9.8 Oxidation and
Reduction – more on redox reactions involving halogens & halide ions
See also
Revision notes on Inorganic and organic REDOX reactions, oxidation state explained etc.
-
chlorate(I),
ClO–, chlorate(VII), ClO4–
etc. oxygen is more electronegative than chlorine.
-
fluorine: F is always (–1) in all compounds,
-
because it
has the highest electronegativity of any element and only
one electron short of a stable noble gas structure
electronically e.g. formation of fluoride ion F [2.7] + e– ==>
F– [2.8]
-
The (–1)
state relates to either gaining an electron to form the
fluoride ion, F–, e.g. in ionic sodium fluoride, NaF
(Na+ Cl– ionic bond, Na is +1),
-
or
share with one other electron to form a covalent bond e.g. in
the molecules hydrogen fluoride, HF (δ+H–Fδ–
polar bond, H is +1), or tetrafluoromethane (carbon
tetrafluoride), CF4 (δ+C–Fδ–
polar bond, C is +4).
A more detailed discussion of some halogen–halide ion REDOX reactions
See also
Revision notes on Inorganic and organic REDOX reactions, oxidation state explained etc.
The oxidation of iodide ions by iron(III) ions
-
Iron(III) ions oxidise iodide ions
to a
dark brown solution of iodine (or black solid) formed with
iron(II) ions.
-
2Fe3+(aq)
+ 2I–(aq) ==> 2Fe2+(aq)
+ I2(aq/s)
-
This accounts
for why iron(III) iodide cannot exist.
-
The oxidation state changes
are ...
-
iron Fe is reduced,
oxidation state changes from +3 to +2
-
and iodine I is oxidised,
oxidation state changes
from –1 to 0
-
The orange–brown
iron(III) ion becomes the pale green iron(II) ion BUT the latter's
colour is obscured by the strong dark colour of the iodine formed.
-
Note that chlorine is a powerful
enough oxidising agent to oxidise iron(II) ion to the iron(III) ion (see
next reaction described), BUT iodine is not a strong enough
oxidising agent to achieve this. It is in fact the iron(III) ion that will
oxidise the iodide ion, rather than the reverse.
-
The oxidising power series for
these two situations is
-
Cl2 (EØCl2/Cl–
+1.36V) > Fe3+ (EØFe3+/Fe2+ +0.77V)
> I2 (EØI2/I– +0.54V),
-
which of course is numerically
paralled by the decreasing values of the standard redox potentials of the
half–reactions i.e. becoming less positive as the oxidising power decreases.
The oxidation of iron(II) to iron(III) using chlorine
-
The oxidation of iron(II)
ions to iron(III) ions is readily achieved by chlorine – a powerful
oxidising agent.
-
Note if chlorine gas is passed
over hot iron(II) chloride, brown iron(III) chloride is formed.
The reaction
between sulfur dioxide and sulfite ions and halogens
-
If neutral molecules or more
complex ions are involved, a bit more care must be taken e.g. when the
sulphur dioxide is oxidised to sulphate by bromine (or the reduction of
bromine to bromide).
-
SO2(aq)
+ Br2(aq) + 2H2O(l) ===> SO42–(aq)
+ 2Br–(aq) + 4H+(aq)
-
(i) the oxidation half
reaction is: SO2(aq) + 2H2O(l) ===> SO42–(aq) + 4H+(aq)
+ 2e–
-
(ii) the reduction
half–reaction is: Br2(aq) + 2e– ===> 2Br–(aq)
-
The hydrogen (+1) and
oxygen (–2) do not change oxidation state.
-
(i) + (ii)
equals the balanced equation, 2 electrons gained and lost or an ox.
state rise and fall of 2 units.
-
Bromine is the
oxidising agent (gain/accept e–s, lowered ox. state),
-
and sulphur dioxide is the reducing agent (loses e–s,
inc. ox. state of S).
-
Sulphur dioxide does
ionise to a small extent in water to give the sulphite ion, and adding a
strong non–oxidising acid like dilute hydrochloric acid to sodium
metabisulphite produces the ion, which means another equation can also adequately describe
the redox change in terms of sulphur and bromine.
The reaction
between the chlorate(V) ion and solid manganese(IV) oxide
The reaction of chlorine with hot and cold
sodium hydroxide
-
In all the
reactions quoted below the oxidation states of
hydrogen (+1) and oxygen (–2) remain unchanged and (ii) the
process descriptions are over simplified but the main reactions
described provide good examples of the redox chemistry of
chlorine.
-
With cold dilute sodium hydroxide solution alkali sodium chlorate(I) (NaClO, the bleach sodium
hypochlorite) is formed as well as sodium chloride.
