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晶格能

離子化合物晶格能是指在標準條件中(298K,1atm),由相距无穷远的气态正、负离子形成1 mol 離子晶体所释放的能量,或是1 mol 離子晶体变成相距无穷远的气态正、负离子所吸收的能量。离子半径越小,晶格能越大。而离子的电荷越大,晶格能就越大。晶格能的大小与溶解度,硬度,挥发性等诸多物理性质相关。晶格能通常不能直接测出,但可通过玻恩-哈伯循环计算出。

你也可以通过伯恩-兰德方程计算出晶格能

公式为U=(1-1/n)138490Z+Z-A/r

其中Z+与Z-分别代表阳离子与阴离子的电荷数的绝对值r为阴阳离子半径的和(单位取pm),A则为马德隆常数,与晶格类型有关。[1]

意义

[编辑]

晶格能的概念最早应用于岩盐氯化钠)与闪锌矿硫化锌)等高对称性的矿物形成过程中。以氯化钠为例,晶格能为以下反应的能量变化:

Na+ (g) + Cl (g) → NaCl (s)

其数值大小约为-786kJ/mol。[2]

除此之外,部分教科书[3]采取上过程的相反过程作为晶格能的定义。在这种定义下,晶格能的符号为正号。两种定义的应用都很广泛。

部分有代表性的晶格能值

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化合物 实验测得的晶格能[4] 晶体类型 备注
LiF −1030 kJ/mol NaCl 由于离子势更大,使得晶格能随之上升
NaCl −786 kJ/mol NaCl 氯化钠晶型的标准物质
NaBr −747 kJ/mol NaCl 比氯化钠更弱的晶格
NaI −704 kJ/mol NaCl 比溴化钠更弱的晶格,在丙酮中可溶
CsCl −657 kJ/mol CsCl 氯化铯晶型的标准物质
CsBr −632 kJ/mol CsCl 趋势与氯化钠晶型相同
CsI −600 kJ/mol CsCl 趋势与氯化铯晶型相同
MgO −3795 kJ/mol NaCl M2+R2-的晶格能比M+R-显著高,其在绝大多数溶剂中难溶
CaO −3414 kJ/mol NaCl M2+R2-的晶格能比M+R-显著高,其在绝大多数溶剂中难溶
SrO −3217 kJ/mol NaCl M2+R2-的晶格能比M+R-显著高,其在绝大多数溶剂中难溶
MgF2 −2922 kJ/mol
TiO2 −12150 kJ/mol


  1. ^ 宋, 天佑. 无机化学. 吉林大学: 高等教育. 2015: 232. ISBN 978-7-04-042426-3. 
  2. ^ Johnson, D. A.; Open University. Metals and chemical change. Cambridge: Royal Society of Chemistry https://www.worldcat.org/oclc/232637537. 2002. ISBN 978-1-84755-791-9. OCLC 232637537.  缺少或|title=为空 (帮助)
  3. ^ Zumdahl, Steven S. Chemistry. 4th ed. Boston: Houghton Mifflin https://www.worldcat.org/oclc/36896511. 1997. ISBN 0-669-41794-7. OCLC 36896511.  缺少或|title=为空 (帮助)
  4. ^ Atkins, P. W. Shriver & Atkins' inorganic chemistry. 5th ed. Oxford: Oxford University Press https://www.worldcat.org/oclc/430678988. 2010. ISBN 978-0-19-923617-6. OCLC 430678988.  缺少或|title=为空 (帮助)
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晶格能
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