Kinetics of the mutarotation reaction of glucose

Introduction
Optical isomers
Most simple chemical compounds can be superimposed on their mirror image. For example, Figure 1 gives
a molecule of 2-propanol and the mirror image of the molecule. The mirror image can be superimposed on the
original molecule and is therefore not distinguishable, but is in fact the same molecule.

Figure 1. 2-propanol and its mirror image.

There is, however, a class of molecules that cannot be superimposed on their mirror image. A simple
example of such a molecule is 2-butanol, shown in Figure 2. The two molecules of 2-butanol in the figure are
mirror images of one another, just as was the case in Figure 1. However, unlike the mirror images in Figure 1, the 2butanol molecule and its mirror image cannot be superimposed on one another, and therefore represent distinct
molecules. Molecules that cannot be superimposed on their mirror image are called optically active molecules, for
reasons discussed below, with the non-superimposable forms of the molecules called optical isomers.

Figure 2. 2-butanol and its mirror image.

Additional information concerning optically active molecules and optical isomers can be found in reference
[1] or most other standard organic chemistry texts.
Rotation of light
The physical property that distinguishes an optically active molecule from an optically inactive molecule is
the way in which the molecule interacts with polarized light. Polarized light is light where the electromagnetic
oscillations have been oriented in a particular plane perpendicular to the direction in which the light is moving.
Polarized light can be produced by reflection of light from a surface or by passing light through a crystal or oriented
polymeric film. When polarized light passes through a solution containing only optically inactive molecules, no
change in the plane of polarization of the light is observed. However, if an optically active molecule is present in
the solution, the plane of polarization of the light will be rotated either to the right (positive, D, or dextrorotatory) or
to the left (negative, L, or levorotatory). The angle of rotation of the plane of polarization of the light is given the
symbol . Some of the properties of polarized light and its interaction with optically active molecules are discussed
in reference [2].

The amount of rotation that a plane polarized beam of light undergoes when passing through a solution
containing optically active molecules depends on many factors, including the concentration of optically active
molecules in solution, the wavelength of the polarized light, the pathlength, the temperature, and the solvent.
Because of this, a reference condition is needed for reporting optical activity. The specific rotation of an optically
active compound, given the symbol []DT, is defined as the observed rotation for a 1 g/mL concentration of the pure
optically active compound in a 10 cm polarimeter cell, at a fixed temperature T, using polarized light from the D line
of a sodium emission lamp (actually a closely spaced doublet line occurring at 589.3 nm, corresponding to the 2P
2
S electronic transition). The relationship between obsd, the rotation observed for a particular concentration and
pathlength, and []DT, the specific rotation of the compound is
[]DT = 10(obsd)/c

(1)

where c is the concentration of the optically active compound (in g/mL) and is the pathlength of the polarimeter
cell (in cm).
The mutarotation reaction
Glucose (dextrose) is a monosaccharide, a sugar with the chemical formula C 6H12O6. In water, glucose
exists in two cyclic forms (which themselves have non-superimposable forms that are their optical isomers), called
-D (+) glucopyranose and -D (+) glucopyranose, as shown in Figure 3. These two forms of glucose are not
mirror images of one another because there is more than one optically active site in the molecule. As it happens,
both of these molecules are dextrorotatory.

Figure 3. Several representations of the and isomers of D-glucose.

The mutarotation reaction occurs by protonation of the ring oxygen atom followed by formation of the
linear, or aldehydic, form of the sugar, as indicated in Figure 4. When the cyclic form of the sugar is regenerated
either the or the configuration can occur. Thus one cyclic form of glucose may be converted to the other cyclic
form of glucose. Whether we begin with the or the form of glucose, the aldehydic intermediate is the same.
The mutarotation reaction thus generates an equilibrium concentration of and forms from any initial
nonequilibrium concentration of starting material.

Figure 4. The mutarotation reaction of D-glucose. The specific rotations for the two isomers
are []D25 = + 112.0 for -D glucose and []D25 = + 18.7 for -D glucose.
Kinetics [3]
The mutarotation reaction is a kinetic system with the form
A B

(2)

where
A = -D (+) glucose = -D (+) glucopyranose
B = -D (+) glucose = -D (+) glucopyranose
k1 = rate constant for conversion of A into B
k-1 = rate constant for conversion of B into A
The rate law in differential form is then
d[A]/dt = -k1 [A] + k-1 [B]

(3)

where d[A]/dt is the rate of change in the concentration of A with time. Note that at equilibrium (with equilibrium
quantities labeled eq)
(d[A]/dt)eq = 0 = -k1 [A]eq + k-1 [B]eq

(4)

or
[B]eq/[A]eq = Keq = k1/k-1

(5)

which gives a simple relationship between the equilibrium constant for the reaction and the rate constants for the
reaction.
Returning to equation (3), we may integrate to obtain the time dependence of the concentration of A. The
result [4] is
([A]t - [A]eq)/([A]0 - [A]eq) = exp[ - (k1 + k-1) t]

