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Chemistry Times July 18

1
Chemistry Times July 18

By: P. BRAHMA REDDY


(Alumni of IIT Delhi)
Introduction
The determination of composition and structural formula of an organic compound is known as characterization
of the compound.

Qualitative analysis (Detection of elements)


 Organic compounds primarily consist of carbon and hydrogen atoms. Other than this, some compounds also
contain Oxygen, Nitrogen, Sulphur, Halogens, and Phosphorus.
 The order of abundance of these elements in organic compounds is given below:
Carbon - always present
Hydrogen - nearly always present
Oxygen - generally present
N, P, and S - less commonly present
P and metals - rarely present
In order to qualitatively determine the presence of different elements in an organic compound, scientists
have devised various methods. Following are some of the most commonly used methods:
(A)Detection of Carbon and Hydrogen
Copper oxide test: Carbon and hydrogen are detected by heating the organic compound with
dry copper (II) oxide (CuO, is hygroscopic, it is always ignited before use as to make it completely dry).

2
Chemistry Times July 18

Little more: If the substance under examination contains sulphur also, the gases evolved are first passed
through an acidified solution of potassium dichromate which absorbs all the sulphur dioxide and then
through lime water and which turns milky.
S  2CuO 
 2Cu  SO2
K 2 Cr2 O7  H 2 SO4  3SO2 
 K 2 SO4  Cr2 ( SO4 )3  H 2 O
SO2 like CO2 turns lime water milky due to formation of CaSO3 .
Organic compounds (suppose to contain P) are heated with oxidizing agents (like Na2 O2 ). The phosphorus
present in the organic compound is oxidized to phosphate.

(B) Detection of N, S and Halogens


N, S, and halogens present in an organic compound are detected by “Lassaigne’s test”. The organic compound
(N, S or halogens) is fused with sodium metal as to convert these elements into ionizable inorganic substances,
i.e., nitrogen into sodium cyanide, sulphur into sodium sulphide and halogens into sodium halides. Following
reactions take place:

Na  C  N   NaCN

2Na  S   Na2 S

Na  X   NaX ( X  Cl , Br or I )
C, N, S and X come from organic compound
Cyanide, sulphide and halide of sodium so formed on sodium fusion are extracted from the fused mass by
boiling it with distilled water. This extract is known as sodium fusion extract or Lassaigne’s filtrate. It is
usually alkaline, if it is not alkaline, a few drops of NaOH solution may be added to make it alkaline.

Little more
 Lithium is not used in Lassaigne’s test as it reacts slowly moreover its compounds are covalent. Potassium
cannot be used in this test as its reaction is violent.
 Instead of sodium metal, mixture of sodium carbonate and zinc can be used. It is called Middleton’s fusion
method.

(1) Detection of Nitrogen


To a portion of sodium fusion extract, freshly prepared FeSO4 solution is added and warmed. As the
solution is alkaline (excess of Na reacts with water to form NaOH), a green ppt of Fe(OH ) 2 appears. The
mixture is boiled for two minutes, cooled and acidified with dil. H 2 SO4 (dil H 2 SO4 dissolves Fe(OH ) 2 ).
Appearance of a green (or) Prussian blue color confirms the presence of nitrogen. Alternatively FeCl3 and
dil. HCl may be added.

Na  C  N   NaCN
2 Na  2 H 2 O   2 NaOH  H 2
When the filtrate is boiled with ferrous sulphate solution, the following reactions takes place.
FeSO4  2 NaOH 
 Fe(OH ) 2 [Green]  Na2 SO4
Fe(OH ) 2  6 NaCN   Na4 [ Fe(CN ) 6 ]  NaOH
At the same time some ferrous sulphate is converted to ferric sulphate. This reacts with sodium ferrocyanide
to form ferric ferrocyanide which gives prussian blue color or precipitate.
3 Na4 [ Fe(CN )6 ]  2 Fe2 (SO4 )3 
 Fe4 [ Fe(CN )6 ]3  6 Na2 SO4
Prussian blue

3
Chemistry Times July 18

 To a small portion of sodium extract, a few drops of


acetic acid and cadmium acetate are added. Yellow
precipitate of cadmium sulphide is formed.

 Sometimes when the amount of nitrogen present is Na2 S  Cd (CH 3COO) 2  CdS (Yellow ppt)
small, the prussian blue is present in colloidal form 2CH 3COONa
and the solution looks green.  Oxidation test: The organic compound is fused
 When the alkaline solution is acidified with HCl, with fusion mixture (a mixture of sodium carbonate
the yellow color of ferric chloride produced by the and potassium nitrate). The sulphur, is present in
acid with ferric ions makes the blue color to appear the organic compound, is oxidised to sodium
as green. sulphate.
 When the organic substance contains both N and
S, sodium thiocyanate is formed which gives a Na2 CO3  S  3O  Na2 SO4  CO2
blood red coloration of ferric sulphocyanide (or The fused mass is dissolved in water and the
ferric thiocyanate) with ferric ions. solution is acidified with HCl. BaCl2 solution is
3 NaCNS  FeCl3 
 Fe(CNS )3  3 NaCl then added. The formation of a white ppt. indicates
Blood red
the presence of sulphur.
If sodium fusion is carried out with excess of
sodium, the thiocyanate decomposes to give Na2 SO4  BaCl2   BaSO4 (white ppt)  2NaCl
cyanide and sulphide. These ions give usual tests (3) Detection of Halogens
The sodium fusion extract is acidified with nitric
NaSCN  2 Na   NaCN  Na2 S
acid and then treated with silver nitrate. A white
 This test is not given by compounds which do not precipitate, soluble in ammonium hydroxide
contain C atoms but contain N atoms, (aqueous ammonia) shows the presence of
for example, NH 2 NH 2 , NH 2 OH . Since these chlorine, a yellowish precipitate, sparingly soluble
compounds do not contain C atoms, so in sodium in ammonium hydroxide shows the presence of
bromine and a yellow precipitate, insoluble in
fusion extract, CN  ion is not formed and Prussian
ammonium hydroxide shows the presence of iodine.
blue color is not observed.
 This test is not given by diazonium salt also, AgNO3  NaCl 
 AgCl (White ppt)  NaNO3
although they contain both C and N elements, AgNO3  NaBr 
 AgBr (Pale yellow ppt)
because they decompose and loses N 2 on heating
 NaNO3
much before they have a chance to react with the
fused sodium metal. AgNO3  NaI 
 AgI (Yellow ppt)  NaNO3
 If nitrogen or sulphur is also present in the
(2) Detection of sulphur compound, the sodium fusion extract is first boiled
Sulphur is present in the sodium extract in the form with concentrated nitric acid to decompose cyanide
of sodium sulphide ( Na2 S ) . Sulphur is tested in or sulphide of sodium formed during Lassaigne’s
the sodium extract in the following manner: test. These ions would otherwise interfere with
 The sodium fusion extract is acidified with acetic silver nitrate test for halogens. If these ions are not
acid and lead acetate is added to it. A black removed, they would give a white precipitate of
precipitate of lead sulphide indicates the presence AgCN or Ag 2 S with AgNO3 and will confuse it
of sulphur. for AgCl.
Na2 S  Pb(CH 3COO ) 2  PbS (Black ppt)
Little More
2CH 3COONa
 On treating sodium fusion extract with sodium Chlorine water test (layer test) for Br2 and I 2 :
nitroprusside, appearance of a violet color further From the color of AgBr and AgI, it is difficult to
indicates the presence of sulphur. judge whether the organic compound contains Br
or I. A small portion of Na extract is acidified with
Na2 S  Na2 [ Fe( NO)(CN )5 ]  Na4 [ Fe( NOS )(CN )5 ]
Sodium nitroprusside Sodium thionitroprusside dilute HNO3 or H 2 SO4 and add CS2 Cl3 or CCl4 .

4
Chemistry Times July 18

Now shake with excess of Cl2 water. If the color of the CCl4 layer becomes yellow or brown ‘Br’ is present.
2 NaBr  Cl2 
 2 NaCl  Br2
(turns CS2 layer orange)
If the color of the CCl4 layer turns violet ‘iodine’ is present.
2 NaI  Cl2 
 2 NaCl  I 2
(turns CS2 layer violet)

Beilstein’s test or copper wire test:


By this test, we can confirm the absence or presence of halogens by heating the organic compound on
copper wire.
a. If copper wire with the compound gives no green flame again, halogens are absent.
b. If a bluish green flame (due to vapors of CuX 2 ) is observed, halogens may or may not be present
c. Pyridine, thiourea also give green color in this test
d. Beilstein test is not given by fluorine as CuF2 in nonvolatile.
e. This test does not tell which halogen is present in the compound.

5
Chemistry Times July 18

(C) Detection of Phosphorus

(D) Detection of Oxygen


There is no satisfactory qualitative method for the detection of oxygen. However, its presence can be
inferred indirectly.
 If the organic compound is heated alone in a dry test tube in presence of nitrogen, the formation of water
drops on cooler parts of the tube may indicate the presence of oxygen.
 The presence of oxygen can be inferred by testing the presence of functional groups known to contain
oxygen, e.g., hydroxyl, aldehydic, carboxyl, and nitro, etc.
Quantitative Analysis [Estimation of elements]
Quantitative analysis is an analysis method used to determine the quantity of elements or molecules produced
during the reaction. The various methods used for the measurement of percentage composition of elements
in an organic compound are explained below:

6
Chemistry Times July 18

Determination of molecular mass


Mass of the substance
The molecular mass of organic compounds can be MW   22400
determined by various methods. The methods may Volume of the vapors at NTP
be divided into two groups: (ii) For non – volatile substances
1. Physical methods: These are two types: (a) Elevation in boiling point method
(i) For volatile compounds
(a) Victor Meyer’s method
w2 1000 K b  w2  1000
(b) Hofmann’s method Tb  Kb  ; MW2 
(ii) For non - volatile compounds MW2  w1 Tb  w1
(a) Ebullioscopic mehod or elevation in Where, Tb  Elevation in boiling point
boiling point method
(b) Cryoscopic method or depression in K b  Molal elevation constant
freezing point method w2  weight or mass of solute
2. Chemical methods:
(i) Silver salt method for acids w1  weight or mass of solvent
(ii) Platinichloride method for bases MW2  molecular mass of solute
(iii) Volumetric method for both acids and bases
(b) Depression in freezing point method
1. Physical Methods:
(i) For volatile compounds: w2 1000 K f  w2 1000
(a) Victor Meyer’s method Tf  K f  ; MW2 
MW2  w1 T f  w1
A known mass of compound (w g) is vaporized in
an instrument called Victor Meyer tube. The vapors
so obtained displace an equal volume of air into a Where, T f  Depression in freezing point
graduated tube. The volume of vapors is measured
and reduced to STP. K f  Molal depression constant
Let, the volume of vapors at STP be V mL 22400 mL w2  weight or mass of solute
of vapors are obtained from 1 mol of the compound
w1  weight or mass of solvent
V mL
V mL of vapors are obtained from mol MW2  molecular mass of solute
22400 mL
of compound 2. Chemical Methods:
(a) Silver salt method for carboxylic acids
Mass of the compound (w) Most of the organic acids form sparingly soluble
Mole 
Molecular mass of the compound(MW) silver salts, which on ignition leave a residue of
metallic silver. This forms the basis of the silver
V salt method for the determination of molecular mass

22400 of the acids.
The organic acid solution is neutralized with
wx 22400 Mass of compoun x 22400
MW   NH 4 OH and heated to boil off excess NH 3 . It is
V Volume of vapors at STP
(b) Hofmann’s Method: then treated with excess of AgNO3 solution and
The method is applied to those substances which the precipitated silver salt is filtered, washed and
are not stable at their boiling points but which may dried. A known mass of the dry silver salt is ignited
be volatilised without decomposition under in a crucible to a constant mass.
reduced pressure. A known mass of the substance RCOOAg  
 Ag
is vaporised above a mercury column in a
Let, the equivalent weight of acid (RCOOH) be E
barometric tube and the volume of the vapor formed
The equivalent weight of
is recorded. It is then reduced to NTP conditions.
The molecular mass of the organic substance can RCOOAg  E  1  108  E  107
be calculated by the application of following Equivalent weight of Ag = 108
relationships.

7
Chemistry Times July 18

Weight of RCOOAg = W gm
W w  W 195 
Weight of Ag = w gm   E      205
1 equivalent of RCOOAg = 1 equivalent of Ag 2 E  410 195 w 2 
(c) Volumetric method for organic acids and bases
W w
 i. A known mass of organic acid is dissolved in water
E  107 108 or alcohol and titrated against a standard NaOH or
W  108 KOH solution. From the volume of alkali used, the
E  107 equivalent weight of organic acid can be calculated.
w
V mL of ‘N’ NaOH = w gm of organic acid
(MW of an acid = E x x – factor)
(b) Chloroplatinate or Platinichloride method for w  1000
1000 mL of ‘N’ NaOH   1gm
organic bases V
Organic bases form salts with HCl and the chlorides equivalent of the base  EW of the base
give double salts with platinum chloride. Organic
Equivalent of acid = EW of the organic acid
bases react with dibasic chloroplatinic acid
Where ‘V’ is volume of ‘N’ NaOH used for
( H 2 PtCl6 ) and form double salts and are called neutralizing ‘w’ gm of acid.
chloroplatinates or platinichlorides. These salts ii. Organic bases: A known mass of organic base is
leave a residue of metallic platinum on ignition. titrated against a standard acid (e.g., HCl or oxalic
Equivalent weight of organic base = E acid). From the volume of the acid used, the
Mass or weight of chloroplatinate salt = W gm equivalent weight of organic base can be calculated.
Mass or weight of platinum = w gm V mL of ‘N’ HCl = w gm of the organic base
Equivalent weight of platinum = 195 w1000
 1000 mL of ‘N’ HCl   1gm equivalent of
2E  H 2 PtCl6 
 E2 H 2 PtCl6   Pt V N
Equivalent weight of E2 H 2 PtCl6  2 E  2  195 the base  EW of the base
(6  35.5)  2E  410 Where ‘V’ is volume of ‘N’ HCl used for neutralizing
‘w’ gm of base.
1 equivalent of E2 H 2 PtCl6  1 equivalent of Pt
Calculation of Empirical Formula and Molecular Formula
 An empirical formula represents the simplest whole number ratio of various atoms present in a compound
whereas the molecular formula shows the exact number of different types of atoms present in a molecule of
a compound.
 If the mass percent of various elements present in a compound is known, its empirical formula can be
determined. Molecular formula can further obtained if the molar mass is known. The following steps illustrates
this sequence:

• Writing molecular formula


(a) Determine empirical formula mass
Add the atomic masses of various atoms present in the empirical formula
Molecular mass
(b) Divide molecular mass by empirical formula mass, n 
Empirical formula mass
(c) Multiply empirical formula by ‘n’ obtained above to get the molecular formula
Molecular formula  n  empirical formula
8
Chemistry Times July 18

(a) 23.01%, 4.58% (b) 4.58%, 23.01%


(c) 35.91%, 42% (d) 42%, 35.91%
8. 0.92 g of an organic compound containing carbon,
hydrogen and oxygen was analysed by
combustion method. The increase in mass of the
1. The sodium extract of an organic compound on U-tube and the potash (KOH) bulbs at the end of
treatment with FeSO4 solution, FeCl3 and HCl the operation was found to be 1.08 g and 1.76 g
gives a red solution. The organic compound respectively. The sum of the percentage of carbon
contains: and oxygen is
(a) both nitrogen and sulphur (a) 65.21% (b) 86.96% (c) 52.17% (d) 47.83%
(b) Nitrogen only 9. In Duma’s method for estimation of nitrogen, 0.3 g
(c) Oxygen only of an organic compound gave 50 mL of nitrogen
(d) Halogen collected at 300K temperature and 715 mm pressure.
2. Lassaigne’s test is not shown by diazonium salts The percentage composition of nitrogen in the
because they compound (Aqueous tension at 300K = 15mm) is
(a) form NH 3 gas on heating much before the (a) 20% (b) 17.83% (c) 50% (d) 35%
10. During estimation of nitrogen present in an organic
reaction with sodium compound by Kjeldahl’s method, the ammonia
(b) form N 2 gas on heating much before the evolved from 0.5g of the compound in Kjeldahl’s
reaction with sodium estimation of nitrogen, neutralized 10 mL of 1M
(c) are highly volatile and evaporate before the H 2 SO4 . Find out the percentage of nitrogen in the
reaction with sodium compound.
(d) All of the above (a) 30% (b) 35% (c) 28% (d) 50%
3. The Lassaigne’s extract is boiled with conc. HNO3 11. 0.2 g of an organic compound was analysed by
while testing for halogens. Because it Kjeldahl’s method. Ammonia evolved was
(a) decomposes Na2 S and NaCN, if formed absorbed in 60 mL of N / 5 H 2 SO4 . Unused acid
(b) helps in the precipitation of AgCl required 40 mL of N/10 NaOH for complete
(c) Increases the solubility product of AgCl neutralisation. Find the percentage of nitrogen in
the compound.
(d) Increases the concentration of NO3 ions.
(a) 28% (b) 56% (c) 46% (d) 75%
4. In carius method of estimation of halogens, 250 mg 12. 0.1170 g of an organic compound on heating with
of an organic compound gave 141 mg of AgBr. The conc. HNO3 and silver nitrate in Carius furnace gave
percentage of bromine in the compound is 0.42 g of AgCl. Find the percentage of chlorine in
[JEE Main 2015] the compound.
(a) 48 (b) 60 (c) 24 (d) 36 (a) 88.8% (b) 77.7% (c) 66.6% (d) 55.5%
5. An organic compound which produces a bluish 13. In sulphur estimation, 0.157 g of an organic
green coloured flame on heating in presence of compound gave 0.4813 g of barium sulphate.
copper is What is the percentage of sulphur in the
(a) benzaldehyde (b) benzoic acid compound?
(c) aniline (d) chlorobenzene (a) 10% (b) 20% (c) 32% (d) 42%
6. Catalyst used in Kjeldahl’s method for the 14. 0.12g of an organic compound containing
estimation for nitrogen is
(a) sodium (b) magnesium phosphorus gave 0.22 g of Mg 2 P2 O7 by the usual
(c) mercury (d) copper analysis. Calculate the percentage of P in the
7. On complete combustion, 0.246g of an organic compound.
compound gave 0.198g of carbon dioxide and (a) 51% (b) 62% (c) 72% (d) 81%
0.1014g of water. The percentage composition of 15. In a Victor meyer’s determination, the following
carbon and hydrogen in the compound are, observations have been made:
respectively Mass of compound = 0.17 g
Volume of air collected = 34.2 mL

