Effectiveness of Photolysis in the Remediation of

Contaminated Groundwater

Alexander Yu
2017
 Table of Contents
I. Abstract ---------------------------------------------------------------------------------1

II. Purpose----------------------------------------------------------------------------------2

III. Background Research-----------------------------------------------------------------2

IV. Hypothesis------------------------------------------------------------------------------7

V. Variables--------------------------------------------------------------------------------7

VI. Materials--------------------------------------------------------------------------------7

VII. Experimental Procedure --------------------------------------------------------------8

VIII. Data Tables and Graphs---------------------------------------------------------------10

IX. Data Analysis---------------------------------------------------------------------------17

X. Conclusion------------------------------------------------------------------------------19

XI. Recommendations for Further Study------------------------------------------------21

XII. Bibliography----------------------------------------------------------------------------22
 1

I. Abstract
Water is a critical resource to the human race. Yet, it is also one of the most vulnerable,

and is at perpetual risk of contamination. Several water treatment methods such as activated

carbon treatment or reverse osmosis already exist, but are limited by their high costs. This

project explores the efficacy of photolysis—the dissociation of molecules via exposure to

electromagnetic radiation—as a potential novel technique. Samples of water artificially

contaminated with common organic contaminants such as gasoline or diesel were first allowed to

evaporate naturally as a control test. Then, identical samples were exposed to ultraviolet

radiation to measure whether or not a detectable increase in the rate of vaporization occurred.

The rate of vaporization was determined by measuring the change in mass of the contaminated

sample—precise to the milligram—over the course of two hours. It was experimentally observed

that photolysis achieved an effect, increasing the rate of vaporization by a statistically significant

amount. As such, photolysis is capable of removing contaminant from the water sample.

However, since it operates rather slowly, the process of photolysis needs to be improved before it

may be considered a reliable and applicable water treatment technique. Nonetheless it does hold

plentiful future promise with respect to potential cost-effectiveness and ability to treat both

chemical and biological contaminants. To address photolysis’s slow treatment rate,

investigations in the direction of using higher power UV light, exposing a greater area of water

to UV light, or utilizing a catalyst may be conducted.

 2

II. Purpose

This experiment aims to explore the viability of photolysis as a novel treatment option for

water contaminated by volatile organic compounds. The criteria of both ability to remove

contamination and rate of treatment will be used to assess the effectiveness of photolysis in

treating contaminated water.

III. Background Research

Fresh water is critical for sustaining society’s industrial, agricultural, and domestic systems. 23%

of this freshwater exists as subterranean groundwater, and an astonishing 8.26x1010 gallons of it are

withdrawn per day. Yet, this critical water source is at constant risk of being polluted by various

contaminants, rendering it unusable or unpotable [5]. For example, the Keystone Pipeline running over the

Great Plains has been identified as a potential source for large-scale gasoline contamination; were it to

burst, gasoline would percolate into the Ogallala Aquifer, which supplies the majority of drinking water to

the central US.

Several remediation techniques already exist to counteract said contamination, the more

prevalent of which include: activated carbon adsorption, reverse osmosis, and rhizofiltration. Activated

carbon treats water by filtering it through solid carbon granules with extremely high surface area. These

granules attract and capture contaminant molecules, rapidly removing them from water. However,

activated carbon treatment suffers the need for an expensive and sometimes unrecyclable catalyst.

Reverse osmosis, perhaps the most common treatment for commercially available drinking water, utilizes

a semipermeable membrane to separate contaminants from water. However, it too suffers from a rather

expensive cost. Lastly, rhizofiltration uses a mass of plant roots to remove and/or capture contaminants.

It is not burdened by high costs, but instead suffers from inflexibility, being able to treat only shallow
 3

groundwater that falls within the reach of plant roots [7]. So, as a result of such shortcomings in existing

remediation techniques, new methods are always being sought and developed.

This project will examine the viability of photolysis as a novel treatment option of groundwater

contaminated by VOCs, or volatile organic compounds: substances which exist as liquids at room

temperature, but are close to their normal boiling point [6].

