Physical Chemistry Laboratory Experiment

Belousov-Zhabotinskii Reaction

Letitia Sarah
06130856
Lab partner: Akane Hattori
Experiment period: 6 November 2015 9 November 2015

Day I
Purpose: to recreate Belousov-Zhabotinskii reaction
Procedure
1. Prepare 10% KNO3 (aq.) as salt bridge for the internal solution of the reference
electrode.
2. Fill 100 mL of distilled water in a beaker and stir with magnetic stirrer. Then, add
9 mL of concentrated H2SO4
3.121 g of malonic acid (0.275 M)
1.138 g of KBrO3 (0.0625 M)
0.23912 g of (NH4)2Ce(NO3)6 (0.004 M)
Several drops of 0.025 M ferroin solution ([Fe(Ph) 3]SO4(aq.))
3. Carefully observe changes over time (color, bubble, etc.) of the solution.
4. In order to observe the phenomenon quantitatively, immerse the reference
electrode and platinum electrode in the solution
5. Measure the potential difference simultaneously with the observation work.
6. Graph the potential difference values obtained over time.
Data

Potential difference (mV) vs. time (s) graph of the BZ solution

Three graphs of potential difference vs. time of BZ reaction measured at different

time
Discussion
The first graph above shows the potential difference and time relationship of the BZ
reaction. It can be seen that the graph is consisted of several peaks with relatively
same height and width. Because of this, it can be said that the reaction oscillate. The
reaction oscillates such that the concentrations of some species increase and then
decrease during the time between two limits.
Furthermore, second graph shows three potential difference vs. time graphs which
are taken in different period of time. The potential difference is measured and plotted
in order from Voltage, Voltage 1, and Voltage 2. These three graphs show that
the later the measurement is taken, the longer the oscillation period is. This might be
because as the reaction advances in time, the concentrations of the ions in the
solution get closer to the equilibrium.
Exercises
1. The appropriate term in [1] is The second law of thermodynamics
2. The standard salt bridge employs KCl. Why is KNO 3 selected in this particular case
for the salt bridge?
Platinum can go undergo bulk corrosion when it is negatively polarized (used as
cathode). Some salts used as electrolytes can change the property of cathode from
electrical conductor with electronic conduction to semi-conductor with ionic
conduction. Particularly, filling the salt bridge with KCl solution is not recommended
because chloride ions can adsorp on most metals, causing corrosion.
In addition, chloride ions are halide ions just like bromide ions which participate in
the overall reaction of BZ. If the standard salt bridge uses KCl, Cl - might be
incorporated and reacts with BrO3- and H+. This might alter the result of the reaction.
3. Ferroin solution is a redox indicator. Discuss how it works.
Ferroin compound has chemical formula of [Fe(o-phen) 3]SO4, which o-phen is an
abbreviation for 1,10-phenanthroline, a bidentate ligand. [Fe(o-phen) 3]2+ ion per se,
is a chromophore or part of the molecule responsible for the color observed. In
addition, ferroin compound shows different color when it is reduced and oxidize. This
is the reason it can be used as redox indicator.
Fe[(o-phen)3]2+ Fe[(o-phen)3]3+
Eo = 1.06 V

3.syngenta.com

4. Describe what the measured electromotive force is. Explain.

Redox reaction occurs spontaneously due to the difference in potential energy

between two substances. The difference between the anode and cathode dictates
the direction of electronic movement. This difference which acts as driving force for
the reaction is called the cell potential (or electromotive force). For a spontaneous
reaction, the cell potential is positive and G (Gibbs free energy) is negative.
The relationship between Gibbs free energy and cell potential can be described in
Nernst equation
Go=nFEo
Note: n = number of electron transferred in the reaction
F = Faraday constant
Eo = Eo reduction - Eo oxidation
Also from the measured electromotive force of the solution, we can determine the
oscillating behavior of the solution.
5. What is the relationship between the change in electromotive force and change in
solution color? Explain the cause of these changes.
Ce4+ (yellow)
Eo =
1.70V

Fe3+ (blue)

