Spectroscopy Tutorial

Applied Spectroscopy Practica

2024, Vol. 2(2) 1–10
Interpretation of the Infrared Spectra of © The Author(s) 2024
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Metal-Stearate Salts sagepub.com/journals-permissions
DOI: 10.1177/27551857241253834
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Peter J. Larkin1 and Andrew Jackson1

Abstract
Fourier transform infrared (FT-IR) spectra were measured of the sodium, zinc, and calcium metal salts of stearic acid. The
normal mode analysis of sodium decanoate provides guidance on the group frequency-based band assignments for these
metal stearates. The principal absorption bands are assigned to the vibrations of specific molecular groups, carboxylate
and methylene (CH2), and to a lesser extent methyl species. Highly characteristic group frequencies without significant
mechanical coupling are observed above 1500 cm–1. Below 1500 cm–1, the vibrational modes of the carboxylate and alkane
chain exhibit mechanical coupling. The prominent carboxylate stretching vibrations differ based on the metal, metal coordi-
nation structure, and metal-stearate polymorphic form. The nature of the mechanical coupling of the CH2 wag is discussed in
order to understand the empirical correlation between the number of observed infrared bands (1360–1160 cm–1 spectral
region) and the number of carbons in the n-alkane chain.

Keywords
Stearate salts, Fourier transform infrared spectroscopy, FT-IR, spectral interpretation, soaps, vibrational analysis, vibrational
mode
Date received: 28 February 2024; accepted: 2 April 2024

Introduction is highly likely to encounter stearic acid metal salts on multi-

ple occasions and should be knowledgeable of their charac-
Fatty acid metal salts are widely used in multiple industries teristic infrared spectral bands.
and final products.1 Typically, they are produced from a reac-
tion of a fatty acid such as stearic acid with a metal oxide Chemical Structure of Stearic Acid Sodium Salt. n-alkyl fatty acids
resulting in a long-chain aliphatic compound with a terminal such as stearic acids consist of an unbranched saturated long
carboxylate (RCO–2). They are a major soap component chain aliphatic unit and a terminal carboxylic acid. Following
and are used in plastics, rubber, paints and finishes, cosmet- deprotonation, this structure results in the observed hydro-
ics, greases, and oils. phobic–hydrophilic double nature of metal RCO–2. The chemi-
In general, the organic salt of a metal cation and a RCO–2 cal structure of sodium stearate (Na+ CH3 (CH2)16 CO–2) is
anion containing eight or more carbon atoms in the alkyl shown below.2 The energetically favored structure finds the
chain is termed a soap. Commercial fatty acid metal salts methylene (CH2) groups in the trans (zig-zag) configuration
derive from stearic, palmitic, lauric, oleic, and tall oil acids. and is typically encountered in fatty acid salts. The sodium cat-
The most common metals encountered include sodium, cal- ion forms a simple ionic interaction between the anionic
cium, and zinc. However, only alkaline or ammonium salts are RCO–2. Both oxygen atoms interact equally with the sodium
typically regarded as classic soaps. The use of other metals cation.
results in a different class of metal soaps with decreased
water solubility along with increased solubility in non-polar
solvents. The physicochemical properties of these metal 1
Syensqo SA, Technology Solutions, Stamford, Connecticut, USA
soaps are related to their structure and the nature of the
Corresponding Author:
metal. The differing physicochemical properties of these Peter J. Larkin, Syensqo Analytical, 1937 West Main Street, Stamford,
metal soaps result in their use in a wide variety of applica- Connecticut 06902, USA.
tions.1 Consequently, a practicing vibrational spectroscopist Email: [email protected]

Creative Commons Non Commercial CC BY-NC: This article is distributed under the terms of the Creative Commons Attribution-
NonCommercial 4.0 License (https://creativecommons.org/licenses/by-nc/4.0/) which permits non-commercial use, reproduction and distribution
of the work without further permission provided the original work is attributed as specified on the SAGE and Open Access page (https://us.sagepub.com/en-
us/nam/open-access-at-sage).
2 Applied Spectroscopy Practica

Scheme 1. Chemical structure of sodium stearate (octadecanoic acid, sodium salt).

