Inuence of organic lms on the evaporation and

condensation of water in aerosol

James F. Davies, Rachael E. H. Miles, Allen E. Haddrell, and Jonathan P. Reid
1
School of Chemistry, University of Bristol, Bristol BS8 1TS, United Kingdom
Edited by Mark H. Thiemens, University of California at San Diego, La Jolla, CA, and approved April 23, 2013 (received for review March 20, 2013)
Uncertainties in quantifying the kinetics of evaporation and conden-
sationof water fromatmospheric aerosol are a signicant contributor
to the uncertainty in predicting cloud droplet number and the indirect
effect of aerosols on climate. The inuence of aerosol particle surface
composition, particularly the impact of surface active organic lms, on
the condensation and evaporation coefcients remains ambiguous.
Here, we report measurements of the inuence of organic lms on
the evaporation and condensation of water from aerosol particles.
Signicant reductions in the evaporation coefcient are shown to
result when condensed lms are formed by monolayers of long-chain
alcohols [C
n
H
(2n+1)
OH], with the value decreasing from 2.4 10
3
to 1.7 10
5
as n increases from 12 to 17. Temperature-dependent
measurements conrm that a condensed lm of long-range order
must be formed to suppress the evaporation coefcient below 0.05.
The condensation of water on a droplet coated in a condensed lmis
shown to be fast, with strong coherence of the long-chain alcohol
molecules leading to islanding as the water droplet grows, opening
up broad areas of uncoated surface on which water can condense
rapidly. We conclude that multicomponent composition of organic
lms on the surface of atmospheric aerosol particles is likely to pre-
clude the formation of condensed lms and that the kinetics of water
condensation during the activation of aerosol to form cloud droplets
is likely to remain rapid.
water transport
|
organic monolayers
|
mass accommodation
|
surface lms
T
he transport of volatile and semivolatile components between
the condensed and gas phases in aerosol during evaporation or
condensation is important for understanding cloud microphysics,
atmospheric chemistry, the delivery of drugs to the lungs, and the
applications of aerosols in materials and combustion science. For
example, the uptake of chemical species to atmospheric aerosol
particles facilitates chemical reactions (1), the condensation of
water on cloud condensation nuclei allows cloud droplets to form
(2), the uptake of water on pharmaceutical aerosol can affect their
deposition pattern within the lungs (3), and the evaporation rates
of solvents in spray drying processes inuence the structure and
morphology of the nal microparticle (4). The rate of mass trans-
port to or from an aerosol particle can be considered to involve the
interplay of three mechanistic steps: gas phase diffusion, interfacial
transfer, and bulk condensed phase diffusion. Different limiting
regimes can be identied under which the rate of evaporation or
condensation is determined by any one of these steps (5).
The Knudsen number is the ratio of the mean free path of gas
phase molecules to the particle radius. At low Knudsen number,
in the limits of large particle size and high gas pressure, gas phase
diffusion usually determines evaporation and condensation rates.
Bulk phase diffusion is limiting when the viscosity of the particle
impedes transport to or from the surface and kinetically arrested
states are formed, for example, glassy (6) and semisolid aerosol
particles (7). The magnitude of any limitation imposed on the rate
of mass transfer across the interface is characterized by the mass
accommodation coefcient (
m
), which is dened as the fraction
of molecules colliding with the surface that accommodate into the
bulk liquid phase. By microscopic reversibility, the mass accom-
modation coefcient can be assumed to be equivalent to the
evaporation coefcient () with the two parameters describing the
depression in the net ux of molecular trafc below that expected
from gas kinetic theory and the HertzKnudsen equation (8).
Numerous attempts to measure mass accommodation and evap-
oration coefcients for water at an aqueousgas surface have
reported values ranging over orders of magnitude (9, 10). More
recent work, including a sensitivity analysis of previous studies,
has narrowed the possible value of
m
for pure water to greater
than 0.5 (11). The interplay of the limiting regimes governed by
slow gas phase diffusion and slow interfacial transport is shown in
Fig. 1A. Evaporation and condensation uxes from small particles
(Knudsen numbers of >0.1) are suppressed by even small devia-
tions of the evaporation coefcient from unity; larger particles
only show a measurable suppression in ux due to slow interfacial
transport when the evaporation coefcient is <<1 and gas phase
diffusion is otherwise limiting.
