ARTICLE

pubs.acs.org/EF

Advanced Distillation Curve Analysis on Ethyl Levulinate as a

Diesel Fuel Oxygenate and a Hybrid Biodiesel Fuel
Bret C. Windom,† Tara M. Lovestead,† Mark Mascal,‡ Edward B. Nikitin,‡ and Thomas J. Bruno*,†
†
Thermophysical Properties Division, National Institute of Standards and Technology, Boulder, Colorado 80305, United States
‡
Department of Chemistry, University of California Davis, Davis, California 95616, United States

ABSTRACT: Recently, a new processing technique was developed that converts the carbohydrates found in plant biomass into
ethyl levulinate, which has properties making it a possible diesel fuel oxygenate additive. Additionally, the new processing technique
applied to oil-containing seeds can create a biodiesel fuel at high yields, while possibly enhancing the cold flow properties that
commonly plague biodiesel fuels. The first part of this two-part study focused on ethyl levulinate as a possible diesel fuel oxygenate
additive, by investigating the volatility of petroleum diesel/ethyl levulinate mixtures. Volatility was measured with the advanced
distillation curve (ADC) method for mixtures containing 1, 2.5, 5, 10, and 20% ethyl levulinate (v/v) and compared with unblended
petroleum diesel fuel. In addition, the concentration of ethyl levulinate was tracked during the distillation for each mixture by use of
the composition explicit data channel. The second part of this study investigated fatty acid
levulinate ester biodiesel fuel blends as
viable petroleum diesel fuel extenders/replacements. This was done by measuring their volatilities and comparing them to a
commercially available biodiesel fuel, and also to a petroleum diesel fuel. In addition, distillate fractions were withdrawn to measure
the changing composition and energy content during the distillation of the fatty acid
levulinate ester biodiesel blends and
commercial biodiesel fuel.

’ INTRODUCTION conditions.14
17 Indeed, the high lubricity is particularly helpful

Diminishing petroleum reserves, the potential of supply dis-
ruptions, and price volatility, as well as environmental considera-
tions resulting from polluting emissions, have led to development
of alternative liquid fuels and fuel additives produced from
renewable feedstocks. For example, bioderived diesel fuels have
shown promise as extenders for diesel fuels. Compared to gaso-
line engines, diesel engines have higher efficiencies, requiring less
fuel for equivalent work, have longer working lifetimes, and
produce less carbon monoxide emissions. On the other hand, a
primary concern regarding the diesel engine is the high soot and
NOx emissions, and the subsequent environmental impact.
Currently, there are numerous research efforts to develop solu-
tions to these problems, including engine and system modifica-
tions as well as the development and reformulation of diesel
fuels.1
7 For example, many studies have focused on investigating
oxygenates and their effect on soot reduction as well as their effect
on the overall performance of the fuel.3
5,8
11 In fact, it has been
shown that completely smoke-free operation can be obtained
when 38% (mass/mass) oxygen is incorporated into the diesel
fuel.12 We note that a formulation of fuel to include this amount of
oxygen would not be cost-effective and would lead to increased
fuel consumption; however, this figure does show the importance
of oxygen in reducing soot emission. Unfortunately, many of the
oxygenate additives investigated are petroleum derived, while
others are very expensive and energy intensive to produce.
Biodiesel fuel has many favorable properties as a possible
renewable extender for petroleum diesel fuel.13 In addition to its
renewability, other advantages of biodiesel include biodegrad-
ability, miscibility with petroleum diesel, increased lubricity, high
flash point, and reduced emissions of particulate matter, unburned
hydrocarbons, and carbon monoxide during fully warmed-up
since the trend toward ultra low sulfur diesel fuel (ULSD) has
proven problematic in this regard.17
19 On the other hand, some
of the known problems with biodiesel fuel include thermal and
oxidative instability, poor low temperature flow properties
(higher cloud point), increase in NOx emissions, increased
fuel consumption due to lower net heat of combustion, and
increased unburned fuel and carbon monoxide emissions
under cold start conditions.20
26 A number of feedstocks are
currently used to produce oils that can be processed into
biodiesel fuel.27
36 Soybean, palm, rapeseed, sunflower seed,
coconut, peanut, cottonseed oils, jatropha, algae, and cuphea
seeds along with animal fats and waste oils are just a few of the
feedstocks sources that have been proven technologically viable,
although not necessarily economical.27
32 Typically, the feed-
stock that is selected depends on the crop economics, geography,
climate, and crop availability.32 Because of the small oil yield
extracted from plant sources, however, a great deal of crop
feedstock is needed for commercialization of biodiesel fuel. This
requires large areas of land, and can result in competition with
food crops. For these reasons, many scientists are looking for
crop sources and new processing techniques that result in higher
yields of fuel while requiring less land.
Recently, a new process has been developed to convert
carbohydrates found in raw biomass (cotton, wood, straw, other
plant materials, and even newsprint) into simple organic mol-
ecules that may be further processed into either fuel or fuel
additives.37 This technology uses a biphasic acid/solvent biomass
Received: February 15, 2011
Revised: March 10, 2011
Published: March 10, 2011

r 2011 American Chemical Society 1878 dx.doi.org/10.1021/ef200239x | Energy Fuels 2011, 25, 1878–1890
Energy & Fuels
Table 1. Data on the Additive Studied in This Work91
a fuel) and ethyl levulinate. The transesterfication of the triglycer-
ethyl levulinate :
CAS No. 539-88-8
INChI = 1S/C7H12O3/c1-3-10-7(9)5-4-6(2)8/h3-5H2,1-2H3
RMM = 144.1684
Tboil = 205.8 °C
Tfus =
32.8 °C
density = 1.00831 g/mL (25 °C)
refractive index, Nad = 1.4225 (20 °C)
flash point: 90.6 °C (TCC)
ΔHcomb =
3523 kJ/mol
a
Synonyms: Pentanoic acid, 4-oxo-, ethyl ester; Levulinic acid, ethyl
ester; Ethyl laevulinate; Ethyl levulate; Ethyl 3-acetylpropionate; Ethyl
4-ketovalerate; Ethyl 4-oxopentanoate; Ethyl 4-oxovalerate; ELA; Ethyl
ketovalerate.
digester to convert the carbohydrates (mono, di, or poly
saccharides) into a mixture of 5-(chloromethyl)furfural (CMF)
and levulinic acid in combined yields up to 95% (generally
70
90% CMF and less than 10% levulinic acid). By use of a
suitable alcohol post-treatment, the CMF/levulinic acid mixture
can be converted into levulinate esters. Ethyl levulinate contains
∼14% (mol/mol) oxygen and properties enabling it to be a viable
bioderived petroleum diesel fuel oxygenate additive. Some prop-
erties of ethyl levulinate are provided in Table 1. We note that
these properties include a high flash point (90 °C), a normal
boiling temperature (206 °C) similar to the initial boiling
temperature of typical diesel fuel, and a higher energy content
compared to that of many other oxygenate candidates. Prelimin-
ary tests have even shown that ethyl levulinate as an oxygenate can
be blended with petroleum diesel up to 10% without a change in
the cetane number.38 In addition, the same tests have shown that
ethyl levulinate enhances the lubricity of the diesel fuel. We note
that these results are encouraging for use of this material as a diesel
blending component, but considerable additional data and testing
are needed. Specifically, it must be shown that ethyl levulinate

