CHAPTER 21

CHEMISTRY OF THE MAIN-GROUP ELEMENTS I:

GROUPS 1, 2, 13, AND 14
PRACTICE EXAMPLES
1A 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 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 NaCl aq  + 2 H 2O l  electrolysis
  2 NaOH aq  + H 2 g  + Cl2 g 
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
the addition of S to the boiling solution: Na 2SO3  aq  + S(s) 
boil
Na 2S2 O3  aq  .

2A 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 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 C N

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3A The first two reactions, are those from Example 21-3, used to produce B2 O3 .
 4 B  OH 3 (s) + Na 2SO 4 (s) + 5 H 2 O(l)
Na 2 B4 O7 10 H 2 O(s) + H 2SO 4 (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 Na2B4O7.10 H2O(s) + H2SO4(aq)  4 B(OH)3(s) + Na2SO4(aq) + 5 H2O(l)


2 B(OH)3(s)   B2O3(s) + 3 H2O(l)

B2O3(s) + 3 CaF2(s) + 3 H2SO4(l)   2 BF3(g) + 3 CaSO4(s) + 3 H2O(g)

INTEGRATIVE EXAMPLE
A 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 É HCN+OH
1.0 / /
1.0-x x x
14
Kw 1.0  10
Kb    1.6  10 5
K a (HCN ) 6.2  10 10
[HCN ][OH  ] xx x2
Kb  
   1.6  10 5
[CN ] 1.0  x 1.0  x
Assume, x<<1 and 1.0-x1.0
x 2  1.6  10 5  x  1.6  10 5  4.0  10 3
[OH  ]  4.0  10 3
On mixing, [OH-]=2.010-3 M and [Al3+]=0.50 M. The precipitation will occur according
to the following equation:
3+ -
Al (aq)+3OH (aq) É Al(OH)3 (s)
The product [Al3+][OH-]3=0.50(2.010-3)3=4.010-9 is much greater than KSP for Al(OH)3
(1.310-33) and therefore precipitation will occur.

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

B 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. (a) 2 Cs(s) + Cl2 (g) 

 2 CsCl(s)
(b) 2 Na(s) + O 2 (g) 
 Na 2 O2 (s)
(c) Li 2 CO3  s  

 Li 2 O  s  + CO 2  g 
(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 

3. 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.

5. 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.
Ksp = 3.5  10-8
1. 
MgCO3   Mg2+(aq) + CO32-(aq) Let “s” = molar solubility of MgCO3
excess – s s s
s2 = 3.5×10-8 s = 1.9×10-4 M

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

K = 2.5  10- 2
2. 
sp

Li2CO3  2 Li+(aq) + CO32-(aq) Let “s” = molar solubility of Li2CO3
excess – s 2s s
2.5×10-8
(2s)2×(s) = 2.5×10-8 4s3 = 2.5×10-8 s= = 0.18 M
3
4
We can conclude that Li2CO3 is more soluble than MgCO3. Thus, the expected order of
increasing solubility in water is: MgCO3 < Li2CO3 < Na2CO3.

7. (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.

 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.

.  103 mol OH 
126
[OH  ]  .  103 M
 145 pOH =  log(1.45  103 )  2.839
0.872 L soln
pH=14.000  2.839  11.161

(b) 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.

9. (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

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

(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
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.

11. Use G of values to calculate G o for the reaction and then the equilibrium constant
K at 298 K.
1
Na 2O 2 (s) É Na 2O(s)+ O 2 (g)
 2
G of (kJmol-1 ) -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
70.54  1000Jmol-1
ln K   28.47  K  e28.47  4.32  10 13
8.314JK mol  298K
-1 -1

1
Since K  pO22  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.

Group 2: The Alkaline Earth Metals

13.  CO2 HCl electrolysis

CaO CaCO3 Ca(OH)2 CaCl2 Ca

H3PO4 H2SO4
CaHPO4 CaSO4

The reactions are as follows. Ca  OH 2  s  + 2 HCl  aq   CaCl2  aq  + 2H 2 O(l)

CaCl2  l  
 ,electrolysis
 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 2 O(l) 
 Ca(OH) 2 (s)

