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CHAPTER 21

CHEMISTRY OF THE MAIN-GROUP ELEMENTS I:


GROUPS 1, 2, 13, AND 14
PRACTICE EXAMPLES
1A

(E) From Figure 21-2, the route from sodium chloride to sodium nitrate begins with
electrolysis of NaCl(aq) to form NaOH(aq).
2 NaCl aq + 2 H 2O l electrolysis

2 NaOH aq + H 2 g + Cl2 g followed by addition of

NO2 g to NaOH(aq). 2 NaOH aq + 3 NO 2 g 2 NaNO3 aq + NO g + H 2 O(l)

1B

(E) From Figure 21-2, we see that the route from sodium chloride to sodium thiosulfate
begins with the electrolysis of NaCl(aq) to produce NaOH(aq),

2 NaOH aq + H 2 g + Cl2 g
2 NaCl aq + 2 H 2O l electrolysis
and continues through the reaction of SO2 g with the NaOH(aq) in an acid-base reaction
[ SO2 g is an acid anhydride] to produce
Na 2SO3 aq :

2 NaOH aq + SO 2 g Na 2SO3 aq + H 2 O(l) and (3) concludes with

boil
the addition of S to the boiling solution: Na 2SO3 aq + S(s)
Na 2S2 O3 aq .

2A

(M) The first reaction indicates that 0.1 mol of NaNO2 reacts with 0.3 mol of Na to yield
0.2 mol of compound X and 0.05 mol of N2. Since this reaction liberates nitrogen gas, it is
very likely that compound X is an oxide of sodium. The two possibilities include Na2O
and Na2O2. Na2O2 will not react with oxygen, but Na2O will. Therefore, compound X is
most likely Na2O and compound Y is Na2O2. The balanced chemical equations for two
processes are:
1
NaNO 2 (s)+3Na(s) 2Na 2O(s)+ N 2 (g)
2
1
Na 2O(s)+ O2 (g) Na 2 O2 (s)
2

2B

(M) Since compound X is used in plaster of Paris it must contain calcium. Calcium reacts
with carbon to form calcium carbide, according to the following chemical equation:
Ca(s)+2C(s) CaC2 (s)

Furthermore, compound X or calcium carbide reacts with nitrogen gas to form compound
Y or calcium cyanamide:
CaC2 (s)+N 2 (g) CaCN 2 (s)+C(s)
CN22- anion is isoelectronic with CO2 and it therefore contains 16 electrons. The structure
of this anion is:
N

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Chapter 21: Chemistry of the Main-Group Elements I: Groups 1, 2, 13, and 14

3A

(M) The first two reactions, are those from Example 21-3, used to produce B2 O3 .

Na 2 B4 O7 10 H 2 O(s) + H 2SO 4 (l)


4 B OH 3 (s) + Na 2SO 4 (s) + 5 H 2 O(l)

2 B OH 3 (s)
B2 O3 (s) + 3H 2 O(g)

The next reaction is conversion to BCl3 with heat, carbon, and chlorine.

2 B2 O3 s + 3C s + 6 Cl2 g
4 BCl3 g + 3CO 2 g

LiAlH 4 is used as a reducing agent to produce diborane.

4 BCl3 g + 3LiAlH 4 (s) 2 B2 H 6 g + 3LiCl(s) + 3AlCl3 (s)

3B

(M) Na2B4O7.10 H2O(s) + H2SO4(aq) 4 B(OH)3(s) + Na2SO4(aq) + 5 H2O(l)

B2O3(s) + 3 H2O(l)
2 B(OH)3(s)

B2O3(s) + 3 CaF2(s) + 3 H2SO4(l)


2 BF3(g) + 3 CaSO4(s) + 3 H2O(g)

INTEGRATIVE EXAMPLE
A

(M) NaCN and Al(NO3)3 dissociate in water according to the following equations:
NaCN(aq) Na + (aq)+CN - (aq)
Al(NO 3 )3 (aq) Al3+ (aq)+3NO-3 (aq)
NaCN is a salt of strong base (NaOH) and weak acid (HCN) and its solution is therefore
basic.
We proceed by first determining the [OH]- concentration in a solution which is 1.0M in
NaCN:
CN +H 2O HCN+OH
1.0
/
/
1.0-x
x
x
14
Kw
1.0 10
Kb

1.6 10 5
10
K a (HCN ) 6.2 10
[HCN ][OH ]
xx
x2

1.6 10 5

[CN ]
1.0 x 1.0 x
Assume, x<<1 and 1.0-x1.0
Kb

x 2 1.6 10 5 x 1.6 10 5 4.0 10 3


[OH ] 4.0 10 3
On mixing, [OH-]=2.010-3 M and [Al3+]=0.50 M. The precipitation will occur according
to the following equation:
3+
Al (aq)+3OH (aq) Al(OH)3 (s)
The product [Al3+][OH-]3=0.50(2.010-3)3=4.010-9 is much greater than KSP for Al(OH)3
(1.310-33) and therefore precipitation will occur.

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Chapter 21: Chemistry of the Main-Group Elements I: Groups 1, 2, 13, and 14

(M) When BeCl2 4H 2 O is heated, it decomposes to Be(OH)2(s), H2O(g), and HCl(g), as


discussed in Section 21-3. BeCl2 4H 2 O comprises [Be(H2O)4]2+ and Cl ions. Because of
the high polarizing power of Be2+, it is difficult to remove the coordinated water molecules
by heating the solid and the acidity of the coordinated H2O molecules is enhanced. When
BeCl2 4H 2 O is dissolved in water, [Be(H2O)4]2+ ions react with water, and
[Be(H2O)3(OH)]+ and H3O+ ions are produced. Hence, a solution of BeCl2 4H 2 O is
expected to be acidic.
When CaCl2 6H 2 O is heated, CaCl2(s) and H2O(g) are produced. Because the charge
density and polarizing power of Ca2+ is much less than that of Be2+, it is much easier to
drive off the coordinated water molecules by heating the solid. When CaCl2 6H 2 O is
dissolved in water, Ca2+(aq) and Cl(aq) are produced. However, the charge density of the
Ca2+ ion is too low to affect the acidity of water molecules in the hydration sphere of the
Ca2+ ion. Hence, a solution of CaCl2 6H 2 O has a neutral pH.

EXERCISES
Group 1: The Alkali Metals
1.

2.

3.

(E)

(a)

2 Cs(s) + Cl2 (g)


2 CsCl(s)

(b)
(c)

2 Na(s) + O 2 (g)
Na 2 O2 (s)

(d)

Na 2 SO 4 s + 4 C s Na 2 S s + 4 CO g

(e)

K s + O 2 g
KO 2 s

Li 2 CO3 s
Li 2 O s + CO 2 g

2RbOH aq + H 2 g

(a)

2 Rb s + 2 H 2O l

(b)

2 KHCO3 s
K 2 CO3 aq + H 2 O(l) + CO 2 g

(c)

2 Li s + O 2 g
Li 2 O 2 s

(d)

2 KCl s + H 2 SO 4 aq
K 2 SO 4 aq + 2 HCl g

(e)

LiH s + H 2 O l
LiOH aq + H 2 g

(E) Both LiCl and KCl are soluble in water, but Li 3 PO 4 is not very soluble. Hence the
addition of K 3 PO 4 (aq) to a solution of the white solid will produce a precipitate if the
white solid is LiCl, but no precipitate if the white solid is KCl. The best method is a flame
test; lithium gives a red color to a flame, while the potassium flame test is violet.

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Chapter 21: Chemistry of the Main-Group Elements I: Groups 1, 2, 13, and 14

4.

(E) When heated, Li 2 CO 3 decomposes to CO 2 (g) and Li 2 O(l). K 2 CO3 (s) simply melts when
heated. The evolution of CO 2 (g) bubbles should be sufficient indication of the difference in
behavior. The flame test affords a violet flame if K+ is present, and a red flame if Li+ is present.

5.

(M) First we note that sodium carbonate ionizes virtually completely when dissolved in H2O and
thus is described as highly soluble in water. This is made evident by the fact that there is no Ksp
value for Na2CO3. By contrast, the existence of Ksp values for MgCO3 and Li2CO3 shows that
these compounds have lower solubilities in water than Na2CO3. To decide whether MgCO3 is
more or less soluble than Li2CO3, we must calculate the molar solubility for each salt and then
compare the two values. Clearly, the salt that has the larger molar solubility will be more soluble
in water. The molar solubilities can be found using the respective Ksp expressions for the two
salts.

1.

2.

Ksp = 3.5 10-8

MgCO3
Mg2+(aq) + CO32-(aq)
s
s
excess s
2
-8
-4
s = 3.510
s = 1.910 M
K

= 2.5 10- 2

sp

Li2CO3
2 Li+(aq) + CO32-(aq)

2s

excess s

Let s = molar solubility of MgCO3

Let s = molar solubility of Li2CO3

2.510-8
= 0.18 M
4
We can conclude that Li2CO3 is more soluble than MgCO3. Thus, the expected order of
increasing solubility in water is:
MgCO3 < Li2CO3 < Na2CO3.
(2s)2(s) = 2.510-8

6.

s=

(M) We know sodium metal was produced at the cathode from the reduction of sodium
ion, Na + . Thus, hydroxide must have been involved in oxidation at the anode. The
hydrogen in hydroxide ion already is in its highest oxidation state and thus cannot be
oxidized. This leaves oxidation of the hydroxide ion to elemental oxygen as the remaining
reaction.

Cathode, reduction :
Anode, oxidation :
Net :
7.

4s3 = 2.510-8

Na(l)} 4
{Na + e

O 2 (g) + 2 H 2 O(g) + 4e
4 OH

4 Na + 4 OH
4 Na(l) + O 2 (g) + 2 H 2 O(g)

(M) (a)
H 2 (g) and Cl 2 (g) are produced during the electrolysis of NaCl(aq).
The electrode reactions are:

Anode, oxidation:

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

Cathode, reduction:

2 H 2 O(l) + 2e
H 2 (g) + 2 OH (aq)

We can compute the amount of OH produced at the cathode.

