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Descriptive Inorganic,

Coordination, and Solid


State Chemistry
2nd Edition

Glen E. Rodgers

Student Manual
Chapter 1 Objectives

The student should be able to

• explain what the realm of inorganic chemistry encompasses


• appreciate when chemistry first became recognized as a separate academic discipline
• appreciate when and how inorganic chemistry became established as a subdiscipline of
chemistry
• appreciate the role and some of the accomplishments of inorganic chemists in the latter half
of the nineteenth century
• explain the role of the quantum revolution in changing the nature of inorganic chemistry
• appreciate some of the major accomplishments of inorganic chemists in the first half of the
twentieth century
• appreciate some of the major accomplishments of inorganic chemists in the second half of
the twentieth century

1
Chapter 2
An Introduction to Coordination Chemistry

The sections and subsections in this chapter are listed below.

2.1 The Historical Perspective


2.2 The History of Coordination Compounds
Early Compounds
The Blomstrand-Jørgensen Chain Theory
The Werner Coordination Theory
2.3 The Modern View of Coordination Compounds
2.4 An Introduction to the Nomenclature of Coordination Compounds

Chapter 2 Objectives

You should be able to

• define some important terms used in coordination chemistry


• give a few examples of coordination compounds encountered in earlier courses
• put coordination chemistry into the historical context of the conceptual development of
atomic structure, the periodic table, and chemical bonding
• relate how the formulas and properties of early coordination compounds were but
incompletely rationalized by the Blomstrand-Jørgensen chain theory
• explain how Werner's coordination theory, with its concept of primary and secondary
valences, more completely rationalized the properties of early coordination compounds
• draw structural formulas for coordination compounds using both the Blomstrand-
Jørgensen chain theory and the Werner coordination theory
• explain how Werner established that the secondary valence of cobalt(III) is directed to the
corners of an octahedron
• work with a variety of coordination compounds involving monodentate, multidentate,
bridging, and ambidentate ligands
• name coordination compounds involving a variety of metals, ligands, and counterions

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.

2.9. (a) CrCl3·6H2O + 3AgNO3(aq) → 3AgCl(s) + Cr(NO3)3(aq) + 6H2O

(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.

2.13. There would be three possible isomers.

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

1,2,3 1,2,4 1,3,5

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

(b) Three trigonal prismatic geometrical isomers

4
Cl Cl Cl
Cl Cl Cl
Cl OH2 OH2

H2O Cl H2O
OH2 OH2 OH2
OH2 OH2 Cl

Two octahedral isomers

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.

Formula No. of ionic No. of geometric


nitrites isomers

[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

2.21 (a) Formulas

[Pt(NH3)4](SCN)2 (b), (i) tetraammineplatinum(II) thiocyanage


[Pt(NH3)3SCN]SCN (contains cation of highest charge)
[Pt(NH3)2(SCN)2]
NH4[Pt(NH3)(SCN)3]

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

(b) There would have been four structural isomers.

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

2.25. (a) hexaammineplatinum(IV) chloride


(b) (acetylacetonato)tetrakis(triphenylphosphine)nickel(II) nitrate
(c) ammonium trioxalatoferrate(II)
(d) tricarbonyldinitrosyltungsten(0)

2.27 (a) tris(ethylenediamine)iron(III) hexachloroiridate(III)


(b) amine(methylamine)silver(I) dichlorodinitritoplatinate(II)
(c) dichlorobis(ethylenediamine)vanadium(III) hexacyanoferrate(II)

2.29. (a) bis(ethylenediamine)cobalt(III)-μ-thiocyanato-μ-isothiocyanato-


bis(acetylacetonato)chromium(III) nitrate
(b) triaquacopper(I)-μ-diacetatotriaquacopper(I)
(c) diaquatris(thiocyanato)chromium(III)-μ-hydroxopentaamminecobalt(III) sulfate

2.31. (a) [Ag(CH3NH2)2]C2H3O2


(b) Ba3[CoBr2(C2O4)2]2
(c) NiCO[P(C6H5)3]3

2.33 (a) [Co(NH3)6][CuCl5]


(b) [Pt(C5H5N)4][PtCl4]
(c) [Pd(NH3)2(PPh3)2][Au(C2O4)2]2

(a) (b)
H
O O O

[(NH3)5Cr Cr(NH3)5]Cl5 [(NH3)2(en)Cr Co(NH3)4]Br6

2.35. O O

7
Chapter 3
Structures of Coordination Compounds

The sections and subsections of this chapter include

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

You should be able to

• distinguish among the various types of stereoisomers and structural isomers


• define, describe, test for, and be familiar with the nomenclature of chirality
• determine the number and types of and name stereoisomers commonly encountered in octahedral
coordination compounds
• describe the general approach to resolving isomers of ionic coordination compounds
• demonstrate how Werner forever laid to rest the idea that chirality was a property associated only
with carbon
• determine the number and types of and name stereoisomers commonly encountered in square
planar and tetrahedral coordination compounds
• appreciate and give examples of coordination compounds with coordination numbers other than
four or six
• define and give an example of fluxional five-coordinate compounds
• recognize and predict the incidence of coordination and ionization structural isomers
• describe, name, and predict the incidence of linkage isomers that occur with the common
ambidentate ligands

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

isomer is chiral. The 1,2,5 isomer is its nonsuperimposable mirror image.

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 +

Cl PPh3 H3N HN3 ONO py


Ir Cr Co
OC PPh3 H3N py
HN3 ONO

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.

(i) (ii) (iii)


a A
a B a B
A
A A

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

NO2 H2C NO2

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.

3.29. (a) potassium chloro(nitrilotriacetato)thiocyanatocobaltate(III)

(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.

3.39. [Cu(NH3)4][PtBr4], tetraamminecopper(II) tetrabromoplatinate(II)


[Cu(NH3)3Br][Pt(NH3)Br3], triamminebromocopper(II) amminetribromoplatinate(II)
[Pt(NH3)3Br][Cu(NH3)Br3], triamminebromoplatinum(II) amminetribromocuprate(II)
[Pt(NH3)4][CuBr4], tetraammineplatinum(II) tetrabromocuprate(II)

*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.

3.43. (a) [Pt(NH3)4Cl2]Br2: An ionization isomer would be [Pt(NH3)4Br2]Cl2, dibromotetraammine-


platinum(IV) chloride.
(b) [Cu(NH3)4][PtCl4]: A coordination isomer would be [Cu(NH3)3Cl][Pt(NH3)Cl3],
triamminechlorocopper(II) amminetrichloroplatinate(II).

*3.45. At least one of each type of isomer except optical is possible as shown below.

[Pd(NH3)4][Pd(NO2)4] tetraamminepalladium(II) tetranitropalladate(II)


↑ coordination isomer
[Pd(NH3)2(NO2)2] cis-diamminedinitropalladium(II)
↓ geometric isomer
[Pd(NH3)2(NO2)2] trans-diamminedinitropalladium(II)
↓ linkage isomer
[Pd(NH3)2(ONO)2] trans-diamminedinitritoopalladium(II)

*3.47. [Co(acac)2(NH3)(H2O)][Co(SCN)4] S-cis-bis(acetylacetonato)ammineaquacobalt(III)


optical isomer ↑ tetrathiocyanat0cobaltate(III)
[Co(acac)2(NH3)(H2O)][Co(SCN)4] R-cis-bis(acetylacetonato)ammineaquacobalt(III)
coordination isomer ↓ tetrathiocyanatocobaltate(III)
[Co(acac)2][Co(NH3)(H2O)(SCN)4] bis(acetylacetonato)cobalt(III)
geometric isomer ↓ cis-ammineaquatetrathiocyanatocobaltate(III)
[Co(acac)2][Co(NH3)(H2O)(NCS)4] bis(acetylacetonato)cobalt(III)
linkage isomer ↓ trans-ammineaquatetrathiocyanatocobaltate(III)
[Co(acac)2][Co(NH3)(H2O)(NCS)4] bis(acetylacetonato)cobalt(III)
trans-ammineaquatetraisothiocyanatocobaltate(III))

14
Chapter 4
Bonding Theories for Coordination Compounds

The sections and subsections in this chapter are listed below.

4.1 Early Bonding Theories


The Lewis Acid-Base Definition
Crystal Field, Valence Bond, and Molecular Orbital Theories
4.2 Crystal Field Theory
Shapes of 3d Orbitals
Octahedral Fields
Tetragonally-Distorted Octahedral and Square Planar Fields
Tetrahedral Fields
4.3 Consequences and Applications of Crystal Field Splitting
Crystal Field Splitting Energies versus Pairing Energies
Crystal Field Stabilization Energies
Factors Affecting the Magnitude of the Crystal Field Splitting Energies
Magnetic Properties
Absorption Spectroscopy and the Colors of Coordination Compounds

Chapter 4 Objectives
You should be able to

• explain how Lewis acid-base theory applies to coordination compounds


• define and use the effective atomic number rule for coordination compounds
• briefly outline how the valence bond, molecular orbital, and crystal field theories generally are
applied to coordination compounds
• qualitatively sketch out the shapes of the five independent 3d orbitals
• explain how the two dependent 3dz²-y² and 3dz²-x² orbitals are related to the 3dz² orbital
• explain in detail how the five independent 3d orbitals split in an octahedral field
• explain in detail the changes in the relative energies of the 3d orbitals when the z-axis ligands of
an octahedral field are gradually withdrawn to produce a tetragonally-elongated and ultimately a
square planar crystal field
• explain in detail how the five independent 3d orbitals split in a tetrahedral field
• describe the strong- and weak-field, low- and high-spin cases as applied to coordination
compounds
• calculate the crystal field stabilization energy (CFSE) in terms of the crystal field splitting (Δ) and
pairing (P) energies for any given dn case in an octahedral, tetrahedral, or square planar crystal
field
• explain how factors such as the type of field, the size and charge of the metal ion, and the size and
charge of the ligand should affect the magnitude of the crystal field splitting energy assuming a
completely ionic M-L interaction
• rationalize the degree to which the spectrochemical series can and cannot be explained by the
crystal field theory
• explain how admitting a certain degree of covalent character to the M-L interaction can be used to
better rationalize the spectrochemical series

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

4.1 Hydrogen ions:


(1) Arrhenius acid -- treats acids as substances that produce H+ in solution
(2) Brønsted-Lowry acid -- capable of transferring a proton (H+)
(3) Lewis acid -- H+ is an electron pair acceptor

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.

4.5. (a) Lewis base = hydroxide ion; Lewis acid = Zn2+


(b) Lewis base = water; Lewis acid = SO2 (Sulfurous acid is often better described as SO2·H2O
but also as OS(OH)2, a form that would necessitate a rearrangement after the initial Lewis acid-
base reaction.)
(c) Lewis bases = two ammonias; Lewis acid = Ag+

4.7. Metal electrons Ligand electrons Total Electrons Result


(a) Cu2+ 27 4 NH3 8 35 does not follow EAN
(b) Ag+ 46 2 NH3 4 50 does not follow
(c) Fe2+ 24 6 CN- 12 36 follows EAN
(d) Mo0 42 6 CO 12 54 follows EAN
(e) Fe3+ 23 3C2O42- 12 35 does not follow EAN

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.