Photolysis is a

process by which

molecules are broken

down into smaller

components via the

absorption of

electromagnetic energy
[8]
. The mechanism is as

follows: A chemical

bond consists of

electrons distributed
Fig. 1: The molecular orbital diagram for a C-C single bond. Antibonding
throughout molecular orbitals are designated by the superscript “*” while bonding orbitals lack
said superscript. As shown above, the bonding π2p electron is excited to the
orbitals, some of which
more energetic π*2p antibonding orbital, destabilizing the C-C bond.
are considered

“bonding,” and some of which are considered “antibonding.” An electron occupying a bonding molecular

orbital stabilizes the chemical bond, while an electron occupying an antibonding molecular orbital

destabilizes the chemical bond [4]. In the photolysis of a molecule, electrons in bonding orbitals absorb

electromagnetic radiation, exciting them to the higher energy level antibonding orbital(s). The extra
 4

electron in the antibonding orbital destabilizes the bond, and the molecules dissociate. This process is

illustrated in Figure 1.

Naturally, this process can occur in the Earth’s upper atmosphere, when ozone gas is

decomposed to dioxygen gas, in photosynthesis, and in any other system exposed to electromagnetic

radiation of sufficient energy. However, photolysis can easily be simulated artificially as well. So, it is

highly viable to explore the possibility of photolysis in the remediation of contaminated groundwater.

In order for a molecule to undergo photolysis, it must receive a certain amount of energy from

each photon to overcome its BDE, or bond dissociation energy. In addition, the molecule must also be

capable of absorbing the energy. That is, the wavelength of electromagnetic radiation received must fall

within the molecule’s absorption spectrum. Upon receiving and absorbing said energy, spontaneous

dissociation of the molecule will occur.

As a result, the theoretical wavelengths of light that can induce photolysis in a molecule can be

calculated and approximated. First, the BDE of the molecule is converted from kJ/mol to J/molecule, which

yields the amount of energy needed, in standard units, to dissociate one molecule.

Since the minimum energy of the photon is now known, the maximum wavelength of the photon

can subsequently be calculated. The photon’s minimum energy is used as E in Planck’s equation: 𝐸 = ℎ𝑣,

where E is the energy of a single photon, h is the Planck constant of 6.626x10-34J•s, and v is the frequency

of the wave. Then, in order to find the maximum wavelength of light which has the required energy to
𝑐
break the given bond, the frequency v is entered into the equation 𝜆 = 𝑣, where λ is the maximum required

wavelength and c is the speed of light: 2.998x108 m/s [8].

In this specific experiment, gasoline and diesel will be used as common and general

representations of VOC groundwater contamination. Gasoline itself is not a pure substance, but rather a
 5

mixture of various chemical components, including primarily isooctane (also known as 2, 2, 4-

trimethylpentane), butane, benzene and MTBE (methyl tert-butyl ether). The average hydrocarbon in

gasoline is C8H18 [1].

Diesel too is not a pure substance but also a mixture consisting of primarily saturated

hydrocarbons such as paraffin and aromatic hydrocarbons such as alkylbenzene. Diesel generally

contains larger hydrocarbons with higher molecular masses than those of gasoline; the average

hydrocarbon in diesel is C12H23 [1].

Both gasoline and diesel are volatile organic, light non-aqueous phase liquids; they are both less

dense than water, and volatile at room temperature. Gasoline has a density of .71g/mL and a vaporization

point of 35oC, while diesel has a density of .83g/mL and a vaporization point of approximately 150oC.

Applying the aforementioned wavelength calculation, the maximum wavelength that will

theoretically be able to dissociate a gasoline molecule is 329nm, based off a bond dissociation energy of

364 kJ/mol of isooctane (C8H18). The maximum wavelength that will theoretically dissociate a diesel

molecule is 299nm, based off a BDE of 401 kJ/mol of dodecane (C12H26) [1]. In addition, most organic

compounds and contaminants occurring in water absorb light within the range of 200-280nm [2]. This range

is less than the maximum wavelength of light that can induce photolysis, so as long as light within 200-

280nm is provided, it will theoretically both be absorbed by the molecules and be energetic enough to

induce bond dissociation.

The products of photolysis vary largely from molecule to molecule, but in general, molecules are

split at their weakest bond. Per the Handbook of Bond Dissociation Energies in Organic Compounds [3], the
 6

exact bonds broken in

Fig. 2 (right): 2, 2, 4-
2, 2, 4- trimethylpentane (isooctane or
C8H18). The red bond is the first
trimethylpentane bond broken.
(gasoline) and in
Fig. 3 (below): Dodecane (C12H26).
dodecane (diesel) are
The red bond is the first bond
shown in Fig. 2 and broken.

