Raman spectroscopy of solutions and interfaces containing nitrogen dioxide, water,

and 1,4 dioxane: Evidence for repulsion of surface water by NO2 gas
Garold Murdachaew, Mychel E. Varner, Wytze E. van der Veer, R. Benny Gerber, and Leon F. Phillips

Citation: The Journal of Chemical Physics 140, 184702 (2014); doi: 10.1063/1.4874640
View online: http://dx.doi.org/10.1063/1.4874640
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/140/18?ver=pdfcov
Published by the AIP Publishing

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THE JOURNAL OF CHEMICAL PHYSICS 140, 184702 (2014)
Raman spectroscopy of solutions and interfaces containing nitrogen
dioxide, water, and 1,4 dioxane: Evidence for repulsion of surface water
by NO
2
gas
Garold Murdachaew,
1
Mychel E. Varner,
2
Wytze E. van der Veer,
2
R. Benny Gerber,
1,2
and Leon F. Phillips
2,3,a)
1
Institute of Chemistry and the Fritz Haber Research Center for Molecular Dynamics, Hebrew University,
Jerusalem 91904, Israel
2
Department of Chemistry, University of California, Irvine, California 92697, USA
3
Department of Chemistry, University of Canterbury, Private Bag 4800, Christchurch, New Zealand
(Received 26 November 2013; accepted 21 April 2014; published online 8 May 2014)
The interaction of water, 1,4 dioxane, and gaseous nitrogen dioxide, has been studied as a func-
tion of distance measured through the liquid-vapour interface by Raman spectroscopy with a narrow
(<0.1 mm) laser beamdirected parallel to the interface. The Raman spectra showthat water is present
at the surface of a dioxane-water mixture when gaseous NO
2
is absent, but is virtually absent from
the surface of a dioxane-water mixture when gaseous NO
2
is present. This is consistent with re-
cent theoretical calculations that show NO
2
to be mildly hydrophobic. 2014 AIP Publishing LLC.
[http://dx.doi.org/10.1063/1.4874640]
I. INTRODUCTION
Kolb et al.
1
have presented a thorough review, up to
2010, of outstanding theoretical and experimental problems
relating to the reactions of atmospheric trace gases, including
NO
2
, with a variety of wet and dry surfaces, and it is clear
that there are still many interesting problems that need to be
investigated.
A recent theoretical study
2
of the interaction of nitro-
gen dioxide with the surface of water led to the conclusion
that, even though the binding energy of the O
2
NOH
2
com-
plex was found to be 9.5 kJ mol
1
, a factor of 2 larger than
previously calculated, nitrogen dioxide is at least mildly
hydrophobic. Instead of taking part in hydrogen bonds, the
oxygen atoms of NO
2
were found to be repelled by water
molecules, which led to an unexpected preferential orienta-
tion of NO
2
at the surface, with the oxygen atoms pointing out
of the interface, and suggested that, in a system with mixed
solvents, the surface might actually be depleted of water. This
cast newlight on the processes by which nitrous acid (HONO)
is produced in the troposphere, indicated the need for an ex-
perimental test of the theoretical results, and provided the mo-
tivation for the present study.
Donaldson and co-workers
38
have shown that glancing-
angle Raman spectroscopy is a very useful surface-selective
technique for probing a surface region with a thickness of
the order of 10100 molecular layers, being able to measure
both surface concentrations of solutes and surface depletion
of solvents. Thus, for example, Wren and Donaldson
7
used
glancing-angle Raman spectroscopy to study the reaction of
