Numerical Problems and Issues.

Chapter 6

1. Write the Lewis structures for the following compounds

iónicos: (a) cloruro de calcio; (b) sulfuro de bario; c) óxido de litio; d)
{"fluoruro de sodio":"sodium fluoride","nitruro de magnesio":"magnesium nitride"}
All these structures are ionic, that is, in the molecule the atoms
metallics are in cationic form and non-metallic atoms are in their form
anionic.
Empirical formula: a) CaCl2["b) BaS","c) Li"]2["O","d) NaF","e) Mg"]3N2
Lewis Structures:

2. Indicate what is wrong with each of the following

Lewis structures.

a) It is impossible for hydrogen not to be a peripheral atom, that is

that is surrounded by more than two electrons
b) The number of bonding electrons that are reflected in the molecule
(20) does not correspond to the number of valence electrons of
their atoms: 6+7+6 = 19.
c) The molecule has a carbon atom with hypovalence. Only
It is surrounded by 6 electrons. It is possible that this atom is
surrounded by 8 electrons if nitrogen shares a pair with C
from its valence electrons, forming a triple bond CN.

Note: the Lewis structure given in the problem must have a small
participation in the molecular electronic structure, which allows to explain the
experimental characteristics of the bond (polarity and bond distance)

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 Numerical Problems and Issues. Chapter 6

d) The bond between calcium and oxygen is ionic, therefore it cannot

drawing a line between them that represents a pair of electrons
shared among the nuclei

3. Write the Lewis structures of carbon monoxide and of

sulfur monoxide. Determine the formal charge of each atom.

Carbon monoxide: CO
Construction of the molecular Lewis structure:
Number of valence electrons of C: 4
Number of valence electrons of O: 6
Total valid election numbers :10

Formation of the simple C-O bond and distribution of electron pairs

among the atoms:

Distribution of electrons to fulfill the octet rule:

C O
→ C O
Formal charge on C: 4 - 5 = -1
Formal charge on O: 6 - 5 = 1

Sulfur Monoxide
Number of valence electrons of S: 6
Number of valence electrons of O: 6
Total ballot election number 12

Distribution of electrons to comply with the octet rule:

S O

Formal charge on S: 6 - 6 = 0
Formal charge on O: 6 - 6 = 0

4. Write the Lewis structures of the ammonium ions, [NH4]+ y

borohydride, [BH4]-Determine the formal charge of each atom.
Ammonium Ion
Átomo central: N
Lingandos: the four atoms of H
Number of e and valence: 5 of Al
+ 4 of the 4 atoms of H
-1 of the cation charge
_________________________
8 valence electrons
Four bonds, between the N and the four hydrogen atoms, need the 8
valence electrons that the molecule has. Therefore, all the bonds are
simple.
Lewis structure of the ammonium ion:

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 Numerical Problems and Issues. Chapter 6

H +
H N H

H
Formal charge on N: 5 - 4 = +1
Formal charge on H: 1 - 1 = 0

Boron Hydride Ion

Central atom: B
Lingandos: the four atoms of H
Number of e and valence: 3 of B
+ 4 of the 4 H atoms
+1 from the charge of the anion
_________________________
8 valence electrons
Four links, between the B and the four hydrogen atoms, need the 8
valence electrons that the molecule has. Therefore, all the bonds are
simple.
Lewis structure of the ion:

H -
H B H

5. Write two Lewis structures for cyanamide (NH2CN)

important chemical products of the fertilizer industries and
Plastics. Use the concept of formal charge to choose the structure.
more likely or representative (plausible).
Remember that the hydrogen atoms must be peripheral. Clearly from
the other three atoms, the C atom is the least electronegative, so it will be the
central. Also remember that in Organic Chemistry the formula of the
It is common to write compounds by functional groups. If you observe the
molecule will see that it is composed of two groups the amino group (NH2) and the
nitrile group (CN).
Therefore, a Lewis structure would be:

In this structure, the formal charge on each atom is zero.

