The Group 6A Elements

Group 16 elements - the Chalcogens

▪ Much of the important chemistry of the group 16
elements can be understood on the basis of their
electronic structure and electronegativity.
▪ Since the elements have a [core]ns2 np4 electron
configuration, neutral group 16 compounds can form up to
six bonds.
▪ This provides for common oxidation state from -2 to +6
electrons (with a complete octet) around the group 16
atom, so such compounds are also “electron-rich” but the
high electronegativities of O and S make them good
oxidizing agents.
• The most common oxidation
numbers for group 6A elements are
+4, +6, and -2.
• The group 6A elements can be
found in nature in both free and
combined states.
• These elements are intimately
related to life. We need oxygen all the
time throughout our lives. Sulfur is

responsible for some of the protein

structures in all living organisms. Many

industries utilize sulfur, but emission of

sulfur compounds is often seen more

as a problem than the natural

phenomenon.
• The metallic properties increase as
the atomic number increases.
• The element polonium has no stable
isotopes
Atomic and Physical Properties
and the Periodic Trends
The electron configurations for each
element are given below: Oxygen : 1s2 2s2
2p4 Sulfur : 1s2 2s2p6 3s2p4 Selenium: 1s2
2s2p6 3s2p6d10 4s2p4 Tellurium: 1s2 2s2p6
3s2p6d10 4s2p6d10 5s2p4 Polonium: 1s2 2s2p6
3s2p6d10 4s2p6d10f14 5s2p6d10 6s2p4
• Atomic and Ionic Radii: The atomic and
ionic radius increases as we move from
Oxygen to Polonium.
• Ionization Enthalpy: Ionization enthalpy
decreases with increase in the size of the
central atom. Therefore, it decreases as we
move from Oxygen to Polonium since the
size of the atom increases as we move
down.
• Electron Gain Enthalpy: The electron
gain enthalpy decreases with increase in
the size of the central atom moving down
the group. Oxygen molecule has a less
negative electron gain enthalpy than sulfur.
This is on the grounds that Oxygen,
because of its compressed nature
encounter more repulsion between the
electrons effectively present and the
approaching electron
• Electronegativity: The electronegativity
decreases as we move down the group due to
increase in
nuclear size
• Nature of the Group 16 Elements: The
metallic properties increase in the order
oxygen, sulfur, selenium, tellurium, or
polonium. Oxygen and Sulfur are non-metals,
Selenium and Tellurium are metalloids and
Polonium is a metal under typical conditions.
Polonium is a radioactive element.
• Allotropy: Each one of the element of group
16 displays allotropy. Oxygen has two allotropes:
Oxygen and Ozone. Sulphur exists as many
allotropic forms but only two of them are stable,
which are: Rhombic Sulphur and Monoclinic
Sulphur. Selenium and Tellurium are found in
both amorphous and crystalline forms.
• The Melting and Boiling Points: As

the atomic size increases from oxygen

to tellurium, the melting and boiling

points also increase. The huge

distinction between the melting and

boiling points of oxygen and sulfur

might be clarified on the premise that

oxygen exists as a diatomic atom (O2)

while sulfur exists as a polyatomic
particle (S8).
• Oxidation States: The group 16

elements have a configuration of ns2

np4in their outer shell, they may

accomplish noble gas configuration

either by the gain of two electrons,

framing M-2 or by sharing two

electrons, in this manner shaping two

covalent bonds. Thus, these elements

indicate both negative and positive

oxidation states. The regular oxidation

states showed by the elements of

group 16 incorporate -2, +2, +4 and +

6.
• Oxygen differs from sulfur in
chemical properties due to its small

size. The differences between OO and

SS are more than the differences

between other members.

• Oxygen is paramagnetic because
there are unpaired electrons in O2

molecules.
Atomic radius (pm)
lonic radius (pm)
140 02
184 S2-
198 Se?
221 Te?
94 Po**

