1. THEORY 1.1 Classification of Reactors Chemical reactors may be operated in batch, semi-batch, or continuous modes.

When a reactor is operated in a batch mode, the reactants are charged, and the vessel is closed and brought to the desired temperature and pressure. These conditions are maintained for the time needed to achieve the desired conversion and selectivity, that is, the required quantity and quality of product. At the end of the reaction cycle, the entire mass is discharged and another cycle is begun. Batch operation is labor-intensive and therefore is commonly used only in industries involved in limited production of fine chemicals, such as pharmaceuticals. In a semi-batch reactor operation, one or more reactants are in the batch mode, while the other reactant is fed and withdrawn continuously. In a chemical reactor designed for continuous operation, there is continuous addition to, and withdrawal of reactants and products from, the reactor system. [1]

1.2 Design Equations of Reactors 1.2.1 Batch Reactors General Mole Balance on System Volume V In Out + Generation = Accumulation There is no inflow or outflow during the process in batch reactors. (1)

Assumptions Well mixed (2) (3)

Rearranging and integrating with limits t=0 t = t1 NA = NA0 N A = NA1 (4)

Multiplying by -1 for the reagent A that becomes consumed and changing the limits of integration (5)

This equation gives the time t1 necessary to reduce the number of moles in a batch reactor from NA0 initially to NA1. [2]

1.2.2 Perfect Mixture Continuous Reactors Assumptions Steady State (6) Well mixed (2)

(7)

(8) Figure 1.1. CSTR diagram [3]

This equation gives the CSTR volume necessary to reduce the entering molar flow rate from FA0 to the exit molar flow rate FA1 when species A is disappearing at a rate -rA. [2]

1.2.3 Tubular Reactor Design

Figure 1.2 Cut through a tubular reactor showing (PFR) showing the volume part [4]

Steady State (6) (9)

Differentiate with respect to V (10) (11) Rearranging and integrating between V = 0 FA = FA0 V = V1 FA = FA1 (12) 4

This equation gives the PFR Volume, V1 necessary to reduce the entering molar feed rate from FA0 to the exit molar feed rate FA1 by chemical reaction. [2]

Table 1.1 Reactor Mole Balances In Terms of Conversion [2]

2. EXPERIMENTAL METHOD 2.1 The Aim of the Experiment The aim of the experiment is to learn batch and CSTR systems, their working principles and differences, investigation of the reaction rate constant and reaction order. The experiment was also performed to understand how the reaction rate constant changes with temperature according to Arrhenius Equation and also to learn how to find the conversion. 2.2 Equipment Description 2.2.1 Base Module and Interface In this part, the necessary elements for the use of the diverse reactor modules were provided. Constituted by; Feeding circuits of reagents Flow control system: Two dosing pumps two flowmeters of direct measure for the feeding pumps and also another rotation meter to measure the flow of liquids. Temperature control system Data acquisition and process control system Collecting circuit of products 2.2.2 Chemical Reactor Module in Liquid Phase Pyrex-glass reactor insulated with its maximum capacity of 2 liters. Agitation system with speed control helped the study of the influence of agitation in continuous or discontinuous system. Conductivity cell with conductimeter connected to the electronic module and allowed measuring the evaluation of the reaction in real time.

2.2.3. Accessories used in the experiment Ethyl acetate and Sodium hydroxide are necessary as chemical reagents, as laboratory materials 5L plastic cans, draining containers are needed and they are required as services 210 V /50 Hz. Electric supply and water supply.

2.3 Experimental Procedure 2.3.1 Discontinuous Isothermal Operation (Batch System) 2.3.1.a Obtaining the reaction rate constant (k) and the reaction order ( ) with respect to ethyl-acetate In this experiment, firstly, computer controlled system was started and water was recirculated until a constant flow was obtained. Thermal system was started and the desired working temperature was set to 25 C. Sodium hydroxide valve was opened to the to reactor position and it was allowed 0.02M and 1 L solution to the reactor. When the desired amount of reactant had been in the reactor, the valve was arranged to the recirculation position. Then the stirrer was started and waited for the temperature of 25 C. After that, ethyl-acetate valve was arranged to the to reactor module and it was allowed 1L of 1M solution to the reactor and, the valve was arranged to the recirculation position. When the conductivity had been stayed constant, the reaction was finished. Then, the stirrer was closed and the reactor was emptied. Also experiment was finished with clearing equipment with pure water.

