Chalcogenides

• Oxygen exists only as

two gaseous allotropes
(O2 and O3);
• Sulfur has many
allotropes, all of which
are insulators
• The stable forms of
selenium and tellurium
are semiconductors
• Polonium is a metallic
conductor.
Chalcogenides
• Oxides consists of 47% of the crust minerals, and O2
is 21% of the atmosphere
• Elemental sulfur can be found in volcanic deposits
• Selenium and tellurium are relatively rare
• Polonium has no stable isotope
Chalcogenides
• Oxygen gas is obtained by distilling liquid air
• Lab quantities can be obtained by electrolyzing
hydroxide solutions or cleaving H2O2
• The main industrial use of O2 is in its use in fire
• It is also important for breathing purpouses
• O2 is paramagnetic and its ground state is a triplet

• It can be photoexcited to make it more reactive as

singlet oxygen
Chalcogenides
• Ozone can be generated by passing O2 through an
electric discharge
• It smells like electricity (hospital smell is due to
ozone)
• Ozone absorbs UV light in the upper atmosphere
• Liquid ozone is a very strong oxidant and will react
explosively with anything
Chalcogenides
• Sulfur is extracted through the Frasch Process
where water at 440K is injected under pressure into
the ground to melt sulfur. It is then brought up by
compressed air
• Sulfur can be recovered from crude oil and natural
gas where it exists as H2S
Chalcogenides
• Elemental sulfur has
many many many
allotropes
• Most form rings of
varous sizes
• There is fibrous sulfur
which forms infinite
chain polymers
Chalcogenides
• Elemental sulfur is very reactive
• It will burn in air to give SO2
• It will react with F2, Cl2 and Br2 to form molecular
halides (SF6, S2Cl2 and S2Br2)
• It will dehydrogenate saturated hydrocarbons to
make alkenes
• This is used to crosslink polyisoprene in rubber to make
very large polymers for use in tires
Chalcogenides
• Sulfur selenium and
tellurium rings can be
oxidized to form
cationic chalcogen
molecules
Chalcogenides
• H2S is more toxic than HCN and smells like rotten
eggs
• H2S can be prepared by dissolving sulfides in acid

• H2Se and H2Te can also be prepared by reacting

selenides and tellurides in acid
Chalcogenides
• The reaction of sulfur with metals form sulfides.
• 1-1 sulfides will usually form either ZnS structures
of NiAs structures
• 1-2 sulfides form the CdI2 structure
Chalcogenides
• Polysulfanes can be made by reacting H2S with
sulfur dihalides (n is between 2 to 6)

• Polysulfides can be made by reacting sulfides with

elemental sulfur

• Polysullfides are anionic, and forms complexes with

metals in solution
Chalcogenides
Chalcogenides
• Polyselenanes and polytelluranes do not exist
beyond H2Se2 and H2Te2
• Polyselenides and polytellurides exist and can be
made similar to polysulfides (reacting the element
with the anion)
Chalcogenides
• Sulfur has three fluorides S2F2, SF4 and SF6
• S2F2 is unstable and exists in two isomers
• SF4 is also highly reactive and can be used to make other
sulfur halides and oxyhalides
Chalcogenides
• Sulfur hexafluoride is inert and is made by burning
S in F2
• It is used as an electrical insulator
• Burning sulfur in F2 also makes small amounts of
S2F10
Chalcogenides
• Sulfur chlorides are more restricted than the
fluorides and only S2Cl2 exists
• Its made by reacting sulfur with chlorine gas
• Its main use is making polysulfanes
• Oxohalides of sulfur include SOF2, SOF4, SO2F2,
SO3F2, SOCl2 and SO2Cl2
• SOCl2 is used to make magic acid
Chalcogenides
• Se and Te will form more or less stable dihalides
SeX2 and TeX2
• Like sulfur, the hexafluorides are made by direct
reaction with the elements
• The tetrafluorides can be made by reacting +4
cations (like SeO2 and TeO2) with SF4
• The tetrachlorides and tetrabromides can be made
by direct reaction with the elements
Chalcogenides
• The oxides of sulfur are useful for making sulfuric
acid, which is the most important sulfur compound
• They are made by burning either elemental sulfur
or H2S
• Pure sulfuric acid is made by bubbling SO3 gas into
pure H2SO4 to make oleum H2S2O7 which is then
reacted with water. This makes water a limiting
reactant, and makes the reaction less vigorous and
easier to control
Chalcogenides
• Selenium and tellurium oxides are ionic compounds
which are made by direct combination of the
elements
• Dissolving the oxides in water forms oxoacids
SeO2 + H2O -> H2SeO3
Chalcogenides
• S4N4 form from the reaction of S2Cl2 with NH3

• S4N4 can be polymerized to make a conducting polymer

Halogens
• Fluorine is obtained
from fluorides
• Chlorine and bromine
come from seawater
• Iodine is extracted from
seaweed and iodate
minerals
Halogens
• Stable charges are -1 and 0
• Iodine can have an ionic +1 charge
• The colors of the halogens come from the π* to σ*
homo to lumo transition which shifts from the near
UV to red
• This is why fluorine is yellowish, chlorine is
greenish, bromine is orange and iodine is purple
Halogens
• Fluorine gas is the most reactive element known
• Needs to be handled in Teflon apparatus
• Is a very strong oxidant
• Will oxidize water into mixtures of O2 and O3
• Will react with all elements except O2, N2 and the
lighter noble gases
• The reactivity arises from low bond dissociation
energy and the very high reduction potential
• Cl2, Br2 and I2 reacts in similar ways to F2, but are
much less reactive
Halogens
• Chlorine bromine and iodine form charge transfer
complexes when dissolved in solvents which can act as
electron donors

