CH182: CHEMISTRY FOR ENGINEERS II (2015) - ASSIGNMENT 1

Due date for submission: 17-08-2015 Monday 4 PM

Drop them into my PH (Name: Dr. Jana G.) [Location: First floor of Applied Sciences Dept.]

Instructions:
Answer all questions clearly
Draw neat structures wherever required
Use A4 sheets only
Do not type your answers; only handwritten assignments are accepted

1. Use VSEPR theory to predict the correct structures for the following. Show ALL the steps clearly.
(10)
(a) Thionyl chloride
(b) Chlorine trifluoride

Thionyl chloride, SOCl2

S = 6
O = 2
2 Cl = 2
Balance= 2 1 lonepair (lp)
3 bondpair (bp) + 1 lonepair (lp) = 4 Electronic geometry is TETRAHEDRAL.
Actual shape of the molecule is TRIGONAL PYRAMIDAL.
..

S
S Cl
Cl O
O
Cl
Cl

Chlorine trifluoride, ClF3

Cl = 7
3F = 3
Balance= 4 2 lonepairs (lp)
3 bondpair (bp) + 2 lonepair (lp) = 5 Electronic geometry is TRIGONAL BIPYRAMIDAL.
The 2 lp can be placed in three different ways: (a) diaxial, (b) diequatorial, and (c) axial-equatorial

(a) lp (b) F (c) lp

F lp lp
F Cl F Cl F Cl F
F lp F
lp F F
180 lp-lp = 1 120 lp-lp = 1 120 lp-bp = 2 F Cl
(can be ignored) (can be ignored) (can be ignored)
90 lp-bp = 6 120 lp-bp = 2 90 lp-lp = 1
(can be ignored) 90 lp-bp = 3
90 lp-bp = 4 F
Based on the above three, structure (b) is the correct structure
Actual shape of the molecule is T-SHAPED.

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2. Though LiCl and MgS have similar structure and nearly same internuclear distance, MgS is harder
than LiCl. Explain. (3)

In LiCl, the electrostatic interaction is between singly charged species (Li+ and Cl-) while it is doubly
charged for MgS (Mg2+ and S2-)
Higher charge stronger interaction between the ions stronger ionic bond harder substance
Thus MgS is harder than LiCl

3. Explain the following: (6)

(a) SnCl4 is more covalent than SnCl2
(b) KCl has high melting point than AgCl

(a) SnCl4 is more covalent because Sn4+ (higher charge, smaller size) has greater polarizing power than
Sn2+

(b) This is because Ag+ has pseudo noble gas configuration (or 18 electron outer shell) and hence has
higher polarizing power than K+ which has noble gas configuration (or 8 electron outer shell)
As a result, AgCl is more covalent than KCl and hence it possesses lower melting point

4. Based on electronegativity difference, predict the nature of bonds existing in CsCl and AlCl3. (3)
[Paulings electronegativity values: Cs (0.8); Al (1.6); Cl (3.2)].

Electronegativity difference in CsCl = 3.2 0.8 = 2.4

Electronegativity difference in AlCl3 = 3.2 1.6 = 1.6
Higher the difference, greater is the ionic nature of the bonds
Thus, CsCl is IONIC and AlCl3 is POLAR COVALENT

5. Among each of the following pairs of ions, which cation will have greater polarizing power and
why? (4)
(a) Na+ and Mg2+
(b) Pb2+ and Pb4+

(a) Mg2+ has high charge compared to Na+ Mg2+ will have greater polarizing power
(b) Pb4+ has high charge and hence small size compared to Pb2+ Pb4+ will have greater polarizing
power

6. Draw the complete orbital interaction diagram for ethyne. Indicate the electrons in the orbitals and
specify the hybridization of carbon and the geometry of the molecule. (6)

s orbital Bond formed by sp-sp overlap

H H
C C

2
 bond-1
bond-2
p orbital

H C bond C H

7. Draw the MO energy level diagram for Li6 molecule and fill the orbitals with electrons. Identify
ALL the valence and conduction bands according to band theory. (4)

Conduction band

E
Valence band

In addition to these conduction bands, the vacant 2p orbitals also overlap with 2s orbitals of these
lithium atoms and form conduction bands

8. (a) Write ALL the formulae of alkaline earth metal carbonates. (4)
(b) Arrange them in the order of INCREASING thermal stability.
Explain your choice.

