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Thermochimica Acta
Thermochimica Acta
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A R T I C L E I N F O A B S T R A C T
Keywords: The new ternary complexes of the formula Ln2(nfa)5(phen)(OH)·nH2O (where n = 1 or 1.5; nfa – N-phenylan-
Lanthanide complexes thranilate anion (C13H10NO2), phen – 1,10-phenanthroline (C12H8N2), Ln = La(III), Ce(III), Pr(III) and Nd(III))
N-phenylanthranilic acid were synthesized and characterized by elemental analysis, complexometry, infrared spectroscopy, XRD tech-
1,10-phenanthroline nique, simultaneous thermogravimetry and differential scanning calorimetry (TG–DSC), evolved gas analysis by
Thermal analysis
TG–DSC coupled with FTIR and MS spectroscopy. The detailed thermogravimetic analysis showed that thermal
Pyrolysis
EGA
decomposition of the complexes in nitrogen and air atmosphere occurs in several stages including water elim-
ination, neutral ligand loss and N-phenylanthranilate anion decomposition, respectively. It was found that the
thermal stability and the decomposition path of the studied compounds depend on the metal ion and the applied
atmosphere. Low values of the dehydration enthalpies indicate that dehydration is connected with the release of
crystallization water. By the use of the coupled TG–FTIR–MS techniques the decomposition pathways of the
synthesized compounds were examined and the gaseous products released during pyrolysis and thermal oxi-
dation of the complexes were identified.
⁎
Corresponding author.
E-mail address: lzapala@prz.edu.pl (L. Zapała).
https://doi.org/10.1016/j.tca.2017.12.012
Received 25 September 2017; Received in revised form 3 December 2017; Accepted 6 December 2017
Available online 07 December 2017
0040-6031/ © 2017 Elsevier B.V. All rights reserved.
L. Zapała et al. Thermochimica Acta 659 (2018) 242–252
Table 1
Analytical (complexometric), thermoanalytical (TG) and elemental analyses (EA) data of Ln(III) complexes with N-phenylanthranilic acid and 1,10-phenanthroline where:
nfa = C13H10NO2, phen = C12H8N2.
La2(nfa)5(phen)(OH)·H2O (La-nfa-phen) 1554.14 17.60 17.88 59.84 59.50 3.87 3.96 6.63 6.31 1.29 1.16
Ce2(nfa)5(phen)(OH)·1.5H2O (Ce-nfa-phen) 1565.57 17.77 17.90 58.96 59.07 3.93 3.99 6.25 6.26 1.91 1.73
Pr2(nfa)5(phen)(OH)·1.5H2O (Pr-nfa-phen) 1567.15 18.35 17.98 58.22 59.01 3.96 3.99 6.26 6.26 1.78 1.72
Nd2(nfa)5(phen)(OH)·1.5H2O (Nd-nfa-phen) 1573.82 18.58 18.33 57.58 58.76 3.79 3.97 6.52 6.23 1.76 1.72
Table 2
IR data for the ligands (N-phenylanthranilic acid, 1,10-phenanthroline), sodium N-phenylanthranilate [18] and obtained complexes.
Compound ν(NeΗ) ν(C]O) νas(COO−) νs(COO−) Δν* δ(NH) ν(CeN) δ(CeH) ν(LneO)
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L. Zapała et al. Thermochimica Acta 659 (2018) 242–252
Fig. 3. Thermogravimetric curves of the compounds in nitrogen: (a) La-nfa-phen (2.3579 mg), (b) Ce-nfa-phen (2.0870 mg), (c) Pr-nfa-phen (3.5010 mg), (d) Nd-nfa-phen (4.9830 mg)
and in air: (e) La-nfa-phen (2.2090 mg), (f) Ce-nfa-phen (2.0590 mg), (g) Pr-nfa-phen (3.5440 mg), (h) Nd-nfa-phen (2.4220 mg).
were obtained from POCH, Poland whereas DMSO was from Merck. La Simultaneous TG-DSC curves were recorded using a TGA/DSC1
(III) and Nd(III) chlorides were prepared by treating the appropriately apparatus (Mettler Toledo) in temperature range of 298.15–1273.15 K,
weighted amounts of their oxides with concentrated hydrochloric acid using a heating rate of 20 K min−1. The measurements were conducted
(d = 1.19 kg dm−3) while Ce(III) was used as nitrate and Pr(III) as in dynamic nitrogen and air atmospheres (flow rate 50 mL min−1).
