edited by
Denison University
Inorganic Thermochromism: A Lecture
Demonstration of A Solid State Phase Transition
Roger D. Willett
Washington Stale University
Pullman, WA 99164
CHECKED BY:
Arnold George
Mansfield State College
Mansfield, PA
Students in introductory chemistry courses are introduced
to the concept of phase transitions using the familiar examples
of solid-liquid, liquid-vapor, and solid-vapor transitions.
These are conveniently demonstrated in the lecture situation.
The concept of transitions between two different solid phases,
an important aspect of solid state chemistry and solid state
physics, is not so adequately treated. In part, this is due to the
lack of suitable means to readily demonstrate such transi-
tions.
An easy way to demonstrate a solid state phase transition
is with the thermochromic material [(C2H&NH&CuCL. This
is a low melting solid (T,, = 93°C) which undergoes a phase
transition at 50°C.' The salt is easily prepared by fusing to-
gether stoichiometric amounts of anhydrous cupric chloride
and anhydrous diethylamine hydrochloride. Prolonged or
excessive heating should be avoided to prevent formation of
[(CzHs)2NHz]zCu4Cllo0(this can easily be identified by its
red color). The material is hygroscopic, so it must he stored,
accordingly, in areas of high humidity. The phase transition
is easily observed since the room temperature phase is a deep
ereen and the hieh temnerature ohase is a brieht vellow and
can be convenienTly demonstrated by the follo&gprocedure.
Melt a small amount in a Petri dish and, using a wooden splint,
spread the liquid around so that it is smeared thinly on the
surface. Place the Petri dish in an inverted position on the
overhead projector. Cooling can be facilitated by placing an
ice cube on top of the inverted Petri dish for a short period of
time. As the orange melt cools, the yellow high temperature
Dhase will first crvstallize, followed a short time later by the
weeks if left undisturbed). Indeed, with very pure samples,
we have found it possible to supercool the melt down below
the phase transition temperature and simultaneously grow
both ohases from the melt bv seeding with crvstals of each
phase.
' d.
Willen, D., Haugen, J. A,. Lebsack, J., and Morrey. J., Inorg.
Chem., 13, 2510 (1974).
Simonsen, S. H., "American Crystallographic Association Ab-
stracts.'' Vol. 5, No. 1, Abstract HN-5 (1977).
Bloomquist, D. L.. Ph.D. Thesis, Washington Stale University,
1980.
Harlow. R. L., Wells Ill, W. J., Wan. G. W.. and Simonsen, S. H.,
Inorg. Chem., 13, 2106 (1974).
Bloomquist, D. L., Willett, R. D., and Dodgen, H. W., J Amer. Chem.
Soc., 103, 610, (1981)and references therein.
Granville. Ohio 43023
An alternative method of demonstrating the phase transi-
tion may be preferable if audiovisual equipment is routinely
used. From a clear plastic sheet, two pieces of appropriate size
to fit in a 35 mm slide are cut. A small amount of
[(C2H&NHz]zCuC4 is melted between the two sheets. The
edges are then sealed with tape, and placed in the slide holder.
When placed in a conventional slide projector, the heat from
the lamp is sufficient to induce the phase transition.
The demonstration can also be utilized to demonstrate the
interconnection between coordination eeometrv and color in
transition metal salts. The coordination of isolated
CuCli" ions is a delicate balance between crystal field sta-
bilization, favoring a square planar geometry, and ligand-
lieand electrostatic re~ulsions,favorine a tetrahedral peom-
egy. Crystal structure analyses have shown that theireen
ohase contains nearlv ~ l a n a CuCla2-
r anions? while in the
;ellow phase the geom&y is closer t e t r a h e d ~ a lUnfortu-
.~
natelv. the structure of both uhases are c o m ~ l e xand the
s t r u c k e of the high temperatire phase has not been solved
in detail. Similar thermochromic behavior is exhibited by
[ $ C H Z C H ~ N H ~ C H ~ ] &and U C the
~ ~ .structures of both of its
phases have been dete~mined.~ In the low temperature phase,
the C U C ~ anion ~ ~ - is planar (nearly D4h symmetry). The
C U Cion~ in~the~ high temperature phase has approximate
DZdsymmetry with a trans C1-Cu-C1angle of 138". It has been
shown that the driving. force of these thermochromic phase
tran.iti<,ni 1- R thermally ind~nvddynamic dimnler the
s ~ r ~ , ~wm~terio~ia.
~iit. 'I 111, plm~lr w~iiigur.i!ltmia stahili7e(l
h;strone hvdroeen hondine to the counterion, which with-
draws e l l c t r k density fromihe chloride ions and reduces the
electrostatic renulsion. The onset of dvnamic disorder
weakens the hydrogen bonding and so increases the charge
densitv on the chloride ions. This allows the CuCla2- anions
to d i s k towards the tetrahedral configuration.
Getting a "Bang" Out of Chemical Kinetics
SUBMITTED
BY:
George R. Hague, Jr.
Bernards High School
25 Olcon Ave.
Bernardsvilie. NJ 07924
CHECKED
BY:
David Blackman
University of the District of Columbia
Washington. DC 20005
15,000 people.
T o do this demonstration, use a model 15FC Major Field
Cannon or model 155MM cannon on eight rubber wheels.
' Calcium carbide cannons are sold under the trademark of "Big
Bang". They sell for approximately $30 and are available by writing to
the following:Mr. F. Jay Stralo, Vice President and General Manager,
Conestoga Company, Inc., 732 East Goepp St., Bethlehem, PA 18018.
Be sure to request an educational discount.
Volume 60 Number 4 April 1983 355
Set-up the cannon as per the manufacture's instructions. Push
down twice on the charger plunger in order to add the correct
amount of calcium carhide to the water in the cannon.
Reaction
CaCm + HOHm
calcium carbide +water -- CaOi,) + C ~ H ~ I , )
calcium oxide + acetylene gas
Allow a few seconds for the acetylene gas produced to mix with
the air in the cannon. Pull up on the ignitor plunger (flint and
steel) and then give it a quick push down-a loud hang results
as the mixture is sparked!!!!
Reaction
The expanding gases formed in the rear of the cannon force
the remaining gases, mixed with air, out through the muzzle,
creating a partial vacuum. The resulting report or "bang"
results from the "in-rushing"of the air to fill the vacuum that
has been created by the reaction.
Immediately after the first firing of the cannon, add two
more plungers full of the calcium carbide and refire the can-
non. A small yellow flame and some black smoke will result,
but there will he very little noise (much to the surprise of your
students). Most of the oxygen available for combustion was
used in the first firing. The limited supply of oxygen in the
cannon results in incomplete combustion of the acetylene and
only a small "puff" is heard.
For your third firing, blow your breath through the ignitor
opening after the ignitor has been removed. This will replenish
the oxygen supply. Replace the ignitor, reload the cannon, and
fire-a very loud "hang" will result as combustion will again
he complete. For your erand finale, remove the innitor and
add puie oxygen from-a lecture bottle through the ignitor
opening. Replace the ignitor and reload the cannon. Fire in
the usual manner-a uery loud bang will result because of the
greater concentration of oxygen
~ - (100%versus the usual 21%
in air).
This author has found the cannons safe to handle and has
used them for sound effects in science shows and classroom
demonstrations plus as an accompaniment for the "1812
Overture". Additional uses are for athletic events such as
football games and for general all around fun.

356 Journal of Chemical Education