Fig. 3 respectively.

As shown in

Fig. 2 and Fig. 3,

dissociation of

isooctane will yield the free radical C4H9•, and dissociation of dodecane will yield the free radical C6H13•.

It is clearly seen that the products in both cases are notably smaller than the original compound. As such,

their normal boiling point will consequently be lower, and they should theoretically vaporize, removing the

dissociated molecule from the water.

If it is to function well, photolysis potentially presents several distinct advantages over other

remediation techniques. First and foremost, photolysis does not require the consumption of possibly

expensive expendable materials. While treatment methods such as activated carbon adsorption will

consume tens of thousands of pounds of carbon granules annually, photolysis needs nothing more than UV

light bulbs and energy. In addition, photolysis has the rare attribute of being able to treat for both biological

agents such as pathogens along with chemical contamination such as gasoline. Most other remediation

techniques can only treat for one or the other.

 7

IV. Hypothesis

If water contaminated with the VOCs gasoline and diesel is exposed to ultraviolet light in

the wavelength range of 180 to 290 nanometers, then the VOCs will be vaporized at efficiencies

and rates practical for water remediation, since ultraviolet light should be absorbed and

dissociate the molecules. The resulting parts should each have lower boiling points due to having

weaker London Dispersion Forces.

V. Variables

Independent: Exposure to ultraviolet light

Dependent: Mass of gasoline or diesel

Controls: Ambient temperature, Surface area of liquid, Volume of liquid, Ultraviolet light

wavelength, Ultraviolet light intensity, Ultraviolet light exposure time

VI. Materials

 Distilled water

 Gasoline

 Diesel

 48W 110V 180-290nm ultraviolet lamp

 Stand (See Fig. 4)

 Ultraviolet eye protection

 100mL beaker
 8

 2x 10mL graduated cylinder

 2x 25mL graduated cylinder

 .001g electronic balance

 Timer

 Digital thermometer

 Heater

VII. Experimental Procedure

1. Tare the milligram scale such that it reads 0.000g.

2. Place the 100mL beaker on the scale, and record the measured mass. Repeat two more

times for a total of three measurements. Average the three measurements to find the mass

of the beaker.

3. Measure out 15mL of distilled water, and measure 10mL of gasoline. Pour the measured

liquids into the 100mL beaker

4. Place the beaker containing the two liquids on the scale, and as in (2), record three mass

measurements and take the average to find the initial mass of the beaker and liquids.

5. Put the beaker in a dim, well-ventilated environment with minimal air currents, and place

the digital thermometer next to the beaker. If necessary, use a heater to maintain a

constant ambient temperature throughout the experiment.

6. Every 10 minutes, repeat the measurement performed in (4), and record the ambient

temperature at that time. Continue for a total of 120 minutes.

7. After 120 minutes have elapsed, empty, wash and dry the beaker. Repeat (3-6) for a

second trial. This will measure the rate at which gasoline and water naturally evaporate.
 9

8. Using a stand as shown in Fig. 4, suspend the 180-290nm UV lamp above the 100mL

beaker. Place the thermometer under the UV lamp such that any temperature changes

caused by the light are detected.

9. Repeat (3-6), but instead of leaving the beaker in a dim environment, leave the beaker

underneath the UV lamp as shown in Fig. 5. After each mass measurement, ensure that

the beaker is placed in approximately the same spot such as to receive the same exposure

to UV light. Also ensure that the ambient temperature is roughly equal to the temperature

at which (3-6) were performed.

10. Repeat (8-9) for a second trial. This will measure the rate at which gasoline and water

vaporize while exposed to ultraviolet light.

11. Lastly, perform (3-10) again, but using diesel in place of gasoline. This will measure the

rate at which diesel and water vaporize naturally and while exposed to UV light.

