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Volume 25 No.

3 March 2016

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Chemistry Musing Problem Set 32 8

CONTENTS AIPMT Practice Paper 2016


Advanced Chemistry Bloc
10
22
Concept Booster 26
Chemistry Musing Solution Set 31 30

JEE Accelerated Learning Series 31


Concept Map 46
JEE Main Practice Paper 2016 56
Ace Your Way CBSE XII (Practice Paper 2016) 61
Olympiad Problems 71
AIPMT 2016 (Model Test Paper) 75
AIIMS Special (Assertion & Reason) 82
You Ask, We Answer 86
Crossword 89

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chemistry tODAy
ODA | march ‘16
ODAy 7
CHEMISTRY MUSING
hemistry Musing was started from August '13 issue of Chemistry Today with the suggestion of
C Shri Mahabir Singh. The aim of Chemistry Musing is to augment the chances of bright students preparing for
JEE (Main and Advanced) / AIPMT / AIIMS / Other PMTs & PETs with additional study material.
In every issue of Chemistry Today, 10 challenging problems are proposed in various topics of JEE (Main
and Advanced) / AIPMT. The detailed solutions of these problems will be published in next issue of Chemistry
Today.
The readers who have solved five or more problems may send their solutions. The names of those who send
atleast five correct solutions will be published in the next issue.
We hope that our readers will enrich their problem solving skills through "Chemistry Musing" and stand in better
stead while facing the competitive exams.

Set 32

jee main/PmTs 5. The order of stability of the following three


compounds is
1. The decreasing order of the bond moment in NH3,
PH3, AsH3 and SbH3 is given by CH2 CH CH2+
(a) NH3 > PH3 > AsH3 > SbH3 +
Cl
(b) SbH3 > PH3 > AsH3 > NH3 I II III
(c) NH3 > AsH3 > PH3 > SbH3 (a) III > I > II (b) III > II > I
(d) NH3 > SbH3 > AsH3 >PH3 (c) I > III > II (d) I > II > III
2. In the given sequence of reactions, the compound S jee advanced
is
6. What is the entropy change when 1 kg of water is
H2, Pd/C Br2, hv Mg/ether D2O
P Q R S heated from 27°C to 200°C forming super-heated
steam under constant pressure? (Given : Specific
H H D OD heat of water = 4180 J/kg-K, specific heat of
(a) (b) steam = 1670 + 0.49T J/kg-K (where T is absolute

H D H OD
(c) (d)

3. Mole fraction of K2CO3 in a mixture of K2CO3 and


KHCO3 is 0.5. The volume of 0.1 N HCl required to
neutralize its 1.252 g mixture is
(a) 100 mL (b) 152.5 mL
(c) 157.8 mL (d) 102 mL
4. 4HNO3 + P4O10 4HPO3 + X
In the above reaction, the product X is
(a) NO2 (b) N2O3
(c) N2O4 (d) N2O5

8 chemistry tODAy | March ‘16


temperature) and latent heat of vaporisation = (c) electrophilic addition – elimination
23 × 105 J/kg.) (d) elimination – addition
(a) 7522.4 J (b) 75.22 J O
(c) 7.522 J (d) 445.2 J O
8. When is reacted with two moles of CH3MgI
comPrehension
followed by hydrolysis, the product obtained is
Amides generally in the presence of acids or bases
OH
undergo hydrolysis to form carboxylic acids and
amines. The conditions required here are more (a) OH (b) OH
OH
extreme when compared to those for hydrolysis O
OH OH
of esters, anhydrides or acid chlorides though (c) HO (d)
the mechanism is same and the intermediates
inTeger value
(tetrahedral) are also same.
Thus, these reactions are quite different from the 9. Rn (an a-emitter) emits a-particle having
alkyl substitution reactions. kinetic enery equal to 5.5 MeV and wavelength
equal to 2 × 10–6 sec–1. For 1 Ci Rn, the energy
7. The mechanism involved during hydrolysis of acid released in 1 hr is 72 × x. The value of x is
derivatives is
10. For [Ti(H2O)6]2+, the CFSE value is n × 10–1 Do.
(a) addition – elimination
The value of n is
(b) nucleophilic addition – elimination


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chemistry tODAy | March ‘16 9


Class
XI-XII

*Dr. Sangeeta Khanna


clAss-Xi : chemicAl AnD iOnic equilibrium | thermODynAmics
Kb for fluoride (F–) ion at 298 K is 10, the
1. If pK If 1.0 mol each of all the four gases is taken in a
ionization constant of hydrofluoric (HF) acid in one litre container the concentration of NO2 at
water at this temperature is equilibrium would be
(a) 10–4 (b) 10–10 (c) 104 (d) 10 (a) 1.6 mol L–1 (b) 0.8 mol L–1
–1
2. The solubility product of MgF2 is 7.4 × 10–11. (c) 0.4 mol L (d) 0.6 mol L–1
Calculate the solubility of MgF2 in 0.1 M NaF 7. For which of the following reactions, the degree of
solution dissociation cannot be calculated from the vapour
(a) 7.4 × 10–9 (b) 3.7 × 10–9 density data
–11
(c) 3.7 × 10 (d) 7.4 × 10–11 I. 2HI(g) H2(g)
g
g) g + I2(g)
g) g
g)
3. The aqueous solution of potash alum II. 2NH3(g) g
g) N2(g)
g + 3H2(g)
g) g
g)
[K2SO4⋅Al2(SO4)3⋅24H2O] is acidic due to III. 2NO(g)g
g) N2(g)
g + O2(g)
g) g
g)
(a) hydrolysis of K+ (b) hydrolysis of Al3+ IV. PCl5(g) PCl + Cl
g
g) g
g)
3(g) g
g)
2(g)
(c) hydrolysis of SO42– (a) I and III (b) III and IV
(d) presence of acid in its crystal as impurity. (c) I and II (d) II and III
4. For reaction, 8. The aqueous solutions of four sodium salts Na
NaA,
2NOCl(g)g
g) 2NO(g)
g) g , Kc at 427°C is
g + Cl2(g)
g) NaB, NaC C and NaD has pH 7.0, 9.0, 10.0 and 11.0
3 × 10–6 L mol–1. The value of Kp is nearly, respectively, when each solution is 0.1 M. The
(a) 7.50 × 10–5 (b) 2.50 × 10–5 strongest acid is
–4
(c) 2.50 × 10 (d) 1.75 × 10–4 (a) HA (b) HB
5. Does the number of moles of reaction products (c) HC (d) HD
increase, decrease or remain same when each of 9. In the hydrolytic equilibrium,
the following equilibria is subjected to a decrease in A– + H2O HA + OH–
pressure by increasing the volume? –5
Ka = 1.0 × 10 . The degree of hydrolysis of a 0.001 M
(i) PCl5(g)
g
g) PCl3(g)
g + Cl2(g)
g) g
g) solution of the salt is
(ii) CaO(s) + CO2(g)
g
g) CaCO3(s) (a) 10–2 (b) 10–3
(a) (i) increase, (ii) increase (c) 10–4 (d) 10–5
(b) (i) decrease, (ii) decrease 10. A weak acid HX X has the dissociation constant
(c) (i) increase, (ii) decrease –5
1 × 10 M. It forms a salt Na X on reaction with
NaX
(d) (i) decrease (ii) increase alkali. The degree of hydrolysis of 0.1 M solution
6. At a certain temperature, the equilibrium constant of Na
NaXX is
Kc is 16 for the reaction, (a) 0.0001% (b) 0.01%
SO2(g)
g + NO2(g)
g) g
g) SO3(g)
g + NO(g)
g) g
g) (c) 0.1% (d) 0.15%
*A renowned chemistry expert, Chemistry Coaching Circle, Chandigarh, 09814129205

10 chemistry tODAy
ODA | march ‘16
ODAy
11. On adding 0.1 M solution each of Ag+, Ba2+, Ca2+ in 18. Some chemists at ISRO wished to prepare a
a Na2SO4 solution, species first precipitated is saturated solution of a silver compound and they
[Ksp(BaSO4) = 10–11, Ksp(CaSO4) = 10–6, wanted it to have the highest concentration of silver
Ksp(Ag2SO4) = 10–5] ion possible. Which of the following compounds
(a) Ag2SO4 (b) BaSO4 would they use?
(c) CaSO4 (d) all of these. Ksp(AgCl) = 1.8 × 10–10, Ksp(AgBr) = 5.0 × 10–13
Ksp(Ag2CrO4) = 2.4 × 10–12
12. Calculate the buffer capacity of a solution if its pH (a) AgCl (b) AgBr
changes from 4.745 to 4.832 on addition of 0.01 (c) Ag2CrO4 (d) Any of them
mole of NaOH to its 250 mL solution.
19. Four solutions of NH4Cl are taken with
(a) 0.087 (b) 0.04
concentration 1 M, 0.1 M, 0.01 M and 0.001 M.
(c) 0.46 (d) 0.01
Their degrees of hydrolysis are h1, h2, h3 and h4.
13. Ksp of Fe(OH)3 in aqueous solution is 3.8 × 10–38 What is the graduation of degrees of hydrolysis?
at 298 K. The concentration of Fe3+ will increase (a) h1 > h2 > h3 > h4 (b) h1 = h2 = h3 = h4
when (c) h4 > h3 > h2 > h1 (d) None of these
(a) pH is increased (b) pH is 7 20. Solubility of calcium phosphate (molecular mass, M)
(c) pH is decreased (d) it is exposed to air. in water is W g per 100 mL at 25°C. Its solubility
14. In the interaction of B(CH3)3 with N(CH3)3, product at 25°C will be approximately
(a) B(CH3)3 is a Lewis base and N(CH3)3 is a Lewis 5 5
9 W  W 
acid (a) 10   (b) 107  
M M
(b) B(CH3)3 is a Lewis acid and N(CH3)3 is a Lewis 5 5
W  W 
base (c) 105   (d) 103  
M M
(c) both are Lewis acids
(d) both are Lewis bases. 21. When NH3 is heated in a 0.50 L flask at 700 K and
100 atm pressure, it decomposes into N2 and H2
15. Ksp(BaSO4) is 1.1 × 10–10. In which case is BaSO4
and their equilibrium moles are given below
precipitated?
2NH3(g) N2(g) + 3H2(g)
(a) 100 mL of 4 × 10–3 M BaCl2 + 300 mL of 0.30 0.30 0.90
6.0 × 10–4 M Na2SO4 Which of the pairs given represents correct value?
(b) 100 mL of 4 × 10–4 M BaCl2 + 300 mL of Initial moles of NH3 Kc for NH3 formation
6.0 × 10–8 M Na2SO4 (a) 0.80 9.72
(c) 300 mL of 4 × 10–4 M BaCl2 + 100 mL of (b) 0.90 9.72
6.0 × 10–8 M Na2SO4 (c) 0.80 0.103
(d) In all cases (d) 0.90 0.103
16. Ksp of Mg(OH)2 is 1.8 × 10–11 at 30°C. Its molar 22. Volume of the flask in which species are transferred
solubility at pH = 12 is is double of the earlier flask. In which of the
(a) 1.8 × 10–11 M (b) 1.8 × 10–9 M following cases extent of equilibrium is affected?
–54
(c) 1.34 × 10 M (d) 1.8 × 10–7 M I : N2(g) + 3H2(g) 2NH3(g)
II : N2(g) + O2(g) 2NO(g)
17. Select the correct statements about indicators.
(a) Near the equivalence point pH = pKa for weak III : PCl5(g) PCl3(g) + Cl2(g)
acid indicator and pH = (14 – pKb) for weak IV : 2NO(g) N2(g) + O2(g)
base indicator. (a) I, II (b) II, III
(b) Most indicators have a transition range of two (c) I, III (d) III, IV
pH units. 23. For the reaction, 2A(g) + 2B(g) 3C(g) at a certain
(c) Methyl orange shows coloured form in acid temperature, Kc is 2.5 × 10–2. For which conditions
solution. will reaction proceed to the right at the same
(d) All the above statements are correct. temperature?

chemistry tODAy | march ‘16 11


[A] [B] [C] 29. Which of the following is correct order of acidic
(a) 0.01 M 0.10 M 0.10 M strength?
(b) 1.0 M 1.0 M 1.0 M (a) HF > HCl > HBr
(c) 1.0 M 0.10 M 0.10 M (b) Mn2+ > Mn3+ > Mn4+ (Lewis acid)
(d) 1.0 M 1.0 M 0.10 M (c) N2O5 > NO2 > N2O3
24. One mole of an ideal gas at 300 K is expanded (d) H2SO4 > HNO3 > HClO4
isothermally from an initial volume of 1 litre to 30. How much electrical work will be done in the
10 litres. DU for the process is (R = 8.314 J K–1 mol–1) following redox reaction?
(a) 40 J (b) Zero 5
CH CH + O2 2CO2 + H2O
(c) 340 J (d) 9 litre atm 2
25. What are the signs of DH, DS, and DG for the (a) 5FE° (b) 10FE° (c) 4FE° (d) 8FE°
following spontaneous change? 31. Which of the following is the correct graph for
titration of strong acid with weak base?

7 7
(a) pH (b) pH
(a) DH = +, DS = +, DG = –
(b) DH = +, DS = –, DG = – Vol. of base added Vol. of base added
(c) DH = –, DS = +, DG = –
(d) DH = –, DS = –, DG = –
7
26. A gas expands against a constant external pressure (c) pH (d) None of these
of 2.00 atm from an initial volume of 1.50 L to a final
volume of 3.50 L. The container is well insulated so
Vol. of base added
that no heat enters or leaves the system. Calculate
the change in internal energy DU of the gas in 32. A sample of liquid in a thermally insulated container
joules. [1 L atm = 101 J] (a calorimeter) is stirred for 2 hr by a mechanical
(a) –404 (b) + 404 linkage to a motor in the surrounding, for this
(c) 4.00 (d) 25.3 process
27. The standard enthalpy of formation of CO2(g), CO(g), (a) w < 0; q = 0; DU = 0 (b) w > 0; q > 0; DU > 0
N2O(g) and NO2(g) in kJ mol–1 are –393, –110, +81 (c) w < 0; q > 0; DU = 0 (d) w > 0; q = 0; DU > 0
and 34 respectively. Calculate the standard enthalpy 33. Given the following equations and DH° values,
of reaction (in kJ) given below : H2(g) + F2(g) 2HF(g); DH°1 = –537 kJ
2NO2(g) + 3CO(l) N2O(g) + 3CO2(g)
C(s) + 2F2(g) CF4(g); DH°2 = –680 kJ
(a) –836 (b) +1460
(c) +836 (d) –1170 2C(s) + 2H2(g) C2H4(g); DH°3 = 52 kJ
Determine the enthalpy of reaction at 298 K for the
28. A reaction mixture has concentration such that DG
reaction,
is zero. However, DG° for the reaction is +10 kJ. This
information means that C2H4(g) + 6F2(g) 2CF4(g) + 4HF(g)
(a) further reaction will take place to form more (a) – 1165 kJ (b) – 2486 kJ
products. (c) + 1165 kJ (d) + 2486 kJ
(b) the reverse reaction will take place to form 34. Determine enthalpy of formation for H2O2(l), using
more reactants. these listed enthalpies of reaction.
(c) the reaction mixture is at equilibrium but the N2H4(l) + 2H2O2(l) N2(g) + 4H2O(l);
concentration of products is small DrH°1 = –818 kJ/mol
(d) the reaction mixture is at equilibrium and the N2H4(l) + O2(g) N2(g) + 2H2O(l);
concentration of products is large. DrH°2 = –622 kJ/mol

12 chemistry tODAy | march ‘16


H2(g) + 1/2O2(g) H2O(l); DrH°3 = –285 kJ/mol 40. What will be the pH of a solution obtained by
(a) –383 kJ/mol (b) –187 kJ/mol mixing 800 mL of 0.05 N sodium hydroxide and
(c) –498 kJ/mol (d) None of these 200 mL of 0.1 N hydrochloric acid assuming
complete ionization of the acid and base?
35. Calculate the enthalpy for the following reaction
(a) 12.3010 (b) 2.699
using the given bond energies (kJ/mol).
(c) 10.546 (d) 11.4771
(C H = 414; H O = 463; H Cl = 431,
C Cl = 326; C O = 335) 41. If Ksp (PbSO4) = 1.8 × 10–8 and Ka(HSO4–) = 1.0 × 10–2
CH3 OH(g) + HCl(g) CH3 Cl(g) + H2O(g) The equilibrium constant for the reaction,
PbSO4(s) + H+(aq) HSO–4(aq) + Pb2+(aq) is
(a) –23 kJ/mol (b) –42 kJ/mol
–6 –10
(c) –59 kJ/mol (d) –511 kJ/mol (a) 1.8 × 10 (b) 1.8 × 10
(c) 2.8 × 10–10 (d) 1.0 × 10–2
36. Calculate the heat produced (in kJ) when 224 g of
CaO is completely converted to CaCO3 by reaction 42. For a reaction, A(g) + 3B(g) 2C(g); DH° = –24 kJ
with CO2 at 27°C in a container of fixed volume. The value of DG° is –9 kJ. The standard entropy
Given: DH°f (CaCO3, s) = –1207 kJ/mol; change of reaction is
DH°f (CaO, s) = –635 kJ/mol; (a) 5 J K–1 (b) 50 J K–1
–1
(c) 500 J K (d) 0.5 J K–1
DH°f (CO2, g) = –394 kJ/mol;
[Use R = 8.3 K–1 mol–1] 43. Match the following :
(a) 702.04 kJ (b) 721.96 kJ List I List II
(c) 712 kJ (d) 721 kJ (P) Heat capacity 1. DH is positive
(Q) Standard Gibbs free 2. DG is negative
37. For the reaction, energy changes
CH4(g) + 2O2(g) CO2(g) + 2H2O(g), (R) Endothermic process 3. –2.303RT log K
–1
DHr = –170.8 kJ mol . Which of the following dQ
statements is not true? (S) Spontaneous process 4.
dt
(a) The reaction is exothermic. 5. DH = DngRT
(b) At equilibrium, the concentration of CO2(g) and Codes :
H2O(l) are not equal. P Q R S
(c) The equilibrium constant for the reaction is (a) 5 4 2 1
[CO2 ] (b) 4 3 1 2
given by K P = .
[CH 4 ][O2 ]2 (c) 4 3 2 1
(d) 5 3 2 1
(d) Addition of CH4(g) or O2(g) at equilibrium will
cause a shift to the right. 44. Match the following :
List I List II
38. The pH of solution of both ammonium acetate and
(P) van’t Hoff equation 1. Variation of enthalpy
sodium chloride is 7 due to
of a reaction with tempera-
(a) hydrolysis in both cases
ture
(b) cationic and anionic hydrolysis of the former
(Q) Kirchhoff equation 2. Variation of equilibrium
and not the latter.
constant with temperature.
(c) no hydrolysis in both (R) Second law of 3. Entropy of an isolated
(d) hydrolysis of the latter but not the former. thermodynamics system tends to increase
39. Which of the following solutions on mixing and reach a thermodyna-
will show maximum increase in temperature on mics maximum value.
neutralization? (S) Hess’s law of 4. Enthalpy change in a
(a) 50 mL HCl + 40 mL NaOH of 0.01 Normality constant reaction is always constant
(b) 10 mL HCl + 10 mL NaOH of 0.01 Normality summation and independent of the
(c) 400 mL HCl (0.01N) + 100 mL NaOH (0.01N) manner in which the
(d) 500 mL HCl (0.01 N) + 600 mL NaOH (0.01N) reaction occurs.

chemistry tODAy | march ‘16 13


Codes : 45. For which of the following processes DStotal < 0?
P Q R S (a) Melting of ice below – 4°C at 1 atm
(a) 1 2 3 4 (b) Intermixing of gases
(b) 1 3 2 4 (c) Burning of H2 in oxygen
(c) 2 1 3 4 (d) Evaporation of water above 100°C
(d) 1 2 4 3
clAss-Xii : cOOrDinAtiOn chemistry | p-blOck elements
1. Which one of the following arrangements does not 8. Nitrogen combines with metals to form
truly represent the property indicated against it? (a) nitrites (b) nitrates
(a) Br2 < Cl2 < F2 : Oxidising power (c) nitrides (d) nitrosyl chloride.
(b) Br < Cl < F : Electronegativity 9. SO2 oxidises
(c) Br < F < Cl : Electron affinity
(a) Mg (b) KMnO4
(d) Br2 < Cl2 < F2 : Bond energy
(c) K2Cr2O7 (d) all of these.
2. Which of the following species have undistorted
10. Iodine is formed when KI reacts with a solution
octahedral structure?
of
1. SF6 2. PF6– 3. SiF62– 4. XeF6
(a) ZnSO4 (b) CuSO4
The correct answer is
(c) FeSO4 (d) (NH4)2SO4
(a) 1,2 and 4 (b) 1, 2 and 3
(c) 1,3 and 4 (d) 2,3 and 4 11. Tin reacts with conc. HNO3 to form
3. Hydrolysis of one mole of peroxodisulphuric acid (a) metastannic acid (b) stannic nitrate
produces (c) stannous nitrate (d) tinstone.
(a) one mole of sulphuric acid and one mole of 12. Which of the following statements regarding the
peroxomonosulphuric acid manufacture of H2SO4 by Contact process is not
(b) one mole of sulphuric acid, one mole of peroxo true?
monosulphuric acid and one mole of hydrogen (a) S is burnt in air to form SO2.
peroxide (b) SO2 is oxidized to SO3 in presence of V2O5 as
(c) two moles of sulphuric acid catalyst (or finely divided spongy platinum as
(d) two moles of peroxomonosulphuric acid. catalyst) at a pressure of 2 atm and a temperature
4. When chlorine water is added to a solution of KBr, of about 700 K
the solution immediately turns orange red, because (c) SO3 is dissolved in H2O to get 100% H2SO4.
(a) chlorine is reduced to chloride ion (d) H2SO4 obtained by contact process is of higher
(b) of the formation of Br3– purity than that obtained by lead chamber
(c) of the formation of BrCl process.
(d) bromide ion is oxidised to bromine. 13. Which of the following statements is not true about
5. Copper sulphate solution reacts with KCN to give trimethyl and trisilyl amine?
(a) Cu(CN)2 (b) CuCN (a) Trimethyl amine has a pyramidal shape while
(c) K2[Cu(CN)4] (d) K3[Cu(CN)4] trisilyl amine has a planar shape.
6. Which of the following is tetrabasic acid? (b) Nitrogen atom in both trimethyl and trisilyl
(a) Orthophosphoric acid amines is in a state of sp3 and sp2 hybridization
(b) Pyrophosphorus acid respectively.
(c) Metaphosphoric acid (c) Lone pair of electrons present in p-orbitals of
(d) Pyrophosphoric acid nitrogen in trisilyl amine form pp-dp bond
with the vacant d-orbitals of silicon atom.
7. Calcium cynamide on treatment with steam under
(d) Trisilyl amine is more basic in comparison to
pressure gives NH3 and
trimethyl amine because of the availability of
(a) CaCO3 (b) Ca(OH)2
the lone pair of electrons on nitrogen atom.
(c) CaO (d) CaHCO3

14 chemistry tODAy | march ‘16


14. P2O5 reacts with H2SO4 to give SO3 and HPO3. (b) Increase in bond angle, SbH3 < AsH3 < PH3 <
Which property of P2O5 is depicted in this NH3
reaction? (c) Decrease in bond angle, NH3 > PH3 > AsH3 >
(a) It acts as a strong dehydrating agent. SbH3.
(b) It is a white powder. (d) Increase in boiling point, PH3 < SbH3 < BiH3 <
(c) It sublimes on heating. NH3
(d) It is acidic in nature. 22. A yellow metallic powder is burnt in a stream
15. A greenish yellow gas reacts with an alkali metal of fluorine to obtain a colourless gas X which is
hydroxide to form a halate, which can be used in thermally stable and chemically inert. Its molecule
fire works and safety matches. The gas and halate has octahedral geometry. Another colourless gas Y
respectively are with same constituent atoms as that of X is obtained
(a) Br2, KBrO3 (b) Cl2, KClO3 when sulphur dichloride is heated with sodium
(c) I2, NaIO3 (d) Cl2, NaClO3 fluoride. Its molecule has trigonal pyramidal
structure. X and Y are respectively.
16. 20 V H2O2 means that
(a) SF4 and S2F2 (b) SF6 and SF4
(a) 20 mL of this H2O2 evolves 20 mL of O2 at
(c) NaF and NaCl (d) SF4 and SF6
NTP
(b) 10 mL of this H2O2 evolves 20 mL of O2 at 23. Sometimes a yellow turbidity appears while passing
NTP H2S gas even in the absence of group II radicals.
(c) 1 mL of this H2O2 evolves 20 mL of O2 gas at This is because
NTP (a) sulphur is present in the mixture as impurity
(d) all of the above. (b) group IV radicals are precipitated as sulphides
(c) of the oxidation of H2S gas by some acid
17. Pure nitrogen gas is obtained by heating
radicals
(a) NH3 + NaNO2 (b) NH4Cl + NaNO2
(d) group III radicals are precipitated as
(c) N2O + Cu (d) (NH4)2Cr2O7
hydroxides.
18. Which one of the following oxides of nitrogen
24. The oxidation states of sulphur in the anions
reacts with ferrous sulphate to form a dark brown
SO32–, S2O42– and S2O62– follow the order :
compound used in the detection of nitrate?
(a) N2O (b) NO (a) S2O42– < SO32– < S2O62–
(c) NO2 (d) N2O5 (b) SO32– < S2O42– < S2O62–
19. Which one of the following statements about H2S is (c) S2O42– < S2O62– < SO32–
not correct? (d) S2O62– < S2O42– < SO32–
(a) It is a covalent compound. 25. For making H2O2 in the laboratory
(b) It is a gas at room temperature. (a) MnO2 is added to diluted cold H2SO4
(c) It is a much stronger reducing agent than (b) BaO2 is added to CO2 bubbling through cold
water. water
(d) It is a weak base in aqueous solution. (c) PbO2 is added to an acidified water
20. Which of the following reactions depicts oxidizing (d) Na2O2 is added to an acidified solution of
property of SO2? KMnO4.
(a) SO2 + H2O H2SO3 26. Which of the following statements is not true about
(b) 2H2S + SO2 3S + 2H2O ozone?
(c) Cl2 + SO2 SO2Cl2 (a) It is a pale blue gas at room temperature.
(d) 2MnO4 + 5SO2 + 2H2O 5SO42– + 2Mn2+ + 4H+ (b) It oxidises sulphur and phosphorus evolving
21. Which of the following orders is not correct? oxygen gas.
(a) Decrease in basic strength, NH3 > PH3 > AsH3 (c) It oxidises SnCl2 and SO2 evolving oxygen gas.
> SbH3 (d) It convert BaO2 to BaO and H2O2 to H2O.

