1B
(c)
Hg(l) forms.
2 Cu 2S s + 3 O 2 g 2 Cu 2 O s + 2 SO 2 g
WO3 s + 3 H 2 g W s + 3 H 2 O g
2 HgO s
2 Hg l + O 2 g
3 Si s + 2 Cr2 O3 s
3 SiO 2 s + 4 Cr s
(b)
(c)
2A
, Air
Co 2 O3 s + 3H 2 O g
Roasting is simply heating in air. 2 Co OH 3 s
(M) We write and combine the half-equations for oxidation and reduction. If E o 0 , the
reaction is spontaneous.
Oxidation: {V 3+ aq + H 2 O(l) VO 2+ aq + 2H + aq + e } 3
E o = 0.337V
Reduction: NO3 aq + 4H + aq + 3e NO g + 2H 2 O
E o = +0.956V
Ecell o = +0.619V
Because the cell potential is positive, nitric acid can be used to oxidize V 3+ aq to VO 2+ aq
under standard conditions.
2B
(M) The reducing couple must have a half-cell potential of such a size and sign that a positive
sum results when this half-cell potential is combined with
E o {VO 2 (aq)|V 2 (aq)} 0.041V (this is the weighted average of the VO2+ | V3+ and V3+ | V2+
reduction potentials) and a negative sum must be produced when this half-cell potential is
combined with E o {V 2 (aq)|V(s)}= 1.13V .
So, -Eo for the couple must be > 0.041 V and < + 1.13 V (i.e., it cannot be more positive than
1.13V, nor more negative than 0.041 V). Some possible reducing couples from Table 20-1 are:
E o {Cr 3 (aq)|Cr 2+ (aq)} 0.42 V ; E o {Fe 2+ (aq)|Fe(s)} 0.440 V
E o {Zn 2+ (aq)|Zn(s)} 0.763 V . Thus Fe(s), Cr2+(aq), and Zn(s) will do the job.
INTEGRATIVE EXAMPLE
3A
(M) Because the reduction potential for PtCl62 is more positive than that of V3+, the
following half-reactions occur spontaneously in the cell:
E = +0.255 V
Oxidation: [ V2+ + e V3+ ] 2
2
2
E = +0.68 V
Reduction: PtCl6 + 2 e PtCl4 + 2 Cl
Overall: 2 V2+ + PtCl62 2 V3+ + PtCl42 + 2 Cl E = 0.94 V
1136
2(0.94)
The equilibrium constant for the overall reaction is K 10 0.0592 5.7 1031 . For the
reverse reaction to be spontaneous, we need Q > 5.7 1031. Because Q = [V3+]2 [PtCl42]
[Cl]2/[V2+] [PtCl62], the formation of PtCl62 is favored by using a very low
concentration of V2+ and very high concentrations of V3+, PtCl42, and Cl. In practical
terms, though, the amount of PtCl62 that could be formed spontaneously would be small.
A quick calculation shows that starting from [V3+]o = [PtCl42]o = [Cl]o = 1. M and [V2+]
= [PtCl62]o = 0, the equilibrium concentration of PtC62 would be about 1.6 1011 M.
So, in practical terms, an external voltage source would be required to make a significant
amount of PtCl62 from V3+, PtCl42, and Cl.
3B
(M) The disproportionation reaction is 3 Ti2+ 2 Ti3+ + Ti and E = 1.261 V. Because
E < 0, the reaction is not spontaneous under standard conditions.
EXERCISES
Properties of the Transition Elements
1.
(E) (a) Ti
[Ar]
3d
4s
(b)
V 3+ [Ar]
3d
4s
2.
(c)
Cr 2+
[Ar]
3d
4s
(d)
Mn 4+ [Ar]
3d
4s
(e)
Mn 2+
[Ar]
3d
4s
(f)
Fe 3+
3d
4s
[Ar]
(E) We first give the orbital diagram for each of the species, and then count the number
of unpaired electrons.
Fe
[Ar]
3d
4s
4 unpaired electrons
Sc 3+
[Ar]
3d
4s
0 unpaired electrons
Ti 2+
[Ar]
3d
4s
2 unpaired electrons
Mn 4+
[Ar]
3d
4s
3 unpaired electrons
Cr
[Ar]
3d
4s
6 unpaired electrons
Cu 2+
[Ar]
3d
4s
1 unpaired electron
(M) A given main-group metal typically displays just one oxidation state, usually equal to
its family number in the periodic table. Exceptions are elements such as Tl ( +1 and +3 ), Pb
1137
( +2 and +4 ), and Sn ( +2 and +4 ), for which the lower oxidation state represents a pair of s
electrons not being ionized (a so-called inert pair).
Main group metals do not form a wide variety of complex ions, with Al3+ , Sn 2+ , Sn 4+ , and
Pb 2+ being major exceptions. On the other hand, most transition metal ions form an extensive
variety of complex ions. Most compounds of main group metals are colorless; exceptions
occur when the anion is colored. On the other hand, many of the compounds of transition
metal cations are colored, due to d-d electron transitions. Virtually every main-group metal
cation has no unpaired electrons and hence is diamagnetic. On the other hand, many transition
metals cations have one or more unpaired electrons and therefore are paramagnetic.
4.
(M) As we proceed from Sc to Cr, the valence electron configuration has an increasing
number of unpaired electrons, which are capable of forming bonds to adjacent atoms. As we
continue beyond Cr, however, these electrons become paired, and the resulting atoms are less
able to form bonds with their neighbors. Also, smaller atoms tend to bond more tightly,
making their metallic agglomerations more difficult to melt. (i.e., the smaller the metal atom,
the higher the melting point). This trend of increasing melting point with decreasing size is
clearly visible for the first transition series from Sc to Zn.
