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1.3 The higher value of I2 for Cr relative to Mn is 1.15 n=5, l = 3, and ml = -3,-2,-1,0,1,2,3
a consequence of the special stability of half-
1.16 Li: = Z Zeff ; = 3-1.28 = 1.72
filled subshell configurations and the higher
Zeff of a 3d electron verses a 4s electron. Be: = Z Zeff ; = 4-1.19 = 2.09
1.4 22
10 Ne + He Mg + n
4
2
25
12
1
0 B: = Z Zeff ; = 5-2.42 = 2.58
9 9 12 4 1
1.5 4 Be+ Be C+ He +2 n
4 6 2 0 C: = Z Zeff ; = 6-3.14 = 2.86
1.6 Since helium-4 is the basic building block, N: = Z Zeff ; = 7-3.83 = 3.17
most additional fusion processes will produce
nuclei with even atomic numbers. O: = Z Zeff ; = 8-4.45 = 3.55
F: = Z Zeff ; = 9-5.10 = 3.90
1
Shriver & Atkins: Inorganic Chemistry 5e
Exercises
3.21 (a) Schottky defects
3.1 a b c and = 90, = 90, = 90 (b) Frenkel defects
Self-tests
(a) C5H5N (pyridine)? The conjugate acid ClO4, cannot be studied in sulfuric acid.
is pyridinium ion, C5H6N+.
4.9 Is the CN group electron donating or
(b) HPO42? The conjugate acid is H2PO42. withdrawing?
(c) O2? The conjugate acid is OH. electron withdrawing
(d) CH3COOH? The conjugate acid is 4.11 Is the pKa for HAsO42 consistent with
CH3C(OH)2+. Paulings rules? No. Paulings rules are
only approximate.
(e) [Co(CO)4]? The conjugate acid is
HCo(CO)4. 4.12 What is the order of increasing acid
strength for HNO2, H2SO4, HBrO3, and
(f) CN? The conjugate acid is HCN. HClO4?
4.4 Calculate the [H3O+] and pH of a 0.10 M the order is HClO4 > HBrO3 > H2SO4 >
butanoic acid solution? pH=2.85 HNO2.
4.5 What is the Kb of ethanoic acid? 4.13 Account for the trends in the pKa values of
Kb = 5.6 10 10 the conjugate acids of SiO44, PO43, SO42,
and ClO4?
4.6 What is the Ka for C5H5NH+?
The acidity of the four conjugate acids
Ka = 5.6 106 increases in the order HSiO43 < HPO42 <
4.7
-
Predict if F will behave as an acid or a HSO4 < HClO4.
base in water? 4.14 Which of the following is the stronger acid?
- (a) [Fe(OH2)6]3+ or [Fe(OH2)6]2+? The
F will behave as a base in water.
Fe(III) complex, [Fe(OH2)6]3+, is the stronger
4.8 What are the structures and the pKa values acid.
of chloric (HClO3) and chlorous (HClO2)
(b) [Al(OH2)6]3+ or [Ga(OH2)6]3+?
acid?
O O the aluminum-containing species is more
acidic.
4.18 Which of the following elements form oxide (d) AsF3(g) + SbF5(g) [AsF2][SbF6]?
polyanions or polycations? Al, As, Cu, Mo, The very strong Lewis acid SbF5 displaces the
Si, B, Ti? Lewis acid [AsF2]+ from the Lewis base F.
polycations: Al, Cu, and Ti. (e) EtOH readily dissolves in pyridine? A
polyoxoanions (oxide polyanions): Mo Lewis acidbase complex formation reaction
between EtOH (the acid) and py (the base)
polyoxoanions: As, B, and Si. produces the adduct EtOHpy.
4.19 The change in charge upon aqua ion 4.26 Select the compound with the named
polymerization? characteristic? (a) Strongest Lewis acid:
Polycation formation reduces the average BF3, BCl3, or BBr3? BBr3.
positive charge per central M atom by +1 per BeCl2 or BCl3? Boron trichloride.
M.
B(n-Bu)3 or B(t-Bu)3? B(n-Bu)3.
4.20 Write balanced equations for the formation
of P4O124 from PO43 and for the formation (b) More basic toward BMe3: NMe3 or
of [(H2O) 4Fe(OH)2Fe(OH2)4]4+ from NEt3? NMe3.
[Fe(OH2)6]3+?
2-Me-py or 4-Me-py? 4-Me-py.
4PO43 + 8H3O+ P4O124 + 12H2O
4.27 Which of the following reactions have Keq >
2[Fe(OH2)6]3+ 1? (a) R3PBBr3 + R3NBF3 R3PBF3 +
R3NBBr3? <1
[(H2O)4Fe(OH)2Fe(OH2)4+ + 2H3O+
(b) SO2 + Ph3PHOCMe3 Ph3PSO2 +
4.21 More balanced equations?
HOCMe3? > 1.
(a) H3PO4 and Na2HPO4?
(c) CH3HgI + HCl CH3HgCl + HI? <1
H3PO4 + HPO42- 2H2PO4-
(d) [AgCl2] (aq) + 2 CN (aq) [Ag (CN)2]
4.22 Give the equations for HF in H2SO4 and 4.28 Choose between the two basic sites in
HF in liquid NH3? Me2NPF2?
Both a Brnsted acidbase reaction and a 4.38 Are the f-block elements hard? yes.
Lewis acidbase reaction. 4.39 Calculate the enthalpy change for I2 with
4.32 Write a balanced equation to explain the phenol?
foul odor of damp Al2S3? The foul odor fH = -20.0kJ/mol
suggests H2S formation.
Al2 S 3 + 3H 2 O Al2 O 3 + 3H 2 S
4.33 Describe solvent properties? (a) Favor CHAPTER 5
displacement of Cl by I from an acid
center? If you choose a solvent that
Self-tests
decreases the activity of chloride relative to
iodide, you can shift the following
S5.1 Half-reactions and balanced reaction for
equilibrium to the right:
oxidation of zinc metal by permanganate
acid-Cl- + I- acid-I- + Cl- ions?
2[MnO4 (aq) + 8H+ (aq) + 5e Mn2+(aq)
(b) Favor basicity of R3As over + 4H2O(l)] reduction
R3N? Alcohols such as methanol or ethanol
would be suitable. 5 [ Zn(s) Zn2+(aq) + 2e ] oxidation
+ 3+
(c) Favor acidity of Ag over Al ? An
example of a suitable solvent is diethyl ether. 2MnO4 (aq) + 5Zn(s) + 16H+(aq)
Another suitable solvent is H2O. 5Zn2+(aq) + 2Mn2+(aq) + 8H2O(l)
(d) Promote the reaction 2FeCl3 + ZnCl2 S5.2 Does Cu metal dissolve in dilute HCl? No.
Zn2+ + 2[FeCl4]? A suitable solvent is
acetonitrile, MeCN. S5.3 Can Cr2O72 be used to oxidize Fe2+, and
would Cl oxidation be a problem? Yes.
4.34 Propose a mechanism for the acylation of
Cl- oxidation is not a problem.
benzene? An alumina surface, such as the
partially dehydroxylated one shown below, S5.4 Fuel cell emf with oxygen and hydrogen
would provide Lewis acidic sites that could gases at 5.0 bar?
abstract Cl:
E = 1.25 V.
S5.5 The fate of SO2 emitted into clouds? The
aqueous solution of SO42 and H+ ions
precipitates as acid rain.
S5.6 Can Fe2+ disproportionate under standard
conditions? No.
S5.7 bpy binding to Fe(III) or Fe(II)? Fe(II)
4.35 Why does Hg(II) occur only as preferentially.
HgS? Mercury(II) is a soft Lewis acid, and
so is found in nature only combined with soft S5.8 Potential of AgCl/Ag,Cl couple?
Lewis bases, the most common of which is Eox= 1.38 V
S2.
S5.9 Latimer diagram for Pu? (a) Pu(IV)
4.36 Write Brnsted acidbase reactions in disproportionates to Pu(III) and Pu(V) in
liquid HF? aqueous solution; (b) Pu(V) does not
(a) CH3CH2OH? The balanced equation disproportionate into Pu(VI) and Pu(IV).
is:
CH 3CH 2OH + HF CH 3CH 2OH 2+ + F- S5.10 Frost diagram for thallium in aqueous
acid?
(b) NH3? The equation is
NH + + F-
NH 3 + HF 4
Shriver & Atkins: Inorganic Chemistry 5e
2MnO4 (aq) + 5H2SO3(aq) + H+(aq) 5.13 Calculate the equilibrium constant for
2Mn2+(aq) +5HSO3 (aq) + 3H2O(l) Au+(aq) + 2CN(aq) [Au(CN)2](aq)?
