Kinetics of

hydrogen peroxide
decomposition in a
batch reactor
Aditya Khandelwal (2018CH10190)
Ashish Prasad (2018CH10202)
Deepender Kumar (2018CH10210)
Raghav Ajitsaria (2018CH10936)
 Experimental procedure and
theory

Calculations and Result

Content
Discussion and Key Questions

Possible experimental errors,

improvements and alternate ways
Experiment
• 
Objective: Kinetics of H2O2 decomposition in batch reactor
Reaction Mechanism:
H2O2(aq)+ I−(aq) → H2O(l)+IO−(aq) (slow)
H2O2(aq)+IO−(aq)→H2O(l)+ O2(g)+I−(aq) (fast)
2H2O2(aq)→2H2O(l)+ O2(g) (overall)
The rate law for above reaction is Rate =
Key Experiment:
• Take H2O2 solution with pinch of KI (as catalyst).
• In the experiment we measure the amount of water displaced by the O 2 formed by the reaction in the
apparatus which we used to calculate rate constant of the reaction.
• In order to maintain constant pressure (1 atm) in the system we keep on lowering the outer container
containing water.
• Obtain results with two different methods and compared the results from both:
Differential & Integral
 02 (gas)
The concentration of hydrogen peroxide in
the reaction mixture at any time is given by:

Water Water exiting which is

Water + Bottle replaced by O2 formed

02
formed
Movable platform CA0 = Conc. Of  H2O2 in the initial reaction
Reactor mixture 
(H2O2 + KI) CA = Conc. Of  H2O2 in the
reaction mixture at any time t

Measuring
Cylinder

V∞ = Total volume of O2 prduced at end of

Rate equation
reaction 
Vt = Volume of O2 produced
                               Rate 

Differential method Integral method

• Take log on both sides • Rearrange and integrate on both sides

• Plot ln(-dCA/dt) vs ln CA • Gives: ln(CA0/CA)= kt

• Slope is order of reaction • Plot ln(CA0/CA) vs t

• Intercept gives ln(k) • Slope gives k (order of reaction)


Integral Method
The integral is suitable for
testing specific
mechanisms or simple
rate law or when the data
are so scattered that we
cannot find reliable
derivatives.
The integral method can
only test this or that
mechanism or rate form
Calculation Approach
Differential Method
The differential method is
useful in more
complicated situations but
requires more accurate or
larger amounts of data.
The differential method
can be used to develop or
build up a rate equation
to fit the data.
 Graphs

Analysis from graphs Differential Method Integral Method

By comparing the methods:

1. The differential method

tends to highlight the
uncertainties in the data
2. The integral method
tends to smooth the
data, thereby disguising
the uncertainties in it.
3. In general, it is better
that integral analysis be
tried first, and, if not
successful, that the
differential method be
tried as the method is
simpler and more
accurate
 Results
For 5 mL H2O2
Using differential method  Using integral method 
From
From the
the plot
plot of
of ln(-dC
ln(-dCAA /dt)
/dt) vs
vs ln(C
ln(CAA)) (1)
(1) From
From the
the plot
plot of 
of  ln(C
ln(CA0 /C )) vs t
A0/CA
A vs t
yy == 0.298x
0.298x -- 12.1 
12.1  y =x - 0.394
k == 1/s (rate constant) k = 1/s (rate constant)
n =0.298 (order) n = 1 (order) (∵ =0.921 nearly straight line)
n =0.298 (order)

For 7 mL H2O2
Using differential method  Using integral method 
From the plot of ln(-dCA /dt) vs ln(CA) From the plot of  ln(CA0/CA)) vs t
A A A0 A
y =0.133 x -13  y = x -0.394
k == 1/s (rate constant) k = 1/s (rate constant)
n
n =0.133
=0.133 (order)
(order) n = 1 (order) (∵ =0.89 nearly straight line)
The value obtained from the research paper for pseudo first order reaction is 4.71 1/s that is very close to the
values obtained from integral method.

https://pubs.acs.org/doi/pdf/10.1021/ed073p728
ANALYSIS
In differential method a plot of ln(-dCa/dt) vs ln(Ca) was drawn
Order of reaction = slope of trendline
Rate constant = exp(y-intercept)
For integral method we checked if ln(Cao/Ca) vs time is a straight line

We know that the decomposition reaction of H2O2 is

first order with respect to H2O2 
=> dCa/dt = kCa
Hence, we can observe that ln(dCa/dt) = ln(k) + ln(Ca)
So, varying concentration of H2O2 should not affect the
value of k much.
As we vary H2O2 from 5 mL to 7 mL, integral method
shows value of k as 0.0006 and 0.0008 which are close,
but the variation shown by differential method is quite
large (0.00045 to 0.682)
Integral method is better and can be used for any
duration of the reaction, whereas differential method is
used in conjunction with the initial or intermediate rate
method.
ANALYSIS
Analysis of Differential Rate Method
We saw that differential rate method does give a lot of error when used for
the entire time domain. It is also clearly visible from the graph plotted which
shows a very unexpected oscillatory behavior.

Sensitivity 
Mixing and stability

Although initial rate method is a much better way of evaluation when

using differential rate method (owing to greatest sensitivity), but it does not
let enough time for the reaction to develop and hence we instead use an
intermediate rate method to evaluate the slope and intercept and see it's
coherence with our results from integral method.

The blue points show intermediate points starting with t=57.

Possible Experimental Errors
• Water level should be kept same which if not done will cause pressure
variation
• Oxygen leaking through rubber tube or valves
• Oxygen might dissolve in water
• Exposing hydrogen peroxide to UV/Sunlight and tap water
• Pinch amount of KI was added, not a standard unit
• Parallax and human error while closing stop cock
Ways to improve & Alternative methods

Exothermic reaction, so Use pressure sensor or Monitor the We can use nitrates
choose a reaction vessel glass gas syringe to concentration of H2O2 instead of iodide (better
with good heat transfer calculate the amount of by titration reaction* catalyst for
or add some mechanism O2 generated (only if using other decomposition of H2O2)#
to stir catalyst)

*: Take sample, react with acidified KI, measure Iodine by titration with thiosulphate using starch indicator
#: Source ("Decomposition of Hydrogen Peroxide Experiment." UKEssays. ukessays.com, November 2018.)
 Using distilled water as Spectroscopy can be Add KI solution (at the
impurities in tap water utilised instead of gas same temperature)
lead to side reactions and volumetric instead of a pinch of KI
alter the rate measurements powder.
Thank you