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General Instructions

(a) All questions are compulsory.


(b) Q. no. 1 to 5 are very short answer questions and carry 1 mark each.
(c) Q. no. 6 to 10 short answer questions and carry 2 marks each.
(d) Q. no. 11 to 22 are also short answer questions and carry 3 marks each.
(e) Q. no. 23 is a value based question and carry 4 marks.
(f) Q. no. 24 to 26 are long answer questions and carry 5 marks each.

Very Short Answer Type Questions 12. Write the IUPAC name and type of structure of
1. Draw the structure of 2-(3-chlorophenyl) pentane. following complexes.
(i) [Pt(NH3 ) Cl (NO2 )]
2. What do you mean by molarity of a solution? (ii) [Co (NH3 )4 Cl2 ] Cl
3. Write an example each for primary battery and (iii) Ni (CO)4
secondary battery. 13. (i) Define the terms “ferrimagnetism” and
4. State whether the S—O bond in SO2 is polar or “paramagnetism”. Give suitable examples for
non-polar. each.
(ii) What happens when ferrimagnetic Fe3O4 is
5. Table salt (NaCl) sometimes appear yellow in heated at 850 K?
colour. Explain why?
14. Explain the following terms with suitable examples.
Short Answer Type Questions (I) (i) Cationic detergents
6. Find out the depression in freezing point of water (ii) Anionic detergents
when 10 g of CH3CH2CHCl — COOH is added to (iii) Non-ionic detergents
250 g of water. Ka = 1.4 ´ 10- 3 , Kf = 1.86 K kg mol - 1. 15. Give an example for each of the following:
7. Explain why does the conductivity of germanium (i) Friedel-Crafts reaction
crystals increase on doping with gallium? (ii) Sandmeyer reaction
(iii) Gattermann-Koch reaction
8. Define Henry’s law. Explain the significance of KH .
16. The emf of a standard Cd-cell is 1.018 V at 25°C. The
9. What happens when D-glucose reacts with the temperature coefficient of the cell is
following reagents? - 5.0 ´ 10- 5 VK - 1. Calculate DG, DH and DS for the
(i) Bromine water (ii) HNO3
cell reaction.
10. How can we distinguish ethylamine from 17. Represent the cell in which the following reaction
(i) diethylamine? takes place at 298 K.
(ii) acetamide?
Mg(s) + 2Ag + (0.0001 M) ¾®
Short Answer Type Questions (II)
Mg2 + (0.130M) + 2Ag(s)
11. Draw the structures of the following species. Calculate its Ecell if E°cell = 3.17 V.
(i) H3PO2 (ii) PCl5 (iii) ClF 3

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18. (i) Explain why Answer the following questions :
(a) air becomes dry when passed over (i) Name two fossil fuels other than petrol.
silica gel? (ii) Was the battery used in the vehicle a primary
(b) colloidal medicines are more effective? battery or a secondary battery?
(ii) Give an example of each of the following: (iii) What value do we infer from the above story?
(a) Oil in water type of emulsion. Long Answer Type Questions
(b) Water in oil type of emulsion. 2+
24. (i) (a) Which is stronger reducing agent, Cr or
19. What are polymers? Classify polymers on the basis Fe2 + and why?
of their structures. (b) Explain why Ce4 + is a strong oxidising
20. (i) Why magnesium cannot be used for the agent?
reduction of alumina? (c) Explain why Cu + ion is stable in aqueous
(ii) What do you mean by the term pyrometallurgy? solutions?
(iii) Explain the role of NaCN in the extraction of (ii) Describe the oxidising property of KMnO4 in
silver from its ore. neutral or slightly alkaline medium, when it
21. Give reason reacts with iodide ions and thiosulphate ions.
(i) Solid PCl5 is an ionic compound. 25. (i) Write the reactions for the conversion of
(ii) Ozone is thermodynamically unstable. (a) ethanol to 3-hydroxy butanol.
(iii) Fluorine mostly gives exothermic reactions. (b) benzaldehyde to benzophenone.
(ii) Write chemical tests to distinguish
22. Complete the following equations :
(i) HgCl2 + PH3 ¾® (a) propanal from propanone.
(ii) XeF4 + H2O ¾® (b) acetophenone from the benzophenone
(iii) SO3 + H2SO4 ¾® (c) phenol from benzoic acid.

Value Based Question 26. (i) Find the rate constant of a first order reaction if
its half-life period is 100s.
23. Rajiv goes to buy a scooty. After looking at several (ii) What is a pseudo first order reaction? Give two
models of the two wheeler, he choses a hybrid examples.
scooty which runs on petrol as well as on an
electrically rechargeable battery.

Detailed solution of these questions are available on http://www.arihantbooks.com/Chemistry%20Spectrum.pdf

73
Explanations
1. CHO COOH
CH3—CH2—CH2—CH—CH3
½ Br 2 water ½
(C HOH)4 ¾¾¾¾¾¾® (CHOH)4
½ Oxidation (mild)
½
CH2OH CH2OH
D - glucose Gluconic acid
Cl
2-(3-chlorophenyl) pentane (ii) Reaction of D-glucose with HNO 3 results in the formation of
saccharic acid.
2. Molarity of a solution is the number of moles of solute per litre of
CHO COOH
the solvent. It is denoted by M.
½ HNO 3
½
Moles of solute (C HOH)4 ¾¾¾¾¾® (C HOH)4
M= oxidation
Volume of solvent (in litre) ½ ½
CH2OH COOH
3. Primary battery - Dry cell. D - glucose Saccharic acid
Secondary battery - Lead storage battery.
10. (i) Ethylamine gives carbylamine test. It smells foul when
4. S ¾ O bonds formed in SO 2 are of polar nature. heated with chloroform and alcoholic KOH. Diethylamine
doesn’t give this test.
S S S
D
C 2 H5NH2 + CHCl 3 + 3KOH ¾¾ ® C 2H5NC + 3KCl + 3H2O
O O
(ii) Acetamide when heated with KOH gives smell of ammonia
5. Due to metal excess defect, NaCl generates F-centres in its crystal while ethylamine doesn’t.
which imparts yellow colour to it. D
CH3 CONH2 + KOH ¾¾ ® CH3COOK + NH3
6. DTf (depression in freezing point)= 1000 K f w1i = molality ´ K f ´ i
m1 x w 2 Cl F
Cl
w1 10 g 11. (i) H3PO2 (ii) PCl5 Cl (iii) ClF3 Cl
= moles of solute = P P F
m1 122.5 g mol - 1 H O H Cl
H Cl F
250
w 2 = grams of solvent = 250 g = kg
1000 12. (i) IUPAC name : Amminechloridonitro-N-platinum (II)
Molality = mol kg -1 Structure : Square planar
10 / 122 .5 (ii) IUPAC name : Tetraamminedichloridocobalt (III) chloride
= = 0.3265 mol kg -1 Structure : Octahedral.
0.250
(iii) IUPAC name : Tetracarbonyl nickel (0)
i = van' t Hoff factor
- +
Structure : Tetrahedral
CH3CH2CHCOOH a CH CH CHCOO +H
3 2
13. (i) Ferrimagnetism refers to an arrangement of magnetic
Cl Cl moments where they are aligned in parallel and antiparallel
Weak monobasic acid directions unequally, e.g. Fe 3O 4 , MgFe 2O 4 . Paramagnetic
y=2
substance are weakly and temporarily magnetised in a
i = 1 + ( y - 1) x = (1 + x ) magnetic field. e.g. O 2, Cu + .
By Ostwald’s dilution law (ii) Fe 3O 4 loses ferrimagnetism at 850K and becomes
- 3 para-magnetic.
Ka 1.4 ´ 10
x= = = 0.0655
C 0.3265 14. (i) Cationic detergents are quaternary ammonium salts of
amines with acetates, chlorides or bromides, e.g.
\ i = (1 + x ) = 1.0655
cetyltrimethyl ammonium bromide.
DTf = m K f i = 0.3265 ´ 1.86 ´ 1.0655 = 0.65 K
(ii) Anionic detergents have large anionic part in their
7. When germanium is doped with gallium, the dopant replace molecules. These are further divided into two types:
germanium at some of the lattice site. Since, gallium has one less (a) Sodium alkyl sulphates, e.g. sodium lauryl sulphate.
valence electron (3 versus 4 of germanium), it creates an electron
vacancy which moves through the crystal and increase the (b) Sodium alkyl benzene sulphonates, e.g. sodium dodecyl
conductivity of germanium crystal. This doping results in making benzene sulphonate.
of p-type semiconductor. 15. (i) C 6 H6 + RCOCl ¾ Anhyd.
¾ ¾ ¾¾
AlCl 3
® C 6 H5COR + HCl
8. According to Henry’s law “the partial pressure of the gas in
vapour phase ( p) is directly proportional to the mole fraction of the CuCl/HCl
gas ( x ) in the solution” and is expressed as p = KH x (ii) N2Cl Cl
where, KH is the Henry’s law constant
Benzene diazonium Chlorobenzene
Significance of KH is that the higher value of KH , lower is the
chloride
solubility of the gas.
9. (i) Reaction of D-glucose with Br2 results in the formation of CHO
CO, HCl
gluconic acid. (iii)
Anhyd.AlCl3/CuCl

74
16. (i) DG = - nFE = - 2 ´ 96500 ´ 1.018 J mol - 1 (iii) Silver ore is leached with dilute solution of NaCN in the
presence of oxygen. Ag solubilised in the solution and form
= - 196.474 kJ mol - 1 [Cd 2+ + 2 e - ¾® Cd ]
the sodium argentocyanide [Na[Ag(CN)2 ] complex while
æ ¶E ö
(ii) DS = nF ç ÷ = 2 ´ 96500 ´ ( - 5.0 ´ 10 -5 ) JK -1 mol -1 impurities are filtered off.
è ¶T ø p Ag 2S + 4NaCN ¾® 2Na[Ag(CN)2 ] + Na 2S
= - 9.65 JK -1 mol -1 4Na 2 S + 2H2O + 5O 2 ¾® 2Na 2 SO 4 + 4NaOH + 2S
(iii) DH = TDS + DG = 298 ´ ( - 9.65) + ( - 196474 ) J mol -1 21. (i) Solid PCl 5 ionises as PCl +4 and PCl -6
-1 -1
= - 199349 J mol = - 199.349 kJ mol 2PCl 5 ¾® PCl +4 + PCl -6
Tetrahedral Octahedral
17. The cell can be represented as
(ii) O 3 decomposes into O 2 exothermically.
Mg |Mg 2+ (0.130 M) || Ag + (0.0001 M)| Ag
- Anode Cathode + 2O 3 ¾® 3O 2, DH = -ve
Oxidation at anode: Mg ¾® Mg 2+ + 2 e - Since, randomness increases due to increase in the number
of molecules hence, entropy also increases.
Reduction at cathode: 2Ag + + 2e - ¾® 2Ag We know,
Net cell reaction 2Ag + + Mg ¾® Mg 2+ + 2Ag DG ° = DH ° - TDS ° DH < 0
Thus, DG = - ve, as DS > 0
[Mg 2+ ] 0.130
K= = = 1.3 ´ 10 7 Thus, conversion of O 3 into O 2 takes place spontaneously
[Ag + ]2 (0.0001)2 with decrease in free energy. Hence, O 3 is thermodynamic
By Nernst equation unstable.
2 .303 RT (iii) Most of the reactions of F2 are exothermic due to the small
E = E° - log K and strong bond formation with other elements.
nF
22. (i) 3HgCl 2 + 2PH3 ¾® Hg 3 P2 + 6HCl
2 .303 RT
At 298 K, = 0.0591 (ii) 6XeF4 + 12H2O ¾® 4Xe + 2XeO 3 + 24HF + 3O 2
F
0.0591 (iii) SO 3 + H2SO 4 ¾® H2 S 2O 7
E = Ecell
° - log 1.3 ´ 10 7
2 23. (i) Natural gas and coal.
0.0591 (ii) Secondary batteries are rechargeable.
= 3.17 - log 1.3 ´ 10 7
2 (iii) This story shows that Rajiv is concerned about environment.
= 3.17 - 0.21 = 2.96 V Fossil fuel including petrol cause air pollution whereas
battery run vehicles are ecofriendly. Hybrid vehicle also
18. (i) (a) Silica gel absorbs moisture from the air hence, air
provide Rajiv an option of using both kind of source of
becomes dry.
energy as per his convenience.
(b) Colloidal medicines are more effective in the treatment of
disease because they have large surface area and are 24. (i) (a) Fe 2 + is better reducing agent than Cr 2+, because stability
therefore easily assimilated. increases during the formation of Fe 3+ from Fe 2+ .
(ii) (a) Milk . Fe 2+ Fe3++ e–
(b) Butter
19. A polymer is a large molecule made by linking together repeating 3d5 (more stable)
units of small molecules called monomers. The process of linking 2+ Cr3++ e–
Cr
them up is called polymerisation.
n H2C == CH2 ¾® (—CH2 — CH2 —)n
Ethylene monomer Polyethylene 3d 4 3d 3
4+ - 3+
Classification based on structure (b) Ce +e ¾® Ce
(i) Linear polymers They have long and straight chains and E °Ce 4 + /Ce 3 + = 1.74 V
have high density. e.g. polythene, polyvinyl chloride (PVC). Since, E ° is positive it indicates that Ce 4 + is a better
(ii) Branched chain polymers They have linear chains with oxidising agent.
some branches and have low density. e.g. polyisobutylene. (c) Cu + ion undergoes disproportionation reaction in
(iii) Cross-linked or network polymers They are formed from aqueous medium.
monomers with two and three functional groups. They have
2 Cu + ( aq ) ¾® Cu( s ) + Cu 2+ ( aq ) E ° = + ve
strong covalent bonds. e.g. bakelite.
Thus, DG ° = - nFE ° = - ve
20. (i) Although, thermodynamically possible, in practice,
Thus, it is a spontaneous process and hence, Cu + ion is
magnesium metal cannot be used in the reduction of
stable in aqueous medium.
alumina because in Ellingham diagram, the lines of Al 2O 3
and MgO intersect at about 1400°C. Mg can reduce alumina (ii) Reaction with I- ion
above this temperature but temperature is so high that the 2MnO -4 + H2O + I - ¾® 2MnO 2 + IO -3 + 2OH-
process becomes technically difficult and uneconomical. Reaction with S2O23 - ion
(ii) Pyrometallurgy involves the heating of metal oxide with a
suitable reducing agent in order to extract the metal. 8MnO -4 + 3S 2O 23- + H2O ¾® 8MnO 2 + 6SO 24 - + 2OH-

75
25. (i) (a) Ethanol to 3-hydroxy butanol (c) Phenol Benzoic acid
CH3CH2OH ¾Cu
¾¾ /D
® CH3CHO
Neutral FeCl 3 solution Gives buff-coloured precipitate.
2CH3CHO ¾NaOH
¾¾® CH3 CH CH2CHO : It gives violet colour Gives brisk effervescence due to
Aldol | NaHCO 3 solution : No CO .
OH reaction.
2
3-hydroxy butanal
C 6H5COOH + NaHCO 3 ¾®
(b) Benzaldehyde to benzophenone
CO 2 ­ + C 6 H5 COONa + H2O
Oxidation
CHO COOH
26. (i) For a first order reaction,
Benzaldehyde PCl5 0.693
t1/ 2 =
/AlCl 3 k
0.693
C COCl or k=
Friedel-Crafts t1/ 2
Benzophenone 0.693
or k=
100
(ii) (a) Propanal Propanone k = 6.93 ´ 10 k - 3 s - 1 [Qt1/ 2 = 100 s ]
Iodoform test : negative Positive (ii) Pseudo first order reaction is not truly first order but shows
kinetics of first order under certain conditions. e.g.
D (a) Hydrolysis of ethyl acetate when concentration of water
CH3CCH3+3l2 + 4NaOH
is very large
CH3COOC 2H5 + H2O ¾® CH3COOH + C 2 H5 OH
CH3CONa+CHl3 + 3H2O Rate = k [CH3COOC 2H5 ] [H2O]
(Yellow ppt.)
= k 0 [CH3COOC 2H5 ]
(b) Acetophenone Benzophenone because [H2O] is very large.
Iodoform test : positive Negative (b) Inversion of cane sugar, if the concentration of H2O
(solvent) is very large and catalyst (H3O + ) is not varying.
When [H2O] and [H3O + ] are too large, it becomes a
CCH3+3l2 +4NaOH
pseudo first order reaction.
Rate = k [C12 H22 O 11 ] [H2O] [H3O + ]
CONa+CHl3 + 3H2O = k 0 [C12 H22O 11 ]
(Yellow ppt.)

76
for
Class
XII

General Instructions
(a) All questions are compulsory.
(b) Q.no. 1 to 5 are very short answer questions and carry 1 mark each
(c) Q.no. 6 to 10 are short answer question and carry 2 marks each.
(d) Q.no. 11 to 22 are also short answer questions and carry 3 marks each.
(e) Q.no. 23 is a value based question and carry 4 marks.
(f) Q.no. 24 to 26 are long answer questions and carry 5 marks each.
(g) Use log tables if necessary use of calculators is not allowed.

Very Short Answer Type Questions 10. A solution which is prepared by dissolving 1.25 g of oil
1. The following curve is in accordance of winter green (methylsalicylate) in 99.0 g benzene
has a boiling point of 80.31° C. Find the molecular
log x/m

with Freundlich adsorption isotherm.


mass of this compound.
What is the slope and y-intercept of (Boiling point of pure benzene = 80.10° C and K b for
the curve? log p
benzene = 2.53°C kg mol -1 )
2. What is the covalency of nitrogen in N2 O5 ?
Short Answer Type Questions (II)
3. Write the IUPAC name of the following coordination 11. State briefly the principle involved in the following
compound: operation in metallurgy.
[PtCl2 (en)2 ](NO3 )2 (i) Vapour phase refining (ii) Electrolytic refining
4. H3 PO2 acts as an strong reducing agent. Justify. 12. Give answer for the following questions.
5. Write the name of the product formed when diazonium (a) State Raoult’s law for a solution containing
fluoroborate is heated with aqueous sodium nitrite non-volatile solute. Give, its mathematical
solution. expression also.
(b) Calculate the boiling point of a solution
Short Answer Type Questions (I) containing 0.61 g of benzoic acid in 50 g of CS2 .
6. Why does conductivity of germanium crystals increase Assuming 84% dimerisation of acid. The boiling
on doping with gallium? Explain. point and K b for CS2 are 46.2°C and 2.3 K kg mol
-1
7. The electrode potential for Mg electrode respectively.
varies according to the equation 13. The EMF of the following cell is found to be 0.20 V at
0.0591 1 298 K.
E 2+ = E° 2 + - log . Plot the
Mg / Mg Mg / Mg 2 [ Mg2 + ] Cd|Cd2 + (?)||Ni2 + (2.0M)|Ni
2+
graph between E 2 +
Mg / Mg
versus log[Mg ]. Determine the molar concentration of Cd2 + ion in the
solution.
8. + -
A solid A B has NaCl type close packed structure. If (E° 2 + = - 0.40V, E° 2 + = -0.25 V)
Cd / Cd Ni / Ni
the anion has a radius of 260 pm, what should be the
radius of the cation? Can a cation C + having a radius of 14. Explain the following observations giving appropriate
180 pm be slipped into the tetrahedral site of the crystal reasons.
A+ B- ? Give reason for your answer. (i) CN- ion is known but CP - ion is not known
9. Draw the structure of the following compounds: (ii) Phosphinic acid acts as a monoprotic acid.
(i) H4 P2 O7 (ii) HOClO3 (iii) When KI solution treated with Cl2 gives a brown
colour but excess of Cl2 turns it colourless.

74
15. (a) Predict the magnetic behaviour of [CoF6 ]3 - complex (b) One mole of symmetrical alkene upon ozonolysis
gives two moles of aldehyde which have
(b) Draw structures of geometrical isomers of
molecular mass 44u. Predict the structure of
[Cr(H2 O)4 Cl2 ] + .
alkene.
(c) The CFSE for octahedral [CoCl4 ]4 - is 18,000 cm -1 ,
what will be the CFSE for tetrahedral [CoCl4 ]2 - 21. (i) Draw the structure of the monomers of the
ion? following polymer.
(a) Teflon
16. Explain the following observations:
(b) Polythene
(i) Zeolites are good shape-selective catalysts.
(ii) Arrange the following polymer in the increasing
(ii) High temperature is not a favourable condition for
order of tensile strength nylon-6, buna-S,
physical adsorption.
polythene.
(iii) On dilution of soap solution micelles may revert
(iii) What are condensation polymers? Give one
to individual ions.
example.
17. (i) Toluene reacts with a halogen in the presence of
22. (i) Write the chemical reaction to show that glucose
iron (III) chloride giving ortho and para
contain primary alcoholic (—OH) group.
halocompounds. Write mechanism of the
(ii) What is peptide linkage?
reaction.
(iii) Write the structure of a nucleoside and
(ii) Identify the compound Y in the following reaction.
+ –
nucleotide.
NH3 N2Cl
NaNO2+HCl Cu2Cl2
Y+N2
Value Based Question
273–278K
23. On the occasion of world health day, Delhi government
(iii) The solubility of halo alkanes in water is low. organised a health mela for the poor people living in
Explain why? slum areas. After checkup, doctors were shocked to see
that most of the people suffered from cancer due to
18. Write down the functional isomers of a carbonyl regular exposure to pesticides and many were diabetic.
compound with molecular formula C 3 H6 O. Which Delhi government distributed free medicines to them
isomer will react faster with HCN and why? and decided to provide medical care, financial
Explain the mechanism of the reaction also. Will the assistance.
reaction lead to the completion with the conversion of (i) Write the type of analgesic which is used for the
whole reactant into product at reaction condition? If a relief of pain due to terminal cancer.
strong acid is added to the reaction mixture what will
(ii) Give an example of artificial sweetener that could
be the effect on concentration of the product and why?
have been recommended to diabtic patients.
19. (i) Describe a chemical test in each case to (iii) Name an analgesics which is used in the
distinguish between the following pairs of prevention of heart attacks.
compounds.
(iv) Write the value shown by Delhi government.
(a) Aniline and N-ethylaniline
(b) N-methylpropane-2-amine and N-ethyl-N Long Answer Type Questions
methylethanamine 24. (a) Write the mechanism of dehydration of ethanol to
(ii) Arrange the following in increasing order of basic form ethene.
strength in aqueous medium (b) How are the following conversion carried out?
NH3 , CH3 NH2 , (CH3 )3 NH, (CH3 )3 N (i) Phenol to benzoic acid
20. (a) Exemplify the following reactions: (ii) Chlorobenzene to p-nitrophenol
(i) Wolff-Kishner reduction (c) Give the structure and IUPAC name of the major
(ii) Haloform reaction product obtained in the following reaction.
(b) How will you convert acetaldehyde to acetone? OH
or
(a) Complete the following reaction
+ 3Br2

Cd or
2
(i) Cl
Dry ether (a) Write the mechanism and the product formed in
the following reaction.
CH3
(i) CrO3/(CH3CO)2O CH3
— —

(ii) H2O/OH–(Hydrolysis)
(ii) H3C—C—O—CH3 + HI
CH3

75
(b) Write short note on Reimer Tiemann reaction. (b) Interconvertibility of chromate ion and
(c) Out of o-nitrophenol and p-nitrophenol which is dichromate ion in aqueous solution depends upon
more volatile. pH of the solution.
(c) Potassium permanganate is thermally unstable at
25. Account for the following. 513 K.
(i) Transition elements show highest oxidation state (i) State the term ‘order of reaction’ for chemical
26.
in their oxides than fluorides. reaction.
(ii) Cu has positive electrode potential in the first (ii) A reaction is of first order wrt reactant A and of
transition series. second order wrt reactant B. How is the rate of the
(iii) Ionisation enthalpy of lanthanides is lower than reaction affected when
actinides. (a) the concentration of B is increased to three times?
(iv) Potassium dichromate is a good oxidising agent (b) the concentration of A as well as B are doubled?
in acidic medium. (iii) The decomposition of NH3 on platinum surface.
Pt
(v) Actinides show more number of oxidation states 2NH3 (g) ¾ ¾® N2 (g) + 3H3 (g) is a zero order
than lanthanides. reaction with k = 2.5 ´ 10 -4 Ms -1 . What are the
or rates of production of N2 and H2 ?
(i) Compare non-transition and transition elements or
on the basis the following. (i) What is the rate of a reaction?
(a) variability of oxidation state (ii) The rate constant for a reaction of zero order wrt
(b) stability of oxidaton states A is 0.0030 mol L -1 s -1 How long will it take for the
(ii) Give the chemical reactions for the following initial concentration of A to fall from 010 . M to
observations. 0.075 M?
(a) Potassium permanganate is a good oxidising (iii) The half-life for radioactive decay of 14 C is
agent in basic medium. 5730 yr. An archaeological artifact contained
wood that had only 80% of the 14 C found in living
tree. Estimate the age of the sample.

