Synthesis, characterization, and thermal analysis of ternary complexes of nitrilotriacetic acid and alanine or phenylalanine with some transition metals

Article abstract of DOI:10.1007/s10973-010-0740-x

Ternary complexes of Co(II), Ni(II), Cu(II), and Zn(II) with nitrilotriacetic acid as a primary ligand and alanine or phenylalanine as secondary ligand were prepared in slightly acidic medium. The structures of the complexes were elucidated using elemental, IR, molar conductance, magnetic moment, UV-Vis spectrophotometry, and thermal analyses. The ternary complexes were isolated in 1:1:1 (M:HNTA:alaH) ratios, and the molecular structures were found to be [M(HNTA)(alaH)(H₂O)₂]. Thermogravimetric analysis confirmed this structure and that the water present is coordinated to the central metal atom. UV-Vis spectra showed that the complexes have octahedral symmetry.

Full text of DOI:10.1007/s10973-010-0740-x

J Therm Anal Calorim (2010) 101:129–135
DOI 10.1007/s10973-010-0740-x
Synthesis, characterization, and thermal analysis of ternary
complexes of nitrilotriacetic acid and alanine or phenylalanine
with some transition metals
Mostafa M. H. Khalil
Shaimaa Abdel Azim
•
Eman H. Ismail
Eglal R. Souaya
•
•
Received: 12 July 2009 / Accepted: 25 February 2010 / Published online: 20 March 2010
Ó Akad e´ miai Kiad o´ , Budapest, Hungary 2010
Abstract Ternary complexes of Co(II), Ni(II), Cu(II),
and Zn(II) with nitrilotriacetic acid as a primary ligand and
alanine or phenylalanine as secondary ligand were pre-
pared in slightly acidic medium. The structures of the
complexes were elucidated using elemental, IR, molar
conductance, magnetic moment, UV–Vis spectrophotom-
etry, and thermal analyses. The ternary complexes were
isolated in 1:1:1 (M:HNTA:alaH) ratios, and the molecular
structures were found to be [M(HNTA)(alaH)(H O) ].
the rotation of the single-bonded carbon chains with high
specificity for various polyvalent metal ions. The uses of
transition metal complexes of iminodiacetic acid and
nitrilotriacetic acid (H NTA) [8, 9] have been widely
3
adopted in biology, and are gaining increasing use in
biotechnology, particularly in the protein purification
technique known as Immobilised Metal-ion Affinity
Chromatography (IMAC) [10]. Because of the great bio-
logical applications, much of the studies on the coordina-
2
2
Thermogravimetric analysis confirmed this structure and
that the water present is coordinated to the central metal
atom. UV–Vis spectra showed that the complexes have
octahedral symmetry.
tion of (H NTA) with transition metal to form binary or
3
ternary complexes have been done in neutral or slightly
basic media, where such ligands are the deprotonated acids
3
(NTA ) [11–14]. Also, because of the flexibility of the
-
3
-
NTA , it exhibits interesting conformation and coordi-
nation versatility to form polymeric structure. It has been
noted that the structural characterized divalent d-block
Keywords Alanine ꢀ Mixed-ligand complexes ꢀ
Nitrilotriacetic acid ꢀ Phenylalanine ternary complexes ꢀ
Thermal analyses
3
-
metal NTA
complexes are mainly the mixed ligand
[
15, 16] except for {[CoNa(NTA)(H O) ]ꢀ2H O} [17],
2
3
2
n
while some trivalent lanthanide [18] and monovalent
transition metal [19] complexes are the non-mixed ligand
coordination polymers. Recently, an unusual self-comple-
mentary self-assembly process, containing Cu(II) and Na(I)
Introduction
Ternary complexes of metal (II) containing nitrogen and
oxygen-donor ligands have received much attention
recently as they can display exceptionally high stability
3
-
ions and NTA ligand generated coordination polymer
[20]. On the other hand, synthesis of different types of
complexes using various amino acids is becoming
increasingly important primarily because of the various
applications of such complexes in biological fields [21–24].
Study of the thermal decomposition process of various
aminoacid complexes is helpful to the understanding of the
coordination structure of the complexes [25].
