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\ .
\ .
= 0.0271416 initial mol of hypo (unrounded)
The next steps requires us to assume there has been no volume change in the solution.
( )
3
10 L 0.0378 mol hypo
258 mL
1 mL L
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\ .
\ .
= 0.0097524 remaining mol of hypo (unrounded)
Hypo reacting with AgBr = (0.0271416 - 0.0097524) = 0.0173892 mol hypo (unrounded)
Mass AgBr = ( )
1 mol AgBr 187.8 g AgBr
0.2616636 mol hypo
2 mol hypo 1 mol AgBr
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\ .\ .
= 1.63284588 = 1.63 g AgBr
23.119 a) 1) [Pt(NH
3
)
6
]Cl
4
; 4+ 2) 5 ions form; 4 mol AgCl precipitating
b) 1) [Pt(NH
3
)
4
Cl
2
]Cl
2
; 2+ 2) 3 ions form; 2 mol AgCl precipitating
23.120 a) U = +6; Np = +7 b) +3 for both
23.121 a) 2 Fe
3+
(aq) + 6 OCl
-
(aq) + 4 OH
-
(aq) 2 FeO
4
2-
(aq) + 6 Cl
-
(aq) + 2 H
2
O(l) Fe
6+
b) K
4
[Mn(CN)
6
](s) + 2 K(s) K
6
[Mn(CN)
6
](s) Mn
0
c) 12 NaO
2
(s) + Co
3
O
4
(s) 3 Na
4
CoO
4
(s) + 8 O
2
(g) Co
4+
d) VCl
3
(s) + 4 Na(s) + 6 CO(g) Na[V(CO)
6
](s) + 3 NaCl(s) V
1-
e) BaO
2
(s) + Ni
2+
(aq) + 2 OH
-
(aq) BaNiO
3
(s) + H
2
O(l) Ni
4+
f) 11 CO(g) + 12 OH
-
(aq) + 2 Co
2+
(aq) 2 [Co(CO)
4
]
-
(aq) + 3 CO
3
2-
(aq) + 6 H
2
O(l) Co
1-
g) Cs
2
[CuF
4
])s) + F
2
(g) Cs
2
[CuF
6
](s) Cu
4+
h) 6 TaCl
5
(s) + 15 Na(s) 15 NaCl(s) + Ta
6
Cl
15
(s) Ta
3+
i) Cs
2
[AgF
4
](s) + F
2
(g) Cs
2
[AgF
6
](s) Ag
5+
j) 4 K
2
[Ni(CN)
4
](s) + N
2
H
4
(aq) + 4 OH
-
(aq) 2 K
4
[Ni
2
(CN)
6
](s) + N
2
(g) + 4 H
2
O(l) + 4 CN
-
(aq) Ni
1+
23.122
O
Mn O
O
O
23-19
23.123 Geometric (cis-trans) and linkage isomerism.
NH
3
Pt
NCS NH
3
NCS
NH
3
Pt
H
3
N SCN
NCS
cis-diamminedithiocyanatoplatinum(II) trans-diamminedithiocyanatoplatinum(II)
NH
3
Pt
SCN NH
3
SCN
NH
3
Pt
H
3
N NCS
SCN
cis-diamminediisothiocyanatoplatinum(II) trans-diamminediisothiocyanatoplatinum(II)
NH
3
Pt
NCS NH
3
SCN
NH
3
Pt
H
3
N SCN
SCN
cis-diamminethiocyanatoisothiocyanatoplatinum(II)
trans-diamminethiocyanatoisothiocyanatoplatinum(II)
23.124 Anode: 3(Ag(s) ' Ag
+
(aq) + e
-
) E = -(0.80 V)
Cathode: Au
3+
(aq) + 3 e
-
' Au(s) E = 1.50 V
Total: 3 Ag(s) + Au
3+
(aq) ' Au(s) + 3 Ag
+
(aq) E = +0.70 V
The positive voltage indicates that the reaction is spontaneous.
23.125 [Co(NH
3
)
4
(H
2
O)Cl]
2+
tetraammineaquachlorocobalt(III) ion
2 geometric isomers
Cl
Co
NH
3
NH
3
H
3
N
H
3
N
Cl
Co
NH
3
OH
2
NH
3
H
3
N
H
3
N
H
2
O
2+
2+
trans Cl and H
2
O cis Cl and NH
3
23-20
[Cr(H
2
O)
3
Br
2
Cl] triaquadibromochlorochromium(III)
3 geometric isomers
Cl
Cr
Br
OH
2
H
2
O
Br
Cl
Cr
Br
Br
H
2
O
H
2
O
Cl
Cr
Br
OH
2
Br
H
2
O
H
2
O
H
2
O
H
2
O
Brs trans Brs cis Brs cis
H
2
Os facial H
2
Os meridional
(Unfortunately meridional and facial isomers are not covered in the text. Facial (fac) isomers have three adjacent
corners of the octahedron occupied by similar groups. Meridional (mer) isomers have three similar groups around
the outside of the complex.)