2.3.1.b Variation of the kinetic constant with temperature, Arrhenius Equation In the first part of experiment repeated in temperature of 35 C and k changing with temperature was obtained according to Arrhenius Equation.

2.3.2 Continuous Operation, CSTR System In this part of the experiment, as in the first part, firstly, the program was started and the working temperature was set to 25 C. An equal flow for both reactants was set and the system was kept in recirculation position. When a steady flow was achieved, the valve was turned to the to reactor position. After the reactant level had been reached the stirrers blades, the stirrer system was started. The system was kept working for 1 hour. After that, the reactant valves were turned to the recirculation position and the system was stopped.

3. RESULTS AND DISCUSSION 3.1 Semi- batch/Batch System (25C) For a semi-batch system, reaction was started with 1 L of 0,02 M NaOH solution in the reactor. 1 L of 1M CH3 COOC2H5 solution was added gradually with constant flow rate to the reactor. By the time conductivity values was recorded by computer program with 60 s intervals. End of the reaction determined by observing stabilizing of conductivity values. Ethyl Acetate was used as excess reactant in this process. Table 3.1 shows the moles and concentration values of produced Sodium Acetate after the reaction ended.

Table 3.1 Stoichiometric Table

Species CH3COONa Initially 0 Change (moles) 0,0188 Remaining Concentration (moles) (mol/L) 0,0188 0,0011 Conversion 0,85

The data that was used in the experiment is shown below for 25C. The calculation methods can be seen from sample calculations part in appendix. Colored rows shows when the reactor became batch reactor (reaches 2 L volume).

Table 3.2 Experimental Value at 25 C Time (s)

60 120 180 240 300 360 420 480 540 600

Conductivity (mS)
3,525193115 3,064170410 2,223489746 1,543054810 1,197494995 1,052932251 0,982966370 0,934389404 0,896102112 0,868851929

Volume CEtoNa (L) (mol/L)

1,06 1,11 1,17 1,22 1,28 1,33 1,39 1,44 1,50 1,56 0,0011 0,0031 0,0047 0,0056 0,0059 0,0061 0,0062 0,0063 0,0064 0,0064

NEtoNa (mol)
0,0012 0,0035 0,0055 0,0068 0,0076 0,0081 0,0086 0,0091 0,0095 0,0100

NNaOH CnaOH (dCNaOH/dt) CNaOH. v/V NEtoNa (mol) (mol/L) (mol/L.s) (mol/L.s)
0,0188 0,0165 0,0145 0,0132 0,0124 0,0119 0,0114 0,0109 0,0105 0,0100 0,0178 0,0149 0,0124 0,0108 0,0097 0,0089 0,0082 0,0076 0,0070 0,0064 -0,00010651 -9,7485E-05 -6,2676E-05 -3,9207E-05 -2,9042E-05 -2,5054E-05 -2,2639E-05 -1,9508E-05 -1,9553E-05 -1,7867E-05 1,56529E-05 1,24047E-05 9,84172E-06 8,17772E-06 7,05597E-06 6,19281E-06 5,46760E-06 4,84355E-06 4,30735E-06 3,81803E-06

660 720 780 840 900 960 1020 1080 1140 1200

0,832312744 0,801241028 0,773123657 0,748850220 0,729047791 0,726464844 0,728982544 0,728025391 0,727817871 0,726019226

1,61 1,67 1,72 1,78 1,83 1,89 1,94 2,00 2,06 2,11

0,0065 0,0066 0,0066 0,0067 0,0067 0,0067 0,0067 0,0067 0,0067 0,0084

0,0105 0,0110 0,0114 0,0119 0,0123 0,0126 0,0130 0,0134 0,0138 0,0178

0,0095 0,0090 0,0086 0,0081 0,0077 0,0074 0,0070 0,0066 0,0062 0,0022

0,0059 0,0054 0,0050 0,0046 0,0042 0,0039 0,0036 0,0033 0,0030 0,0010

-1,6634E-05 -1,5421E-05 -1,4729E-05 -1,2107E-05 -1,0662E-05 -1,0470E-05 -9,7343E-06 1,94869E-05 -8,2316E-05 -5,1990E-05

3,38885E-06 3,00864E-06 2,67225E-06 2,37505E-06 2,12779E-06 1,91088E-06 1,71114E-06 1,53110E-06 1,36604E-06 4,56037E-07

dCNaOH +CNaOH. v/V (mol/L.s)

