1.

THEORY

1.1. Reactor Types

1.1.1. CSTR (Continuous Stirred-Tank Reactor)

Figure 1.A Continuous stirrer tank reactor[1]

Characteristics:CSTR is run at steady state with continuous flow of reactants and products;
the feed assumes a uniform composition throughout the reactor, exit stream has the same
composition as in the tank.[2]

Properties of CSTR (Continuous Stirred-Tank Reactor): [2]

 Kinds of Phases Present 1. Liquid phase

2. Gas-liquid rxns

3. Solid-liquid rxns

 Usage 1. When agitation is required

2. Series configurations for different concentration streams

 Advantages 1. Continuous operation

2. Good temperature control

3. Easily adapts to two phase runs

4. Good control

1
 5. Simplicity of construction

6. Low operating (labor) cost

7. Easy to clean

 Disadvantages 1. Lowest conversion per unit volume

2. By-passing and channeling possible with poor

[2]
agitation

1.1.1.1 Design Equation of CSTR

General design equation ; [2]

INLET-OUTLET-REACTION=ACCUMULATION (1)

Each of these parameters are mathematicaly expressed for the A reagent : [2]

V
dN A
FA0  FA   rA dV  (2)
dt

where,

FA0: molar flow of reagent A that is inlet to the reactor,mol/s

FA: molar flow of reagent A that is outlet to the reactor,mol/s

rA : reaction rate constant

V: volume occupied by the reaction mixture,L

NA: moles of reagent A,mol

t: time,s

2
Using Equation 2 and assuming steady state; [2]

dN A
0
dt (3)

Assuming well-mixed; [2]

V
 rA dV  VrA
(4)

Then; [2]

FA0  FA  VrA  0 (5)

or

FA0  FA
V
 rA (6)

1.1.2. Batch Reactor

Figure 2. A Batch reactor[3]

Characteristics: Batch reactor is charged via two holes in the top of the tank; while reaction
is carried out, nothing else is put in or taken out until the reaction is done; tank easily heated
or cooled by jacket.[4]

3
Properties of batch reactor:

 Kinds of Phases Present 1. Gas phase

2. Liquid phase

3. Liquid Solid

 Usage 1. Small scale production

2. Intermediate or one shot production

3. Pharmaceutical

4. Fermentation

 Advantages 1. High conversion per unit volume for one pass

2. Flexibility of operation-same reactor can produce one

product one time and a different product the next

3. Easy to clean

 Disadvantages 1. High operating cost

2. Product quality more variable than with continuous

operation[4]

1.1.2.1 Design Equation of Batch Reactor

General design equation; [4]

V
dN A
FA0  FA   rA dV  (2)
dt

No in flow or out flow the reactor, then, FA = FA0 = 0 ; [4]

4
 dN A V

dt
  rA dV
(7)

With well mix , constant volume; [4]

dN A
 rAV
dt (8)

1.1.3. PFR (Plug Flow Reactor)

Figure 3. A Plug Flow Reactor[5]

Characteristics: Arranged as one long reactor or many short reactors in a tube bank ; no
radial variation in reaction rate (concentration); concentration changes with length down the
reactor.[6]

Properties of plug flow reactor: [6]

 Kinds of Phases Present 1. Primarily Gas Phase

 Usage 1. Large Scale

2. Fast Reactions

3. Homogeneous Reactions

5
 4. Heterogeneous Reactions

5. Continuous Production

6. High Temperature

 Advantages 1. High Conversion per Unit Volume

2. Low operating (labor) cost)

3. Continuous Operation

4. Good heat transfer

 Disadvantages 1. Undesired thermal gradients may exist

2. Poor temperature control

3. Shutdown and cleaning may be expensive[6]

1.1.3.1 Design Equation

Using Equation 2 and examining a small volume element (ΔV) with length Δy and the same
radius as the entire pipe; [6]

If the element is small, then spatial variations in rA are negligible ; [6]

V
 rA dV  rA V
(9)

If volume element is very small, then assuming steady state with no changes in the
concentration of A, Equation 2 is applied and design equation becomes; [6]

FA  y   FA  y  y   rAV  0 (10)

