I A Combined lnfrared and Kinetic
William H. Hohmon
Marietta College
Marietta, Ohio 45750
I Study of linkage homers
I A n inorganic experiment
The following experiment has been carried out by stu-
dents enrolled in the inorganic chemistry lahoratory the
last few years. T h e students prepare the compounds for
study, interpret the infrared spectra, and perform a kinet-
ic study on the compounds. Since this is a multipart ex-
periment dealing with the same two compounds over sev-
eral laboratory periods, much interest has been shown by
the students.
Two linkage isomers, nitro- and nitritopentaammineco-
halt(II1) chloride, with the formulas [Co(NH&NOz]Clz
and [Co(NH&ONO]C12, respectively, are synthesized by
the student and the infrared spectra of the two com-
pounds are studied. T h e nitrite ion ligand is amhidentate
since it can form a coordinate covalent bond t o the Co(II1)
ion a t two non-equivalent sites. The metal-to-ligand
bonding in the nitro complex is through the nitrogen of
the N O 2 ligand, and for the nitrito complex it is through
one of the oxygen atoms. These isomers have relatively
simnle infrared snectra so t h a t the student can easilv
m a i e assignments'of the hands. This allows the instructo"r
..
t o introduce the basic o r i n c i ~ l e sof infrared soectrosco~v
into the laboratory course.
In addition, the nitrito isomer slowly converts into the
nitro isomer in solution and in the solid state. In this ex-
periment, the rate of isomerization of the nitrito t o the
nitro isomer is followed in the solid state using a n infrared
technique. The order of the reaction and the mechanism
for the conversion can he determined.
Experimental
Synthesis of [Co(NH3J50NO]CIZ1
Dissolve 10.0 g of chloropentaamminecohalt(II1) chloride,
[Co(NH&CI]CL, in a solution of 15 ml of concd aqueous NH3 in
160 ml of water while stirring and gently heating. Filter off any
slight precipitate of cobalt oxide that may form and then cool the
filtrate to about 10°C. While cool, add 2 M HCI dropwise in the
solution until just neutral to litmus. Then dissolve 10.0 g of sodi-
um nitrite to the solution before adding 10 ml of 6 M HCI. Allow
the solution to stand in an ice bath for 1 hr and then filter off the
salmon-pink crystals. Wash with 50 ml of ice water, fallowed by
50 ml of alcohol and air dry an filter paper at roam temperature.
Upon standing, isomerization to the nitro isomer occurs.
Synthesis of [ C O ( N H ~ ) ~ N O ~ ] C I ~
Dissolve 4.0 g of the [CO(NHZ)IONO]CI~ in 40 ml of hot water
containing a few drops of aqueous NHs and then add, while cool-
ing. 40 ml of coned HCI. Coal the solution thoroughly and filter
Table 1. lnfrared Absordion Bands (pm)
Nitrito 6.2 6.8 1.6 9.5 11.8
Nitro 6.2 7.1 1.7' 11.8 12.2
a This hand is a combination of two absorption bands.
Table 2. Typical Kinetics Data
Time Absorbance
(da) * A - A-
Absorbance data using the nitrito band a t 9.5 pm
(1060 em-').
off the yellaw-brown crystals. Wash the product with 25 ml of al-
cohol and air dry an filter paper at room temperature.
lnfrared Spectra
An infrared spectrum of each isomer is made as soon as the
complexes are dry, using the KBr pellet method. Assignment of
all absorption bands shown in Table 1 is made for each isomer by
comparing the spectra to known compounds and by using correla-
tion charts. Both compounds have common absorption bands in
the region 5-15 pm (2000-650 cm-') due to NH3 ligand vibra-
tions. A comparison is made to an infrared spectrum of
[ C O ( N H ~ ) ~ ] The
C I ~ nitrito
. isomer has two hands characteristic of
O N = O vibrations and the nitro isomer has two bands charac-
teristic of NOz- vibrations which reflect the difference in struc-
ture and mode of coordination of the ligands. A comparison is
made to an infrared spectrum of Nas[Co(NO&]. After assign-
ments are made, the student is referred to the original literature
to check his work.2 Also, a lab lecture on infrared spectra can be
incorporated at this point. Since the nitrito isomer converts to the
nitro isomer, a study of the nitrito isomer KBr pellet will show
that infrared bands due to the nitrito ligand disappear and those
due to the nitro ligand appear on standing.
'Jolly, William L., "The Synthesis and Characterization of In-
organic Compounds," Prentice-Hall, Inc., Englewad Cliffs, N.J.,
1970, p 463.
2Penland, R. B., Lane. T. J., and Quagliano, J. V., J Arner.
Chem. Soc., 78,887 (1956).
Basolo, F., and Hammaker, G. S., Inorg. Chem., 1,1(1962).
Volume 51, Number 8, Augusf 1974 / 553
Kinetic Study
A quantitative observation of the isomerization of the nitrito to
the nitro isomer is made in the solid state in the infrared region
using the technique of B a s ~ l oThe
. ~ rate of the reaction is first-
order in aqueous solution as well as in the solid state, with the
isomerization taking place faster in aqueous solution. The kinetic
study should he started as soon as a KBr pellet can be made of
the nitrito compound. The pressure at which the KBr pellet is
pressed does not seem to affect the kinetics results. The isomer-
ization is followed by observing the disappearance of the nitrito
hand at appronimstely 9.5 p m ( 1 M em-'). Runs are made on
the KBr pellet at various convenient time intervals over a period
of 3 wk so that there are five or six recordings of the spectra. The
pellet is kept in a desiccator at room temperature or in a metal
container in a constant temperature bath except during the spee-
tral measurement. Using a KBr pellet the cell path length is ean-
stant; therefore, the concentration of the complex is proportional
to log To/T, or absorbance. The T is read directly from % trans-
mittance recording paper and the TOis estimated by connecting
the base line immediately before and after the nitrito band and
averaging the readings. At the end of the kinetics experiment, the
554 / Journal of Chemical Education
KBr pellet is placed in an oven at 100°C for several hours to com-
plete the isomerization and to obtain an A.. measurement. In the
lab, the students are asked to make various plots of the data: (A
- A , ) versus time, 1/(A - A, ) versus time, and log (A - A. ) ver-
sus time in order to determine which plot best suits the kinetic
data. A straight line is obtained from a plot of log (A - A. J versus
time with a slope equal to -k/2.303 indicating first-order kinet-
i a . Typical student data areshown in Table 2.
Extensions
Further experiments include: measuring the visible
spectra of these compounds t o determine the ligand field
splitting and then comparing the results to a series of
other Co(II1) complexes; studying the effect of sunlight,
ultraviolet light, and heat on each of t h e KBr pellets t o
determine interconversions of the isomers; and performing
analogous experiments. on similar Cr(II1) or Rh(II1) com-
plexes t o determine whether similar infrared and kinetics
results are obtained. Also, a comparison of the kinetics in
aqueous solution to the kinetics in the solid state could he
performed.