Chemistry Internal Assessment HL

Research question
How does increasing the concentration of ZnO nanoparticle photocatalyst(0.1, 0.5, 1, 2, 4) g/L affect the
rate of photodegradation(M/min) of methyl orange in the presence of UVA light(365nm) by measuring
the absorbance(470nm) value of the methyl orange solution over time(every 15 minutes for 45 minutes)?

Introduction

As a person who has always been concerned with pollution and climate change which are increasingly
impacting our lives, water pollution has always struck me as a severe issue deserving the most of our
attention. Not only does it harm the ecosystem and the environment and has great implications, but it also
affects us and our health directly. Among the many pollutants, dyes have one of the greatest share in
contributing to water pollution. Used across numerous industrious sectors, such as the textile industry,
dyes have a complex molecular structure which makes them hard to degrade. Hence, much of the dyes
used in industries are released into the environment as waste water, which is especially alarming given the
threat it poses to peoples’ health. To grapple with this problem, scientists have proposed
photodegradation, which uses specific nanoparticles as photocatalysts and UV light radiation, as a safe
and environmentally friendly solution. However, nanoparticles are relatively new materials that haven’t
been in use for long, which makes their production a complex process and their commercial price fairly
high. Therefore, finding the optimum amount of catalyst(nanoparticle) load which gives the maximum
degradation rate at a minimal price is essential. Thus, this IA aims to investigate the following question:

How does increasing the concentration of ZnO nanoparticle photocatalyst(0.1, 0.5, 1, 2, 4) g/L affect the
rate of photodegradation(M/min) of methyl orange in the presence of UVA light(365nm) by measuring
the absorbance(470nm) value of the methyl orange solution over time(every 15 minutes for 45 minutes)?

Out of the many photocatalysts, I settled on ZnO nanoparticles because of its high efficiency and
widespread use in the industries as well as being easily accessible. Moreover, its main rival, titanium
dioxide nanoparticles have been reported to cause irritation, which apparently gives an edge to ZnO over
TiO2. The dye that would be degraded also had to be singled out. Since the dyes most widely in use are
azo dyes, which are synthetic dyes used commonly in textile industries, methyl orange, an azo dye and
also available in the lab, was chosen.

Background information

Methyl orange is a well known dye as well as a PH indicator with the molecular formula: C14H14N3NaO3S

Zinc oxide nanoparticle

A typical zinc oxide is a white powder, with an average size of 0.1 micrometer, and is insoluble in water,
and because of its fairly large size and hence low surface area relative to the size, it cannot function as a
photocatalyst. On the other hand, zinc oxide nanoparticles have a diameter of less than 100 nm, giving
them a high surface area relative to volume ratio, and thus greater efficiency during photodegradation.
This is what makes many nanoparticles useful during
photodegradation and gives them their unique properties.

Zinc oxide nanoparticles are known to absorb UV light(high energy),

due to their high energy gap of 3.37 eV. Energy gap is the difference in
energy between the valence band, a band which is occupied by the
electrons when the atom is in its most natural state, and conduction
band, a band where electrons are delocalized and are free to move
around.

When exposed to UV light, or any light with energy greater than or

equal to the energy gap, the electrons at the valence band become excited and are promoted to the
conduction band, making the valence band, which has lost many of its electrons, less negative and thus
leading to the formation of an imaginary positive electron
hole, while the conduction band, which has gained electrons,
becomes negatively charged.

This can also be expressed through the reaction formula

− +
𝑍𝑛𝑂 + ℎ𝑣 → 𝑍𝑛𝑂(𝑒𝑐𝑏 + ℎ𝑣𝑏 )
(Where hvb + is the electron hole, and ecb - are the excited
electrons, now in the conduction band. )

The positive holes and the excited electrons now move to the
ZnO’s surface, and proceed on to start several redox reactions. This is shown in diagram 3.

The positive holes created are strong oxidizing agents, and hence they start both direct and indirect
oxidation of the dye(pollutant). In direct oxidation, the positive holes themselves directly oxidize the
pollutants. In the indirect oxidation reaction, the positive hole reacts with water and hydroxyl ion, which
leads to the production of an unstable and reactive hydroxyl free radical, which then through a long chain
reaction, oxidizes the dye.

The presence of the positive holes and the excited electrons could possibly lead to a recombination
− +
𝑍𝑛𝑂(𝑒𝑐𝑏 + ℎ𝑣𝑏 ) → 𝑍𝑛𝑂 , but this is swiftly prevented by other electron acceptors such as oxygen,
which combine with the excited electrons to form more free radicals.