chloride. TG-FTIR analyses were performed in air and nitrogen atmosphere
with the use of Mettler Toledo TGA/DSC1 instrument that was coupled
online with FTIR apparatus (Nicolet iS10 − Thermo Scientific) by a
2.2. Experimental equipment and conditions transfer line heated at 493.15 K. The FTIR spectra of the evolved gases
were acquired in the range 4000–400 cm−1 with resolution of 4 cm−1.
Carbon, hydrogen and nitrogen contents were determined with a The evolved gases were then transferred by a quartz capillary heated at
Vario EL elemental analyzer (Elementar, Germany). Metal ions contents 473.15 K into mass spectrometer ThermoStar™ (Pfeiffer Vacuum) where
and hydration water in the obtained complexes were determined based the selected m/z signals were monitored.
on the TG curves. The metal ions contents were also determined by
complexometric titration using standard EDTA solution, after miner-
alization of the complexes by perchloric acid. The Schöniger method 2.3. Preparation of the complexes
was used to determine the chlorine content. FT-IR spectra were re-
corded in KBr pellets with an Alpha FT-IR spectrophotometer (Bruker, The synthesis of the ternary complexes of La(III), Ce(III), Pr(III) and
Germany) in the range 4000–400 cm−1. X-ray diffraction (XRD) pat- Nd(III) ions with N-phenylanthranilic acid and phenanthroline was
terns were collected on solid complexes samples in a Bruker D2 Phaser carried out in methanol-aqueous solutions (1:1) at
powder diffractometer with Cu Kα radiation, λ = 1.5406 Å (position cM:cHnfa:cphen = 1:2:3 (where: cM, cHnfa, cphen – molar concentration of
sensitive detector: 0° ≤ 2θ ≤ 28°). The DSC curves in nitrogen atmo- metal ions, N-phentylanthranilic acid and phenanthroline, respec-
sphere were obtained using Mettler Toledo DSC‐822e (heating rate of tively). The aliquots of 1,10‐phenanthroline were added to adequate
10 K min−1). hot (343.15 K) solutions of lanthanide ions (1 · 10−2 mol dm−3). The
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Table 3
Thermal decomposition data for the complexes of Ln(III) ions with N-phenylanthranilic acid and 1,10‐phenanthroline in nitrogen atmosphere (where: nfa = C13H10NO2,
phen = C12H8N2).
Found Calc.
a
Total mass loss.
Table 4
Thermoanalytical data for dehydration processes of the complexes of Ln(III) ions with N-phenylanthranilic acid and 1,10‐phenanthroline.
Complex Dehydration temperature range (DSC)/K Onset temperature (DSC)/K Peak temperature (DSC)/K Dehydration enthalpy/kJ mol−1
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Table 6
Assignments of m/z signals detected in mass spectra of the evolved gases.
1 H+ 50 C4H2+
2 H2+ 51 C4H3+
12 C+ 52 C4H4+
16 O+ 63 C5H3+
17 OH+/NH3+ 65 C5H5+
18 H2O+ 66 C4H4N+
26 C2H2+ 76 C6H4+
28 CO+ 77 C6H5+
30 NO+ 78 (C6H5 + H)+
39 C3H3+ 79 (C6H5 + 2H)+
44 CO2+ 92 C6H6N+
46 NO2+/12C18O16O+
Fig. 4. Gram–Schmidt curves of the ternary Nd(III) complex in nitrogen and air atmo-
sphere.
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Fig. 6. Ion currents for selected fragments with the corresponding DTG curve for ternary Nd(III) complex in nitrogen.