Eo =
Ce3+
0.77V
(clear)
Fe2+
4+
After the addition of (NH4)2Ce(NO
which is responsible for the yellow solution, is
3)6, Ce
(red)
3+
reduced to Ce by bromide ion. This results in clear solution observed. Then, ferroin
solution is added to the mix which gives pale blue color to the solution in a short
period of time. The blue color of ferroin can only be observed shortly because Fe 3+ is
readily reduced to Fe2+ which has a prominent red color. Due to the relatively low redox
potential between Fe2+ and Fe3 compared to Ce 3+ and Ce4+, the reaction can also
reduce Fe3+ to Fe2+ fast so blue color is hard to be seen.
Moreover, Ce4+ is also completely reduced to Ce 3+ after reduction of the Fe3+ to Fe2+
which gives a clear solution. This clear solution from Ce 3+ is mixed with the red solution
from Fe2+. Thus, the first solution color that we notice after addition of all the reagents
and indicators is pink.

Solution color after addition of (NH 4)2Ce(NO3)6 and ferroin. The color oscillates from
yellow to pink and vice versa.
pale
blue
(Fe3+
)

clear
(Ce 3+ )

yello
w
(Ce 4+ )

pink
(Fe 2+ )

pale
blue
(Fe3+
)

clear
(Ce 3+ )

Cycle of the observed colors on the solutions

Advance Exercise 1
Observation of the reaction over an extended period of time reveals that the change in
solution color ultimately stops. Subsequent mechanical stimulation can restart the
change in colors. Discuss the reason why this may occur.
During the experiment, the solution color turns colorless (clear) after some time and
stays colorless if there is no mechanical stimulation (stopping the stirrer or shaking the
beaker) is done. First, the solution was colorless because there might have been more
Ce3+ in the solution compared to other ions. Also, the solution seems to stop because
the BZ reactions have reached a point where it is close to equilibrium. At equilibrium


Br

. Thus this can be regarded as the point when reaction can switch between
Br O3
k2
path 1 and path 2. However, reaction does not seem to switch between both paths,
instead it just stops because the forward-reverse reaction rates are the same. When
manual stimulation is done, composition of the molecules inside the solution changes
such that there is part of the solution which is more concentrated in BrO 3- or Br-. This
is the reason why reaction can further oscillate after stimulation.

Day 2
Purpose:
to perform calculation and simulation of BZ reaction using Oregonator as the
reaction model
to perform calculation and simulation of Lotka-Volterra reaction mechanism
Procedure
1. Derive the reaction rate law (differential equation) of Belousov-Zhabotinskii (BZ)
reaction
2. Confirm that oscillation actually occurs by mathematically solving the derived
differential equation using Mathematica
3. Compare with experiment results
Experiment: Calculation and Simulation 1
A. For A in the first order reaction (-d[A]/dt = k[A]), determine the concentration [A] at
arbitrary time t when the initial concentration of A is [A]o

d [ A]
=k [ A ]
dt
A

Ao

d [ A]
= k dt
dt

ln [ A ] ln [ Ao ] =kt

ln [ A ] =kt +ln [ Ao]

e ln [ A ]=e ln [ Ao ]kt

[ A ] =[ Ao]ekt
For the reaction AB whose forward reaction and reverse reactions are both first
order, if

A k 1B

B k2 A

And the initial concentration for A and B are [A]o and 0, respectively, determine
concentrations [A] and [B] at arbitrary time t.
At t=0, [A]=[A]o, [B]=0

d[A]
=k 1 [ A ] +k 2 [B]
dt

d[A]
=k 1 [ A ] +k 2( [ Ao ] [ A ] )
dt
[ Ao]
d[A]
=( k 1 +k 2 ) [ A ] +k 2
dt

d[A]
+ ( k 1 +k 2 ) [ A ] =k 2 [ Ao]
dt
Integrating factor:

( t )=e

p ( t ) dt

Multiply the blue equation by

(t)

=e

(t)

d[A]
+ ( t ) ( k 1+ k 2 ) [ A ] = ( t ) k 2 [ Ao]
dt

( [ A ] e(

k 1+k 2 )t

)'=e (

k 1+ k 2) t

k 2 [Ao]

([ A ] e ( k +k ) t ) ' dt = e (k +k ) t k 2 [ Ao]dt
1

( k 1+k 2) t

[A]e

[ A ]=

( k 1+k 2 ) dt

e(

k 1+ k2 ) t

k 2 [ Ao]
+c
k 1 +k 2

[ Ao ]k 2
k +k t
+c e ( )
k 1+ k 2
1

[ Ao]k

2
At t=0 [ Ao ]= k 1 +k 2 +c

( k 1+k 2) t

=e

c= 1

k2
k
[ Ao ] = 1[ Ao ]
k 1 +k 2
k 1 +k 2

k 1 +k 2) t

k 2 +e (
[ A ]=
k 1+ k 2

[ Ao]