Detailed solutions of these questions are available on http://www.arihantbooks.com/Chemistry%20Spectrum.pdf

76
Explanations
1. According to the Freundlich adsorption isotherm This equation represents equation of straight line.
x So, y-intercept (c ) = E ° 2 +
= Kp1/ n Mg /Mg
m 0.0591
x æ1ö Slope ( M ) =
Taking log on both side log = ç ÷ log p + log K 2
m è nø
This equation can be diagrammatically represented as
­ ­ ­ ­
y= m x+c
1
Hence, slope ( m) =
n

EMg2+/Mg
Slope= 0.0591
Intercept (c ) = log K 2
2. Covalency of nitrogen in N 2O 5 is 4. C=EºMg2+/Mg

log [Mg2+]

8. A solid A + B- has NaCl structure, A + ions will be present in


3. Dichloridobis (ethane - 1, 2-diamine) platinum (iv) nitrate. the octahedral voids. The radius of the cation will be equal to
4. Strong reducing behaviour of H 3 PO 2 is due to the presence of the radius of the octahedral voids, as it will touch the anions
and arrangement will be close packed. Thus,
two P — H bonds and one P—OH bond. Radius of the octahedral void = rA+
= 0.414 ´ rB- = 0.414 ´ 260 pm = 107.6 pm
P H Radius of the tetrahedral site
H OH = 0.225 ´ rB-
Hypophosphorous acid
(monobasic) = 0.225 ´ 250 pm = 56.25 pm
In this case radius of the cation (C + ) (180 pm) is larger than
+ –
N2BF4 NO2 the size of the tetrahedral site, so it cannot be slipped into it.
9. (i) The structure of H 4P2O 7 (pyrophosphoric) is as follows :
NaNO2
5. + N2 + NaBF4
Cu, D
P P OH
Diazonium Nitrobenzene HO O OH
Fluoroborate OH
The product formed is nitrobenzene (H4P2O7)
6. Gallium contains only three valence electrons ( ns 2np1 ). When (ii) The structure of HOClO 3 (perchloric acid) is as follows:
germanium is doped with gallium the dopant atoms occupy
H
some of lattice sites. Gallium being trivalent the fourth valence O
electron is missed is called hole. These holes move
throughout the crystal like a positive charge and increase the Cl
conductivity of germanium crystal. It is called p-type
semiconductor.
Positive hole (no ectron) Perchloric acid
(HOClO3)
Ge Ge Ge Ge 10. Given that mass of solute (W B ) = 1.25 g
Ge Ge Ge Trivalent impurities Mass of solvent (W B ) = 99 g
atom gallium
Ge Ge Ge Ge Elevation in boiling point ( DTb ) = 80.31 - 8010
.
. °C
= 021
(p-type) Semiconductor
K b = 2.53 ° C kg mol -1
7. The electrode potential for Mg electrode varies according to W B ´ 1000
the equation Now from, DT = K b
WA ´ M B
0.059 1
EMg 2 + /Mg = E ° - log 2.53 ´ 125
. ´ 1000
Mg 2 + /Mg 2 [Mg 2+ ] 0.21 =
0.0591 99 ´ M B
EMg 2 + /Mg = E ° + log [Mg 2+ ] 2.53 ´ 1.25 ´ 1000
Mg 2 + /Mg 2 or MB =
0.0591 99 ´ 0.21
EMg 2 + /Mg = log [Mg 2+ ] + E ° 2 +
2 Mg /Mg
M B = 152.116 g

77
11. (i) Vapour phase refining It is the process of refining of 0.0591 [Cd 2+ ]
020
. = 015
. - log
metal by converting of it into its volatile compound and 2 2
then decomposing it to obtain a pure metal. For this [Cd 2+ ]
process to occur. log = - 1.6920
2
(a) The metal should form a volatile compound with a
log[Cd 2+ ] - log 2 = - 16920
.
suitable reagent.
(b) The volatile compound should be easily decomposed so log[Cd 2+ ] = - 16920
. + 0.3021 = - 13879
.
that the metal can be easily recovered [Cd 2+ ] = antilog 2 .6121 = 0.0409 M
e.g. Nickel, zirconium and titanium are refined using this 14. (i) Carbon and nitrogen atoms have almost same size.
method. They can make triple bond to form C ºº N - ion in which
(ii) Electrolytic refining It is the process of refining impure pp- pp multiple bond is possible. But similar
metals by using electricity. In this process, the anode is pp - pp multiple bonding is not possible between carbon
made up of impure metal and the cathode is made up of and phosphorus atom due to large atomic size of
a strip of pure metal. A solution of a soluble salt of the phosphorus.
sample metal is taken as the electrolyte. When electric Hence, C ºº P - ion does not exist.
current is passed, metal ions from the electrolyte are (ii) Hypophosphorous acid or phosphinic acid (H 3 PO 2 ) is
deposited at the cathode as pure metal and equivalent monoprotic acid.
amount of impure metal from the anode dissolve into the
electrolyte in the form of ions. The impurities present in
the impure metal get collected below the anode, which P
is known as anode mud. H OH
+
H
Anode : M ® M n + e - The P ¾ H bonds are not ionisable to give H + and do not
Cathode : M n+ -
+ ne ® M play any role in basicity Only those H-atoms which are
(a) Raoult’s law The relative lowering of vapour pressure of attached with oxygen in P—OH form are ionisable and
12.
the solvent for a solution is equal to the mole fraction of cause the basicity. Thus, H 3PO 2 is monobasic or
the non-volatile solute. monoprotic acid because it have only 1 ionisable
H-atom.
The mathematical expression can be written as
(iii) Chlorine is strong oxidising agent, hence, when it reacts
p°1 - p1 n2 é n2 ù
= êsince X 2 = ú with KI liberates I 2. So, the colour of the solution
p°1 n1 + n2 ë n1 + n2 û becomes brown.
Here, n1 and n2 are the number of moles of solvent and Cl 2 + 2KI ( aq ) ¾¾® 2KCl + I 2
solute respectively present in the solution. Brown
When chlorine is present in excess, its bleaching action
(b) The dimerisation reaction
Dimerisation starts and the solution becomes colourless.
2C 6H 5COOH ¾¾® (C 6 H 5 COOH )2 Cl 2 + H 2O ¾® 2HCl +[O ]
i -1 i -1 [O ] + coloured solution ¾¾® Colourless solution
a = = 0.84= = 0.84
1 1 15. (a) In [CoF6 ]3- , oxidation state of cobalt is +3.
-1 -1
n 2 3d 4s 4p 4d
0.84 Co-atom
i = 1- = 1 - 0.42 = 0.58 (Z=27)
2
Molecular mass of benzoic acid = 122 g mol -1 Co3+ ion
0.61 ´ 1000
DTb = iK b × m [Q m = ] Formation
122 ´ 50 of [CoF6]3–
× ××× ××
= 0.58 ´ 2.3 ´ 01
. = 01334
. °C Electron pair donated by six F– ion
Tb = Tb° + DTb
The F - ion is weak ligand and is unable to pair up the
= 46.2 + 01334
. = 46.334° C
unpaired electrons of the 3d orbital. It is highly
13. The complete cell reaction is paramagnetic because of presence of four unpaired
Cd + Ni 2+ ¾® Cd 2+ + Ni electrons.
°
Ecell = - 0.25 - ( -0.40) = 015
. V (b) [Cr(H 2O )4 Cl 2 ]+ shows geometrical isomerism because it
By applying Nernst equation is a MA 4 B2 type coordination compound which contains
0.0591 [Cd 2+ ] two set of equivalent ligands, four H 2O and 2Cl. Hence,
°
Ecell = Ecell - log the possible geometrical isomers are
2 [Ni 2+ ]

78
Cr Cr In this mechanism electrophile Cl + attacks to electron
H2 O H2O H2O Cr
rich benzene ring and replaces hydrogen. So, the
reaction is electrophilic substitution reaction.
Cr and Cr
(ii) The chlorobenzene is formed in this reaction
H2 O H2O H2O H 2O + –
NH3 N2Cl Cl
Cr H 2O NaNO2 + HCl Cu2Cl2
+ N2
trans-isomer cis-isomer

(c) Crystal field stabilisation energy (CFSE) for octahedral Nitrobenzene Y


Chlorobenzene
and tetrahedral complexes are closely related to each
4 (iii) The haloalkanes are slightly soluble in water. In order for
other by formula, D t = D o a haloalkane to dissolve in water, energy is required to
9
overcome the attractions between the haloalkanes
where, D o = CFSE for octahedral compxes and
molecules and break the hydrogen bonds between
Dt = CFSE for tetrahedral complex.
water molecules. Less energy is released when new
According to question, D o = 18000 cm -1 attraction are set up between the haloalkane and water
4 4 molecules as the bond is not as strong as the original
Dt = D o = ´ 18000 cm -1
9 9 hydrogen bonds in water. As a result, the solubility of
= 4 ´ 2000 cm -1= 8,000 cm -1 haloalkanes in water is low.
(i) The catalytic reaction which depends upon the pore 18. The functional isomers of C 3 H 6O containing carbonyl groups
16.
structure of the catalyst and size of the reactant and are
product molecules is called shape-selective catalysis. CH 3CH 2CHO and CH 3COCH 3
Zeolites are good shape-selective catalyst because of Propanal Propanone
their honey comb like structures. They are microporous Propanal, CH 3CH 2CHO will reacts faster with HCN because
aluminosilicates with three dimensional network of there is less steric hindrance and electronic factors, which
silicates in which some silicon atoms are replaced by increases its electrophilicity.
aluminium atom giving Al — O — Si framwork. The The amechanism is as follows:
reaction taking place in zeolites depends upon the pores HCN + OH – 1 · –
·CN + H 2O

and cavities of the zeolites.


H d+ d– O OH
(ii) Physisorption is a process in which adsorbate gets – H+
C O + CN C C
adsorbed on the adsorbent surface by weak van der H CN CN
Waals’ force of attraction. On increasing temperature the
Tetrahedral Cyanohydrine
interaction between adsorbate and adsorbent becomes intermediate
weak and adsorbate particles get desorbed.
The reaction does not lead to completion because it is a
(iii) Because the CMC (critical micelle concentration) for
reversible reaction and equilibrium is established.
soap solution is 10 -4 - 10 -3 mol L -1 and it forms micelle
in this concentration range. On dilution soap solution If strong acid is added to the reaction

mixture the reaction is
behaves as a normal electrolyte and after adding excess inhibited because production of C N ion is prevented.
of water intermolecular forces of attraction between the 19.(i) (a) Aniline is primary amine and N-ethylaniline is secondary
soap particles decreases and soap solution may revert amine. The distinction can be made with the help of
back to individual ions. carbyl amine reaction which is given by primary amine
17. (i) Toluene reacts with a halogen in the presence of iron (iii) and not by secondary amine.
chloride giving ortho and para halocompounds. The NH3 N C
reaction is electrophilic substitution reaction.
Heat
Mechanism: + CHCl3 + 3KOH + 3KCl + 3H2O
FeCl3 – +
Cl—Cl FeCl4 + Cl
(b) N-methylpropane-2-amine is a secondary amine while
N–ethyl-N-methylethanamine is a tertiaryamine. The
CH3 CH3 CH3 distinction can be done with the help of Hinsberg’s
H reagent which is benzene sulphonyl chloride.
+Cl+ Cl or
R R
S Cl + H N S N
H Cl R –HCl R

CH3 CH3
Benzene sulphonyl 2º amine N,N-dialkyl
H Cl chloride benzenesulphonamide
– (insoluble in KOH)
Cl + (FeCl4) + HCl + FeCl3

79
The tertiary amine does not react at all since it does not (b) The moner used in polythene is CH 2 == CH 2
contain replaceable hydrogen on nitrogen atom. 350 - 570K –
(ii) The increasing order of basic strength of methyl n(CH 2 == CH 2 ) ¾-¾® ¾(CH 2 — CH 2 )¾
n
Ethene Traces of oxygen Polyethene
substituted amines is
(ii) The increasing order of tensile strength is
NH 3 < N(CH 3 )3 < CH 3 NH 2 < (CH 3 )2NH
Buna - S< Polythene < nylon -6
There is a subtle interplay of the inductive effect,
solvation effect and steric hinderance of the alkyl (iii) Condensation polymers These are formed by repeated
group which decides the basic strength of alkyl amines condensation reaction between two different bifunctional
in the aqueous state. or trifunctional monomeric units. In this polymerisation
reaction, the elimination of small molecules such as water
20. (a)(i) Wolff-Kishner reduction The carbonyl group of alcohol, hydrogen chloride etc., takes place. The
aldehyde and ketones is reduced to CH 2 group on
examples are terylene (dacron) nylon 6, 6, nylon 6, etc.
treatment with hydrazine followed by heating with
nH 2N(CH 2 )6NH 2 + nHOOC (CH 2 )4 COOH
sodium or potassium hydroxide in high boiling solvent
such as ethylene glycol. Hexamethylene ¯ Adipic acid
NH2 NH2 KOH/ethylene ¾[ NH(CH 2 )6NHCO(CH )2CO ¾ ]4 + nH 2O
C O C NNH2 CH2 + N2
glycol, heat Nylon 66
22. (i) On oxidation with nitric acid glucose as well as gluconic
(ii) Haloform reaction Aldehydes and ketones having at
acid both yield saccharic acid. This indicates the
least one methyl group linked to the carboxyl carbon
presence of primary alcoholic (—OH) group in glucose.
atom (methyl ketones) are oxidised by sodium
hypohalite to sodium salts of corresponding carboxylic CHO COOH COOH
acids having one carbon atom less than that of
carbonyl compound. The methyl group is converted to (CHOH)4 Oxidation (CHOH)4 Oxidation (CHOH)4
haloform.
CH2OH COOH CH2OH
e.g.
H CH3 H CH3 Glucose Saccharic acid Gluconic acid
NaOCl
C C C C + CHCl3
CH3 ONa
H3C C H3 C C (ii) Peptide linkage Proteins are the polymers of a-amino
acid and they are connected to each other by peptide
bond or peptide linkage. Peptide linkage is an amide
(b) Acetaldehyde to acetone formed between —COOH group and —NH 2 group. The
K 2Cr 2O 7 /H 2SO 4 Ca(OH)2
CH 3CHO ¾¾¾® CH 3COOH ¾¾® reaction between two molecules of similar or different
Acetaldehyde oxidation Acetic acid Heat amino acid, proceeds through the combination of the
Heat amino group of one molecule with the carboxyl group of
(CH 3COO)2 Ca ¾¾® CH 3COCH 3 the other. This result in the elimination of a water molecule
—CaCO 3 Acetone
Cal.acetate
and formation of peptide bond —CO—NH.
or
H2N—CH—COOH + H2N—CH—COOH
Cd –H2O CH3
2
(a) (i) Cl + HCl
Dry ether
Benzophenone H2N—CH2—CO—NH —CH—COOH
OCOCH3
CH3 CH CHO Peptide linkage CH3
OCOCH3

(ii) (i) CrO3 (ii) H2O/OH– 5 5


+ 2CH3COOH O – O
(iii) HO—H2C Base, O—P—O—H2C Base
(CH3CO)2O Hydrolysis
4 – 4
(b) Molecular mass of aldehyde (C n H 2nO ) = 44u H H 1 O H H 1
12 ´ n + 2 ´ n + 16 = 44 H 3 2 H H 3 2 H
14n = 44 - 16 = 28
OH OH OH OH
n=2
Nucleoside Nucleotide
Molecular formula of aldehyde is C 2 H 4O
23. (i) Narcotic analgesics
CH3 C +C CH3 CH3 CH CH CH3 (ii) Saccharin, aspartame etc.
(iii) Aspirin is used in the prevention of heart attack because
H H But-2-ene
of its antiblood clotting action.
21. (i) (a) The monomer used in teflon is CF2 == CF2 (iv) Values shown by Delhi government - caring, awareness
Polymerisation
nCF2 == CF2 ¾-¾® —
( CF2 — CF2—
) n and conscious towards the health of poor peoples.
Tetrafluoro ethylene

80
2 4 H SO (a) The reaction follow SN 1 mechanism
24. (a) CH 3CH 2OH ¾¾® CH 2 == CH 2 + H 2O
443 K Mechanism
CH3 CH3
Mechanism
+ Slow +
Step1 Formation of protonated alcohol CH3 C O CH3 CH3 C + CH3OH
H H H H H
Fast CH3 H CH3
+
H C C O H + H+ H C C O H (3º-carbocation)

H H H H CH3 CH3
Ethanol Protonated alcohol + – Fast
(Ethyl oxonium ion) CH3 C +I CH3 C I

Step 2 Formation of carbocation It is the slowest step and hence, CH3 CH3
the rate determining step of the reaction (b) Reimer-Tiemann reaction On treating phenol with
H H H H H chloroform in the presence of sodium hydroxide a
+
Slow + —CHO group is introduced at ortho position of benzene
H C C O H H C C + H 2O
ring. This reaction is known as Reimer Tiemann
H H H H reaction. – +
OH ONa
Step 3 Formation of ethene by elimination of proton CHCl2
H H
H H CHCl3+aq NaOH
+
H C C C C +H+
H Ethene H
H H Intermediate

(b) Phenol to benzoic acid ONa+ OH
OH CH3 CHO CHO
+
NaOH H
Zn dust CH3Cl, Anhyd.
(i)
–ZnO AlCl3 Salicylaldehyde
Phenol Benzene Toluene (c) o-nitrophenol is more volatile than p-nitrophenol due to
COOH
presence of intramolecular hydrogen bonding. In
para-nitrophenol intermolecular hydrogen bonding is
Alk. KMnO 4 present. This intermolecular hydrogen bonding causes
(oxidation)
the association of molecules.

Benzoic acid O H
N
O
Cl OH OH HO N
O HO N
NaOH HNO3 O
(ii)
623K / 300 atm H2SO4 o-nitrophenol p-nitrophenol
(Intramolecular H-bonding) (Intermolecular H-bonding)
Chloro
benzene NO2 25. (i) It is because oxygen forms multiple bonds with transition
p-nitrophenol metals but fluorine does not form multiple bonds.
OH OH (ii) Copper has lower hydration enthalpy which is unbable to
Br Br
compensate the sum of first and second ionisation
+ 3Br 2 enthalpy.
(iii) The actinides have higher ionisation enthalpies then
lanthanides because 5f orbital is more effectively
Br shielded from nuclear charge than 4f.
2,4,6-tribromophenol
(iv) It is because dichromate ions get reduced to chromium
CH3 CH3 ions in acidic medium.
(v) The actinides show more number of oxidation states
(c) CH3 C O CH3 + HI CH3OH + CH 3 C I
than lanthanides because in actinides 5 f, 6d and 7 s
CH3 CH3 orbitals have comparable energies.

or

81
or = k = 2.5 ´ 10 -4 Ms -1
(i) (a) Oxidation states of transition elements differ from Hence, the rate of production of N2 is
each other by unity. In non-transition elements, oxidation d [ N2 ]
= 2.5 ´ 14 -4 Ms -1
states normally differ by a unit or two. dt
(b) In transition elements, higher oxidation states are And the rate of production of H 2 is
favoured by heavier elements whereas in non-transition d [H 2 ]
elements, lower oxidation state is favoured. = 3 ´ 2.5 ´ 10 -4 Ms -1
dt
(ii) (a) 2MnO -4 + H 2O + I - ¾® 2MnO 2 + 2OH - + IO -3 = 7.5 ´ 10 -4 Ms -1
Acid (pH < 7)
(b) 2CrO -4 + 2H + - Cr2O 27- + H 2O or
Alkali (pH > 7)
(i) The rate of reaction is the change in the concentration of
513 K either the reactants or products per unit time.
(c) 2KMnO 4 ¾¾® K 2 MnO 4 + MnO 2 + O 2
(i) The sum of the powers of the concentration of the (ii) For a zero order reaction,
26.
reactants of a chemical reaction in the rate law 1
k = {[ A 0 ] - [ At ]}
expression is known as the order of that chemical t
reaction. 1
\ t = {[ A 0 ] - [ At ]}
(ii) Let the concentration of the reactant A, [ A ] = a and the k
concentration of the reactant B, [B] = b Given, k = 0.0030 mol L -1 s -1
So, rate fo reaction, R = k[ A ][B]2 = kab 2 A 0 = 010. M
(a) When the concentration of reactant B is increased three At = 0.075 M
times, the rate of the reaction would be Substituting values,
R ¢ = K a ( 3b )2 = 9kab 2 = 9R ...(i) 1
t = . - 0.075] = 8.33 s
[010
Therefore, the rate of the reaction would become 9 times 0.0030
of the initial rate. Therefore, it will take 8.33 s to fall concentration of A
(b) When the concentration of both the reactant are from 0.10 M to 0.075 M.
doubled, the rate of the reaction would be (iii) Radioactive decay follows first order kinetics.
R ¢ = k(2 a )(2 b )2 = 8kab 2 = 8R 0.693 0.693 -1
k= = yr
t 1/ 2 5730
Therefore, the rate of the reaction would become 8 times
of the initial rate. 2.303 [ A ]0 2.303 100
t = log = log
(iii) Rate of the given reaction is given by k = 2.5 ´ 1010 Ms -1 k [ A ] ( 0.693 / 5730 yr -1 ) 80
2.303 ´ 5730
Therefore, for the given reaction, rate is given by = ´ 0.0969 yr = 1845 yr
1 d [NH 3 ] d [N 2 ] 1 d [H 2 ] 0.693
- = =
2 dt dt 3 dt

82
General Instructions
(a) All questions are compulsory.
(b) Q.no. 1 to 5 are very short answer questions and carry 1 mark each
(c) Q.no. 6 to 10 are short answer question and carry 2 marks each.
(d) Q.no. 11 to 22 are also short answer questions and carry 3 marks each.
(e) Q.no. 23 is a value based question and carry 4 marks.
(f) Q.no. 24 to 26 are long answer questions and carry 5 marks each.
(g) Use log tables if necessary use of calculators is not allowed.

