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CHAPTER 22

CHEMISTRY OF THE MAIN GROUP ELEMENTS II:


GROUPS 18, 17, 16, 15 AND HYDROGEN
PRACTICE EXAMPLES
1A This question involves calculating E for the reduction half-reaction:
ClO3(aq) + 3 H2O(l) + 6 e  Cl(aq) + 6 OH(aq)
Here we will consider just one of the several approaches available to solve this
problem. The four half-reactions (and their associated E values) that are used in this
method to come up with the “missing E value” are given below. (Note: the E for the
first reaction was determined in Example 22-1)
1) ClO3(aq) + H2O(l) + 2 e  ClO2(aq) + 2 OH(aq) E = 0.295 V G1 = 2FE
2) ClO2(aq) + H2O(l) + 2 e  OCl(aq) + 2 OH(aq) E = 0.681 V G2 = 2FE
3) OCl(aq) + H2O(l) + 1 e  1/2 Cl2(aq) + 2 OH(aq) E = 0.421 V G3 = 1FE
4) 1/2 Cl2(aq) + 1 e  Cl(aq) E = 1.358 V G4 = 1FE
Although the reactions themselves may be added to obtain the desired equation, the E
for this equation is not the sum of the E values for the above four reactions. The E
value for the desired equation is actually the weighted average of the E values for
reactions (1) to (4). It can be calculated by summing up the free energy changes for the
four reactions. (The standard voltages for half-reactions of the same type are not
additive. The G values for these reactions can, however, be summed together.)
When (1), (2), (3) and (4) are added together we obtain
1) ClO3(aq) + H2O(l) + 2 e  ClO2(aq) + 2 OH(aq) E1 = 0.295 V 
+ 2) ClO2(aq) + H2O(l) + 2 e  OCl(aq) + 2 OH(aq) E2 = 0.681 V 
+ 3) OCl(aq) + H2O(l) + 1 e  1/2 Cl2(aq) + 2 OH(aq) E3 = 0.421 V 
+ 4) 1/2 Cl2(aq) + 1 e  Cl(aq) E4 = 1.358 V
           

ClO3(aq) + 3 H2O(l) + 6 e  Cl(aq) + 6 OH(aq) E5 = ?


and G5 = G1 + G2 + G3 + G4
so, 6FE5 = 2F(0.295 V) + 2F(0.681V) + 1F(0.421 V) + 1F(1.358 V)
- 2F(0.295 V)  - 2F(0.681V)  - 1F(0.421 V)  - 1F(1.358 V)
Hence, E5 = = 0.622 V
- 6F

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

1B. This question involves calculating E for the reduction half-reaction:


2 ClO3(aq) + 12H+(aq) + 10 e  Cl2(aq) + 6 H2O(l)
The three half-reactions (and their associated E values) are given below:
(1) ClO3(aq) + 3H+(aq) + 2 e  HClO2(aq) + H2O(l) E = 1.181 V
(2) HClO2(aq) + 2 H+(aq) + 2 e  HClO(aq) + H2O(l) E = 1.645 V
(3) 2 HClO (aq) + 2 H+(aq) + 2 e  Cl2(aq) + 2 H2O(l) E = 1.611 V
(remember that G= nFE)
Although the reactions themselves can be added to obtain the desired equation, the E
for this equation is not the sum of the E values for the above three reactions. The E
for the desired equation is actually the weighted average of the E values for reactions
(1) to (3). It can be obtained by summing up the free energy changes for the three
reactions. (For reactions of the same type, standard voltages are not additive; G
values are additive, however.) When (1) and (2) (each multiplied by two) are added to
(3) we obtain:
2(1) 2 ClO3(aq) + 6 H+(aq) + 4 e  2 HClO2(aq) + 2 H2O(l) E1 = 1.181 V
2(2) 2 HClO2(aq) + 4 H+(aq) + 4 e  2 HClO(aq) + 2 H2O(l) E2 = 1.645 V
(3) 2 HClO (aq) + 2 H+(aq) + 2 e  Cl2(aq) + 2 H2O(l) E3 = 1.611 V
            
 + 
2 ClO3 (aq) + 12 H (aq) + 10 e  Cl2(aq) + 6 H2O(l) E4 = ?
and G4 = G1 + G2 + G3
so, 10FE4 = 4F(1.181 V) + 4F(1.645 V) + 2F(1.611 V)
- 4F(1.181 V)  - 4F(1.645 V)  - 2F(1.611 V)
Hence, E4 = = 1.453 V
- 10 F

2A The dissociation reaction is the reverse of the formation reaction, and thus G  for the
dissociation reaction is the negative of G f

HF  g  
 12 H 2  g  + 12 F2 (g) G  = Gf =   273.2 kJ/mol 

We know that
G  =  RT ln K P +273.2  103 J/mol = 8.3145 J mol1 K 1  298 K  ln K P

273.2  103 J mol1


ln K P = = 110 K p = e110 = 1.7  1048  2 1048
8.3145 J mol1 K 1  298 K
Virtually no dissociation of HF(g) into its elements occurs.

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

2B The dissociation reaction with all integer coefficients is twice the reverse of the
formation reaction.

