EXPERIMENT 3 SYNTHESIS, CHARACTERIZATION AND LIGAND EXCHANGE EQUILIBRIA OF POTAS

SIUM TRIS(OXALATO)FERRATE(III) PURPOSE This three-part laboratory exercise will

expose students to their first synthesis of inorganic compound, in this case a c
oordination compound. It offers an integrative approach in laboratory chemistry,
where in addition to gaining skills in synthesis, you will see how basic charac
terization of a compound is carried out using already familiar techniques of tit
rimetry and spectrophotometry (colorimetry) to help elucidate the structure and
further to explore some aspects of the ligand exchange chemical equilibria. OBJE
CTIVES During and by completing this experiment, you (student) will: 1. Synthesi
ze and purify by recrystallization the coordination compound, potassium tris(oxa
lato)ferrate(III). 2. Determine the oxalate content of the coordination compound
via titrimetric analysis using standardized potassium permanganate. 3. Prepare
and standardize a solution of potassium permanganate. 4. Explore the redox chemi
stry of the reaction between the oxalate and manganate ions. 5. Determine the ir
on content of the coordination compound via colorimetric analysis. 6. Calculate
the number of water of crystallization in the coordination compound. 7. Determin
e the molecular formula of the complex synthesized. 8. Explore some ligand excha
nge reactions of the synthesized compound. INTRODUCTION Coordination chemistry i
s an important aspect of chemistry and the synthesis of these compounds is very
exciting due to the variation in colours that these complexes display due to the
interesting electronic and coordination properties by the metal ions and ligand
s. One of the easiest coordination complexes to prepare is potassium tris(oxalat
o)ferrate(III). Its interesting

chemistry and versatility sees it being used as a starting material in the synth
esis of many other industrial compounds. This experiment will be done over the c
ourse of two lab sessions. In the first, you will synthesize the compound and ca
rry out ligand exchange reactions and in the second you will analyze it to deter
mine its molecular formula. As you have learnt in CHEM 1067, inorganic compounds
may contain a variety of species, including ions, ligands, metal centres, and i
ndependent molecules. In this lab, you will synthesize a coordination compound (
complex iron salt) with the formula KxFey(C2O4)z H2O, where C2O42- is the oxalato l
igand. The " " before H2O indicates the number of "water of hydration/crystallizati
on", which means number of water molecules are loosely bound in the crystal. In in
organic synthesis, the desired product is frequently formed and isolated by crys
tallization from a reaction mixture. Because the reaction mixture may contain ex
cess reactants and other products, the crystals are likely to be relatively impu
re. The crystals can be separated from the impure solution (often called the "mo
ther liquor") by filtration or decantation and then washed. However, washing wil
l not remove impurities occluded within the crystals. A standard method for puri
fying the product is recrystallization. The product is redissolved in a minimal
amount of an appropriate solvent, generally while heating. Slow cooling of the s
olution results in slow crystal growth, producing pure crystalline product. An i
mportant factor in syntheses is the actual quantity of desired product obtained
compared to the theoretical amount predicted on the basis of the stoichiometry o
f the reaction. The ratio of the mass of the actual product to the theoretical a
mount is the percent yield. There are many reasons why the actual yield is not 1
00 %; you will be expected to suggest some reasons based on the chemistry of the
method used. The oxalate ion in the compound will be determined by titration wi
th potassium permanganate (KMnO4) according to the reaction: 5 C2O42- (aq) + 2 M
nO4- (aq) + 16 H+ (aq) 10 CO2 (g) + 2 Mn2+ (aq) + 8 H2O (l)

