Crystallization

4200:360 Chemical Engineering Laboratory

Mohammad Almusaiteer
Zach Benekos
Jesse Braun
12 February 2016

The crystallization lab was designed to improve crystallization skills utilizing knowledge
of material balance and the nature of saturation while providing opportunity to empirically derive
equations using data harvested from a variety of experiments. Crystallization is an important
technique used to synthesize a highly purified product and is often used in the pharmaceutical
and medical industries. This lab established a comprehension of how to determine the order of
cell growth as well as the coefficient of crystal growth. Additionally, the lab was an attempt to
instill an understanding of what factors will cause cell growth, what factors will provide the
highest yield, as well as the rate of cell growth. The data analysis of these experiments can be
applied to any crystallization process to determine crystal growth order and coefficient, and also
which factors will yield the crystals which best meet the specifications required by a process.
The experiments were carried out using a copper sulfate solution which naturally
crystallizes into copper sulfate pentahydrate (CuSO45H2O). An array of diluted copper sulfate
solutions were created using CuSO45H2O crystals in water. The masses of the solute and solvent
were recorded in each of these solutions in order to calculate the concentrations, and each
solution was measured for its conductivity using a conductivity probe. Another set of diluted
solutions were created to determine the densities using the masses of each one divided by the
volume of a flask of known volume. The volume of the flask was found by weighing it full of
water, whose mass is nearly identical in numerical quantity with its volume, according to its
density of 1 g/mL. The conductivity and density of these solutions of calculated concentration
would be used to derive calibration curves for further experiments. Then, a copper sulfate
solution was created using 79.937 g of CuSO45H2O and about 120 g of water in a flask to
dissolve all of the crystals into solution. The crystallization process began after about 2 hours. A
camera was used to take pictures of the setup every 10 minutes so that a growth rate could be
determined, using the changing lengths of the crystal, so that the crystals environment would not
be disturbed. Small samples were also taken and measured for conductivity in order to determine
concentration of solution. Data was recorded in Table 5. Following this, a solution of 160.246 g
of CuSO45H2O in about 240 g of water was made utilizing a magnetic heating pad once again
and used to create 50 g solution samples that were treated in the following ways: Sample A was
used as a control with nothing being done to it, Sample B was cooled in an ice-water bath,
Sample A also was used as a control with nothing being done to it, Sample C was placed on a
shaker set for 100 rpm for 10 s, Sample D was placed on a shaker set for 500 rpm for 10s,
Sample E was seeded with 0.001 g of silica beads and Sample F was seeded with 0.02 g of silica
beads. Following that, Samples G, H, and I were created with supersaturation values of 0.25, 0.5,
and 1.0, respectively. These samples were left undisturbed for a week and then each solution was
weighed followed by the crystals themselves being patted dry or filtered to remove excess
solution and weighed.
The masses of each copper sulfate solution from the conductivity procedure (Tables 3 and
4) were used to calculate the corresponding concentrations which were then plotted with their
respective conductivities on Excel (Graph 2). A trendline was added that derived the following
equation for calculating the concentration given the conductivity of a copper sulfate solution
(here x is the log of the concentration in mass % and y is the log of the conductivity reading in
S/cm):
y = 1.2721x 6.7172
A calibration curve was also created for the set of dilute solutions created to determine
the relationship of the concentration to the density of a copper sulfate solution (Graph 1). Its

