Title: Experimental report two (Tubular reactor)

Name: Amr T Mohamed

ID: 128973

Affiliation: The British University in Egypt

Year 3, Chemical Engineering

Course title (code): Chemical reaction engineering (EAX_5_227.1)

Paper format: APA style with BUE guidelines

Report two 2

Abstract

The aim of this experimental report is to study the kinetics of sodium hydroxide

reaction with ethyl acetate in a tubular flow reactor, it focuses on determining the

reaction order and rate constant (k), conversion (X), the relation between conversion,

residence time, and finally the time required to reach the steady state, the experimental

results were not obtained due to an error in the reactors flow meter. It was required to

obtain the order reaction, with specific rate constant, conversion, graphical relation

between conversion and residence time, and finally the time required reach steady state.

The experimental procedures were to carry on the reaction in a tubular reactor and then to

take a sample and quench it, then to determine the concentration by back titration

technique and some basic analytical chemistry calculations, also the reported mentions

expected sources of errors and how to avoid them. On the theoretical side, the report

discusses tubular reactors mechanism, equations, controls, uses, advantages and

disadvantages. Then finally it discusses chemical kinetics reaction rates, factors affecting

it, specific rate constants, and reactions orders.

Tubular reactors, chemical kinetics, determining reaction order, specific rate

constant, back titration, residence time, conversion, sodium hydroxide reaction with ethyl
acetate
Report two 3

Table of Contents

Abstract ................................................................................................................... 2

Introduction ............................................................................................................. 6

Tubular reactors ...................................................................................................... 6

Definition ............................................................................................................ 6

General information ...........................................Error! Bookmark not defined.

Method of operation (mechanism) ...................................................................... 6

Design equations ................................................................................................. 7

Types, orientations, and classifications .............................................................. 8

Uses ..................................................................................................................... 9

Advantages and disadvantages ......................................................................... 10

Chemical kinetics .................................................................................................. 11

Definition and general brief information .......................................................... 11

Reaction rates .................................................................................................... 11

Factors affecting reaction rates ..................................................................... 11

Rate equations ............................................................................................... 12

Reactions orders ................................................................................................ 12

Zero order...................................................................................................... 13

First order ...................................................................................................... 14

Second order ................................................................................................. 15

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Specific rate constant (k) .............................................................................. 18

Experimental method and procedure .................................................................... 19

Experimental technique .................................................................................... 19

Experimental equipment and materials used .................................................... 19

Chemical reaction equation............................................................................... 20

Experiment schematic diagram ......................................................................... 20

Experimental results.............................................................................................. 21

Approach ........................................................................................................... 21

Readings and initial analytical calculations ...................................................... 23

Tabulated calculations ...................................................................................... 23

Required results ................................................................................................ 24

Discussion ............................................................................................................. 25

Sources of error ..................................................................................................... 27

Human and materials errors .............................................................................. 27

Device and surroundings errors ........................................................................ 28

Ways and techniques to avoid errors ................................................................ 28

Conclusion ............................................................................................................ 29

References ............................................................................................................. 31
Report two 5

List of figures

Figure 1: A simple tubular reactor .......................................................................... 6

Figure 2: Tubular reactor interiors .......................................................................... 8

Figure 4: Single stage tubular reactor ..................................................................... 8

Figure 5: Multistage tubular reactor ....................................................................... 9

Figure 3:Horziontal tubular reactor ........................................................................ 9

Figure 6: A tubular reactor used in tproduction of methyl 2-methylpropenoate. . 10

Figure 7:Kinetics equations .................................................................................. 12

Figure 8: Graphical description of zero order ....................................................... 13

Figure 9: Graphical description of first order ....................................................... 15

Figure 10: Graphical description of second order................................................. 18

Figure 11: Edibon tubular reactor ......................................................................... 19

Figure 12: Titration set.......................................................................................... 20

Figure 13: Experiment schematic diagram ........................................................... 20

List of tables

Table 1: Readings and initial analytical calculations ............................................ 23

Table 2: Tabulated calculations ............................................................................ 23

Table 3; Reaction orders with their R2 values ....................................................... 24

Table 4: Human and materials errors classification and ways to avoid them ....... 27

Table 5: Device and surroundings errors classification ........................................ 28

Report two 6

Introduction

Tubular reactors

Definition

A tubular reactor is a tube (or a pipe) in which reactant(s) enters the inlet then are
converted to product(s) and the outlet.