chemistry tODAy | march ‘16 15


27. An element (X) forms compounds of the formula (c) H2SO4 also oxidizes HI so formed, to I2
XCl3, X2O5 and Ca3X2 but does not form XCl5. (d) H2SO4 form complex with HI.
Which of the following is the element X?
36. Which among the following elements of 3rd period
(a) B (b) Al (c) N (d) P
shows maximum tendency of forming dp-pp
28. The products of the reaction between HNO3 and bond?
P4O10 are (a) Chlorine (b) Silicon
(a) H3PO4 and N2O5 (b) H3PO4, NO2 and O2 (c) Phosphorus (d) Sulphur
(c) HPO3, NO2 and O2 (d) HPO3 and N2O5
37. Correct statements about the hydrogen halides
29. There is a little difference in acid strength in the include that
series H3PO4, H3PO3 and H3PO2 because I. they are all coloured
(a) phosphorus in these acids exists in different II. their thermal stability decreases with increasing
oxidation states atomic number of the halogen
(b) number of unprotonated oxygen atoms III. they all form soluble silver salts
responsible for increase of acidity due to the IV. they all donate protons to water.
inductive effect remains the same (a) I, II, III are correct (b) I, III are correct
(c) phosphorus is not a highly electronegative (c) II, IV are correct (d) IV is correct
element
38. The compound(s) or ion(s), in which iodine is the
(d) phosphorus oxides are less basic.
central atom, isoelectronic with XeO4, XeF2 and
30. Which of the following bonds has the highest XeF6 respectively are
energy? (a) IF6–, IF2–, IO4– (b) IO4–, IF2–, IF6–
(a) Se Se (b) Te Te – –
(c) IF2 , IO4 , IF6–
(d) IF2–, IF6–, IO4–
(c) S S (b) O O
39. Which of the following is a low-spin (spin-paired)
31. Correct order of O O bond length (increasing) in complex?
O2, H2O2 and O3 is (a) [Co(H2O)6]2+ (b) [Fe(CN)6]3–
(a) H2O2 < O3 < O2 (b) O2 < O3 < H2O2
(c) [Ni(NH3)6]2+ (d) [FeF6]3–
(c) O3 < O2 < H2O2 (d) O3 < H2O2 < O2
40. Which one of the following pairs of isomers and
32. Among Al2O3, SiO2, P2O3 and SO2, the correct
types of isomerism are correctly matched?
order of acid strength is
1. [Co(NH3)5(NO2)]Cl2 and [Co(NH3)5(ONO)]Cl2;
(a) SO2 < P2O3 < SiO2 < Al2O3
Linkage
(b) SiO2 < SO2 > Al2O3 < P2O3
2. [Cu(NH3)4][PtCl4] and [Pt(NH3)4][CuCl4];
(c) Al2O3 < SiO2 < SO2 < P2O3
Coordination
(d) Al2O3 < SiO2 < P2O3 < SO2
3. [Pt(NH3)4Cl2]Br2 and [Pt(NH3)4Br2]Cl2;
33. Of the following sets which one does not contain Ionization
isoelectronic species? Select the correct answer using the codes given
(a) PO43–, SO42–, ClO4– (b) CN–, N2, C22– below :
(c) SO32–, CO32–, NO3– (d) BO33–, CO32–, NO–3 (a) 2 and 3 (b) 1, 2 and 3
34. Bromine can be easily prepared by (c) 1 and 3 (d) 1 and 2
(a) heating any bromide with conc. H2SO4 41. Coordination compounds have great importance
(b) heating any bromide with HCl in biological systems. In this context which of the
(c) passing iodine vapour through bromide following statements is incorrect?
solution (a) Carboxypeptidase-A, is an enzyme and contains
(d) heating any bromide with dilute H2SO4. iron
35. HI cannot be prepared by the action of conc. H2SO4 (b) Haemoglobin is the red pigment of blood and
on KI because contains iron.
(a) HI is stronger acid than H2SO4 (c) Cyanocobalamin is B12 and contains cobalt.
(b) HI is more volatile than H2SO4 (d) cis-platin is an anticancer medicine.

16 chemistry tODAy | march ‘16


chemistry tODAy | march ‘16 17
42. Nickel (Z = 28) combines with a uninegative 21. (d) 22. (b) 23. (c) 24. (a) 25. (b)
monodentate ligand X to form a paramagnetic 26. (c) 27. (c) 28. (d) 29. (b) 30. (c)
complex [NiX4]2–. The number of unpaired 31. (b) 32. (d) 33. (c) 34. (a) 35. (c)
electron(s) in the nickel and geometry of this 36. (a) 37. (c) 38. (b) 39. (b) 40. (b)
complex ion, respectively are 41. (a) 42. (b) 43. (b) 44. (d) 45. (d)
(a) one, tetrahedral (b) two, tetrahedral
sOlutiOns
(c) one, square planar (d) two, square planar.
clAss-Xi
43. Among the following metal carbonyls, the C O
bond order is lowest in 2. (a) : MgF2 Mg2+ + 2F–
x (2x + 0.1)
(a) [Mn(CO)6]+ (b) [Fe(CO)5] 2+ – 2
Ksp of MgF2 = [Mg ][F ]
(c) [Cr(CO)6] (d) [Co(CO)5]+
Ksp = x(2x + 0.1)2
44. The correct order of magnetic moments (spin values Ksp = x(4x2 + 0.01 + 0.4x)
in B.M.) of the complexes is Ksp = 4x3 + 0.01x + 0.4x2
(Atomic no. Mn = 25, Fe = 26, Co = 27)
x3 and x2 are negligible in comparison to x
(a) [Fe(CN)6]4– > [CoCl4]2– > [MnCl4]2–
K sp 7.4 × 10−11
(b) [MnCl4]2– > [Fe(CN)6]4– > [CoCl4]2– so, x = = = 7.4 × 10−9
0.01 0.01
(c) [Fe(CN)6]4– > [MnCl4]2– > [CoCl4]2–
H2O
(d) [MnCl4]2– > [CoCl4]2– > [Fe(CN)6]4– 3. (b) : K2SO4⋅Al2(SO4)3
45. Ammonia forms the complex [Cu(NH3)4]2+ with KOH + H2SO4 + Al(OH)3 + H2SO4
copper ions in alkaline solutions but not in acidic Here, hydrolysis is cationic because Al3+ only reacts
solution because with water.
(a) in alkaline solution Cu(OH)2 is precipitated 4. (d) : Dn = 3 – 2 = 1
which is soluble in excess of alkali Kp = Kc (RT)Dn = 3 × 10–6 × (0.0821 × 700)
(b) copper hydroxide is an amphoteric substance = 1.72 × 10–4
(c) in acidic solution hydration protects Cu2+ ions 6. (c) : SO2(g) + NO2(g) SO3(g) + NO(g)
(d) in acidic solution protons coordinate with Initial conc. 1 1 1 1
ammonia molecule forming ions and NH3 At equilibrium 1–x 1–x 1+x 1+x
molecules are not available. [SO3 ][NO] (1 + x )(1 + x )
K= =
[SO2 ] [NO2 ] (1 − x )(1 − x )
ANSWER Keys
(1 + x )2 (1 + x )
16 = ⇒ =4
clAss-Xi 2 (1 − x )
(1 − x )
1. (a) 2. (a) 3. (b) 4. (d) 5. (c) or x = 0.6
6. (c) 7. (a) 8. (a) 9. (b) 10. (b) [NO2] = 1 – x = 1 – 0.6 = 0.4 mol L–1
11. (b) 12. (c) 13. (c) 14. (b) 15. (a)
7. (a) : The degree of dissociation cannot be calculated
16. (d) 17. (d) 18. (c) 19. (c) 20. (b)
from the vapour density data if the number of
21. (d) 22. (c) 23. (d) 24. (b) 25. (d)
moles remain unchanged before and after reaching
26. (a) 27. (a) 28. (c) 29. (c) 30. (b)
equilibrium.
31. (a) 32. (d) 33. (b) 34. (b) 35. (a)
36. (a) 37. (c) 38. (b) 39. (d) 40. (a) 8. (a) : Aqueous solution of NaA has pH 7.0 (lowest
41. (a) 42. (b) 43. (b) 44. (c) 45. (a) value). Hence, HA is the strongest acid.

clAss-Xii Kw
9. (b) : Degree of hydrolysis, h =
1. (d) 2. (b) 3. (a) 4. (d) 5. (d) K a .c
6. (d) 7. (a) 8. (c) 9. (a) 10. (b)
11. (a) 12. (c) 13. (d) 14. (a) 15. (b) 1 × 10−14
=
16. (c) 17. (b) 18. (b) 19. (d) 20. (b) 1 × 10−5 × 0.001

18 chemistry tODAy | march ‘16


15. (a) : Considering dilution factor due to mixing,
1 × 10−14 BaSO4 is precipitated if
=
1 × 10−5 × 1 × 10−3 [Ba2+] [SO42–] > Ksp
= 10−6 = 10−3 2+ 4 × 10−3
(a) [Ba ]mix = = 10−3 M
10. (b) : Hydrolysis reaction is 4
X– + H2O HX + OH–. 4 × 6 × 10−4
[SO24− ]mix = = 4.5 × 10−4 M
For a salt of weak acid with strong base, 3
[Ba2+][SO42–] = 4.5 × 10–7 > Ksp
K 10−14
K h = w = ch 2 \ = 0.1 × h 2 16. (d) : Mg(OH)2 Mg2+ + 2OH–
Ka 10−5
or h2 = 10–8 or h = 10–4 pH = 12
% hydrolysis = 10–4 × 100 = 10–2 = 0.01 pOH = 2
\ [OH– ] = 10–2 M
11. (b) : For Ag2SO4; Ksp = [Ag+]2 [SO42–]
Ksp = [Mg2+][OH–]2
K sp
[SO42–] needed for precipitation of Ag2SO4 > 1.8 × 10–11 = (s)(10–2)2
+ 2
[Ag ] \ s = 1.8 × 10–7 M
−5
10
= = 10−3 M 10W
0.1 × 0.1 20. (b) : s = mol litre
M
For CaSO4; Ksp = [Ca2+] [SO42–] 5
 10W 
5
\ [SO42–] needed for precipitation of Ksp of Ca3(PO4)2 = 108 s = 108 
 M 
K sp 10−6 5
CaSO4 > = = 10−5 M W 
2+
[Ca ] 0.1 = 107   (approx.)
M
10−11
BaSO24− > 21. (d) : 2NH3 (g) N2(g) + 3H2(g)
0. 1 Initial a 0 0
Equil. (a – 2x) x 3x
SO42–> 10 M–10

Thus, minimum [SO42–] is required for precipitation x = 0.30


of BaSO4 and hence it is precipitated out first. \ a – 2x = 0.30
\ a = 0.90
12. (c) : Buffer capacity
Thus, initial moles of NH3 = 0.90 mol
Moles of acid or base added per litre of buffer 3
=  0.30   0.90 
Change in pH 3    
0.01 / 0.25 [N2 ][H2 ] 0.50   0.50 
= = 0.46 Kc = = = 9.72
0.087 [NH3 ]2  0.30 
2
 
13. (c) : Fe(OH)3 Fe3+ + 3OH– 0.50 
1
3HCl 3Cl– + 3H+ Thus, Kc for NH3 formation = = 0.103
9.72
H+ + OH– H2O
22. (c) : Equilibrium is affected when Dng ≠ 0 thus, I
On adding acid (decrease in pH), the equilibrium
and III.
shifts in the forward direction.
\ [Fe3+] increases. [C]3
23. (d) : Q =
14. (b) : N(CH3)3 has vacant lone-pair on N-atom [ A]2 [B]2
which can be donated to electron-deficient B-atom (a) = 1000 >> Kc
of B(CH3)3. (b) = 1 > Kc
(c) = 0.1 > Kc
(d) = 1 × 10–3 < Kc
Reaction proceeds to right when Q < Kc

chemistry tODAy | march ‘16 19


24. (b) : DU = 0, DT = 0 ( it is isothermal) and the gas For PbSO4 + H+(aq) HSO–4(aq) + Pb2+
(aq)
is ideal. If the gas is non ideal or it is some chemical K sp 1.8 × 10−8
reaction then DU ≠ 0. K= =
Ka 10−2
25. (d) : DS = –ve, as molecules are arranged; reaction
42. (b) : DG° = DH° – TDS°
is spontaneous DG = –ve and one of favourable
factors is –DH. clAss-Xii
26. (a) : Pexternal = constant; Wirr = DU 28. (d) : 2HNO3 + P2O5 2HPO3 + N2O5
Wirr = –PDV as q = 0 P2O5 is a strong dehydrating agent.
30. (b) : No. of electrons exchanged by 5 oxygen atoms 32. (d) : With decrease in size from Al to S the basic
= 10 nature of oxide decreases and acidic nature
W(Electrical) = nFE°cell increases.
31. (a) : At end point, medium should be acidic. Al2O3 < SiO2 < P2O3 < SO2
33. (b) : DH° = 2 × DH°1 + 2 × DH°2 – DH°3 Al2O3 is amphoteric, SiO2 is slightly acidic, P2O3
and SO2 are anhydride of the acids H3PO3 and
34. (b) : For H2(g) + O2(g) H2O2(l)
H2SO3. H2SO3 is a stronger acid than H3PO3.
D H° D H°
D f H °(H2O2 , l ) = D r H 3° + r 2 − r 1 33. (c) : SO32– (42 electrons), CO32– (32 electrons) and
2 2
NO3– (32 electrons) are not isoelectronic.
35. (a)
34. (a) : 2KBr+ 2H2SO4 K2SO4 + SO2 + Br2 +2H2O
36. (a) : CaO(s) + CO2(g) CaCO3(s)
DH°f = DH°f (CaCO3) – DH°f (CaO) – DH°f (CO2) 35. (c) : 2HI + H2SO4 2H2O + I2 + SO2
= –1207 – (–635) – (–394) = – 178 kJ/mol 36. (a) : Among the given elements, Cl has maximum
\ DU = DH – Dng RT tendency of dp-pp bonding. On moving across
(−1) × 8.3 × 300 the period, nuclear charge increases and more s, p
DU = −178 − = –175.51 kJ
1000 electrons are added. The atomic size and so the size
224
nCaO = =4 of 3d-orbitals decreases from Si → P → S → Cl.
56

\ qv = n⋅DrU = 4 × (–175.51) = –702.04 kJ
800 × 0.05
40. (a) : Moles of NaOH (n = 1) = = 0.04
1000
200 × 0.1
Moles of HCl (n = 1) = = 0.02
1000
NaOH + HCl NaCl + H2O
0.04 0.02 0 0
0.02 0 0.02 0.02
Total volume of solution = 800 + 200 = 1000 ml
= 1L
− 0.02
[OH ] = = 0.02
1
pOH = –log (2 × 10–2)
pOH = 1.699
pH = 14 – 1.699 = 12.301
Ksp
41. (a) : PbSO4 Pb2+ + SO42–
Ka 0124-6601200 for further assistance.
HSO4– H+ + SO42–

20 chemistry tODAy | march ‘16


chemistry tODAy | march ‘16 21
(CHEMICAL BONDING)
Mukul C. Ray, Odisha

OverpOwering the limitatiOns Of electrOnic Both these points are illustrated by the decreasing
theOry-intrOducing valence BOnd theOry stability of LiH, NaH, KH. In these compounds while
No theory is perfect. It is modified from time to time. hydrogen uses 1s‑orbital, lithium uses 2s, sodium 3s
The bond pair in a covalent bond as per electronic and potassium 4s. These orbitals are increasingly larger
theory is exactly placed in between the atoms. in size and higher in energy hence give poor overlap.
Heisenberg’s uncertainty principle, however, objects head-on and lateral Overlaps
this idea that the position of an electron pair can be In molecules like HF, F2 overlappings found are s-p,
described with accuracy. Similarly, electronic theory p-p respectively. Considering z‑axis as the molecular
hardly sees difference between the bond lengths in axis, these can better be represented as s-pz and pz‑pz.
hydrogen and fluorine molecules. Also it has no idea It is known that s‑orbitals are spherical in shape;
to distinguish the bond strengths of the two bonds of means the electron density is not concentrated along
oxygen molecule. any particular direction. On the other hand, they are
projected along an axis, x, y or z in p‑orbitals. Such
Consider Schrodinger’s wave equation. For a 2p‑orbital
projected lobes give better overlaps. Therefore, bond
say, there are two parts in the wave function, radial strengths decrease in the order: p-p > s-p > s-s. These
and angular parts. The angular part, for example, for are all head‑on overlaps giving rise to what is called
the 2px‑orbital is : as sigma bond.
 3  In oxygen atom there are two half‑filled atomic orbitals.
φ(2 px ) =  sin θ cos φ
 4 p  When two such atoms overlap, there can be one
This angular part when multiplied with radial part head‑on and another lateral overlaps. When z‑axis is the
gives the total wave function. Generally, it is drawn, as molecular axis, pz‑pz is the head‑on overlap and px-px
p‑orbital is the graph of the angular part of the wave or py-py are the possible lateral overlaps. The covalent
function and present it like the graph of y, the total bonding due to lateral overlaps is called pi‑ bond.
wave function. Now depending on whether presenting
y or y2, signs of wave functions appear in the lobes.
In the squared wave function, both the lobes become
positive.
The valence bond theory uses +
the plot of y2 to show orbital
overlaps. Pauling’s Valence Bond

Theory visualizes a bond as the (Plot of ) (Plot of 2) In a pi‑bond one‑half of the cloud lies above and the
result of overlap of half‑filled other half lies below the inter‑nuclear axis.
orbitals. During overlap :
€ Orbitals with similar size overlap more effectively
than orbitals of mis‑matched sizes.
€ Orbitals with nearly identical energy overlap
effectively as compared to orbitals which are widely
different in energies.

22 chemistry tODAy | March ‘16


Sigma bonds have electron density along the axis The index of hybridisation is not necessarily a whole
whereas in pi‑bonds; one‑half lies above and the other number :
half lies below the axis. The stronger counterpart sigma s
cos θ =
bond determines the bond axis and also allows free s −1
rotation. The weaker one only shortens the bond length The bond angle between the hybrids is 107.1°, the
and prevents free rotation around the bond axis. hybridisation is sp3.4. The gradual decrease in bond
an improvisation in the form of inter-mixing of orbitals angles from 180°, lowers the p‑character in the hybrid
was needed : orbitals.
Methane, a household fuel, in the form of natural gas different combinations give rise to different
is a symmetric molecule with all bond lengths identical hybridisations :
and bond angles 109.5°. In the excited state the carbon Types of Geometry Orbitals Example
atom has the configuration 2s1, 2px1 2p1y 2pz1. Involvement of hybridi- hybridised
these orbitals directly in bonding would have produced sation
two types of bonds and bond angles surely other than sp Linear s, pz Monomeric
109.5°. Here comes the need of hybridisation–the inter‑ BeCl2
mixing of orbitals of the central atom before bonding sp2 Trigonal planar s, px, py BF3
takes place. The four half‑filled orbitals of carbon atom 3
sp Tetrahedral s, px, py, pz CH4
inter‑mix to produce four sp3‑hybrid orbitals, which or sd3
subsequently overlap with s‑orbital of hydrogen atom. d xy , d yz , d zx , MnO4–
s
sp3d Trigonal d z2, s, px, py, PCl5
bipyramidal pz
(more
appropriately
Four sp3-hybrid orbitals sp2pd)
Methane is tetrahedral not because of sp3‑hybridisation sp3d2 Octahedral dz2, dx2 – y2, s, SF6
but because of the fact that in tetrahedral configuration px, py, pz
it is most stable.
About the hybrid orbitals, few points are notable like predicting hyBridisatiOn in simple
they form stronger bonds than pure orbitals and they mOlecules Or iOns
never form pi‑bonds. In simple molecules or ions, the hybridisation of the
central atom can be predicted by understanding of
the exact nature Of hyBridisatiOn depends
requirement of orbitals to form sigma bonds and carry
On hyBridisatiOn energy, electrOn repulsiOn lone pairs.
energy and BOnd energy
:

The central oxygen atom in water molecule is O


sp 3 ‑hybridised. The lone pairs are now in hybrid N
S
orbitals that involve some p‑character, which is higher O O H H H
in energy than s‑orbital. By the way the energy of the In SO3, there are three sigma bonds; no lone pairs
system has increased. However, the lone pair repulsion on the central atom. So it must be sp2‑hybridised.
has decreased because of increase in bond angles and In ammonia, the central atom carries three bond pairs
bond strength has increased. This makes a profitable and one lone pair; so four hybrid orbitals are needed
business for the oxygen atom. and it is sp3‑hybridised.
In H2S, the original lone pair repulsion is decreased
There is a short‑cut too developed by A.B.P. Lever.
considerably because of large size of the atom. Now
The value of V is calculated for the given molecule
the system prefers to enter into bonding using p‑rich
or ion.
orbitals having low hybridisation energy. Therefore,
H2S is not considered to have sp3‑hybridisation. V = {S group number} – charge

chemistry tODAy | March ‘16 23


For these calculat7ions, group number of H is taken Out of the two resonating structures of vinyl chloride,
as 7 and all other group numbers are taken as per old the structure with no formal charge is more stable.
convention IA, IIA etc. When the things are seen closely it is realized that;
The value of V is then divided by 8 and the result (say VBT tries to explain the properties by giving various
‘a’ ) is recorded. structures. But none of them really represents the
Remainder, if any, is divided by 2 and the result (say behaviour perfectly. The most stable structure is the
‘b’) is recorded. best attempt of VBT. The gap between the best attempt
The sum of ‘a’ and ‘b’ is determined. If the result is and the original structure in terms of energy is called
2, hybridisation is sp. Similarly, for 3, 4, 5 and 6 the resonance energy.
hybridisations are sp2, sp3, sp3d and sp3d2 respectively. formal charge helps to know which resonating structure
Remember these rules are applicable most effectively to is close to the hybrid :
non‑cyclic molecules/ions of representative elements
There are examples of molecules where bonding
having only one central atom.
situation does not respond to the normal valency of
The state of hybridisation of carbon atom is always easy
the bonded atoms. Such cases can be justified by the
to recognize from the number of pi‑bonds attached
concept of formal charge. A formal charge on an atom is
to it. If there is no pi‑bond then it is sp3. For 2 and
essentially the charge that would remain if all covalent
1 pi‑bonds it is sp and sp2 respectively.
bonds were broken and the electrons are distributed
Consider the hybridisation of the central atom in
equally between the bonded atoms.
I3– ion. For this ion, V = (7 × 3) – (–1) = 22. Thus
a + b = 5 and the state of hybridisation of the central Mathematically,
atom is sp3d. Formal charge = (No. of valence electrons in neutral
The state of hybridisation of various central atoms 1
atom) – (No. of non‑bonding electrons) – (No. of
will be revisited after going through resonance and 2
pp‑dp bonds. electrons involved in bond formation)
a single valence bond structure may not explain all The formal charges for the given structure of
the observed properties – constraint is overpowered diazomethane is :
by resonance : H2C N N
Originally in vinyl chloride, carbon‑chlorine has 1
some double bond character in addition to double Formal charge on carbon = 4 − 0 − (8) = 0
2
bond character in carbon‑carbon bond. This cannot 1
be explained by a single valence bond structure. The Formal charge on central nitrogen = 5 − 0 − (8)
2
following two resonance structures for vinyl chloride = +1
are drawn : 1
Formal charge on the right nitrogen = 5 − 4 − (4)
– + 2
:

H2C CH Cl H2C CH Cl = –1
These two structures donate characters to the For a co‑ordinate covalent bond the rule concerning
original structure called hybrid proportionate to their formal charge is amended, so that both electrons count
stability. for the donor neither for the recipient.
In terms of orbital overlaps, they are : O
N O
H
1
Formal charge on nitrogen = 5 − 2 − (6) = 0
2
These structures really want to say there is a delocalised Formal charge on covalently bonded oxygen
overlap; means simultaneous overlaps of three p-orbitals 1
= 6 − 4 − ( 4) = 0
altogether carrying four electrons in the resonance 2
hybrid. There is no scope to show such bonding in Formal charge on co‑ordinate bonded oxygen
VBT. =6–6–0=0

24 chemistry tODAy | March ‘16


Formal charges are frequently drawn in organic saying the central nitrogen is sp2‑hybridised and the
chemistry, such as the positive charge on trivalent lone pair present in p‑orbital of nitrogen overlaps with
carbon of carbocation and negative charge on carbanion. vacant d‑orbital of one silicon atom in a resonating
They are extremely useful in judging the possibility of structure. The other two resonating structures will
a proposed structure. Some general principles are : carry the only double bond in turn.
€ Structures, if possible without formal charges, are
preferred.
€ Structures with formal charges outside the range
–1 to +1 are generally unfavourable.
€ Negative formal charges should preferably be
assigned to more electronegative atoms, positive Similar case is found in O(SiH3)2, where the oxygen
charges to more electropositive atoms. atom is sp2‑hybridised.
revisiting the concept of hybridisation and bringing normal bonds are 2c-2e but there are bonds with
in pp-dp bonds : 3c-2e :
In SO3, the central sulphur atom is sp2‑hybridised. So In case of Al2Me6 the two, 3c(3 center) ‑ 2e(electron)
naturally it is left with only one pure p‑orbital in the bonds are formed by overlapping of one sp3‑hybrid
valence shell. This can give rise to only one pp‑pp bond. orbital from each aluminium atom and one sp3‑hybrid
What about the other two p‑bonds? The central atom orbital of methyl group. Out of the two hybrid orbitals
must be using d‑orbital to make these p‑bonds. provided by the aluminium atoms, one is half‑filled
In the excited state sulphur has the configuration : and the other is empty.
Me Me Me
3d
Al Al
3s 3p Me
Me Me
And pp‑dp bonds are formed as shown below without
taking into account which d‑orbitals are involved : Al Al

