摘要
本文着重介绍了用Ｃａｉｖｅｔ微量热量计在２９８．１５Ｋ下测定了２０种Ｍ（ＮＴＯ）．·ｍＨ＿２Ｏ（Ｍ＝金属；ＮＴＯ＝３－硝基－１．２．４－三唑－５－酮；Ｍ＝Ｌｉ，ｎ＝１，ｍ＝２：Ｍ＝Ｎａ，Ｋ，ｎ＝１，ｍ＝１；Ｍ＝Ｍｇ．Ｍｎ，Ｃｏ，Ｎｉ，ｎ＝２，ｍ＝８；Ｍ＝Ｃａ，ｎ＝２，ｍ＝４；Ｍ＝Ｂａ，ｎ＝２，ｍ＝３；Ｍ＝Ｙ、Ｙｂ，ｎ＝３，ｍ＝６；Ｍ＝Ｌａ，Ｃｅ，Ｐｒ．Ｓｍ，Ｅｕ，Ｇｄ，ｎ＝３，ｍ＝７；Ｍ＝Ｎｄ，ｎ＝３，ｍ＝８；Ｍ＝Ｔｂ；Ｄｙ，ｎ＝３；ｍ＝５）在水中的溶解焓和ＫＮＴＯ·Ｈ＿２Ｏ（ｃｒ）与ＣｕＳＯ＿４（ａｑ）、Ｐｂ（ＮＯ＿３）＿２（ａｑ）和Ｚｎ（ＮＯ＿３）＿２（ａｑ）的沉淀反应焓．利用测得的溶解焓和沉淀反应治数据，计算了这２０种Ｍ（ＮＴＯ）＿ｎ·ｍＨ＿２Ｏ和３种沉淀反应产物（Ｃｕ（ＮＴＯ）＿２·２Ｈ＿２Ｏ，Ｐｂ（ＮＴＯ）＿２·Ｈ＿２Ｏ和Ｚｎ（ＮＴＯ）＿２·Ｈ＿２Ｏ）的标准生成焓。用Ｋａｐｕｓｔｉｎｓｋｉｉ公式计算了２０种Ｍ（ＮＴＯ）＿ｎ（Ｍ＝Ｌｉ．Ｎａ，Ｋ，ｎ＝１；Ｍ＝Ｍｇ，Ｇａ，Ｍｎ，Ｃｏ，Ｃｕ，Ｚｎ，ｎ＝２；Ｍ＝Ｙ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，Ｇｄ，Ｔｂ，Ｄｙ，Ｙｂ．ｎ＝３）的晶格能，进而算出了它们?
The enthalpies of solution in water of twenty M (NTO)_n·mH_2O(M=metal; NTO=3-nitrol-2.4-triazol-5-one;M=Li,n=1,m=2;M=Na,K,n=1,m=1;M=Mg,Mn,Co,Ni,n=2,m=8;M=Ca,n=2,m=4;M=Ba,n=2,m=23;M=Y,Yb,n=3,m=6;M=La,Ce,Pr,Sm,Eu,Gd,n=3,m=7;M=Nd,n=3,m=8;M=Tb , Dy,n=3,m=5) and the enthalpies of precipitation of KNTO·H_2O(cr) withCuSO_4(aq)、 Pb(NO_3)_2(aq) and Zn(NO_3)_2(aq)have been measured calorimetrically at298. 15K. By using the entiialpies of solution and those of precipitation, the standardenthalpies of formation of above twenty M (NTO)_n· mH_2O and three precipitates of[Cu(NTO)_2·2H_2O,Pb(NTO)_2·H_2O and Zn(NTO)_2·H_2O]were obtained.With the help of Kapustinskii's equation and literature data,the values of the lattice energiesand lattice enthalpies of twenty M(NTO)_n(M=Li,Na,K,n=1;M=Mg,Ca,Mn·Co,Cu,Zn,n=2;M=Y,La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Yb,n=3)were obtained; The results show that there are following linear relationships betweenthe values of and of lanthanide metal salts of NTO and the atomic num-bers (Z)and ionic radii(r) of lanthanide elements:2840-14. 55Z, the correla-tion coefficient R'=-0. 9941; R'=0. 9983;R'=-0. 9955; R'=0. 9998.The magnitude of the lat-tice energy of Y(NTO)_3 falls between those of Gd(NTO)_3 and Tb(NTO)_3. It has beenproved that yttrium belongs to the group of lanthanide elements. The values of [M(NTO)_3]increase with contraction of ionic radius, This shows that lattice energy isin reciprocal ratio to the ionic radius of rare earth cations. According to the lattice en-thalpies of M(NTO)_n,the standard enthalpies of formation of gaseous ions of metalsand the standard enthalpies of formation of NTO￣-(g)derived from the standard en-thalpies of formation of KNTO,NaNTO and NH_4KNTO crystal , the standard enthalpiesof formation of above twenty M(NTO)_n were obtained. The results show thatthe following relationships hold:(except Eu and Yb),R'=0. 9865; (except Eu and Yb),R'=-0. 9920. With the help ofthe standard enthalpies of formation of M(NTO)_n·mH_2O(cr),M￣(n+)a(g)and NTO￣-(g),the lattice e
出处
《含能材料》
EI
CAS
CSCD
1995年第3期9-27,共19页
Chinese Journal of Energetic Materials
关键词
NTO盐
溶解焓
沉淀反应焓
热化学
热力学性质
NTO salt, enthalpy of solution, enthalpy of precipitation, standard en-thalpy of formation, lattice energy, lattice enthalpy, standard enthalpy of dehydration.