Figure 1: A simple tubular reactor

Method of operation (mechanism)

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(Catalano, Plug Flow Reactors, 2015)

Design equations

General mass balance equation

Input - Output + Generation = Accumulation

Can be written as

Where,

FAO is feed molar flow rate

FA is output molar flow rate

rA is rate equation for the reaction

V is reactor volume

But, at steady state:

Differentiating,

The conversion per unit volume for single reactions

That gives the differential form of the plug flow reactors mole balance:

And the integral form can be described as:

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Figure 2: Tubular reactor interiors

(Charles G. Hill, 2014)

Types, orientations, and classifications

Types

1- Single stage tubular reactor (vertical)

Figure 3: Single stage tubular reactor

2- Multistage tubular reactor (vertical)

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Figure 4: Multistage tubular reactor

Orientations:

1- Vertical tubular reactor

2- Horizontal tubular reactor

Figure 5:Horziontal tubular reactor

Classifications:
1- Series
2- Parallel

Uses

1. Gasoline production
2. Polymerization
3. Synthesis of ammonia
4. Cracking of crude oil
5. Oxidation processes of nitrogen and sulphur compounds
6. Other reactions processes.
Report two 10

Figure 6: A tubular reactor used in the production of methyl 2-methylpropenoate.

Advantages and disadvantages

Advantages:
1. Requires low operating and labor costs.
2. High conversion is acquired per unit volume.
3. Maintains continuous production.
4. Easy to clean and maintain
5. Constant and unvarying product quality

Disadvantages:
1. Very hard in temperature controlling.
2. Shutdown, revamping, maintenance and cleaning are very expensive.
3. Exothermic reactions may cause intolerable hotspots.
(5400 Continuous Flow Tubular Reactors, 2012)
Report two 11

Chemical kinetics

Definition and general brief information

The study of motions or kinetics terminology comes from the Greek word kinesis

which means movement, scientifically, chemical kinetics or reaction kinetics is the study

of the reactions rates and other microscopic properties for chemical reactions such as the

creation of intermediates, the re-arrangement and orientation of atoms in and after a

reaction, the sufficient energy for molecules in order to start a reaction (activation

energy), and the order of reactions.

Reaction rates

The reaction rate for a a chemical reaction is a kinetics measure of the reactions

substances concentrations changes across the reaction time. Chemical reactions has

differents speed of occuration, some are fast, and some take years. For each reaction there

is rate for it, for each rate there is an order and a specfic rate constant. Reaction rates

affects the effiecency of the reactions and also depended on many parameters.

Factors affecting reaction rates

1. Reaction temperature.

2. Reactants concentration.

3. Adding a catalyst.

4. The surface area of reactants and catalyst.

5. Nature of reactants.

(Factors That Affect Reaction Rates, 2012)

Report two 12

Rate equations

Figure 7:Kinetics equations

(Chemical Kinetics, 2016)

Reactions orders

Mathematical wise, the reaction order or the order of the reaction is considered as

the exponent for which the concentration parameter in the rate equation is raised to

Reaction orders are most commonly be positive, however it can be negative, zero, or

even fractions.

The reaction order could be equal the stoichiometric coefficients for the reactants

sometimes, however, it is not a general absolute rule. As single-step or elementary

reactions reactants stoichiometric coefficients are equal to their order, also the overall

or the total reaction order is equal to the sum of reactants stoichiometric coefficients or

as it called the molecularity. On the other hand, for Complex or multi-step reactions

(reactions with different orders than their stoichiometric coefficients) due to the fact that
Report two 13

complex reactions has one or more reaction intermediates and includes two or more

elementary reactions. (Chemical Kinetics, 2016)

Zero order

From chemical kinetics perspective. a zero order reaction is a reaction that is

independent on the reactants concentration, as increasing or decreasing the concentration

will not fasten or slow the reaction. However, this type of reactions rate is so rare. Also a

reaction could be a zero order from one reactant perspective only, in case of this reactant

has very small concentration comparing to other reactants.