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

15. 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.
17. (a) 
BeF2 (s) + Mg(s)   Be(s) + MgF2  s 
(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)  Ca 3 PO 4 2 s  + 3 H 2 O l
2 H 3PO 4 aq  + 3 CaO s  

19. 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) BaSO 4  s  
 Ba 2+  aq  + SO 4 2  aq  K sp  1.11010
Ba 2+  aq  + CO32  aq  
 BaCO3  s  1/ K sp = 1/ (5.1109 )
1.11010
BaSO 4  s  + CO32  aq  
 BaCO3  s  + SO 4 2  aq  K= = 2.2 102
5.1109
Thus, the equilibrium lies slightly to the left.

(b) Mg 3  PO 4 2  s  
 3 Mg 2+  aq  + 2 PO 43  aq  K sp = 2.11025
3{Mg 2+  aq  + CO32  aq  
 MgCO3  s } 1/ ( K sp )3 = 1/ (3.5 108 )3
Mg 3  PO 4 2  s  + 3CO32  aq  
 3 MgCO3  s  + 2 PO 43  aq 
2.11025
K= = 4.9  103 Thus, the equilibrium lies to the left.
 3.5 10 
8 3

(c) Ca  OH 2  s  
 Ca 2+  aq  + 2 OH   aq  K sp = 5.5 106
Ca 2+  aq  + 2 F  aq  
 CaF2  s  1/ K sp  1/ (5.3 109 )
6
 CaF2  s  + 2 OH   aq  K = 5.5  109 = 1.0 103
Ca(OH) 2  s  + 2 F  aq  
5.3 10
Thus, the equilibrium lies to the right.

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

21. 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.

Group 13: The Boron Family

23. (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 B—H 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 bonds—electron pairs—as
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 B—B bond joins
these last two B atoms, across the diameter of the ring.). See the diagram that
follows:
H H H H H HH H H H
         

B B B B H B B B B
         

H H H H H H H H H

(c) 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
H C C C C H
H H H H

25. (a) 2BBr3(l) + 3H2(g)  2B(s) + 6HBr(g)

(b) i) B2O3(s) + 3 C(s) 


3 CO(g) + 2 B(s)
ii) 2 B(s) + 3 F2(g) 
 2 BF3(g)


(c) 2 B(s) + 3 N2O(g) 



3 N2(g) + B2O3(s)

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27. (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  } 2
Reduction: {SO 4
2
 aq  + 4 H +  aq  + 2e 
 SO 2  g  + 2 H 2 O(l)} 3
_________________________________________________________________________________________________________________________________

Net: 2 Al  s  + 3 SO 4  aq  +12 H +  aq  
 2 Al3+  aq  + 3 SO 2  aq  + 6 H 2 O(l)
2


29. 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+
 aq  + 3H 2O(l) 
 Al  OH 3  H 2 O 3  s  + 3H 3O +  aq 

3H 3O +  aq  + 3HCO3  aq  
 6 H 2 O(l) + 3CO 2  g 


This gives the same net reaction:

 Al  H 2 O 6 
3+
 aq  + 3HCO3  aq  
 Al  OH 3  H 2 O 3  s  + 3CO 2  g  + 3H 2 O(l)

31. 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.

33. 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, can’t be used because it will dissolve the Al(OH)3(s).

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

35. 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)

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

Ga Ga

H H H

Group 14: The Carbon Family

39. 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
C(diamond) → C(graphite) might occur more rapidly under other conditions. Eventually, of
course, the conversion to graphite occurs.

41. (a) 3 SiO2(s) + 4 Al(s) 



2 Al2O3(s) + 3 Si(s)
(b) K2CO3(s) + SiO2(s) 


CO2(g) + K2SiO3(s)
(c) Al4C3(s) + 12 H2O(l)  3 CH4(g) + 4Al(OH)3(s)

43. 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

45. (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)

47. 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

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

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.