Very Short Answer Type Questions 9. Find out the oxidation state and number of unpaired
1. How much portion of an atom located at corner of a electron of chromium ion in cis-[Cr(en)2 Cl2 ]Cl and
cubic cell lattice? [Mn(H2 O)6 ] SO4 .
2. Suggest two materials other than hydrogen that can or
be used as fuels in fuel cells. Write down the limitations of CFT.
3. What happens when a beam of light is passed
through a colloidal solution? Ea
Slope = – —–
4. What happens when optically active alkyl halides R
react with NaOH?
10. log10 k Intercept = log A
10

5. Deficiency of which vitamin causes convulsion?


1/T
Short Answer Type Questions (I)
From this graph, give the answers.
6. Write the formula of aspirin and its IUPAC name. (i) If temperature increases, what effect on log10 k
Why should it not be taken on empty stomach? takes place?
7. Why formaldehyde is more reactive than (ii) If activation energy increases, what effect on
acetaldehyde towards nucleophilic addition log10 k takes place?
reaction?
Short Answer Type Questions (II)
8. Predict the product.
11. Explain why ortho-nitrophenol is more acidic than
Anhy. AlCl3 ortho-methoxy phenol?
(i) + C6H5COCl ?
CS2
12. Explain with giving two examples to show the
CH3 anomalous behaviour of fluorine.
13. Give reasons for the following:
(i) CrO2Cl2
(ii)
(ii) H3O+
? (i) Why Fe3 + is more stable than Fe2 + ion?
(ii) Why does V2 O5 act as catalyst?
NO2 (iii) Why La(OH)3 is stronger base than Lu(OH)3 ?

77
14. Write down about the following name reactions : 22. (i) How many isomers are possible for
[Co(NH3 )3 Cl3 ]?
(i) Reimer-Tiemann reaction
(ii) What is the difference between the
(ii) Oxymercuration and demercuration of alkenes
[Co(CN)6 ]3 - and [CoF6 ]3 - ?
15. Give reason for the following :
Value Based Question
(i) Sulpha drugs work like antibiotics but they
are not antibiotics. 23. Mohan is a farmer and has 33 acres of land on which
he has grown crops. One day two of his friends come
(ii) Aspirin helps in the prevention of
heart-attack. to visit him. He takes them to show his crops
proudly. One of his friend notices some infection on
(iii) Soaps are biodegradable where as detergents
are non-biodegradable. the leaves of his crops. He advises him to use DDT.
The other friend instead advises him to use dry
16. (i) What is the role of benzoyl peroxide in
powder of neem leaves as an insecticide.
polymerisation of ethene?
(i) Whose advice should Mohan take and why?
(ii) What do you understand by functionality of a
monomer? (ii) What effects can DDT pose?
17. Write chemical reactions for the following: (iii) Write the values associated with the above
decision.
(i) Reaction of ethyl bromide with NH3 .
(ii) Ammonolysis of benzyl bromide followed by Long Answer Type Questions
its reaction with two moles of MeBr. 24. Find out the B, C, D in
(iii) Heating of acylazide followed by hydrolysis. O
Me
18. Calculate the freezing point depression for 0.0711 m (i) MeCHO
LDA
aqueous solution of Na 2 SO4 . If this solution freezes B (ii) H2O
C
at – 0.320°C, what would be the value of van’t Hoff (i) OH–
factor? (Kf for water is 1.86°C mol -1 ) (ii) MeCHO

C+D
19. Give account for the following:
or
(i) Role of silica in the metallurgy of copper.
Find out A, B, C and D in the following reaction
(ii) Role of cryolite in the metallurgy of Al.
(iii) Froth floatation process (only principle). O3 /Red (i) aq. Na 2CO3
B
A (ii) D
20. (i) Describe the mechanism of the addition of
Grignard reagent to the carbonyl group
followed by hydrolysis to yield an alcohol. (i) LAH Pd/C
C D
(ii) Complete the following reaction sequence: (ii) H2O D

O
25. (i) Complete the following reactions:
½½ (i) CH 3MgBr Na
CH3 ¾ Br
CH3 ¾ C ¾ CH3 ¾¾¾® A ¾® B¾¾® C (a) XeF6 (s) + H2 O(l) ¾®
(ii) H 2O Ether
(b) XeF2 + H2 O ¾®
or (c) XeF4 + H2 O ¾®
An organic compound with molecular formula (ii) Explain ‘no distinct chemical compound of
C9 H10 O forms 2,4-DNP derivatives, reduces helium is known’.
Tollen’s reagent and undergoes or
Cannizzaro reaction. On vigorous oxidation, it (i) Draw the structural formula and hybridisation
gives 1, 2-benzene dicarboxylic acid. Identify the of the compound XeF4 .
compound. (ii) Explain why XeF2 is a linear molecule without a
bent.
21. Account for the following :
(i) pKb of aniline is more than that of methyl 26. Discuss the effect of pressure and temperature on
amine. the adsorption of gases on solids. Describe the
application of adsorption in controlling humidity.
(ii) Methyl amine in water reacts with FeCl3 to
precipitate hydrated ferric oxide. or
Action of soap is due to the emulsification and
micelle formation comment.
Detailed solution of these questions are available on http://www.arihantbooks.com/Chemistry%20Spectrum.pdf

78
Explanations
1. An atom at the corner of a cubic cell is shared by eigth (i) CFT does not tell about the covalent character of bonding
neighbouring unit cells. Hence, 1/8th portion of an atom between the ligand and central metal atom.
located at corner. (ii) It does not explain why the anionic ligands are found at the
2. Methane (CH 4 ) and methanol (CH 3OH) can be used as fuels in lower end of the spectrochemical series.
fuel cells. 10. (i) k = A e - E a / RT
3. When a beam of light is passed through a colloidal solution, Ea
scattering of light takes place and the path of light becomes log10 k = log10 A -
RT
visible.
If temperature increases, log10 k also increases.
4. When optically active alkyl halides react with NaOH, SN 2 (ii) E a increases, log10 k decreases.
reaction takes place followed by the inversion of
configuration. 11. Due to strong –R and –I-effect of the ¾ NO 2 group, electron
density in the O ¾ H bond decreases and loss of H + becomes
5. Due to deficiency of vitamin B 6, convulsions occur.
easier. Also o-nitrophenoxide is stabilised by resonance.
OCOCH3
H O O H rO H s
COOH O O
IUPAC name : 2 -acetoxy benzoic acid NO2 r
N N
6. s O
s
O and so on
Aspirin

Aspirin generates salicylic acid on hydrolysis and should not –I and –R-effect
be taken on empty stomach because the acid might damage But due to +I-effect of —OMe in o-methoxy phenol, enhances
to cell walls. electron density in the ring and hence it is very difficult
O O to loose a proton and after loosing the proton it is
½½ ½½ destabilised by resonance and becomes less acidic than
7. H ¾ C ¾ H CH 3 ¾ C ¾ H o-nitrophenol.
Formaldehyde Acetaldehyde s
s
OH O O
Due to the attachment of electron donating group to carbonyl r
s
group in acetaldehyde, it enhances the electron density which OCH3 O CH3 OCH3
reduces the reactivity towards nucleophilic addition reaction.
COC6H5
12. The anomalous behaviour of fluorine is due to its smaller size,
Anhyd. AlCl3 highest electronegativity, low F ¾ F bond dissociation
8. (i) + C6H5COCl CS2 + HCl
enthalpy and non-availability of d-orbitals in its valence shell.
Benzene Benzophenone The two examples are :
(i) F-forms only one oxo-acid while other halogens form a
CH3 CH(OCrCl2OH)2 CHO number of oxo-acids.
(ii) HF is liquid due to strong H-bonding while other HX are
(i) CrO
r gases.
2Cl2 (ii) H3O
(ii)
Etard's reaction
13. (i) Fe 3+ = [Ar]18 3d 5
Fe 2+ = [Ar]18 3 d 6
NO2 NO2 NO2
Due to stable electronic configuration of Fe 3+ , it is more
p-nitrotoluene p-nitrobenzaldehyde
stable than Fe 2+ .
9. Let the oxidation state be ‘ x’.
(ii) Because it has a large surface area. It can form unstable
So, in cis-[Cr(en)2Cl 2 ]Cl
intermediates which readily change into products.
x + ( 0) ´ 2 + ( -1) ´ 2 + ( -1) = 0
(iii) Due to lanthanoid contraction, the size of Lu3+ is smaller
x= +3 than that of La 3+ ion, that’s why Lu ¾ O bond is
Thus, Cr 3+ = [Ar]18 3d 3 stronger than La ¾ O bond, hence La(OH)3 is stronger
n= 3 base.
In [Mn(H 2O)6 ] SO 4 , Mn2+ has [Ar]18 3d 5 14. (i) In Reimer-Tiemann reaction, reaction of phenol with
\ n=5 CHCl 3 in the presence of aqueous alkali at 340 K followed
x + 0 ´ 6 = + 2, x = + 2 by hydrolysis forms salicylaldehyde as the major
or product.

79
OH ONa ONa \ . K kg mol -1 ´ 0.0711 mol kg -1 = 0132
DTf = 186 . K
Observed value of DTf 0.320 K
CHCl2 CHO \ i = = = 2.42
CHCl3 + NaOH (aq) NaOH Calculated value of DTf 0132
. K
340 K
19. (i) Silica acts as a flux to remove FeO, impurity, as slag
Phenol OH FeSiO 3 in the metallurgy of copper.
FeO + SiO 2 ¾® FeSiO 3
CHO Flux Slag
H3O
r (ii) Cryolite lowers the fusion temperature of the bath from
2323 K to about 1140 K.
Salicylaldehyde (iii) In this process, hydrophobic sulphide ores are
(ii) When alkene reacts with mercuric acetate in presence of preferentially wetted by oil, whereas the hydrophilic
THF and water it gives hydroxy mercurial compound. gangue particles are wetted by water.
This is called ‘oxymercuration’, but when NaBH 4
reduces ¾ HgOAc and replaces with hydrogen it is 20. (i) Mechanism
called as demercuration. Step I The nucleophilic addition of Grignard reagent to the
carbonyl group forms an adduct.
Hg(OAc)2
CH3—CH2—CH==CH2 CH3CH2 —CH— CH2 dr sr
THF, H2O ds

1-butene C O Mg X
C O +R Mg X
OH HgOAc
CH3—CH2—CH—CH3 NaBH4 R

Adduct
OH Step II Hydrolysis of adduct gives alcohol.
2-butanol
sr H2O X
15. (i) Because sulpha drugs are purely synthetic while C O Mg X C OH + Mg
antibiotics may be either wholly or partially obtained OH
from microorganisms. R R
Alcohol
(ii) Because of its anti-blood clotting action. O OH
(iii) Soap molecules have straight hydrocarbon chains which ½½ (i) CH 3MgBr ½ Na
are easily degraded by bacteria but detergent (ii) CH 3 ¾ C ¾ CH 3 ¾¾¾® CH 3 ¾C ¾ CH 3 ¾®
(ii) H 2O ether
molecules have branched hydrocarbon chains which ½
are not degraded by bacteria present in sewage water. CH 3
3°alcohol
16. (i) Benzoyl peroxide acts as an initiator in the chain A
È Å
reaction. It dissociates to give radicals. O Na OCH 3
O O ½ ½
CH ¾Br
½½ ½½ CH 3 ¾ C ¾ CH 3 ¾ ¾3 ¾¾® CH 3 ¾C ¾ CH 3
C 6 H 5 ¾ C ¾ O ¾ O ¾ C ¾ C 6 H 5 ¾® ½ ½
O CH 3 CH 3
½½ • B C

2C 6 H 5 ¾ C ¾ O ¾® 2 C 6 H 5 + CO 2 2-methyl-2-methoxy propane
Phenyl or
radical
(i) Given compound with molecular formula C 9 H10 O forms
(ii) Functionality of a monomer, means the number of
a 2, 4-DNP derivative and reduces Tollen’s reagent, thus,
bonding sites in a molecule, e.g. 1, 3-butadiene has two
it must be an aldehyde.
while propene has one functionality.
(ii) As it undergoes Cannizzaro reaction, hence CHO group
17. (i) CH 3CH 2 ¾ Br + NH 3 ¾® CH 3CH 2NH 2 + HBr is directly attached to the benzene ring.
¯ Et ¾ Br (iii) On vigorous oxidation, it gives 1, 2-benzene dicarboxylic
Et ¾Br
HBr + (CH 3CH 2 )3N ¬ ¾¾ ¾ (CH 3CH 2 )2NH + HBr acid. It must be an ortho-substituted benzaldehyde which
N, N-diethyl ethanamine has molecular formula C 9 H10 O is o-ethyl benzaldehyde.
(ii) PhCH 2 Br + NH 3 ¾® PhCH 2NH 2 21. (i) Due to resonance, the lone pair of N-atom in aniline is
Me delocalised which reduces the electron density on
2MeBr ½ N-atom but in o-methyl amine electrons are localised
¾® PhCH 2 ¾ N ¾ Me and enhances the electron density which favours the
N, N-dimethylphenyl
methanamine
less basicity of aniline and hence more value of pK b .
O (ii) CH 3 ¾ NH 2 being more basic than water, accepts a
½½ (i) D proton from water liberating OH - ions. These OH - ions
(iii) R ¾ C ¾ N 3 ¾® R ¾ NH 2 + CO 2 combine with Fe 3+ ions to form brown precipitate of
(ii) H 2O
hydrated ferric oxide.
18. DTf = [27315
. - ( -0.320 + 273.15)] K = 0.320 K FeCl 3 ¾® Fe 3+ + 3Cl -
3+
Q DTf = K f × m 2Fe + 6OH - ¾® 2Fe(OH)3 or Fe 2O 3 × 3H 2O
Hydrated ferric oxide (Brown ppt.)

80
22. (i) Only two isomers are possible (ii) In XeF2, Xe in sp3d hybridised having 2 bond pairs and 3 lone
NH3 NH3 pairs. In order to acquire minimum repulsion F
Cl NH3 Cl NH3 between the bond pairs and lone pairs, the
Xe
Co Co 3 lone pairs are arranged at equitorial
position and the 2 bond pairs lie at axial F
Cl NH3 Cl Cl
Cl NH3 position. Hence, the structure of XeF2 is
Cis Trans linear as shown below.
(ii) Due to the presence of strong CN - ligand [Co(CN)6 ]3- is 26. (i) Effect of pressure We have the Freundlich adsorption
low spin complex having d 2sp3 hybridisation while due x
isotherm for pressure, = k × p1/ n.
to the presence of weak ligand [CoF6 ]3- forms high spin m
complex having sp3d 2 hybridisation. At low pressure, Freundlich adsorption isotherm curve is
23. (i) Since neem powder is natural biodegradable x x
almost sloping and linear µ p or = kp.
insecticide, while DDT is a synthetic non-biodegradable m m
insecticide. Mohan should take the advice of the friend x
asking to use neem. At high pressure, curve becomes straight line, µ p0 or
m
(ii) DDT leads to soil and water pollution. It affects different x x x
= kp0. At intermediate pressure µ p1/ n Þ = kp1/ n
organs in humans like liver and kidneys. m m m
(iii) Values associated with the above decission are concern Value of 1/ n falls between 0 and 1.
towards a better environment.
(ii) Effect of temperature Adsorption is an exothermic process.
O Os Li r O OH
Therefore, in accordance with Le-Chatelier’s principle, the
24. Me Me Me b magnitude of adsorption increases with decrease in
(i) MeCHO a Me
LDA temperature. Actually, physisorption increases with decrease
(ii) H2O
in temperature but chemisorption first increases then
(i) OH– B C
(ii) MeCHO Li-enolate decreases with increase in temperature.
O O OH Application Silica and aluminium gels adsorb humidity from
Me air, hence are commonly used, for storage of delicate
Me
HO + Me instruments which might otherwise be damaged by moisture.

Me D C
O O x x
m m
O3/Red Intramolecular
aldol
T T
Physisorption Chemisorption
D or
A –H2O
When grease or oil on the cloth comes in contact with soap
OH O solution the stearate ions arrange themselves in such a way
that its hydrophobic part is in the oil (or grease) and the
Pd/C (i) LAH hydrophilic parts project outside the grease droplet like
D (ii) H 2O bristles.
Grease
C B Cloth

Pd/C Water
(a)
D
Soap solution
Azulene Oil
D droplet
or
25. (i)(a) XeF6( s ) + H 2O ¾® XeOF4 + 2HF
(b) 2XeF2 + 2H 2O ¾® 2 Xe + 4HF + O 2 (b) (c)
(c) 6XeF4 + 12H 2O ¾® 4 Xe + 2XeO 3 + 24HF + 3O 2
As the hydrophilic part is polar, these polar groups can
(ii) No distinct chemical compound of He is known because of its interact with the water molecules present around the oil
small size and high ionisation energy. droplet which is pulled away from the surface of the cloth into
or water to form ionic micelle. Thus. soap helps in emulsification
F F and washing away of oils and fats. The negatively charged
(i) Xe sheath around the globules prevent them from coming
F together and forming aggregates. It is then washed away with
F
the excess of water.
Hybridisation –sp3d2

81
Paper 1 (Multiple Options Correct) 7. Why As(Ph)3 cannot prepare tetraphenyl arsonium
1. A galvanic cell reaction is represented as ion with Ph — Br?
Cr(s)| Cr3 + (aq)|| Ni2 + (aq)| Ni(s). The voltage of the (a) Because triphenyl arsane is a much weaker nucleophile
than trimethyl arsane
above cell at 25°C when the concentration of Cr 3 + and
Ni2 + are respectively 0.010 M and 0.020 M is (Given (b) Because triphenyl arsane is a much stronger nucleophile
than trimethyl arsane
that E° 3 + = - 0.744 V and E° 2 + = -0.236 V)
Cr / Cr Ni / Ni (c) Because triphenyl arsane is a electrophilic in nature
(a) 0.497 V (b) 0.475 (c) 0.423 (d) 0.593 (d) None of the above
2. Correct reagent to convert back E into A is 8. Given below are the half-cell reactions
O3 Mg + Hg H +
LiAlH4 Mn2 + + 2e - ¾® Mn, E° = -1.18 eV
B C D E
Zn + H2O H2 O D H 2O 2 (Mn3 + + e - ¾® Mn2 + ), E° = + 1.51 eV

A The E° for 3Mn2 + ¾® Mn + 2Mn3 + would be


(a) -2.69 V, the reaction will occur
(a) Al 2 O 3 (b) SOCl 2
(b) -2.69 V, the reaction will not occur
(c) H 3 PO 4 (d) ThO 2 A
(c) -0.33 V, the reaction will not occur
3. The correct order of P—P bond length of the (d) -0.33 V, the reaction will occur
following compounds is
(a) P2 F4 < P2(CH 3 )4 < P2(CF3 )4 < P2 H 4
9. Which of the following represents the correct
(b) P2 F4 < P2(CF3 )4 < P2(CH 3 )4 < P2 H 4
structure of the final product (D) of the reaction
(c) P2 F4 < P2 H 4 < P2(CH 3 )4 < P2(CF3 )4 given below?
(d) P2 F4 < P2(CH 3 )4 < P2 H 4 < P2(CF3 )4 (ii) SOCl2 (i) K2CO3, H2O, D
OH D
A B C
4. In a solid having rock salt structure, if all the atoms (ii) Br2/NBS (ii) H3O+ Al2O3
(iii) HCl
touching one body diagonal planes are removed (i) Br—CH2—NO2, OH–
D
(except at body centre), then the formula of the (ii) H2O/H+
remaining unit cell is
(a) A 3.5B2.5 (b) A 3B5 (c) A 5B3 (d) A 7B3 (a) (b)
O NO2 OH
5. 0.0755 g of selenium vapours occupying a volume of
185 NO2
114.2 mL at 973 K exerts a pressure of atm. NO2
760
For the reaction, Se6 (g) 3Se2 (g),
` (c) (d)
OH
OH
degree of dissociation of Se is 0.59.
NO2
Select the correct answer.
(a) Value of K p is 0.1687 (b) KC = 0.2645 ´ 10 -4 10. Two inflated balloons I and Inner balloon
600mL (I)
2 II have volume 600 mL and
( 0.0821 ´ 293)
(c) KC = ( 0.0821 ´ 293)2 (d) K p = 1500 mL at 300 K as shown 600 mL
293
in the diagram. If
6. Calculate the solubility of 10-4 mol /L of TlN3 in a maximum volume of inner Outer balloon
1500 mL (II)
solution prepared by shaking excess of TlN3 and and outer balloons are 800
Tl3PO4 . The solution contains 1 mmol of PO34 - per mL and 1800 mL respectively then, find the
200 mL solution and Ksp (TlN3 ) = 5.6875 ´ 10-4 . balloon which will burst first on heating.
(a) 1.75 ´ 10 -2 (b) 3.5 ´ 10 -2 (a) Outer balloon (b) Inner balloon
(c) 1.75 ´ 10 -4 (d) 3.5 ´ 10 -4 (c) Both together (d) Data insufficient to predict

54
Section 2 Comprehension Type (Only one option correct) 14. Which of the following represents the structure of
This section contains 3 paragraphs each describing the aromatic compound producing yellow coloured
theory, experiments, data, etc. Each question has only one dye?
NH2 OH NH2
correct answer among the four options (a), (b), (c), (d) : N

Paragraph for Questions 11 and 12 (a) (b) (c) (d)