9
Chemistry Times July 18

Temperature  15 C
Atmospheric pressure = 750 mm
Vapor pressure of water at 15 C  13 mm 1.Sol: It is test for the organic compound containing
The vapor density of the compound is N and S.
(a) 120 (b) 60 (c) 45 (d) 30
16. 40 g of a substance were dissolved in 450 g of 3 NaCNS  FeCl3 
 Fe(CNS )3  3 NaCl
Blood red
water to give a solution which boils at 100.2C . If sodium fusion is carried out with excess of
Calculate molecular weight of substance. K b for sodium, the thiocyanate decomposes to give
cyanide and sulphide. These ions gives usual tests
water  0.51K kg mol 1 .
NaSCN  2 Na 
 NaCN  Na2 S
(a) 227 (b) 40 (c) 250 (d) 100
17. 0.76 g of the silver salt of a dibasic acid was ignited. 2.Sol: Diazonium salts are stable only at 0  5 C . At
It gave 0.54 g of pure silver. The molecular mass of high temperature, it releases N 2 gas.
the acid is
(a) 45 (b) 90 (c) 60 (d) 85 3.Sol: Conc. HNO3 decomposes Na2 S and NaCN, if
18. An aromatic mono basic acid contains 68.87% C formed.
and 4.9 % H. 0.610 g of the acid required 25 mL of 4.Sol:
M/10 diacidic base for neutralization. What is
80 Mass of AgBr formed
molecular formula of acid? % of Br    100
188 Mass of substance taken
(a) C7 H 6 O2 (b) CH 3O (c) C3 H 6 O (d) CHO
19. An organic compound gave the following data: 80 141
   100  24%
0.236 g yielded 0.528 g CO2 and 0.324 g H 2 O on 188 240
combustion. 0.295 g of the compound gave 56 mL 5.Sol: It is an example of Beilstein test
7.Sol:
of N 2 at STP. The compound is a monoacidic base.
12 Mass of CO2
It’s platinic chloride salt contains 36.93% platinum. % of C    100
44 Mass of organic compound
Calculate the molecular formula of the compound.
12 0.198
(a) CH 3 N (b) C3 H 9 N (c) CHN (d) C4 H 8 N % of C    100  23.01%
44 0.246
20. The freezing point constant of C6 H 6 is 4.9 K 2 Mass of H 2 O
% of H    100
kg mol 1 and its melting point is 5.51C . A 18 Mass of organic compound
solution of 0.816 g of compound (A) when 2 0.1014
% of H    100  4.58%
dissolved in 7.5 g of C6 H 6 freezes at 1.59C . The 18 0.246
8.Sol: Increase in mass of U - tube = Mass of water
compound (A) has C = 70.58% and H = 5.88%. formed = 1.08 g
Determine the molecular formula of (A).
2 Mass of H 2 O
(a) CHO (b) C4 H 4 O2 (c) CHO2 (d) C8 H 8O2 % of H    100
18 Mass of organic compound
2 1.08
% of H    100  13.04%
18 0.92
Increase in mass of Potash bulbs = Mass of CO2
1. a 2. b 3. a 4. c 5. d formed = 1.76 g
6. c 7. a 8. b 9. b 10. c 12 Mass of CO2
1. b
11. 12. a 13. d 14. a 15. b % of C    100
44 Mass of organic compound
16. a 17. b 18. a 19. b 20. d
12 1.76
% of C    100  52.17%
44 0.92

10
Chemistry Times July 18

% of O  100  [% of C  % of H ] 13.Sol:

 100  [52.17  13.04]  34.79% 32 Mass of BaSO4


% of S   100
233 Mass of organiccompound
Composition of the compound: C  52.17%,
H  13.04% and O  34.79% 32 0.4813
% of S    100  42.10%
9.Sol: Given conditions STP conditions 233 0.157
V1  50 mL V2  ? 14.Sol:
P1  715mm P2  760mm 62 Mass of Mg 2 P2O7
% of P   100
222 Mass of organic compound
T1  300 K T2  300 K
Applying ideal gas equation, 62 0.22
% of P    100  51.20 %
222 0.12
PV
1 1 PV
 2 2 15.Sol.:Given conditions STP conditions
15.Sol.:
T1 T2 Given conditions STP conditions
Volume of nitrogen at STP, V1  34.2 mL V2  ?
PV T 715  50 273 P1  (750  13) mm  737 mm P2  760 mm
V2  1 1 . 2  .  42.8mL
T1 P2 300 760
T1  288 K T2  300 K
28 V2 Applying ideal gas equation,
% of N    100
22400 Mass of organic compound PV PV
1 1
 2 2
28 42.8 T1 T2
% of N    100  17.83% Volume of nitrogen at
22400 0.3
PV
1 1 T2 737  34.2 273
1.4  N1  V 1.4  1  10 STP, V2  T  P    31.44 mL
10.Sol: % of N    28% 1 2 288 760
W 0.5
Vapour density
11.Sol: Unused acid required  40ML N / 10 NaOH =
W 0.17
40 mL N/10 H 2 SO4  20 mL N/ 5 H 2 SO4    60.08
V2  0.00009 31.4376  0.00009
Acid used for absorption of ammonia Molecular weight  2  Vapour Density
 (60  20) mL N/ 5 H 2 SO4  40 mL N / 5 H 2 SO4
 2  60.08  120.16
1 1000  K b  w2 1000 0.51 40
1.4   40
1.4  N1  V 5 16.Sol: Tb  MW2  W
 0.2 
MW2  450
% of N    56%
W 0.2
Molecular weight of substance = 226.67
12.Sol: 17.Sol:
35.5 Mass of AgCl Massof silver salt 108 0.76
% of chlorine   100 E 107  108 107  45
143.5 Mass of organic compound Massof Silver 0.54
Where, E  Equivalent of acid
35.5 0.42
% of chlorine    100  88.8 % Molecular Mass of acid  Basicity of acid
143.5 0.1170
 Equivalent mass  2  45  90
18.Sol:

11
Chemistry Times July 18

Empirical formula is C7 H 6 O2 , Empirical formula weight is 122


Determination of molecular weight of acid: Meq. Of acid = Meq. Of alkali used
0.610 1
 1000  25   2
MW /1 10
Molecular weight of acid 122
Molecular weight = 122, n  Empirical formula

122
1

Molecular forumula  n  Empirical formula  C7 H 6O2


12 Mass of CO2 12 0.528
19.Sol: % of C  44  Mass of organic compound  100    100  61.07%
44 0.236

2 Mass of H 2 O
% of H    100  12  0.324  100  15.25%
18 Mass of organic compound 18 0.236

28 V2
% of N   100  28  56  100  23.73%
22400 Massof organiccompound 22400 0.295

Calculation of empirical formula based on the percentage composition:


Empirical formula is C 3 H 9 N , Empirical formula weight = 59

1  Mass of Salt  1  100 


Equivalent of base    195  410    195  410  59
2  Mass of Pt  2  36.93 
Molecular weight of base  59  acidity  59  1  59
Molecular formula  C3 H 9 N
20.Sol: Calculation of empirical formula of the compound:

Empirical formula  C4 H 4 O , Empirical formula weight  68


Calculation of molecular formula of the compound:
1000. Kb .w2 1000. Kb .w2 (1000)(4.9)(0.816)
Tb  MW2  
MW2 .W1 , Tb .W1 (3.92)(7.5)
n  136 / 68  2
Molecular formula  (n) (empirical formula)  (2) (C4 H 4 O2 )  C8 H 8O2

12
Chemistry Times July 18

Make Hot Ice From Vinegar and Baking Soda


Sodium acetate or hot ice is an amazing chemical you can prepare yourself from baking soda and vinegar.
You can cool a solution of sodium acetate below its melting point and then cause the liquid to crystallize. The
crystallization is an exothermic process, so the resulting ice is hot. Solidification occurs so quickly you can
form sculptures as you pour the hot ice.
Sodium Acetate or Hot Ice Materials:
1-liter clear vinegar (weak acetic acid), 4 tablespoons baking soda (sodium bicarbonate)
Prepare the Sodium Acetate or Hot Ice:
In a saucepan or large beaker, add baking soda to the vinegar, a little at a time and stirring between
additions. The baking soda and vinegar react to form sodium acetate and carbon dioxide gas. If you don't add
the baking soda slowly, you'll essentially get a baking soda and vinegar volcano, which would overflow your
container. You've made the sodium acetate, but it is too dilute to be very useful, so you need to remove most
of the water. Here is the reaction between the baking soda and vinegar to produce the sodium acetate:
Na+[HCO3]– + CH3–COOH  CH3–COO– Na+ + H2O + CO2
Boil the solution to concentrate the sodium acetate. You could just remove the solution from heat once
you have 100-150 ml of solution remaining, but the easiest way to get good results is to simply boil the
solution until a crystal skin or film starts to form on the surface. This took me about an hour on the stove over
medium heat. If you use lower heat you are less likely to get yellow or brown liquid, but it will take longer. If
discoloration occurs, it's okay.
Once you remove the sodium acetate solution from heat, immediately cover it to prevent any further
evaporation. I poured my solution into a separate container and covered it with plastic wrap. You should not
have any crystals in your solution. If you do have crystals, stir a very small amount of water or vinegar into
the solution, just sufficient to dissolve the crystals.
Place the covered container of sodium acetate solution in the refrigerator to chill.
Activities Involving Hot Ice:
The sodium acetate in the solution in the refrigerator is an example of a supercooled liquid. That is, the
sodium acetate exists in liquid form below its usual melting point. You can initiate crystallization by adding
a small crystal of sodium acetate or possibly even by touching the surface of the sodium acetate solution
with a spoon or finger. The crystallization is an example of an exothermic process. Heat is released as the 'ice'
forms. To demonstrate supercooling, crystallization, and heat release you could:
Drop a crystal into the container of cooled sodium acetate solution. The sodium acetate will crystallize
within seconds, working outward from where you added the crystal. The crystal acts as a nucleation site or
seed for rapid crystal growth. Although the solution just came out of the refrigerator, if you touch the
container you will find it is now warm or hot.
Pour the solution onto a shallow dish. If the hot ice does not spontaneously begin crystallization, you can
touch it with a crystal of sodium acetate (you can usually scrape a small amount of sodium acetate from the
side of the container you used earlier). The crystallization will progress from the dish up toward where you
are pouring the liquid. You can construct towers of hot ice. The towers will be warm to the touch.
You can re-melt sodium acetate and re-use it for demonstrations.

13
Chemistry Times July 18

ORDER OF THE REACTION

Section A: Single Option Correct Type


1. The radioactive element 84 Po 218 (t1/ 2  3.05 min)
decays to 82 Pb 214 (t1/ 2  2.68 min) by  
emission while Pb 214 is  - emitter. The above From the data, the order of the reaction is
(a) 0 (b) 1 (c) 2 (d) 3
reaction follows
5. For the chemical reaction, A  2 B  C , the rate
(a) zero order reaction
(b) first order reaction of reaction is increased by 2.82 times when the
(c) second order reaction concentration of A is doubled and increased by 9
(d) third order reaction times when the concentration of B was tripled.
2. The unit of rate constant of the reaction is given as What is the total order of the reaction?
(a) 3/2 (b) 5/2 (c) 7/2 (d) 3
mol 7/ 2 L7/ 2 s 1 . The order of the reaction is 6. The half life period and initial concentration for a
(a) 7/2 (b) -9/2 (c) 9/2 (d) -7/2 reaction are as follows. What is the order of
3. Consider a reaction aG + bH  Products. When reaction?
concentration of both the reactants G and H is
doubled, the rate increases eight times. However,
when the concentration of G is doubled, keeping
the concentration of H is fixed, the rate is doubled.
The overall order of reaction is
(a) 0 (b) 1 (c) 2 (d) 3
4. The chemical reaction between mercuric chloride
(a) 0 (b) 1 (c) 2 (d) 3
and potassium oxalate proceeds as under:
7. An optically active drug has one chiral center and
2HgCl2  K2 C2 O4  2 KCl  2CO2  Hg2 Cl2 only dextro rotatory isomer is effective.
The mass of Hg 2 Cl2 precipitated from different Morever, it becomes ineffective when its optically
activity is reduced to 35% of original. It was found
solutions in a given time at 100C was as
that mutarotation of this drug was first order
follows:
reaction with a rate constant of 1 x 10 8 s 1 . The

14
Chemistry Times July 18

expiration time of the drug in years is


(a) 1.37 years (b) 2.75 years
(c) 1 year (d) 4.31 years
8. For the irrversible unimolecular type reaction (c) (d)
k
A   B , in a batch reactor, 80%
reactant A (C0  1M ) is converted in a 480 second
12. The Freundlich adsorption isotherm of gas on the
run and conversion is 90% after 18 minute. surface of solid is given below.
The order of this reaction is
(a) 1 (b) 2 (c) 1/2 (d) 1.5 x
 kP1/ n
9. For the reaction, m
H 2  Br2  2 HBr The adsorpion of gas on the surface of solid
The following mechanism has been proposed changes with pressure. What is the order of
reaction if pressure is very low and very high,
k1

Step 1: Br2   2 Br (fast) respectively?
k 1
(a) 1, 0 (b) 0,1 (c) 0,0 (d) 1, 1
k2
Step 2: Br  H 2   HBr  H (slow) [C0  C ]
13. For a certain reaction, a plot of against
k3
Step 3: H  Br2  HBr  Br (fast) C
The order of the reaction is time t, yields a straight line. C0 and C are
(a) 1 (b) 1.5 (c) 2 (d) 3 concentration of reactant at t  0 and t  t
10. For the chemical reaction respectively. The order of reaction is
2 NO2 ( g )  2 NO ( g )  O2 ( g ) , a plot of [ NO2 ] vs (a) 3 (b) Zero (c) 1 (d) 2
Section B: More than one option correct type
time gives a curved line, slope of 1/ [ NO2 ] gives a
14. In an experimental technique involved in
straight line with a positive slope, and a plot of determination of order of reaction, known as intial
ln[ NO2 ] vs time gives a curved line. What is the rate method, rate of reaction is measured at t  0 .
order of reaction? The advantage of this method over instantaneous
(a) zero order reaction (b) first order reaction rate methods is/are
(c) second order reaction (d) a fractional order (a) Initial rate is easier to measure
(b) At t  0 , interference due to any reversible
reaction is negligible.
(c) Reaction order changes with time
(d) It saves the experimental time
11. Which of the following is correct graph for the 15. Order of reaction is detemined by which of the
reaction? following methods?
(a) Initial rate method (b) Graphical method
(c) Isolation method (d) Van’t Hoff method
16. Identify the correct relation about inversion of cane
sugar (follows first order kinetics).
2.303 r r 
(a) k  log  0  
t  rt  r 

(a) (b) 2.303  r0  r 


(b) k  t
ln  
 rt  r0 

1  r0  r 
(c) k  t ln  r  r 
 t 

15
Chemistry Times July 18

2.303  rt  r0  Unit of k  (Conc.)1 n time 1


(d) k  t log  r  r  The differential rate law for nth order may be given
 t 
Section C: Comprehension Type Questions dx n
as:  k  A
The order of reaction is an experimentally dt
determined quantity. It may be zero, positive, Where “A” denotes the reactant.
negative or fractional. The kinetic equation of ‘nth’ 17. For a reaction:
order reaction is
I   OCl   IO   Cl 
1  1 1  in an aqueous medium, the rate of the reaction is
kt    
( n  1)  ( a  x) n 1 a n 1  given by
Half life of ‘nth’ order reaction depends on the d [ IO  ] [ I  ][OCl  ]
initial concentration according to the following k
dt [ OH ]
relation: t1/ 2  a1 n The overall order of the reaction is
The unit of the rate constant varies with the order (a) -1 (b) 1 (c) 0 (d) 2
but general relation for the unit of ‘nth’ order 18. The half life for a zero order reaction equals
reaction is (a) k / 2a 2 (b) a 2 / 2k (c) 2k /a (d) a / 2k
Section D: Match the following
19.

