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Evaporation of Multicomponent Droplets

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Evaporation of Multicomponent Droplets

J. F. Widmann & E. J. Davis

To cite this article: J. F. Widmann & E. J. Davis (1997) Evaporation of Multicomponent Droplets,
Aerosol Science and Technology, 27:2, 243-254, DOI: 10.1080/02786829708965470

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 ELSEVIER

Evaporation of Multicomponent Droplets

J. F. Widmann and E. J. Davis*
DEPARTMENT OF CHEMICAL ENGINEERING, BOX 351750, UNIVERSITY OF WASHINGTON,
SEATTLE, WA 98195-1750, USA

ABSTRACT. The evaporation of multicomponent drops having diameters on the

order 10 p m was investigated using electrodynamic levitation and light-scattering
measurements. Multicomponent drops representative of diesel fuels and binary
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drops were studied. The binary system consisted of the halogenated compounds
1-iododocane and 1-bromotetradecane, and the model fuel drops were composed of
hexadecane, I-methyl naphthalene, and cis- and trans-decahydronaphthalene (de-
calin). The effect of an additive, tertiary butyl peroxide, on the evaporation of the
multicomponent system was explored, and some data are reported for the additive
ethyl hexyl nitrate. The additives were found to have negligible effect on the
evaporation rate. The measured evaporation rates are compared with a theoretical
analysis based upon diffusion-controlledevaporation using the UNIFAC (Reid et al.,
1987) model for liquid phase activity coefficients. The model was found to be in
good agreement with experiment. AEROSOLSCIENCE AND TECHNOLOGY
27:243-254 (1997) O 1997 American Association for Aerosol Research