4.11. (nodes = dashed lines)

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

3dxy 3dxz 3dyz

(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

3dxy 3dxz 3dyz


(b)
Estabilization = Edestabilization

2[(0.37Δ + (0.17Δ - x)] + (0.17Δ - x) = x + (0.83Δ + x)

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

4.35. Cr3+ 3; Co2+ 7; Pd4+ 6; Pt2+ 8; Cu2+ 9

4.37. d3 CFSE = 3(2/5 Δo) = 6/5 Δo


d8 CFSE = 6(2/5 Δo) - 2(3/5 Δo) = 6/5 Δo

4.39. (a) [Fe(CN)6]4- Fe2+ d6 low-spin: CFSE = 12/5 Δo - 2P


(low-spin chosen because the cyanide ligand is so high in the spectrochemical series)
(b) [Ru(NH3)6]3+ Ru3+ d5 low-spin: CFSE = 2 Δo - 2P
(low-spin because ammonia ligand is moderately high in the series and Ru3+ is large and
highly charged leading to a large crystal field splitting energy)
(c) [Co(NH3)6]3+ Co3+ d6 low-spin: CFSE = 12/5 Δo - 2P
(low-spin because ammonia ligand is moderately high in the series and Co3+ is highly charged
leading to a moderately high crystal field splitting energy)

*4.41.

ΔO
0.60ΔO
0.23 ΔO
0.40ΔO 0.43 ΔO

0.086 ΔO

d8 octahedral d8 square planar

CFSE = 6(0.40Δo) - 2(0.60Δo) CFSE = 4(0.428Δo + 0.086Δo) + 2(0.428Δo)


-1(0.228Δo) - 1(0.228Δo + Δo)
= 1.2 Δo = 1.456 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.

CFSE = 4(0.63Δ) - 2(0.11Δ) - 1(0.91Δ + 0.11Δ)


0.91Δ
= 1.28Δ

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.

4.49. Δ(Rh3+) > Δ(Co3+) > Δ(Co2+)


(a) (b)
3+
(a) The larger Rh allows for the fluoride ligands to approach more closely to the d orbitals without
steric hindrance.
(b) The more highly charged Co3+ draws the ligands in more closely and thereby splits the d orbitals
more than the Co2+.

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

4.57. μexptl # of unpaired Mn+ dm elect. spin state


(BM) electrons config.
[Mn(CN)6]4- 1.8 1 Mn2+ d5 t2g5 low-spin
[Mn(CN)6]3- 3.2 2 Mn3+ d4 t2g4 low-spin
[Mn(NCS)6]4- 6.1 5 Mn2+ d5 t2g3eg2 high-spin
[Mn(acac)3] 5.0 4 Mn3+ d4 t2g3eg1 high-spin

4.59. [CoI6]3- Co3+ d6 high-spin t2g4eg2 n = 4 μS = (4)(6) = 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.

4.65. (a) [Ni(H2O)2(en)2] ─ heat → [Ni(en)2] + 2H2O


(b) The [Ni(en)2] could be either tetrahedral or square planar in nature. As shown below, only the square
planar splitting could support the presence of a diamagnetic compound.

tetrahedral -- can only square planar can be paramagnetic


be paramagnetic or diamagnetic

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.

[Ni(H2O)2(deen)2]Br2 (blue) [Ni(deen)2]Br2 (orange)

R O Y G B I V increase in crystal R O Y G B I V
field splitting

absorbed transmitted transmitted absorbed

*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

The sections and subsections in this chapter are listed below.

5.1 A Brief Survey of Reaction Types


5.2 Labile and Inert Coordination Compounds
5.3 Substitution Reactions of Octahedral Complexes
Possible Mechanisms
Experimental Complications
Evidence for Dissociative Mechanisms
Explanation of Inert versus Labile Complexes
5.4 Redox or Electron Transfer Reactions
Outer-Sphere Mechanisms
Inner-Sphere Mechanisms
5.5 Substitution Reactions in Square Planar Complexes: The Kinetic Trans Effect

26
Chapter 5 Objectives

You should be able to

• recognize the various types of reactions that coordination compounds undergo


substitution (including hydrolysis and anation),
dissociation,
addition,
electron transfer (including oxidative-addition and reductive-elimination),
reactions of coordinated ligands
• write expressions for overall and stepwise equilibrium constants for a given substitution
reaction
• distinguish between and correctly use the kinetic terms labile and inert as well as the
thermodynamic terms stable and unstable
• write dissociative (D), associative (A), and interchange (I) mechanisms for substitution
reactions
• explain, when determining the rate law of a given reaction, how the concentration of a reactant
may be masked by certain experimental conditions
• cite evidence from rates of exchange of water molecules as well as anation and aquation
reactions, that substitution reactions of octahedral complexes most often follow a dissociative
mechanism
• discuss the contributions of metal size and charge, steric hindrance among ligands, overall
charge on the complex, and M-L covalent overlap to the energy of activation of the bond-
breaking, rate-determining step of a substitution reaction
• discuss the contribution of the change of crystal field stabilization energy to the energy of
activation of the bond-breaking, rate-determining step of a substitution reaction
• summarize why complexes of the first row transition metal ions, with the exception of Cr3+
and Co3+, are generally labile while those of most second and third row transition metal ions
are inert.
• describe outer-sphere electron transfer mechanisms and how their rates are a function of the
relative M-L distances in the reactants
• describe inner-sphere electron transfer mechanisms and how their rates are a function of the
polarizability of the bridging ligand
• describe the kinetic trans effect and rationalize it in terms of the polarizability of the trans-
directing ligand
• be able to use the kinetic trans effect to outline the synthesis of various square planar
complexes

27
Solutions to Odd-Numbered Problems

5.1. K1K2K3K4 = [{Cu(NH3)(H2O)3}2+] x _[{Cu(NH3)2(H2O)2}2+]__ x


[{Cu(H2O)4}2+][NH3] [{Cu(NH3)(H2O)3}2+][NH3]

___[{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]

K2 = __[Cr(CO)4(PPh3)2]__ β3 = K1K2K3 = [Cr(CO)3(PPh3)3]


[Cr(CO)5PPh3][PPh3] [Cr(CO)6][PPh3]3

K3 = ___[Cr(CO)3(PPh3)3]__
[Cr(CO)4(PPh3)2][PPh3]

5.5. K1 = [{Cr(H2O)4(C2O42-)+}]_
[{Cr(H2O)6}3+][C2O42-]

K2 = ___[{Cr(H2O)2(C2O4)2}-]___ β3 = K1K2K3 = ____[{Cr(C2O4)3}3-]___


[{Cr(H2O)4(C2O4)}+][C2O42-] [{Cr(H2O)6}3+][C2O42-]3

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]

5.9. (a) redox


(b) redox, dissociation
(c) reaction of a coordinated ligand
(d) substitution
(e) addition

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.

5.15. (a) [Co(NH3)6]2+ Co2+ labile


(b) [Co(NH3)5NO2]2+ Co3+, d6, moderately strong-field inert
(c) [CoI6]4- Co2+, d6, weak field labile
(d) [Fe(H2O)5(NCS)]2+ Fe3+ labile
(e) Ni(en)3]2+ Ni2+ labile
(f) [IrCl6]3- Ir3+ 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

*5.19. The situation we are faced with is as follows:


k1
(1) ML5X ─→ ML5 + X (fast)
k-1
k2
(2) ML5 + Y ─→ ML5Y (slow)

The rate-determining step is (2), so therefore,

Overall rate = Rate of step (2) = k2[ML5][Y]

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

Overall rate = k2k1[ML5X] [Y]


k-1[X]

*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.

5.25. Dissociative or interchange-dissociative mechanisms for the substitution reactions in octahedral


coordination compounds are supported by the observed rates of (a) water exchange, (b) anation, and (c)
aquation. The rates of exchange of water molecules in a hydrated metal ion are observed to be faster for
metals of lower charge and/or larger size. Specifically, as the charge density decreases, the rate of
exchange is found to be faster. This observation is consistent with a dissociative (or interchange-
dissociative) mechanism because decreasing the charge density weakens the bond between the metal and
the ligand-to-be-replaced and therefore leads to a faster rate-determining dissociative step. The fact that
the rates of anation reactions are independent of the incoming anion is also consistent with the rate-
determining step being the splitting off of a coordinated ligand followed by the addition of the incoming
anion. Finally, the fact that the rates of aquation reactions are found to be dependent on the identity of
the ligand to be replaced is also consistent with a dissociative mechanism. Data from all three of these
types of reactions indicate that the strength of the original metal-ligand bond (broken in the rate-
determining step of dissociative mechanism) determines the rate at which this ligand is replaced.

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

[Cr(NH3)5H2O]3+ ─ slow → [Cr(NH3)5]3+ + H2O

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.

5.37. For a d6 octahedral case, CFSE = 6(0.40ΔO) - 2P = 2.40 - 2P


For the square pyramidal case, CFSE = 4(0.457ΔO) + 2(0.086ΔO) = 2.00 - 2P
ΔCFSE = -0.40ΔO

5.39. For a d8 octahedral case, CFSE = 6(0.40Δo) - 2(0.60Δo) = 1.20Δo


For a d8 trigonal bipyramidal case, CFSE = 4(0.272Δo) + 3(0.082Δo) - 0.707Δo = 0.627Δo
(a) There is a substantial loss (1.20Δo - 0.627Δo = - 0.57Δo) of CFSE upon going to the trigonal
bipyramidal intermediate transition state, therefore we expect this reaction to be slower than it would be
in the absence of crystal field effects. On the other hand, these ions only have a +2 charge and therefore
would probably not be classified as inert.
(b) The loss in CFSE for the square pyramidal state (see Table 5.4) is only 0.20Δo. Since loss of CFSE
adds directly to the energy of activation, the Ea will most likely be smaller for the mechanism involving
the square pyramidal transition state. This mechanism will therefore be favored rather than the one
involving the trigonal bipyramidal intermediate.

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:

k (M-1s-1) = rate (M/s)


[A][B] M2

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

The sections and subsections in this chapter are listed below.

6.1 Applications of Monodentate Complexes


6.2 Two Keys to the Stability of Transition Metal Complexes
Hard and Soft Acids and Bases
The Chelate Effect
6.3 Applications of Multidentate Complexes
6.4 Chelating Agents as Detergent Builders
6.5 Bioinorganic Applications of Coordination Chemistry
Oxygen Transport
Therapeutic Chelating Agents for Heavy Metals
Platinum Antitumor Agents

Chapter 6 Objectives

You should be able to

• cite examples of transition metal complexes involving monodentate ligands in qualitative


analysis, dyes, silver and gold ore processing, nickel purification, and black/white
photography
• define, characterize, rationalize, and use the concept of hard and soft acids and bases as
applied to the stability of metal-ligand interactions
• define, explain, and give examples of the chelate effect
• cite and explain applications of multidentate complexes drawn from complexometric
quantitative analytical methods
• explain why EDTA is used to remove hard water deposits from hot water boilers and heaters
and often added to foods and other consumer products
• explain the function of detergent builders and the advantages and disadvantages of using
phosphates, nitrilotriacetic acid, and carbonates to carry out that function over the years
• explain the role of hemoglobin and its oxygen complexes in the process of respiration
• explain how carbon monoxide and cyanide poisoning work
• explain how and why EDTA, pencillamine, and British anti-lewisite function as therapeutic
chelating agents for heavy metals
• briefly cite some of the history and symptoms of lead and mercury poisoning
• explain how cisplatin and its derivatives serve as antitumor agents

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.

2CN-(aq) + 2Ag+ ─→ Ag[Ag(CN)2](s)

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.

[Ni(NH3)6]2+(aq) ─→ Ni2+(aq) + 6NH3(aq) K = 1/β = 1/(4.0 x 108)


Ni2+(aq) + 3en(aq) ─→ [Ni(en)3]2+(aq)________________ β = 2.0 x 1018
[Ni(NH3)6]2+(aq) + 3en(aq) ─→ [Ni(en)3]2+(aq) + 6NH3(aq) K = 2.0 x 1018 = 5.0 x 109
4.0 x 108

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:

0.7815g Ni(dmgH)2 x 1 mol Ni(dmgH)2 x ___1 mol Ni____ x 58.69 g Ni = 0.1588g Ni


288.91g Ni(dmgH)2 1 mol Ni(dmgH)2 1mol Ni

% Ni = 0.1588g Ni x 100 = 45.94%


0.3456g ore

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.

