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Student Solutions Manual Rodgers 2nd Ed. Descriptive Inorganic, Coordination, and Solid State Chemistry
Student Solutions Manual Rodgers 2nd Ed. Descriptive Inorganic, Coordination, and Solid State Chemistry
Student Solutions Manual Rodgers 2nd Ed. Descriptive Inorganic, Coordination, and Solid State Chemistry
Glen E. Rodgers
Student Manual
Chapter 1 Objectives
1
Chapter 2
An Introduction to Coordination Chemistry
Chapter 2 Objectives
2
Solutions to Odd-Numbered Problems
2.1. Dalton's atomic theory had three essential components. First, he proposed that all elements were
composed of tiny, indivisible particles called atoms. All the atoms of a given element were the same in
every way while those of different elements were different in properties such as mass and size. Second,
compounds were composed of atoms of more than one element in small, whole number ratios, 1:1, 2:1,
etc. Third, a chemical reaction involved the shuffling of atoms from one compound to another. The idea of
hooks embedded into atoms could have been a way to account for the number of other atoms with which a
given atom could combine. That is, an atom of oxygen, which often combines with two other atoms of a
second element in such compounds as water, H2O, might have two embedded hooks while hydrogen
atoms might have only one.
2.3. In carbon monoxide, the valence of carbon is one while in carbon dioxide it is two. Therefore, these
two compounds are not consistent with the concept of fixed valence. In practice, it is found that a given
element may have several characteristic valences.
2.5. The quantum mechanical atom pictures an electron in an atom to occupy only certain, allowed
energy levels. When this atom is excited, that is, when energy is put into it, the electron can be moved
from one allowed level to a higher one. Once the atom moves away from the energy source, the electron
will return to its lower "ground state" energy level. The energy lost, E, according to Planck's equation, E =
hv, would correspond to a specific frequency or wavelength of light emitted. As various electrons are
excited and then return to their lower levels, a set of energies (and therefore a set of wavelengths),
characteristic of the particular atom, would be emitted. This characteristic set of wavelengths is known as
an emission spectrum.
2.7. The disappointment came when the Blomstrand-Jørgensen chain theory could not predict the
conductivity or the number of ions that would exist in aqueous solution or rationalize the correct number
of isomers of certain compounds. Specifically, IrCl3(NH3)3 was predicted by the chain theory to have two
precipitatable chlorides and a nonzero conductivity. In fact this compound did not form ions in solution
and therefore its aqueous solution was a nonconductor and had no precipitatable chlorides. Furthermore, it
was not clear why this compound could not have a number of different isomers rather than only the two
that could be prepared.
(b) The conductivity should decrease due to fewer and lower charged ions in solutions. For example,
compound (1) would produce a +3 cation and three -1 anions while compound (3) would produce a +1
cation and one -1 anion.
H2O
(c) i) Blomstrand-Jørgensen ii) Werner
Cl
H2O-Cl H2O OH2
/
Co-H2O-H2O-H2O-H2O-Cl
\ Cl Cr Cl
Cl
H2O OH2
H2O
3
iii) Modern [Cr(H2O)5Cl]Cl2
2.11. One would suspect that Jørgensen's idea of putting the more reactive chlorides at the end of a chain
carried over to Werner's idea of putting them outside the coordination sphere.
Cl Cl Cl
Cl NH3 NH3
NH3 NH3 NH3
H3N Cl
NH3 H3N
NH3 Cl
NH3 NH3 NH3
2.15. tricarbonyltrichlorochromium(III)
Cl Cl Cl
OC Cl OC CO OC CO
Pt Pt Pt
OC Cl OC Cl Cl Cl
CO Cl CO
2.17. (a) The chloride ligands satisfy both primary and secondary valences while the waters satisfy only
secondary.
Cl
H2O OH2
Cr
Cl Cl
H2O
4
Cl Cl Cl
Cl Cl Cl
Cl OH2 OH2
H2O Cl H2O
OH2 OH2 OH2
OH2 OH2 Cl
Cl Cl
H2O H2O
OH2 OH2
Cr Cr
Cl H2O
Cl Cl
OH2 Cl
2.19. Only ammonia and nitrite are possible ligands as they are the only ones to have lone pairs that can
be donated to a metal ion.
[Co(NH3)6](NO2)3 3 1
[Co(NH3)5(NO2)](NO2)2 2 1
[Co(NH3)4(NO2)2]NO2 1 2
[Co(NH3)3(NO2)3] 0 2
K[Co(NH3)2(NO2)4] 0 2
K2[Co(NH3)(NO2)5] 0 1
K3[Co(NO2)6] 0 1
5
(NH4)2[Pt(SCN)4] (b), (ii) ammonium tetrathiocyanatoplatinate(II)
(contains anion of highest charge)
(c) SCN
neutral compound:
two isomers, cis and trans
H3N Pt NH3
SCN
2.23 (a)
Cl + H2N CH2 +
CH2
NH2 NH2 NH2
H2C H2C NH2
Co CH2 Co
H2C CH2 H2C
NH2 Cl
NH2 NH2
Cl Cl
NH2 NH2
NH2
NH2
H2C H2C
Cl CH2 H2N CH2
H2C H2C CH2
CH2
NH2 NH2 NH2
Cl
Cl Cl
Cl Cl
NH2 NH2
H2N CH2 CH2
CH2 H2N
CH2
Cl H2N
NH2 Cl
H2C
H2N CH2 NH2
CH2
CH2
6
(c) There are two possible isomers.
H2C
NH2 Cl
H2C
H2N Cl H2N NH2
H2C CH2
Co Co
H2C H N CH2
H2N Cl 2 NH2
H2C NH2 Cl
H2C
(a) (b)
H
O O O
2.35. O O
7
Chapter 3
Structures of Coordination Compounds
3.1 Stereoisomers
3.2 Octahedral Coordination Spheres
Compounds with Monodentate Ligands
Compounds with Chelating Ligands
3.3 Square Planar Coordination Spheres
3.4 Tetrahedral Coordination Spheres
3.5 Other Coordination Spheres
3.6 Structural Isomers
Chapter 3 Objectives
8
Solutions to Odd-Numbered Problems
3.1. Ethanol and dimethylether are isomers because they have the same number and types of atoms but
different properties. Furthermore, they are structural isomers because they have different numbers and types
of chemical bonds. For example, ethanol has one C-O bond while dimethylether has two.
3.3. The two chain theory formulations would be considered to be stereoisomers because they have the
same numbers and types of chemical bonds (three each of Co-N, NH3-NH3, and NH3-Cl) but differ in the
spatial arrangements of those bonds.
3.5. A light beam of a given wavelength can be polarized such that only one plane of the electric or
magnetic field is allowed. A molecule is optically active if it is capable of rotating that plane to the right or
to the left when the light beam is passed through the substance.
*3.7. For each case (MA4B2 and MA3B3), these are geometric isomers because they have the same numbers
B B
and types of chemical bonds but the different spatial arrangements of these bonds result in different
geometries. In the MA4B2 set the 1,6 case does not contain an internal mirror plane and is chiral. The 1,5
B
isomer is actually the nonsuperimposable mirror image of the 1,6 isomer. Similarly, in the MA3B3 the 1,2,4
B
3.9. These two mirror images are nonsuperimposable. No matter how one is rotated in space, it cannot be
made equivalent to the other. Therefore, this molecule is chiral. The same conclusion is arrived at by
considering the fact that this molecule does not contain any internal mirror planes.
Cl Cl
C C
I I
Br Br
F F
3.11. (a) If the mirror image of a molecule cannot be rotated in space so as to be equivalent to the original
molecule, it is said to have a nonsuperimposable mirror image. Such a molecule is chiral. (b) If a molecule
does not possess an internal mirror plane (a plane that passes through the molecule such that every atom in
the molecule can be reflected through the plane into another equivalent atom) it is chiral. [There are a few
exceptions to this rule but they are beyond the scope of this text.]
3.13. Only AlClBrI has an internal mirror plane, the one that the entire molecule sits in. Therefore, this
molecule is not chiral whereas the corresponding phosphorus compound is.
3.15. The structural formulas are as follows: (For (b) and (c), the structure of only the cations are shown.)
9
(a) (b) (c)
Cl + NH3 +
NO2 NH3
3.17. Neither of these compounds is chiral because each contains at least one internal mirror plane.
(a)
Cl
O O O
C
O
K3 C Co C
O C
O O
O
Cl
(b)
AsPh3
H3C
C O Cl
HC
Re
H3C C O
Cl
AsPh3
3.19 (a) [Cr(C2O4)3] chiral due to propeller shape with no internal mirror planes
(b) Not chiral due to several internal mirror planes including the plane of the molecule.
10
Cl NH2
Pt CH2
Cl CH2
NH2
*3.21. Prior to Werner's synthesis and resolution of coordination compounds containing chelating agents,
the evidence for his coordination theory had been "negative." That is to say, his theory often predicted only
two isomers for a given MA4B2 or MA3B3 complex (where A and B are monodentate ligands) if the
B B
geometry of the coordination sphere was octahedral. Planar hexagonal and trigonal prismatic geometries, on
the other hand, yielded three isomers in each case. His and other research groups indeed could synthesize
only two isomers of these compounds. But what if the correct geometry was hexagonal or trigonal prismatic
and the third isomer was just particularly difficult to synthesize? Werner had only "negative" evidence for
his octahedral coordination theory. It was the absence of a given isomer that Werner claimed supported his
ideas. However, octahedral coordination spheres for a complex of general formula M(AA)2B2 (where AA B
= a chelating bidentate ligand) should have one chiral and one nonchiral form. Werner and his group were
able to confirm the existence of this number of isomers and therefore provide "positive" evidence for his
theory and the octahedral configuration of his secondary valence.
*3.23. Structures (iii), (vi) and (vii) are chiral as they lack an internal mirror plane.
a B
a a
B A
B A B
A B B A
a a a a
a a a a
A B A
B A B B
A
(iv) B (v) A (vi) B (vii) A
3.25.
11
1+ 1+
NO2 H2N CH2
CH2
NH2 NH2 NH2
H2C H2C NH2
Co CH2 Co
H2C CH2 H2C
NH2 NO2
NH2 NH2
trans R/S-cis
3.27. No, the structure would then have a plane of symmetry and would no longer be chiral. The plane of
symmetry would contain the C-C bond of the methyl-substituted ethylenediamine, pass through the
platinum cation, and then bisect the C-C bond of the phenyl (C6H5) - substituted ethylenediamine.
(b) Since the four binding cites of the NTA must be adjacent to each other, the two monodentate ligands
(SCN- and Cl-) also must always be cis to each other. However, either the chloride or the thiocyanate could
be trans to the nitrogen of the NTA as shown below. In either case, the complex anion contains an internal
mirror plane and is therefore not chiral.
O O
O C O C
O O
CH2 CH2
C CH2 C CH2
K2 O K2 O
N N
Co CH2 Co CH2
Cl C C
O SCN O
O O
SCN Cl
*3.31. Both of the square planar structures possess a plane of symmetry (the plane of the molecule), but the
12
one tetrahedral structure does not. Therefore the square planar versions are nonchiral while the tetrahedral is
chiral.
NH2 NH2
CH2
C Ni CH2 H2N
O C CH2
O O
O
Ni C
H2N O
O
O O
O NH2 H2C
C C
Ni CH2
H2C
C
O O
NH2
O
*3.33. Since the nitrate ligand is capable only of O-bonding to a metal center, both the bis(ethylene-
diamine)dinitratocobalt(III) chloride and the bis(ethylenediamine)dinitritocobalt(III) chloride possess four
Co3+-N and two Co3+-O interactions. Therefore it follows that both of these compounds should be the same
color while the bis(ethylenediamine)dinitrocobalt(III) chloride, in which the complex cation contains six
Co3+-N interactions, should be a different color.
*3.35. The Lewis and VSEPR structures of thiocyanate are shown in (i) and (ii) below. The sulfur has three
lone pairs available to bind with a metal center while the nitrogen has only one. Assuming the four electron
pairs around the sulfur (three lone pairs and one bonding pair) are tetrahedrally dispersed, S-bonded SCN-
complexes should possess a nonlinear M-S-C interaction. Given the linear arrangement of the triple bond
and the one lone pair about the nitrogen atom, on the other hand (or is it on the other tooth?) N-bonded
thiocyanate complexes should possess a linear M-N-C interaction. These two cases are shown in structures
(iii) and (iv), respectively.
(i) (ii)
_
S C N
S C N
(iii) (iv)
S C N S C N M
*3.37. S-
M <109ο bonded
M 180o
13
thiocyanate will take up more space around a metal atom or ion because the -SCN is able to rotate about the
M-S bond and sweep out a fairly large cone-shaped volume. N-bonded thiocyanate, on the other hand
(tooth?) rotates about the M-N bond and sweeps out a much smaller, needle-like cylindrical volume. In the
[Co(NH3)5NCS]2+ cation, the five ammonia ligands sweep out cone-like volumes and take up a fair amount
of volume. They do not leave much volume available for the thiocyanate so it is more stable in the
isothiocyanate "needle" form that does not require as much volume. In the [Co(CN)5SCN]3- anion, the linear
CN- ligands take up very little volume and so the S-bonded SCN-, that takes up more space, is favored.
*3.41. Since all four positions in a tetrahedral are adjacent to each other, there would only one possible
geometric isomer for [M(dmen)2]. This isomer would chiral because it would lack an internal mirror plane.
*3.45. At least one of each type of isomer except optical is possible as shown below.
14
Chapter 4
Bonding Theories for Coordination Compounds
Chapter 4 Objectives
You should be able to
15
• sketch out how molar susceptibility is measured and how its value can be related to the magnetic
moment, μ, and to the number of unpaired electrons in a coordination compound
• rationalize why so many coordination compounds are highly colored and how these colors can, in
some cases, be simply related to the size of crystal field splitting energy
16
Solutions to Odd-Numbered Problems
Hydroxide ions:
(1) Arrhenius base -- treats bases as substances that produce OH- in solution
(2) Brønsted-Lowry base -- capable of accepting a proton (H+)
(3) Lewis base -- OH- is an electron pair donor
4.3 The oxygen molecule has a number of lone pairs of electrons associated with it. One of these lone
pairs can be donated to the central iron ion (Fe2+) of the hemoglobin. The O2, then, has served as an
electron pair donor and is a Lewis base. The Fe2+ is an electron pair acceptor and is a Lewis acid.
4.9. Coulomb's law says that the potential energy (PE) is equal to Q1Q2/r. If r is infinite, then the PE is
zero. But we also recognize that the two electrons have the same charge and, therefore, the net energy will
be positive for finite values of r. When the two electrons are placed side by side, the distance r between
the two particles decreases and the value of the potential energy (= Q1Q2/r) becomes more and more
positive.
17
*4.13.
4.15. The six independent orbitals are classified as dependent because any one of them can be written as
a linear combination of the others. If one writes a linear combination of the 3dz²- y²_and 3dz²- x²_orbitals to
make the 3d z²_orbital, the resulting five orbitals are no longer dependent but independent.
*4.17.
(a) 3dx2-y2 3dz2-x2 3dz2-x2
1/2ΔO
E barycenter Δ O
1/2ΔO
(b) The 3dxz orbital points in between the x and z axes and therefore avoids, to some extent, the ligands
located on these axes. On the other hand the 3dz²- x² orbital points directly along the x and z axes and
therefore points directly at the ligands. Given these relative positions, it is not surprising that a d
electron prefers not to occupy the 3dz²- x²_orbital. That is, the 3d z²- x²_orbital is of higher energy.
*4.19. Given that the 3dz²_ orbital is a linear combination of the 3dz²-y²_and 3dz²-x²_orbitals which are
identical in shape and relative orientation (that is, they all point directly at the ligands of the octahedral
field) to the 3dx²-y²_orbital, all of these orbitals (including the 3dz² and 3dx² - y²) should be degenerate in
such a crystal field.
*4.21. (a) The 3dz2_ orbital will point directly at the two ligands along the z axis of the linear field. The
3dyz and 3dxz ligands point in between the z axis and either the y or the x axis and therefore are
destabilized somewhat. The 3dxy and 3dx² - y²_orbitals, being fully in the xy plane do not point at the z
axis ligands at all are the most stabilized.
18
3dz2
0.91Δ
3dyz 3dxz
x
barycenter
0.74Δ -x
3dxy 3dx2-y2
(b) To calculate the position of the barycenter, one assigns the position roughly between the first and
second levels and uses the relationship that
Estabilization = Edestabilization
2(0.74Δ - x) = 2x + 1(0.91Δ + x)
1.48Δ - 2x = 3x + 0.91Δ
0.57Δ = 5x
x = 0.11Δ
4.23. By analogy to other fields, the crystal field splitting energy of the 3px 3py 3p
orbitals in a square planar field can be labeled as Δsp. In order for the
energy of stabilization to be equal to the energy of destabilization, the 3px 1/3Δsp
and 3py orbitals (which point directly at the ligands in the xy plane) 2/3Δsp
would have to be destabilized by 1/3 Δsp while the 3pz orbital (which does
not point at any ligand) would be stabilized by 2/3 Δsp. 3pz
4.25. (a) Since a cubic field is two tetrahedral fields superimposed 3dxy 3dyz 3dxz
upon each other (as shown in Figure 4.7), its crystal field
splitting diagram is qualitatively the same as that for a tetrahedral field.
(b) As shown in Figure 4.8, the 3dxy orbital points towards four of the Δc
edges of the cube and therefore is closer to the ligands than the 3dx² - y²_
orbital that points towards the centers of four of the faces of the cube.
It follows that the 3dxy and similar orbitals are destabilized while the 3dz2 3dx2-y2
3dx² - y² (and the similar 3d z²_) orbital is stabilized.
19
*4.27. (a) Both the 3dx²-y² and 3dz² orbitals point directly at ligands and therefore are destabilized. (The
3dx²-y² points at four ligands and is more destabilized than the 3dz² which points at only one.) The 3dxy,
3dyz, and 3dxz orbitals point in between the ligands and are stabilized. (The 3dyz and 3dxz orbitals have
components along the z-axis, where there is only one ligand, and therefore are more stable than the 3dxy
orbital.)
3dx2-y2
3dz2
0.83Δ 0.83 Δ + x
x
0.17 Δ
0.17Δ − x 0.37Δ + (0.17Δ - x)
0.37 Δ
1.25Δ - 3x = 2x + 0.83Δ
0.42Δ = 5x
x = 0.084Δ
Therefore, the barycenter sits about midway between the 3dz_ and 3dxy orbitals.
*4.29.
Pz
2/3Δ L
ΔL
1/3Δ L
Px Py
4.31. Tetrahedral complexes are almost always high spin because Δt is about half the magnitude of Δo
and almost always less than the pairing energy, P.
