Contents

1.0 TITLE ............................................................................................................................... 2

2.0 INTRODUCTION ...................................................................................................... 2
2.1 EXPERIMENTAL BACKGROUND ..................................................................... 2
2.2 THEORIES AND EXPLANATIONS ................................................................... 3
3.0 OBJECTIVE................................................................................................................. 5
4.0 LABORATORY EQUIPMENTS ............................................................................... 5
5.0 PROCEDURE .............................................................................................................. 6
5.1 Ascertain the order of reaction: ......................................................................... 6
5.2 Determining the activation energy of saponification: ............................... 6
6.0 OBSERVATION ......................................................................................................... 7
7.0 EXPERIMENTAL RESULTS / DATA & ANALYSIS ........................................... 7
7.1 EXPERIMENTAL RESULTS ................................................................................. 7
7.2 Activation Energy, E and Frequency (Pre-exponential Factor), k0...... 36
8.0 DISCUSSION/RECOMMENDATION ................................................................ 39
9.0 CONCLUSION .......................................................................................................... 40
10.0 REFERENCES ....................................................................................................... 41
11.0 APPENDIX ............................................................................................................ 41

1
1.0 TITLE
Kinetic Studies in Batch Reactor (Saponification of Ethyl Acetate)

2.0 INTRODUCTION
2.1 EXPERIMENTAL BACKGROUND
A batch reactor may be described as a vessel in which chemicals are
placed to react. Batch operation has the following characteristics

1) Time variant conditions

2) Discontinuous production

3) Downtime for cleaning and filling

4) Flexibility

Many reactors particularly in the fine chemical industry are operated in a pure
batch manner. During the reaction period there is a change in substrate and product
concentration with time; the other periods, e.g. emptying, cleaning, filling, are time
lost.

Figure 1: Batch Reactor

Batch reactors are normally used in small-scale laboratory set-ups to study the
kinetics of chemical reactions. To determine the order and rate constant of a chemical
reaction, the variation of a property of the reaction mixture is observed as the reaction
progresses. Data collected usually consist of changes in variables such as
concentration of a component, total volume of the system or a physical property. The
data are then analyzed using pertinent equations to find desired kinetic parameters.

2
 In this experiment, this can be divided into two parts: (i) to find the reaction
order and the rate constant at constant at constant temperature (ii) to determine the
activation energy for saponification of ethyl acetate. As the reaction rates depend on
the composition and the temperature of the reaction mixture thus, every chemical
reaction occurs at finite rate and therefore can potentially serve as the basis for a
chemical kinetic method of analysis. On the other hand, activation energy is the energy
barrier that has to be overcome for this reaction to happen.

2.2 THEORIES AND EXPLANATIONS

The saponification in ethyl acetate in dilute aqueous solution can be written
as :

CH3COOC2H5 (l) + NaOH (l) = CH3COONa (l) C2H5OH (l)

Because that the reaction saponification of ethyl acetate is a single reaction, let A be
NaOH and B be CH3COOC2H5, the rate equation can be defined as

-rA = k(CA)(CB)

= kf (CA)

= kCAn

When one mole of A reacts with one mole of B

In determining the rate constant of the reaction, we can use the differential
method. The differential method of analysis deals with the differential rate equation
𝒅𝑪𝑨
to be tested, evaluating all terms in the equation including the derivative , and
𝒅𝒕
testing the goodness of fit of the equation with the experiment. By plotting the graph
of concentration CA versus time t, we can find the slope or tangent at point for the
suitably selected concentration values by using mirror method. The slope of these
𝒅𝑪𝑨
points , is the rates of reactions at certain compositions. Then, plot the graph of
𝒅𝒕
𝒅𝑪𝑨
𝐥𝐨𝐠 𝟏𝟎 (− 𝒅𝒕
) vs 𝐥𝐨𝐠 𝟏𝟎 𝑪𝑨

𝒅𝑪𝑨
−𝒓𝑨 = − = 𝒌𝑪𝒏𝑨
𝒅𝒕

3
 𝒅𝑪𝑨
𝐥𝐨𝐠 𝟏𝟎 (− ) = 𝒏 𝐥𝐨𝐠 𝟏𝟎 𝑪𝑨 + 𝐥𝐨𝐠 𝟏𝟎 𝒌
𝒅𝒕

The graph of log [dCA/dt] vs log [CA] is a straight line. The rate constant, k and the
order of the reaction, n can be directly obtained by finding the intercepts and the
𝒅𝑪𝑨
slope from the graph of 𝐥𝐨𝐠 𝟏𝟎 (− 𝒅𝒕
) vs 𝐥𝐨𝐠 𝟏𝟎 𝑪𝑨 .

The Arrhenius eqution:

𝑘 = 𝐴𝑒 −𝐸⁄𝑅𝑇

Where K =rate constant

A =frequency factor

E =activation energy

R = ideal gas constant

T =temperature

Rearranging the Arrhenius equation,

𝑬 𝟏
∴ 𝐥𝐧 𝒌 = (− ) ( ) + 𝐥𝐧 𝑨
𝑹 𝑻

Figure: 2L beaker on a heater.

As shown in the picture, a 2L beaker was heated by a heater to the desired

temperature: 40°C and 50 °C. The beaker was playing a role as a batch reactor. A
magnetic stirrer that acted as an agitator, was placed inside the beaker to stir and
mix the solutions.

4
Justification of Experiment’s Importance

In this study, students were exposed to the simulated mechanism of a batch

reactor, which was similar to an actual mechanism of a commercial batch reactor.
Under three different temperature profiles, different rates of reaction due to the
difference in k values could be observed, and as a result, effects of temperature on
the rate constant could be studied.

3.0 OBJECTIVE
1. To verify that the saponification of ethyl acetate in dilute aqueous solution is
a second order reaction.
2. To report the value of the reaction rate constant.
3. To find the activation energy of the reaction of saponification of ethyl acetate
in dilute aqueous solution.

4.0 LABORATORY EQUIPMENTS

Apparatus and Materials

1. Ethyl Acetate, pure 10 mL

2. NaOH (aqueous, 0.05M) 1 litre
3. HCl (aqueous 0.1M) 500 mL
4. Phenolphthalein indicator
5. Batch reactor (1 litre beaker)
6. A dozen conical flaskS (250 mL)
7. Measuring pipette (5 mL) and burettes 10 mL and 25 mL
8. Pipettes
9. Stop-watch

5
5.0 PROCEDURE
5.1 Ascertain the order of reaction:
1. 1 litre of NaOH solution was placed in a clean 1 litre beaker, which serves as the
reactor.
2. 10 mL of 0.1 M HCl solution was transferred into each of twelve conical flasks,
which were serially labeled.
3. The reactor was placed on a magnetic stirrer and start stirring vigorously. A clean
and dry 10 mL pipette was keep handy.
4. By mean of a clean and dry measuring pipette, exactly 10 mL of ethyl acetate was
transferred into the reactor and the stop watch was started simultaneously. 0.1
M of ethyl acetate solution formed in the reactor itself and saponification reaction
was started from now.
5. At the reaction times 1,2,3,4,5,6,7,8,9,10,11,12 minutes, 10 mL of the reaction
solution mixture was pipette into each one of the labeled conical flasks.
Note: The stopwatch must not stop until all the twelve samples are transfer.
6. The contents of twelve conical flasks were back-titrated with aqueous NaOH from
the burette using phenolphthalein as indicator (appearance of first shade of pink
color is the end point of titration).
7. The experiment should be carried out at room temperature.