-
2NaOH(aq)
+ Cl2(aq) ==> NaCl(aq) + NaClO(aq)
+ H2O(l)
-
2OH–(aq)
+ Cl2(aq) ==> Cl–(aq) +
ClO–(aq) + H2O(l)
-
In terms of
oxidation states the chlorine
disproportionates from 2Cl(0) to 1Cl
(–1, chloride ion) plus 1Cl(+1, chlorate(I)
ion).
-
Overall 1
electron gained, (1 ox. state unit decrease) balanced by 1
electron lost (1 ox. state unit increase).
-
However, with hot concentrated sodium hydroxide solution, above 75oC, the formation of sodium
chlorate(V) predominates as well as sodium chloride.
-
6NaOH(aq)
+ 3Cl2(aq) ==> 5NaCl(aq) + NaClO3(aq)
+ 3H2O(l)
-
6OH–(aq)
+ 3Cl2(aq) ==> 5Cl–(aq)
+ ClO3–(aq) + 3H2O(l)
-
In terms of
oxidation state changes, the chlorine
disproportionates from 6 Cl (0, element) to 5 Cl (–1,
chloride ion) plus 1 Cl (+5, chlorate(V)ion).
-
Overall 5
electrons gained, (5 ox. state unit decrease) balanced by 5
electrons lost (5 ox. state unit increase).
-
The change in reaction mode from
cold to hot sodium hydroxide solution is due to the
instability of the chlorate(I) ion, which at higher temperatures
disproportionates into the chloride ion and the chlorate(V) ion.
-
3NaClO(aq)
==> 2NaCl(aq) + NaClO3(aq)
-
3ClO–(aq)
==> 2Cl–(aq) + ClO3–(aq)
-
In terms of
oxidation states the 'chlorine'
in the chlorate ion disproportionates from 3 Cl(+1)
to 2 Cl(–1, chloride ion) plus 1Cl(+5,
chlorate(V) ion).
-
Overall 4
electrons gained, (4 ox. state unit decrease) balanced by 4
electrons lost (4 ox. state unit increase).
-
A concentrated solution of
sodium chlorate(I) is a useful source
of chlorine in the laboratory because it readily reacts with conc.
hydrochloric acid to give off the gas.
-
NaClO(aq)
+ 2HCl(aq) ==> NaCl(aq) + H2O(l)
+ Cl2(aq/g)
-
ClO–(aq)
+ Cl–(aq) + 2H+(aq)
==> H2O(l) + Cl2(aq/g)
-
In terms of
oxidation states the
'chlorine' here does the opposite of disproportionation and
changes from 1 Cl(+1, chlorate(I) ion) plus 1 Cl(–1,
chloride ion) to give 2 Cl(0, chlorine molecule).
-
Overall 1
electron lost, (1 ox. state unit increase) balanced by
electron gained (1 ox. state unit decrease).
The reaction between
aqueous chlorine and potassium iodide solution
-
Half–cell reaction
data:
-
In terms of
oxidation state changes ...
-
Chlorine
molecules are reduced from ox. state (0) to (–1) of the chloride
ion, 1 electron gain.
-
Iodide ions
are oxidised from ox. state (–1) to (0) of the iodine molecule,
1 electron loss.
-
So chlorine
molecules are the oxidising agent (more powerful e– acceptor, more
+ve EØ) and iodide ions are the reducing agent (e–
donor, less +ve EØ).
-
2 x
oxidation half–cell, (ii) reversed |
2I–(aq) ==>
I2(aq) + 2e– |
2 x
reduction half–cell, (i) |
Cl2(aq) +
2e– ==> 2Cl–(aq) |
added gives
full redox equation |
Cl2(aq)
+ 2I–(aq) ==>
Cl2(aq) + I2(aq) |
-
One method of
estimating chlorine in water e.g. from bleaches, is to add excess
potassium iodide and titrating the liberated iodine with
standardised sodium thiosulphate, which itself is another redox
reaction.
The reaction
between iodate(V) and iodide ions in acidified aqueous solution
-
Half–cell reaction
data:
-
(i)
1/2I2(aq) + e– ==>
I–(aq) (EØ = +0.54V,
iodide gets oxidised, acts as reducing agent, less positive
EØ)
-
(ii) IO3–(aq) +
6H+(aq) + 5e– ==>
1/2I2(aq) + 3H2O(l)
-
In terms of
oxidation state changes ...
-
The iodide
ions (I at –1) are oxidised to iodine molecules (I at 0) by electron
loss to the iodate(V) ion, I –1 to 0 ox. state.
-
The iodate(V)
ions (I at +5) are reduced to iodine molecules (I at 0) by
electron gain from the iodide ions (the reducing agent), I +5
to 0 ox. state.