2HCl  g   H 2  g  + Cl 2  g  G  = 2   95.30 kJ / mol  = +190.6 kJ / mol =  RT ln K p

G  190.6  103 J / mol


ln K p = = = 76.9 K p = e 76.9 = 4  1034
RT 8.3145 J mol1 K 1  298 K
We assume an initial HCl(g) pressure of P atm, and calculate the final pressure of
Cl2(g) and H2(g), x atm.
Reaction: 2 HCl(g) 

 H2(g) + Cl2(g)

Initial: P atm 0 atm 0 atm
Changes: –2x atm +x atm +x atm
Equil: (P – 2x) atm x atm x atm

P{H 2  g }P{Cl2  g }
2
x x  x  x
Kp = = =  = 4  1034  2  1017
P{HCl  g } 2
 P  2x  P  2x 
2
P  2x

x = 2  1017  P  2 x   2  1017 P

2x
% decomposition =  100% = 2  2  1017  100%  4  1015 % decomposed
P

INTEGRATIVE EXAMPLE
A The half-reactions are:
NO-2 +2OH -  NO-3 +H 2O+2e-  E o  0.04V
{NO-2 +H 2 O+e-  NO+2OH - }  2 E o  0.46V
_________________________________________________________________________________________________________
3NO-2  H 2O  NO 3 +2NO+2OH  o
Ecell  0.42V
o
E for the first reaction (oxidation) can be calculated by using the approach in Example
22-1. The calculated value is very small, and so the Eo for the disproportionation
reaction is negative. The disproportionation of NO2- to NO3- and NO is therefore not
spontaneous.

B The half-reactions are:


HNO 2 +H 2O  NO-3 +3H + +2e-  E o  0.934V
{HNO 2 +H + +e-  NO+H 2O}  2 E o  0.996V
________________________________________________________________________________________________________________
3HNO 2  NO-3 +H + +H 2O+2NO o
Ecell  0.062V
o
E for the first reaction (oxidation) can be calculated by using the approach in Example
22-1. Ecell
o
for the reaction is positive and therefore disproportionation of HNO2 to NO3-
and NO is spontaneous under standard conditions.

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

EXERCISES

Periodic Trends in Bonding and Acid-Base Character of Oxides

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

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

The Noble Gasses


5. First we use the ideal gas law to determine the amount in moles of argon.
PV 145 atm  55 L
n  1 1
 3.25  102 mol Ar
RT 0.08206 L atm mol K  299 K
22.414 L Ar STP 100.000 L air
L air = 3.25  102 mol Ar   = 7.8  105 L air
1 mol Ar 0.934 L Ar

+
7. (a) (b) O (c) F
F
O Xe O
O Xe O Xe F
O F
O F

(a) The Lewis structure has three ligands and one lone pair on Xe. XeO3 has a
trigonal pyramidal shape.
(b) The Lewis structure has four ligands on Xe. XeO 4 has a tetrahedral shape.
+
(c) There are five ligands and one lone pair on Xe in XeF5 . Its shape is square
pyramidal.

9. 3 XeF4(aq) + 6 H2O(l)  2 Xe(g) + 3/2 O2(g) + 12 HF(g) + XeO3(s)

11. For these noble gases, the bond energy of the noble gas fluorine is too small to
offset the energy required to break the F—F bond.

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

The Halogens
13. Iodide ion is slowly oxidized to iodine, which is yellow-brown in aqueous solution, by
oxygen in the air.
Oxidation: { 2I   aq  
 I 2  aq  + 2 e  } 2  E  = 0.535 V
Reduction: O 2  g  + 4 H +  aq  + 4 e  
 2 H 2 O(l) E  = +1.229 V
Net: 4 I   aq  + O 2  g  + 4 H +  aq  
 2 I 2  aq  + 2 H 2 O(l) 
Ecell = +0.694 V

Possibly followed by: I 2  aq  + I   aq  


 I3  aq 

15. Displacement reactions involve one element displacing another element from solution.
The element that dissolves in the solution is more “active” than the element supplanted
from solution. Within the halogen group, the activity decreases from top to bottom.
Thus, each halogen is able to displace the members of the group below it, but not those
above it. For instance, molecular bromine can oxidize aqueous iodide ion but
molecular iodine is incapable of oxidizing bromide ion:
Br2(aq) + 2 I(aq)  2 Br(aq) + I2(aq) however, I2(aq) + 2 Br(aq)  NO RXN
The only halogen with sufficient oxidizing power to displace O2(g) from water is F2(g):
2 H2O(l)  4 H+ + O2(g) + 4 e E1/2ox = 1.229 V
{F2(g) + 2 e  2 F(aq)} 2 E1/2red = 2.866 V
2 F2(g) + 2 H2O(l)  4 H+ + O2(g) + 4 F(aq) Ecell = 1.637 V
The large positive standard reduction potential for this reaction indicates that the reaction will
occur spontaneously, with products being strongly preferred under standard state conditions.
None of the halogens reacts with water to form H2(g). In order to displace molecular hydrogen
from water, one must add a strong reducing agent, such as sodium metal.

3
 1000 m 100 cm  1.03 g 1 lb 1 ton 1 g F  37.996 g F2
17. (a) mass F2 = 1 km  
3
     
 1 km 1 m  1 cm 3 454 g 2000 lb 1 ton 18.998 g F 
= 2  109 g F2 = 2  106 kg F2

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

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

19. In order for the disproportionation reaction to occur under standard conditions, the E
for the overall reaction must be greater than zero. To answer this question, we must
refer to the Latimer diagrams provided in Figure 22-4 and the answer to Practice
Example 22-1B.
(i) Reduction half reaction (acidic solution)
Cl2(aq) + 2 e  2 Cl(aq) E1/2 red = 1.358 V
(ii) Oxidation half reaction (acidic solution)
Cl2(aq) + 6 H2O(l)  2 ClO3(aq) + 12 H+(aq) + 10 e E1/2 ox = 1.453 V
Combining (i)  5 with (ii)  1, we obtain the desired disproportionation reaction:
6 Cl2(aq) + 6 H2O(l)  2 ClO3(aq) + 12 H+(aq) + 10 Cl(aq) Ecell = 0.095 V
Since the final cell voltage is negative, the disproportionation reaction will not occur
spontaneously under standard conditions. Alternatively, we can calculate Keq by using
lnKeq = G/RT and G = nFE. This method gives a Keq = 8.6  1017. Clearly,
the reaction will not go to completion under standard conditions.