Zero orders formula derivation can be proved as:

First, write general rate equation

Write the differential form with order (n) equals zero

Rearrange to get

Then integrate both sides

Finally, solve to get

Graphical description:

Figure 8: Graphical description of zero order

(Zero-Order Reactions, 2015)

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First order

A first order reaction is a linear kinetics process which its rate depends on a single

reactant with a concentration term that exponent value of one. In other meaning; the

reaction is directly proportional to the reactants concentration. The mathematical

formula can be proved and concluded as the following:

First write the general differential formula of the rate law

Rearrange to get

Integrate both sides to get

Solve the integration

Therefore,

Rearrange to get
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Hence,

Graphical description:

Figure 9: Graphical description of first order

(First-Order Reactions, 2017)

Second order

A first order reaction is a proportional kinetics process which its rate depends on a

single reactant with a concentration term that exponent value of two. In other meaning;

the reaction is directly proportional to the squared reactants concentration. And it has

two cases:

1- Identical reactants (Two similar reactants in a single elementary step)

2- Different reactants (Two different reactants in single elementary step)

The mathematical formula can be proved and concluded as the following:

For case 1

First write the general differential formula of the rate law for same reactants:
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Rearrange to get

Integrate concentration across period from t=o to another time period t

Solve integration

Hence,

Therefore,

Second case

First write the general differential formula of the rate law for different reactants

Let
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The law becomes

Rearrange

Integrate at t=0 and x=0

Use partial fractions

From integrals:

Simplify algebraically

Hence,

Therefore,
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Graphical description for both cases

Figure 10: Graphical description of second order

(Second-Order Reactions, 2014)

Specific rate constant (k)

The specific constant of the rate equation (referred as k) is the parameter that

relates the proportionality of a reaction to the reactants concentration. However, specific

rate constant depends on the reaction conditional temperature, and always determined

experimentally. Moreover, the higher the specific rate constant the faster the reaction and

vice versa. (Rate Law and Specific Rate Constant, 2008)

Report two 19

Experimental method and procedure

Experimental technique

1. Prepare 0.25L of 0.1M Sodium Hydroxide with 0.25L of 0.1M Ethyl acetate.

2. Put the two reactants in the three neck flask.

3. Assure good mixing for the reactants.

4. Assure temperature equals 30oC for the reaction.

5. Take 5mL samples every five minutes time period.

6. Quench the sample to the reaction with 10ml HCL.

7. Proceed the sample plus the 10ml HCL in a back titration using phenolphthalein

indicator.

8. Write down the measured volume from the titration process.

9. Calculate the unreacted and the remaining number of moles to get the

concentration.

10. Repeat steps 4-8 for four more times

Experimental equipment and materials used

1- Edibon tubular reactor

Figure 11: Edibon tubular reactor

Report two 20

2- Titration set

Figure 12: Titration set

3- 10 Liter of 0.1M Caustic Soda (NaOH).

4- 10 Liter of 0.1M Ethyl acetate (CH3COOC2H5)
5- Phenolphthalein indicator (PhPh)

Chemical reaction equation

NaOH + CH3COOC2H5 CH3COONa + C2H5OH

Sodium hydroxide Ethyl acetate Sodium acetate Ethanol
Experiment schematic diagram

Figure 13: Experiment schematic diagram

(Soliman, 2017)
Report two 21

Experimental results

Approach

1. Get the concentration (CA) at the different times periods

ntotal HCL = n HCL reacted with NaOH + n HCL remaining

Where, n is number of moles

2. Find total number of moles for HCL:

10
n total HCL = N(concentration of HCL) x V (volume of HCL) = 0.1 x 1000 =

0.001 moles

3. Find unreacted number of moles for HCL remaining at each time period as:
(N x V)HCL = (N x V)NaOH
n HCL remaining = (N x V)NaOH
4. Calculate reacted number of moles for n HCL reacted with NaOH as:

Reacted number of moles of HCL with NaOH = ntotal HCL - n HCL remaining

5. Calculate the inlet concentration of NaOH feed (CAi) by this equation:

CAi= (FACAT)/ (FA+FB)

Note: Concentration in normality (N) for HCL and NaOH is equal to their relevant

values in molarity (M) as they both have only one hydrogen ion.

