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[Cr(H2O)6]3+(aq) + 3H2O(l)
1 2 3 4
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)
Cr2O72(aq) + H2O(l)
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)
2Cr3+(aq) + 7H2O(l)
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)
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!