IEEE TRANSACTIONS ON PLASMA SCIENCE, VOL. 42, NO.
5, MAY 2014
Formation of Alcohols and Carbonyl Compounds
from Hexane and Cyclohexane With Water in a
Liquid Film Plasma Reactor
Robert J. Wandell, Stefan Bresch, Kevin Hsieh, Igor V. Alabugin, and Bruce R. Locke, Senior Member, IEEE
Abstract— In this paper, vaporized n-hexane in a flowing argon
carrier gas was mixed with deionized liquid water and injected
into a tubular plasma reactor. A liquid water film forms on the
wall of the tubular reactor and plasma channels propagate along
the gas-liquid interface. Gas-chromatography mass spectrometry
and nuclear magnetic resonance spectroscopic analysis of the
major products and their relative ratios collected in the effluent of
the reactor confirm the formation of 3-hexanol (26%), 2-hexanol
(21%), 3-hexanone (17%), 2-hexanone (17%), 1-hexanol (11%),
and hexanal (8%). The functionalization is likely due to oxidation
of the organic stating material by OH radicals formed from
the dissociation of water by the plasma. The functionalization
of cyclohexane was achieved in the same manner where
analysis showed the formation of cyclohexanone (47%),
cyclohexene (20%), cyclohexanol (19%), hexanal (11%), and
2-cyclohexenone (2%). Hydrogen peroxide was also produced in
the presence of either organic compound and the amount formed
decreased as the amount of organic flowing into the reactor was
increased. It is likely that the hydrogen peroxide is formed in
the gas phase close to the gas-liquid interface by OH radical
recombination. This paper demonstrates the activation of the C-H
bond using low temperature plasma by combining two common
chemical feedstocks (hydrocarbon and water) and transforming
them into the higher value functionalized organic products via a
sequence of reactions where all necessary intermediate reactants
are formed in situ by the electric discharge.
Index Terms— Non thermal plasma, plasma chemistry,
plasma–liquid interactions.
I. I NTRODUCTION
E LECTRICAL discharge plasma contacting liquid phases
has been studied for a wide range of chemical, bio-
medical, environmental, and materials synthesis applications
[1]–[6]. The synthesis for a number of organic and inorganic
compounds by gas-liquid plasma dates to the early work of
Gubkin [7] and the subsequent work of Hickling [8]–[11], who
used glow discharge electrolysis, whereby one electrode was
Manuscript received September 26, 2013; revised January 6, 2014; accepted
January 25, 2014. Date of publication February 20, 2014; date of current
version May 6, 2014. This work was supported in part by the National
Science Foundation under Grant CBET 1236225, and in part by Florida State
University.
R. J. Wandell, K. Hsieh, and B. R. Locke are with the Department of
Chemical and Biomedical Engineering, Florida A&M University-Florida State
University College of Engineering, Tallahassee, FL 32310 USA (e-mail:
rjw05c@my.fsu.edu; hsiehke@eng.fsu.edu; locke@eng.fsu.edu).
S. Bresch and I. V. Alabugin are with the Department of Chemistry and
Biochemistry, Florida State University, Tallahassee, FL 32310 USA (e-mail:
sbresch@chem.fsu.edu; alabugin@chem.fsu.edu).
Color versions of one or more of the figures in this paper are available
online at http://ieeexplore.ieee.org.
Digital Object Identifier 10.1109/TPS.2014.2304183
0093-3813 © 2014 IEEE. Personal use is permitted, but republication/redistribution requires IEEE permission.
See http://www.ieee.org/publications_standards/publications/rights/index.html for more information.
1195
placed inside the liquid phase and one in the gas phase. A wide
range of other gas-liquid contacting schemes has been studied
including falling films, aerosol sprays, and bubble injection
into liquids [2], [5], [12]–[19]. It has been shown that the
presence of the liquid phase not only affects plasma properties
such as electron energy and density, but also the chemical
reactions which take place [5]. The liquid phase can also
serve as a source of additional vapor phase reactant as well
as function as a reservoir to collect the generated products,
protecting those products from degradation by direct electron
attack in the gas phase plasma [14], [20]–[22].