[
1–4]. Ternary complexes have been employed as probes
for biological redox centers [5], and study of the structure
of model ternary complexes provides information about
how biological systems achieve their specificity and
stability [6, 7]. Nitrilotriacetic acid (H NTA) is saturated
3
aliphatic multicarboxic ligand, and its flexibility is due to
In the previous study, ternary complex of ternary com-
plexes of Co(II), Ni(II), Cu(II), and Zn(II) with nitrilotri-
acetic acid as a primary ligand and glycine as secondary
ligand were prepared and their molecular structures were
found to be [M(HNTA)(glyH)(H O) ] [26]. In this study,
M. M. H. Khalil (&) ꢀ E. H. Ismail ꢀ S. A. Azim ꢀ E. R. Souaya
Chemistry Department, Faculty of Science,
Ain Shams University, Abbassia, Cairo, Egypt
e-mail: khalil62@yahoo.com
2
2
123

1
30
M. M. H. Khalil et al.
preparation and characterization of ternary complexes of
the same metals with nitrilotriacetic acid as a primary
ligand and alanine or phenylalanine as secondary ligand in
slightly acidic medium will be discussed.
water thermostated at 25 °C were carried out using WTW
D-812 Weilheium conductivity meter, model LBR, fitted
with a cell model LTA 100.
Instrumentation
Experimental
All measurements were carried out at the microanalytical
laboratories of Cairo University, Ain Shams University and
the National Research Center, Cairo. C, H, and N were
determined by Vario El Elementar. Co, Ni, Cu, and Zn
percentages were determined by atomic absorption spec-
trometry (AAS), using a Perkin-Elmer AAS 3100. IR
spectra of the solid complexes were recorded on a Jasco
FTIR-300 E Fourier Transform Infrared Spectrometer,
Chemicals
All chemicals used in this study are reagent grade. H NTA,
3
alanine, and phenylalanine Merk products were used with-
out further purification. CuCO ꢀCu(OH) ꢀH O, NiCO ꢀ2Ni
3
2
2
3
(
OH) ꢀ4H O, CoCO ꢀ3Co(OH) , ZnCO ꢀ2Zn(OH) ꢀH O
2
2
3
2
3
2
2
-
1
B.D.H. products were used.
using KBr disks in the range 400–4,000 cm and CsI
-
1
technique in the range 200–630 cm . Thermogravimetric
analysis was carried out using a Perkin-Elmer 7 series
thermal analyzer. The measurements were carried out
General procedure for preparation of the (1:1:1) metal
nitrilotriacetate alanine and metal nitrilotriacetate
phenylalanine ternary complexes
-
1
under nitrogen atmosphere at a heating rate 10 °C min
.
Magnetic susceptibilities of the paramagnetic metal com-
plexes were measured by using a magnetic susceptibility
balance Johnson Mtthy, Alfa products; model No MKI at
room temperature. The electronic UV–Vis spectra were
measured at room temperature on a Jasco model V-550
UV/Vis spectrophotometer. Mass spectra were recorded at
350 °C and 70 eV on a GL/MS finnigan mat SSQ 7000
apparatus.
The calculated amounts of metal carbonate, H NTA, and
3
alanine or phenylalanine to give the 1:1:1 complex were
mixed together in 100 mL of distilled water, and the
mixture was heated nearly to boiling. After complete
reaction 96% ethanol was added until dense precipitate
was obtained. Then after filtration of the precipitate it was
washed with alcohol and dried in an oven at 100 °C then
placed in the desiccator over night. This procedure was
followed for the preparation of all the 1:1:1 complexes.
Results and discussion
Potentiometric and conductometric measurements
Elemental analysis and physical properties
Determination of the acidity of the prepared complexes
was carried out by a potentiometric titration of a given
mass of the acid against standard potassium hydroxide
solution at 25 ± 0.2 °C using a Fisher pH meter. Con-
Elemental analyses and physical and chemical properties of
the eight complexes are given in Table 1. All the prepared
complexes have some common features such as thermal
decomposition before melting, effervescence and evolution
-
3
ductivity measurements of 10 M solutions in bidistilled
Table 1 Elemental analysis, mass spectrometry data, and physical properties of the complexes
Complexes
Color
Molecular m/e Magnetic Conductivity/ Elemental analysis found/calc.