20
*4.33. Only d8 would have high- and low-spin
possibilities. d7 would involve the sum of the
top-most energy split and the middle-level split
and so does not meet the condition set in the
statement of the problem.
d8 high-spin d8 low-spin
*4.41.
ΔO
0.60ΔO
0.23 ΔO
0.40ΔO 0.43 ΔO
0.086 ΔO
21
Therefore, the square planar configuration is of lower energy and is favored. The stronger the field
(Δo), the more favorable the square planar configuration becomes.
4.43.
0.11Δ
0.63Δ
4.45. In a tetragonal compression, the ligands located along the z axis move toward the metal ion. This
movement results in more steric hindrance about the metal and causes the ligands located in the xy plane
to move away from the metal center.
4.47. In [Ru(NH3)6]2+, the Ru2+ is a moderately charged, large metal cation and the ammonia ligand is
moderately high in the spectrochemical series. This set of conditions would probably result in a fairly
large crystal field splitting energy and a strong-field low-spin state.
4.51. Phosphines have d orbitals with which to form π-interactions with a transition metal whereas
ammines do not. Phosphines are able to accept π-electron density from filled metal d orbitals and
thereby increase both the partial positive and partial negative charges on the metal and ligands,
respectively. The resulting enhanced electrostatic M-L interaction increases the split between the sets of
metal d orbitals in phosphine complexes. Phosphines, therefore, are generally stronger-field ligands
than ammines.
*4.53. Trifluorophosphine would be the stronger ligand, that is, it would be higher in the
spectrochemical series. Sterically, PF3 is much smaller and compact than the bulky PPh3. Therefore, the
PF3 will get closer to the metal and more significantly influence the relative energies of the d-orbitals.
Electronically, the high electronegativity of the fluorine atoms in PF3 will help draw electron density
toward the ligand. This extra electron-withdrawing power will make the π-back bonding stronger in the
M-PF3 bond than in the M-PPh3 bond. The empty 3d orbital of the phosphorus is capable of accepting
electron density back from a filled t2g type orbital. The presence of the three electron-withdrawing
fluorine atoms enhances this effect. As a result the M-PF3 bond will be more polar and the splitting of
the d orbitals more enhanced.
22
4.55. d6 octahedral: strong-field: t2g6, n = 0, μS = 0
weak-field: t2g4eg2, n = 4, μS = ( 4)(4 + 2) = 4.90 BM
d6 tetrahedral: strong-field: e4t22, n = 2, μS = (4)(2 + 2) = 2.83 BM
weak-field: e3t23, n = 4, μS = 4.90 BM
4.61. For the [RuF6]4- ion, μ = 2.84 (χMT)½ = 2.84[(1.01 x 10-2)(298)]½ = 4.93 BM which is consistent
with 4 unpaired electrons. For the [Ru(PR3)6]2+ ion, χM = 0 indicates that μ = 0 and therefore there are no
unpaired electrons. Four unpaired electrons are consistent with a d6 ion in a weak field while zero
unpaired electrons correspond to a d6 ion in a strong field.
4.63. Yes, it would be surprising if all the compounds involving these complex ions were to be the same
color. Given the spectrum (pun intended) of crystal field splitting abilities of the ligands involved, these
complexes should absorb at a variety of wavelengths and therefore be of various colors.
23
*4.67. When the two water ligands are driven off by heating, the nickel changes from an octahedral to a
square planar environment. We know that [Ni(deen)2]Br2 must be square planar because the alternative
coordination sphere, tetrahedral, cannot yield a diamagnetic species for the product. One way to
rationalize the color change in this reaction is shown below. When the waters are driven off, there is
more room for the somewhat bulky deen bidentates to get closer to the nickel therefore increasing the
magnitude of the splitting between the uppermost two d-orbitals. As shown, this could result in the
observed change of color. Again, we must be wary of such an oversimplification but, in any case, it is
logical that the color should change in a fairly radical manner.
R O Y G B I V increase in crystal R O Y G B I V
field splitting
*4.69. The octahedral [Ni(H2O)6]2+ has a t2g6eg2 configuration corresponding to two unpaired
electrons. The [Ni(CN)4]2- must be a strong-field, square planar complex in order to be diamagnetic.
2+ 2-
H2O
H2O NC CN
OH2 Ni
Ni
NC
H2O CN
OH2
H2O
It must absorb at considerably higher frequencies (most likely into the ultraviolet) than the hexaaqua
complex and therefore transmits or reflects all the visible frequencies and appears colorless.
eg
t2g
24
4.71. To picture the bonding in coordination compounds as strictly ionic is, at first thought, rather
unrealistic. However, this theory does a surprisingly good job at accounting for the existence and high
stability of these compounds as well as their magnetic characteristics and colors. The experimental
evidence for the theory, as covered in this chapter, comes from two major types of studies: magnetic
measurements and absorption spectroscopy. Magnetic measurements generate values for the molar
magnetic susceptibilities of a series of coordination compounds. Molar susceptibilities, in turn, generate
molecular-level magnetic moments that can be related to the number of unpaired electrons and electronic
configurations of a complex. These results are explained quite adequately by the crystal field theory.
Absorption spectroscopy gives information on the frequencies of light absorbed by coordination
compounds. These frequencies vary in ways (depending on the size and charge of the metal and ligands)
that can be explained in many cases by the ionic crystal field theory.
25
Chapter 5
Rates and Mechanisms of Reactions of Coordination Compounds
26
Chapter 5 Objectives
27
Solutions to Odd-Numbered Problems
___[{Cu(NH3)3(H2O)}2+]__ x _____[{Cu(NH3)4}2+]____
[{Cu(NH3)2(H2O)2}2+][NH3] [{Cu(NH3)3(H2O)}2+][NH3]
= ___[{Cu(NH3)4}2+]___ = β4
[{Cu(H2O)4}2+][NH3]4
5.3. K1 = _[Cr(CO)5PPh3]_
[Cr(CO)6][PPh3]
K3 = ___[Cr(CO)3(PPh3)3]__
[Cr(CO)4(PPh3)2][PPh3]
5.5. K1 = [{Cr(H2O)4(C2O42-)+}]_
[{Cr(H2O)6}3+][C2O42-]
K3 = ______[{Cr(C2O4)3}3-]_____
[{Cr(H2O)2(C2O4)2}-][C2O42-]
5.7. Kb = [NH4+][OH-], the value of [H2O] is incorporated into the value of Kb.
[NH3]
5.11. The O17 label would end up in the water molecule that is given as a product of the reaction. The
Cr3+-O bonds in the hexaaquachromium(III) ion are not broken in this reaction of a coordinated ligand.
Instead, the OH- reactant abstracts a proton (H+) from one of the waters leaving an OH- ligand in its
place in the coordination sphere.
*5.13. Strong-field low-spin d6 cobalt(III) complexes are inert to substitution because they lose crystal
field stabilization energy upon breaking a metal-ligand bond to form a five-coordinate transition state.
Accordingly, it is often easier (kinetically) to prepare cobalt(III) compounds by oxidizing Co(II)
28
complexes that are not inert.
5.17. [Ni(CN)4]2- Ni2+ d8 square planar, room for attack of incoming ligand;
assuming an associative mechanism – most likely to be
labile
[Mn(CN)6]3- Mn3+ d4 in between, high charge density but only a moderate
loss of CFSE – an in between case
[Cr(CN)6]3- Cr3+ d3 high charge density; significant loss of CFSE – most
likely to be inert
Now the fast step (1) will establish an equilibrium "behind" the rate-determining second step such that
k1[ML5X] = k-1[ML5][X]
Solving this last equilibrium expression for [ML5] yields [ML5] = k1[ML5X]/k-1[X]
Substituting this expression into the one for the overall rate yields
*5.21. Since the first step is now considered to be faster than the second, the concentration of ML5XY
would now be able to build up to a significant extent. Given that the second step is now much slower
than the first, not much of the ML5XY would be used up in the rate-determining step. It follows that we
expect the concentration of ML5XY to be relatively high.
29
5.23. In the absence of experimental complications, an associative mechanism should yield a rate law
first order in both the reactant complex and the entering ligand while the dissociative mechanism would
yield a rate law first order only in the reactant complex. In addition, an A mechanism might be proven
by the isolation of the seven-coordinate intermediate while the D could be verified by the isolation of the
five-coordinate intermediate.
5.27. These data are generally consistent with a dissociative mechanism. Log k does not vary
appreciably with the identity of the entering ligand, L. (The variations that do occur might very well be
due to the ligand L "lurking" outside the coordination sphere of the reactant as in an Id mechanism.) The
rate-determining step would be
Since the rate-determining step does not involve the L ligand, the rates are not dependent on [L].
5.29. If the rate constant is 1.0 x 10-4 s-1 then log k is -4.0, a value of the same order of magnitude as
those for the anation reactions of Problem 5.26. This similarity implies that again the rate-determining
step is the breaking of the Co3+-OH2 bond and this reaction occurs via a dissociative mechanism.
*5.31. If the rate constant is 3 x 10-6 M-1s-1 then log k is -5.5, a value that differs significantly from most
of the other data given in Problem 5.30. This data seems to lead to the conclusion that these reactions
occur by an associative rather than a dissociative mechanism. If the splitting of a Cr3+-OH2 were the
rate-determining step, than the rates of all these reactions should all be of the same order of magnitude.
5.33. The table shows that these aquation reactions depend quite strongly on the identify of the L-ligand.
This result is consistent with a rate-determining step in which the M-L bond is broken to form a five-
coordinate transition state.
5.35. The change in the CFSE on going from the octahedral reactant to the five-coordinate intermediate
directly affects the kinetics of substitution reactions. If CFSE is gained by forming the five-coordinate
intermediate, the energy of activation (Ea) will be reduced by that amount and the reaction will be faster
than expected in the absence of crystal field effects. If, on the other hand, CFSE is lost upon forming the
30
intermediate, the Ea will be increased by that amount and the reaction will be slower.
5.41. The Fe3+ and V3+, while possessing a 3+ charge do not lose appreciable amounts of crystal field
stabilization energy upon forming a square-pyramidal five-coordinate transition state. The Fe3+ cation is
a d5 case that loses only 0.09ΔO or zero CFSE (strong-field and weak-field cases, respectively), while the
V3+ cation is a d2 case that gains 0.11ΔO of CFSE. In order for a first row transition metal to be inert it
appears that it must be 3+ charged and lose 0.20ΔO or more of CFSE.
*5.43. (a) There would be a loss of 0.20Δo (see Table 5.4) when an octahedral d8 complex goes to a
five-coordinate intermediate. This loss combined with a 3+ charge would make these complexes inert to
substitution. (b) Cu3+ compounds contain d8 metals that are more likely to form square planar
compounds rather than octahedral ones.
*5.45. The greater steric hindrance provided by the bulkier N,N-diethylethylenediamine in complex (b)
should help to weaken the Ni2+- OH2 bond that breaks in the rate determining step.
5.47. Given the lack of a bridging ligand, an inner-sphere mechanism for this cross reaction is not
possible. The rate of this reaction, which presumably then occurs by an outer-sphere mechanism, is
rather slow because the electron that the Co(III) accepts from the Ru(II) must be placed in an eg orbital.
This orbital points directly at the ligands and therefore, because of electron-electron repulsions,
significantly increases the metal-ligand distance. The result is that bond distances in the hexaammine
cobalt complexes must be quite different. The energy necessary to rearrange the Con+-NH3 bonds so that
electron transfer can take place contributes to the energy of activation and is a major factor in causing a
low rate constant for the reaction.
5.49. A second-order rate law for a reaction involving two different reactants would be of the general
form, rate = k[A][B]. Putting units with the rate and concentrations and then solving for the rate
constant yields the following result:
31
5.51. [Ru(en)3]2+ + [Ru(en*)3]3+ ─→ [Ru(en)3]3+ + [Ru(en*)3]2+, where * = a radioactive label
Lacking a potential bridging ligand in the reactant complexes, this self-exchange reaction proceeds by an
outer-sphere mechanism. The reaction should be very rapid because little adjustment of the Ru-N
distances need be made before the electron can be transferred.
5.53. (a) [IrCl6]2- + [W(CN)8]4- ─→ [IrCl6]3- + [W(CN)8]3-: Due to the inert nature of these highly
charged iridium and tungsten ions and the fact that no ligand exchange seems to occur, this is most likely
an outer-sphere mechanism.
(b) [Co(NH3)5CN]2+ + [Cr(H2O)6]2+ ─→ [Cr(H2O)5NC]2+ + [Co(NH3)5(H2O)]2+: With the transfer of
the bridging cyanide ligand and the fact that it reverses its denticity from cyano to isocyano, an inner-
sphere mechanism seems likely.
(c) [*Cr(H2O)6]2+ + [Cr(H2O)5F]2+ ─→ [*Cr(H2O)5F]2+ + [Cr(H2O)6]2+: Again, a bridging ligand
seems to be transferred and an inner-sphere mechanism seems likely.
5.55. The mechanism that produces the S-thiocyanato would be much the same as the above written for
Problem 5.54 except that the thiocyanate would bridge from the cobalt to the chromium ions using two
lone pairs on the sulfur atom of the ligand.
5.57. (a) The most straightforward associative mechanism for the substitution of square planar
complexes would have a rate-determining step in which the entering ligand attacks the square planar
reactant complex to form a five-coordinate intermediate. In this case, the rate would be first-order in the
entering ligand and in the reactant complex and therefore second-order overall. There is, however, a
second possibility. Since most all these reactions are carried out in aqueous solution, the rate-
determining step could be the attack of a water molecule to form a five-coordinate intermediate. The
resulting aqua complex could then react with the incoming ligand to form the final product in a faster,
non-rate-determining step. In this case the rate law would be first order in the reactant complex and first
order in water. However, as in other cases we have discussed, given the large and nearly constant
concentration of water in aqueous solutions, this latter rate law might be pseudo-first order in only the
concentration of the reactant complex. (b) The rate of these associative mechanisms would decrease
with the increasing steric bulk of the nonreacting ligands and the bulk of the entering ligand. It would
increase with the charge of the entering ligand and the overall charge carried by the reactant complex.
5.59. Since the chloride is higher in the trans-directing series than ammonia, the second ammine is
placed preferentially in the cis position. (The charges on the various complexes are omitted for clarity.)
Cl Cl Cl NH3 Cl NH3
NH3 NH3
Pt Pt Pt
Cl Cl Cl Cl Cl NH3
5.61. Organic sulfides are large, polarizable ligands. They should be good trans-directors. The ability
of various ligands to be good trans directors is explained, in part, by the polarization theory attributed to
A. Grinberg.
32
Chapter 6
Applications of Coordination Compounds
Chapter 6 Objectives
33
Solutions to Odd-Numbered Problems
6.1. Diamminesilver(I), [Ag(NH3)2]+, contains Ag(I), a d10 metal. With no vacancies in d orbitals,
coordination compounds containing this cation cannot readily absorb visible light and so remain colorless.
On the other hand, tetraamminecopper(II), [Cu(NH3)4]2+, contains Cu(II), a d9 metal that does have
vacancies in its d orbitals and therefore readily absorbs visible light.
*6.3. Cyanide acts as a halide. In fact, ions such as cyanide (CN-), thiocyanate (SCN-), and others (see
Chapter 18 for more details) are often referred to as pseudohalides because of their similarities to these
ions. Accordingly, cyanide can often be quantitatively analyzed in the same way as the halide ions. One
method of doing this is to add a slight excess of a solution of silver nitrate, AgNO3, to the cyanide until
silver cyanide, AgCN(s), is precipitated, isolated, and then weighed quantitatively. The Liebig method
actually refers to the method in which a standardized solution of silver nitrate is used to titrate a solution
of cyanide until the first appearance of a precipitate of silver dicyanoargentate(I), Ag[Ag(CN)2]. This
reaction becomes the basis of a titrimetric determination of cyanide.
6.5. Since hard acids are small, often highly-charged metal ions (Lewis acids) with high charge densities
and low polarizabilities whereas hard bases are small, highly electronegative ligands (Lewis bases), the
hard-hard M-L interaction is one between fairly highly charged species. It follows that the bonding
between such species would tend to be predominantly ionic. On the other hand, soft acids are large,
highly polarizable metals of low (even zero) oxidation states and soft bases are large, polarizable ligands
of low charge, it follows that the soft-soft M-L bond between such species would not be highly ionic.
6.7. S-thiocyanato complexes involve thiocyanate, SCN-, bound through its relatively soft sulfur atom.
N-thiocyanato complexes are bound through the relatively hard nitrogen atom. Mercury(II) is a soft acid
whereas cobalt(III) is hard. Given the rules of HSABs, the Hg-S and Co-N bonds are favored and not
vice versa.
6.9. The diacetatotetraaquairon(II) ion involves two acetate ions acting as monodentate ligands. The
malonate ion has two acetate moities bound together through a common -CH2- group. Both of the acetate
moities can act as Lewis bases and make malonate a bidentate ligand. The difference between the
equilibrium constants, then, is an example of the chelate effect. The malonate complex involves a
chelating, multidentate ligand that is more stable than the equivalent compound involving monodentate
ligands. These two situations are shown in the following two equations. (The acetates could also form a
trans complex.)
34
H2O
O
C
H2O O
Fe CH3
H2O O
H2O 2+
CH3
2 CH3COO- C
H2O
H2O OH2
Fe O
H2O OH2
-
OOCCH2COO- H2O
H2O
O
H2O C
O
Fe
H2O O CH2
C
H2O
O
6.11. The diacetatotetraaquairon(II) ion involves two acetate ions acting as monodentate ligands. The
oxalate ion has two carboxylate (COO-) moieties bound together through a carbon-carbon bond. Both of
the carboxylate moities can act as Lewis bases and make oxalate a bidentate ligand. The difference
between the equilibrium constants, then, is an example of the chelate effect. The oxalate complex
involves a chelating, multidentate ligand that is more stable than the equivalent compound involving
monodentate ligands. These two situations are shown in the following two equations.
H2O
O
C
H2O O
Co CH3
H2O H2O O
2+
CH3
2 CH3COO- C
H2O
H2O OH2
Co O
H2O OH2
-
OOCCOO- H2O
H2O
H2O O
O
Co C
35 H2O O C
O
H2O
6.13. Acetone is a monodentate ligand whereas acetylacetonate, [CH3COCHCOCH3]-, made up of two
acetone [or acetyl, CH3CO] moities connected together by a common -CH- group, is bidentate. The
difference between the stability of acetone and acetylacetonate, then, is due to the chelate effect. The acac
complexes involve chelating, bidentate ligands that form more stable compounds than the equivalent
compounds involving two monodentate ligands.
6.15. Using Equations (6.9) and (6.10) as shown below, we can calculate the equilibrium constant for the
substitution of three ethylenediamine ligands for six ammines in the Ni(II) coordination sphere.