9,08615E-05 8,50808E-05 5,28340E-05 3,10296E-05 2,19860E-05 1,88613E-05 1,71717E-05 1,46642E-05 1,52453E-05 1,40489E-05 1,32449E-05 1,24120E-05 1,20570E-05 9,73227E-06 8,53373E-06 8,55953E-06 8,02320E-06 1,01000E-06 8,09504E-05 5,15344E-05

ln(-dCNaOHCNaOH. v/V)
-9,306174448 -9,371909371 -9,848355786 -10,38056982 -10,72510525 -10,87839918 -10,97225038 -11,13010175 -11,09124220 -11,17296972 -11,23189482 -11,29684868 -11,32586692 -11,54006300 -11,67148392 -11,66846495 -11,73317305 -13,80217981 -10,42167336 -10,87326078

ln(CNaOH) (mol/L)
-4,02607 -4,20735 -4,39000 -4,52870 -4,63178 -4,71970 -4,80343 -4,88540 -4,96498 -5,04920 -5,13335 -5,21845 -5,30423 -5,39037 -5,46954 -5,54721 -5,62862 -5,71162 -5,79829 -6,86872

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0,025 0,02 0,015 0,01

Concentration (mol/L)

NaOH
EtONa

0,005
0 0 500 Time (s) 1000 1500

Figure 3.1 Variations of Concentrations with Time

Obviously, meantime reaction is going on reactants ( CH3 COOC2H5 and NaOH) concentrations are decreasing, and the products (CH3COONa and C2H5OH) concentrations are increasing with time until equilibrium is achieved. Decrease in the CH3COOC2H5 is negligible. Because of it is assumed excess reactant. This part of the experiment is done at approximately at 25 C.

0 -8 ln(-dCNaOH+ CnaOH. v/V) -7 -6 -5 -4 -3 -2 -1 -2 -4 y = 0,8528x - 6,6611 R = 0,3334 -6 -8 -10 0

-12
-14 lnCNaOH -16

Figure 3.2 Determination of the Reaction Order () and the Reaction Rate Constant (k) 11

ln(-dCNaOH CNaOH.v/V) and ln(CNaOH) values was calculated at the Table 3.2 to find the reaction rate and reaction rate constant k from the semi -batch design equation. To calculate dC A/dt values one of the differential methods (finite differential method) is used. From the slope of the curve the reaction rate is determined. The reaction rate constant is determined by using the intercept of x-coordinate.

T(oC) 25

0,85

k 0,0965

Xfinal 0,85

tfinal (min) 35,45

It can be seen that at 25C reaction rate is found as 0,85 and reaction rate constant is found as 0,0965. Theoretically reaction of ethyl acetate is first order and our result is acceptable accuracy. Also reaction is assumed isothermally for this operation.

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3.2 Semi- batch/Batch System (35C) To study the effect of temperature on reaction order and reaction coefficient, temperature value changed 25oC to 35oC. As in the first part of the experiment the reactor was filled with 1 L of 0,02 M NaOH solution, 1 L of 1M CH3COOC 2H5 solution was added to the reactor gradually.

Table 3.3 shows the moles and concentration values of produced Sodium Acetate after the reaction ended. Table 3.3 Stoichiometric Table Initally Changing Remaining Concentration (mol) (mol) (mol) (mol/l) 0 0,01367 0,01367 0,006478045

Species CH3COONa

Conversion

0,69

The data that was used in the experiment is shown below for 35C. The calculation methods can be seen from sample calculations part in appendix. Colored rows shows when the reactor became batch reactor (reaches 2 L volume). Table 3.4 Experimental Value at 35 C Time Conductivity Volume (s) (mS) (L)
60 120 180 240 300 360 420 480 540 600 660 720 3,202790527 2,193194824 1,539539062 1,281099121 1,170795654 1,097239014 1,042470459 0,996847595 0,963058899 0,927184753 0,899407104 0,873949890 1,05556

CEtoNa (mol/L)

