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) of the methyl orange solution over time with a colorimeter(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. Among the many pollutants, dyes have a large share in contributing to water pollution.
(Source)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 their high efficiency and
widespread use in the industries. The dye that would be degraded also had to be singled out. Since the
dyes most widely in use and causing pollution are azo dyes, which are synthetic dyes used commonly in
textile industries, methyl orange, a typical azo dye and also easily available in the lab, was chosen.

Background information

Methyl orange is a well known azo dye and has a molar mass of about 327g mol.-1 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. (source)

Zinc oxide nanoparticles are known to absorb UV light, due to their high energy gap of 3.37 eV. Energy
gap is the difference in energy between the valence band, where the strong attraction from the positive
nucleus tightly holds the electrons, and conduction band, a band where electrons are delocalized and are
now 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 absorb the energy 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 positively charged electron hole, while the conduction band, which has gained
electrons, becomes negatively charged. (source)

This can also be expressed through the reaction formula

− +
𝑍𝑛𝑂 + ℎ𝑓 → 𝑍𝑛𝑂(𝑒𝑐𝑏 + ℎ𝑣𝑏 ) (1) (source)
(Where hvb + is the electron hole, and ecb - are the excited electrons,
now in the conduction band and 𝑓 is the frequency of light (𝑓> 7.9 *
1014 hz )

The electron holes and the excited electrons now move to the
ZnO’s surface, and proceed on to start several redox reactions. Diagram 2
This is illustrated in diagram 2.

The positive holes created are strong oxidizing agents, and react with water to form hydroxyl free
radicals.

+ • •+
ℎ𝑣𝑏 + 𝐻2𝑂 → 𝑂𝐻 + 𝐻 (2) (source)

The free electrons are strong reducing agents, reducing the oxygen and forming a superoxide anion
radical.

− •−
𝑒𝑐𝑏 + 𝑂2 → 𝑂2 (3) ((source)

The presence of the positive holes and the excited electrons could possibly lead to a recombination as
shown below

− +
𝑍𝑛𝑂(𝑒𝑐𝑏 + ℎ𝑣𝑏 ) → 𝑍𝑛𝑂 + energy (4) ((source)

However, this is swiftly prevented by other electron acceptors such as oxygen, which combine with the
excited electrons to form more free radicals as we had seen in (3).

Eventually the reactive free radicals, through a long cascade of chemical reactions and intermediates,
decompose the dye into harmless compounds such as CO2 and water.
 •
𝑀𝑒𝑡ℎ𝑦𝑙 𝑜𝑟𝑎𝑛𝑔𝑒 + 𝑂𝐻 → 𝑖𝑛𝑡𝑒𝑟𝑚𝑒𝑑𝑖𝑎𝑡𝑒𝑠 → 𝐶𝑂2 + 𝐻2𝑂 + 𝑂2 (source)
•−
𝑀𝑒𝑡ℎ𝑦𝑙 𝑜𝑟𝑎𝑛𝑔𝑒 + 𝑂2 → 𝑖𝑛𝑡𝑒𝑟𝑚𝑒𝑑𝑖𝑎𝑡𝑒𝑠 → 𝐶𝑂2 + 𝐻2𝑂 (source)

Adsorption

When the rate of the reaction is concerned, adsorption of the photocatalyst is a crucial factor. Adsorption
is the adhesion between atoms, ions, and other molecules, and in this case is the attraction between methyl
orange(dye) and the zinc oxide nanoparticles. More adhesion means greater attraction between zinc oxide
nanoparticles and methyl orange, which means that it would be easier for the electron holes, excited
electrons of the zinc oxide and the free radical molecules to degrade the methyl orange particles due to the
greater physical proximity. 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 the 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. (source)

Ultraviolet light

Ultraviolet is an electromagnetic wave, with its wavelength falling into the range of 100 - 400 nm. It
should be noted that a shorter wavelength would mean a greater energy. Not all UV lights are the same,
they are broken into UVA, UVB, and UVC light, in the sequence of decreasing wavelength or increasing
energy. (source) The UV light source in this experiment would provide a UVA light as this is sufficient for
the reaction to be initiated. As mentioned earlier, the energy of the UV light should be greater than the
band gap, and the minimum wavelength can be found through the formula,

