The ion-molecule reactions of disubstituted benzenes with the ion system of acetyl chloride under the chemical ionization condition were examined and the fragmentation reactions of the adduct ions formed by the ion-mo...The ion-molecule reactions of disubstituted benzenes with the ion system of acetyl chloride under the chemical ionization condition were examined and the fragmentation reactions of the adduct ions formed by the ion-molecule reactions were studied by using collision-induced dissociation technique. It was found that the electron-releasing groups favored the adduct reactions and the electron-withdrawing groups did not. The position and properties of substituting groups had an effect on the relative abundance of the adduct ions. The fragmentation reaction of the adduct ions formed by ortho-benzene diamine with the acetyl ion was similar to the reductive alkylation reaction of amine in condensed phase.展开更多
The rate constants of the nucleophilic reactions between amines and benzhydrylium ions were calculated using first-principles theoretical methods. Solvation models including PCM, CPCM, and COSMORS, as well as differen...The rate constants of the nucleophilic reactions between amines and benzhydrylium ions were calculated using first-principles theoretical methods. Solvation models including PCM, CPCM, and COSMORS, as well as different types of atomic radii including UA0, UAKS, UAHF, Bondi, and UFF, and several single-point energy calculation methods （B3LYP, B3P86, B3PW91, BHANDH, PBEPBE, BMK, M06, MP2, and ONIOM method） were examined. By comparing the correlation between experimental rate constants and the calculated values, the ONIOM（CCSD（T）/6-311＋＋G（2df,2p）：B3LYP/6-311＋＋G（2df,2p））//B3LYP/6- 31G（d）/PCM/UFF） method was found to perform the best. This method was then employed to calculate the rate constants of the reactions between diverse amines and diarylcarbenium ions. The calculated rate constants for 65 reactions of amines with diarylcarbenium ions are in agreement with the experimental values, indicating that it is feasible to predict the rate constant of a reaction between an amine and a diarylcarbenium ion through ab initio calculation.展开更多
In chemical ionization mass spectrometry (CIMS) gas phase C60+ or C60can react with fragment ions from three chloromethane and four multichloroethane molecular ions via ion-molecule reactions A dozen of gas-phase addu...In chemical ionization mass spectrometry (CIMS) gas phase C60+ or C60can react with fragment ions from three chloromethane and four multichloroethane molecular ions via ion-molecule reactions A dozen of gas-phase adduct ions of C60 are observed, and most of them contain chlorine atoms The results of the comparison and analysis show that the relative intensities of adduct ions are not directly proportional to the corresponding fragment ions in the MS of reagents,which implies that some fragment ions containing radicals are more reactive with C60+ or C60. This indicates that the alkene-like C60+ or C60 can act as a radical sponge in addition reactions.展开更多
The ion-molecule reactions in acetone were investigated which were induced under the chemical ionization. The structural information of the reaction products were obtained by using collision-induced dissociation (CID)...The ion-molecule reactions in acetone were investigated which were induced under the chemical ionization. The structural information of the reaction products were obtained by using collision-induced dissociation (CID) technique performed at ion kinetic energies of 30eV.展开更多
A thermodynamic model for predicting the equilibrium oxygens of 304 stainless steel was developed based on the theory of slag-steel equilibrium,the law of mass conservation,and the ion and molecule coexistence theory....A thermodynamic model for predicting the equilibrium oxygens of 304 stainless steel was developed based on the theory of slag-steel equilibrium,the law of mass conservation,and the ion and molecule coexistence theory.In the developed model,the Fe-Cr-Mn-Si-Al-S-O-melts reaction system and CaO-MgO-CaF_(2)-FeO-MnO-Al_(2)O_(3)-SiO_(2)-Cr2O_(3)slags were considered.The oxygen contents calculated by the model are in good agreement with experimental results and reference data.The equilibrium oxygen contents in 304 stainless steel mainly decrease with increasing binary basicity(w(CaO)/w(SiO_(2)),where w(i)is the mass percentage of component i)and decreasing temperature.Controlling binary basicity at 2.0 while maintaining temperatures lower than 1823 K will keep the oxygen contents in the 304 stainless steel lower than 15×10^(-6).The equilibrium oxygen contents may also be decreased with increasing content of MgO in slags,which is more significant at lower binary basicity.Besides,a small amount of FeO,MnO,and Al_(2)O_(3)(about 0-2.5 wt.%)in slags has little effect on equilibrium oxygen contents.Furthermore,it is found that the[C]-[O]reaction may occur during refining process but will not significantly affect the equilibrium oxygen contents.展开更多
文摘The ion-molecule reactions of disubstituted benzenes with the ion system of acetyl chloride under the chemical ionization condition were examined and the fragmentation reactions of the adduct ions formed by the ion-molecule reactions were studied by using collision-induced dissociation technique. It was found that the electron-releasing groups favored the adduct reactions and the electron-withdrawing groups did not. The position and properties of substituting groups had an effect on the relative abundance of the adduct ions. The fragmentation reaction of the adduct ions formed by ortho-benzene diamine with the acetyl ion was similar to the reductive alkylation reaction of amine in condensed phase.