Explanation: Note that when a sample of reaction mixture is transferred into the
conical flask containing HCl, the alkali in the reaction mixture gets neutralized and so
the saponification reaction stops. Back-titration of the contents of this flask therefore
helps in determining the amount of unreacted NaOH present in the reaction mixture
at the time of its removal from the reactor. In other words, the experiment helps to
find the alkali concentration (CA) in the reactor as a function of time (t).

5.2 Determining the activation energy of saponification:

Steps 1-6 in section 5.0.1 were repeated. The experiment was conducted at 400C and
500C instead of room temperature.

6
6.0 OBSERVATION
1. White fume is produced when 10 mL of ethyl acetate was added into the reactor.
2. The colour of the solution during back-titration turned from colourless to light pink.
3. At 400C and 500C, there are lipid-like bubbles in the mixture.

7.0 EXPERIMENTAL RESULTS / DATA & ANALYSIS

7.1 EXPERIMENTAL RESULTS
TABLE 7.1 Saponification reaction conducted at T=____________20________ oC

Time, t Reading of burette(ml) Volume of NaOH

(min) used, ∆V , mL
V initial V final

1 0.25 9.00 8.75

2 9.00 18.40 9.40

3 18.40 28.40 9.90

4 28.30 38.50 10.20

5 0.30 10.80 10.50

6 10.80 21.40 10.60

7 21.40 32.40 10.80

8 1.85 32.30 10.80

9 12.65 12.65 10.85

10 23.50 23.50 11.20

11 14.40 25.30 10.90

12 25.30 36.50 11.20

TABLE7.2 Saponification reaction conducted at T=____________40________ oC

Time, t Reading of burette(ml) Volume of NaOH

(min) used, ∆V , mL
V initial V final

1 3.50 9.70 6.20

7
 2 9.70 20.80 11.10

3 20.80 32.60 11.80

4 32.60 43.60 11.00

5 0.00 11.40 11.40

6 5.00 15.20 10.20

7 15.20 25.50 10.30

8 25.50 35.80 10.30

9 10.70 20.90 10.20

10 0.00 10.70 10.70

11 20.90 30.70 9.80

12 30.70 40.70 9.80

TABLE7.3 Saponification reaction conducted at T=____________50________ oC

Time, t Reading of burette(ml) Volume of NaOH

(min) used, ∆V , mL
V initial V final

1 0.00 7.80 7.80

2 0.00 9.30 9.30

3 0.00 10.10 10.10

4 0.00 10.00 10.00

5 0.20 10.30 10.10

6 0.00 10.10 10.10

7 0.00 10.20 10.20

8 0.00 10.00 10.00

9 0.00 9.90 9.90

10 9.90 20.00 10.10

11 20.00 30.10 10.10

12 30.10 40.10 10.00

8
Results Analysis and Graphs

Sample Calculation on Saponification Reaction Conducted at T = 20 oC (Room Temperature)

Table 7.4: Calculated data for Saponification reaction conducted at T = 20 oC (room temperature).

𝟏 𝐝𝐂𝐍𝐚𝐎𝐇 𝐝𝐂𝐍𝐚𝐎𝐇
Time, t (min) VNaOH (mL) CNaOH (𝐦𝐨𝐥⁄𝐋) (𝐋⁄𝐦𝐨𝐥) 𝐥𝐨𝐠 𝟏𝟎 (− ) 𝐥𝐨𝐠 𝟏𝟎 (𝐂𝐍𝐚𝐎𝐇 ) 𝐗𝐀
𝐂𝐍𝐚𝐎𝐇 𝐝𝐭 𝐝𝐭

1 8.75 0.05625 17.77777778 -0.0023 -2.638272164 -1.249877473 0.020922878

2 9.40 0.053 18.86792453 -0.0021 -2.677780705 -1.27572413 0.040988166

3 9.90 0.0505 19.8019802 -0.0019 -2.721246399 -1.296708622 0.060247531

4 10.20 0.049 20.40816327 -0.0017 -2.769551079 -1.30980392 0.078748572

5 10.50 0.0475 21.05263158 -0.0015 -2.823908741 -1.32330639 0.096535213

6 10.60 0.047 21.27659574 -0.0013 -2.886056648 -1.327902142 0.113648047

7 10.80 0.046 21.73913043 -0.0011 -2.958607315 -1.337242168 0.130124653

8 10.80 0.046 21.73913043 -0.0009 -3.045757491 -1.337242168 0.145999863

9 10.85 0.04575 21.8579235 -0.0007 -3.15490196 -1.339608902 0.161306014

10 11.20 0.044 22.72727273 -0.0005 -3.301029996 -1.356547324 0.176073165

11 10.90 0.0455 21.97802198 -0.0003 -3.522878745 -1.341988603 0.190329293

12 11.20 0.044 22.72727273 -1E-04 -4 -1.356547324 0.204100474

9
Note:

1. HCl react with the remaining NaOH from the reaction

2. Back titration is to find back the remaining HCl which have not yet reacted

Order of Reaction, n and Rate Constant, k

Differential Method of Analysis

Overall reaction equation

Taking the experimental of data time, t = 1 min for sample calculation.

𝐍𝐚𝐎𝐇(𝐫𝐞𝐦𝐚𝐢𝐧𝐞𝐝, 𝐦𝟏) × 𝐯𝐨𝐥𝐮𝐦𝐞𝟏 + 𝐍𝐚𝐎𝐇(𝐚𝐝𝐝𝐞𝐝, 𝐦𝟐 ) × 𝐯𝐨𝐥𝐮𝐦𝐞𝟐

= 𝐇𝐂𝐥(𝐚𝐝𝐝𝐞𝐝, 𝐦𝟑) × 𝐯𝐨𝐥𝐮𝐦𝐞𝟑

𝐍𝐚𝐎𝐇(𝐫𝐞𝐦𝐚𝐢𝐧𝐞𝐝, 𝐦𝟏)
(𝐇𝐂𝐥(𝐚𝐝𝐝𝐞𝐝, 𝐦𝟑) × 𝐯𝐨𝐥𝐮𝐦𝐞𝟑 − 𝐍𝐚𝐎𝐇 (𝐚𝐝𝐝𝐞𝐝, 𝐦𝟐) × 𝐯𝐨𝐥𝐮𝐦𝐞𝟐)
=
𝐯𝐨𝐥𝐮𝐦𝐞 𝟏

.
𝒎𝒐𝒍 𝒎𝒐𝒍
𝟎. 𝟏( 𝑳 ) × 𝟏𝟎𝐦𝐥 − 𝟎. 𝟎𝟓( 𝑳 ) × 𝟖. 𝟕𝟓𝐦𝐥
𝐍𝐚𝐎𝐇(𝐫𝐞𝐦𝐚𝐢𝐧𝐞𝐝, 𝐦𝟏) =
𝟏𝟎𝐦𝐥
𝒎𝒐𝒍
𝐍𝐚𝐎𝐇(𝐫𝐞𝐦𝐚𝐢𝐧𝐞𝐝, 𝐦𝟏) = 𝟎. 𝟎𝟓𝟔𝟐𝟓( )
𝑳

10
Graph of concentration of NaOH (mol/L) against time, t (min) at 20 oC

Graph of concentration of NaOH (mol/L) against time, t (min)

0.058

0.056

y = 0.0001x2 - 0.0025x + 0.0577

0.054 R² = 0.9644

0.052
CNaOH (L/mol)

0.05

0.048

0.046

0.044

0.042

0.04
0 2 4 6 8 10 12 14
Time, t (min)

Figure 7.1: Graph of concentration of NaOH (mol/L) against time, t (min) at 22 oC.

