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1st Year Laboratory Report

NAME: CHEAH HAN YONG

GROUP NUMBER: B12

EXPERIMENT NUMBER: 11 (The Hydrolysis of


t-Butyl Chloride)

DATE OF EXPERIEMENT: 24/3/2014

DATE OF SUBMISSION: 31/3/2014

MARK/20(for demonstrator use):

1.1

Learning Outcome
The order for the hydrolysis of t-Butyl Chloride is determined.

CHEAH HAN YONG


BUTYL CHLORIDE

EXPERIMENT 11 HYDROLYSIS OF T-

Understand the effect on the rate constant while varying the ratio of
water and acetone.

1.2 Theory
(CH)CCl + HO (CH)COH + HCl

Hydrolysis is a type of reaction that breaks down a compound with the help of water
molecules. Since t-Butyl Chloride is a tertiary halogenoalkane, it undergoes
hydrolysis via a SN1 mechanism, which is shown below:

STEP ONE:

Slow

Fast
STEP TWO:

OVERALL:

Since the addition of the alkali is small with respect to the large volume of
water, the system can be assumed as a pseudo first-order reaction. A
pseudo first-order reaction is actually a second-order reaction, but with the
ratio of the both reactants to differ greatly. Hence, the rate of reaction for
t-butyl chloride decreases as the concentration of acetone increases. The
function of the acetone is to react immediately with the carbocation to
stabilize it.
Since the reaction is a first-order reaction, the rate equation can be written
as:

[( C H 3 )3 CCl ]t=[ ( C H 3 )3 CCl]0 ekt


ln [ ( C H 3 ) 3 CCl]t =ln[ ( C H 3 )3 CCl ]0kt

CHEAH HAN YONG


BUTYL CHLORIDE

EXPERIMENT 11 HYDROLYSIS OF T-

where [ RCl ] t is the concentration of t-butyl chloride at time t, [ R Cl ] 0


the initial concentration of t-butyl chloride and k is the rate constant.

is

1.3 Relevance
Reactions kinetics is the use of mathematical rate expressions in the
understanding of chemical processes to ensure that a suitable reactor
design and rating for a chemical plant. The knowledge for reaction kinetics
is crucial to allow the concentration of reactants and products to be
calculated at a given time. There are many factors affecting the rate, such
as temperature, pressure and concentration of substrate. In some
reactions such as the production of ammonia, high temperature increases
the rate of reaction. However, the yield decreases due to a forward
exothermic reaction. Hence, a suitable temperature is chosen to ensure
the rate of production to be the most efficient.
2.1 System Used
Water, Acetone, t-Butyl Chloride, Phenolphthalein, Sodium Hydroxide
2.2 Equipment and Procedure

CHEAH HAN YONG


BUTYL CHLORIDE

EXPERIMENT 11 HYDROLYSIS OF T-

White Tile

Stopper
Stopwatch

00:00

Mixture of Water, Acetone & t-Butyl Chloride

Diagram 1: Set Up of Apparatus for the Experiment

Burette
Retort Stand
0.01 M NaOH

Conical Flask

t-Butyl C
Refer to page 39-40 in the Laboratory Handbook for the procedure of this
experiment. The experiment is set up as shown in the diagrams below and
is not drawn to scale.

CHEAH HAN YONG


BUTYL CHLORIDE

EXPERIMENT 11 HYDROLYSIS OF T-

2.3 Hazards

Rinse Hands with water if there is any spillage or came in direct contact
with any chemicals, as t-Butyl Chloride and Sodium Hydroxide are
corrosive.
Shake the conical flask at an open space region to prevent from
knocking into anyone or any apparatus nearby.
Burettes and Pipettes should be handle with care as they are fragile and
may break easily.
Safety Goggles and lab coats should be worn at all times to increase
protection from any unforeseen circumstances occurring while
conducting the experiment.

