Talanta 178 (2018) 1001–1005

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Talanta
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1
H NMR assisted quantification of glycerol carbonate in the mixture of MARK
glycerol and glycerol carbonate
⁎
Avneet Kaur, Ranjana Prakash, Amjad Ali
School of Chemistry and Biochemistry, Thapar University, Patiala 147004, India

A R T I C L E I N F O A B S T R A C T

Keywords: Glycerol carbonate (GLC) is a very important chemical having a variety of application viz., green solvent in
Quantitative nuclear magnetic resonance organic synthesis, an electrolyte in lithium batteries, wetting agent in cosmetics and precursor in polymer and
1
H NMR quantification food industry for the synthesis of 1,3-sn-diglycerides. Hence, it is vital to find out the quick and simple method
Glycerol carbonate for the quantification of GLC when it is synthesized via dimethyl carbonate (DMC) assisted transesterification
Glycerol
with glycerol (GL). Present study, proposes simple, accurate and non destructive quantitative proton nuclear
Dimethyl carbonate
magnetic resonance (qHNMR) method for the determination of GLC. Based upon the study, two different
equations are proposed to calculate the GLC employing the data obtained from the 1H NMR spectra. qHNMR
results were also validated by preparing the standard mixtures of varying concentrations of GL and GLC. Further,
to conform the developed method for a real application, GLC concentration was also estimated during CaO
catalyzed DMC transesterification with GL. The qHNMR assisted GLC quantification were found consistent with
those obtained from high-performance liquid chromatography analysis (R2 = 0.99).

1. Introduction operational procedure, volatile component, and mass spectroscopy for

1
H NMR, a non-destructive analytical technique being used widely
for determining the structure of molecules, has also emerged as an
analytical tool for the quantification of the molecules owing to its ac-
curacy, specificity and selectivity [1,2]. NMR technique has been
widely employed for the quantification of a variety of molecules in-
cluding drugs [3], blood plasma metabolites [4], agricultural chemicals
[5], enantiomers [6], biofuels [7,8] and plant metabolites profiling [9].
The driving principle of quantitative NMR analysis has emerged from
the fact that, integrated peak area of each 1H NMR signal provided is
directly corresponds to the equal number of equivalent nuclei/nucleus
responsible for that signal [10]. Therefore, integrated peak area is di-
rectly related to the number of hydrogen atoms appearing at a specific
chemical shift in NMR spectra of a compound. Absolute and relative
quantification of several molecules can be easily achieved by quanti-
tative proton NMR (qHNMR) analysis. In order to calculate the molar
ratios in a mixture of two compounds the integration value of the
baseline separated signals and number of participating nuclei are con-
sidered [11].
Besides qHNMR, Gas Chromatography (GC) [12] and High Perfor-
mance Liquid Chromatography (HPLC) [13] are the two widely used
chromatographic methods for quantifying the molecules. Out of these
two techniques, GC is destructive in nature and require complicated
product confirmation [14], while HPLC is time consuming technique
demanding costly HPLC grade solvents, set of standards, equilibration
of the columns and/or derivatization of the analyte [3] and also has no
universal detector.
On the other hand qHNMR does not require any complicated sample
preparation method or high purity sample, or longer analysis time, or
sample reference requirement. Additionally qHNMR technique is non-
destructive in nature and hence, compound could be recovered after the
analysis and also helps in determining the molecular structure [15]. The
amount of deuterated solvent needed for qHNMR analysis is minimal
(~ 0.5 mL or less) compared to the larger solvent volume used in HPLC
or large volume of high purity gases required for GC analysis. Thus, the
higher costs for deuterated solvents can be easily compensated.
Glycerol carbonate (GLC), known as green solvent [16], is a deri-
vative of glycerol (GL) and have a variety of applications such as an
ionic liquids substitute, liquid carrier in lithium based batteries [17], as
biobased substitute to organic solvents, a potential solvent for gas se-
paration [18], as a component in building eco-composites [19] and as a
monomer in polymer industry [20]. GLC is used as a precursor for the
formation of 1,3-sn-diglycerides which is having a wide range of ap-
plications in the food industry viz., in maintaining low hydrophilic-li-
pophilic balance, as co-emulsifiers, [21] as rheological modifiers [22]
and also as a coco butter substitute in chocolate industry [23].