5.
(M) When an electron and a proton are added to a main group element to create the element of
next highest atomic number, it is the electron that influences the radius. The electron is added to
the outermost shell (n value), which is farthest from the nucleus. Moreover, the added electron
is well shielded from the nucleus and hence it is only weakly attracted to the nucleus. Thus, this
electron billows out and, as a result, has a major influence on the size of the atom. However,
when an electron and a proton are added to a transition metal atom to create the atom of next
highest atomic number, the electron it is not added to the outermost shell. The electron is added
to the d-orbitals, which are one principal quantum number lower than the outermost shell. Also,
the electron in the same subshell as the added electron offers little shielding. Thus it has small
effect on the size of the atom.
6.
(M) The reason why the radii of Pd (138 pm) and Pt (139 pm) are so similar, and yet so
different from the radius of Ni (125 pm) is because the lanthanide series intrudes between
Pd and Pt. Because of the lanthanide contraction, elements in the second transition row are
almost identical in size to their congeners (family members) in the third transition row.
7.
(M) Of the first transition series, manganese exhibits the greatest number of different
oxidation states in its compounds, namely, every state from +1 to +7 . One possible
explanation might be its 3d 5 4 s2 electron configuration. Removing one electron produces an
electron configuration ( 3d 5 4 s1 ) with two half-filled subshells, removing two produces one
with a half-filled and an empty subshell. Then there is no point of semistability until the
remaining five d electrons are removed. These higher oxidation states all are stabilized by
being present in oxides ( MnO 2 ) or oxoanions (e.g., MnO4 ).
8.
(M) At the beginning of the series, there are few electrons beyond the last noble gas that
can be ionized and thus the maximum oxidation state is limited. Toward the end of the
series, many of the electrons are paired up or the d subshell is filled, and thus a somewhat
stable situation would be disrupted by ionization.
1138
9.
(M) The greater ease of forming lanthanide cations compared to forming transition metal
cations, is due to the larger size of lanthanide atoms. The valence (outer shell) electrons of
these larger atoms are further from the nucleus, less strongly attracted to the positive charge
of the nucleus in diffuse f-orbitals that are do not penetrate effectively and are very
effectively shielded by the core electrons. As a result, they are removed much more readily.
10.
(M) This is not a simple straightforward question. There are a number of factors to consider.
Proceeding across the first transition series, electrons are added to the 3d subshell which is a
shell that is beneath the 4s subshell, the outer most subshell in the valence shell occupied by
one or two electrons. The metallic character of the first transition element, Sc, is rather similar
to that of Ca (e.g., E = 2.03 V compared to 2.84 V). Following this, there is a fairly regular
rise in E, (e.g., 1.63 V for Ti , 1.13 V for V), reaching a maximum of E = 0.340 V with
Cu. These trends can be related to the regular increase in Zeff and other aspects of electron
configurations (half filled shell for Mn2+ and loss of half filled shell for Cr2+). Complicating
matters is the fact that these ions will have different aqueous coordination numbers and
geometries.
In the lanthanide series, it is the 4f subshell that fills at the same time that the 5d subshell is
mostly vacant and the 6s subshell is filled. Differences in electron configurations are
essentially confined to a subshell two shells removed from the outermost valence shell, which
translates into close similarities among all the elements in the series, including E values.
Recall that the lanthanide series is an inner transition seriesa transition series within another
transition series. This inner transition series runs its course between La (E = 2.38 V) and Hf
(E = 1.70 V). The difference between these two E values is about 0.7 V, which is comparable
to the 0.4 V difference between the first (Sc) and second (Ti) members of the first transition series.
12.
(b)
Cr2 O3 s + 2Al s
2 Cr l + Al2 O3 s
(c)
Ag s + HCl aq no reaction
(d)
(e)
MnO 2 s + 2 C s
Mn l + 2CO g
Cr2 O3 s + 2 OH aq + 3 H 2 O(l) 2 Cr OH 4 aq
The oxide must be amphoteric. Thus, Sc 2 O3 , TiO 2 , ZrO 2 , and ZnO could be
substituted for Cr2 O3 .
1139
(c)
2 La s + 6 HCl aq 2 LaCl3 aq + 3 H 2 g
14.
15.
(c)
2 KOH l + TiO 2 s
K 2 TiO3 s + H 2 O g
(d)
electrolysis
(M) (a) 2 Sc 2 O3 l,in Na 3ScF6 + 3 C s
4 Sc l + 3 CO 2 g
(b)
[By analogy with the equation for the electrolytic production of Al]
Cr s + 2 HCl aq Cr 2+ aq + 2 Cl aq + H 2 g
(c)
4 Cr 2+ aq + O 2 g + 4 H + aq 4 Cr 3+ aq + 2 H 2 O(l)
(d)
(M) We write some of the following reactions as total equations rather than as net ionic
equations so that the reagents used are indicated.
(a)
4 Fe 2+ aq + O 2 g + 4H + aq 4Fe3+ aq + 2 H 2 O(l)
Fe3+ aq + 3 OH aq Fe OH 3 s
(b)
16.
N 2 g + 4 H 2 O g + Cr2 O3 s
NH 4 2 Cr2O7 s
Extractive Metallurgy
17.
4 HgS(s) + 4 CaO(s)
4 Hg(l) + 3 CaS(s) + CaSO4(s)
18.
1140
(b)
19.
(M) The plot of Go versus T will consist of three lines of increasing positive slope.