-
Hydrogen (+1)
and oxygen (–2) do not change oxidation state.
-
5 x
ox'n half–cell, (i) reversed |
5I–(aq) ==>
5/2I2(aq) + 5e– |
1 x
reduction half–cell, (ii) |
IO3–(aq) +
6H+(aq) + 5e– ==>
1/2I2(aq) + 3H2O(l)
|
added gives
full equation |
IO3–(aq) + 6H+(aq)
+ 5I–(aq) ==>
3I2(aq) + 3H2O(l) |
-
The reaction
can be used to estimate iodate(V) by adding excess potassium
iodide and titrating the liberated iodine with standardised sodium
thiosulphate or using the liberated iodine from a known quantity
of potassium iodate(V) salt with excess KI(aq) salt
solution to standardise the sodium thiosulphate.
The
oxidation of the chloride ion by acidified
potassium manganate(VII)
-
Half–cell reaction
data:
-
(i) MnO4–(aq) +
8H+(aq) + 5e– ==> Mn2+(aq)
+ 4H2O(l) (EØ
= +1.52, reduction of the
oxidising agent)
-
(ii)
1/2Cl2(aq) +
e– ==> Cl–(aq) (EØ
= +1.36, lower EØ, so cannot act as an oxidising agent)
-
Both chlorine and
potassium manganate(VII) are strong oxidising agents, but chlorine is the
weaker, so chloride ions are oxidised to chlorine.
-
In terms of
oxidation state changes ...
-
Oxidation:
Chlorine as the chloride ions at (–1) lose electrons to give chlorine molecules at
ox. state (0).
-
Reduction:
Mn
(+7) is reduced to Mn (+2), 5e– gain, acts as the
oxidising agent.
-
Hydrogen (+1)
and oxygen (–2) do not change oxidation state.
-
10 x
oxi'n half–cell, (ii) rev. |
10Cl–(aq)
==> 5Cl2(aq/g)
+ 10e– |
2 x
red'n half–cell, (i) |
2MnO4–(aq) +
16H+(aq) + 10e– ==> 2Mn2+(aq)
+ 8H2O(l) |
added – full redox equation |
2MnO4–(aq) +
16H+(aq) + 10Cl–(aq)
==>
2Mn2+(aq)
+ 8H2O(l) + 5Cl2(g/aq)
|
-
This reaction is used to
prepare chlorine gas (green and toxic) by running conc. hydrochloric
acid on to moistened potassium manganate(VII) crystals (old name potassium permanganate).
The
reduction of acidified dichromate(VI) with iodide ions
-
Half–cell reaction
data:
-
In terms of
oxidation state changes ...
-
Oxidation:
Iodide ions at (–1) lose electron to give iodine molecules at
I(0).
-
Reduction:
Each Cr at (+6) is reduced by gaining 3e– to give
Cr at
(+3), so the Cr2O72– ion is the
oxidising agent.
-
Hydrogen (+1)
and oxygen (–2) do not change oxidation state.
-
6 x
oxidation half–cell, (ii) rev. |
3I2(aq) + 6e– ==>
6I–(aq) |
1 x
reduction half–cell, (i) |
Cr2O72–(aq) + 14H+(aq)
+ 6e– ==> 2Cr3+(aq) + 7H2O(l)
|
added
full redox equation |
Cr2O72–(aq)
+
14H+(aq) + 6I–(aq)
==>
2Cr3+(aq)
+ 3I2(aq) + 7H2O(l) |
-
This reaction
can be used to quantitatively measure chromium(VI) in dichromates, Cr2O72–,
or chromates, CrO42– (which change to
dichromate(VI) on acidification, yellow ==> orange). Excess
potassium iodide is added and the liberated iodine
See also
Revision notes on Inorganic and organic REDOX reactions, oxidation state explained etc.
WHAT NEXT?
PLEASE NOTE
GCSE Level GROUP 7 HALOGENS NOTES are on a separate webpage
INORGANIC Part 9
Group 7/17 Halogens sub–index:
9.1 Introduction, trends
& Group 7/17 data * 9.2 Halogen displacement
reaction and reactivity trend * 9.3 Reactions of
halogens with other elements - halides * 9.4
Reaction between halide salts and conc.
