University of San Carlos

Department of Chemical Engineering

CHE 4118L Chemical Engineering Laboratory Investigations 2

Experiment Plan
(Form CHE 4118L-1)

Prepared and submitted by:

Arcenal, Cindy F. Celeres, John Rich F. Pelayo, Jan Daniel V.

Experiment: Reaction Rate Kinetics, Temperature Effects and Performance of a Plug Flow Reactor
Objectives of the Experiment
1. Determine the reaction order and the rate constant for the ethyl acetate-NaOH reaction system using
plug flow reactor data.
2. Determine the variation of conversion with respect to the residence time.
3. Verify the temperature dependence of the reaction rate constant.
Methodological Framework
Objective 1: Determine the reaction order and the rate constant for the ethyl acetate-NaOH reaction system
using plug flow reactor data.
• Set the desired volumetric flowrate of sodium hydroxide (NaOH) solution and ethyl acetate (EtOAc)
solution. Determine the overall volumetric flowrate (𝑣0 ).
• Calculate for the residence time.
𝑉
𝜏 = 𝑃𝐹𝑅 ( 1)
𝑣0
• Determine the NaOH concentration of the effluent given by the equation
𝐶𝐴 = 𝐶𝐻𝐶𝑙 − 0.1(𝐶𝑁𝑎𝑂𝐻 )(𝑉𝑁𝑎𝑂𝐻) (2)

• Plot effluent NaOH concentration (𝐶𝐴 ) against residence time at different orders. For zero order
(n=0), simply plot 𝐶𝐴 against residence time. For first order (n=1), plot effluent ln 𝐶𝐴 against
1
residence time. For second order (n=2), plot effluent 𝐶 against residence time.
𝐴

• Determine the correlation coefficient (R 2) of each plot. Compare and select the plot with an R 2
closest to 1 as that plot determines the order of the reaction.
• Use the slope of the plot which fits the data and evaluate it accordingly to determine the specific
rate constant. If it is a zero and first order reaction, take the negative value of the slope of the line.
If it is a second order reaction, the slope of the line is the specific rate constant.

1
Objective 2: Determine the variation of conversion with respect to the residence time.
• Set the desired volumetric flowrate of sodium hydroxide (NaOH) solution and ethyl acetate (EtOAc)
solution. Determine the overall volumetric flowrate (𝑣0 ).
𝑣0 = 𝑣𝑁𝑎𝑂𝐻,0(𝐵) + 𝑣𝐸𝑡𝑂𝐴𝑐,0(𝐵) (3)
• Calculate for the residence time using Equation 1.
• Determine the molar flow rate of NaOH entering the reactor.
𝐹𝑁𝑎𝑂𝐻(0) = 𝐶𝑁𝑎𝑂𝐻,0(𝐵) 𝑣𝑁𝑎𝑂𝐻,0(𝐵) (4)
• Calculate for the concentration of NaOH entering the reactor using the overall volumetric flow rate.
𝐹𝑁𝑎𝑂𝐻 (0)
𝐶𝑁𝑎𝑂𝐻(0) = ( 5)
𝑣0
• Solve for the volume of unreacted HCl used in the sample for titration process.
𝐶𝑁𝑎𝑂𝐻 (𝑡)
𝑉2(𝑈) = × 𝑉1 (6)
𝐶𝐻𝐶𝑙(𝑠)

• Determine the volume of HCl reacted with NaOH in the sample.

𝑉3(𝑅) = 𝑉𝐻𝐶𝑙 (𝑠) − 𝑉2 (𝑈) ( 7)
• Solve for the number of moles of HCl reacted with NaOH in the sample.
𝑛1(𝑅) = 𝐶𝐻𝐶𝑙(𝑠) × 𝑉3(𝑅) (8)
• Determine the number moles of unreacted NaOH in the sample.
𝑛2(𝑈) = 𝑛1(𝑅) ( 9)
• Calculate for the concentration of unreacted NaOH in the effluent.
𝑛2(𝑈)
𝐶𝑁𝑎𝑂𝐻(𝑈) = 𝑉 (10)
𝑁𝑎𝑂𝐻 (𝑠)

• Determine the conversion of NaOH in the reactor.

