edited by
GEORGE L. GILBERT
A Versatile Demonstration with Calcium Carbide
SUSMITTEO BY
Ariel A. Fender
John Abbon College
St. Anne de Bellevue, PQ. Canada
Davld N. HarDD
MCGIII unlversltG '
Montreal, PO, H3A 2KB Canada
Joseph A. Schwarcz
Vanier College
Montreal. PO, H3X 2N9 Canada
CHECKED
BY
Erwln Boschmann
IU-PU at lndlanapolis
lndlanapolis, IN 46202
The generation of acetylene by the addition of calcium
carbide to water and its subsequent comhustion have been
reactions of great practical utility; such devices as "starter
cannons" use this chemistry.' We wish to report a useful
means whereby the necessity for the presence of oxygen in
the comhustion is effectively demonstrated. More impor-
tantly perhaps, this technique provides a completely avail-
able and inexpensive methodology to carry out the experi-
ment.
Fifty milliliters of water are placed in a 250-mL vacuum
filter flask followed by -1 g of calcium carbide lumps. Pow-
dered calcium carbide should not he used because the reac-
tion proceeds too quickly. The flask is then lightly cork-
stoppered and immediately (2-3 s) a lighted match is placed
next to the vacuum opening on the flask. Within a few
seconds the acetylene in the flask explodes, rocketing out the
stopper with a sharp report. The calcium carbide is allowed
to react further (more can he added) and the flask is then
lightly restoppered. After 10-15 s a match is placed next to
the opening and with everyone expecting an even louder
explosion, the acetylene now meekly ignites a t the opening
with a soft squeak. The flame can he allowed to burn out, or
extinguished by covering the opening with a small glass
plate.
The explanation for this seemingly surprising result is
that initially the flask contains an explosive mixture of oxy-
gen and acetylene leading to the expected effect; further
evolution of acetylene, however, drives the remaining oxy-
gen from the flask so that comhustion takesplace only where
the cornhustible gas, acetylene, comes into contact with the
oxidizing agent, oxygen gas. Initially, if the match is not
quickly placed near the vacuum opening, the acetylene may
have displaced the oxygen and no "explosion" will take
place. This apparatus can he used to demonstrate the differ-
&es hetwee~n~controlled mmbustion and explosionand also
clearly illustrares the principle of the6'carbidelamps" of the
early mining days.
This demonstration has been executed nearly 200 times
' Hague, G. R., Jr. J. Chem. Educ. 1983, 60, 355.
444 Journal of Chemical Education
Denison University
(2anville. Ohio 43023
with a perfect safety record. For added safety, the flask
could he selectively taped (so as not to obscure the reaction)
and placed in a glass or clear plastic container to reach just
below the take-off arm. Further, safety shields can he placed
in front and behind the demonstration for complete protec-
tion.
The Induction by lron(li) of the Oxidation of iodide
by Dichromate
SUMlrn BY
Wllliam L. Jolly
U n l ~ e r s i t y01 Calllordlt
Berkeley, CA 94720
The ideal lecture demonstration is thought-provoking as
well as pertinent to the topic under discussion. When, in a
course in inorganic chemistry, I have almost finished dis-
cussine the mechanisms of inorganic reactions in aaueous
soluti&s, I like to present this dekonstration. ~ l t h o u g hthe
procedure and results are fairlv simole.
. . one is able to deduce
a rather surpriring mechanism.
First consider the reductim potentials for dichromate and
triiodide
Cr(V1) + 3eC p Cr(II1) Eo = 1.33 V
I t is obvious that dichromate (represented above by Cr(V1)
for simplicity) is a stronger oxidizing agent than triiodide
and that it is capable of oxidizing iodide to triiodide. The
first step in the demonstration is actually to add an iodide
solution to a weakly acidic dichromate solution. Nothing
much happens. (Only after an hour or two is a gradual dark-
ening of the solution perceptible, due to the formation of
brown 13-.) The predicted reaction takes place very slowly, if
a t all.
The second step of the demonstration is to add a solution
containing ferrous ion to the reaction mixture. Essentially
instantaneous formation of brown IS- occurs upon adding
the reducing agent Fe(II)! This result can serve as the basis
for discussion with the class. Probably a student will suggest
that the Fe(I1) acts as a catalyst for the oxidation of iodide
by dichromate, that is, that the Fe(I1) is oxidized to Fe(II1)
by dichromate, and that the Fe(III), in turn, oxidizes the
iodide:
However, if the proposed catalytic mechanism is correct,
then the reaction of Fe(II1) with I- must he at least as fast as
the overall reaction, which was found to occur almost instan-
taneously. This point can he tested.
The next step of the demonstration is to add an iodide
solution to a solution of Fe(II1) having the same acidity as
the dichromate solution. Nothing happens. Obviously the
brown 13- color forms a t a rate much lower than the rate of
oxidation of iodide by dichromate in the presence of Fe(I1).
Hence we conclude that the Fe(I1) ion does not simply a d as
a catalyst for the dichromate-iodide reaction. Another ex-
planation, and further discussion with the class, are re-
quired. It may take some prompting to get someone to sug-
gest that perhaps the Fe(I1) reacts with the dichromate to
form an intermediate species which is able to oxidize the
iodide ion rapidly. Indeed, the reaction is believed to pro-
ceed by such a mechanism.' The Fe(I1) is said to "induce"
the dichromate-iodide reaction.