11
From Figure 7.1, the nonlinear equation obtained was:

𝐶𝑁𝑎𝑂𝐻 = 0.0001𝑥 2 − 0.0025𝑥 + 0.0577

Differentiating the equation with respect to time,

𝑑𝐶𝑁𝑎𝑂𝐻
= 0.0002𝑥 − 0.0025
𝑑𝑡

Now, substitute the value of t into the above equation,

𝒅𝑪𝑵𝒂𝑶𝑯
∴ = 0.0002(1) − 0.0025
𝒅𝒕
𝒅𝑪𝑵𝒂𝑶𝑯
∴ = −𝟎. 𝟎𝟎𝟐𝟑
𝒅𝒕

General equation for rate of reaction,

𝒅𝑪𝑨
−𝒓𝑨 = − = 𝒌𝑪𝒏𝑨
𝒅𝒕

The following shows the transformation the general equation of rate of reaction above
into logarithms form:

𝑑𝐶𝐴
log10 (− ) = log10(𝑘𝐶𝐴𝑛 )
𝑑𝑡
𝑑𝐶𝐴
log10 (− ) = log10 (𝑘) + log10 (𝐶𝐴𝑛 )
𝑑𝑡
𝑑𝐶𝐴
log10 (− ) = log10 𝑘 + 𝑛 log10 𝐶𝐴
𝑑𝑡
𝒅𝑪𝑨
∴ 𝐥𝐨𝐠 𝟏𝟎 (− ) = 𝒏 𝐥𝐨𝐠 𝟏𝟎 𝑪𝑨 + 𝐥𝐨𝐠 𝟏𝟎 𝒌
𝒅𝒕

Standard linear equation,

𝑦 = 𝑚𝑥 + 𝑐

By comparing the derived logarithmic general equation of rate of reaction with the
standard linear equation, we discovered that the slope of the graph of
𝑑𝐶𝐴
log10(− 𝑑𝑡
) against log10 𝐶𝐴 (Figure 7.2), we can determine the order of reaction, 𝑛
while through the y-intercept of the same graph, we can determine the value of 𝑘
which is the rate constant of the Saponification reaction.

12
Graph of log10 (-dCA/dt) against log10 (CA) at 20 oC.

Graph of log10 (-dCA/dt) against log10 (CA)

0
-1.38 -1.36 -1.34 -1.32 -1.3 -1.28 -1.26 -1.24
-0.5

-1

-1.5
y = 9.2701x + 9.2045
R² = 0.5656
-2

-2.5

-3

-3.5

-4

-4.5

Figure 7.2: Graph of log10 (-dCA/dt) against log10 (CA) at 20 oC.

13
From Figure 7.2, the linear equation obtained was:

𝒚 = 𝟗. 𝟐𝟕𝟎𝟏𝒙 + 𝟗. 𝟐𝟎𝟒𝟓

This equation can be further modified into the equation as shown below in order to
predict the subsequent variables that needed in the later calculations that involved in
determined the outcome of the experiment.

𝒅𝑪𝑨
∴ 𝐥𝐨𝐠 𝟏𝟎 (− ) = 𝟗. 𝟐𝟕𝟎𝟏𝐥𝐨𝐠 𝟏𝟎 𝑪𝑨 + 𝟗. 𝟐𝟎𝟒𝟓
𝒅𝒕

Hence, the slope of the graph in Figure 7.2 represents the value order of reaction,

∴ 𝒏 = 𝟗. 𝟐𝟕𝟎𝟏

𝑇ℎ𝑒 𝑖𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡 𝑜𝑓 𝑦 − 𝑎𝑥𝑖𝑠 = log10 𝑘

9.2045 = log10 𝑘

𝑘 = 10𝟗.𝟐𝟎𝟒𝟓

∴ 𝒌 = 𝟏. 𝟗𝑿𝟏𝟎^𝟗 (𝐦𝐨𝐥⁄𝐋) ⁄𝐦𝐢𝐧

Therefore, the order of the reaction, 𝒏 = 𝟏. 𝟔𝟖𝟕𝟎𝟒𝟗𝟕𝟗𝟒𝟎 and 𝒌 ∴ 𝒌 =

𝟏. 𝟗𝑿𝟏𝟎^𝟗 (𝐦𝐨𝐥⁄𝐋) ⁄𝐦𝐢𝐧

Integral Method of Analysis

Assumption: The rate of saponification reaction is a second order reaction.

𝑑𝐶𝐴
−𝑟𝐴 = − = 𝑘𝐶𝐴2
𝑑𝑡

Integrating with limits at 𝑡 = 0, then 𝐶𝐴 = 𝐶𝐴0 , and 𝑡 = 𝑡 𝑚𝑖𝑛, then 𝐶𝐴 = 𝐶𝐴 .

𝐶𝐴 𝑡
𝑑𝐶𝐴
∫ = −𝑘 ∫ 𝑑𝑡
𝐶𝐴𝑜 𝐶𝐴2 0

1 𝐶𝐴
[− ] = −𝑘𝑡
𝐶𝐴 𝐶
𝐴𝑜

1 1
[− + ] = −𝑘𝑡
𝐶𝐴 𝐶𝐴𝑜

1 1
− = 𝑘𝑡
𝐶𝐴 𝐶𝐴𝑜

𝟏 𝟏
∴ = 𝒌𝒕 +
𝑪𝑨 𝑪𝑨𝒐

14
Graph of 1/CNaOH (L/mol) against time, t (min) at 20 oC.

24

23

22

21

20
y = 0.394x + 18.435
19 R² = 0.869

18

17

16

15
0 2 4 6 8 10 12 14
Time, t (min)

Figure 7.3: Graph of 1/CNaOH (L/mol) against time, t (min) at 20 oC.

15
From Figure 7.3, the graph plotted gives a straight line with positive slope, hence,
the reaction is proven as second order reaction.