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

(a) BrF3: 28 valence electrons F


VSEPR class: AX3E2
Thus BrF3 is T-shaped
F Br F

F
(b) IF5 42 valence electrons
VSEPR class: AX5E F F
I
Thus IF5 is square pyramidal F F

(c) Cl3IF 36 valence electrons Cl F


VSEPR class: AX4E2 I
Thus Cl3IF  is square planar Cl Cl

23. (a) The half-reactions are:


Oxidation: 3I-  I-3 +2e-
Reduction: I2 (aq)+2e-  2I- (aq)
_________________________________________________________________________________________________________
Overall: I2 (aq)+I- (aq)  I-3 (aq)
From the known value of the equilibrium constant at 25 oC, we can calculate G o and
consequently E o :

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

G o  RT ln K  nFE o
8.314JK -1mol-1  298.15K ln K  2  96485Cmol-1  E o
8.314JK -1mol-1  298.15K ln 7.7  10 2
E o
 0.085V
2  96485Cmol-1
(b) Set up the ICE table and solve for the equilibrium concentrations:
- -
I2 (aq) + I (aq) É I3 (aq)
0.0010M 0.0050M 0
0.0010-x 0.0050-x x
x x
K  7.7  10 2   6
(0.0010  x)  (0.0050  x) 5.0  10  0.0060x  x 2
7.7  10 2  (5.0  10 6  0.0060x  x 2 )  x
7.7  10 2 x 2  5.62x  3.85  10 3  0
Solving the quadratic equation gives x=7.6510-3 M.

Oxygen
 
25. (a) 2HgO(s) 
  2Hg(l)  O 2 (g) (b) 2KClO 4 (s) 
  2KClO 3 (s)  O 2 (g)

27. We first write the formulas of the four substances: N 2 O 4 , Al 2 O 3 , P4 O 6 , CO 2 . The one
constant in all these substances is oxygen. If we compare amounts of substance with
the same amount (in moles) of oxygen, the one with the smallest mass of the other
element will have the highest percent oxygen.
3 mol N 2 O 4 contains 12 mol O and 6 mol N: 6  14.0 = 84.0 g N
4 mol Al 2 O 3 contains 12 mol O and 8 mol Al: 8  27.0 = 216 g Al
2 mol P4 O 6 contains 12 mol O and 8 mol P: 8  31.0 = 248 g P
6 mol CO 2 contains 12 mol O and 6 mol C: 6  12.0 = 72.0 g C
Thus, of the oxides listed, CO 2 contains the largest percent oxygen by mass.

29. Recall that fraction by volume and fraction by pressure are numerically equal.
Additionally, one atmosphere pressure is equivalent to 760 mmHg. We combine these
two facts.
0.04 mmHg of O3
P{O3 } = 760 mmHg  6
= 3 105 mmHg
10 mmHg of atmosphere

31. The electrolysis reaction is 2H 2O(l) electrolysis


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

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

33. Since the pKa for H2O2 had been provided to us, we can find the solution pH simply by
solving an I.C.E. table for the hydrolysis of a 3.0 % H2O2 solution (by mass). Of
course, in order to use this method, the mass percent must first be converted to molarity.
We must assume that the density of the solution is 1.0 g mL1.
3.0 g H 2 O 2 1 g solution 1 mol H 2 O 2 1000 mL
[H2O2] =    = 0.88 M
100 g solution 1 mL solution 34.015 g H 2 O 2 1L

The pKa for H2O2 is 11.75. The Ka for H2O2 is therefore 1011.75 or 1.8  1012. By
comparison with pure water, which has a Ka of 1.8  1016 at 25 C, one can see that
H2O2 is indeed a stronger acid than water but the difference in acidity between the two
is not that great. Consequently, we cannot ignore the contribution of protons of pure
water when we work out the pH of the solution at equilibrium.
K = 1.8  10-12
Reaction: 
a
H2O2(aq) + H2O(l)  H3O+(aq) + HO2(aq)

Initial: 0.88 M  1.0  107 M 0M


Change: x M  +xM +x M
Equilibrium: (0.88x) M  (1.0  107 + x)M xM
(~0.88 M)
x(x  1.0  107 )
So, 1.8  1012 = x2 + 1.0  107x  1.58  1012 = 0
~0.88

 1.0 x 107  1.0  1014  4(1.58 10 12 )


x=
2
The root that makes sense in this context is x = 1.2  106 M.
Thus, the [H3O+] = 1.2  106 M + 1.0  107 M = 1.3  106 M
Consequently, the pH for the 3.0 % H2O2 solution (by mass) should be 5.89
(i.e., the solution is weakly acidic)

35. 3 O = O 
 2 O    O   O
Bonds broken: 3  (O=O) = 3  498 kJ/mol = 1494 kJ/mol
Bonds formed: 4  (O    O)

H o = +285 kJ/mol = bonds broken  bonds formed = 1494 kJ/mol  4  (O    O)


4  (O    O) = 1494 kJ/mol  285 kJ/mol = 1209 kJ/mol
O    O = 1209 kJ/mol + 4 = 302 kJ/mol

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

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

(b) All electrons are paired in O3 , producing a diamagnetic molecule and thus a
liquid at room temperature.