The extent of the suppression of evaporation/condensation by
slow interfacial transport is expected to depend on the surface
composition (12). Dissolved species in an aqueous solution can
preferentially partition to the surface to lower the Gibbs energy by
minimizing hydrophobic interactions with water, reducing the
surface tension and possibly leading to profound changes in mass
accommodation and evaporation coefcients. However, the limi-
tations imposed on the interfacial transport of water between the
gas and aqueous phases due to the presence of species at the sur-
face of aerosol particles remains ambiguous (13, 14). For example,
Saykally and coworkers (15) have investigated ion adsorption at
water surfaces and the resulting impact on mass transfer. Although
ammonium sulfate was not found to inuence the evaporation ki-
netics of water (16), subtle effects due to the presence of more
surface active perchlorate ions were observed (17).
Organic molecules are more surface active than ionic salts and
would be expected to have a greater impact on interfacial transport.
Organic lms are of particular interest in cloud microphysics owing
to their potential abundance in the atmosphere (18, 19). The effect
of monomolecular lms on the uptake coefcient of N
2
O
5
has been
investigated by Cosman et al. (20) and is one of few examples in
which the effect of a surface lmon mass transport at the surface of
an aerosol has been unambiguously identied. The inuence of
organic surface lms on water transport has been mostly inferred
from studies on at surfaces and large droplets (2126), mea-
surements that are largely insensitive to the kinetics of interfacial
transfer due to the low Knudsen numbers involved, and the mag-
nitude of the suppression for aerosol particles remains unclear.
The packing density and ordering of organic surfactant mole-
cules in a monomolecular lm can show 2D phase behavior
analogous to that observed in bulk gas, liquid, and solid phases
(27). For a densely packed lm of a long-chain alcohol, with
a surface area per molecule of <20
2
, a 2D solid lm is formed
with long-range ordering and a coherent arrangement of hydro-
phobic chains. From molecular-dynamic simulations, the chains
Author contributions: J.P.R. designed research; J.F.D., R.E.H.M., and A.E.H. performed
research; J.F.D. analyzed data; and J.F.D., R.E.H.M., A.E.H., and J.P.R. wrote the paper.
The authors declare no conict of interest.
This article is a PNAS Direct Submission.
1
To whom correspondence should be addressed. E-mail: j.p.reid@bristol.ac.uk.
www.pnas.org/cgi/doi/10.1073/pnas.1305277110 PNAS | May 28, 2013 | vol. 110 | no. 22 | 88078812
C
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are predicted to align perpendicular to the surface with little tilt
relative to the surface normal (28). As the packing density de-
creases and the lm is allowed to expand, the surface area per
molecule increases and the lm behaves more like a liquid phase,
retaining only short-range interactions but losing long-range or-
der. The chains tilt relative to the surface normal and the layer is
expected to become more permeable to water (28). Finally, a
gaseous lm is characterized by the loss of even short-range
interactions, and individual surfactant molecules can be assumed
to act independently. The accessible area theory, proposed by
Barnes et al. (29), suggests that resistance to evaporation imposed
by a molecular lm is governed by the availability of holes large
enough for water molecules to pass through. As such, tighter
packing and longer chains are expected to increase resistance
to evaporation.
In this study, we investigate the inuence of monomolecular
lms of long-chain fatty alcohols [functional form C
n
H
(2n+1)
OH]
on the evaporation of water from single aqueous aerosol droplets,
520 m in radius. The size (and Knudsen) regime attainable
through our technique confers signicantly increased sensitivity to
the evaporation coefcient compared with other single-particle
and at-surface measurements. Indeed, an evaporation coefcient
of 0.05 can be unambiguously identied following an assessment
of the associated uncertainties (5, 11). More specically, we report
the dependence of the evaporation coefcient on the length of the
aliphatic chain and on temperature, and compare evaporation
with the condensation of water on coated aqueous NaCl droplets.
Results and Discussion
Mass Transport of Water Across a Hexadecanol Monolayer. The in-
uence of initially submillimolar concentrations of hexadecanol
(n = 16; Fluka; 99%) on the evaporation of water from a drop-
let held in a gas phase at a relative humidity (RH) of 80% is
shown in Fig. 1B. Within the rst 200 ms, the ethanol used to
solubilize the fatty alcohol in the aqueous droplet rapidly evap-
orates, leaving only water and hexadecanol. Water then con-
tinues to evaporate at a rate consistent with that observed from
pure water droplets before an abrupt and marked decrease in the
evaporation rate is observed. We have demonstrated previously
that we can accurately track the concentration prole of an
evaporating droplet through knowledge of the initial conditions,
the droplet size and solute concentration (5). The concentration
of the fatty alcohol in the droplet at the radius at which the
evaporation rate decreases can be used to estimate the surface
packing of the lm, under the assumption that all of the fatty
alcohol resides at the surface. The surface area per molecule was
found to be between 20 and 22
2
at the point where evapora-
tion retardation was observed (Table 1) for all three of the
starting solute concentrations studied. The calculated values are
consistent with literature data for the surface area of a molecule
in a condensed alkylic monolayer (3032) and suggest that the
slowing of the evaporation rate is due to the formation of a
condensed monolayer lm.
