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The Chemistry of CHROMIUM

CHROMIUM(III) oxidation state chemistry


Chromium forms the stable green (greyish dark green
almost violet sometimes?) chromium(III) ion,
[Cr(H2O)6]3+(aq).
Aqueous solutions of chromium(III) chloride are suitable
for investigating the aqueous chemistry of the
chromium(III) ion.
With aqueous ammonia (alkaline) or sodium hydroxide, chromium(III) ions form a
green gelatinous precipitate of chromium(III) hydroxide.
Cr3+(aq) + 3OH(aq) ==> Cr(OH)3(s) (but the structures can be quite complex)
or [Cr(H2O)6]3+(aq) + 3OH(aq) ==> [Cr(OH)3(H2O)3](s) + 3H2O(l)
The hydroxide readily dissolves in acids to form salts,
Cr(OH)3(s) + 3H+(aq) ==> Cr3+(aq) + 3H2O(l)
or more elaborately: [Cr(OH)3(H2O)3](s) + 3H3O+(aq)

[Cr(H2O)6]3+(aq) + 3H2O(l)

or more simply Cr(OH)3(s) + 3H+(aq)


Cr3+(aq) + 3H2O(l)thus showing amphoteric
behaviour, since the hydroxide ppt. also dissolves in excess strong alkali to give a
dark green solution and the hydroxide ppt. does not dissolve in the weak
base aqueous sodium carbonate. However, it will dissolve in excess ammonia because
a new green complex ion is formed. (more details on these reactions below)
The whole sequence of each theoretical step of chromium(III) hydroxide precipitation
and its subsequent dissolving in strong basealkali is shown the series of diagrams
below.
All are, for simplicity, treated as octahedral complexes of 6 ligands either water H 2O
or hydroxide ion OH
[Cr(H2O)6]3+ => [Cr(OH)(H2O)5]2+ => [Cr(OH)2(H2O)4]+ => [Cr(OH)3(H2O)3]
(s) precipitate
dissolving => [Cr(OH)4(H2O)3] => [Cr(OH)5(H2O)]2 => [Cr(OH)6]3

The sequence of chr


hydroxide precipitate f
its subsequent dissolv
strong alkali. Each step
one of proton remova
complex (from 3+

1 2 3 4

From 1 to 7 happen as you add more alkali, increasing pH and the


OH concentration, removing protons from the chromium(III) complex.

From 7 back to1 represents what happens when you add acid, decreasing pH,
5 6 7 * increasing H+/H O+ concentration and protonating the chromium(III) complex.
3
Chromium(III) ions with aqueous sodium carbonate form the green hydroxide
precipitate (as above) and carbon dioxidebecause of the acidity of the
hexaaquachromium(III) ion (see Appendix 1.):
*initially 2[Cr(H2O)6]3+(aq) + CO32(aq) ==> 2[Cr(H2O)5(OH)]2+(aq) + H2O(l) +
CO2(g)
this process of proton donation (deprotonation) continues until [Cr(OH)3(H2O)3]
(s) is formed
No Cr2(CO3)3 is formed because of the acidbase reaction above, due to the
acidity of the chromium(III) ion. Note the similarly highly charged small
ions Al3+ and Fe3+ behave in the same way.
* the acidity of a the hexaaquachromium(III) ion can be expressed as ...
[Cr(H2O)6]3+(aq) + H2O(l)

[Cr(H2O)5(OH)]2+(aq) + H3O+(aq)

With excess sodium hydroxide or ammonia, further complex ions are formed
from chromium(III) ions by ligand displacement/replacement reactions:
[Cr(H2O)6]3+(aq) + 6OH(aq) ==> [Cr(OH)6]3(aq) + 6H2O(l) (from original hexa
aqua ion)
or [Cr(OH)3(H2O)3](s) + 3OH(aq) ==> [Cr(OH)6]3(aq) + 3H2O(l) (from hydroxide
ppt.)
or more simply Cr(OH)3(s) + 3OH(aq) ==> [Cr(OH)6]3(aq)

showing amphoteric behaviour, since the hydroxide ppt. also dissolves in acid.
[Cr(H2O)6]3+(aq) + 6NH3(aq) ==> [Cr(NH3)6]3+
(aq) + 6H2O(l) (from original hexaaqua ion)
or [Cr(OH)3(H2O)3](s) +
6NH3(aq) ==> [Cr(NH3)6]3+(aq) + 3OH(aq) +
3H2O(l) (from hydroxide ppt.)
or more simply Cr(OH)3(s) + 6NH3(aq) ==> [Cr(NH3)6]3+(aq) + 3OH(aq)
The uncharged ligand molecules ammonia NH3 and water H2O are similar in
size and ligand exchange occurs without change in coordination number. They
all octahedral complexes with a coordination number of 6.
Chromium(III) complexes are extremely numerous and varied, including many
examples of isomerism.
Ionisation isomerism in chromium(III) chloride based on Cr3+, 3Cl and 6H2O
[Cr(H2O)6]3+(Cl)3 (violet or greyblue?)
[CrCl(H2O)5]2+(Cl)2.H2O (pale green)
[CrCl2(H2O)4]+ Cl.2H2O (dark green)
[CrCl3(H2O)3]0*.3H2O ? (brown?, this I found reference to on a Russian
website, doesn't seem to be in textbooks? *the 0 to signify an overall electrically
neutral complex can be omitted)
and this is not all, the 3rd one down with two chloride ligands can exist as cis (1)
or trans (2) geometric isomers (Z/E isomers) illustrated below, and also serve as
models for representing the other octahedral complexes which exhibit cis/trans or
Z/E isomerism.