Hence,

6. Calculate LnCA/CAo and 1/CA for first and second order respectively

From previous calculated parameters

7. Calculate the specific rate constant (k) also it will be the slope of the two graphs

after determining the order:

A. First order trial using this equation:

B. Second order trial using this equation:

Report two 22

8. Calculate reactors volume (V) using this equation

= d L (Where, diameter(d) = 0.006m, and length(L) = 14.7m2)

9. Calculate the residence time () using this equation

= V/F (Where, F is feed molar rate)

10. Calculate the reactions conversion (X) using this equation

11. Plot a graph between CAo and residence time ()

12. Plot a graph between the conversion (X) and residence time ()

13. Determine the suitable time to reach steady state conditions

 Report two 23

Readings and initial analytical calculations

Table 1: Readings and initial analytical calculations

Time Volume of Underreacted Reacted of moles of

(minute) NaOH number of moles NaOH Concentration (N) Ln CA/CAo) 1/Concentration
5 0.0027 0.00027 0.00073 0.146 0.378436 6.849315
10 0.0025 0.00025 0.00075 0.15 0.405465 6.666667
15 0.003 0.0003 0.0007 0.14 0.336472 7.142857
20 0.005 0.0005 0.0005 0.1 0 10

Tabulated calculations

Table 2: Tabulated calculations

Flow (L/S) Total flow (L/S) Residence Concentration of Conversion (X)

F= FNaOH + FACOET time () (min) NaOH (M)
FNaOH FACOET = V/F CAi CAo
----- ----- ----- ----- 0.146 0.1 0.315068

----- ----- ----- ----- 0.15 0.1 0.333333

----- ----- ----- ----- 0.14 0.1 0.285714

----- ----- ----- ----- 0.1 0.1 0

Report two 24

Required results

Reaction order

Order R2 value
First -----
Second -----
Table 3; Reaction orders with their R2 values

Therefore, this reaction is second order

Specific rate constant (k):

Equation of nth order graph is: y = mx + C

From second order rate equation it is concluded that the slope is equal to k

Rate equation

-rA= KCAn
Report two 25

Discussion

Unfortunately, some experimental readings were missing due to an error with the

flowmeter in the tubular reactor device, consequently, one could not measure the flow rates

for none of the experimental samples. Therefore, in the tubular reactor (a steady state

continuous conditions) a fixed flow rate will result constant residence time, hence, the same

time of where the reaction will acquire, and with the near assumption that there is no any

other parameter affects the reactions conditions according to Le Chatelier principle; a

constant rate of reaction will be obtained, thus, concentration and conversion will be

constants throughout the experiment with no respect to the time parameter, however, the

concentrations changed in every sample and this error is explained in sources of errors part,

but again the reaction order could not be determined based on wrong concentration values.

Also, based on the direct relation between the residence time and the flow rate, one could not

obtain the residence time, hence, both the two graphs between the residence time vs

conversion, and the resident time vs initial concentration will not be attained.

Explained mathematically

There is no neither FA nor FB as:

CAi= (FACAT)/ (FA+FB)

No CAi value will be obtained

Hence,

The conversion depends on CAi as:

Conversion will not be calculated

Also,
Report two 26

First order trial using this equation is:

And

Second order trial using this equation is:

Hence, they both also depend on the undetermined CAi

Order of reaction will not be acquired

Finaly,

Residence time ()= V/FTotal

Residence time values will not be obtained

However, if the missing readings were present, all the required results would have

been easy to obtain. Also, they are easy to be predicted, as in case of steady state

conditions with variable flow rates; a variable concentration values directly proportional

to the flow rates would have be obtained, hence, the reaction order and specific rate

constant could have been concluded, also the residence time values which are inversely

proportional to flow rates would have eased the need to create the graphical relation

between it and the conversion, and the concentrations, which their relations would have

been inversely proportional, and directly proportional respectively.

 Report two 27

Sources of error

Human and materials errors

Table 4: Human and materials errors classification and ways to avoid them

Random errors Intrinsic errors

Error How to avoid error Error

Using dirty equipment Wash equipment properly Endpoint is not identical to equivalence point

Leakage of equipment Assure equipments cleaning Volumetric equipment accuracy

Titrating at variable Maintain surroundings Using wrong concentrations solutions

temperatures temperature

Titrating excess Carry out volumes carefully Measuring values less than the minimum

volume of samples degradation

Washing equipment Use proper washing solutions Indicators color change is not immediate

with non-suitable

solutions

Using excess or lack Assure accurate amount of

of indicator indicator

Misreading the Measure volumes precisely

volumes

Observing wrong Observe the color in a proper light

indicators color and background

 Report two 28

Device and surroundings errors

Table 5: Device and surroundings errors classification

Type one Type two (intrinsic)

Configuration Power Determinate Indeterminate
Model error Influence error
error error error error

Failure with Device

Not fixing the improper Standard error Instrument
Electronic noise
flow rate reactor. power percentage parts wearing
usage

Device Chemical
Maximum error
improper Device tearing influence
percentage
calibration (Concentrations)
Physical
Lag time Sensitivity influence
(Vibrations)
Ways and techniques to avoid errors