6.17. The dmgH ligand has a molecular formula of C4H7O2N2 and a molecular weight of 115.11 g/mol.
Since one mole of Ni yields one mole of Ni(dmgH)2, we can calculate the mass of nickel in the ore as
follows:
6.19. One mole of EDTA complexes one mole of Ca2+, therefore we can calculate the grams and
percentage of calcium in the sample as follows.
*6.21. One mole of trien complexes one mole of Cu2+, therefore we can calculate the grams of copper in
the 10.00mL aliquot (or portion) of the original solution.
If there are 0.01446g Cu2+ in the 10.00mL aliquot, there must be 0.1446g in the full 100mL volumetric
flask. Therefore we can calculate the percentage of copper in the sample as follows:
6.23. ___8.7g P__ x 1 mol P x 1mol Na5P3O10 x 367.85g Na5P3O10 = 34g Na5P3O10 = 34%
100g sample 30.97g P 3 mol P 1 mol Na5P3O10 100g sample
36
6.25. Dear Econ Major:
Phosphates have been an important component of synthetic detergents because they let the
soap-like part of a detergent do its job unhindered by hard water. In other words, phosphates render the
hard water ions (calcium, magnesium, and iron) incapable of interfering with the action of the soap-like
molecules in detergents. Phosphates have also been important because they are inexpensive and readily
available to the detergent manufacturer. (See footnote at the end of this chapter.)
750-610 red
610-590 orange
590-570 yellow
570-500 green
500-450 blue
450-370 violet
6.31. This is potentially an octadentate ligand. It would literally surround a Mn ion. Some of its Lewis
base sites would most likely go unused.
37
- CH2 CH2 CH2 CH2 CH2COO- 5-
OOCH2C
N N N
: : :
-
OOCH2C CH2COO- CH2COO-
6.33. Mercury is a soft metal and will prefer to interact with soft groups like the sulfur-containing
mercaptans.
6.35. Both histidine and cysteine are tridentates that could readily coordinate with cobalt and remove it.
This sequestering effect would be the basis of its use for cobalt detoxification.
6.37. Of serine and cysteine, the latter with its soft mercapto (-SH) group, would be the better antidote
against the soft heavy metals.
Footnote:
(Dear readers: I know you can do better than I did in writing letters to various academic majors and
professionals. I would love to see the various short paragraphs that you all come up with. You'll be
famous; I might put your paragraph in the next version of this Solution Manual! (If there is a next
version.) Submit your entries to the author at Department of Chemistry, Allegheny College, Meadville,
PA 16335.
38
Chapter 7
Solid State Structures
39
Chapter 7 Objectives
• distinguish among and characterize the various types of crystals: ionic, metallic, covalent, and
atomic/molecular
• identify and characterize common A-type structures by the coordination number of a given
sphere, the number of spheres per unit cell, the fraction of space occupied, and the density
expression
• identify and appreciate the significance of the Bravais lattices
• characterize atomic, van der Waals, and metallic radii
• calculate the density of a given metallic crystal knowing its structure and relevant atomic
weight and radii data
• identify and determine the relative sizes of cubic, octahedral, and tetrahedral holes in various
A-type structures
• use radius ratios to predict the type of hole occupied by the smaller species in an ABn structure
• rationalize why the radius ratio represents the lower limit to the range in which a given type of
hole will be occupied
• discuss the origin and variation of Shannon-Prewitt ionic radii
• identify and characterize common AB structures (rock salt, zinc blende, wurtzite, and cesium
chloride) by the structure and coordination numbers of both their anions and cations
• calculate the density of a given compound knowing the type of AB structure it assumes
• identify and characterize common AB2 structures (fluorite, cadmium iodide, rutile, and anti-
fluorite) by the structure and coordination numbers of both their anions and cations
• identify and discuss ABn structures involving polyatomic molecules and ions
• identify and characterize common defect structures such as Schottky and Frenkel defects and
edge dislocations
• characterize normal and inverse spinel structures and provide a rationale for the structure of a
given compound based on calculations of crystal field stabilization energies
40
Solutions to Odd-Numbered Problems
7.1. Metallic Crystals – a lattice of cations held together by a sea of free electrons, for example, metallic
copper. Covalent Crystals – atoms or groups of atoms in a lattice held together by an interlocking
network of covalent bonds, for example, diamond. Atomic/Molecular Crystals – a lattice of atoms or
molecules held together by intermolecular forces (Van der Waals, dipole-dipole, hydrogen bonds), for
example, argon, water.
7.7. The free, non-hydrogen-bonded water molecules fill some of the large, hexagonal holes in the ice
structure resulting in a greater mass in approximately the same volume, that is, a higher density.
7.9.
7.11. As shown below, there is 1 (= 8 x 1/8) circle and 1 (= 2 x 1/2) "x" in the unit cell for a total of two
particles per unit cell.
7.13. A corner 12 x 1/6 = 2 Since there are three A and three B atoms in a unit
face 2 x 1/2 = 1 cell, the empirical formula would be AB.
B interior 3 x 1 = 3
41
7.15. This formula corresponds to the fraction of space occupied in a body-centered cubic unit cell
composed of spheres of diameter d. There are two spheres per unit cell [ 1 + 8 (1/8)] and each sphere
has a volume of 4/3πr3 or, substituting d/2 for r, 4/3 π(d/2)3. The volume of the unit is the cell edge
(2d/ 3 , see Figure 7.9) cubed.
(a)
4r = l 2
1 = 4.070A
r = (l 2 ) / 4 = (4.070 2 ) / 4
r = 1.44Å
The actual density is 19.3 g/cm3, therefore the percent error is zero.
42
7.25. In a simple cubic lattice, the eight spheres
are in contact along the cell edge. The diagram 2rsphere+2rhole
at right shows a cross section through the face
diagonals of the top and bottom faces.
( 3 - 1) rsphere = rhole
(a) r(Be2+) = 0.59 = 0.47 predicts c.n. = 6 (b) r(Be2+) = 0.59 = 0.35 predicts c.n. = 4
r(O2-) 1.26 r(S2-) 1.70
incorrect, BeO assumes correct, BeS assumes
wurtzite structure zinc blende structure
(c) r(Mg2+) = 0.86 = 0.68 predicts c.n. = 6 (d) r(Mg2+) = 0.86 = 0.51 predicts c.n.
=6
r(O2-) 1.26 r(S2-) 1.70
correct, MgO assumes correct, MgS assumes
rock salt structure rock salt structure
(e) r(Ag+) = 1.29 = 0.77 predicts c.n. = 8 (f) r(Ag+) = 1.29 = 0.71 predicts c.n. = 6
r(Cl-) 1.67 r(Br-) 1.82
incorrect, AgCl assumes correct, AgBr assumes
43
rock salt structure rock salt structure
(g) r(Ag+) = 1.29 = 0.63 predicts c.n. = 6 (h) r(Tl+) = 1.64 = 0.98 predicts c.n. = 8
r(I-) 2.06 r(Cl-) 1.67
incorrect, AgI assumes correct, TlCl assumes
wurtzite structure CsCl structure
7.31. Cs+Au-
Assume that dCs-Au = r(Cs+) + r(Au-) = 3.69Å r(Cs+) = 1.81 = 0.96; predicts c.n. = 8;
r(Au-) = 3.69 - r(Cs+) = 3.69 - 1.81 = 1.88Å 1.88
7.35. (a) If all the cubic holes of fluorite were occupied by calcium ions, the stoichiometry would be 1
to 1, i.e., CaF. (b) If all the octahedral holes in cadmium iodide were occupied by cadmium ions, the
stoichiometry would also be 1 to 1, i.e., CdI.
7.37. Start with a calculation of the radius ratio: r(F-) = 1.19 = 0.66
r(Cs+) 1.81
(a) This result predicts a rock salt structure for CsF in which the Cs+ cations form a face-centered cubic
lattice and the F- anions occupy all the octahedral holes. (b) There would be 4 Cs+ cations [8(1/8) +
6(1/2)] and 4 F- anions [12(1/4) + 1] in the lattice. The cations and anions are in contact along the cell
edge, therefore l = 2r(Cs+) + 2r(F-) = 2(1.81Å) + 2(1.19Å) = 6.00Å.
7.39. In the NaCl (rock salt) structure, the anions are in a close-packed arrangement whereas in CsCl
they are not. Accordingly, the CsCl should be more compressible under conditions of high pressure and
could give way to the close-packed NaCl structure.
*7.41. KCl, according to Table 7.8, has the rock salt structure. Since the cations and anions can be
assumed to be contact along a cell edge (but note that the face-centered cubic anions cannot be assumed
to be contact along the face diagonal – see the figure in the solution to Problem 7.38), it follows that l,
44
the cell edge, is just equal to 2r(K+) + 2r(Cl-).
7.43. CaF2 assumes a fluorite structure (see Table 7.10). When one pictures a Ca2+ cation in the middle
of the unit cell, the body diagonal of the unit cell is just 4r(Ca2+) + 4r(F-).
(Note that the radius for the Ca2+ is the c.n. = 8 value.)
*7.45. We cannot assume that the oganium(II) cations are in contact along the cell edge, However, the
cations and anions can be assumed to be in contact along the body diagonal. Therefore, body diagonal =
l 3 = 2(1.26Å) + 2(1.5Å) = 5.5Å and l = 3.2Å.
7.47. r(Rb+) = 1.66 = 0.912 It follows that a reasonable structure would be CsCl since the
r(Br-) 1.82 radius ratio predicts a coordination number of eight for the cation.
The ions would be in contact along the body diagonal of the unit cell such that
45
The actual density is given as 3.35 g/cm3. These values are significantly different (percent
error = 26%). If the c.n. = 8 value of 1.75Å for the Rb+ cation is used, the calculated density
comes out to be 3.92 g/cm3, only 17% off from the actual density.
If instead of a CsCl structure, RbBr assumes a rock salt structure (as, in fact, Table 7.8 indicates), then
the ions would be in contact along the edge of the face-centered unit cell.
Therefore, l = 2r(Rb+) + 2r(Br-) = 2(1.66) + 2(1.82) = 6.96Å and the density would be
This latter value is much closer to the experimental value (percent error = 3%).
7.49. r(NH4+) = 1.37 = 0.665 r(NH4+) = 1.37 = 0.820 r(F-) = 1.19 = 0.869
r(I-) 2.06 r(Cl-) 1.67 r(NH4+) 1.37
7.51. Assuming the Na+ and SbF6- ions to be in contact along the cell edge, we can set up the following
expression for the density of NaSbF6. (FW of SbF6- = 235.75 g/mole)
7.53. Transition metal oxides are more frequently non-stoichiometric because these elements usually
have a variety of oxidation states, more so than non-transition metal oxides. With more oxidation states,
the charge of missing ions can be made up by oxidizing some of the remaining ions to a higher stable
oxidation state.
7.55. The oxide ions are face-centered cubic, therefore there are [8(1/8) + 6(1/2) =] 4 per unit cell.
There are 8 tetrahedral holes in a fcc unit cell (1 for each corner of the cube). If 1/8 of these are
occupied by the AII cations, there is 1 AII per unit cell. There are 1 + 12(1/4) = 4 octahedral holes in a
fcc unit cell. If one half of these are occupied by BIII cations, there are 2 BIII's per unit cell. It follows
that the stoichiometry of such a unit cell and therefore the entire compound is AIIB2IIIO4.
B
7.57. Mn3O4 is made up of Mn(II) and Mn(III), that is, it is MnIII2MnIIO4. In a normal spinel structure,
the Mn(III) ions would occupy half the octahedral holes in the face-centered cubic array of oxide ions
while the Mn(II) ions would occupy one eighth of the tetrahedral holes. In an inverse spinel the Mn(II)
would exchange places with one half of the Mn(III) cations. Manganese has an electronic configuration
46
of [Ar]4s23d5, therefore Mn(II) is [Ar]3d5 and Mn(III) is [Ar]3d4. In a high-spin crystal field, the CFSE
of a d5 ion is zero for both tetrahedral and octahedral cases. (See Figure 7.27(b) for these calculations.)
The calculations of the CFSE for a d4 ion in both octahedral and tetrahedral fields is shown below. We
see that the Mn(III) d4 ion clearly prefers an octahedral environment. Therefore, since the AIII ions
occupy the octahedral holes in a normal spinel, this is the structure that the compound is expected to
assume.
Mn(III) d4
3/5ΔO t2
2/5Δ t
2/5ΔO 3/5Δ t
e
47
Chapter 8
Solid State Energetics
Chapter 8 Objectives
• define and discuss both the electrostatic and short-range repulsive forces that contribute to the
overall lattice energy of an ionic compound
• derive and discuss the components of the Born-Landé equation for the lattice energy of an
ionic compound
• discuss the role of charge density as a factor in determining the magnitude of the lattice energy
of a compound
• discuss the role of Kapustinskii equation in estimating the lattice energy of an ionic compound
• write a Born-Haber thermodynamic cycle that can be used to derive a value of the lattice
energy of an ionic compound
• discuss the conditions under which significant covalent contributions to lattice energy would
be expected
• use thermodynamic cycles and the Born-Landé or Kapustinskii equations to estimate values of
electron affinity, heats of formation for unknown compounds, and thermochemical radii
• account qualitatively and quantitatively for the role of crystal field effects in determining the
cationic radii and lattice energies of transition metal salts
48
Solutions to Odd-Numbered Problems
Z+ Z- M ⎛ 1⎞ (+1)(−1)(1.763) ⎛ 1⎞
(b) Uo = 1389 ⎜1 − ⎟ = 1389 ⎜1 − ⎟ = - 633 kJ/mol
ro ⎝ n⎠ (1.66 + 1.82) ⎝ 10 ⎠
8.3. There are two reasonable approaches to this problem. (1) Since we do not know the crystal
structure, we can simply use the Kapustinskii Equation and solve for r(Fr+).
(2)(+1)(−1) ⎛ 0.345 ⎞
- 632 kJ/mol = 1202 ⎜⎜1 − ⎟⎟
ro ⎝ ro ⎠
Solving for ro yields a value of 3.42Å; 3.42Å = r(Fr+) + r(Cl-) = r(Fr+) + 1.67
Therefore, r(Fr+) = 1.75Å
(2) A second approach: since all the other alkali halides assume the rock salt structure, it would be
logical to assume that FrCl does also. In that case we can use the Born-Landé Equation with n = 14 for
Fr+, which has a [Rn] shell (the value of 14 was obtained by extrapolating from the data given in Table
8.2), n = 9 for Cl- which has an [Ar] shell. The average value of n is 11.5.
(+1)(−1)(1.748) ⎛ 1 ⎞
Uo = 1389 ⎜1 − ⎟ = - 632 kJ/mol; Solving for ro yields a value of 3.51Å
ro ⎝ 11.5 ⎠
*8.5. (a) r(Bk4+) = 0.97 = 0.77 which is consistent with a coordination number of 8 and
r(O2-) 1.26 a fluorite lattice.
Z+ Z- M ⎛ 1⎞ (+4)(−2)(2.519) ⎛ 1 ⎞
Uo = 1389 ⎜1 − ⎟ = 1389 ⎜1 − ⎟ = 111,500 kJ/mol
ro ⎝ n⎠ (0.97 + 1.26) ⎝ 10.5 ⎠
The value of n is obtained by averaging n = 7 for O2-, which has a [Ne] shell and a value of n = 14 for
Bk4+, which has a [Rn]4f7 electronic configuration. n = 14 is obtained by extrapolation of the data in
Table 8.2.
49
(b) For a CdI2 structure, M = 2.191 instead of 2.519 for fluorite.
Now the lattice energy comes out to be – 9880 kJ/mol, about a 13% difference.
The Kapustinskii value lies in between the above two values. Without knowing for sure what the crystal
structure of BkO2 is, the UKap seems to be a reasonable approximation of the lattice energy.
8.7. The lattice energy of MgO should be approximately four times that of NaF because the former is a
+2/-2 lattice while the latter is +1/-1. This difference will make MgO harder, as well as higher melting
and boiling.
*8.9. Assumptions to be made for the estimation of the lattice energy of Xe+F-:
(1) radius of Xe+ (isoelectronic with I but with one more proton;
one more electron and proton than I-):
rI (metallic) = 1.96Å
r(I-) = 2.06Å
Use r(Xe+) = 1.90Å (a little smaller than I)
(2) r(F-) = 1.19 = 0.63 Since this is consistent with c.n. = 6, we can
r(Xe+) 1.90 reasonably assume a rock salt structure.
Z+ Z- M ⎛ 1⎞ (+1)(−1)(1.748) ⎛ 1 ⎞
Born-Landé: Uo = 1389 ⎜1 − ⎟ = 1389 ⎜1 − ⎟ = - 703 kJ/mol
ro ⎝ n⎠ (1.19 + 1.90) ⎝ 9.5 ⎠
dU = - NAZ+Z-M - n NB = 0 when r = ro
dr r2 rn+1
AZ+ Z- M ron +1
Solving for B yields B = − ⋅
ro2 n
Substituting this expression for B in the original expression for U yields the following:
50
AZ+ Z - M ron +1
U = NAZ+Z-Mr -1 + Nr – n ⋅ ⋅
ro2 n
└────────────┘
- NAZ+Z-Mro-1 (1/n)
NAZ+ Z - M ⎛ 1⎞
U= ⎜1 − ⎟
ro ⎝ n⎠
8.13.
Born-Haber Cycle: ΔHof
Ba(s) + Cl2(g) BaCl2(s)
2ΔH(g) U
ΔHsubl
2 EA
2 Cl(g) 2 Cl-(g) + Ba2+(g)
IE1 + IE2
Ba(g)
Born-Landé Equation:
Z+ Z- M ⎛ 1⎞ (+2)(−1)(2.519) ⎛ 1 ⎞
Uo = 1389 ⎜1 − ⎟ = 1389 ⎜1 − ⎟ = - 2000 kJ/mol
ro ⎝ n⎠ (1.49 + 1.67) ⎝ 10.5 ⎠
51
8.15. ΔHof
Cu(s) + 1/2 F2(g) CuF(s)
ΔH(g) U
ΔHsubl
EA
X(g) F-(g) + Cu+(g)
Cu(g) IE
Z+ Z- M
⎛ 1⎞ + -
Uo = 1389 ⎜1 − ⎟ Cu , n = 9; F , n = 7
ro ⎝ n⎠
(+1)(−1)(1.638) ⎛ 1 ⎞
= 1389 ⎜1 − ⎟ = - 948.0 kJ/mol
(0.91 + 1.19) ⎝ 8 ⎠
8.17.
ΔHof
1/2 Cl2(g) + 1/2 F2(g) ClF(g)
Cl(g) + F(g)
-DCl-F
ΔH°f = ½DCl-Cl + ½DF-F - DF-Cl
*8.19. We want to calculate a value for the ΔH° for the following equation:
When we calculate the ΔH°f for these two compounds, all the factors will be the same except the lattice
energies. In fact, the ΔH of the above process can be calculated as follows:
52
= U(rock salt form) - U (ordinary form)
The lattice energies will differ only because the Madelung constants differ. Knowing this, we can
calculate the Born-Landé lattice energies for each form and proceed to calculate ΔH.