The volume of an element is the product of the length and cross-sectional area, ΔV = A Δy.
Then design equation: [6]

6
  FA  y  y   FA  y 
 y   ArA
  (11)

Then taking the limit where the size of a volume element becomes infinitesimally small; [6]

dFA
lim  ArA
y 0 dy and V=AΔy

then

(12)

1.1.4.Semi-Batch Reactor

Figure 4. A Simple Semi-batch Reactor [7]

A semi-batch reactor is operated with both continuous and batch inputs and outputs. A
fermenter, for example, is loaded with a batch, which constantly produces carbon dioxide,
which has to be removed continuously. Analogously, driving a reaction of gas with a liquid is
usually difficult, since the gas bubbles off. Therefore, a continuous feed of gas is injected into
the batch of a liquid. An example of such a reaction is chlorination.[8]

 Advantages
1. The heat evolved from highly exothermic reactions can be easily controlled. If the
reactor temperature increases too rapidly, closing the feed valve will make the reaction
stop on its own accord.
2. Product selectivity can be adjusted by feed addition.
3. The residence time of the reaction is readily determined.
4. High conversions can be achieved.

7
 5. As with the laboratory batch reactor, only small amounts of reagents and feed are
required for a reaction.[9]

 Disadvantages
1. The volume of the reactor contents changes with time.
2. Because the volume is time-dependent, simulating the unit with a computer model is
extremely difficult.
3. As for the batch reactor, the degree of mixing is hard to determine as the size of the
reactor increases.
4. Again as for the batch reactor, achieving the required heat-transfer rate for
commercial-size reactors can be tough. [9]

design equation for semi-batch reactor was shown on Appendix.

1.2 Arrhenius Equation

In short, the Arrhenius equation gives "the dependence of the rate constant k of chemical
reactions on the temperature T and activation energy[3] Ea", as shown below:[10]

(13)

where A is the pre-exponential factor or simply the prefactor and R is the gas constant. The
units of the pre-exponential factor are identical to those of the rate constant and will vary
depending on the order of the reaction. If the reaction is first order it has the units s −1, and for
that reason it is often called the frequency factor or attempt frequency of the reaction. Most
simply, k is the number of collisions that result in a reaction per second, A is the total number

of collisions (leading to a reaction or not) per second and is the probability that any
given collision will result in a reaction. When the activation energy is given in molecular units
instead of molar units, e.g., joules per molecule instead of joules per mole, the Boltzmann
constant is used instead of the gas constant. It can be seen that either increasing the
temperature or decreasing the activation energy (for example through the use of catalysts) will
result in an increase in rate of reaction.[10]

8
2. EXPERIMENTAL METHOD

2.1. The Aim Of The Experiment

The aim of the experiment to understand working principles of batch and continuous systems
and differences between two reactors. To determine the reaction rate constant and reaction
order with respect to sodium hydroxide. To find the conversion in batch and continuous
systems. Additionaly, to understand how the reaction rate changes with temperature by using
Arrhenius equation.

2.2. Description of the Apparatus

 Feeding circuits of reagents

 Flow control system: Two pumps of with a max. flow of 14 L/h.
 Two flowmeters of direct measure for the feeding pumps.
 A rotameter to adjust the flow rate of liquids.
 The temperature control system
 A thermostatic bath of 9 liters
 Data acquisition and process control system
 Collecting circuit of products

Figure 2.1. Base Service Unit(computer controlled)[11]

9
 Isothermal Reactor with Stirrer in Liquid Phase

 Pyrex-glass reactor, insulated and max. capacity of 2L.

 Agitation system
 Conductivity cell with conductimeter , connected to the electronic module.