2.4 Results
(a) Observed Data

CHEAH HAN YONG


BUTYL CHLORIDE

EXPERIMENT 11 HYDROLYSIS OF T-

Table 1: Table for Composition of Acetone Mixture, Initial Volume


of Burette, and Final Temperature of Mixture

% Water
% Acetone
Initial Volume (ml)
Final Temperature (
)

Experiment 1 Experiment 2 Experiment 3


90%
80%
60%
10%
20%
40%
16.0
25.0
34.0
26.0

27.0

27.5

Table 2: Table for Volume of NaOH added and Time Taken for the
Hydrolysis of t-Butyl Chloride

Volume of
NaOH added,
V0.1 ml
0.0
2.0
3.5
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
8.5
9.0

Time, t1 min:s
Experiment
1
00:00
00:43
02:15
03:40
04:30
05:30
06:37
08:06
09:43
12:08
16:24
-

Experiment
2
00:00
01:04
02:38
04:06
05:00
05:50
07:09
08:42
10:15
12:05
15:13
21:50
-

Experiment
3
00:00
02:35
06:52
09:55
11:20
13:17
15:05
17:39
20:23
24:29
29:50
36:20
-

(b) Derived Results


Table 3: Table for Volume of NaOH added and Time Taken for the
Hydrolysis of t-Butyl Chloride after Units Conversion

Volume of
NaOH added,
(V0.1) dm3
0.0000
0.0020
0.0035
0.0045
0.0050

Time, (t1) s
Experiment 1
0
43
135
220
270

Experiment 2 Experiment 3
0
64
158
246
300

0
155
412
595
680

CHEAH HAN YONG


BUTYL CHLORIDE

EXPERIMENT 11 HYDROLYSIS OF T-

0.0055
0.0060
0.0065
0.0070
0.0075
0.0080
0.0085
0.0090

330
397
486
583
728
984
-

Table 4: Table for the Derivation of

Number of
moles of
NaOH
Reacted,
(nNaOH) mol
0.000000
0.000020
0.000035
0.000045
0.000050
0.000055
0.000060
0.000065
0.000070
0.000075
0.000080
0.000085
0.000090

Number of
moles of
(CH3)3CCl
Reacted, (
n(C H ) CCl )
mol
0.000000
0.000020
0.000035
0.000045
0.000050
0.000055
0.000060
0.000065
0.000070
0.000075
0.000080
0.000085
0.000090
3 3

33

ln

ln
0
43
135
220
270
330

[ ( C H 3 )3 CCl ]t
[ ( C H 3 )3 CCl]0
0.000
-0.302
-0.586
-0.821
-0.959
-1.116

797
905
1059
1223
1469
1790
2180
-

[ ( C H 3 )3 CCl ]t

Number of
moles of
Unreacted
(CH3)3CCl,
(n( C H ) CCl )t
mol
0.0000863
0.0000663
0.0000513
0.0000413
0.0000363
0.0000313
0.0000263
0.0000213
0.0000163
0.0000113
0.0000063
0.0000013
0.0000000

Table 5: Table of Time against

Time,
(t1) s

350
429
522
615
725
913
1310
-

Total
Volume of
Mixture in
Conical
Flask,
(VTotal) dm3
0.0510
0.0530
0.0545
0.0555
0.0560
0.0565
0.0570
0.0575
0.0580
0.0585
0.0590
0.0595
0.0600

[ ( C H 3 ) 3 CCl]t
[( C H 3 )3 CCl]0

Concentratio
n of
Unreacted
(CH3)3CCl,
[ ( C H 3 )3 CCl ]t
mol dm-3
0.00169
0.00125
0.00094
0.00074
0.00065
0.00055
0.00046
0.00037
0.00028
0.00019
0.00011
0.00002
0.00000

for Experiment 1

CHEAH HAN YONG


BUTYL CHLORIDE

397
486
583
728
984

EXPERIMENT 11 HYDROLYSIS OF T-

-1.299
-1.519
-1.795
-2.169
-2.761

Graph of Time against ln{[RCl]t/[RCl]0} for Experiment 1


0.000
0
200 400 600
-0.500 f(x) = - 0x - 0.18
R = 0.99
-1.000

800

1000 1200

ln{[RCl]t/[RCl]0} -1.500
-2.000
-2.500
-3.000
Time, (t1) s

ln

Figure 1: Graph of Time against

ln

Table 6: Table of Time against

Time, t1
s
0
64
158
246
300
350
429
522
615
725
913
1310

ln

[( C H 3 )3 CCl ]t
[ ( C H 3 )3 CCl]0
0.000
-0.302
-0.586
-0.821
-0.959
-1.116
-1.299
-1.519
-1.795
-2.169
-2.761
-4.341

