J o h n J.

A l e x a n d e r
I The Synthesis
- and Reactions of a Cobalt
and J o h n G. D o r s e y
University of Cincinnati
Cincinnati, Ohio 45221

I A project for freshman laboratory

T h e design of suitable experiments for t h e general chem- Spectra 01 Co Complexes'

istry l a h o r . & y presents a challenging prnblem. Appn~priate Complex Adnml Color
activities a t the freshman level ought t o introduce students
to needed lat~oratorytechniques and hasic chemical principles. cisCo(~H~).(H~0)Co~+ 510.363 redYiolet
At the same time the experimenrs should capture students' cisCo(NH3),(NOd2+ 506, 358. 295(sh) redviolet
interest. An important factor in maintaining this interest i s C~SCO(NH~)~~H~OI~~+ 502, 355 red-violet
Co(NHd4NO&' 440 yellow
t h e opportunity for successful completion of t h e laboratory transCo(NH3)&lr2+ 490 (sh) yellowqreen
work. Students t e n d to become rather discouraged if their
efforts seem t o produce few results. . ~ ~ a s u r eindaqueous solution.
Added to these reauirements in manv institutions are other
pressures resulting from the large sizes nf freshman laboratory
sections and the artenrlant loeistical vroblems. T h e work must
fit conveniently into three-hour modules. Chemicals must not
b e inordinately expensive. Required equipment m u s t b e (X = NOS NOz, Br)
readily available. T h e principles of t h e experiment m u s t b e
grasped b y t h e teaching assistantships who staff t h e labora- [Co(NH3)&03](N03) + 2HaOf + 3 C 1 - A
tories and have the most direct contact with students. Finally,
t h e results should b e amenable t o "objective" grading pref- cis-[Co(NH3)a(HzO)Cl]Clz CO? + + NOs- + 2HzO (2)
red-violet
erably involving unknowns andlor product yields to h e handed
in. Results of this kind encourage useful discussions among If the reaction mixture is immediately cooled in an ice bath without
students b u t prevent excessive cooperation i n writing labo-
ratory reports.
With so manv criteria to b e satisfied i t is little wonder t h a t
[Co(NH3)&03](NO3) 2H30+ 3X- +
~is-[Co(NH3)~(HzO)z]X3 + CO1
+ -
the heating step, a diaquo product can be isolated.

+ NOa- + Hz0 (3)

large numbers of freshman experiments d o n o t also offer
nossibilities for interestine discussions with briehter students,
?or extending t h e work inGolved and for conveying some of the
excitement of a developing research problem ( 1 ) .
Description of t h e Experiment and Student Results
At the University of Cincinnati we have had considerable success
with a project-type experiment lasting far three laboratory periods
during the first quarter of the freshman laboratory.
During the first week students prepare a sample of [Co(NH&-
COd(NOd.0.6
~ ~ . . ,., ~
H.0
~
(21.. (uide
' . ~ . infral.
I'reparation of the reIraamin? rarbonato mmplex from 1Og of
Co(NO,<v.ti HzO rrsulted in an awmge yirld of 3.5 I: I4Vh4 from 510
freshmen in the Aurmnn of 19X. The literature repunsa yeld of 7W
from n rlmilar prrpnrntwe pr,rrcdurr 12,. I t is likely that our student
yirlds n d d haw been increased hy wurking on o larger ~cnle(say, 15
X I and by adding portimr of (I\'H4),CO? to the mother liquor from
the fint rn,p tuubtnin a sewnd m,p 111r r y s u k . Althw~ghthe pndurt
(X = NO3, CI, Br)
Average student yields for the products are as follows: cis-[Co-
(NH~)~(H~O)CI]CIZ 64%; [Co(NH3)~(N02)2](N0z) 59%; trans-
ICo(NH3)dBrzJBr61% (Lit. 80% (3)).
Our students did not prepare the dinitrato complex (Lit. 33%yield
(3)) because its spectrum was indistinguishable from that of
[CO(NH~)~(H~O)CIIC~Z in the region accessible on Spectronic 20 in-
struments. If more sophisticated spectrophotameters were available,
the compound could be included. The diaquo visible spectrum is also
indistinguishable from that for the dinitrato compound. However,
infrared measurements could distinguish these.
A few students who were given 48% HBr as an unknown obtained
a brown product containing COO instead of the anticipated green
trans-[Co(NHa)bBrz]Br. We are uncertain as to the reason for this
behavior unless it could have resulted from heating to too high a
temoerature.
~ i r i n ethe remainder of the lahoratorv ~,time (after
~ .~~
. ,. the
drvine ~~~~

