Chemistry : Periodic Properties & Chemical Bonding

SECTION - I
SUBJECTIVE TYPE PROBLEMS
Problem 1: The 1st and 2nd I.E. of K are 419 kJ/m and 3052 kJ/mol and Ca are 590 kJ/mol and
1145 kJ/mole respectively. Compare their values and explain the differences.
Solution : Removal of 2nd electron from K is extremely difficult because K acquires stable noble gas
configuration after removing one electron while removal of both the electrons for Ca is
comparatively easy, as it acquires stable configuration after removal of both the electrons.
Problem 2 : Explain why the 2nd ionisation energy of Cr is higher than that of Mn.
Solution : After losing one electron Cr will get converted into Cr+ which will have stable half filled
elecronic configuration (d5) with respect to configuration Mn+ (d5s1).
Problem 3: Why the 1st Ionisation energy of phosphorous is greater than that of sulpur.
Solution : Phosphorous has got a stable half filled electronic configuration hence the 1st I.E. of P is
higher than that of S1.
N0 N
Problem 4: atoms of X (g) are converted into X+ (g) by energy H, KJ. 0 atom atoms of X
2 2
N
(g) are converted into X + (g) and 0 atoms of X (g) are converted into X – (g) by
2
energy H2. Calculate the ionisation energy and electron affinity of X.
Solution : Let the I.E. of X be I and electron affinity X be E kJ/mole.
X(g)  X+ (g) + e
 1 N 
  0  = H
 NA V 2  1

 2H1  NAV 
 I =  NO  kJ/mol
 
(where NAV is the Avogadro’s No.)
Similarly
X (g) X+ (g) + e
X (g) + e X– (g)
 E o N 
H1 +  N  2  = H2
 AV 

 2 (H2  H1) 
 E=   kJ / mol
 N0 

Problem 5: Two atoms A1 and A2 have the electronic configurations [Ne] 3s2 3p6 and [Ne] 3s23p64s1.
The first ionisation energy of one is 2762 Kj/mole and that of the other is 692 kJ/mole.
Match each ionisation energy with one of he electronic configuration. Justify your
choice.
Chemistry : Periodic Properties & Chemical Bonding

Solution : [Ne] 3s2 3p6 : 2762 kJ/mole

[Ne] 3s2 3p64s1 : 692 kJ/mole
Completely filled configurations have higher ionisation energy than other configurations due
to their extra stability.

Problem 6: Ice has lesser density than water. Explain.

Solution : In the crystal structure of ice, the O-atom is surrounded by four H-atoms. Two H atoms are
linked to O-atoms by covalent bonds and remaining two hydrogen atoms are linked to
O-atom by two H-bonds shown by dotted lines in the figure. Thus in ice every water molecule
is associated with 4 other water molecules by H-bonding in tetrahedral fashion. Ice has an
open structure with a large empty space due to the existence of H-bonds. As ice melts at
0°C a no. of H-bonds are broken down and space between water molecules decreases so
that water molecules come closer together. The density of water increases, therefore from
0°C to 4°C at which it is at maximum.

H H

O water molecule

H H H

O H O

H O H

Problem 7: Arrange the following in decreasing order of bond angels NH3, PH3, AsH3and SbH3.
Solution : NH 3  PH3  AsH 3  SbH3 . With decreasing electronegativity of the central atom as in
the series NH3 , PH3 and AsH3 (where order of electronegativity is N  P  As ) the
bonding electron pairs are drawn closer to hydrogen atom and further away from the
central atom. Therefore, repulsion between the bonding pairs of lectrons decreases and
so also the bond angles decrease progressively as given below:

NH3 PH 3 AsH3 SbH 3

106.5 93.3 91.8 91.3
 Chemistry : Periodic Properties & Chemical Bonding

Problem 8: C(NHMe)4 is more acidic than Si(NHMe)4.

Solution : This is due to p – d back bonding between N-atom and Si (vacant d-orbitals are available)
taking place in Si(NHMe) 4 whereas that does not take place in C(NHMe) 4 due to
unavailability of d-orbitals in C-atom.
Problem 9: NF3 can not be hyrolysed but NCl3 gets hyrolysed.
Solution : In NF3 , both N and F atoms are having no vacant orbtials (d-orbitals also). Hence H 2 O
molecule neither can attack N or F atoms,hence no hydrolysis. In case of NCl3 , although
N-atom is not having any vacant d-orbital but Cl is having and thus if water added it
preferentially attacks Cl-atoms.