𝐶𝑁𝑎 𝑂𝐻 (0)−𝐶𝑁𝑎𝑂𝐻 (𝑈)
𝑋𝑁𝑎𝑂𝐻 = × 100 % (11)
𝐶𝑁𝑎𝑂𝐻 (0)

• Plot the calculated conversion of NaOH (𝑋𝑁𝑎𝑂𝐻 ) with respect to residence time (𝜏) to analyze the
variation between conversion and residence time for the specific reaction.

Objective 3: Verify the temperature dependence of the reaction rate constant.

• Set the volumetric flowrate at a constant value as well as the molar flowrate of reactants.
• Vary the temperature setting at 30°C, 40°C, and 50°C.
• Use the specific rate constant, k, obtained from Objective 1 which will be the y-axis of the ln(k) versus
1/T plot.
• Verify the temperature dependence of the reaction rate constant by examining the linearized trend
in the plot generated.
• From the equation of the line in the plot, solve for the activation energy , E, and the frequency factor,
A, of the reaction by rearranging and simplifying the equations below:
𝐸
𝑚=− (12)
𝑅
𝑏 = ln(𝐴) (13)

2
 Materials, Measuring Apparatus & Equipment

Material Quantity
0.1M Sodium Hydroxide (NaOH) Solution 18 L
0.1M Ethyl Acetate (EtOAc) Solution 18 L
0.1 M Hydrochloric acid (HCl) Solution 10 mL
Phenolphthalein indicator solution 5 mL
Distilled water 1L

Apparatus Size Quantity

Volumetric pipette 10 mL 1
Erlenmeyer flask 200 mL 3
Magnetic bars - 3
Stirrer - 1
Dropper - 3

Equipment Specifications
Titration setup with base burette -
Tubular Flow Reactor Set-up Brand: Armfield
Height: 1.075m
Width: 1m
Depth: 0.66 m
Reactor Volume (inside area
of tube x length): 0.4 L

Task Plan

Time Task Person Responsible

A. Feed Preparation
Prepare 18 L each of 0.1M NaOH solution and 0.1M ethyl acetate Arcenal
(EtOAc) solution. Note: Ensure that NaOH granules are completely
10:00-10:30 dissolved.
AM Pour the NaOH and EtOAc solutions into the empty compartments A and Celeres
B (feed tanks) respectively.
Cover the storage compartments.
B. Equipment Pre-startup
Fully open the main water supply valve. Pelayo
Switch ON the two power supply circuit breakers. Arcenal
Turn 90° clockwise the water bath drain valve (colored black) located
under the reactor water bath to close it.
Set the temperature setting in the control console to 0°. Celeres
10:30-12:00
PM Switch ON the main power switch. Note: Water should start filling the Pelayo
water bath.
When the water bath starts to overflow, turn the stirrer switch ON and
increase the temperature setting to 30.
Note: The error dial located in the temperature control console indicates
the difference between the actual bath temperature and the temperature