The first line is joined to the second line at the melting point for Ca(s), while the second
line is joined to the third at the boiling point for Ca(l).
The graph should be similar to that for 2 Mg(s) + O2(g) 2 MgO(s). We expect a
positive slope with slight changes in the slope after the melting point (839 C) and boiling
point (1484 C) , mainly owing to changes in entropy. The plot will be below the
G line for 2 Mg(s) + O2(g) 2 MgO(s) at all temperatures.
20.
Oxidation-Reduction
21.
22.
23.
Oxidation:
Reduction:
VO 2+ aq + 2H + aq + e V3+ aq + H 2O (l)
Cr 2+ aq Cr 3+ aq + e
Fe OH 3 s + 5 OH aq FeO4
aq + 4 H 2O(l) + 3e
Ag CN 2 aq + e Ag s + 2 CN aq
2
(M) (a) First we need the reduction potential for the couple VO+2 aq / V2 + aq . We will
use the half-cell addition method learned in Chapter 20.
VO 2 aq + 2 H + aq + e VO 2+ aq + H 2 O(l)
G o = 1 F +1.000 V
VO 2+ aq + 2 H + aq + e V 3+ aq + H 2 O(l)
G o = 1 F +0.337 V
V 3+ aq + e V 2+ aq
G o = 1 F 0.255 V
VO 2 aq + 4 H + aq + 3 e V 2+ aq + 2 H 2 O
G o = 3 FE o
Eo =
1141
E o = 1.065 V
o
Ecell
= 0.704V
Thus, this reaction does not occur to a significant extent as written under standard
conditions.
(b)
Oxidation: Fe 2+ aq Fe3+ aq + e
Reduction: VO 2 aq + 2 H + aq + e VO 2+ aq + H 2 O(l)
+
Net:
E o = 0.771V
E o = +1.000V
o
Ecell
= +0.229V
This reaction does occur to a significant extent under standard conditions.
(c)
Oxidation: H 2 O 2 2 H + aq + 2 e + O 2 g
E o = 0.695 V
E o = +1.23V
Ecell = +0.54V
Thus, this reaction does occur to a significant extent under standard conditions.
24.
(D) When a species acts as a reducing agent, it is oxidized. From Appendix D, we obtain
the potentials for each of the following couples.
o
Ecell
= E o {Cr2 O7 (aq) / Cr 3 (aq)} E o {Zn 2 (aq) / Zn(s)}
o
Ecell
= +1.33 V + 0.763 V = +2.09 V Yes
o
Ecell
= E o {Cr2 O7 (aq) / Cr 3 (aq)} E o {Sn 4 (aq) / Sn 2+ (aq)}
o
Ecell
= +1.33 V 0.154 V = +1.18 V Yes
2
o
Ecell
= E o {Cr2O7 (aq) / Cr 3 (aq)} E o {I 2 (s) / I (aq)}
o
Ecell
= +1.33 V 0.535 V = +0.80 V Yes
1142
(b)
(c)
o
Ecell
= E o {SO 4 (aq)/SO 2 (g)} E o {Zn 2+ (aq)/Zn(s)}
o
Ecell
== +0.17 V + 0.763 V = +0.93 V Yes
o
Ecell
= E o {SO 4 2 (aq)/SO 2 (g)} E o {Sn 4+ (aq)/Sn 2+ (aq)}
o
Ecell
= +0.17 V 0.154 V = +0.02 V
Yes (barely)
o
Ecell
= E o {SO 4 (aq)/SO 2 (g)} E o {I 2 (s)/I (aq)}
o
Ecell
= +0.17 V 0.535 V = 0.37 V
25.
No
(M) The reducing couple that we seek must have a half-cell potential of such a size and
sign that a positive sum results when this half-cell potential is combined
with E o {VO 2 (aq)|V 3 (aq)} 0.337 V and a negative sum must be produced when this
+
(M) There are two methods that can be used to determine the MnO4-/Mn2+ reduction potential.
Method 1:
MnO4 1.70 V MnO2 1.23 V Mn2+
EMnO4-/ Mn2+ =
3 (1.70 V) + 2 (1.23 V)
= 1.512 V ~1.51 V
5
1143
27.
(M) Table D-4 contains the following data: Cr 3+ /Cr 2+ reduction potential = -0.424 V,
Cr2 O7 2- /Cr 3+ reduction potential = 1.33 V and Cr 2+ /Cr reduction potential = -0.90 V.
By using the additive nature of free energies and the fact that G = -nFE, we can
determine the two unknown potentials and complete the diagram.
3(1.33V) - 0.424 V
Cr2 O7 2- /Cr 2+ : E =
= 0.892 V
(i)
4
(ii)
28.
Cr 3+ /Cr : E =
0.424 V + 2(-0.90 )V
= 0.74 V
3
(M) From Table 23.4 we are given: VO2+/VO2+ reduction potential = 1.000 V, VO2+/V3+
reduction potential = 0.337 V, V3+/V2+ reduction potential = -0.255 V and V2+/V reduction
potential = -1.13 V. By taking advantage of the additive nature of free energies and the fact that
G = -nFE, we can determine the three unknown potentials and complete the diagram.
(i)
(ii)
(iii)
1.000 V + 0.337 V
= 0.669 V
2
1.000 V + 0.337 V + (-0.255 V)
= 0.361 V
VO2+/V2+: E =
3
1.000 V + 0.337 V + (-0.255 V) + 2(-1.13 V)
VO2+/V: E =
= 0.24 V
5
VO2+/V3+: E =
(M) Orange dichromate ion is in equilibrium with yellow chromate ion in aqueous
solution.
