Periodic Trends (Halogens)

The periodic trends observed in the halogen group:

Melting and Boiling Points (increases down the group)

The melting and boiling points increase down the group because of the van der Waals forces. The size of the molecules increases down the
group. This increase in size means an increase in the strength of the van der Waals forces. (F<Cl<Br<I<At)

Atomic Radius (increases down the group)

The size of the nucleus increases down a group (F < Cl < Br < I < At) because the numbers of protons and neutrons increase. In addition,
more energy levels are added with each period. This results in a larger orbital, and therefore a longer atomic radius.

Ionization Energy (decreases down the group)

If the outer valence electrons are not near the nucleus, it does not take as much energy to remove them. Therefore, the energy required to
pull off the outermost electron is not as high for the elements at the bottom of the group since there are more energy levels. Also, the high
ionization energy makes the element appear non-metallic. Iodine and astatine display metallic properties, so ionization energy decreases
down the group (At < I < Br < Cl < F).
Electronegativity (decreases down the group)
The number of valence electrons in an atom increases down the group due to the increase in energy levels at progressively lower levels. The
electrons are progressively further from the nucleus; therefore, the nucleus and the electrons are not as attracted to each other. An increase in
shielding is observed. Electronegativity therefore decreases down the group (At < I < Br < Cl < F).

Electron Affinity (decreases down the group)

Since the atomic size increases down the group, electron affinity generally decreases (At < I < Br < F < Cl). An electron will not be as attracted to
the nucleus, resulting in a low electron affinity. However, fluorine has a lower electron affinity than chlorine. This can be explained by the small
size of fluorine, compared to chlorine.

Reactivity of Elements (decreases down the group)

The reactivities of the halogens decrease down the group ( At < I < Br < Cl < F). This is due to the fact that atomic radius increases in size with an
increase of electronic energy levels. This lessens the attraction for valence electrons of other atoms, decreasing reactivity. This decrease also
occurs because electronegativity decreases down a group; therefore, there is less electron "pulling." In addition, there is a decrease in oxidizing
ability down the group.

