GROUP 17 ELEMENTS

[Link]. Chemistry
Semester I

Dr. ASHOK KUMAR SINGH

Assistant Professor
University of Lucknow
Lucknow
Members
• The group 17 elements include fluorine (F), chlorine (Cl),
bromine(Br), iodine(I) and astatine (At) from the top to the bottom.
• They are called “halogens” because they give salts when they react
with metals.
• The valence shell electronic configuration of these electrons is
ns2np5. Thus, there are 7 electrons in the outermost shell of these
elements.
• The element misses out on the octet configuration by one electron.
• Thus, these elements look out to share one electron and form a
covalent bond or gain one electron and form an ionic bond.
Therefore, these are very reactive non-metals.
Physical Properties
• Physical state: The group 17 elements are found in
diverse physical states. For example, Fluorine and
Chlorine are gases. On the other hand, Bromine is a liquid
and Iodine is solid.
• Colour: These elements have a variety of colours. For
example, while Fluorine is pale yellow in colour, Iodine is
dark violet in colour.
• Solubility: Fluorine and Chlorine are soluble in water. On
the other hand, Bromine and Iodine are very less soluble
in water.
• Melting and boiling points: Melting and boiling points of
these elements increase as we move down the group
from Fluorine to Iodine. Thus, Fluorine has the lowest
boiling and melting points.
General outer electronic configuration of elements of group 17 is ns2np5
Element Atomic Number Electronic
Configuration

F 9 [He]2s22p5
Cl 17 [Ne]3s23p5
Br 35 [Ar]3d104s24p5
I 53 [Kr]4d105s25p5
At 86 [Xe]4f145d106s26p5

Covalent and Ionic radius

Covalent and ionic radii increase on moving down the group
Element F Cl Br I
Covalent radius (pm) 64 99 111 128