[ ( C H 3 ) 3 CCl]t
[ ( C H 3 )3 CCl]0

[ ( C H 3 ) 3 CCl]t
[( C H 3 )3 CCl]0

for Experiment 1

for Experiment 2

CHEAH HAN YONG


BUTYL CHLORIDE

EXPERIMENT 11 HYDROLYSIS OF T-

Graph of Time against ln{[RCl]t/[RCl]0} for Experiment 2


0.000
-1.000

= - 0x400
+ 0 600 800 1000 1200 1400
0 f(x)200
R = 0.99

-2.000
ln{[RCl]t/[RCl]0}
-3.000
-4.000
-5.000
Time, (t1) s

ln

Figure 2: Graph of Time against

ln

Table 7: Table of Time against

Time, t1
s
0
155
412
595
680
797
905
1059
1223
1469
1790
2180

ln

[ ( C H 3 )3 CCl ]t
[ ( C H 3 )3 CCl]0

0.000
-0.302
-0.586
-0.821
-0.959
-1.116
-1.299
-1.519
-1.795
-2.169
-2.761
-4.341

[ ( C H 3 ) 3 CCl]t
[( C H 3 )3 CCl]0

[ ( C H 3 ) 3 CCl]t
[( C H 3 )3 CCl]0

for Experiment 2

for Experiment 3

CHEAH HAN YONG


BUTYL CHLORIDE

EXPERIMENT 11 HYDROLYSIS OF T-

Graph of Time against ln{[RCl]t/[RCl]0} for Experiment 3


0

f(x) = - 0x
500+ 0.21
R = 0.95

1000

1500

2000

2500

Time, (t1) s

Figure 3: Graph of Time against

ln

[ ( C H 3 ) 3 CCl]t
[( C H 3 )3 CCl]0

for Experiment 3

Comparison of Graphs for Experiment 1, Experiment 2 & Experiment 3


0

500

1000

1500

2000

2500

Experiment 1
Linear (Experiment 1)
Experiment 2
Linear (Experiment 2)
Experiment 3
Linear (Experiment 3)

Time, (t1) s
Figure 4: Comparison of Graphs for Experiment 1, 2 & 3

3.0 Calculations

CHEAH HAN YONG


BUTYL CHLORIDE

EXPERIMENT 11 HYDROLYSIS OF T-

The calculations shown below are when 2ml of NaOH is added in


Experiment 1.

Volume of NaOH, V

1
3
=0.0020 dm
1000
Time Taken, t
t=0 min 43 s=43 s
V =2 ml=2

Number of moles of NaOH Reacted, ( n NaOH )

n NaOH =MV =0.01 mol dm 0.0020 dm =0.000020 mol


Number of moles of (CH3)3CCl Reacted, ( n(C H ) CCl )

3 3

The stoichiometry ratio of NaOH and (CH3)3CCl is 1:1,

n(C H ) CCl =0.000020 mol


Density of Acetone,
=791 kg m3
Mass of Acetone, m A
m A= V A , where V A 1 cm3
3 3

as volume of t-butyl chloride is

negligible.

791
g cm3 1 cm3=0.791 g
1000
Mass of t-Butyl Chloride, m R
m A=

Since %w/w of t-Butyl Chloride is 1%,

mR =0.791

Number of Moles of Initial t-Butyl Chloride, (n( C H ) CCl )0


The Molar Mass of t-Butyl Chloride, M R is 92.57,
33

(n( C H

CCl )t =
3 )3

mR 0.00799
=
=0.00008 63 mol
MR
92.57

(n( C H ) CCl )t
) CCl )t =(n( C H ) CCl )0 n( C H ) CCl =0.00008630.000020=0.0000663

Number of Moles of Unreacted t-Butyl Chloride,

(n( C H

1
=0.00799 g
99

m A : mR =99 :1

33

33

33

33

Total Volume of Mixture in Conical Flask, (VTotal)