Oxidation States of Halogens in Compounds

As a general rule, halogens usually have an oxidation state of -1. However, if the halogen is bonded to oxygen or to another halogen, it can
adopt different states: the -2 rule for oxygen takes precedence over this rule; in the case of two different halogens bonded together, the more
electronegative atom takes precedence and adopts the -1 oxidation state.
Hydrogen Halides and Halogen Oxoacids
Hydrogen Halides
A halide is formed when a halogen reacts with another, less electronegative element to form a binary compound. Hydrogen, for example,
reacts with halogens to form halides of the form HX:
• Hydrogen Fluoride: HF
• Hydrogen Chloride: HCl
• Hydrogen Bromide: HBr
• Hydrogen Iodide: HI
Hydrogen halides readily dissolve in water to form hydrohalic (hydrofluoric, hydrochloric, hydrobromic, hydroiodic) acids. The properties of
these acids are given below:
• The acids are formed by the following reaction: HX (aq) + H2O (l) → X- (aq) + H3O+ (aq)
• All hydrogen halides form strong acids, except HF
• The acidity of the hydrohalic acids increases as follows: HF < HCl < HBr < HI
Hydrofluoric acid can etch glass and certain inorganic fluorides over a long period of time.
It may seem counterintuitive to say that HF is the weakest hydrohalic acid because fluorine has the highest electronegativity. However,​ the H-
F bond is very strong; if the H-X bond is strong, the resulting acid is weak. A strong bond is determined by a short bond length and a large
bond dissociation energy. Of all the hydrogen halides, HF has the shortest bond length and largest bond dissociation energy.
Halogen Oxoacids
A halogen oxoacid is an acid with hydrogen, oxygen, and halogen atoms. The acidity of an oxoacid can be determined through analysis of the
compound's structure. Halogens generally form four series of oxoacids namely hypohalous acids (+1 oxidation state), halous acids
(+3 oxidation state), halic acids (+5 oxidation state) and perhalic acids (+7 oxidation state). Chlorine forms four types of oxoacids. The halogen
oxoacids are given below:
•Hypochlorous Acid: HOCl
•Chlorous Acid: HClO2
•Chloric Acid: HClO3
•Perchloric Acid: HClO4
•Hypobromous Acid: HOBr
•Bromic Acid: HBrO3
•Perbromic Acid: HBrO4
•Hypoiodous Acid: HOI
•Iodic Acid: HIO3
•Metaperiodic Acid: HIO4; H5IO6
In each of these acids, the proton is bonded to an oxygen atom; therefore, comparing proton bond lengths is not useful in this case. Instead,
electronegativity is the dominant factor in the oxoacid's acidity. Acidic strength increases with more oxygen atoms bound to the central atom.
Interhalogens
The halogens react with each other to form interhalogen compounds. The general formula of most interhalogen compounds is XYn, where n
= 1, 3, 5 or 7, and X is the less electronegative of the two halogens. The compounds which are formed by the union of two different
halogens are called inter halogen compounds. There are never more than two types of halogen atoms in an interhalogen molecule. There
are of four general types:
1. AX- type : ClF, BrF, BrCl, ICl, IBr,
2. AX3-type: ClF3, BrF3, (ICl3)2,
3. AX5-type: ClF5, BrF5, IF5,
4. AX7-type: IF7.
The interhalogen compounds of type AX and AX3 are formed between the halogen having very low electronegative difference (e.g., ClF,
ClF3). The interhalogen compounds of type AX5 and AX7 are formed by larger atoms having low electronegativity with the smaller atoms
having high electronegativity. This is because it is possible to fit the greater number of smaller atom around a larger one (e.g. BrF5, IF7).
Interhalogen are all prone to hydrolysis and ionize to give rise to polyatomic ions. The inter halogens are generally more reactive than
halogens except F. This is because A-X bonds in interhalogens are weaker than the X-X bonds in dihalogen molecules. Reaction of inter
halogens are similar to halogens. Hydrolysis of interhalogen compounds give halogen acid and oxy-acid.
Nomenclature
To name an Interhalogen compound, the less electronegative element is placed on to the left in formulae and naming is done straight
forward.
Structures
The structures found for the various interhalogens conform to what would be expected based on the VSEPR model. For XY3 the shape can be
described as T-shaped with 2 lone pairs sitting in equatorial positions of a trigonal bipyramid. For XY5 the shape is a square pyramid with the
unpaired electrons sitting in an axial position of an octahedral and XY7 is a pentagonal bipyramid.

• All Interhalogens are volatile at room temperature. All are polar due to difference in their electronegativity. These are usually covalent
liquids or gases due to small electronegativity difference among them. Some compounds partially ionize in solution. For example:
2ICl → I+ + ICl2−
• Interhalogen compounds are more reactive than normal halogens except fluorine.
Pseudohalogen
➢ Pseudohalogens are polyatomic analogues of halogens, whose chemistry, resembling that of the true halogens, allows them to
substitute for halogens in several classes of chemical compounds. Well-known pseudohalogen functional groups include cyanide,
cyanate, thiocyanate, and azide.
➢ The term pseudohalogen was first introduced by Lothar Birckenbach in 1925 and further developed and justified in a series of papers in
the following years. The anions CN–, CNO–, N3–, OCN–, and SCN– can be coined classical linear pseudohalides. A small species can be
classified as a classical pseudohalogen when it fulfills the following criteria with respect to a halogen-like chemical behavior:
➢ A pseudohalogen (X) forms
• a strongly bound (linear) univalent radical (X×),
• a singly charged anion (X–),
• a pseudohalogenhydrogen acid of the type HX,
• Mostly contain a nitrogen atom.
 Polyhalide
• Polyhalogen ions/polyhalides are a group of polyatomic cations and anions containing halogens only.
• The ions can be classified into two classes, isopolyhalogen ions which contain one type of halogen only, and heteropolyhalogen ions with
more than one type of halogen.
• A chemical compound of metal halides and halogens. Polyhalides containing bromine (polybromides) and iodine (polyiodides) are known—
for example, potassium triiodide, KI3; cesium pentabromide, CsBr5; and potassium enneaiodide, KI9.
• Polybromides and polyiodides dissociate into ions in aqueous solutions. For example, KI3 yields the ions K+ and [I3]-
Potassium polyiodide solutions, which contain KI3 and KI5, are of the greatest importance. They are produced by adding a calculated
amount of iodine to an aqueous KI solution and are used whenever a concentrated iodine solution is required (the intrinsic solubility of
Iodinein water is negligible). In addition to polyhalides that contain only one type of halogen, polyhalides composed of various halogens
may be produced (for example, K[IF6]).
• The two classes of compounds have in common that they are, or contain, complexes of halogen atoms; the interhalogen compounds are
electrically neutral polyhalogen complexes, the polyhalides contain negatively charged polyhalide ions.