The potential decreases as the pH increases. K = 5.7 1038
5.14 Find the approximate potential of an
aerated lake at pH = 6, and predict the
5.7 Write the Nernst equation for (a) The
predominant species? (a) Fe? 0.5 0.6 V
reduction of O2?
(b) Mn? E = 0.55 V
Q = 1/(p(O2)[H+]4)
(c) S? At pH 0, 0.387 V. At pH 14, SO42
and
would again predominate. HSO4 is the
E = E [(0.059V)/4][log(1/(p(O2)[H+]4)] predominant sulfur species at pH 6.
(b) The reduction of Fe2O3(s)? 5.15 Frost diagram and standard potential for
+ 6
Q = 1/[H ] and E = E (RT/nF)(13.8 pH) the HSO4/S8(s) couple? 0.387 V
5.8 Using Frost diagrams? (a) What happens 5.16 Equilibrium constant for the reaction
when Cl2 is dissolved in aqueous basic Pd2+(aq) + 4 Cl(aq) [PdCl4]2(aq) in 1 M
solution? Cl2 is thermodynamically HCl(aq)? K = 4.37 1010
susceptible to disproportionation to Cl and 5.17 Reduction potential for MnO4 to MnO2(s)
ClO4 when it is dissolved in aqueous base. at pH = 9.00? E = 0.98 V
The oxidation of ClO is slow, so a solution of 5.18 Tendency of mercury species to act as an
Cl and ClO is formed when Cl2 is dissolved oxidizing agent, a reducing agent, or to
in aqueous base. undergo disproportionation? Hg2+ and
(b) What happens when Cl2 is dissolved in Hg22+ are both oxidizing agents. None of
aqueous acid solution? Cl2 will not these species are likely to be good reducing
agents. Hg22+ is not likely to undergo
disproportionate. Cl2 is thermodynamically
disproportionation.
capable of oxidizing water.
5.19 Thermodynamic tendency of HO2 to
(c) Should HClO3 disproportionate in undergo disproportionation? E = +1.275 V.
aqueous acid solution? Kinetic. (is positive), HO2 will undergo
5.9 Write equations for the following disproportionation.
reactions: (a) N2O is bubbled into aqueous 5.20 Dissolved carbon dioxide corrosive towards
NaOH solution? iron? Carbon dioxide and water generate
carbonic acid which encourages the corrosion
5N2O(aq) + 2OH(aq) 2NO3(aq) + process by lowering solution pH.
4N2 (g) + H2O(l)
5.21 What is the maximum E for an anaerobic
(b) Zinc metal is added to aqueous acidic environment rich in Fe2+ and H2S? 0.1 V.
sodium triiodide?
5.22 How will edta4 complexation affect M2+
2+
Zn(s) + I3 (aq) Zn (aq) + 3I (aq)
M0 reductions? The reduction of a M(edta)2
complex will be more difficult than the
(c) I2 is added to excess aqueous acidic reduction of the analogous M2+ aqua ion.
HClO3?
5.23 Which of the boundaries depend on the
3I2(s) + 5ClO3 (aq) + 3H2O(l) 6IO3 choice of [Fe2+]? Any boundary between a
(aq) + 5Cl (aq) + 6H+(aq) soluble species and an insoluble species will
5.10 Electrode potential for Ni2+/Ni couple at pH change as the concentration of the soluble
species changes. The boundaries between the
= 14? E = 0.21 V
two soluble species, and between the two
5.11 Will acid or base most favour the following insoluble species, will not depend on the
half-reactions? (a) Mn2+ MnO4? Base choice of [Fe2+].
(b) ClO4 ClO3? Acid 5.24 Under what conditions will Al reduce
(c) H2O2 O2? Base MgO? Above about 1400C.
S6.11 Orbital symmetry for a square-planar (d) SO42? three different S4.
array of H atoms? B2g. 6.3 Assigning point groups: (a) NH2Cl? Cs
S6.12 Which Pt atomic orbitals can combine with (b) CO32? D3h
which of these SALCs? The atomic orbitals
much have matching symmetries to (c) SiF4? Td
generate SALCs. 5s and 4dz2 have A1g
(d) HCN? Cv.
symmetry; the dx2-y2 has B1g symmetry; and
5px and 5py have Eu symmetry. (e) SiFClBrI? C1.
S6.13 Predict how the IR and Raman spectra of (f) BrF4? D4h.
SF5Cl differ from that of SF6?
Shriver & Atkins: Inorganic Chemistry 5e
6.4 How many planes of symmetry does a 6.12 [AuCl4] ion? of all 3N displacements
benzene molecule possess? What chloro- and irreducible representations?
substituted benzene has exactly four planes A1g + A2g + B1g + B2g + Eg + 2A2u + B2u + 3Eu
of symmetry? 7,and C6H3Cl3.
6.5 The symmetry elements of orbitals? (a) An 6.13 IR and Raman to distinguish between: (a)
s orbital? Infinite number of Cn axes, plus planar and pyramidal forms of PF3, (b)
an infinite number of mirror planes of planar and 90o-twisted forms of B2F4 (D2h
symmetry, plus center of inversion, i. and D2d respectively)?
(b) A p orbital? An infinite number of mirror (a) Planar PF3, D3h, vibrations are: A1
planes that pass through both lobes and (Raman, polarized) + 2E (IR and Raman) +
include the long axis of the orbital. In A2 (IR).
addition, the long axis is a Cn axis, where n Pyramidal PF3, C3v, vibrations are: 2A1 (IR
can be any number from 1 to . and Raman, polarized) + 2E (IR and Raman)
(c) A dxy orbital? Center of symmetry, three (b) For the planar form of B2F4 (D2h):
mutually perpendicular C2 axes, three The vibrations are:
mutually perpendicular mirror planes of 3Ag (Raman, polarized) + 2B2g (Raman) +
symmetry, two planes that are rotated by 45 B3g (Raman) + Au(inactive) + 2B1u (IR) +
about the z axis from the xz plane and the yz B2u (IR) + 2B3u (IR).
plane.
(d) A dz2 orbital? In addition to the For the 90o-twisted form of B2F4 (D2d)
The vibrations are: 3A1 (Raman, polarized) +
symmetry elements possessed by a p orbital:
B1 (Raman) + 2B2 (IR and Raman ) + 3E (IR
(i) a center of symmetry, (ii) a mirror plane
and Raman).
that is perpendicular to the C axis, (iii) an
infinite number of C2 axes that pass through
6.14 (a) Take the 4 hydrogen 1s orbitals of CH4
the center of the orbital and are perpendicular and determine how they transform under
to the C axis, and (iv) an S axis. Td. (b) Confirm that it is possible to reduce
6.6 SO32 ion? (a) Point group? C3v this representation to A1 + T2. (c) Which
atomic orbitals on C can form MOs with
(b) Degenerate MOs? 2 H1s SALCs?
(c) Which s and p orbitals have the Using symmetry Td, 3N reduces to: A1 + T2.
maximum degeneracy? 3px and 3py orbitals The MOs would be constructed from SALCs
are doubly degenerate. with H1s and 2s and 2p atomic orbitals on C.
CHAPTER 7 Exercises
7.1 Name and draw the structures of the
Self-tests complexes? (a) [Ni(CO)4]? Nickel
tetracarbonyl or tetracarbonyl nickel(0).
S7.1 Give formulas corresponding to the
following names? (a) Cis- CO
diaquadichloroplatinum(II)? cis-
[PtCl2(OH2)2],
Ni
trans-diaquadichloroplatinum(II), trans- CO
OC
[PtCl2(OH2)2]. CO
(b) Diamminetetra(isothiocyanato) (b) [Ni(CN)4]2? Tetracyanonickelate (II).
chromate(III)?
[Cr(NCS)4(NH3)2] . ,can exist as, cis- 2-
[Cr(NCS)4(NH3)2] or trans-
[Cr(NCS)4(NH3)2] . NC CN
Ni
(c) Tris(ethylenediamine)rhodium (III)? NC CN
[Rh(en)3]3+.
(d) Bromopentacarbonylmanganese
(I)? [MnBr (CO)5]. (c) [CoCl4]2? Tetrachlorocobaltate (II)
(e) Chlorotris(triphenylphosphine)rhodium
(I)? [RhCl(PPh3)3]. 2-
Cl
S7.2 What type of isomers are possible for
[Cr(NO2)26H2O]? The hydrate isomers
and linkage isomers of the NO2 group. Also, Co
Cl
[Cr(ONO)(H2O)5]NO2 H2O. Cl
Cl
S7.3 Identifying isomers? Note that the two
phosphine ligands in the trans isomer are (d) [Mn(NH3)6]2+?
related, therefore, they exhibit the same Hexaamminemanganesium (II)
2+
chemical shift.