INTRODUCTION expected to affect droplet combustion, do

Single levitated droplets are frequently used
to study aerosol behavior to eliminate the
complicating effects of polydispersity, parti-
cle-particle interactions, and particle-con-
tainer interactions. By suspending a drop in
an electrodynamic balance (EDB), the par-
ticle position can be spatially fixed for
quantitative and qualitative analysis. The
EDB has been used for a variety of studies
involving aerosol thermodynamics, trans-
port, and chemical phenomena.
The focus of this work is the thermody-
namics of levitated, multicomponent or-
ganic droplets. The effects of oxygenated
additives on fuel droplets are of particular
interest. Although such additives can be
*Author to whom correspondence should be addressed.
Aerosol Science and Technology 27:243-254 (1997)
Q 1997 American Association for Aerosol Research
Published by Elsevier Science Inc.
they alter the evaporation characteristics of
the multicomponent mixture?
Rube1 (1981) was the first to use an EDB
to conduct measurements on multicompo-
nent oil drops, reporting evaporation rates
for Number 2 diesel fuel and a high boiling
petroleum fraction (100 pale oil). Rube1
and Milham (1984) later obtained "effec-
tive" vapor pressures of 100 pale oil by
modeling the mixture as a 15 component
system and assuming ideal solution behav-
ior. Since the mass of a levitated drop hav-
ing constant charge is proportional to the
dc levitation voltage, Rube1 determined the
change in mass from measurements of the
dc voltage.
Ravindran and Davis (1982) used elastic
light-scattering measurements to explore
the evaporation kinetics of levitated submi-
 244 J. F. Widman and E. J. Davis
crometer droplets composed of dioctyl ph-
thalate and dibutyl phthalate. Based on
diffusion-controlled evaporation theory and
ideal solution behavior, they predicted the
evaporation rate of this binary system with
satisfactory results. Subsequently, Rube1
(1982) reported evaporation rates for the
same binary system determined by using
supermicrometer droplets.
Allen et al. (1990) determined liquid ac-
tivity coefficients for binary organic mix-
tures via microdroplet evaporation experi-
ments by using binary pairs of l-bromo-
dodecane, 1,8-dibromooctane, hexadecane,
and heptadecane. Their analysis was not,
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however, extended to ternary systems.
Buehler et al. (1991) used inelastic light
scattering to monitor the evaporation of
multicomponent aerosols by following the
distillation of a droplet consisting of 1,8-di-
bromooctane and hexadecane, and by mea-
suring the intensity of the Raman peak
corresponding to the C-Br bond. Re-
cently, Aardahl et al. (1996) combined elas-
tic and inelastic light-scattering techniques
to follow the evaporation of levitated
droplets composed of 1-iodododecane and
1-bromotetradecane, both of which have
Raman active carbon-halogen bonds. In
this paper we use elastic light scattering to
investigate the thermodynamics of droplets
composed of up to five components.
THEORY
DifSusion-Controlled Evaporation
At ambient temperature and pressure, the
evaporation of a pure component liquid
droplet below its boiling point is controlled
by diffusion of vapor into the surrounding
gas. For a pure component, the analysis of
this process is attributed to Maxwell (1890).
His result for quasi-steady state evapora-
tion may be written in the form
dm,
-- - -
dt R enthalpy of vaporization of species i.
in which m i is the droplet mass, a is its
radius, R is the gas constant, and D,,is the
diffusion coefficient of vapor i, with molec-
Aerosol Science and Technology
27:2 August 1997
ular weight Mi, in stagnant gas j. The
vapor pressure at surface temperature T, is
p"~,), and pi,, and T, are the partial
pressure and temperature of vapor in the
bulk gas, respectively. In general, the sur-
face temperature of the drop differs from
the bulk gas temperature, for the heat of
vaporization must be supplied by heat
transfer to the interface from the gas and
liquid phases.
For a slowly evaporating drop of density
p,, the evaporation can be assumed to oc-
cur isothermally (To = T, = T) and Eq. 1
can be integrated to give
where a, is the radius at time t , . From Eq.
2, a plot of the radius squared versus time
should yield a straight line. The slope Sij