mass
moment
microS
C/%
H/%
N/%
Metal/%
[
[
[
[
[
[
[
[
Co(HNTA)(ala)(H
2
O)
O)
O)
O)
Co(HNTA)(pheH)(H
2
]
Pink
373.18
333 4.08
821
717
623
594
874
961
850
684
28.22/28.97 5.13/4.86 7.17/7.51 15.68/15.79
27.22/28.98 5.10/4.86 6.82/7.57 15.71/15.74
28.00/28.44 5.00/5.26 7.12/7.37 16.48/16.82
28.10/28.47 5.04/4.78 7.00/7.38 16.97/17.23
40.10/38.55 4.94/5.18 6.24/5.99 12.93/13.12
39.88/40.12 5.12/4.94 6.19/6.24 12.88/13.07
39.15/39.69 4.08/4.89 6.00/6.17 13.91/14.00
39.11/39.53 4.16/4.78 6.00/6.15 14.01/14.35
Ni(HNTA)(ala)(H
2
2
]
Green 372.94
Blue 377.79
White 379.66
Pink 449.27
Green 449.03
Blue 453
White 455.75
373 2.97
372 1.85
375 Diam.
450 5.0
Cu(HNTA)(ala)(H
2
2
]
Zn(HNTA)(ala)(H
2
2
]
2
O)
2
]
Ni(HNTA)(pheH)(H
2
O)
O)
O)
2
]
450 3.33
454 1.7
Cu(HNTA)(pheH)(H
2
2
]
Zn(HNTA)(pheH)(H
2
2
]
453 Diam.
1
23

Synthesis, characterization and thermal analysis of ternary complexes of nitrilotriacetic acid
131
of carbon dioxide on reaction with sodium bicarbonate.
The molecular masses of the eight complexes suggest the
presence of two water molecules, Table 1. Comparing the
four sites and to form an octahedral structure, two water
molecules could be coordinated to the metal. The proposed
structure of the 1:1:1 complex is thus as shown in Fig. 1.
From the proposed structure, there are two ionisable pro-
tons, one due uncoordinated COOH group and the other
1
0 Dq values of the complexes of this study with the lit-
erature values of Co, Ni, and Cu octahedral complexes,
respectively, it was concluded that the octahedral structure
is recommended for the ternary complexes of this study
and the two water molecules are coordinated to the metal.
The pH values of the solution at which all the complexes
under study were crystallized ranged from 2.8 to 4.0. In this
(
a)
b)
2
-
pH range HNTA and alaH or pheH in their zwitter form
2
predominate. At this pH, HNTA has three coordination
-
-
sites (N and two COO ) while alaH or phenylalanine
(
coordinate in slightly acid medium via its carboxylic
oxygen after being converted into the zwitter ion form
?
-
(
H N CH COO ). This means that under the reaction
3 2
condition used in this study, the amino acids coordinated as
monodentate ligand. Accordingly, the metal coordinates to
O
(c)
O
H
+
N
CH
R
C
OH
O
M
H
O
H
N
O
(d)
H O
2
4
000 3500 3000 2500 2000 1500 1000 500
Wavenumber/cm–1
O
R = CH , alaH
3
OH2
R = CH ph, pheH
2
O
M = Co, Ni, Cu, Zn
Fig. 2 IR spectra of (a) [Co(HNTA)(ala)(H
O)
2
O)
2
], (b) [Co(HNTA)
(pheH)(H
(H O)
2
2
], (c) [Ni(HNTA)(ala)(H O) ], (d) [Ni(HNTA)(pheH)
2 2
Fig. 1 The proposed structure of the ternary complexes
2
2
]
Table 2 Infrared data of the ternary complexes
Complex
mOH
mCO
mCOO
mM–O
298
mM–N
[
Co(HNTA)(alaH)(H
2
O)
2
]
3396(m,br)
1734 (s)
1668 (s),
541
1
1
581 (vs) 1468 (m),
451 (s) 1425 (s)
[
Ni(HNTA)(alaH)(H
2
O)
2
]
3489 (m)
1729 (s)
1729 (s)
1583 (vs),
463 (m) 1408 (s)
1653 (s),
600 (vs) 1409 (s)
354
350
547
457
1
[
Cu(HNTA)(alaH)(H
2
O)
2
]
3588 (m) 3429 (m)
1
[
Zn(HNTA)(alaH)(H
2
O)
2
]
3464 (m)
3412 (m)
1731 (m)
1639 1584
1685 (s)
304
285
563
541
[
Co(HNTA)(pheH)(H
2
O)
2
]
1730 (w, sh)
1
588 (vs) 1424 (s)
1587 (vs)
462 (vs) 1410 (s)
1642 (sh)
601 (vs) 1407 (s)
1641 (s) 1581 (vs)
[
[
[
Ni(HNTA)(pheH)(H
2
O)
2
]
3484 (s, br)
3589 (s)
1730 (s)
368
357
548
635
522
1
Cu(HNTA)(pheH)(H
2
O)
2
]
1730 (s)
1
Zn(HNTA)(pheH)(H
2
O)
2
]
3464 (m)
1728 (m)
468, 359
123

