APPROVAL SHEET

The complete report of Physical Chemistry II Experiment with the title

Determination of Reaction Order and Constant of Reaction Rate was made by:
name : Nuraeni Rahman
id : 1413440001
group :I
class : ICP A of Chemistry
after checked and consulted by assistant and assistant coordinator. So, this report
was accepted.

Makassar, November 2016

Assistant Coordinator, Assistant,

Rahmawati Yasin Muh. Rezky Yusuf

ID. 1313041015 ID. 1313140012

Known by,
Responsibility Lecturer

Dr. Muhammad Syahrir, S.Pd., M.Si

ID. 197409 072005 01 2004
A. TITLE OF EXPERIMENT
Determination of Reaction Order and Constant of Reaction Rate

B. OBJECTIVES
1. Show that saponification reaction of ethyl acetate by hydroxide ion is a second
order reaction.
2. Determine the reaction rate constant of ethyl acetate saponification by
hydroxide ion with titration.

C. REVIEW OF LITERATURE
The first steps in the kinetic analysis of reactions are to establish the
stoichiometry of the reaction and identify any side reactions. The basic data of
chemical kinetics are then the concentrations of the reactants and products at
different times after a reaction has been initiated. The rates of most chemical
reactions are sensitive to the temperature, so in conventional experiments the
temperature of the reaction mixture must be held constant throughout the course
of the reaction. This requirement puts severe demands on the design of an
experiment (Atkins, 2006: 791).
An elementary reaction is a single reaction step. When only a single
molecule is involved (AP) the elementary reaction is unimolecular with a first
order rate law (rate=k[A]). If two reactant molecules are involved (A+BP) the
elementary reaction is bimolecular with a second order rate law (rate=k[A][B]). A
complex reaction is one which proceeds through more than one constituent
elementary reaction step. This is the assumption that the concentrations of all
intermediate species in a reaction mechanism remain constant during the reaction.
Hence the net change in concentration [I] of any intermediate with time can be set
to zero, d[I]/dt0 which means that the rates of formation and removal for each
intermediate must balance (Whittaker, 2000: 179).
 Consider a reaction of the form A + 2B 3C + D, in which at some
instant the molar concentration of a participant J is [J] and the volume of the
system is constant. The instantaneous rate of consumption of one of the reactants
at a given time is d[R]/dt, where R is A or B. This rate is a positive quantity (Fig.
21.4). The rate of formation of one of the products (C or D, which we denote P) is
d[P]/dt (note the difference in sign). This rate is also positive. It follows from the
stoichiometry for the reaction A + 2B 3C + D that
d [ D ] 1 d [ C ] d [ A ] 1 d [ B ]
= = =
dt 3 dt dt 2 dt
so the rate of the reaction is related to the rates of change of concentration of
products and reactants in several ways (Atkins, 2010: 786).
The overall rate law of a complex reaction mechanism is formulated by
combining the first and second order rate laws of the constituent elementary
reactions, usually by applying the steady state assumption or, analogously, by
assuming that some equilibrium is attained. The formulated rate law must be
consistent with the observed rate law. The rate determining step is the slowest step
in a reaction mechanism. The rate of this reaction determines the maximum
overall rate of formation of products (Whittaker, 2000: 179).
 The rate of reaction is often found to be proportional to the concentrations
of the reactants raised to a power. For example, the rate of a reaction may be
proportional to the molar concentrations of two reactants A and B, so we write
v = kr [A][B]
with each concentration raised to the first power. The coefficient kr is called the
rate constant for the reaction. The rate constant is independent of the
concentrations but depends on the temperature. An experimentally determined
equation of this kind is called the rate law of the reaction (Atkins, 2010: 787).
Saponification Reaction of Ethyl Acetate and Sodium Hydroxide is an
irreversible 2nd order overall, 1st order with respect to reactants furthermore
reaction order decreases and become sequential rather than 2nd order when
equimolecular concentrations of both reactants are used. This reaction is non-
catalytic and carried out in a constant density system. This is a homogeneous
phase (liquid/liquid) reaction and mild exothermic in nature.
CH3COOC2H5 + NaOH CH3COONa + C2H5OH (Muchtar, 2015: 46).
As the reaction proceeds, each hydroxide ion removed in the formation of
ethanol removes one molecule of ethyl acetate, being the number of moles of
either OH- or ethyl acetate so removed, the concentration of the reactants
decreases. If we start with equal concentrations of the reactants, the concentration
of NaOH can be conveniently followed at different time intervals by withdrawing
an aliquot from the reaction mixture and determining the NaOH measure of the
rate of reaction, so the greater the value of the rate constant, the faster the
reaction. Each reaction has a definite value of the rate constant at a particular
temperature and the value of the rate constant for the same reaction changes with
temperature and the values do not depend upon the concentration of reaction but
depend upon order of reaction (Ikhazuangbe, 2015: 2).
Ethyl acetate saponification reaction with hydroxide ions is not a simple
reaction, but it turns out that this reaction is a second order reaction, reaction rate
law can be given as:

OH
d [ ester ]
=k 1 [ ester ]
dt
or as,
dx
=k 1 ( ax ) ( bx )
dt
With:
a = the first concentration of Ester, in mole Liter-1
b = the first concentration of OH ion, in mole Liter-1
x = amount mole Liter-1 of ester or base that has reaction
k1 = constanta of reaction rate (Team Lecturer, 2016: 1).
A second-order reaction is a reaction whose rate depends on the
concentration of one reactant raised to the second power or on the concentrations
of two different reactants, each raised to the first power. The simpler type involves
only one kind of reactant molecule:
A product
Where,
[ A ]
rate=
t
From the rate law,
2
rate=k [ A ]
As before, we can determine the units of k by writing
rate M /s 1
k= = 2 = .s
[A]
2
M M

Another type of second-order reaction is

A + B product
And the rate law is given by
rate=k [ A ][ B ]
The reaction is fi rst order in A and fi rst order in B, so it has an overall reaction
order of 2. Using calculus, we can obtain the following expressions for A
product second-order reactions:
 1 1
=kt +
[ A ]t [ A ]0

As Figure 13.13 shows, a plot of 1/[A]t

versus t gives a straight line with slope 5 k and
y intercept = 1/[A]0. (The corresponding
equation for A + B product
reactions is too complex for our discussion.) We
can obtain an equation for the half-life of a
second-order reaction by setting [A]t =[A]0/2 (Chang,
2010: 577-578).

The optimum parameters for saponification of PET waste powder were

determined by gravimetric measurement of product terepthalic acid (TPA). All
kinetics measurements were carried at optimum parameters (Table 1). In kinetic
measurements, three vertical neck round bottom flask was fixed with refluxed
water condenser, an internal digital temperature measurement probe, a
conductivity measuring cell and a micro-controller based vertical type stirrer. A
digital conductivity monitoring instrument made of Equiptronic India Ltd. was
used to measure conductivity. High precision thermostat and digital temperature
measurement probe was used in the present work (Patil, 2014: 1228).
Addition of excess percent of NaOH solution plays significant advantage
in saponification reaction. At 50% excess NaOH fetched 88% increase in rate
constant k beyond which it started showing depleted results. The rate constant
values are show in Table 2. Beyond 120C, the role play of mass transfer comes in
picture simultaneous to kinetic process. Saponification as such appears to be
simple and somewhat fast reaction except the fear of foaming during reaction
which might overflow the reactor contents. However, conducting in-situ
saponification in viscous base oils in grease making is more challenging and
equally interesting for the design of grease kettleagitator assembly. Therefore, On
addition of sodium hydroxide (NaOH) solution to fat, the density of fat increased
and RI decreased (Patil, 2016: 501).
D. APPARATUS AND CHEMICALS
1. Apparatus
a. Erlenmeyer shaper 250 mL 6 pieces
b. Erlenmeyer 250 mL 4 pieces
c. Burette 50 mL 2 pieces
d. Statif 2 pieces
e. Clamp 2 pieces
f. Spray botte 1 piece
g. Stopwatch 1 piece
h. Drop pipette 3 pieces
i. Ball pipette 2 pieces
j. Volumetric flask 5 mL, 10 mL, 20 mL @1 piece
k. Rough cloth 1 piece
l. Soft cloth 1 piece
2. Chemicals
a. Ethyl acetate 0.02M (CH3COOC2H5)
b. Sodium Hydroxide 0.02M (NaOH)
c. Hydrochloric acid 0.02M (HCl)
d. Phenolphthlein indicator
e. Water (H 2O)