depends only on the material properties,
temperature, vapor pressure, and gas phase
diffusion coefficient. If the gas far from the
drop is free of the diffusing vapor, the slope
is given by
From the theory of nonuniform dilute
gases (Chapman and Cowling, 1970; Bird et
al., 1960), the diffusion coefficient is pro-
portional to T"~/R,,,,, in which R,,,, is
the collision integral, a weak function of
temperature. Empirical correlations such as
"
those of Fuller et a1 (1966) yield a relation-
ship of the form D,, = A T ' where A is a
proportionality constant that is a function
of the molecular weights and sizes of the
molecules. In this approximation, S,,. varies
with temperature as T075p,('(T). Using the
Clausius-Clapeyron equation to relate thc
vapor pressure to the temperature, we may
write
in which B is a constant and A, is the
Using this result and the dependence of
DL,on T in Eq. 3, one obtains
 Aerosol Science and Technology
27:2 August 1997
Thus, provided that the enthalpy of vapor-
izatio; may be assumed to be constant over
the temperature range of interest, we ex-
pect to vary linearly with T-'.
Rapid evaporation complicates the the-
ory because- the heat and mass transfer
become coupled. Since the thermal conduc-
tivity of the droplet is much larger than
that of the gas/vapor mixture, the droplet
temperature is nearly spatially uniform, and
the heat of vaporization is supplied largely
by conduction from the surrounding gas.
Including an energy balance in the analyses
results in a surface temperature depression
given by
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where K, is the thermal conductivity of the
gas. In addition, convective flow due to
rapid transport of vapor from the
surface-Stefan flow-occurs and further
complicates the analysis. For the experi-
ments described here, a temperature de-
pression was calculated for the most volatile
component and was determined to be neg-
ligible. Therefore, the vapor pressryes of all
of the components are sufficiently low so
that the evaporation may be assumed to
occur isothermally, and the Stefan flow can
be neglected.
Multicomponent Evaporation
When a multicomponent droplet evapo-
rates into a vapor-free medium, the rate of
droplet evaporation can be calculated from
a total mole balance written for the drop,
yielding
where x i is the mole fraction of species i;
Vm is the mean molar volume of the droplet
defined by the approximation
Evaporation of Multicomponent Droplets 245
and yi is the activity coefficient of species i
in the mixture.
A mass balance on species i within the
drop yields
for the rate of change of the mole fraction
of species i. For an N-component mixture,
there are N - 1 equations in the form of
Eq. 9 subject to the constraint C, x, = 1. In
deriving Eqs. 7 and 9, it is assumed that the
volumes mix ideally (A&,, = 0).
To apply Eq. 7, it is necessary to know
the diffusion coefficients in the surrounding
gas, the vapor pressures at the temperature
of the drop, and the activity coefficients for
each of the species present. The gas phase
diffusion coefficients were estimated using
the Wilke and Lee correlation recom-
mended by Reid et al. (1987), and the vapor
pressures of the individual components
were obtained from the literature or deter-
mined experimentally. Vapor pressure data
were obtained from Indritz et al. (1978) for
tertiary butyl peroxide (t-BP), from Stull
(1947) for trans- and cis-decalin (DEC),
and from Weast (1967) for hexadecane
(HEX). The vapor pressures of other chem-
icals used in this study [1-methyl naphtha-
lene (METH), 1-bromotetradecane (BTD),
and 1-iodododecane (IDD)] were obtained
experimentally by applying Eqs. 2 and 3 to
the radii determined from light-scattering
data.
The activity coefficients depend not only
on the temperature of the droplet, but also
on the composition, requiring continual up-
dating of the values of y, during the com-
putation of the evaporation rate. Liquid
activity coefficients were predicted using
the UNIFAC model, which is based upon a
molecular group contribution approach
(Reid et al.). Molecules are "constructed"
from appropriate functional subgroups,
such as -CH,-, - C = C -, and
-CH2-0-. The relative volume R,, the
relative surface area Q,, and the interac-
tion parameter a,,, of the kth subgroup
 246 J. F. Widman and E. J. Dauis Aerosol Science and Technology
27:2 August 1997