Reactions with organic compounds in plasma discharges
have been investigated for a wide range of applications and
conditions including cases of plasma polymerization [23],
plasma discharge in organic liquids, and the more commonly
studied cases of organic compounds in liquid water for
pollution control [2], [24]–[28]. Plasma generated directly
in an organic liquid phase has been demonstrated to form
diamond coatings [29] and other carbonized materials such
as nanofibers [30]. Gas phase plasma (spark discharge:
3 to 12 W) generated with argon over heavy oils (n-C10 to
n-C25 hydrocarbons) leads to significant chain breakage to
form one to four carbon containing compounds with ethylene
and hydrogen being the predominate species [31], [32]. Liquid
n-hexadecane was studied as a model of a hydrocarbon oil
and was cracked into C6 to C15 hydrocarbons using a dielec-
tric barrier discharge with a methane carrier over the liquid
hydrocarbon [33]. In another example, crude oil was treated
with a dielectric barrier discharge for various carrier gases
(H2 , CO2 , CH4 ) where rheological analysis showed a decrease
in viscosity of the crude oil treated by plasma, and nuclear
magnetic resonance (NMR) analysis showed that the plasma
treatment primarily led to water extraction from the naturally
occurring emulsified water in the crude [34]. Finally, an 80-W
microwave plasma with water vapor over a heavy oil liquid
demonstrated a series of reaction products from long chain
aromatics to linear and shorter aromatic rings and, finally,
syngas, CO2 , and small alkanes and alkenes, as well as traces
of other carbonaceous products [35].
Previous studies have also demonstrated efficient production
of H2 from methanol and water/methanol mixtures, as well as
other alcohol solutions, using a spray reactor [36]. Clearly at
high enough plasma power and exposure time, a wide range
of hydrocarbons, even from heavy oils, can be cracked to rel-
atively small compounds. The key issues that will make these
1196
types of applications useful for chemical synthesis of valuable
products are to control or stop the plasma-induced radical
reactions and to promote reaction selectivity. For example,
some selectivity was demonstrated in a gas phase microwave
plasma with n-hexane vapor in flowing argon through changes
in the plasma input power, feed flow rates, and location of the
feed [37].
Oxidation of the C-H group in alkanes under low tem-
perature and pressure conditions is a significant challenge
due to selectivity issues and over oxidation by harsh con-
ditions [38]–[40]. While catalysts have been developed that
use hydrogen peroxide [38]–[40] to form OH radicals capable
of functionalizing alkanes, the reactions are quite complex.
Hydrogen abstraction of alkanes at high temperature primarily
for combustion has also been studied [41]–[49].
Plasma processes have been demonstrated to produce
methanol from methane with high efficiency [50]–[56]. Much
of the extensive literature on methane conversion in plasma
reactors focuses on methane conversion in dry gas to higher
hydrocarbons [57]–[59] and some effort has been devoted
toward methane to methanol and/or formaldehyde conversion
with water vapor and or liquid water films [12], [15], [54],
[60], [61]. As with the formation of hydrogen peroxide [20],
[62], [63] and hydrazine [14], [16], the formation of methanol
may be optimized under conditions where degradation reac-
tions with radicals are minimized and over oxidation to
CO and CO2 is suppressed [61].
Alkanes and other compounds have been oxygenated by
oxygen radicals in oxygen plasma as well [17], [64]–[80].
However, oxidation with hydroxyl radicals from liquid water
in gas-liquid plasma systems has mostly been used to oxidize
organic compounds in liquid water for pollution control [4].
Reactions of alkanes such as n-hexane and cyclohexane with
OH radicals produced from liquid water by plasma discharge
where the plasma channels propagate along a gas-liquid
interface have not, to our knowledge, been reported.
There are three important differences between the func-
tionalization of hydrocarbons to produce small intermediate
products by plasma and the more extensively studied plasma
polymerization processes [23]. In plasma polymerization, the
desired goal is to form a surface polymer coating using gas
phase plasma containing the precursor molecules. In such
cases, a large conversion is required to form the coating.
To produce a large conversion, a large plasma energy is
required, which leads to complete dissociation of the precur-
sor compounds into small organic fragments. The resulting
recombination reactions are not significantly selective due to
the large number of possible reactions which can occur [23].