E. WORK PROCEDURES
1. Prepared 2 pieces of Erlenmeyer shaper and gave the number (I and II) in
each Erlenmeyer.
2. 40 mL of NaOH 0.02M was putted into Erlenmeyer I.
3. 40 mL of CH3COOC2H5 0.02M was putted into Erlenmeyer II.
4. Prepared sixth Erlenmeyer (gave number 1-6) and putted 20 mL of HCl
0.02M in each Erlenmeyer.
5. NaOH 0.02M (Erlenmeyer I) and CH3COOC2H5 0.02M (Erlenmeyer II) was
mixtured (during mixtured, stopwatch was activated).
6. 5 minutes after reaction was started, 10 mL of mix solution was putted into
Erlenmeyer 1 that contained 20 mL of HCl 0.02M.
7. Added 3 drops of phenolphthalein indicator into solution.
8. The first volume of NaOH was record.
9. Erlenmeyer 1 was titrated by NaOH 0.02M standard solution.
10. The volume of NaOH that used was record.
11. The treatment 6-10 was doing for Erlenmeyer 2-6 (at 10, 15, 20, 25 and 30
minutes).

F. OBSERVATION RESULT

No. Activities Result

1 40 mL of NaOH 0.02M was putted into Colorless
Erlenmeyer I
2 40 mL of CH3COOC2H5 0.02M was putted Colorless
into Erlenmeyer II
3 NaOH 0.02M and CH3COOC2H5 0.02M Yellow and foam
was mixtured
4 20 mL of HCl 0.02M was putted into six Colorless
(6) Erlenmeyer
5 At t = 5, 10, 15, 20, 25 and 30 minutes Colorless
20 mL of HCl 0.02M + 10 mL of mix
solution + 3 drops of phenolphthalein
6 Titration with NaOH 0.02M standard Volume of NaOH
solution.
a. 5 minutes 30.5 mL (pink)
b. 10 minutes 30.9 mL (pink)
c. 15 minutes 31.5 mL (pink)
d. 20 minutes 32.5 mL (pink)
e. 25 minutes 32.9 mL (pink)
f. 30 minutes 33.5 mL (pink)
G. DATA ANALYSIS
Known:
M ethyl acetate = 0.02M
V ethyl acetate = 40 mL
M NaOH = 0.02M
V NaOH = 40 mL
Question:
k = ?
Solution:
1. t = 5 minutes
t = 5 X 60 s = 300 s
V NaOH = 30.5 mL
n NaOH =M NaOH V NaOH
0.02 M 30.5 mL
0.61 mole

nNaOH
x=
V NaOH
0.61 mole

40 mL
1
0.0152 mole mL
0.0152 M

1 x
k 1=
t ( ax )
1 0.0152 M

300 s ( 0.02 M 0.0152 M )
1 0.0152 M

300 s 4.83 M
1 0.0152 M

300 s 4.83 M
3 1
3.33 s 3.17
0.0106 s1

For,
 x 0.0152 M
=
a ( ax ) 0.02 M ( 0.02 M 0.0152 M )
0.0152 M

0.02 M ( 4.83 M )
0.0152 M

9.65 M
158.33

2. t = 10 minutes
t = 10 X 60 s = 600 s
V NaOH = 30.9 mL
n NaOH =M NaOH V NaOH
0.02 M 30.9 mL
0.618 mole

