Spectrochimica Acta Part A 68 (2007) 656–664

Spectroscopic characterization of natural calcite minerals

S. Gunasekaran a,∗ , G. Anbalagan b
a PG and Research Department of Physics, Pachaiyappa’s College, Chennai 600030, India
b PG and Research Department of Physics, Presidency College, Chennai 600005, India

Received 18 October 2006; received in revised form 15 December 2006; accepted 19 December 2006

Abstract
The FT-IR, FT-Raman, NMR spectral data of ten different limestone samples have been compared. FT-IR and FT-Raman spectral data show that
calcium carbonate in limestone, principally in the form of calcite, as identified by its main absorption bands at 1426, 1092, 876 and 712 cm−1 . The
sharp diffractions at the d-spacings, 3.0348, 1.9166 and 1.8796 confirm the presence of calcite structure and the calculated lattice parameters are:
a = 4.9781 Å, c = 17.1188 Å. The range of 13 C chemical shifts for different limestone samples is very small, varying from 198.38 to 198.42 ppm.
The observed chemical shifts are consistent with the identical C–O bonding in different limestone samples. 27 Al MAS NMR spectra of the samples
exhibit a central line at 1 ppm and another line at 60 ppm corresponding to octahedral and tetrahedral Al ions, respectively. The five component
resonances were observed in 29 Si MAS NMR spectrum of limestone and these resonances were assigned to Si (4 Al), Si (3 Al), Si (2 Al), Si (1 Al)
and Si (0 Al) from low field to high field.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Limestone; 13 C NMR; 29 Si NMR; 27 Al NMR

1. Introduction
Limestone is a sedimentary rock composed of more than
50% carbonate minerals. The estimated limestone deposits
in India are about 169,941 million tonnes. Limestone, the
principal raw material for cement manufacture forms one of
the most important mineral deposits of India and provides a
solid base for the industrial prosperity of the country. Calcium
carbonate occurs in three different forms—hexagonal crystal
known as calcite, orthorhombic form aragonite and hexagonal
form vaterite. Calcite is the most abundant form and widely
distributed in the Earth’s crust followed by aragonite, vaterite
and comparatively rare dolomite. Most calcite is relatively
pure. Common impurities include magnesium, ferrous ion and
manganese. The structure of calcite is of more interest because
a number of important mineral constituents of sedimentary
rocks, including magnesium and iron-bearing carbonate, have
structures which are identical with or closely related to the
calcite pattern. Therefore, the structure of calcite serves as a
logical starting point in describing the structures of such miner-
als. Calcite has a trigonal structure with two molecules per unit
∗ Corresponding author. Fax: +91 44 26426900.
E-mail address: sethugunasekaran@rediffmail.com (S. Gunasekaran).
cell. The calcium ions and the carbon atoms of the carbonate
ions all lie on the trigonal axis and the orientations of the two
carbonate ions are staggered relative to each other so that there
is a centre of symmetry. High-resolution nuclear magnetic
resonance spectroscopy using magic angle sample spinning
(MAS) is a powerful tool in the study of crystal structure and has
been applied extensively to the study of mineral systems such
as clays and zeolites [1–20]. In NMR spectroscopy, a nucleus
with non-zero spin is used as a sensitive probe for its local
electronic environment. The most useful parameter obtained is
the chemical shift (or shielding), which characterizes the degree
to which nearby electrons shields the probe nucleus from a large
external magnetic field. Nuclei in different bonding sites or
environments are shielded differently and hence absorb energy
at different frequencies. In polycrystalline solid, however,
spectral features are broadened by the orientational anisotropy
of chemical shielding and by interactions between nuclei. By
rapidly spinning a powdered sample at the magic angle 54.7◦ ,
relative to the external magnetic field, the broadened lineshapes
break up to a center peak located at the isotropic chemical shift
plus a series of spinning sidebands spaced at the rotational
frequency, typically 1–4 kHz [3,4]. For crystalline samples,
sideband intensities can be analyzed to obtain the principal
values of the chemical shielding tensor [5,6], but are often made
negligible by spinning rapidly compared to static linewidth