Simultaneously, in the spectra of the complexes, the new characteristic for obtained complexes and sodium N-phenylanthranilate [32]. More-
absorption band from stretching vibrations of Ln–O bond (ν(Ln-O)) ap- over, mixed bridging– chelating character of the carboxylate group can
pears in the range of 433–440 cm−1. These facts indicate that the car- not be also excluded [33].
boxylate groups of N-phenylantranilate ligands have formed co- Furthermore, the IR spectra of the complexes show two bands as-
ordinative bonds with the investigated lanthanide ions [26,30,31]. signed to CeH stretching vibration δ(CeH) of phenanthroline ring in the
Taking into consideration the values of Δν (νas(COO−) − νs(COO−)) for range of 841–842 cm−1 and at 730 cm−1, respectively. These bands are
all studied complexes, which are slightly lower than that of the sodium red shifted compared to the free 1,10-phenanthroline from 853 cm−1
N-phenylanthranilate, we concluded that bidentate bridging coordina- and 738 cm−1, respectively. This fact indicates that 1,10-phenanthro-
tion takes place [29]. What is more, asymmetrical bidentate chelating line is involved in the formation of these complexes and is coordinated
mode of the coordination may occur due to the comparable values of Δν by two nitrogen atoms [34]. The presented analysis leads to the
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conclusion that both ligands are coordinated to metal ions thus the connected with medium and broad peaks on the DTG curves centered at
ternary complexes have been received. 533.15 K (La), 578.15 K (Pr) and 591.15 K (Nd). Similar degradation
stage has already been reported for ternary lanthanide complexes with
phenanthroline ligand and assigned to the release of phenanthroline
3.3. Thermal behaviors of the synthesized complexes
and part of secondary ligand [1,20,37] or partial phenanthroline de-
composition [19]. The percentage weight loss allows to suggest partial
The thermal decomposition processes of the obtained in solid state
loss of phenanthroline in case of La(III) (TG = 2.80%; calc. = 2.90%),
ternary lanthanide complexes were investigated in air and nitrogen
Pr(III) (TG = 10.00%; calc. = 9.77%) and Nd(III) (TG = 9.11%;
atmosphere by simultaneous TG-DSC technique. The TG, DTG and DSC
calc. = 9.16%) complexes. In case of cerium ternary complex, the
curves obtained in both atmospheres are presented in Fig. 3 and dis-
phenantroline partial loss is not connected with distinguishable peak on
cussed separately as follows.
DTG curve and is overlapped by next degradation stage.
The next step of the decomposition process connected with the
3.3.1. Thermal decomposition of the complexes in nitrogen atmosphere biggest mass loss (in range 55.65–70.67%) is observed between
The simultaneous TG/DTG-DSC curves of the ternary complexes in 563.15–855.15 K (La), 453.15–863.15 K (Ce), 620.15–823.15 K (Pr),
nitrogen atmosphere are presented in Fig. 3a–d. These results show that 617.15–815.15 K (Nd). For the complexes with La(III) and Ce(III) two
La(III) complex decomposes in five steps while for the complexes with overlapping steps, characterized by narrow peaks on the DTG curves at
Ce(III), Pr(III) and Nd(III) four decomposition stages are observed. The 682.15 and 726.15 K (La) or 692.15 and 728.15 K (Ce) are observed,
thermal decomposition data are summarized in Table 3. whereas for Pr(III) and Nd(III) compounds this process occurs in the
The first mass loss observed between 303.15 and 458.15 K takes two hardly distinguishable steps. This stage is related to loss of the
place without significant thermal event on the simultaneous registered remaining phenanthroline molecule [19] and degradation of nfa ligands
DSC curves and is attributed to the dehydration. In case of lanthanum [38,39]. Above 853.15 K the TG profiles show two consecutive steps
complex, 1 molecule of water is lost (1.29%; calc. = 1.16%) while in which correspond to small mass losses and weak, broad peaks on the
case of cerium (1.91%; calc. = 1.73%), praseodymium (1.78%; DTG curves at 938.15 and 1197.15 K (La), 937.15 and 1144.15 K (Ce),
calc. = 1.72%) and neodymium (1.44%; calc. = 1.72%) complexes 1.5 942.15 and 1170.15 K (Pr) or 935.15 and 1221.15 K (Nd). Their pre-
molecules of water are lost. On the DSC curves there are no en- sence confirms that during thermal decomposition of these complexes
dothermic peaks assigned to the dehydration step. This is probably formation of stable intermediate solid products is observed [39–44]. It
because of that the mass loss occurs slowly and the heat involved in this is postulated formation of carbonate derivatives (La oxycarbonate,
step is not sufficient to cause such thermal event [35]. basic carbonates of Ce and Nd, Pr carbonate) and carbon (in case of
In order to accurate analysis of the nature of water molecules and lanthanum, praseodymium and neodymium complexes) based on the
the stability of the obtained complexes the DSC curves were ad- found amounts of the intermediate residues as well as mass losses
ditionally recorded in nitrogen atmosphere in temperature range of (Table 3) [41,42,44–47].