[ B ] =[ A o ] [ A ]
Mathematica simulation of the above differential equation

In this simulation, it is assumed that k1=3, k2=2, and [Ao]=1

The simulation graph of the differential equation for reaction AB is reasonable since
the concentration of A must decrease (shown by blue line) to give rise to concentration
of B (brown line). However as the reaction advances, the reaction would reach
equilibrium. In this equilibrium, the concentration of substance does not change and
thus results in plateau region in the plot.
Reaction Mechanism
The main characteristic of BZ reaction can be qualitatively reproduced by these 6
following reactions
Br- +BrO3- +2H+ HBrO2 + HOBr
(rate-determining step)
1
Path
Br- + HBrO2 + H+ 2HOBr
1
BrO3- +HBrO2 +H+ 2BrO2 +H2O
23
Path
BrO2 + Ce3+ + H+ HBrO2 + Ce4+
2
+
2HBrO2 BrO3 + HOBr + H
4
4 Ce4+ +BrCH(COOH)2 + H2O + HOBr 2 Br-+ 4Ce3+ + 3CO2 + 6H+
5
Then, the overall reaction could be written as follows
6
3H+ + 3BrO3- + 5CH2(COOH)2 3BrCH(COOH)2 + 2HCOOH + 4CO2 + 5H2O
At the beginning of the reaction, there is large amount of Br- and little amount of
HBrO2. Because of this condition, Path 1 reactions (1 and 2) are preferred. However,
Path 2 reactions are preferred when concentration of HBrO 2 is increasing. Because

HBrO2 is produced in reaction 1 and at the same time it is consumed in reaction 2, the
concentration of HBrO2 can be considered constant and steady state approximation
can be applied.

+
H
Br O3

[HBr O2 ]=

k1

k2

Moreover, reaction can switch from path 1 to path 2 when concentration of Br- drops
(Br- is consumed on both reaction 1 and 2). The drop of Br- and the abundance of
HBrO2 cause reaction 3 to be preferred because HBrO 2 is readily consumed.

Br O3

Br < k 3
k2

At the very point when reaction is about to switch path from 1 to 2, the critical
concentration of Br- can be described as follows

Br

Br O3

After reaction shifts to path 2, reaction 3 to 6 takes place. The massive generation of
HOBr and Ce4+ in the system leads to regeneration of Br- in reaction 6. The presence of
Br- in great amount triggers the reaction to shift back to path 1. Hence, oscillation
reaction can be observed.
Exercise 6
Derive the formulas (8) and (10). (Read the description above, and understand the
emergence of oscillation through the shifting between Path 1 to Path 2)
Formula 8

d [HBr O2 ]
=0
dt


Br

Br O3

+
H

+
H

d [HBr O2 ]
=k 1
dt

Br

Br O3

+
H

+
H
Br [HBr O2 ]

k1

B r O 3

+
H
[HBr O2 ]=

proven

k2

k1

Formula 10
The critical concentration of Br- when the reaction shifts from path 1 to path 2

Br

Br O3
k2

Br O3
k
Br = 3
k2

Oregonator
The complete mechanism of the BZ reaction was formulated by R. M. Noyes, R. J. Fields
and E. Krs. It counts 18 reactions with 21 different chemical species. Due to its
complexity, a simplified mechanism was proposed by the same authors and named
"Oregonator" in reference to the University of Oregon where they worked in this
period.
The Oregonator mechanism steps are listed below

+ k 1 X + P

11

A +Y +2 H
+ k 2 2 P

12

X +Y + H
+ k 3 2 X +2 Z

A+ X + H
2 X k 4 A+ P

13

+ H

14

Z + B k 5 hY

15

Note: A = Br O3

, B = CH2(COOH)2 + Br CH2(COOH)2, P = HOBr, Y =

Br , and Z =

Ce4+, h shows how much Y is generated for consumption of 1 Ce 4+ ion.

