An Inorganic Spectrophotometry Experiment

for General Chemistry

A Simplified Graphical Approach for Determining
~ i ~ a n d - t o - ~ 'Complexation
etal Ratio
Henry N. Po and Kenneth S.-C. Huang
California State University, Long Beach, CA 90840
There are several spectrophotometric methods ( I , 2) for
determining the stoichiometric ratio of ligand coordinated
to transition metal ion. These methods include the molar
ratio method ( 1 4 ) , Job's method of continuous variation
(1,2, 4, 51, the slope-ratio method (2) and the Bjerrum
method ( I , 6). I n the Job's method of continuous variation,
absorbance is plotted against the mole fraction of the met-
al and the ligand. This method is adopted by several gen-
eral chemistry laboratory textbooks (7,8,9). I n this paper
we describe an approach that simplifies and reduces the
calculations for determining the stoichiometric ratio
within a metallo complex.
A complexation reaction for a metal ion, M, with a n or-
ganic ligand, L, is shown below. For simplicity, the charges
are not included.

The stoichiometric ratio, bla, corresponds to the number

of moles of ligand coordinated to one metal ion.
mL Fe(ll)
Procedure and Results Absorbance versus volume Fe(ll) plot for ~e(phen)?+complex. +
The following solutions are needed for the Fe(phenhh spee symbol, 1.5 x lo3 M Fe(ll) ;squares, 1.0 x 10"M Fe(ll);and trian-
trophotometry experiment: 1.00 x 1@M (NHdzFe(S0dz gies, 0.70 x 10" M Fe(ll).
(with 3 mL wnc. HzS04added to 1L solution), 1.26 x lo3 M
1,lO-phenanthroline (phen), 2 M sodium acetate, and 3 M lines a s shown in the figure. For each series of Fez+, a
NHzOH. lhnsfer exactly 0,2,3,4,6,8,10,12,14,16,18, and "peak" volume of Fez+is obtained a t the intersedion of the two
20 mLFe2+solutionto 100-mLvo1umetricflasks. Add in serial data lines. This corresponds to a fully wmplexed imn(I1)-phen.
order to the above solutions 20, 18,17,16, . . .8,6,4,2, and 0 The "peak" volume of phen is by difference because the total
mL phen solution. 'lb each flask add 5 mL of 2 M sodium ace- volume of Fez+and phen is kept constant a t 20 mL. Alter-
tate. about 4 mL of 3 M NH?OH. dilute to mark with distilled nately, one can obtain "peak" milliliters of phen directly from
wa&, and mix. Wait five to i 0 mjnutes. S d u m acetate buffer a double abscissa plot where the volume of phen (in reverse
is used to maintain the solution at pH 5 while hydroxylamine order of 20, 18, 16, . . .2,O mL)is the second abscissa. Mole
ensures that iron is in +2 oxidation state. lhe absorbance of ratios calculated as phen/Fe(II) are listed in the table.
each Fe(I1,-ohen solution is measured at L ..510 nm usinaa Two other polypyridines, 2,Z'-hipyridine (bipy) and
Shimadm lh160 spectmphotometer. (other models of s 6 e
2,2',2"-terpyridine (terpy), were used in the experiment.
trophotometers can be used just as well.) The data points for
three Fez+concentrations are plotted and fitted with straight These results are also listed in the table. The stoichiomet-
ric ratios determined by this simplified approach for the
Stoichiometry of Fe(ll) Complexes three iron(I1)-polypyridine complexes are precise and ac-
of Terpy, Bipy, and Phen curate. The deviation from the theoretical value is less
than 1.3% for bipy and phen and 6.2 % for terpy.
mole ratio I n the figure, one observes that the peak location is
UFe(ll) changed when Fez+concentration is varied. Thus, it is pos-
sible for students to prepare different concentrations of
1.50 1.39x 10" bipy 3.02 Fe(I1) and ligand for the spectrophotometry experiment.
1.OO 1.39 x bipv 2.95 The peak volume may change for a series of M-L combina-
1.50 1 . 2 6 104ph;n
~ 3.07 tion but the same stoichiometry should be obtained.
I .OO 196~10~phen 2.94
0.70 1 . 2 6 103phen
~ 3.00 Literature Cited
1.50 1.00 x lo4 terpy 2.13 1. Bauer, H.H.;Christian. G. D.; O%illy, J.E.InsfrumnfolAn~lysU;AllynandBam:
Boston.1978;Chapter 7.
1.OO 1O
. O x 10" terpv 2.12 2. Wlllard. H. H.:Memitt, L. L.,Jr; Dean,J. A Instrumntd Methtbods ofAndysis, 5th
Absorbance measured at the following Lax: Fe(bipy)z2*= 521 nm: sd.; 0. Van Nostrand: New York,1974:Chapter 4.
Fe(phen)s2*=
510 nm: ~e(ter~~)2~'=552
nm. 3. Jakubiec, R.;BolU,D. EAm1. Chem. 1969,41,13.

62 Journal of Chemical Education

4. Cheng, K h lnSpPetmekmimlMethodpofAnalyais; Wlnefordner J. D.. Ed.; Wiley-
Interstienee: New York, 1971: Chapter&
6. a. Job, P A M I Chim 1988,9, 113. b.Vo8burgh. W C.: Cooper, G. R.J h r Chem.
SN. 1941, M , 437.
6. Bjermm, J. Kg1 Don& Vhnskab. S d ~ k a b Mot3ys.
, MPdd l s M , Z 1 H ) . Olemp, H.
JmKlori&mos Komplerilel Thesis: Lund, 1944
7. Whitten, K W.; Gailey, K D.;Bishop, C. B.; Bishop, M . 8. Exprimenfs in & m r d
Chemistry: Saundem: Philadelphia, 1988; Experiment 25.
8. WahLey, J. A ; Walmsley, E Chemical Principles, P m p w t b , and &mtions in fk
Lobomfory: Addison-Wealey: Reading MA, 1986: Experiments 12 and 14.
9. BaLer, A. D.:Glies, L. F;Nsridi, M. H. Labomtory Monild to Accompany Chemistry:
West: St. Paul MN,1990; Experiment 32.
Volume 72 Number 1 January 1995 63