sulfuric acid *
9.5 Tests for halogens and halide ions *
9.6 Extraction of halogens from natural sources
* 9.7 Uses of halogens & compounds * 9.8
Oxidation & Reduction – more on redox reactions
of halogens & halide ions * 9.9 Volumetric
analysis – titrations involving halogens or halide ions * 9.10
Ozone, CFC's and halogen organic chemistry
links * 9.11 Chemical bonding in halogen
compounds * 9.12
Miscellaneous aspects of
halogen chemistry
Advanced
Level Inorganic Chemistry Periodic Table Index:
Part 1
Periodic Table history
Part 2
Electron configurations, spectroscopy,
hydrogen spectrum,
ionisation energies *
Part 3
Period 1 survey H to He *
Part 4
Period 2 survey Li to Ne * Part
5 Period 3 survey Na to Ar *
Part 6
Period 4 survey K to Kr and important
trends down a group *
Part 7
s–block Groups 1/2 Alkali Metals/Alkaline Earth Metals *
Part 8
p–block Groups 3/13 to 0/18 *
Part 9
Group 7/17 The Halogens *
Part 10
3d block elements & Transition Metal Series
*
Part 11
Group & Series data & periodicity plots
Group numbering and the modern periodic
table
The original group numbers of
the periodic table ran from group 1 alkali metals to group 0
noble gases (= group 8). To account for the d block elements and
their 'vertical' similarities, in the modern periodic table,
group 3 to group 0/8 are numbered 13 to 18. So, the halogen
elements are referred to as group 17 at a higher academic level,
though group 7 is still used, usually at a lower academic level.
|
keywords phrases formula oxidation states balanced
symbol equations electrode potentials: 2Fe3+(aq) + 2I–(aq) ==> 2Fe2+(aq) +
I2(aq/s) Cl2 (EØCl2/Cl– +1.36V) > Fe3+ (EØFe3+/Fe2+ +0.77V) > I2 (EØI2/I–
+0.54V) 2Fe2+(aq) + Cl2(aq) ==> 2Fe3+(aq) + 2Cl–(aq) 2FeCl2(s) + Cl2(g) ==>
2FeCl3(s) SO2(aq) + Br2(aq) + 2H2O(l) ==> SO42–(aq) + 2Br–(aq) + 4H+(aq) SO2(aq)
+ 2H2O(l) ==> SO42–(aq) + 4H+(aq) + 2e– Br2(aq) + 2e– ==> 2Br–(aq) SO32–(aq) +
Cl2(aq) + H2O(l) ==> SO42–(aq) + 2Cl–(aq) + 2H+(aq) 3MnO2 + 6OH– + ClO3– ==>
3MnO42– + 3H2O + Cl– 2NaOH(aq) + Cl2(aq) ==> NaCl(aq) + NaClO(aq) + H2O(l)
2OH–(aq) + Cl2(aq) ==> Cl–(aq) + ClO–(aq) + H2O(l) 6NaOH(aq) + 3Cl2(aq) ==>
5NaCl(aq) + NaClO3(aq) + 3H2O(l) 6OH–(aq) + 3Cl2(aq) ==> 5Cl–(aq) + ClO3–(aq) +
3H2O(l) 3NaClO(aq) ==> 2NaCl(aq) + NaClO3(aq) 3ClO–(aq) ==> 2Cl–(aq) + ClO3–(aq)
NaClO(aq) + 2HCl(aq) ==> NaCl(aq) + H2O(l) + Cl2(aq/g) ClO–(aq) + Cl–(aq) +
2H+(aq) ==> H2O(l) + Cl2(aq/g) 1/2Cl2(aq) + e– ==> Cl–(aq) (EØ = +1.36 Cl2(aq) +
2e– ==> 2Cl–(aq) Cl2(aq) + 2e– ==> 2Cl–(aq) 1/2I2(aq) + e– ==> I–(aq) (EØ =
+0.54V) I2(aq) + 2e– ==> 2I–(aq) IO3–(aq) + 6H+(aq) + 5e– ==> 1/2I2(aq) +
3H2O(l) IO3–(aq) + 6H+(aq) + 5I–(aq) ==> 3I2(aq) + 3H2O(l) MnO4–(aq) + 8H+(aq) +
5e– ==> Mn2+(aq) + 4H2O(l) (EØ = +1.52 2MnO4–(aq) + 16H+(aq) + 10Cl–(aq) ==>
2Mn2+(aq) + 8H2O(l) + 5Cl2(g/aq) Cr2O72–(aq) + 14H+(aq) + 6I–(aq) ==> 2Cr3+(aq)
+ 3I2(aq) + 7H2O(l)
[SEARCH
BOX]
|
 |
 |
 |
 |
 |
 |
 |
 |
 |
 |
 |
 |
 |
 |
 |
Website content © Dr
Phil Brown 2000+. All copyrights reserved on revision notes, images,
quizzes, worksheets etc. Copying of website material is NOT
permitted. Exam revision summaries & references to science course specifications
are unofficial. |
|