Experiment: Calculation and Simulation 2
1. There are three reaction intermediates of the Oregonator: X, Y, and Z. create reaction
rate equations for the respective intermediates, based on reactions (11) to (15). For
convenience, it is important to make the reaction rate dimensionless.
Let :

x=

X
Xo ,

k HA
Xo= 1
,
k2
Use

s=

d [Z ]
=2 k 3 [ A ][ X ]
dt
dz dZ dz d
=
dt dz d dt

Y
Yo ,

k A
Y o= 3
k2 ,

k3
k1 H ,

+
H

y=

w=

z=

Z
Zo ,

t
t0

2k k H A
Zo= 1 3
k2 k5 B
k5 B

(k

3 2
k3 H A ) ,

q=

, and

t o=

1
(k 1 k 3 H 3 A 2)

2k 1 k 4
k 2 k 3 , and f = 2h = 1

dz
dz 1 z o dz
=z o
=
dt
d t o t o d
+
H

z o dz
=2 k 3 [ A ] [ X ]
t o d
Substitute X =

Xo x

and Z =

Zo z

+ k 5 z Z o B
z o dz
=2 k 3 Ax X o H
t o d
Substitute Xo and Zo
2

z o dz
k HA
2k k H A
=2 k 3 AX 1
k 5 z 1 3
B
t o d
k2
k2 k5 B
z o dz 2 k 1 k 3 H 2 A2
=
(xz)
t o d
k2
2

t
dz 2 k 1 k 3 H A
=
(xz ) o
d
k2
zo
2

k2 k5 B
2 k1 k3 H A
dz
1
=
(xz )
2 2
3
2
d 2 k 1 k 3 H A ( k 1 k 3 H A )
k2
dz
=w(x z)
d
Furthermore, these are the reaction rates for intermediates X and Y (The calculation
steps for dz/d and dy/d would not be shown.)

dx
2
=s ( yxy + xq x )
d
dy 1
= ( yxy + z)
d s

2. Use the reaction rate law determined in 1 above, perform the simulation of the
oscillation reaction, and plot the changes over time for x, y, and z. Use the following
values:

k 1=2 M 3 s1
k 2=3 106 M 2 s1
2 1

k 3 =42 M s

16

k 4=3 103 M 1 s1
k 5 =0.02 s1

Original graph of

dx ( ) dy ( ) dz
,
()
d
d d

X= HBrO2
Y= BrZ= Ce4+

From the graph above, we could observe how concentration of reaction intermediates:
X, Y, and Z changes over time. First, the red graph represents the change of HBrO 2
concentration over time. When the reaction just occurs, the concentration of HBrO 2
increases steeply because of the abundant supply of reagent Br-, BrO 3-, and H+.
Br- +BrO3- +2H+ HBrO2 + HOBr
Br- + HBrO2 + H+ 2HOBr
Furthermore, the abundance of HBrO2 causes reaction to switch from path 1 to path 2,
where HBrO2 is consumed. Because of this, the concentration of HBrO 2 drops
significantly at a certain point. While HBrO 2 concentration decreases, the concentration
of Ce4+ (blue graph) starts to increase. Nevertheless, the slope of graph noting this
Ce4+ concentration is not as steep as that for HBrO 2. This is because in order to
increase Ce4+ concentration, HBrO2 has to undergo two reactions such that it takes
more time to generate BrO2 and to let BrO2 be consumed.
BrO3- +HBrO2 +H+ 2BrO2 +H2O
BrO2 + Ce3+ + H+ HBrO2 + Ce4+
2HBrO2 BrO3- + HOBr + H+
4+
Right after HOBr and Ce are generated, they react with BrCH(COOH) 2 and H2O to
produce Br- and other products. From the graph it can be observed that when
concentration of Ce4+ starts to decrease, the Br- concentration rises (green graph). The

rise of Br- concentration is fairly prominent because only one reaction is needed to
generate Br- hence slight rise of the Ce 4+ and HOBr can give rise to Br- concentration
right away.
4 Ce4+ +BrCH(COOH)2 + H2O + HOBr 2 Br-+ 4Ce3+ + 3CO2 + 6H+
Exercise 7
Differential equations cannot be analytically solved, except for special cases (such as
the Oregonator). Use an example of Eulers method, one of the easiest numerical
analyses, to explain what numerically solving a differential equation means.
The vast majority of first order differential equations cannot be solved. In this case, we
resort to numerical methods that will allow us to approximate solutions to differential
equations. There are many different methods that can be used to approximate
solutions to a differential equation. One of the oldest and easiest methods is called
Eulers Method.
For example:

dy
=f (t , y ) y ( t o )= y o
dt

If ft and fy are continuous function then there would be unique solution to the
differential equation in some interval surrounding t and t o. First, we want to estimate
the solution of

dy
=f ( t , y ) near t = t . Then we can plug the initial condition (t = t ) to
o
o
dt

the differential equation, such that

dy
|t =to =f (t o , y o)
dt

On the other hand, we can also write the equation of the tangent line to the solution at
t = to

y= y o + f (t o , y o)(tt 0 )

If the t1 is close enough to t o then the point y1 on tangent line should be fairly close to
the actual value of the solution at t1 or y(t1).

y 1= y o + f (t o , y o )(t 1t 0)
Now, to get an approximation to the solution at t = t2 we will hope that this new line
will be fairly close to the actual solution at t2 and use the value of the line at t2 as an
approximation to the actual solution. This gives

y 2= y 1 +f (t 1 , y 1)(t 2t 1)

We can continue in this fashion. Use the previously computed approximation to get
the next approximation. So,

y 3= y 2 + f (t 2 , y 2)(t 3t 2)
etc.
Often, we will assume that the step sizes between the points t 0 , t1 , t2 , are of a
uniform size of h.

t n+1t n=h

In summary, we need to follow two steps in order to perform Eulers method

1. Have the differential equations to be solved, starting points, and step size (h)
2. Then starting with (t0, y0) we repeatedly evaluate

y n+1= y n+ f (t n , y n)(t n+1t n )

We continue until we get the desired number of steps or reached the desired time.
This will give us a sequence of numbers y1 , y2 , y3 , yn that will approximate the
value of the actual solution at t1 , t2 , t3 , tn.
Exercise 8
Within the simulated changes over time for x, y, and z where are the corresponding
parts to reaction path 1 and path 2? Keep in mind which chemical species x, y, and z
correspond to, and discuss which aspects the calculations results by this Oregonator
model reproduce and do not reproduce the experimental results, and the related
reasons.
1. X corresponds to concentration of HBrO2
Corresponding reaction to the formation of HBrO 2: Br- +BrO3- +2H+ HBrO2 + HOBr
(path 1) and to the depletion of HBrO 2: BrO3- +HBrO2 +H+ 2BrO2 +H2O (path 2)
2. Y corresponds to concentration of BrCorresponding reaction which leads to depletion of Br- is Br- + HBrO 2 + H+ 2HOBr
(path 1) and to the formation of Br- is 4 Ce 4+ +BrCH(COOH)2 + H2O + HOBr 2 Br-+
4Ce3+ + 3CO2 + 6H+ (path 2)
3. Z corresponds to concentration of Ce4+
Corresponding reaction which leads to formation of Ce 4+ is BrO2 + Ce3+ + H+ HBrO2
+ Ce4+ (path 2) and depletion of Ce 4+ is 4Ce4+ +BrCH(COOH)2 + H2O + HOBr 2 Br-+
4Ce3+ + 3CO2 + 6H+ (path 2)
Because the original model for the numerical analysis for three reaction intermediates
of Oregonator (X,Y, and Z) has been discussed in Calculation and Simulation 2, then
this part would discuss how the reaction responds to some changes during the
simulation.
Original graph of

dx ( ) dy ( ) dz
,
()
d
d d

Increased H+ concentration (from 1.5 M to 5 M)

Increased H+ concentration would result in shifting of the three plots. Because of H +

abundance, reaction 1 and 2 would take longer time to proceed. Then, domino effect
occurs because the late formation of HBrO2 makes other reactions occur later as well
Br- +BrO3- +2H+ HBrO2 + HOBr
(rate-determining step)
Br- + HBrO2 + H+ 2HOBr
Increased A (concentration of BrO3-) value (from 0.0625 M to 0.5 M)

Increase in concentration of BrO3- also shifts the three plots because of the similar
reason as the previous explanation. BrO 3- is one of the reagents needed in reaction 1.
However, the shifts in this simulation are more prominent that the shift noticed when
concentration of H+ is increased. This is because in BrO 3- concentration is increased by
8x in this simulation, while H+ is only increased by 3x in previous simulation.
Increased initial Z value (from 0.004 M to 0.07 M)