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Chapter 21: Chemistry of the Main-Group Elements I: Groups 1, 2, 13, and 14

60s 0.810C 1mole


2 molOH
mol OH 2.50 min

1.26 10 3 molOH

1min
1s
96,500C
2 mole

Then we compute the [OH ] and, from that, the pH of the solution.
126
. 103 mol OH
145
. 103 M
0.872 L soln
pH=14.000 2.839 11.161

[OH ]

(b)

8.

pOH = log(1.45 103 ) 2.839

As long as NaCl is in excess and the volume of the solution is nearly constant, the
solution pH only depends on the number of electrons transferred.

(M) (a)

total energy = 3.0 V 0.50 A h

3600s 1C/s
1J

5.4 103 J
1hr
1A 1V C

We obtained the first conversion factor for time as follows.


5.0 W

1 106 W 1J / s 5.0 106 J

1 W
1W
1s

time = 5.4 103 J


(b)

9.

1s
1hr
1day
1y
1.1 109 s

34 y
6
5 10 J
3600s 24 hr 365days

The capacity of the battery is determined by the mass of Li present.


1 C/s 3600 s 1 mol e 1 mol Li 6.941 g Li
mass Li = 0.50 A h
= 0.13 g Li

1A
1h
96485 C 1 mol e 1 mol Li

(M) (a)
We first compute the mass of NaHCO3 that should be produced from 1.00 ton
NaCl, assuming that all of the Na in the NaCl ends up in the NaHCO3. We use the
unit, ton-mole, to simplify the calculations.
1 ton-mol NaCl 1ton-mol Na
mass NaHCO3 1.00 ton NaCl

58.4 ton NaCl 1ton-mol NaCl

1tol-mol NaHCO3 84.0 ton NaHCO3

= 1.44 ton NaHCO3


1ton-mol Na
1 ton mol NaHCO3
1.03 ton NaHCO 3 produced
% yield =
100% = 71.5% yield
1.44 ton NaHCO 3 expected

(b)

NH 3 is used in the principal step of the Solvay process to produce a solution in which
NaHCO 3 is formed and from which it will precipitate. The filtrate contains NH 4 Cl,
from which NH 3 is recovered by treatment with Ca(OH) 2 . Thus, NH 3 is simply used

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Chapter 21: Chemistry of the Main-Group Elements I: Groups 1, 2, 13, and 14

during the Solvay process to produce the proper conditions for the desired reactions.
Any net consumption of NH 3 is the result of unavoidable losses during production.
10.

CaSO 4 (s) 2 OH (aq)


Ca(OH) 2 (s) SO 4 2 (aq)

(M) (a)
(b)

We sum two solubility reactions and combine their values of Ksp


Ca 2 (aq) 2 OH (aq)
Ca(OH) 2 (s)
CaSO 4 (s)
Ca 2 (aq) SO 4 2 (aq)

1 / Ksp 1 / 9.1 106

CaSO 4 s + 2 OH aq
Ca OH 2 s + SO 4 2 aq

Keq =

Ksp 55
. 106

5.5 106
= 0.60
9.1 106

Because Keq is close to 1.00, we conclude that the reaction lies neither very far to the
right (it does not go to completion) nor to the left.
(c)

CaSO4 (s) 2OH (aq)


Ca(OH) 2 (s) SO 4 2 (aq)

Reaction:
Initial:
Changes:
Equil:

OH

K=

x=

SO 4

= 0.60 =

1.00 M
-x M
(1.00x) M
4x2
1.00 x

4 x 2 = 0.60 0.60 x

0M
+2x M
2x M
4 x 2 + 0.60 x 0.60 = 0

b b 2 4ac 0.60 0.36 + 9.60


= 0.32 M
=
8
2a

SO 4 2 = 1.00 x = 0.68 M
11.

OH = 2 x = 0.64 M

(M) Use G of values to calculate G o for the reaction and then the equilibrium constant

K at 298 K.

G of (kJmol-1 )

1
Na 2O 2 (s) Na 2O(s)+ O 2 (g)
2

-449.63
-379.09

G o 379.09 (449.63) 70.54kJmol-1


G o RT ln K
8.314JK -1mol-1 298K ln K 70.54 1000Jmol-1
ln K

70.54 1000Jmol-1
28.47 K e28.47 4.32 10 13
8.314JK -1mol-1 298K

1069

Chapter 21: Chemistry of the Main-Group Elements I: Groups 1, 2, 13, and 14

1
2
O2

Since K p pO2 K 2 1.87 10 25 . The equilibrium constant and partial pressure of

oxygen are both very small at 298 K. Therefore, Na2O2(s) is thermodynamically stable
with respect to Na2O(s) and O2(g) at 298 K.
12.

(M) Use G of values to calculate G o for the reaction and then the equilibrium constant

K at 298 K.
3
2KO 2 (s) K 2O(s)+ O 2 (g)
2

-1
o
G f (kJmol )
-240.59
-322.09
o
G 322.09 (2 240.59) 159.1kJmol-1

G o RT ln K
8.314JK -1mol-1 298K ln K 159.1 1000Jmol-1
ln K

159.1 1000Jmol-1
64 K e64 1.604 10 28
-1
-1
8.314JK mol 298K
3
2
O2

2
3

Since K p pO2 K 2.952 10 19 . The equilibrium constant and partial pressure


of

oxygen are both very small at 298 K. Therefore, KO2(s) is thermodynamically stable
with respect to K2O(s) and O2(g) at 298 K.

Group 2: The Alkaline Earth Metals


13.

(M) CaO

CO2

CaCO3
CaHPO4

Ca(OH)2

H3PO4

HCl

H2SO4

CaCl2

electrolysis

Ca

CaSO4

Ca OH 2 s + 2 HCl aq CaCl2 aq + 2H 2 O(l)

The reactions are as follows.

,electrolysis
CaCl2 l
Ca l + Cl2 g Ca OH 2 s + CO 2 g CaCO3 s + H 2 O g

CaCO3 s
CaO s + CO 2 g

Ca OH 2 s + H 2SO 4 aq CaSO 4 s + 2 H 2 O(l)

Ca OH 2 s + H 3 PO 4 aq CaHPO 4 aq + 2H 2 O(l) . Actually CaO s is the industrial

starting material from which Ca(OH) 2 is made. CaO(s) + H 2O(l)


Ca(OH) 2 (s)
14.

(M) MgO

MgCO3
MgHPO4

CO2

Mg(OH)2 HCl

H3PO4

H2SO4

MgCl2

electrolysis

Mg

N2

Mg3N2

MgSO4

Once we return to Mg(OH)2 from MgSO4, the other substances can be made by the indicated
pathways. The return reaction is: MgSO 4 (aq) + 2 NaOH(aq) Mg(OH) 2 (s) + Na 2SO 4 (aq).
Then the other reactions are

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Chapter 21: Chemistry of the Main-Group Elements I: Groups 1, 2, 13, and 14

Mg(OH) 2 (s) + 2 HCl(aq) MgCl 2 (aq) +2 H 2O(l)


, electrolysis
MgCl 2 (l)
Mg(l) + Cl2 (g) ;

Mg(OH) 2 (s) + CO 2 (g) MgCO3 (s) + H 2 O(g)

MgCO3 (s)
MgO(s) + CO 2 (g); Mg(OH)2 (s) + H 2 SO4 (aq) MgSO 4 (s) + 2H 2 O(l)
Mg(OH) 2 (s) + H 3 PO 4 (aq) MgHPO 4 (aq) + 2H 2 O(l)
15.

(M) The reactions involved are:


Mg2+(aq) + Ca2+(aq) + 2OH(aq) Mg(OH)2(s) + Ca2+(aq)
Mg(OH)2(s) + 2 H+(aq) + 2 Cl(aq) Mg2+(aq) + 2 H2O(l) + 2 Cl(aq)

Mg2+(aq) + 2 Cl(aq)
MgCl2(s)
MgCl2(s) (electrolysis) Mg(l) + Cl2(g)
Mg(l) Mg(s)
Mg2+ + 2 Cl(aq) Mg(s) + Cl2(g) (Overall reaction)
As can be seen, the process does not violate the principle of conservation of charge.

16.

(M) (a)
MgO vs. BaO: MgO would have the higher melting point because, although
2+
Mg and Ba2+ have the same charge, Mg2+ is a smaller ion. Smaller ions have a
larger electrostatic attraction to anions (here, in both cases, the anion is O2), which is
due to the smaller charge separation (Coulomb's law).

MgF2 vs. MgCl2 solubility in water. F is smaller than Cl, hence, electrostatic attraction
between Mg2+ and the halide is greater in F than Cl. If we assume that hydration of the
ions is similar, we expect that MgF2 is less soluble than MgCl2. (Note: Ksp given for
MgF2, which is sparingly soluble, while no Ksp value is given for readily soluble MgCl2.)

(M) (a)
BeF2 (s) + Mg(s)
Be(s) + MgF2 s

(b)

17.

18.

(b)

Ba s + Br2 l
BaBr2 s

(c)

UO 2 s + 2 Ca s
U s + 2 CaO s

(d)

MgCO3 CaCO3 s
MgO s + CaO s + 2 CO 2 g

(e)

2 H 3PO 4 aq + 3 CaO s
Ca 3 PO 4 2 s + 3 H 2 O l

(M) (a)
(b)

electrolysis
BaCl2 l
Ba l + Cl2 g

(c)

Sr s + 2 HBr aq
SrBr2 aq + H 2 g

(d)
(e)
19.

heat
Mg HCO3 2 s
MgO s + 2 CO 2 g + H 2O(l)

H 2SO 4 aq + Ca OH 2 aq
CaSO 4 s + 2H 2O l

CaSO 4 2 H 2 O s
CaSO 4 12 H 2O s + 32 H 2O g

(D) Let us compute the value of the equilibrium constant for each reaction by combining
the two solubility product constants. Large values of equilibrium constants indicate that the
reaction is displaced far to the right. Values of K that are much smaller than 1 indicate
that the reaction is displaced far to the left.
(a)

Ba 2+ aq + SO 4 2 aq
BaSO 4 s

1071

K sp 1.11010

Chapter 21: Chemistry of the Main-Group Elements I: Groups 1, 2, 13, and 14

BaCO3 s
Ba 2+ aq + CO32 aq

1/ K sp = 1/ (5.1 109 )

BaCO3 s + SO 4 2 aq
BaSO 4 s + CO32 aq

K=

1.11010
= 2.2 102
9
5.1 10

Thus, the equilibrium lies slightly to the left.


