Crystal Growth in Gels
Steven L. Suib
University of Connecticut, Storrs. CT 06268
The ability to prepare large single crystals of inorganic and
organic compounds is important in several fields in science
and in many industrial and technological products. With large
single crystals a scientist is capable of accurately describing
bond distances and coordination environments through the
aid of X-ray diffraction and neutron diffraction methods.
There are several uses of crystals with special physical prop-
erties. such as the oiezoelectric nature of quartz and the
semicbnductiug properties of materials like silicon, germa-
nium, and gallium arsenide.
Several methods are used to grow large single crystals of
inorganic and organic compounds. Growing crystals from
aqueous solutions can he a hobby for children and is often one
of the first experiences in science that young people encounter.
An enormous numher of high school and undergraduate
general chemistry experiments have been developed for the
growth of large crystals and there are many hooks discussing
this matter (1-3). Most of the simple procedures in crystal
growth deal with aqueous solutions and crystallization that
is either induced by cooling or by evaporation. Other solution
mowth methods include flux erowth ( 4 ) . electrolvtic methods
75), hydrothermal synthesis c6) of m&rials likezeolites and
eel "
"~ erowth (7).
More elal;oiate techniques such as the Czochralski method
use nulline rods and melts for materials like calcium turnstate
( 8 ) . ' ~ h egridgeman-~tockhar~er furnace is a special appa-
ratus for controlled melt erowth of cadmium fluoride crvstals
(9). Finally, several methods for crystal growth include the use
of the vapor phase such as vapor phase transport methods
used in the production of metal dichalcogenide crystals (10)
and sublimation techniaues.
One ot'the simplrst, and yet relatively unknnwn, methods
of crvstnl erowth in\.olves the EPI technique (7). Several ex-
peri&tli~involving crystal growth in gels are presented below.
These areeasy to perform and require very littlr equipment.
However, the romplrte understanding of the experiments is
not straightforwnrd since it rrquires the knowledge of a
numher of rather complex prope&es of gels, crystals, and the
structures of these materials. Nevertheless, the simple ex-
periments can he used to explain rather suhtle phenomena
such as syneresis and nucleation (7). Once these are under-
=
stood qualitatively, other phenomena surh Liesegang ring
formation ( 1 1 ) and Ostwald ripening (12) can hestudied much
more intelligently.
The experiments are performed with an aqueous silicate
gel, hut the phenomena observed are characteristic for many
other types of gels such as agar or, for that matter, a common
. . substance. .iellv.
evervdav . Cwstal
. growth in gels attained
importanrr many years ago; for example, Pb12 crystals were
erown in fruit iells a r k in the late 1800's (1.1).More recently
ihe gel growth te&ique has heen used for the preparation
of several semiconducting materials such as CsSn21S and
RbSnBrs (14). These latter materials could he prepared by
solution and melt growth techniques, hut the size of the
crsstal?i was much sialler. For instance, CsSnllS crystals as
large as 1 mm on an edgr ran he grown by the gel technique,
hu<onlv fme nowders result fromsolution mowth orocedures.
The gei technique has been recently u s 2 to prepare large
derivatives of hydroquinone crystals in a nonaqueous gel (15).
The crystals are of excellent quality and as large as 2 mm on
edge; such large crystals are not ohtained by most other
methods.
These experiments described below have been developed
as a part of an undergraduate curriculum for a laboratory
course in chemistry. The students are typically juniors or se-
niors and have already or are concurrently studying physical
chemistry. The students are expected to do two of the four
experiments described below and to make as many ohserva-
tions as oossihle for 14 weeks concernine the size. color. habit.
and changes that occur from gel formacon throigh cristalli:
zation. The students are encouraged to think of all the vari-
ables that could he important in these experiments and to
change some of the variahles and reoort their results. More
detal'is on some of the common variables are given in the ex-
perimental section.
Crystal Growth in Gels
A gel can he defined as a two-component system that is
semi-solid and is particularly rich in liquid. Several materials
exist that are called gels, such as silica materials, oleates,
gelatin, polyvinyl alcohol, and agar. Each of these types of gel
has been used in various ways for crystal growth, hut the sil-
ica-tvne materials derived from water class or sodium me-
tasilriate have been the most widely us&.
Gels that are used for crvstal erowth are usuallv. hvdrogels.
. .
That is, water is used to dfsper; different media such as so-
dium silicate or sodium metasilicate. Once the gel sets, a
three-dimensional cross-linked polymeric network results. It
has been estimatrd that even thouch these gels look likesolids
and indeed have certain properties similario solids that they
are 90% to 97% water.
