1

Determining the rate constant of sucrose hydrolysis using polarimetry

Austin Cao, CHEM 368

INTRODUCTION

When light is polarized, a material selects for light oscillate in a particular plane and
blocks all other light from passing through. Plane-polarized light can then be rotated after
passing through other materials, a property called optical activity. Only chiral molecules can be
optically active, and they are referred to as either dextrorotary (rotate plane of light clockwise) or
levorotary (rotate plane of light counterclockwise). For example, cholesterol is levorotary, while
sucrose is dextrorotary. Optical activity has uses in a wide-range of applications, including
determining the concentration of substances, studying organic and inorganic substances, and
developing optical communications systems.[1]

In the sucrose hydrolysis reaction, measuring the total optical activity can be used to
monitor the concentration of each species in the reaction. In the first reaction conducted, HCl is
in excess and the reaction can be approximated using a first order model. In the second part, HCl
and sucrose are set at the same concentration to challenge this assumption. A second order model
will be then used to fit this data. The objectives of this experiment are to develop an
understanding of polarimetry and derive pseudo-first order and second order rate equations for
the sucrose hydrolysis reaction.

METHODOLOGY

The experiment was generally carried out according to the protocol titled “Determination
of Rate Constant of Acid Catalyzed Sucrose Hydrolysis” provided in the CHEM 368 Laboratory
Manual, with some modifications.[2] A polarimeter measurement was taken using distilled water
to calibrate the instrument. Since distilled water is not optically active, this value is used to
correct the α values recorded during the experiment. The first reaction was initiated by mixing 10
mL of sucrose (200 g/L) with 10 mL HCL (6 M). The reaction mixture was placed in the
polarimeter, and readings were taken over the course of 30 minutes. The second reaction was
 2

initiated by mixing 20 mL sucrose (400 g/L) with 3.8 mL HCL (6 M) and readings were
similarly taken. Polarimeter angles were recorded in a lab notebook.

DATA

To read the polarimeter, the mark on the right scale that matched up to the 0 mark on the
left scale indicated the unit integer. Then, the mark on the left scale that perfectly lined up with
any mark on right scale indicated the decimal values. The data was manually imported into
Microsoft Excel from the lab notebook. A calibration value of 𝛼 = -0.1 from distilled water
measurement was used to correct the α values shown in Table 1.

Table 1. Optical rotation over time recorded by polarimeter. Time started when solution was
mixed. Calibration using distilled water gave 𝛼 = -0.1. All data shown accounts for this
correction.

time (min) 𝛼1 (°) 𝛼2 (°)

3 8.9 42.6
4 7.6 41.65
5 6.25 40.6
6 5.6 40.2
7 4.7 39.55
8 3.5 38.45
9 3.1 37.9
10 2.25 37.1
12 1 35.7
14 0.25 35.1
16 -0.7 32.7
18 -1.35 31.45
20 -1.85 29.8
22 -2.4 28.5
24 -2.6 27.3
26 -2.95 25.65
28 -3.3 24.5
30 -3.5 23.4
 3

RESULTS & CALCULATIONS

The first reaction was conducted with a HCl in excess (at a concentration of 3 M), so the
assumption of a first order reaction was made for simplicity, where c is equal to the
concentration of sucrose:

𝑑𝑐
= −𝑘𝑎𝑝𝑝 𝑐, 𝑐 = 𝑐0 𝑒 −𝑘𝑡
𝑑𝑡

Equation 10 from the lab manual gives a relationship between c and α, and it can be
substituted into the equation above to write a linear equation, with the new variable Z1 set equal
to the y-term:[2]

∝ −∝∞
𝑍1 = 𝑙𝑛 ( ) = −𝑘𝑎𝑝𝑝 𝑡
∝0 −∝∞

To calculate values of Z1 for the first data set, α0 and α∞ must be determined. From the lab
manual, we know that:
∝0 = [∝𝑠 ]20
𝐷 ∗ 𝑏 ∗ 𝑐0

∝∞ = ([∝𝑔 ]20 20
𝐷 + [∝𝑓 ]𝐷 ) ∗ 𝑏 ∗ 𝑐0

Where b is path length (2 dm), c0 is the initial concentration of sucrose, and [α] is the
specific rotation constant for each species in the reaction, given in the lab manual. α0 and α∞ are
calculated for both data sets in Table 2 below.

Table 2. Calculating α0 and α∞ for both solutions.

Solution 1 Solution 2

c0 0.1 g/cm2 0.3361 g/cm2

α0 13.3° 44.70588°

α∞ -7.94° -26.6891°
 4

Now, Z1 can be calculated for the first data set. Time and Z1 are plotted against one
another, as directed by the linear relationship derived earlier.

PLOT OF TIME VS. Z 1 FOR SOLUTION

1
0
-0.2
-0.4
-0.6
-0.8 y = -0.0499x - 0.1896
Z1

-1 R² = 0.9772
-1.2
-1.4
-1.6
-1.8
0 5 10 15 20 25 30
time (minutes)

Figure 1. Calculating kapp for reaction of sucrose solution 1 with HCL. Z1 is defined in the
calculations section. Rate constant is equal to the negative slope of the linear regression line.

The regression line was generated using the trendline and LINEST functons in Excel.
Although the data set appears to be slightly non-linear, the R2 value of 0.9772 indicates a strong
fit for the regression line and relatively high precision in the measurements taken. The plot
reveals an apparent rate constant kapp = 4.99e-2 ± 1.91e-3 min-1*mol-1, or when converted to
seconds-1, 8.32e-4 ± 3.18e-5 s-1*mol-1.

