Brenda Wiputeri

9747180

1st Year Laboratory Report

Name: Brenda Wiputeri

Group Number: D30

Experiment Number: 9

Date of Experiment: 11/12/2015

Date of Report Submission: 18/12/2015

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EXPERIMENT 9
THE HYDROLYSIS OF T-BUTYL CHLORIDE
By Brenda Wiputeri
The University of Manchester School of Chemical Engineering and Analytical Sciences

1. INTRODUCTION
1.1 Learning Outcome
This experiment aims on determining the order of the hydrolysis reaction of t-Butyl
chloride, and also investigating the effect of water to acetone ratio of the solution on the
rate constant of the hydrolysis reaction. [1]

1.2 Theory
The overall reaction equation of the hydrolysis of t-Butyl Chloride is:
(CH3)3CCl + H2O -> (CH3)3COH + HCl
In general kinetics theory, this would be considered as a 2nd order reaction, having the
rate equation:
Rate = 𝓀[(CH3)3CCl][H2O]
The rate is expressed in mol dm-3 s-1, whereas 𝓀 is the 2nd order rate constant with units
mol-1 dm3 s-1, [(CH3)3CCl] is the concentration of t-Butyl Chloride, and [H2O] is the
concentration of H2O with units mol dm-3. However, since the concentration of H2O is
significantly greater, the consumption of H2O would be relatively small, such that it can
be assumed that its change in concentration is negligible in the on-going reaction.[1] This
enables the system to be treated as pseudo first-order. Multiplying the rate constant with
the concentration of water, to produce a new rate constant 𝓀[H2O]= 𝓀′ , giving the
derived pseudo first-order rate equation[2] as:
Rate = 𝓀′[(CH3)3CCl]
Where 𝓀′ is the pseudo 1st order rate constant with units s-1. In theory, since 𝓀′
encompasses [H2O], this rate constant would thereby be dependent on the concentration
of water. This effect will be discussed further in the report based on the experiment
findings.
The hydrolysis of t-Butyl Chloride occurs in a SN1 two-steps mechanism: [3]
First step (slow) (CH3)3CCl -> (CH3)3C+ + Cl-
Second step (fast) (CH3)3C+ + H2O -> (CH3)3COH + H+
Overall Reaction (CH3)3CCl + H2O -> (CH3)3COH + HCl
The slow step is the rate-determining step, giving the rate dependent on the
concentration of (CH3)3CCl, with the rate expression written as:
Rate = 𝓀′[(CH3)3CCl]
The rate of the overall reaction is represented by the change in concentration of a
reactant with time. It can essentially be written as the rate of consumption of (CH3)3CCl
or generation of (CH3)3COH or HCl: [3]
−𝑑[(CH3 )3 CCl] 𝑑[(CH3 )3 COH] 𝑑[HCl]
Rate = = = 𝑑𝑡
𝑑𝑡 𝑑𝑡
Using the rate of consumption of (CH3)3CCl, equating it to the previously defined rate
expression gives a differential equation:
−𝑑[(CH3 )3 CCl]
= 𝓀′[(CH3 )3 CCl]
𝑑𝑡
Integrating the differential equation, obtains a semi-logarithmic function:
[(CH ) CCl]
−ln [(CH 3) 3CCl] 𝐴 = 𝓀′𝑡 (Equation 1)
3 3 𝐴𝑜

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Where 𝓀′ is the rate constant with units s-1, [(CH3 )3 CCl]𝐴 and [(CH3 )3 CCl]𝐴𝑜 is the
concentration of t-Butyl Chloride at any time elapsed, t, and at time = 0 respectively,
both concentrations with units mol dm-3.
[(CH ) CCl]
A graph of −ln [(CH 3) 3CCl] 𝐴 on the Y-axis, and time (t) on the X-axis could be plotted to
3 3 𝐴𝑜
determine the value of 𝓀′ from the value of the slope. Since it is a semi-logarithmic, the
approximate slope could be determined from the equation of the best-fit line of the data
points. [4] Perceiving Equation 1 as a linear function, the best-fit line of the data points
should intercept at (0,0) as the y-intercept value in the function is essentially zero.
To determine the progress of the hydrolysis reaction, alkali (0.01M of NaOH) is to be
added successively. In this reaction, HCl reacts with NaOH, producing water and salt:
NaOH + HCl -> NaCl + H2O
Each successive additions of NaOH will consume a certain amount of HCl produced in
the hydrolysis reaction, which enables the moles and concentration of the t-Butyl
Chloride at that time to be known. Noting the time for the indicator in the solution to
change color (from pink to colorless), which indicates the solution changing from basic
to acidic, will enable the progress of the hydrolysis to be determined.[1] Knowing the
changes in concentration and time would enable the order of reaction and rate constant
to be determined, with reference to Equation 1.
𝐸𝑎
According to Arrhenius Equation, ln 𝑘 = ln 𝐴 − 𝑅𝑇 (where k is rate constant, A is a
factor, Ea is activation energy, R is the gas constant, and T is temperature), the rate
constant is inversely related to temperature. [5] This relationship will be investigated in
the experiment.