Following lm formation, water loss continues at a reduced
rate with an approximately linear decrease in radius with time.
This can be contrasted with the linear dependence of the radius-
squared on time observed when gas diffusion limits the rate of
evaporation from pure water droplets in the continuum (gas
diffusion limited) regime. The reduced evaporation rate can be
used to estimate the value of the evaporation coefcient from the
semianalytic treatment described in the Materials and Methods.
Independent of the initial concentration of hexadecanol, the
evaporation of water is consistent with a of (2.85 0.20) 10
5
,
with the model accurately reproducing both the rate and linearity
of the time dependence in radius for the remainder of the droplet
evaporation. The invariable value of the evaporation coefcient
as the droplet radius (and total surface area) diminishes suggests
that the packing density of molecules in the surface lm remains
constant. If the monolayer does not compress further, transfer of
the fatty alcohol molecules from the surface lm into the aqueous
bulk must occur.
Fig. 1. (A) Calculated values of the mass ux from evaporating water droplets
with variation in evaporation coefcient over a size range covering four orders
of magnitude. The gas phase pressure is 100 kPa and the temperature is 293 K.
(B) Evaporation of 1:1 by volume waterethanol droplets doped with hex-
adecanol at initial alcohol concentrations of 0.62, 0.33, and 0.165 mM (red,
orange, and green, respectively) into a surrounding RH of 80%. The evapo-
ration prole for pure water (blue) is shown for reference. Droplet evaporation
shown over an extended timescale highlights the continued steady decrease in
radius with time. The model simulation for = 2.85 10
5
is shown for com-
parison (black dash), along with the uncertainty in RH (gray envelope). This
equates to a 7% uncertainty in the value of the evaporation coefcient.
Table 1. Initial size (R
0
) and concentration (C
0
) of the droplets
reported in this work
n C
0
, mM R
0
, m R
def
, m A
mol
,
2

12* 0.200 22.5 8.9 16.1 2.35 0.15 10

3
13 0.200 22.2 9.7 20.0 1.2 0.1 10
3
14 0.090 25 7.9 20.7 4.0 0.4 10
4
15 0.130 24.5 9.4 22.0 8.0 0.6 10
5
16 0.620 22.5 17.8 22.4 2.85 0.20 10
5
16 0.330 25.5 14.8 20.0 2.85 0.20 10
5
16 0.165 25 10.4 20.9 2.85 0.20 10
5
17 0.025 24 7.7 21.9 1.65 0.05 10
5
The concentration of the fatty alcohol [functional form C
n
H
(2n+1)
OH] at
the point of deection in the evaporation rate was calculated from the
particle size (R
def
). Assuming all molecules resided at the surface, a surface
area per molecule was calculated (A
mol
).
*Data for dodecanol data were recorded at 283 K, not 293 K, as explained in
the text.
8808 | www.pnas.org/cgi/doi/10.1073/pnas.1305277110 Davies et al.
The uncertainty associated with interpreting the kinetics of mass
transfer arises primarily from the uncertainty in RH (2%), esti-
mated from the rate of water evaporation following complete loss
of ethanol and before the inuence of the lm. The inuence of this
uncertainty on the model predictions is shown in Fig. 1B as a gray
envelope and equates to an uncertainty in the evaporation co-
efcient of 7%. From our previous work, we have noted uncer-
tainties associated with the thermophysical parameters, specically
the gas phase diffusion and thermal conductivity constants (11).
However, when the evaporation coefcient is <<1, as in the case
here, these uncertainties have negligible effect on the value esti-
mated for the evaporation coefcient.
Previous studies have qualitatively investigated the effect of
hexadecanol on the evaporation rate of water. Garrett (23) noted
a decrease in the evaporation rate for water droplets 50250 m
in radius coated with hexadecanol sitting on a Teon mesh, al-
though the exact droplet size was not reported. A decrease in the
evaporation rate of around an order of magnitude was reported
compared with the evaporation of pure water droplets, much less
pronounced than the decrease in evaporation rate observed in
our measurements of around two orders of magnitude. When the
difference in Knudsen number is accounted for, however, these
observations are broadly consistent. A decrease in the mass ux
of an order of magnitude below that expected from a water
surface is expected for a droplet size of 160 m in radius (Fig.
1A), well within the size range measured by Garrett.
Dependence of the Evaporation Coefcient on the Carbon Chain Length.
