Chapter 9: Periodic Trends

83

Chapter 9 Periodic Trends

Self-test Exercises
S9.1

Found in aluminosilicate minerals or sulfides? Refer to the Figure 9.9 in your textbook. Cd and Pb are classified
as chalcophiles and give soft cations. Thus, they will be found as sulfides. Rb and Sr are lithophiles and are hard.
They can be found in aluminosilicate minerals. Cr and Pd are siderophiles and give cations of intermediate
hardness.. As such they can be found as both oxides and sulphides. Palladium can also be found elemental.

S9.2

Sulfur forms catenated polysulfides whereas polyoxygen anions are unknown? Oxygen forms a double bond
that is three times more stable than its single bond. Owing to this tendency to form strong double bonds, it is very
unlikely that longer chain polyoxigen anions would exist. Sulfur is much less likely to form bonds and therefore
more likely to generate catenated polysulfide anions.

S9.3

Shape of XeO4 and identify the Z + 22 compound with the same structure? Xe is the central atom. With 8
valence electrons from Xe and 24 electrons (6 from each O) we have 32 total electrons and 16 electron pairs. We
would predict a tetrahedral geometry to minimize electron pair repulsions. Note that in order to minimize formal
charge, the xenon will form double bonds with each oxygen. Because the atomic number of Xe is 54, the Z + 22 is
Os (Z = 76). The compound with the same structure is OsO4.

S9.4

Comment on fH values? The energy required to convert solid elements into the gaseous atomic form drops
going down the group. This is expected since the bond strengths decrease in the same order and it becomes easier
to break the molecules in solids. It is evident from the values that as we move down the group from S to Se to Te,
the steric crowding of the fluorine atoms is minimized owing to the increasing radius of the central atom. As a
result, the enthalpy values become larger and more negative (more exothermic) and the higher steric number
compounds (such as TeF6) are more likely to form.

S9.5

Further data useful when drawing comparisons with the value for V 2O5? We would have to know the
products formed upon thermal decomposition for P4O10 and thermodynamic data for the product. We could use
data for V2O5 from the Exercise 9.5.

End of Chapter Exercises

9.1

Maximum stable oxidation state? (a) Ba; +2, (b) As; +5, (c) P; +5, (d) Cl; +7.

9.2

Form saline hydrides, oxides and peroxides, and all the carbides react with water to liberate a
hydrocarbon? The group is the alkaline earth metals or Group 2 elements. Consult Sections 12.8 and 12.9 for
detailed reactions.

9.3

Elements vary from metals through metalloids to non-metals; form halides in oxidation states +5 and +3
and toxic gaseous hydrides? These elements are Group 15. This group is very diverse. N and P are nonmetals; As
and Sb are metalloids; and Bi is metallic. The +5 and +3 oxidation states are common for the group electron
configuration of ns2p3. Phoshine and arsine are well known toxic gases.

9.4

BornHaber cycle for the formation of the hypothetical compound NaCl 2? Which thermochemical step is
responsible for the fact that NaCl2 does not exist? The key steps in the BornHaber cycle are:
Na(s)

Cl2(g)

Na(g)

+
Na (g)

2Cl(g) + 2 e

Na2+(g) + 2 Cl (g)

Na(g)
2Cl(g)
Na+(g) + 1e
Na2+(g) + 1e
2Cl (g)
NaCl2(s)

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sublimation
dissociation
first ionization
second ionization
electron gain
lattice enthalpy

subH
disH
ion1H
ion2H
egH
LH

Chapter 9: Periodic Trends

84

We can use Figure 3.44 to construct a comparable cycle. You can calculate the lattice enthalpy by moving around
the cycle and noting that the enthalpy of formation fH = subH + disH + ion1H + ion2H egH LH. The
second ionization energy of sodium is 4562 kJ mol-1 and is responsible for the fact that the compound does not
exist as it would result in a large, positive enthalpy of formation.
9.5

Inert pair effect beyond Group 15? The relative stability of an oxidation state in which the oxidation number is 2
less than the group number is an example of the inert pair effect. This is a recurring theme in the heavier p-block
elements. Beyond Group 15 where we see inert pair effect influencing the favored 3+ oxidation state for elements
such as Bi and Sb, we also find stable +5 oxidation states for the halogens in Group 17. Examples include BrO 3
and IO3. As a result of this intermediate oxidation state, these compounds can function as both oxidizing and
reducing agents. Group 16 elements (except oxygen) also form several stable compounds with +4 oxidation states
including SF4 and SeF4. The inert pair effect would manifest itself the most for Po, the heaviest member of the
Group 16.