(6)

or

ln{([A]t - [A]eq)/([A]0 - [A]eq)} = - (k1 + k-1)t = - kt

(7)

where we have defined [A]0 as the concentration of A at some convenient starting time t = 0 (which, because the
reaction is first order, is arbitrary), [A] eq as the concentration of A at equilibrium, and k as the sum of the forward
and reverse rate constants for the reaction (that is, k = k 1 + k-1). Note that the rate at which the system approaches
equilibrium is determined by the sum of k1 and k-1.
The optical rotation of a solution containing -D (+) glucose and -D (+) glucose is directly proportional to
the concentration of the -isomer for a fixed path length and total glucose concentration. Equation (7) can therefore
be rewritten as
ln{(0 -eq)/(t -eq)} = kt

(8)

where t is the observed rotation of the solution at time t, 0 is the observed rotation at t = 0, and eq is the rotation
observed when the system has reached equilibrium. Notice that we do not need to convert the observed rotation of
the solution to a specific rotation, nor do we need to know the constant of proportionality that relates t to [A]t.
A plot of the left hand side of equation (8) versus time has a slope equal to k. The equilibrium constant for
the mutarotation reaction can be found by measuring the optical rotation of a solution that has achieved equilibrium,
given the total concentration of glucose in the polarimeter cell, the path length of the cell, and the specific rotation of
each glucose isomer. From k and Keq, the values of k1 and k-1 can be found.
Experimental
A stock solution of perchloric acid (PCA, HClO4) is prepared by carefully diluting 2.0 mL of 70% PCA to a
final volume of 100.0 ml with water. This results in a solution that is 0.232 M in PCA. From this stock solution,
prepare four additional solutions as follows:
Solution

PCA stock solution

(mL)

Water
(mL)

5.0

45.0

10.0

40.0

15.0

35.0

20.0

30.0

The hydrogen ion concentration should be calculated for each solution. Remember that PCA is a strong acid, so
[H+] = [PCA].
The procedure for carrying out a kinetic run is as follows. Place the 50.0 mL diluted PCA solution and a
magnetic stir bar to a 100 mL beaker. Add approximately 5.0 g of glucose to the beaker while stirring the solution
vigorously. Be sure to record the exact mass of glucose used as you will need this information in calculating the
equilibrium constant for the mutarotation reaction. When the glucose has completely dissolved, fill a 10 cm
polarimeter cell with solution so that there is at most only a small air bubble inside the cell (you might want to
practice filling the polarimeter cell with distilled water before attempting a kinetic run). Place the polarimeter tube
inside the polarimeter, and measure the rotation due to the solution. This initial value of rotation is 0. Continue to
measure the rotation of the solution at time intervals over which the rotation changes by about 0.2, until the initial
rotation (which will be about 10) decreases to about 6. Label and save the excess solution. A final measurement
of the observed rotation should be made after sufficient time has elapsed so that equilibrium between the two forms
of glucose has occurred. The value of the rotation measured at that time is eq.

On each day that experimental data are taken you should also measure the observed rotation when there is
no sample in the pathway. We will call this value for rotation null. The rotation that is observed should in principle
be equal to 0.0 . However, it will be slightly different from zero due to drifting in the calibration of the polarimeter.
All of your experimental values for rotation should be corrected for this small drift in calibration by
subtracting the value of null from each data point. This must be done before any additional data analysis is
carried out, and using the value of null found on the data that the data were obtained.
You should also record the temperature of the room for each day that data is taken. While the temperature
will not be used in your calculations, differences in temperature on different days can affect the rate constant (and, to
a lesser extent, the equilibrium constant) for the reaction.
Lab report
Your laboratory report should include the following:
1) The experimental values of k and Keq for each [H+] at which data are taken. You have to derive an
equation for finding Keq based on the information you have available to you.
2) The experimental values of k1 and k-1, which can be calculated once k and K eq are known. The details of
the calculation of k1 and k-1 from k and Keq should be given. Use your average value for Keq in the calcumtions of
k1 and k-1.
3) A discussion of the effect of hydrogen ion concentration on the value of k. How does k depend on [H +],
or pH (a plot of k vs [H+] might be useful here)? If possible give a quantitative relationship between hydrogen ion
concentration and k. Can you suggest any additional experimental work that could be carried out to test your
proposed relationship?
You do not need to find literature values for k or Keq.
References
1. T. W. G. Solomons, Organic Chemistry, Sixth Edition, (Wiley, New York, 1996) pp. 193-199.
2. C. W. Garland, J. W. Nibler, D .P. Shoemaker, Experiments in Physical Chemistry, Seventh Edition,
(McGraw-Hill, Philadelphia, 2003), pp. 667-668.
3. A general discussion of first order reversible reactions is given in P. W. Atkins, J. de D .P. Shoemaker,
aula, Physical Chemistry, Seventh Edition, (W. H. Freeman Company, New York, 2002), pp. 876-877.
4. S. W. Benson, Foundations of Chemical Kinetics, (McGraw-Hill, New York, 1960), pp. 27-29.
Acknowledgements: Figures 1-4 are taken from T. W. G. Solomons, Organic Chemistry, Sixth Edition,
(Wiley, New York, 1996).
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Revised 1/13