KINETICS OF SUCROSE INVERSION AT 20̊C BY POLARIMETRY

Laura Brazuelo, and Hong Winkelman

Chemistry Department
Christian Brothers University
Memphis, TN 38104
28 February 2020
 Abstract
The rate of the reaction in which sucrose is hydrolyzed to glucose and fructose is
determined by observing the change in the optical rotation of sucrose as the reaction
proceeds. Each sample has a different specific rotation and the rate of inversion can be
measured using polarimetry. The rate constant (k) of the first-order kinetics helps to
understand how the rate of reaction is affected by the concentration of sucrose. It is
found to be 1.23x10−2 ± 0.05 min−1 M −1 at 20 degrees and using 2.0M HCl.

Introduction
Kinetics of hydrolysis of sucrose to fructose and glucose in a dilute HCl solution

has had an important role in the development of the theory of reaction kinetics. 14 The

rate of reaction between sucrose and water catalyzed by a hydrogen ion is followed by

measuring the angle of rotation of polarized light passing through the solution. The

angle of rotation of polarized light passing through the solution is measured using a

polarized beam. Using the optical method to study the properties of a solution is helpful

to maintain the original chemical structures. As polarized light passes through a chiral

molecule with optical activity, the plane of polarization will be rotated clockwise or

anticlockwise depending on the chirality of molecules. 1As the sucrose is used up and the

glucose-fructose mixture is formed, the angle of rotation to the right becomes less and

less, and finally the light is rotated to the left. The rotation is determined at the

beginning (αο) and at the end of the reaction (α ∞), and the difference between these two

readings is a measure of the original concentration of the sucrose. The reaction proceeds

too slowly to be measured in pure water, but it is catalyzed by hydrogen ions. The rate

constant will vary with the electrolyte concentration, and the resulting change in the

concentration of the collision complex will cause a change in the measured rate constant

k.2
 Experimental section

The magnitude of the optical activity is measured using a monochromatic light

source and a polarimeter. A polarimeter is a standard scientific instrument which is

commonly used to measure the angle of rotation. A monochromatic light source passes

through the polarizer and through the solution. The second polarizer, called an analyzer,

is initially aligned without the optically active sample in place so that all the polarized

light passes through. With the sample in place, the polarized light is rotated, and the

analyzer must be turned through an angle α to allow the light to pass. The unpolarized

light, often from the sodium D-line, is incident upon a polarizer which has the function

of forming a polarized beam. At the interface, one component is totally reflected to the

side, where it is absorbed by a black surface. The other component is freely transmitted

through the medium whose optical activity is to be examined and then intercepted by

the analyzer. If the analyzer is turned to the right, or clockwise as viewed looking

toward the light source, the sample is said to be dextrorotatory. The angle is then given

a positive sign. If the optical rotation causes the analyzer to be turned to the left, the

sample is said to be levorotatory and the angle is given a negative sign. The reason for

the observed rotation is that the chiral centers interact with the right- and the left-

circularly polarized light vectors in the polarized light as though the sample has two

refractive indices.1 During this process, the solution undergoes a transformation at 20

degrees Celsius, converting it to a mixture of fructose, glucose and sucrose S5-500

Certified ACS Crystalline Fischer Scientific. As this process takes place, the amount of

rotation is diminished until it reaches a solution that is fully converted, and the rotation

direction has been inverted, now from positive to negative.

