe(II) salts both give red colouration with dimethylglyoxime in ammonical solution. If not
then which iron salt gives red colouration with dimethylglyoxime ?
D-4. Which colour precipitate is formed by Fe(II) salt with potassium ferrocyanide, (i) in complete absence of air
and (ii) under ordinary atmospheric conditions ?
D-5. Which basic radical(s) decolourise acidic KMnO 4 solution ?
Section (E) : IVth Group

E-1. Partial precipitation of Mn2+ as Mn(OH)2 occurs with ammonia solution but the precipitate is soluble in
ammonium salts. Explain ?
E-2. Why Zn(II) salt is not precipitated as Zn(OH)2 by ammonia solution in the presence of excess of ammonium
chloride ?
E-3. In the absence of copper ion, zinc ion form a white precipitate with the ammonium tetrathio-cyanatomercurate(II)
How the presence of Cu2+ ion affect this test ?
ADVQUA - 242
E-4. Identify (A) to (D).
(A)  (B) + (C) (On cooling (C) turns white)


Colourless water (Brown gas) (Yellow residue)
soluble compound
(D)
(White ppt.)
Section (F) : Vth, VIth and Zero Group

F-1. What is the formula of iodide of Millon's base ?
F-2. What happens when ammonia gas is passed into a solution of sodium cobaltinitrite ?
F-3. CaSO4 is insoluble in water but when excess of (NH4)2SO4 is added in CaCl2 solution, CaSO4 is not precipitated,
why ?
F-4. What will happen if the precipitation of Vth group cation by ammonium carbonate is uplaced by Na2CO3 ?
F-5. What happens when ammonium sulphate solution is added to a solution containing both Sr2+ and Ca2+ ions?
F-6. Which colour precipitate is obtained when a solution of Ca2+ ions reacts with potassium ferrocyanide.
F-7.

(A) (colourless solid)  (B) (residue) + (C) (gas) + (D) gas
(D)
Solution of (B)   milky
(A) gives brick red colour in flame and decolouries MnO4– /H+. Gas (C) burns with blue flame. Identify (A), (B)
(C) and (D).
Section (A) : Ist Group

A-1. A metal nitrate reacts with KI solution to give yellow precipitate which on addition of excess of more
concentrated solution (6 M) of KI dissolves forming a solution. The cation of metal nitrate is :
(A) Hg22+ (B) Ag+ (C) Pb2+ (D) Cu2+
A-2. Three separate samples of a solution of a single salt gave these results. One formed a white precipitate with
excess ammonia solution, one formed a white precipitate with dilute NaCl solution and one formed a black
precipitate with H2S. The salt could be :
(A) AgNO3 (B) Pb(NO3)2 (C) Hg(NO3)2 (D) Mn(NO3)2
A-3. Consider the following observation :

 CrO 24 –
Mn+ + HCl (dilute)  white precipitate  water soluble   yellow precipitate.
The metal ion Mn+ will be :
(A) Hg2+ (B) Ag+ (C) Pb2+ (D) Sn2+
ADVQUA - 243
A-4. A white crystalline substance dissolves in water. On passing H2S in this solution, a black precipitate is
obtained. The black precipitate dissolves completely in hot HNO3. On adding a few drops of concentrated
H2SO4, a white precipitate is obtained. This precipitate is that of :
(A) BaSO4 (B) SrSO4 (C) PbSO4 (D) CdSO4
A-5. When calomel reacts with NH4OH solution the compound formed is :
(A) Hg2Cl2 (B) Hg(NH2)Cl (C) Hg(NH3)2Cl (D) HgCl2.NH3
A-6. Which of the following cations form coloured (not white) precipitates with aqueous solution of KI and this
precipitate does not dissolve in excess of reagent ?
(A) Hg2+ (B) Hg22  (C) Ag+ (D) Cu2+
A-7. Consider the following equilibrium :

AgCl  + 2NH3 [Ag(NH3)2]+ + Cl–
White ppt of AgCl appears on adding
(A) NH3 (B) aq. NaBr (C) aq. HNO3 (D) aq. NH4I
A-8. AgCl with NH3 forms a complex :

(A) [Ag(NH3)2]Cl (B) AgNO3 (C) [Ag(NH2)2]Cl (D) Ag mirror
Section (B) : IIA Group

B-1. Sometimes yellow turbidity appears while passing H2S gas even in slightly acidic medium in the absence of
 group radicals. This is because :
(A) sulphur is present in the mixture as impurity.
(B) IV group radicals are precipitated as sulphides.
(C) of the oxidation of H2S gas by some acid radicals.
(D)  group radicals are precipitated as hydroxides.
B-2. H2S in the presence of HCl precipitates  group but not V group because :
(A) HCl activates H2S (B) HCl increases concentration of Cl–
(C) HCl decreases concentration of S2– (D) HCl lowers the solubility of H2S in solution
B-3. When small amount of SnCl2 is added to a solution of Hg2+ ions, a silky white precipitate is obtained. The
silky white precipitate is due to the formation of :
(A) Hg2Cl2 (B) SnCl4 (C) Sn (D) Hg
B-4. When excess of dilute NH4OH is added to an aqueous solution of copper sulphate an intense blue colour is
developed. This is due to the formation of :
(A) [Cu(NH3)6]2+ (B) Cu(OH)2 (C) [Cu(NH3)4]2+ (D) (NH4)2SO4
B-5. A black sulphide is formed by the action of H2S on :

(A) cupric chloride (B) cadmium chloride (C) zinc chloride (D) ferric chloride.
B-6. Which one of the following salts will produce clear and transparent original solution in 2M HCl ?
(A) Ag2CO3 (B) Pb(CO3) (C) Hg2CO3 (D) CuCO3
B-7. When bismuth chloride is poured into a large volume of water the white precipitate produced is of :
(A) BiO.OH (B) Bi2 O3 (C) BiOCl (D) Bi (OH)3
B-8. In which of the following pairs the precipitates are red and black coloured respectively and both precipitates
are soluble in excess KI solution ?
(A) HgI2 , Hg2I2 (B) HgI2 , BiI3 (C) Cu2I2 , AgI (D) CdI2 , PbI2
ADVQUA - 244
B-9. Which diagram correctly represents change for given nitrate solution.
H2S
Cd(NO3 )2 CdS
dil.
dil.
CH3COOH
(A) HNO3 (B)
dil.
Cd(OH) 2 Cd(CH3 COO)2
NaOH
NaCN
Cd(NO3 )2 Cd(CN) 2
dil. NaCN
(C) HNO3 excess (D)
H2 S 2–
CdS [Cd(CN) 4]
B-10. A metal chloride original solution (i.e. O.S) on mixing with K2CrO4 solution gives a yellow precipitate soluble
in aqueous sodium hydroxide. The metal may be :
(A) mercury (B) iron (C) silver (D) lead
Section (C) : IIB Group

C-1. As2S3 dissolve in NaOH solution to form
(A) Na3AsS4 (B) Na3AsO4 (C) Na3AsS3 (D) Na AsO2
C-2. When white crystalline precipitate of magnesium ammonium arsenate is treated with acidified silver nitrate
solution, precipitate of silver arsenate is formed . The colour of precipitate is :
(A) Yellow (B) Brownish red (C) White (D) Brownish black
C-3. Which of the following metal sulphide is soluble in YAS (yellow ammonium sulphide) :
(A) HgS (B) PbS (C) Bi2S3 (D) Sb2S3
Section (D) : IIIrd Group

D-1. When NH4Cl is added to a solution of NH4OH :
(A) the dissociation of NH4OH increases. (B) the concentration of OH– increases.
(C) the concentrations of both OH– an NH4+ increase. (D) the concentration of OH– ion decreases.
D-2. To avoid the precipitation of Hydroxides of Zn2+, Mn2+ and Ni2+ along with those of Fe3+, Al3+ and Cr3+ the third
group solution should be :
(A) Concentrated HNO3 is added (B) Treated with excess of NH4Cl
(C) Concentrated H2SO4 is added (D) Treated with excess of NH4OH
D-3. An inorganic lewis acid (X) fumes in moist air, and intensity of fumes increases when and rod dipped in
NH4OH is brought near to it. An acidic solution of (X) on addition of NH 4Cl and NH4OH gives a precipitate
which dissolves in NaOH solution. An solution of (X) does not give precipitate with H 2S Hence, compounds
(X) is :
(A) FeCl3 (B) AlCl3 (C) CrCl3 (D) ZnCl2
D-4. An original solution of an inorganic salt in dilute HCl gives a brown colouration with potassium hexacyanidoferrate
(III) and reddish brown colouration with sodium acetate solution. The cation of the salt is :
(A) Ni2+ (B) Fe3+ (C) Cu2+ (D) none
D-5. Turnbull’s blue is a .................... .

(A) ferricyanide (B) ferrous ferricyanide (C) ferrous cyanide (D) ferri ferrocyanide
D-6. Fe(OH)3 and Cr(OH)3 precipitates can be completely separated by :

(A) Aq. NH3 (B) HCl (C) NaOH/H2O2 (D) H2SO4
Section (E) : IVth Group

E-1. A coloured solution of a salt gives following reactions.
(i) It gives white precipitate with sodium hydroxide which becomes brown on exposure to air.
(ii) It gives white precipitate with ammonia solution which is soluble in ammonium salts.
(A) Mn2+ (B) Zn2+ (C) Al3+ (D) Ni2+
ADVQUA - 245
E-2. A metal salt form precipitate with H2S in presence of (NH4OH + NH4Cl) and this precipitate is soluble in acetic
acid then metal sulphide could be :
(A) ZnS (B) CoS (C) MnS (D) NiS
E-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)
E-4. An aqueous solution of colourless metal sulphate M, gives a white precipitate with NH4OH. This was soluble
in excess of NH4OH. On passing H2S gas through this solution a white precipitate is formed. The metal M in
the salt is :
(A) Ca (B) Ba (C) Al (D) Zn
E-5. A aqueous solution of colourless metal sulphate M gives a white ppt, with NH4OH. This is soluble in excess
of NH4OH . On passing H2S through this solution a white ppt is formed. The metal M in the salt is :
(A) Ca (B) Ba (C) Al (D) Zn
E-6. A metal salt cobalt form brown solution with excess of KCN solution. This brown solution yellow when boiled
for a longer time in air due to formation of :
(A) Co(CN)2 (B) K4[Co(CN)6] (C) K3[Co(CN)6] (D) K2 [Co(CN)6]
E-7. A metal salt solution when treated with dimethyl glyoxime and NH4OH gives a rose red complex. The metal
is :
(A) Ni (B) Zn (C) Co (D) Mn.
E-8. The ion that can not be precipited by H2S in presence of dil. HCl
(A) Pb2+ (B) Bi3+ (C) Cu2+ (D) Ni2+
Section (F) : Vth, VIth and Zero Group

F-1. Aqueous Solution of BaBr2 gives yellow precipitate with :
(A) K2CrO4 (B) AgNO3 (C) (CH3COO)2Pb (D) (A) and (B) both
F-2. The addition of K2CO3 (aq) to the following solution is expected to produce a precipitate in every case but that
one which does not produce precipitate is :
(A) BaCl2(aq) (B) CaBr2(aq) (C) Na2SO4(aq) (D) Pb(NO3)2 (aq)
F-3. An aqueous solution of salt gives white precipitate with AgNO3 solution as well as with dilute H2SO4. It may
be
(A) Pb(NO3)2 (B) Ba(NO3)2 (C) BaCl2 (D) CuCl2
F-4. Mg is not precipitated in V group because :

(A) MgCO3 is soluble in water. (B) Ksp of MgCO3 is high.
(C) MgCO3 is soluble in NH4OH. (D) None.
F-5. A metal salt solution form a yellow ppt with potassium chromate in acetic acid, a white ppt with dilute
sulphuric acid but gives no ppt with sodium chloride or iodide it is :
(A) Lead carbonate (B) Basic lead carbonate
(C) Barium nitrate (D) Strontium nitrate
F-6. The yellow precipitate formed by passing ammonia into Nessler’s reagent in due to the formation of
(A) Hgl42– (B) NH2O–Hg–Hgl (C) NH2–Hg–O–Hg–I (D) NH3–Hg–I
F-7. Orange coloured sodium cobaltinitrite Na3[Co(NO2)6] is used for the detection of K+ ions which gives ..... ppt.
due to the formation of Pot. Sod. Cobaltinitrite K2Na[Co(NO2)6]
(A) White (B) Orange (C) Yellow (D) Brown
ADVQUA - 246
1. Match the colour of the precipitates listed in column-I with the suitable reagent(s) in column-II.
Column-I Column-II
(A) Bi give(s) black precipitate with
3+
(p) H2S (saturated solution in water)
(B) Cu2+ give(s) black precipitate with (q) Potassium thiocyanate solution
(C) Zn2+ give(s) white precipitate with (r) Potassium iodide solution
(D) Ag+ give(s) white precipitate with (s) Potassium ferrocyanide solution
2. Match the precipitates listed in column-I with their suitable solvents listed in column-II.
Column I Column II
(precipitate) (solvent)
(A) AgCl (white) (p) Concentrated HCl.
(B) CuS (black) (q) Dilute ammonia solution (excess).
(C) Zn(OH)2 (white) (r) Potassium cyanide solution.
(D) Ba(CO3) (white) (s) Hot 50% nitric acid.
(t) Sodium hydroxide solution.
3. Match the basic radicals listed in column-I with the properties listed in column-II.
Column-I Column-II
(Basic radical) (Properties)
(A) Mn2+ (p) Forms coloured metaborate in oxidising flame in borax bead test.
(B) Cr3+ (q) Forms white precipitate with sodium hydroxide but on exposure to air
turns rapidly brown.
(C) Al3+ (r) With both potassium cyanide (not in excess) and ammonia solution
separately forms reddish brown precipitate.
(D) Fe3+ (s) With excess of sodium hydroxide forms soluble complex but on adding
acid to soluble complex, a precipitate is obtained which redissolves on
adding excess of acid.

1. Which of the following compound does not gives ppt with dil. HCl ?
(A) AgNO3 (B) Pb(NO3)2 (C) Hg2(NO3)2 (D) Hg(NO3)2
2. KI gives precipitate with all the cations given :

(A) Ag+, Hg22+, Pb2+ (B) Cu2+, Zn2+, Ni2+ (C) Na+, Ca2+, Mg2+ (D) Ag+, Ca2+, Sr2+
3. Three test tubes A, B, C cation Pb2+, Hg22+ and Ag+ (but unknown to each, aqueous solution NaOH is added
in excess). Following changes occur.
A : Black ppt, B : Brown ppt, C : White ppt but dissolves in excess of NaOH
A, B and C contain respectively :
(A) Pb2+, Hg22+, Ag+ (B) Hg22+, Ag+, Pb2+ (C) Ag+, Pb2+, Hg22+ (D) Ag+, Hg22+, Pb2+
4. Salt mixture   white ppt.

dil. HCl

salt mixture contains cations of :

(A) Pb2+ and Hg2+ (B) Pb2+ and Hg22+ (C) Pb2+ and Ag+ (D) None of these
ADVQUA - 247
5. A compound (X) reacts in the following ways.
The compound (X) is likely to be

(A) Pb(NO3)2 (B) CaCrO4 (C) Hg(NO3)2 (D) AgNO3
6. When excess of SnCl2 is added to a solution of HgCl2, a white ppt turning grey is obtained. The grey colour
is due to the formation of :
(A) Hg2Cl2 (B) SnCl2 (C) Sn (D) Hg
7. An aqueous solution of a substance gives a white ppt. on treatment with dil HCl, which dissolves on heating.
When hydrogen sulphide is passed through the hot acidic solution, a black ppt is obtained.The subtance is
a:
(A) Hg2+ salt (B) Cu2+ salt (C) Ag+ salt (D) Pb2+ salt
8. Three seperate sample of a solution of a single salt gave these results one formed a white precipitate with
excess of ammonia solution, one formed a white precipitate with dil. NaCl solution and one formed a black
precipitate with H2S. The salt could be :
(A) AgNO3 (B) Pb(NO3)2 (C) Hg(NO3)2 (D) MnSO4
9. In the separation of Cu2+ and Cd2+ in 2nd group qualitative analysis of cations tetraammine copper(II) sulphate
and tetrammine cadmium(II) sulphate react with KCN to form the corresponding cyano complexes. Which
one of the following pairs of the complexes and their relative stability enables the separation of Cu 2+ and
Cd2+?
(A) K3[Cu(CN)4] more stable and K2[Cd(CN)4] less stable
(B) K2[Cu(CN)4] less stable and K2[Cd(CN)4] more stable
(C) K2[Cu(CN)4] more stable and K2[Cd(CN)4] less stable
(D) K3[Cu(CN)4] less stable and K2[Cd(CN)4] more stable
10. A pale green crystalline metal salt of M dissolves freely in water. On standing it gives a brown ppt on addition
of aqueous NaOH. The metal salt solution also gives a black ppt on bubbling H 2S in basic medium. An
aqueous solution of the metal salt decolourizes the pink colour of the permanganate solution. The metal in
the metal salt solution is :
(A) copper (B) aluminum (C) lead (D) iron
11. K4[Fe(CN)6] can be used precipitate one or more out of Fe2+ , Fe3+, Zn2+, Cu2+, Ag+ , Ca2+ :
(A) only Fe2+, Fe3+ (B) only Fe3+,Zn2+,Cu2+ (C) all but not Ca2+ (D) all of these.
12. Ferric alum gives deep red colour with NH4SCN due to the formation of :
(A) Al(SCN)3 (B) [Fe(SCN)3]– (C) Fe(SCN)3 (D) None of these.
13. Nessler's reagent is used to detect.

(A) CrO42– (B) PO43– (C) MnO4– (D) NH4+
14. On the addition of a solution containing CrO42– & CH3COOH acid to the solution of Ba2+, Sr2+ and Ca2+ ions,
the ppt obtained first will be of :
(A) CaCrO4 (B) SrCrO4 (C) BaCrO4 (D) a mixture of all the three
15. A salt on treatment with dil. HCl gives a pungent smelling gas and a yellow precipitate. The salt gives green
flame when tested. The solution gives a yellow precipitate with potassium chromate. The salt is :
(A) NiSO4 (B) BaS2O3 (C) PbS2O3 (D) CuSO4
ADVQUA - 248
16. A chloride dissolves appreciably in cold water. When placed on a platinum wire in Bunsen flame, no distinctive
colour is noticed. The cation of chloride is :
(A) Mg2+ (B) Ba2+ (C) Pb2+ (D) Ca2+
17. In fifth group, (NH4)2CO3 is added to precipitate out the carbonates. We do not add Na2CO3 because :
(A) CaCO3 is soluble in Na2CO3
(B) Na2CO3 increases the solubility of fifth group carbonates
(C) MgCO3 will be precipitated out in fifth group
(D) none
18. 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 :
(A) lead carbonate (B) basic lead carbonate
(C) barium carbonate (D) strontium carbonate

1. An aqueous solution contains Hg2+, Hg22+, Pb2+, Ag+, Bi3+ and Cd2+. Out of these, how many ions will
produce white precipitate with dilute HCl ?
2. A solution of Hg2+ ion on treatment with a solution of cobalt(II) thiocyanate gives rise to a deep blue crystalline
precipitate. Then the coordination number of mercury in the deep blue coloured compound is :
dil. HCl
3. As3+ + H2S    "yellow ppt of A"
A + yellow ammonium sulphide  C + D

How many different type of oxidation states of sulphur are possible in "C" and "D".
4.
The sum of number of p-pbonds present in gas (Y) & (Z) ?
5. An alcoholic solution of dimethylglyoxime is added to an aqueous solution of nickel(II) chloride. Slow
addition of ammonium hydroxide led to the precipitation of a bright-red coloured metal complex.
Find out the number of hydrogen bonds present in the structure of the complex.
6. In how many of the following reactions, one of the product is obtained as a yellow precipitate :
(a) Ba2+ + CrO42–  product (b) NH4+ + [PtCl6]2–  product
3–  product
(c) NH4 + [Co(NO2)6]
+
(d) Ca2+ + [Fe(CN)6]4– + K+  product
(e) Sr2+ + CO32–  product
7. Total number of metal nitrates given below, which give the following reaction,
Excess NH3.H2 O
No change in colour and
number ppt remains in the
test tube
aq. solution of Metal Nitrate
AgNO3, Pb(NO3)2, Cu(NO3)2, Cd(NO3)2, Zn(NO3)3, Ni(NO3)2, Al(NO3)2
ADVQUA - 249
8. Aqueous CuSO4 decolorizes on addition of KCN due to formation of complex (A).
In complex "A". If
(i) Number of d orbitals participating in hybridisation is / are 'a'
(ii) Coordination number of Cu is "c".
then find 8a + 5c.
9. Co2+ + CN–  "A" (reddish brown) ppt.

"A" + CN– (excess)  "B" (brown solution)
"B" + O2 + 2H2O  "C" (yellow solution)
then find (a + b) for complex "C" if a = coordination number of Co
b = charge on complex (consider the magnitude)
10^. How many of the following reactions give yellow ppt.

(i) NaBr + AgNO3  (ii) NaI + AgNO3
(iii) NaBr + Pb(NO3)2  (iv) NaI + Pb(NO3)2 
(v) Na2S + Cd(CH3COO)2  (vi) K2CrO4 + Pb(CH3COO)2 
(vii) K2CrO4 + AgNO3 
(viii) NaBr + Chlorine water (excess) 

1. An aqueous solution containing Hg2+, Hg22+, Pb2+ and Cd2+ ions will give precipitates of ........... with HCl.
(A) HgCl2 (B) Hg2Cl2 (C) PbCl2 (D) CdCl2
2. Which of the following is/are correctly matched ?

(A) BiI3   Black (B) Cu2I2   White precipitate
(C) PbI2   Yellow precipitate (D) HgI2   Red precipitate
3. Which of the following are completely soluble in concentrated ammonia solution?
(A) AgCl (B) AgBr (C) Ag2CrO4 (D) Ag
boiled
4. Hg2I2 (green)   products
with H2 O
Which of the following statement is / are correct with respect to the products ?
(A) Black precipitate of mercury(I) oxide is formed.
(B) Violet colour gas is evolved.
(C) Red precipitate of HgI2 is formed.
(D) Mercury is obtained
5. Cu2+ ions give white precipitate with :

(A) potassium iodide solution. (B) potassium thiocyanate and saturated solution of SO 2.
(C) excess of potassium cyanide solution. (D) potassium hydroxide solution.
6. Which of the following statements is/are true ?

(A) Ag+ ions do not give white precipitate with excess of concentrated HCl.
(B) Cu2+ ions produce a white precipitate when KCN solution is added in a small quantity.
(C) Hg2+ ions give deep blue precipitate with cobalt acetate and ammonium thiocyanate.
(D) Black precipitate of BiI3 turns orange when heated with water.
7. K solution is the reagent for :
(A) Hg2+ (B) Pb2+ (C) Ag+ (D) Cu2+
8. Which of the following cations form(s) black precipitate(s) with H2S (g) ?
(A) Cu2+ (B) Sb3+ (C) Pb2+ (D) Bi3+
9. Which of the following process result in a prussain blue ppt ?

(A) Fe2+ + [Fe(CN)6]3–  (B) Fe2+ + [Fe(CN)6]4– 
SnCl 2
(C) Fe + [Fe(CN)6] 
3+ 3–
(D) Fe3+ + [Fe(CN)6]3  P  
ADVQUA - 250
10. Which of the following statement(s) is /are false ?
(A) Fe3+ gives red precipitate with dimethyl glyoxime in alkaline solution.
(B) Cu2+ ion with potassium iodide solution gives a dirty brownish white precipitate which turns white on
adding hypo solution.
(C) A filter paper soaked in mercurous nitrate turns black in contact with ammonia gas.
(D) Ag2O does not dissolve in nitric acid and ammonia solution.

(A) An aqueous solution of Co(II) thiocyanate (10% freshly prepared) and mercuric nitrate solution taken in
equal volumes on stirring the wall of the vessel with a glass rod produce deep-blue precipitate.
(B) White precipitate of Al(OH)3 is soluble in sodium hydroxide as well as in ammonia solution.
(C) Green precipitate of Cr(OH)3 readily dissolves in excess of sodium hydroxide forming a green solution.
(D) Chromium (III) salts give green coloured borax bead in both oxidising and reducing flame.
12. Which of the following mixture of cations can be separated by adding excess NH3 solution ?
(A) Zn2+, Mn2+ (B) Zn2+, Cd2+ (C) Zn2+, Pb2+ (D) Zn2+, Cu2+
13. Co2+ + KCN (not in excess)  precipitate.

Select the correct statement(s) with respect to the precipitate.
(A) It is yellow in colour.
(B) It is reddish-brown in colour.
(C) It dissolves in excess of the reagent forming a brown solution.
(D) It is obtained when brown solution (option (C)) is acidified with dilute HCl in the cold.
14. CoCl2 + KNO2 + CH3COOH  [X] + H2O + KCl + CH3COOK + NO

(Unbalanced equation)
Which is / are correct for 'X'?
(A) X is a yellow crystalline solid which is insoluble in water.
(B) X is a green coloured compounds known as Rinman's green.
(C) IUPAC name of X is potassium hexanitrito –N– cobaltate (II)
(D) The compound X is an inner orbital complex.
15. 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/white precipitate with Zn2+.
(D) It develops a deep red colouration with Fe3+.
Comprehension # 1
H2 S ( g )
Aqueous solution of ‘A’   Black precipitate ‘B’, soluble in 50% HNO3 forming ‘C’.
White precipitate dissolves in Black precipitate ‘D’

hydrochloric acid but on dilution with
water again white turbidity appears 'E'.
Moreover, the salt 'A' on heating with solid K2Cr2O7 and concentrated H2SO4 produces deep red vapours
which dissolve in sodium hydroxide solution forming a yellow solution. This yellow solution gives yellow
precipitate with Ba(NO3)2 solution.
ADVQUA - 251
On the basis of the aforesaid characteristic informations answer the following questions :
1. Acidified solution of ‘A’, on treatment with KI gives black precipitate 'F' which dissolves in excess of reagent
forming the coloured compound 'G'. The chemical composition of 'F' and 'G' are respectively :
(A) HgI2 and [HgI4]2– (B) PbI2 and [PbI4]2– (C) BiI3 and [BiI4]– (D) Cu2I2 and CuI2.
2. The black precipitate 'F' on heating with water produces :

(A) Hg(OH)2 (B) BiOI (C) BiO.OH (D) CuO.OH
3. Select the correct statement.

(A) Aqueous solution of 'A' reacts with AgNO3 solution to give white precipitate which turns into yellow on
treatment with sodium arsenite.
(B) Aqueous solution of 'A' produces white precipitate with sodium hydroxide which turns into yellowish-white
on boiling.
(C) White turbidity 'E' is soluble in dilute mineral acids.
(D) All of these.
Reaction involved in comprehension :


H Bi S  (black) (B) + 6 H+
2Bi3+ (A) + 3H2S  2 3
Bi2 S3 + 8HNO3  2Bi (NO3)3 (C) + 2NO + 3S + 4H2O

NaOH
Bi3+ + 3OH–  Bi(OH)3 (white) ; 2Bi(OH)3  (white) + 3[Sn(OH)4]2–  2Bi (D) + 3[Sn(OH)6]2–
NH4OH
Bi3+ + 3OH–   Bi(OH)3 (white) ; Bi(OH)3 (white) + 3HCl  BiCl3 + 3H2O
BiCl3 + H2O  BiOCl  (bismuth oxychloride) (E) + 2HCl

4NaCl + K2Cr2O7 + 3H2SO4 (conc.)  2CrO2Cl2 (deep red vapours) + 2Na2SO4 + K2SO4 + 3H2O
CrO2Cl2 + 4OH–  CrO42– + 2Cl– + 2H2O
CrO42– + Ba2+  BaCrO4 (yellow).
Comprehension # 2
A student was given a sample of colourless solution containing three cations and was asked to identify the
cations. Student carried out a series of reactions as given below.
4. Precipitates ‘A’, ‘B’ and ‘C’ are respectively :

(A) Al(OH)3, BaSO4 and AgCl (B) AgCl, BaSO4 and Zn(OH)2
(C) AgCl, Ca(OH)2 and ZnSO4 (D) ZnCl2, BaSO4 and Al(OH)3
5. White precipitate 'A' is not soluble in :

(A) NH3 (B) 2M HCl (C) KCN (D) Na2S2O3
ADVQUA - 252
6. Which of the following statement is correct ?
(A) Precipitate 'C' gives Rinmann's green test.
(B) Precipitate 'B' is appreciably soluble in boiling concentrated H2SO4.
(C) Precipitate (A) on exposure to sunlight or ultraviolet radiations turns black.
(D) All of these.
ADVQUA - 253
EXERCISE - 1
PART - I
A-1. PbCl2 is soluble in hot water and it also dissolves in concentrated HCl and KCl solutions forming soluble
complex. ; PbCl2 + 2HCl  H2PbCl4 (soluble complex).
A-2. Pb2+ + H2S (atmospheric)  PbS (black) + 2H+.
A-3. PbCl2 + 2KI 

 PbI2(yellow) + 2KCl ; PbCl2 + H2S 
 PbS (Black)
PbI2 + KI K2(PbI4) (aq)
A-4. Hg2Cl2 + 2 NH4OH  HgNH Cl  ( white )  Hg  (black ) + NH4Cl + 2 H2O

2
black
Disproportionation reaction.
A-5. Hg22+ + 2OH–  Hg2O  (black) + H2O

Hg2O   HgO  + Hg  (grey) ; Disproportionation reaction.
A-6. Hg22  2 –  Hg2  2 

green
A-7. AgI + 2CN–  [Ag(CN)2]– + I–, AgI + 2S2O32–  [Ag(S2O3)2]3– + I–

for formation of soluble complex
A-8. 4[Ag(NH3)2]+ + H2N–NH2.H2SO4  4Ag + N2 + 6NH4+ +2NH3+SO42–
A-9. (A) is AgBr (present in photographic plate)

AgBr + 2Na2S2O3  Na3[Ag(S2O3)2] + NaBr
soluble
(B)
NH3 HClHNO3
[Ag(NH3 )2 Cl]   AgCl  Ag2S

(E) (D) (C)
B-1. With Na2S, along with 2nd group cations, some cations of higher groups i.e., IIIrd and IVth groups may be
precipitated because the higher concentration of S2– ions is obtained according to following reaction.
Na2S 2 Na+ + S2–
To precipitate II group cations lower concentration of S2– ions is required (because of low Ksp of IInd group
nd
sulphides) and this can be obtained easily by H2S in presence of dilute HCl.
H2 S 2 H+ + S2– ; HCl H+ + Cl–
Due to common ion effect the ionisation of H2S is suppressed and the concentration of S2– ions obtained is
just sufficient to precipitate the cations of IInd group.
ADVQUA - 254
B-2. Yes, Hg2+ + 2OH– 
 HgO + H2O
yellow
Hg22+ + 2OH– 
 Hg2O + H2O
black
B-3. It turns yellowish–white owing to the formation of BiO.OH .

Bi(OH)3  BiO.OH  + H2O
B-4. Yes. By the reaction of ammonia according to the following reactions.

Cu2+ + 4NH3  [Cu(NH3)4]2+ (deep blue solution).
Cd2+ + 4NH3  [Cd(NH3)4]2+ (colourless solution).
B-5. (A) : CuSO4 (B) : BaSO4 (C) : HCl (D) : (Cu2I2 + I3–)
(E) (Cu2I2 + I– + S4O62–) (F) Cu2 [Fe(CN)6]
C-1. Presence of Sb3+ or Bi3+ their chloride hydrolyse to oxychlorides in presence of excess of water.
BiCl3 + H2O  BiOCl + 2HCl
SbCl3 + H2O  SbOCl + 2HCl
C-2. Yes, If Sn2+ is absent then NaOH, KOH or colourless ammonium sulphide may be used. Except SnS, all the
sulphides of group-II (B) are soluble in these solutions also.
C-3. HNO3 is a powerful oxidising solution. Causing confusion with CdS, AS2S3 (both yellow ppt) . Colloidal
solution can not be filtered causing unnecessary trouble.
C-4. As3+

AsCl3 (x) + 3H2S  As2S3  (yellow) + 6HCl
H
C-5.
3As2S3 + 28HNO3+4H2O  6H3AsO4(y)+ 9SO2–
4 +18H + 28 NO
+
H3 AsO4(y) + 12 NH4MaO4+21 HNO3  (NH4) AsO4.12MoO3(yellow)+21 NH4NO3+12H2O
C-6. (A) is SnCl2
D-1. Fe2+ salt are oxidised to Fe3+ salt by boiling with conc. HNO3, before adding NH4Cl and NH4OH, otherwise
Fe2+ would not be precipitated in group .
D-2. 2Al2O3 +2CO2+ + 4NO3– 

 2COAl2O4 (thenard blue) +4NO2+ O2
In case of excess of Co(NO3)2, CoAl2O3 will produce black cobalt oxide (CO3O4), which will mask the blue
colour.
D-3. Only Fe(II) salts give soluble red iron(II) dimethylglyoxime in ammonical solution.
D-4. (i) White precipitate, K2Fe[Fe(CN)6] and (ii) Pale blue precipitate.
D-5. Ferrous and stannous (Fe2+ and Sn2+) both act as reducing agents and decolourize acidic KMnO 4.
MnO4– + 5Fe2+ + 8H+  5Fe3+ + Mn2+ + 4H2O.
E-1. Mn2+ + 2 NH3 + 2 H2O Mn(OH)2  (white) + NH4+ .

In presence of ammonium salts, the reaction proceeds in backward direction.
E-2. Zn2+ + 2 NH3 + 2 H2O Zn(OH)2 + 2 NH4+

It is due to the lowering of OH ion concentration because of common ion effect of NH4+ to such a value that
–
the Ksp of Zn(OH)2 is not attained.
ADVQUA - 255
E-3. 
 Cu2+ + [Hg(SCN)4]2–  Cu[Hg(SCN)4]

* In the presence of the copper ions, the copper complex Co-precipitated with that of zinc complex and
colour become violet
E-4. (A) : Zn (NO3)2 (B) : NO2 (C) : ZnO (D) : ZnS
F-1. Hg2ONH2I or or . HgO
F-2. A yellow precipitate of ammonium cobaltinitrite is formed.

3 NH4+ + Na3[Co(NO2)6]  (NH4)3 [Co(NO2)6] (yellow) + 3 Na+
F-3. Because CaSO4 precipitate form a complex with (NH4)2 SO4 which is water soluble
CaSO4 + (NH4)2SO4   (NH4)2Ca(SO4)2 (soluble)
F-4. Mg2+ ions will also be precipitated.
F-5. Sr2+ + NH4+ + SO42–  SrSO4  (white) + NH4+

Ca2+ + 2 NH4+ + 2 SO42–  (NH4)2[Ca(SO4)2] (soluble complex).
F-6. White precipitate is obtained.

Ca2+ + 2K+ + [Fe(CN)6]4–  K2Ca[Fe(CN)6] 
F-7. (A) : CaC2O4 (B) : CaO (C) : CO (D) : CO2
PART - II
A-1. (C) A-2. (B) A-3. (C) A-4. (C) A-5. (B)
A-6. (B) A-7. (C) A-8. (A) B-1. (C) B-2. (C)
B-3. (A) B-4. (C) B-5. (A) B-6. (D) B-7. (C)
B-8. (B) B-9. (C) B-10. (D) C-1. (C) C-2. (B)
C-3. (D) D-1. (D) D-2. (B) D-3. (B) D-4. (B)
D-5. (B) D-6. (C) E-1. (A) E-2. (C) E-3. (B)
E-4. (D) E-5. (D) E-6. (C) E-7. (A) E-8. (D)
F-1. (D) F-2. (C) F-3. (C) F-4. (B) F-5. (C)
F-6. (C) F-7. (C)
PART - III
1. (A - p,r) ; (B - p,q) ; (C - p,s) ; (D - q,s) 2. (A - p,q,r ; B - r,s ; C - p,q,s,t ; D - p,s)
3. (A - p,q ; B - p,s ; C - s ; D - p,r)
EXERCISE - 2
PART - I
1. (D) 2. (A) 3. (B) 4. (C) 5. (D)
6. (D) 7. (D) 8. (B) 9. (A) 10. (D)
11. (D) 12. (C) 13. (D) 14. (C) 15. (B)
16. (A) 17. (C) 18. (C)
ADVQUA - 256
PART - II
1. 3 2. 4 3. 3 4. 4 5. 2
6. 3 7. 3 8. 20 9. a=6 ; b=3,a+b=9
10^. 5
PART - III
1. (B,C) 2. (A,B,C,D) 3. (A,B,C) 4. (C,D) 5. (A,B)
6. (A,B,C,D) 7. (A,B,C,D) 8. (A,C,D) 9. (A,D) 10. (A,D)
11. (A,C,D) 12. (A,C) 13. (B,C,D) 14. (A,D) 15. (A,B,C)
PART - IV
1. (C) 2. (B) 3. (D) 4. (B) 5. (B)
6. (D)
ADVQUA - 257

4 above.
1. Identify the compound which turns black with ammonia solution.

(1) Lead chloride (2) Mercurous chloride
(3) Mercuric chloride (4) Silver chloride
2. A white crystalline substance dissolves in water. On passing H2S in this solution, a black precipitate is
obtained. The black precipitate dissolves completely in hot HNO3. On adding a few drops of concentrated
H2SO4, a white precipitate is obtained which is soluble in ammonium acetate. The white precipitate is that of:
(1) BaSO4 (2) SrSO4 (3) PbSO4 (4) Ag2SO4
3. The composition of golden spangles is :

(1) PbCrO4 (2) PbI2 (3) As2S3 (4) BaCrO4
4. In which of the following solvents, AgBr will have the highest solubility ?
(1) 10–3 M NaBr (2) 10–3 M NH4OH (3) Pure water (4) 10–3 M HBr
5. Which one among the following pairs of ions can not be separated by passing H2S gas in presence of dilute
hydrochloric acid?
(1) Cd2+, Sn2+ (2) Al3+, Hg2+ (3) Zn2+, Cu2+ (4) Ni2+, Bi3+
6. Which of the following is not precipitated as sulphide by passing H2S in the presence of concentrated HCl ?
(1) Copper (2) Arsenic (3) Cadmium (4) Lead
7. Which of the following metal cation is reduced from its higher oxidation state (+2) to (+1) by both KI solution
and excess of KCN solution ?
(1) Zn2+ (2) Hg2+ (3) Cu2+ (4) None
8. Which of the following reagents give an orange coloured soluble complex when dissolved in excess with Bi +3
ions ?
(1) Ammonia solution (excess).
(2) Dilution in water
(3) Potassium iodide solution.
(4) Freshly prepared 0.125 M alkaline sodium tetrahydroxidostannate (II) solution.
9. Which of the following ions on reaction with NaOH and subsequent heating produce black ppt.
(1) Cu+2 (2) Zn+2 (3) Al+3 (4) Sn+2
ADVQUA - 258
10. FeCl3 + K3[Fe(CN)6] + H2O2  Precipitate. The colour of the precipitate is :
(1) sky blue (2) brown (3) prussian blue (4) white
ether
11. CrO42– + H+ + H2O2   X + H2O
Identify the correct statement with respect to X.
(1) It is an acid anhydride of chromic acid.
(2) It is a red colour compound which can be extracted easily into the ethereal phase.
(3) It is chromium peroxide which produces blue colouration in ethereal layer on gentle shaking.
(4) It is Cr2O3 which is used as a green pigment.
12. White precipitate of Mn(OH)2 on heating with PbO2 and concentrated HNO3 gives red-violet (purple) colour
due to the formation of :
(1) HMnO4 (2) Mn2O7 (3) MnO(OH)2 (4) PbMnO4
13. Zn(OH)2 precipitate is soluble in :

(1) excess of sodium hydroxide (2) excess of ammonia solution
(3) solutions of ammonium salts (4) all of these
14. Select the correct statement with respect to Ca2+ ions.

(1) K2CrO4 gives white precipitate in the presence of acetic acid.
(2) Potassium hexacyanidoferrate (II) solution gives white precipitate.
(3) It gives lilac colour in Bunsen flame.
(4) Prolonged passage of carbon dioxide gas through its aqueous solution produces white precipitate.
15. A mixture of two salts is not water soluble but dissolves completely in dilute HCl to form a colourless
solution. The mixture could be :
(1) AgNO3 and KBr (2) BaCO3 and ZnS
(3) FeSO4 and Na2CO3 (4) Mn(NO3)2 and MgSO4
16. The reagents, NH4Cl and aqueous NH3 will precipitate :

(1) Ca2+ (2) Al3+ (3) Mg2+ (4) Zn2+ .
17. In the precipitation of the iron group in qualitative analysis, ammonium chloride is added before adding
ammonium hydroxide to :
(1) decrease concentration of OH– ions (2) prevent interference by phosphate ions
(3) increase concentration of Cl– ions (4) increase concentration of NH4+ ions
18. Fe2+ does not give prussian blue colour with K4[Fe(CN)6] but on its reaction with (X), prussian blue colour
appears (X) can be :
(1) MnO4–/ H+ (2) Zn/NaOH (3) NH3 (aq) (4) all true
19. Select the correct statement with respect to Fe3+ ions.

(1) Iron (III) ions react with H2S in acidic solution to give a black precipitate of Fe2S3.
(2) Iron (III) ions react with ammonium sulphide to give the black precipitate of Fe2S3.
(3) Iron (III) ions react with ammonium thiocyanate solution to produce deep red colouration.
(4) All of these
20. Which of the following cation does not give red colour precipitate/solution with dimethylglyoxime (DMG) in
alkaline solution ?
(1) Zn+2 (2) Ni+2 (3) Fe2+ (4) both (1) and (3)
21. A suspension containing insoluble substances ZnS, MnS, HgS, Ag2S and FeS, is treated with 2N HCl. On
filtering, the filtrate contains appreciable amounts of which one of the following?
(1) Zinc and mercury (2) Silver and iron
(3) Manganese and mercury (4) Zinc, manganese and iron
22. Potassium chromate K2CrO4 is NOT used to identify.

(1) Pb+2 (2) Ba+2 (3) Ag+ (4) Ca+2
ADVQUA - 259
23. When H2S gas is passed through HCl containing aqueous solution of CuCl2 , HgCl2, BiCl3, and CaCl2 it does
not precipitate out :
(1) CuS (2) HgS (3) Bi2S3 (4) CaS
24. Ag2S is soluble in NaCN due to formation of :

(1) Na[Ag(CN)2] (2) Ag(CN)2 (3) Na2[Ag(CN)3] (4) Na2[Ag(CN)2]
25. Cu2+ and Ag+ are both present in the same solution. To precipitate one of the ions and leave the other in
soluton, which reagent should be added :
(1) H2S (aq) (2) HCl (aq) (3) HNO3 (aq) (4) NH4NO3 (aq)
aq. NH3
26. Aqueous (A) + K2CrO4  (B)   (C)
(Red ppt.) (soluble)
A is :
(1) AgNO3 (2) Pb(NO3)2 (3) Hg2(NO3)2 (4) Ca(NO3)2
27. The ion most difficult to remove as a precipitate is :

(1) Ag+ (2) NH4+ (3) Fe3+ (4) Cu2+
28. CuSO4 reacts with NH4OH to give deep blue complex of :

(1) [Cu(NH3)4]SO4 (2) [Cu(NH3)4](OH)2 (3) Both (1) and (2) (4) none of these
29. Thenard blue is :

(1) Cu(NH3)4SO4 (2) CoAl2O4 (3) K2Fe[Fe(CN)6] (4) Fe4[Fe(CN)6]3
30. Among the species A (CrCl3), B (CuS), C (AlCl3), D (ZnCl2), which will be soluble in excess of NaOH ?
(1) A,C and D (2) C and D only (3) B and C only (4) A and D only

Que. 1 2 3 4 5 6 7 8 9 10
Ans.
Que. 11 12 13 14 15 16 17 18 19 20
Ans.
Que. 21 22 23 24 25 26 27 28 29 30
Ans.

1. A 0.1 M solution of certain cation will precipitate with 0.1 M solutions of all these anions OH –, CO3–2 &
SO4–2. This description is true for the cation. [NSEC-2000]
(A) Fe2+ (B) Mg2+ (C) Ba2+ (D) Pb2+
2. If H2S gas is passed in a acidified ZnSO4, the precipitation of ZnS does not take place because
[NSEC-2002]
(A) Ksp of ZnS is not exceeded (B) Ksp of ZnS is decreases
(C) Ksp of ZnS is increases (D) none of these
3. A solution containing Co2+ , Zn2+ and AI3+ is mixed with an excess of KSCN solution. The resulting solution
besides the unreacted ions, should contain [NSEC-2003]
(A) [Co(SCN)6] 4-
(B) [Zn(NCS)6] 2-
(C) AI(SCN)3 (D) Zn(SCN)2.
ADVQUA - 260
(A) K4[Fe(CN)6] (B) K2[Fe(CN)4(NH3)2]
(C) Fe4[Fe(CN)6]3 (D) Na2[Fe(CN)5NO].
5. When H2S is passed through a solution containing Cu2+ , Cd2+ and an excess of cyanide ions, cadmium
6. Generation of a blue colour which is not due to metal ammonia complex formation is seen when
[NSEC-2003]
(A) sodium is dissolved in liquid ammonia
(B) copper (II) sulphate is reacted with ammonium hydroxide
(C) cobalt (II) chloride is reacted with ammonium hydroxide
(D) formaldehyde is reacted with ammonuim hydroxide.
7. There is a mixture of Cu(II) chloride and Fe (II) sulphate. The best way to separate the metal ions from this
mixture in qualitative analysis is by treating it with [NSEC-2003]
(A) hydrogen sulphide in mild acidic medium, where only Cu(II) sulphide will be precipitated
(B) ammonium hydroxide buffer, where only Fe(II) hydroxide will be precipitated
(C) hydrogen sulphide in mild acidic medium, where only Fe(II) sulphide will be precipitated
(D) ammonium hydroxide buffer, where only Cu(II) hydroxide will be precipitated.
8. Aqueous solutions having equimolar quantities of Pb(NO3)2, AgNO3, AgSO4, BaCl2 and K2CrO4 are allowed to
react and the reaction mixture is then filtered. Which ions in the filtrate in appreciable quantity ?
[NSEC-2007]
(A) Pb2+, Ag+, Ba2+, K+, NO3, SO42 CrO42 Cl (B) Ba2+, K+, NO3, CrO42
(C) Pb2+, Ba2+, K+, NO3,CrO42 (D) K+, NO3
9. 1 mL of concentrated aqueous ammonia is added dropwise to 1 mL of a dilute aqueous solution of Cu(II).

