Você está na página 1de 41

CHAPTER 22

CHEMISTRY OF THE MAIN GROUP ELEMENTS II:


GROUPS 18, 17, 16, 15 AND HYDROGEN
PRACTICE EXAMPLES
1A

(D) This question involves calculating E for the reduction half-reaction:


ClO3(aq) + 3 H2O(l) + 6 e Cl(aq) + 6 OH(aq)
Here we will consider just one of the several approaches available to solve this
problem. The four half-reactions (and their associated E values) that are used in this
method to come up with the missing E value are given below. (Note: the E for the
first reaction was determined in Example 22-1)
1) ClO3(aq) + H2O(l) + 2 e ClO2(aq) + 2 OH(aq)

E = 0.295 V

G1 = 2FE

2) ClO2(aq) + H2O(l) + 2 e OCl(aq) + 2 OH(aq)

E = 0.681 V

G2 = 2FE

3) OCl(aq) + H2O(l) + 1 e 1/2 Cl2(aq) + 2 OH(aq) E = 0.421 V

G3 = 1FE

4) 1/2 Cl2(aq) + 1 e Cl(aq)

G4 = 1FE

E = 1.358 V

Although the reactions themselves may be added to obtain the desired equation, the E
for this equation is not the sum of the E values for the above four reactions. The E
value for the desired equation is actually the weighted average of the E values for
reactions (1) to (4). It can be calculated by summing up the free energy changes for the
four reactions. (The standard voltages for half-reactions of the same type are not
additive. The G values for these reactions can, however, be summed together.)
When (1), (2), (3) and (4) are added together we obtain
1)

ClO3(aq) + H2O(l) + 2 e ClO2(aq) + 2 OH(aq) E1 = 0.295 V

+ 2)

ClO2(aq) + H2O(l) + 2 e OCl(aq) + 2 OH(aq)

+ 3)

OCl(aq) + H2O(l) + 1 e 1/2 Cl2(aq) + 2 OH(aq) E3 = 0.421 V

+ 4)

1/2 Cl2(aq) + 1 e Cl(aq)

ClO3(aq) + 3 H2O(l) + 6 e Cl(aq) + 6 OH(aq)

E2 = 0.681 V
E4 = 1.358 V

and

G5 = G1 + G2 + G3 + G4

so,

6FE5 = 2F(0.295 V) + 2F(0.681V) + 1F(0.421 V) + 1F(1.358 V)

Hence, E5 =

E5 = ?

- 2F(0.295 V) - 2F(0.681V) - 1F(0.421 V) - 1F(1.358 V)


= 0.622 V
- 6F

1095

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

1B. (D) This question involves calculating E for the reduction half-reaction:

2 ClO3(aq) + 12H+(aq) + 10 e Cl2(aq) + 6 H2O(l)


The three half-reactions (and their associated E values) are given below:
(1)

ClO3(aq) + 3H+(aq) + 2 e HClO2(aq) + H2O(l)

(2)

HClO2(aq) + 2 H+(aq) + 2 e HClO(aq) + H2O(l) E = 1.645 V

(3)

2 HClO (aq) + 2 H+(aq) + 2 e Cl2(aq) + 2 H2O(l)


(remember that G= nFE)

E = 1.181 V
E = 1.611 V

Although the reactions themselves can be added to obtain the desired equation, the E
for this equation is not the sum of the E values for the above three reactions. The E
for the desired equation is actually the weighted average of the E values for reactions
(1) to (3). It can be obtained by summing up the free energy changes for the three
reactions. (For reactions of the same type, standard voltages are not additive; G
values are additive, however.) When (1) and (2) (each multiplied by two) are added to
(3) we obtain:
2(1) 2 ClO3(aq) + 6 H+(aq) + 4 e 2 HClO2(aq) + 2 H2O(l)
2(2) 2 HClO2(aq) + 4 H+(aq) + 4 e 2 HClO(aq) + 2 H2O(l)
(3) 2 HClO (aq) + 2 H+(aq) + 2 e Cl2(aq) + 2 H2O(l)

2 ClO3 (aq) + 12 H (aq) + 10 e Cl2(aq) + 6 H2O(l)


and

G4 = G1 + G2 + G3

so,

10FE4 = 4F(1.181 V) + 4F(1.645 V) + 2F(1.611 V)

Hence, E4 =
2A

E1 = 1.181 V
E2 = 1.645 V
E3 = 1.611 V

E4 = ?

- 4F(1.181 V) - 4F(1.645 V) - 2F(1.611 V)


= 1.453 V
- 10 F

(M) The dissociation reaction is the reverse of the formation reaction, and thus G for
the dissociation reaction is the negative of G f
HF g
12 H 2 g + 12 F2 (g)

G = Gf = 273.2 kJ/mol

We know that
G = RT ln K P

ln K P =

+273.2 103 J/mol = 8.3145 J mol1 K 1 298 K ln K P

273.2 103 J mol1


= 110 K p = e110 = 1.7 1048 2 1048
8.3145 J mol1 K 1 298 K

Virtually no dissociation of HF(g) into its elements occurs.

1096

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

2B

(M) The dissociation reaction with all integer coefficients is twice the reverse of the
formation reaction.
2HCl g H 2 g + Cl 2 g

G = 2 95.30 kJ / mol = +190.6 kJ / mol = RT ln K p

G
190.6 103 J / mol
=
= 76.9
ln K p =
RT
8.3145 J mol1 K 1 298 K

K p = e 76.9 = 4 1034

We assume an initial HCl(g) pressure of P atm, and calculate the final pressure of
Cl2(g) and H2(g), x atm.
Reaction:

2 HCl(g)

Initial:
Changes:
Equil:

P atm
2x atm
(P 2x) atm

H2(g)

0 atm
+x atm
x atm

P{H 2 g }P{Cl2 g }
x x
x
Kp =
=
=

2
2
P{HCl g }
P 2x P 2x

Cl2(g)
0 atm
+x atm
x atm

x
= 4 1034 2 1017
P 2x

x = 2 1017 P 2 x 2 1017 P

% decomposition =

2x
100% = 2 2 1017 100% 4 1015 % decomposed
P

INTEGRATIVE EXAMPLE
A

(M) The half-reactions are:


NO-2 +2OH - NO-3 +H 2O+2e{NO-2 +H 2 O+e- NO+2OH - } 2

E o 0.04V
E o 0.46V

_________________________________________________________________________________________________________
o
3NO-2 H 2O NO 3 +2NO+2OH
Ecell
0.42V
o
E for the first reaction (oxidation) can be calculated by using the approach in Example
22-1. The calculated value is very small, and so the Eo for the disproportionation
reaction is negative. The disproportionation of NO2- to NO3- and NO is therefore not
spontaneous.

(M) The half-reactions are:


HNO 2 +H 2O NO-3 +3H + +2e{HNO 2 +H + +e- NO+H 2O} 2

E o 0.934V
E o 0.996V

________________________________________________________________________________________________________________
o
3HNO 2 NO-3 +H + +H 2O+2NO
Ecell
0.062V
o
E for the first reaction (oxidation) can be calculated by using the approach in Example
o
22-1. Ecell
for the reaction is positive and therefore disproportionation of HNO2 to NO3and NO is spontaneous under standard conditions.

1097

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

EXERCISES
Periodic Trends in Bonding and Acid-Base Character of Oxides
1.

(E) LiF, BeF2, BF3, CF4, NF3, OF2. LiF is an ionic compound, BeF2 is a network
covalent compound, and the others are molecular covalent compounds.

2.

(E) NaF, MgF2, AlF3, SiF4, PF5, SF6, and ClF5. NaF and MgF2 are ionic compounds,
AlF3 is a network covalent compound, and the others are molecular covalent
compounds.

3.

(E) The metallic character of the elements increases as we move down a group, and
so too does the basic character of the oxides. Bi2O3 is most basic, P4O6 is least basic
(and is actually acidic), and Sb4O6 is amphoteric.

4.

(M) The metallic character of the elements increases as we move down a group, and
so too does the basic character of the oxides. Stated another way, the acidic character
of the oxides decreases as we move down a group. On this basis, we expect SeO2 to
be the acidic oxide and TeO2 to be the amphoteric oxide.

The Noble Gasses


5.

(M) First we use the ideal gas law to determine the amount in moles of argon.

PV
145 atm 55 L

3.25 102 mol Ar


1
1
RT 0.08206 L atm mol K 299 K

L air = 3.25 102 mol Ar


6.

22.414 L Ar STP 100.000 L air

= 7.8 105 L air


1 mol Ar
0.934 L Ar

(M) First we compute the volume occupied by 5.00 g of He at STP, and then the
volume of natural gas. From Chapter 6 we saw that 1 mol of gas at STP occupied
22.414 L.
natural gas volume = 5.00 g He

1 mol He 22.414 L He 100 L air

4.003 g He
1 mol He
8 L He

natural gas volume = 3.5 102 L air at STP 300 L

7.

(M) (a)

O Xe
O

(b)

(c)

O
O Xe
O

1098

Xe

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

8.

(a)

The Lewis structure has three ligands and one lone pair on Xe. XeO3 has a
trigonal pyramidal shape.

(b)

The Lewis structure has four ligands on Xe. XeO 4 has a tetrahedral shape.

(c)

There are five ligands and one lone pair on Xe in XeF5 . Its shape is square
pyramidal.

(M) We use VSEPR theory to predict the shapes of the species involved.
(a)

O 2 XeF2 has a total of 2 6 + 8 + 2 7 = 34 valence electrons = 17 pairs.

(b)

O3 XeF2 has a total of 3 6 + 8 + 2 7 = 40 valence electrons = 20 pairs.

(c)

OXeF4 has a total of 6 + 8 + 4 7 = 42 valence electrons = 21pairs.

We draw a plausible Lewis structure for each species below.


O

(a)
F

Xe
O

(b)
F

F
F
O Xe O
O

(c)

F
F
F Xe F
O

(a)

There are four ligands and one lone pair on Xe in O 2 XeF2 . Its shape is a see-saw.

(b)

There are five ligands and no lone pairs on Xe in O3 XeF2 . Its shape is trigonal
bipyramidal.

(c)

The Lewis structure has five ligands and one lone pair on Xe. OXeF4 has a
square pyramidal shape.

9.

(E) 3 XeF4(aq) + 6 H2O(l) 2 Xe(g) + 3/2 O2(g) + 12 HF(g) + XeO3(s)

10.

(E) 2 XeF6(aq) + 16 OH(aq) Xe(g) + XeO64(aq) + O2(g) + 8 H2O(l) + 12 F(aq)

11.

(E) For these noble gases, the bond energy of the noble gas fluorine is too small to
offset the energy required to break the FF bond.

12.

(E) The bond energy of the Xe=O bond is too small to offset the energy required to
break the O=O bond.

1099

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

The Halogens
13.

(M) Iodide ion is slowly oxidized to iodine, which is yellow-brown in aqueous


solution, by oxygen in the air.

Oxidation: { 2I aq
I 2 aq + 2 e } 2

E = 0.535 V

2 H 2 O(l)
Reduction: O 2 g + 4 H + aq + 4 e

Net:

E = +1.229 V

4 I aq + O 2 g + 4 H + aq
2 I 2 aq + 2 H 2 O(l)

Ecell
= +0.694 V

Possibly followed by: I 2 aq + I aq


I3 aq

2 MnF4
2 MnF3 + F2 g

14.

(E) MnF6 2 + 2SbF5


MnF4 + 2SbF6 ;

15.