Such pp‑dp bonds are best formed when one element Me


is from 2nd and the other is from 3rd period. Consider
few more examples : 
O
Solution Senders of Chemistry Musing
P Set 31
S HO OH
O 1. rahul Dey, Jharkhand
O HO
One p-d bond One p-d bond 2. rajat Gupta, Mumbai
(sp2) (sp3) 3. rishabh Dutta roy, Jharkhand
O O 4. hrishikesh Sarmah, assam
Cl S 5. Sayak Mandal, West Bengal
O OH O OH 6. ashwin Shenoy, Karnataka
O OH
Three p-d bonds Two p-d bonds 7. Samrat Gupta, West Bengal
(sp3) (sp3) 8. aVN Prasad, Visakhapatnam
Another fine example is trisilylamine, (SiH3)3N, which 9. Yakaiah chennori, Warangal
fails to form an adduct with BF3 implying the absence 10. arunesh Varade, Nashik
of lone pair on the nitrogen atom. This is explained by 11. Langa Bebarta, Odisha

chemistry tODAy | March ‘16 25


Dear students!! Last article was based on the reduction reactions and now this article is on oxidation reactions. coupling both you
can definitely make your concept strong to solve these type of questions asked in competitive examinations. all the very best for the
board examinations. Thanks
*Arunava Sarkar

DeALiNG With OXiDAtiON These reagents cannot oxidise a 3° alcohol or benzene


ring as obvious in the above cases.
Some Common Aspects
€ In general, oxidation of primary alcohols follows € 3° H is oxidised to —OH :
the following path : Me Alkaline
Me
[O] [O] Me C H Me C OH
Primary alcohol Aldehyde Carboxylic KMnO4
(–CH2OH) (–CHO) acid Me Me
(–COOH) 3°H is oxidised to –OH
Cold, dilute alkaline KMnO4 or aqueous KMnO4
For this purpose either hot, alkaline or acidic Popularly, this reagent is known as Baeyer’s reagent.
KMnO4 or acidic K2Cr2O7 is used. They will not
Main function of this reagent is syn-hydroxylation of
stop the oxidation at the aldehydic stage so, the final
product is carboxylic acid. multiple bond as shown below :
R1 CH CH R2 R1 CH CH R2
€ With hot alkaline KMnO4 or acidic KMnO4, the cis-alkene
following transformations take place : OH OH
CH2 CO2; CH R RCOOH;
R
C RCOR
R
CH CO2; C R RCOOH
CH2X COOH
R1 R1
CHOH C O; Na2Cr2O7 + Conc. H2SO4, in acetone
R2 R2
(X = halogen) Cr (VI) is oxidising in nature. During the oxidation, it
COOH R gets converted to Cr(III). Cr(VI) form is available with
Na2Cr2O7, K2Cr2O7 or CrO3. Oxidation of this type is
better known as Jones oxidation. One of the best uses of
(R = alkyl group containing this oxidation is to convert 2° alcohols to ketones. i.e.
benzylic hydrogen) OH O
Na2Cr2O7
CH CH2 COOH CH C
R1 R2 Conc. H2SO4 R1 R2
Reaction proceeds via the formation of chromate ester.
In general, Jones Reagent is H2CrO4 in anhydrous
* Institute of Chemistry (IOC)- Asansol, Durgapur, Dhanbad, Burdwan, Kolkata, Jamshedpur, Bokaro, Patna

26 chemistry tODAy | March ‘16


chemistry tODAy | March ‘16 27
acetone or CrO3 + H2SO4 in acetone. It does not affect 1. Converts 1° alcohol into aldehyde only. No further
multiple bond or 3° alcohol. However, it converts 1° oxidation is possible.
alcohol to carboxylic acid and 2° alcohol to ketone. 2. Converts 2° alcohol into ketone.
3. Does not disturb multiple bond or 3° alcohol.
Q. Can you identify the product? 4. Oxidises allylic primary alcohol to aldehyde with
Cold, dil.
(a) Me C C H alkaline KMnO ? no further oxidation.
4
Cold, dil.
Remember that the success of PCC to stop the oxidation
(b) HC CH alkaline KMnO ? of alcohol at aldehydic stage is due to the absence of
4
Ans: (a) water and presence of pyridine base. Follow these
Me C C H + H2O + [O] examples :
Me C C H
PCC CHO
OHOH OH CH2Cl2
2H2O + [O]
PCC/Al2O3
O O OH OH n-hexane
Further –2H2O OH O
Me C C H Me C C H
oxidation A similar reagent is PDC (Pyridinium dichromate) with
OH OH the structure :
Further
Me C C OH oxidation Me COH + CO2
O O O
[Remember, —CHO on oxidation gives —COOH]
(b)
H C C H + H2O + [O] H C C H
OHOH
H2O + [O]

O O OH OH
Further –2H2O
oxidation
H C C H H C CH

HOC C C OH OH OH

O O
(Oxalic acid)
Usually, at the beginning, formation of nascent
oxygen is shown as below :
2KMnO4 + H2O 2KOH + 2MnO2 + 3[O]
PCC
PCC is better known as pyridinium chlorochromate
and its structure is sepresented as :

The best use of PCC is to stop the oxidation of alcohol


at the aldehydic stage. PCC is used in dichloromethane
(CH2Cl2) which is used as a solvent. Primary points
0124-6601200 for further assistance.
regarding PCC are :

28 chemistry tODAy | March ‘16


NMO with TPAP catalyst 3° alcohols are usually not oxidisable and therefore are
NMO has the full form N-methyl morpholine-N-oxide dehydrated under similar conditions.
with the structure : CH3 H3C
Cu
H3C — C — OH 573 K (–H2O)
C CH2
H2 C H3 C
H
TPAP (tee-pap) has the full form tetra-n-propyl
ammonium perruthenate. Structure can be given as CrO3 in Glacial CH3COOH
below : CrO3 is a strong oxidising agent. It carries out the
following conversions :
(a) CH2OH CHO COOH
Now, function of both of these together is same as
that of PCC, particularly, in converting 1° alcohol into (b) CHOH C O
aldehyde. C C
(c) COOH
The use of this reagent has become popular because in
chromium oxidation toxic heavy metal byproducts are It does not affect C C and 3° alcohol.
obtained.
TsCl (Tosyl chloride) + DMSO + NaHCO3
Hot Cu/573 K TsCl DMSO
R CH2OH RCH2OTs R CHO
Conversion usually obtained are : NaHCO3
OH O
R1 TsCl R1 DMSO R1
RCH2OH R CHO; CH C CHOH CHOTs NaHCO C O
R2 R2 3 R2
R1 R2 R1 R2
nn
SolutionS oF JAnuAry 2016 CroSSWord SolutionS oF FebruAry 2016 CroSSWord
1 1 2
I V R
2 3 4
S K N O C K R A T I N G A I
3
P E
O R G 4 5
5 6
C E L L U L O S E M O L A R M A S S
B P N I C O L P R I S M L 6
B C L O
A H E Y
7 8 E O Y L
C R O W N E T H E R S C T C 8
7
S N A H O
L T A U T O M E R S P U
9
9
P H A S E D I A G R A M Y N Y A I R D T
10 11 12
10
U D B
11
S U B L
12
I M A T E M S T H E R M O C H R O M I C
13
B R O O Y C A L O R I E Y L T L O
13 14 14 15
S A L I C I N I M E I S E N H E I M E R O N D M E L T I N G P O I N T
A Q N D A G 16
L A C T A M S C C M H
15
N U H E T E R O C Y C L I C N L
T T I I
D I O G O 17
16
M I C H A E L F A R A D A Y T O
N P X E B 18
17 18 P V O E K
N O S I R W I L L I A M S I E M E N S I 19 20
I I D N
H S P E C T R O S C O P Y C O
N
19
C O P E E L I M I N A T I O N E O S L U L
21 22 23
O S I
20
F S F L I N T G L A S S B O R A N E S
21 24
T T U N G S T E N B R O N Z E S P H T I U
22 25
I I R L H Y D R O G E N O L Y S I S C T
23 24
N G A L V A N I C H Y D R A T E O M N I
E E E U 26
R O G L A B I L E
D C 27
25
U M E L A N I N E
P H O S P H O R I
26 S O
H Y P O G L Y C E M I A X T
E
G
I
28
27
S P E C T R O S C O P E N S O L U B I L I T Y

Winners of January 2016 Crossword Winners of February 2016 Crossword


• Anshul Agnihotri (Chandigarh) • Tia Sharma (Surat)
• Subhangi Gupta (Meerut) • Ajay Bhardwaj (Punjab)

chemistry tODAy | March ‘16 29


So, normality of Na2CO3 in the sample
CHEMISTRY MUSING =
100 1
= = 0. 1 N
1000 10
sOLUtiON set 31 Strength in g L–1 = N × Eq. wt. = 0.1 × 53 = 5.3 g L–1
1. (b) : [Co(NH3)6]Cl3 ionises to give 4 ions. 7. (b) : Since (D) gives aniline on treatment with Br2
[Co(NH3)5Cl]Cl2 ionises to give 3 ions. and KOH.
[Co(NH3)4Cl2]Cl ionises to give 2 ions.
Higher the number of ions a complex produces Hence (D) must be
in solution, higher will be the conductivity of
complex.
1 1 1
2. (b) : Since t1/2 ∝ n−1 ⇒ t1/2 ∝ 1−1 ⇒ t1/2 ∝ 0
a a a
i.e., t1/2 is independent of a, hence order of reaction
is 1.

3. (c) :

Hence (A) must be which undergoes


4. (b) : Due to smaller size of oxygen there is higher
charge density on oxygen as compared to sulphur.
Thus, there is higher bond dissociation energy of Cannizzaro reaction to give and
H—O bond in H2O which leads to difficulty in
furnishing H+ ions than in the case of H— S bond in .
H2S.
5. (d) : FeSO4 · 7H2O (pale green salt)
Fe2+ Fe3+
Fe3+ + 3OH– Fe(OH)3
Brown
2+
Fe + H2S FeS + 2H+
Black ppt.
5Fe2+ + 8H+ + MnO4– Mn + 5Fe3+ + 4H2O
2+

6. (a) : When phenolphthalein is used, Na2CO3 gets


converted into NaHCO3.
2Na2CO3 + H2SO4 2NaHCO3 + Na2SO4
NH2SO4 = 2MH2SO4 = 2 × 0.1 = 0.2 N 8. (b) : As compound
, its
meq of H2SO4 = NH2SO4 × VH2SO4 = 0.2 N × 2.5 –1
= 0.5 meq of H2SO4 molecular weight is 108 g mol .
0.5 meq of H2SO4 is used to convert Na2CO3 to 9. (3) : NaCN + HCl is not a buffer but if HCl is
NaHCO3 using phenolphthalein as indicator. present in less amount then, it produces HCN.
When methyl orange is used as an indicator, the Let a moles of HCl be used for this purpose.
end point appears when NaHCO3 is completely NaCN + HCl NaCl + HCN
converted into CO2. Initial moles 0.01 a 0 0
Moles after reaction (0.01 – a) 0 a a
NH2SO4 = 2 × MH2SO4 = 2 × 0.2 = 0.4 N This is buffer of HCN + NaCN.
No. of meq of 0.4 N H2SO4 used to neutralise total 0.01 − a
NaHCO3 into CO2 = 0.4 × 2.5 = 1 meq \ pH = − log K a + log
a
No. of meq of H2SO4 used to neutralise NaHCO3 0.01 − a
initially present in the sample solution = 1.0 – 0.5 8.5 = − log 4.1 × 10−10 + log
a
= 0.5 meq \ a = 8.85 × 10–3 mole of HCl
Total meq of H2SO4 used to neutralise Na2CO3 10. (4) : In alkaline condition KMnO4 reduces to
completely = 0.5 + 0.5 = 1.0 meq MnO2
10 mL of Na2CO3 1 meq of Na2CO3 2KMnO4 + H2O 2MnO2 + 2 KOH + 3[O]
1000 mL of Na2CO3 100 meq of Na2CO3 Oxidation number of Mn in MnO2 is 4.


30 chemistry tODAy | March ‘16


Class
XI-XII

ACCELERATED LEARNING SERIES


Unit 9 PRINCIPLES RELATED TO PRACTICAL CHEMISTRY

Practical Organic chemistry nitrogen, sulphur and halogens are less commonly
l Detection of Extra Elements in Organic Compounds present thus are known as extra elements.
l Detection of Functional Groups in Organic Compounds ‰ The elements are usually tested in the form of
ions. Since organic compounds are covalent in
l Preparation of Organic Compounds
nature, they do not ionise. Therefore, to convert
tiPs tO remember elements present in organic compounds into ions,
the organic compound is fused with sodium metal
Detection of Extra Elements in Organic Compounds
which is then plunged in distilled water, boiled and
‰ The principle elements present in organic filtered. The filtrate is called Lassaigne’s extract or
compounds are carbon, hydrogen and oxygen while sodium extract.

Element Lassaigne’s extract Confirmatory test Reactions


(L.E.)
Nitrogen Na + C + N  NaCN L.E. + FeSO4 + NaOH, boil and FeSO4 + 2NaOH Fe(OH)2 + Na2SO4
(L.E.) cool + FeCl3 + conc. HCl Fe(OH)2 + 6NaCN
Gives blue or green colour. Na4[Fe(CN)6] + 2NaOH
HCl
Na4[Fe(CN)6] + FeCl3
NaFe[Fe(CN)6] + 3NaCl
Prussian blue
or 3Na4[Fe(CN)6] + 4FeCl3
Fe4[Fe(CN)6]3 + 12NaCl
Prussian blue
Sulphur 2Na + S  Na2S (i) L.E. + sodium nitroprusside (i) Na2S + Na2[Fe(CN)5NO]
A deep violet colour. Sodium nitroprusside
(L.E.)
(ii) L.E. + CH3COOH Na4[Fe(CN)5NOS]
Deep violet
+ (CH3COO)2Pb CH COOH
Gives a black ppt. (ii) Na2S + (CH3COO)2Pb 3
PbS↓ + 2CH3COONa
Black ppt.

chemistry tODAy | March ‘16 31


Halogens Na + X  NaX L.E. + HNO3 + AgNO3 NaX + AgNO3
HNO3
AgX↓ + NaNO3
(L.E.) (i) White ppt. soluble in ppt.
aq. NH3 (or NH4OH) AgCl + 2NH4OH(aq.)
confirms Cl. White ppt.
(ii) Pale yellow ppt. partially [Ag(NH3)2]Cl + 2H2O
soluble in aq. NH3 (or Soluble
NH4OH) confirms Br. AgBr + NH4OH(aq) Sparingly soluble
Pale yellow
(iii) Yellow ppt. insoluble in
ppt.
aq. NH3 (or NH4OH)
AgI + NH4OH(aq) Insoluble
confirms I. Yellow ppt.
Nitrogen Na + C + N + S  As in test for nitrogen, instead 3NaSCN + FeCl3
and NaSCN of green or blue colour, blood [Fe(SCN)3] + 3NaCl
sulphur (L.E.) red colouration confirms Blood red colour
together Sodium thiocyanate presence of N and S both.

KEY POINT

• When sodium fusion is carried out with excess of NaCNS + 2Na NaCN + Na2S
sodium, thiocyanate decomposes to cyanide and Sodium thiocyanate
sulphide ions which give their usual tests. Thus, • Lassaigne’s test fails in case of compounds which
we do not get blood red colour with ferric chloride contain nitrogen but no carbon e.g., hydrazine
even though N and S both are present. (NH2NH2) and hydroxylamine (NH2OH).

Detection of Functional Groups in Organic Compounds


Test Reaction Confirmation
(A) Detection of unsaturation
(i) Baeyer’s or KMnO4 2KMnO4 + H2O 2KOH + 2MnO2 + 3[O] Disappearance of pink
test colour of KMnO4.

(ii) Br2 - CCl4 test Disappearance of brown


colour.
Red
brown

(B) Detection of alcoholic group


(i) Ester test Fruity smell of ester
 indicates – OH group.
(ii) Ceric ammonium 2ROH + (NH4)2[Ce(NO3)6] Appearance of pink or red
nitrate test [(ROH)2Ce(NO3)4] + 2NH4NO3 colour.
Pink or red

(iii) Xanthate test ROH + KOH(s)  RO–K+ + H2O Formation of yellow ppt.
Pot. alkoxide

32 chemistry tODAy | March ‘16


(C) Detection of phenolic group
(i) FeCl3 test FeCl3 + 6C6H5OH [Fe(OC6H5)6]3– + 3H+ + 3HCl Appearance of violet
Violet colouration.

(iI) Azo dye test 0-5°C Formation of orange or


C6H5NH2 + NaNO2 + HCl C6H5N2+Cl–
red dye.
pH 9-10
C6H5N2+Cl– + C6H5OH
(p)HO C6H4 N N C6H5
p-Hydroxyazobenzene

(iii) Phthalein test or


fluorescein test

Appearance of green, blue, pink, purple or red fluorescent solution.


(iv) Br2-H2O test Appearance of white ppt.

(v) Liebermann nitroso


test

Appearance of deep blue or green colour which turns red on dilution and again blue
on adding sodium hydroxide solution.

chemistry tODAy | March ‘16 33


(D) Detection of carbonyl group
Aldehydic/Ketonic group
(i) Brady’s reagent NO2 Appearance of yellow,
(2, 4-DNP) test orange or red ppt.
C O + H2NHN NO2
2,4-Dinitrophenylhydrazine
NO2

C NHN NO2
Yellow, orange or red ppt.
(ii) Sod. bisulphite test Appearance of white ppt.

Aldehydic group
(i) Tollens’ test RCHO + 2[Ag(NH3)2]OH RCOONH4 + 3NH3 + Formation of silver mirror
H2O + 2Ag(s) along the sides of the test
Silver mirror
tube.
(ii) Fehling’s test RCHO + 2Cu2+ + 5OH– Cu2O↓ + RCOO– + 3H2O A red ppt. is formed (only
Red ppt. by aliphatic aldehydes).
(iii) Schiff ’s test RCHO + p-rosaniline hydrochloride in saturated Appearance of pink
solution of SO2 in water (colourless solution) colour.
Ketonic group
(i) Iodoform test R – CO – CH3 + 3I2 + 4NaOH Formation of yellow
3NaI + CHI3↓ + RCOONa + 3H2O ppt. of CHI3 (for methyl
Yellow ppt. ketones only).
(ii) Sodium nitroprusside RCOR + sodium nitroprusside solution + NaOH Appearance of wine-red
test colour (for methyl ketones
only).
(E) Detection of carboxylic group
(i) Litmus test Blue litmus paper turns red. –COOH group may be
present.
(ii) NaHCO3 test RCOOH + NaHCO3 RCOONa + H2O + CO2↑ Brisk effervescence of
CO2 indicates –COOH
group.
(iii) Ester test Conc. H2SO4 Fruity smell of esters
RCOOH + C2H5OH 
RCOOC2H5 + H2O
formed.
(iv) FeCl3 test 3RCOOH + 3NH4OH + FeCl3 Red : acetic acid, formic
(RCOO)3Fe + 3NH4Cl + 3H2O acid
Coloured ppt. No colour change or light
H2O yellow colour : oxalic acid

Fe(OH)(OOCR)2 + RCOOH Violet : salicylic acid


Basic iron salt Buff : benzoic acid

34 chemistry tODAy | March ‘16


(F) Detection of amino group
Primary amines
(i) Nitrous acid test R – NH2 + HNO2 N2 effervescence indicates
R – OH + N2­↑­+ H2O
1° amino group.
(ii) Carbylamine test R – NH2 + CHCl3 + 3KOH
 Offensive smell of isocya-
R N C + 3KCl + 3H2O nide indicates 1° aliphatic
Isocyanide or aromatic amino group.
(iii) Azo dye test 0-5°C A red or orange coloured
C6H5NH2 + NaNO2 + HCl 5-10 atm C6H5N2+Cl–
dye confirms 1° aromatic
amino group.

Secondary amines
(i) Liebermann nitroso CH3 Formation of a yellow oily
test C6H5 N H + HNO2 C6H5 N N O + H2O nitrosoamine indicates
Nitrosoamine 2° aliphatic or aromatic
CH3 amino group.
(G) Detection of nitro group
(i) Mulliken Barker test Zn + NH4Cl Appearance of grey black
RNO2 + 4[H] RNHOH + H2O
ppt.
RNHOH + 2[Ag(NH3)2]OH RNO + 2H2O
+ 4NH3 + 2Ag↓
Grey black ppt.
(ii) Ferrous hydroxide RNO2 + 6Fe(OH)2 + 4H2O RNH2 + 6Fe(OH)3↓ Appearance of brown
test Light green Brown ppt. ppt.
‰ Distinction tests Peroxy acid Acid is formed. Ester is
Test Phenol Alcohol (Caro’s acid, peroxy formed.
Blue litmus test Turns red O benzoic acid)
FeCl3 test Gives blue, violet, green or O KEY POINT
red colouration • Ceric ammonium nitrate test : Many easily
Azo dye test Forms orange-red colour O oxidisable aromatic amines also give this test.
dye Some phenols also give green or brown ppt.
Br2-water test Gives white ppt. O • Ferric chloride test : Also given by enols
OH
Test Phenol Carboxylic acid
C C
NaHCO3 test O Gives brisk effervescence • Sodium bisulphite test : Aliphatic aldehydes and
methyl ketones which are not sterically hindered
Test Aldehyde Ketone
such as acetaldehyde, acetone, ethyl methyl
Tollens’ test Gives shiny silver O ketone give this test. Among aromatic aldehydes
mirror and ketones, only benzaldehyde gives this test but
Fehling’s solution test Gives red ppt. O acetophenone, benzophenone do not give this
Schiff ’s reagent test Gives pink colour O test.
• NaHCO3 test : Some phenols such as
Reduction with Reduced to 1° Reduced to
2,4-dinitrophenol and 2,4, 6-trinitrophenol (picric
LiAlH4 alcohol 2° alcohol
acid) also respond to this test.

chemistry tODAy | March ‘16 35


• Carbylamine test : Isocyanide formed has very ‰ Aniline yellow : It is prepared by coupling
offensive smell and may also be poisonous hence benzenediazonium chloride with aniline in acidic
must be carefully decomposed by adding conc. medium.
+ H+
HCl before throwing it in the sink. N NCl – + NH2

SELF CHECK
HCl + H2N N N
1. For the identification of b-naphthol using dye test,
Aniline yellow
it is necessary to use (p-Aminoazobenzene)
(a) dichloromethane solution of b-naphthol
‰ Iodoform : It is prepared by treating organic
(b) acidic solution of b-naphthol OH O
(c) neutral solution of b-naphthol
compound containing CH3 CH or CH3 C
(d) alkaline solution of b-naphthol.
group with iodine in presence of sodium hydroxide.
(JEE Advanced 2014)
2. Which of the following reagents may be used to 

distinguish between phenol and benzoic acid?


(a) Aqueous NaOH (b) Tollens’ reagent
(c) Molisch reagent (d) Neutral FeCl3
(AIEEE 2011)

Preparation of Organic Compounds
CHI3 + CH3COONa
‰ Acetanilide : It is prepared by acetylation of aniline
which is a nucleophilic acyl substitution reaction. KEY POINT
O O • Nitrating mixture is the equimolar mixture
CH3COOH
NH2 + CH3 C O C CH3 of conc. HNO3 and conc. H2SO4. The role of
Acetic anhydride conc. H2SO4 is that it reacts with HNO3 to form
Aniline (electrophile)
(nucleophile) O nitronium ion.
CH3COOH + CH3 C NH
Practical inOrganic chemistry
Acetic acid Acetanilide
O l Preparation of Inorganic Compounds
Pyridine l Qualitative Salt Analysis
NH2 + CH3 C Cl
Acetyl chloride
l Titrimetric Analysis
Aniline
O tiPs tO remember
HCl + CH3 C NH Preparation of Inorganic Compounds
Acetanilide
‰ Mohr’s salt (Ferrous ammonium sulphate)
‰ p-Nitroacetanilide : It is prepared by nitration
of acetanilide with nitrating mixture which is an  It is a double salt containing ferrous sulphate and

electrophilic substitution reaction. ammonium sulphate in equimolar amounts.


 It is prepared by dissolving an equimolar
mixture of hydrated ferrous sulphate and
+ +
ammonium sulphate in water containing a little
(electrophile) of sulphuric acid.
(nucleophile) FeSO4⋅7H2O + (NH4)2SO4
FeSO4⋅(NH4)2SO4⋅6H2O + H2O
‰ Potash alum (Phitkari)
 It is a double salt containing potassium
sulphate and aluminium sulphate in equimolar
amounts.