N N

Cl Cl OH 2 
 Cl  Cl O H

Cl Cl H

NH 3  3HOCl 
 Cl N H  HOCl
Cl

Problem 10 : Example the followings:—

(a) C2H5OH is having much higher boiling point than C2H5SH
(b) Ortho nitrophenol is more volatile than p-nitrophenol.
Solution : (a) C2 H5OH molecules remain entangled with each other by extensive, intermolecular
hydrogen bonding but C2H5SH does not undergo hydrogen bonding because of larger
size of S-atom as well as less polarity of S—H bond.
(b) Ortho nitrophenol undergoes intramolecular H-bonding as, As a result, it does not get
involved in intermolecular H-bonding. But p-nitrophenol involves extensive intermolecular
H-bonding.
Chemistry : Periodic Properties & Chemical Bonding

SECTION - II
SINGLE CHOICE PROBLEMS
Problem 1 : An element is having the electronic configuration ns2 np5, a very high jump in I.E. values is
associated with
(a) IP1  IP2 (b) IP2  IP3
(c) IP3  IP4 (d) IP4  IP5
Solution : From IP2 to IP3 electrons will be ejected from half filled p(stable) orbitals.
(b)
Problem 2 : Which transition involves maximum amount of energy
(a) X– (g)  X(g) + e (b) X– (g)  X+ 3+ + 2e
(c) X+ (g)  X2+ (g) + 2e (d) X2+ (g)  X(g) + e
Solution : High amount of energy would be necessary to put to eject one electron from dipositive
gaseous ion.
(d)
Problem 3 : Ionisation potential of Li+ is
(a) Lesser than He (b) Greater than He
(c) Greater than He2+ (d) Equal to He
Solution : High amount of energy always would be necessary to remove and electron from a catil.
(b)
Problem 4 : Two elements X and Y having the electronic configurations 3s2 3p3 and 3s2 3p5.
(a) E.A. of X > E.A. of Y (b) E.A. of Y > E.A. of X
(c) E.A. of X = E.A. of Y (d) None is correct
Solution : X is having half filled stable p-subshell as compared to Y.
(a)
Problem 5 : Oxidation states of Nitrogen varies from
(a) –3 to + 5 (b) +3 to – 5
(c) –1 to – 5 (d) –3 to –5
Solution : Nitrogen is having compounds from hydride (NH3) to oxide (N2O5).
(a)
Problem 6 : Which does not use sp3 hybrid orbitals in its bonding
(a) BeF3– (b) OH3

(c) NH 4 (d) NF3

Solution : BeF3– involves sp 2 hybridization

(a)
 Chemistry : Periodic Properties & Chemical Bonding

Problem 7 : The correct order of dipolemoment is;

(a) CH 4  NF3  NH3  H 2O (b) NF3  CH 4  NH3  H 2O

(c) NH3  NF3  CH 4  H 2O (d) H 2 O  NH3  NF3  CH 4

Solution : The dipole moment of symmetrical molecule is always less than unsymmetrical molecules.
Higher the number of lone pairs/vector moment, higher the dipole moment.
(a)
Problem 8 : Among the following species, identify the iso-structural pairs.

NF3 , NO3– , BF3 , H 3O  , NH 3

(a) [NF3 , NO3– ] and [BF3 , H 3O  ] (b) [NF3 , NH 3 ] and [NO3– , BF3 ]

(c) [NF3 , H3 O  ] and [NO3– , BF3 ] (d) [NF3 , H3 O  ] and [HN 3 , BF3 ]

Solution : NF3 and H3 O  have sp3 hybridization; NO3– and BF3 have sp 2 hybridization.
(c)
Problem 9 : Among KO2 , AlO 2– , BaO 2 and NO2 unpaired electron is present in:

(a) NO 2 and BaO 2 (b) KO2 and AlO 2–

(c) KO2 only (d) BaO 2 only

Solution : KO2 has K  O 2– structure having one unpaired electron.

(c)
Problem 10 : The hybridization of atomic orbitals of nitrogen in NO 2 , NO3– and NH 4 are:

(a) sp, sp3 and sp 2 respectively (b) sp, sp 2 and sp3 respectively

(c) sp 2 , sp and sp3 respectively (d) sp 2 , sp3 and sp respectively..