(M) Displacement reactions involve one element displacing another element from
solution. The element that dissolves in the solution is more active than the element
supplanted from solution. Within the halogen group, the activity decreases from top to
bottom. Thus, each halogen is able to displace the members of the group below it, but
not those above it. For instance, molecular bromine can oxidize aqueous iodide ion but
molecular iodine is incapable of oxidizing bromide ion:

Br2(aq) + 2 I(aq) 2 Br(aq) + I2(aq) however, I2(aq) + 2 Br(aq) NO RXN


The only halogen with sufficient oxidizing power to displace O2(g) from water is F2(g):
2 H2O(l) 4 H+ + O2(g) + 4 e
{F2(g) + 2 e 2 F(aq)} 2

E1/2ox = 1.229 V
E1/2red = 2.866 V

2 F2(g) + 2 H2O(l) 4 H+ + O2(g) + 4 F(aq) Ecell = 1.637 V


The large positive standard reduction potential for this reaction indicates that the reaction will
occur spontaneously, with products being strongly preferred under standard state conditions.
None of the halogens reacts with water to form H2(g). In order to displace molecular hydrogen
from water, one must add a strong reducing agent, such as sodium metal.
16.

(M) We first list the relevant values of halogen properties.


(a)
(b)
(c)
(d)
(e)
(f)

Covalent radius (pm):


Ionic radius(pm):
First ionization energy (kJ/mol):
Electron affinity(kJ/mol):
Electronegativity:
Standard reduction potential:

F
Cl
Br
I
71
99
114
133
133
181
196
220
1681
1251
1140
1008
328.0
349.0
324.6
295.2
4.0
3.0
2.8
2.5
+2.886 V +1.358 V +1.065 V +0.535 V

We can do a reasonably good job of predicting the properties of astatine by


simply looking at the difference between Br and I and assuming that the same
difference exists between I and At.

1100

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

(a)

Covalent radius: 152 pm

(b) Ionic radius: 244 pm

(c)

1st ionization energy: 876 kJ/mol

(d) Electron affinity: 265 kJ/mol

(e)

Electronegativity: 2.2

(f) E 0.005 V to 0.010V

Depending on the technique that you use, you will arrive at different answers.
For example, 260 kJ/mol is a reasonable estimation of the electron affinity by
the following reasoning. The difference between the value for Cl and Br is 24
kJ/mol, the difference between the values for Br and I is 29 kJ/mol, so the
difference between I and At should be about 35 kJ/mol.
17.

(M) (a)
3

1000 m 100 cm 1.03 g 1 lb


1 ton
1 g F 37.996 g F2
mass F2 = 1 km

1 km
1 m
1 cm 3 454 g 2000 lb 1 ton 18.998 g F
3

= 2 109 g F2 = 2 106 kg F2
(b)

Bromine can be extracted by displacing it from solution with Cl2 g . Since there
is no chemical oxidizing agent that is stronger than F2(g), this method of
displacement would not work for F2(g). Even if there were a chemical oxidizing
agent stronger than F2(g), it would displace O 2 (g) before it displaced F2(g).
Obtaining F2(g) would require electrolysis of one of its molten salts, obtained
from seawater evaporate.

18.

(E) Mass F2 = 1.00 103 kg rock

19.

1000 g 1 mol 3 Ca 3 PO 4 2 CaF2


2 mol F

1 kg
1 mol 3 Ca 3 PO 4 2 CaF2
1009 g

19.00 g F 1 kg
= 37.7 kg fluorine

1 mol F 1000 g

(M) In order for the disproportionation reaction to occur under standard conditions, the
E for the overall reaction must be greater than zero. To answer this question, we must
refer to the Latimer diagrams provided in Figure 22-4 and the answer to Practice
Example 22-1B.

(i)

Reduction half reaction (acidic solution)


Cl2(aq) + 2 e 2 Cl(aq) E1/2 red = 1.358 V

(ii)

Oxidation half reaction (acidic solution)


Cl2(aq) + 6 H2O(l) 2 ClO3(aq) + 12 H+(aq) + 10 e E1/2 ox = 1.453 V

Combining (i) 5 with (ii) 1, we obtain the desired disproportionation reaction:


Ecell = 0.095 V
6 Cl2(aq) + 6 H2O(l) 2 ClO3(aq) + 12 H+(aq) + 10 Cl(aq)
Since the final cell voltage is negative, the disproportionation reaction will not occur

1101

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

spontaneously under standard conditions. Alternatively, we can calculate Keq by using


lnKeq = G/RT and G = nFE. This method gives a Keq = 8.6 1017. Clearly,
the reaction will not go to completion under standard conditions.
20.

(D) To find out whether the reaction will go to completion, we must first calculate the
standard potential for the disproportionation of hypochlorous acid (HOCl). As was the
case for Exercise 15, we will use information contained in Fig. 22.4 to answer this
question.

(i)
(ii)
(iii)

2 HOCl(aq) + 2 H2O(l) 2 HClO2(aq) + 4 H+(aq) + 4 e -E(i) = 1.645 V) (oxidation)


2 HOCl(aq) + 2 H+(aq) + 2 e Cl2(aq) + 2 H2O(l)
E(ii) = +1.611 V
Cl2(aq) + 2 e 2 Cl(aq)
E(iii) =+1.358 V

Next we need to determine the potential of the following half reaction using the
relationship between standard free energies and standard potential
(iv)

2 HOCl(aq) + 2 H+(aq) + 4 e 2 Cl(aq) + 2 H2O(l)

E(iv)

We can determine this using half reaction (ii) and(iii) since adding (ii) and (iii) give (iv).
Hence,
4F E(iv) = 2F(1.611 V) + 2F(1.358 V)

So, E(iv) = 1.485 V

Therefore, by adding equation (i) to equation (iv), we can obtain the standard cell voltage for
the disproportionation of HOCl. We divide by 2 to give the target
(i)2
(iv)2

HOCl(aq) + H2O(l) HClO2(aq) + 2 H+(aq) + 2 e


HOCl(aq) + H+(aq) + 2 e Cl(aq) + H2O(l)

-E(i) = 1.645 V)
E1/2 red = 1.485 V

2 HOCl(aq) HClO2(aq) + Cl(aq) + H+(aq)


(disproportionation reaction of HOCl(aq))

Ecell = 0.160 V

Since the standard cell potential is negative, the equilibrium will favor the reactants and
thus the reaction will not go to completion as written (i.e., reactants will predominate at
equilibrium and thus the reaction will be far from complete). Alternatively, we can
calculate Keq from the reaction by using lnKeq = G/RT and G = nFE. This
gives Keq = 3.9 106. Clearly, the reaction will not go to completion because Keq is
very small (reactants strongly predominate at equilibrium, not products).
21.

(M) First we must draw the Lewis structure for all of the species listed. Following this, we
will deduce their electron-group geometries and molecular shapes following the VSEPR
approach.
(a)

BrF3: 28 valence electrons


VSEPR class: AX3E2
Thus BrF3 is T-shaped

1102

F
F

Br

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

(b)

(c)

22.

IF5 42 valence electrons


VSEPR class: AX5E
Thus IF5 is square pyramidal
Cl3IF 36 valence electrons
VSEPR class: AX4E2
Thus Cl3IF is square planar

F
F
F

Cl
Cl

F
I

F
I

Cl

(M) To answer this question we need to apply the VSEPR method to each species:
(i)

(ii)

ClF2+ (total number of valence electrons = 20 e)


Molecular shape: AX2E2 angular (<109.5 due to lone
pairs on Cl atom)

Cl

IBrF(total number of valence electrons = 22 e)


Molecular shape: AX2E3 linear (~180 )

Br

Cl

(iii) OCl2 (total number of valence electrons = 20 e)


Molecular shape: AX2E2 angular (<109.5 due to lone
pairs on O or Cl atom)
Note: ClOCl preferred over ClClO because
all atoms have a formal charge of zero.

Cl

or
Cl

(iv) ClF3 (total number of valence electrons = 28 e)


Molecular shape: AX3E2 T-shaped molecule

F
F

(v)

Cl

SF4(total number of valence electrons = 34 e)


Molecular shape: AX4E See-saw molecular geometry
(or distorted tetrahedron)

Cl

F
F

The VSEPR treatment of each species indicates only IBrF has a linear structure.
Since (i) and (iii) belong to the same VSEPR class (AX2E2), it is not unreasonable to
assume that they have the same bent structure.
23.

(M) (a) The half-reactions are:


Oxidation:
3I- I-3 +2eReduction:
I2 (aq)+2e- 2I- (aq)
_________________________________________________________________________________________________________

Overall: I2 (aq)+I- (aq) I-3 (aq)


From the known value of the equilibrium constant at 25 oC, we can calculate G o and
consequently E o :

1103

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

G o RT ln K nFE o
8.314JK -1mol-1 298.15K ln K 2 96485Cmol-1 E o
8.314JK -1mol-1 298.15K ln 7.7 10 2
E
0.085V
2 96485Cmol-1
(b) Set up the ICE table and solve for the equilibrium concentrations:
I2 (aq) + I (aq) I3 (aq)
0.0010M 0.0050M 0
0.0010-x 0.0050-x
x
x
x
K 7.7 10 2

6
(0.0010 x ) (0.0050 x ) 5.0 10 0.0060 x x 2
o

7.7 10 2 (5.0 10 6 0.0060 x x 2 ) x


7.7 10 2 x 2 5.62 x 3.85 10 3 0
Solving the quadratic equation gives x=7.6510-3 M.
24.

(M) (a) Cl3 has the same structure as I 3 , which is given in Figure 22.7
(b) Set up the ICE table and solve for the equilibrium concentrations:
Cl- (aq) + Cl2 (aq)
Cl 3 (aq)
0
0.0010M 0.0010M
x
0.0010-x 0.0010-x
(0.0010 x ) (0.0010 x ) 0.0010 2 1.0 10 6
K 5.5

x
x
x
6
1.0 10
x
1.8 10 7 M
5.5

Oxygen
25.

(E)(a) 2HgO(s)

2Hg(l) O 2 (g)

(b) 2KClO 4 (s)

2KClO 3 (s) O 2 (g)

26.

(E) (a) O3 g + 2 I aq + 2 H + aq I 2 aq + H 2 O(l) + O 2 g

(b) S s + H 2O l + 3 O 3 g H 2 SO 4 aq + 3 O 2 g
(c) 2 Fe CN 6
27.

aq +

O3 g + H 2 O(l) 2 Fe CN 6

aq +

O 2 g + 2 OH aq

(M) We first write the formulas of the four substances: N 2 O 4 , Al 2 O 3 , P4 O 6 , CO 2 . The


one constant in all these substances is oxygen. If we compare amounts of substance
with the same amount (in moles) of oxygen, the one with the smallest mass of the other
element will have the highest percent oxygen.

3 mol N 2 O 4 contains 12 mol O and 6 mol N: 6 14.0 = 84.0 g N


4 mol Al 2 O 3 contains 12 mol O and 8 mol Al: 8 27.0 = 216 g Al
2 mol P4 O 6 contains 12 mol O and 8 mol P: 8 31.0 = 248 g P

1104

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

6 mol CO 2 contains 12 mol O and 6 mol C: 6 12.0 = 72.0 g C


Thus, of the oxides listed, CO 2 contains the largest percent oxygen by mass.
C
28. (M) 2NH 4 NO 3 (s) 400

2N 2 (g) O 2 (g) + 4H 2 O(g)


2H 2 O 2 (l) 2H 2 O(l) O 2 (g)

2KClO 3 (s)

2KCl(s) 3O 2 (g)

(a) All three reactions have two moles of reactant, and the decomposition of
potassium chlorate produces three moles of O2 g , compared to one mole of
O 2 g for each of the others. The potassium chlorate decomposition produces
the most oxygen per mole of reactant.
(b) If each reaction produced the same amount of O2 g , then the one with the
lightest mass of reactant would produce the most oxygen per gram of reactant.
When the first two reactions are compared, it is clear that 2 mol H 2 O 2 have less
mass than 2 mol NH 4 NO 3 . (Notice that each mole of NH 4 NO 3 contains the
amounts of elements2 mol H and 2 mol Opresent in each mole H 2 O 2 plus
some more.) So now we need to compare hydrogen peroxide with potassium
chlorate. Notice that 6 H 2 O 2 produces the same amount of O2 g as 2 KClO 3 .
6 mol H 2 O 2 has a mass of 34.01 6 = 204.1 g , while 2 mol KClO 3 has a mass
of 122.2 2 = 244.2 g . Thus, H 2 O 2 produces the most O 2 g per gram of
reactant.
29.