With excess chloride ion you get the formation of the tetrahedral
tetrachlorochromate(III) ion
[Cr(H2O)6]3+(aq) + 4Cl(aq) ==> [CrCl4](aq) + 6H2O(l)
You also get geometrical cis/trans isomers (Z/E) with
tetraamminedichlorochromium(III) complexes.


A similar case of isomerism occurs with the chromium(III) complexes with ammonia
and chloride ligands shown above. All the complex ions above have a plane of
symmetry and cannot exhibit optical isomerism.
Again, these are all octahedral complexes with a coordination number of 6.
[Cr(H2NCH2CH2NH2)3]3+, H2NCH2CH2NH2, ethane1,2diamine
(ethylenediamine), is often represented in shorthand by en,
and the complex simply written as [Cr(en)3]3+.
This complex has mirror image forms i.e. enantiomers of optical isomers.
This optical isomerism can be illustrated thus

H2NCH2CH2NH2

where LL represents

The ligand bonds via the lone pairs of electrons on the nitrogen
which are donated to form the metalligand dative covalent bonds.
Both the hexaaqua ions of chromium(II) and chromium(III) readily complex with EDTA
[Cr(H2O)6]2+(aq) + EDTA4(aq) ===> [Cr(EDTA)]2(aq) + 6H2O(l)
Kstab = {[Cr(EDTA)3]2(aq)} / {[Cr(H2O)6]2+(aq)} [EDTA4(aq)]
Kstab = 1.0 x 1013 mol1 dm3 [lg(Kstab) = 13.0]
[Cr(H2O)6]3+(aq) + EDTA4(aq) ===> [Cr(EDTA)](aq) + 6H2O(l)
Kstab = {[Cr(EDTA)3](aq)} / {[Cr(H2O)6]3+(aq)} [EDTA4(aq)]
Kstab = 1.0 x 1024 mol1 dm3 [lg(Kstab) = 24.0]
From the Kstab values, you can see that the more highly charged Cr 3+
(aq)

ion complexes more strongly than the Cr2+(aq) ion.

CHROMIUM(VI) oxidation state chemistry


The 'simple' hexaaquachromium(VI) cation, [Cr(H2O)6]6+, cannot exist in aqueous
media.
In fact, I doubt if the 'simple' Cr6+ ion can exist in any ionic compound.
Note that chromium(VI) oxide, CrO3 and chromium(VI) fluoride, CrF6, (both
compounds have Cr in +6 oxidation state), are covalent compounds, despite
the relatively large electronegativity difference between the metal and nonmetal.
If the oxidation state of the central metal ion is over +3, it appears that
deprotonation via proton transfer to water is so facilitated that in most cases
(there may be exceptions?) all protons are 'theoretically' lost to give
the oxyanion.
ie the theoretical [Cr(H2O)6]6+ ends up in reality
as Cr2O72 or CrO42 depending on pH.
The reason for this situation is that the high charge density of the
'theoretical' central metal ion, gives it a high polarising power.
You can theoretically conceive the situation of imagining the central
metal ion pulling on the electrons of the MOH 2 and MOH ligand
bonds in two stages to leave a M=O bond in the oxyanion
ie considering one coordinated water molecule (and
ignoring the charge on intermediate complexes) ...
MOH2 ==proton loss==> MOH ==proton
loss==> M=O
There is, theoretically, always an equilibrium between the chromate(VI) ion and
the dichromate(VI) ion.
2CrO42(aq) + 2H+(aq)

Cr2O72(aq) + H2O(l)

Therefore from Le Chatelier's principle, high pH (alkaline) favours the


formation of the chromate(VI) ion and low pH (acid) favours dichromate(VI)
ion formation.
When hydrogen peroxide is added to an alkaline chromium(III) solution,
oxidation occurs to give the yellow chromate(VI) ion CrO42 .
2Cr3+(aq) + 3H2O2(aq) + 10OH(aq) ==> 2CrO42(aq) + 8H2O(l)
Redox changes: oxidation 2Cr(+3) ==> 2Cr(+6), reduction 6 O(1) in 3H 2O2 ==>
6(2) in 6 of the 8H2O, total of 6 'units' oxidation state change.
Both H2O2 and Cr(VI) compounds are oxidising agents but in alkaline solution
H2O2 is the stronger oxidising agent.
E = +?V details to add???