Identify the correct relation,


(a) A, Q, N and B, S, L and C, P, M and D, R, K

16
Chemistry Times July 18

(b) A, S, R and B, Q, K and C, P, L and D, R, N


0.0068 a b
(c) A, Q, N and B, P, M and C, S, L and D, R, K  k  0.0836  0.404 .....(i)
(d) None of the above 65
Section E: Integer Answer Type Question 0.0031 a b
20. The concentration of R in the reaction R  P was  k  0.0836  0.202 .....(ii)
120
measured as a function of time and the following
data were obtained. What is the order of the 0.0032 a b
 k  0.0418  0.404 ....(iii)
reaction? [IIT JEE 2010] 60
Dividing equation (i) by (ii), we get, 4  2b
2 2  2b  b  2
Dividing equation (i) by (iii), we get, 2  2a
a 1
Thus, overall order, a  b  1  2  3
5.Sol: A  2 B  C
Section A: r1  k [ A]m [ B ]n ....(i)
1. b 2. c 3. d 4. d 5. c
r2  2.82 r1  k [2 A]m [ B ]n ....(ii)
6. c 7. a 8. b 9. b 10. c
11. a 12. a 13. a m
r3  9r1  k [ A] [3B ] n
....(iii)
Section B: Dividing equation (ii) by (i),
14. a, b 15. a, b, c, d 16. a, c
Section C: 2.82r1 k[2 A]m [ B ]n
  2.82  2 m  (2)3/ 2  2 m
17. b 18. d r1 k [ A][ B ]n
Section D:
19. c m  3/ 2
Section E: Dividing equation (iii) by (i),
20. 0 9r1 k[ A]m [3B ]n
  9  3n  (3) 2  3n  n  2
r1 k[ A]m [ B ]n
Total order of reaction  m  n  3 / 2  2  7 / 2
6.Sol: t1/ 2  a1 n
1.Sol: Radioactive disintegration reactions are
examples of first order reaction For I  425  (350)1 n ....(i)
2.Sol: Unit of nth order rate constant  mol L s 1 n n 1 1
For II  275  (540)1 n ....(ii)
Compare the above relation with the unit given in
question, For III  941  (158)1 n ....(iii)
1 n
1  n  7 / 2 425  350 
By equation (i) and (ii),  
n 9/2 275  540 
3.Sol: When the concentration of G is doubled, Taking logarithms of both sides,
keeping the concentration of H is fixed, the rate is  425   350 
doubled then the order of reaction wrt G is one.
log    (1  n) log  n2
 275   540 
When concentration of both the reactants G and H 7.Sol: The optical activity remained  35%
is doubled, the rate increases eight times then the So 65% optical activity has been lost, it means 35%
order of reaction is three and order wrt H is 2. of dextro rotatory isomer has been converted to
Total order of reaction  1  2  3 laevo rotatory isomer.
4.Sol: Since mass  moles  M Applying integrated rate law for first order
a b
reaction,
Rate  k  HgCl2   K 2 C2 O4 

17
Chemistry Times July 18

Substituting this in the rate expression results in,


2.303  a 
k log   1/ 2
t ax  k 
Rate  k2  1  [ H 2 ][ Br2 ]1/ 2  k[ H 2 ][ Br2 ]1/ 2
 100   k1 
108 s 1 x t  2.303log  
 65 
  k1  
 where, k k2  k  
t  4.31107 s  1.37 years 
  1  
8.Sol: Let the reaction is of 1st order,
The overall order is 3/2.
2.303 [A ]
k log 0 10.Sol: NO2 decomposition follows second order
t A
reaction.
From 1st data, 11.Sol: As the reaction occurs in the presence of a
2.303 100 catalyst and H 2 ( g ) absorbs on the surface of Ni,
k log  3.35  10 3
480 100  80 therefore it is a zero order reaction.
From 2nd data,
12.Sol: At low pressure, x  kP1 i.e., first order
2.303 100 m
k log  2.131 10 3
18  60 100  90 x
At high pressure,  kP 0 i.e., zero order..
Hence, it is not for 1st order m
As pressure increases, rate of adsorption of gas on
1 1 1 
Now try for 2nd order, k     solid increases. But adsorption will not take place
t  [ A] [ A]0  after certain amount of pressure.
 dC A
  13.Sol: For II order  k [C A ]2 on integrating
1  1 1  3
dt
From 1st data, k   20    8.33  10
480  1 1
1  kt  const .( at t  0, C A  C0 )
 100  CA
From 2nd data,
1 1
 kt 
  C C0
1  1 1
k     8.33  103 (C0  C )
18  60  10 1   kt
1 C0 .C
 100 
Since, the data is following 2nd order kinetics, the [C 0  C ]
or  k . C0 . t ( y  mx  0)
reaction is of 2nd order.. C
9.Sol: For a problem of this type, you should give the 15.Sol: All the methods are used to determine order
rate law according to the slow elementary process. of reaction.
In this case, step 2 is the rds, and the rate law is 17.Sol: Overall order of the reaction = 1
Rate  k2 [ H 2 ][ Br ] 18.Sol: k  x/ t
Since [Br] is not one of the reactants, its relation- t  t1/ 2 , x  a / 2
ship with the concentration of the reactants must
be sought. The rapid reaction in both direction of k  a / 2k
step 1 implies the following relationship, 20.Sol: On careful observations, it can be concluded
that the rate of the reaction is not decreasing with
2 1/ 2
k
K eq  1 
 Br   [ Br ]   k1  [ Br ] decrease in the concentration of the reactant, so
  2 the order of the reaction must be zero.
k1  Br2   k1 

18
Chemistry Times July 18

PAPER-1

Section- I: Maximum Marks: 24)


1. The compound (s) with generate (s) N 2 gas upon
 This section contains six (06) questions
 Each question has FOUR options for correct thermal decomposition below 300C is (are)
answer(s). ONE OR MORE THAN ONE of these (a) NH 4 NO3 (b) ( NH 4 )2 Cr2 O7
four option(s) is (are) correct option(s).
 For each question, choose the correct option(s) to (c) Ba ( N 3 ) 2 (d) Mg 3 N 2
answer the question. 2. The correct statement (s) regarding the binary
 Answer to each question will be evaluated transition metal carbonyl compounds is (are)
according to the following marking scheme: (Atomic numbers: Fe  26 , Ni  28 )
Full Marks: + 4 If only (all) the correct (a) Total number of valence shell electrons at metal
option(s) is (are) choosen.
centre in Fe (CO)5 or Ni (CO) 4 is 16
Partial Marks: + 3 If three or more options
are correct but ONLY two options are chosen, (b) These are predominantly low spin in nature
both of which are correct options. (c) Metal-carbon bond srtengthens when the
Partial marks: +2 If two or more options are oxidation state of the metal is lowered
correct but ONLY one option is chosen and (d) The carbonyl C - O bond weakens when the
it is a correct option. oxidation state of the metal is increased
Partial marks: + 1 If two or more options 3. Based on the compounds of group 15 elements,
are correct but ONLY one option is chosen the correct statement (s) is (are)
and it is a correct option. (a) Bi2 O5 is more basic than N 2 O5
Zero marks: 0 If none of the options is
(b) NF3 is more covalent than BiF3
chosen (i.e. the question is unanswered).
Negative Marks: -2 In all other cases. (c) PH 3 boils at lower temperature than NH 3
 For Example: If first, third and fourth are the (d) The N  N single bond is stronger than the
ONLY three correct options for a question with
second option being an incorrect option; selecting P  P single bond
4. In the following reaction sequence, the correct
only all the three correct options will result in + 4
structure (s) of X is (are)
marks. Selecting only two of the three correct
options (e.g. the first and fourth options), without
selecting any incorrect option (second option in
this case), will result in +2 marks. Selecting only
one of the three correct options (either first or third
or fourth option), without selecting any incorrect
option(s) (second option in this case), with or (a) (b)
without selection of any correct option(s) will
result in -2 marks.

19
Chemistry Times July 18

 For each question, enter the correct numerical


(c) (d) value (in decimal notation, truncated/rounded-off
to the second decimal place; e.g. 6.25, 7.00, -0.33,
5. The reaction (s) leading to the formation of 1,3,5- -0.30, 3.27, -127.30) using the mouse and the on-
trimethylbenzene is (are) screen virtual numeric keypad in the place
designated to enter the answer.
(a)  Answer to each question will be evaluated
according to the following marking scheme.
(b) Full Marks: +3 If ONLY the correct numerical
value is entered as answer.
Zero Marks: 0 In all other cases.
7. Among the species given below, the total number
of diamagnetic species is ______ .
(c) H atom, NO2 monomer, O2 (superoxide), dimeric
sulphur in vapour phase, Mn3O4 ,
( NH 4 ) 2 [ FeCl4 ] , ( NH 4 ) 2 [ NiCl4 ] , K 2 MnO4 ,
K 2 CrO4 .
8. The ammonia prepared by treating ammonium
(d) sulphate with calcium hydroxide is completely
used by NiCl2 .6 H 2 O to form a stable coordination
6. A reversible cyclic process for an ideal gas is compound. Asume that both the reactions are 100%
shown below. Here, P, V, and T are pressure, complete. If 1584 g of ammonium sulphate and
volume and temperature, respectively. The 952 g of NiCl2 .6 H 2 O are used in the preparation,
thermodynamic parameters q, w, H and U are heat, the combined weight (in grams) of gypsum and
work, enthalpy and internal energy, respectively. the nickelammonia coordination compound thus
produced is ______ .
(Atomic weights in g mol 1 : H =1, N =14,
O = 16, S= 32, Cl = 35.5, Ca = 40, Ni = 59)
9. Consider an ionic solid MX with NaCl structure.
Construct a new structure (Z) whose unit cell is
constructed from the unit cell of MX following
the sequential instructions given below. Neglect
The correct option (s) is (are) the charge balance.
(i) Remove all the anions (X) except the central
(a) q AC   U BC and WAB  P2 (V2  V1 ) one
(b) WBC  P2 (V2  V1 ) and qBC  H AC (ii) Replace all the face centered cations (M) by
anions (X)
(c)  H CA   U CA and q AC   U BC (iii) Remove all the corner cations (M)
(d) qBC   H AC and H CA   U CA (iv) Replace the central anion (X) with cation (M)
 number of anions 
Section II (Maximum Marks: 24) The value of   in Z is
 number of cations 
 This section contains EIGHT (08) questions. The ______ .
answer to each question is a NUMERICAL
10. For the electrochemical cell,
VALUE.
Mg ( s ) Mg 2  ( aq,1M ) Cu 2  (aq,1M ) Cu ( s ) the

20
Chemistry Times July 18

standard emf of the cell is 2.70 V at 300 K. When


the concentration of Mg 2  is changed to x M, the
cell potential changes to 2.67 V at 300 K. The value
F
of x is (given,  11500 K V 1 , where F is
R
Faraday constant and R is the gas constant, The
value of ln (10)  2.30 )
11. A closed tank has two components A and B, both
filled with oxygen (assumed to be ideal gas). The
partition separating the two compartments is fixed On addition of equal number of moles of a non-
and is a perfect heat insulator (Figure 1). If the old volatile solute S in equal amount (in kg) of these
partition is replaced by a new partition which can solvents, the elevation of boiling point of solvent
slide and conduct heat but does NOT allow the X is three times that of solvent Y. Solute S is known
to undergo dimerization in thses solvents. If the
gas to leak across (Figure 2), the volume (in m3 ) degree of dimerization is 0.7 in solvent Y, the
of the compartment A after the system attains degree of dimerization in solvent X is ______ .
equilibrium is ______ .
Section - III: (Maximum Marks: 12)
 This section contains Two paragraphs. Based on
each paragraph there are Two(02) questions.
 Each question has FOUR options. ONLY ONE
of these four options corresponds to the correct
answer.
 For each question, choose the option corresponds
to a correct answer.
12. Liquids A and B form ideal solution over the entire
 For each question, marks will be awarded
range of composition. At temperature T, equimolar
according to the following marking scheme:
binary solution of liquids A and B has vapour
Full Marks: +3 If ONLY the correct option
pressure 45 Torr. At the the same temperature, a
corresponding to the correct answer.
new solution of A and B having mole fractions xA Zero Marks: 0 If none of the options is chosen
and xB , respectively, has vapour pressure of 22.5 (i.e. the question is unanswered).
Negative Marks: - 1 In all other cases.
Torr. The value of x A /xB in the new solution is Paragraph for Q.No. 15 & 16
______ . (given that the vapour pressure of pure Treatment of benzene with CO/HCl in the presence
liquid A is 20 Torr at temperature T) of anhydrous AlCl3 / CuCl followed by reaction
13. The solubility of a salt of weak acid (AB) at pH 3
with Ac2 O / NaOAc gives compound X as the
is Y  103 mol L1 . The value of Y is ______ .
major product. Compound X upon reaction with
(Given that the value of solubility product of AB
Br2 / Na2 CO3 , followed by heating at 473 K with
( K sp )  2  10 10 and the value of ionization
moist KOH furnishes Y as the major product.
constant of HB ( K a )  1 10 8 ) Reaction of X with H 2 / Pd  C , followed by
14. The plot given below shows P - T curves (where P H 3 PO4 treatment gives Z as the major product.
is the pressure and T is the temperature) for two
solvents X and Y and isomolal solutions of NaCl 15. The compound Y is
in these solvents. NaCl completely dissociates in
both the solvents.
(a) (b)

21
Chemistry Times July 18

(c) (d)
(c) (d)
16. The compound Z is

(a) (b)

Section- I: 1. b,c 2. b,c 3. a,b,c


4. b 5. a,b,d 6. b,c
(c) (d)
Section- II: 7. 1.00 8. 2992.0 9. 3.00
10. 10.00 11. 2.22 12. 19.00
13. 4.47 14. 0.05
Paragraph for Q.No. 17 & 18 Section- III:
An organic acid P (C11 H12 O2 ) can easily be 15. c 16. a 17. a
oxidized to a dibasic acid which reacts with 18. b
ethyleneglycol to produce a polymer dacron. Upon
ozonolysis, P gives an aliphatic ketone as one of
the products. P undergoes the following reaction
sequences to furnish R via Q. The compound P
also undergoes another set of reactions to produce 1.Sol: NH 4 NO3 ( s )  N 2 O( g )  2 H 2 O
S.
( NH 4 ) 2 Cr2 O7( s )  Cr2 O3 ( s )  4 H 2 O  N 2 ( g )
1) H2 / Pd C
2) NH3 /  1) H2 / Pd C 1) HCl
S 3) Br2 / NaOH
 P 
Q 
R 2) SOCl2 2) Mg / Et2O Ba ( N 3 ) 2  Ba  3 N 2 ( g )
4)CHCl3 , KOH , 3) MeMgBr ,CdCl2 3)CO2 ( dryice)
5) H2 / Pd C 4) NaBH4 4) H3O
Mg 3 N 2 doesn’t undergo thermal decomposition
below 300C .
17. The compound R is
2.Sol: Total number of valence shell electrons at metal
centre in Fe (CO)5 or Ni (CO) 4 is 18.
(a) (b) Metal carbonyl compounds are predominantly low
spin in nature.
Metal - Carbon bond strengthens when the
oxidation state of the metal is lowered.
3.Sol: Metal oxides are basic in nature while non-metal
(c) (d) oxides are acidic in nature.
 Bi2 O5 is more basic than N 2 O5
18. The compound S is Non-metals mainly forms covalent bonds while
metal forms ionic bond.
 NF3 is more covalent than BiF3
Boiling point: NH 3  PH 3
(a) (b) Bond energy P  P  N  N

22
Chemistry Times July 18

4.Sol:

5.Sol:

6.Sol:

AB  Isothermal process,  E or  U  0
AC  Isochoric process,  v   U
BC  Isobaric process,  p   H
7.Sol: K 2 CrO4 i.e. Cr  6  d 0 (diamagnetic)
Paramagnetic  H-atom, NO2 (monomer), O2 (superoxide), S2 (vap), Mn3O4 , ( NH 4 ) 2 [ FeCl4 ] ,
( NH 4 ) 2 [ NiCl4 ], K 2 MnO4 .

8.Sol: (NH 4 )2 SO4  Ca (OH )2 


1584 g 12 mol
 CaSO4  2NH3  2H2O
12 mol 24 mol

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Chemistry Times July 18

NiCl2 .6H2O  6 NH3 


 [ Ni( NH3 )6 ] Cl2  6H2O nA  No. of moles in vessel - A
952 g  4 mol 24 mol 4 mol

Total mass  12 172  4  232  2992 g 5 1 1


  ....(1)
R  400 80 R
9.Sol: MX have NaCl type structure
M  occupies all FCC positions and X  occupies nB  No. of moles in vessel - B
all octahedral voids. 1 3 1
  ....(2)
R  300 100R

Pressure and temperature on the both sides are must


be same.
 number of anions  3 Px
 The value of  number of cations  in Z  n'A  No. of moles in vessel  A  ....(3)
  1 RT
2 2
10.Sol: Mg ( s ) Mg ( aq.1M ) Cu ( aq.1M ) Cu( s ) P (4  x)
n'B  No. of moles in vessel  B  ....(4)
RT
RT  [ Mg 2 ]  Using equation 1, 2, 3 and 4, we get
E  E0  ln  
2 F  [Cu 2 ]  20
x  2.22
2 2 9
E  E 0  2.70 , when [ Mg ]  [Cu ]
12.Sol: The vapour pressure of pure liquid A,
Mg( s )  Mg(aq2 ) (aq, x M )Cu 2 (aq.1M | Cu( s ) PA  20 torr
Mg ( s )  Cu(aq2 )  Cu( s )  Mg (aq2 ) The vapour pressure of pure liquid B, PB  ?

