Summary

In this experiment, rate constant between ethyl acetate and sodium hydroxide are
determined under batch condition. With different time used during the experiment,
rate constant was measured by using integrated rate law method as the concentration
of ethyl acetate and sodium hydroxide are same. Rate constant, k 0.0350 was obtained
in the experiment as phenolphthalein was acts as indicator, ethyl acetate was taken
and mixed with hydrochloric acid and stirred them. Safety precautions were took to
ensure the best accuracy possible for the results.

Aim

The aim of the experiment is to measure the rate constant of the reaction between
ethyl acetate and sodium hydroxide under batch conditions.

Introduction

When chemical reaction occurs, there is rate of reaction or also known as reaction
rate. The rate of chemical reaction at a constant temperature depends only on the
concentration of the substances that influence the rate. Catalysts can also influence
reaction rate if it appear in the balanced overall chemical reaction. Changes in
concentration of a reactant or product with time reaction rate can be obtained.

For example; reaction between reactants A and B to form product C.

𝑎𝐴 + 𝑏𝐵 = 𝑐𝐶

Theory

The second-order rate constant for the reaction can be determined in two different
ways.

a) Integrated rate law method;

The experiment is a simple, irreversible and second-order process, the rate law for the
experiment is,

d[ester]
Rate = − = k[ester][OH − ]
dt

where,

d[ester] = change in concentration of ester

dt = change in time
[ester] = concentration of ester
[OH − ] = concentration of hydroxide ion
k = rate change
Suppose that the concentration of the ester and hydroxide are equal at the start of the
experiment and same to 𝑐0 mol/𝑑𝑚3 , and that at some time t later, both ester and
hydroxide concentration have fallen to c. So, it can be written:

𝑑𝑐
− = 𝑘[𝑒𝑠𝑡𝑒𝑟][𝑂𝐻 − ] = 𝑘𝑐 2
𝑑𝑡

Separating the variables and integrating with appropriate boundary conditions:

𝑐 𝑡
𝑑𝑐
∫ 2 = 𝑘 ∫ 𝑑𝑡
𝑐
𝑐0 0

1 1
− = 𝑘𝑡 (1)
𝑐 𝑐0

1
When a graph of against t was plotted should give a straight line with gradient k.
𝑐

b) Half-life method;

From the equation (1) can be arranged to give:

1 𝑐0 − 𝑐
𝑘= .
𝑡 𝑐0 𝑐

Let 𝑡1 be the time taken for the concentration of ester to be halved. Then,
2

1
𝑘=
𝑡1 𝑐0
2

The time taken to halve the concentration of ester is inversely proportional to the
initial concentration.
Experimental method

1. 250 cm3 of 0.1M ethyl acetate solution was pipette into a clean dry conical
flask, and 250 cm3 of 0.1M sodium hydroxide into a large beaker.
2. Six clean conical flasks were labeled and 25 cm3 of 0.1M HCl was pipette into
the conical flasks.
3. Mechanical stirrer was placed in the sodium hydroxide solution and turn on the
stirrer.
4. The ethyl acetate solution quickly pour into the beaker and stopwatch started at
roughly the mid-point of pouring.
5. 25 cm3 of mixture was pipette after 5 minutes into flask labeled.
6. Temperature of the reacting mixture in the beaker was recorded.
7. The mixtures content in flask was titrated against 0.1M sodium hydroxide and
using 2-3 drops of phenolphthalein as indicator.
8. The procedure was repeated by further the samples at roughly 10, 20, 30, 50
and 75 minutes.
Experimental Results

No Time, t Volume of Number of Number of Concentrations

(s) NaOH used moles of 0.1 moles of of
for titration NaOH used 0.1 NaOH Ester, 𝑐
(cm3) for titration in mixture (×10-2mol cm-3)
(×10-3mol) (×10-3mol)
1 300.00 20.00 2.00 0.50 2.00
2 600.00 20.90 2.09 0.41 1.64
3 1200.00 21.50 2.15 0.35 1.40
4 1800.00 21.70 2.17 0.33 1.32
5 3000.00 22.70 2.27 0.23 0.92
6 4500.00 23.50 2.35 0.12 0.48
Table 1 : table of time, volume and number of moles of NaOH used, number of
moles and concentrations of ester
0.1(25−𝑦)
Number of moles of NaOH in 25 cm3 sample from the mixture = 1000

NaOH concentration in 25 cm3sample from the mixture = ester concentration (c)

𝑛(1000)
c= 25cm3
Analysis and Discussion:

a) Integrated rate law method

1⁄ 50.00 60.98 71.43 75.76 108.70 208.33

𝑐
(mol-1cm3)
Time, t (s) 300.00 600.00 1200.00 1800.00 3000.00 4500.00
Table 2 : table of time and 1⁄𝑐

Figure 1: graph 1/c against t

1/c, (mol-1cm3) 250

(120 − 50)mol−1 cm3

𝑘=
200 (2600 − 600)s

𝑘 = 0.0350mol−1 cm3 s-1

150

100

1
= 58.82
𝑐1⁄ 50
2

1
= 29.49
𝑐0
0
0 1000 2000 3000 4000 5000
t, (s)
840s

1 1
− = 𝑘𝑡
𝑐 𝑐0

1 1
= 𝑘𝑡 +
𝑐 𝑐0

𝑦 = 𝑚𝑥 + ∁

Since; 𝑘 = 𝑚 then,
𝑦 −𝑦
𝑘 = 𝑥2−𝑥1
2 1

𝑘 = 0.0350mol−1 cm3 s
b) Half-life method
1
Since; ∁= 𝑐 then,
0

1
= 29.49
𝑐0

𝑐0 = 3.4 × 10−2 mol cm−3

From 𝑐0 , we can find the 𝑐1⁄ because;

