Article

Advanced Science,
Copyright © 2019 American Scientific Publishers
Engineering and Medicine
All rights reserved Vol. 11, 1–8, 2019
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Synthesis, Spectroscopic Characterization and

Application of 1,3,5-Tris-(monoethylamino)-
Cyclotrichlorophosphonitrile for Acidic Soil Reclamation
H. K. Sharma1 , Pramod Kumar1 , Rahul Nag2 , Ishanki Sharma1 , Jyoti Sharma3 , and Manu Vashishtha4 ∗
1
Department of Chemistry, Jawaharlal Nehru Rajkiya Mahavidyala, Port Blair, Andaman and Nicobar Island 744104, India
2
Department of Chemistry, Indian Institute of Technology, Bombay, Powai 400076, India
3
Department of Physics, Jawaharlal Nehru Rajkiya Mahavidyala, Port Blair, Andaman and Nicobar Island 744104, India
4
Department of Chemistry, Dr. B. R. Ambedkar Institute of Technology, Port Blair, Andaman and Nicobar Island 744103, India

The reaction of (PNCl2 3 with ethylamine was carried out in organic medium using ethanol as
solvent and the reaction product or the functionalized derivative of (PNCl2 3 was characterized by
FT-IR, UV-NIR, 1 H and 31 P-NMR, ESI-MS, SEM, TEM and XRD analysis. The reaction product was
found to be a cross-linked polymer with energy gap 0.13 eV suggesting semiconductive nature. The
polymer was utilized in the reclamation of acidic soil of South Andaman. It has also been found
that the derivative (EtAmCCTPN) has utility in modulating the pH of acidic soil, from pH 4.0 to
pH 7.2, which is the most suitable state for farming. EtAmCCTPN also has potential as efficient
biodegradable fertilizer which can help in not only increasing the pH of the soil but also improves
the soil health by replenishing the deficiency of important primary macro-nutrients like nitrogen and
phosphorous in the acidic as well as normal soil of South Andaman island.
Keywords: Cyclophosphazene, Polymer, Reclamation of Acidic Soil.

1. INTRODUCTION
Soil pH is an important parameter which measures the
acidity or alkalinity of soil. Plant growth and most soil pro-
cesses, including nutrient availability and microbial activ-
ity, are favoured by a soil pH range of 5.5–8 [1–4].
Soil becomes acidic due to various reasons one of which
is excessive rainfall, which leaches out the basic ele-
ments like sodium, potassium, calcium and magnesium
produces more hydrogen ions, decaying of organic mat-
ter, use of fertilizers containing ammonium and nitrates
and high-yield crops absorb the basic elements, and causes
increased acidity [5, 6]. Acidic soil creates deficiencies
in the available supply of primary macro-nutrients like
nitrogen, phosphorus, potassium and magnesium which
are important macronutrients required in large quantity to
survive the growth of plants [7]. The growth of bacte-
ria, fungi and micro-organisms which transforms the nutri-
ents into plant absorbable form, is suppressed at a soil of
pH 5.5 and below resulting poor nutrient availability for
∗
Author to whom correspondence should be addressed.
the plants [8, 9]. This causes significant loss in produc-
tion as well as reduction in profitable market opportuni-
ties where the choice of crops is restricted to acid tolerant
species and varieties.
Andaman and Nicobar Islands (A&N Islands), an
archipelago, situated in the Bay of Bengal, about 1,200 km
south-east of peninsular India, a Union Territory of India,
consists of 576 islands which experience heavy rain
fall (approximately 3000 m.m.) during monsoon sea-
son [10, 11]. Excess rain-water leaches base cation present
in top soil and creates base unsaturation increasing the
percentage of hydrogen ion leading to the acidic soil
which in turn causes deficiency of primary macro-nutrients
to plants. Therefore plants/fodder growing on such soils
experience poor growth because of lower content of these
minerals. As a consequence animals reared on these will
thus also get lower mineral content which no doubt may
support maintenance of body function but will certainly
affect the growth rate, fertility and milk production of
animals as these conditions requires additional nutrients
including minerals [12].