RT  [ Mg 2 ]  PTotal  PA X A  PB X B


E  E0  ln e  2 
2F  [Cu ]  1 1
45  20    PB  
300  x 2 2
2.67  2.70  ln e  
2  11500  1  90  20  PB  PB  70 torr

300 For new solution, PTotal  22.5  PA X A  PB X B


 0.03  ln e ( x)
2  11500 22.5  20 x  70 (1  x)
 0.03  2  11500 x  0.95  X A
ln e x   2.30
300
X B  1  x  0.05
x=10.00
X A 0.95
   19.00
X B 0.05

11.Sol:  [n  ] 
13.Sol: Solubility  K sp  1  
 Ka 

24
Chemistry Times July 18

 103 
Y  103  2 1010 1  8   2  105
 10 

Y 103  20 106  20 103


Y  20  4.47
14.Sol: (Tb ) X  iNaCl ( K b ) X m  362  360  2
( Tb )Y  iNaCl ( K b )Y m  368  367  1
(Kb ) X
 2
( Kb )Y
On addition of equal no. of moles of a non-volatile solute, S in equal amount (in kg) of these solvent.
Solute-S undergo dimerisation in solvent - X and Y

Van’t Hoff factor  i  1  (   degree of ionization)
2
0.7
iY  1   1  0.35  0.65
2
iX  ?
( Tb ) X  3(Tb )Y
iX ( K b ) X m  iY ( K b )Y m

 X 
1  2  ( K B ) X m  (0.65) ( K b )Y m
 
 X  0.05

15, 16.Sol:

25
Chemistry Times July 18

17, 18.Sol:
[O ] ethylene glycol
Organic Acid (C11 H12 O2 )  dibasic acid   polymer (dacron)

O3
( P) 
Zn / H 2O
 aliphatic ketone  other products.
alkene

 Mg|Et2 O
 CO2 ( dryice)
 H 3O 

26
Chemistry Times July 18

ATOMIC STRUCTURE

Introduction
The belief of John Dalton that atom is indivisible  In 1897, J.J.Thomson determined e/m value (or
was disapproved by experimental evidences of charge/mass value) as -1.7588x108 C/g and
different isotopes of elements with different masses proved that whatever gas be taken in the
which ultimately led for the discovery of the discharge tube and whatever be the material of
fundamental particles such as electron, proton and the electrodes, the value of e/m is always the
neutron. same.
 Electrons are, thus, common universal
Sub-atomic particles constituents of all atoms.
(1) Electron:  The charge (e) on electrons was determined
 The nature and existence of electron was (Millikan Oil drop experiment) to be -1.602 x 10-19
established by experiments on conduction C or -4.803 x 10-10 esu or unit negative charge.
electricity through gases i.e., discovery of
cathode rays. e
Rest Mass of electron : m e = e/m
e

1.60×10-19
= kg =9.1094×10 -31kg
1.758820×1011
Some of the characteristics of cathode rays are
given below: = 0.000548 amu (or) 1/1837 times of proton
 Cathode rays travel with high speed of the order of
107 m/s, in straight lines and produce shadows of
the objects placed in their path.
 Cathode rays can penetrate through thin layers of
matter. Mass of electron in motion
 Cathode rays possess high kinetic energy and
Rest mass of electron
therefore m' 
(i) they exert mechanical pressure on the object on 1   u c  2 
 
which they fall
(ii) they produce heat when stopped by matter u = Velocity of electron
(iii) they can ionise a gas c = Velocity of light
 Cathode rays are deflected by electric and magnetic if u = c then mass of moving electron  
field both
 Cathode rays produce fluorescence when they fall  Lorentz named “a subatomic particle i.e., a
on certain substances like ZnS. The colour of fundamental constituent of all matter, having a
fluorescence depends upon the chemical nature of mass of 9.08  10-31 kg and charge equal to -1.602
substance.  10-19 C” as electron (usually represented as
o
 Cathode rays on striking metal target of high atomic e-1).
number such as tungsten, produce highly  The Radius of electron = 4.28  10-14 cm
penetrating X - rays.  1 mole of electrons have 1 Faraday (96500 C)
charge.

27
Chemistry Times July 18

Mass of 1 mole electron = N  me = 6.023  1023


 9.11  10-31 = 5.5  10-7 kg
 The volume of 1 electron = 4/3 ( r 3 )  Mass of 1 mole proton = N  mP = 1.0076 g
= 4/3 [  (4.28  10-14)3]=3.285  10-40 cm3  The radius of proton = 0.88  10-13 cm
(2) Proton:  The volume of proton = 2.85  10-39 cm3
 The nature and existence of proton was
established by the discovery of positive rays or (3) Neutrons:
canal rays by Goldstein in 1886.  Chadwick (1932) bombarded Be or B - atoms
 The specific charge e/m of proton is 9.58  108 sheet with high speed alpha particles, i.e.,
C/kg determined by Thomson and it is named Neutrons mass nearly equal to proton.
as proton by Rutherford. 9
Be  42 He 12 1
4 6 C 0 n
 The specific charge (e/m) of canal rays particles
 A neutron is, therefore, a subatomic particle, a
was found to vary with nature of gas and was
fundamental constituent of matter having a mass
maximum if H2 gas is used.
1.675  10-27 kg and no net charge and usually
 Proton is a subatomic particle which carries
represented as on1.
charge 1.609  10-19 C or one positive charge and
 The e/m value of neutron is zero.
has mass 1.672  10-27 kg i.e., 1.0072 amu.

Atomic models He observed that,


(1) Thomson model of atom:  most of the   particles passed without any
 This model is referred as Plum pudding, Raisin deflection or deflected through small angles of
pudding or Watermelon model. It is visualised
the order of 1o.
as a pudding or watermelon of positive charge  Some of them were deflected away from their
with plums or seeds (electrons) embedded into path by an angle as large as 90o or more.
it.  Only a few (one in about 10,000) were returned
 An important feature of this model is that the back to their original deflection of propagation.
mass of atom is considered to be evenly spread  The scattering i.e., number of scattered
over the atom.   particles (N) is inversely proportional to the
 Drawback : Although this model was able to square of the kinetic energy of the incident
explain the overall neutrality of the atom, but particle. Higher the energy of the incident
was not consistent with the results particle, the smaller will be number of scattered
particle.
(2) Rutherford model of atom:  The scattering of   particles involves perfectly
Rutherford proposed atomic model based on elastic nuclear collisions and obey the law of
 - ray scattering experiment. conservation of energy, momentum and angular
momentum.

28
Chemistry Times July 18

 The scattering i.e., number of scattered (3)If the motion of an electron in orbits is leading
  particles (N) is proportional to the square to the instability of the atom. Considering
of the atomic number (Z) of both the incident electrons as stationary around the nucleus
particles (i.e., Z  ) and the target scatterer (Zt). electrostatic attraction between the dense
The number of   particles showing scattering nucleus and the electrons would pull the
is inversely proportional to the fourth power of electrons toward the nucleus to form a miniature
sin  / 2 where  is the scattering angle i.e., version of Thomson’s model of atom which was
already rejected.
sin 4 ( / 2).  Rutherford model says nothing about the
 The number of   particles showing scattering electronic structure of atoms i.e., how the
is minimum when  / 2 = 900 i.e.,  = 180o electrons are distributed around the nucleus and
Rutherford model or Planetry model what are the energies of these electrons.
 Nucleus is small portion of atom where the Atomic number and Mass number
positive charge and most of the mass of the  A neutral atom contains equal number of
atom is concentrated. electrons and protons.
 Electrons move around the nucleus with a very  Atomic number(Z) : The number of protons or
high speed in circular paths called orbits. electrons(in neutral atoms)
 These observation led Rutherford to propose  Moseley discovered the relationship between
the concept of nucleus in an atom. The size of frequencies of the characteristic X-rays of an
the various nuclei can be calculated from the element and its atomic number. v=a(Z-b), v is
relation,
the frequency of characteristic x-rays, ‘a’ and
r = (1.33  10-13)A1/3
‘b’ are constants having definite values for that
where r is the radius of the nucelus (in cm) with
element.
mass number A.
 Electrons and the nucleus are held together by
electrostatic forces of attraction. The centrifugal
force arising due to fast moving electrons
balances the coulombic force of attraction of
the nucleus and the electrons.
q1q 2
Coulombic force = k
r2
q1 and q2 are charges, r is the distance of
separation of the charges and
k is proportionality constant between electron
and the nucleus.
 Defects of Rutherford’s atomic model
(1) It cannot explain Stability of Atom.  These values are different for different elements.
According to the electromagnetic theory of Thus it became evident that Atomic number is
Maxwell, charged particles when accelerated responsible for chemical reactivity of elements.
should emit electromagnetic radiation (This  Mass Number(A) : The sum of protons and
feature does not exist for planets since they are neutrons in the atom of an element. Mass
uncharged). Therefore, an electron in an orbit number is always a whole number.
will emit radiation, the energy carried by radiation  Number of neutrons(n) = A - Z.
comes from electronic motion. The orbit will thus  Isotopes : Same Z but different A or A - Z
continue to shrink. Calculations show that it Isobars : Different Z but Same A
should take an electron only 10–8 s to spiral into Hydrogen : 1H1, (1D2 or 1H2), (1T3 or 1H3). C14 and
the nucleus. But this does not happen. 7
N14
(2) It fails to explain the atomic spectrum or line Carbon : 6C12, 6C13, 6C14
spectrum. Isotones : Different Z, A but same A-Z

29
Chemistry Times July 18

Chlorine :17Cl35, 17Cl37, 9F19, 10Ne20  These fields are transmitted in the forms of
Isoelectronic: Different Z,A and A-Z but same waves called electromagnetic waves or
no. of electrons CO and N2 electromagnetic radiation.
 Maxwell revealed that light waves are
associated with oscillating electric and magnetic
Developments leading to the Bohr’s character which are perpendicular to each other
model of atom and perpendicular to the direction of
The developments played a major role in the propagation of the wave.
formulation of Bohr’s model of atom were:  Electromagnetic waves do not require medium
 Dual character of the electromagnetic radiation for propagation and can move in vacuum.
(EMR) i.e., wave and particle nature.  There are many types of electromagnetic
 Experimental results of atomic spectra can be radiations, which differ from one another in
explained only by assuming quantised electronic wavelength (or frequency). These constitute
energy levels in atoms. what is called electromagnetic spectrum.
(1) Wave nature of Electromagnetic (I) Electromagnetic spectrum:
radiation (Maxwell) The arrangements of the various types of
 When electrically charged particle moves under electromagnetic radiation in order of their
acceleration, alternating electrical and magnetic increasing (or decreasing) wavelengths or
fields are produced and transmitted. frequencies is known as electromagnetic
spectrum.

Sources of EMR:
 Gamma rays: Produced from nuclei of radioactive atoms through the process of radioactive disintegration
going on spontaneously in nature.
 X - rays: Produced by placing a metal obstacle in the path of a fast moving stream of electrons.
 UV radiation: Present in sun’s rays. The laboratory sources of UV radiation are arc lamps containing Hg
vapour, Xe or hydrogen gas.
 Visible radiation: Produced from stars, arc lamps, hot filaments as of tungsten in an electric bulb, etc. It is
important to note that our eye is sensitive only to radiation lying between wavelengths of 3800-7600 Ao i.e.,
visible radiation
 IR radiation: Emitted by incandescent objects.
 Microwaves: Generated by special generators, e.g., Klystron tube. These waves are used in telephone
circuits.
 Radiowaves: Generated from alternating electric currents of high frequencies.

(II) Wave Characteristics


(A) Wave length (  ) is the distance between two neighbouring troughs or crests in wave. The units of
wave length are m, cm, A0, nm or m .

30
Chemistry Times July 18

(IV) Line spectra of atoms with special reference to


(B) Frequency    : The number of waves that hydrogen.
pass through a given point in one second is (I) Black body radiation (Max Planck):
known as frequency. The units of frequency 
When solids are heated they emit radiation over
are sec-1, cycles per second (cps) or Hertz (Hz). a wide range of wavelengths.
1cps = 1 Hz 
The frequency of emitted radiation goes from a
lower frequency to a higher frequency as the
(C) Wave number   :The number of temperature increases.
 Black Body : Ideal body which emits and absorbs
wavelengths per centimetre or the reciprocal of
radiations of all frequencies. Radiation emitted
wavelength is known as wave number. The units
by such a body is called Black body radiation.
of wave number are cm-1.
Intensity v/s frequency curve of the radiation
(D) Amplitude (A) : The height of the crest or depth
from a black body depends only on its
of the trough of a wave is called Amplitude.
temperature.
Amplitude is a measure of the intensity or
At a given temperature, intensity of radiation
brightness of a beam of light.
emitted increases with decrease of wavelength,
(E) Velocity (C) : The distance travelled by a wave
reaches a maximum value at a given wavelength
in one second is called its velocity. The units of
and then starts decreasing with further
velocity are m/sec or cm/sec.
decrease of wavelength.
 The above experimental results cannot be
explained satisfactorily on the basis of the wave
theory of light.
 All types of electromagnetic radiations have the
same velocity which is equal to 3  1010 cm/sec or
3  108 m/sec
 Relationship between wave characteristics

(II) Planck’s quantum theory:


 Atoms and Molecules could emit (or absorb)
energy only in discrete quantities and not in a
(2) Particle Nature of EMR
continuous manner.
 Some of the experimental phenomenon such as
 The smallest quantity of energy that can be
Diffraction and Interference can be explained
emitted or absorbed in the form of EMR is named
by the wave nature of the electromagnetic
as quantum.
radiation.
 The energy (E) of a quantum of radiation is
 However, following are some of the
proportional to its frequency (v) and is
observations which could not be explained with
expressed by equation
the help of even the electromagnetic theory
i.e., classical physics. E  hv or E  hc / 
(I)The nature of emission of radiation from hot ‘h’ is known as Planck’s constant.
bodies (black -body radiation). Its value is = 6.626× 10–34 J s.
(II)Ejection of electrons from metal surface when  Thus, a body can radiate or absorb energy in
radiation strikes it (photoelectric effect). whole number multiples of a quantum i.e., hv,
(III)Variation of heat capacity of solids as a function 2hv, 3hv....nhv; where n is an integer.
of temperature.

31
Chemistry Times July 18

 With this theory, Planck was able to explain the the phenomena of interference and diffraction.
distribution of intensity in the radiation from The particle nature of light was explained by the

black body as a function of frequency or Black Body Radiation and photoelectric effect.
wavelength at different temperatures. Whenever radiation interacts with matter, it

displays particle like properties and whenever
radiation propagates it displays wave like
properties.
 Some microscopic particles like electrons also
 One quantum is packet of energy not necessarily exhibit this wave-particle duality.
light. Photon is not a material body but it is a packet
(4) Evidence for the quantised electronic
of light energy.
 Intensity of light (number of photons falling per energy levels (Spectra):
unit area per sec) depends upon the number of A ray of white light is spread out into a series of
these photons and if intensity of light is referred coloured bands called spectrum.
as amount of energy falling per unit area per sec; E.g:White light consists of waves with all the
then it also depends upon the wavelength of wavelengths in the visible range - Rainbow
photons used.  When electromagnetic radiation interacts with
 The rest mass of photon is zero. matter, atoms and molecules may absorb energy
and reach to a higher energy state.
 With higher energy these are in an unstable
(III) Photoelectric effect:
state and to return back normal (more stable,
 Ejection of the electrons from metal surface when
lower energy states) energy state, the atoms and
exposed to a beam of light is called as
molecules emit radiations in various regions of
Photoelectric Effect.
the electromagnetic spectrum.
E.g:Potassium, Rubidium, Caesium etc.
 Emission spectrum: The spectrum of radiation
 Einstein (1905) was able to explain the
emitted by a substance that has absorbed energy
photoelectric effect using Planck’s quantum
is known as emission spectrum
theory
 Absorption spectrum : It is like the photographic
(A) Light particles are referred as the photons.
negative of an emission spectrum. A continuum
When a photon of sufficient energy strikes
of radiation is passed through a sample which
an electron in the atom of the metal, it
absorbs radiation of certain wavelengths. The
transfers its energy instantaneously to the
missing wavelength which corresponds to the
electron during the collision and the electron
radiation absorbed by the matter, leave dark
is ejected without any time lag or delay.
spaces in the bright continuous spectrum.
(B) Kinetic energy of the ejected electron is
 The spectrum of the visible light is continuous
proportional to the frequency of the EMR
as all wavelengths (red to violet) are represented
(C) Since the striking photon has energy equal
in the spectra.
to hv and the minimum energy required to
 The emission spectra of atoms in the gas phase
eject the electron is hv0 (also called work
is called line spectra or atomic spectra. Each
function, W0 )
element has a unique line emission spectrum.
(D) The difference in energy (hv – hv0 ) is
Elements like Helium (He), Rubidium (Rb),
transferred as the kinetic energy of the
Caesium (Cs), Thallium (Tl), Indium (In), Gallium
photoelectron.
(Ga) and Scandium (Sc) were discovered by
K.E of ejected electron =1/2meV2 = hv – hv0
spectroscopic methods.
(me = mass of electron)
(V = Velocity of ejected electron.) Hydrogen spectrum
(E) A more intense beam of light consists of The hydrogen spectrum is the simplest of all the

larger number of photons, consequently the atomic spectra.
number of electrons ejected is also larger.  Although H - atom has only one electron, yet its
(3) Dual nature of EMR spectrum consists of several lines. A sample of H2
The wave behaviour of light could account for
 gas, contains infinite number of molecules.

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Chemistry Times July 18

 The hydrogen spectrum consists of several series  Line spectrum becomes more and more complex
of lines named after their discoverers. for heavier atom but certain features which are
The wavelength or wave number of various lines in
 common to all line spectra are
the visible region can be expressed by Rydberg’s i) Line spectrum of element is unique and
equation. ii) There is regularity in the line spectrum of each
element.
1  1 1 
 = = RH 2- 2
λ  n1 n 2 
The value of RH = 1,09,678 cm-1 is valid only for the
lines in the hydrogen spectrum.