Before you can perform the titration, you will need to standardize the potassium
permanganate using sodium oxalate (Na2C2O4), according to the same reaction. Th
e amount of iron in the complex will be determined spectrophotometrically. First
, the compound is to form ferrous ions, then a reagent, bipyridine, another chel
ating ligand is added which will exchange the oxalate and bind to the metal ion.
The intensity of the red colour is a measure of the concentration and the iron
content is determined from a calibration curve of standards. An important aspect
of the [Fe(C2O4)3]3 complex anion is that it is a very useful product for explor
ing chemical equilibria, offering an overall picture of how ligand coordination,
displacement/exchange and precipitation equilibria are interrelated. The suffic
ient quantity of complex obtained in the synthesis permits utilization of the su
bstance to show students a practical example of the chemistry of complexes in so
lution. The anion presents an ideal balance between stability and lability such
that a number of reactions can be displaced in one direction or the other, depen
ding on the quantity and properties of the reagents involved. APPARATUS AND CHEM
ICALS Fe(NH4)2(SO4)26H2O (5 g) 20 volume H2O2 (9 mL) 1 M H2SO4 (50 mL) 0.005 M FeSO
4 (15 mL) 10 % aqueous hydroxylamine 6 M HCl (few drops) Buchner setup 250 mL vo
lumetric flask 50 mL burette Bunsen/hotplate SAFETY PRECAUTIONS Remember your PP
E: lab coat, gloves and safety glasses should be worn at all times. H2C2O42H2O (4
.5 g) 95 % ethanol (50 mL) 0.02 M KMnO4 K2C2O4.H2O (3.5 g) Acetone (20 mL) Na2C2
O4 (0.4 0.6 g)
0.1 % aqueous bipyridine (30 mL) sodium acetate pH buffer 5 (30 mL) 0.5 M KSCN (
few drops) Filter paper 20 mL Vol. Flasks (3) Foil sheet Spectrophotometer 3 M K
F (few drops) 250 mL beaker 250 mL conical flasks (6) Cuvettes


Potassium permanganate and sulphuric acid and hydrogen peroxide can cause chemic
al burns. The KMnO4 solution is a powerful oxidant and the dilute solution is a
disinfectant will stain skin and clothing. Oxalic acid and oxalates are toxic an
d must not be ingested. Avoid skin contact with these chemicals, but if you spil
l them on yourself, simply wash with cold water. Clean up all spills immediately
. Be cautious when using glassware. Should breakage occur, inform your demonstra
tor, clean up broken glass and place in the broken glass bin, NOT the regular tr
ash (glass in regular trash can injure our custodial staff). Please follow all l
aboratory safety guidelines. Please review current Material Safety Data Sheets f
or additional safety, handling, and disposal information.

EXPERIMENTAL Part A: Preparation of the Complex (Week 1) Mark the level of 45 mL

water in a 250 mL beaker. To a well stirred solution of 5 g of ferrous ammonium
sulphate in 20 mL of warm water containing 1 mL of dilute sulphuric acid in the
beaker, add a solution of 2.5 g of oxalic acid dihydrate in 25 mL of water. Slo
wly heat the mixture to boiling (beware of bumping) then allow the yellow precip
itate to settle. Decant the supernatant through a Buchner funnel making sure it
has a properly fitted filter paper. Add 15 mL of hot water to the solid precipit
ate then stir and filter. Drain well and then transfer all the precipitate from
the paper, back into the beaker with 10 mL hot water. Add 3.5 g solid potassium
oxalate monohydrate and heat to approximately 40 oC. Add slowly, using a dropper
, 9 mL of 20 volume hydrogen peroxide. (If the precipitate looks yellowish, not br
own and settles readily, decant the supernatant, add a solution of 0.2 0.4 g pot
assium oxalate monohydrate in 1 2 mL water and then hydrogen peroxide dropwise u
ntil the precipitate dissolves. Then add the previously decanted supernatant) an
d heat to boiling. Add a solution of 2 g of oxalic acid dihydrate in 30 mL of wa
ter in portions, add 20 mL initially, then, if the brown precipitate still remai
ns, add more solution little by little until it all dissolves. Boil the clear so
lution down to a volume of 40 50 mL,

filter through a Buchner funnel with well fitting paper and add 95 % ethanol slo
wly until a precipitate starts to form (~ 30 mL). Redissolve any crystals by hea
ting (beware of fire assuming...using a flame) and leave to crystallise until ne
xt lab session. On your return to the lab filter and wash the crystals on the Bu
chner with a 1:1 ethanol/water mixture and finally with acetone, (beware fire ag
ain). Dry in the air and weigh. The complex is photosensitive and should not be
exposed to light unnecessarily. Store in a sample bottle wrapped in foil. Part B
: Chemical Equilibria Ligand Exchange Reactions (Week 1) Approximately 0.1 M s
tock solution of potassium tris(oxalate)ferrate(III) is available to the class f
or use. Place 1 mL of the green stock solution 1 in a test tube and add 3 drops
of 6 M HCl. Note the colour change of this solution 2; To 2 add 3 drops of 0.5 M
KSCN and note the colour of this new solution 3. To 3 add 10 drops of 3 M KF an
d note the change of this new solution 4. Finally, add to 4 15 drops of 2 M K2C2
O4, and record the change. Write reaction equilibria for each step and give a ra
tionale for the changes taking place. Part C 1: Determination of Oxalate Content
by Titrimetry (Week 2) a. Standardization The permanganate solution should be s
tandardized accordingly: Weigh accurately two portions of about 0.2 g AnalaR sod
ium oxalate into conical flasks. Dissolve each in water, acidify with 50 mL of 1
M sulphuric acid and titrate slowly with permanganate at 60 oC until the soluti
on retains a pin colouration after standing for about 30 seconds. b. Titration o
f Sample In duplicate, weigh accurately about 0.2 g of the potassium tris(oxalat
e)ferrate(III) complex previously prepared. Boil the sample with 50 mL of 1 M su
lphuric acid in a conical flask.