We could draw another Lewis structure similar to the one given in the
problem 2c.

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 Numerical Problems and Issues. Chapter 6

Form b) is a dipole; one of the nitrogens (the one from the nitrile group) remains
with excess negative charge and the other (the amino group) remains charged
positively.
The most representative Lewis structure of the cyanamide molecule
(cyan + amine) is the first.
The following figure illustrates its real structure.

6. Write an acceptable Lewis structure for NO2 and indicate if the

The molecule will be paramagnetic or diamagnetic. Two molecules of NO.2
They can dimerize (bind to each other) obtaining the N.2O4Write
An acceptable Lewis structure for this last molecule and
comment on their magnetic properties.

Number of valence electrons to form the molecule:

Nitrogen: 5
2xOxygen=2x6=12
17
This odd number of electrons will cause the octet rule not to be fulfilled.
for the central atom that will be a radical.
Most representative Lewis structure of the molecule:

This molecule has an unpaired lone electron, which indicates that the
the molecule must be paramagnetic. It is clear that, since the molecule
it is symmetrical the double bond can form with either one or the other
oxygen atom, so the molecule will be a resonance hybrid

The bond order of O-N in the molecule will be 1 + 1/2 = 1.5

The molecule is a radical and will be quite reactive, for this reason at low
temperature, due to the pairing of unpaired electrons, dimerizes,
producing

O O

N N

O O

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 Numerical Problems and Issues. Chapter 6

Just as mentioned earlier for the monomer, the double bonds

they can be in these positions or in other equivalent ones, therefore the order
the N-O bond has not changed compared to nitrogen dioxide, it remains the same.
1+2/4=1.5. The bond order N-N is 1.

7. Describe the carbon-sulfur bond in H 2CSF4that is to say, indicate if

It is more likely to be simple, double, or triple.
The way the molecule is written gives the impression of being
formed by a group H2C (methylen) and a SF4 group. So that the
the most representative Lewis structure of the molecule would be:

In this case, and with a double bond C=S, the formal charge on each atom
It is 0. S has saturated its maximum valence (6) through the formation of
four simple links with four F atoms and a double bond with the
carbon atom.
With these same two functional groups, the existence of a single bond
C-S involves an unpaired electron on C and another on S, which does not
it seems like a very stable electronic structure.
We can assume a simple C-S bond if we distribute the F atoms of
another way, H2FCSF3giving rise, evidently, to a different molecule.

where S acts with a valence of 4.

The formation of a triple bond CS with the number of atoms we have
It would be impossible. A triple bond implies the disappearance of at least two.
of the peripheral atoms.

8. Propose all possible Lewis structures, resonance forms,

for the sulfate anion. What would be the most suitable Lewis structure?
representative for that molecule?
Sulfate Ion: SO4 2-

Valence electrons: 6 (S) + 24 (O) + 2 (anion) = 32

Central atom: S
Ligands: O
4 simple links = 8 electrons
Distribute the 24 electrons among the 4 ligands: 24/4= 6
That is, 6 lone pair electrons on each O.

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 Numerical Problems and Issues. Chapter 6

-1
O

O
+2 O -1
S
-1
O
-1 (a)

This Lewis structure obeys the octet rule, both for sulfur.
like for the oxygen atoms. The calculation of the formal charge on each
The atom contributes a charge of 2+ on the S and -1 on each of the
oxygens. This distribution of formal charges indicates a structure
molecular multipolar very unlikely. This situation can be fixed.
situating the lone pairs of electrons as bonding electrons of the
peripheral atoms, since the element is in the third period, which
it implies that it does not have to follow the octet rule (it has 3d orbitals
(empty). This is what Lewis's rules say for molecules with
central atoms with hypervalence.

