Department of Chemical Engineering University of San Carlos Technological Center Nasipit, Talamban, Cebu City

ChE 512L Chemical Engineering Laboratory 2

REACTION RATE KINETICS, TEMPERATURE EFFECTS AND PERFORMANCE OF A PLUG FLOW REACTOR (Tubular Flow Reactor)

An final report submitted to Engr. Ramelito Agapay Instructor, ChE 512L

By

Ancot, Mark Ervin T.

August 17, 2011 [1.] Introduction

1

Suppose a single-phase reaction,

aA + bB rR + sS The most useful measure of reaction rate for reactant A is then

-rA=-1VdNAdt=amount of A disappearingvolume(time),molm3.s

[1]

[2] The reaction rate is a function of the concentration of the reactants and the temperature. In general, the rate expression is: -rA = f(concentration dependent terms, temperature dependent terms) [3]

The algebraic equation (1 & 2) that relates rA to the species concentration is called the kinetic expression or rate law. The dependence of the reaction rate, -rA, on the concentrations of the species present is almost without exception determined by experimental observation. Although the functional dependence on concentration may be postulated from theory, experiments are necessary to confirm the proposed form. One of the most common general forms of this dependence is the power law model. Here the rate law is the product of the concentrations of the individual reacting species each of which is raised to a power such as the one shown in equation 3 (Fogler, 2006).
-rA=kCACB

[4] An elementary reaction is a single-step reaction where the reactants are converted directly to products without any intermediate steps. In its rate equation, the powers to which the concentrations of the reactants are raised are the same as the stoichiometric coefficients of the reaction. Supposing equation 1 is an elementary reaction, the rate law is,
-rA=kCAaCBb

[5]

The order of the reaction refers to the powers to which the concentrations are raised. For instance in equation 5, the reaction is a order with respect to A and b order with respect to B. The overall order of the reaction is a + b (Fogler, 2006). For many reactions, and particularly elementary reactions, the rate expression can be written as a product of a temperature-dependent term and a composition dependent term, or ri = f1(temperature) x f2(composition) = k f2(composition) [6]

For such reactions, the temperature-dependent term, the reaction rate constant, has been found practically all cases to be well represented by Arrhenius law: k = k0-Ea/RT [7]

where k0 is called the frequency factor or pre-exponential factor and Ea is called the activation energy of the reaction. This expression fits experiment well over wide temperature ranges and is strongly suggested from various standpoints as being a very good approximation to the true temperature dependency (Levienspiel, 1999). There are three types of ideal reactors namely, batch, mixed flow reactor, and plug-flow reactor. In the batch reactor, the reactants are initially charged into a container, are well mixed, and are left to react for a certain period. The resultant mixture is then discharged. This is an unsteady-state operation where composition changes with time; however, at any instant the composition throughout the reactor is uniform. A mixed flow reactor or a constant-stirred flow reactor it is a reactor in which the contents are well stirred and uniform throughout. A plug-flow reactor (PFR) is characterized by the fact that the flow of fluid through the reactor is orderly with no element of fluid overtaking or mixing with any other element ahead or behind. Actually, there may be lateral mixing of fluid in a plug flow reactor; however, there must be no mixing or diffusion along the flow path
(Levenspiel, 1999). The tubular flow reactor used in the experiment is an example of

a plug flow reactor.

[2.] Objectives

Determine the reaction order and the rate constant for the ethyl acetateNaOH reaction system using plug flow reactor data. Determine the variation of conversion with respect to the residence time. Verify the temperature dependence of the reaction rate constant.

