Hume-Rothery Rules

Hume-Rothery Rules are a set of basic rules describing the conditions under which an
element could dissolve in a metal, forming a solid solution. There are two sets of rules,
one which refers to substitutional solid solutions, and another which refers to interstitial
solid solutions.

Hume-Rothery first pointed out that these intermediate phases are found to exist at or
near compositions in each system that have a definite ratio of valence electrons to atoms
and are therefore called electron compounds.

The Hume-Rothery rules give the conditions that have to be satisfied for metallic solid
solutions to form:

1. Concerns the atomic size factor and claims that if the atomic diameter of the
solvent differs in size from that of the solute by more than 14%, the chances of
solubility are small.

2. The more electronegative is one component and the more electropositive the
other, the more they are likely to form compounds rather than solutions. And,
finally, a metal of lower valency is more likely to dissolve one of higher valency
than vice versa.

Substitutional Solid Solution

In this type of solution, the atoms of the solute substitute for atoms of the solvent in the
lattice structure of the solvent.

For example, silver atoms may substitute for gold atoms without losing the f.c.c. (face-
centered cubic) structure of gold, and gold atoms may substitute for silver atoms in the
f.c.c. lattice structure of silver.

All alloys in the silver-gold system consist of an f.c.c. lattice with silver and gold atoms
distributed at random through the lattice structure .This entire system consists of a
continuous series of solid solutions
In substitutional solid solution, the arrangement of the solute atoms may
be disordered (random) or ordered.

Some alloy systems exhibit complete solid solubility (e.g. Cu-Ni, Cd-Mg), others show
only limited solubility at any temperature

Several factors determine the limits of solubility. These are expressed as a series of rules
often called William Hume-Rothery Rules. These are:

Hume-Rothery Rule 1:Atomic Size Factor (the 15%) Rule.

Extensive substitutional solid solution occurs only if the relative difference between the
atomic diameters (radii) of the two species is less than 15%. If the difference > 15%, the
solubility is limited. Comparing the atomic radii of solids that form solid solutions, the
empirical rule given by Hume-Rothery is given as:
Hume-Rothery Rule 2: Crystal Structure Rule.

For appreciable solid solubility, the crystal structures of the two elements must be
identical.

Hume-Rothery Rule 3: Valency Rule.

A metal will dissolve a metal of higher valency to a greater extent than one of lower
valency. The solute and solvent atoms should typically have the same valence in order to
achieve maximum solubility.

Hume-Rothery Rule 4: The Electronegativity Rule.

Electronegativity difference close to 0 gives maximum solubility.The more

electropositive one element and the more electronegative the other, the greater is the
likelihood that they will form an intermetallic compound instead of a substitutional solid
solution. The solute and the solvent should lie relatively close in the electrochemical
series.

Interstitial Solid Solutions

These are formed when atoms of small atomic radii fit into the spaces or interstices of the
lattice structure of the larger solvent atoms.

Since the spaces of the lattice structure are restricted in size, only atoms with atomic radii
less than 1 angstrom are likely to form interstitial solid solutions.

Interstitial solid solutions normally have very limited solubility and generally are of little
importance. Carbon in iron is a notable exception and forms the basis for hardening steel.

Similar to Hume-Rothery rules can be applied for interstitial solid solutions, Interstitial
solid solutions are formed if:

1. Solute atoms must be smaller than the pores in the solvent lattice.
2. The solute and solvent should have similar electronegativity.
There are very few elements that create ions, small enough to fit in interstitial positions,
therefore, appreciable solubility is rare for interstitial solid solutions. Ions that often may
be a solute in solid solutions are: H, Li, Na, B. Most interstitial solid solutions have a
strong tendency to spontaneous ordering. Examples of ordered or partially interstitial
solid solutions PdHn, AlLin, BeLi.

Examples and applications

FIGURE: Classification scheme for the various alloys