1.3 Relevance
The understanding of reaction rates is relevant in areas like industrial processes of such
as food and materials, also the environment, such as limestone erosions and ozone
decomposition. [6] Second order reactions are relatively more challenging to determine
the rate constant because it requires two reactants to be measured concurrently, which
often makes the method more complicated and potentially less economically efficient.[2]
It is why pseudo first-order reactions are relevant and often used. An example of where
pseudo first-order reactions are used for analysis in industry would be in the hydrolysis
of sucrose. [7]

2. EXPERIMENTAL WORK
2.1 System Used
Water, t-Butyl Chloride ((CH3)3CCl) in acetone, and sodium hydroxide (NaOH).

2.2 Equipment and Procedure

Figure 1 – Experiment Set-Up
Burette
Filled with Clock timer[8]
(Image from: "Taylor Timer."
NaOH
Photograph. Target. N.p., n.d. Web. 16 Dec. )

Water Beaker with

1% t-Butyl Chloride in acetone
Phenolphthalein
Indicator
Pipette
Measuring
Cylinder
Conical flask with solution

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Procedure
Prepare a 50cm3 solution comprised of 90% water and 10% acetone by volume into a
125cm3 conical flask. Add a few drops of phenolphthalein indicator into the solution,
which enables color change to be visible later, when indicating a basic or acidic solution
(pink when basic and colorless when acidic), and shake the flask. Prepare a 50cm3 burette
filled with 0.01M NaOH. Add 2cm3 of the NaOH solution to the solution in the flask and
shake. Pipette 1cm3 of the 1% t-Butyl Chloride in acetone into the solution and start the
clock after discharging 0.5cm3 of it. Shake the solution in the flask and record the time for
the color of the solution to change from pink to colorless, as it becomes in acidic state.
Then add 1.5cm3 of NaOH from the burette, shake, and record the time for the color
change again. Reiterate this with successively fewer volumes of NaOH. Determine the
volume of NaOH needed to complete neutralization, which is once there is no more color
change. Finally, measure the temperature of the solution in the conical flask. Repeat the
entire experiment with other varieties of water to acetone ratios (80% water with 20%
acetone and 70% water with 30% acetone). For more information, refer to handbook. [1]

2.3 Hazards
Sodium hydroxide and t-Butyl Chloride should be handled carefully and washed off
immediately when there is contact as it is slightly corrosive. All glassware used should
also be handled carefully. Safety glasses and lab coats should also be worn at all times
as the experiment is done in the lab where other experiments with other hazards are
taking place.

2.4 Results
Table 1 – Experimental measurements for each run corresponding to each water to
acetone ratio solution, comprising of total volume and moles of NaOH, initial moles and
concentration of t-Butyl Chloride ((CH3)3CCl)
Initial moles of Initial concentration
Total Volume Moles of NaOH
Water Acetone (CH3)3CCl (nAo) (CAo)
Run of NaOH (mL) (mol)
(%) (%) (mol) (mol L-1)
(± 0.05 mL) (± 5x10-7 mol)
(±4.52x10-7 mol) (± 1.96x10-5 mol L-1)
1 90 10 7.90 7.90 x10-5 9.04 x10-5 1.77 x10-3
2 80 20 8.50 8.50 x10-5 9.04 x10-5 1.77 x10-3
3 70 30 8.40 8.40 x10-5 9.04 x10-5 1.77 x10-3

Table 2 – Derived results from Run 1 of the experiment (90% Water and 10 % Acetone
ratio), comprising of time, volume and moles of NaOH added, cumulative moles of
NaOH, moles of (CH3)3CCl, concentration of (CH3)3CCl (CA), -ln(CA/CAo) and its error

Time Volume Cumulative Moles of Concentration

Moles of
Elapsed, NaOH moles of (CH3)3CCl (CA) ±Error CA ±Error
NaOH (mol) -ln(CA / CAo)
t, (s) (mL) NaOH (mol) (nA) (mol) (mol L-1) (mol L-1) -ln(CA / CAo)
(± 5x10-7 mol)
(±0.5 s) (± 0.05 mL) (± 5x10-7 mol) (± 6.74x10-7 mol)
0.0 0.00 0.0 0.0 9.04 x10-5 1.77 x10-3 2.19 x10-5 0.00 1.66 x10-2
37.0 2.00 2.0 x10-5 2.0 x10-5 7.04 x10-5 1.33 x10-3 1.79 x10-5 0.29 1.74 x10-2
158.0 1.50 1.5 x10-5 3.5 x10-5 5.54 x10-5 1.02 x10-3 1.55 x10-5 0.56 1.88 x10-2
220.0 1.30 1.3 x10-5 4.8 x10-5 4.24 x10-5 7.59 x10-4 1.39 x10-5 0.85 2.14 x10-2
298.0 1.00 1.0 x10-5 5.8 x10-5 3.24 x10-5 5.70 x10-4 1.29 x10-5 1.13 2.52 x10-2
296.0 0.70 7.0 x10-6 6.5 x10-5 2.54 x10-5 4.41 x10-4 1.23 x10-5 1.39 3.01 x10-2
464.0 0.30 3.0 x10-6 6.8 x10-5 2.24 x10-5 3.87 x10-4 1.21 x10-5 1.52 3.32 x10-2

