Experiment 8 Solution Kinetics: Oxidation of Ethanol by Dichromate

Introduction The oxidation of ethanol (E) by dichromate (D) is represented by the reaction:
3 CH3CH2OH + Cr2O72- + 8 H+ E D 3 CH3CHO + 2 Cr3+ + 7 H2O P

The product ethanal (P) can be further oxidized to ethanoic acid. We will run this experiment with a large excess of ethanol so that dichromate will preferentially oxidize the ethanol and not the product ethanal. The rate law can be written as:
d [ P] d [ D] = = k[ E ][ D] ------ (1) dt dt The reaction will be first order in E, first order in D, and second order overall. We will use a large excess of ethanol. Consequently, the ethanol concentration will remain almost constant throughout and the reaction will be pseudo 1st-order.

d [ D] = k '[ D] ------ (2) where k=k[E] dt

On integration this becomes:

ln

[ D]o = k ' t ------(3) [ D]

The dichromate ion has a yellow-orange color and is readily monitored by its absorption in the blue region of the four-channel photometer. To study the reaction kinetics we monitor the concentration of dichromate in an excess of ethanol, by measuring the absorbance A. A is directly proportional to the concentration of dichromate. At time zero the absorbance is Ao while the initial concentration of dichromate is [D]o. The concentration of dichromate at time t is [D] and the absorbance is At. At long times, t, some absorption will remain and A0 and this background absorption must be corrected for all our measurements.

Expt.8-1

The equation becomes:

ln(

Ao A ) = k ' t or ln( Ao A ) ln( At A ) = k ' t ------(4) At A

Plot ln( At A ) versus t will be a straight line whose slope equals -k. The temperature dependence of the rate constant is described by the Arrhenius equation:
Ea

k = ae RT ------(5)

where a is the preexponential factor and Ea is the activation energy. In our case we measure a pseudo first order rate constant k, that can be used to determine the second order rate constant k. where k = k x (concentration of ethanol)
k' concentration of ethanol
Ea RT 1 will T

k=

In logarithmic form:
ln k = ln a

If rate constants are available at several temperatures, a plot of ln k versus have a slope Ea and an intercept ln a. R T should be in absolute temperature.

Procedure Preparation of reagents

1. Prepare 250 mL of a stock solution of 4 M sulfuric acid. 2. Prepare 100 mL of 0.02 M potassium dichromate solution. 3. Obtain 10 mL of absolute ethanol. 4. Pipet 5 mL of dichromate solution and 50 mL of the stock sulfuric acid in a conical flask. Shake the solution well.
Expt.8-2

Running the experiment at room temperature

1. Measure the blank potential Eo by using the 4 M sulfuric acid. 2. Place the acidic dichromate solution in a water bath at room temperature for a few minutes (record the temperature). (Fig. 1) 3. Add 0.15 mL pure ethanol into the acidified dichromate solution and start the timer immediately. 4. Stir the solution. 5. When the time is getting close to 1-minute interval, use a dropper to transfer a few mL of solution to the measuring cell. 6. Measure the potential by the 4-channel photometer. (Fig. 2) 7. Repeat the measurements at 2, 3, 4 and 5 minute intervals. 8. Allow the reaction solution to stand undisturbed for 30 minutes. (Fig. 3) 9. Determine the absorbance corresponding to the infinite time.

Fig. 1

Fig. 2

Fig. 3

Repeat the experiment at different temperatures 1. Prepare an ice-water bath and repeat the experiment. (Fig. 4)
2. Use a heater to maintain the temperature of water bath at about 30C. Repeat the experiment. (Fig. 5)

Fig. 4
Expt.8-3

Fig. 5

Measuring the absorbance 1. Turn on the photometer and select the blue LED at least 5 minutes before measurement. 2. Measure the blank TP2 potential Eo of the blank solution (4 M sulfuric acid). 3. Measure the TP2 potential E of the reaction solution. 4. The absorbance can be calculated: A = log
Eo E

Results
Blank potential Eo = Time (min) 1 2 3 4 5 Room temp. ( E (V) A C) Low temp. ( E (V) C) A High temp. ( E (V) C) A

Data Treatment
Assume the addition of ethanol does not change the volume of acidified dichromate solution. 1. Calculate the initial concentrations of dichromate ion and ethanol in the solution. Can we assume the concentration of the ethanol constant throughout the reaction? 2. Plot ln( At A ) versus t for each run and determine the pseudo first order rate constant k. 3. Calculate the second order rate constant k for each run. 1 and determine the activation energy and the preexponential T

4. Plot ln k versus
factor.

Reference
1. P. W. Atkins, Physical Chemistry, 7th Ed., Oxford University Press, 2002.

Expt.8-4