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

(a) H2O2(aq) + 2 H+(aq) + 2 e 




 2 H2O(l) E1/2red = +1.763 V
  
2 I (aq)  
 I2(s) + 2 e E1/2ox = 0.535 V

H2O2(aq) + 2 H+(aq) +2 I(aq) 





 I2(s) + 2 H2O(l) E1/2cell = +1.228 V(n = 2 e )
1.228 V  2
lnKeq = = 95.56 Keq = 3.2  1041
0.0257 V
Therefore the reaction goes to completion (or very nearly so).

(b) O2(g) + 2 H2O(l) +4 e 


 
 4 OH (aq) E1/2red = +0.401 V
4 Cl(aq) 

 2 Cl2(g) + 4 e

E1/2ox = 1.358 V

O2(g) + 2 H2O(l) +4 Cl(aq) 


 
 2 Cl2(g) + 4 OH (aq) E1/2cell = 0.957 V
(n = 4 e)
-0.957 V  4
lnKeq = = 148.95 Keq = 2.1  1065
0.0257 V
The extremely small value of Keq indicates that reactants are strongly preferred and
thus, the reaction does not even come close to going to completion.

(c) O3(g) + 2 H+(aq) + 2 e 




 O2(g) + H2O(l) E1/2red = +2.075 V
 
Pb2+(aq) + 2 H2O(l) 
+
 PbO2(s) + 4H (aq) + 2 e E1/2ox = 1.455 V

O3(g) + Pb2+(aq) + H2O(l) 
+
 PbO2(s) + 2 H (aq) + O2(g) Ecell = 0.620 V

0.62 V  2
lnKeq = = 48.25 Keq = 9.0  1020
0.0257 V
Therefore the reaction goes to completion (or very nearly so).
(d) HO2(aq) + H2O(l) + 2 e 
 

 3 OH (aq) E1/2red = +0.878 V
2 Br(aq) 
 
 Br2(l) + 2 e

E1/2ox = 1.065 V

HO2(aq) + H2O(l) + 2 Br(aq) 





 Br2(s) + 3 OH (aq) E1/2cell = 0.187 V
-0.187 V  2
lnKeq = = 14.55 Keq = 4.8  107
0.0257 V

618
Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

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


41. The reaction is 2 KClO3(s) 
MnO 2 (s)
 2 KCl(s) + 3 O2(g).
1 mol 3 molO 2 32 gO 2
1.0 gKClO 3     0.391gO 2
122.549 g 2 molKClO 3 1molO 2
nRT 0.01224  8.314 JK 1mol 1  298.15K
pV  nRT  V    30L
p 1atm
101kPa 
101.325kPa

Sulfur

43. (a) ZnS, zinc sulfide (b) KHSO3 , potassium hydrogen sulfite
(c) K 2S2 O3 , potassium thiosulfate (d) SF4 , sulfur tetrafluoride

45. (a) FeS  s  + 2 HCl  aq  


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

(b) CaSO3  s  + 2 HCl  aq  


 CaCl2  aq  + H 2 O(l) + SO 2  g 

SO 2  aq  + 2 H 2 O(l)   aq  + 4H +  aq  + 2 e
2
(c) Oxidation:  SO 4
Reduction: MnO 2  s  + 4 H +  aq  + 2 e  
 Mn 2+  aq  + 2 H 2O(l)

SO 2  aq  + MnO 2  s  
 Mn 2  aq  + SO 4  aq 
2
Net:

(d) Oxidation: S2 O3  aq  + H 2O(l) 


2
 2SO 2  g  + 2 H +  aq  + 4e 
S2 O3  aq  + 6 H +  aq  + 4 e  
 2S  s  + 3H 2 O(l)
2
Reduction:

Net: S2 O3
2
 aq  + 2 H +  aq  
 S  s  + SO 2  g  + H 2 O(l)

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

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

Na +  aq  will not hydrolyze, being only very weakly polarizing. But HSO 4  aq  will

49.
ionize further, K 2 = 1.1 102 for HSO 4  aq  . We set up the situation, and solve the

quadratic equation to obtain  H 3O +  .

619
Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen


12.5 g NaHSO 4 1000 mL 1 mol NaHSO 4 1 mol HSO 4
 HSO 4   =
  250.0 mL soln  1 L soln  120.1 g NaHSO  1 mol NaHSO = 0.416 M
4 4

Reaction: HSO 4  aq  + H 2 O(l) 



 SO 4  aq  + H 3O  aq 
2 +

Initial: 0.416 M  0M 0M


Changes: x M  + xM + xM
Equil:  0.416  x  M  xM xM
Noting the moderate value of the equilibrium constant (K = 0.011), the full quadratic
equation must be solved (i.e. no assumption can be made here).
 H 3 O +  SO 4 2  x2
K2 = = 0.011 = x 2 = 0.0046  0.011 x
 HSO 4   0.416  x
0 = x 2 + 0.011 x  0.0046

