Activation Energy

Abstract
In this work, the activation energy of for the formation reaction of tert-amyl ethyl ether
(TAEE) from isoamylenes (2-methyl-1-butene and 2-methyl-2-butene) and the
ethanol was determined as equivalent to 90.67 kJ/mol. The reaction was studied in
the presence of Amberlyst 15 resin as a catalyst in a stirred batch reactor. The
calculation was based on an elementary reaction model without consideration of
reaction equilibrium.

Table of contents
1.

Introduction ............................................................................................... 1

2.

Materials and methods ............................................................................. 2

3.

Results ...................................................................................................... 5

4.

Discussion .............................................................................................. 14

5.

Conclusions ............................................................................................ 14

6.

Feedback on the work ............................................................................ 15

7.

References ............................................................................................. 15

Appendix A: List of other useful data tables ................................................... 16

Appendix B: Other useful equations............................................................... 19

1. Introduction
In this particular work the activation energy of the formation reaction of tert-amyl ethyl ether
(TAEE) from isoamylenes and the ethanol was studied. Ethers, TAEE and tert-amyl methyl
ether (TAME) are used as oxygenates in gasoline fuel. Due to their high octane number, they
offer excellent fuel properties for instance enhancement of fuel burning. Also use of
oxygenates in gasoline contribute to reduction of emissions such as CO, hydrocarbons (HC),
volatile organic compounds (VOCs) and particulates (PM) [1, 2]. Furthermore, substitution of
ethers such as TAEE in gasoline instead of ethanol is said to provide better energy efficiency
(meaning less consumption of fuel) and consequently notable reduction in CO2 emissions
[2, 3]. The studied reaction is presented in Scheme I.

Scheme I
The reaction shown in Scheme I was assumed to behave as an elementary reaction which
proceeds according to reaction Equation (1), where A, B and C represents ethanol
isoamylenes, and tert-amyl ethyl ether respectively.
+

(1)

2. Materials and methods

Reagent and equipment
A solution mixture of reactants, ethanol and isoamylenes diluted in cyclohexane was
provided. The mixture contained ethanol and isomylene in a mole ratio of 2:1 respectively
with 50 mol% cyclohexane. Amberlyst 15 ion exchange resin was applied as the catalyst.
The laboratory equipment used in the test work included: an 80 ml stainless steel batch
reactor, a water bath, stop clock and a magnetic stirrer.
Experimental Methods
Reactor step-up
First as catalyst packing was prepared by hanging the catalyst containing basket on top of
the mixing baffle. The baffle with the catalyst was fitted into the batch reactor gently in
presence of a magnetic stirrer. Caution was observed to ensure that the magnetic stirrer
could freely move at the bottom of the reactor without coming into contact with the mixing
baffle. The reactor was then filled with a known amount of reaction mixture solution to a level
of at least 0.5 cm of void space below the top of the reactor. After, the reactor was
immediately tightly closed to minimized evaporation of the reaction mixture. The reactor with
its contents was immersed in a water bath which was already equilibrated at a desired
temperature (40-70C) and simultaneously the timer was started. This was followed by
immediate start of mixing at 1000 rpm. The sampling line from the reactor was put in an ice
box and covered in order to minimize loss of sample through vapors during sampling. The
reactor was pressurized to 10 bar with use of nitrogen. In each experiment total run time was
about 85 min.
Sampling and shutdown
First a feed sample of obtained from the reaction mixture before startup of the experiment.
During the experiment, samples were taken every after 15 minutes of time interval via the
sampling line. The actual time of sampling for each sample was recorded. A total of five
samples were collected, put into vials, tightly closed and submitted for gas chromatographic
analysis.
At the end of each experimental run, the reactor was removed from the water bath and left to
cool in the ice box for about 10 min. After, the pressure inside the reactor was released
through the sampling line and any solution mixture was collected into a glass beaker and
later discharged into a waste bottle. The reactor was opened, emptied and cleaned. The
used catalyst was recovered and kept aside for future use.

Calculation methods
Determination of response factors
In the gas chromatographic (GC) analytical method, cyclohexane was used as the internal
standard. The GC response factor for each component was determined using Equation (2)
and based on the slopes of the given calibration curves (See Appendix A, Table A-1).

(2)

,
,

Mass fraction calculation

Mass fractions of components were obtained using Equation (3). From the mass fractions,
the mole fractions of component were computed based on the mass of the solution mixture
and equivalent molecular weight. Also the necessary GC data is given in the Appendix A,
Table A-2. Determination of the molar mass of the feed mixture was done as shown in
Appendix B, Figure B-1. In converting mass fractions to mole fractions, the formula shown in
the Appendix B, Figure B-2 was applied.