gas-phase ozone with NaBr and NaI at the surfaces of aque-
ous solutions.
a)
Author to whom correspondence should be addressed. Electronic mail:
leon.phillips@canterbury.ac.nz
The experiments reported here do not require surface se-
lectivity of the kind employed in the experiments of Donald-
son et al.,
38
but simply exploit the ability of Raman spec-
troscopy with a narrow (<0.1 mm) laser beam to obtain
spectra that arise from species close to and within the in-
terface. This limited selectivity, perhaps somewhat unexpect-
edly, proves to be sufcient to detect the mutual repulsion be-
tween water molecules and NO
2
molecules at the gas-liquid
interface. To make the experiment work, it was necessary to
use a mixed solvent comprised of water and 1,4 dioxane, the
purpose of the dioxane being to provide a reference surface
relative to which the displacement of water could be observed.
Surface tension measurements
9
indicate that 1,4 dioxane be-
haves as a weak surfactant in water, but this surfactant effect
plays no role in our experiments, which could not resolve a
surface monolayer. Dioxane was chosen as the reference sub-
stance because it is both unreactive and totally miscible with
water, properties that have often been exploited by electro-
chemists and spectroscopists.
As in the earlier study of NO
2
gas interacting with ni-
tric acid,
10
Raman spectra of H
2
O.NO
2
species were sought
but, consistent with the theoretical prediction of very weak
binding between H
2
O and NO
2
and the small calculated fre-
quency differences between the vibrations of unbound and
bound species (Table I), no such spectra were found. The
absence of large red shifts in the IR upon formation of the
NO
2
H
2
O complex is another indication that normal hydro-
gen bonds are not formed, but rather the relatively weaker and
longer bonds discussed in Ref. 2.
Low-resolution uorescence spectra of gaseous NO
2
were observed with comparable intensity to the Raman spec-
tra. The long (100 s) radiative lifetime
11
of NO
2
at the ex-
citation wavelength (523 nm) used in our experiments caused
the uorescence spectrum of NO
2
gas excited close to the in-
terface to be distinctly different from that of gas excited only
0021-9606/2014/140(18)/184702/7/$30.00 2014 AIP Publishing LLC 140, 184702-1
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184702-2 Murdachaew et al. J. Chem. Phys. 140, 184702 (2014)
TABLE I. Calculated vibrational frequencies (harmonic, unscaled, using
BLYP-D2/aug-cc-pVDZ, see Ref. 2 for details) for NO
2
and H
2
O and for
two isomers of the H
2
O.NO
2
complex. Experimental frequencies for NO
2
and H
2
O are also shown.
NO
2
calc. H
2
O calc.
753 1393 1704 1616 3791 3903
C
s
H
2
O.NO
2
calc. C
s
H
2
O.NO
2
calc.
754 1398 1712 1610 3792 3906
C
2v
H
2
O.NO
2
calc. C
2v
H
2
O.NO
2
calc.
754 1396 1707 1610 3789 3903
NO
2
expt. H
2
O expt.
750 1318 1618 1595 3657 3756
a few millimeters higher in the cell (Figs. 1(a) and 1(b)). The
low-wavenumber Raman spectrum of the bulk solution sev-
eral millimeters below the interface (Fig. 1(c)) showed peaks
that could be assigned to HNO
3
, HNO
2
, N
2
O
4
, N
2
O
3
, NO
2
,
NO, N
2
O, nitrite and nitrate ions, as well as dioxane. The odd
members of this collection are NO, formed by decomposition
of N
2
O
3
, N
2
O
3
, which is responsible for the blue colour of
the solution, and N
2
O (not shown in Fig. 1(c)), for which a
plausible production mechanism
12
is
H
2
O +N
2
O
4