The linear equation obtained from the graph was given as follows:

𝒚 = 𝟎. 𝟑𝟗𝟒𝒙 + 𝟏𝟖. 𝟒𝟑𝟓

𝑆𝑙𝑜𝑝𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑔𝑟𝑎𝑝ℎ = 𝑟𝑎𝑡𝑒 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

∴ 𝒌 = 𝟎. 𝟑𝟗𝟒 𝑳⁄𝒎𝒐𝒍 ∙ 𝒎𝒊𝒏

1
𝐼𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡 𝑜𝑛 𝑡ℎ𝑒 𝑦 − 𝑎𝑥𝑖𝑠 = 18.435
𝐶𝐴𝑜

Hence, the initial concentration of NaOH,

𝟏
∴ 𝑪𝑨𝟎 = = 𝟎. 𝟎𝟓𝟒𝟐𝟒𝒎𝒐𝒍/𝑳
𝟏𝟖. 𝟒𝟑𝟓

7.3.1.2 Conversion, XA

1 1
= 𝑘𝑡 +
𝐶𝐴 𝐶𝐴𝑜

By rearranging the equation above,

𝐶𝐴𝑜 − 𝐶𝐴
𝑘𝑡𝐶𝐴𝑜 =
𝐶𝐴

𝑋𝐴
𝑘𝑡𝐶𝐴𝑜 =
1 − 𝑋𝐴

𝑘𝑡𝐶𝐴𝑜 (1 − 𝑋𝐴 ) = 𝑋𝐴

𝑘𝑡𝐶𝐴𝑜 − 𝑘𝑡𝐶𝐴𝑜 𝑋𝐴 = 𝑋𝐴

𝑘𝑡𝐶𝐴𝑜 = 𝑋𝐴 + 𝑘𝑡𝐶𝐴𝑜 𝑋𝐴

𝑋𝐴 (1 + 𝑘𝑡𝐶𝐴𝑜 ) = 𝑘𝑡𝐶𝐴𝑜

𝒌𝒕𝑪𝑨𝒐
∴ 𝑿𝑨 =
𝟏 + 𝒌𝒕𝑪𝑨𝒐

Substitute 𝑘 = 6.894 𝐿⁄𝑚𝑜𝑙 ∙ 𝑚𝑖𝑛 (𝑖𝑛𝑡𝑒𝑔𝑟𝑎𝑙 𝑚𝑒𝑡ℎ𝑜𝑑), 𝑡 = 1 𝑚𝑖𝑛 and 𝐶𝐴𝑜 = 0.04 𝑚𝑜𝑙/
𝐿.

(0.394)(1)(0.05424)
𝑋𝐴 𝑎𝑡 𝑡=1 𝑚𝑖𝑛 =
1 + (0.394)(1)(0.05424)

∴ 𝑿𝑨 𝒂𝒕 𝒕=𝟏 𝒎𝒊𝒏 = 𝟎. 𝟎𝟐𝟎𝟗𝟐

16
Graph of conversion, XA against time, t (min) at 20 oC.

0.25

y = 0.0166x + 0.0104
R² = 0.9967
0.2

0.15
CONVERSION, XA

0.1

0.05

0
0 2 4 6 8 10 12 14
TIME, T (MIN)

Figure7.4: Graph of conversion, XA against time, t (min) at 20 oC

17
Sample Calculation on Saponification Reaction Conducted at T = 40 oC

Table 7.5: Calculated data for saponification reaction conducted at T = 40 oC.

𝟏 𝐝𝐂𝐍𝐚𝐎𝐇 𝐝𝐂𝐍𝐚𝐎𝐇
Time, t (min) VNaOH (mL) CNaOH (𝐦𝐨𝐥⁄𝐋) (𝐋⁄𝐦𝐨𝐥) 𝐥𝐨𝐠 𝟏𝟎 (− ) 𝐥𝐨𝐠 𝟏𝟎 (𝐂𝐍𝐚𝐎𝐇 ) 𝐗𝐀
𝐂𝐍𝐚𝐎𝐇 𝐝𝐭 𝐝𝐭

1 6.20 0.069 14.49275362 -0.004 -2.39794 -1.161150909 0.070026969

2 11.10 0.0445 22.47191011 -0.0032 -2.49485 -1.351639989 0.130888232

3 11.80 0.041 24.3902439 -0.0024 -2.61979 -1.387216143 0.184272779

4 11.00 0.045 22.22222222 -0.0016 -2.79588 -1.346787486 0.231478635

5 11.40 0.043 23.25581395 -0.0008 -3.09691 -1.366531544 0.273519797

6 10.20 0.049 20.40816327 0 UNDEFINED -1.30980392 0.31119989

7 10.30 0.0485 20.6185567 0.0008 UNDEFINED -1.314258261 0.345164036

8 10.30 0.0485 20.6185567 0.0016 UNDEFINED -1.314258261 0.375936096

9 10.20 0.049 20.40816327 0.0024 UNDEFINED -1.30980392 0.403945878

10 10.70 0.0465 21.50537634 0.0032 UNDEFINED -1.332547047 0.429549344

11 9.80 0.051 19.60784314 0.004 UNDEFINED -1.292429824 0.453043811

12 9.80 0.051 19.60784314 0.0048 UNDEFINED -1.292429824 0.474679555

18
Order of Reaction, n and Rate Constant, k

Differential Method of Analysis

Overall reaction equation

Taking the experimental data of time, t = 1 min for sample calculation with same
procedure as shown in previous section.

𝐍𝐚𝐎𝐇(𝐫𝐞𝐦𝐚𝐢𝐧𝐞𝐝, 𝐦𝟏) × 𝐯𝐨𝐥𝐮𝐦𝐞𝟏 + 𝐍𝐚𝐎𝐇(𝐚𝐝𝐝𝐞𝐝, 𝐦𝟐 ) × 𝐯𝐨𝐥𝐮𝐦𝐞𝟐

= 𝐇𝐂𝐥(𝐚𝐝𝐝𝐞𝐝, 𝐦𝟑) × 𝐯𝐨𝐥𝐮𝐦𝐞𝟑

𝐍𝐚𝐎𝐇(𝐫𝐞𝐦𝐚𝐢𝐧𝐞𝐝, 𝐦𝟏)
(𝐇𝐂𝐥(𝐚𝐝𝐝𝐞𝐝, 𝐦𝟑) × 𝐯𝐨𝐥𝐮𝐦𝐞𝟑 − 𝐍𝐚𝐎𝐇 (𝐚𝐝𝐝𝐞𝐝, 𝐦𝟐) × 𝐯𝐨𝐥𝐮𝐦𝐞𝟐)
=
𝐯𝐨𝐥𝐮𝐦𝐞 𝟏

.
𝒎𝒐𝒍 𝒎𝒐𝒍
𝟎. 𝟏 ( 𝑳 ) × 𝟏𝟎𝐦𝐥 − 𝟎. 𝟎𝟓 ( 𝑳 ) × 𝟔. 𝟐𝐦𝐥
𝐍𝐚𝐎𝐇(𝐫𝐞𝐦𝐚𝐢𝐧𝐞𝐝, 𝐦𝟏) =
𝟏𝟎𝐦𝐥
𝒎𝒐𝒍
𝐍𝐚𝐎𝐇(𝐫𝐞𝐦𝐚𝐢𝐧𝐞𝐝, 𝐦𝟏) = 𝟎. 𝟎𝟔𝟗( )
𝑳

19
Graph of concentration of NaOH (mol/L) against time, t (min) at 40 oC

0.08

0.07 y = 0.0004x2 - 0.0048x + 0.061

R² = 0.3144

0.06
CNaOH (mol/L)

0.05

0.04

0.03

0.02

0.01

0
0 2 4 6 8 10 12 14

Time, t (min)

Figure 7.5: Graph of concentration of NaOH (mol/L) against time, t (min) at 40 oC.