(b)

3 Mg 2+ aq + 2 PO 43 aq
Mg 3 PO 4 2 s

K sp = 2.11025

MgCO3 s }
3{Mg 2+ aq + CO32 aq

1/ ( K sp )3 = 1/ (3.5 108 )3

3 MgCO3 s + 2 PO 43 aq
Mg 3 PO 4 2 s + 3CO32 aq

K=
(c)

2.11025

3.5 10

8 3

= 4.9 103 Thus, the equilibrium lies to the left.

Ca 2+ aq + 2 OH aq
Ca OH 2 s

K sp = 5.5 106

CaF2 s
Ca 2+ aq + 2 F aq

1/ K sp 1/ (5.3 109 )

CaF2 s + 2 OH aq K =
Ca(OH) 2 s + 2 F aq

5.5 106
= 1.0 103
5.3 109

Thus, the equilibrium lies to the right.


20.

(M) We expect the reaction to occur to a significant extent in the forward direction if its
equilibrium constant is >> 1.
Ba 2+ aq + CO32 aq
(a) BaCO3 s
K sp = 5.1109

2H + aq + 2C 2 H 3O 2 aq
2 HC2 H 3O 2 aq

K a 2 = 1.8 105

HCO3 aq
H + aq + CO32 aq

1/ K a 2 = 1/ (4.7 1011 )

H 2 CO3 aq
H + aq + HCO3 aq

1/ K a1 = 1/ (4.2 107 )

Ba C2 H 3O 2 aq + H 2CO3 aq
BaCO3 s + 2 HC2 H 3O 2 aq
2
K=

5.1 10 9 1.8 10 5
11

= 8.4 10 2

4.7 10 4.2 10
Thus, no significant reaction occurs (the equilibrium mixture contains appreciable
amounts of all four species involved in the reaction.

(b)

Ca 2+ aq + 2 OH aq
Ca OH 2 s
2 NH3 aq + 2 H 2 O(l)
2 NH 4 + aq + 2 OH aq

K sp = 5.5 106
1/ K b 2 = 1/ 1.8 105

Ca 2+ aq + 2 NH 3 aq + 2 H 2 O(l)
Ca OH 2 s + 2 NH 4 + aq

K=

5.5 106

1.8 10

5 2

= 1.7 104

Thus, this reaction would occur to a significant extent.

1072

Chapter 21: Chemistry of the Main-Group Elements I: Groups 1, 2, 13, and 14

(c)

Ba 2+ aq + 2 F aq
BaF2 s

K sp = 1.0 106

2 HF aq + 2 H 2 O(l)
2 H 3O + aq + 2 F aq

1/ K a 2 = 1/ 6.6 104

6
Ba 2+ aq + 2HF aq + 2H 2 O(l); K = 1.0 10 2 = 2.3
BaF2 s + 2H 3O aq
6.6 104

This reaction would occur to some extent, but certainly not to completion.
21.

(M)

The SO42 ion is a large polarizable ion. A cation with a high polarizing power
will polarize the SO42 ion and kinetically assist the decomposition to SO3.
Because Be2+ has the largest charge density of the group 2 cations, we expect Be2+
to be the most polarizing and thus, BeSO4 will be the least stable with respect to
decomposition.

22.

(M)

The CO32 ion is a large polarizable ion. A cation with a high polarizing power
will polarize the CO32 ion and kinetically assist the decomposition to CO2. A
cation with a low polarizing power will not polarize the anion as much; thus, the
decomposition of CO32 to CO2 will not occur as readily in the presence of such a
cation. Because Ba2+ has the smallest charge density of the group 2 cations, we
expect Ba2+ to be the least polarizing; thus, BaSO4 will be the most stable with
respect to decomposition.

Group 13: The Boron Family


23.

(M) (a)
B4 H10 contains a total of 4 3 +10 1 = 22 valence electrons or 11 pairs. Ten of
these pairs could be allocated to form 10 BH bonds, leaving but one pair to bond
the four B atoms together, which is clearly an electron deficient situation.
(b)

In our analysis in part (a), we noted that the four B atoms had but one electron pair to
bond them together. To bond these four atoms into a chain requires three electron
pairs. Since each electron pair in a bridging bond replaces two normal bonds, there
must be at least two bridging bonds in the B4 H10 molecules. By analogy with B2 H 6 ,
we might write the structure below left. But this structure uses only a total of 20
electrons. (The bridge bonds are shown as dots, normal bondselectron pairsas
dashes.) In the structure at right below, we have retained some of the form of B2 H 6 ,
and produced a compound with the formula B4 H10 and 11 electron pairs. (The
experimentally determined structure of B4 H10 consists of a four-membered ring of
alternating B and H atoms, held together by bridging bonds. Two of the B atoms
have two H atoms bonded to each of them by normal covalent bonds. The other two
B atoms have one H atom covalently bonded to each. One final BB bond joins
these last two B atoms, across the diameter of the ring.). See the diagram that
follows:

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Chapter 21: Chemistry of the Main-Group Elements I: Groups 1, 2, 13, and 14

H
B

(c)

HH

H B
H

H
B

B
H

C4 H10 contains a total of 4 4 +10 1 = 26 valence electrons or 13 pairs. A plausible


Lewis structure follows. (Note that each atom possess an octet of electrons.)
H H H H

C H

H H H H
24. (E) (a)

F
F

(b)
F

(M) (a)

H H H
+
B N C C H
F

25.

H H H

2BBr3(l) + 3H2(g) 2B(s) + 6HBr(g)

B2O3(s) + 3 C(s)

3 CO(g) + 2 B(s)

2 B(s) + 3 F2(g)
2 BF3(g)

(b)

i)
ii)

(c)

2 B(s) + 3 N2O(g)

3 N2(g) + B2O3(s)

26.

(M) Each boron atom has an oxidation number of +3. The hydroxyl oxygens are each 2,
while the bridging oxygens are each 1. Finally, the hydroxyl H atoms are all in the +1
oxidation state. The oxidation numbers for the all the constituent atoms add up to the
charge on the perborate ion, namely, 2.

27.

(M) (a)

2 Al s + 6 HCl aq 2 AlCl 3 aq + 3 H 2 g

(b)

2 NaOH aq + 2 Al s + 6 H 2 O l 2 Na + aq + 2 Al OH 4 aq + 3 H 2 g

(c)

Oxidation: {Al s
Al3+ aq + 3 e }
Reduction: {SO 4

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

_________________________________________________________________________________________________________________________________

Net: 2 Al s + 3 SO 4
28. (M) (a)
(b)

2 Al3+ aq + 3 SO 2 aq + 6 H 2 O(l)
aq +12 H + aq

2 Al(s) + 3 Br2(l)
2 AlBr3(s)

2 Al s + Cr2O 3 s heat
2 Cr l + Al2 O 3 s

1074

Chapter 21: Chemistry of the Main-Group Elements I: Groups 1, 2, 13, and 14

(c)

Fe 2 O3 s + OH aq
no reaction

Al2 O3 s + 2 OH aq + 3 H 2 O(l)
2 Al OH 4 aq
29.

(M) One method of analyzing this reaction is to envision the HCO 3 ion as a combination
of CO 2 and OH . Then the OH reacts with Al 3+ and forms Al OH 3 . This method of

envisioning HCO 3 does have its basis in reality. After all,


H 2 CO3 = H 2 O + CO 2 + OH
HCO3 + H 2 O

Al 3+ aq + 3 HCO 3 aq
Al OH 3 s + 3 CO 2 g
Another method is to consider the reaction as, first, the hydrolysis of hydrated aluminum
ion to produce Al OH 3 s and an acidic solution, followed by the reaction of the acid
with bicarbonate ion.
Al H 2 O 6

3+

Al OH 3 H 2 O 3 s + 3H 3O + aq
aq + 3H 2O(l)

3H 3O + aq + 3HCO3 aq
6 H 2 O(l) + 3CO 2 g

This gives the same net reaction:


Al H 2 O 6

30.

3+

Al OH 3 H 2 O 3 s + 3CO 2 g + 3H 2 O(l)
aq + 3HCO3 aq

(E) The Al 3+ aq ion hydrolyzes. Al3+ aq + 3 H 2 O(l)


Al OH 3 s + 3 H + aq

Subsequently, the hydrogen ion that is produced reacts with bicarbonate ion to liberate CO 2 g .
H + aq + HCO3 aq
H 2 O(l) + CO 2 g

31.

(M) Aluminum and its oxide are soluble in both acid and base.
2 Al s + 6 H + aq
2 Al3+ aq + 3 H 2 g

Al2 O3 s + 6 H + aq
2 Al3+ aq + 3 H 2 O(l)

2 Al s + 2 OH aq + 6 H 2 O(l)
2 Al OH 4 aq + 3 H 2 g

Al2 O3 s + 2 OH aq + 3 H 2 O(l)
2 Al OH 4 aq
Al(s) is resistant to corrosion only over the pH range 4.5 to 8.5. Thus, aluminum is inert only
when the medium to which it is exposed is neither highly acidic nor highly basic.
32.

(M) Both Al and Mg are attacked by acid and their ions are both precipitated by hydroxide
ion.
2 Al s + 6 H + aq
2 Al3+ aq + 3 H 2 g
Mg s + 2 H + aq
Mg 2+ aq + H 2 g

Al3+ aq + 3 OH aq
Al OH s
3

1075

Mg 2+ aq + 2 OH
Mg OH s
2

Chapter 21: Chemistry of the Main-Group Elements I: Groups 1, 2, 13, and 14

But, of these two solid hydroxides, only Al OH 3 s redissolves in excess OH aq .

Al OH 3 s + OH aq
Al OH 4 aq

Thus, the analytical procedure consists of dissolving the sample in HCl(aq) and then
treating the resulting solution with NaOH(aq) until a precipitate forms. If this precipitate
dissolves completely in excess NaOH(aq), the sample is aluminum 2S. If at least some of
the precipitate does not dissolve, the sample was magnesium.
33.

(M) CO 2 g is, of course, the anhydride of an acid. The reaction here is an acid-base
reaction.

Al OH 4 aq + CO 2 aq
Al OH 3 s + HCO 3 aq
HCl(aq), being a strong acid, cant be used because it will dissolve the Al(OH)3(s).

