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Passage : 1
Read the following passage carefully and answer the questions. (Q.1 to Q.5)
The minimum amount of energy required to remove the most loosely bound electron from an isolated atom in
the gaseous state is known as ionisation energy or first ionisation energy or ionisation enthalpy (E1) of the
element. The energy required to remove the second electron from the monovalent cation is called second
ionisation enthalpy (E2). Similarly, we have third, fourth ......... ionisation enthalpies. The values of ionisation
enthalpies. The values of ionisation energy depends on a number of factors such as (i) size of the atom (ii)
screening effect (iii) nuclear charge (iv) half filled and fully filled orbitals (v) shape of orbital. In periodic table
ionisation energy increases from left to right except few exceptions and decreases from top to bottom in the
group. Inert gas has the highest value of .E. in the period.
IONISATION ENERGIES OF THREE HYPOTHETICAL ELEMENTS ARE GIVEN BELOW (in kJ/mole):
X. 122 340 1890
Y. 99 931 1100
Z. 118 1220 1652 [Made 2008, SK Sir]
2. Which of the following pair represents elements could be of the same group [2 Marks, 2 min]
(A*) Y, Z (B) X, Y (C) X, Z (D) X, Y, Z
3. What could be the value of the first electron affinity of Z++ in kJ mol–1 [2 Marks, 2 min]
(A) 118 (B*) 1220 (C) 1652 (D) 734
5. For the element 'A', the first ionisation energy will be numerically equal to : [3 Marks, 3 min]
(A*) EA of A+ (B) EA of A2+ (C) E of A2+ (D) None of these
6. A certain volume of ethylene after partial reduction with hydrogen in presence of a metal catalyst
required 10% more oxygen for complete combustion than it would have originally. Calculate the ethane:
ethylene ratio after partial reduction. [3 Marks, 3 min]
(A) 2 : 3 (B*) 3 : 2 (C) 6 : 7 (D) 7 : 6
7. A hydrogen like ion having wavelength difference between first Balmer and Lyman series equal 593 Å has Z
equal to [3 Marks, 3 min]
(A) 2 (B*) 3 (C) 4 (D) 1
8. The energy required to remove an electron from metal X is E = 3.31 × 10–20 J. Calculate the maximum
wavelength of light that can photoeject an electron from metal X. [3 Marks, 3 min]
(A) 4 m (B*) 6 m (C) 7 m (D) 5 m
hc ( 6.63 10 34 J . s )(3.00 10 8 m / s)
Sol. = = 6.01 × 10–6 m
E 3.31 10 20 J
10. An electron in an isolated hydrogen like atom makes a transition from an excited state to the ground state by
emitting a maximum of three spectral lines. The electron stays in that excited state for a period of 1 nano
second (uncertainty in time). The percentage of minimum uncertainty in energy is 2.4 × 10–6. Determine
(a) The principal quantum number of the excited state.
h
(b) The hydrogen like species. (Calculate Z ) (Take = 3.28 × 10–16 eV.sec.)
4
[ Hint : Take the energy in excited state as the base for calculation of percentage uncertainty]
[5 Marks, 5 min]
Sol. (a) n = 4 (The hydrogen atom is isolated)
h h
(b) E.t = E =
4 4.t
E h
= 2
n2
E 4 t 13.6 z
E h 16
= z2 = 16 z=4
E 4 t 13.6 z 2
The species is Be+3
Comprehesion :
The amount of energy released when an electron is added to an isolated gaseous atom to produce a
monovalent anion is called electron affinity of first electron affinity or electron gain enthalpy. The first
electron affinity is given a negative sign as the addition of an electron to a neutral atom atom is an
exoergic process. The addition of electron to A – repquires energy to overcome the force of repulsion.
Thus, the second electron affinity is an endoergic process. The magnitude of electron affinity depends
on a number of factors such as (i) atomic size (ii) effective nuclear charge (iii) screeeing effects (iv) half
and fully filled orbitals and (v) shape of orbital.
In general, electron affinity increase as the atomic radii decrease in a period. However, there
are exceptions when the atoms have stable configurations. In a group, electron affinity decreases as
the size increases. However, the members of 3rd period have somewhat higher values than the members
in the 2nd period of the same subgroups.
18. The first ionization potential of Na, Mg, Al and Si are in the order
(A*) Na < Mg > Al < Si (B) Na > Mg > Al > Si (C) Na < Mg < Al > Si (D) Na > Mg > Al < Si
19. The correct order of second ionization potential of carbon, nitrogen, oxygen and fluorine is
(A) C > N > O > F (B) O > N > F > C (C*) O > F > N > C (D) F > O > N > C
Comprehension # 1
Electronegativity [Made 2006, AP]
In 1931, Pauling defined the electronegativity of an atom as the tendency of the atom to attract electrons
to itself when combined in a compound. The implication of this is that when a covalent bond is formed,
the electrons used for bonding need not be shared equally by both atoms. If the bonding electrons
spend more time round one atom, that atom will have a ¯ charge, and consequently the other atom
will have a + charge. In the extreme case where the bonding electrons are round one atom all of the
time, the bond is ionic. Pauling and others have attempted to relate the electronegativity difference
between two atoms to the amount of ionic character in the bond between them.