36 chemistry tODAy | March ‘16


 It is prepared by dissolving an equimolar using platinum wire. Some basic radicals impart
mixture of hydrated aluminium sulphate and characteristic colour to the flame.
potassium sulphate in water containing a little Colour of flame Radicals
of sulphuric acid. +
 Golden yellow Na
K2SO4 + Al2(SO4)3⋅18H2O + 6H2O
Lilac or violet K+
K2SO4⋅Al2(SO4)3⋅24H2O
Brick red Ca2+
Qualitative Salt Analysis
Apple green Ba2+, Mo2+
‰ Preliminary tests
Crimson red Sr2+
 Physical examination
+ 2+ 3+ 2+ 2+ Greenish blue Cu2+, BO33–
— Colour : NH4 , Pb , Al , Zn , Ba ,
2+ 2+ 2+
Ca , Sr , Mg (white), Cu (blue),2+  Borax bead test : Coloured salts are heated on the
Ni2+, Cr3+ (green), Fe2+ (light green), glassy bead, coloured metaborates are formed.
Fe3+ (brown), Co2+ (pink), Mn2+ (light pink ∆
Na2B4O7·10H2O Pt wire Na2B4O7 
or flesh colour) Borax 2NaBO2 + B2O3
+
— Odour : NH4 (ammoniacal smell),
CH3COO– (smell of vinegar), S2– (smell of Colourless glassy bead
rotten eggs) — In oxidising flame :
CuSO4 + B2O3 Cu(BO2)2 + SO3
 Dry heating test Copper metaborate
Observation Radicals (Blue)
Gas evolved — In reducing flame :
2Cu(BO2)2 + C 2CuBO2 + B2O3 + CO
Colourless CO32–, SO32–, S2–, Cl–
(Colourless)
Brown Br–, NO3– 2Cu(BO2)2 + 2C 2Cu + 2B2O3 + 2CO
Violet I– (Brown red)

Residue Hence, different colours appear in different


flames.
Yellow when hot,
Zn2+ Colour in
white when cold
Brown when hot, Metal Oxidising flame Reducing flame
Pb2+
yellow when cold Hot Cold Hot Cold
2+
Reddish brown Fe Cu Green Blue Colourless Brownish
Black Ni2+, Co2+, Mn2+, Cu2+ red
Change in colour of salt Fe Brownish Pale Bottle Bottle green
yellow yellow green
Blue to white CuSO4⋅5H2O
Cr Green Green Green Green
Pink to blue CoCl2
Co Blue Blue Blue Blue
Green to yellow Ni2+ salt
Blue/green to Mn Violet Amethyst Grey Grey
Cu2+ salt red
brown/black
Ni Violet Brown Grey Grey
Sound produced
NaCl, KI, Pb(NO3)2,  Charcoal cavity test (Reduction test) : Salt is
Crackling sound heated with fusion mixture (Na2CO3 and
Ba(NO3)2
K2CO3) in a charcoal cavity in reducing flame to
 Flame test : A paste of salt with 1 or 2 drops of
form metallic oxides which are left as coloured
conc. HCl is introduced in the non-luminous
residues. The colour of the residue being
(oxidising part) flame of the Bunsen burner
characteristic of the basic radical present.

chemistry tODAy | March ‘16 37


Residue (hot) Residue (cold) Radical KEY POINT
Yellow White Zn2+ • Flame test should not be performed in the presence
Reddish brown Yellow Pb2+ of As, Sb, Bi, Sn and Pb as these radicals form alloy
with platinum and hence, the wire is spoiled.
 Cobalt nitrate test : If the residue in charcoal
• The yellow colouration due to sodium masks the
cavity test is white, it is moistened with a drop
colour due to potassium. In such cases, view the
of cobalt nitrate and on heating in an oxidising
flame through cobalt glass, the yellow sodium
flame, colour of the residue changes. For colour is absorbed and the potassium flame
example, ZnSO4 gives green residue. appears crimson.
ZnSO4 + Na2CO3 ZnCO3 + Na2SO4
• Cobalt nitrate test should be performed with 2-3
ZnCO3 ZnO + CO2 drops of cobalt nitrate solution otherwise black
2Co(NO3)2 2CoO + 4NO2 + O2 cobalt oxide is formed which will mask the colour
ZnO + CoO CoZnO2 of the residue.
Rinnmann’s green
Observation Inference ‰ Identification and confirmatory tests of acidic
Blue mass Aluminium radicals
Green residue Zinc  Group I acidic radicals : Effervescence or
Pink residue Magnesium evolution of gases on addition of dilute HCl or
dilute H2SO4 to the salt indicates the presence
Bluish green Tin of group I acidic radicals.

Gas Radical Confirmatory Tests


CO2 Carbonate Na2CO3 + H2SO4 Na2SO4 + H2O + CO2↑
(Colourless, odourless gas) (CO32–) Salt
Ca(OH)2 + CO2 CaCO3↓ + H2O
Limewater White ppt. (milky)
CaCO3 + H2O + CO2 Ca(HCO3)2
Soluble
H2S Sulphide • Na2S + H2SO4 Na2SO4 + H2S↑
(Colourless gas with smell of (S2–) Salt
rotten eggs) (CH3COO)2Pb + H2S PbS↓ + 2CH3COOH
Black ppt.
• Na2S + Na2[Fe(CN)5NO] Na4[Fe(CN)5NOS]
Sodium nitroprusside Violet
SO2 Sulphite • Na2SO3 + H2SO4 Na2SO4 + H2O + SO2↑
(Colourless gas with suffocating (SO32–) Salt
odour having smell of burning K2Cr2O7 + 3SO2 + H2SO4 K2SO4 + Cr2(SO4)3 + H2O
sulphur) Green
• Na2SO3 + BaCl2 BaSO3↓ + 2NaCl
White ppt.
BaSO3 + 2HCl BaCl2 + H2O + SO2↑
Soluble
NO2 Nitrite 2NaNO2 + H2SO4 Na2SO4 + 2HNO2
(Brown gas) (NO2–) Salt Nitrous acid
3HNO2 H2O + 2NO + HNO3
2NO + O2 2NO2↑
Brown
FeSO4⋅7H2O + NO [Fe(H2O)5NO]SO4 + 2H2O
Brown

38 chemistry tODAy | March ‘16


CH3COOH Acetate • 2CH3COONa + H2SO4 2CH3COOH + Na2SO4
(Colourless gas with smell of (CH3COO–) Salt
vinegar) • 3CH3COONa + FeCl3 (CH3COO)3Fe + 3NaCl
Blood red
COOH COONa
• 2CH3COONa + + 2CH3COOH
COOH COONa Smell of vinegar

KEY POINT • Before testing CH3COO– ion with neutral FeCl3


• SO2 gas evolved from SO32–
ion, also turns solution, make sure that the solution is free from
limewater milky. Thus, for test of CO32– ion, odour CO32–, SO32–, PO43– and I– ions as they combine
of gas should be carefully observed as SO2 is a with Fe3+ ions.
pungent gas while CO2 is odourless gas. • Carbonates of Bi and Ba are not easily decomposed
by dil. H2SO4 thus, dil. HCl should be used.
• PbS, CdS, NiS, CoS, Sb2S3 and SnS are not
decomposed by dil. H2SO4, therefore a pinch of  Group II acidic radicals : Effervescence or
evolution of gases on addition of conc. H2SO4 or
zinc dust is added along with it. Conc. HCl should
conc. HCl to the salt (heat if necessary) indicates
also be used. the presence of group II acidic radicals.

Gas Radical Observations and Reactions Confirmatory Tests


HCl Chloride • NaCl + H2SO4 NaHSO4 + HCl↑ Chromyl chloride test :
(Colourless – Salt
(Cl ) NaCl + H2SO4 NaHSO4 + HCl
gas with NH4OH + HCl NH4Cl↑ + H2O Salt (Conc.)
pungent White dense fumes K2Cr2O7 + 2H2SO4 2KHSO4
smell)
• NaCl + AgNO3 AgCl↓ + NaNO3 + 2CrO3 + H2O
White ppt. CrO3 + 2HCl CrO2Cl2↑ + H2O
AgCl + 2NH4OH [Ag(NH3)2]Cl + Chromyl chloride
Soluble 2H2O (Deep red vapours)

Cl2 • 2NaCl + MnO2 + 3H2SO4 2NaHSO4 CrO2Cl2 + 4NaOH


(Yellowish + MnSO4 + 2H2O + Cl2↑ Na2CrO4 + 2NaCl + 2H2O
Yellow colour
green,
suffocating Na2CrO4 + (CH3COO)2Pb
odour) PbCrO4↓ + 2CH3COONa
Yellow ppt.
Br2 Bromide • NaBr + H2SO4 NaHSO4 + HBr Layer test :
Salt
(Brown gas) (Br–) 2NaBr + Cl2 water
dil. H2SO4
2HBr + H2SO4 Br2↑ + 2H2O + SO2 CHCl3 or CCl4
Brown
• AgNO3 + NaBr AgBr↓ + NaNO3 2NaCl + Br2
Pale yellow ppt. Brown
coloured
AgBr + 2NH4OH
layer
[Ag(NH3)2]Br + 2H2O
Sparingly soluble
• 2NaBr + MnO2 + 3H2SO4 2NaHSO4
+ MnSO4 + 2H2O + Br2↑

chemistry tODAy | March ‘16 39


I2 Iodide • 2KI + 2H2SO4 2KHSO4 + 2HI Layer test :
(Deep violet (I–) Salt 2NaI + Cl2 2NaCl + I2
gas) 2HI + H2SO4 I2↑ + SO2 + 2H2O Salt
Violet I2 + Chloroform Violet coloured
• AgNO3 + NaI AgI↓ + NaNO3 layer
Yellow ppt. Starch paper test :
AgI + NH4OH Not soluble I2 + Starch I2-starch complex
• 2KI + MnO2 + 3H2SO4 2KHSO4 Violet Blue colour
vapours
+ MnSO4 + 2H2O + I2↑
NO2 Nitrate NaNO3 + H2SO4 NaHSO4 + HNO3 Brown ring test :
Salt
(Light brown (NO3–) NaNO3 + H2SO4 NaHSO4
gas having 4HNO3 2H2O + 4NO2↑ + O2 Salt + HNO3
pungent Light brown fumes 6FeSO4 + 2HNO3 + 3H2SO4(conc.)
smell)
Cu + 4HNO3 Cu(NO3)2 + 3Fe2(SO4)3 + 4H2O + 2NO
2NO2↑ + 2H2O [Fe(H2O)6]SO4⋅H2O + NO
Ferrous sulphate [Fe(H2O)5NO]SO4 +
Brown ring
2H2O
CO + CO2 Oxalate Na2C2O4 + H2SO4 Na2SO4 + H2C2O4 Na2C2O4 + CaCl2
(Colourless, (C2O42–) Salt Sodium carbonate CaC2O4↓ + 2NaCl
odourless gas) extract White ppt.
H2C2O4 + [H2SO4] CO + CO2
Burns with CaC2O4 + H2SO4(dil.)
Turns lime
blue flame water milky H2C2O4 + CaSO4
+ H2O + [H2SO4] 2KMnO4(few drops) + 3H2SO4
Purple
K2SO4 + 2MnSO4 + 3H2O + 5[O]
Colourless
COOH
+ [O] 2CO2 + H2O
COOH

KEY POINT
Br2 + Cl2 2BrCl
• Chromyl chloride test : Dry test tube should be Bromine monochloride
used to prevent the hydrolysis of chromyl chloride (pale yellow colour)
vapours. Br2 + 2H2O + Cl2 2HBrO + 2HCl
Hypobromous acid
CrO2Cl2 + 2H2O H2CrO4 + 2HCl (colourless)
In case of chlorides of Hg, Sn, Ag, Pb and Sb, this I2 + 5Cl2 + 6H2O 2HIO3 + 10HCl
test is performed by taking residue obtained after Iodic acid
evaporation of sodium carbonate extract. (colourless)

• Brown ring test is not reliable in the presence of


 Group III acidic radicals : These radicals cannot
NO2–, Br–, I– ions.
be detected by either dil. H2SO4 or conc.
• While performing layer test for Br– and I– ions,
H2SO4. For detection of these acidic radicals
excess of Cl2 water should be avoided.
some specific tests are required.

40 chemistry tODAy | March ‘16


Radical Observations and Reactions
Sulphate Na2SO4 + BaCl2 BaSO4↓ + 2NaCl
(SO42–) Salt White ppt. (insoluble in conc. HNO3)
Phosphate Ca3(PO4)2 + 6HNO3 3Ca(NO3)2 + 2H3PO4
(PO43–) Salt
H3PO4 + 12(NH4)2MoO4 + 21HNO3 (NH4)3PO4·12MoO3↓­+ 21NH4NO3 + 12H2O
Ammonium molybdate Conc. Canary yellow ppt.
Borate 2Na3BO3 + 3H2SO4 3Na2SO4 + 2H3BO3
(BO33–) Salt
H3BO3 + 3C2H5OH (C2H5)3BO3↑ + 3H2O
Ethyl borate (burns with green edged flame)
Fluoride 2NaF + H2SO4 Na2SO4 + H2F2
(F–) Salt Hydrofluoric acid
SiO2 + 2H2F2 SiF4 + 2H2O
Silica Silicon tetrafluoride
3SiF4 + 4H2O H4SiO4 + 2H2SiF6
Silicic acid
(Gelatinous white)

KEY POINT • During the test of F– ion, if HgCl2 and NH4Cl are
• Test for F– ion should be performed in perfectly present then they also produce a deposit under
dry test tube, otherwise waxy white deposit will these conditions, but this deposit is crystalline in
not be formed on the rod. nature.
‰ Identification of basic radicals
Group I
Separate
Original Dil. HCl AgCl, PbCl2, Hg2Cl2 (All white) solution Solution containing groups
solution Ksp values of their chlorides are low, hence from ppt. II, III, IV, V and VI
H2S
Kip > Ksp and they get precipitated.

Group III Group II


Fe(OH)3 (Reddish brown), HgS, PbS, Bi2S3, CuS (Black),
Separate CdS, As2S3, SnS2 (Yellow),
Cr(OH)3 (Green), Al(OH)3 (White) NH4OH in Solution containing
Sb2S3 (Orange), SnS (Brown)
Common NH4+ ion from NH4Cl presence of
groups III, IV, V
solution
NH4Cl from ppt. Due to common ion H+ from
decreases the ionisation of NH4OH thus and VI HCl, the ionisation of H2S
low [OH –]. Hence, only these
decreases thus low [S2–]. Hence
hydroxides of lower Ksp values are Group IV these sulphides of lower Ksp
precipitated. ZnS (Greenish white), MnS (Buff), values are precipitated.
CoS, NiS (Black)
Separate
Basic medium increases the ionisation Solution containing
solution
Separate H2S in
of H2S, thus high [S 2–]. Hence, these groups V and VI
from ppt.
solution Solution containing presence of sulphides with high values of Ksp
from ppt. groups IV, V and VI NH4OH undergo precipitation. (NH4)2CO3 in presence
of NH4OH

Group V
Na2HPO4 Separate
Group VI in presence Solution containing solution
BaCO3, SrCO3, CaCO3 (All white)
Mg(NH4)PO4 (White) group VI from ppt. These carbonates have lower Ksp values
of NH4OH
than that of Mg 2+ hence, they are
precipitated before Mg 2+

chemistry tODAy | March ‘16 41


‰ Confirmatory tests of basic radicals
Precipitates of Confirmatory Tests
Group I
AgCl Dissolves in NH4OH, white ppt. of AgCl is again obtained on adding dil. HNO3. Yellow ppt. of
AgI is formed on adding KI.
PbCl2 Dissolves in hot water, gives yellow ppt. of PbCrO4 with K2CrO4 and yellow ppt. of PbI2 with
KI.
Hg2Cl2 Turns black with NH4OH. Black residue {Hg + Hg(NH2)Cl} dissolves in aqua-
regia. Add stannous chloride solution to it then white ppt. is formed which turns grey.
Group II A Precipitates do not dissolve in yellow ammonium sulphide.
HgS Dissolves in aqua-regia, grey ppt. of Hg is obtained with SnCl2 or Cu turnings.
PbS Dissolves in dil. HNO3, white ppt. of PbSO4 is obtained on adding dil. H2SO4.
Bi2S3 Dissolves in dil. HCl, white ppt. of BiOCl is obtained on adding excess of water. Black ppt. of Bi
is obtained on adding Na2SnO2 solution.
CuS Blue coloured solution is obtained on adding dil. HNO3 and excess of NH4OH which gives
chocolate brown ppt. of Cu2[Fe(CN)6] with K4[Fe(CN)6].
CdS Colourless solution is obtained on adding dil. HNO3 and excess of NH4OH which gives yellow
ppt. of CdS again on adding H2S.
Group II B Precipitates dissolve in yellow ammonium sulphide.
As2S3 Insoluble sulphide, As2S5 is obtained by treating with conc. HCl which gives yellow ppt. of
ammonium arsenomolybdate on adding conc. HNO3 and heating with ammonium molybdate.
SnS2 or SnS Filtrate of sulphide in conc. HCl is reduced to SnCl2 by treating with Fe or Zn
which on adding HgCl2 solution initially gives white ppt. of Hg2Cl2 and finally
turns to grey Hg.
Sb2S3 Filtrate of sulphide in conc. HCl gives white ppt. of SbOCl on adding excess of water and orange
ppt. of Sb2S3 on passing H2S gas.
Group III
Fe(OH)3 Dissolves in dil. HCl, gives prussian blue solution or ppt. of Fe4[Fe(CN)6]3 on adding K4[Fe(CN)6]
and blood red coloured Fe(CNS)3 on adding KCNS.
Cr(OH)3 The solution obtained on heating precipitate with NaOH and Br2 water contains Na2CrO4 which
gives yellow ppt. of PbCrO4 on treating with acidified lead acetate solution.
Al(OH)3 Dissolves in NaOH and is again precipitated out on boiling with NH4Cl.
Group IV Soluble in conc. HCl
ZnS Solution (ZnCl2) is treated with NaOH, a white ppt. of Zn(OH)2 appears which dissolves in
excess of NaOH and on passing H2S, white ppt. of ZnS is obtained.
MnS Precipitate of MnO2 is obtained on heating the solution with NaOH and Br2 water. Pink colour
of HMnO4 is formed on supernatant liquid on treating the ppt. with excess of HNO3 and red
lead (Pb3O4).
Group IV Insoluble in conc. HCl
CoS Dissolves in aqua-regia. Yellow ppt. of potassium cobaltnitrite K3[Co(NO2)6] is obtained on
adding CH3COOH in excess and KNO2.
NiS Dissolves in aqua-regia. Red ppt. of Ni-dmg complex is obtained on adding NH4OH in excess
and dimethyl glyoxime.

42 chemistry tODAy | March ‘16


Group V Soluble in acetic acid
BaCO3 Yellow ppt. of BaCrO4 is obtained on adding K2CrO4 to solution.
SrCO3 White ppt. of SrSO4 is obtained on adding (NH4)2SO4 to solution.
CaCO3 White ppt. of CaC2O4 is obtained on adding (NH4)2C2O4.
Group VI
Mg2+ White ppt. of Mg(NH4)PO4 is formed on adding Na2HPO4 and NH4OH to solution.
Zero
NH4+ Salt evolves NH3 gas on heating with NaOH which gives dense white fumes of
NH4Cl with HCl and a brown ppt. of H2N⋅HgO⋅HgI on adding Nessler’s reagent, K2HgI4.

KEY POINT ‰ In this process, known volume of solution of known


• NH4Cl is added in group-V to convert NH4HCO3 concentration (standard solution) is allowed to react
(always contain in (NH4)2CO3) into (NH4)2CO3 with the other solution of unknown concentration
so that Ba2+, Sr2+ and Ca2+ are completely till the reaction is complete.
precipitated. ‰ Standard solution : It is a solution of known
strength.
SELF CHECK  Primary standard solutions : They can be
3. An aqueous solution of a salt X turns blood red prepared directly by dissolving a known weight
on treatment with SCN– and blue on treatment of the substance and making a known volume of
with K4[Fe(CN)6]. X also gives a positive chromyl the solution. e.g., oxalic acid, sodium carbonate,
chloride test. The salt X is Mohr’s salt.
(a) CuCl2 (b) FeCl3  Secondary standard solutions : They cannot be

(c) Cu(NO3)2 (d) Fe(NO3)3 prepared directly by weighing. e.g., KMnO4


(JEE Main 2015) or hygroscopic substances like NaOH, KOH,
or whose concentrations are known only
4. The cation that will not be precipitated by H2S in
approximately like HCl, H2SO4, etc.
the presence of dil. HCl is
(a) Cu2+ (b) Pb2+ ‰ Titrate : It is the substance whose concentration is
3+ to be determined by titration.
(c) As (d) Co2+ (JEE Main 2015)
5. Upon treatment with ammoniacal H2S, the metal ‰ Titrant : It is the solution of known strength (usually
taken in the burette).
ion that precipitates as a sulphide is
(a) Fe(III) (b) Al(III) ‰ Indicator : It is the substance which indicates the
(c) Mg(II) (d) Zn(II) end point of titration (by change of colour).
(JEE Advanced 2013) ‰ Equivalence point : It is the point at which the
6. Passing H2S gas into a mixture of Mn2+, Ni2+, Cu2+ chemical reaction involved in the titration is just
complete.
and Hg2+ ions in an acidified aqueous solution
precipitates ‰ Strength of a solution : It is the amount of solute in
(a) CuS and HgS (b) MnS and CuS grams present per litre of the solution.
(c) MnS and NiS (d) NiS and HgS  Strength (g/L) = Normality × Eq. wt.

(IIT-JEE 2011)  Strength (g/L) = Molarity × Mol. mass

Titrimetric Analysis ‰ Normality equation : N1V1 = N2V2


(Solution 1) (Solution 2)
‰ Titrimetric or volumetric analysis is a method of ‰ Molarity equation : M1V1n1 = M2V2n2
finding the volume of one solution which reacts (Solution 1) (Solution 2)
with a definite amount of another solution. [ N = M × n, where n = valency factor]

chemistry tODAy | March ‘16 43


‰ Percentage purity of a given salt  pH range of indicators :
Strength of given sample Indicators pH Colour of indicator
= × 100
Strength of pure sample range Acid Basic
Types of Titrations medium medium
‰ Acid-base titrations : In acid-base titration, the Methyl orange 3.1 – 4.4 Red Orange
strength of an acid or a base is determined by Bromophenol 3 – 4.6 Yellow Blue
titrating it against a standard solution of base or acid blue
respectively. It involves neutralisation reaction. Methyl red 4.2 – 6.3 Red Yellow
H+ + OH– H2O Litmus 5 – 8 Red Blue
From acid From base Water
Bromothymol 6 – 7.6 Yellow Blue
 Choice of indicators : The choice of an indicator blue
should be made in such a way that indicator
Phenol red 6.8 – 8.4 Yellow Red
used shows change in colour in the same pH
Thymolphthalein 9.3 – 10.5 Colourless Blue
range as developed around the equivalence
point. Phenolphthalein 8.3-10 Colourless Pink

Acid Alkali Indicator End point


Strong acid (HCl, H2SO4, Strong alkali (NaOH, KOH) Phenolphthalein or Pink to colourless or yellow/
HNO3) methyl orange orange to red, vice versa
Weak acid (oxalic acid, Strong alkali (NaOH, KOH) Phenolphthalein Pink to colourless, vice versa
acetic acid)
Strong acid (HCl, H2SO4, Weak alkali (Na2CO3, Methyl orange Yellow/orange to red, vice
HNO3) NaHCO3, KHCO3, NH4OH) versa
‰ Redox titrations : These titrations proceed with KEY POINT
transfer of electrons among the reacting ions in • When the reaction is just complete the stage of
aqueous solutions. titration is called equivalence point but when one
extra drop is added which is utilised by indicator
 Titration of oxalic acid vs KMnO4
to show a visual change then this stage is called
COOH end point.
— 2KMnO4 + 3H2SO4 + 5 ⋅2H2O
COOH
Practical Physical chemistry
l Enthalpy of Solution of CuSO4
K2SO4 + 2MnSO4 + 18H2O + 10CO2 l Enthalpy of Neutralisation of Strong Acid and Strong Base
— Calculations l Preparation of Lyophilic and Lyophobic Sols
MKMnO × VKMnO l Kinetic Study of Reaction of Iodide Ion with Hydrogen
4 4 2 Peroxide at Room Temperature
=
Moxalic acid × Voxalic acid 5
tiPs tO remember
 Titration of Mohr’s salt vs KMnO4 Enthalpy of Solution of CuSO4
— 2KMnO4 + 8H2SO4 + ‰ Enthalpy of solution is the heat change involved
10FeSO4·(NH4)2SO4·6H2O during the dissolution of one mole of a solute in
K2SO4 + 2MnSO4 + 5Fe2(SO4)3 + such a large excess of solvent so that no further heat
10(NH4)2SO4 + 68H2O change occur on dilution.
CuSO4(s) + H2O CuSO4(aq); DsolH°
— Calculations
‰ Dissolution of CuSO4 in water is exothermic.
MKMnO × VKMnO 1 The enthalpy of solution of CuSO4(s) is calculated
4 4
=
MMohr’s salt × VMohr’s salt 5 from the highest temperature attained during its
dissolution.

44 chemistry tODAy | March ‘16


‰ Calculations : If dissolution of w g of CuSO4 in Kinetic Study of Reaction of Iodide Ion with Hydrogen
200 g solvent (water) causes Dt°C change in Peroxide at Room Temperature
temperature, then ‰ It is based on the principle of set of following three

Heat evolved (q) = Mass × Specific heat × reactions, collectively called clock reaction.
Change in temperature  Main reaction : Hydrogen peroxide oxidises
q = (200 + W) × 4.2 × Dt J, where W is water iodide ion (from KI) to iodine in acidic
equivalent of calorimeter (given). medium.
Slow
Enthalpy of solution per mole of CuSO4 in water H2O2(aq) + 2I–(aq) + 2H+(aq) I2(aq)
+ 2H2O(l)
q × 159.5 × 10−3
=− kJ mol −1  Monitor reaction : When this reaction is carried
w
[Q Molar mass of CuSO4 = 159.5 g mol–1] out in presence of a small amount of sodium
thiosulphate and starch, the iodine produced
Enthalpy of Neutralisation of Strong Acid and Strong Base first reacts with sodium thiosulphate as
‰ Enthalpy of neutralisation is the enthalpy change follows :
Fast
accompanying neutralisation of one gram 2S2O2–3(aq) + I2(aq) S4O2– –
6(aq) + 2I (aq)
equivalent of a base by an acid in dilute solutions at  Indicator reaction : When thiosulphate ions
a given temperature. get completely consumed, the liberated iodine
NaOH(aq) + HCl(aq) NaCl(aq) + H2O(l) reacts with starch solution to give blue coloured
It is an exothermic reaction. complex.
‰ The heat of neutralisation of a strong acid by a I2(aq) + Starch(aq) Blue complex
As the concentration of thiosulphate ion is
strong base in their dilute solutions is generally
kept constant, the different time taken (tc) for
57.3 kJ. The reaction may be represented as the appearance of blue colour with change in
H+(aq) + OH–(aq) H2O, DH = –57.3 kJ concentration of either reactant indicates the
‰ Calculations : Heat evolved during neutralisation relative rate of reaction.
of 100 mL of 0.5 N HCl, 1
Initial rate ∝
q = (200 + W) × Dt × 4.2 J, where W is water tc
equivalent of calorimeter (given). The rate of reaction decreases with decrease in
Thus, enthalpy of neutralisation of 1000 mL of concentration of KI.
q The graph of 1/tc versus volume of KI solution is
1 N HCl and NaOH = − kJ a straight line.
0.5 × 100
Preparation of Lyophilic and Lyophobic Sols 0.10
0.09
‰ Preparation of lyophilic sols : These sols are 0.08
1/tc(s–1)

0.07
prepared by shaking the lyophilic material with the 0.06
0.05
dispersion medium. e.g., colloidal sols of gelatin, 0.04
0.03
gum, starch, egg albumin, etc. 0.02
0.01
‰ Preparation of lyophobic sols : These sols do not 0
4 8 12 16 20
form simply by mixing the lyophobic material
Volume of KI solution (mL)
with dispersion medium instead they are prepared
indirectly. e.g., colloidal sols of ferric hydroxide and Rate of reaction ∝ Concentration of KI
Similarly, by keeping I– ion concentration
aluminium hydroxide can be prepared by hydrolysis
constant and taking different concentrations of
of FeCl3 and AlCl3 with boiled distilled water. HCl
H2O2, the rate with respect to H2O2 can be found
produced, is removed with dialysis. out.
FeCl3 + 3H2O  Fe(OH)3 + 3HCl
answer Keys (self checK)
Red or brown sol
 1. (d) 2. (d) 3. (b) 4. (d) 5. (d)
AlCl3 + 3H2O Al(OH)3 + 3HCl 6. (a)
Colourless sol ‰‰

chemistry tODAy | March ‘16 45


C
CONCEPT THE p-BLOCK Si
Ge
Group 14 elements show a
pronounced discontinuity in their
general properties between the

ELEMENTS (Group 14) Sn

Pb
first and second row elements
followed by a gradual transition
towards more metallic character.