34.

(M) (a)
(b)

35.

Oersted: 2 Al2O 3 s + 3 C s + 6 Cl2 g


4 AlCl3 s + 3 CO 2 g

Whler: AlCl3 s + 3 K s
Al s + 3 KCl s

(M) 2 KOH(aq) + 2 Al(s) + 6 H2O(l) 2 K[Al(OH)4](aq) + 3 H2(g)

2 K[Al(OH)4](aq) + 4 H2SO4(aq) K2SO4(aq) + Al2(SO4)3(aq) + 8 H2O(l)


crystallize 2 KAl(SO4)2(s)
36.

(E) HCO3 and CO32 solutions are basic (they produce an excess of OH). Al3+(aq) in the
presence of OH(aq) will precipitate as the hydroxide Al(OH)3(s).

37.

(E) The structure of, and bonding in, digallane is similar to the structure of and bonding
in diborane, B2H6.
H

Ga

Ga
H

38.

(M) The structure of, and bonding in, GaH2Cl2 is similar to the structure of and bonding
in Al2Cl6, except that the terminal Cls in Al2Cl6 are replaced by Hs.
Cl

Ga
H

Ga
Cl

Group 14: The Carbon Family


39.

(E) In the sense that diamonds react imperceptibly slowly at room temperature (either with
oxygen to form carbon dioxide, or in its transformation to the more stable graphite), it is
essentially true that diamonds last forever. However, at elevated temperatures, diamond
will burn to form CO2(g) and thus the statement is false. Also, the transformation
1076

Chapter 21: Chemistry of the Main-Group Elements I: Groups 1, 2, 13, and 14

C(diamond) C(graphite) might occur more rapidly under other conditions. Eventually, of
course, the conversion to graphite occurs.
40. (E) The graphite in the pencil lead is a good dry lubricant that will make slippery the
stickiness (or reluctance) in the lock and enable it to work smoothly. The key carries the
graphite to the site that needs to be lubricated within the lock mechanism.
41.

42.

43.

3 SiO2(s) + 4 Al(s)

(M) (a)

2 Al2O3(s) + 3 Si(s)

CO2(g) + K2SiO3(s)

(b)

K2CO3(s) + SiO2(s)

(c)

Al4C3(s) + 12 H2O(l)

3 CH4(g) + 4Al(OH)3(s)

(M) (a)
2 KCN(aq) + AgNO3(aq)
KAg(CN)2(aq) + KNO3(aq)
or KCN(aq) + AgNO3(aq) Ag(CN)(s) + KNO3(aq)
(b)

Si3H8(l) + 5 O2(g)

(c)

N2(g) + CaC2(s)

3 SiO2(s) + 4 H2O(l)

CaNCN(s) + C(s)

(M) A silane is a silicon-hydrogen compound, with the general formula Si n H 2 n +2 . A silanol is


a compound in which one or more of the hydrogens of silane is replaced by an OH group.
Then, the general formula becomes Si n H 2 n +1 OH . In both of these classes of compounds, the

number of silicon atoms, n, ranges from 1 to 6. Silicones are produced when silanols condense
into chains, with the elimination of a water molecule between every two silanol molecules.
HO Si n H 2 n OH + HO Si n H 2 n OH
HO Si n H 2 n O Si n H 2 n OH + H 2O
44.

(M) Both the alkali metal carbonates and the alkali metal silicates are soluble in water.
Hence, they also are soluble in acids. However, the carbonates will produce gaseous carbon
dioxide CO 2 on reaction with acid,

CO

2
3

(aq) + 2 H + (aq)
H 2 CO3
H 2 O(l) + CO 2 (g) , while the silicates will

produce silica SiO 2 in an analogous reaction

SiO

45.

4
4

(aq) + 4H + (aq)
H 4SiO 4
2 H 2 O(l) + SiO 2 (s) . The silica is produced in

many forms depending on reaction conditions: a colloidal dispersion, a gelatinous precipitate,


or a semisolid gel. Silicates of cations other than those of alkali metals are insoluble in water,
as are the analogous carbonates. However, the carbonates will dissolve in acids (witness the
reaction of acid rain on limestone carvings and marble statues, both forms of CaCO3 ), while
the silicates will not. (Silicate rocks are not significantly affected by acid rain.)
(M) (1)
2 CH 4 g + S8 g
2 CS2 g + 4 H 2S g
(2)

CS2 g + 3 Cl2 g
CCl4 l + S2 Cl2 l

(3)

4 CS2 g + 8 S2 Cl2 g
4 CCl4 l + 3 S8 (s)

1077

Chapter 21: Chemistry of the Main-Group Elements I: Groups 1, 2, 13, and 14

46.

(M) (a)
2

CH 3 3 Si OH(aq) + HCl(aq)
CH3 3 SiCl(l) + H 2 O(l)
CH 3 3 Si O Si CH 3 3 (s) + H 2 O(l)
CH3 3 Si OH(aq)

(b)

A silicone polymer does not form from CH 3 3 Si Cl . Only a dimer is produced.

(c)

The product that results from the treatment of CH 3SiCl3 is two long SiOSi
chains, with CH 3 groups on the outside, linked by SiOSi bridges. Part of one of
these chains and the beginnings of the bridges are shown below.
O
O

Si

O
O

CH3

Si

O
O

CH3

Si

O
O

CH3

Si

O
O

CH3

Si

O
O

CH3

Si

CH3

47.

(D) Muscovite or white mica has the formula KAl2(OH)2(AlSi3O10). Since they are not
segregated into O2 units in the formula, all of the oxygen atoms in the mineral must be in
the 2 oxidation state. Potassium is obviously in the +1 oxidation state, as are the
hydrogen atoms in the hydroxyl groups. Up to this point, we have -24 from the twelve
oxygen atoms and +3 from the potassium and hydrogen atoms for a net number of -21 for
the oxidation state. We still have three aluminum atoms and three silicon atoms to account
for. In oxygen-rich salts such as mica, we would expect that the silicon and the aluminum
atoms would be in their highest possible oxidation states, namely +4 and +3, respectively.
Since the salt is neutral, the oxidation numbers for the silicon and aluminum atoms must
add up to +21. This is precisely the total that is obtained if the silicon and aluminum atoms
are in their highest possible oxidation states: (3 (+3) + 3 (+4) = +21). Consequently,
the empirical formula for white muscovite is consistent with the expected oxidation state
for each element present.

48.

(D) Crysotile asbestos has the formula [Mg3Si2O5(OH)4]. Since they are not segregated to
O2 units in the formula, all of the oxygen atoms in the mineral must be in the 2 oxidation
state. The three magnesium atoms are obviously in the +2 oxidation state, while hydrogen
atoms in the hydroxyl groups have an oxidation state of +1. Up to this point, then, the sum
of the oxidation numbers equals 8 (18 from O-atoms, +6 from Mg-atoms, and + 4 from
H-atoms). Since the mineral is neutral, the two silicon atoms must have oxidation states
that sum to +8 (8 + 8 = neutral mineral), therefore, each silicon would need to be in the
+4 oxidation state. In oxygenrich salts such as asbestos, we would expect that the silicon
atoms would be in their highest possible oxidation state, namely +4. Thus, the oxidation
states for the element, in this mineral are precisely consistent with expectations.
(M) (a)
PbO s + 2 HNO3 aq
Pb NO3 2 s + H 2 O(l)

49.

(b)

SnCO 3 s
SnO s + CO 2 g

(c)

PbO s + C s
Pb l + CO g

1078

Chapter 21: Chemistry of the Main-Group Elements I: Groups 1, 2, 13, and 14

(d)

2 Fe 3+ aq + Sn 2 + aq
2 Fe 2+ aq + Sn 4 + aq

(e)

2 PbS s + 3 O 2 g
2 PbO s + 2 SO 2 g

2 SO 2 g + O 2 g
2 SO3 g
SO 3 g + PbO s
PbSO 4 s

Or perhaps simply: PbS s + 2 O 2 g


PbSO 4 s
Yet a third possibility:
PbO s + SO 2 s
PbSO3 s , followed by 2 PbSO3 s + O 2 s
2PbSO 4 s
50.

(M) (a)
Treat tin(II) oxide with hydrochloric acid.
SnO s + 2 HCl aq
SnCl 2 aq + H 2O(l)
(b)

Attack tin with chlorine. Sn s + 2 Cl2 g


SnCl 4 s

(c)

First we dissolve PbO 2 s in HNO 3 aq and then treat the resulting solution with
K 2CrO 4 aq to precipitate PbCrO4(s)
2 PbO 2 s + 4 HNO3 aq
2 Pb NO3 2 aq + O 2 g + 2 H 2 O(l)
Pb NO3 2 aq + K 2 CrO 4 aq
PbCrO 4 s + 2 KNO3 aq

51.

(M) We start by using the Nernst equation to determine whether the cell voltage still is
positive when the reaction has gone to completion.
(a)

Oxidation: Fe 2+ aq Fe3+ aq + e } 2

E = 0.771 V

Reduction: PbO 2 s + 4 H + aq + 2 e
Pb 2+ aq + 2 H 2 O(l) E = +1.455 V
Net: 2 Fe2+ aq + PbO 2 s + 4 H + (aq)
2 Fe3+ aq + Pb 2+ aq + 2 H 2 O(l)

Ecell
= 0.771 V +1.455 V = +0.684 V

In this case, when the reaction has gone to completion,


Fe 2+ = 0.001 M , Fe 3+ = 0.999 M, and Pb 2+ = 0.500 M.
0.0592
[Fe3 ]2 [Pb 2 ]
0.0592
[0.999]2 [0.500]
=
0.684
V
= 0.515 V.
log

log
2
[Fe 2 ]2
2
[0.001]2
Thus, this reaction will go to completion.

Ecell = Eocell

(b)

2
S2 O8 aq + 2 e
E = 2.01V
aq
Reduction: PbO 2 s + 4 H + aq + 2 e
Pb 2+ aq + 2 H 2 O(l)
E = +1.455 V
2
2
2 SO 4 aq + PbO 2 s + 4 H + (aq)
S2 O8 aq + Pb 2+ aq + 2 H 2 O(l)

Oxidation: 2 SO 4

1079

Chapter 21: Chemistry of the Main-Group Elements I: Groups 1, 2, 13, and 14

Ecell
= 2.01+1.455 = 0.56 V This reaction is not even spontaneous initially.