Figure 2.2 Isothermal Reactor with Stirrer[11]

 Required elements used in the experiment

 Chemical reagents; Ethyl -Acetate(EtOAc) solution and Sodium Hydroxide(NaOH)
solution
 Laboratory materials; draining containers, plastic cans

10
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 (α) with respect
to sodium hydroxide

In first part of experiment, semibatch reactor is used as a rector. Firstly, the software
programme(SACED-QRIA) was started. Around the reactor, jacket is used to protect
isothermal conditions for all parts of experiment. Firstly, the temperature which is desired
working temperature was adjusted to 25 °C. To set desired flow rate of ethly acetate in the
reactor, recirculation was made by using rotameter. After that, 1L of 0.02 M sodium
hydroxide solution was put into the reactor with using computer control system. And then,
ethyl-acetate valve was positioned to the ‘to reactor’ position and it was allowed 1L of 1M
ethyl acetate solution to the reactor. It was waited until 2L solution had been in the reactor
and the time was recorded as 18.26 min. After the conductivity had been stayed constant, the
reaction was finished. Conductivity values were recorded on CD. The system was stopped and
all of the parts were cleaned with water.

2.3.1.b. Variation of the kinetic constant with temperature, Arrhenius Equation

The desired working temperature was adjust to 35oC. The same procedure was performed as
in the section 2.3.1.a. The time was recorded as 16.42 min when level 2L. Conductivity values
were recorded on CD,again. The system was stopped and all of the parts were cleaned with
water.

2.3.2. Continuous Operation, CSTR System

For this part of experiment, continuous reactor (CSTR) was used.Firstly, the software
programme(SACED-QRIA) was started. The desired working temperature was set to 25°C.
To set desired flow rates of ethly acetate and sodium hydroxide in the reactor, recirculation
was made by using rotameter. Equal molar (1M) of reactants was sent to reactor at the same
time continuously. When the reactant level had been reached 0.5L, 1L, and 2L, the time
values were recorded as 4.14 min, 9.26 min, 18.51 min , respectively. Conductivity values
were recorded on CD. The system was stopped and all of the parts were cleaned with water.

11
3. RESULTS AND DISCUSSION

3.1 Semi-batch/ batch System (25 0C)

3.1.1 Stoichiometric Table

NaOH + CH3COOC2H5→CH3COONa+ C2H5OH

aA+bB→cC+dD

The reaction between sodium hydroxide and ethyl acetate was performed in semi-batch
reactor. 0.02 mol/L sodium hydroxide was filled to half of the reactor ( the volume of the
reactor is 2 L) before the reaction was started. 1 mol/ L ethyl acetate was fed to reactor during
the reaction. As shown above the saponification of ethyl acetate, the stoichiometric proportion
between the sodium hydroxide and ethyl acetate was 1/1. In other words 1 mol sodium
hydroxide react with 1 mol ethyl acetate. But in this system the concentrations of them were
different. The concentration of ethyl acetate was bigger than sodium hydroxide. So that the
ethyl acetate was excess reactant in contrast to sodium hydroxide was limiting reactant.

Table 3.1 was made up with reference to limiting reactant by using appropriate data. Species
A that indicates to sodium hydroxide was the basis of calculation and NA0 was number of
moles of A initially present in the reactor. Of these N A0X moles of A were consumed in the
system as a result of chemical reaction, leaving (NA0- NA0X) moles of in the system. That
was the number of moles of A remaining in the reactor. Additionally this table showed that
the change of number of moles for each species such as c/a NA0X and d/a NA0X.(c/ a) and
(d/a) indicated the stoichiometric proportion the basis of A. In addition to (d/a+c/a-b/a-1)
represented the total number of moles per mole of A reacted.

12
Table 3.1 Stoichiometric table for semi-batch/batch system in terms of symbols

Molecules Species Initially(mol) Change(mol) Remaining (mol)

NaOH A NA0 - NA0X NA= NA0- NA0X
CH3COOC2H5 B NB0 -b/a NA0X NB= NB0 -b/a NA0X
CH3COONa C - c/a NA0X NC= c/a NA0X
C2H5OH D - d/a NA0X ND= d/a NA0X
Totals NT0= NA0+ NB0 NT=NT0+(d/a+c/a-b/a-1) NA0X

Table 3.2 showed that experimental concentration of at the start time of the reaction. But
when this table was built up, the volume of reactor was not equal to 1 L. Since the
conductivity values could not be measured at zero time. The volume of increased by the time.
However we assumed that concentrations of sodium hydroxide and ethyl acetate were equal to
start time although the volume of reactor was not equal to 1 L was corresponding to start time
volume. The purpose of assumption was to obtain more accuracy graphs. The conversion of
sodium hydroxide to sodium acetate was calculated as 0.285. For this assumption the
conversion value may be incorrect. Additionally as shown in table total number of moles was
preserved during the reaction.