complex in air fur at least 15 minl students were asked to make up

can be pur~fiedby rwrystall:rarron 121, it is ruff&n~ly pure for
synthrt~cpurposrs. When we askrd some students to actrmpt re-
crvsrnllizntim, a significant fraction could not Atain a crystalline
pnduct on dirsolurmn in hot water, iiltration, nrJing, and addition
of alcohol.
I)urr~gthe serond lnbwator\ perid rtudcntc wen givrn unknuwnd
and naked to allow there lo rrnet with J g portions of ICdNHd,-
CO~l~h'Ozl.0.5H70. The unknown^ all contarn arid which induces
hydhysisof the &rhonato ligand. The presence of anions in solution
will lead to anation on heating, the net reactions being
Presented, in part, at the 173rd National Meeting of the American
Chemical Societv. New Orleans. March. 1967.
Because the second synthesis and spectral measurements will not
require a full six hours of working time, we have found it advantageous
to dovetail this experiment with others.
% T h ecis-[Co(NH3)r(H20)CI]C12 isolated from this procedure is
sometimescontaminated with small quantitiesof trnn~-[Co(NH3)~-
ClzlCl and [Co(NH3)&1]2. This does not affect the identification from
the spectrum. However, purification may be easily effected by con-
verting the chloride to the sulfate. See Reference (3).
solutions of the products they prepared and tu mrasurs the G l r l e
spectrum using Spectrunic 20's. The pmduc~5wuld thrn he identified
by comparison of the measured spectrum with posted spectra of the
complexes.' A solution of proper concentration can be obtained by
weighing precisely around 0.5 g of product and using a 250-ml volu-
metric flask. ICdNH~IaBnlBris not very soluble and onlv about 0.2
e will dissolv; in 250ml &water.
"
Spectral paramrtcrs of products mcaiured on a Cary 11 arc re-
pndutnl in the table. 'The apema reveal that c ~ . ~ - I O ~ ( ~ H ~ , l ~ ~ N 0 3 1 ~ ~
end c i r - I C ~ ) ( N H H20~Clli*
~l~l are dirtinguishnhle mly in the region
below 370 nm. Thus, unless either an instrument having a range in
this region or an infrared spectrophotometer is available, only one of
these complexes is suitable for student preparati~n.~
In our laboratories some 86% of freshman students correctly
identified their complexes from the visible speetnun. After completing
identification, students were asked to write a balanced chemical
equation descrihing the reaction of [Co(NH3)&03]N03 with a salt
containing the appropriate anion in acid solution. They were given
the information that carbonate ion reacts with acid to afford carbon
dioxide and water. This was a particularly challenging aspect of the
experiment for many students who were accustomed to balancing

