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A.

SUMMARY

The topic investigated in this experiment was liquid phase chemical reactors with the effect of temperature on reaction rate constant. This is significant in Chemical Engineering because of the underlying importance it has in understanding how a chemical reaction works ( i.e. chemical kinetics). In addition, knowing the kinetics of a reaction will help chemical engineers in optimum reactor design. The major objective of this lab was to find the reaction rate constant in a batch stirred tank reactor for the saponification ethyl acetate with dilute sodium hydroxide. Another objective was to study the effect of temperature on reaction rate constant, and also to find the values of the rate constant and the Arrhenius parameters; activation energy, Ea and pre-exponential factor, A). In carrying out the experiment, a chemical reactor service unit fitted with batch chemical reactor was used (see figure 1 for the diagram of the experimental set up). From the experiment, some key results were obtained. One of such result was that for any given chemical reaction, the reaction rate is temperature dependent. Thus, an increase in temperature causes an increase in the reaction. Also, the conductivity of the reactants decreases with time as the reactants loses their ions and become less conductive. Another important finding was that as the concentration of the hydroxide reduces, the reaction rate increases. Going by the objectives of the lab, the Arrhenius parameters were estimated to be 197.87 and 501.625 kJ/mol respectively (i.e. the pre-exponential factor and activation energy). In addition, the reaction rate constant (k) for the reactions were estimated to be 0.0101 M-1s-1 at 25C, 0.2853 M-1s-1 at 30C and 0.0089 M-1s-1 at 40C respectively. From the experiment, it can be concluded that temperature plays a major part in chemical kinetics (rate increases as temperature increases). Also, in a chemical reaction, as the reactant (s) are been converted into products, the conductivity changes. Finally, in homogenous (same phase) reaction that is second order overall (first order in both components) like the one done in the lab, the concentration of the reactants also affects the reaction rate.

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B. INTRODUCTION: One of the major objectives of this lab was to find the reaction rate constant using a batch stirred tank reactor for the saponification ethyl acetate with dilute sodium hydroxide. Another objective was to study the effect of temperature on reaction rate constant, and also to find the values of the rate constant and the Arrhenius parameters; activation energy, Ea and pre-exponential factor, A). In the course of the experiment, the effect of concentration of reactants on a homogenous reaction was also considered. One of the three types of reactors in chemical processes is the batch reactor. In this type of reactor, the total feed is introduced at the beginning and no withdrawal is made until the reaction has reached the degree of completion desired; hence it is a closed system reactor. It differs from a continuous stirred tank reactor (CSTR) which has material exchange taking place during the reaction. For this experiment, a stirred tank batch reactor was used; meaning it has a stirrer to ensure continuous mixing of the reactants to aid in a homogenous concentration throughout the mixture. Another important thing to note about this type of reactor is that it works with an unsteady process (that is all variables change with time). Also, the mixture in the volume is assumed to be perfectly mixed (that is there will be uniform concentrations). In addition, temperature will be uniform throughout the reactor; however it may change with time (Basu, 2012). Also, batch reactors are often used for liquid-phase reactions particularly when the required production is small (Smith, 1981). Generally, the mass balance for a stirred tank reactor can be written as: Rate of change within the reactor = Input Output Loss by reaction. For any liquid phase chemical reactor with a constant volume such as the batch stirred tank reactor, this can be rearranged to give: Rate of change within the reactor = loss by reaction. Thus for any given reaction in constant volume, the rate equation can be given as: (1) Where: is the rate of disappearance of reactant A among the reacting species is the concentration of reactant A in the exit stream
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t is the time in seconds it takes for reactant A to disappear For a bimolecular reaction like the one in the experiment; the saponification of ethyl acetate with dilute sodium hydroxide which is given as:

The rate law for such reaction can be written as: (2) Where: is the rate constant n and m are appropriate powers based on experimental result is the concentration of reactant A in the exit stream is the concentration of reactant B in the exit stream Generally several factors could influence the rate of a chemical reaction. Some of these factors include: (i) (ii) (iii) (iv) (v) Temperature Concentration (if homogenous) State of reactants (that is if they are solid, liquid or gas) Order of reaction Pressure

Out of the above mentioned factors, the effect of temperature on the reaction rate was the one studied. Though, the effect of concentration was also observed because the reaction that was studied was a homogenous reaction. The relationship between reaction rate and temperature is explained by Arrhenius equation which is given as: (3)