1386-1425/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.saa.2006.12.043
 S. Gunasekaran, G. Anbalagan / Spectrochimica Acta Part A 68 (2007) 656–664 657

expressed in Hz. One can obtain well-resolved spectra of Table 1

isotropic chemical shifts, similar to NMR spectra commonly Results of the chemical analysis (%)
obtained from liquids. At least four magnetically active nuclei Sample CaO MgO SiO2 Fe2 O3 Al2 O3 K2 O Na2 O
have been used in studying carbonate minerals with magic angle code
spinning (MAS) NMR: carbon-13, silicon-19, aluminium-27 L01 46.38 0.60 12.11 0.92 2.01 0.11 0.18
and oxygen-17. The natural abundance of 13 C however, is L02 46.05 0.70 13.32 1.18 1.75 0.06 0.20
only 1.1% making spectrum acquisition slow [15]. 27 Al is a L03 52.19 0.59 4.93 0.72 0.44 0.04 0.09
quadrupolar nucleus with spin of 5/2. It is 100% abundant, with L04 51.46 0.65 4.41 0.64 0.84 0.05 0.14
L05 50.53 0.61 2.20 4.10 1.09 0.03 0.11
relative sensitive with respect to the proton of 0.21. 29 Si has a L06 49.22 0.60 9.38 0.58 1.11 0.20 0.21
spin of 1/2 and natural abundance of 4.70%. Thus the chemical L07 49.02 0.73 6.51 0.83 1.59 0.38 0.24
shift does not suffer from such a quadrupole broadening effects L08 49.87 0.62 5.62 0.89 1.57 0.28 0.19
[21]. The spinning side bands for 29 Si may be caused by the L09 54.35 0.69 – 0.40 0.29 0.02 0.09
presence of chemical shift anisotropy (CSA) [21],by various L10 52.50 0.68 2.08 0.53 0.50 0.04 0.10
magnetic impurities or by dipolar interactions [22].
The major objectives of this study were to determine the 13 C
NMR chemical shifts of the carbonate phases to investigate the X-band EPR spectra of the samples were recorded on a
effects of structure and composition on these chemical shifts. JEOL JES-TE100 , EPR spectrometer with a field modulation
Also, we present high-resolution solid-state 29 Si and 27 Al MAS of 100 kHz and 1 mW microwave power. DPPH was used as a
NMR data for different limestone samples. field marker.

2. Materials and methods 3. Results and discussion

Limestone minerals were ground with agate mortar and pes-
tle. The powder sample was sieved, and particles with diameter
smaller than 50 ␮m were submitted to X-ray diffraction (XRD),
Fourier-transform infrared spectroscopy (FT-IR), and Fourier-
transform Raman (FT-Raman), and solid-state nuclear magnetic
resonance spectral analysis. XRD analyses were performed
with a SEIFERT X-ray diffractometer with Cu K␣ radiation
(λ = 1.54 Å), Cu filter on secondary optics, 45 KV power and
20 mA current. The powder sample was mounted on a quartz
support to minimize background.
Perkin-Elmer spectrum one FT-IR spectrometer was used,
and the samples were analyzed in KBr pellets. Spectra were
traced in the range 4000–400 cm−1 , and the band intensities
were expressed in transmittance (%).
Bruker IFS FT-IR spectrometer with FRA Raman attachment
was used and Nd:YAG laser of wavelength 1064 nm was used as
the source. The spectra were traced in the range 3500–50 cm−1
with 500 scans at 0.1 cm−1 resolutions. Both infrared and Raman
analysis permitted the identification of the main molecular
groups present in the samples.
Approximately 2 mg of powdered sample was used to acquire
the 13 C, 29 Si and 27 Al NMR spectra under magic-angle spin-
ning (MAS) conditions. The spectrometer used was DSX 300.
Spectra were obtained at a frequency 59.617 MHz for 29 Si,
75.45 MHz for 13 C and 78.19 MHz for 27 Al. Rapid (8–9 kHz)
sample spinning at the magic angle to the external magnetic field
was used. In most cases, conventional FT NMR with 7 ␮s radio
frequency pulses and 5 s time intervals was used.
3.1. FT-IR
The chemical compositions, FT-IR spectral data of the natural
limestone samples are compiled in Tables 1 and 2. The data indi-
cate that the main CaCO3 composition in limestone, principally
in the form of calcite, as identified by its main absorption bands
at 1426, 1092, 876 and 712 cm−1 . The bands observed in the
present study were compared in Table 2 with those already pub-
lished in the literature [23–28]. In the FT-IR spectra of carbonate
samples the out-of-plane bending (υ2 ), the asymmetric stretch-
ing (υ3 ), and the in-plane-bending (υ4 ) modes of the carbonate
ion group are found to be active (Fig. 1) as predicted from factor
group analysis [29]. Besides the first order internal modes, the
υ1 + υ4 , 2υ2 + υ4 , 2υ3 combination modes are observed. The
presence of non-splitting peaks υ2 and υ4 in the samples L1 –L10
(Fig. 1) indicate the presence of calcite structure in those sam-
ples [30]. Sterzel [31] found that the observed υ2 band occurs
at 877 cm−1 for 12 C. This band shifts to 850 and 826 cm−1 ,
respectively, for 13 C and 14 C owing to isotopic shift. But in the
present study, the observed υ2 band occurs at 876 cm−1. This
clearly indicates that there is no isotopic shift. All the samples
have strong bands related to the presence of bound water (around
3400 cm−1 ). The water might be bound to hydraulic com-
pounds, like silicate and aluminate hydrates. The bands at 1040,
799, 525 and 462 cm−1 (Fig. 1) indicate the presence of silicate
phases (Si–O vibrations) [32]. Roy [33] found that the pure
silicate band at 1100 cm−1 shifted to lower wave numbers on
substitution of aluminium or iron in the clay mineral lattice. The

