CH4510: CRE AND TDC LAB

Study of Kinetics of Dye Oxidation Reaction

CH10B074: Vipindas CH10B075: Vipiul Gupta CH10B076: Yashwant Pankaj CH10B077: Abhinav Date of submission: 21/11/ 2013

Study of Kinetics of Dye Oxidation Reaction

1 Aim
o To determine the rate expression of the dye oxidation reaction (k, m and n) o To determine the order of reaction with respect to both the dye and oxidizer (sodium hypochlorite) o To determine the stoichiohmetric coefficient of the oxidizer (b)

2Apparatus required
Beakers, test tubes, test tube holder, spatula, weighing machine, spectrophotometer, computer, distilled water, dye, sodium hypochlorite solution (4% wt/vol equivalent to 40,000 ppm)

3 Procedure:
3.1 Solution Preparation

A master solution of concentration 5000 ppm was prepared by mixing 1 g of dye in 200 ml of distilled water. Solutions of various concentrations were prepared by mixing master solution and distilled water in appropriate proportions. The following table tells us what volumes of dye solution and distilled water are required in order to make a dye solution of specified concentration. Table 1:
Concentration of solution (ppm) 5000 500 400 200 100 50 25 25

Volume of solution (ml) 1 80 50 50 50 50

50 40

Volume of distilled water 99 (ml) 20 50 50 50 50

50 10

Concentration of resulting 500 solution 400 (ppm) 200 100 50 25

12.5 20

4 % wt/vol (equivalent to 40,000 ppm) Sodium hypochlorite (Oxidizer) solution was available. For reaction the solutions of various concentrations were prepared. The following table tells us what volumes of Oxidizer solution and distilled water are required in order to make a dye solution of specified concentration. Table 2: Proportions of dye solution

Concentration of solution (ppm) 40,000 400

Volume of solution (ml) 1 50

Volume of distilled water (ml) 99 50

Concentration of resulting solution 400 (ppm) 200

200 100 50 25 25

50 50 50
50 40

50 50 50
50 10

12.5 20

100 50 25

3.2 Determination of Wave Length Corresponding to Maximum Absorbance

Interface used for determination of wave length corresponding to maximum absorbance was opened on computer. Two couetts (one for reference and the other for determining samples absorbance) filled with distilled water were kept in spectrophotometer. Then absorbance corresponding various wavelengths were recorded (Blank run). This run acts like a reference for future readings. Later the couette containing distilled water was filled with 50 ppm solution and the wave length spectrum corresponding to this solution was obtained. From the spectrum, the wavelength corresponding to maximum absorbance was determined. The following figure shows the wave length spectrum of 50 ppm solution. Figure 1: Wave length spectrum corresponding to 50 ppm solution

From the spectrum, it was found that the wave length corresponding to maximum absorbance as 478 nm. The value of absorbance (intensity) corresponding to this wave length is 0.755567.

3.3 Calibration of Spectrophotometer

Choose the interface which measures the absorbance value of a given dye sample. A Blank Run was carried out by placing distilled water in both couettes. The wave length was kept at 478 nm (wave length corresponding to maximum absorbance). Once Blank Run is over, solutions of different concentrations (50, 100, 25 and 12.5 ppm) were placed in the spectrophotometer and

the absorbance value corresponding to each concentration was recorded. A least square solution was fitted for the data points. This equation was

used for estimating the concentration of a given solution whose absorbance is known. This completes the calibration process. The following table and figure shows data points and the least square fit. Table 3: Absorbance values corresponding to different dye concentrations Concentration (ppm) Absorbance 100 1.5119 50 0.755567 25 0.3714 12.5 0.1849 Figure 2: Calibration of spectrophotometer (Least square fit)
1.6 1.4 1.2 ABSORBANCE 1 0.8 0.6 0.4 0.2 0 0 20 40 60 CONCENTRATION (PPM) 80 100 120 Absorbance Least Square fit
y = 0.0151x R = 0.9999