b  b 2  4ac 0.011  1.2  104 +1.8 102


x= = = 0.062 =  H 3O + 
2a 2
pH = log  0.062  = 1.21

51. The question is concerned with assaying for the mass percent of copper in an ore. The assay
in this instance involves the quantitative determination of the amount of metal in an ore by
chemical analysis. The titration for copper in the sample does not occur directly, but rather
indirectly via the number of moles of I3(aq) produced from the reaction of Cu2+ with I:
2 Cu2+ + 5 I(aq)  2 CuI(s) + I3(aq)
The number of moles of I3(aq) produced is determined by titrating the iodide-treated sample
with sodium thiosulfate. The balanced oxidation reaction that forms the basis for the titration is:
I3(aq) + 2 S2O32(aq)  3 I(aq) + S4O62(aq)
The stoichiometric ratio is one I3(aq) reacting with two S2O32(aq) in this titration.
The number of moles of I3 formed
2 
0.1000 moles S2 O 3 1 mol I 3
= 0.01212 L S2O32(aq)  2
 2
= 6.060  104 moles I3
1 L S2 O 3 2 mol S2 O 3
2+
Therefore, the number of moles of Cu released when the sample is dissolved is
2 mol Cu 2
= 6.060  104 moles I3  
= 1.212  103 moles of Cu2+
1 mol I3
Consequently, the mass percent for copper in the ore is
63.546 g Cu 2 1
1.212  103 moles of Cu2+  2
  100% = 7.002%
1 mol Cu 1.100 g of Cu ore
53. (a) +4; (b) +5; (c) -2 and (d) +4

620
Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

Nitrogen Family
55. (a) The Haber-Bosch process is the principal artificial method of fixing atmospheric
nitrogen. N 2  g  + 3 H 2  g  
 2 NH 3  g 

(b) The first step of the Ostwald process:


850 C, Pt
4NH 3 (g)  5 O 2 (g)   4NO(g)  6H 2O(g)

(c) The second and third steps of the process: 2 NO g  + O 2 g   2 NO 2 g 


3 NO 2 g  + H 2 O l   2 HNO 3 aq  + NO g 

57. Begin with the chemical formulas of the species involved:


Na 2CO 3 aq  + O 2 g  + NO g   NaNO 2 aq 
Oxygen is reduced and nitrogen (in NO) is oxidized. We use the ion-electron method.
NO  g   NO 2  aq 

Two couples: and O 2  products

Balance oxygens: H 2 O + NO  NO 2 O2  2 H 2O

Balance hydrogens: H 2 O + NO  NO 2 + 2 H + 4 H + + O2  2 H 2O

Balance charge: H 2 O + NO  NO 2 + 2 H + + e  4 e  + 4 H + + O2  2 H 2 O

Combine: 4 H 2 O + 4 NO + 4 H + + O 2  2 H 2 O + 4 NO 2 + 8 H +

Simplify: 2 H 2 O + 4 NO + O 2  4 NO 2 + 4 H +
2 2
Add spectator ions: 4 Na + + 2CO 3  4 Na + + 2CO 3
2 Na 2 CO3 + 2 H 2 O + 4 NO + O 2  4 NaNO2 + 2 H 2 O + 2 CO2
simplify:
2 Na 2 CO 3 aq  + 4 NO g  + O2 g   4 NaNO2 aq  + 2 CO2 g 

15 miles 5 g 1 kg
59. 75  109 gal    = 6  109 kg of nitrogen oxides released.
1 gal 1 mile 1000 g

61. (a) 2 NO2  g  


 N 2 O 4  g 

(b) i) HNO2(aq) + N2H5+(aq)  HN3(aq) + 2H2O(l) + H+(aq)


ii) HN3(aq) + HNO2(aq)  N2(g) + H2O(l) + N2O(g)
(c) H3PO4(aq) + 2 NH3(aq)  (NH4)2HPO4(aq)

621
Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

63.
(a) (CH3)2NNH2: H
Each molecule has a total of
H C N N H
26 valence electrons.
H H C H
H H

(b) ClNO2: O
Each molecule has a total of
24 valence electrons. Cl N O

(c) H3PO3 O
Each molecule has a total of
26 valence electrons. H O P O H

2
65. (a) HPO 4 , hydrogen phosphate ion
(b) Ca 2 P2 O7 , calcium pyrophosphate or calcium diphosphate
(c) H 6 P4 O13 , tetrapolyphosphoric acid

67. (i) 2 H+(aq) + N2O4(aq) + 2 e  2 HNO2(aq) E1 = +1.065 V


(ii) 2 HNO2(aq) + 2 H+(aq) + 2 e  2 NO(aq) + 2 H2O(l) E2 = +0.996 V
(iii) N2O4(aq) + 4 H+(aq) + 4 e 2 NO(aq) + 2 H2O(l) E3 = ? V

Recall that G = nFE and that G values, not standard voltages are additive for
reactions in which the number of electrons do not cancel out.
So, 4FE3 = 2F(1.065 V) + 2F(0.996 V) E3 = 1.031 V (4 sig figs)

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

Hydrogen

71. The four reactions of interest are: (Note: H combustion = Hf products - Hf reactants)
CH4(g) + 2 O2(g)  CO2(g) + 2 H2O(l) H combustion = -890.3 kJ
(Molar mass CH4 = 16.0428 g mol-1)

622
Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

C2H6(g) + 7/2 O2(g)  2 CO2(g) + 3 H2O(l) H combustion = -1559.7 kJ


(Molar mass C2H6 = 30.070 g mol-1)
C3H8(g) + 5 O2(g)  3 CO2(g) + 4 H2O(l) H combustion = -2219.9 kJ
(Molar mass C3H8 = 44.097 g mol-1)
C4H10(g)+13/2 O2(g) 4 CO2(g) + 5 H2O(l) H combustion = -2877.4 kJ
(Molar mass C4H10 = 58.123 g mol-1)

73. (a) 2 Al s  + 6 HCl aq   2 AlCl3 aq  + 3 H 2 g 


(b) 3 CO g  + 7 H 2 g   C 3H 8 g  + 3 H 2 O g 

(c) MnO 2 (s)  2H 2 (g) 
  Mn(s)  2H 2 O(g)