2CrO 4 2 aq + 2H + aq
Cr2 O7 2 aq + H 2 O(l)
The chromate ion in solution then reacts with lead(II) ion to form a precipitate of yellow
PbCrO 4 s
lead(II) dichromate. Pb 2+ aq + CrO 4 2 aq
PbCrO 4 s will form until H + from the first equilibrium increases to the appropriate
level and both equilibria are simultaneously satisfied.
30.
1144
31.
Reduction: Cr2 O 7
3 Zn s + Cr2 O7
Net:
Oxidation:
aq +14 H + aq 3 Zn 2+ aq + 2 Cr 3+ aq + 7 H 2O(l)
Zn s Zn 2 + aq + 2e
Reduction:
Net:
Zn s + 2 Cr 3+ aq Zn 2+ aq + 2 Cr 2+ aq
The green color is most likely due to a chloro complex of Cr3+, such as Cr H 2 O 4 Cl2 .
+
32.
Oxidation:
Reduction:
O 2 g + 4 H + aq + 4e 2 H 2 O(l)
Net:
4 Cr 2+ aq + O 2 g + 4 H + aq 4 Cr 3+ aq + 2 H 2 O(l)
(M) CO 2 g , as the oxide of a nonmetal, is an acid anhydride. Its function is to make the
solution acidic. A reasonable guess of the reactions that occur follows.
Cr2O7 2 aq + H 2O(l)
2 CrO 4 2 aq + 2 H + aq
2H + aq + 2 HCO3 aq
2 H 2 O(l) + 2CO2 aq
Cr2 O7 2 aq + 2 HCO3 aq
2 CrO 4 2 aq + 2 CO 2 aq + H 2 O(l)
33.
2
(M) Simple substitution into Equation (23.19) yields Cr2 O7 in each case. In fact, the
expression is readily solved for the desired concentration as follows:
2
Cr2 O7 2 = 3.2 1014 H + CrO 4 2 . In each case, we use the value of pH to determine
+
pH
H = 10 .
(a)
(b)
2
2
Cr2O 7 = 3.2 1014 108.85 0.20 2 = 2.6 105 M
1145
34.
Cr2 O 27
2
= 3.2 1014 H + = 3.2 1014 10 7.55
2 2
CrO 4
CrO 4
initial
2
8 2
14
0.345 L soln
161.97 g Na 2 CrO 4 1mol Na 2 CrO 4
Reaction:
2CrO 4 2 aq
Initial:
Changes:
Equil:
0.0269 M
2 x M
0.0269 2 x
2H + aq
Cr2O 27 aq + H 2 O (l)
0M
2.8 10 (fixed)
Cr2 O7 2
x
= 0.254 =
2
2 2
0.0269 2 x
CrO 4
+x M
xM
Cr2O7 2 = x = 0.00016 M
We carry extra significant figures to avoid a significant rounding error in this problem.
35.
(E) Each mole of chromium metal plated out from a chrome plating bath (i.e., CrO3 and
H2SO4) requires six moles of electrons.
3600 s 3.4 C 1 mol e 1 mol Cr 52.00 g Cr
= 1.10 g Cr
mass Cr =1.00 h
1 hr
1s
96485 C 6 mol e 1mol Cr
36.
1 cm
104 cm 2 7.14 g Cr 1 mol Cr
2
mol Cr = 0.0010 mm
= 5.1 102 mol Cr
0.375 m
2
3
10 mm
1 m 1 cm Cr 52.0 g Cr
Recall that the deposition of each mole of chromium requires six moles of electrons. We
now compute the time required to deposit the 5.1102 mol Cr .
6 mol e 96485 C 1s
1h
time = 5.1102 mol Cr
= 2.3 h
1 mol Cr 1mol e
3.5C 3600s
37.
(M) Dichromate ion is the prevalent species in acidic solution. Oxoanions are better
oxidizing agents in acidic solution because increasing the concentration of hydrogen ion
favors formation of product. The half-equation is:
Cr2 O72-(aq) 14 H (aq) 6 e
2 Cr 3 (aq) 7H 2O(l) Note that precipitation occurs
1146
Cr 3+ aq + 3 OH aq Cr OH 3 s
Because chromium(III) oxides and hydroxides are amphoteric (and those of magnesium
ion are not), Cr OH 3 s will dissolve in excess base.
Cr OH 3 s + NaOH aq Na + aq + Cr OH 4 aq
E = 0.44 V
[Fe2+] = [Fe3+]; pH = 3.25 or [H+] = 5.6 10-4 and PO2 = 0.20 atm
0.0592
[Fe3+ ]4
log 2+ 4 + 4
E = E [Fe ] [H ] PO
n
[Fe3+ ]4
0.0592
log
= 0.44 V 2+ 4
-3.25 4
4
[Fe
]
[10
]
0.20
}2
Eox
Ered
Cd(s) Cd2+(aq) + 2 e
Eox = 0.403 V
1
= 0.403 V
Cd (aq) + 2 OH (aq) Cd(OH)2(s) Ecell = 0.0592 log 1 = 0.0592 log
-14
K
n
2
2.5
10
sp
2+
}2
} 1
Ered
Eox = 0.806 V
1147
41.
[III]
[II]
[II]
[II]
42.
[II]
[III]
[II]
Group 11 Metals
43.
44.
(E) (a) Cu 2 + aq + H 2 g Cu s + 2H + aq
(b)
Au + aq + Fe 2+ aq Au s + Fe 3+ aq
(c)
2Cu 2+ aq + SO 2 g + 2 H 2 O(l) 2 Cu + aq + SO 4
aq + 4 H + aq
(M) In either case, the acid acts as an oxidizing agent and dissolves silver; the gold is
unaffected.
