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Related Concept Videos

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The axial and equatorial protons in cyclohexane can be distinguished by performing a variable-temperature NMR experiment. In this process, except for one proton, the remaining eleven protons are replaced by deuterium. The deuterium substitution avoids the possible peak splitting caused by the spin-spin coupling between the adjacent protons. The remaining proton flips between the axial and equatorial positions.
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When proton-coupled carbon-13 spectra are simplified by a broadband proton decoupling technique, structural information about the coupled protons is lost. Distortionless enhancement by polarization transfer (DEPT) is a technique that provides information on the number of hydrogens attached to each carbon in a molecule. While the DEPT experiment utilizes complex pulse sequences, the pulse delay and flip angle are specifically manipulated. The resulting signals have different phases depending on...
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At room temperature, the chair conformer of cyclohexane undergoes rapid ring flipping between two equivalent chair conformers at a rate of approximately 105 times per second. These two chair conformers are in equilibrium. The rapid ring flipping results in the interconversion of the axial proton to an equatorial proton and an equatorial to the axial proton. Such interconversions are too rapid and cannot be detected on the NMR timescale. Hence, the NMR spectrometer cannot distinguish between the...
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Some solids can transition directly into the gaseous state, bypassing the liquid state, via a process known as sublimation. At room temperature and standard pressure, a piece of dry ice (solid CO2) sublimes, appearing to gradually disappear without ever forming any liquid. Snow and ice sublimate at temperatures below the melting point of water, a slow process that may be accelerated by winds and the reduced atmospheric pressures at high altitudes. When solid iodine is warmed, the solid sublimes...
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The physical form of a substance changes on changing its temperature. For example, raising the temperature of a liquid causes the liquid to vaporize (convert into vapor). The process is called vaporization—a surface phenomenon. Vaporization occurs when the thermal motion of the molecules overcome the intermolecular forces, and the molecules (at the surface) escape into the gaseous state. When a liquid vaporizes in a closed container, gas molecules cannot escape. As these gas phase molecules...
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An anomalous high-pressure phase and decompression-induced amorphization in dinitrotoluene.

Ashutosh Mohan1, Krishan K Pandey1, Ajay K Mishra1

  • 1High Pressure & Synchrotron Radiation Physics Division, Bhabha Atomic Research Centre, Mumbai 400085, India and Homi Bhabha National Institute, Mumbai 400094, India.

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High pressure transforms 2,4-dinitrotoluene (2,4-DNT) via phase transitions and altered hydrogen bonding. Decompression reveals distinct recovery paths, including amorphization, impacting energetic molecular solid stability.

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Area of Science:

  • Materials Science
  • Chemistry
  • Physics

Background:

  • Energetic molecular solids are crucial for various applications.
  • Understanding their high-pressure behavior is key to predicting stability and performance.
  • 2,4-dinitrotoluene (2,4-DNT) is an energetic material whose response to pressure is not fully understood.

Purpose of the Study:

  • To investigate the high-pressure behavior of 2,4-dinitrotoluene (2,4-DNT).
  • To characterize phase transitions, structural changes, and compressibility under pressure.
  • To compare the behavior of 2,4-DNT with trinitrotoluene (TNT) and understand decompression pathways.

Main Methods:

  • In situ Raman spectroscopy up to ~19 GPa.
  • Synchrotron X-ray diffraction up to ~12.3 GPa.
  • Analysis of compression, phase transitions, and decompression recovery.

Main Results:

  • Raman spectroscopy detected conformational changes near 1.5 GPa and a phase transition between 4-8 GPa.
  • X-ray diffraction confirmed the phase transition onset at ~4.5 GPa, completing by ~8.4 GPa.
  • Both ambient and high-pressure phases exhibited negative linear compressibility; the high-pressure phase showed 1D order and new hydrogen bonds.
  • 2,4-DNT has a larger phonon gap (~104 cm-1) than TNT (~80 cm-1), suggesting lower impact sensitivity.
  • Decompression from ≤10 GPa led to hysteresis-bound recovery to the ambient phase.
  • Decompression from ≥12.3 GPa induced amorphization due to hydrogen bond network changes.

Conclusions:

  • High pressure induces significant structural and conformational changes in 2,4-DNT, including a phase transition and altered hydrogen bonding.
  • The pressure-induced changes influence the impact sensitivity and decompression behavior of 2,4-DNT.
  • Functional group interactions and pressure history critically affect phase stability and amorphization in energetic molecular crystals like 2,4-DNT and TNT.