Mulliken
In 1934 Mulliken suggested an alternative approach to electronegativity based on the ionization energy
and electron affinity of an atom. Consider two atoms A and B . If an electron is transferred from A to B,
forming ions A+ and B¯, then the energy change is the ionization energy of atom A(A) minus the
electron affinity of atom B (EB), that is A – EB. Alternatively, if the electron was transferred the other way
to give B+ and A¯ ions, then the energy change would be B – EA. If A+ and B¯ are actually formed, then
this process requires less energy, and
(A – EB) < (B – EA)
Rearranging (A + EA) < (B + EB).
Now with respect to electronegativity for the same change ; E.N A < E.NB .
Thus Mulliken suggested that electronegativity is proportional to .E. + E.A. and could be regarded as
the average of the ionization energy and the electron affinity of an atom.
( E)
Electronegativity =
2
Mulliken used and E values measured in electron volts, and the values were about 2.8 times larger
than the Pauling values.It is to be noted that I.E and E.A values are defined for singular gaseous atoms.
20. We have X atoms of A. If all the atoms gain one electron each the energy released is a eV. If Y atoms of A
lose one electron each, then the energy absorbed is b eV. Then the electronegativity of A on the Mulliken
scale will be : [Made 2006, AP]
1 a b 1 1 a b
(A) a b (B*) (C) a b Na (D) 2 X Y Na
2 2 X Y 2
a
Sol. For A electron affinity per atom = ev
x
b
For A Ionisation energy per atom + ev
Y
1 a b
E.N (Mulliken) =
2 x Y
21. For the reaction A(g) + e¯ A’ (g) Hr = Heg . The enthalpy change will be equal to (magnitude wise) :
[Made 2006, AP]
(A) Heg of A¯ (g) (B) H.E. of A (g)(C) HE.N of A(g) (D*) H.E. of A¯ (g)
Sol. A¯(g) A(g) + e– Hr = HI.E of A¯(g)
22. For a reaction A(g) + B (g) AB(s) the enthalpy change for the reaction will be (assuming AB(s) to be an
ionic compound) If .EA + E.AA < .EB + E.AB. [Made 2006, AP]
(A*) H H
.E A H
egA L.E AB ( s )
(B) HegA H.EB HL.E AB ( s )
25. A sample of hydrogen gas has some atoms in one excited state and some atoms in other excited state. It
emits three different types of photons. When the sample was irradiated with radiations of energy 2.85eV, it
emits 10 different photons, all having energy equal to or less than 13.46 eV.
(i) Find the principle quantum numbers of initially excited electrons.
(ii) Find the maximum and minimum energies of the initially emitted photons. [6 marks, 8 min.]
Ans. (i) n = 2, n = 3 (ii) 12.09 eV, 1.9 eV
26. A compound which contains one atom of X and two atoms of Y for each three atoms of Z is made by mixing
5.00 g of X, 1.15 × 1023 atoms of Y and 0.03 mole Z atoms. Given that only 4.40 g of compound results.
Calculate the atomic weight of Y if the atomic weights of X and Z are 60 and 80 amu. respectively.
Ans. 70 amu [4 Marks, 5 min.]
27. The absorption of energy by an atom of hydrogen in ground state, results in the ejection of the electron with
de Broglie wavelength = 4.70 × 10–10 m. Given that the ionisation energy is 13.6 eV, calculate the energy
of the photon which caused the ejection of electron. [4 Marks, 5 min.]
Ans. 3.27 × 10–18 J
28. Photons of equal energy were incident on two different gas samples. One sample containing
H-atoms in the ground state and the other sample containing H-atoms in some excited state with a principal
quantum number ‘n’. The photonic beams totally ionise the H-atoms. If the difference in the kinetic energy of
the ejected electrons in the two different cases is 10.2 eV. Then find the principal quantum ‘n’ number of the
excited state. [4 Marks, 5 min.]
Sol. E = EeV
K.E1 = EHO – wf ...............(i)
EHO
K.E2 = – wf ...............(ii)
n2
1
K.E2 – K.E1 = EHo 2 1
n
10.2eV 1
=– = 2 –1
13.6eV n
1
= 0.25
n2
n=2
EHo
EHO = – 13.6 eV is energy of e¯ in G.S. of H atom , = Energy of e¯ in nth state
n2
Ans. n = 2
29. A sample of hydrogen gas is irradiated with photons of energy 10.2 eV. The radiations from the above sample
is used to irradiate two other samples of excited He+ and excited Li2+ respectively. Both the Ionised samples
which were already in the excited state, further get excited by absorbing the incident radiations. Find
(i) The maximum number of spectral lines obtained in the spectra of helium and lithium
respectively.
(ii) What are the smallest wavelengths in each spectra. [6 Marks, 12 min.]