diesel blends are stable in the presence of water, and that ethyl
levulinate is compatible with fuel system materials. In addition,
engine performance and emissions data are also required.
As a follow up study, the new carbohydrate conversion tech-
nique was applied to oil-containing seeds effectively increasing the
yield in biodiesel production.39 During the typical production of a
biodiesel fuel from a plant source, the oils are extracted and
converted from triglycerides into single chain fatty acid esters.
This is done by transesterification, in which an alcohol, typically
methanol or ethanol, is mixed with the triglycerides and an acid or
base catalyst, resulting in glycerol and three monoalkyl esters.
Applying the biphasic acid/solvent biomass digester mentioned
earlier, the carbohydrates found in the seeds can be converted into
CMF and levulinic acid while simultaneously extracting the oils
from the seeds.39 Following an ethanol treatment at 200 °C for 6 h,
the CMF/triglyceride mixture can be converted into a mixture
1879
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of fatty acid ethyl esters (FAEEs, commonly found in biodiesel
ides is catalyzed as a result of the in situ production of the
catalytic acid produced during the ethanolysis of the CMF. The
above process, when carried out on the seeds of the safflower
plant, yields a 24% increase in fuel production when compared to
standard transesterfication of the available oil from equal masses
of feedstock.39 It is conceivable that if the carbohydrates found in
the entire plant were processed (leaves, stalks, and seeds), an
even greater yield of the levulinate component of the fuel could
be achieved. As an added benefit, the high concentration of the
ethyl levulinate in the safflower biodiesel fuel blend is a possible
approach to enhance the cold flow properties associated with
biodiesel fuel and reduce the associated performance and emis-
sion problems that can occur at low temperatures.39 In contrast,
the majority of feedstocks currently used for biodiesel fuel
production produce long carbon chain fatty acid esters, specifi-
cally unsaturated fatty acid esters, that are responsible for the
poor cold flow properties. Oil seed biodiesel fuel blends pro-
duced in the manner described above contain many of these same
fatty acid esters. The blends also contain a large amount of ethyl
levulinate which has a lower melting and boiling temperature
than those of any of the FAEEs. We should note that the
influence of the ethyl levulinate on the oxidative stability of the
FAEEs has not been investigated and is unknown at this time.
Reliable measurements of the thermophysical properties of
both the biodiesel fuel blend and the ethyl levulinate oxygenate
will aid in better understanding how the fuel will perform, and
help determine the optimal conditions for peak performance.
The first part of the work presented here focuses on ethyl
levulinate as a potential oxygenate additive for petroleum derived
diesel fuel. Specifically, we measure the volatility (as an approx-
imation of vapor/liquid equilibrium) of mixtures of diesel fuel
with ethyl levulinate. The second part of this study investigates
fatty acid
levulinate ester biodiesel blends by accurately mea-
suring their volatility and comparing it to that of a commercially
available soy-based biodiesel fuel. These two families of fluids are
linked by the common carbohydrate conversion processing
technique discussed above. Each has a different purpose, how-
ever, and thus for the remainder of this paper they will be
addressed separately.
Advanced Distillation Curve Measurement. One of the
most important and informative thermophysical properties that
is measured for complex fluid mixtures is the distillation (or
boiling) curve.40
42 Simply stated, the distillation curve is a
graphical depiction of the boiling temperature of a fluid or fluid
mixture plotted against the volume fraction distilled. Distillation
curves are typically associated with petrochemicals and petroleum
refining.43 Such curves are of great value in assessing the proper-
ties of any complex fluid mixture; indeed, the distillation curve is
one of the few properties that can be used to characterize a
complex fluid by providing an approximation of the vapor/liquid
equilibrium. Thus, distillation curves are used commonly in the
design, operation, and specification of liquid fuels such as gasoline,
diesel fuel, rocket propellant, and gas turbine fuel.44
46
The standard test method for the measurement of the
distillation curve, ASTM D-86, provides the usual approach,
yielding the initial boiling point, the temperature at predeter-
mined distillate volume fractions, and the final boiling point.47
The ASTM D-86 test suffers however from several drawbacks,
including large uncertainties in temperature measurements and
little theoretical significance.48
dx.doi.org/10.1021/ef200239x |Energy Fuels 2011, 25, 1878–1890
Energy & Fuels
In earlier work, we described an improved method and appa-
ratus for distillation curve measurement that is especially applic-
able to the characterization of fuels.48
55 This method, called the
advanced distillation curve (ADC), is a significant improvement
over current approaches such as ASTM D-86. First, we incorporate
a composition-explicit data channel for each distillate fraction (for
qualitative, quantitative, and trace analysis). Sampling very small
distillate volumes (5
25 μL) yields a composition-explicit data
channel with nearly instantaneous composition measurements.
Chemical analysis of the distillate fractions allows for determina-
tion of how the composition of the fluid varies with volume
fraction and distillation temperature, even for complex fluids.
These data can be used to approximate vapor
liquid equilibrium
(volatility) of complex mixtures and presents a more complete
picture of the fluid under study. The ADC approach provides
consistency with historical data, an assessment of the energy
content of each distillate fraction and, where needed, a corrosivity
assessment of each distillate fraction. Suitable analytical techniques
include gas chromatography with either flame ionization detection
(GC-FID) or mass spectral detection (GC-MS), element specific
detection (such as GC with sulfur or nitrogen chemiluminescence
detection, GC-SCD or GC-NCD), and Fourier-transform infrared
spectrophotometry (FTIR).56,57
Another advantage of the ADC approach is that it provides
temperature, volume, and pressure measurements of low uncer-
tainty, and the temperatures obtained are true thermodynamic
state points that can be modeled with an equation of state.58
62
Such thermodynamic model development is simply impossible
with the classical approach to distillation curve measurement. We
have applied this metrology to hydrocarbon mixtures, azeotropic
mixtures, gasolines, diesel fuels (including biodiesel fuels), crude
oils, aviation fuels, and rocket propellants.48
52,54
57,63
82
The ADC method was applied to each of the two families of
