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THERMOCHEMICAL AND THERMODYNAMICAL PROPERTIES OF M(NTO)n AND M(NTO)n·mH2O
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    Abstract:

    The enthalpies of solution in water of twenty M(NTO)n·mH2O(M=metal;NTO=3-nitro-1,2,4-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=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)and the enthalpies of precipitation of KNTO·H2O(cr)with CuSO4(aq),Pb(NO3)2(aq)and Zn(NO3)2(aq)have been measured calorimetrically at 298.15K.By using the enthalpies of solution and those of precipitation,the standard enthalpies of formation of above twenty M(NTO)n·mH2O and three precipitates of [Cu(NTO)2·2H2O,Pb(NTO)2·2H2O and Zn(NTO)2·2H2O]were obtained.With the help of Kapustinskii's equation and literature data,the walues of the lattice energies (△UOL)and lattice enthalpies (△HOL)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 are following linear relationships between the values of-△UOLand-△HOL of lanthanide metal salts of NTO and the atomic numbers (Z)and ionic radii (r) of lanthanide elements;△UOL=-2840-14.55Z,the correlation coefficient R'=-0.9941;△UOL=-4664+950.6r,R'=0.9983;△HOL=-2837-14.77Z,R'=-0.9955;△HOL=-4689+964.8r·R'=0.9998.The magnitude of the lattice 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 -△UOL[M(NTO)3] increase with contraction of ionic radius.This shows that lattice energy is in reciprocal ratio to the ionic radius of rare earth cations.According to the lattice enthalpies of M(NTO)n,the standard enthalpies of formation of gaseous ions of metals and the standard enthalpies of formation of NTO-(g) derived from the standard enthalpies of formation of KNTO,NaNTO and NH4KNTO crystal,the atandard enthalpies of formation (△sup>fHOm)of above twenty M(NTO)n were obtained.The results show that the following relationships hold;△sup>fHOm=-1873+17.57Z,(except Eu and Yb),R'=0.9865;△sup>fHOm=266.5-1083r,(except Eu and Yb),R'=-0.9920.With the help of the standard enthalpies of formation of M(NTO)n·mH2O(cr),Mn-(g) and NTO-(g),the lattice enthalpies and lattice energies of twenty M(NTO)n·mH2O(M=Li,n=1,m=2;M=Na,K,n=1,m=1;M=Mg,Mn,Co,n=2;m=8;M=Ca,n=2,m=4;M=Cu,n=m=2;M=Zn,n=2,m=1;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) were obtained,By means of the thermochemical equations of the above twenty M(NTO)n·mH2O,their standard enthalpies of dehydration were obtained.

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胡荣祖,孟子晖. M(NTO)n和M(NTO)n. mH2O的热化学和热力学性质[J].含能材料,1995,3(3):9-27.
Hu Rong-zu, Meng Zi-hui. THERMOCHEMICAL AND THERMODYNAMICAL PROPERTIES OF M(NTO)n AND M(NTO)n·mH2O[J]. Chinese Journal of Energetic Materials,1995,3(3):9-27.

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  • Received:June 16,1995
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  • Online: November 02,2011
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