Where: is the reaction rate constant is the universal gas constant is temperature is the activation energy (8.314 J mol-1K-1) (K) (J mol-1)

is Arrhenius constant or pre-exponential factor (s-1) for a first order reaction By applying natural logarithm to both sides, equation (3) can be re-written as: (4)
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From equation (4), a plot of

against 1/T would yield a straight line graph from

which A can be obtained as the intercept of the line at 1/T = 0. The activation energy (Ea) can be obtained from the slope of the graph which is given as Thus if the slope, S = , then the activation energy can be estimated as: (5) It is noteworthy to mention here that reactions with low activation energy are relatively temperature-insensitive while those with high activation energies are very temperature sensitive. Therefore, any given reaction is much more temperaturesensitive at a low temperature than at a high temperature (Levenspiel, 1999). From the above, it shows that the reaction rate constant has to be obtained first before applying Arrhenius equation to find the Arrhenius parameters. This can be done by referring to reaction to be studied: .

The rate of the reaction can be said to depend on the concentrations of both reactant A ( and reactant B ( . The order of the reaction studied is known to be first order with respect to both A, and B , hence second order overall. Thus by combining equation (1) and (2), an expression for the reaction rate constant in terms of the concentration of A and B can be obtained as: (6) Where: All the parameters are as defined in equation (2) If the initial concentration of reactant A (CA0) and reactant B (CB0) are made to be equal, then equation (6) can be reduced to: (7)

Integrating equation (7) yields:

(8)

Where:
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and

are as defined before. against will give a straight line

From equation (8), it can be seen that a graph of graph with slope equal to

(reaction rate constant) and intercept , the conductivity of the one of the reactants; in this

For the experiment, to calculate

case reactant A (Sodium hydroxide) can be measured at various time intervals. With this, the concentration of the hydroxide can be calculated as: (9)

Where: is the concentration of reactant A in the exit stream at time t is the initial concentration of NaOH is the conductivity of the solution at time t is the conductivity of the solution at the end of reaction is the initial conductivity at time t = 0 Note: can be found by plotting a graph of the measured conductivity (k) against time and extrapolating to t = 0. can also be found from the same graph by extrapolating to large t. The rationale for calculating the concentration of the hydroxide by evaluating conductivity is that the degree of conversion of reactants affects the conductivity of the reactant contents, so that recording the conductivity with respect to time helps to calculate the amount of conversion (Denbihh and Turner, 1971).

C.

EXPERIMENTAL EQUIPMENT
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The major equipment used in the experiment was a chemical reactor service unit fitted with batch chemical reactor. A diagram of the experimental set up is shown in figure 1. Other equipment used include; thermostatic bath to control the temperature stability of the two reactants to be added in at any time, 1 litre glass flasks containing the reactants, conductivity meter to measure the conductivity of the solution, stopwatch and stock solutions of 0.1M solution of sodium hydroxide and 0.1M of ethyl acetate. A batch reactor is one of the three types of reactors in chemical processes. It is similar to the continuous stirred tank reactor in the sense that the mixture in the volume is stirred but unlike the continuous stirred tank reactor where there is a continuous supply of feed while products are continually removed, in the case of the batch reactor; there is no inflow or outflow of material. The total feed is introduced at the beginning and no withdrawal is made until the reaction has reached the degree of completion desired.

This type of reactor is mostly used for liquid-phase chemical reactions, especially on a small scale. Thus when used for liquid-phase reactions, the reactor volume does not change significantly with the extent of reaction. For a gas-phase reaction, it may be constant pressure sometimes. In addition, since the mixture in the tank is assumed to be perfectly mixed, there will be uniform concentrations, and temperature will also be uniform throughout the reactor; however with time it may change. See figure 1 and 2 for a schematic diagram of a batch stirred tank reactor and the experimental set-up respectively. The picture of the experimental set up is also shown in figure 3.

Reactant components Stirrer

Figure 1: Schematic diagram of a batch stirred tank reactor Source: http://www.rpi.edu/dept/chem-eng/Biotech-Environ/IMMOB/stirredt.htm

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Figure 2: Schematic diagram of the experimental set up

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Ethyl acetate NaoH Temperature adjuster Reaction vessel Conductivity probe Conductivity meter Temperature probe

Figure 3: Diagram of the experimental set-up

D.

