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table. As expected, these elements have certain properties in common. They all form
diatomic molecules (H2, F2, Cl2, Br2, I2, and At2), for example, and they all form
negatively charged ions (H-, F-, Cl-, Br-, I-, and At-).
When the chemistry of these elements is discussed, hydrogen is separated from the
others and astatine is ignored because it is radioactive. (The most stable isotopes
of astatine have half-lives of less than a minute. As a result, the largest samples
of astatine compounds studied to date have been less than 50 ng.) Discussions of
the chemistry of the elements in Group VIIA therefore focus on four elements:
fluorine, chlorine, bromine, and iodine. These elements are called the halogens
(from the Greek hals, "salt," and gennan, "to form or generate") because they are
literally the salt formers.
None of the halogens can be found in nature in their elemental form. They are
invariably found as salts of the halide ions (F-, Cl-, Br-, and I-). Fluoride ions
are found in minerals such as fluorite (CaF2) and cryolite (Na3AlF6). Chloride ions
are found in rock salt (NaCl), the oceans, which are roughly 2% Cl- ion by weight,
and in lakes that have a high salt content, such as the Great Salt Lake in Utah,
which is 9% Cl- ion by weight. Both bromide and iodide ions are found at low
concentrations in the oceans, as well as in brine wells in Louisiana, California,
and Michigan.
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Fluorine (F2), a highly toxic, colorless gas, is the most reactive element known
--so reactive that asbestos, water, and silicon burst into flame in its presence.
It is so reactive it even forms compounds with Kr, Xe, and Rn, elements that were
once thought to be inert. Fluorine is such a powerful oxidizing agent that it can
coax other elements into unusually high oxidation numbers, as in AgF2, PtF6, and
IF7.
Chlorine (Cl2) is a highly toxic gas with a pale yellow-green color. Chlorine is a
very strong oxidizing agent, which is used commercially as a bleaching agent and as
a disinfectant. It is strong enough to oxidize the dyes that give wood pulp its
yellow or brown color, for example, thereby bleaching out this color, and strong
enough to destroy bacteria and thereby act as a germicide. Large quantities of
chlorine are used each year to make solvents such as carbon tetrachloride (CCl4),
chloroform (CHCl3), dichloroethylene (C2H2Cl2), and trichloroethylene (C2HCl3).
Bromine (Br2) is a reddish-orange liquid with an unpleasant, choking odor. The name
of the element, in fact, comes from the Greek stem bromos, "stench." Bromine is
used to prepare flame retardants, fire-extinguishing agents, sedatives, antiknock
agents for gasoline, and insecticides.
Iodine is an intensely colored solid with an almost metallic luster. This solid is
relatively volatile, and it sublimes when heated to form a violet-colored gas.
Iodine has been used for many years as a disinfectant in "tincture of iodine."
Iodine compounds are used as catalysts, drugs, and dyes. Silver iodide (AgI) plays
an important role in the photographic process and in attempts to make rain by
seeding clouds. Iodide is also added to salt to protect against goiter, an iodine
deficiency disease characterized by a swelling of the thyroid gland.
Some of the chemical and physical properties of the halogens are summarized in the
table below. There is a regular increase in many of the properties of the halogens
as we proceed down the column from fluorine to iodine, including the melting point,
boiling point, intensity of the color of the halogen, the radius of the
corresponding halide ion, and the density of the element. On the other hand, there
is a regular decrease in the first ionization energy as we go down this column. As
a result, there is a regular decrease in the oxidizing strength of the halogens
from fluorine to iodine.
Melting
Point
(C) Boiling
Point
(C) Color Natural
Abundance
(ppm) 1st
Ionization
Energy
(kJ/mol) Electron
Affinity
(kJ/mol) Ionic
Radius
(nm) Density
(g/cm3)
F2 -218.6 -188.1 colorless 544 1680.6
322.6 0.133 1.513
Cl2 -101.0 -34.0 pale green 126 1255.7
348.5 0.184 1.655
Br2 -7.3 59.5 dark red-brown 2.5 1142.7
324.7 0.196 3.187
I2 113.6 185.2 very dark violet
almost black 0.46 1008.7 295.5 0.220 3.960
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The halogens can be made by reacting a solution of the halide ion with any
substance that is a stronger oxidizing agent. Iodine, for example, can be made by
reacting the iodide ion with either bromine or chlorine.
The best way of producing a strong reducing agent is to pass an electric current
through a salt of the metal. Sodium, for example, can be prepared by the
electrolysis of molten sodium chloride.
electrolysis
2 NaCl(l) ----> 2 Na(s) + Cl2(g)
In theory, the same process can be used to generate strong oxidizing agents, such
as F2.
Finally, in 1886 Henri Moissan successfully isolated F2 gas from the electrolysis
of a mixed salt of KF and HF and noted that crystals of silicon burst into flame
when mixed with this gas. Electrolysis of KHF2 is still used to prepare fluorine
today, as shown in the figure below.
electrolysis
2 KHF2(s) ----> H2(g) + F2(g) + 2 KF(s)
graphic
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Oxidation
Number Examples
-1 CaF2, HCl, NaBr, AgI
0 F2, Cl2, Br2, I2
+1 HClO, ClF
+3 HClO2, ClF3
+5 HClO3, BrF5, BrF6-, IF5
+7 HClO4, BrF6+, IF7
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General Trends in Halogen Chemistry
1. Neither double nor triple bonds are needed to explain the chemistry of the
halogens.
3. Chlorine, bromine, and iodine have valence shell d orbitals and can expand their
valence shells to hold as many as 14 valence electrons.
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The hydrogen halides are compounds that contain hydrogen attached to one of the
halogens (HF, HCl, HBr, and HI). These compounds are all colorless gases, which are
soluble in water. Up to 512 mL of HCl gas can dissolve in a single mL of water at
0oC and 1 atm, for example. Each of the hydrogen halides ionizes to at least some
extent when it dissolves in water.
H2O
HCl(g) ----> H+(aq) + Cl-(aq)
Several of the hydrogen halides can be prepared directly from the elements.
Mixtures of H2 and Cl2, for example, react with explosive violence in the presence
of light to form HCl.
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ClF3 and BrF5 are extremely reactive compounds. ClF3 is so reactive that wood,
asbestos, and even water spontaneously burn in its presence. These compounds are
excellent fluorinating agents, which tend to react with each other to form positive
ions such as ClF2+ and BrF4+ and negative ions such as IF2- and BrF6-.
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Chlorine reacts with the OH- ion to form chloride ions and hypochlorite (OCl-)
ions.
reaction
When the solution is hot, this reaction gives a mixture of the chloride and
chlorate (ClO3-) ions.
The names of the oxyanions of the halogens use the endings -ite and -ate to
indicate low and high oxidation numbers and the prefixes hypo- and per- to indicate
the very lowest and very highest oxidation numbers, as shown in the table below.
Each of these ions can be converted into an oxyacid, which is named by replacing
the -ite ending with -ous and the -ate ending with -ic.
Oxyanions Oxyacids
Oxidation State
of the Chlorine Compound Name Compound Name
+1 ClO- hypochlorite HClO hypochlorous acid
+3 ClO2- chlorite HOClO chlorous acid
+5 ClO3- chlorate HOClO2 chloric acid
+7 ClO4- perchlorate HOClO3 perchloric acid
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