⁎
Corresponding author.
E-mail address: amjadali@thapar.edu (A. Ali).

http://dx.doi.org/10.1016/j.talanta.2017.08.103
Received 15 June 2017; Received in revised form 29 August 2017; Accepted 30 August 2017
Available online 01 September 2017
0039-9140/ © 2017 Elsevier B.V. All rights reserved.
A. Kaur et al.
Transesterification of GL with dimethyl carbonate (DMC) is considered
as greener route for the GLC synthesis [24].
In literature two chromatographic methods, viz., GC [12] and HPLC
[13] have been employed for GLC quantification. Fourier transform
infrared spectroscopy (FTIR) has also been employed for the GLC
quantification, when its concentration is in the range of 70–75% in a
mixture of GL and GLC [25].
To the best of our knowledge, qHNMR technique has not been ex-
plored for the GLC quantification in the literature. Herein, we have
purposed qHNMR spectroscopic method to determine the composition
of samples obtained from the transesterification of dimethyl carbonate
with glycerol to produce glycerol carbonate without any requirement of
sample derivatization.
2. Experimental
2.1. Materials and reagents
Glycerol 1,2 dicarbonate (≥ 98%) and glycerol (≥ 98%) were
purchased from TCI Chemicals, JAPAN and LOBA Chemie, INDIA re-
spectively. HPLC grade hexane and isopropanol solvents were pur-
chased from Spectrochem, INDIA. Dimethyl sulfoxide-d6 and
Deuterated water (D2O) were purchased from Sigma-Aldrich, USA.
2.2. GL and GLC sample preparation
To test the linearity, and reproducibility of the qHNMR technique,
different samples were prepared by mixing the known amount of GL
and GLC in various molar ratios as described in Table 2. From these
prepared mixtures, a known amount (8 mg) was weighed which were
finally diluted with 0.6 mL of D2O or DMSO and subjected to the proton
NMR analysis.
All weighing were performed with Shimadzu analytical balance
(ATX224), having the maximum weighing capacity of 220 g and ac-
curacy of 0.1 mg.
2.3. 1H NMR analysis
The 1H NMR spectra were obtained at central frequency of 400 MHz
on JEOL JNM-ECS 400 using 5 mm NMR tube. Longitudinal relaxation
time (T1) was determined by dissolving GL and GLC in D2O solvent. The
relaxation time of the protons employed for the quantitative analysis
were determined by the inversion recovery experiment at 90◦ pulse
angle, using the Delta NMR software supplied with the JEOL equip-
ment. Relaxation delay (d1), for the proton signal employed in quan-
tification, must be ≥ 5 times to the value of longest relaxation time
(T1) [1]. During the experiments, maximum value of the T1 was found
to be 2.8 s and hence, d1 was fixed at 14 s for quantification experi-
ments. 1H NMR spectra were recorded in either D2O or DMSO-d6 with
the following acquisition parameters: 45° pulse angle of 4.87 µs pulse
width; transmitter frequency offset (O1P) of 5 ppm; acquisition time
2.18 s; 64 scans; spectral acquisition temperature 291–298 K. Two
different relaxation delay (d1) time; 4 s (by default) and 14 s (obtained
from inversion recovery experiment) were opted for carrying out the
qHNMR analysis. Spectra obtained at both the relaxation delay were
compared for finding out the accuracy of the 1H NMR signals. All
spectra were processed by the MestReNova package (6.0.2-5475). To
obtain the integral value, each 1H NMR spectrum was normalized by
assigning a value of 1 to one of the methylene proton (c1) of glycerol
carbonate molecule.
2.4. HPLC analysis
For HPLC analysis, different samples were prepared by mixing the
known amount of GL and GLC in various molar ratios as described in
Table 2. These samples were dissolved in hexane: isopropanol (20:80,
1002
