Abstract
An energetic Copper (II) complex based on 3,5 dinitrobenzoic acid (DNBA) was synthesized from copper nitrate, DNBA and 2,2' bipyridine and characterized by elemental analysis, FTIR, UV–Vis and single crystal X-ray diffraction techniques. The XRD results confirmed that the complex consists of one dimensional linear chains in which three ligands coordinated with copper metal via nitrogen and oxygen atoms of bipyridine and two DNBA molecules, respectively. The decomposition, kinetics and reaction mechanism for the decomposition reaction were studied by using thermogravimetry and differential scanning calorimetry analyses. The results indicate that the copper (II) complex possesses high thermal stability, above 230 °C. The values of the activation energy were found to be 182.2 kJ/mol from Flynn–Wall–Ozawa (FWO) and 183.1 kJ/mol from Kissinger-Akahira-Sunose (KAS) method, respectively. The pre-exponential factors of the copper (II) complex for different ranges of conversions were determined by using the compensation effect. The reaction model for decomposition reactions is probably best described by Avrami-Erofeev (A2) model. Furthermore, computation of the thermodynamic parameters for formation of activated complex were carried out using DSC data. The results of sensitivity tests show that the copper (II) complex is insensitive in nature towards impact and friction forces.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Akahira T, Sunose T (1971) Method of determining activation deterioration constant of electrical insulating materials. Res Rep CHIBA Inst Technol 6:22–31
Baran EJ, Wagner CC, Torre MH et al (2000) Vibrational spectra of the Cu(II) complexes of aspartic and glumatic acids. Acta Farm Bonaerense 19:231–234
Bayat V, Zeynali V (2011) Preparation and characterization of nano-CL-20 explosive. J Energ Mater 29:281–291. https://doi.org/10.1080/07370652.2010.527897
Boonchom B, Puttawong S (2010) Thermodynamics and kinetics of the dehydration reaction of FePO42H2O. Phys B Condens Matter 405:2350–2355. https://doi.org/10.1016/j.physb.2010.02.046
Boonchom B, Thongkam M (2010) Kinetics and thermodynamics of the formation of MnFeP4O12. J Chem Eng Data 55:211–216. https://doi.org/10.1021/je900310m
Fischer N, Klapötke TM, Stierstorfer J (2009) New nitriminotetrazoles—synthesis, structures and characterization. Z Anorg Allg Chem 635:271–281. https://doi.org/10.1002/zaac.200800430
Fischer D, Klapötke TM, Stierstorfer J (2014) Potassium 1,1’-Dinitramino-5,5’-bistetrazolate: a primary explosive with fast detonation and high initiation power. Angew Chem Int Ed 53:8172–8175. https://doi.org/10.1002/anie.201404790
Flynn JH, Wall LA (1966) General treatment of the thermogravimetry of polymers. J Res Natl Bur Std-A Phys Chem 70:487–523. https://doi.org/10.6028/jres.070a.043
Friedman Y, Goldberg I (2018) Tetrazole-bridged manganese coordination polymer as high energy material. Polyhedron 139:327–330. https://doi.org/10.1016/j.poly.2017.11.010
Galwey AK (2015) Solid state reaction kinetics, mechanisms and catalysis: a retrospective rational review. Reac Kinet Mech Cat 114:1–29. https://doi.org/10.1007/s11144-014-0770-7
Haiges R, Christe KO (2015) 5-(Fluorodinitromethyl)-2H-tetrazole and its tetrazolates—Preparation and characterization of new high energy compounds. Dalton Trans 44:10166–10176. https://doi.org/10.1039/C5DT00291E