NH3
S7.4 Sketches of the mer and fac isomers of H3N NH3
[Co(gly)3]? Mn
H3N NH3
NH3
M M
L L L L
L
7.15 Draw all possible isomers for [MA2BCDE]? identical reflections to those of rutile TiO2 but
Including optical isomers, 15 isomers are shifted to slightly higher diffraction angles.
possible! .
S8.2 TiO2 in sunscreens?
A A A
B A B A B A
Titania articles absorb this ultraviolet
M M M radiation
C D E C D E
E D C S8.3 Molecular shape and vibrational modes for
XeF2? Trigonal bipyramidal, 4 total
vibrational modes.
A A A
B E B E B C
S8.4 (a) 77Se-NMR spectrum consists of a triplet
M M M of triplets? The triplet of triplets.
D C C D D E
A A A (b) Proton resonance of the hydrido ligand
consist of eight equal intensity lines? yes.
S8.5 EPR signal of new material arises from W
A A A
E A D A C A sites?
M M M
B
C
D E
B
C D
E
B 14% of naturally occurring tungsten is 183W,
which has I = . Thus, the signal is split into
2 lines.
7.16 Which of the following complexes are S8.6 Isomer shift for iron in Sr2FeO4? The
chiral? (a) [Cr(ox)3]3? Chiral Smaller and less positive.
(b) cis-[PtCl2(en)]? Chiral (The en is not S8.7 Why does the mass spectrum of ClBr3 have
planar). five peaks separated by 2 u? Halogen
isomers.
(c) cis-[RhCl2(NH3)4]+? not chiral.
(d) [Ru(bipy)3]2+? chiral
Exercises
(e) fac-[Co(NO2)3(dien)]? Not chiral.
8.1 How would you determine crystalline
(f) mer-[Co(NO2)3(dien)]? Chiral (dien is components in mineral sample? Powder X-
not planar). ray diffraction.
7.17 Which isomer, or , is the complex 8.2 Why are there no diffraction maxima in
Mn(acac)3, shown in the exercise? The borosilicate glass? Glass has no long-range
isomer. periodicity or order.
7.18 Draw both isomers, or , of the complex 8.3 What is the minimum size of a cubic
[Ru(en)3]+2 ? crystal that can be studied? 0.5 m by 0.5
m by 0.5 m.
N N
7.20 Compare these values with those of 8.6 Wavenumber for OO in O2+? In the region
ammonia given in exercise 7.19 and suggest of 1800 cm 1.
why they are different? The chelate effect. 8.7 UV photoelectron spectrum of NH3? The
band at 11 eV is due to the lone pair and the
pyramidal angle. The ionised molecule has
CHAPTER 8 greater planarity, thus the long progression.
8.8 Raman bands assignments? N(SiH3)3 is
Self-tests planar. N(CH3) 3 is pyramidal.
8.9 Single 13C peak in NMR? Chemically S9.1 Found in aluminosilicate minerals or
distinct carbonyls are exchanging position sulfides?
sufficiently quickly. Cd and Pb will be found as sulfides.
Rb and Sr can be found in aluminosilicate
8.10 Form of 19F-NMR and 77Se-NMR spectra minerals.
of 77SeF4? 19F NMR spectrum reveals two Cr and Pd can be found in both oxides and
1:3:3:1 quartets. The 77Se-NMR spectrum is a sulfides.
triplet of triplets.
8.11 NMR spectral features for XeF5? All 5 of S9.2 Sulfur forms catenated polysulfides
the F atoms are chemically equivalent. whereas polyoxygen anions are unknown?
Approximately 25% is present as 129Xe, I = Owing to a strong tendency to form strong
1/2, and in this case the 19F resonance is a double bonds, it is more likely that
doublet. The final result is a composite: two polyoxygen anions will form pi bonds that
lines of 12.5% intensity from the 19F coupled limit extended bonding owing to restrictions
to the 129Xe, and one remaining line of 75%. on pi orbital overlap through multiple
bridging centres.
8.12 g-values? 1.94, 1.74, and 1.56.
8.13 Slower process, NMR or EPR? NMR. S9.3 Shape of XeO4 and identify the Z + 8
compound with the same structure?
8.14 Differences in EPR spectrum for d-metal A tetrahedral geometry. The same structure is
with one electron in solution versus frozen? SmO4.
In aqueous solution at room temperature,
molecular tumbling removes the effect of the S9.4 Comment on fH values? It is evident from
g-value anisotropy. In frozen solution, g- the values that as we move down the group,
value anisotropy can be observed. steric crowding of the fluorines is minimized.
8.15 Isomer shift for iron in BaFe(VI)O4? A S9.5 Further data useful when drawing
positive shift for Fe(VI) well below +0.2 mm comparisons with the value for V2O5? We
s-1. would have to know the products formed
8.16 Charge on Fe atoms in Fe4[Fe(CN)6]3? EPR upon decomposition.
and Mssbauer.
8.17 No quadrupole splitting in Mssbauer Exercises
spectrum of SbF5? The geometry must be
close to cubic in the solid state. 9.1 Maximum stable oxidation state? (a) Ba;
+2, (b) As; +5, (c) P; +5, (d) Cl; +7.
8.18 No peak in the mass spectrum of Ag at 108
u? Two isotopes, 107Ag (51.82%) and 109Ag
9.2 Form saline hydrides, oxides and
(48.18%). Compounds that contain silver will peroxides, and all the carbides react with
have two mass peaks. water to liberate a hydrocarbon?
8.19 Peaks in mass spectrum of the alkaline earth metals or Group 2 elements.
Mo(C6H6)(CO)3? 258, 230, 200, 186, and
174. 9.3 Elements vary from metals through
metalloids to non-metals; form halides in
8.20 Cyclic voltammogram of Fe(III) complex? oxidation states +5 and +3 and toxic
The complex undergoes a reversible one- gaseous hydrides? Elements in Group 15.
electron reduction with a reduction potential
of 0.21 V. Above 0.720 V the complex is 9.4 BornHaber cycle for the formation of the
oxidized. hypothetical compound NaCl2? Which
thermochemical step is responsible for the
8.21 Zeolite of composition CaAl2Si6O16.nH2O,
fact that NaCl2 does not exist?
determine n.? n=7.2 As an integer, n = 7.
The second ionization energy of
8.22 Ratio of cobalt to acetylacetonate in the sodium is 4562 kJ mol-1 and is responsible for
product? The ratio is 3:1. the fact that the compound does not exist.
9.6 Ionic radii, ionization energy, and metallic 10.3 Assign oxidation numbers to elements?
character? Metallic character, ionic radii
(a) H2S? H = +1, S = 2.
decrease across a period and down a group.
Ionization energy increases across a period (b) KH? H = 1, K = +1.
and decreases down a group.
(c) [ReH9]2? H = 1, Re = +7.
9.7 Names of ores? (a) Mg; MgCO3 magnesite, (d) H2SO4? H = +1, O = 2, S = +6.
(b) Al; Al2O3 bauxite, and (c) Pb; PbS galena.
(e) H2PO(OH)? H bonded to an oxygen
9.8 Identify the Z + 8 element for P. atom = +1. H bonded to the phosphorus atom?
Similarities? V (vanadium). If they are assigned an oxidation number of
+1, and O = 2, then P = +1.
10.4 Preparation of hydrogen gas?
9.9 Calculate fH for SeF6?
fH = 1397 kJ mol-1. (i) CH4(g) + H2O CO(g) + 3H2(g) (1000C)
(ii) C(s) + H2O CO(g) + H2(g) (1000C)
Na+Et3Sn + CH3Br Et3MeSn + NaBr 10.8 Name and classify the following?
(a) BaH2? barium hydride.
Exercises (b) SiH4? silane.
10.1 Where does Hydrogen fit in the periodic (c) NH3? ammonia,
chart? (a) Hydrogen in group 1? Hydrogen
has one valence electron like the group 1 (d) AsH3? Arsine.
metals and is stable as H+, especially in (e) PdH0.9? palladium hydride.
aqueous media.
(f) HI? hydrogen iodide.
(b) Hydrogen in group 17? Hydrogen can
fill its 1s orbital and make a hydride H. The 10.9 Chemical characteristics of hydrides?
halogens are diatomic gases just like (a) Hydridic character? Barium hydride
hydrogen, but chemically it fits well in both
group 1 and group 17. (b) Brnsted acidity? Hydrogen iodide.
(c) Hydrogen in group 14? There is no (c) Variable composition? PdH0.9 .
reason for hydrogen to be placed in this
(d) Lewis basicity? Ammonia.
group.
