Determination of nitroaromatic and nitramine type energetic materials in synthetic and real mixtures by cyclic voltammetry

Ayşem Üzer; Şener Saǧlam; Yasemin Tekdemir; Belkis Ustamehmetoǧlu; Esma Sezer; Erol Erçaǧ; Reşat Apak

doi:10.1016/j.talanta.2013.06.047

Determination of nitroaromatic and nitramine type energetic materials in synthetic and real mixtures by cyclic voltammetry

Ayşem Üzer, Şener Saǧlam, Yasemin Tekdemir, Belkis Ustamehmetoǧlu, Esma Sezer, Erol Erçaǧ, Reşat Apak^*

^*Corresponding author for this work

Department of Chemistry

Istanbul University

Research output: Contribution to journal › Article › peer-review

31 Citations (Scopus)

Abstract

Nitro-explosives contain reducible aromatic -NO₂ groups or cyclic >N-NO₂ bonds that may undergo reductive cleavage. This work reports the development of a cyclic voltammetric (CV) assay for nitro-aromatics (trinitrotoluene (TNT), dinitrotoluene (DNT)) and nitramines (1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) and octahydro-1,3,5,7-tetranitro- 1,3,5,7-tetrazocine (HMX)) using a glassy carbon electrode. This determination was first used for these energetic materials by resolving current responses of reduction potentials primarily due to one constituent but partly contributed by other constituents. Calibration curves of current intensity versus concentration were linear in the range of 30-120 mg L^-1 for RDX with a limit of detection (LOD) of 10.2 mg L^-1, 40-120 mg L^-1 for HMX (LOD=11.7 mg L^-1), 40-120 mg L^-1 for TNT (LOD=11.2 mg L^-1), and 40-140 mg L^-1 for DNT (LOD=10.8 mg L ^-1). Results showed that the CV method could provide a sensitive approach for the simultaneous determination of RDX and TNT in synthetic and real mixtures. Deconvolution of current contributions of mixtures at peak potentials of constituents was performed by multiple linear regression. The proposed method was successfully applied to the analysis of military explosives comp A5 and octol, and method validation was performed both against HPLC on a comp B (TNT+RDX) sample and against GC-MS on real post-blast residual samples containing both explosives.

Original language	English
Pages (from-to)	768-778
Number of pages	11
Journal	Talanta
Volume	115
DOIs	https://doi.org/10.1016/j.talanta.2013.06.047
Publication status	Published - 2013

Funding

The authors wish to express their gratitude to the Ministry of National Defence, Office of Technical Services, to Machinery & Chemistry Industries Institution (MKEK) for the donation of nitro- and composite explosive samples, Additionally, the authors thank the Turkish Republic Ministry of Science, Industry and Technology−General Directorate of Science and Technology (T.C. Bilim, Sanayi ve Teknoloji Bakanlığı−Bilim ve Teknoloji Genel Müdürlüğü) for the San-Tez Project 00601.STZ.2010-1. The Ministry wishes to declare that none of the ideas (originally belonging to the authors) presented in this article represents their official view. All authors wish to repeat their thanks to MKEK for their general support by taking part in the indicated San-Tez Project. The authors extend these thanks to Istanbul University Research Fund for the support given to Normal Project-12110 and 14412. One of the authors (Dr. Erol Erçağ) extends his thanks to Istanbul University Research Fund for the support given to UDP Project-22511, which enabled him to present a part of this work in the 15th International Seminar on New Trends in Research of Energetic Materials in Pardubice, Czech Republic. Two authors (Ş. Sağlam and Y. Tekdemir) wish to thank the Turkish Academy of Sciences (TUBA) for research expenses support conveyed by Dr. Reşat Apak (Academy member).

Funders	Funder number
Istanbul Üniversitesi	14412

Keywords

Cyclic voltammetry
DNT
HMX
Nitro explosives analysis
RDX
TNT

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title = "Determination of nitroaromatic and nitramine type energetic materials in synthetic and real mixtures by cyclic voltammetry",