文摘The rate constants of the nucleophilic reactions between amines and benzhydrylium ions were calculated using first-principles theoretical methods. Solvation models including PCM, CPCM, and COSMORS, as well as different types of atomic radii including UA0, UAKS, UAHF, Bondi, and UFF, and several single-point energy calculation methods （B3LYP, B3P86, B3PW91, BHANDH, PBEPBE, BMK, M06, MP2, and ONIOM method） were examined. By comparing the correlation between experimental rate constants and the calculated values, the ONIOM（CCSD（T）/6-311＋＋G（2df,2p）：B3LYP/6-311＋＋G（2df,2p））//B3LYP/6- 31G（d）/PCM/UFF） method was found to perform the best. This method was then employed to calculate the rate constants of the reactions between diverse amines and diarylcarbenium ions. The calculated rate constants for 65 reactions of amines with diarylcarbenium ions are in agreement with the experimental values, indicating that it is feasible to predict the rate constant of a reaction between an amine and a diarylcarbenium ion through ab initio calculation.
文摘In chemical ionization mass spectrometry (CIMS) gas phase C60+ or C60can react with fragment ions from three chloromethane and four multichloroethane molecular ions via ion-molecule reactions A dozen of gas-phase adduct ions of C60 are observed, and most of them contain chlorine atoms The results of the comparison and analysis show that the relative intensities of adduct ions are not directly proportional to the corresponding fragment ions in the MS of reagents,which implies that some fragment ions containing radicals are more reactive with C60+ or C60. This indicates that the alkene-like C60+ or C60 can act as a radical sponge in addition reactions.
文摘The ion-molecule reactions in acetone were investigated which were induced under the chemical ionization. The structural information of the reaction products were obtained by using collision-induced dissociation (CID) technique performed at ion kinetic energies of 30eV.
基金This work was financially supported by Key R&D Plan of Shandong Province in 2021(Grant No.2021CXGC010209).
文摘A thermodynamic model for predicting the equilibrium oxygens of 304 stainless steel was developed based on the theory of slag-steel equilibrium,the law of mass conservation,and the ion and molecule coexistence theory.In the developed model,the Fe-Cr-Mn-Si-Al-S-O-melts reaction system and CaO-MgO-CaF_(2)-FeO-MnO-Al_(2)O_(3)-SiO_(2)-Cr2O_(3)slags were considered.The oxygen contents calculated by the model are in good agreement with experimental results and reference data.The equilibrium oxygen contents in 304 stainless steel mainly decrease with increasing binary basicity(w(CaO)/w(SiO_(2)),where w(i)is the mass percentage of component i)and decreasing temperature.Controlling binary basicity at 2.0 while maintaining temperatures lower than 1823 K will keep the oxygen contents in the 304 stainless steel lower than 15×10^(-6).The equilibrium oxygen contents may also be decreased with increasing content of MgO in slags,which is more significant at lower binary basicity.Besides,a small amount of FeO,MnO,and Al_(2)O_(3)(about 0-2.5 wt.%)in slags has little effect on equilibrium oxygen contents.Furthermore,it is found that the[C]-[O]reaction may occur during refining process but will not significantly affect the equilibrium oxygen contents.