Table 2
Vibrational frequency assignments (FT-IR)
υ1 (cm−1 ) υ2 (cm−1 ) υ3 (cm−1 ) υ4 (cm−1 ) υ1 + υ4 (cm−1 ) 2υ2 + υ4 (cm−1 )

Ref. [16,17] – 876 1435 712 1812 2545

This work – 874 1425 712 1798 2514
658 S. Gunasekaran, G. Anbalagan / Spectrochimica Acta Part A 68 (2007) 656–664

Table 4
Unit cell parameters of limestone samples

Sample code a (Å) c (Å) c/a (Å) Volume (Å3 )

L01 4.9945 17.1003 3.4238 369.414

L02 4.9894 17.1050 3.4283 368.770
L03 4.9999 17.0983 3.4197 370.170
L04 4.9945 17.0759 3.4189 368.891
L05 4.9980 17.0985 3.4279 368.414
L06 4.9973 17.1086 3.4236 370.016
L07 4.9914 17.1128 3.4285 369.230
L08 4.995 17.1005 3.4235 369.504
L09 4.9961 17.0851 3.4197 369.323
L10 4.9986 17.1022 3.4214 370.073

Table 5
13 C chemical shift and full width half maximum (FWHM) value of limestone

samples
Sample code Chemical shift (ppm) FWHM (Hz)

L01 198.38 72.56

L02 198.41 76.83
Fig. 1. FT-IR spectra of limestone samples. L03 198.42 76.83
L04 198.40 72.56
L05 198.40 123.78
L06 198.38 81.1
silicate bands probably indicating the content of silicate phases L07 198.41 85.36
in the sample, which is in agreement with the chemical analysis L08 198.40 76.83
data. L09 198.42 55.49
L10 198.43 76.83

3.2. FT-Raman
The Raman spectra of the limestone minerals are shown in
Fig. 2a–c, and it is evident that the internal A1g,int mode (υ1 ,
symmetric stretch) of the carbonate anion, located at approx-
imately 1092 cm−1 , is the strongest feature in each spectrum.
The weak lines located in the regions of 1450 and 714 cm−1
are attributable to the υ3 and υ4 vibrational modes, respec-
tively. The two smaller frequency shifts 162 and 288 cm−1
observed in Raman spectra arise from the external vibrations
of the CO3 groups which involve translatory and rotatory oscil-
lations of those groups [34]. A weak line observed at 1750 cm−1
(Fig. 2a–c; Table 3) may be regarded as the combination band
of υ1 + υ4 [35]. This interpretation is also favoured by Schaefer
[36]. However, Krishnan [37] assigned this band to 2υ2 . Exter-
nal modes observed in Raman spectra in the region 150–190 and
285–310 cm−1 are due to the relative translations between the
cation and anionic groups [34]. The frequency shift observed
at 91 cm−1 in all the limestone samples is due to the rotational
oscillations of the CO3 groups about the trigonal axis of symme-
try [34]. The strong Raman vibration at 1092 cm−1 corresponds
to the case in which all the CO3 groups vibrate in identical phases
[34].
3.3. XRD
Typical X-ray diffraction pattern obtained on limestone min-
erals are reported in Fig. 3a and b. The intensity of the peaks
is quite sharp with little background absorption. The various
Bragg’s reflections are compared with those given in Joint Com-
mittee on Powder Diffraction Standards (JCPDS) files Card
5–586 (Calcite). Except for few reflections, the agreement is
found to be good confirming that the crystal structures of the
mineral L1 –L10 (limestone) are calcite [38,39]. The extra reflec-
tions at the glancing angles 26.6150◦ , 50.0830◦ . d-Spacings
3.34656, 1.81786 Å indicate the presence of aragonite phase
also in some of the limestone samples. The calculated lattice
parameters are given in Table 4.
3.4. 13 C NMR spectra
Fig. 4a and b shows the 13 C NMR spectra of limestone
samples and Table 5 lists the 13 C NMR chemical shifts (peak
maxima) and peak widths (FWHM). The calcite (space group
R3̄c) has nearly identical peak positions and narrow peak widths
(Fig. 4a and b). The observed average 13 C chemical shifts and