9.6

Ionic radii, ionization energy, and metallic character? Metallic character and ionic radii decrease across a
period and down a group. Ionization energy increases across a period and decreases down a group. Large atoms
typically have low ionization energies and are more metallic in character.

9.7

Names of ores? (a) Mg; MgCO3 magnesite, (b) Al; Al2O3 bauxite, and (c) Pb; PbS galena.

9.8

Identify the Z + 8 element for P. Similarities? The atomic number of P is 15. The Z + 8 element has an atomic
number of 23 and is V (vanadium). Both form compounds with varying oxidation states up to a maximum value of
+5. Both form stable oxides including ones in +5 oxidation state (V 2O5 and P2O5). Like phosphorus, vanadium
forms oxoanions including ortho-, pyro- and meta-anions. Consult Section 15.5 for analogous phosphorus
oxoanions.

9.9

Calculate B(Se F) in SeF4 and SeF6? What we are looking for are Se F bond dissociation energies in SeF4 and
SeF6. To determine these values we have to use the Born-Haber cycle. Looking first at SeF6, we have:
Se(s) + 3F2(g) SeF6(g), fH = - 1030 kJ/mol
We can break this reaction into three elementary steps:
1. Se(s) Se(g); aH(Se) = +227 kJ/mol
2. 3F2(g) 6F(g); aH(F) = +159 kJ/mol 3
3. Se(g) + 6F(g) SeF6(g); rxnH = X
Note that aH for reaction 2. has to be multiplied by 3 since we need to atomize (break bonds in) 3 moles of F 2(g).
Also note that in reaction 3 we form 6 Se F bonds and no other physical or chemical transformation takes place.
If we sum reactions 1 3 we get our first reaction given above. Thus, we can write:
fH = aH(Se) + 3aH(F) + rxnHNow substitute given values:
- 1030 kJ/mol = 227 kJ/mol + 3159kJ/mol + X.
From here:
X = - 1030 kJ/mol 227kJ/mol - 3159kJ/mol = - 1575 kJ/mol.
Since X gives energy released per 6 Se F bonds and we need only one Se F, we have to divide X by 6, and get 262.5 kJ/mol. Further, we have to change the sign because B(Se F) is bond dissociation energy (energy required
to break the bond) not bond formation energy (energy released when a bond is formed) to finally obtain B(Se F)
in SeF6 as 262.5 kJ/mol.
In a similar way we can determine the B(Se F) for SeF4.
Se(s) + 2F2(g) SeF4(g), fH = - 850 kJ/mol
Elementary steps are:
1. Se(s) Se(g); aH(Se) = +227 kJ/mol
2. 2F2(g) 4F(g); aH(F) = +159 kJ/mol 2
3. Se(g) + 4F(g) SeF4(g); rxnH = X
Note that this time aH(F) is multiplied by 2 and that in equation 3 four Se F bonds are formed. We have:
- 850 kJ/mol = 227 kJ/mol + 2159kJ/mol + X
And
X = - 850 kJ/mol 227kJ/mol - 2159kJ/mol = - 1359 kJ/mol.

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Chapter 9: Periodic Trends

And the bond dissociation energy B(Se F) in SeF4 is (-1359 kJ/mol -1)/4 = 348.7 kJ/mol.
Comparing the Se F bond strength in SeF4 and S F bond strength in SF4 we see that Se F bond is slightly
stronger (for about 8 kJ/mol) than S F bond. However, the Se F bonds in SeF6 are significantly weaker in
comparison to the S F bonds in SF6. This reflects the general periodic trend according to which E X bond
decrease in strength on going down the group.

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