Enthalpies of Formation of Hydrazine and Its Derivatives

Abstract

Enthalpies of formation, ΔH, in both the gas and condensed phase, and enthalpies of sublimation or vaporization have been estimated for hydrazine, NHNH, and its 36 various derivatives using quantum chemical calculations. The composite G4 method has been used along with isodesmic reaction schemes to derive a set of self-consistent high-accuracy gas-phase enthalpies of formation. To estimate the enthalpies of sublimation and vaporization with reasonable accuracy (5-20 kJ/mol), the method of molecular electrostatic potential (MEP) has been used. The value of ΔH(NHNH,g) = 97.0 ± 3.0 kJ/mol was determined from 75 isogyric reactions involving about 50 reference species; for most of these species, the accurate ΔH(g) values are available in Active Thermochemical Tables (ATcT). The calculated value is in excellent agreement with the reported results of the most accurate models based on coupled cluster theory (97.3 kJ/mol, the average of six calculations). Thus, the difference between the values predicted by high-level theoretical calculations and the experimental value of ΔH(NHNH,g) = 95.55 ± 0.19 kJ/mol recommended in the ATcT and other comprehensive reference sources is sufficiently large and requires further investigation. Different hydrazine derivatives have been also considered in this work. For some of them, both the enthalpy of formation in the condensed phase and the enthalpy of sublimation or vaporization are available; for other compounds, experimental data for only one of these properties exist. Evidence of accuracy of experimental data for the first group of compounds was provided by the agreement with theoretical ΔH(g) value. The unknown property for the second group of compounds was predicted using the MEP model. This paper presents a systematic comparison of experimentally determined enthalpies of formation and enthalpies of sublimation or vaporization with the results of calculations. Because of relatively large uncertainty in the estimated enthalpies of sublimation, it was not always possible to evaluate the accuracy of the experimental values; however, this model allowed us to detect large errors in the experimental data, as in the case of 5,5'-hydrazinebistetrazole. The enthalpies of formation and enthalpies of sublimation or vaporization have been predicted for the first time for ten hydrazine derivatives with no experimental data. A recommended set of self-consistent experimental and calculated gas-phase enthalpies of formation of hydrazine derivatives can be used as reference ΔH(g) values to predict the enthalpies of formation of various hydrazines by means of isodesmic reactions.

Experimental and numerical analysis of the autoignition behavior of NH3 and NH3/H2 mixtures at high pressure

“…The reason for the discrepancy between the theoretical rate coefficients for NH 2 + NH 2 ( + M) = N 2 H 4 ( + M) and the shock tube measurements of the reverse step is not known at present. The heat of formation of N 2 H 4 has been in question, but the current value [29] is in excellent agreement with the recent recommendations by Dorofeeva et al [45] and Feller et al [46] . It is an issue whether the experimental data are truly obtained at the lowand high-pressure limits, respectively, but more work is required to resolve this issue.…”

Enthalpy of Formation of N2H4 (Hydrazine) Revisited

“…Table contains the experimental values discussed earlier, together with a wider list of selected theoretical literature values for the enthalpy of formation of hydrazine. − ,− ,,,,,− Ignoring the negative B3LYP enthalpy of formation, one can find a low Δ f H °(0 K) of 99.85 kJ/mol and a high of 115.4 ± 2.0 kJ/mol. The ATcT ver.…”

Experimental and numerical studies of the ignition of ammonia/additive mixtures and dimethyl ether burning velocities

“…The reason for the discrepancy between the theoretical rate coefficients for NH2 + NH2 (+M) = N2H4 (+M) and the shock tube measurements of the reverse step is not known at present. The heat of formation of N2H4 has been in question, but the current value [30] is in excellent agreement with the recent recommendations by Dorofeeva et al [96] and Feller et al [97]. It is an issue whether the experimental data are truly obtained at the low and high pressure limits, respectively, but more work is required to resolve this issue.…”