3
 setting. It is recommended to start the experiment proper five minutes
after the zero-error is reached.
Remove the sampling beaker positioned at the right side of the water
bath and extend downward the outlet drain.
Switch ON the two feed pump switches. Arcenal
Turn the flowmeter valves to increase the flow (floater should be above
250 scale). Maintain this for around three minutes to purge trapped air
and rinse the TFR.
C. Experiment Proper
C.1 Reaction Rate Kinetics and Plug Flow Reactor Steady-state Performance
Adjust both flowmeters to your desired setting. Celeres
Note: Flow range: 10 – 250 cm3/min, start with the lowest setting, and it
is not necessary that the two flows are equal if 𝛷 𝑉𝑁𝑎𝑜𝐻,𝑖𝑛 𝐶𝑁𝑎𝑂𝐻,𝑖𝑛 =
𝛷𝑉𝐸𝑡𝑂𝐴𝑐,𝑖𝑛 𝐶𝐸𝑡𝑂𝐴𝑐,𝑖𝑛
12:00-2:00 PM Allow sufficient time to reach steady state after two reactor volumes or
one liter of effluent have accumulated.
Record the actual temperature and collect effluent sample for NaOH Pelayo
analysis (refer to Appendix 51B-8a for the procedure). Perform at least
two trials.
Repeat at least three more different values of flows. All
C.2 Influence of Temperature on Reaction
Adjust the temperature setting to 40°C. Adjust both flowmeters to your Arcenal
desired setting and maintain these flows for the rest of the experimental
2:00-3:30 PM period.
Repeat steps 2-3 of part C.1. All
Repeat at a temperature setting of 50°C.
D. Post Experiment
Switch OFF feed pumps and stirrer. Celeres
Drain the storage compartments and rinse with distilled/deionized water.
Fill the storage compartments with distilled water and switch ON the feed Pelayo
pumps (adjust to maximum flow) to rinse the reactor. After rinsing (five
minutes), switch OFF the feed pumps and drain the storage
3:30-4:00 PM compartments.
Drain the water in the water bath.
Switch OFF the power supply. Arcenal
Switch OFF the two circuit breakers.
Close the main water supply line.
Clean and dry the area. All
E. Determination of NaOH Concentration in Effluent
Collect 10.0 ml effluent sample using the volumetric pipette into the Celeres
Erlenmeyer flask.
Immediately pour 10.0 ml of 0.1 M HCl solution into the flask. Pelayo
-
Add a few drops indicator solution. Arcenal
Titrate with 0.1 M NaOH solution until end point (slight tinge of pink). Celeres
Calculate the NaOH solution concentration. All

4
 Information Flow Diagram

Objective 1. Determination on the reaction order and the rate constant for the ethyl acetate-NaOH reaction
system using plug flow reactor data.

Symbol Meaning Unit

𝑉𝑃𝐹𝑅 Volume of the plug-flow reactor L
𝑣0 Total feed volumetric flow rate L/min
𝜏 Mean residence time min
𝐶𝐴 Concentration of sodium hydroxide (NaOH) at the effluent mol/L
𝑣𝑁𝑎𝑂𝐻 ,0 Feed volumetric flow rate of sodium hydroxide (NaOH) before mixing L/min
𝑣𝐸𝑡𝑂𝐴𝑐 ,0 Feed volumetric flow rate of ethyl acetate (EtOAc) before mixing L/min
𝐶𝑁𝑎𝑂𝐻 Concentration of sodium hydroxide (NaOH) mol/L
𝐶𝐻𝐶𝑙 Concentration of hydrochloric acid (HCl) mol/L
𝑉𝑁𝑎𝑂𝐻 Volume of sodium hydroxide (NaOH) added mol/L
𝑅2 Correlation coefficient

5
Objective 2. Determination on the variation of conversion with respect to the residence time.

Legend:
Symbol Meaning Unit
𝑉𝑃𝐹𝑅 Volume of the plug-flow reactor L
𝑣0 Total feed volumetric flow rate L/min
𝜏 Mean residence time min
𝐶𝑁𝑎𝑂𝐻,0(𝐵) Concentration of sodium hydroxide (NaOH) before mixing mol/L
𝑣𝑁𝑎𝑂𝐻,0(𝐵) Feed volumetric flow rate of sodium hydroxide (NaOH) before mixing L/min
𝑣𝐸𝑡𝑂𝐴𝑐 ,0(𝐵) Feed volumetric flow rate of ethyl acetate (EtOAc) before mixing L/min
𝐹𝑁𝑎𝑂𝐻 (0) Feed molar flow rate of (NaOH) mol/min
𝐶𝑁𝑎𝑂𝐻(0) Entering concentration of sodium hydroxide (NaOH) mol/L
𝐶𝑁𝑎𝑂𝐻(𝑡) Concentration of sodium hydroxide (NaOH) used in titration mol/L
𝐶𝐻𝐶𝑙(𝑠) Concentration of hydrochloric acid (HCl) applied in the sample mol/L
𝑉1 Volume of sodium hydroxide (NaOH) used in titration L
𝑉2(𝑈) Volume of unreacted HCl in the sample L
𝑉3(𝑅) Volume of HCl reacted with NaOH in the sample L
𝑉𝐻𝐶𝑙 (𝑠) Total volume of HCl used in the sample L
𝑛1(𝑅) Moles of HCl reacted with NaOH in the sample mol
𝑛2(𝑈) Moles of unreacted NaOH in the sample mol
𝑉𝑁𝑎𝑂𝐻 (𝑠) Total volume of NaOH sample used L
𝐶𝑁𝑎𝑂𝐻(𝑈) Concentration of unreacted NaOH in the effluent mol/L
𝑋𝑁𝑎𝑂𝐻 Conversion of NaOH in the reactor %
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Objective 3. Verification on the temperature dependence of the reaction rate constant.