Ans. A photon of energy 10.2 eV is emitted by H-atom when transition take place from n = 2 to n = 1
13.6eV
i.e. E = 13.6 eV –
4
= 13.6 eV – 3.4 eV = 10.2 eV
Energy diagram for He+ Energy diagram for Li2+
34. Element of which of the following atomic nos. has lowest EN? [3 Marks, 3 min.]
(A) 37 (B*) 55 (C) 87 (D) 105
Rb Cs
37
55
, 87 & 105 ® are atomic no. Being Radisactive & thus ganeral not consideered to give
Sol. Cs Rb
Comprehension : (Q. 1 to 5)
The properties of the elements (atomic/ionic radii, electron gain enthalpy, ionization enthalpy, electronegativ-
ity, valence, oxidising/reducing power, acid/base character, etc.) which are directly or indirectly related to
their electronic configurations are called periodic properties. These properties show a regular gradation on
moving from left to right in a period or from top to bottom in a group. Down a group, the atomic/ ionic radii,
metallic character and reducing character increase while ionization enthalpy and electronegativity decrease.
Along a period from left to right, atomic/ionic radii and metallic character decrease while ionization enthalpy,
electronegativity, non-metallic characterand oxidising power increase. However, electron gain enthalpy be-
comes less negative down a group but more negative along a period. In contrast, inert gases have positive
electron gain enthalpies which do not show any regular trend.
37. If the ionic radii of K+ and F– are about 1.34 Å each, then the expected values of atomic radii of K and F should
be respectively : [3 Marks, 3 min.]
(A*) 2.31 and 0.64 Å (B) 2.31 and 1.34 Å (C) 0.64 and 2.31 Å (D) 1.34 and 1.34 Å
38. Which of the following isoelectronic ions has the lowest first ionization enthalpy ? [3 Marks, 3 min.]
(A) K+ (B) Ca2+ (C) Cl¯ (D*) S2–
39. The outermost electronic configuration of the most electrongeative element is : [3 Marks, 3 min.]
(A) ns2 np3 (B) ns2 np4 (C*) ns2 np5 (D) ns2 np6
40. Amongst the following elements (whose electronic configurations are given below) the one having the highest
ionization enthalpy is : [3 Marks, 2 min.]
(A) [Ne] 3s2 3p1 (B*) [Ne] 3s2 3p3 (C) [Ne]3s2 sp2 (D) [Ar] 3d10 4s2 4p3
41. Thick the correct order of second ionisation enthalpy in the following : [3 Marks, 2 min.]
(A) F > O > N > C (B*) O > F > N > C (C) O > N > F > C (D) C > N > O > F
42. Which of the following relation is correct : [3 Marks, 3 min.]
(A) 2 I.P. – E.A. – E.N. = 0 (B) 2 I.P. – E.A. + E.A. = 0
(C*) 2 E.N. – I.P. – E.A. = 0 (D) E.N. – I.P. – E.A. = 0
Sol. [O] Use mulliken scale
43. Select the correct answer: [3 Marks, 3 min.]
(i) The first ionisation potentials (in electron volts) of N and O atoms are repectively given by:
(a) 14.6, 13.6 (b) 13.6, 14.6 (c) 13.6, 13.6 (d) 14.6, 14.6
(a) IE2 < IE1 (b) IE2>> IE1 (c) IE2 = IE1 (d) IE2 = 0
Sol. (i) a (ii) b
Passage :
Pauling gave method to calculate univalent ion radii by assuming that
(i) In ionic crystals (let M+ X–) cations and anions are in contact of each other and sum of their radii is
equal to interionic distance i.e.
(ii) The radius of an ion having noble gas configuration is inversely proportional to the effective nuclear
charge felt at the periphery of the ion i.e.
C C
r (M ) and r( X )
Z eff .(M ) Z eff .( X )
Here C is constant of proportionality whose value depends an electronic configuration of ion. Thus
C C
d( M – X – ) pm
Z eff . (M ) Z eff . ( X – )
Zeff is the effective nuclear charge whose value can be calculated by the formula Zeff. = Z –
Here is shielding constant and for neon, the value of when calculated by slater’s rule, was found to be
4.5
45. The value of univalent radii for F– as calculated by pauling method is (Given that interionic distance in
NaF = 231 pm) [3 Marks, 3 min.]
(A) 94.5 pm (B) 136.5 pm (C) 111.68 pm (D) 115.5 pm
46. The interionic distance by using univalent radii of Mg2+ and O2– , as calculated by Pauling’s method will be
(A) 257.4 pm (B) 205 pm (C) 210.7 pm (D) 219.6 pm [3 Marks, 3 min.]