One goal of this paper is to introduce selectivity. Although
selectivity may come at the cost of lower conversion, this
cost can be compensated in synthetic chemistry by component
recirculation as well as series or parallel reactor designs. The
second issue relates to the site of the main polymerization
reactions. In plasma polymerization, there is still debate on
whether the main polymerization reactions occur in the gas
phase or on the surface. Both cases are predicted to lead
to the irregular structure of the polymer, where the reactor
pressure and plasma pulsing can affect the location of these
IEEE TRANSACTIONS ON PLASMA SCIENCE, VOL. 42, NO. 5, MAY 2014
reactions [23]. In gas-liquid plasma systems, the physical
location of the plasma chemical synthesis will depend, in part,
on the volatility of the precursor molecule. Under conditions
of low volatility, the plasma radicals may directly impinge
on the liquid surface initiating reactions at the interface or
even generate some radicals in the liquid phase. For high
volatility cases, the organic liquid is fully vaporized and can
react directly in the gas phase. Different product distributions
are expected in these different conditions. A third issue relates
to modification of reactor/reaction conditions involving gen-
eration of pulses by the power supply. Shorter plasma pulses
(or with superimposed pressure pulses) have been shown to
control chain propagation in plasma polymerization, but again
at the cost of yield [23].
The goal of this paper is to assess the viability of using
a pulsed plasma reactor with a flowing liquid water film
and an inert carrier gas containing organic vapor for the
synthesis of more useful organic compounds. In this paper, the
conversion of the normal alkane n-hexane and the cyclic alkane
cyclohexane into oxygenated products (alcohols, ketones, and
aldehydes) by hydroxyl radical attack was investigated. Reac-
tion products were determined by gas-chromatography mass
spectrometry (GC-MS) and NMR spectroscopy.
II. E XPERIMENTAL M ETHODS
A. Reactor and Apparatus
Fig. 1 shows the general process schematic diagram of
the experimental setup. High purity argon gas (Air Gas;
Tallahassee, FL) at 414 kPa was used, resulting in a flow rate
of 0.5 L/min as measured by a rotameter (Cole Palmer; Vernon
Hills, IL). The argon was allowed to flow unrestricted into the
reactor inlet. Thus, the resulting flow rate was a function of the
pressure head and the inner diameter of the reactor inlet nozzle
(0.25 mm). The argon gas contacts a small amount of liquid
organic at Mixing Zone 1 (1/16 in Swagelok nylon tee joint,
Jax Fluid System Technologies; Jacksonville, FL). The organic
starting materials were both introduced into the system at a
constant rate of 0.002 mL/min with a syringe pump (Harvard
Apparatus, PhD 2000 Infusion; Holliston, MA) equipped with
a 10-mL glass syringe (Hamilton, GASTIGHT; Reno, NV).
Due to the high volatility of n-hexane and cyclohexane and the
small amount used in comparison with the argon flow rate, the
organics were rapidly vaporized into the gas phase in Mixing
Zone 1. The resulting gas phase mixture then contacts a liquid
stream of deionized water flowing at 0.5 mL/min (pH–5.0 ±
0.2, conductivity–5.0 ± 1.0 μS/cm) at Mixing Zone 2 (1/16
in Swagelok nylon tee joint, Jax Fluid System Technologies;
Jacksonville, FL). The deionized water was delivered to the
system with a high pressure, pulse injection pump (Optos
Series, Eldex Laboratories; Napa, CA). High pressure mixing
occurs between these three components (argon, organic, and
water) in Mixing Zone 2, after which the mixture flows
through the inlet nozzle of the reactor and into the plasma
discharge region where chemical reactions are induced.
After exiting the discharge region, the liquid phase of the
effluent was directly collected in a vessel while the gas phase
was allowed to flow through a series of condensers submerged
WANDELL et al.: FORMATION OF ALCOHOLS AND CARBONYL COMPOUNDS 1197

Fig. 1. Overall process schematic. n-Hexane was vaporized into a stream of ultrahigh purity argon gas, which then mixes at high pressure with a stream of
deionized water. This mixture was then sprayed into a tubular plasma discharge region after which the liquid effluent was collected in a series of collection
traps.

in cold baths consisting of dry ice and acetone (−78 °C) to

condense out any compounds still vaporized in the argon gas.
A 4 h run time was used where afterward the resulting three
liquid phases were analyzed individually using GC-MS, NMR,
and UVis spectroscopy.
