离子极化和离子晶体的晶格能——离子极化能的理论计算和适用于所有离子晶体的晶格能公式

A theoretical formula has been developed for the calculation of polarization energy in ionic erystals by using the concept of effective nuclear charge and theorems in electrostatics Up=-1/2 NBZ^*e^2α r0^A This applies to all types of crystals, i.e., nonstandard as well as standard type erystals with a small polarization energy. Ionic polarization energies of 393 compounds and lattice energies of 330 compounds were calculated with this formula, and the agreement between calculated and experimental values is generally good.     

晶体化学第二定律研究水滑石热稳定性与离子交换性能

水滑石层间阴离子热稳定性、离子交换性能等物化性质与LDHs材料主客体间以静电作用为主的超分子作用密切相关,但LDHs材料的晶格能计算目前仍相当困难。本文以层间阴离子作为负电荷基团、对应等电量氢氧化物层板作为正电荷基团,构建水滑石(LDHs)主客体静电作用模型。采用晶体化学第二定律,对LDHs材料晶格能进行理论计算,并与层间阴离子交换性能以及热稳定性等物化性质进行了比较。研究结果表明:改变层间阴离子种类,晶格能大小次序为Mg3Al-F-LDHs>Mg3Al-OH-LDHs>Mg3Al-Cl-LDHs>Mg3Al-Br-LDHs>Mg3Al-I-LDH,Mg3Al-CO3-LDHs>Mg3Al-CrO4-LDHs>Mg3Al-SO4-LDHs>Mg3Al-NO3-LDHs,与文献报道的LDHs层间阴离子交换性能相一致。改变层板金属离子比例,计算得到晶格能大小顺序为Mg2Al-CO3-LDHs>Mg3Al-CO3-LDHs>Mg4Al-CO3-LDHs,与层间碳酸根热稳定性相一致。改变层板金属离子种类,预测得到层间碳酸根热稳定顺序为:Mg3Al-CO3-LDHs>Cu3Al-CO3-LDHs>Ni3Al-CO3-LDHs>Zn3Al-CO3-LDHs-Co3Al-CO3-LDHs>Fe3Al-CO3-LDHs>Mn3Al-CO3-LDHs>Cd3Al-CO3-LDHs>Ca3Al-CO3-LDHs;Mg3Al-CO3-LDHs>Mg3Ni-CO3-LDHs-Mg3Co-CO3-LDHs-Mg3Fe-CO3-LDHs>Mg3Cr-CO3-LDHs。本文中对于LDHs材料晶格能的计算,为其热稳定性与离子交换性能的预测提供了理论依据。此外,LDHs材料的静电作用模型构建方法,对于其他层状主客体材料晶格能计算也有较高的参考价值。     

稀土掺杂板钛矿的光催化活性的第一性原理研究

基于第一性原理,以板钛矿相TiO2和稀土掺杂板钛矿相TiO2原胞为基本模型,利用MS4.0软件的castep模块结合ATK软件计算了17种稀土掺杂板钛矿相TiO2的态密度、晶格能和能隙等参数。结果证实,除Sc、Y外,其余稀土元素均有利于降低板钛矿相TiO2的能隙,这一现象与稀土外层的4f电子结构相对应。Sc和Y有利于降低板钛矿相TiO2的晶体形成能,这与此类化合物的合成能相关。     

氯化镁及其水合物的标准溶解焓与生成焓

利用精密量热仪测定了MgCl_2、MgCl_2·2H_2O、MgCl_2·4H_2O和MgCl_2·6H_2O在298.15°K溶于水的积分溶解热,并利用Pitzer电解质溶液的。~ΦL方程,计算了溶质的相对表观摩尔热焓,从而得到标准溶解焓分别为(KJ·mol~(-1))—155.86±0.17、—79.45±O.17,—41.78±O.18和—14.58±0.16;晶格能分别为—2490.36,—3158.37,—3772.70和—4376.56。二、四、六水合物的标准生成焓分别为—1289.39,—1898.72和—2497.58;水合焓分别为—76.41,—114.08和—141.28。     

离子极化和离子晶体的晶格能——离子极化能的经验计算和非标准型离子晶体的晶格能

In this paper, the discrepancy between lattice energies theoretically calculated and those experimentally determined for the ionic crystals which contain ions having non-inert gas configuration is discussed with the Fajans‘ concept of ionic polarization.Thus, the actual lattice energy U is expressed as the sum of the purely ionic lattice energy Ui calculated from Kapustinskii equation and the polarization energy Up;U=Ui Up An empirical equation is proposed to calculate ionic polarization energy;Up=α Z^*2/r bα c where Z^*z/r is the polarizing power of the cation,a is the polarizability of the anion,ar b and c are the empirical constants which depend on the type of the compounds concerned.Using above expressions,lattice energies of 317 non-standard type erystalline compounds are caleulated and the results well agree with the experimental values and are better than the ealeulations by other authors.     

论太平洋水体中元素行为的周期性

尽管海洋水及自生矿物相的复杂性，但我们仍发现了：１．周期表中的绝大多数元素在海洋铁锰结核氧化物中的富集程度Ｋｐ、在海水中的滞留时间τ，以及在氧化物相中的晶格能ｕ三参数间存在非常好的相关性；２．该三参数各自随元素原子序数的增加而展示出了好的化学周期性；３．晶格能ｕ是控制化学元素在海洋中的行为和迁移等性质的一极其重要参数．