Read this article for polyhalides.

https://en.wikipedia.org/wiki/Polyhalogen_ions
Group 18 (VIIIA) Nobel gases
The noble gases (Group 18) are located in the far right of the periodic table and were previously referred to as the "inert gases" due to the
fact that their filled valence shells (octets) make them extremely nonreactive. The noble gases were characterized relatively late compared
to other element groups.
History
The first person to discover the noble gases was Henry Cavendish in the late 180th century. Cavendish distinguished these elements by
chemically removing all oxygen and nitrogen from a container of air. The nitrogen was oxidized to NO2 by electric discharges and absorbed
by a sodium hydroxide solution. The remaining oxygen was then removed from the mixture with an absorber. The experiment revealed that
1/120 of the gas volume remained un-reacted in the receptacle. The second person to isolate, but not typify, them was William Francis
(1855-1925). Francis noted the formation of gas while dissolving uranium minerals in acid.

The Electron Configurations for Noble Gases

•Helium 1s2
•Neon [He] 2s2 2p6
•Argon [Ne] 3s2 3p6
•Krypton [Ar] 3d10 4s2 4p6
•Xenon [Kr] 4d10 5s2 5p6
•Radon [Xe] 4f14 5d10 6s2 6p6
The Atomic and Physical Properties
• Atomic mass, boiling point, and atomic radii increase down a group in the periodic table.
• The first ionization energy decreases down a group in the periodic table.
• The noble gases have the largest ionization energies, reflecting their chemical inertness.
• Down Group 18, atomic radius and interatomic forces increase resulting in an increased melting point, boiling point, enthalpy of
vaporization, and solubility.
• The increase in density down the group is correlated with the increase in atomic mass.
• Because the atoms increase in atomic size down the group, the electron clouds of these non-polar atoms become increasingly
polarized, which leads to weak van Der Waals forces among the atoms. Thus, the formation of liquids and solids is more easily attainable
for these heavier elements because of their melting and boiling points.
• Because noble gases’ outer shells are full, they are extremely stable, tending not to form chemical bonds and having a small tendency to
gain or lose electrons.
• Under standard conditions all members of the noble gas group behave similarly.
• All are monatomic gases under standard conditions.
• Noble gas atoms, like the atoms in other groups, increase steadily in atomic radius from one period to the next due to
the increasing number of electrons.
• The size of the atom is positively correlated to several properties of noble gases. The ionization potential decreases with
an increasing radius, because the valence electrons in the larger noble gases are further away from the nucleus; they are therefore held
less tightly by the atom.
• The attractive force increases with the size of the atom as a result of an increase in polarizability and thus a decrease in ionization
potential.
• Overall, noble gases have weak interatomic forces, and therefore very low boiling and melting points compared with elements of other
groups.
Compounds of Nobel gases
The heavier noble gases have more electron shells than the lighter ones. Hence, the outermost electrons are subject to a shielding
effect from the inner electrons that makes them more easily ionized, since they are less strongly attracted to the positively charged nucleus.
This results in an ionization energy low enough to form stable compounds with the most electronegative elements, fluorine and oxygen, and
even with less electronegative elements such as nitrogen and carbon under certain circumstances.