[3.] Methodology [3.1] Materials

0.1 M NaOH solution 0.1 M ethyl actetate 0.1 M HCl 3 pcs 10 mL volumetric pipette 6 pcs 200 mL Erlenmeyer flasks 1pc stopwatch 2 pcs magnetic bars and stirrers base burette 1 pc 2L graduated cylinder

[3.2] Equipment

Tubular Flow Reactor (TFR) Specifications: (height=1.075m; width= 1m; depth=0.66m; reactor volume=0.4L)

[3.3] Procedure A. Feed Preparation and Equipment Pre-start-up 18 L of 0.1 M NaOH and 18 L of 0.1 M ethyl acetate were prepared and were standardized to determine their actual concentrations. To determine the actual concentration of ethyl acetate in the feed, 10 mL NaOH was mixed with 7 mL ethyl acetate feed and the solution was allowed to stand and react for 2 hours for complete conversion. This was done by continuous stirring of the mixture for 2 hours. Afterwards, the unreacted NaOH was titrated with 0.1M NaOH. The actual feed concentrations of NaOH and ethyl acetate were 0.0985mol/L and 0.1059mol/L, respectively. The prepared solutions were then poured to their respective tanks in the tubular flow reactor equipment. During the pre-start-up of the equipment, the water drain valve under the reactor water bath was closed. The beaker was removed in the sampling point and the outlet drain of the products was extended downward to the sump tray. The main water supply valve was fully open to supply water to the water bath, and then the two power supply circuit breakers were switched on. Afterwards, the temperature setting in the control console was set to 00 and then the main power switch was switch on. The stirrer was switched on when the water bath starts to overflow and also during this time the temperature setting in the control console was increased to 30. Then the two feed pump switches (ethyl acetate and NaOH) was switched on the flow rate of both feed were set to 255 cm3/min. This was maintained for 3 minutes to purge the trapped air and rinse the TFR. B. Experiment Proper B.1 Reaction Rate Kinetics and Plug-Flow Reactor Steady state Performance
5

The flow rates of the reactants were adjusted so that their molar flow rates are equal. In the first run, the flow rate of ethyl acetate and NaOH were set to 47cm3/min and 50cm3/min, respectively and the temperature setting in the control console was set as is to 30C. Steady-state was allowed to reach after two reactor volumes of effluent have accumulated. Effluent sampling was done at steady-state and the temperature of the reaction was taken during effluent sampling. Two10 ml effluent samples were collected in the sampling point of the products using a volumetric pipette. As soon as the 10 ml effluent sample was collected, 10.0 M HCl was immediately poured into it to stop the undergoing reaction between NaOH and ethyl acetate. Afterwards, two drops of phenolphthalein indicator was added to the sample and then the sample was titrated with 0.1 M NaOH to determine the concentration of the unreacted HCl so as to determine the concentration of the unreacted NaOH in the effluent. The same procedure was done with the first flow rate setting. The succeeding reactant feed flow rate settings (EtOAc : NaOH) in cm3/min were 93:100, 139: 150, and 186:200.

B.2 Influence of Temperature on Reaction Rate Constant The temperature setting in the control console was increased to 40C and the second flow rate setting in part B.1 was used which is 47:50 (EtOAc:NaOH) cm3/min. The reaction was allowed to reach steady state before two 10 mL effluent samples were collected. Similar procedure in part B.1 was done in taking and analyzing the effluent sample. The temperature of the reaction was also taken during effluent sampling For the second run, the temperature setting in the control console was set to 50C while maintaining the feed flow rate setting. Similar procedure was also done as in the first run (T=40C).

[4.] Results and Discussions Reaction Order and Reaction Rate Constant NaOH + CH3CH2OOCH3 CH3CH2O + CH3OO-Na+ [8]

The reaction order of the ethyl acetate-NaOH reaction[8] is determined by trial and error method that is assuming a certain reaction order. Since the said reaction is an elementary reaction, the reaction order must be an integer. As such, the reaction orders assumed were 0, 1, and 2. Applying least-square analysis of the data using the assumed reaction order, the assumed reaction order with the highest regression coefficient, r2 is the reaction order of the ethyl acetate-NaOH reaction.

Figure 1. Zero-order reaction model (rA = k) fit for the Ethyl acetate-NaOH reaction.

Figure 2. First-order reaction model fit (rA = kCA) for the Ethyl acetate-NaOH reaction.

Figure 3. Second order reaction model fit (rA = kCA2) for the Ethyl acetate-NaOH reaction.