 Results and discussion

The concentration of sucrose remaining in the solutions at any time may be

assumed to be proportional to the quantity α t-αf, where αt is the optical rotation at any

time during the experiment, and αf is the final rotation value. In the first phase of the

analysis, it is necessary to determine the order of the reaction with respect to sucrose

concentration. The table below will help to find out some values needed for the order

determination in the graph:

αt αt-αf ln (αt-αf) 1/(αt-αf)

8.9 14.4 2.667 0.069

7.1 12.6 2.534 0.079

5.4 10.9 2.389 0.092

4.55 10.05 2.308 0.100

3.05 8.55 2.146 0.117

2.35 7.85 2.061 0.127

1.25 6.75 1.910 0.148

0.5 6 1.792 0.167

-0.05 5.45 1.696 0.183

-1.05 4.45 1.493 0.225

-1.45 4.05 1.399 0.247

-2.4 3.1 1.131 0.323

-3 2.5 0.916 0.400

-3.45 2.05 0.718 0.488

-3.6 1.9 0.642 0.526

-4 1.5 0.405 0.667

-4.4 1.1 0.095 0.909

-4.55 0.95 -0.051 1.053

-4.75 0.75 -0.288 1.333

-4.9 0.6 -0.511 1.667

-5.15 0.35 -1.050 2.857

-5.3 0.2 -1.609 5.000

-5.35 0.15 -1.897 6.667

-5.5 0 #¡NUM! #¡DIV/0!

αt equal to 5.3833
 Since the levorotatory fructose has a greater molar rotation than the

dextrorotatory glucose, the resulting mixture of the glucose is slightly levorotatory. As

the sucrose is used up and the glucose-fructose mixture is formed, the angle of rotation

to the right becomes less and less, and finally the light is rotated to the left.

Figure 1-3 demonstrate the linearity of the various possible plots, which in turn

will reveal the order of the reaction.

(αt-αf) vs t
12

10

8
(αt-αf)

0
0 50 100 150 200 250
time (min)

Figure 1. Concentration versus time to determine if the reaction is zero order.

 ln (αt-αf) vs t
0,003
f(x) = − 0.0245868303096189 x + 2.94487549378728
0,002

0,001
ln (αt-αf)

0,000
0 20 40 60 80 100 120 140 160 180 200
-0,001

-0,002

-0,003
time (min)

Figure 2. Natural logarithm of the sucrose concentration versus time showing a first order reaction.

1/(αt-αf) vs t
0,007

0,006

0,005

0,004
1/(αt-αf)

0,003

0,002

0,001

0,000
0 20 40 60 80 100 120 140 160 180 200
time (min)

Figure 3. Inverse of the sucrose concentration versus time to determine if is a second order reaction.

The hydrolysis of sucrose catalyzed by hydrochloric acid is a first-order reaction

(figure 2). According to chemical kinetics, the equation of the first order reaction can be

written as

ln (αt-α∞) = -kt + ln(α0-α∞) (equation 1)

where k is the hydrolysis rate constant which is determined by the concentration of

hydrochloric acid. α0 is the initial optical rotation of the system when sucrose has not

converted. αt represents the optical rotation at which the reaction lasts for t minutes. α∞

is the final optical rotation. There is a positive correlation between the hydrochloric acid

concentration and the reaction rate constant k without changing the temperature, which

indicates that the concentration of catalyst hydrochloric acid has a great influence on the

hydrolysis rate of sucrose. Following Figure 2, the rate constant was found to be 0.0246

min-1. The measuring process does not involve any mechanical adjustment of optical

elements once the experimental setup is established and thereby realizes a real-time

detection of the dynamic chemical reaction.

Before calculating the rate constants, it is necessary to calculate a more accurate

value for αf, the final optical rotation. This measurement is known as α ∞, although the

elapsed time was considerably less than infinity. The criterion we would look for in

determining whether a plotted line was straight would be an optimizing of the

correlation coefficient (or standard deviation) for the best straight line through the

points. With a correlation of 0.9954, α∞ was found to be -5.75̊ for t=∞. Once that this

value is found, a data table is needed to posteriorly make the graph and show the

linearity. The data table with the values using αα is shown in Table I.

Using these results, the best linear fit is shown is Figure 4. It is possible to make

a graph showing the best straight line, that is the one that has the correlation coefficient

closest to 1. This graph is shown below.

 ln (αt-α∞) vs t
0,003

R² = 0.995402431248018
0,002

0,001
ln (αt-α∞)

0,000
0 20 40 60 80 100 120 140 160 180 200

-0,001

-0,002
time (min)

Figure 4. Graph using the appropriate data points to show the best possible straight line.