HONO +HNO
3
, (1)
HONO +HONO

H
2
O +N
2
O
3
, (2)
HONO +HONO

HNO +HNO
3
, (3)
HNO +HNO

H
2
O +N
2
O, (4)
where everyone of these reversible processes involves some
interesting dynamics. In our system, the resonance Raman
spectrum of NO
2
is about 150 times more intense than the
non-resonance Raman spectrum of N
2
O. The N
2
O peak at
2223.5 cm
1
is overlapped by a uorescence band of NO
2
but could be observed when the NO
2
concentration, as indi-
cated by the intensity of the blue colour of the frozen sample,
was low.
II. EXPERIMENTAL
The Raman spectrometer and sample cell were the same
as before
10
except that, on the viewing window of the cell,
the curved parts of the meniscus where it met the windows
at right angles to the viewing window were obscured by nar-
row, vertical strips of metal foil glued onto the outside of the
cell, and a Dove prism was inserted into the optical system
for collecting scattered light, in order to rotate the horizon-
tal green image of the laser-irradiated solution to match the
vertical spectrometer slit. Otherwise the laser diode, notch l-
ter, spectrometer, and CCD detector were as previously de-
scribed. All of the experiments reported here used a spec-
FIG. 1. (a) Fluorescence spectrum of NO
2
measured close to the liquid
surface (<0.5 mm away). The wave-number scale indicates displacement
from the 523 nm exciting line. (b) Fluorescence spectrum of NO
2
measured
2 mm above the liquid surface. The wave-number scale indicates displace-
ment from the 523 nm exciting line. (c) Raman spectrum of a blue solution
of NO
2
in a 20:80 (by volume) mixture of water and 1,4 dioxane, showing
the detectable components below 2200 cm
1
.
trometer slit width of 0.25 mm. Exposure times varied be-
tween 15 and 180 s, and Raman intensities, plotted in arbitrary
units in the graphs that follow, were scaled inversely with
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184702-3 Murdachaew et al. J. Chem. Phys. 140, 184702 (2014)
exposure time, so that the intensity values indicated along the
vertical axes of the graphs are signicant. The sample cell
was mounted on a micrometer-driven platform that enabled
the vertical separation of the laser beam from the liquid sur-
face to be adjusted reproducibly to within about 0.01 mm.
The calculated beam waist within the cell was less than 0.1
mm in diameter but, because the beam intensity prole is ex-
pected to be Gaussian, the effective spatial resolution of the
Raman scattering was somewhat greater than this. As a result,
spectra taken at 0.1 mm intervals were slightly contaminated
with spectra from adjacent 0.1 mm steps. This contamination
was not fatal to our objective, which was to compare the sur-
face distributions of water and 1,4 dioxane in the presence
and absence of NO
2
. Many of the spectra, especially those
with long exposure times, were also affected by cosmic-ray
spikes. The spikes, which were almost invariably positive-
going and seldom more than 3 pixels wide, were removed
by hand, using a computer program written in Chipmunk
Basic.
13
A mixture of spectroscopic grade 1,4 dioxane with milli-
Q water, of known composition by volume, was degassed
in the side-arm of the cell by a series of freeze-pump-thaw
cycles. For most of the experiments, the mixture comprised
equal volumes of the two liquids. An equilibrium mixture
of nitrogen dioxide and dinitrogen tetroxide was prepared
by adding a large excess of oxygen to nitric oxide that had
been puried by trap-to-trap distillation. The mixture was left
overnight before trapping the NO
2
/N
2
O
4
as a white solid at
liquid nitrogen temperature and pumping off the excess oxy-
gen. The resulting bulb of gas at a pressure of a few hundred
torr was used to introduce NO
2
/N
2
O
4
into the cooled side-arm
of the cell until the frozen solid was a more-or-less intense
dark blue. Most of the spectra shown here were obtained with
dark blue samples. The side-arm was then shut off from the
vacuum system, the solid was allowed to thaw, and the cell
was shaken well before being transferred to the micrometer-
driven platform, where it remained for up to a week while
spectra were being taken. Measurements made at intervals
of several days were in excellent agreement, which implies
that any observed depletion of water in the surface layer was
not merely the result of slow dissolving of NO
2
from the gas
phase.
III. RESULTS AND DISCUSSION
The aim of these experiments was to determine whether
the presence of NO
2
gas above the interface affected the con-
centration of H
2
O at the interface. As a rst step, we needed
to obtain Raman spectra of pure 1,4 dioxane and of a dioxane-
water mixture in our system, as shown in Figs. 2(a) and 2(b),
respectively, and of dioxane vapour very close to the surface,
as shown in Fig. 2(c). The water peak at 3400 cm
1
is a dis-
tinctive feature of Fig. 2(b).
The next step was to obtain Raman spectra in the
3400 cm
1
region for a 1:1 water-dioxane mixture, without
NO
2
, at a series of heights that included the interface. Typical
spectra are shown in Figs. 3(a)3(f), with the beam height in
mm indicated on each graph, the height increasing as the laser
beam rose through the interface. The dioxane peak intensity
FIG. 2. (a) Part of the Raman spectrum of pure 1,4 dioxane. (b) Raman spec-
trum of a 1:1 mixture of water and 1,4 dioxane. (c) Raman spectrum of diox-
ane vapour near the liquid surface, with no NO
2
present.
decreased by a factor of ten as the beam height rose from 6.0
to 6.6 mm, and the water peak was still present at 6.6 mm.
At 6.7 mm and above, a comparison with Fig. 2(c) reveals
that much of the remaining dioxane peak was due to dioxane