When a silicate solution is acidified the silicate ion reacts
to form mnnnsiliric arid, which can react with iwelf to produce
water and Si-O-Sihonds. These siloxano bnnds are important
linkaaes in silicate gels. Siloxane hond formation nmtinues
untilaeveral siloxane bonds stick together via cross-linked
chains. The side product, water, evaporates, and the gel
shrinks before it hardens. This process is known as syneresis.
The resultant structure of the gel includes open channels and
pockets. Such channels are very important for the formation
of crystals in the gel.
Usually one ion or reactant is dissolved in the gel hefore the
gel is allowed to set. The gel is allowed to set in a test tube or
beaker and a solution of the other ion or reactant is added to
the top of the gel. Then, the ion in solution slowly diffuses
through the pockets in the gel allowing the reaction to take
place gradually and in certain cases producing large well-
formed crvstals.
noth he; phenomenon is noticed when the two ions that
interact on diffusion throuzh the gel form an insoluble pre-
cipitate. Instead of the formationif a uniform mass of pre-
cipitate or of interdispersed crystals a ring or rings of pre-
cipitate are formed with interspersed layers of gel. These rings,
known as Liesegang rings, have been studied for quite some
time (13). There are natural formations such as rings in
minerals like agates that are believed to he the result of
Liesegang ring formation.
There are several variahles that are important in the
preparation of crystals in gels. The main variables are the pH
before gel formation, the concentration of reartants, the choice
of
.- where
~ to~~~ disnerse
~~. -the~
~ reactants. the temoerature during the
nucleation andcrystallization process, the method for bringing
all of the reactants together before gel formation, and finally
Volume 62 Number 1 January 1985 81
 the type of tube to use during the experiment. Other variables,
such as the incorooration of electrodes into the nel - to induce
crystallization, a;e also possible.
I n the eel formation process pH is quite important. If the
p H is tollow, a gel ma; never form. if it is too high, the gel
may form instantaneously. Usually a setting time of 8 to 12
h r is desirable to form a gel that will yield large single crystals.
During formation of the gel pH can be monitored with a p H
meter. I n experimenting with different types of gels, such as
sodium metasilicate and agar, this is especially advisable.
The concentrations of the reagents to be used will depend
on the particular system being studied. The choice of dis-
peming one or another reagent in the gel is u s u d y determined
after experimentation. I t is usually hest to add one rewent to
the unset gel solution and then toadd the gel solutionto the
acid. Adding acid to the gel solution often results in instan-
tnneous gel formation which is nor desirable. The temperature
during pel formation is usually nx)m temperature, but during
rrvstallization la1'u.r the addition o i a reaeent t the ton of the
set gel) the temperature can he a n impGtant factor (16).
The type of tuhe is usually a test tube or a U-tube. The U-
tuhe experiment is used to produce very large single crystals.
The fourth experiment listed below deals with the use of a
U-tube. The usual procedure is to acidify the gel and allow it
to set in the U-tube. Then the two reagents are added to OD-
posite sides of the U-tube and allowedto diffuse together
form crystals.
If the original reactant concentrations in the U-tube ex-
periment are fairlv low, and, if the solutions are periodically
;eplaced with successively higher concentration of reactants,
then exceedingly large crystals can he formed. This method
is known as concentration programming (7) and relies on the
phenomenon of Ostwald ripening. Originally only a few
crvstals are formed. After the solutions are chaneed and the
concentrations are higher the original crystals will become
larger rather than new crystals being formed. Reseeding
methods which employ the use of seed crystals in gels can
sometimes he emnloved t o svnthesize ahnormallv larne crvs-
tals. For the most iuthoriiative account of thk gr&th"of
crystals in gels, refer to the excellent book by Henisch (7).
Scientists often visit our teaching laboratory and marvel
a t the crystals growing in the gels. A question most often asked
concerns how to isolate the crystals from the gel.' Usually the
procedure involves a phvsical separation with spatulas.
However, the gel is water Soluble, a i d if the c r y s t a ~ ~ anot
re
soluble in aqueous solution this is also a viable alternative.
Other solvents like dilute acids can sometimes he used.
Experimental Sectlon
Each student should do two of the following experiments. The
preparations should be labelled and allowed to stand in the laboratory
for observation during the semester.
Two test tuhes. -15 X 200 mm will he used to hold the eel. Preoare
30 ml of sodium ki~icatesolut~onof density 1.Ofi glml b;dilutrA of
the rommercial wlution. ' l ' h ~amount of commercial silirat~a,lution
to make :l0.0 rnl of density 1.116 may be calculated irom the firlhrwing
relationship:
where D is the densitv of commercial solution
We ohtain our sdium silicate solution, which has a density of 1.37
glml. frmn Fisher Scientific Company. Kxartly 13 ml of the silicate
solution is used in each experiment.