Infrared Spectroscopy: Characterization of Metal–RCO–2 Species. the diamond ATR, and measurement of the sample FT-IR scan.
Fourier transform infrared spectroscopy (FT-IR) is an estab- The ATR element was then cleaned using a wet Kimwipes tissue
lished technique to investigate the chemical state and interac- and the ATR element was confirmed to be free of chemical con-
tions of carbonyl and RCO–2 groups.3–6 Infrared (IR) tamination by a simple FT-IR absorbance scan relative to the sin-
spectroscopy is well suited to study metal–soap complexes gle beam background scan.
using both RCO–2 stretching and selected CH2 vibrations.7–9 In ATR spectral correction, the ATR spectrum differs
The environmental sensitivity of both the RCO–2 and CH2 from a classic transmission spectrum because the light pene-
vibrations exhibit characteristic differences depending on trates into the sample at a depth proportional to the wave-
the metal, the type of metal– RCO–2 coordination species, length of light. Longer wavelength light (i.e., smaller
and the crystalline form. wavenumbers) passes through more of the sample and exhib-
Here, we review the characteristic IR group frequencies its greater absorbance. Thus, when compared to a classic
of the common stearic acid salts. We highlight the impor- transmission spectrum, the absorbance at lower frequencies
tance of the mechanical coupling of vibrations involving is proportionally greater than at higher frequencies. The
RCO–2 and CH2 groups in the IR fingerprint spectral region important parameters in the ATR depth of penetration
(below 1500 cm–1). A normal mode analysis of sodium dec- include the incident light wavelength, the angle of incidence
anoate is used to provide a solid foundational understanding to the ATR element, the refractive index of the ATR element,
of the characteristic IR bands of metal-stearate salts. and the refractive index of the sample. Minor differences in
Representative IR spectra of sodium, calcium, and zinc stea- peak frequencies and bandshape are also expected in an
rate are presented, and the effect of polymorphic forms and ATR-measured infrared spectrum compared to a standard
metal–RCO–2 coordination species on the IR spectrum are transmission spectrum.
discussed. The ATR spectrum is corrected using the ATR Correct
Algorithm 2 in the Resolutions Pro software with a sample
refractive index of 1.5, a crystal angle of incidence of
Experimental 45.00°, a crystal name of diamond or Ge with a correspond-
ing refractive index of 2.4 and 4.0, respectively.
Materials and Methods Sodium decanoate (Sigma-Aldrich, SLCP6498) and sodium
Fourier transform infrared spectroscopy measurements stearate (Sigma-Aldrich, SLRC0584) were used as supplied.
were conducted using an Agilent Technologies Cary 670 Zinc stearate (FACI USA) and calcium stearate (Univar
FT-IR spectrometer at 4 cm–1 resolution and 32 scans using Solutions) were used as supplied.
ResolutionsPro FT-IR spectroscopy software (v.5.3.0, For the computational chemistry, Schrodinger software
Agilent Technologies). The interferometer utilized an v.23.2 was used to perform the theoretical work. A single
extended-range potassium bromide (KBr) beamsplitter and conformer of the anion with the alkyl group in a linear con-
a cooled deuterated L-alanine doped tri-glycine sulfate detec- formation was optimized in the gas phase using the
tor. A Norton–Beer medium apodization was employed. ω-B97X-D4 functional and the def2-TZVP basis set.
Attenuated total reflection (ATR) sampling of the stearic Subsequently, a single point energy calculation was per-
acid salts was used to minimize perturbation of the metal– formed at the W-B97X-D4/def2-TZVP(-F) level of theory
RCO–2 structure. Stearic acid salts often have several different using the optimized geometry to calculate the IR and
polymorphic forms which can be affected by temperature, Raman vibrational frequencies. The def2-TZVP(-F) basis
physical grinding, and pressure. KBr disc, NUJOL mulls, and set is required for vibration analysis because F-orbitals can-
cast films can potentially change the polymorph and there- not be included. Selected calculated frequencies and inten-
fore the measured FT-IR spectra. sities can be found in Table S1 (Supplemental Material).
An in-compartment diamond ATR accessory (GladiATR, Pike
Technologies) was used for the FT-IR spectral measurements.
The FT-IR spectra were collected in the 4000–400 cm–1 spectral Results and Discussion
region for the diamond ATR and the 4000–600 cm–1 spectral
region for the Ge ATR. The FT-IR measurement procedure Infrared Spectroscopy of Sodium Stearate
included the measurement of a single beam background scan Alkane RCO–2 such as stearic acid salts have infrared bands
of the cleaned ATR element, transfer of the solid sample onto characteristic of normal alkane methyl and CH2 groups as
Larkin and Jackson 3

