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610
Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen
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 mol1 K 1 298 K ln K P
611
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.
P{H 2 g }P{Cl2 g }
2
x x x x
Kp = = = = 4 1034 2 1017
P{HCl g } 2
P 2x P 2x
2
P 2x
x = 2 1017 P 2 x 2 1017 P
2x
% decomposition = 100% = 2 2 1017 100% 4 1015 % 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.
612
Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen
EXERCISES
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.
+
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.
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.
613
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
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 E1/2ox = 1.229 V
{F2(g) + 2 e 2 F(aq)} 2 E1/2red = 2.866 V
2 F2(g) + 2 H2O(l) 4 H+ + O2(g) + 4 F(aq) Ecell = 1.637 V
The large positive standard reduction potential for this reaction indicates that the reaction will
occur spontaneously, with products being strongly preferred under standard state conditions.
None of the halogens reacts with water to form H2(g). In order to displace molecular hydrogen
from water, one must add a strong reducing agent, such as sodium metal.
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.
614
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) E1/2 red = 1.358 V
(ii) Oxidation half reaction (acidic solution)
Cl2(aq) + 6 H2O(l) 2 ClO3(aq) + 12 H+(aq) + 10 e E1/2 ox = 1.453 V
Combining (i) 5 with (ii) 1, we obtain the desired disproportionation reaction:
6 Cl2(aq) + 6 H2O(l) 2 ClO3(aq) + 12 H+(aq) + 10 Cl(aq) Ecell = 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 1017. 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.
F
(b) IF5 42 valence electrons
VSEPR class: AX5E F F
I
Thus IF5 is square pyramidal F F
615
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=7.6510-3 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
= 3 105 mmHg
10 mmHg of atmosphere
616
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 mL1.
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 1011.75 or 1.8 1012. By
comparison with pure water, which has a Ka of 1.8 1016 at 25 C, one can see that
H2O2 is indeed a stronger acid than water but the difference in acidity between the two
is not that great. Consequently, we cannot ignore the contribution of protons of pure
water when we work out the pH of the solution at equilibrium.
K = 1.8 10-12
Reaction:
a
H2O2(aq) + H2O(l) H3O+(aq) + HO2(aq)
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)
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.
617
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 Ecell =
(0.0257/n)lnKeq.
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) E1/2red = +0.878 V
2 Br(aq)
Br2(l) + 2 e
E1/2ox = 1.065 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
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:
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 = 1.1 102 for HSO 4 aq . We set up the situation, and solve the
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
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
= 6.060 104 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
= 6.060 104 moles I3
= 1.212 103 moles of Cu2+
1 mol I3
Consequently, the mass percent for copper in the ore is
63.546 g Cu 2 1
1.212 103 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
15 miles 5 g 1 kg
59. 75 109 gal = 6 109 kg of nitrogen oxides released.
1 gal 1 mile 1000 g
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
Recall that G = nFE and that G values, not standard voltages are additive for
reactions in which the number of electrons do not cancel out.
So, 4FE3 = 2F(1.065 V) + 2F(0.996 V) E3 = 1.031 V (4 sig figs)
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 = Hf products - Hf 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
(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.
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
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)
{ 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)
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.
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.
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.
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.
3 104 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
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 8 105 M, which corresponds to a pH of 4.1
Thus, the solution is still acidic.
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)
627
Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen
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.
628
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 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
(?) (?)
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
629
Chapter 22: Chemistry of the Main- Group Elements II: Groups 18, 17, 16, 15, and Hydrogen
SELF-ASSESSMENT EXERCISES
120. (b)
121. (d)
122. (c)
123. (a)
124. (d)
125. (b)
630
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.
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.
631