Eventually the reactive hydroxyl free radicals, through a long series of chemical reactions, decompose the
dye into non harmful compounds such as CO2 and water.

Adsorption
For the reaction to be as efficient as possible, adsorption of the photocatalyst is a crucial factor.
Adsorption is the adhesion between atoms, ions, and other molecules, and in this case is the adhesion, or
attraction, between methyl orange(dye), and the zinc oxide nanoparticles. More adhesion means greater
the attraction between zinc oxide nanoparticles and methyl orange, which means that it would be easier
for the positive holes of the zinc oxide to oxidize the methyl orange particles. Hence, greater adsorption
implies greater degradation of the pollutants.

Beer-lambert law

Beer-lambert law is a formula outlining the relationship between the absorbance(Measured by a

colourimeter) and concentration of a solution with a formula

A = εlc
(A = absorbance, ε = Absorbance coefficient, l = length of the cuvette, c = concentration)

Here, absorbance coefficient is a unique value which depends on the type of solution, and the wavelength
of light the colorimeter transmits through the sample. For this experiment, the value would be 25100 M -1
cm -1, where the wavelength of light is set at 470 nm, where the methyl orange solution gives maximum
absorbance.

Aim and hypothesis

The ultimate aim of this IA is to find the optimum photocatalyst load that would yield the highest
degradation percentage as well as rate of reaction. It is hypothesized that the rate of reaction and
degradation percentage would initially increase with increasing photocatalyst dosage, but gradually the
amount of increase would get smaller and smaller until barely any increase is seen. I believe so since
although higher catalyst concentration means more active sites for photodegradation, increased
concentration inhibits the penetration of UVA light, reducing the amount of light hitting the zinc oxide
particles and hence slowing down photodegradation.

Variables
Independent variable The concentration of the photocatalyst in the
solution. The concentration of the photocatalyst
was altered by adjusting the mass of zinc
oxide(nps) added to a 200ml solution, with the
concentration being: 0.1g/L, 0.5g/L, 1g/L, 2g/L,
4g/L

Dependent variable The rate of degradation was found by extracting a

sample of solution every 15 minutes and
measuring its absorbance using the colorimeter.
The beer-lambert law was then used to find the
concentration of methyl orange, and these values
were plotted against a time/ concentration graph
and the gradient, the rate of photodegradation, was
found.
 List of controlled variables Method of control Significance of control

Temperature Experiments were conducted at Constant temperature ensures

room temperature(around 25 oC) that the experiment is carried out
and this was controlled using air in the same condition(since
conditioning and the temperature affects the rate of
temperature controlling function reaction).
of the magnetic stirrer.

Distance between lightbulb and The distance(10cm) between the This ensures that the methyl
solution light bulb and the center of the orange solution is exposed to the
beaker which holds the solution. same intensity of ultraviolet
light emitted by the lamp.

The length of time the solution By placing the solution in the The extent of adsorption can
is stirred in the dark dark and stirring it(using a affect the degree of
magnetic stirrer) for 30 minutes photodegradation as mentioned
by using a stopwatch on the before. Greater adsorption
phone. means greater attraction between
zinc oxide and methyl orange, or
faster degradation of methyl
orange by the positive holes in
zinc oxide nps.

External light intensity Solutions were placed in a box, It should be noted that sunlight
not letting any external light in its ray contains UV light
come in. which can be absorbed by ZnO
for degradation. Thus, the
solution should be isolated with
minimal exposure to external
light.

Methyl orange concentration The concentration of methyl Higher concentration of methyl

orange was kept the same by orange would mean more
diluting the exact same volume frequent collisions/adhesions
of methyl orange into 200 ml of between the ZnO, which would
water. raise the rate of reaction.

Material and Apparatus

ZnO (nps 40 - 60 nm) Box

Colorimeter Beaker(250ml)
 Magnetic stirrer UV light lamp(370 - 420 nm) (15W)

Magnetic stirring rod Measuring cylinder (50ml)

Gas syringe Syringe filter (0.22 micrometer)

Methyl orange Distilled water

Stopwatch(Phone) Cuvette (1cm width)

Weighing boat Balance

Procedure:

Prior preparation
1. Prepare a slightly diluted solution of methyl orange by adding 0.015g of pure methyl orange into
200 ml of water. This gives a pure methyl orange solution of 2.3 * 10-4 M. Repeat this twice, and
store them in a glass bottle.
2. At the same time, get a large-sized shoe box where the beaker would be placed. Using a knife, cut
out one side of the shoe box out into a circular shape, with the diameter of this circular hole being
the same as that of the UV lamp(11.5cm)