Figure 1. The FT-IR spectrum shown in percent transmission of sodium stearate measured at 4 cm–1 resolution using a Ge ATR. An ATR
correction was employed.

well as RCO–2.3–6 Figure 1 shows the FT-IR spectrum of and sym stretches, respectively, and 1381 cm–1 from the
sodium stearate measured with a Ge ATR (corrected) with CH3 sym bend. In the fingerprint region, the RCO–2 vibrations
only moderate pressure. Some of the general characteristic involving both the RCO–2 sym stretch and the in-plane bend
infrared bands are identified in Figure 1 and are summarized mechanically couple with the CH2 group CH2 wag, twist, and
in the group frequencies assigned in Table I. rock vibrations (see Supplemental Material for vibrational
The FT-IR spectrum of fatty acid salts exhibits infrared analyses).
absorption bands due to the RCO–2 group including A convenient dividing line is revealed by examination of
the out-of-phase (antisymmetric/asymmetric = asym)10,† the group frequencies of sodium stearate assigned in
stretch at 1600–1520 cm–1, the in-phase (symmetric = Table I. Highly characteristic group frequencies without signif-
sym) stretch at 1440–1380 cm–1 and the in-plane bend icant mechanical coupling are observed above 1500 cm–1.
(deformation) at 740–670 cm–1. The RCO–2 asym and Below 1500 cm–1, the vibrational modes of the RCO–2 and
sym stretches can be understood in terms of the mechan- the CH2 group exhibit mechanical coupling.
ical coupling of equivalent bonds of a triatomic moiety Group frequencies arise when a molecule contains a bond
such as carbon dioxide (CO2). When both C=O bonds or group with a vibrational frequency significantly different
stretch, they are in phase with one another leading to a from adjacent groups. In this case, the vibrations are localized
sym stretch. When one C=O bond stretches while the primarily at this functional group. Good quality group fre-
other contracts, the individual C=O vibrations are quencies are typically encountered between 4000 and
out-of-phase causing an asym stretch. The RCO–2 asym 1500 cm–1. The IR fingerprint region usually involves the
stretch observed at 1570 and 1559 cm–1 in sodium stea- mechanical coupling of differing bonds and adjacent groups.
rate is an excellent group frequency. The two bands For sodium stearate, this results in multiple bands associated
observed for sodium stearate have been previously with the RCO–2 sym stretch interacting with the CH2 wag,
reported and attributed to possible different sub-cell the CH2 wag progression, and the RCO–2 in-plane bend inter-
arrangements.7 The IR RCO–2 asym stretch is a strong action with the CH2 rock.
absorber, provides useful information about the local envi-
ronment, and is often isolated from the characteristic
vibrations of other functional groups. Carboxylate (RCO–2) Stretch Mechanical Interaction
For a long chain aliphatic such as a stearate (C18), the In carboxylic acid salts (RCO–2), the RCO–2 effectively exists as
dominant infrared bands of the CH2 group include the two equivalent carbon–oxygen bonds that are intermediate
CH2 stretches (2915 cm–1 and 2848 cm–1 for the asym and in their force constant between a double-bonded carbonyl
sym stretches, respectively), the CH2 bend/deformation (C=O) and a single-bonded ether (C–O). The RCO–2 group
(1472 cm–1) and the CH2 wag progression 1360–1160 cm–1.3,4 type bond order is consequently termed a bond-and-a-half
Only minor contributions from the methyl group are observed and behaves as a functional group with characteristic IR and
with weak bands at 2953 and 2872 cm–1 from the CH3 asym Raman bands.3–6
4 Applied Spectroscopy Practica

Scheme 2. The RCO–2 group type bond order.

Table I. Selected group frequency band assignments of sodium stearate (Na+ CH3–(CH2)16–CO–2).

Resolution
4 cm–1
Sample prep
Sodium stearate Ge ATR Structure
–1
Functional group Bands (cm ) Assignment Intensities1 IR

Water 3145 OH str m

H2O
Carboxylate 1570–1559 RCO2 asym str. s
RCO–2 1434–1407 RCO2 sym str + CH2 wag m
756, 716, 696, 668 RCO2 i-pl bend + CH2 rock m-w
632 RCO2 o-pl bend + CH2 rock w
Aliphatic
Methylene 2915 CH2 asym str s
2849 CH2 sym str s
1472 CH2 def m
1350–1180 Trans-CH2 wag progression w
716 CH2 (n > 4) rock (+RCO2 i-pl def) m
Methyl 2953 CH3 asym str w
2871 CH3 sym str w
1381 CH3 umbrella (sym def) w
C–C chain 1109 C–C–C asym str w
s: strong; m: medium; w: weak; str: stretch; asym: antisymmetric/asymmetric; sym: symmetric; def: deformation (i.e., bend).