20
From Figure 7.5, the nonlinear equation obtained was:

𝐶𝑁𝑎𝑂𝐻 = 0.0004𝑥 2 − 0.0048𝑥 + 0.061

Differentiating the equation with respect to time,

𝑑𝐶𝑁𝑎𝑂𝐻
= 0.0008𝑥 − 0.0048
𝑑𝑡

Now, substitute the value of t into the above equation,

𝒅𝑪𝑵𝒂𝑶𝑯
= 𝟎. 𝟎𝟎𝟎𝟖(𝟏) − 𝟎. 𝟎𝟎𝟒𝟖 = −𝟎. 𝟎𝟎𝟒
𝒅𝒕

21
Graph of log10 (-dCA/dt) against log10 (CA) at 40 oC.

0
-1.4 -1.35 -1.3 -1.25 -1.2 -1.15 -1.1

-0.5

-1
y = 4.5761x + 4.9
R² = 0.0347

-1.5

-2

-2.5

-3

-3.5

Figure 7.6: Graph of log10 (-dCA/dt) against log10 (CA) at 40 oC.

22
From Figure 7.6, the linear equation obtained was:

𝒚 = 𝟒. 𝟓𝟕𝟔𝟏𝒙 + 𝟒. 𝟗

𝒅𝑪𝑨
∴ 𝐥𝐨𝐠 𝟏𝟎 (− ) = 𝟒. 𝟓𝟕𝟔𝟏 𝐥𝐨𝐠 𝟏𝟎 𝑪𝑨 + 𝟒. 𝟗
𝒅𝒕

Hence, the slope of the graph in Figure 7.6 represents the value order of reaction,

∴ 𝒏 = 𝟒. 𝟓𝟕𝟔𝟏

𝑇ℎ𝑒 𝑖𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡 𝑜𝑓 𝑦 − 𝑎𝑥𝑖𝑠 = log10 𝑘

4.9 = log10 𝑘

𝑘 = 104.9

∴ 𝒌 = 𝟕𝟗𝟒𝟑𝟑 (𝐦𝐨𝐥⁄𝐋) ⁄𝐦𝐢𝐧

Therefore, the order of reaction is 𝒏 = 𝟒. 𝟓𝟕𝟔𝟏, and 𝒌 = 𝟕𝟗𝟒𝟑𝟑 (𝐦𝐨𝐥⁄𝐋) ⁄𝐦𝐢𝐧

A. Integral Method of Analysis

Assumption: The rate of saponification reaction is a second order reaction.

Based on the integration performed in previous section:

𝟏 𝟏
= 𝒌𝒕 +
𝑪𝑨 𝑪𝑨𝒐

23
Graph of 1/CNaOH (L/mol) against time, t (min) at 40 oC.

26

24 y = 1.1954x + 15.871
R² = 0.4103

22
1/CNaOH (L/mol)

20

18

16

14

12

10
0 2 4 6 8 10 12 14

Time, t (min)

Figure 7.7: Graph of 1/CNaOH (L/mol) against time, t (min) at 40 oC.

24
From Figure 7.7, the graph plotted gives a straight line with positive slope, hence,
the reaction is proven as second order reaction.

The linear equation obtained from the graph was given as follows:

𝒚 = 𝟏. 𝟏𝟗𝟓𝟒𝒙 + 𝟏𝟓. 𝟖𝟕𝟏

𝑆𝑙𝑜𝑝𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑔𝑟𝑎𝑝ℎ = 𝑟𝑎𝑡𝑒 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

∴ 𝒌 = 𝟏. 𝟏𝟗𝟓𝟒 𝑳⁄𝒎𝒐𝒍 ∙ 𝒎𝒊𝒏

1
𝐼𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡 𝑜𝑛 𝑡ℎ𝑒 𝑦 − 𝑎𝑥𝑖𝑠 = = 15.871
𝐶𝐴𝑜

Hence, the initial concentration of NaOH,

𝟏
∴ 𝑪𝑨𝟎 = = 𝟎. 𝟎𝟔𝟑 𝒎𝒐𝒍/𝑳
𝟏𝟓. 𝟖𝟕𝟏

7.3.2.2 Conversion, XA

𝒌𝒕𝑪𝑨𝒐
𝑿𝑨 𝒂𝒕 𝒕=𝟏 𝒎𝒊𝒏 =
𝟏 + 𝒌𝒕𝑪𝑨𝒐

Substitute 𝑘 = 0.0498 𝐿⁄𝑚𝑜𝑙 ∙ 𝑚𝑖𝑛 (𝑖𝑛𝑡𝑒𝑔𝑟𝑎𝑙 𝑚𝑒𝑡ℎ𝑜𝑑) , 𝑡 = 1 𝑚𝑖𝑛 and 𝐶𝐴𝑜 =

0.0484 𝑚𝑜𝑙/𝐿.

(1.1954)(1)(0.063 )
𝑋𝐴 𝑎𝑡 𝑡=1 𝑚𝑖𝑛 =
1 + (1.1954)(1)(0.063)

∴ 𝑿𝑨 𝒂𝒕 𝒕=𝟏 𝒎𝒊𝒏 = 𝟎. 𝟎𝟕

25
Graph of conversion, XA against time (minutes) at 40 C
̊ .

0.6

y = 0.0359x + 0.0735
R² = 0.9751
0.5
Conversion, XA

0.4

0.3

0.2

0.1

0
0 2 4 6 8 10 12 14
Time, t (min)

Figure 7.8: Graph of conversion, XA against time (minutes) at 40 C

̊ .

26
Sample Calculation on Saponification Reaction Conducted at T = 50 oC

Table 3.6: Calculated data for saponification reaction conducted at T = 50 oC.

𝟏 𝐝𝐂𝐍𝐚𝐎𝐇 𝐝𝐂𝐍𝐚𝐎𝐇
Time, t (min) VNaOH (mL) CNaOH (𝐦𝐨𝐥⁄𝐋) (𝐋⁄𝐦𝐨𝐥) 𝐥𝐨𝐠 𝟏𝟎 (− ) 𝐥𝐨𝐠 𝟏𝟎 (𝐂𝐍𝐚𝐎𝐇 ) 𝐗𝐀
𝐂𝐍𝐚𝐎𝐇 𝐝𝐭 𝐝𝐭

1 7.80 16.39344262 -0.003 -2.602059991 -1.214670165 0.009704892

0.061
2 9.30 0.0535 18.69158879 -0.002 -2.677780705 -1.271646218 0.019223225

3 10.10 0.0495 20.2020202 -0.002 -2.769551079 -1.305394801 0.028560326

4 10.00 0.05 20 -0.001 -2.886056648 -1.301029996 0.037721324

5 10.10 0.0495 20.2020202 -9E-04 -3.045757491 -1.305394801 0.046711153

6 10.10 0.0495 20.2020202 -5E-04 -3.301029996 -1.305394801 0.055534567

7 10.20 0.049 20.40816327 -1E-04 -4 -1.30980392 0.064196144

8 10.00 0.05 20 0.0003 UNDEFINED -1.301029996 0.072700297

9 9.90 0.0505 19.8019802 0.0007 UNDEFINED -1.296708622 0.081051277

10 10.10 0.0495 20.2020202 0.0011 UNDEFINED -1.305394801 0.089253188

11 10.10 0.0495 20.2020202 0.0015 UNDEFINED -1.305394801 0.097309984

12 10.00 0.05 20 0.0019 UNDEFINED -1.301029996 0.105225483

27
Order of Reaction, n and Rate Constant, k

Differential Method of Analysis

Overall reaction equation

Taking the experimental data of time, t = 1 min for sample calculation with same
procedure as shown in previous section.