Chemical Properties
· Reactivity towards air :
Ø They form oxides of the formula EO and EO2 on
heating with air.
Ø Acidic strength of their oxides decreases down the group.
Atomic and CO2,SiO2 GeO2 SnO2,PbO2
Physical Properties
· Elements : C, Si, Ge, Sn, Pb
GROUP 14 : Acidic Less acidic Amphoteric

THE CARBON · Reactivity towards water :


· Electronic configuration : [Noble gas] ns2np2 Ø Only Sn can decompose water.
· Oxidation states : +2 and +4 FAMILY Sn + 2H2O D SnO2 + 2H2
· Atomic radii, metallic character and stability of +2 O.S. : Ø Pb is unaffected by water due to formation of protective oxide
Generally increase down the group. film.
· Ionisation enthalpy, melting point, boiling point, reducing · Reactivity towards halogens :
character and stability of +4 O.S. : Ø They form halides of the formula EX4 and EX2.
Generally decrease down the group. Ø Except C, all react directly with halogens.
Ø IE of Pb is slightly higher than Sn due to lanthanide contraction. Ø Except C and Si, all form dihalides.
Ø IE1 and IE2 are higher and lower than the corresponding group 13
elements respectively.
· Catenation : Tendency of catenation decreases down the Anomalous
group. Behaviour of C
· Allotropy : Except Pb, all others show allotropy. · The anomalous behaviour of C is due to
· Complex formation : Except C, all other small size, high ionisation energy and
form complexes due to presence of absence of d-orbitals.
vacant d-orbitals. · C is hardest having highest m.pt. and b.pt.
amongst the elements of group 14.
· C shows maximum covalency of 4 while rest
show maximum covalency of 6.
· C has maximum tendency for
O– catenation and multiple bonding
O–
(pp-pp) and shows
Si O allotropy.

O O– –
O O–
O = Oxygen C O C O
O– or C O
= Silicon
Discrete SiO44–
tetrahedron

ë Silicates Carbon Monoxide (CO)


ë
· Basic unit is SiO44– . · Preparation :
· They exist either as discrete unit or joined together by Important Ø C + H2O CO + H2
sharing 1, 2, 3 or 4 oxygen atoms per silicate unit to form Compounds Water gas
different structures like chain, ring, sheet or 3-D network. of 1273 K
Ø 2C + O2 + 4N2 2CO + 4N2
· Zeolites are 3-D silicates in which some of the Si atoms are C and Si
replaced by Al3+ ions and to balance the negative charge Producer gas

some cations like Na+, K+ or Ca2+ are incorporated. They · Highly poisonous due to the formation of a complex with
are used in water softening. haemoglobin (Hb) which is 300 times more stable than
O2–Hb complex thus, prevents Hb in the RBCs from
carrying O2 round the body.

ë Silicon Dioxide (SiO2) ë Carbon Dioxide (CO2) Silicones


ë
· Covalent, three dimensional network solid. · Preparation : · Synthetic organosilicon polymers containing
· Almost non-reactive due to high Si – O bond Ø CaCO3 + 2HCl CaCl2 + CO2 + H2O repeated R2SiO units held by Si – O – Si linkage.
enthalpy. · It is consumed during photosynthesis. · They are water repelling due to non-polar alkyl
hu
6CO2 + 12H2O C6H12O6 + 6O2 + 6H2O groups.

Si O Si O Si +
O C O R R
O O O
O C O
Si O Si O Si O Si O Si R
O O O + – R
O C O nR
Si O Si O Si
1. Which of the following compounds is responsible (c) The unknown compound will only react with
for yellow colour in the xanthate test for alcoholic dilute nitric acid and not with barium nitrate.
group? (d) The acid must be added directly to the solution
to test the presence of carbonates.
(a) (b) 8. In Lassaigne’s test, organic compound is fused with
a piece of sodium metal so as to
(a) convert the covalent compound into a mixture
(c) (d) of ionic compounds
(b) decrease the melting point of the compound
2. Radical that gives rosy red ppt. with DMG is
(c) increase the reactivity of the compound
(a) Cd2+ (b) Ni2+
2+ (d) increase the ionisation of the compound.
(c) Mn (d) Ba2+
9. Which salt would give SO2 with hot and dilute
3. In the green edged flame test for borate, the flame is
H2SO4 and also decolourise Br2 water?
green only on the edges because
(a) Na2SO3 (b) NaHSO4
(a) edges represent hottest part of flame where (c) Na2SO4 (d) Na2S
combustion of ethyl borate is complete
(b) it is characteristic property of ethyl borate 10. An excess of sodium hydroxide is added to an
(c) ethyl borate vapourises only on the edges aqueous solution of salt X and boiled. Ammonia
(d) ethyl borate decomposes only on the edges. gas is only given off after aluminium foil is added to
the hot solution. What could be X?
4. The number of moles of KMnO4 needed to react (a) Sodium nitrate (b) Ammonium nitrate
completely with one mole of ferrous oxalate in (c) Calcium sulphate (d) Barium nitrate
acidic solution is
11. H2S in the presence of HCl precipitates group II but
3 2
(a) (b) not group IV because
5 5 (a) HCl activates H2S
4
(c) (d) 1 (b) HCl increases concentration of Cl–
5 (c) HCl decreases concentration of S2–
5. Identify the correct order of solubility of (d) HCl lowers the solubility of H2S in solution.
Na2S, CuS and ZnS in aqueous medium.
(a) CuS > ZnS > Na2S (b) ZnS > Na2S > CuS 12. Sodium carbonate cannot be used in place of
(c) Na2S > CuS > ZnS (d) Na2S > ZnS > CuS (NH4)2CO3 for the identification of Ca2+, Ba2+
6. Before testing for halogens, the Lassaigne’s extract and Sr2+ ions (in group V) during mixture analysis
is boiled with because
(a) Mg2+ ions will be precipitated
(a) conc. HCl (b) NaOH
(b) concentration of CO2–3 ions is very low
(c) conc. HNO3 (d) all of these.
(c) sodium ions will react with acid radicals
7. A student is given a solution which may contain (d) Na+ ions will interfere with the detection of
carbonate ions. She decides to add aqueous barium Ca2+, Ba2+, Sr2+ ions.
nitrate to the solution first, followed by dilute nitric
13. To perform azo dye test, the organic compounds
acid. Choose the correct statements about her needed are
experiment. (a) 1° aliphatic amine and CHCl3
(a) Dilute nitric acid reacts with both soluble and (b) 1° aromatic amine and 2-naphthol
insoluble carbonates. (c) phenol and aniline
(b) The above procedure is strictly to test the (d) both (b) and (c).
presence of sulphate ions only.

52 chemistry tODAy | March ‘16


14. Which of the following salts on strong heating in 20. Sometimes a brown precipitate of hydrated MnO2
a dry test tube becomes yellow and on cooling it (i.e., MnO2·H2O) is observed in KMnO4 titrations.
becomes white again? This is due to
(a) BaCO3 (b) ZnCO3 (a) insufficient quantity of dil. H2SO4 which results
(c) (NH4)2CO3 (d) PbCO3 in incomplete reduction of KMnO4
(b) overheating of the solution
15. Match the list I with list II and select the correct
(c) dropwise addition of KMnO4 with constant
answer using the code given below the lists.
shaking
List I List II
(d) addition of hydrochloric acid.
P. Sr2+ 1. Golden yellow
Q. K+ 2. Apple green 21. Excess of KI reacts with CuSO4 solution and then
R. Na+ 3. Crimson red Na2S2O3 solution is added to it. Which of the
S. Ba2+ 4. Lilac following statements is incorrect for this reaction?
P Q R S (a) Na2S2O3 is oxidised.
(b) CuI2 is formed.
(a) 1 2 3 4 (c) Cu2I2 is formed.
(b) 3 4 1 2 (d) Evolved I2 is reduced.
(c) 2 1 4 3
(d) 4 3 1 2 22. The formula mass of an acid is 82 amu. In a titration,
100 cm3 solution of this acid containing 39 g of
16. A yellow turbidity, sometimes appears on passing the acid per litre was completely neutralised by
H2S gas even in the absence of the second group 95 cm3 of an aqueous solution of NaOH, containing
radicals. This happens because 40 g NaOH per litre of solution. What is the basicity
(a) sulphur is present in the mixture as an of the acid?
impurity (a) 4 (b) 2
(b) the fourth group radicals are precipitated as (c) 1 (d) 0
sulphides
23. Which of the following cannot be used as starting
(c) H2S is oxidised by some acidic radical present
material for the preparation of iodoform?
in solution
(a) Butan-2-one (b) Acetophenone
(d) the third group radicals are precipitated.
(c) Propan-2-ol (d) Propan-1-ol
17. Aqueous sodium hydroxide reacts with a metal ion
24. Ferric hydroxide sol can be prepared by shaking
producing a coloured precipitate. This precipitate
(a) FeCl3 solution with dilute NaOH solution
changes colour on standing. Identify the ion
(b) freshly precipitated Fe(OH)3 with water
present.
(c) freshly precipitated Fe(OH)3 with sufficient
(a) Fe2+ (b) Fe3+
amount of dilute HCl
(c) Cu+ (d) Cu2+
(d) FeCl3 with boiling water.
18. Enthalpy of neutralisation of H2SO4 with NaOH is 25. Small amount of zinc dust is added to reaction
(a) same as that of HCl with NaOH mixture during preparation of acetanilide because
(b) double than that of HCl with NaOH (a) zinc catalyses the reaction
(c) half than that of HCl with NaOH (b) zinc helps in crystallisation
(d) double than that of HNO3 with NaOH. (c) zinc protects aniline from oxidation
19. ‘X’ is a colourless salt giving following reactions : (d) zinc hydrolyses acetic anhydride.
AgNO3/HNO3
White ppt. NaOH X 26. Identify P and Q in the following series of
(dissolves in NH4OH/H2S reactions.
excess of NaOH) White ppt. P + dil. H2SO4 Brown colour vapours turning
White ppt. (soluble in
aq. NH3 )
(KI + starch) paper blue.
P  Q(g) + R(g)
‘X’ can be
R is a liquid at room temperature.
(a) AlCl3 (b) ZnCl2
(a) NaOH, O2 (b) NH4NO2, N2
(c) Zn(CH3COO)2 (d) ZnBr2
(c) NH4OH, N2 (d) NO2, O2

chemistry tODAy | March ‘16 53


27. A test tube containing nitrate and another containing
4. (a) :
bromide and MnO2 are treated with conc. H2SO4.
In acidic medium, MnO4– changes to Mn2+ and
The brown fumes evolved are passed in water. The
consumes 5e–.
water will be coloured by
\ 3e– will be consumed by 3/5 moles of KMnO4.
(a) the nitrate (b) the bromide
(c) both of these (d) none of these. 5. (d) : Na2S is strongly electrovalent. Copper belongs
to group II and precipitates first as CuS (black)
28. Salt which does not respond to dilute and whereas zinc belongs to group IV and precipitates
concentrated sulphuric acid is later as ZnS (greenish white), hence solubility order
(a) Na2SO4 (b) Na3PO4 is Na2S > ZnS > CuS.
(c) CaF2 (d) all of these. 6. (c) : Lassaigne’s extract is boiled with conc. HNO3 to
29. How do we differentiate between Fe3+ and Cr3+ in decompose Na2S and NaCN which would otherwise
qualitative analysis of group III? interfere with the tests of halogens. HCl cannot be
(a) By taking excess of NH4OH. used because we cannot add Cl– ion when we have
(b) By increasing NH4+ ion concentration. to test for Cl in the organic compound. NaOH also
(c) By decreasing OH– ion concentration. cannot be used because it would precipitate AgNO3
(d) Both (b) and (c) as AgOH.
7. (a) : When barium nitrate is added, a white
30. In a charcoal cavity test in an oxidising flame
precipitate of barium carbonate is formed. This
(using cobalt nitrate), salts of aluminium, zinc and
precipitate reacts with dilute nitric acid added, to
magnesium produce residues of specific colour.
produce effervescence with the liberation of CO2
Which of the following gives the correct match of gas.
the composition and colour of the residue? Ba2+(aq) + CO32–(aq) BaCO3(s)
(a) CoAl2O4 → Thenard’s blue BaCO3(s) + 2H+(aq) Ba2+(aq) + CO2(g) + H2O(l)
(b) CoZnO2 → Rinnmann’s green
8. (a) : This is done to get a mixture of ionic compounds
(c) CoMgO2 → Pale pink
such as NaCN, Na2S, NaX, etc.
(d) All of these
9. (a) : Na2SO3 + H2SO4 Na2SO4 + H2O + SO2
sOlutiOns Na2SO3 + Br2 + H2O 2HBr + Na2SO4
1. (b) : ROH + KOH RO–K+ + H2O 10. (a) : This is a specific test for nitrate ions (NO3–). If
ammonia is evolved before the aluminium foil, then
salt X contains ammonium ions. Since ammonia is
only liberated when heated with aluminium foil,
2. (b) : Ni2+ in presence of ammonia gives rosy red the presence of nitrate ions is confirmed.
ppt. of bis(dimethylglyoximato)nickel(II) complex. 11. (c) : Due to common ion effect, HCl decreases
concentration of S2– ions and only group II basic
radicals are precipitated.
12. (a) : In group V, (NH4)2CO3 is used in the presence
of NH4Cl. In presence of NH4Cl dissociation of
(NH4)2CO3 decreases and due to low concentration
of CO2– 3 ions only group V radicals are precipitated
out. If Na2CO3 is used, concentration of CO2– 3 ions
will increase and group VI radical, Mg2+ ions will
also be precipitated.
13. (d)
14. (b) : ZnCO3 ZnO + CO2↑
It is an example of decomposition reaction. Colour
of zinc oxide product is yellow when hot and white
3. (a)
when cold.

54 chemistry tODAy | March ‘16


15. (b) for the preparation of iodoform. Propan-1-ol,
16. (c) : Radicals such as NO–3 oxidise H2S to S which CH3CH2CH2OH does not contain such groups.
appears as yellow turbidity. 24. (d) : Fe(OH)3 sol is prepared by shaking FeCl3 with
17. (a) : Both Fe2+ and Fe3+ ions form coloured boiling water.
precipitates of metal hydroxides i.e., dirty green 25. (c)
Fe(OH)2 and reddish brown Fe(OH)3. Ion with the 26. (b) : When ammonium nitrite (P) treated with dil.
lower oxidation number, Fe2+ changes the colour
H2SO4 gives light brown fumes of NO2. The light
on standing.
brown gas (NO2) decomposes iodides to free iodine
18. (a) : H2SO4 and NaOH are strong acid and strong which when treated with starch solution gives blue
base. HCl and NaOH are also strong acid and strong colour.
base. Hence, their enthalpies of neutralisation are 2KI + 2NO2 2KNO2 + I2
same. I2 + starch Starch iodide (Blue)
HNO3 
19. (b) : ZnCl2 + 2AgNO3 Zn(NO3)2 + NH4NO2 N2↑ + 2H2O
(X) 2AgCl↓ (P) (Q) (R)
White ppt.
(soluble in aq. NH3) 27. (b) : NO3– gives NO2 with conc. H2SO4 which
ZnCl2 + 2NaOH Zn(OH)2↓ + 2NaCl when passed through water gives HNO3 which
(X) White ppt. is colourless. On the other hand, Br– + MnO2 on
Zn(OH)2 + 2NaOH Na2ZnO2 + 2H2O heating with conc. H2SO4 gives Br2 which gives its
Soluble
colour (orange) to water when added to it.
NH4OH 28. (d) : Salts of sulphate, phosphate, fluoride and
ZnCl2 + H2S ZnS↓ + 2HCl
(X) White ppt. borate do not respond to dilute and concentrated
sulphuric acid.
20. (a) : A brown ppt. of hydrated MnO2 will be formed,
if insufficient quantity of dil. H2SO4 is added or 29. (d) : Ksp of Fe(OH)3 < Ksp of Cr(OH)3. Thus,
H2SO4 is not added at all in the titration process. Fe3+ is precipitated at lower OH– concentration.
This is due to incomplete reduction of KMnO4. 30. (d)
21. (b) : 4KI + 2CuSO4 I2 + Cu2I2 + 2K2SO4 qq
(0) (0, +4) (0, +5) (−1) Form IV
I2 + 2 Na 2S2O3 Na 2S4 O6 + 2 NaI 1. Place of Publication : New Delhi
22. (b) : NNaOH = 1 N (Q 40 g/L 1 N NaOH) 2. Periodicity of its publication : Monthly
3. Printer’s and Publisher’s Name : Mahabir Singh
N1V1(acid) = N2V2(NaOH)
Nationality : Indian
N1 × 100 = 1 × 95
Address : Chemistry Today,
N1 = 0.95 N 406, Taj Apartment,
w × 1000 New Delhi - 110029.
N= B
EB × V 4. Editor’s Name : Anil Ahlawat
39 × 1000 Nationality : Indian
0.95 = E × 1000 Address : Chemistry Today,
B 19, National Media
EB = 41 Centre, Gurgaon
Molecular mass Haryana - 122002
Equivalent mass = 5. Name and address of : Mahabir Singh
Basicity
82 individuals who own the 406, Taj Apartment,
41 = newspapers and partners or New Delhi
Basicity
shareholders holding more than
or, Basicity= 2 one percent of the total capital
23. (d) : Organic compound having either I, Mahabir Singh, here by declare that particulars given above are
true to the best of my knowledge and belief.
Mahabir Singh
group or group is used Publisher

chemistry tODAy | March ‘16 55


Exam Dates
OfflinE : 3rd April
OnlinE : 9th & 10th April

1. Indicate the organic structure for product expected 6. Which one of the following cyano complexes
when 2-methylpropene is heated with acetyl would exhibit the lowest value of paramagnetic
chloride in the presence of anhydrous ZnCl2. behaviour?
(a) (a) [Cr(CN)6]3– (b) [Mn(CN)6]3–
3–
(c) [Fe(CN)6] (d) [Co(CN)6]3–
7. If the nitrogen atom has electronic configuration 1s7,
(b) it would have energy lower than that of the normal
ground state configuration 1s22s22p 2 3, because the
electrons would be closer to the nucleus. Yet, 1s7 is
not observed because it violates
(c) (a) Heisenberg uncertainty principle
(b) Hund’s rule
(c) Pauli’s exclusion principle
(d) (d) Bohr’s postulates of stationary orbits.
8. Amoxicillin is semi-synthetic modification of
2. Phospholipids are esters of glycerol with (a) penicillin (b) streptomycin
(a) three carboxylic acid residues (c) tetracycline (d) chloramphenicol.
(b) two carboxylic acid residues and one phosphate 9. The decreasing order of the ionisation potential of
group the following elements is
(c) one carboxylic acid residue and two phosphate
(a) Ne > Cl > P > S > Al > Mg
groups
(b) Ne > Cl > P > S > Mg > Al
(d) three phosphate groups.
(c) Ne > Cl > S > P > Mg > Al
3. Which of the following alkali metal ions has the
(d) Ne > Cl > S > P > Al > Mg
highest conductivity in aqueous solution?
(a) Li+ (b) Cs+ (c) Na+ (d) K+ 10. Which of the following factors is of no significance
4. In order to convert aniline into chlorobenzene, the for roasting sulphide ores to the oxides and not
reagent used is subjecting the sulphide ores to carbon reduction
(a) NaNO2/HCl, CuCl (b) Cl2/CCl4 directly?
(c) Cl2/AlCl3 (d) CuCl2 (a) CO2 is more volatile than CS2.
5. For the given structure, the site (b) Metal sulphides are thermodynamically more
marked as S is a stable than CS2.
(a) tetrahedral void (c) CO2 is thermodynamically more stable than
(b) cubic void CS2.
(c) octahedral void (d) Metal sulphides are less stable than the
(d) none of these. corresponding oxides.

56 ODA | march ‘16


chemistry tODAy
ODAy
11. In the following sequence of reactions, the alkene What is the relationship between E1 and E2?
affords the compound B. (a) E2 = 0 ≈ E1 (b) E1 > E2
O Zn/H2O
CH3CH CHCH3 3 A B (c) E1 < E2 (d) E1 = E2
The compound B is 18. Which of the following does not have optical
(a) CH3CHO (b) CH3CH2CHO
isomer?
(c) CH3COCH3 (d) CH3CH2COCH3
(a) [Co(NH3)3Cl3] (b) [Co(en)3]Cl3
12. The volume of a colloidal particle, Vc as compared (c) [Co(en)2Cl2]Cl (d) [Co(en)(NH3)2Cl2]Cl
to the volume of a solute particle in a true solution
Vs could be 19. 29.5 mg of an organic compound containing
(a) ~ 1 (b) ~ 1023 nitrogen was digested according to Kjeldahl’s
–3
(c) ~ 10 (d) ~ 103 method and the evolved ammonia was absorbed
13. The isomeric cis-but-2-ene and trans-but-2-ene can in 20 mL of 0.1 M HCl solution. The excess of the
be distinguished on the basis of acid required 15 mL of 0.1 M NaOH solution for
(a) their physical states complete neutralisation. The percentage of nitrogen
(b) their reduction products in the compound is
(c) the products they give on ozonolysis (a) 29.5 (b) 59.0
(d) the products they give on addition of bromine. (c) 47.4 (d) 23.7
Ca(OH)2 CO2
(S) CaCO3 (T) 20. The basic character of the transition metal
H2O

Milky monoxides follows the order
14. CuCO3 Clear soln.
(a) VO > CrO > TiO > FeO
heat with conc. HNO3
CuO (P) (Q) (b) CrO > VO > FeO > TiO
CuS
liquid NH3 (c) TiO > FeO > VO > CrO
(d) TiO > VO > CrO > FeO
Blue solution
Identify P, R, S and T 21. Match list I (compounds) with list II (uses) and
P R S T select the correct answer using the code given below
(a) Cu CO2 Ca(HCO3)2 [Cu(NO3)4]2+ the lists :
(b) Cu2S Cu Cu2O Ca(HCO3)2 List I List II
(c) Cu [Cu(NH3)4]2+ CO2 Ca(HCO3)2 i. Acetyl salicylic acid (A) Insecticide
(d) CO2 [Cu(NO3)4]2+ Cu2O Ca(HCO3)2 ii. DDT (B) Drug
15. Which of the following has pp-dp bonding? iii. Naphthalene (C) Moth repelling
(a) NO3– (b) SO32– iv. Carbon tetrachloride (D) Fire extinguisher
(c) BO33– (d) CO32– (E) Refrigerant
16. The degree of hardness of water is usually expressed (a) i-(B), ii-(A), iii-(C), iv-(D)
in terms of (b) i-(E), ii-(C), iii-(D), iv-(A)
(a) parts per million by weight of MgSO4 (c) i-(B), ii-(C), iii-(D), iv-(A)
(b) grams per litre of CaCO3 and MgCO3 actually (d) i-(E), ii-(A), iii-(C), iv-(D)
present
(c) parts per million by weight of CaCO3 regardless 22. A welding fuel gas contains carbon and hydrogen
of whether it is actually present only. Burning a small sample of it in oxygen gives
(d) parts per million of CaCO3 actually present in 3.38 g carbon dioxide, 0.690 g of water and no other
water. products. A volume of 10.0 L (measured at STP)
17. The emf of a Daniell cell at 298 K is E1 of this welding gas is found to weigh 11.6 g. The
Zn | ZnSO4(0.01 M) || CuSO4 (1.0 M) | Cu molecular formula of gas is
When the concentration of ZnSO4 is 1.0 M and that (a) C2H2 (b) CH4
of CuSO4 is 0.01 M, the emf is changed to E2. (c) C2H4 (d) C2H6

chemistry tODAy | march ‘16 57


23. 18 g of glucose (C6H12O6) is added to 178.2 g of (a) q = W = 500 J, DU = 0
water. The vapour pressure of water for this aqueous (b) q = DU = 500 J, W = 0
solution at 100°C is (c) q = W = 500 J, DU = 500
(a) 759.00 torr (b) 7.60 torr (d) DU = 0, q = W = –500 J
(c) 76.00 torr (d) 752.40 torr
30. A dilute solution of H2O2 can be concentrated by
24. Charge distribution in iodine monochloride is best
(a) drying it over anhydrous CaCl2
represented as
(a) I+ Cl– (b) Id+ Cld– (b) drying it over concentrated H2SO4

(c) I Cl +
(d) Id– Cld+ (c) drying it over anhydrous MgSO4
25. Bromine monochloride, BrCl decomposes into (d) heating it under reduced pressure.
bromine and chlorine and reaches the equilibrium : sOlutiOns
2BrCl(g) Br2(g) + Cl2(g) for which Kc = 32 at 500 K.
If initially pure BrCl is present at a concentration of CH3
 – ZnCl (anhyd.)
3.3 × 10–3 mol L–1, what is its molar concentration 1. (c) : CH3 C CH2+ CH3COCl
2

in the mixture at equilibrium? 2-Methylpropene


(a) 3 × 10–4 mol L–1 (b) 4 × 104 mol L–1 CH3
(c) 5 × 10–2 mol L–1 (d) 7 × 10–5 mol L–1 CH3 C CH2COCH3
26. After understanding the assertion and reason, Cl
choose the correct option. 2. (b) : In phospholipids, two of the three hydroxyl
Assertion : NaCl reacts with concentrated H2SO4 groups of glycerol are esterified with two carboxylic
to give colourless fumes with pungent smell. But on
acids and third hydroxyl group is esterified with
adding MnO2 the fumes become greenish yellow.
some derivative of phosphoric acid.
Reason : MnO2 oxidises HCl to chlorine gas which
is greenish yellow. 3. (b) : Cs+ being least hydrated shows maximum
(a) Assertion and reason are correct and reason is ionic mobility and thus, highest conductivity.
the correct explanation for the assertion.
(b) Assertion and reason are correct but reason is
not the correct explanation for the assertion. 4. (a) :
(c) Assertion is correct, reason is incorrect.
(d) Assertion is incorrect, reason is correct.
27. Solid XeF6 exists as
(a) XeF4+ and F2– (b) XeF5+ and F–
(c) XeF7– and F+ (d) Xe4+ and F4–
28. Which of the following are characteristics of
thermosetting polymers? 5. (c) : Octahedral voids occupy the position of edge
I. Heavily branched cross linked polymers. centre and body centre.
II. Linear slightly branched long chain molecules. 6. (d) : [Co(CN)6]3–
III. Become infusible on moulding so cannot be
Co → [Ar] 3d7 4s2
reused.
Co3+ → [Ar] 3d6 4s0
IV. Soften on heating and harden on cooling, can
be reused.
(a) I and IV (b) II and III
(c) I, II and III (d) I and III In presence of strong field ligand CN–, pairing of
29. When one mole of a gas is heated at constant electrons takes place.
volume, temperature is raised from 298 to 308 K.
Heat supplied to gas is 500 J. Then which of the
following is correct?