1
32
M. M. H. Khalil et al.
one from the protonated uncoordinated NH2 group of
amino acids used. Potentiometric titrations of the eight acid
complexes were carried out for the determination of their
acidities. Metal complexes solution was prepared by dis-
solving the complex in about 20 mL bidistilled water then
the volume was then made up to 50 mL by distilled water
Table 2. IR spectra of the cobalt and nickel complexes with
H NTA and alanine or phenylalanine are shown in Fig. 2.
3
The ir spectrum of nitrilotriacetic acid (H NTA) showed
3
-
1
bands at 3,041 and 1,733 cm which were attributed to
tOH with intermolecular hydrogen bonding and undisso-
ciated carboxylic groups, respectively. The IR spectra of
the ternary complexes with alanine or phenylalanine as
-
3
to give 5 9 10 M solutions and titrated potentiometri-
cally against potassium hydroxide solution. As expected
the eight prepared complexes showed that they have two
ionized protons. The obtained results confirm our structure
proposed. In the following sections IR spectra, thermal
analysis, mass spectra, and conductivity measurements will
be discussed to support the above conclusion about octa-
hedral structure of the complexes.
-
1
secondary ligand exhibited bands 1,728–1,734 cm
,
Table 2, suggesting the presence of non-coordinated free
carboxylic group of H NTA ligand. On the other hand, the
3
ternary complexes with alanine exhibited new strong
-
1
absorption at 1668, 1583, 1653 and 1639 cm for Co, Ni,
Cu and Zn complexes, respectively. These new bands can
be assigned to the stretching vibration t(CO) of the coor-
dinated carboxylate group, COOM [27]. Similar data for
phenylalanine ternary complexes were observed with
appropriate shift of COOM due to complex formation,
Table 2. The IR spectra the free ligands show sharp bands
IR spectra
The IR spectra of the H NTA, alanine, phenylalanine, and
3
-
1
their metal complexes were carried out in the range of
at 1,594 and 1,409 cm for alanine and at 1,561 and
-1
1,407 cm for phenylalanine assigned for asymmetric and
-
,000–400 cm and the important bands were listed in
1
4
Table 3 Temperature values for the decomposition along with the species lost in each step
Complexes Molecular mass TG range/K DTG/K Found/calculated
Assignment
Mass loss
Total mass loss
[
[
[
Co(HNTA)(alaH)(H
2
O)
2
]
373.18
372.94
377.79
303–503
453.8
18.83/18.3
60.47/60.83
20.37/20.12
19.47/18.3
54.05/57.66
26.48/23.69
5.2/4.8
79.27
73.52
77.1
2 3
2H O ? CH OH
5
8
03–873
704.2–833.8
Organic compounds
CoO
73–1273 Above 873
Ni(HNTA)(alaH)(H
2
O)
2
]
303–563
543.7
658.7
2 3
2H O ? CH OH
5
6
63–673
Organic compounds
Mix., Ni and NiO
73–1273 Above 673
Cu(HNTA)(alaH)(H
2
O)
2
]
303–373
357.8
1H
1H
2
O
4
7
73–773
506–556.4
59.8/61.1
2 3
O ? CH OH ? organic cpd
73–1173 813–1163
12.1/11.7
CO
Mix Cu and CuO
2H O ? CH OH
2
1
173–1273 Above 1173
303–573 168–527
73–1213 683–1186
213–1273 Above 1223
303–513 504.5
669.1–713.62 53.8/54.2
22.9/22.6
[
[
[
[
Zn(HNTA)(alaH)(H
2
O)
2
]
379.66
449.27
449.03
453
17.4/17.9
76.96
2
3
5
59.56/59.8
24.04/21.4
Organic compounds
1
Mix., Zn ? ZnO
Co(HNTA)(pheH)(H
2
O)
2
]
28.95/28.93 82.75
2
2H O ? phenol
6
7
33–718
18–1273 Above 718
562.6
Organic compounds
CoO
17.25/16.7
Ni(HNTA)(pheH)(H
2
O)
2
]
303–573
29.21/28.95 82.16
2