0.02394L x 0.04672 mol EDTA x __1 mol Ca__ x 40.08 g Ca = 0.04483g Ca


L 1 mol EDTA 1 mol Ca

% Ca = _0.04483g Ca__ x 100 = 22.41%


0.2000 g sample

*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.

0.02275L x 0.01000 mol trien x _1 mol Cu_ x 63.54g Cu = 0.01446g Cu


L 1 mol trien 1 mole Cu

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:

% Cu = _0.1446g Cu__ x 100 = 72.10%


0.2005g sample

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.)

*6.27. Dear Biology Major:


You may recall from your mind-bending introductory chemistry class that things are colored
because they absorb some wavelengths of visible light and either allow other wavelengths through or
reflect them to our eyes so that we perceive something to be colored. Sometimes this process is
expressed by a color wheel like the one shown on the next page. This wheel says that if an object, for
example, absorbs blue-green wavelengths it will therefore reflect or transmit red light to our eyes. Red
light has a wavelength in the range of 750-610 nm. What causes light to be absorbed? Usually this is
attributed to various energy levels in an atom or molecule. In the hemoglobin of the blood there are a
number of iron ions surrounded by a so-called heme group. This heme group causes a split among the d
orbitals of the iron resulting in the absorption of blue-green light so that our blood appears red. When
the blood is oxygenated, an oxygen molecule (O2) also exerts a slight influence on the split among the d
orbitals of the iron. Now the "oxyhemoglobin" absorbs at a slightly different range of wavelengths so
that the blood now appears a brighter shade of red. (See footnote at the end of this chapter.)

Wavelength Range (nm) Color

750-610 red
610-590 orange
590-570 yellow
570-500 green
500-450 blue
450-370 violet

6.29. Dear Doctor:


You may recall a group of molecules called the hemes. Hemes are made up of four nitrogen
atoms (incorporated into a impressive array of organic heterocyclic rings) that are bound to a central iron
cation. For example, hemes are an essential part of hemoglobin that is, as you know, responsible for
transporting oxygen molecules (O2) from the lungs to the cells. Hemes are also a vital part of the
cytochromes (c, a, a3, etc.) that play a large role in cellular respiration, the process whereby O2 is
converted to water. The problem with cyanide, CN-, is that it binds or coordinates to the central iron
cation of cytochromes and essentially shuts down cellular respiration. For this reason, of course, it is
important to minimize patient exposure to cyanide. (See footnote at the end of this chapter.)

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.

*6.39. Dear English Major:


You may recall from your AP chem course that cis means "on the same side of" while trans
means "over" or "across." (These terms are both from the Latin.) Cisplatin then has two groups
(chlorine atoms as it turns out) on the same side of a platinum atom. When cisplatin interacts with fast-
growing tumor tissue, many researchers believe that the two chlorides are replaced with adjacent
sections ("nitrogen-bases" if you recall this much from that long ago AP experience) of DNA. In this
form (attached to a platinum atom) the DNA is incapable of reproducing faithfully and the growth of the
tumor cells is retarded or even reversed. When the trans analog of cisplatin is used, it cannot interact
with adjacent sections of DNA and cannot significantly interfere with the replication of the tumor cells.
The tumor continues to grow unchecked. (See following footnote.)

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

The sections and subsections in this chapter are listed below.

7.1 Types of Crystals


Ionic Crystals
Metallic Crystals
Covalent Network Crystals
Atomic/Molecular Crystals
7.2 A-type Crystal Lattices
A-type Lattices
7.3 ABn-type Crystal Lattices
Cubic, Octahedral, and Tetrahedral Holes
Radius Ratios
Ionic Radii
AB Structures
AB2 Structures
7.4 Structures Involving Polyatomic Molecules and Ions
7.5 Defect Structures
7.6 Spinel Structures: Connecting Crystal Field Effects with Solid State Structures

39
Chapter 7 Objectives

You should be able to

• 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.

*7.3. C covalent network interlocking covalent bonds (diamond)


CCl2F2 molecular London dispersion forces and dipole-dipole forces
CaCO3 ionic ionic bonds among Ca2+ and CO32- ions
NH4F ionic ionic bonds among NH4+ and F- ions

*7.5. Ca metallic metallic forces


CaF2 ionic ionic bonds among Ca2+ and F- ions
CF4 molecular London dispersion forces

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.

= in body of eight unit cells


(7 dotted, 1 solid)

= at corner of solid unit cell

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.

7.17. Gold is face-centered cubic.

(a)
4r = l 2
1 = 4.070A
r = (l 2 ) / 4 = (4.070 2 ) / 4

r = 1.44Å

(b) (4 atoms) x 196.67 g/mol __


density = 6.02 x 1023 atoms/mol = 1.31 x 10-21 grams = 19.3 g/cm3
[2(1.44 x 10-8cm) 2 ]3 6.76 x 10-23 cm3

The actual density is 19.3 g/cm3, therefore the percent error is zero.

7.19. Europium is body-centered cubic.

(2 atoms) x 151.96 g/mol_____


density = 5.26 g/cm3 = 6.02 x 1023 atoms/mol )
l3 cm3
l = 4.58 x 10-8 cm or 4.58Å

2d = 4r = l 3 , therefore, r = (4.58 3 )/4 = 1.98Å

7.21. Krypton is cubic close-packed or face-centered cubic.


(a) 4 atoms per unit cell

(b) (4 atoms) x 83.80 g/mol_____


density = 3.5 g/cm3 = (6.02 x 1023 atoms/mol )
l3 cm3
-8
l = 5.4 x 10 cm or 5.4Å
(c) 2d = 4r = l 2 , therefore r = l 2 /4 = 5.4 2 /4 = 1.9Å

7.23. Magnesium is hexagonal close-packed.

Mg-Mg distance = 2rMg, therefore rMg = 1.602Å

(6 atoms) 24.3 g/mol_____


density = (6.02 x 1023 atoms/mol ) = 2.42 x 10-22 grams = 1.74 g/cm3
24 2 (1.602 x 10-8cm)3 1.39 x 10-22 cm3

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.

From the Pythagorean theorem,


cell edge =
(2rsphere + 2rhole)2 = (2rsphere)2 + (2rsphere 2 )2 2rsphere

2rsphere + 2rhole = (2 3 ) rsphere

( 3 - 1) rsphere = rhole

rhole/rsphere = 0.732 face diagonal =


2rsphere 2
7.27.

(a) Fluorite [see Figure 7.23(a)]


The M atoms are in a cubic close-packed unit cell and therefore there are 4 per unit cell. The X atoms
are in all the tetrahedral holes and therefore there are 8 per unit cell. It follows that there are 4 MX2
formula units per cell.

(b) Rutile [see Figure 7.23(c)]


The M atoms are located at the cell corners [8(1/8)] and in the center (1) and therefore there are two M
atoms per cell. There are 4 X atoms in the top and bottom faces of the cell giving 2 [ = 4(1/2)] atoms.
The other 2 X atoms are fully within the cell giving a total of 4 X atoms/cell. It follows that there are 2
MX2 formula units per unit cell.

*7.29. All radii in Ångstrom units for coordination number = 6

(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

Therefore, a CsCl structure is reasonable.

7.33. Zinc blende

S2- ions are in a face-centered cubic or cubic


close-packed (ABCABC) structure.
Zn2+ ions occupy half of the tetrahedral holes.

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.

Density (4 atoms) x 132.9 g/mol + (4 atoms) x 19.00 g/mol____


g/cm3 23
= __________(6.02 x 10 atoms/mol) (6.02 x 1023 atoms/mol)
(6.00 x 10-8)3 cm3
3
= 4.67 g/cm

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-).

l = 2(1.52) + 2(1.67) = 6.38Å

Volume of unit cell = l3 = (6.38Å)3 = 260Å3 (or 2.60 x 10-22 cm3)

4(39.1) + 4(35.45) grams


Density = 6.02 x 1023 = 1.91 g/cm3
-22 3
2.60 x 10 cm

The actual density is listed as 1.984 g/cm3.

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-).

body diagonal = l 3 = 4(1.26) + 4(1.19) = 9.80Å

(Note that the radius for the Ca2+ is the c.n. = 8 value.)

Therefore, l = 5.65Å or 5.65 x 10-8 cm

4(40.08) + 8(19.00) grams


Density = 6.02 x 1023 = 2.88 g/cm3
(5.65 x 10-8 cm)3

The actual density is listed as 3.180 g/cm3.

*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.

1(298) + 1(16.0) grams


Density = 6.02 x 1023 = 16 g/cm3
(3.2 x 10-8 cm)3

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

l 3 = 2r(Rb+) + 2r(Br-) = 2(1.66) + 2(1.82) = 6.96Å; therefore, l = 4.02Å

1(85.47) + 1(79.90) grams


Density = 6.02 x 1023 = 4.23 g/cm3
-8 3 3
(4.02 x 10 ) cm

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

4(85.47) + 4(79.90) grams


Density = 6.02 x 1023 = 3.26 g/cm3
(6.96 x 10-8)3 cm3

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

indicates c.n. = 6; indicates c.n. = 8; indicates c.n. = 8;


correct, NH4I correct, NH4Cl incorrect, NH4F
has a rock salt has a CsCl structure has a wurtzite
structure structure

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)

4(22.99) + 4(235.75) grams


Density = 6.02 x 1023 = 4.37 g/cm3
-8 - 3 3
[2(1.16 x 10 ) + 2r(SbF6 )] cm

Solving for r(SbF6-) yields a value of 2.50 x 10-8 cm or 2.50Å

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

octrahedral field tetrahedral field

3/5ΔO t2
2/5Δ t

2/5ΔO 3/5Δ t
e

CFSE = 3(2/5ΔO) -1(3/5ΔO) CFSE = 2(3/5Δ t) -2(2/5Δ t) = 2/5Δ t


= 3/5ΔO = 1/5ΔO

47
Chapter 8
Solid State Energetics

The sections and subsections in this chapter are listed below.

8.1 Lattice Energy: A Theoretical Evaluation


8.2 Lattice Energy: Thermodynamic Cycles
Electron Affinities
Heats of Formation for Unknown Compounds
Thermochemical Radii
8.3 Lattices Energies and Ionic Radii: Connecting Crystal Field Effects with Solid State
Energetics

Chapter 8 Objectives

You should be able to

• 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

8.1. (a) r(Rb+) = 1.66 = 0.91 Br Br


r(Br-) 1.82
Br Br
This radius ratio is consistent with a coordination number of eight.
Therefore, a reasonable* unit cell would be that of cesium chloride, Rb Br
that is, a simple cubic array of bromide ions with rubidium cations
in the center of each cell. A sketch of such a cell is found at right. Br Br
(*The actual unit cell of RbBr is rock salt, but CsCl is a reasonable structure
nevertheless for this compound.)

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 ⎠

r(Fr+) + r(Cl-) = r(Fr+) + 1.67 = 3.51Å; therefore, r(Fr+) = 1.84Å

*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.

(3)( +4)(−2) ⎛ 0.345 ⎞


(c) UKap = 1202 ⎜1 − ⎟ = - 10,900 kJ/mol
0.97 + 1.26 ⎝ 2.23 ⎠

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.