4 Calculations
4.1 Reaction between 200 ppm dye and 200 ppm oxidizer
Concentration of the dye in the reacting mixture at t=0 (CA0) = 140.43 ppm (from spectrophotometer) Concentration of the oxidizer in the reacting mixture at t=0 (CB0) =200/2 = 100 ppm Figure 3 shows the absorbance of reacting mixture as a function of time and the Figure 4 shows polynomial fit for the first 10% data points. (Data points were converted to concentration units using calibration equation)

Figure 3: Absorbance of reacting mixture as a function of time

2.5

Absorbance

1.5

0.5

0 0 50 100 150 200

Time (s)

250

300

350

400

450

Figure 4: Polynomial fit for the first 10% data points

160 140 120 Experimental Data Polynomial fit

Concentration (ppm)

100 80 60 40 20 0 0 10 20 y = 7E-06x4 - 0.001x3 + 0.0608x2 - 3.0093x + 140.22 R = 1

Time (s)

30

40

50

Differentiating the polynomial equation with respect to time at t=0 gives the initial rate of reaction (-rA). Therefore, in this case the rate expression can be written as:
|=0 = = 0 | 0
=0

(3.0093) = 3.0093 = (140.43)

(100) . (1)

In this case CA0 is not equal to 100 ppm. This implies that the volume of both oxidizer and the dye are not same (could be because of an error in pipette).

4.2 Reaction between 100 ppm dye and 100 ppm oxidizer
While diluting the 200 ppm dye solution, accidentally excess water fell into the glass cylinder. So, instead of getting a 100 ppm solution we got a 94.11 ppm solution and the experiment was done with this solution. Concentration of the dye in the reacting mixture at t=0 (CA0) = 53.799 ppm (from spectrophotometer) Concentration of the oxidizer in the reacting mixture at t=0 (CB0) =100/2 = 50 ppm Figure 5 shows the absorbance of reacting mixture as a function of time and the Figure 6 shows polynomial fit for the first 10% data points. (Data points were converted to concentration units using calibration equation) Figure 5: Absorbance of reacting mixture as a function of time
0.9 0.8 0.7 0.6 Experimental Data

Absorbance

0.5 0.4 0.3 0.2 0.1 0 0 50 100 150 200 250 300 350 400 450

Time (s)

Figure 6: Polynomial fit for the first 10% data points

60 50 Experimental Data Polynomial Fit

Concentration (ppm)

40 30 20 10

y = 2E-06x4 - 0.0002x3 + 0.0086x2 - 0.6597x + 53.859 R = 1

0 0 10 20

Time (s)

30

40

50

Differentiating the polynomial equation with respect to time at t=0 gives the initial rate of reaction (-rA). Therefore, in this case the rate expression can be written as:
|=0 = = | 0 =0 0 (0.6597) = 0.6597 = (53.799)
(50) . (2)

4.3 Reaction between 25 ppm dye and 25 ppm oxidizer

Concentration of the dye in the reacting mixture at t=0 (CA0) = 12.563 ppm (from spectrophotometer) Concentration of the oxidizer in the reacting mixture at t=0 (CB0) =25/2 = 12.5 ppm Figure 7 shows the absorbance of reacting mixture as a function of time and the Figure 8 shows polynomial fit for the first 10% data points. (Data points were converted to concentration units using calibration equation) Figure 7: Absorbance of reacting mixture as a function of time
0.2 0.18 0.16 0.14 Experimental Data

Absorbance

0.12 0.1 0.08 0.06 0.04 0.02 0 0 100 200 300 400 500 600 700

Time (s)

Figure 8: Polynomial fit for the first 10% data points

14 12 Experimental Data polynomial Fit

Concentration (ppm)

10 8 6 4 2 y = -4E-09x4 + 5E-06x3 - 0.0002x2 - 0.0517x + 12.56 R = 1

0 0 10 20 30 Time (s) 40 50 60 70

Differentiating the polynomial equation with respect to time at t=0 gives the initial rate of reaction (-rA). Therefore, in this case the rate expression can be written as:
|=0 = = 0 | 0
=0