OH
Photosynthesis is the most vital part for the survival of
both plants and animals. In photosynthesis, green plants Paragraph for Questions 15 and 16
utilise CO2 and water to produce glucose and oxygen
Potassium permanganate acts as a strong oxidising agent
inside chloroplast. This reaction takes place in the
due to maximum oxidation state of Mn(+7) in KMnO4 . It is
presence of sunlight in which the chloroplast receives a
reduced either to MnO24 - , MnO2 or Mn2 + depending upon
light of particular wavelength. The D f H° and S° values for
different molecules involved during the reaction are given the concentration of H + ion in the solution. The E° value
below. for the reduction of MnO4- to MnO24 - , MnO2 and Mn2 + are
respectively 0.56 V, 1.69 V and 1.52 V.
Molecule D f H° S °(J mol -1K -1 )
15. The moles of electrons required for the reduction of
CO 2( g ) -393.5 213.2
one mole of potassium permanganate to Mn2 + in
H2O( l ) -285.8 69.9 acidic medium is
C 6 H12O 6( s ) -1273.3 212.1 (a) 3 (b) 5 (c) 8 (d) 4
O 2( g ) 0 205.0 16. During the reduction of permanganate ion to Mn2 +
in acidic medium, the concentration of Mn2 + and
11. The DG ° value for the formation of 1 molecule of MnO4- were respectively 1.0 ´ 10-3 M and
glucose at 300 K is around 2.0 ´ 10-3 M and the pH of the solution was 3. The
(a) 4.78 ´ 10 -18 J (b) 2.39 ´ 10 -18 J
reduction potential of MnO4- during this condition is
-18
(c) 2.39 ´ 10 kJ (d) 4.78 ´ 10 -18 kJ
(a) 0.62 V (b) 1.24 V
12. If all of the photosynthesis on earth stores (c) 1.56 V (d) 1.43 V
3.4 ´1018 kJ of energy, the number of moles of CO2
Section 3 Matching Type (Only One Option Correct)
removed from atmosphere by photosynthesis every
year is (take temperature as 300 K) 17. Match Column I and Column II, where Column I
(a) 7.1 ´ 10 15
(b) 3.55 ´ 10 15 represents the structure of the organic compounds
16 15 and Column II represents the reaction it gives or the
(c) 1.42 ´ 10 (d) 5.6 ´ 10
product it forms.
Paragraph for Questions 13 and 14 Column I Column II
In an experiment to prepare different coloured dyes, P. 1. Green colour with HNO 2
benzene diazonium chloride was treated with a suitable CH2NH2
aromatic compound in either acidic or basic medium. In
three different reactions of benzene diazonium chloride Q. 2. Insoluble alkali with
with three different aromatic compounds an orange dye, a OH Hinsberg’s reagent
yellow dye and methyl orange were obtained.
13. Which of the following represents the structure of R. 3. Orange dye with benzene
the aromatic compound producing orange coloured NH—CH3 diazonium chloride
dye?
NH2
N S. CH3 4. Carbylamine test
N
(a) (b) CH3

Codes
OH NH—C—CH3
P Q R S P Q R S
(a) 1 2 4 3 (b) 3 2 1 4
(c) (d) (c) 4 3 2 1 (d) 4 1 2 3

55
18. Match Column I and Column II, where Column I 20. Match Column I and Column II, where Column I
represents the axes of the graph and Column II represents the name of the method to remove
represents the structure of the graph. hardness of water and Column II represents the
Column I Column II chemical reaction involved during the removal of
hardness of water.
P. Amount of gas adsorbed per unit 1.
æ xö
mass of adsorbent ç ÷ versus Column I Column II
è mø
2-
temperature (T ) in physisorption P. Clark’s method 1. Na 4P6 O 18 + M 2+ ¾®
(pressure = constant) [Na 2 MP6O 18 ]2- + 2 Na + ( M = Ca , Mg )

Q. Synthetic resins 2. Ca (HCO 3 )2 + Ca (OH)2 ¾®


method 2 CaCO 3 + 2 H2O

Q. æ xö 2. R. Ion-exchange 3. 2 NaAlSiO 4 + M 2+ ( aq ) ¾®
ç ÷ versus T in chemisorption method
è mø M( AlSiO 4 )2( s ) ¯ + 2 Na + ( aq )
(pressure = constant) ( M = Ca , Mg )
2+
S. Calgon’s 4. 2 RNa( s ) + M ( aq ) ¾®
method
R2M( s ) + 2 Na + ( aq ) (R = alkyl group
and M = Ca , Mg)

R. æ xö 3. Codes
ç ÷ versus p (T = constant)
è mø P Q R S P Q R S
(a) 2 4 1 3 (b) 2 3 4 1
(c) 2 1 3 4 (d) 2 4 3 1

Paper 2
1. SbF5 reacts with HF according to the following
S. æ xö 4. equation. SbF5 + 2HF ¾¾®[H2F]+ [SbF6 ]-
ln ç ÷ versus In p
è mø Which of the following is/are true regarding the
above reaction?
(a) Hybridisation of SbF5 changes from sp3d in reactant to
sp3d 2 in the product [SbF6 ]-
(b) [H 2 F]+ is linear with sp2 hybridisation
(c) [H 2 F]+ has bent structure with sp2 hybridisation
Codes (d) The shape of SbF5 is triangular bipyramidal and acts as a
P Q R S P Q R S Lewis acid
(a) 3 2 4 1 (b) 2 3 4 1 2. H2S is a weak acid and is used to precipitate
(c) 2 3 3 1 (d) 2 3 1 4 different metal ions by controlling pH. Which of the
19. Match Column I and Column II, where Column I following is/are correct regarding H2S (Given, K1
represents molecular formulae of the complex and K2 for H2S are respectively 5.7 ´ 10-8 and
compound and Column II represents its shape and 1.3 ´ 10-13 ).
magnetic nature. (a) The equilibrium constant for overall ionisation of H 2S to S 2-
Column I Column II is 7.4 ´ 10 -21
(b) For a solution with the concentration of H 2S, Bi 3+ and H +
P. [Ni(CN)4 ]2- 1. Octahedral and diamagnetic
respectively 0.1 M, 1.5 mM and 10 mM, Bi 2 S 3 will be
Q. [CuCl 4 ]2- 2. Octahedral and paramagnetic
. ´ 10 -72)
precipitated in the solution (Ksp for Bi 2 S 3 is 16
R. [Fe (CN)6 ]4 - 3. Tetrahedral and paramagnetic
(c) For a solution with the concentration of H 2 S, Mn2+ and H +
S. [Co(H2O )6 ]2+ 4. Square planar and diamagnetic respectively 0.1 M, 1.5 mM and 10 mM, MnS will be
precipitated (Ksp for MnS is 3.0 ´ 10 -11)
Codes (d) For a solution with the concentration of H 2S, Mn2+ and H +
P Q R S P Q R S respectively 0.1 M, 1.5 mM and10 mM, MnS will not be
(a) 3 4 1 2 (b) 4 3 1 2 precipitated
(c) 3 4 2 1 (d) 4 3 2 1

56
3. 2 moles of a triatomic linear gas with neglected 7. Which of the following monomers when polymerise
vibrational degree of freedom is taken through a form a biodegradable polymer?
reversible process starting from A as shown in the CH3
V
figure below. The ratio of B is equal to 2. If the (a) H2C==C—CH==CH2
VA
temperature at A is 200 K, then which of the (b) H2N N NH2
following is/are correct?
N N and HCHO
C
NH2
B OH
V(L)
|
A (c) CH 3 ¾ CH ¾ CH 2 ¾ COOH and
OH
T(K) |
CH 3 CH 2 ¾ CH ¾ CH 2COOH
(a) Work done by the gas from A to B is 3.33 kJ
(b) The total enthalpy change from A to C is 11.64 kJ (d) NH 2CH 2COOH and NH 2 ¾ (CH 2 )5 ¾ COOH
(c) Work done by the gas from A to B is 6.66 kJ 8. Which of the following will produce a stable planar
(d) The total enthalpy change from A to C is 5.82 kJ carbocation?
4. Which of the following represent the correct (a) Addition of SbF5 to cycloheptatrienyl fluoride
statement regarding physisorption of a gas on a (b) Addition of bromonium ion to propene
solid surface? (c) Addition of acid to propene
(a) Physisorption is characterised by decrease in entropy and (d) Addition of argentium ion to triphenylmethyl chloride
increase in enthalpy
9. For the following consecutive reaction
(b) Physisorption increases with increase in the ease of
K1 ( Time -1 ) K2 ( Time -1 )
liquefaction of gases A ¾¾¾® B ¾¾¾® C , the following curves were
(c) Physisorption can be converted into chemisorption at obtained depending upon the relative values of K1
higher temperature and K2 .
(d) As adsorption proceeds, DH approaches to TDS and DG
C C
becomes zero when equilibrium is reached
5. The following reactions represent the reaction of
Conc.

Conc.

A A
primary amines with HNO2 and the major product
formed after dehydration. Which of the following B B
reactions correctly represent the reaction and its Time Time
major product? I II
NaNO2+HCl Which of the following is/are correct?
(a) NH2
(a) For fig. I, K1 > K 2 (b) For fig I, K1 < K 2
(c) For fig II, K1 > K 2 (d) For fig II, K1 < K 2
NaNO2+HCl x
(b) NH2 10. The following graph represents logæç ö÷ versus log p
è mø
for the physisorption of CO2 gas over charcoal,
NaNO2+HCl
(c) NH2 x
where represents the amount of CO2 adsorbed
m
NaNO2+HCl per unit mass of charcoal and p represents the
(d) NH2
pressure in atm.
6. Which among the following correctly represents the
order of the properties mentioned in the right side
bracket? log x/m

(a) B > Te > Ga > Al > In (order of first ionisation energy) 45°
log 2
(b) Be < B < C < N (order of first ionisation energy)
(c) Mg 2+ < Na+ < F - < O 2- (order of ionic radius)
(d) CH 4 < SiH 4 < SnH 4 < PbH 4 (order of reducing power of log p
hydrides)

57
(a) The n value for the adsorption of CO 2 is 1 16. How many of the following species are
(b) The K value for the adsorption of CO 2 is 2 paramagnetic according to molecular orbital theory
(c) The amount of CO 2 adsorbed per unit mass of charcoal at (MOT)?
4 atm pressure is 8 units
NO2 , Ne2 ,Li2 , N2O4 N2 ,C2 ,B2 , NO,O2
(d) The value of n for the adsorption of CO 2 is 2
17. Antiaromaticity is a characteristic of cyclic organic
Section 2 (Only integer value correct type) compounds with a p-electron system that has higher
This section contains 10 questions. Each question, when energy. How many of the following cyclic
worked out will result in one integer from 0 to 9. (both compounds are antiaromatic?
inclusive)
11. Find out the ratio of pH of a solution containing , , ,
1 mole of CH3COONa and 2 moles of CH3COOH I II III IV
per litre to the pH of another solution containing
2 moles each of CH3COONa and HCl per litre of the
solution? (Ka for CH3COOH is 1.8 ´ 10-4 )
, ,
12. The standard enthalpy of combustion of H2 , C6H10 V VI VII
and C6H12 at 25°C are respectively - 241 kJ mol -1,
18. Among the following Newmann projections of
- 3800 kJ mol -1, - 3920 kJ mol -1. The magnitude
2,3-dichlorobutane, how many are optically
of heat of hydrogenation of 3.4 g of C6H10 (in kJ) is active?
around Cl Cl

13. How many optically active stereoisomers are H CH3 H 3C H


possible by all the products formed during the
ozonolysis of the following compound? H CH3 H CH3
Cl
(i) O 3 I II
(ii) Zn/AcOH Cl Cl

14. Different isomers of an organic compound with H3C H H CH3


molecular formulae C4H8O2 and containing
O H3C H H3C H
||
Cl Cl
¾ C ¾ O group were taken separately and their
III IV
solubilities in water were measured. How many of
these isomers will be substantially less soluble than 19. Nitrobenzene and water which are two immiscible
the rest? liquids when mixed, boil at 99°C. The partial vapour
pressure of water and that of nitrobenzene are
15. How many of the given compounds have square
respectively 733 mm Hg and 27 mm Hg. Calculate
planar geometry XeF4 SiF4 , SF4 ,[Rh(PPh3 )3 Cl],
the ratio of the weight of nitrobenzene and water in
[PtCl2 ( NH3 )2 ],[Pt(C2H4 )Cl3 ]- the mixture.
[CuCl4 ]2 - ,[Ni(CN)4 ]2 - , XeO2F2 , IOF3 20. Find out the total number of isomers exist for the
following complex compound:
[CoCl2 ( NH3 )2 (en)]+

Answers
Paper 1
1. (a) 2. (c) 3. (b) 4. (a) 5. (b) 6. (a) 7. (a) 8. (a) 9. (c) 10. (a)
11. (a) 12. (a) 13. (c) 14. (d) 15. (b) 16. (b) 17. (c) 18. (b) 19. (b) 20. (d)

Paper 2
1. (a,d) 2. (a,b,d) 3. (a,b) 4. (b,c,d) 5. (a,c,d) 6. (a,c,d) 7. (a,c,d) 8. (a,b,c) 9. (a,d) 10. (a,b,c)
11. (2) 12. (5) 13. (5) 14. (4) 15. (5) 16. (4) 17. (4) 18. (2) 19. (4) 20. (4)

58
Answer with Explanations
Paper I 5. (b) We know that,
1. (a) The balanced cell reaction can be written as K p = Kc ( RT )Dn
- 3+
[Cr + 3e ® Cr ] ´ 2 Se 6( g ) ` 3Se 2( g )
[Ni 2+ + 2 e - ® Ni ] ´ 3 Intial 1 0
2 Cr + 3Ni 2+ ® 2 Cr 3+ + 3Ni At Eqm. 1- x 3x
Total pressure at equilibrium
\ n = 6, [Cr 3+ ] = 0.010 M, [Ni 2+ ] = 0.020 M
=1- x + 3x =1+2 x
Applying Nernst equation
3x
0.0591 ( 0.010 )2 p Se 2 = ´p
E = E° - log 1+2 x
6 ( 0.020 )3 1- x
pSe 6 =
Here, E ° = - ( -0.744 V ) - 0.236 V = 0.508 V 1+2 x
0.0591 æ 100 ö pSe 32
\ E = 0.508 - ´ log ç ÷ Kp =
6 è 8 ø pSe 6
= 0.508 - 0.0108 = 0.1687
» 0.497 V. \ K p = Kc ( RT )Dn

2. (c) Kp
Kc =
O3 / Zn+H2O ( RT )Dn
0.1687
=
( 0.0821 ´ 973 )2
A B
= 0.2645 ´ 10 -4

Mg+Hg/H 2O H+ 6. (a) Given [PO 3-


4 ] = 5 ´10
-3
M
HO OH HO
D Tl 3PO 4 ` 3Tl+ + PO 34-
3 ´ 5 ´ 10 -3 5 ´ 10 -3
C
-3
+
\ [ Tl ] = 3 ´ 5 ´ 10 = 1.5 ´ 10 -2 M
Rearrangement LiAlH 4 For dissociation of TlN3,
TlN3 ` Tl+ + N-3
H—O O HO
D E ( 5 + 1.5 ´ 10 -2 ) s
\ Ksp for TlN3 = 5.6875 ´ 10 -4
Ring
Conc.H 2SO4 expansion H +
or S (S + 1.5 ´ 10 -2 ) = 5.6875 ´ 10 -4
H3PO4 Þ S = 1.75 ´ 10 -2 mol L -1

7. (a) Because As(Ph )3 is a much weaker nucleophile than (CH3 )3 As


3. (b) On increasing electron withdrawing capacity of the group, the it does not form [(Ph )4 As ]+ .
extent of back p-bonding decreases. As a result bond multiplicity
decreases and therefore bond length decreases. 8. (a) E ° can be calculated as
Hence, the correct order of P — P bond length is °
Ecell = ER - EP
P2F4 < P2(CF3 )4 < P2(CH3 )4 < P2H4 where, E R = SRP of reactant
4. (a) NaCl (rock salt) type structure is fcc type E P = SRP of product
\ Zeff = 4 (4 Na + and 4 Cl - ) °
If Ecell = +ve, then reaction is spontaneous otherwise
- non-spontaneous.
Number of B ions removed
1 1 3 E10 = 1.51V
= 4 ´ +2 ´ = Mn 3+ ¾¾® Mn 2+
8 2 2
1 1 E 20 = -1.18V
Number of A+ ions removed = 2 ´ = Mn 2+ ¾¾® Mn
4 2
But body centre A+ ion is not removed. \ For Mn 2+ disproportionation,
3 5 E ° = - 1.51 V - 1.18 V
\ Number of B - ions left = 4 - = = 2.5
2 2 = - 2.69 V
1 7
\ Number of A+ ions left = 4 - = = 3.5
2 2
Formula = A3.5B2.5

59
9. (c) 14. (d) Yellow coloured dye is obtained when benzene diazonium
(i) SOCl2 chloride reacts with aniline.
OH OH
(ii) Br2/NBS NH2
Br N2Cl + H
(ii) HCl
A
(i) K2CO3, H2O, D Al2O3
(ii) H2O+ OH N N NH2 + HCl
OH (Yellow coloured dye)
B
CH2—NO2, OH – 15. (b) The balanced reaction during the reduction of KMnO 4 to Mn 2+
can be written as
Br
OH OH MnO -4 + 8 H+ + 5e - ¾® Mn 2+ + 4H2O
1 mol 5 mol
NO2
CH2—NO2+ OH– Hence, the moles of electrons required is 5 moles.
NO2
H3 O
16. (b) Given E ° = 1.52 V
H MnO -4 /Mn 2 +

OH [Mn 2+ ] = 1.0 ´ 10 -3 M,
D [MnO -4 ] = 2.0 ´ 10 -3 M
10. (a)
pH = 3 Þ [H+ ] = 10 -3
Case I For inner balloon
600 800 Applying Nernst equation
= Þ T2 = 400 K 0.0591 [Mn 2+ ]
300 T2 ERed = E °Red - log
n [MnO -4 ][H+ ]8
Case II For outer balloon
1500 1800 0.0591 1.0 ´ 10 -3
= Þ T2 = 360 K = 1.52 - log
300 T2 5 2.0 ´ 10 -3 ´ (10 -3 )8
Hence, the outer balloon will burst first on heating, as 0.0591 æ 10 24 ö
= 1.52 - log ç ÷ = 1.52 - 0.0591 ´ 23.7
T2(Case I) >T2 (Case II) 5 ç 2 ÷ 5
è ø
11. (a) The chemical reaction occurring during photosynthesis is = 1.52 - 0.28 V = 1.24 V
given as
17. (c) Only 1° amines give carbyl amine test.
6CO 2 + 6H2O ¾® C 6H12O 6 + 6O 2
D f H ° for the above reaction is alc. KOH
CH2NH2 + CHCl3 CH2N C
D f H ° = - 1273.3 + 0 - [ 6 ´ ( -393.5) + 6 ´ ( -285.8 )]
= 2802.5 kJ
Phenol gives orange coloured dye with benzene diazonium
DS ° for the above reaction
chloride.
= 212.1 + 6 ´ (205.0 ) - [ 6 ´ (213.2 ) + 6 ´ 69.9 ]
= - 256.5 J mol -1K -1 HO H + Cl N2

DG ° = D f H ° - TDS °
= 2802.5 kJ - 300 ´ ( -256.5 k mol -1K -1 )
= 2802.5 kJ + 76.95 kJ = 2879.45 kJ mol -1 OH N N
DG ° per molecule (Orange dye)
2879.45 ´ 10 3
= » 4.78 ´ 10 -18 J 2° amines give an insoluble alkali with Hinsberg’s reagent.
6.0823 ´ 10 23

12. (a) As DG value at 300 K is 2879.45 kJ mol -1, NH—CH3 + S Cl


2879.45 kJ removes = 6 mole of CO 2
18
6 ´ 3.4 ´ 10 kJ
\ 3.4 ´1018 kJ will remove =
2879.45 kJ
= 7.1 ´ 1015 mol CO 2 S N
13. (c) An orange coloured dye in obtained when benzene diazonium CH3
chloride reacts with phenol.
Insoluble alkali

N2Cl + H OH N, N-dimethyl amine gives green colour with HNO 2 .


