Based on thermoelectrochemical equation for an electrode reaction, the entropy change of it can be obtained by the thermoelectrochemical technology(TECT). The entropy changes of Fe(CN)-36/Fe(CN)-46,H+/H2(P0), Cu+2/Cu...Based on thermoelectrochemical equation for an electrode reaction, the entropy change of it can be obtained by the thermoelectrochemical technology(TECT). The entropy changes of Fe(CN)-36/Fe(CN)-46,H+/H2(P0), Cu+2/Cu and Zn+2/Zn electrode reaction systems and the dilute enthalpies of the H+, Cu2+ and Zn2+ ions under the ion concentrations studied have been determined by a specially designed thermoelectrochemical equipment. The enthalpy change and entropy change for the five systems at unlimitedly diluted concentrations agree well with the literature.展开更多
Information about the forty nine nitraminic plastic bonded explosives(PBXs)and different nitramines were collected.Fillers of these PBXs are nitramines 1,3,5-trinitro-1,3,5-triazinane(RDX)and β-1,3,5,7-tetranitro-1,3...Information about the forty nine nitraminic plastic bonded explosives(PBXs)and different nitramines were collected.Fillers of these PBXs are nitramines 1,3,5-trinitro-1,3,5-triazinane(RDX)and β-1,3,5,7-tetranitro-1,3,5-tetrazocane(β-HMX),cis-1,3,4,6-tetranitro-octahydroimidazo-[4,5-d]imidazole(bicyclo-HMX,BCHMX)and e-2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane(e-HNIW,CL-20)which are bonded by polyfluoro-elastomers,polydimethyl-siloxane,poly-glycidyl azide,polyisobutylene,polystyrene-butadiene,poly-acrylonitrile-butadiene and hydroxyl-terminated polybutadiene in addition to a melt cast compositions based on 2,4,6-trinitrotoluene.For thirty two of these PBXs the relationships are specified and analyzed between heats of their combustion and relative explosive strengths;by means of these relationships it might be possible to estimate,which groupings in the macromolecule of binder could be liable to their primary fission in the PBXs initiation.Similarly,for forty two of these explosives,the relationships are described and analyzed between their enthalpies of formation and impact sensitivities;here is especially attention paid to PBXs filled by BCHMX.Specific rate constants from Vacuum Stability Test(VST)of four nitramines and twenty PBXs are introduced into relationships with their enthalpies of formation.Regarding to all the mentioned cases,increasing of energy content of the studied explosives leads to increase of the relative explosive strength or initiation reactivity,respectively.Exception with the opposite trend,the outputs of VST are for BCHMX,where in PBXs are matrices with the esteric plasticizers or the energetic poly-glycidyl azide.Admixture of RDX or HMX,respectively,into the BCHX PBXs gives ternary PBXs whose thermal stability,in the sense of applied VST,is higher comparing to the original binary explosives.展开更多
To study the mechanism of unsteady heat-moisture transfer of wet surrounding rock in deep mining, a series of experiments with different initial and boundary conditions were carried out. Test results show that rock te...To study the mechanism of unsteady heat-moisture transfer of wet surrounding rock in deep mining, a series of experiments with different initial and boundary conditions were carried out. Test results show that rock temperature decreases quickly at the initial stage, and reduces slowly to be a constant value finally for transient heat-moisture transfer. The quasi-steady surface temperature of wet airway is lower than that of dry airway due to the moisture transfer. The diffusion radius is less than the cooling radius owing to the large diffusion resistance. The outlet airflow enthalpy of wet airway is much larger than that of dry airway. Latent heat caused by the moisture transfer plays a significant role in a deep thermal environment. For periodic heat-moisture transfer, temperature, humidity and enthalpy of outlet airflow and rock temperature also change periodically. The wave amplitude of rock temperature decreases gradually with increasing distance away from the airway surface, and the wave phase of rock temperature is also behind that of airflow. Moreover, direction of the heat-moisture transfer between airway and airflow is bidirectional, which is different from results of transient transfer.展开更多