58 chemistry tODAy | march ‘16


There is no unpaired electron, so the lowest value of 14. (c) :
Ca(OH)2 CO2 + H2O
paramagnetic behaviour is observed. CO2 CaCO3
(S) Milky
7. (c) : According to Pauli’s exclusion principle an Ca(HCO3)2

orbital can accommodate a maximum of two CuCO3 Clear soln.
(T)
electrons.
Heat with conc. HNO3
CuO Cu Cu(NO3)2
8. (a) : Amoxicillin (an antibiotic) is semi-synthetic CuS
(P) (Q)
modification of penicillin. Liquid NH3
[Cu(NH3)4](NO3)2
9. (b) : Ionisation energy increases from left to right
in a period but ionisation energy of group-2 is greater Blue solution

than ionisation energy of group-13 and ionisation 15. (b) : In SO32–, d-orbital of sulphur overlaps with
energy of group-15 is greater than ionisation energy p-orbital of oxygen to form pp-dp bond. N, B and C
of group-16. do not have d-orbitals.
This is because of stable electronic configuration of 16. (c) : Degree of hardness of water is expressed in
group 2 (ns2) and group 15 (ns2np3). Thus, order of terms of parts per million by weight of CaCO3
ionisation potential is Ne > Cl > P > S > Mg > Al. equivalent to various calcium and magnesium salts
present.
10. (d) : The reduction process of metal sulphides
17. (b) : Daniell cell reaction :
by carbon is non-spontaneous while the
Cu2+ + Zn → Zn2+ + Cu ; n = 2
reduction process of metal oxides by carbon is
spontaneous. Thus, it can be concluded that CO2 ° 0.0591 [Zn2+ ]
Ecell = Ecell − log
is thermodynamically more stable than CS2 and 2 [Cu2+ ]
the metal sulphides are more stable than the ° 0.0591 0.01
E1 = Ecell − log ,
corresponding oxides. 2 1.0
11. (a) : The complete reaction sequence is as follows : ° 0.0591 1.0
E2 = Ecell − log
H H H O H 2 0.01
O3
C C C C On increasing [Zn2+] and decreasing [Cu2+], E2
H3C CH3 H3 C CH3 becomes less than E1 i.e., E1 > E2.
O O 18. (a) : Octahedral complexes of type [MA3B3] does
Mono-ozonide
Zn-H2O not show optical isomerism.
2CH3CHO + ZnO
Cleavage 19. (d) : The % of N according to Kjeldahl’s method
12. (d) : For true solution the diameter range is 1 to 10 Å 1.4 × N1 × V
=
and for colloidal solution diameter range is 10 to w
1000 Å. N1 = Normality of the standard acid = 0.1 N
3
w = Mass of the organic compound taken
3
Vc (4 / 3) prc r  = 29.5 mg = 29.5 × 10–3 g
= = c
Vs (4 / 3)prs3  rs  V = Volume of N1 acid neutralised by ammonia
3 = (20 – 15) = 5 mL
 10 
Ratio of diameters =   = 103 1.4 × 0.1 × 5
1 ⇒ %N = = 23.7
Vc 29.5 × 10−3
 103 20. (d) : Metal oxide with more ionic character will
Vs
be more basic. Ionic radii of metal ion decreases
13. (d) : cis-but-2-ene yields racemic mixture whereas from Ti2+ to Fe2+, the basic character of their metal
trans-but-2-ene gives the meso compound on oxides decrease from TiO to FeO. Thus, order of
addition of bromine. basic character is TiO > VO > CrO > FeO.

chemistry tODAy | march ‘16 59


21. (a) : Acetyl salicylic acid - Drug 24. (b) : Interhalogen compounds are covalent
DDT - Insecticide compounds. Since chlorine has higher
Naphthalene - Moth repelling electronegativity than iodine, iodine monochloride
Carbon tetrachloride - Fire extinguisher can be represented as Id+Cld–.
3.38 25. (a) : 2BrCl(g) Br2(g) + Cl2(g)
22. (a) : Number of moles of CO2 = = 0.0768
No. of moles of C = 0.0768 44 Initial 3.30 × 10–3 mol L–1 0 0
–3 x x
0.690 At eq. (3.30 ×10 – x)
2
No. of moles of H2O = = 0.0383 ( x / 2)( x / 2)
2
18 Kc = = 32 (Given)
\ No. of moles of H = 2 × 0.0383 = 0.0766 (3.30 × 10−3 − x )2
(i) The ratio of moles of C to H is 0.0768 : 0.0766 x
or = 32 = 5.66
or 1 : 1 2(3.30 × 10−3 − x )
Therefore, empirical formula = CH
(ii) 10.0 L of fuel gas at STP weighs or x = 11.32(3.30 × 10–3 – x)
11.6 × 22.4 or 12.32x = 11.32 × 3.30 × 10–3
= = 25.98 g or x = 3.0 × 10–3
10
\ At eq., [BrCl] = (3.30 × 10–3 – 3.0 × 10–3)
\ Molar mass of gas = 25.98 g ≈ 26 g mol–1
= 0.30 × 10–3
molar mass 26
(iii) n = = =2 = 3.0 × 10–4 mol L–1
empirical formula mass 13
26. (a) : Colourless fumes of HCl become greenish
\ Molecular formula = (empirical formula)n
yellow because MnO2 oxidises HCl to chlorine gas.
= (CH)2 = C2H2
°
p − ps n 27. (b) : Solid XeF6 exists as XeF5+ and F–.
23. (d) : = 28. (d)
ps N
760 − ps 18 / 180 1 / 10 29. (b) : As volume is constant, DV = 0
= =
ps 178.2 / 18 9.9 W = –PDV = 0,
1 DU = q + W
⇒ 760 − ps = p ⇒ 760 × 99 − 99 ps = ps DU = 500 J + 0
99 s
⇒ 100ps = 760 × 99 \ DU = q = +500 J
760 × 99 30. (d) : A dilute solution of H2O2 can be concentrated
⇒ ps = = 752.4 torr
100 by heating (distillation) under reduced pressure.
qq

60 chemistry tODAy | march ‘16


Exam on
9th March

PRACTICE PAPER 2016


Time Allowed : 3 hours Maximum Marks : 70
GENERAL INSTRUCTIONS
(i) All questions are compulsory.
(ii) Q. no. 1 to 5 are very short answer questions and carry 1 mark each.
(iii) Q. no. 6 to 10 are short answer questions and carry 2 marks each.
(iv) Q. no. 11 to 22 are also short answer questions and carry 3 marks each.
(v) Q. no. 23 is a value based question and carries 4 marks.
(vi) Q. no. 24 to 26 are long answer questions and carry 5 marks each.
(vii) Use log tables if necessary, use of calculators is not allowed.

1. Why are powdered substances more effective Formulate the galvanic cell for their combination.
adsorbents than their crystalline forms? What will be the standard cell potential for it?
2. Arrange the following alkyl halides in the order of Calculate DrG° for the cell reaction.
increasing dipole moment. 8. (i) In the transition series, starting from lanthanum
CH3 F, CH3 Cl, CH3 Br, CH3 I (57La), the next element hafnium (72Hf) has an
3. Trimethylamine and n-propylamine have the same atomic number of 72. Why do we observe this
molecular weight but the former boils at lower jump in atomic number?
temperature than the latter. Give reason. (ii) Ce(IV) is a good analytical reagent. Why?

4. Why is Frenkel defect not found in pure alkali metal 9. Give reason for the following :
halides? (i) Ferric iodide is very unstable but ferric chloride
is stable.
5. Why outer octahedral complexes are called high
(ii) ClF3 molecule has a T-shaped structure and
spin complexes?
not a trigonal planar one.
6. 4% NaOH solution (mass/volume) and 6% urea
10. How can propan-2-one be converted into tert- butyl
solution (mass/volume) are equimolar but not
alcohol?
isotonic. Why?
OR
7. The E° values corresponding to the following two
reduction electrode processes are : What happens when
Cu+/Cu = + 0.52 V (i) ethyl alcohol reacts with red P and Br2?
Cu2+/Cu+ = + 0.16 V (ii) ethanol is heated with conc. H2SO4 at 443 K?

chemistry tODAy | March ‘16 61


11. (i) Explain why does conductivity of germanium central metal atom/ion and determine the magnetic
crystals increase on doping with gallium. moment value for the following :
(ii) Why does table salt, NaCl, sometimes appear [FeF6]3–, [Fe(H2O)6]2+, [Fe(CN)6]4–
yellow in colour? 18. Compound (A) with molecular formula C4H9Br
12. (i) Heptane and octane form ideal solution. At is treated with aqueous KOH solution. The rate of
373 K, the vapour pressure of the two liquid this reaction depends upon the concentration of
components are 105.2 kPa and 46.8 kPa the compound ‘A’ only. When another optically
respectively. What will be the vapour pressure active isomer ‘B’ of this compound was treated
of a mixture of 26.0 g of heptane and 35.0 g of with aqueous KOH solution, the rate of reaction
octane? was found to be dependent on concentration of
compound and KOH both.
(ii) Give an example of a material used for making
(i) Write down the structural formula of both
semipermeable membrane for carrying out
compounds ‘A’ and ‘B’.
reverse osmosis.
(ii) Out of these two compounds, which one will
13. Write the overall reaction that occurs during the be converted to the product with inverted
use of nickel-cadmium cell. Is it a primary or a configuration.
secondary cell? Mention its one merit over the lead
19. Accomplish the following conversions :
storage cell.
(i) Aniline to 2,4,6-tribromofluorobenzene
14. (i) What is meant by van’t Hoff factor? (ii) Benzamide to toluene
(ii) The osmotic pressure of a 0.0103 molar 20. (i) Mention the type of linkage responsible for the
solution of an electrolyte is found to be formation of the following :
0.70 atm at 27°C. Calculate the van’t Hoff (a) Primary structure of protein
factor. (R = 0.082 L atm K–1 mol–1) (b) Cross linkage of polypeptide chains
What conclusion do you draw about (c) a-helix formation
the molecular state of the solute in the (d) b-sheet structure
solution? (ii) What is meant by reducing sugars?
15. Explain the following : 21. Explain each of the following terms with one
(i) CO2 is a better reducing agent below 710 K whereas suitable example.
CO is a better reducing agent above 710 K. (i) A sweetening agent for diabetic patients
(ii) Silica is added to the sulphide ore of copper in (ii) Enzymes
the reverberatory furnace. (iii) Analgesics
(iii) Vapour phase refining method is used for the 22. (i) Write the name of the reagents and equations
purification of Ti. in the conversion of
OR (a) phenol to salicylaldehyde
(i) Indicate the principle behind the method used (b) anisole to p-methoxyacetophenone.
(ii) Ethers are soluble in water. Why?
for the refining of zinc.
(ii) How is cast iron different from pig iron? 23. Seema went to market to buy vegetables. The vendor
(iii) Which form of the iron is the purest form of put the vegetables in the polythene bag but Seema
commercial iron? refused to take polythene bag and told the vendor
to put the things in the cloth bag which she was
16. (i) What type of battery is mercury cell? Why is it
carrying with her.
more advantageous than dry cell?
(i) What values are shown by Seema?
(ii) Electrolysis of aqueous CuCl2 solution liberates
(ii) Why did Seema carry cloth bag with her
Cl2 at anode not O2. Why?
instead of taking polythene bag from vendor?
17. Using crystal field theory, draw energy level (iii) What are the bad effects of non-biodegradable
diagram, write electronic configuration of the polymers?

62 chemistry tODAy | March ‘16


24. Compound ‘A’ (C6H12O2) on reduction with LiAlH4 how long will it take for three-fourth of initial
yields two compounds ‘B’ and ‘C’. The compound quantity of HCO2H to decompose?
‘B’ on oxidation gives ‘D’ which on treatment with (Given : log 4 = 0.6021)
aqueous alkali and subsequent heating furnishes (ii) The decomposition of a compound is found
‘E’. The later on catalytic hydrogenation gives ‘C’. to follow a first order rate law. If it takes
The compound ‘D’ on further oxidation gives 15 minutes for 20 percent of original material
CH3COOH. Deduce the structures of A, B, C, D and E. to react, calculate
OR (a) the specific rate constant
(i) Give chemical tests to distinguish between the (b) the time at which 10 percent of the original
following pairs of compounds : material remains unreacted
(a) Propanoyl chloride and propanoic acid (c) the time it takes for the next 20 percent of
(b) Benzaldehyde and acetophenone the reactant left after the first 15 minutes.
(ii) How would you account for the following?
(a) Aldehydes are more reactive than ketones 26. (i) Why do noble gases form compounds with
towards nucleophiles. fluorine and oxygen only?
(b) The boiling points of aldehydes and (ii) Why HF is stored in wax coated glass bottles?
ketones are lower than the corresponding (iii) SF6 is not easily hydrolysed though
acids. thermodynamically it should be. Why?
(c) The aldehydes and ketones undergo a (iv) Structures of xenon fluorides cannot be
number of addition reactions. explained by valence bond approach. Explain?
25. (i) The graph for the reaction, (v) Draw the structure of H2SO5.
R P OR
is represented by (i) Explain the Ostwald’s process for the
[R]0 manufacture of nitric acid.
of reactant (R)

(ii) Write the balanced reactions when nitric acid


Concentration

reacts with
(a) I2 (b) C
(c) S8 (d) P4
Time (t) (iii) Give any two uses of HNO3.
(a) Predict the order of the reaction in this sOlutiOns
case. 1. Powdered substances have large surface area
(b) What does the slope of the graph represent? which increases the extent of adsorption than their
(ii) The following data were obtained during the
crystalline forms.
first order thermal decomposition of SO2Cl2 at
a constant volume : 2. Increasing order of dipole moment :
SO2Cl2(g)  → SO2(g) + Cl2(g) CH3 I < CH3 Br < CH3 F < CH3 Cl
Experiment Time/s Total 3. n-Propylamine has two H-atoms on N-atom and
pressure/atm hence, undergoes intermolecular H-bonding
1 0 0.4 whereas trimethylamine being a 3° amine does not
undergo H-bonding.
2 100 0.7
Calculate the rate constant. 4. Frenkel defect is not found in pure alkali metal
[Given : log 4 = 0.6021, log 2 = 0.3010] halides because alkali metal ions cannot fit into the
OR interstitial sites.
(i) The thermal decomposition of HCO2H is a 5. Pairing does not occur in outer octahedral
first order reaction with a rate constant of complexes, hence, they have unpaired electrons
2.4 × 10–3 s–1 at a certain temperature. Calculate and show large values of magnetic moments.

chemistry tODAy | March ‘16 63


6. Both the solutions, 4% NaOH (W/V) and 6% urea O
(W/V) have same concentration (1 M) but these are Dry ether
CH3 C CH3 + CH3MgBr
not isotonic because NaOH undergoes dissociation Propanone Methyl magnesium
in solution. Therefore, number of particles in NaOH bromide
solution is more than that in urea solution. OH OMgBr
+ – HO H +/H2O
7. At cathode : Cu + e 
→ Cu E° = + 0.52 V Mg + CH3 C CH3 CH3 C CH3
+
→ Cu2+ + e–
At anode : Cu  E° = + 0.16 V Br
CH3 CH3
Cell reaction : 2Cu+  → Cu + Cu2+ tert-butyl alcohol
Cell representation is OR
Cu+ | Cu2+ || Cu+ | Cu
E °cell = E °cathode − E °anode = 0.52 – 0.16 = 0.36 V (i) CH3CH2OH CH3CH2Br + H3PO3
Ethyl alcohol Ethyl bromide
DrG° = – nE°F = – 1 × 0.36 × 96500
(ii) C2H5OH CH2 CH2
= –34740 J mol–1 Ethanol Ethene
8. (i) This is because after 57La, filling of 4f-orbital 11. (i) When germanium is doped with gallium,
starts which is completed at atomic number 71. some of the positions of lattice of germanium
These 14 elements therefore, belong to f-block are occupied by gallium. Valence electrons in
and are placed separately at the bottom of the germanium are four while gallium has only
periodic table. three valence electrons. The vacancy of fourth
(ii) The E° value for Ce4+/Ce3+ is 1.74 V which valence electron of germanium creates an
suggests that it can oxidise water however, the electron hole or electron vacancy. Under the
reaction rate is very slow and hence, Ce (IV) is influence of electric field the electron starts
a good analytical reagent. moving towards positively charged plates
9. (i) Iodide ion (I–) is a strong reducing agent and through the holes and conduct electricity.
reduces Fe3+ ion to Fe2+ ion. Therefore, ferric (ii) Yellow colour in sodium chloride is due to
iodide does not exist. metal excess defect due to which unpaired
electrons occupy anionic sites. These sites are
Chloride ion (Cl–) being a weak reducing agent
called F-centres. These electrons absorb energy
cannot reduce Fe3+ ion hence, ferric chloride is
from the visible region for the excitation which
quite stable.
makes crystal appear yellow.
(ii) In ClF3, central atom Cl has three bond pairs
and two lone pairs. According to VSEPR theory, 12. (i) Molar mass of heptane (C7H16) = 100 g mol–1
the two lone pairs will occupy the equatorial Molar mass of octane (C8H18) = 114 g mol–1
positions to minimise lp – lp and lp – bp 26.0 g
Number of moles of heptane =
repulsions. In addition, the axial fluorine atoms 100 g mol −1
will be bent towards the equatorial fluorine in = 0.26 mol
order to minimise the lp –lp repulsions. That is 35.0 g
why ClF3 has a bent T-shaped structure. No. of moles of octane = = 0.31 mol
114 g mol −1
F 0.26
x(heptane) = = 0.456
0.26 + 0.31
:

Cl F
x(octane) = 1– 0.456 = 0.544
:

p(heptane) = 0.456 × 105.2 kPa = 47.97 kPa


F
p(octane) = 0.544 × 46.8 kPa = 25.46 kPa
10. can be converted into tert-butyl PTotal = 47.97 + 25.46 = 73.43 kPa
(ii) Cellulose acetate is used for making
alcohol by its reaction with Grignard’s reagent semipermeable membrane for carrying out
(CH3MgBr) as shown : reverse osmosis.

64 chemistry tODAy | March ‘16


13. Nickel-cadmium batteries are rechargeable storage OR
batteries. It has anode cadmium metal and a metal (i) Zinc is refined by electrolytic refining.
grid containing nickel (IV) oxide as cathode In this method, the impure metal is made
immersed in KOH soution. to act as anode. A strip of the same metal in
Reactions during discharging, pure form is used as cathode. They are put in
At anode : Cd(s) + 2OH–(aq) → Cd(OH)2(s) + 2e– a suitable electrolytic bath containing soluble
At cathode : salt of the same metal. When electric current

NiO2(s) + 2H2O(l) + 2e– → Ni(OH)2(s) + 2OH(aq) is passed, Zn2+ ions from the electrolyte are
_________________________________________________________
Cd (s) + NiO2(s) + 2H2O(l) → Cd(OH)2(s) + Ni(OH)2(s)
deposited at the cathode and an equivalent
________________________________________
amount of metal goes into the electrolyte as
When charging takes place, reactions are reversed.
Zn2+ ions.
It is a secondary cell. It has longer life than the lead
At anode : Zn Zn2+ + 2e–
storage cell but is more expensive to manufacture.
At cathode : Zn2+ + 2e– Zn
Since reactant and product are metals or solids, emf
(ii) The iron obtained from Blast furnace contains
remains constant throughout in its operation. about 4% carbon and many impurities in
14. (i) van’t Hoff factor is the ratio of the normal smaller amount (e.g., S, P, Si, Mn). This is
molecular mass to the observed molecular known as pig iron and cast into variety of
mass or the ratio of the observed colligative shapes.
property to the normal colligative property. Cast iron is different from pig iron and is made
by melting pig iron with scrap iron and coke
(ii) p = iCRT using hot air blast. It has slightly lower carbon
or, 0.70 = i × 0.0103 × 0.082 × (27 + 273) content (about 3%) and is extremely hard and
0.70 brittle.
or, i = = 2.76
0.0103 × 0.082 × 300 (iii) Wrought iron is the purest form of commercial
Since i >1, solute molecules are dissociated in iron. It contains 0.2–0.5% carbon besides traces
the solution. of P and Si in the form of slag.
15. (i) According to Ellingham diagram, at 16. (i) Mercury cell is a primary battery hence, it can
temperature below 710 K, be used only once and cannot be recharged
DG°(C, CO ) < DG°(C, CO) hence CO2 is better after discharging.
2
reducing agent. Advantage : The cell potential remains constant
At temperature above 710 K, during its life time. Hence, it is useful for
DG°(C, CO2) > DG°(C, CO) hence CO is better devices requiring constant current e.g., hearing
reducing agent. aids and watches.
(ii) Copper pyrites contain iron sulphide in addition (ii) During electrolysis of aqueous CuCl2 following
to copper sulphide. In the reverberatory reactions take place :
furnace, copper ore is roasted to give oxides. CuCl2 Cu2+ + 2Cl–
FeO is removed by adding silica from the matte At cathode, Cu2+ + 2e– Cu(s)
containing Cu2S and some unchanged FeS. At anode, two reactions are possible
2FeS + 3O2 2FeO + 2SO2 2Cl– Cl2(g) + 2e–; E° = 1.36 V
FeO + SiO2 FeSiO3 1
H2O 2 H + + O2 + 2e − ; E° = 1.23 V
(Slag) 2
(iii) Ti reacts with iodine to form TiI4 which is At anode the reaction with lower value of
volatile and decomposes to give Ti at high E° should take place and thus, water should
temperature to give extra pure titanium. get oxidised to give O2. But on account of
Ti + 2I2 TiI4, TiI4 Ti + 2I2 overpotential of oxygen, chlorine is produced
Impure Pure at anode.

chemistry tODAy | March ‘16 65


17. [FeF6]3– : NH2 NH2
Fe3+ = 3d5 Br2/Water Br Br (i) NaNO2 / HCl
19. (i)
273 - 278 K
Aniline (ii) HBF4
Br
F N2+BF4–
Br Br Br Br

Number of unpaired electrons = 5
Magnetic moment = 5(5 + 2) = 5.92 B.M. Br Br
2,4,6-Tribromofluorobenzene
[Fe(H2O)6]2+ :
Fe2+ = 3d6
(ii)

Number of unpaired electrons = 4


Magnetic moment = 4(4 + 2) = 4.9 B.M. 20. (i)
[Fe(CN)6]4– : Biomolecule Type of linkage
Fe2+ = 3d6 (a) Primary structure Peptide bond (linkage)
of protein
(b) Cross linkage of Hydrogen bond, disulphide
polypeptide chain linkage, electrostatic force
of attraction
Diamagnetic and its magnetic moment is zero.
(c) a-helix formation Hydrogen bond
CH3 CH3
(d) b-sheet structure Intermolecular hydrogen
aq. KOH
18. (i) CH C CH3 CH3 C CH3 bond.
3
Br OH (ii) Carbohydrates which reduce Tollens’ reagent
(A) 2-Methylpropan-2-ol are reducing sugars. All monosaccharides,
2-Bromo-2-methylpropane aldoses or ketoses are reducing sugars.
21. (i) Artificial sweetening agents are chemical
substances which are sweet in taste but do
not add calories to our body. For example,
aspartame, it is 150 times sweeter than
sucrose.
(ii) Compound (B) will be converted to product (ii) Enzymes are bio-catalysts which accelerate
with inverted configuration as it undergoes various cellular reactions without themselves
undergoing any apparent change during the
SN2 nucleophilic substitution in which the
course of action. Enzymes are highly specific
nucleophile attaches itself on the side opposite in their action on substrate. Almost all the
to the one where the halogen atom is present. enzymes are globular proteins. For example,
Compound (A) being a tertiary halide, urease catalyses decomposition of urea to CO2
undergoes SN1 substitution which is and NH3.
(iii) Analgesics are chemical compounds which
accompanied by racemisation.
are used for relieving pain. Analgesics relieve

66 chemistry tODAy | March ‘16


pain by acting on central nervous system environmental pollution while cloth bags are
or on peripheral pain mechanism, without biodegradable and can be reuse again.
significantly affecting consciousness. There are (iii) Non-biodegradable polymers are quite resistant
two types of analgesics : to the environmental degradation processes
Narcotics – Morphine, codeine, heroine and cause accumulation of solid polymeric
Non-narcotics – Aspirin, ibuprofen, etc waste materials. These waste materials remain
22. (i) (a) Reagents : Chloroform and alcoholic undegraded for quite a long time and cause
alkali. acute environmental problems.
OH OH O
CHCl3 + 3KOH CHO
(Alcoholic) 24. CH3 C O CH2 CH2 CH2 CH3 LiAlH4
+ 3KCl + 2H2O (A)
Butyl ethanoate
Phenol Salicylaldehyde
CH3 CH2 OH + CH3CH2CH2CH2 OH
(b) Reagents : Acetyl chloride and Lewis acid (B) (C)
catalyst. Ethanol Butan-1-ol
OCH3 [O] [O]
CH3CH2OH CH3CHO CH3COOH
AlCl3 (B) (D) Ethanoic acid
+ CH3COCl Ethanal
Friedel–Craft reaction
Anisole
OH
OCH3 OCH3 NaOH 
CH3CHO CH3 C CH2 CHO
COCH3 (D)
+ H2/Ni
H
CH3 CH CH CHO
o-Methoxyacetophenone (E)
COCH3 CH3 CH2 CH2 CH2OH
p-Methoxyacetophenone (C)
(ii) The oxygen present in ether forms H–bond O
with water due to which they are soluble in Hence (A) CH3 C O CH2 CH2 CH2 CH3
water.
(B) CH3CH2OH
R O H O
(C) CH3CH2CH2CH2OH
R H
(D) CH3CHO
23. (i) Concern, aware and alert for environmental
pollution are the values displayed by Seema. (E) CH3 CH CH CHO
(ii) Polythene is non-biodegradable which causes OR
(i) (a) Propanoic acid reacts with aq. NaHCO3
with the evolution of CO2 gas while
propanoyl chloride does not react with
NaHCO3.
CH3CH2COOH + NaHCO3
CH3CH2COONa + H2O + CO2↑
(b) Iodoform test : Warm each compound
with iodine and sodium hydroxide
solution on a water bath.
Acetophenone (C6H5COCH3) gives yellow
precipitate of iodoform, benzaldehyde
does not give this test.