Measurements of evaporation from droplets containing fatty alco-
hols of varying chain length have been used to investigate the in-
uence of the thickness of the monolayer lm on the evaporation
rate (Fig. 2), retaining the same OH head group for all measure-
ments. In addition to hexadecanol, we have studied dodecanol (n =
12; Fluka; 98%), tridecanol (n = 13; Sigma-Aldrich; 97%), tet-
radecanol (n = 14; Fluka; 99%), pentadecanol (n = 15; Sigma-
Aldrich; 99%), and heptadecanol (n = 17; Sigma-Aldrich; 98%). As
the carbon chain length is increased, the degree of slowing in the
evaporation rate following monolayer formation becomes more
signicant.
The evaporation of water from droplets doped with dodecanol
(n = 12) is consistent with that observed from pure water
droplets at room temperature with no slowing that could be at-
tributed to the formation of a monolayer. Despite the droplets
reaching a concentration of dodecanol required for monolayer
formation at around 10 m, they continued to decrease in size at
the same rate until they were lost from the trap when <6 m in
radius. However, at a lower gas phase temperature (283 K as
opposed to 293 K), a marked decrease in the evaporation rate
was once again observed at a dodecanol concentration corre-
sponding to monolayer formation. The melting point of dodec-
anol is 297 K, and at room temperature it exists as a waxy liquid.
On reducing the temperature, the dodecanol forms a condensed
solid lm with long-range coherence of the alkyl chains and an
evaporation coefcient consistent with the trend observed at 293
K for the longer-chain alcohols.
An evaporation coefcient inferred from the data presented by
Tuckermann et al. (33) of the evaporation rate of water from
aqueous droplets doped with octadecanol (n = 18), held in an
acoustic trap at 293 K, is also included in Fig. 2. The authors ob-
served a reduction in the evaporation rate following formation of
a monolayer consistent with an evaporation coefcient of 8.5
10
6
, a value in consistent with the trend found in our experiments.
For each of the alcohols studied at 293 K, the surface area per
molecule at the onset of monolayer formation was estimated and
fell within the range of 2022
2
(Table 1), with a slightly lower
area for lm formation in dodecanol-doped droplets at 283 K.
Henry et al. (28) reported that the hydrocarbon chains are fully
extended with very little tilt when the area falls below 24
2
,
providing the maximum barrier to water transport. Although the
surface packing density responsible for inhibiting water transport
does not change signicantly along the homologous series, the
magnitude of the suppression does. An increasing resistance to
water transport through the lm is indeed expected (28), con-
sistent with an increase in the escape path (barrier length) that
water molecules must pass through from the aqueous phase into
the gas phase.
Dependence of the Evaporation Coefcient on Temperature. Evap-
oration rates from hexadecanol-doped droplets were measured
over a range of temperatures (Fig. 3A). The evaporation co-
efcient shows a marked increase with temperature over the
range of 283 to 312 K, above which the increase becomes even
more pronounced. It is worth noting that, in this regime, the
droplet and gas phase will be at signicantly different temper-
atures, due to the removal of latent heat during the evaporation
of water. The ambient and low-temperature measurements re-
ported in the previous sections were performed under humid
conditions, in which the droplet temperature depression due to
loss of latent heat via evaporation of water from the droplet is
minimal. When the gas phase temperature is increased, there is
an associated increase in the saturation vapor pressure of water,
leading to a reduction in the RH at which the evaporation rate is
measured. Thus, measurements at higher temperatures are
performed under much drier conditions, with an associated in-
crease in the uncertainty in the RH (<20% 10% RH) at T >
315 K. The semianalytic treatment of mass ux can be used to
estimate the steady droplet temperature during evaporation, and
the results of these calculations are also shown by correcting the
apparent droplet temperature in Fig. 3A. The dramatic rise in
evaporation coefcient appears to be consistent with the ap-
proach to the melting temperature of the condensed surface lm,
mirroring the effect of decreasing the temperature on the effect
of a dodecanol lm.
The surface area per molecule at the point of monolayer for-
mation is reported for each temperature in Fig. 3B. As the tem-
perature increases, the packing density decreases, and a correlation
between packing density and the associated evaporation coefcient
is observed. This behavior is qualitatively consistent with previous
work measuring reactive uptake of N
2
O
5
onto aqueous surfaces
coated with organic species of varying packing density (20) and is
again consistent with the phase of the monolayer, as described by
Fig. 2. The evaporation coefcient (on a log
10
scale) as a function of carbon
chain length. The low-temperature data (283 K) associated with n = 12 is
shown in gray, and the calculated value for data presented by Tuckermann
et al. (33) for octadecanol (n = 18) is shown as a black circle. The range
of evaporation coefcients possible for pure water, as discernible by our
technique, is shown by the gray shaded region.
