Fajans' rules

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In inorganic chemistry, Fajans' rules, formulated by Kazimierz Fajans in 1923, [1] [2] [3] are used to predict whether a chemical bond will be covalent or ionic, and depend on the charge on the cation and the relative sizes of the cation and anion. They can be summarized in the following table:

Chart illustrating the relationship between atomic and ionic radius Atomic vs Ionic Radius.png
Chart illustrating the relationship between atomic and ionic radius
Ionic CharacterCovalent Character
Low positive chargeHigh positive charge
Large cationSmall cation
Small anionLarge anion

Although the bond in a compound like X+Y- may be considered to be 100% ionic, it will always have some degree of covalent character. When two oppositely charged ions (X+ and Y-) approach each other, the cation attracts electrons in the outermost shell of the anion but repels the positively charged nucleus. This results in a distortion, deformation or polarization of the anion. If the degree of polarization is quite small, an ionic bond is formed, while if the degree of polarization is large, a covalent bond results. [4]

Non-polar covalent bond (left), polar covalent bond (center), ionic bond(right) Covalent and ionic bonds.jpg
Non-polar covalent bond (left), polar covalent bond (center), ionic bond(right)

Polarization of the anion depends upon:

Two contrasting examples can illustrate the variation in effects:

Graph of percentage ionic character Ionic character vs electronegativity 01.jpg
Graph of percentage ionic character

Thus sodium chloride (due to a relatively large cation) and aluminum fluoride (due to a relatively small anion) are both ionic; but aluminium iodide is covalent. Likewise, CaCl2 (having a noble gas configuration in cation,) is ionic but HgCl2 is covalent.

References

  1. Fajans, K. (1923). "Struktur und Deformation der Elektronenhüllen in ihrer Bedeutung für die chemischen und optischen Eigenschaften anorganischer Verbindungen". Die Naturwissenschaften . 11 (10): 165–72. Bibcode:1923NW.....11..165F. doi:10.1007/BF01552365.
  2. Fajans, K.; Joos, G (1924). "Molrefraktion von Ionen und Molekülen im Lichte der Atomstruktur". Zeitschrift für Physik . 23: 1–46. Bibcode:1924ZPhy...23....1F. doi:10.1007/BF01327574.
  3. Fajans, K. (1924). "II. Die Eigenschaften salzartiger Verbindungen und Atombau" . Zeitschrift für Kristallographie - Crystalline Materials. 61 (1): 18–48. doi:10.1524/zkri.1924.61.1.18.
  4. "Polarizability". Chemistry LibreTexts. 2015-11-27. Retrieved 2024-12-30.