fluids (the petroleum diesel fuel/ethyl levulinate mixtures and
the fatty acid
levulinate ester biodiesel blends). Thermodyna-
mically consistent distillation curves were measured for mixtures
of petroleum diesel fuel and ethyl levulinate at varying concen-
trations. The composition-explicit data channel was used to track
the amount of ethyl levulinate during the distillation of the
mixtures. These measurements show the changes in thermo-
physical properties that can be expected when varying concen-
trations of ethyl levulinate are added to petroleum diesel fuel,
which is important when considering a new oxygenate additive.
Thermodynamically consistent distillation curves were measured
for the fatty acid
levulinate ester biodiesel blends while the
composition-explicit data channel was used to characterize
the curve in terms of composition and available energy content.
The results following the ADC analysis of the fatty acid
levu-
linate ester biodiesel blends were compared to results from a
previously measured commercially available soy-based biodiesel
fuel.52 Thus, we provide a basis of comparison among these
fuels in terms of the fundamental thermophysical properties.
This comparison is critical in determining the applicability and
suitability of the fatty acid
levulinate ester biodiesel blends for
use as renewable replacements or extenders for petroleum
diesel fuel.
’ EXPERIMENTAL SECTION
1. Materials. 1.1. Study of Ethyl Levulinate as an Oxygenate. The
diesel fuel used in this work was obtained from a commercial source and
was stored in a tightly sealed container to preserve any volatile
1880
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components. The fuel was a summer grade, low wax, ULSD fuel that
incorporated a red dye (specifying off-road use), and was refined locally
from petroleum of the Denver-Julesburg field. This fluid was used
without any purification or modification. The composition was studied
with a gas chromatographic method (30-m capillary column of 5%
phenyl
95%-dimethyl polysiloxane having a thickness of 1 μm, tem-
perature program from 90 to 275 °C, 9 °C per minute) using flame
ionization detection and mass spectrometric detection.83
85 This anal-
ysis was unremarkable in that the typical pattern of commercial petro-
leum derived diesel fuel was observed.
The n-hexane used as the solvent in this work was obtained from a
commercial supplier. Prior to use, the n-hexane was analyzed by gas
chromatography (same column as above, temperature program from 50
to 170 °C, 5 °C per minute) by use of flame ionization detection and mass
spectrometric detection. These analyses revealed the purity to be
approximately 99.9% (mass/mass), and the fluids were used without
further purification.
The ethyl levulinate used in the diesel oxygenate study was obtained as
a pure fluid from a commercial source. It was a reagent grade fluid with
reported purities of 98
99% (mass/mass). This fluid was analyzed with
chromatographic methods confirming that the purity of the fluid was in
fact higher than specified. Ethyl levulinate and ULSD mixtures were
prepared as stock solutions of 1, 2.5, 5, 10 and 20% oxygenate by volume.
This ensured that there were no variations in composition among
measurements done with each mixture. It should be noted that the
solubility limit, indicated by the onset of phase separation, was measured
to be approximately 16% (v/v) ethyl levulinate in ULSD at room
temperature (23 °C). No phase separation was noticed in the 20%
mixture at 35 °C, therefore, the 20% mixture was made up in the
distillation flask allowing the heating and stirring during the distillation
measurements to dissolve the ethyl levulinate into the ULSD. As we will
describe later, the marginal miscibility of the 20% mixture affected our
ability to characterize the distillate composition of this mixture. The
miscibility issues need to be further investigated, more specifically, in
terms of what minor impurities (i.e., water) and conditions (i.e.,
temperature) may trigger phase separations at lower blend levels.
Some discussion is warranted regarding our choice of mixture ratios.
Mixtures that contain 20% (v/v) of a given oxygenate additive might not
be practical fuels for all circumstances, and the performance of an engine
using such a mixture could potentially be poor. Even when high
concentrations of oxygenates are workable or even advantageous, they
may not be economically viable. Our study of a particular mixture ratio
does not imply that mixtures with very high oxygenate concentrations are
practical formulations for fuels, nor that we advocate such as mixtures for
use as fuels. Rather, our mixtures were chosen to cover as large a range of
composition as practical for the purpose of modeling the results with
equations of state. Likewise, our reason for the use of reagent grade
oxygenating fluids rather than the technical grade fluids that might be
used industrially speaks to the same issue.
1.2. Study of the Fatty Acid
Levulinate Ester Biodiesel Fuel. The
acetone used as a solvent in this work was obtained from a commercial
supplier, and was analyzed by gas chromatography (same column
described above, temperature program from 50 to 170 °C at a heating
rate of 5 °C per minute) with flame ionization and mass spectrometric
detection. These analyses revealed the purity to be approximately 99%,
and the fluid was used without further purification.
Two batches of the safflower fatty acid
levulinate ester biodiesel
blend (FLBB) produced with two different compositions were analyzed
in this study. The commercial biodiesel fuel (B100) chosen for
comparison to these two FLBBs was produced from a soybean feedstock
via a traditional transesterification processing using methanol. The
biodiesel fuel samples were stored tightly sealed in plastic bottles, and
care was taken to minimize exposure to the atmosphere to limit
oxidation, evaporation of the more volatile components, and the uptake
dx.doi.org/10.1021/ef200239x |Energy Fuels 2011, 25, 1878–1890
Energy & Fuels
of moisture. No other precautions were taken, nor were the samples
physically or chemically dried.
The biodiesel fuel blends were subjected to chemical analysis before
the measurement of the distillation curve. They were analyzed with GC-
MS in scanning mode with a 30-m capillary column with a 0.1-mm
coating of the stationary phase, 50% cyanopropyl
50% dimethyl poly-
siloxane. This stationary phase provides separations primarily based upon
polarity and is specifically intended for the analysis of fatty acid ester
compounds that make up biodiesel fuels.69 Samples were injected with a
syringe into a split/splitless injector set with a 50 to 1 split ratio. The
injector was operated at a temperature of 300 °C and a constant head
pressure of 82.7 kPa (12 psig). A temperature program of 80 °C for 2 min
followed by temperature ramping at 8 °C per minute to 225 °C was used.
The temperature was then held at 225 °C for 5 min. Mass spectra were