2H O ? phenol
6
7
73–773
688.19–746.2 52.95/54.1
Organic compounds
Mix., Ni and NiO
73–1273 Above 773
17.68/16.64
4.00/3.97
61.3/64.8
10.24/9.7
24.46/24.8
27.8/28.5
48.6/48.5
23.6/24.0
Cu(HNTA)(pheH)(H
2
O)
2
]
303–373
343.6
503.3
796.2
75.54
76.4
1H
1H
2
O
4
6
8
73–673
73–873
2
O ? phenol ? organic cpd
CO
Mix Cu and CuO
2H O ? phenol
Organic compounds
CO ? Zn
2
73–1273 Above 873
[
Zn(HNTA)(pheH)(H
2
O)
2
]
455.75
303–513
436.3–509.2
614.7–670.8
2
5
8
73–873
73–1273 Above 873
2
1
23

Synthesis, characterization and thermal analysis of ternary complexes of nitrilotriacetic acid
133
symmetric stretching vibrations of the carboxylate moiety,
respectively. These two bands of the free ligands are either
shifted to lower or higher frequencies, indicating that these
ligands coordinated to the metal ions via deprotonated
carboxylate group [28]. On the other hand, the IR spectrum
of alanine and phenylalanine showed medium broad bands
Magnetic moments and electronic spectra
The UV–Visible spectra of the metal complexes were
-
3
-1
carried out in deionized H O (10 mol L ) solution. For
2
ternary Co(II) complexes, the effective magnetic moment
values are 4.08 B.M. and 5.10 B.M. for [Co(HNTA)
-
1
at 3,087 and 3,135 cm , respectively, which attributed to
?
NH3 group of the amino acid. The IR spectra then suggest
(alaH)(H O) ] and [Co(HNTA)(PheH)(H O) ], respec-
2 2 2 2
tively. These values are higher than spin only moment for
three unpaired electrons 3.89 due to a considerable orbital
contribution [30]. The UV–Vis spectra of the two com-
2
-
that in ternary complexes HNTA is a tridentate ligand
-
two –COO ) and (one nitrogen), and that the secondary
(
-
ligands are monodentate (one –COO ). All the prepared
-1
plexes show one band at 19,685 cm which are assigned
4
4
complexes exhibited bands in the range of 3,558–
-
to T1g(F) ? T1g(P) transition, assuming an octahedral
geometry for Co(II) complex. For ternary Ni(II) com-
plexes, the magnetic moments leff of [Ni(alaH(HNTA)
1
3
,412 cm signifying that H O molecules exist in these
2
complexes. The mass spectra of the complexes support the
proposed complexes with the two water molecules coor-
dinated to the central atom to form an octahedral structure.
Further elucidation of the participation of nitrogen and
(H O) ] and [Ni(HNTA)(PheH)(H O) ] have values of
2 2 2 2
2.97 B.M. and 3.3 B.M., respectively, which suggest an
octahedral geometry [30]. The electronic spectrum of
Ni(II) complexes displays two bands in the range of
2
-
carboxylic groups in HNTA and the used amino acids
was confirmed by recording the IR spectra of the com-
-
1
3
3
15,627 cm and 25,379 cm assigned as A2g ? T1g(F)
-
1
3
3
plexes in the range 200–630 cm . The t(MO) frequencies
and A2g ? T1g(P), respectively. The mixed-ligand com-
plexes of Cu(II) with alaH and pheH showed magnetic
moment values, leff, in the range 1.77–1.85 B.M. These
values correspond to one unpaired electron and thus offer
evidence for mononuclear structures of the complexes. The
UV–Vis spectrum of Cu(II) complexes consists of a broad
3
-
-1
of NTA as ligand are at 343, 347, 380, and 355 cm for
Co, Ni, Cu and Zn complexes, respectively [29]. Thus one
may assign the bands in the complexes in the range 285–
-
1
4
68 cm for the M–O vibrational frequencies, Table 2.