[Cr(NH
3
)
2
(H
2
O)
2
Br
2
]
+
diamminediaquadibromochromium(III) ion
6 isomers (5 geometric)
NH
3
Cr
NH
3
Br
OH
2
H
2
O
Br
+ NH
3
Cr
NH
3
Br
Br
H
2
O
H
2
O
+
All pairs are trans Only NH
3
s are trans
NH
3
Cr
OH
2
Br
NH
3
H
2
O
Br
+
NH
3
Cr
Br
NH
3
OH
2
H
2
O
Br
+
Only H
2
Os are trans Only Brs are trans
NH
3
Cr
Br
NH
3
Br
H
2
O
H
2
O
+
NH
3
Cr
Br
OH
2
OH
2
H
3
N
Br
+
All pairs are cis. These are optical isomers of each other.
23.126 In exposing the film, a photoredox reaction takes place, forming Ag and Br atoms. In developing, more Ag
+
is
reduced to Ag(s). In fixing the image, excess Ag
+
is removed by the formation of the Ag(S
2
O
3
)
2
3-
ion.
23.127 The ligand field strength of NH
3
is greater than that of H
2
O. Therefore, the crystal field splitting energy () is
larger, and higher energy (shorter wavelength) light is required to excite the electrons of [Cr(NH
3
)
6
]
3+
. When
[Cr(NH
3
)
6
]
3+
absorbs higher energy blue-violet light, yellow-orange light (the compliment of blue-violet light) is
observed. When [Cr(H
2
O)
6
]
3+
absorbs lower energy red light, blue-gray light is observed.
23-21
23.128 a) The oxidation state of Mn in MnO
4
2-
is +6, in MnO
4
-
is +7, and in MnO
2
is +4.
b) The two half-reactions are
reduction: MnO
4
2-
(aq) MnO
2
(s)
balancing gives: MnO
4
2-
(aq) + 4 H
+
(aq) + 2 e
-
MnO
2
(s) + 2 H
2
O(l)
oxidation: MnO
4
2-
(aq) MnO
4
-
(aq) + e
-
Multiply the oxidation half-reaction by 2 and add to get
3 MnO
4
2-
(aq) + 4 H
+
(aq) 2 MnO
4
-
(aq) + MnO
2
(s) + 2 H
2
O(l)
23.129 a) 2K
2
MnO
4
(aq) + 2H
2
O(l) 2KMnO
4
(aq) + 2KOH(aq) + H
2
(g)
b) Moles MnO
4
-
= ( )
4
1 mol MnO 12 C 3600 s 1 mol e
96 h
s 1 h 96500 C 1 mol e
| | | | | |
| |
| |
| |
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\ .
\ .
\ .\ .
= 42.976 = 43 mol MnO
4
-
23.130 a) The uranium is 8 coordinate.
b) The uranium is +5 (because Na is +1 and F is -1.)
c)
F
F
F
U
F
F
F
F F
3-
23.131 a) V is +5 in VO
3
-
and VO
2
Cl
2
-
; Al is +3 in AlCl
4
-
and AlOCl
2
-
b) No elements change oxidation state so no redox occurs in either reaction.
The balanced equations are:
V
2
O
5
+ 2 HCl VO
2
Cl
2
-
+ VO
3
-
+ 2 H
+
V
2
O
5
+ 6 HCl 2 VOCl
3
+ 3 H
2
O
c) ( )
2 5 2 2 2 2
2 5
2 5 2 5 2 2
1 mol V O 1 mol VO Cl 153.84 g VO Cl
10.0 g V O
181.88 g V O 1 mol V O 1 mol VO Cl
| || | | |
| | |
| |
\ .\ .\ .
= 8.458324 = 8.46 g VO
2
Cl
2
-
( )
2 5 3 3
2 5
2 5 2 5 3
1 mol V O 2 mol VOCl 173.29 g VOCl
10.0 g V O
181.88 g V O 1 mol V O 1 mol VOCl
| || || |
| | |
\ .\ .\ .
= 19.055421 = 19.1 g VO
2
Cl
2
-
23.132 a) chlorophyll: Mg; heme: Fe; vitamin B
12
: Co.
b) They all have the central metal in the center of a large planar ring containing four N donor atoms.