(M) Recall that fraction by volume and fraction by pressure are numerically equal.
Additionally, one atmosphere pressure is equivalent to 760 mmHg. We combine these
two facts.

P{O3 } = 760 mmHg


30.

0.04 mmHg of O3
= 3 105 mmHg
10 mmHg of atmosphere
6

(M)

0.08206 L atm
1
mol
O
12
3
220 K
5 10 molecules

molecule
mol K

6.022 1023

nRT
mole
P

1L
V
1 cm3
1000 cm 3
760 mmHg
= 1.1 104 mmHg
P = 1.5 107 atm
1 atm

1105

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

31.

(M) The electrolysis reaction is 2H 2O(l) electrolysis

2H 2 (g) O 2 (g) . In this reaction, 2


moles of H 2 g are produced for each mole of O2 g . By the law of combining
volumes, we would expect the volume of hydrogen to be twice the volume of oxygen
produced. (Actually the volumes are not exactly in the ratio of 2:1 because of the
different solubilities of oxygen and hydrogen in water.)

32.

(M) The electrolysis reaction is 2H 2O(l) electrolysis

2H 2 (g) O 2 (g) . In this reaction, 2

moles of water are decomposed to produce each mole of O2 g . We use the data in the
problem to determine the amount of O 2 g produced, which we then convert to the
mass of H 2 O needed.

1L
1 atm
736.7 mmHg 760 mmHg 22.83 mL 1000 mL 2 mol H O
2
mass H 2 O(l)=

0.08206 L atm
1 mol O 2
(25.0 273.2)K
mol K
18.02 g H 2 O

= 0.03259 g H 2 O decomposed
1 mol H 2 O

33.

(D) Since the pKa for H2O2 had been provided to us, we can find the solution pH simply
by solving an I.C.E. table for the hydrolysis of a 3.0 % H2O2 solution (by mass). Of
course, in order to use this method, the mass percent must first be converted to molarity.
We must assume that the density of the solution is 1.0 g mL1.

[H2O2] =

3.0 g H 2 O 2
1 mol H 2 O 2
1 g solution
1000 mL
= 0.88 M

1L
100 g solution 1 mL solution 34.015 g H 2 O 2

The pKa for H2O2 is 11.75. The Ka for H2O2 is therefore 1011.75 or 1.8 1012. By
comparison with pure water, which has a Ka of 1.8 1016 at 25 C, one can see that
H2O2 is indeed a stronger acid than water but the difference in acidity between the two
is not that great. Consequently, we cannot ignore the contribution of protons of pure
water when we work out the pH of the solution at equilibrium.
Reaction:
Initial:
Change:
Equilibrium:

K = 1.8 10-12

H2O2(aq) + H2O(l)

0.88 M
x M
(0.88x) M
(~0.88 M)

So, 1.8 1012 =


x=

1.0 107 M
+xM
(1.0 107 + x)M

x(x 1.0 107 )


~0.88

1.0 x 107

H3O+(aq)

HO2(aq)
0M
+x M
xM

x2 + 1.0 107x 1.58 1012 = 0

1.0 1014 4(1.58 10 12 )


2
1106

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

The root that makes sense in this context is x = 1.2 106 M.


Thus, the [H3O+] = 1.2 106 M + 1.0 107 M = 1.3 106 M
Consequently, the pH for the 3.0 % H2O2 solution (by mass) should be 5.89
(i.e., the solution is weakly acidic)
34.

(E) Oxide ion reacts essentially quantitatively with water to form hydroxide ion.
Li 2 O s + H 2 O l
2 Li + aq + 2 OH aq

We first calculate OH and then the solutions pH.


0.050 g Li 2 O 1000 mL 1 mol Li 2O 2 mol OH
OH =
= 0.00446 M

750.0 mL
1L
29.88 g Li 2 O 1 mol Li 2 O
pOH = log 0.00446 = 2.350

35.

pH = 14.000 pOH = 14.000 2.350 = 11.650

(E) 3 O = O
2 O O O

Bonds broken: 3 (O=O) = 3 498 kJ/mol = 1494 kJ/mol


Bonds formed: 4 (O O)
H o = +285 kJ/mol = bonds broken bonds formed = 1494 kJ/mol 4 (O O)
4 (O O) = 1494 kJ/mol 285 kJ/mol = 1209 kJ/mol
O O = 1209 kJ/mol + 4 = 302 kJ/mol
36.

(E)

3 O O

Average bond energy =


37.

O==O +OO
=
2

498 +142
2

(all gaseous species)

kJ
mol = 320 kJ
mol

(E) (a) H 2S, while polar, forms only weak hydrogen bonds. H 2 O forms much
stronger hydrogen bonds, leading to a higher boiling point.
(b)

38.

2 O O O

All electrons are paired in O3 , producing a diamagnetic molecule and thus a


liquid at room temperature.

(M) (a) O

The OO bond in O 2 is a double bond, which should be short (121 pm). That in
O3 is a one-and-a-half bond, of intermediate length (128 pm). And that in
H 2 O 2 is a longer (148 pm) single bond.

1107

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

(b)

The O 2 ion has one less electron than does the O 2 molecule. Based on Lewis

structures,
O O
O O
+

one would predict that O 2 would have a bond order of 1.5, thereby making its
OO bond weaker than the double bond of O 2 , and therefore longer, in
contradiction to the experimental evidence. The molecular orbital picture of the
two species suggests the opposite. According to this model, O2 has a bond order of
2.0 while that for O2+ is 2.5. Thus MO theory predicts a shorter bond for O2+.
1s

1s

2s

2s

2p

2p

2p

2p

O2

bond order = no. bonding electrons no. antibonding electrons 2


bond order = 10 6 + 2 = 2.0
1s

1s

2s

2s

2p 2p

2p

2p

O2
bond order = no. bonding electrons no. antibonding electrons 2 = 10 5 2 = 2.5
39.

(M) Reactions that have Keq values greater than 1000 are considered to be essentially
quantitative (i.e., they go virtually 100% to completion). So to answer this question we need
only calculate the equilibrium constant for each reaction using the equation Ecell =
(0.0257/n)lnKeq.
(a)

H2O2(aq) + 2 H+(aq) + 2 e

2 H2O(l)

2 I (aq)

I2(s) + 2 e

E1/2red = +1.763 V
E1/2ox = 0.535 V

H2O2(aq) + 2 H+(aq) +2 I(aq)

I2(s) + 2 H2O(l) E1/2cell = +1.228 V(n = 2 e )

1.228 V 2
= 95.56
Keq = 3.2 1041
0.0257 V
Therefore the reaction goes to completion (or very nearly so).
lnKeq =

(b)

O2(g) + 2 H2O(l) +4 e
4 OH (aq)

4 Cl(aq)
2 Cl2(g) + 4 e

E1/2red = +0.401 V
E1/2ox = 1.358 V

O2(g) + 2 H2O(l) +4 Cl(aq)


2 Cl2(g) + 4 OH (aq)

lnKeq =

-0.957 V 4
0.0257 V

= 148.95

1108

Keq = 2.1 1065

E1/2cell = 0.957 V
(n = 4 e)

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

The extremely small value of Keq indicates that reactants are strongly preferred and
thus, the reaction does not even come close to going to completion.
(c)

O3(g) + 2 H+(aq) + 2 e

O2(g) + H2O(l)
+

Pb2+(aq) + 2 H2O(l)

PbO2(s) + 4H (aq) + 2 e

E1/2red = +2.075 V
E1/2ox = 1.455 V

O3(g) + Pb2+(aq) + H2O(l)

PbO2(s) + 2 H (aq) + O2(g) Ecell = 0.620 V

0.62 V 2
= 48.25 Keq = 9.0 1020
0.0257 V
Therefore the reaction goes to completion (or very nearly so).

HO2(aq) + H2O(l) + 2 e
E1/2red = +0.878 V

3 OH (aq)

E1/2ox = 1.065 V
2 Br(aq)

Br2(l) + 2 e

lnKeq =

(d)

HO2(aq) + H2O(l) + 2 Br(aq)

Br2(s) + 3 OH (aq)

lnKeq =

-0.187 V 2
0.0257 V

= 14.55

E1/2cell = 0.187 V

Keq = 4.8 107

The extremely small value of Keq indicates the reaction heavily favors reactants at
equilibrium and thus, the reaction does not even come close to going to completion.
40.

(M) (a) HgO(s)

Hg(l) + 1/2 O2(g)

(b)
(c)

KClO4(s)

KCl(s) + 2 O2(g)

Hg(NO3)2(s)

Hg(l) + 2 NO2(g) + O2(g)


or

Depending on
the temperature

Hg(NO2)2(g) + O2(g)
Hg(NO3)2(s)

(d)

41.

H2O2(l)

H2O(l) + 1/2 O2(g)

(M) The reaction is 2 KClO3(s)


2 KCl(s) + 3 O2(g).
MnO2 (s)

1.0 gKClO 3

1 mol
3 molO 2
32 gO 2

0.391gO 2
122.549 g 2 molKClO 3 1molO 2

nRT 0.01224 8.314 JK 1mol 1 298.15K


pV nRT V

30L
1atm
p
101kPa
101.325kPa

42.

2 Hg(l) + O2(g).
(M) The reaction is 2 HgO(s)

1109

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

1 mol
1 molO 2

2.31 10 3 mol O 2
216.589 g HgO 2 mol HgO
(756 23.76) 752mmHg

1.0 g HgO
pO2

pV nRT V

nRT 2.31 10 3 8.314 JK 1mol 1 298.15K

5.8L
1atm
p
752mmHg
760mmHg

Sulfur
43.

(E) (a) ZnS, zinc sulfide


(c) K 2S2 O3 , potassium thiosulfate

(b)
(d)

KHSO3 , potassium hydrogen sulfite


SF4 , sulfur tetrafluoride

44.

(E) (a) CaSO 4 2H 2 O , calcium sulfate dehydrate

(b)

H 2S aq , hydrosulfuric acid

(d)

H 2S2 O7 aq , disulfuric acid

(c)
45.

NaHSO 4 , sodium hydrogen sulfate

(M) (a) FeS s + 2 HCl aq


FeCl2 aq + H 2S aq MnS(s), ZnS(s), etc. also are

possible.
(b)

CaSO3 s + 2 HCl aq
CaCl2 aq + H 2 O(l) + SO 2 g

(c)

Oxidation:
Reduction:

(d)

46.

SO 2 aq + 2 H 2 O(l)
SO 4

aq + 4H + aq + 2 e
MnO 2 s + 4 H + aq + 2 e
Mn 2+ aq + 2 H 2O(l)
2

Net:

SO 2 aq + MnO 2 s
Mn 2 aq + SO 4

Oxidation:

S2 O3

aq

Reduction:

2SO 2 g + 2 H + aq + 4e
aq + H 2O(l)
2
S2 O3 aq + 6 H + aq + 4 e
2S s + 3H 2 O(l)

Net:

S2 O3

S s + SO 2 g + H 2 O(l)
aq + 2 H + aq

(M) (a) S s + O 2 g
SO 2 g
2 Na s + 2 H 2 O(l)
2 NaOH aq + H 2 g
2 NaOH aq + SO 2 g
Na 2SO3 aq + H 2 O(l)

(b)

S s + O 2 g
SO 2 g

SO 2 g + 2 H 2 O(l) + Cl2 g
SO 4

aq + 2 Cl aq + 4 H + aq
2 Na s + 2 H 2 O(l)
2 NaOH aq + H 2 g
2
2 NaOH aq + 2 H + aq + SO 4 aq
Na 2SO4 aq + 2 H 2 O(l)

1110

cell

= +1.19V

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

(c)

S s + O 2 g
SO 2 g
2 Na s + 2H 2 O(l)
2 NaOH aq + H 2 g
2 NaOH aq + SO 2 g
Na 2SO3 aq + H 2 O(l)
Na 2SO3 aq + S s
NaS2 O3 aq

(Thus, one must boil the reactants in an alkaline solution.)