has been tabulated for a number of sub- TABLE 1. UNIFAC Model Parameters Rk and Q,
groups. The activity coefficient is consid- Main Groups Subgroups Qk Rk
ered to be comprised of two terms: a "com-
binatorial" term y;, which accounts for CH3
molecular size and shape differences, and a CH,
CH
"residual" term y:, which accounts for C
molecular interactions. That is, the activity CH,=CH
coefficient is given by CH =CH
CH,=C
CH=C
C=C
ACH
The combinatorial and residual terms can AC
be evaluated for a solution of subgroups ACCH,
ACCH,
from ACCH
OH
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CH, C1
I
Br
COO

and

and

In the preceding equations, the subscript i

refers to the species, j is a dummy index, k
corresponds to the subgroup, and m identi-
where fies the main group. The number of sub-
groups of type k in the molecule uf), the
values of the subgroup parameters Rk and
Q,,and the interaction parameter a,, used
in this work are listed in Tables 1 and 2.

TABLE 2. UNIFAC G r o u ~Interaction Parameters a:,

The mam groups corre~pond~ng

to the numbers 1-9 are shown In Table 1
 Aerosol Science and Technology
27:2 August 1997
EXPERIMENTAL
Materials
The chemicals used in this research were
obtained from Aldrich Chemical Company.
The purities and refractive indices of the
chemicals were BTD (97%, N = 1.4600),
IDD (98%, N = 1.4844), t-BP (98%, N =
1.3891), ethyl hexyl nitrate (EHN, 97%, N
= 1.4320), HEX (99%, N = 1.4340), METH
(98%, N = 1.6150), and DEC (98%, N =
1.4750). All of the chemicals were used as
purchased without further purification.
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The Electrodynamic Balance
The experiments described here were con-
ducted by levitating a charged drop in an
electrodynamic balance (EDB) using super-
imposed ac and dc electric fields. Levitation
of single particles has been widely applied
in aerosol science, and Davis (1992) has
reviewed the theory and application of
electrostatic, electrodynamic, and optical
trapping. The EDB used for these experi-
AIR EXIT
LASER
COMPUTER
ROTAMETER
AIR INLET
FIGURE 1. Schematic of the experimental apparatus used for the evaporation rate measurements.
Evaporation of Multicomponent Droplets 247
ments, shown in Fig. 1, has a classical bihy-
perboloidal electrode configuration intro-
duced by Wuerker et al. (1959).
A dc potential is applied across the top
and bottom electrodes to balance any verti-
cal forces such as aerodynamic drag and
gravity. An alternating potential is applied
to the center ring electrode to provide
time-dependent axial and radial restoring
forces, keeping the particle centered in the
chamber, Typical operating values for the
ac potential were 1.0-1.5 kV at 100-150
Hz. A hole in the top electrode was used to
-
introduce the droplet into the balance from
a charged hypodermic needle, and a similar
hole in the bottom electrode allowed gas to
enter the chamber, thereby removing any
vapors introduced by the evaporation pro-
cess.
The particle was suspended in the path
of a 10 mW He-Ne laser, which was the
light source for light-scattering measure-
ments. Using a 1024 pixel photodiode array
(PDA) and a photomultiplier tube (PMT),
elastically scattered light was collected and
then compared with Mie theory (1908) to
MICROSCOPE
AYLEIGH HORN
TEMPERATURE
 248 J. F. Widman and E. J. Davis
establish the size of the drop. Thorough
discussions of Mie theory are available in
Kerker (1969), van de Hulst (19811, and
Bohren and Huffman (1983). The PMT was
located at 90' from the direction of propa-
gation of the laser beam, and the PMT
measured the intensity of the scattered light
at a fixed position (c,b,O) as a function of
time. This record is called a resonance
spectrum, and an example of a representa-
tive experimental resonance spectrum for a
BTD droplet evaporating in air at 32.7"C is
presented in Fig. 2. The theoretical spec-
trum computed from Mie theory is also
shown for comparison. Using the match
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between theory and experiment, the evapo-
ration rate can be determined very pre-
cisely as indicated by Ray et al. (1991).
In addition to the resonance spectrum,
the intensity of the scattered light was also
measured as a function of the polar angle
using the PDA. The intensity of the scat-
tered light as a function of polar angle is
called a phase function and provides a
measure of the droplet size at an instant in
MIE THEORY
4 1.5
m
>-
& 1.0
Z
W
F
+ 0.5
'121.6 120.8 120
SIZE PARAMETER, X
FIGURE 2 T w l y ison of an experimental resonance spectrum collected during the evaporation of a BTD drop