2

𝑐0
𝑐1⁄ =
2 2
3.4 × 10−2 mol cm−3
𝑐1⁄ =
2 2
𝑐1⁄ = 1.7 × 10−2 mol cm−3
2

1
= 58.82(mol−1 cm3 )
𝑐1⁄
2

1
At 𝑡1⁄ , the 𝑐 = 58.82(mol−1 cm3 )
2 1⁄
2

From the graph, we get the 𝑡1⁄ =840 s

2

1
𝑘=
𝑡1⁄ 𝑐0
2

1
𝑘=
840s(3.4 × 10−2 mol−1 cm3 )

𝑘 =0.0350molmol−1 cm3 s-1

Reaction order is the power of the component concentrations in the rate law. Reaction
kinetics of ethyl acetate saponification is studied by measuring the concentration of
hydroxide ions for reaction progress. Hydroxide ion concentration was measured
batch conditions. The order of a reaction describes the mathematical form in which
the results of the changes can be demonstrated. Reaction order can only be calculated
in experiment and can only be predicted if the reaction mechanism is known
throughout the reaction order can be determined as the sum of the exponents for each
of the reactants, whereas only exponent for each reactant known as the order of the
reaction to that component. In general, the order of the reaction to a particular
substance is not the same as the stoichiometric coefficients in the reaction equation
(Hiskia, 2001). In this experiment we will determine the value of the order reaction
between ethyl acetate and NaOH by titration method. The reaction is:

CH3COOC2H5 + OH-→ CH3COO- + C2H5OH

This is the saponification reaction and the second order reaction. We mix the solution
and it must be stirred well to make the solution homogenous. Then, we wait until it
reaches the 5, 10, 20, 30, 50 and 75 minutes. After that, we pour it into the conical
flask that contain 25 cm3 of HCl 0.1 M

CH3CHOO- + H+ → CH3COOH

HCl functions is to stop the saponification reaction, and then we titrate the excess of
HCl with 0.1 M NaOH

H+ (excess) + OH- → H2O

Before performing titrations, we must add phenolphthalein as indicator to show that

the titration reaches the equivalent point. If the titration of neutralisation process
between HC1 and NaOH reaches the equivalent point, the phenolphthalein will turns
the titrate colours from colourless to pale pink. This shows that the volume of NaOH
that is needed for titration, y (cm3) is equal to volume of excess HC1 that have been
neutralised in conical flask. After that, we can calculate the number of moles of
NaOH present in the sample. Since the volume of NaOH from the sample is equal to
acid that have been neutralised in the sample, we need to calculate the difference
amount of HC1 between the original amount of HC1 and the amount of excess HC1
that neutralised in titration.

0.1(25−𝑦)
= number of moles of NaOH from reacting mixture
1000

Thus, from the number of moles of NaOH, we can find the NaOH concentration in the
sample and find the ester concentration, c (mol-1cm3) since the NaOH concentrations
is equal to ester concentration, c (mol-1cm3). Then we plot the graph 1/c against t. We
can find the rate constant, k (mol-1cm3s-1) by comparing the equations of the graph
with the integrated rate equation for second order reaction.

1 1
− = 𝑘𝑡
𝑐 𝑐0

1 1
= 𝑘𝑡 +
𝑐 𝑐0

𝑦 = 𝑚𝑥 + ∁

From the graph we can get rate constant, k from the gradient of the graph. We can see
the relation between 1/c is increasing as time, t increasing. So the rate constant, k is
increasing at each time and we can say that the saponification is second order
reaction. From the integrated rate law we get the reaction constant, k =
0.0350mol−1 cm3 s-1 and from the half-life method the reaction constant,
k=0.0350mol−1 cm3 s-1.

In this experiment, may have some error that has been done during the experiment
like parallax error. During take the reading from the burette, we may get the wrong
reading value due to our eyes that not parallel to the burette reading. So we must
make sure our eyes are parallel to the reading value of the burette. The next mistake is
when we titrate the NaOH to neutralise with HC1 which is we let the solution in
conical flask turns to the purple not the pale pink. This may cause the volume of
NaOH that needed to neutralise the acid excess from real amount of HC1 that have
been left in conical flask and may affect our result.
Conclusion

Based on this experiment the rate of reaction constant, k obtained for integrated rate
law method is 0.0350mol−1 cm3 s-1 and reaction constant, k for half life method is
0.0350mol−1 cm3 s-1. This reaction has second order of reaction because a We can
see the relation between 1/c is increasing as time, t increasing from the graph.

References

Raymond Chang, General Chemistry the Essential Concept, 3rd edition, Mc Graw
Hill, 2003.

Atkins, P.W.: Physical Chemistry (various eds), OUP, 1976 onwards 541

Frost, A.A. & Pearson, R.G.: Kinetics and Mechanism (2nd ed.), Wiley, 1961
541.394

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