47.

(M) The decomposition of thiosulfate ion is more highly favored in an acidic solution. If
the white solid is Na2SO4, there will be no reaction with strong acids such as HCl. By
contrast, if the white solid is Na2S2O3, SO2(g) will be liberated and a pale yellow
precipitate of S(s,rhombic) will form upon addition of HCl(aq).
2
S2 O3 aq + 2 H + aq
S s + SO 2 g + H 2 O(l)

Consequently, the solid can be identified by adding a strong mineral acid such as HCl(aq).
48.

(M) Sulfites are easily oxidized to sulfates by, for example, O 2 in the atmosphere. On the
other hand, there are no oxidizing agents naturally available in reasonable concentrations
2
2
that can oxidize SO 4 to a higher oxidation state, such as in S2 O8 . Similarly, the

atmosphere of Earth is an oxidizing one, reducing agents are not present to reduce SO 4
to a species with a lower oxidation state, except in localized areas.
49.

(D) Na + aq will not hydrolyze, being only very weakly polarizing. But HSO 4 aq

will ionize further, K 2 = 1.1102 for HSO 4 aq . We set up the situation, and solve

the quadratic equation to obtain H 3O + .

12.5 g NaHSO 4 1000 mL 1 mol NaHSO 4


1 mol HSO 4
HSO 4 =

250.0 mL soln 1 L soln 120.1 g NaHSO 1 mol NaHSO = 0.416 M


4
4

2
+
SO 4 aq + H 3O aq
Reaction:
HSO 4 aq + H 2 O(l)
Initial:
0.416 M
0M

0M
x M

Changes:
+ xM
+ xM
xM
xM
Equil:
0.416 x M
Noting the moderate value of the equilibrium constant (K = 0.011), the full quadratic
equation must be solved (i.e. no assumption can be made here).
H 3 O + SO 4 2
x2
K2 =
=
0.011
=
0.416 x
HSO 4

x 2 = 0.0046 0.011 x

0 = x 2 + 0.011 x 0.0046
b b 2 4ac 0.011 1.2 104 +1.8 102
=
= 0.062 = H 3O +
2a
2
pH = log 0.062 = 1.21

x=

1111

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

50.

2
SO 4 aq + 2H + aq + 2 e }
aq + H 2O(l)

Mn 2+ aq + 4 H 2 O(l)} 2
Reduction: {MnO 4 aq + 8 H + aq + 5e

(M) Oxidation: {SO3

Net: 5 SO3

2
5SO 4 aq + 2 Mn 2+ aq + 3 H 2 O(l)
aq + 2 MnO4 aq + 6 H + aq
2

1L
0.0510 mol MnO 4
5 mol SO3
1 mol Na 2SO3
mass Na 2SO3 = 26.50 mL

2
1000 mL
1 L soln
2 mol MnO 4
1 mol SO3

51.

126.0 g Na 2SO3
= 0.426 g Na 2SO3
1 mol Na 2SO3

(M) The question is concerned with assaying for the mass percent of copper in an ore. The
assay in this instance involves the quantitative determination of the amount of metal in an ore
by chemical analysis. The titration for copper in the sample does not occur directly, but
rather indirectly via the number of moles of I3(aq) produced from the reaction of Cu2+ with
I:
2 Cu2+ + 5 I(aq) 2 CuI(s) + I3(aq)
The number of moles of I3(aq) produced is determined by titrating the iodide-treated sample
with sodium thiosulfate. The balanced oxidation reaction that forms the basis for the titration is:
I3(aq) + 2 S2O32(aq) 3 I(aq) + S4O62(aq)
The stoichiometric ratio is one I3(aq) reacting with two S2O32(aq) in this titration.
The number of moles of I3 formed

2
1 mol I 3
0.1000 moles S2 O 3

= 6.060 104 moles I3


2
2
2 mol S2 O 3
1 L S2 O 3
2+
Therefore, the number of moles of Cu released when the sample is dissolved is
2 mol Cu 2
= 6.060 104 moles I3
= 1.212 103 moles of Cu2+

1 mol I3
Consequently, the mass percent for copper in the ore is

= 0.01212 L S2O32(aq)

63.546 g Cu 2
1
100% = 7.002%

2
1.100 g of Cu ore
1 mol Cu
(M) First you must realize that pressure and temperature are irrelevant to answering this
question. The reaction is
Pb2+(aq) + H2S(aq) 2 H+(aq) + PbS(s)
This means that there is a one to one relationship between the moles of PbS and H2S.
If we realize that 1 m3 is 1000 L (40 times larger than the sample used), then we can
calculate the mass of PbS in 1 m3, namely, 40 0.535 g PbS = 21.4 g PbS.
1.212 103 moles of Cu2+

52.

The mass of sulfur can be calculated using stoichiometry.


1 mol S
32.066 g S
1 mol PbS
mass of S = 21.4 g PbS
= 2.87 g S (per 1 m3)

239.3 g PbS 1 mol PbS 1 mol S

1112

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

53.
54.

Alternatively, knowing that the mass percent of S in PbS is 13.40 %. We can calculate the
13.40 g S
= 2.87 g S (per 1 m3 natural gas).
mass of sulfur as: 21.4 g PbS
100 g PbS
(E) (a) +4; (b) +5; (c) -2 and (d) +4
(E) (a) +1; (b) +2; (c) +2 and (d) +2.5

Nitrogen Family
55.

(M) (a) The Haber-Bosch process is the principal artificial method of fixing
2 NH 3 g
atmospheric nitrogen. N 2 g + 3 H 2 g
(b) The first step of the Ostwald process:
850 C, Pt
4NH3 (g) 5 O 2 (g)
4NO(g) 6H 2 O(g)
(c)

56.

The second and third steps of the process:


2 NO g + O 2 g 2 NO 2 g
3 NO 2 g + H 2 O l 2 HNO 3 aq + NO g

400C
(M) (a) 2 NH 4 NO3 (s)
2 N 2 (g) + O 2 (g) + 4 H 2 O(g)

The equation was balanced by inspection, by realizing first that each mole of
NH 4 NO 3 s would produce 1 mol N 2 g and 2 mol H 2O l , with 1 mol O [or
1/2 mol O2 g ] remaining.
(b)
(c)

NaNO 3 s NaNO 2 s +1 / 2 O 2 g

2 NaNO 3 s 2 NaNO 2 s + O 2 g

or

Pb NO 3 2 s PbO s + 2 NO 2 g +1 / 2 O 2 g
2 Pb NO 3 2 s 2 PbO s + 4 NO 2 g + O 2 g

57.

(D) Begin with the chemical formulas of the species involved:

Na 2CO 3 aq + O 2 g + NO g NaNO 2 aq
Oxygen is reduced and nitrogen (in NO) is oxidized. We use the ion-electron method.
Two couples:
Balance oxygens:

NO g NO2 aq

H 2 O + NO NO 2

O 2 products

and

O2 2 H 2O

Balance hydrogens:

H 2 O + NO NO 2 + 2 H

4 H + + O2 2 H 2O

Balance charge:

H 2 O + NO NO 2 + 2 H + + e

Combine:

4 H 2 O + 4 NO + 4 H + + O 2 2 H 2 O + 4 NO 2 + 8 H +

Simplify:

2 H 2 O + 4 NO + O 2 4 NO 2 + 4 H +

Add spectator ions:

4 Na + + 2CO 3 4 Na + + 2CO 3
2 Na 2 CO3 + 2 H 2 O + 4 NO + O 2 4 NaNO2 + 2 H 2 O + 2 CO2

4 e + 4 H + + O2 2 H 2O

1113

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

simplify:
2 Na 2 CO 3 aq + 4 NO g + O 2 g 4 NaNO 2 aq + 2 CO 2 g

58.

63.01 g HNO 3
1 mol HNO 3
(E) mass % HNO 3
100% 67% HNO 3
1000 mL
141
. g
1 L soln

1L
1 mL soln

59.

(E) 75 109 gal

60.

(E) 2 NH3(g) + 3 NO(g) 5/2 N2(g) + 3 H2O(g) (or, dividing by 2):

15 mol HNO 3

15 miles
5 g
1 kg
= 6 109 kg of nitrogen oxides released.

1 gal
1 mile 1000 g

NH3(g) + 3/2NO(g) 5/4N2(g) + 3/2H2O(g)

Hrxn = Hf products - Hf reactants


Hrxn = [5/4 mol(0 kJ mol-1) + 3/2 mol(-241.8 kJ mol-1)]
-[3/2 mol(90.25 kJ mol-1) + 1 mol(-46.11 kJ mol-1)] = -452 kJ
61.

62.

63.

N 2 O 4 g
(M) (a) 2 NO 2 g

HNO2(aq) + N2H5+(aq) HN3(aq) + 2H2O(l) + H+(aq)


HN3(aq) + HNO2(aq) N2(g) + H2O(l) + N2O(g)

(b)

i)
ii)

(c)

H3PO4(aq) + 2 NH3(aq) (NH4)2HPO4(aq)

(M) (a) 3 Ag s + 4 H + aq + 4 NO3 aq


3 AgNO3 aq + NO g + 2 H 2O(l)

(b)

2 CO 2 g + 4 H 2 O l + N 2 g
CH3 2 NNH 2 l + 4 O2 g

(c)

NaH2PO4(s) + 2Na2HPO4(s)
2H2O(l) + Na5P3O10(s)

(M)
(a) (CH3)2NNH2:
Each molecule has a total of
26 valence electrons.

H
H C
H

H C H
H

(b)

ClNO2:
Each molecule has a total of
24 valence electrons.

O
Cl

1114

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

(c)

H3PO3
Each molecule has a total of
26 valence electrons.

O
H

H
64.

(M) Hyponitrous acid is a weak diprotic acid while nitramide has an amide
group, NH 2
H

65.

66.

67.

H O

H O N N O H

H N O N O

H N N O

Both Lewis structures for nitramide are plausible based on the information supplied. To
choose between them would require further information about #2 and #3, such as
whether the molecule contains a nitrogen-nitrogen bond. Experimental evidence
indicates the structure adopted is the one with the nitrogen-nitrogen bond, i.e. structure
#3.
2
(E) (a) HPO 4 , hydrogen phosphate ion
(b) Ca 2 P2 O7 , calcium pyrophosphate or calcium diphosphate
(c) H 6 P4 O13 , tetrapolyphosphoric acid
(E) (a) HONH 2 , hydroxylamine
(b) CaHPO 4 , calcium hydrogen phosphate
(c) Li3 N , lithium nitride
(M) (i) 2 H+(aq) + N2O4(aq) + 2 e 2 HNO2(aq)
(ii)
2 HNO2(aq) + 2 H+(aq) + 2 e 2 NO(aq) + 2 H2O(l)

(iii)

N2O4(aq) + 4 H+(aq) + 4 e 2 NO(aq) + 2 H2O(l)

E1 = +1.065 V
E2 = +0.996 V
E3 = ? V

Recall that G = nFE and that G values, not standard voltages are additive for
reactions in which the number of electrons do not cancel out.
So, 4FE3 = 2F(1.065 V) + 2F(0.996 V) E3 = 1.031 V (4 sig figs)
68.