ℎ𝑐
𝐸 = λ
> 3. 37 𝑒𝑉 = 5.4 * 10-19 J

Solving this gives λ < 369 𝑛𝑚

Hence UV lamp providing UVA ray with λ = 360 nm has been used for the experiment.
The intensity of this light, given as power per area, is also an important factor. Greater intensity means
more light rays entering the solution and stirring up more reaction, and vice versa, which means that the
intensity of the light should be kept constant. (Tsokos, 2014)

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 into the solution, reducing the amount of light hitting
the zinc oxide particles and hence slowing down photodegradation. (source)

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

Dependent The rate of degradation was found by extracting a sample of solution every 15 minutes
variable 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.

Controlled variables Method of control Significance of control

Temperature Experiments were conducted Constant temperature ensures that the

at room temperature( 25 oC) experiment is carried out in the same
and this was controlled using condition(since temperature affects the rate of
air conditioning and the reaction because it affects the frequency of
temperature control function collisions).
of the magnetic stirrer(the dial
was turned to 25 oC.

Distance between The distance between the light This ensures that the methyl orange solution is
lightbulb and bulb and the center of the exposed to the same intensity of ultraviolet
solution beaker which holds the light emitted by the lamp. As discussed in the
solution was kept at a constant background information section, intensity is all
10cm. about how much light rays are entering the
solution. More of these light rays would mean
more reaction, and vice versa.

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

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

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

Material and Apparatus

ZnO (nps 40 - 60 nm with 98% purity) (50g) Box x1

Colorimeter (± 0.01) x1 Beaker(250ml) x1

Magnetic stirrer x1 UV light lamp(360 nm) (15W) x1

Magnetic stirring rod x1 Measuring cylinder (50ml) (± 0.5ml)

Gas syringe x4 Syringe filter (0.22 micrometer) x 60

Pure Methyl orange Distilled water (3L)

Stopwatch (± 1 sec) x1 Cuvette (1cm width) (± 0.05cm) x4

Weighing boat Balance x1

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, and gloves were
irritation. worn.

UV light UV light can prove to be Protective goggles had been worn throughout the
harmful for our eyes. experiment.

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

To calculate both the rate of photodegradation, the concentration of the solution, the beer lambert’s law
should be used as discussed in background information, given by the formula:

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

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

0.423
C= (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

The Changing concentration

over time of methyl orange
when zinc oxide
concentration is 0.1g/L is
shown below.

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 ±0.5 ml
as its absolute uncertainty with 50 ml volume. To fill up the beaker up to 200ml, the measuring cylinder
with 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 ±2ml.

%uncertaintyamount of volume = 2/200 = ±1 %.

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 = 11%.

The absolute uncertainty for the zinc oxide concentration when it is 0.1g/L is

0. 11 * 0. 1 = 0. 011 = 0. 01 ( 1 𝑠𝑖𝑔 𝑓𝑖𝑔)

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 %

%Average uncertaintyconcentration = (7.36 + 7.54 + 7.80 + 8.03 )/4 = 7.68%

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 * 0.000086 mM/min = = +/-0.00000667 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 along with

the error bars gives the
graph below.
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 concentration 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

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 be equally spread out in the solution.. 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/short How could this have affected the rate? Potential improvements
comings

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

Assumptions Rate was assumed to be constant from the very Conducting the experiment
about rate start to the first 45 minutes, although the rate over a shorter time interval(For
(Systematic error) would have slowed down slightly as time went instance, 0 -30 min)
by. The rate at 0 minute would be higher than
the rate at 45 minutes, due to there being less
methyl orange molecules(many had been
degraded)

Uncertainties in As mentioned before, the uncertainty in the Using a more precise balance
the Catalyst catalyst concentration has been fairly high due with less uncertainties.
concentration to a very small amount of zinc oxide being used
(Random error) while the balance has not been as specific.

Type of zinc oxide The size of the zinc oxide nanoparticles were Purchasing zinc oxide
nps not always the same, ranging from 40 - 60 nm, nanoparticles with more
(Random error) which might affect the degradation. Smaller size constant sizes, if possible.
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.
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