Application of thermal electrochemical equation to metal-hydride half-cell system was investigated, and the influence of state of charge on the thermal electrochemical performance of hydrogen storage materials was stu...Application of thermal electrochemical equation to metal-hydride half-cell system was investigated, and the influence of state of charge on the thermal electrochemical performance of hydrogen storage materials was studied. The results show that both the absolute value of the molar enthalpy change and the internal resistance of evolution hydrogen reaction are less than that of absorption hydrogen reaction at the same state of charge. The molar reaction enthalpy change of absorption and evolution of hydride electrode change contrarily with the enhancement of filling degree of hydrogen in hydride electrode. The relation curve of molar reaction enthslpy change to state of charge, both absorption and evolution hydrogen reaction, is close to a constant when the state of charge is 10%- 60%, and during state of charge below 10% or state of charge above 60%, the molar reaction enthalpy change varies sharply. Meanwhile, the internal resistance of electrode reaction has an ascending trend with the enhancement on filling degree of hydrogen in hydride electrode in both absorption and evolution hydrogen reaction.展开更多
The heat effect of the reaction between metallic aluminum and HCl(aq) solution of various concentrations were calorimetrically determined. Combining with the thermodynamic properties of related substances led to the ...The heat effect of the reaction between metallic aluminum and HCl(aq) solution of various concentrations were calorimetrically determined. Combining with the thermodynamic properties of related substances led to the thermodynamic properties of Al3+ (aq)展开更多
The work addresses to the study of the molecular and crystal structure and properties of a new energyintensive compound 3,6-bis(2,2,2-trinitroethylnitramino)-1,2,4,5-tetrazine(NBTAT),first obtained by the authors in 2...The work addresses to the study of the molecular and crystal structure and properties of a new energyintensive compound 3,6-bis(2,2,2-trinitroethylnitramino)-1,2,4,5-tetrazine(NBTAT),first obtained by the authors in 2020.NBTAT compound crystallizes in the monoclinic system,space group P2(1)/n,density at room temperature 1.939 g/cm^(3).The energies of crystal packing and pairwise intermolecular interactions in NBTAT and its unnitrated analogue BTAT were calculated,and their comparative analysis was carried out.The enthalpy of formation of NBTAT molecules was calculated by quantum-chemical methods using Gaussian 09,and the enthalpy of formation of NBTAT in the solid phase(618 kJ/mol)was estimated.The energy capabilities of NBTAT as an oxidizer of solid composite propellants are estimated.It is shown that in metal-free compositions NBTAT is significantly superior to ammonium perchlorate(AP),dinitramide ammonium salt(ADN),HMX,BTAT at all stages of rocket systems,and is comparable to the superdense CL-20 yielding to the latter at the lower stages and slightly winning at the upper stages.展开更多
The dissolving processes,thermochemical properties and thermokinetic parameters of manganese carbohydrazide styph-nate([Mn2(CHZ)2(TNR)2(H2O)4]),nickel carbohydrazide styphnate([Ni(CHZ),(TNR)],)and lead carbohydrazide ...The dissolving processes,thermochemical properties and thermokinetic parameters of manganese carbohydrazide styph-nate([Mn2(CHZ)2(TNR)2(H2O)4]),nickel carbohydrazide styphnate([Ni(CHZ),(TNR)],)and lead carbohydrazide styphnate([Pb_(2)(CHZ)_(2)(TNR)_(2)(H_(2)O)_(2)])in N,N-dimethylformamide(DMF)at 298,15 K were studied by a SETARAM C80 calorime-ter.The results show that the dissolving process of them in DMF are exothermic,however the exothermic peaks are different.The results are associated with the different molecular structure and polarity of solutes.The empirical formulas for the enthalpies of dis-solution(△mH),the relative apparent molar enthalpies(ΦL;),the relative partial molar enthalpies(L,),and the enthalpies of di-lution(△aHt.:)are respectively deduced by polynomial fitting of experimental data.The standard enthalpies of dissolution(Aai H)are calculated respectively as-17.75kJ·mol^(-1),-29.76kJ·mol^(-1)and-15.35 kJ·mol^(-1).The rate constant of dissolution reaction(k),and the reaction order(n)are obtained from the kinetic formulas.展开更多
文摘Based on thermoelectrochemical equation for an electrode reaction, the entropy change of it can be obtained by the thermoelectrochemical technology(TECT). The entropy changes of Fe(CN)-36/Fe(CN)-46,H+/H2(P0), Cu+2/Cu and Zn+2/Zn electrode reaction systems and the dilute enthalpies of the H+, Cu2+ and Zn2+ ions under the ion concentrations studied have been determined by a specially designed thermoelectrochemical equipment. The enthalpy change and entropy change for the five systems at unlimitedly diluted concentrations agree well with the literature.