NEtoNa (mol)

NNaOH CNaOH. CnaOH (dCNaOH/dt) NEtoNa v/V (mol/L) (mol/L.s) (mol) (mol/L.s)
0,02 0,018947 -0,000126227 1,6620E-05

1,11294E-09 1,17E-09

1,11112 0,002375520 0,002639 0,017361 0,015624 -9,66378E-05 1,3020E-05 1,16668 0,003913534 0,004566 0,015434 0,013229 -5,31839E-05 1,0499E-05 1,22224 0,004521628 0,005527 0,014473 0,011842 -3,47971E-05 8,9709E-06 1,27780 0,004781166 0,006109 0,013891 0,010871 -2,91156E-05 7,8772E-06 1,33336 0,004954240 0,006606 0,013394 0,010045 -2,54243E-05 6,9759E-06 1,38892 0,005083107 0,007060 0,012940 0,009317 -2,31883E-05 6,2109E-06 1,44448 0,005190455 0,007498 0,012502 0,008655 -2,02734E-05 5,5482E-06 1,50004 0,005269958 0,007905 0,012095 0,008063 -1,95520E-05 4,9770E-06 1,55560 0,005354368 0,008329 0,011671 0,007502 -1,75409E-05 4,4656E-06 1,61116 0,005419727 0,008732 0,011268 0,006994 -1,63068E-05 4,0192E-06 1,66672 0,005479626 0,009133 0,010867 0,006520 -1,49540E-05 3,6221E-06

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780 840 900 960 1020 1080 1140 1200

0,850325195 0,821458862 0,799355713 0,781799927 0,776269531 0,772639404 0,772503357 0,772023804

1,72228 0,005535214 0,009533 0,010467 0,006077 -1,49928E-05 3,2673E-06 1,77784 0,005603134 0,009961 0,010039 0,005646 -1,36099E-05 2,9408E-06 1,83340 0,005655142 0,010368 0,009632 0,005254 -1,28494E-05 2,6532E-06 1,88896 0,005696450 0,010760 0,009240 0,004891 -1,08725E-05 2,3976E-06 1,94452 0,005709462 0,011102 0,008898 0,004576 -1,02030E-05 2,1789E-06 2,00008 0,005718004 0,011436 0,008564 0,004282 -9,24329E-06 1,9821E-06 2,05564 0,005718324 0,011755 0,008245 0,004011 -0,000450806 1,8067E-06 2,11120 0,005719452 0,012075 0,007925 0,003754 -1,34033E-05 1,6463E-06

-dCNaOH -CNaOH. v/V (mol/L.s)

0,00010961 8,3618E-05 4,2685E-05 2,5826E-05 2,1238E-05 1,8448E-05 1,6977E-05 1,4725E-05 1,4575E-05 1,3075E-05 1,2288E-05 1,1332E-05 1,1725E-05 1,0669E-05 1,0196E-05 8,4748E-06 8,0241E-06 1,0134E-06 0,00044900 1,1757E-05

ln(-dCNaOH- CNaOH. v/V)

-9,11861 -9,38926 -10,0617 -10,5641 -10,7597 -10,9005 -10,9836 -11,1260 -11,1362 -11,2448 -11,3069 -11,3879 -11,3537 -11,4482 -11,4935 -11,6784 -11,7331 -13,8022 -7,70849 -11,3511

ln(CNaOH)(mol/L)
-3,96609 -4,15893 -4,32533 -4,43612 -4,52168 -4,60063 -4,67596 -4,74958 -4,82047 -4,89253 -4,96275 -5,03288 -5,10319 -5,17672 -5,24885 -5,32028 -5,38696 -5,45343 -5,51871 -5,58498

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0,025

Concentration (mol/L)

0,02 0,015 0,01 EtONa NaOH

0,005 0 0 500 1000 1500

Time (s)
Figure 3.3 Variations of Concentration with Time

As seen in the Figure 3.3, concentration changes of CH3COONa and NaOH were plotted with respect to time. Same as first part it can be observed limiting reactant NaOH concentration is decreasing, desired product CH3 COONa concentration is increasing.