Adv. Sci. Eng. Med. 2019, Vol. 11, No. xx 2164-6627/2019/11/001/008 doi:10.1166/asem.2019.2387 1
Synthesis, Spectroscopic Characterization and Application
Normally soil acidity can be corrected by liming the
soil, or adding basic materials to neutralize the acid
present. The most commonly used liming material is agri-
cultural limestone which is required in large amount to
achieve a favourable pH where chances of overdose may
cause toxicity as well danger for plant growth. Other than
this it takes long time (a year or more) for a measurable
change in pH [13–17].
Therefore, it is required to develop or use efficient
chemical which can not only reduce the soil acidity
but also supplement the deficiency of important primary
macro-nutrients like phosphorus and nitrogen in sustain-
able manner. Poly(organo)phosphazenes are an important
class of inorganic polymers used in a wide range of alter-
native industrial applications due to the vast array of sub-
stituted derivatives [18–23]. Survey of literature reveals
that the reaction of (PNCl2 3 with ethylamine and appli-
cation of its reaction product have not been sufficiently
explored from the reclamations of acidic soil aspect [24].
The current paper deals with synthesis and thorough
characterization of the (PNCl2 3 derivative, 1,3,5-tris-
(monoethylamino)-cyclotrichlorophosphonitrile (EtAmC-
CTPN) by using various spectroscopic and microscopic
techniques. Since nitrogen and phosphorous are important
constituents of EtAmCCTPN as well as for plant nutri-
tion, the preliminary work has been done in finding the
application of EtAmCCTPN as an efficient biodegradable
fertilizer which can not only reclaim acidic nature but also
improves the soil health by replenishing the deficiency of
important primary macro-nutrients like nitrogen and phos-
phorous in the acidic soil of South Andaman island.
2. EXPERIMENTAL DETAILS
All the chemicals of Sigma-Aldrich, USA and analytical
grade were used in the present study.
2.1. Synthesis of CCTPN
1,3,5-cyclohexachlorotriphosphonitrile [(PNCl2 3 ]
(CCTPN) was prepared by the reported method [25].
Briefly 0.5 mol each of PCl5 and NH4 Cl in 80 mL
s-tertrachloroethane was refluxed for 72 h. Colorless mass
formed was separated followed by successive washing
with distilled water and s-tetrachloroethane to remove
unreacted NH4 Cl and PCl5 , if any. The product was
extracted with concentrated H2 SO4 which takes out mainly
the trimer which is then recovered by diluting the acid with
water and then back extracted with petroleum ether [26]
and the formation of cyclic trimer was confirmed by
reported melting point and FT-IR spectral studies [27].
2.2. Synthesis of 1,3,5-Tris-(monoethylamino)-
Cyclotrichlorophosphonitrile
(EtAmCCTPN)
To prepare EtAmCCTPN, 1.74 g (5 mM) of (PNCl2 3
was added in 20 mL ethanol and to this 3 ml (45 mM)
2 Adv. Sci. Eng. Med. 11, 1–8, 2019
Sharma et al.
ethylamine was added slowly with constant stirring and the
reaction mixture was refluxed for 24 h resulting the for-
mation of colorless precipitate. This colorless precipitate
was separated from the solution by filtration followed by
successive washing with ethanol and diethyl ether respec-
tively to remove unreacted reactants if any. The reac-
tion product was analyzed quantitatively and qualitatively.
Molecular weight was determined by Rast method using
camphor as solvent, found to be 1110. Melting point of
the reaction product was found to be 375  C. Characteri-
zation of reaction product was carried out by using FT-IR
(Perkin Elmer Spectrum One FT-IR spectrometer), U.V.
(Shimadzu UV2101PC Spectrophotometer), 1 H and 31 P-
NMR (Bruker NMR Spectrometer, 500 MHz), ESI-MS
spectra (maXis Impact High Resolution Mass Spectrom-
eter), SEM micrographs (FEG-SEM JSM-7600F), TEM
micrographs (JEOL 2100F FEG-TEM microscope) and
X-ray diffractogram (PANalytical’s X’Pert PRO) by using
Cu K as source of radiation  = 1.5418 Å.
2.3. Reclamation of Acidic Soil of South Andaman
To study the effect of polymeric EtAmCCTPN on varying
pH of acidic soil (pH 4.0–5.5), the soil samples were col-
lected up to desired depth (30 cm) by means of sampling
tools from different places of south Andaman (Bambooflat,
Sippighat and Gyaracharma). Each soil sample (20 g) was
taken in 100 ml beaker to which 40 mL distilled water
was added. The suspension was stirred well just before the
immersing the pH electrodes and the pH of each extract
was noted before and after 5 minutes of each addition
of fixed quantity (10 mg) of polymeric EtAmCCTPN. In
each determination, the electrodes were rinsed with dis-
tilled water followed by drying with filter paper. Qualita-
tive analysis of soil samples were performed by standard
methods.
3. RESULTS AND DISCUSSION
Cyclization reaction between PCl5 and NH4 Cl leads to
CCTPN (Scheme 1) which has been further substituted by
ethylamine to lead to the final polymeric product of EtAm-
CCTPN (Scheme 2). Probable mode of polymerization of
monomeric-EtAmCCTPN has been shown in Scheme 3.
It can be observed that each of the monomeric unit linked
with the adjacent ones by means of –NH group attached
to the P-atom of one unit and –Cl group attached to the
Cl Cl
1460C, 72h N
P P
PCl5 + NH4Cl Cl Cl
C2H2Cl4 N N
P
Cl Cl
Scheme 1. Reaction of phosphorous pentachloride (0.5 mol) with
ammonium chloride (0.5 mol) for the synthesis of CCTPN.
Sharma et al. Synthesis, Spectroscopic Characterization and Application

