CHEMICAL BONDING 124

TYPES OF SYMMETRIES OF MO’s

s-s combinations of orbitals:
Atomic Orbitals Molecular Orbitals
+ + +
Bonding orbital
s s (g)
(g)
Node
Antibonding orbital
+ – + – (u)
s s
(u)

s-s combinations of atomic orbitals

In the bonding MO there is increased electron density between the nuclei where as in the anti-bonding MO the
electron density between the nuclui is zero (since the two lobes of opposite sign cancel the function). Both in the
atomic orbital pair before interaction and tthe MO’s formed after interaction, there is cylindrical symmetry
around the bond axis i.e, any point on the orbital surface describes a circle as the MO is rotated around the
bond axis. This circle is a plane perpendicular to the bond axis. All the points on such a circle have either a
positive sign or negative orbital sign. There is no change of sign i.e, no node as we move over the circle. This is
term cyclindrical symmetry and orbitals with cyclindrical symmetry are designated,  , if they are bonding and
* , if they are antibonding.
s-p combinatinos of orbitals:
Atomic Molecular
orbitals orbitals
– + + – +  overlap
px
bonding orbital
s (g)

Node

+ – + –+ – + 
 overlap
px
antibonding orbital
s
(u)

s-p combinatino of atomic orbitals

p-p combinations of orbitals:

Molecular
Atomic orbitals
orbitals
– + + – – + –  overlap
bonding orbital
px px
(g)

+ – + – + – + –  overlap
antibonding orbital
px px

(u)

p-p combinations of atomic orbitals

CHEMICAL BONDING 125

Molecular Orbitals
Atomic Orbitals
+
+ +  overlap
Nodal plane bonding orbital
– –
px px
–
(u)

+ – + –
 overlap
– Nodal plane antibonding orbital
+
– +
px px
(g)

p-p combinations giving -bonding

p-d combinations of orbitals:

Molecular Orbitals
Atomic Orbitals
+ –
+ + –
 overlap
– – bonding orbital
+ +
–
py dyz
(u)

+ – + + –
 overlap
antibonding orbital
– + – – +

py dyz
(g)

p-d combinations of atomic orbitals

d-d combinations of orbitals:

–
+
+ + –
–
– +
z
d x2–y2

 bonding by d-orbitals
(sideways overlap of two d x2–y2 orbitals)
Non-bonding combinations of orbitals: In the combinations shown in the figure below any stabilization
which occurs from overlapping + with + is destabilized by an equal amount of overlap of + with –. There is no
overall change in energy, and this situation is termed non-bonding. It should be noted that in all these non-
bonding cases the symmetry of the two atomic orbitals is different, i.e. rotation about the axis changes the sign
of one.
CHEMICAL BONDING 126

+ + –
+
– +
– – +
s py px dyz

Some non-bonding combinations of atomic orbitals

Energy level diagram for molecular orbitals:

BMO’s :   2s    2p z    2p x    2p y 

ABMO’s : *  2s  *  2p z  *  2p x  *  2p y 
The energy levels of these molecular orbitals have been determined experimentally from spectroscopic data.
Total bonding MO 's  Total antibonding MO 's

NOTE:
(1) If total number of electrons in a molecular  14, the energy level of MO’s follow this sequence.
*
2 px *2 px
1s , 1s , 2s , *2s , 2 pz , *2 pz
 2 py , *2 py ,


Increaseing order of energy


2pz
2p 2px 2py 2p

2px 2py

Energy 2pz)

2s)

2s 2s
2s)

Energy level diagram

Mixing of Orbitals: However spectroscopic studies have reverse sequence of energy levels of MO’s is not
correct for all molecules.
It has been observed that in case of homonuclear diatomic molecules of second row elements, 2p z MO is
higher in energy than the 2px and 2py MO’s. Therefore the sequence of energy levels of MO’s is due to the
possibility of mixing of 2s and 2p z atomic orbitals.