0
O

-1 +1 -1
O S O

O
(b) -1
This other structure distributes a formal load of +1 for the S, 0 for the
oxygen with a double bond and -1 for the rest. For the same reason that
As mentioned earlier, another double bond can be formed with a
peripheral oxygen.
0
O

-1 0
O S O0

-1 O
(c)
This Lewis structure assumes the saturation of the valence 6 of S.
leaving this one with a net charge of 0. This is the predominant Lewis structure.
for the sulfate anion. The formation of more double bonds between the S and another
oxygen atom would imply a net negative charge on the S and one of the
oxygens, which would be considerably less acceptable than structure (c).
Note: remember that the sulfate anion leads to sulfuric acid SO4H2, where the atoms
the H atoms are bonded to the oxygen atoms, forming OH bonds.

On the other hand, the form has different resonant structures

equivalents:

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 Numerical problems and Questions. Chapter 6

2- 2- 2-
O O O

O S O O S O O S O

O O O

2- 2- 2-
O O O

O S O O S O O S O

O O O

All these forms have the same weight in the overall structure of the anion. Thus
that the anion is a completely symmetric structure with a bond order of CS
nCS= 1+2/4 = 1.5
a formal charge of 0 on S and a formal charge of -0.5 (-2/4) on each of
the oxygen atoms.

9. Knowing the dissociation energies of the nitrogen-oxygen bond

in NO, 631 kJ/mol; H-H in H 2436 kJ/mol; N-H in NH 3389
kJ/mol; O-H and H 20, 463 kJ/mol, calculate theΔH from the following
reaction:
2NO(g) + 5H2(g)→2 NH3(g) + 2 H20 (g)

In this reaction, 3 NH bonds are formed for each molecule of ammonia.

a total of) and two OH links for each water molecule (four in total).
In addition, a bond is broken NOT for each molecule (2 in total) and a bond.
for each molecule of hydrogen (5 in total). Thus, the energy balance
it will be:
ΔH = 2(-3x389) + 2(-2x463) – [2(-631) + 5(-436)] = -1.184 kJ

10. Use your knowledge of electronegativities and without using

no table or figure from the recommended texts or the ones used
in theory class, arrange the following links according to their nature
increasing ionic, Explain why

{"C-H":"C-H","F-H":"F-H","Na-Cl":"Na-Cl","Br-H":"Br-H","K-F":"K-F"}
We have established that a bond will have a more polar character the more
the greater the difference in electronegativities between its atoms. Without
check the number in any table, we must know that the elements
halogens are the most electronegative and alkaline elements are the
less electronegative (more electropositive) in the periodic table. Therefore,
the NaCl and KF links are much more polarized than the rest, in the
that a bond forms between a nonmetal and H. In fact, these two
compounds form ionic bonds, while the rest of the bonds are
more or less polarized covalent.

We must also know that electronegativity within a group,

increases as the atomic number decreases. Thus, F is more

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 Numerical Problems and Issues. Chapter 6

more electronegative than Cl and K is more 'electropositive' than Na. With this
We could say that 'the KF bond is more ionic than NaCl'.

For this same reason, the FH link must be much more polarized than the
BrH, since Br is less electronegative than F.

The least polarized bond must be the C-H.

Therefore, the order regarding the polarity of the bond would be:
K-F > Na-Cl > F-H > Br-H > C-H

11. The water molecule has a bond angle of 104º and its
The dipole moment is 1.84 D. What is the value of the dipole moment of
O-H bond? Use the same methodology to estimate the angle of
link of the hydrogen sulfide molecule if it is known that its
the dipole moment is 0.93 D and the dipole moment of the S-H bond is
0.67 D.

The H molecule2It has a bond angle of 104º. Its dipole moment

it is the result of the composition of the two dipole moments of the
OH link. The previous figure shows a diagram of this vector sum.
Therefore, the dipole moment of water will be:

μ (H2O) = 2μ (OH) Cos 52º = 1.84 D

μ (OH)= 1,84/2. Cos 52º

The molecule of H2It is analogous to the water molecule, so its moment

dipolar will be given by:
μ (H2S) = 2μ (SH) Cos (α/2)º =
0.93 = 2. 0.67 Cos (α/2)º
Cosα0.69
α = 2. arc Cos 0.69

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