Allow the solution to cool to about 60 C and titrate slowly with the standardized
potassium permanganate solution. Continue until the warm solution retains a sli
ght pink colouration after standing for about 30 seconds. Calculate the percenta
ge by weight of oxalate in the complex, compare this with the theoretical value
and thus obtain the percentage purity of the complex.

Part C 2: Determination of Iron Content by Spectrophotometry (Week 2) a. Prepari

ng Sample and Standards Accurately weigh a portion of about 0.15 g of the potass
ium tris(oxalate)ferrate(III) compound and dissolve it in distilled water and ma
ke up 100 mL in a volumetric flask. Label this solution A1. Prepare solution B1 by
accurately transferring using a pipette 1 mL of solution A1 to a 50 mL volumetr
ic flask and dilute to the mark with deionised water. To this add 10 mL of 0.1 %
aqueous bipyridine solution, 2 mL 10 % aqueous hydroxylamine solution (to reduc
e Fe(III) to Fe(II)) and 5 mL of 2 M sodium acetate buffer (pH range 5 7) and fi
nally dilute to the mark with deionized water and mix thoroughly. Prepare a dupl
icate by repeating the first two steps, labelling the solutions A2 and B2 accord
ingly. Prepare the five ferrous standards as follows. To a 50 mL volumetric flas
k add 2 mL of 0.0005 M FeSO4, 10 mL of 0.1 % aqueous bipyridine solution, 2 mL 1
0 % aqueous hydroxylamine solution (to reduce Fe(III) to Fe(II)) and 5 mL of 2 M
sodium acetate buffer (pH range 5 7) and finally dilute to the mark with deioni
zed water and mix thoroughly. b. Repeat this using 3, 4, 5, and 6 mL of 0.0005 M
FeSO4 and label these solutions appropriately. Colorimetric Analysis Compare th
e colour intensities of all the solutions using the spectrophotometer. At the se
lected wavelength (522 nm) measure the absorbance of the solutions at least thre
e times and tabulate the results and calculate the average of the absorbance. Pl
ot a graph of absorbance, A, against iron concentration, [Fe], using values from
the five standard solutions. Determine the equation of the line and use it to d
etermine the

concentration of the unknown samples. Certainly, one will have to work back to d
etermine the actual amount of iron based on the mass of sample used. Ensure prop
er use of instrument with respect to zeroing during the measurement; please cons
ult the instrument manual on myelearning prior the lab session. Part C 3: Determ
ination of Water of Crystallization (Week 2) Weigh 0.5 0.7 g (
0.0001g) of the co
mplex salt into a pre weighed evaporating dish. Label or mark the dish so you ca
n identify it and place the evaporating dish and complex salt in an oven set at
110 oC for approximately 45 minutes. Cool the dish and contents and weigh to the
nearest
0.1 mg. Calculate the % H2O in the crystals. EXCERCISES a. Pre Lab 1. U
sing examples, explain the difference between complex, complex ion and a coordin
ation compound. 2. Identify the type of and draw the structure of the oxalato an
d bipyridine ligands. 3. Draw the structure of tris(oxalato) ferrate(III) and tr
is(bipyridine) ferrate(III) complex ions and identify any isomerism in each. 4.
In the synthesis of the coordination compound, identify the purpose of the hydro
gen peroxide and write a balanced equation of this reaction step in the synthesi
s. 5. Identify and draw the structure of another ligand that has similar coordin
ation to the bipyridine ligand forming a similar complex. b. Post Lab 1. From th
e percentages of oxalato ligand, Fe3+ ion and water of crystallization, propose
a formula for the complex ion and coordination compound. 2. Using crystal field
theory (crystal field splitting energy), give an account of the colour changes i
n the ligand exchange reactions in part B.