Note: If the difference between 2s and 2p atomic orbital are small, these is a possibility of the mixing of these
orbitals to form mixed atomic orbitals. Which would be comparatively more stable.
MO’s as 2s and * 2s obtained from mixed atomic orbitals would be lower in energy while 2pz and
*2pz MO’s would be higher in energy than the corresponding MO’s obtained from mixed atomic orbitals.
CHEMICAL BONDING 127


 2pz

2pz

   
 2px  2py  2px  2py

2pz
Energy
2px 2py 2px 2py


 s


 s
s

s
MO before
MO after mixing
mixing
Molecular orbital diagrams of molecules:
(1) N 2 , N= 1s2 2s2 2p3 = K 2s2 2p3
Total number of electrons in N2 molecule (7 + 7) = 14

2pz

2px 2py








2p
 

2p
2p)z





2px 2py
 

 2s)
2s 2s
 

2s)
Atomic Atomic
orbitals orbitals
MO of N2
of N of N
1 1 1
• Bond order =  N b  N a  = 10  4   6  3 (triple bond between two N atoms)
2 2 2
non-bonding
So,
N2  •• N N •• •• N N lone pair of
electrons
non-bonding lone
pair of electrons
There is no unpaired electron in N2 molecule and hence diamagnetic.
CHEMICAL BONDING 128
Electronic configuration:

2 *2 2
22px 2 *0
*2 2px 0 2 *2 2 *2
22px 2
 ,  ,  ,  , 2  2pz , *0 ,  2pz or 1s , 1s , 2s , 1s , 2  pz
1s 1s 2s 2s
2py , 2py 2py ,
Note: MO diagrams follow the same sequence of energy levels(same as N2) of molecular orbitals for
H 2 , H 2 , He 2 , Li 2 , Be 2 , B2 , C 2 , N 2 , etc. i.e, for those homodiatomic moleculaes in which the total number of
electrons are equal to 14 or less than 14.
Note: If total number of electrons in molecule > 14, then the energy sequence of energy of molecular orbitals
in MO diagram will be

* *
2p x *2px
1s     2s    2p z 
1s 2s  *
 *2 pz
2p y  2p y

MO diagram of O2:
O  1s 2 2s 2 2p 4  2s2 2p 4
Total number of electrons in O2 molecules = ( 8 + 8) = 16, i.e, > 14. So MO diagram follows the following
sequence of energy level of molecular orbitals. 16  14 , then.

 2pz



 
 2px  2py











2p





2p
2px 2py
 

2pz)
 


 2s)





2s 2s
 

2s)
Atomic Atomic
orbitals orbitals
of O MO of O2
of O
1 4
Bond order  1  N B  N A   8  4   2 (two bonds between oxygen atoms)
2 2 2
O2  O  O
• Paramagnetic due to presence of two unpaired electrons in *2px and *2py antibonding molecular orbitals.
Electronic configuration:

2 *2 2 *2 2
22px *1
2px
 , , , ,
1s 1s 2s 2s 2pz , 2 1
2py , 2py

Note: Same MO diagram for O 2 , O22  , F2 , etc.

CHEMICAL BONDING 129
MO diagram for hetero diatomic molecules:
AB molecule


A
B
B  A , where   electronegativity
Atomic Atomic
orbitals  orbitals
MO of AB molecule

eg. NO

7N  1s 2 2s 2 2p3  7 eS  
2 2 4 
  15 eS  14
0  1e 2s 2p  8eS 
2pz


 
 2px  2py







2p 2px 2py





2p



 

2pz)
 
 


 2s)
 

2s
2s


Atomic Atomic


orbitals 2s) orbitals

of N of O
MO of NO

2 *2 2 *2 2
22px *1
2px
Electronic Configuration:  ,  ,  ,  , 
1s 1s 2s 2s 2pz ,
22py , 2py
0

1 5
Bond order  10  5    2.5 , hence paramagnetic molecule.
2 2
Note: MO of NO and NO+ are same.
NO+ Total eS  14
Diamagnetic molecule

Bond order  1 10  4  6  3 ;  N  O 



3 2
O  1s 2 2s 2 2p 4 
MO diagram for CO: 2 2 2
 14 e 
C  1s 2s 2p 
 CHEMICAL BONDING 130

2pz

 
 2px  2py







2p



2p


2pz)





2px 2py

 
 

 2s)


2s
2s


Atomic orbitals Atomic


of carbon 2s) orbitals
of O
MO of CO molecule
1 1 6
Bond order   N b  N a   10  4   3 (Triple bond between carbon and oxygen atom)
2 2 2
CO  C  O (diamegnetic)

(1) Coulson’s Treatment of CO molecules:

CO is ionised to give CO+ by removing of one electron from the 2pz orbital then the bond order should be
1
reduced to 2 and the bond lenght increased. Infact the bond lenght of CO+ decreases and the bond order
2
increasess. This cannot be explained by simple CO, MO diagram.
Coulson modified the MO diagram of CO by using concept of hybridization.