at 32.7"C ,. i rhr t:.~oreticalresonance spectrum calculated from Mie theory.
Aerosol Science and Technology
27:2 August 1997
time. For the apparatus used here, the PDA
collected light over the range 34.85" 5 9 5
55.15", and scans could be recorded at 50
ms intervals. An example of an experimen-
tal phase function for BTD and the match-
ing theoretical phase function are shown in
Fig. 3. The droplet associated with Fig. 3
had a size parameter, X = 27ra/h = 123,
corresponding to a radius of 12.4 pm. Al-
though phase functions can be used to de-
termine the size to 2 parts in 104 (Ray et
al., 1991), we made no attempt to match
the fine structure of the angular scattering
data. Our precision is limited to approxi-
mately + 1%.
A droplet was introduced into the EDB
-
by applying a high voltage ( 4-5 kV) pulse
to the needle of a microliter syringe con-
taining the material to be trapped. An elec-
trospray of polydisperse droplets was
formed, and one of the droplets with a
charge to mass ratio in the appropriate
range was then trapped. The required
charge to mass ratio depends on the magni-
tude and frequency of the potentials ap-
119.2 118.4 117.6 116.8 116
 Aerosol Science and Technology
27:2 August 1997
35 40 45 50
SCATTERING ANGLE, deg
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FIGURE 3. Comparison of an experimental and theo-
retical phase function for a BTD droplet. The size
parameter X is 123.
plied to the electrodes. To provide temper-
ature control, the top and bottom elec-
trodes were hollowed out to allow circula-
tion of a constant-temperature fluid. A de-
focused microscope was used to view the
droplet and ensure that it remained bal-
anced. The dc voltage required to levitate
the droplet can be used as an independent
measure of the droplet mass (in the ab-
sence of convection within the chamber),
but we did not apply this technique here.
RESULTS AND DISCUSSION
Single Component Evaporation
Based on Eq. 2, a2 should be a linear
function of time for single component
evaporation. A number of experiments were
performed on the pure components of in-
terest to examine the reproducibility of re-
sults and to obtain the parameters needed
to interpret multicomponent results. Rep-
resentative results for the evaporation of
droplets of 1-methyl naphthalene (METH)
in air at 293.9 f 0.2 K are presented in Fig.
4. These results demonstrate the repro-
ducibility of the technique and the agree-
ment between the radii determined from
phase functions and resonance spectra. The
Evaporation of Multicomponent Droplets 249
t 0 RESONANCE DATA 1
55
FIGURE 4. The evaporation of pure METH drops at
+
20.7 0.2"C.
slopes of the lines shown in the figure are
very nearly the same, and are given by
S,, = - 4.036 f 0.206 pm2/s. These results
for METH were used in the multicompo-
nent studies discussed in the following text.
Similar data were obtained for the pure
components BTD and IDD over a range of
temperatures (288 K < T < 310 K) to ex-
plore temperature effects on the evapora-
tion of the binary system BTD/IDD. Based
on Eq. 5 , we expect l n ( S , , / ~ ~ ) 'to
~ ) be a
linear function of T p l , so the results are
plotted in this form in Fig. 5 with S,, in
units of pm2/s. Scatter in the data can be
attributed to fluctuations in the tempera-
ture and errors associated with measuring
the temperature, because the droplet tem-
perature can vary slightly from the chamber
temperature. The uncertainty in the tem-
perature measurements is estimated to be
AT = 0.2-0.3"C. Because the vapor pres-
sure is a strong function of temperature,
this uncertainty in the temperature can re-
sult in the scatter shown in Fig. 5.
The results presented in Fig. 5 can be
used to determine the vapor pressure of
BTD and IDD over the temperature range
shown provided the diffusion coefficient is
known or can be estimated. A variety of
estimation procedures are available for cal-
culation of gas phase diffusivities, as re-
viewed by Reid and his co-authors.
 250 J. F. Widman and E. J. Davis
FIGURE 5. The variation of the evaporation rate of
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BTD and IDD with temperature. Sij is the slope of the
aZ versus time plot.
Binary Evaporation
Preliminary studies were conducted on bi-
nary droplets of BTD and IDD, which can
be expected to follow ideal solution behav-
ior. Aardahl et al. showed this system to be
ideal and presented evaporation rate data
that could be used for comparison. The
interpretation of light-scattering data for