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545.0 0.20 2.0 x10-6 7.0 x10-5 2.04 x10-5 3.51 x10-4 1.20 x10-5 1.62 3.59 x10-2
594.0 0.20 2.0 x10-6 7.2 x10-5 1.84 x10-5 3.16 x10-4 1.19 x10-5 1.72 3.93 x10-2
646.0 0.10 1.0 x10-6 7.3 x10-5 1.74 x10-5 2.98 x10-4 1.18 x10-5 1.78 4.12 x10-2
723.0 0.20 2.0 x10-6 7.5 x10-5 1.54 x10-5 2.63 x10-4 1.17 x10-5 1.91 4.60 x10-2
852.0 0.20 2.0 x10-6 7.7 x10-5 1.34 x10-5 2.28 x10-4 1.16 x10-5 2.05 5.23 x10-2
1032.0 0.20 2.0 x10-6 7.9 x10-5 1.14 x10-5 1.93 x10-4 1.16 x10-5 2.22 6.09 x10-2
Table 3 – Derived results from Run 2 of the experiment (80% Water and 20 % Acetone ratio),
comprising of time, volume and moles of NaOH added, cumulative moles of NaOH, moles of
(CH3)3CCl, concentration of (CH3)3CCl (CA), -ln(CA/CAo) and its error
Time Volume Cumulative Moles of Concentration
Moles of
Elapsed, NaOH moles of (CH3)3CCl (CA) ±Error CA ±Error
NaOH (mol) -ln(CA / CAo)
t, (s) (mL) NaOH (mol) (nA) (mol) (mol L-1) (mol L-1) -ln(CA / CAo)
(± 5x10-7 mol)
(±0.5 s) (± 0.05 mL) (± 5x10-7 mol) (± 6.74x10-7 mol)
0.0 0.00 0.0 0.0 9.04 x10-5 1.77 x10-3 2.19 x10-5 0.00 1.66 x10-2
124.0 3.20 3.2 x10-5 3.2 x10-5 5.84 x10-5 1.08 x10-3 1.59 x10-5 0.50 1.85 x10-2
251.0 1.50 1.5 x10-5 4.7 x10-5 4.34 x10-5 7.79 x10-4 1.40 x10-5 0.82 2.11 x10-2
347.0 1.00 1.0 x10-5 5.7 x10-5 3.34 x10-5 5.89 x10-4 1.30 x10-5 1.10 2.47 x10-2
445.0 0.50 5.0 x10-6 6.2 x10-5 2.84 x10-5 4.96 x10-4 1.26 x10-5 1.27 2.76 x10-2
540.0 0.50 5.0 x10-6 6.7 x10-5 2.34 x10-5 4.05 x10-4 1.22 x10-5 1.48 3.21 x10-2
584.0 0.20 2.0 x10-6 6.9 x10-5 2.14 x10-5 3.69 x10-4 1.21 x10-5 1.57 3.45 x10-2
620.0 0.10 1.0 x10-6 7.0 x10-5 2.04 x10-5 3.51 x10-4 1.20 x10-5 1.62 3.59 x10-2
671.0 0.20 2.0 x10-6 7.2 x10-5 1.84 x10-5 3.16 x10-4 1.19 x10-5 1.72 3.93 x10-2
751.0 0.20 2.0 x10-6 7.4 x10-5 1.64 x10-5 2.80 x10-4 1.18 x10-5 1.84 4.35 x10-2
796.0 0.10 1.0 x10-6 7.5 x10-5 1.54 x10-5 2.63 x10-4 1.17 x10-5 1.91 4.60 x10-2
831.0 0.10 1.0 x10-6 7.6 x10-5 1.44 x10-5 2.45 x10-4 1.17 x10-5 1.98 4.89 x10-2
919.0 0.20 2.0 x10-6 7.8 x10-5 1.24 x10-5 2.11 x10-4 1.16 x10-5 2.13 5.62 x10-2
1036.0 0.20 2.0 x10-6 8.0 x10-5 1.04 x10-5 1.76 x10-4 1.15 x10-5 2.31 6.64 x10-2
1162.0 0.20 2.0 x10-6 8.2 x10-5 8.38 x10-6 1.42 x10-4 1.14 x10-5 2.53 8.16 x10-2
1342.0 0.30 3.0 x10-6 8.5 x10-5 5.38 x10-6 9.04 x10-5 1.14 x10-5 2.98 1.26 x10-1

