552 J. Phys. Chem.

B 2001, 105, 552-561

Intermolecular Interactions and the Structure of Fatty Acid-Soap Crystals

Matthew L. Lynch,*,† Fred Wireko,† Mounir Tarek,‡,§ and Michael Klein‡

The Procter & Gamble Company, Corporate Research DiVision, Miami Valley Laboratories, Ross, Ohio 45061,
Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, Maryland 20899,
and Center for Molecular Modeling, Department of Chemistry, UniVersity of PennsylVania,
Philadelphia, PennsylVania 19104-6323
ReceiVed: July 22, 2000; In Final Form: October 30, 2000

Single crystals of NaHP2 (sodium hydrogen dipalmitate) have been prepared from mixtures of NaP (sodium
palmitate) and HP (palmitic acid) in ethanol. The phase compound crystallizes in the P21/a space group, with
a ) 9.906 Å, b ) 7.163 Å, c ) 45.580 Å, β ) 92.78°, and 4 molecules per unit cell. The arrangement of the
headgroups is unique among known soap and fatty acid structures by accommodating both hydrogen bonding
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and electrostatic interactions. Carboxylate and acid-like pairs couple perpendicular to the bilayer to
accommodate a “short” hydrogen bond, and the sodium is shared among laterally adjacent carboxylate anions
to create a pseudo-six-member ring, which adds to the crystal stability. Molecular dynamic (MD) simulations
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establish a set of interaction parameters to describe the structure and energetics of acid-carboxylate bonds,
which accounts for the solid-state miscibility of HP and NaP. Infrared data, collected by ATR-FTIR on very
pure, powdered NaH2P3, Na2H3P5, and NaHP2 acid-soap standards reveal peculiar changes in the carbonyl
and hydroxyl spectral regions. These spectra were analyzed on the basis of crystal structure and MD simulation
data.