Oxidation:
{Ag s Ag + aq + e }
3
Reduction:
NO 3 aq + 4H + aq + 3e NO g + 2H 2 O (l)
Net:
Oxidation:
{Ag s Ag + aq + e }
Reduction:
SO 4
Net:
45.
aq + 4H + aq + 2e SO2 g + 2H 2O(l)
2
2 Ag s + SO 4 aq + 4 H + aq 2 Ag + aq + SO 2 g + 2 H 2 O(l)
2
Cu 2+
(M) The Integrative Example showed K c = 1.2 106 =
or
2
Cu +
2
2+
6
+
Cu = 1.2 10 Cu
2
(a) When Cu + = 0.20 M, Cu 2+ = 1.2 106 0.20 = 4.8 104 M. This is an
impossibly high concentration. Thus Cu + = 0.20 M can never be achieved.
(b) When Cu + = 1.0 1010 M, Cu 2+ = 1.2 106 1.0 1010 = 1.2 1014 M . This is
an entirely reasonable (even though small) concentration; Cu + = 1.0 1010 M can
2
be maintained in solution.
46.
1148
Combination of the reactions labeled "overall" and "total" gives the following result.
2 Cu(s) + O2(g) + H2O(l) + CO2(g) 2 Cu2+(aq) + 2 OH (aq) + CO32 (aq)
The ionic product of the resultant reaction combine in a precipitation reaction to form
2 Cu2+(aq) + 2 OH (aq) + CO32 (aq) Cu2(OH)2CO3 (s)
Group 12 Metals
47.
(E) Given: Hg2+/Hg reduction potential = 0.854 V and Hg22+/Hg reduction potential = 0.796 V
Using the additive nature of free energies and the fact that G = -nFE, we can determine the
2(0.854V) - 0.796V
= 0.912 V
Hg2+/Hg22+ potential as
1
48.
Keq = Kp = 87 atm-1 =
49.
1
PO2
Therefore, PO2 =
1
1
=
= 0.011 atm
KP
87
(M) (a) Estimate Kp for ZnO(s) + C(s) Zn(l) + CO(g) at 800 C (Note: Zn(l) boils at 907 C)
G = 35 kJ
0.05223 (61,960)
+ 8.118 = 2.742
298
1149
n
P
= [Hg] =
V RT
PV = nRT
1atm
)
760 mmHg
= 9.744 10 8 mol L 1
L atm
0.08206
(298K)
K mol
(0.001811mmHg)(
Next, convert to mg Hg m 3:
mol 1000 L 200.59 g Hg 1000 mg
3
[Hg] = 9.874 x 108
= 19.5 mg Hg m
3
L m 1mol Hg 1g Hg
(This is approximately 400 times greater than the permissible level of 0.05 mg Hg m 3)
51.
(M) We must calculate the wavelength of light absorbed in order to promote an electron
across each band gap.
Ephoton = hv
For CdS, =
6.022 10
23
c = v or v = c/
or
34
= N A hc/Emole
1
violet light
The blue light absorbed by CdS is subtracted from the white light incident on the surface
of the solid. The remaining reflected light is yellow in this case. When the violet light is
subtracted from the white light incident on the ZnO surface, the reflected light appears
white.
52.
(D) The color that we see is the complementary color to the color absorbed. The color
absorbed, in turn, is determined by the energy separation of the band gap. If the
wavelength for the absorbed color is short, the energy separation for the band gap is large.
The yellow color of CdS means that the complementary color, violet, is absorbed. Since
violet light has a quite short wavelength (about 410 nm), CdS must have a very large band
gap energetically.
HgS is red, meaning that the color absorbed is green, which has a moderate wavelength
(about 520 nm). HgS must have a band gap of intermediate energy.
CdSe is black, meaning that visible light of all wavelengths and thus all energies in the
visible region are absorbed. This would occur if CdSe has a very small band gap, smaller
than that of least energetic red light (about 650 nm).
1150
Oxidation :
{Cu(s)
Cu 2 (aq) 2 e } 2
Reduction :
O 2 (g) 2 H 2 O(l) 4 e
4 OH (aq)
Net :
This oxidation-reduction reaction produces an alkaline solution. SO3(g) dissolves in this alkaline
solution to produce hydrogen sulfate ion in an acid-base reaction.
Step (a) :
HSO 4 (aq)
SO 3 (g) OH (aq)
Step (b) :
SO 4 (aq) H 2 O(l )
HSO 4 (aq) OH (aq)
Total :
SO 3 (g) 2 OH (aq)
SO 4 (aq) H 2 O(l)
The combination of the reactions labeled Net: and Total: gives the following result.
57. (M) The noble gas formalism requires that the number of valence electrons possessed by the
metal atom plus the number of sigma electrons be equal to the number of electrons in the
succeeding noble gas atom.
(a) Mo(CO)6 ; Mo has 42 electrons, 6 CO contribute another 12 for 54, which is the number
of electrons in Xe
1151
(b) Os(CO)5 ; Os has 76 electrons, 5 CO contribute another 10 for 86, which is the number
of electrons in Rn
(c) Re(CO)5-; Re anion has 76 electrons, 5 CO contribute another 10 for 86, which is the
number of electrons in Rn
(d) The trigonal bipyramidal shape of nickel and iron carbonyls does not fit well in
crystalline lattices, either because of its symmetry or repulsions with its neighbors and,
consequently, these five-coordinate carbonyls are liquids at room temperature.
