Fachhochschule Mannheim Hochschule f r Technik und Gestaltung

Institute for Physical Chemistry Experiment 5a Reaction Kinetics

Reaction Kinetics Investigation: Inversion of Sucrose

1. Background: d-Sucrose is hydrolyzed in the presence of H+ ions to d-glucose and l-fructose:

[a]l' = specific rotation at temperature J, and the wavelength l, generally Na-D line: l=589nm d-Sucrose is optically dextrorotary while the resulting inverted sugar (the mixture of equal parts d-glucose and l-fructose) is optically levorotary. Therefore as the reaction proceeds the dextrorotation decreases proportionally to the converted d-sucrose. The course of the inversion reaction can therefore be easily monitored by measuring the optical rotation. 2. Derivation of the Rate Equation: The inversion reaction: Sucrose ( S ) + H2O [H+]

Glucose ( G ) + Fructose ( F )

is a complex reaction: in an equilibrium reaction initially a proton is added to the sucrose (S); in the subsequent reaction the intermediate product decomposes to glucose and fructose.

1. Equilibrium Reaction

S + H+

kH SH+ kR kF SH + H2O G + F + H+
+

2. Subsequent (secondary) Reaction

The protonation of sucrose quickly reaches an equilibrium state. The following equation is valid for the reaction rate constant K for this equilibrium:

K=

c + kH = SH k R cS * c H +

(1)

The subsequent reaction occurs slowly and is, therefore, the rate-determining step of the reaction sequence.

dcS = -kF * cSH+ * cH2O dt

Combining equations (1) and (2) :

(2)

dcS = - k F * K * cS * cH + * cH2O dt

(3)

In the case of dilute solutions, a large excess of water is present, and the water concentration can be taken as a constant. The H+ ions are only catalytically active and thus the H+ ion concentration (cH+) also remains constant during the reaction. The reaction order is then lowered from a thirdorder reaction to a first-order reaction. With k1=kF*K*cH+*cH2O equation (3) can be rewritten as:

dcS = - k1 * cS dt

(4)

The experimental reaction rate constant k1 depends on the concentration of the H+ ions. It increases with increasing H+ ion concentration. Integration of equation (4) gives:

ln

cS ,0 = k1 * t cS

(5)

cS0=cS at time t=0

The reaction can be monitored with the help of the optical rotation. The following definitions apply:

at a0 a [a]x
d c

angle of rotation at time t angle of rotation at beginning of reaction (t=0) angle of rotation at end of reaction (t = ) specific angle of rotation of substance X path length of the irradiated solution molar concentration of substance X

During the inversion reaction the concentration of sucrose, cS, decreases while the concentration of the inverted sugar, cI, increases. For the angle of rotation at time t the following equation applies:

at = [a]S*d*cS + [a]I*d*cI = [a]S*d*cS + [a]I*d*(cS0-cS)

Rearranging, the concentration of sucrose can be expressed as:

(6)

cS =

a t - [ a ]I * d * cS 0 ([ a ]S - [ a ]I )* d

(7) (8) (9)

Equation (6) has the following boundary conditions: at t = (i.e. cS = 0) a = a= [a]I*d*cS0 at t = 0 (i.e. cS=cS0) a = a0 = [a]S*d*cS0 Equations (7), (8) and (9) are combined to give:

cS 0 a 0 - a = cS a t - a
Thus, from equations (5) and (10) :

(10)

ln

a0 - a = k*t a t -a
ln

Plotting as a function of t results in a straight line with a slope equal to the reaction rate constant k1.

a0 -a at -a

3. Necessary Equipment: 1 Polarimeter (Polartronic I, Schmidt and Haensch) 1 temperature-controlled Polarimeter tube (path length d=20 cm) 1 Thermostat 1 Thermometer 0-50C, 0.1 divisions 1 stop-watch 4. Experimental Procedure

a. Starting solution: Mix 10g d-sucrose with distilled water to make a solution with a volume of 50ml. b. Determination of a0 : Dilute 20 mL of the sucrose solution in an Erlenmeyer flask with 30 mL distilled water. Mix the solution well and place in the polarimeter tube pre-heated to 20C. It is important to ensure that no air bubbles are present in the light path. Once temperature equilibrium is obtained, the angle of rotation, a0, can be read. c. Reaction Separately pre-heat the sucrose solution and the hydrochloric acid (l mol/L) to 20C. Mix 20 mL of the sucrose solution with 30 mL of the hydrochloric acid in an Erlenmeyer flask. Start the stopwatch upon addition of the acid. Put the reaction mixture in the clean and dry polarimeter tube and read-off the angle of rotation, at at the following times: t= 5, 10, 15, 20, 30, 40, 50,60, 75, 90 min. The value for a is obtained after about 24 hours. After the measurement, wash the polarimeter tube with distilled water. 5. Evaluation:

ln
a. Plot

a0 -a at -a

as a function of t and determine the reaction rate constant, kl, from the

slope. b. Calculate the time at which half of the sucrose is converted. c. Calculate a0 and a, and compare them with the measured values. (d-sucrose M = 342.3 g/mol, invert sugar M = 360.3 g/mol)

6. Operating instructions for using the polarimeter Polaritronic I: a. Setting the zero point First set the micrometer screw to the zero position by turning it from the top setting to the bottom setting. An index on the lower side of the projection scale now indicates the zero point. Using the large knob on the right side wall, turn the analyzer and the semicircle attached to it to the position 0 , at which the zero point of the circular graduation is the same as the zero point of the projection scale. The polarimeter is only exactly set to zero if the pointer of the zero instrument and the feeder are set at zero. If that is not the case a correction must be made by using the front left knob of the polarimeter. Occasionally check the zero point during the measurement. b. Reading the scale : The semi-circle attached to the analyzer is fitted with a degree scale, which is magnified and projected onto a screen. The line projected onto the semi-circle indicates both the degree and 1/10 degree of the measurement. Using the micrometer screw, ensure that the transition from one degree to the next matches the indicated 1/10 degree readings. The degree and 1/10 degree value can now be read from the projected scale. The 1/100 and 1/200 degree values can be read from the micrometer screw. For dextrorotary samples the value can be directly read from the scale, while for levorotary samples the complimentary angle to 360 has to be calculated. c. Measurement: Make a series of measurements with the sample placed in the enclosed groove and observe the deflection of the needle. Turn the driving knob in the direction of the deflection of the needle until the zero setting of the needle is reached (Avoid parallel axis). Turn the micrometer screw until the projected line matches the 1/10 degree settings. Read the measurement value on the projection scale and micrometer screw. 7. Operation of the photoelectric polarimeter Operating scheme:

The light from a sodium discharge vapor lamp travels through the lens L1, through the aperture Bll, the objective lens L2, and the interference filter IF, to the polarizer P. The interference filter IF filters out light of wavelength 589 nm with high spectral purity from the spectrum of the light source. The light is linearly polarized through the polarizer. The polarizer lies in a semicircle and can, therefore, be turned by a measurable amount relative to the opposing analyzer A. The light, after it passes through the exit aperture Bl2, passes through the substance M. The lens L3 projects the exit aperture onto the analyzer, so that a well-defined beam of light also passes through the

glass rod in the magnetic coil F (Faraday modulator). The analyzer remains in place during the measurement and can be finely adjusted to correct for any drift in the zero point setting. The light then travels to the photoelectron multiplier PEV. For the correct setting of the instrument the oscillation planes of the linearly polarized light and the analyzer are exactly transposed (90 dark position, Fig. 1). Due to the Faraday effect, the Faraday modulator, which runs on an alternating current, causes a corresponding fluctuation of the angle of rotation, which results in a periodic lightening, which is symmetrical to the dark setting (Fig. 2).

If a polarimeter tube with an optically active substance is placed in the path of light, the oscillation plane of the polarized light is rotated by an angle n from the original position. (Fig. 3). The photoelectron multiplier gives rise to a current proportional to the angle upon which is superimposed an alternating current with frequency n. When the analyzer is exactly transposed (90o to the plane of polarized light) the alternating current is 2 n. In the subsequent resonance amplifier the alternating current with frequency n is filtered out, adjusted phase dependently, and displayed on the zero instrument. Because of the phase-dependent alignment of the alternating current, the instrument indicates also the direction of the optical rotation. The polarizer is turned back by the now active angle of rotation of the measured substance until the reading on the instrument disappears. Hence, optical rotation is compensated by rotation of the polarizer, whereby this angle of rotation is equal to the angle of rotation of the measured substance. Faraday effect : All substances in a magnetic field acquire an optical rotation if there is a permanent component in the flux of the magnetic field in the direction of the light path or in the opposite direction. The effect of the field reaches a maximum if the lines of the magnetic field run parallel or antiparallel to the path of the rays of light.

.
d-Sucrose

. .

Invert sugar