CH3 CH3
N + HONO O N N
CH3 CH3
N N OH + HCl
(Green colour)

60
18. (b) In case of physisorption, æç x ö÷ decreases with increase in 2. (a,b,d) H2 S - 2H+ + S 2-
è mø K = K1 ´ K 2 = 7.4 ´ 10 -21
temperature.
[H+ ]2[S 2- ] (0.01)2 ´ [S 2- ]
æ xö
Increase of chemisorption, ç ÷ increases with increase in K= = = 7.4 ´ 10 -21
[H2S] 0.1
è mø
temperature till the achievement of activation energy for the Þ [S 2- ] = 7.4 ´ 10 -18
chemical reaction. However, once the activation energy is Ksp for Bi 2S 3 = [Bi 3+ ]2 ´ [S 2- ]3 = 1.6 ´ 10 -72
x
achieved, on increasing the temperature further, decreases. IP for Bi 2 S 3 = (1.5 ´ 10 -3 )2 ´ (7.4 ´ 10 -18 )3
m
Freundlich equation is given as = 9.1 ´ 10 -58
x x
= Kp1/ n Þ µ p1/ n As IP > Ksp , Bi 2S 3 will be precipitated.
m m for MnS,
Taking logarithm to both sides of the above equation Ksp = 3.0 ´ 1011
æ xö 1
In ç ÷ = ln p + ln K I.P = (1.5 ´ 10 -3 ) ´ (7.4 ´ 10 -18 )
è mø n
æ xö = 1.1 ´ 10 -20
Hence, ln ç ÷ vs ln p, graph will be a straight line.
As IP < Ksp hence precipitation of MnS will not occur.
è mø
19. (b) CN- is a strong field ligand, hence pairing of unpaired 3. (a, b) For A to B
electrons takes place. However, H2O and Cl - are weak field W = - pDV = - nRDT
TB
ligand, hence no pairing will occur. = 2 or TB = TA ´ 2 = 400 K
TA
[Ni (CN)2]2–
\ W = - nRDT
= - 2 ´ 8.314 ´ ( 400 - 200 )
dsp3 (Square planar) » 3.33 kJ
n = 0, diamagnetic
Again, DH total = DH AB + DH BC
[CuCl4]2– = nC p (TB - TA ) + 0
= nC p ( 400 - 200 ) + 0
sp3 (Terathedral) 7
= 2 ´ R ´ 200
2
Similarly, [Fe (CN)6 ]4 - will have octahedral shape and is
» 11.64 kJ
diamagnetic due to complete pairing of electrons and
[Fe (H2O )6 ]2+ will have octahedral shape and is paramagnetic 4. (b, c, d) Physisorption is characterised by both decrease in
due to presence of 4 unpaired electrons. entropy and enthalpy. Hence, option (a) is incorrect and the rest
options are correct.
20. (d) Clark’s method is a process to remove temporary hardness of
water, in which calculated amount of lime (CaCO 3 ) is added to 5. (a, c, d) As the reaction of HNO 2 with primary amine proceeds via
hard water. In Calgon’s method Na 6 P6 O 18 (calgon) is added to carbocation formation, hence rearrangement of carbocation will
hard water, which gives the following reaction. take place forming the most stable product.
2-
Na 6P6O 18 ¾® 2 Na + + Na 4P6O 18
CH2—NH2 CH2
2-
Na 4P6O 18 + M 2+ ¾® [Na 2MP6O 18 ]2- + 2 Na + NNO2 Ring expansion
The chemical reaction involving ion-exchange method is
2 NaAlSiO 4 ( s ) + M 2+ ( aq ) ¾® –
OH
+
M( AlSiO 4 )2( s ) ¯ + 2 Na ( aq )
OH

Paper 2 H
+ 3 –H2O
1. (a,d) [H2 F] has bent structure with sp hybridisation. Hence,
both (b) and (c) are wrong. (Major product)

The hybridisation of SbF5 is sp3d 6. (a,c,d) The first ionisation energy of Be is greater than that of B,
5+7 ´5 due to stable fulfilled S-electronic configurations in Be-atom.
SbF5 =
8
7. (a,c,d) Melamine and formaldehyde on condensation give
40
= = 5( sp3d ) melamine formaldehyde polymer which is bio-nondegradable.
8
NH2 N NH2 H2 N N NHCH2OH
Hybridisation of SbF6- is sp3d 2
+ HCHO
5+7 ´6 +1 N N N N
SbF6- =
8
48 NH2 NH2
= = 6( sp3d 2 )
8 (Melamine) (Bio-nondegradable)

61
8. (a, b, c) F = 2 Ka
1
pH2 = - log[H+ ] = - log 2 K a = - log2 K a
SbF5 2
(a) [SbF6]
pH1 - log2 K a
\ = =2
Cyclo hepta Planar carbocation pH2 1
trienyl fluoride - log2 K a
2
Br
12. (5) Given, H2 + 1 O 2 ¾¾® H2O, DH1 = - 241 kJ ...(i)
(b) + Br+ 2
Bromonium ion 17
C 6 H10 + O 2 ¾¾® 6CO 2 + 5H2O , DH 2 = - 3800kJ ...(ii)
(planar) 2
H C 6H12 + 9O 2 ¾¾® 6CO 2 + 6H2O , DH 3 = - 3920 kJ ...(iii)

(c) + H+ Adding Eqs. (i) and (ii) then subtracting Eq. (iii), we get
Þ C 6 H10 + H2 ¾¾® C 6H12
2º– carbocation
(planar) \ DH = DH1 + DH 2 - DH 3
Cl = ( - 241 - 3800 + 3920) kJ
= - 121 kJ
(d) C + Ag+ C
45º tilted to \ Heat of hydrogenation for 1 mole (82 g) of C 6 H 10 = - 121 kJ
each other Þ Heat of hydrogenation for 3.4g
- 121
= ´ 3.4 kJ » 5 kJ
82
Non planar
13. (5) The ozonolysis of the compound gives the following products.
This is a non-planar carbocation as the cation is delocalised to
all the three rings. The non-planar structure is due to steric
hindrance of these three phenyl rings. All three phenyl ring is
tilted to plane by 45 like wings of a fan.
9. (a, d) By considering the graphs we can conclude that O3 / Zn/AcOH
In fig (I), B increases to a maximum value during reaction. This is
CH3 CH3 CH3
possible, when rate of formation of B is more than rate of decay
of B into C.
CH3 CH 2—C—CHO + OHC—C—C—CHO + HCHO
\ K1 > > K 2
In fig. (II), B is maintained to a very low value. This suggests that H H H
B is decaying as soon as it is formed. This possible when A B C
K 2 >> K1.
A is optically active and has 2 optically active isomers. B is also
10. (a, b, c) According to Freundlich equation x = Kp1/ n optically active and has 3 optically active isomers.
m \ Total optically active isomers = 2 + 3 = 5 .
æ xö 1
or ln ç ÷ = ln K + ln p 14. (4) C 4H8O 2 exhibits 6 isomers with ¾ COO group which are
è mø n
given as
Comparing the above equation with the given graph CH3
1 ½½
= tan 45 Þ n = 1
n CH 3CH2CH2 COOH ,CH3 ¾ CH ¾ COOH
ln K = log 2 Þ K = 2 I II
æ xö CH3 CH2 COOCH3,CH3C OOCH2 CH3
Again, ç ÷ = Kp1/ n = 2 ´ ( 4 )1/1 = 8 units. III O IV
è mø
½½
11. (2) Case I [CH3COONa] = 1 M CH3 CH2C H2O ¾ C ¾ H, CH3 ¾ CH¾ CH3
V ½
[CH3COOH] = 2 M
O ¾ CHO
[CH3COONa] VI
pH1 = pK a + log
[CH3COOH] Out of three 6 isomers, III IV V, and VI are substantially less
æ 1ö soluble than the first two due to absence of hydrogen bonding.
= - log K a + log ç ÷
è2 ø 15. (5) XeF4 , [Rh(PPh 3 )3Cl), (PtCl 2(NH3 )2 ] , [Pt(C 2H4 )Cl 3 ]- and
= - log2 K a [Ni(CN)4 ]2- have square planar geometry. XeF4 is square planar
Case II CH3COONa + HCl -
CH3COOH + NaCl due to presence of 2 lone pairs electrons. [Ni(CN)4 ]2- has square
Initial conc. 2M 2M 0 0 planar structure due to formation of inner orbital complex. SiF4
Final conc. 0 0 2M 2M has tetrahedral shape due to absence of lone pairs electrons.
\ [CH3COOH] = 2M SF4 , XeO 2 F2 and IOF3 has see-saw geometry due to presence of
[H+ ] = K a ´ C [Q CH3COOH in a weak acid] 1 lone pair electron in each.

62
16. (4) NO 2, B 2,NO , and O 2 are paramagnetic due to presence of On solving (i) and (ii), we get
unpaired electrons. W1
=4
W2
17. (4) Cyclic organic compounds containing 4n p-electrons and
lone pair electrons are called antiaromatic. Hence, among these 20. (4) [CoCl 2(NH3 )2(en)]+ exhibit both optical and geometrical
structures, II, III, IV and V contains 4, 12, 8 and 8 electrons isomerism.
respectively. Hence, they are antiaromatic. + +
Cl Cl
Cl NH3
18. (2) Among the given Newman projections of 2,3 dichlorobutane,
en Co en Co
I and III are optically active.We can know it by converting Newman
NH3 NH3
projection formulae to sawhorse formula followed by Fischer
NH3 Cl
projection formula.
cis-form trans-form
19. (4) The total vapour pressure of the solution (optically active) (optically inactive)
pT = pwater + pnitrobenzene = 733 + 27 = 760 mmHg 2 optical isomers
If cwater is the mole fraction of water NH3 +
é W1 ù Cl
1 ê 18 ú en Co
then p = pT ´ cwater Þ 733 = 760 ´ ê ú …(i)
W W
ê 1 + 2 ú Cl
NH3
ë 18 123 û
trans-form
Similarly for nitrobenzene
(optically inactive)
é W2 ù
ê 123 ú Hence, total isomers = 4
27 = 760 ´ ê ú …(ii)
ê W1 + W2 ú
ë 18 123 û

63
Instructions
This question paper contains 30 questions each having 5. The energy required during the reduction of 18.45 g of
four options, out of which only one option is correct. nitrobenzene to aniline, if the potential drop across the
1 cell is 2.5 V is around
1. The 2 versus time graph
[ A]t (a) 217.12 kJ (b) 108.56 kJ
for a reaction is given below, (c) 278.15 kJ (d) 54.28 kJ
1
where [ A]t is the [A]2t 6. Potassium dichromate solution acts as an oxidising
concentration of reactant 0.25 45° agent in acidic medium. During a redox reaction, the
(in mol L-1 ) at time t. Which –
concentration of Cr2 O27 and Cr3 + was found to be
of the following is wrong?
1.0 ´10 -3 M and 2.0 ´ 10 -3 M, respectively. The
(a) The reaction is a third order t /(min) reduction potential of potassium dichromate if pH of
reaction the solution was measured to be 3 is (Given,
(b) The rate constant for the reaction is 8.33 ´ 10 -2 L2 mol -2 s -1 E° 2- 3+ = 1.33 V)
Cr2 O7 / Cr
(c) Initial concentration of the reactant is 2 mol L-1 (a) 0.47 V (b) 1.88 V (c) 0.94 V (d) 0.74 V
(d) None of the above
7. The pH of a buffer solution prepared by dissolving
2. A propellent for rocket is obtained by mixing liquid 26.5 g of Na2 CO3 in 500 mL of an aqueous solution
hydrazine and N2 O4 . These compounds react to give containing 150 mL of 1 M HCl is (Given, pK a for HCO3-
nitrogen gas and water vapour. If the standard is 10.25)
enthalpy of reaction of N2 O4 is -1049 kJ mol -1 , the heat (a) 10.07 (b) 9.83 (c) 9.27 (d) 11.07
evolved when 6.4 g of hydrazine reacts is
(a) 209.8 kJ (b) 104.9 kJ
8. The reaction given below achieved equilibrium inside
a closed container at temperature T.
(c) 52.45 kJ (d) 78.2 kJ
A+ B sC + D
3. A very small amount of a non-volatile solute, which
doesn’t dissociate or associate was dissolved in 100 mL The initial concentration of B was twice that of the
of benzene (density 0.876 g cm -3 ). The vapour initial concentration of A and during equilibrium, the
pressure of this solution at room temperature is concentration of C was twice to that of equilibrium
98.5 mm Hg, while that of pure benzene is 100 mm Hg. concentration of A . The K C for the above reaction is
If freezing point of pure benzene is 5.5°C, the freezing (a) 1 (b) 1.5 (c) 2 (d) 3
point of the solution is (Given, K f value for benzene is 9. In order to estimate the concentration of Pb2 + in a
5.12°C kg mol -1 ) polluted water sample, an excess of Na2 SO4 was added
(a) 4.49 °C (b) 6.51°C to 1 L of the polluted water. The dry mass of the
(c) 4.82 °C (d) 5.02 °C
precipitation obtained was found to be 190.5 mg. The
4. Calcium chloride and sodium carbonate were mixed concentration of Pb (in ppm) in the polluted water
with water and an infinitely dilute solution was sample is around
prepared. The enthalpy change for the reaction is (a) 260 (b) 130 (c) 180 (d) 95

(Given, D f H° for Ca2 + (aq), CO 23 (aq) and CaCO3 (s) are
10. Which of the following represents the correct order of
respectively -129.80 kcal mol -1 , - 161.65 kcal mol -1 N— O bond length for the following species?
and -288.5 kcal mol -1 )
(a) NO + < NO < NO - (b) NO - < NO < NO +
(a) 579.95 kcal (b) 289.95 kcal + -
(c) 5.9 kcal (d) 2.95 kcal (c) NO < NO < NO (d) NO - < NO + < NO

23
11. The following set of quantum numbers represent 20. Buna-N is a non-biodegradable polymer which is
different electrons of an atom. resistant to the action of petrol, lubricating oil and
1 organic solvent. Which of the following represents the
(i) n = 4, l = 0, m = 0, s = +
2 monomers of the rubber?
1
(ii) n = 3, l = 1, m = 1, s = + NH2 N NH2
2 (a)
1 and CH2 CH CN
(iii) n = 3, l = 2, m = 0, s = - N N
2
Which of the following represent proper order of NH2
energy of these electrons? (b) CH2 CH CH CH2 and CH2 CH CN
(a) 3 > 1 > 2 (b) 1 > 2 > 3
(c) 3 > 2 > 1 (d) 1 > 3 > 2 CH CH CN
12. Which of the following combination correctly (c) CH2 CH CH CH2 and
represents the inorganic compound and its shape?
(a) SF4 – see-saw CH CH2
(b) HgCl 2 – angular (d) CH2 CH CH CH2 and
(c) ClF3 – triangular planar
(d) ICl 4 – – tetrahedral 21. Which of the following represents the structure of an
13. Which of the following represents the correct order of antidepressant drug?
SO2NH2
acidic character of the oxides?
(a) Cl 2 O 7 > SO 3 > CaO > PbO 2 NHNH2
(b) SO 3 > Cl 2 O 7 > PbO 2 > CaO (a) (b)
(c) Cl 2 O 7 > PbO 2 > SO 3 > CaO
(d) Cl 2 O 7 > SO 3 > PbO 2 > CaO
NH2
14. For the following balanced redox reaction O
y
2MnO + xPbO2 + yH+ ¾® 2MnO4- + xPb2+ + H2 O C
2 HN
the values of x and y respectively are (c) NH (d)
(a) 5 and 8 (b) 4 and 8 (c) 5 and 10 (d) 5 and 14 SO2 N NH2

15. During an experiment, a positron and an electron were 22. Which of the following chemical reaction given by
collided. They were neutralised and two g-rays of equal glucose confirms that the carbonyl group present in
energy were emitted. The wavelength of the emitted glucose is an aldehyde group?
g-ray is (a) C 6 H12 O 6 + NH 2 OH ¾® Product
(a) 1.21 pm (b) 1.71 pm (c) 4.84 pm (d) 2.42 pm 2 H O
(b) C 6 H12 O 6 + Br2 ¾® Product
16. Which of the following represents the correct order of
D
solubility of different halides of alkali metals? (c) C 6 H12 O 6 + HI ¾® Product
(a) LiI > NaI > KI > RbI (b) LiF > NaF > KF > RbF (d) C 6 H12 O 6 + (CH 3COO )2O ¾® Product
(c) Both (a) and (b) (d) None of these
23. The major product obtained in the following reaction is
17. Which of the following represents the correct order of CH3
stability of different oxidation states of p-block H2SO4
elements? OCH3 + C CH2
(a) Tl 3+ > Tl + (b) In+ < Ga +
(c) Pb 2+ > Pb 4+ (d) Ga + > Ga . 3+
O
(a)
18. Which among the following species show
paramagnetic behaviour?
(a) N 2 O 5 (b) NO
O
(c) N 2 O 3 (d) All of these (b)
19. Which of the following represents the correct order of O
the magnetic moment of different complexes of iron?
(a) Fe(H 2 O)6 ]3+ > [Fe(CN)6 ]3- > [Fe(CN)6 ]4 - (c)
4- 3- 3+
(b) [Fe(CN)6 ] > [Fe(CN)6 ] > Fe(H 2O)6 ]
(c) [Fe(CN)6 ]3- > [Fe(CN)6 ]4 - > [Fe(H 2O)6 ]3+ O
(d)
(d) [Fe(H 2O)6 ]3+ > [Fe(CN)6 ]4 - > [Fe(CN)6 ]3-

24
24. Which of the following reactions of aniline is not 27. Match Column I which represents the complex
feasible at the given reaction condition mentioned compound with Column II represents the isomerism
below? shown by the compound using the codes.
NH2
Column I Column II
A. [Co(NH3 )6 ] [Cr(C 2O 4 )3 ] 1. Optical
(a) + Br2 + H2O
B. [Co(NH3 )4 Cl 2 ] 2. Ionisation

NH2 C. [Co(en)2(NO 2 )Cl(SCN)] 3. Geometrical


D. cis-[Co(en)2Cl 2 ] 4. Coordination
Anhyd.AlCl3
(b) + CH3CH2Cl Codes
A B C D A B C D
NH2 (a) 1 2 3 4 (b) 1 3 4 2
(c) 4 3 2 1 (d) 2 1 3 4
HNO3 + H2SO4
(c) 288 K
28. The major product obtained in the following reaction is

NH2 HNO3 /H2SO4

(i) (CH3CO)2O + Pyridine


(d)
(ii) Br2 + CH3COOH
NO2
(a) (b)
25. Which of the following statement is correct regarding
Freundlich isotherm for physisorption of a gas on solid NO2
adsorbent?
(a) The rate of adsorption is directly proportional to pressure
1
when = 0
n (c) (d) Both (a) and (b) in
1 NO2 equal proportion
(b) can have any value between 1 to infinite
n
(c) Freundlich isotherm fails at high pressure
29. Which of the following is the most reactive alkyl halide
æ xö
towards Gabriel phthalimide synthesis reaction?
(d) The plot of log ç ÷ versus log p gives a straight line with (a) CH 3 CH 2 Br (b) CH 3 C H — Br
è mø
|
slope n( n > 1) and y-intercept log k
CH 3
26. Which of the following represents the correct structure
CH 3
of the product C formed from the following series of
|
reactions? (c)
Br
(d) CH 3 — C — Br
CH3 MgBr (i) CO2 H2SO4 / HgSO4 |
CHºº CH ¾¾¾® A ¾¾® B ¾¾¾¾® C CH 3
+
(ii) H3 O

O 30. Equal volume of 0.5 M R-2-butanol and 0.5 M racemic


|| COOH mixture of 2-butanol are mixed and placed inside a
(a) C H == CH — C — OH (b) CH 2
| COOH polarimeter tube of 10 cm length. If the observed
OH rotation of the mixture is 0.4°, the specific rotation of
the mixture will be
(c) CH 3 CH 2COOH (d) C H 2 — C H 2
| | (a) + 10.81° (b) + 43.24°
OH OH (c) + 27.74° (d) + 21.62°

Answers
1. (d) 2. (b) 3. (a) 4. (d) 5. (a) 6. (c) 7. (a) 8. (a) 9. (b) 10. (a)
11. (a) 12. (a) 13. (d) 14. (a) 15. (d) 16. (a) 17. (c) 18. (b) 19. (a) 20. (b)
21. (a) 22. (b) 23. (a) 24. (b) 25. (c) 26. (a) 27. (c) 28. (b) 29. (a) 30. (d)

Detailed solutions of these questions are available on http://www.arihantbooks.com/Chemistry%20Spectrum.pdf

25
Explanations
1 5. (a) The chemical reaction can be written as
1. (d) For nth order reaction, versus time graph is a straight
[ A]n - 1 +3 –3
C 6 H5 N O 2 + 6H+ + 6 e - ¾® C 6 H5 N H2 + 2H2O
line. Hence, the reaction is third order reaction.
Again for nth order reaction, \ n=6
M 123
tan q = k( n - 1) Equivalent weight of nitrobenzene = =
6 6
tan 45° = 1
EIt
1 w=
Þ k = L2 mol -2 min -1 96500
2
123 ´ It
1 \ 18.45=
= L2 mol -2 s -1 6 ´ 96500
2 ´ 60
18.45 ´ 6 ´ 96500
= 8.33 ´ 10 -2 L2 mol -2 s -1 \ It = = 86850 C
123
Again y-intercept C = 0.25 \ Energy required = V ´ Q = 2.5 ´ 86850 = 217125 J = 217.125 kJ
1 6. (c) The reduction half reaction of K 2Cr2O 7 can be written as
=
[ A]20 –
Cr2O 27 + 14H+ + 6e - ¾® 2 Cr 3+ + 7H2O
1
Þ [ A]0 = = 2 mol L-1 \ n=6
0.25
Given, [Cr2O 2-
7 ] = 1.0 ´ 10
-3
M
2. (b) The balanced chemical reaction can be written as and [Cr 3+ ] = 2 .0 ´ 10 -3 M
2N2 H4 ( l ) + N2O 4 ( l ) ¾® 3N2( g ) + 4H2O( g ), 0.059 [Cr 3 + ]2
Hydrazine -1 E = E °- log
D r H° = - 1049 kJ mol 6 [Cr2O 27- ][H+ ]14

Moles of N2 H4 =
6.4 g
= 0.2 mol 0.059 4 ´ 10 - 6 éQ pH = 3 ù
= 1.33 - log êÞ [H+ ] =10 -3 ú
32 g 6 10 3 ´ (10 - 3 )14
-
ë û
2 moles of N2 H4 gives = - 1049 kJ heat 0 .059
= 1.33 - log 4 ´ 10 39
-1049 6
\ 0.2 mole of N2 H4 gives = ´ 0.2 = - 104.9 kJ
2 0 .059
= 1.33 - ´ 39 .6 = 1.33 - 0 .3894 = 0.94 V
3. (a) Applying the formula 6
p° - p nsolute 100 ´ 0.876 26.5
= , Nsolvent = 7. (a) Equivalent of Na 2 CO 3 = = 0.25 = 250 meq
p° Nsolvent 76 106
= 1.1526 Na 2CO 3 + HCl ¾® NaCl + NaHCO 3
100 - 98.5 nsolute Initial (meq) 250 150 0 0
or =
100 1.1526
Final (meq) 100 0 150 150
1.5 ´ 11526
.
or nsolute = = 0.0173
100 Here, a buffer solution is obtained due to Na 2CO 3 and HCO -3 .
0.0173 ´ 1000 [CO 23- ] 100
\ m= \ pH = pK a + log = 10.25 + log
100 ´ 0.876
[HCO -3 ] 150
= 0.1975
= 10.25 + 0.3010 - 0.4771 = 10.07
\ DTf = K f ´ m
= 5.12 ´ 0.1975 8. (a) Let the initial concentration of A be a mol L-1.
= 1.01° C A+ B s C + D
\ Freezing point of solution = 5.5 - 1.01 Initial equilibrium a 2a 0 0
= 4.49 ° C At equilibrium ( a - x ) (2 a - x ) x x
4. (d) At infinite dilution, each species is 100% dissociated. Hence, Given, [C ] = 2 [ A]
Ca 2+ ( aq ) + 2Cl - ( aq ) + 2Na + ( aq ) + CO 23- ( aq ) 2a
Þ x = 2( a - x ) or x =
3
½ 2a 2a
¯ ´
x2 3 3
KC = =
CaCO 3( s ) ¯ + 2Na + ( aq ) + 2Cl - ( aq ) (2 a - x )( a - x ) æ 2 a öæ 2aö
ç2 a - ÷ça - ÷
Ca 2+ ( aq ) + CO 23- ( aq ) ¾® CaCO 3( s ) è 3 øè 3 ø
\ DH ° = SD f H °product - SD f H °reactant 2 2
´
= - 288.5 - [ -129.80 - 161.65] = 3 3 =1
= - 288.5 + 291.45 4 1
´
= 2.95 kcal 3 3