Cl Cl NH Cl 16
N N
P P C2H5OH, Reflux P P
Cl Cl + C2H5NH2 Cl N 14 800
N N N H 912
P 24 h N 12
P
2000 1093
Cl Cl N Cl 10
H 548
%T 8
Scheme 2. Reaction of CCTPN with ethyl amine for the synthesis of 1300
477
6 1751
EtAmCCTPN.
4
3138 2800
P-atom of adjacent unit. Release of HCl results in weak 2
3000 1400
linkage between P and N atom of amine of adjacent units 0
suggesting the formation of polymer. 4000 3500 3000 2500 2000 1500 1000 500
ν(cm–1)
3.1. Characterization of EtAMCCTPN Figure 1. FT-IR spectra of polymer of EtAmCCTPN.
Elemental ananlysis: % found (calcd.): P 31.66 (31.65),
C 18.38 (18.39), N 21.44 (21.44), H 4.35 (4.34), Cl
24.17 (24.18) and M.W. = 1175 determination suggest group. Vibrations at 1400 and 1751 are due to P–N–P
that the molecular formula of the reaction products is linkage. The band at 2000, 2800 and 3000 cm−1 corre-
[P3 N3 Cl2 H2 (NC2 H5 2 ]3 . Molecular weight was also sup- sponds to the –CH2 CH3 group. The bands at 3119 suggest
ported by the mass spectrum from which molecular weight the presence of cyclic P3 N3 ring with delocalized  elec-
was found to be 1110 which suggests that the spectral val- trons. Band at 3138 corresponds to the terminal –NH band.
ues and experimental values are in good agreement. The FTIR spectrum of EtAMCCTPN has been compared
FT-IR has been utilized to validate the presence of dif- (Table I) with the starting material, (PNCl2 3 which con-
ferent functional groups present in EtAMCCTPN (Fig. 1). firms the substitution of the cyclophosphazene ring, result-
FT-IR spectrum of the reaction product shows character- ing in –NH as well as alkyl group. The substitution of
istic bands at 477, 548 and 800 cm−1 due to coordinated the cyclophosphazene ring with alkyl groups has already
N–P–N groups attached to the ring. Whereas, bands at been shown in reported article, [28, 29] which supports
912, 1093 and 1300 cm−1 suggest the presence of P = N successful functionalization of CCTPN in the present
article.
Absorption spectrum was measured using 1 mg/mL
Cl Cl H
N stock solution of reaction product in water and final
P P N Cl
NH
N
Cl H N N N cuvette concentration was 0.5 mg/mL. Electronic spectrum
N N H P P
P P P Cl N of the reaction product shows shoulder at 400 nm and
Cl N N N H
N N H N Cl P absorption band at 1100 and 1250 nm which indicates the
P
H Cl
N Cl conjugation. Absorption at 1100 and 1250 nm suggest that
N Cl Cl H
H N N electrons on N atom are easily available for conduction.
H P P
N This view is also supported by the energy gap (0.13 eV)
N N H
P
N Cl
H Table I. Comparison of FTIR spectrum of (PNCl2 )3 and
EtAmCCTPN.