• This is why dissolving the halogens in benzene gives colored

solutions
Halogens
• When dissolved in water halogens from clathrates
• Clathrates are cage like arrangements of H2O which
surround a guest atom, in this case the halogens
Halogens
• All metal halides of group 1 metals form either NaCl
or CsCl
• Most metal difluorides form CaF2 or rutile
• Metal trihalides form different structures but
symmetrical 3d structures are common
• Most tetrahalides are molecular species
• Metal pentahalides form chains or rings
• Most hexahalides are octahedral and molecular
Halogens
• Interhalogen compounds are prepared by reacting
the elements.
• The type of compound can be controlled by
temperature and reactant stoichiometry
• XY, XY3, XY5 and XY7 can form
Halogens
• The structures of
interhalogens will
follow VSEPR
Halogens
Halogens
• Diatomic interhalogens will have intermediate
properties between their parent compounds
• The higher oxidation state interhalogens act as
fluoride donors and acceptors (acidic or basic)
Halogens
• Polyhalogen cations can be made by reacting the
halogens with sufficiently strong oxidizing agents
Halogens
• Polyhalide anions can also form from bromine and
iodine
Halogens
• Only iodine will form a stable oxide I2O5
• Chlorine oxides can form readily but will
decompose explosively
• Bromine oxides are even more unstable
Halogens
• Chlorine dioxide is a bleaching material used to
whiten flour and paper pulp

• It is made by reacting perchlorate salts with acid

Halogens
• Cl2O7 is an anhydride of perchloric acid which is
made by dehydrating HClO4 with P2O5

• It is a highly explosive oily liquid

Halogens
• Several families of
halogen oxofluorides
also exist
• Their structures are
consistent with VSEPR
• They can be made by
fluorinating halide
oxoanions
Halogens
• The halogens form various oxoacids with strength
increasing with the number of O’s, and going down
the group

• Hypofluorous acid is the only oxoacid known for

fluorine, which is unstable and will not ionize in
water
Halogens
• The hypohalites are unstable with respect to
disproportionation

• Chlorite solutions are unstable in acid, but can be

stabilized in basic solution

• Chloric acid and bromic acid are also not isolable, but
XO3- salts are sufficiently stable to be obtained pure
Halogens
• Perchloric acid is the only oxoacid for chlorine
which can be obtained pure
• It is made by heating KClO3 and H2SO4 together
under reduced pressure
• Pure perchloric acid is super dangerous and is likely
to explode when heated
• Dilute chlorate solutions are stable and not so easy
to reduce due to kinetics
Halogens
• Several periodic acids
exists because
periodate anions link
together to form larger
anions
Halogens
• In water, the oxohalides will usually react via redox
reactions as oxidants or reductants
Noble Gases
• The main source of He is natural gas (7% by volume),
where it is believed to come from radioactive decay
• It is extracted from natural gas by liquefying the other
components
• Argon is the second most important noble gas and is
distilled from liquid air (0.92% argon)
• Argon co-distills with O2, and O2 is removed by igniting
H2 in the Ar-O2 mixture
• Neon is also obtained from liquid air as the only
component that doesn’t liquify
Noble Gases
• Helium and argon are both used as inert atmosphere, but
the most important use of helium is as a cryogen

• He/O2 mixtures are used in place of N2/O2 mixtures for deep

sea divers because He is less soluble in blood than N2
Noble Gases
• No compounds of noble gases exist except for
xenon
• XeF2 is made by reacting Xe and F2 while irradiating
it with UV light
• XeF4 and XeF6 are made by reacting Xe and F2 and
sparking it with an electrical arc
• It is impossible to make XeF4 and XeF6 pure
Noble Gases
• The three fluorides are readily decomposed by
water

• All three fluorides are strong oxidizing and

fluorinating agents
• Their structures follow VSEPR
Noble Gases
• XeF2 will react with
fluoride acceptors like
AsF5, SbF5 and forms a
cation XeF+ and the
fluorometallate
Noble Gases
• XeF6 will react in the
same way to make an
XeF5+ cation and a
fluorometallate
• In the solid state
however, the XeF5+ are
considered to form a
halide bridge to form
an Xe2F112+ cation
Noble Gases
• XeF4 and XeF6 can also act as fluoride acceptors to
form XeF5- and XeF7- respectively
• The two anions form when reacting with metal
fluorides
• XeF7- is difficult to isolate because it is easily
fluorinated to XeF82-
Noble Gases
• Xenon dichloride can be made with difficulty by
microwaving Cl2 with an excess of Xe
• XeCl+ can be made by reacting the fluorine salt
[XeF][Sb2F11] with SbCl5
Noble Gases
• XeO3 forms in the hydrolysis of XeF4 and XeF6
• It is an extremely explosive solid
• Reacting it with alkali metal hydroxides gives
xenates (XeO42-) which disproportionate in solution
into perxenate XeO64- and xenon
Noble Gases
• XeO4 can be made by slow addition of H2SO4 to
perxenate salts (Na2XeO6 and BaXeO6)
• XeO4 is a highly explosive gas
Noble Gases
• Several oxofluorides can be made in various methods
XeF4 + H2O -> XOF2 + 2HF

• Reacting metal halides with XeO3 gives a solid oxohalide

with a polymeric chain structure
Noble Gases
• The XeF2 can be used to make AXeF compounds
through the elimination of HF

The reaction is based on XeF+ formation

Noble Gases
• XeF2 can react with hydrocarbons through the HF
elimination scheme to bond Xe to carbon
Noble Gases
• Xenon can form bonds with gold

• When xenon is removed with a vacuum, a square

planar complex with the fluoroantimonate anion
forms
Noble Gases
• The only compound
with Kr is KrF2. it reacts
in a similar manner as
XeF2
• It fluorinates several
pentafluorides to make
the KrF+ cation