Group 17

The Halogens:
Fascinating
aspects

1
The elements in group 17 of the periodic
table, on the right, are called the
HALOGENS.
F fluorine

Cl chlorine

Br bromine

I
iodine
At
astatine
2
Why the name ….. HALOGEN??

* Halogen-metal compounds
are salts occurring in sea
water
(e.g. NaCl; sodium
chloride),
* halos = sea salts;
genes=born. 3
 STATE OF HALOGENS

• Astatine is radioactive and is one of the

rarest of the chemical elements.

4
Halogen Greek name meaning

Fluorine fluere Flow

(Fluorite melts when heated)
Chlorine chloros Greenish yellow

Bromine bromos Stench

Iodine iodes Violet

Astatine astatos Unstable (decay product of U, Th)

5
 GENERAL PROPERTIES OF THE HALOGENS

 Have 7 e- in their outer shells

 Exists as separate diatomic molecules ... F2, Cl2, Br2
 Colored and color darkens as we go down through the
group
 non-metals
 do not conduct electricity
 never found free in nature because of their reactivity
– they are found as compounds with metals (eg.
NaCl).
 poisonous and smelly.
 They are all toxic or harmful because they are
so reactive
6
Electron configuration of halogens

Fluorine 1s2 2s2 2p5

[Ne]3s2 3p5
Chlorine [Ar]3d10 4s2 4p5
[Kr]4d10 5s2 5p5
Bromine [Xe]4f14 5d10 6s2
Iodine 6p5
Astatine 7
 Electronic structure of halogens......
All halogens have seven electrons in their outer shell but one e- short of
the nearest noble gas configuration.
fluorine
 They can easily attain a full and complete 2,7 (9)
outer shell by gaining one electron.
 They all gain an electron in reactions to
form negative ions with a -1 charge.
chlorine
 So, they have similar chemical 2,8,7
properties. (17)
 Fluorine is the most electronegative
element in the periodic table and it has
no d orbitals in its valence shell, so it can't
expand its valence shell. bromine
2,8,8,7 (35)
 Cl2, Br2 and I2 have valence shell d orbitals
and can expand their valence shells to hold
as many as 14 valence electrons.
8
 How do halogen molecules exist?
All halogen atoms require one more electron to
obtain a full outer shell to become STABLE (8e-).
Each atom can achieve this by sharing one electron
with another atom to form a single covalent bond.

F + F  F F

So all halogens exist as diatomic molecules:

F2, Cl2, Br2 and I2. 9
10
 Physical properties of halogens

• Ionization energy
• Electron affinity
• Electronegativity
• Oxidizing states
• Oxidizing power

• Metals are electropositive (eg.

Na)
• Non-metals are electronegative (Cl2)
11
Ionization Energy (decreases down the group)

Ionization energy (IE) is defined as the amount of

energy required to remove the most loosely valence
electron, of an isolated gaseous atom to form a cation.
If the outer valence electrons are far away from the
nucleus, it does not take as much energy to remove
them. So the energy required to pull off the
outermost electron will be less for the elements at the
bottom of the group since there are more energy
levels. Iodine lose an e- and forms I+
Also, the high ionization energy makes the element
appear non-metallic. Iodine and astatine display
metallic properties 12
 Electronegativity (decreases down the group)

Electronegativity is a measure of the tendency of an atom

to attract a bonding pair of electrons towards itself.

The valence electrons will be at a distance from the

nucleus as we go down the group and therefore, the
nucleus and the electrons are not that much attracted
to each other. An increase in shielding is observed.

Electronegativity therefore decreases down the group.