49. (a) PbO  s  + 2 HNO3  aq  

 Pb  NO3 2  s  + H 2 O(l)

(b) SnCO 3 s  

 SnO s  + CO 2 g 

(c) PbO s  + C s  

 Pb l + CO g 

(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 

51. 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.

o 0.0592 [Fe3 ]2 [Pb 2 ] 0.0592 [0.999]2 [0.500]

Ecell = E cell  log = 0.684 V  log = 0.515 V.
2 [Fe 2 ]2 2 [0.001]2
Thus, this reaction will go to completion.

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

(b) Oxidation: 2 SO 4  aq  
2
 S2 O8  aq  + 2 e
2
 E  = 2.01V
Reduction: PbO 2  s  + 4 H +  aq  + 2 e  
 Pb 2+  aq  + 2 H 2 O(l) E  = +1.455 V
2 SO 4  aq  + PbO 2  s  + 4 H + (aq)   S2 O8  aq  + Pb 2+  aq  + 2 H 2 O(l)
2 2

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

(c) Oxidation: {Mn 2+ 1  10 -4

M  MnO 4 aq +8H + aq +5 e- } 2 ;  E o =  1.51 V
+4H 2O(l) 
Reduction: {PbO 2  s  +4 H +  aq  +2 e  
 Pb 2+  aq  +2 H 2O(l)}×5 E o =+1.455 V
Net: 2Mn 2+ 1  10 -4
M  + 5PbO2  s  + 4H + 
 2MnO 4  aq  + 5Pb 2+  aq  + 2H 2 O(l)


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.

53. 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.

INTEGRATIVE AND ADVANCED EXERCISES

58. 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 I I

1
59. 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) É Li2O(s)+ O 2 (g)
 2
G of [kJ / mol] -419.02 -466.40

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

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
47.38  1000Jmol-1
ln K   5.70  K  e5.70  298
8.314JK mol  1000K
-1 -1

1
K  P  PO2  K 2  298 2  8.8  10 4
2
O2

62. (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)
1 mol Mg 2 mol MgO 40.30 g MgO
mass MgO  0.200 g Mg     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)

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

mass Mg 3N 2 =0.200 g Mg    =0.277 g Mg 3N 2
24.305 g Mg 3 mol Mg 1 mol Mg 3N 2
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)
0.315  0.277
f   0.69 The product is 69% by mass MgO.
0.332  0.277
C
63. 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 (1347°C) than K (773.9°C), 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 (678.5°C) than K (773.9°C), 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+.

64. (a) 2 Al(s) + Fe2O3(s)  2 Fe(s) + Al2O3(s) H = -852 kJ

(b) 4 Al(s) + 3 MnO2(s)  2 Al2O3(s) + 3 Mn(s) H = -1792 kJ

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

(c) 2 Al(s) + 3 MgO(s)  Al2O3(s) + 3 Mg(s) H = +129 kJ

66. The partial pressure of H2 is 748 mmHg – 21 mmHg = 727 mmHg

amount H 2 
PV


727 mm Hg  (1 atm/760 mmHg)  0.104 L 
=4.10  103 mol H 2
RT 0.08206 Latm K mol  296 K
-1 -1

The electrode reactions are the following.

Anode : 2 Cl  (aq) 
 Cl 2 (g)  2 e  Cathode : 2 H 2 O(l)  2 e  
 2 OH  (aq)  H 2 ( g )
Thus 2 mol OH (aq) are produced per mole of H2(g); 8.20 × 10 mol OH–(aq) are produced.
– –3

8.20  10 3 mol OH 
[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.

67. (a) We determine the amount of Ca2+ associated with each anion in 106 g of the water.
2
2 2 1 mol SO 4 1 mol Ca 2 
amount Ca 2  (SO 4 )  56.9 g SO 4  2
 2
 0.592 mol
96.06 g SO 4 1 mol SO 4
 
1 mol HCO 3 – 1 mol Ca 2 
amount Ca 2  (HCO 3 )  176 g HCO 3  
 
 1.44 mol
61.02 g HCO 3 2 mol HCO 3
Then we determine the total mass of Ca2+, numerically equal to the ppm Ca2+.

