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Thermal hazard analysis and thermokinetic calculation of 1,3-dimethylimidazolium nitrate via TG and VSP2

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Abstract

In this study, the thermal stability and thermokinetic parameters of 1,3-dimethylimidazolium nitrate ([Mmim]NO3) were investigated by thermogravimetric analysis under non-isothermal conditions in a nitrogen atmosphere. The results showed that [Mmim]NO3 exhibited three decomposition stages from 93.3 to 350.0 °C, and the onset temperature of [Mmim]NO3 was obtained at approximately 161.0–182.0 °C under five heating rates. The apparent activation energy was 119.0–124.0 kJ mol−1, as calculated by different well-known equations, and the pre-exponential factor was 3.6 × 1012 min−1. The reaction mechanism of [Mmim]NO3 was carried out with the reaction order n = 1.0, and the decomposition mechanism function was further obtained. Moreover, vent sizing package 2 was employed to acquire the maximum self-heating rate (39,828.0 °C min−1) and pressure rise rate (73,331.0 psig min−1) for simulating cooling system failure in a practical process. The findings indicated that [Mmim]NO3 showed the possibility of a runaway reaction, leading to a potential thermal hazard. The approach of these results is vital for obtaining inherently safer process information for [Mmim]NO3 during production, storage, and transportation.

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Abbreviations

A :

Pre-exponential factor (min−1)

E a :

Apparent activation energy (kJ mol−1)

h :

Planck constant (J s)

k :

Reaction rate constant (min−1)

k B :

Boltzmann constant (J K−1)

n :

Reaction order

P max :

Maximum pressure (psig)

R :

Molar gas constant (J mol−1 K−1)

r :

Linear correlation coefficient

T :

Reaction temperature (K)

T end :

Termination temperature of decomposition (°C)

T max :

Maximum temperature (°C)

TMRad :

Time to maximum rate under adiabatic condition (h)

T NR :

No return temperature (°C)

T onset :

Onset temperature of decomposition (°C)

T p :

Peak temperature of decomposition (°C)

T start :

Start temperature of decomposition (°C)

ΔG ≠ :

Gibbs free energy (kJ mol−1)

ΔH ≠ :

Enthalpy (kJ mol−1)

ΔS ≠ :

Entropy (J mol K−1)

ΔP ad :

Adiabatic pressure rise (psig)

ΔT ad :

Adiabatic temperature rise (°C)

α :

Degree of conversion

β :

Heating rates (°C min−1)

Φ :

Thermal inertia

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Acknowledgements

The authors would like to express their appreciation to the Anhui Province Education Department Natural Sciences Key Fund, China, under the Contract Number KJ2017A078, as well as the donors of the Anhui University of Science and Technology, China, under the Contract Number QN201613 for financial support of this study.

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Authors and Affiliations

  1. School of Chemical Engineering, Anhui University of Science and Technology, Huainan, 232001, Anhui, China

    Bin Zhang & Shang-Hao Liu

  2. Department of Fire Science, Wu Feng University, 117 Jianguo Rd., Sec.2, Minsyong, Chiayi, 62153, Taiwan, ROC

    Jen-Hao Chi

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Correspondence to Shang-Hao Liu.

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Zhang, B., Liu, SH. & Chi, JH. Thermal hazard analysis and thermokinetic calculation of 1,3-dimethylimidazolium nitrate via TG and VSP2. J Therm Anal Calorim 134, 2367–2374 (2018). https://doi.org/10.1007/s10973-018-7557-4

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