The reactor was constructed from prefabricated round tub-
ing giving it a cylindrical geometry. Because of its simple
construction from prefabricated materials, an added benefit to
this reactor design is that it can be considered disposable. The
inlet and outlet of the reactor consist of 316 stainless steel
capillary tubing with an outer diameter of 1.59 mm (Supelco;
Bellefonte, PA) incased by fused quartz tubing spacers with an
inner diameter of 1.6 mm (AdValue Technology; Tucson, AZ);
the tubing was positioned such that the ends of the stainless Fig. 2. Photographs of the plasma discharge region with (a) rapid shutter
speed (1/12 000 s) and (b) slow shutter speed (1/60 s) depicting filamentous
steel and quartz tube spacers were flush at the entrance and plasma channels propagating along the liquid gas interface.
exit of the discharge region. The inlet and outlet assemblies
were inserted into either end of an additional piece of fused
quartz tubing with an I.D. of 3.0 mm (AdValue Technology; previously mentioned flow regions. Fig. 2(a) is a photograph of
Tucson, AZ), which served as the reactor wall and viewing the plasma zone region of the reactor taken with a rapid shutter
port for high speed imaging. The inlet and outlet assemblies speed of 1/12 000 s and shows a single filamentous plasma
were positioned such that a 4-mm gap existed between the channel traveling along the gas-liquid interface. Fig. 2(b) is a
entrance and exit of the discharge region. photograph taken with a slow shutter speed 1/60 s and captures
A key aspect of this reactor system is the flow pattern gener- the many filamentous plasma channels produced during this
ated inside the reactor volume. Because the inlet capillary tube time period. These photographs indicate that the discharge
has an inner diameter of 0.25 mm and that of the discharge takes place along the gas-liquid interface and not within the
region is 3 mm, a well-mixed radial spray is generated as liquid film flow region or in the middle of the high velocity
the high pressure mixture exits the inlet nozzle and enters the gas stream. In Fig. 2(a) and (b), the reddish streamer channels
reactor volume. This spray rapidly contacts the reactor wall arise from the water flow while the lighter bluish-green parts
creating a highly turbulent liquid film, which flows along the come from the organic vapor.
wall in combination with a high velocity gas flow region in An additional key aspect of this reactor design was that the
the center of the reactor. stainless steel capillary tubing, which acted as the entrance
High speed imaging was performed with a VW-9000 series and exit to the reactor volume also function as the anode
high speed microscope system with a VH-00R 0–50× lens and cathode, which generate the plasma discharge, as shown
(Keyence; Itasca, IL) to confirm the existence and analyze the in Fig. 1. This configuration provides maximum contact of
1198
Fig. 3. Sample waveforms for the voltage, current, and instantaneous power of the discharge.
the reactants with the plasma by minimizing bypass regions
where the gas-liquid flow does not contact the plasma. In the
specific setup, the high voltage lead was attached to the inlet
nozzle of the reactor while the outlet nozzle was grounded.
The power supply (dc 1740B BK Precision; Yorba Linda, CA)
was driven by a pulse generator (2 MHz 4010A BK Precision;
Yorba Linda, CA) to provide pulsed 12 V direct current to an
automobile ignition coil (VW-AG, ERA Germany). A high
voltage diode was placed between the ignition coil and the
reactor to protect the coil from unwanted upstream voltage
surges back to the ignition coil from the reactor. The pulse
frequency and duty cycle was held constant for all experiments
at 500 Hz and 40%. The power supply and pulse forming
circuit is similar to that used in [36], [62], and [81]–[85].
The voltage, current, and power waveforms of the discharge
were measured with an oscilloscope (DPO 3014 Tektronix;
Beaverton, OR). The sampling rate of the oscilloscope was
104 points for the 100-ms acquisition window. The discharge
voltage was measured with a high-voltage probe (P6015
Tektronix; Beaverton, OR) connected to the lead electrode.
The current was measured with a 100  shunt in the secondary
of the ignition coil. The instantaneous power was calculated
by multiplication of the individual data points in the current
and voltage waveforms. The mean discharge power was deter-
mined by averaging the instantaneous power across the time
period of acquisition window. Sample current, voltage, and
power waveforms are shown in Fig. 3. It should be noted that
IEEE TRANSACTIONS ON PLASMA SCIENCE, VOL. 42, NO. 5, MAY 2014
the power reported in this paper was the power delivered to the
discharge and that the overall efficiency also depends upon the
power and efficiency of the transformer.
