Experiment 5: Report Sheet

Preparation of K3[Fe(C2O4)3]3H2O
Table 1. Preparation of potassium tris(oxalato)ferrate(III)
Mass (g) Number of moles Remarks
Barium chloride 25.5240 0.104487 Excess
Potassium oxalate monohydrate 18.7345 0.101685 Limiting
Ferric sulfate 13.0649 0.0326721 Excess
Potassium oxalate monohydrate 20.1226 0.109219 Excess
K3[Fe(C2O4)3]3H2O 33.3012 0.06779 Theoretical
Note: Indicate which reactant is limiting or in excess in the remarks column. For mass of
K3[Fe(C2O4)3]3H2O, place the theoretical yield.

Actual mass of K3[Fe(C2O4)3]3H2O: __21.7324 g__ Percent yield: ___65.26 %___

Table 2. Thiocyanate test for selected ferric salts

Color with KSCN
Conc.
before after
K3[Fe(C2O4)3]3H2O 0.1M Green Green
Ferric sulfate 0.05M Yellow-brown Red
Ferric ammonium sulfate 0.05M Yellow-brown Red
Account for the difference in the colors observed.
Three kinds of salts are compared here. Ferric sulfate (Fe2(SO4)3) is a simple salt,
composed of one cation and one anion neither of which are complexes. Ferric ammonium
sulfate (NH4Fe(SO4)212H2O) is a double salt, composed of two cations and one anion and
is obtained by combination of two different salts which crystallized in the same lattice.
Potassium tris(oxalato)ferrate(III) is a complex salt, composed of a cation and an anion
where either or both are complexes; in this case, the iron(III) is present as a complex with
oxalate ligands. In solution, the iron in potassium ferrioxalate exists as the ferrioxalate
complex, [Fe(C2O4)3]3- whereas in both ferric sulfate and ferric ammonium sulfate it exists
as the hexaaquairon(III) complex, [Fe(H2O)6]3+.
When KSCN is used to test for the presence of iron(III) ions in solution, what occurs
is a ligand substitution reaction where one of the thiocyanate ions displaces a ligand from
irons coordination sphere. The colors the three salts give with KSCN reflect the ease by
which ligand exchange can occur. The red color is a result of the
pentaaquathiocyanatoiron(III) complex:
[(2 )6 ]3+ + [(2 )5 ()]2+ + 2
The ferrioxalate ion does not react with the thiocyanate ion to form the red complex,
however for discussions sake the theoretical reaction is shown below:
[(2 4 )3 ]3+ + 2 [(2 4 )2 ()2 ]3+ + 2 42
 The bonds between the aquo ligands and the iron(III) center are labile and are easily broken,
thus the thiocyanato ligand can replace water in the coordination sphere. Additionally, this
is an example of the chelate effect, where polydentate ligands form very inert complexes
compared to monodentate ligands since it is much harder to break a large number of bonds
at the same time. The chelate effect is primarily entropy driven and can explain why the
hexaaquairon(III) complex reacts with thiocyanate, but not with tris(oxalato)ferrate(III).
When the hexaaquo complex reacts with thiocyanate, two species react to form two new
species: there is no change in the total number of species before and after reaction, so there
is no useful contribution to an increase in entropy. When the tris(oxalato) complex is added
with thiocyanate, however, three species react to form two new species: there is a decrease
in the total number of species before and after, so there is a decrease in entropy. The second
reaction would mean moving from a disordered state to a more ordered state; this isnt
likely to happen, which makes the tris(oxalato) complex more inert than the hexaaquo
complex.

Table 3. Color tests of some ferric salts

Color with
Solution Color Reagent added Color produced
KSCN
Fe2(SO4)3 Yellow-brown H2SO4 Colorless Red
Fe(NO3)3 Yellow HNO3 Yellow Red
FeCl3 Yellow-orange HCl Yellow-orange Red
H3PO4 Pale yellow Pale yellow
FeCl3 in HCl Yellow-orange
KF Colorless Colorless
What makes a coordination compound different from simple salts?
Salts are formed from the combination of acids and bases, and dissociate into
cations and anions when in solution. Coordination compounds differ from simple salts in
the identity of the constituent ions. Simple salts are derived from acids and bases where the
hydrogen ions of the acid are replaced by the metallic ions from the base, e.g. sodium
chloride (NaCl). Complex ions are much the same, except that in complex salts there are
two different types of metal atoms, one of which does not ionize when in solution (e.g.
potassium ferrioxalate).
The differences between simple and complex salts are demonstrated by the tests
performed in Table 3. When iron is present in simple salts, it dissociates in solution to form
the hexaaquairon(III) ion; adding sulfuric and nitric acid simply adds counter-ions to the
solution. Thus when KSCN is added, the thiocyanate ion can displace one water ligand
from irons coordination sphere (as it is a stronger-field ligand than water) and form the
red pentaaquathiocyanatoiron(III) complex.
 Iron(III) chloride is a simple salt of ferric hydroxide and hydrochloric acid. It reacts
with excess chloride ions in solution to form the yellow, tetrahedral tetrachloroferrate(III)
complex:
[(2 )6 ]3+ + 4 [4 ] + 62
A red color is observed when KSCN is added to a solution of tetrachloroferrate(III). Ligand
exchange reactions occur when thiocyanate is added to solutions of [4 ] because the
thiocyanato ligand is a stronger-field ligand than the chloro ligand and so can displace it
from the coordination sphere, forming the red thiocyanatoiron(III) complex. This effect is
also entropy-driven as five species react to form seven species, resulting in a net
contribution to an increase in entropy.
Phosphate and fluoride ions are further added to the tetrachloroferrate(III) ion in
solution. Both of these form stable complexes with the iron(III) center, as evidenced by the
absence of a red color when KSCN is added.