For one electron species like He+, Li2+ .... etc, the
value of R = RH x Z2

 Different Series of hydrogen spectrum:


Name of series n1 n2 Spectral region
Lyman series 1 2, 3, 4, 5.. Ultraviolet
Balmer series 2 3, 4, 5, 6.. Visible
Paschen series 3 4, 5, 6, 7.. Near infrared
Brackett series 4 5, 6, 7, 8.. Infrared
Bohr’s model for hydrogen atom
Pfund series 5 6, 7, 8, 9.. Far infrared (1) Postulates
 The electrons in an atom revolves round the
nucleus in definite circular orbits or shells or
energy levels.
 As long as an electron revolves in a certain orbit,
 The spectral lines get closer when the n2 value is its energy remains constant and does not
increased. If n2 is taken as infinity the wavelength radiate energy. These orbits are called stationary
of the limiting line in the series is obtained. orbits or stationary states. Shells are named as
E.g: For Balmer series K, L, M, N .... or numbered as 1, 2, 3, 4 ... from the
1 1 1  R nucleus. As the distance of shell increases from
ν = =R  2 - 2  = = 27,419cm-1 the nucleus, energy level of shell increases.
λ 2   4
 Electrons can revolve only in those stationary
 The first line of each series corresponds to n1 = 1 orbits in which their angular momentum is equal
for Lyman, n1 = 2 for Balmer and n2 = n1 + 1 for the
to integral multiple of h 2
corresponding line.
 The wavelength of line in each series is maximum h
for 1st line as energy is minimum. mvr = n

 For n1 = 6 and n2 > 6, the Humphry series has also
where m = mass of electron,
discovered.
v = velocity of electron
r = radius of orbit
 Balmer series is observed in visibile region while
n = 1 , 2 , 3 ,4 ......
the other series in the hydrogen spectrum are
h = Plank’s constant
invisible. The first line in Balmer series is called
 When an electron drops from a higher orbit to a
H  line and its wavelength is 6563 A0. The second lower orbit, energy is released when an electron
jumps from a lower orbit to a higher orbit, energy
line is called H  line and its wavelength is 4861 is absorbed. The absorbed or evolved energy
A0 . is equal to the difference in energies of two
orbits, which is equal to quanta.

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Chemistry Times July 18

E  E2  E1  hv (vi) Energy of electron in given orbit in


hydrogen atom ( Z = 1 )
E2,E1= Energy of higher & lower orbit,
h = Planck’s constant, -2.179 ×10
-11

 = Frequency of radiation En = 2
ergs/atom
n
 The line spectrum is obtained due to the
electronic transition from one orbit to another
-18
orbit -2.179 ×10
= Joules/atom
(2) Some important results of Bohr’s n
2

equation:
 The force of attraction between the nucleus and -13.6
= eV/atom
the electron = -Ze 2 r 2 n
2

 The centrifugal force of the electron due to


-313.6 -1312
revolving round the nucleus = -mV 2 r = 2
K.cal/mol=
2
KJ/mole
n n
n 2h 2 (vii) Energy of electron in given orbit in H atom
 Radius of Bohr’s orbit r = and H atom like ions
4π 2 m Ze 2
For Hydrogen
r = radius of orbit
n = 1, 2, 3, 4 ..... E1 R H
= En =
h = Planck’s constant n2 n2
m = mass of electron For Hydrogen like ions.
Z = atomic number
e = charge of electron Z2 R H Z2
En =× E 1 =
(i) Radius of orbits in hydrogen atom ( Z = 1 ) n2 n2
r = 0.529  10-8  n2 cm = 0.529  n2 A0 En = Energy of nth orbit in hydrogen atom/
(ii) Radius of orbits in H atom like ions hydrogen like atom .
E1 = Energy of first orbit in hydrogen atom
r = 0.529 × n 2 Z A 0
n = 1, 2, 3, 4 .........
 Energy of electron : Z = Atomic number
(i) Kinetic energy of electron  Ze 2 2r RH = Rydberg’s constant
(viii) Difference of energy between two Bohr
(ii) Potential energy of electron = -Ze2 r
orbits of Hydrogen atom H atom like ions.
(iii) Total energy of electron = KE+PE =
1 1
 Ze 2
2r  - Ze 2 r = -  Ze 2 2r  Δ E = Rhc  2 - 2 
 n1 n 2 
(iv) Expression for the energy of Bohr’s orbit
-2π 2 m Z 2 e 4 1 1
E= Δ E = Z2 Rhc  2 - 2 
n2 h2  n1 n 2 
E = Energy of orbit  E = Energy difference
n = 1,2,3,4,..... (ix) As the value of n increases, the difference
h = Planck’s constant of energy becomes smaller.
m = mass of electron After a certain stage the energy becomes nearly
Z = atomic number equal and this position of continuum is called
e = charge of electron critical energy. If energy is slightly greater than
(v)As we go to higher orbits, kinetic energy this value the electron will be completely
decreases, potential energy increases and removed from the atom.
the total energy decreases.  Velocity of electron (V) in hydrogen atom

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Chemistry Times July 18


This confirms that as the photon has momentum
2π Ze 2 2.188×108
V= = cm/sec as well as wavelength, electrons should also
nh n have momentum as well as wavelength.
For hydrogen atom Vn = V1 n h h
For H atom like ions Vn = ZV1 n  de-Broglie’s equation is λ = mν = p
 Ionisation potential Bohr’s theory and de Broglie’s concept:
For hydrogen atom, I.P= -E1 n 2  According to de Broglie, an electron behaves
as a standing or stationary wave which extends
For H atom like ions, I.P= -Z 2 E1 n 2 round the nucleus in a circular orbit when it
(3) Merits of Bohr’s model: revolves in those orbits.
 It successfully explained the hydrogen spectrum  There is constructive interference of electron
and spectra of ions having one electron. waves and the electron motion has a character
 Energies, radii of possible orbits, Ionisation of standing wave or non-energy radiating
enthalpy and Rydberg constant of hydrogen motion.
atom are in good agreement with experimental  An electron wave to be in phase, the
values circumference of the Bohr’s orbit should be an
(4) Limitations of Bohr’s model: integral multiple of the wavelength of the
 It failed to explain - the spectra of atoms or ions electron wave.
having more than one electron, fine structure of nλ = 2πr
spectral lines, Zeeman effect and Stark effect.
nh h nh
=2πr(λ= ) on rearranging mvr= (Bohr concept)
mv mv 2π

 The splitting of spectral lines of an atom into a


group of fine lines under the influence of a magnetic
field is called Zeeman effect. The splitting of
spectral lines of an atom into group of fine lines
under the influence of an electric field is called
Stark effect.
 It is against to Heisenberg’s uncertainty principle.

Towards quantum mechanical model


of the atom
Two important developments which contributed
significantly for quantum model were :
(1) Dual behaviour of matter  In case the circumference of the Bohr’s orbit
(2) Heisenberg uncertainty principle (2 r ) is bigger or smaller than n , the electron
wave is said to be out of phase. Then destructive
(1) Dual behaviour of matter interference of waves occurs causing radiation
De-Broglie concept : of energy. Such an orbit possibly cannot exist.
 Every object in motion has a wave character.
The wavelengths associated with objects
having large masses are very short hence wave
properties cannot be detected. Electrons and
particles having very small mass are detected  = h/[2m(KE)]1/2
experimentally.

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Chemistry Times July 18

(2) Heisenberg’s uncertainty principle: ψ = Wave function or amplitude of the wave


 Uncertainty principle is the consequence of dual m = Mass of electron
behaviour of matter and radiation. h = Planck’s constant
 It states that it is impossible to determine
simultaneously, the exact position and exact E = Total energy of the electron
momentum (or velocity) of an electron.
 Mathematically, it can be given as in equation V = Potential energy of electron x, y, z are co -
h ordinates.
Δ x .Δ p   The solution of Schrodinger wave equation gives

Principal, Azimuthal and Magnetic quantum number
h but not the spin quantum number.
Δx .mΔv 
4π Quantum numbers
where A set of four numbers used to provide a complete
 x = uncertainty in position description of an electron in an atom are called
quantum numbers. First three were obtained as
 p = uncertainty in momentum natural consequence on solving Schrodinger wave
 v = uncertainty in velocity equation.
m = mass of the particle The quantum numbers are
h = Planck’s constant (1) Principal quantum number
 The uncertainty principle is mainly applicable
for microscopic particles. (2) Azimuthal quantum number
 Significance of Uncertainty Principle : It rules (3) Magnetic quantum number
out existence of definite paths or trajectories of (4) Spin quantum number (not obtained as natural
electrons and other similar particles. consequence on solving wave equation)
(1) Principal quantum number (n)
 It was proposed by Niels Bohr
Quantum mechanical model of atom  The values of n =1, 2, 3, 4 ..... or K, L, M, N .......
 Classical mechanics, based on Newton’s laws of
respectively
motion, successfully describes the motion of all
 It indicates the size and energy of the orbit.
macroscopic objects such as a falling stone, orbiting
 The maximum number of electrons in an orbit
planets etc., which have essentially a particle-like
= 2n2
behaviour.
 Total number of orbitals = n2
 Fails when applied to microscopic objects like
where n = no.of the orbit
electrons, atoms, molecules etc.
 Angular momentum of an electron in an orbit is
Reason : Classical mechanics ignores the concept
of dual behaviour of matter especially for sub- nh 2π
atomic particles and the uncertainty principle. (2) Azimuthal quantum number ( l )
 The branch of science that takes into account this It was proposed by Sommerfield
dual behaviour of matter is called Quantum The values of l = 0, 1, 2, .....( n-1 )
mechanics. The values of l represents various subshells.
 The fundamental equation of quantum mechanics When l = 0, 1, 2, 3 ...... etc they are called as s, p,
was developed by Schrödinger which incorporates d, f ....... sub-shells respectively.
wave-particle duality of matter as proposed by de Energies are in the order of s < p < d < f.
Broglie. It is quite complex and knowledge of  It indicates the shape of orbit or orbital and
higher mathematics is needed to solve it. angular momentum of electron.
Schrodinger’s wave equation  Number of sub-shells in an energy level = n,
where n = no.of the orbit
 2   2   2  8 2 m
   E  V   0  Angular momentum of the electron in an orbital
x 2 y 2 z 2 h2

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Chemistry Times July 18

wave functions” or orbitals form the basis of


h  h 
= l(l+l) = h l  l+1 h  the electronic structure of atoms. In each n
2π  2  orbital, the electron has a definite energy. An
where h = Plank’s constant orbital cannot contain more than two electrons.
l = Azimuthal quantum number  In a multi-electron atom, the electrons are filled
(3) Magnetic quantum number ( m ) in various orbitals in the order of increasing
It was proposed by Lande. energy. For each electron of a multi-electron
The values of m = +l ..... 0 ..... -l atom, there shall be an orbital wave function
The total m values = 2l + 1 characteristic of the orbital it occupies. All the
The total number of m values indicates the total information about the electron in an atom is
number of orbitals in the sub-shell. stored in its orbital wave function ψ and
 The number of orbitals in s, p, d and f sub shells quantum mechanics makes it possible to extract
are 1, 3, 5 and 7 respectively. this information out of ψ .
 It indicates the orientation of orbitals in space.  The probability of finding an electron at a point
 The number of orbitals in an energy level = n2 within an atom is proportional to the square of
 The number of orbitals in a sub-shell = 2l + 1
 Maximum number of electrons in a sub-shell the orbital wave function i.e., ψ 2 at that point.
= 2 (2l +1) l = Azimuthal quantum number. ψ 2 is known as probability density and is
(4) Spin quantum number (s):
always positive. From the value of ψ 2 at
It was proposed by Goudsmit and Uhlenbeck.
 All the above quantum numbers are not enough different points within an atom, it is possible to
to explain the line spectra observed in the case predict the region around the nucleus where
of multi-electron atoms, that is, some of the electron will most probably be found.
lines actually occur in doublets (two lines  The probability of finding an electron at a certain
closely spaced), triplets (three lines, closely distance from the nucleus is called radial
spaced) etc. This suggests the presence of a probability.
few more energy levels than predicted by the  The curves obtained by plotting probability
three quantum numbers. function D=4πr 2 drψ 2 and radial distance (r) are
 An electron spins around its own axis, much in called radial probability distribution curves.
a similar way as earth spins around its own axis  Number of peaks obtained in a curve = n - l
while revolving around the sun. In other words, where n = principal quantum number
an electron has, besides charge and mass, l = Azimuthal quantum number
intrinsic spin angular quantum number. Spin  The region where the probability density
angular momentum of the electron — a vector function reduces to zero is called nodal surfaces
quantity, can have two orientations relative to or simply nodes. No. of radial nodes for any
the chosen axis. These two orientations are particular orbital is given by (n + 1) and number
distinguished by the spin quantum numbers ms of nodes increases with increase of principal
or s which can take the values of +½ or –½. quantum number (n)
represented as    for  12    for  1
2 . E.g: ns-orbital- No.of nodes for 1s orbital is Zero,
for 2s orbital is one, two for 3s etc.
 For each value of m, there can be two s values.
 The nodal surface of 2s orbital exists at a
Thus, maximum number of electrons in an orbital
= 2. Thus the maximum number of electrons distance of 2a 0 from the nucleus. Where a 0 is
present in s, p, d and f shells are 2, 6, 10 and 14 the Bohr radius (0.529A0 or 0.53A0).
respectively.  The curve for 2s orbital two peaks the curve
The following are the important features of the passes through lower maximum at 0.53 A0 and
quantum mechanical model of atom: higher maximum at 2.6A0 radial distance.
 An atomic orbital is the wave function ψ for
an electron in an atom. “One electron orbital

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Chemistry Times July 18

atom. It is characterised by three quantum numbers


(n, l and ml) and its value depends upon the
coordinates of the electron.
 has, by itself, no physical meaning. the square
of the wave function i.e.,  2 which has a physical
meaning.
Angular nodes : Besides the radial nodes
  2 at any point in an atom gives the value of
(probability density function is zero), the probability density at that point.
probability density functions for the np and nd
orbitals are zero at the plane (s), passing through
the nucleus (origin). These are referred as
Angular nodes.
Number of angular nodes : l’, Shapes of atomic orbitals
 The total number of nodes are given by (n–1), (a) s-orbital : Spherical
i.e., Sum of angular nodes and radial nodes. (b) p-orbitals : Dumb-bell shaped.
Orbital No.of Nodal planes Nodal Plane (c) d-orbitals : Double dumbell.(Except dz2) .
s 0 Nil (d) f-orbitals : Fourfold dumbell shape.

px 1 YZ Energies of orbitals:
 The energy of an electron in a hydrogen atom is
py 1 ZX determined solely by the principal quantum number.
pz 1 XY Thus the energy of the orbitals increases as
follows:1s < 2s = 2p < 3s = 3p = 3d <4s = 4p = 4d=
d xy 2 YZ, ZX 4f < ......
d yz 2 ZX, XY  The energy of an electron in a multielectron atom,
depends not only on its principal quantum number
d zx 2 XY, YZ (shell), but also on its azimuthal quantum number
d x 2  y2 (subshell) i.e., for a given principal quantum
2 YZ, ZX
number, s, p, d, f ... of same energy level have
Two planes parallel to Z - axis and making angle of different energies.
45o relative to X or Y - axes.  Effective nuclear charge(Zeff) : The net positive
charge experienced by the outer electrons is known
Orbit, orbital and its Importance as effective nuclear charge. For a given value of ‘n’
Orbit and orbital are not synonymous. the Zeff experienced by the electron decreases with
 Orbit : An orbit, as proposed by Bohr, is a circular increase of azimuthal quantum number (l),
path around the nucleus in which an electron  Shielding effect : The attractive effect will be
moves. A precise description of this path of the lowered due to the partial screening of positive
electron is impossible according to Heisenberg charge on the nucleus by the inner shell electrons.
uncertainty principle. Bohr orbits, therefore, have Effective sheilding order is s > p > d > f even if all
no real meaning and their existence can never be are present in same ‘n’
demonstrated experimentally.  (n+l)rule : Mathematically, the dependence of
 Orbital : Shape of the orbital which encloses a energies of the orbitals on n and l are quite
region or volume in which the probability of complicated but one simple rule is that,
finding the electron is very high, say, 90%. Enclosed a)The lower the value of (n + l) for an orbital, the
region is referred as Boundary surface diagram or lower is its energy.
contour surface diagram. An atomic orbital, on the b)If two orbitals have the same value of (n + l), the
other hand, is a quantum mechanical concept and orbital with lower value of ‘n’ will have the lower
energy.
refers to the one electron wave function  in an