Z+ Z- M ⎛ 1⎞ (+1)(−1)(1.748) ⎛ 1 ⎞
Uo (rock salt form) = 1389 ⎜1 − ⎟ = 1389 ⎜1 − ⎟ = - 631 kJ/mol
ro ⎝ n⎠ (1.81 + 1.67) ⎝ 10.5 ⎠
Z+ Z- M ⎛ 1⎞ (+1)(−1)(1.763) ⎛ 1 ⎞
Uo (ordinary form) = 1389 ⎜1 − ⎟ = 1389 ⎜1 − ⎟ = - 637 kJ/mol
ro ⎝ n⎠ (1.81 + 1.67) ⎝ 10.5 ⎠
ΔH = - 631 kJ/mol - (- 637 kJ/mol) = 6 kJ/mol
ΔH(g) U
ΔHsubl
EA
Br(g) Br-(g) + Rb+(g)
IE
Rb(g)
(b) From part (b) of Problem 8.1, we know that UoB-L = - 633 kJ/mol
This result is somewhat different from the value given in Table 8.3 (- 324.7 kJ/mol) because RbBr
actually assumes the rock salt (NaCl) structure not the CsCl structure used in Problem 8.1.
Z+ Z- M ⎛ 1⎞ (+2)(−2)(1.641) ⎛ 1⎞
*8.23. Uo = 1389 ⎜1 − ⎟ = 1389 ⎜1 − ⎟ = - 3320 kJ/mol
ro ⎝ n⎠ (0.74 + 1.70) ⎝ 9⎠
(b) ΔHof
Zn(s) + S(s) ZnS(s)
ΔH(g) U
ΔHsubl
S(g) EA1 EA2
S2-(g) + Zn2+(g)
IE1 + IE2
Zn(g)
53
ΔH°f = ΔHsubl + IE1 + IE2 + ΔH(g) + EA1 + EA2 + U
EA2 = ΔH°f - ΔHsubl - IE1 - IE2 - ΔH(g) - EA1 - U
EA2 = - 192.6 - 130.8 - 906.4 - 1733 - 278.8 - (- 200.4) - (- 3320) = 280 kJ/mol
(Note: there are only two significant figures in this value.)
Yes, we would predict that this reaction would probably occur. It has a negative heat of reaction and
since there are two moles of solids on either side of the equation, the ΔS is probably not appreciably
negative. These factors would make ΔG negative and the reaction (under standard state conditions)
spontaneous from left to right as written.
ΔHof
8.27. Ne(g) + 1/2 Cl2(g) Ne+Cl-(s)
ΔH(g) U
EA
Cl(g) Cl-(g) + Ne+(g)
IE
ΔH°f = IE + ΔH(g) + EA + U
Table 7.2 gives a value of 1.54Å for the Van der Waals radius of neon. Removing one electron from a
filled shell should not decrease the size much at all. Let's arbitrarily use a value of 1.40Å for the radius
of Ne+. This combined with the ionic radius of Cl- of 1.67Å gives a value for ro of 3.07Å.
NeCl would not form because the ionization energy of neon is too large. Not enough energy is released
during the formation of the NeCl(s) lattice to make up for the energy needed to ionize an electron from
the stable noble gas electronic configuration of neon.
*8.29. The equation representing the reaction in which CaCl3 might be produced from its constituent
elements in their standard states would be as follows:
54
The entropy change accompanying the above reaction would be negative since one and a half moles of
gaseous reactants is going to zero moles of gaseous products. This negative ΔSf°, combined with the
+1600 kJ/mol calculated for the ΔH°f of this compound, would always yield a positive value for ΔG°f.
Given these values of ΔH°f and ΔSf°, the entropy (which will always be negative) could never be used to
force the formation of CaCl3.
8.31. The effective radius (or so-called thermochemical radius) of a polyatomic ion can be measured by
taking a series of salts containing the ion for which the all the relevant thermochemical data are known
except the lattice energies. Using Born-Haber cycles, the lattice energies can then be determined. Next,
assuming the crystal structures of these salts are known, we can use the Born-Landé equation to estimate
the radius of the polyatomic ion in each salt. (If the crystal structures are not known, we can use the
Kapustinskii equation to estimate to estimate the radius in each case.) These radii can then be averaged
to yield an estimate of the effective radius of the polyatomic ion.
U
ΔΗsubl ΔHof[OH-(g)]
OH-(g) + Na+(g)
Na(g)
IE
Solving for ro yields values of 2.31 and 0.41Å, the latter value being physically impossible.
This result is within 14% of the value given in Problem 7.50. This latter value is obtained by averaging
the results of a number of thermochemical calculations involving the hydroxide anion.
55
8.35.
ΔHof[NaBH4(s)]
Na(s) + B(s) + 2 H2(g) NaBH4(s)
U
ΔHsubl
ΔHof[BH4-(g)]
BH4-(g) + Na+(g)
IE
Na(g)
8.37. ΔHof[K2PtCl6(s)]
2 K(s) + Pt(s) + 3 Cl2(g) K2PtCl6(s)
U
2ΔHsubl
ΔHof[PtCl62-(g)]
PtCl62-(g) + 2 K+(g)
2 x IE
2 K(g)
Solving for ro yields values of 2.91 and 0.39Å, the latter value being physically impossible.
If ro = r(Ca2+) + r(C22-) = 1.14 + r(C22-) = 2.91Å, then r(C22-) = 1.77Å
(4 AW Na +
+ 4 AWClO −
4
) [4(22.99) + 4(99.45]
23
6.02 x10 6.02 x10 23
8.41. density =
(
2rNa + + 2rClO −
4
) 3
=
[ ]
(2.32 x10 −8 )+ (4.80 x10 −8 ) 3
= 2.25 g/cm3
56
8.43.
eg
eg
t2g
t2g
The high-spin Fe2+ has two electrons occupying the eg orbitals that point directly at the octahedrally-
placed ligands, therefore pushing these ligands back. The result is that the high-spin iron(II) is
effectively larger than the low-spin.
*8.45.
4200
actual lattice
energies
4000
50
3800 240
3400
d0 d1 d2 d3 d4 d5 d6 d7 d8 d9 d10
Ca2+ Ti2+ V2+ Mn2+ Fe2+ Co2+ Ni2+ Zn2+
Number of d electrons
57
Chapter 9
Building a Network of Ideas to Make Sense of the Periodic Table
Chapter 9 Objectives
• discuss the contributions of Dmitrii Mendeleev in formulating the periodic table of the elements
• calculate and rationalize values of effective nuclear charges
• discuss the central role of effective nuclear charge in determining the major periodic trends in
atomic radii, ionization energy, electron affinity, and electronegativities
• define the uniqueness principle and discuss the three main reasons behind it
• define the diagonal effect and discuss the three main factors behind it
• define the inert pair effect and discuss the two main reasons behind it
• locate the metal/nonmetal line on the periodic table and discuss why it is positioned the way it is
• summarize the first five components of the interconnected network of ideas for making sense of
the periodic table
58
Solutions to Odd-Numbered Problems
9.1. The properties of eka-silicon (germanium) can be interpolated from those of silicon and tin (above
and below it) and gallium and arsenic (to its left and right). Some reasonable predicted and actual values
are given below.
9.3. Main-group or representative elements are defined in this chapter as those in which the ns and np
orbitals are partially filled. Under this definition, the noble gases, with their filled shells, would not be so
defined. On the other hand, if the noble gases are not representative elements, how should we classify
them? The only alternative would be to designate a separate term for them, a designation that is probably
not worth making.
9.5. According to Webster's New Universal Unabridged Dictionary, 2nd Edition, Dorset & Baber, 1979,
the prefix chalco- is the combining form of copper or brass while the suffix -gen indicates "something that
produces." Therefore the word chalcogen means something that produces copper or brass. Sulfides and
oxides are the main components of copper ores and therefore do produce copper. This is the origin of the
group name for the Group 6A elements.
9.7. The periodic law as applied to the table of the elements refers to the fact that elemental properties are
periodic, that is, they occur at regular intervals. For example, the properties of lithium resemble those of
sodium that occurs eight elements later in a list of the elements ordered by atomic number. After another
eight elements, potassium has properties also resembling those of lithium and sodium.
9.9. If the atomic volume of rubidium was missing from the plot of atomic volumes given in Problem 9.8,
one could interpolate its value from those of potassium and cesium. Roughly, potassium has a volume of
45 while cesium is about 70. The average of these is about 58, which is very close to the actual atomic
volume of rubidium.
59
Thallium [Xe] ↑ ↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑__ ___ ___
6s 4f 5d 6p
9.13. Uuo, element-116, is a chalcogen. Starting with Rn, its abbreviated orbital diagram follows:
[Rn] ↑ ↓ ↑ ↓ ↑ ↓ ↑ ↓ ↑ ↓ ↑ ↓ ↑ ↓ ↑ ↓ ↑ ↓ ↑ ↓ ↑ ↓ ↑ ↓ ↑ ↓ ↑↓ ↑_ ↑_
7s 5f 6d 7p
Its most prevalent oxidation state is most likely +4.
*9.17. Slater's rules are listed in Table 9.1. (a) Ne has the electronic configuration 1s22s22p6. An electron
occupying the 3s orbital will be shielded by a factor of 0.85 by the eight electrons in the 2s and 2p orbitals
and by a factor of 1.00 by the two electrons in the 1s orbital. Therefore,
(b) On the other hand, a 2p electron being ionized from neon will be shielded by a factor of only 0.35 by
the other seven electrons in the 2s,2p group and by a factor of 0.85 by the two inner core 1s electrons.
Therefore,
Again we see that the effective nuclear charge attracting an incoming electron to a noble gas such as neon
is very small (but not zero) while the Zeff holding a valence electron against ionization is very large (but
not 8 as calculated in Problem 9.16).
9.19. Effective nuclear charge is the nuclear charge experienced by a valence electron. From lithium to
neon, the number of shielding electrons remains the same (2), while the actual nuclear charge increases
from +3 to +10. therefore, the effective nuclear charge (= Z- σ) increases from +1 to +8.
*9.21. For the purposes of calculating the effective nuclear charge using Slater's rules, the electronic
configuration of calcium is written as follows: 1s22s22p63s23p64s2.
9.23. The electronic configurations and Zeff's of Al, Al+, Al2+, and Al3+ are as follows:
Al 1s22s22p63s23p1 Zeff = 13 - 2(0.35) - 8(0.85) - 2(1.00) = 3.50
+ 2 2 6 2
Al 1s 2s 2p 3s Zeff = 13 - 1(0.35) - 8(0.85) - 2(1.00) = 3.85
60
Al2+ 1s22s22p63s1 Zeff = 13 - 8(0.85) - 2(1.00) = 4.20
Al3+ 1s22s22p6 Zeff = 13 - 7(0.35) - 2(0.85) = 8.85
Based on these results, we expect that the ionization energies will gradually increase for Al, Al+, and Al2+
and then be much larger for Al3+.
*9.25. As can be seen by close inspection of the plot, the 3s, 3p, and 4s orbitals all have small but
significant probabilities of placing electrons very close to the nucleus. That is, these orbitals penetrate
through the inner-core electrons to the nucleus just a little better than does a 3d orbital. (nf orbitals, not
shown in the figure, have an even smaller probability of placing electrons close to the nucleus.)
Therefore, Slater's rules give a smaller contribution to the shielding constant for orbitals inside an (ns,np)
group than they do for orbitals inside an (nd) or (nf) group.
9.27. Ionization energy: the amount of energy required to completely remove an electron from a neutral,
gaseous atom (or ion). Horizontally, ionization energies increase because Zeffs increase. Vertically,
ionization energies decrease down a group because the electrons to be removed are farther and farther
away from the same Zeff (as calculated assuming σ is the number of inner shell electrons).
*9.29. P [Ne]3s23p3 The ionization energy is less for sulfur because the fourth 3p elec-
2 4
S [Ne]3s 3p tron is paired with one of the others. Therefore, this 3p electron,
being repelled by its partner electron, is easier to remove than might normally be expected on the basis of
trends in effective nuclear charge.
9.31. To see the trends in electron affinities, it helps to have the electron configurations to refer to.
Al [Ne]3s23p1
Si [Ne]3s23p2
P [Ne]3s23p3
As the effective nuclear charge increases from Al to Si to P, we expect the electron affinities to increase in
magnitude. However, at phosphorus the incoming electron would have to be paired with an electron
already occupying a 3p orbital. The extra electron-electron repulsion involved in this interaction makes
the electron affinity of phosphorus of lower magnitude than expected.
9.33. C [He]2s22p2 The electron affinity of nitrogen is less than that of carbon be-
2 3
N [He]2s 2p cause the electron being added to nitrogen must be paired with an
electron already occupying the 2p orbital. The extra electron-electron repulsion involved in this
interaction makes the electron affinity of nitrogen of lower magnitude than expected.
9.35. The polarizing power, in this case of a cation, is the ability to induce a dipole moment in a
neighboring anion (or atom). The greater the cationic charge, the greater the pull it has on the electron
cloud of the anion and the more easily a dipole moment can be induced in that anion. Also, the closer the
cation can get to the anion, the greater its ability to induce a dipole moment. The center of the positive
charge of a smaller cation can get closer to a neighboring anion than that of a larger cation, so decreasing
the radius of cation increases its polarizing power.
9.37. Beryllium chloride should be more covalent than magnesium chloride because the charge density of
beryllium (Z+/r+ = 4.9, see Figure 9.14 for radii) is greater than that of magnesium (Z+/r+ = 2.8) and
therefore the polarizing power of the former cation is greater. The Be2+ distorts or polarizes the electron
cloud of the Cl- increasing the likelihood of orbital overlap or covalent character in BeCl2.
61
Noting how similar the values of charge density are for the beryllium and aluminum cations, one would
expect that BeCl2 might be very similar to AlCl3, that is, that they would have similar degrees of covalent
character.
9.39. The planar molecular layers of graphite are held together by pi bonds formed by the parallel overlap
of 2p orbitals. Because silicon atoms are larger than carbon atoms, this pπ-pπ overlap is much less
effective. Silicon is characterized by strong σ bonds but weak pπ bonds.
9.41. Nitrogen atoms can form strong π bonds because they are so small. Phosphorus, on the other hand
is significantly larger and therefore pπ-pπ overlap is much less effective. Phosphorus is characterized by
strong σ bonds but weak pπ bonds.
9.43. Nitrogen only forms compounds such as nitrogen trichloride whereas phosphorus, arsenic, and
antimony can form both tri- and pentachlorides because nitrogen does not have readily available d orbitals
and therefore cannot form compounds in which the central atom exhibits an expanded octet. P, As, and
Sb do have available nd orbitals which can participate in the bonding in the compounds of these heavier
elements. Specifically, P, As, and Sb can form dsp3 hybrid orbitals and readily form the pentachlorides.
9.45. Oxygen only forms compounds such as OF2 but sulfur, selenium, and tellurium form the
hexafluorides because the oxygen does not have readily available d orbitals and therefore cannot form
compounds in which the central atom expands its octet. S, Se, and Te do have available nd orbitals,
which can participate in the bonding in the compounds of these heavier elements. Specifically, S, Se, and
Te can form d2sp3 hybrid orbitals used in the bonding of these hexafluorides.
9.47. Carbon only forms compounds such as CCl4 but tin forms polyatomic anions such as SnCl62-
because the carbon does not have readily available d orbitals and therefore cannot expand its octet. Tin
has available 5d orbitals that can participate in the bonding in SnCl62-. Tin forms SnCl2 because of the
inert pair effect. The cost in energy required to ionize the two 5s2 electrons in tin is sometimes not repaid
by forming the two additional Sn-Cl bonds.
9.49. The inert pair effect refers to the fact that the ns2 electrons going down a group (3A, 4A, 5A
principally) become more stable and less readily ionized. This leads to an increased stability of the n-2
oxidation state where n equals the group number. The ns2 electrons are less readily ionized because
ionization energies increase somewhat after an nd10 or nf14 subshell is filled. (The d10 or f14 electrons do
not effectively shield succeeding electrons from the nucleus very well and therefore the electrons outside
these filled subshells "feel" a greater than expected effective nuclear charge.) At the same time that IE is
slightly increasing or not decreasing as much, the M-X bond energies are decreasing going down the
groups because the bonds get longer and weaker. The combination of higher than expected IEs and lower
bond energies means that the cost in energy required to persuade the ns2 electrons to participate in bonds
is not fully repaid when bonds are formed. Therefore the elements lower in these groups often do not
form the extra two bonds as their lighter congeners do.
9.51. When moving from mercury to indium to germanium to phosphorus to oxygen, one crosses the
metal-nonmetal line. Going from bottom left to top right in the periodic table means that the elements
move from being metals (Hg, In) to metalloids (Ge) to nonmetals (P, O).
62
Chapter 10
Hydrogen and Hydrides
63
Chapter 10 Objectives
64
Solutions to Odd-Numbered Problems
10.1. “Ylem” is the word Aristotle used to describe the substance out of which all the universe was
created. Today we tend to use a word such as “singularity” to describe the nature of the universe before
the big bang or what is referred to in the text as the “expansion of ylem”. The big bang is the accepted
scientific theory for how the universe came into being. For reasons not known, the ylem or singularity, at
a definite point in time, exploded to create the very fabric of space and, eventually, the universe as we
know it. The first elements to appear were hydrogen and helium. Gradually, as these swirling clouds
began to cool and coalesce together due to gravitational forces, the hydrogen started to sequentially fuse
to produce elements as heavy as iron. So the first stars started to “burn” hydrogen and lighted up the
blackness of space.
11
10.3. 5B 5 protons, 6 neutrons
17
8O 8 protons, 9 neutrons
60
27Co 27 protons, 33 neutrons
239
94Pu 94 protons, 145 neutrons
Δm = Σm(reactants) - Σm(products)
= 4(1.007825) - [4.0015 + 2(5.488 x 10-4)]
= 0.0287 u
*10.9. While Robert Boyle was, according to Asimov, the first chemist to collect a gas and demonstrate
that the volume of a gas is inversely related to its pressure, no mention is made about his work with
hydrogen. Even though others (including Boyle) had worked with hydrogen before him, Henry
Cavendish is credited with the discovery of this element because, to quote Asimov, he "was the first to
65
investigate its properties systematically."
10.15. The atomic weight or mass of an element is the weighted average of a collection of its isotopes.
In this case,
AWH = 0.99985(1.007825) + 0.00015(2.0140) = 1.00798u
10.17. Temperature is a measure of mean kinetic energy, which is given by ½mv². The heavier D2O
molecules move slower than the lighter H2Os and therefore need a higher temperature to achieve
sufficient velocity to escape from the surface of the solid or the liquid, that is, to melt or boil.
