硝酸1-烷基-4-氨基-1,2,4-三唑鎓含能离子液体的蒸气压及其摩尔汽化焓的理论研究
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摘要
合成了硝酸1-烷基-4-氨基-1,2,4-三唑鎓含能离子液体([RATZ]NO3),并通过核磁和红外进行了结构表征;采用Gaussian09/B3LYP/6-311+G(d,p)密度泛函理论计算了[RATZ]NO3的离子间相互作用能及摩尔体积;在298K～323K温度范围内,测定了不同配比[RATZ]NO3-Et OH混合溶液的饱和蒸气压。研究了[RATZ]NO3-Et OH混合溶液的饱和蒸气压、[RATZ]NO3的蒸气压及摩尔汽化焓与温度、离子间相互作用能以及结构之间的关系。结果表明,[RATZ]NO3-Et OH混合溶液的饱和蒸气压随温度的升高、离子间作用能的减小以及阳离子体积的增大而增大,其沸点比纯溶剂高,且在298K～323K温度范围内[RATZ]NO3的平衡蒸气压均低于250mPa,说明含能离子液体具有不挥发性;通过理论计算得到离子间相互作用能及体积,解释了[RATZ]NO3的摩尔汽化焓随烷基链增长而降低的原因。
1-Alkyl-4-amino-1,2,4-triazolium nitrate energetic ionic liquids(EILs) were synthesized and characterized by1 H NMR and FT-IR.Their interaction energies of ion pairs and standard molar volume were calculated by DFT/B3 LYP/6-311+G(d,p).The saturated vapor pressure of different molar ratio(xA,EtOH= 0.984,0.996,0.999 and 1.000) of the [RATZ]NO3-EtOH mixed solution were measured within the temperature range of 303 K ～ 353 K.The relationship between the saturated vapor pressure of [RATZ]NO3-EtOH,vapor pressure and molar enthalpy of vaporization of [RATZ]NO3 and temperature(303 to 353) K,molecular structure,and the interaction energies of ion pairs were discussed.The results showed that the saturated vapor pressure of [RATZ]NO3-EtOH mixed solution increases with the increase of temperature,the decrease of interionic energy and the increase of cation size,and its boiling point is higher than that of pure solvent(EtOH).The vapor pressure of vaporization of [RATZ]NO3 are lower than 250 mPa at 303 K ～ 353 K,indicating that the energetic ionic liquid is non-volatile.Finally,the reason of the molar enthalpy of vaporization of [RATZ]NO3 decreases with the elongation of the alkyl chain length on cation is explained by the cation size and interaction energies of ion pairs through calculation.
1-Alkyl-4-amino-1,2,4-triazolium nitrate energetic ionic liquids(EILs) were synthesized and characterized by1 H NMR and FT-IR.Their interaction energies of ion pairs and standard molar volume were calculated by DFT/B3 LYP/6-311+G(d,p).The saturated vapor pressure of different molar ratio(xA,EtOH= 0.984,0.996,0.999 and 1.000) of the [RATZ]NO3-EtOH mixed solution were measured within the temperature range of 303 K ～ 353 K.The relationship between the saturated vapor pressure of [RATZ]NO3-EtOH,vapor pressure and molar enthalpy of vaporization of [RATZ]NO3 and temperature(303 to 353) K,molecular structure,and the interaction energies of ion pairs were discussed.The results showed that the saturated vapor pressure of [RATZ]NO3-EtOH mixed solution increases with the increase of temperature,the decrease of interionic energy and the increase of cation size,and its boiling point is higher than that of pure solvent(EtOH).The vapor pressure of vaporization of [RATZ]NO3 are lower than 250 mPa at 303 K ～ 353 K,indicating that the energetic ionic liquid is non-volatile.Finally,the reason of the molar enthalpy of vaporization of [RATZ]NO3 decreases with the elongation of the alkyl chain length on cation is explained by the cation size and interaction energies of ion pairs through calculation.
引文
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[7]M Armand,F Endres,D R Mac Farlane et al.Nat.Mater.,2009,8:621~629.
[8]Y Yoshida,G Saito.Phys.Chem.Chem.Phys.,2010,12(8):1675~1684.
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[10]Y Wei,Y Jin,Z J Wu et al.J.Chem.Eng.Data,2013,58(2):349~356.
[11]Q S Liu,P P Li,U Welz-Biermann et al.J.Chem.Eng.Data,2012,57:2999~3004.
[12]P Navarro,M Larriba,E Rojo et al.J.Chem.Eng.Data,2013,58(8):2187~2193.
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