(M) (i) 2 NO3(aq) + 2 H2O(l) + 2 e N2O4(aq) + 4 OH(aq)


(ii)
N2O4(aq) + 2 e 2 NO2(aq)

(iii)

E1 = 0.86 V
E2 = +0.87 V

2 NO3(aq) + 2 H2O(l) + 4 e 2 NO2(aq) + 4 OH(aq) E3 = ? V

Recall that G = nFE and that G values, not standard voltages, are additive for
reactions in which the numbers of electrons do not cancel out.
So,

4FE3 = 2F(0.86 V) + 2F(0.87 V)


4FE3 = 1.72F 1.74 F = 0.02F (1 sig fig)
E3 = 0.005 V (1 sig fig)
1115

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

69.

(M) (a)The nitrogen atom cannot bond to five fluorine atoms because, as a
second-row element, it cannot accommodate more than four electron pairs.
(b) the NF3 molecule is trigonal pyramidal. The lone pair on the N atom causes the
FNF
bond angle to decrease from the ideal tetrahedral bond angle of 109 to
102.5.

70. (M) On the basis of electronegativities, the NH and NF bonds are both quite polar.
However, the polarities of the bonds are opposite. In NH3, the H atoms are slightly
positive and in NF3, the N atom is slightly positive. The lone pair on N presumably
enhances the bond dipoles in NH3 and diminishes the bond dipoles in NF3.
Consequently, the NH3 is very polar and NF3 is less so.

Hydrogen
71.

72.

(M) The four reactions of interest are: (Note: H combustion = Hf products - Hf


reactants)

CH4(g) + 2 O2(g) CO2(g) + 2 H2O(l)


(Molar mass CH4 = 16.0428 g mol-1)

H combustion = -890.3 kJ

C2H6(g) + 7/2 O2(g) 2 CO2(g) + 3 H2O(l)


(Molar mass C2H6 = 30.070 g mol-1)

H combustion = -1559.7 kJ

C3H8(g) + 5 O2(g) 3 CO2(g) + 4 H2O(l)


(Molar mass C3H8 = 44.097 g mol-1)

H combustion = -2219.9 kJ

C4H10(g)+13/2 O2(g) 4 CO2(g) + 5 H2O(l)


(Molar mass C4H10 = 58.123 g mol-1)

H combustion = -2877.4 kJ

(M) Using the answers obtained in question 57, the per gram energy release is:
CH4(g) -55.5 kJ; C2H6(g) -51.9 kJ; C3H8(g) -50.3 kJ; C4H10(g) -49.5 kJ
(a)
(b)
(c)

73.

(E) (a) 2 Al s + 6 HCl aq 2 AlCl 3 aq + 3 H 2 g


(b) 3 CO g + 7 H 2 g C 3H 8 g + 3 H 2 O g
(c)

74.

C4H10(g) evolves the most energy on a per mole basis (-2877.4 kJ).
CH4(g) evolves the most energy on a per gram basis (-55.5 kJ).
CH4(g) is the most desirable alkane from the standpoint of emission, producing
the least quantity of CO2(g) per mole and/or per gram of fuel burned (as well per
kJ of energy produced).

MnO 2 (s) 2H 2 (g)

Mn(s) 2H 2 O(g)

(M) (a) 2H 2 O(l) electricity

O 2 (g) 2H 2 (g)
(b) 2 HI aq + Zn s ZnI2 aq + H 2 g Any moderately active metal is
suitable.
(c) Mg s + H 2SO 4 aq MgSO 4 aq + H 2 g Any strong acid is suitable.

1116

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

(d)
75.

CO g + H 2 O g CO 2 g + H 2 g

(M) CaH 2 s + 2 H 2 O(l) Ca OH 2 aq + 2 H 2 g

Ca s + 2 H 2 O(l) Ca OH 2 aq + H 2 g

2 Na s + 2 H 2 O(l) 2 NaOH aq + H 2 g
(a)

The reaction that produces the largest volume of H 2 g per liter of water also
produces the largest amount of H2(g) per mole of water used. All three reactions
use two moles of water and the reaction with CaH 2 s produces the most H2(g).

(b) We can compare three reactions that produce the same amount of hydrogen; the
one that requires the smallest mass of solid produces the greatest amount of H 2
per gram of solid. The amount of hydrogen we will choose, to simplify matters,
is 2 moles, which means that we compare 1 mol CaH 2 (42.09 g) with 2 mol Ca
(80.16 g) and with 4 mol Na (91.96 g). Clearly CaH 2 produces the greatest
amount of H 2 per gram of solid.
76.

(M) The balanced equation is C17 H 33COOH l + H 2 g C17 H 35 COOH s . One


mole of oleic acid requires one mole of H 2 g .

nRT

L atm
298 K
0.95 L calculated
mol K

23.5 L H 2 (g)
1 atm
1.0 L produced
752 mm Hg
760 mmHg

1.00 mol 0.08206

77. (M) Greatest mass percent hydrogen:


The atmosphere is mostly N2(g) and O2(g) with only a trace of hydrogen containing gas
molecules. Seawater is H2O(l), natural gas is CH4(g) and ammonia is NH3(g). Each of
these compounds has one non-hydrogen atom, and the non-hydrogen atoms have
approximately the same mass (~14 + 2 g mol-1). Since CH4 has the highest hydrogen
atom to non-hydrogen atom ratio, this molecule has the greatest mass percent hydrogen.
78.

(M) The reaction is CaH 2 s + 2 H 2O l Ca OH 2 aq + 2 H 2 g

First we calculate the amount of H 2 g needed and then the mass of CaH 2 s
required.
1 atm
235 L
PV
760 mmHg
mol H 2

9.29 mol H 2
RT 0.08206 L atm mol 1K 1 (273.2 19.7) K
722 mm Hg

mass CaH 2 = 9.29 mol H 2

1 mol CaH 2 42.09 g CaH 2

= 196 g CaH 2
2 mol H 2
1 mol CaH 2
1117

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

79. (M) NH2 has 8 valence electrons (and is isoelectronic with H2O). The first four MOs

are fully occupied. Because the 2px orbital on N is strongly bonding in the bent
configuration, as shown in Figure 22-27, the energy of the NH2 will be much lower
for the bent configuration. (The same argument applies to H2O.) On the basis of
molecular orbital theory, we expect that NH2 will be bent.
80. (M) NH2+ has 6 valence electrons and is isoelectronic with CH2. On this basis, we

anticipate that structure of NH2+ will be similar to that of CH2: a slightly bent
molecule with two unpaired electrons.

INTEGRATIVE AND ADVANCED EXERCISES


81.

82.

1
O2(g)
2
H2O(l). Step (2) ensures that unreacted hydrogen from step (1) is also converted to
H2O(l). The dehydrated zeolite has a very strong affinity for water molecules and
thus, H2O(l) is removed from the gas mixture.
(M) In step (1), oxygen is converted to H2O by the reaction H2(g) +

(M) The AsF6 is octahedral. The FAsF bond angles are 90. The most important
Lewis structure for the HCNKrF+ ion is shown below. If we assume that the lone
pairs on Kr occupy equatorial positions (to minimize lone pair repulsions), then the
HCNKrF+ ion is linear:

HC N Kr:F:
+1

2 H 2 (g) O 2 (g) . In this reaction, 2


83. (E) The electrolysis reaction is 2 H 2 O(l) electroysis
moles of water are decomposed to produce one mole of oxygen and two moles of
hydrogen. We use the data in the exercise to determine the volumes of oxygen and
hydrogen produced.
n(H 2O)
V (O 2 )=

V (H 2 )=

17.3g
m

0.96mol
M 18.00g/mol

1molO 2
0.08206Latm/molK 298.15K
nRT
0.96molH 2O

11.8L
1atm
p
2molH 2O
755mmHg
760mmHg
2molO 2
0.08206Latm/molK 298.15K
nRT
0.96molH 2O

23.6L
1atm
p
2molH 2O
755mmHg
760mmHg

1118

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

84. (M) NaNO2 decolorizes acidic solution of KMnO4 according to the following balanced
chemical equation:
2KMnO4 + 3H2SO4 + 5NaNO2 5NaNO3 + K2SO4 + 2MnSO4 + 3H2O
NaNO3 does not react with acidic solution of KMnO4.
85. (D) First we balance the equation, then determine the number of millimoles of NH3(g)
that are produced, and finally find the [NO3] in the original solution.
NH 3 (g)
The skeleton half-equations: NO3 (aq)

Zn(s)
Zn(OH) 42- (aq)

Balance O's and H's: NO3 (aq)


NH 3 (g) 3 H 2 O(l)

NO3 (aq) 9 H (aq)


NH 3 (g) 3 H 2 O(l)
Balance charge and add OH (aq)

NH3 (g) 9 OH (aq)


NO3 (aq) 6 H 2 O(l) 8 e

Zn(OH) 2-4 (aq) 2 e


Add OH (aq)'s and then electrons: Zn(s) 4 OH (aq)

Oxidation:
Reduction:

{ Zn(s) 4 OH (aq)
Zn(OH)2-4 (aq) 2 e }

NO3 (aq) + 6 H 2 O(l) + 8 e-


NH 3 (g) + 9 OH - (aq)

Net: NO3 (aq) + 4 Zn(s) + 6 H 2 O(l) + 7 OH - (aq)


Zn(OH)2-4 (aq) + NH3 (g)
The titration reactions are the following.
HCl(aq) NaOH(aq)
NaCl(aq) H 2 O(l)
mmol excess HCl 32.10 mL

NH 3 (aq) HCl(aq)
NH 4 Cl(aq)

0.1000 mmol NaOH


1 mmol HCl

3.210 mmol HCl


1 mL soln
1 mmol NaOH

0.1500 mmol HCl


7.500 mmol HCl
1 mL soln
1 mmol NH 3
produced (7.500 3.210) mmol HCl
4.290 mmol NH 3
1 mmol HCl

mmol HCl at start 50.00 mL


mmol NH 3

[NO3

1 mmol NO3
4.290 mmol NH
3 1 mmol NH 3
0.1716 M
]
25.00 mL soln

Notice that it was not necessary to balance the equation, since NO3 and NH3 are the only
nitrogen-containing species involved, and thus they must be in a one-to-one molar ratio.
86. (M) First we compute the root-mean-square speed of O at 1500 K.
3
3RT
3 8.314 J mol 1 K 1 1500 K

1.5 10 m/s
rms
0.0160 kg/mol
M
Kinetic Energy =
0.0160 kg/mol
KE 12 mu 2 0.5
(1.5 103 m/s) 2 3.0 1020 J/atom
6.022 1023 atoms/mol

1119

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

87. (M) Reduction: { 2 NO-3(aq) + 10 H + (aq) + 8 e- N 2O(g) + 5 H 2O(l) } 7


Oxidation:{C6 H11O(aq)+3H 2O(l) HOOC(CH 2 )4COOH(aq)+7H + (aq)+7e- } 8
Net: 14 NO-3 (aq) + 14 H + (aq) + 8 C6 H11O(aq) 7 N 2O(g) + 8 HOOC(CH 2 )4COOH(aq) + 11 H 2O(l)

88. (D) The Lewis structures for the two compounds are drawn below. The four bonded
groups in XeO4 and no lone pairs on the central atom give it a tetrahedral shape in which
there are four oxygen atoms on the periphery of the molecule. These rounded tetrahedral
should not stick well together. In fact, each oxygen is slightly negatively charged and
they should repel each other. Thus, we expect weak intermolecular forces between
XeO4 molecules. In XeO3, on the other hand, the three bonds and one lone pair produces
a trigonal pyramidal molecule in which the central Xe (carrying a slight positive charge),
is exposed to other molecules. There thus can be strong dipole-dipole forces leading to
strong intermolecular forces and a relatively high boiling point vis--vis XeO4.
O
O

4+

Xe

3+

Xe

Note: You can also expand the octets to reduce


formal charges. There are a number of
resonance
forms,
however,
Lewis
structures(octets) are shown.