𝐍𝐚𝐎𝐇(𝐫𝐞𝐦𝐚𝐢𝐧𝐞𝐝, 𝐦𝟏) × 𝐯𝐨𝐥𝐮𝐦𝐞𝟏 + 𝐍𝐚𝐎𝐇(𝐚𝐝𝐝𝐞𝐝, 𝐦𝟐 ) × 𝐯𝐨𝐥𝐮𝐦𝐞𝟐

= 𝐇𝐂𝐥(𝐚𝐝𝐝𝐞𝐝, 𝐦𝟑) × 𝐯𝐨𝐥𝐮𝐦𝐞𝟑

𝐍𝐚𝐎𝐇(𝐫𝐞𝐦𝐚𝐢𝐧𝐞𝐝, 𝐦𝟏)
(𝐇𝐂𝐥(𝐚𝐝𝐝𝐞𝐝, 𝐦𝟑) × 𝐯𝐨𝐥𝐮𝐦𝐞𝟑 − 𝐍𝐚𝐎𝐇 (𝐚𝐝𝐝𝐞𝐝, 𝐦𝟐) × 𝐯𝐨𝐥𝐮𝐦𝐞𝟐)
=
𝐯𝐨𝐥𝐮𝐦𝐞 𝟏

.
𝒎𝒐𝒍 𝒎𝒐𝒍
𝟎. 𝟏 ( 𝑳 ) × 𝟏𝟎𝐦𝐥 − 𝟎. 𝟎𝟓 ( 𝑳 ) × 𝟕. 𝟖𝐦𝐥
𝐍𝐚𝐎𝐇(𝐫𝐞𝐦𝐚𝐢𝐧𝐞𝐝, 𝐦𝟏) =
𝟏𝟎𝐦𝐥
𝒎𝒐𝒍
𝐍𝐚𝐎𝐇(𝐫𝐞𝐦𝐚𝐢𝐧𝐞𝐝, 𝐦𝟏) = 𝟎. 𝟎𝟔𝟏( )
𝑳

28
Concentration of NaOH (mol/L) against time, t (min) at 50 oC.
0.065

0.06
CNaOH (mol/L)

0.055

0.05

y = 0.0002x2 - 0.0029x + 0.06

0.045 R² = 0.6933

0.04
0 2 4 6 8 10 12 14

Time, t (min)

Figure 7.9: Concentration of NaOH (mol/L) against time, t (min) at 50 oC.

29
From Figure 7.9, the nonlinear equation obtained was:

𝐶𝑁𝑎𝑂𝐻 = 0.0002𝑥 2 − 0.0029𝑥 + 0.06

Differentiating the equation with respect to time,

𝑑𝐶𝑁𝑎𝑂𝐻
= 0.0004𝑥 − 0.0029
𝑑𝑡

Now, substitute the value of t into the above equation

𝒅𝑪𝑵𝒂𝑶𝑯
= 𝟎. 𝟎𝟎𝟎𝟒(𝟏) − 𝟎. 𝟎𝟎𝟐𝟗 = −𝟎. 𝟎𝟎𝟐𝟓
𝒅𝒕

30
Graph of log10 (-dCA/dt) against log10 (CA) at 50 oC.

0
-1.32 -1.3 -1.28 -1.26 -1.24 -1.22 -1.2

-0.5

-1

-1.5
y = 7.9066x + 7.1404
R² = 0.3192
-2
log10 (-dCA/dt)

-2.5

-3

-3.5

-4

-4.5
log10 (CA)

Figure 3.10: Graph of log10 (-dCA/dt) against log10 (CA) at 50 oC.

31
From Figure 7.10, the linear equation obtained was:

𝒚 = 𝟕. 𝟗𝟎𝟔𝟔𝒙 + 𝟕. 𝟏𝟒𝟎𝟒

𝒅𝑪𝑨
∴ 𝐥𝐨𝐠 𝟏𝟎 (− ) = 𝟕. 𝟗𝟎𝟔𝟔 𝐥𝐨𝐠 𝟏𝟎 𝑪𝑵𝒂𝑶𝑯 − 𝟕. 𝟏𝟒𝟎𝟒
𝒅𝒕

Hence, the slope of the graph in Figure 7.6 represents the value order of reaction,

∴ 𝒏 = 𝟕. 𝟗𝟎𝟔𝟔

𝑇ℎ𝑒 𝑖𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡 𝑜𝑓 𝑦 − 𝑎𝑥𝑖𝑠 = log10 𝑘

−7.1404 = log10 𝑘

𝑘 = 10−𝟕.𝟏𝟒𝟎𝟒

∴ 𝒌 = 𝟕. 𝟐𝟒 (𝐦𝐨𝐥⁄𝐋)−𝟖⁄𝐦𝐢𝐧

Therefore, the order of reaction is 𝒏 = 𝟕. 𝟗𝟎𝟔𝟔, and 𝒌 = 𝟕. 𝟐𝟒 (𝐦𝐨𝐥⁄𝐋)−𝟖 ⁄𝐦𝐢𝐧

A. Integral Method of Analysis

Assumption: The rate of saponification reaction is a second order reaction.

Based on the integration performed in previous section:

𝟏 𝟏
= 𝒌𝒕 +
𝑪𝑨 𝑪𝑨𝒐

32
Graph of 1/CNaOH (L/mol) against time, t (min)

21

20

y = 0.1814x + 18.513
R² = 0.3363
1/CNaOH (L/mol)

19

18

17

16

15
0 2 4 6 8 10 12 14

Time, t (min)

Figure 7.11: Graph of 1/CNaOH (L/mol) against time, t (min)

33
From Figure 7.11, the graph plotted gives a straight line with positive slope, hence,
the reaction is proven as second order reaction.

The linear equation obtained from the graph was given as follows:

𝒚 = 𝟎. 𝟏𝟖𝟏𝟒𝒙 + 𝟏𝟖. 𝟓𝟏𝟑

𝑆𝑙𝑜𝑝𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑔𝑟𝑎𝑝ℎ = 𝑟𝑎𝑡𝑒 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

∴ 𝒌 = 𝟎. 𝟏𝟖𝟏𝟒 𝑳⁄𝒎𝒐𝒍 ∙ 𝒎𝒊𝒏

1
𝐼𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡 𝑜𝑛 𝑡ℎ𝑒 𝑦 − 𝑎𝑥𝑖𝑠 = = 18.513
𝐶𝐴𝑜

Hence, the initial concentration of NaOH,

𝟏
∴ 𝑪𝑨𝟎 = = 𝟎. 𝟎𝟓𝟒 𝒎𝒐𝒍/𝑳
𝟏𝟖. 𝟓𝟏𝟑

7.3.3.2 Conversion, XA

𝒌𝒕𝑪𝑨𝒐
𝑿𝑨 𝒂𝒕 𝒕=𝟏 𝒎𝒊𝒏 =
𝟏 + 𝒌𝒕𝑪𝑨𝒐

Substitute 𝑘 = 4.785 𝐿⁄𝑚𝑜𝑙 ∙ 𝑚𝑖𝑛 (𝑖𝑛𝑡𝑒𝑔𝑟𝑎𝑙 𝑚𝑒𝑡ℎ𝑜𝑑) , 𝑡 = 1 𝑚𝑖𝑛 and 𝐶𝐴𝑜 =

0.00497 𝑚𝑜𝑙/𝐿.

