Studies on the thermodynamic and kinetic properties of the insertion reactions for
                    <sup>1</sup>
                    XAl (X = H, Na, F, Cl, SH) with polar molecule hydrogen chloride at 200–1000 K

Yin, Ping; Hu, Yucai; Kong, Lingyan; Pi-jian, Zhang; Tang, Qinghua; Sun, Lin; Xu, Xiaohui

doi:10.1209/0295-5075/77/23001

Cited by 2 publications

(1 citation statement)

References 18 publications

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“…On the other hand, by using general statistical thermodynamics and Eyring transition state theory with Wigner correction, we examined the influence of temperature on the reaction channel. All computations of the thermodynamic and kinetic parameters ( H • , G • , S • , K, k, A) were obtained in the same way as in our previous work, 18,19 and the required optimized geometries, harmonic vibration frequencies, and electronic energies are all at the B3LYP/6-311+G (d,p) level.…”

Section: Methodsmentioning

confidence: 99%

Studies on the Hydrogen Transfer Reaction Mechanism of Singlet Thiol Phosphinidene Complex and the Temperature Effect

Yin

Chen

Wang

et al. 2009

Phosphorus, Sulfur, and Silicon and the Related Elements

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The hydrogen transfer reaction mechanism of the complex of a singlet thiol phosphinidene and a polar molecule hydrogen fluoride (HSP---HF) has been investigated at the B3LYP/6-311+G (d,p) level in order to better understand the reactivity of singlet phosphinidene. The results show that the relevant reaction, including step 1 [HSP---HF(1) → TS1 (2) → HSPH(F) (3)] and step 2 [HSPH(F) (3) → TS2 (4) → H 2 SPF (5)], are very different from the reactions of hydroxyl phosphinidene with hydrogen fluoride. Furthermore, theoretical studies on the thermodynamic and kinetic properties of the reaction have been carried out over the temperature range of 200-1200 K using the DFT/B3LYP method, the general statistical thermodynamics, and Eyring transition state theory with Wigner correction, which is used to examine the temperature effects the reaction channel. It is concluded that step 1 has both thermodynamic and kinetic advantages over step 2, and the high temperature is favorable to step 2. Moreover, the order of lgK and lgk for the steps are consistent with the order of their exoergic energies E and barrier height, but the differences of lgK and lgk for the steps decrease with the temperature increases.

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Section: Methodsmentioning

confidence: 99%

Studies on the Hydrogen Transfer Reaction Mechanism of Singlet Thiol Phosphinidene Complex and the Temperature Effect

Yin

Chen

Wang

et al. 2009

Phosphorus, Sulfur, and Silicon and the Related Elements

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Thermodynamic and Kinetic Aspects of the Reactions of Titanium(I) ion with the Sulfurtransfer Reagent SCO via the C22O Bond Activation Pathway

Yin

Xua

et al. 2007

Progress in Reaction Kinetics and Mechanism

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Theoretical studies on the thermodynamic and kinetic aspects of the reactions of Ti+ ion with the sulfur-transfer reagent SCO via the C22O bond activation pathway have been carried out over the temperature range 200 — 1200K using the DFT=B3LYP method, general statistical thermodynamics and Eyring transition state theory with the Wigner correction. The relevant reactions comprise: reaction 1 [Formula: see text], and reaction 2 [Formula: see text] in which the spin multiplicity changes from the quartet state to the doublet state in the crossing region. It is concluded that the order of the equilibrium constants (K) and the reaction rate constants (k) are consistent with that of their corresponding exoergic energies DE and reaction barriers, respectively, and their differences at low temperature are larger than those at high temperature. Step 2 of reaction 1 is both thermodynamically and kinetically favoured over the entire temperature range. Moreover, both reactions 1 and 2 are exothermic and proceed spontaneously in which their entropy increases, and the magnitudes of their thermodynamic constants all decrease with rising temperature. The calculated DH8, DG8, and DS8 values of the two reactions are relatively similar. However, because reactants 4Ti+ and SCO have a lower energy than that of reactants 2Ti+ and SCO, it is reaction 2, in which the quartet state is changed to the doublet state through intersystem crossing, which should be seen as dominant.

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Studies on the thermodynamic and kinetic properties of the insertion reactions for ¹ XAl (X = H, Na, F, Cl, SH) with polar molecule hydrogen chloride at 200–1000 K

Cited by 2 publications

References 18 publications

Studies on the Hydrogen Transfer Reaction Mechanism of Singlet Thiol Phosphinidene Complex and the Temperature Effect

Studies on the Hydrogen Transfer Reaction Mechanism of Singlet Thiol Phosphinidene Complex and the Temperature Effect

Thermodynamic and Kinetic Aspects of the Reactions of Titanium(I) ion with the Sulfurtransfer Reagent SCO via the C22O Bond Activation Pathway

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Studies on the thermodynamic and kinetic properties of the insertion reactions for 1 XAl (X = H, Na, F, Cl, SH) with polar molecule hydrogen chloride at 200–1000 K

Cited by 2 publications

References 18 publications

Studies on the Hydrogen Transfer Reaction Mechanism of Singlet Thiol Phosphinidene Complex and the Temperature Effect

Studies on the Hydrogen Transfer Reaction Mechanism of Singlet Thiol Phosphinidene Complex and the Temperature Effect

Thermodynamic and Kinetic Aspects of the Reactions of Titanium(I) ion with the Sulfurtransfer Reagent SCO via the C22O Bond Activation Pathway

Contact Info

Product

Resources

About

Studies on the thermodynamic and kinetic properties of the insertion reactions for ¹ XAl (X = H, Na, F, Cl, SH) with polar molecule hydrogen chloride at 200–1000 K