2 2 40.08 g Ca 2 
mass Ca  (0.592  1.44) mol Ca  2
 81.4 g Ca 2  
 81.4 ppm Ca 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.
 Ca 2  (aq)  2 OH  (aq)
CaO(s)  H 2 O(l) 
 2
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).
 
176 g HCO 3 1 mol HCO 3 1 mol OH 
mass CaO  602  10 3 g water   
1.000  10 6 g water 61.02 g HCO 3  1 mol HCO 3


1 mol CaO 56.08 g CaO

   48.7 g CaO
2 mol OH  1 mol CaO

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

(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+ 
Ca 2+ =  (0.592+1.44) mol Ca 2+
+ 48.7 g CaO   = 2.09 mol Ca 2+
 1  106 kg   56.08 g CaO 1 mol CaO 

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 ]    2.03  10 3 M
10 6 g water 1 L water
To consider the Ca2+ “removed”, its concentration should be decreased to 0.1% (0.001) of
its initial value, or 2.03 × 10–6 M. We use the Ksp expression for CaCO3 to determine the
needed [CO32–]
Ksp  [Ca 2 ][CO32 ]  2.8  109  1.46  106 M
2.8  109
[CO32 ]   0.0014 M
2.03  106
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- 
n CO-2 = 602 L     3
2+ 
+ 3 2-
 = 2.1 mol CO3
3
 1 L water 1 mol Ca  1 L water 

This CO32– comes from the added Na2CO3(s).

2 1 mol Na 2 CO 3 105.99 g Na 2 CO 3
mass Na 2 CO 3  2.0 mol CO 3    2.2  10 2 g Na 2 CO 3
1 mol CO 32 – 1 mol Na 2 CO 3

68. (a) In the cell reaction, three moles of electrons are required to reduce each mole of Al 3+.
3600 s 1.00  105 C 1 mol e  1 mol Al 26.98 g Al
mass Al  8.00 h     
  2.68  105 g Al
1h 1s 96,485 C 3 mol e 1 mol Al
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).
3600 s 1.00  10 5 C 1J 1 kJ
(b) total energy  4.5 V  8.00 h      1.3  10 7 kJ
1h 1s 1 V  C 1000 J
1 kJ heat 1gC 1 g coal 1 metric ton
mass coal = 1.3  107 kJ electricity    
0.35 kJ electricity 32.8 kJ 0.85 g C 106 g
mass coal = 1.3 metric tons of coal

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

69. 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
E = -1.605 V Note: this is just an estimate because G values are at 298 K, whereas
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-.
G o 1.520  106 J
E = E o = =  -2.626 V 
nF 6 mole-  96485C/mole-

70. It would not be unreasonable to predict that Raoult’s law holds under these circumstances.
This is predicated on the assumption, of course, that Pb(NO3)2 is completely ionized in
aqueous solution.
Pwater
Pwater  xwater Pwater xwater   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.
1 mol H 2O 1 mol Pb(NO 3 ) 2 331.2 g Pb(NO 3 ) 2
mass Pb(NO = 100.0 g H 2O    = 19 g Pb(NO3 ) 2
3 )2
18.02 g H 2O 97 mol H 2O 1 mol Pb(NO 3 ) 2

If we did not assume complete ionization of Pb(NO3)2, we would obtain 3 moles of un-
ionized 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.

73. (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 NH3–1.00 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 NH3–1.00 M NH4Cl.
 Mg 2 (aq)  CO32 (aq)
MgCO3 (s)  K sp  3.5 108
NH 4  (aq)  OH  (aq) 
 NH3 (aq)  H 2 O(l) 1/K b  1/1.8  105
CO32 (aq)  H 3O  (aq) 
 HCO3 (aq)  H 2 O(l) 1/K 2  1/ 4.7 1011

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

 H 3O  (aq)  OH  (aq)