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Chemistry Times July 18

Filling of electrons in Orbitals of an 2. An oil drop has 6.39 1019 C charge. The number
Atom of electrons in this drop is
The filling of electrons into the orbitals of different (a) 2 (b) 3 (c) 4 (d) 5
atoms takes place according to the aufbau principle 3. Which of the following statements is wrong about
which is based on the Pauli’s exclusion principle, cathode rays?
the Hund’s rule of maximum multiplicity and the (a) They travel in straight line towards cathode.
relative energies of the orbitals. (b) They produce heating effect.
(c) They are carrying negative charge.
(1) Aufbau principle:
(d) They produce X - rays when strike with material
Electron filling follows energy ranking. The
having high atomic masses.
orbitals are successively filled in the order of
4. Rutherford’s experiment which establishes the
their increasing energy.The energy value of an
nuclear atom model of the atom, used a beam of
orbital increases as its (n + l) value increases.
(a)   particles, which impinged on a metal foil
(2) Pauli’s exclusion principle:
(I) No two electrons in the same atom can have the and got absorbed
same values for all the four quantum numbers. (b)   particles which impinged on a metal foil
(II) Maximum number of electrons in an orbital is and ejected electrons
two. (c)   particles which impinged on a metal foil
(3) Hund’s rule: and got scattered
Pairing does not take place unless degenerate (d) Helium atoms which impinged on a metal foil
(same energy containing) orbitals are occupied and got scattered
singly. Unpaired electrons have parallel spin and 5. According to Bohr’s atomic theory, the correct
are paramagnetic in behaviour. statement is
Extra Stability of Half and fully Filled Orbitals Z2
due to maximum exchange energy. (a) Potential energy of electron 
n2
E.C of Cr - atom is1s2 2s2 2p6 3s2 3p6 3d5 4s1 but not
1s2 2s2 2p6 3s2 3p6 3d4 4s2. (b) The product of velocity of electron and principal
E.C of Cu - atom is 1s2 2s2 2p6 3s2 3p6 3d10 4s1 but quantum number (n)  Z 2
not 1s2 2s2 2p6 3s2 3p6 3d9 4s2 (c) Frequency of revolution of electron in an orbit
(4) Electronic configuration of an Z2
element is represented by the notation  3
n
(nlx)
x : number of electrons present in an orbital, (d) Coulombic force of attraction on the electron
l : denotes the sub-shell
Z2
n : principal quantum number. 
n2
6. The ionisation energy of He is 19.6 1018 J
atom1 . The energy of the first stationary state of
Li 2 will be
(a) 21.2 1018 J/atom (b) 44.10 1018 J/atom
1. When beryllium is bombarded with   particles
(Chadwick’s experiment) extremely penetrating (c) 63.2 1018 J/atom (d) 84.2 1018 J/atom
radiations which cannot be deflected by electric 7. The energy of electron in first Bohr’s orbit of H-
or magnetic field are given out. These are atom is -13.6 eV. What will be its potential energy
(a) A beam of protons in 4th orbit ?
(b) Alpha rays (a) -13.6 eV (b) -3.4 eV
(c) A beam of neutrons (c) -0.85 eV (d) -1.70 eV
(d) A beam of neutrons and protons

39
Chemistry Times July 18

8. The frequency of line spectrum of sodium is 15. The photoelectric effect supports quantum nature
14 1
5.09 10 sec . Its wavelength (in nm) will be of light because
(a) there is a minimum frequency of light below
 c  3  108 m / sec  which no photoelectrons are emitted
(a) 510 nm (b) 420nm (c) 589 nm (d) 622 nm (b) the maximum kinetic energy of photoelectrons
9. The correct expression derived for the energy of an depends only on the frequency of light and not on
electron in the nth energy level is for H-atom its intensity
(c) even when metal surface is faintly illuminated
2 2 me 4 2 2 me 4 thephotoelectrons leave the surface immediately
(a) En  (b) En 
n2 h2 nh 2 (d) electric charge of photoelectrons is quantised
16. Which transition of the hydrogen spectrum would
2 2 me 2 2 2 me 4 have the same wavelength as the Balmer transition,
(c) En  2 2 (d) En   2 2
nh nh n=4 to n=2 of He spectrum?
10. For H-atom, the energy required for the removal of
(a) n2  2 to n1  1 (b) n2  3 to n1  1
electron from various sub-shells is given as under.
(c) n2  4 to n1  2 (d) n1  2 to n1  3
17. The shortest wavelength in H spectrum of Lyman
series when RH  109678cm 1 is

(a) 1215.67 Å (b) 911.7 Å


The order of the energies would be
(c)1002.7 Å (d) 1127.30 Å
(a) E1  E2  E3 (b) E3  E2  E1 18. A 200g cricket ball is thrown with a speed of
(c) E1  E2  E3 (d) None of these 3.0 103 cm sec1 . What will be its de Broglie’ss
11. The correct order of the wave number of the 27 2 1
wavelength  h  6.6  10 g cm sec 
following radiations: IR, UV, radio waves, X-rays
and visible light is 32
(a) 1.1 1032 cm (b) 2.2 10 cm
(a) X-rays > IR > visible > UV > radio waves 32
(b) radio waves > IR > visible > UV > X-rays (c) 0.55 1032 cm (d) 11.0  10 cm
(c) X-rays > UV > visible > IR > radio waves 1 h
(d) UV > visible > IR > radio waves > X-rays 19. The uncertainty in position of a particle is
2m 
12. How many photons of light having a wavelength
We can say that
0
of 4000 A are necessary to provide 1 J of energy? (a) Uncertainty in position is twice that of
momentum.
( h  6.63  10 34 J .s, c  3  108 m / s )
(b) Only the position of particle is altered by impact
(a) 2.01  1018 (b) 4.97  1018 of light.
18
(c) 10 (d) 6  1023 (c)Uncertainty in momentum is very large compared
13. What would be the ratio of energy of a photon of to uncertainty in position.
frequency x s-1 to y s-1? (d)Uncertainty in position and velocity are equal.
(a) xy (b) x/y (c) y/x (d) x+y 20. The uncertainty in position of an electron is equal
14. The minimum energy required to overcome the to its de Brogile wavelength. The minimum % error
attractive forces of electron and surface of Ag metal in its measurement of velocity under this
is 7.52 1019 J. What will be the maximum K.E. of circumstance approximately is
electron ejected out from Ag which is being (a) 6% (b) 5% (c) 7% (d) 8%
21. The d-orbital that does not have four lobes is
exposed to U. V. light of   360Å?
(a) 36.38 1019 Joule (b) 6.92 1019 Joule (a) d x 2  y 2 (b) d xy (c) d yx (d) d z 2
22. Which of the following sets of quantum numbers
(c) 57.68 1019 Joule d) 67.68 1019 Joule
is correct for an electron in 4 f-orbital?

40
Chemistry Times July 18

27. If n and l are the principal and azimuthal quantum


1
(a) n  4, l  3, m  4, s   numbers, then the expression for calculating the
2 total number of electrons an energy level can
1 accommodate is
(b) n  4, l  4, m  4, s  
2 l n l  n 1

(a)  2(2l  1) (b)  2(2l  1)


1 l 1 l 1
(c) n  4, l  3, m  1, s  
2 l  n 1 l  n 1

1 (c)  2(2l  1)
l 0
(d)  2(2l  1)
l 0
(d) n  3, l  2, m  2, s  
2 28. Which is the correct order of increasing energy of
the listed orbitals in the atom of titanium?
(At. no. Z = 22)
(a) 4s 3s 3p 3d (b) 3s 3p 3d 4s
23. The above (c) 3s 3p 4s 3d (d) 3s 4s 3p 3d
29. Which of the following is responsible to rule out
configuration is not correct as it violates the existence of definite paths or trajectories of
(a) Only Hund’s rule electrons?
(b) Only Pauli’s exclusion principle (a) Pauli’s exclusion principle.
(c) (n + l)rule (b) Heisenberg’s uncertainty principle.
(d) (Hund + Pauli) rule (c) Hund’s rule of maximum multiplicity.
24. The orbital diagram in which ‘Aufbau principle’ is (d) Aufbau principle.
violated is 30. The energy of an electron moving in nth Bohr’ss
13.6 2
(a) orbit of an element is given by En  Z eV/
n2

(b) atom. The graph of E vs Z 2 (keeping ‘n’ constant)


will be
(c)

(d)
25. An electron of velocity ‘v’ is found to have a certain
value of de Broglie wavelength. The velocity (a) (b)
possessed by neutron to have the same de Broglie
wavelength is
v
(a) 1840 v (b)
1840
1840
(c) 3 v (d)
v
26. An electron, a proton and an alpha particle have (c) (d)
kinetic energies of 16E, 4E and E respectively. What
is the qualitative order of their de broglie
wavelengths?
(a) e   p   (b)  p    e (a) 1  106 cm s 1 (b) 1  105 cm s 1
(c)  p  e   (d)   e   p (c) 1  1011 cm s 1 (d) 1.1 109 cm s 1

41
Chemistry Times July 18

c 3  108 ms 1
8.Sol:   
v 5.09  1014 s 1
1. c 2. c 3. a 4. c 5. c  0.589 106 m  589nm
6. b 7. c 8. c 9. d 10. c 9.Sol: Conceptual
11. c 12. a 13. b 14. b 15. a 10.Sol: In case of H atom, energy of 3s, 3p, 3d is as
16. a 17. b 18. a 19. d 20. d follows 3s=3p=3d
21. d 22. c 23. d 24. b 25. b 11.Sol: Increasing order of wavelength of EMR: X -
26. a 27. d 28. c 29. b 30. a rays < UV < Visible < IR < Radiowaves
Wavelength is inversely proportional to wave
number
Decreasing order of wave number of EMR: X - rays
> UV > Visible > IR > Radiowaves
1.Sol: Neutron carrying no electrical charge
hc
2.Sol: Charge on oil drop  6.39  1019 C 12.Sol: Energy of a photon  hv 

Now we know that
1.602  1019 C is the charge on one electron (6.63  1034 J .s )(3  108 m / s )

(4000  10 10 m)
 6.39  1019 C will be charge on
 4.97 1019 J .
6.39  1019
 Number of photons required
1.602  1019
1J
 4 electrons   2.01 1018
3.Sol: They travel in straight lines towards anode as 4.97  10 19 J
they carry negative charge. E1 v1 x
4.Sol:   particles which impinged on a metal foil 13.Sol: E  v  E  v  y
2 2
and got scattered.
Z n2 hc
5.Sol: v  ;r  14.Sol: Energy absorbed 
n Z 

v 6.625 1027  3.0 1010



Frequency of revolution  2 r 360  108
n

 5.52  1011 erg


Ze2
Coulombic force of attraction 
(4 0 )r 2  5.52 1018 Joule

6.Sol: E1 for Li 2  E1 for H  Z 2  E1 for H  9   7.52  10 19    .552  10 19 

E1 for He   E1 for H  Z 2 He  E1 for H  4  6.92 1019 Joule


15.Sol: The photoelectric effect supports quantum
2 9 nature of light because there is a minimum
or E1 for Li  E1 for He 
4 frequency of light below which no photoelectrons
are emitted.
9
 19.6  1018  16.Sol: For He ion, we have
4
 44.10 1018 J/atom 1  1 1 
 RH Z 2  2  2 
7.Sol: En for H = -13.6 eV/n2   n1 n2 
E4 for H = -13.6 eV/42 = -0.85 eV

42
Chemistry Times July 18

1 1 h
 RH [2]2  2  2  18.Sol:  
2 4  mv

3 h
 RH ...(A) 19.Sol:  x  p  
4 4
Now for H atom
2 h h
1  1 1 
 p     p  
4 4
 RH  2  2  ...(B)
  n1 n2 
h 1 h
Equating (A) and (B) we have mv   v 
4 2m 
1 1 3
 2  h  h
 x    
2
n1 n2 4 20.Sol: x.P 
4  p
Obviously n1  1 and n1  2. Hence the transition
h h P v 1
n  2 to n  1 in hydrogen atom, will have the    P     
p
  4 P v 4
same wavelength as the transition n  4 to n  2
in He species. v 1
% Uncertainty   100  8%
17.Sol: For Lyman series n1  1 v 4
21.Sol: dz2 contains only two lobes
For shortest '  ' of Lyman series is the energy
25.Sol: Since the mass of the neutron is 1840 times the
difference in two levels showing transition should
mass of an electron.
be maximum (i.e., n2   ).
h
1 1 1  26.Sol:  
 RH  2  2  2m( K .E.)
 1  
28.Sol: Ti (22) :1s 2 2 s 2 2 p 6 3s 2 3 p 6 3d 2 4 s 2
 109678
 Order of increasing energy is 3s,3 p, 4 s,3d .
   911.7 108
29.Sol: According to Heisenberg’s uncertainty
0
 911.7 A principle.

43
Chemistry Times July 18

SOME BASIC CONCEPTS OF CHEMISTRY

1. Excess of NaOH (aq) was added to 100 mL of (a) X 2 O3 (b) X 2 Cl3


FeCl3 (aq) resulting into 2.14 g of Fe(OH )3 . The
(c) X 2 ( SO4 )3 (d) XPO4
molarity of FeCl3 (aq) is: 7. A sample of a hydrate of barium chloride weighting
(Given molar mass of Fe  56 g mol 1 and molar 61 g was heated until all the water of hydration is
removed. The dried sample weighted 52 g. The
mass of Cl  35.5 g mol 1 ) [2017] formula of the hydrated salt is: [2015]
(a) 0.2 M (b) 0.3 M (c) 0.6 M (d) 1.8 M (atomic mass, Ba = 137 amu , Cl=35.5 amu)
2. What quantity (in Ml) of a 45% acid solution of a (a) BaCl2 , 4 H 2 O (b) BaCl2 ,3H 2 O
mono-protic strong acid must be mixed with a 20%
(c) BaCl2 , H 2 O (d) BaCl2 , 2 H 2 O
solution of the same acid to product 800 mL of a
29.875% acid solution? [2017] 8. A  2 B  3C  AB2 C3
(a) 320 (b) 325 (c) 316 (d) 330
Reaction of 6.0 g of A, 6.0 1023 atoms of B, and
3. 5 L of an alkane requires 25 L of oxygen for its
complete combustion. If all volumes are measured 0.036 mol of C yields 4.8 g of compound AB2 C3 .
at constant temperature and pressure, the alkane If the atomic mass of A and C are 60 and 80 amu,
is: [2016] respectively, the atomic mass of B is (Avogadro
(a) Isobutane (b) Ethane
no.  6 1023 ): [2015]
(c) Butane (d) Propane
4. The amount of arsenic pentasulphide that can be (a) 50 amu (b) 60 amu
obtained when 35.5 g arsenic acid is treated with (c) 70 amu (d) 40 amu
9. Dissolving 120 g of a compound of (mol.wt.60)
excess H 2 S in the presence of conc. HCl in 1000 g of water gave a solution of density 1.12
(assuming 100% conversion) is: [2016] g/mL. The molarity of the solution is: [2014]
(a) 0.25 mol (b) 0.50 mol (a) 1.00 M (b) 2.00 M
(c) 0.333 mol (d) 0.125 mol (c) 2.50 M (d) 4.00 M
5. The volume of 0.1 N dibasic acid sufficient to 10. The amount of oxygen in 3.6 moles of water is:
neutralise 1 g of a base that funnishes 0.04 mole [2014]
of OH  in aqueous solution: [2016] (a) 115.2 g (b) 57.6 g (c) 28.8 g (d) 18.4 g
(a) 400 mL (b) 600 mL 11. A gaseous compound of nitrogen and hydrogen
(c) 200 mL (d) 0.125 mL contains 12.5 % (by mass) of hydrogen. The
6. Choose the incorrect formula out of the four density of the compound relative to hydrogen is
compounds for an element X below: [2016] 16. The molecular formula of the compound is:
[2014]

44
Chemistry Times July 18

(a) NH 2 (b) N 3 H 9V V
  160   239  V  316
(c) NH 3 (d) N 2 H 4 20 5
3.Sol: Since the compound undergoing combustion
12. The amount of BaSO4 formed upon mixing 100
is an alkane, hence the combustion reaction can
mL of 20.8% BaCl2 solution with 50 mL of 9.8% be written as
H 2 SO4 solution with 50 mL of 9.8%  3n  1 
Cn H 2 n  2    O2 
 nCO2  (n  1) H 2 O
H 2 SO4 solution will be: [2014] 5L  2 
25 L
(a) 23.3 g (b) 1.65 g (c) 30.6 g (d) 33.2 g Since volumes are measured at constant T&P,
13. The density of 3M solution of sodium chloride is hence According to Avogadro’s law
1.252 g mL1 . The molarity of the solution will be: C3 H 8  5O2  3CO2  4 H 2 O
1
(molar mass, NaCl  585 g mol ) [2013] Conc . HCl
4.Sol: 2 H 3 AsO4 5 H 2 S As2 S5 8H 2O
(a) 260 m (b) 2.18 m (c) 2.79 m (d) 3.00 m 2 moles
1 mole
1 mole
1/2 mole

14. Number of atoms in the following samples of


substances is the largest in: [2013] 35.5
 number of mole of H 3 AsO4  0.25
(a) 4.0 g of hydrogen (b) 7.10 g of chlorine 142
(c) 127.0 g of iodine (d) 48.0 g of magnesium
0.25
 number of moles of As2 S5  0.125 mol
2
5.Sol: Applying law of equivalence
Equivalence of acid = Equivalence of base
1. a 2. c 3. d 4. d 5. a 0.1 v  0.04  1
6. b 7. d 8. a 9. b 10. b v  0.4 L  0.4  1000  400 ml
11. d 12. a 13. c 14. c
6.Sol: X 2 O3  X 3  O 2
X 2 Cl3  X 3  Cl 2
X 2 ( SO4 )3  X 3  SO4 2
1.Sol: XPO4  X 3  PO43
FeCl3 (aq) 3NaOH (aq)  Fe(OH )3 ( s)  3NaCl (aq)
limiting ( Excess amount ) 7.Sol: Weight of hydrated BaCl2  61 g
reagent Notbehaveas
lim itingreagent
Weight of anhydrous BaCl2  52 g
weight in g Loss in mass  9g
Moles of Fe(OH )3 
M .weight of Fe(OH )3
Assuming BaCl2 . xH 2 O as hydrate
2.14 g
  0.02 mol 9
107 g / mol Moles of H 2 O   0.5
18
1.0 mole of Fe(OH )3 is obtained from  1.0 mole
Gram molecular weight of BaCl2  208
of FeCl3
% of H 2 O in this hydrated
0.02 mole of Fe(OH )3 will be obtained from
9
 0.02 mole FeCl3 BaCl2   100  14.75 %
61
No.of moles 0.02 mole
Molarity    0.2 M 18 x
Volume in L 0.1 L   100 on solving x  2
208  18 x
V  45 (800  V )  20 800  29.875
2.Sol:   So, the formula is BaCl2 .2 H 2 O
100 100 100