Figures 1 and 2 show respectively that the zero-order and the first-order reaction model do not fit well with the data gathered. The ethyl acetate-NaOH reaction is best fitted by a second-order reaction model as shown in Figure 3 with r2 value equal to 0.9645. The reaction between ethyl acetate and NaOH therefore is a second order reaction. This means that the reaction is first order with respect to each of the reactant. Since the molar flow rates of the two reactants were set equal in this experiment, the rate equation then can be written as: rA = -kCA2 [9]

1 1 = + k CA C A0

where CA is the concentration of either of the reactants, k is the rate constant and rA is the rate of reaction. The rate constant is equal to the slope of the graph in Figure 3 and is calculated to be equal to 2.7959 L/mol-min. Thus, the rate equation for the ethyl acetate-NaOH reaction can be written as: rA = -2.7959CA2 [mol/L-min] [10]

Performance of the Tubular Flow Reactor Residence time or space time is defined as the time required to process one reactor volume of feed measured at specified conditions. The space time is defined as the ratio of the volume of the reactor to the feed volumetric flow rate. Since the volume of the reactor is constant (Vr = 0.4 L), the space time is only a function of the feed flow rate of the reactants. The flow rate is varied in the

experiment in order to determine its effects on the conversion and the data obtained are as shown in Table 2.

Table 2. Residence Time and Conversion Data (T = 31C).

vnet (mL/min) 97 193 289 386

(min) 4.1237 2.0725 1.3841 1.0363

CA(mol/L) 0.0316 0.0354 0.0395 0.0417

XA 0.3780 0.3056 0.2267 0.1828

Figure 4. Plot of XA vs (T=31C).

It can be seen from Figure 4 that by increasing the space time at constant temperature, T = 31C, the conversion of the reactants to products also increases. Increasing the flow rate decreases the space time which decreases the time of contact between the reactants in the reactor. Hence, the conversion decreases. To have higher conversion, the contact between the reactants should be increased by increasing the residence time of the elements of the fluid inside the reactor. This is done by decreasing the flow rates of the feed.

Temperature Dependence of the Reaction Rate Constant

To investigate the effect of temperature on the reaction rate constant, the temperature is changed at constant flow rate. In this experiment, the net flow rate 193 mL/min of the reactants is used.

Table 3. The effect of temperature on the rate constant, k.

T (C) 31 42 51.6

T (K) 304.15 315.15 324.75

(min) 2.0725 2.0725 2.0725

k (L/mol-min) 8.7145 11.8237 14.3448

Figure 5. Temperature dependency of the rate constant, k

Figure 3 shows that the rate constant, k, increases with an increase in temperature at constant residence time. The rate constant normally depends on the absolute temperature, and the functional form of this relationship was first proposed by Arrhenius in 1889 (Davis, et al., 2002). The model is shown in equation 7. In order to determine the frequency factor, the Arrhenius equation [7] is linearized to: ln k = -Ea/(RT) + ln k0 [11]

Taking the exponential of the y-intercept yields the frequency factor k0 which is equal to 4896347.12 L/mol.min. The slope of equation 10 multiplied by the gas constant 8.314J/mol-K gives the activation energy of the reaction which is equal
10

to 35390.2 J/mol or 35.39 kJ/mol. This value is 20% lower compared to the literature value of the activation energy of the ethyl acetate-NaOH reaction which is equal to 44 kJ/mol.

Figure 6. Plot of ln k vs 1/T

[5] Conclusion The ethyl k0= exp(15.404)=4896347.12 order reaction and the rate acetate-NaOH reaction is a second constant, k of the said reaction is found to be equal to 2.9759 L/mol.min at T = 31C. The rate constant, k is indeed a function of temperature as shown in figure 5. The extent of conversion increases with increasing space time.
[L/mol.min]

[6.] References Levenspiel, O. (1998) Chemical Reaction Engineering. 3rd Edition, John Wiley & Sons, Inc.,New York. Fogler, HS. Elements of Chemical Engineering. 4th Edition, Prentice Hall, New Jersey. Davis, M. & Davis, R. (2003). Fundamentals of Chemical Reaction Engineering. International Edition, McGraw-Hill Inc. ,Singapore.

11

12