mass was divided by its volume to find the density (Tables 1 and 2) and this curve yielded the
following equation where x corresponds to mass % and y is the density of the copper sulfate
solution:
y = 0.903x 0.9032
In practice, only the conductivity plot was used to find the concentration of the solutions
because the method was faster than that of the density technique and a smaller amount of sample
was needed resulting in less disturbance to the crystal growth system. A key to good crystal
growth is a minimization of disturbance, which resulted in the outlawing of the density
technique.
From the crystal growth which was photographed, a plot was made in Excel that
displayed the length of the crystal in centimeters over time in minutes (Graph 3). A trendline was
added to yield the equation:
y = -3E-05x2 + 0.0112x + 0.1278
Where x is time in minutes and y is the length of the crystal in centimeters. There derivative of
this equation is the growth rate (G) which has an equation of its own:
G=2 K ( y ys)n / m
This equation was graphed in a log-log plot to yield the overall growth coefficient (K) as 20.2
and the order of the crystal growth, n=2.
From Experiment 2, sample B yielded more crystals than Sample A suggesting that
cooling the solution increases nucleation. Sample A had larger crystals suggesting that if the
solution is left to cool naturally, the crystals will grow larger. Sample C yielded more crystals
than A and D which could mean that a small amount of mechanical disturbance can increase
nucleation. The crystals of Sample A were larger than those of C and D, meaning a lower level
of mechanical disturbance could cause an increase in crystal size. Sample E and F have nearly
equal crystal yields so seeding may not have an effect on nucleation, but the crystal size
distribution of Sample E is less spread out than F which means that less seeding can provide a
more reliable crystal size. Sample G has the least amount of crystals of any sample, but the
largest crystals of any sample too. This may mean that a low amount of supersaturation leads to
large crystal size. Sample I had the highest crystal yield with the smallest crystal size, which
means that a high amount of supersaturation leads to low crystal size, but a high yield.
To conclude, the main objective of the experiment was to determine which parameters
will affect the crystal size as well as the crystal growth rate by using experimental data and
calculations. Values of mass transfer coefficient, overall crystal coefficient, and the order of the
overall crystal growth were calculated as well as other parameters to help discover which
parameters will help the most to create the biggest crystal, as well have the fastest growth rate at
room temperature. The cooling rate as well as the mechanical disturbance will have an important
impact on how large the crystals will form. When the cooling rate is slow, it will lead to larger
crystals as well as less nucleation, and that is why the smallest crystals during the experiment in
the petri dishes were the ones that were inserted into the cold bath. In addition, when the
mechanical disturbance is at minimum, the nucleation will be less and the crystals will be large,
and that was tested during the lab, where the 100 RPM per 10 seconds was significantly larger in
terms of large formed crystals than the 500 RPM per 10 seconds. Moreover, the degree of the

super-saturation will affect the quality of crystal. Therefore, large single crystals can be formed
with ease when the degree of super-saturation is at low. Other parameters like concentration and
mole fraction y impact. The larger the concentration or mole fraction y, the faster the growth rate
will be.

References
"Search Chemicals." COPPER SULFATE PENTAHYDRATE. N.p., n.d. Web. 11 Feb. 2016.
W.L. McCabe, J. C. Smith, and P. Harriott Unit Operations of Chemical Engineering 6th Ed.,
McGraw-Hill, New York, 2001.

Appendix I: Spreadsheets

PreLab

Table 1: Concentration vs Density Raw Data

Graph 1: Calibration Curve for Density

Concentration VS Density
0.20
0.15

f(x) = 0.9x - 0.9

R = 1

CuSO4 Concentration (mass fraction) 0.10

0.05
0.00
0.90

1.00

1.10

1.20

Density (g/mL)
Table 2: Calibration Curve
Data Points

Table 3: Concentration vs Conductivity Raw Data

Table 4: Calibration Curve Data

Points

Graph 2: Calibration Curve for Conductivity

Concentration VS Conductivity
0.00
2.000
3.000
4.000
-0.50
-1.00
-1.50
-2.00
LOG[ Concentration (mass fraction) ]
-2.50
f(x) = 1.27x - 6.72
-3.00
R = 1
-3.50
-4.00
-4.50

LOG[Conductivity (S/cm) ]

Table 5: Raw Data Table for Experiment 1

Graph 3: Length vs Time curve to determine Growth Rate (G)