Talanta 178 (2018) 1001–1005
O
HO O Catalyst
OH O O CH 3 OH
HO O O
OH
Glycerol Dimethyl carbonate Glycerol Carbonate Methanol
Fig. 1. Dimethyl carbonate assisted transesterification of glycerol.
v/v) solvent mixture to prepare the solutions of 0.01 M concentrations.
All samples were syringe filtered prior to the injection and were ana-
lyzed by using Agilent infinity 1200 HPLC equipped with a RI detector.
The RX-SIL normal phase column (4.6 mm inner diameter × 250 mm,
5 µm particles) at 35 °C was employed as stationary phase and hexane:
isopropanol (20:80, v/v) as mobile phase at flow rate of 0.3 mL min−1
with injection volume of 20 µL. In the HPLC chromatogram of standard
mixture of GL and GLC, the content of GL and GLC was calculated from
the percentage of the peak area corresponding to each compound in
relation to the total area of the chromatogram as shown in Fig. 5S–8S,
in electronic supporting information.
2.5. Transesterification of glycerol with dimethyl carbonate
In order to quantify the GLC in the reaction mixture, transester-
ification of dimethyl carbonate with glycerol in presence of CaO was
conducted as shown in Fig. 1. In a typical reaction, GL (21.7 mmol, 2 g),
DMC (43.4 mmol, 3.9 g) and CaO (100 mg) were added to the 25 mL
two necked round-bottomed flask equipped with an oil bath, magnetic
stirrer and reflux condenser. The mixture was heated with continuous
stirring at 85 °C temperature for 1 h. After the stipulated time the re-
action mixture was filtered to remove the solid catalyst and liquid phase
was rotary evaporated at 65 °C to remove the excess DMC and me-
thanol. The reaction mixture thus obtained was analyzed by proton
NMR and HPLC techniques.
3. Results and discussion
3.1. Choice of solvent for NMR (DMSO versus D2O)
In literature 1H NMR spectra of GLC, recorded in deuterated DMSO,
was primarily used for determining the chemical structure of the mo-
lecule [20,26] but not for quantitative purpose. Proton NMR spectrum
of a mixture of GL and GLC in DMSO-d6, shows d, e1 and e2 proton
signals of GL superimposes with a1 protons of GLC in the region of
4.33–4.48 ppm and H2O peak of DMSO-d6 in the range of
3.273–3.412 ppm, as shown in Fig. 2. This difficulty could be overcome
by recording the proton NMR spectra of GL as well GLC in D2O. As
could be seen from the Fig. 2, each signal of GL and GLC proton is well
resolved and could be easily assigned to the respective protons without
having the issue of D2O signal overlapping with sample proton signals.
In D2O, the comparison of 1H NMR spectra of GL with that of GLC
(Fig. 2) shows that signal a1, a2, b, c1 and c2 were observed only for
GLC and signal d, e1 and e2 observed for GL. Table S1 (in supplemen-
tary information) gives the descriptions of all the signals observed in
proton NMR spectrum of both the molecules and overlapping signals
(used for quantification purpose) are shown in italics. In a proton NMR
spectrum of a mixture of GL and GLC in D2O, d proton signal of GL
overlaps with one of the doublet of c2 proton signal (3.557–3.640 ppm)
of GLC as shown in Fig. 3. In this overlapping zone, peak area corre-
sponding to GLC proton (c2) would be equal to the peak area of non
overlapping GLC proton (c1,a1and a2). This analogy is used while de-
riving the Eqs. (1) and (2) for calculating the molar %age of GLC in a
mixture of GL and GLC.
3.1.1. Selection of relaxation delay (d1)
Beside the selection of suitable solvent, instrumental parameter like
relaxation delay (d1) need to be optimised to develop an accurate
qHNMR method as it may influence the appearance and intensity of the
A. Kaur et al. Talanta 178 (2018) 1001–1005