6 C  1s 2 2s 2 2p 2 =
2s 2p
2 1
2 2 4
C   sp c  sp c 2p0z p y1 
8 O  1s 2s 2p = 2 1 
2s 2p O   sp  0  sp 0 2p z1 2p y 2 
sp-hybridization

Note: Elcetron pairs in  sp c and  sp O hybrid orbitals are not involved in bonding and hence are called 

Non-bonding electron pairs  nb  pairs  .  sp c hybrid orbital containing a lone pair of electron has higher
energy and higher degree of p-character, is very reactive and hence accounts for the properties of CO.
• (sp)O hybrid orbital containing a lone pair of electrons, lower in energy than (sp)O hybrid orbital containing a
single electron, has high degree of s-orbital character and hence is very stable (i.e. unreactive) hybrid-orbital.
Now we are left with two singly filled  sp  c and  sp O hybrid orbitals and two 2p-atomic orbitals (2px
and 2py) on both the atoms which overlap together in pair to give the following molecular orbitals.
•  sp c   sp O give sp and *sp molecular orbitals
CHEMICAL BONDING 131

• 2px atomic orbital on C-atom + 2px- atomic orbital on O-atom give x and *x MO’ss

• 2py atomic orbital on C-atom + 2py atomic orbital on O-atom give 2p y and *y MO’s.
s.

The relative order of energy of different MO’s in CO:

 sp O   sp b  x b  y b   sp c  *x  *y  sp*

and hence molecular orbital configuration of CO is -

2 2 2 2 2
 sp O ,  sp b  ,   x b     y b  ,  sp  c ,  *x   *y  sp*

1
Bond order   6  0   3 , showing that C and O in CO molecule are linked together by a triple bond
2

1  2 bonds 
• sp b molecular orbitals is mostly on oxygen atom  x b and y b molecular orbitals are mostly on O-atom.
Since o-atoms contributes more to the formation of these MO’s than does C-atom.
These MO’s are leaning some what toward oxygen atom are shown in figure. The other  -MO’s are
at right angles i.e, in front and behind the paper to the one shown below.
In the formation of *x and *y molecular orbitals (degenerate MO’s) carbon atom makes a larger

contribution than O-atom. Both of these degerate  * MO’s are also at right sides to each other. The  *
MO’s are much closer to C-atom and are, therefore concentrated mostly on C-atom.
Note: Both these  * MO’s are empty and can therefore, accept electron pairs by interacting with appropri-
ate, filled orbitals of transitional elements. These  * MO’s are therefore, called acceptor MO’s. This acceptor
property of these MO’s is very important in considering the M  L bond in metal carbon and hence M is the
metal an L indicates  - ligand such as CO.
 CHEMICAL BONDING 132

sp

 
2p x y

x y

2p
(sp)C (sp)C (lp)
Energy
x y

(sp)C
x y

(sp)O
C–atom

sp
atomic atomic
orbital orbital
of C (sp)O (lp) (sp)O of O

Molecular orbitals of CO.

Problem: Why CO molecule, co-ordinated through carbon ?

Soln. Electron pairs in (sp)c and (sp)O hybrid orbitls in Coulson; CO diagram, are not involved in bonding, hence
called non-bonding electron pairs. Lone pair of electrons in non-bonding (sp)c hybrid orbital, has highest
energy i.e. HOMO. It is concentrated on carbon atoms and easily available for bonding with other atoms/
metals. This is the reason CO coordinate with other atoms through carbon atom.

Problem: Why CO has negligible dipole moment ?

Soln. Lone pair of electrons on carbon atom in CO molecule points away from O-atom (i.e. extends away from C—
O bond). This reduce the effective electronics charge between carbon and oxygen atoms. This accounting for
low dipole moment of CO.
C O Lone pair on carbon atom reduces
charge separation and hence it has
negligible dipole moment.
 CHEMICAL BONDING 133
Molecular orbital diagram of HF:

An orbital interaction diagram for the formation of HF .