(0.0517) = 0.0517 = (12.563)

(12.5) . (3)

4.4 Reaction between 12.5 ppm dye and 12.5 ppm oxidizer
Concentration of the dye in the reacting mixture at t=0 (CA0) = 6.21 ppm (from spectrophotometer) Concentration of the oxidizer in the reacting mixture at t=0 (CB0) =12.5/2 = 6.25 ppm Figure 9 shows the absorbance of reacting mixture as a function of time and the Figure 10 shows polynomial fit for the first 10% data points. (Data points were converted to concentration units using calibration equation) Figure 9: Absorbance of reacting mixture as a function of time
0.1 0.09 0.08 0.07 Experimental Data

Absorbance

0.06 0.05 0.04 0.03 0.02 0.01 0 0 100 200 300 400 500 600 700

Time (s)

Figure 10: Polynomial fit for the first 10% data points
7 6 Experimental Data Polynomial Fit

Concentration (ppm)

5 4 3 2 1 0 y = -2E-08x4 + 2E-06x3 + 8E-05x2 - 0.0262x + 6.2226 R = 0.9998

10

20

30

Time (s)

40

50

60

70

Differentiating the polynomial equation with respect to time at t=0 gives the initial rate of reaction (-rA). Therefore, in this case the rate expression can be written as:
|=0 = = 0 | 0
=0

(0.0262) = 0.0262 = (6.21)

(6.25) . (4)

5 Determination of unknown parameters

5.1 Estimation of rate constant, order of reaction with respect to both species
Taking natural logarithm on both sides of equations (1), (2), (3) and (4) and writing it matrix for we get: 1 ln 140.43 ln 100 ln ln 3.0093 ln 0.6597 1 ln 53.799 ln 50 ] [ [ ]=[ ] ln 0.0517 1 ln 12.563 ln 12.5 ln 0.0262 ln 6.25 1 ln 6.21

41 = 43 31

Least square method was used to determine the unknown parameters. Therefore, the above equation was pre-multiplied with AT matrix and the resulting 3X3 system was solved simultaneously. This procedure is employed in MATLAB. The screen shot of the output is shown below: Figure 11: Screen shot of the output

Therefore the values of = . = . , = . =

.
. Hence, the required rate expression is = .

5.2 Estimation of stoichiometric coefficient (b)

For the reaction + , b corresponds to stoichiometric coefficient of oxidizer. It implies that one mole of dye requires b moles of oxidizer. On doing mole balance, a rate expression in terms of concentration was obtained. Consider the following table containing mole balance of each species.

Dye Oxidizer Initial concentration CA0 CB0 Moles consumed CA0XV* b CA0XV* CA CB0 bCA0X Concentration of remaining species *X = Conversion and V = Volume of solution Conversion can be written as CA0X = CA0 CA. Substituting this expression for conversion and writing the rate expression, we get = 1.49 103 2.2337

(0 (0 ))

0.7425

. (5)

Values of CA, CA0 and CB0 were substituted and rate of the reaction at different time instants was obtained from the polynomial approximation. b value was adjusted in such a way that the rate of the reaction obtained from both polynomial expression and the rate expression (Eq. (5)) are same. Reaction of 200 ppm dye solution with oxidizer was considered. The dots correspond to the rate of reaction obtained from the polynomial fit and the solid line correspond to the rate of the reaction obtained from Equation (5). The equation corresponding to the Experimental rate is 28 106 3 0.003 2 + 0.1216
3.0093

And the equation corresponding to solid line is given below. The concentration of A at different time intervals was obtained from experimental data. = 1.49 103 2.2337
3.5 3 Experimental rate Predicted rate

(100 0.55(140.43 ))

0.7425

rate of the reaction (ppm/s)

2.5 2 1.5 1 0.5 0 0 10 20

Time (s)

30

40

50

60

Therefore, values of the unknown parameters are shown in the following expression. + . = .
.
.