EXPERIMENTAL PROCEDURE AND OBSERVATIONS

For safety reasons safety goggles and protective gloves were worn during the course of the experiment advised to wear safety goggles and protective gloves. After this, 0.1M sodium hydroxide and 0.1 M ethyl acetate were provided to run the experiment. Then the reaction temperature was set to 25C on the thermostatic bath. Then the two 1 litre flasks were filled to the mark with sodium hydroxide solution and ethyl acetate solution respectively and placed in a bath. The reaction temperature was then set on the reactor control panel. After this, the conductivity meter was set and the probe end was placed in the bath to get to get to the reaction temperature. The flasks were also allowed to reach the reaction temperature.

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The 1 litre of sodium hydroxide solution was added to the reactor, followed by the 1 litre of ethyl acetate solution, and the clock was started when ca. 50% of ethyl acetate solution was added. After waiting for about 30 seconds, ca. 200ml was withdrawn an d the conductivity was measured, and then the sample was returned to the reactor while the probe was returned to the bath. The conductivity readings were taken every 30 seconds for about 10 minutes. It was then allowed to run for further 20 minutes and th e readings were taken after every 3 minutes. The experiment was then repeated for reaction temperatures of 30 C and 40C. Some observations were then made, one of which was that with time the conductivity of the solution decreases. This could be as a result of loses of ions in the solution, thereby making it less

conductive.

E.

RESULTS AND CALCULATIONS

The results (both experimental and calculated, and extrapolated results) obtained in the experiment are shown in table 1- 4 below. The graphs are shown in figures 3 - 9

Table 1: Measured conductivity values at different reaction temperatures


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t (s) 30 60 90 120 150 180 210 240 270 300 330 360 390 420 450 480 510 540 570 600 780 960 1140 1320 1500

Conductivity, k @ 25C (S/m) 1.511 1.398 1.308 1.246 1.188 1.140 1.100 1.066 1.037 1.011 0.988 0.968 0.950 0.934 0.918 0.906 0.893 0.882 0.871 0.862 0.818 0.787 0.765 0.748 0.735

Conductivity, k @ 30C (S/m) 0.601 0.544 0.498 0.462 0.431 0.407 0.387 0.37 0.355 0.343 3.33 0.324 0.317 0.31 0.305 0.3 0.296 0.292 0.289 0.287 0.276 0.271 0.268 0.266 0.265

Conductivity, k @ 40C (S/m) 1.698 1.511 1.386 1.304 1.246 1.199 1.161 1.13 1.105 1.084 1.065 1.049 1.035 1.022 1.011 1.001 0.984 0.976 0.969 0.955 0.936 0.913 0.896 0.882 0.87

Table 2: Calculated hydroxide concentration CA at different temperatures

t (s)

CA @ 25C

CA @ 30C

CA @ 40C
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30 60 90 120 150 180 210 240 270 300 330 360 390 420 450 480 510 540 570 600 780 960 1140 1320 1500

0.1250 0.1156 0.1082 0.1031 0.0983 0.0943 0.0910 0.0882 0.0858 0.0836 0.0817 0.0801 0.0786 0.0773 0.0759 0.0749 0.0739 0.0730 0.0720 0.0713 0.0677 0.0651 0.0633 0.0619 0.0608

0.1383 0.0710 0.0593 0.0501 0.0422 0.0361 0.0310 0.0267 0.0229 0.0198 0.0173 0.0150 0.0132 0.0115 0.0102 0.0089 0.0079 0.0069 0.0061 0.0056 0.0028 0.0015 0.0008 0.0003 0.000

0.1322 0.1177 0.1079 0.1015 0.0970 0.0934 0.0904 0.0880 0.0860 0.0844 0.0829 0.0817 0.0806 0.0796 0.0787 0.0779 0.0766 0.0760 0.0754 0.0744 0.0729 0.0711 0.0698 0.0687 0.0677

Table 3: Calculated reciprocal of hydroxide concentration (1/CA) at different temperatures.

t (s)

1/CA @ 25C

1/CA @ 30C

1/CA @ 40C
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30 60 90 120 150 180 210 240 270 300 330 360 390 420 450 480 510 540 570 600 780 960 1140 1320 1500

8.001 8.648 9.243 9.703 10.177 10.605 10.991 11.341 11.659 11.958 12.237 12.490 12.726 12.944 13.170 13.344 13.539 13.707 13.881 14.026 14.780 15.362 15.804 16.163 0.000

7.231 14.086 16.867 19.949 23.675 27.676 32.213 37.429 43.667 50.385 57.794 66.610 75.577 87.333 98.250 112.286 126.774 145.556 163.750 178.636 357.273 655.000 1310.000 3930.000 0.000