1. Introduction Acid-soaps have both commercial and academic importance.

Chevreul is widely recognized as having made the first
reference to acid-soaps in 1823.1 However, it was not until
the work of Ekwall2-4 and McBain5-8 that the existence of these
compounds was proved by systematic experimental methods.
A summary of subsequent studies is contained in a recent
review.9 The miscibility of fatty acid and sodium carboxylate
in the solid state is postulated to be a consequence of the strong
hydrogen bond between the fatty acid headgroup and the
carboxylate anion. While the fatty acid is the hydrogen-bond
donor, the carboxylate anion is likely a stronger hydrogen-bond
acceptor than the acid. However, the nature of these interactions
remains elusive as no crystal structures of acid-soaps with long
alkyl chains have been reported.
Clues about the structure of acid-soaps have come from
extrapolation to single-crystal data collected for fatty acids,10-14
short-chain acid-soap crystals such as sodium hydrogen diac-
etate,15 and potassium hydrogen phenylacetate16 and to a survey
of existing single-crystal data of similar compounds.17 Structural
details are crucial to understanding the “anomalous” infrared18-22
and NMR20,23,24 data on powder acid-soap crystals, which show
that acid-soap crystals maintain some carboxylic acid-like
character and some carboxylate anion-like character, which are
quantitatively different from the character of either the parent
fatty acid or the sodium carboxylate. The present combined
crystallographic and molecular dynamics (MD) simulation study
has been undertaken to provide the first structural description
of these long chain length acid-soaps that allows for detailed
understanding of the spectroscopy and solid-state chemistry of
these compounds.
* Corresponding author. Tel.: (513) 627-0392. Fax: (513) 627-1233.
E-mail: lynch.ml@pg.com.
† The Procter & Gamble Company.
‡ University of Pennsylvania.
§ National Institute of Standards and Technology.
10.1021/jp002602a CCC: $20.00 © 2001 American Chemical Society
Published on Web 12/20/2000
These compounds are ubiquitous in consumer products. They
are found in superfatted, transparent, and traditional soap bars,
cleaning products, cosmetics, facial cleaners, shaving creams,
deodorants, and topical-delivered products.25-26 Sodium car-
boxylates can be used to form rheological solids with less than
2% organic material27 and can soften with the incorporation of
acid-soaps as a consequence of the inherent differences in
crystal habit.28 The study of fatty acid-carboxylate bonding is
also of academic importance. For example, aqueous sodium and
potassium hydrogen oleate systems have been employed as
potential model membranes.29-31 Further, they are excellent
systems for studying the spectroscopy associated with carboxylic
acid-carboxylate systems, as the stretching frequencies and
peak intensities are dramatically different from those of the
parent compounds. These findings can possibly be transferred
to the study of more complex peptide and protein structures
involving, for example, bonding to aspartate and glutamate
residues. Finally, it is likely that acid-soaps will continue to
be of interest, as similar hydrogen bonds are a main design
element in both crystal engineering and supramolecular
assembly.32-34
2. Experimental Section
Preparation of Single-Crystal NaHP2. Single crystals of
NaHP2 were prepared from mixtures of NaP and HP in ethanol.
The phase behavior of HP-NaP-ethanol mixtures was first
established to ensure the formation of NaP2 crystals. The optimal
situation entailed mixing 0.45 g of HP and 0.05 g of NaP in 50
mL of ethanol (HPLC grade) in a shallow recrystallization dish.
The mixture was gently heated to speed the dissolution of NaP
and HP. The dish was fitted with a plastic cover, which
contained a small 1 mm diameter hole in the center. Crystals
began to form after the first few hours. The sample was allowed
Structure of Fatty Acid-Soap Crystals
Figure 1. Powder XRD patterns of crystal standards: (A) palmitic acid, (B) sodium palmitate, (C) NaH2P3, and (D) Na2H3P5.
to sit for 2-3 weeks. Remaining ethanol was removed by
filtration. Crystals of optimal size (about 1 mm) were culled
by looking for sharp extinction in birefringence upon rotation
of the crystals in a polarized light microscope.
Preparation of Polycrystalline Acid, Soap, and Acid-Soap
Standards. Palmitic acid was purchased from NuCheck Prep,
Inc. GC analysis of the methyl ester derivative (prepared using
methanesulfonic acid in methanol) indicated the percentage
composition, as determined by peak area, to be 0.03 C7, 0.03
C12, 0.16 C14, 0.08 C15, 99.52 C16, 0.07 C17, and 0.11 C18. The
acid was melted and cooled to generate form-C crystals. To
prepare sodium palmitate, a 10% w/w palmitic acid-deionized
water solution was heated to 85 °C and neutralized with 0.1 M
sodium hydroxide (standardized with potassium acid phthalate).
The solution was cooled. A Buchner funnel was used to filter
the resulting crystals, which were allowed to air-dry to constant
weight (about 1 week). No further effort was undertaken to
remove the water of hydration.
NaH2P3 crystals were created by partial neutralization of a