75. CaH 2  s  + 2 H 2 O(l)  Ca  OH 2  aq  + 2 H 2  g 


Ca  s  + 2 H 2 O(l)  Ca  OH 2  aq  + H 2  g 
2 Na  s  + 2 H 2 O(l)  2 NaOH  aq  + H 2  g 

(a) The reaction that produces the largest volume of H 2 g  per liter of water also
produces the largest amount of H2(g) per mole of water used. All three reactions
use two moles of water and the reaction with CaH 2 s  produces the most H2(g).
(b) We can compare three reactions that produce the same amount of hydrogen; the
one that requires the smallest mass of solid produces the greatest amount of H 2
per gram of solid. The amount of hydrogen we will choose, to simplify matters,
is 2 moles, which means that we compare 1 mol CaH 2 (42.09 g) with 2 mol Ca
(80.16 g) and with 4 mol Na (91.96 g). Clearly CaH 2 produces the greatest
amount of H 2 per gram of solid.

77. Greatest mass percent hydrogen:


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

79. NH2− has 8 valence electrons (and is isoelectronic with H2O). The first four MO’s
are fully occupied. Because the 2px orbital on N is strongly bonding in the bent
configuration, as shown in Figure 22-27, the energy of the NH2− will be much lower
for the bent configuration. (The same argument applies to H2O.) On the basis of
molecular orbital theory, we expect that NH2− will be bent.

623
Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

INTEGRATIVE AND ADVANCED EXERCISES


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

84. NaNO2 decolorizes acidic solution of KMnO4 according to the following balanced
chemical equation:
2KMnO4 + 3H2SO4 + 5NaNO2  5NaNO3 + K2SO4 + 2MnSO4 + 3H2O
NaNO3 does not react with acidic solution of KMnO4.

85. First we balance the equation, then determine the number of millimoles of NH3(g) that
are produced, and finally find the [NO3–] in the original solution.
The skeleton half-equations: NO3 (aq) 
 NH 3 (g) Zn(s) 
 Zn(OH) 42- (aq)

Balance O's and H's: NO3 (aq) 


 NH 3 (g)  3 H 2 O(l)

NO3 (aq)  9 H (aq) 
 NH 3 (g)  3 H 2 O(l)

Balance charge and add OH  (aq) NO3 (aq)  6 H 2 O(l)  8 e 


 NH3 (g)  9 OH  (aq)

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


 Zn(OH) 2-4 (aq)  2 e

{ Zn(s)  4 OH  (aq) 

Oxidation:  Zn(OH)2-4 (aq)  2 e } 4
Reduction: NO3 (aq) + 6 H 2 O(l) + 8 e- 
 NH 3 (g) + 9 OH - (aq)

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


 Zn(OH) 2-4 (aq) + NH3 (g)
The titration reactions are the following.
HCl(aq)  NaOH(aq) 
 NaCl(aq)  H 2 O(l) NH 3 (aq)  HCl(aq) 
 NH 4 Cl(aq)
0.1000 mmol NaOH 1 mmol HCl
mmol excess HCl  32.10 mL    3.210 mmol HCl
1 mL soln 1 mmol NaOH
0.1500 mmol HCl
mmol HCl at start  50.00 mL   7.500 mmol HCl
1 mL soln
1 mmol NH 3
mmol NH 3 produced  (7.500  3.210) mmol HCl   4.290 mmol NH 3
1 mmol HCl
1 mmol NO3
4.290 mmol NH 
 3 1 mmol NH 3
[NO3 ]  0.1716 M
25.00 mL soln

624
Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

Notice that it was not necessary to balance the equation, since NO3– and NH3 are the only
nitrogen-containing species involved, and thus they must be in a one-to-one molar ratio.

86. First we compute the root-mean-square speed of O at 1500 K.


3RT 3  8.314 J mol 1 K 1  1500 K 3
u    1.5  10 m/s
rms M 0.0160 kg/mol
Kinetic Energy =
0.0160 kg/mol
KE  12 mu 2  0.5   (1.5 103 m/s) 2  3.0 1020 J/atom
6.022 1023 atoms/mol

89. The N center in the ammonium ion is the reducing agent, while Cl in the perchlorate anion is
the oxidizing agent.
2 NH 4 ClO 4 (s) 
 N 2 (g)  4 H 2 O(g)  Cl 2 (g)  2 O 2 (g)

92. Each simple cubic unit cell has one Po atom at each of its eight corners, but each corner is
shared among eight unit cells. Thus, there is a total of one Po atom per unit cell. The edge of
that unit cell is 335 pm. From this information we obtain the density of polonium.
1 mol Po 209 g Po
1 Po atom  
density  6.022  10 Po atoms 1 mol Po  9.23 g/cm 3
23

3
 1m 100 cm 
 335 pm  12  
 10 pm 1 m 

Cl Cl
94. (a)
F C Cl F C    Cl
Cl Cl

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

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


339  10 3 J/mol
  8.50  10 14 s 1
6.626  10 34 J  s  6.022  10 23 / mol
c 3.00  10 8 m/s 10 9 nm
  7
 3.53  10 m   353 nm
 8.50  1014 / s 1m
This radiation is in the near ultraviolet region of the electromagnetic spectrum.