Only the valence atomic orbitals and electrons are shown.
Comparison between valence bond theory and molecular orbital theory:
Common features: valence bond and molecular orbital theories have following feactures in common.
(i) Both the theories are the interpretation of covalent bonds.
(ii) According to both theories the Atomic orbitals of the two atoms must overlap to form a covalent bond. The
Atomic orbitals overlapping each other must have the same symmetry and must be of same energy.
(iii) According to both, the electronic charge reside in the region between the atomic nuclei.
(iv) The basic principles involved in the distribution of electrons are similar. Thus an orbital, whether atomic or
molecular cannot have more than two electrons. They are filled in order of increasing energy.
(v) Both the theory postulate that a covalent bonds possesses directional properties.
Differences:
MOT VBT
(1) Molecular orbitals are formed by LCAO (1) Two atomic orbitals give an
approximation method. The atomic interatomic orbital obtained by the
orbitals involved in the formation of these combination of the space function
molecules orbitals are from valence shell of two unpaired electrons; one
of two atoms. being in each of the two AO’s
(2) Atomic orbitals of the resulting molecule (2) The resulting molecule consists of
lose their individual identity. atoms which although interacting
retain a large measure of their
individual character.
(3) Molecular orbitals are polycentric. (3) Atomic orbitals are mono-centric.
(4) MOT explains the paramagnetic character (4) VBT fails to explain paramagnetic
of oxygen character of O2.
(5) Resonance play no role in MOT (5) Resonance play an important role
in VBT
(6) The MOT inherently gives an equal (6) However in the initial stage of
weightage to the covalent and ionic development the VBT ignored the
structures ionic contribution to chemical bond
 CHEMICAL BONDING 134
SOLVED PROBLEMS

1. Which one of the following statements concerning H 2 is incorrect? [BHU 2011,15]

(a) The non-degenerate LCAO–MOs (without spin) must be either symmetric or anti-symmetric for inversion
(b) The lowest energy MO (without spin) of the molecule is anti-symmetric for inversion
(c) The ground state has a multiplicity of two
(d) The MOs transform into AOs of the helium ion as the two nuclei are fused together

1su
Soln. H H
1s 1s

1sg

1 1
Ground state : 1g  spin multiplicity  2s+1  2×  1  2
2
The lowest energy MO (wihtout spin) of the molecule is symmetric for inversion.
Correct option is (b)
2. Which of the following combination of atoms of A and B forms bonding molecular orbitals?
A
(a)   A   B  (b)   A   B  (c)   A   B  (d)  [BHU 2012]
B

Soln. The additive linearly combination of wave function of atom A   A  and B   B  is responsible formation of
bonding molecular orbital

 AB  N  C1 A  C2  B 
Correct option is (b)
3. Which of the following processes involves increasing in bond order ? [BHU 2012]
(a) N 2  N 2  e  (b) CO  e   CO  (c) NO  NO   e  (d) O 2  e   O 2
Soln. According to Molecular Orbital Theory

NO   1s2  1s
*2 2
  2s  *2 2 2 2 * * *
2s  2px  2py   2pz  2px   2py   2pz

10  4
Bond order = 3
2
Correct option is (c)
4. Which molecule has zero bond order ? [BHU 2012]

(a) H 2 (b) H2 (c) HeH (d) He2

2 *2
Soln. He2  1s  1s   2s  *2s
22
Bond order  0
2
5. What is the bond order in NO molecule ? [BHU 2012,13]
(a) 2.5 (b) 2 (c) 1.5 (d) 1

Soln. NO  1s2  1s

*2 2
 2s  *2 2 2 2 *1 * *
2s  2px   2py   2pz  2px   2py   2pz
 CHEMICAL BONDING 135

10  5
Bond order   2.5
2
Correct option is (a)
6. Which molecule has zero bond order? [BHU 2014]
(a) H2+ (b) H2 (c) HeH (d) He2
Soln. He 2  1s2  1s
*2

22
Bond order  0
2
Correct option is (d)
7. What is the bond order in NO molecule? [BHU-2014]
(a) 2.5 (b) 2 (c) 1.5 (d) 1
Soln. Electronic configuration of
NO  1s2  1s*2  22s  *2 2 2 2 *1 * *
2s  2px   2py   2pz  2px  2py   2pz

