Chemistry of the Main Group Elements
Collection Editor:
Andrew R. Barron
Chemistry of the Main Group Elements
Collection Editor:
Andrew R. Barron
Authors:
Andrew R. Barron
Christopher E. Hamilton
Carissa Smith
Online:
< http://cnx.org/content/col11124/1.25/ >
CONNEXIONS
Rice University, Houston, Texas
This selection and arrangement of content as a collection is copyrighted by Andrew R. Barron. It is licensed under
the Creative Commons Attribution License 3.0 (http://creativecommons.org/licenses/by/3.0/).
Collection structure revised: August 20, 2010
PDF generated: March 22, 2014
For copyright and attribution information for the modules contained in this collection, see p. 511.
Table of Contents
Preface to the Chemistry of the Main Group Elements
......................................... 1
1 General Concepts and Trends
Fundamental Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Structure and Bonding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Acids, Bases, and Solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
Chemical Reactivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
Periodic Trends for the Main Group Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
1.1
1.2
1.3
1.4
1.5
2 Hydrogen
Discovery of Hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . 65
The Physical Properties of Hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
Synthesis of Molecular Hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
Atomic Hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
The Proton . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . 73
Hydrides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
The Hydrogen Bond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
Isotopes of Hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
Nuclear Fusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
Storage of Hydrogen for Use as a Fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
2.1
2.2
2.3
2.4
2.5
2.6
2.7
2.8
2.9
2.10
3 Group 1: The Alkali Metals
The Alkali Metal Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
Compounds of the Alkali Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
The Anomalous Chemistry of Lithium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
Organolithium Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
3.1
3.2
3.3
3.4
4 Group 2: The Alkaline Earth Metals
4.1
4.2
4.3
4.4
The Alkaline Earth Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
Calcium the Archetypal Alkaline Earth Metal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
Dierences for Beryllium and Magnesium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
Organometallic Compounds of Magnesium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . 173
5 Group 12
5.1
5.2
5.3
5.4
The Group 12 Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
Group 12 Chalcogenides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
Organometallic Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
The Myth, Reality, and History of Mercury Toxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
6 Group 13
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
The Group 13 Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
Trends for the Group 13 Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219
Borides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . 221
Hydrides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
Oxides, Hydroxides, and Oxygen Donor Ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
Boron Compounds with Nitrogen Donors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
Gallium Arsenide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . 249
Chalcogenides of Aluminum, Gallium, and Indium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260
Group 13 Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . 264
iv
Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 276
7 Group 14
7.1
7.2
7.3
The Group 14 Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . 288
Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 333
8 Group 15: The Pnictogens
8.1
8.2
8.3
8.4
8.5
The Group 15 Elements: The Pnictogens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
Reaction Chemistry of Nitrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 364
Hydrides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 364
Oxides and Oxoacids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 388
Halides of Phosphorous . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . 405
9 Group 16
9.1
9.2
9.3
9.4
9.5
9.6
9.7
9.8
9.9
The Group 16 Elements: The Chalcogens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409
Ozone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 429
Water: The Fuel for the Medieval Industrial Revolution . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . 432
Hydrogen Peroxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 437
Hydrogen Peroxide Providing a Lift for 007 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 438
Comparison of Sulfur to Oxygen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . 443
Chalconide Hydrides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 445
Oxides and Oxyacids of Sulfur . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . 447
Sulfur Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 451
10 Group 17: The Halogens
The Group 17 Elements: The Halogens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . 457
Compounds of Fluorine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 473
Compounds of Chlorine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 476
Oxyacids of Chlorine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 481
Bromine Triuoride as a Solvent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 483
Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 485
10.1
10.2
10.3
10.4
10.5
11 Group 18: The Noble Gases
11.1
The Group 18 Elements: The Noble Gases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 487
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 498
Attributions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .511
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Preface to the Chemistry of the Main
Group Elements
1
The main group (s- and p-block) elements are among the most diverse in the Periodic Table. Ranging from
non-metallic gases (e.g., hydrogen and uorine), through semi-metals (e.g., metalloids such as silicon) to
highly reactive metals (e.g., sodium and potassium). The study of the main group elements is important
for a number of reasons. On an academic level they exemplify the trends and predictions in structure and
reactivity that are the key to the Periodic Table. They represent the diversity of inorganic chemistry, and
the fundamental aspects of structure and bonding that are also present for the transition metal, lanthanide
and actinide elements.
The main group elements represent the most prevalent elements in the Earth's crust, as well as most of
the key elements of life, and have enormous industrial, economic, and environmental importance. In this
regard an understanding of the chemistry of the main group elements is vital for students within science,
engineering, and medicine; however, it is hoped that those who make political and economic decisions would
make better ones (or at least more responsible ones) if they had a fraction of the knowledge of the world
around them.
Since the position of the main group elements within the Periodic Table denes their properties (and
visa versa) this represents a logical organization of the topics. Prior to introducing the elements, a series
of general and background topics are covered to provide the basis for further discussion. The subsequent
organization is based upon a Chapter for each Group of the s- and p-block elements; however, hydrogen
is given its own chapter due to its importance as an element. Although the Group 12 elements are often
omitted from a discussion of main group elements they have been included herein.
Some chapters are organized with regard to individual elements (e.g., carbon, silicon, etc.) and others
are arranged with regard the types of compounds (e.g., oxides, halides, etc.). This is based upon particular
interest or importance of an element. An eort has been made to ensure that topics are not covered twice
(unless necessary) and so in general a particular subject is covered in the Group chapter associated with
the lower Group number. For example, the halides of boron are described in the Chapter on the Group 13
elements rather than Group 17 elements.
In addition to the basic synthesis, structure, properties, and reactivity of the elements and their compounds, sections describing some industrial use, as well as historical or social perspective have been added.
These sections were as a result of attempts within class to put the chemistry into a context outside of the
classroom. It is important that the discovery and use of elements be understood to be a human endeavor
rather than a series of abstract concepts or facts. It is only by an appreciation of the past that we can
advance the future.
Although this book was developed from the Rice University course Chem 360 (Inorganic Chemistry),
and is not intended to be either encyclopedic or overly detailed, as with all Connexions courses there is an
evolution of the topics covered. Thus, some topics will be covered at a greater or lesser depth depending on
the relevance or interest. Given the continued expansion in the chemistry of the main group elements it is
intended that appropriate modules will be added as they are developed.
1 This content is available online at <http://cnx.org/content/m33078/1.1/>.
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1
2
Andrew R. Barron
Rice University, Houston, TX 77005. E-mail: [email protected].
Available for free at Connexions <http://cnx.org/content/col11124/1.25>