89. (E) The N center in the ammonium ion is the reducing agent, while Cl in the perchlorate anion
is the oxidizing agent.
2 NH 4 ClO 4 (s)
N 2 (g) 4 H 2 O(g) Cl 2 (g) 2 O 2 (g)
90. (E)Hf = Bonds broken in reactants Bonds formed in products
(a) Cl2(g) + F2(g) ClF(g)
Hf = (159 kJ) + (243 kJ) 251 kJ = -50 kJ
(b) O2(g) + F2(g) FOF(g)
Hf = (498 kJ) + (159 kJ) 2(213 kJ) = -18 kJ
(c) O2(g) + Cl2(g) ClOCl(g) Hf = (498 kJ) + (243 kJ) 2(205 kJ) = +82 kJ
(d) N2(g) + 3/2 F2(g) NF3(g)
Hf = (946 kJ) + 1.5 (159 kJ) 3(280 kJ) = -128.5 kJ
91. (E) The electrode reaction is:

F2 (g) 2 e
2 F (aq)

G o 2 G of [F (aq)] G of [F2 (g)] 2( 278.8 kJ/mol) (0 kJ/mol)


G o 557.6 kJ/mol 2nFE o
557.6 10 3 J/mol
o
E
2.890 V
2 96,485 C/mol
This value compares favorably with the value of +2.866 V in Appendix D.
92. (M) Each simple cubic unit cell has one Po atom at each of its eight corners, but each corner
is shared among eight unit cells. Thus, there is a total of one Po atom per unit cell. The edge
of that unit cell is 335 pm. From this information we obtain the density of polonium.

1120

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

209 g Po
1 mol Po

6.022 10 23 Po atoms 1 mol Po 9.23 g/cm 3


3

1m
100 cm
335 pm 12

1
m
10
pm

1 Po atom
density

93. (M) First we write the molecular orbital diagram of each of the species. From each
molecular orbital diagram we determine the number of bonding electrons (b) and the number
of antibonding electrons (*) and thus the bond order [(number of bonding electrons
number of antibonding electrons) 2 ]. Species with high bond order have strong bonds,
which are short. Those with low bond order have weak bonds, which are long.

Number of e+

1sb

1s*

b
*
2s
2s
2b p 2b p

2* p

2* p Antibonding

Bond
order

(2 8) 1 =
15

2.5

O2

(2 8) = 16

O2

(2 8) + 1 =
17

1.5

O22 (2 8) + 2 =
18

1.0

O2

We have only listed the number of antibonding electrons above because, for each
species, the number of bonding electrons is the same, namely 10. Recall that the bond
order is determined as follows: bond order = (number of bonding electrons number of
antibonding electrons) 2
(a) In order of increasing bond distance: O2+ < O2 < O2 < O22
(b) In order of increasing bond strength: O22 < O2 < O2 < O2+
Cl

94. (M)(a)
F

C
Cl

Cl
Cl

C Cl
Cl

As shown in the Lewis structures above, the net result of this reaction is breaking a C
Cl bond. From Table 10-3, the energy of this bond is 339 kJ/mol, and this must be the
energy of the photons involved in the reaction.

1121

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

(b) E = h or = E/h on a molecular basis. Thus, we have the following.


339 10 3 J/mol
8.50 10 14 s 1
23
34
6.626 10 J s 6.022 10 / mol
c 3.00 10 8 m/s
10 9 nm
7
3.53 10 m
353 nm

8.50 10 14 / s
1m

This radiation is in the near ultraviolet region of the electromagnetic spectrum.


95. (M) (a) % P indicates the number of grams of P per 100 g of material, while % P4O10
indicates the number of grams of P4O10 per 100 g of material.
1 mol P4 O10
4 mol P
30.974 g P
mass P 1.000 g P4 O10

0.436 g P
283.89 g P4 O10 1 mol P4 O10
1 mol P
Thus, multiplying the mass of P4O10 by 0.436 will give the mass (or mass percent)
of P. %BPL indicates the number of grams of Ca3(PO4)2 per 100 g of material.

mass Ca 3 (PO 4 ) 2 1.000 g P4 O10

1 mol P4 O10
4 mol P

283.89 g P4 O10 1 mol P4 O10

1 mol Ca 3 (PO 4 ) 2 310.18 g Ca 3 (PO 4 ) 2

2.185 g Ca 3 (PO 4 ) 2
2 mol P
1 mol Ca 3 (PO 4 ) 2

Thus, multiplying the mass of P4O10 (283.88) by 2.185 will give the mass (or mass %) of BPL.
(b) A %BPL greater than 100% means that the material has a larger %P than does pure Ca3(PO4)2.
(c) %P

1 mol 3Ca 3 (PO 4 ) 2 CaF2


6 mol P
30.974 g P

100% 18.43% P
1mol 3Ca 3 (PO 4 ) 2 CaF2 1008.6 g 3Ca 3 (PO 4 ) 2 CaF2
1 mol P
%P
18.43
%P4 O10

42.3% P4 O10
0.436 0.436
%BPL 2.185 %P4 O10 2.185 42.3% P4 O10 92.4% BPL

2 Cl(g) . From Appendix D,


96. (M) The chemical equation is Cl2 (g)
o
H f [Cl(g)] 121.7 kJ/mol , 243.4 kJ/2 mol Cl or 243.4 kJ/mol Cl2.
o
S rxn
2 S o [Cl(g)] S o [Cl 2 (g)] (2 165.2) 223.1 107.3 J K 1 .

We assume the values of H o and S o are unchanged from 298 K to 1000 K, and we
calculate the value of G o at 1000 K.
G o H o T S o 243.4 kJ (1000 K 0.1073 kJ K 1 ) 136.1 kJ

G o RT ln K p

G o
136.1 103 J/mol

16.37
K p e16.37 7.8 10 8
RT
8.314 J mol1 K 1 1000 K
Since the value of Kp is so small, we assume the initial Cl2(g) pressure is 1.00 atm.
ln K p

1122

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

Reaction:

Cl2 (g)

Initial:

1.00 atm

Changes:

x atm

Equil:

(1.00 x)

2Cl(g)
0 atm
2x atm
2x atm

Kp

PCl 2
(2 x) 2
4x2
7.8 108

PCl2
1.00 x 1.00

7.8 108
1.4 104
4

Our assumption, that x << 1.00 atm, obviously is valid. x is the degree of dissociation.
The % dissociation now can be calculated. % dissociation = x 100% = 1.4 104 100%
= 0.014 %
97. (E) The peroxo prefix of peroxonitrous acid hints at the presence of a O O
linkage in the molecule.

nitric acid

peroxonitrous acid

H O O N O

98. (M)
The Lewis structures of these two compounds are similar. If we designate CH3
Me N Me
Sl N Sl
as Me and SiH3 as Sl, the two Lewis structures are
Me

Sl

The pyramidal structure of N(CH3)3 indicates a tetrahedral electron pair geometry, with
sp3 hybridization for N in N(CH3)3 and the lone pair of electrons residing in an sp3
hybrid orbital. The NC bond involves the overlap of N( sp 3 ) C( sp 3 ) . The CH
bonds are C( sp 3 ) H(1s ) . The planar arrangement of N(SiH3)3 indicates that the
nitrogen atom is sp2 hybridized; the lone pair is in a 2p atomic orbital on the central N
atom, perpendicular to the N Si plane in the center of the molecule. If we assume that
the Si atom is sp3 hybridized (to account for the four bonds each Si atom forms), the N
Si bond involves the overlap between N( sp 2 ) Si( sp 3 ) . Thus, the SiH bonds are
Si( sp 3 ) H(1s ) .
99. (M) pH = 3.5 means [H+] = 103.5 = 3 104 M. This is quite a dilute acidic solution, and we
expect H2SO4 to be completely ionized under these circumstances.
mass H 2 SO 4 1.00 103 L

3 104 mol H 1 mol H 2 SO 4 98.1 g H 2 SO 4

15 g H 2 SO 4
1L
1 mol H 2 SO 4
2 mol H

70 g Br2
1 mol Br2 1 mol Cl 2
1000 cm 3 1.03 g

3
1L
1 cm 10 g seawater 159.8 g Br2 1 mol Br2
70.9 g Cl 2
115 g Cl 2 used

37 g Cl 2
1 mol Cl 2 100 g Cl 2 needed

mass Cl 2 1.00 10 3 L

1123

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

100.(M)

0.0592
log 10 Q ;
n
assuming E 0 for a process that is no longer spontaneous:
E Eo

nE o
(16)(0.065)

17.6
0.0592
0.0592
(P SO )8 (1 10-6 )8
17.6
17
Q 10 3.9 10 8 2 16 8 16
1 (H )
1 (H )
log 10 Q

SO 2

1 10-6

Solving for [H ] yields a value of 8 105 M, which corresponds to a pH of 4.1


Thus, the solution is still acidic.
101. (M)
In the process of forming XeF2 and XeCl2, either a ClCl bond or a FF
bond is broken. We note that the FF bond is much weaker than the ClCl bond and
thus much less energy is required to break it. Since greater stability indicates that the
resulting product is of lower energy, the greater stability for XeF2 compared to XeCl2
can be partially explained by the need to expend less energy to break the bonds of the
reactants. (Another reason, of course, is that the shorter XeF bond is stronger, and
hence more stable, than the somewhat longer XeCl bond.)
102. (M)

Oxidations :

XeF4 (g) 3 H 2 O
XeO 3 (g) 4 HF(aq) 2 H (aq) 2 e

{2 H 2 O(l)
O 2 (g) 4 H (aq) 4 e } 32
Reduction:

{XeF4 (g) 4 e
Xe(g) 4 F (aq)}

Net:

3 XeF4 (g) 6 H 2 O(l)


2 XeO3 (g) 12 HF(aq)

2
3
2

O 2 (g) 2 Xe(g)

The fact that O2 is also produced indicates that there are two oxidation half-reactions.
The production ratio of Xe and XeO3 indicates the amount by which the other two halfreactions must be multiplied before they are added. Then the half-reaction for the
production of O2 is multiplied by 32 to balance charge.
103.

(M) S(s) + 2 H+(aq) + 2 e- H2S(g)


E = 0.174 V
S(s) + 2 H+(aq) + 2 e- H2S(aq) E = 0.144 V

The difference is that one results in an aqueous solution being formed, while the other gives
a gaseous product. They can both be correct because the product has a different phase
(the products have different Gf values, hence one would expect different values).
104.

(M) The initial concentration of Cl2(aq)=

1124

6.4g
0.090M
70.9g/mol

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

-4

K c 4.4 10

Cl 2 (aq) H 2 O(l)
HOCl(aq) H (aq) Cl (aq)
initial 0.090 M
0M
0M
0M

equil.