Experiment
1. Dilute 14 ml of 2.3 * 10-4 M of methyl orange, which was prepared before into 200 ml of distilled
water in a beaker. This would give a methyl orange solution of 1.6 * 10-5 M.
2. After the solution is fully mixed, add ZnO Nps powder accordingly(from 0.02, 0.1, 0.2, 0.4, 0.8)g
to adjust the catalyst concentration(0.1, 0.5, 1, 2, 4)g/L.
3. Then, put a magnetic stirring rod inside the beaker and place the beaker inside a box. The stirring
was set to level 3 all the time.
4. Place the box on a magnetic stirrer and leave it in the dark for 30 minutes, such that there is some
time for adsorption between methyl orange and ZnO to take place.
5. Once this is done, switch the UV lamp on, fix it in the circular hole of the box drilled before, and
fix it at a distance 10 cm from the center of the beaker. This is done to minimize the amount of
external light reaching the solution.
6. Extract a 4 ml sample of the stirred solution with a syringe, and filter it using a 0.22 μm syringe
filter, and measure its absorbance by using a colorimeter. The wavelength should be set at 470
nm, as this is the range where the absorbance value of methyl orange is at its peak.
7. Now, every 15 minutes until 45 minutes have passed, extract the same amount of sample using a
syringe, filter it, and measure the absorbance by using a colorimeter.
8. Repeat steps 1 - 7 thrice for each catalyst concentration values
9. Repeat steps 1 - 8, changing the catalyst concentration each time(from 0.1, 0.5, 1, 2, 4)g/L.
Safety, environment and ethical considerations

Risk Reason Solution

Zinc oxide Zinc oxide can cause skin Protective goggles were worn,
irritation. and gloves were worn.

UV light UV light can prove to be Protective goggles had been

harmful for our eyes. worn throughout the experiment.

Methyl orange Methyl oranges can cause skin Gloves were worn so as not to
irritation. touch the methyl orange directly
with the hands.

Ethical & environmental considerations

Since the methyl orange dye solution can cause pollution and damage the environment, the remaining
solutions after the experiments have been SAFELY disposed of in accordance with the existing guidelines
at school.

Raw Data
Qualitative data

Right to left(0 min -> 75 min)

Throughout the course of the experiment, it could be observed through naked eyes that the color of the
solution was gradually dimming, from a strong yellow to a fainter one. The color change initially was not
as easily discernible, but the change in color became more marked by the end of the experiment.

Data processing

Beer lambert law

To calculate both the rate of photodegradation, the concentration of the solution, and how it changes over
time should be found, and this can be done by using beer lambert’s law, given by the formula:

A = εlc
(A = absorbance, ε = Absorbance coefficient, l = length of the cuvette, c = concentration)

For this experiment, the length of the cuvette was 1cm and it was measured using a ruler. The absorbance
coefficient of methyl orange at 470 nm(the colorimeter was set at 470 nm, since methyl orange has the
highest absorbance in this range) is approximately 25100 M -1 cm -1. Source

The below would show example calculations of the concentration.

Firstly, since each experiment was for three times, and there hence are three absorbance values, the
average of these values should be found.

For example, for 0.1g/L catalyst concentration at 0 minutes,

0.43 + 0.42 + 0.42
Average absorbance = 3
= 0. 423

The average absorbance value can now be put into the beer lambert law.

0.423 = 25100 * 1 *C

C = 0.423/ (25100 * 1) = 1.70 * 10-5 mol dm-3

This procedure was done and repeated for all time intervals as well for all different concentrations of zinc
oxide photocatalyst.

Rate of degradation

As seen above, this table shows the concentration of methyl orange over time from 0 minute to 45
minutes. Plotting these values gives the graph below.

𝐶ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛
Because the graph is concentration against time graph, the gradient, which is 𝑡𝑖𝑚𝑒
is
essentially the rate of degradation = 0.000086 mM min -1.

In the graph above, the high R2 value of 0.9757 is a testament to the clear linear relationship between the
concentration of methyl orange and flowing time. Although a strong linear relationship is shown, after
some time passes(1 ½ hour), the linear relationship will no longer hold as the rate will slow down. In the
data shown above, there does not seem to be any anomaly in any form.

Discussion of uncertainty

Uncertainty in catalyst concentration

To find the uncertainty in catalyst concentration, uncertainty in the mass of zinc oxide used and the
uncertainty in the amount of water should be determined.

The balance used to measure the mass had 0.01g as its smallest scale division, meaning that the balance
has ±0.01 as its absolute uncertainty. For instance, when making a solution with 0.5g L-1 zinc oxide
solution, 0.10g of zinc oxide had been diluted into 200 ml of water.

