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Introductory Laboratory Energy Science and Technology

Experiment 8-2
Physical Chemistry

Sucrose inversion

reaction rate constants and activation energy


(kinetics)

Study the kinetics of sucrose inversion by polarimetry


1. Task:
1. Determine the reaction rate constants of the sucrose cleavage at 20, 25, 30 and 35 degrees
Celsius on computational and graphical way.
2. Determine graphically the activation energy of hydrolysis (in kJ/mol) from the thus
determined reaction rate constants.

2. Fundamentals:
Sucrose is a disaccharide of glucose and fructose. By addition of an acid, the sucrose cleaves into
its components. The activation energy of the reaction can be determined from the reaction rate
constants of this cleavage reaction at different temperatures. To determine the reaction rate
constant, we make use of the differences in the optical rotation properties between sucrose and its
components (differing in terms of magnitude and, in some cases, in their signs). After
equilibration, the products of the splitting reaction show a different sign in the optical rotation
than the starting molecule, which led to the name "invert sugar".

2.1

Mechanism of sucrose splitting:

Sucrose consists of one molecule of D-glucose and one molecule of D-fructose. Both molecules
are acetal-like linked.

Fig. 1 Saccharose (o-D-glucopyranosyl--D-fructofuranoside) or sucrose.

As a matter of fact, no cleavage occurs initially when sucrose is dissolved in water. However, the
cleavage can be catalyzed (the cleavage can be measure in a time scale of a few hours) by adding
an acid. By the addition of an acid, the bridging oxygen atom is protonated. This increases the
partial positive charge of the adjacent carbon atoms where the lone pair orbitals of oxygen in the
water molecules can attack. Consequently, the cleavage of the disaccharide and subsequent
deprotonation takes place:

While the protonation proceeds too fast to be measurable with our investigation method, the
splitting process is tracked by polarimetry.

2.2

Sucrose and invert sugar / stereochemistry

Glucose and fructose are formed during the cleavage of sucrose (specific rotation [D] = +66.5).
In aqueous solution, glucose exists in three forms: the -D-glucose, -D-glucose and the openchain form., cf. fig. 2.
When both pure -D-glucose and pure -D-glucose are dissolved in water, one can observe a
continuous change in optical rotation, until a constant final value is eventually reached. This socalled "mutarotation" takes place with an immeasurably rapid rate upon addition of small
amounts of alkali. The conversion of -and -form into each other proceeds via the abovementioned open form, however, only about 0.024 mole-percent is present in solution at pH = 7
(see figure below).

Fig. 2 Saccharose, its cleavage products and the present forms in the equilibrium
For these reasons, the sucrose cleavage will, in addition to the direct splitting products -Dglucose and -D-fructose, also result in -D-glucose as well as the open form of glucose,
depending on the equilibrium of the mutarotation. In addition to the glucose molecules, there are
also two possible conformers (equatorial and axial form). The adjustment of all related equilibria
is faster than the cleavage reaction of sucrose itself.
The specific rotation values for D-glucose and D-fructose are [] D = +52.5 and [] D = -92,
respectively.
Since the levorotatory fructose has a greater molar rotation than the dextrorotatory glucose, the
resulting mixture of glucose and fructose is slightly levorotatory.

2.3

The origin of optical activity. The phenomenon of optical activity and its

experimental measurement.
Isomeric forms of molecules that only differ in their behavior regarding linearly polarized light
(identical chemical and physical properties except for their ability to rotate the plane of linearlypolarized light by equal amounts in opposite directions) are called enantiomers. The two
enantiomeric forms of molecules behave according to their symmetry as an object to its mirror
image. All kinds of isomerism of molecules, which do not fall within the definition of
enantiomers, are called diastereomer. If a type of molecules is an enantiomer to another one, it
can not simultaneously be diastereomeric to that type of molecules and vice versa.

Think about:
What requirements regarding the molecular symmetry are required from a molecule to be
optically active, i.e., to show enantiomeric forms? Does the occurrence of so-called asymmetric
carbon atoms satisfy the requirements for optical activity, or are there cases in which there is an
asymmetric carbon atom, but there is no optical activity? Are there also cases in which optical
activity is not observed although an asymmetric carbon atom does exist? What about the presence
of optically activity without an asymmetric carbon atom ?

"FOR INTERESTED"
Using the present experimental set-up, the optical rotation is only measured at a fixed wavelength,
namely that of the Na-D-line. In general, polarimetry is a spectroscopic method: the optical
rotation of optically active compounds changes over the wavelengths. Actually, to describe the
molecular conformation clearly, the chemist can use different nomenclature principles. Find out
about the D, L- and R-, S-notation! Keep in mind that neither the absolute nor relative molecular
conformation has anything to do about the occurring rotation. Therefore, it is essentially
necessary to denote the occurring rotation in the unified name. (By d, l-, or nowadays by +, -)
The measurement of optical activity is performed by means of a polarimeter. Such a device
basically consists of a light source with a monochromator, a polarizer, which produces the
linearly polarized light (how does the natural light differ from linearly polarized light?) and an
analyzer, which determines whether the plane of polarization is rotated, and if so, at what angle.

In order to improve the accuracy of the detection of the rotation angle caused by the substance,
the polarimeter configuration was modified by Lippich (penumbra polarimeter). How?