The formlulae of alkaline earth metal carbonates - BeCO3, MgCO3, CaCO3, SrCO3, BaCO3
Increasing order of thermal stability: BeCO3 < MgCO3 < CaCO3 < SrCO3 < BaCO3
Since the charge on the metals are same (2+) and the anion is also the same (CO32-), the above trend
can be explained on the basis of decreasing polarizing power of the cation as we move from left to
right hand side since the size increases from Be to Ba
Larger size lower polarizing power greater ionic bond higher thermal stability

9. Work out the MOST COMMON Lewis structure for dinitrogen trioxide. Show ONLY the steps. Use
both the skeletons provided below. BASED on these Lewis structures, which do you think is the best
structure and why? (5)
O O

(a) N N (b) O N O N O

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 Formal Charge (FC) calculation:
2 "N" = 10 e

: :
3 "O" = 18 e O FC = 6 - 1 - 6 = -1

..
Total = 28 e
O O N FC = 5 - 3 - 0 = +2
N N ..
N FC = 5 - 2 - 2 = +1
O
-1 ..
:..O : :O:
(8 e used for forming skeleton) +1 +2 -1
Balance = 20 e N
.. N
..
:..O : :O: -1
.. :
:O
..N N
0 ..
:..O O:
0 ..
:..O :O:
.. :
:O 0 +1 0
0 +1 -1
(20 e used for satisfying octet) ..N N
(OR) ..N N
Balance = 0 e -1 0
.. :
:O O
.. :

2 "N" = 10 e Formal Charge (FC) calculation:

3 "O" = 18 e : :
Total = 28 e O FC = 6 - 1 - 6 = -1
..
O N O N O ..
(8 e used for forming skeleton) ..O FC = 6 - 2 - 4 = 0
Balance = 20 e ..
.. .. .. .. .. N FC = 5 - 2 - 2 = +1
:..O N O
.. N .. :
O
-1 ..
+1
.. .. 0 +1
.. .. -1
(20 e used for satisfying octet)
:..O N O
.. N .. :
O
Balance = 0 e 0
.. .. 0 0..
0 .. .. 0
:O N O
.. N O:

The second structure is the best structure because the formal charge for ALL the atoms is ZERO.

10. Apply valence bond theory and deduce the shape and hybridization in phosphorus pentachloride. Use
electron-in-box diagram. (4)

forms 5 sigma bonds with 5 Cl atoms

3d
Hybridization
3p sp3d
3s Remaining four
d orbitals

2p
E
2s

1s

Hybridization: sp3d Shape: Trigonal bipyramidal

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11. What types of bonds are formed when the following are reacted together? (2.5)
(a) Potassium and chlorine
(b) Sulphur and oxygen
(c) Phosphorus and chlorine
(d) Cesium and sulphur
(e) Trimethylamine and boron trifluoride

(a) Ionic bond

(b) Covalent bond
(c) Covalent bond
(d) Ionic bond
(e) Coordinate bond

12. Identify ALL types of bonds (covalent, metallic, etc.) present in sodium chlorate. (2)

Sodium chlorate = NaClO3

Ionic bond present between sodium ion and chlorate ion
In the chlorate ion, covalent bonds are present between Cl and O

13. Identify the hybridization of EACH OF THE NON-HYDROGEN ATOMS present in the following
molecule. (6.5)
sp2
sp3
sp2
O sp2
sp2 sp3 sp3 sp2 H sp3
sp 2 3 N
sp
sp2 sp3
sp3 sp 3
sp3 sp
sp2 sp
2 sp 3 sp3
sp sp2
2
sp sp2
TOTAL MARKS = 60