Figure 2. The FT-IR spectrum of sodium decanoate shown in percent transmission in the 1700–1400 cm–1 region measured at 4 cm–1
resolution using a diamond ATR. An ATR correction was employed.
Larkin and Jackson 5

Table II. General RCO–2 stretching vibrations, their typical spectral

ranges, and approximate intensities.

Vibrational assignment Spectral range IR Raman

–1
Out-of-phase (asym) 1610–1520 cm Strong Weak
RCO–2 stretch
In-phase (sym) RCO–2 1450–1360 cm–1 Medium Medium
stretch (+ CH2 wag)

Figure 4. Vibrations of the RCO–2 anion and the attached CH2

groups. The carbon atoms are depicted by the grey spheres, the
oxygen atoms by the red spheres, and the hydrogen atoms by the
smaller blue spheres. The ionically bound sodium cation is not
shown. C and S represent contract and stretch, while B is bend. The
movement of the atoms is depicted by arrows or by + and – signs if
the atom movement is out of the plane defined by the page. The
blue dashed arrows help to identify the CH2 twist and rock
vibrations.

Figure 3. Vibrations of the CH2 group. The carbon atoms are

depicted by the grey spheres and the hydrogen atoms by the smaller
the vibrations of an isolated CH2 group.3–6 The characteristic
blue spheres. C and S denote contract and stretch, while B is bend.
The movement of the atoms is depicted by arrows or by + and – CH2 stretching vibrations are observed near 2915 and 2849
signs if the atom movement is out of the plane defined by the page. cm–1 and the CH2 bend at 1472 cm–1. The CH2 wag, twist,
Nodal planes are used to help differentiate the vibrations. The blue and rock vibrations are found below 1450 cm–1 and are thus
dashed arrows help to identify the CH2 twist and rock vibrations. prone to mechanically couple with RCO–2 group vibrations.
Since the stearate aliphatic unit includes 16 adjacent CH2
Both bond-and-a-half oscillators in the RCO–2 are equiva- units in the trans-configuration, multiple bands from the CH2
lent and thus strongly mechanically coupled via the coupled wag, twist, and rock vibrations occur.3,4
oscillator mechanism.4,6 This results in two characteristic The RCO–2 anion group is polar, which results in a strong
vibrations, the RCO–2 asym stretch, which occurs at a higher infrared absorbance at (1570–1560 cm–1) from the RCO–2
frequency, and the RCO–2 sym stretch, which occurs at a asym stretch and a cluster of moderately absorbing bands
lower frequency. These stretching vibrations are useful infra- from 1434–1407 cm–1 involving the RCO–2 sym stretch.3–6
red bands for metal RCO–2 analysis. The asym (RCO–2) stretch The band cluster of moderate to weakly absorbing bands
is particularly sensitive to changes in the RCO–2 environment observed between 760 and 632 cm–1 involves both the
reflecting various metal cations, their bonding geometry, and RCO–2 in-plane bend and the RCO–2 out-of-plane wag.
solid-state crystallinity interactions.7–9 Figure 4 illustrates the vibrations of the RCO–2 group along
Figure 2 shows the characteristic infrared spectrum of with selected CH2 wag, twist, and rock vibrations. A normal
sodium decanoate (Na+ CH3 (CH2)8 CO–2) in the 1700–1400 mode analysis of sodium decanoate was calculated to more
cm–1 region and Table II summarizes the generally observed fre- fully understand the vibrational bands observed for n-alkyl car-
quency ranges and expected intensities for the RCO–2 stretches. boxylic acid salts (see Supplemental Material). The RCO–2
asym stretch is a relatively isolated vibration with minimal cou-
pling with CH2 wag. However, the lower frequency RCO–2 sym
Vibrations of the CH2 and RCO–2 Groups stretch is significantly coupled with the CH2 wag resulting in a
Most of the prominent infrared bands observed in sodium stea- well-defined band cluster (1450–1400 cm–1) in the infrared
rate derive from the CH2 and RCO–2 groups. Figure 3 illustrates spectrum of sodium decanoate and sodium stearate. Similarly,
6 Applied Spectroscopy Practica

