Universidad Central del Ecuador

Faculty of Chemical Engineering

Career of Chemical Engineering

Laboratory of Chemical Reactions Engineering 2

PRACTICE No. 2
“Non-Isothermal Reactions”
Semester: Eight

Group No: Mena Fernando

Quito – Ecuador
2016 - 2017
 UNIVERSIDAD CENTRAL DEL ECUADOR
FACULTY OF CHEMICAL ENGINEERING
CAREER OF CHEMICAL ENGINEERING
LABORATORY OF CHEMICAL REACTIONS ENGINEERING 2

PRÁCTICA 1
PSICROMETRIA Y CALOR SENSIBLE

1. OBJETIVES
1.1. Obtain ethyl acetate from the esterification reaction of acetic acid catalyzed by acid in a batch
reactor
1.2. Study the reaction kinetics for the preparation of ethyl acetate in a batch reactor
1.3. Determine the yield of de esterification reaction of ethyl acetate and the achieved conversion
1.4. Understand the importance of the temperature for a reaction in a Batch reactor

2. TEORY
2.1.Residence Time
2.2.Batch Reactor
2.3.Equation for Molar Balance and Design Equation for a Batch Reactor
2.4.General Equation of Energy Balance for a No-Isothermal Batch Reactor
2.5.Temperature dependent factors on Kinetics Equation
2.5.1. The Arrhenius Equation
2.5.2. Activation Energy
2.5.3. Jacobus Henricus Van 't Hoff Equation

3. EXPERIMENTAL SECTION

3.1.Material y equipment
 Batch Reactor
 Beakers
 Chronometer
 Thermometer
 Burette
 Graduated Cylinder
 Weighing scale
 Separation funnel
 Distillation Equipment
 Hoses
 Bunsen Burner
 Tripod
 Universal support

3.2.Substances and Reagents

 Distillated Water H2O(l)
 Glacial Acetic Acid [97%] C2H4O2
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 Ethanol [96%] C2H6O

 Sodium Hydroxide [1.5 N] NaOH
 Concentrated Sulfuric Acid [98%] H2SO4
 Phenolphthalein
 Ice
 Sodium Bicarbonate

3.3.Procedure
 Determine the Reactor’s dimensions
 Prepare 1 L of sodium hydroxide solution (1.5 N).
 Prepare a bicarbonate solution at 10% W/V.
 Verify the correct functioning of the batch reactor and clean it perfectly
 Place 175 mL of glacial acetic acid on the storage tank of the batch reactor and 275 ml of
ethanol (96%) on other and couple correctly the suction hoses of the peristatic bombs
 Place 24 mL of Concentrated Sulfuric Acid on the Reactor
 Turn on the peristatic bombs and set the reaction temperature to 25°C (Increase the temperature
in 4.5°C every 8 min)
 Set the agitation system to 160 RPM
 When the reagents are contacted take a 3 mL sample and pour it into a Erlenmeyer flask that
contains approximately 300 mL of cool water and titrate with sodium hydroxide (1.5 N),
obtaining the initial concentration.
 Take samples every 5 min within an hour treating like the step before
 Titrate the samples as soon as possible with the validated NaOH solution (1.5) using
phenolphthalein as indicator (Turn form Light Yellow to Pink)
 Register in a table the values of volume of titrant agent consumed for each reaction time
 Assemble the Simple Distillation Equipment verifying that there are no leaks
 Once finished the reaction let cool the products and pour to the distillation balon
 Heat the mixture taking on count that the boiling temperature of ethyl acetate is 77 °C
approximately
 Once finished the distillation process pour the product on a Separation Funnel and let the
product cool until it reaches room temperature
 To separate the sodium acetate, add 5g of sodium bicarbonate to the distilled product to
neutralize the remaining acids
 Open the funnel to let the carbon dioxide escape that comes from the neutralization of the acids
 Separate the organic phase that contain the ethyl acetate from the inorganic, and measure the
pH, if it is still acid, made again the washing with sodium bicarbonate until it reaches a neutral
value
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CAREER OF CHEMICAL ENGINEERING
LABORATORY OF CHEMICAL REACTIONS ENGINEERING 2