Table 3.2 Stoichiometric table for semibatch/batch system in terms of real values

Molecules Species Initially(mol/L) Change(mol/L) Remaining(mol/L)

NaOH A 0.02 -0.0057 0.0143
CH3COOC2H5 B 1 -0.0057 0.994
CH3COONa C - 0.0057 0.0057
C2H5OH D - 0.0057 0.0057
Totals CT0= 1.02 CT=1.02

3.1.2 Table From Sample Calculation

Table 3.3 showed that calculated some variables such as conductivity, volume, concentration
were necessary to find the order of reaction and reaction rate constant. During the experiment
total conductivity in the reactor were measured with time. The concentrations of sodium
acetate were passed from the conductivity values at different time intervals. At the same time

13
the volume of reactor increased with time because being semi- batch reactor. The number of
moles of sodium acetate which indicated that the amount of sodium hydroxide was converted
to it, was calculated by using volume of reactor and the concentration of sodium acetate. At
any time the concentration of sodium hydroxide was obtained by substrating the amount of
sodium acetate from the initial amount of sodium hydroxide. After that these processes, other
parameters which were required for design equation of semi-batch reactor.

From these data (only some parts of data were presented ) it can be said that the conductivity
of reactor decreased regularly with time. This result was an evidence that the reaction was
irreversible. Because if the reaction had been reversible, it would be expected that firstly the
conductivity decreases with time but after some period of time, the conductivity increases
again because of conversion of some sodium acetate to sodium hydroxide. Since the
conductivity value of sodium hydroxide is much bigger than the conductivity of sodium
acetate.

Table 3.3 Sample calculation table

Time(s) K(mS) Volmue(L) CEtoNa x10- NEtoNa x10- NNaOH(0) - NEtoNa(mol)

7 7
(mol/L) (mol)
0 1.3 1.430918 0 0 0.028618360
15 1.26 1.445508 3.2258 4.66293 0.028617894
30 1.22 1.460098 6.4516 9.41999 0.028617418
45 1.19 1.474688 8.8710 13.0819 0.028617052
60 1.16 1.489287 11.290 18.1440 0.028616679

CNaOH CNaOHϑ/V dCNaOH/dt -dCNaOH/dt- ln (-dCNaOH/dt- ln

5 5 7
(mol/L) (mol/L.s)x10- (mol/L.s)x10- CNaOHϑ/Vx10- CNaOHϑ/V) (CNaOH)
0.02 1.26352 -1.3614 9.7852 -13.8372 -3.91202
0.019798 1.23813 -1.3345 9.6354 -13.8526 -3.92218
0.019600 1.21349 -1.3077 9.4229 -13.8749 -3.93224
0.0192405 1.18958 -1.2817 9.2155 -13.8972 -3.94422
0.019215 1.16637 -1.2565 9.0134 -13.9194 -3.95206

14
3.1.3 The Concentration Changes of Sodium Hyroxide and Sodium Acetate with Time

0,016
0,014
0,012
0,01
CNaOH(mol/L)

0,008
0,006
0,004
0,002
0
0
30
60
90

270
120
150
180
210
240

300
330
360
390
420
450
480
510
540
570
Time (s)

Figure 3.1 The concentration change of sodium hydroxide with time at 25 0C

Figure 3.1 represents that the relationship between the concentration of NaOH and time at 25
0
C. As shown in figure the concentration of NaOH was approximately 0.014 mol/L at start up
of reaction. During the reaction it was expected that the concentration NaOH was decreasing
with time. It can be said that the concentration difference between start up reaction and at any
time reaction of NaOH was equal to product concentration it was assumed that no loss of
material. At the end of the reaction the concentration was approximately 0.01 mol/L. From
figure 3.1 it can be said that the conversion of this reaction was pretty low. Since there was no
big difference between the initial and final concentration of NaOH. The reason of low
conversion can be that there was no good mixing. Therefore the interaction between NaOH
and CH3COOC2H5 was not sufficient. Moreover can not be providing and adjusting optimum
conditions such as temperature and being initial low concentration of NaOH can cause the
low conversion.