The first order assumption was only made because HCl was in excess in the first reaction.
In the second reaction, the concentration of HCl and sucrose were made to equal, increasing the
significance of HCl concentration on the rate of the reaction.
 5

𝑑𝑐
= −𝑘𝑐 2
𝑑𝑡

This rate equation is derived by noting that the concentration of sucrose and H+ were
equal in the second experiment (and have a stoichiometric ratio of 1:1). The equation is then
integrated:

1 1
= 𝑘𝑡 +
𝑐 𝑐0

Equation 10 from the lab manual can be used to find an equation for c in terms of α. The
previous equation then becomes:

∝0 −∝∞ 1
𝑍2 = = 𝑘𝑡 +
𝑐0 (∝ −∝∞ ) 𝑐0

For simplicity, a new variable Z2 is set equal to the y-term in the linear equation. By
plotting t vs. Z2, the actual rate constant k can then be calculated.

PLOT OF T VS. Z 2 FOR SOLUTION 2

1.5
1.45
1.4 y = 0.0148x + 0.9948
1.35 R² = 0.9943
1.3
Z2

1.25
1.2
1.15
1.1
1.05
1
0 5 10 15 20 25 30
time (min)

Figure 2. Calculating k for reaction of sucrose solution 2 with HCL. Z2 is defined above.
Rate constant is equal to the negative slope of the linear regression line.
 6

The regression was once again generated using the trendline function and LINEST,
giving a strong R2 = 0.9943, indicating high precision in the measurements taken as well.
Interpreting the slope of the regression line in Figure 3 indicates a rate constant k = 1.48e-2 ±
2.8e-4 min-1*mol-1 = 2.47e-4 ± 4.67e-6 s-1*mol-1.

DISCUSSION

The relationship between the rate constants calculated, kapp and k, can be determined by
comparing the rate equations listed above. In the first reaction, HCl was held in excess, and
therefore did not contribute significantly to the rate equation. In the second reaction, this
assumed is challenged with a substantially lower HCl concentration. By accounting for the
concentration of H+, it is apparent that:

𝑘𝑎𝑝𝑝 = 𝑘[𝐻 + ]

For the first set of data, a H+ concentration of 3 M was used, indicating that the apparent
rate constant should be three times the value of the actual rate constant. Sure enough, the
calculated rate constants have a ratio of 3.37, with a percent difference of 12.4% when
comparing the experimental and calculated actual rate constants. It is clear that when HCl is no
longer in excess, an assumption of first-order can no longer made. To investigate this point, the
pseudo first-order model was used to calculate the apparent rate constant of the second-order of
data, resulting in kapp = 0.012 min-1*mol-1 (Appendix 1). This value is also approximately three
times smaller than kapp for the first-order data, which is expected given the substantially lower
concentration of HCl in the second-order data. The value is also slightly smaller than the actual k
constant calculated for the same set of data, which is expected given the HCl concentration of
0.98 M in the second reaction. All in all, the second-order equation gives a more accurate
estimate for the actual rate constant than the first-order equation.

A few potential sources of error contributed to the variance in the final calculations. One
difficulty with operating a polarimeter is the nature of reading the measurement. The researcher
must carefully adjust the lens so that the colors match, which is an extremely subjective task.
This relies on the user to discern between a gradient of colors and ignores the fact that people
have varying abilities in discriminating between colors. The task also relies on the user to
 7

carefully adjust the dial, which is subject to the user’s fine motor skills. Since the experiment
was only conducted with one replicate, there is no way to eliminate these sources of variability.
Future experiments should conduct multiple replicates with different users and determine
standard errors for each rate constant calculation.

A few assumptions were made in the experiment that may contribute to error. It was
assumed that α0 and α∞ could be calculated theoretically, instead of determining experimentally.
Any inaccuracy in path length, sucrose concentration, or any general factor that may have
skewed the polarimeter readings would hurt the correlation between the theoretical α0 and α∞
values and the experimental values. By allowing 3 minutes to pass before taking the first reading,
it is impossible to accurately measure the α0 without more complex instrumentation. However,
allowing the experiment to run longer may allow future experimenters the ability to approximate
α∞ without relying on a theoretical calculation. Moreover, the experiment assumed a perfect 1:1
ratio between species in the reaction. Mixing was a relatively cursory affair, and any sucrose that
may not have solubilized or remained in the beaker after pouring into the polarimeter would
certainly change this ratio.

CONCLUSION

In this experiment, polarimetry was used to monitor the sucrose hydrolysis reaction with
HCl. In a solution with excess HCl, a first-order model was used to calculate the apparent rate
constant of the reaction. Next, in a reaction mixture with equal concentrations of sucrose and
HCl, a second-order equation was used to fit the data and calculate the actual rate constant, since
the concentration of HCl would now have a significant effect on the rate. Comparing these two
values establishes a relationship between actual and apparent rate constants that is dependent on
the concentration of H+, which was 3 M in this experiment. Lastly, possible sources of error in
the experiment were discussed and possible improvements were provided for future experiments.
 8

REFERENCES

[1]
Einhorn, A. Electro-Optics Principles and Applications 1973.

[2]
Link, S; Tauzin, J. CHEM 368 Laboratory Manual. Rice Department of Chemistry, 2018.
 9

APPENDIX

PLOT OF TIME VS. Z 1 FOR SOLUTION 2

0
-0.05
-0.1
-0.15
-0.2 y = -0.012x + 0.0075
Z

R² = 0.9979
-0.25
-0.3
-0.35
-0.4
0 5 10 15 20 25 30
time (minutes)

Figure 3. Calculating kapp for reaction of sucrose solution 2 with HCL. Z1 is defined in the
calculations section. Rate constant is equal to the negative slope of the linear regression line.