Table 4 – Derived results from Run 3 of the experiment (70% Water and 30 % Acetone ratio),
comprising of time, volume and moles of NaOH added, cumulative moles of NaOH, moles of
(CH3)3CCl, concentration of (CH3)3CCl (CA), -ln(CA/CAo) and its error
Time Volume Cumulative Moles of Concentration
Moles of
Elapsed, NaOH moles of (CH3)3CCl (CA) ±Error CA ±Error
NaOH (mol) -ln(CA / CAo)
t, (s) (mL) NaOH (mol) (nA) (mol) (mol L-1) (mol L-1) -ln(CA / CAo)
(± 5x10-7 mol)
(±0.5 s) (± 0.05 mL) (± 5x10-7 mol) (± 6.74x10-7 mol)
0.0 0.00 0.0 0.0 9.04 x10-5 1.77 x10-3 2.19 x10-5 0.00 1.66 x10-2
67.0 2.00 2.0 x10-5 2.0 x10-5 7.04 x10-5 1.33 x10-3 1.79 x10-5 0.29 1.74 x10-2
181.0 1.50 1.5 x10-5 3.5 x10-5 5.54 x10-5 1.02 x10-3 1.55 x10-5 0.56 1.88 x10-2
268.0 1.00 1.0 x10-5 4.5 x10-5 4.54 x10-5 8.18 x10-4 1.42 x10-5 0.77 2.06 x10-2
329.0 0.50 5.0 x10-6 5.0 x10-5 4.04 x10-5 7.21 x10-4 1.37 x10-5 0.90 2.19 x10-2
374.0 0.40 4.0 x10-6 5.4 x10-5 3.64 x10-5 6.45 x10-4 1.33 x10-5 1.01 2.33 x10-2
415.0 0.30 3.0 x10-6 5.7 x10-5 3.34 x10-5 5.89 x10-4 1.30 x10-5 1.10 2.47 x10-2
440.0 0.20 2.0 x10-6 5.9 x10-5 3.14 x10-5 5.51 x10-4 1.28 x10-5 1.17 2.57 x10-2
460.0 0.10 1.0 x10-6 6.0 x10-5 3.04 x10-5 5.33 x10-4 1.27 x10-5 1.20 2.63 x10-2
491.0 0.20 2.0 x10-6 6.2 x10-5 2.84 x10-5 4.96 x10-4 1.26 x10-5 1.27 2.76 x10-2

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530.0 0.20 2.0 x10-6 6.4 x10-5 2.64 x10-5 4.60 x10-4 1.24 x10-5 1.35 2.92 x10-2
561.0 0.20 2.0 x10-6 6.6 x10-5 2.44 x10-5 4.23 x10-4 1.23 x10-5 1.43 3.10 x10-2
606.0 0.20 2.0 x10-6 6.8 x10-5 2.24 x10-5 3.87 x10-4 1.21 x10-5 1.52 3.32 x10-2
646.0 0.10 1.0 x10-6 6.9 x10-5 2.14 x10-5 3.69 x10-4 1.21 x10-5 1.57 3.45 x10-2
682.0 0.10 1.0 x10-6 7.0 x10-5 2.04 x10-5 3.51 x10-4 1.20 x10-5 1.62 3.59 x10-2
712.0 0.10 1.0 x10-6 7.1 x10-5 1.94 x10-5 3.34 x10-4 1.20 x10-5 1.67 3.75 x10-2
741.0 0.10 1.0 x10-6 7.2 x10-5 1.84 x10-5 3.16 x10-4 1.19 x10-5 1.72 3.93 x10-2
786.0 0.10 1.0 x10-6 7.3 x10-5 1.74 x10-5 2.98 x10-4 1.18 x10-5 1.78 4.12 x10-2
844.0 0.20 2.0 x10-6 7.5 x10-5 1.54 x10-5 2.63 x10-4 1.17 x10-5 1.91 4.60 x10-2
878.0 0.10 1.0 x10-6 7.6 x10-5 1.44 x10-5 2.45 x10-4 1.17 x10-5 1.98 4.89 x10-2
928.0 0.10 1.0 x10-6 7.7 x10-5 1.34 x10-5 2.28 x10-4 1.16 x10-5 2.05 5.23 x10-2
986.0 0.10 1.0 x10-6 7.8 x10-5 1.24 x10-5 2.11 x10-4 1.16 x10-5 2.13 5.62 x10-2
1031.0 0.10 1.0 x10-6 7.9 x10-5 1.14 x10-5 1.93 x10-4 1.16 x10-5 2.22 6.09 x10-2
1123.0 0.10 1.0 x10-6 8.0 x10-5 1.04 x10-5 1.76 x10-4 1.15 x10-5 2.31 6.64 x10-2
1255.0 0.10 1.0 x10-6 8.1 x10-5 9.38 x10-6 1.59 x10-4 1.15 x10-5 2.41 7.32 x10-2
1455.0 0.10 1.0 x10-6 8.2 x10-5 8.38 x10-6 1.42 x10-4 1.14 x10-5 2.53 8.16 x10-2
1520.0 0.10 1.0 x10-6 8.3 x10-5 7.38 x10-6 1.24 x10-4 1.14 x10-5 2.66 9.24 x10-2
1765.0 0.10 1.0 x10-6 8.4 x10-5 6.38 x10-6 1.07 x10-4 1.14 x10-5 2.80 1.07 x10-1
Figure 2 – Relationship between -ln(CA/CAo) and time elapsed for Run 1 (90 % Water and
10 % Acetone ratio)
-ln(CA/CAo) vs. Time

