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Mata Kuliah : Kinetika Kimia

Kode/sks : MAK3211/3

WEEK 2
Pseudo order reactions
Measurement of reaction rate

Dr.Muhdarina,M.Si
Lab.Riset Sains Material, Jurusan Kimia FMIPA UR
Email: muhdarina.m@lecturer.unri.ac.id
Pseudo order

• For hydrolysis of sucrose,


C12H22O11 + H2O C6H12O6 + C6H12O6

We know:
R = k [C12H22O11]
However, since the solvent H2O participates in
the reaction, the rate law is:
R = k’ [C12H22O11]w [H2O] v
Pseudo order
Because H2O is always present in great excess,
its concentration remains nearly constant,
therefore [H2O] v is essentially constant and the
rate law is apparently
R = k [C12H22O11] where k = k’ [H2O] v

This reaction is said to be pseudo first order…


(kinetic data indicate v ≈ 6, this explained by
reaction mechanism that involved a hexahydrate
of sucrose)
Example
• An example of a reaction governed by this rate
law is given in
NH4+ + NO2- N2(g) + 2H2O

NH4+ NO2- N2 2H2O


initial 0.002 0.10 0
change -0.002 -0.002 0.002
final 0 0.098 0.002

NO2- >> NH4+


• A simpler approach, a kinetics run is performed
on a solution that initially contains a substantial
excess of one of the reactants, say B. If the
initial concentration of B is more than 10
times larger than the initial concentration
of A, the concentration of B will be nearly the
same at the end of the reaction as at the
beginning; consequently it may be considered to
be constant during reaction.
• Thus the concentration of NO2- remains essentially
constant while NH4+ is consumed, and the rate law
simplifies as shown:

d[N2]/dt = k[NH4+][NO2-] = k'[NH4+]

k [NO2-] = k'

• This simplified rate law, which may be integrated or


subjected to finite difference analysis, is called a
pseudo-first order rate law. The prefix, pseudo-,
reminds us that the reaction is not truly first-
order, but has only been made to appear that way
by imposition of a large concentration of NO2-.
Worked Problem 1
Question. Show that the following fits the condition above.
Initially: [B] = 0.150 mol dm-3, [A] = 1.0 10-4 mol dm-3
Hint. consider concentrations at 90 per cent reaction.
Answer.
Let 90 per cent of A have reacted:
90/100 x 1.0 10-4 mol dm-3 = 0.9 x 10-4 mol dm-3,
leaving [A] at time t = 0.1 x 10 -4 mol dm3.
At time t,
[B] has dropped by 0.9 x 10-4 mol dm-3,
leaving [B] at time t = 1499.1 x 10-4 mol dm-3
0.150 mol dm -3 .
͌
Most of the reaction [B] has remained effectively constant.
Worked Problem 2
Question. The acid-catalysed hydrolysis of an ester is first
order in both H3O+ and ester. In an experiment [H3O+] is
kept in constant excess at 0.0100 mol dm -3, and a first order
k’ = 5.0 x 10-5 s -1 is found. Calculate the true second order
rate constant.
Answer.
R = k [ester] [H3O+] = k’ [ester]
where
k’ = k [H3O+]
and k’ is the pseudo-first order rate constant
k = k’/[H3O+] = 5.0 x10-5 s-1 / 0.0100 mol dm-3
= 5.0 x 10-3 mol-1 dm-3 s-1
Home work: (collect the answer on the next week)
Question. The rate of reaction between A and B depends
on the concentrations of both A and B. In one experiment
the following data were collected when the initial
concentrations were: [A] = 8x10-4 mol dm -3,
[B] = 0.1 mol dm-3
Find the order with respect to A, and the pseudo-rate
constant k’. In a further series of experiments, with B still in
large excess, the pseudo-rate constant k’ varied with the
concentration of B as

Find the order of the reaction with respect to B, and


hence the overall order and the true rate constant.
Measurement of reaction rate
Its follow the concentration of a reactant or product
as a function of time
• Chemical method, one places several reaction
vessels with identical initial compositions in a
constant-temperature bath, slows down or stops
reaction (cooling the sample, removing a catalyst,
greatly diluting the reaction mixture, or adding a
species that quickly combines with one of reactant),
and rapidly analyzes the mixture chemically (mass
spectrometer, gas chromatograph, etc)
Measurement of reaction rate
• Physical method, one measures a physical
property of the reacting system as a function of
time. This allows the reaction to be followed
continuously as it proceeds. For a gas-phase
reaction, change in gas pressure can be followed. In
a liquid-phase that occurs with a measurable
volume change, V can be followed by running the
reaction in a dilatometer. Ionic reactions in solution
by measuring the electrical conductivity
Measurement of reaction rate

• Static method, reactants are mixed and kept in a


closed vessel
• Flow method, reactants continuously flow into the
reaction vessel and product continuously flow out
(used in industrial chemical production). Rate law
and rate constant can be found by measuring the
outlet concentration for several different inlet
concentration and flow rate.
Spectroscopic Techniques
• There are three important features of spectra which
are of prime interest to the kineticist.
1.The frequency and the fine structure of the lines give
the identity of the molecule; this is particularly
important in detecting intermediates and minor
products.
2.The intensity of the lines gives the concentration;
this is useful for monitoring the concentrations of
reactants and intermediates with time.
3.The line width enables kinetic features of the
transition and the excited state to be determined.
Spectroscopic Techniques
• Identification of species present during a
reaction; microwave, infrared, Raman, visible
and UV spectra are all used extensively for
identification. In the gas phase these show sharp
lines so that identification is easy. In solution,
the complexity of the spectra gives them
sufficient features to make them recognizably
specific to the molecule in question.
Spectroscopic Techniques
• Concentration determination;
Using Beer’s law, concentrations can be found
from the change in intensity of the radiation
passed through the sample. The absorbance, A,
of the sample at a given wavelength is defined as

A = log10 Io/I

where Io is the incident intensity and I the final


intensity.
Spectroscopic Techniques
• Concentration determination;
Beer’s law relates this absorbance to the
concentration of the species being monitored:

A λ = ε λ cd
where ε λ is the absorption coefficient for the
molecule in question. ε λ depends on the
wavelength and the identity of the molecule,
λ is the wavelength, d is the path-length and c is
the concentration of the absorbing species.
Spectroscopic Techniques
• Special features of absorbance measurements;

If the reaction being monitored is first order, i.e. has


rate
(R) ≈ [reactant]1,
or is being studied under pseudo-first order
conditions, the absorbance can be used directly,
eliminating the need to know the value of ε λ. The
reactions can be quantified by plotting log[reactant]
vs time.
Spectroscopic Techniques
• Special features of absorbance measurements;

Since absorbance ≈ [reactant], then log absorbance,


A can be plotted directly vs time without the need to
convert absorbance to concentration using Beer’s
law
A = ε cd c = A/εd

log c = log A/εd = log A – log εd


Spectroscopic Techniques
• Special features of absorbance measurements;
Since εd is a constant in any given experiment, then
log εd is also a constant, and

log c = log A – constant

For (R) ≈ [reactant]1

log[reactant] vs time ≡ log absorbance vs time


Spectroscopic Techniques
Spectroscopic Techniques
• A plot of log A versus time differs from a plot of
log c versus time only in so far as it is displaced
up the y-axis by an amount equal to log εd.
• The slope of the graph of log A versus time is the
same as the slope of the graph of log[c] versus
time. The slope of this latter graph gives the
quantity which characterizes the reaction.