Physical Organic 1 Post-Lab Report

Hammett Plots for Nitrophenyl Benzoate Hydrolysis

Name: Sam Daly Group: Y1 Date: 09/03/18

Introduction
In this experiment multiple p-nitrophenyl benzoate esters were synthesised with different
substituent groups attached. They were then hydrolysed with sodium hydroxide and the rate
of hydrolysis was observed using UV-Vis spectroscopy. The synthesis of our compound in
particular is shown below:

Figure 1: Synthetic route to create the m-methyl-p-nitrophenyl benzoate ester.

This synthesis yielded 25% of the desired benzoate ester:

0.160
Yield = × 100 = 25 %
0.646
The melting point was determined to be 71.0 - 72.5C, which is close to 75C quoted by
literature suggesting good purity [1].

Practical
The ester was kept at fixed concentration (4 × 10-5 mol dm-3) and hydrolysed with excess
NaOH at various concentrations. The decompositions were followed using UV-Vis absorption
spectroscopy at a fixed wavelength (405 nm) as the reaction proceeded as the nitrophenolate
anion formed is a good UV absorber. The data from the hydrolysis are presented in tables 1,
2 and 3 on the next page.

[1] Borsche; Berkhout. Justus; Liebigs. Annalen der Chemie. 1904. vol. 330, p. 101

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 Table 1: Kinetic data for reaction Table 2: Kinetic data for reaction Table 3: Kinetic data for reaction
of the p-nitrophenyl benzoate of the p-nitrophenyl benzoate of the p-nitrophenyl benzoate
ester with 0.0050 M NaOH. ester with 0.0083 M NaOH. ester with 0.0133 M NaOH.

Absorbance Time / s Absorbance Time / s Absorbance Time / s

0.004 0 0.040 0 0.124 0
0.097 15 0.171 15 0.300 15
0.176 30 0.282 30 0.447 30
0.246 45 0.380 45 0.563 45
0.309 60 0.464 60 0.658 60
0.366 75 0.535 75 0.735 75
0.418 90 0.600 90 0.798 90
0.466 105 0.656 105 0.851 105
0.510 120 0.707 120 0.893 120
0.550 135 0.750 135 0.929 135
0.587 150 0.785 150 0.958 150
0.623 165 0.817 165 0.984 165
0.653 180 0.849 180 1.000 180
0.682 195 0.875 195 1.020 195
0.712 210 0.896 210 1.030 210
0.735 225 0.920 225 1.050 225
0.753 240 0.936 240 1.060 240
0.776 255 0.951 255 1.070 255
0.795 270 0.964 270 1.070 270
0.815 285 0.977 285 1.070 285
0.829 300 0.990 300 1.080 300

From this data graphs of absorbance vs. time could be plotted, see figures 2, 3 and 4, which
can be used to calculate the rate constant of reaction.

0.9
0.8
0.7
0.6
Absorbance

0.5
0.4
0.3
0.2
0.1
0
0 50 100 150 200 250 300
Time / s
Figure 2: The absorbance over time for the hydrolysis of the benzoate ester with NaOH at
0.0050 mol dm-3.

2
 1.1
1
0.9
0.8
0.7
Absorbance

0.6
0.5
0.4
0.3
0.2
0.1
0
0 50 100 150 200 250 300
Time / s
Figure 3: The absorbance over time for the hydrolysis of the benzoate ester with NaOH at
0.0083 mol dm-3.

1.2
1.1
1
0.9
0.8
Absorbance

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0 50 100 150 200 250 300
Time / s
Figure 4: The absorbance over time for the hydrolysis of the benzoate ester with NaOH at
0.0133 mol dm-3.

Analysis
The hydrolysis monitored is a pseudo first order as [OH-] is in excess and it hardly changes;
hence the pseudo first order rate constant can be determined by conducting a non-linear
regression using the equation for a pseudo first order reaction:
At = b - ce-kt (equation 1.1)

Where At is absorbance at a given time t, b and c are constants and k is the pseudo first order
rate constant. This allowed the value to be calculated at different concentrations of NaOH.
Thus, using equation 1.2 (where the pseudo first order rate constant is denoted k obs):
kobs = k[OH- ] (equation 1.2)
A plot of kobs v. [OH]- therefore will yield a gradient of k, the second order rate constant. See
figure 5 below.