Jia X, Hou C, Tan Y et al (2017) Fabrication and characterization of PMMA/HMX-based microcapsules via in situ polymerization. Cent Eur J Energ Mater 14:559–572
Jia X, Wei L, Liu X et al (2019) Fabrication and characterization of submicron scale spherical RDX, HMX, and CL-20 without soft agglomeration. J Nanomater 2019:1–8. https://doi.org/10.1155/2019/7394762
Kaur M, Yathirajan HS, Byrappa K et al (2014) Crystal structure of desvenlafaxinium 3,5-dinitrobenzoate 3,5-dinitrobenzoic acid monohydrate, C30H35N5O15. Z Kristallogr NCS 229:488–490. https://doi.org/10.1515/ncrs-2014-0131
Kissinger HE (1956) Variation of peak temperature with heating rate in differential thermal analysis. J Res Natl Bur Stand 57:217–221
Kissinger HE (1957) Reaction kinetics in differential thermal analysis. Anal Chem 129:1702–1706. https://doi.org/10.1021/ac60131a045
Klapötke TM, Sabate CM (2009) Safe 5-nitrotetrazolate anion transfer reagents. Dalton Trans 10:1835–1841. https://doi.org/10.1039/B818900P
Klapötke TM, Stierstorfer J (2007) Nitration Products of 5-Amino-1H-tetrazole and methyl-5-amino-1H-tetrazoles–structures and properties of promising energetic materials. Helv Chim Acta 90:2132–2150. https://doi.org/10.1002/hlca.200790220
Klapötke TM, Stierstorfer J (2008) The new energetic compounds 1,5-Diaminotetrazolium and 5-Amino-1-methyltetrazolium dinitramide—synthesis, characterization and testing. Eur J Inorg Chem 26:4055–4062. https://doi.org/10.1002/ejic.200890071
Klapötke TM, Stierstorfer J (2009) Azidoformamidinium and 5-aminotetrazolium dinitramide-two highly energetic isomers with a balanced oxygen content. Dalton Trans 4:643–653. https://doi.org/10.1039/B811767E
Klapötke TM, Mayer P, Sabate CM et al (2008a) Simple, Nitrogen-rich, energetic salts of 5-nitrotetrazole. Inorg Chem 47:6014–6027. https://doi.org/10.1021/ic800353y
Klapötke TM, Sabate CM, Welch JM (2008b) 1,5-Diamino-4-methyltetrazolium 5 nitrotetrazolate—synthesis, testing and scale up. Z Anorg Allg Chem 634:857–866. https://doi.org/10.1002/zaac.200700539
Klapötke TM, Sabate CM, Welch JM (2008c) Alkali metal 5-nitrotetrazolate salts: prospective replacements for service lead(II) azide in explosive initiators. Dalton Trans 45:6372–6380. https://doi.org/10.1039/b811410b
Klapötke TM, Stierstorfer J, Wallek AU (2008d) Nitrogen-rich salts of 1-methyl-5- nitriminotetrazolate: an auspicious class of thermally stable energetic materials. Chem Mater 20:4519–4530. https://doi.org/10.1021/cm8004166
Klapötke TM, Sabate CM, Rasp M (2009a) Synthesis and properties of 5-nitrotetrazole derivatives as new energetic materials. J Mater Chem 19:2240–2252. https://doi.org/10.1039/B818925K
Klapötke TM, Sabate CM, Welch JM (2009b) Alkaline earth metal salts of 5-Nitro-2H-tetrazole: prospective candidates for environmentally friendly energetic applications. Eur J Inorg Chem 6:769–776. https://doi.org/10.1002/ejic.200801080
Klapötke TM, Stierstorfer J, Weber B (2009c) New energetic materials: synthesis and characterization of copper 5-nitriminotetrazolates. Inorg Chim Acta 362:2311–2320. https://doi.org/10.1016/j.ica.2008.10.014
L’vov BV, (2014) Activation effect in heterogeneous decomposition reactions: fact or fiction? React Kinet Mech Cat 111:415–429. https://doi.org/10.1007/s11144-014-0675-5
L’vov BV, (2015) On the way from the activation model of solid decomposition to the thermochemical model. React Kinet Mech Cat 116:1–18. https://doi.org/10.1007/s11144-015-0886-4