Solution : NO 2 NO3– NH 4

5 –1
 2 sp hybridized sp 2 hybridized sp3 hybridised
2
(b)
Chemistry : Periodic Properties & Chemical Bonding

SECTION - III
MULTIPLE CHOICE PROBLEMS
Problem 1: Which of the following are not d-block elements?
(a) [Xe] 5d1 6s2 (b) [Rn] 6d1 7s2
(c) [Xe] 4f1 4d1 6s2 (d) [Rn] 5d2 7s2
Solution : (c, d)
(c) and (d) are f block elements
Problem 2 : In which of the following pairs, both the species have nearly the same size?
(a) K+, F– (b) Rb+, O2–
(b) Li+, Mg2+ (d) Mg2+, Al3+
Solution : (a, b, c)
Problem 3: Which of the following sets contain only isoelectronic ions?
(a) Zn2+, Ca2+, Ga3+, As3+ (b) K+, Ca2+, Sc3+, Cl–
(c) P3–, S2–, Cl–, K+ (d) Ti4+, Ar, Cr6+, V5+
Solution : (b, c, d)
Zn+2, Ca2+, Ga3+ and As3+ contain 28, 18, 28 and 30 electrons respectively
Problem 4 : Mark the correct statements out of the following :
(a) Helium has the highest first ionization enthalpy in the periodic table
(b) Fluorine has less negative electron gain enthalpy than chlorine
(c) In any period, atomic radius of the noble gas is the highest
(d) Hg and Br and liquids at room temperature
Solution : (a, b, c, d)
All are correct
Problem 5 : Which of the following sequence contains atomic numbers of only representative elements
(a) 3, 33, 53, 87 (b) 6, 14, 17, 38, 55
(c) 7, 17, 25, 37, 48 (d) 9, 35, 54, 88
Solution : (a, b, d)
Problem 6 : Which of the following species have the same shape and same bond order?
(i) CO2 (ii) N3–
(iii) O3 (iv) NO2–
(a) (i) and (ii) (b) (iii) and (iv)
(c) (i) and (iii) (d) (ii) and (iv)
 Chemistry : Periodic Properties & Chemical Bonding

Solution : (a, b)
CO2 and N3– are linear with bond order 2 in each case, O3 and NO2– are V-shaped with bond
order 1.5 in each case.
Problem 7 : Which of the following statements about CO32– ion are correct?
(a) The C—O bond order is 1.333
(b) The formal charge on each oxygen atom is 0.67 units
(c) It has two C—O single bonds and one C=O double bond
(d) The hybridization of central atom is sp3
Solution : (a, b)
Problem 8 : Diamagnetic species are
(a) N2 (b) N22–
(c) O2 (d) O22–
Solution : (a, d)
Problem 9 : The linear structure is assumed by
(a) SnCl2 (b) NCO–
(c) NO2+ (d) CS2
Solution : (a, c, d)
NCO–, NO2+ and CS2 all have linear structure while SnCl2 is angular.
Problem 10 : Paramagnetic species are
(a) O2+ (b) O2–
(c) N2+ (d) N2–
Solution : (a, b, c, d)
All are paramagnetic
Chemistry : Periodic Properties & Chemical Bonding

MISCELLANEOUS PROBLEMS
SECTION - IV
COMPREHENSION TYPE PROBLEMS

Write up – I
Screening effect is the effect produced by intervening electrons between nucleus and valence
electrons. They shield the nucleus from valence electron and effective nuclear charge decreases if
there is less shielding effect, the effective nuclear charge decreases. Valence electrons are attracted
by nucleus and repelled by other electrons.
Net attractive force on elctrons under consideration = Z – S = (Nuclear charge – screening effect)
Slater’s Formula for screening constant
If one electron is present in outermost orbit, there will be no screening in that orbital.
Each electron contributes 0.35 (total electrons minus 1) present in outermost shell.
In penultimate energy level, electrons contribute 0.85.
A contribution of 1.0 is from remaining electrons (present in last but one energy level)

Problem 1 : The effective nucleus charge for 4s electrons of Zn will be

(a) 26.85 (b) 4.35
(c) 15.30 (d) 10
Solution : Ans. (a)
For 4s-electrons : 1 × 0.35 + 10 × 0.85 + 1.0 × 18 = 0.35 + 8.5 + 18.0 = 26.85
Problem 2 : The number of lobes in most of the f-orbitals are
(a) 6 (b) 8
(c) 10 (d) 4
Solution : Ans. (a)
There are six lobes in most of the f-orbitals.
Problem 3 : The atomic size of Ga is smaller than Al becuase
(a) poor shielding effect of electrons in d-orbitals, effective nuclear charge increases in
Gallium
(b) More shielding effect of d-electrons
(c) Poor shielding effect of f-orbital in Galliun
(d) High shielding effect of 3s, 3p and 3d electrons.
Solution : Ans. (a)
lesser the shielding effect, more will be force of attraction between valence electron and
nucleus, smaller will be atomic size.
 Chemistry : Periodic Properties & Chemical Bonding