So electrons can be easily removed from iodine. 13

Electron Affinity (decreases down the group)

Electron affinity of an atom or molecule is the amount of

energy released or spent when an electron is added to a
neutral atom or molecule in the gaseous state to form a
negative ioni.e X-

Since the atomic size increases down the group, electron

affinity generally decreases but only gradually
(At < I < Br < F < Cl)
However, fluorine has a lower electron affinity than
chlorine and this can be explained by the small size of
fluorine, compared to chlorine.
14
 Oxidizing states of halogens
Oxidation States in
Halogen
Compounds
Fluorine (always) -1
-1, +1, +3, +5, +7
Chlorine -1, +1, +3, +4, +5
-1, +1, +5, +7
Bromine -1, +1, +3, +5, +7
Iodine
-1 NaCl, Astatine
+1 HClO, +3 BrF3, +5 HClO3 , +7 IF7
15
 Oxidizing Power
(decreases down the halogen group)
• The halogens are strong oxidizing agents.
• The oxidizing power decreases from fluorine to
Iodine. Fluorine is the strongest oxidizing agent.
• It oxidizes other halide ions to halogens in
solution or when dry.
F2 + 2X-  2F- + X2; X- = Cl- , Br- , I-
(F2 has high e- affinity)
• Halogen of low atomic number oxidizes the
halide ion of higher atomic number.

16
17
Oxidation or reduction?

18
 How does electron structure affect reactivity?
Reactivity of alkali metals decreases going down the group

 The atoms of each element get larger F

going down the group.

decrease in reactivity
 This means that the outer shell gets
further away from the nucleus and is
shielded by more electron shells. Cl
 The farther the outer shell is from the
positive attraction of the nucleus, the
harder it is to attract another
electron to complete the outer shell.
 This is why the reactivity of the halogens Br
decreases going down group 17.
Reactivity: F > Cl > Br > I 19
 Difficulties encountered in the
isolation of fluorine
• Fluorine is so reactive that it attacks the materials of all
the vessels. For example, fluorine attacks carbon and
silicon present in the glass vessels forming CF4 and SiF4
respectively.

• It also attacks the electrodes and vessels made of Pt to

form PtF4. Lead, iron and tin vessels were also found to
be unsuitable for the preparation.

• Isolation of fluorine from HF got failed because HF is so

stable that it cannot be decomposed by oxidizing
agents. 20
 Isolation of Fluorine: Dennis’
Method:
Fluorine is prepared by the electrolysis of fused potassium
hydrogen fluoride.

Electrolysis is carried out between graphite electrodes in a V-

shaped electrically heated copper tube. The ends of the tube are
covered with copper caps into which the graphite electrodes are
fixed with Bakelite cement. The copper tube is thickly bagged
to prevent loss of heat.

KHF 2 KF +HF HF H +F

2 + H2 (At cathode) 2F 2e F2 (At

H 2e Anode)
21
Fluorine liberated at the anode is passed through the U-tube containing
sodium fluoride. This removes the hydrogen fluoride vapors
coming with fluorine.
N aF +H F NaHF2
22
 Abnormal behavior of fluorine
Fluorinediffers from the other
members of the halogen family. This is
due to

i) Small size
ii) High electronegativity
iii)Non availability of d orbitals in fluorine

23
 Peculiarity of fluorine
Oxidation state : Halogens exhibit oxidation states of -
1,0,+1,+3,+5 and +7 where as fluorine exhibits only -1
oxidation state
Reactivity: Fluorine is the most reactive element among the
halogens. This is due to strong electrostatic repulsion
between the non bonding electrons present in fluorine
molecule. The F- F bond is very weak.
Behavior of hydrogen fluoride: Hydrogen fluoride has
abnormally high melting and boiling points than the other
hydrogen halides due to hydrogen bonding.