(0.1814)(1)(0.054)
𝑋𝐴 𝑎𝑡 𝑡=1 𝑚𝑖𝑛 =
1 + (0.1814)(1)(0.054)

∴ 𝑿𝑨 𝒂𝒕 𝒕=𝟏 𝒎𝒊𝒏 =0.0097

34
Graph of conversion, XA against time, t (min) at 50 oC.

0.12

y = 0.0087x + 0.0025
R² = 0.9992
0.1
Conversion, XA

0.08

0.06

0.04

0.02

0
0 2 4 6 8 10 12 14

Time, t (min)

Figure 3.12: Graph of conversion, XA against time, t (min) at 50 oC.

35
7.2 Activation Energy, E and Frequency (Pre-exponential Factor), k0
A. Graphical Method

From Arrhenius equation,

𝑘 = 𝐴𝑒 −𝐸⁄𝑅𝑇

Rearranging the equation,

𝑬 𝟏
∴ 𝐥𝐧 𝒌 = (− ) ( ) + 𝐥𝐧 𝑨
𝑹 𝑻

Table 7.7: Rate constant calculated based on previous section with their relative temperatures.

Temperature, T (K) 1/T (1/K) Rate constant, k ln (k)

293.2 0.003411 0.394 -0.9314

313.2 0.003193 1.1954 0.1785

323.2 0.003094 0.1814 -1.7071

Graph of ln k against 1/T (K-1).

0.5

0
0.00305 0.0031 0.00315 0.0032 0.00325 0.0033 0.00335 0.0034 0.00345

-0.5
ln k

-1
y = 1207.8x - 4.7245
R² = 0.0427
-1.5

-2
1/T (K-1)

Figure 7.13: Graph of ln k against 1/T (K-1).

From Figure 7.13,

𝐸
𝑆𝑙𝑜𝑝𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑔𝑟𝑎𝑝ℎ = − = 1207.8
𝑅

𝐸 = −1207.8 × 8.314 𝐽/𝑔 𝑚𝑜𝑙 ∙ 𝐾

𝐸 = −10041.65 𝐽⁄𝑚𝑜𝑙

36
 ∴ 𝑬 = −𝟏𝟎. 𝟎𝟒𝟏 𝒌𝑱/𝒎𝒐𝒍

y-intercept,

𝑙𝑛 𝐴 = −4.7245

𝐴 = 𝑘0 = 𝑒 −4.7245

∴ 𝒌𝟎 = 𝟎. 𝟎𝟎𝟖𝟗 𝑳⁄𝒎𝒐𝒍 ∙ 𝒎𝒊𝒏

B. Arrhenius Equation
E
− E 1 1
𝑘2 e RT2 ( − )
R T1 T2
= E = e
𝑘1 −
e RT1

Now, taking natural logarithm on both sides on the equation above to eliminate the exponent term,

𝒌𝟐 𝑬 𝟏 𝟏
∴ 𝑰𝒏 ( ) = ( − )
𝒌𝟏 𝑹 𝑻𝟏 𝑻𝟐

Substitute𝑘1 = 8.2273, 𝑘2 = 5.5632, 𝑇1 = 313.2 𝐾, 𝑇2 = 323.2 𝐾, 𝑅 = 8.314 J⁄g mol ∙ K,

0.1814 𝐸 1 1
𝐼𝑛 ( )= ( − )
1.1954 8.314 313.2 𝐾 323.2 𝐾
0.1814 8.314
𝐸 = 𝐼𝑛 ( )×
1.1954 1 1
313.2 − 323.2

𝐸 = −158685.39 𝐽⁄𝑚𝑜𝑙

∴ 𝑬 = −𝟏𝟓𝟖. 𝟔𝟖𝟓 𝒌𝑱⁄𝒎𝒐𝒍

For 𝑘1 = 0.394, 𝑎𝑡 𝑇 = 293.2 𝐾,

𝐸 1
ln 𝑘 = (− ) ( ) + ln 𝐴
𝑅 𝑇

J
−158685.39 1
2.3013 = (− mol) ( ) + lnA
J 293.2 K
8.314
g mol ∙ K

lnA = −11.1617

𝐴 = 𝑘𝑜 = 𝑒 −11.1617

∴ 𝒌𝒐 = 𝟏. 𝟒𝟐𝟏 × 𝟏𝟎−𝟓 𝑳⁄𝒎𝒐𝒍 ∙ 𝒎𝒊𝒏

Mole Balance

General mole balance equation,

37
 𝑑𝑁𝐴
𝐹𝐴0 − 𝐹𝐴 + ∫ 𝑟𝐴 𝑑𝑉 =
𝑑𝑡

A batch reactor mixture has neither inflow nor outflow of reactants or products while the reaction is being
carried out: 𝐹𝐴0 = 𝐹𝐴 = 0.
𝑉
𝑑𝑁𝐴
= ∫ 𝑟𝐴 𝑑𝑉
𝑑𝑡 0

If the reaction is perfectly mixed so that there is no variation in the rate of reaction throughout the reactor
volume. Hence, 𝑟𝐴 can be taken out of the integral, integrate, and write the mole balance in the form

𝑑𝑁𝐴
= 𝑟𝐴 𝑉
𝑑𝑡

Rearranging,

𝑑𝑁𝐴
𝑑𝑡 =
𝑟𝐴 𝑉

And integrating with limits that at 𝑡 = 0, then 𝑁𝐴 = 𝑁𝐴0 , and at 𝑡 = 𝑡1 , then 𝑁𝐴 = 𝑁𝐴1 , we obtain
𝑁𝐴0
𝑑𝑁𝐴
𝑡1 = ∫
𝑁𝐴1 −𝑟𝐴 𝑉

𝑡1 = Time necessary to reduce the initial number of moles from 𝑁𝐴0 to a final desired number 𝑁𝐴1 .

Below is the summarized data,

Room 40°C 50°C

Temperature
Part 1:
Integral k = 0.394 L/mol min k = 1.1954 L/mol k = 0.1814 L/mol
Rate
constant Method CA0 = 0.05425 mol/L min min
and order CA0 = 0.063 mol/L CA0 = 0.054 mol/L
of reaction
Differential k = 1.924 L/mol min k = 7.943 L/mol min k = 7.24 L/mol min
Method n = 9.2701 n = 4.5761 n = 7.9066

Graphical
E = -10.041 kJ/mol
Part 2: Method
A = 0.0089 L/mol∙min
Activation
Energy and
By using
Frequency E = -158.685 kJ/mol
Factor Arrhenius
A = 1.421 x 10-5 L/mol∙min
equation
Figure 7.14: summarized data

38
8.0 DISCUSSION/RECOMMENDATION

A saponification reaction is the hydrolysis of an organic compound, under basic condition, in which
a carboxylic acid salt is one of the products (Stoker, 2009). In this experiment, saponification between
NaOH and ethyl acetate was carried out in batch operation and the rate constants of different temperatures
were determined.