(3) n(Xe+) = 12, n(Ne) = 7, therefore, average n = 9.5

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 ⎠

ν Z + Z- ⎛ 0.345 ⎞ (2)(+1)( −1) ⎛ 0.345 ⎞


Kapustinskii: UKap = 1202 ⎜⎜1 − ⎟⎟ = 1202 ⎜1 − ⎟ = - 691 kJ/mol
ro ⎝ ro ⎠ 3.09 ⎝ 3.09 ⎠

*8.11. U = NAZ+Z-Mr-1 + NBr-n

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)

U = ΔH°f - ΔHsubl - IE1 - IE2 - 2ΔH(g) - 2EA


= -858.6 - (175.6) - (502.7) - (965.0) - 2(243.0) - 2 (-349.0) = - 2289.9 kJ/mol

Born-Landé Equation:

r(Ba2+) = 1.49 = 0.89 Indicates c.n. = 8, so a fluorite structure is reasonable.


r(Cl-) 1.67

Ba2+ has a [Xe] configuration, therefore n = 12


Cl- has an [Ar] configuration, so n = 9

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 ⎠

There is 12.5% difference between these two results.

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

ΔH°f = ΔHsubl + IE + ΔH(g) + EA + U

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 ⎠

ΔH°f = 338.3 + 745.3 + 79.0 + (- 328.0) + (- 948.0) = -113.4 kJ/mol

8.17.
ΔHof
1/2 Cl2(g) + 1/2 F2(g) ClF(g)

1/2 DCl-Cl 1/2 DF-F

Cl(g) + F(g)
-DCl-F
ΔH°f = ½DCl-Cl + ½DF-F - DF-Cl

½ DF-F = ΔH°f - ½ DCl-Cl + DCl-F

= - 56.1 - ½(243.4) + 246.4 = 68.6 kJ/mol

DF-F = 137.2 kJ/mol

*8.19. We want to calculate a value for the ΔH° for the following equation:

CsCl (ordinary form) → CsCl (rock salt form)

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:

ΔH = ΔH°f (rock salt form) - ΔH°f (ordinary form)

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

8.21. (a) ΔHof


Rb(s) + 1/2 Br2(l) RbBr(s)

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

EA = ΔH°f - ΔHsub - IE - ΔH(g) - U

EA = -394.6 - 80.9 - 403.1 - 111.9 - (- 633) = - 358 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⎠

[The value of r(Zn2+) is for coordination number 4.]

(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.)

8.25. 2CaCl(s) ─→ CaCl2(s) + Ca(s)

ΔH = ΔH°f [CaCl2(s)] + ΔH°f [Ca(s)] - 2ΔH°f [CaCl(s)]


ΔH = -792 + 0 - 2(- 130) = - 532 kJ/mol

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

ν Z + Z- ⎛ 0.345 ⎞ (2)(+1)( −1) ⎛ 0.345 ⎞


UKap = 1202 ⎜⎜1 − ⎟⎟ = 1202 ⎜1 − ⎟ = - 695 kJ/mol
ro ⎝ ro ⎠ 3.07 ⎝ 3.07 ⎠

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.

ΔH°f = 2080 + 121.7 + (- 349.0) + (- 695) = 1158 kJ/mol

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:

Ca(s) + 3/2 Cl2(g) ─→ CaCl3(s)

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.

8.33. (a) ΔHof[NaOH(s)]


Na(s) + 1/ 2 O2(g) + 1/2 H2(g) NaOH(s)

U
ΔΗsubl ΔHof[OH-(g)]
OH-(g) + Na+(g)

Na(g)
IE

ΔH°f [NaOH(s)] = ΔH°f [OH-(g)] + ΔHsubl + IE + U


U = ΔH°f [NaOH(s)] - ΔH°f [OH-(g)] - ΔHsubl - IE
U = - 425.6 - (- 143.5) - 107.3 - 495.9 = - 885.3 kJ/mol

ν Z + Z- ⎛ 0.345 ⎞ (2)(+1)(−1) ⎛ 0.345 ⎞


(b) UKap = 1202 ⎜⎜1 − ⎟⎟ = 1202 ⎜⎜1 − ⎟⎟ = - 885.3
ro ⎝ ro ⎠ ro ⎝ ro ⎠

Solving for ro yields values of 2.31 and 0.41Å, the latter value being physically impossible.

ro = r(Na+) + r(OH-) = 1.16 + r(OH-) = 2.31Å

Solving for r(OH-) yields a value of 1.15Å

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)

ΔH°f [NaBH4(s)] = ΔH°f [BH4-(g)] + ΔHsubl + IE + U


ΔH°f [BH4-(g)] = ΔH°f [NaBH4(s)] - ΔHsubl - IE - U
ΔH°f [BH4-(g)] = - 183.3 - 107.3 - 495.9 - (- 703) = - 84 kJ/mol

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)

ΔH°f [K2PtCl6(s)] = ΔH°f [PtCl62-(g)] + 2(ΔHsubl) + 2(IE) + U


ΔH°f [K2PtCl6(s)] = -774 + 2(89.2) + 2(418.9) + (-1468) = - 1226 kJ/mol

ν Z + Z- ⎛ 0.345 ⎞ (2)(+2)(−2) ⎛ 0.345 ⎞


8.39. UKap = 1202 ⎜⎜1 − ⎟⎟ = 1202 ⎜⎜1 − ⎟ = - 2911 kJ/mol
ro ⎝ ro ⎠ ro ⎝ ro ⎟⎠

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

low-spin Fe2+ (d6) high-spin Fe2+ (d6)

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

gradual increase expected


due to decrease in radii of
3600
M2+ ions

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

The sections and subsections of this chapter are listed below.

9.1 The Periodic Law


Effective Nuclear Charge
Atomic Radii
Ionization Energy
Electron Affinity
Electronegativity
9.2 The Uniqueness Principle
The Small Size of the First Elements
The Increased Likelihood of π-bonding in the First Elements
The Lack of Availability of d orbitals in the First Elements
9.3 The Diagonal Effect
9.4 The Inert Pair Effect
9.5 Metal, Nonmetal, and Metalloid Regions
9.6 Conclusions

Chapter 9 Objectives

You should be able to

• 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.

Actual for Ge Predicted vertically Predicted horizontally

atomic weight (g/mol) 72.59 73.4 72.3


density (g/cm3) 5.32 4.8 5.8
melting point (ºC) 937 823 421
boiling point (ºC) 2830 2312 ---
electronegativity 1.8 1.8 1.8
ionization energy (kJ/mol) 760 748 763
electron affinity (kJ/mol) -118 -120 -56
atomic radius (Å) 1.39 --- ---

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.

9.11. Orbital diagrams:

Phosphorus [Ne] ↑ ↓ ↑ ↑ ↑__


3s 3p
Copper [Ar] ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓
4s 3d
Arsenic [Ar] ↑ ↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑ ↑__
4s 3d 4p

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.

9.15. Effective nuclear charge, Zeff = Z - σ


(a) calcium, Zeff = 20 - 18 = 2
(b) silicon, Zeff = 14 - 10 = 4
(c) gallium, Zeff = 31 - 28 = 3, where the 28 electrons are the [Ar]3d10 pseudonoble gas
configuration.
(d) argon, Zeff = 18 - 10 = 8

*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,

Zeff = 10 - 8(0.85) - 2(1.00) = 1.20

(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,

Zeff = 10 - 7(0.35) - 2(0.85) = 5.85

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.

For a 4s electron of calcium, Zeff = 20 - 1(0.35) - 8(0.85) - 10(1.00) = 2.85


For a 3p electron of calcium, Zeff = 20 - 7(0.35) - 8(0.85) - 2(1.00) = 8.75

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

The sections and subsections of this chapter are listed below.

10.1 The Origin of the Elements (and of Us!)


10.2 The Discovery, Preparation, and Uses of Hydrogen
10.3 Isotopes of Hydrogen
10.4 Radioactive Processes involving Hydrogen
Alpha and Beta Decay, Nuclear Fission, and Deuterium
Tritium
10.5 Hydrides and the Network
Covalent Hydrides
Ionic Hydrides
Metallic Hydrides
10.6 The Role of Hydrogen in Various Alternative Energy Sources
Hydrogen Economy
Nuclear Fusion

63
Chapter 10 Objectives

You should be able to

• explain the nature of the "big bang" theory


• give a brief general account of the origin of the elements
• represent the nucleus of an element properly
• explain the source of energy in nuclear reactions
• explain the difference between fusion and fission
• relate how and by whom hydrogen was discovered
• explain how hydrogen gas is commonly generated in the laboratory
• describe the common industrial preparations and uses of hydrogen
• describe the dangers and uses of the reaction between hydrogen and oxygen
• describe the similarities and differences among the three isotopes of hydrogen
• describe the isolation and uses of "heavy water," D2O
• describe, represent and explain the deuteration of various compounds
• describe and give examples of α, ß-, and ß+ decay
• explain the concept of half life as it applies to radioactive isotopes
• explain and represent fission
• describe the conditions for the occurrence of a nuclear fission chain reaction
• relate the first example of nuclear transmutation
• describe how tritium is produced in nature and by humankind
• discuss the placement of hydrogen among the groups of the representative elements
• describe the three major oxidation states of hydrogen
• describe and give examples of covalent hydrides
• describe and give examples of ionic or "saline" hydrides and their uses
• describe and give examples of metallic hydrides and their uses
• discuss the nature of nonstoichiometric interstitial hydrides
• describe what is meant by the "hydrogen economy"
• describe the potential of nuclear fusion as a future energy source

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

10.5. (a) 126C + 11H ─→ 13


7N
(b) 137N ─→ 13
6C
0
+ +1e (positron)
(c) 136C + 11H ─→ 147N
(d) 147N + 11H ─→ 158O
(e) 158O ─→ 15 0
7N + +1e (positron)
(f) 157N + 11H ─→ 126C + 42He (alpha particle)

10.7. (a) 11H + 11H ─→ 21H + 0+1e


Δm = Σm(reactants) - Σm(products)
= 2(1.007825) - (2.0140 + 5.488 x 10-4)
= 0.0011 u

⎛ 8.984 x 1010 kJ/mol ⎞


E = (0.0011 u) ⎜⎜ ⎟⎟ = 9.88 x 107 kJ/mol
⎝ u ⎠

(b) proton-proton cycle: 4 11H ─→ 4


2He + 2 0+1e

Δm = Σm(reactants) - Σm(products)
= 4(1.007825) - [4.0015 + 2(5.488 x 10-4)]
= 0.0287 u

⎛ 8.984 x 1010 kJ/mol ⎞


E = (0.0287 u) ⎜⎜ ⎟⎟ = 2.58 x 109 kJ/mol
⎝ 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."

*10.11.ΔH = ΔH°f[CO(g)] + ΔH°f[H2(g)] - ΔH°f[C(graphite)] - ΔH°f[H2O(g)]


ΔH = (-110.5) + 0 - 0 - (-241.8) = 131.3 kJ/mol
Since this is an endothermic reaction, heat is absorbed and is a reactant. Therefore when the temperature
is raised to higher values, this reaction, according to Le Châtelier's principle, shifts to the right. Recall
from your previous study of this principle that when the pressure of a reaction at equilibrium is
decreased, it will shift in the direction producing the larger number of moles of gases. This reaction goes
from one mole of gaseous reactants to two moles of gaseous products, therefore lowering the pressure
will shift the reaction to the right and increase its yield.
(Standard heats of formation vary somewhat from source to source, so your values may not be exactly the same as those given
here.)

10.13. MO(s) + H2(g) ─→ M(s) + H2O(l)


M is reduced from 2+ to 0; H is oxidized from 0 to 1+
Ag2O(s) + H2(g) ─→ 2Ag(s) + H2O(l)
Bi2O3(s) + 3H2(g) ─→ 2Bi(s) + 3H2O(l)

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.

⎛ 1 cup D 2 O ⎞ ⎛ 0.236 L D 2 O ⎞ ⎛ 1000 mL D 2 O ⎞ ⎛ 1.10 g D 2 O ⎞ ⎛ 1 gal water ⎞ g D 2O


⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ ⎜ ⎟ = 0.172
⎝ 400 gal water ⎠ ⎝ 1 cup D 2 O ⎠⎝ L D 2O ⎠ ⎝ mL D 2 O ⎠ ⎝ 3.78 L water ⎠ L water

Next we can calculate the liters of water in the oceans.