10% w/w palmitic acid-deionized water solution, as previously
noted.20 The mixture was heated to 85 °C and partially
neutralized with 0.1 M sodium hydroxide. The sample was
cooled. Crystals were removed with a Buchner funnel and
allowed to air-dry to constant weight (about 1 week). These
crystals were determined to be anhydrous, which was confirmed
by infrared analysis.
J. Phys. Chem. B, Vol. 105, No. 2, 2001 553
An isothermal mixing process was developed to generate
high-quality Na2H3P5 and NaHP2 standards. Unlike the prepara-
tion of NaH2P3, the preparation of these standards by the
aforementioned heating/cooling method resulted in mixtures of
crystals. Instead, a 1 g total of NaP and NaH2P3 crystals (ratios
defined by the stoichiometry needed to form the acid-soaps)
was added to 50 mL of deionized water in a small beaker to
create a slurry (using the NaH2P3 crystals was tantamount to
providing solubility of fatty acid in water). A Teflon stir bar
was added to the beaker, and the slurry was stirred for 10-12
h. Large chucks of NaH2P3 and NaP crystals evident at the start
gave way to a fine dispersion of acid-soap crystals. The crystals
were removed by pouring the slurry through filter paper and
allowed to air-dry.
The purity of each acid-soap standard was confirmed with
powder X-ray diffraction (XRD) methods by inspecting the
number of sets of [00L] reflections. These are intense reflections,
which correspond to the bilayer distances. Each acid-soap has
a single set of these reflections based on their unique bilayer d
spacings (45.6 Å for NaHP2, 42.8 Å for NaH2P3, and 42.2 Å
for Na2H3P3), as predicted by Bragg’s Law, mλ ) 2d sin θ (m
is the number of different orders). All the standards, except for
NaP, are pure in this respect (Figure 1). The NaP sample has
two crystal phases such as the β and δ phases in soap vernacular,
and it is difficult to synthesize pure soap phases with any known
preparation procedures. The powder XRD pattern for the NaHP2
554 J. Phys. Chem. B, Vol. 105, No. 2, 2001
Figure 2. Powder XRD patterns of NaHP2 standard at 150 K compared
with (superimposed lines) a computed powder pattern derived from
the single-crystal unit cell data at 298 K (see text).
TABLE 1: Unit Cell Data at Different Temperatures
unit cell
parameter at 150 K at 293 K
a 9.906 Å 9.989 Å
b 7.163 Å 7.379 Å
c 45.58 Å 45.77 Å
β 92.78° 92.78°
is highlighted in Figure 2, superposed on the intense reflections
(I/Imax > 1%) computed from the single crystal data. It should
be noted that the original data were collected at 150 K and the
computed reflections did not suitably match the XRD pattern
of ambient temperature. However, the unit cell dimension was
remeasured at 293 K (Table 1). There was a thermal expansion
of the unit cell. The 2θ positions, calculated from the ambient
temperature cell parameters, now match the powder diffraction
data (Figure 2). The stoichiometry of the crystals was confirmed
by the elemental analysis of pure powders.
Single-Crystal XRD Measurements and Analysis. X-ray
diffraction data were collected using the Siemens (Bruker) P4-
diffractometer with monochromatic CuKR radiation. The XS-
CANS data acquisition software was used. The crystal structure
was solved and refined in the SHELXTL suite of programs.
All nonhydrogen atoms were located experimentally and refined
anisotropically. Hydrogen atoms were fixed in a riding model
except the carboxylic acid H, which was put in a calculated
position after the refinement.
Refinements were carried out on F2 for all reflections. The
weighted R-factor, Rw, and the goodness of fit, S, are based on
F2. The conventional R-factor is based on F, with F set to zero
for reflections with negative F2.35 The observed criterion of F2
> 2σ(F2) was used for calculating the R-factor. R-factors based
on F2 are statistically about twice as large as those based on F,
and R-factors based on all data are even larger. The relatively
large R-factor for this structure is due to crystal quality and
possibly the entropy of the long chains. Further data collection,
refinement details, atomic coordinates, and thermal parameter
tables will be given as Supporting Information.
Powder X-ray Measurements. The powder XRD studies were
done with a Philips PW1830 automated powder diffraction
system. X-rays were generated from a Cu anode tube at 45 kV
and 40 mA, and the diffracted X-rays were measured using a
proportional counter. Standard measurements were made from
2.0° to 40.0° 2θ at 0.05° 2θ increments. The signal was
Lynch et al.
integrated for 2 s at each step. The data were collected and
normalized on an interfaced computer using Philips diffraction
software. Precise crystallographic spacings were made with 1/4°
slits, 0.005 °2θ increments, and 5 s integration times at angles
less than 2° 2θ and with 1/2° slits, 0.01 °2θ increments, and 2
s integration times at angles greater than 15° 2θ. All X-ray
spacings were standardized using a powdered crystalline silicon
standard (NBS 640b).
Infrared Measurements. The FT-IR measurements were made
using a Digilab FTS 7 spectrometer. All spectra were measured
on powder samples using an attenuated total reflection (ATR)
accessory with a zinc selenide internal reflection element (IRE)