nNaOH
x=
V NaOH
0.618 mole

40 mL
0.0154 mole mL1
0.0154 M

1 x
k 2=
t ( ax )
1 0.0154 M

600 s ( 0.02 M 0.0154 M )
1 0.0154 M

600 s 4.63 M
1 0.0154 M

600 s 4.63 M
1.673 s1 3.35
0.0056 s1

For,
x 0.0154 M
=
a ( ax ) 0.02 M ( 0.02 M 0.0154 M )
0.0154 M

0.02 M ( 4.63 M )
 0.0154 M

9.25 M
167.39

3. t = 15 minutes
t = 15 X 60 s = 900 s
V NaOH = 31.5 mL
n NaOH =M NaOH V NaOH
0.02 M 31.5 mL
0.63 mole

nNaOH
x=
V NaOH
0.63 mole

40 mL
0.0158 mole mL1
0.0158 M

1 x
k3 =
t ( ax )
1 0.0158 M

900 s ( 0.02 M 0.0158 M )
1 0.0158 M

900 s 4.23 M
1 0.0158 M

900 s 4.23 M
3 1
1.11 s 3.76
0.0042 s1

For,
x 0.0158 M
=
a ( ax ) 0.02 M ( 0.02 M 0.0158 M )
0.0158 M

0.02 M ( 4.23 M )
0.0158 M

8.45 M
188.09

4. t = 20 minutes
 t = 20 X 60 s = 1200 s
V NaOH = 32.5 mL
n NaOH =M NaOH V NaOH
0.02 M 32.5 mL
0.65 mole

nNaOH
x=
V NaOH
0.65 mole

40 mL
1
0.0162 mole mL
0.0162 M

1 x
k 4=
t ( ax )
1 0.0162 M

1200 s ( 0.02 M 0.0162 M )
1 0.0162 M

1200 s 3.83 M
1 0.0162 M

1200 s 3.83 M
4 1
8.33 s 4.26
0.0035 s1

For,
x 0.0162 M
=
a ( ax ) 0.02 M ( 0.02 M 0.0162 M )
0.0162 M

0.02 M ( 3.83 M )
0.0162 M
5
7.6 M
213.16

5. t = 25 minutes
t = 25 X 60 s = 1500 s
V NaOH = 32.9 mL
n NaOH =M NaOH V NaOH
0.02 M 32.9 mL
0.658 mole
 nNaOH
x=
V NaOH
0.658 mole

40 mL
1
0.0164 mole mL
0.0164 M

1 x
k5 =
t ( ax )
1 0.0164 M

1500 s ( 0.02 M 0.0164 M )
1 0.01664 M

1500 s 3.63 M
1 0.0164 M

1500 s 3.63 M
4 1
6.67 s 4.56
0.0030 s1

For,
x 0.0164 M
=
a ( ax ) 0.02 M ( 0.02 M 0.0164 M )
0.01664 M

0.02 M ( 3.63 M )
0.0164 M
5
7.2 M
227.78

6. t = 30 minutes
t = 30 X 60 s = 1800 s
V NaOH = 30.5 mL
n NaOH =M NaOH V NaOH
0.02 M 33.5 mL
0.67 mole

nNaOH
x=
V NaOH
0.67 mole

40 mL
 0.0168 mole mL1
0.0168 M

1 x
k6 =
t ( ax )
1 0.0168 M

1800 s ( 0.02 M 0.0168 M )
1 0.0168 M

1800 s 3.23 M
1 0.0168 M

1800 s 3.23 M
4 1
5.56 s 5.25
0.0029 s1

For,
x 0.0168 M
=
a ( ax ) 0.02 M ( 0.02 M 0.0168 M )
0.0168 M

0.02 M ( 3.23 M )
0.0168 M
5
6.4 M
262.5

k + k +k + k +k + k
k = 1 2 3 4 5 6
6
( 0.0010+ 0.0056+0.0042+0.0035+0.0030+ 0.0029 ) s1