What observations can be made during this process ? [NSEC-2008]
(A) The colorless Cu(II) nitrate solution turns blue and yields a dark blue precipitate
(B) The colorless copper (II) nitrate solution yields a white precipitate which turns dark blue upon standing.
(C) The light blue copper (II) nitrate solution yields a white precipitate which redissolves to form a dark blue
solution.
(D) The light blue copper (II) nitrate solution turns dark
10. Two white solids, lead (II) chloride and silver chloride can be distinguished from each other by -
[NSEC-2008]
(A) adding cold water to each : the silver chloride will dissolve.
(B) adding hot water to each : the lead (II) chloride will dissolve.
(C) adding sodium chloride solution to each : the lead (II) chloride will become warm and release chlorine
gas.
(D) adding zinc chloride solution to each : the silver chloride will change to metallic silver.
11. CuSO4 reacts with KCN to form water insoluble CuCN. This insoluble precipitate dissolves in excess of KCN,
due to formation of the following complex [NSEC-2008]
(A) K2[Cu(CN)4] (B) K3[Cu(CN)4] (C) Cu(CN)2 (D) Cu[KCu(CN)4]
12. The pair of cations which cannot be separated by H2S in a 0.3N acid solution is - [NSEC-2011]
(A) Al+++, Hg++ (B) Bi+++, Pb++ (C) Zn++, Cu++ (D) Ni++, Cd++
13. An aqueous of a salt ‘X’ gives white precipitate with dilute H2SO4. The same solution with a few drops of aq.
KI gives golden yellow precipitate which dissolves on heating. The salt ‘X’ is : [NSEC-2012]
(A) Ba(NO3)2 (B) Sr(NO3)2 (C) Pb(NO3)2 (D) Zn(NO3)2
ADVQUA - 261
14. The ions which give black precipitates on passing H2S gas in acidic medium are [NSEC-2013]
(A) Al3+ and Ni2+ (B) Ni2+ and Co2+ (C) Cu2+ and Bi3+ (D) Zn2+ and Mn2+
15. The pair of compounds that will not react with each other in an aqueous solution, at room temperature is
[NSEC-2014]
(A) FeCl3 ,SnCl2 (B) HgCl2 ,SnCl2 (C) FeCl2 ,SnCl2 (D) FeCl3 ,K
16. The colorless salt that gives white precipitate with BaCl2 in aqueous HCl is [NSEC-2014]
(A) K 2 SO4 (B) K 2 SO3 (C) KNO3 (D) KBr
1. Does mercuric sulphide dissolve in sodium sulphide solution (of 2M) ?
2. What happens when black precipitate of HgS is dissolved in aquaregia ?
3. Which basic radical is tested with the help of alkaline sodium stannite solution ?
4. Does tartaric acid can be used to distinguish SbOCl and BiOCl ?
5. What happens when Mn(II) ions free from chloride ions react with acidified solution of (NH4)2S2O8 or K2S2O8
in presence of a few drops of AgNO3 solution ?
6. How bromine water test (Alkaline medium) can be used to distinguish between Co2+ and Ni2+ ions ?
7. A mixture consists (A) (red solid) and (B) (colourless solid) which gives lilac colour in flame.
(a) Mixture gives black precipitate (C) on passing H2S (g).
(b) (C) is soluble in aquaregia and on evaporation of aquaregia and adding SnCl 2 gives
greyish black precipitate (D).
The salt solution with NH4OH gives a brown precipitate.
(i) The sodium extract of the salt with CCl4/FeCl3 gives a violet layer.
(ii) The sodium extract gives yellow precipitate with AgNO3 solution which is insoluble in dilute ammonia
solution.
Identify (A) and (B), and the precipitates (C) and (D). [JEE 2003, 4/60]
8. When a crystaline compound (X) is heated with K2Cr2O7 and concentrated H2SO4, a deep red gas (A) is
evolved. On passing (A) into caustic soda solution, a yellow coloured solution of (B) is obtained. Neutralizing
the solution of (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
K2Hg4 solution, a reddish brown precipitate (D) is formed. Identify (A), (B), (C), (D) and (X). Write the equations
of reactions involved. [JEE 2002, 5/150]

9. Dissolution of white precipitate of Hg2Cl2 in aquaregia evolved the gas
(A) Cl2 (B) NO (C) NO2 (D) HCl
10. White ppt of silver gives brown ppt on boiling but when it is heated (>300°C), then a metallic black ppt. is
obtained. Identify the compound of silver having white ppt.
(A) Ag2SO3 (B) Ag2S2O3 (C) Ag2CO3 (D) AgCl
11. Which of the following reagents gives white precipitate with Hg(NO 3)2 solution ?
(A) Cobalt (II) thiocyanate (B) Tin (II) chloride (excess)
(C) Ammonia solution (D) Potassium cyanide solution
ADVQUA - 262
12. Which of the following is insoluble in dil. HNO3 but dissolves in aquaregia ?
(A) HgS (B) PbS (C) Bi2 S3 (D) CuS.
13. In regards to Sn2+ and Sn+4 which statement is incorrect -

(A) Sn2+ sulphides is black while Sn+4 sulphide is golden yellow.
(B) Sn2+ sulphides is Brown while Sn+4 sulphide is golden yellow.
(C) Both sulphides dissolve in HCl.
(D) Both chloride does not react with HgCl2.
14. Which metal sulphide is soluble in concentrated HCl ?

(A) AS2S3 (B) SnS (C) HgS (D) None of these
15. SnCl2 solution, when treated with excess of KOH on heating produces
(A) K2SnO2 (B) K2SnO3 (C) K4SnO4 (D) K3SnO3
16. Intense blue precipitate of Fe4[Fe(CN)6]3 and potassium hydroxide solution when mixed gives :
(A) K2Fe[Fe(CN)6] - white precipitate (B) Fe(OH)3 - reddish–brown precipitate
(C) Fe(CN)3 – reddish–brown precipitate (D) KFe[Fe(CN)6] - Turnbull's blue
17. CoS (black) obtained in group IV of salt analysis is dissolved in aqua regia and is treated with an excess of
NaHCO3 and then Br2 water. An apple green coloured stable complex is formed. It is :
(A) sodium cobaltocarbonate (B) sodium cobaltibromide
(C) sodium cobalticarbonate (D) sodium cobaltobromide
18. [SDC_Jan 2015]
Colour of precipitate of " X " is :

(A) green (B) black (C) yellow (D) Reddish Brown
19. The presence of magnesium is confirmed in the qualitative analysis by :

(A) titan yellow solution + 2M NaOH solution (B) disodium hydrogen phosphate +NH4Cl + NH3 (aq.)
(C) magneson(I) reagent (D) all of these
20. To a solution of a substance, gradual addition of ammonium hydroxide results in a brownish black
precipitate which does not dissolve in excess of NH4OH. However, when KI (not in excess) is added to the
original solution, a green precipitate is formed. The solution contained :
(A) Lead salt (B) Silver salt (C) Mercurous salt (D) Copper salt.
21. Which of following is soluble in yellow ammonium sulphide ?

(A) CdS (B) CuS (C) SnS (D) PbS
22. A mixture of chlorides of cadmium, chromium, iron and aluminium was dissolved in water acidified with HCl
and hydrogen sulphide gas was passed for sufficient time. It was filtered, boiled and a few drops of nitric acid
were added while boiling. To this solution ammonium chloride and sodium hydroxide were added in excess
of filtered. The filtrate shall give test for :
(A) sodium and iron ion (B) sodium, chromium and aluminium ion
(C) aluminium and iron ion (D) sodium, iron, cadmium and aluminium ion.
23. Which one of the following cations will give a green coloured ash when a piece of filter paper dipped in a
solution containing its salt and Co(NO3)2 is burned ?
(A) Cu2+ (B) Mg2+ (C) Al3+ (D) Zn2+
24. To avoid the precipitation of hydroxides of Ni2+, Co2+, Mn2+ along with those of the third group cations, the
solutions should be :
(A) heated with few drops of concentrated HNO3. (B) boiled with excess of ammonium chloride.
(C) concentrated to small volume. (D) none of these.
ADVQUA - 263
25. A metal M and its compound can give the following observable changes in a sequence of reactions,
 Colourless solution        White 

excess
very dilute
M HNO

aqueous White    Colourless  H2S / OH
–
3
and no gas is evolved NaOH precipitate NaOH(aq.) solution      precipitate
 
The metal M can be :
(A) Mg (B) Pb (C) Zn (D) Sn
26. Identify the correct order of solubility of Na2S, CuS and ZnS in aqueous medium. [JEE 2002, 3/150]
(A) CuS > ZnS > Na2S (B) ZnS > Na2S < CuS
(C) Na2S > CuS > ZnS (D) Na2S > ZnS > CuS

27. When a metal rod M is dipped into a aqueous, colourless conc. solution of compound N, which is a nitrate
of metal ‘P’, the solution turns light blue. Addition of aqueous. NaCl to the blue solution given a white ppt ‘O’.
Addition of aqueous NH3, dissolve ‘O’ and give an deep blue solution. The final solution contains [M(NH 3)x]n+
and [P(NH3)y]m+. (M) & (N) both belongs to same groups in periodic table. Calculate the value of x + y + n +
m?
dil. HCl
28. Snn+ + H2S    (A) Yellow ppt.
If yellow ppt of (A) has "p" number of atom (per molecule). Then what is the value of (p + n).
29. Na2CrO4 + dil.H2SO4  Na2SO4 + H2CrO4

amyl alcohol
H2CrO4 + 2H2O2     'A' (blue colouration) + H2O
then find a + b, if a = number of O – O bonds in ''A''
b = number of Cr – O (sigma) bonds in ''A''
30. NaBiO3 + Mn(NO3)2 + HNO3  Product

Sum of oxidation number of Bi, N and Mn in products
31. Solution of AsO43– ion containing considerable excess of HNO3 on boiling with Ammonium molybdate test
gives a yellow crystalline precipitate (X). Number of oxygen atom present in per molecule of precipitated (X)
are :

32. Which of the following statement(s) is/are correct ?
(A) Yellow precipitated of silver arsenite is soluble in both nitric acid and ammonia.
(B) Potassium cyanide when added in very small quantity to copper sulphate solution, produces first yellow
precipitate which quickly converts in to white precipitate.
(C) Black precipitate of BiI3 turns orange on heating with water.
(D) White precipitate of Bi(OH)3 turns yellowish brown, when boiled.
33. Ammonium molybdate is used to detect the radical :

(A) PO43– (B) AsO43– (C) Cu2+ (D) Ag+
34. Which of the following sulphides do not dissolve in 50% HNO3 but dissolve in aquaregia ?
(A) CoS (B) NiS (C) CuS (D) HgS
35. Ni + H2SO4 (hot and concentrated)  X(g).

The liberated gas (select the correct statement(s)) :
(A) develops blue colour spots on the filter paper moistened with potassium iodate and starch solution.
(B) turns acidified K2Cr2O7 solution green.
(C) produces black precipitate with lead acetate solution.
(D) reacts with Cl2 water to produce an acid which gives white fumes with ammonia.
ADVQUA - 264
36. Select the incorrect statement(s).
(A) Ammonium ions produce yellow colour solution with sodium hexanitrito-N-cobaltate (III).
(B) Ammonia gas develops a brown colour on filter paper moistened with a solution of MnCl2 and H2O2.
(C) Ammonium ions produce white precipitate with saturated sodium hydrogen tartrate solution.
(D) Ammonium salts in presence of sodium hydroxide solution produces red precipitate with 4-nitrobenzene
diazonium chloride reagent.
37. Which of the following statements is incorrect?

(A ) The black precipitate 'D' is of bismuth.
(B) The black precipitate 'D' is of Hg + Hg(NH2)NO3.
(C) Aqueous solution of 'A' gives yellow precipitate with freshly prepared 10% solution of pyrogallol.
(D) Aqueous solution of 'A' gives red precipitate with 8-hydroxyquinoline (5%) and potassium iodide (6M) in
acidic medium.

A. General %
8. Section 5 contains 1 multiple choice questions. Question has two lists (list-1 : P, Q, R and S; List-2 :
1, 2, 3 and 4). The options for the correct match are provided as (A), (B), (C) and (D) out of which ONLY
ONE is correct.
C. Marking Scheme :

1. A solution containing SCN– ions can be used to test one or more out of : Fe3+, Co2+ , Cu2+, Ag+ and Hg2+.
(A) Fe3+ and Co2+ only (B) Co2+, Cu2+, Ag+ and Hg2+
(C) Fe3+, Cu2+, Co2+ and Hg2+ (D) all
ADVQUA - 265
2. A blue colouration (in solution or precipitate) is not obtained when :
(A) ammonium hydroxide dissolves in copper sulphate.
(B) cobalt chloride reacts with NH4SCN in presence of amyl alcohol.
(C) ferric chloride reacts with sodium ferrocyanide.
(D) aqueous ammonia reacts with white precipitate of silver (I) chloride.
3. A metal nitrate solution reacts with dilute hydrochloric acid to give a white precipitate which is soluble in
concentrated potassium chloride. White precipitate on passing of hydrogen sulphide gas is converted into
black precipitate. The black precipitate on boiling with hydrogen peroxide (3%) is converted again to a white
precipitate which is soluble in ammonium acetate. The cation of the metal nitrate is :
(A) Pb2+ (B) Ag+ (C) Hg2+ (D) Bi3+
4. A metal nitrate solution does not give white precipitate with concentrated hydrochloric acid but on dilution
with water produces a white precipitate. The metal nitrate solution with K2CrO4 and Na2HPO4 reagents gives
red and yellow precipitates respectively which are soluble in ammonia solution. The cation of the metal
nitrate is :
(A) Pb2+ (B) Ag+ (C) Cu2+ (D) Bi3+
5. Which of the following pairs comprise the red precipitates ?

(A) Ag2CrO4 and Hg2CrO4 (B) HgI2 and Ni(dmg)2
(C) BiOI and Cu2[Fe(CN)6] (D) (A) and (B) both
6. A coloured solution of an inorganic salt reacts with potassium thiocyanate to give first a black precipitate,
which slowly turns white. The salt solution also gives black precipitate with H2S gas in slightly acidic medium.
The black precipitate dissolves in potassium cyanide forming a colourless solution. The basic radical present
in the inorganic salt is :
(A) Bi3+ (B) Cu2+ (C) Hg2+ (D) None
7. Select the incorrect statement.

(A) Marsh's test involves the reduction of soluble arsenic compound to arsine by nascent hydrogen in acidic
solution and its subsequent decomposition into hydrogen and metallic arsenic as a brownish-black mirror on
heating in a glass tube mixed with hydrogen.
(B) Ammonical silver nitrate gives metallic silver mirror with saturated solution of hydrazine sulphate.
(C) Red precipitate of silver (I) chromate is soluble in dilute nitric acid and ammonia solution.
(D) None of these

8. The following can be used to regulate the concentration of OH¯ ions for the scheme of basic radical analysis
(III group).
(A) NH4NO3 (B) NH4Cl (C) (NH4)2SO4 (D) (NH4)2CO3
9. White precipitate of PbSO4 gets dissolved in :

(A) concentrated H2SO4 on heating (B) concentrated NaOH
(C) (NH4)2CO3 (D) dilute HNO3
10. Select the correct statement(s).

(A) In group III, Fe3+ and Cr3+ can be differentiated by increasing NH4+ ion concentration
(B) In Vth group, Na2CO3 is added to precipitate out only the carbonates of Ba2+, Sr2+ and Ca2+.
(C) Like brown ring test, diphenylamine test is given only by salts containing NO 3–.
(D) Sodium chloride on heating with aqueous solution of K2Cr2O7 and concentrated H2SO4 produces deep red
vapours.
ADVQUA - 266
11. Which of the following statement(s) is/are not correct ?
(A) Nickel salts give rosy red precipitate with dimethyl glyoxime in excess of NH4OH.
(B) Fe (III) salts give red colour with potassium sulphocyanide.
(C) In nitroprusside, the iron and NO exist as Fe(III) and NO.
(D) Mn (II) salts give white precipitate with NaOH which turns brown on adding Br 2 water.
12. Potassium ferrocyanide is used for testing

(A) Cu2+ and Zn2+ (B) Fe3+ and Ca2+ (C) Ag+ and Zn2+ (D) Th4+ and Cu2+

13. How many of the following pairs of ions can be separated by H2S in dilute HCl ?
Bi3+ and Sn4+, Al3+ and Hg2+, Cd2+ and Zn2+, Fe3+ and Cu2+, As3+ and Sb3+
14. In how many of the following reactions, one of the product is obtained as a yellow precipitate ?
Ba2+ (aq) + CrO42– (aq)  product
Ag+ (aq) + Br – (aq)  product
Pb2+ (aq) + I– (aq)  product
NH4+ (aq) + [PtCl6]2– (aq)  product
15. In how many of the following cases solubility of salt is greater in acidic solution than in pure water?
AgCl, AgCN, MnS,
Zn(OH)2, Ag3PO4, AgNO2,
Al(OH)3, CH3COOAg, BaSO3
16. How many statements are correct ?

(i) Like CO32–, SO32– also gives test with lime water.
(ii) In the test of NO3– , brown ring is formed due to the formation of [Fe (H2O)5 NO]2+ .
(iii) Aqueous solution of Ag+ ions gives brick red/red precipitate with K2CrO4.
(iv) Lead salts turn black on prolonged exposure in a chemical laboratory.
(v) In analysis of group IInd cations, H2S gas is passed in presence of hydrochloric acid to enhance the
concentration of S2– ions.
(vi) Aqueous solution of Cu2+ ions forms a green complex with K4[Fe(CN)6].
17. How many of the following reaction result in the formation of colored precipitate (not white).
(a) HgCl2 + SnCl2 (excess)  (b) HgCl2 + KI 
(c) Pb(NO3)2 + KCl  (d) NH4Cl + NO2– + Co3+ 
(e) Ni2+ + + NH4OH 
aq. Pb 2
(f) K2Cr2O7 + conc.H2SO4 + Cl2  A  B   ?
NaOH
(g) K2CrO4 + Hg22+  (h) Hg2+ + Co2+ + SCN– 
(i) Cu2+ + I– 
(k) Cd2+ + CN– 
18._ Which of the following sulphides are not black in colour.

PbS, CdS, As2S3, Sb2S3, SnS, CoS, HgS, ZnS, MnS.
ADVQUA - 267

This section contains 1 paragraphs, each describing theory, experiments, data etc. 3 questions relate to the
paragraph. Each question has only one correct answer among the four given options (A), (B), (C) and (D)
19. Compound (A) is :

(A) HgI2 (B) K2HgI4 (C) Hg(NO3)2 (D) Hg2(NO3)2
20. (D) + (NH4)2SO4  brown ppt. (G). Hence, compound (G) is :
in basic medium
(A) HgI2 (B) NH4I (C) HgO.Hg(NH2)I (D) Hg(NH2)I
21. White ppt. (B) + (NH3  Black ppt. (H). Hence, (H) is due to the formation of :
in basic medium
(A) Hg(NH2)CI (B) Hg (C) Hg(NH2)Cl + Hg (D) Hg(NH2)2

22. Match the reactions/reaction conditions listed in column-I with the characteristics/ precipitate colour of the
reaction products listed in column-II.
Column  Column 

(P) 2NiS + 2HNO3 + 6HCl       
 (1) Black precipitate & its chloride imparts greenish blue
extract with water
flame.
amyl alcohol
(Q) CoCl2 + 4NH4 CNS 
 (2) Blue colour in organic layer.

(R) CuCl2 + NaOH  (3) White precipitate soluble in ammonium acetate.
(S) Sr(CH3COO)2 + (NH4)2 C2O4  (4) Green colour solution.
(T) H2SO4 + PbCl2  (5) Yellow precipitate soluble in NaOH.
(U) Na2CrO4 + (CH3OO)2 Pb  (6) Scarlet / red precipitate.
(V) HgCl2 + KI (Not in excess)  (7) White precipitate & its chloride imparts crimson flame.
Code :
P Q R S T U V
(A) 1 3 2 4 7 6 5
(B) 3 2 7 6 5 4 1
(C) 4 2 1 7 3 5 6
(D) 7 3 5 6 4 2 1
ADVQUA - 268
Que. 1 2 3 4 5 6 7 8 9 10
Ans.
Que. 11 12 13 14 15 16 17 18 19 20
Ans.
Que. 21 22
Ans.

Problem 1 [IChO-1998]
The following 8 steps describe the procedure for analyzing a sample of an alloy that contains tin and lead.
1. A 0.4062 g sample of alloy was dissolved by heating it in a small beaker with a mixture of 11 M hydrochloric
acid and 16 M nitirc acid, The beaker was heated unitl all the alloy dissolved. In this procedure, lead is
oxidised to Pb(II) and in becomes Sn(IV) .
2. After 5 minutes of heating to expel oxides of nitrogen and chlorine, then a precipitate of some tin compounds
and a lead compound appeared.
3. A 25.00 mL a liquid of 0.20000 M N2EDTA solution was added. The precipitate dissolved and a clear, colourless
solution was obtained.
4. This solution was quantitatively transferred to a 250.0 mL volumetric flask and made up to the mark with
distilled water.
5. A 25.00 mL a liquid of this solution was treated with 15 mL of a 30% w/v solution of hexamine
(hexamethylenetramine), 130 mL of water and two drops of Xylenol Orange solution. The pH of the solution
was 6.
6. The clear, yellow solution from step 5 was titrated with standard 0.009970 M lead nitrate solution until the
colour just changed from yellow to red. The titre at this endpoint was 24.05 mL.
7. 2.0 g of solid NaF was added to the titration flask The solution immediately turned back to yellow.
8. The solution was titrated with more standard 0.009970 M lead nitrate solution until the colour changed to red
again. The titre at this endpoint was 15.00 mL.
Hexamine and Xylenol Orange have the structures shown below. The pKb of hexamine is 9.5. Xylenol Orange
red is below pH 4, yellow above pH 5.
N
N N
N
Hexamine
O
||
O S
OH O
||
O
||
OH
||
O O
||
||
HO OH
OH OH
Xylenol Orange (Xo)
ADVQUA - 269
K’ MY is the conditional formation constant =  KMY K’ MY for the formation of the EDTA complexes of Pb(II)
and Sn (IV), in the presence and absence of fluoride, are shown in the following figure.
Sn + ESTA
22
STA
20 Pb + E
18
16 Pb + ESTA + F
14
12
10
8
6 Sn + EDTA + F
4
2
0
-2 1 2 3 4 5 6 7 8 9 10 11 12
-4
1.1 What is the lead compound that precipitates in step 2 ?
1.2 Write a balanced ionic equation that explains the disappearance of the lead compound that precipitated in
step 3 (at pH 6).
1.3 What is the purpose of hexamine in step 5 of this analysis?
1.4 What is the purpose of Xylenol Orange in this analysis?
1.5 Write balanced ionic equations for the reactions that occur (i) during the titration and (ii) are responsible for
the colour change at the endpoint in step 6 of the analysis.
1.6 What is the purpose of NaF in step 7 of this analysis ?
1.7 Write a balanced ionic equation for the reaction that occurs in step 7.
1.8 Write a balanced equation that explains why the colour changed from red to yellow in step 7 of this analysis.
1.9 Write a balanced ionic equation that explains why the lines on the graph above of log K’MY versus. pH for Pb
+ EDTA and Pb + EDTA + F are coincident below pH 2.
1.10 Calculate the percentage by mass of Sn and Pb in the alloy.
ADVQUA - 270
PART - I
1. (2) 2. (3) 3. (2) 4. (2) 5. (1)
6. (3) 7. (3) 8. (3) 9. (1) 10. (3)
11. (3) 12. (1) 13. (4) 14. (2) 15. (2)
16. (2) 17. (1) 18. (1) 19. (3) 20. (1)
21. (4) 22. (4) 23. (4) 24. (1) 25. (2)
26. (1) 27. (2) 28. (1) 29. (2) 30. (1)
PART - II
1. (D) 2. (A) 3. (C) 4. (C) 5. (B)
6. (A) 7. (A) 8. (D) 9. (C) 10. (B)
11. (B) 12. (B) 13. (C) 14. (C) 15. (C)
16. (A)
PART - III
1. Yes , forming a soluble complex.
HgS + S2–   [HgS2]2–
2. 3HgS +6HCl +2HNO3  3HgCl2 +3S + 2NO +4 H2O
3. Bi3+ ; Bi3+ + 3OH– 

 Bi(OH)3  ; 2Bi(OH)3  + 3[Sn(OH)4]2– 
 2Bi  (black) + 3[Sn(OH)6]2–.
4. Yes : SbOCl is soluble in tartaric acid but BiOCl is insoluble in tartaric acid.
5. Reddish–violet colouration is obtained owing to the formation of MnO4–.

2 Mn2+ + 5 S2O82– + 8 H2O   MnO4– + 10 SO42– + 16 H+
AgNO3 acts as catalyst.
6. Ni2+ gives black ppt (Ni2O3) with NaHCO3 and bromine water on heating. Where as Co2+ gives green coloured
solution.
NiCl2 + 2NaHCO3   NiCO3 + 2NaCl + H2O
2 NiCO3 +[O]   Ni2O3  (Black) +2CO2
7. (A), (B), (C) and (D) are HgI2, KI, HgS and Hg respectively.
8. (X) = NH4Cl, (A) = CrO2Cl2 , (B) = Na2CrO4 , (C) = PbCrO4 , (D) =
9. (B) 10. (C) 11. (C) 12. (A) 13. (A)
14. (B) 15. (A) 16. (B) 17. (C) 18. (B)
19. (D) 20. (C) 21. (C) 22. (B) 23. (D)
24. (B) 25. (C) 26. (D) 27. 9 28. 7
29. 2+5=7 30. 7 + 3 + 5 = 15 31. 40 32. (A,B,C) 33. (A,B)
34. (A,B,D) 35. (A,B,D) 36. (A,D) 37. (B)
ADVQUA - 271
PART - IV
1. (D) 2. (D) 3. (A) 4. (B) 5. (D)
6. (B) 7. (D) 8. (A,B) 9. (A,B) 10. (A)
11. (C) 12. (A,B,C,D) 13. 3 14. 4 15. 8
16. 4 17. 07 18. 6 19. (D) 20. (C)
21. (C) 22. (C)
PART - V
1.1 PbCl2 or any hydroxo species etc.
1.2 PbCI2(s) + H2Y2–  PbY2– + 2H+ + 2 Cl– or similar
1.3 It forms a pH buffer.
1.4 It is a metallochromic indicator.
1.5 (i) The reaction that occurs during the titration:

Pb2+ + H2Y2–  PbY2– + 2 H+
(ii) At the endpoint, a slight excess of Pb2+ forms a red complex with the xylenol orange indicator:
Pb2+ + XO (yellow)  PbXO2+ (red)
1.6 The role of the NaF: It forms a complex with tin.
1.7 From the graph of log K'MY VS pH, it can be seen that the fluoride forms a stable complex with Sn4+ but not
with Pb2+ at pH 6, displacing EDTA:
SnY + nF– + 2H+  SnFn(n–4)– + H2Y2– where n is typically 4 - 6.
1.8 The released EDTA destroys the small amount of red PbXO complex, producing free (yellow) XO. (Charge on
XO ignored)
H2Y2– + PbXO2+  PbY2– + XO(yellow) + 2 H+
1.9 Below pH 2, F– is protonated and does not compete effectively with Y for Pb2+ H+ + F–  HF.
1.10 The percentage by mass of Sn and Pb in the alloy:

The amount of EDTA in excess from the amount of standard Pb2+ titrant:
n(EDTA) = n(Pb2+) = 0.02405 dm3 × 0.009970 mol dm –3 = 2.398 × 10–4 mol.
The original amount of EDTA:
n(EDTA)init. = 0.1  25.00 dm 3  0.2000 mol dm -3 = 5.000 10-4 mol
EDTA consumed by the Pb2+ and Sn4+ in a 25 cm3 aliquot:
n(EDTA)consumed = 5.000 × 10–4 – 2.398 × 10–4 mol = 2.602 × 10–4 mol = n(Pb2+ + Sn4+) in a 25 cm3 aliquot.
The amount of EDTA released from SnY by reaction with fluoride:
n(EDTA) released = n(Pb2+)stand. = 15.00 cm3 × 0.009970 mol dm –3 = 1.496 × 10–4 mol
= n(Sn4+) in the 25 cm3 aliquot
in a 25 cm3 aliquot n(Pb2+) = (2.602 × 10–4 – 1.496 × 10–4) mol = 1.106 × 10–4 mol
In the original 0.4062 g sample of alloy:
m(Sn) = 10 × 1.496 × 10–4 mol × 118.69 g mol–1 = 0.1776 g
m(Pb) = 10 × 1.106 × 10–4 mol × 207.19 g mol–1 = 0.2292 g
The percentages of tin and lead:
Sn: 100 × (0.1776 / 0.4062) = 43.7 %
Pb: 100 × (0.2292 / 0.4062) = 56.4 %
ADVQUA - 272
PART - I
Cl
1. Hg2Cl2 + 2NH3  Hg  (white) + Hg (black) + NH4Cl
NH2

Black
2. The white precipitate obtained with H2SO4 is that of PbSO4. The white crystalline substance may be that of
Pb(NO3)2.
Pb2+ + S2–  PbS  (black) ; 3PbS  + 8HNO3  3Pb2+ + 6NO3– + 3S  + 2NO + 4H2O
Pb2+ + SO42–  PbSO4  (white)
PbSO4 + 2CH3COONH4  (NH4)2[Pb(CH3COO)4] + (NH4)2SO4
BaS and SrS are not precipitated. Ag2SO4 is white precipitate but does not dissolve in ammonium acetate.
3. PbI2 is yellow (known as golden spangles).
4. AgBr has the highest solubility in 10–3 M NH4OH

AgBr dissolves in all other solvents poorly.
5. Both Cd2+ and Sn2+ are precipitated as yellow sulphides in the presence of dilute HCl.
6. Cd2+ + H2S  CdS + 2H+, reaction is reversible; if the concentration of strong acid in the solution is
above 0.5 M, precipitation is incomplete. Concentrated acid dissolves the precipitate for the same reason.
7. 2Cu2+ + 4I–  Cu2I2 + I2

Cu2+ + 3CN–  CuCN  + (CN)2
8. (1) Bi3+ + 3NH4OH  Bi(OH)3 (white) + 3NH4+

(2) Bi3+ + NO3– + H2O  BiO(NO3)  (white) + 2H+
Bi3+ + Cl– + H2O  BiOCl  (white) + 2H+
(3) Bi3+ + 3I–  BiI3 (black) ; BiI3 + I–  [BiI4]– (orange solution)
(4) Bi3+ + 3OH–  Bi(OH)3 (white) ; 2Bi(OH)3 + 3[Sn(OH)4]2–  2Bi(black) + 3[Sn(OH)6]2–
9. (1) Cu+2 + 2OH–  Cu(OH)2 

 CuO  +H2O
black ppt.
(2) Zn + 2OH  Zn(OH)2
+2 –
white ppt.
(3) Al+3 + 3OH–  Al(OH)3
white ppt.
(4) Sn+2 + 2OH–  Sn(OH)2
white ppt.
10. On adding H2O2 in alkaline medium or SnCl2 solution in acidic medium, the [Fe(CN)6]3– part of the compound
is reduced and prussian blue is precipitated.
11. CrO42– + 2H+ + 2H2O2  CrO5 (chromium peroxide) + 3H2O

It in etheral layer develops blue colouration.
12. Mn(OH)2 + 2HNO3  Mn(NO3)2 + 2H2O.

2Mn(NO3)2 + 5PbO2 + 6HNO3  2HMnO4 (red – violet or purple colour) + 5Pb(NO3)2 + 2H2O.
ADVQUA - 273
13. (1) Zn(OH)2 + 2OH– [Zn(OH)4]2–
(2) and (3) Zn(OH)2 + 4NH3 [Zn(NH3)4]2+ + 2OH–
or NH4+
14. (1) No precipitate with K2CrO4 in acetic acid as its Ksp is high.
(2) Ca2+ + 2K+ + [Fe(CN)6]4–  K2Ca[Fe(CN)6] (white)
(3) It imparts brick red colour to Bunsen flame.
(4) Ca(HCO3)2 is formed which is water soluble.
15. (2) BaCO3 + ZnS mixture dissolves in HCl but is insoluble in water. Further the solution in HCl will be
colourless due to the formation of soluble BaCl2 and ZnCl2.
16. The KSP of Al(OH)3 is low as compared to that of the hydroxides of other metals. The OH– concentration
provided by ammonium hydroxide in presence of NH4Cl is just sufficient to precipitate Al3+ as Al(OH)3.
NH 4 Cl
Al3+ + NH3 + H2O    Al(OH)3  (gelatinous white) + NH4+ .
17. Group 3rd radicals are precipitated as hydroxides and the addition of NH4Cl suppresses the ionisation of
NH4OH so that only the group 3 cations are precipitated as hydroxides because of their low solubility
products.
18. MnO4– in acidic medium oxidises Fe2+ to Fe3+.
19. (1) 2Fe3+ + H2S  2Fe2+ + 2H+ + S (white)

(2) 2Fe3+ + 3S2–  2FeS (black) + S
(3) Fe3+ + 3SCN–  Fe(SCN)3 deep red colouration
20. Ni2+ and Fe2+ both on reaction with alkaline solution of dimethyl glyoxime give red precipitate and red solution
respectively but not zinc.
21. Ag2S + 2HCl  AgCl  + 2H2S ; HgS is also insoluble in 2N HCl so silver and mercury do not pass into
filtrate while ZnS, MnS and FeS dissolve in 2N HCl forming their soluble chlorides and thus pass into filtrate.
22. (1) Pb+2 + CrO4–2  PbCrO4 (yellow ppt)
(2) Ba+2 + CrO4–2  BaCrO4 (Yellow ppt)
(3) Ag + CrO4–2  Ag2CrO4 (Brick like red ppt)
(4) Ca+2 + CrO4–2  CaCrO4 (soluble)
23. CaS belongs to Vth group and precipitate by H2S in presence of NH4OH and NH4Cl
24. Ag2S + NaCN  Na[Ag(CN)2] (soluble)
25._ (1) Cu2+ + H2S  CuS (ppt.)

Ag2+ + H2S  Ag2S (ppt.)
(2) Cu2+ + HCl  CuCl2 (soluble)
Ag2+ + HCl  AgCl (ppt.)
with HNO3 and (NH4)2NO3 both Ag+ and Cu2+ form soluble compound.
 Ag(NH3 )2   CrO 24 –

2Ag   CrO 24–  Ag 2 CrO 4  
NH
26. 3
(red ppt .) ( So lub le )
27. Because NH4+ form soluble compounds.
28. CuSO4 + NH4OH  [Cu(NH3)4]SO4 + H2O
ADVQUA - 274
29. 2Al2O3 + 2Co+2 + 4NO3–  2CoAl2O4 (thenard blue) + 4NO2 + O2
30. CrCl3 + NaOH  Cr(OH)3  [Cr(OH4)]– (soluble)
AlCl3 + NaOH  Al(OH)3  [Al(OH4)]– (soluble)
ZnCl2 + NaOH  Zn(OH)2  [Zn(OH4)]2– (soluble)

CuCl2 + NaOH  Cu(OH)2  (not soluble in excess NaOH)
PART - III
7. (A) + (B)  lilac colour in flame. So one of the cation may be K+ .
H2 S ( g )
(a) (A) + (B)   (C) black precipitate.
so lub le Evaporatio n SnCl 2
(b) (C)   soluble      Residue   Greyish black precipitate (D).
in aqua regia
NH 4 OH
(A) + (B)   brown precipitate. So second cation may be Hg2+.
CCl 4 / FeCl 3
(i) Sodium carbonate extract of salt    violet colour..
AgNO 3 NH3
(ii) Sodium extract of salt   yellow precipitate   soluble.
So the anion may be I .
–
(a) HgI2 + H2S  HgS (C)  (black) + 2HI.
(b) 3HgS + 6HCl + 2HNO3  3HgCl2 + 2NO + 4H2O + S.

HgCl2 + SnCl2  Hg  (D) (greyish black) + SnCl4.
2KI (B) + HgI2 (A)  K2[HgI4] (colourless).
2K2[HgI4] + NH3 + 3KOH  [HgOHg(NH2)I]  ( brown).

Sodium carbonate extract of salt contains NaI.
CCl
2NaI + 2Fe3+   4
 I2  (violet)+ 2Na+ + 2Fe2+.
I2 dissolves in CCl4 giving violet colour solution.
AgNO3 + NaI  AgI  (yellow) + NaNO3.
AgI is insoluble in ammonia solution.
So, (A), (B), (C) and (D) are HgI2, KI, HgS and Hg respectively.
8. 4Cl– + Cr2O72– + 6H+  2CrO2Cl2  (A)(deep red) + 3H2O

CrO2Cl2 + 4OH–  CrO42– (B)(yellow solution) + 2Cl– + 2H2O
CrO42– + Pb2+  PbCrO4  (C)(yellow)
NH4Cl + NaOH  NaCl + NH3 + H2O
NH3 + K2Hg4 + H2O  (D) + 4K + 3H
So, (X) = NH4Cl, (A) = CrO2Cl2 , (B) = Na2CrO4 , (C) = PbCrO4 , (D) =
ADVQUA - 275
9. aquaregia is HNO3 + HCl
1 : 3
3Hg2Cl2 + 2HNO3 + 6HCl 
 6HgCl2 +2NO + 4H2O
10.
11. (A) Hg2+ + Co2+ + 4SCN–  Co[Hg(SCN)4 (deep blue) ;

(B) 2Hg2+ + Sn2+ + 2Cl–  Hg2Cl2 (white) + Sn4+ ; Hg2Cl2 + Sn2+  Hg  (black) + Sn4+ + 2Cl–
(C) 2Hg2+ + NO3– + 4NH3 + H2O  HgO.Hg(NH2)NO3 (white)
(D) KCN no effect i.e. no reaction.
12. PbS, Bi2S3 and CuS dissolve in dilute HNO3 forming nitrates but HgS dissolves in aquaregia forming HgCl2.
13. Sn2+ chloride react with HgCl2 and formed black or grey ppt of Hg
SnCl2 + HgCl2  SnCl4 + Hg2Cl2
SnCl2 + HgCl2  SnCl4 + 2Hg (black grey ppt)
Sn+4 does not react with HgCl2. It is first treated with Aluminium foil which reduces Sn+4 to Sn+2 (Stannous
ion); then it with HgCl2
3SnCl4 + 2Al  2AlCl3 + 3SnCl2 (Stannous chloride)
15. SnCl2 + KOH 

 SnO
SnO + KOH (excess) 
 K2SnO2 + 2H2O
16. Fe4[Fe(CN)6]3 + 12OH–  4Fe(OH)3  (reddish brown) + 3[Fe(CN)6]4–
17. 2CoS + 6HCl + 2HNO3  3CoCl2 + 2NO + 3S + 4H2O

CoCl2 + 6NaHCO3  Na4 [Co(CO3)3] + 2NaCl + 3H2O + 3CO2
2Na4 [Co(CO3)3] + Br2  2Na3 [Co(CO3)3] + 2NaBr
(Green)
18. NiCl2 + KCN (excess)  K2[Ni(CN)4]
19. (A) titan yellow is absorbed by magnesium hydroxide producing a deep-red colour or precipitate.
(B) Mg2+ + NH3 + HPO42–  Mg(NH4)PO4  (white).
(C) Blue lake is formed by the adsorption of reagent on Mg(OH)2.
Cl
20. Hg2Cl2 + 2NH3  Hg  (white) + Hg (black) + NH4Cl
NH2

black
Hg22+ + 2I–  Hg2I2  (green)
21. Sn2+ belongs to second B group.
ADVQUA - 276
boiled
22. (Cd2+, Cr3+, Fe2+, Al3+) + H2S   CdS (yellow ppt.) + Filtrate (Cr , Fe , Al )  
dil. HCl 
3+ 2+ 3+
 HNO3
(Cr3+, Fe3+, Al3+) excess

  Fe(OH) (ppt.) + Filtrate, (Na+, Cr(OH) –, Al(OH) –, )
NH OH & NaOH
4
3 4 4
23. The filter paper ash test is substitute for cobalt nitrate charcoal cavity test. Double oxide ZnO.CoO formed is
green in colour. It is called Rinmann's green.
24. Function of strong electrolyte NH4Cl is to suppress the ionisation of NH4OH so that the concentration of OH–
ions in the solution is decreased but it is sufficient to precipitate the third group basic radicals because the
solubility product of group III hydroxides is lower than IV, V and VI group hydroxides. The Cr(OH) 3 is slightly
soluble in excess of precipitant, upon boiling the solution, Cr(OH)3 is precipitated.
25. 4Zn + 10H+ + NO 3–  4Zn2+ + NH4+ + 3H2O.
Zn2+ + 2OH–  Zn(OH)2  (white) ; Zn(OH)2 + 2OH–  [Zn(OH)4]2–.

[Zn(OH)4]2– + H2S  ZnS  (white) + 2OH– + 2H2O.
26. Sodium sulphide is water soluble and Ksp of ZnS is higher than that of CuS. So correct order is
Na2S > ZnS > CuS
27. Metal P is Ag & metal M is Cu.

NaCl
Cu + 2AgNO3  Cu(NO3 )2 + 2Ag + AgNO3 Cu(NO 3)2 + AgCl
(M) (P)
Blue solution Whit e ppt
NH3 (excess)
[Cu(NH3) 4]2+ + [Ag(NH 3) 2]+

 x = 4, y = 2, m = 1, n = 2
 x+y+m+n=4+2+2+1=9
dil. HCl
28. Sn4+ + H2S  
 SnS2 (yellow ppt)
n = 4, p = 3, n + p = 7
29. A is CrO5
30. HMnO4 + Bi(NO3)2 + NaNO3
31. AsO43– + NO3 + (NH4)MoO4  (NH4)3AsMo12O40
32. (A) Correct.