625
Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

95. (a) % P indicates the number of grams of P per 100 g of material, while % P4O10
indicates the number of grams of P4O10 per 100 g of material.
1 mol P4 O10 4 mol P 30.974 g P
mass P  1.000 g P4 O10     0.436 g P
283.89 g P4 O10 1 mol P4 O10 1 mol P
Thus, multiplying the mass of P4O10 by 0.436 will give the mass (or mass percent)
of P. %BPL indicates the number of grams of Ca3(PO4)2 per 100 g of material.
1 mol P4 O10 4 mol P
mass Ca 3 (PO 4 ) 2  1.000 g P4 O10  
283.89 g P4 O10 1 mol P4 O10
1 mol Ca 3 (PO 4 ) 2 310.18 g Ca 3 (PO 4 ) 2
   2.185 g Ca 3 (PO 4 ) 2
2 mol P 1 mol Ca 3 (PO 4 ) 2
Thus, multiplying the mass of P4O10 (283.88) by 2.185 will give the mass (or mass %) of BPL.

(b) A %BPL greater than 100% means that the material has a larger %P than does pure Ca3(PO4)2.

6 mol P 1 mol 3Ca 3 (PO 4 ) 2  CaF2 30.974 g P


(c) %P     100%  18.43% P
1mol 3Ca 3 (PO 4 ) 2  CaF2 1008.6 g 3Ca 3 (PO 4 ) 2  CaF2 1 mol P
%P 18.43
%P4 O10    42.3% P4 O10
0.436 0.436
%BPL  2.185  %P4 O10  2.185  42.3% P4 O10  92.4% BPL

99. pH = 3.5 means [H+] = 10–3.5 = 3 × 10–4 M. This is quite a dilute acidic solution, and we
expect H2SO4 to be completely ionized under these circumstances.
3  104 mol H  1 mol H 2 SO 4 98.1 g H 2 SO 4
mass H 2 SO 4  1.00  103 L     15 g H 2 SO 4
1L 2 mol H  1 mol H 2 SO 4

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


mass Cl 2  1.00  10 L 
3
 3
 6  
1L 1 cm 10 g seawater 159.8 g Br2 1 mol Br2
70.9 g Cl 2 115 g Cl 2 used
   37 g Cl 2
1 mol Cl 2 100 g Cl 2 needed

626
Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen

100. 0.0592
E  Eo  log 10 Q ;
n
assuming E  0 for a process that is no longer spontaneous:
nE o (16)(0.065)
log 10 Q    17.6 P SO 2
 1 10-6
0.0592 0.0592
( P SO )8 (1  10-6 )8
Q  10  3.9  10  8 2 16  8  16
17.6 17

1 (H ) 1 (H )
Solving for [H  ] yields a value of 8  105 M, which corresponds to a pH of 4.1
Thus, the solution is still acidic.

102. Oxidations :  XeO 3 (g)  4 HF(aq)  2 H  (aq)  2 e 


XeF4 (g)  3 H 2 O 
 O 2 (g)  4 H  (aq)  4 e }  32
{2 H 2 O(l) 
Reduction: {XeF4 (g)  4 e  
 Xe(g)  4 F (aq)} 2
Net: 3 XeF4 (g)  6 H 2 O(l) 
 2 XeO3 (g)  12 HF(aq)  3
2 O 2 (g)  2 Xe(g)
The fact that O2 is also produced indicates that there are two oxidation half-reactions.
The production ratio of Xe and XeO3 indicates the amount by which the other two half-
reactions must be multiplied before they are added. Then the half-reaction for the
production of O2 is multiplied by 32 to balance charge.

6.4g
104. The initial concentration of Cl2(aq)=  0.090M
70.9g/mol
-4
K c  4.4  10

Cl 2 (aq)  H 2 O(l)    
 HOCl(aq)  H (aq)  Cl (aq)
initial 0.090 M 0M 0M 0M
equil. (0.090-x) M xM xM xM
{where x is the molar solubility of Cl 2 in water}
[HOCl(aq)][ H  (aq)] [Cl (aq)] x3
K   4.4  10-4
[Cl 2 (aq)] 0.090-x
By using successive approximations, we find x  0.030 M, so:
[HOCl(aq)]  [H  (aq)]  [Cl (aq)]  0.030 M and [Cl 2 (aq)]  0.090  0.030  0.060 M

105.
2e-  N 2 (g)  4 H + (aq) + 2H 2 O(l)  2 NH 3 OH + (aq) E o = -1.87 V
2 NH 3 OH + (aq) + H + (aq) + 2e-  N 2 H 5 + (aq) + 2 H 2 O(l) E o = 1.42 V
N 2 H 5 + (aq) + 3 H + (aq) + 2e-  2 NH 4 + (aq) E o = 1.275 V
N 2 (g) + 8 H + (aq) + 6e-  2 NH 4 + (aq) Eo = 0.275 V (see below)

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

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


o n 1 Eo 1 n 2 Eo 2  n 3 Eo 3
E tot =
n tot
E o tot = [2(-1.87) +2(1.42) + 2(1.275)]/6 = 0.275 V
moving on...
2 HN 3 (aq)  3 N 2 ( g )  2H + (aq)  2 e- Eo   3.09 V (oxidation)
3 N 2 (g)  24 H + (aq)  18e-  6 NH 4 + (aq) Eo  0.275 V (top equation multiplied by 3)
2 HN 3 (aq)  22 H + (aq)  16 e-  6 NH 4 + (aq) [ sum]
[divide by 2]
HN 3 (aq)  11 H + (aq)  8 e-  3 NH 4 + (aq) E o  0.70 V
since
G o total = G o 1 +G o 2 = -nFE o tot = -nFE o 1 -nFE o 2
o
E total = [2(3.09) +18(0.275) ]/16 = 0.70 V

107. Both molecules are V shaped, with a lone pair of electrons on the central atom.
For O3, the structure is a hybrid of two equivalent structures. In each of these
structures, the central atom has a formal charge of +1. The oxygen–oxygen bond
order is between 1 and 2. Although many resonance structures can be drawn for SO2,
in the most important structure, the formal charge on the S atom is zero and the
sulfur–oxygen bonds are double bonds.
3
109. H fo = [ (498) − 3 (36)] = 639 kJ mol−1
2
The formation reaction is very endothermic and thus energetically unfavorable. This
result supports the observation that Xe(g) does not react directly with O2(g) to form
XeO3(g). Because the reaction converts 2.5 moles of gas into 1 mole of gas, we
expect Sfo < 0; thus, the reaction is also entropically unfavorable.

