CHAPTER 4

GROWTH OF PURE AND DOPED POTASSIUM HYDROGEN

TARTRATE CRYSTALS IN SILICA GEL

4.1 INTRODUCTION

Since a long period of the history of science growing single crystals has received
interest of scientists and engineers because of their unique properties those make them
highly applicable in many fields like pharmaceuticals and optics for frequency
measurements, piezoelectric effect, a variety of high technology device and sensors
applications. There are varieties of crystals grown having different numerous applications
in science, technology and industry. Crystal growth is an interdisciplinary area, which is a
key to the development of material science, crystallography, and solid-state physics.

Melt and vapour growth reported by Henisch, Joshi et al, Saraf et al, Armington et
al [1,2,3,4,5] is one of the most popular low temperature crystal growth technique and the
grown crystals are strain free. Various types of gels can be used for the synthesis of the
crystals. Gel is the easy and suitable and economic process for growing the single crystals
which are sparingly water soluble and decomposed after melting point reported by Rana
dive et al, Barkley et al [6,7,8]. Though there exist a number of methods, each of them
used for the growth of single crystal from melt and vapour has advantages and
disadvantages. Single crystals can be grown by following methods.

1) Melt growth method [9,10]

2) Solution growth method [11,12 ]
3) Vapour Phase growth method [13]

This chapter explains the crystal growth technique used to grow the crystals of
pure and doped potassium hydrogen tartrate.

44
4.2 CRYSTAL GROWTH

In the present work, the gel growth method [1,18,19] was applied because of its
simplicity and efficiency. The following paragraphs explain the experimental details and
the chemical reactions.

4.2.1 Apparatus used

1) Borosil glass test tube (2.5 cm in diameter and 25 cm in length)

2) Magnetic stirrer
3) Digital pH meter
4) Burettes
5) Pipettes
6) Beakers
7) Specific gravity bottle
8) Digital balance
9) Aluminium Stand for tubes
10) Bottles for different solutions
11) Rubber caps

4.2.2 Chemicals used

1) Sodium Meta silicate (Na2SiO3)

2) Tartaric acid (C4H6O6)
3) Potassium chloride (KCl)
4) Sodium Chloride (NaCl)
5) Lithium Chloride (LiCl)
6) Double distilled water for dilution

4.2.3 Chemical reaction

1) Chemical reaction for growing crystals of Pure Potassium Hydrogen Tartrate:
KCl + C4H6O6 + 2H2O → KH C4H4O6 ∙ H2O + 2HCl

2) Chemical reaction for growing crystals of doped Potassium Hydrogen Tartrate:

45
A) Chemical Reaction for growing Crystals of Lithium doped Potassium Hydrogen
Tartrate:
To grow crystals of Lithium doped potassium hydrogen tartrate, solution of the
Potassium chloride was first added to the aqueous solution of Lithium chloride of a
particular molarity

LiCl + KCL + C4H4O6 + 2H2O K Li H C4H4O6 ∙ H2O + 2HCL

B) Chemical Reaction for growing Crystals of Sodium doped Potassium Hydrogen

Tartrate:

To grow crystals of sodium doped potassium hydrogen tartrate, solution of

Potassium chloride was first added to the aqueous solution of sodium chloride of a
particular molarity

NaCl + KCL + C4H4O6+ 2H2O K Na H C4H4O6 ∙ H2O + 2HCL

4.2.4 Preparation of Sodium Meta silicate solution:

At first, calculated weights of sodium meta silicate were dissolved in double

distilled water to prepare Sodium meta-silicate solution of different densities as shown in
Table 4.1. The density of sodium meta silicate solution was measured by specific gravity
bottle. Sodium meta silicate is diluted in double distilled water diluted to 250 ml. During
preparation of the solution, the mixture was continuously stirred for well mixing with the
help of magnetic stirrer. Then the mixture was filtered by Whattmann filter paper and
filled in airtight coloured bottle to avoid contact from atmosphere. The graph of density
against concentration of sodium meta silicate is as shown in Fig. 4.1.