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 0.018

0.016

0.014
kobs / s-1
0.012

0.01

0.008
y = 0.861x + 0.002
0.006 R² = 1.000

0.004
0.004 0.006 0.008 0.01 0.012 0.014 0.016 0.018
[OH-] / moldm-3

Figure 5: The relationship between kobs (the pseudo first order rate constant) and [OH-] for
the hydrolysis of the m-methyl-p-nitrophenyl benzoate ester.

Hence using a linear regression yielded a gradient, and therefore a value for k, of 0.861 dm3
mol-1 s-1. Thus, using error analysis:
k = (0.861 ± 0.003) dm3 mol-1 s-1
Data was collected as a whole group for the various substituted benzoate esters, table 4.

Table 4: Group data of the second order rate constant for the benzoate esters with
different substituents.

Variable Second order rate constant

 value
R X / dm3 mol-1 s-1
H (1.30 ± 0.03) 0
p-Me -0.17
H p-CF3 (17.8 ± 0.7) 0.54
m-MeO (1.5 ± 0.3) 0.11
p-Cl (2.35 ± 0.03) 0.22
H (0.861 ± 0.003) 0
p-Me (0.6 ± 0.2) -0.17
Me m-CF3 (5.1 ± 0.8) 0.43
m-MeO (1.6 ± 0.4) 0.11
p-Cl (2.04 ± 0.05) 0.22

From this group data a Hammett plot was able to be constructed using  values found in the
data book.

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 𝑘𝑋
log ( ) = 𝜌 ∙ 𝜎 (equation 1.3)
𝑘𝐻
It is clear to see the linear relationship between this inductive effect of the substituent in the
ring and the rate of reaction with respect to the non-substituted p-nitrophenyl benzoate
ester. In both cases the y-intercept is effectively equal to 1 which satisfied the Hammett
equation, equation 1.3.

1.4
1.2
1
0.8
0.6
log(kx/kH)

0.4
y = 2.1257x - 0.0872
0.2 R² = 0.9733
0
-0.2 -0.1 0 0.1 0.2 0.3 0.4 0.5 0.6
-0.2
-0.4
-0.6
σ

Figure 6: Hammett plot for the hydrolysis of p-nitrophenyl benzoate esters.

From figure 6 above it can be deduced that ρ = (2.1 ± 0.2).

0.8

0.6
log(kx/kH)

0.4

0.2 y = 1.5738x + 0.0684

R² = 0.9801
0
-0.2 -0.1 0 0.1 0.2 0.3 0.4 0.5
-0.2

-0.4
σ

Figure 7: Hammett plot for the hydrolysis of m-methyl-p-nitrophenyl benzoate esters.

From the Hammett plot in figure 7 above it is possible to deduce that ρ = (1.57 ± 0.12).

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Discussion
A large positive rho value is associated with a large build-up of negative charge (or reduction
of positive charge) in the RDS. Hence out of the proposed mechanisms the one which
corroborates best with experimental data is the first, shown below.

Figure 8: Proposed mechanism for the hydrolysis of phenyl benzoate esters (scheme from script - VC).

Here the incoming nucleophile gives rise to a large build-up of negative charge at the reaction
centre which does not happen in the second proposed mechanism and charge neutrality
takes hold as the incoming nucleophile is neutral.
Furthermore, this mechanism is compatible with the overall order of reaction as the reaction
is second order meaning two species are involved in the elementary RDS. Hence, the rate
equation is:
rate = k [Ester][OH- ] (equation 1.4)

The other proposed mechanism is first order as the ester dissociates by itself, and hence
doesn’t fit with the second order kinetic observed here.
+ and - are used when the substituent is capable of mesomeric effects and delocalises it’s
electron density into the aromatic ring as the Hammett equation can only deal with one
effect (i.e. inductive). These altered values of  account for direct conjugation, and as there
are no cases of direct conjugation with the substituent here, they are not needed.

x O

X HO O NO2

Figure 9: There is no conjugation from the reaction centre to the substituent so there is no need for + or -.

From the Hammett plot it is clear that the p-nitrophenyl benzoate ester undergoes
hydrolysis much faster than m-methyl-p-nitrophenyl benzoate. This makes sense when
considering the steric hindrance caused by the methyl group on the ring which could hinder

6
the approach of the OH- ion, which helps prove that the mechanism is the one proposed in
figure 8.