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:

⎛ 1.0080 x 2 g ⎞ ⎛ 1 mol ⎞ ⎛ 2.0140 x 2 g ⎞ ⎛ 1 mol ⎞


H2 ⎜ ⎟ ⎜⎜ ⎟⎟ = 0.0900 g/L D2 ⎜ ⎟ ⎜⎜ ⎟⎟ = 0.180 g/L
⎝ mol ⎠ ⎝ 22.4 L ⎠ ⎝ mol ⎠ ⎝ 22.4 L ⎠

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.

10.29. beta-minus decay: 4019K ─ β-→ 0-1e + 4020Ca


beta-plus decay: 4019K ─ β-→ 0+1e + 4018Ar
238
10.31. 92U + 10n ─→ [23992U] ─ β-→ 0
-1e + 23993Np

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

10.41. 11H + 147N ─ cosmic rays→ 14


8O + 10n

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

*10.45. Using the Born-Haber cycle shown at right, ΔH


1/2 X2(g) + e-(g) X-(g)
we see that ΔH = ½D + EA
1/2 D
For X = H
ΔH = ½D + EA = ½(436.4) + (-77) = 141 kJ/mol
EA
X(g)
For X = F
ΔH = ½D + EA = ½(150.6) + (-333) = -258 kJ/mol

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⎠

where ro = r(K+) + r(H-) = 1.52 + 1.53 = 3.05Å; where n = (9 + 5)/2 = 7


(values from Tables 7.4 and 7.6) (values from Table 8.2)
There is a 3.5% difference between the values obtained from the Born-Haber cycle and the Born-Landé
equation (with the Born-Haber cycle taken as the most accurate value).

ν Z + Z- ⎛ 0.345 ⎞ (2)(+1)( −1) ⎛ 0.345 ⎞


10.49. UKap = 1202 ⎜⎜1 − ⎟⎟ = 1202 ⎜1 − ⎟ = - 846 kJ/mole
ro ⎝ ro ⎠ 2.44 ⎝ 2.44 ⎠

where ro = r(Cu+) + r(H-) = 0.91 + 1.53 = 2.44Å


(Note: there is a very small difference, 0.2 on the Pauling scale, between the electronegativities of
copper and hydrogen. This result is indicative of a high degree of covalent character in the Cu-H bond.

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.)

ν Z + Z- ⎛ 0.345 ⎞ (3)(+2)(−1) ⎛ 0.345 ⎞


10.51. UKap = 1202 ⎜⎜1 − ⎟⎟ = 1202 ⎜1 − ⎟ = - 2350 kJ/mole
ro ⎝ ro ⎠ 2.67 ⎝ 2.67 ⎠

where ro = r(Ca2+) + r(H-) = 1.14 + 1.53 = 2.67Å

10.53. 5CaH2(s) + Ta2O5(s) ─→ 5CaO(s) + 2Ta(s) + 10H2(g)

*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

The sections and subsections of this chapter are listed below.

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

You should be able to

• relate how and by whom oxygen was discovered


• explain why Priestley was able to isolate many more gases than scientists before him
• describe the influence of the phlogiston theory of combustion on the discovery of oxygen
• explain why Priestley could be called the "father of the modern soft drink industry"
• explain the general relationship between carbon dioxide and oxygen in the biosphere
• explain and represent how oxygen gas is generally prepared industrially and in the laboratory
• describe some of the most important uses of oxygen
• describe the structure and polarity of an individual water molecule
• describe the utility of the FONCl rule of hydrogen bonding
• relate the nature and properties of ice and snowflakes to the structure of solid water
• describe and represent the "flickering cluster" model of water structure
• describe, explain, and represent the solubility of ionic and covalent substances in liquid water
• describe and represent the self-ionization of water
• describe the utility and limitations of the concept of the hydronium ion in water and as a product
of acids in aqueous solution
• show and explain the distribution of ionic, covalent polymeric, and discrete molecular oxides in
the periodic table
• explain why metal oxides are basic anhydrides
• explain why nonmetal oxides are acidic anhydrides
• describe and give an example of an amphoteric anhydride and oxide
• explain why substances containing an M-O-H unit are basic in aqueous solution: give several
examples
• explain why substances containing an NM-O-H unit are acidic in aqueous solution; give several
examples
• explain the effect on the strength of an oxoacid of changing the central atom; give several
examples
• explain the effect on the strength of an oxoacid of changing the number of nonhydroxyl oxygens
attached to the central atom; give several examples
• name a variety of oxoacids and their salts
• explain the variation of acid strength in hydroacids within a period and a group of the periodic
table; give several examples
• describe and represent ozone
• describe how ozone is formed and some of its beneficial uses
• describe and represent how ozone is formed and destroyed in the stratosphere in the absence of
external agents
• describe the manner in which various greenhouse gases potentially cause radiative forcing and
global warming
• list some methods whereby the amount of greenhouse gases released to the atmosphere could be
reduced

71
Solutions to Odd-Numbered Problems

11.1. HgO(s) ─heat→ Hg(l) + O(g)

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

*11.7. AW = 0.99763(15.994915) + 0.00037(16.999134) + 0.00200(17.999160) = 15.999u


This result is the same as listed on the periodic table (at least to 3 places to the right of the decimal point).

11.9. C5H12(l) + 8O2(g ) ─→ 5CO2(g) + 6H2O(l)

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

(c) CO2 (d) OF2


O
O C O O C O F O F F F
o
<109.5
o
180
(e) NO2- (f) CS2
- - S C S
N
O N O O N O O o O S C S o
<120 180

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.

*11.19. Dear English Major:

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

11.31. H2O + H2O H3O+(aq) + OH-(aq) H

Kw = [H3O+(aq)][OH-(aq)] = x2 = 1.0 x 10-14


x = [OH-(aq)] = [H3O+(aq)] = 1.0 x 10-7
pH = - log[H3O+(aq)] = 7.00

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.

11.35. Strong acids + provide


a high concentration H
of H3O+, hydronium ions, O
in solution. These species
are hydrated by other H
H2O groups as shown
at right. If these
hydrates are stable
enough (and of high
enough concentrations) = H11O5+
they may be isolated from
such solutions. O
H
H
H O H
O
H H
O H
H
H

11.37. Oxides: K2O, Ga2O3, As2O3 or As2O5, SeO2 or SeO3


basic amphoteric acidic but close acidic
(along M/NM to borderline
border)

11.39. The existence of S3 (if analogous to O3)


depends on the strength of S=S double bonds. S S S S S S
Sulfur atoms are considerably larger than oxygen
atoms (re: uniqueness principle) and therefore parallel overlap among their p orbitals (so-called
pπ-pπ overlap) is much less effective. Therefore, we are unlikely to find an S3 analog of ozone.

*11.41. N2O3 + H2O ─→ 2HNO2 ─→ 2H+(aq) + NO2-(aq)



O Oδ O
+ O
δ O O
N H N
+ N
δ H N

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.

11.51. (a) NO(OH) acidic


(b) Be(OH)2 amphoteric
(c) Ti(OH)4 basic
(d) Si(OH)4 acidic

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

11.57. (a) HIO2


(b) HBrO4
(c) H2SO5

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+
+

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

The sections and subsections of this chapter are listed below.

12.1 Discovery and Isolation of the Elements


12.2 Fundamental Properties and the Network
Hydrides, Oxides, Hydroxides, and Halides
Application of the Uniqueness Principle and Diagonal Effect
12.3 Reduction Potentials and the Network
12.4 Peroxides and Superoxides
Peroxides
Superoxides
12.5 Reactions and Compounds of Practical Importance
12.6 Selected Topic in Depth: Metal-Ammonia Solutions

Chapter 12 Objectives

You should be able to

• 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

12.1. Cavendish report of his discovery of hydrogen, 1766


Priestley published discovery of dephlogisticated air (oxygen), 1774
Lavoisier characterization of dephlogisticated air as oxygen, late 1770s
Davy discovery of Group 1A and 2A elements, 1807-1808
Arfwedson discovery of lithium, 1817
Bunsen discovery (with Kirchhoff) of cesium and rubidium by spectroscopy,
Mendeleev formulation of periodic table, 1869

*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.

atomic radii (A) ionzation energy (kJ/mol)


3.0 500

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

12.11. K2O(s) + H2O ─→ 2 KOH(aq)

12.13. Na+H-(s) + H2O ─→ Na+(aq) + OH-(aq) + H2(g)

*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.

12.19. 2 [ Li(s) ─→ Li+(aq) + e- ] Ε° = +3.05v; ΔG° = -2(96.5kJ/v)(3.05v) = -589 kJ


______1 [ 2H+(aq) + 2e- ─→ H2(g) ]____ Ε° = 0.00v; ΔG° = 0.00 kJ
2 Li(s) + 2H+(aq) ─→ 2 Li+(aq) + H2(g) ΔG° = -589 kJ
E° = - ___-589kJ__ = 3.05V
Li = reducing agent; H+ = oxidizing agent (2)(96.5kJ/V)

*12.21. Li+(aq) + e- ─→ Li(s) E° = -3.05V; ΔG° = -(1)(96.5kJ/v)(-3.05v) = 294 kJ


Na+(aq) + e- ─→ Na(s) E° = -2.71V; ΔG° = -(1)(96.5kJ/v)(-2.71v) = 261 kJ
Based on these standard reduction potentials, it will be more difficult to electrolyze LiCl to lithium metal
than it will be to electrolyze NaCl to sodium metal (under standard state conditions).

*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.

*12.29. 2 [ H2O2(aq) + 2H+(aq) + 2e- ─→ 2H2O(l) ] E° = +1.77V


1 [ 2H2O(l) ─→ O2(g) + 4H+(aq) + 4e- ] E° = - 1.23V
2H2O2(aq) ─→ O2(g) + 2H2O(l) E° = +0.54V

12.31. Half reactions under acid conditions:

2 [ Co2+(aq) ─→ Co3+(aq) + e- ] E° = - 1.82V


1 [2H+(aq) + H2O2(aq) + 2e- ─→ 2H2O(l) ] E° = +1.77V
2Co2+(aq) + 2H+(aq) + H2O2(aq) ─→ 2Co3+(aq) + 2H2O(l) E° = - 0.05V

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:

Al3+(aq) + Na(s) ─→ Al(s) + Na+(aq)

1 [Al3+(aq) + 3e- ─→ Al(s) ] E° = - 1.66V


3 [______Na(s) ─→ Na+(aq) + e-_]_______ E° = +2.71V
Al3+(aq) + 3 Na(s) ─→ 3 Na+(aq) + Al(s) E° = +1.05V

Yes, sodium could be used to reduce Al3+(aq) to Al(s).

*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

12.39. The oxidation state of each oxygen in O2- is -½.

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.

12.43. 2 [ Na+ + e- ─→ Na(s) ] E° = -2.71V Note that a significant amount


- -
1 [___2Cl ─→ Cl2(g) + 2e ______] E° = -1.36V of energy is needed to make
2Na+ + 2Cl- ─→ 2Na(s) + Cl2(g) E° = -4.07V this reaction go.
ΔG° = -(2)(96.5kJ/V)(-4.07V) = 785 kJ
12.45. (a) TiCl4(s) + 4Na(s) ─→ Ti(s) + 4NaCl(s)
(b) ZrCl4(s) + 4Na(s) ─→ Zr(s) + 4NaCl(s)

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

The sections and subsections of this chapter are listed below.