(B) Cu + 2CN  Cu(CN)2 (yellow)
2+ –
2Cu(CN)2  2Cu(CN)2 (white) + (CN)2

boiled
(C) BiI3 + H2O   BiOI (orange) + 2HI

(D) Bi(OH)3  BiO.OH (yellowish white) + H2O
33.  PO43– and AsO43– both radical give ammonium molybdate test.
34. CuS dissolves in 50% HNO3 ; 3CuS + 8HNO3  3Cu2+ + 6NO3– + 3S + 2NO + 4H2O
But NiS, CoS and HgS do not dissolve in 50% HNO3 and dissolve in aquaregia forming their chlorides.
ADVQUA - 277
35. (A) 5SO2 + 2IO3– + 4H2O  I2 + 5SO42– + 8H+ ; I2 + starch)  blue colour..
(B) 2H+ + 3SO2 + Cr2O72–  2Cr3+ (green ) + 3SO42– + H2O
(C) Pb2+ + SO32–  PbSO3  (white)
(D) SO2 + 2H2O + Cl2  H2SO4 + HCl
HCl + NH3  NH4Cl
Ni + H2SO4 + 2H+  Ni2+ + SO2 [X] + 2H2O
With dilute H2SO4, hydrogen gas is liberated.
36. (A) 3NH4+ + [Co(NO2)5]3–  (NH4)3[Co(NO2)6] (yellow)

(B) 2NH3 + Mn2+ + H2O2 + H2O  MnO(OH)2 (brown) + 2NH4+
(C) NH4+ + HC4H4O6–  NH4HC4H4O6(white)
(D) O2N N=N—Cl + NH4+ + 2OH–  O2N N=NONH4 (red colouration) + Cl– + H2O
37. (A) Bi3+ + 3 OH–  Bi(OH)3  ; 2Bi(OH)3  + [Sn(OH)4]2–  2Bi  + 3 [Sn(OH)6]2–.
(B) is not correct as 'D' is precipitate of bismuth.
(C) Bi3+ + C6H3(OH)3  Bi(C6H3O3 )  (yellow) + 3H+.
(D) Bi3+ + C9H7ON + H+ + 4I–  C9H7ON. HBiI4  (red)
PART - IV
ether
1. CoCl2 + 4NH4SCN   (NH4)2 [Co(SCN)4] (blue colour in ethereal layer) + 2NH4Cl.
Cu + 3SCN  CuSCN (white) + (SCN)2 .
2+ –
ether
FeCl3 + 3NH4SCN   Fe(SCN)3 (blood red colour) + 3NH4Cl.
Ag+ + SCN–  AgSCN  (white).
Co2+ + 4SCN– + Hg2+  Co[Hg(SCN)4]  (deep blue) or Hg[Co(NCS)4].
2. (A), (B) and (C) all gives blue colouration in solution or blue precipitate.
(D) AgCl  + 2NH3  [Ag(NH3)2]+ Cl– (colourless solution)
3. Pb2+ + 2Cl–  PbCl2 (white) ; PbCl2 + 2Cl–  [PbCl4] 2– (colourless soluble complex)
PbCl2 + H2S  PbS (black) + 2HCl
PbS + 4H2O2  PbSO4 (white) + 4H2O
PbSO4 + 2CH3COONH4  (NH4)2SO4 + (NH4)2[Pb(CH3COO)4]
4. Ag+ + 2Cl–  [AgCl2]– (soluble complex) ; Ag+ + Cl– (dilute HCl)  AgCl (white)
2Ag+ + CrO42–  Ag2CrO4(red) ; Ag2CrO4 + NH3  2[Ag(NH3)2]+ + CrO42–
3Ag+ + HPO42–  Ag3PO4 (yellow) + H+ ; Ag3 PO4 + 6NH3   [Ag(NH3)2 ]+ + PO43–
5. (A) Both are red precipitates

(B) Ni2+ + 2dmg + NH4OH  Ni(dmg)2  (red)
(C) BiOI (orange) and Cu2[Fe(CN)6] (brown)
6. Cu2+ + 2SCN–  Cu(SCN)2 (black)

2Cu(SCN)2  2CuSCN (white) + (SCN)2
H
Cu2+ + H2S 
 CuS (black) + 2H+
2CuS + 8CN–  2[Cu(CN)4]3– + S22–
ADVQUA - 278

7. (A) As3+ + 3Zn + 3H+  AsH3  + 3Zn2+ ; 4AsH3  4As  + 6H2 
(B) 4[Ag(NH3)2]+ + H2N–NH2.H2SO4  4Ag  + N2  + 6NH4+ + 2NH3  + SO42–
(C) 2Ag2CrO4  + 2H+ 4Ag+ + Cr2O72– + H2O
Ag2CrO4  + 4NH3 2[Ag(NH3)2]+ + CrO42–
So, all statements are correct.
8. (NH4)2 CO3 and (NH4)2 SO4 can not be used as they would also precipitate the IV and Vth group cations.
9. (A) PbSO4 + H2SO4 (hot and concentrated)  Pb2+ + 2HSO4– (soluble)
(B) It dissolves forming Na2[Pb(OH)4] soluble complex.
10. (A) Cr3+ + 3NH3 + 3H2O Cr(OH)3 + 3NH4+

The above reaction is reversible. On addition of NH4+ , shifts to backward direction. Thus if excess of
NH4+ salt is added, then precipitation of Cr(OH)3 will not take place. However, because of very small
Ksp of iron (III) hydroxide complete precipitation will take place even in the presence of ammonium
salts. (Ksp = 3.8 × 10–38)
(B) Concentration of CO32– provided by Na2CO3 in aqueous solution is just sufficient to precipitate Mg2+
ion as MgCO3 along with Ba2+ , Ca2+ and Sr2+ as their carbonates.
(C) The oxidising anions like MnO4–, Cr2O72–, ClO4–, etc., also respond to this test.
(D) K2Cr2O7 + NaCl + H2SO4  CrO2Cl2
11. Iron and NO exist as Fe(II) and NO+ respectively.
12. (A) Cu2 [Fe(CN)6] ; K2 Zn3 [Fe(CN)6]2 ; (B) Fe4 [Fe(CN)6]3 ; K2Ca [Fe(CN)6]
(C) Ag4[Fe(CN)6] ; K2Zn3 [Fe(CN)6] ; (D) Th[Fe(CN)6] ; Cu2[Fe(CN)6]
H
13. (1) Al3+ and Hg2+ 
 HgS  (black) + Al3+ (in solution)
H2S
H
(2) Cu2+ and Zn2+ 
 CuS  (black) + Zn2+ (in solution)
H2S
H
(3) Cd2+ and Zn2+ 
 CdS  (yellow) + Zn2+ (in solution)
H2S
14. Ba2+ (aq) + CrO42– (aq)  BaCrO4  (yellow)

Ag+ (aq) + Br – (aq)  AgBr  (yellow)
Pb2+ (aq) + 2I– (aq)  PbI2  (yellow)
2NH4+ (aq) + [PtCl6]2– (aq)  (NH4)2 [PtCl6]  (yellow)
15. AgCN, MnS, Ag3PO4, Zn(OH)2, AgNO2, FeS, BaSO3, Al(OH)3, CH3COOAg  solubility in acidic solution
is greater than that in pure water due to protonation of anion.
16. TTTTFF
(i) SO32– + Ca (OH)2  CaSO3  (white) + H2O
CO32– + Ca (OH)2  CaCO3  (white) + H2O
(ii) FeSO4 + NO + 5H2O  [Fe(H2O)5 NO]2+ SO42–
(iii) 2AgNO3 + K2CrO4  Ag2CrO4  (red) + 2KNO3
(iv) Pb2+ + H2S  PbS + 2H+
(v) S2– concentration in presence of dil HCl is sufficient to ppt the II nd group cations only. Due to common ion
effect ionization of H2S is suppressed.
(iv) 2Cu2+ + [Fe(CN)6]4-  Cu2[Fe(CN)6]  (chocolate brown)
ADVQUA - 279
17. (a) HgCl2 + SnCl2 (excess) Hg + SnCl4
black precipitated
(b) HgCl2 + KI  K2HgI4 (soluble)
(d) NH4Cl + NO2– + Co3+ (NH4)3 [Co(NO2)6]  yellow
(e) Ni2+ + + NH4OH Ni(dmg)2  (red)
aq. Pb 2
(f) K2Cr2O7 + conc.H2SO4 + Cl2  CrO2Cl2  Na2CrO4   PbCrO4
NaOH
(g) K2CrO4 + Hg22+  HgCrO4 (red ppt.)
(h) Hg2+ + Co2+ + SCN–  Co[Hg(SCN)4] or Hg[Co(NCS)4] (deepblue crystalline ppt.)
18. PbS  Black, CdS  yellow, As2S3  yellow, Sb2S3  Orange, SnS  Brown, CoS  Black,
HgS  Black, ZnS  White, MnS  Pink.
(19-21)
K2[HgI4] + OH– + (NH4)2SO4  HgO.Hg(NH2)I (brown ppt)

(D) (G)
HgCl2 + NH3  Hg(NH2)Cl + Hg (black ppt)

(B) (H)
NO–2 / NO3– + dil. HCl/con.HCl  NO

 Fe2+ NO + 5H2O  [Fe(H2O)5NO]2
22. (P) Aqueous solutions of nickel (II) salts are green, owing to the colour of the [Ni(H 2O)6]2+ complex.
(Q) Co2+ + 4SCN–  [Co(SCN)4]2– (blue colour complex). In amyl alcohol or diethyl ether dissolves forming
H2[Co(SCN)4].

(R) Cu2+ + 2OH–  Cu(OH2)  (blue) ; Cu(OH)2   CuO  (black) + H2O. Copper salts imparts
greenish blue colour to the Bunsen flame.
(S) Sr2+ + 2C2O42–  SrC2O4  (white) .
Strontium salts imparts crimson colour to the Bunsen burner.
(T) Pb2+ + SO42–  PbSO4  (white) ; PbSO4  + 2CH3COONH4  (CH3COO)2Pb + (NH4)2SO4.
(U) CrO42 + Pb2+  PbCrO4  (yellow) ; PbCrO4  + 4OH– [Pb(OH)4]2– + CrO42–.
(V) Hg + 2I  HgI2  (scarlet / red).
2+ – 
ADVQUA - 280
SOLUTION & COLLIGATIVE PROPERTIES [281]
EXERCISE I
Raoult’s law
Q.1 At 25°C, the vapour pressure of methyl alcohol is 96.0 torr. What is the mole fraction of CH3OH in a
solution in which the (partial) vapor pressure of CH3OH is 23.0 torr at 25°C?
Q.2 The vapour pressure of pure liquid solvent A is 0.80 atm. When a nonvolatile substance B is added to the
solvent its vapour pressure drops to 0.60 atm. What is the mole fraction of component B in the solution?
Q.3 The vapour pressure of pure water at 26°C is 25.21 torr. What is the vapour pressure of a solution
which contains 20.0 glucose, C6H12O6, in 70 g water?
Q.4 The vapour pressure of pure water at 25°C is 23.76 torr. The vapour pressure of a solution containing
5.40 g of a nonvolatile substance in 90.0 g water is 23.32 torr. Compute the molecular weight of the
solute.
Raoult’s law in combinaton with Dalton’s law of P.P. and V.P. lowering
Q.5 The vapour pressure of ethanol and methanol are 44.5 mm and 88.7 mm Hg respectively. An ideal
solution is prepared at the same temperature by mixing 60 g of ethanol with 40 g of methanol. Calculate
total vapour pressure of the solution.
Q.6 Calculate the mole fraction of toluene in the vapour phase which is in equilibrium with a solution of
benzene and toluene having a mole fraction of toluene 0.50. The vapour pressure of pure benzene is
119 torr; that of toluene is 37 torr at the same temperature.
Q.7 What is the composition of the vapour which is in equilibrium at 30°C with a benzene-toluene solution
with a mole fraction of benzene of 0.40? With a mole fraction of benzene of 0.60?
Pb =119 torr and Pt = 37 torr
Q.8 At 90°C, the vapour pressure of toluene is 400 torr and that of -xylene is 150 torr. What is the
composition of the liquid mixture that boils at 90°C, when the pressure is 0.50 atm? What is the composition
of vapour produced?
Q.9 Two liquids A and B form an ideal solution at temperature T. When the total vapour pressure above the
solution is 400 torr, the mole fraction of A in the vapour phase is 0.40 and in the liquid phase 0.75. What
are the vapour pressure of pure A and pure B at temperature T?
Q.10 Calculate the relative lowering in vapour pressure if 100 g of a nonvolatile solute (mol.wt.100) are
dissolved in 432 g water.
Q.11 What weight of the nonvolatile solute, urea needs to be dissolved in 100 g of water, in order to decrease
the vapour pressure of water by 25%? What will be the molality of the solution?
Q.12 The vapour pressure of an aqueous solution of glucose is 750 mm Hg at 373 K. Calculate molality and
mole fraction of solute.
Q.13 The vapour pressure of pure benzene at 25° C is 639.7 mm of Hg and the vapour pressure of a solution
of a solute in C6H6 at the same temperature is 631.7 mm of Hg. Calculate molality of solution.
Q.14 The vapour pressure of pure benzene at a certain temperature is 640 mm of Hg. A nonvolatile nonelectrolyte
solid weighing 2.175 g is added to 39.0 of benzene. The vapour pressure of the solution is 600 mm of
Hg. What is molecular weight of solid substance?
Q.15 The vapour pressure of water is 17.54 mm Hg at 293 K. Calculate vapour pressure of 0.5 molal
solution of a solute in it.
Q.16 Benzene and toluene form two ideal solution A and B at 313 K. Solution A (total pressure PA) contains
equal mole of toluene and benzene. Solution B contains equal masses of both (total pressure PB). The
vapour pressure of benzene and toluene are 160 and 60 mm Hg respectively at 313 K. Calculate the
value of PA/PB.
Boiling point elevation and freezing point depression
Q.17 When 10.6 g of a nonvolatile substance is dissolved in 740 g of ether, its boiling point is raised 0.284°C.
What is the molecular weight of the substance? Molal boiling point constant for ether is 2.11°C·kg/mol.
Q.18 A solution containing 3.24 of a nonvolatile nonelectrolyte and 200 g of water boils at 100.130°C at
1atm. What is the molecular weight of the solute? (Kb for water 0.513°C/m)
Q.19 The molecular weight of an organic compound is 58.0 g/mol. Compute the boiling point of a solution
containing 24.0 g of the solute and 600 g of water, when the barometric pressure is such that pure water
boils at 99.725°C.(Kb for water 0.513°C/m)
Q.20 An aqueous solution of a nonvolatile solute boils at 100.17°C. At what temperature will this solution
freeze? [Kf for water 1.86°C/m ]
Q.21 Pure benzene freeze at 5.45°C. A solution containing 7.24 g of C 2H2Cl4 in 115.3 g of benzene was
observed to freeze at 3.55°C. What is the molal freezing point constant of benzene?
Q.22 A solution containing 6.35 g of a nonelectrolyte dissolved in 500 g of water freezes at – 0.465°C.
Determine the molecular weight of the solute.[Kf for water 1.86°C/m ]
Q.23 The freezing point of a solution containing 2.40 g of a compound in 60.0 g of benzene is 0.10°C lower
than that of pure benzene. What is the molecular weight of the compound? (Kf is 5.12°C/m for benzene)
Q.24 The elements X and Y form compounds having molecular formula XY2 and XY4. When dissolved in 20 gm
of benzene, 1 gm XY2 lowers the freezing point by 2.3°, whereas 1 gm of XY4 lowers the freezing point by
1.3°C. The molal depression constant for benzene is 5.1. Calculate the atomic masses of X and Y.
Q.25 Calculate the molal elevation constant, Kb for water and the boiling of 0.1 molal urea solution. Latent
heat of vaporisation of water is 9.72 kcal mol–1 at 373.15 K.
Q.26 Calculate the amount of ice that will separate out of cooling a solution containing 50g of ethylene glycol
in 200 g water to –9.3°C. (Kf for water = 1.86 K mol1 kg)
Q.27 A solution of 0.643 g of an organic compound in 50ml of benzene (density ; 0.879 g/ml) lowers its
freezing point from 5.51°C to 5.03°C. If Kf for benzene is 5.12 K, calculate the molecular weight of the
compound.
Q.28 The cryoscopic constant for acetic acid is 3.6 K kg/mol. A solution of 1 g of a hydrocarbon in 100 g of
acetic acid freezes at 16.14°C instead of the usual 16.60°C. The hydrocarbon contains 92.3% carbon.
What is the molecular formula?
Osmotic pressure
Q.29 Find the freezing point of a glucose solution whose osmotic pressure at 25oC is found to be 30 atm.
Kf(water) = 1.86kg.mol1.K.
Q.30 At 300 K, two solutions of glucose in water of concentration 0.01 M and 0.001 M are separated by
semipermeable membrane. Pressure needs to be applied on which solution, to prevent osmosis? Calculate
the magnitude of this applied pressure.
Q.31 At 10oC, the osmotic pressure of urea solution is 500 mm. The solution is diluted and the temperature
is raised to 25°C, when the osmotic pressure is found to be105.3 mm. Determine extent of dilution.
Q.32 The osmotic pressure of blood is 7.65 atm at 37°C. How much glucose should be used per L for an
intravenous injection that is to have the same osmotic pressure as blood?
Q.33 What would be the osmotic pressure at 17°C of an aqueous solution containing 1.75 g of sucrose
(C12H22O11) per 150 cm3 of solution?
Q.34 A 250 mL water solution containing 48.0 g of sucrose, C12H22O11, at 300 K is separated from pure
water by means of a semipermeable membrane. What pressure must be applied above the solution in
order to just prevent osmosis?
Q.35 A solution of crab hemocyanin, a pigmented protein extracted from crabs, was prepared by dissolving
0.750 g in 125 cm3 of an aqueous medium. At 4°C an osmotic pressure rise of 2.6 mm of the solution
was observed. The solution had a density of 1.00 g/cm3. Determine the molecular weight of the protein.
Q.36 The osmotic pressure of a solution of a synthetic polyisobutylene in benzene was determined at 25°C. A
sample containing 0.20 g of solute/100 cm3 of solution developed a rise of 2.4 mm at osmotic equilibrium.
The density of the solution was 0.88 g/cm3. What is the molecular weight of the polyisobutylene?
Q.37 A 5% solution (w/v) of cane-sugar (Mol. weight = 342) is isotonic with 0.877%(w/v) of urea solution.
Find molecular weight of urea.
Q.38 10 gm of solute A and 20 gm of solute B are both dissolved in 500 ml water. The solution has the same
osmotic pressure as 6.67 gm of A and 30 gm of B dissolved in the same amount of water at the same
temperature. What is the ratio of molar masses of A and B?
Van’t Hoff factor & colligative properties

Q.39 A storage battery contains a solution of H2SO4 38% by weight. What will be the Van't Hoff factor if the
Tf(experiment) in 29.08. [Given Kf = 1.86 mol–1 Kg]
Q.40 A certain mass of a substance, when dissolved in 100 g C6H6, lowers the freezing point by 1.28°C. The
same mass of solute dissolved in 100g water lowers the freezing point by 1.40°C. If the substance has
normal molecular weight in benzene and is completely ionized in water, into how many ions does it
dissociate in water? Kf for H2O and C6H6 are 1.86 and 5.12K kg mol1.
Q.41 2.0 g of benzoic acid dissolved in 25.0g of benzene shows a depression in freezing point equal to 1.62K.
Molal depression constant (Kf) of benzene is 4.9 K.kg.mol1. What is the percentage association of the acid?
Q.42 A decimolar solution of potassium ferrocyanide is 50% dissociated at 300K. Calculate the osmotic
pressure of the solution.(R=8.314 JK1 mol1)
Q.43 The freezing point of a solution containing 0.2 g of acetic acid in 20.0g of benzene is lowered by 0.45°C.
Calculate the degree of association of acetic acid in benzene. (Kf for benzene = 5.12 K mol1 kg)
Q.44 0.85 % (w/v) aqueous solution of NaNO3 is apparently 90% dissociated at 27°C. Calculate its osmotic
pressure. (R= 0.082 l atm K1 mol1 )
Q.45 A 1.2% solution (w/v) of NaCl is isotonic with 7.2% solution (w/v) of glucose. Calculate degree of
ionization and Van’t Hoff factor of NaCl.

PROFICIENCY TEST
Q.1 Fill in the blanks with appropriate items :
1. Lowering of vapour pressure is ______ to the mole fraction of the solute.
2. The ratio of the value of any colligative property for NaCl solution to that of equimolal solution of sugar
is nearly______.
3. Semipermeable membrane allows the passage of ________through it.
4. A binary solution which has same composition in liquid as well as vapour phase is called______.
5. The molal elevation constant of solvent is also called _____.
6. The 0.1 M aqueous solution of acetic acid has boiling point _______ than that of 0.1 M aqueous
solution of KCl.
7. For ideal solutions, the plot of total vapour pressure v/s composition is ______.
8. A solution of CHCl3 and acetone shows________deviation.
9. Gases which react with water are generally _________ soluble in it.
10. Assuming complete dissociation, Van’t Hoff’s factor for Na2SO4 is equal to ________.
11. The osmotic pressure of a solution _______ with increase in temperature.

12. Water will boil at 101.5°C at pressure of _______76 cm of Hg.
13. Vant’s Hoff’s factor ‘i’ for dimerisation of CH3COOH in benzene is_________.
nB
14. = RT is known as_________.
V
15. The molal elevation constant is the ratio of the elevation in boiling point to _________.
Q.2 True or False Statements :
1. Relative lowering of vapour pressure is a colligative property.
2. Lowering of vapour pressure of a solution is equal to the mole fraction of the non-volatile solute present in it.
3. The components of an azeotropic solution can be separated by simple distillation.
4. Vapour pressure of a liquid depends on the size of the vessel.
5. Addition of non-volatile solute to water always lowers it vapour pressure.
6. Reverse osmosis is generally used to make saline water fit for domestic use.
7. A 6% (w/v) solution of NaCl should be isotonic with 6% (w/v)solution of sucrose.
8. A real solution obeys Raoult’s law.
9. Boiling point is a characteristic temperature at which vapour pressure of the liquid becomes higher than
the atmospheric pressure.
10. Molal depression constant is independent of the nature of solute as well as that of solvent.
11. The real solutions can exhibit ideal behaviour at high concentrations.
12. The osmotic pressure decreases on addition of solvent to the solution.
13. For urea the value of Vant’s Hoff’s factor ‘i’ is equal to 1.
14. The unit of kb is kg K–1 mol–1.
15. 0.1 M solution of urea would be hypotonic with 0.1 M solution of NaCl.
EXERCISE II
Q.1 An aqueous solution containing 288 gm of a non-volatile compound having the stoichiometric composition
CxH2xOx in 90 gm water boils at 101.24°C at 1.00 atmospheric pressure. What is the molecular formula?
Kb(H2O) = 0.512 K mol–1 kg
Tb(H2O) = 100°C
Q.2 The addition of 3 gm of substance to 100 gm CCl4(M = 154 gm mol–1) raises the boiling point of CCl4
by 0.60°C of Kb (CCl4) is 5.03 kg mol–1 K. Calculate
(a) the freezing point depression
(b) the relative lowering of vapour pressure
(c) the osmotic pressure at 298 K
(d) the molar mass of the substance
Given Kf(CCl4) = 31.8 kg mol–1K and  (density) of solution = 1.64 gm/cm3
Q.3 Vapour pressure of C6H6 and C7H8 mixture at 500C is given by P (mm Hg) = 180 XB + 90, where XB
is the mole fraction of C6H6. A solution is prepared by mixing 936g benzene and 736g toluene and if the
vapours over this solution are removed and condensed into liquid and again brought to the temperature
of 500C, what would be mole fraction of C6H6 in the vapour state?
Q.4 At 100oC, benzene & toluene have vapour pressure of 1375 & 558 Torr respectively. Assuming these
two form an ideal binary solution, calculate the composition of the solution that boils at 1 atm & 100oC.
What is the composition of vapour issuing at these conditions?
Q.5 Calculate the boiling point of a solution containing 0.61g of benzoic acid in 50g of carbon disulphide
assuming 84% dimerization of the acid. The boiling point and Kb of CS2 are 46.2°C and
2.3 K kg mol–1, respectively.
Q.6 The molar volume of liquid benzene (density = 0.877 g ml1) increases by a factor of 2750 as it vaporizes
at 20°C and that of liquid toluene (density = 0.867gml1) increases by a factor of 7720 at 20°C.
Solution of benzene & toluene has a vapour pressure of 46.0 torr. Find the mole fraction of benzene in
the vapour above the solution.
Q.7 Dry air was drawn thorugh bulbs containing a solution of 40 grams of urea in 300 grams of water, then
through bulbs containing pure water at the same temperature and finally through a tube in which pumice
moistened with strong H2SO4 was kept. The water bulbs lost 0.0870 grams and the sulphuric acid tube
gained 2.036 grams. Calculate the molecular weight of urea.
Q.8 The vapour pressure of two pure liquids, A and B that form an ideal solution are 300 and 800 torr
respectively, at temperature T. A mixture of the vapour of A and B for which the mole fraction of A is
0.25 is slowly compressed at temperature T. Calculate
(a) the composition of the first drop of the condensate,
(b) the total pressure when this drop is formed,
(c) the composition of the solution whose normal boiling point is T,
(d) the pressure when only the last bubble of vapour remains, and
(e) the composition of the last bubble.

Q.9 The degree of dissociation of Ca(NO3)2 in a dilute aqueous solution containing 7 gm of the salt per
100 gm of water at 100°C is 70%. If the vapour pressure of water at 100°C is 760 mm. Calculate the
vapour pressure of the solution.
Q.10 A 10% (w/w) solution of cane sugar has undergone partial inversion according to the reaction:
Sucrose + Water  Glucose + Fructose. If the boiling point of solution is 100.27°C.
(a) What is the average mass of the dissolved materials?
(b) What fraction of the sugar has inverted? Kb(H2O) = 0.512 K mol–1 kg
Q.11 1.5 g of a monobasic acid when dissolved in 150g of water lowers the freezing point by 0.165°C. 0.5 g
of the same acid when titrated, after dissolution in water, requires 37.5 ml of N/10 alkali. Calculate the
degree of dissociation of the acid (Kf for water = 1.86°C mol–1).
Q.12 Sea water is found to contain 5.85% NaCl and 9.50% MgCl2 by weight of solution. Calculate its normal
boiling point assuming 80% ionisation for NaCl and 50% ionisation of MgCl2 [Kb(H2O) = 0.51kgmol1K].
Q.13 The latent heat of fusion of ice is 80 calories per gram at 00C. What is the freezing point of a solution of
KCl in water containing 7.45 grams of solute in 500 grams of water, assuming that the salt is dissociated
to the extent of 95%?
Q.14 A complex is represented as CoCl3 · x NH3. It's 0.1 molal solution in aq. solution shows Tf = 0.558°C.
Kf for H2O is 1.86 K mol–1 kg . Assuming 100% ionisation of complex and coordination no. of Co is six,
calculate formula of complex.
Q.15 At 25OC, 1 mol of A having a vapor pressure of 100torr and 1 mol of B having a vapor pressure of
300 torr were mixed. The vapor at equilibrium is removed, condensed and the condensate is heated
back to 25OC. The vapors now formed are again removed, recondensed and analyzed. What is the
mole fraction of A in this condensate?
Q.16 Phenol associates in benzene to a certain extent to form a dimer. A solution containing 20 × 10 –3 kg
phenol in 1 kg of benzene has its freezing point depressed by 0.69 K. Calculate the fraction of phenol
that has dimerised. Kf for benzene = 5.12 kg mol–1K.
Q.17 30 ml of CH3OH (d = 0.7980 gm cm–3) and 70 ml of H2O (d=0.9984 gm cm–3) are mixed at 25°C to
form a solution of density 0.9575 gm cm–3. Calculate the freezing point of the solution. Kf (H2O) is
1.86 kg mol–1 K. Also calculate its molarity.
Q.18 When the mixture of two immicible liquids (water and nitrobenzene) boils at 372 K and the vapour
pressure at this temperature are 97.7 kPa (H2O) and 3.6 kPa (C6H5NO2). Calculate the weight % of
nitrobenzene in the vapour.
Q.19 A very dilute saturated solution of a sparingly soluble salt A3B4 has a vapour pressure of 20 mm of Hg
at temperature T, while pure water exerts a pressure of 20.0126 mm Hg at the same temperature.
Calculate the solubility product constant of A3B4 at the same temperature.
Q.20 If the apparent degree of ionization of KCl (KCl =74.5 gm mol–1) in water at 290 K is 0.86. Calculate
the mass of KCl which must be made up to 1 dm3 of aqueous solution to the same osmotic pressure as
the 4.0% solution of glucose at that temperature.

Q.21 An ideal solution was prepared by dissolving some amount of cane sugar (nonvolatile) in 0.9 moles of
water. The solution was then cooled just below its freezing temperature (271 K), where some ice get
separated out. The remaining aqueous solution registered a vapour pressure of 700 torr at 373 K.
Calculate the mass of ice separated out, if the molar heat of fusion of water is 6 kJ.
Q.22 The specific conductivity of a 0.5 M aq. solution of monobasic acid HA at 27°C is 0.006 Scm –1. It's
molar conductivity at infinite dilution is 200 S cm2 mol–1.
Calculate osmotic pressure (in atm) of 0.5 M HA (aq) solution at 27°C.
atm L
Given R = 0.08 .
mol K
Q.23 The freezing point of 0.02 mol fraction solution of acetic acid (A) in benzene (B) is 277.4K. Acetic acid
exists partly as a dimer 2A = A2. Calculate equilibrium constant for the dimerisation. Freezing point of
benzene is 278.4 K and its heat of fusion Hf is 10.042 kJ mol1.
Q.24 Tritium, T (an isotope of H) combines with fluorine to form weak acid TF, which ionizes to give T+.
Tritium is radioactive and is a –emitter. A freshly prepared aqueous solution of TF has pT (equivalent of
pH) of 1.5 and freezes at –0.3720C. If 600ml of freshly prepared solution were allowed to stand for
24.8 years. Calculate (i) ionization constant of TF. (ii) Number of –particles emitted.
(Given Kf for water = 1.86 kg mol K–1, t1/2 for tritium = 12.4 years)

EXERCISE III
Single correct
Q.1 For an ideal binary liquid solution with PA > PB , which relation between XA (mole fraction of A in liquid
phase) and YA(mole fraction of A in vapour phase) is correct?
YA X A YA X A
(A) YA < YB (B) XA > XB (C) Y  X (D) Y  X
B B B B
Q.2 Mole fraction of A vapours above the solution in mixture of A and B (XA = 0.4) will be
[Given : PA = 100 mm Hg and PB = 200 mm Hg]
(A) 0.4 (B) 0.8 (C) 0.25 (D) none of these
Q.3 The exact mathematical expression of Raoult’s law is
P 0  Ps n P 0  Ps N P 0  Ps n P 0  Ps
(A)  (B)  (C)  (D) =n×N
P0 N P0 n Ps N P0
Q.4 A mixture contains 1 mole of volatile liquid A ( PA =100 mm Hg) and 3 moles of volatille liquid
B ( PB = 80 mm Hg). If solution behaves ideally, the total vapour pressure of the distillate is
(A) 85 mm Hg (B) 85.88 mm Hg (C) 90 mm Hg (D) 92 mm Hg
Q.5 Which of the following aqueous solution will show maximum vapour pressure at 300 K?
(A) 1 M NaCl (B) 1 M CaCl2 (C) 1 M AlCl3 (D) 1 M C12H22O11
Q.6 The Van’t Hoff factor for a dilute aqueous solution of glucose is
(A) zero (B) 1.0 (C) 1.5 (D) 2.0
Q.7 The correct relationship between the boiling points of very dilute solution oif AlCl 3 (T1K) and
CaCl2 (T2K) having the same molar concentration is
(A) T1 = T2 (B) T1 > T2 (C) T2 > T1 (D) T2  T1
Q.8 A 0.001 molal solution of a complex [MA8] in water has the freezing point of –0.0054°C. Assuming
100% ionization of the complex salt and Kf for H2O = 1.86 km–1, write the correct representation for
the complex
(A) [MA8] (B) [MA7]A (C) [MA6]A2 (D) [MA5]A3
Q.9 The vapour pressure of a solution of a non-volatile electrolyte B in a solvent A is 95% of the vapour
pressure of the solvent at the same temperature. If the molecular weight of the solvent is 0.3 times the
molecular weight of solute, the weight ratio of the solvent and solute are
(A) 0.15 (B) 5.7 (C) 0.2 (D) 4.0
Q.10 At a given temperature, total vapour pressure in Torr of a mixture of volatile components A and B is
given by
PTotal = 120 – 75 XB
hence, vapour pressure of pure A and B respectively (in Torr) are
(A) 120, 75 (B) 120, 195 (C) 120, 45 (D) 75, 45

Q.11 Assuming each salt to be 90 % dissociated, which of the following will have highest boiling point?
(A) Decimolar Al2(SO4)3
(B) Decimolar BaCl2
(C) Decimolar Na2SO4
(D) A solution obtained by mixing equal volumes of (B) and (C)
Q.12 The vapour pressure of a solvent decreased by 10 mm of Hg when a non-volatile solute was added to
the solvent. The mole fraction of solute in solution is 0.2, what would be mole fraction of the solvent if
decrease in vapour pressure is 20 mm of Hg
(A) 0.2 (B) 0.4 (C) 0.6 (D) 0.8
Q.13 Elevation of boiling point of 1 molar aqueous glucose solution (density = 1.2 g/ml) is
(A) Kb (B) 1.20 Kb (C) 1.02 Kb (D) 0.98 Kb
Q.14 What will be the molecular weight of CaCl2 determined in its aq. solution experimentally from depression
of freezing point?
(A) 111 (B) < 111 (C) > 111 (D) data insufficient
Q.15 1.0 molal aqueous solution of an electrolyte A2B3 is 60% ionised. The boiling point of the solution at 1
1
atm is ( K b( H 2O)  0.52 K kg mol )
(A) 274.76 K (B) 377 K (C) 376.4 K (D) 374.76 K
Q.16 Which of the following plots represents an ideal binary mixture?

(A) Plot of Ptotal v/s 1/XB is linear (XB = mole fraction of 'B' in liquid phase).
(B) Plot of Ptotal v/s YA is linear (YB = mole fraction of 'A' in vapour phase)
1
(C) Plot of P v/s YA is linear
total
1
(D) Plot of P v/s YB is non linear
total
Q.17 Pressure over ideal binary liquid mixture containing 10 moles each of liquid A and B is gradually decreased
isothermally. If PAo =200 mm Hg and PBo =100 mm Hg, find the pressure at which half of the liquid is
converted into vapour.
(A) 150 mm Hg (B) 166.5 mm Hg (C) 133 mm Hg (D) 141.4 mm Hg
Q.18 Two liquids A & B form an ideal solution. What is the vapour pressure of solution containing 2 moles of
A and 3 moles of B at 300 K? [Given : At 300 K, Vapour pr. of pure liquid A ( PAo ) = 100 torr,,
Vapour pr. of pure liquid B ( PBo ) = 300 torr ]
(A) 200 torr (B) 140 torr (C) 180 torr (D) None of these

Q.19 Which of the following represents correctly the changes in thermodynamic properties during the formation
of 1 mol of an ideal binary solution.
(A) (B)
(C) (D)
Q.20 FeCl3 on reaction with K4[Fe(CN)6] in aqueous solution gives blue

colour. These are separated by a semipermeable membrane AB as
shown. Due to osmosis there is
(A) blue colour formation in side X.
(B) blue colour formation in side Y.
(C) blue colour formation in both of the sides X and Y.
(D) no blue colour formation.
Q.21 A liquid mixture having composition corresponding to point z in the figure

shown is subjected to distillation at constant pressure. Which of the
following statement is correct about the process
(A) The composition of distillate differs from the mixture
(B) The boiling point goes on changing
(C) The mixture has highest vapour pressure than for any other
composition.
(D) Composition of an azeotrope alters on changing the external pressure.
Q.22 The vapour pressure of a saturated solution of sparingly soluble salt (XCl3) was 17.20 mm Hg at
27°C. If the vapour pressure of pure H2O is 17.25 mm Hg at 300 K, what is the solubility of
sparingly soluble salt XCl3 in mole/Litre.
(A) 4.04 × 10–2 (B) 8.08 ×10–2
(C) 2.02 × 10–2 (D) 4.04 × 10–3
Q.23 At 300 K, the vapour pressure of an ideal solution containing 3 mole of A and 2 mole of B is 600 torr. At
the same temperature, if 1.5 mole of A & 0.5 mole of C (non-volatile) are added to this solution the
vapour pressure of solution increases by 30 torr. What is the value of PBo ?
(A) 940 (B) 405
(C) 90 (D) none of these

Q.24 The following graph represents variation of boiling point with composition of liquid and vapours of binary
liquid mixture. The graph is plotted at constant pressure.
Which of the following statement(s) is incorrect. Here X & Y stands for mole fraction in liquid and
vapour phase respectively
(A) Xbenzene = 0.5 and Ytoluene = 0.2 (B) Xtoluene = 0.3 and Ybenzene = 0.6
(C) Xbenzene = 0.3 and Ytoluene = 0.4 (D) if Xbenzene = 0.7 than Ytoluene < 0.3
Q.25 The freezing point depression of a 0.1 M aq. solution of weak acid (HX) is –0.20°C.
What is the value of equilibrium constant for the reaction?
HX (aq)  H +(aq) + X¯ (aq)
[Given : Kf for water = 1.8 kg mol–1 K. & Molality = Molarity ]
(A) 1.46×10–4 (B) 1.35 × 10–3 (C) 1.21 × 10–2 (D) 1.35 × 10–4
Q.26 The van’t Hoff factor for 0.1 M Ba(NO3)2 solution is 2.74. The degree of dissociation is
(A) 91.3% (B) 87% (C) 100% (D) 74%
Q.27 The vapour pressure of an aqueous solution is found to be 750 torr at certain temperature 'T'. If 'T' is the
temperature at which pure water boils under atmospheric pressure and same solution show elevation in
boiling point Tb = 1.04 K, find the atmospheric pressure (Kb = 0.52 K kg mol–1 )
(A) 777 (B) 779 (C) 782 (D) 746
More than one may be correct
Q.28 Acetone and carbon disulphide form binary liquid solution showing positive deviation from Raoult law.
The normal boiling point (Tb) of pure acetone is less than that of pure CS2. Pick out the incorrect
statements among the following.
(A) Boiling temperature of mixture is always less than boiling temperature of acetone.
(B) Boiling temperature of Azeotropic mixture is always less than boiling temperature of pure CS2.
(C) When a small amount of CS2 (less volatile component) is added to excess of acetone boiling point
of resulting mixture increases.
(D) A mixture of CS2 and CH3COCH3 can be completely separated by simple fractional distillation.
Assertion & Reasoning type questions
Q.29 Statement-1 : The freezing of water is an endothermic process.
Statement-2 : Heat must be removed from the water to make it freeze.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false. (D) Statement-1 is false, statement-2 is true.
Q.30 Statement-1 : Additon of ethylene glycol (non-volatile) to water lowers the freezing point of
water hence used as antifreeze.
Statement-2 : Addition of any substance to water lowers its freezings point of water.
(C) Statement-1 is true, statement-2 is false. (D) Statement-1 is false, statement-2 is true.

EXERCISE IV
Q.1 The van’t Hoff factor for 0.1 M Ba(NO3)2 solution is 2.74. The degree of dissociation is
(A) 91.3% (B) 87% (C) 100% (D) 74% [JEE 1999]
Q.2 In the depression of freezing point experiment, it is found that

(I) The vapour pressure of the solution is less than that of pure solvent.
(II) The vapour pressure of the solution is more than that of pure solvent.
(III) Only solute molecules solidify at the freezing point.
(IV) Only solvent molecules solidify at the freezing point.
(A) I, II (B) II, III (C) I, IV (D) I, II, III [JEE 1999]
Q.3 To 500 cm3 of water, 3×10–3 kg of acetic acid is added. If 23% of acetic acid is dissociated, what will
be the depression in freezing point ? Kf and density of water are 1.86 K kg–1 mol–1 and 0.997 g cm–3
respectively. [JEE 2000]
Q.4 The vapour pressure of two miscible liquids (A) and (B) are 300 and 500 mm of Hg respectively. In a
flask 10 mole of (A) is mixed with 12 mole of (B). However, as soon as (B) is added, (A) starts
polymerising into a completely insoluble solid. The polymerisation follows first-order kinetics. After 100
minute, 0.525 mole of a solute is dissolved which arrests the polymerisation completely. The final vapour
pressure of the solution is 400 mm of Hg. Estimate the rate constant of the polymerisation reaction.
Assume negligible volume change on mixing and polymerisation and ideal behaviour for the final solution.
[JEE 2001]
Q.5 During depression of freezing point in a solution, the following are in equilibrium
(A) liquid solvent-solid solvent (B) liquid solvent-solid solute
(C) liquid solute-solid solute (D) liquid solute-solid solvent [JEE 2003]
Q.6 Match the boiling point with Kb for x, y and z, if molecular weight of x, y and z are same.[JEE 2003]
b.pt. Kb
x 100 0.68
y 27 0.53
z 253 0.98
Q.7 A 0.004 M solution of Na2SO4 is isotonic with a 0.010 M solution of glucose at same temperature. The
apparent degree of dissociation of Na2SO4 is
(A) 25% (B) 50% (C) 75% (D) 85% [JEE 2004]
Q.8 1.22 g of benzoic acid is dissolved in (i) 100 g acetone (Kb for acetone = 1.7) and (ii)100 g benzene
(Kb for benzene = 2.6). The elevation in boiling points Tb is 0.17°C and 0.13°C respectively.
(a) What are the molecular weights of benzoic acid in both the solutions?
(b) What do you deduce out of it in terms of structure of benzoic acid? [JEE 2004]
Q.9 The elevation in boiling point, when 13.44 g of freshly prepared CuCl2 are added to one kilogram of
water, is [Some useful data, Kb (H2O) = 0.52 kg K mol–1, mol. wt. of CuCl2 = 134.4 gm]
(A) 0.05 (B) 0.1 (C) 0.16 (D) 0.21 [JEE 2005]

Q.10 72.5 g of phenol is dissolved in 1 kg of a solvent (kf = 14) which leads to dimerization of phenol and
freezing point is lowered by 7 kelvin. What percent of total phenol is present in dimeric form?
[JEE 2006]
Q.11 When 20 g of naphtholic acid (C11H8O2) is dissolved in 50 g of benzene (Kf = 1.72 K kg mol–1), a
freezing point depression of 2 K is observed. The van’t Hoff factor (i) is
(A) 0.5 (B) 1 (C) 2 (D) 3 [JEE 2007]
Paragraph for Question No. Q.12 to Q.14

Properties such as boiling point, freezing point and vapour pressure of a pure solvent change when solute
molecules are added to get homogeneous solution. These are called colligative properties. Applications
of colligative properties are very useful in day-to-day life. One of its examples is the use of ethylene
glycol and water mixture as anti-freezing liquid in the radiator of automobiles.
A solution M is prepared by mixing ethanol and water. The mole fraction of ethanol in the mixture is 0.9.
Given : Freezing point depression constant of water   = 1.86 K kg mol–1
Freezing point depression constant of ethanol   = 2.0 K kg mol–1
Boiling point elevation constant of water   = 0.52 K kg mol–1
Boiling point elevation constant of ethanol   = 1.2 K kg mol

–1
Standard freezing point of water = 273 K

Standard freezing point of ethanol = 155.7 K
Standard boiling point of water = 373 K
Standard boiling point of ethanol = 351.5 K
Vapour pressure of pure water = 32.8 mm Hg
Vapour pressure of pure ethanol = 40 mm Hg
Molecular weight of water = 18 g mol–1
Molecular weight of ethanol = 46 g mol–1
In answering the following questions, consider the solutions to be ideal dilute solutions and solutes to be
non-volatile and non-dissociative.
Q.12 The freezing point of the solution M is [JEE 2008]
(A) 268.7 K (B) 268.5 K (C) 234.2 K (D) 150.9 K
Q.13 The vapour pressure of the solution M is [JEE 2008]

(A) 39.3 mm Hg (B) 36.0 mm Hg (C) 29.5 mm Hg (D) 28.8 mm Hg
Q.14 Water is added to the solution M such that the mole fraction of water in the solution becomes 0.9. The
boiling point of this solution is [JEE 2008]
(A) 380.4 K (B) 376.2 K (C) 375.5 K (D) 354.7 K
Q.15 The Henry’s law constant for the solubility of N 2 gas in water at 298 K is 1.0 × 105 atm. The mole
fraction of N2 in air is 0.8. The number of moles of N2 from air dissolved in 10 moles of water at 298 K
and 5 atm pressure is [JEE 2009]
(A) 4.0 × 10–4 (B) 4.0 × 10–5 (C) 5.0 × 10–4 (D) 4.0 × 10–5

COMPREHENSIONS
Comprehension # 1
PA = x A PA & PB = xBPB
PT = x A PA + xBPB (Note : PA > PB ; A is more volatile than B)
Vapour pressure of mixtures of Benzene (C6H6 ) & toluene (C7H8) at 50ºC are given by PM = 179 XB + 92 where
XB is mole fraction of C6H6.
1. What is vapour pressure of pure liquids ?

(A) PB = 92 mm, PT = 179 mm (B) PB = 271 mm, PT = 92 mm
(C) PB = 180 mm, PT = 91 mm (D) none of these
2. Vapour pressure of liquid mixture obtained by mixing 936 g C6H6 & 736 g tolene is :
(A) 300 mm Hg (B) 250 mm Hg (C) 199.4 mm Hg (D) 180.6 mm Hg
Comprehension # 2
Answer the questions (given below) which are based on the
following diagram.
Consider some facts about the above phase diagram :
Vapour pressure diagram for real solutions of two liquids A and B
that exhibit a positive deviation from Raoult’s law. The vapour
pressure of both A and B are greater than predicted by Raoult’s
law. The dashed lines represented the plots for ideal solutions.
3. A : This is observed when A...B attractions are greater than average of A...A and B...B attraction:
B : Hmix = +ve, Vmix = +ve
C : Boiling point is smaller than expected such that vaporisation is increased
D : Mixture can form azeotropic mixture
Select correct facts
(A) A, B, C (B) B, C, D (C) A, C, D (D) A, B, C, D
4. Total vapour pressure of mixture of 1 mol of volatile component A (p°A = 100 mm Hg) and 3 mol of volatile
component B (p°B = 60 mm Hg) is 75 mm. For such case :
(A) There is positive deviation from Raoult’s law
(B) Boiling point has been lowered
(C) Force of attraction between A and B is smaller than that between A and A or between B and B.
(D) All the above statements are correct.