10.10 Phases of hydrides of the elements? BaH2
10.2 Low reactivity of hydrogen? Hydrogen
and PdH0.9 are solids, none is a liquid, and
exists as a diatomic molecule (H2). It has a
SiH4, NH3, AsH3, and HI are gases.
high bond enthalpy. It also only has two
electrons shared between two protons. 10.11 Structures of H2Se, P2H4, and H3O+? The
Lewis structures of these three species are:
Shriver & Atkins: Inorganic Chemistry 5e
10.15 The synthesis of binary hydrogen S11.4 Sketch the thermodynamic cycle of Group
compounds? (i) direct combination of the 1 carbonate.
elements, (ii) protonation of a Brnsted base,
and (iii) metathesis using a compound such as M2CO3(s) M2O(s) +
LiH, NaBH4, or LiAlH4. CO2(g)
10.16 Compare BH4, AlH4, and GaH4? Since
AlH4 is more hydride-like, it is the
strongest reducing agent.
10.17 Compare period 2 and period 3 hydrogen
compounds? Period 2 compounds:
- except for B2H6, are all exoergic
2M+(g) + CO32(g) 2M+(g) +
- tend to be weaker Brnsted acids and O2(g) + CO2(g)
stronger Brnsted bases
- bond angles in period 2 hydrogen S11.5 Explain the differences in temperature of
compounds reflect a greater degree of sp3 decomposition of LiNO3 and KNO3? KNO3
hybridization decomposes in two steps at two different
temperatures.
- Several period 2 compounds exhibit strong
hydrogen bonding. KNO3(s) KNO2(s) + 1/2O2(g)
- boiling points of HF, H2O, and NH3 are all
higher than their respective period 3 2KNO2(s) K2O(s) + 2NO2(g) + 1/2O2(g)
homologues.
LiNO3 decomposes in one step.
10.18 Suggest a method for the preparation of
BiH3?
LiNO3(s) 1/2 Li2O(s) + NO2(g) + 1/4O2(g)
The redistribution of methylbismuthine,
BiH2Me. S11.6 Predicted 7Li NMR of Li3N? Two peaks in
the NMR spectrum at low temperature. Only
3BiH2Me 2BiH3 + BiMe3
one resonance in the NMR at high
10.19 Describe the compound formed between temperature.
water and Kr? A clathrate hydrate.
Exercises
10.20 Potential energy surfaces for hydrogen
bonds? (See Figure 10.9) The surface for 11.1 (a) Why are group 1 metals good reducing
the H2O, Cl system has a double minimum, agents? They have one valence electron in
while the surface for the bifluoride ion has a the ns1 subshell, and relatively low first
single minimum. ionization energies.
Shriver & Atkins: Inorganic Chemistry 5e
11.6 Trends in solubility? Higher for LiF and Be has large polarizing power and a high
CsI, lower for CsF and LiI. charge density due.
11.7 Thermal stability of hydrides versus 12.2 Why are the properties of beryllium more
carbonates? Hydrides decompose to similar to aluminium and zinc than to
elements. Carbonates decompose to oxides. magnesium?
Because of a diagonal relationship between
11.8 The structures of CsCl and NaCl? Be and Al.
6-coordinate Na+, 8-coordinate Cs+.
12.3 Identify the compounds A, B, C, and D of
11.9 The effect of the alkyl group on the the group 2 element M?
structure of lithium alkyls? Whether a
molecule is monomeric or polymeric is based on M + H2O M(OH)2; A = M(OH)2
the streric size of the alkyl group less bulky M(OH)2 + CO2 MCO3; B = MCO3
alkyl groups lead to polymerization. 2MCO3 + 5C 2MC2 + 3CO2; C = MC2
MC2 + 2H2O M(OH)2 + C2H2
11.10 Predict the products of the following M(OH)2 + 2HCl MCl2 + 2H2O; D = MCl2.
reactions?
(a) CH3Br + Li Li(CH3) + LiBr 12.4 Why does beryllium fluoride form a glass
when cooled from a melt?
(b) MgCl2 + LiC2H5 Mg(C2H5)Br + LiBr BeF2 adopts SiO2 like arrangement.
(c) C2H5Li + C6H6 LiC6H5 + C2H6 12.5 Why is magnesium hydroxide a much more
effective antacid than calcium or barium
hydroxide? Mg(OH)2 is sparingly soluble
and mildly basic.
Shriver & Atkins: Inorganic Chemistry 5e
11
12.6 Explain why Group 1 hydroxides are much S13.1 B nuclei have I = 3/2. Predict the number
more corrosive to metals than Group 2 of lines and their relative intensities in the
1
hydroxides? H-NMR spectrum of BH4? 4. Relative
intensity ratio is 1:3:3:1.
Group 1 hydroxides are more soluble than
group 2 hydroxides, and therefore have higher S13.2 Write an equation for the reaction of
OH concentrations. LiBH4 with propene in ether solvent and a
1:1 stoichiometry and another equation for
12.7 Which of the salts MgSeO or BaSeO would
4 4 its reaction with ammonium chloride in
be expected to be more soluble in water? THF with the same stoichiometry?
MgSeO4 Simple alkenes are inert towards LiBH4.
THF
12.8 Which Group 2 salts are used as drying LiBH4 + NH4Cl BH3NH3 + LiCl + H2
agents and why?
S13.3 Write and justify balanced equations for
Anhydrous Mg, and Ca sulphates are
plausible reactions between (a) BCl3 and
preferred as drying agents, because of the
ethanol, (b) BCl3 and pyridine in
higher affinity of Mg and Ca sulphates for
hydrocarbon solution, (c) BBr3 and
water.
F3BN(CH3)3?
12.9 How do group 2 salts give rise to scaling (a) BCl3 and ethanol?
from hard water?
BCl3(g) + 3 EtOH(l) B(OEt)3(l) + 3 HCl(g)
Salts of divalent ions have low solubility.
(b) BCl3 and pyridine in hydrocarbon
solution?
12.10 Predict structures for BeTe and BaTe.
BeTe, close to ZnS-like structure. BaTe, close BCl3(g) + py(l) Cl3B py(s)
to CsCl-like structure. (c) BBr3 and F3BN(CH3)3?
BBr3(l) + F3BN(CH3)3(s) BF3(g) +
12.11 Use the data in Table 1.7 and the Ketelaar
Br3BN(CH3)3(s)
triangle in Fig. 2.38 to predict the nature of
the bonding in BeBr , MgBr , and BaBr .
S13.4 Suggest a reaction or series of reactions for
2 2 2
C2H5MgBr will be tetrahedral with two category does it belong? Sketch its
molecules of solvent coordinated to the structure?
magnesium. The bulky organic group in
7, arachno species.
2,4,6-(CH3)3C6 H2MgBr leads to a
The structure of B4H10:
coordination number of two.
[B10H11 (AlCH3)]
Self-tests
Shriver & Atkins: Inorganic Chemistry 5e
1,2 - B10C2H12
1,7-B10C2H12 (90%) + 1,12- No, it explodes in air.
B10C2H12 (10%) B2H6 + 3 O2 B2O3 + 3 H2O2
H 2-
B
H
H H
B
B B
H H
B B
H
C B
13.13 Which boron hydride would you expect to H
be more thermally stable, B6H10 or B6H12? C B
H H B H
Give a generalization by which the thermal
Fe
stability of a borane can be judged? H B H H
B C
B6H10 H
B C H
13.14 How many skeletal electrons are present in B B H
H
B5H9? 14 B B
H B H
13.15 (a) Give a balanced chemical equation H
(including the state of each reactant and B
product) for the air oxidation of H
pentaborane(9). (b) Describe the probable
disadvantages, other than cost, for the use 13.18 (a) What are the similarities and
of pentaborane as a fuel for an internal differences in structure of layered BN and
combustion engine? graphite (Section 13.9)? (b) Contrast their
Heat reactivity with Na and Br2. (c) Suggest a
(a) 2B5H9 (l) + 12O2 (g) rationalization for the differences in
5B2O3 (s) + 9H2O (l) structure and reactivity.
(a) Their structures? Both of these
(b) The boron containing product of substances have layered structures.
combustion is a solid, B2O3. (b) Their reactivity with Na and
13.16 (a) From its formula, classify B10H14 as Br2? Graphite reacts, boron nitride is
closo, nido, or arachno. (b) Use Wades
unreactive.
rules to determine the number of
framework electron pairs for (c) Explain the differences? The large
decaborane(14). (c) Verify by detailed HOMOLUMO gap in BN means it is more
accounting of valence electrons that the difficult to remove an electron from it than
number of cluster valence electrons of from the HOMO of graphite.
B10H14 is the same as that determined in
(b)? 13.19 Devise a synthesis for the borazines (a)
(a) nido . Ph3N3B3Cl3 and (b) Me3N3B3H3, starting
(b) 12. with BCl3 and other reagents of your
(c) The total number of valence elections is choice. Draw the structures of the
(10x3)+(14x1)=44; the number of cluster products?
valence is the remainder of 44-20=24. (a) Ph3N3B3Cl3?