III. C HEMICAL A NALYSIS
The concentration of hydrogen peroxide formed in the
liquid fractions was measured using a colorimetric test with a
UV-Vis spectrophotometer (Perkin-Elmer, Lambda 35;
Waltham, MA) where 2-mL liquid samples were taken and
mixed with 1 mL of a titanium oxysulfate-sulfuric acid
complex [86]. The absorbance of the formed yellow complex
was measured at a 410-nm wavelength and converted to
hydrogen peroxide concentration by a calibration curve
generated with stock solutions of hydrogen peroxide where
concentration was confirmed by titration with 0.1 N potassium
permanganate [86].
For GC-MS analysis, the three separate aqueous fractions
collected from the reactor were combined, extracted with chlo-
roform, and dried over sodium sulfate. The resulting extract
was then left open to the atmosphere for a period of time to
concentrate the products by solvent evaporation. The analysis
was performed on a Clarus 500 GC with an Elite-Wax column
length of 30 m and diameter size of 250 μm in conjunction
with a Clarus 550d MS (Perkin Elmer). Standards of the
identified products as well as the starting materials were used
to provide additional verification for the identified compounds.
WANDELL et al.: FORMATION OF ALCOHOLS AND CARBONYL COMPOUNDS 1199

For NMR analysis, successive extractions on the three

separate aqueous fractions collected from the reactor were per-
formed with deuterated chloroform and the resulting extracts
dried over sodium sulfate. Analysis of each individual fraction
was executed with a 600-MHz ultrashield (Bruker) where
an acquisition time of 1 h was used. Identification of the
product compounds was performed by comparing the chemical
shift and the multiplicity of key NMR signature peaks of
the particular compound to reference NMR spectra obtained
from the spectral database of organic compounds organized
by the National Institute of Advanced Industrial Science and
Technology, Japan. In most of the cases, the signature peaks
originated from functional groups bonded closely to the main
characteristic functional group, i.e., CH3 bonded to a carbonyl
group.
Fig. 4. Complete NMR-spectra of liquid effluent after extraction. The bottom
A quantitative analysis on the three liquid fractions collected spectrum represents the starting material (DI water and n-hexane). The top
was also performed with NMR by adding known concentra- spectrum represents the sample after subjection to plasma discharge.
tions of benzyl phenyl ether to the three separate extracts of the
aqueous phases. The integrated signals of all functional groups
of interest were then compared with the integrated singlet
signal of the benzyl phenyl ether CH2 -group at 5.05 ppm
to allow the back calculation of the concentration of each
compound.

IV. R ESULT
Fig. 4 shows an example NMR spectrum demonstrating
the presence of reaction products from n-hexane. In this
figure, the bottom spectrum represents the unreacted starting
material while the top spectrum represents the liquid effluent
from the reactor after extraction. Comparison of these clearly
shows the presence of both alcohol and ketone products in
the characteristic regions of the functional groups. The major
products and their relative ratios as identified with NMR
were 3-hexanol (26%), 2-hexanol (21%), 3-hexanone (17%)
and 2-hexanone (17%), 1-hexanol (11%), hexanal (8%).
A significant amount of unreacted n-hexane was also found.
Additionally, the NMR analysis also suggests the presence
of organic peroxides; however, they could not be reliable
assigned due to relatively low stability.
Fig. 5 shows a gas chromatogram of the reaction products
from n-hexane. As with the NMR analysis the main
products identified were 1-hexanol (4.95 min), 2-hexanol
(3.90 min), 3-hexanol (3.68 min), hexanal (2.81 min),
2-hexanone (2.81 min), and 3-hexanone (2.60 min). It should
be noted that separation of 2-hexanone from hexanal was
not achieved and the two compounds appear as one peak.
Furthermore, an additional peak appears at 4.52 min, which
could not been identified but may be accounted for by the
suggested presence of organic peroxides given in the NMR
analysis.
A similar analysis was performed to assess the products
generated when cyclohexane was used as the organic feedstock
instead of n-hexane. A comparison of the major product
distributions of the two experiments can be found in Table I.
When cyclohexane was used as the organic starting material
the major products identified and their relative distributions
were cyclohexanone (47%), cyclohexene (20%), cyclohexanol
Fig. 5. Complete gas chromatogram of liquid effluent after extraction and
solvent evaporation. Products identified are 1-hexanol (4.95 min), 2-hexanol
(3.90 min), 3-hexanol (3.68 min), hexanal (2.81 min), 2-hexanone (2.81 min),
and 3-hexanone (2.60 min).