Comprehension # 3
Addition of non–volatile solute to a solvent always increases the colligative properties such as osmotic
pressure, P, Tb and Tf . All these colligative properties are directly proportional to molality if solutions are
dilute. The increases in colligative properties on addition of non–volatile solute is due to increase in number
of solute particles.
5. For different aqueous solutions of 0.1 M NaCI, 0.1 M urea , 0.1 M Na2SO4 and 0.1 M Na3PO4 solution at 270
C, the correct statements are : (Consider the solutions to be dilute)
1. The order of osmotic pressure is, NaCl > Na2SO4 > Na3PO4 > urea
Tb
2.  = K × ST for urea solution
b
3. Addition of salt on ice increases its melting point
4. Addition of salt on ice brings in melting of ice earlier
(A) 2 , 3 ,4 (B) 2, 4 (C) 1 , 2 , 3 (D) 3 , 4
6. 1 g mixture of glucose and urea present in 250 mL aqueous solution shows the osmotic pressure of 0.74 atm
at 27ºC. Assuming solution to be dilute , which are correct ?
1. Percentage of urea in mixture is 17.6.
2. Relative lowering in vapour pressure of this solution is 5.41 × 10–4.
3. The solution will boil at 100.015ºC , if Kb of water is 0.5 K molality–1.
4. If glucose is replaced by same amount of sucrose, the solution will show higher osmotic pressure at 27ºC.
5. If glucose is replaced by same amount of NaCl, the solution will show lower osmotic pressure at 27ºC.
(A) 1 , 2 , 3 (B) 1 , 2 , 3 , 5 (C) 2 , 4 , 5 (D) 1 , 4 , 5
MATCH THE COLUMNS

1. Column – I Column – II
If at a particular temperature, the density of 18 M H2SO4 is 1.8 g cm –3. Then :
(A) Molality (p) 0.1
(B) % concentration by wt. of solute (q) 0.9
(C) mole fraction of H2SO4 (r) 500
(D) mole fraction of H2O (s) 98

(A) Acetone + CHCl3 (p) Smix. > 0
(B) Ethanol + Water (q) Vmix. > 0
(C) C2H5Br + C2H5I (r) Hmix. < 0
(D) Acetone + Benzene (s) Maximum boiling azeotropes
(t) Minimum boiling azeotropes

Assuming all the solutes are non volatile and all solutions are ideal and neglect the hydrolysis of cation and
anion.
(A) 10 ml 0.1 M NaOH aqueous solution is added (p) Osmotic pressure of solution increases
to 10 ml 0.1 M HCl aqueous solution
(B) 10 ml 0.1 M NaOH aqueous solution is added (q) Vapour pressure of solution increases
to 10 ml 0.1 M CH3COOH aqueous solution
(C) 10 ml 0.1 M HCl aqueous solution is added (r) Boiling point of solution increases
to 10 ml 0.1 M NH3 aqueous solution
(D) 10 ml 0.1 M HCl aqueous solution is added (s) Freezing point of solution increases
to 10 ml 0.1 M KOH aqueous solution

ANSWER KEY
EXERCISE I
Q.1 0.24 Q.2 0.25 Q.3 24.5 torr

Q.4 57.24 g/mol Q.5 66.13 mm Hg Q.6 0.237
Q.7 0.682, 0.318; 0.829, 0.171 Q.8 92 mol% toluene; 96.8 mol % toluene
Q.9 PA = 213.33 torr, PB = 960.0 torr Q.10 0.04
Q.11 111.1g, 18.52 molal Q.12 0.741 m, 0.013 Q.13 0.162 m
Q.14 65.25 Q.15 17.38 Q.16 0.964
Q.17 106 g/mol Q.18 64.0 g/mol Q.19 100.079°C
Q.20 – 0.62°C Q.21 5.08°C/m Q.22 50.8 g/mol
Q.23 2050 g/mol Q.24 x = 25.6, y = 42.6
Q.25 Kb= 0.512 kg mol K–1, Tb = 373.20 K Q.26 38.71 g
Q.27 156.06 Q.28 C 6H 6 Q.29 Tf = –2.28oC
Q.30 P = 0.2217 atm should be applied Q.31 (Vfinal = 5.Voriginal)
Q.32 54.2 g Q.33 0.81 atm Q.34 13.8 atm
Q.35 5.4 × 105 g/mol Q.36 2.4 × 105 g/mol Q.37 59.99
Q.38 MA/MB = 0.33 Q.39 i = 2.5 Q.40 3 ions
Q.41  = 99.2% Q.42 7.482 ×105 Nm–2 Q.43 94.5 %
Q.44 4.64 atm Q.45 0.95; 1.95
PROFICIENCY TEST
Q.1 1. proportional 2. 2 : 1 3. solvent molecules
4. azeotropic mixture 5. Ebullioscopic constant 6. lesser
7. straight line with slope  0 8. negative 9. more
10. 3 11. increases 12. greater than
13. less than 1 14. Van’t Hoff’s solution equation 15. molality

Q.2 1. T 2. F 3. F 4. F 5. T 6. T
7. F 8. F 9. F 10. F 11. F 12. T
13. T 14. F 15. T
EXERCISE II
Q.1 C44H88O44 Q.2 (a) 3.79°C, (b) 0.018, (c) 4.65 atm, (d) 251.5
Q.3 0.93 Q.4 xb = 0.2472, Yb = 0.4473 Q.5 46.33°C
Q.6 0.73 Q.7 M = 53.8
Q.8 (a)0.47, (b) 565 torr, (c) xA=0.08, xB= 0.92, (d) 675 torr, (e) x'A= 0.11, x'B= 0.89
Q.9 746.24 mm/Hg Q.10 (a) 210.65, (b) 62.35% Q.11 18.34%
Q.12 Tb = 102.3oC Q.13 Tf = – 0.73°C Q.14 [Co(NH3)5Cl]Cl2
Q.15 xa" = 0.1 Q.16 a = 0.7333 Q.17 –19.91°C, 7.63 M
Q.18 20.11 % Q.19 5.4 × 10–13 Q.20 8.9 gm
Q.21 12.54 Q.22 12.72 Q.23 K = 3.36
Q.24 (i) Ka = 7.3 × 10–3 (ii) 4.55 × 1022
EXERCISE III
Q.1 C Q.2 C Q.3 C Q.4 B Q.5 D Q.6 B Q.7 B

Q.8 C Q.9 B Q.10 C Q.11 A Q.12 C Q.13 D Q.14 B
Q.15 D Q.16 C Q.17 D Q.18 D Q.19 C Q.20 D Q.21 D
Q.22 A Q.23 C Q.24 B Q.25 B Q.26 B Q.27 A Q.28 A,C,D
Q.29 D Q.30 C
EXERCISE IV
Q.1 B Q.2 C Q.3 0.229 Q.4 1.0 × 10–4
Q.5 A Q.6 Kb(x) = 0.68, Kb(y) = 0.53, Kb(z) = 0.98 Q.7 C
Q.8 (a)122, (b) It means that benzoic acid remains as it is in acetone while it dimerises in benzene
O H O
as C C
O H O
Q.9 C Q.10 35% phenol is present in dimeric form Q.11 A

Q.12 D Q.13 B Q.14 B Q.15 A

COMPREHENSIONS
Q.1 (B) Q.2 (C) Q.3 (B) Q.4 (D) Q.5 (B)
Q.6 (A)
MATCH THE COLUMN

Q.1 (A – r) ; (B – s) ; (C – q) ; (D – p) Q.2 (A – p, s, r); (B – p, q, t); (C – p); (D – p, q, t)
Q.3 (A – q, s) ; (B – q, s) ; (C – q, s) ; (D) – q, s)

Electrochemistry [300]
EXERCISE I
GALVANIC CELL :
Representation of Cell diagrams, complete and half cell reactions :
Q.1 Write cell reaction of the following cells :
(a) Ag | Ag+ (aq) | | Cu2+ (aq) | Cu
(b) Pt | Fe2+ , Fe3+ | | MnO 4 , Mn2+, H+ | Pt
(c) Pt | Cl2 | Cl– (aq) | | Ag+ (aq) | Ag
(d) Pt | H2 | H+ (aq) | | Cd2+ (aq) | Cd
Q.2 Write cell representation for following cells.

(a) Cd2+ (aq) + Zn (s)  Zn2+ (aq) + Cd (s)
(b) 2Ag+ (aq) + H2 (g)  2H+ (aq) + 2Ag (s)
(c) Cr2 O 72 (aq.) + 14H+ (aq) + 6Fe2+ (aq)  6Fe3+ (aq) + 2Cr3+ (aq) + 7H2O (l)
Electrode potential and standard electrode potential :

Q.3 For the cell reaction 2Ce4+ + Co  2Ce3+ + Co2+
E ocell is 1.89 V. If E o is – 0.28 V, what is the value of E o ?
Co 2  | Co Ce 4  | Ce 3
Q.4 Determine the standard reduction potential for the half reaction :
Cl2 + 2e–  2Cl–
Given Pt2+ + 2Cl–  Pt + Cl2, E oCell = – 0.15 V
Pt2+ + 2e–  Pt E° = 1.20 V
Q.5 Is 1.0 M H+ solution under H2SO4 at 1.0 atm capable of oxidising silver metal in the presence of 1.0 M
Ag+ ion?
o
Eo = 0.80 V, E H  |H = 0.0 V
Ag  |Ag 2 ( Pt )
Q.6 If for the half cell reactions Cu2+ + e–  Cu+ E° = 0.15 V

Cu + 2e  Cu
2+ – E° = 0.34 V
Calculate E° of the half cell reaction
Cu+ + e–  Cu
also predict whether Cu+ undergoes disproportionation or not.
o o
Q.7 If E Fe 2 | Fe = – 0.44 V, E oFe3 | Fe 2 = 0.77 V. Calculate E Fe3 | Fe .
Q.8 Calculate the EMF of a Daniel cell when the concentration of ZnSO4 and CuSO4 are 0.001 M and
0.1M respectively. The standard potential of the cell is 1.1V.
Q.9 For a cell Mg(s) | Mg2+(aq) || Ag+ (aq) | Ag, Calculate the equilibrium constant at 25°C. Also find the
maximum work per mole Ag that can be obtained by operating the cell.
E0 (Mg2+/Mg) = 2.37V, E0 (Ag+/Ag) = 0.8 V.
Q.10 The EMF of the cell M | Mn+ (0.02M) || H+ (1M) | H2(g) (1 atm), Pt at 25°C is 0.81V. Calculate the
valency of the metal if the standard oxidation of the metal is 0.76V.
Q.11 Equinormal Solutions of two weak acids, HA (pKa = 3) and HB (pKa = 5) are each placed in contact
with equal pressure of hydrogen electrode at 25°C. When a cell is constructed by interconnecting them
through a salt bridge, find the emf of the cell.
Q.12 Calculate E0 and E for the cell Sn | Sn2+ (1M) || Pb2+(103M) | Pb, E0 (Sn2+| Sn) = 0.14V,
E0 (Pb2+| Pb) = 0.13V. Is cell representation is correct?
Q.13 At what concentration of Cu2+ in a solution of CuSO4 will the electrode potential be zero at 25°C?
Given : E0 (Cu | Cu2+) = 0.34 V.
Q.14 A zinc electrode is placed in a 0.1M solution at 25°C. Assuming that the salt is 20% dissociated at this
dilutions calculate the electrode potential. E0 (Zn2+| Zn) = 0.76V.
Q.15 From the standard potentials shown in the following diagram, calculate the potentials E1 and E 2 .
CONCENTRATION CELLS :
Q.16 Calculate the EMF of the following cell
Zn | Zn2+ (0.01M) || Zn2+ (0.1 M) | Zn
at 298 K.
Q.17 Calculate the EMF of the cell,

Zn – Hg(c1M) | Zn2+ (aq)| Hg – Zn(c2M)
at 25°C, if the concentrations of the zinc amalgam are: c1 = 10g per 100g of mercury and
c2 = 1g per100 g of mercury.
Q.18 Calculate pH using the following cell :

Pt (H2) | H+ (x M) | | H+ (1 M) | Pt (H2) if Ecell = 0.2364 V.
1 atm 1 atm
EQUILIBRIUM CONSTANT :
Q.19 Calculate the equilibrium constant for the reaction
Fe2+ +Ce4+  Fe3+ + Ce3+ , [given : E 0 Ce 4  / Ce3 1.44V;E 0 Fe3 / Fe 2 0.68V ]
Q.20 Calculate the equilibrium constant for the reaction Fe + CuSO4  FeSO4 + Cu at 25°C.
Given E0 (Fe/Fe2+) = 0.44V, E0 (Cu/Cu2+) = 0.337V.
Q.21 The standard reduction potential at 25°C for the reduction of water
2H2O + 2e  H2 + 2OH is 0.8277 volt. Calculate the equilibrium constant for the reaction
2H2O  H3O+ + OH at 25°C.
Q.22 At 250C the value of K for the equilibrium Fe3+ + Ag  Fe2+ + Ag+ is 0.531mol/litre. The standard
electrode potential for Ag + + e –  Ag is 0.799V. What is the standard potential for
Fe3+ + e–  Fe2+ ?
Q.23 For the reaction, 4Al(s) + 3O2(g) + 6H2O + 4 OH–  4 [Al(OH)4–] ; Ecell = 2.73 V. If
G f (OH  ) = –157 kJ mol–1 and G f ( H 2 O ) = –237.2 kJ mol–1, determine G f [Al (OH)4–].
ELECTROLYTIC CELL :
Q.24 Calculate the no. of electrons lost or gained during electrolysis of
(a) 3.55 gm of Cl– ions (b) 1 gm Cu2+ ions (c) 2.7 gm of Al3+ ions
Q.25 How many faradays of electricity are involved in each of the case
(a) 0.25 mole Al3+ is converted to Al.
(b) 27.6 gm of SO3 is convered to SO 32
(c) The Cu2+ in 1100 ml of 0.5 M Cu2+ is converted to Cu.
Q.26 0.5 mole of electron is passed through two electrolytic cells in series. One contains silver ions, and the
other zinc ions. Assume that only cathode reaction in each cell is the reduction of the ion to the metal.
How many gm of each metals will be deposited.
Q.27 The electrosynthesis of MnO2 is carried out from a solution of MnSO4 in H2SO4 (aq). If a current of
25.5 ampere is used with a current efficiency of 85%, how long would it take to produce 1 kg of MnO2?
Q.28 If 0.224 litre of H2 gas is formed at the cathode, how much O2 gas is formed at the anode under identical
conditions?
Q.29 Assume 96500 C as one unit of electricity. If cost of electricity of producing x gm Al is Rs x, what is the
cost of electricity of producing x gm Mg?
Q.30 Chromium metal can be plated out from an acidic solution containing CrO3 according to following equation:
CrO3(aq) + 6H+ (aq) + 6e–  Cr(s) + 3H2O
Calculate :
(i) How many grams of chromium will be plated out by 24000 coulombs and
(ii) How long will it take to plate out 1.5 gm of chromium by using 12.5 ampere current
Q.31 Calculate the quantity of electricity that would be required to reduce 12.3 g of nitrobenzene to aniline, if
the current efficiency for the process is 50 percent. If the potential drop across the cell is 3.0 volts, how
much energy will be consumed?
Q.32 How long a current of 2A has to be passed through a solution of AgNO 3 to coat a metal surface of
80cm2 with 5m thick layer? Density of silver = 10.8g/cm3.
Q.33 A metal is known to form fluoride MF2. When 10A of electricity is passed through a molten salt for 330
sec., 1.95g of metal is deposited. Find the atomic weight of M. What will be the quantity of electricity
required to deposit the same mass of Cu from CuSO4?
Q.34 10g solution of CuSO4 is electrolyzed using 0.01F of electricity. Calculate:

(a)The weight of resulting solution (b)Equivalents of acid or alkali in the solution.
Q.35 Cadmium amalgam is prepared by electrolysis of a solution of CdCl2 using a mercury cathode. How
long should a current of 5A be passed in order to prepare 12% CdHg amalgam on a cathode of 2gm
Hg (Cd=112.4)
Q.36 After electrolysis of NaCl solution with inert electrodes for a certain period of time. 600 mL of the
solution was left. Which was found to be 1N in NaOH. During the same time, 31.75 g of Cu was
deposited in the copper voltameter in series with the electrolytic cell. Calculate the percentage yield of
NaOH obtained, if the yield of CuSO4 cell is 100 %.
Q.37 A solution of Ni(NO3)2 is electrolysed between platinum electrodes using a current of 5 ampere for
20 mintue. What mass of Ni is deposited at the cathode?
Q.38 A current of 3.7A is passed for 6hrs. between Ni electrodes in 0.5L of 2M solution of Ni(NO3)2.
What will be the molarity of solution at the end of electrolysis?
CONDUCTANCE
Conductivities and cell constant:
Q.39 The resistance of a conductivity cell filled with 0.01N solution of NaCl is 210 ohm at18oC.Calculate
the equivalent conductivity of the solution. The cell constant of the conductivity cell is 0.88 cm 1.
Q.40 The molar conductivity of 0.1 M CH3COOH solution is 4.6 S cm2 mole1 . What is the specific
conductivity and resistivity of the solution ?
Q.41 The conductivity of pure water in a conductivity cell with electrodes of cross sectional area 4 cm 2
and 2 cm apart is 8 × 107 S cm1.
(i) What is resistance of conductivity cell ?
(ii) What current would flow through the cell under an applied potential difference of 1 volt?
Q.42 For 0.01N KCl, the resistivity 709.22 mho cm. Calculate the conductivity and equivalent
conductance.
Q.43 A solution containing 2.08 g of anhydrous barium chloride is 400 CC of water has a specific
conductivity 0.0058 ohm–1cm–1. What are molar and equivalent conductivities of this solution.
Application of Kohlrausch's law:

Q.44 For the strong electroytes NaOH, NaCl and BaCl2 the molar ionic conductivities at infinite dilution
are 248.1×10–4, 126.5 ×10–4 and 280.0 ×10-4 mho cm2 mol–1 respectively. Calculate the molar
conductivity of Ba(OH)2 at infinite dilution.
Q.45 Equivalent conductance of 0.01 N Na2SO4 solution is 112.4 ohm–1 cm2 eq–1. The equivalent
conductance at infinite dilution is 129.9 ohm –1 cm2eq–1. What is the degree of dissociation in 0.01
N Na2SO4 solution?
Q.46 The value of m for HCl, NaCl and CH3CO2Na are 426.1, 126.5 and 91 S cm2 mol–1 respectively..
Calculate the value of m for acetic acid. If the equivalent conductivity of the given acetic acid is 48.15
at 25° C, calculate its degree of dissociation.
Q.47 Specific conductance of a saturated solution of AgBr is 8.486×10–7 ohm–1cm–1 at 250C. Specific
conductance of pure water at 25°C is 0.75 ×10–6 ohm–1 cm–2. m for KBr , AgNO3 and KNO3
are 137.4 , 133 , 131 ( S cm2 mol–1) respectively. Calculate the solubility of AgBr in gm/litre.
Q.48 Saturated solution of AgCl at 25°C has specific conductance of 1.12×10–6 ohm–1 cm–1. The
 Ag+ and Cl– are 54.3 and 65.5 ohm–1 cm2 / equi. respectively. Calculate the solubility product
of AgCl at 25°C.
Q.49 Hydrofluoric acid is weak acid. At 25°C, the molar conductivity of 0.002M HF is
176.2 ohm–1 cm2 mole–1. If its m = 405.2 ohm–1 cm2 mole–1, calculate its degree of dissociation
and equilibrium constant at the given concentration.
Q.50 At 25°C,  (H+) = 3.4982 ×10 –2 S m2 mol–1 and  (OH–) = 1.98 ×10–2 S m2mol–1.
Given: Sp. conductnace = 5.7 ×10–6 S m–1 for H2O, determine pH and Kw.
PROFICIENCY TEST
Q.1 True or False :
1. In highly alkaline medium, the anodic process during the electrolytic process is
4OH–  O2 + 2H2O + 4e–.
2. Compounds of active metals (Zn, Na, Mg) are reducible by H2 whereas those of noble metals (Cu, Ag,
Au) are not reducible.
EIt
3. The mass of a substance deposited on the cathode or anode during electrolysis is given by w = .
F
4. Faraday’s second law of electrolysis is related to the equivalent mass of the electrolyte.
5. Equivalent conductance at infinite dilution of salt AB is equal to the sum of equivalent conductances of
ions, A+ and B– at infinite dilution.
6. The standard reduction potential of Cl– | AgCl | Ag half-cell is related to that of Ag+ | Ag half-cell through
RT
the expression E    E    In KSP (AgCl).
Ag |Ag Cl |AgCl|Ag F
7. The cell potential is given by Ecell = ERP(cathode)– ERP(anode).
8. A half-cell reaction is A (x+n) + ne–  Ax+. It is possible to determine the value of n from the
measurements of cell potential.
9. In a galvanic cell, the half-cell with higher reduction potential acts as a reducing agent.
10. In an electrode concentration cell, the cell reaction Zn(c1)  Zn(c2) will be spontaneous if c1 > c2.
11. The absolute value of electrode potential cannot be determined.
12. All chemical reactions used in galvanic cells are redox reactions.
13. The amount of the product formed by the passage of 1 coulomb of electricity through electrolyte is called
electrochemical equivalent of the substance.
14. The redox reaction involved in galvanic cell is a non- spontaneous process.
15. In galvanic cell, the cathode is a – ve terminal of the cell.
Q.2 Fill in the blanks:
1. The specific conductance of a 0.1 N KCl solution at 23°C is 0.012 ohm–1 cm–1. The resistance of the
cell containing the solution at the same temperature was found to be 55 ohms. The cell constant is ____.
2. Dilute sulphuric acid on electrolysis liberates___________ at the anode.
3. The electrical conductivity of a solution of acetic acid will _______ if a solution of sodium hydroxide is
added.
4. A cation having a ________reduction potential is preferentially reduced at the cathode.
5. When an aqueous solution of sodium sulphate is electrolysed, the gases liberated at the anode &
cathode are ________ and __________, respectively.
6. A cell in which two electrodes of the same metal are dipped in solutions of metal ion of different
concentrations in called___________.
7. The half-cell involving the reaction,

Cr2 O 72 (aq.) +14H+(aq.) + 6e– 2Cr3+(aq.) + 7H2O
is represented as _____________.
8. During discharge of lead storage battery, the overall reaction is___________.
9. In the calomel half-cell, the reduction reaction is ___________.
10. Temperature coefficient and change in enthalpy are related by the expression__________.
11. In salt bridge, the electrolyte used should be _________.
12. In electrochemical cell, the electrical neutrality in two half cells is maintained by _________.
13. The E° value for H2  2H+ + 2e– is ____________.
14. E°cell of E°oxi.(anode) + __________.
15. Coulomb refers to _______ of electricity while ampere refers to ________ at which it flows.
16. The cathodic reactions always involve__________.
17. During electrolysis of aqueous solution of CuSO4 using Pt electrodes the product at anode is ______.
18. The quantity of electricity required for complete reduction of 0.5 mole MnO 4 to Mn2+ is ______C.
19. During electrolysis process ________energy is converted into _______.
20.  eq × normality = _________.
EXERCISE II
Q.1 The standard reduction potential values, E0(Bi3+|Bi) and E0(Cu2+|Cu) are 0.226V and 0.344V
respectively. A mixture of salts of bismuth and copper at unit concentration each is electrolysed at 25°C.
to what value can [Cu2+] be brought down before bismuth starts to deposit, in electrolysis.
Q.2 The cell Pt, H2(1 atm) | H+(pH=x) || Normal calomel Electrode has an EMF of 0.67V at 25°C. Calculate
the pH of the solution. The oxidation potential of the calomel electrode on hydrogen scale is 0.28 V.
Q.3 Voltage of the cell Pt, H2 (1 atm)|HOCN (1.3 × 103 M)||Ag+ (0.8 M)|Ag(s) is 0.982 V . Calculate
the Ka for HOCN . Neglect [H+] because of oxidation of H2(g) .
Ag+ + e  Ag(s) = 0.8 V.
Q.4 Calculate the potential of an indicator electrode versus the standard hydrogen electrode, which originally
contained 0.1M MnO4 and 0.8M H+ and which was treated with 90% of the Fe2+ necessary to reduce
all the MnO4 to Mn+2.
MnO4 + 8H+ + 5e  Mn2+ + 4H2O, E0 = 1.51V
Q.5 Calculate the emf of the cell
Pt, H2(1.0 atm) | CH3COOH (0.1M) || NH3(aq, 0.01M) | H2 (1.0 atm),
Pt Ka(CH3COOH) = 1.8 × 105, Kb (NH3) = 1.8 × 105.
Q.6 The Edison storage cell is represented as Fe(s) | FeO(s) | KOH(aq) | Ni 2O3 (s) | Ni(s) The halfcell
reaction are
Ni2O3(s) + H2O(i) + 2e  2NiO(s) + 2OH E0 = + 0.40V
FeO(s) + H2O(l) + 2e Fe(s) + 2OH E0 =  0.87V
(i) What is the cell reaction?
(ii) What is the cell e.m.f.? How does it depend on the concentration of KOH?
(iii) What is the maximum amount of electrical energy that can be obtained from one mole of Ni2O3?
Q.7 The standard reduction potential for Cu 2+ / Cu is 0.34 V. Calculate the reduction potential at
pH = 14 for the above couple. Ksp of Cu(OH)2 is 1 × 1019.
Q.8 Determine the degree of hydrolysis and hydrolysis constant of aniline hydrochloride in M/32 solution of
salt at 298 K from the following cell data at 298 K.
Pt | H2 (1 atm) | H+(1M) || M/32 C6H5NH3Cl | H2 (1 atm) | Pt ; Ecell= – 0.188 V.
Q.9 The emf of the cell, Pt | H2 (1 atm), | H+ (0.1 M, 30 ml) || Ag+ (0.8 M) | Ag is 0.9 V. Calculate the emf
when 40 ml of 0.05 M NaOH is added to the anodic compartment.
Q.10 The emf of the cell Ag|AgI|KI(0.05M) || AgNO3(0.05M) |Ag is 0.788V. Calculate the solubility product
of AgI.
Q.11 Consider the cell Ag|AgBr(s)|Br ||AgCl(s), Ag | Cl at 25º C . The solubility product constants of AgBr
& AgCl are respectively 5 × 1013 & 1 × 1010 . For what ratio of the concentrations of Br & Cl ions
would the emf of the cell be zero ?
Q.12 The pKsp of Agl is 16.07 . If the Eº value for Ag+Ag is 0.7991 V . Find the Eº for the half cell reaction
AgI (s) + e  Ag + I.
Q.13 For the galvanic cell : Ag|AgCl(s)| KCl (0.2M) || K Br (0.001 M)| AgBr(s) | Ag,
Calculate the EMF generated and assign correct polarity to each electrode for a spontaneous process
after taking into account the cell reaction at 250C.
[K sp( AgCl)  2.8 1010 ;K sp ( AgBr)  3.3 1013 ]
Q.14 Given, E° = –0.268 V for the Cl– | PbCl2 | Pb couple and – 0.126 V for the Pb2+ | Pb couple, determine
Ksp for PbCl2 at 25°C?
Q.15 Calculate the voltage, , of the cell at 25° C

Mn(s) | Mn(OH)2(s) | Mn2+(x M), OH –(1.00 x 10–4M) || Cu2+(0.675M) | Cu(s)
given that Ksp = 1.9 × 10–13 for Mn(OH)2(s) E0 (Mn2+/Mn) = –1.18 V
Q.16 Calculate the voltage, E, of the cell

Ag(s) | AgIO3(s) | Ag+(x M), HIO3 (0.300M) || Zn2+ (0.175M) | Zn(s)
if Ksp = 3.02 × 10–8 for AgIO3(s) and Ka = 0.162 for HIO3.
Q.17 Estimate the cell potential of a Daniel cell having 1 M Zn++ & originally having 1 M Cu++ after sufficient
NH3 has been added to the cathode compartment to make NH3 concentration 2 M.
Kf for [Cu(NH3)4]2+ = 1 × 1012, E0 for the reaction,
Zn + Cu2+  Zn2+ + Cu is 1.1 V.
Q.18 The overall formation constant for the reaction of 6 mol of CN with cobalt (II) is
1 × 1019. The standard reduction potential for the reaction
[Co(CN)6]3 + e  Co(CN)64 is 0.83 V. Calculate the formation constant of [Co(CN)6]3
Given Co3+ + e  Co2+ ; E0 = 1.82 V
Q.19 Calculate E° for the following reactions at 298 K,

Ag( NH3 ) 2 + e– Ag + 2NH3
Ag(CN ) 2 + e–  Ag + 2CN–
Given: E    0.7991 V, K Ins [Ag( NH 3 ) 2 ] = 6.02 × 10–8 and K Ins [Ag(CN) 2 ] = 1.995 ×10–19
Ag |Ag
Q.20 Calculate the equilibrium constant for the reaction:

3Sn(s) + 2Cr2O72– + 28H+  3Sn4+ + 4Cr3+ + 14H2O
E0 for Sn/Sn2+ =0.136 V E0 for Sn2+/Sn4+ = – 0.154 V
E0 for Cr2O72–/Cr3+ = 1.33 V
Q.21 Calculate the equlibrium concentrations of all ions in an ideal solution prepared by mixing 25.00 mL of
0.100M Tl+ with 25.00mL of 0.200M Co3+.
E0 ( Tl+ /Tl3+ )= –1.25 V ; E0 (Co3+/Co2+ ) = 1.84 V
Q.22 One of the methods of preparation of per disulphuric acid, H2S2O8, involve electrolytic oxidation of
H 2 SO 4 at anode (2H 2 SO 4  H 2 S 2 O 8 + 2H + + 2e  ) with oxygen and hydrogen as
byproducts. In such an electrolysis, 9.722 L of H2 and 2.35 L of O2 were generated at STP. What is
the weight of H2S2O8 formed?
Q.23 A current of 3 amp was passed for 2 hour through a solution of CuSO4 ,3 g of Cu2+ ions were deposited
as Cu at cathode. Calculate percentage current efficiency of the process.
Q.24 An acidic solution of Cu2+ salt containing 0.4 g of Cu2+ is electrolyzed until all the copper is deposited.
The electrolysis is continued for seven more minutes with the volume of solution kept at 100 ml and the
current at 1.2 amp. Calculate the volume of gases evolved at NTP during the entire electrolysis.
Q.25 In the refining of silver by electrolytic method what will be the weight of 100 gm Ag anode if
5 ampere current is passed for 2 hours? Purity of silver is 95% by weight.
Q.26 Dal lake has water 8.2 ×1012 litre approximately. A power reactor produces electricity at the rate of
1.5×106coulomb per second at an appropriate voltage.How many years would it take to electrolyse the
lake?
Q.27 A lead storage cell is discharged which causes the H2SO4 electrolyte to change from a concentration of
34.6 % by weight (density 1.261g ml–1 at 25°C) to 27 % by weight. The original volume of electrolyte
is one litre. Calculate the total charge released at anode of the battery. Note that the water is produced
by the cell reaction as H2SO4 is used up. Over all reaction is
Pb(s) + PbO2(s) + 2H2SO4(l)  2PbSO4(s) + 2H2O(l)
Q.28 Determine at 298 for cell

Pt | Q, QH2, H+ || 1M KCl | Hg2Cl2(s) | Hg(l) | Pt
(a) it's emf when pH = 5.0
(b) the pH when Ecell = 0
(c) the positive electrode when pH = 7.5
given E0RP(RHS) = 0.28, E0RP(LHS) = 0.699
Q.29 Calculate the cell potential of a cell having reaction: Ag2S + 2e–  2Ag + S2– in a solution buffered at
pH = 3 and which is also saturated with 0.1 M H2S.
For H2S : K1 = 10–8 and K2 = 1.1 × 10–13, Ksp(Ag2S) = 2 × 10–49, E Ag / Ag  0.8.
Q.30 The equivalent conductance of 0.10 N solution of MgCl2 is 97.1 mho cm2 equi–1 at 25°C. a cell
with electrode that are 1.5 cm2 in surface area and 0.5 cm apart is filled with 0.1 N MgCl2 solution.
How much current will flow when potential difference between the electrodes is 5 volt.
Q.31 A dilute aqueous solution of KCl was placed between two electrodes 10 cm apart, across which a
potential of 6 volt was applied. How far would the K+ ion move in 2 hours at 25°C? Ionic
conductance of K+ ion at infinite dilution at 25°C is 73.52 ohm–1 cm2 mole–1?
Q.32 When a solution of specific conductance 1.342 ohm–1 metre–1 was placed in a conductivity cell
with parallel electrodes, the resistance was found to be 170.5 ohm. Area of electrodes is
1.86×10–4 m2. Calculate separation of electrodes.
Q.33 The specific conductance at 25°C of a saturated solution of SrSO 4 is 1.482×10–4 ohm–1 cm–1while
that of water used is 1.5×10–6 mho cm–1. Determine at 25°C the solubility in gm per litre of SrSO 4
in water. Molar ionic conductance of Sr2+ and SO42– ions at infinite dilution are 59.46 and
79.8 ohm–1 cm2 mole–1 respectively. [ Sr = 87.6 , S = 32 , O = 16 ]
Q.34 Calculate the solubility and solubility product of Co2 [Fe(CN)6] in water at 250C from the following
data:
Conductivity of a saturated solution of Co2[Fe(CN)6] is 2.06 × 10–6–1 cm–1 and that of water used
4.1 × 10–7–1 cm–1 . The ionic molar conductivities of Co2+ and Fe(CN)64– are 86.0 –1 cm2 mol–1
and 444.0 –1 cm–1mol–1.
Q.35 In two vessels each containing 500ml water, 0.5m mol of aniline (Kb= 109) and 25mmol of HCl are
added separately. Two hydrogen electrodes are constructed using these solutions. Calculate the emf of
cell made by connecting them appropriately.
EXERCISE III
Single correct
Q.1 One gm metal M+2 was discharged by the passage of 1.81 × 1022 electrons. What is the atomic weight
of metal?
(A) 33.35 (B) 133.4 (C) 66.7 (D) 55
Q.2 One mole of electron passes through each of the solution of AgNO3, CuSO4 and AlCl3 when Ag, Cu
and Al are deposited at cathode. The molar ratio of Ag, Cu and Al deposited are
(A) 1 : 1 : 1 (B) 6 : 3 : 2 (C) 6 : 3 : 1 (D) 1 : 3 : 6
Q.3 Salts of A (atomic weight = 7), B (atomic weight =27) and C (atomic weight = 48) were electrolysed
under identical conditions using the same quantity of electricity. It was found that when 2.1 g of A was
deposited, the weights of B and C deposited were 2.7 and 7.2 g. The valencies of A, B and C
respectively are
(A) 3, 1 and 2 (B) 1, 3 and 2 (C) 3, 1 and 3 (D) 2, 3 and 2
Q.4 The density of Cu is 8.94 g cm–3. The quantity of electricity needed to plate an area 10 cm × 10 cm to
a thickness of 10–2 cm using CuSO4 solution would be
(A) 13586 C (B) 27172 C (C) 40758 C (D) 20348 C
Q.5 During electrolysis of an aqueous solution of sodium sulphate, 2.4 L of oxygen at STP was liberated at
anode. The volume of hydrogen at STP, liberated at cathode would be
(A) 1.2 L (B) 2.4 L (C) 2.6 L (D) 4.8 L
Q.6 During electrolysis of an aqueous solution of CuSO4 using copper electrodes, if 2.5 g of Cu is deposited
at cathode, then at anode
(A) 890 ml of Cl2 at STP is liberated (B) 445 ml of O2 at STP is liberated
(C) 2.5 g of copper is deposited (D) a decrease of 2.5 g of mass takes place
Q.7 The charge required for the oxidation of one mole Mn3O4 into MnO 24 in presence of alkaline medium is
(A) 5 × 96500 C (B) 96500 C (C) 10 × 96500 C (D) 2 × 96500 C
Q.8 A solution of sodium sulphate in water is electrolysed using inert electrodes. The products at the cathode
and anode are respectively.
(A) H2, O2 (B) O2, H2 (C) O2, Na (D) none
Q.9 When an aqueous solution of lithium chloride is electrolysed using graphite electrodes
(A) Cl2 is liberated at the anode.
(B) Li is deposited at the cathode
(C) as the current flows, pH of the solution around the cathode remains constant
(D) as the current flows, pH of the solution around the cathode decreases.
Q.10 A standard hydrogen electrons has zero electrode potential because

(A) hydrogen is easier to oxidise
(B) this electrode potential is assumed to be zero
(C) hydrogen atom has only one electron
(D) hydrogen is the lighest element.
Q.11 If the pressure of H2 gas is increased from 1 atm to 100 atm keeping H+ concentration constant at 1 M,
the change in reduction potential of hydrogen half cell at 25°C will be
(A) 0.059 V (B) 0.59 V (C) 0.0295 V (D) 0.118 V
Q.12 The equilibrium constant for the reaction

Sr(s) + Mg+2 (aq)  Sr+2 (aq) + Mg(s) is 2.69 × 1012 at 25°C
The E° for a cell made up of the Sr/Sr+2 and Mg+2/Mg half cells
(A) 0.3667 V (B) 0.7346 V (C) 0.1836 V (D) 0.1349 V
Q.13 A silver wire dipped in 0.1 M HCl solution saturated with AgCl develops oxidation potential of –0.25 V.
If E  = – 0.799 V, the Ksp of AgCl in pure water will be
Ag / Ag 
(A) 2.95 × 10–11 (B) 5.1 × 10–11 (C) 3.95 × 10–11 (D) 1.95 × 10–11
Q.14 Consider the reaction of extraction of gold from its ore

1 1
Au + 2CN– (aq.) + O2 (g) + H2O  Au (CN) 2 + OH–
4 2
Use the following data to calculate G° for the reaction
Kf {Au (CN) 2 } = X
O2 + 2H2O + 4e–  4OH– ; E° = + 0.41 volt
Au3+ + 3e–  Au ; E° = + 1.5 volt
Au3+ + 2e–  Au+ ; E° = + 1.4 volt
(A) – RT ln X + 1.29 F (B) – RT ln X – 2.11 F
1
(C) – RT ln + 2.11 F (D) – RT ln X – 1.29 F
X
Q.15 Consider the following Galvanic cell.
By what value the cell voltage change when concentration of ions in anodic and cathodic compartments
both increased by factor of 10 at 298 K
(A) +0.0591 (B) –0.0591 (C) –0.1182 (D) 0
Q.16 For the cell

Pt | H2(0.4 atm) | H+(pH=1) || H+(pH = 2) | H2 (0.1 atm) | Pt
The measured potential at 25°C is
(A) –0.1 V (B) –0.5 (C) –0.041 (D) none
o
Q.17 For the fuel cell reaction 2H2(g) + O2(g)  2H2O(l) ;  f H 298 (H 2O, l ) = –285.5 kJ/mol
What is So298 for the given fuel cell reaction?

Given: O2(g) + 4H+(aq) + 4e–  2H2O(l) E° = 1.23 V
(A) – 0.322 J/K (B) – 0.635 kJ/K (C) 3.51 kJ/K (D) – 0.322 kJ/K
Q.18 The standard reduction potentials of Cu2+/ Cu and Cu2+ / Cu+ are 0.337 and 0.153 V respectively. The
standard electrode potential of Cu+ / Cu half cell is
(A) 0.184 V (B) 0.827 V (C) 0.521 V (D) 0.490 V
Q.19 A hydrogen electrode X was placed in a buffer solution of sodium acetate and acetic acid in the ratio
a : b and another hydrogen electrode Y was placed in a buffer solution of sodium acetate and acetic acid
in the ratio b : a. If reduction potential values for two cells are found to be E1 and E2 respectively w.r.t.
standard hydrogen electrode, the pKa value of the acid can be given as
E1  E 2 E 2  E1 E1  E 2 E1  E 2
(A) (B) (C)  (D)
0.118 0.118 0.118 0.118
Q.20 The resistance of 0.5 M solution of an electrolyte in a cell was found to be 50 . If the electrodes in the
cell are 2.2 cm apart and have an area of 4.4 cm 2 then the molar conductivity
(in S m2 mol–1) of the solution is
(A) 0.2 (B) 0.02 (C) 0.002 (D) None of these
Q.21 Equivalent conductance of 0.1 M HA(weak acid) solution is 10 Scm2equivalent–1 and that at infinite
dilution is 200 Scm2equivalent–1 Hence pH of HA solution is
(A) 1.3 (B) 1.7 (C) 2.3 (D) 3.7
Q.22 If x is specific resistance of the electrolyte solution and y is the molarity of the solution, then ^m is given
by
1000 x y 1000 xy
(A) (B) 1000 (C) (D)
y x xy 1000
Q.23 The dissociation constant of n-butyric acid is 1.6 × 10–5 and the molar conductivity at infinite dilution is
380 × 10–4 Sm2mol–1. The specific conductance of the 0.01 M acid solution is
(A) 1.52 × 10–5 Sm–1 (B) 1.52 × 10–2 Sm–1
(C) 1.52 × 10–3 Sm–1 (D) None
Q.24 The conductivity of a saturated solution of Ag3PO4 is 9 × 10–6 S m–1 and its equivalent conductivity is
1.50 × 10–4 S m2 equivalent–1. The Ksp of Ag3PO4 is
(A) 4.32 × 10–18 (B) 1.8 ×10–9 (C) 8.64 × 10–13 (D) None of these
Q.25 A saturated solution in AgA (Ksp = 3×10–14) and AgB (Ksp = 1×10–14) has conductivity of
375 × 10–10 Scm–1 and limiting molar conductivity of Ag+ and A¯ are 60 Scm2 mol–1 and
80 Scm2 mol–1 respectively then what will be the limiting molar conductivity of B¯ (in Scm2 mol–1)
(A) 150 (B) 180 (C) 190 (D) 270
Q.26 Equal volumes of 0.015 M CH3COOH & 0.015 M NaOH are mixed together. What would be molar
conductivity of mixture if conductivity of CH3COONa is 6.3 ×10–4 S cm–1
(A) 8.4 S cm2 mol–1 (B) 84 S cm2 mol–1 (C) 4.2 S cm2 mol–1 (D) 42 S cm2 mol–1
Q.27 During discharging of lead storage battery, which of the following is/are true ?
(A) H2SO4 is produced (B) H2O is consumed
(C) PbSO4 is formed at both electrodes (D) Density of electrolytic solution decreases
Q.28 Which of the following arrangement will produce oxygen at anode during electrolysis ?
(A) Dilute H2SO4 solution with Cu electrodes.
(B) Dilute H2SO4 solution with inert electrodes.
(C) Fused NaOH with inert electrodes.
(D) Dilute NaCl solution with inert electrodes.
Q.29 If 270.0 g of water is electrolysed during an experiment performed by miss Abhilasha with 75% current
efficiency then
(A) 168 L of O2 (g) will be evolved at anode at 1 atm & 273 K
(B) Total 504 L gases will be produced at 1 atm & 273 K.
(C) 336 L of H2 (g) will be evolved at anode at 1 atm & 273 K
(D) 45 F electricity will be consumed
Q.30 Pick out the correct statements among the following from inspection of standard reduction potentials
(Assume standard state conditions).
Cl 2 (aq.) + 2e  2Cl–(aq.) E oCl  = + 1.36 volt
2 / Cl
Br2 (aq.) + 2e  2Br–(aq.) E oBr  = + 1.09 volt

2 / Br
I2(s) + 2e  2I– (aq.) E oI  = + 0.54 volt

2/I
S2 O82 (aq.) + 2e  2SO 24 (aq.) E So 2 2

= + 2.00 volt
2O8 / SO 4
(A) Cl2 can oxidise SO 24 from solution

(B) Cl2 can oxidise Br– and I– from aqueous solution
(C) S2 O82 can oxidise Cl–, Br– and I– from aqueous solution
(D) S2O82– is added slowly, Br– can be reduce in presence of Cl–
Q.31 The EMF of the following cell is 0.22 volt.