to preserve the crystal structure and eliminate perturbation of
the data due to sample preparation. Each spectrum represents
64 scans taken at 4 cm-1 resolution referenced to the spectrum
of a clean zinc selenide IRE. The spectra were not corrected
for the distortion of peak intensities by ATR. Peak frequencies
were determined using the three-center weighted algorithm in
the GRAMS/386 software. Intensities are shown in unnormal-
ized absorption units.
3. Results and Discussion
Crystal Structure and Hydrogen Bonding in NaHP2. The
structure of NaHP2 is illustrated in Figure 3. The carboxylate
and acid headgroups are arranged in pairwise fashion to form
a bilayer structure. The carboxylate headgroup was differentiated
from the acid headgroup on the basis of carbon-oxygen bond
lengths (Figure 3C and Table 2). The hydrogen atom was fixed
in a calculated position for illustrative purposes. The carboxylate
and acid groups are held together via two interactions: H-
bonding and coordination to a common Na atom as part of a
six-member ring defined by hydrogen, O2′, NaB, O1A, C1A,
and O2A (Figure 3B). The strength of the interaction between
the hydroxyl group of the acid and the carboxylate oxygen
manifests itself in the short distance of about 2.44 Å and a
possible angle of about 176° subtended at the hydrogen (Figure
3C).
The Na ions are sandwiched between the carboxylate and
acid headgroups, but each carboxylate-oxygen interacts sepa-
rately with a symmetry-related sodium ion. The immediate
coordination sphere of Na is comprised of five oxygens, three
of which are symmetry-related carboxylate oxygens while the
other two come from symmetry-related acids. The average
O-Na distance is about 2.37 Å, while the closest Na is about
3.35 Å away.
The long hydrocarbon chains assume all-trans conformation
with some twist around the headgroup area. The twist of the
chain with respect to the mean-plane defined by the carboxylic
acid/carboxylate headgroup is 35° for the acid and about 7.5°
for the carboxylate. Headgroup twist values similar to the above
have been observed for lauric acid and potassium palmitate.
Discussion of the MD Simulations. We used empirical
interaction potentials with the following form:
U ) Ubond + Uangles + Utorsions + Unonbonded
Here, Ubond and Uangles are harmonic terms that account for
intramolecular bond stretching and bond angle deformations,
and Utorsions is a appropriate periodic torsion term. Unonbonded
describes the intermolecular potential and is based on pairwise
additive site-site electrostatic and Lennard-Jones contributions.
To model the hydrocarbon part of the long-chain molecules,
we used the all-atom potential that reproduces the structures of
solid and liquid alkanes well.36 The sodium ion parameters were
Structure of Fatty Acid-Soap Crystals
Figure 3. Structure of the NaHP2 crystal. The top drawing (A) shows the alkyl chain and headgroup arrangement, while the bottom drawing (B)
delineates the headgroup region. The local coordination around sodium should be noted. (C) Illustration of the specific bonding distances (in Å)
associated with an acid-carboxylate pair with the NaHP2 crystal.
taken from Chandrasekhar et al.37 without further modification.
The carboxylate headgroup was modeled using parameters from
Jorgensen and Gao,38 while for the acid headgroups we used
parameters from Briggs et al.39
Most of the components of the force field have been tested
independently and exhibited reasonable agreement with experi-
mental results for the structural and thermodynamic properties
of model compounds and/or single component systems. How-
ever, there is no guarantee that they will work equally well when
combined in the systems under study. To test these models, we
set up MD simulations for pure acid crystals. Most fatty acids
are known by powder X-ray diffraction to exist in three
crystalline polymorphs, named A(triclinic), B (monoclinic), and
C (monoclinic),40 all of which are stable. We have generated
trajectories at equilibrium for the A-super form of the lauric
acid C12 and the B-form of stearic acid C18 (see descriptions
of the structures below). These included the A-super form of
J. Phys. Chem. B, Vol. 105, No. 2, 2001 555
the lauric acid C11H23COOH and the B-form of stearic acid
C17H23COOH. To our knowledge, there is no atomic-resolution
crystallographic data on sodium soaps against which to compare
MD simulations.
The crystal structure of the A-super form of the lauric acid
was taken from Goto and Asada11,41 (Figure 4a). The symmetry
operators of the triclinic P1h space group were used to generate
the atomic coordinates from the asymmetric units. All of the
hydrogens were added in the simulation, including the carboxyl-
group protons, whose positions were set such that the lauric
acid molecules form hydrogen-bonded dimers. The MD simula-
tion cell comprised 60 molecules in a 5a × b × c lattice (i.e.,
2280 atoms). We note here that, as is commonly found in fatty
acids, the molecules are bound together to form dimers through
hydrogen bonds between the carboxyl groups; however, for this
somewhat unusual structure, the carboxyl groups are not all
located in the same plane.
556 J. Phys. Chem. B, Vol. 105, No. 2, 2001 Lynch et al.