23.133 a) [Co(NH
3
)
6
][Cr(CN)
6
] hexaamminecobalt(III) hexacyanochromate(III)
b) [Co(NH
3
)
5
CN][CrNH
3
(CN)
5
] pentaamminecyanocobalt(III) amminepentacyanochromate(III)
23.134 a) [Pt(NH
3
)
4
][PtCl
6
] tetraammineplatinum(II) hexachloroplatinum(IV)
There are two platinum complexes present, not one as stated in the problem.
b) [Pt(NH
3
)
4
Cl
2
][PtCl
4
] tetraamminedichloroplatinum(IV) tetrachloroplatinum(II)
There are two platinum complexes present, not one as stated in the problem.
23.135 a) A plane that includes both ammonia ligands and the zinc ion is a plane of symmetry. The complex does not
have optical isomers because it has a plane of symmetry.
b) The Pt
2+
ion is d
8
, so the complex is square planar. Any square planar complex has a plane of symmetry, so the
complex does not have optical isomers.
c) The trans octahedral complex has the two chloride ions opposite each other. A plane of symmetry can be
passed through the two chlorides and platinum ion, so the trans-complex does not have optical isomers.
d) No optical isomers for same reason as in part (c).
e) The cis-isomer does not have a plane of symmetry, so it does have optical isomers.
23-22
23.136 Assume a 100-g sample (making the percentages of each element equal to the mass present in grams) and convert
the mass of each element to moles using the elements molar mass. Divide each mole amount by the smallest
mole amount to determine whole number ratios of the elements to determine the empirical formula.
Note, the intermediate values are unrounded to minimize rounding errors.
moles Pt = ( )
1 mol Pt
38.8 g Pt
195.1 g Pt
| |
|
\ .
= 0.198872 mol Pt
moles C1 = ( )
1 mol Cl
14.1 g Cl
35.45 g Cl
| |
|
\ .
= 0.397743 mol Cl
moles C = ( )
1 mol C
28.7 g C
12.01 g C
| |
|
\ .
= 2.389675 mol C
moles P = ( )
1 mol P
12.4 g P
30.97 g P
| |
|
\ .
= 0.400387 mol P
moles H = ( )
1 mol H
6.02 g H
1.008 g H
| |
|
\ .
= 5.972222 mol H
Divide each of the moles just calculated by the smallest value (Pt) gives:
Pt = 1 Cl = 2 C = 12 P = 2 H = 30
The empirical formula for the compound is PtCl
2
C
12
P
2
H
30
. Each triethylphosphine ligand, P(C
2
H
5
)
3
accounts for
one phosphorus atom, 6 carbon atoms, and 15 hydrogen atoms. According to the empirical formula, there are
two triethylphosphine ligands: 2 P(C
2
H
5
)
3
equals C
12
P
2
H
30
. The compound must have two P(C
2
H
5
)
3
ligands and
two chloro ligands per Pt ion. The formula is [Pt[P(C
2
H
5
)
3
]
2
Cl
2
]. The central Pt ion has 4 ligands and is square
planar, existing as either a cis or trans compound.
P
Pt
Cl
P
Cl
C
2
H
5
C
2
H
5
P
Pt
P
Cl
Cl
C
2
H
5
C
2
H
5
C
2
H
5
C
2
H
5
C
2
H
5
C
2
H
5
cis-dichlorobis(triethylphosphine)platinum(II) trans-dichlorobis(triethylphosphine)platinum(II)
23.137 a) The longest distance will be for two of the long bonds trans to each other.
Longest distance = 2 (262 pm) = 524 pm
b) The shortest distance will be for two of the short bonds trans to each other.
Shortest distance = 2 (207 pm) = 414 pm
23.138 Use the ideal gas equation, PV = nRT
P = nRT / V = ( ) ( )
3 3 3
3
20.0 mg Hg 10 g 10 m 1 mol Hg L atm
0.0821 273 25 K
1 mg 1 L 200.6 g Hg mol K m
(
| || || |
| |
+ ( | |
| |
| |
\ . ( \ .
\ .\ .
= 2.439262 x 10
-6
= 2.44 x 10
-6
atm
23.139 Zinc ions prefer a tetrahedral environment. The other ions listed prefer other environments. If the other ions are
placed in a tetrahedral environment in place of the zinc, they cannot behave as well as zinc.