3

V Total =0.05+0.01+0.02=0.053 dm

Concentration of Unreacted (CH3)3CCl,

[( C H 3 )3 CCl ]t=

( n(C H ) CCl )t
33

V Total

[( C H 3 )3 CCl ]t

0.0000663
=0.00125 mol dm3
0.053

[ ( C H 3 ) 3 CCl]t
0.00125
=ln
=0.302
0.00169
[( C H 3 )3 CCl] 0
Rate Constant for Experiment 1, k 1
k 1=gradient=(0.0027 ) =0.0027 s1
ln

4.0 Discussion
1.For first order rate constants,

[ k ]=

[ Rate]
mol dm3 s1 1
=
=s
[Concentration]
mol dm3

CHEAH HAN YONG


BUTYL CHLORIDE
For

second

EXPERIMENT 11 HYDROLYSIS OF Torder

rate

constants,

3 1

[ k ]=

[Rate ]
mol dm s
=
=mol1 dm3 s1
2
3 2
[Concentration]
( mol dm )

2.A pseudo first-order reaction is actually a second-order reaction, but with


the ratio of the both reactants to differ greatly. Hence, the reactant with
lower concentration is assumed to have negligible concentration and the
reaction is 0th order with respect to that reactant. In this experiment, the
volume of water is large and in excess. Therefore, the rate equation is
written as Rate=k[(CH)CCl] instead of Rate=k[(CH)CCl] [HO].

=k [ A ]
dt
A
3.
d
Rate=
d [ A]
=k d t
[A]
A

ln [ A ] tln [ A]0=kt
ln [ A ] t=kt + ln [ A ]0

4.

ln

{ }

[ A ]t
=kt
[ A ]0

y=mx
The graph of

ln

{[[ ]] }
At
A0

against t is plotted and the gradient of the straight line is

obtained. The rate constant can be calculated with the expression as shown below:

k=gradient =m
5.The slope of a semi-logarithmic plot is obtained by calculating the
instantaneous gradient at that particular point. This can be done by
determining the gradient of two points on the curve that are tightly
spaced together.
The gradient for the graph of Experiment 2 is the steepest, follow by
Experiment 1 and Experiment 3. This result may be due to errors arises
while conducting the experiment. There will always be a delay when
adding the NaOH into the conical flask and would contribute to the sources
of errors in this experiment. Human errors such as parallax errors while
taking measurements are also one of the sources of errors. As only few

CHEAH HAN YONG


BUTYL CHLORIDE

EXPERIMENT 11 HYDROLYSIS OF T-

drops of Phenolphthalein is used, the colour change is still not very


significant even when a white tile is used for a clearer observation.
5.0 Conclusion
The order for the hydrolysis of t-Butyl Chloride is concluded as a pseudo
first-order reaction. The rate constant is higher when a larger composition
of water is used for the hydrolysis reaction. By the study of reaction
kinetics, it is deduced that the gradient of the graph for natural logarithm
of concentration against time is the rate constant multiply by a negative
sign.
6.0 Nomenclature
Symbol

Description

Units

Volume

m3

Density

kg m-3

Molarity

mol dm-3

Mass

kg

Time

Rate Constant

s-1

Molar Mass

g mol-1

MR

7.0 Reference

The University of Manchester (2013). First Year Practical Work,


Propagation of Errors (pp. 50-51)
The University of Manchester (2013). First Year Practical Work,
Experiment 11 The Hydrolysis of t-Butyl Chloride (pp. 39-40)
UC Davis ChemWiki. Pseudo-1st-order reactions
http://chemwiki.ucdavis.edu/Physical_Chemistry/Kinetics/Reaction_Ra
tes/Second-Order_Reactions/Pseudo-1st-order_reactions
Wikipedia Tert-Butyl Chloride
http://en.wikipedia.org/wiki/Tert-Butyl_chloride
TU DELFT Chemical Reaction Kinetics in Practice
http://www.tnw.tudelft.nl/index.php?id=35714
The University of Manchester. Extra Reading Materials The
Hydrolysis of t-Butyl Chloride (pp.1-3)