(3)

,





Determination of the reaction rate and kinetic constant
For a batch reactor the reaction rate can be expressed as in Equation (4). Conversion of
ethanol (component A) was used in calculations and was obtained according to equation (5).
Based on the reaction conversion, Equations (6) and (7) were deduced.


= =

, = 0 (1 )

0
(1 )
0

(0 )
0

(4)

(5)

0 , 0 & ,
, .
0 ,

0
= 0 (1 )
(1 )

0
= .
(1 )2

(6)

(7)

Integrating Equation (7) yields Equation (8) from which k can be determined (See
Appendix B, Figure B-3 for further details about integration) [4].

0
= .

1
0

(8)

Determination of activation energy

Using Arrhenius equation which is shown in Equation (9), the activation energy (Ea) was
estimated graphically from the linear form of Equation (10). Plotting lnk against 1/T according
to Equation (10), activation energy was determined from the slope. The frequency factor, A
was also determined from the intercept.

(9)

() =
() ,

() = ln

(10)

3. Results
The results obtained are presented here and include analytical assays, reaction conversion,
reaction rates, rate constants and the estimated activation energy.

Analytical assays
Determination of Response factors
From Equation (2) response factors of individual components were calculated. As an
example, determination of the response factor of ethanol is shown below. Response factor
results are given in Table 1.

159575
=
= 2.05

77793

Table 1. Gas chromatographic analysis response factors of components.

Component

Slope

Response factor

Cyclohexane

159575

1.00

Isoamylenes

146812

1.09

Ethanol

77793

2.05

TAEE

118434

1.35

Determination of mass and mole fractions

Mass fractions of components in the samples were computed as below from Equation (3).
The assay of the feed sample is used here as an example for the calculation of mass
fractions of individual components in the samples using obtained gas chromatograph peak
areas and response factors. Composition of cyclohexane was considered to be constant in
feed and experimental samples. Examples for calculating mass fractions of components in
the reaction mixture are given below.

. . (2.05 17548.7 0.609)

=
= 0.212
(103214.4 1)
.

. . (1.09 23377.5 0.609)

=
= 0.150
(103214.4 1)
.

. . (1.35 29.2 0.609)

=
= 0.000232
(103214.4 1)
.

As a calculation example for mole fractions, component mole fractions of feed sample are
calculated below (where MW represents molecular weight).

(
) (0.212 69.125)

=
=
= 0.318

46.07
(
)

(
)
= (0.150 69.125) = 0.148
=

70.13
(
)

(
) (0.000232 69.125)

=
=
= 0.000157

102.17
(
)

The full analytical results showing the composition of samples (mass and mole fractions) are
presented in Table 2.

Table 2. Analytical results of samples according to gas chromatographic analysis.