It can be noticed that increasing initial Z (Ce 4+) brings no effect to the total reaction. It
is because Ce4+ only acts as redox indicator in this experiment. The presence of cerium
and ferroin indicator is only important for observing the oscillating phenomenon. This
is why increasing Ce4+ indicator does not change the kinetics of the reaction.
Increased initial k5 value (from 0.02

s1

to 0.3

s1

Increasing k5 value brings tremendous change to the plot of three graphs. It could be
seen that it takes around 250 s for 1 oscillation to occur in the original graph, but it
only takes 25 s in this simulation.

Z + B k 5 hY

Note: B = CH2(COOH)2 + Br CH2(COOH)2, Y =

Br , and Z = Ce4+, h shows how much

Y is generated for consumption of 1 Ce4+ ion.

Because the reaction shows above is responsible for generating Br-, then it is an
important step in the reaction. When the reaction rate is increased by 15x, Br- can be
obtained in a really fast time such that the reaction would fast flip back to path 1. This
causes oscillation to happen more frequently given the same period of time.
Increased k1 value (from 2 M-3s-1 to 15 M-3s-1)

Increasing k1 value causes reaction 1 to happen faster. However, looking at the

general trend of the three graphs, the oscillation occurs more slowly than when k1 is 2
M-3s-1. One of the possible explanations is that the fast generation of HBrO 2 makes
other reaction appears slower. In this simulation, more HBrO 2 needs to be converted to
other reaction intermediates. In the case when k1 is the only reaction rate constant
that changes value, imbalance between speed of HBrO 2 generation and consumption
results in longer oscillation time.

Lotka-Volterra Mechanism
Experiment: Calculation and Simulation 3
1. Derive a reaction rate equation for reaction intermediates X and Y for the LotkaVolterra mechanism.
2. Use Mathematica and numerically solve the reaction rate equation derived in 1,
and plot [X] and [Y] over time.
3. Vary the parameter values (k1, k2, k3, A) several ways, and investigate how [X]
and [Y] change over time.
Data
Reaction rate:

d[X]
2
=k 1 [ A ][ X ] + k 1 [ X ] k 2 [ X ][ Y ] =k 1 [ A ][ X ] k 2 [X ][Y ]
dt
d [Y ]
2
=k 2 [ X ] [ Y ] +k 2 [ Y ] k 3 [ Y ] =k 2 [ X ][ Y ] k 3[Y ]
dt

The original graph of the change of concentration of X and Y following the LotkaVolterra Mechanism

From the original graph, it could be seen that the emergence and disappearance of X
and Y are cyclic with a phase shift between them. Red plot represents d[X]/dt and
green plot represents d[Y]/dt.

Increase in A from 2 to 20

Increased in value of A for about 10x would cause the oscillation to occur more
frequently in a certain period of time. In the original graph, there are 1 cycle of
reaction every 4000 s. However, there are 3.5 cycles for every 4000s in this graph.
The observed phenomenon might occur because higher concentration of A would drive
the reaction faster, generating Y in a shorter time.
Increase k1 to 1

In this graph, the value of k1 is increased 1000x its initial value. The great increase of
k1 causes reaction 1 to happen faster and in turn this would generate Y faster. Hence,
one cycle of the reaction takes place in a shorter time.
Increase Xo to 0.11

When the starting concentration of X is increased to 0.11, the overall graphs do not
significantly change. However, it could be observe that one cycle now occurs at
shorter time. In the original graph, it takes about 4000 s to complete one cycle, but it
only takes around 2000 s in this graph. One of the reasons for the observed change is

because higher concentration of X would drive the reaction faster towards equilibrium,
hence one cycle of reaction is also completed faster.
Exercise 9
Qualitatively explain the oscillating mechanism of reaction intermediates for the LotkaVolterra mechanism. Discuss the relationship between the parameters and oscillation
cycle.
The Lotka-Volterra mechanism represents a simpler example of oscillating reaction.
The Lotka-Volterra mechanism is usually used to describe an ecological predator-prey
(or parasite-host) model.