(0.090-x) M

xM

xM

xM

{where x is the molar solubility of Cl 2 in water}


K

[HOCl(aq)][ H (aq)] [Cl (aq)]


x3

4.4 10-4
[Cl 2 (aq)]
0.090-x

By using successive approximations, we find x 0.030 M, so:


[HOCl(aq)] [H (aq)] [Cl (aq)] 0.030 M and [Cl 2 (aq)] 0.090 0.030 0.060 M
105. (M)
2e- N 2 (g) 4 H + (aq) + 2H 2 O(l) 2 NH 3 OH + (aq)
E o = -1.87 V
2 NH 3 OH + (aq) + H + (aq) + 2e- N 2 H 5 + (aq) + 2 H 2 O(l) E o = 1.42 V
N 2 H 5 + (aq) + 3 H + (aq) + 2e- 2 NH 4 + (aq)

E o = 1.275 V

N 2 (g) + 8 H + (aq) + 6e- 2 NH 4 + (aq)

Eo = 0.275 V (see below)

G o total = G o 1 + G o 2 +G o 3 = -n tot FE o tot = -nFE o 1 -nFE o 2 -nFE o 3


E

o
tot

n 1 Eo 1 n 2 Eo 2 n 3 Eo 3
=
n tot

E o tot = [2(-1.87) +2(1.42) + 2(1.275)]/6 = 0.275 V


moving on...
2 HN 3 (aq) 3 N 2 ( g ) 2H + (aq) 2 e-

Eo 3.09 V (oxidation)

3 N 2 (g) 24 H + (aq) 18e- 6 NH 4 + (aq)

Eo 0.275 V (top equation multiplied by 3)

2 HN 3 (aq) 22 H + (aq) 16 e- 6 NH 4 + (aq) [ sum]

[divide by 2]
HN 3 (aq) 11 H + (aq) 8 e- 3 NH 4 + (aq)

E o 0.70 V

since
G o total = G o 1 +G o
E

o
total

= -nFE o tot = -nFE o 1 -nFE o

= [2(3.09) +18(0.275) ]/16 = 0.70 V

106. (E) Ignoring distortions arising from different bond lengths and different bond orders,

we can say the following:


(a) in FClO2, the Cl atom is bonded to three atoms and a lone pair of electrons. The

electron group geometry is tetrahedral. The molecular structure is ammonia-like


(trigonal pyramidal).

1125

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

(b) In FClO3, the Cl atom is bonded to four atoms and has no lone pairs. The electron

group geometry is tetrahedral. The molecular structure is methane-like (tetrahedral).


(c) In F3ClO, the Cl atom is bonded to four atoms and has one lone pair. The electron

group geometry is trigonal bipyramidal with the lone pair in an equatorial position.
The molecular structure is SF4-like (seesaw).
107.

(E) Both molecules are V shaped, with a lone pair of electrons on the central atom.

For O3, the structure is a hybrid of two equivalent structures. In each of these
structures, the central atom has a formal charge of +1. The oxygenoxygen bond
order is between 1 and 2. Although many resonance structures can be drawn for SO2,
in the most important structure, the formal charge on the S atom is zero and the
sulfuroxygen bonds are double bonds.

108. (M)

F
F

F
Sb

F
F

HN

109.

3
(M) H fo = [ (498) 3 (36)] = 639 kJ mol1
2
The formation reaction is very endothermic and thus energetically unfavorable. This
result supports the observation that Xe(g) does not react directly with O2(g) to form

1126

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

XeO3(g). Because the reaction converts 2.5 moles of gas into 1 mole of gas, we
expect Sfo < 0; thus, the reaction is also entropically unfavorable.

FEATURE PROBLEMS
110. (D) The goal here is to demonstrate that the three reactions result in the decomposition
of water as the net reaction: Net: 2 H 2 O 2 H 2 + O 2 First balance each equation.

(1)

3 FeCl 2 + 4 H 2 O Fe 3O 4 + HCl + H 2 Balance by inspection. Notice that there


are 3 Fe and 4 O on the right-hand side. Then balance Cl.
3 FeCl 2 + 4 H 2 O Fe 3O 4 + 6 HCl + H 2

(2)

Fe 3O 4 + HCl + Cl 2 FeCl 3 + H 2 O + O 2 Try the half-equation method.


Cl 2 + 2 e 2 Cl But realize that Fe3O 4 = Fe 2 O 3 FeO .
2 FeO 2 Fe 3+ + O 2 + 6 e Now combine the two half-equations.
2 FeO + 3 Cl 2 2 Fe 3+ + O 2 + 6 Cl
Add in 2 Fe 2 O 3 +12 H + 4 Fe 3+ + 6 H 2 O
2 Fe 3O 4 + 3 Cl 2 +12 H + 6 Fe 3+ + O 2 + 6 Cl + 6 H 2 O
And 12 Cl spectators: 2 Fe 3O 4 + 3 Cl 2 +12 HCl 6 FeCl 3 + O 2 + 6 H 2 O

(3)

FeCl 3 FeCl 2 + Cl 2 by inspection 2 FeCl 3 2 FeCl 2 + Cl 2

One strategy is to consider each of the three equations and the net equation. Only
equation (1) produces hydrogen. Thus, we must run it twice. Only equation (2)
produces oxygen. Since only one mole of O2(g) is needed, we only have to run it once.
Equation (3) can balance out the Cl 2 required by equation (2), but we have to run it
three times to cancel all the Cl2(g).
2 1 6 FeCl2 (s) + 8 H 2 O(l) 2 Fe3 O 4 (s) +12 HCl(l) + 2 H 2 (g)
1 2 2 Fe3 O 4 (s) + 3 Cl2 (g) +12 HCl(g) 6 FeCl3 (s) + O 2 (g) + 6 H 2 O(l)
3 3 6 FeCl3 (s) 6 FeCl2 (s) + 3 Cl2 (g)

Net:

2 H 2 O(l) 2 H 2 (g) + O 2 (g)

111. (D) We begin by calculating the standard voltages for the two steps in the decomposition
mechanism. Step 1 involves the reduction of Fe3+ and the oxidation of H2O2. The two halfreactions that constitute this step are:

(i)
(ii)

2+

Fe3+(aq) + e

Fe (aq)
+

H2O2(aq)

O2(g) + 2 H (aq) + 2 e

1127

E1,red = 0.771 V
E2,ox = 0.695 V

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

The balanced reaction is obtained by combining reaction (i), multiplied by two, with
reaction (ii).
2+

2(i) 2(Fe3+(aq) + e

Fe (aq))
+

(ii) H2O2(aq)

O2(g) + 2 H (aq) + 2 e
2+
+

2 Fe3+(aq) + H2O2(aq)

2 Fe (aq) +O2(g) + 2 H (aq),

(iii)

for which Ecell = Ei(red) + Eii(ox) = 0.771 V + (0.695 V) = 0.076 V


Since the overall cell potential is positive, this step is spontaneous. The next step
involves oxidation of Fe2+(aq) back to Fe3+(aq), (i.e. the reverse of reaction (i) and the
reduction of H2O2(aq) to H2O(l) in acidic solution, for which the half-reaction is

(iv) H2O2(aq) + 2 H+(aq) + 2 e


Eiv(red) = 1.763 V

2 H2O(l)
Combining (iv) with two times the reverse of (i) gives the overall reaction for the
second step:

iv)

3+

{Fe2+(aq)

Fe (aq) + e } 2

H2O2(aq) + 2 H+(aq) + 2 e

2 H2O(l)

(v)

3+

2 Fe2+(aq) + H2O2(aq) + 2 H+(aq)

2 Fe (aq) + 2 H2O(l)

(i)

Thus the overall cell potential for the second step in the mechanism, via equation (v) is

Ecell = Ei(red) + Eiv(red) = 0.771 V + (1.763 V) = 0.992 V.


Since the overall standard cell potential is positive, like step 1, this reaction is spontaneous.
The overall reaction arising from the combination of these two steps is:

Step 2

2+
+

2 Fe3+(aq) + H2O2(aq)

2 Fe + (aq) + O2(g) + 2 H (aq)


3+

2 Fe2+(aq) + H2O2(aq) + 2 H+(aq)

2 Fe (aq) + 2 H2O(l)

Overall

2 H2O2(aq)

O2(g) + 2 H2O(l)

Step 1

The overall potential, Eoverall = Estep1+ Estep2 = 0.076 V + 0.992 V = 1.068 V


Therefore, the reaction is spontaneous at standard conditions.
To determine the minimum and maximum E values necessary for the catalyst, we need to
consider each step separately.
In step 1, if E(1) is less than 0.695 V, the overall voltage for the first step will be
negative and hence non-spontaneous. In step 2, if the oxidation half-reaction has a
potential that is more negative than 1.763 V, the overall potential for this step will be
negative, and hence non-spontaneous. Consequently, E(1) must fall between 0.695 V
and 1.763 V in order for both steps to be spontaneous. On this basis we find that
(a)

Cu2+(aq) + 2 e

Cu(s)

E1/2red = 0.337 V cannot catalyze the reaction.

1128

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

(b)
(c)
(d)

Br2(l) + 2 e

2 Br (aq)

Al3+(aq) + 3 e

Al(s)
+

Au3+(aq) + 2 e

Au (s)

E1/2red = 1.065 V may catalyze the reaction.


E1/2red = 1.676 V cannot catalyze the reaction.
E1/2red = 1.36 V may catalyze the reaction.

In the reaction of hydrogen peroxide with iodic acid in acidic solution, the relevant
half-reactions are:

2 IO3(aq) + 12 H+(aq) + 10 e

I2(s) + 6 H2O(l) E1/2red = 1.20 V


+

E1/2ox= 0.695 V
H2O2(aq)

O2(g) + 2 H (aq) + 2e
Thus, both steps in the decomposition of H2O2, as described above, are spontaneous if
IO3 is used as the catalyst. As the iodate gets reduced to I2, the I2 forms a highly
colored complex with the starch, resulting in the appearance of a deep blue color
solution. Some of the H2O2 will be simultaneously oxidized to O2(g) by the iodic acid
When sufficient I2(s) accumulates, the reduction of H2O2 by I2 begins to take place and
the deep blue color fades as I2 is consumed in the reaction. Additional iodate is formed
concurrently, and this goes on to oxidize the H2O2(aq), thereby causing the cycle to
repeat itself. Each cycle results in some H2O2 being depleted. Thus, the oscillations of
color can continue until the H2O2 has been largely consumed.

112.

(D) ClO3

(?)

(?)

ClO2

HClO2

1.1181 V

In order to add ClO2 to the Latimer diagram drawn above, we must calculate the voltages
denoted by (?) and (??) . The equation associated with the reduction potential (?) is
(i)

2 H+(aq) + ClO3(aq) + 1 e ClO2(g) + H2O(l)


The standard voltage for this half-reaction is given in Appendix D:

To finish up this problem, we just need to calculate the standard voltage (??) for
the half-reaction (ii):
(ii) H+(aq) + ClO2(aq) + 1 e HClO2(g)

Eo = (??)

To obtain the voltage for reaction (ii), we need to subtract reaction (i) from reaction (iii)
below, which has been taken from Figure 22-2:
o

(iii) 3 H+(aq) + ClO3(aq) + 2 e

HClO2(g) + H2O(l) E = 1.181 V

Thus,
o

(iii) 3 H+(aq) + ClO3(aq) + 2 e

HClO2(g) + H2O(l) E (iii) = 1.181 V


1 (i) 2 H+(aq) + ClO3(aq) + 1 e ClO2(g) + H2O(l)
Eo(i) = 1.175 V

Net (ii)

H+(aq) + ClO2(g) + 1 e HClO2(g)

Eo(ii) = (??)

Since reactions (i) and (iii) are both reduction half reactions, we cannot simply subtract the
potential for (i) from the potential for (iii). Instead, we are forced to obtain the voltage for
1129

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

(ii) via the free energy changes for the three half reactions. Thus,
G(ii) = G(iii) G(i) = 1FEo(ii) = 2F(1.181 V) + 1F(1.175 V)
Dividing both sides by F gives

Eo(ii) = 2(1.181 V) 1.175 V

So, Eo(??) = 1.187 V.

113. (D) (a) As before, we can organize a solution around the balanced chemical equation.