10.19. The electrolysis of water first produces H2 and O2 gases. Although naturally occurring water
also contains small amounts of D2O and HDO, these are electrolyzed to D2 (and O2) slower because the
heavier D+ cation travels more slowly to the electrodes. The result is that the concentration of D2O
increases in a sample of water as it is being electrolyzed. As D2O has a greater density than H2O, the
overall density of the water sample increases during the process of electrolysis.
*10.21. First we can calculate the grams of D2O per L of ordinary water.
3 3
8 ⎛ 1000 m ⎞ ⎛ 100 cm ⎞ ⎛ 1 mL ⎞ ⎛ 1 L ⎞
3 20
(3.2 x 10 km ) ⎜ ⎟ ⎜ ⎟ ⎜ 3 ⎟ ⎜ ⎟ = 3.2 x 10 L
⎝ km ⎠ ⎝ m ⎠ ⎝ 1 cm ⎠ ⎝ 1000 mL ⎠
Finally we are able to calculate the grams of D2O in the oceans of the world.
⎛ 0.172 g D 2 O ⎞
(3.2 x 1020 L) ⎜ 19
⎟ = 5.5 x 10 g D2O (whew!)
⎝ L water ⎠
66
10.23. Assume 1 mole of each substance:
Assuming ideal behavior, the calculated densities are very close to the actual.
10.25. Only the hydrogen atoms bound directly to oxygen atoms will be replaced with deuterium when
mixed with heavy water, D2O. This is because the polar O-D bonds of deuterium oxide will interact
with the polar O-H bonds of the glucose but not with the essentially nonpolar C-H bonds.
10.27. The allies support an undercover mission to destroy a heavy water plant under Nazi control in
Norway. The allies were concerned that the heavy water could be used as a moderator in a possible Nazi
effort to produce an atomic bomb.
10.33. Lise Meitner was an Austrian-Swedish physicist who, in 1906, was the first woman to receive a
Ph.D. in physics at the University of Vienna. She was a pioneer in the field of radioactivity for more
than 30 years, most of them working with Otto Hahn in Germany. Immediately after the first world war,
they announced their discovery of protactinium, the 91st element. When Hitler came to power,
Meitner, a Jew, was forced to leave Germany and took a position in Sweden. Hahn wrote to her that
he had some somewhat surprising evidence that the bombardment of uranium with neutrons
apparently yielded the element barium. Meitner, working with her cousin, Otto Frisch, wrote a paper
in which they calculated that this experimental result was due to the fission of uranium to produce
both barium and krypton. Element 109 was named Meitnerium in honor of this pioneering woman of
nuclear physics.
235
10.35. 92U + 10n ─→ 96
37Rb + 13855Cs + 210n
232
10.37. 90Th + 10n ─→ 233 Th
90 ─ β-→ 233
91Pa + 0
-1e ─ β-→ 233
92U + 0
-1e
113 1
10.39. 48Cd + 0n ─→ 11448Cd + γ
10 1
5B + 0n ─→ 42He + 73Li
67
10.43. +
sp3
H+ sp3 O
H O
H
H H
H
with its very large charge density and
polarizing power, the proton severely H3O+
distorts the sp3 orbital of water forcing
overlap and covalent character
In the process of forming a salt such as NaF, we see that the formation of F-(g) is an exothermic process
and therefore will make a negative (and therefore favorable) contribution to the ΔH°f of such alkali metal
fluorides. On the other hand if a saline hydride such as NaH is formed, the formation of the
corresponding H-(g) is endothermic and does not make a favorable contribution to the ΔH°f of these
hydrides. If such hydrides are to form, they must involve highly electropositive metals that have low
ionization energies. Such metals will take little energy to ionize and will still have negative lattice
energies and therefore have negative standard heats of formation.
Z+ Z- M ⎛ 1⎞ (+1)(−1)(1.748) ⎛ 1⎞
10.47. Uo = 1389 ⎜1 − ⎟ = 1389 ⎜1 − ⎟ = - 682 kJ/mol
ro ⎝ n⎠ 3.05 ⎝ 7⎠
68
The high degree of covalent character causes the actual (Born-Haber) lattice energy to be much higher in
magni-tude than that derived from the Kapustinskii equation. See the text for further discussion of these
ideas.)
*10.55. Adding these three equations together yields the net reaction H2O(g) ─→ H2(g) + ½O2(g)
The heats of reaction for the three reactions can be calculated as follows:
(1) ΔH = ΔH°f [H2(g)] + 6ΔH°f[HCl(g)] + ΔH°f[Fe3O4(s)] - 3ΔH°f[FeCl2(s)] - 4ΔH°f[H2O(g)]
= 0 + 6(-92.3) + (-1118.4) - 3(-341.8) - 4(-241.8) = 320.4 kJ/mol
(2) ΔH = ½ΔH°f [O2(g)] + 3ΔH°f[H2O(g)] + 3ΔH°f[FeCl3(s)]
- ΔH°f[Fe3O4(s)] - 3/2ΔH°f[Cl2(g)] - 6ΔH°f[HCl(g)]
= ½(0) + 3(-241.8) + 3(-399.5) - (-1118.4) - 3/2(0) - 6(-92.3) = -251.7 kJ/mol
(3) ΔH = 3/2ΔH°f [Cl2(g)] + 3ΔH°f[FeCl2(s)] - 3ΔH°f[FeCl3(s)]
= 3/2(0) + 3(-341.8) - 3(-399.5) = 173.1 kJ/mol
The sum of these heats is ΔH1 + ΔH2 + ΔH3 = 241.8 kJ/mol
The heat of the reaction H2O(g) ─→ H2(g) + ½O2(g) can also be calculated as follows:
ΔH = ½ΔH°f [O2(g)] + ΔH°f[H2(g)] - ΔH°f[H2O(g)]
ΔH = ½(0) + (0) - (-241.8) = 241.8 kJ/mol
(Standard heats of formation vary somewhat from source to source, so your values may not be exactly the same as those given
here.)
10.57. High temperatures ensure high atomic or nuclear velocities and kinetic energies. This kinetic
energy, at the moment of impact of a collision, is largely converted to the potential energy needed to get
over the energy of activation of the reaction. High temperatures also increase the number of atomic or
nuclear collisions which will serve to increase the rate of these reactions. One significant difference
between chemical and nuclear reactions is the magnitude of the energy of activation. The very large
repulsions between nuclei make Eas for nuclear reactions very large indeed.
69
Chapter 11
Oxygen, Aqueous Solutions, and the Acid Base Character of
Oxides and Hydroxides
11.1 Oxygen
Discovery
Occurrence, Preparation, Properties, and Uses
11.2 Water and Aqueous Solutions
The Structure of the Water Molecule
Ice and Liquid Water
Solubility of Substances in Water
The Self-Ionization of Water
11.3 The Acid-Base Character of Oxides and Hydroxides in Aqueous Solution
Oxides: Survey and Periodic Trends in
Oxides in Aqueous Solution (Acidic and Basic Anhydrides)
The E-O-H Unit in Aqueous Solution
An Addition to the Network
11.4 The Relative Strengths of Oxo- and Hydroacids in Aqueous Solution
Oxoacids
Nomenclature of Oxoacids and corresponding salts (Optional)
Hydroacids
11.5 Ozone
11.6 The Greenhouse Effect and Global Warming
70
Chapter 11 Objectives
71
Solutions to Odd-Numbered Problems
11.3. Of the major components of air (N2, O2, H2O, Ar), only O2 will react with NO to produce NO2. Air
is approximately 20 percent oxygen while "dephlogisticated air" is, of course, 100 percent oxygen.
therefore, "dephlogisticated air" would have consumed four or five (depending on his experimental
accuracy) times as much NO as "common air."
NO(g) + ½O2(g) ─→ NO2(g)
15
11.5. 8O ─ β+→ 0
+1e + 157N
11.11.
(a) NH3
H N H N
H H
H
o
H 107.5
(b) SO3 O
μnet= 0
O S O O S O O S O S
O o O
O O O 120
11.13. A lone pair of electrons is confined by (or is under the influence of) only one nucleus whereas a
bonding pair is confined by two nuclei. The lone pair is therefore freer to spread out and occupy more
space.
72
*11.15. If every zinc and sulfur atom of the wurtzite structure (Figure 7.22d) were replaced by an oxygen
of a water molecule (with hydrogen atoms bridging among oxygens), the wurtzite structure would become
the ice structure (Figure 11.3).
11.17. Of CH4, CHF3, CH3OH, glucose, and CH3COOH, only the last three have hydrogen atoms bonded
to an electronegative FONCl atom, in this case, oxygen. Only the hydrogen atoms covalently bonded to
the oxygen atoms could participate in hydrogen bonds. In CHF3 the hydrogen atom is not bound to the
fluorine atom but rather to the nonFONCl (how about that for a word?) carbon atom.
Ice floats because its structure contains large hexagonally shaped holes. Thus it contains much
open space and is light. (A poem could be written about what it would be like to be in one of those open
spaces!) When ice melts, water molecules break off the ice structure and wander into some of the holes.
Therefore, dear EM, liquid water contains less open space and is heavier than ice. The lighter ice rises to
float upon the heavier liquid. (Dear readers: I know you can do better than I did. I would love to see the
various short paragraphs that you all come up with. You'll be famous; I might put your paragraph in the
next version of this Solutions Manual! (If there is next version.) Submit your entries to the author at
Department of Chemistry, Allegheny College, Meadville, PA 16335.
11.21. The boiling points of the Group 7A hydrides (HF, HCl, HBr, HI) should, in the absence of
hydrogen-bond effects, gradually increase because the molecular weight (and therefore the number of
electrons) increases in that direction. The more electrons there are, the greater the chance of
instantaneous dipole-induced dipole (London) forces. The greater these London forces the higher
temperature is needed to vaporize the substance.
11.23. Carbon dioxide, while non-polar, has individual bond dipole moments that can interact with the
polar water. Therefore CO2 is reasonably water-soluble. Sulfur dioxide is a polar molecule and interacts
even more with the polar water. Ammonia is a polar molecule that interacts with water molecules by
strong (for intermolecular forces) hydrogen bonds. Ammonia is also roughly the same shape as a water
molecule (with only an additional hydrogen atom) that fits nicely into the existing structure of liquid
water. Therefore, ammonia is very soluble in water.
*11.25. O2 is nonpolar and does not appreciably dissolve in polar water. The water molecules prefer-
entially hydrogen-bond to each other and exclude the dioxygen molecules. (Although, of course, given
the abundance of aquatic life, some of these molecules must dissolve in water.) NO, by virtue of the fact
that the electronegativity of oxygen is slightly greater than that of nitrogen, is slightly polar and therefore
more soluble in water. NO2 is a much more polar molecule possessing a significant permanent dipole
moment. Therefore, it is significantly more soluble in liquid water. The structure of the resulting
solution is shown below.
73
H
O
H
H
O
H
H H
O O H O
H H H
N H
O O O
H
H H O free water
O O H H
H
H
11.27. Glucose has 5 -OH groups and also an oxygen atom in the ring. These 6 polar groupings can
interact with water molecules and therefore make glucose soluble. A linear hydrocarbon, on the other
hand, is nonpolar. The water molecules will therefore prefer to hydrogen bond among themselves and
exclude (and therefore not dissolve) this solute.
H
*11.29. O
H
H
H H O H
H O H H
O O 1-
O
O
H 3+ H H
Co N
H O O
O O
H
H O H H H
H H O O H
74
11.33. In aqueous solution, the equilibrium among hydronium ions, hydroxide ions, and water
molecules must always be satisfied. That is, Kw = [H3O+(aq)][OH-(aq)] must always be equal to 1.0 x
10-14. Therefore, if [H3O+(aq)] is raised, then it follows that [OH-(aq)] must be lowered such that Kw is
still equal to 1.0 x 10-14.
O
δ− O
H H
75
11.43. (One resonance structure of SO2 is used here for clarity.)
H H
_
−
δ O O O
S δ+ H2O + H3O+
H S S
δ+ H H
O O O O O O
δ−
11.45. δ−
O
2-
Sr2+ O Sr2+ + 2OH-
H H
+
δ
11.47. A polar X-H bond (in which X is a highly electronegative atom) would readily interact with a
polar heavy water molecule, D2O. In the course of this interaction, the H of the X-H bond could be
exchanged with a deuterium atom. However, a non-polar C-H bond of a hydrocarbon is not polar enough
to be attracted to the a polar heavy water molecule and therefore cannot be deuterated.
11.49. Sulfuric acid has two non-hydroxyl oxygen atoms as well as two hydroxyl groups (-OH) bound
to the central sulfur atom. The SO2(OH)2 representation better portrays this situation.
11.53. (a) HClO3 > HIO3 due to the higher electronegativity of the chlorine
(b) H3AsO4 > H3SbO4 due to the higher electronegativity of the arsenic
(c) H3PO3 > H3AsO3 due to the higher electronegativity of the phosphorus
(d) HSO4- > HSeO4- due to the higher electronegativity of the sulfur
11.55. (a) HClO2 HBrO2 > HBrO due to additional nonhydroxyl oxygen atom
HClO2 > HBrO2 due to the more electronegative central atom
(b) HClO4 H2SO3 > H2SeO3 due to the more electronegative central atom
HClO4 >> H2SO3 due to the more electronegative central atom and
(c) H3PO4 H3AsO4 > H3AsO3 due to the extra nonhydroxyl oxygen atom
H3PO4 > H3AsO4 due to the more electronegative central atom
76
11.59. (a) HSeO3-
(b) BrO2-
(c) H2AsO3-
(d) IO4-
*11.61.
O
Cl I
δ+ δ−
O H O
O
−
O δ O δ−
H δ+
+
Hδ
perchloric acid iodous acid
(b) Perchloric acid would be the stronger because it has two additional oxygen atoms to withdraw
electron density from its O-H bond. In addition, the electronegativity of chlorine is greater than that of
iodine also helping to make the O-H bond of HClO4 more polar and more susceptible to attack by water
molecules.
(c) The acid anhydride of perchloric acid is dichlorine heptoxide: Cl2O7 + H2O ─→ 2 HClO4. The
acid anhydride of iodous acid is diiodine trioxide: I2O3 + H2O ─→ 2 HIO2.
11.63. HCl is a stronger hydroacid than H2S because while the H-Cl and H-S bonds are about the same
length and strength, the H-Cl bond is the more polar and the more susceptible to attack by polar water
molecules.
*11.65. Electronegativity differences are not the only effect in determining acid strengths. The length
and strength of H-X bonds are also very important. For example, H-F bonds are more polar than H-Cl
bonds but the latter are significantly longer and weaker making HCl a stronger hydroacid than HF.
11.67. What articles did you find? Can anyone say that the greenhouse effect has actually started to
lead to global warming? Have any other gases started to challenge carbon dioxide as the primary
greenhouse gas? Have we actually started to slow the increase of the output of any of these gases to the
atmosphere? Has this action led to any type of economic slowdown in the United States or other
developed countries?
*11.69. What articles did you find? The Kyoto protocol was a tentative agreement among industrialized
countries to try to reduce the level of greenhouse gases released to the atmosphere. Is it still viable?
What countries have actually ratified the protocol? What countries have not? What are the primary
issues that the national governments cite as standing in the way of their ratification? Is there any
evidence that steps taken have actually reduced the level of greenhouse gases that the world releases to
the atmosphere?
77
Chapter 12
Group 1A: The Alkali Metals
Chapter 12 Objectives
• briefly relate how and by whom the alkali metals were discovered
• rationalize the trends in radii, ionization energies, electron affinities, and electronegativities of
the group
• describe the general nature of the hydrides, oxides, hydroxides, and halides of the group
• describe and represent the uniqueness of lithium in the group
• describe and represent the diagonal relationship between lithium and magnesium
• define and use the concepts of oxidation, reduction, oxidizing agent, reducing agent, and
standard reduction potential
• describe the role of the standard hydrogen electrode in defining standard reduction potentials
• describe and represent the relationship among standard reduction potential, change in free
energy, and the spontaneity of a reaction
• predict the spontaneity of an oxidation-reduction reaction by analyzing its net reduction
potential
• explain the trends in the reduction potentials of the alkali metals
• explain why the lighter alkali metals are less reactive than the heavier
• describe and represent the general preparation, structure, and uses of hydrogen peroxide
• describe the occurrence and uses of superoxides
• describe the application of various alkali metals as fertilizers, treatment for bipolar disorders,
reducing agents, battery components, and agents for chronometric procedures
• rationalize the properties of alkali/alkaline earth metal liquid ammonia solutions in terms of
the solvated electron
• describe and give several examples of electrides and alkalides
78
Solutions to Odd-Numbered Problems
*12.3. According to my dictionary, a voltaic pile, named after Alessandro Volta, is a device that produces
current electricity, as distinguished from static electricity. So a voltaic pile is a name for one of the first
types of battery.
12.5. Melting point (or freezing point) depression is a so-called colligative property, dependent only
upon the number of solute particles present in a solution. Adding some CaCl2 provides other particles
(ions, in this case) that make it more difficult to freeze out the "solvent," in this case sodium chloride. In
order to freeze out the sodium chloride, a lower temperature must be achieved. Turning this argument
around means that the melting point of NaCl is also lowered.
223 4
12.7. 87Fr —α→ 2He + 21985At
*12.9. In each of the plots (shown on the next page) the rate of increase (of radii) or decrease (of the
other properties as plotted) slows down at rubidium. Rubidium is the first alkali metal after the filling of
the first period of transition metals. The electrons in the filled 3d10 sub-shell do not shield the succeeding
electrons as well from the effective nuclear charge. Rubidium therefore is a little smaller and has higher
values of ionization energy and electronegativity, and absolute value of electron affinity than otherwise
might be expected.
2.5 450
2.0 400
1.5 350
Li Na K Rb Cs Fr Li Na K Rb Cs Fr
79
elecron affinity (kJ/mol) electronegativity
(Pauling)
-70 1.2
-60 1.0
-50 0.8
-40 0.6
-30 0.4
Li Na K Rb Cs Fr Li Na K Rb Cs Fr
*12.15. Sodium nitride would be of greater ionic character than lithium nitride. Lithium has a greater
charge density and polarizes a relatively large anion like N3- to produce a significant degree of covalent
character.
12.17. LEORA stands for "loses electrons oxidized reducing agent." That is, if a substance loses
electrons its oxidation state increases and we say it is oxidized. The electrons it loses go to another
substance, which is in turn reduced. The substance that is oxidized then is serving as a reducing agent.
GEROA stands for "gains electrons reduced oxidizing agent." In this case, the substance gains electrons,
which causes a decrease in its oxidation state, and we say it is reduced. The electrons that it gains must
come from another substance, which in turn is oxidized. The substance that is reduced then is serving as
an oxidizing agent.