Ag(s) | AgCl(s) | KCl (1M) | H+(1M) | H2(g) (1atm) ; Pt(s).
Which of the following will decrease the EMF of cell.
(A) increasing pressure of H2(g) from 1 atm to 2 atm
(B) increasing Cl– concentration in Anodic compartment
(C) increasing H+ concentration in cathodic compartment
(D) decreasing KCl concentration in Anodic compartment.
Q.32 Statement -1 : The voltage of mercury cell remains constant for long period of time.
Statement -2 : It is because net cell reaction does not involve active species.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.
Q.33 Statement -1 : The SRP of three metallic ions A+,B2+, C3+ are –0.3, –0.5, 0.8 volt respectively, so
oxidising power of ions is C3+ > A+ > B2+.
Statement -2 : Higher the SRP, higher the oxidising power.
Q.34 Statement -1 : We can add the electrode potential in order to get electrode potential of net reaction.
Statement -2 : Electrode potential is an intensive property.
Comprehension
Paragraph for Question Nos. 35 to 37
A sample of water from a large swimming pool has a resistance of 10000  at 25°C when placed in a
certain conductance cell. When filled with 0.02 M KCl solution, the cell has a resistance of 100  at
25°C. 585 gm of NaCl were dissolved in the pool, which was throughly stirred. A sample of this solution
gave a resistance of 8000 .
[Given : Molar conductance of NaCl at that concentration is 125 –1 cm2 mol–1 and molar conductivity
of KCl at 0.02 M is 200 –1 cm2 mol–1.]
Q.35 Cell constant (in cm–1) of conductance cell is:
(A) 4 (B) 0.4 (C) 4 ×10–2 (D) 4 ×10–5
Q.36 Conductivity (Scm–1) of H2O is:

(A) 4 × 10–2 (B) 4 × 10–3 (C) 4 × 10–5 (D) None of these
Q.37 Volume (in Litres) of water in the pool is:

(A) 1.25 × 105 (B) 1250 (C) 12500 (D) None of these
Paragraph for Question Nos. 38 & 39
Copper reduces NO3 into NO and NO2 depending upon conc. of HNO3 in solution. Assuming
[Cu2+] = 0.1 M, and PNO= PNO =10–3 atm and using given data answer the following questions:
2
Eo = + 0.34 volt
Cu 2  / Cu
Eo = + 0.96 volt
NO3 / NO
Eo = + 0.79 volt
NO3 / NO 2
RT
at 298 K (2.303) = 0.06 volt
F
Q.38 ECell for reduction of NO3  NO by Cu(s), when [HNO3] = 1M is [At T = 298]
(A) ~ 0.61 (B) ~ 0.71 (C) ~ 0.51 (D) ~ 0.81
Q.39 At what HNO3 concentration thermodynamic tendency for reduction of NO3 into NO and NO2 by
copper is same?
(A) 101.23 M (B) 100.56 M (C) 100.66 M (D) 100.12 M
Match the column

Q.40 Column I Column II
(Electrolysis product using inert electrode)
(A) Dilute solution of HCl (P) O2 evolved at anode
(B) Dilute solution of NaCl (Q) H2 evolved at cathode
(C) Concentrated solution of NaCl (R) Cl2 evolved at anode
(D) AgNO3 solution (S) Ag deposition at cathode
EXERCISE IV
Q.1 Calculate the equilibrium constant for the reaction, 2Fe 3+ + 3I  2Fe2+ + I3. The standard
reduction potentials in acidic conditions are 0.77 and 0.54 V respectively for Fe 3+ / Fe2+ and I3 / I
couples. [JEE 1998]
Q.2 Find the solubility product of a saturated solution of Ag2CrO4 in water at 298 K if the emf of the cell
Ag|Ag+ (satd.Ag2 CrO4 soln.) || Ag +(0.1 M) | Ag is 0.164 V at 298K. [JEE 1998]
Q.3 A gas X at 1 atm is bubbled through a solution containing a mixture of 1 M Y and 1 M Z at 25°C. If the
reduction potential of Z > Y > X, then
(A) Y will oxidise X and not Z (B) Y will oxidise Z and X
(C) Y will oxidise both X and Z (D) Y will reduce both X and Z. [JEE 1999]
Q.4 For the electrochemical cell, M | M+ || X– | X, E° (M+/M) = 0.44 V and E° (X/X–) = 0.33V. From this
data , one can deduce that
(A) M + X  M+ + X– is the spontaneous reaction
(B) M+ + X–  M + X is the spontaneous reaction
(C) Ecell= 0.77 V
(D) Ecell= –0.77 V [JEE 2000]
Q.5 Copper sulphate solution (250 mL) was electrolysed using a platinum anode and a copper cathode. A
constant current of 2 mA was passed for 16 mintue. It was found that after electrolysis, the absorbance
(concentration) of the solution was reduced to 50% of its original value. Calculate the concentration of
copper sulphate in the solution to begin with. [JEE 2000]
Q.6 The following electrochemical cell has been set up

Pt(I) | Fe3+, Fe2+(a =1) || Ce4+ , Ce3+ (a = 1) | Pt(II)

E Fe 3 / Fe 2  = 0.77 V and E Ce 4  / Ce 3 = 1.61 V
If an ammetter is connected between the two platinum electrodes. predict the direction of flow of current.
Will the current increase or decrease with time? [JEE 2000]
Q.7 The reaction,
3ClO–(aq)  ClO 3 (aq) + 2Cl–(aq)
is an example of
(A) Oxidation reaction (B) Reduction reaction
(C) Disproportionation reaction (D) Decomposition reaction [JEE 2001]
Q.8 The correct order of equivalent conductance at infinite dilution of LiCl, NaCl and KCl is
(A) LiCl > NaCl > KCl (B) KCl > NaCl > LiCl
(C) NaCl > KCl > LiCl (D) LiCl > KCl > NaCl [JEE 2001]
Q.9 Saturated solution of KNO3 is used to make salt bridge because

(A) velocity of K+ is greater than that of NO3
(B) velocity of NO3 is greater than that of K+
(C) velocities of both K+ and NO3 are nearly the same

(D) KNO3 is highly soluble in water [JEE 2001]
Q.10 The standard potential of the following cell is 0.23 V at 15° C & 0.21 V at 35° C
Pt | H2(g) | HCl (aq) | AgCl(s) | Ag(s)
(i) Write the cell reaction.
(ii) Calculate H0 ,S0 for the cell reaction by assuming that these quantities remain unchanged in the range
15°C to 35°C.
(iii) Calculate the solubility of AgCl in water at 25°C. Given standard reduction potential of the
Ag+/Ag couple is 0.80 V at 25°C. [JEE 2001]
Q.11 Standard electrode potential data are useful for understanding the suitablilty of an oxidant in a redox
titration. Some half cell reactions and their standard potentials are given below:
MnO 4 (aq) + 8H+(aq) + 5e–  Mn2+ (aq) + 4H2O (l); E° = 1.51 V
Cr2 O 72 (aq) + 14 H+ (aq) + 6e–  2Cr3+ (aq) +7H2O (l); E° = 1.38 V
Fe3+ (aq) + e–  Fe2+ (aq); E° = 0.77 V
Cl2 (g) + 2e–  2Cl– (aq); E° = 1.40 V
Identify the only incorrect statement regarding quantitative estimation of aqueous Fe(NO3)2
(A) MnO 4 can be used in aqueous HCl (B) Cr2 O 72 can be used in aqueous HCl
(C) MnO 4 can be used in aqueous H2SO4 (D) Cr2 O 72 can be used in aqueous H2SO4
[JEE 2002]
Q.12 In the electrolytic cell, flow of electrons is from:
(A) Cathode to anode in solution (B) Cathode to anode through external supply
(C) Cathode to anode through internal supply (D) Anode to cathode through internal supply.
[JEE 2003]
Q.13 Two students use same stock solution of ZnSO4 and a solution of CuSO4. The e.m.f of one cell is
0.03 V higher than the other. The conc. of CuSO4 in the cell with higher e.m.f value is 0.5 M. Find out
 2.303 RT 
the conc. of CuSO4 in the other cell   0.06  . [JEE 2003]
 F 
Q.14 Zn | Zn2+ (a = 0.1M) || Fe2+ (a = 0.01M)|Fe. The emf of the above cell is 0.2905 V. Equilibrium
constant for the cell reaction is
(A) 100.32/0.0591 (B) 100.32/0.0295
(C) 100.26/0.0295 (D) e0.32/0.295 [JEE 2004]
Q.15 Find the equilibrium constant at 298 K for the reaction,

Cu2+(aq) + In2+(aq)  Cu+(aq) + In3+(aq)
  
Given that E Cu 2 |Cu   0.15V , E In 3 |In   0.42V , E In 2  |In   0.40V [JEE 2004]
Q.16 The half cell reactions for rusting of iron are: [JEE 2005]
1
2H+ + O + 2e–  H2O; E0 = + 1.23 V, Fe2+ + 2e–  Fe; E0 = –0.44 V
2 2
G0 (in kJ) for the reaction is:
(A) –76 (B) –322
(C) –122 (D) –176
Q.17
0
(a) Calculate G f of the following reaction
Ag  (aq ) + Cl  (aq )  AgCl(s)

0 0 0
Given : G f (AgCl) = –109 kJ/mole, G f (Cl–) = –129 kJ/mole, G f (Ag+) = 77 kJ/mole
Represent the above reaction in form of a cell
Calculate E0 of the cell. Find log10KSP of AgCl
(b) 6.539 × 10–2 g of metallic Zn (amu = 65.39) was added to 100 ml of saturated solution of AgCl.
2
Calculate log10 [ Zn ] , given that
[Ag  ]2
Ag+ + e– Ag E0 = 0.80 V ; Zn2+ + 2e– Zn E0 = –0.76V
Also find how many moles of Ag will be formed? [JEE 2005]
Question No. 18 to 20 (3 questions)

Tollen’s reagent is used for the detection of aldehyde when a solution of AgNO3 is added to glucose with
NH4OH then gluconic acid is formed
Ag+ + e–  Ag ; E 0red = 0.8 V
C6H12O6 + H2O  C6H12O7 (Gluconic acid) + 2H+ + 2e– ; E 0red = – 0.05 V

0
Ag( NH 3 ) 2 + e– Ag(s) + 2NH3 ; E = – 0.337 V
RT F
[Use 2.303 × = 0.0592 and = 38.92 at 298 K] [JEE 2006]
F RT
Q.18 2Ag+ + C6H12O6 + H2O  2Ag(s) + C6H12O7 + 2H+
Find ln K of this reaction
(A) 66.13 (B) 58.38 (C) 28.30 (D) 46.29
Q.19 When ammonia is added to the solution, pH is raised to 11. Which half-cell reaction is affected by pH
and by how much?
(A) Eoxd will increase by a factor of 0.65 from E 0oxd
(B) Eoxd will decrease by a factor of 0.65 from E 0oxd
(C) Ered will increase by a factor of 0.65 from E 0red
(D) Ered will decrease by a factor of 0.65 from E 0red
Q.20 Ammonia is always is added in this reaction. Which of the following must be incorrect?
(A) NH3 combines with Ag+ to form a complex.
(B) Ag( NH 3 ) 2 is a weaker oxidising reagent than Ag+.
(C) In absence of NH3 silver salt of gluconic acid is formed.
(D) NH3 has affected the standard reduction potential of glucose/gluconic acid electrode.
Q.21 We have taken a saturated solution of AgBr.Ksp of AgBr is 12 × 10–14. If 10–7 mole of AgNO3 are
added to 1 litre of this solution find conductivity (specific conductance) of this solution in terms of 10–7
S m–1 mol–1.
0
Given :  ( Ag ) = 6 ×10–3 S m2 mol–1 ; 0
0
= 8 ×10–3 S m2 mol–1 ;  = 7×10–3 S m2 mol–1
( Br  ) ( NO3 )
[JEE 2006]
Paragraph for Question Nos. 22 to 24 (3 questions)

Chemical reactions involve interaction of atoms and molecules. A large number of atoms/molecules
(approximately 6.023 × 1023) are present in a few grams of any chemical compound varying with their
atomic/molecular masses. To handle such large numbers conveniently, the mole concept was introduced.
This concept has implications in diverse areas such as analytical chemistry, biochemistry, electrochemistry
and radiochemistry. The following example illustrates a typical case, involving chemical/ electrochemical
reaction, which requires a clear understanding of the mole concept.
A 4.0 molar aqueous solution of NaCl is prepared and 500 mL of this solution is electrolysed. This leads
to the evolution of chlorine gas at one of the electrodes (atomic mass : Na = 23,
Hg = 200; 1 Faraday = 96500 coulombs) [JEE 2007]
Q.22 The total number of moles of chlorine gas evolved is
(A) 0.5 (B) 1.0 (C) 2.0 (D) 3.0
Q.23 If the cathode is a Hg electrode, the maximum weight (g) of amalgam formed from this solution is
(A) 200 (B) 225 (C) 400 (D) 446
Q.24 The total charge (coulombs) required for complete electrolysis is

(A) 24125 (B) 48250 (C) 96500 (D) 193000
Paragraph for Question Nos. 25 & 26 (2 questions)

Redox reactions play a pivoted role in chemistry and biology. The values of standard redox potential
(E°) of two half-cell reactions decide which way the reaction is expected to proceed. A simple example
is a Daniel cell in which zinc goes into solution and copper gets deposited. Given below are a set of
half-cell reactions (acidic medium) along with their E° (V with respect to normal hydrogen electrode)
values. Using this data obtain the correct explanations to Questions 14-16.
I2 + 2e–  2I– E° = 0.54
Cl2 + 2e–  2Cl– E° = 1.36
Mn + e  Mn
3+ – 2+ E° = 1.50
Fe + e Fe
3+ – 2+ E° = 0.77
O2 + 4H+ + 4e–  2H2O E° = 1.23 [JEE 2007]
Q.25 Among the following, identify the correct statement.
(A) Chloride ion is oxidised by O2 (B) Fe2+ is oxidised by iodine
(C) Iodine ion is oxidised by chlorine (D) Mn2+ is oxidised by chlorine
Q.26 While Fe3+ is stable, Mn3+ is not stable in acid solution because
(A) O2 oxidises Mn2+ to Mn3+
(B) O2 oxidises both Mn2+ to Mn3+ and Fe2+ to Fe3+
(C) Fe3+ oxidises H2O to O2
(D) Mn3+ oxidises H2O to O2
Q.27 Electrolysis of dilute aqueous NaCl solution was carried out by passing 10 milli ampere current. The time
required to liberate 0.01 mol of H2 gas at the cathode is (1 Faraday = 96500 C mol–1)
(A) 9.65 × 104 sec (B) 19.3 × 104 sec (C) 28.95 × 104 sec (D) 38.6 × 104 sec
[JEE 2008]
Q.28 For the reaction of NO3¯ ion in an aqueous solution, E° is +0.96 V. Values of E° for some metal ions are
given below
V2+ (aq) + 2e¯  V E° = – 1.19 V
Fe (aq) + 3e¯  Fe
3+ E° = – 0.04 V
Au (aq) + 3e¯  Au
3+ E° = + 1.40 V
Hg2+ (aq) + 2e¯  Hg E° = + 0.86 V
The pair(s) of metal that is(are) oxidised by NO3¯ in aqueous solution is(are) [JEE 2009]
(A) V and Hg (B) Hg and Fe
(C) Fe and Au (D) Fe and V
Q.29 Among the following, the intensive property is (properties are) [JEE 2010]
(A) molar conductivity (B) electromotive force
(C) resistance (D) heat capacity
Paragraph for Questions 30 to 31

The concentration of potassium ions inside a biological cell is at least twenty times higher than the outside.
The resulting potential difference across the cell is important in several processes such as transmission of
nerve impulses and maintaining the ion balance. A simple model for such a concentration cell involving a
metal M is:
M(s) | M+(aq; 0.05 molar) | | M+ (aq; 1 molar) | M(s)
For the above electrolytic cell the magnitude of the cell potential | Ecell | = 70 mV. [JEE 2010]
Q.30 For the above cell
(A) Ecell < 0; G > 0 (B) Ecell > 0; G < 0
(C) Ecell < 0 ; G° > 0 (D) Ecell > 0; G° < 0
Q.31 If the 0.05 molar solution of M+ is replaced by a 0.0025 molar M+ solution, then the magnitude of the
cell potential would be
(A) 35 mV (B) 70 mV (C) 140 mV (D) 700 mV
COMPREHENSION
Comprehension # 1
If an element can exist in several oxidation states, it is convenient to display the reduction potentials
corresponding to the various half reactions in diagrammatic form, known as Latimer diagram. The Latimer
diagram for chlorine in acid solution is
ClO4–  1
.20 1
V  ClO –  .18
 1
V  HClO  .60
V  HClO 1
.67
 V  Cl 1
.36
 V  Cl–
3 2 2
in basic solution.
0.37 V 0.30 V 0.68 V 0.42 V 1.36 V
ClO4–    ClO3–    ClO2–    ClO–    Cl2   Cl–
The standard potentials for two nonadjacent species can also be calculated by using the concept that G°
as an additive property but potential is not an additive property and G° = – nFx0. If a given oxidation state is
a stronger oxidising agent than in the next higher oxidation state, disproportionation can occur. The reverse
of disproportionation is called comproportionation. The relative stabilities of the oxidation state can also be
understood by drawing a graph of G°/F against oxidation state, known as Frost diagram, choosing the
stability of zero oxidation state arbitrarily as zero. The most stable oxidation state of a species lies lowest in
the diagram. Disproportionation is spontaneous if the species lies above a straight line joining its two product
species.
1. Which of the following couple have same value of potential at pH = 0 and pH = 14?
ClO 4 ClO2 ClO Cl2

(A) (B) (C) (D)
ClO 3 Cl2 Cl2 Cl
ClO
2. What is the potential of couple at pH = 14 ?
Cl
(A) 1.78 V (B) – 0.94 V (C) 0.89 V (D) – 0.89 V

(A) Cl2 undergoes disproportionation into Cl– and ClO– both at pH = 0 and pH = 14.
(B) Cl2 undergoes disproportionation into Cl– and ClO– at pH = 14 but not at pH = 0.
(C) Cl2 undergoes disproportionation into Cl– and ClO– at pH = 0 but not at pH = 14.
(D) None of these
4. For a hypothetical element, the Frost diagram is shown in figure?

Which of the following oxidation state is least stable?
(A) – 1
(B) 0
(C) + 2
(D) + 3
5. Which of the following statement is correct ? According to Q.4

(A) A+1 undergoes disproportionation into A and A2+.
(B) A2+ undergoes disporportionation in A and A3+.
(C) A undergoes comporportionation in A+1 and A–1.
(D) All of the above.
Comprehension # 2
The molar conductance of NaCl varies with the concentration as shown in the following table.
and all values follows the equation
Cm = m – b C Where Cm = molar specific conductance
m = molar specific conductance at infinite dilution

C = molar concentration
Molar Concentration Molar Conductance
of NaCl in ohm-1 cm2 mole-1
4 x 10-4 107
9 x 10-4 97
16 x 10-4 87
When a certain conductivity cell (C) was filled with 25 x 10–4 (M) NaCl solution. The resistance of the cell was
found to be 1000 ohm. At Infinite dilution, conductance of Cl– and SO4–2 are 80 ohm–1 cm2 mole–1 and 160
ohm–1 cm2 mole–1 respectively.
6. What is the molar conductance of NaCl at infinite dilution ?
(A) 147 ohm–1 cm2 mole–1 (B) 107 ohm –1 cm2s mole–1
(C) 127 ohm cm mole
–1 2 –1
(D) 157 ohm–1 cm2 mole–1
7. What is the cell constant of the conductivity cell (C)
(A) 0.385 cm–1 (B) 3.85 cm–1 (C) 38.5 cm –1 (D) 0.1925 cm–1
8. If the cell (C) is filled with 5 x 10–3 (N) Na2SO4 the observed resistance was 400 ohm. What is the molar
conductance of Na2SO4.
(A) 19.25 ohm–1 cm2 mole–1 (B) 96.25 ohm–1 cm2 mole–1
(C) 385 ohm cm mole
–1 2 –1
(D) 192.5 ohm–1 cm2s mole–1
9. If a 100 mL solution of 0.1M HBr is titrated using a very concentrated solution of NaOH, then the conductivity
(specific conductance) of this solution at the equivalence point will be (assume volume change is negligible
due to addition of NaOH) . Report your answer after multipling it with 10 in Sm –1.
º
[Given (Na ) = 8 × 10–3 Sm2 mol–1 , º(Br  ) = 4 × 10–3 S m2 mol–1]
(A) 6 (B) 12 (C) 15 (D) 24
MATCH THE COLUMN

1. Match the column
Column I Column II
(A) Zn | Zn | | Mg | Mg
+2 2+
(p) Ecell = 0
c1 c2 (c1 = c2)
(B) Zn | Zn | | Ag | Ag
+2 +
(q) E0cell 0
at. equilibrium
(C) Ag | Ag+ | | Ag+ | Ag (r) E0cell = +ve
c1 c2 (c1 = c2)
(D) Fe | Fe | | Ag | Ag+
+2
(s) E0cell = –ve
c1 c2 (c1 = c2)
0
2.^ Match Matrix ( E Ag / Ag = 0.8).
(A) Pt | H2 (0.1 bar) | H (0.1 M) || H (1 M) | H2 (0.01 bar) | Pt
+ +
(p) Concentration cell
(B) Ag | Ag+ (10–9 M) || Ag+ (10–2 M) | Ag (q) Ecell > 0
(C) Cu | Cu (0.1 M) || Cu (0.01 M) | Cu
2+ 2+
(r) Eºcell = 0 but cell is working.
(D) Pt | Cl2 (1bar) | HCl (0.1 M) || NaCl (0.1M) | Cl2 | Pt (1 bar) (s) non working condition
ANSWER KEY
EXERCISE I
Q.1 (a) 2Ag + Cu2+  2Ag+ + Cu, (b) MnO 4 + 5Fe2+ + 8H+  Mn2+ + 5Fe3+ + 4H2O
(c) 2Cl– + 2Ag+  2Ag + Cl2, (d) H2 + Cd2+  Cd + 2H+
Q.2 (a) Zn | Zn2+ | | Cd2+ | Cd, (b) Pt | H2 | H+ | | Ag+ | Ag ,

(c) Pt | Fe2+, Fe3+ | | Cr2 O 72 , H+ , Cr3+ | Pt
Q.3 1.61 V Q.4 1.35 V
Q.5 – 0.80 V, NO Q.6 0.53 V, disproportionation
Q.7 – 0.0367 V Q.8 E =1.159V
Q.9 Kc = 1.864 × 10107, G0 = – 611.8 kJ Q.10 n=2
Q.11 E = 0.059
Q.12 E0cell = +0.01V, Ecell = 0.0785V, correct representation is Pb|Pb2+ (103M)||Sn2+(1M)|Sn
Q.13 [Cu2+] = 2.97 × 1012M for E =0 Q.14 E = 0.81 V
Q.15 0.52 V, 0.61 V Q.16 0.0295 V
Q.17 0.0295 V Q.18 pH = 4
Q.19 Kc = 7.6 × 1012 Q.20 Kc = 1.96 × 1026
Q.21 Kw 1014 Q.22 E0 = 0.7826 V
Q.23 –1.30 ×103 kJ mol–1
Q.24 (a) 6.02 × 1022 electrons lost, (b) 1.89 × 1022 electrons gained, (c) (b) 1.80 × 1023 electrons gained
Q.25 (a) 0.75 F, (b) 0.69 F, (c)1.1 F Q.26 (i) 54 gm, (ii) 16.35 gm
Q.27 1.023 × 105 sec Q.28 0.112 litre
Q.29 Rs. 0.75 x Q.30 (i) 2.1554 gm ; (ii) 1336. 15 sec
Q.31 115800C, 347.4 kJ Q.32 t = 193 sec
Q.33 A = 114, Q = 5926.8C Q.34 Final weight = 9.6g, 0.01 Eq of acid
Q.35 t = 93.65 sec. Q.36 60 %
Q.37 1.825 g Q.38 2M
Q.39 419 S cm2 equivalent –1 Q.40 0.00046 S cm1 ; 2174 ohm cm
Q.41 (i) 6.25 × 105 ohm, (ii) 1.6 × 106 amp Q.42 0.0141 mho g equiv–1 m2, 0.141 mho m–1
Q.43 (i) 232 Mho cm2 mol–1 , (ii) 116 Mho cm2 equivalent–1
Q.44 523.2 ×10–4 mho cm2 mol–1 Q.45 0.865
Q.46 (i) 390.6 S cm2 mol–1 (ii) 12.32% Q.47 1.33 ×10–4 gm/litre
Q.48 8.74 × 10–11 mole2 /litre2 Q.49  = 0.435 , k = 6.7×10–4
Q.50 (i) 6.98 (ii) 1.08 × 10–14
PROFICIENCY TEST
Q.1
1. T 2. F 3. T 4. T 5. T 6. F 7. T
8. T 9. F 10. T 11. T 12. T 13. T 14. F
15. F
Q.2
1. 0.66 cm–1 2. O2 3. increase 4. higher
5. O 2 & H2 6. Electrolyte concentration cell
7. Cr2 O72 (aq.), Cr3+(aq.), H+ | Pt
8. Pb(s) + PbO2(s) + 2H2SO4  2PbSO4(s) + 2H2O (l)

  dE  
9. Hg2Cl2(s) + 2e–  2Hg(l) + 2Cl–(aq.) 10. H = nF T   E 
  dT  
11. inert, i.e., should not interfere with net cell reaction
12. Salt bridge or porous partition 13. zero 14. E°red cathode
15. Amount, rate 16. reduction process 17. Oxygen
18. 2.5 × 96500 C
EXERCISE II
Q.1 [Cu2+] = 104M Q.2 pH = 6.61
Q.3 Ka = 6.74 × 104 Q.4 1.39V
Q.5 – 0.46 V Q.6 (ii). 1.27 V, (iii) 245.1 kJ
Q.7 E0 = 0.22 V Q.8 h = 2.12 ×10–2, Kh= 1.43 × 10–5 M
Q.9 0.95 V Q.10 Ksp = 1.1 × 1016
Q.11 [Br ] : [Cl] = 1 : 200 Q.12 E0 = 0.1511V
Q.13 – 0.037 V Q.14 1.536 ×10–5 M3
Q.15 1.66V Q.16 –1.188V
Q.17 E0 = 0.71V Q.18 Kf = 8.227 × 1063
Q.19 0.372 V , – 0.307 V Q.20 K = 10268
Q.21 Tl+ = 10–8; Co3+ = 2 × 10–8 Q.22 43.456g
Q.23 42.2 %
Q.24 V(O2) = 99.68 mL, V(H2) = 58.46 mL, Total vol. = 158.1 mL
Q.25 57.5894 gm Q.26 1.9 million year
Q.27 1.21 × 105 coulomb Q.28 (a) –0.124 V, (b) 7.1, (c) calomel electrode
Q.29 – 0.167 V Q.30 0.1456 ampere
Q.31 3.29 cm Q.32 4.25×10–2 metre
Q.33 0.1934 gm/litre Q.34 KSP = 7.682 × 10–17
Q.35 E = 0.395 V
EXERCISE III
Q.1 C Q.2 B Q.3 B Q.4 B Q.5 D Q.6 D Q.7 C
Q.8 A Q.9 A Q.10 B Q.11 A Q.12 A Q.13 B Q.14 A
Q.15 C Q.16 C Q.17 D Q.18 C Q.19 C Q.20 C Q.21 C
Q.22 C Q.23 B Q.24 A Q.25 D Q.26 B Q.27 C,D
Q.28 B,C,D Q.29 A,B Q.30 B,C Q.31 A,D Q.32 A Q.33 A Q.34 D
Q.35 B Q.36 C Q.37 A Q.38 B Q.39 C
Q.40 (A) P, Q (B) P, Q (C) Q, R, (D) P,S
EXERCISE IV
Q.1 KC = 6.26 × 107 Q.2 Ksp = 2.287 × 1012 Q.3 A Q.4 B
Q.5 7.95 × 10–5M Q.6 decrease with time Q.7 C Q.8 B Q.9 C
Q.10 H0 = – 49987 Jmol–1 , S0 = – 96.5 J mol–1 K–1 , s = 1.47 ×10–5 M Q.11 A
Q.12 C Q.13 0.05 M Q.14 B Q.15 KC = 1010 Q.16 B
Q.17 (a) E0 = 0.59 V, log10KSP = –10, (b) 52.8, 10–6 moles Q.18 A
Q.19 A Q.20 D Q.21 55 S m–1 Q.22 B Q.23 D Q.24 D
Q.25 C Q.26 D Q.27 B Q.28 A,B,D Q.29 A,B Q.30 B
Q.31 C
COMPREHENSION
Q.1 (D) Q.2 (C) Q.3 (B) Q.4 (D) Q.5 (A)
Q.6 (C) Q.7 (D) Q.8 (D) Q.9 (B)
MATCH THE COLUMN

Q.1 (A - s) ; (B - p,r) ; (C - p,q) ; (D - r) Q.2 (A - p, q, r) ; (B - q) ; (C - p, s) ;(D - p, s)
Chemical Kinetics [327]
EXERCISE-I
RATE OF REACTION AND STOICHIOMETRIC COEFFICIENT
Q.1 Ammonia and oxygen reacts at higher temperatures as
4NH3(g) + 5O2(g)  4NO(g) + 6H2O(g)
In an experiment, the concentration of NO increases by 1.08 ×10–2 mol litre–1 in 3 seconds. Calculate.
(i) rate of reaction.
(ii) rate of disappearance of ammonia
(iii) rate of formation of water
Q.2 In the following reaction 2H2O2  2H2O + O2

rate of formation of O2 is 3.6 M min–1.
(a) What is rate of formation of H2O?
(b) What is rate of disappearance of H2O2?
Q.3 In a catalytic experiment involving the Haber process, N2 + 3H2  2NH3, the rate of reaction was
measured as
[ NH 3 ]
Rate = = 2 × 10–4 mol L–1 s–1.
t
If there were no sides reactions, what was the rate of reaction expressed in terms of (a) N2, (b) H2?
Q.4 The reaction 2A + B + C  D + E is found to be first order in A second order in B and zero order in C.
(i) Give the rate law for the reaction in the form of differential equation.
(ii) What is the effect in rate of increasing concentrations of A, B, and C two times?
Q.5 At 27°C it was observed during a reaction of hydrogenation that the pressure of hydrogen gas decreases
from 2 atmosphere to 1.1 atmosphere in 75 minutes. Calculate the rate of reaction (in M sec–1) and rate
of reaction in terms of pressure.
Q.6 For the elementary reaction 2A + B2  2AB. Calculate how much the rate of reaction will change if
the volume of the vessel is reduced to one third of its original volume?
Q.7 For the reaction 3BrO—  BrO3— + 2Br— in an alkaline aquesous solution, the value of the second
— [BrO – ]
order (in BrO ) rate constant at 80°C in the rate law for – was found to be 0.056L mol–1s–1.
t
[BrO3– ] [Br – ]
What is the rate constant when the rate law is written for (a) , (b) ?
t t
Q.8 Dinitropentaoxide decomposes as follows :

1
N2O5(g)  2NO2(g) + O2(g)
2
Given that –d [N2O5] / dt = k1[N2O5]
d [NO2] / dt = k2[N2O5]
d [O2] / dt = k3[N2O5]
What is the relation between k1, k2 and k3?

Q.9 Suppose that the Sun consists entirely of hydrogen atom and releases the energy by the nuclear reaction,
4 11H  42 He with 26 MeV of energy released. If the total output power of the Sun is assumed to
remain constant at 3.9 × 1026 W, find the time it will take to burn all the hydrogen. Take the mass of the
Sun as 1.7 × 1030 kg.
Q.10 The reaction A(g) + 2B(g)  C(g) + D(g) is an elementary process. In an experiment, the initial
partial pressure of A & B are PA = 0.6 and PB = 0.8 atm. Calculate the ratio of rate of reaction relative
to initial rate when PC becomes 0.2 atm.
ZERO ORDER
Q.11 In the following reaction, rate constant is 1.2 × 10–2 M s–1 A  B. What is concentration of B after
10 and 20 min., if we start with 10 M of A.
Q.12 For the following data for the zero order reaction A  products. Calculate the value of k.
Time (min.) [A]
0.0 0.10 M
1.0 0.09 M
2.0 0.08 M
Q.13 The rate constant for a zero order reaction is 2 × 10–2 mol L–1sec–1, if the concentration of the reactant
after 25 sec is 0.25 M, calculate the initial concentration.
Q.14 A drop of solution (volume 0.10 ml) contains 6 × 10–6 mole of H+, if the rate constant of disappearance
of H+ is 1 × 107 mole litre–1 sec–1. How long would it take for H+ in drop to disappear?
Q.15 A certain substance A is mixed with an equimolar quantity of substance B. At the end of an hour A is 75%
reacted. Calculate the time when A is 10% unreacted. (Given: order of reaction is zero)
FIRST ORDER
Q.16 A first order reaction is 75% completed in 72 min.. How long time will it take for
(i) 50% completion (ii) 87.5% completion
Q.17 A first order reaction is 20% complete in 10 min. calculate (i) the specific rate constant , (ii) the time
taken for the reactions to go to 75% completion.
Q.18 Show that in case of unimolecular reaction, the time required for 99.9% of the reaction to take place in
ten times that required for half of the reaction.
Q.19 A drug is known to be ineffective after it has decomposed 30%. The original concentration of a
sample was 500 units/ml. When analyzed 20 months later, the concentration was found to be
420 units/ml. Assuming that decomposition is of I order, what will be the expiry time of the drug?
Q.20 A viral preparation was inactivated in a chemical bath. The inactivation process was found to be first
order in virus concentration. At the beginning of the experiment 2.0 % of the virus was found to be
inactivated per minute . Evaluate k for inactivation process.

Q.21 If a reaction A Products, the concentrations of reactant A are C0, aC0, a2C0, a3C0, ............. after
time interval 0, t, 2t, 3t, ............. where a is a constant. Given 0 < a < 1. Show that the reaction is of first
order. Also calculate the relation in k, a and t.
Q.22 The reaction SO2Cl2(g)  SO2(g) + Cl2(g) is a first order gas reaction with k =2.2 × 10–5 sec–1 at
320°C. What % of SO2Cl2 is decomposed on heating this gas for 90 min.
Q.23 Two substances A (t1/2= 5 mins) and B (t1/2 = 15 mins) follow first order kinetics are taken in such a way
that initially [A]= 4[B]. Calculate the time after which the concentration of both the substance will be
equal.
ORDER OF REACTION & RATE LAW

Q.24 At 800° C the rate of reaction
2 NO + H2  N2 + H2O
Changes with the concentration of NO and H2 are
1 d[ NO]
[NO] in M [H2] in M  in M sec–1
2 dt
(i) 1.5 × 10–4 4 × 10–3 4.4 × 10–4
(ii) 1.5 × 10–4 2 × 10–3 2.2 × 10–4
(iii) 3.0 × 10 –4 2 × 10–3 8.8 × 10–4
(a) What is the order of this reaction?
(b) What is the rate equation for the reaction?
(c) What is the rate when
[H2] = 1.5 ×10–3 M and [NO] = 1.1 × 10–3M?
Q.25 The catalytic decomposition of N2O by gold at 900°C and at an initial pressure of 200mm is 50%
complete in 53 minutes and 73% complete in 100 minutes.
(i) What is the order of the reaction?
(ii) Calculate the rate constant.
(iii) How much of N2O will decompose in 100 min. at the same temperature but at initial pressure of 600 mm?
Q.26 The pressure of a gas decomposing at the surface of a solid catalyst has been measured at different times
and the results are given below
t (sec) 0 100 200 300
Pr. (Pascal) 4 × 103 3.5 × 103 3 × 103 2.5 × 103
Determine the order of reaction, its rate constant.
Q.27 The half life period of decomposition of a compound is 50 minutes. If the initial concentration is halved,
the half life period is reduced to 25 minutes. What is the order of reaction?
CALCULATION OF RATE CONSTANT USING DIFFERENT PARAMETERS

Q.28 In this case we have
A B + C
Time t 
Total pressure of A + B+C P2 P3
Find k.

Q.29 A B + C
Time t 
Total pressure of ( B+C) P2 P3
Find k.
Q.30 S G + F
Time t 
Rotation of Glucose & Fructose rt r
Find k.
3
Q.31 The reaction AsH3(g) As(s) + H (g) was followed at constant volume at 310°C by measuring
2 2
the gas pressure at intervals Show from the following figures that reaction is of first order.
Time (in hrs) 0 5 7.5 10
Total pressure (in mm) 758 827 856 882
Q.32 The thermal decomposition of dimethyl ether as measured by finding the increase in pressure of the
reaction
(CH3)2O(g)  CH4(g) + H2(g) + CO(g)
at 500°C is as follows:
Time (sec.) 390 1195 3155 
Pressure increase (mm Hg) 96 250 467 619
the initial pressure of ether was 312 mm Hg. Write the rate equation for this reaction and determine
the rate constant of reaction.
Q.33 From the following data show that decomposition of H2O2 in aqueous solution is first order.
Time (in minutes) 0 10 20
Volume (in c.c. of KMnO4) 22.8 13.3 8.25
Q.34 The following data were obtained in experiment on inversion of cane sugar.
Time (minutes) 0 60 120 180 360 
Angle of rotation (degree) +13.1 + 11.6 + 10.2 +9.0 +5.87 –3.8
Show that the reaction is of first order. After what time would you expect a zero reading in
polarimeter?
Q.35 At 100°C the gaseous reaction A  2B + C was observed to be of first order. On starting with pure
A it is found that at the end of 10 minutes the total pressure of system is 176 mm. Hg and after a long time
270 mm Hg. From these data find (a) initial pressure of A (b) the pressure of A at the end of 10 minutes
(c) the specific rate of reaction and (d) the half life period of the reaction?
Q.36 The decomposition of N2O5 according to the equation 2 N2O5 (g)  4 NO2(g) + O2(g) is a first
order reaction. After 30 min. from start of decomposition in a closed vessel the total pressure
developed is found to be 284.5 mm Hg. On complete decomposition, the total pressure is
584.5 mm Hg. Calculate the rate constant of the reaction.

Q.37 A definite volume of H2O2 under going spontaneous decomposition required 22.8 c.c. of standard
permanganate solution for titration. After 10 and 20 minutes respectively the volumes of
permanganate required were 13.8 and 8.25 c.c.
(a) Find order of reaction. How may the result be explained?
(b) Calculate the time required for the decomposition to be half completed.
(c) Calculate the fraction of H2O2 decomposed after 25 minutes.
Q.38 The reaction given below, rate constant for disappearance of A is 7.48 × 10–3 sec–1. Calculate the time
required for the total pressure in a system containing A at an initial pressure of 0.1 atm to rise to 0.145 atm
and also find the total pressure after 100 sec.
2A (g) 4B(g) + C(g)
Q.39 The reaction A(aq) B (aq) + C (aq) is monitered by measuring optical rotation of reaction mixture
at different time interval. The species A, B and C are optically active with specific rotations 20°, 30° and
– 40° respectively. Starting with pure A if the value of optical rotation was found to be 2.5° after 6.93
minutes and optical rotation was –5° after infinite time. Find the rate constant for first order conversion
of A into B and C.
PARALLEL AND SEQUENTIAL REACTION
[ x ]t
Q.40 For a reaction , calculate value of ratio, at any given instant t.
[ y]  [ z ]
[C]
Q.41 k1 = x hr–1; k1 : k2 = 1 : 10. Calculate after one hour from the start of the reaction.
[ A]
Assuming only A was present in the beginning.
Q.42 How much time would be required for the B to reach maximum concentration for the reaction
k1 k2 ln 2 ln 2
A  B  C. Given k1 = , k2 = .
4 2
Q.43 For first order parallel reaction k1 and k2 are 8 and 2 min–1 respectively at
300 K. If the activation energies for the formation of B and C are respectively 20
and 28.314 kJ/mol respectively find the temperature at which B and C will
be obtained in molar ratio of 2 : 1.
[Given : ln 4 = 1.4 ]
TEMPERATURE DEPENDENCE OF RATE (ACTIVATION ENERGY)

Q.44 In gaseous reactions important for understanding the upper atmosphere, H2O and O react bimolecularly
to form two OH radicals. H for this reaction is 72 kJ at 500 K and Ea = 77 kJ mol–1, then calculate Ea
for the biolecular recombination of 2OH radicals to form H2O & O at 500 K
Q.45 The energy of activation of a first order reaction is 104.5 kJ mole–1 and pre – exponential factor (A) is
5 ×1013 sec–1. At what temperature, will the reaction have a half life of 1 minute?
Q.46 The specific rate constant for a reaction increases by a factor of 4, if the temperature is changed from
27°C to 47°C. Find the activation energy for the reaction.

Q.47 The energy of activation and specific rate constant for a first order reaction at 25°C are 100 kJ/ mole and
3.46 × 10–5 sec–1 respectively. Determine the temperature at which half life of the reaction is 2 hours.
Q.48 A catalyst lowers the activation energy for a certain reaction from 75 kJ to 25 kJ mol–1. What will be the
effect on the rate of reaction at 25°C, other things being equal.
Q.49 Given that the temperature coefficient for the saponification of ethyl acetate by NaOH is 1.75. Calculate
activation energy for the saponification of ethyl acetate.
Q.50 At 380°C, the halflife period for the first order decomposition of H 2O2 is 360 min.The energy of
activation of the reaction is 200 kJ mol1. Calculate the time required for 75% decomposition at 4500C.
Q.51 The Arrhenius equation for two first order equation

A  B and C  D is given by
k1 = 1012 e 81.28( kJ ) / RT
k2 = 1011 e 43.10( kJ ) / RT
At what temperature k1 becomes equal to k2. The unit of activation energy is kJ/mol
Use: ln 10 = 2.3 and R = 8.3 J/K/mol
MECHANISM OF REACTION
Q.52 The reaction 2NO + Br2  2NOBr, is supposed to follow the following mechanism
(i) NO + Br2 NOBr2 (ii) NOBr2 + NO slow
  2NOBr
Suggest the rate law expression.
Q.53 For the reaction 2H2 + 2NO N2 + 2H2O, the following mechanism has been suggested:
2NO  N2O2 equilibrium constant K1 (fast)
k2
N2O2 + H2  N2O+ H2O (slow)
k3
N2O + H2  N2 + H2O (fast)
Establish the rate law for given reaction.
Q.54 Reaction between NO and O2 to form NO2 is 2NO + O2  2NO2 follows the following mechanism
k1
NO + NO N2O2 ( in rapid equilibrium)
k–1
k2
N2O2 + O2  2NO2 (slow)
1  d[ NO 2 ] 
Show that the rate of reaction is given by 2  dt  = K[NO]2[O2]
Q.55 Deduce rate law expressions for the conversion of H2 and I2 to HI at 400°C corresponding to each
of the following mechanisms:
(a) H2 + I2  2HI (one step) (b) I2  2I
2I + H2  2HI (slow)
(c) I2  2I
I + H2  IH2
IH2 + I  2HI (slow)
(d) Can the observed rate law expression rate = k[H2][I2] distinguish among these mechanisms?
(e) If it is known that ultraviolet light causes the reaction of H2 and I2 to proceed at 200°C with the
same rate law expression, which of these mechanisms becomes most improbable?

PROFICIENCY TEST
Q.1 Fill in the blanks with appropriate items :
1. For collision to be effective the energy possessed by the colliding molecules should be equal to or
greater than the ____________.
2. In the reaction, H2 + I2  2HI, the rate of disappearance of H2 is _______ the rate of appearance
of HI.
3. For an endothermic process, the minimum value of activation energy can be _______.
4. The rate of a reaction is ________ to the collision frequency.
5. The rate constant for the zero order reaction has the dimensions___________.
6. The reactions with molecularity more than three are _________.
7. A catalyst increases the rate of the reaction by__________ activation energy.
8. If activation energy of reaction is low, it proceeds at _______ rate.
9. In a multistep reaction, the ________ step is rate determining.
10. Rate constant of a reaction __________ with increase in temperature.
11. The ratio t7/8 / t1/2 for a first order reaction would be equal to _________.
12. For a zero order reaction, the rate of the reaction is equal to the ______ of the reaction.
13. The value of temperature coefficient is generally between _________.
14. For a certain reaction, xM  yL, the rate of reaction increases by 4 times when the concentration of
M is doubled. The rate law is _________.
15. The rate equation r = k [A][B]1/2 suggests that order of overall reaction is _______.
16. A plot of [A] vs t for a certain reaction A  B with r = k [A]0 will be a straight line with slope equal
to ________.
17. [Eactivated complex – Ereactants] = ____________.
18. In the Arrhenius equation k = Aexp (–E/RT), A may be termed as the rate constant at __________.
19. For a ______ order reaction the half-life (t1/2) is independent of the initial conc. of the reactants.
20. For a first order reaction A  P, a graph of log [A] vs t has a slope equal to __________.

Q.2 True or False Statements :
1. Order of a reaction can be written from the balanced chemical equation.
2. In a complex reaction the rate of overall reaction is governed by the slowest step.
3. If t1/2 for a first order reaction is 6.93 s, the value of rate constant for the reaction would be 10s–1.
4. Molecularity of a reaction is always whole number.
5. Order and molecularity of a single step reaction may or may not be same.
6. The activation energy of a catalysed reaction is more than the activation energy of the uncatalysed
reaction.
7. For a zero order reaction t3/4 is related to t1/2 as t3/4 = 1.5 t1/2
8. The rate of an exothermic reaction increases with the rise in temperature.
9. Partial orders are never negative.
10. Order of reaction may be change with change in practical conditions
11. The rate of reaction is uniform in zero order reaction
12. The rate law of the elementary reaction; 3A  B must be r = k [A]3
13. If the partial orders are equal to corresponding coefficients in the balanced reaction, the reaction must
be elementary.
14. Every species that appears in the rate law of reaction must be a reactant or product in that reaction.
15. Molecularity defined only for RDS.
16. Product can form only when the required orientation and energy conditions are met.
17. Activated complex is always an intermediate product.
18. The pre-exponential factor A has the same units for all reactions.
19. All collisions between reactants yield the desired product.
20. If the partial orders differ from the coefficients in the balanced reaction, the reaction must be complex.

EXERCISE -II
Q.1 A solution of A is mixed with an equal volume of a solution of B containing the same number of moles,
and the reaction A+B=C occurs. At the end of 1h, A is 75 % reacted. How much of A will be left
unreacted at the end of 2 h if the reaction is (a) first order in A and zero order in B; (b) first order in both
A and B ; and (c) zero order in both A and B ?
Q.2 The reaction CH3CH2NO2 + OH–  CH3CHNO2 + H2O obeys the rate law for pseudo first
order kinetics in the presence of a large excess of hydroxide ion. If 1% of nitro ethane undergoes reaction
in half a minute when the reactant concentration is 0.002 M, What is the pseudo first order rate constant?
Q.3 The decomposition of a compound P, at temperature T according to the equation

2P(g)  4Q(g) + R(g) + S(l)
is the first order reaction. After 30 minutres from the start of decomposition in a closed vessel, the total
pressure developed is found to be 317 mm Hg and after a long period of time the total pressure observed
to be 617 mm Hg. Calculate the total pressure of the vessel after 75 mintute, if volume of liquid S is
supposed to be negligible. Also calculate the time fraction t7/8.
Given : Vapour pressure of S (l) at temperature T = 32.5 mm Hg.
Q.4 Hydrogen peroxide solution was stored in a mild steel vessel. It was found, however, that the hydrogen
peroxide decomposed on the walls of the vessel (a first order reaction). An experiment with 100 ml of a
solution gave 10.31 ml oxygen (corrected to 1 atm & 273 K) after 5.1 days. Find how long the peroxide
can be stored before the loss of 20.00 ml oxygen occurs (per 100 ml solution) under similar storage
conditions. if complete decomposition of the sample to H2O2 gave 46.34 ml oxygen.
Q.5 Decomposition of H2O2 is a first order reaction. A solution of H2O2 labelled as 20 volumes was left
open. Due to this, some H2O2 decomposed. To determine the new volume strength after 6 hours, 10 mL
of this solution was diluted to 100mL. 10mL of this diluted solution was titrated against 25mL of 0.025M
KMnO4 solution under acidic conditions. Calculate the rate constant for decomposition of H2O2.
Q.6 A metal slowly forms an oxide film which completely protects the metal when the film thickness is
3.956 thousand ths of an inch. If the film thickness is 1.281 thou. in 6 weeks, how much longer will it be
before it is 2.481 thou.? The rate of film formation follows first order kinetics.
Q.7 An optically active compound A upon acid catalysed hydrolysis yield two optically active compound B
and C by pseudo first order kinetics. The observed rotation of the mixture after 20 min was 5° while
after completion of the reaction it was – 20°. If optical rotation per mole of A, B & C are 60°, 40° &
– 80°. Calculate half life of the reaction.
Q.8 A vessel contains dimethyl ether at a pressure of 0.4 atm. Dimethyl ether decomposes as
CH3OCH3(g)  CH4(g) + CO(g) + H2(g). The rate constant of decomposition is 4.78×103 min1.
Calculate the ratio of initial rate of diffusion to rate of diffusion after 4.5 hours of initiation of decomposition.
Q.9 At room temperature (20°C) orange juice gets spoilt in about 64 hours. In a referigerator at 3°C juice
can be stored three times as long before it gets spoilt. Estimate (a) the activation energy of the reaction
that causes the spoiling of juice. (b) How long should it take for juice to get spoilt at 40°C?
Q.10 A first order reaction, A  B, requires activation energy of 70 kJ mol1. When a 20% solution of A was
kept at 25°C for 20 minutes, 25% decomposition took place. What will be the percent decomposition
in the same time in a 30% solution maintianed at 40°C? Assume that activation energy remains constant
in this range of temperature.

Q.11 Two reations (i) A  products (ii) B  products, follow first order kinetics. The rate of the reaction
(i) is doubled when the temperature is raised from 300 K to 310K. The half life for this reaction at 310K
is 30 minutes. At the same temperature B decomposes twice as fast as A. If the energy of activation for
the reaction (ii) is half that of reaction (i), calculate the rate constant of the reaction (ii) at 300K.
Q.12 A certain organic compound A decomposes by two parallel first order mechanism
If k1 : k2 = 1 : 9 and k1 = 1.3 × 10–5 s–1.