Ionic Radii X- 136 181 195 216

(pm)
Ionization energies
• Members of group 17 have very little or no tendency to lose an
electron.
• Thus, they have a very high value of ionisation enthalpy.
Ionisation enthalpy decreases from top to bottom in the group
due to the increase in atomic size.
• As a consequence iodine possess some metallic character.
Electron Affinity
• The atoms of group 17 elements are only one electron short of
attaining stable noble gas configurations.
• Thus, these elements have a maximum negative electron gain
enthalpy in the corresponding periods.
• Electron gain enthalpy of these elements becomes
less negative as we move down the group due to the
increase in atomic size.
• However, chlorine has a more negative value of
electron gain enthalpy with respect to fluorine.
Electronegativity
• The elements of group 17 have a very high value of
electronegativity.
• The electronegativity decreases down the group
due to the decrease in effective nuclear charge.
• Thus, fluorine is the most electronegative element.
Oxidation states
• All the elements of the halogen family exhibit -1 oxidation
state. However, elements such as chlorine, bromine, and
iodine also show +1, +3, +5 and +7 state.
• This higher oxidation state of chlorine, bromine,
and iodine is realized when these halogens are in
combination with small and highly electronegative atoms
such as fluorine and oxygen.
• The oxides and oxoacids of chlorine and bromine have +4
and +6 states. There are no valence shells d orbitals in
fluorine atom and therefore it cannot expand its octet.
• Fluorine being the most electronegative element exhibits
only -1 oxidation state.
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.
Oxidising Power
• All the halogens are great oxidizing agents.
• Of the list, fluorine is the most powerful oxidizing
agent. It is capable of oxidizing all the halide particles
to halogen.
• The oxidizing power reduces as we move down the
group. The halide particles also act as reducing
agents.
• However, their reducing capacity decreases down the
group as well.
Reaction with Metals
• As halogens are very reactive, they react with most
of the metals instantly and form the resulting metal
halides.
• For example, sodium reacts with chlorine gas and
forms sodium chloride.
2Na(s) + Cl2(g) → 2NaCl(s)
• This process is an exothermic one and gives out a
bright yellow light and a lot of heat energy.
• Metal halides are ionic in nature. This ionic
character of the halides reduces from fluorine to
iodine.
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 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.
Structures of the Oxoacids of Halogens
• In these oxoacids, the focal halogen molecule is sp3
hybridized.
• One X-OH bond is basically present in each oxoacid.
In the majority of these oxoacids, "X = O" bonds are
available. The double bond introduced in an
oxoacid between the focal halogen particle and
oxygen is dπ- pπ in nature.
• Hypohalous acids incorporate hypofluorous acid,
hypochlorous acid, hypobromous acid and
hypoiodous acid. The halogen has the oxidation
condition of +1 in hypohalous acids.
• HOF has been isolated by reaction of difluorine gas
with ice at 230 K but it does not ionise in water or
give stable salts and on warming to room
temperature it decomposes to HF.
2 HOF → 2 HF + O2
• The hypohalous acids (X=Cl, Br, I) are conveniently
prepared by the reaction of the dihalogen with mercury
oxide:
2X2 + 3 HgO + H2O → 2 HOX + Hg3O2X2
• The hypohalous salts formed from the heavier halogens
are all weak acids with the hypochlorites being important
industrial reagents.
• Bleaching powder is a mixture of CaCl2, Ca(OH)2 and
Ca(OCl)2 and is manufactured by the reaction of dichlorine
on Ca(OH)2.
• The sodium salt is a well known disinfectant and bleaching
agent
• Each of these hypohalites are unstable and
disproportionate at room temperature to the halates and
halide ion:
3[OX]- → [XO3]- + 2X-
• Hypohalous acids, have a tendency of making halic
acids as they are less stable.
3HOX → HOXO2 + 3HX
Hypohalous acid Halic acid
• Halous acids, includes only chlorous acid. The
chlorine has an oxidation state of +3 in chlorous
acid. The chlorite ion possess V - shape.
• Halic acids, includes chloric acid, bromic acid and
iodic acid in which halogens possess +5 oxidation
state.
• The individual halate ions are pyramidal shaped.
• Perhalic acids, includes perchloric acid, perbromic
acid and periodic acid. The oxidation state of the
halogen in these oxoacids is+7. The shape of the
perhalate ion is tetrahedral.
• In any series of oxoacids of halogens, the first
member possesses high acidic strength. This is due
to the high electro-negativity and small size of the
respective halogens.
• Among perhalic acids, perchloric acid has high