Fig. 4: The stand used to suspend the UV Fig. 5: The fully operational experimental
light. Note the nails used to anchor the UV apparatus. Note the digital thermometer
light in place, and the perpendicular lines placed under the light, and the placement of
drawn to ensure that the beaker is replaced the beaker centered on the reference lines.
in the same location after each weighing.
.
 10

VIII. Data Tables and Graphs

Gasoline Evaporation T1 Gasoline Evaporation T2

Time (min) Mass (g) ΔM (g) T (oC) Time (min) Mass (g) ΔM (g) T (oC)
0 21.745 --- 18.0 0 21.822 --- 18.0
10 21.402 -0.343 18.1 10 21.453 -0.369 18.0
20 21.155 -0.590 18.4 20 21.202 -0.620 18.3
30 20.948 -0.797 18.3 30 20.994 -0.828 18.3
40 20.705 -1.040 18.4 40 20.810 -1.012 18.0
50 20.577 -1.168 18.7 50 20.660 -1.162 18.4
60 20.417 -1.328 18.7 60 20.527 -1.295 18.6
70 20.252 -1.493 18.2 70 20.360 -1.462 18.6
80 20.114 -1.631 18.7 80 20.216 -1.606 18.3
90 19.970 -1.775 18.0 90 20.101 -1.721 18.3
100 19.859 -1.886 18.0 100 19.993 -1.829 18.4
110 19.762 -1.983 18.0 110 19.902 -1.920 18.2
120 19.672 -2.073 18.6 120 19.805 -2.017 18.0

Gasoline Evaporation T3 Gasoline Evaporation Average

Time (min) Mass (g) ΔM (g) T (oC) Time (min) ΔM (g)
0 21.752 --- 18.2 0 ---
10 21.434 -0.318 18.3 10 -0.343
20 21.188 -0.564 18.4 20 -0.591
30 20.983 -0.769 18.3 30 -0.798
40 20.804 -0.948 18.2 40 -1.000
50 20.651 -1.101 18.1 50 -1.144
60 20.511 -1.241 18.0 60 -1.288
70 20.388 -1.364 18.2 70 -1.440
80 20.271 -1.481 18.2 80 -1.573
90 20.172 -1.580 18.3 90 -1.692
100 20.070 -1.682 18.3 100 -1.799
110 19.948 -1.804 18.3 110 -1.902
120 19.897 -1.855 18.3 120 -1.982
 11

Gasoline Ultraviolet T1 Gasoline Ultraviolet T2

Time (min) Mass (g) ΔM (g) T (oC) Time (min) Mass (g) ΔM (g) T (oC)
0 21.596 --- 18.0 0 21.782 --- 18.2
10 21.220 -0.376 18.0 10 21.434 -0.348 18.2
20 20.960 -0.636 18.3 20 21.184 -0.598 18.1
30 20.745 -0.851 18.3 30 20.967 -0.815 18.2
40 20.556 -1.040 18.0 40 20.768 -1.014 18.2
50 20.362 -1.234 18.4 50 20.596 -1.186 18.1
60 20.203 -1.393 18.6 60 20.439 -1.343 18.1
70 20.053 -1.543 18.6 70 20.292 -1.490 18.2
80 19.906 -1.690 18.3 80 20.164 -1.618 18.2
90 19.781 -1.815 18.3 90 20.044 -1.738 18.1
100 19.650 -1.946 18.4 100 19.924 -1.858 18.0
110 19.518 -2.078 18.2 110 19.820 -1.962 18.0
120 19.431 -2.165 18.0 120 19.720 -2.062 18.0

Gasoline Ultraviolet T3 Gasoline Ultraviolet Average

Time (min) Mass (g) ΔM (g) o
T ( C) Time (min) ΔM (g)
0 21.829 --- 18.2 0 ---
10 21.528 -0.301 18.2 10 -0.342
20 21.243 -0.586 17.9 20 -0.607
30 21.044 -0.785 18.2 30 -0.817
40 20.834 -0.995 17.9 40 -1.016
50 20.693 -1.136 18.3 50 -1.185
60 20.541 -1.288 18.3 60 -1.341
70 20.406 -1.423 18.0 70 -1.485
80 20.294 -1.535 18.2 80 -1.614
90 20.185 -1.644 18.4 90 -1.732
100 20.073 -1.756 18.2 100 -1.853
110 19.974 -1.855 17.9 110 -1.965
120 19.886 -1.943 18.0 120 -2.057
12
 13