Calculate the concentration ratio of C to A, if an experiment is started with only A and allowed to run for
one hour.
Q.13 The reaction

cisCr(en)2(OH)+2 transCr(en)2(OH)+2
is first order in both directions. At 25°C the equilibrium constant is 0.16 and the rate constant k 1 is
3.3 × 10 4s 1. In an experiment starting with the pure cis form, how long would it take for half the
equilibrium amount of the trans isomer to be formed ?
Q.14 For a reversible firstorder reaction A B
k1 = 10 2 s 1 and [B]eq /[A] eq = 4. If [A]0 = 0.01 mole L 1 and [B]0 = 0, what will be the concentration
of B after 30 s ?
Q.15 For the system A(g)  B(g), H for the forward reaction is –33 kJ/mol (Note : H = E in this case).
[B]
Show that equilibrium constant K = = 5.572 × 105 at 300 K. If the activation energies Ef & Eb are
[A]
in the ratio 20 : 31, calculate Ef and Eb at this temperature. Assume that the pre-exponential factor is the
same for the forward and backward reactions.
Q.16 The complex [Co(NH3)5F]2+ reacts with water according to the equation.
[Co(NH3)5F]2+ + H2O  [Co(NH3)5(H2O)]3+ + F
The rate of the reaction = rate const. x[complex]ax[H+]b. The reaction is acid catalysed i.e. [H+] does
not change during the reaction. Thus rate = k[Complex]a where k’ = k[H+]b, calculate ‘a’ and ‘b’ given
the following data at 250C.
[Complex]M [H+]M T1/2hr T3/4hr
0.1 0.01 1 2
0.2 0.02 0.5 1
k1 k2
Q.17 For the two parallel reactions A  B and A  C, show that the activation energy E for the
disappearance of A is given in terms of activation energies E1 and E2 for the two paths by
k1E 1  k 2 E 2
E =
k1  k 2
k1 k
Q.18 For the mechanism A+B k
C ; C  3
D
2
(a) Derive the rate law using the steady-state approximation to eliminate the concentration of C.
(b) Assuming that k3 << k2, express the pre-exponential factor A and Ea for the apparent second-order rate
constant in terms of A1, A2 and A3 and Ea1, Ea2 and Ea3 for the three steps.

Q.19 The reaction of formation of phosgene from CO and Cl2 is CO + Cl2  COCl2
The proposed mechanism is
(i) Cl2 2Cl (fast equilibrium) (ii) Cl + CO COCl (fast equilibrium)
(iii) COCl + Cl2 K 3 COCl2 + Cl (slow)
d[COCl 2 ]
Show that the above mechanism leads to the following rate law =K[CO][Cl2]3/2.
k 1/ 2 dt
Where K = k3. 2  1  .
k
k 2  k  1 
Q.20 For the following first order gaseous reaction
The initial pressure in a container of capacity V litres is 1 atm. Pressure at time t = 10 sec is 1.4 atm and
after infinite time it becomes 1.5 atmosphere. Find the rate constant k 1 and k2 for the appropriate
reactions.

EXERCISE -III
Single correct
Q.1 The rate of a reaction is expressed in different ways as follows :
1 d[C] 1 d[ D] 1 d[ A ] d[ B]
   
2 dt 3 dt 4 dt dt
The reaction is:
(A) 4 A + B  2C + 3D (B) B + 3 D  4 A + 2 C
(C) A + B  C + D (D) B + D A + C
Q.2 For the reaction A + B  C; starting with different initial concentration of A and B, initial rate of
reaction were determined graphically in four experiments.
–1
S.No. [A]0/M (Initial conc.) [B]0/M (Initial conc.) rate/(M sec )
–3 –2 –3
1 1.6 × 10 5 × 10 10
–3 –2 –3
2 3.2 × 10 5 × 10 4 × 10
–3 –1 –3
3 1.6 × 10 10 2 × 10
–3 –1 –3
4 3.2 × 10 10 8 × 10
Rate law for reaction from above data is
(A) r = k[A]2 [B]2 (B) r = k[A]2 [B] (C) r = k[A] [B]2 (D) r = k[A] [B]
Q.3 The rate law for a reaction between the substances A and B is given by
rate = k [A]n [B]m
On doubling the concentration of A and halving the concentration of B, the ratio of the new rate to the
earlier rate of the reaction will be as
(A) 2 (n–m) (B) 1 / 2 (m+n) (C) (m + n) (D) (n – m)
Q.4 For the reaction system 2NO (g) + O2 (g)  2NO2 (g) volume is suddenly reduced to half of its
value by increasing the pressure on it. If the reaction is first order with respect to O2 and second order
with respect to NO, the rate of reaction will
(A) increase to four times of its initial value (B) diminish to one-fourth of its initial value
(C) diminish to one-eight of its initial value (D) increase to eight times of its initial value
Q.5 In a first order reaction, the concentration of the reactant, decreases from 0.8 to 0.4 M in 15 minutes.
The time taken for the concentration to change from 0.1 M to 0.025 M is
(A) 30 minutes (B) 15 minutes (C) 7.5 minutes (D) 60 minutes
Q.6 The rate equation for the reaction 2A + B  C is found to be : rate = k [A] [B]. The correct statement
in relation to this reaction is
(A) unit of k must be s–1
(B) t1/2 is a constant
(C) rate of formation of C is twice the rate of disappearance of A
(D) value of k is independent of the initial concentrations of A and B.
Q.7 t1/4 can be taken as the time taken for the concentration of a reactant to drop to 3/4 of its value. If the
rate constant for a first order reaction is k, the t1/4 can be written as [ln2 = 0.695, ln3 = 1.1]
(A) 0.69 / k (B) 0.75 / k (C) 0.10 / k (D) 0.29 / k

Q.8 A reaction was found to be second order with respect to the concentration of carbon monoxide. If the
concentration of carbon monoxide is doubled, with everything else kept the same, the rate of reaction will
(A) Double (B) remain unchanged (C) Triple (D) Increase by a factor of 4
Q.9 The energies of activation for forward and reverse reactions for A2 + B2 2AB are 180 kJ mol–1
–1
and 200 kJ mol respectively. The presence of catalyst lowers the activation energies of both (forward
and reverse) reactions by 100 kJ mol–1. The magnitude of enthalpy change of the reaction
(A2 + B2  2AB) in the presence of catalyst will be (in kJ mol–1).
(A) 300 (B) 120 (C) 20 (D) –20
Q.10 Which graph represents zero order reaction [A(g)  B(g)] :
d[B] t1/2 t3/4

[B] dt
(A) (B) (C) (D)
t t [A]0
[A]0
Q.11 For a hypothetical reaction,

A + 3B  P H = –2 x kJ/mole of A
& M  2Q + R H = + x kJ/mole of M
If these reactions are carried simultaneously in a reactor such that temperature is not changing. If rate of
disappearance of B is y M sec–1 then rate of formation (in M sec–1) of Q is :
2 3 4 3
(A) y (B) y (C) y (D) y
3 2 3 4
Q.12 Gaseous reaction A  B + C follows first order kinetics. Concentration of A changes from 1 M to
0.25 M in 138.6 minutes. Find the rate of reaction when concentration of A is 0.1 M.
(A) 2×10–3 M min–1 (B) 10–3 M min–1 (C) 10–4 M min–1 (D) 5 × 10–4 M min–1
Q.13 The initial rate of zero order reaction of the gaseous reaction A(g)  2B(g) is 10–2 M min–1. If the
initial concentration of A is 0.1 M, what would be the concentration of B after 60 sec.?
(A) 0.09 M (B) 0.01 M (C) 0.02 M (D) 0.002 M
Q.14 Consider the following first order competing reactions:

k1 k
X  A + B and Y  2
C+D
if 50% of the reaction of X was completed when 96% of the reaction of Y was completed, the ratio of
their rate constants (k2/k1) is
(A) 4.06 (B) 0.215 (C) 1.1 (D) 4.65

Q.15 Consider the reaction A  B, graph between half life (t1/2) and initial concentration (a) of the
reactant is
t1/2
a
d[A ]
Hence graph between  and time will be
dt
d[A ] d[A ]
(A)  (B) 
dt dt
t
d[A ] d[A ]
(C)  (D) 
dt dt
t t
Q.16 At certain temperature, the half life period for the thermal decomposition of a gaseous substance depends
on the initial partial pressure of the substance as follows
P(mmHg) 500 250
t1 2 (in min.) 235 950
Find the order of reaction [Given log (23.5) = 1.37 ; log (95) = 1.97; log 2 = 0.30]
(A) 1 (B) 2 (C) 2.5 (D) 3
Q.17 Consider the reaction :
A  B + C
Initial concentration of A is 1 M. 20 minutes time is required for completion of 20 % reaction.
d[ B]
If = k[A], then half life (t1/2 ) is
dt
(A) 55.44 min. (B) 50 min (C) 62.13 min (D) None of these
Q.18 If decomposition reaction A (g)  B (g) follows first order kinetics then the graph of rate of formation
(R) of B against time t will be
(A) (B) (C) (D)

Q.19 For the first order decomposition of SO2Cl2(g),
SO2Cl2(g)  SO2(g) + Cl2(g)
a graph of log (a0 – x) vs t is shown in figure. What is the rate constant (sec–1)?
Time (min) 
2 4 6 8 10
(0,0)
| | | | |
log (a0 – x)
-1–
-2–
-3–
(A) 0.2 (B) 4.6 × 10–1 (C) 7.7 × 10–3 (D) 1.15 × 10–2
Q.20 The rate constant for the forward reaction A (g)  2B(g) is 1.5 × 10–3 s–1 at 100 K. If 10–5 moles of
A and 100 moles of B are present in a 10 litre vessel at equilibrium then rate constant for the
backward reaction at this temperature is
(A) 1.50× 104 L mol–1 s–1 (B) 1.5 × 1011 L mol–1 s–1
(C) 1.5 × 1010 L mol–1 s–1 (D) 1.5 × 10–11L mol–1 s–1
1 1

Q.21 Reaction A + B  C + D follows following rate law : rate = k [A] 2 [ B] 2 . Starting with initial conc.
of 1 M of A and B each, what is the time taken for concentration of A of become 0.25 M.
Given : k = 2.303 × 10–3 sec–1.
(A) 300 sec. (B) 600 sec. (C) 900 sec. (D) 1200 sec.
Q.22 The variation of concentration of A with time in two experiments starting with two different initial
concentration of A is given in the following graph. The reaction is represented as A(aq) B(aq).
What is the rate of reaction (M/min) when concentration of A in aqueous solution was 1.8 M?
(A) 0.072 M min–1

Concentration(M) 
1.5
(B) 0.036 M min–1

1.2
(C) 0.08 M min–1 1
0.8 Experiment-1
(D) 1 M min–1 0.6 Experiment-2
5 10 15 20
time(min.) 
Q.23 In respect of the equation k = A exp (– Ea / RT), which one of the following statements is correct?
(A) R is Rydberg's constant
(B) k is equilibrium constant
(C) A is adsorption factor
(D) Ea is the energy of activation

Q.24 Rate of a reaction can be expressed by Arrhenius equation as :
k = Ae–E/RT
In this equation, E represents
(A) The fraction of molecules with energy greater than the activation energy of the reaction
(B) The energy above which all the colliding molecules will react
(C) The energy below which colliding molecules will not react
(D) The total energy of the reacting molecules at a temperature, T
Q.25 The rate constant, the activation energy and the Arrhenius parameter (A) of a chemical reaction at 25°C are
3.0 × 10–22 s–1, 104.4 kJ mol–1 and 6.0 × 1014s–1 respectively. The value of the rate constant at T   is
(A) 2.0 × 1018 s–1 (B) 6.0 × 1014 s–1
(C) infinity (D) 3.6 × 1030 s–1
Q.26 A first order reaction is 50% completed in 20 minutes at 27°C and in 5 min at 47°C. The energy of
activation of the reaction is
(A) 43.85 kJ/mol (B) 55.14 kJ/mol (C) 11.97 kJ/mol (D) 6.65 kJ/mol
Q.27 For the first order reaction A — B + C, carried out at 27 ºC if 3.8 × 10–16 % of the reactant molecules
exists in the activated state, the Ea (activation energy) of the reaction is [log 3.8 = 0.58]
(A) 12 kJ/mole (B) 831.4 kJ/mole
(C) 100 kJ/mole (D) 88.57 kJ/mole
Q.28 In a reaction carried out at 400 K, 0.0001% of the total number of collisions are effective. The energy of
activation of the reaction is
(A) zero (B) 7.37 k cal/mol (C) 9.212 k cal/mol (D) 11.05 k cal/mol
Q.29 The following mechanism has been proposed for the exothermic catalyzed complex reaction.
k k2
A+ B I AB  1 AB + I  P+A
If k1 is much smaller than k2. The most suitable qualitative plot of potential energy (P.E.) versus reaction
coordinate for the above reaction.
(A) (B) (C) (D)
Q.30 The following mechanism has been proposed for the reaction of NO with Br2 to form NOBr :
NO(g) + Br2(g) NOBr2(g)
NOBr2(g) + NO(g)  2NOBr(g)
If the second step is the rate determining step, the order of the reaction with respect to NO(g) is
(A) 2 (B) 1 (C) 0 (D) 3

Q.31 Choose the correct set of identifications.
(1) (2) (3) (4)

(A) E for Ea for Eoverall Ea for
E + S  ES ES  EP for S  P EP  E + P
(B) Ea for E for Ea for overall
E + S  ES E + S  ES ES  EP for S  P
(C) Ea for Ea for Eoverall E for
ES  EP EP  E + P for S  P EP  E + P
(D) Ea for Ea for Ea for Eoverall
E + S  ES ES  EP EP  E + P for S  P
(E) E for Eoverall E for l Ea for
E + S  ES for S  P EP  E + P EP  E + P

d[A ]
Q.32 For the reaction A  B, the rate law expression is  d t = k [A]1/2. If initial concentration of [A] is
[A]0, then
2 1/ 2
(A) The integerated rate expression is k = (A  A1 / 2 )
t 0
(B) The graph of A Vs t will be
K
(C) The half life period t1 / 2 =
2[A]10/ 2
[A]0
(D) The time taken for 75% completion of reaction t 3 / 4 =
k
Q.33 Consider the reaction, –1

0 mi
–2 n B
.93×1
k 1=6
A
k2 =1
3 .8 6 ×
10 –2m
C in –1
A, B and C all are optically active compound . If optical rotation per unit concentration of A, B and C are
60°, –72°, 42° and initial concentration of A is 2 M then select write statement(s).
(A) Solution will be optically active and dextro after very long time
(B) Solution will be optically active and levo after very long time
(C) Half life of reaction is 15 min
(D) After 75% conversion of A into B and C angle of rotation of solution will be 36°.
Q.34 Select incorrect statement(s):
(A) Unit of pre-exponential factor (A) for second order reaction is mol L–1 s–1.
(B) A zero order reaction must be a complex reaction.
(C) Molecularity is defined only for RDS in a complex reaction.
(D) Decay constant () of radioactive substance is affected by temperature.
Q.35 Which of the following is/are correct statement?

(A) Stoichiometry of a reaction tells about the order of the elementary reactions.
(B) For a zero order reaction, rate and the rate constant are identical.
(C) A zero order reaction is controlled by factors other than concentration of reactants.
(D) A zero order reaction is always elementary reaction.
Q.36 Which of the following statement is incorrect?

(A) The order of reaction is the sum of powers of all the concentration terms in the rate equation.
(B) The order of reaction with respect to one reactant is the ratio of the change of logarithm of the rate
of the reaction to the change in the logarithm of the concentration of the particular reactant, keeping the
concentrations of all other reactants constant.
(C) Orders of reactions can not be fractional.
(D) The order of a reaction can only be determined from the stoichiometric equation for the reaction.
Q.37 Statement-1 : A fractional order reaction must be a complex reaction.

Statement-2 : Fractional order of RDS equals to overall order of a complex reaction.
Q.38 Statement-1 : The time of completion of reactions of type A  product (order <1) may be
determined.
Statement-2 : Reactions with order  1 are either too slow or too fast and hence the time of
completion can not be determined.
Q.39 Statement-1 : Temperature coefficient of an one step reaction may be negative.

Statement-2 : The rate of reaction having negative order with respect to a reactant decreases
with the increase in concentration of the reactant.

Q.40 Statement-1 : The overall rate of a reversible reaction may decrease with the increase in
temperature.
Statement-2 : When the activation energy of forward reaction is less than that of backward
reaction, then the increase in the rate of backward reaction is more than that of
forward reaction on increasing the temperature.
Q.41 Statement-1 : In a reversible endothermic reaction, Eact of forward reaction is higher than that
of backward reaction
Statement-2 : The threshold energy of forward reaction is more than that of backward reaction
Q.42 Statement-1 : A catalyst provides an alternative path to the reaction in which conversion of
reactants into products takes place quickly
Statement-2 : The catalyst forms an activated complex of lower potential energy, with the
reactants by which more number of molecules are able to cross the barrier per
unit of time.
Comprehension
Oxidation of metals is generally a slow electrochemical reaction involving many steps. These steps involve
electron transfer reactions. A particular type of oxidation involve overall first order kinetics with respect
to fraction of unoxidised metal (1– f ) surface thickness relative to maximum thickness (T) of oxidised
surface, when metal surface is exposed to air for considerable period of time
df
Rate law : = k(1 – f ), where f = x/T,,
dt
x = thickness of oxide film at time 't'
& T = thickness of oxide film at t = 
A graph of ln(1 – f ) vs t is shown in the adjacent figure.
Q.43 The time taken for thickness to grow 50% of 'T' is

(A) 23.1 hrs (B) 46.2 hrs (C) 100 hrs (D) 92.4 hrs
Q.44 The exponential variation of 'f' with t(hrs) is given by

3t / 200 3t / 200 3t / 200
(A) [1  e 3t / 200 ] (B) e 1 (C) e (D) e

k1 1
For a hypothetical elementary reaction where 
k2 2
Initially only 2 moles of A are present.
Q.45 The total number of moles of A, B & C at the end of 50% reaction are
(A) 2 (B) 3 (C) 4 (D) 5
Q.46 Number of moles of B are
(A) 2 (B) 1 (C) 0.666 (D) 0.333
A reaction is said to be first order if it's rate is proportional to the concentration of reactant. Let us
consider a reaction
A(g)  B(g) + C(g)
At t = 0 a 0 0
At time t a–x x x
dx
The rate of reaction is given by the expression = k(a – x) and integrated rate equation for a given
dt
1  a 
reaction is represented as k = ln   where a = initial concentration and (a – x) = concentration
t ax
of A after time t.
Q.47 Thermal decomposition of compound X is a first order reaction. If 75% of X is decomposed in 100
min. How long will it take for 90% of the compound to decompose?
Given : log 2 = 0.30
(A) 190 min (B) 176.66 min (C) 166.66 min (D) 156.66 min
Q.48 Consider a reaction A(g)  3B(g) + 2C(g) with rate constant 1.386 × 10–2 min–1. Starting with
2 moles of A in 12.5 litre vessel initially, if reaction is allowed to takes place at constant pressure & at
298K then find the concentration of B after 100 min.
(A) 0.04 M (B) 0.36 M (C) 0.09 M (D) None of these
Paragraph for Question Nos. 49 to 51

The gaseous reaction : n1A (g)  n2B (g) is first order with respect to A. The true rate constant of
reaction is k. The reaction is studied at a constant pressure and temperature. Initially, the moles of A
were 'a' and no B were present.
Q.49 How many moles of A are present at time, t?
(A) a · e–kt (B) a · e  n1kt (C) a · e  n 2 kt (D) a (1  e  n1kt )
Q.50 If the initial volume of system were v0, then the volume of system after time, t, will be
n 1v 0 n 2 v0
(A) n (B) n
2 1
 n 2  n 2   n1kt   n 2  n 2   n1kt 
(C) v 0  n  1  n  · e  (D) v 0  n   n  1 · e 
 1  1    1  1  

Q.51 What will be the concentration of A at time t, if n1 = 1 and n2 = 2?
 e  kt   e  kt 
(A) [A0] · e–kt (B) 0 
[ A ]  kt

 (C) 0 
[ A ]  kt

 (D) [A0] (1–2 · e–kt )
 2e  1 e 

For the given sequential reaction
k1 k2
A  B  C
the concentration of A, B & C at any time 't' is given by
k1[A ]0
[A]t = [A]0 e  k1t ; 
[B]t = (k  k ) e  k1t  e  k 2 t
2 1

[C]t = [A0] – ( [A]t + [B]t )
Q.52 The time at which concentration of B is maximum is

k1 1 k1 1 k1 k2
(A) k  k (B) k  k ln k (C) k  k ln k (D) k  k
2 1 2 1 2 1 2 2 2 1
Q.53 Select the correct option if k1 = 1000 s–1 and k2 = 20 s–1.
[C]t
Conc.
[C]t
conc.
(A) [B]t (B)

[B] t [A]t
[A]t
time time
[C]t [C]t
Conc.
Conc.
[B] t [B]t
(C) (D)
[A] t [A] t
time time

Q.54 For the reaction of type A(g)  2B(g)
Column-I contains four entries and column-II contains four entries. Entry of column-I are to be matched
with ONLY ONE ENTRY of column-II
Column I Column II
d[ B]  d[A ]
(A) vs for first order (P)
dt dt
(B) [A] vs t for first order (Q)
(C) [B] vs t for first order (R)
(D) [A] vs t for zero order (S)
Q.55 Column-I and column-II. Entry of column-I are to be matched with ONE OR MORE THAN ONE
ENTRIES of column-II and vice versa.
Column I Column II
(Graphs reaction A Products) (Co-ordinates)
(A) (P) ln [A] (y-axis), t (x-axis) (order = 1)
(B) (Q) t1/2 (y-axis), [A0] (x-axis) (order = 1)
(C) (R) r (y-axis), t (x-axis) (order = 0)
(D) (S) t1/2 (y-axis), [A0] (x-axis) (order > 1)
(T) r (y-axis), [A] (x-axis) (order = 1)

EXERCISE-IV
OBJECTIVE PROBLEM
Q.1 Which of the following statement(s) is (are) correct
(A) A plot of log Kp versus 1/T is linear
(B) A plot of log [X] versus time is linear for a first order reaction, X  P
(C) A plot of log P versus 1/T is linear at constant volume.
(D) A plot of P versus 1/V is linear at constant temperature. [JEE 1999]
Q.2 The rate constnat for the reaction [JEE SCR 2000]
2N2O5  4NO2+O2
is 3.0 × 10–5 sec–1. if the rate is 2.4 × 10–5 mol litre–1 sec–1, then the concentration of N2O5
(in mol litre–1 ) is
(A) 1.4 (B) 1.2 (C) 0.004 (D) 0.8
Q.3 If I is the intensity of absorbed light and C is the concentration of AB for the photochemical proces
AB + hv  AB*, the rate of formation of AB* is directly proportional to [JEE SCR 2001]
(A) C (B) I (C) I2 (D) CI
Q.4 Consider the chemical reaction, N2(g) + 3H2(g)  2NH3(g). The rate of this reaction can be expressed
in term of time derivative of concentration of N2(g), H2(g) or NH3 (g). Identify the correct relationshiop
amongst the rate expressions. [JEE SCR 2002]
(A) Rate = – d[N2]/dt = – 1/3 d[H2]/dt = 1/2d[NH3]/dt
(B) Rate = – d[N2]/dt = – 3 d[H2]/dt = 2d[NH3]/dt
(C) Rate = d[N2]/dt = 1/3 d[H2]/dt =1/2d[NH3]/dt
(D) Rate = – d[N2]/dt = – d[H2]/dt = d[NH3]/dt
Q.5 In a first order reaction the concentration of reactant decreases from 800 mol/dm3 to 50 mol/dm3 in
2 × 104 sec. The rate constant of reaction in sec–1 is [JEE SCR 2003]
4 –5 –4
(A) 2 × 10 (B) 3.45 × 10 (C) 1.3486 × 10 (D) 2 × 10–4
Q.6 The reaction, X  Product follows first order kinetics. In 40 minutes the concentration of X changes
from 0.1 M to 0.025 M. Then the rate of reaction when concentration of X is 0.01 M
(A) 1.73 × 10 –4 M min –1 (B) 3.47 × 10 –5 M min –1
(C) 3.47 × 10 –4 M min –1 (D) 1.73 × 10 –5 M min –1 [JEE SCR 2004]
Q.7 Which of the following statement is incorrect about order of reaction? [JEE 2005]
(A) Order of reaction is determined experimentally
(B) It is the sum of power of concentration terms in the rate law expression
(C) It does not necessarily depend on stoichiometric coefficients
(D) Order of the reaction can not have fractional value.
Q.8 Consider a reaction aG + bH  Products. When concentration of both the reactants G and H is
doubled, the rate increases by eight times. However, when concentration of G is doubled keeping the
concentration of H fixed, the rate is doubled. The overall order of the reaction is [JEE 2006]
(A) 0 (B) 1 (C) 2 (D) 3

Q.9 Under the same reaction conditions, initial concentration of 1.386 mol dm–3 of a substance becomes half
 k1 
in 40 seconds and 20 seconds through first order and zero order kinetics, respectively. Ratio   of
 k0 
the rate constants for first order (k1) and zero order (k0) of the reactions is [JEE 2008]
–1
(A) 0.5 mol dm 3 (B) 1.0 mol dm –3 (C) 1.5 mol dm –3 (D) 2.0 mol dm3
–1
Q.10 Plots showing the variation of the rate constant (k) with temperature (T) are given below. The plot that
follows Arrhenius equation is [JEE 2010]
k k k k
(A) (B) (C) (D)
T T T T
SUBJECTIVE PROBLEM
Q.1 The rate constant for an isomerisation reaction A  B is 4.5 × 10–3 min–1. If the initial concentration of
A is 1 M. Calculate the rate of the reaction after 1 h. [JEE 1999]
Q.2 A hydrogenation reaction is carried out at 500 K. If the same reaction is carried out in the presence of a
catalyst at the same rate, the temperature required is 400 K. Calculate the activation energy of the
reaction if the catalyst lowers the activation barrier by 20 kJmol–1. [JEE 2000]
Q.3 The rate of a first order reaction is 0.04 mole litre–1 s–1 at 10 minutrs and 0.03 mol litre–1 s–1 at 20 minutes
after initiation. Find the half life of the reaction. [JEE 2001]
Q.4 2X(g)  3Y(g) + 2Z(g)

Time (in Min) 0 100 200
Partial pressure of X 800 400 200
(in mm of Hg)
Assuming ideal gas condition. Calculate
(a) Order of reaction (b) Rate constant
(c) Time taken for 75% completion of reaction (d) Total pressure when PX = 700 mm. [JEE 2005]
Q.5 The concentration of R in the reaction R  P was measured as a function of time and the following data
is obtained:
[R ](molar) 1.0 0.75 0.40 0.10
t (min .) 0.0 0.05 0.12 0.18
The order of the reaction is: [JEE 2010]

COMPREHENSION
Comprehension # 1
A(g)  2B(g) + C(g)
Initially at t = 0 gas A was present along with some amount of gas C. At t = 0 mole fraction of gas C is
1/3. After some time t = t1, total pressure is half of the final total pressure at t = tx (a very long time). Assume
this decomposition is a first order, at a constant temperature. It is also given at t = t x, final total pressure is
35 bar.
1. At t = t1 pressure of gas B is :

(A) 2.5 bar (B) 1.25 bar (C) 5.0 bar (D) data is insufficient
2. Rate constant (k) = (log 64 – log 49) s–1. Value of t1 in seconds is :
(A) 2.15 s (B) 1.5 s (C) 2.3 s (D) 1.15 s
3. Ratio of rate constant at t = 0 to t = t1 to t = tx is :

(A) 2 : 3 : 4 (B) 1 : 1 : 1 (C) 1 : 3 : 5 (D) 1 : 3 : 5
Comprehension # 2
4. For the (Set-1) :

(A) if T1 > T2, k1 > k2 always (B) if T1 > T2, k1 > k2 (for exothermic reaction)
(C) if T1 > T2, k1 < k2 (for endothermic reaction) (D) Ea1  Ea2
5. For the (Set-1) :

(A) Ea1 > Ea2 if T1 > T2 (B) Ea1 < Ea2 if T1 > T2
(C) Ea1 = Ea2 (D) Ea1 = 0.5 Ea2
6. Comparing set-I and II :

(A) k4 > k3 & k2 > k1, if T2 > T1 (endothermic) (B) k4 < k3 & k2 > k1, if T2 < T1 (endothermic)
(C) k4 > k3 & k2 > k1, if T2 < T1 (exothermic) (D) k4 < k3 & k2 < k1, if T2 > T1 (exothermic)
Comprehension # 3
Competing First-Order Reactions
Frequently a species can react in different ways to give a variety of products. For example, toluene can be
nitrated at the ortho, meta, or para positions, We shall consider the simplest case, that of two competing
irreversible first-order reactions :
A  k1 C and A k 2 D
 
where the stoichiometric coefficients are taken as unity for simplicity. The rate law is
 d[A] 
  = – k [A] – k [A] = – (k + k ) [A]  [A] = [A]0 e (k1 k 2 )t .
 dt  1 2 1 2
 d [C] 
For C, we have   = k [A] = k [A] e (k1 k 2 )t . Multiplication by dt and integration from time 0
 dt  1 1 0

k 1[ A ]0 ( k 1  k 2 ) t
(where [C]0 = 0) to an arbitary time t gives [C] = k  k (1  e )
1 2
 d [D]  k 2 [ A ]0
Similarly, integration of   gives [D] = k  k (1 – e (k1  k 2 )t )
 dt  1 2
The sum of the rate constants k 1 + k2 appears in the exponentials for both [C] and [D].
[C] k1
At any time we also have = k
[D] 2
7. A starting initially with only A Which of the following is correct at time t
(A) [A]0 = [A]t +[B]t + [C]t (B) [A]0 = [A]t + 2 [B]t + 3 [C]t
[B] t [C] t 2
(C) [A]0 = [A]t + + (D) [A]0 = [A]t +[B]t + [C]t
2 3 3
[ X] t
8. X starting with only 'X', ratio [ Y ]  [ Z]
t t
1
(A) Independent of time (B) kt
(e  1)
(C) Depends upon initial concentration of X (D) [A]0 (ekt –1)
9. At high temperature acetic acid decomposes into CO2 & CH4 and simultaneously into CH2CO (ketene) and
H2O
1 1
k1 3s
(i) CH3COOH  k 2  4s
 CH4 + CO2 (ii) CH3COOH   CH2CO + H2O
What is the fraction of acetic acid reacting as per reaction (i) ?
3 3 4
(A) (B) (C) (D) none of these
4 7 7
10. For A starting with pure A ratio of rate of production of B to C is :
(A) Independent of time (B) Independent of temperature

(C) Depends upon initial concentration of A (D) Independent of mechanism of reaction

MATCH THE COLUMN
1. Match the following :
Column-I Column -II
(Graph) (Slope)
(A) C vs t (abscissa) for zero order (p) unity
(B) log C vs t (abscissa) for first order (q) zero
  dc 
(C)  dt  vs C for zero order (r) – k
 
  dc  k
(D) ln  dt  vs log C for first order (s) –
  2.303
2. Match the following :

(A) A + B  C + D (p) Unit of rate constant possess concentration unit

r = k1 [A] [B]
(B) A + B  C + D (q) Rate constant for the reaction of both the reactants are equal
r = k2 [A] [B]º
(C) A + B  C + D (r) Rate of consumption of at least one of the reactants is equal to rate of
r = k3 [A]º [B]º production of at least one of the products
(D) 2A + B  2C + 3D (s) If both reactants are taken in stoichiometric ratio, half life for both
r = k3 [A]º [B]º reactants are equal.
3. Match the following :

Column I Column II
(A) If the activation energy is 65 kJ then how much time (p) 2
faster a reaction proceed at 25°C than at 0°C
(B) Rate constant of a first - order reaction is 0.0693 min–1. (q) Zero
If we start with 20 mol L–1, it is reduced to 2.5 mol L–1
in how many minutes
(C) Half - lives of first - order and zero order reactions are same. (r) 11
Ratio of rates at the start of reaction is how many times of 0.693
Assume initial concentration to be same for the both.
(D) the half-life periods are given , (s) 30
[A]0 (M) 0.0677 0.136 0.272
t1/2 (sec) 240 480 960
order of the reaction is :

ANSWER KEY
EXERCISE-I
1 d[ NO]
Q.1 (i) r = = 9 ×10–4mol litre–1 sec–1, (ii) 36 × 10–4mol litre–1sec–1, (iii) 54×10–4 mol litre–1sec–1
4 dt
Q.2 (i) 7.2 mol litre–1min–1, (ii) 7.2 mol litre–1 min–1
Q.3 (a) 1 × 10–4 mol L–1 s–1 , (b) 3 × 10–4 mol L–1 s–1
dx
Q.4 (i) = k[A][B]2, (ii) rate increases by 8 times Q.5 8.12 × 10–6 Ms–1, 0.012 atm min–1
dt
Q.6 rate increase by 27 times Q.7 (a) 0.019 mol L–1 s–1, (b) 0.037 mol L–1 s–1
Q.8 2k1 = k2 = 4k3 Q.9 8 3  1018 sec Q.10 1/6 Q.11 (i) 7.2 M, (ii) Think
Q.12 K = 0.01 M min–1 Q.13 0.75 M Q.14 6 × 10–9 sec Q.15 1.2 hr
Q.16 (i) 36 min., (ii) 108 min. Q.17 (i) 0.0223 min–1, (ii) 62.17 min
2.303 1
Q.19 expiry time = 41 months Q.20 3.3 × 104s1 Q.21 k= log
t a
Q.22 11.2% Q.23 15 min
Q.24 (a) Third order, (b) r = k[NO]2[H2], (c) 8.85 ×10–3 M sec–1.
Q.25 (i) first order (ii) k = 1.308 × 102 min1 (iii) 73% Q.26 (i) Zero order, (ii) K = 5 Pa/s
l P3 l P3 l r
Q.27 Zero order Q.28 k = t ln 2( P  P ) Q.29 k = t ln ( P  P ) Q.30 k = t ln ( r  r )
3 2 3 2  t
Q.31 First order Q.32 (i) r= K[(CH3)2 O], 0.000428 sec–1 Q.33 First order
Q.34 966 min Q.35 (a) 90 mm, (b) 47 mm, (c) 6.49 × 10–2 per minutes, (d) 10.677 min.
Q.36 k1 = 2.605 × 103 min1 Q.37 (a) first order, (b) 13.75 minutes, (c) 0.716
1
Q.38 0.180 atm, 47.69 sec Q.39 0.1 min–1 Q.40 ( K1  K 2 )
e t 1
[C] 10
Q.41 = (e11x – 1) Q.42 t = 4 min Q.43 0379.75 K
[A] 11

Q.44 5 kJ mol–1 Q.45 349.1 k Q.46 55.33 kJ mole–1 Q.47 306 k
Q.48 rate of reaction increases 5.81× 108 times Q.49 10.757 k cal mol–1
Q.50 t = 20.4 minutes Q.51 2000 K Q.52 r = K' [NO]2[Br2]
Q.53 r = K [NO]2 [H2], where K = k2 × K1 Q.55 (d) No, (e) mechanism (a) is incorrect
PROFICIENCY TEST
Q.1
1. threshold energy 2. half 3. equal to H 4. directly proportional
5. mol L–1s–1 6. rare 7. lowering 8. fast
9. slowest 10. increases 11. 3 12. rate constant
1
13. 2 and 3 14. rate = k[M]2 15. 1 16. –k
2
17. Activation energy for forward reaction 18. infinte temp. or for zero Ea
k
19. first 20.  ]
2.303
Q.2 1. F 2. T 3. F 4. T 5. F 6. F 7. T
8. T 9. F 10. T 11. T 12. T 13. F 14. F
15. F 16. T 17. F 18. F 19. F 20. T
EXERCISE -II
Q.1 (a) 6.25 ; (b) 14.3 ; (c) 0% Q.2 2 × 10–2 min–1
Q.3 Pt = 379.55 mm Hg, t7/8 = 399.96 min Q.4 11.45 days
Q.5 k = 0.022 hr–1 Q.6 15.13 week
Q.7 20 min Q.8 0.26 : 1
Q.9 (a) 43.46kJmol-1, (b) 20.47 hour Q.10 % decomposition = 67.21%
Q.11 k = 0.0327 min–1 Q.12 0.537 Q.13 4.83 mins Q.14 0.0025 m
Q.15 Ef = 6 × 104 J; Eb = 9.3 × 104J Q.16 a=b=1
d(D) k 1 k 3 (A)(B) A1A 3

Q.18 (a)  ; (b) Ea = Ea1 + Ea3 – Ea2. A = Q.20 0.0805
dt k2  k3 A2

EXERCISE -III
Q.1 B Q.2 B Q.3 A Q.4 D Q.5 A Q.6 D Q.7 D
Q.8 D Q.9 C Q.10 D Q.11 C Q.12 B Q.13 C Q.14 D
Q.15 C Q.16 D Q.17 C Q.18 C Q.19 C Q.20 D Q.21 B
Q.22 A Q.23 D Q.24 C Q.25 B Q.26 B Q.27 C Q.28 D
Q.29 A Q.30 A Q.31 B Q.32 A, B, D Q.33 A, D

Q.34 A, C, D Q.35 A, B, C Q.36 C, D
Q.37 C Q.38 C Q.39 D Q.40 A Q.41 C Q.42 A Q.43 B
Q.44 A Q.45 B Q.46 C Q.47 C Q.48 C Q.49 B Q.50 D
Q.51 B Q.52 C Q.53 C Q.54 (A) S, (B) R, (C) P, (D) Q
Q.55 (A) P (B) Q,R (C) S (D) T
EXERCISE-IV
OBJECTIVE PROBLEM
Q.1 A, B, D Q.2 D Q.3 B Q.4 A Q.5 C Q.6 C
Q.7 D Q.8 D Q.9 A Q.10 A
SUBJECTIVE PROBLEM
Q.1 3.435 × 10–3 M/min Q.2 100 kJmol–1 Q.3 t1/2 = 24.14 min
Q.4 (a) 1, (b) 6.93 × 10–3 min–1 , (c) 200, (d) 950 mm Q.5 0
COMPREHENSION
Q.1 (A) Q.2 (D) Q.3 (B) Q.4. (A) Q.5 (C)
Q.6 (A) Q.7 (C) Q.8 (B) Q.9 (B) Q.10 (A)
MATCH THE COLUMN
Q.1 (A – r) ; (B – s) ; (C – q) ; (D – p) Q.2 (A) p, q, r, s ; (B) q, r, s ; (C) p, q, r, s ; (D) p, r, s
Q.3 (A – r ; B – s ; C – p ; D – q)

Solid State [358]
EXERCISE I
Formula of ionic solid from unit cell description
Q.1 A cubic solid is made up of two elements A and B. Atoms B are at the corners of the cube and A at the
body centre. What is the formula of compound.
Q.2 A compound alloy of gold and copper crystallizes in a cubic lattice in which gold occupy that lattice point
at corners of the cube and copper atom occupy the centres of each of the cube faces. What is the
formula of this compound.
Q.3 A cubic solid is made by atoms A forming close pack arrangement, B occupying one. Fourth of tetrahedral
void and C occupying half of the octahedral voids. What is the formula of compound.
Q.4 What is the percent by mass of titanium in rutile, a mineral that contain Titanium and oxygen, if structure
can be described as a closet packed array of oxide ions, with titanium in one half of the octahedral holes.
What is the oxidation number of titanium?
Q.5 Spinel is a important class of oxides consisting of two types of metal ions with the oxide ions arranged in
CCP pattern. The normal spinel has one-eight of the tetrahedral holes occupied by one type of metal ion
and one half of the octahedral hole occupied by another type of metal ion. Such a spinel is formed by
Zn2+, Al3+ and O2–, with Zn2+ in the tetrahedral holes. Give the formulae of spinel.
Edge length, density and number of atoms per unit cell
Q.6 KF crystallizes in the NaCl type structure. If the radius of K+ ions 132 pm and that of F– ion is 135 pm,
what is the shortest K–F distance? What is the edge length of the unit cell? What is the closet K–K
distance?
Q.7 A closed packed structure of uniform spheres has the edge length of 534 pm. Calculate the radius of
sphere, if it exist in
(a) simple cubic lattice (b) BCC lattice (c) FCC lattice
Q.8 Calculate the density of diamond from the fact that it has face centered cubic structure with two atoms
per lattice point and unit cell edge length of 3.569 Å.
Q.9 An element crystallizes into a structure which may be described by a cubic type of unit cell having one
atom on each corner of the cube and two atoms on one of its body diagonals. If the volume of this unit
cell is 24×10–24 cm3 and density of element is 7.2 g cm–3, calculate the number of atoms present in
200 g of element.
Q.10 Silver has an atomic radius of 144 pm and the density of silver is 10.6 g cm–3. To which type of cubic
crystal, silver belongs?
Q.11 AgCl has the same structure as that of NaCl. The edge length of unit cell of AgCl is found to be 555 pm
and the density of AgCl is 5.561 g cm–3. Find the percentage of sites that are unoccupied.
Q.12 Xenon crystallises in the face-centred cubic lattice and the edge of the unit cell is
620 pm. What is the nearest neighbour distance and what is the radius of xenon atom?
Solid State [359]

Q.13 The two ions A+ and B– have radii 88 and 200 pm respectively. In the closed packed crystal of compound
AB, predict the co-ordination number of A+.
Q.14 CsCl has the bcc arrangement and its unit cell edge length is 400 pm. Calculate the interionic distance in CsCl.
Q.15 Gold crystallizes in a face centered cubic lattice. If the length of the edge of the unit cell is 407 pm,
calculate the density of gold as well as its atomic radius assuming it to be spherical. Atomic mass of
gold = 197 amu.
Q.16 The density of KBr is 2.75 g cm–3 . The length of the edge of the unit cell is 654 pm. Show that KBr has
face centered cubic structure.
(N = 6.023 ×1023 mol–1 , At. mass : K = 39, Br = 80)
Q.17 An element crystallizes in a structure having FCC unit cell of an edge 200 pm. Calculate the density, if
200 g of this element contains 24×1023 atoms.
Q.18 The effective radius of the iron atom is 1.42 Å. It has FCC structure. Calculate its density
(Fe = 56 amu)
Q.19 A crystal of lead(II) sulphide has NaCl structure. In this crystal the shortest distance between Pb+2 ion
and S2– ion is 297 pm. What is the length of the edge of the unit cell in lead sulphide? Also calculate the
unit cell volume.
Q.20 If the length of the body diagonal for CsCl which crystallises into a cubic structure with Cl– ions at the
corners and Cs+ ions at the centre of the unit cells is 7 Å and the radius of the Cs+ ion is 1.69 Å, what is
the radii of Cl– ion?
Solid State [360]

PROFICIENCY TEST
1. Crystalline solids are isotropic.
2. Rhombohedral, triclinic and hexagonal are the unit cells, which have only primitive arrangement possible.
3. Packing fraction of FCC and HP units cells are same.
4. The minimum void fraction for any unit cell in any shape having only one type of atom and all voids
unfilled is 0.26.
5. Packing fraction of a lattice structure depends on the radius of the atom crystallizing in it.
6. The location of tetrahedral voids in FCC unit cell are the centers of 8 minicubes forming a large cube.
7. Effective number of octahedral voids in a unit cell is equal to the effective number of atoms in the unit cell.
8. Radius ratio for co-ordination number 4 having tetrahedral and square planar geometry is same.
9. The radius ratio value for co-ordination number 4 having square planar geometry and co-ordination
number 6 having octahedral geometry is same.
10. A metallic element crystallises into a lattice containing a sequence of layers of AB AB AB ...... . Any
packing of spheres leaves out voids in the lattice 26% percent by volume of this lattice is empty space.
11. The relation between edge length (a) and radius of atom (r) for BCC lattice is_______.
12. The relation between edge length (a) and radius of atom (r) for FCC lattice is________.
13. ABCABC......layering pattern is called ________ packing, found in _______ lattice.
14. ABABAB.....layering pattern is called _______packing , found in _______ lattice.
15. Height (c) of the hexagonal primitive unit cell in terms of radius of atom (r) is________.
16. Anions would be in contact with each other only if the cation to anion radius for a given co-ordination
number is_______.
17. The number of tetrahedral voids in hexagonal primitive unit cell is________.
18. The limiting radius for co-ordination number 8 is_________.
19. For cesium chloride structure, the interionic distance (in terms of edge length, a) is equal to _______.
20. Density of a crystal ___due to Schottky defect and _____due to Frankel defect.
Solid State [361]