(c)

Oxidation: {Mn 2+ 1 10

-4

MnO 4 aq +8H + aq +5 e- } 2 ; E o = 1.51 V


+4H 2O(l)

Pb 2+ aq +2 H 2O(l)}5
Reduction: {PbO 2 s +4 H + aq +2 e

Net: 2Mn 2+ 1 10

-4

E o =+1.455 V

2MnO 4 aq + 5Pb 2+ aq + 2H 2 O(l)


+ 5PbO 2 s + 4H +

o
Ecell
= 1.51+1.455 = 0.06 V. The standard cell potential indicates that this reaction is
not spontaneous when all concentrations are 1 M. Since the concentration of a reactant
Mn 2 + is lower than 1.00 M, this reaction is even less spontaneous than the standard

cell potential indicates.


52.

(M) A positive value of Ecell


indicates that a reaction should occur.
2+
(a) Oxidation : Sn aq
Sn 4+ aq + 2 e
E = 0.154 V

Reduction : I 2 s + 2 e
2 I aq
Net :

E = +0.535 V

Sn 2+ aq + I 2 s
Sn 4+ aq + 2 I aq

_________________________________________

Ecell
= +0.381 V

Yes, Sn 2+ aq will reduce I 2 to I .


(b)

Oxidation : Sn 2+ aq
Sn 4+ aq + 2 e

E = 0.154 V

Reduction : Fe 2+ aq + 2 e
Fe s
Sn aq + Fe s
aq + Fe aq
2+
No, Sn aq will not reduce Fe 2 + aq to Fe(s).
Net :

(c)

Sn

2+

2+

E = 0.440 V
________________________________________

Ecell
= 0.594 V

4+

Oxidation : Sn 2+ aq
Sn 4+ aq + 2 e

E = 0.154 V

Reduction : Cu 2+ aq + 2 e
Cu s

E = +0.337 V
______________________________________________________

Net :

Sn 2+ aq + Cu 2+ aq
Sn 4+ aq + Cu s

Ecell
= +0.183 V

Yes, Sn 2+ aq will reduce Cu 2 + aq to Cu(s).


(d)

Oxidation : Sn 2+ aq
Sn 4+ aq + 2 e

E = 0.154 V

Reduction : {Fe3+ aq + e
Fe 2+ aq } 2

E = +0.771 V
___________________________________________________________

Sn aq + 2 Fe aq
aq + 2 Fe aq
Yes, Sn 2+ aq will reduce Fe 3+ aq to Fe 2 + aq .
Net :

53.

Sn

2+

3+

4+

2+

Ecell
= +0.617 V

(M) As we move down a group, the lower oxidation state is generally favored. Thus, we
expect PbCl2, with lead in the +2 oxidation state, to be the product.

1080

Chapter 21: Chemistry of the Main-Group Elements I: Groups 1, 2, 13, and 14

54.

(M) As we move down a group, the lower oxidation state is generally favored. The higher
oxidation state is favored for elements higher in the group. Thus, we expect GeF4, with
lead in the +4 oxidation state, to be the product.

INTEGRATIVE AND ADVANCED EXERCISES


55. (M) What most likely happened is that a deliquescent solid has absorbed water vapor from
the air over time and formed a saturated solution. This saturated solution can be used in any
circumstance where the solid would be used to prepared an aqueous solution. Of course, the
concentration will have to be determined by some means other than weighing, such as a
gravimetric analysis or using a standard to react with the substance in a titration.
Alternatively, the saturated solution can be heated in a drying oven to drive off the water and
the solid may be recovered. Often, unfortunately, a solid with an unknown percent of water
results from this treatment.
56.

(D) (a) A solution of CO2(aq) has [CO32-] = Ka2[H2CO3] = 5.610-11 M. Since the Ksp =
2.810-9 for CaCO3, the [Ca2+] needed to form a precipitate from this solution can be
computed.
K sp
2.8 10-9
[Ca2+] =
=
= 50. M
[Ca 2+ ] 5.6 10-11

This is too high to reach by dissolving CaCl2 in solution. The reason a solid forms is that
the OH- produced by the Ca(OH)2 neutralized some of the HCO3- from the ionization of
CO2(aq), thereby increasing the [CO32-] above a value of 5.610-11 M.
(b) The equation for redissolving can be obtained by combining several equations.

CaCO3(s) Ca2+(aq) + CO32-(aq)


CO32-(aq) + H3O+(aq) HCO3-(aq) + H2O(l)
CO2(aq) + 2 H2O(l) HCO3-(aq) + H3O+(aq)

Ksp = 2.810-9
1/Ka2 = 1/(5.610-11)
Ka1 = 4.210-7

CaCO3(s) + CO2(aq) + H2O(l) Ca2+(aq) + 2 HCO3-(aq) K =

K sp K a1
K a2

[Ca 2+ ][HCO-3]2
(2.8 10-9 ) (4.2 10-7 )
-5
K=
= 2.1 10 =
[CO 2 ]
(5.6 10-11 )
2+
If CaCO3(s) is precipitated from 0.005 M Ca (aq) and then redissolved, [Ca2+] =
0.005 M and [HCO3-] = 20.005 M = 0.010 M. We use these values in the above
expression to compute the [CO2].
[Ca 2+ ][HCO-3]2
[CO 2 ] =
= 0.002 M
(2.1 10-5 )
We repeat the calculation for saturated Ca(OH)2, in which [OH-] = 2 [OH-], after
first determining [Ca2+] in this solution.

1081

Chapter 21: Chemistry of the Main-Group Elements I: Groups 1, 2, 13, and 14

Ksp = [Ca2+][OH-]2 = 4[Ca2+] = 5.5 10-6 [Ca2+] =


[Ca 2+ ][HCO-3]2

5.5 106
= 0.011 M
4

(0.011)(0.022)2
= 0.25 M
(2.1 10-5 )
2.1 10-5
Thus, to redissolve the CaCO3 requires that the [CO2] = 0.25 M, assuming the solution
is initially saturated with Ca(OH)2(aq).
(c) follow the solution for (b) above.
[CO 2 ] =

57. (M) There are two principal reasons why the electrolysis of NaCl(l) is used to produce sodium
commercially rather than the electrolysis of NaOH(l). First, NaCl is readily available whereas
NaOH is produced from the electrolysis of NaCl(aq). Thus the raw material NaCl is much cheaper
than is NaOH. Second, but less important, when sodium is produced from the electrolysis of
NaCl(l), a by-product is Cl2(g), whereas O2(g) is a by-product of the production of NaOH(l).
Since O2(g) can be produced more cheaply by the fractional distillation of liquid air, Cl2(g) can be
sold for a higher price than O2(g). Thus, the two reasons for producing sodium from NaCl(l)
rather than NaOH(l) are a much cheaper raw material and a more profitable by-product.
58. (M)
The triiodide ion is linear (AX2E3). The Li+ ion has a high charge density and
significant polarizing power. The Li+ ion will polarize the I3 to a significant extent and
presumably assists the decomposition of I3 to I2 and I.
I

59. (M)

I
1

Use Gfo values to calculate G o for the reaction and then K. Because K PO22 , the

value of K can then be used to calculate PO2 .


1
Li2 O 2 (s) Li2O(s)+ O 2 (g)
2

G of [ kJ / mol ]

-419.02

-466.40

G o 466.40 (419.02) 47.38kJmol-1


G o RT ln K
8.314JK -1mol-1 1000K ln K 47.38 1000Jmol-1
ln K

47.38 1000Jmol-1
5.70 K e5.70 298
8.314JK -1mol-1 1000K

1
2
O2

K P PO2 K 2 298 2 8.8 10 4

60. (M)

o
o
o
o
Use Shydr.
T1 H hydr.
Ghydr.
values:
to calculate Shydr.

1082

Chapter 21: Chemistry of the Main-Group Elements I: Groups 1, 2, 13, and 14

o
S hydr.
(Li )

1
298

o
(Na )
S hydr.
o
(K )
S hydr.

522 (481) 0.14J/Kmol


407 (375) 0.11J/Kmol
324 (304) 0.07J/Kmol
299 (281) 0.06J/Kmol
274 (258) 0.05J/Kmol

1
298

1
298

o
(Rb )
S hydr.

1
298

o
(Cs )
S hydr.

1
298

o
All the S hydr.
values are negative because, in the process, a gas is being converted into a
o
o
liquid solution. However, S hydr.
is most negative for Li+. The S hydr.
values increase as

we move down the group from Li+ to Cs+. As the charge density and polarizing power of
the metal cation decreases, so too does the degree of order (or organization) in the
hydration sphere. Thus, the entropy change should be most negative for Li+ and least
negative for Cs+.

61.

120, 200 z z
34.5
1
, with
r r
r r
r+ and r in picometers, to calculate U in kJ mol1. For LiO2, z+ = +1, z = 1, and = 2.
(b) When we apply the BornFajansHaber cycle to the reaction Li(s) + O2(g) LiO2(s),
o
o
+ IE(1)Li 43 + U. Values of H f,Li(g)
and IE(1)Li are given in
we get H fo = H f,Li(g)

(M) (a)

Use the Kapustinskii equation in the form U

Appendix D and in Table 21.2, respectively. (c) For the reaction 2 LiO2(s) Li2O(s) +
o
o
o
3
2 O2(g), H = H f,Li 2 O(s) 2 H f,LiO2 (s) . (d) The decomposition reaction is exothermic
( H o < 0) and, with the assumption that entropy effects are not important, the
decomposition of LiO2(s) to Li2O(s) and O2(g) is thermodynamically favorable.
62. (M) (a) The mass of MgO(s) that would be produced can be determined with information
from the balanced chemical equation for the oxidation of Mg(s).

2 Mg(s) O 2 (g )
2 MgO(s)
mass MgO 0.200 g Mg

1 mol Mg
2 mol MgO 40.30 g MgO

0.332 g MgO
24.305 g Mg 2 mol Mg
1 mol MgO

(b) If the mass of product formed from the starting Mg differs from the 0.332 g MgO
predicted, then the product could be a mixture of magnesium nitride and magnesium
oxide. This scenario is not implausible since molecular nitrogen is readily available in the
atmosphere. 3 Mg(s) N 2 (g)
Mg 3 N 2 (s)

mass Mg 3N 2 =0.200 g Mg

1 mol Mg 3N 2 100.93 g Mg 3N 2
1 mol Mg

=0.277 g Mg 3N 2
3 mol Mg
1 mol Mg 3N 2
24.305 g Mg

1083

Chapter 21: Chemistry of the Main-Group Elements I: Groups 1, 2, 13, and 14

We can use a technique similar to determining the percent abundance of an isotope.