chemistry tODAy | March ‘16 67


(ii) (a) Ketones are less reactive than aldehydes OR
towards nucleophilic addition reactions (i) For a first order reaction,
because the two electron releasing alkyl 2.303 [R]0
groups decrease the magnitude of positive t= log
k [R]t
charge on carbonyl carbon and make it
less susceptible to nucleophilic attack. Given k = 2.4 × 10–3 s–1
R R [R]0
C O C O [R]t = ,t =?
R 4
H
Ketone Aldehyde Substituting these values in the equation, we
Also, the two bulkier alkyl groups hinder get
the approach of the nucleophile to the 2.303 [R]0
t= log
carbonyl carbon. This is called steric 2.4 × 10−3 s −1 [R]t
factor. 2.303 2.303
(b) The boiling points of aldehydes and t= log 4 = × 0.6021 s
−3 −1
2.4 × 10 s 2.4 × 10−3
ketones are lower than the corresponding
t = 577.7 s ≈ 578 s
acids and alcohols due to absence of
(ii) (a) For a first order reaction,
intermolecular hydrogen bonding.
2.303 [R]0
(c) Aldehydes and ketones undergo a number k= log
of addition reactions as both possess the t [R]t
carbonyl functional group which reacts Given t = 15 min, [R]t = 0.8[R]0
with a number of nucleophiles such 2.303 [R]0
or, k = log
as HCN, NaHSO3, alcohols, ammonia 15 0.8 [R]0
derivatives and Grignard reagents. 2.303 10
or, k = log ...(i)
25. (i) (a) The reaction is of zero order. 15 8
(b) Slope of the straight line graph gives rate or, k = 0.015 min–1
constant. (b) When [R]t = 0.1 [R]0, t = ?
d[R] 2.303 [R]0 2.303
−k = k= log = log 10
dt t1 0.1 [R]0 t1
(ii) The given reaction is
2.303
SO2Cl2(g) SO2(g) + Cl2(g) or, 0.015 min −1 =
t1
At t = 0, 0.4 atm 0 0
2.303
At time t, (0.4 – x) atm x atm x atm or, t1 =
Total pressure at time t will be 0.015 min −1
PTotal = (0.4 – x) + x + x = 0.4 + x t1 = 153.53 min
x = (PTotal – 0.4) \ After 153.53 min, 10% of the original
Pressure of SO2Cl2 at time t will be material remains unreacted.
pSO2Cl2 = 0.4 – x = 0.4 – (PTotal – 0.4) (c) Also,
= 0.8 – PTotal 2.303 0.8 [R]0 2.303 10
k= log = log
At time (t = 100 s), PTotal = 0.7 atm t2 0.64 [R]0 t2 8
\ pSO2Cl2 = 0.8 – 0.7 = 0.1 atm ...(ii)
According to first order kinetic equation, From (i) and (ii), we get
 pSO2Cl 2 (initial)  2.303 10 2.303 10
2.303 log = log
k= log   15 8 t2 8
t  pSO2Cl 2 (after reaction)  \ t2 = 15 min
2.303  0.4 
= log   = 1.38 × 10 −2 s −1 26. (i) Fluorine and oxygen are the most
100  0.1  electronegative elements hence, they are very

68 chemistry tODAy | March ‘16


chemistry tODAy | March ‘16 69
reactive and form compounds with noble OR
gases, particulary with xenon. (i) This method is based on catalytic oxidation of
(ii) HF does not attack wax but attacks sodium NH3 by atmospheric oxygen.
silicate which is the main constituent of glass. Pt
4 NH3( g ) + 5 O2( g ) 
→ 4 NO( g ) + 6 H2O( g )
As a result, the glass bottles are slowly corroded 500 K, 9 bar

or eaten up. Nitric oxide thus formed combines with


Na2SiO3 + 6HF Na2SiF6 + 3H2O oxygen to give NO2.
(iii) In SF6 molecule, sulphur is surrounded by six 2NO(g) + O2(g) 2NO2(g)
fluorine atoms which protect sulphur atom Nitrogen dioxide so formed dissolves in water
from attack by reagents to such an extent that to give nitric acid HNO3.
even thermodynamically most favourable
3NO2(g) + H2O(l) 2HNO3(aq) + NO(g)
reactions like hydrolysis do not occur. So, H2O
cannot attack SF6 easily. (ii) (a) I2 + 10HNO3 2HIO3 + 10NO2 + 4H2O
(iv) According to the valence bond approach, (b) C + 4HNO3 CO2 + 2H2O + 4NO2
orbitals containing unpaired electrons only (c) S8 + 48HNO3(conc.) 8H2SO4 + 48NO2
take part in covalent bond formation. Xenon + 16H2O
has no unpaired electrons. Hence, structure
(d) P4 + 20HNO3(conc.) 4H3PO4 + 20NO2
of its fluorides cannot be explained by valence
+ 4H2O
bond approach.
(iii) (a) Nitric acid is used to manufacture
(v) O ammonium nitrate for fertilisers.
S (b) It is used for the preparation of
O OHO O H trinitrotoluene and other organic nitro
Peroxomonosulphuric acid or Caro’s acid compounds.
qq

70 chemistry tODAy | March ‘16


OLYMPIAD
PROBLEMS
1. The line spectra of two elements are not identical but enters into reaction with phenyl hydrazine.
because Ozonolysis of (A) gives acetaldehyde and C3H4O2
(a) the elements do not have the same number of which readily loses CO to form acetaldehyde. A is
neutrons (a) CH3CH CHCOCH3
(b) they have different mass numbers (b) CH3CH CHCH2CHO
(c) their outermost electrons are at different energy (c) CH2 CHCH2COCH3
levels (d)
(d) they have different valencies.
2. Identify Y in the given reaction. 6. The enthalpy change involved in the oxidation of
OH O glucose is –2880 kJ mol–1. 25% of this energy is
H +/ (i) O3 available for muscular work. If 100 kJ of muscular
(X) (Y) NaOH
(ii) Zn/CH3COOH work is needed to walk one km. What is the
H3C CH OH maximum distance that a person will be able to
walk after eating 120 g of glucose?
(a) (a) 4.80 km (b) 5.2 km
(b) CH3COCH2CH2CH2CHO (c) 100 km (d) 30 km
(c) CH3COCH2CH2CH2CH2⋅CHO 7. Which of the following diagrams shows correct
CH2CH2OH change in the polarity of bond?
Decrease
(d) O H Cl H
(a) Decrease Increase
3. One litre of oxygen at NTP weighs 1.46 g. How many Decrease
litres of oxygen are needed for the combustion of S H F H
1 Decrease
21.0 g of Mg whose equivalent weight is mole? O H Cl H
2 (b) Decrease
(a) 2.5 L (b) 9.59 L Increase
(c) 8.42 L (d) 32 L Decrease
S H F H
4. How does H2O2 differ from O3 in its chemical Increase
O H Cl H
action?
(a) In oxidising PbS to PbSO4 (c) Decrease Increase
Decrease
(b) In liberating I2 from KI S H F H
(c) In decolorising acidified KMnO4 Decrease
O H Cl H
(d) In oxidising K4[Fe(CN)6] to K3[Fe(CN)6]
(d) Increase Increase
5. An organic compound (A) C5H8O adds Br2 to give Decrease
C5H8Br2O. If does not react with Tollen’s reagent S H F H

chemistry tODAy | mARCH ‘16 71


8. Which one of the following is most stable? 13. Which of the following statements is not correct?
Cl (a) (s + py) produces sp hybrid orbitals which are
lying in the yz plane.
(a) (b) (b) (s + py) produces sp hybrid orbitals which are
+
lying in the xz plane.
:OH (c) (s + px + pz) produces sp2 hybrid orbitals which
:

Cl Cl are lying in the xz plane.


+ (d) None of these
(c) (d) +
14. Which of the following compounds is an amine?
OH OH (a) (b) OH
9. A sample of MnSO4⋅4H2O is strongly heated in air. N N
The residue is Mn3O4.
I. The residue is dissolved in 100 mL of 0.1 N N N
(c) (d) O
FeSO4 containing dilute H2SO4.
II. The solution reacts completely with 50 mL of H H
KMnO4 solution. 15. The rate constant for two parallel reactions
III. 25 mL of KMnO4 solution used in step (II) were found to be 1.0 × 10–2 dm3 mol–1 s–1 and
requires 30 mL of 0.1 N FeSO4 solution for the 3.0 × 10–2 dm3 mol–1 s–1. If the corresponding
complete reaction. energies of activation of the parallel reactions are
Find the amount of MnSO4⋅4H2O in the sample. 60.0 kJ mol–1 and 70.0 kJ mol–1 respectively, what is
(Mn =55, Fe = 56, S = 32) the apparent overall energy of activation?
(a) 1.4210 g (b) 1.50 g (a) 130.0 kJ mol–1 (b) 67.5 kJ mol–1
–1
(c) 1.338 g (d) 2.2 g (c) 100.0 kJ mol (d) 65.0 kJ mol–1
10. A colourless solid (X) on heating evolved CO2 and 16. Consider the following statements :
also gave a white residue, soluble in water. Residue (i) IUPAC name of K2[OsCl5N] is Potassium
also gave CO2 when treated with dilute acid. (X) is pentachloronitridoosmate (VI).
(a) Na2CO3 (b) CaCO3 (ii) [Cr(H2O)6][Fe(CN)6] contain four unpaired
(c) Ca(HCO3)2 (d) NaHCO3 electrons.
(iii) [Fe(acac)3] is high spin organometallic
11. A is complex.
(iv) [Ni(H2O)6]2+ has 6 electrons in t2g and
CH3
2 electrons in eg orbital.
(a) OH (b)
Give initial ‘T’ for true statement and ‘F’ for false
CH3 statement.
OH (a) TTTT (b) FTFT (c) TTFF (d) FFTT
(c) OH (d)
D D 17. An organic compound CxH2yOy was burnt
12. Barium titanate has a pyrolusite structure (a cubic with twice the oxygen needed for complete
lattice), with barium ions occupying the corners combustion to produce CO2 and H2O.
of the unit cell, oxide ions the face centres and The hot gases when cooled at 0°C and
titanium ions the centres. Assuming that Ti4+ ions 1 atm pressure measured 2.24 litre. The water
occupy the holes of the BaO lattice, what type of collected during cooling was 0.9 g. The vapour
hole and what fraction of such holes do these ions pressure of pure water at 20°C is 17.5 mm of Hg
occupy? and it reduces by 0.104 mm when 50 g of organic
(a) 25% of the octahedral holes compound is dissolved in 1000 g of water. The
(b) 75% of the tetrahedral holes molecular formula of the organic compound is
(c) 50% of the tetrahederal holes (a) C6H12O6 (b) C5H10O5
(d) 100% of the octahedral holes (c) C2H4O2 (d) C8H16O8

72 chemistry tODAy | mARCH ‘16


18. For 1 mol of an ideal gas, V1 > V2 > V3 in Fig. (I), Lu3+
T1 > T2 > T3 in Fig. (II), P1 > P2 > P3 in Fig. (III),

Ionic size/pm
and T1 > T2 > T3 in Fig. (IV), then which curves are
correct. (a)
V1 T1
V2 T2 La3+
V3 T3
P P
I. II. Atomic number
Lu3+

Ionic size/pm
T 1/V
P1 (b)
P2
P3
P
log P

III. IV. La3+


T1
T2 Atomic number
T3
T log V La3+
(a) I, II (b) I, II, III
(c) II, IV (d) I, III, IV Ionic size/pm
(c)
19. A jeweller is selling 22-carat gold articles with 95%
purity, it is approximately
(a) exact (b) 3.5% higher Lu3+
Atomic number
(c) 3.5% lower (d) 5% lower.
20. Consider the following reaction : La3+ Lu3+
Ionic size/pm

Br2
FeBr3 Product;
(d)
The product is
(a) Br
Atomic number
(b) 23. The major product of the following reaction is
Br
(c)
Br
(d)
Me SPh
Br
F
21. A piece of charcoal from the ruins of a settlement
(a) (b)
in Japan was found to have 14C/12C ratio that was
0.617 times that found in living organisms. How old NO2
is this piece of charcoal? (t1/2 for 14C is 5770 years)
Me Br Me SPh
(a) 4400 years (b) 2123 years
(c) 1529 years (d) 4023 years SPh SPh
(c) (d)
22. Which of the following graphs shows correct trend
in the size of +3 ions of lanthanides? NO2 NO2

chemistry tODAy | mARCH ‘16 73


24. A 100 watt, 110 volt incandescent lamp is connected 29. In the following reaction sequence, the correct
in series with an electrolytic cell containing cadmium structures of E, F and G are :
sulphate solution. What weight of cadmium will
be deposited by the current flowing for 10 hours?
[Atomic weight of Cd = 112.4]
(a) 20.02 g (b) 35.52 g O O
(c) 19.06 g (d) 11.11 g (a) E = F= – + G = CHI3
Ph * CH3 Ph * ONa
25. In the following statements which combination of O O
true (T) and false (F) options is correct? (b) E = *
F= – + G = CHI3
Ph CH3 Ph ONa
I. Ionic mobility is the highest for I– in water as
O O
compared to other halides. (c) E = F=
*
G = CHI3
* – +
II. Stability order is Cl– > Br– > I– Ph CH3 Ph ONa
III. Reactivity order is F < Cl > Br > I O O *
IV. Oxidizing power order is F2 < Cl2 < Br2 < I2. (d) E = F= – + G = CH3I
Ph *
CH3 Ph ONa
(a) TFTF (b) TTFF
(c) TFFT (d) FTFT 30. A mixture of formic acid and oxalic acid is heated
with concentrated H2SO4. The gas produced is
26. In the compound given below : collected and on its treatment with KOH solution
+ +
H3N NH3 the volume of the gas decreased by one-sixth.
(Y) (Z) Calculate the molar ratio of the two acids in the
COOH original mixture.
(X) (a) 2 : 1 (b) 4 : 1
The correct order of acidic nature is (c) 3 : 4 (d) 3 : 2
(a) Z > X > Y (b) X > Y > Z
(c) X > Z > Y (d) Y > X > Z ANSWER Keys
27. When KI (excess) is added to 1. (c) 2. (c) 3. (b) 4. (c) 5. (a)
6. (a) 7. (d) 8. (b) 9. (c) 10. (d)
I : CuSO4 II : HgCl2 III : Pb(NO3)2
11. (b) 12. (a) 13. (b) 14. (c) 15. (b)
(a) a white ppt. of CuI in I, an orange ppt. of HgI2
16. (a) 17. (b) 18. (c) 19. (b) 20. (c)
in II and a yellow ppt. of PbI2 in III
21. (d) 22. (c) 23. (a) 24. (c) 25. (b)
(b) a white ppt. of CuI in I, an orange ppt. dissolving 26. (b) 27. (b) 28. (b) 29. (c) 30. (b)
HgI42– in II and a yellow ppt. of PbI2 in III

(c) a white ppt. of CuI, HgI2 and PbI2 in each case
(d) none of these.
28. A solution containing NH4Cl and NH4OH has
[OH–] = 10–6 mol L–1, which of the following
hydroxides would be precipitated when this solution
is added in equal volume to a solution containing
0.1 M of metal ions?
(a) Mg(OH)2, (Ksp = 3 × 10–11)
(b) Fe(OH)2, (Ksp = 8 × 10–16)
(c) Cd(OH)2, (Ksp = 8 × 10–6)
(d) AgOH (Ksp = 5 × 10–3)

74 chemistry tODAy | mARCH ‘16


Exam on 1st May

AIPMT 2016 Model TesT PaPer


1. From the stability constants (hypothetical values) the equivalent weight of the metal is 20, the volume
given below, predict which is the strongest ligand? of alkali that would be consumed is
(a) Cu2+ + 4NH3  [Cu(NH3)4]2+; (K = 4.5 × 1011) (a) 50 mL (b) 25 mL
(b) Cu2+ + 4CN–  [Cu(CN)4]2–; (K = 2.0 × 1027) (c) 75 mL (d) 100 mL
(c) Cu2++ 2en  [Cu(en)2]2+ ; (K = 3.0 × 1015) 7. A polymer formed by coordination polymerisation is
(d) Cu2++ 4H2O  [Cu(H2O)4]2+; (K = 9.5 × 108) (a) low density polythene
2. Which of the following molecules has the maximum (b) high density polythene
number of stereoisomers? (c) nylon-6
(a) (b) (d) dacron.
8. A compound which does not give a positive
Lassaigne’s test for nitrogen is
(a) urea (b) hydrazine
(c) azobenzene (d) phenyl hydrazine.
(c) H3C CH3 (d)
Br 9. The correct order of increasing ionic character?
Br
(a) BeCl2 < MgCl2 < CaCl2 < BaCl2
H H (b) BeCl2 < MgCl2 < BaCl2 < CaCl2
3. Which one of the following oxides is expected to (c) BeCl2 < BaCl2 < MgCl2 < CaCl2
exhibit paramagnetic behaviour? (d) BaCl2 < CaCl2 < MgCl2 < BeCl2
(a) CO2 (b) SiO2 10. Which of the following metal oxides is antiferromagnetic
(c) SO2 (d) ClO2 in nature?
4. Which of the following reagents can be used to (a) MnO2 (b) TiO2 (c) NO2 (d) CrO2
convert benzenediazonium chloride into benzene? 11. In context with the transition elements, which of
(a) CH3OH (b) H3PO2 the following statements is incorrect?
(c) Br2 – H2O (d) LiAlH4 (a) In addition to the normal oxidation states,
5. Following are the isomers of molecular formula, the zero oxidation state is also shown by these
C5H12. elements in complexes.
(b) In the highest oxidation states, the transition
metals show basic character and form cationic
Decreasing order of their boiling points is complexes.
(a) I < II < III (b) I > II > III (c) In the highest oxidation states of the first five
(c) II > I > III (d) III > I > II transition elements (Sc to Mn), all the 4s and 3d
6. 2.5 g of the carbonate of a metal was treated with electrons are used for bonding.
100 mL of 1 N H2SO4. After the completion of the (d) Once the d5 configuration is exceeded, the
reaction, the solution was boiled off to expel CO2 tendency to involve all the 3d electrons in
and was then titrated against 1 N NaOH solution. If bonding decreases.

chemistry tODAy | March ‘16 75


12. Which of the following statements is not correct? 18. The coordination number of a central metal atom
(a) The efficiency of a solid catalyst depends upon in a complex is determined by
its surface area. (a) the number of ligands around a metal ion
(b) Catalyst operates by providing alternate path bonded by sigma bonds
for the reaction that involves a lower energy of (b) the number of ligands around a metal ion
activation. bonded by pi-bonds
(c) the number of ligands around a metal ion
(c) Catalyst lowers the energy of activation of the bonded by sigma and pi-bonds both
forward reaction only. (d) the number of only anionic ligands bonded to
(d) Catalyst does not affect the overall enthalpy the metal ion.
change of the reaction.
19. For carbocations,
13. There are several criteria of purity of organic
compounds. Which is considered to be the best?
(a) Melting point
(b) Mixed melting point Correct order of stability is
(c) Colour (a) A > B > C (b) C > B > A
(d) Microscopic examination (c) B > A > C (d) C > A > B
14. Predict the product C obtained in the following
reaction of 1-butyne. 20. Zn gives H2 gas with H2SO4 and HCl but not with
HNO3 because
(a) Zn acts as an oxidising agent when reacted with
HNO3
(a) (b) HNO3 is weaker acid than H2SO4 and HCl
(c) in electrochemical series Zn is above hydrogen
(d) NO3– ion is reduced in preference to hydronium ion.
(b) 21. Calculate the energy of first stationary state of Li2+
if ionisation energy of He+ is 19.6 × 10–18 J atom–1.
(c) (a) 176.4 × 10–18 J atom–1
(b) 4.9 × 10–18 J atom–1
(d) (c) 8.7 × 10–18 J atom–1
(d) 44.1 × 10–18 J atom–1

15. When [Zn2+] = [Cu2+] = 1, the electrical potential 22. The dipole moment of o, p and m-dichlorobenzene
of Daniell cell is 1.1 V. However, will be in the order
(a) when Eext < 1.1 V, current flows from Zn to Cu (a) o > p > m (b) p > o > m
(b) when Eext = 1.1 V, current flows from Cu to Zn (c) m > o > p (d) o > m > p
(c) when Eext > 1.1 V, current flows from Zn to Cu 23. Fluorine is not tested by Beilstein’s test because
(d) when Eext < 1.1 V, electrons flow from Cu to Zn. (a) it does not react with copper
16. In which of the following the hydration energy is (b) copper fluoride is not volatile
higher than the lattice energy? (c) F2 is evolved as a gas
(a) MgSO4 (b) RaSO4 (d) none of these.
(c) SrSO4 (d) BaSO4
24. Which of the following is most basic?
17. Kc for A + B 
 
 
 C + D is 10 at 25°C. If a container (a) Ce(OH)3 (b) Lu(OH)3
contains 1, 2, 3 and 4 mol per litre of A, B, C and D
(c) Yb(OH)3 (d) Tb(OH)3
respectively at 25°C, then
(a) forward reaction should be favoured 25.
(b) backward reaction should be favoured
(c) the reaction should be at equilibrium
(d) none of these. The chemical formulae of A, B and C are

76 chemistry tODAy | March ‘16


A B C (a)
(a) Ca(OH)2 NaOH CaCO3 (b)
(b) NaOH Ca(OH)2 CaCO3
(c)
(c) NaOH CaO CaCO3
(d)
(d) CaO Ca(OH)2 NaOH
26. Which of the following is true? 34. Which of the following acids does not exhibit
(a) tert-Butoxide is a stronger base as well as optical isomerism?
stronger nucleophile than ethoxide. (a) Maleic acid (b) -amino acids
(b) tert-Butoxide is a weaker base but stronger (c) Lactic acid (d) Tartaric acid
nucleophile than ethoxide.
(c) tert-Butoxide is a stronger base, but weaker
nucleophile than ethoxide. 35. Given :
(d) tert-Butoxide and ethoxide are equally strong
bases as well as strong nucleophiles. The products P and Q are
27. Which one of the following information can be P Q
obtained on the basis of Le-Chatelier's principle? (a) p-bromonitrobenzene p-bromoaniline
(a) Dissociation constant of a weak acid. (b) o-bromonitrobenzene o-bromoaniline
(b) Entropy change in a reaction. (c) o,p-dibromonitrobenzene o,p-dibromoaniline
(c) Equilibrium constant of a chemical reaction. (d) m-bromonitrobenzene m-bromoaniline
(d) None of these. 36. The preparation of ammonia by Haber’s process is
an exothermic reaction. If the precipitation follows
28. The compound is used as the following temperature-pressure relationship for
its % yield, then for temperatures T1, T2 and T3 the
correct option is
(a) antiseptic (b) antibiotic
(c) analgesic (d) pesticide.
29. The average osmotic pressure of human blood is
7.8 bar at 27°C. What is the concentration of an
aqueous NaCl solution that could be used in the
blood stream?
(a) 0.16 mol/litre (b) 0.32 mol/litre (a) T3 > T2 > T1
(c) 0.60 mol/litre (d) 0.45 mol/litre
(b) T1 > T2 > T3
30. Ethylene oxide when treated with Grignard reagent (c) T1 = T2 = T3
yields (d) nothing could be predicted.
(a) primary alcohol (b) secondary alcohol
37. The prefixes syn and anti are used to denote
(c) tertiary alcohol (d) cyclopropyl alcohol.
(a) structural isomers
31. The third line of the Balmer series, in the emission (b) conformational isomers
spectrum of the hydrogen atom, is due to the (c) geometrical isomers
transition from the
(d) optical isomers.
(a) fourth Bohr orbit to the first Bohr orbit
(b) fifth Bohr orbit to the second Bohr orbit 38. Half-life period of a first order reaction is 1386 s.
(c) sixth Bohr orbit to the third Bohr orbit The specific rate constant of the reaction is
(d) seventh Bohr orbit to the third Bohr orbit. (a) 0.5 × 10–2 s–1 (b) 0.5 × 10–3 s–1
–2 –1
(c) 5.0 × 10 s (d) 5.0 × 10–3 s–1
32. Hybridisation in are respectively
39. The bond order of a molecule is given by
(a) sp2, sp2, sp3 (b) sp , sp , sp3
2 3
(a) the difference between the number of electrons
(c) sp3, sp3, sp2 (d) sp3, sp2, sp2 in bonding and antibonding orbitals
33. Which one of the following pairs is not correctly (b) total number of electrons in bonding and
matched? antibonding orbitals

chemistry tODAy | March ‘16 77


(c) twice the difference between the number of sOlutiOns
electrons in bonding and antibonding orbitals 1. (b) : Higher the stability constant of ligand, lesser is
(d) half the difference between number of electrons the dissociation of complex and more is its stability.
in bonding and antibonding orbitals. Hence, stronger is the ligand.
40. The order of increasing freezing points for the 2. (d) : Compound (d) has two dissimilar chiral
solutions of following solutes : carbon atoms hence has maximum stereoisomers.
C2H5OH, Ba3(PO4)2, Na2SO4, KCl and Li3PO4 (In option (c) one meso form will exist).
(a) Ba3(PO4)2 < Na2SO4 < Li3PO4 < C2H5OH < KCl 3. (d) :
(b) Ba3(PO4)2 < C2H5OH < Li3PO4 < Na2SO4 < KCl
(c) C2H5OH < KCl < Na2SO4 < Ba3(PO4)2 < Li3PO4
(d) Ba3(PO4)2 < Li3PO4 < Na2SO4 < KCl < C2H5OH
41. Impure nickel is purified by
(a) the Mond's carbonyl process
(b) electrolytic refining 4. (b) :
(c) the van-Arkel process
(d) the zone refining process.
42. Which process is suitable for the purification of
aniline?
(a) Vacuum distillation
(b) Steam distillation 5. (b) : The n-alkanes have the most extended structure
(c) Fractional distillation and larger surface area in comparison to branched
(d) Fractional crystallisation chain isomers having compact structure (as the
43. In the accompanied diagram, ER, EP and EX represent shape approaches that of a sphere in the branched
the energy of the reactants, products and activated chain isomers). Thus, intermolecular forces are
complex respectively. Which of the following is the weaker in branched chain isomers, therefore, they
activation energy for the backward reaction? have lower boiling points in comparison to straight
chain isomers i.e., higher the branching, lower the
boiling point, hence, the order is I > II > III.
6. (a) : Equivalent weight of metal carbonate = 20 + 30
= 50
2. 5
2.5 g of metal carbonate = = 0.05 eq.
50
Number of equivalents of H2SO4 that would react
(a) A (b) B (c) C (d) D = 0.05
44. 1.00 g of a non-electrolyte solute (molar mass 100 × 1
Number of equivalents of H2SO4 taken = = 0. 1
250 g mol–1) was dissolved in 51.2 g of benzene. 1000
If the freezing point depression constant, Kf of Number of equivalents of H2SO4 which remains
benzene is 5.12 K kg mol–1, the freezing point of unreacted = 0.1 – 0.05 = 0.05 eq.
\ Number of equivalents of alkali consumed
benzene will be lowered by
= 0.05 eq.
(a) 0.2 K (b) 0.4 K meq. = Normality × Volume (in mL)
(c) 0.3 K (d) 0.5 K ∴ 1.0 × V = 0.05 × 1000
45. What formal charges are present in the molecule 0.05 × 1000
V= = 50 mL
C6H5C N — O? 1. 0
(a) N is – 1 and C is + 1 7. (b) : High density polythene is obtained by
(b) N is + 1 and C is – 1 coordination polymerisation.
(c) O is – 1 and C is + 1 8. (b) : Lassaigne’s test for nitrogen fails if the nitrogen
(d) O is – 1 and N is + 1 containing compound does not contain carbon.