Xenon compounds
After the initial 1962 studies on XeF4 and XeF2, xenon compounds that have been synthesized include other fluorides (XeF6), oxyfluorides
(XeOF2, XeOF4, XeO2F2, XeO3F2, XeO2F4) and oxides (XeO2, XeO3 and XeO4).
Xenon fluorides react with several other fluorides to form fluoroxenates, such as sodium octafluoroxenate Na2+XeF 8 2−), and
fluoroxenonium salts, such as trifluoroxenonium hexafluoroantimonate (XeF3+SbF 6 −).
Compounds of Xe (Xenon)
Uses of Nobel Gases
Helium
• Helium is used as a component of breathing gases due to its low solubility in fluids or lipids. This is important because other gases are
absorbed by the blood and body tissues when under pressure during scuba diving. Because of its reduced solubility, little helium is taken
into cell membranes; when it replaces part of the breathing mixture, helium causes a decrease in the narcotic effect of the gas at far
depths. The reduced amount of dissolved gas in the body means fewer gas bubbles form, decreasing the pressure of the ascent.
• Helium and Argon are used to shield welding arcs and the surrounding base metal from the atmosphere.
• Helium is used in very low temperature cryogenics, particularly for maintaining superconductors (useful for creating strong magnetic
fields) at a very low temperatures. Helium is also the most common carrier gas in gas chromatography.
Neon
• Neon has many common and familiar applications: neon lights, fog lights, TV cine-scopes, lasers, voltage detectors, luminous warnings,
and advertising signs.
• The most popular application of neon is the neon tubing used in advertising and elaborate decorations. These tubes are filled with neon
and helium or argon under low pressure and submitted to electrical discharges. The color of emitted light is depending on the
composition of the gaseous mixture and on the color of the glass of the tube. Pure Neon within a colorless tube absorbs red light and
reflects blue light, as shown in the figure below. This reflected light is known as fluorescent light.
Argon
• Argon has a large number of applications in electronics, lighting, glass, and metal fabrications.
• Argon is used in electronics to provide a protective heat transfer medium for ultra-pure silicon crystal semiconductors and for growing
germanium.
• Argon can also fill fluorescent and incandescent light bulbs, creating the blue light found in "neon lamps." By utilizing argon's low thermal
conductivity, window manufacturers provide a gas barrier needed to produce double-pane insulated windows. This insulation barrier
improves the windows' energy efficiencies.
• Argon also creates an inert gas shield during welding, flushes out melted metals to eliminate porosity in casting, and provides an oxygen-
and nitrogen-free environment for annealing and rolling metals and alloys.
Krypton
• Similarly, to argon, krypton can be found in energy efficient windows. Because of its superior thermal efficiency, krypton is sometimes
chosen over argon for insulation.
• It is estimated that 30% of energy efficient windows sold in Germany and England are filled with krypton; approximately 1.8 liters of
krypton are used in these countries.
• Krypton is also found in fuel sources, lasers and headlights. In lasers, krypton functions as a control for a desired optic wavelength.
• It is usually mixed with a halogen (most likely fluorine) to produce excimer lasers. Halogen sealed beam headlights containing krypton
produce up to double the light output of standard headlights.
• In addition, Krypton is used for high performance light bulbs, which have higher color temperatures and efficiency because the
krypton reduces the rate of evaporation of the filament.
Xenon
• Xenon has various applications in incandescent lighting, x-ray development, plasma display panels (PDPs), and more.
• Incandescent lighting uses xenon because less energy can be used to obtain the same light output as a normal incandescent lamp.
• Xenon has also made it possible to obtain better x-rays with reduced amounts of radiation.
• When mixed with oxygen, it can enhance the contrast in CT imaging. These applications have had great impact on the health care
industries. Plasma display panels (PDPs) using xenon as one of the fill gases may one day replace the large picture tubes in television and
computer screens.
• Nuclear fission products may include several radioactive isotopes of xenon, which absorb neutrons in nuclear reactor cores. The
formation and elimination of radioactive xenon decay products are factors in nuclear reactor control.

Radon
• Radon is reported as the second most frequent cause of lung cancer, after cigarette smoking. However, it also has beneficial applications
in radiotherapy, arthritis treatment, and bathing.
• In radiotherapy, radon has been used in implantable seeds, made of glass or gold, primarily used to treat cancers. It has been said that
exposure to radon mitigates auto-immune diseases such as arthritis.
• Some arthritis sufferers have sought limited exposure to radioactive mine water and radon to relieve their pain.
• "Radon Spas" such as Bad Gastern in Austria and Onsen in Japan offer a therapy in which people sit for minutes to hours in a high-radon
atmosphere, believing that low doses of radiation will boost up their energy.