Diesel Evaporation T1 Diesel Evaporation T2

Time (min) Mass (g) ΔM (g) T (oC) Time (min) Mass (g) ΔM (g) T (oC)
0 22.855 --- 18.1 0 22.887 --- 18.2
10 22.844 -0.011 18.1 10 22.883 -0.004 18.1
20 22.837 -0.018 18.1 20 22.878 -0.009 18.2
30 22.830 -0.025 18.2 30 22.873 -0.014 18.2
40 22.825 -0.030 18.2 40 22.869 -0.018 18.2
50 22.818 -0.037 18.3 50 22.863 -0.024 18.2
60 22.817 -0.038 18.2 60 22.859 -0.028 18.2
70 22.814 -0.041 18.2 70 22.856 -0.031 18.2
80 22.809 -0.046 18.2 80 22.850 -0.037 18.2
90 22.805 -0.050 18.2 90 22.847 -0.040 18.2
100 22.801 -0.054 18.2 100 22.842 -0.045 18.2
110 22.799 -0.056 18.2 110 22.839 -0.048 18.2
120 22.795 -0.060 18.2 120 22.835 -0.052 18.2

Diesel Evaporation T3 Diesel Evaporation Average

Time (min) Mass (g) ΔM (g) T (oC) Time (min) ΔM (g)
0 22.906 --- 18.2 0 ---
10 22.896 -0.010 18.2 10 -0.008
20 22.892 -0.014 17.9 20 -0.014
30 22.888 -0.018 18.2 30 -0.019
40 22.882 -0.024 17.9 40 -0.024
50 22.881 -0.025 18.3 50 -0.029
60 22.878 -0.028 18.3 60 -0.031
70 22.877 -0.029 18.0 70 -0.034
80 22.875 -0.031 18.2 80 -0.038
90 22.875 -0.031 18.4 90 -0.040
100 22.873 -0.033 18.2 100 -0.044
110 22.870 -0.036 17.9 110 -0.047
120 22.864 -0.042 18.0 120 -0.051
 14

Diesel Ultraviolet T1 Diesel Ultraviolet T2

Time (min) Mass (g) ΔM (g) T (oC) Time (min) Mass (g) ΔM (g) T (oC)
0 23.083 --- 18.2 0 22.578 --- 18.3
10 23.078 -0.005 18.0 10 22.564 -0.014 18.2
20 23.074 -0.009 18.1 20 22.562 -0.016 18.0
30 23.067 -0.016 18.1 30 22.558 -0.020 18.2
40 23.064 -0.019 18.1 40 22.554 -0.024 18.2
50 23.058 -0.025 18.1 50 22.548 -0.030 18.2
60 23.056 -0.027 18.1 60 22.544 -0.034 18.3
70 23.049 -0.034 18.2 70 22.542 -0.036 18.2
80 23.045 -0.038 18.2 80 22.535 -0.043 18.2
90 23.041 -0.042 18.2 90 22.532 -0.046 18.2
100 23.035 -0.048 18.2 100 22.527 -0.051 18.3
110 23.030 -0.053 18.2 110 22.521 -0.057 18.2
120 23.027 -0.056 18.1 120 22.520 -0.058 18.1

Diesel Ultraviolet T3 Diesel Ultraviolet Average

Time (min) Mass (g) ΔM (g) T (oC) Time (min) ΔM (g)
0 22.797 --- 18.2 0 ---
10 22.794 -0.003 18.4 10 -0.007
20 22.787 -0.010 18.5 20 -0.012
30 22.777 -0.020 17.8 30 -0.019
40 22.770 -0.027 17.8 40 -0.023
50 22.768 -0.029 18.0 50 -0.028
60 22.764 -0.033 18.2 60 -0.031
70 22.758 -0.039 18.3 70 -0.036
80 22.753 -0.044 18.5 80 -0.042
90 22.748 -0.049 18.1 90 -0.046
100 22.741 -0.056 18.2 100 -0.052
110 22.742 -0.055 18.5 110 -0.055
120 22.729 -0.068 18.4 120 -0.061
15
 16

Notes:

 Graphs are plotted using data from the “Average” data tables.

The values in these tables were obtained by averaging the mass

values in the three corresponding trials at a specific time.

 ΔM values indicate the change in mass of the entire VOC-

water mixture from T=0min. For example, the ΔM value for

T=50min is calculated by subtracting the original mass at

T=0min from the sample’s mass at T=50min.

 While both graphs may appear to indicate similar slopes and

rates of change, note the scale. The scale on gasoline’s graph is

in increments of 0.500g while the scale on diesel’s graph is

only 0.010g.

 Error bars in both graphs at all points take on a value of

±0.004g. This is the sensitivity error range of the electronic

balance. The error bars for “Change in Mass of Gasoline as a

Function of Time” are present but are too small to be visible.