47. The actual interionic distance in MgO may be (assuming bivalent ion) [3 Marks, 3 min.]
(A) 205 pm (B) 257.4 pm
(C) 276.0 pm (D) Can’t be predicted
48. The value of ‘C’ for Na+, Mg2+ and Al3+ will be in the order : [3 Marks, 3 min.]
(A) Al3+ > Mg2+ > Na+ (B) Al3+ < Mg2+ < Na+
(C) Al3+ = Mg2+ = Na+ (D) Can not be compared
49. Electronegativity value on Mullikan scale for two different elements are given as 7 and 1.4 respectively. If
bond is formed between then calculate the percentage ionic character of the bond between them. [ENP =
ENM / 2.8 ] [3 Marks, 3 min.]
7
Sol. E.N. on pauling scale = = 2.5
2 .8
1. 4
E.N. on pauling scale for 2nd element = = 0.5
2 .8
Electronegativity difference = 2.5 – 0.5 = 2
% ionic character = 16 + 3.5 2 = 16 × 2 + 3.5 × 22 = 32 + 14 = 46%
Ans. 46
50. For the gaseous reaction K + F K+ + F –, H was calculated to be 19 kcal under conditions where the
cations and anions were prevented by electrostatic separation from combining with each other. The
ionization energy of K is 4.3 eV. What is the E.A of F. [3 Marks, 3 min.]
Sol.
4.18 10 3
19 kcal 1 eV 1 mol
= 0.82 eV
H =
kcal 19 23
mol 1.60 10 J 6.02 10 atoms
4.3 eV – EA = 0.82 eV
EA = 3.5 eV
Another method :
K(g) + F(g) F – (g) + K+ (g) H = 19 kcal = 0.82 eV
K(g) K+ (g) + e– E = 4.3 eV
F(g) + e– F –(g) EA = H – IE = 4.3 – 0.82 = 3.5 eV
51. Ionisation potential of atoms A and B are 350 and 250 kcal mol–1 respectively. The electron affinities of these
atoms are 70 and 90 respectively then [3 Marks, 3 min.]
(A*) Electron cloud is more attracted by A (B) Electron cloud is more attracted by B.
(C*) Electron cloud is less repelled by A. (D) Electron cloud is less repelled by B.
52. Among the elements with atomic no. 9,12, 36. Identify by atomic number of an element which is :
(a) highly electronegative (b) an inert gas (c) highly electropositive
Sol. (a) 9F (b) 36Kr (c) 12Mg [3 Marks, 2 min.]
53. The first .E. of carbon atom is greater than that of Boron atom, whereas reverse is true for the second
ionisation energy. Explain. [3 Marks, 3 min.]
Sol. For 1st .E. C 2s2 2p2
[C < B Regular order]
B 2s2 2p1
54. A monoatomic ion has a charge of + 2. The nucleus of the ion has a mass number of 62. The number
of neutrons in the nucleus is 1.21 times that of the number of protons. How many electrons are in the
ion ? What is the name of the element ? [3 Marks, 4 min.]
62 2+
[Ans. 28Ni , Ni , 26]
55. The angular momentum of an electron in a Bohr’s orbit of H-atom is 4.2178 × 10 –34 kg-m 2/sec. Calcu-
late the spectral line emitted when electron falls from this level to next lower level. [3 Marks, 4 min.]
Ans. 1.8 × 10–4 cm
56. Azurite is a coppercontaining mineral that is a mixture of copper(II) carbonate and copper(II) hydroxide,
[CuCO 3] x·[Cu(OH)2] y. If the mineral is 55.31% Cu, 0.58% H and 6.97% C, with the remainder oxygen,
what are x and y in the general formula? [3 Marks, 4 min.]
[Ans: x = 2 and y = 1]
+ 2+ 2+ +
n 2a 0
(b) K , Ca , Ar [Ans: Ca < K < Ar (decide by rn = )]
z*
(c) Mg, Mg+, Mg2+ (Ans: Mg2+ < Mg+ < Mg)
1
(d) O2–, N3–, F– (Ans: F– < O2– < N3–)(In isoelectronic species)(rn x )
z
(e) O, O–, O2– (Ans: O < O– < O2–)
(f) Mg2+, Ca2+ (Ans: Mg2+ < Ca2+)
(g) Na+, Ne (Ans: Na+ < Ne)
(h) P3–, N3– (Ans: N3– < P3–)
58(a) What is the basic difference in approach between the Mendeleev's Periodic Law and the Modern Periodic
Law ?
(b) On the basis of quantum numbers, justify that the sixth period of the periodic table should have 32 elements.
[5 Marks, 5 min]
59(a) In terms of period and group where would you locate the element with Z = 114 ?
(b) Write the atomic number of the element present in the third period and seventeenth group of the periodic
table. [5 Marks, 5 min]
60(a) Why do elements in the same group have similar physical and chemical properties ?
(b) What do you understand by isoelectronic species ? Name a species that will be isoelectronic with each of
the following atoms or ions.
(i) F– (ii) Ar (iii) Mg2+ (iv) Rb+ [5 Marks, 5 min]
63(a). The first .E. of carbon atom is greater than that of Boron atom, whereas reverse is true for the second
ionisation energy. Explain.