Hence in this case, %uncertaintymass of ZnO catalyst = 0.01/0.1 = 10%.

Now, the uncertainty in the amount of water should be found. The measuring cylinder used had ±xL as its
absolute uncertainty with 50 ml volume. To fill up the beaker up to 200ml, the measuring cylinder with
approximately 50 ml of water had been used 4 times.

Since the cylinder was used 4 times, the absolute uncertainty should be added up as well, resulting in
absolute uncertainty ±4x.

%uncertaintyamount of volume = 4x/0.2 = ±20x %.

Formula for the concentration of zinc oxide solution = (mass of zinc oxide)/(amount of water), so we
would have to add the %uncertaintymass of zinc oxide catalyst and %uncertaintyamount of volume.
Thus %uncertaintyconcentration of catalyst = 10 + 20x.

The same steps were repeated with different masses of zinc oxide(from 0.02g, 0.1g, 0.2g, 0.4g, 0.8g) with
values in the data table in the processed data section. .

Uncertainty in the rate of degradation

Error in time

Firstly, there is the much simpler uncertainty in time. The stopwatch used for the experiment had +/- 1
second as its lowest division, so +- 1 second must be the absolute uncertainty in this case. Thus the
percentage uncertainty of time at 15 minutes, for instance is
percentage uncertainty in time = 1/ (15 *60) * 100 = 0.1% (1 sig fig)

Repeating this for all time intervals gives the graph below
Error in concentration of methyl orange(for every time)

Now comes the more complicated part of calculating the uncertainty in concentration value as it involves
consideration of different factors. The uncertainty of the concentration of methyl orange with catalyst
concentration of 0.1g/L at time = 0 min would be found.

Firstly the uncertainty in the absorbance values must be considered. A digital colorimeter has been used,
with +-0.01 as its lowest division, which means that +-0.01 is the uncertainty of the absorbance value.
Each experiment was repeated thrice, which means that for each concentration, the average in the
uncertainty of concentration for each three trials should be found.

For instance, for concentration of methyl orange with catalyst concentration 0.1g/L at 0 minutes.

%uncertaintyTrial 1 = 0.01/0.43 * 100 = 2.33% (3 sig fig)

%uncertaintyTrial 2 = 0.01/0.42 * 100 = 2.38% (3 sig fig)

%uncertaintyTrial 3 = 0.01/0.42 * 100 = 2.38% (3 sig fig)

Averaging the three values gives

(2.33 + 2.38 + 2.38)/3 = 2.36%

Secondly, the uncertainty in the length of the cuvette should be taken into account. The path length
measured by a ruler was 1cm, with a +- 0.05cm uncertainty. The exact same type of cuvettes was used
throughout the experiment. Hence the percentage uncertainty in the length of the cuvette is given as:

%uncertaintylength of cuvette = 0.05/1 * 100 = 5% (to 1 decimal place)

The concentration had been calculated by using the beer lambert with the formula

C = A/(Lε)

Here the percentage uncertainty of concentration is given simply by the addition of percentage uncertainty
of cuvette length and absorbance, so percentage in concentration at 0 minute when catalyst concentration
is 0.1g/L is given below

%uncertaintyconcentration = 5 + 2.36 = 7.36% (to 3 sig fig)

Overall uncertainty of rate of degradation

Since the rate of photodegradation was found by using the average change in time and average change in
the concentration, the real uncertainty of degradation would be the addition of the average uncertainty in
concentration and the average uncertainty in time.
%Average uncertaintytime = (0.167 + 0.111 + 0.0556 + 0.037 + 0.0222)/5 = 0.0786 % (3 sig fig)

%Average uncertaintyconcentration = (7.36 + 7.54 + 7.80 + 8.03 )/4 = 7.68to 3 sig fig)

Now, adding the two value gives the uncertainty for the rate of degradation when catalyst concentration is
0.1g/L

%uncertaintyrate of photodegradation = 7.68 + 0.0786 = 7.76% (to 3 sig fig)

Multiplying the %uncertaintyrate of photodegradation by the rate gives the absolute uncertainty.
0.0776 * 0.0086 * 10-5 = +/- 6.78 * 10^-9 = +/-0.000000667 mM min-1
This exact procedure was repeated for different concentrations of zinc oxide catalyst.

Processed data

The table below shows the rate of degradation with changing catalyst concentration.