molecules (i.e., 6a × 8b × 2c lattice) and 48 sodium ions (i.e.,

about 4800 atoms). The carboxyl-group protons whose positions
were not determined from the X-ray analysis were added in the
simulation. Their positions were set such that two opposing
molecules (in c direction) are hydrogen bonded (Figure 4c).
The MD trajectories were carried out with three-dimensional
periodic boundary conditions. For every system, short equilibra-
tion runs were performed at constant temperature and volume,
followed by a longer run at constant temperature, and pressure
(NPT) using the hybrid MD algorithm developed by Martyna
et al.42,43 The extended system (ES) equations of motion were
integrated by using an iterative Verlet-like algorithm. The
fictitious masses of the ES variables were chosen according to
the prescript ion given by Martyna et al.,44 with time scales of
0.5 ps for the thermostats and 1 ps for the volume and cell
variables. The Nosé-Hoover thermostat chain length was five.
The Ewald method was used to compute the electrostatic
interactions, and the minimum image convention was employed
Figure 4. Initial arrangement of crystal structures used to validate the to calculate the real-space part of the Ewald sum and the van
interaction parameters in the molecular dynamic simulations: (a) the der Waals interactions with simple truncation at 10 Å.45 Bonds
A-super form of lauric acid, (b) the B-form of stearic acid, and (c) the
NaHP2 acid-soap defined by the present crystallographic data.
involving hydrogen atoms were constrained using the SHAKE
algorithm.46
TABLE 2: Carboxylate/Carboxylic Acid Headgroup and The A-super form of the lauric acid remained stable during
H-bond Parameters for NaHP2 the 160 ps simulation. Since we are dealing with solid phases,
Bond Lengths a NPT simulation of a 160 ps is adequate in testing for “local”
CdO 1.199 Å stability. Any tendency to “transform” to a different structure
C-O 1.313 Å usually manifests itself in large fluctuations in unit cell
CdO 1.258 Å
CdO 1.300 Å parameters, which serve as precursors to a transition. In the
O f Na (avg) 2.37 Å present case, no such latent instability was apparent. The overall
agreement of the unit cell parameters with experiment is
H-bond Parameter
satisfactory, with variations less than 3% (Table 3). For stearic
atoms (D-H‚‚‚A)‡ D‚‚‚A (Å) H‚‚‚A(Å) ∠DHA
O2-H‚‚‚O2′a 2.444 Å 1.5 Å 176.2° acid, the crystal remained stable during the 160 ps NPT
simulation. We compare the average cell parameters to the
The initial configuration for the stearic acid crystal was taken experimental values (Goto et al.)12 in Table 4. Overall the
from Goto et al.12 and corresponds to the B-form (Figure 4b). agreement is very good; the most significant deviations are less
The space group P21/a operators and lattice translations were than 2.7% in the a and b dimensions. In Table 5, we report the
used to generate all of the atomic coordinates from the average cell parameters from the MD simulation for the NaHP2
asymmetric units. The carboxyl-group protons whose positions acid crystal; the agreement again with experiment is very
were not determined from the X-ray analysis were added in the satisfactory. The crystal remained stable during the 160 ps NPT
simulation. Their positions were initially set to reproduce the simulation (Figure 5). Taken together, these results validate the
double hydrogen bonding involving the carboxyl dimers. The force field parameters used in the calculation.
MD simulation cell contained 100 molecules in a 5a × 5b × c To compare the headgroup organization of the acid and acid-
lattice (i.e., about 5600 atoms). soap molecules, we display in Figure 4 snapshots of the
For the sodium palmitate-palmitic acid 1:1 acid-soap assemblies for the A-super form of the lauric acid, the B-form
crystal, the initial configuration was taken from the X-ray data of the stearic acid, and the NaHP2 sodium acid-soap. In the
analysis (cf. above). Accordingly, the space group P21/a first two cases, the molecules labeled 1 and 2 form hydrogen-
operators and lattice translations were used to generate all of bonded dimers. In the latter case, an acid molecule (1) forms a
the atomic coordinates from the asymmetric units in a 3a × 4b single hydrogen bond with a palmitate ion (2) and shares a
× c lattice. The resulting simulation box contained 48 × 2 sodium ion with a second neighboring ion (4) while the ionic