Sol. For 1st .E. C 2s2 2p2
[C < B Regular order]
B 2s2 2p1
64(a). Identify the element of third period whose successive .E.s are given below [10 Marks, 5 min]
(b). Match the electronic corfiguration with the values of (E) of the elements in the nth period (n 1)
EC E (KJ / mol)
ns2 (I) 4000
ns2np1 (II) 1500
ns2np3 (III) 1200
ns2np6 (IV) 1400
Ans: ns2 IV,, ns2np1 III, ns2np3 II, ns2np6 I.
67(a). The (E)1 and the (E)2 in KJ/ mol of a few elements is as shown below [10 Marks, 5 min]
Element (E)1 (E)2
I 2372 5251
II 520 7300
III 900 1760
IV 1680 3380
Which of the above element is likely to be
(a) reactive metal (Ans. II)
(b) reactive non-metal (Ans. IV)
(c) Noble gas (Ans. I)
(d) Metal that forms a stable bivalent halide of formula AX2 ( Ans.III)
(b) Write the order of 2nd IE. of the elements from helium to sodium.
Sol. 2nd I.E. of He Li Be B C N O F Ne Na
Li < B < Be < C < O < N < F < Ne < H < He
is same as
1st I.E. of H He Li Be B C N O F Ne
Be < C < B < N < F < O < Ne < Na < He < Li
70. A single electron orbit around a stationary nucleus of charge +Ze, where Z is constant and e is the
magnitude of the electronic charge. It requires 47.2 eV to excite the electron from the second Bohr
orbit to the third Bohr orbit. Calculate
(a) Value of Z
(b) The energy required to excite the electron from the third orbit to the fourth Bohr orbit.
(c) The wavelength of the electromagnetic radiation required to remove the electron from the first Bohr
orbit to infinity.
(d) The kinetic energy, potential energy and angular momentum of electron in the first Bohr orbit.
(e) The radius of the first Bohr orbit.
(Given E1H = – 13.6 eV, c = 3 × 1010 cm/sec ; h = 6.6 × 10–77 erg-sec, r 1H = 0.539 Å)
Ans. (a) 5, (b) 16.53 eV (c) 36.4 × 10–8 cm,
(d) P.E. = – 668.75 eV, K.E. = + 334.37 eV, h/2 (e) 1.078 × 10–9 cm.
71. Which transition in Li 2+ would have the same wavelength as the 1 3 transition in hydrogen atom.
h
72. Find the orbital angular momentum of electron if it is in 2p orbital of H in terms of .
2
h h
Sol. For any orbital, the angular momentum is = ( 1)
2
= 2 . 2
73. The longest wavelength of the Lyman series for Hydrogen atom is the same as the wavelength of a certain
line in the spectrum of He+ when the electron makes a transition from n 2. The value of n is:
(A) 3 (B*) 4 (C) 5 (D) 6
75. H-atom in a sample are excited to same energy level n = 5 and it is found that photons of all possible
wavelengths are released when the atoms return back to the ground state find the minimum number of H
atoms in the sample.
Sol.
All possible transition are shown in the figures above. It can be seen, to get all possible transitions we need
at least six atoms (a, b, c, d, e, f,)
76. The electron gain enthalpies of halogens are as given below.
F = – 332, Cl = – 349, Br = – 324, = – 295 kJ mol–1.
The less negative value for F as compared to that of Cl is due to : [3]
(A) Strong electron-electron repulsions in the compact 2–p sub shell of F.
(B) Weak electron -electron repulsions in the bigger 3–p sub shell of Cl
(C) Smaller electronegativity value of F than Cl
(D) (A) & (B) both
Sol. (D)
Due to small size of F atom, the electron-electron repulsions in compact 2-p sub shell are large and hence
the incoming electron is not accepted with the same ease as is the case with Cl (less electron - electron
repulsions)
Sol. (D)
E.C of Mg+ = 1s2 2s2 2p6 3s1 ; E.C of Na+ = 1s2 2s2 2p6 3s0. In case of Na+ the valence electron is to be taken
out from inert gas configuration. Hence much higher energy is required for removal of valence electron.
81. By what amount does the angular momentum of an electron in the hydrogen atom change when it
emits a photon of energy 12.09 eV? [3]
Sol.
E = 12.09 ev
i.e. when electron make transition from n = 3 to n = 1
3h h
angular momentum in n = 3 = ; angular momentum in n = 1 =
2 2
3h h h
chane in angular momentum is = – Ans.
2 2
82. If 100 ml of 1M H2SO4 solution is mixed with 100 ml of 98%(w/w) H2SO4 solution (d = 0.1 gm/ml) then :
[5]
(A*) concentration of solution remains same (B*) volume of solution become 200 ml
(C) mass of H2SO4 in the solution is 98 gm (D*) mass of H2SO4 in the solution is 19.6 gm
10 d x
Sol. (a) Molarity of second solution is = =1M
M
(b) Volume = 100 + 100 = 200 ml
200 1
(c) Mass of H2SO4 = × 98 = 19.6 gm.
