The Halogen Family – Group 7A(17)
- Elements such as fluorine, chlorine, bromine, iodine, and astatine belong to Group 17, the halogen group.
- Exists as diatomic molecules
- Have high ionization energy and form the most electronegative group
Physical Properties of Halogens
- Display regular trends in their physical properties
- EXCEPT: melting point, boiling point, heats of fusion, and vaporization
o They increase down Group 7A
o This is because of the different type of bonding in the elements
o Halogens exist as diatomic molecules through dispersion forces, thus increases in strength when atoms
become larger and more polarized
Alkali metals, on the other hand, are held together by metallic bonding, thus decreases in strength
when atoms become larger
- Fluorine – very pale yellow gas
- Chlorine – yellow-green gas (pale green at room temperature)
- Bromine – brown-orange liquid (red at room temperature)
- Iodine – purple-black solid
- Astatine – radioactive element that exist only in small amounts in nature
Reactivity of Halogens
- Group 7A(17) reacts with metal and nonmetal to form ionic and covalent compounds
o Metal and nonmetal halides, halogen oxides, and oxoacids
- Halogen reactivity occurs as it is because of an electron configuration one electron away from that of a noble gas
o Their electron configuration, ns2np5 allows them to easily react with Group 1 and 2 metals
o 7A nonmetal must gain one electron to fill its outer level
o Two ways of filling the outer level:
1. Gaining an electron from a metal atom, thus forming a negative ion as the metal forms a
positive one
2. Sharing an electron pair with a nonmetal atom, thus forming a covalent bond
- Down the group, reactivity reflects the decrease in electronegativity.
o Fluorine is the most reactive, while iodine is the least reactive
Exceptional reactivity of F2 is due to the weakness of F-F bond
Despite F being small and having short bonds, the lone pairs on each F atom repel those on the
other, thus weakening the bond
Because of these factors, F2 explosively reacts with every elements
Halogens as Oxidizing Agents
- Fluorine
o Too strong to be an oxidizing agent
o Oxidizes water to oxygen, making it impossible to carry out simple reactions
o Reaction:
- Chlorine, Bromine, and Iodine
o halogen higher in the group can oxidize the ions of one lower down
o Chlorine oxidizes both bromide ions and iodide ions.
o Bromine and iodine cannot reclaim those electrons from the chloride ions formed—chlorine is a more
powerful oxidizing agent than either bromine or iodine.
- Halogens display largest range of electronegativity and are all electronegative enough to behave as nonmetals,
thus acting as oxidizing agents in majority of their reactions
- Halogens higher in the group can oxidize halide ions lower down
o Reaction:
- Oxidizing ability of X2 decreases down the group
o The lower the EN, the less strongly each X atoms pill electrons
- Reducing ability of X—increases down the group
o The larger the ion, the more easily it gives up its electron
- Halogens undergo important aqueous redox chemistry
o Fluorine is such a powerful oxidizing agent that it tears water apart, oxidizing the O to produce O2, some
O3, and HFO (hypofluorous acid)
- Other halogens undergo disproportionation
o Reaction:
- At equilibrium, very little product is present unless excess OH ion is added, which reacts with the HX and HXO
and drives the reaction to completion
o Reaction:
- Example: Chlorine Reaction. The product mixture acts a bleach: household bleach is a dilute solution of sodium
hypochlorite (NaClO). Heating causes XO to disproportionate further, creating oxoanions with X in a higher
oxidation state.
o Reaction:
Reaction with Water
- Iodine and bromine cannot oxidize water to oxygen because they have smaller reduction potential than oxygen.
Thus, they cannot react with water.
- Fluorine and Chlorine have larger reduction potentials and can oxidize water.
o Fluorine Reaction:
o Fluorine Reaction:
o Chlorine Reaction:
Hydrogen Halides
- Halogens form gaseous hydrogen halides (HX) when reacted directly with H 2 or through the action of a
concentrated acid on the metal halide
o Reaction:
o Reaction:
o Reaction:
- All the halogens react directly with hydrogen, forming covalent bonds and—at sufficient levels of purity—
colorless gases at room temperature.
o Hydrogen reacts with fluorine, chlorine, bromine, and iodine, forming HF, HCl, HBr, and HI,
respectively.
o The bond strength of these molecules decreases down the group: HF > HCl > HBr > HI
- All hydrogen halides are soluble in water, forming strong acids with exception of HF
- General Equation:
- In water, gaseous HX molecules form a hydrohalic acid. Only HF, with its relatively short, strong bond, forms a
weak acid.
- The others dissociate completely to form the stoichiometric amount of H3O ions.
o Reaction:
o Reaction:
Interhalogen Compounds: The Halogen Halides
- Halogens have the ability to form compounds with other halogens.
- Halogens react exothermically with another to form many interhalogen compounds
o Simplest compounds are diatomic molecules: ClF or BrCl
- The more electronegative halogen is in the -1 oxidation state, and the less electronegative is in the +1 state.
- Interhalogens of general formula XYn (n = 3, 5, 7) form when the larger members of the group (X) use d orbitals
to expand their valence shells.
- The central atom has the lower electronegativity and a positive oxidation state.
- Commercial used of interhalogens: powerful fluorinating agents
o Reaction:
o Reaction:
o Reaction:
o Their reactions with water are nearly explosive and yield HF and the oxoacid in which the central halogen
has the same oxidation state
o Reaction:
Oddness and Evenness of Oxidation State
- Odd-numbered groups exhibit odd-numbered oxidation state, while even-numbered groups exhibit even-
numbered oxidation state
o This general behavior can be attributed to the fact that almost all stable molecules have paired electrons,
either as bonds or lone pairs. Thus, when bonds break or form, two electrons are always involved, making
the oxidation state change by 2