Ethanol

Isoamylenes

TAEE

Cyclohexane

Temp. Time,
, C
h

Mass
fraction

Mole
Mass
fraction fraction

Mole
Mass
fraction fraction

Mole
fraction

Mass
fraction

Mole
fraction

39.9

0.00

0.2123

0.3186

0.1499

0.1477

0.00023

0.00016

0.609

0.50

0.25

0.1987

0.2982

0.1634

0.1611

0.00121

0.00082

0.609

0.50

0.54

0.1980

0.2971

0.1606

0.1583

0.00155

0.00105

0.609

0.50

0.75

0.1991

0.2988

0.1583

0.1560

0.00216

0.00146

0.609

0.50

1.22

0.1974

0.2962

0.1588

0.1566

0.00365

0.00247

0.609

0.50

1.42

0.1974

0.2961

0.1581

0.1559

0.00424

0.00287

0.609

0.50

0.00

0.2123

0.3186

0.1499

0.1477

0.00023

0.00016

0.609

0.50

0.28

0.1971

0.2958

0.1587

0.1564

0.00475

0.00321

0.609

0.50

0.50

0.1977

0.2966

0.1576

0.1553

0.00426

0.00288

0.609

0.50

0.75

0.1968

0.2953

0.1551

0.1528

0.00600

0.00406

0.609

0.50

1.02

0.1958

0.2937

0.1513

0.1491

0.00944

0.00639

0.609

0.50

1.40

0.1949

0.2924

0.1485

0.1464

0.01296

0.00877

0.609

0.50

0.00

0.2123

0.3186

0.1499

0.1477

0.00023

0.00016

0.609

0.50

0.26

0.1997

0.2997

0.1564

0.1542

0.00328

0.00222

0.609

0.50

0.50

0.1976

0.2965

0.1543

0.1521

0.00842

0.00570

0.609

0.50

0.82

0.1954

0.2932

0.1511

0.1489

0.01450

0.00981

0.609

0.50

1.00

0.1935

0.2903

0.1478

0.1457

0.01991

0.01347

0.609

0.50

1.26

0.1906

0.2860

0.1440

0.1420

0.02523

0.01707

0.609

0.50

0.00

0.2123

0.3186

0.1499

0.1477

0.00023

0.00016

0.609

0.50

0.26

0.1982

0.2973

0.1513

0.1492

0.01164

0.00788

0.609

0.50

0.50

0.1934

0.2902

0.1447

0.1426

0.01991

0.01347

0.609

0.50

0.93

0.1862

0.2793

0.1338

0.1319

0.03829

0.02591

0.609

0.50

1.25

0.1812

0.2719

0.1253

0.1235

0.05129

0.03470

0.609

0.50

1.42

0.1762

0.2644

0.1199

0.1182

0.05998

0.04058

0.609

0.50

50.4

60.7

70.9

Reaction conversion and reaction rates

First reaction conversion was calculated based on ethanol from Equation (5). As an example,
reaction conversion at 70.9 C after 1.42 h was determined as follows. Figure 1 shows the
observed conversion of the reaction at different temperatures.

(0 ) (0.3186 0.2644 )
=
= 0.170
0
0.3186
,

0,18
T=39.9C
T=50.4C
T=60.7C
T=70.9C

0,16

Conversion,-

0,14
0,12
0,10
0,08
0,06
0,04
0,02
0,00
0,0

0,2

0,4

0,6

0,8
t, h

1,0

1,2

1,4

1,6

Figure 1. Reaction conversion based on ethanol.

Conversion rate in Equation (6)-(7) was calculated by finite difference using the three-point
differentiation formulas [4] (See Appendix B, Figure B-3). The calculation method is
demonstrated below using the data collected at 70.9 C, particularly for the feed sample (for
time =0), sample at 0.26 h and the last sample at 1.42 h (representing the three point
differentiation formulas respectively).
For time equal to zero (t=0) the derivative was solved as follows,

30 + 4 1 2 (3 0) + (4 0.0667) 0.0891
(
) =
=
=0
2 ()
2 (0.26 0) ()
= 0.3469 (1)

For internal time intervals, such as t = 0.26 h

(0.0891 0)

1
(2 0 ) =
(
)
=
= 0.1856 (1)
=0.26 2
2 (0.5 0.26)

Considering the last sample in that particular series, at t = 1.42 h, conversion rate was
computed as shown below.

1
0.123 (4 0.1466) + (3 0.170)
(3 44 + 35 ) =
(
)
=
=1.42 2
2 (1.42 1.25)
1
= 0.140 ( )

Reaction rates were calculated from the conversion rate and initial concentration of ethanol.
Initial concentrations were estimated from the initial moles and volume of feed solutions (See
Appendix A, Tables A-3 & A-4 for detailed data). But in order to determine the volume,
density of the feed mixture was first estimated as illustrated in the Appendix B, Figure B-1.
Examples of calculated reaction rates for selected samples are given below.

For time equal to zero sample or feed sample at 70.9 C

)
=0

0 (

= 3.667 () 0.3469 (1) = 1.272 . 1 . 1

For time, t = 0.26 h at 70.9C

0 (
)
= 3.667 () 0.1856 (1) = 0.680 . 1 . 1
=0.26

Similary for the last sample, t = 1.42 h at 70.9 C, reaction rate was calculated as follows,

0 (
)
= 3.667 () 0.140 (1) = 0.5134 . 1 . 1
=1.42

Figure 2 shows the reaction rate results obtained. Conversion and reaction rates results are
summarized in Table 3.

-CA0 dXA/dt, mol/L/h

1,6
1,4

T=39.9 C

1,2

T=50.4 C

1,0

T=60.7 C

0,8

T=70.9 C

0,6
0,4
0,2
0,0
-0,2

0,0

0,2

0,4

0,6

0,8

1,0

1,2

t, h
Figure 2. Reaction rate against residence time.

10

1,4

1,6

Table 3. Reaction conversion and reaction rate results.