1000
83. The correct order of second ionisation potential of carbon, nitrogen, oxygen and fluorine is : [3]
(A) C > N > O > F (B) O > N > F > C (C) O > F > N > C (D) F > O > N > C
Sol. (C)
O+ = 2s2 2p3– half filled configuration has extra stability & F+ = 2s2 2p4 partially filled less stable thus IE2 of
O > F. As nuclear charge increases the IE2 increases.
(B) The first ionisation energies of Be and Mg are more than ionisation energies of B and Al respectively
(C) Atomic and ionic raddii of Niobium and Tantalum are almost same
(D) Metallic and covalent radii of potassium are 2.3 Å and 2.03Å respectively.
Sol. (A,B,C,D)
(A) Screening effect , effective nuelear charge thus valence shell electron is loosely bound. Hence I.E
(B) Be and Mg has ns2 configuration (stable configuration)
(C) Due to lanthanide contraction
(D) rmetallic > rcovalent (covalent bond formation involves the overlapping of orbitals)
86. Which of the following statement(s) is / are true for IA elements ? [3]
(A) Na is regarded as a typical/representative element
\
(B) Basic character of their oxides increases down the group
(C) Among alkali metal ions degree of hydration is highest in Li
(D) In general electron affinity values decrease from top to bottom in the group.
Sol. (A,B,C,D)
All are obvious facts.
87. Which of the following pair(s) represent(s) the isoelectronic species ? [3]
(A) S2– & Sc3+ (B) SO2 & NO3– (C) N2 & CN– (D) NH3 & H3O+
Sol. (A,B,C,D)
Species having same number of electrons are called isoelectronic specis.
88. Which of the following represent(s) the correct order of electron affinities ? [3]
(A) F > Cl > Br > (B) C < N < O < F (C) N < C < O < F (D) C < Si > P > N
Sol. (C, D)
Electron gain enthalpies in kJ mol–1 are :
C = – 121; Si = - 134 ; P = – 74 ; N O ; O = – 142 ; F = – 328
90(a) What is the basic difference in approach between the Mendeleev's Periodic Law and the Modern Periodic
Law ?
(b) On the basis of quantum numbers, justify that the sixth period of the periodic table should have 32 elements.
[5 Marks, 5 min]
91(a) In terms of period and group where would you locate the element with Z = 114 ?
(b) Write the atomic number of the element present in the third period and seventeenth group of the periodic
table. [5 Marks, 5 min]
92(a) Why do elements in the same group have similar physical and chemical properties ?
(b) What do you understand by isoelectronic species ? Name a species that will be isoelectronic with each of
the following atoms or ions.
(i) F– (ii) Ar (iii) Mg2+ (iv) Rb+ [5 Marks, 5 min]
95(a). The first .E. of carbon atom is greater than that of Boron atom, whereas reverse is true for the second
ionisation energy. Explain.
Sol. For 1st .E. C 2s2 2p2
[C > B Regular order]
B 2s2 2p1
(b) Arrange the following atoms in order of increasing radii [5 Marks, 5 min]
Na+, O2–, Ne
Sol. All ions are isoelectronic
Na
O 2 Ne
+ 2–
Na /O /Ne iso electronic
Vanderwaal 's
n 2a 0
(b) K+, Ca2+, Ar [Ans: Ca2+ < K+ < Ar (decide by rn = )]
z*
(c) Mg, Mg+, Mg2+ (Ans: Mg2+ < Mg+ < Mg)
1
(d) O2–, N3–, F– (Ans: F– < O2– < N3–)(In isoelectronic species)(rn x )
z
(e) O, O–, O2– (Ans: O < O– < O2–)
(f) Mg2+, Ca2+ (Ans: Mg2+ < Ca2+)
(g) Na+, Ne (Ans: Na+ < Ne)
(h) P3–, N3– (Ans: N3– < P3–)
97(a). Identify the element of third period whose successive .E.s are given below [10 Marks, 5 min]
Element E1 E2 E3
X 513 4562 6920
Y 738 1451 7733
Z 1521 2666 3931
Ans: X : Na its (E)2 is very high
Y : Mg its (E)3 is very high
Z : Ar its (E)1 is very high
98(a). Which has smaller value of second E, Na or Mg? [10 Marks, 5 min]
(Ans: Mg)
99(a). Which has large .E. in each pair. [10 Marks, 5 min]
(a) N or O+ (Ans: O+)
(b) Be+ or B+ (Ans: B+)
(c) Be or B (Ans: Be)
(d) Na+ or Ne (Ans: Na+)
(b). Match the electronic corfiguration with the values of (E) of the elements in the nth period (n 1)
EC E (KJ / mol)
ns2 (I) 4000
ns2np1 (II) 1500
ns2np3 (III) 1200
ns2np6 (IV) 1400
Ans: ns IV,,
2
ns2np1 III, ns2np3 II, ns2np6 I.
(c) Arrange the following isoelectronic species in order of increasing IE.