Write-up II
According to molecular orbital theory, in a molecule electrons are added in molecular orbitals in
order of their increasing energy. The number of electrons in the molecular orbitals is equal to the
sum of all the electrons in the bonding atoms. Like an atomic orbital each molecular orbital can
accommodate upto two electrons with opposite spins (in accordance with the Pauli exclusion principle).
When electrons are added to molecular orbitals of the same energy, the most stable arrangement is
predicted by Hund’s Rule; i.e., electrons enter these molecular orbitals singly with parallel spins.
Constructive and destructive interaction between the wave functions of two 1s orbitals of hydrogen
atom lead to the formation of a bonding (s) and an antibonding molecular orbitals ( *s ). In the
bonding molecular orbital, there is concentration of electron cloud between the nuclei of atoms
which acts as a negatively charged glue to hold the positively charged nuclei together. In the
antibonding molecular orbital there is a node between the nuclei that signifies zero electron density.
However, the energies of molecular orbitals actually increase as follow.
*
1s  1s   2s  *2s  2p y  2p z   2p x  *2p y  *2pz  *2p x

This order is valid upto z  7  2. The energy of  2p x is lower in energy than the 2p y and 2p z
orbitals for O2 and F2. To evaluate the stabilities of species we determine their bond order, defined
as

1
Bond order = (No. of electrons in B.M.Os – No. of electrons in ABMOs)
2
A bond order zero means the bond has no stability and the molecule cannot exist. The bond order
indicates the strength of a bond. Presence of unpaired electron in molecular orbitals make the
species paramagnetic, and the removal of electron from bonding M.O is more difficult than that of
anti bonding M.O.

Problem 4 : The species C2

(a) has one  bond and one  bond (b) has both  bonds
(c) has both  bonds (d) does not exist
Solution : Ans. (b)
Double bond in C2 has both  bonds betwen the twoC-atoms because 4 electrons are
present in  molecular orbitals
Problem 5 : In the formation of N2 molecules according to M.O.T. the outermost electron goes to
(a)  MO (b) sp hybid orbital
(c)  MO (d) 2p orbital
Solution : Ans. (c)
The outermost electron in N2 goes to -MO
Problem 6 : Which of the following species is paramagnetic?
(a) O 2 (b) N 2
2–
(c) O 2 (d) H 2
Solution : Ans. (a)
Only O2 has two unpaired electrons and hence is paramagnetic.
Chemistry : Periodic Properties & Chemical Bonding

MATCHING TYPE PROBLEM

7. Match the following :

Column (I) Column (II)
(a) CN – (p) Bond order 2, diamagnetic
(b) C2 (q) Bond order is 3, diamagnetic
(c) NO (r) Bond order is 1/2, paramagnetic
+
(d) Ne (s) Bond order is 5/2, paramagnetic
Sol. (a)  (q); CN– (6 + 7 + 1 = 14) 1s2 *1s2 2s2 *2s22px 22py22pz2
B.O. = 1/2 (10 – 4) = 6/2 = 3, Diamagnetic due to absence of unpaired electrons.
(b)  (p); C2(12) 1s2*1s22s2*2s22px22py2
B.O. = 1/2 (8 – 4) = 4/2 = 2, diamagnetic
(c) (s); NO (15) 1s2*1s22s2*2s22pz22px22py2*2px1
B.O. = 1/2 (10 – 5) = 5/2, paramagnetic due to presence of one unpaired electron.
(d) (r); Ne2+ (19) 1s2 *1s2 2s2 *2s2 2pz2 2px2 2py2 *2px2 2py2 2pz1
B.O. = 1/2 (10 – 9) = 1/2, paramagnetic due to presence of unpaired electrons.

ASSERTION-REASON TYPE PROBLEMS

The question given below consist of an ASSERTION and the REASON. Use the following key for the
appropriate answers
(a) If both Assertion and Reason are correct and Reason is the correct explanation for Assertion
(b) If both Assertion and Reason are correct and Reason is not the correct explanation for
Assertion
(c) If Assertion is correct but Reason is not correct.
(d) If Assertion is incorrect but Reason is correct.
8. Assertion : Zn2+ is diamagnetic.
Reason : The electrons are lost from 4 s-orbital to from Zn2+
Solution : Ans. (b)
9. Assertion : LiCl is covalent whereas NaCl is ionic.
Reason : Greater the size of the cation, greater is its polarising power.
Solution : Ans. (c)
Smaller the size of the cation, greater is polarising power.
10.Assertion : All F–S–F angles in SF4 are greater than 90° but less than 180°.
Reason : The lone pair - bond pair repulsion is weaker than bond pair - bond pair repulsion.
Solution : Ans. (c)
Due to greater lone pair bond pair repulsions than bond pair-bond pair repulsion, the
F—S—F bond angle decreases from 180°.