acidic strength. As chlorine is more electro-negative
than bromine or iodine, the shared electron pair
lies relatively nearer to chlorine in a Cl-O bond than
bromine in a Br-O bond or iodine in an I-O bond. As
a consequence, the O-H bond becomes much
weaker in case of perchloric acid, thereby
facilitating the release of a proton readily.
HOClO3 > HOBrO3 > HOIO3
• The acidic strength of an oxoacid increases with an
increase in the oxidation number of the halogen.
• EX: Among the four oxoacids of chlorine, the acidic
strength increases markedly from hypochlorous
acid to perchloric acid.
• Chlorous acid, chloric acid and bromic acid cannot be
isolated as pure compounds but exist in aqueous
solution and are prepared from the barium salts.
Ba(ClO2)2 + H2SO4(aq) → 2HClO2(aq) + BaSO4(s)
Ba(XO3)2 + H2SO4 → 2 HXO3 + BaSO4 (X= Cl, Br)
• Iodic acid (HIO3) is a stable white solid at room
temperature and is prepared from I2 and nitric acid or
from I2O5 in water.
I2O5 + H2O → 2HIO3
Potassium chlorate is a white crystalline substance that is used:
• as a pesticide; as an oxidizing agent; to prepare oxygen; as a
disinfectant; in safety matches, and in explosives and fireworks.
• Potassium chlorate will readily decompose if heated in contact
with a catalyst, typically manganese (IV) dioxide (MnO2). Thus,
it may be simply placed in a test tube and heated over a burner
and this can provide a convenient source of dioxygen for school
laboratories. The reaction is as follows:
2 KClO3(s) + heat → 3 O2(g) + 2 KCl(s)
• Both potassium bromate and iodate are used in volumetric
analysis and in particular the iodate is a primary standard being
available in high purity and with excellent stablity.
[IO3]- + 5 I- + 6 H+ → 2I2 + 3 H2O
• Several different I(VII) oxyacids are known including
periodic acid (HIO4) and orthoperiodic acid (H5IO6).
• In the latter case there is extensive H-bonding
present in the solid state resulting in a 3D network.
• Perchloric acid exists as discrete monomeric units,
HIO4 is again extensively H-bonded through cis- edge-
sharing octahedra.
• The reactions involving the various oxyacids in
aqueous solution is complicated, as seen by the
following equilibria:
[H3IO6]2- + H+ → [IO4]- + 2H2O
2[H3IO6]2- → 2[HIO5]2- + 2H2O
2[HIO5]2- → [H2I2O10]4- → [I2O9]4- + H2O
Oxides of Halogens
• Fluorine forms two compounds with oxygen.
• Oxygen difluoride, OF2, is formed from the reaction
of F2 with hydroxide ions, and has structure of
water as predicted by VSEPR.
• Dioxygen difluoride, FOOF, is produced by
photolysis of a mixture of F2 and O2, and is a very
good fluorinating agent, eg. in the fluorination of
Plutonium.
• Chlorine oxides occur with many chlorine oxidation
numbers.
• Cl2O7 is the most stable of the oxychlorides.
Cl2O ClO2 Cl2O6 Cl2O7
Brown-Yellow Yellow Gas Dark Red Colourless
Gas Liquid Liquid
• Cl2O has the bent structure of F2O, but here the Cl-O-Cl
bond angle is smaller due to the presence of Opπ-Cldπ
interactions, which favour the use of p rather than sp3-
hybrid orbitals on the O for bonding, and hence have a
bond angle closer to the 90o of the orthogonal p-
orbitals.
• ClO2 is used as a bleaching agent and disinfectant when
used in dilute solutions. The oxidizing properties of
ClIV make it useful for these purposes.
 Interhalogen Compounds
• 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.
• There are never more than two types of halogen
atoms in an interhalogen molecule. There are of four
general types:
• AX- type : ClF, BrF, IF, BrCl, ICl, IBr
• AX3-type: ClF3, BrF3, ICl3
• AX5-type: BrF5, IF5,
• 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.
• 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.
XY diatomic interhalogens
Preparation
By direct combination of halogens
Cl2+F2 → 2ClF (at 250 °C )
I2 + F2 → 2IF (-45 °C)
Other methods
Cl2 + ClF3 → 3ClF (300 °C)
I2 + AgF → IF + AgI (0 °C)
• The interhalogens with formula XY have physical properties
intermediate between those of the two parent halogens.
• The covalent bond between the two atoms has some ionic
character, the larger element, X, becoming oxidised and
having a partial positive charge. Most combinations of F, Cl,
Br and I are known, but not all are stable.
• Chlorine monofluoride (ClF), the lightest interhalogen, is a
colorless gas with a boiling point of 173 °K.
• Bromine monofluoride (BrF) has not been obtained pure - it
dissociates into the trifluoride and free bromine. Similarly, iodine
monofluoride is unstable - iodine reacts with fluorine to form a
pentafluoride.
• BrF is also unstable and undergo disproporationation rapidly and
irreversibly
3BrF → Br2 + BrF3
• Iodine monofluoride (IF) is unstable and disproportionates
rapidly and irreversibly at room temperature:
5IF → 2I2 + IF5.