Li S, Wang Y, Qi C, Zhao X et al (2013) 3D energetic metal-organic frameworks: synthesis and properties of high energy materials. Angew Chem Int Ed 52:14031–14035. https://doi.org/10.1002/anie.201307118
Liu X, Su Z, Ji W et al (2014a) Structure, physicochemical properties, and density functional theory calculation of high-energy-density materials constructed with intermolecular interaction: nitro group charge determines sensitivity. J Phys Chem C 118:23487–23498. https://doi.org/10.1021/jp5062418
Liu X, Yang Q, Su Z et al (2014b) 3D high-energy-density and low sensitivity materials: synthesis, structure and physicochemical properties of an azide-Cu(II) complex with 3,5-dinitrobenzoic acid. RSC Adv 4:16087–16093. https://doi.org/10.1039/C4RA00635F
Pinheiro GFM, Lourenco VL, Iha K (2002) Influence of the heating rate in the thermal decomposition of HMX. J Therm Anal Calorim 67:445–452. https://doi.org/10.1023/A:1013984813195
Singla P, Singh A, Sahoo SC, Soni PK, Kishore P (2021) Synthesis, characterization and thermal decomposition kinetics of energetic copper complex based on 3,5 Dinitrobenzoic acid and 1,10 Phenanthroline. Chemical Papers. https://doi.org/10.1007/s11696-021-01992-2
Singh A, Soni PK, Singh M et al (2012) Thermal degradation, kinetic and correlation models of poly(vinylidene-fluoride–chlorotrifluoroethylene) copolymers. Thermochim Acta 548:88–92. https://doi.org/10.1016/j.tca.2012.08.031
Singh A, Soni PK, Shekharam T et al (2013) A study on thermal behavior of a poly(VDF-CTFE) copolymers binder for high energy materials. J Appl Polym Sci 127:1751–1757. https://doi.org/10.1002/app.37780
Singh A, Kishore P, Singh M et al (2015) A changes in the structural and thermal properties of poly(vinylidene fluoride–chlorotrifluoroethylene) irradiated with 4 MeV protons. Radiat Eff Def Solids 70:845–853. https://doi.org/10.1080/10420150.2015.1121391
Singh A, Sharma TC, Kishore P (2017a) Thermal degradation kinetics and reaction models of 1,3,5-triamino-2,4,6-trinitrobenzene-based plastic-bonded explosives containing fluoropolymer matrices. J Therm Anal Calorim 129:1403–1414. https://doi.org/10.1007/s10973-017-6335-z
Singh A, Singh S, Sharma TC et al (2017b) Physicochemical properties and kinetic analysis for some fluoropolymers by differential scanning calorimetry. Polym Bull 75:2315–2338. https://doi.org/10.1007/s00289-017-2153-5
Singh A, Kumar R, Soni PK et al (2019a) Compatibility and thermokinetics studies of octahydro- 1,3,5,7-tetranitro-1,3,5,7-tetrazocine with polyether-based polyurethane containing different curatives. J Energ Mater 37:141–153. https://doi.org/10.1080/07370652.2018.1552337
Singh A, Soni PK, Sarkar C et al (2019b) Thermal reactivity of aluminized polymer-bonded explosives based on non-isothermal thermogravimetry and calorimetry measurements. J Therm Anal Calorim 136:1021–1035. https://doi.org/10.1007/s10973-018-7730-9
Singh A, Singh S, Soni PK et al (2020) Non-isothermal thermogravimetric degradation kinetics, reaction models and thermodynamic parameters of vinylidene fluoride based fluorinated polymers. J Macromol Sci Part B-Phys 59:1–24. https://doi.org/10.1080/00222348.2019.1679986
Srinivasan K, Stalin T (2014) Study of inclusion complex between 2,6-dinitrobenzoic acid and b-cyclodextrin by 1H NMR, 2D 1H NMR (ROESY), FT-IR, XRD, SEM and photophysical methods. Spectrochim Acta A Mol Biomol Spectrosc 130:105–115. https://doi.org/10.1016/j.saa.2014.03.106