Fig. 2. 1H NMR spectra of standard (i) GLC (ii) 30:70 (m/m) mixture of GL/GLC and (iii) GL in DMSO; standard (iv) GLC (v) 40:60 (m/m) mixture of GL/GLC and (vi) GL in D2O
respectively.

peaks in the 1H NMR spectra. T1 values for the protons employed for
the quantitative analysis were found 2.8 s, 2.3 s, 1.8 s for GLC, GL and
mixture of GL/GLC respectively. In order to satisfy the underlying
principal of proton qNMR technique (d1 ≥ 5T1), d1 value of 14 s was
used.
In order to reduce analysis time, in few reports shorter relaxation
time were also employed during the qHNMR experiments [27]. Even in
present study at shorter relaxation delay (4 s), ~ 90% signal recovery
was observed as given in Fig. 2S (electronic supplementary informa-
tion). Further, quantification results obtained by qHNMR either at 14 s

Fig. 3. Expanded region (3.53–3.91 ppm) of 1H NMR spectra in D2O; (i) pure GLC, (ii) 40/60 (m/m) GL/GLC mixture and (iii) pure GL.

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A. Kaur et al. Talanta 178 (2018) 1001–1005

Table 1 Table 2
The actual glycerol carbonate concentrations and those predicted by the qHNMR at dif- The actual glycerol carbonate concentrations and those predicted by the qHNMR and
ferent relaxation delays. HPLC techniques.

S. No. Mole % taken Predicted % CGLC by NMR S. No. Mole % taken Predicted % CGLC by NMR Predicted % CGLC
by HPLC
GLC GL d1 = 4 s d1 = 14 s GLC GL Eq. (1) ( ± S.D.) Eq. (2) ( ± S.D.)

1 90 10 87.71 87.28 1 90 10 88.9 ± 1.05 89.28 ± 0.81 89.58

2 80 20 78.70 79.50 2 80 20 79.66 ± 0.97 79.45 ± 0.40 80.53
3 70 30 69.44 68.75 3 70 30 69.07 ± 1.59 68.44 ± 1.54 70.87
4 60 40 62.10 62.65 4 60 40 60.38 ± 1.64 60.38 ± 1.64 59.87
5 50 50 49.26 45.02 5 50 50 49.28 ± 0.21 49.28 ± 0.21 49.7
6 40 60 41.49 40.39 6 40 60 40.26 ± 1.08 40.12 ± 1.24 41.34
7 30 70 30.21 28.97 7 30 70 29.24 ± 0.88 29.32 ± 1.81 30.57
8 20 80 20.07 19.20 8 20 80 18.86 ± 1.96 18.52 ± 2.09 21.1
9 10 90 10.01 10 9 10 90 9.67 ± 0.42 9.5 ± 0.52 10.87
10 CaO based 75.01 75.0 78.44
GLC = Glycerol carbonate, GL = Glycerol, CGLC = % Molar concentration of glycerol reaction
carbonate, d1 = Relaxation delay.
Values predicted by qHNMR technique are average of three measurements, S.D. =
Standard Deviation, GLC = Glycerol carbonate, GL = Glycerol, CGLC = % Molar con-
or 4 s relaxation delay, yielded comparable results as shown in Table 1.
centration of glycerol carbonate.
Hence, in order to save the analysis time, qHNMR experiments were
performed at 4 s of relaxation delay.

3.2. Quantifying the GLC and GL in a mixture with qHNMR

In mixture of GLC and GL, which is practically observed during the

GL transformation into GLC, both the molecules could be quantified by
comparing the integration of proton signals corresponding to the c1 of
GLC and d of GL. As the reaction will progress the integration value of
GL peaks will decrease while the integration value corresponding to
GLC signals will increase. The equation was derived by considering that
the integrated peak area in the 1H NMR spectra of a molecule is directly
proportional to the number of protons which in turn will depend on the
molar concentration of that molecule [10].
In proton NMR spectra of GLC, protons c1, c2 and a1, a2 appears as
doublet of doublets having equivalent areas as they corresponds to one
proton each as shown in Fig. 1S (electronic supporting information).
Thus, % molar concentration of GLC (CGLC) in a mixture of GL and GLC Fig. 4. Linearity curve of the observed GLC molar ratio versus expected GLC ratio for the
can be calculated by substituting the integrated peak areas corre- signal c1 (Eq. (1)) and a1or a2 (Eq. (2)) obtained in the 1H NMR spectrum of GLC.
sponding to either c1, a1 or a2 protons of GLC and d proton of GL in
either Eqs. (1) or (2). the equations, viz.,Ia1, Ia2 and Ic2 , corresponds to one proton each and
the integration value corresponding to the GL proton viz., Id, is constant
Ic1 ⎞
%CGLC = 100 × ⎛⎜ ⎟ in both the equations. The linearity of the proposed qHNMR technique
⎝ Id + Ic2 ⎠ (1) was also evaluated for both the equations (Fig. 4) which demonstrates
Another formula employing the integrated peaks areas Ia1 orIa2 of the correlation coefficient of > 0.99. The reproducibility of the method
GLC can be used for the quantification purpose. was tested by 3 different students using the same experimental condi-
tions and employing Eqs. (1) and (2). The obtained results show the
Ia orIa2 ⎞ acceptable agreement with the true concentrations as shown in Table
%CGLC = 100 × ⎜⎛ 1 ⎟