233.15–383.15 K and the broad, weak endothermic peaks are observed. The amount of the final solid residue at 1273.15 K estimated from
Both low values of the dehydration enthalpies per one molecule of the TG curve of Ce(III) ternary complex is suitable to cerium oxide
water and the range of dehydration temperature (Table 4) confirm that (CeO2) [35]. The solid residues obtained for La(III), Pr(III) and Nd(III)
for all investigated compounds, the dehydration is connected with the complexes are considerably higher than these calculated for the ap-
release of the weakly bonded water molecules [36]. propriate oxides (La2O3, Pr6O11 and Nd2O3) and they contained a black
On the basis of the onset dehydration temperatures it can be stated solid which may be carbon derived from undecomposed nfa ligand.
that the thermal stability of the series of the ternary lanthanide com- These facts suggest that the final products of thermal decomposition
plexes is as follows: consist of the metal oxides and carbon, resulting from the uncompleted
pyrolysis of the La(III), Pr(III) and Nd(III) complexes [43,48–50].
Ce ∼ Pr < Nd < La
The second decomposition step of the investigated compounds, ex- 3.3.2. Thermal decomposition of the complexes in air atmosphere
cept for cerium complex, occurs below 593.15 K. The mass loss is The simultaneous TG/DTG-DSC curves of the ternary complexes in
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L. Zapała et al. Thermochimica Acta 659 (2018) 242–252
Fig. 9. Ion currents for selected fragments with the corresponding DTG curves for ternary Nd(III) complex in air.
3.4.1. EGA for Nd-nfa-phen in nitrogen Whereas, in the FT-IR spectrum at 591.15 K the low-intensity ab-
Stacked plots of the FTIR spectra of the gaseous species for neody- sorption bands of CO2 (doublet at 2358 and 2321 cm−1, 669 cm−1) are
mium complex during decomposition in nitrogen are shown in Fig. 5a. observed, the signals corresponding to second step of the thermal de-
Selected FTIR spectra of the gaseous species in different temperature composition are hardly distinguishable in the MS spectra (Fig. 6). The
are presented in Fig. 5b. lack of the bands characteristic for other small molecules may indicate
During heating in the temperature range 303.15–458.15 K, the mass that the aromatic rings of the organic ligands have not been broken.
spectra and the FTIR spectra of evolved gaseous products show signals In the temperature range 617.15-815.15 K, where the main mass
and absorption bands characteristic only for water molecules that prove loss is noted, in mass spectra the signals with m/z 12, 16, 44 and 46
the release of the crystal water and this fact is consistent with the TG (Fig. 6b, e) were detected, related to CO2, but no evolution of hydro-
experiment. carbons was detected by EGA-MS. In the FT-IR spectrum at 722.15 K,
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L. Zapała et al. Thermochimica Acta 659 (2018) 242–252
besides the bands in the range 2400–2250 cm−1 and 750–600 cm−1 have been synthesized and their spectroscopic properties as well as
attributed to carbon dioxide, also the bands characteristic for aromatic thermal decomposition were characterized. The characteristics of the
hydrocarbons were noted at 3057, 1597, 1507, 1302, 742 and complexes were done based on elemental analysis, gravimetry, infrared
720 cm−1 [51]. The similar effect was observed in the case of pre- spectroscopy, X-ray powder diffraction and thermoanalytical techni-
viously reported binary complexes [39]. The signals with m/z 26, 39, ques. The following general formula of the obtained complexes was
50, 51, 52, 63, 65, 66, 76, 77, 92 (Fig. 6c, d) are diagnostic for benzene proposed: Ln2(nfa)5(phen)(OH)·nH2O (where nfa – N-phenylan-
ring compounds as well as the products of the fragmentation of the thranilate anion; phen – 1,10‐phenanthroline). XRD analysis indicated
aromatic ligands and they were detected slightly above the third tem- that these compounds are amorphous.