H F H F F
Formation
H of HF 2
- ions : Due to hydrogen bonding the
fluoride ion forms the anion HF -. On the other hand
2
halides do not form such ions. E.g., KHF2
24
 Peculiarity of fluorine ….. continued
• Maximum covalency: As fluorine lacks d orbitals it
cannot have covalency more than one. But the other
halogens can have covalency up to 7. (eg. IF7)

• Formation of SF6: Due to small size and high

electronegativity, fluorine brings about the + 6 state in
sulphur forming SF6. Other halogens do not form
such hexahalides

• Complex formation: Flouride ion a greater tendency to

form [FeF6]3-, [AlF6]3-
• Formation of polyhalides: Due to the non-
availability of d-orbitals fluorine does not form any
polyhalides. But +other −halogens form polyhalide ions.
[Cl
E.g.3] , [Br3] , [I3] [I3] , [Br4] , [I4] etc [Br2]+, [I2]+ , 25
+ + 2− 2−
 Electropositive nature of iodine
• It has the lowest electronegativity value ,
i.e. highly electropositive. It behaves like a
metal
• Like the other halogens, it has one electron short of
a full octet and reacts with many elements in order
to complete its outer shell, although in keeping
with periodic trends, it is the weakest oxidizing
agent among the stable halogens
• Similarly, the iodide anion, I−, is the strongest
reducing agent among the stable halogens, being
the most easily oxidized back to diatomic I2.
26
 Basic Iodine
Metallic or basic properties increase down the group

Among the halogens, iodine shows strong basic

character.
For e.g. Iodine has a metallic lustre
has a tendency to form unipositive I+
ion and tripositive I3 + ion.

Atomic size increases from fluorine to iodine.

Thus the nucleus of I2 holds the electrons in the
orbit less firmly. So Iodine looses one e-
easily forming unipositive cation. I2  2I+ + 2e- 27
 Evidence for basic iodine
ICl acts as a strong electrophilic iodinating
agent. This again confirms the basic character
of iodine.
OH OH
COOH COOH
+
+
2ICl I I 2HCl
Salicylic acid
3, 5- di-iodo
salicyclic
acid
28
 IODINE TEST …. A TEST FOR STARCH

Starch gives an intense "blue-black" color upon

of addition
aqueous solutions of the triiodide anion (I3-), due to
the formation of an intermolecular charge-transfer
complex. In the absence of starch, the brown color of the
aqueous solution remains. This interaction between starch
and triiodide is the basis for iodometry.

KI + I2  I3-

29
 Uses of halogens

Halogen Uses
Fluorine In tooth pastes, Teflon®
Chlorine purify water in wells, swimming pools etc as it
kills bacteria (chlorination)

Bromine Fire extinguishers, disinfectant, camera films

Iodine Iodized salt, in artificial rain, dyes, specialized soaps,
lubricants, photographic film, tincture, and
pharmaceuticals, test for starch, treatment of thyroid
disorders

30
 Facts about halogens in human …
• There are 3 to 6 grams of fluorine,
• 95 grams of chlorine,
• 260 milligrams of bromine,
• 10 to 20 milligrams of iodine in a 70 kg person.
• Chlorine is found in human blood in a
concentration of 0.3%.

31
Interhalogen Compounds….
32
 Interhalogen Compounds
• These covalent compounds are formed when two
different halogens react .
• These are formed due to the electronegativity difference
among the halogens.
Classification:
• Interhalogens have the general formula Axn where n=1, 3,
5 &7.
Type AX eg: ClF, BrF, BrCl, ICl, Ibr
Type AX3: eg : ClF3, BrF3, ICl3
Type AX5 eg: BrF5 ClF5
Type AX7 eg: IF7
When representing the compound, the less electro
33
 Iodine mono chloride ….. ICl
is formed by passing chlorine over
solid iodine at temperature below 0 0C.

I2 +Cl2
2ICl
• It is a red-brown chemical compound
• melts near room temperature.
• Because of the difference in the
electronegativity of iodine and chlorine, ICl is
highly polar ; I+Cl-
* In organic synthesis, estimation of iodine No. of 34
 Bromine trifluoride… BrF3
• It is obtained by mixing bromine vapor and
fluorine in a stream of nitrogen at 20oC.

Br 2 +3F 2 2BrF 3
It is a straw-colored liquid with a pungent odor.