⎝ d + Ic2 ⎠
I (2) S2 (electronic supporting information).
In order to demonstrate the application of these equations for the
Similarly the unconverted amount of glycerol (%CGL ) can also be real samples, GLC produced from the CaO assisted transesterification
calculated by substituting the peak areas corresponding to c1 protons of reaction was also quantified employing Eqs. (1) and (2) and obtained
GLC and d protons of GL in Eq. (3). results were given in Table 2. As evident from the Table 2, the GLC
(Id + Ic2) − Ic1 ⎫ quantification by qHNMR technique demonstrates the acceptable
%CGL = 100 × ⎧ agreements with those obtained by HPLC technique.
⎨
⎩ Id + Ic2 ⎬
⎭ (3)

Where i) %CGLC = molar percentage of glycerol carbonate; (ii) Ic1 =
integration of c1 of GLC at 3.736–3.793 ppm; (iii) Ia1 = integration of
a1 of GLC at 4.534–4.470 ppm; (iv) Ia2 = integration of a2 of GLC at
4.242–4.303 ppm (v) Id + Ic2 = total integration of d proton of GL and
c2 proton of GLC superimposed at 3.557–3.640 ppm.
A comparison between the actual GLC concentrations and those
predicted by the Eqs. (1) and (2) following the NMR method (Table 2),
shows the acceptable agreements with a standard deviation value of up
to ± 2%. Thus, either of these two equations could be engaged to
quantify the GLC present in a reaction mixture. It is due to the fact that
integration values corresponding to the GLC protons employed in both
3.3. GLC quantification with HPLC
The prepared standard samples containing different molar ratios of
GL and GLC were analyzed by HPLC technique to compare the results
obtained by the qHNMR technique for GLC quantification. In HPLC
chromatogram, retention times of glycerol and glycerol carbonate were
found to be 14.176 and 15.30 min, respectively, using a mixture of
hexane: isopropanol [20:80 (v/v)] as mobile phase. In the HPLC chro-
matogram of standard mixtures of GL/GLC, % age peak area values
were found directly proportional to the % age molar concentration of
respective compounds (Fig. 5S-8S, in supporting information). The

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A. Kaur et al.
Fig. 5. Plot showing the comparison of HPLC and 1H NMR predicted GLC molar values
versus theoretical GLC molar ratios in standard GL/GLC mixtures (R2 = 0.999, 0.996
respectively).
results obtained by HPLC are comparable to those obtained by qHNMR
technique as shown in Fig. 5.
4. Conclusion
The present study purposes, for the first time, a straightforward
equation for the quantification of GLC on the basis of qHNMR tech-
nique. No significant difference in the GLC quantification values were
obtained when method was employed either at 14 s or 4 s of relaxation
delay. The method proposed in present study is simple, fast, non-de-
structive and accurate compared to those reported on the basis of GC
and HPLC techniques. GLC quantification values obtained by qHNMR
method were found to show the acceptable correlation with those ob-
tained by HPLC technique. Therefore qHNMR could be employed as a
quick, non-destructive and cost effective alternative for the quantifi-
cation of GLC in a mixture of GLC and GL which is usually obtained
during the dimethyl carbonate assisted transesterification reaction of
GL.
Acknowledgements
Avneet Kaur is grateful to DST for INSPIRE fellowship (No. DST/
INSPIRE Fellowship/2015/IF150596). We acknowledge DST for the
financial support (Ref No. EMR/2014/000090) and DST-FIST (Ref No.
SR/FST/CSI-217/2010) for funding the instrumentation facility in the
School of Chemistry and Biochemistry. We are also thankful to SAI
laboratories, Thapar University, Patiala for NMR study.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at http://dx.doi.org/10.1016/j.talanta.2017.08.103.
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