Table 3
Vibrational frequency assignments (FT-Raman)
υ1 (cm−1 ) υ2 (cm−1 ) υ3 (cm−1 ) υ4 (cm−1 ) υ1 + υ4 (cm−1 )

Refs. [17–20] 1085 – 1435 711 1748

This work 1092 – 1437 716 1754
S. Gunasekaran, G. Anbalagan / Spectrochimica Acta Part A 68 (2007) 656–664 659

Fig. 2. (a–c) FT-Raman spectra of limestone samples.

660 S. Gunasekaran, G. Anbalagan / Spectrochimica Acta Part A 68 (2007) 656–664
Fig. 3. (a and b) XRD pattern of limestone samples.
peak widths (FWHM) are 198.439 ppm and 79.808 Hz, respec-
tively. One of the samples show larger peak width, 123.788 Hz
probably the result of Fe3+ and Mn2+ substitution for Ca2+ ,
which is typical in calcite. The most interesting result of this
study is the very small-observed range of 13 C chemical shifts
(193.382–198.6 ppm). Data for calcite extend this range to
167.6 ppm [15]. It is less than the range for 29 Si chemical shift in
Al-free orthosilicates (no bridging oxygen) ≈11 ppm [18]. This
result is not surprising, given that all the samples examined have
isolated CO3 2− groups and contain no bridging oxygens. Thus
only changes in the large cations, which are next nearest neigh-
bours to the carbon atoms, and changes in structure are available
to cause in the 13 C NMR chemical shifts. Each CO3 2− group in
calcite is coordinated to six large cations and the increased peak
breadth must be due to different number of Ca and Mg atoms
coordinated to different individual CO3 2− groups. The spectra of
limestone samples show no multiple, resolvable peaks in order
to the investigate (Mg, Ca) order–disorder phenomena in these
phases.
The CO3 2− ion consists of a central sp2 hybridized C-atom
with three O atoms at the corners of an equilateral triangle. The
three atoms are about 2.3 Å apart and the whole group lies in a
plane at right angles to the three-fold C-axis [19]. Since O has
a low abundance of the magnetic isotope 17 O (0.037%, I = 3/2),
with a small magnetogyric ratio [−3.6279 × 107 rad/(T S)] and a
large quadrupole moment (−2.6 × 1026 Q/m2 ), the dipolar inter-
action between the O and C atoms is negligible. The line width
of the MAS spectrum is determined mainly by the distribution
of isotopic shifts and other residual interactions, since chemical
shift anisotropy is averaged out by MAS and would not con-
tribute to line broadening [12,13]. Therefore, difference in line
width suggests that the distribution of isotopic chemical shift
is due to different microscopic environments. In addition to the
data, presented above, an attempt has been to investigate sev-
eral natural paramagnetic phases present in the samples. EPR
spectrum of limestone shows intense paramagnetic absorptions
(Mn2+ ion) (Fig. 5). These results strongly indicate that the spin-
ning side bands observed in the MAS NMR spectra may be due
not to chemical anisotropy, but rather to the paramagnetic or
ferromagnetic ions [17].
3.5. 27 Al NMR spectra
27 Al NMR spectra of limestone samples are shown in
Fig. 6(A–D). The spectra consist in general of a strongly broad
central band accompanied at both sides by one or two symmet-
rically located peaks of low intensity which represent spinning
side bands. According to the previous work [40,41], the central
line at ≈1 ppm must assign to the octahedral Al ions and the
line at ≈60 ppm to tetrahedral Al ions. These assignments are
in agreement with the structural composition of these samples.
Thus limestone L4 , L6 , L9 contains only Aloct (Fig. 6A–C) while
 S. Gunasekaran, G. Anbalagan / Spectrochimica Acta Part A 68 (2007) 656–664
Fig. 4. (a and b) 13 C NMR spectra of different limestone samples.
L1 has (Fig. 6D) has both Aloct and Altet . The chemical shift of
tetrahedrally coordinated aluminium varied from one sample to
another in the range from 50 to 70 ppm. 27 Al chemical shift is
related to the neighborhood of an AlO4 5− tetrahedron. Exten-
Fig. 5. X-band EPR spectra of limestone samples.
661