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-ln(CA/CAo) = 0.0027t
R² = 0.81769

2.5

2
-ln(CA/CAo)

1.5
Run 1

Linear (Run 1)

0.5

0
0 200 400 600 800 1000 1200
Time, t (s) (±0.5 s)

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Figure 3 – Relationship between -ln(CA/CAo) and time elapsed for Run 2 (80 % Water and
20 % Acetone ratio)
-ln(CA/CAo) vs. Time

3.5 -ln(CA/CAo) = 0.0024t

R² = 0.94732

2.5
-ln(CA/CAo)

1.5
Run 2

1
Linear (Run 2)

0.5

0
0 200 400 600 800 1000 1200 1400 1600
Time, t (s) (±0.5 s)

Figure 4 – Relationship between -ln(CA/CAo) and time elapsed for Run 3 (70 % Water
and 30 % Acetone ratio)

-ln(CA/CAo) vs. Time

4
-ln(CA/CAo)= 0.002t
R² = 0.83983
3.5

2.5
-ln(CA/CAo)

2
Run 3

1.5

1
Linear (Run 3)

0.5

0
0 200 400 600 800 1000 1200 1400 1600 1800 2000
Time, t (s) (±0.5 s)

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In Figures 2,3, and 4, the Y-error bars represent the respective propagated errors of the
-ln(CA/CAo) values. They increase proportionally with the -ln(CA/CAo) values as the error is
dependent on it, which is explained further in the errors section. The X-error bars represent the
error of the time, which comes from the uncertainty of the clock (±0.5 s). Due to its comparison
to the scale of the X-axis, although present, the X-error bars are not visible.

Table 5 – Derived rate constants and measured final temperature of the solution for each run
Run (Water to Acetone Ratio) Rate Constant, 𝓀′, (s-1) Temperature (oC)
(±0.5 oC)
-3 -5
1 (90% Water and 10% Acetone) 2.70 x10 ± 6.51 x10 27.0
-3 -5
2 (80% Water and 20% Acetone) 2.40 x10 ± 5.93 x10 27.0
-3 -5
3 (70% Water and 30% Acetone) 2.00 x10 ± 5.75 x10 31.0

3. CALCULATIONS
The following specimen calculations refer to the data in Run 1 of Table 1.
The moles of NaOH is calculated by multiplying the concentration of NaOH in the solution
with the volume. The volume should first be converted to liters.
𝑚𝑜𝑙 1𝐿
0.01 × 7.9 𝑚𝐿 × = 7.9 × 10−5 𝑚𝑜𝑙
𝐿 1000 𝑚𝐿
The initial moles (nAo) is calculated by multiplying the density and volume, and dividing it
by its molecular weight. The density (0.836 gr mL-1) and molecular weight (92.5 gr mol-1) is
given.[1] The volume is obtained by multiplying the percentage of (CH3)3CCl in the acetone
solution by the volume of acetone solution added (1 mL).
1
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 (CH3 )3 CCl = × 1 𝑚𝐿 = 0.01 𝑚𝐿
100
𝑔𝑟
0.836 × 0.01 𝑚𝐿
n𝐴𝑜 = 𝑚𝐿 = 9.04 × 10−5 𝑚𝑜𝑙
92.5 𝑔𝑟 𝑚𝑜𝑙 −1
The concentration (CAo) is calculated by dividing the moles (nAo) with the total volume of
the solution, and converting it to SI units, mol L-1:
9.04 × 10−5 𝑚𝑜𝑙 1000 𝑚𝐿
C𝐴𝑜 = × = 1.77 × 10−3 𝑚𝑜𝑙 𝐿−1
51 𝑚𝐿 1𝐿
The following specimen calculations depict the methodology to obtain the derived results in
Table 2, 3, and 4. The following sample refers to those of the second row of Table 2. The
errors, including columns 7 and 9, are to be discussed in the errors section.
The cumulative moles of NaOH are the sum of the total moles of NaOH added since the
initial time (0 s). It is calculated by summing the additional moles of NaOH to the prior
cumulative moles of NaOH (corresponding to the previous time recorded).
𝐶𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑣𝑒 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 NaOH = 0 𝑚𝑜𝑙 + 0.00002 𝑚𝑜𝑙 = 2 × 10−5 𝑚𝑜𝑙
From the chemical equations of the two reactions, it can be assumed that the moles of
(CH3)3CCl (nA) reacted is equivalent to the moles of NaOH. The moles of (CH3)3CCl is then
calculated by subtracting the initial moles (from Table 1) by the moles reacted.
𝑛𝐴 = 9.04 × 10−5 𝑚𝑜𝑙 − 0.00002 𝑚𝑜𝑙 = 7.04 × 10−5 𝑚𝑜𝑙
The concentration (CA) of (CH3)3CCl is then derived by dividing the moles by cumulative
total volume of the solution (which adds up every time NaOH is added), and converting it to
in terms of SI units mol L-1.
7.04 × 10−5 𝑚𝑜𝑙 1000 𝑚𝐿
𝐶𝐴 = × ≈ 1.33 × 10−3 𝑚𝑜𝑙 𝐿−1
51 𝑚𝐿 + 0 𝑚𝐿 + 2 𝑚𝐿 1𝐿