7.564 8.500 9.266 9.849 10.307 10.711 11.062 11.365 11.623 11.848 12.059 12.243 12.409 12.567 12.703 12.830 13.052 13.159 13.254 13.448 13.721 14.067 14.334 14.561 0.000

Initial Initial conductivity,k0 conductivity,k0 @ 25C (S/m) @ 30C (S/m)

Conductivity Conductivity Conductivity at end of at end of at end of Initial reaction, k reaction, k reaction, k conductivity,k0 @ 25C @ 30C @ 40C @ 40C (S/m) (S/m) (S/m) (S/m)
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1.209

0.4346

1.2843

Table 4: Extrapolated data

k0 was extrapolated to t = 0 from a graph of measured k against t in figure 4, 5 and 6 k was extrapolated to large t from a graph of measured k against t in figure in figure 4, 5 and 6.

Table 5: Reaction rate constants at different temperatures

Reaction rate constant, k @ 30C ( M-1s-1 )

Reaction rate constant, k @ 30C ( M-1s-1 )

Reaction rate constant, k @ 40C ( M-1s-1 )

0.0101

0.2853

0.0089

These values were obtained from figures 7, 8 and 9.

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1.600 1.400 1.200 1.000 0.800 0.600 0.400 0.200 0.000 0 200 400 600 800 Time, t (seconds) 1000 1200 1400 1600

Measured conductivity, k (S/m)

y = -0.0004x + 1.209

Figure 4: Graph of conductivity against time at reaction temperature of 25 C

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0.700 0.600

Measured Conductivity, k (S/m)

0.500 0.400 0.300 0.200 0.100 0.000 0 200 400 600 800 1000 1200 1400 1600

y = -0.0002x + 0.4346

time, t (seconds)

Figure 5: Graph of conductivity against time at reaction temperature of 30 C


1.800 1.600

Measured Conductivity, k (S/m)

1.400 1.200 1.000 0.800 y = -0.0004x + 1.2843 0.600 0.400 0.200 0.000 0 200 400 600 800 1000 1200 1400 1600

time, t (seconds)

Figure 6: Graph of conductivity against time at reaction temperature of 40 C

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16 14 12 10 1/CA (M) 8 6 4 2 0 0 100 200 300 400 500 600 700 time, t (seconds) y = 0.0101x + 8.5495

Figure 7: Graph of 1/CA against time at reaction temperature of 25 C


200

150

y = 0.2853x - 20.577

100 1/CA (M) 50

0 0 -50 100 200 300 400 500 600 700

time, t (seconds)

Figure 8: Graph of 1/CA against time at reaction temperature of 30 C

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16.000 14.000 Measured conductivity, k (S/m) 12.000 10.000 8.000 6.000 4.000 2.000 0.000 0 100 200 300 400 500 600 700 y = 0.0089x + 8.6792

time, t (seconds)

Figure 9: Graph of 1/CA against time at reaction temperature of 40 C


0 0.00329 0.0033 0.00331 0.00332 0.00333 0.00334 0.00335 0.00336 -0.5 -1 -1.5 -2 In k -2.5 -3 -3.5 -4 -4.5 -5 y = -60335x + 197.87 1/T (K) Series1 Linear (Series1)

Figure 10: Graph of In (k) against 1/T showing the effect of temperature on reaction rate constant.

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Note: When plotting the graph of ln (k) against 1/T, the value of the reaction rate constant (k) gotten when the reaction temperature was 40 C as shown in figure 9 was not used. This was because from the readings gotten from the experimental as shown in table 1, an experimental error was suspected to have occurred thereby giving wrong readings. This error could possibly be in the reading of the conductivity meter.

SAMPLE CALCULATIONS: (A) Sample calculation for the concentration of the hydroxide. Hydroxide concentration at 25C in 30 seconds.

Using equation (9) When CA0 = 0.1 M, k (t) = 1.511 S/m, k = 0, k0 = 1.209 = 0.1250 M 1/CA = 1/0.1250 = 8.001 Using same procedure, the hydroxide concentration (CA) and its reciprocal (1/CA) at 30C and 40C at various time intervals were also calculated. (B) Calculation of Arrhenius parameters (A and Ea)

From equation (4): A graph of In (k) against 1/T as shown in figure 8 will yields a straight line with intercept A Arrhenius parameter (A) = 197.87 Activation energy (Ea): From equation (5): Where slope in figure 8 = - 60335, R = 8.314 *10-3 kJ mol K-1 8.314 *10-3) = 501.625 kJ/mol = 501625.19 J/mol

F.