It is a powerful fluorinating agent

It is used to produce uranium hexafluoride (UF6) in the

processing and reprocessing of nuclear fuel.
35
 Bromo pentafluoride … BrF5
It is pale yellow liquid

By the direct reaction of bromine with

excess fluorine at temp. over 150°C

Br2 + 5 F2 → 2 BrF5

It is an extremely effective fluorinating agent, converting

most uranium compounds to the hexafluoride at room
temperature like BrF3 .

36
 Iodine heptafluoride….IF7
• It is a colorless gas
• It is prepared by passing a mixture of iodine
pentafluoride vapors and fluorine through
a platinum tube at 300 0C.
IF5 +F 2 IF7

• It is a strong oxidizing agent

• Used to prepare periodic acid.

37
Shapes of interhalogens

38
 Pseudohalides
and
Pseudohalogens …
39
 Pseudohalides & Pseudohalogens
Pseudohalides are univalent negative inorganic
radicals, composed of two or more electronegative
atoms (ions), which exhibit reactions similar to
those of the halide ions (X-).
E.g. Cyanide CN- , Thiocyanide SCN- , Azide N3-

Covalent dimers of such pseudohalides are called

pseudohalogens These possess properties similar to
those of halogens. Examples.,
– Cyanogens (CN)2 -Thiocyanogen(SCN)2
Selenocyanogen (SeCN)2 etc. 40
 Similarities between pseudohalogens and halogens

1. Dimeric and isomorphic nature:

Cl2 is isomorphous to (CN)2; Br2 is isomorphous to
(SCN)2.

2. Like halogens, pseudohalogens combine with metals like

silver, lead &mercury to form insoluble salts.
AgCN, Pb(CNS)2 (CN, CNS are
pseudohalogens) Ag+ + Cl-  AgCl; Ag+
+ CN-  AgCN
3. Pseudohalogens also react with alkalis
Cl2 + 2OH-  Cl- + OCl- + H2O;
41
- - -
 Similarities … continued

4. Formation of monobasic hydracids:

Cl2 + H2  2HCl; (CN)2 + H2 
2HCN

5. Addition to ethylenic bonds: Like

halogens, pseudohalogens also form
addition compounds with unsaturated
hydrocarbons.
42
Preparation and properties of
pseudohalogens …
43
 Preparation of cyanogen (CN)2
• Dry cyanogen is obtained by heating a mixture
of mercuric cyanide and mercuric chloride

2Hg(CN)2 Hg2(CN)2 + (CN)2

• It is a colorless, toxic gas with a pungent odor.

• The two cyano groups are bonded together at
their carbon atoms: N≡C−C≡N
• Uses: an important intermediate in the production of
many fertilizers. It is also used as a stabilizer in the
production of nitrocellulose.
44
 Preparation of Thiocyanogen (SCN)2
• Adding lead thiocyanate to Br2 in methylene
chloride solution at 0oC.
Pb(SCN)2 + Br2  PbBr2 + (SCN)2

• PbBr2 (solid) is filtered off under argon

gas and the filtrate on evaporation yields
free thiocyangen.

45
Compd Uses
Na3AlF6 Manufacture of aluminum BF3
Catalyst
CaF2 Optical components, manufacture of HF,
metallurgical flux
Fluorinating agent, reprocessing nuclear fuels
ClF3 Manufacture of F2, AlF3, Na3AlF6, and fluorocarbons
HF Ceramics manufacture, welding, and soldering
LiF Fluoridating water, dental prophylaxis, insecticide
NaF Insulating gas for high-voltage electrical equipment
SF6 Manufacture of toothpaste
SnF2 Manufacture of uranium fuel for nuclear reactors
UF6 46
47
DISPLACEMENT REACTIONS OF HALOGENS

Reactive halogen displaces less reactive one

from its salt solution…

Cl2 + 2NaBr  2NaCl + Br2

48
SUMMARY OF GROUP I7

49