 17

IX. Data Analysis

To collect the data in this experiment, the mass of the liquid and beaker was measured

every 10 minutes. Since the milligram scale measures in extremely fine increments and is prone

to yielding different measurements for the same mass, three measurements were performed each

time to reduce the effect of any sensitivity errors, and the average was then taken. Three trials

were performed as such for each group.

To control temperature, a heater was used and adjusted. The power of the heater was

altered until the temperature around the beaker equilibrated at 18.5±0.5oC. As the temperature

rose, the power was decreased, and as the temperature fell, the heater power was increased, until

the temperature stabilized. In addition, to compensate for any heat generated by the ultraviolet

light, the heater power was decreased, and it was ensured that the temperature remained at

18.5±0.5oC in spite of the light.

This experiment is based upon two assumptions. First, that any evaporation which occurs

is that of the VOC and only that of the VOC; the water does not evaporate. Both being LNAPLs,

the gasoline and diesel both form a layer over the water, so it is assumed that the evaporation of

water is suppressed and therefore negligible. Second, the water is assumed to be incapable of

being dissociated by ultraviolet radiation. Not only does the VOC form a protective barrier, but

the higher BDE of water means that if photolysis does occur, it will occur in the VOC first.

Preliminary testing confirms this assumption; UV light exposure has no effect on the rate of

water’s vaporization.

In terms of error, the approximate error range of the scale was experimentally found to be

±0.004g. This is the value used to represent all error bars in the graphs, for no other measuring
 18

instrument with appreciable influence on experimental results was utilized. Since no

manufacturer specification regarding error was provided, a 20g test weight was repeatedly

weighed 50 times, resetting the scale between each measurement. The highest absolute deviation

from the true 20g value was taken as the error range in either the positive or negative direction.

The experiment shows that exposure of gasoline to ultraviolet light has a statistically

significant effect on its rate of vaporization. All three trials indicate that gasoline’s rate of

vaporization while exposed to ultraviolet light is clearly higher than its natural rate of

evaporation (see graph “Change in Mass of Gasoline as a Function of Time”). A gradual

separation occurs during the 120 minutes between the ΔM values of the experimental and control

groups, suggesting that photolysis did occur, expediting gasoline’s vaporization. Were the mass

to be observed for a longer period, the data suggests that this separation would increase over

time. Yet, the apparent effect of photolysis was more minute than expected. Calculations show

that exposure to ultraviolet light increased the total mass of gasoline vaporized in 120 minutes by

(on average) 0.075 grams, or 3.78% more than the original 1.982 grams vaporized by

evaporation. Though this percentage difference is relatively small, it lies well outside the margin

of error, so much so that the error bars on the gasoline graph are nearly imperceptible. As such,

the results are considered to be statistically valid and significant.

In the case of diesel, the effects of photolysis are noticeable and statistically significant as

well. But, its magnitude is much smaller. A larger molecule, diesel naturally evaporates very

slowly, losing on average only .051g over the course of 2 hours. UV exposure increased this

value by only 0.01g, or 19%, for a total of 0.61g lost. This is just a large enough increase such

that the error bars of the evaporation control group and UV exposure experimental group are
 19

mutually exclusive. Thus, UV light is deemed to also have an apparent but smaller effect on the

rate of evaporation of diesel.

X. Conclusion

The data obtained in the experiment partially supports the hypothesis. It was originally

hypothesized that exposing VOC contaminated water to ultraviolet light would provide an

efficient and quick way of removing contaminants through photolysis. While it was observed

that photolysis does not occur rapidly enough under experimental conditions to render it a

practical method for treating large volumes of contaminated water, it was still proven to be

consistently effective nonetheless.

In the case of gasoline, over the course of two hours, a total 25mL of contaminated water

(consisting of 15mL pure water and 10mL VOC contaminant), was subjected to the suggested

treatment process. This resulted in the removal of .075g or .105mL (based off gasoline’s density

of .71g/mL) more contaminant. As such, when gasoline-contaminated water was exposed to UV

light the mass lost to vaporization over the course of two hours increased by a significant value.

A similar situation occurs with respect to diesel’s photolysis: a small amount of extra

diesel—0.010g—was removed by photolysis from the water sample. This exceptionally small

value falls outside the margin of error—though only barely.