TABLE 3: Experimental and Simulation Results for Super-A Form Lauric Acid
a (Å) b (Å) c (Å) R (deg) β (deg) γ (deg)
X-ray 5.415(2) 25.96(1) 35.18(13) 69.82(4) 113.14(4) 121.15(3)
simulation 5.44(3) 25.63(30) 34.66(89) 70.67(73) 112.0(10) 118.0(13)

TABLE 4: Experimental and Simulation Results for Form B Stearic Acid

a (Å) b (Å) c (Å) R (deg) β (deg) γ (deg)
X-ray 5.587(10) 7.386(10) 49.33(8) 90.0 117.2(9) 90.0
simulation 5.44(3) 7.59(5) 49.01(9) 90.01(40) 117.53(35) 89.99(36)

TABLE 5: Experimental and Simulation Results for NaHP2

a (Å) b (Å) c (Å) R (deg) β (deg) γ (deg)
X-ray 9.906(1) 7.163(1) 45.580(6) 90.0 92.78(1) 90.0
simulation 9.80(6) 7.11(4) 45.25(6) 90.00(54) 93.40(31) 89.99(24)
Structure of Fatty Acid-Soap Crystals J. Phys. Chem. B, Vol. 105, No. 2, 2001 557

Figure 5. Unit cell dimensions as a function of time for the NaHP2 crystal as it evolved in the molecular dynamics simulation.