Graph 4: Curve used to determine Overall Growth Coefficient

L VS t

LOG[G] VS LOG[y-ys]

1.200

-1.85

-1.8

-1.75

-1.7

f(x) = - 0x^2 + 0.01x + 0.13

R = 1

1.000

-1

Overall Growth Coefficient and

LOG[G(cm/min)]
Order

L (cm) 0.600

-1.5

0.400

f(x) = 2.38x + 1.88

R = 0.98

0.200
0.000

20

40

60

t (min)

80

0
-1.6
-0.5

Experiment 1: Determining

0.800

-1.65

100

120

140

-2
-2.5
-3

LOG[y-ys]

Experiment 2: Determining Effects of Experimental Parameters on the Formation of

Crystals
Table 6: Raw and Calculated data from experiment 2

Table 7: Supersaturation data for samples (G,H,I)

The Crystal Growth

Distribution (CSD) Results can
be located in Appendix III

Appendix II: Crystal Size Distribution Figures (CSD)

Ambient Control for Cooling Rate

50.00%
40.00%
30.00%
20.00%
10.00%
Xi
0.00%

Ice Water Bath

42.97%

100.00%
28.80%

28.22%

83.53%

80.00%
60.00%

Xi

40.00%
16.47%

20.00%
0.00%

Crystal Length

<2mm

2-3.35mm

Crystal Length

Figure 1: Control sample (A) for effect of cooling rate

crystal size, sample (B)

Figure 2: Effect of cooling rate on

Ambient Control for Mechanical Disturbance

90.00%
80.00%
70.00%
60.00%
50.00%
Xi 40.00%
30.00%
20.00%
10.00%
0.00%

83.92%

6.38%

9.69%

10-15mm

15-20mm

>20mm

Crystal Length

Mechanical Disturbance of 100 RPM for 10 seconds

100.00%
80.00%
60.00%
40.00%
20.00%
Xi
0.00%

93.38%

6.34%

0.28%

Crystal Length

Figure 3: Control sample (A') for effect of mechanical disturbance

mechanical disturbance, sample (C)

Figure 4: Effecting crystal size with

Mechanical Disturbance of 500 RPM for 10 seconds

70.00%
60.00%
50.00%
40.00%
Xi 30.00%
20.00%
10.00%
0.00%

61.11%
38.89%

<2mm

2-3.35mm

Crystal Length

Figure 5: Effecting crystal size with mechanical disturbance, sample (D)

Effect of Seeding with 0.001g Silica Beads

80.00%

67.09%

70.00%
60.00%
50.00%
40.00%
30.00%

Xi 20.00%

17.30%
10.44%
10.00%
2.30%
1.38%
1.20%
0.28%
0.00%

Crystal Length

Effect of Seeding with 0.02g Silica Beads

40.00%

34.01%

35.00%
30.00%
25.00%
20.00%
15.00%

21.75%
15.19%

Xi 10.00%
5.00%
0.00%

15.48%
11.07%

0.53%1.96%

Crystal Length

Figure 6: Seeding effect on CSD for sample (E)

sample (F)

Figure 7: Seeding effect on CSD for

Supersaturation effect at s = 0.25

92.17%

100.00%
80.00%
60.00%

Xi

40.00%
20.00%
0.00%

2.36%

5.43%

5-10mm

10-20mm

20-40mm

Crystal Length

Supersaturation effect at s = 0.50

36.38%
40.00%
35.00%
30.00%
21.09%
25.00%
16.88%
20.00%
11.73%
11.18%
15.00%
10.00% 2.74%
Xi 5.00%
0.00%

Crystal Length

Figure 8: Supersaturation effect from sample (H)

effect from sample (G)

Figure 9: Supersaturation

Supersaturation effect at s = 1.00

100.00%

100.00%

75.00%

Xi

50.00%
25.00%
0.00%

<2mm

Crystal Length

Figure 10: Supersaturation effect from sample (I)