As for the cause behind photolysis’s long treatment time, there are several possible

explanations. Though electromagnetic radiation of theoretically appropriate wavelength was

provided to cause dissociation of the molecules, the molecules were either not dissociated, or did

not vaporize.
 20

The first possible explanation lies in the fact that while light may be of the proper

wavelength to dissociate a molecule, it may lack the necessary intensity or amplitude to do so. In

the experiment, a light of only 48W was used to bombard chemicals with UV radiation. 48W of

power may be vastly insufficient to dissociate meaningful quantities of contaminant within a

reasonable amount of time.

The second possible explanation lies in the stability of the results of photolysis. After an

organic compound such as 2, 2, 4-trimethylpentane undergoes photolysis, the production of the

free radical •C4H9 is expected. As these free radicals are highly reactive and unstable, it is

entirely possible that they will dimerize or re-bond to reform the original molecule before they

can vaporize due to their weak intermolecular forces. Thus, though a molecule may undergo

photolysis, the products may not necessarily be stable enough to vaporize to achieve the desired

effect.

Methods to improve photolysis’ efficiency and rates must first be investigated and

implemented before it may be considered a widespread remediation technique in water treatment

processes. The financial implications of photolysis are beyond the scope of this project.

Though results were excellent, certain errors existed which degraded the quality of data.

The beaker was inevitably shaken when taken to find the mass. Upon shaking, a thin film of

gasoline/diesel and water was formed on the sides of the beaker. This film created more surface

area on which liquids could vaporize and receive exposure to UV light. Lastly, the ±.004g error

of the electronic balance is significant when considered in the context of mere .061g changes

observed in diesel’s vaporization and certainly played a role in creating the more uneven trends.
 21

XI. Recommendations for Further Study

While the underdeveloped nature of photolysis has been established in this experiment,

photolysis does indeed hold further promise. If such a method were to function properly and

efficiently, the benefits would be large. Though not tested in this experiment, it is a well-

established fact that UV light can act as a powerful germicidal agent. Thus, a photolysis-based

remediation technique could both double as a way to remove chemical contamination and

harmful biological agents.

Possible future research to pursue may involve stronger, more intense classes of UV

lights may be conducted. While the light used in this experiment is considered a low pressure

ultraviolet light, there exist medium and high pressure lights which emit stronger UV rays which

may elevate the rate of photolysis to acceptable speeds. UV lights of higher power—reaching up

to 1000W—are also available. As such, experiments utilizing high power UV lights may also

yield more favorable results.

A larger liquid surface area may be investigated. Since the liquid samples were contained

in a 100mL beaker in the experiment, only a small disc of liquid on the surface of the beaker was

exposed to UV light. However, if a flat and shallow container were to be used, a larger surface

area of liquid could receive UV radiation, accelerating the rate of photolysis.

Lastly, the usage of a catalyst to expedite photolysis may be considered. Such catalysts

already exist for the photolysis of water in the production of hydrogen gas, so it is feasible that

such a catalyst may be developed for non-polar organic compounds as well. If such a catalyst

could be developed, and be of minimal toxicity, it would unlock the full potential of photolysis.
 22

XIII. Bibliography

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Ullmann's Encyclopedia of Industrial Chemistry

[2] Harvey, Monica. "THE IMPACTS OF UV DIRECT PHOTOLYSIS AND UV/H2O2

ADVANCED OXIDATION PROCESSES ON THE FORMATION OF NITROSAMINES AND

ORGANIC CHLORAMINES FROM SUBSEQUENT CHLOR(AM)INATION." (n.d.): n. pag.

Department of Civil Engineering University of Toronto, 2009. Web. 28 Mar. 2017.

[3] Luo, Yu-Ran. "Handbook of Bond Dissociation Energies in Organic Compounds."

(n.d.): n. pag. CRC Press, 2003. Web.

[4] "Molecular Orbital Theory." Molecular Orbital Theory. Purdue, n.d. Web. 28 Mar.

2017.

[5] Perlman, USGS Howard. "Groundwater Use in the United States." Groundwater Use,

the USGS Water Science School. N.p., n.d. Web. 09 Jan. 2017.

[6] "Table of Regulated Drinking Water Contaminants." EPA. Environmental Protection

Agency, 04 Oct. 2016. Web. 09 Jan. 2017.

[7] "Treatment Technologies Screening Matrix." (n.d.): n. pag. Federal Remediation

Technologies Roundtable. Web.

[8] "18.2 The Outer Regions of the Atmosphere." Chemistry: The Central Science,

Chapter 18, Section 2. Prenhall, n.d. Web. 28 Mar. 2017.