molecule (2) shares another sodium ion with the upper molecule
(3). Comparison of panels a-c of Figure 4 shows that the dimer
1-2, instead of sharing a double hydrogen bond like the acid
crystal, shares only one hydrogen bond and compensates for
the extra (layer-to-layer) binding energy by ionic interactions
with a pair of sodium ions.
It is difficult, considering only the local arrangement of the
dimers or dimers plus first neighboring molecules, to compare
quantitatively the energetics involved. In the acid crystal case,
the headgroup-to-headgroup interaction can be considered
primarily due to the hydrogen-bonded pairs; however, for the
NaHP2 crystal, a likely strong interaction with neighboring ions
is involved in the headgroup region. Rather than isolating
specific pairwise interactions, we compare the energetics of the
acid-like arrangements for the B-stearic acid with that of the
NaHP2 crystal by investigating the leaflet to leaflet binding
energies. To do so, we have calculated, using the force field
parameters that reproduced both crystal structures well, the van
der Waals and electrostatic interaction profiles between the upper
and lower layers as a function of their separations. The two
leaflets are pulled apart a distance r along the c axis, and the
intermolecular nonbonded interactions are estimated for the
whole system while considering periodic boundary conditions.
For the B-stearic acid, the successive configurations, obtained
by increasing r from 0.0 Å (equilibrium) to 2.0 Å, lead to
breaking the hydrogen bonds between molecules in opposite
layers (Figure 6). For the NaHP2 crystal, the positions of the
Figure 6. Energy necessary to separate the acid-soap and fatty acid
sodium ions were held fixed (in contrast to allowing them to as a function of distance.
move with the leaflets). The calculation included the contribution
from the chain-chain interactions within the same leaflet. shallower for the acid crystal compared to that of the sodium
The variation of the individual components contributing to acid-soap, which indicates that in the later case the leaflets
the nonbonded energies is shown as a function of r in Figure 6. are much more strongly bound.
To aid the comparison, we shifted the curves to a common Discussion of Spectroscopy of Acid-Soaps. The infrared
minimum. The results show that the energy variation is much spectra for HP and NaP are generally well understood. For HP
558 J. Phys. Chem. B, Vol. 105, No. 2, 2001
Figure 7. Entire midrange IR spectra of the standards: (A) HP, (B) NaP, (C) NaH2P3, (D) Na2H3P5, and (E) NaHP2.
crystals, the CdO stretch is at ∼1690 cm-1 47 (Figures 7A and
8A). However, the frequency of the stretch is known to be
susceptible to intermolecular interactions. Fatty acid crystals
contain dimers, in which a pair of acid molecules aligns head-
to-head to form two hydrogen bonds using the acid proton on
one molecule and the carbonyl oxygen on the other. Unasso-
ciated fatty acids (i.e., not dimerized) can have CdO stretches
as high as 1760 cm-1. In addition, there is a broad OH stretch
envelope for HP between 2200 and 3500 cm-1 (Figure 7A).
Lynch et al.
NaP has a strong asymmetric stretching band (νasym COO-)
center at about ∼1550 cm-1 (Figures 7B and 8B). In general,
carboxylate groups also have symmetric stretches (νsym COO-)
as low as ∼1400 cm-1, which are broad and generally have
two to three peaks. These bands are obscured in the NaP spectra.
Finally, there may be a broad OH stretch envelope between
3000 and 3600 cm-1, which arises from the water of hydration.
Spectra for acid-soap show distinct changes in the carbonyl
and the OH stretching bands. The acid-carbonyl stretching band
Structure of Fatty Acid-Soap Crystals
Figure 8. Expansion of the carbonyl regions of the standards: (A) HP, (B) NaP, (C) NaH2P3, (D) Na2H3P5, and (E) NaHP2.
moves to higher frequencies: 1722.8, 1725.0, and 1724.0 cm-1
for NaH2P3, Na2H3P5, and NaHP2, respectively (Table 6). At
the same time, the asymmetric carboxylate stretching band shifts
to lower frequencies, about 1520 cm-1 for NaH2P3, Na2H3P5,
and NaHP2. The band becomes broad and far less intense. There
is an additional carboxylate stretching band in the NaHP2 spectra
at 1623 cm-1. The OH stretching band for acid-soaps shift to
a broad, weak envelope between 2200 and 3000 cm-1. There
has been no reported hydration within acid-soap crystals.
J. Phys. Chem. B, Vol. 105, No. 2, 2001 559
The change in the νasym COO- bands seems to reflect the
change in bond order or strength of the CO bond. By classical
arguments, the frequency of the vibration is proportional to the
square root of the force constant.48 It is reasonable to suggest
that longer bond distances imply weaker force constants, and