46
 Table 4.1: Density of Sodium Meta silicate solution

Obs.
Weight in gm Solution Density in gm/cc
No.
1 20 1.038

2 22 1.040

3 24 1.042

4 26 1.044

5 28 1.046

6 30 1.048

7 32 1.05

1.052

1.05

1.048
Solution Density in gm/cc

1.046

1.044

1.042

1.04

1.038

1.036
20 22 24 26 28 30 32 34

Concentration in gm

Fig. 4.1: Density against concentration of sodium meta silicate solution

47
4.3 PREPARATION OF THE GEL
For the preparation of the gel of particular pH, various combinations of density of
sodium meta silicate (1.030 gm/cc – 1.050 gm/cc) and amount and concentration of the
tartaric acid were taken. As shown in Table 4.2

Table 4.2: Preparation of Gel of sodium meta silicate with tartaric acid
Obs. No. Sodium meta silicate solution (1.04 Required Tartaric acid (1M)
gm/cc) volume (ml) volume (ml)
1 16 5
2 17 6
3 18 7
4 19 8
5 20 9
6 21 10

11

10
Tartaric acid volume (1M) ml

5
16 17 18 19 20 21 22

Sodium Meta silicate solution volume (ml)

Fig. 4.2: Sodium meta silicate solution volume (ml) Vs required volume of tartaric acid

48
Silica gel was prepared by adding a solution of sodium meta silicate prepared by above
procedure to L-tartaric acid. Gel of particular pH was prepared by 7ml of tartaric acid
taken in a beaker and 18 ml sodium meta silicate in burettes. Sodium meta silicate was
added drop by drop to the tartaric acid slowly with continuous stirring by magnetic stirrer
till the pH of the solution is 4.2 which is measured by the digital pH meter. Tartaric acid
was used for setting of the gel which acts as a reactant. Both solutions are mixed with
each other slowly drop by drop with continuous stirring to prevent any local ion
concentration which otherwise cause premature local gelling making the final solution
inhomogeneous and turbid.
After preparation of the gel solution, a fixed amount of gel solution with the
desired value of pH was transferred to several test tubes. The test tubes were sealed with
some suitable material like cotton buds or rubber or wooden caps to limit the evaporation
and of the exposed gel surface contamination. The gel setting time strongly depends on
pH and temperature of the surrounding and in turn that of the gel. Time required for the
gel to settle is 24 hours in summer (35-40 oC) whereas it can be long - 14 days in winter
(10-15 oC). Whereas in rainy season (18-20oC) it would take more than 20 days for gel
setting as shown in Table 4.3. Once the gel sets, an aqueous solution of potassium
chloride of a particular molarity was added carefully and gently to the gel along the walls
of a test tube for avoiding any gel breakage.

Table 4.3: Nature of crystal according to environmental condition

Environmental Temperature Gel setting Gel ageing

Nature of crystal
conditions time(days) time

Summer 35-40 oC 1 72 hrs Good

Winter 10-15 oC 14 75 hrs Satisfactory

Rainy Season 18-20 oC More than 20 80-90 hrs Not so satisfactory

49
4.4 EXPERIMENTAL PROCEDURE FOR GROWTH OF PURE
POTASSIUM HYDROGEN TARTRATE CRYSTALS
The crystallization apparatus for the growth of pure potassium hydrogen tartrate
consists of borosilicate glass tubes of length 20 cm and diameter 2.5 cm placed vertically
on aluminium stand. For the growth of pure crystal gel encapsulation technique was
employed [14,1516,17]. Silica gel was prepared by adding a solution of sodium meta
silicate which was prepared by above procedure to L-tartaric acid. Both solutions were
mixed with each other slowly with continuous stirring to avoid any local ion
concentration which would otherwise cause premature local gelling and make the final
solution inhomogeneous. To prevent fast evaporation and contamination of gel, test tubes
were sealed with cotton or rubber caps. The tubes were kept in stand for gel setting
depending on pH of solution and environmental conditions. In summer the gel setting
time is comparatively shorter than that in winter. The rainy season is not so good for
formation and growth of crystals while summer and month of October is the best season
for formation and growth of crystals.
After confirmation of gel setting, an aqueous solution of potassium chloride of
particular molarity was poured over the gel surface along the walls of the test tube gently
and carefully so that gel does not break. The ions of K1+ diffuse through the pours of the
gel and react with HC4H4O6 in gel. The following action takes place leading to the
formation of pure potassium hydrogen tartrate crystal.

