CHEM110 Intensive School – Chapters 5, 6 & 7

1. Draw the Lewis structure for each of the following polyatomic ions, and predict their electron-domain and
molecular geometries: (a) ClO
4
-
(b) BrO
2
-
(c) CO
3
2-

Assign the hybridization of the bolded atom in each case.

(a) Firstly calculate the number of valence electrons (from the periodic table)
Cl = 7
O = 6 × 4 = 24
Negative charge add 1e
-
= 1
Total = 32 e
-

Next for single bond framework (most electronegative atoms on the outside; in this case O)


8 e- used in bonds therefore 24 left.

Place 6 valence e
-
on each outer atom (except H)


32 e- used in bonds therefore 0 left to assign.

Finally calculate formal charges and reduce if required:
FC = (Valence e
-
for the atomic state of the atom) – (Valence e
-
in Lewis structure) -


(shared e
-
)
Cl
fc
= 7 – 0 -


(8) = +3
O
fc
= 6 - 6 -


(2) = -1


Therefore O atoms can share some more electrons with each Cl to minimize formal charges on each.

Cl
fc
= 7 – 0 -


(14) = 0
O
fc
= 6 - 4 -


(4) = 0
One O remains unchanged with FC of -1, resulting in -1 charge for the molecule.

From this Lewis structure it can be seen there is 4 electron domains around Cl (all bonding domains)
Therefore the electron geometry is tetrahedral and the molecular geometry is also tetrahedral.
The hybrization is sp
3
as there are four electron domains around Cl. (from a combination of 1× s and 3 × p
atomic orbitals).


(b) Firstly calculate the number of valence electrons (from the periodic table)
Br = 7
O = 6 × 2 = 12
Negative charge add 1e
-
= 1
Total = 20 e
-

Next for single bond framework (most electronegative atoms on the outside; in this case O)


4 e- used in bonds therefore 16 left.

Place 6 valence e
-
on each outer atom (except H)


16 e- used in bonds therefore 4 left to assign.

Place final 4e
-
on the central Br atom


Finally calculate formal charges and reduce if required:
FC = (Valence e
-
for the atomic state of the atom) – (Valence e
-
in Lewis structure) -


(shared e
-
)
Br
fc
= 7 – 4 -


(4) = +1
O
fc
= 6 - 6 -


(2) = -1

Therefore O atoms can share some more electrons with each Br to minimize formal charges on each.

Br
fc
= 7 – 4 -


(6) = 0
O
fc
= 6 - 4 -


(4) = 0
One O remains unchanged with FC of -1, resulting in -1 charge for the molecule.

From this Lewis structure it can be seen there is 4 electron domains around Br (2 bonding domains and 2
lone pairs)

Therefore the electron geometry is tetrahedral and the molecular geometry is bent.
The hybrization is sp
3
as there are four electron domains around Br. (from a combination of 1× s and 3 ×
p atomic orbitals).

(c) Firstly calculate the number of valence electrons (from the periodic table)
C = 4
O = 6 × 3 = 18
Negative charge add 2e
-
= 2
Total = 24 e
-

Next for single bond framework (most electronegative atoms on the outside; in this case O)


6 e- used in bonds therefore 18 left.

Place 6 valence e
-
on each outer atom (except H)


24 e- used in bonds therefore 0 left to assign.

Finally calculate formal charges and reduce if required:
FC = (Valence e
-
for the atomic state of the atom) – (Valence e
-
in Lewis structure) -


(shared e
-
)
C
fc
= 4 – 0 -


(6) = +1
O
fc
= 6 - 6 -


(2) = -1

Therefore an O atom can share some more electrons with each C to minimize formal charges on each.

C
fc
= 4 – 0 -


(8) = 0
O
fc
= 6 - 4 -


(4) = 0
Two O remains unchanged with FC of -1, resulting in -2 charge for the molecule.

From this Lewis structure it can be seen there is 3 electron domains around C(3 bonding domains)

Therefore the electron geometry is trigonal planar and the molecular geometry is trigonal planar.
The hybrization is sp
2
as there are three electron domains around C. (from a combination of 1× s and 2 ×
p atomic orbitals).



2. (a) From the relevant molecular orbital diagrams below determine which species out of C
2
2-
and C
2
has the
stronger bond? Use bond order calculations to justify your choice.

(b) Use the relevant molecular orbital diagrams to ascertain whether formation of Be
2
or Be
2
2+
is possible.

BO (C
2
2-
) = ½ ((e
-
in BOs)-(e
-
in ABOs)
BO (C
2
2-
) = ½ (8- 2) = 3

BO (C
2
) = ½ ((e
-
in BOs)-(e
-
in ABOs)
BO (C
2
) = ½ (6- 2) = 2

Therefore C
2
2-

has the stronger bond due to its higher bond order


1s
2s
1s
2s
Be
2
1s
2s
1s
2s
Be
2
2+

BO (Be
2
) = ½ ((e
-
in BOs)-(e
-
in ABOs)
BO (Be
2
) = ½ (4- 4) = 0

BO (Be
2
2+
) = ½ ((e
-
in BOs)-(e
-
in ABOs)
BO (Be
2
2+
) = ½ (4- 2) = 1

Therefore Be
2
doesn’t exist but Be
2
2+
can exist












(a)

(b)

3. Consider the apparatus shown in the diagram on
the right:
(a) Calculate the amount (in moles) of N
2
and O
2

present and determine the mole fraction of each.
(b) Determine the total pressure of gas in the
apparatus and find the partial pressure of each
gas after the valve is opened and the gases are
allowed to mix thoroughly.