A + X k 12 X

X +Y k 2 2Y

Y k3 B

2
3

Because A is present abundantly, it can be considered constant in concentration. In

addition the generated B does not directly participate in the oscillation reaction.
Hence, the reaction seems to proceed one way and converts A to B, but reaction
intermediates X and Y oscillate in reaction 1-3.

d[X]
2
=k 1 [ A ][ X ] + k 1 [ X ] k 2 [ X ][ Y ] =k 1 [ A ][ X ] k 2 [X ][Y ]
dt

d [Y ]
2
=k 2 [ X ] [ Y ] +k 2 [ Y ] k 3 [ Y ] =k 2 [ X ][ Y ] k 3[Y ]
dt
The concentration of X is affected by its generation at reaction 1. As a reagent, X will
react with A to produce more X. While in turn, Y needs to react with X to produce more
Y which later turns to be B. Due to the production and consumption of X and Y (which
depends on each other), the reaction oscillates.

2.
3.
4.
5.

Day 3
Purpose: to perform experiment regarding space change of BZ reaction
Procedure:
1. Prepare these solutions A-E in each 300 mL beaker
Solution A: 40 mL of distilled water and dissolve 5 g of sodium bromate
Solution B: 40 mL of distilled water and 1 g of sodium bromide
Solution C: 40 mL of distilled water and 1 g of malonic acid
Solution D: 20 mL of distilled water and 6.8 mL of concentrated sulfuric acid, further
diluted to produce
40 mL solution
Solution E: ferroin solution
Add 4 mL of solution A, 2 mL of solution B, 4 mL of solution C, and 2 mL of solution D in
sequence to a
petri dish
Once the solution turns yellow, gently shake the petri dish until yellow color disappears
Add 5 drops of solution E. The solution begins to turn blue. Gently shake the petri dish
to mix the solution and let stand until the entire solution turns blue.
Take photos of the solution.
Exercise 10
Observe carefully the reaction that occurs in the Petri dish. Explain qualitatively about
how the patterns are formed.

1. right after addition of ferroin

minutes

3. 2 minutes after addition

2. 1 minute after ferroin additon 4. 6 minutes

5.

10

Tilted petri dish: solution turns red and then blue

In this experiment, BZ reaction is about to be observed, similar to the experiment
performed in day 1. The differences to day 1 experiment are that we use petri dish
instead of beaker and we do not add (NH 4)2Ce(NO3)6. Petri dish is used for this
experiment because it enables us to observe the space change of BZ reaction.
After addition of solution A, B, and C, solution is colorless. However, it starts to turns
yellow after addition of sulfuric acid. Yellow color appears due to generation of
bromine. After shaking the petri dish, the yellow color disappears and ferroin solution
is added. The addition of ferroin gives a strong orange color to the solution. Because
we put slightly too much ferroin in the solution, it appears as orange blob in the center
of petri dish.
After a few minutes, we observe that the orange blob starts to move from the center to
the outer edge of the petri dish. This is due to diffusion effect between ferroin and the
mix of solution A, B, C, and D. Ferroin solution diffuses from the zone with high
concentration to low concentration. This diffusion effect can be observed on photo 4
and 6 which show that the orange blob is not as big as it used to be. Furthermore it
can also be noticed in photo 4 and 6 that there is blue lining surrounding the orange
blob. This blue lining appears as some of the iron in ferroin get oxidized to Fe 3+ which
exhitibit blue color.
As time passes and some shaking is applied, the solution in petri dish becomes
colorless. Nevertheless, the solution turns red when the petri dish is tilted. This is
because the equilibrium of the reaction is disturbed. Hence, some part of the solution
has more Fe2+ ions (showing red color). When tilted, the solution would oscillate from
red to blue due to oxidation and reduction of Fe ion.
Exercise 11
State your impressions of this student laboratory experiment.
To be honest, I always think Physical Chemistry is hard and this experiment doesnt fail
to make me think like that. Ive never used Mathematica before and it was hard to be
used, but the explanation given was easy to be understood and TA-san was so nice to
write the function one by one.
During first year, I did experiment with BZ reaction but at that time we did not go into
much details so it is interesting to know more about this topic, especially the
oscillating color is to observe. However, as my Japanese is not good , it was
so hard for me to understand this experiment. Fortunately, Akane-san helped me a lot
during the lab. One comment from me: I wish that the English translation of the lab

guide could be improved, because sometimes its hard (at least for me) to understand
the meaning. Also, I notice that there are many references for this experiment, but
most of them are in Japanese (except the research papers). I think it would be nice if
there are more references in English as well, besides the papers.
Overall even though its hard, I enjoyed this lab. Keep up the good work!
Advanced Exercise 2
How can the patterns formed in the Petri dish be qualitatively reproduced in a
simulation?
The simulation of the BZ reaction patterns in Petri dish can be reproduced qualitatively
by incorporating Gaussian function to the Oregonator function. In mathematics, a
Gaussian function is a function of the form:

for arbitrary real constants a, b and c.