78 chemistry tODAy | March ‘16


9. (a) : Ionic character of compounds of metals Thus, stability order
increases down the group.
10. (a) : MnO2 is antiferromagnetic in nature. 20. (d) : Zn + 2HCl ZnCl2 + H2
11. (b) : When the transition metals are in their highest Zn + H2SO4 ZnSO4 + H2
oxidation state, they no longer have tendency to Dil.

give away electrons, thus they are not basic but 4Zn + 10HNO3 4Zn(NO3)2 + N2O + 5H2O
show acidic character and form anionic complexes. Thus, NO3– ions are reduced to N2O whereas in
12. (c) : Catalyst affects the energy of activation of both first two reactions H+ is reduced to H2.
forward as well as backward reaction. 21. (d) : E1 i.e., I.E. of He+ = E1 of H × 22
13. (b) E1 i.e., I.E. of Li2+ = E1 of H × 32
E1 of Li2+ 9
14. (c) : =
E1 of He+ 4
9
E1 of Li2+ = × 19.6 × 10−18
4
(B) (C) = 44.1 × 10−18 J atom −1
According to Markownikoff ’s rule, during hydro-
halogenation to unsymmetrical alkene, the negative
part of the addendum adds to less hydrogenated 22. (d) :
(i.e. more substituted) carbon atom.
15. (c)
16. (a) : When hydration energy exceeds lattice energy,
the compound becomes soluble in water. The In p-dichlorobenzene, two C–Cl dipoles cancel
solubility of alkaline earth metal sulphates decreases each other
in the order \ m = 0.
In o-dichlorobenzene, the two C–Cl dipoles (say x)
are inclined at an angle of 60°. Therefore, according
The solubilities of BeSO4 and MgSO4 are due to to parallelogram law of forces, the resultant
high energy of solvation of smaller Be2+ and Mg2+ = x 2 + x 2 + 2 x 2 × cos 60°
ions.
= x 2 + x 2 + 2 x 2 × 1 / 2 = 3x 2 = 3x
17. (a) : For the reaction A + B  
 C+D In m-dichlorobenzene, the two dipoles are inclined to
[C][D] 3 × 4
Q= = =6 each other at an angle of 120°, therefore, resultant
[ A][B] 1 × 2
But K c = 10; as Q < K c thus forward reaction should = x 2 + x 2 + 2 x 2 × cos 120°
occur.
= x 2 + x 2 + 2 x 2 × (−1 / 2) = x 2 = x
18. (a) : The number of atoms of the ligands that are
Thus, the decreasing order of dipole moments is
directly bound to the central metal atom or ion
o > m > p.
by coordinate bonds is known as the coordination
number of the metal atom or ion. 23. (b) : Fluoride cannot be detected by this test because
Coordination number of metal = number of s the CuF2 formed loses fluorine only at a molten stage
bonds formed by metal with ligands. above 950°C, which is difficult to be attained in the
19. (c) : Due to resonance effect stability of carbocation lab i.e., it is not volatile and hence, the presence of
increases as fluoride cannot be detected by this test.
24. (a) : Ce(OH)3 is the strongest base. As the size of
the lanthanide ions decreases from Ce3+ to Lu3+,
As compared to O electronegativity of nitrogen is
the covalent character of M – OH bond increases
lesser. Thus, cation B is more stable than A and C is
and hence, the basic strength decreases.
least stable due to absence of resonance effect.

chemistry tODAy | March ‘16 79


Thus, Ce(OH)3 is most basic while Lu(OH)3 is least –NO2 group is a deactivating and m-directing
basic. group so it directs the incoming Br– ion to the
25. (a) : m-position thereby leading to the formation of
bromonitrobenzene. Upon reduction with Sn/HCl,
26. (c) the –NO2 group reduces to –NH2 i.e., the final
27. (d) : According to Le-Chatelier’s principle, if product is m-bromoaniline.
a system at equilibrium is subjected to change 36. (b) : For exothermic reactions as temperature
of concentration, pressure or temperature, the increases yield decreases thus
equilibrium shifts in the direction that tends to T1 > T2 > T3
undo the effect. So, it can predict only the direction
37. (c) : Syn and anti prefixes are used to denote
of equilibrium.
geometrical isomers involving either C N or
28. (c) : The given compound is aspirin which is used
as an analgesic. N N bond.
29. (a) : p = 7.8 bar = 7.8 atm (1 bar = 1 atm) 38. (b) : Given, t1/2 = 1386 s
T = 273 + 27 = 300 K For a first order reaction,
i = 2 (for NaCl) 0.693
t1/ 2 = (k = rate constant)
p = iCRT k
p 7.8 0.693
C= = = 0.16 mol/ L. ⇒ 1386 =
iRT 2 × 0.0821× 300 k
⇒ k = 5 × 10–4 s–1 = 0.5 × 10–3 s–1
30. (a) : 1
39. (d) : Bond order (B.O.) = ( Nb − N a ) .
2
40. (d) : DTf i
i for C2H5OH = 1
31. (b) : For Balmer series, n1 = 2
i for KCl = 2
For nth line in any series, n2 = n1 + n
i for Ba3(PO4)2 = 5
\ For 3rd line in Balmer series n2 = 2 + 3 = 5.
• i for Na2SO4 = 3
32. (a) : CH3 (methyl free radical) has planar structure i for Li3PO4 = 4
with sp2 hybridisation of ‘C’ atom. The odd electron Thus, depression in freezing point will be in order:
is present in unhybridised 2pz orbital. C2H5OH < KCl < Na2SO4 < Li3PO4 < Ba3(PO4)2
+
CH3 (methyl carbonium ion) also has trigonal Thus, freezing point will be in the order
planar structure (sp2). Ba3(PO4)2 < Li3PO4 < Na2SO4 < KCl < C2H5OH

CH3 (methyl carbanion) has tetrahedral structure 41. (a)
(sp3) and one of the hybrid orbital contains the lone
42. (b) : Aniline is steam volatile.
pair of electrons.
43. (a) : For backward reaction, activation energy is the
33. (b) : energy difference between product and activated
34. (a) : Maleic acid shows geometrical isomerism and complex.
not optical isomerism. 1000 × K f × w 1000 × 5.12 × 1
44. (b) : m = or 250 =
W × DT 51.2 × DT

1000 × 5.12 × 1
35. (d) : ∴ DT = = 0.4 K
51.2 × 250
1
45. (d) : For nitrogen, formal charge = 5 − (8) = +1
2
1
For oxygen, formal charge = 6 − 6 − (2) = –1.
2


80 chemistry tODAy | March ‘16


chemistry tODAy | March ‘16 81
PRACTICE QUESTIONS ON
Assertion & Reason

 PhysicAl chemistry  OrgAnic chemistry


 inOrgAnic chemistry

Directions : In the following questions, a statement of 6. Assertion : Most probable velocity is the velocity
Assertion is followed by a statement of Reason. Mark the possessed by maximum fraction of molecules at the
correct choice as : same temperature.
(a) If both assertion and reason are true and reason is the Reason : On collision, more and more molecules
correct explanation of assertion. acquire higher speed at the same temperature.
(b) If both assertion and reason are true but reason is not the
7. Assertion : The molecules on the surface have lesser
correct explanation of assertion.
energy.
(c) If assertion is true but reason is false.
Reason : During adsorption, the surface of solid is
(d) If both assertion and reason are false.
in a state of relaxation.
PhysicAl chemistry
8. Assertion : Enthalpy of formation of O2 molecule
1. Assertion : The cell potential of mercury cell is 1.35 V at 298 K and 1 atm pressure is zero.
which remains constant. Reason : Enthalpy of formation of all the elements
Reason : In mercury cell, the electrolyte is a paste at STP is zero.
of HgO and ZnO.
9. Assertion : If the solubility of AgCl in water is
2. Assertion : The transition of electrons n3 → n2 in H
1.5 × 10–10, then its solubility in 0.01M NaCl
atom will emit greater energy than n4 → n3.
aqueous solution is 1.5 × 10–8 M.
Reason : n3 and n2 are closer to nucleus than n4.
Reason : NaCl dissociates completely so [Cl–] = 0.01 M.
3. Assertion : If more and more solute is added to a
solvent, the freezing point of the solution keeps on 10. Assertion : In caesium chloride crystals, Cs+ ions
becoming higher and higher. adopt bcc arrangement.
Reason : Presence of large amount of the solid Reason : For bcc arrangement, number of tetrahedral
solute does not allow the solution to freeze. sites is double the number of atoms in the packing.
4. Assertion : van der Waals’ equation explains the OrgAnic chemistry
behaviour of ideal gases.
11. Assertion : In the Friedel-Crafts acylation of benzene,
Reason : Ideal gases can only be compressed.
the attacking electrophile is an acyl carbocation
5. Assertion : In an electrochemical cell, concentration +
(RCO).
of the anodic half-cell increases while that of
Reason : The reaction of benzene with CH3CH2CH2Cl
cathodic half-cell decreases when the two electrodes
in presence of AlCl3 gives n-propylbenzene.
are joined by a wire.
Reason : At anodic half-cell metal oxidises to 12. Assertion : Vinylic halides are reactive towards
metal ion dissolving the ion in the solution thus, its nucleophilic substitution reactions.
concentration increases at anode and decreases at Reason : Reactivity is due to the polarity of carbon
cathode due to reduction of metal ions. halogen bond.

82 chemistry tODAy | MARCH ‘16


13. Assertion : Hydration of 3, 3-dimethyl-l-butene 23. Assertion : Decreasing order of van der Walls’ radii
with acid gives 2,3-dimethyl-2-butanol. is : Cl > N > O > H.
Reason : Hydration of alkenes with acids occur Reason : van der Waals’ radii increase as the number
through carbanion formation. of energy level increases and decrease as nuclear
14. Assertion : Ketones do not react with monohydric charge increases.
alcohols but do so with dihydric alcohols to give 24. Assertion : Geometry of SF4 molecule can be
cyclic ketals. termed as distorted tetrahedron, a folded square or
Reason : Ketal formation is used to protect the see-saw.
carbonyl group in organic synthesis. Reason : Four fluorine atoms surround or form
15. Assertion : Formic acid is a reducing agent. bond with sulphur molecule.
Reason : Formic acid is used as preservative for fruits.
25. Assertion : Sodium reacts with oxygen to form
16. Assertion : Oxidation of 1-nitro naphthalene gives Na2O2 whereas potassium reacts with oxygen to
o-nitro phthalic acid whereas 1-amino naphthalene form KO2.
on oxidation gives phthalic acid. Reason : Potassium is more reactive than sodium.
Reason : An amino group attached to the benzene
ring makes it resistant to oxidation whereas nitro 26. Assertion : The maximum and minimum oxidation
group makes the benzene ring susceptible to number of sulphur are – 2 and +6 respectively.
oxidation. Reason : SO2 behaves both as an oxidising as well
as reducing agent. However, SO3 can only as an
17. Assertion : Chemical substances which are used to
oxidising agent.
check pregnancy in women are called antifertility
drugs. 27. Assertion : There is a dip in the melting point of
Reason : Antifertility drugs are also called birth Mn in the first transition series.
control drugs or oral contraceptives. Reason : It has high enthalpy of atomization.
18. Assertion : Orlon is used as synthetic fibres. 28. Assertion : A nearly tetrahedral arrangement of the
Reason : The monomer of orlon is vinyl chloride. orbitals about the oxygen atom allows each water
19. Assertion : Chloroform and benzene form a pair of molecule to form hydrogen bonds with as many as
miscible liquids and they are separated by fractional four neighbouring water molecules.
distillation. Reason : In ice each water molecule form four
Reason : Boiling point of benzene is less than that hydrogen bonds as each molecule is fixed in the
of chloroform. space.
20. Assertion : Amino acids mostly exist as dipolar ions. 29. Assertion : BF3 molecule has zero dipole moment.
Reason : The dipolar structure of amino acids is Reason : F is electronegative and B – F bonds are
known as zwitterion or internal salt. polar in nature.
inOrgAnic chemistry 30. Assertion : The degree of complex formation in
21. Assertion : Isomorphous substances form crystals actinides decreases in the order M4+ > MO22+ > M3+ >
of same shape and can grow in saturated solution of MO2+.
each other. Reason : Actinides form complexes with p-bonding
Reason : They have similar constitution and ligands such as alkyl phosphines and thioethers.
chemical formulae.
sOlutiOns
22. Assertion : Zinc is obtained from the roasted or
1. (b) : The overall reaction in a mercury cell is given as :
calcined ore (ZnO) by heating with calculated
Zn(s) + HgO(s) → ZnO(s) + Hg (l)
quantity of coal or coke in a reverberatory furnace,
The cell potential remains constant during its life
when C reduces the metal oxide to free metal.
as the overall reaction does not involve any ion in
Reason : The process of extracting the metal by
reduction of its oxide ore with carbon is called solution whose concentration may change during
smelting. its life time.

chemistry tODAy | MARCH ‘16 83


2. (a) : The difference between the energies of adjacent effect. Resonance gives rise to partial double bond
energy levels decreases as we move away from the character to the carbon-halogen bond making it
nucleus. Thus in H atom stronger and therefore more difficult to cleave than
E2 – E1 > E3 – E2 > E4 – E3..... a Csp3 – X bond. It also reduces the polarity of the
3. (d) : The freezing point keeps on becoming lower carbon-halogen bond thereby making heterolysis
and lower when more and more solute is added to a difficult.
solvent. Depression in freezing point is a colligative
property as it depends on the number of particles
13. (c) : Hydration of alkenes by acids occur through
present in solution, so solution will freeze more
carbocation intermediate. The initially formed
rapidly on adding large amount of solute.
carbocation (2°) being less stable rearranges to the
4. (d) : van der Waals’ equation
more stable carbocation (3°), which in turn gives
 an2 
 P + V 2  (V − nb ) = nRT (for n mol of gas) explains
2, 3-dimethyl-2-butanol.
  14. (b) :
the behaviour of real gases, where a and b are van
der Waals’ constants, whose values depend on the
nature of the gas. Real gases can be compressed.
5. (a)
6 (c) : On collision, some molecules are speeded up
while others are slowed down. The ketals can be decomposed back to the original
7. (d) : The molecules on the surface, have higher ketone by treatment with acid.
energy than those inside. 15. (b) : Formic acid is readily oxidised to CO2 and
The surface of a solid or a liquid is in a state of strain H2O, and thus acts as a strong reducing agent.
or tension on account of the unbalanced or residual
HCOOH [O]
→ H2O + CO2
forces.
16. (c) : An amino group increases the electron density
8. (c) : Enthalpy of formation of the most stable
in the benzene ring to which it is attached thereby
allotrope of the element is taken as zero.
making it susceptible to oxidation while a nitro
9. (b) : NaCl dissociates completely and so in 0.01 M
group decreases the electron density in the benzene
NaCl solution, [Cl–] = 0.01 M.
ring to which it is attached thereby making it
If s is the solubility of AgCl in mol L–1 then
[Ag+] = [Cl–] = s mol L–1 resistant to oxidation. Instead, the other benzene
and hence total [Cl–] = s + (0.01) mol L–1  0.01 mol L–1 ring gets oxidised giving o-nitrophthalic acid as
\ Ksp = [Ag+][Cl–] = s (0.01) shown below :

1.5 × 10−10
\ s= = 1.5 × 10−8 mol L−1
0.01
10. (c) : Number of tetrahedral sites is double the
number of atoms in the packing for a closed packed
arrangement (hcp and ccp) and not for bcc.
11. (c) : In the reaction of benzene with CH3CH2CH2Cl
in presence of AlCl3, attacking species is secondary 17. (b)
+
carbocation CH3CHCH3 and not primary carbocation
+ 18. (c) : The monomer of orlon is acrylonitrile.
CH3CH2CH2. Therefore, the product obtained is
isopropyl benzene. 19. (c) : Chloroform (b.pt. 60°C) and benzene
(b.pt. 80° C) can be separated by fractional distillation
12. (d) : Vinylic halides are unreactive towards nucleo-
philic substitution reactions because of resonance since the difference in boiling points is very less.

84 chemistry tODAy | MARCH ‘16


20. (b) : The –COOH group and –NH2 group of amino 27. (c) : Mn has exactly half-filled d-orbitals so its
acids neutralise each other involving the transfer electronic configuration is stable. Electrons are held
of a proton from the –COOH group to the –NH2 tightly by the nucleus and this results in less
group within the molecule. So, amino acids largely delocalisation of electrons and therefore, metallic
exist as dipolar ions. bond is weaker than the previous element.
+ 28. (a) : At any given instant in liquid water at room
NH2 NH3 temperature, each water molecule forms hydrogen
R CH COOH R CH COO– bonds with an average 3.4 other water molecules.
Zwitter ion or The liquid water molecules are disorganized and
internal salt
are in continuous motion so hydrogen bonds are
21. (a) : Examples of isomorphous compounds are
constantly and rapidly broken and formed. In ice
K2SO4, K2CrO4, K2SeO4 (valency of S, Cr, Se=6)
H2O molecules are, however fixed in the space
and ZnSO4.7H2O, MgSO4.7H2O, FeSO4.7H2O lattice.
(valency of Zn, Mg, Fe = 2).
29. (b) : BF3 is sp2 hybridized. Dipole moment is a
22. (b) : The reactions involved are : vector quantity. The three bond moments give a net
sum of zero, as the resultant of any two is equal and
opposite to the third.
23. (a) : As number of energy shells for H, O, N and Cl
is l, 2, 2 and 3 respectively so van der Waals’ radius
of H is the smallest and Cl is the biggest. Both 30. (b) : Higher the charge on the metal ion, smaller
O and N have two energy levels but the nuclear is the ionic size and more is the complex forming
charge on O (+8) is higher than that of N (+7). ability. Thus, the degree of complex formation
Thus, the van der Waals’ radius of N is bigger than decreases in the order
that of O. M4+ > MO22+ > M3+ > MO2+
So, the decreasing order is : Cl > N > O > H. The higher tendency of complex formation of MO22+
as compared to M3+ is due to high concentration of
24. (b) : SF4 has five electron pairs whose arrangement charge on metal atom M in MO22+.
should be trigonal bipyramidal according to VSEPR 
theory. Two structures are possible.
EXAM DATES 2016
JEE Main : 3rd April (offline),
9th & 10th April (online)
vitEEE : 6th to 17th April
MgiMs : 17th April
AMU (Engg.) : 24th April
Kerala pEt : 25th & 26th April
25. (b) : K+ being larger in size than Na+ has a weaker Kerala pMt : 27th & 28th April
positive field around it which cannot prevent the ApEAMCEt : 29th April
conversion of peroxide ion (O22–) to superoxide ion (Engg. & Med.)
(O2–). AipMt : 1st May
26. (b) : Since oxidation number of S in SO2 is +4, so, COMED K : 8th May
it can be either increased or decreased (minimum Karnataka CEt : 4th & 5th May
O.N. of S is –2 and maximum O.N. of S is +6). BitsAt : 14th to 28th May
Therefore, SO2, behaves both as an oxidising as wB JEE : 17th May
well as a reducing agent. On the contrary, the JEE Advanced : 22nd May
oxidation number of S in SO3 is +6 which can AiiMs : 29th May
only be decreased. Therefore, SO3 can act only as AMU (Med.) : 1st June
an oxidising agent. JipMER : 5th June

chemistry tODAy | MARCH ‘16 85


Y U ASK
Now,
(i) When liquid water is treated as incompressible
fluid the molar volume becomes independent of
the pressure then,

WE ANSWER Vm = constant
Therefore,
Pf
Do you have a question that you just can’t get
answered?
Gm(P ) − Gm(P ) = Vm
f i ∫ dp
Pi
Use the vast expertise of our mtg team to get to the
= Vm(Pf – Pi)
bottom of the question. From the serious to the silly,
the controversial to the trivial, the team will tackle the (ii) When water vapour is treated as perfect gas,
questions, easy and tough. Vm varies with pressure and it is given as :
The best questions and their solutions will be printed in RT
Vm = (Ideal gas equation)
this column each month. P
Therefore,
Q 1. How can we calculate the change in the molar Pf Pf
Gibbs’ energy if we RT dP
(i) treat liquid water as an incompressible fluid
Gm(P ) − Gm(P ) =
f i ∫ P
dP = RT ∫ P
Pi Pi
and
( R and T are constant)
(ii) treat water vapour as a perfect gas.
 Pf 
–Geeta Rastogi, Surat (Gujarat) = RT ln  
Ans. Gibbs’ energy, G is given as :  Pi 
G = H – TS
For infinitesimal change in each property, we
have
dG = dH – TdS – SdT ...(i)
As we know,
Enthalpy is related to internal energy (U) as :
H = U + PV
Then,
Q 2. What are Chiral drugs? Why are they so
dH = dU + PdV + VdP
important?
For a closed system, where there is no –Tanya Mehra, (Bangaluru)
non‑expansion work, Ans. Chiral drugs are the drugs that contain a single
dU = TdS – PdV enantiomer rather than a racemate.
Then, equation (i), becomes Chiral drugs are important in pharmaceutical
dG = (TdS – PdV) + PdV + VdP – TdS – SdT industry as in many drugs the enantiomers have
dG = VdP – SdT ...(ii) (At constant distinctly different effects. Then, stereoselective
composition) synthesis plays the role in the preparation of
The change in molar Gibbs’ energy is obtained by enantiomerically pure drugs.
integrating equation (ii) at constant temperature, The antihypertensive drug methyldopa (aldomet)
Pf owes its effect exclusively to the S‑isomer.
Gm(P ) − Gm(P ) =
f i ∫ VmdP CH3
Pi
HO CH2 C COOH
This equation, gives the variation of molar Gibbs’
energy with pressure. HO NH2
Methyldopa

86 chemistry tODAy | March ‘16


chemistry tODAy | March ‘16 87
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ACROSS 9. The element formed after a-emission. (11)


1. A polymorph of quartz. (12) 10. The selective reactivity of one functional group in the
3. The theory which mainly deals with the geometry and presence of others is called. (16)
magnetic properties of the complex was developed 13. Common name of prop-1-ene-1,2,3-tricarboxylic acid
by______. (7) found in sugarcane and beetroot. (12)
5. One of the allotropic forms of pure iron. (9) 14. H4C4B2H2 is a pentagonal pyramidal ________. (13)
8. The more stable shape of SF4. (12) 15. The process of separation of colloidal sol into liquid phases.
9. The process that occurs without change of enthalpy. (11) (12)
11. The molecular fragments obtained after disconnection of an 18. The commercial name of solid CO2 which is used as
organic compound. (8) refrigerant. (7)
12. Mercuric sulphide is used as a _______. (8)
22. Graph of entropy of a substance against temperature. (9)
16. Ligand used in organic synthesis for enantioselective
21. Polyethylene glycol polymers used in ointment bases as
transformations. (5)
water soluble ingredient. (10)
17. The scientist who introduced the term isotope. (5)
24. The reactive intermediate that appears after electrophilic
19. Device used to measure the intensity of flame colouration. (17)
substitution of benzene. (7)
20. The temperature at which antiferromagnetic substance

changes to paramagnetic. (4)
23. Another name of non stoichiometric solid
compounds. (11)
25. In 1935, Yukawa introduced a meson theory
which accounts for the stability of _______.(7)
26. An electrically neutral molecule, whose name is
derived from sugar beets (Beta vulgaris). (7)
27. The process that take place when vapour pressure
of both the solid and liquid form of a substance
are equal. (8)
28. The temperature above which gas shows heating
effect on expansion while below it gas cools on
expansion. (9)
29. The reagent used for the conversion of alkene
into diol which further gets oxidised to aldehyde
or ketone. (7)
DOWN
2. Phenomenon used to distinguish between a
colloidal and true solution. (13)
4. Substance identified by Dustan’s test. (8)
6. Chemical name of Sindri fertilizer. (16)
7. Rearrangement which involves conversion
of hydroxamic acid into an isocyanate via
intermediate of its o-acyl derivative. (6)

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90 chemistry tODAy | March ‘16