## Monday, April 28, 2014

### Acid Catalyzed Iodination of Acetone - Physical Chemistry - Lu Le Laboratory

Purpose

1.     To determine the order of the reaction of iodine-acetone.
2.     To determine the rate constant at an assigned temperature

Principles

Acid catalyzed iodination of acetone is a complex reaction. The rate law for overall reaction cannot be determined from the balanced equation for the reaction but from experiments.
When an aqueous iodine solution is reacted with acetone in the prescence of an acid, the yellow color slowly fades as the iodine, I2, is consumed. The products of the reaction are iodoacetone and hydrogen iodide. Hydrogen ion is a catalyst for this reaction. The mechanism of the reaction is as follow:

Hydrogen ion participate in the reaction as a catalyst in step on and step two and also be produced as a product in step three. This kind of reaction is called an autocatalysis reaction. The rate equation can be represented as follow

The reaction progress can be tracked by the determination of the concentration of iodine and triiodide ion.

For the reaction, the K- =700 and the absorbance of the solution can be represented as follow
A = A(I3-)+A(I2) = ε(I3-)L[I3-] +ε(I2)L[I2]

When we set the wavelength of the light source of the spectrometer at 565nmthe molar absorbance of I2 and I3- is equal: ε(I3-) = ε(I2)

Absorbance = ε(I3-)L[I3- + I2]

Since the concentration of acetone and hydrochloric acid is much larger than the concentration of iodine/triiodide ion so we can assume the concentration of acetone and acid as a constant at the beginning of the reaction:

r = k[A]α[I3-]β[H+]δ = k[A]α[H+]δ = constant

Finally, we can figure out the reaction order and the activation energy of the reaction from Arrhenius equation:

Chemicals

1.     Iodine/KI solution (standardized): 0.02134M
2.     Acetone aqueous: 3.3738M
3.     Hydrochloric acid: 1.436M
4.     Distilled water

Apparatus

1.     Computer

2.     722S Spectrometer

3.     Cuvette
4.     Thermostatic water bath
5.     Pipette
6.     Dropper
7.     Washing bottle

Procedure

1.     Calibration the spectrometer with distilled water before use.
2.     Turn on the thermostatic water bath and set the temperature at 25.
Put the vessels with distilled water, acetone aqueous, hydrochloric acid, iodine solution in the water bath for at least 10 minutes.

3.     Measurement the εL value of iodine solution:
Turn on the 722S spectrometer and warm it up for at least 10 minutes. Put the cuvette with d.d. water into the spectrometer as a blank. Pour 25.00mL iodine  solution into a 25mL volumetric flask and dilute to the mark line with distilled water. Rinse the cuvette with the solution for twice, and add the solution to the two-third full of the cuvette, and determine the absorbance with the spectrometer.

4.     Mix the reactants in a volumetric flask as follow and dilute to the mark line then put into the spectrometer:

 Sample Iodine solution (mL) Acetone aqueous (mL) Hydrochloric acid(mL) 1 5.00 5.00 5.00 2 5.00 2.50 5.00 3 5.00 5.00 2.50 4 7.50 5.00 5.00 5 7.50 5.00 5.00

Experimental Record

Table 1. Concentration of Reagents
 Reagent Concentration Iodine/KI solution 0.02134 M Acetone aqueous 3.3738  M Hydrochloric acid 1.436   M

Table 2. The εL value
 The εL value of the diluted iodine solution (λ=565nm) 0.3636 Data Process

First, do linear fitting for each diagram.
Take 30~300s for sample 1.
Take 30~300s for sample 2.

Take 30~300s for sample 3.

Take 30~300s for sample 4.

Take 30~150s for sample 5.

Second, figure out the absorbance constant of iodine solution by the equation as follow:
Abs. x constant = Concentration

=> Abs.=0.3636, concentration = (0.02134*2.5/25)=0.002134M
=> constant= 5.869x10-3.

Third, multiply the constant with each slopes which we get from the figure above and the rates of reactions are as follow:

Table 3. Rate of Reaction
 Sample rate 1 -4.4796x10-6 2 -2.1737 x10-6 3 -2.4358 x10-6 4 -4.3071 x10-6 5 -9.1560 x10-6

The reaction orders can be found by the calculations as follow:

=>   β= 1.0420

=>   δ= 0.8781

=>   α= -0.0953
The rate equation can be represented as follow:

Then the reaction constant k can also be found:
Table 4. Reaction constant k
 Sample k 1 1.199X10-5 2 1.199X10-5 3 1.199X10-5 4 1.199X10-5 5 2.549X10-5

Finally the activation energy can be fiqure out from Arrhenius equation:

References

  傅献彩, 沈文霞, 姚天扬. 物理化学, 上册欧4 . 北京:高等教育出版社, 1990:144.
  清华大学化学系物理化学实验编写组. 物理化学实验. 北京：清华大学出版社, 1991.
  Robert C. Wcast Handbook of Chemistry and Physics. Physics. 58th ed. Ohio: CRC Press, 1977.
  朱文涛. 物理化学. 北京：清华大学出版社，1995.