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CHEM 2060 Lecture 15: Radius Ratio Rules L15-1

Radius Ratio Rule

En cristales iónicos ideales, los números de coordinación se determinan en gran parte por
consideraciones electrostáticas.

1. Los cationes se rodean con tantos aniones como sea posible y viceversa.

2. Esto se puede relacionar con los tamaños relativos de los iones. Regla de cociente de los radios

Radius ratio rule states:

1. Conforme el tamaño (radio iónico r) de un catión aumenta, más aniones pueden empaquetarse
alrededor él.

2. Conociendo el tamaño de los iones, deberíamos ser capaces de predecir qué tipo de
empaquetamiento cristalino se observará.

3. Podemos explicar el tamaño relativo de ambos iones utilizando la proporción de los radios iónicos:
CHEM 2060 Lecture 15: Radius Ratio Rules L15-2

Limiting Radius Ratios

Para una estructura específica, podemos calcular la relación de radio límite, que es el valor mínimo permisible para la relación de
radios iónicos (r+/r-) para que la estructura sea estable.

Revisando la
estructura del
ClCs
CHEM 2060 Lecture 15: Radius Ratio Rules L15-3

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

2r  2r 
Recall: we know the length of each side of the
triangle:
2r 3
cube edge (1), face diagonal ( 2), body diagonal ( 3)
r  3 1 

0.732
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:
cube edge & face diagonal! 
4r   2r   2r   2
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  
r  r     r  
  2

 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)
Examples: 0.414 – 0.732 NaCl, TiO2, CdCl2
4 (tetrahedral) 0.225
r 2+
– 0.414 antifluorite, ZnS
3 (triangular)
Beryllium sulfide, BeS 0.155
Be – 0.2250.35
0.59 C.N. = 4
r 2- 1.7
S

r +
Sodium chloride, NaCl Na 1.16 0.69 C.N. = 6
r - 1.67
Cl

r
Cs+ 1.81
Cesium chloride, CsCl 1.08 CN = 8
r - 1.67
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