45
Chemistry Times July 18

 AB2C3 ....(1) 11.Sol: In an unknown compound containing N and


8.Sol: A  2 B  3C 
H
6.0 g given % of H  12.5%
No. of moles of A  60 g / mol  0.1 mol
 % of N  100  12.5  87.5%
23
No. of moles of B  6.00  0  0.1 mol
6.000  10 23
No. of moles of C  0.036 mol
AB2 C3 is formed accordingly to C, which is a
limiting reagent.
Since 3 mole of C are used in (1)
So it gives 1 mole of AB2 C3 2 vapour density = Mol.wt ; mol wt.
 16  2  32
Molecular formula  n  empirical formula mass
0.036 Given mass (4.8)
n AB2 C3   0.012  32
3 Molecular mass (M.M) n 2
16
4.8  Molecular formula of the compound will be
Mol.mass   400
0.012  ( NH 2 ) 2  N 2 H 4
 400  60  (2  x)  (80  3)  x  50
12.Sol: BaCl2  H 2 SO 
 BaSO4  2 HCl
9.Sol: Given 208 g 98 g 73 g
233 g
7.3 g
2.8 g 9.8 g 23.3 g
mass of solute ( w)  120 g
13.Sol: The relation between molarity (M) and
mass of solvent ( w)  1000 g molality (m) is
Mol.mass of solute  60 g 1 M 
d  M   2  , M 2  Mol. mass of solute
density of solution  1.12 g / ml  m 1000 
From the given data, On putting value
Mass of solution  1000  120  1120 g  1 58.5 
1.252  3   
Mol. mass Mol. mass  m 1000 
 d or V 
V d on solving m  2.79

1120 14.Sol: 4g of hydrogen = 4 mole of hydrogen atoms


Volume of solution V   1000 ml or
1.12  4  6.023 1023 atom
 1 litre 71.0
71.0 gm of chlorine   1 moles of chlorine
W 71.0
Now molarity ( M ) 
Mol  mass  V (lit )  6.023 1023 chlorine atoms
120 127 gm of iodine =1 mole of I atoms
  2M
60  1  6.023 1023 atoms
48.0 gm of magnesium
10.Sol: 1 mole of water contains  16gm of O2
 3.6 mole of water contains 48.0
  2  6.023  1023
 16 13.6  57.6 g 24.0
 4.0 gm H 2 has the largest number of atoms.

46
Chemistry Times July 18

PAPER-2

Section- I: (Maximum Marks: 24)


 This section contains SIX (06) questions 1. The correct option (s) regarding the complex
 Each question has FOUR options for correct
answer(s). ONE OR MORE THAN ONE of these [Co (en) ( NH 3 )3 ( H 2 O )]3
four option(s) is (are) correct option(s). (en  H 2 NCH 2 CH 2 NH 2 ) is (are)
 For each question, choose the correct option(s) to (a) It has two geometrical isomers
answer the question. (b) It will have three geometrical isomers if
 Answer to each question will be evaluated bidentate ‘en’ is replaced by two cyanide
according to the following marking scheme: ligands
Full Marks: + 4 If only (all) the correct option(s) (c) It is paramagnetic
is (are) choosen. (d) It absorbs light at longer wavelength as
Partial Marks: +3 If all the four options are correct
but ONLY three options are chosen. compared to [Co(en)( NH 3 ) 4 ]3
Partial Marks: + 2 If three or more options are 2. The correct option (s) to distinguish nitrate salts
correct but ONLY two options are chosen, both of of Mn2 and Cu 2  taken separately is (are)
which are correct options.
Partial marks: + 1 If two or more options are (a) Mn2 shows the characteristic green colour in
correct but ONLY one option is chosen and it is a the flame test
correct option. (b) Only Cu 2  shows the formation of precipitate
Zero marks: 0 If none of the options is chosen
by passing H 2 S in acidic medium
(i.e. the question is unanswered).
Negative Marks: -2 In all other cases. (c) Only Mn2 shows the formation of precipitate
 For Example: If first, third and fourth are the
by passing H 2 S in faintly basic medium
ONLY three correct options for a question with
second option being an incorrect option; selecting (d) Cu 2+ /Cu has higher reduction potential than
only all the three correct options will result in + 4
Mn2+ /Mn (measured under similar
marks. Selecting only two of the three correct
conditions)
options (e.g. the first and fourth options), without
selecting any incorrect option (second option in 3. Aniline reacts with mixed acid (conc. HNO3 and
this case), will result in +2 marks. Selecting only conc. H 2 SO4 ) at 288K to give P(51%), Q(47%)
one of the three correct options (either first or third
and R(2%). The major product (s) of the following
or fourth option), without selecting any incorrect
reaction sequence is (are)
option(s) (second option in this case), with or
without selection of any correct option(s) will
result in -2 marks.

47
Chemistry Times July 18

concentration [ A]0 , and t1/3 is the time required


for the partial pressure of A to reach 1/3rd of its
initial value. The correct option(s) is (are) (Assume
that all these gases behave as ideal gases)

(a) (b)
(a) (b)

(c) (d)
(c) (d)

4. The Fischer presentation of D - glucose is given


below. 6. For a reaction, A  P , the plots of [A] and [P]
with time at temperatures T1 and T2 are given
below.

The correct structure (s) of   L  glucopyranose


is (are)
If T2  T1 , the correct statements (s) is (are)
(Assume  H  and  S  are independent of
temperature and ratio of lnK at T1 to lnK at T2 is
(a) (b)
greater than T2 /T1 . Here H,S,G and K are enthalpy,,
entropy, Gibbs energy and equilibrium constant,
respectively.)
(a)  H   0,  S   0 (b)  G   0,  H   0
(c)  G   0,  S   0 (d)  G   0,  S   0
(c) (d)
Section II (Maximum Marks: 24)
 This section contains EIGHT (08) questions. The
5. For a first order reaction A( g )  2 B( g )  C ( g ) at answer to each question is a NUMERICAL
constant volume and 300 K, the total pressure at VALUE.
 For each question, enter the correct numerical
the begining (t  0) and at time t are P0 and Pt , value (in decimal notation, truncated/rounded-off
respectively. Initially, only A is present with to the second decimal place; e.g. 6.25, 7.00, -0.33,

48
Chemistry Times July 18

-.30, 30.27, -127.30) using the mouse and the undergo self-reduction. The weight (in kg) of Pb
onscreen virtual numeric keypad in the place produced per kg of O consumed is ______ .
2
designated to enter the answer.
 Answer to each question will be evaluated (Atomic weights in g mol 1 : O  16, S  32, Pb  207 )
according to the following marking scheme. 9. To measure the quantity of MnCl2 dissolved in
Full Marks: + 3 If ONLY the correct numerical an aqueous solution, it was completely converted
value is entered as answer.
Zero Marks: 0 In all other cases. to KMnO4 using the reaction,
MnCl2  K2S2O8  H2O  KMnO4  H2 SO4  HCl
7. The total number of compounds having atleast one
(equation not balanced).
bridging oxo group among the molecules given
Few drops of concentrated HCl were added to this
below is ______ .
solution and gently warmed. Further, oxalic acid
N 2 O3 , N 2 O5 , P4 O6 , P4 O7 , H 4 P2 O5 , H 4 P3O10 , (225 mg) was added in portions till the colour of
H 2 S 2 O3 , H 2 S 2 O5 the permanganate ion disappered. The quantity of
8. Galena (an ore) is partially oxidized by passing MnCl2 (in mg) present in the initial solution is
air through it at high temperature. After some time, ______ . (Atomic weights in
the passage of air is stopped, but the heating is g mol 1 : Mn  55, Cl  35.5 )
continued in a closed furnace such that the contents

10. For the given compound X, the total number of optically active stereoisomers is ______ .

11. In the following reaction sequence, the amount of D (in g) formed from 10 moles of acetophenone is
______ . (Atomic weights in g mol 1 : H = 1, C = 12, N = 14, O = 16, Br = 80. The yield (%) corresponding
to the product in each step is given in the parenthesis)

12. The surface of copper gets tarnished by the formation of copper oxide. N 2 gas was passed to prevent the
oxide formation during heating of copper at 1250 K. However, the N 2 gas contains 1 mole % of water
vapour as impurity. The water vapour oxidises copper as per the reaction given below.
2Cu ( s )  H 2 O ( g ) 
 Cu2 O ( s )  H 2 ( g )
PH 2 is the minimum partial pressure of H 2 (in bar) needed to prevent the oxidation at 1250 K. The value

of ln ( pH 2 ) is ______ .

49
Chemistry Times July 18

(Given: total pressure = 1 bar, R (universal gas corresponding to the correct matching is chosen
1 1
constant)  8 JK mol , ln(10)  2.3 . Zero Marks: 0 If none of the options is chosen
(i.e. the question is unanswered).
Cu(s) and Cu2 O ( s ) are mutually immiscible. Negative Marks: - 1 In all other cases.
15. Match each set of hybrid orbitals from List-I with
At 1250K: 2Cu ( s )  1/ 2 O2 ( g ) 
 Cu2 O ( s );
complex (es) given in List-II.
G   78, 000 J mol 1 List - I List - II
H 2 ( g )  1/ 2 O2 ( g ) 
 H 2 O ( g ); P. dsp 2 1. [ FeF6 ]4 

G   1, 78, 000 J mol 1 ; G is theGibbs energy ) Q. sp 3 2. [Ti ( H 2 O)3 Cl3 ]


13. Consider the following reversible reaction, R. sp 3 d 2 3. [Cr ( NH 3 ) 6 ]3
 AB( g ) .
A( g )  B( g )  S. d 2 sp 3 4. [ FeCl4 ]2 
The activation energy of the backward reaction
5. Ni (CO ) 4
exceeds that of the forward reaction by
2 RT (in J mol 1 ) . If the pre-exponential factor of 6. [ Ni (CN ) 4 ]2 
the forward reaction is 4 times that of the reverse The correct option is:
reaction, the absolute value of G  (in J mol 1 ) (a) P  5; Q  4, 6; R  2,3; S  1
for the reaction at 300 K is ______ . (Given; (b) P  5, 6; Q  4; R  3; S  1, 2
ln(2)  0.7, RT  2500 J mol 1 at 300 K and G is (c) P  6; Q  4,5; R  1; S  2,3
Gibbs energy) (d) P  4, 6; Q  5, 6; R  1, 2; S  3
14. Consider an electrochemical cell: 16. The desired product X can be prepared by reacting
A( s ) An  ( aq, 2 M ) B 2 n  ( aq,1M ) B ( s ) . The value the major product of the reactions in List-I with
one or more appropriate reagents in List-II. (given,
of H  for the cell reaction is twice that of G  order of migratory aptitude: ary1 > alky1>
hydrogen)
at 300 K. If the emf of the cell is zero, the S  (in
J K 1 mol 1 ) of the cell reaction per mole of B
formed at 300 K is ______ . (Given: ln(2)  0.7 ,
R (universal gas constant)  8.3 J K 1mol 1 .
H, S and G are enthalpy, entropy and Gibbs energy,
respectively.)

Section - III: Maximum Marks: 12


 This section contains FOUR (04) questions.
Each question has TWO (02) matching lists: List
- I and List - II
 FOUR options are given representing matching
of elements from List - I, List - II. ONLY ONE
of these four options corresponds to a correct
matching.
 For each question, choose the option corresponds
to a correct matching
 For each question, marks will be awarded
according to the following marking scheme:
Full Marks: +3 If ONLY the option

50
Chemistry Times July 18

The correct option is


(a) P  1; Q  2,3; R  1, 4; S  2, 4 (b) P  1,5; Q  3, 4; R  4,5; S  3
(c) P  1,5; Q  3, 4; R  5; S  2, 4 (d) P  1,5; Q  2,3; R  1,5; S  2,3
17. List-I contains and List-II contains major products.

Match each reaction in List-I with one or more products in List-II and choose the correct option.
(a) P  1,5; Q  2; R  3; S  4 (b) P  1, 4; Q  2; R  4; S  3
(c) P  1, 4; Q  1, 2; R  3, 4; S  4 (d) P  4,5; Q  4; R  4; S  3, 4
18. Dilution processes of different aqueous, with water, are given in List-I. The effects of dilution of the
solutions on [ H  ] are given in List-II. (Note: Degree of dissociation ( ) of weak acid and weak base is <
< 1; degree of hydrolysis of salt < < 1; [ H  ] represents the concentration of H  ions)
List - I List - II
P. (10 mL of 0.1M NaOH + 20 mL of 1. The value of [ H  ] does not change
0.1 M acetic acid) diluted to 60 mL on dilution
Q. (20 mL of 0.1 M NaOH + 20 mL of 2. The value of [ H  ] changes to half of its initial
0.1 M acetic acid) diluted to 80 mL value on dilution
R. (20 mL of 0.1 M HCl + 20 mL of 3. The value of [ H  ] charges to two times of its initial
0.1 M ammonia solution) diluted to value on dilution
80 mL
S. 10 mL saturated solution of 4. The value of [ H  ] charges to 1/ 2 times of its initial
Ni (OH ) 2 in equilibrium with excess value on dilution
solid Ni (OH ) 2 is diluted to 20 mL
(solid Ni (OH ) 2 is still present after
dilution). 5. The value of [ H  ] changes to 2 times of its
initial value on dilution

51
Chemistry Times July 18

Match each process given in List - I with one or more effect(s) in List-II. The correct option is
(a) P  4; Q  2; R  3; S  1 (b) P  4; Q  3; R  2; S  3
(c) P  1; Q  4; R  5; S  3 (d) P  1; Q  5; R  4; S  1

Section- I: 1. a,b,d 2. b, d 3.d


3. 4. d 5. a,d 6. a,c

Section- II: 7. 5.00 or 6.00 8. 6.47 9. 126.00 10. 7.00


11. 495.00 12. -14.60 13. 8500.00 14. -11.62

Section- III: 15. c 16. d 17. b 18. d

1.Sol: Complex [Co (en)( NH 3 )3 ( H 2 O )]3 has two geometrical isomers.

[Co ( NH 3 )3 ( H 2 O )(CN ) 2 ] has three geometrical isomers.

[Co (en)( NH 3 )3 ( H 2 O )]3 is diamagnetic


Co  [ Ar ]18 4 s 2 3d 7 ;
Co 3  [ Ar ]18 3d 6
en is strong field ligand.

52
Chemistry Times July 18

hc
0 

1
 0 

[Co (en) ( NH 3 )3 ( H 2 O )]3 absorbs light at longer wavelength as compared to [Co (en) ( NH 3 ) 4 ]3
2.Sol: Both Cu+2 and Mn+2 gives green colour in the flame test.
K sp (CuS )  K sp ( MnS )

 Only Cu 2 shows the formation of precipitate by passing H 2 S in acidic medium.


0 0
ECu 2
/ Cu
 EMn 2
/ Cu

Less electro positive metals have higher reduction potential.


3.Sol:

4.Sol:

53
Chemistry Times July 18

5.Sol: A( g )  2 B( g )  C( g ) 6.Sol: From the graph (1) and (2), we get H  ve
i.e. exothermic.
1  2 P0 
k  ln e   ln K1 T2
t  3P0  Pt  Given : ln K  T
2 1
kt  ln (2 P0 )  ln (3 P0  Pt )
 ln (3P0  Pt )  ln(2 P0 )  kt S  H   1 
  
R R  T1  T2
 
S  H   1  T1
  
R R  T2 

S 
 (T2  T1 ) 0
R
At t  t1/3  S   0
7.Sol:
ln 3
t1/3 
k
N 2 O3 :
 t1/3 is independent of [ A]0

N 2 O5 :

P4 O6 :
For 1st order reaction, rate constant is independent
of initial concentration of reaction.