abstract = "Nitro-explosives contain reducible aromatic -NO2 groups or cyclic >N-NO2 bonds that may undergo reductive cleavage. This work reports the development of a cyclic voltammetric (CV) assay for nitro-aromatics (trinitrotoluene (TNT), dinitrotoluene (DNT)) and nitramines (1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) and octahydro-1,3,5,7-tetranitro- 1,3,5,7-tetrazocine (HMX)) using a glassy carbon electrode. This determination was first used for these energetic materials by resolving current responses of reduction potentials primarily due to one constituent but partly contributed by other constituents. Calibration curves of current intensity versus concentration were linear in the range of 30-120 mg L-1 for RDX with a limit of detection (LOD) of 10.2 mg L-1, 40-120 mg L-1 for HMX (LOD=11.7 mg L-1), 40-120 mg L-1 for TNT (LOD=11.2 mg L-1), and 40-140 mg L-1 for DNT (LOD=10.8 mg L -1). Results showed that the CV method could provide a sensitive approach for the simultaneous determination of RDX and TNT in synthetic and real mixtures. Deconvolution of current contributions of mixtures at peak potentials of constituents was performed by multiple linear regression. The proposed method was successfully applied to the analysis of military explosives comp A5 and octol, and method validation was performed both against HPLC on a comp B (TNT+RDX) sample and against GC-MS on real post-blast residual samples containing both explosives.",

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T1 - Determination of nitroaromatic and nitramine type energetic materials in synthetic and real mixtures by cyclic voltammetry

AU - Üzer, Ayşem

AU - Saǧlam, Şener

AU - Tekdemir, Yasemin

AU - Ustamehmetoǧlu, Belkis

AU - Sezer, Esma

AU - Erçaǧ, Erol

AU - Apak, Reşat

PY - 2013

Y1 - 2013

N2 - Nitro-explosives contain reducible aromatic -NO2 groups or cyclic >N-NO2 bonds that may undergo reductive cleavage. This work reports the development of a cyclic voltammetric (CV) assay for nitro-aromatics (trinitrotoluene (TNT), dinitrotoluene (DNT)) and nitramines (1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) and octahydro-1,3,5,7-tetranitro- 1,3,5,7-tetrazocine (HMX)) using a glassy carbon electrode. This determination was first used for these energetic materials by resolving current responses of reduction potentials primarily due to one constituent but partly contributed by other constituents. Calibration curves of current intensity versus concentration were linear in the range of 30-120 mg L-1 for RDX with a limit of detection (LOD) of 10.2 mg L-1, 40-120 mg L-1 for HMX (LOD=11.7 mg L-1), 40-120 mg L-1 for TNT (LOD=11.2 mg L-1), and 40-140 mg L-1 for DNT (LOD=10.8 mg L -1). Results showed that the CV method could provide a sensitive approach for the simultaneous determination of RDX and TNT in synthetic and real mixtures. Deconvolution of current contributions of mixtures at peak potentials of constituents was performed by multiple linear regression. The proposed method was successfully applied to the analysis of military explosives comp A5 and octol, and method validation was performed both against HPLC on a comp B (TNT+RDX) sample and against GC-MS on real post-blast residual samples containing both explosives.

AB - Nitro-explosives contain reducible aromatic -NO2 groups or cyclic >N-NO2 bonds that may undergo reductive cleavage. This work reports the development of a cyclic voltammetric (CV) assay for nitro-aromatics (trinitrotoluene (TNT), dinitrotoluene (DNT)) and nitramines (1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) and octahydro-1,3,5,7-tetranitro- 1,3,5,7-tetrazocine (HMX)) using a glassy carbon electrode. This determination was first used for these energetic materials by resolving current responses of reduction potentials primarily due to one constituent but partly contributed by other constituents. Calibration curves of current intensity versus concentration were linear in the range of 30-120 mg L-1 for RDX with a limit of detection (LOD) of 10.2 mg L-1, 40-120 mg L-1 for HMX (LOD=11.7 mg L-1), 40-120 mg L-1 for TNT (LOD=11.2 mg L-1), and 40-140 mg L-1 for DNT (LOD=10.8 mg L -1). Results showed that the CV method could provide a sensitive approach for the simultaneous determination of RDX and TNT in synthetic and real mixtures. Deconvolution of current contributions of mixtures at peak potentials of constituents was performed by multiple linear regression. The proposed method was successfully applied to the analysis of military explosives comp A5 and octol, and method validation was performed both against HPLC on a comp B (TNT+RDX) sample and against GC-MS on real post-blast residual samples containing both explosives.

KW - Cyclic voltammetry

KW - DNT

KW - HMX

KW - Nitro explosives analysis

KW - RDX

KW - TNT

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U2 - 10.1016/j.talanta.2013.06.047

DO - 10.1016/j.talanta.2013.06.047

M3 - Article

AN - SCOPUS:84880361404

SN - 0039-9140

VL - 115

SP - 768

EP - 778

JO - Talanta

JF - Talanta

ER -

Determination of nitroaromatic and nitramine type energetic materials in synthetic and real mixtures by cyclic voltammetry

Abstract

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Keywords

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