Legend:
Symbol Meaning Unit
𝐴 Frequency factor mol/L-min or L/min or L/mol-min
𝑏 y-intercept of the equation of the line -
𝐸 Activation Energy J/mol
𝑘 Rate Constant mol/L-min or L/min or L/mol-min
𝑚 Slope of the equation of the line -
𝑅 Gas Constant J/mol-K
𝑇 Temperature of the Reactor K

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 Raw Data Sheets

A. Feed Preparation
Mass of NaOH (𝑚 𝑁𝑎𝑂𝐻 ), g
Concentration of original EtOAc (𝑉𝐸𝑡𝑂𝐴𝑐 ) solution, M
Concentration of original HCl (𝑉𝐻𝐶𝑙 ) solution, M
Volume of EtOAc (𝑉𝐸𝑡𝑂𝐴𝑐 ) used for preparation, mL
Volume of HCl (𝑉𝐻𝐶𝑙 ) used for preparation, mL
Volume of distilled water used for NaOH solution, L
Volume of distilled water used for EtOAc solution, L
Volume of distilled water used for HCl solution, L

Relevant equations for feed preparation:

Ethyl acetate (𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻2 𝐶𝐻3 ) in liquid state – required volume (L)

𝐶2 𝑉2
𝑉1 =
𝐶1
where: 𝑉1 = volume of ethyl acetate to be used from the original solution (L)
𝐶1= concentration of the original ethyl acetate solution (mol/L)
𝑉2 = volume of ethyl acetate required in the experiment (L)
𝐶1= concentration of the original ethyl required in the experiment (mol/L)

Sodium Hydroxide (𝑁𝑎𝑂𝐻) in solid phase – required mass (g)

𝑚 𝑁𝑎𝑂𝐻 = 𝐶𝑁𝑎𝑂𝐻 × 𝑀𝑊𝑁𝑎𝑂𝐻 × 𝑉𝑁𝑎𝑂𝐻

where: 𝑚 𝑁𝑎𝑂𝐻 = mass of NaOH pellets to be used (g)

𝐶𝑁𝑎𝑂𝐻 = concentration of the NaOH solution (mol/L)
𝑉𝑁𝑎𝑂𝐻 = volume of NaOH required in the experiment (L)
𝑀𝑊𝑁𝑎𝑂𝐻 = molecular weight of NaOH (40.0 g/mol)

Hydrochloric Acid (𝐻𝐶𝑙) in liquid state – required volume (L)

𝐶4 𝑉4
𝑉3 =
𝐶3
where: 𝑉3 = volume of HCl to be used from the original solution (L)
𝐶3 = concentration of the original HCl solution (mol/L)
𝑉4 = volume of HCl required in the experiment (L)
𝐶4 = concentration of the HCl required in the experiment (mol/L)

8
B. Reaction Rate Kinetics
Temperature
Flowrate of Flowrate of Trial 1 Trial 2
(°C)
NaOH EtOAc
Volume of NaOH, mL Volume of NaOH, mL
(cm3/min) (cm3/min) Set Actual
Initial Final Initial Final

C. Influence of Temperature on Reaction

Temperature (°C) Flowrate Flowrate Trial 1 Trial 2
of NaOH of EtOAc Volume of NaOH, mL Volume of NaOH, mL
Set Actual (cm3/min) (cm3/min) Initial Final Initial Final

D. Determination of NaOH Concentration in the Effluent

HCl Concentration NaOH Concentration Volume of NaOH Added
Reaction Rate Kinetics

Influence of Temperature on Reaction