2 H 2 O(l)  K w  1.0  1014
MgCO3 (s)  NH 4  (aq) 
 Mg 2  HCO3 (aq )  NH 3 (aq)

K sp  K w 3.5  108  1.0  1014

K  5 11
 4.1  107
Kb  K2 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
K  
[NH 4  ] 1.00  x 1.00
x  3 4.1 107  7.4 103 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 NH3–1.00 M NH4Cl
Reaction: MgCO3 (s)   Mg 2 (aq)  HCO3 (aq)  NH3 (aq)
NH 4  (aq) 
Initial:  1.00 M 0M 0M 1.00 M
Changes:  x M x M x M x M
Equil:  (1.00  x)M xM  xM (1.00  x)M
[Mg 2 ][HCO3 ][NH 3 ] x  x  (1.00  x) x 2 1.00
K  
[NH 4  ] 1.00  x 1.00

x  4.1  107  6.4  104 M  molar solubility of MgCO3 in 1.00 M NH 3 -1.00 M NH 4 Cl

( x  1.00 M, thus the approximation was valid)
(c) In 0.100 M NH3–1.00 M NH4Cl
Reaction: MgCO3 (s)  NH 4  (aq) 
 Mg 2 (aq)  HCO3 (aq)  NH 3 (aq)
Initial:  1.00 M 0M 0M 0.100 M
Changes:  x M x M x M x M
Equil:  (1.00  x )M xM  xM (0.100  x)M

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

[Mg 2 ][HCO3 ][NH 3 ] x  x  (0.100  x) x 2  0.100

K  
[NH 4  ] 1.00  x 1.00
4.1  107
x  2.0  103 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)

76. 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: Mg(s)  O 2 (g) 
 MgO(s) 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)  e 
Mg(g)  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)  e  

 O  (g) EA 1  141 kJ
O(g) electron affinity: O - (g)  e  
 O 2 (g) EA 2  744 kJ
Lattice energy: Mg 2  (g)  O 2  (g)  MgO(s) L.E = -3789 kJ(see below)
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)  e 
Mg(g)  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)  e  

 S  (g) 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

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

1 1 1
77. In one unit cell, there are ×8+ × 6 = 4 fulleride ions and × 12 + 1 + 8 = 12 alkali
8 2 4
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.

FEATURE PROBLEMS
78. Li(s)  Li(g) 159.4 kJ; (UsingHrxn = Hfproducts  Hfreactants in Appendix D)
Li(g)  Li+(g) + e 520.2 kJ; (Data given in Table 21.2, Chapter 21)
Li+(g)  Li+(aq) 506 kJ; (Provided in the question)
Li(s)  Li+(aq) + e  174 kJ
1/2 H2(g)  H(g) 218.0 kJ (UsingHrxn = Hfproducts  Hfreactants in Appendix D)

+
H(g)  H (g) + e 1312 kJ (Use RH(NA)Bohr theory = 2.179  1018 J(6.022  1023))
H+(g)  H+(aq) 1079 kJ (Provided in the question)
+ 
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
G o
277  10 J3
J
Eox =  = 2.87 = 2.87 V
nF  C  C
1 mol e   96,485  
 mol e 

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 = Sproducts - Sreactants

 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
 Kmol   Kmol  K
 J  1kJ
G = H  TS = 277 kJ – 298.15 K  49.6    292  103 J
 K  1000 J

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

G o 292  103 J J
Eox =  = 3.03 = 3.03 V
nF  C  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 half-
reaction and has a potential of -3.03 V. This is in excellent agreement with -3.040 V
given in Appendix D.

SELF-ASSESSMENT EXERCISES
83. (c) MgO

84. (f) PbO2

85. (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. 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. (b) Ca(s) and CaH2(s)

88. (a) Li2 CO 3 (s) 

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

89. (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. (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)

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

(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. CaSO 4  2H 2 O(s)+(NH 4 )2CO 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. (a) 2B(OH)3 (s) 

 B2O 3 (s)+3H 2O(g)
(b) no reaction
1 3
(c) CaSO 4  2H 2O(s)[gypsum] 
 CaSO 4  H 2 O(s)[plaster of Paris]+ H 2O(g)
2 2
93. (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.

94. (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.

95. Dolomite, molar mass of 184.4 g/mol yields 2 mol CO2(g) per mol of dolomite on
decomposition. The 5.00103 kg sample yields 5.42104 mol CO2 which, under the
stated conditions occupies a volume of 1.27103 m3.

609