26
9. (b) Na 2 SO 4 + Pb 2+ ¾® PbSO 4 ( s ) ¯ + 2Na + = 2 ´ 9.11 ´ 10 -31 kg ´ ( 3 ´ 10 8 ms -1 )2
207.2 = 1.64 ´ 10 -13J
Percentage of Pb in PbSO 4 = = 68.32%
303.3 E
Energy of one photon =
Amount of Pb in the precipitated PbSO4 2
68.22 = 8.2 ´ 10 -14 J
= 190.5 mg ´
100 hc
Again, E=
= 130.15 mg in 1 L l
130.15 ´ 10 -3g hc 6.62 ´ 10 -34 ´ 3 ´ 10 8
= Þ l= =
10 3 mL E 8.2 ´ 10 -14
= 130.15 ´ 10 - 6 g mL-1 » 2 .42 ´ 10 -12 m
» 130 ppm or 2.42 pm
10. (a) The bond order can be calculated as 16. (a) The correct order of solubility of different alkali metal iodides is
NO (15 electrons) : LiI >NaI >KI >RbI .
s 1s 2, *s s 2, s 2 s 2, *s2 s 2, s 2 pz2, Because due to large size of I - , the decrease in lattice energy is
p 2 px2 » p 2 py2, p* 2 p1x » p* 2 py not as fast as decrease in hydration energy. Hence, more
N b - N a 10 - 5 decrease in hydration energy result a decrease in solubility down
Bond order = = = 2 .5 the group.
2 2
Similarly, bond order of NO + and NO - are 3 and 2, respectively. However, in case of fluorides, due to small size of F - ion, the
1 reverse of the above mentioned trend is observed and hence, the
As bond length µ hydration energy increases down the group.
Bond order
The correct order of N — O bond length is NO + <NO <NO - ) 17. (c) The stability of +3 oxidation state decreases and that of
+1 oxidation state increases down the group in case of group
11. (a) The order of energy of different electrons can be calculated by 13 elements. Hence, the correct order is Tl + > Tl 3+ , In+ <Ga +
( n + l ) rule, according to which, higher the value of ( n + l ), higher is and Ga + >Ga 3+ .
the energy and for same ( n + l ), orbital with lower value of n will
have lower energy. Hence, the correct order is 3 >1 > 2 . In case of group 14 elements, the stability of +4 oxidation state
decreases down the group and that of +2 oxidation state
12. (a) SF4 has see-saw shape due to the presence of one lone pair increases down the group due to inert pair effect. Hence,
and 4 bond pair of electrons and the structure is given by Pb 2+ >Pb 4+ .
F
F 18. (b) Among NO, N2 O 3 and N2 O 5, only NO is paramagnetic due to
the presence of unpaired electron. The structures of different
S oxides of nitrogen are given as

F
F
(See-saw shape)
On the other hand, HgCl 2 is linear, ICl -4 is square planar due to the NO N2O3
presence of 2 lone pairs and ClF3 is linear. (1 unpaired electron) (No unpaired electron)

13. (d) Acidic character of different oxides is directly proportional to


the non-metallic character of different oxides.
Hence, the order of non-metallic character of different elements
attached to oxygen is Cl >S >Pb >Ca . N2O5
Hence, the order of acidity is Cl 2 O 7 >SO 3 >PbO 2 > CaO . (No unpaired electron)
14. (a) The reaction in acidic medium can be balanced as 19. (a) As CN- is a strong field ligand, it will cause pairing of unpaired
2 ´ [MnO + 3H2O ¾® MnO -4 + 6H+ + 5 e - ] electrons, whereas H2O being a weak field ligand doesn’t cause
[PbO 2 + 4H+ + 2 e - ¾® Pb 2+ + 2H2O] ´ 5 pairing of electrons. Hence,
2MnO + 6H2O + 5PbO 2 + 20H+ ¾® 2MnO -4 + 12 H+ 3d 4s 4p 4d
2+ [Fe(H2O)6]3 +
+ 5Pb + 10H2O
(n=5)
or 2MnO + 5PbO 2 + 8H+ ¾® 2MnO -4 + 5Pb 2+ + 4H2O
\ x = 5 and y = 8
[Fe(CN)6]3–
15. (d) When a positron and an electron are collided, the following (n=1)
reaction occurs.
0 0
1e + -1e ¾® 2 g-rays (equal energy)
[Fe(CN)6]4–
Energy of the two g-rays
(n=0)
E = 2 mec 2

27
20. (b) Buna-N rubber is a polymer of butadiene and acrylonitrile. 25. (c) Freundlich equation is given as x = kp1/ n, n >1
nCH2 ==CH — CH==CH2 + nCH2==CH — CN m
1, 3-butadiene Acrylonitrile Taking log on both sides
½ x 1
log = log k + log p, n >1
¯ CN m n
| 1
—CH2 — CH == CH — CH2 — CH2 —CH— Hence, Î[ 0, 1]
n
n 1 x
(Buna-N-rubber) When = 0, = constant
n m
NHNH2 æ xö
The plot of log ç ÷ vs log p gives a straight line with slope
21. (a) is the structure of phenelzine (nardil) which
è mø
acts as an antidepressant. equals to 1/n. The above equation works only upto a certain
22. (b) Glucose when reacts with bromine water, it is oxidised to pressure and doesn’t work at higher pressure.
gluconic acid which is given by an aldehyde group and not by a 26. (a) The reaction proceeds through the following way.
ketone group. CH 3 M g Br CO 2
CHO Br2 + H2O CH ºº CH ¾¾¾® CH ºº CMgBr ¾¾®
H 3O +
| A
C H —OH C OOH
| | 2 4 H SO
C H —OH C H —OH CH ºº C — COOH ¾¾® C H == CH— COOH
HgS O 4 |
| |
C H —OH C H —OH OH
| | B C
C H —OH C H —OH
| | 27. (c) The isomerism shown by the complexes are
CH2OH C H —OH
| [Co(NH3 )4 Cl 2 ] Geometrical
CH2OH cis-[Co(en)2Cl 2 ] Optical
Gluconic acid [Co(en)2(NO 2 )Cl (SCN)] Ionisation
23. (a) The reaction proceeds through the following way. [Co(NH3 )6 ][Cr(C 2O 4 )3 ] Coordination

CH3 CH3
28. (b) — C(CH3 )3 is a weakly activating group and hence,
o- or p- product will be the major product but as — C(CH3 )3 is a
+ bulky group, steric hindrance will be caused for the addition of
C CH2 + H+ C CH3
— NO 2 at ortho-position. Hence, para-product will be the major
A product.
CH3
29. (a) Since Gabriel phthalimide synthesis proceed through SN 2
H2SO4
A+ OCH3 C OCH3 reaction, hence the order of reactivity is 1°>2°>3°.

CH3 30. (d) As a racemic mixture doesn’t cause any optical rotation,
hence the rotation will be only due to R-2-butanol. However, the
—OCH3 being an activating group, the attack will occur at racemic mixture will decrease the concentration of the mixture.
para-position. 0.5 M ´ V
Hence, the molarity of mixture = = 0.25 M
24. (b) Aniline doesn’t give Friedel-Crafts reaction as it forms salt with 2V
AlCl 3, in which N-atom acquires positive charge and acts as a \ Concentration (in g mL -1)
strong deactivating group. 74 ´ 0.25g
= [Q Molecular mass of butanol = 74]
+ – 1000 mL
NH2 NH2 AlCl3
= 1.85 ´ 10 -2 g mL -1
Given, observed rotation = 0.4 °
+ AlCl 3 and length of tube,
l = 10 cm = 1 dm
(Deactivating agent for a 0.4
\ [ a ]l = obs =
q
= + 21.62 °
further reaction) l ´ C 1 ´ 1.85 ´ 10 -2

28
Instructions This question paper contains 30 questions each having four options, out of which only one option is correct.

1. If the time period of revolution of an electron 5. Which of the following is true regarding the
moving in second Bohr orbit of He + is T1 and that of Newman projection formulae of 2, 3-dichlorobutane
T given below?
the third Bohr orbit of Li2 + is T2 , then the ratio 1
T2 Cl Cl
equals to H CH3 CH3 H
2 3 27 16
(a) (b) (c) (d)
3 2 16 27 H H
CH3 CH3
2. Which of the following doesn’t represent the correct Cl Cl
order of the property indicated in the right side (I) (II)
bracket?
(a) O 2- > F - > Na + (order of ionic radius) (a) I is a meso compound
(b) Be < B < C < N (order of first ionisation enthalpy) (b) II is optically active
(c) Cl 2O 7 > Cl 2O 3 > Cl 2O (order of acidity) (c) Both I and II are optically active
(d) s > p > d > f (order of screening effect) (d) I is optically active

3. The standard reduction potential for the reduction 6. Which of the following represents the correct
of MnO4- to MnO2 in acidic medium is (Given structure of the major product formed from the
E°MnO- / Mn2+ = 1.51 V and E°MnO / Mn2+ = 1.23 V) reaction given below?
4 2 CH3
(a) 0.85 V (b) 1.70 V
Conc.H2SO3
(c) 2.34 V (d) 1.25 V CH3CH2CH—C—CH3 Major product
D
4. Biodegradable polymers are environmental friendly OH CH3
and can easily be degraded by microorganisms.
Which of the following is an example of (a) (b)
biodegradable polymer?

(a) —O—CH2CH2—O—C— —C—


(c) (d)
n

(b) —CH2—CH CH—CH2—CH—CH2—


n
7. In which among the following group of species, all
have the same bond order values?
(a) B 2,C 2,O 2 (b) C 2,O 2,F2 (c) C 2,O 2, CN + (d) C 2,O 2,CN -
8. The value of the x and y of the following balanced
(c) —O—CH—CH2—C—O—CH—CH2—C—
redox reaction in acidic medium are respectively.
n
CH3 O C2H5 O 2MnO4- + xC2 O24 - + yH+ ¾¾®
y
2Mn2 + + 2xCO2 + H2 O
(d) —C—(CH2)5—NH— 2
n (a) 5 and 10 (b) 4 and 8
(c) 4 and 14 (d) 5 and 16

20
9. Which of the following chemical reactions 14. Which of the following amines on reaction with
represents ion-exchange method for the removal of NaNO2 + HCl forms a soluble nitrile salt which on
permanent hardness of water? further heating gives a yellow oily liquid?
(a) M 2+ + Na 4P6O18 2-
¾¾®[Na 2MP6O18 ]2- 2Na +
(M = Ca, Mg) (a) NH (b) CH3 CH2CH2 NH2

(b) M 2+ ( aq ) + 2 RNa( s ) ¾¾® R 2M ( s ) + 2Na + ( aq )


(M = Ca, Mg)
(c) NH CH3 (d) (CH3)3N
(c) 2NaAISiO 4 ( s ) + M 2+ ( aq ) ¾¾® M ( AlSiO 4 )2( s ) + 2Na + (aq )
( M = Ca, Mg)
(d) MSO 4 + Na 2CO 3 ¾¾® MCO 3( s ) + Na 2 SO 4 15. Which of the following represents the most
(M = Ca, Mg) appropriate structure of the final product E formed
through the following reactions?
10. Which of the following represents the correct order
of solubility of different compounds of alkaline
earth metals? AICl3 Zn(Hg) SOCl2
(a) BeCO 3 < MgCO 3 < CaCO 3 < BaCO 3 + O A B C
HCl
(b) MgSO 4 < CaSO 4 < SrSO 4 < BaSO 4
AICl3 LiAlH4
(c) Mg(OH)2 < Ca(OH)2 < Sr(OH)2 < Ba(OH)2 D E
(d) CaF2 > CaCl 2
11. Which of the following alkyl/aryl substituted silicon (a) (b)
chlorides acts as a chain terminating group and is
used to control the length silicon polymer?
OH
(a) (C 2 H 5 )3SiOH
(b) (C 2 H 5 )2Si(OH)2 OH
(c) (C 6 H 5 )2Si(OH)2 (c) (d)
(d) C 6 H 5 Si(OH)3
12. Which of the following is true regarding the OH
structure of disaccharides sucrose and maltose?
(a) The two monosaccharide units of sucrose have pyranose
16. The most appropriate structure of the products
structure formed from the following reaction is
(b) The two monosaccharide unit in sucrose are held together CHO
NaOH
by a glycosidic linkage between C 1 of a-D-glucose and C 4 + HCHO
D
of b-D-fructose
(c) The two monosaccharide units of maltose have furanose – +
COONa
structure
(a) and CH 3OH
(d) The monosaccharide units of maltose are held together by
a glycosidic linkage between C 1 and C 4 of the two – +
a-D-glucose units COONa
–+
(b) and HCOO Na
13. Food preservatives prevent the damage of food due
to microbial infection. Which of the following CH2OH
–+
structure is an example food preservative? (c) HCOO Na and
OH
– +
CH2OH COONa
(a) (b) NH (d) and
SO2
Cl 17. Which of the following is wrong regarding the major
product obtained from the following reaction?
H3O+
C—ONa SO2NH2 Major product

(c) (d) (a) Reacts with Lucas reagent


(b) Contains 2 chiral carbons
(c) Is optically active
NH2
(d) Is dehydrated easily

21
18. Which of the following represents the correct order C6 H6 + 3H2 ¾® C6 H12 , DH = - 49.2 kcal
of nucleophilicity of the following nucleophiles? (a) 48.9 kcal (b) - 48.9 kcal (c) 147.3 kcal (d) - 147.3 kcal
I. CH3 CH2 CH2 COO - II. CH3 CH2 CH2 S- 26. The following data were obtained at a certain
III. CH3 CH2 CH2 O - temperature for the decomposition of NH3 in
(a) II > III > I (b) III > II > I (c) I > III > II (d) I > II > III contact process with tungsten.
19. Match the Column where, Column I represents the Intial partial pressure of NH3 (mm Hg) 50 100 200
molecular formulae of the complex compound and
t1 / 2 3.64 1.82 0.91
Column II represents number of unpaired electrons.
Column I Column II The order of the above reaction is
A. [Fe(H2O)6 ]2+ 1. 0 (a) 1 (b) 2 (c) 3 (d) 4
B. [Fe(CN)6 ]3- 2. 1 27. Gold crystallises in fcc lattice with edge length of
C. [NiCl 4 ]2- 3. 2 4.05 Å. The density of gold in the fcc lattice in g/C is
2- (Given, atomic mass of Au = 197 amu)
D. [Ni(CN)4 ] 4. 4
(a) 19.7 (b) 24.3 (c) 12.4 (d) 15.6
A B C D A B C D 28. A buffer solution was prepared by adding one mole
(a) 1 2 3 4 (b) 4 2 3 1 of CH3 COOH and one mole of CH3 COONa . Now,
(c) 4 2 1 3 (d) 2 4 1 3
6g of NaOH is added to the buffer solution. The new
20. Which of the following complex compound will be pH of the solution will be (Given, pKa for CH3 COOH
formed when excess of KCN is added to aqueous is 4.745 and log 135 . )
. = 013
solution of CuSO4 ? (a) 4.875 (b) 5.235 (c) 5.745 (d) 4.445
(a) K 3[Cu(CN)4 ] (b) K 2[(Cu(CN)4 ]
29. Which of the following graph represents the plot of
(c) Cu(CN)2 (d) K [Cu(CN)2 ]
the amount of gas absorbed per unit mass of
21. While calculating the percentage of nitrogen adsorbent (x / m) versus temperature (T ) in
present in an organic compound, by Kjeldahl’s chemisorption at constant pressure?
method, the ammonia evolved required 20.10 mL of
1M H2 SO4 for complete neutralisation. If 1g of the
organic compound was taken initially, the (a) x (b) x p=constant
m p=constant m
percentage composition of N in the compound is
(a) 28.15 (b) 56.30 (c) 14.075 (d) 34.2
T T
22. Which of the following represents the correct order
of boiling point of the hydrides of nitrogen family?
(a) NH 3 > PH 3 > AsH 3 > SbH 3 (b) PH 3 < NH 3 < AsH 3 < SbH 3 p=constant
(c) x (d) x p=constant
(c) PH 3 < AsH 3 < NH 3 < SbH 3 (d) SbH 3 < PH 3 < AsH 3 < NH 3 m m

23. An athlete inhales 150 g of oxygen during an event.


T T
If 40% of this oxygen is used for the complete
oxidation of glucose, the moles of glucose oxidised 30. Which of the following represents the correct order
during the event is of basicity of the following amines?
(a) 0.21 (b) 0.115 (c) 0.42 (d) 0.30
NH2 NH2 NH2
24. A solution of urea of unknown concentration has a NO2
boiling point of 101.12° C. The freezing point of the
(a)
same solution will be (Given, Kf and Kb for water are
1.86 and 0.512 respectively) NO2
(a) 4.07°C (b) - 4.07°C (c) 2.035°C (d) - 2.035°C NO2

25. The resonance energy of benzene calculated from (b) C 2H 5NH 2 < (C 2 H 5)2NH < (C 2H 5 )3N
the following thermochemical equations is (c) N(CH 3 )3 < CH 3 NH 2 < (CH 3 )2NH
C2 H4 + H2 ¾® C2 H6 , DH = - 32.7 kcal (d) All of the above

Answers
1. (a) 2. (b) 3. (b) 4. (c) 5. (d) 6. (a) 7. (c) 8. (d) 9. (c) 10. (c)
11. (a) 12. (d) 13. (c) 14. (d) 15. (d) 16. (c) 17. (b) 18. (a) 19. (b) 20. (a)
21. (b) 22. (c) 23. (a) 24. (b) 25. (b) 26. (b) 27. (a) 28. (a) 29. (c) 30. (c)

Detailed solutions of these questions are available on http://www.arihantbooks.com/Chemistry%20Spectrum.pdf

22
Answer with Explanations
1. (a) The time period of revolution of an electron in Bohr’s orbit is Cl
n 3h 3
given by T= H CH3
4p 2 me k 2 Z 2e 4
H 3C H
n3
Hence, Tµ Cl (Optically active)
Z2
where, n and Z are Bohr’s orbit of revolution and atomic number Similarly, the Fischer projection formula of II can be written as:
respectively. Hence, Cl

T1 n13 ´ Z 22 2 3 ´ 3 2 H3C H
= = [Q n1 = 2 , Z1 = 2 , n 2 = 3 , Z 2 = 3]
T2 n 23 ´ Z12 3 3 ´ 2 2 H3C H
2 Cl
=
3 (Meso-compound)

2. (b) For isoelectronic species, radius is inversely proportional to Z. 6. (a) The reaction proceeds in the following way.
Hence, the order of ionic radius is O 2 - > F - > Na + . The first
H+
ionisation enthalpy of Be is greater than that of B, due to full-filled
–H2O
s-orbital configuration in Be. Hence, the correct order of
OH OH2
ionisation enthalpy is B < Be < C < N.
(2º)
Acidity of oxides of same element increases with oxidation state.
+
Hence, the order of acidity is Cl 2O 7 > Cl 2O 3 > Cl 2O . The order –H
of screening effect of different orbitals are s > p >d > f . 1,2-methyl
shift
3. (b) The balanced equation for the reduction of MnO -4 and MnO 2 in
acidic medium is 7. (c) The bond order value can be calculated as
MnO -4 + 8H+ + 5 e - ¾® Mn 2 + + 4H2O ; E ° = 1.51 V ...(i) C 2 : s1s 2 *s1s 2 s2 s 2 s2 s 2, p 2 px2 » p 2 py2
DG1° = - nFE ° N - Na 8 - 4
\ \ BO = b = =2
2 2
= - 5 ´ 1.51 F = - 7.55 F
O 2 : s1s 2 *s1s 2 s2 s 2 *s2 s 2 s 2 pz2 p 2 px2 » p 2 py2
MnO 2 + 4H+ + 2 e - ¾® Mn 2+ + 2H2O , E ° = 1.23 V ...(ii)
*p 2 p1 » *p 2 p1
DG2° = - nFE ° = - 2 ´ 1.23 F = - 2 .46 F x y
10 - 6
Subtracting Eq. (ii) from Eq. (i), we get \ BO = =2
2
MnO -4 + 4H+ + 3 e - ¾® MnO 2 + 2H2O +
As C 2 and CN are isoelectronic species, they have same bond
\ DG ° = DG1° - DG2° = - 7.55 F - ( - 2 .46 F ) order of 2. Again the bond order of B 2 = 1, F2 = 1 and CN- = 3.
= - 5.09 F 8. (d) Oxidation half C 2O 24 - ¾¾® 2CO 2 + 2 e - ...(i)
DG ° - 5.09 F
\ E ° MnO –4 / MnO 2 = = = 1.70 V Reduction half 2MnO -4 +16H+ + 10 e - ¾¾® 2Mn 2 + + 8 H2O ...(ii)
- nF -3 F
By multiplying Eq. (i) by 5 and adding Eq. (ii), we get
4. (c) PHBV is an example of biodegradable polymer which is 2MnO -4 + 5C 2O 24 - + 16H+ ¾¾® 2Mn 3 + + 10CO 2 + 8H2O
obtained through the following reaction.
Hence, x and y are respectively, 5 and 16.
OH OH
9. (c) In ion-exchange method for the removal of permanent
CH3— CH—CH2COOH +CH3—CH2—CH—CH2 COOH hardness of water, sodium aluminium silicate (NaAlSiO 4 ) is
added to hard water. Ca 2+ and Mg 2+ ions are removed due to ion
3-hydroxybutanoic acid 3-hydroxypentanoic acid exchange reaction. Given below
2Na AlSiO 4 ( s ) + M 2 + ( aq ) ¾¾® M(AlSiO 4 )2( s ) + 2 Na + ( aq )
—O—CH—CH2—C—O—CH—CH2—C— (M = Ca and Mg)
n
CH3 O C2H5 O 10. (c) The solubility of hydroxides of alkaline earth metals increases
(PHBV) down the group. Hence, the correct order is
Mg(OH)2 < Ca(OH)2 < Sr(OH)2 < Ba(OH)2 . This is because, in
5. (d) This problem can be solved by converting Newman projection case of alkaline earth metal hydroxides, lattice enthalpy
formulae into Fischer projection. decreases much more than the hydration enthalpy down the
Cl group. Again due to larger size of SO 2- 2-
4 and CO 3 ions, the lattice
H H
CH3 energy remains, almost constant down the group, whereas
H CH3 CH3
hydration enthalpy decreases. Hence, the solubility of carbonates
Cl CH3
Cl Cl and sulphates decrease down the group.
H CH3 H
H 11. (a) Trialkyl/aryl substituted silicon chlorides are used to terminate
Cl CH3 Cl the polymerisation reaction, as they block the — OH group of the
I
chain from all sides ceasing the further dehydration.