Su H, Zhang JC, Du Y et al (2017) New roles for metal-organic frameworks: fuels for environmentally friendly composites. RSC Adv 7:11142–11148. https://doi.org/10.1039/C6RA28679H
Takeo O (1965) A new method of analyzing thermogravimetric data. Bull Chem Soc Jpn 38:1881–1886. https://doi.org/10.1246/bcsj.38.1881
Tao GH, Parrish DA, Shreeve JM (2012) Nitrogen-rich 5-(1-methylhydrazinyl)tetrazole and its copper and silver complexes. Inorg Chem 51:5305–5312. https://doi.org/10.1021/ic300242e
Vyazovkin S, Burnham AK, Criado JM et al (2010) ICTAC kinetics committee recommendations for performing kinetic computations on thermal analysis data. Thermochim Acta 520:1–19. https://doi.org/10.1016/j.tca.2011.03.034
Wang K, Zeng D, Zhang JG et al (2015) Controllable explosion: fine-tuning the sensitivity of high-energy complexes. Dalton Trans 44:12497–12501. https://doi.org/10.1039/C5DT01462J
Wu Q, Kou B, Zhang Z et al (2017) The search for new powerful energetic transition metal complexes based on 3,3′-dinitro-5,5′-bis-1,2,4-triazole-1,1′-diolate anion: a DFT study. J Mol Model 23:254–263. https://doi.org/10.1007/s00894-017-3425-6
Xu CX, Zhang JG, Yin X et al (2015) Cd (II) complexes with different nuclearity and dimensionality based on 3-hydrazino-4-amino-1,2,4-triazole. J Solid State Chem 226:59–65. https://doi.org/10.1016/j.jssc.2015.02.004
Xue H, Gao H, Twamley B et al (2007) Energetic salts of 3-nitro-1,2,4-triazole-5-one, 5-nitroaminotetrazole, and other nitro-substituted azoles. Chem Mater 19:1731–1739. https://doi.org/10.1021/cm062964g
Yang Q, Chen S, Xie G et al (2011) Synthesis and characterization of an energetic compound Cu(Mtta)2(NO3)2 and effect on thermal decomposition of ammonium perchlorate. J Hazard Mater 197:199–203. https://doi.org/10.1039/C5DT01462J
Ye BY, An CW, Wang JY et al (2017) Formation and properties of HMX-based microspheres via spray drying. RSC Adv 7:35411–35416. https://doi.org/10.1039/C7RA02737K
Yin P, Parrish DA, Shreeve JM (2015) Energetic multifunctionalized nitraminopyrazoles and their ionic derivatives: Ternary hydrogen-bond induced high energy density materials. J Am Chem Soc 137:4778–4786. https://doi.org/10.1021/jacs.5b00714
Yu XK, Zheng YQ (2013) Syntheses, structures, dielectric and ferroelectric properties of a chiral coordination compound with m-nitro-benzoic acid. J Coord Chem 66:2208–2216. https://doi.org/10.1080/00958972.2013.803219
Zhang J, Yin P, Mitchell LA et al (2016a) N-functionalised nitroxy/azido fused-ring azoles as high-performance energetic materials. J Mater Chem A 4:7430–7436. https://doi.org/10.1039/C6TA02384C
Zhang S, Yang Q, Liu X et al (2016b) High-energy metal–organic frameworks (HE-MOFs): synthesis, structure and energetic performance. Coord Chem Rev 307:292–312. https://doi.org/10.1016/j.ccr.2015.08.006
Acknowledgements
We would like to extend our sincere gratitude and appreciation to Sh. Niladri Mukherjee, Technology Director for his encouragement and cooperation to execute this work.
Author information
Authors and Affiliations
Corresponding author
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Information
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Singla, P., Singh, A., Sahoo, S.C. et al. Synthesis, characterization and reaction kinetics of an energetic copper (II) complex based on 3,5 dinitrobenzoic acid and 2, 2' bipyridine. Chem. Pap. 76, 2153–2165 (2022). https://doi.org/10.1007/s11696-021-02000-3
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11696-021-02000-3