collected for each peak from 15 to 550 relative molecular mass (RMM)
units. Peaks were identified with guidance from the NIST/EPA/NIH
Mass Spectral Database,83 and also on the basis of retention indices.
2. Distillation Curve Measurements. The method and appara-
tus for ADC measurements has been reviewed in detail elsewhere,48
52
and thus only a limited description of a typical measurement is provided
herein. In brief, 200 mL of each sample fuel (either the FLBB or the
ULSD/ethyl levulinate mixture) was placed into the boiling flask with a
200 mL volumetric pipet (equipped with an automatic pipet) for each
distillation curve measurement. Thermocouples were then inserted into
the proper locations to monitor Tk, the temperature in the fluid, and Th,
the temperature at the bottom of the takeoff position in the distillation
head. Enclosure heating was then commenced with a four-step program
based upon a previously measured distillation curve and knowledge of
the neat sample composition.29 Volume measurements were made in a
level-stabilized receiver, and sample aliquots were collected at the
receiver adapter hammock. Due to the oxidative instabilities of the fatty
acid esters in the biodiesel fuels, an argon sparge was used to remove and
exclude air from the apparatus during their distillations. This procedure
has been described in detail elsewhere and shown to give highly
reproducible distillation curve results.29,69,81 In short, a capillary inserted
into the biodiesel sample contained inside the kettle bubbled ∼5 mL/
min of argon into the sample for ∼20 min prior to heating. Once heating
began, the sparge tube was removed from the fluid (to avoid affecting the
fluid temperature during the distillation) and positioned directly above
the boiling fluid. An argon purge of the atmosphere above the fluid was
maintained throughout the distillation at a flow rate of 5 mL/min. This
flow rate has no measurable effect on the observed temperatures.
Because the measurements of the distillation curves were performed
at an elevation of ∼1650 m resulting in an ambient atmospheric pressure
of ∼83 kPa (measured with an electronic barometer), temperature
readings were adjusted for what should be obtained at standard atmo-
spheric pressure (1 atm =101.325 kPa). This adjustment was done with
the modified Sydney Young equation, in which the constant term was
assigned a value of 0.000109.86
88 This value corresponds to a carbon
chain of 12. In the chemical analysis of the ULSD sample, as well as in
previous work on diesel fuel, it was found that n-dodecane can indeed
represent the fluid as a very rough surrogate, not accounting for the
presence of the oxygenate additive. Clearly, biodiesel fuel is better
represented by a hydrocarbon chain length greater than 12. We chose
not to use a predicted value for the constant term (for a larger chain) in
our data presentation in order to be consistent with previous measure-
ments, and with measurements on ULSD. We note, however, that for a
carbon chain of 18, the predicted constant would be 0.000095; use of this
value (in place of that for a chain length of 12) would lower the
presented temperatures uniformly by 1.2 °C. The shapes of the
distillation curves would be unchanged. The magnitude of the Sydney
Young correction depends on the extent of the deviation from standard
atmospheric pressure. The pressure adjustment resulted in a typical
temperature adjustment of ∼8 °C. The actual measured temperatures
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Table 2. Comparison of the Initial Boiling Conditions of the
Ethyl Levulinate/ULSD Mixturesa
sample (pressure) (kPa) vapor rise (° C) first drop (° C)
1% (83.1) 215.4 216.0
2.5% (83.5) 212.9 213.4
5% (83.7) 210.0 210.4
10% (83.6) 202.6 203.3
20% (83.5) 199.6 197.0
ULSD (83.9) 217.6 217.9
a
The vapor rise temperature is the initial boiling temperature (IBT) of
the mixture. These temperatures have been corrected to 1 atm (101.325
kPa) with the Sydney Young equation. The pressures at which the
measurements were made are provided in the first column to permit
recovery of the actual measured temperature. The uncertainties are
discussed in the text.
are easily recovered from the Sydney Young equation at each measured
atmospheric pressure which is reported for every measurement through-
out this work.
To provide the composition channel information to accompany the
temperature data grid on the distillation curves, sample aliquots were
withdrawn for selected distillate volume fractions. To accomplish this,
aliquots of ∼7 μL of emergent fluid were withdrawn from the sampling
hammock in the receiver adapter with a blunt-tipped chromatographic
syringe and added to a crimp-sealed vial containing a known mass
(∼1 mL) of solvent (hexane for the oxygenate study and acetone for the
biodiesel fuel). Distillate samples were withdrawn at the first drop of
fluid from the condenser and then at each of 11 additional volume
fractions of distillate, for a total of 12 sample aliquots. Each distillate
volume aliquot underwent two analyses. First, each aliquot was sub-
jected to chemical analysis and peak identification by GC-MS as
described above for the analyses of the neat samples. Once the
compounds in each aliquot were identified, the aliquots were analyzed
with GC-FID with external standards to determine the compound
concentrations.83
85 The quantitative GC-FID analyses were per-
formed by injecting 3 μL of the solvent/sample mixtures from the
crimp-sealed vials into the chromatograph with an automatic sampler.
High-purity nitrogen was used as the carrier and makeup gas. The split/
splitless injection inlet was maintained at 300.0 °C, and the detector was
maintained at 275.0 °C for all the analyses performed with the GC-FID.
The column and temperature programs used were identical to those of
the GC-MS analyses previously discussed. The GC-FID analysis was
applied to the oxygenate study so that we could quantitatively track the
concentration of the ethyl levulinate during the distillation. For the
biodiesel blends, following standardization, the GC-FID results allowed
us to quantitatively determine the composition of each distillate fraction.
By knowing the distillate composition, the enthalpy of combustion for
each distillate fraction was determined in a process that has been
described in detail in previous work.54
’ RESULTS AND DISCUSSION
1. Study of Ethyl Levulinate as an Oxygenate. The initial
boiling behavior as described by the vapor rise temperature and
the temperature of the first drop of condensate from the
condenser for the ethyl levulinate/ULSD mixtures is provided
in Table 2. All temperatures are corrected to standard atmo-
spheric temperature using the modified Sydney Young equa-
tion, discussed above. The temperatures provided in Table 2
represent an average of three separate measurements. All
the temperatures recorded in Table 2 have uncertainties
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Energy & Fuels ARTICLE