基金supported by means of the financial resources of Students Grant Projects No. SGS_2018_002 of the Faculty of Chemical Technology at the University of Pardubice
文摘Information about the forty nine nitraminic plastic bonded explosives(PBXs)and different nitramines were collected.Fillers of these PBXs are nitramines 1,3,5-trinitro-1,3,5-triazinane(RDX)and β-1,3,5,7-tetranitro-1,3,5-tetrazocane(β-HMX),cis-1,3,4,6-tetranitro-octahydroimidazo-[4,5-d]imidazole(bicyclo-HMX,BCHMX)and e-2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane(e-HNIW,CL-20)which are bonded by polyfluoro-elastomers,polydimethyl-siloxane,poly-glycidyl azide,polyisobutylene,polystyrene-butadiene,poly-acrylonitrile-butadiene and hydroxyl-terminated polybutadiene in addition to a melt cast compositions based on 2,4,6-trinitrotoluene.For thirty two of these PBXs the relationships are specified and analyzed between heats of their combustion and relative explosive strengths;by means of these relationships it might be possible to estimate,which groupings in the macromolecule of binder could be liable to their primary fission in the PBXs initiation.Similarly,for forty two of these explosives,the relationships are described and analyzed between their enthalpies of formation and impact sensitivities;here is especially attention paid to PBXs filled by BCHMX.Specific rate constants from Vacuum Stability Test(VST)of four nitramines and twenty PBXs are introduced into relationships with their enthalpies of formation.Regarding to all the mentioned cases,increasing of energy content of the studied explosives leads to increase of the relative explosive strength or initiation reactivity,respectively.Exception with the opposite trend,the outputs of VST are for BCHMX,where in PBXs are matrices with the esteric plasticizers or the energetic poly-glycidyl azide.Admixture of RDX or HMX,respectively,into the BCHX PBXs gives ternary PBXs whose thermal stability,in the sense of applied VST,is higher comparing to the original binary explosives.
基金Foundation item： Project（2012CB026103） supported by the National Basic Research Program of China Project（51204170） supported by the National Natural Science Foundation of China+2 种基金 Project（2011M500974） supported by Postdoctoral Science Foundation of China Project （2011QNA16） supported by Fundamental Research Funds for the Central Universities, China Project（PDll01） supported by Postdoctoral Foundation of State Key Laboratory for Geomechanics and Deep Underground Engineering, China
文摘To study the mechanism of unsteady heat-moisture transfer of wet surrounding rock in deep mining, a series of experiments with different initial and boundary conditions were carried out. Test results show that rock temperature decreases quickly at the initial stage, and reduces slowly to be a constant value finally for transient heat-moisture transfer. The quasi-steady surface temperature of wet airway is lower than that of dry airway due to the moisture transfer. The diffusion radius is less than the cooling radius owing to the large diffusion resistance. The outlet airflow enthalpy of wet airway is much larger than that of dry airway. Latent heat caused by the moisture transfer plays a significant role in a deep thermal environment. For periodic heat-moisture transfer, temperature, humidity and enthalpy of outlet airflow and rock temperature also change periodically. The wave amplitude of rock temperature decreases gradually with increasing distance away from the airway surface, and the wave phase of rock temperature is also behind that of airflow. Moreover, direction of the heat-moisture transfer between airway and airflow is bidirectional, which is different from results of transient transfer.