Figure 5. The FT-IR % transmission spectra of sodium decanoate (blue trace) and sodium stearate (red trace) in the 1400–1150 cm–1
spectral region highlighting the CH2 wag progression of bands. The infrared bands used to calculate the n-alkyl chain length are peak-picked.
The FT-IR spectra were measured using a Ge ATR. The illustration shows the –CH2–CH2– in-phase and out-of-phase wag vibrations
resulting in two different frequencies.4

the band cluster observed in the 780–680 cm–1 region involves identified spectral bands in this region. Similar correlations
the RCO–2 in-plane bend and the CH2 rock. in progression bands have also been observed for paraffins
and nylon.11,12 However, both paraffins and nylon differ
from the n-alkyl metal soaps, involving other vibrations
Methylene (CH2) Wag Band Progression is Predictive of such as the C–C stretch and the CH2 twist and rock in the
Aliphatic Chain Length in Metal Soaps observed progressions.
The CH2 wag results in a progression of weak bands in a As a general rule of thumb, the number of bands in this
broad spectral region (1360–1160 cm–1) due to the –CH2– spectral region for n-alkyl metal soaps (1360–1160 cm–1) is
CH2– wag interaction in the trans-configured (zigzag) equivalent to half the number of CH2 groups in the aliphatic
n-alkane chain.3,4 This characteristic behavior in the 1360– chain of the acid or salt.
1160 cm–1 spectral region has been identified for n-aliphatic The number of infrared bands in this spectral region has
carboxylic acids, acid salts (soaps), and esters and attributed been empirically correlated with the number of CH2 groups
to a progression of the CH2 wag.4 These bands are more by the following4
prominent in materials in a solid, crystalline state and the w = N / 2 (for acid / salts with an even number of carbons)
number of these bands increases as the length of the
w = (N − 1) / 2 (for acid / salts with an odd number of carbons)
n-alkyl chain increases (Figure 5). Due to minimal spectral
interferences, the n-alkyl metal soaps provide distinct, easily (1)
Larkin and Jackson 7

where w equals the number of infrared bands and N equals the this region3,4 (see Supplemental Material), which is used in
total number of carbon atoms. Thus, for sodium decanoate 5 the n-alkane chain length estimation.
infrared bands × 2 = 10 carbon atoms, i.e., C10H19O2 Na.
While for sodium stearate: 9 infrared bands × 2 = 18 carbon
atoms, i.e., C18H35O2 Na. Metal RCO–2 Structures
A closer examination of the form of the CH2 wag of two As depicted in Figure 6, the RCO–2 group can interact with
adjacent CH2 groups helps to explain this phenomenon. The metal cations in four different modes: ionic (structure a),
CH2 wag rotates the CH2 group as a whole without much bidentate (structure b), unidentate (structure c), and bridging
change in the HCH angle. The vibration mostly changes the (structure d).7,13 The metal type (i.e., ion mass, electronega-
angle between the CH2 group and the adjacent C–C tivity, and effective charge) will play a significant role in which
bonds.4 The CH2 wag also moves the carbon of the adjacent metal RCO–2 structure is favored and the resulting RCO–2
CH2 group. As a result of this strong mechanical coupling, the stretching frequencies. A comparison of the observed fre-
phase of the vibration of the adjacent trans-CH2 groups is quencies for the RCO–2 asym and sym stretches can be
important (Figure 5). The frequencies of the in-phase and used to assign the mode of metal–RCO–2 structure and is
out-of-phase vibrations will be separate and distinct with dependent upon the coordination symmetry.7,9,13 The
the out-of-phase (cooperation in coupled oscillator mecha- more isolated, strongly absorbing RCO–2 asym stretch is
nism) vibration at a higher frequency and the in-phase (oppo- very sensitive to subtle changes in coordination geometry.
sition) at a lower frequency.4 As the n-alkane chain becomes Table III summarizes some of the general average RCO–2
longer, this increases the possible in- and out-of-phase stretching frequencies for some common metal–RCO–2
combinations. structures.
The various CH2 wag vibrational modes differ in relative The simplest metal–RCO–2 interaction is the ionic type
phases and are spread out over a wide frequency range. As typically observed for alkali metal salts (i.e., Na+ and
mentioned above, some CH2 wag vibrational modes mechan- K+).7,13 The two oxygen atoms of the RCO–2 group associate
ically couple with the RCO–2 sym stretch while other lower equally with the metal cation. The metal RCO–2 has a higher
frequency modes result in the progression shown in symmetry which results in the smallest frequency difference
Figure 5. The various normal modes for selected CH2 wag (Δν = 115 cm–1) between the asym and sym RCO–2 stretching
vibrations are shown for sodium decanoate in Supplemental frequencies (cf. FT-IR spectra in Figures 1 and 2).
Material. Lastly, although the progression of infrared bands The chelating bidentate structure for the metal–RCO–2
in the 1360–1160 cm–1 region derives predominantly from structure (Figure 6c) has a similar local symmetry as
various phases of CH2 wags, both CH2 rock and twist vibra- observed for the simple ionic structure. Zinc– RCO–2 com-
tions will also contribute to the weakly absorbing band(s) in plexes typically exhibit bidentate geometry, as seen in zinc
stearate Zn (CH3–(CH2)16–CO–2)2. Figure 7 shows the
FT-IR spectrum of the zinc stearate complex (green trace).
The strong RCO–2 bands at 1535 and 1398 cm–1 derive
from the RCO–2 asym and sym stretches, respectively.7,14,15
The existence of different crystalline forms is known to
cause frequency shifts in the selected group frequencies in