13.1 Discovery and Isolation of the Elements


13.2 Fundamental Properties and the Network
Hydrides, Oxides, Hydroxides, Halides
Uniqueness of beryllium and diagonal relationship to aluminum
13.3 Reactions and Compounds of Practical Importance
Beryllium Disease
Radiochemical Uses
Metallurgical Uses
Fireworks and X-rays
Hard water
13.4 Selected Topic in Depth: The Commercial Uses of Calcium Compounds
CaCO3 (limestone)
CaO (quicklime) and Ca(OH)2 (slaked lime)

83
Chapter 13 Objectives

You should be able to

• explain the origin of the term "alkaline earth"


• briefly relate how and by whom the alkaline earth metals were discovered
• describe the process by which the Curies isolated radium
• rationalize the trends in radii, ionization energies, electron affinities, and electronegativities of
the group
• rationalize, on the basis of standard reduction potentials, why the alkaline earths are good
reducing agents
• describe the general nature of the hydrides, oxides, hydroxides, and halides of the group
• list and briefly rationalize the ways in which beryllium is different from its heavier congeners
• list and briefly rationalize the ways in which beryllium is similar to aluminum
• briefly describe the role of the alkaline earths in beryllium disease, neutron production, nuclear
fission products, metallurgy, fireworks, x-ray technology, and hard water
• describe how limestone and marble structures are damaged by acid rain
• briefly describe and represent the Solvay process
• briefly describe and represent the use of calcium carbonate in smokestack scrubbers
• briefly list some other uses of calcium carbonate
• briefly describe the use of calcium oxide (quicklime) in the steel and glass industries and in
acetylene production
• briefly describe the use of calcium hydroxide (slaked lime) as a mortar, for water treatment, in
the paper and pulp industries, and for bleaches
• list several uses of calcium sulfate

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.]

13.3. 3SrO(s) + 2Al(s) ─→ 3Sr(s) + Al2O3(s)

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

13.9. BeF2(s) + Mg(s) ─→ MgF2(s) + Be(s)

ΔG° = ΔG°f [MgF2(s)] + ΔG°f [Be(s)] - ΔG°f [BeF2(s)] - ΔG°f [Mg(s)]


ΔG° = -1070.2 + 0 - (-979.4) - 0 = -90.8 kJ/mol
226
13.11. 88Ra ─β-→ 0
-1e + 22689Ac
226 4
13.13. 88Ra ─α→ 2He + 22286Rn

*13.15. FrCl(s) + Ag+(aq) ─→ AgCl(s) + Fr+(aq)


0.00476 g 0.00263 g

⎛ 1 mol AgCl ⎞ ⎛ 1 mol FrCl ⎞


(0.00263 g AgCl) ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ = 1.84 x 10-5 mol FrCl
⎝ 143.32 g AgCl ⎠ ⎝ 1 mol AgCl ⎠

Formula weight of FrCl = __0.00476 g__ = 259 g/mol


1.84 x 10-5 mol

Atomic Weight of Fr = FW of FrCl - AW of Cl


= 259 - 35.453 = 224 g/mol

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.

1 [Ca(s) ─→ Ca2+(aq) +2e- ] E° = +2.87v; ΔG° = -2(96.5kJ/v)(+2.87) = -554 kJ


1 [2H2O + 2e- ─→ 2OH-(aq) + H2(g) ]______ E° = - 0.83v; ΔG° = -2(96.5kJ/v)(- 0.83)
=+160 kJ
Ca(s) + 2 H2O ─→ Ca2+(aq) +2OH-(aq) + H2(g) ΔG° = -394 kJ
E° = - _(-394kJ) = 2.04V
2(96.5kJ/V)

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)

In general, ΔHred = -(ΔHatom + Sum of n IEs + ΔHhyd)

ΔHred[Li] = -[159 + 520 + (-519)] = - 160 kJ/mol E° = -3.05V


ΔHred[Be] = -[324 + 899 + 1757 + (-2494)] = -486 kJ/mol E° = -1.85V

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."

13.29. Be(OH)2 + 2OH-(aq) ─→ Be(OH)42-

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.

13.33. 13153I ─β-→ 0-1e + 13154 Xe


While Sr 90 would replace calcium in bone structure and cause radiation damage, I 131 would go to the
thyroid where it would be used to make thyroxine.

13.35. ZrCl4 + 2Mg(s) ─Δ→ Zr(s) + 2MgCl2

87
HfCl4 + 2Mg(s) ─Δ→ Hf(s) + 2MgCl2

13.37. CaCO3(s) + 2HCl(aq) ─→ H2O + CO2(g) + CaCl2(aq)


*13.39.
δ+
O H O
δ−
C O O C CO2 + H2O + CO32-
δ−
O H O
δ+
13.41. CaCO3(s) + 2HCl(aq) ─→ CO2(g) + H2O(l) + CaCl2(aq)

13.43. NaHCO3(aq) + HCl(aq) ─→ H2O + CO2(g) + NaCl(aq)

*13.45. Na2CO3 2 Na+(aq) + CO32-(aq)

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.

Ksp = [Na+(aq)]2[CO32-(aq)] = (2x)2(x) = 4x3

⎛ 7.1 g Na 2 CO 3 ⎞ ⎛ mol ⎞ ⎛ cm 3 ⎞ ⎛ 1000 mL ⎞


x can be determined from the solubility: x = ⎜ 3 ⎟ ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ ⎜ ⎟ = 0.67M
⎝ 100 cm ⎠ ⎝ 106.0 g ⎠ ⎝ mL ⎠ ⎝ L ⎠

Ksp = 4(0.67)3 = 1.2

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

The sections and subsections of this chapter are listed below.

14.1 Discovery and Isolation of the Elements


Boron
Aluminum
Gallium
Indium and Thallium
14.2 Fundamental Properties and the Network
Hydrides, Oxides, Hydroxides, and Halides
14.3 Structural Aspects of Boron Chemistry
Allotropes
Borides
Borates
14.4 Aluminum, Gallium, Indium, and Thallium
Aluminum Metal and Alloys
Alum
Alumina
Gallium, Indium, and Thallium Compounds
14.5 Selected Topic in Depth: Electron-Deficient Compounds

Chapter 14 Objectives

You should be able to:

• 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)

14.3. Turkish samples:


AW = 0.2030(10.01294) + (0.7970)(11.00931) = 10.807u
California samples:
AW = (0.1910)(10.01294) + (0.8090)(11.00931) = 10.819u
204
14.5. 81Tl ─β-→ 0-1e + 204
82Pb

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.

14.17. 2Al(s) + 3Cl2(g) ─→ 2AlCl3(s)


Al(OH)3(aq) + 3HCl(aq) ─→ AlCl3⋅ 3H2O(s)

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.

1 [Tl3+(aq) + 2e- ─→ Tl+(aq) ] E° = +1.25V; ΔG° = -2(96.5)(1.25) = - 241 kJ


2 [Tl(s) ─→ Tl+(aq) + e- ] E° = +0.33V; ΔG° = -2(96.5)(0.33) = - 64 kJ
3+ +
Tl (aq) + 2 Tl(s) ─→ 3Tl (aq) ΔG° = - 305kJ

Yes, this reaction would be spontaneous. Tl+(aq) is more stable (under standard state conditions) than is
Tl3+(aq).

14.27. (a) Tl(s) + 2H+(aq) ─→ Tl+(aq) + H2(g)

2 [Tl(s) ─→ Tl+(aq) + e- ] E° = +0.33V; ΔG° = -(2)(96.5)(0.33) = -64 kJ


1 [2H+(aq) + 2e- ─→ H2(g)] E° = 0.00V; ΔG° = 0.00
2Tl(s) + 2H+(aq) ─→ 2Tl+(aq) + H2(g) E° = 0.33V; ΔG° = -64 kJ

(b) 2Tl(s) + 6H+(aq) ─→ 2Tl3+(aq) + 3H2(g)

2 [Tl(s) ─→ Tl3+(aq) + 3e-] E° = -0.72V; ΔG° =-(6)(96.5)(-0.72) = 417 kJ


3 [ 2H+(aq) + 2e- ─→ H2(g)] E° = 0.00V; ΔG° = 0.00
2Tl(s) + 6H+(aq) ─→ 2Tl3+(aq) + 3H2(g) E° = -0.72V; ΔG° = 417 kJ

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.

*14.37. Al(s) ─→ Al3+(aq) + 3e- E° = +1.66V ΔG° = -(3)(96.5kJ/v)(1.66v) = -481 kJ


Fe(s) ─→ Fe2+(aq) + 2e- E° = +0.44V ΔG° = -(2)(96.5kJ/v)(0.44v) = -85 kJ

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

*14.43. 2Al(s) + Fe2O3(s) ─→ Al2O3(s) + 2Fe(s)


ΔH° = ΔHf°[Al2O3(s)] + 2ΔHf°[Fe(s)] - 2ΔHf°[Al(s)] - ΔHf°[Fe2O3(s)]
= -1675.7 + 2(0) - 2(0) - (-822.2) = -853.5 kJ/mol

2Al(s) + Cr2O3(s) ─→ Al2O3(s) + 2Cr(s)


ΔH° = ΔHf°[Al2O3(s)] + 2ΔHf°[Cr(s)] - 2ΔHf°[Al(s)] - ΔHf°[Cr2O3(s)]
= -1675.7 + 2(0) - 2(0) - (-1128.4) = -547.3 kJ/mol

14.45. B6H10 -- consult Figure 14.15(e) for structure


H H
Available electrons: Distribution of electrons:
B B
-
6B x 3e = 18e -
6 B-H = 12e - H
H H
10H x 1e- = 10e- 5 B-H-B = 10e-
B
28e- 2 BBB = 4e- B B
1 B-B =_ 2e- H H
28e- H B H

14.47. B3H6+ cation H +

Available electrons: Distribution of electrons:


B
- - - H H
3B x 3e = 9e 3 B-H = 6e Each boron is
6H x 1e- = 6e- 3 B-H-B = 6e-sp3 hybridized.
(+) = -1e- 1 BBB = _2e- B B
H H
14e- 14e-
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.

H3C CH3 H CH3


H H

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

The sections and subsections of this chapter are listed below.

15.1 Discovery and Isolation of the Elements


Carbon, Tin, and Lead
Silicon
Germanium
15.2 Fundamental Properties and the Network
Hydrides
Oxides and Hydroxides
Halides
15.3 An Eighth Component of the Interconnected Network: pπ-dπ Bonding involving Elements
of the Second and Third Periods
15.4 Reactions and Compounds of Practical Importance
Diamond, Graphite and the Graphenes
Tin Disease
Radiochemical Uses
Carbon Compounds
Lead Compounds and Toxicology
15.5 Silicates, Silica, and Aluminosilicates
Silicates and Silica
Aluminosilicates
15.6 Selected Topics in Depth: Semiconductors and Glass
Semiconductors
Glass

96
Chapter 15 Objectives

You should be able to:

• 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

15.1. SnO2(cassiterite) + 2C(s) ─→ Sn(l) + 2CO(g)

15.3. SiO2(s) + 4HF(aq) ─→ SiF4(g) + 4H2O(l)

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.

15.15. Structures for tetrasilane and pentasilane

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

Li2O BeO B2O3 CO2 ───→ direction of increasing


covalent character
v. ionic intermediate predominantly
covalent

basic amphoteric weakly acidic acid-base character


anhydride anhydrides anhydrides helps characterize 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

This oxidation is possible under standard state conditions.

15.33. The phosphorus atom is sp3 hybridized. Each of these four


hybrid orbitals is used to form a single bond with an oxygen atom. _ +
Three of these oxygen atoms are, in turn, singly bonded to a hydrogen +
atom. The fourth oxygen atom does not have a hydrogen bonded to it P O
but rather forms a second bond with the phosphorus atom. This _
+ _
second bond is formed using a 3d orbital of phosphorus and a 2p
orbital of oxygen as shown at right. (The signs are the phases of the orbitals.) 3d 2p

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

The sections and subsections of this chapter are listed below.