Davies et al. PNAS | May 28, 2013 | vol. 110 | no. 22 | 8809
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Donaldson et al. (27). Indeed, Henry et al. (28) suggested that an
increase in temperature would lead to expansion of an octadecanol
monolayer lm and increased permeability.
Water Condensation on Monolayer-Coated Aqueous Aerosol. Water
condensation has been studied by rst forming, by evaporation,
a droplet with a complete monolayer coverage of hexadecanol.
Specically, an aqueous sodium chloride droplet, doped with
hexadecanol, was allowed to evaporate into a gas phase held at an
RH of 60% (Fig. 4A). The monolayer reduced considerably the
evaporation rate at the point at which a condensed lm was
formed. To then study water condensation on the coated droplet,
the RH was rapidly increased from 60% to 80%. Measurements
were performed on both coated and uncoated (pure sodium
chloride solution) droplets for comparison. Following equilibra-
tion at 60% RH, the uncoated droplet responded rapidly to the
increase in RH and displayed a repeatable size change on cycling
the RH between 60% and 80%. Indeed, the time dependence of
the droplet size was used to retrieve the typical time variance in
water activity experienced by a growing droplet in these mea-
surements (shown in Fig. 4B). Perhaps surprisingly, the coated
droplet also responded rapidly to the increase in RH, even after
the monolayer had formed. On subsequent decrease in RH, the
droplet size response was again rapid until it reached its size
before the RH increase. Evaporation then continued in a slow
manner and another cycle of the RH displayed similar behavior.
Following equilibrium, both condensation and subsequent evap-
oration of water behaved in the same way as the uncoated droplet.
Fig. 4B compares more closely the sequential condensation
proles (ad), conrming that the timescales for condensational
growth are similar to the variation in water activity retrieved
from the uncoated droplet. Notably, the direction of mass ux
does not reverse and water does not start to condense on the
coated droplet until the RH has surpassed the water activity that
the droplet has reached during evaporation. For example, there
is a signicant time lag between the RH change and the response
in droplet size for the rst increase in RH, with the RH in the gas
phase rst needing to climb up to a value that surpasses the
water activity in the droplet. We suggest that the strong cohesion
of alcohol chains as the droplet surface area begins to expand,
with the alcohol persisting as islands, leads to regions of the
droplet surface that are free from surfactant and condensation
kinetics that show no inhibition. The coherence of surfactant
molecules in islands on lm expansion is not uncommon and has,
for example, been seen for palmitic acid and stearic acid lms on
a water surface (34). On such a short timescale, the long-chain
alcohol molecules that have partitioned into the particle bulk
Fig. 3. (A) The effect of varying the gas phase temperature (black points) on
the evaporation coefcient for water droplets doped with 0.2 mM hex-
adecanol. The melting point of hexadecanol is indicated. Note that the
droplet will be at a lower temperature than the gas phase due to evaporative
cooling, an effect that becomes more important at high temperatures where
the RH is lower and evaporation is more rapid. The droplet temperature,
estimated from the mass ux equations, is plotted in gray, and the un-
certainty in both axes is estimated based on the uncertainty in the RH. In cases
in which no error bar is present, the point itself is equal to or much larger than
the uncertainty in the measurement. (B) The dependence of the evaporation
coefcient on the surface area per molecule of the monolayer, calculated for
each of the temperatures presented in A. The uncertainty in surface area
comes primarily from the initial size uncertainty, which increases with more
the rapid evaporation at higher temperatures. The largest error bar is due to
an anomaly in the observed formation of the monolayer, and the radius at
the point of monolayer formation was less clear.
Fig. 4. (A) Kinetics of evaporation and condensation during RH cycling
between 60% and 80% for a sodium chloride droplet coated with a hex-
adecanol monolayer. (B) Size changes for events ad (labeled in A). t = 0 s on
this plot indicates when the RH change was initiated. The size response of an
uncoated droplet is shown by the dashed black line, whereas the corre-
sponding change in RH inferred from the response of this pure sodium
chloride droplet, is indicated by the dashed gray line.
8810 | www.pnas.org/cgi/doi/10.1073/pnas.1305277110 Davies et al.
(largely as micelles) are unable to sustain a complete condensed
lm on growth.
Implications for Water Transport in Atmospheric Aerosol. The de-
pendence of the evaporation coefcient on the composition and
phase of an organic surface lm is now clear. The packing density
at the point at which the evaporation rate arrests, the lowering of
temperature required for dodecanol-coated droplets to show
a similar behavior to longer chain alcohols, and the temperature
dependence of the evaporation coefcient for hexadecanol lms,
all indicate that a solid condensed lm must form for the evap-
oration coefcient of water to be reduced below a value of 0.05.