Table III. A summary of an average frequency for the RCO–2

out-of-phase (asym) and in-phase frequencies for the four general
structures of metal–RCO–2.

∼RCO2 op ∼RCO2 ip ∼Δν

RCO–2 form (asym) str (sym) str (op – ip) Comment

Ionic 1560 cm–1 1425 cm–1 115 cm–1 Na+, K+

higher
symmetry
Bidentate 1535 cm–1 1400 cm–1 135 cm–1 Zn2+ higher
symmetry
Unidentate 1580 cm–1 1425 cm–1 155 cm–1 Ca2+ Lower
symmetry
Bridging Higher
Figure 6. Chemical structures of metal RCO–2: (a) ionic form of symmetry
monovalent metal ions (M=Na+ or K+); (b) unidentate
coordination; (c) chelating bidentate coordination where M=Zn2+ op: out-of-phase (asym); ip: in-phase (sym); str: stretch.
or Ca2+; and (d) bridging bidentate coordination to calcium ions. General trend of RCO2 op str = νUnidentate > νIonic > νBridging ∼ νBidentate.
8 Applied Spectroscopy Practica

Figure 7. The FT-IR spectra shown in percent transmission of zinc stearate (green trace) and calcium stearate (blue trace). Both spectra
were measured at 4 cm–1 resolution using a diamond ATR and used an ATR correction.

the infrared spectrum. Zinc stearate is known to exist in Figure 8 shows the FT-IR absorbance spectrum of a differ-
crystalline forms (Types A and B) with very different orienta- ent sourced zinc stearate (Faci USA, LLC) sample in the
tions and symmetries.15,16 The RCO–2 asym stretching band 1640–1460 cm–1 spectral region. The corresponding second
(s) is(are) particularly sensitive to subtle changes in the coor- derivative spectrum is also shown to clearly identify the over-
dination geometry. Previous work15 indicates: lapping peaks involving the RCO–2 asymmetric stretching
bands of the two polymorphic forms. This particular zinc
(i) Type A has three bands at 1590, 1546, and 1529 cm–1 stearate sample (Faci USA, LLC) has similar amounts of crys-
due to lower crystal symmetry and relative RCO–2 talline form A and form B.
orientation. The chelating unidentate structure for the metal–RCO–2
(ii) Type B has one band at 1537 cm–1 due to higher crys- structure (Figure 6b) has only one oxygen atom coordi-
tal symmetry (and RCO–2 orientation). nated with the metal cation. Calcium stearates include
this chelating unidentate structure (see below). Here
The multiple RCO–2 asym stretch bands for crystalline type A the symmetry is lower compared to either the ionic or
zinc stearate have been assigned to a tetrahedral coordina- bidentate RCO–2 species (Figures 6a and 6c). One conse-
tion by the oxygen atoms from four different RCO–2 groups. quence of this metal RCO–2 structure is a higher frequency
Since the dipole moments of the involved RCO–2 are not for the RCO–2 asym stretch. In general, the asym and sym
aligned, the asym RCO–2 stretch differs in phase resulting in RCO–2 stretching frequencies of unidentate RCO–2 struc-
multiple bands.15 The much more symmetric crystalline tures are closer to the carboxylic acid (RCOOH) carbonyl
structure of type B zinc stearate results in only one RCO–2 C=O stretch at 1700 cm–1, and the C–O stretch at
asym stretch band.15 1400 cm–1. This results in the largest frequency difference
Larkin and Jackson 9