16.1 Discovery and Isolation of the Elements


Antimony and Arsenic
Phosphorus
Bismuth
Nitrogen
16.2 Fundamental Properties and the Network
Uniqueness Principle
pπ-dπ Bonding involving Elements of the Second and Third Periods
Other Network Components
Hydrides
Oxides and Hydroxides
Halides
16.3 A Survey of Nitrogen Oxidation States
Nitrogen (-3) Compounds: Nitrides and Ammonia
Nitrogen (-2), Hydrazine, N2H4
Nitrogen (-1), Hydroxylamine, NH2OH
Nitrogen (+1), Nitrous Oxide, N2O
Nitrogen (+2), Nitric Oxide, NO
Nitrogen (+3), Dinitrogen Trioxide, N2O3, and Nitrous Acid, HNO2
Nitrogen (+4), Nitrogen Dioxide, NO2
Nitrogen (+5), Dinitrogen Pentoxide, N2O5, and Nitric Acid, HNO3
16.4 Reactions and Compounds of Practical Importance
Nitrogen Fixation
Nitrates and Nitrites
Nitrogen Air Bags
Matches and Phossy Jaw
Phosphates
16.5 Selected Topic in Depth: Photochemical Smog

104
Chapter 16 Objectives

You should be able to

• 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.

16.3. As2S3(s) + 3CaCO3(s) + 6O2(g) ─Δ → As2O3(s) + 3CaSO4(s) + 3CO2(g)


2As2O3(s) + 3C(s) ─→ 4As(s) + 3CO2(g)

*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)

16.7. The N-N H H


bond is weaker
<109.5o
due to the
close proximity N N C C
of the lone pairs H H H H
o
on the two <109.5
nitrogen atoms. H H H H

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.

(-) (-) - sp3 - sp sp - sp


-
O C N O C N O C N O C N
px - px
I II
py - py
180o

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.

16.19. (a) Na2HPO4


(b) (NH4)H2PO4
(c) K2H2P2O7
(d) CaHPO4
O
*16.21. H4P2O6, three acidic hydrogens

16.23. Only the one hydrogen atom bound to an oxygen P H


atom is acidic. The P-H bonds are nonpolar and not H
susceptible to attack by water. O

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

16.29. NH3(g) + F2(g) ─Cu→ NF3(g) + 3HF(g)

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.

16.35. (dashed lines = hydrogen bonds)

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.

*16.39. (a) 1 [ N2H5+(aq) ─→ N2(g) + 5H+(aq) + 4e- ] E° = +0.23V


__________ 4 [ Fe3+(aq) + e- ─→ Fe2+(aq) ]_________ E° = +0.77V
N2H5+(aq) + 4Fe3+(aq) ─→ N2(g) + 5H+(aq) + 4Fe2+(aq) E° = +1.00V

108
Yes, hydrazine could accomplish this reduction under standard state conditions.

(b) 5 [ N2H5+(aq) ─→ N2(g) + 5H+(aq) + 4e- ] E° = +0.23V


______4 [MnO4-(aq) + 8H+(aq) + 5e- ─→ Mn2+(aq) + 4H2O(l) ]_______ E° = +1.51V
5N2H5+(aq) + 4MnO4-(aq) + 7H+(aq) ─→ 5N2(g) + 4Mn2+(aq) + 16H2O(l) E° = +1.74V
This would be a most spontaneous reaction (thermodynamically) reaction.

16.41. As shown on the right, there


are several possible sites within the
hydroxylamine molecule where H
hydrogen bonding could take place.
N
H
O H O H

H N

H
H

H O H

*16.43. 1 [ 2e- + N2O + 2H+ ─→ N2 + H2O ] E° = +1.77V


1 [ N2O + H2O ─→ 2NO + 2H+ + 2e- ] E° = - 1.59V
2N2O ─→ N2 + 2NO E° = + 0.18V
Since E° is greater than zero, ΔG° will be less than zero and the reaction should be spontaneous under
standard state conditions.

16.45. N2(g) + O2(g) ─→ 2NO(g), ΔS° = 24.7 J/mol-K


This entropy change favors the increased production of NO at high temperatures because ΔG° = ΔH° -
TΔS°. A positive ΔS° leads to a negative contribution to ΔG°, which in turn makes the reaction more
spontaneous left to right.

*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

180o >120o <120o

The expected bond angles decrease as the nitrogen atom first adds a single nonbonding electron and then
a full lone pair.

16.53. N2O5 + H2O ─→ 2HNO3


This is not a redox equation; the oxidation state of nitrogen is +5 in both N2O5 and HNO3.

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.

*16.57. P2O5 + 2HNO3 + 2H2O ─→ N2O5 + 2H3PO4

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.

16.67. KHC4H4O6 + NaHCO3 ─→ CO2(g) + H2O + KNaC4H4O6(s)

*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

The sections and subsections of this chapter are listed below.

17.1 Discovery and Isolation of the Elements


Sulfur
Tellurium and Selenium (Earth and Moon)
Polonium
17.2 Fundamental Properties and the Network
Hydrides
Oxides and Oxoacids
Halides
17.3 Allotropes and Compounds Involving Element-Element Bonds
Allotropes
Polycations and Anions
Catenated Halides and Hydrides
Catenated Oxoacids and Corresponding Salts
17.4 The Sulfur Nitrides
17.5 Reactions and Compounds of Practical Importance
Sodium-Sulfur Batteries
Photoelectric Uses of Selenium and Tellurium
Sulfuric Acid
17.6 Selected Topic in Depth: Acid Rain

112
Chapter 17 Objectives

You should be able to

• 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).

17.7. H2O H2S H2Se H2Te H2Po

bp (°C) 100 -61 -41 -2 ---

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.

*17.9. Oxidizing agent: oxygen (reduced from 0 to -2)


Reducing agent: silver (oxidized from 0 to +1)
Tarnished silver objects (and therefore silver sulfide) are black

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.

17.13. SO2 ·H2O(aq) + H2O HSO3-(aq) + H3O+(aq)

*17.15. SO32-(aq) + H2O HSO3-(aq) + OH-(aq)

Kb = Kw = __[H+][OH-]__ = [HSO3-][OH-] = 1.00 x 10-14 = 1.6 x 10-7


Ka2 [H+][SO32-] [SO32-] 6.3 x 10-8
-
[HSO3 ]

17.17. SO32-(aq) + Cl2(g) ─→ SO42-(aq) + Cl-(aq)

Balance by half equations:

SO32- + H2O ─→ SO42- + 2H+ + 2e- ]1


Cl2 + 2e- ─→ 2Cl- ]1
SO3 + Cl2 + H2O ─→ SO4 + 2H + 2Cl-
2- 2- +

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.

2e- + S(s) + 2H+(aq) ─→ H2S(g) E° = 0.14V; ΔG° = -(2)(96.5kJ/V)(0.14V) = -27 kJ


SO42-(aq) + 8H+(aq) + 6e- ─→ S(s) + 4H2O(l) E° = 0.37V; ΔG° = -(6)(96.5kJ/V)(0.37V) =-
214kJ
8e- + 10H+(aq) + SO42-(aq) ─→ H2S(g) + 4H2O(l) ΔG° = -241 kJ

E° = - __ -241kJ__ = 0.31V
(8)(96.5kJ/V)

17.25. (a) Sn(s) ─→ Sn2+(aq) + 2e- E° = +0.14V


2e- + 2H+(aq) ─→ H2(g) E° = 0.00V
SO42-(aq) ─→ 2-
SO4 (aq)___________________________________
Sn(s) + 2H+(aq) + SO42-(aq) ─→ Sn2+(aq) + H2(g) + SO42-(aq) E° = +0.14V

(b) Sn(s) ─→ Sn2+(aq) + 2e- E° = +0.14V


2+
Sn (aq) ─→ Sn4+(aq) + 2e- E° = -0.13V
2 [SO42-(aq) + 4H+(aq) + 2e- ─→ SO2(g) + 2H2O(l) ] E° = +0.20V
Sn(s) + 2SO42-(aq) + 8H+(aq) ─→ 2SO2(g) + 2H2O(l) + Sn4+(aq) E° = +0.21V

*17.27. Fluorine is isoelectronic with OH so fluorosulfuric acid


is analogous with sulfuric acid but with an OH replaced by a F.
F
Fluorine is more electronegative than oxygen so even more
electron density is removed from the one remaining O-H O S O
bond than in sulfuric acid. That bond is therefore more polar
O
and more susceptible to attack by polar water molecules.
H

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.

*17.33. 2[ 4H2O(l) + Mn2+(aq) ─→ MnO4-(aq) + 8H+(aq) + 5e- ] E° = -1.51V


- 2- 2-
______ 5[ 2e + S2O8 (aq) ─→ 2SO4 (aq) ] E° = 2.01V
8H2O(l) + 2Mn2+(aq) +5S2O82-(aq) ─→ 2MnO4-(aq) +16H+(aq) +10SO42-(aq) E° = +0.50V

ΔG° = -nFE° = -(10)(96.5 kJ/V)(+0.50V) = -482 kJ/mole

1[ 7H2O(l) + 2Cr3+(aq) ─→ Cr2O72-(aq) + 14H+(aq) + 6e- ] E° = -1.33V


______ 3[ 2e- + S2O82-(aq) ─→ 2SO42-(aq) ] E° = 2.01V
7H2O(l) + 2Cr3+(aq) + 3S2O82-(aq) ─→ Cr2O72-(aq) + 14H+(aq) + 6SO42- E°= +0.68V

ΔG° = -(6)(96.5 kJ/V)(+0.68V) = -394 kJ/mol

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.

17.37 FeCl3 ⋅ 6H2O(s) + 6SOCl2(l) ─→ FeCl3(s) + 6SO2(g) + 12HCl(g)


Thionyl chloride is an excellent dehydrating agent.

*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

Electrons in cation as shown at right: Te Te


1) single bonds 9 x 2 = 18e-
2) lone pairs 6 x 2 = 12e- Te Te
30e-
The structure cannot be accounted for using all single bonds. The extra two electrons might very well be
delocalized in the triangular faces giving some dπ-pπ character to these bonds and therefore making them
slightly stronger and shorter.
boiling
*17.45. S(s) + SO32-(aq) S2O32-(aq)

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)

Ag+(aq) + 1e- ─→ Ag(s) ]2


2- 2- + -
2H2O + S2O4 (aq) ─→ 2SO3 (aq) + 4H (aq) + 2e ]1
2Ag+(aq) + 2H2O + S2O42-(aq) ─→ 2Ag(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

The VSEPR structure is the same as Figure 17.8(a).

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)

SO3(g) + H2SO4(aq) ─→ H2S2O7(aq)


H2S2O7(aq) + H2O(l) ─→ 2H2SO4(aq)

17.59. 2NH4OH(aq) + H2SO4(aq) ─→ (NH4)2SO4(aq) + 2H2O


The water could be continuously evaporated off to leave solid ammonium sulfate.

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

The sections and subsections of this chapter are listed below.

