CHEM 2060 Lecture 15: Radius Ratio Rules L15-1

Radius Ratio Rule

In ideal ionic crystals, coordination numbers are determined largely by

electrostatic considerations.

• Cations surround themselves with as many anions as possible and vice-versa.

• This can be related to the relative sizes of the ions. ⇒ radius ratio rule

Radius ratio rule states:

• As the size (ionic radius r) of a cation increases, more anions of a

particular size can pack around it.

• Thus, knowing the size of the ions, we should be able to predict a priori
which type of crystal packing will be observed.

• We can account for the relative size of both ions by using the RATIO of
the ionic radii:
r+
ρ= −
r
 CHEM 2060 Lecture 15: Radius Ratio Rules L15-2

Limiting Radius Ratios

For a specific structure, we can calculate the limiting radius ratio, which is the
minimum allowable value for the ratio of ionic radii (r+/r-) for the structure to
be stable.

Let’s start
by looking
at the
CsCl
structure.
 CHEM 2060 Lecture 15: Radius Ratio Rules L15-3

CsCl (8:8) …Let’s calculate the limiting radius ratio for this structure.

2r − + 2r + = 2r − 3
Recall: we know the length of
each side of the triangle: r+
= 3 −1 = 0.732
cube edge (1), face diagonal (√2), body diagonal (√3) r −
 CHEM 2060 Lecture 15: Radius Ratio Rules L15-4

NaCl (6:6) …Now we’ll calculate the limiting r+/r- for rock salt.

The plane is just the face of the unit cell.

Recall: we know the length of
each side of the triangle: 4r − = ( 2r − + 2r + ) 2
cube edge & face diagonal! r+ 2
−
= −1 = 0.414
r 2
 CHEM 2060 Lecture 15: Radius Ratio Rules L15-5

ZnS (4:4) …limiting radius ratio for zinc blende and wurtzite

The easiest plane to select is simply half of a tetrahedron!

1
r− = a 2
4
r− 1
= a
2 4
2
" r− % − 2
' + (r )
− +
r +r = $
# 2&
r+ 6
−
= −1 = 0.225
r 2
 CHEM 2060 Lecture 15: Radius Ratio Rules L15-6

So, there is a range to the radius ratio r+/r- for a given arrangement of ions.

C.N. of cation r+/r- range possible structures

8 (cubic) ≥ 0.732 CsCl, CaF2
6 (octahedral) 0.414 – 0.732 NaCl, TiO2, CdCl2
4 (tetrahedral) 0.225 – 0.414 antifluorite, ZnS
3 (triangular) 0.155 – 0.225

Examples:

r
Be2+
Beryllium sulfide, BeS r 2-
= 0.59
1.7
= 0.35 ∴ C.N. = 4
S

r
Na +
Sodium chloride, NaCl r
= 1.16
1.67
= 0.69 ∴ C.N. = 6
Cl-
€
r
Cs+ 1.81 = 1.08
Cesium chloride, CsCl r
= 1.67 ∴ CN = 8
Cl-
€

€
 CHEM 2060 Lecture 15: Radius Ratio Rules L15-7

Radius Ratio rule doesn’t always

work…

Zinc sulfide, ZnS

r+/r- = 0.52
∴ C.N. = 6 is predicted…WRONG!

Both forms of ZnS (zinc blende and

wurtzite) have C.N.= 4.

QUESTION: Why do you think the Radius Ratio rule breaks down in this
example? (Hint: Remember what we said about assumptions!)
 CHEM 2060 Lecture 15: Radius Ratio Rules L15-8

This graph compares actual structures

with predictions by radius ratio rules
from r+/r-
(r-/r+ if cation is larger – in purple)

NaCl structure is observed more than

is predicted!

Radius ratios are only correct ca. 50%

of the time, not very good for a family
of ionic solids!

(Don’t spend too much time

analyzing this graph…it is only meant
to show you that the radius ratio rules
are not very good at predicting
structures…)
 CHEM 2060 Lecture 15: Radius Ratio Rules L15-9

Close Packing

• An alternative way of looking at ionic solids.

• Anions are often larger than cations and therefore “touch”.

• Small cations then fit in the “holes” between anions.

• Think of co-packing softballs and golf balls in the most efficient way.

1926 Goldschmidt proposed ions could be

considered as hard spheres when packing in
solids.

This reduces the problem of examining the

packing of like atoms to that of examining the
most efficient packing of any spherical object.

e.g., how oranges are most effectively packed…

 CHEM 2060 Lecture 15: Radius Ratio Rules L15-10

CLOSE-PACKING OF SPHERES

A single layer of spheres is closest-packed with

a HEXAGONAL coordination of each sphere!
 CHEM 2060 Lecture 15: Radius Ratio Rules L15-11

A second layer of spheres is placed in the indentations left by the first layer.

Space is trapped between the layers

that is not filled by the spheres:

TWO different types of HOLES (so-

called INTERSTITIAL sites) are
left:

• OCTAHEDRAL (O) holes with 6

nearest sphere neighbors

• TETRAHEDRAL (T±) holes with

4 nearest sphere neighbors
 CHEM 2060 Lecture 15: Radius Ratio Rules L15-12

When a third layer of spheres is placed in the indentations of the second

layer there are TWO choices:

Option #1 - The third layer lies in indentations

directly in line (eclipsed) with the1st layer

Layer ordering may be described as ABA

(hexagonal close packed – hcp)

Option #2 - The third layer lies in the

alternative indentations leaving it staggered
with respect to both previous layers

Layer ordering may be described as ABC

(cubic close packed – ccp)
 CHEM 2060 Lecture 15: Radius Ratio Rules L15-13

Close-Packed Structures

The most efficient way to fill space with spheres

Is there another way of packing spheres that is more space-efficient?

In 1611 Johannes Kepler asserted that there was no way of packing equivalent
spheres at a greater density than that of a face-centered cubic arrangement. This
is now known as the Kepler Conjecture.

This assertion has long remained without rigorous proof, but in August 1998
Prof. Thomas Hales of the University of Michigan announced a computer-based
solution. This proof is contained in over 250 manuscript pages and relies on over
3 gigabytes of computer files and so it will be some time before it has been
checked rigorously by the scientific community to ensure that the Kepler
Conjecture is indeed proven!

An article by Dr. Simon Singh © Daily Telegraph, 13th August 1998

http://www.chem.ox.ac.uk/icl/heyes/structure_of_solids/Lecture1/oranges.html
 CHEM 2060 Lecture 15: Radius Ratio Rules L15-14

Features of Close-Packing

Coordination Number = 12
74% of space is occupied

Simplest Close-Packing Structures

ABABAB.... repeat gives Hexagonal Close-Packing (HCP)

Unit cell showing the full symmetry of the arrangement is Hexagonal
 CHEM 2060 Lecture 15: Radius Ratio Rules L15-15

ABCABC.... repeat gives Cubic Close-Packing (CCP)

Unit cell showing the full symmetry of the arrangement is
Face-Centred Cubic
 CHEM 2060 Lecture 15: Radius Ratio Rules L15-16

The most common close-packed structures are METALS.

A NON-CLOSE-PACKED structure adopted by some metals is:-

(Like CsCl)
 CHEM 2060 Lecture 15: Radius Ratio Rules L15-17

Copper

Tungsten