Figure 8. The FT-IR absorbance spectra (green trace) and the second derivative spectra (blue trace) of the zinc stearate sample in the
1640–1460 cm–1 spectral region. The diagnostic infrared bands for the Type A and B crystalline forms are marked. This particular sample has
roughly equivalent amounts of the A and B crystalline forms.

(Δν = 155 cm–1) between the asym and sym RCO–2 stretch (iii) Water is typically present in the calcium–RCO–2 spe-
frequencies (Table III). cies (hydrated salts).
The chelating bridging structure for the metal–RCO–2
structure (Figure 6d) has similarities with both the unidentate The RCO–2 asym stretch of calcium stearate (Figure 7) exhibits
and bidentate coordination states. Each oxygen atom is coor- two strong distinct bands at 1601 and 1560 cm–1 and a shoulder
dinated with one metal atom, but the symmetry is higher. at 1544 cm–1. These multiple bands derive from different coor-
Because of this, the frequencies of the asym and sym dination geometries of the calcium–RCO–2 species. Calcium
RCO–2 stretches and their Δν values should be similar to stearate is also known to be polymorphous and the crystalline
that of the bidentate metal RCO–2. phases may be differentiated by the infrared absorptions in the
RCO–2 asym stretching region near 1550 cm–1.7,18 The stable
crystalline form is characterized by a doublet at 1577 and
Calcium Ion Coordination with RCO–2 1540 cm–1 while the metastable crystalline form results in infra-
The FT-IR spectrum of calcium stearate is typically more red bands at 1601 and 1562 cm–1.7,18
complex than the spectra for sodium or zinc stearates.
One obvious feature in the FT-IR spectrum of calcium stea- Conclusion
rate is the strong doublet attributed to the RCO–2 asym Stearic acid metal salts are used in a wide variety of applica-
stretch and the presence of water (Figure 7, blue trace). tions and can be encountered by analysts when making FT-IR
The water hydrate results in the infrared bands observed spectral measurements. Due to the characteristic group fre-
at 3416 and 1631 cm–1. As shown in Figure 6, calcium can quencies and environmental sensitivity of both the RCO–2 and
coordinate with the RCO–2 group in either the unidentate, CH2 (–CH2–) vibrations, IR spectroscopy is well suited
bidentate, or bridging structure. In addition, calcium stearate for both routine identification and detailed studies of
is known to be polymorphous which will also affect the FT-IR metal–soap complexes. In this study, the FT-IR spectra are
spectrum.17 presented of the sodium, zinc, and calcium stearate com-
In general, calcium cations exhibit a strong preference to plexes. A better fundamental understanding of the form of
bind to oxygen atoms. Typically, the calcium cation will bond the vibrations of characteristic IR bands of metal–stearate
to both water and RCO–2 anions in six, seven, and eight coor- salts is provided by a normal mode analysis of sodium
dinate structures in calcium RCO–2 species: decanoate.
The RCO–2 asym and sym stretching frequencies provide
(i) Sixfold calcium coordination with RCO–2 is typically information about the metal complex species and their coor-
unidentate. dination geometry. In the FT-IR spectrum the RCO–2 asym and
(ii) Sevenfold and eightfold calcium coordination with sym stretch doublets separation frequency (Δν) is diagnostic
RCO–2 is either unidentate or bidentate. of the metal cation and the coordination structure. The
10 Applied Spectroscopy Practica

RCO–2 asym stretch (1600–1520 cm–1) is particularly useful 3. L.J. Bellamy. The Infrared Spectra of Complex Molecules:
because it is a strong absorber, provides useful information Volume Two: Advances in Infrared Group Frequencies.
about the local environment, and is often isolated from the New York: Chapman and Hall, 1980. Pp. 18-20.
characteristic vibrations of other functional groups. The influ- 4. N.B. Colthup, L.H. Daly, S.E. Wiberley. Introduction to Infrared
and Raman Spectroscopy. New York: Academic Press, 1990.
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