Time, h
0.00

Conversion
fraction
0.000

dXA/dt,
1/h
0.3763

Reaction
rate,
CA0*dXA/dt
(mol/L/h)
1.3798

0.25
0.54
0.75
1.22
1.42

0.064
0.067
0.062
0.070
0.070

0.1157
0.0044
0.0029
0.0205
0.0189

0.4242
0.0160
0.0108
0.0751
0.0693

50.4

0.00
0.28
0.50
0.75
1.02
1.40

0.000
0.071
0.069
0.073
0.078
0.082

0.3904
0.1533
-0.0029
0.0166
0.0121
0.0099

1.4316
0.5621
-0.0107
0.0610
0.0445
0.0363

60.7

0.00

0.000

0.3256

1.1940

0.26
0.50
0.82
1.00
1.26

0.059
0.069
0.080
0.089
0.102

0.1430
0.0322
0.0527
0.0442
0.0619

0.5242
0.1181
0.1931
0.1622
0.2269

0.00
0.26
0.50
0.93
1.25
1.42

0.000
0.067
0.089
0.123
0.147
0.170

0.3469
0.1823
0.0652
0.0907
0.1411
0.1414

1.2720
0.6686
0.2390
0.3325
0.5174
0.5186

Temp., C
39.9

70.9

Rate constants and activation energy

Determination of the reaction rate constant
Rate constants at different temperatures were estimated graphically using Equations (8). In
each case, the rate constant was calculated from the slope of linearized plots of (1 )
against time, t (See Appendix A, Table A-5). Figure 3 shows the obtained linearized plots
and the slopes used for calculating the kinetic constant. Since initial concentration of
reactants were already known (Appendix A, Table A-4c), k was easily determined. As an
illustration, rate constant at 70.9 C was calculated from the corresponding slope as shown

11

below. The results of rate constants at different temperatures are presented in Table 4 (See
also Appendix A, Table A-6).

= 0.1286

0
3.667

= 0.1286
= 0.2572
0
1.833
.

T=39.9 C
0,08

y = 0,0066x + 0,0661
R = 0,5488

y = 0,0131x + 0,0704
R = 0,8656

0,09

XA/(1-XA)

0,075

XA/(1-XA)

T=50.4 C
0,1

0,07

0,065
0,06

0,08
0,07
0,06

0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4

0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4

t, h

t, h

T=60.7 C

T=70.9 C
0,25

y = 0,0495x + 0,049
R = 0,9885

0,1

y = 0,1286x + 0,021
R = 0,9632

0,2

XA/(1-XA)

XA/(1-XA)

0,12

0,08
0,06

0,15
0,1
0,05
0

0,04
0,0

0,2

0,4

0,6

0,8

1,0

1,2

0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4

1,4

t, h

t, h

Figure 3. Plots for determination of rate constants, k at different reaction temperatures based on
reaction conversion of ethanol.

Table 4. Rate constants at different temperatures.

Temp.C

Reaction rate coefficient, k

(L/mol/h)

39.9

0.01320

50.4

0.02620

60.7

0.09900

70.9

0.25720

12

Determination of the activation energy

Arrhenius plot shown in Figure 4 was generated according to Equations (9)& (10). From the
slope of the plot as indicated in Equation (10), activation energy was calculated. The
calculation is also demonstrated below.

1/T, (K-1)
-1
0,0029
-1,5

0,00295

0,003

0,00305

0,0031

0,00315

0,0032

0,00325

-2

ln(k)

-2,5

y = -10906x + 30,34
R = 0,9786

-3
-3,5
-4
-4,5
-5

Figure 4. Arrhenius plot for determination of activation energy.

= (. ) 10906 (1 ) = 8.314 10906 = 90672.48 /

Activation energy of 90.67 kJ/mol was obtained and a frequency factor (A), of 1.5e13. More
details are given in the Appendix A, Table A-6.

13

4. Discussion
In general, the rate of the reaction is slow. Appreciable conversion requires use of higher
temperature e.g. 70C. At this lower temperatures for instance <40C, the reaction is much
slower. This effect can also be observed in Figure 3 where it was relatively difficult to
estimate the rate constant. However, it is important to note that, initially (within the 15 min
time) the reaction rate was reasonably fast but after slowed down dramatically. This behavior
was more pronounced at lower temperatures studied (40-50C). The reasons for this kind of
phenomenon were not clearly understood. Among the speculated reasons would be due to
mass transfer constraints in the catalyst particles, slow chemical reaction and probably the
effect of reaction equilibrium.