Students vary at least one of the several variables that influence
crystal growth in each experiment. Control experiments are also
The author thanks a reviewer for questioning this matter.
82 Journal of Chemical Education
carried our. Variahler that are must rasilychanged are the tempera-
ture, wncentrnrrm of reartanb, type of rube, whether the acid is
added r u the gel or vice versa, and how the reactants are dissolved in
the gel or in the layer above the set gel.
The time for the gel to harden is usually 8 hr. Students prepare the
gel one week, allow the gel to set, and the next week add the solutions
to the top of the gel far crystal growth.
Experiment 1: Lead Iodide Crystals
Add 1ml of 1 M lead acetate solution to 15ml ofthe sodium silicate
solution. This solution is then mixed with 15 ml of 1 M acetic acid.
Pour the mixture into one of the prepared test tuhes (to about 213 full)
and allow to set. When the gel is firm, add a solution of 1.0 g KI in 5
ml HzOand cork. At first a solid layer of lead iodide is formed at the
surface, hut soon frond-like crystals grow down into the gel, and, at
a still lower level, single hexagonal crystals of the salt gradually appear
and mow to the size of several millimeters in the course of a few week.
On Golonged exposure to light the crystals darken somewhat.
Experiment 2: Copper Crystals
Mix 15ml of the diluted sodium silicate solution..15 rnl~of 1 M. nretir~
~~~~~~~~-~ ~~~~ ~ ~
arid, and 0.2 g CUSOISH~O.F~llme 111the prepared test tubesZ3full
and allow to sot. 'Then, add n solutron of 1%hydruxylaminr hydro-
chloride. In the course of a few weeks fine tetrahedral crystals of
copper appear.
Experiment 3: Banded HgI2
Mix 15 ml of the diluted sodium silicate solution and 15 ml of 1 M
acetic acid containing KI. (Usebetween 0.2 g and 2 g KI; record the
amount on the label.) Fill one of the test tuhes 213 full of this solution,
and. when set. add asolution of HeCI"- (1.0
. e.. in 15 ml of water).. In a
feudays brighi rrrl I.iewgang rinm of Hg12will have formed;the form
~
and color i,i the hands depends greatly un the concentration uf KI.
Experiment 4: Calcite Crystals
Mix 15ml ofthe diluted sodium silicate solution, 15ml of 1M acetic
sad. Fill a U-tube with the gel-acid mixture and allow to set. Then add
an aqueous solution of CaCh to one side of the U-tube and an aqueous
solution of NaaC03 to the other side. The reagents will diffuse from
both sides and form calcite where they meet.
Concluslon
The variahilitv of these simple experiments allows the
student to make;ndividual choices on'how ro grow the crys-
tals. The principles ran he easilv extended to other simple
inorganic >omp&nds. Several characterization methods can
he applied to the Pb(CH&00)2, HgIz, Cu, and CaC03 crys-
tals. One of the simplest is X-ray powder diffraction. The
copper crystals can be tested with a volt-ohm meter for con-
duction. All of these crystals show excellent faces and habits,
and they can easily he ohserved under a microscope without
taking the crystals out of the gel.
Literature Cited
- (1) Holdeo.A.and Singer, P.."Crystala and Cmtal Ge&ng," Anchor kEn,Doubkday
aod CO.,New YO&. 1960.
(2) Wmd, E. A. "Crystals a Handbook for Schml Teachers."Polycrrntsl Book Service.
Pittsbwh, 1972.
(a) oitman. ht ~sdenceo f ~ r - n g clyatals: J O wdey
J. J., ( ~ d i t ~ ~ ) ;~' ~land ~ and
Sons, Ine.. 1963,Chaps. 8 and 11.
(O l h o f e w s , V A., Belysev, L.M..Umulyak,N. O.,BeltaLii, A. V., Bykw, A.B.,Mepo,
V. M., J ClyalalGmmfh,52,633 (1981).
(51 Deoree. M. T.. Vaidvsn. V. K.. K ~ r r lTach..
. . IS..653 119801.
. .
(4 R O ~ S ; ~ R.
; , them ?&, 8,176 (1978).
(1) Henisch, H. K., 'CwstalGroanh in Gels,"ThePennsylvania StateUniveraity Press,
University Park, PA, 1973.
(8) Nassau,K., and Brayer, A. M., J. Appl. Phys., 33,3064 (1962).
(9) Jane, D. A., and Jones, R V., Roc. Phys Soe., 79,351 (1962).
(10) Thompson, A. H., Gamble, F. R.,and Symon,C. R., Mat. Re& Bull., 10,915 (1975).
(11) Stem,K.H., "Bibliography dLiesegang Rings,"National Bureauof Standards,Mix.