15
 45
40
35
CEtoNa (mol/L *10^-7)

30
25
20
15
10
5
0

Time (s)

Figure 3.2 The concentration change of sodium acetate with time at 25 0C

Figure 3.2 shows that the product concentration changes with time for saponification of ethyl
acetate at 25 0C. As shown in figure there was no sodium acetate at the end of the reaction. It
can be well observed that as there was gradual increase in product concentration with time.
The source of exponential increase that the order saponification of ethyl acetate reaction was
first order in terms of NaOH and was independent CH3COOC2H. according design equation
of semi-bath reactor in terms of NaOH, the concentration of NaOH was a function of C NaOH(0)
and exponential of time (CNaOH= CNaOH(0)e-kt). Finally as it is understood from figure the
concentration of sodium acetate was equal to 4x10-6. It was evidence that the reaction
perform was not sufficient.

16
3.1.4 The Reaction Rate Constant for Saponifications of Ethlyacetate for 25 0C

-13,8
-4,3 -4,25 -4,2 -4,15 -4,1 -4,05 -4 -3,95 -3,9 -3,85
-13,9
ln(-d(CNaOH)/dt -CNaOH*ν/V)

y = 2,0232x - 5,9246 -14

-14,1

-14,2

-14,3

-14,4

-14,5

-14,6
ln(CNaOH)

Figure 3.3 The reaction rate constant and the order of reaction for saponifications of ethyl
acetate for 25 0C

Figure 3.3 gives the relationship between reaction rate and both reaction rate constant and the
order of reaction in terms of sodium hydroxide. This graph was made up according to design
equation of semi batch reactor in terms of limiting reactant. The slope of graph gave the order
of reaction in terms of limiting reactant. As shown in figure the reaction order was 2 but the
real order in terms of NaOH 1. The difference can arise from calculation error. The intercept
of reaction rate constant. Unfortunately the reaction rate constant was found bigger than the
expected. Similarly, the calculation error, in appropriate experimental conditions could cause
the difference.

Table 3.4 was consisted of the order of reaction, reaction rate constant, final conversion and
time required for completing the reaction at 250C. These values were arrangement
circumstance of obtaining results from above. As it was understood from having results, there
was pretty difference between theoretical and experimental parameters. For example, the
order of reaction was not match with real order of reaction. It was a pretty important error
since the other parameters such as reaction rate constant was determined on the basis of
reaction order. The reaction rate constant was dependent the order of reaction from the
equation (k=(concentration/time)1-n). Moreover the reaction rate constant was a function of
time. As it was thought that during the reaction there was no temperature change, the reactor
17
operated under isothermal condition, it can be said that the difference between actual and
experimental reaction rate constant only arise from the finding error order of reaction. As it
was mentioned above, calculation error caused the error order of reaction. When these errors
were associated, then the final conversion of reaction was smaller than expected as well as be
showed from table.

Table 3.4 Some variables that effect the rate of reaction for 25 0C

Temperature The order of reaction Reaction rate constant Xtfinal tfinal(s)

(oC) (α) (k)
250C 2 0.00267 0.285 1878

3.2 Semi-batch/ batch System (35 0C)

3.2.1 Table From Sample Calculation

This part of the reaction was performed at 35 0C instead of 25 0C to observe the effect of
temperature on the rate of reaction by following the toatl conversion of the reaction. Table 3.5
was made up at same path with table 3.3. The concentrations were calculated by using
conductvity values. It was passed from concentration to other parameters such as conversion
by following identical procedure like table 3.3.

When table 3.3 and 3.5 was compared that, it was seen that at table 3.5 the conductivity
values were bigger than table 3.3 at same range of time. Since the rate of ions which were
responsible for the conduction raised with increasing temperature. Therefore, the probability
of collisions of ions in a sense the number of ions leaved from the atom orbital. The number
of ions increased in ambience, this circumstance remarks that as more number of ions so the
conductivity. At 35 0C the conversion of reaction was bigger than at 25 0C. Forwhy according
to Arrhenius equation the reaction rate constant was directly proportional to temperature in
terms of exponential, as it was thought that the order of reaction did not change with time, the
rate of reaction increased with temperature due to increasing the reaction rate constant, too.
As shown in table 3.5 the volume of reactor increased with time due to using semi-batch
reactor whose volume was not constant.