The graph of Gaussian peak has shape of a symmetric bell curve. The parameter a is
the height of the curve's peak, b is the position of the center of the peak and c (the
standard deviation) controls the width of the "bell". For this simulation, the
normalization constant a essentially represents how many non-interacting particles
we have in the system.
The plot of change of concentration for Oregonator reaction combined with Gaussian
function give us approximation on how the molecules diffuse in the petri dish. For
example, at early times the peak in the center of the dish is high and as the time
passes. This means particles are localized around the area where they were first
introduced. Later, as the time passes the peak starts to spread out to the surrounding.

Note:. The concentration of the substrate may be thought of as a function of time and
position with a term that considers diffusion originating from differences in
concentration.
Experiment: Calculation and Simulation 4
1. Establish [X], [Y], and [Z] as functions of time and position, consider substance
diffusion to occur at a rate
proportional to the concentration gradient and
develop a differential equation for diffusion.

q x2 + xxy + y + k 6 (

d[X]
=s
d

x 2
)
p

D(x [ t , a ] )
( 2)
2
y [ t , p ] x [ t , p ] y [ t , p ] + x [ t , p ] q ( x [ t , p ] ) + k 6
D [ x ( t , p ) , t ] =s

d [Y ] 1
y 2
= ( yxy + z ) +k 6 ( ) )
d
s
a
D ( y [ t , p ] , p)
k 6 ( 2)

y [ t , p ] x [ t , p ] y [ t , p ] + z [ t , p ] +
1
D [ y ( t , p ) ,t ] =
s

d [Z ]
z 2
=w (xz+ k 6
)
d
a

( )

D ( z [ t , p] , p)
k 6 ( 2)

x [ t , p ] z [ t , p ] +
D [ z ( t , p ) ,t ] =w
2. Solve numerically with Mathematica the simultaneous differential equation consisting
of the previous
reaction rate formula and diffusion equation.

positio
n

tim
e
The two figures below show the simulation model when Gaussian function is
incorporated to the Oregonator reaction. This simulation model can give us the big
picture of how solution diffuses from region with higher concentration value to other
region with lower concentration value and an idea about how the reaction oscillates in
Petri dish.
In this simulation, the 3D simulation is graphed based on the position and time of the
solution in the petri dish. Notice that when time is 0, there is only 1 peak in located in
the middle. Later, this peak would diffuse out to the surrounding giving rise in

concentration for the surrounding regions (marked by orange triangle). After that,
there would be another peak, but this time there are 2 smaller peaks (marked by red
dot) because the previous diffusion has already given the peak concentration to the
surrounding.
Looking at the pictures above, it can be seen that the succeeding peak decreases in
height. In addition, the number of peaks are 1,2,4, etc (multiplication of 2) and lower
peak height is noticed for the region with more number of peaks.

Reference
1. Diffusion of Solid Particles Confined in a Viscous Fluid. Retrieved from
http://www.rpgroup.caltech.edu/courses/aph162/2006/Protocols/diffusion.pdf on 14
November 2015
2. G. Dupuis and N. Berland. Oscillating reactions - Chemical waves. Retrieved from
http://www.faidherbe.org/site/cours/dupuis/oscil.htm on 11 November 2015
3. Richard J. Field, Endre Koros, and Richard M. Noyes. (1972). Oscillations in chemical
systems. II. Thorough analysis of temporal oscillation in the bromate-cerium-malonic
acid system. Journal of the American Chemical Society 1972 94 (25), 8649-8664
DOI: 10.1021/ja00780a001
4. Steven S. Jacobs and Irving R. Epstein. (1976). Effects of chloride ion on oscillations
in the bromate-cerium-malonic acid system. Journal of the American Chemical
Society 1976 98 (7), 1721-1724 DOI: 10.1021/ja00423a015