1 1 5
Bond order  ( N b  N a )  (10  5)   2.5
2 2 2
Correct answer is (a)
8. Arrange the following oxygen molecular ions and the molecule in order of increasing bond energy or in
decreasing order of (O-O) bond length. The molecular ions and the molecule are : O22+, O2+, O2, O2– and
O22–. The possible orders are given below. Choose the correct one: [BHU 2016]
+ – 2+ 2–
(a) O2 < O2 < O2 < O2 < O2 (b) O2 < O2 < O2 < O2 < O22+
2– – +

(c) O2 < O2– < O22– < O2+ < O22+ (d) O2– < O22– < O2 < O22+ < O2+
1
Soln. Bond order  bond energy 
bond length
2 *2 2
O 2  1s  1s   2s  *2 2 2 2 *1 *1 *
2s   2pz   2px   2py  2px  2py   2pz

1 4
Bond order  10  6    2
2 2
O 2  1s2  1s
*2 2
 2s  *2 2 2 2 *1 * *
2s   2pz  2px  2py   2px   2py   2pz

1 5
Bond order  10  5    2.5
2 2
O 22  1s2  1s
*2 2
  2s  *2 2 2 2 * * *
2s   2pz  2px   2py   2px  2py   2pz

1  10  4 
Bond order   3
2 2 

O 2  1s2  1s
*2 2
  2s  *2 2 2 2 *2 *1 *
2s   2pz   2px   2py  2px  2py   2pz

1 3
Bond order =  10  7    1.5
2 2
O 22  1s2  1s
*2 2
 2s  *2 2 2 2 *2 *2 *
2s   2pz   2px  2py  2px   2py   2pz

1 2
Bond order  10  8    1
2 2
Correct option is (b)
 CHEMICAL BONDING 136
9. Which one of the following M , O.’s of (HF2)– is correct? [BHU 2016]

(a) (b)
H F F H

(c) (d)
H+ F H F


Soln. Molecular orbital diagram for  HF2 

Energy H
2F

Correct option is (b)

10. Out of the following diatomic molecules, the paramagnetic ones are
(A) Be2 (B) B2 (C) C 2 (D) N 2
+
(E) O 2 (F) F2 (G) C2 (H) C2 –
(a) Be2, B2 and C2, N2 (c) B2, C2, N2 and C2– [BHU 2016]
(b) C2, N2, O2 and C2+ (d) B2, O2, C2+, C2–
Pick the correct choice out the above four choices.
2 *2 2
Soln. B2  1s  1s   2s  *2 1 1
2s  2px  2py
Number of unpaired electrons = 2
C2  1s2  1s
*2 2
 2s  *2 2 1
2s   2px  2py
Number of unpaired electron = 1
C2  1s2  1s
*2
 22s  *2 2 2 1
2s   2px  2py   2pz
Number of unpaired electron = 1
2 *2 2
N 2  1s  1s   2s  *2 2 2 2
2s  2px  2py   2pz
Number of unpaired electron = 0
Be 2  1s2  1s
*2 2
 2s  *2
2s
Number of unpaired electron = 0
2 *2 2
O 2  1s  1s   2s  *2 2 2 2 *1 *1 *
2s   2pz   2px   2py  2px  2py   2pz
Number of unpaired electron = 2
F2  1s2  1s
*2 2
  2s  *2 2 2 2 *2 *2 *
2s   2pz  2px   2py  2px  2py   2pz
Number of paired electron = 0
Correct option is (d)
11. Which of the following has a bond order 2.5:
(a) HCl (b) CO (c) NO (d) N 2
2 *2 2
Soln. NO  1s  1s   2s  *2 2 2 2 *1 *
2s  2px  2py   2pz   2px   2py   2pz

10  5
Bond order   2.5
2
N 2  1s2  1s
*2 2
  2s  *2 2 2 2 * *
2s  2px   2py   2pz  2px  2py   2pz
 CHEMICAL BONDING 137

10  4
Bond order  3
2
N2 and CO both are isoelectronic hence same bond order.
Correct option is (c)
12. According to M.O. theory, the ground state of H2 is 1s2 . In addition to the ground state, there are following
excited states of H2 : [BHU 2017]
     ..
(1)   *
(2)  (3) 1s *
* (4) 1b 1*
1s 1s 1s 1 1s 1s 1s 1s

The highest and lowest energy states of H2 will respectively be :