18
Table 3.5 Sample calculation table

Time(s) K(mS) Volmue(L) CEtoNa x10- NEtoNa x10- NNaOH(0) - NEtoNa(mol)

7 7
(mol/L) (mol)
0 1.31 1.347062 0 0 0.02
15 1.29 1.362368 1.5625 2.13011 0,019999787
30 1.27 1.379474 3.1250 4.31086 0,019999569
45 1.27 1.395680 3.1250 4.36150 0,019999564
60 1.24 1.411886 5.4687 7.72125 0,019999228

CNaOH CNaOHϑ/V dCNaOH/dt -dCNaOH/dt- ln (-dCNaOH/dt- ln

(mol/L) (mol/L.s)x10-5 (mol/L.s)x10-5 CNaOHϑ/Vx10-7 CNaOHϑ/V) (CNaOH)
0,014847 1.09998 -1.19151 9.15292 -13.9040 -4.209946
0,014670 1.07397 -1.16386 8.98911 -13.9221 -4.221918
0.014498 1.04888 -1.13618 8.73026 -13.9513 -4.233747
0,014330 1.02466 -1.11022 8.55561 -13.9715 -4.245427
0,014165 1.00125 -1.08541 8.41555 -13.9880 -4.256988

3.2.2 The Concentration Changes of Sodium Hyroxide and Sodium Acetate with Time

0,016
0,014
0,012
0,01
CNaOH (mol/L)

0,008
0,006
0,004
0,002
0
0
30
60
90

180
120
150

210
240
270
300
330
360
390
420
450
480
510
540
570
600

Time (s)

Figure 3.4 The concentration change of sodium hyroxide with time at 35 0C

19
Figure 3.4 shows that the concentration of NaOH with time. Similar to figure 3.1 the
concentration of NaOH decreased with time due to the conversion of some amount of NaOH
to sodium acetate during the reaction of saponification of ethyl acetate. When figure 3.1 and
3.4 were compared between each other, both at 35 0C and 25 0C final concentrations of NaOH
were equal to 0.01 mol/L. But for these temperatures the initial concentration of NaOH was
bigger at 35 0C than at 25 0C because of having high initial conductivity at 35 0C. So that the
conversion of was higher than the first situation on the point of expected. Moreover the
reaction time for two temperature was different. For first temperature the completed reaction
time was approximately 570 s in contrast to for second temperature the completed reaction
time was approximately 600 s. This result showed that the interaction of sodium hydroxide
and ethyl acetate was greater at 35 0C. It was proof that having higher conversion in second
circumstance temperature.

45
40
35
CEtoNa (mol/L)

30
25
20
15
10
5
0

Time (s)

Figure 3.5 The concentration change of sodium acetate with time at 35 0C

Figure 3.5 give us the information about the change of concentration of sodium acetate with
time. As it was mentioned above the final concentration of sodium acetate was larger than
first temperature situation ( the initial sodium hydroxide temperature was 25 0C) due to high
conversion. As it was expected at 350C the amount of product was greater than because of
initial conductivity value was big. Additionally the reason of the shape (exponential) of
concentration change of sodium acetate was the actual order of reaction was equal to 1.

20
3.2.3 The Reaction Rate Constant for Saponifications of Ethly Acetate for 35 0C

-13,8
-4,7 -4,6 -4,5 -4,4 y = 1,9974x
-4,3 - 5,4887 -4,2 -13,9 -4,1
ln(-d(CNaOH)/dt -CNaOH*ν/V)

-14
-14,1
y = 1,9974x - 5,4887
-14,2
-14,3
-14,4
-14,5
-14,6
-14,7
-14,8
ln(CNaOH)

Figure 3.6 The reaction rate constant and the order of reaction for saponifications of ethly
acetate for 35 0C

Figure 3.6 shows that reaction rate constant and the order of reaction in terms of sodium
hydroxide at 35 0C. This graph was made up according to design equation of semi batch
reactor in terms of limiting reactant. The main difference of figure 3.6 from figure 3.3 was
that for second circumstance the reaction rate constant was greater than for the first situation.
Since according o Arrhenius equation reaction rate constant increased with raising the
temperature. As it was observed for both two figures the order of reaction in terms of limiting
reactant was 2. In the same way as the reasons of error order of reaction that were mentioned
in the discussion part of figure 3.3 were valid for comment for this figure.