Compare this to octahedral complexes (Cr(CO)6 and others), which are solids because
they fit well into these lattices. Weak intermolecular attractions in the low molecular
mass, symmetrical nickel and iron carbonyls result in the liquid state at room
temperature. Because of the two metal atoms in the higher molecular mass, less
symmetrical cobalt carbonyl molecules, stronger intermolecular attractions lead to the
solid state.
(e) This compound would be an ionic, salt-like material consisting of Na+ and V(CO)6- ions.
58. (M) (a) Breaks occur at the melting point and boiling point due to changes in the states of
the metals (solid liquid gas).
(b) Slopes of these lines become more positive as the temperature increases due to the sign of
S for these reactions. The slope should be equal to -S, where S is a negative
number in these cases that becomes more negative with a change in phase (higher
temperature).
(c) The break at the boiling point is sharper than the break at the melting point because
Sfusion <<Svaporization.
59.
(M) Oxidation :
2 I (aq)
I 2 (s) 2 e
Reduction:{Cu 2 (aq) e
Cu (aq)}
E 0.535 V
2
E 0.159 V
Net:
Cu 2 (aq) 2 I (aq)
2 Cu (aq) I2 (s) E cell 0.376 V
G nFE RT ln K
ln K
29.3
RT
8.3145 J mol1 K 1 298.15 K
K e29.3 2 1013
K redox 2 1013
1/ K sp 2 1/(1.1 1012 ) 2
Cu 2 (aq) 4 I (aq)
2 CuI s I 2 (s)
K redox
2 1013
2 1011
12)2
K sp 2
(1.1 10
n2
I2 and I- form I3- in aqueous solution. So, adding an additional mole of I- to the last
reaction yields:
Cu 2 (aq) 5 I (aq)
2 CuIs I 3 (s)
1152
60. (D) A detailed calculation would involve determining the final concentrations of all
species. But we can get approximate values of the gold-containing ions by determining
values of the equilibrium constants for the reactions involved. First, we determine the value
of the equilibrium constant for the disproportionation of Au+(aq). To accomplish this, find
the value of Eo for the couple Au+(aq)|Au(s).
Au (aq)
Au 3 (aq) 2 e
Oxidation
E 1.36 V
Reduction:
{Au (aq) e
Au(s)} 2
E 1.83 V
Net:
3Au (aq)
Au 3 (aq) 2 Au(s)
Ecell
0.47 V
ln K
36.6
RT
8.3145 J mol1 K 1 298.15 K
K e36.6 8 1015
Then we determine the value of the equilibrium constant for dissolving and disproportionation.
Disproportionation :
3 Au (aq)
Au 3 (aq) 2 Au(s) K disp 8 1015
Dissolving :
{AuCl(s)
Au (aq) Cl (aq)} 3
Net :
3 AuCl(s)
Au 3 (aq) 2 Au(s) 3 Cl (aq)
K K disp K sp 8 10 (2.0 10
3
15
13 3
) 6.4 10
23
K sp (2.0 10 13 ) 3
K
6.4 1023
1 106 M [Au 3 ]
27
AgO(s) 2 H (aq)
Ag 2 (aq) H 2 O(l)
Dissolution:
Oxidation :
2 H 2 O(l)
O 2 (g) 4 H (aq) 4 e
2
E 1.229 V
Reduction :
{Ag (aq) e
Ag (aq)}
E 1.98 V
Net :
2 H 2 O(l) 4 Ag 2 (aq)
O 2 (g) 4 H (aq) 4 Ag (aq)
Association:
Elimination:
2 HCrO 4 (aq)
2 H (aq) 2 CrO 4 2 (aq)
Cr2O7 2 (aq) H 2 O(l)
2 HCrO 4 (aq)
1/ K a 2 1/ (3.2 107 ) 2
K
1153
63. (D) The presence of both acetate ion and acetic acid establishes a buffer and fixes the pH of
the solution. This, in turn, fixes [CrO42]. We then can determine the concentration of each
of the cations that can coexist with this [CrO42] before precipitation occurs. First we
determine [H3O+], with the aid of the Henderson-Hasselbalch equation.
pH pK a log
[C 2 H 3 O 2 ]
1.0 M
log (1.8 105 ) log
4.74
[HC2 H3 O2 ]
1.0 M
[Cr2 O7 2 ]
0.0010 M
3.1 106
3.1 106
9.8 105 M
14
3.2 10
K sp
1.2 1010
1.2 106 M
2
5
[CrO4 ] 9.8 10
[CrO 4 2 ]
[Ba 2 ]max
2.2 105
0.22 M
9.8 105
7.1 104
7.2 M
9.8 105
[Sr 2 ]max
[Ca 2 ]max
Each cation is initially present at 0.10 M. Neither strontium ion nor calcium ion will
precipitate, while BaCrO4 will precipitate until [Ba2+] has declined to far less than 0.1% of
its original value. Thus, barium ion is effectively separated from the other two cations by
chromate ion precipitation under these conditions.
64. (D) The equations are balanced with the ion-electron method. Oxalic acid is oxidized in each
case.