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

FEATURE PROBLEMS
110. The goal here is to demonstrate that the three reactions result in the decomposition of
water as the net reaction: Net: 2 H 2 O  2 H 2 + O 2 First balance each equation.
(1) 3 FeCl 2 + 4 H 2 O  Fe 3O 4 + HCl + H 2 Balance by inspection. Notice that there
are 3 Fe and 4 O on the right-hand side. Then balance Cl.
3 FeCl 2 + 4 H 2 O  Fe 3O 4 + 6 HCl + H 2

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


Cl 2 + 2 e   2 Cl  But realize that Fe3O 4 = Fe 2 O 3  FeO .
2 FeO  2 Fe 3+ + O 2 + 6 e  Now combine the two half-equations.

2 FeO + 3 Cl 2  2 Fe 3+ + O 2 + 6 Cl 

Add in 2 Fe 2 O 3 +12 H +  4 Fe 3+ + 6 H 2 O

2 Fe 3O 4 + 3 Cl 2 +12 H +  6 Fe 3+ + O 2 + 6 Cl  + 6 H 2 O

And 12 Cl  spectators: 2 Fe 3O 4 + 3 Cl 2 +12 HCl  6 FeCl 3 + O 2 + 6 H 2 O


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

(?) (?)
112. ClO3- ClO2 HClO2

1.1181 V
In order to add ClO2 to the Latimer diagram drawn above, we must calculate the voltages
denoted by (?) and (??) . The equation associated with the reduction potential (?) is
(i) 2 H+(aq) + ClO3(aq) + 1 e  ClO2(g) + H2O(l)
The standard voltage for this half-reaction is given in Appendix D:
To finish up this problem, we just need to calculate the standard voltage (??) for

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

the half-reaction (ii):


(ii) H+(aq) + ClO2(aq) + 1 e  HClO2(g) Eo = (??)
To obtain the voltage for reaction (ii), we need to subtract reaction (i) from reaction (iii)
below, which has been taken from Figure 22-2:

(iii) 3 H+(aq) + ClO3(aq) + 2 e 




o
 HClO2(g) + H2O(l) E = 1.181 V
Thus,
(iii) 3 H+(aq) + ClO3(aq) + 2 e 


o
 HClO2(g) + H2O(l) E (iii) = 1.181 V
1 (i) 2 H+(aq) + ClO3(aq) + 1 e  ClO2(g) + H2O(l) Eo(i) = 1.175 V
Net (ii) H+(aq) + ClO2(g) + 1 e  HClO2(g) Eo(ii) = (??)
Since reactions (i) and (iii) are both reduction half reactions, we cannot simply subtract the
potential for (i) from the potential for (iii). Instead, we are forced to obtain the voltage for
(ii) via the free energy changes for the three half reactions. Thus,
G(ii) = G(iii) G(i) = 1FEo(ii) = 2F(1.181 V) + 1F(1.175 V)
Dividing both sides by –F gives
Eo(ii) = 2(1.181 V) – 1.175 V So, Eo(??) = 1.187 V.

SELF-ASSESSMENT EXERCISES
120. (b)

121. (d)

122. (c)

123. (a)

124. (d)

125. (b)

126. (a) and (b)

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


(b) 2NaI(s)+2H 2SO 4 (concd aq)  Na 2 SO 4 (a)+2H 2 O(g)+SO 2 (g)+I2 (g)
(c) Cl2 (g)+2KI3 (aq)  2KCl(aq)+3I2 (s)
(d) 3NaBr(s)+H 3PO 4 (concd aq)  Na 3PO 4 +3HBr(g)
(e) 5HSO-3 (aq)+2MnO-4 (aq)+H + (aq)  5SO 2-4 (aq)+2Mn 2+ (aq)+3H 2O(l)

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

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

129. (a) LiH(s)+H 2O(l)  LiOH(aq)+H 2 (g)


(b) C(s)+H 2 O(g)  CO(g)+H 2 (g)
(c) 3NO 2 (g)+H 2O(l)  2HNO 3 (aq)+NO(g)

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


130.
Cl2 (g)+2Br - (aq)  2Cl- (aq)+Br2 (aq)

131. One conversion pathway is ton  lb  kg  g H2SO4  g S  mg S  L


seawater  m3  kg3 seawater, leading to about 5.0 kg3 of seawater.

132. (a) AgAt, (b) sodium perxenate, (c) MgPo, (d) tellurous acid, (e) K2SeSO3, (f)
potassium perastatate
133. Convert the E o values to G o values for the reduction of H2SeO3 to Se and from
Se to H2Se. Add those two G o values to obtain G o for the reduction of
H2SeO3 to H2Se. Convert this G o value to E o , which proves to be 0.38 V.

134. (a) SO3, (b) SO2, (c) Cl2O7, (d) I2O5

135. (a) false, (b) true, (c) true.

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