(a) (2) and (1) (b) (3) and (1) (c) (1) and (2) (d) (2) and (3)
Soln. Highest and lowest energy excited states are

1s 1s* 1s 1s*

Highest energy state Lowest energy state
Correct option is (b)
13. Which of the following is a paramagnetic molecule? [HCU-2013]
(a) H2 (b) B2 (c) C 2 (d) N 2
Soln. B2   12s   1*2s   22s   2*2s   21 px   1 2 py
Number of unpaired = 2
Hence, paramagnetic
H2, C2 and N2 has no unpaired electron hence diamagnetic.
Correct option is (b)
14. Consider four diatomic molecules M1, M2, M3 and M4 of same atoms with bond orders 2.5, 3, 4 and 2
respectively. Which of the following arrangements describes them with decreasing bond energy?
(a) M3 > M4 > M1 > M2 (b) M1 > M2 > M3 > M4 [HCU-2013]
(c) M3 > M2 > M4 > M1 (d) M3 > M2 > M1 > M4
Soln. Bond order  bond energy
Hence, order of bond energy will be M3 > M2 > M1 > M4
Thus, correct option is (d)
15. The bond order and bond type in the C2 molecule are, respectively [HCU-2014]
(a) 2; one sigma bond and one pi bond (b) 3; one sigma bond and two pi bonds
(c) 2; two pi bonds (d) 2; two sigma bonds
Soln. C2   12s   1*2s   22s   2*2s   22 px   22 py
1
Bond order = 8  4   2
2
as both the bonds are formed by  -bonding orbitals hence both the bonds are  -type.
Correct option is (c)
16. Identify the species with the lowest bond order among the following [HCU-2015]
(a) C 2 (b) NO (c) Cl2+ (d) O2 +

Soln. Cl2  1s2  1s

*2 2
 2s  *2 2 2 2 *2 *2
2s   2pz  2px  2py   2px   2py

 *2 2 *2 2 2 2 *2 *1
2pz  3s  3s  3pz  3px  3py  3px  3py

1
Bond order  18  15  1.5
2
 CHEMICAL BONDING 138

1
2
C2  1s *2
 1s 2
  2s  *2 2 2
2s  2px  2py , Bond order = 8  4   2
2
NO  1s2  1s
*2 2
  2s  *2 2 2 2 *1 *2
2s  2px   2py   2pz  2px   2py

1
Bond order = 10  5   2.5
2
O 2  1s2  1s
*2 2
 2s  *2 2 2 2 *1 * *
2s   2pz  2px  2py   2px   2py   2pz

1
Bond order  10  5   2.5
2
Correct option is (c)
17. The species having the shortest bond length among the following is : [HCU 2017]
(a) NO (b) NO+ (c) NO2+ (d) NO–
Soln. NO  1s2  1s
*2 2
  2s  *2 2 2 2 *1 *
2s  px  2py   2pz   2pxz  2py

1
Bond order = 10  5   2.5
2
NO   1s2  1s
*2
 22s  *2 2 2 2
2s   px  2py   2pz

1
Bond order  10  4   3
2
NO   1s2  1s
*2 2
  2s  *2 2 2 2 *1 *1
2s  px  2py   2pz   2px   2py

1
Bond order  10  6   2
2
NO 2  1s2  1s
*2
 22s  *2 2 2 1
2s   px  2py   2pz

1 5
Bond order = 10  4    2.5
2 2
Correct option is (c)
18. Among the following, the most unstable molecule is
(a) Li2 (b) Be2 (c) B2 (d) C 2 [HCU-2012]
Soln. Electronic configuration of
1
Li 2 (6)  12s 1*2s 22 s *0
2 s  Bond order  (4  2)  1
2
1
Be 2 (8)  12s 1*2s 22 s *0
2 s  Bond order  (4  4)  0
2
1
B2 (10)  12s 1*2s  22 s *2 1
2 s 2 p x  Bond order  (6  4)  1
2
12 p y

1
C 2 (12)  12s 1*2s  22 s *2 2 2
2 s 2 p x  2 pz  Bond order  (10  4)  3
2
 22 p y
Be2 is most unstable because the bond order is zero.
Correct answer is (b)
 CHEMICAL BONDING 139
19. The common features among the species CN–, CO and NO+ are [DU-2014]
(a) Bond order three and isoelectronic (b) Bond order three and weak field ligands
(c) Bond order two and stronger field ligands (d) Iso-electronic and weak field ligand
Soln. CN–  14 electrons
CO  14 electrons
NO+  14 electrons, they are iso-electronic