Let f = the mass fraction of MgO in the product. The (1.000 f) is the mass fraction of
Mg3N2 in the product. product mass = mass MgO f + [mass Mg3N2 (1.000 f)]
0.315 g product = 0.332 f + [0.277 (1.000 f)] = 0.277 + f(0.332 0.277)
f

0.315 0.277
0.69
0.332 0.277

The product is 69% by mass MgO.

C
63. (M) Reaction (21.4) is KCl(l) Na(l) 850

NaCl(l) K(g) It is practical when the


reactant element is a liquid and the product element is a gas at the same temperature.

(a) Since Li has a higher boiling point (1347C) than K (773.9C), a reaction similar to
(21.4) is not a feasible way of producing Li metal from LiCl.
(b) On one hand, Cs has a lower boiling point (678.5C) than K (773.9C), and thus a
reaction similar to (21.4) is a feasible method of producing Cs metal from CsCl.
However, the ionization energy of Na is considerably larger than that of Cs, making it
difficult to transfer an electron from Na to Cs+.

2 Al(s) + Fe2O3(s) 2 Fe(s) + Al2O3(s)

64. (M) (a)

H = -852 kJ

(b) 4 Al(s) + 3 MnO2(s) 2 Al2O3(s) + 3 Mn(s)

H = -1792 kJ

(c) 2 Al(s) + 3 MgO(s) Al2O3(s) + 3 Mg(s)

H = +129 kJ

65. (M) Li+(aq) + e- Li(s) G = -293.3 kJ = -nFE = -1 mol e- (96,485 C/mol e-)E

E = -3.040 V (this value is the same as the one that appears in Table 21.2.)
66. (M) The partial pressure of H2 is 748 mmHg 21 mmHg = 727 mmHg

amount H 2

727 mm Hg (1 atm/760 mmHg) 0.104 L


PV

=4.10 103 mol H 2


-1
-1
RT
0.08206 Latm K mol 296 K

The electrode reactions are the following.


Cl 2 (g) 2 e
2 OH (aq) H 2 ( g )
Anode : 2 Cl (aq)
Cathode : 2 H 2 O(l) 2 e
Thus 2 mol OH(aq) are produced per mole of H2(g); 8.20 103 mol OH(aq) are produced.

[OH ]

8.20 10 3 mol OH
3.28 10 2 M 0.0328 M
0.250 L soln

Then we compute the ion product and compare its value to the value of Ksp for Mg(OH)2.
Qsp [Mg 2 ][OH ] 2 (0.220)(0.0328) 2 2.37 10 4 1.8 10 11 K sp for Mg(OH) 2
Thus, Mg(OH)2 should precipitate.

1084

Chapter 21: Chemistry of the Main-Group Elements I: Groups 1, 2, 13, and 14

67. (D) (a) We determine the amount of Ca2+ associated with each anion in 106 g of the water.
2
1 mol SO 4
1 mol Ca 2
2
2
2

0.592 mol
amount Ca (SO 4 ) 56.9 g SO 4
2
2
96.06 g SO 4
1 mol SO 4

amount Ca 2 (HCO 3 ) 176 g HCO 3

1 mol HCO 3
61.02 g HCO 3

1 mol Ca 2
2 mol HCO 3

1.44 mol

Then we determine the total mass of Ca2+, numerically equal to the ppm Ca2+.
mass Ca 2 (0.592 1.44) mol Ca 2

40.08 g Ca 2
81.4 g Ca 2
81.4 ppm Ca 2
2
1 mol Ca

(b) The reactions for the removal of HCO3(aq) begin with the formation of hydroxide ion
resulting from dissolving CaO(s). Hydroxide ion reacts with bicarbonate ion to form carbonate
ion, which then combines with calcium ion to form the CaCO3(s) precipitate.

CaO(s) H 2 O(l)
Ca 2 (aq) 2 OH (aq)

OH (aq) HCO 3 (aq)


H 2 O(l) CO 3 (aq)
2

Ca 2 (aq) CO 3 (aq)
CaCO 3 (s)
For each 1.000 106 g of water, we need to remove 176 g HCO3(aq) with the added CaO(s).
mass CaO 602 10 g water
3

176 g HCO 3

1 mol HCO 3

1.000 10 6 g water 61.02 g HCO 3

1 mol OH
1 mol HCO 3

1 mol CaO 56.08 g CaO

48.7 g CaO
2 mol OH 1 mol CaO

(c) Here we determine the total amount of Ca2+ in 602 kg of water, and that added as CaO.

602 kg
1 mol CaO 1 mol Ca 2+
2+
(0.592+1.44)
mol
Ca
+
48.7
g
CaO

= 2.09 mol Ca 2+

1 106 kg
56.08 g CaO 1 mol CaO

Ca 2+ =

The amount of Ca2+ that has precipitated equals the amount of HCO3 in solution, since each
mole of HCO3 is transformed into 1 mole of CO32, which reacts with and then precipitates
one mole of Ca2+. Thus the amount of Ca2+ that has precipitated is (0.602)(1.44) = 0.867 mol
Ca2+ as CaCO3(s). Then we can determine the concentration of Ca2+ remaining in solution.
2.09 mol Ca 2 total 0.867 mol Ca 2 10 3 g water
[Ca ]

2.03 10 3 M
6
1 L water
10 g water
2

To consider the Ca2+ removed, its concentration should be decreased to 0.1% (0.001) of
its initial value, or 2.03 106 M. We use the Ksp expression for CaCO3 to determine the
needed [CO32]
Ksp [Ca 2 ][CO32 ] 2.8 109 1.46 106 M
[CO32 ]

2.8 109
0.0014 M
2.03 106

1085

Chapter 21: Chemistry of the Main-Group Elements I: Groups 1, 2, 13, and 14

This carbonate ion concentration can readily be achieved by adding solid Na2CO3.
(d) The amount of CO32 needed is that which ends up in the precipitate plus that needed to
attain the 0.0014 M concentration in the 602 kg = 602 L of water.
0.00203 mol Ca 2+ 1 mol CO 2- 0.0014 mol CO 2-
23
3

n CO-2 = 602 L
+
= 2.1 mol CO3
2+
3
1
L
water
1
L
water
1 mol Ca

This CO32 comes from the added Na2CO3(s).


mass Na 2 CO 3 2.0 mol CO 3

1 mol Na 2 CO 3 105.99 g Na 2 CO 3

2.2 10 2 g Na 2 CO 3
1 mol CO 32
1 mol Na 2 CO 3

68. (M) (a) In the cell reaction, three moles of electrons are required to reduce each mole of Al 3+.
mass Al 8.00 h

3600 s 1.00 105 C 1 mol e 1 mol Al 26.98 g Al

2.68 105 g Al

1h
1 mol Al
96,485 C 3 mol e
1s

The 38% efficiency is not considered in this calculation. All of the electrons produced
must pass through the electrolytic cell; they simply require a higher than optimum voltage
to do so, leading to resistance heating (which consumes some of the electrical energy).
(b) total energy 4.5 V 8.00 h

3600 s 1.00 10 5 C
1J
1 kJ

1.3 10 7 kJ
1s
1h
1 V C 1000 J

mass coal = 1.3 107 kJ electricity

1 kJ heat
1gC
1 g coal 1 metric ton

0.35 kJ electricity 32.8 kJ 0.85 g C


106 g

mass coal = 1.3 metric tons of coal

69. (M) We begin by rewriting Equation 21.25 for the electrolysis of Al2O3(s) with n = 12 e-.

3 C(s) + 2 Al2O3(s) 4 Al(s) + 3 CO2(g)


G = 4(0 kJ/mol) + 3(-394 kJ) [3(0 kJ/mol) + 2(-1520 kJ/mol)] = +1858 kJ
G = 1.858 106 J = -nFE = -12 mole e-(96,485 C/mol e-)E

Note: this is just an estimate because G values are at 298 K, whereas


E = -1.605 V
the reaction occurs at a temperature that is much higher than 298 K.
If the oxidation of C(s) to CO2(g) did not occur, then the cell reaction would just be the
reverse of the formation reaction of Al2O3 with n = 6 e-.
E = E o =

G o
1.520 106 J
=
-2.626 V
nF
6 mole- 96485C/mole-

70. (M) It would not be unreasonable to predict that Raoults law holds under these
circumstances. This is predicated on the assumption, of course, that Pb(NO3)2 is completely
ionized in aqueous solution.