4. DATA
4.1.Experimental Data

Table 1. Experimental Data

Sample Time [min] Volume of NaOH 1,5N Temperature
[ml] [°C]
1 35 45-52
0
2 5 29.6 50-55

3 10 27.3 55-59

4 15 22.4 60-65

5 20 24.4 65-69

6 25 21.5 70-75

7 30 21 75-80

8 35 20 80-85

Residence Time 35 min

Table 2. Reaction Volumes

Substance Initial Volume Recovered Volume
[mL] [mL]
Acetic Acid 175 ---
Ethanol 275 ---
Ethyl Acetate with Water 450 161.2

4.1.1. Adicional Data

Table 3. Additional Data (Density)

Reagent Density Enthalpy of Cp = f(T)
[g/cm3] Formation
[KJ/mol] Cp = a +bT + cT2 + dT3
[KJ/mol]
Acetic Acid 1.05 -486.18 0.1231
Ethanol 0.81 -277.63 0.1031
Sodium 2.1 -469.4 0.4195
Hydroxide
Sulfuric Acid 1.84 -811.32 0.1391
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Table 4. Additional Data (Boiling Temperature)

Substance Boiling Temperature
[°C]
Ethanol 78.5
Ethyl Acetate 77.1

Table 5. Additional Data (Boiling Temperature)

Dimension Value
[cm]
Height 15
Diameter 10

4.2.Reactions

𝑵𝒂(𝑶𝑯) + 𝑪𝑯𝟑 𝑪𝑶𝑶𝑯 → 𝑪𝑯𝟑 𝑪𝑶𝑶𝑵𝒂 + 𝑯𝟐 𝑶

1
𝑯𝟐 𝑺𝑶𝟒
𝑪𝑯𝟑 𝑪𝑯𝟐 𝑶𝑯 + 𝑪𝑯𝟑 𝑪𝑶𝑶𝑯 ⇔ 𝑪𝑯𝟑 𝑪𝑶𝑶𝑪𝑯𝟐 𝑪𝑯𝟑 + 𝑯𝟐 𝑶
2

5. CALCULATIONS
5.1.Determine the Volume of the Reactor

𝑽 = 𝝅 ∗ 𝒓𝟐 ∗ 𝒉
(1)
2
𝑉 = 0.25𝜋 ∗ 10 ∗ 15
𝑉 = 1178.09 𝑐𝑚3 = 1.1781 𝐿

5.2.Calculation of the final concentration of Acetic Acid

𝑪 𝟏 ∗ 𝑽𝟏 = 𝑪 𝟐 ∗ 𝑽𝟐
(2)

1.5 N ∗ 27.3 mL = 𝐶2 ∗ 3 mL
𝐶2 = 13,65 𝑁
5.3.Obtain ∆𝐇R(T)
𝑻
∆𝐇𝐑 (𝐓) = ∆𝐇𝐑 (𝐓𝐑 ) + ∫ ∆𝑪𝒑𝒊 𝒅𝑻
𝐓𝐑
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(3)
∆𝐇𝐑 (𝐓𝐑 ) = 𝐇𝐑 (𝐜) + 𝐇𝐑 (𝐝) − 𝐇𝐑 (𝐚) − 𝐇𝐑 (𝐛)
(4)

∆HR (TR ) = −463.2 − 285.84 − (277.63) − (486.18)

KJ
∆HR (TR ) = 14.77
mol

∆𝐂𝐩𝒊 = 𝐂𝐩(𝐜) + 𝐂𝐩(𝐝) − 𝐂𝐩(𝐚) − 𝐂𝐩(𝐛)