Increasing the length of the carbon chain from n = 12 to 18
reduces the evaporation coefcient by a factor of 300, decreasing
the value from 2.4 10
3
to 8.5 10
6
. The trend of decreasing
evaporation coefcient with increased packing density (Fig. 3B)
is qualitatively consistent with molecular-dynamic simulations of
the mass accommodation coefcient of water on aqueous sur-
faces coated by long-chain fatty acids. For example, Takahama
and Russell (35) reported a value of 0 (upper possible limit, 0.04)
for water accommodating on a surface coated with myristic acid
at approaching full coverage. These observations strongly suggest
that, for all but the most coherent of lms, the evaporation co-
efcient, and by microscopic reversibility the mass accommoda-
tion coefcient, will be larger than 0.05. It should be noted that
the thermal accommodation coefcient is assumed to remain
unaffected, and future work may elucidate whether this is valid
through the use of gas phases with different thermal conductiv-
ities, such as helium.
For ambient aerosol, it can be largely assumed that the full
complexity of organic composition prevents the formation of
a solid coherent lm of long-range order with the high packing
density characteristic of a condensed lm required for suppres-
sion of water transport. This conclusion is broadly consistent with
a recent analysis of a wide range of growth kinetic measurements
made on ambient aerosols at various geographic locations, which
concluded that the mass accommodation coefcient must be
larger than 0.1 for cloud condensation nuclei (36). It is also
consistent with laboratory-based measurements that have shown
that the presence of surface-active ions or lowmolecular-weight
organic compounds (e.g., acetic acid) have little to no effect on
the evaporation coefcient (16, 17). However, it must be re-
membered that tropospheric temperatures are largely lower than
studied here. This fact may yet lead to a role for organic lms in
leading to marked suppressions of interfacial transport under
certain circumstances.
The increasing impermeability to water transport of organic
lms with increasing carbon chain length will provide invaluable
data for molecular-dynamic simulations and should allow us to
more fully understand the mechanism of water transport across an
organic layer. Furthermore, the apparent sustained coherence of
an organic lm when water condensation occurs, and the rapid
response in droplet size through condensation, suggests that the
growth of a droplet preserves islands of organic surfactants and
opens up areas of uncoated water surface on which water con-
densation can occur rapidly. Molecular-dynamic simulations for
droplets coated in a long-chain fatty acid could provide further
insights into the dynamics that are occurring (11, 28, 37). Finally,
although it is not possible to determine the lowest possible limit on
the evaporation coefcient, with the value declining up to n = 18
chain length, the inuence of longer-chain surfactants will provide
greater insight into the mechanism of interfacial transport.
Materials and Methods
The experimental technique has been discussed by us previously and will
be only briey reviewed here (5, 38). The sample solution is placed in the
reservoir of a microdispenser (Microfab MJ-ABP-01; 30-m orice). Single
droplets are produced by the application of a voltage pulse, and an in-
duction electrode imparts a charge on the droplet as it forms, allowing it to
be manipulated by the elds of an electrodynamic balance (EDB), formed
from two pairs of concentric cylindrical electrodes. The strong electric eld
connes the droplet within 100 ms of generation. The trapped droplet is
illuminated with a cw-laser beam (532 nm) and the evolving droplet size is
estimated from the angularly resolved elastic scattering pattern using a
geometrical optics approximation to determine the radius (39). The time
resolution of size measurements made during the initial rapid evaporation is
chosen to be 10 ms, with measurements following slower size changes av-
eraged every second. During connement, a ow of nitrogen of xed RH is
passed over the droplet surface, allowing precise control of the gas phase
environment. The chamber design allowed the temperature to be controlled
between 283 and 330 K, with a stability of <<1 K, and a nitrogen airow
although the outer cylindrical electrode to be introduced, permitting the use
of greater ow rates. Coupled with a four-way valve, the chamber could be
rapidly cycled between two xed gas phase conditions, with a half-time of
<5 s for the change in RH.
The fatty alcohols used in this study are largely insoluble in water, but
partially soluble in ethanol. Solutions of these fatty alcohols at submillimolar
concentrations (Table 1) were made up in a 50% (vol/vol) aqueous mixture
of ethanol and water. Droplets generated from these solutions were in-
troduced into the cylindrical EDB and the effect of the fatty alcohol on water
evaporation alone was investigated at an RH of 80%, following the initial
rapid evaporation of ethanol in the rst few 100 ms. Measurements were
made on multiple droplets with the same initial size and composition, and
an average evaporation trend determined. No dependence of the long-time
evaporation from the water droplet due to the initial presence of ethanol
was observed. For measurements of water uptake, droplets generated from
a sodium chloride solution in water/ethanol containing hexadecanol were
conned in the EDB at an RH of 60%. The RH was cycled between 60% and
80% RH, and the droplet response was recorded as water condensation and
evaporation occurred.
