| Computer-Interfaced
Experiments - Absorbance Measurement Acid-catalyzed Iodination of Acetone - Pseudo Zero Order Reaction Objectives: Determination of Rate Constants, Test for a Pseudo Zero Order Reaction Peter Keusch | ||||||||||||||||||||||||||||||
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The reaction of acetone with iodine producing iodine acetone, represents in the acid aqueous medium, (like other ketone
halogenations) a irreversible redox reaction catalyzed by protons. In a first step (reaction 1) acetone (A) is protonated producing
AH+:
Reaction 1 (fast)
AH+ is formed in very small concentrations. AH+ decomposes in the reverse reaction to regenerate hydrogen ion
and acetone (keto- or enol-form).
Reaction 2 (slow)
Reaction 1 is like many other protonation-deprotonation reactions relatively fast. However, the formation of the enol (reaction step
2) takes place slowly. Since the H + taken up by the acetone is regenerated by the formation of enol, a hydrogen
catalyzed keto-enol-isomerization reaction takes place. Iodine reacts with the enol irreversibly to form iodine acetone (AI) and
hydroiodic acid (HI):
Reaction 3 (fast)
Since this reaction is very fast (k3 >> k2), the enol formed in reaction step 2 is immediately converted.
The second reaction step is rate-determining. The formed enol reacts in the third step immediately with iodine to form iodoacetone.
When all the iodine is used up the reaction will stop.
Kinetic equations
(Download)
50 mL of the reaction solution should have the following proton- and iodine concentrations:
cH = 0.08 mol · L -1
cI2 = 0.004 mol · L -1
for the first mesurement: cAc = 0.675 mol · L -1
for the second mesurement: cAc = 1.35 mol · L -1
for the third mesurement: cAc = 4.05 mol · L -1
Calculation of the appropriate volumes
(Download)
Calibration of the photometer and matching of the program Chemex
is carried out analog to the procedure described in experiment Bromination of reactive
Aromatics
Spectronic 20 (Download) features an analog output on the bottom of
the instrument. The analog output of the photometer is connected to the input Sensor1 of the CHEMBOX.
The photometer has been designed so that when it displays 100 % transmittance, the analog signal at its output connector is 1 VDC;
when the instrument displays 0 % transmittance, the output voltage is 0 VDC.
The absorbance wavelength is set to 490 nm.
The calibration of the photometer is performed using a decolorized mixture of 2 ml of iodine solution and 2 ml of acetone.
Experimental procedure:
Fig. 1: Experiment set-up |
7 mL of 0.5 molar sulfuric acid are pipetted into a 50 mL graduated cylinder and via a burette the calculated volume of acetone is added. Afterwards the acid acetone solution is accurately made up to a volume of 46 mL with distilled water. Now the solution is poured into a beaker. 4 mL of 0.05 molar iodine solution are pipetted into a further beaker. The top of the beaker is covered with a piese of parafilm foil. The plastic film is firmly fastened around the mouth of the beaker to prevent the release of iodine into the air. The two beakers are placed in a thermostated water bath at approx. 35°C (temperature within the sample compartment of the photometer) and left there about 15 minutes until thermal equilibrium to be reached. During the thermal equilibration period the photometer is calibrated and the program Chemex is matched (see above). After thermal equilibrium has been reached the reaction temperature is read to nearest 0.1 °C. The acetone solution is poured smoothly and rapidly to the iodine solution. A cuvette is filled about 3/4 full with the reaction solution. The cuvette covered with a bit of Parafilm, is inverted 2-3 times to ensure proper mixing and placed into the light-tight sample compartment of the photometer. Simultaneously the sensing software is started. The change in transmittance and in absorbance is displayed simultaneously on the measuring screen (Fig. 2). The in-situ determination of the reaction rate on the basis of a continuous logging of photometrical data is allowed in rapid reactions (small change in temperature during te reaction). |
Chemex 1.5 permits the overlay of the individual series of measurements. Already using the measuring program the experiment can be
analyzed accurately. Through the linear portions of absorbance graphs a straight line is drawn. If the center of the cursor is
positioned at the point the straight lines meets the abscissa, 'Chemex' displays the time t for the reaction to complete.
Calculation of the rate constants k according to equation (21)
Kinetic equations (Download)

The 3 measurements yielded a mean value of 0.394 [ L · mol-1 · h -1 ]
For a zero-order reaction, the rate of reaction is a constant. When the limiting reactant has been completely consumed the reaction
will stop abruptly (Fig. 2).
References:
Computer-Interfaced Experiments Kinetics: Acid-catalyzed Iodination of Acetone - Pseudo Zero Order
Reaction
Kinetics of the Iodination of Acetone
Bromination of Acetone
Index of Chembox Experiments