KCL + C4H6O 6 + 2H2O → KHC4H4O6 + 2HCl

4.5 EFFECT OF VARIOUS PARAMETERS ON THE GROWTH

RATE OF CRYSTAL
During crystal growth, the growth parameters give some interesting information.
The Growth parameters such as gel density, concentration of reactants, pH of gel,
concentration of supernatant, effect of gel setting time, effect of gel aging time have
considerably effect on the rate of growth of crystal.

50
 The optimum conditions for growing crystals of Pure Potassium hydrogen
Chloride were found which are given in Table 4.4. The grown crystals in gel are shown in
Fig. 4.3.

Table 4.4 Optimum conditions for growth of potassium hydrogen chloride

Optimum Condition Crystal growth of potassium
hydrogen chloride
Density of Sodium meta silicate solution 1.04gm/cc
Concentration of Tartaric acid 0.5M
Volume of sodium meta silicate 18ml
Volume of Tartaric acid 7ml
pH of Gel 4
Concentration of KCl 1M
Time required to appear silver white coloured 24 hrs
crystal on the surface of gel
Gel setting time 24hrs
Gel aging time 75hrs
Crystal growth time 6 weeks
Temperature 35-40 oC

Different parameters mentioned in above table have considerable effect on the growth
rate.
Thus, series of experiments are performed and the optimum conditions were
obtained for growing good quality, large size crystals at 1M concentrations of tartaric
acid as shown in Table 4.4.showing the effect of different concentrations of reactants on
quality, transparency, size and development of the crystals.

51
a) Pure Potassium Hydrogen Tartrate b) Sodium Doped Potassium Hydrogen Tartrate
Crystals Tartrate Crystals

c) Lithium Doped Potassium Hydrogen Tartrate Crystals

Fig. 4.3: Crystals of pure and doped Potassium hydrogen tartrate grown in silica gel by
Tube encapsulation

4.5.1 Effect of Gel density

Gel is prepared by mixing sodium meta silicate with tartaric acid slowly drop by
drop till the pH of solution becomes 4. It was observed that transparency of the gel
decreases as the gel density increases which set more rapidly. Gel with higher densities

52
set more rapidly than the gels with lower densities. Gel having lower densities results in
smaller pore size decreases nucleation density. Table 4.5 shows variations of the gel
density against nucleation density. These variations are shown with graph in Fig. 4.4.
The various shapes of crystals of pure and doped Potassium hydrogen tartrate are shown
in Fig. 4.4, 4.5, 4.5(a) and 4.6.

Table 4.5 Variations of the gel density against nucleation density

Test
Density of No. of nuclei
tube Observation
gel (gm/cc) formed
No.
Formation of very small size, tiny crystals less
1 1.036 50
in number, not isolated from each other.
Formation of small size crystals, less in number
2 1.038 45
which are not well isolated.
Formation of well-defined large size
satisfactory transparent silver white colour
3 1.040 40
crystals sufficient in no. and isolated from each
other.

1.042 36 Large size, semi-transparent crystals.

4

1.044 30 Few small size crystals.

5

53
 55

50

No. of nuclei formed

45

40

35

30

25
1.035 1.036 1.037 1.038 1.039 1.04 1.041 1.042 1.043 1.044 1.045
Density of gel (gm/cc)

Fig. 4.4 Variations of the gel density against nucleation density

(a) Normal shaped b) Elongated shaped

Fig. 4.5: Normal and elongated shaped Crystals of Pure Potassium Hydrogen Tartrate

54
 (a) Normal shaped b) Elongated shaped
Fig. 4.5(a): Normal and elongated shaped Crystals of Sodium doped Potassium Hydrogen
Tartrate

(a) Normal shaped b) Elongated shaped

Fig. 4.6: Normal and elongated shaped Crystals of Lithium doped Potassium Hydrogen
Tartrate
4.5.2 Effect of pH of gel
Transparency of the gel decreases as the pH of the gel increases. The effect of pH
of gel was studied by taking different combinations of sodium Meta silicate and tartaric
acid. In the present work pure crystals of potassium hydrogen tartrate were obtained at
pH 4. As the relative quantity of sodium meta silicate increases in the mixture pH of the
gel increases which decreases transparency of the gel. Inferior crystals were observed at
higher gel pH values due to improper formation of the cells. At higher pH values the
crystals are not well defined due to combination of the crystals with silica gel. The
number of crystals decreases as the gel pH increases. The growth of pure potassium
hydrogen tartrate crystals at pH 4 is reported in Table 4.6. The graph of variation of pH
with Gel setting time is shown in Fig. 4.7.