Equation:
Initial:
Initial:
Changes:
Equil:

I 2 aq

I 2 CCl4

3
1.33 10 M
0.0133 mmol
x mmol
0.0133 x mmol

x
[I (CCl4 )]
10.0 mL

K c 85.5 2
0.0133 x
[I 2 (aq)]
10.0 mL

0M
0 mmol
+ x mmol
x mmol

1.137
= 0.01315 mmol I2 in CCl4
86.5
I 2 aq = 0.0133 0.01315 mmol = 0.00015 mmol

x 1.137 85.5 x

86.5 x 1.137

mass I 2 = 0.00015 mmol


(b)

x=

253.8 mg I 2
= 3.8 102 mg I 2 = 0.038 mg I 2 remaining
1 mmol I 2

We have the same set-up, except that the initial amount I 2 aq = 0.00015mmol .
[I 2 (CCl4 )]
x

[I 2 (aq)]
0.00015 x
x 0.0128 85.5 x
86.5 x 0.0128
0.0128
= 0.0001480 mmol = I 2 CCl4 ,
x=
86.5
I 2 aq = 0.00015 0.0001480 = 2.0 106 mmol I 2

K c = 85.5

mass I 2 = 2.0 106 mmol in H 2 O


(c)

253.8 mg I 2
= 5.1104 mg I 2 = 0.00051 mg I 2
1 mol I 2

If twice the volume of CCl4 were used for the initial extraction, the equilibrium
concentrations would have been different from those in part (a).
I 2 aq

I 2 CCl4

Initial:
Initial:
Changes:

3
1.33 10 M
0.0133 mmol
x mmol

0M
0 mmol
+ x mmol

Equil:

0.0133 x mmol

x mmol

Equation:

x 2 1.137 85.5 x

86.0 x 1.137

1130

x=

x
[I 2 (CCl4 )]
20.0 mL
K c = 85.5
0.0133 x
[I 2 (aq)]
10.0 mL
1.137
= 1.32 102 mmo I2 CCl4
86.0

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

1.33 103 mmol I 2


253.8 mg I 2
10.0 mL soln
= 3.376 mg I 2
1 mL
1 mol I 2
253.8 mg I 2
mass I 2 in CCl4 =1.322 102 mmol
= 3.356 mg I 2
1 mol I 2
mass I 2 remaining in water = 3.376 mg 3.356 mg = 0.020 mg
Thus, two smaller volume extractions are much more efficient than one large
volume extraction.
total mass I 2 =

114. (D) (a) The pyroanions, a series of structurally analogous anions with the general
formula X2O7n, are known for Si, P and S. The Lewis structures for these three
anions are drawn below: (Note: Every member of the series has 56 valence e)

O
O

O
O

X = Si : Si2O76-

X = P : P2O74X = S 2+: S2O72-

Based upon a VSEPR approach, we would predict tetrahedral geometry for each
X atom (i.e. Si, P+, S2+) and a bent geometry for each bridging oxygen atom
Therefore, a maximum of five atoms in each pyroanion can lie in a plane:
O
O
X
O
(b)

O
O

X
O

Atoms labeled 1-5 are all in the same plane.

The related mononuclear acids, which contain just one third-row element are
H4SiO4, H3PO3 and H2SO4. A series of pyroacids can be produced by strongly
heating the mononuclear acids in the absence of air. In each case, the reaction
proceeds via loss of water:

2 H4SiO4

H6Si2O7(l) + H2O(l)

2 H3PO3
H4P2O7(l) + H2O(l)

2 H2SO4

H2S2O7(l) + H2O(l)

(c)

The highest oxidation state that Cl can achieve is VII (+7); consequently, the
chlorine containing compound that is analogous to the mononuclear acids
mentioned earlier is HClO4. The strong heating of perchloric acid in the absence
of air, should, in principle, afford Cl2O7, which is the neutral chlorine analogue of
the pyroanions. Thus, Cl2O7 is the anhydride of perchloric acid.

2 HClO4

Cl2O7(l) + H2O(l)

1131

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

115. (D) (a) The bonding in the XeF2 molecule can be explained quite simply in terms of
a 3center, 4 electron bond that spans all three atoms in the molecule. The
bonding in this molecular orbital description involves the filled 5pz orbital of Xe
and the half-filled 2pz orbitals of the two F-atoms. The linear combination of
these three atomic orbitals affords one bonding, one non-bonding and one antibonding orbital, as depicted below:

(b)

+
Non-bonding MO

+
+
F(2pz)

+
Antibonding MO

Xe(5pz)

+
F(2pz)

If one assumes that the order of energies for molecular orbitals is:
bonding MO < non-bonding MO < antibonding MO,
the following molecular orbital representation of the bonding can be sketched.
Thus, a single bonding pair of electrons is
responsible for holding all three atoms
together. The non-bonding pair of electrons is
localized primarily on the two Fatoms. This
suggests that the bond possesses substantial
ionic character. Bond order is defined as onehalf the difference between the number of
bonding electrons and the number of
antibonding electrons. In the case of XeF2, the
overall bond order is
2 e 0 e
1.0 .
2 e
(i.e., each XeF bond has a bond order of 0.5)

Antibonding
2pz 2pz

5pz

Non-bonding

Bonding

therefore:

(c)

+
+
Bonding MO

Xe
Atomic
Orbital

XeF2
Molecular
Orbitals

2 xF
Atomic
Orbitals

By invoking a molecular orbital description based upon three-center bonding for the
three FXeF units in XeF6, one obtains an octahedral structure in which there are
six identical XeF bonds. The extra nonbonding pair of electrons is delocalized over
the entire structure in this scheme. In spite of its manifest appeal, this explanation of
the bonding in XeF6 is incorrect, or at best a stretch, because the actual structure for
this molecule is a distorted octahedron. A more accurate description of the
stereochemistry adopted by XeF6 is provided by VSEPR theory. In this approach, the

1132

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

shape of the molecule is determined by repulsions between bonding and non-bonding


electrons in the valence shell of the central Xe atom.
Accordingly, in XeF6, six bonding pairs and one lone pair of electrons surround the
Xe. Having the repulsions of 7 pairs of electrons to cope with, the XeF6 molecule
adopts a distorted structure that approaches either a monocapped octahedron or a
pentagonal bipyramidal arrangement of electron pairs, depending on how one
chooses to view the structure. In either case, these two shapes are much closer to the
true shape for XeF6 than that predicted by the molecular orbital treatment involving
three, three-center bonds. By contrast, the molecular orbital description involving
three-center bonds gives far better results when applied to XeF4. In this instance,
with two three-center FXeF bonds in the structure, molecular orbital theory
predicts that XeF4 should adopt a square planar structure.
The result here is quite satisfactory because XeF4 does in fact exhibit square planar
geometry. It is worth noting, however, that a square planar shape for XeF4 is also
predicted by VSEPR theory. Despite the fact that the molecular orbital method has
made some inroads as of late, VSEPR is still the best approach available for
rationalizing the molecular geometries of noble gas compounds.
116. (D) (a) In the phase diagram sketched in the problem, extend the liquid-vapor
equilibrium curve (the vapor pressure curve) to lower temperatures (supercooled
liquid region). Extend the S-vapor equilibrium curve (sublimation curve) to the
temperature at which it intersects the extended vapor pressure curve. This should
come at 113 C. Draw a line from this point of intersection to the peak of the S
phase region. Erase the three lines that bound the S region in the original sketch.
The remaining three lines would represent the equilibria, S-V, S-L, and L-V,
producing the phase diagram if S (rhombic) were the only solid form of sulfur.
(b)

If rhombic sulfur is heated rapidly, the transition to monoclinic sulfur at 95.3 C


might not occur. (Solid-state transitions are often very slow.) In this case,
rhombic sulfur would melt at 113 C, as described in the modified phase diagram
in part (a). If the molten rhombic sulfur is further heated and then cooled, the
liquid very likely will freeze at the equilibrium temperature of 119 C, producing
monoclinic, not rhombic, sulfur.

1133

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

SELF-ASSESSMENT EXERCISES
117. (E)

(a) The halogens can combine with each other to form interhalogens and
polyhalide ions. (b) Polyphosphates are anionic phosphate polymers linked
between hydroxyl groups and hydrogen atoms. (c) The halogens react with each
other to form interhalogen compounds. The general formula of most
interhalogen compounds is XYn, where n = 1, 3, 5 or 7 (X is the less
electronegative of the two halogens). (d) Disproportionation is the chemical
reaction in which the same element is spontaneously oxidized and reduced.

118. (E)

(a) The Frasch process is a method to extract sulfur from underground deposits.
(b) The water-gas shift reaction is a chemical reaction in which carbon monoxide
reacts with water vapor to form carbon dioxide and hydrogen: CO + H2O CO2
+ H2. It is a very important industrial reaction. (c) Eutrophication is an increase
in the concentration of chemical nutrients in an ecosystem to an extent that
increases the primary productivity of the ecosystem. (d) Electrode potential
diagrams are used to simplify actual electrochemical cells.

119. (E)

(a) An acid anhydride is an organic compound that has two acyl groups bound to
the same oxygen atom. Acid salt is an anionic compound. (b) Azide
functionality is -N3. A nitride is a compound of nitrogen with a less
electronegative element where nitrogen has an oxidation state of 3. (c)
Elemental phosphorus exists in two major forms - white phosphorus and red
phosphorus, they are structurally different. (d) Both terms are similar and
represent a class of compounds in which hydrogen is bound to a very
electropositive element (such as alkali earth metals).

120. (E)

(b)

121. (E)

(d)

122. (E)

(c)

123. (E)

(a)

124. (E)

(d)

125. (E)

(b)

126. (E)

(a) and (b)

127. (M) (a) Cl2 (g)+2NaOH(aq) NaCl(aq)+NaOCl(aq)+H 2O(l)


(b) 2NaI(s)+2H 2SO 4 (concd aq) Na 2 SO 4 (a)+2H 2 O(g)+SO 2 (g)+I2 (g)
(c) Cl2 (g)+2KI3 (aq) 2KCl(aq)+3I2 (s)
(d) 3NaBr(s)+H 3PO 4 (concd aq) Na 3PO 4 +3HBr(g)

1134

Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

(e)

5HSO-3 (aq)+2MnO-4 (aq)+H + (aq) 5SO 2-4 (aq)+2Mn 2+ (aq)+3H 2O(l)

128. (M) (a) 2KClO 3 (s) 2KCl(s)+3O 2 (g) a catalyst such as MnO2 is required,
electrolysis of H2O is an alternate method.
(b) 3Cu(s)+8H+(aq)+2NO-3 (aq) 3Cu 2+ (aq)+4H 2O(l)+2NO(g) , difficult to
control reaction so that NO(g) is the only reduction product.
(c) Zn(s)+2H + (aq) Zn 2+ (aq)+H 2 (g) , a number of other metals can be used.
(d) NH 4 Cl(aq)+NaOH(aq) NaCl(aq)+H 2 O(l)+NH 3 (g) , other ammonium salts
and other bases work as well.
(e) CaCO 3 (s)+2HCl(aq) CaCl2 (aq)+H 2 O(l)+CO 2 (g) , other carbonates and
acids can be used.
129. (M) (a) LiH(s)+H 2O(l) LiOH(aq)+H 2 (g)
(b)
C(s)+H 2 O(g) CO(g)+H 2 (g)
(c) 3NO 2 (g)+H 2O(l) 2HNO 3 (aq)+NO(g)
130. (M)

3Cl2 (g)+I- (aq)+3H 2 O(l) 6Cl- (aq)+IO-3 (aq)+6H + (aq)


Cl2 (g)+2Br - (aq) 2Cl- (aq)+Br2 (aq)

131. (M) One conversion pathway is ton lb kg g H2SO4 g S mg S L


seawater m3 kg3 seawater, leading to about 5.0 kg3 of seawater.
132. (M) (a) AgAt, (b) sodium perxenate, (c) MgPo, (d) tellurous acid, (e) K2SeSO3, (f)
potassium perastatate
133. (D) Convert the E o values to G o values for the reduction of H2SeO3 to Se and from
Se to H2Se. Add those two G o values to obtain G o for the reduction of
H2SeO3 to H2Se. Convert this G o value to E o , which proves to be 0.38 V.
134. (M) (a) SO3, (b) SO2, (c) Cl2O7, (d) I2O5
135. (M) (a) false, (b) true, (c) true.

1135