13.17 Starting with B10H14 and other reagents of 3 PhNH3+Cl + 3 BCl3 Ph3N3B3Cl3 + 9 HCl
your choice, give the equations for the (b) Me3N3B3H3?
synthesis of [Fe(nido-B9C2H11)2]2-, and
sketch the structure of this species? 3 MeNH3+Cl + 3 BCl3 Me3N3B3Cl3 + 9 HCl
(1) B10H14 + 2SEt2 Me3N3B3Cl3 + 3 LiH Me3N3B3H3 + 3 LiCl
B10H12(SEt2)2 + H2
The structures:
Shriver & Atkins: Inorganic Chemistry 5e
Exercises
14.1 Silicon forms the chlorofluorides SiCl3F,
SiCl2F2, and SiClF3. Sketch the structures
of these molecules?
14.7 Use the data in Table 14.2 and the 14.13 Preferably without consulting reference
additional bond enthalpy data given here material, draw a periodic table and
to calculate the enthalpy of hydrolysis of indicate the elements that form saline,
CCl4 and CBr4. Bond enthalpies/(kJ mol1): metallic, and metalloid carbides?
OH = 463, HCl = 431, HBr = 366? Ionic(silane) Metallic Metalloid
hHCCl4 = 110 kJmol1 carbides carbides carbides
hHCBr4 = 86 kJmol1 Group I Li, Na, K,
elements Rb, Cs
14.8 Identify the compounds A to F:? Group II Be, Mg, Ca,
(A) SiCl4 (B) SiRCl3 (C) RSi(OH)3. (D) elements Sr, Ba
RSiOSiR +H2O (E) SiR4 (F)? SiO2 Group 13 Al B
elements
YYYYY14.9 (a) Summarize the trends in Group 14 Si
relative stabilities of the oxidation states of elements
the elements of Group 14, and indicate the 3d-Block Sc, Ti, V,
elements that display the inert pair effect. elements Cr, Mn, Fe,
(b) With this information in mind, write Co, Ni
balanced chemical reactions or NR (for no 4d-Block Zr, Nb, Mo,
reaction) for the following combinations, elements Tc, Ru
and explain how the answer fits the trends.
5d-Block La, Hf, Ta,
(i) Sn2+(aq) + PbO2(s) (excess) (air elements W, Re, Os
excluded) (ii) Sn2+(aq) + O2(air) ? 6d-Block Ac
(a) +4 is the most stable oxidation state for elements
the lighter elements, but +2 is the most stable Lanthanides Ce, Pr, Nd,
oxidation state of Pb. Pb therefore displays Pm, Sm,
the inert-pair effect. Eu, Gd, Tb,
(b) (i) Sn2+ + PbO2 + 4 H+ Sn4+ + Pb2+ + Dy, Ho, Er,
2H2O, (ii) 2Sn2+ + O2 + 4H+ 2Sn4+ + Tm, Yb, Lu
2H2O.
14.14 Describe the preparation, structure and
14.10 Use data from Resource section 3 to classification of (a) KC8, (b) CaC2, (c) K3C60?
determine the standard potential for each (a) KC8? Formed by heating graphite with
of the reactions in Exercise 14.5 (b). In potassium vapor or by treating graphite with a
each case, comment on the agreement or solution of potassium in liquid ammonia.
disagreement with the qualitative There is a layered structure of alternating sp2
assessment you gave for the reactions? carbon atoms and potassium ions, a saline
(i) V = +1.31 V. (ii) V= 1.08 V. Both carbide.
reactions agree with the predictions made in
Excercise 14.5. (b) CaC2? Ca(l) + 2C(s) CaC2(s) or
CaO(s) + 3C(s) CaC2(s) + CO(g)
Shriver & Atkins: Inorganic Chemistry 5e
CHAPTER 15
15.2 (a) Give complete and balanced chemical
equations for each step in the synthesis of
Self-tests H PO from hydroxyapatite to yield (a)
3 4
LiAlH4
The rate law must be more than first order in how they could be distinguished by 19F
NO concentration. NMR?
15.14 Give balanced chemical equations for the The cis isomer gives two 19F signals and the
reactions of the following reagents with trans isomer gives one signal.
PCl and indicate the structures of the
5
15.19 Use the Latimer diagrams in Resource 16.3 Which hydrogen bond would be stronger:
section 3 to determine which species of N SH . . . O or OH . . . S?
and P disproportionate in acid conditions?
OH hydrogen bonds are stronger.
The species of N and P that disproportionate
16.4 Which of the solvents ethylenediamine
are N2O4, NO, N2O, NH3OH+, H4P2O6, and P.
(which is basic and reducing) or SO (which
2
CHAPTER 16
ethylenediamine is a better solvent than sulfur
dioxide.
Self-tests
16.5 Rank the following species from the
S16.1 Determine whether the decomposition of strongest reducing agent to the strongest
H O is spontaneous in the presence of
2 2
oxidizing agent: SO42,SO32,O3SO2SO32?
either Br or Cl ? 2 2
S2O82 > SO42 > SO32
The decomposition of H2O2 is 16.6 Predict which oxidation states of Mn will
thermodynamically favored in presence of Br be reduced by sulfite ions in basic
In Presence of Cl conditions?
Given the Latimer diagram The SeO32 is marginally more stable in acid
solutions.
-0.13 1.51
O2 HO2- H2O2 16.10 Predict whether any of the following will be
reduced by thiosulfate ions,S2O32, in acidic
in acidic solution, calculate rG for the conditions: VO2+, Fe3+, Cu+, Co3+?
disproportionation of hydrogen superoxide
(HO ) into O and H O , and compare the
2
2 2 2
Fe3+ and Co3+ will be reduced.
result with its value for the
disproportionation of H O ? 2 2
16.11 SF reacts with BF to form [SF ][BF ]. Use
4 3 3 4
(a) The disproportionation of H2O2 and VSEPR theory to predict the shapes of the
HO2? 1.068 V. cation and anion?
(b) Catalysis by Cr2+? Cr2+ is not capable SF4+ trigonal pyramidal, BF4 tetrahedral.
of decomposing H2O2.
(c) The disproportionation of HO2? rG = 16.12 Tetramethylammonium fluoride (0.70 g)
157 kJ. For the disproportionation of H2O2 reacts with SF (0.81 g) to form an ionic
4
(part (a)), rG = 103 kJ. product. (a) Write a balanced equation for
Shriver & Atkins: Inorganic Chemistry 5e
17.4 Sketch the form of the vacant s* orbital of shapes of IF and the cation and anion in X,
3
a dihalogen molecule and describe its role (c) predict how many 19F-NMR signals
in the Lewis acidity of the dihalogens? would be observed in IF and X? 3
a). X = IF4N(CH3)4
b) Different possible arrangements of
IF3:
Lewis base. (a) Describe the origins of this 17.9 Use the VSEPR model to predict the shapes
very large difference in volatility. (b) of SbCl , FClO , and [ClF ]+?
5 3 6
17.12 (a) Use the VSEPR model to predict the 17.19 Explain why CsI (s) is stable with respect to
3
symmetry.
17.15 Predict whether each of the following
17.21 (a) Give the formulas and the probable
solutes is likely to make liquid BrF a 3
relative acidities of perbromic acid and
stronger Lewis acid or a stronger Lewis
periodic acid. (b) Which is the more stable?
base: (a) SbF , (b) SF , (c) CsF?
5 6
(d) S Cl ?
2 2
(a) The expected trend? E decreases as the
pH increases.
(a) SbF5? Since SbF5 cannot be oxidized, it
will not form an explosive mixture with BrF3. (b) E at pH 0 and pH 7 for ClO4?
(b) CH3OH? Methanol, being an organic E = 1.201 V (see Appendix 2).
compound, is readily oxidized by strong
At pH 7, V = 0.788 V
oxidants.
17.23 With regard to the general influence of pH
(c) F2? No. on the standard potentials of oxoanions,
(d) S2Cl2? S2Cl2 will be oxidized to higher explain why the disproportionation of an
valent sulfur fluorides. oxoanion is often promoted by low pH?
Low pH results in a kinetic promotion:
protonation of an oxo group aids oxygen
17.18 The formation of Br from a 3
halogen bond scission.
tetraalkylammonium bromide and Br is 2
only slightly exoergic. Write an equation 17.24 Which oxidizing agent reacts more readily
(or NR for no reaction) for the interaction in dilute aqueous solution, perchloric acid
of [NR ][Br ] with I in CH Cl solution and
4 3 2 2 2
or periodic acid? Give a mechanistic
give your reasoning? explanation for the difference?
17.25 (a) For which of the following anions is 18.2 Which of the noble gases would you choose
disproportionation thermodynamically as (a) The lowest-temperature
favourable in acidic solution: OCl , ClO2 , 2 refrigerant? Helium.