55
 Table 4.6: Effect of pH Gel

Test Sodium Gel

Tartaric
tube meta pH of setting
acid (1M) Observation
No. silicate mixture time
ml
ml Hrs
Gel does not set
1 11 11 2 -

Gel does not set

2 10.5 11.5 2.2 -

Gel does not set

3 10 12 2.6 -

Gel does not set

4 9.5 13 2.8 -

Milky and unstable gel

5 9 14 3 140

Very small and few crystals on

6 8.5 15 3.2 120
interface are observed
Small and some remarkable
7 8 16 3.4 96 crystals are observed away from
gel interface
Small and some remarkable
8 7.5 17 3.8 84
crystals are observed
Large in size, large in number
9 7 18 4 75 whitish colour transparent
crystals are observed
Large, few whitish colour
10 6.5 20 4.1 60
transparent crystals are observed
small, whitish colour transparent
11 6 21 4.2 48 crystals few in number are
observed
Crystals are not well defined,
12 5 22 4.3 36
isolated and less in number

Crystals are not well defined,

13 4.5 23 4.4 24
isolated and less in number
Crystals are not well defined,
14 4 24 4.5 12
isolated and less in number

56
 160

140

Gel setting time (Hr) 120

100

80

60

40

20

0
2 2.5 3 3.5 4 4.5
pH of mixture

Fig. 4.7: Graph of pH of mixture Vs Gel setting time

Table 4.6 (a) Optimum conditions for crystal growth

Optimum Condition Crystal growth of potassium
hydrogen chloride
Density of Sodium meta silicate solution 1.04gm/cc
Concentration of Tartaric acid 0.5M
Volume of sodium meta silicate 18ml
Volume of Tartaric acid 7ml
pH of Gel 4
Concentration of KCl 1M
Time required to appears silver white coloured 24 hrs
crystal on the surface of gel
Gel setting time 24hrs
Gel aging time 72hrs
Crystal growth time 6 weeks
Temperature 35-40 oC

57
4.5.3 Effect of concentration of reactants
It is a substance that takes part in chemical reaction and undergoes changes during a
reaction . while writing chemical reaction it is always at the left side while products are
on the right side.

As the concentration of the tartaric acid is increased more volume of sodium meta
silicate was required to adjust the pH of the solution to the value 4. As the concentration
of tartaric acid is increased more and more tartrate ions combine with potassium ions.
Thus, as the concentration of the tartaric acid is increases, nucleation density increases.
Nucleation density can be reduced by increasing the aging time. Thus, crystals can be
grown with higher concentration of tartaric acid which creates problems in growth rate.
Fast growth rate at high concentration of tartaric acid results in dendritic growth. The
variation of reactant with number of nuclei is shown in Table 4.7 and graph is shown in
Fig. 4.8.
Table 4.7: Concentration of reactant above gel Vs. No. of Nuclei observed
Test Concentrati No. of Nuclei Nature of crystals formed
tube on of observed
numbe reactant
r above gel
1 0.2 2 Few crystals of small size and not well
develop and defined
2 0.4 6 Few crystals of increased size and well
develop
3 0.6 10 Sufficient number of isolated crystals of
increased size and well develop, various
shaped
4 0.8 15 Large number of isolated transparent
crystals of good size and well develop
5 1.0 20 Large number of isolated transparent
crystals of large size and well develop
6 1.2 25 Large Number of crystals which are not
isolated

58
 30

25

No. of Nuclei observed

20

15

10

0
0 0.2 0.4 0.6 0.8 1 1.2 1.4

Concentration of reactant above gel

Fig. 4.8: Concentration of reactant above gel Vs. No. of Nuclei observed

4.5.4 Effect of concentration of Supernatants-

Supernatant is a clear liquid lying above a solid residue after crystallization,

Precipitation, centrifugation or other process.