1086

Chapter 21: Chemistry of the Main-Group Elements I: Groups 1, 2, 13, and 14

Pwater xwater Pwater

xwater

Pwater
97% 0.97
P water

Thus, there are 97 mol H2O in every 100 mol solution. The remaining 3 moles are 1 mol
Pb2+ and 2 mol NO3. Thus there is 1 mol Pb(NO3)2 for every 97 mol H2O. Compute the
mass of Pb(NO3)2 in 100 g H2O.
mass Pb(NO

3 )2

= 100.0 g H 2O

1 mol H 2O
18.02 g H 2O

1 mol Pb(NO3 ) 2
97 mol H 2O

331.2 g Pb(NO3 ) 2
1 mol Pb(NO3 ) 2

= 19 g Pb(NO3 ) 2

If we did not assume complete ionization of Pb(NO3)2, we would obtain 3 moles of unionized Pb(NO3)2 in solution for every 97 moles of H2O. Then there would be 57 g
Pb(NO3)2 dissolved in 100 g H2O. A handbook gives the solubility as 56 g Pb(NO3)2/100 g
H2O, indicating only partial dissociation or, more probably, extensive re-association into ion
pairs, triplets, quadruplets, etc.
71. (M) Considerable energy is required to produce the Pb4+ cationfour ionization steps, one
for the removal of each electron. It therefore needs quite a large lattice energy to compensate
for its energy of production. Both Br and I are large anions, and therefore the Pb4+Br
and Pb4+I interionic distances are long. But lattice energy depends on the charge of the
cation (which is quite large) multiplied by the charge of the anion (which is reasonably
small) divided by the square of the interionic distance (long, as we have said). Thus, we
predict a small lattice energy that is insufficient to stabilize the Pb4+ cation. We would
predict, however, that PbF4 and PbCl4 (both with small anions) and PbO2 and PbS2 (both
with small, highly charged anions) would be stable compounds.
In addition, notice that
Eo {Pb4+|Pb2+} = 1.5 V (from Table 21-6) is sufficient to oxidize Br to Br2 and I to I2, since
Eo {Br2|Br} = +1.065 V and Eo {I2|I} = +0.535 V. Thus, even if PbI4 or PbBr4 could be
prepared they would be thermodynamically unstable.
72. (M) Na2B4O7.10 H2O(s) + 6 CaF2(s) + 8 H2SO4(aq) 4 BF3(aq) + 6 CaSO4(aq) + 17 H2O(l) + 2
NaHSO4(aq)

73. (D) (a) 1.00 M NH4Cl is a somewhat acidic solution due to hydrolysis of NH4+(aq); MgCO3
should be most soluble in this solution. The remaining two solutions are buffer solutions,
and the 0.100 M NH31.00 M NH4Cl buffer is more acidic of the two. In this solution,
MgCO3 has intermediate solubility. MgCO3 is least soluble in the most alkaline solution,
namely, 1.00 M NH31.00 M NH4Cl.

Mg 2 (aq) CO32 (aq)


MgCO3 (s)

K sp 3.5 108

NH3 (aq) H 2 O(l)


NH 4 (aq) OH (aq)
1/K b 1/1.8 105
HCO3 (aq) H 2 O(l) 1/K 2 1/ 4.7 1011
CO32 (aq) H 3O (aq)
H 3O (aq) OH (aq)
2 H 2 O(l)

K w 1.0 1014

Mg 2 HCO3 (aq ) NH 3 (aq)


MgCO3 (s) NH 4 (aq)

1087

Chapter 21: Chemistry of the Main-Group Elements I: Groups 1, 2, 13, and 14

K sp K w
Kb K2

3.5 108 1.0 1014


4.1 107
5
11
1.8 10 4.7 10

In 1.00 M NH4Cl
Reaction: MgCO3 (s)

NH 4 (aq)

Mg 2 (aq) HCO3 (aq)

NH 3 (aq)

Initial:

1.00 M

0M

0M

0M

Changes:

x M

x M

x M

xM

Equil:

(1.00 x)M

xM

xM

xM

[Mg 2 ][HCO3 ][NH 3 ] x x x


x3

[NH 4 ]
1.00 x
1.00

x 3 4.1 107 7.4 103 M molar solubility of MgCO3 in1.00 M NH 4 Cl


( x 1.00 M, thus the approximation was valid)

(b) In 1.00 M NH31.00 M NH4Cl

Reaction:
Initial:
Changes:
Equil:
K

MgCO3 (s)

Mg 2 (aq) HCO3 (aq) NH3 (aq)


NH 4 (aq)
1.00 M
0M
0M
1.00 M
x M
x M
x M
x M
xM
xM
(1.00 x )M
(1.00 x)M

[Mg 2 ][HCO3 ][NH 3 ] x x (1.00 x) x 2 1.00

[NH 4 ]
1.00 x
1.00

x 4.1 107 6.4 104 M molar solubility of MgCO3 in 1.00 M NH3 -1.00 M NH 4 Cl

( x 1.00 M, thus the approximation was valid)


(c) In 0.100 M NH31.00 M NH4Cl
Reaction:
Initial:

Mg 2 (aq) HCO3 (aq) NH 3 (aq)


MgCO3 (s) NH 4 (aq)

1.00 M
0M
0M
0.100 M

Changes:

x M

Equil:

(1.00 x )M

x M
xM

x M

x M

xM

(0.100 x)M

[Mg 2 ][HCO3 ][NH 3 ] x x (0.100 x) x 2 0.100

1.00 x
1.00
[NH 4 ]

4.1 107
2.0 103 M solubility of MgCO3 in 0.100 M NH 3 -1.00 M NH 4 Cl
0.100
(x is 2 % of 0.100 M, so the approximation was valid)
x

1088

Chapter 21: Chemistry of the Main-Group Elements I: Groups 1, 2, 13, and 14

74. (M) If the value of the equilibrium constant for the reaction is quite large, then the
conversion will be almost complete. We write the net ionic equation and then add the two
solubility reactions to obtain the net ionic equation for the conversion. The equilibrium
constants are multiplied together to give the equilibrium constant for the conversion.

CaCO3 (s) 2 OH (aq)


Ca(OH) 2 (s) CO32 (aq)

Net ionic equation:

Ca 2 (aq) 2 OH (aq)
Ca(OH) 2 (s)

K sp 5.5 106

CaCO3 (s)
Ca 2 (aq) CO32 (aq)

1/K sp 1/ 2.8 109

Ca(OH) 2 (s) CO3

5.5 106

(aq) CaCO3 (s) 2 OH (aq) K ovedrall


2.0 103
9
2.8 10

Because Koverall > 1000, the conversion is substantially complete.


75. (M) The density of each metal depends on two factors: its atomic size and the masses of the
individual atoms. Density is thus, proportional to the atomic mass divided by the cube of the
atomic radius. We calculate this ratio for each of the elements.
Li:

atomic mass
atomic mass
atomic mass
Na:
K:
3
3
(atomic radius)
(atomic radius)
(atomic radius)3
39.10 (g/mol)
6.941 (g/mol)
22.99 (g/mol)

3.34

1.98

3.57
3
3
3

[2.27 (A)]
[1.52 (A)]
[1.86 (A)]

We see that the calculated ratios follow the same pattern as the densities: Na K Li, thus
explaining why Na has a higher density than both Li and K.
76.

(M) We would expect MgO(s) to have a larger value of lattice energy than MgS(s) because
of the smaller interionic distance in MgO(s).
Lattice energy of MgO:

Enthalpy of formation:

MgO(s)
Mg(s) O 2 (g)

H f 6.02 10 2 kJ

Sublimation of Mg(s):

Mg(s)
Mg (g)

H sub 146 kJ

Ionization of Mg(g)

Mg(g)
Mg (g) e

I 1 737.7 kJ

Ionization of Mg(g):

Mg (g)
Mg 2 (g) e

I 2 1451 kJ

1
2

Dissociation O2(g):

1
2

O 2 (g)
O(g)

DE 12 497.4 248.7 kJ

O(g) electron affinity:

O (g)
O(g) e

EA 1 141 kJ

O(g) electron affinity:

O 2 (g)
O - (g) e

EA 2 744 kJ

Lattice energy:

Mg 2 (g) O 2 (g) MgO(s)

L.E = -3789 kJ(see below)

1089

Chapter 21: Chemistry of the Main-Group Elements I: Groups 1, 2, 13, and 14

L.E = -602 kJ 146 kJ 737.7 kJ 1451 kJ 248.7 kJ + 141 kJ 744 kJ = -3789 kJ


Lattice energy of MgS:

Enthalpy of formation:

Mg(s) S(g)
MgS(s)

H f 3.46 10 2 kJ

Sublimation of Mg(s):

Mg(s)
Mg (g)

H sub 146 kJ

Ionization of Mg(g)

Mg(g)
Mg (g) e

I 1 737.7 kJ

Ionization of Mg(g):

Mg (g)
Mg 2 (g) e

I 2 1451 kJ

1
2

Dissociation of S2(g):

1
2

S rhombic (g)
S(g)

DE 12 557.6 278.8 kJ

S(g) electron affinity:

S (g)
S(g) e

EA 1 200.4 kJ

S(g) electron affinity:

S - (g) e
S 2 (g)

EA 2 456 kJ

Lattice energy:

Mg 2+ (g) + S2- (g) MgS(s)

L.E = -3215 kJ

L.E = -346 kJ 146 kJ 737.7 kJ 1451 kJ 278.8 kJ + 200.4 kJ 456 kJ = -3215 kJ


1
1
1
8+
6 = 4 fulleride ions and
12 + 1 + 8 = 12
8
2
4
alkali metal ions. The ratio of cations to anions is 12:4 = 3:1, and so the fulleride ion is C603
and the empirical formula is M3C60.

77. (M)

In one unit cell, there are

FEATURE PROBLEMS
78.

(D) Li(s) Li(g)


Li(g) Li+(g) + e
Li+(g) Li+(aq)
Li(s) Li+(aq) + e

159.4 kJ; (UsingHrxn = Hfproducts Hfreactants in Appendix D)


520.2 kJ; (Data given in Table 21.2, Chapter 21)
506 kJ; (Provided in the question)
174 kJ

1/2 H2(g) H(g)


218.0 kJ (UsingHrxn = Hfproducts Hfreactants in Appendix D)
+

1312 kJ
(Use RH(NA)Bohr theory = 2.179 1018 J(6.022 1023))
H(g) H (g) + e
1079 kJ (Provided in the question)
H+(g) H+(aq)
+

1/2 H2(g) H (aq) + e 451 kJ

(a) Li(s) + H+(aq) Li+(aq) + 1/2 H2(g)


H = 174 kJ 451 kJ = 277 kJ G
o
3
G
277 10 J
J
Eox =

= 2.87 = 2.87 V
C
nF
C

1 mol e 96,485

mol e

1090

Chapter 21: Chemistry of the Main-Group Elements I: Groups 1, 2, 13, and 14

In this reaction, Li(s) is being oxidized to Li+(aq). If we wish to compare this to the
reduction potential for Li+(aq) being reduced to Li(s), we would have to reverse the
reaction, which would result in the same answer only as a negative value.
Alternatively, we can change the sign of the oxidation potential (Li Li+) to -2.87 V
for the reduction potential for Li+ Li.
(it apears as -3.040 V in Appendix D; here, we see much better agreement.)
(b) S = Sproducts - Sreactants
J
J

= [1 mol 13.4
+ 0.5 mol 130.7
]
Kmol
Kmol

J
J
J

[1 mol 29.12
+ 1 mol 0
] = 49.6
K
Kmol

Kmol
J 1kJ

G = H TS = 277 kJ 298.15 K 49.6


292 103 J
K 1000 J

G o
292 103 J
J
Eox =

= 3.03 = 3.03 V
C
nF
C

1 mol e 96,485

mol e

As mentioned in part (a) of this question, we have calculated the oxidation potential
for the half reaction Li(s) Li+(aq) + e-. The reduction potential is the reverse halfreaction and has a potential of -3.03 V. This is in excellent agreement with -3.040 V
given in Appendix D.
79.