Oxidation: H 2 C 2 O 4 (aq)
2 H (aq) 2 CO 2 (g) 2 e
Reduction:MnO 2 (s) 4 H (aq) 2 e
Mn 2 (aq) 2 H 2 O(l)
Net: H 2 C2 O 4 (aq) MnO 2 (s) 2 H (aq)
Mn 2 (aq) 2 CO 2 (g) 2 H 2 O(l )
Oxidation:{H 2 C 2 O 4 (aq)
2 H (aq) 2
CO 2 (g) 2 e
} 5
1 L soln
2 mol MnO 4
126.07 g H 2 C 2 O 4 2H 2 O
0.9474 g H 2 C 2 O 4 2H 2 O
1 mol H 2 C 2 O 4 2H 2 O
1154
Thus, the mass of oxalic acid that reacted with MnO2 is 1.651 g 0.9474 g = 0.704 g
H2C2O42H2O. Now we can determine the mass of MnO2 in the ore.
mass MnO 2 0.704 g H 2 C2 O 4 2H 2 O
86.94 g MnO 2
0.485 g MnO 2
1 mol MnO 2
1 mol H 2 C 2 O 4 .2H 2 O
1 mol MnO 2
126.07 g H 2 C2 O 4 2H 2 O 1 mol H 2 C2 O 4
%MnO 2
0.485 g MnO 2
100% 82.3%
0.589 g ore
1.67 mL soln
2
2
volume
6 mmol Fe
0.1000 mmol Cr2 O 7
titrant
1 mmol MnO 4
1 mL solution
3
volume 1.00 mmol Fe 5 mmol Fe 2 0.1000 mmol MnO 2.00 mL soln
4
1 mL soln
1 mmol Cr2 O7 2
5 mmol Fe 2
1 mL soln
29.40 mL of 0.1000 mmol MnO 4
66. (M) A high oxidation state of a metal can only be stabilized by an anion of an element that is
highly electronegative. Fluorine and oxygen are the two most electronegative elements in
the periodic table and thus should be most effective at stabilizing a high oxidation state of a
metal.
67. (D) The precipitation reaction of dichromate ion permits us to determine from the formula of
barium chromate the amount of chromium present, while the redox reaction of
permanganate ion permits us to determine the amount of manganese present in the 250.0 mL
solution. The 15.95 ml volume of Fe2+ titrant assumes (contrary to what the problem
implies) that the chromate has been removed by precipitation. Ba(MnO4)2 is quite water
1155
Equation:
0.549 g BaCrO 4
1 mol BaCrO 4
1 mol Cr
52.00 g Cr
mass of Cr 2.82 g Cr
equation:
10 ml 1 mol Cr 3 6 mol Fe 2
10.00 mL sample
1 mL titrant
5 mmol Fe 2
1 mmol Mn
54.94 mg Mn
1 g Mn
0.3286 Mn
1 mmol Mn 1000 mg Mn
1 mmol MnO 4
%Mn
0.3286 g Mn
2.82 g Cr
100% 3.286% Mn %Cr
100% 28.2% Cr
10.000 g steel
10.000 g steel
dimethylglyoximate.
1 mol Ni
0.3461 mol Ni
58.69 g Ni
1 mol C
33.26 g C
2.769 mol C
12.011 g C
20.31 g Ni
4.88 g H
1 mol H
1.008 g H
4.84 mol H
1 mol O
1.384 mol O
15.999 g O
1 mol N
19.39 g N
1.384 mol N
14.007 g N
22.15 g O
0.3461
1.000 mol Ni
0.3461
8.001 mol C
0.3461
14.0 mol H
0.3461
3.999 mol O
0.3461
3.999 mol N
0.104 g NiDMG
1 mol NiDMG
58.69 g Ni
1 mol Ni
10.00 mL
288.91 g NiDMG 1 mol NiDMG 1 mol Ni
1156
0.528 g Ni
0.528 g Ni
% Ni in steel
100% 3.52%
15.020 g steel
A
69. (M)
look
at
Appendix
indicates
that
Cr(OH)3, K sp 6.3 10 31 ;
The concentration is smaller than the lower limit of the normal range.
71. (M)
(a)
(b)
(c)
O
O
Hg
72.
(M)
O
Mn
Hg
O
Mn
Os
O
O
O
(7)(1.60 1019 C)
4500 C mm 3
9
3
(4/3)(39 10 mm)
This value is more than 4 times the value given in Table 21.4 for Be2+ (1108 C mm3).
We know that there is significant covalent bonding in beryllium compounds. We expect
1157
the bonding in Mn2O7 to be primarily covalent. With such a large charge density, a Mn7+ ion
would be very strongly polarizing, drawing electron density away from surrounding anions and
leading to bonds with primarily covalent character.
1
73.
(M) ? Ti per unit cell = Ti per corner 8 corners per cell = 1 Ti
8
? Ni per unit cell = 1
The empirical formula is NiTi. The % Ti by mass is 100 47.88/(47.88 + 63.55) = 45%
FEATURE PROBLEMS
74.
Consequently, the plot of G for the net reaction as a function of temperature will
be a straight line with a slope of [{S (Rxn b)} {S (Rxn c)}] (in kJ/K) and a
y-intercept of [{H (Rxn b)} {H (Rxn c)}] (in kJ).
Since Ho (Rxn b) = 393.5 kJ, Ho (Rxn c) = 566 kJ, So (Rxn b) = 2.9 J/K and
So (Rxn c) = 173.1 J/K, the plot of G vs. T for the reaction
C(s) + CO2(g) 2 CO(g) will follow the equation y 0.176 x 172.5
From the graph, we can see that the difference in G (line b line c at 1000 C) is
~ 40 kJ/mol. Kp is readily calculated using this value of G.