(19%), hexanal (11%), and 2-cyclohexenone (2%). As with
the conversion of n-hexane, NMR analysis also suggests the
presence of organic peroxides (i.e., C6 H11 OOH) derived from
cyclohexane. In both experiments, only a small fraction of
the organic starting material was functionalized, 1.7% for
n-hexane and 2.0% for cyclohexane. While this is a small
fraction it should be noted that a large portion of the organic
starting material not accounted for in the form of functional-
ized products does not undergo further oxidation but instead
remains unreacted. This is evident from the significant amount
of unreacted organic feed detected in the NMR analysis;
unfortunately, accurate quantification of these compounds was
not possible due to the overlap of the compound’s NMR
signals with the NMR signals for the aliphatic parts of the
starting compounds. Nonetheless, a rough quantification was
determined showing approximately 10% of the n-hexane start-
ing material was collected and 22% for cyclohexane. It should
be noted that additional organic starting material was detected
in the gas effluent after passage through both cold traps,
and likely accounts for a large fraction of organic starting
material not collected, but could not be quantified with the
1200
TABLE I
M AJOR P RODUCT D ISTRIBUTION OF THE C OMPOUNDS F ORMED FROM n-H EXANE (T OP ) AND C YCLOHEXANE (B OTTOM ) AS W ELL AS P ERCENT
C ONVERSION , OVERALL P RODUCTION R ATE , AND E NERGY Y IELD . A LL VALUES P RESENTED A RE ON A P ER M OLE BASIS
instrumentation available. The fact that only a portion of the
starting material was chemically modified and that most of
the products generated were the result of only one or two
oxidative steps of the parent molecule indicates that our reactor
system provides soft activation, thus justifying the viability of
this setup for potential chemical synthesis routes in partial
oxidation of the alkanes.
When the distribution of products generated from the
oxidation of n-hexane is examined, the OH radical appears to
preferentially attack the C2 and C3 carbons of the n-hexane
molecule as indicated by the lower ratios of 1-hexanol and
hexanal in comparison with the ketones and secondary alco-
hols. This preferential attack is consistent with data reported
in the literature for oxygen plasma reactions with n-hexane in
DBD [17].
When the distribution of the products generated from the
oxidation of cyclohexane is examined, it is clear that reaction
selectivity is higher when compared with the oxidation of
n-hexane as evident from the large portion of cyclohexanone,
47%, found relative to the other products. The fact that there
is no distinction between carbons in the cyclohexane molecule
likely leads to this increase in selectivity. However, it is not
clear why the ketone product dominates when cyclohexane
is used while the alcohols dominate in the case of n-hexane.
IEEE TRANSACTIONS ON PLASMA SCIENCE, VOL. 42, NO. 5, MAY 2014
This result differs from those found when cyclohexane was
oxidized with oxygen in DBD where an almost equal ratio of
cyclohexanone to cyclohexanol was produced [17]. It should
additionally be pointed out that the generation of cyclohexene
is likely to result from the loss of hydrogen atom from
cyclohexyl radical. It known that β-C-H bond energy in the
alkyl radicals is nearly a factor of 3 smaller than that in
respective alkanes [87], [88]. Furthermore, this product was
not reported in the above-mentioned studies with oxygen
in DBD.
The overall production rate and energy yield for the major
products generated are also shown in Table I. The energy
yield for products generated from n-hexane was found to be
8.6 × 10−9 mol/J and 9.0 × 10−9 mol/J for cyclohexane.
These values are approximately an order of magnitude lower
than those found for the degradation of n-hexane and cyclo-
hexane by oxygen plasma reactions in DBD where the authors
reported 1.1 × 10−7 and 1.9 × 10−7 mol/J, respectively [17].
However, it should be noted that this does not represent the
total energy yield for all generated products because hydrogen
peroxide is also produced at an energy yield of 0.54 mol/kWh
(1.5 × 10−7 mol/J). Future efforts should be directed toward
capitalizing on the hydrogen peroxide generated, as it too has
a high oxidative potential.