Table 3.6 indicates that at 35ºC reaction parameters such as reaction rate constant and reaction
order according to limiting reactant (NaOH), final conversion and time required that
completed reaction. When table 3.6 and table 3.5 were compared between each other it was
observed that for second temperature final conversion was greater than for first temperature.
Because theoretically at high temperatures, the rates of molecules, the possibility of collisions
of molecules and the interactions between reactant increased with raising temperature,
respectively. Also it was expected that the combinations of Arrhenius equation and reaction
rate equation, the conversion increased. Similarly, the order of reaction and reaction rate

21
constant were improper although in concurrence with what the main reason was for obtaining
error values.

Table 3.6 Some variables that effect the rate of reaction for 25 0C

Temperature The order of reaction Reaction rate constant Xtfinal tfinal(s)

o
( C) (α) (k)
350C 2 0.00413 0.325 1375

3.3 Variation of Kinetic Constant with Temperature, Arrhenius Equation

Table 3.7 represents that the comparison of reaction rate constant at different temperature by
both theoretically and experimentally. The reaction rate constant increased with increasing
temperature for both experimentally and theoretically. At different temperature the
comparison of reaction rate constant in terms of theoretical was performed by using the ratio
of Arrhenius equation at different temperature. The comparison of reaction rate constant in
terms of experimental was performed by utilizing the intercept of graph for figure 3.5 and 3.6.
The reasons of increasing reaction rate constant with raising temperature could the reaction of
molecules, the number of collisions, the average kinetic energy and the activated complex
increased, respectively consequently the reaction rate constant increased. When it was looked
at theoretical and experimental reaction rate constant values were pretty different between
each other. High errors could be obtained due to certain causes as keeping temperature or
flow rate stable.

Table 3.7 Variation of Kinetic Constant with Temperature

Temp. (°C) ktheo kexp

25 0,111 0.00267
35 0,242 0.00413

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3.4 CSTR (Continuous Stirred-Tank Reactor)

3.4.1 Stoichiometric Table

Table 3.8 shows us to clearly derive expressions for each species conversion in terms of
overall reaction progression (conversion of reactants A and B to product C and D). As it was
observed from table, the initial concentration of sodium hydroxide and ethyl acetate were
identical and equal to 0.02 mol/L. For this reason in contrast to semi batch system, there was
no limiting reactant in CSTR system. It can be said that the order of reaction was dependent
both the concentration of sodium hydroxide and ethyl acetate, and it can not be assumed that
ethyl acetate was excess. As a result, it can be decided that the overall order of reaction would
be 2 if the reaction had been elementary. When initial and final concentration of sodium
hydroxide were compared between each other, it can be sight easily there was a pretty
difference. It showed us the conversion of reaction was great. In addition for these
information, this table can be built up on the basis of specie B (CH3COOC2H5) because the
concentration of B not excess and equal to concentration of A.

Table 3.8 Stoichiometric table for CSTR

Molecules Species Initially(mol/L) Change(mol/L) Remaining(mol/L)

NaOH A 0.02 -0.012 0.008
CH3COOC2H5 B 0.02 -0.012 0.008
CH3COONa C - 0.012 0.012
C2H5OH D - 0.012 0.012
Totals CT0= 0.04 CT=0.04

Table 3.8 shows that experimental and theoretical conversion of reaction. There was a small
difference between experimental and theoretical conversion values. It can be commented that
it was more possible that experimental conversion was incorrect. The conductivity values
could not be measured from start time of reaction because of inappropriate reactor design. The
conductometer was middle of the reactor and the reactants were fed to reactor at the bottom of
the reactor.