consequently, the band will shift to lower frequencies. Compar-
ing the CO bond distance of NaHP2 with known potassium soaps
(Table 7) shows that the bond distances are indeed longer in
the acid-soap. The increase in bond order likely reflects both
560 J. Phys. Chem. B, Vol. 105, No. 2, 2001
TABLE 6: Carbonyl Band Frequencies for Sodium
Palmitate, Palmitic Acid, and Acid-Soaps
other
acid-soap acid-carbonyl carboxylate-carbonyl carboxylate
crystal stretch (νasym stretch) stretch
NaP 1557.1 cm-1
HP 1696.6 cm-1
NaH2P3 1722.8 cm-1 ∼1520 cm-1 (weak)
Na2H3P5 1725.0 cm-1 ∼1520 cm-1 (weak)
NaHP2 1724.0 cm-1 ∼1520 cm-1 ∼1623 cm-1
TABLE 7: Comparison of Carboxylate, Carboxylic Acid,
and Acid-Soap Bond Distances (Å)
the hydrogen bonding and placement of the carbonyl within
the lattice. The shift of the νasym COO- in the other acid-soaps
implies a comparable situation. It is impossible to explain the
additional carbonyl peak in the NaHP2 by this argument.
However, it was previously noted that the νsym COO- band is
often observed as multiple peaks, which would be a reasonable
assignment for this band.
Differences in the acid CdO and O-H stretching bands seem
to reflect changes in the intermolecular interactions. The acid
group is not dimerized in the acid-soap, which, as previously
noted, causes the CO stretching band to shift to higher
frequencies. Further, the hydrogen bond in the NaHP2 crystal
is short (2.444 Å). Short hydrogen bonds are known to shift
the OH groups to lower frequency.49 So rather than a broad
envelop between 3000 and 3600 cm-1, the envelop shifts to
2200-3000 cm-1. A comparison of acid CO bond distances
within NaHP2 and other fatty acid crystal data suggests these
bond lengths are comparable and, consequently, cannot be used
to explain the shift. Again, it is assumed from parity with other
acid-soap spectra that these crystals must have a similar type
of arrangement.
While we have attempted to qualitatively describe the changes
in the intermolecular vibrational spectra when going from pure
acid-and-soap compounds to the acid-soap crystal, it is clear
that a quantitative description of the changes observed is much
more complicated. Indeed, the vibrational properties (i.e.,
frequencies and intensities) of the carbonyl and carboxylate
moieties are dependent on the interactions of these moieties with
their immediate environment.50,51 The molecular dynamics
simulation trajectories can in principle be used to compute the
IR spectra for the crystals understudy. However, the force field
used in this study is not optimized for such an analysis. A
quantitative analysis of the IR spectra therefore necessitates
either the use of a more suitable force field (cf. Ishioka et al.)52
or a quantum calculation.
4. Conclusions
The present study employs a combination of crystallography,
MD simulation, and infrared spectroscopy to explore the nature
Lynch et al.
of intermolecular interactions in long chain length acid-soaps.
The crystallography data provide succinct evidence for distinct
acid and carboxylate groups within the acid-soap crystal, which
eliminates the conjecture of acid dimers and carboxylate groups
and some “blending” arrangement. The advantage of using MD
simulation is its ability to incorporate the entire crystal struc-
tureand thermal effects, rather than just chain fragments.
Comparisons between the experimental data and the MD
simulations provide a quantitative test of the carboxylate and
fatty acid interactions. These interaction potentials utilized in
the present study indicate that the sum of Coulombic and van
der Waals interactions is stronger in the acid-soap than in the
fatty acid. The present data can also be used to explain the
peculiar changes observed in the IR spectroscopy of acid-soaps.
The presence of definitive acid and carboxylate fractions in these
crystals explains why both acid-like and carboxylate-like
features are observed in the IR spectra. However, subtle
variations in bond distances (and, hence, intermolecular interac-
tions) are reflected in deviations of these spectral features from
the parent acid and soap crystals. Comparisons with other acid-
soaps allow us to make reasonable assessments as to the nature
of all these crystals and thereby broaden our understanding of
the field.
Acknowledgment. The authors would like to acknowledge
Robert Laughlin and Curt Marcott, both from Procter and
Gamble’s Corporate Research Division, for many useful dis-
cussions. The simulation work at the University of Pennsylvania
was supported by a generous grant from the Procter and Gamble
Company.
Supporting Information Available: Five tables describing
the crystallographic data. This material is available free of charge
via the Internet at http://pubs.acs.org.
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