P7 O7 :

54
Chemistry Times July 18

207
w pb   6.47 kg
32
H 4 P2 O5 :
9.Sol:

H 2 P3O10 :

H 2 S2 O3 :

No.of equivalents of MnCl2 = No. of eq. of KMnO4


= No. of eq. of H2C2O4
H 2 S2 O5 : 5  nMnCl2  2  nH 2C2O4

w 225
8.Sol: PbS  O2  Pb  SO2 5  2
126 90
nO2  nPb [Equal moles]
2  225  126
 w  126 mg
wo2 wpb wo2 wpb 90  5
   10.Sol: Total number of stereomers of compound - X
M O2 M pb 32 207
=8
Let, wo2  1 kg X has 7 optically active stereisomers
X has 1 optically inactive

11.Sol:

55
Chemistry Times July 18

No.of moles of D  1.5


Mass of (C6 H 4 NBr3 )  1.5  330  495 gm
12.Sol:

2Cu( s )  H 2 O( g ) 
 Cu2 O( s )  H 2( g )
1
At 1250 K 2Cu( S )  O2( g )   Cu2 O( s ) G   78000 J/mol   78 kJ/mol
2
1
H 2 O( g )  H 2( g ) O2( g ) G  17800 J/mol=  178 kJ/mol
2

2Cu( s )  H2O( g ) 
Cu2O( s )  H2 ( g ) ; G  100 kJ/mol

G  G   RT ln K G   RT ln 4e2
( pH 2 )  2500 ln 4e 2
0  100  RT ln
( pH 2 O )  2500 (ln 4  ln e 2 )
8 pH 2  2500 (2 ln 2  2)
100   1250 ln
1000 pH 2 O  2500 (2(0.7)  2)
Given : pH 2 O  1% of total pressure (1 bar)  2500  3.4
1  8500
 1 Absolute value of G  8500.00
100
2 n
n
8 pH 14.Sol: A( s ) A( aq, 2 M ) B( aq ,1M ) B( s )
100   1250  ln 22
1000 10 Oxidation
10  ln pH 2  ln102 A  An   ne ....(1)
10  ln pH 2  2 ln10 Reduction

10  ln pH 2  2 (2.3) B2n  2ne  B ....(2)


multiply equation (1) by (2) and add both
10  ln pH 2  4.6
 2 An   B
2 A  B 2 n  
ln pH 2  14.60 bar
Given E.M.F. of the cell is zero; the system is in
 AB( g )
13.Sol: A( g )  B( g )  equilibrium,  G  0
Eb  Ea  2 RT J/mol ; A f  4 Ab G   RT ln K
RT  2500 J/mol ; T  300 K [ An  ]2
G    RT ln
G    RT ln K [ B 2n  ]
Kf Af e  Ea / RT G    RT ln (2) 2
K 
Kb Ab e  Eb / RT G   H   T S 
 Eb  Ea 
G  2G  T  S  (Given H   2G  )
AF  RT 

 e G   T S 
Ab
G
2 RT  S 
 4e RT
 4e 2 T

56
Chemistry Times July 18

 RT ln 4 Ti 3  3d 1
  2 R ln 2
T
  8.3  0.7  2
 11.62 J K -1 mol 1 Weak ligands  H 2 O, Cl
2
15.Sol: P : dsp - (6) d 2 sp 3 - octahedral
[ Ni (CN ) 4 ]2  (3) [Cr ( NH 3 )3 ]36
Ni  4 S 2 3d 8 Cr :  4 s1 3d 5 ; Cr 3  4 s 0 3d 3

CN  is a strong ligand - Pairing takes place. d 2 sp 3 - octahedral


dsp 2 hybridization - square planar soln. (c)
16.Sol:
Q : sp 3  (4), (5) (P):
(4) [ FeCl4 ]2  Fe  4 s 2 3d 6

Cl - Weak ligand - No pairing takes pace


sp 3 hybridization - Tetrahedral structure
Iodo form reaction
(5) Ni (CO) 4 P - (1), (5)
(Q):
Ni  4 s 2 3d 8

CO - strong ligand - pairing from electrons of s


orbital.
sp 3 hybridization - Tetrahedral
R; (1)
(1) [ Fe F6 ]4  Gives Tollens & Fehlings Test
(Q)- (2), (3)
Fe  4 s 2 3d 6 ; Fe 2   3d 6 (R)

F- weak field ligand - No pairing


sp 3 d 2 hybridization - octahedral
S ; d 2 sp 3  2, 3
(2) [Ti ( H 2 O )3 Cl3 ]
Ti  4s 2 3d 2

57
Chemistry Times July 18

(S)

17.Sol: (P) -(1), (4)

(Q)

(R) (S)

R - (4)

18.Sol:
P: [ H1 ] C2 0.025
 
CH 3COOH  NaOH 
 CH 3COONa  H 2 O [ H 2 ] C1 0.05
20 ml of 0.1 M 10 ml of 0.1 M

[ H 2 ] 0.05
The value of H  does not change on dilution for   2
[ H1 ] 0.025
buffer solution P - (1)
Q: [ H 2 ]  2  H1 
NaOH  CH 3COOH 
 CH 3COONa  H 2 O R :
20 ml of 0.1M 20 ml of 0.1M

C1  0.05M NH 4 OH  HCl  NH 4 Cl  H 2 O

20 ml of 0.1M 20 ml of 0.1M

C2  0.025M on dilution to 80 ml C1  0.05 M


M 1V1  M 2V2 C2  0.025 M
  K  [H  ]  KnC
[ H ]  [OH  ] 
 
[H  ]  C
K
[OH  ]  K h C  C [ H1 ] C1 [ H 2 ] C2 0.025 1
Ka 
    
[H 2 ] C2 [ H1 ] C1 0.05 2
K  k a
[H  ]  1
C [ H 2 ]  [ H1 ]
2
1 R - (4)
 [H  ] 
C S: The value of [ H  ] does not change on dilution

58
Chemistry Times July 18

SOLUTIONS

1. If molality of the dilute solutions is doubled the (a) 0.177 (b) 0.0354
value of molal depression constant (K f ) will be:- (c) 0.0177 (d) 1.770
[2017] 6. The boiling point of 0.2mol kg 1 solution of X in
(a) Halved (b) Tripled water is greater than equimolal solution of Y in
(c) Unchanged (d) Doubled water. Which one of the following statements is
2. Which of the following is dependent on true in the case?
temperature ? [2017] [2015]
(a) Molarity (b) Mole fraction (a) X is undergoing dissociation in water.
(c) Weight percentage (d) Molality (b) Molecular mass of X is greater than the molecu-
3. Which of the following statements about the lar mass of Y.
composition of the vapour over an ideal 1:1 molar (c) Molecular mass of X is less than the molecular
mixture of benzene and toluene is correct? Assume mass of Y.
that the temperature is constant at 250 C . (Given, (d) Y is undergoing dissociation in water while X
undergoes no change
vapour pressure data at 250 C , benzene = 12.8 kPa, 7. Which one of the following electrolyte has the same
toluene = 3.85 kPa)
value of van’t Hoff factor (i) as that of Al2 ( SO4 )3
[2016]
(a) The vapour will contain a higher percentage of (if all are 100% ionised)?
toluene. [2015]
(b) The vapour will contain equal amounts of (a) K 2 SO4 (b) K3 [ Fe(CN )6 ]
benzene and toluene.
(c) Al ( NO3 )3 (d) K 4 [ Fe(CN )6 ]
(c) The vapour will contain a higher percentage of
benzene. 8. Of the following 0.10 m aqueous solutions, which
(d) Not enough information is given to make a one will exhibit the largest freezing point
prediction. depression?
[2014]
4. At 1000 C the vapour pressure of a solution of 6.5
(a) C6 H12 O6 (b) KCl
g of a solute in 100 g water is 732 mm. If
Kb  0.52 , the boiling point of this solution will (c) K 2 SO4 (d) Al2 ( SO4 )3
be: [2016] 20
9. 6.02  10 molecules of urea are present in 100
(a) 103 C (b) 102 C (c) 100 C (d) 1010 C
0 0 0 mL of its solution. The concentration of solution
5. What is the mole fraction of the solute in a 1.00 m is: [2013]
aqueous solution? [2015] (a) 0.01 M (b) 0.02 M (c) 0.1 M (d) 0.001 M

59
Chemistry Times July 18

10. Which of the following compounds can be used as (a) 0.56 K (b) -1.12 K (c) 1.12 K (d) -0.56 K
antifreeze in automobile radiators? [2012] 17. 1.0 g of a non-electrolyte solute (molar mass 250
(a) Methyl alcohol (b) Nitrophenol g mol 1 ) was dissolved in 51.2 g of benzene. If the
(c) Ethylene glycol (d) Ethyl alcohol
freezing point depression constant of benzene is
11. p A and pB are the vapour pressure of pure liquid 1
5.12 K kg mol , the lowering in freezing point
components, A and B, respectively of an ideal will be [2006]
binary solution. If X A represents the mole fraction (a) 0.2 K (b) 0.3 K (c) 0.5 K (d) 0.4 K
of component A, the total pressure of the solution 18. A solution containing 10 g per dm3 of urea (molar
will be [2012] mass = 60) is isotonic with a 5 g per 100cm3 of
(a) pB  xA ( pB  p A ) (b) pB  xA ( p A  pB ) non-volatile solute. The molecular mass of non
volatile solute is [2006]
(c) p A  x A ( pB  pA ) (d) p A  x A ( p A  pB )
(a) 250 (b) 200 (c) 350 (d) 300
12. The freezing point depression constant for water 19. During osmosis, flow of water through a semi
is 1.860 C m 1 . If 5.00 g Na2 SO4 is dissolved in permeable membrane, [2006]
(a) from solution having higher concentration only
45.0 g H 2O, the freezing point is changed by
(b) from both sides of semipermeable membrane
3.820 C , Calculate the van’t Hoff factor for with equal flow rates
(c) from the sides of semipermeable membrane with
Na2 SO4 . [2011]
unequal flow rates.
(a) 2.05 (b) 3.11 (c) 0.381 (d) 2.63 (d) from solution having lower concentration only
13. The van’t Hoff factor i for a compound which 20. The vapour pressure of two liquids P and Q are 80
undergoes dissociation in one solvent and torr and 60 torr respectively. The total vapour
association in other solvent is respectively pressure obtained by mixing 3 mole of P and 2 of
[2011] Q would be [2005]
(a) less than one and less than one (a) 140 torr (b) 72 torr (c) 68 torr (d) 20 torr
(b) greater than one and less than one 21. A solution of urea (molar mass 60) boils at
(c) greater than one and greater than one
(d) less than one and greater than one 100.180 C at atmospheric pressure. If K f and K b
14. A solution of sucrose (molar mass 342 g mol 1 ) for water are 1.86 and 0.512 K molality 1
has been produced by dissolving 68.5 g sucrose in respectively, the above solution will freeze at
1000 g water. The freezing point of the solution [2005]
obtained will be ( K f for H 2 O  1.86 kg / mol ) (a) 0.6540 C (b) 0.6540 C
[2010] (c) 6.540 C (d) 6.540 C
(a) 0.3720 C (b) 0.5700 C 22. A solution has a 1:4 mole ratio of pentane to hexane.
The vapour pressures of pure hydrocarbons at
(c) 0.3720 C (d) 0.5200 C
15. A 0.0020 m aqueous solution in an ionic compound 200 C are 440 mmHg for pentane and 120 mmHg
for hexane. The mole fraction of pentane in vapour
Co( NH 3 )5 ( NO2 )Cl freezes at 0.007320 C .
phase would be [2005]
Number of moles of ions which 1 mol of ionic (a) 0.549 (b) 0.200 (c) 0.786 (d) 0.478
compound produces on being dissolved in water
will be
( K f  1.860 C / m) [2009]
(a) 3 (b) 2 (c) 1 (d) 4
16. A 0.5 molal aqueous solution of a weak acid (HX) 1. c 2. a 3. c 4. d 5. c
is 20 percent ionised. The lowering in freezing point 6. a 7. d 8. d 9. a 10. c
11. b 12. d 13. b 14. c 15. b
of this solution is (K f  1.86 K / m for water) 16. c 17. d 18. d 19. c 20. b
[2007] 21. a 22. d

60
Chemistry Times July 18

T  0  (3.82)  3.82 K

4.Sol: At. B.P., P0  760 torr for elevation of B.P 1000  1.86  5  i  i  2.63
3.82 
142  45
P 0  Ps WB / M B 760  732 6.5 / M
   14.Sol: T f  molality  K f
Ps WA / M A 732 100 /18
On solving M = 30.6 68.5  1000
  1.86  0.372
342  1000
 6.5 
 
Tb  1K b m  1 0.52  
30.6 
 1000  1.1
 T f  0  0.372  0.3720 C
100
15.Sol: T f  i  K f ' molality
Tb  TbS  Tbo so TbS  Tb  TbO
0.00732  i  1.86  0.002
TbS  1.1  100C  101.10 C
 i  1.96  2
5.Sol: 1.00 m solution means 1 mole solute is present
in 1000 g of water.  [Co( NH 3 )5  ( NO2 )]Cl  [Co( NH 3 )5 NO2 ]  Cl 
1000 16.Sol: T f  iK f m
nwater   55.5 mol
18
i 1
nsolute 1 we know,   ( dissociation)
X solute    0.0177 n 1
nsolute  nwater 1  55.5
i 1
6.Sol: Tb  ikb m  i   1
2 1
For equilibrium solutions, elevation in boiling
point will be higher if solution undergoes so, T f  (  1) K f m
dissociation i.e., i  1 . Given   0.2, molality  0.5, K 'f  1.86
 2 Al 3  3SO42  , i  5
7.Sol: Al2 ( SO4 )3 
 T f  0.5  1.2  1.86  1.116 K
 Al 3  3 NO3 , i  4
Al ( NO3 )3  17.Sol:
 4
K 4 [ Fe(CN ) 6 ] 
 4 K  [ Fe(CN ) 6 ] , i  5 1000  K f  w
1000  5.12  1
Tf    0.4 K
K 2 SO4  
 2 K  SO , i  3 2 mw 250  51.2
4
18.Sol: For isotonic solutions of two non-electrolytes
 3K   [ Fe(CN ) 6 ]3 , i  4
K 3 [ Fe(CN ) 6 ] 
C1  C2
6.02  1020
9.Sol: Number of moles of urea   0.001 10 5
6.02  1023   (1 dm3  103 cm3 )
60  1000 mw  100
Molarity of solution of urea
Number of moles of urea  mw  300 g mol 1
  1000
Volume in mL 20.Sol: PT  PP  PQ  PPo  X P  PQO  X Q
0.001 3 2
 1000  0.01M
 PT  80   60   48  24  72
100 5 5
10.Sol: Ethylene glycol is used as antifreeze
compound in automobile radiators. Tb Kb
21.Sol: T  K
11.Sol: pM  p ' A  p ' B f f

 p A  x A  pB  xB ( p ' A  p A  x A ) Kf 1.86
 T f   Tb   0.18  0.654
 pB  x A ( p A  pB ) Kb 0.512
100  K f  w  f.pt.  0  0.654  0.6540 C
12.Sol: T f  i
mw
61
Chemistry Times July 18

By: A.N.S. SANKARA RAO (Hyderabad)

INORGANIC STRUCTURES

Questions based on structures of inorganic species(molecules/ions) are most common in all competitive
exams. One can learn them systematically by knowing CHEMISTRICK
“E.C. Lewis covered
cov hybrid love
l apple plants,
p s, B plantss behind dat
Bo p date palm trees for double bon
bonanza”.

1. Electronic Configuration (E.C.): Write E.C. of Xe = 2, 4, 6, 8 (1st, 2nd , 3rd, 4th E.S.)
central atom of the species, if needed go for excited (G.S. = Ground state, E.S.= Excited state)
E.C.s. For example write 4. Hybridisation:
Hybrid If the sum of the powers of s, p, d is
1st excited E.C. for Be in BeCl2 (Be = 2s12px1) equal to no. of surrounded atoms/no. of B.P.s/ no.
or B in BCl3 (B= 2s12px12py1) of covalent bonds, then the species get regular
or C in CH4 (C= 2s12px12py12pz1) shapes.
or P in PCl5 (P= 3s13px13py13pz13d1)
2nd excited E.C.
for S in SF6 (S= 3s13px13py13pz13d13d1)
3rd excited E.C.
for I in IF7 (I= 3s13px13py13pz13d13d13d1)
4th excited E.C.
for Xe in XeO4 (Xe=5s15px15py15pz15d15d15d15d1)
2. Lewis dot Structure: Write Lewis dot structure for
central atom

3. Covalency: One can get an idea of covalency(no. Even hybridisation of different species
of covalent bonds formed by central atom) by is same, their geometry may not be same when L.P.s
observing E.C. and Lewis dot structures. Covalency are present.
of any group element upto IV group is equal to its eg: NH4+, CH4 (sp3, tetrahedral),
group number(G). For atoms of V group onwards NH3 & H3O+ (sp3, pyramidal, 1 L.P.),
(except 1st member of the group, as it does not H2O(sp3, Angular, 2L.P.s)
contain d orbitals, could not expand its octet) If you compare CH4, NH3, H2O, with
minimum covalency is 8-G and maximum covalency the increase of one lone pair, one covalent bond
is G. decreases i.e. shape from tetrahedral to pyramidal
Valency of P = 3, 5 (G.S., 1st E.S.) to angular. Same logic must be applied for unknown
S = 1, 4, 6 (G.S., 1st, 2nd E.S.) species also.
Cl = 1, 3, 5, 7 (G.S., 1st, 2nd , 3rd E.S.)

62
Chemistry Times July 18

1. PCl6- No. of H.O.S This is due to the presence of different number of


L.P.S and B.P.S on the central atom.
1 1 It is found that
 G  M  C   5  6  1
2 2 No. of L.P.S + B.P.S (on central atom) =G


 6 s1 p3 d 2 , octahedral  eg: N= 1L.P. + 3B.P.  1 2  31

2. SF4 No. of H.O.S  5Group No.  G 


1 Dative bonds or double bon
6. Dat bonds: As per modern
  6  4 concepts we must show dative bond as double
2
bond.

 5 s1 p3 d 1 , see  saw  eg:

PO43- SO2
3. ClF3 No. of H.O.S
1
 7  3
2

 
 5 s1 p3 d 1 , Bent ' T '
SO3 SO3-2

Sometimes students may misunderstand that the


shape of SF4 as Trigonal pyramidal, ClF3 as planar SO4-2 ClO2-
triangle. Do not forget that
L.P. - L.P. > L.P. - B.P. > B.P. - B.P.
These electron pairs try to minimise repulsion by
maximising separation between them.
.S and B.P.S:
5. No. of L.P.S .S All the isoatomic molecules
B.P.S
may not be isostructural.
eg: CH4=tetrahedral, SF4=See-saw, ClO3- ClO4-
XeF4=Square planar.

RANK EDGE AKADEMI OF CHEMISTRY


Deepthisri nagar, Hyderabad.
Mobile No: 9848685179
Email: rasayanam.Jeeneet@gmail.Com

63
Chemistry Times July 18

64
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