• Bromine monochloride (BrCl) is an unstable red-brown gas with

a boiling point of 5 °C.
2BrCl ⇌ Br2 + Cl2
• Iodine monochloride (ICl) consists of red transparent
crystals which melt at 27.2 °C to form a choking brownish
liquid (similar in appearance and weight to bromine). It
reacts with HCl to form the strong acid HICl2. The crystal
structure of iodine monochloride consists of puckered zig-
zag chains, with strong interactions between the chains.
• Iodine monobromide (IBr) is made by direct combination of
the elements to form a dark red crystalline solid. It melts at
42 °C and boils at 116 °C to form a partially dissociated
vapor.
Reactions
ICl + 2Na → NaI + NaCl
BrCl + H2O → HOBr + HCl
ICl + H2O → HOI + HCl
-CH=CH- + BrCl → -CH(Br)-CH(Cl)-
XY3 interhalogens
Preparation
Cl2 + 3F2 → 2ClF3 (200-300 °C)
ClF + F2 → ClF3 (200-300 °C)
Br2 + 3F2 → 2BrF3
ClF3 + Br2 → BrF3 + BrCl
3BrF → BrF3 + Br2
I2 + 3Cl2 → 2ICl3
ICl + Cl2 → ICl3
I2O5 + 10HCl → 2ICl3 + 5H2O + 2Cl2
• ClF3 is a colourless gas which on condensation gives green
liquid.
• If acts as a strong fluorinating agent and converts chlorides
into fluorides
2AgCl + ClF3 → 2AgF + Cl2 + ClF
• It converts oxides such as MgO, NiO, Al2O3, Co3O4 to
fluorides
NiO + ClF3 → NiF2 + Cl2 + O2
Co3O4 + ClF3 → CoF3 + Cl2 + O2
• It reacts with NH3 and N2H4 to give HF
NH3 + ClF3 → HF + N2 + Cl2
N2H4 + ClF3 → HF + N2 + Cl2
• It reacts with Uranium to give UF6
U + ClF3 → UF6 + ClF
ClF3 ⇌ ClF2+ + ClF4+
• Bromine trifluoride (BrF3) is a yellow green liquid that
conducts electricity - it ionises to form [BrF2+] + [BrF4-].
• It reacts with many metals and metal oxides to form similar
ionised entities; with some others it forms the metal
fluoride plus free bromine and oxygen.
M + BrF3 → MF + Br2
MCl + BrF3 → MF + BrCl3
• It dissolves in certain fluorides viz. KF to yield BrF4-
KF + BrF3 → KBrF4
• It displaces oxygen from oxides like SiO2, B2O3, As2O3 etc
SiO2 + BrF3 → SiF4 + Br2 + O2
B2O3 + BrF3 → BF3 + Br2 + O2
• It is used in organic chemistry as a fluorinating agent. It has
the same molecular shape as chlorine trifluoride.
• ICl3 is a bright yellow solid which fumes readily.
• In crystalline state it exist as I2Cl6.
• It dissociates on heating at 68oC
ICl3 → ICl + Cl2
• It undergoes self-dissociation
2ICl3 ⇌ ICl2+ + ICl4-
• It is used in medicine
XY5 interhalogens
• Chlorine pentafluoride (ClF5) is a Colorless gas, made by
reacting chlorine trifluoride with fluorine at high
temperatures and high pressures.
Cl2 + 5F2 → ClF5 (350 oC and 250 atm)
ClF3 + F2→ ClF5
• It reacts violently with water and most metals and non-
metals.
• Bromine pentafluoride (BrF5) is a colourless fuming liquid,
made by reacting bromine trifluoride with fluorine at 200°
C.
Br2 + 5F2 → 2BrF5 (excess F2 above 150oC)
KBr + 3F2 → KF + BrF5 (25oC)
• It is physically stable, but reacts violently with water and
most metals and non-metals.
• It is used in organic synthesis.
• Iodine pentafluoride (IF5) is a colorless liquid, made by
reacting iodine pentoxide with fluorine, or iodine with silver
fluoride.
I2 + 5F2 → 2IF5
2I2O5 + 10F2 → 4IF5 + 5O2
I2 + 10AgF → 2IF5 + 10Ag
• It is highly reactive, even slowly with glass. It reacts with
elements, oxides and carbon halides.
2IF5 ⇌ IF4+ + IF6-
• It reacts with I2O5 to give iodine oxofluoride
I2O5 + IF5 → IOF3
• The molecule has the form of a tetragonal pyramid.
• Primary amines react with iodine pentafluoride to form
nitriles after hydrolysis with water.
R−CH2−NH2→R−CN
XY7 interhalogens
• Iodine heptafluoride (IF7) is a Colorless gas.
• It is made by reacting the pentafluoride with fluorine.
IF5 + F2 → IF7 (250-300 °C)
• IF7 is chemically inert, having no lone pair of electrons in the
valency shell; in this it resembles sulfur hexafluoride.
IF7 + SiO2 → IOF5 + SiF4
IF7 + H2O → IOF5 + HF
• The molecule is a pentagonal bipyramid.
• This compound is the only interhalogen compound possible
where the larger atom is carrying seven of the smaller atoms.
• All attempts to form bromine heptafluoride have met with
failure; instead, bromine pentafluoride and fluorine gas are
produced.
Point to Remember
• 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-
References

• Concise Inorganic Chemistry, 5th Edition, J.D. Lee.

• Principles of Inorganic Chemistry, B.R. Puri, L. R. Sharma and
K. C. Kalia