The eighth column data is the negative natural logarithm of CA divided by CAo, which
produces a dimensionless quantity as the units cancel out:

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1.328 × 10−3 𝑚𝑜𝑙 𝐿−1
−ln ≈ 0.289
1.722 × 10−3 𝑚𝑜𝑙 𝐿−1
To obtain the rate constant, Equation 1 is used. As elaborated in the theory, the slope of the
best-fit line corresponds to the rate constant. Thus, the values for the rate constants are
derived from the slopes of the best-fit line in Figures 2,3, and 4 corresponding to each runs.
For example in run 1 (Figure 2), the equation of the best-fit line is -ln(CA/CAo) = 0.0027t.
The rate constant, 𝓀′ , is therefore:
[(CH3 )3 CCl]𝐴
𝑑 (−ln )
′ [(CH3 )3 CCl]𝐴𝑜
𝓀 = = 0.0027 𝑠 −1 ≈ 2.70 × 10−3 𝑠 −1
𝑑𝑡

Calculations for errors

The uncertainty for the volume of NaOH is ±0.05 mL, which is half the scale of the
instrument used to measure the volume (burette with 0.1 mL scale).
The other errors are derived through propagation of errors analysis [1] as the values are
derived from multiple calculations, and are as follows:
Case function -> 𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑁𝑎𝑂𝐻 = 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 × 𝑣𝑜𝑙𝑢𝑚𝑒
Propagated error -> ∆𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑁𝑎𝑂𝐻 = 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 × ∆𝑣𝑜𝑙𝑢𝑚𝑒
𝑚𝑜𝑙
∆𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑁𝑎𝑂𝐻 = 1 × 10−5 × ±0.05 mL = ±5 × 10−7 𝑚𝑜𝑙
𝑚𝐿
𝜌 × 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓(CH3)3CCl
Case function -> nAo = 𝑀𝑟
1
Propagated error -> ∆𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 (CH3)3CCl = 100 × ∆𝑝𝑖𝑝𝑒𝑡𝑡𝑒
1
∆𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 (CH3)3CCl = × ±0.005 𝑚𝐿 = ±5 × 10−5 𝑚𝐿
100
𝑔𝑟
𝜌 0.836 × ±5 × 10−5 𝑚𝐿
∆𝑛𝐴𝑜 = × ∆ 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓(CH3)3CCl = 𝑚𝐿 = ±4.52 × 10−7 𝑚𝑜𝑙
𝑀𝑟 92.5 𝑔𝑟 𝑚𝑜𝑙 −1
𝑛
Case function -> CAo =𝑉 𝐴𝑜
𝑡𝑜𝑡𝑎𝑙
2 2
Propagated error -> ∆𝐶𝐴𝑜 = 𝐶𝐴𝑜 √(∆𝑉
𝑉
𝑡𝑜𝑡𝑎𝑙 ∆𝑛
) + ( 𝐴𝑜 )
𝑛
𝑡𝑜𝑡𝑎𝑙 𝐴𝑜

∆𝑉𝑡𝑜𝑡𝑎𝑙 = √(∆𝑚𝑒𝑎𝑠𝑢𝑟𝑖𝑛𝑔 𝑐𝑦𝑙𝑖𝑛𝑑𝑒𝑟)2 + (∆𝑝𝑖𝑝𝑒𝑡𝑡𝑒)2 + (∆𝑏𝑢𝑟𝑒𝑡𝑡𝑒)2

= √(±0.5 mL)2 + (±0.005 mL)2 + (± 0.05 mL)2 ≈ ±5.02 × 10−4 𝐿
2 2
−3 −1 √
±5.02 × 10−4 𝐿 ±4.52 × 10−7 𝑚𝑜𝑙
∆𝐶𝐴𝑜 = 1.722 × 10 𝑚𝑜𝑙 𝐿 ( ) +( ) = ±1.96 × 10−5 𝑚𝑜𝑙 𝐿−1
0.051 𝐿 9.03784 × 10−5 𝑚𝑜𝑙
Case function -> 𝑛𝐴 = 𝑛𝐴𝑜 − 𝑛𝑁𝑎𝑂𝐻
Propagated error -> ∆𝑛𝐴 = √(∆𝑛𝐴𝑜 )2 + (∆𝑛𝑁𝑎𝑂𝐻 )2
= √(±4.52 × 10−7 𝑚𝑜𝑙)2 + (±5 × 10−7 𝑚𝑜𝑙 )2 = ±6.74 × 10−7 𝑚𝑜𝑙