The M–N band frequencies were found in the range 457–
-
63 cm for Co, Ni, Cu, and Zn complexes, respectively,
1
-1
2
2
5
band centered at 12,135 cm that assigned as E ? T2g
g
Table 2.
(
a)
(b)
DTG
mg/min
DTG
mg/min
TG
TG
0
.1
%
00
%
1
100
80
60
40
20
0
0.1
0
–
.0
8
6
4
2
0
0
0
0
0
0.0
0.1
–
–
0.1
–0.2
–
–
0.3
0.4
0.2
4
00
600
800
1000 1200
400
600
800
1000 1200
Temperature/K
Temperature/K
(
c)
(d)
DTG
mg/min
DTG
mg/min
TG
TG
0
0
–
–
.05
%
00
%
100
1
0.1
0.0
.00
8
0
8
6
0
0
0.05
0.10
6
4
0
0
–0.1
–0.2
–0.3
4
2
0
0
–0.15
–0.20
2
0
4
00
600
800
1000 1200
400
600
800
1000 1200
Temperature/K
Temperature/K
Fig. 3 TG and DTG of ternary complexes: a [Co(HNTA)(alaH)(H
d [Zn(HNTA)(alaH)(H O)
2 2 2 2 2 2
O) ], b Ni(HNTA)(alaH)(H O) ], c [Cu(HNTA)(alaH)(H O) ],
2
2
]
123

1
34
M. M. H. Khalil et al.
(
a)
DTG
(b)
DTG
mg/min
TG
mg/min
TG
0
.1
0.1
%
%
1
00
100
0
.0
8
6
4
2
0
0
0
0
0
0.0
80
60
40
20
–0.1
–
–
0.1
–0.2
0.2
–0.3
4
00
600
800
1000 1200
400
600
800
1000
1200
Temperature/K
Temperature/K
(
c)
DTG
(d)
DTG
mg/min
0.10
TG
mg/min
TG
%
0.1
%
1
00
100
0
.05
0
–
–
.0
8
6
4
2
0
0
0
0
80
60
40
20
0.00
0.1
0.2
–
–
0.05
0.10
4
00
600
800
1000 1200
400
600
800
1000
1200
Temperature/K
Temperature/K
Fig. 4 TG and DTG of ternary complexes: a [Co(HNTA)(pheH)(H
d [Zn(HNTA)(pheH)(H O)
2 2 2 2 2 2
O) ], b [Ni(HNTA)(pheH)(H O) ], c [Cu(HNTA)(pheH)(H O) ],
2
2
]
transition with expected splitting of these states as a result
9
of tetragonal distortion of the octahedral Cu(II) ion, d .
that the final thermal decomposition residue is mixture of
metal and metal oxide or metal oxide although thermal
decomposition was made under nitrogen atmosphere [32].
Mass spectra
The mass spectra of the eight complexes were recorded.
All the spectra contain molecular ion peaks confirm the
molecular mass of the complexes. The data are presented in
Table 1.
Conclusions
The Co, Ni, Cu, and Zn nitrilotriacetic acid and aniline or
phenylalanine ternary complexes prepared in slightly acidic
medium have an octahedral structure of the general form
[M(HNTA)(alaH)(H O) ] and [M(HNTA)(PheH)(H O) ],
Thermal analysis
2
2
2
2
in which nitrilotriacetic acid acts as a tridentate ligand and
alanine or phenylalanine acts as a monodentate ligand. Two
coordinated water molecules are required to complete
octahedral coordination. These complexes, thus, behave as
dibasic acids.
Thermogravimetric analyses of our complexes were carried
out under nitrogen atmosphere. The results are shown in
Table 3 and Figs. 3, 4. Interpretation of the thermal mass
losses shows that the complexes thermally decompose in
the same patterns exhibited by the parent ligands. It was
shown that H NTA thermally decompose in two overlap-
3
ping steps [26], into glycine and maleic acid. Both thermal
products, on further heating, decompose giving organic
residue overlapping steps. The first mass loss in our com-
plexes was found to be equivalent to the water molecules
which supported our suggested structure for these prepared
complexes and methyl alcohol or phenol with respect to
aniline or phenylalanine [31] in which their decomposed
temperatures are very close to the coordinate water tem-
perature decomposition. It may be observed from (Table 3)
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