First lonization Energy

Electronegativity
1500
12 TL

91000
99
941
869
813
Energy (kJ/mol
Electronegativity

O
S
Se
Te Po
o
S
Se
Te Po

Melting and Boiling Points

Density

1000
Temperature ("C)
Density (g/cm)
143 x 10

-250
-219
S
Se
Te Po
S
Se
Te
Po
Sources
▪ Large-scale production of oxygen is by
fractional distillation of liquid air. Liquid
oxygen is stored and shipped at its boiling
point of -183oC in vacuum- walled bottles.
▪ The Frasch process is used to mine sulfur
from underground deposits. A well is drilled
into a sulfur bed and a set of concentric
tubes installed. Superheated water melts
the sulfur. Compressed air forces it to the
surface.
▪ Sulfur is also produced from hydrogen
sulfide, H2S, and sulfur dioxide, SO2.
2H2S(g) + SO2(g) → 2H2O(l) + 3S(s)
▪ Selenium and tellurium are by-products of
the processing of sulfide ores for other
metals.
▪ Polonium is formed by the radioactive
decay of radium in minerals such as
pitchblende.
Oxidation states and trends in
chemical reactivity:
1. Since electronegativity of oxygen is very
high, it shows only negative
oxidation state as –2 except in the case of
OF2 where its oxidation state is + 2 2. The
stability of + 6 oxidation state decreases
down the group and stability
of + 4 oxidation state increase (inert pair
effect)
Anomalous behavior of oxygen: 1. The
anomalous behavior of oxygen, like other
members of p-block
present in second period is due to its small
size and high electronegativity. One typical
example of effects of small size and high
electronegativity is the presence of strong
hydrogen bonding in H2O which is not found
in H2S. 2. The absence of d orbitals in
oxygen limits its covalency to four and in
practice, rarely exceeds two. On the other
hand, in case of other elements of the
group, the valence shells can be expanded
and covalence exceeds four.
Reactivity with hydrogen
All the elements of Group 16 form hydrides
of the type H2E (E =O, S, Se, Te, Po).
H2O, H2S, H2Se, H2Te : BDE Decreases

Stability decreases Acidity increases

Reducing nature increases

Reactivity with oxygen:
• All these elements form oxides of the EO2

and EO3 types where E = S, Se, Te or Po. •

Ozone (O3) and sulphur dioxide (SO2) are

gases while selenium dioxide (SeO2) is

solid. • Reducing property of dioxide

decreases from SO2 to TeO2; SO2 is

reducing while TeO2 is an oxidising agent •

Both types of oxides are acidic in nature.

Reactivity towards the halogens.
• The stability of the halides decreases in
the order F– > Cl– > Br– > I–.
• Amongst hexahalides, hexafluorides are
the only stable halides.
• They have octahedral structure.
• Sulphurhexafluoride, SF6 is exceptionally
stable for steric reasons.
• Tetrafluorides, have sp3d hybridisation
and thus, have trigonal bipyramidal
structures in which one of the equatorial
positions is occupied by a lone pair of
electrons. This geometry is also regarded
as see-saw geometry.
• Dihalides have sp3 hybridisation and
thus, have tetrahedral structure.
• The well known monohalides are

dimeric in nature. Examples are S2F2,

S2Cl2, S2Br2, Se2Cl2 and Se2Br2.
• These dimeric halides undergo
disproportionation as given below:

2Se2Cl → SeCl4 + 3Se

Important compounds and reactions
• Oxygen reacts with almost all other
elements to form oxides.
Example:
• Ozone, O3, is produced directly from
oxygen, O2, during lightening strikes.
• Oxygen is necessary for releasing energy

from fuels, such as glucose, in organisms.

• Oxygen is used to produce steel and to
oxidize hydrogen in fuel cells.
• Sulfur compounds often have unpleasant
odors. Hydrogen sulfide, H2S, smells like a

rotten egg. It forms when metallic sulfides

and hydrochloric acid react.

• Concentrated sulfuric acid, H2SO4, is
a strong dehydrating agent. Example:
• So people will know when there is a
natural gas leak, ethyl mercaptan,

CH3CH2SH, is added to supplies of

odorless natural gas.
• Sodium thiosulfate, Na2S2O3, also
known as hypo, is used in the

development of film.
• The addition of cadmium selenide,
CdSe, gives glass a beautiful ruby
color.
DIOXYGEN
2H2O3(aq) → 2H20(1) + O2(g)

(iv) On large scale it can be prepared from water or air.

Electrolysis of water leads to the release of hydrogen at
the cathode and oxygen at the anode.

Properties

1. Molecular oxygen, O, is unique in being

paramagnetic inspite of having even number of
electrons.