According to the observed activation energy of 90.67 kJ/mol, it is relatively high which would
indicate a fairly slow reaction at lower temperatures even in the presence of the catalyst. In
literature, Linnekoski and Krause [5] reported activation energy for formation of TAEE from
2-methyl-1-butene and 2-methyl-2-butene to be equivalent to 90 kJ/mol and 108 kJ/mol
respectively. Gonzlez-Rugerio et al. [6], reported activation energies of 76.8 kJ/mol and
95.9 kJ/mol corresponding to use of 2-methyl-1-butene and 2-methyl-2-butene respectively.
Comparing the results in both cases, the observed activation energy in this work is within
range.
However, in the present work the reaction was taken as an elementary reaction but from
theory [5, 6] different steps may occur as shown in scheme I and thus affect the overall
estimation of kinetic parameters.

5. Conclusions
The observed activation energy of 90.67 kJ/mol was comparable to the literature values even
though, the reaction mechanism was simplified to an elementary reaction and the effects of
isomerization, equilibrium were not taken into account. Furthermore, the reaction
demonstrated fast initial reaction rates but overall exhibited low conversion especially at
temperatures of 39.9-50.4C.

14

6. Feedback on the work

The experimental work was an interesting experience with clear instructions for experimental
setup and operation. The use of two reactors also was advantageous not only to complete
the work in ample time but also for hands on experience for the participants. The instructor
did a great job in guidance through experimental procedures and treatment of analytical
results. Overall it is a very good experimental assignment.

7. References
1. European Fuel Oxygenates Association. Fuel Ethers improve Air Quality and reduce GHG
emissions, [online], Available: http://www.efoa.eu/en/fuel-ethers/fuel-ethers-improve-airquality-and-reduce-ghg-emissions.aspx [April 6, 2016]
2. The European Fuel Oxygenates Association. Fuel Ethers enable the Use of Biofuels, [online],
Available: http://www.efoa.eu/en/fuel-ethers/fuel-ethers-enable-the-use-of-biofuels.aspx
[April 06, 2016]
3. Hart Energy Consulting (2011) Relative CO2 Savings Comparing Ethanol and TAEE as a
Gasoline Component [online], Available:
http://www.efoa.eu/documents/document/20110328150906-2011-0323_relative_co2_savings_comparing_ethanol_and_taee_as_a_gasoline_component.pdf [April
6, 2016]
4. Fogler HS, Elements of Chemical Reaction Engineering, 4th edn, Pearson, Westford, 2005
5. Linnekoski JA, Krause,O.A and Rihko KL, Kinetics of the Heterogeneously Catalyzed
Formation of tert-Amyl Ethyl Ether. Industrial & Engineering Chemistry Research 36 (2):310316 (1997).
6. Gonzlez-Rugerio CA, Keller T, Pilarczyk J, Saacki W and Grak A, TAEE synthesis from
isoamylenes and ethanol by catalytic distillation: Pilot plant experiments and model validation.
Fuel Processing Technology, 102:1-10 (2012).

15

Appendix A: List of other useful data tables

Table A-1. Gas chromatographic analysis calibration curves.

Table A-2 GC data for reactor samples

Peak areas
Reactor
samples

Cyclohexane

Time, h

T=39.9C

0.00

Isoamylenes

Ethanol

TAEE

103214.4

23377.5

17548.7

29.2

0.25

103211.3

25494.6

16426.7

152.2

0.54

105302.9

25552.5

16695.6

198.4

0.75

104300.7

24951.2

16632.3

274.2

1.22

104604.5

25110.5

16535.9

465.4

1.42

103846.8

24817.6

16413.3

537.3

Time, h

T=50.4C

0.00

103214.4

23377.5

17548.7

29.2

0.28

104768.5

25121.2

16539.8

606.9

0.50

104279.8

24832.1

16506.8

541.2

0.75

104876.2

24578.3

16531.2

767.8

1.02

103239.5

23603.3

16184.7

1188.3

1.40

105138.5

23603.3

16407.5

1661.0

Time, h

T=60.7C

0.00

103214.4

23377.5

17548.7

29.2

0.26

104409.2

24682.1

16698.5

417.4

0.50

104915.4

24460.9

16605.3

1077.3

0.82

103527.2

23639.7

16198.3

1830.1

1.00

103370.1

23094.6

16016.3

2508.7

1.26

104725.4

22797.5

15987.4

3221.0

Time, h

T=70.9C

0.00

103214.4

23377.5

17548.7

29.2

0.26

103547.7

23683.3

16432.6

1469.6

0.50

106286.5

23243.3

16460.1

2580.6

0.93

104730.4

21173.9

15614.6

4889.1

1.25

104907.7

19871.9

15222.0

6560.5

1.42

106323.2

19261.6

15001.8

7774.6

16

Table A-3. Physical properties of components

Molar mass, g/mol
Isoamylenes
Ethanol
70.13
46.07
Density, g/cm3
Isoamylenes
Ethanol
0.650
0.789

