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Hume-Rothery Rules


Hume-Rothery (1899-1968) was a metallurgist who studied the
alloying of metals. His research was conducted at Oxford
University where in 1958, he was appointed to the first chair
in metallurgy.
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.
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.

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In substitution solid solution, the arrangement of the solute
atoms maybe 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:




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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:
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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 maybe a solute in solid solutions is: H, Li, Na,
B. Most interstitial solid solutions have a strong tendency
to spontaneous ordering.

Industrial application
The phase diagram of the figure shows an alloy of two metals
that form a solid solution to all the relative concentrations
of the two species. In this case, the pure phase of both is
of identical crystal structure, and the similar properties of
the two elements allows partial replacements across the wide
range of relative concentrations of the two metals.

Solid solutions have important commercial and industrial
applications such as mixtures having properties superior to
pure materials. Many metal alloys are solid solutions. Even
small amounts of solute can affect the physical and
electrical properties of the solvent.







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Example:
a) The major component is the solvent, and the minor
component is the solute:
SOLVENT = Cu, SOLUTE = Ni
b) Here's a great chance to use the Hume-Rothery Rules, which
tell us how easily we will form a substitutional solid
solution.
First thing to check- the crystal structures. According to
Schaeffer, et al., both Cu and Ni have the FCC crystal
structure (and they happen to be correct...). This is
necessary to have a good substitutional solid solution.
Second Hume-Rothery Rule (H-R) is atomic size; are they
within about 15% of each other? The atomic radii are the ones
we use, and p 773 tells us that r(Cu) = 128 pm, while r(Ni) =
125 pm (a pm = pico-meter = 1e-12 m). The ratio of these
tells us that the two radii are within about 2.4% of each
other, well within the H-R rule of less than 15%. Another
good indicator of a substitutional solid solution.
Third H-R Rule is electronegativity. The Schaeffer table
gives the electronegativities as EN(Cu) = 1.90 and EN(Ni) =
1.91. Since these are nearly identical, we again satisfy the
H-R rule for a substitutional solution.
Fourth, and final, H-R rule is valence. Since both Cu and Ni
are transition metals, they have the valence electrons in the
4s shell. Ni has 2 electrons there, for a valence of 2, and
Cu has only 1, for a valence of 1. This is the least
important of the H-R rules, and since the valence is very
similar, it is somewhat neutral in determining the liklihood
of forming a substitutional solid solution.
Based on the above reasoning, the chances are very good
that Cu and Ni will form a substitutional solid solution.
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c) Also, based on the above reasoning, Cu and Ni should be
completely soluble in each other.






















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Referencias
http://www.msm.cam.ac.uk/phase-
trans/2004/titanium/hume.rothery.html
http://es.wikipedia.org/wiki/Soluci%C3%B3n_s%C3%B3lida
Hume-Rothery Rules pdf

http://oregonstate.edu/instruct/engr321/Homework/HomeworkW00/HW4.h
tml