EXERCISE II
Q.1 Iron has body centered cubic lattice structure. The edge length of the unit cell is found to be 286 pm.
What is the radius of an iron atom?
Q.2 Cesium chloride forms a body centered cubic lattice. Cesium and chloride ions are in contact along the
body diagonal of the unit cell. The length of the side of the unit cell is 412 pm and Cl– ion has a radius of
181 pm. Calculate the radius of Cs+ ion.
Q.3 In a cubic closed packed structure of mixed oxides the lattice is made up of oxide ions, one eighth of
tetrahedral voids are occupied by divalent ions (A2+) while one half of the octahedral voids occupied
trivalent ions (B3+). What is the formula of the oxide?
Q.4 A solid A+ and B– had NaCl type closed packed structure. If the anion has a radius of 250 pm, what
should be the ideal radius of the cation? Can a cation C+ having a radius of 180 pm be slipped into the
tetrahedral site of the crystal of A+B– ? Give reasons for your answer.
Q.5 Calculate the value of Avogadro’s number from the following data:
Density of NaCl = 2.165 cm–3
Distance between Na+ and Cl– in NaCl = 281 pm.
Q.6 If the radius of Mg2+ ion, Cs+ ion, O2– ion, S2– ion and Cl– ion are 0.65 Å , 1.69 Å, 1.40 Å, 1.84 Å, and
1.81 Å respectively. Calculate the co-ordination numbers of the cations in the crystals of MgS, MgO
and CsCl.
Q.7 Iron occurs as bcc as well as fcc unit cell. If the effective radius of an atom of iron is 124 pm. Compute
the density of iron in both these structures.
r  r 
Na 0.5 Na 0.7
Q.8 KCl crystallizes in the same type of lattice as does NaCl. Given that and Calculate:
rCl  rK 
(a) The ratio of the sides of unit cell for KCl to that for NaCl and
(b) The ratio of densities of NaCl to that for KCl.
Q.9 An element A (Atomic weight = 100) having bcc structure has unit cell edge length 400 pm. Calculate the
density of A and number of unit cells and number of atoms in 10 gm of A.
Q.10 Prove that the void space percentage in zinc blende structure is 25%.
Q.11 A unit cell of sodium chloride has four formula units. The edge of length of the unit cell is 0.564 nm.
What is the density of sodium chloride.
Q.12 In a cubic crystal of CsCl (density = 3.97 gm/cm3) the eight corners are occupied by Cl– ions with Cs+
ions at the centre. Calculate the distance between the neighbouring Cs+ and Cl– ions.
Q.13 KF has NaCl structure. What is the distance between K+ and F– in KF if density of KF is 2.48 gm/cm3.
Q.14 The composition of a sample of wustite is Fe0.93O1.0. What percentage of iron is present in the form of
Fe(III)?
Solid State [362]

Q.15 BaTiO3 crystallizes in the prevoskite structure. This structure may be described as a cubic lattice with
barium ions occupying the corner of the unit cell, oxide ions occupying the face-centers and titanium ion
occupying the center of the unit cell.
(a) If titanium is described as occupying holes in BaO lattice, what type of holes does it occupy?
(b) What fraction of this type hole does it occupy?
Q.16 Rbl crystallizes in bcc structure in which each Rb+ is surrounded by eight iodide ions each of radius
2.17 Å. Find the length of one side of RbI unit cell.
Q.17 If NaCl is dopped with 10–3 mol % SrCl2, what is the numbers of cation vacancies?
Q.18 Find the size of largest sphere that will fit in octahedral void in an ideal FCC crystal as a function of
atomic radius 'r'. The insertion of this sphere into void does not distort the FCC lattice. Calculate the
packing fraction of FCC lattice when all the octahedral voids are filled by this sphere.
Q.19 A cubic unit cell contains manganese ions at the corners and fluoride ions at the center of each edge.
(a) What is the empirical formula of the compound?
(b) What is the co-ordination number of the Mn ion?
(c) Calculate the edge length of the unit cell, if the radius of Mn ion is 0.65 Å and that of F– ion is 1.36 Å.
Q.20 NaH crystallizes in the same structure as that of NaCl. The edge length of the cubic unit cell of NaH is
4.88 Å.
(a) Calculate the ionic radius of H–, provided the ionic radius of Na+ is 0.95 Å.
(b) Calculate the density of NaH.
Q.21 Metallic gold crystallises in fcc lattice. The length of the cubic unit cell is a = 4.07 Å.
(a) What is the closest distance between gold atoms.
(b) How many “nearest neighbours” does each gold atom have at the distance calculated in (a).
(c) What is the density of gold?
(d) Prove that the packing fraction of gold is 0.74.
Q.22 Ice crystallizes in a hexagonal lattice. At the low temperature at which the structure
was determined, the lattice constants were a = 4.53 Å, and b = 7.60 Å(see figure).
How many molecules are contained in a given unit cell? [density (ice) = 0.92 gm/cm3)]
Q.23 Using the data given below, find the type of cubic lattice to which the crystal belongs.
Fe V Pd
a in pm 286 301 388
 in gm cm–3 7.86 5.96 12.16
Q.24 Potassium crystallizes in a body-centered cubic lattice with edge length, a = 5.2 Å.
(a) What is the distance between nearest neighbours?
(b) What is the distance between next-nearest neighbours?
(c) How many nearest neighbours does each K atom have?
(d) How many next-nearest neighbours does each K atom have?
(e) What is the calculated density of crystalline potassium?
Q.25 Prove that void space in fluorite structure per unit volume of unit cell is 0.243.
Q.26 A compound formed by elements X & Y, Crystallizes in a cubic structure, where X is at the corners of
the cube and Y is at six face centers. What is the formula of the compound? If side length is 5Å, estimate
the density of the solid assuming atomic weight of X and Y as 60 and 90 respectively.
Solid State [363]

Q.27 The metal nickel crystallizes in a face centred cubic structure. Its density is 8.9 gm/cm3. Calculate
(a) the length of the edge of the unit cell.
(b) the radius of the nickel atom. [Atomic weight of Ni = 58.89]
Q.28 The olivine series of minerals consists of crystals in which Fe and Mg ions may substitute for each other
causing substitutional impurity defect without changing the volume of the unit cell. In olivine series of
1
minerals, oxide ion exist as FCC with Si4+ occupying th of octahedral voids and divalent ions occupying
4
1 th
of tetrahedral voids. The density of forsterite (magnesium silicate) is 3.21 g/cc and that of fayalite
4
(ferrous silicate )is 4.34 g/cc. Find the formula of forsterite and fayalite minerals and the percentage of
fayalite in an olivine with a density of 3.88 g/cc.
Q.29 The mineral hawleyite, one form of CdS, crystallizes in one of the cubic lattices, with edge length 5.87Å.
The density of hawleyite is 4.63 g cm–3.
(i) In which cubic lattice does hawleyite crystallize?
(ii) Find the Schottky defect in g cm–3.
Q.30 A strong current of trivalent gaseous boron passed through a germanium crystal decreases the density of
the crystal due to part replacement of germanium by boron and due to interstitial vacancies created by
missing Ge atoms. In one such experiment, one gram of germanium is taken and the boron atoms are
found to be 150 ppm by weight, when the density of the Ge crystal decreases by 4%. Calculate the
percentage of missing vacancies due to germanium, which are filled up by boron atoms.
Atomic wt. Ge = 72.6, B = 11
Solid State [364]

EXERCISE III
Single correct
Q.1 A solid has a structure in which W atoms are located at the corners of a cubic lattice, O atom at the
centre of the edges and Na atom at centre of the cubic. The formula for the compound is
(A) NaWO2 (B) NaWO3 (C) Na2WO3 (D) NaWO4
Q.2 The density of CaF2 (fluorite structure) is 3.18 g/cm3. The length of the side of the unit cell is
(A) 253 pm (B) 344 pm (C) 546 pm (D) 273 pm
Q.3 Which of the following statements is correct in the rock-salt structure of an ionic compounds?
(A) coordination number of cation is four whereas that of anion is six.
(B) coordination number of cation is six whereas that of anion is four.
(C) coordination number of each cation and anion is four.
(D) coordination number of each cation and anion is six.
Q.4 The coordination number of cation and anion in Fluorite CaF2 and CsCl are respectively
(A) 8:4 and 6:3 (B) 6:3 and 4:4 (C) 8:4 and 8:8 (D) 4:2 and 2:4
Q.5 The interstitial hole is called tetrahedral because

(A) It is formed by four spheres.
(B) Partly same and partly different.
(C) It is formed by four spheres the centres of which form a regular tetrahedron.
(D) None of the above three.
Q.6 The tetrahedral voids formed by ccp arrangement of Cl– ions in rock salt structure are
(A) Occupied by Na+ ions (B) Occupied by Cl– ions
(C) Occupied by either Na+ or Cl– ions (D) Vacant
Q.7 The number of nearest neighbours around each particle in a face-centred cubic lattice is
(A) 4 (B) 6 (C) 8 (D) 12
Q.8 If the anions (A) form hexagonal closest packing and cations (C) occupy only 2/3 octahedral voids in it,
then the general formula of the compound is
(A) CA (B) CA2 (C) C2A3 (D) C3A2
Q.9 A solid is formed and it has three types of atoms X, Y, Z. X forms a FCC lattice with Y atoms occupying
all the tetrahedral voids and Z atoms occupying half the octrahedral voids. The formula of the solid is:
(A) X2Y4Z (B) XY2Z4 (C) X4Y2Z (D) X4YZ2
Q.10 The intermetallic compound LiAg crystallizes in cubic lattice in which both lithium and silver have
coordination number of eight. The crystal class is
(A) Simple cubic (B) Body centred cubic (C) Face centred cubic (D) None
Q.11 A compound XY crystallizes in BCC lattice with unit cell edge lenght of 480 pm. If the radius of Y– is
225 pm, then the radius of X+ is
(A) 127.5 pm (B) 190.68 pm (C) 225 pm (D) 255 pm
Solid State [365]

Q.12 The mass of a unit cell of CsCl corresponds to
(A) 1 Cs+ and 1 Cl– (B) 1 Cs+ and 6 Cl– (C) 4 Cs+ and 4 Cl– (D) 8 Cs+ and 1 Cl–
Q.13 In the closest packing of atoms A (radius : ra), the radius of atom B that can be fitted
into tetrahedral voids is
(A) 0.155 ra (B) 0.225 ra (C) 0.414 ra (D) 0.732 ra
Q.14 Which one of the following schemes of ordering closed packed sheets of equal sized spheres do not
generate close packed lattice.
(A) ABCABC (B) ABACABAC (C) ABBAABBA (D) ABCBCABCBC
Q.15 An ionic compound AB has ZnS type structure. If the radius A+ is 22.5 pm, then the ideal radius of B–
would be
(A) 54.35 pm (B) 100 pm (C) 145.16 pm (D) none of these
Q.16 NH4Cl crystallizes in a body-centered cubic type lattice with a unit cell edge length of 387 pm. The
distance between the oppositively charged ions in the lattice is
(A) 335.1 pm (B) 83.77 pm (C) 274.46 pm (D) 137.23 pm
Q.17 In diamond, carbon atom occupy FCC lattice points as well as alternate tetrahedral voids. If edge length
of the unit cell is 356 pm, then radius of carbon atom is
(A) 77.07 pm (B) 154.14 pm (C) 251.7 pm (D) 89 pm
Q.18 Which of the following will show schottky defect

(A) CaF2 (B) ZnS (C) AgCl (D) CsCl
Q.19 Copper metal crystallizes in FCC lattice. Edge length of unit cell is 362 pm. The radius of largest atom
that can fit into the voids of copper lattice without disturbing it.
(A) 53 pm (B) 45 pm (C) 93 pm (D) 60 pm
Q.20 In FCC unit cell, what fraction of edge is not covered by atoms?
(A) 0.134 (B) 0.24 (C) 0.293 (D) None of these
Assertion & Reason
Q.21 Statement-1 : KCl is more likely to show schottky defect, while LiI is more likely to show Frenkel
defect.
Statement-2 : Schottky defect is more likely in ionic solids in which cations and anions are of
comparable size while Frenkel defect is more likely is which cations and anions have
large differences in their ionic sizes.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1
Solid State [366]

Q.22 Statement-1 : Increasing temperature increases the density of point defects
Statement-2 : The process of formation of point defects in solids in endothermic and has S > 0.
Q.23 Statement-1 : Increase in dielectric constant is observed in Frenkel defect.

Statement-2 : Anions come in interstitial space in case of Frenkel defect.
Q.24 Statement-1 : Distance between nearest lattice points in BCC is greater than the same in FCC for the
atoms of comparable size.
Statement-2 : FCC has greater packing efficiency than BCC.

Q.25 Which of the following statements is/are correct :
(A) The coordination number of each type of ion in CsCl is 8.
(B)A metal that crystallises in BCC structure has a coordination number 12.
(C) A unit cell of an ionic crystal shares some of its ions with other unit cells
(D) The length of the unit cell in NaCl is 552 pm.
[ rNa = 95 pm ; rCl  = 181 pm ]
Q.26 Which of the following statements is/are correct :

(A) In an anti-fluorite structure anions form FCC lattice and cations occupy all tetrahedral voids.
(B) If the radius of cations and anions are 0.2 Å and 0.95 Å then coordinate number of cation in the
crystal is 4.
(C) An atom/ion is transferred from a lattice site to an interstitial position in Frenkel defect.
(D) Density of crystal always increases due to substitutinal impurity defect.
Q.27 80.0 gm salt of weak base & strong acid XY is dissolved in water and formed 2 litre of aqueous solution.
The pH of the resultant solution was found to be 5 at 298 K. If XY forms CsCl type crystal having
rX  (radius of X+) = 1.6 Å & rY – (radius of Y¯) = 1.864 Å then select write statement(s).
(Given : Kb (XOH) = 4 × 10–5 ; NA = 6 × 1023)
(A) Molar mass of salt is 100 g/mol
(B) % Degree of dissociation of salt is 0.25
(C) Edge length of AB is 4Å
(D) Density of solid salt XY is 2 in gm/cc
Solid State [367]

Q.28 Select write statement(s)
(A) 8 Cs+ ions occupy the second nearest neighbour locations of a Cs+ ion
(B) Each sphere is surrounded by six voids in two dimensional hexagonal close packed layer
(C) If the radius of cations and amions are 0.3 Å and 0.4 Å then coordinate number of cation in the
crystal is 6.
(D) In AgCl, the silver ion is displaced from its lattice position to an interstitial position such a defect is
called a frenkel defect
Comprehension:
(Q.29 to Q.32)
Calcium crystallizes in a cubic unit cell with density 3.2 g/cc. Edge-length of the unit cell is 437 picometre (pm)
Q.29 The type of unit cell is
(A) Simple cubic (B) BCC (C) FCC (D) Edge-centred
Q.30 The nearest neighbour distance is

(A) 154.5 pm (B) 309 pm (C) 218.5 pm (D) 260 pm
Q.31 The number of nearest neighbours of a Ca atom are

(A) 4 (B) 6 (C) 8 (D) 12
Q.32 If the metal is melted, density of the molten metal was found to be 3 g/cc. What will be the percentage of
empty space in the melt?
(A) 31% (B) 36% (C) 28% (D) 49%
(Q.33 & Q.34)

Silicon carbide (SiC) and diamond are covalent solids which crystallize in cubic strucures. In SiC, carbon
atoms occupy points of the face centred cubic lattice (FCC positions) and silicon atoms occupy half of
the tetrahedral voids available. In diamonds, same position of the tetrahedral voids are occupied by
other carbon atoms.
Also the density of SiC and diamond are 3.2 and 3.6 g/cc respectively. Answer the following four
questions based on the above information: (M : Si = 28)
Q.33 The radius of silicon atom is
(A) 0.76 Å (B) 1.12 Å (C) 3.54 Å (D) 4.75 Å
Q.34 Which of the following will not change the density of SiC solid?
(A) Substitution of some Si atoms by some carbon atoms
(B) Schottky defects
(C) Interchange of some Si atom by some C atom
(D) Decreasing the temperature of solid.
Solid State [368]

Match the Column:
Q.35 Column I Column II

[Distance in terms of edge length of cube (a)]
(A) 0.866 a (P) Shortest distance between cation & anion in

CsCl structure.
(B) 0.707 a (Q) Shortest distance between two cation in CaF2

structure.
(C) 0.433 a (R) Shortest distance between carbon atoms in

diamond.
(S) Shortest distance between two cations in rock

salt structure.
Q.36 Match the column:

Column I Column II
(A) Rock salt structure (P) Co-ordination number of cation is 4
3a
(B) Zinc Blend structure (Q) = r+ + r–
4
(C) Flourite structure (R) Co-ordination number of cation and anion
are same
a
(S) Distance between two nearest anion is
2
Solid State [369]

EXERCISE IV
Q.1 The packing efficiency of the two-dimensional square unit cell shown below is [JEE 2010]
L
(A) 39.27 % (B) 68.02 % (C) 74.05 % (D) 78.54 %
Q.2 The correct statement(s) regarding defects in solid is (are) [JEE 2009]
(A) Frenkel defect is usually favoured by a very small difference in the sizes of cation and anion.
(B) Frenkel defect is a dislocation defect
(C) Trapping of an electron in the lattice leads to the formation of F-center.
(D) Schottky defects have no effect on the physical properties of solids.
Paragraph for Question No. 3 to 5

In hexagonal systems of crystals, a frequently encountered arrangement of atoms is described as a
hexagonal prism. Here, the top and bottom of the cell are regular hexagons and three atoms are sandwiched
in between them. A space-filling model of this structure, called hexagonal close-packed (HCP), is
constituted of a sphere on a flat surface surrounded in the same plane by six identical spheres as closely
as possible. Three spheres are then placed over the first layer so that they touch each other and represent
the second layer. Each one of these three spheres touches three spheres of the bottom layer. Finally, the
second layer is covered with a third layer that is identical to the bottom layer in relative position. Assume
radius of every sphere to be ‘r’.
Q.3 The number of atoms in this HCP unit cells is [JEE 2008]
(A) 4 (B) 6 (C) 12 (D) 17
Q.4 The volume of this HCP unit cell is [JEE 2008]

64 3
(A) 24 2 r 3 (B) 16 2 r 3 (C) 12 2 r 3 (D) r
3 3
Q.5 The empty space in this HCP unit cell is [JEE 2008]
(A) 74% (B) 47.6 % (C) 32% (D) 26%
Q.6 Match the crystal system / unit cells mentioned in Column I with their characteristic features mentioned in
Column II. Indicate your answer by darkening the appropriate bubbles of the 4 × 4 matrix given in the ORS.
Column I Column II
(A) simple cubic and face-centred cubic (P) have these cell parameters a = b = c
and  =  = 
(B) cubic and rhombohedral (Q) are two crystal systems
(C) cubic and tetragonal (R) have only two crystallographic angles of 90°
(D) hexagonal and monoclinic (S) belong to same crystal system.
[JEE 2007]
Q.7 The edge length of unit cell of a metal having atomic weight 75 g/mol is 5 Å which crystallizes in cubic
lattice. If the density is 2 g/cc then find the radius of metal atom. (NA = 6 × 1023). Give the answer in pm.
[JEE 2006]
Solid State [370]

Q.8 An element crystallises in FCC lattice having edge length 400 pm. Calculate the maximum diameter
which can be placed in interstital sites without disturbing the structure. [JEE 2005]
Q.9 Which of the following FCC structure contains cations in alternate tetrahedral voids?
(A) NaCl (B) ZnS (C) Na2O (D) CaF2 [JEE 2005]
Q.10
(i) AB crystallizes in a rock salt structure with A : B = 1 : 1. The shortest distance between A and B is
Y1/3 nm. The formula mass of AB is 6.023 Y amu where Y is any arbitrary constant. Find the density in kg m-3.
(ii) If measured density is 20 kg m-3. Identify the type of point defect. [JEE–2004]
Q.11 Marbles of diameter 10 mm each are to be arranged on a flat surface so that their centres lie within the area
enclosed by four lines of length each 40 mm. Sketch the arrangement that will give the maximum number of
marbles per unit area, that can be enclosed in this manner and deduce the expression to calculate it.[JEE 2003]
Q.12 A substance AxBy crystallises in a FCC lattice in which atoms “A” occupy each corner of the cube and atoms
“B” occupy the centres of each face of the cube. Identify the correct composition of the substance AxBy.
(A) AB3 (B) A4B3
(C) A3B (D) composition cannot be specified [JEE-2002]
Q.13 The figures given below show the location of atoms in three crystallographic planes in FCC lattice. Draw
the unit cell for the corresponding structure and identify these planes in your diagram.
[JEE-2000]
Q.14 In a solid “AB” having NaCl structure “A” atoms occupy the corners of the cubic unit cell. If all the
face-centred atoms along one of the axes are removed, then the resultant stoichiometry of the solid is
(A) AB2 (B) A2B (C) A4B3 (D) A3B4 [JEE-2000]
Q.15 In any ionic solid [MX] with schottky defects , the number of positive and negative ions are same.[T/F]
[JEE-2000]
Q.16 The coordination number of a metal crystallising in a hcp structure is [JEE-2000]

(A) 12 (B) 4 (C) 8 (D) 6
Q.17 A metal cryatallises into two cubic phases, FCC and BCC whose unit cell lengths are 3.5 and 3.0 Å
respectively. Calculate the ratio of densities of FCC and BCC. [JEE-1999]
Solid State [371]

COMPREHENSION
Read the following comprehension carefully and answer the questions.
Comprehension # 1
Consider the figure given for solid XY. Answer the following questions
Figure
1. The site Y represents
(A) tetrahedral void (B) Octahedral void (C) triangular void (D) cubical void.
2. The number of XY units per unit cell is

(A) 4 (B) 3 (C) 3 (D) 8
3. Co-ordination number of Y is
(A) 3 (B) 4 (C) 6 (D) 8
Comprehension # 2
When an atom or an ion is missing from its normal lattice site, a lattice vacancy (Schottky defect) is created.
In stoichiometric ionic crystals, a vacancy of one ion has to be accompanied by the vacancy of the oppositely
charged ion in order to maintain electrical neutrality.
In a Frenkel defect an ion leaves its position in the lattice and occupies an interstitial void. This is the Frenkel
defect commonly found along with the Schottky defects and interstitials. In pure alkali halides, Frenkel
defects are not found since the ions cannot get into the interstitial sites. Frenkel defects are found in silver
halides because of the small size of the Ag+ ion. Unlike Schottky defects, Frenkel defects do not change the
density of the solids. In certain ionic solids (e.g. AgBr) both Schottky and Frenkel defects occur.
The defects discussed above do not disturb the stoichiometry of the crystalline material. There is large
variety of non-stoichiomertic inorganic solids which contain an excess or deficiency of one of the elements.
Such solids showing deviations from the ideal stoichiometric composition form an important group of solids.
For example in the vanadium oxide, VOx, x can be anywhere between 0.6 and 1.3. There are solids which are
difficult to prepare in the stoichiometric composition. Thus, the ideal composition in compounds such as
FeO is difficult to obtain (normally we get a composition of Fe0.95 O but it may range from Fe0.93 O to Fe0.96O).
Non-stoichiometric behaviour is most commonly found for transition metal compounds though is also known
for some lanthanoids and actinoids.
Zinc oxide loses oxygen reversibly at high temperatures and turns yellow in colour. The excess metal is
accommodated interstitially, giving rise to electrons trapped in the neighbourhood. the enhanced electrical
conductivity of the non-stoichiometric ZnO arises from these electrons.
Anion vacancies in alkali halides are produced by heating the alkali halide crystals in an atmosphere of the
alkali metal vapour. When the metal atoms deposit on the surface they diffuse into the crystal and after
ionisation the alkali metal ion occupies cationic vacancy whereas electron occupies anionic vacancy. Electrons
trapped in anion vacancies are referred to as F-centers ( from Farbe the German word for colour) that gives
rise to interesting colour in alkali halides. Thus, the excess of potassium in KCl makes the crystal appear
violet and the excess of lithium in LiCl makes it pink.
4. When LiCI is heated into the vapour of lithium, the crystal acquires pink colour. This is due to
(A) Schottkty defects (B) Frenkel defects
(C) Metal excess defect leading to F-centers (D) Electronic defect
5. Strongly heated ZnO crystal can conduct electricity. This is due to
(A) Movement of extra Zn2+ ions present in the interstitial sites
(B) Movement of electrons in the anion vacancies
(C) Movement of both Zn2+ ions and electrons
Solid State [372]

(D) None of these
6. AgCl is crystallized from molten AgCl containing a little CdCl2. The solid obtained will have
(A) cationic vacancies equal to number of Cd2+ ions incorporated
(B) cationic vacancies equal to double the number of Cd2+ ions
(C) anionic vacancies
(D) neither cationic nor anionic vacancies
7. Which of the following is most appropriate crystal to show Frenkel defect.
(A) CsCl (B) NaCl (C) AgBr (D) CaCl2
MATCH THE COLUMN

1. We are good at matching things let us try our hand on the following columns :
Solid Constituent particle Binding force
(a) Diamond (e) Ion (i) Metallic
(b) Sodium Chloride (f) Atom (j) Dipole dipole
(c) HCl (g) Kernel (k) Ionic
(d) Aluminium (h) Molecule (l) Covalent
2. Column I (Arrangement of the atoms/ions) Column II (Planes in fcc lattice)
(A) (p)
(B) (q)
(C) (r)
(D) (s)
3. Column I Column II

(A) ZnS crystal (p) fcc
(B) CaF2 crystal (q) hcp
3
(C) NaCl crystal (r) Distance between closest particles is a.
4
(D) Diamond crystal (s) Only one type of voids are occupied
Solid State [373]

ANSWER KEY
EXERCISE I
Q.1 A-B Q.2 AuCu3
Q.3 A4B2C2 Q.4 59.95%, +4
Q.5 ZnAl2O4 Q.6 267 pm, 534 pm, 378 pm
Q.7 267 pm, 231.2 pm, 188.8 pm Q.8 3.5 g cm–3
Q.9 3.472 × 1024 atoms Q.10 FCC
Q.11 0.24% Q.12 438.5 pm, 219.25 pm
Q.13 6 Q.14 346.4 pm
Q.15 19.4g/cm3 , 143.9 pm Q.17 41.67 g cm–3
Q.18 5.74 g cm–3 Q.19 a =5.94×10–8cm, V=2.096×10–22 cm–3
Q.20 1.81Å
PROFICIENCY TEST
1. F 2. T 3. T 4. T 5. F 6. T 7. T
8. F 9. T 10. T 11. 3 a = 4r 12. 2 a = 4r
2
13. cubic close, FCC 14. hexagonal close, HP 15. c = 4r
3
16. least or minimum 17. 12 18. 0.732
3a
19. 20. decreases, remains constant
2
EXERCISE II
Q.1 123.84 pm Q.2 175.8 pm
Q.3 AB2O4 Q.4 103.4 pm, No
Q.5 6.01×1023 Q.6 4, 6, 8
Q.7 7.887 g/cc , 8.59 gm/cm3 Q.8 (a) 1.143, (b) 1.172
Q.9 5.188 gm/cm3, 6.023×1022 atoms of A, 3.0115×1022 unit cells
Q.11 2.16 gm/cm3 Q.12 3.57 Å
Solid State [374]

Q.13 2.685 Å Q.14 15.053
Q.15 (a) octahedral, (b) 1/4 Q.16 4.34 Å
Q.17 6.02 × 1018 mol–1 Q.18 0.414 r, 79.3%
Q.19 (a) MnF3, (b) 6, (c) 4.02Å Q.20 (a) 1.49 Å, (b) 1.37 g/cm3
Q.21 (a) 2.88 Å, (b) 12 , (c) 19.4 g/cc Q.22 4 molecules of H2O
Q.23 for Fe is bcc, for V is bcc, for Pd is face centered
Q.24 (a) 4.5 Å, (b) 5.2 Å, (c) 8, (d) 6, (e) 0.92 g/cm3
Q.26 XY3, 4.38 g/cm3 Q.27 (a) 3.52 Å,(b) 1.24 Å
Q.28 Mg2SiO4, Fe2SiO4, 59% Q.29 (i) 3.90, (ii) 0.120 g/cc
Q.30 2.376%
EXERCISE III
Q.1 B Q.2 C Q.3 D Q.4 C Q.5 C Q.6 D Q.7 D
Q.8 C Q.9 A Q.10 B Q.11 B Q.12 A Q.13 B Q.14 C
Q.15 B Q.16 A Q.17 A Q.18 D Q.19 A Q.20 C Q.21 A
Q.22 A Q.23 C Q.24 A Q.25 A,C,D Q.26 A,C Q.27 A,C Q.28 B,D
Q.29 C Q.30 B Q.31 D Q.32 A Q.33 B Q.34 C
Q.35 (A) P (B) Q,S (C) R Q.36 (A) R,S (B) P,Q,R,S (C) Q
EXERCISE IV
Q.1 D Q.2 B,C Q.3 B Q.4 A Q.5 D
Q.6 (A) P, S (B) P,Q (C) Q (D) Q,R Q.7 216.5 pm Q.8 117.1 pm Q.9 B
Q.10 (i) = 5 kg m–3

(ii) There is huge difference in theoretically calculated density and observed density. It is only possible if
some foreign species occupies interstitial space i.e. substitution defect.
Q.11 Q.12 A Q.13 Q.14 D Q.15 True Q.16 A
Q.17 1.259
Solid State [375]

COMPREHENSION
Q.1 (B) Q.2 (A) Q.3 (C) Q.4 (C) Q.5 (B)
Q.6 (A) Q.7 (C)
MATCH THE COLUMN

Q.1 (a - f,l); (b - e,k); (c - h,j); (d - g,i) Q.2 (A - r,s); (B - r,s); (C - p); (D - q)
Q.3 (A - p,q,r,s); (B - p,r,s); (C - p,s); (D - p,r,s)
Solid State [376]

Surface Chemistry [377]

Section (A) : Adsorption
A-1. Why adsorption is always exothermic ?
A-2. What is the difference between physical adsorption and chemisorption ?
A-3. What are the factors which influence the adsorption of a gas on a solid ?
A-4. What is an adsorption isotherm ?
A-5. What do you understand by activation of adsorbent ? How is it achieved ?
A-6. Which will be adsorbed more readily on the surface of charcoal and why– NH3 or CO2 ?
A-7. In an Adsorption experiment a graph between log x/m versus log P was found to be linear with a slope of 45º
the intercept of the log x/m was found to be 0.3010. Calculate the amount of gas adsorbed per gram of
charcoal under a pressure of 0.6 bar.
A-8. 1 g of charcoal adsorbs 100 mL of 0.5 M CH3COOH to form mono layer and there by the molarity of CH3COOH
reduces to 0.49 M. Calculate the surface area of the charcoal adsorbed by each molecule of CH 3COOH.
Surface area of charcoal = 3.01 × 102 m2/g.
A-9. What role does adsorption play in heterogeneous catalysis ?
A-10. How many grams of gas would be adsorbed per gram of a substance at 8 atm by assuming Freundlich
adsorption isotherm.
x
= kp1/n and k = 10–2 atm–1/3 & n = 3.
m
A-11. 10 mg of an adsorbate gets adsorbed on a surface. This causes the release of 3J of heat at constant
pressure and at 27ºC. [Molar mass of adsorbate = 100 g/mol].
(i) Find Hadsorption.
(ii) Argue whether the adsorption is physical or chemical ?
(iii) If 20 mg of adsorbate is adsorbed at temperature T 0. Then compare T0 and 27ºC :
Section (B) : Catalysis

B-1. Give two examples of heterogeneous catalysis.
B-2. Identify the correct order of steps in hetereogeneous catalysis.
(i) Adsorption of reactant molecules on the surface of the catalyst.
(ii) Diffusion of reactant to the surface of the catalyst.
(iii) Formation of reactions product on the catalyst surface.
(iv) Diffusion of reactions product from the catalyst surface or desorption.
(v) Formation of activated intermediate.
Section (C) : Classification and Preparation of Colloid

C-1. How are the colloidal solutions classified, on the basis of physical states of the dispersed phase and dispersion
medium ?
C-2. Explain the following terms with suitable examples.
(a) Gel (b) Liquid Aerosol (c) Hydrosol
C-3. How are associated colloids different from multimolecular and macromolecular colloids ?
C-4. Give one example of multimolecular and macromolecular colloids.

Section (D) : Purification and Preparation of Colloid
D-1. Describe a method each for the preparation of sols of sulphur and platinum in water
D-2. Explain the following terms :
(a) Peptization (b) Electrophoresis (c) Dialysis (d) Brownian movement
D-3. Why the sun looks red at the time of setting ?
D-4. Why is osmotic pressure of a colloidal solution less than that of true solution ?
Section (E) : Coagulation, Protection And application of colloid

E-1. Which one of the following electrolytes is most effective for the coagulation of Fe(OH) 3 sol and why ? NaCl,
Na2SO4, Na3PO4.
E-2. What do you understand by "isoelectric point" of a colloid ?
E-3. Rivers form delta on meeting with ocean, why ?
E-4. Artificial rain is made by spraying salt over clouds, why ?
Section (F) : Emulsion, Micelle and Gel

F-1. Name two demulsifier.
F-2. What is the difference between sols and emulsions.
F-3. What is demulsification ?
F-4. What is phase inversion in emulsion ?

Section (A) : Adsorption
A-1. Which of the following statements about chemisorption is not applicable?
(A) It involves chemical forces between adsorbent and absorbate
(B) It is irreversible in nature
(C) It involves high heat of adsorption
(D) It does not require activation energy
A-2. Following is the variation of physical adsorption with temperature:
(A) (B) (C) (D)
A-3. Adsorption is the phenomenon in which a substance :

(A) accumulates on the surface of the other substance
(B) goes into the body of the other substances
(C) remains close to the other substance
(D) none of these
A-4. Finely divided catalyst has greater surface area and has greater catalytic activity than the compact solid. If
a total surface area of 6291456 cm 2 is required for adsorption in a catalysed gaseous reaction, then how
many splits should be made to a cube of exactly 1 cm in length to achieve required surface area.
(Given : One split of a cube gives eight cubes of same size)
(A) 60 (B) 80 (C) 20 (D) 22
A-5. Volume of N2 at NTP required to form a mono layer on the surface of iron catalyst is 8.15 ml/gram of the
adsorbent. What will be the surface area of the adsorbent per gram if each nitrogen molecule occupies
16 × 10–22 m2.
(A) 16 × 10–16 cm2 (B) 0.35 m2/g (C) 39 m 2/g (D) 22400 cm2
A-6. There is desorption of physical adsorption when :
(A) temperature is increased (B) temperature is decreased
(C) pressure is increased (D) concentration is increased
A-7. The rate of chemisorption :
(A) decreases with increase of pressure (B) increases with increase of pressure
(C) is independent of pressure (D) is independent of temperature
A-8. Softening of hard water is done using sodium aluminium silicate (zeolite). This causes :
(A) adsorption of Ca2+ and Mg2+ ions of hard water replacing Na+ ions.
(B) adsorption of Ca2+ and Mg2+ ions of hard water replacing Al3+ ions
(C) both (A) and (B)
(D) none of these
Section (B) : Catalysis
B-1. Which one is false in the following statement ?
(A) A catalyst is specific in its action
(B) A very small amount of the catalyst can alter the rate of a reaction.
(C) The number of free valencies on the surface of the catalyst increases on sub-division
(D) Ni is used as a catalyst in the manufacture of ammonia
B-2. A catalyst increases rate of reaction by :
(A) Decreasing enthalpy (B) Decreasing internal energy
(C) Decreasing activation energy (D) Increasing activation energy
Section (C) : Classification and Preparation of Colloid
C-1. Colloidal solution of gold prepared by different methods of different colours because of :
(A) different diameters of colloidal gold particles (B) variable valency of gold
(C) different concentration of gold particles (D) impurities produced by different methods
Section (D) : Purification and Preparation of Colloid
D-1.  A colloidal solution can be purified by the following method :
(A) dialysis (B) peptization (C) filtration (D) oxidation
D-2. Peptisation is :
(A) conversion of a colloidal into precipitate form
(B) conversion of precipitate into colloidal sol
(C) conversion of metal into colloidal sol by passage of electric current
(D) conversion of colloidal sol into macromolecules
D-3. Bleeding is stopped by the application of ferric chloride. This is because :
(A) the blood starts flowing in opposite direction
(B) the blood reacts and forms a solid, which seals the blood vessel
(C) the blood is coagulated and thus the blood vessel is sealed
(D) the ferric chloride seals the blood vessel.
Section (E) : Coagulation, Protection And application of colloid
E-1. Gold number of a lyophilic sol is such property that :
(A) the larger its value, the greater is the peptising power
(B) the lower its value, the greater is the peptising power
(C) the lower its value, the greater is the protecting power
(D) the larger its value, the greater is the protecting power
E-2. Protective sols are:
(A) lyophilic (B) lyophobic (C) both (A) and (B) (D) none of (A) and (B)
E-3. For the coagulation of 200 mL of As2S3 solution, 10 mL of 1 M NaCl is required. What is the coagulating value
(number of milli moles of solute needed for coagulation of 1 liter of solution) of NaCl.
(A) 200 (B) 100 (C) 50 (D) 25

E-4. Which of the following ions is most effective in the coagulation of an arsenious sulphide solution ?
(A) K+ (B) Mg2+ (C) Al3+ (D) C
E-5. Which of the following ions is most effective in the coagulation of ferric hydroxide solution ?
(A) Cl¯ (B) Br – (C) NO2¯ (D) SO42–
Section (F) : Emulsion, Micelle and Gel
F-1. Small liquid droplets dispersd in another liquid is called :
(A) Suspension (B) Emulsion (C) Gel (D) True solution
F-2. At CMC, the surfactant molecules :
(A) Decomposes (B) Become completely soluble
(C) Associate (D) Dissociate

1. Match list I with list II and select the correct answer :
List I List II
(A) Mechanical property of colloid (p) Dialysis
(B) Purification (q) Peptization
(C) Gold number (r) Brownian movement
(D) Formation of a sol (s) Protection
2. List I List II
(A) Gold sol (p) Bredig's Arc method
(B) Purification of colloidal solution (q) Negatively charged
(C) As2S3 sol (r) Dialysis
(D) Zeta potential (s) Electro kinetic potential
(E) Casein (t) Double decomposition reaction
(u) Protective colloid

1. Which of the following statements is correct for a lyophilic solution ?
(A) It is not easily solvated (B) It is unstable
(C) The coagulation of this sol is irreversible in nature (D) It is quite stable in a solvent
2. Liquid-liquid sol is known as
(A) aerosol (B) foam (C) emulsion (D) gel
3. The colloidal system consisting of a liquid adsorbate in a solid adsorbent is termed as :
(A) aerosol (B) foam (C) emulsion (D) gel
4. Which of the following statements is not correct ?
(A) A colloidal solution is a heterogeneous two-phase system
(B) Silver sol in water is an example of lyophilic solution.
(C) Metal hydroxides in water are examples of lyophobic solution
(D) Liquid-liquid colloidal solution is not a stable system
5. Size of colloidal particles may range from :
(A) 1 to 1000 nm (B) 10 to 100 pm (C) 1 to 100 µm (D) 1 to 10 mm
6. Which of the following represents a multimolecular colloidal particles?
(A) Starch (B) A sol of gold (C) Proteins (D) Soaps

7. Which of the following anions will have minimum flocculation value for the ferric oxide solution ?
(A) Cl¯ (B) Br¯ (C) SO42– (D) [Fe(CN)6l3-
8. Which of the following represents a macromolecular colloidal particles ?
(A) Solution of gold (B) Cellulose (C) Soaps (D) Synthetic detergents
9. Gold number of some lyophilic sols are :
 : Casein : 0.01
 : Haemoglobin : 0.03
 : Gum arabic : 0.15
V : Sodium oleate : 0.40
Which has maximum protective power :
(A)  (B)  (C)  (D) V
10. Arsenic () sulphide forms a sol with a negative charge. Which of the following ionic substances should be
most effective in coagulating the sol ?
(A) KCl (B) MgCl2 (C) Al2(SO4)3 (D) Na3PO4
11. Smoke is a dispersion of :

(A) gas in gas (B) gas in solid (C) solid in gas (D) liquid in gas
12. Smoke has generally blue tinge. It is due to :

(A) scattering (B) coagulation (C) Brownian motion (D) electro-osmosis
13. Which one of the following statements is false for hydrophilic sols ?
(A) they do not require electrolytes for stability
(B) their viscosity is of the order of that of water
(C) their surface tension is usually lower than that of dispersion medium.
(D) none of these
14. Soaking of sponge by water is an example of :

(A) Simple adsorption (B) Physical adsorption (C) Chemisoption (D) Absorption
15. Identify the appropriate graph between enthalpy and progress of physical adsorption.
(A) (B) (C) (D)
16. Hydrolysis of ester in catalysed by acid. Rate of hydrolysis of ester were obtained initially and after some
ester has been hydrolysed as R0 and Rt then (same temp.)
(A) R0 = Rt (B) R0 < Rt (C) R0 > Rt (D) Cannot be determined
PART - II : SINGLE OR DOUBLE INTEGER TYPE

1. When a graph is plotted between log x/m and log p, it is straight line with an angle 45° and intercept 0.3010
on y-axis. If initial pressure is 0.3 atm, what will be the amount of gas adsorbed per gram of adsorbent :
(Report your answer after multiplying by 10)
2. The volume of nitrogen gas (measured at STP) required to cover a sample of silica gel with a mono-molecular
layer is 129cm3/g of gel. Calculate the surface area per gram of the gel if each nitrogen molecule occupies
16.2 x 10-20m2. (Report your answer after dividing by 10)

3. How many of these reactions are homogeneously catalyzed?
(i) 2SO 2 (g)  O 2 (g)   2SO3 (g)
NO( g )
H2SO 4 (  )
(ii) C12H22O11(aq.)  H2O()   C 6H12 O 6 (aq.)  C 6H12O 6 (aq.)
Glucose Fructose
(iii) 2SO 3 (g)  O 2 (g)   2SO3 (g)

Pt ( s )
(iv) N2 (g)  3H2 (g)   2NH3 (g)
Fe( s )
(v) 4NH3 (g)  5O2 (g)   4NO(g)  6H2O(g)

Pt ( s )
(vi) CH3 COOCH3 ()   CH3 COOH(aq)
HCl(  )
(vii) Vegetable oils ()  H2 (g)   Vegetable ghee (s).

Ni( s )
4. Coagulation value of the electrolytes AlCl3 and NaCl for As2S3 sol are 0.093 and 52 repectively. How many
times AlCl3 has greater coagulating power than NaCl.
5. Among the following number of correct statements are :
(i) Stability of lyophilic colloids is mainly due to the strong interaction between dispersed particle and dispersion
medium.
(ii) Entropy change for adsorption of gases over solid is positive.
(iii) Gelatin has considerably low value of gold number and is effective protective colloid.
(iv) Zeta potential is also responsible for stability of lyophobic colloid solution.
(v) Surface tension of lyophilic colloidal solution is lesser than that of dispersion medium.
6. For the just coagulation of 250 mL of Fe(OH)3 sol, 2 mL of 1 M Na2SO4 electrolyte is required. What is the
coagulating value of Na2SO4 electrolyte.
7. The minimum concentration of an electrolyte required to cause coagulation of a sol is called its flocculation
value. It is expressed in millimoles per litre. If the flocculation value of MgSO 4 for standard As2S3 sol is 3.33.
How many milligrams of MgSO4 is to be added to 20 ml standard As2S3 sol so that flocculation just starts ?
PART - III : ONE OR MORE THAN ONE OPTION CORRECT TYPE

1. Which of the following statements about physical adsorption is correct ?
(A) It is always monolayer
(B) It is reversible in nature
(C) It involves van der Waals interactions between adsorbent and adsorbate
(D) It involves small enthalpy of adsorption as compared to chemisorption.
2. Which of the following statements regarding adsorption is correct ?
(A) Extent of adsorption of gases on charcoal increases with increase in pressure of the gas
(B) Extent of adsorption is independent of temperature
(C) Extent of chemisorption by a given mass of adsorbent is limited
(D) Extent of adsorption is dependent on the nature of adsorbent
3. Which of the following is characteristic of chemisorption?
(A) it is irreversible (B) it is specific
(C) it is multilayer phenomenon (D) heat of adsorption of about – 400 kJ
4. Which is/are a purely surface phenomena :
(A) surface tension (B) adsorption (C) absorption (D) none of these
5. Which of the following are correct statements ?
(A) Spontaneous adsorption of gases on solid surface is an exothermic process as entropy decreases during
adsorption
(B) Formation of micelles takes place when temperature is below Kraft Temperature (Tk) and concentration is
above critical micelle concentration (CMC)
(C) Longer the length of hydrophobic chain, smaller is the value of critical micelle concentration (CMC)
(D) According to Hardy-Schulze rules the coagulation (flocculating) value of Fe3+ ion will be more than Ba2+ or Na+.

6. Which of the following statements are true for physisorption?
(A) Extent of adsorption increases with increase in pressure.
(B) It needs activation energy
(C) It can be reversed easily
(D) It occurs at high temperature.
7. Identify the reactions that includes inhibtors in the reactions mixture.
Fe Ni
(A) N2  3H2 
 2NH3 (B) Vegetable Oil + H2  Vegetable ghee.
Mo Cu
Fe Pd
(C) N2  3H2  2NH3 (D) RCOCl  H2  RCHO  HCI
CO / H2 S BaSO4
8. Which of the following are the correct :

(A) A Catalyst remains unchanged in mass and chemical compositions at the end of reactions.
(B) Finely devided state of catalyst is more efficient for the reactions.
(C) Catalyst change equilibrium state of the reaction.
(D) A catalyst changes the entropy and the free energy of a reaction.
9. The diameter of colloidal particle is of the order :
(A) 10–3 m (B) 10–6 m (C) 10–15 m (D) 10–7 m
10. Which of the following are examples of aerosols?
(A) Whipped cream (B) Cloud (C) Fog (D) Soap lather
11. Which of the following are hydrophobic sols ?
(A) Protein sol (B) Gold sol (C) Gum sol (D) Fe(OH)3 sol.
12. Which of the following are multimolecular colloids ?
(A) Sulphur (B) Egg albumin in water
(C) Gold sol (D) Soap solution
13. The origin of charge on colloidal solution is
(A) Self dissociation (in soaps and detergents) (B) Electron capture during Bredig's arc method
(C) Selective adsorption of ion on their surface (D) It is due to addition of protective colloids
14. Which of the following is/are not true for lyophilic colloid ?
(A) These are prepared by special indirect methods.
(B) The particles must travel towards the anode or cathode depending on their charge under the influence of
an electric field.
(C) These are called on intrinsic colloid
(D) Small quantity of electrolyte is sufficient to cause precipitation of these.
15. Which of the following are based on Tyndall effect.
(A) Tail of comets (B) Deltas
(C) Blue colour of sky (D) Coagulation
16. Which of the following statements is correct?
(A) Peptization is the process by which certain substances are converted into the colloidal state.
(B) Metal sols of gold, silver and platinum can be prepared by Bredig's arc method.
(C) Impurities present in a solution makes it more stable.
(D) Dialysis is a process to remove impurities of ions and molecules from a solution.
17. Which is an example of coagulation?
(A) curdling of milk (B) purification of water by addition of alum
(C) formation of deltas at the river beds (D) formation of ice
18. When negatively charged colloids like As2S3 sol is added to positively charged Fe(OH)3 sol in suitable
amounts
(A) Both the sols are precipitated simultaneously. (B) This process is called mutual coagulation.
(C) They become positively charged colloids. (D) They become negatively charged colloids.