Table 3. Representative Distillation Curve Data (Given As the Average of Two Distillation Curves) for Mixtures of Diesel Fuel
with Ethyl Levulinate Additive in 1, 2.5, 5, 10, and 20% (v/v) Concentrationsa
1% (83.1 kPa) 2.5% (83.5 kPa) 5% (83.7 kPa) 10% (83.6 kPa) 20% (83.9 kPa) ULSD (83.9 kPa)
distillate volume fraction (%) Tk (° C) Tk (° C) Tk (° C) Tk (° C) Tk (° C) Tk (° C)

5 223.1 220.2 216.8 210.6 205.5 225.5

10 228.3 225.0 221.2 214.4 207.9 230.1
15 233.7 231.0 226.6 218.4 210.7 235.4
20 239.5 236.5 232.4 222.7 213.7 240.9
25 244.7 242.1 238.0 228.1 217.3 245.9
30 250.1 247.9 244.5 234.2 221.6 251.2
35 255.7 253.7 251.0 240.8 226.7 256.5
40 261.4 259.6 257.6 248.0 234.1 261.9
45 268.0 266.5 264.9 256.0 245.5 268.2
50 273.9 272.3 271.1 264.3 257.2 273.8
55 280.1 278.9 277.9 272.4 269.1 280.2
60 287.3 286.3 285.0 281.0 279.3 287.1
65 294.4 294.1 292.3 289.0 287.7 294.3
70 302.4 302.0 300.2 298.7 296.3 301.6
75 310.6 310.7 309.0 305.9 306.8 310.0
80 320.0 319.9 317.9 316.6 317.3 319.2
85 330.1 330.0 328.7 327.5 329.4 328.9
a
Data for the neat diesel fuel are also provided. The uncertainties are discussed in the text. These temperatures have been corrected to 1 atm with the
Sydney Young equation.

Figure 1. Distillation curves of diesel fuel with 1, 2.5, 5, 10, and 20% (v/v) ethyl levulinate. Also include is the distillation curve measured for the neat
ULSD. Here we present Tk, the temperature measured directly in the fluid. The hashes along the y-axis represent the initial boiling temperature (IBT) of
the fluid. The uncertainties are discussed in the text.

(expressed as the average standard deviation for each volume
fraction) less than 0.6 °C. The vapor rise temperature repre-
sents the initial boiling temperature (IBT) of the fluid and is
marked by the rapid increase in the head temperature (Th) as
the vapor begins to travel out of the kettle and into the
distillation head. The boiling temperature of ethyl levulinate,
at 205.8 °C, is less than the IBT (indicated by the vapor rise
temperature) of neat ULSD. The addition of ethyl levulinate
lowers the IBT and has greater affect as its concentration is
increased.
The distillation curve data for the 1, 2.5, 5, 10 and 20% (v/v)
ethyl levulinate in ULSD are provided in Table 3 and presented
graphically in Figure 1. The results from a neat ULSD are also
presented. The data are presented in Tk (fluid temperature
measured directly). The Tk values represent the true thermo-
dynamic state point (the temperature of the mixture itself).

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Energy & Fuels ARTICLE

Figure 2. Histogram plot showing the results of the quantitative analysis for ethyl levulinate as a function of distillate volume fraction for the four starting
mixtures in ULSD (1, 2.5, 5, and 10% ethyl levulinate in diesel fuel). There is no detectable ethyl levulinate in any mixture after the 60% distillate cut. The
analysis of the 20% ethyl levulinate mixture is not presented in the above figure for reasons explained in the text.

Figure 3. Representative chromatograms of the neat fatty acid
levulinate ester biodiesel fuel blends. The y-axes are arbitrary units of intensity, and the
x-axes are retention time (RT) in min. The details of the chromatography are discussed in the text.