The following propagated errors (columns seven and nine of Table 2, 3, and 4) vary for each
CA value so the following are examples for CA value of row 2 Table 2:
𝑛
Case function -> 𝐶𝐴 = 𝑐𝑢𝑚𝑚𝑢𝑙𝑎𝑡𝑖𝑣𝑒𝐴𝑡𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒
∆𝑉𝑡𝑜𝑡𝑎𝑙 2 ∆𝑛 2
Propagated error -> ∆𝐶𝐴 = 𝐶𝐴 √(𝑉 ) + ( 𝑛 𝐴)
𝑐𝑢𝑚𝑚𝑢𝑙𝑎𝑡𝑖𝑣𝑒 𝑡𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝐴

±5.02×10−4 𝐿 2 ±6.74×10−7 𝑚𝑜𝑙 2

= 1.328 × 10−3 𝑚𝑜𝑙 𝐿−1 √( ) +( ) =±1.789× 10−5 𝑚𝑜𝑙 𝐿−1
0.053 𝐿 7.03784×10−5 𝑚𝑜𝑙
𝐶𝐴 𝐶𝐴𝑜
Case function -> −ln = ln
𝐶𝐴𝑜 𝐶𝐴
𝐶
𝐶𝐴𝑜 ∆ 𝐴𝑜 ∆𝐶𝐴 2 ∆𝐶𝐴𝑜 2
𝐶𝐴
Propagated error -> ∆ln = 𝐶𝐴𝑜 = √( ) +( )
𝐶𝐴 𝐶𝐴 𝐶𝐴𝑜
𝐶𝐴

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±1.789×10−5 𝑚𝑜𝑙 𝐿−1 2 ±1.96×10−5 𝑚𝑜𝑙 𝐿−1 2

= √( 1.328 ×10−3 𝑚𝑜𝑙 𝐿−1 ) + (1.722 × 10−3 𝑚𝑜𝑙 𝐿−1 ) = ±0.0174
The error of the rate constant is also derived from the propagated errors analysis, with
reference to the point that lies on the best-fit line on each figure.
For example, for Run 1, the point that lies on the best-fit line in Figure 2 is at
time=723±0.5s and -ln(CA/CAo)=1.91±4.60 x10-2 (refer values to Table 2):
[(CH3 )3 CCl]𝐴
−ln
′ [(CH3 )3 CCl]𝐴𝑜
Case function ->𝓀 = 𝑡

[(CH3 )3 CCl]𝐴 2
∆ −ln ∆𝑡 2
[(CH3 )3 CCl]𝐴𝑜
Propagated error ->∆𝓀′ = 𝓀′√( [(CH3 )3 CCl]𝐴 ) +(𝑡)
−ln
[(CH3 )3 CCl]𝐴𝑜

2
±4.60 × 10−2 ±0.5s 2
= 2.7 × 10−3 𝑠 −1 √( ) +( ) = ±6.5 × 10−5 𝑠 −1
1.91 723 𝑠
4. DISCUSSION
The results of this experiment show that there is positive correlation between -ln(CA/CAo)
and time, based on the positive slopes for their respective best-fit lines, displayed in Figures
2,3, and 4. This supports the proposed relationship from Equation 1, in which the positive
slopes represent the pseudo 1st order rate constant, 𝓀′ . The rate constants derived from the
slopes are 2.70x10-3 s-1 for Run 1, 2.40x10-3 s-1 for Run 2, and 2.00x10-3 s-1 for Run 3. This
shows a positive correlation between the rate constant and the water to acetone ratio of the
initial solution. As the ratio decreases (less fraction of water), the rate constant also
decreases. This supports the theory that because the pseudo 1st order rate constant 𝓀′
consists of the term of concentration of water, the rate constant and water concentration
would be directly proportional. Since the initial concentrations of (CH3)3CCl for all runs are
the same, this trend of the rate constant in relation to ratio also shows that the rate of
reaction increases as the water to acetone ratio increases. From Table 5, it can be seen that
the final temperature of the solution is 27oC for Run 1 and 2, and 31oC for Run 3. These
measurements do not show any particular coherent relationship between the temperature and
the rate constants. This contradicts the theory of Arrhenius Equation, in which case states
the temperature to be inversely related to the rate constant. This contradiction is most likely
due to errors committed in the experiment.