WANDELL et al.: FORMATION OF ALCOHOLS AND CARBONYL COMPOUNDS 1201

TABLE II
I NDIVIDUAL P RODUCTION R ATES AND E NERGY Y IELDS FOR THE G ENERATED P RODUCTS P RODUCED AS W ELL AS THE R ELATIVE
D ISTRIBUTION OF W HERE THE P RODUCTS W ERE C OLLECTED . A LL VALUES P RESENTED A RE ON A P ER M OLE BASIS

Table II shows the individual production rates and energy
yields for all products generated in the experiments. This table
also provides a breakdown of where the generated products
were collected, i.e., the relative ratios of products in the three
separate liquid fractions, which were collected and extracted.
One of the more important generalizations of Table II is that
no n-hexane, cyclohexane, or cyclohexene was detected in the
liquid effluent collection vessel and conversely no hydrogen
peroxide was detected in either the primary or secondary cold
trap. This result can be explained by the vastly different vapor
pressures and water solubility of these organic compounds
compared with hydrogen peroxide, in that the high water
solubility of hydrogen peroxide as well its relativity low vapor
pressure allow the product to be rapidly dissolved into the
liquid water phase leaving no detectable amounts vaporized in
the flowing argon gas. In contrast, the high volatility and low
solubility in water of n-hexane, cyclohexane, and cyclohexene
hinders them from dissolving into the liquid effluent making
these compounds difficult to collect. As previously mentioned,
it is likely a significant amount of these volatile compounds is
still present in the gas effluent of the secondary cold trap. This
result demonstrates the importance of the relative chemical
properties of the products of interest to those of the liquid
absorbent, which is in this case water. Because the volatility
and solubility of the other major products lies between the
extremes of the previously mentioned organic compounds and
hydrogen peroxide, these compounds are collected in both the
liquid effluent and cold traps. As a result, it is reasonable to
conclude that almost all of the hydrogen peroxide produced
in the reactor is collected but a portion of the other organic
products generated as well as a large amount of unreacted
starting material may remain vaporized in the argon gas even
after subjection to two cold traps. Our future experiments will
determine whether it is possible to improve overall yield by
choosing a parent compound whose oxidative products are
more soluble in water and less volatile.
Additional experiments were conducted to determine the
radical scavenging potential of increasing amounts of organic
1202
Fig. 6. (a) Mean discharge power and (b) production rate of hydrogen
peroxide for various n-hexane to water feed ratios. Water flow rate held
constant at 0.5 mL/min while the organic flow rate was varied from 0 to
0.002, 0.005, 0.01, 0.02, and 0.04 mL/min.
starting material to assess the impact on the production rate
of hydrogen peroxide. In these experiments, the water flow
rate was held constant at 0.5 mL/min while the n-hexane
flow rate was varied from 0 to 0.002, 0.005, 0.01, 0.02, and
0.04 mL/min. The values for hydrogen peroxide production
rate as well as the discharge power under these conditions are
shown in Fig. 6(a) and (b).
Fig. 6(a) shows that as the amount of n-hexane added to
the reactor was increased, the power of the discharge also
increased. Fig. 6(b) shows the production rate of hydrogen
peroxide increased from the case with pure water when only
a very small amount of n-hexane (0.002–0.005 mL/min) was
added to the reactant feed. This increase can be explained
by the slight increase in power that occurred when the
n-hexane was added to the gas phase. The result also shows
that when only a small amount of n-hexane is added to the
reactant feed the hydroxyl radical reactions with the organic
compounds do not affect the hydrogen peroxide formation rate.
When this experiment was performed with cyclohexane as the
organic starting material almost identical trends were found. It
is possible that the hydroxyl radical reactions, which produce
the hydrogen peroxide, occur very close to the liquid-gas
interface, and thus are unaffected by gas phase organic radical
scavengers at low enough concentration. This hypothesis is
supported by the fact that when the ratio of organic to
water was increased further, the production rate of hydrogen
peroxide decreased even though the discharge power continued
to increase. A similar finding, whereby increasing radical
probe concentration reduced hydrogen peroxide formation,
was found in a pulsed corona discharge directly in liquid
water [89].
IEEE TRANSACTIONS ON PLASMA SCIENCE, VOL. 42, NO. 5, MAY 2014
This relatively large production rate of hydrogen peroxide in
combination with the production of alcohols and ketones sug-
gests that further work with catalysts that promote hydrogen
peroxide reactions with the organic compounds could increase
the synthetic utility of plasma-mediated organic transforma-
tions. However, it is also important to note that the formation
of hydrogen peroxide by the hydroxyl radicals may also serve
to limit the over oxidation of the organic compounds.