ClO2 , and ClO4 ? (If you do not know the
(b) An electric discharge light source
properties of these ions, determine them
from a table of standard potentials.) (b) requiring a safe gas with the lowest
For which of the favourable cases is the ionization energy? Xenon.
reaction very slow at room temperature? (c) The least expensive inert
The rates of disproportionation are probably atmosphere? Argon.
HClO > HClO2 > ClO3. 18.3 By means of balanced chemical equations
17.26 Which of the following compounds present and a statement of conditions, describe a
an explosion hazard? (a) NH ClO , (b) 4 4
suitable synthesis of (a) XeF2? Xe and F2
Mg(ClO ) , (c) NaClO , (d) [Fe(H O) ][ClO ] .
4 2 4 2 6 4 2
at 400C, or photolyze Xe and F2 in glass:
Explain your reasoning? Xe(g) + F2(g) XeF2(s)
(a) NH4ClO4? Ammonium perchlorate is a (b) XeF6? High temperature, but have a large
dangerous compound, since the N atom of the excess of F2:
NH4+ ion is in its lowest oxidation state and
can be oxidized. Xe(g) + 3 F2(g) XeF6(s)
(b) Mg(ClO4)2? Not an explosion hazard. (c) XeO3?
(c) NaClO4? Not an explosion hazard. XeF6(s) + 3 H2O(l) XeO3(s) + 6 HF(g)
(d) [Fe(H2O)6] [ClO4]2? An explosion 18.4 Draw the Lewis structures of (a) XeOF4?
hazard, since Fe(II) can be oxidized to Fe(III). (b) XeO2F2? (c) XeO64?
Exercises
18.1 Explain why helium is present in low
concentration in the atmosphere even
though it is the second most abundant
element in the universe?
(b) Speculate on its possible structures by
Helium present in todays atmosphere is the using the VSEPR model and analogy with
product of ongoing radioactive decay. other xenon fluoride anions? Pentagonal
bipyramid.
Shriver & Atkins: Inorganic Chemistry 5e
18.7 Use molecular orbital theory to calculate the group oxidation number is not achieved
the bond order of the diatomic species E2+ by N?
with E=He and Ne? He22+ = 0.5, Ne22+ = 0.5.
S19.3 Describe the probable structure of the likely to form a sulfide in the presence of
compound formed when Re3Cl9 is dissolved H S? (b) Rationalize your answer with the
2
Metalmetal bonded halide compounds are 19.9 Speculate on the structures of the following
found within bold border. Example: Sc5Cl6. species and present bonding models to
justify your answers:
(a) [Re(O)2 (py)4]+, (b) [V (O)2 (ox)2]3, (c)
[Mo(O)2(CN)4]4, (d) [VOCl4]2? The first
three are dioxo complexes and will have cis-
dioxometal structural units. (d) VOCl42, has a
square-pyramidal structure with an apical oxo
ligand.
19.7 Write a balanced chemical equation for the
reaction that occurs when cis- 19.10 Which of the following are likely to have
[RuLCl(OH2)]+ (see Fig. 19.9) in acidic structures that are typical of (a)
solution at +0.2 V is made strongly basic at predominantly ionic, (b) significantly
the same potential. Write a balanced covalent, (c) metal-metal bonded
equation for each of the successive compounds: NiI , NbCl , FeF , PtS, and
2 4 2
reactions when this same complex at pH = WCl ? Rationalize the differences and
2
6 and +0.2 V is exposed to progressively speculate on the structures? (a) NiI2? ionic
more oxidizing environments up to +1.0 V. compound with significant degree of covalent
Give other examples and a reason for the character
redox state of the metal center affecting the
extent of protonation of coordinated (b) NbCl4? significantly covalent.
oxygen. (c) FeF2? ionic.
II +
cis-[Ru LCl(OH2)] + Ox + OH cis- (d) PtS ? significant amount of covalent
[RuIIILCl(OH)]+ + Red + H2O character.
cis-[RuIILCl(OH2)]+ + H2O cis- (e) WCl2 ? metalmetal bonding.
[RuIIILCl(OH)]+ + H3O+ + e
19.11 Indicate the probable occupancy of s, p,
cis-[RuIIILCl(OH2)]+ + H2O cis- and d bonding and antibonding orbitals,
[RuIVLCl(OH)]+ + H3O+ + e and the bond order for the following
tetragonal prismatic complexes?
As oxidation state of the metal increases,
ability to accept electron density from an OH (a) [Mo2(O2CCH3)4]? 242 configuration,
or O2 ligand increases. molybdenum-molybdenum quadruple bond.
19.8 Give plausible balanced chemical reactions (b) [Cr2(O2CC2H5)4]? 242,chromium
(or NR for no reaction) for the following chromium quadruple bond.
combinations, and state the basis for your
answer: (a) MoO42 (aq) plus Fe2+ (aq) in (c) [Cu2(O2CCH3)4]? 242*2*4*2
acidic solution? No reaction. configuration, no metalmetal bond in this
molecule.
(b) The preparation of [Mo6O19]2(aq) from
K2MoO4(s)? 6 MoO42(aq) + 10 H+(aq) 19.12 Explain the differences in the following
[Mo6O19]2(aq) + 5 H2O(l) redox couples, measured at 25oC?
Higher oxidation states become more stable
(c) ReCl5 (s) plus KMnO4(aq)? on descending a group.
5 ReCl5(s) + 2 MnO4(aq) + 12 H2O(l)
19.13 Addition of sodium ethanoate to aqueous
5 ReO4(aq) + 2 Mn2+(aq) + 25 Cl(aq) + solutions of Cr(II) gives a red diamagnetic
24 H+(aq) product. Draw the structure of the
product, noting any features of interest?
(d) MoCl2(s) plus warm HBr(aq)?
6 MoCl2(s) + 2 Br(aq) [Mo6Cl12]2(aq)
+ Br2(aq)
(e) TiO(s) with HCl(aq) under an inert
atmosphere? 2TiO (s) + 6H+ (aq)
3+
2Ti + H2(g) + 2H2O(l) E = +0.37 V.
(f) Cd(s) added to Hg2+(aq)?
Hg2+ (aq) + Cd(s) Hg(l) + Cd2+ (aq)
Shriver & Atkins: Inorganic Chemistry 5e
20.12 Give the Russell-Saunders terms of the max52 dm3 mol-1 cm-1, and a strong band at
configurations and identify the ground higher energy with max= 2 x 104 dm3 mol1
term? (a) 4 s1? 2S. cm1. What do you suggest for the origins
of these transitions? First, the intense band
(b) 3p2? 1
D, 3P, 1S. The ground term is 3P.
at relatively high energy is undoubtedly a
20.13 The gas-phase ion V3+ has a 3F ground term. spin-allowed charge-transfer transition. The
The 1D and 3P terms lie, respectively, 10 two bands with max = 60 and 80 M1 cm1 are
642 and 12 920 cm1 above it. The energies probably spin-allowed ligand field transitions.
of the terms are given in terms of Racah The very weak peak is most likely a spin-
parameters as E(3F) = A - 8B, E(3P) = A + forbidden ligand field transition.
7B, E(1D) = A - 3B + 2C. Calculate the
20.20 Ordinary bottle glass appears nearly
values of B and C for V3+. B = (12920 cm
1 colorless when viewed through the wall of
)/(15) = 861.33 cm1 and C = 3167.7 cm1.
the bottle but green when viewed from the
20.14 Write the d-orbital configurations and use end so that the light has a long path
the TanabeSugano diagrams (Resource through the glass. The color is associated
section 6) to identify the ground term of (a) with the presence of Fe3+ in the silicate
Low-spin [Rh(NH3)6]3+? 1A1g. matrix. Suggest which transitions are
responsible for the color? The faint green
(b) [Ti(H2O)6]3+? 2T2g. color, which is only observed when looking
(c) High-spin [Fe(H2O)6]3+? 6A1g. through a long pathlength of bottle glass, is
caused by spin-forbidden ligand field
20.15 Using the Tanabe-Sugano diagrams in transitions.
Resource section 6, estimate O and B for
(a) [Ni(H2O)6]2+ (absorptions at 8500, 15400 20.21 Solutions of [Cr(OH2)6]3+ ions are pale blue
and 26000 cm-1) ? 0 = 8500 cm1 and B green but the chromate ion, CrO42, is an
770 cm1. intense yellow. Characterize the origins of
the transitions and explain the relative
(b) [Ni(NH3)6]2+ (absorptions at 10750, intensities. The blue-green color of the Cr3+
17500 and 28200 cm-1)? 0 = 10,750 cm1 ions in [Cr(H2O)6]3+ is caused by spin-
and B 720 cm1. allowed but Laporte-forbidden ligand field
20.16 The spectrum of [Co(NH3)6]3+ has a very transitions. The relatively low molar
weak band in the red and two moderate absorption coefficient is the reason that the
intensity bands in the visible to near-UV. intensity of the color is weak. The oxidation
How should these transitions be assigned? state of chromium in dichromate dianion is
The first two transitions listed above Cr(VI); the intense yellow color is due to
correspond to two low-spin bands. The very LMCT transitions.