The coefficients of determination (R2) values are 0.81769 for Run 1, 0.94732 for Run 2, and
0.83983 for Run 3. This indicates strong linear correlation for Run 2, but relatively weak for
Run 1 and Run 3 as they are below 0.9. This deviation from a linear correlation shows the
room for error in the measurements data. As it can be seen from Figures 2,3, and 4, most of
the data points do not line coherently on the linear trend-line, which indicates random errors
in the experiment or systematic errors in the design of the experiment. A reason for the weak
linear correlation in Run 3 may be due to the fact that it is assumed that the excess volume
of water has negligible change in concentration. However, since there is less percentage of
water in Run 3, the concentration change of water would relatively have more effect to the
rate of reaction, so disregarding its effect on the rate expression would thereby lead to a
misconception in the experiment findings. For Run 1, the weak linear correlation is most
likely due to random errors.

Uncertainties represent the possible errors in the data obtained from the experiment. A
potential source of error in this experiment is human error, which may occur during the
recording of the time for when the solution changes color. This is especially relevant for

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when successive smaller amounts of alkali is added and causes the color change to happen
rapidly. Errors in the recorded time would affect the data plotted, which impacts the rate
constant derived. Being more meticulous when observing the time for color change and
repeated trials of this experiment would reduce this error and increase precision. Parallax
error may have occurred as well when reading the measurements of the volumes with the
various instruments used, especially the burette when it is placed not at eye-level. This
affects the accuracy of the volumes recorded. The error can be reduced by having another
individual to take the reading as well. There is also systematic error in the clock used, but is
relatively small relative to the scale of the data for time obtained from the experiment. Other
unpredictable random errors potentially occurred as well, which caused fluctuations and
affects the precision of the results. Random errors could be reduced to increase precision by
being more meticulous and repeating more trials of the experiment.

5. CONCLUSION
In conclusion, the hydrolysis of t-Butyl Chloride can be regarded as a pseudo first-order
reaction. The experiment findings show that the water to acetone ratio in the initial solution
effects and has positive relationship with the rate constant, which supports the initial
theories. However, the experimental findings have relatively low correlation coefficients and
do not support the Arrhenius Equation theory that relates the rate constant with temperature
and, which indicates errors in the findings. From the experiment, theories such as the order
of the hydrolysis reaction and pseudo first-order reactions were learned. Insights on
confirming the order of reaction through plotting the data and deriving a method to
determine the rate constant through the slope of the semi-logarithmic plot were also
obtained. In addition, the relationship between the rate constant and the water to acetone
ratio and also the temperature effect were also learned. Furthermore, the errors were
evaluated and safety precautions of this experiment were studied.

6. NOMENCLATURE
Symbol Quantity Unit
nd
𝓀 2 Order Rate Constant mol dm3 s-1
-1

Concentration of t-Butyl
[(CH3)3CCl] chloride mol dm-3
[H2O] Concentration of water mol dm-3
𝓀′ 1st Order Rate Constant s-1
Concentration of t-Butyl
[(CH3)3CCl]A chloride at time = t mol dm-3
Concentration of t-Butyl
[(CH3)3CCl]Ao chloride at time = 0 mol dm-3
Moles of t-Butyl
nAo chloride at time = 0 mol
Concentration of t-Butyl
CAo chloride at time = 0 mol dm-3
t Time (elapsed) s
Height of the water in
the column of the
manometer for the first
nA chosen point mol
Concentration of t-Butyl
CA chloride at time = t mol dm-3
𝜌 Density (0.836 gr mL-1) gr mL-1
Molecular weight (92.5
Mr gr mol-1) gr mol-1

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7. REFERENCES
1. Scully, Patricia. School of Chemical Engineering and Analytical Sciences First Year
Practical Work 2015-2016. Manchester: University of Manchester, 2015. Print.
2. "Pseudo-1st-order Reactions - Chemwiki." The Dynamic Chemistry Hypertext. UC
Davis, n.d. Web. 15 Dec. 2015.
3. "The Hydrolysis of Tertiary-Butyl Chloride A Chemical Kinetic Study." The
University of Manchester, Blackboard. Web. 14 Dec.
4. "Experimental Data Analysis for Hydrolysis of t-Butyl Chloride." The University of
Manchester, Blackboard.. Web. 15 Dec.
5. "Rate Constants and the Arrhenius Equation." Chemguide: Helping You to
Understand Chemistry - Main Menu. N.p., n.d. Web. 17 Dec. 2015.
6. Cunningham, Kevin. "Applications of Reaction Rate." J. Chem. Educ 84.3 (2007):
430. Print.
7. "Abstract." UNCW Faculty and Staff Web Pages. N.p., n.d. Web. 16 Dec. 2015.
8. "Taylor Timer." Photograph. Target. N.p., n.d. Web. 16 Dec

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