*12.23. The heats of hydration of the gaseous alkali metal cations would be negative. The formation of
ion-dipole forces among the cations and water molecules would be an exothermic process. Because the
charge densities of the cations decrease going down the group, the heats of hydration would become less
negative in that direction. Water molecules would be farther and farther away from the centers of charge
80
and the interactions would be become weaker going down the group.
12.25. Hydrogen peroxide should be very soluble in water due to the formation of hydrogen bonds
among the O-H groups and lone pairs of H2O2 and the water molecules.
12.27. Based on the ideas we have discussed under the uniqueness principle, the O-O bond distance in
H2O2 is considerably shorter than the corresponding S-S bond distance in H2S2. This longer bond
distance lets the lone pairs on the two sulfur atoms rotate by each other freely so that there is no
significant hindered rotation in dihydrogen disulfide.
Under standard state conditions, H2O2 would not oxidize Co2+(aq) to Co3+(aq).
12.33. In order to decide whether sodium metal could be used to reduce Al3+ to aluminum metal, we need
to calculate the E° of the following equation:
*12.35. (a) When H2O2 acts as an oxidizing agent, the oxidation state of the oxygen atoms in the molecule
is reduced from –1 to the –2 found in water.
(b) 1 [H2O2(aq) + 2H+(aq) + 2e- ─→ 2H2O(l) ]
1_[ 2I-(aq) ─→ I2(s) + 2e- ]__________________
H2O2(aq) + 2H+(aq) + 2I-(aq) ─→ 2H2O(l) + I2(s)
12.37. As shown below, the standard reduction potentials increase in the order oxygen, dichromate,
permanganate, and then hydrogen peroxide. This means that, under standard state conditions, hydrogen
peroxide is the best oxidizing agent of these four while oxygen is actually the worst. All four, however,
are excellent oxidizing agents.
O2(g) +1.23V
Cr2O72-(aq) +1.33V
MnO4-(aq) +1.51V
81
H2O2(aq) +1.77V
12.41. When a person inhales oxygen from and exhales carbon dioxide and water vapor into breathing
equipment based on potassium superoxide, the reaction is put into motion. Removing oxygen shifts the
net reaction, shown in Equation (12.21c), to the right as does supplying carbon dioxide. The more CO2
supplied and the more O2(g) removed by the user, the more the equipment responds to his or her needs.
12.47. Potassium-argon dating is based on the beta plus decay of potassium 40 to argon 40 gas. When
volcanic magma hardens to form a crystal structure from which argon gas cannot escape, the gas starts to
accumulate within the crystal. If the rock is left undisturbed, it can eventually be crushed in the
laboratory to release the argon gas that then can be monitored quantitatively. Knowing the half-life of
the beta plus decay, the amount of Ar 40 measured can be directly linked to the volcanic event. When
various remains are found in such volcanic rock, they too can be linked to the time when the volcanic
rock formed.
135
12.49. 55Cs ─β-→ 0
-1e + 13556Ba
12.51. 12-crown-4, shown below, is not quite as large as 18-crown-6 and therefore might not as readily
accommodate the large cesium cation.
O O
CH2
CH2 CH2
CH2
CH2
O O
CH2 CH2
CH2 CH2
CH2 CH2
CH2
12.53. 2,2,2-crypt is just the right size to bind to the sodium cation. The larger Cs+ does not fit in the
cage of this molecule while the smaller Li+ slips right through it.
82
Chapter 13
Group 2A: The Alkaline Earth Metals
83
Chapter 13 Objectives
84
Solutions to Odd-Numbered Problems
13.1. Limelight: a brilliant light created by the oxidation of lime and formerly used in theaters to throw an
intense beam of light upon a particular part of the stage. (Limelight is actually the result of heating
calcium oxide, CaO, to incandescence with a very hot hydrogen/oxygen or acetylene/oxygen torch. [See
J. Chem. Educ., 64(4), 306 (1987) for further information.]
13.5. The Greek "barys" meaning "heavy" is the source of the name of baryta, the oxide of barium that
has a high density. It would seem likely that the same Greek name was used to designate baryons, the
heavier subnuclear particle compared to hadrons.
*13.7. First we need to find out what weight 0.01% of seawater is. This is how much magnesium will
have to be removed.
3 3
9 ⎛ 1000 m ⎞ ⎛ 100 cm ⎞ ⎛ 1.025 g seawater ⎞ ⎛ 0.01 g Mg ⎞
3
(1.5 x 10 km ) ⎜ ⎟ ⎜ ⎟ ⎜ 3 ⎟ ⎜⎜ ⎟⎟ = 1.5 x 1020 g Mg
⎝ km ⎠ ⎝ m ⎠ ⎝ 1 cm seawater ⎠ ⎝ 100 g seawater ⎠
Now we can calculate how long it would take to consume the above weight of magnesium.
⎛ 1 1b ⎞ ⎛ 1 ton ⎞ ⎛ yr ⎞
1.5 x 1020 g Mg ⎜⎜ ⎟⎟ ⎜ ⎟ ⎜⎜ 6
⎟⎟ = 1.7 x 106 yrs, i.e., between 1 and 2 million
⎝ 454 g ⎠ ⎝ 2000 lb ⎠ ⎝ 100 x 10 tons ⎠
years
85
13.17. No, barium has a very low ionization energy and therefore should readily be ionized when
heated.
13.19. We need to see if calcium will reduce water. The half reactions will be as shown below.
The reaction in which calcium reduces water is thermodynamically spontaneous under standard state
conditions.
*13.21.
ΔHred
Mn+(aq) + ne- M(s)
ΔHhyd ΔHatom
Sum of n IEs
Mn+(g) M(g)
As mentioned in the start of Section 13.2, the standard reduction potential for beryllium is not the most
negative in its group as is lithium within the alkali metals. The reason for this difference, it was cited in
the third paragraph [starting with "Presumably (here we go again)..."] of Section 13.2, is "because the
energy required to ionize the beryllium to the +2 state is not fully compensated for by the energy
released when the Be2+ is hydrated." Here we have an opportunity to test the above hypothesis. Note
that it takes 2136 kJ [= (899+1757) - 520] more to ionize the two electrons of beryllium than the one of
lithium. Further note that only 1975kJ [= 2494 - 964] more energy is released when Be2+ is hydrated
than when Li+ is. So the above statement comparing the ionization energies with the energies of
hydration has been shown to be true.
*13.23. δ−
O
δ+ H2O
2+
H Ca H 2H H Ca2+(aq) + H2(g) + 2OH-(aq)
13.25. Picture calcium hydroxide as containing two Ca-O-H units as shown below.
86
δ+ δ- δ+ δ- δ+
H---O---Ca---O---H
The most polar bonds in this structure are those between the calcium and the oxygen atoms. The partial
charges caused by the larger difference in electronegativity between calcium and oxygen (as opposed to
between hydrogen and oxygen) are shown in a larger font. When this compound is placed in water, the
polar water molecules will attack the more polar sites within the molecule, that is, the Ca-O bonds. The
calcium-oxygen bonds will be broken producing Ca2+ and OH- ions in solution. It follows that this
compound will be basic and should be written as Ca(OH)2, calcium hydroxide, rather than H2CaO2,
which might be referred to as "calcic acid."
13.27. According to my dictionary, formality is defined as "something done merely for form's sake."
Referring to a separate Be2+ ion is something we do for form's sake. That is, we write this ion in this
form because its similar to that used to write other metallic cations. However, Be(II) compounds are
highly covalent due to the high charge density of the Be2+ cation so its separate existence as a free ion is
highly doubtful. That is, the Be2+ is "really a formality."
H H
2-
H O O
: O:
H : O : Be : O : H Be Be H
H O
O O
: O: O
H O H O
H
H H
All O-Be-O bond angles would be 109.5o; All Be-O bonds would be sp3-sp3;
all H-O-Be bond angles would be somewhat all O-H bonds would be sp3-s
less than 109.5o
*13.31. As we know from the diagonal effect, the aluminum +3 cation will be much like the beryllium
+2 cation. Both ions have large charge densities and will form more covalent compounds than we might
otherwise expect. Therefore, we might predict that AlCl3 will not be as soluble in water as we would
expect. (It turns out, however, that AlCl3 is quite water-soluble.) We also would predict that it will be
more soluble in non-polar organic solvents than otherwise might be expected. This last prediction is, in
fact, quite true as this compound is soluble in carbon tetrachloride and ether. Being electron deficient,
aluminum chloride will act as an electron-pair acceptor, that is, as a Lewis acid.
87
HfCl4 + 2Mg(s) ─Δ→ Hf(s) + 2MgCl2
When x moles of sodium carbonate dissolve in 1L of water, 2x moles of Na+ and x moles of CO32-are
produced. The solubility product, Ksp, will be as follows.
13.47. Equations (13.22) are not redox. The oxidation states of the various elements do not change in
the course of these reactions.
88
Chapter 14
The Group 3A Elements
Chapter 14 Objectives
• briefly state how and by whom the Group 3A elements were discovered
• rationalize the trends in radii, ionization energies, electron affinities, and electronegativities of
the group with particular emphasis on the anomalies in these properties shown by the heavier
elements
• describe the general nature of the group oxides, hydroxides, and halides
• list and briefly rationalize the ways in which boron is different from its heavier congeners
• list and briefly rationalize how the chemistry of the heavier Group 3A congeners is organized
by the inert pair effect
• describe the relationship between the general chemical nature of the borides and their
applications
• describe the general molecular nature and a few of the applications of ortho-, meta-, and
perborates
• list and briefly rationalize several applications of aluminum and its alloys
• list and briefly rationalize several applications of alums and alumina
• describe the safety and health hazards that accompanied the discovery of the borohydrides
• describe the nature of three-center, two-electron bonds
• draw and rationalize semi-topological diagrams of the simple boranes
• represent and rationalize the preparations and major reactions of the boranes
• describe and represent several electron-deficient compounds other than the boranes
89
Solutions to Odd-Numbered Problems
14.1. (a) Gay-Lussac and Thénard's preparation of boron: 6K(s) + B2O3(s) ─Δ → 2B(s) + 3K2O(s)
(b) Wöhler's preparation of aluminum: AlCl3(s) + 3K(s) ─Δ → Al(s) + 3KCl(s)
14.7. (a) Periodic law: (i) atomic radii increase whereas ionization energies, electronegativities, and (the
magnitudes of) electron affinities generally decrease going down the group; (ii) all the elements have
three valence electrons.
(b) Uniqueness principle: (i) the B3+ cation does not exist as a separate entity – if it did, it would be
very small and have a correspondingly high charge density. Because its polarizing power would be high,
the +3 oxidation state is only found in covalent compounds. (ii) The electron affinity of boron is less than
that of aluminum. This anomaly is attributed to the fact that boron is so small making it more difficult to
add an electron to this atom than expected on the basis of the usual trends in size and effective nuclear
charge.
14.9. Acid-base character: (i) B2O3 is an acidic anhydride whereas Tl2O is a basic anhydride. (ii)
Aluminum hydroxide, Al(OH)3, is amphoteric acting as either an acid or a base depending on the
circumstances.
14.11. We would expect the atomic radii to increase down the group because the electrons occupy larger
and larger orbitals. The actual values show that the expected trend is observed. Thallium, however, does
not have a very much larger radius than indium because its 6p electron experiences a slightly greater
effective nuclear charge then expected due to the relative inability of the filled d and f subshells to shield
it from the nuclear charge.
14.13. If boron trichloride were to be an ionic compound and therefore be written as B3+Cl-3, the highly
polarizing (charge density = 12.0, a very large value) B3+ ion (that exists only in a formal sense) would
severely distort the chloride ion resulting in a large degree of covalent character. In the final analysis,
BCl3 is best thought of as a covalent compound.
14.15. Boron oxide reacts with water to produce boric acid that is characterized by 3 B-O-H units in
which the O-H bonds are (just slightly) more polar than the B-O bonds. Although one might suspect that
polar water molecules would attack at least one of these O-H bonds and split it to produce H+ and H2BO3-
ions, this turns out not to be the case. Instead B(OH)3 is an acid in the sense explained in the solution to
Problem 14.14. Indium oxide, on the other hand, does react with water to produce an E-O-H unit in
which the E-O bond is clearly more polar and more susceptible to attack by water molecules. Therefore,
the In-O-H unit yields hydroxide ions in aqueous solution and indium oxide is considered to be basic.
90
14.19. In BF4-, the boron is sp3 hybridized and there is no chance for pπ interactions. In BF3, however,
there is an opportunity for the filled p
orbitals of the fluorine to donate
electron density to the unfilled, 2p
unhybridized p orbital of the
F -
boron. Such a pπ-pπ interaction sp3-p 2p 2p 2 F
makes the B-F bond stronger and 3 2 sp -p
p-sp p-sp
shorter. B F B 2p
F 2
sp3-p F sp -p
sp3-p F
F
14.21. This diagram is shown in Figure 14.6. The carbons and boron are sp3-hybridized while the
fluorines use either sp3 hybrids or just native p orbitals. The hydrogens, of course, use 1s orbitals.
14.23. Thallium is a metal and therefore does not tend to form the covalent bonds that characterize the
M2X6 structures. In addition, as per the inert pair effect, thallium usually forms compounds of general
formula TlX.
14.25. In order to determine the ΔG° of Tl3+(aq) + Tl(s) going to Tl+(aq), we need to use the various half
equations and accompanying standard reduction potentials that are available to us.
Yes, this reaction would be spontaneous. Tl+(aq) is more stable (under standard state conditions) than is
Tl3+(aq).
Note that the reaction to Tl+(aq) is spontaneous (E° = 0.33v) but that to Tl3+(aq) is not (E° = -0.72V).
14.29. There are 4 B12 [ = 8(1/8) +6(1/2)] in the unit cell. (Note that the diagram, for purposes of clarity,
does not show the B12 units in the back faces or the back left corner of the cube.) There are also 4 Sc
atoms [ = 12(1/4) + 1] in the unit cell. (Again, the diagram omits the M's found in back edges and in the
91
center of the cube.)
14.31.
3-
O O O 2-
O
B B
O B
O O
B O
B
O
O
The hybridization of the boron atoms is sp2. All O-B-O bond angles are 120°. B-O-B bond angles are
somewhat less than 109.5°.
14.33. The diagrams for these two anions are found in Figure 14.13 (d) and (e). In perborate, the O-B-O
angles are all 109.5° while all the others are somewhat less than 109.5°. Both the oxygen and boron
atoms are sp3 hybridized. In borax, the boron atoms at the top and the bottom of the figure have O-B-O
angles of 109.5° and are sp3 hybridized. The borons on the left and right of the figure have O-B-O angles
of 120° and are sp2 hybridized. All the oxygen atoms are sp3 hybridized. The H-O-B bond angles are
somewhat less 109.5°.
14.35. Pure aluminum metal is not very strong structurally so it cannot be used for such things
as aircraft frames or automobile engines. A copper alloy is used for aircraft while a Cu/Si
alloy is used for automobile engines.
From the E°'s and ΔG°'s, we see that under standard state conditions, it is easier to oxidize aluminum than
it is iron.
14.39. When AlCl3 is dissolved in water, the hydrated Al(H2O)63+ cation is formed. When four
equivalents of OH- are added, each one removes a hydrogen ion from a water attached to the Al3+ ion to
produce [Al(OH)4 (H2O)2]-. No Al-O bonds are broken during this process.
92
14.41. Given the structure of Al2Cl6 and the multiple HO Cl OH
lone pairs on a hydroxide ion, the structure given at
right might be a reasonable one for Al2(OH)5Cl⋅ 2H2O.
M M
The two waters of hydration might be hydrogen-bonded
to the OH groups.
HO O OH
H
14.49. In going from B6H62- to B5H9 to B4H10 a boron atom is removed from a closo octahedron to form a
nido square pyramid and then another is removed to produce the arachno structure.
14.51. One of the easiest ways to make diborane in the laboratory is to react boron trifluoride with
sodium hydride.
8BF3 + 6NaH ─→ 6NaBF4 + B2H6
This is quite different from the method that Stock used which was to react magnesium boride with
hydrochloric acid to produce a mixture of various boranes. After laboriously separating the highly
93
reactive boranes from each other, B4H10 was gently heated to decompose it to diborane.
*14.53.
H H
H H Be
H H H H
B Be B
H H B B
H H H H
H
H
*14.55. B5H8- _
H H
Available electrons: Distribution of electrons:
B B
5B x 3e- = 15e- 5 B-H = 10e- H
8H x 1e- = 8e- 3 B-H-B = 6e-
B
(-) 1e- 3 B-B = 6e- H H
24e- 1 BBB = 2e-
24e- 20e-
B B
There would be two additional resonance structures. H H
H
3
14.57. The carbon and boron atoms use sp hybrids. The interior H-B-H bond angles are probably close
to 95o as in diborane. The exterior H (or CH3)-B-H angles are probably greater than 109.5o.
B B B B
H H H H H CH3
H3C H
H
B B
H H CH3
94
14.59.
H
H3 CH3 H H
H3C
C C
Al Al
H3C C CH3 Al Al
H3
In general, the bonding in Al2(CH3)6 is similar to that in diborane with aluminum atoms replacing borons
and methyl groups replacing hydrogen atoms. All the carbon and aluminum atoms are sp3 hybridized.
The aluminum-carbon-aluminum bond is a 3c-2e bond with the carbon and one of the aluminums
providing the electrons (as shown by shading in the figure).
95
Chapter 15
The Group 4A Elements
96
Chapter 15 Objectives
• briefly describe the form in which some of the Group 4A elements were known to the ancients
• briefly relate how and by whom the remaining Group 4A elements were discovered
• outline the general manner in which the periodic law, uniqueness principle, inert pair effect, and
the acid-base character of oxides are applicable to this group
• explain why catenation is much more prevalent in the carbon hydrides than it is in those of the
heavier congeners, particularly silicon
• compare and contrast the incidence of pπ-pπ bonding in carbon compounds with pπ-dπ bonding
in those of silicon
• compare and contrast the bonding in trimethyl- and trisilylamines
• describe why pπ-dπ bonding becomes important in Group 4A chemistry and will become more so
going farther right in the third period
• describe the general nature of the group oxides, hydroxides, and halides
• compare and contrast the major allotropes of carbon
• describe the discovery and the modes of preparation of the fullerenes and nanotubes
• give some examples of elements that have been incorporated into fullerenes of various sizes
• list three types of reactions that the fullerenes undergo and give an example of each
• describe the structures, properties, and applications of the nanotubes
• briefly describe the role of the Group 4A elements in tin disease, radiochemical chronometry, and
tracing methods
• describe several applications of carbon oxides; ionic, covalent, and interstitial carbides; carbon
disulfide; and cyanides
• discuss some major applications of lead compounds including the storage battery
• discuss the general toxicology of lead compounds
• list, represent, and discuss the variety of silicates including the relationship of submicroscopic
structures to macroscopic properties
• describe the structure and uses of aluminosilicates
• describe the nature of intrinsic, n-type, and p-type Group 4A semiconductors
• represent and describe the preparation of semiconductor-grade silicon
• describe the general nature of common, quartz, laboratory-grade, crystal, colored, photochromic,
and fiber glasses
97
Solutions to Odd-Numbered Problems
15.5. Amorphous (re: Webster's New Universal Unabridged Dictionary, Deluxe 2nd Edition, Simon &
Schuster, NY, 1983) means having no regular structure, noncrystalline; formless, characterless,
unorganized, vague. This definition implies that Berzelius isolated an impure, poorly characterized form
of silicon.