sive measurements of 29 Si spectra of aluminosilicates [16,42,43]
indicate that tetrahedral aluminium is present in only two near-
est neighbor tetrahedral environments: either Al (4 Si) or Al
(3Al), but never both in the sample [16]. Consequently, unless
there are topographically equivalent tetrahedral Al atoms in the
sample, only one 27 Al peak will be observed for each sample,
unlike 29 Si where up to five peaks are simultaneously present.
The range of 27 Al NMR shifts, for four coordinated aluminium,
from 55 ppm in aluminosilicates up to 80 ppm in aluminates,
indicates that the chemical shift values are influenced not only
by the coordination of the Al but also effects by the second
coordinate sphere [21]. The spinning side bands observed in
many natural aluminosilicates may be due not to chemical shift
anisotropy, but rather to the presence of large magnetic suscep-
tibility broadenings [17] as is observed. If there is any Al–Si
disorder, Al atoms can occupy all four kinds of crystallographi-
cally non-equivalent sites. For each of these crystallographically
non-equivalent sites, there will be 11 chemically non-equivalent
sites, corresponding to 0–10 Al atoms in the second nearest
neighbor tetrahedral sites. Unfortunately, because of peak broad-
ening by second-order quadrupole interaction and the relatively
small effect on the isotropic chemical shift, this increase in the
number of chemically non-equivalent Al sites results only in an
increased peak breadth and not in an increase in the number of
peaks [44].
662 S. Gunasekaran, G. Anbalagan / Spectrochimica Acta Part A 68 (2007) 656–664
Fig. 6. (A–D) 27 Al NMR spectra of limestone sample (a) 8 kHz, (b) 6 kHz.
3.6. 29 Si NMR spectra
29 Si NMR spectra of two different limestone samples are
given in Fig. 7. The total range of 29 Si chemical shifts in sil-
icates is appreciable from −60 to −120 ppm with analytically
significant sub division into well separated range for monosili-
cates (Q0 ), disilicates and chain end groups (Q1 ), middle group
in chains (Q2 ), chain branching sites (Q3 ) and the three dimen-
sional cross-linked frame work (Q4 )[45]. Any phase in which
Fig. 7. 29 Si NMR spectra of different limestone samples.
all Si sites are crystallographically silicon–oxygen tetrahedral,
such as Q2 and Q3 or tetrahedral of the same type, but of a differ-
ent degree of aluminium substitution in the second coordination
sphere such as Q4 (3 Al) and Q4 (2 Al), two or more 29 Si lines
were registered in the NMR spectrum [45]. In the present study,
five components were observed at −76, −84, −94, −101 and
−107 ppm in one sample (Fig. 7) and this may be attributed
to the differences in chemical octahedral environment of Si or
probably due to the presence of other mineralogical phases in
the sample [46]. The peaks can be assigned to Si (4 Al), Si (3
Al), Si (2 Al), Si (1 Al) and Si (0 Al) from low field to high
field on the basis of the empirical relation derived by Ramdas,
Klinowski, et al. [47]. However, the other sample (Fig. 7) exhibit
only two components at −88 and −93.116 ppm and these peaks
assigned to Si (3 Al) and Si (2 Al) [27]. The NMR spectra are
considered to a first approximation to be split into five reso-
nances due to the placing of first nearest neighbor aluminium
atoms. With the second and further nearest neighbor interac-
tions, and additionally crystallographic in equivalence in some
cases, many different environments are created and substantial
line broadening results [48]. In some cases, the crystallographic
in equivalence may be comparable in magnitude to the effect
of the first nearest neighbors giving overlap of the peaks and a
deceptively simple spectrum [48]. Increasing condensation of
the SiO4 tetrahedra leads to high field shifts and substitution of
Si ion in SiO4 tetrahedra by Al ions leads to low field shifts [1],
 S. Gunasekaran, G. Anbalagan / Spectrochimica Acta Part A 68 (2007) 656–664