Potassium chloride is used as Supernatants. Solution of Potassium chloride with different

concentration from 0.2 M to 1.2 M is added over the set gel as shown in Table 4.8. Effect
of this is shown graphically in fig 4.9.

59
 Table 4.8 Effect of concentration of Supernatants on number of crystals:

Tartaric Sodium Conc.

No.
Test acid meta of the Observations
of
tube (1M) silicate supernatant
nuclei
No. ml (ml) M
Very few nuclei are
1 7 18 0.2 2 observed. Small size crystals
which are not well defined.
Nucleation density increases.
Small size crystals are
2 7 18 0.4 6
observed which are not well
defined.
Isolated shining crystals of
3 7 18 0.6 10 various size and different
shape are observed.
Well-developed number of
4 7 18 0.8 15 crystals of different size and
shape are observed.
Good well developed whitish
silver dull colour isolated
5 7 18 1.0 20
crystals without any
transparency are observed.
No. of crystals increased
6 7 18 1.2 25
which are not isolated
No. of crystals increased
7 7 18 1.4 30
which are not isolated.

60
 35

30

No. of Nuclei observed

25

20

15

10

0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6

Conc. of the supernatant, M

Fig. 4.9: Effect of concentration of Supernatants on number of nuclei crystals

4.5.5 Effect of aging of Gel

After the formation of gels, gels were allowed for hardening called as gel aging
time for different period before adding the feed solutions. It was observed that as aging
time of gel increased, the number of crystals decreased. This is because gel aging reduces
the cell size and consequently the rate of diffusion of ions into gel [18,19]. Table 4.9
shows effect of gel aging time on number of crystals obtained. The dependence of gel
aging time on number of crystals developed is shown graphically in fig 4.10.

61
 Table 4.9 Effect of gel aging time on number of crystals obtained

Numbe
Test Sodium Gel
Tartaric r of
tube meta Aging
acid crystals Observation
No. silicate time
(1M) ml obtaine
ml (hrs)
d
Immediate nucleation, whisker
1 7 18 24 80
growth is observed at the interface
Nucleation observed bellow the
2 7 18 48 48
interface in controlled manner.
Induction period increases up to 8
3 7 18 72 25 hours, crystals were observed
bellow the interface
Well-developed crystals, Crystals
are developed near the interface as
4 7 18 96 12 well as inside the gel with different
morphology. Crystals are
transparent, whitish observed.
Nucleation density decreases
improved the crystal quality which
5 7 18 108 5
are well developed are larger in
size.
After long time there was no
6 7 18 120 -
nucleation observed.

Crystals of sodium doped potassium hydrogen tartrate were grown by mixing of

potassium chloride solution with aqueous solution of sodium chloride of particular
molarity. Diffusion of Na1+ , K1+ and HC4H4O6 - ions leads to the formation of sodium
doped potassium hydrogen tartrate crystals.
Similarly, Crystals of lithium doped potassium hydrogen tartrate were grown by
mixing of potassium chloride solution with aqueous solution of Lithium chloride of
particular molarity. Diffusion of Li1+, K1+ and HC4H4O6 - ions leads to the formation of

62
Lithium doped potassium hydrogen tartrate crystals. Thus in both cases gel aging time
varies inversely with Number of crystals formed.

90

80

70
No. of Crystals Obtained

60

50

40

30

20

10

0
0 20 40 60 80 100 120 140

Gel Aging time (Hr)

Fig. 4.10: Effect of gel aging time on number of crystals obtained

Conclusion:-

Durring crystal growth , growth parameters give some interesting information. The
growth parameters such as gel density , concentration of reactant, pH of gel,
concentration of supernant, effect of gel setting time, effect of gel aging time have
considerably effect on the rate of growth of crystal.

Gel density, pH , gel aging time directly varies with number of nuclei, gel setting time
and number of crystals formed respectively. While concentration of supernants and
reactant varies inversely with number of nuclei formed.

63
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