15.7. Going down the group, the ionic radii increase fairly regularly except for lead. Here's another
example in which the electrons in filled d and f subshells do not shield valence electrons from the nuclear
charge as effectively as electrons in other subshells do.
15.9. The ionization energies, like the ionic radii and electronegativities, behave fairly regularly going
down the group. For the most part, it gets progressively easier to ionize the valence electrons of the
Group 4A elements. As usual, the exception comes in the heavier elements, particularly lead in this case.
Once again, we see that the valence electrons must experience a greater than expected effective nuclear
charge due to the relative inability of electrons in filled d and f subshells to shield succeeding electrons
from the nuclear charge.
15.11. LiH, while not as saline as the other hydrides in its group, is still of significant ionic character.
BeH2 is a polymeric, electron-deficient hydride showing significant covalent character while B2H6 is the
most famous borane also with largely (but atypical) covalent character. With methane, CH4, we reach an
almost fully covalent hydride characterized by good ole normal two-center, two-electron bonds.
15.13. Given the elaborate element-to-element bonds in the allotropes of boron, it is most certainly
appropriate to include boron as an element that shows catenation.
H H H H H H H
(a) H Si Si Si Si H H Si Si Si H
H H H H H H
H Si H
98
H H H H H H H H
(b) H Si Si Si Si H H Si Si Si Si H
H H H H H H H H
H Si H
H Si H H
H H
H Si Si Si H
HH H
Si H
H
15.17. The alcohol can react more readily with silane because the oxygen of the alcohol can donate one
of its lone pairs into one of the empty d orbitals of the silicon atom and readily form a low- energy
transition state. Since no low-energy d orbitals exist in the carbon of methane, this mode of attack is not
open and methane reacts less readily.
15.19.
H H H H H H H H H H H
H Ge Ge Ge Ge Ge Ge H H Ge Ge Ge Ge Ge H
H
H H H H H H H H H H
H Ge H
H Ge H
H H H
H
H
H Ge Ge Ge Ge H
H Ge H
H H H H H H H H
H H H
H Ge H
H Ge Ge Ge Ge H H Ge Ge Ge Ge Ge H
H
H H H H H H H
H Ge H H Ge H
H H
99
15.21. Ionic character of Li, Be, B, C oxides
15.23. The double bonds found in the C3O2 suboxide are made possible by pπ-pπ bonds between the
carbon and oxygen atoms. Due to ineffective overlap, the larger elements beyond the second period do
not form stable pπ-pπ bonds. Therefore a silicon analog of C3O2 does not exist.
15.25. The direct combination of elemental germanium and tin with chlorine yields the tetrachlorides.
Other measures must be taken to produce the dichlorides.
(a) GeCl4 + Ge ─→ 2GeCl2
Ge + 2Cl2 ─→ GeCl4
(b) Sn + HCl(g) ─→ SnCl2 + H2
Sn + 2Cl2 ─→ SnCl4
15.27. The carbon halides are not electron deficient as are most of the Group 3A halides. Therefore, the
carbon halides need not form bridged structures in order to achieve an octet of electrons around the central
atom.
15.29. PbCl2 would be more soluble as it is the more ionic. The charge density of Pb2+ is less than that of
Pb4+ giving the latter a greater polarizing power and an increased ability to form more covalent
compounds.
15.31.
1 [2Cl-(aq) ─→ Cl2(g) + 2e- ] E° = - 1.36V; ΔG° = -(2)(96.5kJ/v)(-1.36v) = 262kJ
1 [PbO2(s) + 4H+(aq) + 2e- ─→
_______________ Pb2+(aq) + 2H2O(l) ] E° = +1.46V; ΔG° = -(2)(96.5kJ/v)(1.46v) = -282kJ
2Cl-(aq) + PbO2(s) + 4H+(aq) ─→
Cl2(g) + Pb2+(aq) + 2H2O E° = +0.10V; ΔG° = -20kJ
100
15.35. The chlorine atom is sp3 hybridized. Each of these four _ +
hybrid orbitals is used to form a single bond with an oxygen atom. +
One of these oxygen atoms is, in turn, singly bonded to a hydrogen Cl O
atom. The other three oxygen atoms do not have hydrogens _
+ _
bonded to them but rather form a second bond with the chlorine atom.
This second bond is formed using a 3d orbital of chlorine and a 2p 3d 2p
orbital of oxygen as shown at right. (The signs are the phases of the
orbitals.)
15.37. Charcoal is composed of very small pieces of graphite. The electrical conductivity of graphite
relies upon keeping its horizontal planes intact. (The conductivity is possible because of the mobility of
pπ electrons delocalized above and below a plane of carbon atoms in graphite.) If these planes are
broken into very small bits, the substance loses its ability to conduct electricity.
15.39. The fullerenes can be described as graphite sheets that are formed into spheres. They still have pπ
electrons delocalized above and below the plane, a situation that translates into delocalized pi electron
density both inside and outside the C60 sphere, for example.
15.41. On the website entitled “Fullerene Structure Library,” presented by MitsuhoYoshida, the largest
fullerene listed is C100 and the smallest is C20. Did you find any larger or smaller?
http://shachi.cochem2.tutkie.tut.ac.jp/Fuller/fsl/fsl.html (accessed July, 2001)
15.43. SWNTs are exceptionally strong materials while still being very light weight. Any application
where this combination of properties is important may well employ SWNTs. Such applications would
include aircraft, space craft, automobile and truck parts (SWNTs in a new generation of NASA Space
Shuttles); fibers, ropes and cables (a cosmic funiculaire is only the most spectacular of such applications);
bridge supports allowing longer spans then present day materials; and, of course, sports equipment!
SWNTs can also be excellent electrical conductors. Combined with their lightweight, they may be used
in a new generation of transmission power lines.
15.45. Tin disease is characterized by metallic (or white or β-Sn) changing to gray (or α-Sn) tin when the
metal is exposed to prolonged periods of temperatures below 55.8ºF. Gray tin has a diamond structure but
the single bonds holding it together are both longer and weaker and therefore it tends to crumble quite
easily. When metallic tin materials change to gray tin, they lose their metallic qualities. Tin organ pipes
in unheated European cathedrals, churches and priories are a good example where tin disease has been
devastating. Tin disease may have changed the course of European history when (in addition to the
harassment by defending Russian troops and their campaign of devastating the land as they retreated) the
tin buttons on the uniforms of Napoleon’s army crumbled away as he drove his troops toward Moscow in
the unusually cold winter of 1812.
15.47. One reason is that rocks do not take in carbon. Therefore there is no steady state concentration or
ratio of C 14 to C 12 in rocks. The second reason is that rocks are generally too old to be measured by C
14 dating. The half-life of C 14 is only about 5730 years, not a very long time compared to the age of
rocks, which is often in the millions of years.
15.49. Now we can see that radium will be found with uranium of which it is a radioactive daughter and
not necessarily with its congener barium.
101
*15.51. Each source of lead is the product of a different combination of three radioactive series. The lead
impurities derived from the combustion of coal will have a different set of isotopes than that set from a
smelter. A set of isotopes is, in essence, the signature of that particular source of lead. The set of lead
isotopes used in a smelter in Missouri is very likely to have a different signature than that of the lead used
in a Californian smelter.
15.53. “Supra” was a sweetener popular in Roman times. It was prepared by boiling down sour wines in
lead pans. The widespread use of this Roman sugar may have been responsible for spreading a low level
of lead poisoning throughout the Roman ruling class. The early signs of lead poisoning include anemia,
fatigue, headache, irritability, and psychological problems. Greater neurological damage can result from
higher levels of lead. Leaders with such symptoms would show less sound judgment than healthy ones.
Lead in paint and pottery could both be modern parallels of supra. Improperly glazed pottery that releases
lead into various liquids, particularly those with a mildly acidic character is a direct parallel. Children
who eat lead-containing paint chips is also quite similar, particularly because these chips are said to have a
sweet taste.
15.55. O O
O p-p sp2 - sp2
>120o
Cl C Cl C C
3 2
sp - sp sp2 - sp3
Cl Cl Cl
<120o Cl
15.57. The equation representing the overall reaction occurring in a lead storage battery shows sulfuric
acid as a reactant. If the battery had been used extensively and needed charging, a significant amount of
H2SO4 would have been consumed and the density of the electrolyte solution would be low.
*15.59.
*15.61. The AlP pair is isoelectronic with two silicon atoms. If we reformulate AlPO4 as AlO2PO2 we see
that AlPO4 is isoelectronic with two SiO2 units. Another way to look at this situation is that AlPO4 is SiO2
(quartz) with half of the silicon atoms replaced by aluminum and the other half replaced by phosphorus.
It stands to reason then that aluminum phosphate forms in quartzlike structures.
102
*15.63. Dear Aunt Emily,
So, as I was saying, aluminosilicates are made up of aluminum, silicon, and oxygen atoms. They
form structures with atomic- or molecule-sized holes in them. These structures also contain more
electrons than protons and therefore are negatively charged molecules, or what my professor calls
“polyatomic anions.” I know you’ve heard the term “hard water” but many people think this means it is
somehow literally harder than regular water. However, hard water is just an expression meaning regular
water that contains significant amounts of calcium, magnesium, and iron ions (atoms that have lost one or
more electrons to form positively charged “cations”). If not neutralized in some way, these hard water
ions can interfere with the cleansing action of soaps and detergents. (They also form a gummy solid with
hand and bath soaps – this is the stuff that “bathtub rings” are made up of.) Anyway, when the detergent
is added to hard water, the calcium, magnesium, or irons ions are attracted into the holes of the
negatively-charged aluminosilicates and we say the water is “softer”. Sodium carbonate is also a water
softener. Easily dissolved in water, it forms shiny crystalline precipitates with hard water ions and so
prevents them from interfering with soaps and detergents. (The precipitates containing the hard water
ions simply get thrown out with the wash water.) Some detergent manufacturers use only “suspended
sodium carbonate” (suspended in the sense that it is uniformly scattered throughout the product) to soften
water whereas others have been starting to use both sodium carbonate and aluminosilicates. It’s difficult
to know for sure, but perhaps using the combination of the two ingredients makes for an even better
detergent because there are then two ways to neutralize the effect of the hard water ions. This double-
barreled action would be particularly important in geographic areas where the water is particularly hard
and the consumer does not have a water softener installed in the house. Anyway, I hope you enjoyed and
understood my explanation of how aluminosilicates and sodium carbonate work in detergents. Thanks for
asking about how things are going in my inorganic chemistry course.
15.65. Gallium arsenide, GaAs, is isoelectronic with germanium and therefore would also serve as an
intrinsic semiconductor. We can prepare n-type semiconductors from GaAs by doping it with atoms such
as germanium or selenium that carry one more electron than gallium or arsenic, respectively. Similarly,
p-type semiconductors are prepared by doping GaAs with atoms such as zinc or germanium that carry one
less electron than gallium or arsenic, respectively.
15.67. When sodium carbonate or limestone (CaCO3) is heated (as they would be in the preparation of
glass) they liberate carbon dioxide gas and sodium oxide and calcium oxide, respectively.
103
Chapter 16
Group 5A: The Pnicogens
104
Chapter 16 Objectives
• briefly describe the relationship between some of the Group 5A elements and the ancient
practice of alchemy
• briefly relate how and by whom the Group 5A elements were discovered
• outline the general manner in which the periodic law, uniqueness principle, inert pair effect, and
the acid/base character of oxides are applicable to this group
• explain how the phosphazenes summarize the relative π-bonding abilities of nitrogen and
phosphorus
• compare and contrast the hydrides of the nitrogen, phosphorus and arsenic
• discuss the role of pπ-dπ bonding in phosphorus chemistry
• represent the structural similarities among P4, P4O6, and P4O10
• discuss and represent the structures of phosphoric acid, ortho-phosphate, and the various
condensed phosphates
• discuss and represent the structures of phosphorous acid, ortho-phosphites and the various
condensed phosphites
• discuss the structures, preparations, and properties of the phosphorus halides
• describe and draw the structure of borazine
• briefly describe the oxidation state, structure, properties, history, preparations and reactions of
1) ammonia
2) hydrazine
3) nitrous oxide
4) nitric oxide
5) nitrous acid and nitrites
6) nitrogen dioxide
7) nitric acid and nitrates
• briefly discuss three methods of nitrogen fixation
• explain why nitrogen compounds are often components of high explosives; give three examples
• briefly explain how automobile air bags work
• briefly relate the history and hazards of matchmaking
• briefly explain the role of phosphates in fertilizers, food processing, soft drink formulations, and
dental hygiene
• compare and contrast the general causes and characteristics of London and photochemical smog
• describe the daily production and abatement of both the primary and secondary pollutants that
constitute photochemical smog
105
Solutions to Odd-Numbered Problems
16.1. The name pnicogen means "choking producer." Obviously if we breathed in just nitrogen and not
"common air" we would choke. If phosphorus is burned in air, it consumes the oxygen and makes the
air a "choker." The same could be said of Priestley's test for the goodness of air, reacting it with nitric
oxide. The result would be an "air" that would serve as a choker. Arsenic, the famous poison, and its
compounds could also be loosely viewed as chokers as they cut off life.
*16.5 The mouse consumed a good portion of the oxygen (dephlogisticated air) in the air by respiration.
Burning a candle and phosphorus would consume any left over oxygen. A strong alkali (potassium or
sodium hydroxide) would react with the carbon dioxide originally in the air plus that generated by the
mouse and the burning candle. Some of these processes are represented by the following equations:
C(s) + O2(g) ─→ CO2(g)
P4(s) + O2(g) ─→ P4O6(s) (oxygen is the limiting reagent)
2NaOH(s) + CO2(g) ─→ Na2CO3(s) + H2O(l)
16.9. The nitrogen of N(SiH3)3 has a filled 2p orbital that can be used to overlap the empty 3d orbitals of
the silicon atom. The resulting pπ-dπ bond of this planar molecule is shown in Figure 15.4. The filled
3p orbital of the phosphorus atom of P(SiH3)3 is not large enough to form an effective pπ-dπ bond with
the silicon atoms. While the 3d orbital of the phosphorus might be able to stretch to form a dπ-dπ bond
with the silicon, neither of these 3d orbitals has any electrons in them so no π bond can form.
16.11. There are two possible resonance structures for the isocyanate ion. (I) is favored as it places a -1
formal charge on oxygen, the most electronegative atom. Analogous phosphorus compounds are not
possible as this element is not capable of pπ-pπ bonding.
106
16.13. The arsenic atom is sp3 hybridized using its 4s and
4p orbitals. Each hybrid orbital overlaps with oxygen 2p orbital
orbitals (sp3 for the OH oxygens and sp2 for the non-
hydroxyl oxygen) to form a single bond. The shorter O
As-O bond is a double bond where the second pπ-dπ
bond is formed using the empty 4d orbital of arsenic and pπ-dπ 4d orbital
a filled 2p orbital of the oxygen. bond As
HO OH
16.15. Of NH3 and PH3, phosphine is the stronger acid because HO the P-H
bonds are longer and weaker than the N-H bonds of ammonia.
sp3 hybridized
16.17. Phosphoric acid (H3PO4) versus arsenic acid (H3AsO4):
Phosphorus is more electronegative than arsenic and therefore
the P would draw more electron density from the O-H bond then would the As. The O-H bond of H3PO4
would be more susceptible to attack by water molecules and H3PO4 would be the stronger acid.
H
16.25.
O O
H H
As H As H
O O
O O
O H
H
arsenic acid arsenious acid
16.27. (a) H3SbO3
(b) CuHAsO3
(c) NH4H2AsO4
107
16.31. E2O3(s) + 6HF(g) ─→ 2EF3(s) + 3H2O
2E + X2(g,l,s) ─→ 2EX3(s)
where E = As or Sb; X = Cl, Br, or I
*16.33. Borazine is shown in Figure 16.7 while the trimeric phophazene is shown in Figure 16.3(a).
The similarities include (a) alternating X (= B or P) and N in a 6-membered ring, (b) both have
delocalized X-N bonds, (c) nitrogen is sp2 hybridized in both compounds, and (d) all the π electrons in
both structures come from the 3 nitrogen atoms. The differences include (a) two chlorine atoms are
bonded to each phosphorus in P3N3Cl6 but there is one each on each of the three boron and nitrogen
atoms in B3N3Cl6, (b) the phosphorus is sp3 hybridized in its compound but the boron is sp2 hybridized
B
in the borazine derivative, and (c) the phosphorus uses its d orbitals for π bonding while the boron uses p
orbitals.
H N H
H H
N H
N H
H
H
N H
H
H
N
H
H N H
H
H
H
16.37. -3 +1 +6 -2 0 +1 -2 +3 -2
(NH4)2Cr2O7(s) ─→ N2(g) + 4H2O(g) + Cr2O3(s)
The nitrogen is oxidized from -3 to 0; the chromium is reduced from +6 to +3.
108
Yes, hydrazine could accomplish this reduction under standard state conditions.
H N
H
H
H O H
*16.47. Internet search for NO: What did you find? NO news is definitely still good news. In addition
to those uses given in this text, the following quote is from the “Nitric Oxide Homepage,”
<http://www.apnet.com/no/>, (accessed August 2001): “From diabetes to hypertension, cancer to drug
addiction, stroke to intestinal motility, memory and learning disorders to septic shock, sunburn to
anorexia, male impotence to tuberculosis, there is probably no pathological condition where nitric
oxide does not play an important role. Only recently (within the last 13 years) discovered as a product
of enzymatic synthesis in mammals, there are more than 32,000 scientific papers dealing with this
remarkable molecule with most of these published within the last five years.”
109
16.49.
sp2 - sp2
O N N O N N N N
sp2 - sp2 sp2 - sp2
<120o
O O O 2p-2p 2p-2p O
*16.51.
NO2+ NO2 NO2-
+ -
O N O O N O O N O
-
O N O O N O
N N
O N O N N
O O O O
The expected bond angles decrease as the nitrogen atom first adds a single nonbonding electron and then
a full lone pair.