基金Project(2001AA501433) supported by the National High Technology Research and Development Programof China
文摘Application of thermal electrochemical equation to metal-hydride half-cell system was investigated, and the influence of state of charge on the thermal electrochemical performance of hydrogen storage materials was studied. The results show that both the absolute value of the molar enthalpy change and the internal resistance of evolution hydrogen reaction are less than that of absorption hydrogen reaction at the same state of charge. The molar reaction enthalpy change of absorption and evolution of hydride electrode change contrarily with the enhancement of filling degree of hydrogen in hydride electrode. The relation curve of molar reaction enthslpy change to state of charge, both absorption and evolution hydrogen reaction, is close to a constant when the state of charge is 10%- 60%, and during state of charge below 10% or state of charge above 60%, the molar reaction enthalpy change varies sharply. Meanwhile, the internal resistance of electrode reaction has an ascending trend with the enhancement on filling degree of hydrogen in hydride electrode in both absorption and evolution hydrogen reaction.
文摘The heat effect of the reaction between metallic aluminum and HCl(aq) solution of various concentrations were calorimetrically determined. Combining with the thermodynamic properties of related substances led to the thermodynamic properties of Al3+ (aq)
基金The Ministry of Science and Higher Education of the Russian Federation(Agreement with Zelinsky Institute of Organic Chemistry RAS No 075-15-2020-803).
文摘The work addresses to the study of the molecular and crystal structure and properties of a new energyintensive compound 3,6-bis(2,2,2-trinitroethylnitramino)-1,2,4,5-tetrazine(NBTAT),first obtained by the authors in 2020.NBTAT compound crystallizes in the monoclinic system,space group P2(1)/n,density at room temperature 1.939 g/cm^(3).The energies of crystal packing and pairwise intermolecular interactions in NBTAT and its unnitrated analogue BTAT were calculated,and their comparative analysis was carried out.The enthalpy of formation of NBTAT molecules was calculated by quantum-chemical methods using Gaussian 09,and the enthalpy of formation of NBTAT in the solid phase(618 kJ/mol)was estimated.The energy capabilities of NBTAT as an oxidizer of solid composite propellants are estimated.It is shown that in metal-free compositions NBTAT is significantly superior to ammonium perchlorate(AP),dinitramide ammonium salt(ADN),HMX,BTAT at all stages of rocket systems,and is comparable to the superdense CL-20 yielding to the latter at the lower stages and slightly winning at the upper stages.
基金Technology fund on Applied Physical Chemistry Laboratory(9140C3703051105 and 9140C370303120C37142)State Key Laboratory of Explosion Science and Technology(QNKT12-02)
文摘The dissolving processes,thermochemical properties and thermokinetic parameters of manganese carbohydrazide styph-nate([Mn2(CHZ)2(TNR)2(H2O)4]),nickel carbohydrazide styphnate([Ni(CHZ),(TNR)],)and lead carbohydrazide styphnate([Pb_(2)(CHZ)_(2)(TNR)_(2)(H_(2)O)_(2)])in N,N-dimethylformamide(DMF)at 298,15 K were studied by a SETARAM C80 calorime-ter.The results show that the dissolving process of them in DMF are exothermic,however the exothermic peaks are different.The results are associated with the different molecular structure and polarity of solutes.The empirical formulas for the enthalpies of dis-solution(△mH),the relative apparent molar enthalpies(ΦL;),the relative partial molar enthalpies(L,),and the enthalpies of di-lution(△aHt.:)are respectively deduced by polynomial fitting of experimental data.The standard enthalpies of dissolution(Aai H)are calculated respectively as-17.75kJ·mol^(-1),-29.76kJ·mol^(-1)and-15.35 kJ·mol^(-1).The rate constant of dissolution reaction(k),and the reaction order(n)are obtained from the kinetic formulas.