Last, there was no visual evidence of polymerization
products in this experiments further justifying that over oxi-
dation was prevented. However, additional analysis of the
gas effluent is necessary to determine if there is indeed
additional product still vaporized in the argon and to quantify
the remaining starting material in this phase to close the mass
balance.
V. C ONCLUSION
The results of this paper clearly show that chemical
synthesis by oxidation with hydroxyl radicals is possible with
the reactor system described in this paper. Significant amounts
of alcohol, ketone, and aldehyde products were produced
from both n-hexane and cyclohexane after attack on the
molecules by hydroxyl radicals produced from the liquid water
phase contacting the plasma. This paper also proves that
some selectivity of the reaction products can be gained by
the choice of a parent compound, and also suggests that it
may be possible to further control selectivity with alterations
to such experimental conditions as water flow rate, organic
to water feed ratio, reactor pressure, and pulse parameters.
Additionally, substantial amounts of hydrogen peroxide were
also produced despite the addition of the organic compounds
to the reactor feed, which have been shown to act as gas phase
radical scavengers at high enough concentrations. It was also
found that the selection of a parent compound, which yields
chemical species with a low volatility and a high solubility in
water upon oxidation could make collection of the generated
products easier and increase the overall yield of the process.
Finally, due to the high concentration of hydrogen peroxide
produced in conjunction with the other major functionalized
products, additional work is warranted to capitalize on this
aspect of the system.
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Robert J. Wandell received the B.S. degree in
chemical engineering from Florida State University,
Tallahassee, FL, USA, where he is currently pursu-
ing the Ph.D. degree in chemical engineering.
He has a significant interest in the transfer of
university technologies to commercial markets. His
current research interests include the study and
development of electrical discharge plasma reactors
for the synthesis of useful chemical species.
WANDELL et al.: FORMATION OF ALCOHOLS AND CARBONYL COMPOUNDS 1205

Stefan Bresch received the Diplom-Physiker degree
in physics from the University of Magdeburg,
Magdeburg, Germany. He is currently pursuing the
Ph.D. degree in organic chemistry with Florida State
University, Tallahassee, FL, USA.
His current research interests include electrical
discharge plasma chemistry, structural organic chem-
istry, and general physics.
Kevin Hsieh received the B.S. degree in chemistry
from the Georgia Institute of Technology, Atlanta,
GA, USA, and the M.S. degree in chemistry from
Florida State University, Tallahassee, FL, USA,
where he is currently pursuing the Ph.D. degree in
chemical engineering degree.
His current research interests include gliding-
arc electrical discharge plasma for environmental,
energy, and materials synthesis applications.
Bruce R. Locke (M’99–SM’08) received the B.S.
degree in chemical engineering and environmental
and water resources engineering from Vanderbilt
University, Nashville, TN, USA, the M.S. degree
in chemical engineering from the University of
Houston, Houston, TX, USA, and the Ph.D. degree
from North Carolina State University, Raleigh, NC,
USA.
He is a Professor and Chairman with the Depart-
ment of Chemical and Biomedical Engineering,
Florida State University, Tallahassee, FL, USA. He
is a Distinguished University Research Professor with Florida State University.
He has published over 115 peer-reviewed journal papers. He is involved in
networks of chemical reactions coupled with diffusion and convection in
bioreactors, tissue engineering, and other bioengineering applications. His
current research interests include the development and analysis of electrical
discharge plasma reactors for initiating chemical reactions in air and water
pollution control, green chemistry, and disinfection.
Dr. Locke is a member of the American Institute of Chemical Engineers
and the American Chemical Society.

Igor V. Alabugin received the B.S. and Ph.D.

degrees in chemistry from Moscow State University,
Moscow, Russia.
He joined the Department of Chemistry and Bio-
chemistry, Florida State University, Tallahassee, FL,
USA, in 2000, where he is currently a Professor,
after his post-doctoral research with the University
of Wisconsin-Madison, Madison, WI, USA. His
current research interests include theoretical and
experimental organic chemistry with biochemistry
and materials science, electronic and conformational
control of organic reactions, design of new radical transformations includ-
ing electrical discharge plasma reactions, construction of precisely cut and
functionalized graphene nanoribbons, development photochemical double-
stranded DNA cleavage agents with built-in selectivity to cancer cells,
pH-gated biological processes, and the study and application of stereoelec-
tronic effects in chemistry.