The data in Table 3 and Figure 1 are the average of between two
and five separate measurements performed for each fluid mix-
ture. The uncertainty in the temperature measurements was less
than 0.4 °C, and the uncertainty in the volume measurements
was 0.05 mL (expressed as the standard deviation among the
replicate curves). The ethyl levulinate has the greatest influence
on the boiling temperatures of the early distillate fractions. As
represented in Figure 1, the distillation curves deviate further
from the ULSD curve as the ethyl levulinate concentration is
increased. The shapes of the distillation curves, especially for the
higher concentration ethyl levulinate mixtures, provide a better
understanding of the evolving composition of the mixtures as the
vaporization progresses. For example, the 20% ethyl levulinate
mixture is initially flat because it is ethyl levulinate that is
primarily being vaporized. This results in the greatest deviation
from the ULSD curve at the 35% volume fraction. Following the
35% volume fraction, the slope of the curve begins to increase as
the heavier components making up the diesel fuel begin to
volatize. The 20% ethyl levulinate mixture does not approach the
temperatures of the ULSD curve until the 85% distillate volume
1883
fraction. For the 1 and 2.5% concentrated mixtures, the distilla-
tion curves only slightly deviate from the ULSD curve initially
and coincide with it following the 45% volume fraction.
The concentration of the ethyl levulinate was traced during the
distillation by withdrawing and analyzing samples taken during
the distillation by use of the explicit data channel. The results of
these sequential analyses for the 1, 2.5, 5, and 10% mixtures can
be seen in Figure 2. Similar analyses were also performed on the
20% ethyl levulinate mixture, but these measurements yielded
very high uncertainties and are not presented. The high uncer-
tainty is probably due to the onset of phase separation
(liquid
liquid equilibrium) in the condenser during the mea-
surement. It is simply not possible to reproducibly sample and
analyze a two phase liquid.
The evolution of the ethyl levulinate concentration during the
distillation follows the same trend for each mixture. The max-
imum concentration occurs at the 10% volume fraction and
continues to decrease until the ethyl levulinate has been com-
pletely vaporized, which occurs following the 60% volume
fraction. Since the boiling point of ethyl levulinate is less than
dx.doi.org/10.1021/ef200239x |Energy Fuels 2011, 25, 1878–1890
Energy & Fuels
Table 4. List of Components and Their Relative Amounts in the Two Batches of the Fatty Acid
Levulinate Ester Biodiesel Fuel
Blend Identified by GC-MS and Determined by GC-FID
batch 1
components mass fraction (%) mol fraction (%)
ethyl levulinate 20.05% 34.91%
ethyl palmitate 5.38% 4.74%
ethyl stearate 2.59% 2.08%
ethyl oleate 58.62% 47.39%
ethyl linoleate 13.36% 10.87%
Table 5. Comparison of the Initial Boiling Conditions of the
Fatty Acid
Levulinate Ester Biodiesel Fuel Blends, the Soy
Based B100 Sample, and Neat ULSDa
sample (pressure) (kPa) vapor rise (° C) first drop (° C)
batch 1 (83.3 kPa) 249.9 251.2
batch 2 (84.5 kPa) 281.5 283.4
B100 (82.9 kPa) 345.6 341.6
ULSD (83.9 kPa) 217.6 217.9
a limitations prevented additional replicate measurements. The
The vapor rise temperature is the initial boiling temperature (IBT) of
the mixture. These temperatures have been corrected to 1 atm (101.325
kPa) with the Sydney Young equation. The pressures at which the
measurements were made are provided in the first column to permit
recovery of the actual measured temperature. The uncertainties are
discussed in the text.
that of the vapor rise temperature of the ULSD, one would expect
the first drop to contain the highest concentration of ethyl
levulinate, however, the diesel fuel contains small amounts of
components that have boiling points lower than that of ethyl
levulinate. The presence of these fluids therefore decreases the
concentration of the ethyl levulinate in the first drop.
2. Study of the Fatty Acid
Levulinate Ester Biodiesel Fuel.
As discussed above, two compositions of FLBB were analyzed
during this study. Prior to any distillation measurements, the
compositions of the two different batches were identified by use
of GC-MS and quantified by use of GC-FID measurements. The
chromatograms of the neat FLBB samples can be seen in Figure 3.
A list of components along with their associated mass and mole
percents for the two FLBB samples is provided in Table 4. The
difference between the two batches was the relative amount of
ethyl levulinate (and presence of appreciable residual solvent in
the second sample). Batch 1 contained approximately twice as
much ethyl levulinate (by mass) as Batch 2. This reflects the
natural variability in composition with respect to the oil seed
source of the FLBB, which ranges from about 10% for jatropha
fruits to about 20% for safflower seeds, by use of the carbohy-
drate/fatty acid processing technique described earlier.39 Based
on previous measurements performed on the B100 sample, it is
clear the ethyl levulinate is what distinguishes the FLBB from an
ordinary biodiesel fuel.
The initial boiling behavior of the two FLBB batches, the
B100, and the ULSD are provided in Table 5. The uncertainties
in these measurements were less than 0.3 °C. It is interesting to
note the significant difference in the IBTs of the two FLBB
batches. Batch 1, which has more ethyl levulinate, has an IBT that
is ∼11% less than that of Batch 2. Because ethyl levulinate has a
considerably lower boiling point compared to the IBT of the
FAEEs, its concentration has the greatest effect on the initial
1884
ARTICLE
batch 2
components mass fraction (%) mol fraction (%)
ethyl levulinate 10.00% 19.16%
ethyl palmitate 8.78% 8.53%
ethyl stearate 2.32% 2.05%
ethyl oleate 64.20% 57.10%
ethyl linoleate 14.69% 13.15%
boiling temperature and the boiling temperatures of the early
volume fractions. The addition of ethyl levulinate significantly
lowers the boiling point as compared to B100, making it more
comparable to the initial boiling temperature of ULSD.
Representative distillation curve data for the two FLBB
batches, the B100 sample, and the ULSD are given in Table 6.
These data are presented in both Tk (fluid temperature measured
directly) and Th (head temperature). The data are the average of
two separate measurements performed for each fluid. Sample
uncertainties in the temperature measurements for each fluid
were less than 0.4 °C. The Tk data for each mixture are presented
graphically in Figure 4. The effect of the ethyl levulinate is
apparent early in the distillation curves. In addition, the concen-
tration of the ethyl levulinate has a pronounced effect on the
boiling temperatures of the early distillate fractions as seen by the
differences in the curves for Batch 1 and Batch 2. Following the
complete vaporization of ethyl levulinate, the FLBB distillation
curves flatten and resemble that of the B100. The curves flatten
because the remaining components (the FAEEs) all have similar
boiling points. The points at which the curves begin to flatten are
different for the two batches because of the different initial
concentrations of ethyl levulinate. The ethyl levulinate does
not completely vaporize in Batch 1 until the 20% volume fraction,
whereas removal of the ethyl levulinate in Batch 2 occurs at
approximately the 10% volume fraction. This is because there is
approximately twice as much ethyl levulinate in Batch 1 com-
pared to Batch 2 (see Table 4). Following the flattening of the
curves, we note that the FLBB boils at slightly higher tempera-
tures than the B100. This is because the FAEEs have higher
boiling temperatures compared to the FAMEs which make up
the B100 fluid. Beginning at ∼75% volume fraction, the FLBB
and the B100 curves sharply increase. This is a result of the fatty
acid esters polymerizing into larger molecules resulting in the
increase in the boiling temperature of the fluid.89
While the gross examination of the distillation curves is
instructive and valuable for many design purposes, the composi-
tion channel of the ADC approach provides more information
that can aid in developing a better understanding of the thermo-
physical behavior of the fluid. A series of chromatograms for the
two FLBB batches is provided in Figure 5a and 5b. The analysis
of the first drop of Batch 2 showed higher concentrations of
hexane and ethanol, which are two reagents used during proces-
sing of the FLBBs. The chromatograms show higher concentra-
tions of the FAEEs in the 10% volume fraction in Batch 2
compared to the 10% volume fraction of Batch 1. This is because
the ethyl levulinate in Batch 2 is nearly completely removed from
the boiling fluid by the 10% volume fraction. The 50% volume
fractions of both batches are nearly identical and primarily
dx.doi.org/10.1021/ef200239x |Energy Fuels 2011, 25, 1878–1890
Energy & Fuels ARTICLE