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184702-4 Murdachaew et al. J. Chem. Phys. 140, 184702 (2014)
FIG. 3. (a)(f) Raman spectra of a 1:1 by volume mixture of water and 1,4 dioxane, with no NO
2
, as a function of the height of the laser beam. The height of
the surface is between 6.4 and 6.6 mm and water is present all the way to the surface.
vapour, so we can conclude that, in the absence of NO
2
, there
is no evidence for a marked decrease in the water concen-
tration relative to dioxane as the beam moves up through the
interface. This shows incidentally that, with a height resolu-
tion of the order of 0.05 mm, the surfactant nature of dioxane
in dioxane-water mixtures did not result in signicant exclu-
sion of water from the surface of the mixed solvent. This is
expected, because such behaviour should result in the forma-
tion of a monolayer, which would not be detectable in our
experiments.
Next, we examined the effect of moving the laser beam
up through the interface for a cell containing water, dioxane,
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184702-5 Murdachaew et al. J. Chem. Phys. 140, 184702 (2014)
FIG. 4. (a)(d) Low wave-number Raman spectrum of a 1:1 (by volume) mixture of water and 1,4 dioxane in the presence of NO
2
, as a function of the
height of the laser beam. As the beam height increases the dioxane peaks diminish and the NO
2
peaks and uorescence background increase. The height
of the liquid surface is about 8.6 mm. Peak assignments for Fig. 4(a) are the same as in Fig. 1(c), with minor differences due to the differing solvent
composition.
and NO
2
, looking rst at the 1300 cm
1
region. Typical spec-
tra are shown in Figs. 4(a)4(c). The height scale does not
correspond precisely to that in Fig. 3 because the cell had to
be moved to the vacuum system to introduce the NO
2
and
then back again, but the height scales in Figs. 4 and 5 do cor-
respond exactly. The spectrum in Fig. 4(a) is similar to that in
Fig. 1(c), showing mainly dioxane peaks with almost no
NO
2
gas. Small, gas-like NO
2
and NO peaks are to be
expected from the liquid because, in the 1:1 solvent mix-
ture, some of the NO
2
and NO molecules will be sur-
rounded by solvent shells composed entirely of dioxane.
The peaks of NO
2
gradually increase and those of diox-
ane decrease as the beam moves upward, and it appears
that the interface is located at a beam height of about
8.6 mm.
The plots in Figs. 5(a)5(c), for the 3400 cm
1
re-
gion show, in addition to the composite dioxane peak, a
change from a small water peak with superimposed NO
2
bands at a height of 8.5 mm, to the spectrum of NO
2
gas
close to the liquid surface at a height of about 8.7 mm.
The plot of Fig. 5(b), at the level of 8.6 mm that we
now assign to the interface region, appears to consist of a
dioxane peak adjoining the NO
2
uorescence of Fig. 1(a),
with no sign of the water peak at 3400 cm
1
. The plot in
Fig. 5(d) is intended to make this point more obvious. The
portion of the plot that is identical with Fig. 5(b) is over-
laid quite neatly by the scaled NO
2
uorescence spectrum
of Fig. 1(a) in the 3400 cm
1
region. The plot of Fig. 5(a)
has been scaled to t the dioxane peak of Fig. 2(a) between
2800 and 3000 cm
1
, where it too ts well. However, the
3400 cm
1
water peak of Fig. 2(b) is not able to be accom-
modated anywhere. Hence it appears that, in the presence
of NO
2
, the surface layer of liquid is strongly depleted of
water.
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184702-6 Murdachaew et al. J. Chem. Phys. 140, 184702 (2014)
FIG. 5. (a)(c) As in Fig. 4, but observing in the region of the water peak at 3400 cm
1
. The spectrum in Fig. 5(a) shows the dioxane peak and the water peak
with weak NO
2
uorescence superimposed on the water peak. The spectrum obtained at a beam height of 8.6 mm shows the dioxane peak between 2800 and
3000 cm
1
and the NO
2
uorescence close to the liquid surface, but the water peak at 3400 cm
1
is not evident above 8.5 mm. (d) The Raman spectrum of
Fig. 5(b), analysed into the dioxane spectrum, plus NO
2
uorescence. The water peak of Fig. 3(a) (shown by the relatively noise-free solid line) clearly is not
present in Fig. 5(b).
IV. CONCLUSIONS
The mutual repulsion of water and NO
2
, which occurs at
the molecular level, has been found to have signicant con-
sequences on a macroscopic scale at the surface of a blue so-
lution of 1,4 dioxane and water in the presence of gaseous
NO
2
. The thickness of the relevant surface layer is of the or-
der of 0.05 mm, which is much greater than the thickness of
the region probed by grazing-incidence Raman spectroscopy.
This possibly surprising observation depends critically on the
total miscibility and lack of mutual reactivity of the dissimi-
lar solvents 1,4 dioxane and water, which permit the surface
layer to become depleted of water in the presence of NO
2
gas.
Thus, the present paper supports the theoretical conclusion
1
that direct formation of HONO from water and NO
2
under
atmospheric conditions is not a facile process, because water
and gas-phase NO
2
tend to repel one another in the surface re-
gion. It might also be regarding as providing indirect support
for the suggestion
14
that the formation of atmospheric HONO
could involve NO
2

ions formed by electron capture by NO

2
from electrically charged surfaces.
ACKNOWLEDGMENTS
We are grateful to Professor Barbara Finlayson-Pitts for
providing the environment and stimulus for this work, which
was supported by Grant No. 0909227 from the United States
National Science Foundation (NSF).
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