23
C2H5 C2H5 15. (d) The reaction proceeds in the following way.
n HO—Si—OH+HO—Si—C 2H 5
C
C2H5 C2H5 AICl3 Zn(Hg)
+ O
Polymerisation HCl
C C
C2H5 C2H5 HO HO
A B
HnO—Si—O—Si—C2H5
Termination
of chain SOCl2 AICl3 LiAlH 4
C2H5 n C2H5

12. (d) The structure of sucrose and maltose are given as : C


Cl
6 OH
CH2OH C D E

5 O
1
O 16. (c) This is an example crossed Cannizzaro reaction, in which,
H H HOH2C H
formaldehyde undergoes oxidation to give HCOONa and
H 5 CH2OH
4
OH H O H OH
1 2 benzaldehyde undergoes reduction to give
HO CH2OH .
3 2 3 4

H OH OH H 17. (b) The major product formed is


a-D-glucose b-D-fructose CH3 CH2—CH — CH CH—CH3
(Sucrose)
6 6 CH3
CH2OH CH2OH H3O+
5 O 5 O 1,2- hydride
H H H H CH3 CH2—CH—CH—CH2CH3 CH3 CH2—C—CH2CH2CH3
H H shift
4 4 1
OH H O OH H CH3 CH3
1 OH
HO (2º) (3º more stable)
3 2 3 2 OH
H OH H OH H2 O
a-D-glucose a-D-glucose C2H5—C—C3H7 (Optically active)
–H+
(Maltose)
CH3
Hence, C1 - C 2 glycosidic linkage is found in sucrose, where (Contains 1 chiral carbon)
C1 - C 4 glycosidic linkage is found in maltose. Again glucose
has pyranose structure, where as fructose has furanose Since, it is a 3° alcohol it is dehydrated easily and reacts with
structure. Lucas reagent (HBr) to give white turbidity.

13. (c) Sodium benzoate is used in small amount as food 18. (a) Nucleophilicity is directly proportional to the acidic nature of
preservative. The rest options are given as the nucleophile. The correct of acidity of nucleophile are
OH OH SO2NH2 II > III > I
Because CH3CH2CH2COO - is the conjugate base of the
NH strongest acid CH3CH2CH2COOH and CH3CH2CH2S - is the
conjugate base of the weakest acid CH3CH2CH2SH.
SO2
Cl 19. (b) [Fe(H2O)6 ]2+ and [NiCl 4 ]2- will form outer orbital complex and
NH2
Chloroxylenol Saccharin Sulphanilamide hence no pairing of electrons will occurs. Whereas, [Fe(CN)6 ]3-
(Antiseptic) (Artificialsweetner) (Antibiotics) and [Ni(CN)4 ]2- will form inner orbital complex and pairing of
electron pair will occur.
14. (d) Tertiary amines give soluble nitrile salt with
HNO 2(NaNO 2 + HCl) which on further heating produces yellow Hence, the number of unpaired electrons in
oily compound. The reaction is given below : [Fe(H2O)6 ]2 + = 4, [Fe(CN)6 ]3 - = 1, [NiCl 4 ]2 - = 2
and [Ni(CN)4 ]2- = 0
(CH3)3 N + HONO [(CH3)3 NH] NO2
Trimethyl ammonium 20. (a) The following reaction occurs when excess of KCN is added to
nitrite (soluble) CuSO 4 solution.
D Cu 2+ + CN- ¾¾® CuCN
CH3 CuCN + CN- ¾¾® [Cu(CN)4 ]3 -

(Excess)
CH3—N—N O + CH3OH
(Yellow oil) or K 3[Cu(CN)4 ]

24
21. (b) The reaction occurring during Kjeldahl’s estimation of N is 27. (a) For fcc lattice, r = a
given as, 2 2
organic compound + H2SO 4 ¾¾®(NH4 )2SO 4 Again in fcc lattice, number of atoms per unit cell = 4
2NaOH \ Mass of the 4 atoms in the unit cell (m)
¾® Na 2SO 4 + 2NH3 + 2H2O
¾¾¾
= 4 ´ 197 u
2 NH3 + H2SO 4 ¾¾® (NH4 )2SO 4
= 4 ´ 197 ´ 1.66 ´ 10 -24 g [1u = 1.66 ´ 10 -24 g]
\ 1M 20.10 mL H2SO 4 will react with = 1M 40.02 mL NH3
= 1.31 ´ 10 -21 g
1000 mL of 1M NH3 contains = 14 g NH3
14 Volume of unit cell = a 3
\ 40.20 mL of 1M NH3 will contain = ´ 40.20 g N
1000 = ( 4.05 ´ 10 -8 )3 cc
14 ´ 40.20 = 6.64 ´ 10 -23 cc
\ Percentage of N = ´ 100 » 56.3%
1000 ´ 1 g
m 1.31 ´ 10 -21 g
\ Density of gold = = = 19.7 g /cc
22. (c) Due to hydrogen bonding in NH3 , boiling point of NH3 is more V 6.64 ´ 10 -23 cc
than that of PH3 and AsH3 . But due to increase in molecular mass
down the group, the boiling point of SbH3 and BiH3 are higher than 28. (a) Concentration of NaOH in the solution = 6 = 0.15 M
40
NH3 .
The following neutralisation reaction takes place when NaOH is
Hence, the correct order of boiling point is added to the solution.
PH3 < AsH3 < NH3 < SbH3 CH3COOH + NaOH -
CH3COONa + H2O
Initial 1M 0.15 1M 0
23. (a) The oxidation of glucose proceeds through the following Final (1 - 0. 15 ) 0 1 + 0. 15 0.15
reaction.
\ [CH3COONa] = 1.15 M ,[CH3COOH] = 0.85 M
C 6 H12O 6 + 9O 2 ¾¾® 6CO 2 + 6H2O
Applying Henderson’s equation
\ 9 moles of O 2 oxidises = 1 mole of glucose [Salt] 115
.
It is given that 40% of oxygen is used for oxidation of glucose. pH = pK a + log = 4.745 + log
[Acid] 0.85
150 ´ 40
\ Moles of oxygen used = = 1.875 mol = 4.745 + 0.13 = 4.875
100 ´ 32
9 moles of oxygen oxidises = 1 mole glucose
29. (c) Chemisorption increases with increase in temperature, till the
activation energy for the chemical reaction is achieved. Once the
1
\ 1.875 moles of oxygen oxidises = ´ 1.875 » 0.21 mol activation energy is achieved on increasing the temperature
9 further, the rate of chemisorption decreases. Hence, (c) is the
24. (b) Let the molality of the solution be m . Then, most appropriate graph for dependence of chemisorption on
DTf DTb temperature.
m= = [Q As the solution remain same]
Kf Kb 30. (c) —NO 2 has a strong electron withdrawing effect and o and
K 1.86 p-nitroaniline are more resonance stabilised than m-nitroaniline.
\ DTf = DTb ´ f = 1.12 ´ = 4.07 °C
Kb 0.512 Hence, the correct order of basicity.
Hence, the freezing point of the solution will be - 4.07 ° C. NH2 NH2 NH2
25. (b) Since, C 6H6 has 3 isolated carbon-carbon double bonds, its NO2
heat of hydrogenation should be nearly equals to three times the
value for the heat of hydrogenation of C 2 H4.
NO2
\ Resonance energy of C 6H6 = 3 ´ ( - 32 .7 ) - ( - 49.2 ) = - 48.9 kcal
NO2
26. (b) Let, the order of reaction be ‘n’, then t1 / 2 µ 1n - 1
[ A] Due to solvation effect and steric hindrance, the order of basicity
n-1 n-1 for different aliphatic amines are
(t1 / 2 )1 æp ö 3.64 æ 100 ö n-1
\ =ç 2÷ Þ =ç ÷ Þ 2 =2 (CH3 )2NH > CH3NH2 > (CH3 )3N
(t1 / 2 )2 çè p1 ÷ø 1.82 è 50 ø
and (C 2H5 )2NH > (C 2H5 )3N > C 2H5NH2
Þ n - 1 = 1Þ n = 2
Hence, order of the reaction is 2.

25
General Instructions
1. All questions are compulsory.
2. Q. no. 1 to 5 are very short answer questions and carry 1 mark each.
3. Q. no. 6 to 10 are short answer questions and carry 2 marks each.
4. Q. no. 11 to 22 are also short answer questions and carry 3 marks each.
5. Q. no. 23 is a value based question and carry 4 marks.
6. Q. no. 24 to 26 are long answer questions and carry 5 marks each.
7. Use log tables if necessary, use of calculator is not allowed.

Very Short Answer Type Questions Short Answer Type Questions (II)
1. What is the set of four quantum numbers for the 11. What is the Einstein’s equation for kinetic energy of
valence electron of sodium (Z = 11)? photoelectrons? Calculate the kinetic energy of an
2. What does the catenation property of carbon mean? electron when radiation of wavelength 10- 2 m.
3. What causes the diagonal relationship in the (Threshold frequency of metal is 2 ´ 10-10 s -1 ).
periodic table? 12. PCl5 has trigonal bipyramidal whereas IF5 has
4. What is average atomic mass? square pyramidal geometry. Why?
5. Write the IUPAC name of the following compound. 13. What is a state function? q and W are not a state
Cl function but q + W is a state function. Explain.
H 14. Discuss the effect of change in temperature and
Cl pressure on the reaction given below.
Short Answer Type Questions (I) 2 AB(g) - A (g) + 2B (s), DH = + ve
2

6. Consider the following reaction and its enthalpy of 15. Equal volumes of 1 ´ 10- 4 M CaCl2 and 5.0 ´ 10- 3 M
reaction. Is the enthalpy of formation of the K2 SO4 solutions are mixed. Show whether a
compound is equal to the enthalpy of reaction value? precipitation of CaSO4 will be formed or not.
Give reason. (Solubility product of CaSO4 is 2.4 ´ 10- 5 ).
MgO(s) + CO2 (g) ¾® MgCO3 (s) 16. A solution of volume 500 mL is prepared by adding
D f H° = x kJ mol - 1 2g of NaNO3 in distilled water. What will be the
7. The value of KC for the equilibrium reaction molarity of the solution prepared?
N2 (g) + 3H2 (g)
- 2NH3 (g) is 1 ´ 10- 1 at 500 K. 17. Balance the following redox reaction by ion
Calculate the value of Kp for the reaction. - electron method.
8. Define allotropes. Name the two allotropes of MnO4- + Fe2 + ¾® Mn2 + + Fe3 + (in acidic medium)
carbon. 18. What do you mean by electrochemical series? How
9. How the hydration enthalpy of alkali metal ions vary it can be helpful in determining the appropriate
down the group? element that can displace another element from its
10. How many moles of KCl are present in 45 mL of solution?
0.250 M KCl solution?

68
19. Explain 25. What does the term electron gain enthalpy
(i) How boiling can remove temporary hardness of means? How does it vary along a group and
water? along a period? Which of the following elements
(ii) Why hydrogen peroxide is stored in wax lined has most negative electron gain enthalpy?
bottles? P,S,Cl,F
(iii) Water has higher boiling point than hydrogen 26. How would you convert the following?
sulphides.
(i) Benzoic acid to benzene
20. Complete the following chemical equations. (ii) 2-bromopropane to 1-bromopropane
(i) A + 3LiAlH4 ¾® B + 3LiF + 3AlF3
D D
(iii) Benzene to m-chloronitrobenzene
(ii) H3 BO3 ¾¾ ® A ¾¾ ®B (iv) Benzene to acetophenone
(iii) SiO2 + 2NaOH ¾® A + B (v) 1-butene to but-1, 2-diol
21. (i) What do you mean by the process of crystallisation? Detailed solutions of these questions are available on
(ii) What is the principle behind chromatography and http://www.arihantbooks.com/Chemistry%20Spectrum.pdf
distillation?
22. Draw the resonance structures of the following
compounds.
CHEMISTRY
(i) CH2 —
— CH—Cl
(ii) CH2 == CH — CH == CH2
Hair Dye Could be used to Track
(iii) CH2 == CH— C == O Down Criminals
|
H It would be absurd but a well known chemistry
technique that could help authorities in
Value Based Question identifying criminals based on their artificial
23. Manvi and Sunaina were returning home after hair colour. Usually hairs left behind at a crime
attending the school. They found some cows on the scene are associated with DNA testing but such
roadside, Manvi took out few pieces of bread in a a procedure requires a complete hair and is
polythene and wanted to give it to cows. Sunaina often time consuming.
stopped her and asked to remove polythene before
This technique uses Surface Enhanced Raman
giving it to cows.
Spectroscopy (SERS) to precisely measure how
(i) Why Sunaina told Manvi to remove polythene? light from a LASER bounces off a hair.
(ii) How the materials like polythene should disposed? Vibrations within the molecules on the hair’s
(iii) Draw the structure of a biodegradable synthetic surface change the energy of reflected photons
polymer. and are caught by a detector. If the sample has a
(iv) What values are associated with Sunaina? dye on it (on blood, drugs, ink, explosives etc.)
the LASER will reflect differently and each dye
Long Answer Type Questions creates a unique pattern.
24. A non-metallic element of group 13, which is used in The techniques is so precise that scientists are
making bulletproof vests is extremely hard solid of able to identify distinct brands of dye and even
black colour. It can exist in many allotropic forms and determine whether the dye was temporary or
has unusually high melting point. Its trifluoride acts as permanent even when sampling a microscopic
a Lewis acid towards ammonia. The element exhibits piece of hair. Further, because SERS is fast and
maximum covalency of four. Identify the element and doesn’t destroy the sample, so it can be used for
write the reaction of its trifluoride with ammonia. DNA analysis in later stages too.
Explain why does the fluoride act as a Lewis acid?

69
Explanations
1 In IF5 , iodine is the central atom which hybridises as follows:
1. n = 3, l = 0, m = 0, s = +
2 s p d
Iodine in ground state
2. Catenation property of carbon means the tendency of carbon
atom to link with each other. Due to this property, carbon can Iodine in excited state
form a long chain of carbon atoms.
sp 3d 2 hybridisation
3. Similarity in ionic sizes and charge/radius ratio are the causes
Due to the presence of one lone pair and 5 bond pair, IF 5 has
for a diagonal relationship.
square pyramidal geometry.
4. It is defined as the average of atomic mass of all the isotopes 13. State functions are those quantities that depends only on the
of an element.
state of the system irrespective of the path followed to achieve
5. 2, 5-dichlorohexanal this state.
6. Enthalpy of formation of a compound is the change in q (heat) and W (work done) are the quantities that depends on
the path followed but q + W = DU (change in internal energy)
enthalpy when one mole of compound is formed from its
depends on the initial and final state of the system. Hence, q + W
constituent atoms in their most stable state. Here in the given
is a state function.
reaction, MgCO 3 is not formed from its constituent atoms,
hence D f H° is not same as D r H°. 14. DH for the forward reaction is positive, i.e. endothermic
process. Hence, on increasing temperature, forward reaction
7. For the reaction,
will be favoured while on decreasing temperature backward
Dn = (2 ) - (1 + 3 ) = - 2
reaction will be favoured. On moving towards forward
Use K p = Kc ( RT )Dn = 1 ´ 10 - 1 ( 0.0831 ´ 500 )- 2 = 5.79 ´ 10 - 5 reaction, the number of gaseous moles decreases. Hence, on
8. Allotropes are the different forms of an element that have increasing pressure, forward reaction will be favoured while
different physical properties but have same chemical on decreasing pressure, backward reaction will be favoured.
properties. Two allotropes of carbon are diamond and 15. Concentration of CaCl 2 in the solution becomes half as the
graphite. volume becomes double after mixing.
9. On moving down the group, the ionic size of the alkali metals 1
Concentration of CaCl 2 = 1 ´ 10 -4 ´ = 5.0 ´ 10 -5 M
increases, hence tendency for hydration of these ions 2
decreases. Hence, the hydration energy of alkali metal ions Similarly, concentration of K 2SO 4 becomes half.
varies as follows : 1
Concentration of K 2SO 4 = 5.0 ´ 10 -3 M ´ = 2.5 ´ 10 -3 M
Li + > Na + > K + > Rb + > Cs + 2
Now, ionic product of CaSO 4 = [Ca 2 + ] [SO 24 - ]
10. 0.250 mole of KCl are present in 1L of solution.
0.250 mol = ( 5.0 ´ 10 - 5 )(2 .5 ´10 - 3 ) = 12 .5 ´ 10 - 8 = 125
. ´10 - 7
Number of moles of KCl present in 45 mL = ´ 45 mL
1000 mL Since ionic product is less than the solubility product of CaSO 4 ,
= 0.011mol precipitation does not occur.
2g 1
11. Einstein’s equation for kinetic energy of photoelectron is 16. Number of moles of NaNO 3 = = mol
1 85 g mol - 1 42.5
KE = me v 2 = h( n - n 0 )
2 Number of moles of solute
Molarity of a solution =
where, me is mass of an electron, v is the velocity of electron, n is Volume of solution (in L)
the frequency of radiation, n 0 is the threshold frequency of metal 1 1
= mol ´ ´ 1000 = 0.047 mol L-1
c 3 ´ 10 8 m/s 42.5 500 L
Frequency of radiation ( n ) = = = 3 ´ 1010 s -1
l 10 - 2 m 17. Consider the reduction half reaction
KE of photoelectron = h( n - n 0 ) MnO -4 ¾® Mn 2 +
= (6.626 ´ 10 -34 Js) (3 ´ 1010 s -1 - 2 ´ 1010 s -1 ) MnO -4 ¾® Mn 2 + + 4H2O
= 6.626 ´ 10 -34 Js (1 ´ 1010 s -1 ) = 6.626 ´ 10 -24 J MnO -4 + 8H+ ¾® Mn 2 + + 4H2O
2 3 0
3s 3p 3d MnO -4 + 8H+ + 5e - ¾® Mn 2 + + 4H2O ... (i)
12. Phosphorus in ground state
Now, consider oxidation half reaction.
Phosphorus in excited state Fe 2 + ¾® Fe 3 + ; Fe 2 + ¾® Fe 3 + + e - … (ii)
Multiply the Eq. (ii) by 5 to balance the number of electrons
sp3d hybridisation
transferred in oxidation and reduction half reactions.
3
For sp d hybridisation, geometry of the molecule is trigonal
5Fe 2 + ® 5Fe 3 + + 5 e - ... (iii)
bipyramidal. In PCl 5 , phosphorus is central atom and its five
Adding Eqs. (i) and (iii), we get
hybridised orbitals overlap with atomic orbitals of five chlorine
atoms. MnO -4 + 8H+ + 5Fe 2 + ¾® 5Fe 3 + + Mn 2 + + 4H2O

70
18. Electrochemical series is a list of elements/ions/molecules
arranged such that their standard reduction potential 22. (i) CH2 CH—Cl CH2—CH Cl
increases from top to bottom of the series. This series is
helpful in determining the metal or element that can displace (ii) CH2 CH—CH CH2 CH2—CH CH—CH2
another metal ion from its solution. The metal that lies above a
particular metal can displace it from its solution because the (iii) CH2 CH—C O CH2—CH C—O
metal that lies above have lower reduction potential or higher
H H
oxidation potential. That means the metal lies above has
23. (i) The polythene is a non-biodegradable material that does
higher tendency to form ion than the lower metal.
not degraded by bacteria on its own. Thus, polythenes if
19. (i) Temporary hardness of water is due to soluble magnesium consumed by the cattle, it may cause the cattle to be dead.
and calcium hydrogen carbonates. During boiling, these Hence, Sunaina stops Manvi to give bread in polythene bag
hydrogen carbonates are converted into magnesium to the cows as cows may have swallowed breads alongwith
hydroxide and calcium carbonate which are insoluble and polythene which may lead to their death.
get deposited at the bottom of the flask and can be filtered (ii) Materials like polythene which are non-biodegradable
off. should be collected separately and recycle them. This type
Mg(HCO 3 )2 ¾Boiling
¾ ¾® Mg(OH)2 ¯ + 2CO 2 ­ of waste should not be disposed alongwith biodegradable
Ca(HCO 3 )2 ¾Boiling
¾ ¾® CaCO 3 ¯ + H2O + CO 2 ­ wastes to the landfills because it remains as over a long
period of time and causes pollution and may mix with
(ii) Hydrogen peroxide decomposes slowly on exposure of groundwater that further polluted the water.
light.
(iii) Poly-b-hydroxybutyrate-co-b-hydroxyvalerate (PHBV) is an
2H2O 2( l ) ¾® 2 H2O( l ) + O 2( g ) example of biodegradable synthetic polymer having the
If it is stored in metal container, its decomposition is following structure.
catalysed by metal. If it is stored in glass container then the æ ö
alkali metal ion in glass catalysis the decomposition ç ÷
reaction. Thus, to prevent its decomposition, it is stored in ç ¾ O ¾ C H ¾ CH ¾ C ¾ O ¾ CH ¾ CH ¾ C ¾ ÷
2 2
ç ½ ½½ ½ ½½ ÷
wax lined bottles. ç ÷
è CH 3 O C H
2 5 O øn
(iii) Water molecules exhibit hydrogen bonding due to which
these molecules remain associated with each other and PHBV
hence, its boiling point is higher. Such type of bonding does (iv) Values associated with sunaina are responsibility towards
not exist in hydrogen sulphide due to smaller the health of animals and proper use of scientific knowledge
electronegativity difference between H and S. Hence, at right time.
molecules of H2 S (hydrogen sulphide) are unable to
associate strongly which causes lower boiling point. 24. The non-metallic element is boron. Boron is hard solid of
black colour. It exists in many allotropic forms and due to its
20. (i) 4BF3 + 3LiAlH4 ¾® 2B 2H6 + 3LiF + 3AlF3
A B
strong crystalline lattice, it has an unusually high melting
D
(ii) H3BO 3 ¾¾ D
® HBO 2 ¾¾® B 2O 3
point. Its trifluoride, BF3 acts as a Lewis acid because boron
A B has six electrons around it, thus it is electron deficient to
(iii) SiO 2 + 2NaOH ¾® Na 2SiO 3 + H2O complete its octet. When it reacts with ammonia, it accepts
A B the lone pair of nitrogen to form an adduct.
21. (i) Crystallisation is the process for the purification of solid BF3 + NH3 ¾® F3B ¬ NH3
organic compounds. The principle involved in this
The maximum covalency of boron is four because it has no
technique is the difference in solubilities of the compound
empty d -orbital to expand its octet.
and the impurities. The impure compound is dissolved in a
suitable solvent in which it is sparingly soluble at room 25. When a neutral gaseous atom takes up an electron to form a
temperature, completely soluble at high temperature but negatively charged ion (anion), the enthalpy released during
insoluble at low temperature. The solution of the compound this process is called electron gain enthalpy.
is first heated to get a saturated solution, then on cooling A(g) + e - ¾® A- (g)
the pure compound separates as crystals while impurities As the atomic size increases, the effective nuclear charge on the
remain in the solution. incoming electron decreases, thus the electron gain enthalpy
(ii) The principle behind chromatography is movement of decreases. Thus, on moving down the group, the atomic size
mixture with the solvent or mobile phase over the stationary increases and electron gain enthalpy decreases.
phase. In this technique, mixture is placed over stationary On moving from left to right along a period, the atomic size
phase and the mobile phase move over stationary phase decreases, nuclear charge increases thus electron gain enthalpy
along with the mixture components. The distance travelled increases.
by each component of the mixture is different which F should have the highest negative value of electron gain
separates the mixture. enthalpy, but chlorine has the highest negative electron gain
The principle behind the distillation technique is the enthalpy because in fluorine, extra electron is added to very
difference in the boiling points of compound and impurities. small 2 p-orbital which causes repulsion between electrons while
The desired compound having lower boiling point vaporise in chlorine, the added electron is in 3 p-orbital which is bigger in
on increasing temperature but non-volatile impurities having size and hence less repulsion.
higher boiling point remain in the flask. The vapours of Hence, among the given elements, chlorine has the highest
compound are collected in another flask and condense to negative electron gain enthalpy.
get the pure compound.