binary droplets requires information about
the refractive index of the mixture. Tang
and Munkelwitz (1991) used electrody-
namic levitation to measure the density and
refractive index of aqueous solution
droplets, showing that the molar refraction
is a linear function of mole fraction of
solute. The molar refraction R is related to
the molar volume V and the refractive in-
dex by (Moelwyn-Hughes, 1961)
The molar refraction of a binary system
is given by
in which R, is the partial molar refraction
of the solvent, A, is the partial molar re-
fraction of the solute, and x, is the mole
fraction of the solute.
If the molar volumes of components 1
and 2 of a binary mixture do not change
Aerosol Science and Technology
27:2 August 1997
upon mixing and if the refractive index
change is not too great, the refractive index
of a mixture can be approximated by a
linear function of the volume fractions of
the components. Allen et al. (1990) used
such a mixing rule in the analysis of their
binary evaporation rate data, and we ap-
plied their method to analyze the
BTD/IDD data. Allen and her co-workers
examined interpolation formulas for the re-
fractive index of organic binary mixtures
based upon mass fraction, volume fraction,
and mole fraction, and found that interpo-
lation based upon volume fraction yielded
the best agreement with experiment. The
interpretation of resonance data requires a
two-parameter fit of Mie theory, because
the size and refractive index vary as distilla-
tion proceeds. However, the size and the
composition of the binary system are re-
lated by a material balance on the droplet,
and the composition and the refractive in-
dex are related. These relations simplify
the analysis of the data, because it is only
necessary to assume values of the size tb
match Mie theory.
Figure 6 presents a comparison between
an experimental and theoretical resonance
spectrum for an evaporating droplet of BTD
and IDD at 295.9 I(. The initial mole frac-
tion of BTD was 0.508. The match between
theory and experiment is seen to be good,
providing an accurate measure of the evap-
oration rate over the time interval shown in
the figure. Using the evaporation rate de-
termined by matching the experimental res-
onance spectrum with theory, a plot of the
radius squared versus time can be gener-
ated. This is shown in Fig. 7. The evapora-
tion rate calculated by assuming idealsolu-
tion behavior is also shown. The curvature
seen in the data is due to the distillation
process. The more volatile IDD preferen-
tially distills from the drop, leaving a higher
concentration of the lower volatility species,
BTD. As a result the evaporation rate de-
creases with time.
Although the agreement between diffu-
sion theory and experiment shown in Fig. 7
is reasonably good, the measured evapora-
tion rates are somewhat higher than the
 Aerosol Science and Technology
27:2 August 1997
EXPERIMENT
= 1.51
m
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FIGURE 6. A comparison between an experimental and theoretical resonance spectrum collected during the
evaporation of a binary droplet composed of BTD and IDD at 22.7"C.
predicted results for short times and lower
for long times. Spectroscopic grade IDD
and BTD were not available and the origi-
nal chemicals contained unknown impuri-
ties which could effect the evaporation rate,
1.-IDEAL SOLUTION THEORY
EXPERIMENT
FIGURE 7. Radius squared versus time for a BTD/
+
IDD mixture at 22.8 0.2"C. The theoretical evapora-
tion rate based upon ideal solution theory is also
shown.
Evaporation of Multicomponent Droplets 251
particularly at longer times when any low-
volatility impurities accumulate. High-vola-
tility impurities increase the evaporation
rate for short times until the contaminants
distill from the droplet. It is also reason-
able that the system is slightly nonideal,
resulting in deviation from ideal solution
behavior.
Multicomponent Evaporation and the Eflect
of Additives
To improve the combustion characteristics
of fuel mixtures, additives such as peroxides
and nitrates are often added. These addi-
tives can effect the combustion process ei-
ther thermodynamically, kinetically, or
both. If the additives affect the kinetics of
the combustion process, their influence
could not be revealed in our experiments;
however, thermodynamic effects may ap-
pear in the microdroplet evaporation data.
To explore possible thermodynamic effects,
small amounts of the oxygenated additives
 252 J. F. Widman and E. J. Davis Aerosol Science and Technology
27:2 August 1997