To make comparison with literature values more meaningful, it is necessary to

perform a calculation which takes into account the concentration of the hydrogen-ion

catalyst. Dividing the previously calculated value of k (0.0246 min -1) by the molarity of

hydrogen ions in the solution, k will have units of min -1M-1. Substituting with the correct

values, we found k to be 1.23x10-2min-1M-1. Measurements for the rate constant were

reported by some investigators using 2.0M HCl at 20̊C.

Investigator Rate constant,k, (min-1M-1)

J.H. Reeves and A.M. Halpern10 1.08x10-2

Deborah A. Moore , José E. Cortés-Figueroa11 1.60x10-2

F. A. Long and M. A. Paul12 2.02x10-2

Edward S. Amis13 1.13x10-2

Dai-LanNguyen-Tran1 0.85x10-2

Key-Martinez-Mendler1 1.16x10-2

H. Iloukhani, S. Azizian and N. Samadani3 2.016x10-3

Robert N. Goldberg*, Yadu B. Tewaril, and Jagdish 1.387x10-3

 C. Ahluwalia4

Pedley, J. B., Naylor, R. D., and Kirby, S. P5 1.204x10-3

E. Tombari, G. Salvetti, C. Ferrari, and G.P. Johari7 1.156x10-3

Kenneth W. Busch Carlos Calleja-Amador Denis H. 1.135x10-3

Rabbe Marianna Busch6

Comparing this data, it is possible to calculate the standard deviation for our

experimental value, that is 1.23x10-2±0.05min-1M-1. Due to the quantum noise of a

coherent light source and the limited extinction ratio of polarizers, the accuracy is

always lower than 10−3 degrees.8 Moreover, the measurement of chemical reaction

inevitably involves manual adjustment of optical elements, such as polarizers and wave

plates, resulting in long manipulation times. The specific rotation depends upon the

wavelength of the light, and this dependence is called optical rotatory dispersion. The

dispersion of optical rotation is closely related to light absorption; in the vicinity of

absorption bands, the optical rotation usually increases rapidly and then decreases

through zero to give an opposite rotation as the wavelength is changed. This is referred

to as the Cotton effect. 1These changes are more sensitive than most properties to

changes in molecular conformation. Because of the error inherent in locating the point

of minimum intensity, it is better to employ a scheme in which the eye is required only

to compare one field with another field of nearly the same intensity. 2 When a linearly

polarized light is reflected or refracted on an optical interface, the photonic SHE (spin

hall effect) manifested itself as spin-dependent shifts which are perpendicular to the

incident plane. The photonic spin-Hall shifts provide important information of optical

interface, and therefore, it can be employed as the pointer in precision measurements. 9

Also, the linear equation has two important and well-known consequences. The first
problem concerns the effect of experimental error. The raw data in kinetics experiments

usually has a constant error for every data point. That is, the uncertainty in the early

measurements is the same as in later measurements when the reaction is almost

complete. When the natural logarithm is taken, early data points are little affected by the

errors, but data points toward the end of the reaction have large deviations caused by the

basic nature of logarithms. Therefore, for a linear fit involving the logarithm, the error

in the data points at the end of the kinetics run have an inordinate effect on the fit

values.1

Conclusion

Kinetics of hydrolysis of sucrose to fructose and glucose in a dilute HCl solution

has had an important role in the development of the theory of reaction kinetics, and it

has been studied by a variety of techniques. The angle of rotation of the solution

changed as the sucrose converted to glucose and fructose. By measuring the angle over

a period of time with the polarimeter, we were able to determine the reaction rate. To

understand how the rate of reaction is affected by the concentration of sucrose, we

reaction rate constant, that was found to be 1.23x10 -2±0.05min-1M-1 using 2.0M HCl and

at a temperature of 20̊C.

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