When the resulting solution from above is acidified with dilute sulphuric acid,
the orange dichromate(VI) ion Cr2O72 is formed.
The equilibrium is pH dependent. From 'Le Chatelier's Principle':
in more acidic solution, more H+, decrease pH ==> more orange (net
change L to R) or in
more alkaline, less H+ (removed by OH), increase pH <= more yellow
(net change R to L).
2CrO42(aq) + 2H+(aq)

Cr2O72(aq) + H2O(l) (no change in ox. state)

The dichromate(VI) ion is reduced in two stages by a zinc/dilute sulphuric acid


mixture.
Cr(VI, +6) ==> Cr(III, +3): Cr2O72(aq) + 14H+(aq) + 6e

2Cr3+(aq) + 7H2O(l)

orange (+6) ==> green (+3), E = +1.33V


Cr(III, +3) ==> Cr(II, +2): Cr3+(aq) + e

Cr2+(aq)

green (+3) ==> blue (+2), E = 0.41V, so Cr(II) is readily oxidised by dissolved
oxygen and can only be retained in an inert atmosphere.
Note the EZn(s)/Zn2+(aq) is 0.76V, so the reducing power of zinc is sufficient to effect
either of the two chromium oxidation state reduction changes.
The full redox equations for the reactions which happen on the surface of the zinc are:
Cr2O72(aq) + 3Zn(s) + 14H+(aq)
2Cr3+(aq) + Zn(s)

2Cr3+(aq) + 3Zn2+(aq) + 7H2O(l)

2Cr2+(aq) + Zn2+(aq)

You will see hydrogen formed as a byproduct of the zincacid reaction but the
reductions take place on the surface of the zinc.
Potassium dichromate(VI), K2Cr2O7, can be crystallised to high purity standard
without water of crystallisation, and is a valuable 'standard' redox volumetric reagent.
e.g. It can used to titrate iron(II) ions in solution acidified with dilute sulphuric acid,
using a redox indicator like barium diphenylamine sulphonate which is less readily
oxidised than iron(II) ions, but once all the iron(II) ions are oxidised the indicator is
oxidised to a blue colour.
The iron(III) ions formed affect the indicator to give an inaccurate end point so
phosphoric(V) acid is also added at the start to complex the Fe 3+ ions as they form.
Cr2O72(aq) + 14H+(aq) + 6Fe2+(aq) ==> 2Cr3+(aq) + 6Fe3+(aq) + 7H2O(l)
Theoretically, there are actually two simultaneous colour changes, both masked by the
redox indicator change.
The orange dichromate(VI) ion changes on reduction to the green chromium(III) ion,
and the pale green iron(II) ion changes on oxidation to the orange iron(III) ion,
so without the indicator I'm not sure exactly how the colour change you would really
observe would pan out!

See also fully worked examples of redox volumetric titration calculation


questions.
The dichromate(VI) ion is a strong oxidising agent examples of oxidising
action:
See above for oxidation of iron(II) ions.
It oxidises iodide ions to iodine.
Cr2O72(aq) + 14H+(aq) + 6I(aq) ==> 2Cr3+(aq) + 3I2(aq) + 7H2O(l)
The released iodine can be titrated with standard sodium thiosulphate solution
using starch indicator.
2S2O32(aq) + I2(aq) ==> S4O62(aq) + 2I(aq) (black/brown ==> colourless
endpoint)
This reaction between the released iodine and sodium thiosulfate can be used to
estimate oxidising agents like dichromate(VI) ions.
The iodine is titrated with standardised sodium thiosulphate (e.g. 0.10 mol
dm3) using a few drops of starch solution as an indicator. Iodine gives a
blue colour with starch, so, the endpoint is very sharp change from the
last hint of blue to colourless.
See also fully worked examples of redox volumetric titration
calculation questions.
Soluble chromate(VI) salts give yellow solutions, but lead(II) ions give a yellow
ppt. of lead(II) chromate(VI) and silver ions a dark red ppt. of silver chromate(VI).
Pb2+(aq) + CrO42(aq) ==> PbCrO4(s) and 2Ag+(aq) + CrO42(aq) ==> Ag2CrO4(s)
A few drops of silver chromate is used as an indicator when titrating chloride
solutions with silver nitrate solution in neutral solution. The solubility product for
the white ppt. of silver chloride
Ksp = [Ag+(aq)][Cl(aq)] = 2 x 1010 mole2dm6
is exceeded before the solubility product of silver chromate(VI)
Ksp = [Ag+(aq)]2[CrO42(aq)] = 3 x 1012 mole3dm9, until all the chloride is
precipitated. The next drop of silver nitrate causes the precipitation of brownish
red silver chromate, so the end point is the formation of the dark red ppt
CHROMIUM(II) oxidation state chemistry:
The blue hexaaquachromium(II) ion,
[Cr(H2O)6]2+(aq), can be formed by reducing
chromium(III) salt solutions with zinc and
hydrochloric acid but it is rapidly oxidised back to
green chromium(III) ions by dissolved oxygen
unless protected by an inert atmosphere.V 3+/V2+E = 0.26V, O2+H+/H2O E =
+1.23V