weak band in the red corresponds to a spin- 20.22 Classify the symmetry type of the d orbital
forbidden transition. in a tetragonal C4v symmetry complex, such
20.17 Explain why [FeF6]3- is colorless whereas as [CoCl(NH3)5] , where the Cl lies on the
[CoF6]3 is colored but exhibits only a z-axis. (a) Which orbitals will be displaced
single band in the visible. No spin-allowed from their position in the octahedral
transitions are possible for the Fe3+; the molecular orbital diagram by
complex is expected to be colorless. The d6 interactions with the lone pairs of the Cl
Co3+ ion in [CoF6]3 is also high spin, but in ligand? (b) Which orbital will move
this case a single spin-allowed transition because the Cl ligand is not as strong a
makes the complex colored and gives it a one- base as NH3? (c) Sketch the qualitative
band spectrum. molecular orbital diagram for the C4v
complex. The Cl atom lone pairs of electrons
20.18 The Racah parameter B is 460 cm1 in can form molecular orbitals with dxz and dyz.
[Co(CN)6]3- and 615 cm-1 in [Co(NH3)6]3+. These metal atomic orbitals are -antibonding
Consider the nature of bonding with the MOs, and so they will be raised in energy.
two ligands and explain the difference in
nephelauxetic effect? Ammonia and cyanide
ion are both -bases, but cyanide is also a -
acid.
20.19 An approximately octahedral complex of
Co(III) with ammine and chloro ligands
gives two bands with max between 60 and
80 dm3 mol1 cm1, one weak peak with
Shriver & Atkins: Inorganic Chemistry 5e
with a single d-block metal atom such as spectrum? Check your answer and give the
cobalt? (a) C2H4? 2 number of expected bands for each by
(b) Cyclopentadienyl? Can be 5, 3, or 1. consulting Table 22.7.
Cs symmetry complex, 3
(c) C6H6? 6, 4, and 2.
22.8 Provide plausible reasons for the
(d) Cyclooctadiene? 2 and 4 . differences in IR wavenumbers between each of the
following pairs:
(e) Cyclooctatetraene?8, 6, 4, 2. (a) Mo(PF3)3(CO)3 2040, 1991 cm1 versus
Mo(PMe3)3(CO)3 1945, 1851 cm1? CO
22.4 Draw plausible structures and give the bands of the trimethylphosphine complex are
electron count of (a) Ni(3-C3H5)2 (b) 100 cm1 or more lower in frequency. PMe3 is
Co(4-C4H4)(5-C5H5) (c) Co(3- primarily a -donor ligand. PF3 is primarily
C3H5)(CO)3. If the electron count deviates
a -acid ligand.
from 18, is the deviation explicable in
terms of periodic terms. (b) MnCp(CO)3 2023, 1939 cm1 vs.
MnCp*(CO)3 2017, 1928 cm1? CO bands
(a) Ni(3-C3H5)2 16, very common for group of the Cp* complex are lower in frequency
9 and group 10 elements. than the corresponding bands of the Cp
complex. Cp* is a stronger donor ligand than
(b) Co(4-C4H4)(5-C5H5)? 18. Cp.
(c) Co(3-C3H5)(CO)3? 18. 22.9 The compound Ni3(C5H5)3(CO)2 has a
single CO stretching absorption at 1761
cm1. The IR data indicate that all C5H5
ligands are pentahapto and probably in
identical environments. (a) On the basis of
these data, propose a structure.
RuCp2 has 18 electrons. (b) Can these CVE values be derived from
22.21 Give the equation for a workable reaction the 18-electron rule? No.
for the conversion of Fe(5-C5H5)2 to Fe(5-
(c) Determine the probable geometry of
C5H5) (5-C5H4COCH3) and (b) Fe(5-
[Fe6(C)(CO)16]2 and [Co6(C)(CO)15]2-
C5H5) (5-C5H4CO2H)
? The iron complex probably contains an
(a) Fe(5 C5H5)2 + CH3COCl octahedral Fe6 array. The cobalt complex
Fe( C5H5)(5 C5H4COCH3) + HCl
5
probably contains a trigonal-prismatic Co6
array.
state and correlate this deviation with 23.10 Predict a structure type for BkN based on
electronic structure. ? (a) Balanced the ionic radii r(Bk3+) = 96 pm and r(N3) =
equation 2 Ln(s) + 6 H3O+(aq) 146 pm.
The rock-salt structure.
2 Ln3+(aq) + 3 H2(g) + 6 H2O(l)
23.11 Describe the general nature of the
(b) Redox potentials The potentials for the
distribution of the elements formed in the
Ln0/Ln3+ oxidations in acid solution range thermal neutron fission of 235U, and
from a low of 1.99 V for europium to 2.38 V. decide which of the following highly
(c) Two unusual lanthanides Ce4+, Eu2+. radioactive nuclides are likely to present
the greatest radiation hazard in the spent
23.2 Explain the variation in the ionic radii fuel from nuclear power reactors: (a) 39Ar,
between La3+ and Lu3+. (b) 228Th, (c) 90Sr, (d) 144Ce. 90Sr and 144Ce.
The lanthanide contraction.
23.3 From a knowledge of their chemical CHAPTER 24
properties, speculate on why Ce and Eu
were the easiest lanthanoids to isolate Self-tests
before the development of ion-exchange
chromatography. Ce4+ and Eu2+, unusual S24.1 Synthesis for Sr2MoO4? Sealed tube, high
oxidation states were used in separation temperature, 6 SrO(s) + Mo(s) + 2 MoO3(s)
procedures. 3 Sr2MoO4.
23.4 How would you expect the first and second S24.2 Why does increased pressure reduce the
ionization energies of the lanthanoids to conductivity of K+ more than that of Na+ in
vary across the series? Sketch the graph
-alumina? Because K+ is larger than Na+.
that you would get if you plotted the third
ionization energy of the lanthanoids versus
atomic number? Identify elements at any
S24.3 Rationalize the observation that FeCr2O4 is
peaks or troughs and suggest a reason for
a normal spinel? The A2+ ions (Fe2+ in this
their occurrence? First and second IEs
example) occupy tetrahedral sites and the B3+
would show general increase across the
ions (Cr3+) occupy octahedral sites.
lanthanoids. With the third, anomalies arise.
7
23.5 Derive the ground state of the Tb3+ ion. F6
Exercises
23.6 Predict the magnetic moment of a 24.1 NiO doped with Li2O? The electronic
compound containing the Tb3+ ion. conductivity of the solid increases owing to
= 9.72 B formation of Ni1xLix)O.
24.2 What is a crystallographic shear plane?
23.7 Explain why stable and readily isolable Both.
carbonyl complexes are unknown for the 24.3 How might you distinguish between a solid
lanthanoids? Carbonyl compounds need solution and a series of discrete
back-bonding from metal orbitals of the crystallographic shear plane structures? A
appropriate symmetry. solid solution would contain a random
collection of crystallographic shear planes.
23.8 Suggest a synthesis of neptunocene from
NpCl4? 24.4 Wurtzite crystal structure and bottleneck?
Np(COT)2 was prepared by the reaction of The wurtzite structure is shown in Figure
K2COT with NpCl4 under inert 3.35. The normal sites for cations in this
atmosphere. structure are the tetrahedral holes. The
bottleneck involves the space formed by three
23.9 Account for the similar electronic spectra close packed anions.
of Eu3+ complexes with various ligands and
the variation of the electronic spectra of 24.5 Synthesis of? (a) MgCr2O4 - heat
Am3+ complexes as the ligand is varied. (NH4)2Mg(CrO4)2 gradually to 1100-1200C;
The 5f orbitals of the actinide ions interact (b) SrFeO3Cl - heat SrO + SrCl2 + Fe2O3 in a
strongly with ligand orbitals, and the splitting sealed tube; (c) Ta3N5 - heat Ta2O5 under
of the 5f subshell, as well as the color of the NH3 at 700C.
complex, varies as a function of ligand.
24.6 Products of reactions? (a) LiNiO2, (b)
Sr2WMnO6.