To quantitatively interpret our measurements, the evaporation meas-
urements are compared with simulations froma semianalytic mass ux model
based on the well-established framework of Kulmala et al. (40). We have
discussed previously the applicability of this model in the interpretation of
our measurements (5, 11, 13, 38). The transition regime correction factors of
FuchsSutugin are used to account for the marked reduction in the contin-
uum mass and heat uxes observed due to the slow interfacial transfer ki-
netics and the considerable diminution of the evaporation coefcient when
an organic lm is formed. The thermal accommodation coefcient is as-
sumed to be unity throughout, consistent with previous experimental work
(41) on water surfaces. However, it should be noted that the effect of sur-
face lms on the thermal accommodation coefcient is unknown. Values of
the thermophysical parameters required by the model were taken from the
recommendations of Miles et al. (11).
ACKNOWLEDGMENTS. We thank the Engineering and Physical Sciences
Research Council for nancial support through a Leadership Fellowship
awarded to J.P.R. (Grant EP/G007713/1). R.E.H.M. acknowledges Natural
Environment Research Council for nancial support within the Aerosol
Cloud InteractionsA Directed Programme to Reduce Uncertainty in Forcing
(Grant NE/I020075/1).
1. Davidovits P, Kolb CE, Williams LR, Jayne JT, Worsnop DR (2006) Mass accommodation
and chemical reactions at gas-liquid interfaces. Chem Rev 106(4):13231354.
2. Laaksonen A, Vesala T, Kulmala M, Winkler PM, Wagner PE (2005) Commentary on
cloud modelling and the mass accommodation coefcient of water. Atmos Chem Phys
5:461464.
3. Haddrell AE, Hargreaves G, Davies JF, Reid JP (2013) Control over hygroscopic growth of
saline aqueous aerosol using Pluronic polymer additives. Int J Pharm 443(12):183192.
4. Lin J-C, Gentry JW (2003) Spray drying drop morphology: Experimental study. Aerosol
Sci Technol 37(1):1532.
5. Davies JF, Haddrell AE, Miles REH, Bull CR, Reid JP (2012) Bulk, surface, and gas-phase
limited water transport in aerosol. J Phys Chem A 116(45):1098710998.
6. Bones DL, Reid JP, Lienhard DM, Krieger UK (2012) Comparing the mechanism
of water condensation and evaporation in glassy aerosol. Proc Natl Acad Sci USA
109(29):1161311618.
7. Shiraiwa M, Ammann M, Koop T, Pschl U (2011) Gas uptake and chemical aging of
semisolid organic aerosol particles. Proc Natl Acad Sci USA 108(27):1100311008.
8. Li W, Davis EJ (1996) Aerosol evaporation in the transition regime. Aerosol Sci Technol
25(1):1121.
Davies et al. PNAS | May 28, 2013 | vol. 110 | no. 22 | 8811
C
H
E
M
I
S
T
R
Y
9. Davidovits P, et al. (2004) Mass accommodation coefcient of water vapor on liquid
water. Geophys Res Lett 31:L22111.
10. Marek R, Straub J (2001) Analysis of the evaporation coefcient and the condensation
coefcient of water. Int J Heat Mass Transfer 44(1):3953.
11. Miles REH, Reid JP, Riipinen I (2012) Comparison of approaches for measuring the
mass accommodation coefcient for the condensation of water and sensitivities to
uncertainties in thermophysical properties. J Phys Chem A 116(44):1081010825.
12. Nathanson GM (2004) Molecular beam studies of gas-liquid interfaces. Annu Rev Phys
Chem 55:231255.
13. Miles REH, Knox KJ, Reid JP, Laurain AMC, Mitchem L (2010) Measurements of mass
and heat transfer at a liquid water surface during condensation or evaporation of
a subnanometer thickness layer of water. Phys Rev Lett 105(11):116101.
14. Julin J, et al. (2013) Mass accommodation of water: Bridging the gap between mo-
lecular dynamics simulations and kinetic condensation models. J Phys Chem A 117(2):
410420.
15. Otten DE, Shaffer PR, Geissler PL, Saykally RJ (2012) Elucidating the mechanism of
selective ion adsorption to the liquid water surface. Proc Natl Acad Sci USA 109(3):
701705.