(O2–, F–, Na+, Mg2+)
Ans: O2– < F– < Na+ < Mg2+
100(a). The (E)1 and the (E)2 in KJ/ mol of a few elements is as shown below [10 Marks, 5 min]
Element (E)1 (E)2
I 2372 5251
II 520 7300
III 900 1760
IV 1680 3380
Which of the above element is likely to be
(a) reactive metal (Ans. II)
(b) reactive non-metal (Ans. IV)
(c) Noble gas (Ans. I)
(d) Metal that forms a stable bivalent halide of formula AX2 ( Ans.III)
(b) Write the order of 2nd IE. of the elements from helium to sodium.
Sol. 2nd I.E. of He Li Be B C N O F Ne Na
Li < B < Be < C < O < N < F < Ne < H < He
is same as
1st I.E. of H He Li Be B C N O F Ne
Be < C < B < N < F < O < Ne < Na < He < Li
102(a). Which of the following statements are correct [10 Marks, 5 min]
(A) F is the most electronegative and Cs is the most electropositive element
(B) The EN of halogens decreases from F to I
(C) The E.A. of Cl is higher than that of F though their EN values are in the reverse order
(D) The E.A. of noble gases is low.
Sol. A, B,. C, D
103. Explain the following, giving appropriate reasons. [10 Marks, 5 min]
(i) The value of electronegativity decreases on moving from top to bottom in the same group.
(ii) The electronegativity values of noble gases are zero, while those of halogens are the highest in
each period.
(iii) The electronegativity increases as s-character increases in the hybrid orbital.
(iv) The metallic character of elements decreases from left to right in a period, but increases from top
to bottom in a group.
(v) F has the highest electronegativity, while Cl has largest electron affinity.
Sol. (a) Size factor (b) Noble gas Rarely exhibit combined state
halogens due to max Z*
(c) % s charac ENF EN
(d) Across the period : EN Non-metallic charge
Down the Grp : IE Metallic charge
(e) F max. Z* is 2nd period
Cl greater due to more e– density on 2nd period element
i. The element with atomic number 56 is likely to have the same outer shell configuration as the element with
atomic number :
(A*) 12 (B) 18 (C) 14 (D) 20
Sol. Elements with atomic no. 56 & 12 belongs to alkaline earth metal group having configuration ns2.
iii. If aufbau rule is not followed, Ca-20 will be placed in _____ block.
(A) s- (B) p- (C*) d- (D) f-
Sol. If aufbau rule is not followed then 3d will be filled before 4s. So last electron of Ca-20 will go to 3d-subshell.
iv. What is the position of the element in the periodic table satisfying the electronic configuration
(n – 1) d1 ns2 for n = 4
(A) 3rd period and 3rd group (B) 4th period and 4th group
(C) 3rd period and 2nd group (D*) 4th period and 3rd group
Sol. When n = 4, the configuration will be[Ar]18 3d1 4s2 and thusperiod is tourth and group no is third.
v. In Mendeleeff’s periodic table, silver belongs to B group. The group to which silver belongs in long form of
periodic table is
(A) first (B) tenth (C) sixteenth (D*) eleventh
Sol. Electronic configration is [Kr] 3d10 4s1. so group is 10 + 1 = 11.
112. The correct order of second ionisation potential of carbon, nitrogen, oxygen and fluorine is :[3 min, 3 marks]
(A) C > N > O > F (B) O > N > F > C (C) O > F > N > C (D) F > O > N > C
Sol. (C)
O+ = 2s2 2p3– half filled configuration has extra stability & F+ = 2s2 2p4 partially filled less stable thus IE2 of
O > F. As nuclear charge increases the IE2 increases.
(B) The first ionisation energies of Be and Mg are more than ionisation energies of B and Al respectively
(C) Atomic and ionic raddii of Niobium and Tantalum are almost same
(D) Metallic and covalent radii of potassium are 2.3 Å and 2.03Å respectively.
Sol. (A,B,C,D)
(A) Screening effect , effective nuelear charge thus valence shell electron is loosely bound. Hence I.E
(B) Be and Mg has ns2 configuration (stable configuration)
(C) Due to lanthanide contraction
(D) rmetallic > rcovalent (covalent bond formation involves the overlapping of orbitals)
115. Which of the following statement(s) is / are true for IA elements ? [3 min, 3 marks]
(A) Na is regarded as a typical/representative element
(B) Basic character of their oxides increases down the group
(C) Among alkali metal ions extend (degree) of hydration is highest in Li
(D) In general electron affinity values decrease from top to bottom in the group.
Sol. (A,B,C,D)
All are obvious facts.
116. Which of the following pair(s) represent(s) the isoelectronic species ? [3 min, 3 marks]
(A) S2– & Sc3+ (B) SO2 & NO3– (C) N2 & CN– (D) NH3 & H3O+
Sol. (A,B,C,D)
Species having same number of electrons are called isoelectronic specis.