perature of maximum mass loss. The EGA-MS and EGA-FTIR analyses The infrared spectroscopic data of obtained complexes demon-
confirm that decomposition of intermediate derivate of lanthanide strated that in coordination of lanthanide ions the oxygen atoms of the
carbonate in the next step of the thermal degradation is connected with carboxylate group of N-phenylanthranilate ligand and nitrogen atoms
the evolution of CO2. Additionally, the FTIR spectrum at 895.15 K of the neutral ligand – phenanthroline are involved. The values of Δν
shows simultaneous emission of the carbon monoxide at this stage. The suggest a bridging bidentate or mixed bridging–chelating mode for the
presence of these bands with the intensity almost equal to the intensity N-phenylanthranilate ions.
of CO2 bands, confirms the influence of the size of the evolved mole- The TG/DTG-DSC analysis provided, previously unreported in-
cules on variations in the time of their detection in inert atmosphere formation, about the thermal stability and thermal decomposition of
[52]. these compounds as well as indicated that complexes are stable at room
In the temperature range 1073.15-1273.15 K the fragments related temperature. During thermal decomposition firstly occurred the dehy-
to carbon dioxide are noted in MS spectra. In the FT-IR spectrum at dration and then phenanthroline ligand was decomposed.
1221.15 K only the bands derived from CO2 and CO are detected. Thus, The final solid residues of thermal decomposition were lanthanide
the mass spectra as well as the FT-IR spectra clearly confirm that inert oxides Ln2O3 (Ln = La, Nd), CeO2 and Pr6O11 in air atmosphere. In
flow of nitrogen does not give a constant final residue at 1273.15 K and nitrogen atmosphere it was CeO2 or mixture of lanthanide oxide (La2O3,
slow pyrolysis of the charred residue is not completed. Nd2O3, and Pr6O11) and carbon resulting from the uncompleted de-
Taking into account results of both thermoanalytical techniques composition of the La(III), Pr(III) and Nd(III) complexes. The thermal
(TG-DTG-DSC, TG- FTIR-MS) the decomposition pathways for the stu- stability of the obtained complexes is slightly different due to the nature
died compounds in nitrogen atmosphere have been proposed and of the metal ion and also depends on the applied atmosphere.
shown in Fig. 7. The EGA analysis by TG-FTIR and TG-MS proved that gaseous
products formed during thermal decomposition of the studied com-
3.4.2. EGA for Nd-nfa-phen in air plexes were the same. These gases included water, carbon monoxide,
The EGA-3D FTIR spectra and the FT-IR evolution curves of the carbon dioxide, diphenylamine, fragments from partial decomposition
gaseous species recorded as absorbance vs. temperature are shown in of organic ligands in nitrogen atmosphere and water, carbon monoxide,
Fig. 8, while the EGA-MS evolution curves as ion currents of the carbon dioxide, nitrogen monoxide, ammonia, fragments from partial
characteristic mass fragments are presented in Fig. 9. decomposition of organic ligands in air atmosphere.
The pathway of thermal decomposition of the ternary complex in
the temperature range 303.15–613.15 K in air and nitrogen atmosphere Acknowledgements
is very similar. On the basis of EGA-MS and EGA-FTIR analyses it was
confirmed that in the first and second steps of the thermal decom- The authors are grateful to Dr Beata Mossety-Leszczak from
position only the evolution of water and carbon dioxide takes place. Department of Industrial and Materials Chemistry, Rzeszow University
However, the atmosphere change has significant impact on the next of Technology for performance of DCS analyses.
degradation stages. In temperature range corresponding to third step of We thank also Piotr Szałański for made X-ray analysis in the
mass loss, in MS spectra (Fig. 9b, f and d, respectively), the signals Laboratory of Spectrometry, Faculty of Chemistry, Rzeszow University
originate from the evolution of both CO2 (m/z 12, 16, 44 and 46) and of Technology.
NO (m/z 30) were detected. The FT-IR spectrum recorded at 700.15 K
shows characteristic bands attributed to carbon dioxide molecules. No References
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