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Coordination # and Ionic Radii

1) The coordination number of cations in ionic crystals increases with cation radius from 2 for radii less than 0.155 nm to 6 for radii between 0.225-0.414 nm and 8 for radii 0.732-1.0 nm. 2) For FeO, the ratio of cation (Fe2+) radius (0.077 nm) to anion (O2-) radius (0.140 nm) is 0.550. This predicts an octahedral coordination and the NaCl crystal structure. 3) For ionic crystals with the ratio of cation to anion radii between 0.414-0.732, such as MgO and NaCl, cations occupy octa

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118 views9 pages

Coordination # and Ionic Radii

1) The coordination number of cations in ionic crystals increases with cation radius from 2 for radii less than 0.155 nm to 6 for radii between 0.225-0.414 nm and 8 for radii 0.732-1.0 nm. 2) For FeO, the ratio of cation (Fe2+) radius (0.077 nm) to anion (O2-) radius (0.140 nm) is 0.550. This predicts an octahedral coordination and the NaCl crystal structure. 3) For ionic crystals with the ratio of cation to anion radii between 0.414-0.732, such as MgO and NaCl, cations occupy octa

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Aaila Akhter
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Coordination # and Ionic Radii

r cation
• Coordination # increases with r
anion
To form a stable structure, how many anions can
surround around a cation?
r cation Coord ZnS
r anion # (zinc blende)
Adapted from Fig. 3.7,
< 0.155 2 linear Callister & Rethwisch 3e.

0.155 - 0.225 3 triangular NaCl


(sodium
0.225 - 0.414 4 tetrahedral chloride)
Adapted from Fig. 3.5,
Callister & Rethwisch 3e.

0.414 - 0.732 6 octahedral CsCl


(cesium
chloride)
0.732 - 1.0 8 cubic Adapted from Fig. 3.6,
Adapted from Table 3.3, Callister & Rethwisch 3e.
Callister & Rethwisch 3e.
1
Computation of Minimum Cation-Anion
Radius Ratio
• Determine minimum rcation/ranion for an octahedral site (C.N. = 6)

2ranion  2rcation  2a

a  2ranion
2ranion  2rcation  2 2ranion

ranion  rcation  2ranion rcation  ( 2 1)ranion

rcation
 2  1  0.414
 ranion 
2
AX Crystal Structures
NaCl (Rock Salt)

rNa = 0.102 nm

rCl = 0.181 nm

rNa/rCl = 0.564

 Cations (Na+) prefer octahedral sites


Adapted from Fig. 3.5,
Callister & Rethwisch 3e.

3
FeO
• On the basis of ionic radii, what crystal structure
would you predict for FeO?
Cation Ionic radius (nm) • Answer:
Al 3+ 0.053 rcation 0.077

Fe 2+ 0.077 ranion 0.140
Fe 3+ 0.069  0.550
Ca 2+ 0.100
based on this ratio,
-- coord # = 6 because
Anion
0.414 < 0.550 < 0.732
O2- 0.140
-- crystal structure is NaCl
Cl - 0.181
F-
Data from Table 3.4,
0.133 Callister & Rethwisch 3e.
4
MgO
MgO also have the NaCl structure

O2- rO = 0.140 nm

Mg2+ rMg = 0.072 nm

rMg/rO = 0.514

 cations prefer octahedral sites

Adapted from Fig. 3.5,


Callister & Rethwisch 3e.

So each Mg2+ (or Fe2+) has 6 neighbor oxygen atoms

5
CsCl
Cesium Chloride structure:

rCs  0.170
  0.939
rCl 0.181

 Since 0.732 < 0.939 < 1.0,

cubic sites preferred


Adapted from Fig. 3.6, So each Cs+ has 8 neighbor Cl-
Callister & Rethwisch 3e.

6
AX2 Crystal Structures
Fluorite structure

• Calcium Fluorite (CaF2)


• Cations in cubic sites

• UO2, ThO2, ZrO2, CeO2

• Antifluorite structure –
positions of cations and
anions reversed
Adapted from Fig. 3.8,
Callister & Rethwisch 3e.

7
ABX3 Crystal Structures
• Perovskite structure

Ex: complex oxide


BaTiO3

Adapted from Fig. 3.9,


Callister & Rethwisch 3e.

8
c03tf05

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