19. Which of the following are incorrect statements ?
(A) Hardy schulz rule is related to coagulation
(B) Brownian movement and Tyndall effect are the characteristic of colloids.
(C) In gel, the liquid is dispersed in liquid
(D) Higher the gold number, more is the protective power of lyophillic sols.
20. Which of the following sols is positively charged?
(A) Arsenious sulphide (B) Aluminium hydroxide
(C) Ferric hydroxide (D) Silver iodide in silver nitrate solution
Comprehension # 1
Many lyophilic sols and few lyophobic sols when coagulated under some special conditions changes into
semi rigid mass, enclosing whole amount of liquid within itself, it is called gel and the process is called
gelation. Gelatin Agar-agar, gum-Arabic can be converted into gels by cooling them under moderate
concentration conditions. Hydrophobic sols like silicic acid. Al(OH)3 are prepared by double decomposition
and exchange of solvent method.
Types of Gel :
(i) Elastic gel : Those gel which have elastic properties.
Eg : Gelatin, Strach, Agar-Agar etc.
(ii) Non- elastic gel : Those gel which are rigid.
Eg : Silica gel.
Properties of Gel :
1.Syneresis/weeping of gel : The spontaneous liberation of liquid from a gel is called syneresis or weeping
of gels. It is reverse of swelling.
Eg : Gelatin, Agar-Agar show syneresis at low concentration while sillicic acid shows it at high concentration.
2. Imbibition or swelling of gel : When gel is kept in a suitable liquid (water) it absorb large volume of
liquid. The phenomenon is called imbibition or swelling of gel.
3.Thixotropic : Some gels when shaken to form a sol, on keeping changes into gel are termed as thixotropic
gel and phenomenon is called thixotropy.
Eg : Gelatin and silica liquify on shaking changing into corresponding sol and the sol on keeping changes
back into gel.
1. Which of the following is used to adsorb water ?
(A) Silica gel (B) Calcium acetate (C) Hair gel (D) Cheese
2. The process of imbibing water when elastic gel are placed in water is called :
(A) imbibition (B) synerisis (C) coagulation (D) thixotropy
3. Some types of gels like gelatin and silica liquify on shaking thereby changing into sols. The sols on standing
change back into gels. This process is know as
(A) syneresis (B) thixotropy
(C) double decompostion (D) peptization
Comprehension # 2
The clouds consist of charged particles of water dispersed in air. Some of them are +vely charged, others are
–vely charged. When +vely charged clouds come closer they cause lightening and thundering whereas when
+ve and –ve charged colloids come closer they cause heavy rain by aggregation of minute particles. It is
possible to cause artificial rain by throwing electrified sand or silver iodide from an aeroplane and thus
coagulating the mist hanging in air.
Smoke screen is a cloud of smoke used to hide military, naval police etc. it consists of fine particles of TiO 2.
4. When excess of AgNO3 is treated with KI solution, AgI forms
(A) +ve charged sol (B) –vely charged sol (C) neutral sol (D) true solution

5. AgI helps in artificial rain because :
(A) it helps in ionisation of water (B) it helps in dispersion process
(C) it helps in coagulation (D) all of them
6. Smoke screens consist of
(A) fine particles of TiO2 dispersed in air by aeroplanes
(B) fine particles of AgI dispersed in air by aeroplanes
(C) fine particles of Al2O3 dispersed in air by aeroplanes
(D) None of these

EXERCISE - 1
PART - I
A-1. Adsorption is accompanied by decrease of randomness, i.e. this factor opposes the process, i.e. S is – ve.
For the process to be spontaneous, G must be – ve. Hence, according to eqn, G = H – TS, G can be
–ve only if H is –ve.
A-2. Difference between physical adsorption and chemical adsorption :
Physical Adsorption Chemical Adsorption
The forces between the adsorbate molecules and the The forces between the adsorbate molecules and the
adsorbent are weak van der Waal’s forces. adsorbent are strong chemical forces.
Low heat of adsorption of the order of 20-40 kJ mol –1 High heat of adsorption of the order 80-240 kJ mol–1
Usually occurs at low temperature and decreases with It occurs at high temperature decreases with
increasing temperature. increasing temperature.
It is reversible. It is irreversible.
The extent of adsorption depends upon the ease of There is no correlation between extent of adsorption
liquefication of the gas. and the ease of liquefication of gas.
It is less specific in nature, all gases are adsorbed on It is highly specific in nature and occurs only when
the surface of a solid to some extent adsorbent and there is bond formation between extent.
adsorbate molecules.
It forms multimolecular layers. It forms mono-molecular layer.
A-3. (i) The nature of the gas (i.e. nature of the adsorbate). The easily liquefiable gases such as HCl, NH3,
Cl2 etc. are adsorbed more than the permanent gases such as H2, N2 and O2. The ease with which a gas can
be liquefied is primarily determined by its critical temperature. Higher the critical temperature (T c) of a gas,
the more easily it will be liquefied and, therefore, more readily it will be adsorbed on the solid.
Gas SO2 CH4 H2
TC 330K 190 K 33 K
(ii) Nature of adsorbent. The extent of adsorption of a gas depends upon the nature of adsorbent. Activated
charcoal (i.e. activated carbon), metal oxides (silica gel and aluminium oxide) and clay can adsorb gases
which are easily liquified. Gases such as H2, N2 and O2 are generally adsorbed on finely divided transition
metals Ni and Co.
(iii) Activation of adsorbent.
(a) Metallic adsorbents are activated by mechanical rubbing or by subjecting it to some chemical reactions.
(b) To increase the adsorbing power of adsorbents, they are sub-divided into smaller pieces. As a result, the
surface area is increased and therefore, the adsorbing power increases.
(iv) Effect of temperature.
Mostly the process of adsorption is exothermic and the reverse process or desorption is endothermic. If the
above equilibrium is subjected to increase in temperature, then according to Le-Chaterlier’s principle, with
increase in temperature, the desorption will be favoured. Physical adsorption decreases continuously with
increase in temperature whereas chemisorption increases initially, shows a maximum in the curve and then
it decreases continuously.
x x
m m
Temperature Temperature
The initial increase in chemisorption with increase in temperature is because of activation energy required.
This is why the chemical adsorption is also known as “Activated adsorption”.
A graph between degree of adsorption (x/m) and temperature ‘t’ at a constant pressure of adsorbate gas is
known as adsorption isobar.

(v) Effect of pressure. The extent of adsorption of a gas per unit mass of adsorbent
depends upon the pressure of the gas. The variation of extent of adsorption expressed as x/m (where x is the
mole of adsorbate and m is the mass of the adsorbent) and the pressure is given as below. A graph between
the amount of adsorption and gas pressure keeping the temperature constant is called an adsorption isotherm.
It is clear from the figure that extent of adsorption (x/m) increases with pressure and becomes maximum
corresponding to pressure Ps called equilibrium pressure. Since adsorption is a reversible process, the
desorption also takes place simultaneously. At this pressure (Ps) the amount of gas adsorbed becomes
equal to the amount of gas desorbed.
A-4. It represents the variation of the mass of the gas adsorbed per gram of the adsorbent with pressure at
constant temperature.
A-5. It means increasing the adsorption power of an adsorbent and is done by increasing the surface area of the
adsorbent by a suitable method.
A-6. NH3 has higher critical temperature than that of CO2, i.e. NH3 is more easily liquefiable than CO2 because,
NH3 has greater intermolecular forces of attraction and hence will be adsorbed more readily.
A-7. 1.2 A-8. 5 × 10–19 m2 .
A-9. In heterogeneous catalysis, generally the reactants are gaseous where as catalyst is a solid. The reactant
molecules are adsorbed on the surface of the catalyst. As a result, the concentration of the reactant molecules
on the surface increases and hence the rate of reaction increases.
x
A-10. = 10–2 × 81/3 = 0.02 g A-11. T0 < 27ºC
m
B-1. (i) Mfg. of NH3 (Haber's process) – using iron as catalyst

(ii) Mfg. of H2SO4 – using platinised asbestos or V2O5 as catalyst.
B-2. (ii)  (i)  (v)  (iii)  (iv)
C-1. On the bases of physical state of D.P. and D.M. colloidal solution may be divided into eight system.
Table : Type of Colloidal Systems
DP DM Type of colloid Examples
Solid Solid Solid Sol Some coloured glasses and gem stones
Solid Liquid Sol Paints, cell fluids
Solid Gas Aerosol Smoke, dust
Liquid Solid Gel Cheese, butter, jellies
Liquid Liquid Emulsion Milk, hair cream
Liquid Gas Liquid Aerosol Fog, mist, cloud, insecticide sprays
Gas Solid Solid Sol Pumice stone, foam rubber
Gas Liquid Foam Froath, whipped cream, soap lather.
C-2. (a) Gel – a colloidal dispersion of a liquid in a soild, e.g., butter
(b) Liquid aerosol – a colloidal dispersion of a liquid in a gas, e.g., fog
(c) Hydrosol – a colloidal sol of a solid in water as the dispersion medium, e.g, starch sol or gold sol.

C-3. Associated colloids are formed by electrolytes so that they are dissociated into ions and these ions associate
together to form ionic micelles whose size lies in the colloidal range, e.g. soaps.
Multimolecular colloids–formed by the aggregation of a large number of simple molecules. Macromolecular
colloids – due to large size of the molecules themselves.
C-4. Multimolecular – S8 ; Macromolecular – starch
D-1. Sol of sulphur – oxidation method or by exchange of solvent.
Sol of platinum – Bredig's electro–disintegration method.
D-2. (a) Peptization: The term has originated from the digestion of proteins by the enzyme pepsin. Peptization
may be defined as (the process of converting a precipitate into colloidal sol by shaking it with dispersion
medium in the presence of a small amount of electrolyte). The electrolyte used for this purpose is called
peptizing agent. This method is applied, generally, to convert a freshly prepared precipitate into a colloidal
sol. During peptization, the precipitate adsorbs one of the ions of the electrolyte on its surface. The ion
adsorbed on the surface is common either with the anion or cation of the electrolyte. This causes the
development of positive or negative charge on precipitates which ultimately break up into smaller particles
having the dimensions of colloids.
(b) Electrical Properties (Electrophoresis) :The particles of the colloids are electrically charged and carry
positive or negative charge. The dispersion medium has an equal and opposite charge making the system
neutral as a whole. Due to similar nature of the charge carried by the particles, they repel each other and do
not combine to form bigger particles. That is why, a sol is stable and particles do not settle down. Arsenious
sulphide, gold, silver and platinum particles in their respective colloidal sols are negatively charged while
particles of ferric hydroxide, aluminium hydroxide are positively charged. The existence of the electric charge
is shown by the phenomenon of electrophoresis. It involves the 'movement of colloidal particles either towards
the cathode or anode, under the influence of the electric field'. The apparatus used for electrophoresis as
shown in fig.
(Fig. : A set up for electrophoresis.)

The colloidal solution is placed in a U-tube fitted with platinum electrodes. On passing an electric current, the
charged colloidal particles move towards the oppositely charged electrode. Thus, if arsenic sulphide sol is
taken in the U-tube, in which negatively charge particle of arsenic sulphide move towards the anode.
*Earlier this process was called cataphoresis because most of the colloidal sols studied at that time were
positively charged and moved towards cathode.
(c) Dialysis : It is a process of removing a dissolved substance from a colloidal solution by means diffusion
through suitable membrane. Since particles in true solution (ions or smaller molecules) can pass through
animal membrane or parchment paper or cellophane sheet but colloidal particle do not, the appratus used for
this purpose is called Dialyser.
A bag of suitable membrane containing the colloidal solutions is suspended in a vessel through which fresh
water continously flow. The molecules and ions (crystalloids) diffuse through membrane into the outer water
& pure colloidal solution is left behind.

(d) Mechanical Properties :
Brownian movement: Robert Brown, a botanist, discovered in 1827 that pollen grains placed in water do
not remain at rest but move about continuously and randomly. Later on, this phenomenon was observed in
case of colloidal particles when they were seen under an ultramicroscope. The particles were seen to be in
constant zig-zag motion as shown in fig. This zig-zag motion is called Brownian movement.
Figure : Brownian movement

D-3. At the time of settings, the sun is at the horizon. The light emitted by the sun has to travel a longer distance
through the atmosphere. As a result, blue part of the light is scattered away by the dust particles in the
atmosphere. Hence, the red part is visible.
D-4. Because colloidal solutions being bigger aggregate of a large number of molecule, the effective number of
particles in colloidal solution is relative much smaller.
E-1. According to Hardy – schulze rule, greater the charge on the oppositely charged ion of the electrolyte added,
more effective it is in bringing about coagulation. Hence Na3PO4 (PO4–3) is most effective.
E-2. Isoelectric point : The H+ concentration at which the colloidal particles have no charge is known as the
isoelectric point. At this point stability of colloidal particles becomes very less & do not move under influence
of electric field.
E-3. Formation of deltas : The river water contains colloidal particles of sand and clay which carry negative
charge. The sea water contains +ve ions such as Na+, Mg2+, Ca2+, etc. As the river water meets sea water,
these ions discharge the sand or clay particle which are precipitated in the form of delta.
E-4. Artificial rain : Cloud consists of charged particle of water dispersed in air. Rain is caused by aggregation
of these minute particles. Artificial rain can be done by throwing electrified sand of Agl from aeroplanes,
colloidal H2O particle present in cloud will get coagulated by these sand or Agl particles to form bigger water
drops causing rain.
F-1. Alcohol, phenol.
F-2. (i) Sols are dispersions of solids in liquids while emulsions are dispersions of liquids in liquids.
(ii) Sols are quite stable wheres as emulsions are less stable.
F-3. The process of separation of the constituent liquids of an emulsion is called demulsification.
F-4. Changing of W/O emulsion to O/W emulsion and vise-versa is known as phase inversion.
PART - II
A-1. (D) A-2. (B) A-3. (A) A-4. (C) A-5. (B)
A-6. (A) A-7. (B) A-8. (A) B-1. (D) B-2. (C)
C-1. (A) D-1. (A) D-2. (B) D-3. (C) E-1. (C)
E-2. (A) E-3. (C) E-4. (C) E-5. (D) F-1. (B)
F-2. (C)
PART - III
1. (A)  (r) ; (B)  (p) ; (C)  (s) ; (D)  (q) 2. (A – p, q) ; (B–r) ; (C – q, t) ; (D – s) ; (E – u)

EXERCISE - 2
PART - I
1. (D) 2. (C) 3. (D) 4. (B) 5. (A)
6. (B) 7. (D) 8. (B) 9. (A) 10. (C)
11. (C) 12. (A) 13. (B) 14. (D) 15. (A)
16. (B)
PART - II
1. 6 2. 56 3. 3 (i, ii, vi) 4. 560 5. 4
6. 8 7. 8
PART - III
1. (B,C,D) 2. (A,C,D) 3. (A,B,D) 4. (A,B) 5. (A,C)
6. (A,C) 7. (C,D) 8. (A,B) 9. (B,D) 10. (B,C)
11. (B,D) 12. (A,C) 13. (A,B,C) 14. (A,B,D) 15. (A,C)
16. (A,B,D) 17. (A,B,C) 18. (A,B) 19. (C,D) 20. (B,C,D)
PART - IV
1. (A) 2. (A) 3. (B) 4. (A) 5. (C)
6. (A)


4 above.
1. For adsorption of a gas on a solid, the plot of log (x/m) Vs log P is linear with a slope equal to
[n being a whole number]
(1) K (2) log K (3) n (4) 1/n
2. Surface tension of lyophilic sols is :

(1) Lower than that of H2O (2) More than that of H2O
(3) Equal to that of H2O (4) None of the above
3. On passing light from collidal solution, the effect due to scattering of light is known as :
(1) Electrophoresis (2) Tyndall effect (3) Electromosis (4) Coagulation
4. Tyndall effect is shown by :

(1) Sol (2) Solution (3) Plasma (4) Precipitation
5. Milk is an example of :
(1) True solution (2) Gel (3) Suspension (4) Emulsion
6. Most effective ion to coagulate a negative sol is :

(1) PO43– (2) Al3+ (3) Ba2+ (4) K+
7. Which of the following electrolytes will be most effective in the coagulation of gold sol :
(1) NaNO3 (2) K4[Fe(CN)6] (3) Na3PO4 (4) MgCl2
8. The stability of lyophilic colloid is due to which of the following :

(1) Charge on their particles (2) Large size of their particles
(3) Small size of their particles (4) Solvation by dispersion medium
9. A colloidal solution is subjected to an electrical field. The particles move towards anode. The coagulation of
the same solution is studied using NaCl, BaCl2 and AlCl3 solutions. Their coagulating power should be
(1) NaCl > BaCl2 > AlCl3 (2) BaCl2 > AlCl3 > NaCl
(3) AlCl3 > BaCl2 > NaCl (4) BaCl2 > NaCl > AlCl3
10. Which of the following is most effective in coagulating a ferric hydroxide sol :
(1) KCl (2) KNO2 (3) K2SO4 (4) K3[Fe(CN)6]

11. Fog is an example of colloidal system of :
(1) Liquid dispersed in gas (2) Gas dispersed in gas
(3) Solid dispersed in gas (4) Solid dispersed in liquid
12. The charge on As2S3 sol is due to the adsorbed :

(1) H+ (2) OH– (3) O–2 (4) S–2
13. The sky looks blue due to :

(1) Dispersion (2) Reflection (3) Transmission (4) Scattering
14. Tyndall effect will be observed in :

(1) Solution (2) Percipitate (3) Sol (4) Vapour
15. The Brownian motion is due to :

(1) Temperature fluctuation within the liquid phase
(2) Attraction and repulsion between charge on the colloidal particles
(3) Impact of molecules of the dispersion medium on the colloidal particles
(4) Convective current
16. In coagulating the colloidal solution of As2S3 which has the minimum coagulating value :
(1) NaCl (2) KCl (3) BaCl2 (4) AlCl3
17. Positive sol is :

(1) Gold (2) Gelatin (3) As2 S3 (4) None
18. Which one is a lyophobic colloid :

(1) Gelatin (2) Starch (3) Sulphur (4) Gum arabic
19. Smoke is an example of :

(1) Gas dispersed in liquid (2) Gas dispersed in solid
(3) Solid dispersed in gas (4) Solid dispersed in solid
20. A colloidal solution of arsenious sulphide is most readily coagulated by the addition of a normal solution?
(1) NaCl (2) CaCl2 (3) Na3PO4 (4) Al2 (SO4)3
21. A colloid always :

(1) Contains two phases (2) Is a true solution
(3) Contains three phases (4) Contains only water soluble particles
22. Which of the following ions has maximum flocculation value :

(1) [Fe(CN)6)]4– (2) Cl– (3) SO2–4
(4) PO–34
23. Which of the following gases, will be adsorbed maximum on a solid surface :
(1) CO2 (2) O2 (3) N2 (4) H2
24. Which of the following is a mismatch :

(1) Lyophilic colloids – reversible sols
(2) Associated colloids – micelles
(3) Tyndall effect – scattering of light by colloidal particle
(4) Electrophoresis – movement of dispersion medium under the influence of electric field
25. A negative catalyst will

(1) raise the energy of activation for a given reaction
(2) take away the internal energy of reactants and deactivate them
(3) catalyse the backward reaction more than the forward one, thereby shifting equilibrium backward.
(4) none of these
26. A liquid is found to scatter a beam of light but leaves no residue when passed through the filter paper. The
liquid can be described as :
(1) a suspension (2) Oil (3) a colloidal sol (4) a true solution

27. Which of the following kinds of catalysis can be explained by the adsorption theory?
(1) heterogeneous catalysis (2) enzyme catalysis
(3) homogeneous catalysis (4) acid base catalysis
28. Which of the following relations is (are) correct according to Freundlich ?

(i) x/m = constant
(ii) x/m = constant × p1/n (n > 1)
(iii) x/m = constant × pn (n > 1)
(1) All are correct (2) All are wrong (3) (ii) is correct (4) (iii) is correct
29. The physical adsorption of gases on the solid surface is due to :

(1) vander Waals forces (2) covalent bonding
(3) hydrogen bonding (4) All of these
30. Correct equation of Freundlich isotherm is :

x 1 x 1
(1) log  m  = log K + log C (2) log  n  = log m + log C
  n   m
x 1 x 1
(3) log  m  = log C + log C (4) log  m  = log C + log K
  K   n

Que. 1 2 3 4 5 6 7 8 9 10
Ans.
Que. 11 12 13 14 15 16 17 18 19 20
Ans.
Que. 21 22 23 24 25 26 27 28 29 30
Ans.
PART - II : ADDITIONAL PROBLEMS
1. A 1 cm × 1 cm square paper coated with a suitable adsorbent on both sides. The paper is dipped in a
aqueous solution of glucose of volume 20 mL and concentration 20 ppm. Final concentration glucose was
dropped to 19 ppm due to adsorption. Find the number of glucose particles per unit area of the paper.
2. When 9.0 ml of arsenius sulphide sol and 1.0 ml of 1.0 × 10–4 M BaCl2 are mixed, turbidity due to precipitation
just appears after 2 hours. Find the coagulating value of the effective ion.

3. Some type of gels like gelatin loose water slowly. The process is known as :
(A) Synerisis (B) Thixotropy (C) Peptisation (D) Imbibition

4. Select correct statement (s) :
(A) hydrophilic colloid is a colloid in which there is a strong attraction between the dispersed phase and
water
(B) hydrophobic colloid is a colloid in which there is a lack of attraction between the dispersed
phase and water
(C) hydrophobic sols are often formed when a solid crystallises rapidly from a chemical reaction
or a supersaturated solution
(D) all of the above
5. A reddish brown sol (containing Fe3+) is obtained by:

(A) the addition of small amount of FeCl3 solution to freshly prepared Fe(OH)3 precipitate
(B) the addition of Fe(OH)3 to freshly prepared FeCl3 solution
(C) the addition of NH4OH to FeCl3 solution dropwise
(D) the addition of NaOH to FeCl3 solution dropwise
6. The stabilisation of a lyophobic colloid is due to :

(A) preferential adsorption of similiar charged particle on colloids surface.
(B) the large electro-kinetic potential developed in the colloid.
(C) the formation of a covalent bond between two phases.
(D) the viscosity of the medium.
7. Compared to common colloidal sols, micelles have :

(A) higher colligative properties (B) lower colligative properties
(C) same colligative properties (D) none of these
8. Graph between log x/m and log p is a straight line inclined at an angle of 45º. When pressure is 0.5 atm and
ln k = 0.693, the amount of solute adsorbed per gram of adsorbent will be :
(A) 1 (B) 1.5 (C) 0.25 (D) 2.5
9. The coagulation of 200 mL of a positive colloid took place when 0.73 g HCl was added to it without changing
the volume much. The flocculation value of HCl for the colloid is :
(A) 0.36 (B) 36.5 (C) 100 (D) 150

10. 0.02 g of gelatin is required to protect 10 mL of gold sol from 10% NaCl, then find the gold number for
gelatin. Report your answer by multiplying by 100.

11. The incorrect statements are -
(A) For coagulation of As2S3 sol, +ve ions are effective.
(B) For coagulation of aluminium hydroxide sol Ba2+ ions are more effective than Na+
(C) Cellulose solution is an example of multimolecular colloid system
(D) Colloidal sol of metals such as gold, silver etc are prepared by Bredig's arc method.
12. An example of extrinsic colloid (lyophobic colloids) is :

(A) As2S3 sol (B) Fe(OH)3 sol (C) Egg albumin (D) Au sol
13. Which of the following are the characteristic of chemisorption :

(A) Multilayer adsorption (B) Exothermic nature
(C) Strong adsorption by adsorption sites (D) Irreversible
14. If Cl2 gas is enclosed in presence of powdered charcoal in a closed vessel, the pressure of the gas decreases.
It is because
(A) the gas molecules are absorbed at the surface
(B) the gas molecules concentrate at the surface of the charcoal
(C) the gas molecules are adsorbed at the surface
(D) the gas molecules are desorbed by the surface
15. Which of the following colloidal solutions contain negatively charged colloidal particles?
(A) Fe(OH)3 sol (B) As2 S3 sol (C) Blood (D) Gold sol
16. Which of the following statements is correct for a lyophobic solution ?

(A) It can be easily solvated (B) It carries charges
(C) The coagulation of this sol is irreversible in nature (D) It is less stable in a solvent
17. Which one of the following statements is/are not correct ?

(A) Brownian movement is more pronounced for smaller particles than for bigger ones
(B) Sols of metal sulphides are lyophilic
(C) Schulze-Hardy law states, the bigger the size of the ion, the greater is its coagulating power
(D) One would expect charcoal to adsorb hydrogen gas more strongly than chlorine.

A. General :
2, 3 and 4). The options for the correct match are provided as (A), (B), (C) and (D) out of which ONLY
ONE is correct.
C. Marking Scheme :

This section contains 7 multiple choice questions. Each questions has four choices (A), (B), (C)
and (D) out of which Only ONE option is correct.
1. An arsenious sulphide sol carries a negative charge. The maximum precipitating power of this sol is :
possessed by :
(A) K2SO4 (B) CaCl2 (C) Na3PO4 (D) AlCl3
2. According to Hardy - Schulze rule, the coagulating power of cation follows the order :
(A) Na+ > Ba2+ > Al3+ (B) Al3+ > Ba2+ > Na+ (C) Ba2+ > Al3+ > Na+ (D) Al3+ > Na+ > Ba2+

3. Which of the following electrolytes is least effective in causing flocculation of ferric hydroxide sol :
(A) K4[Fe(CN)6] (B) K2CrO4 (C) KBr (D)K2SO4
4. Lyophobic colloids are :

(A) Reversible colloids (B) Irreversible colloids
(C) Protective colloids (D) Gum proteins
5. Which among the following statements is false ?

(A) Increase of pressure increases the amount of adsorption.
(B) Increase of temperature may decrease the amount of adsorption.
(C) The adsorption may be monolayered or multilayered.
(D) Particle size of the adsorbent will not affect the amount of adsorption.
6. (i) At 298 K the volume of NH3 adsorbed by 1 g of charcoal is higher than that of H2 under similar conditions.
(ii) The movement of collodial particles towards the oppositely charged electrodes on passing electric
current is known as Brownian movement.
(A) T, T (B) T, F (C) F, T (D) F, F
7. Identify the correct statement regarding enzymes.

(A) Enzymes are specific biological catalysts that can normally function at very high tempt. (T  1000 K)
(B) Enzymes are normally heterogeneous catalysts that are very specific in action
(C) Enzymes are specific biological catalysts that can not be poisoned
(D) Enzymes are non-biological catalysts.

This section contains 5 multiple choice questions. Each questions has four choices (A), (B), (C)
and (D) out of which ONE or MORE THAN ONE are correct.
8. Which of the following statements is correct?

(A) The efficiency of a heterogeneous catalyst depends upon its surface area.
(B) Catalyst operates by providing alternate path for the reaction that involves a lower activation energy.
(C) Catalyst lowers the energy of activation of the forward direction without affecting the energy of activation
of the backward direction.
(D) Catalyst does not affect the overall enthalpy change of the reaction.
9. Which of the following statements is (are) true?

(A) The concentration of a homogeneous catalyst may appear in the rate expression.
(B) A catalyst is always consumed in the reaction.
(C) A catalyst must always be in the same phase as the reactants.
(D) None of these
10. The correct statement(s) pertiaining to the adsorption of a gas on a solid surface is (are)
(A) Adsorption is always exothermic
(B) Physisorption may transform into chemisorption at high temperature
(C) Physisorption increases with increasing temperature but chemisorption decreases with increasing
temperature
(D) Chemisorption is more exothermic than physisorption, however it is very slow due to higher energy of
activation.
11. The incorrect statements are -

(A) For coagulation of As2S3 sol, +ve ions are effective.
(B) For coagulation of aluminium hydroxide sol Ba2+ ions are more effective than Na+
(C) Cellulose solution is an example of multimolecular colloid system
(D) Colloidal sol of metals such as gold, silver etc are prepared by Bredig's arc method.

12. Select the CORRECT statements :
(A) Langmuir adsorption isotherm is expected to be applicable at low gas pressure and moderately high
temperature.
(B) The rate of an enzyme catalysed reaction depends upon enzyme concentration.
(C) A negative catalyst raises the activation energy barrier of a reaction and thus reduces its rate.
(D) Gases having higher critical temperature are adsorbed to a greater extent than those with lower critical
temperature.

13. On addition of one ml solution of 10% NaCl to 10 ml gold sol in the presence of 0.0250 gm of starch the
coagulation is just prevented. Starch has the following gold number :
x
14. At 2 atm pressure the value of will be : (log 2 = 0.3010)
m
15. 1 L of 0.6 M acetic acid is shaken with 2 g activated carbon. Activated carbon absorbs some acetic acid on
its surface only. This process is called adsorption. The final concentration of the solution after adsorption is
0.5 M. What is the amount of acetic acid adsorbed per gram of carbon.
16. A detergent (C12H25SO4Na) solution becomes a colloidal solution at a concentration of 10–3 mol/lit. On an
average 1013 colloidal particles are present in 1 mm 3 what is average number of C12H25SO4Na in one
colloidal particle.
17. For the coagulation of 200 mL of As2S3 solution, 10 mL of 1 M NaCl is required. What is the coagulating
value of NaCl.
18. A solution of palmitic acid (Molar mass = 256) in Benzene contain 5.12 g of acid per litre of solution. When
this solution is dropped on a water surface, the Benzene evaporates and acid forms a monolayer film of
V
solid type. If 500 cm2 are is to be covered by a monolayer, then find X, where X = , when V is volume
100
required of solution. The area covered by 1 molecule = 0.2 nm 2.

(A), (B), (C) and (D)

The Colloidal particles are electrically charged as is indictated by their migration towards cathode or anode
under the applied electric field. In a particular colloidal system, all particles carry either positive charge or
negative charge.

The electric charge on colloidal particles originate in several ways. According to preferential adsorption
theory, the freshly obtained precipitate particles adsorb ions from the dispersion medium, which are common
to their lattice and acquire the charge of adsorbed ions. For example, freshly obtained Fe(OH) 3 precipitated
is dispersed, by a little FeCI3, into colloidal solution owing to the adsorptions of Fe3+ ions in preference.
Thus sol particles will be positively charged.
In some cases the colloidal particles are aggregates of cations or anions having amphiphilic character.
When the ions possess hydrophobic part (hydrocarbon end) as well as hydrophilic part (polar end group),
they undergo association in aqueous solution to form particles having colloidal size. The formation of such
particles, called micelles plays a very important role in the solubilization of water insoluble substances,
(hydrocarbon, oils, fats, grease etc.). In micelles, the polar end groups are directed towards water and the
hydrocarbon ends into the centre.
The charge on sol particles of proteins depends on the pH. At low pH, the basic group of protein molecule
is ionized (protonated) and at higher pH (alkaline medium), the acidic group in ionized. At Isoelectric pH,
characteristic to the protein, both basic and acidic groups are equally ionized.
The stability of colloidal solution is attributed largely to the electric charge of the dispersed particles. This
charge causes them to be coagulated or precipitated. On addition of small amount of electrolytes, the ions
carrying opposite charge are adsorbed by sol particles resulting in the neutralization of their charge.When
the sol particles either with no charge or reduced charge, come closer due to Brownian movement, they
aggregate to form bigger particles resulting in their separation from the dispersion medium. This is what is
called coagulation or precipitation of the colloidal solution. The coagulating power of the effective ion,
which depend on its charge, is expressed in terms of its coagulating value, defined as its minimum
concentration (m mol/L) needed to precipitate a given sol.
19. How would you obtain a sol of AgI, the particles of which migrate toward cathode under the electric field ?
(A) By adding little excess of K to AgNO3 solution
(B) By adding little excess of AgNO3 to K solution
(C) By mixing equal volumes of 0.010 M AgNO3 and 0.010 M K
(D) None of these
20. 100 ml each of two sols of Ag, one obtained by adding AgNO3 to slight excess of K and another obtained
by adding K to slight excess of AgNO3, are mixed together. Then
(A) The two sols will stabilize each other (B) The sol particles will acquire more electric charge
(C) The sols will coagulate each other mutually (D) A true solution will be obtained
21. Under the influence of an electric field, the particles in a sol migrate towards cathode. The coagulation of
the same sol is studied using NaCl, Na2SO4 and Na3PO4 solutions. Their coagulating values will be in the
order
(A) NaCl > Na2 SO4 > Na3 PO4 (B) Na2 SO4 > Na3 PO4 > NaCl
(C) Na3 PO4 > Na2 SO4 > NaCl (D) Na2 SO4 > NaCl > Na3 PO4

This section contains 1 questions, each having two matching lists. Choices for the correct
combination of elements from List-I and List-II are given as options (A), (B), (C) and (D) out of which
one is correct
22. Match list I with list II and select the correct answer and select the correct answer using the code given
below the lists.
List I List II
P. Coagulation 1. Scattering of light
Q. Dialysis 2. Formation of colloidal solution from precipitates.
R. Peptization 3. Purification of colloids
S. Tyndall effect 4. Accmulation of collidal sols
Code :
P Q R S P Q R S
(A) 3 4 1 2 (B) 1 2 4 3
(C) 3 3 2 1 (D) 2 3 1 4

Que. 1 2 3 4 5 6 7 8 9 10
Ans.
Que. 11 12 13 14 15 16 17 18 19 20
Ans.
Que. 21 22
Ans.

PART - I
1. (4) 2. (1) 3. (2) 4. (1) 5. (4)
6. (2) 7. (4) 8. (4) 9. (3) 10. (4)
11. (1) 12. (4) 13. (4) 14. (3) 15. (3)
16. (4) 17. (2) 18. (3) 19. (3) 20. (4)
21. (1) 22. (2) 23. (1) 24. (4) 25. (1)
26. (3) 27. (1) 28. (3) 29. (1) 30. (1)
PART - II
1. 3.33 × 10 cm
16 –2
2. Ba2+, 10 m mol/L 3. (A)
4. (D) 5. (A) 6. (A) 7. (B) 8. (A)
9. (C) 10. 20 11. (B,C) 12. (A.B.D) 13. (B,C,D)
14. (B,C) 15. (B,C,D) 16. (B,C,D) 17. (B,C,D)
PART - III
1. (D) 2. (B) 3. (C) 4. (B) 5. (D)
6. (B) 7. (B) 8. (A,B,D) 9. (A) 10. (A,B,D)
11. (B,C) 12. (A,B,D) 13. 25 14. 4 15. 03
16. 60 17. 50 18. 2 19. (B) 20. (C)
21. (A) 22. (C)
PART - I
x x 1
1. = KP1/n, log = logK + logP
m m n
2. That's why lyophilic colloid has affinity for water.
3. Scattering of light by colloidal particles is known as Tyndall effect.
4. Tyndall effect is shown by colloidal solution.
5. In milk, liquid fat particles are dispersed in water.
6. Higher the charge on coagulating ion, higher the coagulating power.
7. Gold sol is – ve sol, so coagulating ion is cation.
8. Lyophilic colloid is solvated by dispersion medium and becomes more stable.
9. Coagulating power  charge on coagulating ion.
10. Effectiveness of coagulation by electrolyte  charge on coagulating ion.

11. Fog is an example of liquid dispersed in gas.
12. As2S3 colloidal sol is obtained when As2O3 is saturated with H2S :
As2O3 + 3H2S  As2S3 + 3H2O.
As2S3 adsorbs S2– ions (common between H2S and As2S3 and thus is negatively charged).
As2S3 + H2S  As2S3 S2– : 2H+.
13. Light is scattered by colloidal particles present in environment so sky looks blue.
14. Colloidal particle shows Tyndall effect because of it's larger size.
15. Brownian motion is due to impact of molecules of the dispersion medium on the colloidal particles.
16. As2S3 is negatively charged sol so more positively charged ion will have minimum coagulating value .
17. Gelatin is positive sol.
18. Sulphur is a lyophobic colloid.
19. Smoke is an example of solid dispersed in gas.
20. Arsenious sulphide is negatively charged sol so more the charge on cation of electrolyte, more the efficiency
of electrolyte for coagulation.
21. Colloid is heterogeneous, biphasic solution.
22. Smaller the charge on coagulating ion, higher the flocculation value.
23. Easily liquefiable gases like CO2 are adsorbed to a greater extent than gases like O2, N2 and H2
24. Electrophoresis means movement of colloidal particles under the influence of electric field.
25. Negative catalyst provides a path of higher activation energy
26. These are the properties of colloidal solution.
27. Adsorption theory is given for heterogeneous catalyst. Example : adsorption of gas on solid surface.
x
28. According to Freundlich adsorption isotherm,  kp1/n (n > 1).
m
29. Physical adsorption is due to vander waals forces.
x x 1
30. According to Freundlich isotherm : = Kp1/n or log = log K + logP (For solution, P = C).
m m n
PART - II
20
1. Mass of glucose adsorbed = (20 – 19) × = 2 × 10–5 g.
10 6
2  10 5 10 6
Moles of glucose adsorbed = = .
180 9
10 6 20
Number of glucose molecules = × 6 × 1023 = × 1016
9 3
1 20
Number of glucose molecules per unit area = × × 1016 = 3.33 × 1016 cm–2.
2 3

10 4
2. Conc. of Ba2+ = M = 10–2 M = 10 mmole/L.
10  10 3
3. Loss of water from gel is known as synerisis.
4. All are facts to remember.
5. Reddish brown sol is prepared by adding FeCl3 in Fe(OH)3 precipitate.
6. Similar charged colloidal particles will repel each other so colloidal system will not be suspended.
7. Micelles have large molar mass so less colligative property.
x 1
8. log = log k + log P
M n
1
= tan 45° ln k = 0.69
n
n=1 k=2
x
= 2 x (0.5)1
m
x=1
9. 200 mL of the sol require = 0.73 g HCl

0.73
= mol = 0.02 mol = 20 m mol.
36.5
20mmole
So, flocculation value of HCl = = 100
0.2lit
10. Gold number is minimum amount of protective colloid which can protect 10 mL standard gold sol from
coagulation when 1 mL of 10% NaCl is added.
11. (B) Aluminium hydroxide is a +ve sol, so – ve ions are effective in coagulation.
(C) Cellulose solution is an example of macromolecular colloid.
12. Egg albumin is lyophlic colloid.
13. Monolayer is formed during chemisorption.
14. This is because of absorption.
15. Fe(OH)3 is postive sol, remaining all three are negative sol.
16. Lyophobic colloid are solvent hating.
17. Small particles has more random behaviour.
PART - III
1. – ve charged sol is coagulated by cation of electrolyte. More the charge on cation, higher the precipitating
power.
2. More the charge on cation, higher the coagulating power.
3. Ferric hydroxide sol is + vely charged sol.
4. Lyophobic colloids are irreversible colloids.
5. Particle size of the adsorbent affects the amount of adsorption.
6. (i) NH3 is easily liquifiable, so ordered more than H2.

(ii) This phenomenon is known as electrophoresis, not Brownian movement.

7. Enzymes are highly specific heterogeneous catalyst.
8. Efficiency of a heterogeneous catalyst increases with its surface area.

Catalyst provides a path of lower activation energy but enthalpy of reaction is not affected.
9. Catalyst may appear in rate expression. But it is not consumed in the reaction.
10. (A) H = –ve for adsorption

(B) fact
(D) chemical bonds are stronger than vander waal’s forces so chemical adsorption is more exothermic.
11. (B) Aluminium hydroxide is a +ve sol, so – ve ions are effective in coagulation.
(C) Cellulose solution is an example of macromolecular colloid.
12. A negative catalyst does not raises the activation energy barrier of a reaction; it actually functions to re-
move the active intermediate from the reaction and thus, it retards the rate of a reaction.
13. Gold number is minimum amount of protective colloid which can protect 10 ml standard gold sol from
coagulation when 1 ml of 10% NaCl is added.
15. Mass of acetic acid adsorbed = (0.6 – 0.5) × 1 × 60 = 6 gm

6
Mass of acetic acid adsorbed per gram of carbon = = 3 gm.
2
16. 1 litre colloidal solution contains = 10–3 × NA molecule of C12H25SO4Na.
10 3  NA  1
1 mm 3 colloidal solution contains = = 6 × 1014 molecule of C12H25SO4Na.
10 6
1013 colloidal particles = 6 × 1014 molecule of C12H25SO4Na.
6  1014
1 colloidal particle = molecule of C12H25SO4Na = 60 molecules.
1013
17. 10 ml of 1 M NaCl contains NaCl = 10 × 1 = 10 milli mole

200 ml of As2S3 required NaCl for the coagulation = 10 milli mole
 1000 ml of As2S3 required NaCl for the coagulation = 10 × 1000/ 200 = 50 milli mole
18. Let V litre of palmitic acid is required.

5.12 V
Number of molecules = × 6.023 × 1023 = 1.2 × 1022 V
256
Area covered = (1.2 × 1022 V)(0.2 × 10–14 cm2) = 2.4 × 107 V cm2
2.4 × 107 V cm2 = 500 cm 2
2
V = 0.02 cm3 = cm3
100
X=2
19. We want to prepare sol of Ag having positively charged particles, so a little excess of Ag+ should be added
to K.
20. The sols will neutralise each other so will coagulate each other because of opposite charge.
21. Greater the charge on negative ions of salt used (since sol is positively charged) smaller will be its coagulating
value.
22. (A) Coagulation is known as accmulation of collidal sols.
(B) Dialysis is purification of colloids.
(C) Peptization is formation of colloidal solution from precipitates.
(D) Tyndall effect is scattering of light by colloidal particle

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Coordination Compounds

 Marked Questions may have for Revision Questions.

PART - I : SUBJECTIVE QUESTIONS

Section (B) : Nomenclature of coordination compounds

Section (C) : Werner's Theory

Section (D) : Valence Bond Theory + Crystal Field Theory (Part-I)

D-2. Predict the hybridisation and geometry of the following complexes.

Section (E) : Valence Bond Theory + Crystal Field Theory (Part-II)

E-2. Predict the hybridisation and geometry of the following complexes.

Section (F) : Applications of crystal field theory

Section (G) : Isomerism in Coordination compounds

G-1. What type of isomers are the following :

Section (H) : Organometallic Compounds

PART - II : ONLY ONE OPTION CORRECT TYPE

A-2. The donor sites of (EDTA)4– are ?

A-4. Ligands are :

A-5. The oxidation state of Mo in its oxido-complex species [Mo2O4(C2H4)2(H2O)2]2– is

Section (B) : Nomenclature of coordination compounds

B-3. The formula of the complex tris(ethylenediamine)cobalt(III) sulphate is :

B-4. The correct IUPAC name for the compound [Co(NH3)4CI(ONO)]Cl is :

B-5. The hypothetical complex triamminediaquachloridocobalt(III) chloride can be represented as :

C-2. The EAN of platinum in potassium hexachloridoplatinate(IV) is (Atomic number of Pt = 78) :

C-4. Which of the following will exhibit maximum ionic conductivity?

C-5. Which of the following shows maximum molar conductance ?

C-6. The complex [Cr(H2O)4Br2]Cl gives the test for :

Section (D) : Valence Bond Theory + Crystal Field Theory (Part-I)

Section (E) : Valence Bond Theory + Crystal Field Theory (Part-II)

E-2. Which of the following molecules is not tetrahedral ?

E-3. The complex [Pt(NH3)4]2+ has ..... structure :

E-5. The hybridisation and unpaired electrons in [Fe(H2O)6]2+] ion are :

E-7. Which of the following is a high spin complex ?

E-8. Which has maximum paramagnetic nature ?

E-9. The number of unpaired electrons present in complex ion [FeF6]3- is :

E-11. Select the correct statement.

E-12. Amongst Ni(CO)4, [Ni(CN)4]2– and NiCI42– :

F-1. The compound which does not show paramagnetism ?

Section (G) : Isomerism in Coordination compounds

G-1. The complexes [Pt(NH3)4] [PtCl6] and [Pt(NH3)4Cl2] [PtCl4] are :

G-2. [Co(NH3)5NO2]Cl2 and [Co(NH3)5ONO]Cl2 are related to each other as :

G-3. The number of geometrical isomer of [Co(NH3)3(NO3)3] are :

G-4. Geometrical isomerism is found in coordination compounds having coordination number :

G-6. Geometrical isomerism can be shown by :

Section (H) : Organometallic Compounds

H-2. Formula of ferrocene is:

MATCH THE COLUMN

 Marked Questions may have for Revision Questions.

PART - I : ONLY ONE OPTION CORRECT TYPE

8. Which of the following statements is not correct?

PART - II : SINGLE AND DOUBLE VALUE INTEGER TYPE

6. How many of the following is correctly matched complex ?

(1) K3[Co(C2O4)3] +3 t 62g e 0g

(2) (NH4)2[CoF4] +2 t 52g e 2g

8. The number of coordination isomers possible for [Fe(NH3)6]3+ [Cr(C2O4)3]3– is _______

9. Find the sum of number of geometrical isomers for following complexes.

PART - III : ONE OR MORE THAN ONE OPTIONS CORRECT TYPE

3. Select the correct statements ;

4. Consider the following statements :

5. Which of the following is/are correctly matched ?

7. 'Spin only' magnetic moment of Ni in [Ni(dmg)2] is same as that found in :

8. Which complex of the following pairs has the larger value of 0 ?

12. Following Sidwick's rule of EAN, Co(CO)x will be :

1. The correct formula of the complex is :

A-4. (A) nitrito-N M  O—N=O nitrito-O

(B) M  SCN thiocyanato or thiocyanato-S, M  NCS isothiocyanato or thiocyanato-N