CH3COOC2H5 + OH- CH3COO- + C2H5OH

In this experiment, we conducted the saponification reaction at three different temperature, which
are at T = 20°C, T = 40°C, and T = 50°C. Based on the graph (Figure 7.1, Figure 7.5 and Figure 7.9)
plotted, we can find out that the concentration of NaOH decreased when the reaction time increased.

By differentiating and taking log10 on the graph equation of concentration of NaOH versus time,
𝑑𝐶𝑁𝑎𝑂𝐻
the graph of log10 (− 𝑑𝑡
) versus log10 𝐶𝑁𝑎𝑂𝐻 (Figure 7.2, Figure 7.6 and Figure 7.10) is plotted. The
𝑑𝐶𝑁𝑎𝑜𝐻
value of log10 (− ) increased as the value of log10 𝐶𝑁𝑎𝑂𝐻 increased. By using integral method of
𝑑𝑡
𝟏 𝟏 𝟏
analysis, we got the equation of 𝑪𝑨
= 𝒌𝒕 + 𝑪 . Therefore, we plotted the graph of 𝑪𝑵𝒂𝑶𝑯
against time
𝑨𝒐

𝟏
(Figure7.3, Figure 7.7 and Figure 7.11). The value of 𝑪𝑵𝒂𝑶𝑯
also increased as reaction time increased.

By using differential method analysis, the reaction order of saponification of ethyl acetate, n is
9.2701 while the rate constant, k is 𝟏. 𝟗𝟐𝟒 (𝐦𝐨𝐥⁄𝐋) ⁄𝐦𝐢𝐧 at T= 20 oC. For T= 40 oC, the value of
n is 𝟒. 𝟓𝟕𝟔𝟏 and k is 𝟕. 𝟗𝟒𝟑𝟑 (𝐦𝐨𝐥⁄𝐋) ⁄𝐦𝐢𝐧 . At T=50 oC, n is 𝟕. 𝟗𝟎𝟔𝟔 while the rate constant, k is
𝟕. 𝟐𝟒 (𝐦𝐨𝐥⁄𝐋) ⁄𝐦𝐢𝐧. IMHERE

1 1
By using integral method, the graph of against time is plotted. The value of is not a
𝐶𝑁𝑎𝑂𝐻 𝐶𝑁𝑎𝑂𝐻

constant throughout whole experiment but in general, it is an increasing trend. For integral method, the
rate constant, k is 𝟗. 𝟗𝟖𝟕𝟖𝟓𝟔𝟗𝟎𝟑𝟕 𝑳⁄𝒎𝒐𝒍 ∙ 𝒎𝒊𝒏 at T= 20 o
C. For T= 40 o
C, the value of k is
𝟖. 𝟐𝟐𝟕𝟑𝟑𝟒𝟓𝟐 𝑳⁄𝒎𝒐𝒍 ∙ 𝒎𝒊𝒏. For T=50 oC, the rate constant, k is 𝟓. 𝟓𝟔𝟑𝟏𝟔𝟒𝟕𝟖 𝑳⁄𝒎𝒐𝒍 ∙ 𝒎𝒊𝒏.

The converstion of NaOH, XNaOH is calculated in this experiment. From the graph (Figure 3.13)
plotted, the converstion NaOH is directly proportional to the reaction time. The data of ln k versus 1/T is
analyzed and plotted to determine the activation energy, E and frequency (pre-exponential factor). k0.
There are two method to determine the value of activation energy, E, which are by finding the slope of
the graph of ln k against 1/T and the by using Arrhenius Equation. For the method of using the slope of

39
graph of ln k against 1/T, the value of E is −𝟏𝟎. 𝟎𝟒𝟏 𝒌𝑱/𝒎𝒐𝒍 while by using Arrhenius Equation, the value
of E is −𝟏𝟓𝟖. 𝟔𝟖𝟓 𝒌𝑱⁄𝒎𝒐𝒍. For the method of using the slope of graph of ln k against 1/T, the value of k0
is 𝟎. 𝟎𝟎𝟖𝟗 𝑳⁄𝒎𝒐𝒍 ∙ 𝒎𝒊𝒏 whereas by using Arrhenius Equation, the value of k0 is 𝟏. 𝟒𝟐𝟏 ×
𝟏𝟎−𝟓 𝑳⁄𝒎𝒐𝒍 ∙ 𝒎𝒊𝒏. The theorectical value of E is different with the value of E that analysised from graph
as there are errors occured during conducting this experiment.

In this experiment, the order of saponification reaction varies very much due to several errors
occurred while conducting the experiment. Therefore, the accuracy of obtained value is affected. During
the back-titration process, we did not notice the first shade of pink colour immediately hence there is
inaccuracy of volume of NaOH used. It affected the results obtained in the experiment.

There are some errors during conducting this experiment:

1) To obtain the more accuracy result, there are some precaution steps should be taken such as:
2) When taking the reading from the burette, parallax error should be avoided by placing our eye
level parallel to the meniscus of the solution.
3) During the titration process, the titration should be stopped carefully and immediately once the
solution has changed to light pink color to enhance the accuracy.
4) The experiment shall be repeated a few times in order to get the average values which give us a
more accurate result.
5) Before conducting the experiment, all the apparatus should be rinsed with distilled water to ensure
they’re free from impurities.
6) When transferring the 10mL solution from beaker to conical flask each minute, we should manage
the skill well and pipette the exact volume of the solution into the conical flask.

9.0 CONCLUSION
In a nutshell, the saponification of ethyl acetate with NaOH does not follow elementary rate law. It is not
2nd order reaction. By using different temperature, the order of reaction might different. In 20oC, n=
9.2701, at 40oC, n = 𝟒. 𝟓𝟕𝟔𝟏 and finally at 50oC, n = 𝟕. 𝟗𝟎𝟔𝟔. From the calculation we also found that
20oC is the optimum temperature for the saponification compare to 40oC and 50oC.

40
10.0 REFERENCES
KC30201 Laboratory 6 Manual

Fogler, H. S. (2006). Elements of Chemical Reaction Engineering. United States: Pearson Hall.

Lab Manual 6. (2013).

Lee, C. C. (2005). Environmental Engineering Dictionary. Oxford: Government Institutes.

Smith, P. G. (2011). Introduction to Food Process Engineering. New York: Springer.

Stoker, H. S. (2009). General, Organic and Biological Chemistry. New York: Cengage Learning.

Trimm, H. H. (2011). Physical Chemistry: Chemical Kinetics and Reaction Mechanisms. Canada: CRC Press.

11.0 APPENDIX

Figure 11.1: Mixture heated by heater and stirred with magnetic stirrer.

41
Figure 11.2: Ethyl Acetate is transferred into the mixture (reactor).

Figure 11.3: Titration process carried out by student.

Figure 11.4: Colour of solution after titration.

42