2. Its combination with other elements is often strongly

exothermic which helps in sustaining the reaction.
However, to initiate the reaction, some external heating
is required as bond dissociation enthalpy of oxgyen-
oxygendouble bond is high (493.4 kJ mol-1). 2.Some
compounds are catalytically oxidised. For e.g.,
SILI
LIT

2502 + O2 → 2803 5HCI + O2 + 2Cl + 2H20

CuCl2
Oxides
OZONE
• Ozone is an allotropic form of
oxygen.
• It is too reactive to remain for long in

the atmosphere at sea level.

• At a height of about 20 kilometres, it

is formed from atmospheric oxygen in

the presence of sunlight.

• This ozone layer protects the earth’s
surface from an excessive

concentration of ultraviolet (UV)

radiations.
Properties of Ozone
▪ Ozone is thermodynamically
unstable with respect to oxygen since
its decomposition into oxygen results
in the liberation of heat (∆H is
negative) and an increase in entropy
(∆S is positive). These two effects
reinforce each other, resulting in large
negative Gibbs energy change(∆G) for
its conversion into oxygen.
▪ Due to the ease with which it liberates
atoms of nascent oxygen (O3 → O2 + [O] ), it
acts as a powerful oxidising agent. For
example, it oxidizes lead sulphide to lead
sulphate and iodide ions to iodine.
• Estimation of ozone: When ozone reacts
with an excess of potassium iodide solution
buffered with a borate buffer (pH 9.2),
iodine is liberated which can be titrated
against a standard solution of sodium
thiosulphate. This is a quantitative method
for estimating O3 gas.
• Nitrogen oxides (particularly nitric oxide)
combine very rapidly with ozone and there
is, thus, the possibility that nitrogen oxides
emitted from the exhaust systems of
supersonic jet aeroplanes might be slowly
depleting the concentration of the ozone
layer in the upper atmosphere.
NO + O3 → NO2 + O2
Uses of Ozone:
• Ozone is used as a germicide,
disinfectant and for sterilising water.
• It is also used for bleaching oils,
ivory, flour, starch, etc.
• It acts as an oxidising agent in the
manufacture of potassium

permanganate.
SULPHUR
• Sulfur is a solid at room temperature
and 1 atm pressure. It is usually

yellow, tasteless, and nearly odorless.

• It exists naturally in a variety of
forms, including elemental sulfur,

sulfides, sulfates, and organosulfur

compounds
• Sulfur is unique in its ability to form a

wide range of allotropes, more than

any other element in the periodic table.

• The most common state is the solid
S8 ring, as this is the most
thermodynamically stable form at room

temperature.
• Sulfur exists in the gaseous form in

five different forms (S, S2, S4, S6, and

S8). In order for sulfur to convert

between these compounds, sufficient

heat must be supplied.

▪ Yellow rhombic sulphur = Monoclinic
sulphur Transition temp = 369 K
▪ Both rhombic and monoclinic sulphur have
S8 molecules.
▪ At elevated temperatures (~1000 K), S2 is
the dominant species and is paramagnetic
like O2
▪ In vapour state sulphur partly exists as S2
molecule which has two unpaired electrons
in the antibonding π* orbitals like O2 and,
hence, exhibits paramagnetism
• Two common oxides of sulfur are

sulfur dioxide (SO2) and sulfur trioxide

(SO3).
• Sulfur dioxide is formed when sulfur

is combusted in air, producing a toxic

gas with a strong odor.

• These two compounds are used in

the production of sulfuric acid, which

is used in a variety of reactions.

• Sulfur also exhibits a wide range of

oxidation states, with values ranging

from -2 to +6. It is often the central ion

in a compound and can easily bond

with up to 6 atoms.
• In the presence of hydrogen it forms

the compound hydrogen sulfide, H2S,

a poisonous gas incapable of forming

hydrogen bonds and with a very small

dipole moment. Hydrogen sulfide can

easily be recognized by its strong odor

that is similar to that of rotten eggs, but

this smell can only be detected at low,

nontoxic concentrations.
• A variety of sulfur-containing
compounds exist, many of them

organic.
• The prefix thio- in from of the name

of an oxygen-containing compound

means that the oxygen atom has been

substituted with a sulfur atom.

• General categories of sulfur-
containing compounds include thiols
(mercaptans), thiophenols, organic

sulfides (thioethers), disulfides,

thiocarbonyls, thioesters, sulfoxides,

sulfonyls, sulfamides, sulfonic acids,

sulfonates, and sulfates

SELENIUM
• Selenium appears as a red or black
amorphous solid, or a red or grey

crystalline structure; the latter is the

most stable.
• Selenium has properties very similar

to those of sulfur; however, it is more

metallic though it is still classified as a

nonmetal.
• It acts as a semiconductor and
therefore is often used in the

manufacture of rectifiers, which are

devices that convert alternating

currents to direct currents.