The following reactions are believed to be important.
Cr(V1) + Fe(I1) - Cr(V) + Fe(II1)
followed by
CrW) + 31- - Cr(II1) + I<
and
CrW) + 2Fe(II) - Cr(II1) + 2Fe(III)
The relative rates of the latter two reactions would be ex-
pected to depend on the iodide concentration. I t has been
shown' that, when the iodide is in large excess, the first
reaction predominates and two equivalents of iodide are
consumed for each equivalent of Fe(I1).
As is often the case in kinetic studies, this mechanism is
not the only one consistent with the data that we have
considered so far. For example, the following mechanism
would also fit the facts.
Cr(V1) + Fe(I1) - Cr(II1)+ Fe(V)
followed by
Fe(V) + 31- - Fe(1II) + IS-
and
Fe(V) + 2Fe(II) - 3Fe(III)
However, Cr(V) has been identified2a3as an intermediate in
reductions of Cr(VI), whereas there is no supporting evi-
dence for Fe(V). Hence the former mechanism seems much
more plausible.
Suggested Reagents and Procedure
Dichrornate Solution: Prepare 1L of asolution0.005M inNanCrz07
and 0.20 M in H3PO4.
Iodide Solution:Prepare 100 mL of 0.20 M KI.
Fe(I1) Solution: Prepare 100 mL of 0.05 M FeS04.
Fe(II1)Solution: Prepare 1 L of a solution 0.05 M in Fe(NO& and
0.20 M in HIPOI.
Step 1: Add 20 mL of iodide solution to 200 mL of dichromate
solution.
Step 2: To the above mixture, add 20 rnL of Fe(I1) solution.
Step 3: To 200 rnL of Fe(II1)solution, add 20 mL of iodide solution.
' Wagner, C.: Preiss, W. 2.Anorg. Chem. 1928, 166, 265: alsosee
Sykes, A. G. Kinetics of Inorganic Reactions; Pergamon: London,
1966. o 204.
ddnon. F. A.; Wilkinson. G. Advanced Inorganic Chemisrty 4th
ed.; Wiley-Interscience: New York. pp 732-733.
Haight. G. P.; Jurslch. G. M.: Kelso. M. T.: Merriil. P. J. Inorg.
Chem. 1985, 24, 2740 and references therein.
The Cola Clock: A New Flavor to an Old Classic
SWMIITEO
BY
Rlchard A. Russell and Robert W. Swltzer
Unlverslty College, UNSW, ACT, Australia 2600
CKCKEOBY
Davld Speckhard
Lorao College
Dubuoue. IA 52001
Clock reactions are frequently used in lecture demonstra-
tionsand have been thesuhiect ufa number ofarticles in thic
Recently we have developed a new variation of
this theme that seemed ~articularlvrelevant in the lieht of
current events. Using the phenolphthalein-formalin'clock
reaction conducted in a cola bottle, we have involved the
audience by asking them to help change the clear solution to
their favorite cola by chanting the appropriate brand name.
T o their dismay they end up with strawberry soda. At a later
stage in the lecture we introduce a second demonstration
that, with appropriate audience support, does produce cola.
The basis of this experiment is the classical iodine clock
reaction2? however. instead of usine starch as an indicator
we have s"bstituted'vitex4, which inappropriate concentra-
tion affords a d e e brown
~ color with the reaction nroducts.
This demonstration has proved very popular with-students
and provides an interesting variation in flavor to an old
classic.
Procedure
Prepare two stock solutions containing iodic acid (50
gL-'F and anhydrous sodium sulfite (21 gL-'1, respectively.
Place approximately 690 mL of water containing Vitex (0.5
onstmtiun, with a magnetic stirrer."he
.. throu~houtthe dem-
a) in a cola bottle. and stir vieorouslv.
addition uf 30 ml.
uf each of the stock solutions will ~ r o d u c the
e desired hrown
color in approximately 15-20 s. his time may be varied with
appropriate changes in concentration.
' Bartlen, R. L. J. Chem. Educ. 1955, 32,78, and references cited
therein.
Bailey, P. S.; Bailey, C. A,; Anderson. J.: Koski, P. G.; Rech-
steiner. C. J. Chem Educ. 1975, 52, 552.
'Lambert, J. L.; Fina, G.T. JChem. Educ. 1984, 61, 1037.
Vitex is a cold-water-soluble starch-based iodometry indicator
manufactured by J. D. Bolton (Hornchurch,Essex, UK), and suppled by
Ajax Chemicals, P.O. Box 83, Auburn, N.S.W., Australia 2144. An
equally acceptable cold-water-soluble indicator can be prepared by
heating to reflux, a finely ground miaure (l:19 by mass) of starch and
urea in xylene, so that the starch dissolves in the molten urea. When
-
Cold. the solid mass is collected bv filtration. washed with a link liaht
perro!eLm, an0 tfnelypowdered Some varoation in t ming of the clock
reaction may be ooserved wlth dltterenl preparations of this mdicalor
ana ue recommend that each balch oe checked prnor to Jse n a
demonstration.
If iodic acid is unavailable, an appropriate solution of potassium
iodate in dilute sulfuric acid may be substituted.
Vigorous stirring ensures a sharp color change in both demon-
strations.
Volume 64 Number 5 May 1987 445