Shriver & Atkins: Inorganic Chemistry 5e
allow for the precise spatial control over 25.11 (a) Homogeneous versus heterogeneous?
atoms and molecules. Homogeneous nucleation leads to solid
formation throughout the vapour phase. (b)
25.6 (a) What are SPMs? A method to image the thin film? Heterogeneous nucleation is
microscale features by scanning a very small preferred in thin-film growth. (c)
probe over the surface and measuring some nanoparticles? Homogeneous nucleation is
physical interaction between the tip and the generally preferred for nanoparticle synthesis.
material. (b) SPM and a specific
nanomaterial? Local magnetic domains of 25.12 PVD versus CVD? In CVD, the atomic
magnetic nanomaterials, such as nanorods of species of interest are bound chemically to
iron oxide, can be imaged using magnetic other species. Also, their thermal energies are
force microscopy. typically rather low. In PVD, the atomic
species of interest are typically atomic.
25.7 SEM versus TEM? SEM, an electron beam
is scanned over a material, and an image is 25.13 (a) Purpose of QD layers? Multiple layers of
generated by recording the intensity of quantum dots can increase the intensity of any
secondary or back-scattered electrons. TEM, optical absorption or emission. They can also
an electron beam is transmitted through the be used to form quantum cascade lasers. (b)
materials, and the image is the spatial Limitations? The limitations come from the
variation in the number of transmitted requirements on how coherent the interface
electrons. between the two materials must be.
SEM sample preparation, ensure the material
is conductive. In TEM, the sample needs to be 25.14 (a) Applications of quatum wells? Lasers
made transparent to the electron beam.. and optical sensors. (b) Why are they used
over other materials? They exhibit
25.8 (a) Steps in solutions synthesis of properties that are not observed in molecular
nanoparticles? (i) solvation; (ii) stable nuclei or traditional solid state materials. (c) How
of nanometer dimensions formed; (iii) growth are they made? Molecular beam epitaxy.
of particles to desired size occurs.
(b) Why should the last two steps occur 25.15 Superlattices and improved properties?
independently? So that nucleation fixes the AlN and TiN - different elastic constants,
total number of particles and growth leads to large number of interfaces spaced on the
controlled size and narrow size distribution. nanoscale.
(c) Stabilizers? Prevent surface oxidation and Results are much improved hardness values.
aggregation, and they limit traps for the holes
and electrons, and improve quantum yields 25.16 (a) Self-assembly? (a) Offers methods to
and luminescence. bridge bottom-up and top-down approaches to
synthesis. (b) In nanotechnology? Offers a
25.9 Vapor-phase versus solution-based route to assemble nanosized particles into
techniques? (a) Vapor-phase, large sizes. (b) macroscopic structures.
Vapor-phase, more agglomeration.
25.17 Common features of self-assembly?
25.10 (a) What is a core-shell nanoparticle? (i) molecular or nanoscale subunits; (ii)
spontaneous assembly of the subunits; (iii)
Shell noncovalent interactions between the
assembled subunits; (iv) longer-range
Core structures arising from the assembly process.
25.19 Compare SAMs and cell membranes? SAM S26.4 Demonstate that the polymerization of
can structurally resemble a phospholipid propene with a simple Cp2ZrCl2 catalyst
bilayer. would give rise to atactic polypropene?
25.20 What is morphosynthesis? Control of
Without R groups attached to the Zr center
nanoarchitectures in inorganic materials
there is no preference for specific binding
through changes in synthesis parameters.
during polymerization.
25.21 (a) What are the two classes of inorganic-
organic nanocomposites? Class I, hybrid Exercises
materials where no covalent or ionic bonds
are present. Class II, at least some of the 26.1 Which of the following constitute catalysis?
components are linked through chemical (a) H2 and C2H4 in contact with Pt? An
bonds. (b) Examples? Class I, block example of genuine catalysis.
copolymers. Class II, polymer/clay (b) H2 plus O2 plus an electrical arc? Not
nanocomposites. catalysis..
25.22 (a) Why is dispersion important in (c) The production of Li3N and its reaction
nanocomposites? They lead to increased with H2O? Not catalysis.
exposed surface areas. (b) Why is dispersion 26.2 Define the following terms? (a) Turnover
difficult? The often nonpolar organic frequency? The amount of product formed
polymers do not have strong interactions with per unit time per unit amount of catalyst.
the polar or ionic inorganic components.
(b) Selectivity? How much of the desired
25.23 A bionanomaterial and its application? product is formed relative to by-products.
PPF/PPF-DA is an injectable bionanomaterial (c) Catalyst? A substance that increases the
used for bone-tissue engineering. rate of a reaction but is not itself consumed.
25.24. (a) Biomimetics? Designing nanomaterials (d) Catalytic cycle? Sequence of chemical
that mimic biological systems. (b) example of reactions involving the catalyst that transform
biomimetics? Cellulose fibers in paper have the reactants into products.
been used to template the growth of titanium (e) Catalyst support? Generally a ceramic
oxide nanotubes. like -alumina or silica gel.
turnover frequency? The catalytic species exchange of the methyl group in the
that enters the cycle is RhCl(PPh3)2(Sol) (Sol chemisorbed CHR(CH3) group (R =
= a solvent molecule). C(CH3)2(C2H5)).
26.6 Explain the trend in rates of H2 absorption 26.14 Why does CO decrease the effectiveness of
by various olefins catalyzed by Pt in catalyzing the reaction 2H+(aq) + 2e
RhCl(PPh3)3? In both cases, the alkene that H2(g)? Platinum has a strong tendency to
is hydrogenated more slowly has a greater chemisorb CO.
degree of substitution and so is sterically
26.15 Describe the role of an electrocatalyst?
more demanding.
Platinum is the most efficient electrocatalyst
26.7 Hydroformylation catalysis with and for accelerating oxygen reduction at the fuel
without added P(n-Bu)3? The cell cathode, but is expensive.
transformation of (E) into CoH(CO)4 must be
the rate-determining step in the absence of
added P(n-Bu)3. In the presence of added
P(n-Bu)3, the formation of either (A) or (E) is CHAPTER 27
the rate-determining step.
Self-tests
26.8 How does starting with MeCOOMe instead
of MeOH lead to ethanoic anhydride S27.1 Is Iron (II) expected to be present in the
instead of ethanoic acid using the cell as uncomplexed ions? No.
Monsanto acetic acid process? The reaction S27.2 Unusual coordination of Mg? The proteins
of the ethanoate ion with the acetyl iodide 3D structure can place any particular atom in
leads to ethanoic anhydride. a suitable position for axial coordination.
S27.3 Why does saline contain NaCl? Osmotic
26.9 Suggest a reason why? (a) Ring opening balance.
alkene metathesis polymerization (ROMP)
proceeds? ROMP can result in reduced S27.4 Explain the significance of the Calcium ion
steric strain. (b) Ring-closing metathesis pumps activation by calmodulin? The
(RCM) reaction proceeds? RCM results in binding of calmodulin is a signal informing
the loss of ethane. the pump that the cytoplasmic Ca2+ level has
risen above a certain level.
26.10 (a) Attack by dissolved hydroxide?
Structure C in Figure 26.11 (b) Attack by S27.5 Why are iron-porphyrin complexes unable
coordinated hydroxide? Structure E given in to bind O2 reversibly? The Fe(II) gets
Figure 26.11 (c) Can one differentiate the oxidized to Fe(III), yielding an oxo-Iron(III)
stereochemistry? Yes. porphyrin complex.
26.11 (a) Enhanced acidity? When Al3+ replaces
Si4+ on lattice site charge is balanced by S27.6 What is the nature of binding at Cu blue
H3O+. centers as indicated by the EPR spectrum?
There is greater covalence in blue Cu centers
(b) Three other ions? Ga3+, Co3+, and Fe3+. than in simple Cu(II) compounds.
26.12 Why is the platinum-rhodium in S27.7 What is the nature of an active site with
automobile catalytic converters dispersed Copper (III)? Diamagnetic with square-
on the surface of a ceramic rather than planar geometry.
used in the form of thin foil? A thin foil of S27.8 Why mercury is so toxic because of the
action of enzymes containing cobalamin?
platinum-rhodium will not have as much
Cobalamins are very active methyl transfer
surface area as an equal amount of small
reactions, which can methylate anything in
particles finely dispersed on the surface of a
the cell.
ceramic support.
26.13 Devise a plausible mechanism to explain S27.9 Suggest experiments that could establish
the deuteration of 3,3-dimethylpentane? the structure of the MoFe cofactor? EPR,
(i) The mechanism of deuterium exchange is single-crystal X-ray diffraction, and EXAFS.
probably related to the reverse of the last two S27.10 Why might Cu sensors be designed to bind
reactions in Figure 26.20. Cu(I) rather than Cu(II)? Cu(I) has an
almost unique ability to undergo linear
(ii) The second observation can be explained coordination by sulphur-containing ligands.
by invoking a mechanism for rapid deuterium
Shriver & Atkins: Inorganic Chemistry 5e
Exercises