6 Validation of the rate expression

The data points available for the remaining two cases (50 ppm and 20 ppm cases) were used for validation.

6.1 Reaction between 50 ppm dye and 50 ppm oxidizer

The following figure shows (a). Absorbance value of the reaction mixture as a function of time and (b). The polynomial fit for concentration as a function of time for the first 10% data points. The polynomial expression was used to determine the rate of the reaction for the first 50 seconds. These values are represented as the experimental data in the validation graph. The values of the rate of the reaction were also estimated using the rate expression developed in the previous section. These two values i.e. experimental value and the predicted value were compared and conclusion was made based on the results. Figure 12: (a). Absorbance of the reactin mixture as a function of time (b). Polynomial fit for the first 10% of the data points
0.4 0.35 0.3

(a)

Experimental Data

24 23 22

(b)

Experimental Data Polynomial Fit

Concentration (ppm)

Absorbance

0.25 0.2

21 20 19 18 17 16 15 0 y = -3E-07x4 + 3E-05x3 - 0.0006x2 - 0.1131x + 23.068 R = 0.9998 10 20

0.15 0.1 0.05 0 0 100 200

Time (s)

300

400

500

Time (s)

30

40

50

Figure 13: Comparison of experimental rate with the predicted rate

0.16 0.14 Predicted rate Experimental Rate

Rate of the reaction (ppm/s)

0.12 0.1 0.08 0.06 0.04 0.02 0

10

20

Time (s)

30

40

50

60

6.2 Reaction between 50 ppm dye and 50 ppm oxidizer

The following figure shows (a). Absorbance value of the reaction mixture as a function of time and (b). The polynomial fit for concentration as a function of time for the first 10% data points. The polynomial expression was used to determine the rate of the reaction for the first 50 seconds. These values are represented as the experimental data in the validation graph. The values of the rate of the reaction were also estimated using the rate expression developed in the previous section. These two values i.e. experimental value and the predicted value were compared and conclusion was made based on the results. Figure 14: (a). Absorbance of the reaction mixture as a function of time (b). Polynomial fit for the first 10% of the data points
0.18 0.16 0.14 0.12 11.5 Experimental Data 11 10.5 Experimental Data Polynomial Fit

Absorbance

0.1 0.08 0.06 0.04 0.02 0 0 200

Concentration (ppm)

10

9.5 9 y = -5E-08x4 + 9E-06x3 - 0.0003x2 - 0.0403x + 11.181 R = 0.9999 0 20

8.5 8

Time (s)

400

600

800

Time (s)

40

60

80

Figure 15: Comparison of experimental rate with the predicted rate

0.07 Predicted value Experimental data

Rate of the reaction (ppm/s)

0.06 0.05 0.04 0.03 0.02 0.01 0 0 10 20 30 40 50

60

70

Time (s)

7 Results and Discussion

The balanced chemical equation for the oxidation of dye can be written as + .

. The rate expression for this reaction can be written as = .

Stoichiometric coefficient of the oxidizer = 0.55. Order of the reaction with respect to dye = 2.2337. Order of the reaction with respect to oxidizer = -0.7425 and the overall order of the reaction = 1.4912. The rate constant of the reaction = 1.49*10-3. On comparing theoretical rate and the experimental rate, it was found that the error in the predicted rate and the actual rate is as high as 35%. So, we concluded that the rate expression developed is not appropriate. This could be because of error in initial concentration of Oxidizer. If the volume of the dye and the oxidizer is not equal (as in the case of 200 ppm, 100ppm, and 50 ppm) the initial concentration of oxidizer cannot be estimated. This leads to an error in the estimation of the order of the reaction and the rate constant.

8 Conclusion
The developed rate expression is off from experimental values by at least 35%. So, this expression cannot be used to determine the rate of the reaction at different concentrations. The predicted rate of the reaction will be in between 35% of the actual rate. A better rate expression can be obtained by doing more number of experiments with repeats.