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Table 3.9 The comparison of conversion both experimentally and theoretically in CSTR.

Xtheo Xexp % error

0.53 0.6 13.2

As a result if a comparison had been made in terms of conversion for semi-bath and CSTR
system, it would be expected that the conversion of semi-batch was higher than the
conversion of CSTR. Since the main reason of using semi- batch reactor was obtaining high
conversion by adjusting selectivity. In contrast to generally, the conversion of CSTR was low
due to small retention time. But we obtained unexpected result at the end of the reaction. The
conversion of CSTR was greater than semi-batch reactor. This error can arise from calculation
errors.

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4. CONCLUSION

The goals of the experiment were that to find out advantages of disadvantages of batch and
continuous reactors, to observe the effect of temperature on conversion of reaction in a semi-
batch reactor and to determine the order of reaction and reaction rate constant. For these
purposes the experiment was consist of three main parts.

The aim of first part of the experiment was to determine the conversion of reaction at definite
temperature (25 0C) when the concentration of one of the reactant was too high in accordance
with other reactant concentration. For this goal, 0.02 mol/L sodium hydroxide was filled at the
start time of the reactor and 1 mol/L ethyl acetate was fed to reactor. During the reaction , the
total conductivity value where inside the semi-batch reactor were measured, after the various
required calculations, it was passed to concentration from conductivity the graph was drawn
and the order of reaction from slope of graph which was only dependent the concentration of
sodium hydroxide and reaction rate constant from intercept were found as 2 and 0.00267,
respectively. The conversion of reaction was calculated as 0.285. The conversion of reaction
was not sufficient.

The aim of the second part of experiment was observe the temperature effects on reaction rate
constant, the conversion. This part of the experiment was performed at 35 0C instead of 25 0C.
After similarly same procedures were applied like as first part, the reaction rate constant and
conversion were determined as 0.00413 and 0.325 respectively. They were expected
conclusion since according to Arrhenius equation the reaction rate constant increased with
raising the temperature. The reaction rate increased too due to being directly proportional
reaction rate constant. Increasing reaction rate indicated that the amount of consumed sodium
hydroxide per unit time was increased and therefore it was proof that higher conversion than
low temperature. Additionally the order of reaction was same as being. It did no change with
increasing temperature.

The aim of the last part of the experiment was to compare semi-batch reactor and CSTR in
terms of conversion at same temperature. The difference from first part was that the
concentration of sodium hydroxide and ethyl acetate were identical and they were fed to
reactor at same time continuously. The experimental conversion of CSTR was found as 0.6.
when this value was compared to semi-batch reactor, it can observed that it was pretty bigger
than semi- batch reactor. Unfortunately it was undesired conversion value. As it was

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mentioned result and discussion part calculation error could cause incorrect conversion. In
addition to in CSTR when experimental and theoretical conversion values were compared
between each other, there was a small difference whose source can be design difficulty of
reactor.

Consequently, in some situations semi batch reactor was more necessary than CSTR such as
controlling heat production of reaction and controlling of concentration of reactants to
improve the selectivity of a reaction.

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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

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

τ ; spatial time

ΔV ; differentia element of volume, L

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6.REFERENCES

[1] http://www.mathworks.com/matlabcentral/fileexchange/13556-continuously-stirred-tank-
reactor-cstr

[2] http://www.engin.umich.edu/~cre/asyLearn/bits/cstr/index.htm

[3] http://wiki.biomine.skelleftea.se/wiki/index.php/Well-stirred_batch_reactors

[4] http://www.engin.umich.edu/~cre/asyLearn/bits/batch/index.htm

[5] http://www.pilot-plant.com/reactions.htm

[6] http://www.engin.umich.edu/~cre/asyLearn/bits/pfrfinal/index.htm

[7] http://www.umich.edu/~essen/html/06chap/html/prs_cstr.htm

[8] http://www.scribd.com/doc/22995623/Batch-Reactors

[9] http://findarticles.com/p/articles/mi_qa5350/is_200006/ai_n21465362/

[10] http://www.edurite.com/kbase/arrhenius-equation-constant

[11] http://www.edibon.com/products/?area=chemicalengineering&subarea=reactors

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