16. Drisdell WS, Saykally RJ, Cohen RC (2009) On the evaporation of ammonium sulfate
solution. Proc Natl Acad Sci USA 106(45):1889718901.
17. Drisdell WS, Saykally RJ, Cohen RC (2010) Effect of surface active ions on the rate of
water evaporation. J Phys Chem C 114(27):1188011885.
18. Ellison GB, Tuck F (1999) Atmospheric processing of organic aerosols. J Geophys Res
104(D9):1163311641.
19. Kolb CE, et al. (2010) An overview of current issues in the uptake of atmospheric trace
gases by aerosols and clouds. Atmos Chem Phys 10:1056110605.
20. Cosman LM, Knopf DA, Bertram AK (2008) N
2
O
5
reactive uptake on aqueous sulfuric
acid solutions coated with branched and straight-chain insoluble organic surfactants.
J Phys Chem A 112(11):23862396.
21. Docking AR, Heymann E, Kerley LF, Mortensen KN (1940) Evaporation of water
through multimolecular lms. Nature 146:265.
22. Fox R (1965) An oilwaxsurfactant system for retarding the evaporation of water.
Nature 205:10041005.
23. Garrett W (1971) Retardation of water drop evaporation with monomolecular surface
lms. J Atmos Sci 28:816819.
24. Gill P, Graedel T, Weschler C (1983) Organic lms on atmospheric aerosol particles,
fog droplets, cloud droplets, raindrops, and snowakes. Rev Geophys 21(4):903920.
25. Donaldson DJ, Vaida V (2006) The inuence of organic lms at the air-aqueous
boundary on atmospheric processes. Chem Rev 106(4):14451461.
26. Tuckermann R, Bauerecker S, Cammenga HK (2007) Generation and characterization
of surface layers on acoustically levitated drops. J Colloid Interface Sci 310(2):559569.
27. Donaldson DJ, Tuck AF, Vaida V (2001) Spontaneous ssion of atmospheric aerosol
particles. Phys Chem Chem Phys 3:52705273.
28. Henry DJ, et al. (2010) Monolayer structure and evaporation resistance: A molecular
dynamics study of octadecanol on water. J Phys Chem B 114(11):38693878.
29. Barnes G, Quickenden T, Saylor J (1970) A statistical calculation of monolayer per-
meation by water. J Colloid Interface Sci 33(2):236243.
30. Kaganer V, Mhwald H, Dutta P (1999) Structure and phase transitions in Langmuir
monolayers. Rev Mod Phys 71(3):779819.
31. Onorato RM, Otten DE, Saykally RJ (2009) Adsorption of thiocyanate ions to the
dodecanol/water interface characterized by UV second harmonic generation. Proc
Natl Acad Sci USA 106(36):1517615180.
32. Can SZ, Mago DD, Esenturk O, Walker RA (2007) Balancing hydrophobic and hydro-
philic forces at the water/vapor interface: Surface structure of soluble alcohol mon-
olayers. J Phys Chem C 111(25):87398748.
33. Tuckermann R, Bauerecker S, Cammenga HK (2007) The generation of octadecanol
monolayers on acoustically levitated water drops. Coll Surf A Physicochem Eng As-
pects 309(1-3):198201.
34. Sierra-Hernndez MR, Allen HC (2010) Incorporation and exclusion of long chain
alkyl halides in fatty acid monolayers at the air-water interface. Langmuir 26(24):
1880618816.
35. Takahama S, Russell LM (2011) A molecular dynamics study of water mass accom-
modation on condensed phase water coated by fatty acid monolayers. J Geophys Res
116:D02203.
36. Raatikainen T, et al. (2013) Worldwide data sets constrain the water vapor uptake
coefcient in cloud formation. Proc Natl Acad Sci USA 110(10):37603764.
37. Vieceli J, Roeselov M, Tobias DJ (2004) Accommodation coefcients for water vapor
at the air/water interface. Chem Phys Lett 393:249255.
38. Davies JF, Haddrell AE, Reid JP (2012) Time-resolved measurements of the evapora-
tion of volatile components from single aerosol droplets. Aerosol Sci Technol 46(6):
666677.
39. Glantschnig WJ, Chen S-H (1981) Light scattering from water droplets in the geo-
metrical optics approximation. Appl Opt 20(14):24992509.
40. Kulmala M, Vesala T, Wagner PE (1993) An analytical expression for the rate of binary
condensational particle growth. Proc R Soc Lond A 441:589605.
41. Winkler PM, et al. (2004) Mass and thermal accommodation during gas-liquid con-
densation of water. Phys Rev Lett 93(7):075701.
8812 | www.pnas.org/cgi/doi/10.1073/pnas.1305277110 Davies et al.