2.4

The inversion of sucrose

We use the following abbreviations:


S: Sucrose
F: fructose
G: glucose.
The actual inversion reaction (1)

is catalyzed by protons. The actual cleavage reaction is in front of the equilibrium (2):

This equilibrium is relatively faster compared to the overall reaction (1). The equilibrium
constant of this equilibrium is given by:

Further reaction proceeds according to the scheme:

The water is, if working in (sufficiently) diluted solutions, available in large excess, the H2O
concentration may therefore be regarded as practically constant and is thus included in the
reaction rate constant k'. This results in c = cs:

The H+ ions are only catalytically active, hence, the concentration cH+ can also be considered as a
constant during the reaction. Thus we obtain: (k = k'KcH+)

(3)
Therefore, the cleavage proceeds in a pseudo-first reaction order.
Do you know any reactions with another reaction orders? Are there any zero-order reactions? The
order of a reaction does not coincide with the reaction stoichiometry. Try to understand the
differences between these values. Why is it so important for a chemist to get detailed information
about the kinetics of a reaction? What conclusions can be drawn from the reaction kinetics?
By integrating equation (3) (with c = c0 at time t = t0)

(4)
Since optical rotation is directly proportional to the concentration of optically active molecular
species (at least in the low concentration regime), a change in optical rotation can be exploited to
monitor the reaction. The variation of the rotation angle is proportional to the change in
concentration of sucrose. The rotation angle of a chiral substance depends on the temperature,
the wavelength, the length d that the light passes through the substance, and the concentration c
of the chiral substance:
= [] d c
where [] means the specific rotation.
During the inversion reaction, the concentration of sucrose (= c) decreases and the concentration
of invert sugar (= c ') increases. At a given time t, the angle of rotation is obtained by:
= [] dc + [ '] d c' = [] dc + [ '] d (C-c)

(5)

(C: weight concentration of sucrose)


[], [']: specific rotation of sucrose or of invert sugar. Thus, with 0 being the angle of rotation
at time t0 :

and

(6)
From equation (5), the following equation is found for t (i.e., c 0)
['] d C =
Thus, we obtain from (4) and (6):

(7)
Using this relationship, the reaction rate constant k can be calculated from the readings of the
rotation angle during the reaction. When transforming equation (4) into an exponential form, we
recognize that the concentration decreases exponentially with time. This means that the frequency
of measurements must be higher in the beginning than later in chronological order.
Are there other methods to determine reaction rate constants? Do you know any special
procedures for the determination of reaction rate constants for very rapid reactions? Does this
optical method have a special advantage ?
The reaction rate constants k determined by this method strongly depend on the temperature.
Considerations such as Arrhenius equation is an exponential dependence:

(8)
(A: prefactor, T: absolute temperature, A molar activation energy)
The reaction rate constant is related to the energy of the reacting molecules according to the
Arrhenius law. The reaction can only occur for those molecules with an energy that is at least as
large as is the activation energy. The prefactor A essentially includes geometric characteristics of
molecule collision.
The qualitative form of the Arrhenius expression suggests a relation to the Boltzmann distribution.
What is this?
From equation (8) we obtain (with k0: rate constant at temperature T0):

So k is determined at different temperatures, one can calculate EA by lg(k/k0) plotting against l/T.

implementation

Sucrose cleavage
Preheat a 0.5 M sucrose solution and a 2 M HCl solution to 20C. When the temperature
compensation is established, mix 25 mL of 2M HCl solution and 25 mL of the sucrose solution in
a beaker. Now, fill the preheated polarimeter tube as quickly as possible with the reaction
solution, be careful that no bubbles are formed in the beam path. Furthermore, measure the exact
temperature of the reaction solution. When the temperature equilibrium is established, read off
the angle of rotation. Get close to the eyepiece so that the vision field is sharp. Then rotate the
analyzer until the two fields appear equally bright. This point is approached several times by both
sides, read the vernier and average the values. Read the rotation angle at certain time intervals, at
the beginning of the reaction in shorter, later in longer intervals. The experimental preparation
should be conducted carefully but as soon as possible so that you can follow from the beginning
of the reaction quantitatively.
How to determine
Fill a 50 mL-flask with the reaction solution. The flask is put into a water bath (50 - 60 C) and
heated for 30 min (fill the 500 ml-beaker with hot water and refill it when the temperature drops
below 50 C).
The cooled solution returns to the polarimeter tube and measure the rotation of 20. By increasing
the temperature, the reaction rate of the inversion significantly increased, so that it proceeds
almost completely in a short time. Perform the measurements for the other temperatures
analogously.

For test preparation:


- Origin of the optical activity (crystal and molecular symmetry, asymmetric carbon atoms, etc.)
- Terminology and classification systems for optically active compounds (+, - / d, l / D-, L- / R-,
S-).
- What is the role of optically active compounds in (organic) chemistry?
- What is a racemic mixture, why is meso-tartaric acid not optically active?
- How does a simple (Lippich-/ penumbra-) polarimeter work?
- What other methods do you know to determine the kinetics of a chemical reaction?
- Why is it important for a chemist to know the kinetics of a chemical reaction? What conclusions
can we draw from kinetics?
- What is the advantage of determining the reaction rate by optical methods?
- Learn about the Arrhenius equation, the theory of the transition state!
Put your findings in the theoretical part of the lab report in concise form.

Experimental measurement protocol 6 (sucrose inversion)


Group No.:
Name:
Temperature:
T / min

=
k=

C
/

T / min

18

19

20

22

24

26

28

30

32

10

34

11

36

12

38

13

40

14

45

15

50

16

55

17

60

Phvsical Chemistry Basic Training


Experiment 6
Investigation of the kinetics of sucrose inversion by polarimetry

Name (l):
Name (2):
Group No.:
Date:
Results:

l. Reaction rate constants


Temperature

2. Activation energy:
EA=

Rate constant