Table 6. Representative Distillation Curve Data (Given As the Average of Two Distillation Curves) for the Fatty Acid
Levulinate
Ester Biodiesel Fuel Blends, the Soy Based B100 Sample, and Neat ULSDa

batch 1 (83.3 kPa) batch 2 (84.5 kPa) B100 (82.9 kPa) ULSD (83.9 kPa)
distillate volume fraction (%) Tk (° C) Th (° C) Tk (° C) Th (° C) Tk (° C) Th (° C) Tk (° C) Th (° C)

5 261.5 223.3 316.7 218.7 347.6 345.1 225.5 206.8

10 280.8 227.2 351.5 291.2 350.0 345.9 230.1 212.4
15 318.8 214.0 356.6 349.1 350.7 346.9 235.4 219.3
20 354.7 350.5 357.7 351.1 351.4 347.3 240.9 224.3
25 355.8 352.2 358.5 353.1 351.7 347.8 245.9 229.2
30 356.7 353.0 359.2 352.8 352.2 348.2 251.2 235.2
35 357.1 353.4 359.9 353.0 352.8 348.5 256.5 241.0
40 357.7 353.8 360.5 353.5 353.5 349.2 261.9 246.1
45 358.4 353.8 361.4 354.0 354.0 349.5 268.2 252.0
50 358.7 354.3 362.3 354.3 354.8 349.9 273.8 257.4
55 359.6 355.0 363.4 354.7 355.7 350.1 280.2 264.6
60 360.2 355.4 364.8 355.4 356.7 350.6 287.1 271.7
65 361.1 355.8 366.6 355.7 358.6 350.9 294.3 279.0
70 362.5 356.6 368.9 356.7 360.4 351.4 301.6 285.4
75 364.4 356.8 372.2 357.0 363.4 351.9 310.0 294.7
80 368.1 357.0 377.7 358.0 369.4 351.9 319.2 303.5
85 375.1 357.6 387.1 357.9 382.3 351.9 328.9 312.6
90 391.3 350.7 404.6 350.6 404.5 347.0 - -
a
The uncertainties are discussed in the text. These temperatures have been corrected to 1 atm with the Sydney Young equation.

Figure 4. Representative distillation curves of the two batches of fatty acid
levulinate ester biodiesel fuel presented as Tk (the temperature measured in
the fluid). The distillation curve for a representative ULSD and a previously measured commercial soy based biodiesel fuel sample52 are also presented.
Although only one curve for each fluid is shown, each curve was measured two times. The uncertainties are discussed in the text and are smaller than the
symbols used.

composed of the FAEEs. This explains the flat and nearly
identical distillation curves in this region. The decrease in
concentration of the ethyl linoleate, which is an unsaturated
carbon-carbon double bonds, observed in the 80% GC plots
supports the thermal compositional transitions previously
mentioned.89
The composition-explicit data channel allows the addition of
thermochemical data, such as the enthalpy of combustion, to the
distillation curve.50,51,54 The total enthalpy of combustion
(which we represent as
ΔHc) can be found by multiplying
the enthalpy of combustion of each of the pure (or individual)
components by the mole fraction of that component, and then
adding the contributions of the individual components to obtain
the total enthalpy of combustion:50,51,54

ΔHc ¼ ∑xi ð
ΔHi Þ ð1Þ

1885 dx.doi.org/10.1021/ef200239x |Energy Fuels 2011, 25, 1878–1890

Energy & Fuels ARTICLE

Figure 5. (a) and (b) Representative chromatograms of four distillate volume fractions of the two fatty acid
levulinate ester biodiesel fuel blends. The
major peaks are labeled in the first fraction in which they were observed. The y-axes are arbitrary units of intensity, and the x-axes are retention time (RT)
in min. The details of the chromatography are discussed in the text.

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Energy & Fuels ARTICLE

Table 7. Total Enthalpy of Combustion, Presented in
kJ/mol, for Four Distillate Volume Fractions of the Two Fatty
Acid
Levulinate Ester Biodiesel Fuel Blends, the Soy Based B100, and a ULSD Sample (Uncertainties Are Presented in
Parentheses)
distillate volume fraction (%) batch 1 batch 2 B100 ULSD

0.025 3352 (111) 2021 (67) 10403 (343) 5090 (168)

10 3790 (125) 4597 (152) 10468 (345) 6258 (207)
50 11151 (368) 11130 (367) 10579 (349) 9847 (325)
80 11153 (368) 11221 (370) 10689 (353) 10572 (355)

Figure 6. Enthalpy of combustion for the two fatty acid
levulinate ester biodiesel fuel blend batches presented at four distillate cuts, 0.025% (the first
drop), 10%, 50%, and 80%. The uncertainties are discussed in the text.