which are clearly inferred, from the spectra. 29 Si NMR chem-
ical shifts are sensitive to Si–O–T bond angles and to lesser
degree Si–O bond lengths [49]. If a good angle/shift correla-
tion exists, then it may be possible to assign peaks for a known
crystal structures. In general, for a particular Qn , the larger the
mean Si–O–Si bond angles for a tetrahedran, the more negative
its 29 Si chemical shifts (Fig. 7) [49].
The line position of tetrahedral Si and Al depend on the nature
of the cations located as second nearest neighbors of these nuclei
in the tetrahedral sheet, the octahedral sheet and the inter layer
space. In the case of Aloct , the line position of the NMR line
seems to depend only on the nature of cations located as sec-
ond neighbors in the octrahedral sheet [46]. With even a slight
degree of disordering, all five types of chemically non-equivalent
Si sites from tetrahedral linkage could be present [50]. Lippmma
et al. [45] found a correlation between a high field (more neg-
ative) chemical shift and increasing degree of polymerization
(Q0 –Q4 ) and also found distinct range of chemical shifts for Q0 ,
Q1 , Q2 , Q3 and Q4 Si sites for those phases with no Al in the
tetrahedral sites [14]. However, in the present study, the reso-
nances observed in the region 62.6 ppm indicate the presence
of Al in the tetrahedral sheets (Fig. 6). The signal observed at
the highest field (−107 ppm) in Fig. 7 is close to that of quartz
and should correspond to the unsubstituted Si (0 Al) units [51].
The 29 Si peak breadth of the limestone relative to aluminosili-
cate crystals is probably due to both an increase in the range of
the number of aluminium NNN to silicon and an increase in the
range of bond angles and bond distances for each type of silicon
site [52].
The observed five peaks and peak spacing in the 29 Si NMR
spectrum of limestone (Fig. 7) would be to assign each peak to
different NNN configuration [49]. The line broadening and side
band formation may be attributed to the presence of paramag-
netic ion (Mn2+ ) present in the samples (Fig. 5). This result was
confirmed by the EPR spectra of the samples. The presence of
substitutional impurities is expected to affect isotropic chemical
shift. The effect of paramagnetic impurities would be to reduce
the shielding (i.e. because more positive or less negative chemi-
cal shifts). The inherent chemical shift anisotropy also probably
makes a contribution to the side bands, but in most instances
the side bands are quite prominent and correlate well with the
presence of magnetic susceptibilities [22].
4. Conclusion
The limestone minerals show characteristic infrared and
Raman bands and XRD pattern confirms the calcite structure
present in all the samples. High-resolution NMR spectroscopy
affords a valuable adjunct to diffraction methods in crystal struc-
ture analysis of silicates. It permits one to distinguish between
tetrahedral and octahedral coordinated aluminium and also the
different chemical environments of tetrahedrally coordinated sil-
icon. From these results, it is possible to elucidate the local
ordering schemes in the distribution of isomorphous replace-
ments (Si, Al), which is difficult to be established by X-ray
diffraction methods. Paramagnetic impurities in the natural sam-
663
ples cause extensive spinning sidebands, which complicate the
spectral analysis. The average 13 C chemical shift is 198.439 ppm
and the average peak width (FWHM) is 79.808 Hz. 27 Al MAS
NMR spectra of the samples exhibit a central line at 1 ppm and
another line at 60 ppm. These lines are assigned to octahedral and
tetrahedral Al ions. Five component resonances were observed
in 29 Si MAS NMR spectrum of limestone and these resonances
were assigned to Si (4 Al), Si (3 Al), Si (2 Al), Si (1 Al) and Si
(0 Al) from low field to high field.
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