Find moles of each gas using ideal gas equation.

݌ܸ = ܴ݊ܶ

∴ ݊ =
݌ܸ
ܴܶ


݊


=
௣௏
ோ்
݊


=
௣௏
ோ்


݊


=
ଵ× ଵ଴

௉௔ × ଶ× ଵ଴
షయ


଼.ଷଵସ ௃ ௠௢௟
షభ

షభ
×ଶଽ଼ ௄
݊


=
ଶ× ଵ଴

௉௔ × ଷ× ଵ଴
షయ


଼.ଷଵସ ௃ ௠௢௟
షభ

షభ
×ଶଽ଼ ௄


Note: 1L = 1 × 10
-3
m
3

݊


= 0.08 ݉݋݈ ݊


= 0.24 ݉݋݈

݊
௧௢௧௔௟
= 0.08 ݉݋݈ + 0.24 ݉݋݈ = 0.32 ݉݋݈

Calulcate mole fractions
ݔ


=

ಿ


೟೚೟ೌ೗
=
଴.଴଼
଴.ଷଶ
= 0.25 ݔ


=




೟೚೟ೌ೗
=
଴.ଶସ
଴.ଷଶ
= 0.75

Calculate total pressure after tap is opened using ideal gas equation using total volume and total moles of
gas


݌ܸ = ܴ݊ܶ

∴ ݌ =
ܴ݊ܶ
ܸ


݌
௧௢௧௔௟
=
0.32 ݉݋݈ × 8.314 ܬ ݉݋݈
ିଵ
ܭ
ିଵ
× 298 ܭ
5 × 10
ିଷ
݉

= 158564 ܲܽ = 1.6 × 10

ܲܽ (2 ݏ݅݃. ݂݅݃. )


Calculate partial pressure from mole fraction and total pressure

2.0 L
1.0 × 10
5
Pa
298K
3.0 L
2.0 × 10
5
Pa
298K
݌


= ݔ


× ݌
௧௢௧௔௟
݌


= ݔ


× ݌
௧௢௧௔௟


݌


= 0.25 × 1.6 × 10

ܲܽ ݌


= 0.75 × 1.6 × 10

ܲܽ

݌


= 4.0 × 10

ܲܽ ݌


= 1.2 × 10

ܲܽ




4. For each of the following pairs of substances indicate which one you would expect to have the lower
vapour pressure (a) CH
3
OH and CH
3
SH (b) HF and HCl (c) Cl
2
and F
2
(d) decane (C
10
H
22
) and octadecane
(C
18
H
38
)



(a) CH
3
OH and CH
3
SH
CH
3
OH has H bonding whilst CH
3
SH only possesses dipolar forces. Therefore CH
3
OH has lower vapour
pressure to stronger intermolecular forces




(b) HF and HCl
HF has H bonding whilst HCl only possesses dipolar forces. Therefore HF has lower vapour pressure to
stronger intermolecular forces




(c) Cl
2
and F
2
Both compounds are symmetrical and therefore no polar inteactions are present. The amount of electrons
dictates the strength of dispersion forces therefore Cl
2
has a lower vapour pressure,

as it has more electrons
than F
2





(d) decane (C
10
H
22
) and octadecane (C
18
H
38
)
Both compounds have no strong dipolar inteactions. Therefore the amount of electrons dictates the strength of
dispersion forces. Hence octadecane (C
18
H
38
) has a lower vapour pressure,

as it has more electrons than
decane (C
10
H
22
)















5. Iron crystallises in the unit cell shown to the right:
(a) What type of unit cell is this?
(b) How many iron atoms are present in the unit cell?
(c) If the radius of an iron atom is 126 pm, what is the length of the
edge of the unit cell?

(a) Body centred cubic
(b) 2
(c)

y = 4r; using pythagoras’ theorem
y
2
= a
2
+ x
2
and
x
2
= a
2
+ a
2
= 2a
2

therefore
y
2
= a
2
+

2a
2
= 3a
2
substituting for y:
(4r)
2
= 3a
2

Rearrange to solve for a:
ܽ ൌ

ሺ4ݎሻ

3


ሺ4 ൈ 126 ݌݉ሻ

3

a = 291

pm

a
y
x









6. Sketch the phase diagram for O
2
from the following data: Normal melting point = 55 K; normal boiling
point = 90 K; triple point = 54 K and 1.52 × 10
2
Pa; critical point = 154 K and 5.02 × 10
6
Pa. Indicate on
the diagram the regions in which each phase is stable.


55 K
90 K
154 K
1.52 × 10
2
Pa
in K
in Pa
54 K
1.52 × 10
2
Pa
1.52 × 10
2
Pa
54 K