EtAmCCTPN (PNCl2 )3 [28]

−1
477, 548 and 800 cm : N–P–N 528 and 612 cm−1 –PCl2
669 cm−1 –N–P–N
a
Cl
1 HN Cl
776 cm−1 —ring breathing
N
c 3P P 5 870 cm−1 –PN2 twisting
NH N NH
N 4
N P 912, 1093 and 1300 cm−1 : P = N 1196 cm−1 –PN2
P P N N N N
P2 P asymmetric stretching
Cl N
N N H N Cl Cl N P
Cl
6
1218 cm−1 –PN2
P b
NH symmetric stretching
Cl
N Cl N N 1400 and 1751 cm−1 :
H
H P P P–N–P stretching
N
N N H 2000, 2800 and 3000 cm−1 :
P
CH2 CH3 stretching
N Cl 3119 cm−1 : cyclic
H
P3 N3 stretching
3138 cm−1 : terminal –NH
Scheme 3. Mechanism of polymerization of EtAmCCTPN.

Adv. Sci. Eng. Med. 11, 1–8, 2019 3

Synthesis, Spectroscopic Characterization and Application
Figure 2. UV-NIR spectra of polymer of EtAmCCTPN.
calculated from electronic spectrum using the following
formula [30].
Eg = Ev1 − Ev2 /2 where Eg = energy gap
The shoulder band at 400 nm having 0.035 molar extinc-
tion coefficient suggest the conducting nature of the poly-
mer. The values of energy gap suggest the semi-conductive
nature of the polymer formed (Fig. 2).
Presence of phosphorus in the polymer has been estab-
lished through solid state 31 P-MAS-NMR of EtAmC-
CTPN. As can be seen from Figure 3, single peak at
0.18 ppm suggest that all the phosphorus atoms of EtAm-
CCTPN are equivalent in nature. Comparing the 31 P
NMR spectrum of EtAmCCTPN with that of CCTPN or
(PNCl2 3 , [31, 32] it has been confirmed that the alkyl
amine substitution at phosphorus centers lead to the down-
field shift of 31 P peak of EtAmCCTPN.
31
Figure 3. P-NMR spectra of polymer of EtAmCCTPN.
4 Adv. Sci. Eng. Med. 11, 1–8, 2019
Sharma et al.
1
H-NMR spectrum was recorded using D2 O as solvent.
All the characteristic peaks of EtAmCCTPN has been
observed (Fig. 4). Peak at 1.330 ppm (doublet) corre-
sponds to the –CH3 proton whereas peak at 3.118 ppm
is of –CH2 proton which is directly attached to N atom
of the ring. Peak at 7.203 ppm is due to terminal –NH
group. Thus 1 H-NMR spectrum supports the formation of
EtAmCCTPN.
Formation of the polymeric product of EtAmCCTPN
has been validated through ESI-MS spectrum. The peak at
m/z = 366 (Fig. 5) is due to P3 N3 Cl3 (N+ CH2 = CH2 3
which supports the polymerization of the reaction product.
M.W. = 1011 determined from mass spectrum also support
the polymerization.
Powder-XRD spectrum of EtAmCCTPN (Fig. 6) was
measured from dry reaction product and the corresponding
hkl values, d spacing, lattice parameters and bond angles
were calculated. hkl values suggest that most of the h2 +
k2 + l2 values are even and few values are odd. Even val-
ues suggest the b.c.c. structure while the odd values sug-
gest the linkage of one phosphorous atom through N with
antipodal phosphorous atom of the other ring. Blurring and
very weak peak observed in the XRD spectrum also sup-
ports the polymerization of reaction product. Angles and
lattice parameters enlisted (Table II) suggest that P1 -Na -P4 ,
N1 -P3 -Cl3 , P6 -Nb -P7 , N1 -P1 -N2 and P2 -N2 -P1 linkages hav-
ing bond angles respectively 180, 105.45, 180 , 124.8
and 124.36. Repetition of angles suggests the linear
polymerization. Lattice parameter calculated from XRD
spectrum is tabulated also supports the polymerization.
(Table III).
To study the morphology of the polymeric EtAmC-
CTPN, SEM measurements were carried out. Samples
were prepared for SEM microscopic measurement by