Cyclohexane
84.16

TAEE
102.17

Feed solution mixture

69.125

Cyclohexane
0.7781

Table A-4a. Initial mole fractions details

39.9

Reactor
feed
solution
49

0.709

0.354

0.236

0.118

0.5

0.333

0.167

50.4

47.4

0.686

0.343

0.229

0.114

0.5

0.333

0.167

60.7

52.47

0.759

0.380

0.253

0.127

0.5

0.333

0.167

70.9

53.73

0.777

0.389

0.259

0.130

0.5

0.333

0.167

Experiment
Temp. C

Total
moles

Moles of components
Cyclohexane

Ethanol

Isoamylenes

Mole fractions
Cyclohexane

Ethanol

Isoamylenes

Table A-4b. Initial mass fractions details

Experiment

Reactor feed
solution

Masses of Components

Mass fractions

Temp. C
39.9
50.4

mass, g
49
47.4

Cyclohexane
29.829
28.855

Ethanol
10.886
10.530

Isoamylenes
8.285
8.015

Cyclohexane
0.6088
0.6088

Ethanol
0.2222
0.2222

Isoamylenes
0.1691
0.1691

60.7
70.9

52.47
53.73

31.941
32.708

11.657
11.937

8.872
9.085

0.6088
0.6088

0.2222
0.2222

0.1691
0.1691

Table A-4c. Initial concentrations details

Experiment
Temp
39.9
50.4
60.7

Reactor feed
solution, mL
64.4
62.3
69.0

Component moles
Cyclohexane Ethanol
0.354
0.236
0.343
0.229
0.380
0.253

Isoamylenes
0.118
0.114
0.127

Concentration, mol/L
Cyclohexane Ethanol
5.500
3.667
5.500
3.667
5.500
3.667

Isoamylenes
1.833
1.833
1.833

70.9

70.7

0.389

0.130

5.500

1.833

0.259

17

3.667

Table A-5. Calculated (plotted) data for determination of the rate constant
Experiment

t, h

XA/1-XA

1/t

0.2500

0.0683

4.000

0.5417

0.0724

1.846

0.7500

0.0662

1.333

1.2167

0.0755

0.822

1.4194

0.0757

0.705

0.2778

0.0770

3.600

0.5028

0.0741

1.989

0.7500

0.0786

1.333

1.0194

0.0845

0.981

1.4000

0.0895

0.714

0.2583

0.0631

3.871

0.5000

0.0742

2.000

0.8167

0.0867

1.224

1.0028

0.0973

0.997

1.2556

0.1137

0.796

0.2556

0.0714

3.913

0.5000

0.0979

2.000

0.9333

0.1404

1.071

1.2500

0.1718

0.800

1.4167

0.2050

0.706

Temp. C
39.9

50.4

60.7

70.9

Table A-6. Estimated rate constant from generated slopes

T, K

Slope =
k*CB0/CA0

K
(L/mol/h)

313.05

0.00660

0.01320

-4.32754 0.003194

323.55

0.01310

0.02620

-3.642 0.003091

333.85

0.04950

0.09900

-2.31264 0.002995

343.05

0.12860

0.25720

-1.3579 0.002915

LN(k)

1/T, (1/K)

Note: subscript A represents ethanol & B for isomylenes.

18

Appendix B: Other useful equations

Molecular weight of the mixture calculation

( ) = ( ) ( ) + (

)( ) + ( )( )
= (84.16 0.5) + (46.07 0.333) + (70.13 0.167) = 69.13 /
Density of the mixture calculation

( 3 ) = ( ) ( 3 ) + ( ) ( 3 ) +

( ) ( 3 )

= (0.7781 0.5) + (0.789 0.333) + (0.650 0.167) = 0.760 /3

Figure B-1 Formulas used in the calculation of molar mass and density of feed solution

Figure B-2. (Source: Wikipedia 2016)

19

Figure. B-3. (Source: Fogler, 2005)

20