where i refers to the individual components that have been
identified or selected, and the enthalpy of mixing is ignored.
We have discussed the contributions to the overall uncertainty
of the total enthalpy of combustion elsewhere.50,51,54 The main
sources of uncertainty in the enthalpy of combustion calculation
here are due to (1) uncertainty in the values tabulated for the
individual enthalpy of combustion values for each component,
(2) uncertainty in the measured mole fraction, and (3) the
uncertainty arising from the absence of data for experimental
enthalpy of combustion for some of the constituents. There is
also uncertainty in neglecting the enthalpy of mixing; however,
this value has been shown previously to be less than 0.01% of the
enthalpy of combustion. Additionally, there may be uncertainty
in the enthalpy of combustion due to the inability to resolve very
closely related isomers via the analytical protocol, the complete
misidentification of a component, and neglecting components
present at very low concentrations. The FLBBs contain a small
number of easily resolved and identifiable peaks, thus, these
analytical metrology contributions to the uncertainty are also
negligible. In past work, we determined that neglecting peaks
with total uncalibrated area percentages of up to 4% increased the
uncertainty of the calculated enthalpy by only 1.5%. Thus,
neglecting minor components in the biodiesel fuel distillate
fractions does not significantly affect the uncertainty of the total
enthalpy of combustion. In view of these sources of uncertainty,
the overall combined uncertainty in our total enthalpy of
combustion calculations (with a coverage factor k = 2)90 was less
1887
than 3%.69 The uncertainty is dominated by the analytical
measurement and determination of the component mole
fractions.
The total enthalpy of combustion of both FLBB batches
(taking into account peaks with area % in excess of 2%) was
calculated at four distillate volume fractions: 0.025% (the first
drop), 10%, 50%, and 80%. Table 7 and Figure 6 present the
calculated enthalpies of combustion, in
kJ/mol, for the dis-
tillate volume fractions of both FLBB batches. For comparison,
the previously determined enthalpies of combustion for B100
and the ULSD sample are also presented in Table 6. Notice that
the molar enthalpy of combustion of the first drop for Batch 2 is
less than that for Batch 1. This is due to the higher concentrations
of hexane and ethanol remaining in Batch 2 following the
processing. The molar energy content of Batch 2 is greater at
the 10% volume fraction than Batch 1 because of the smaller
amount of ethyl levulinate at this volume fraction. At higher
distillate volume fractions, the energies of the two batches are
identical because the composition of these distillate fractions is
very similar. The presence of ethyl levulinate in the FLBB results
in lower enthalpies of combustion in the early volume fractions
compared to B100; however, following the exhaustion of the
ethyl levulinate, the FLBB energy content becomes very similar
to that of B100.
An alternative representation of the enthalpy of combustion
that is perhaps more practical for applied engineering would be to
present
ΔHc in terms of mass or volume, expressed in
kJ/g
dx.doi.org/10.1021/ef200239x |Energy Fuels 2011, 25, 1878–1890
Energy & Fuels
Table 8. Total Enthalpy of Combustion, Presented in
kJ/g and
kJ/L, for Four Distillate Volume Fractions of the Two Fatty
Acid
Levulinate Ester Biodiesel Fuel Blends and the Soy Based B100 for Comparison (Uncertainties Are Presented in
Parentheses)
mass-basis
distillate volume fraction (%) batch 1 (
kJ/g) batch 2 (
kJ/g)
0.025 25 (1) 30 (1)
10 25 (1) 27 (1)
50 36 (1) 36 (1)
80 36 (1) 36 (1)
or
kJ/L, respectively. The conversion to a per-mass basis
requires only the relative molecular mass (RMM) of the con-
stituents of each sample; the uncertainty of this calculation
remains less than 3%. Table 8 shows that Batch 2 has a 17%
higher per-mass enthalpy of combustion than Batch 1 in the first
drop. This is because of the higher concentrations of hexane and
ethanol in the first drop of Batch 2 (which contains more energy
per-mass than ethyl levulinate) which is the primary component
in the first drop of Batch 1. The FAEEs contain more energy than
ethyl levulinate, which accounts for the increase in the per-mass
enthalpy during the distillation for both FLBB batches. Once the
ethyl levulinate has been volatilized, the per-mass energy content
is equal to that of the B100 sample.
Presentation of the data on a per-volume basis is also valuable.
Consumers are more accustomed to thinking about fuel on a per-
volume basis instead of a per-mole or per-mass basis. The conver-
sion to a per-volume basis requires both the RMM and the density
of the constituents of each sample at each distillate temperature.
For the fluids measured here, reliable density data of the constitu-
ents of each sample are available as a function of the distillation
temperatures, and the uncertainty of this calculation remains less
than 3%.91 Table 8 indicates that the first drop of Batch 2 has a
slightly lower per-volume enthalpy than that of Batch 1. This is
because of the lower energy content per-volume of ethanol, which
makes up nearly half of the volumetric concentration of the first
drop for Batch 2. Since fatty acid esters have greater per-volume
energy content than ethyl levulinate, the total per-volume enthal-
pies of combustion of the initial volume fractions of the FLBB are
less than that of B100. As the distillation progresses and the ethyl
levulinate is removed, the FLBB per-volume energy content
increases to within the experimental uncertainty of the B100.
’ CONCLUSION
Recently, a new processing technique was developed that
converts the carbohydrates found in plant biomass into ethyl
levulinate, which has properties making it a possible diesel fuel
oxygenate additive. The volatility properties of ethyl levulinate/
diesel fuel were investigated using the ADC method and
apparatus. Mixtures containing 1, 2.5, 5, 10, and 20% ethyl
levulinate (v/v) were analyzed. The distillation curves of the
oxygenated mixtures showed the greatest deviation from the
ULSD curve early in the distillation, with a more pronounced
deviation occurring as the concentration of the ethyl levulinate
was increased. In fact, the boiling temperatures of the less
concentrated mixtures (i.e., 1 and 2.5 volume percent) deviated
very little from those measured for the neat ULSD. Composition-
explicit data analysis performed on each mixture revealed that
detectable amounts of ethyl levulinate remained in the boiling
fluid until the 60% distillate volume fraction. Based on these data,
ARTICLE
volume-basis
B100 (
kJ/g) batch 1 (
kJ/L) batch 2 (
kJ/L) B100 (
kJ/L)
36 (1) 24752 (817) 23087 (762) 31517 (1040)
36 (1) 24881 (821) 26256 (866) 31502 (1040)
36 (1) 31447 (1038) 31457 (1038) 31663 (1045)
37 (1) 31400 (1036) 31508 (1040) 31772 (1049)
it appears that modest additions of ethyl levulinate to diesel fuel
will not significantly affect the volatility.
The second part of this study focused on biodiesel fuel blends
produced from safflower oil seeds via a new processing technique
that converts both the oils and the carbohydrates in the seeds into
a hybrid biodiesel fuel resulting in an increase in fuel yield
compared to traditional processing techniques. The new biodie-
sel blends contain a mixture of FAEEs, commonly found in most
biodiesel fuels, and ethyl levulinate. Two compositions of the
new biodiesel fuel blend were analyzed with the ADC and
compared to a commercial soy-based biodiesel fuel and ULSD
fuel. Distillate fractions were withdrawn to measure the changing
composition and energy content during the distillation. Reduc-
tions in boiling temperatures for the fatty acid
levulinate ester
blends in the early distillate fractions as compared to the
commercial biodiesel fuel were noticed. In addition, the enthal-
pies of combustion in the initial distillate fractions were lower in
the fatty acid
levulinate ester blends than the commercial
biodiesel. The measurements presented in this paper will assist
in the evaluation of ethyl levulinate as a potential additive for
ULSD. Moreover, by examining the impact of the addition of
ethyl levulinate on biodiesel fuel properties (specifically the
volatility), this work will assist in the evaluation of this additive
to enhance the cold flow properties of biodiesel fuel.
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: bruno@boulder.nist.gov.
’ ACKNOWLEDGMENT
T.M.L. and B.C.W. both acknowledge National Academy of
Sciences/National Research Council postdoctoral fellowships at
the National Institute of Standards and Technology. M.M. and E.
B.N. acknowledge the support of National Science Foundation
grant CBET 0932391.
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