Volume 55, Number 3. March 1978 / 207

chemical equations as a formal exercise rather than using them to
deserihe actual reactions.
From the balanced equation students were asked to calculate the
yield. Although mast were able to do this correctly, it came as acon-
siderable surprise to many that a yield of considerably less than 1W
was obtained and that this was to be expected in actual chemical
preparations.
Finally, students located the positions of peak maxima and calcu-
lated molar absorptivity. The values of r varied considerably and were
usually not particularly close to literature values owing presumably
t o the fact that no recrystallization was carried out and t o inadequa-
cies in technique in using volumetric flasks.
Procedure
Preparation of [Co(NH&C03] N03.0.5H20
About 10 g of Co(N03).6H20 is weighed by difference into a 50-ml
beaker and dissolved in 10 ml distilled water. This solution is poured
into a 250-ml Erlenmeyer flask containing 15 g (NHdzC03 dissolved
in 20 rnl of distilled water to which has been added 25 ml conc. NHs.
After all the C O ( N O ~ ) ~ . ~solution
H ~ O is rinsed into the ~ r l e n m e y e r
the flask is swirled gently to mix the reactants.
The solution is then cooled to 5" in an ice bath while the student
obtains 10 ml30% H2OZ3(CAUTION: Keep H202off skin and eyes;
it is a powerful oxidizing agent and can cause painful burns.) The
hydrogen peroxide is added dropwise t o the Erlenmeyer flask with
swirling. The addition should he carried out sufficiently slowly that
the solution temperature does not rise above 10". (Alternatively, air
could he bubbled through thesolution for two hours (2).Oxygen has
also heen cmphyed m similar rcnctimr 11)).
After dl tlw H,O> hsr b w n added, the tlnrk is heated to 5040" for
twent\, minutes w t h t,co&iunnl swding. r\lwrnatirrlg the Flmm hath
may be employed.
The flask is then cooled in ice t o complete precipitation of the
water and methanol.
We have found it best to isolate the product during the first working
period since a week's standing of the reaction mixture sometimes
vields red ICO(NHI)ICO~I(NO~. Many students obtain a second crop
of crystalsof the t&aa&e after a week, however.
Dr. Glen Direen of the University of Wisconsin. Madison, has
suggested the use of 10% Hz02 to decrease the likelihood of peroxide
hurns.
208 1 Journal of Chemical Education
Reaction of [CC(NH~)~CO~](NO~)
with Unknown
Students are prvvid~dwith sut'rhent unknown t < r react with :l y
of thc rarhonatocomplex. Suitable unknowns arc. 10 ml conr. HCI;
ISml 1 HBr: 10ml I:] e m r . HSO,: H:O: 10ml 1:1 r u n r . H N O : H z O
and I g N ~ N in O separate
~ vials.-~he3-g sample of the carbonato
complex is suspended in 15 ml distilled water and the liquid unknown
added a little at o time followed by the solid, if any. The solution is
maintained a t 55-65' for half an hour using a burner. At the end of
this time, the mixture is m l e d in an ice hath and the product collected
on a Biichner funnel and washed with cold water and methanol.
Student Discussion and Extension of Work
Several features can serve to stimulate discussion and suggestions
for further work with bright students. Far example, some possibilities
include the purpose of using ammonium carbonate in the synthesis
as opposed to other carbonates (4). the mechanism of CO1 loss on
hydrolysis (4) and the mechanism of anation ( 5 , 6 ) .Extension of the
work could involve elemental analyses (7). synthesis of related
products (9,20, l l ) , or infrared spectra af products (2'413).
We are currently pursuingsome of these problems in the freshman
laboratory at the University of Cincinnati and will report our results
in future publications in this Journal.
Literature Cited
(11 One experiment dealing unthasimiiarsystem which ineorporatesaomeof these features
isdoscribed in0lsen.G. R., J. CHEM. EDUC.,44508(19691.
(2) The preparation ia a slight modification of that described by Schlessinger. G., lnorp
Synfh..6,173 (19601.
(3) Sehlesringer, G.."lnorgenic Laboratory Preparations." Chemical Publishing C a , New
York. 1962.
(4) Dasgupte,T.S.andHarria,G. M . , J Amer Chrm. Soc..91,32W (19691.
(5) (a) Chang, F. C.,end Wondlandf W. W., Thermmhimicc Aclo, 3.59 119711. IblSee
also Ref. (31.
(8) Lsngf",d. C. H. and Gray, H. 8. l'Ligsnd Svhrtitution Prcrernes.'' W. A. Benjamin,
New York, 1965.
(71 ( 4 H U E ~ R. , Endiwft,J. F. Hoffman, M. 2. and House, D. R..J. CHEM. EDUC.,
~ G..
46. 440(19691. (bl Wilson, L. R., J. CHEM. EDUC..46.U7 11969).
(81 Werner. A., 2. Anorg. Chm. 43,338 119051.
(9) Mellow,J.W.."ACompreh~nsivoTrestiseonInorganicandThmreticalChemistry,"
Vol. 14, Lungmans,Green and Co., London, 1935, p. 688
(10) (a1 Jorgcmen,S. M., 2. Anurg Chem., 14,415 (18971. lbl Palmer, W. G., "Experimental
Inarganie Chemislry,nCambridgoUniversity Press. Cambridge. 1954. p. 546
(11) Jorgens~n,S. M.L Anorg. Chrm.. 16.184 118981.
(12) Nakamoto, K.,'lnfrared Spectra of Inorganicand CwrdinationCompounds",Wilcy
Interncience. New Yurk, 1910.pp. 98. 1 6 9 1 2
(13) See, for example, Alexander, J. J. and Steffd,M, d.. "Chemistry in the Laborstary,"
Harcourt B m e Jovanovieh. New York, 1976. Experiment 8.