18.1 Discovery and Isolation of the Elements


Chlorine
Iodine
Bromine
Fluorine
Astatine
18.2 Fundamental Properties and the Network
Hydrides
Halides
Oxides
18.3 Oxoacids and Their Salts
Hypohalous Acids, HOX, and Hypohalites, OX-
Halous acids, HOXO and Halites, XO2-
Halic acids, HOXO2 and Halates, XO3-
Perhalic acids, HOXO3 and Perhalates, XO4-
18.4 Neutral and Ionic Interhalogens
18.5 Reactions and Compounds of Practical Importance
Fluoridation
Chlorination
Bleaches
Bromides
18.6 Selected Topic in Depth: Chlorofluorocarbons (CFCs) – A Threat to the Ozone Layer

120
Chapter 18 Objectives

You should be able to

• briefly relate how and by whom the halogens were discovered


• outline the general manner in which the periodic law, uniqueness principle, acid-base
character of oxides, and standard reduction potentials are applicable to the group
• explain why fluorine is such an extraordinarily powerful oxidizing agent and how this property
made it so difficult to isolate
• discuss the preparations and properties of the hydrogen halides
• summarize and give representative examples of the various ways to prepare halides of the
representative elements
• list and discuss the major applications of the halogen oxides
• discuss the preparations, properties, and applications of
1) the hypohalous acids and the hypohalites
2) the halous acids and the halites
3) the halic acids and the halates
4) the perhalic acids and the perhalates
• discuss the preparation, structures, and major reactions of the interhalogens
• discuss the history of and the chemistry central to systemic and topical fluoridation
• briefly explain the role of the halogens in the chlorination of water supplies, the nature of
bleaches, and the applications of the bromides
• discuss the history of and chemistry central to identifying the role of chlorofluorocarbons and
halons as threats to the ozone layer

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.

18.3. 2NaI(s) + 2H2SO4(aq) ─→ I2(s) + SO2(g) + 2H2O + Na2SO4(aq)


An analogous attempt to make chlorine gas, Cl2(g), would produce only HCl because sulfuric acid is not
a strong enough oxidizing agent to oxidize chlorides to chlorine.

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.

18.7. Gay-Lussac ─→ Fremy ─→ Moissan ─→ Stock

18.9. halogen mp covalent ionization


(°C) radius (Å) energy (kJ/mol)

F -220 0.72 1680


Cl -101 0.99 1251
Br -7.3 1.14 1143
I 114 1.33 1009
At 302 ----- 916

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.

18.11. (a) 2F2(g) + CH4(g) ─→ 4HF(g) + CF4(g)


(b) 3F2(g) + 2NH3(g) ─→ 6HF(g) + 2NF3(g)

18.13. H2(g) + F2(g) ─→ 2HF(g)


The weakness of the F-F bond in F2 combined with the high strength of the H-F bond in HF means that a
great amount of energy is released in the above reaction. In other words, much more energy is released
when the bonds of the products are formed than is needed to break the bonds of the reactants. The above
situation makes for an extremely exothermic reaction.

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)

ΔHored = ΔH(g) + ΕΑ + ΔHhyd

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.

18.19. NaF(aq) + H2SO4(aq) ─→ 2HF(aq) + Na2SO4(aq)


NaCl(aq) + H2SO4(aq) ─→ 2HCl(aq) + Na2SO4(aq)
2NaBr(aq) + 2H2SO4(aq) ─→ Br2(l) + SO2(g) + 2H2O(l) + Na2SO4(aq)
2NaI(aq) + 2H2SO4(aq) ─→ I2(s) + SO2(g) + 2H2O(l) + Na2SO4(aq)

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.

18.21. 2[ 2I-(aq) ─→ I2(s) + 2e- ] E° = - 0.54V


1[O2(g) + 4H (aq) + 4e- ─→ 2H2O(l)
+
] E° = +1.23V
4HI(aq) + O2(g) ─→ 2I2(s) + 2H2O(l) E° = +0.69V

2[ 2Br-(aq) ─→ Br2(l) + 2e- ] E° = - 1.07V


1[O2(g) + 4H (aq) + 4e- ─→ 2H2O(l)
+
] E° = +1.23V
4HBr(aq) + O2(g) ─→ 2Br2(l) + 2H2O(l) E° = +0.16V

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.

18.23. Note that the H-F- - -H F


hydrogen bonds must be linear. H H
F F

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

No, HNO3 could not be used to produce chlorine from chloride.

18.27. Al2O3(s) + 6HF(g) ─→ 2AlF3(s) + 3H2O(l)


2Al(s) + 3Cl2(g) ─→ 2AlCl3(s)

18.29. (a) 2Co3O4(s) + 6ClF3(g) ─→ 6CoF3(s) + 3Cl2(g) + 4O2(g)


(b) 2B2O3(s) + 4BrF3(l) ─→ 4BF3(g) + 2Br2(l) + 3O2(g)
(c) 3SiO2(s) + 4BrF3(l) ─→ 3SiF4(g) + 2Br2(l) + 3O2(g)

18.31. (a) PCl3(s) + 3H2O ─→ H3PO3(aq) + 3HCl(aq)


(b) PCl5(s) + 4H2O ─→ H3PO4(aq) + 5HCl(aq)

*18.33. NaSCN(aq) + AgNO3(aq) ─→ AgSCN(s) + NaNO3(aq)

18.35. Cl2O ClO2

Cl O Cl O Cl O

O Cl

Cl Cl O O
o o
<109.5 <109.5

18.37. Oxidizing agent: I2O5


Reducing agent: CO

*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-.

18.41. Ba(BrO3)2(aq) + H2SO4(aq) ─→ BaSO4(s) + 2HBrO3(aq)


Because barium sulfate is a fine white precipitate, this is sometimes called a "milkshake"
reaction.

*18.43. HIO3 + 5HI ─→ 3I2 + 3H2O


Oxidizing agent: HIO3
Reducing agent: HI
83 2-
18.45. 34SeO4 ─β-→ 83
35BrO4
-
+ 0-1e

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

The above reaction is thermodynamically feasible.

18.49. 2NH4ClO4(s) ─Δ→ N≡N(g) + Cl2(g) + 2 O=O(g) + 4H2O(l)


This reaction is very exothermic because large amounts of energy are released when the very strong
N≡N and O=O bonds are formed.

18.51. The bromine atom is sp3 hybridized. Three of these four _ +


hybrid orbitals are used to form a single bond with an oxygen atom. +
The remaining hybrid orbital contains a lone pair of electrons. Br O
One of the three oxygen atoms is singly bonded to a hydrogen _
+ _
atom. The other two oxygen atoms do not have hydrogens bonded
to them but rather form a second bond with the bromine atom. 4d 2p
This second bond is formed using a 4d orbital of bromine and a 2p
orbital of oxygen as shown at right. (The signs are the phases of the
orbitals.)

18.53. Br2(s) + F2(g) ─→ 2BrF(g)


Br2(s) + 3F2(g) ─→ 2BrF3(l)
BrF3(l) + F2(g) ─→ BrF5(l)

18.55. (a) Se(s) + 4ClF(g) ─→ SeF4(s) + 2Cl2(g)


(b) 6NiO(s) + 4ClF3(g) ─→ 6NiF2(s) + 2Cl2(g) + 3O2(g)
(c) 3SiO2(s) + 4BrF3(l) ─→ 3SiF4(s) + 2Br2(l) + 3O2(g)
(d) P4(s) + 20ICl(s) ─→ 4PCl5(s) + 10I2(s)

18.57. IF3 + 2H2O ─→ 3HF + HIO2


IF5 + 3H2O ─→ 5HF + HIO3
IF7 + 4H2O ─→ 7HF + HIO4

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.

*18.65. Dear Aunt Emily,


I enjoyed our last talk about aluminosilicates, sodium carbonate, and water softeners in general.
(See the answer to Problem 15.63). Have you had a chance lately to inspect some more detergent box
labels to see if aluminosilicates are catching on with other manufacturers? Now, in my class, we are
discussing fluoride additives in toothpastes. Water fluoridation (an example of “systemic fluoridation”),
I’m sure you know, continues to be a controversial topic in some communities, but these toothpaste
fluoride additives (an example of “topical fluoridation”) don’t seem to be a problem. That is probably
the case because people can choose these topical products but are forced to drink fluoridated water if that
is what his or her community has decided to do. Colgate’s MFP is based on phosphate, another
polyatomic anion like the silicates and aluminosilicates we discussed last. Phosphate has a formula of
PO43-; it has a phosphorus atom in the middle and four oxygen atoms around it. MFP stands for
monofluorophosphate and has a fluorine atom in place of one of the oxygen atoms. When MFP is
placed in water, it releases some fluoride ions that can protect teeth, particularly the developing teeth in
young children, against tooth decay. Evidently, when fluoride becomes part of a child’s tooth enamel,
her teeth are less susceptible to attack by the acids that result when saliva breaks down sugars in the
mouth. Crest’s fluoristat is simply sodium fluoride (very similar to ordinary table salt with fluoride in
place of chloride) that dissolves in water when the toothpaste is used. Again, this fluoride ion can be
taken in and made a part of the tooth enamel. You also asked about fluoristan, the additive that Crest
used before fluoristat. The –stan suffix comes from the Latin stannum for relating to or containing tin,
so fluoristan was Crest’s word for stannous fluoride. The tin was incompatible with newer forms of
tooth polishing compounds in toothpastes so stannous fluoride had to be replaced. There were also some
worries about the toxic effects of tin so perhaps that was another reason to go from –stan to –stat stat.
(My chemistry professor really enjoys puns like that!) Anyway, thanks for continuing to be interested in
my studies. It’s fun to explain these things to you.

18.67. Cl2(g) + 2NaOH(aq) ─→ NaOCl(aq) + NaCl(aq) + H2O


2Cl2(g) + 2Ca(OH)2(aq) ─→ Ca(OCl)2(aq) + CaCl2(aq) + 2H2O

*18.69. Dear Aunt Emily,


I enjoyed our earlier conversation about water softeners (see Problem 15.63) and our more
recent talk about various fluoride toothpaste additives (see Problem 18.66). I hear that you are interested
in talking about threats to the ozone layer as represented in Figure 18.6. You may have wondered if we
have any concrete evidence – a “smoking gun” so to speak – that chlorine compounds really are a threat

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

The sections and subsections of this chapter are listed below.

19.1 Discovery and Isolation of the Elements


Argon
Helium
Krypton, Neon, and Xenon
Radon
19.2 Fundamental Properties and the Network
19.3 Compounds of Noble Gases
History
Fluorides
Structures
Other Compounds
19.4 Physical Properties and Elements of Practical Importance
19.5 Selected Topic in Depth: Radon as a Carcinogen

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

19.1. P4(s) + 5O2(g) ─→ P4O10(s)

*19.3. NaOH(s) + CO2(g) ─→ NaHCO3(s)

19.5. Assuming air to be 20% oxygen (O2) and 80% nitrogen (N2), its average molecular weight is
given by the following equation:

Average MW = 0.20(32) + 0.80(28) = 29u

⎛ 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.

19.15. 235UF6(g), being slightly lighter, diffuses faster than 238UF6(g).

rate of diffusion of 235


UF6 (238) + 6(19.0) 352
= = = 1.004
rate of diffusion of 238
UF6 (235) + 6(19.0) 349

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.

19.19. 4KI(s) + XeF4(g) ─→ 4KF(s) + Xe(g) + 2I2(s)

*19.21. Oxidizing agent: XeF2


Reducing agent: H2O

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.

19.27. The F-Xe-F may be slightly less than


90º but not much because the xenon atom is + F
very large and there is plenty of room for the ~90o
F F
lone pair to spread out without unduly F F
influencing the Xe-F bonds Xe F Xe F
F F o
~90
F

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

19.33. Oxidizing agent: O3


Reducing agent: XeO3

*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.

19.37. 3[ XeO64-(aq) + 12H+(aq) + 8e- ─→ Xe(g) + 6H2O ]


2+ - + -
4[ 7H2O + Mn (aq) ─→ MnO4 (aq) + 8H + 5e ]
XeO64-(aq) + 2H2O + 2Cr3+(aq) ─→ 3Xe(g) + 4Cr2O72-(aq) + 20H+(aq)
131
238 4 234
*19.39. 92U ─α→ 2He + 90Th
(from clevite)
218 4 214
19.41. 84 Po ─α→ 2He + 82Pb

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