CN   12s 1*2s 22 s *2 2 2 *

2 s  2 pz 2 px  2 px

22 p y *2 p y

1 1 6
Bond order = ( N b  N a )  (10  4)   3
2 2 2
CO  12s 1*2s 22 s *2 2 2
2 s  2 pz  2 px

22 py

1
Bond order  (10  4)  3
2
NO   12s  1*2s  22 s  *2 2 *1 2 2 *
2 s  2 p x   2 px   2 pz   2 p y   2 p y

1 6
Bond order  (10  4)   3
2 2
Correct answer is (a)
20. The HOMO in CO is? [ISM-2015]
(a)  -bonding (b)  -bonding (c)  -antibonding (d)  -antibonding
Soln. Correct answer is (d)
21. Among the following molecules, the shortest bond length is to be found in
(a) C 2 (b) N 2 (c) O 2 (d) F2
Soln. Bond order is reciprocal to bond length, so, the molecule with higher bond order will have shorter bond
length.
1 1
Bond order of C2 = (Nb – Na) = (6 – 2) = 2
2 2
1 1
Bond order of N2 = (Nb – Na) = (8 – 2) = 3
2 2
1
Bond order of O2 = (8 – 4) = 2
2
1
Bond order of F2 = (8 – 6) = 1
2
N2 has highest value of bond order, so it will have shortest bond length.
Correct answer is (b)
22. The bond order for N2, O2, N2–, O2– varies as
(a) N2 > N2– > O2 > O2– (b) N2 > O2 > N2– > O2–
(c) O2 > N2 > O2– > N2– (d) N2– > N2 > O2– > O2
1 1
Soln. Bond order of N2 = (Nb – Na) = (10 – 4) = 3
2 2
 CHEMICAL BONDING 140

1
Bond order of O2 = (10 – 6) = 2
2
1
Bond order of N2– = (10 – 5) = 2.5
2
1
Bond order of O2– = (10 – 7) = 1.5
2
Thus, the bond order is N2 > N2– > O2 > O2–
Correct answer is (a)
23. According to MO theory for the atomic species C2
(a) bond order is zero and paramagnetic (b) bond order is zero and diamagnetic
(c) bond order is two and paramagnetic (d) bond order is two and diamagnetic
Soln. Electronic configuration of C2 is
1s2  1s
*2
 22s  *2 2 2 * * *
2s   2px  2py   2pz   2px   2py   2pz

1 84
Bond order = ( Nb  N a )  2
2 2
No unpaired electrons, So, C2 is diamagnetic
Correct answer is (d)
24. On the basis of LCAO-MO theory, the magnetic characteristics of N2 and N2+ are
(a) both diamagnetic (b) both paramagnetic
(c) N2 diamagnetic and N2+ paramagnetic (d) N2 paramagnetic and N2+ diamagnetic
* * 2 2 2
Soln. N2(14) = 1s 2  1s2   2 s2   2 s2   2 px   2 p y   2 pz
* * 2 2 1
N2+(13) = 1s 2  1s2  2 s 2  2 s 2   2 px   2 p y   2 pz
Nitrogen has no unpaired electron, so it is diamagnetic while N2+ has one unpaired electron, so it is
paramagnetic in nature.
Correct answer is (c)
25. The highest occupied molecular orbital of HF is
(a) bonding (b) anti-bonding (c) ionic (d) non-bonding
Soln. Correct answer is (d)
26. Which of the following have identical bond order
(a) CN – (b) O2 – (c) NO+ (d) CN+
Soln. CN– and NO+ are isoelectronic, have the same bond order of 3.
Correct answers are (a) and (c)
27. Given the species N2, CO, CN– and NO+
which of the following statements are true for these
(a) All species are paramagnetic (b) All species are isoelectronic
(c) All the species have dipole moment (d) All the species are linear
Soln. All the species are isoelectronic (total electron is 14)
N 2  1s 2 1s *2  2 s 2  2 s*2 2 p x 2 2 p z 2 (diamagnetic)
2 p y 2
All species are diamagnetic (i.e., N2 is diamagnetic) and linear.
Correct answers are (b) and (d)