• Selenium is also photoconductive,

which means that in the presence of

light the electrical conductivity of

selenium increases.
• Selenium is also used in the drums
of laser printers and copiers.
Selenium is now used in “xerox”
machines and laser printers. They use

a drum coated with selenium that is

exposed to an electric field. The

regions on the drum that are exposed

to high light intensity lose their charge.

Toner powder adheres only to the

charged areas of the drum which

correspond to the printed areas on the

page.
Photocopiers
• It is rare to find selenium in its
elemental form in nature; it must

typically be removed through a refining

process, usually involving copper.

• Selenium is often found in soils and
in plant tissues that have

bioaccumulated the element. In large

doses, the element is toxic; however,

many animals require it as an essential

micronutrient.
• Selenium atoms are found in the

enzyme glutathione peroxidase, which

destroys lipid-damaging peroxides. In

the human body it is an essential

cofactor in maintaining the function of

the thyroid gland.

TELLURIUM
▪ Tellurium is the metalloid of the oxygen
family, with a silvery white color and a
metallic luster similar to that of tin at room
temperature.
▪ Like selenium, it is also displays
photoconductivity.
▪ Tellurium is an extremely rare element,
and is most commonly found as a telluride
of gold.
▪ Tellurium is often used in metallurgy in
combination with copper, lead, and iron.
▪ Tellurium is used in solar panels and
memory chips for computers.
▪ It is not toxic or carcinogenic; however,
when humans are exposed to too much of it
they develop a garlic-like smell on their
breaths.
POLONIUM
• Polonium is a very rare, radioactive metal.

There are 33 different isotopes of the

element and all of the isotopes are

radioactive.
• Polonium exists in a variety of states, and
has two metallic allotropes.
• It dissolves easily into dilute acids.
• Polonium does not exist in nature in
compounds, but it can form synthetic

compounds in the laboratory.

• It is used as an alloy with beryllium to act

as a neutron source for nuclear weapons.

• Polonium is a highly toxic element.
• The radiation it emits makes it very
dangerous to handle. It can be

immediately lethal when applied at the

correct dosage, or cause cancer if

chronic exposure to the radiation

occurs.
• Methods to treat humans who have

been contaminated with polonium are

still being researched, and it has been

shown that chelation agents could

possibly be used to decontaminate

humans.
Summary
• The chalcogens have no stable
metallic elements.
• The tendency to catenate, the strength
of single bonds, and the reactivity all
decrease moving down the group.
• Because the electronegativity of
the chalcogens decreases down the
group, so does their tendency to
acquire two electrons to form
compounds in the −2 oxidation state.
• The lightest member, oxygen, has the
greatest tendency to form multiple
bonds with other elements.
• Oxygen does not form stable
catenated compounds, due to
repulsions between lone pairs of
electrons on adjacent atoms.
• Because of its high electronegativity,
the chemistry of oxygen is generally
restricted to compounds in which it has
a negative oxidation state, and its bonds
to other elements tend to be highly
polar. nonmetals are amphoteric.
• Metal oxides are usually basic, and
nonmetal oxides are acidic, whereas

oxides of elements along the dividing line

between metals and

• The reactivity, the strength of multiple
bonds to oxygen, and the tendency to

form catenated compounds all decrease

down the group, whereas the maximum

coordination numbers increase.

• Because Te=O bonds are
comparatively weak, the most stable

oxoacid of tellurium contains six Te–OH

bonds.
• The stability of the highest oxidation
state (+6) decreases down the group.
• Double bonds between S or Se and
second-row atoms are weaker than the

analogous C=O bonds because of

reduced orbital overlap.
• The stability of the binary hydrides
decreases down the group.
References
• Cotton F.A., G. Wilkinson, and Gauss, P.A, Basic
inorganic Chemistry, Wiley & Sons.,
• Rayner-Canham, G., Descriptive Inorganic

Chemistry, 2nd edition, W.H Freeman & Co, New

York,
• Shriver, D.F and Atkin, P.W., 2006, Inorganic

Chemistry, 4th ed, WH Freeman & Co, New York

• Suyanta, 2013, Kimia Unsur, Gadjah Mada
University Press, Yogyakarta
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