(5)
KJ
∆Cp𝑖 = 0.1096 + 75.4 ∗ 10−3 − 0.1231 − 0.1031 [ ]
mol ∗ K
KJ
∆Cp𝑖 = −0.0412 [ ]
mol ∗ K
𝑇
∆HR (T) = 14.77 + ∫ −0.0412 𝑑𝑇
298

∆HR (T) = 2.4924 − 0.0412𝑇

5.4.Find T=f(XA) replacing the previous equation in

𝒎
𝑵𝑨𝟎 ∗ ∆HR (T) 𝒅𝑿𝑨 𝒗𝒊 𝒅𝑻
( ) + ∑ (𝑵𝑨𝟎 + 𝑵𝑨𝟎 ∗ 𝑿𝑨 ) Cp𝑖 ∗ =𝟎
𝒂 𝒅𝒕 𝒂 𝒅𝒕
𝒊=𝟏
(5)
1.05𝑔 1 𝑚𝑜𝑙 97
𝑁𝐴0 = 175 mL ∗ ∗ ∗ = 2.9696
𝑚𝐿 60,02 𝑔 100
2.9696 ∗ (2.4924 − 0.0412𝑇) 𝑑𝑋𝐴
( )
1 𝑑𝑡
275 24 𝑑𝑇
+ 2.9696 (0.1231 + (0.1031) + (0.1391) + ∆Cp𝑖 ∗ 𝑋𝐴 ) ∗ =0
175 175 𝑑𝑡
𝑑𝑋𝐴 𝑑𝑇
2.4924 − 0.0412𝑇 ( ) + (0.30419 − 0.0412𝑋𝐴 ) ∗ =0
𝑑𝑡 𝑑𝑡

Evaluating at given initial conditions:

(2.4924 − 0.0412(318)) ∗ 𝑋𝐴
𝑇 = 318 +
0.30419 − 0.0412𝑋𝐴
10.6092𝑋𝐴
𝑇 = 318 +
0.30419 − 0.0412𝑋𝐴
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5.5.Find K=f(T) replacing the previous equation on the Arrhenius equation:

1
𝐾(80°𝐶) = 0.3452
𝑚𝑖𝑛
𝑘𝐽
𝐸 = −38.40
𝑚𝑜𝑙
𝑬 𝟏 𝟏
𝑲(𝑻) = 𝑲(𝑻𝒐 ) 𝐞𝐱𝐩 [ ( − )]
𝑹 𝑻𝒐 𝑻
(6)

−38.40 × 103 1 1
𝑘(𝑇) = 0.3452 exp [ ( − )]
8.314 80 + 273 𝑇

𝑇 − 353
𝑘(𝑇) = 0.3452 exp [−13.0841 ( )]
𝑇
5.6.Determine the reaction’s conversion [XA]
𝑿𝑨
𝒅𝑿𝑨
𝒕𝒓 = 𝑪𝑨𝟎 ∗ ∫
𝟎 −𝒓𝑨
(6)

Where:

−𝒓𝑨 = 𝐾(𝑇)𝐶𝐴𝑜 (1 − 𝑋𝐴 )
𝑋𝐴
𝑑𝑋𝐴
𝑡𝑟 ∗ 𝐾(𝑇) = ∫
0 (1 − 𝑋𝐴 )

𝑋𝐴 = 1 − exp(𝑡𝑟 ∗ 𝐾(𝑇))
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6. RESULTS
Table 6. Results

Time Vol. NaOH (1.5N) XA Temperature [°C] k -ra

35
0
0 52 1.45698553 0.07649174
5 29.6 0.154 55 1.13840918 0.050545368

10 27.3 0.220 59 1.02422959 0.041942202

15 22.4 0.360 65 0.81674203 0.027442532

20 24.4 0.303 69 0.89598092 0.032792902

25 21.5 0.386 75 0.78333881 0.025262677

30 21 0.400 80 0.76535692 0.024108743

35 20 0.429 85 0.7305841 0.021917523

Table 7. Mathematical Models Obtained

Model Equation R2

K=f(T) 𝑇 − 353 0.9871

𝑘(𝑇) = 0.3452 exp [−13.0841 ( )]
𝑇

-rA=f(T) 𝑇 − 353 0.9751

−𝑟𝐴 = 0.3452 exp [−13.0841 ( )]
𝑇
∗ (1 − 𝑋𝐴 )
T=f(XA) 10.6092𝑋𝐴 0.9997
𝑇 = 318 +
0.30419 − 0.0412𝑋𝐴