23-23
23.140 a) The first reaction shows no change in the number of particles. In the second reaction, the number of reactant
particles is greater than the number of product particles. A decrease in the number of particles means a decrease in
entropy, while no change in number of particles indicates little change in entropy. Based on entropy change only,
the first reaction is favored.
b) The ethylenediamine complex is more stable with respect to ligand exchange with water because the entropy
change is unfavorable.
23.141 a) [Cr(H
2
O)
6
]
3+
562 nm
E = hc / =
( )( )
34 8
23
9
6.626 x 10 J s 3.00 x 10 m/s
1 nm 6.022 x 10
562 nm mol 10 m
| |
| |
|
|
|
\ .
\ .
= 2.1299878 x 10
5
= 2.13 x 10
-19
J/mol
[Cr(CN)
6
]
3-
381 nm
E = hc / =
( )( )
34 8
23
9
6.626 x 10 J s 3.00 x 10 m/s
1 nm 6.022 x 10
381 nm mol 10 m
| | | |
| |
| |
\ .\ .
= 3.14187 x 10
5
= 3.14 x 10
-19
J/mol
[CrCl
6
]
3-
735 nm
E = hc / =
( )( )
34 8
23
9
6.626 x 10 J s 3.00 x 10 m/s
1 nm 6.022 x 10
735 nm mol 10 m
| | | |
| |
| |
\ .\ .
= 1.62864 x 10
5
= 1.63 x 10
-19
J/mol
[Cr(NH
3
)
6
]
3+
462 nm
E = hc / =
( )( )
34 8
23
9
6.626 x 10 J s 3.00 x 10 m/s
1 nm 6.022 x 10
462 nm mol 10 m
| | | |
| |
| |
\ .\ .
= 2.591024 x 10
5
= 2.59 x 10
-19
J/mol
[Ir(NH
3
)
6
]
3+
244 nm
E = hc / =
( )( )
34 8
23
9
6.626 x 10 J s 3.00 x 10 m/s
1 nm 6.022 x 10
244 nm mol 10 m
| | | |
| |
| |
\ .\ .
= 4.9059555 x 10
5
= 4.91 x 10
-19
J/mol
[Fe(H
2
O)
6
]
2+
966 nm
E = hc / =
( )( )
34 8
23
9
6.626 x 10 J s 3.00 x 10 m/s
1 nm 6.022 x 10
966nm mol 10 m
| | | |
| |
| |
\ .\ .
= 1.239185 x 10
5
= 1.24 x 10
-19
J/mol
[Fe(H
2
O)
6
]
3+
730 nm
E = hc / =
( )( )
34 8
23
9
6.626 x 10 J s 3.00 x 10 m/s
1 nm 6.022 x 10
730 nm mol 10 m
| | | |
| |
| |
\ .\ .
= 1.6397988 x 10
5
= 1.64 x 10
-19
J/mol
[Co(NH
3
)
6
]
3+
405 nm
E = hc / =
( )( )
34 8
23
9
6.626 x 10 J s 3.00 x 10 m/s
1 nm 6.022 x 10
405 nm mol 10 m
| | | |
| |
| |
\ .\ .
= 2.9556868 x 10
5
= 2.96 x 10
-19
J/mol
[Rh(NH
3
)
6
]
3+
295 nm
E = hc / =
( )( )
34 8
23
9
6.626 x 10 J s 3.00 x 10 m/s
1 nm 6.022 x 10
295 nm mol 10 m
| | | |
| |
| |
\ .\ .
= 4.057807 x 10
5
= 4.06 x 10
-19
J/mol
23-24
b) Comparing the energies of the chromium complexes, we find the energy increases in the order:
Cl
-
< H
2
O < NH
3
< CN
-
This is an abbreviated spectrochemical series.
c) The higher the oxidation number (Fe
3+
versus Fe
2+
) the greater the crystal field splitting ().
d) When moving down a column on the periodic table, in this case from Co to Rh to Ir, the greater the energy
required, and the greater the crystal field splitting ().
23.142 a) The immediate reaction with AgNO
3
to yield a red precipitate (Ag
2
CrO
4
) indicates that the chromate is not
directly coordinated to M. The potassium will not be coordinated to M. Silver nitrate does not easily form a white
precipitate thus the chloride must be coordinated to M as part of an inert complex. The ammonia is probably
coordinated to M. The coordination number of M comes from two chlorides plus four ammonia to give a total
of 6.
b) The ammonia and chloride ligands are covalently bonded to M, and the potassium and chromate are ionically
bonded.
c) The ability of oxalate to displace chloride from only one form is the clue. Oxalate is chelating, and will only
displace chlorides in a cis arrangement, not a trans arrangement. Form A is the cis complex, and form B is the
trans complex.