16.55. Within nitrogen chemistry there are both excellent oxidizing agents (for example, HNO3) and
excellent reducing agents (for example, hydrazine). Therefore, it is an overgeneralization to claim that
all the good oxidizing agents are on the right side of the table and all the good reducing agents on the
left.
iron
*16.59. N2(g) + 3H2(g) ──────→ 2NH3(g) ΔH° = -92.6 kJ/mol
high T&P
High pressure is justified because it would favor the side (in this case the product side) with the fewer
moles of gases. Higher temperature would be justified thermodynamically only if this were an
endothermic reaction, which it is not. The high temperature must be necessary in order to increase the
rate of the reaction to an acceptable level. The iron is a catalyst that increases the rate but does not affect
the thermodynamic spontaneity of the reaction.
110
16.61. The oxidation state of the nitrogen atom in
hydroxylamineis –1. This compound will be very soluble
in water because the lone pairs of both the oxygen and O
nitrogen atoms as well as the hydrogen atoms themselves H
are capable of hydrogen bonding with water N H
molecules.
H
16.63. Ammonium nitrate, NH4NO3, as shown in Equation (16.52), can explode to produce dinitrogen
(with its strong N≡N bond), dioxygen (with its strong O=O bond), and water (with its relatively strong O-
H single bonds). The production of these strong bonds makes this reaction highly exothermic.
16.65. The double bonds of the phosphorus sulfides cannot be of the pπ-pπ type because this overlap is
not effective in the third period elements. These bonds cannot be of the dπ-dπ type either because the d
orbitals are empty in both of these elements. The bonds must be of the pπ-dπ type with each sulfur
providing two electrons in its 4p orbital to overlap with the empty d orbitals of the phosphorus atoms.
Note that the phosphorus atoms are sp3 hybridized and cannot provide the p orbitals.
*16.69. PO3F2- is isoelectronic with the orthophosphate ion, PO43-. One would speculate, then, that the
ion would be tetrahedral in structure.
16.71. Hydroxyl radicals serve as “reaction intermediates” in the production of photochemical smog.
They combine with the lower hydrocarbons to produce various methyl, ethyl, etc. radicals that, in turn,
can readily keep the oxidant-producing photochemical reactions going that facilitate the production of
smog.
111
Chapter 17
Sulfur, Selenium, Tellurium, and Polonium
112
Chapter 17 Objectives
• briefly relate how and by whom sulfur, selenium, tellurium, and polonium were discovered
• outline the general manner in which the periodic law, uniqueness principle, inert pair effect,
acid-base character of oxides, standard reduction potentials, and pπ-dπ bonding involving
elements of the second and third periods are applicable to the Group 6A elements
• summarize the preparations and properties of the non-catenated hydrides of sulfur and its
heavier congeners
• summarize the preparations and properties of the oxides and non-catenated oxoacids of sulfur
and its heavier congeners
• summarize the preparations and properties of the non-catenated halides of sulfur and its
heavier congeners
• discuss the major allotropes of sulfur in the solid, liquid, and gaseous phases
• give some examples and discuss the properties and structures of some catenated polycations
and anions of sulfur and its heavier congeners
• give some examples and discuss the properties, preparations, and structures of the catenated
halides and hydrides of sulfur and its heavier congeners
• give some examples and discuss the properties, preparations, and structures of catenated
sulfur-containing oxoacids and their corresponding salts
• give some examples and discuss the properties, preparations, and structures of some
representative sulfur nitrides
• describe the nature of sodium-sulfide batteries
• describe the role of selenium and tellurium in the Xerox process and in II-VI semiconductors
• describe the industrial preparation and some of the uses of sulfuric acid
• describe the causes, consequences, and possible control of acid rain
113
Solutions to Odd-Numbered Problems
17.1. Since gunpowder was introduced in the thirteenth century and matches soon after the discovery of
phosphorus in late seventeenth century by Brandt, these inventors most likely did not regard sulfur as an
element. Only in the first decade of the nineteenth century was sulfur so recognized.
210 4
17.3. 84Po ─α→ 2He + 20682Pb
17.5. The Zeff is essentially constant but atomic sizes increase down the group. Therefore, the atomic
radii increase, electronegativites decrease (electrons are attracted to positions farther from the Zeff) and
ionization energies decrease (electrons to be removed are also farther from the Zeff).
H2O has the highest boiling point due to the strong hydrogen bonds that characterize its inter-molecular
forces. Oxygen is significantly more electronegative than its heavier congeners due to its ability to attract
bonding electrons to positions much closer to its effective nuclear charge. Therefore O-H bonds are
much more polar than bonds between H and S, Se, and Te. It follows that compounds characterized by O-
H bonds are capable of forming the stronger hydrogen bonds and are higher boiling.
17.11. The acid strength should increase in the order H2S to H2Se to H2Te. The H-X bond strength
decreases down the group (because the bond length increases) and therefore the acids are readily
dissociated into H+ and HX- ions.
Given that H+ is a product, high acid concentrations would shift the position of equilibrium of this
114
reaction back toward the left. This is an example of Le Châtelier's Principle.
17.19.
O O
Structures with terminal S=O bonds
using pπ-dπ bonds are also possible S
here. O O
S
O O
O O O O
S S
O O O
S S
O O
O
O O
17.21. Sulfuric acid has one more nonhydroxyl-group oxygen atom withdrawing electron density from
the O-H bonds. This makes these bonds more polar and therefore more susceptible to attack by polar
water molecules. It follows that H2SO4 is the stronger acid.
17.23.
E° = - __ -241kJ__ = 0.31V
(8)(96.5kJ/V)
115
17.29. Sulfamide O
H
H
N H H
S
O S O N
N
H N O H
H H
17.31. The intermolecular forces in Te(OH)6, telluric acid, should be hydrogen bonds among adjacent O-
H groups.
17.35.
H H
H H 3
sp
O O O O O O
O O
O S O S O
S S S S
O O <109.5 o
O O O
O sp3 sp3
H H O O
O O
<109.5o
All the terminal S-O bonds could also be shown as double bonds involving pπ-dπ bonds. For simplicity,
they all are shown as single bonds.
*17.39. (a) The single bond energy of sulfur is greater than that of oxygen because, although the S-S
bond distances are longer and therefore, one might suspect, weaker than the O-O bonds, the repulsions
among the lone pairs of electrons on the oxygen atoms in a O-O bond make it a weaker bond than
expected. (b) The double bond energy of O=O is greater than that of S=S because the pi bond between
oxygen atoms is of the stronger (more effective overlap) pπ-pπ type while that between sulfur atoms is of
116
the dπ-pπ type.
17.41. Cyclohexasulfur, S6 S
S S
The 6-membered ring most likely exists in "chair"
and/or "boat" forms much like cyclohexane.
S S
S
17.43. Total electrons available in Te64+
6 x 6 - 4 = 32e- Te Te
The addition of H+ to the SO32- reactant forms "H2SO3" (sulfurous acid) which immediately breaks apart
to SO2(g) and H2O. The sulfur dioxide is driven off and the above equilibrium shifts to the left decreasing
the concentration of thiosulfate and increasing the amount of solid elemental sulfur present.
17.47.
Pb2+(aq) + 2e - ─→ Pb(s) ]1
2- 2- + -
2H2O + S2O4 (aq) ─→ 2SO3 (aq) + 4H (aq) + 2e ]1
Pb2+(aq) + 2H2O + S2O42-(aq) ─→ Pb(s) + 2SO32-(aq) + 4H+(aq)
*17.49. S4N4
S S
N N N N
-
4S = 24e
4N = 20e- S S S S
44e-
N N N N
S S
117
17.51. S4N4 (4x6) + (4x5) = 44e- two transannular S-S bonds needed
S82+ (8x6) - 2e- = 46e- one transannular S-S bonds needed
S8 (8x6) = 48e- no transannular S-S bonds needed
For S4(NH)4, there are (4x6) + (4x5) + (4x1) = 48e-, therefore we would predict that this cycloocta ring
with alternating S and N atoms should contain no transannular S-S bonds. The hydrogen atoms would be
single-bonded to the nitrogens.
*17.53. For O, EN = NO, nitrogen oxide, a stable, discrete odd-electron species best
represented as shown at right. This molecule is characterized by strong pπ-pπ
bonds typical of the second period elements (re: the uniqueness principle). For S,
EN =SN, the polymeric, fibrous material that acts as a one-dimensional metal. N O
The S-N bonds of this polymer are characterized by dπ-pπ, S-N bonds. Again
the nitrogen employs p orbitals to form π bonds while the sulfur uses d orbitals
to accept the electron density from the nitrogen.
*17.55. Silicon is an intrinsic semiconductor of the type covered in Chapter 15 (p. 401). It is not
surprising to expect that AlP is a III-V intrinsic semiconductor isoelectronic with Si (or 2Si).
17.57. roasting
2MS + 3O2 ────→ 2SO2(g) + 2MO
V2O5
SO2(g) + O2 ────→ 2SO3(g)
(as air)
17.61. Both wet and dry scrubbers work on the principle that adding calcium oxide (or calcium carbonate
that loses carbon dioxide to produce the oxide) to power plant effluents serves to convert sulfur dioxide to
calcium sulfite, CaSO3, and sulfur trioxide to calcium sulfate, CaSO4. In wet scrubbers, an aqueous
solution of the calcium oxide or carbonate is sprayed into the smokestack and the result is a difficult-to-
manage slurry of the sulfites and sulfates. In dry scrubbers, less water is used so that the excess is driven
off and the result is a dry mixture of the sulfites and sulfates.
*17.63. <109.5o
0 0 0
<109.5o
O S O H
S
O O
0
H O
0 O
>109.5 o
<109.5o
118
.
The Lewis structure gives formal charges of zero for all atoms. (Resonance structures with single S-O
bonds would also be important for this molecule.)
17.65. The burning of fossil fuels would still produce carbon dioxide, a major greenhouse gas. If we
were to continue to strongly rely on combustion of coal to produce our energies, enormous amounts of
this gas might accumulate in the atmosphere resulting in significant global warming.
119
Chapter 18
Group 7A: The Halogens
120
Chapter 18 Objectives
121
Solutions to Odd-Numbered Problems
*18.1. (a) Priestley’s isolation of hydrogen chloride gas: NaCl + HX ─→ HCl(g) + NaX, where HX
is a strong acid. He used mercury because HCl gas is soluble in water. (b) Scheele’s isolation of
chlorine gas: 4NaCl(aq) + 2H2SO4(aq) + MnO2(s) ─→ 2Na2SO4(aq) + MnCl2(aq) + 2H2O(l) +
Cl2(g). MnO2 is the oxidizing agent and NaCl is the reducing agent.
18.5. Cl AW = 35.45u
Br Predicted AW of Br = 35.45 + 126.9 = 81.2u
I AW = 126.9u 2
The actual AW of bromine is 79.9u. There is only a 1.6% error between the predicted and actual values.
These are very regular periodic trends. The melting points increase as the number of electrons (and
atomic weight) increase making for stronger intermolecular forces. The covalent radii increase as the
sizes of the individual atoms regularly increase down the group. The ionization energies regularly
decrease as the electrons to be ionized are farther and farther away from an approximately constant
effective nuclear charge.
18.15. Fluorine is thought to have an anomalously low electron affinity because of its very small size.
When an eighth electron is added to the valence shell of fluorine to produce a neon inert gas electronic
configuration, that incoming electron is severely repelled by the seven existing electrons occupying the n
= 2 shell. It is therefore more difficult to add the eighth electron than expected and the amount of energy
122
released is also less than expected.
*18.17.
ΔHored
1/2 F2(g) + e- F-(aq)
ΔH(g) ΔHhyd
EA
F(g) F-(g)
The above reaction is very thermodynamically spontaneous because (a) ΔH(g), corresponding to
breaking of the weak F-F bond of F2, is so low and (b) the ΔHhyd of F-(g) is so large and negative. The
latter is due to the very high charge density of F- leading to a very strong and exothermic interaction with
the polar water solvent.
Sulfuric acid is a strong enough oxidizing agent to convert bromides to bromine and iodides to iodine
but it is not strong enough to produce fluorine and chlorine from the fluorides and chlorides,
respectively.
Both of these reactions are spontaneous under standard state conditions. The hydrohalic acids are not
immediately converted to the halogens because the concentration or partial pressure of O2(g) is not great
enough in aqueous solutions.
H H
F F
H H
F
123
*18.25. 2 [ NO3-(aq) + 4H+(aq) + 3e- ─→ NO(g) + 2H2O ] E° = 0.96V
2[ 2Cl-(aq) ─→ Cl2(g) + 2e- ] E° = -2.87V
2NO3-(aq) + 8H+(aq) + 6Cl-(aq) ─→ 2NO(g) + 3Cl2(g) + 4H2O E° = -1.91V
Cl O Cl O Cl O
O Cl
Cl Cl O O
o o
<109.5 <109.5
*18.39. Equation (18.30) is a redox reaction with X2 being both the oxidizing and the reducing agent.
That is, X2 disproportionates to HOX and X-.
124
18.47. 1 [ BrO3-(aq) + H2O(l) ─→ BrO4-(aq) + 2H+(aq) + 2e- ] E° = -1.74V
+ -
1 [XeF2(aq) + 2H (aq) + 2e ─→ Xe(g) + 2HF(aq) ] E° = +2.64V
XeF2(aq) + H2O(l)(aq) + BrO3-(aq) ─→ Xe(g) + 2HF(aq) + BrO4-(aq) E° = +0.90V
18.59.
(a) F <90o
+
F F F
I I <120o
F F
F
I
<109.5o F
+ I
(b) I I I I
125
18.61. Fluorine-20 can be incorporated in small amounts into teeth and bones in the form of fluoro-
apatite, Ca10(PO4)620F2. For a given geographical area with a given amount of fluoride in the water
supply, a hominid should have a predictable amount of fluoride in his or her bones or teeth. Knowing
the isotopic abundance of fluorine-20, one could calculate the expected levels of F-20 in the teeth or
bones at death. After death, the amount of F-20 would decrease. Measurement of the existing level of
F-20 (by counting beta minus particles), combined with knowledge of the half life of F-20 would yield a
determination of the age of the sample.
18.63. Fluoridation is a good idea because there is significant evidence that it reduces the number of
dental caries in children without subjecting them to undue health risks. It is not a good idea, some
would argue, because it forces a medication on an entire population area whether they (a) want it or not
and (b) in the case of adults, they can significantly benefit from it or not.
126
to ozone. In the mid-70s, back when you and Uncle Tim had those wonderful suntans I have seen in
pictures – suntans due to the uv component of sunlight – chlorofluorocarbons (CFCs) were implicated to
pose a threat to the stratospheric ozone that shields us from receiving too much solar uv radiation. (Too
much of this powerful radiation is dangerous because it can cause skin cancer.) The theory proposed at
that time was that CFCs, very inactive in the troposphere (the part of the atmosphere where we live), are
eventually swept up into the stratosphere where the chlorine atoms are broken off by uv radiation and
start to destroy ozone. The theory proposed in the 1970s said that chlorine oxide, ClO, was an integral
part of that reaction system and the compound that actually reacted directly with the ozone, O3. (At that
time no one knew for sure if this was true even though CFCs were quickly removed from products such
as aerosol spray cans.) Figure 18.6, which plots data gathered in the 1980s as aircraft flew towards the
South Pole, shows the intimate connection between ClO and O3. Notice that the concentration of ozone
(represented in the upper light line of the graph) always decreases when the concentration of ClO (the
lower darker line) increases. These two lines are very nearly mirror images of each other(!) and this plot
was solid proof that ClO concentrations directly affect ozone concentrations – a chemical smoking gun if
there ever was one! Again, it was fun to “talk chemistry” with you, Aunt Emily.
18.71. The Antarctic gets colder than the Arctic and the Antarctic polar vortex is more stable. This
means that during the Antarctic winter, inert chlorine reservoirs can be readily set up from which active
ozone-destroying chlorine and chlorine compounds can be released in the polar Spring.
127
Chapter 19
Group 8A: The Noble Gases
Chapter 19 Objectives
You should be able to
• briefly relate how and by whom the noble gases were discovered
• outline the general manner in which the periodic law is applicable to this group
• briefly relate how Bartlett came to prepare the first compound of xenon
• discuss the preparations, properties and structures of some representative fluorides and
oxides of xenon
• give several examples of compounds of the noble gases other than xenon
• list a few representative uses of the noble gases
• relate and discuss the discovery and mechanism of radon as a major environmental health
problem
128
Solutions to the Odd-Numbered Problems
19.5. Assuming air to be 20% oxygen (O2) and 80% nitrogen (N2), its average molecular weight is
given by the following equation:
⎛ 1.78g Ar ⎞ ⎛ 22.4L ⎞
*19.7. ⎜ ⎟⎜ ⎟ = 39.9 g/mol
⎝ L ⎠ ⎝ mol ⎠
19.9 The ionization energies decrease going down the group because the electron to be ionized
becomes farther and farther away from an approximately constant effective nuclear charge.
*19.11. The effective nuclear charges felt by the valence electrons are indeed very large but the Zeff
felt by an incoming electron (that would occupy an ns orbital outside of the closed shell of valence
electrons) is very small. Therefore, these atoms do not attract free electrons.
19.13. The only intermolecular forces operating between xenon and water molecules in xenon
hydrates are London dispersion forces.
19.17. Radon would be more reactive toward such a strong oxidizing and fluorinating agent as PtF6
because it has a lower ionization energy than does xenon.
129
*19.23.
F -
F F
F Pt F F
Pt
F F
F
F
F
19.25. (b), (f), and (h) are consistent with the VSEPRT.
(b)
F F
F
Xe F Xe F
F o
F 90
F
(f) O
4-
O O
O O
Xe O Xe O
O O 90 o
O O
O
(h) O
90o
O F
F F
Xe F Xe F
F F o
90
F
130
(d) There would be nine pairs of electrons around the large xenon atom in the XeF82- anion.
Consistent with VSEPR theory, eight pairs would logically be dispersed in a square antiprism. The
ninth pair is theorized to occupy the spherical 5s orbital of xenon and not affect the geometry of the
other eight.
19.29. XeO3F2
F
O O
O O
Xe O Xe <120o
F F
O
F <90o
19.31. 129
53ICl2
-
─β-→ 0
-1e + 129
54XeCl2
Cl
Cl Xe Cl Xe 180o
Cl
*19.35. Xe=F double bonds are not likely because they require a +1 formal charge on the fluorine
atom. Xe=O double bonds are not forbidden because of formal charges but would involve dπ-pπ
bonding between a 6d orbital of xenon and a 2p orbital of the oxygen atom. The disparity in size
would make this 6d-2p orbital overlap not particularly effective.
19.43. Smokers are at a greater risk to the hazards of radon than nonsmokers because the
radioactive products (especially Po-218) of radon decay adhere to the smoke particles deposited
in smokers’ lungs.
132