DISCUSSION OF RESULTS:
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From the results obtained in the experiment, it shows that reaction rate is dependent on temperature, through the dependence of reaction rate constant on k on temperature T. This can be seen from figure 9 where a plot of In (k) against 1/T gave a straight line graph. This can also be seen from table 1 where at a temperature of 25 C, the reaction rate constant was 0.010 M-1s-1, while at 30 C it was 0.2853 M-1s-1 . At 40 C, the reaction rate constant was 0.0089 M-1s-1. Thus reaction rate increases with an increase in temperature. This is because as temperature increases, the reactants will acquire a lot of kinetic energy; hence there will be more collision between the reacting molecules. In addition, this temperature rise will also bring the reaction closer to its activation energy which is the minimum amount of energy needed for a chemical reaction to occur. It is noteworthy to mention here that even though there is suppose to be an increasing trend in the reaction rate with time, at 40 C there was a decrease. The reason could be because of an experimental error. This could be due to the readings of the conductivity meter. Thus when a graph of In (k) was plotted against 1/T to estimate the Arrhenius parameters, the values of the reaction rate constant (k) obtained when the temperature was 40 C was not used so as to obtain a straight line (linear) graph. From figures 3, 4 and 5, it shows that conductivity decreases with time. This is could be due to loses of some ions. This can also explain why at the start, only sodium hydroxide would contribute to the conductivity. As reaction proceeds, sodium acetate would start forming after consumption of sodium hydroxide resulting in different conductivity results (Fogler, 1999). Hence in the experiment carried out, there was a reduction in the concentration of the hydroxide (NaOH) at various time intervals. The reason for this could be that since it is a batch reactor, the reactants would be converted into products while remaining in the reactor since there is no inflow or outflow; thus as the reactants are been converted into products, there would be less and less reactant and more and more products. It can then been inferred that close to time t = 0, there would be a lot of reactant and little product while close to time = infinity, there would be more product and less reactant (Missen et al, 1999).
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Finally, this goes to show that for a second order reaction (first order in each reacting components) like the saponification of ethyl acetate with dilute sodium hydroxide, the reaction rate is also dependent on one or both of the reactants concentrations; in this case that of the sodium hydroxide. For the reaction studied in this experiment, a decrease in one of the reactant concentrations; in this case sodium hydroxide causes and increase in the reaction rate. This is in line with the collision theory.

G.

CONCLUSIONS:

From the experiment, the following conclusions can be drawn. (i) The rate of a chemical reaction is temperature dependent. It increases with an increase in temperature and vice versa. (ii) In a batch reactor, since there is no inflow or outflow, the reactants concentration reduces with time. (iii) For an overall second order reaction (first order in both components) like the one that was done in the lab, the reaction rate is also dependent on the concentration of the reactants unlike a zero order reaction that is independent of the concentrations of the reactants. (iv) Conductivity of a solution reduces with time as the solution loses it ions and become less conductive.

Nomenclature

Symbols A

Units

Meaning Arrhenius parameter (pre-exponential factor)


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CA

CA0 CB

M M

exit concentration of reactant A in the exit stream input concentration of A in the input stream concentration of reactant B in the exit stream Arrhenius parameter (activation energy) Reaction rate constant Conductivity of solution at various time intervals initial conductivity at time t = 0

Ea

kJ/mol M-1s-1

k k0

S/m S/m

S/m

conductivity of the solution at the end of reaction Order of reaction of reactant component A Order of reaction of reactant component B

n T C

Reaction temperature

References: Denbihh, K. G., and Turner, J. C. R. (1971) Chemical Reactor Theory. 2nd ed. Cambridge: Cambridge University Press. Fogler, H.S. (1999) Elements of Chemical Reaction Engineering. 3rd ed .New Jersey: Prentice Hall.
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Levenspiel, O. (1999) Chemical Reaction Engineering. 3rd ed. New York: John Wiley & Sons, Inc., Missen, R. W., Charles, A. M. and Bradley, A. S (1999) Introduction to Chemical Reaction Engineering and Kinetics. 3rd ed. New York: John Wiley & Sons, Inc., Smith, J.M. (1981) Chemical Engineering Kinetics. 3rd ed .New York: McGraw-Hill.

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