G = -RTlnKp = -40 kJ = (8.3145 10-3 kJ K-1 mol-1)( 1273 K)(ln Kp)
lnKp = 3.8 Hence, Kp = 44
The equilibrium partial pressure for CO(g) is then determined by using the
Kp expression:
1158
P
K CO
p
PCO
(PCO2 )
44
(0.25 atm)
Alternatively, we can determine the partial pressure for CO2 at 1000 C via the calculated
H and S values for the reaction C(s) + CO2(g) 2 CO(g) to find G at 1000 C ,
and ultimately Kp with the relationship G = -RTlnKp (here we are making the
assumption that H and S are relatively constant over the temperature range 298 K to
1273 K). The calculated values of H and S (using Appendix D) are given below:
H = [2 110.5 kJ] [ 393.5 kJ + 0 kJ] = 172.5 kJ
S = [2 197.7 J K-1] [1 5.74 J K-1 + 213.7 J K-1] = 176.0 J K-1
To find G at 1000oC, we simply plug x =1273 K into the straight-line equation we
developed above and solve for y (G).
So, y 0.176(1273K) 172.5 ; y 51.5 kJ
Next we need to calculate the Kp for the reaction at 1000oC.
P
K CO
p
75.
(PCO2 )
PCO
(0.25 atm)
(M) (a) The amphoteric cations are Al3+, Cr3+, and Zn2+.
-
(c)
1159
(d)
Co3+ is reduced to Co2+ by the H2O2 in solution. The other hydroxides simply
dissolve in strong acid:
+
(e)
(ii)
(iii)
(iv)
NH3(aq) + H2O(l)
Fe(OH)3(s);
Both Co3+ and Ni2+ form soluble complex ions with ammonia ligands rather than
hydroxide precipitates.
SELF-ASSESSMENT EXERCISES
76.
(E) (a) A key feature of ferromagnetism is that in the solid state, the metal atoms are
thought to be grouped together into small regions called domainscontaining rather
large numbers of atoms.
(b) Flotation is a process used to determine metal concentration.
(c) Leaching is the process by which metal ions are extracted (leached) from the ore by a
liquid. Leaching agents include water, acids, bases, and salt solutions. Oxidation
reduction reactions may also be involved.
(d) Mercury alloys, called amalgams, are commonly made with most metals, and some of
these amalgams are of commercial importance.
77.
(E) (a) In the series of elements in which the 4f subshell is filled, atomic radii decrease
somewhat. This phenomenon occurs in the lanthanide series ( Z=58 to 71) and is called
the lanthanide contraction.
(b) Zone melting (or zone refining or floating zone process) is a group of similar methods
of purifying crystals, in which a narrow region of a crystal is molten, and this molten
zone is moved along the crystal (in practice, the crystal is pulled through the heater). The
molten region melts impure solid at its forward edge and leaves a wake of purer material
solidified behind it as it moves through the ingot. The impurities concentrate in the melt,
and are moved to one end of the ingot.
(c) Basic oxygen process is a steelmaking method in which pure oxygen is blown into a
bath of molten blast-furnace iron and scrap. The oxygen initiates a series of intensively
exothermic (heat-releasing) reactions, including the oxidation of such impurities as
carbon, silicon, phosphorus, and manganese.
1160
(E) (a) Ferromagnetism is the basic mechanism by which certain materials (such as iron)
form permanent magnets, or are attracted to magnets. Paramagnetism is a form of
magnetism which occurs only in the presence of an externally applied magnetic field.
Paramagnetic materials are also attracted to magnetic fields.
(b) An ore is roasted (heated to a high temperature) to convert a metal
compound to its oxide, which can then be reduced. The oxidation number of a metal
decreases as a result of reduction.
(c) Hydrometallurgy is part of the field of extractive metallurgy involving the use of
aqueous chemistry for the recovery of metals from ores, concentrates, and recycled or
residual materials. Pyrometallurgy is a branch of extractive metallurgy. It consists of the
thermal treatment of minerals and metallurgical ores and concentrates to bring about
physical and chemical transformations in the materials to enable recovery of valuable
metals.
(d) Chromates are the salts that contain CrO42- anions. Dichromates, on the other hand,
contain Cr2O72- anions. In both compounds chromium is in +6 oxidation state.
79.
(E) (a) Pig iron is impure iron (95% Fe) formed in the reduction of iron ore in a blast
furnace.
(b) Ferromanganese is an iron-manganese alloy formed by the reduction of a
mixture of iron and manganese oxides.
(c) Chromite ore, Fe(CrO2)2 is the principal chromium ore.
(d) Brass is an allow of Zn and Cu with small amounts of Sn, Pb, and Fe.
(e) Aqua regia is a mixture of HCl(aq) and HNO3(aq) that dissolves inactive metals by a
combination of oxidation and complex ion formation.
(f) Blister copper, formed in the
reduction of a mixture of Cu2O(s) and Cu2S(s), is
impure Cu(s) containing SO2(g).
(g) Stainless steel is an iron alloy with varying quantities of metals such as Cr, Mn,
and Ni, and a small and carefully controlled percentage of carbon.
80.
81.
(E) (b)
82.
(E) (d)
83.
(E) (a)
84.
(E) (d)
85.
86.
(M) CrO3(s), (b) potassium manganate, (c) chromium carbonyl, (d) BaCr2O7, (e)
lanthanum(III) sulfate nonahydrate, (f) Au(CN)33H2O.
1161
87.
88.
89.
(M) HNO3 is the oxidizing agent for oxidizing the metal to Au3+ but Au3+ must be
stabilized in solution. In aqua regia, Cl- ions combine with Au3+ to form [AuCl4]-, which
is stable in solution.
90.
(M) The Fe3+ ion forms a complex ion, Fe(H2O)63+, in aqueous solution. The complex
behaves as a weak monoprotic acid in solution. See Equation (23.36).
1162