6
1
0.0202 s

6
1
0.0034 s

NO x
t (minutes) x (M) k (s-1)
. a ( ax )
1 5 0.0152 0.0106 158.33
2 10 0.0154 0.0056 167.39
3 15 0.0158 0.0042 188.09
4 20 0.0162 0.0035 213.16
5 25 0.0164 0.0030 227.78
6 30 0.0168 0.0029 262.50
 x
Graphic 1. Relationship between and times.
a ( ax )
35

30
f(x) = 5x
25 R = 1

20

15

10

0
0 1 2 3 4 5 6 7

t (minutes)

H. DISCUSSION
Percobaan ini bertujuan untuk menentukan bahwa reaksi penyabunan etil
asetat oleh ion hidroksida adalah reaksi orde kedua dan untuk menentukan tetapan
laju reaksi penyabunan etil asetat oleh ion hidroksida dengan cara titrasi.
Pada percobaan ini yang pertama dilakukan adalah memasukkan masing-
masing 40 mL larutan NaOH 0,02M dan etil asetat 0,02M ke dalam labu
Erlenmeyer bertutup. Erlenmeyer bertutup digunakan agar larutan tidak
terkontaminasi dengan udara luar sehingga larutan tersebut tidak menguap.
Adapun reaksi yang terjadi pada saat pencampuran NaOH dengan etil asetat
menghasilkan garam dan alcohol.
CH3COOH + OH- CH3COO- + C2H5OH
NaOH + HCl NaCl + H2O
HCl(sisa) + NaOH NaCl + H2O
 Campuran antara etilasetat dengan NaOH harus terus dikocok agar reaksi
penguraiannya dapat berlangsung terus. Pada saat pencampuran, stopwatch
dijalankan dan setelah lima menit larutan tersebut dimasukkan kedalam
Erlenmeyer yang berisis asam klorida. Penambahan asam klorida berfungsi untuk
mengasamkan campuran. Setelah itu dilakukan penambahan indicator pp untuk
mengetahui titik ekivalen pada saat dilakukan titrasi. Kemudian campuran
tersebut segera dititrasi dengan NaOH 0,02M. Perlakuan ini berfungsi untuk
mengikat HCl yang berlebih sehingga reaksi penyabunannya berhenti. Titrasi
dilakukan dengan cepat agar campuran larutan tidak menguap karena reaksi
tersebut menghasilkan alcohol yang mudah menguap.
Percobaan ini dilakukan sebanyak enam kali titrasi dengan waktu lima
sampai tiga puluh menit. Variasi waktu tersebut ditujukan agar nantinya dapat
digunakan dalam menentukan orde reaksi 2. Untuk setiap titrasi yang dilakukan
dicatat volume NaOH yang digunakan sebagai data dalam perhitungan
menentukan tetapan laju reaksi.
Dari hasil analisis data diperoleh nilai tetapan laju reaksi untuk
Erlenmeyer 1 sampai 6 yakni: 0,0106 s -1; 0,0056 s-1; 0,0042 s-1; 0,0035 s-1; 0,0030
s-1; dan 0,0029 s-1. Sehingga diperoleh nilai k rata-rata yakni 0,0034 s -1. Adapun
berdasarkan grafik diperoleh nilai R = 1, yang berarti bahwa reaksi penyabunan
etilasetat denga ion hidroksida merupakan orde reaksi kedua.

I. CONCLUSION AND SUGGESTION

1. Conclusion

a. Saponification reaction of ethyl acetate by hydroxide ions is second order

reaction, as shown by the value of R = 1 obtained from the graph of time with

x
.
a ( ax )
b. The reaction rate constant of ethyl acetate saponification by hydroxide ions can
be determined by titration, where titration is performed using 0,02M NaOH
standard solution six times with times varying titration
2. Suggestions
 for further praktikan expected that in doing agitation should be constant
and at the time of titration to be quick so that the results obtained can be
maximized
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