For systematic (type one) errors:

1. Calibration.
2. Proper device installation.
3. Regular maintenance.

Random (type two) errors:

1. Apply repeatability and reproducibility analysis.
2. By other statistical methods.
3. Take measurements several and calculate average.
Report two 29

Conclusion

All in all, this experimental report did not reach its aim which was to study the

kinetics of sodium hydroxide reaction with ethyl acetate in a tubular flow reactor, it, the

experimental results were not obtained due to an error in the reactors flow meter. It was

required to obtain the order reaction, with specific rate constant, conversion, graphical

relation between conversion and residence time, and finally the time required reach

steady state. The fixed flow rate resulted constant residence time, hence, the same time of

where the reaction will acquire, a constant rate of reaction will be obtained, thus,

concentration and conversion will be constants throughout the experiment with no respect to

the time parameter, however, the concentrations changed in every sample and this error is

explained in sources of errors part, but again the reaction order could not be determined

based on wrong concentration values. Also, based on the direct relation between the

residence time and the flow rate, one could not obtain the residence time, hence, both the two

graphs between the residence time vs conversion, and the resident time vs initial

concentration will not be attained.

However, if the missing readings were present, all the required results would have

been easy to obtain., as in case of steady state conditions with variable flow rates; a

variable concentration values directly proportional to the flow rates would have be

obtained, hence, the reaction order and specific rate constant could have been concluded,

also the residence time values which are inversely proportional to flow rates would have

eased the need to create the graphical relation between it and the conversion, and the

concentrations, which their relations would have been inversely proportional, and directly

proportional respectively.
Report two 30

On the theoretical side, the report discussed tubular reactors mechanism,

equations, controls, uses, advantages and disadvantages. Then finally it discusses

chemical kinetics reaction rates, factors affecting it, specific rate constants, and reactions

orders.
Report two 31

References

5400 Continuous Flow Tubular Reactors. (2012). Retrieved from Parr insturment

company: http://www.parrinst.com/products/tubular-reactor-systems/5400-

continuous-flow-tubular-reactors/

Catalano, S. (2014). Batch reactors. Retrieved from Visual Encyclopedia of Chemical

Engineering:

http://encyclopedia.che.engin.umich.edu/Pages/Reactors/Batch/Batch.html

Catalano, S. (2015). Plug Flow Reactors. Retrieved from Visual Encyclopedia of

Chemical Engineering:

http://encyclopedia.che.engin.umich.edu/Pages/Reactors/PFR/PFR.html

Charles G. Hill, J. (2014). Introduction to Chemical Engineering Kinetics and Reactor

Design,2nd ed (2014).

Chemical Kinetics. (2016). Retrieved from Science Uwaterlo.:

http://www.science.uwaterloo.ca/~cchieh/cact/c123/chmkntcs.html

Factors That Affect Reaction Rates. (2012). Retrieved from Lardbucket:

https://2012books.lardbucket.org/books/principles-of-general-chemistry-v1.0/s18-

01-factors-that-affect-reaction-r.html

First-Order Reactions. (2017, July 4). Retrieved from LibreTexts:

https://chem.libretexts.org/Core/Physical_and_Theoretical_Chemistry/Kinetics/R

eaction_Rates/First-Order_Reactions

Fogler, H. S. (2010, November 22). Essentials of Chemical Reaction Engineering: Mole

Balances. Retrieved from inform it:

http://www.informit.com/articles/article.aspx?p=1652026&seqNum=3
Report two 32

Rate Law and Specific Rate Constant. (2008). Retrieved from ck-12:

https://www.ck12.org/book/CK-12-Chemistry-Concepts-

Intermediate/section/18.8/

Second-Order Reactions. (2014, May 24). Retrieved from LibreTexts:

https://chem.libretexts.org/Core/Physical_and_Theoretical_Chemistry/Kinetics/R

eaction_Rates/Second-Order_Reactions

Soliman, M. (2017). Lab manual. Cairo: BUE.

Yaqoob, M. A. (2011). Batch reactor. Retrieved from slideshare:

https://www.slideshare.net/Awaischaudhary/batch-reactor-34739669

Zero-Order Reactions. (2015, April 15). Retrieved from Libretexts:

https://chem.libretexts.org/Core/Physical_and_Theoretical_Chemistry/Kinetics/R

eaction_Rates/Zero-Order_Reactions