7. DISCUSSION
8. CONCLUSIONS

8.1.The experimental rate of reaction of ethyl acetate formation follows a model of a first order
kinetics regarding to the acetic acid as it can be seen in the correlation coefficient, with this
assumption (See Table 7)
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LABORATORY OF CHEMICAL REACTIONS ENGINEERING 2

8.2.It can be said that the Temperature of Reaction follows a linear model thus due to the very less
influence that has the increase of Temperature in the Reaction’s Formation Enthalpy, it can be
verified with the correlation coefficient that approximates very nearly to one (See Table 7)

8.3.The experimental reaction rate constant as a function of temperature adjust very well to an
Arrhenius model, as it can be seen in the correlation factor which approximates to one (See
Table 7), it can be said that due to the value of frequency factor (0.3452) the rate of reaction
will be very slow at any given temperature below the experimental conditions. A high
temperature of reaction is recommended under the limits of the reagents, products, catalyzer
and the equipment.

8.4.The conversion to ethyl acetate calculated through the titration of samples shows that the
esterification reaction slows down during the process, as it can be seen in the calculated values
of rate of reaction, this occur due to the increase in reaction temperature, as heat interchange
only occurs with the surroundings the reaction is merely adiabatic. (See Table 6)

9. BIBLIOGRAFIC REFERENCES

9.1.Bibliography
9.1.1. Fogler, H. S. (2001). Elementos de ingeniería de las reacciones químicas. Pearson
Education
9.2.Bibliographic citations

10. BIBLIOGRAFIC REFERENCES

10.1. Equipment Diagram (See Annex 1)
10.2. Diagram K=f(T) (See Annex 2)
10.3. Diagram -rA = f(T) (See Annex 3)
10.4. Diagram T = f(XA) (See Annex 4)
 10.5.
10. ANNEX
10.1 Equipment Diagram

ANNEX 1

Figure 1. Equipment Diagram

NAME DATE UNIVERSIDAD CENTRAL DEL

ECUADOR
DRAW Mena F FACULTY OF CHEMICAL ENGINEERING
CAREER OF CHEMICAL ENGINEERING
REVIEW Manosalvas J.

SCALE THEME: Non-Isothermal Reactions SHEET

01
10.2 Diagram K = f(T)

ANNEX 2

Figure 2. 𝐾 = 𝑓(𝑇)

NAME DATE UNIVERSIDAD CENTRAL DEL

ECUADOR
DRAW Mena F. FACULTY OF CHEMICAL ENGINEERING
CAREER OF CHEMICAL ENGINEERING
REVIEW Manosalvas J.

SCALE THEME: Non-Isothermal Reactions SHEET

02
10.2 Diagram -rA = f(T)

Figure 3. -rA = f(T)

NAME DATE UNIVERSIDAD CENTRAL DEL

ECUADOR
DRAW Mena F FACULTY OF CHEMICAL ENGINEERING
CAREER OF CHEMICAL ENGINEERING
REVIEW Manosalvas J.

SCALE THEME: Non-Isothermal Reactions SHEET

03
10.3 Diagram T=f(XA)

ANNEX 3

Figure 4. K=f(T)

NAME DATE UNIVERSIDAD CENTRAL DEL

ECUADOR
DRAW Mena F FACULTY OF CHEMICAL ENGINEERING
CAREER OF CHEMICAL ENGINEERING
REVIEW Manosalvas J.

SCALE THEME: Non-Isothermal Reactions SHEET

04