71
COOH
C—CH3
CaO
26. (i) + NaOH + Na2CO3
Anhyd.AICl3
(iv) + Cl—C—CH3 + HCl
Benzoic acid Benzene
Benzene Acetophenone
Alc.KOH
(ii) CH3—CH—CH3 CH3—CH CH2
–HBr
Br (v) CH3—CH2—CH == CH2 + H2O + [O]
2-bromopropane
HBr 1-butene (From dil. KMnO4)
CH3CH2CH2Br
(C6H5CO)2O2 273 K
CH3—CH2—CH—CH2
1-bromopropane
OH OH

NO2 NO2 But-1,2-diol

Conc. HNO3 Cl2


(iii)
Conc. H2SO4 Anhyd. AlCl3
D Cl
Benzene
m-chloronitrobenzene

72
General Instructions
1. All questions are compulsory.
2. Q. no. 1 to 5 are very short answer questions and carry 1 mark each.
3. Q. no. 6 to 10 are short answer questions and carry 2 marks each.
4. Q. no. 11 to 22 are also short answer questions and carry 3 marks each.
5. Q. no. 23 is a value based question and carry 4 marks.
6. Q. no. 24 to 26 are long answer questions and carry 5 marks each.
7. Use log tables if necessary, use of calculator is not allowed.

Very Short Answer Type Questions Short Answer Type Questions (II)
+
1. What is effective nuclear charge? 11. (i) Write the electronic configuration of Cu ion
2. The fluorides of alkaline earth metals are relatively (Z = 29).
less soluble than the chlorides. Why? (ii) Compare the energies of the two radiations with
3. Why beryllium forms compounds which are largely wavelength 6000 Å and 4000 Å.
covalent in nature? (iii) Which one of the following is not possible and
4. What do you understand by free expansion? why ?
2s, 2d, 4f, 5p
5. Write the chemical equation for the standard
enthalpy of combustion (D cH°) of C2 H6 (g). 12. Arrange the elements N, P, O and S in order of
(i) increasing first ionisation enthalpy
Short Answer Type Questions (I) (ii) increasing negative electron gain enthalpy
6. What will be the wavelength of a stone of mass (iii) increasing non-metallic character
0.2 kg moving with a velocity of 40 ms -1 . 13. For the reaction, A (g)+ B (g) ¾® 3C (g) at 298K
7. Write the equilibrium constant expressions for the DU° = - 7.5 kJ and DS° = - 38 JK -1 . Calculate DG° for
following reactions: the reaction and predict whether the reaction is
(i) CH3 COOH (aq) = CH3 COO - (aq) + H+ (aq) spontaneous or not.
(ii) CaCO3 (s) = CaO (s) + CO2 (g) 14. 0.05M CH3 COOH solution has pH value 2.35.
8. Give the chemical equations for the preparation of Calculate its ionisation constant.
diborane from 15. For the reaction, N2 (g) + 3H2 (g) =2NH3 (g). How
(i) boron trifluoride and will the values of Kp and composition of equilibrium
(ii) sodium borohydrides (NaBH4 ) mixture be affected by
9. Why do beryllium and magnesium not impart colour (i) increasing the pressure ?
to the flame in the flame test? (ii) increasing the temperature?
10. Calculate the standard free energy change, DG° for (iii) using a catalyst?
the reaction, 2HgO (s) ¾® 2Hg (l ) + O2 (g) 16. Consider the reaction, A (g) + B(g) = C (g) + D(g)
having Kc equals to 64. We take 1 mole of each of the
DH° = 91 kJ mol -1 at 298 K, S(HgO)
° = 72.0 JK -1 mol -1 ,
reactants and products in 1L container. Calculate
-1 -1
° = 77.4 JK mol and
S(Hg) the equilibrium concentration of all the reactants
° ) = 205 JK -1 mol -1 at 298 K
S(O and products.
2

70
17. Calculate the oxidation number of nitrogen in the Long Answer Type Questions
following compounds. 24. (i) Define buffer solution.
(i) N2 O (ii) NO2 (iii) NO (ii) What will be the change in reaction quotient, Q
18. Balance the following equations of redox reactions for the following reaction when pressure is
using half reactions method and name the species increased?
which are oxidised and reduced in the reactions. A (g) + 2B (g) =C (g)
(i) I- + IO3- + H+ ¾® I2 + H2 O (iii) The degree of ionisation of 0.5 M HX
(ii) Bi + NO3- + H+ ¾® NO2 + Bi3+ + H2 O (weak acid) is 0.45. Calculate the pH and pKa of
(iii) I- + O2 + H2 O ¾® I2 + OH - the acid.
25. An unsaturated hydrocarbon A adds two
19. (i) Determine the strength of 10 L volume H2 O2 molecules of H2 and on reductive ozonolysis gives
solution.
butane-1, 4-dial, ethanal and propanone. Give the
(ii) Arrange the following compounds in order of structure of A, write its IUPAC name and explain
increasing reducing property NaH, MgH2 and the reactions involved.
H2 O.
26. (i) BCl3 exists as a monomer whereas AlCl3 is
20. (i) Why silicon shows a higher covalency than dimerised through halogen bridging. Explain.
carbon?
(ii) Give the reactions involved in the Solvay
(ii) Why CO2 is a gas whereas SiO2 is a solid? process for the preparation of sodium
(iii) Why CO is a poisonous gas? carbonate.
21. Draw the resonance structure of the following (iii) What happens when borax is heated strongly?
compounds if applicable.
O The solutions of these questions are available on
½½ http://www.arihantbooks.com/Chemistry%20Spectrum.pdf
(i) CH3 ¾ CH ==CH ¾ CH2 ¾ C ¾ CH3
O
½½
(ii) CH2 ==CH ¾ C ¾ H
O
JEE Advanced 2015
½½
(iii) CH3 ¾ C ¾ NH2 Application process starts from May 02, 2015
The candidates of JEE (Main) 2015 who qualify to write
22. Complete the following reactions:
JEE (Advanced) 2015 have to register themselves online
(C6 H5 CO)2 O2
(i) CH3 ¾ CH2 ¾ CH==CH2 + HBr ¾¾¾¾® A between May 02, 2015 to May 07, 2015. The top 1, 50,000
candidates (including all categories) who qualify JEE (Main)
Hg2+ / H+
(ii) CH3 ¾ C ººCH + H2 O ¾ ¾ ¾ ¾
¾® B 2015 are eligible to write JEE Advanced 2015. The
333 K
JEE advanced 2015 examination will be conducted on
OH
May 24, 2015. The results of the JEE Advanced 2015 will be
declared on 18th June 2015.
(iii) D
+ Zn C
Exam Pattern
The paper will consist of two question papers. Each paper
Value Based Question will be of three hours duration. Each paper will consist of of
23. Abhishek was returning home from his friend’s three separate sections with Section I - Physics, Section II -
home on his bicycle. On his way he was stuck for Chemistry, Section III - Mathematics. Section 1 - Physics:
few minutes on a traffic signal. After two minutes will enclose 10 Multiple Choice Questions with four options
standing on the traffic signal, he felt dizziness due out of which one option Only will be the correct answer
Section 2 - Chemistry: will have 5 Multiple Choice
to air pollutants expelled by the vehicles. This
Questions with four options each out of which one or more
showed that the exhaust of vehicles have harmful
are correct. Section 3 - Mathematics: will have 5 questions
pollutants that affects our health.
and the answer to each will be a single digit integer ranging
(i) What are the exhaust of motor vehicles that from 0 to 9.
causes air pollution?
(ii) What are the steps we should take to check the
air pollution?

71
Explanations
1. The net positive charge experienced by the outer shell electrons = 0.215 kJK -1 mol -1
from the nucleus after shielding by the inner shell electrons is DG° = 91 kJ mol -1
- (298K) (0.215 kJ K -1 mol -1 )
known as effective nuclear charge (Zeff e ).
= (91 - 64.30) kJ mol -1
2. Fluorides of alkaline earth metals have high lattice energies as
= 26.69 kJ mol -1
compared to chlorides. Thus, the fluorides are less soluble than
their chlorides. 11. (i) Electronic configuration of Cu is 1s 2 2 s 2 2 p6 3 s 2 3 p6 4 s1 3d 10.
3. Beryllium is small in size, thus have high value of ionisation Now, electron in the outermost orbital will be removed first
enthalpy because of which it forms covalent compounds unlike its which is 4s orbital. Hence, electronic configuration of Cu +
other group members. ion is 1s 2 2 s 2 2 p6 3 s 2 3 p6 4 s 0 3 d 10 .
4. Expansion of a gas in vacuum, i.e. in absence of external pressure (ii) Energy of a radiation is calculated as
( pext = 0 ) is called free expansion. Work done for such expansion hc
for an ideal gas is zero irrespective of process is reversible or E = hn =
l
irreversible.
When wavelength of the radiation is high then the energy of
5. Standard enthalpy of combustion is the enthalpy change per the radiation is low and vice-versa.
mole of a substance, when it undergoes combustion and all the
Hence, energy associated with shorter wavelength, i.e.
reactants and products are in its standard state at specified
4000 Å will be higher as compared to radiation of
temperature.
wavelength 6000Å.
7
C 2H6 ( g ) + O 2 ( g ) ¾® 2CO 2 ( g ) + 3H2O ( l ) (iii) 2 s
2
n = 2, l = 0
h
6. According to de-Broglie’s equation, l = It is possible.
mv
2 d n = 2, l = 2
6.626 ´ 10 -34 kg m 2s -1
l= Here, l = 2 is not a permissible value for n = 2 because l
0.2 kg ´ 40 ms -1
should have permissible values from 0 to ( n - 1).
6.626 ´ 10 -34 4 f n = 4, l = 3
l= m
8 Hence, l = n - 1 = ( 4 - 1 ) = 3 is a permissible value. Thus, it is
l = 8.283 ´ 10 -35 m possible.
- + 5p n = 5, l = 1
7. (i) Kc = [CH3COO ] [H ] Here, l = 1 = ( 5 - 4)
[CH3COOH ]
[CaO] [CO 2 ] As l can have values from to ( n - 1) . Hence, 5p is possible.
(ii) Kc =
[CaCO 3 ] 12. (i) Among the four elements N and P has half-filled valence
Since, CaCO 3 and CaO are in pure solid state, their orbital, thus has higher ionisation energy than O and S
concentration remains constant. Thus, equilibrium constant can respectively. Now, bigger the atomic size easier is to ionise
be modified as and lower is the ionisation enthalpy.
[CaCO 3 ] Thus, the increasing first ionisation enthalpy order is
Kc¢ = [CO 2 ] where Kc¢ = Kc
[CaO] S<P<O<N
or K p = pCO2 (ii) Electron gain enthalpy (negative) increases on moving
where, ( pCO 2 = pressure of CO 2 ) across a period from left to right due to increase in nuclear
charge and decreases on moving top to bottom in a group.
8. (i) Boron trifluoride reacts with LiAlH4 in ether to give diborane.
However, N and O belongs to second period which has
4BF3 + 3LiAlH4 ¾® 2B 2 H6 + 3LiF + 3AlF3 2p orbital as valence orbital which is small in size and
(ii) Sodium borohydride (NaBH4 ) when undergoes oxidation causes repulsion for the incoming electron.
with iodine gives diborane. Thus, the order of negative electron gain enthalpy is
2NaBH4 + I 2 ¾® B 2H6 + 2NaI + H2 N<P<O<S
9. The energy required to excite the outer electrons in beryllium and (iii) Non-metallic character increases on moving left to right
magnesium atoms are quite high due to their completely filled across a period and decreases on moving top to bottom in
orbital that require higher energy. This energy does not lie in a group.
visible range of radiation. Thus, these atoms does not impart Thus, the order of non-metallic character becomes
colour in flame test. P<S<N<O
10. Expression to evaluate DG° is as follows : 13. DG ° = DH ° - TDS ° ... (i)
DG ° = DH ° - TDS ° DH ° = DU ° + Dn g RT
° ° °
DSreaction = SSproducts - SSreactants = - 7.5 kJ + (3 - 2) mol 8.314 JK -1 mol -1 ´ 298 K
° ° °
= S(O + 2 S(Hg) - 2 S(HgO) = - 7500 J + 2477.57 J = - 5022.43 J
2)
-1 -1 From Eq. (i) DG° = - 5022.43 J - (298 K) ( - 38 JK -1 )
= [205 + 2 (77.4 ) - 2 (72 .0 )] JK mol
= ( - 5022.43 + 11324) J = 6301.57 J
= 215.8 JK -1 mol -1
As DG is positive, the reaction is non-spontaneous.

72
14. pH = - log [H+ ] (iii) NO x + (- 2 ) = 0
2.35 = - log [H ] + Þ x = +2
\ Oxidation state of nitrogen is + 2.
4.46 ´ 10 -3 = [H+ ]
CH3COOH = CH3COO - + H+
18. (i) Oxidation half reaction 2I - ¾® I 2 + 2 e - ] ´ 5
Initial conc. 0.05 0 0 Reduction half reaction
Equilibrium conc. 0.05 ( 1 - a ) 0.05 a 0.05 a 2IO -3 + 12H+ + 10 e - ¾® I 2 + 6H2O
where, a is the degree of dissociation. 2IO -3 + 12H+ + 10I - ¾® 6I 2 + 6H2O
[H+ ] [CH3COO - ]
\ Equilibrium constant, K a = or IO -3 + 6H+ + 5I - ¾® 3I 2 + 3H2O
[CH3COOH]
Here, I - is oxidised to I 2 and IO -3 is reduced to I 2 .
(0.05 a ) (0.05 a ) 0.05a 2
Ka = = (ii) Oxidation half reaction Bi ¾® Bi 3+ + 3 e -
0.05(1 - a ) 1-a
Reduction half reaction
K a » 0.05 a 2
2H+ + NO -3 + e ¾® NO 2 + H2O] ´ 3
Ka
=a Bi + 3NO -3 + 6H+ ¾® Bi 3+ + 3NO 2 + 3H2O
0 .05
Ka Here, Bi is oxidised to Bi 3+ and NO -3 is reduced to NO 2 .
Now, H+ = 0.05a = 0.05 = K a 0.05
0 .05 (iii) I - + O 2 + H2O ¾® I 2 + OH-
( 4.46 ´ 10 -3 )2 = K a( 0.05) Oxidation half reaction 2I - ¾® I 2 + 2 e - ] ´ 2
-6 -3
19.89 ´ 10 = K a(2.5 ´ 10 ) Reduction half reaction
K a » 4 ´ 10 -4 O 2 + 2H2O + 4 e - ¾® 4OH-
O 2 + 2H2O + 4I - ¾® 2I 2 + 4OH-
15. (i) On increasing the pressure, the value of K p does not
change. On increasing the pressure the reaction will shift in Here, I - is oxidised to I 2 and O 2 is reduced to OH- .
forward direction due to lower number of gaseous (i) 10 volume of H2O 2 means 1L of this H2O 2 solution will
molecules on product side. Thus, composition of
19.
produce 10 L of oxygen on decomposition of H2O 2 .
equilibrium mixture will be affected.
2H2O 2 ( l ) ¾® 2H2O ( l ) + O 2 ( g )
(ii) On increasing the temperature, the value of K p changes.
The equilibrium reaction is endothermic, thus K p increases So, 2 moles of H2O 2 gives 1 mole of O 2
on increasing temperature. Also, according to 68 g of H2O 2 gives 22.7 L of O 2 at STP.
Le-Chatelier’s principle, it favours forward reaction because {Q Molar volume of a gas at STP is 22.7 L}
heat is consumed in the reaction. Hence, composition of 68g
equilibrium mixture also changes. So, 10L of oxygen is produced by ´ 10 L of H2O 2
22.7 L
(iii) On using a catalyst the value of K p does not change. While
= 30 g of H2O 2
it changes the composition of equilibrium mixture by
promoting the formation of product. So, 30 g of H2O 2 per litre solution will give 10 L of oxygen.
30 g
16. A( g ) + B( g ) = C( g ) + D( g ) Hence, the strength of H2O 2 solution is .
L
Initial conc. 1 1 1 1 (ii) The species which has higher tendency to undergo
Equilibrium conc. 1- x 1- x 1+ x 1+ x oxidation will have higher tendency to act as reducing
[C ] [ D] agent. Hence, the increasing order of reducing property is
Kc = 64 =
[ A] [ B ] H2O < MgH2 < NaH
(1 + x ) (1 + x ) (1 + x )2 20. (i) Carbon in its valence shell has 4 valence electrons. To
64 = =
(1 - x ) (1 - x ) (1 - x)2 complete its valence shell and to complete its octet it shares
(1 + x ) 4 more electrons and becomes stable. No further expansion
8= is possible. But in case of silicon which after completing its
(1 - x )
valence orbital 3 p there exist on empty 3d orbital in valence
8 - 8x =1+ x shell. Thus, silicon can show higher covalency by accepting
x = 0.77 moles electrons in 3d orbital.
Concentration of A and B at equilibrium = 1 - x = 1 - 0.77 = 0.23 (ii) Both carbon and silicon has oxidation state of +4 in CO 2
moles. Concentration of C and D at equilibrium and SiO 2 but due to small size of carbon it favours C ¾O,
. moles
= 1 + x = 1 + 0.77 = 177 p-bond formation. While silicon is bigger in size cannot form
17. (i) Let the oxidation state of N be x. strong C ¾O, p-bonds, hence it forms a network of Si ¾O
bonds. This network of Si ¾O bonds result the SiO 2 to be
2( x) + ( - 2 ) = 0
solid while CO 2 molecules do not have that much strong
2 x =2 interactions between their molecules and remain in gaseous
x = +1 state.
\ Oxidation state of nitrogen is + 1. (iii) CO is a poisonous gas due to its very high tendency of
(ii) x + 2 ( - 2 ) = 0 formation of complex with haemoglobin. This tendency of
x - 4 = 0, x = + 4 CO is 300 times more than oxygen. Thus, CO competes with
\ Oxidation state of nitrogen is + 4.

73
oxygen and restricts haemoglobin to carry oxygen around (iii) HX = H+ + X-
the body that causes death due to deficiency of oxygen. Initial conc. 0.5 0 0
21. (i) There is no resonance structure possible for the given Equilibrium conc. 0.5 (1 - 0.45) 0.5(0.45) 0.5(0.45)
compound. Concentration of H+ , [H+ ] = 0.5 (0.45) = 0.225 M

pH = - log[H+ ], pH = - log(0.225), pH = 0.64
+
(ii) CH2==CH—C—H CH2—CH==C —H [H+ ] [ X - ] [0.5(0.45)]2 0.101
Ka = = = = 0.18
– [HX ] 0.5(1 - 0.45) 0.55
+ pK a = - log K a = - log (0.18) = 0.74
(iii) CH3—C—NH2 CH3—C==NH2
25. On ozonolysis of the unsaturated hydrocarbon the products are
6 5
22. (i) CH3 ¾ CH2 ¾ CH==CH2 + HBr ¾¾¾¾®2 2 (C H CO) O CH3CHO, O==CHCH2CH2CH==O , H3C
Ethanal Butane -1, 4 -dial C ==O
CH3 ¾ CH2 ¾ CH2 ¾ CH2Br H3C
Therefore, the hydrocarbon A should be
1-bromobutane Propanone
CH3
(A)
½
Hg2+/H+ Isomerisation CH3CH== CHCH2CH2CH== C ¾ CH3
(ii) CH3—C CH + H—OH CH3—C==CH2
333K 2-methyl octa-2, 6-diene
OH (A)
Reactions involved are
CH3—C— CH 3 CH3
½ 2H 2
O (i) CH3CH == CHCH2CH2CH== C ¾ CH3 ¾ ¾¾ ® CH3CH 2
Propanone A
(B) CH3
OH
½
CH2CH2CH2CH2 CH ¾ CH3
CH3
(iii) + Zn D + ZnO
2O3
(ii) CH3CH CH CH 2 CH2 CH C—CH 3
Benzene
(C) O O
CH3
23. (i) The fuel of motor vehicles are petrol and diesel that burns in CH3CH CHCH2 CH3CH C
the engine of motor vehicle to generate power. The petrol CH3
and diesel contains sulphur and nitrogen atoms which on O O O O
oxidation produces various oxides of sulphur and nitrogen CH3 Zn+H2O
that have an adverse effect on our health when we inhale CH3CHO + CHOCH2 CH2CHO + C
these gases. The carbon is another major constituent of CH3
petrol and diesel that oxidises to form oxides of carbon like
26. (i) Electronic configuration of boron, B = 1s 2 2 s 2 2 p1
carbon dioxide and carbon monoxide. These gases causes
air pollution. In excited state, electronic configuration of boron becomes
(ii) (a) A substitute fuel such as CNG should be used in our 1s 2 2 s1 2 p1x 2 p1y
vehicles that does not generate such harmful pollutants. 2s 2p
(b) We should regularly check our vehicles that it does not
exhaust excessive harmful gases than normal. Otherwise,
sp2 hybridised
we should repair or replace the vehicle.
(c) We should use public transport and pooling of car to Here, in boron there is no empty d-orbitals available to expand
check air pollution. its electronic configuration. Hence, it does not form dimer.
(i) A buffer solution is the solution that restrict the change in pH But in case of AlCl 3 there is empty 3d-orbital so that aluminium
24. can expand its electronic configuration and form dimer.
of the solution on addition of small amount of acid or alkali
Cl Cl Cl
or on dilution of the solution. Al Al
=
(ii) A ( g ) + 2 B ( g ) C (g ) Cl Cl Cl
Dn g = 1 - (1 + 2 ) = - 2 (ii) 2NH3 + H2O + CO 2 ¾® (NH4 )2CO 3
[C ] (NH4 )2CO 3 + H2O + CO 2 ¾® 2NH4 HCO 3
Q=
[ A] [ B ] 2 NH4 HCO 3 + NaCl ¾® NH4 Cl + NaHCO 3
D
When pressure is increased then to maintain the temperature 2NaHCO 3 ¾¾ ® Na 2CO 3 + CO 2 + H2O
constant the volume will decrease. The gaseous molecules are (iii) Borax (Na 2B 4 O 7 × 10H2O) on heating gives sodium
higher on reactant side whose concentration appears in metaborate and boric anhydride.
denominator in the expression of Q. Hence, the value of Q D
Na 2B 4 O 7 × 10H2O ¾¾ ® Na 2 B 4 O 7
decreases. Borax - 10 H 2O

Therefore, reaction moves in forward direction. D


¾¾ ® 2NaBO 2 + B 2O 3
Sodium metaborate Boric anhydride

74