The Group 16 Elements:

The Chalcogens

“Read in the name your God who created “ )I( Inorganic Chemistry 3 )I( Miftahul Khair, M.Sc (miftah@fmipa.unp.ac.id1)

http://kimia.unp.ac.id

Jurusan Kimia
Chemistry Department

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 The discovery of oxygen ended of the phlogiston theory of
combustion ( burning involved the loss of phlogiston) :

•Guyton de Morveau : burning a metal gave a product that had a

greater weight.

•Antoine Lavoisier : something had to be added in the combustion

process. It was oxygen.
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Group Trends

semimetal

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 Contrasts in the Chemistry of Oxygen
and Sulfur

Like nitrogen, the oxygen-

oxygen double bond is much
stronger than the two oxygen-
oxygen single bond

multiple bonding is
only common for
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Oxygen
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Compounds containing -O-O-

are usually strong oxidizing
agents, and compounds
containing >= 3 oxygen
atoms bonded together are
rare and tend to be highly Possible
explosive. for
catenati
on

O tends to bond to other

elements rather than to
itself.
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Oxygen

2 allotropic:

Dioxygen, O2

Trioxygen, O3
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Dioxygen, O2
molar mass <<
nonpolar molecule m.p and b. p <<

• support combustion.
• almost all elements will react with O2 at RT or when heated.
exceptions are the “noble” metals ( ex: Pt) and the noble gases

very finely powdered

pyrophoric

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 • 21 % of Earth’s atmosphere

•O2 is not very soluble in water,

but enough to support marine
organisms.

T ↑ Solubility ↓ Gas mixture released by heating air-saturated

water will actually be enriched in O2 because N2 is
less soluble

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Determinants of the health of a river or lake

Dissolved oxygen (DO).
Low levels of dissolved O2 can be
caused by eutrophication (excessive
algae and plant growth)
or, an input of high-T water from an
industrial cooling system.

Biological oxygen demand (BOD) :

the opposite of DO , potential for O2
consumption by aquatic organisms.

DO << or BOD >> problems !

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Use • synthesis of HNO3 from NH3
• hospital facilities to raise the O2 partial
pressure in gas mixtures given to people with
respiratory problems, making absorption of O2 gas
easier for poorly functioning lungs.

Preparation • mostly by fractional distillation of liquid air

•.

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E= 95 kJ/mol

By shining UV on
paramagnetic oxygen in
the presence of a
sensitizing dye
paramagnetic

Reverts to the paramagnetic

form in seconds or minutes,

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 E= 95 kJ/mol

paramagnetic

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Trioxygen (Ozone)
•Unstable, Diamagnetic gas with a strong odor.
•Extremely toxic;
•produced in regions of high voltages;

More powerful oxidizing agent than O2 :

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More powerful oxidizing agent than O2 :
bactericide :

•bottled waters
•PDAM - swimming pools (beside Cl2 gas )

chlorine gas
Ozone
Long lasting but it reacts
with any organic
Short lasting but innocuous
contaminants to form
hazardous organochlorine
compounds

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Ozone :
- at Earth surface, a dangerous pollutant, effect on lung
tissue, reacts with the rubber of tires, become brittle and
crack.
upper

- ozone in the stratosphere provides a vital protective layer

for life on Earth.

Production :
photolysis

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u san stiion
K im a
Chemistry Department
engines

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Ozone :
- ozone in the stratosphere provides a vital protective layer
for life on Earth.

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Chemistry Department

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16.7 Water

1. dissolve ionic substances

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 2. Water dissolve polar covalent compounds ;

3. water controls our acid-base chemistry

through its autoionizing

4. as a Lewis base.
hexaaquanickel(II) ion, [Ni(:OH2)6) 2+

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5. water also controls the redox limits in aqueous solution.

No aqueous redox reaction can happen outside the boundaries of the oxidation of water
to oxygen or its reduction to hydrogen:

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16.8 Hydrogen Peroxide

high viscosity due to high degree of H-bonding

Preparation :

Kinetically slow

uses :
paper bleaching,
household products,
hair bleaches.

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 16.9 Hydroxides
Hydroxide ion :
•colorless
•the strongest base in aqueous solution.
•very hazardous, because it reacts with the proteins of the skin

Reaction :
With the acidic CO2.

-Selaed hydroxide solutions

- Sealed NaOH glass bottles with a rubber
stopper rather than glass stopper.

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Ca(OH)2

Preparation:

Reaction:

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Overview of Sulfur Chemistry

sulfate ion is only weakly oxidizing. tends to be reduced,

usually reduced
in acidic environments but oxidized
base
completelynonoxidizing.
Most stable sulfur
species
tends to be oxidixez

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Chemistry Department

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 S is prone to catenate (after C)

However, only 2 bonds available.

chains of S with some other element or group of elements
at each end:

Ex :
dihydrogen polysulfides HS-Sn-SH
polysulfur dichlorides, ClS-Sn-SCl,
(n = 0 – 20).

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16.12 Sulfur
Polymorphs = different crystal forms in which
identical units of the same compound are packed
differently

Alotropes = forms of the same element that contain

different molecular units.

S8, cyclo-octasulfur (monoclinic and rhombic

crystals), differ simply in the way in which the
molecules pack.
These two forms are polymorphs of each
other,

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cyclo-Hexasulfur

Synthesis

H2Sx + SyCl2 ,
such that (x + y) the desired ring size.

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cyclo-Octasulfur
is the allotrope found almost exclusively in nature
and as the product of almost all chemical reactions :

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 cyclo-Octasulfur

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The Industrial Extraction of Sulfur

The Frasch method of extraction of sulfur.

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Chemistry Department The Frasch method of extraction of sulfur

Kawah Ijen

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Uses of sulfur :

-synthesis of sulfuric acid

-synthesize sulfur chemicals such as CS2 for the
vulcanization (hardening) of rubber.
-synthesis of sulfur-containing organic dyes.
- added to asphalt mixes to make more frost-resistant
highway surfaces.

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 16.13 Hydrogen Sulfide
-“rotten eggs,” smell
-extremely toxic—more toxic than HCN

Used in :
Separation of “heavy water” from regular water.

Preparation :

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16.14 Sulfides

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16.16 Sulfites

Na2SO3 is used as a reducing agent

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16.17 Sulfuric Acid
- oily, dense liquid that freezes at 10°C.
- Concentrated H2SO4 has concentration of 18 mol/L
- mixes with water very exothermically

Not vice versa !!!!

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Reactions of Sulfuric Acid

1. Dilute sulfuric acid is used most often as an acid.

2. dehydrating agent.

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Reactions of Sulfuric Acid

3. oxidizing agent.

4, sulfonating agent.

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The Industrial Synthesis of Sulfuric Acid

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Sekian

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