(D) (a)
0. 438 mol NaCl 58.443 g NaCl

= 26.6 g NaCl
L
1 mol NaCl
0. 0512 mol MgCl2
95.211 g MgCl2

= 4.87 g MgCl2
L
1 mol MgCl2

31.5 g of salt
per liter of
seawater

10 g NaHCO3
307 g of salt per
= 180 g NaHCO3
1 tbs NaHCO3
gal. of lake water
(3.7854 L/gal)
10 g NaCl
10 tbs NaCl
= 100 g NaCl
1 tbs NaCl
1 tbs 10 g MgSO 4 7 H 2O
8 tsp MgSO4 7 H2O

= 27 g MgSO4 7 H2O
3 tsp 1 tbs MgSO 4 7 H 2 O
18 tbs NaHCO3

(b)

The pH of the lake will be determined by the amphiprotic bicarbonate ion, (HCO3),
which hydrolyzes in water ( K a1 = 4.4 107 or pK a1 = 6.36 and K a 2 = 4.7 1011
or pK a 2 = 10.33). We saw earlier (Chapter 18, Exercise 100) that the pH of a
solution of alanine, a diprotic species is independent of concentration (as long as it is
1091

Chapter 21: Chemistry of the Main-Group Elements I: Groups 1, 2, 13, and 14

relatively concentrated). The pH =

(pK a1 pK a 2 )
2

(6.36 10.33)
= 8.35
2

This is not as basic as the actual pH of the lake. Addition of borax (sodium salt of
boric acid) would aid in increasing the pH of the solution (since borax contains an
anion that is the conjugate base of a weak acid). The lake may be more basic due to
the presence of other basic anions, namely carbonate ion (CO32).
(c)

Tufa are mostly made of calcium carbonate (CaCO3(s)). Since they form near
underwater springs, one must assume that the springs have a high concentration of
calcium ion (Ca2+(aq)). We then couple this with the fact that the lake has a high
salinity (high carbonate and bicarbonate ion content). We can thus conclude that two
major reactions are most likely responsible for the formation of a tufa (see below):
Ca2+(aq) + CO32(aq) CaCO3(s)
Ca2+(aq) + 2 HCO3(aq) Ca(HCO3)2(q) CaCO3(s) + H2O(l) + CO2(g)

SELF-ASSESSMENT EXERCISES
80.

(E) (a) A dimer is a chemical or biological entity consisting of two structurally similar
subunits called monomers, which are joined by bonds, which can be strong or weak.
(b) An adduct is a product of a direct addition of two or more distinct molecules, resulting
in a single reaction product containing all atoms of all components, with formation of two
chemical bonds and a net reduction in bond multiplicity in at least one of the reactants.
(c) Calcination is a thermal treatment process applied to ores and other solid materials in
order to bring about a thermal decomposition, phase transition, or removal of a volatile
fraction.
(d) An amphoteric oxide is an oxide that can act both as an acid and as a base. An
example is aluminum oxide Al2O3.
(e) A three-center two-electron bond is an electron deficient chemical bond where three
atoms share two electrons. The combination of three atomic orbitals form three molecular
orbitals: one bonding, one non-bonding, and one anti-bonding. The two electrons go into
the bonding orbital, resulting in a net bonding effect and constituting a chemical bond
among all three atoms.

81.

(E) (a) A diagonal relationship exists between certain pairs of diagonally adjacent
elements in the second and third periods of the periodic table. These pairs (Li and Mg, Be
and Al, B and Si, etc.) exhibit similar properties. For example boron and silicon are both
semiconductors.
(b) One way to prepare deionized water is by passing it through an ion exchange column.
The latter is composed of insoluble chemicals which remove both positive and negative
ions from water.
(c) Thermite is a pyrotechnic composition of a metal powder and a metal oxide, which
produces an aluminothermic reaction known as a thermite reaction.

1092

Chapter 21: Chemistry of the Main-Group Elements I: Groups 1, 2, 13, and 14

(d) The inert pair effect is the tendency of the outermost s electrons to remain un-ionized
or unshared in post-transition compounds.
82.

(E) (a) A peroxide is a compound containing an oxygen-oxygen single bond. Superoxide


is an anion with the chemical formula O-2 .
(b) Calcium oxide (CaO) is commonly known as burnt lime, lime or quicklime. Calcium
hydroxide (Ca(OH)2) on the other hand is commonly known as slaked lime, hydrated lime,
or slack lime.
(c) Soap is an anionic surfactant used in conjunction with water for washing and cleaning.
Soap consists of sodium or potassium salts of fatty acids and is obtained by reacting
common oils or fats with a strong alkaline solution in a process known as saponification.
Detergents, on the other hand, are prepared synthetically.
(d) A silicate is a compound containing an ion in which one or more central silicon atoms
are surrounded by electronegative ligands. Silicones are compounds containing siliconoxygen and silicon-carbon bonds that have the capability to act as bonding intermediates
between glass and organic compounds, and to form polymers with useful properties such
as impermeability to water, flexibility and resistance to chemical attack.
(e) The sol-gel process is a chemical solution deposition technique widely used in the
fields of materials science and ceramic engineering. Typical precursors are metal alkoxides
and metal chlorides, which undergo various forms of hydrolysis and polycondensation
reactions.

83.

(E)

(c) MgO

84.

(E)

(f) PbO2

85.

(M) (a) BCl3NH3(g) (an adduct); (b) KO2(s); (c) Li2O(s); (d) Ba(OH)2(aq) and H2O2(aq);

H2O2(aq) slowly disproportionates into H2O(l) and O2(g).


86.

(M) The thermite reaction is evidence that aluminum will readily extract oxygen from

Fe2O3. Aluminum can be used for making products that last and for structural purposes,
because aluminum develops a coating of Al2O3 that protects the metal beneath it.
87.

(M) (b) Ca(s) and CaH2(s)

88.

(M) (a)
(b)
(c)
(d)
(e)

Li2 CO 3 (s)
Li2O(s)+CO 2 (g)
CaCO 3 (s)+2HCl(aq)
CaCl2 (aq)+H 2O(l)+CO 2 (g)
2Al(s)+2NaOH(aq)+6H 2 O(l)
2Na[Al(OH)4 ](aq)+2H 2 (g)
BaO(s)+H 2 O(l)
Ba(OH)2 (aq,limited solubility)
2Na 2O 2 (s)+2CO 2 (g)
2Na 2CO 3 (s)+O 2 (g)

1093

Chapter 21: Chemistry of the Main-Group Elements I: Groups 1, 2, 13, and 14

89.

(M) (a) MgCO 3 (s)+2HCl(aq)


MgCl2 (aq)+H 2 O(l)+CO 2 (g)
(b) 2Na(s)+2H 2O(l)
2NaOH(aq)+H 2 (g) followed by the reaction in Exercise
82(c)
(c) 2NaCl(s)+H 2 SO 4 (concd.,aq)
Na 2 SO 4 (s)+2HCl(g)

90.

(M) (a) K 2CO 3 (aq)+Ba(OH)2 (aq)


BaCO 3 (s)+2KOH(aq)

(b) Mg(HCO 3 )2 (aq)


MgCO 3 (s)+H 2 O(l)+CO 2 (g)
(c) SnO(s)+C(s)
Sn(l)+CO(g)
(d) CaF2 (s)+H 2SO 4 (concd. aq)
CaSO 4 (s)+2HF(g)
(e) NaHCO 3 (s)+HCl(aq)
NaCl(aq)+H 2O(l)+CO 2 (g)
(f) PbO 2 (s)+4HBr(aq)
PbBr2 (s)+Br2 (l)+2H 2O(l)
(g) SiF4 (g)+4Na(l)
Si(s)+4NaF(s)

91.

(M) CaSO 4 2H 2 O(s)+(NH 4 )2 CO 3 (aq)


CaCO 3 (s)+(NH 4 )2 SO 4 (aq)+2H 2 O(l) . The
reaction proceeds to the right because Ksp for CaCO3<Ksp for CaSO4

92.

(M) (a) 2B(OH)3 (s)


B2O 3 (s)+3H 2O(g)
(b) no reaction

3
1
H 2 O(s)[plaster of Paris]+ H 2O(g)
2
2
(M) (a) Pb(NO 3 )2 (aq)+2NaHCO 3 (aq)
PbCO 3 (s)+2NaNO 3 (aq)+H 2 O(l)+CO 2 (g) In
NaHCO3(aq) the concentration of CO32-(aq) is high enough that Ksp of PbCO3 is
exceeded.
(b) Li2 O(s)+(NH 4 )2 CO 3 (aq)
Li2 CO 3 (s)+2NH 3 (g)+H 2 O(l) . Li2O(s) is the
anhydride of the strong base LiOH, which reacts with acidic NH4+(aq) to liberate
NH3(g). Li2CO3(s) is only slightly soluble, so most of it precipitates.
(c) H 2 SO 4 (aq)+BaO 2 (aq)
H 2 O 2 (aq)+BaSO 4 (s) . The forward reaction is
favored by the formation of a precipitate, BaSO4(s).
(d) 2PbO(s)+Ca(OCl)2 (aq)
CaCl2 (aq)+2PbO 2 (s) . Hypochlorite ion oxidizes
lead(II) oxide to lead(IV) oxide.
(c) CaSO 4 2H 2O(s)[gypsum]
CaSO 4

93.

94.
95.

(M) (a) Stalactites are primarily CaCO3(s). (b) Gypsum is CaSO4x2H2O(s). (c)
Suspension of BaSO4(s) in water. (d) Al2O3(s) with Fe3+ and Ti4+ replacing some Al3+ in
the crystal structure.
(M) Dolomite, molar mass of 184.4 g/mol yields 2 mol CO2(g) per mol of dolomite on
decomposition. The 5.00103 kg sample yields 5.42104 mol CO2 which, under the
stated conditions occupies a volume of 1.27103 m3.

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