Graphing this gives

Each individual point had been connected by a line, and error bars had been added to aid in visuals.
Conclusion and analysis
From the processed data above, it can be seen that initially, an increase in the concentration of the
photocatalyst(zinc oxide)is met by an increase in the rate of degradation. However, something that should
be noted is that once the concentration of a catalyst exceeds 2g/L, any visible increase in the rate of
degradation is not seen anymore. Rather, an asymptote is formed, and the rate of degradation stays fairly
constant, if not slightly decreasing, after the 2g/L point. It is likely that only a certain amount of zinc
oxide particles can reach adsorption-desorption equilibrium and thus take part in the actual degradation.
The slight fall in the rate at 4g/L seems to be attributed to the fact that a high concentration of zinc oxide,
making the solution more milkier, inhibits the penetration of light, thus less photodegradation happening.

The uncertainty in the rate of degradation was at a range from 7 -9 %, certainly not being negligible, but
still at a reasonable range. However, it should be noted that the uncertainty in the concentration of zinc
oxide catalyst, especially for 0.1g/L solution, remains high, at a percentage uncertainty higher than 50%.
Although the uncertainty of catalyst concentration decreases as the dosage of zinc oxide increases, the
uncertainty remains to be high for 0.1g/L and 0.5g/L. Although some uncertainty exists, the results show
a clear trend.

Evaluation

Strengths

The experiment in itself has several strengths. In the first place, it did everything possible such that there
would not be any factors other than catalyst load affecting the degradation. To minimize the effects of
outside/natural light, the beaker with the solution was isolated in a dark box, with the solution being
constantly stirred such that the ZnO would not sink to the bottom. A sophisticated syringe filter(0.22
micrometer) was used to sequester the ZnO from the methyl orange solution for better measurements by
the colorimeter.

Shortcomings and improvements

Weaknesses/shortcomings How could this have affected the Potential improvements

rate?

Exposure to outside light When the sample solutions were The experiment could be
(Random error) being extracted, there was a conducted in almost perfect
slight exposure to outside light dark, such that there would be
as the box had to be opened. minimal outside light.

Assumptions about rate Rate was assumed to be constant Conducting the experiment over
(Systematic error) from the start to the first 45 a shorter time interval(For
minutes, although it would have instance, 0 -30 min)
slowed slightly as time went by.
 Uncertainties in the Catalyst As mentioned before, the Using a more precise balance
concentration uncertainty in the catalyst with less uncertainties.
(Random error) concentration has been high due
to a very small amount of zinc
oxide being used while the
balance has not been as specific.

Uncertainties in the As seen in the absorbance The reason for the discrepancies
concentration of methyl orange values, the initial concentration in the values seems to lie in the
(Systematic error) of methyl orange was not always fact that I made 2 slightly
exactly the same. diluted methyl orange solutions,
which were stored in separate
bottles, and somehow, their
concentration slightly varied.
Using the same methyl orange
solution from the same source
which would be diluted would
improve this part of the problem.

Type of zinc oxide nps The size of the zinc oxide Purchasing zinc oxide
(Random error) nanoparticles were not always nanoparticles with more
the same, ranging from 40 - 60 constant sizes, if possible.
nm, which might affect the
degradation. Smaller size would
mean greater rate due to
increased surface area to volume
ratio.

Extension

More experiments can be done about zinc oxide nanoparticles and photodegradation as it is such a
promising field of studies. For instance, experimenting with different concentrations of methyl orange
with other elements, or comparing the efficiency of different types of nano photocatalysts might be a good
place to start.

Resources:

http://eprints.utar.edu.my/2040/1/PE-2016-1102436-1.pdf
https://chalcogen.ro/1241_ArroyoOrtegaG.pdf
https://www.researchgate.net/figure/Aqueous-Methyl-Orange-absorbance-spectrum-Molar-absorbance-co
efficient-e-25100-M-1-cm_fig1_27362656#:~:text=Molar%20absorbance%20coefficient%20%CE%B5%
20%3D%2025100,irradiation%20lamps%20is%20also%20given.
https://byjus.com/physics/derivation-of-beer-lambert-law/#:~:text=Asked%20Questions%20%E2%80%9
3%20FAQs-,Beer%2DLambert%20Law%20Statement,A%20%3D%20%CE%B5Lc
https://byjus.com/jee/adsorption/
https://energyeducation.ca/encyclopedia/Band_gap
https://www.youtube.com/watch?v=6PIPXIyL_ms
https://www.youtube.com/watch?v=kuvg7rDc2Sc
https://byjus.com/chemistry/methyl-orange/#:~:text=Methyl%20orange%20is%20a%20popular,the%20co
lour%20changes%20to%20yellow.
https://en.wikipedia.org/wiki/Zinc_oxide_nanoparticle