117. Which of the following represent(s) the correct order of electron affinities ? [3 min, 3 marks]
(A) F > Cl > Br > (B) C < N < O < F (C) N < C < O < F (D) C < Si > P > N
Sol. (C, D)
Electron gain enthalpies in kJ mol–1 are :
C = – 121; Si = - 134 ; P = – 74 ; N 0 ; O = – 142 ; F = – 328
118. The process(es) requiring the absroption of energy is/are : [3 min, 3 marks]
(A) Cl – Cl– (B) S S2– (C) H H– (D) Ar Ar –
Sol. (B, D)
(B) Addition of second electron to S– is opposed by electrostatic repulsion due to same charge. Hence
energy is given for the addition of IInd electron.
(D) Ar has stable electronic confiugration (ns2 np6). Hence energy has to be given to add an extra electron to
form Ar –
123. Which one of the following statements is incorrect in relation to ionisation enthalphy ?
(A) Ionization enthalpy increases for each successive electron
(B) As we move along the period the greatest increase in ionizaiton enthalpy is experienced on removal of
electron from core of noble gas configuration.
(C) End of valence electrons is marked by a big jump in ionization enthalpy.
(D) Removal of electron from orbitals bearing lower n value is easier than from orbital having higher n value.
Sol. (D)
Orbitals bearing lower value of n will be more closer to the nucleus and thus electrons will experience greater
attraction from nucleus and so its removal will be difficult not easier.
124. Considering the elements F, Cl, O and N, the correct order of their electron affinity values is :
(A) F > Cl > O > S (B) F > O > Cl > S
(C) Cl > F > S > O (D) O > F > S > Cl
Sol. (C)
Heg kJ mol–1 Cl = – 349 ; F = – 328 ; S = – 200 ; O = – 141.
125. Assuming the additivity of covalent radii in the C – I bond, what would be the iodine-iodine distance in each
of the diiodobenzenes ? Assume that the ring is regular hexagon and that each C – I bond lies on a line
through the centre of the hexagon. (Take C – C bond-length = 1.40 Å radius of iodine atom
= 1.33 Å, radius of carbon atom = 0.77 Å [4 min, 4 marks]
3
= (1.40 + 0.77 + 1.33) sin 60° = 3.50 sin 60° = 3.50 × = 3.03 Å
2
CD = 6.06 Å
(BD = AC as in (a))
(c) OC = OD = 3.50 Å
CD = 2 × 3.50 = 7.0 Å
126. An ionic compound AX3 (s) is formed between a metal A and a non-metal X (outermost shell configuration of
X = ns2 np5). Find the enthalpy of formation (magnitude) of AX3(s) with the help of the following data. (Non-
metal X is found to exist in nature as a diatomic gas) [4 min, 4 marks]
HSublimation A(s) = 100 Kcal/mol H.E1 A(g) = 60 Kcal/mol
Sol.
3
Hf = Hsub + H.E1 + H.E2 + H.E3 + Hdiss + 3 He.g + HL.E
2
3
= 100 + 60 + 150 + 280 + × 80 – 3 × 110 – 470
2
= 100 + 60 + 150 + 280 + 120 – 330 – 470
= – 90 Kcal/mol
Ans. 90
127. Calculate the lattice energy of LiF given that enthalpy of [4 min, 4 marks]
(i) Hsub for lithium is 155.2 is 155.2 kJ mol–1
1
(ii) Hdiss of mole of F2 is 75.3 kJ
2
(iii) I.E of Lithium = 520 kJ mol–1
(iv) E.A. of Fluorine = – 333 kJ mol–1
(v) Hf for overall = – 594.1
Ans. – 1011.6 kJ mol–1
128. Draw an electron-dot structure for each of the following molecules: [3 min, 3 marks]
(a) AlCl3 (b) Cl3 (c) XeOF4 (d) HOBr
Ans. (a) (b) (c) (d) H – O – Br
129. What type of bonds are present in the following molecules ? [2 min, 2 marks]
(i) MgF2 (ii) BrCl (iii) CBr4 (vi) H2O
(v) H2SO4 (vi) SO2 (vii) HNO3
130. Oxalic acid, H2C2O4, is a poisonous substance found in uncooked spinach leaves. If oxalic acid has a
C–C single bond and no C–H bond, draw its electron-dot structure. [2 min, 2 marks]
131. Li is soluble in water but LiF is not, why ? [1 min, 1 marks]
Sol. Although Li is same in both the compounds yet difference in the size of F¯ and I¯ is not same. Since F¯ is
+
smaller than I¯hence lattice energy of LiF is more than that of Li. Similarly heat of hydration of F¯ is more
than that of I¯. But the decrease of L.E. from LiF to Li is much more than the decrease in heat of hydration
from LiF to Li. Hence solubility increases from LiF to Li.
132. Arrange the solubility of NaCl in decreasing order in the following solvents :
CH3COCH3 (dielectric constant = 12) ;
CH3CH2OH (dielectric constant = 35) ;
H2O (dielectric constant = 80) ; [1 min, 1 marks]
Hint : Greater is the dielectric constant of solvent more is the solubility of an ionic compound in it
H2O > CH3CH2OH > CH3COCH3