tertiary butyl peroxide (t-BP) and ethyl TABLE 3. Mole Fractions of the Individual Compo-
hey1 nitrate (EHN) were added to droplets nents Present in the Mixture Without the Additive
and With t-BP
composed of pure components and of mix-
tures. Figure 8 shows the evaporation rates, Component Mole Fraction x i
presented as a 2 versus time, of METH
Without t-BP
droplets with and without the additives. The HEX 0.182
data presented in Fig. 8 show no significant METH 0.475
effect of the additives. For the experiments cis-DEC 0.172
with the additives, S i j = - 3.828 + trans-DEC
With 0.00326 mole fraction t-BP
0.172
0.098 pm2/s for EHN and Sij = - 3.826 t- HEX 0.181
0.094 pm2/s for t-BP. These slopes vary METH 0.473
little from those associated with the METH cis-DEC 0.171
evaporation data of Fig. 4 given by Si.= trans-DEC 0.171
- 4.036+ 0.206 pm2/s. ~t is apparent that
the slopes of the data for the two additives
Downloaded by [123.142.191.206] at 13:11 28 January 2016

are nearly identical.

incorporate this chemical into the UNIFAC
Experiments were performed with
model could not be found in the literature.
droplets consisting of a four component
Attempts to "build" a peroxide group from
mixture (METH, HEX, cis-DEC, and trans-
two ether groups yielded unrealistically high
DEC) with and without the additive t-BP.
values of activity coefficients. The values
The compositions of the droplets are given
for the nitrate group were also not avail-
in Table 3. Results from several experi-
able. It is obvious, however, that the effect
ments with and without the additive are
of the activity coefficients for the additives
shown in Fig. 9. The experiments con-
is very small because they are present in
ducted with the t-BP were at 21.O"C and
small quantities and thus have a negligible
those without were at 20.7"C. The theoreti-
effect on the evaporation process.
cal evaporation rates based upon the UNI-
The agreement between the experiment
FAC model are also shown. The activity
and theory shown in Fig. 9 enables the
coefficient for the additive t-BP was as-
UNIFAC model to be used for this system
sumed to be unity because the necessary
values for the peroxide group needed to

0 NO ADDITIVE o NO ADDITIVE
n t-BP
WITH t-BP

0 20 40 60 80 100
0 10 20 30 40 50 60 TIME, s
TIME, s
FIGURE 9. A comparison of experimental evapora-
FIGURE 8. A comparison of the evaporation of tion rates with the UNIFAC model for a four compo-
METH drops with and without additives at 20.7 nent mixture (METH, HEX, cis-DEC, and trans-DEC)
0.3"C. with and without the additive t-BP.
 Aerosol Science and Technology
27:2 August 1997
with confidence. Figure 10 shows mole frac-
tions and activity coefficients calculated for
one of the runs corresponding to Fig. 9.
The initial size of the droplet was a, =
28.81 p m and t-BP was excluded. As ex-
pected, the more volatile cis-DEC and
trans-DEC distill from the droplet quickly,
leaving a droplet composed of primarily
METH and HEX. The METH, being more
volatile than HEX, is the next to distill
leaving a droplet consisting of mainly pure
HEX. Note that even for long times, there
will still be residual traces of the lower-
volatility components. The activity coeffi-
cients shown in Fig. 10 are greater than
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unity, indicating that the evaporation rate
is greater than that calculated from ideal
solution theory. For long times, the activity
coefficients of the cis- and trans-DEC com-
ponents are less than unity, but these
species reach negligible concentrations well
before this occurs and do not affect the
evaporation.
CONCLUSIONS
The theory of binary droplet evaporation
was extended to an N-component system
and compared with experiment. The binary
system BTD/IDD was found to follow ideal
0 20 40 60 80 100
TIME, s
FIGURE 10. Mole fractions xi and activity coefficients
yi calculated from the UNIFAC model during the
evaporation of a four component droplet. The initial
radius of the drop is 28.82 Km, and the temperature is
21.O0C.
Evaporation of Multicomponent Droplets 253
solution behavior, and the UNIFAC model
for activity coefficients together with a dif-
fusion-controlled evaporation rate model
were shown to be in good agreement with
evaporation rate data for multicomponent
droplets consisting of HEX, METH, cis-
DEC, and trans-DEC. The additives, ter-
tiary butyl peroxide and ethyl hexyl nitrate,
were found to have a negligible effect on
the evaporation rate of multicomponent
fuel drops. It is likely that these chemicals
improve combustion properties of fuel mix-
tures either by decomposition at elevated
temperatures and pressures or by their ef-
fects in the gas phase.
The authors are grateful to Ethyl Petroleum Additives
Coiporation for primaly support of this research and to
the National Science Foundation (grant number CTS-
9528897) for partial suppott. We also acknowledge the
assistance of Tae Hun for light-scatteringdata analysis.
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Received 28 October 1996; accepted 14 Febru-
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