0 -6 -5 -4 -3 -2 -1 -2 0

ln(-dCNaOH/dt-CNaOH v/V)

-4

y = 1,1226x - 5,4301 R = 0,1859

-6 -8 -10 -12

-14

lnCNaOH

-16

Figure 3.4 Determination of the Reaction Order () and the Reaction Rate Constant (k)

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From Figure 3.4 the slope and x- intercept of the graph were determined. Reaction rate constant is calculated. (see Sample Calculation) T(oC) 35 k 0,162 Xfinal 0,69 tfinal (min) 32

It can be seen that at 35C reaction rate constant is found as 0,162. Theoretically reaction of ethyl acetate is first order and our result is acceptable. Also reaction is assumed isothermally for this operation. Data show that temperature values usually around 35C. 3.3 Arrhenius Equation Table 3.5 compares the change of reaction constant with temperature. Theoretically it is higher at 35oC and also experimentally, k is higher at 35oC as expected. the error between experimental and theoretical values are 13,1% and 33,1% respectively.

Table 3.5 Changes of Reaction Constant according to Temperature Temperature oC 25 35 k theoretical 0,111 0,242 k experimental 0,0965 0,1620 Error % 13,1 33,1

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3.4 Continuous Operation (CSTR System) Table 3.8 Stoichiometric Table for CSTR Sytem Initally (mol) Changing (mol) Remaining Concentration (mol) (mol/l) 4,7 x 10-4 2,35 x 10-4

Species CH3COONa

0 4,7 x 10-4

As it can be seen, calculated concentration datas are very small. And conductivity values are nearly same during the reaction. It is obvious that there are some mistakes on the measured conductivity values.

Xtheo 1.25

Xexp 1.82

% Error 45

Normally observed conductivity values must decrease with time. But recorded conductivity value was higher than the initial value. And this situation causes to wrong calculations.

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4. CONCLUSION The aim of this experiment is to learn the working principles and types of chemical reactors. There are three types of reactors that we study on (Batch, semi-batch and CSTR).

In the first part of the experiment, conductivity values had been recorded during the reaction. With using the data other values were calculated. Using this values and k values were determined. These values calculated as; for ; 0,85 and for k 0,0965. Same procedures had been done at the temperature of 35oC. After calculations k was found as 0,162. This higher value was expected because k values are proportional to temperature. Although, when theoretical and experimental k values were compared, error values found respectively high. This error can occur because of the position of the conductometer. Or error can come from the quite small concentration values. We dont know how used conductometers work with such small concentration values in the experiment setup. More effective concentration measurement equipments can be used (pH meter, refractometer). Molarity of solutions can be increased or more suitable reactions can be used for this experiment. In the second part, CSTR setup was started and the desired working temperature was set to 35oC. Two components were fed to the reactor at same time and same concentrations (0,02 M). For the CSTR design equation, some assumptions were made. For example, we are assuming that the reactor volume is constant and reactor is stirred well. But it was clearly seen blades of the stirrer was too close to bottom of the reactor. And conductometer was taking the data from near to feed line. According to the calculations, there are very big mistakes in the conductivity measuring.

As a result it can be said that experiment was helpful and really instructive. The difference between batch and continuous systems can obviously be seen with respect to this experiment results. In addition application of the Arrhenius Equation evidently observed.

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5. NOMENCLATURE A ; pre-exponential factor CA0 ; concentration of the reagent A at he beginning, mol/L Ci ; concentration of I, mol/L Ci0 ; initial concentration, mol/L EA ; activation energy of the gases, J/mol FA0 ; molar flow of reagent A that is fed to the reactor, mol/s k ; reaction rate constant NA0 ; moles of reagent A at the beginning of the process, mole Q ; volumetric flow rate of the reagent, L/s -rA ; disappearance velocity of I component ri ; reaction rate of i component R ; constant of the gases, J/mol.K t ; time, s T ; temperature, K V ; volume occupied by the reaction mixture, L xA ; conversion factor ; spatial time V ; differentia element of volume, L ; resident time, s , ; reaction order

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6. REFERENCES [1] McGraw-Hill Encyclopedia of Science and Technology, 5th edition, published by The McGraw-Hill Companies, Inc. [2] http://www.engin.umich.edu/~cre/344/index.htm [3] http://commons.wikimedia.org/wiki/File:Continuous_bach_reactor_CSTR.svg [4] http://www.schwiedernoch.de/english/work/dipl_sim1.htm

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