Chapter 3.

The Structures of Simple Solids Outline

A. Fundamental Aspects of Solids & Sphere Packing B. Common unit cells C. The crystal structures of metals (or other elements) D. The Crystal Structures of Ionic Solids E. The Energetic Aspect of Ionic Solids
References: 1. Inorganic Chemistry, Catherine E. Housecroft and Alan G. Sharpe, 3rd Ed., Pearson Education Ltd, 2008, Chapter 6. 2. Inorganic Chemistry, D.F.Shriver, P.W.Atkins et al, 3rd Ed., Oxford University Press, 2006, Chapter 3. 3. Basic Inorganic Chemistry , F. A. Cotton, G. Wilkinson and P. L. Gaus, 3rd Ed., John Wiley & Sons, Inc. 1995, Chapter 4. 4. Concepts and Models of Inorganic Chemistry, B. Douglas, D. McDaniel and J. Alexander, 3rd Ed., John Wiley Sons, Inc. 1994, Chapter 5. 5. Introduction to Coordination, Solid State, and Descriptive Inorganic Chemistry, G. E. Rodgers, McGraw- Hill, 1994, Chapters 7 and 8. 6. Inorganic Chemistry, G. L. Miessler, D. A. Tar, Prentice Hall: Pearson 1 Education Inc., 2004, Chapters 7.

A. Fundamental Aspects of Solids & Sphere Packing.

Many inorganic materials are crystalline solids. e.g. Metals Ionic solids (e.g. NaCl) Covalent solid (e.g. diamond) Atomic or Molecular solid (e.g. Ar, CO2) In term of crystal structures, they can be thought as formed by packing of atoms, ions or molecules to extended crystal lattices.

Concept of unit cell

How to describe the structures of solids? A crystal structure is composed of a motif, a set of atoms arranged in a particular way, and a lattice (,). Motifs are located upon the points of a lattice, which is an array of points repeating periodically in three dimensions Examples of two-dimensional Lattices

A crystal structure can be

represented by a threedimensional lattice

Lattice are usually described in terms of unit cell.

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A unit cell is a subdivision (or smallest component) of a crystal that, when stacked together without rotation or reflection, reproduces the crystal. Start with a lattice, one can define unit cells For a given periodical arrangement, the number of choices in unit cell can be more than one.

a lattice point a lattice point

Preferred one are those of smaller size and higher

3-D Lattices and unit cells: The seven crystal systems or essential unit cells

or rhombohedral

A note on Hexagonal unit cell

120o 60o

conventional hexagonal unit cell

primitive hexagonal unit cell

Each essential system can have different lattice types, e.g. for cubic system:

Primitive (P)

Body-centered (I)

Face-centered (F)

The 14 possible BRAVAIS LATTICES

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Location of motif in a unit cell: Fractional atomic coordinates and projections

y x
z y x

y x

(0,1) (1/2) (0,1) (0,1)

(0,1)

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Another example

y x (1/2) (0,1) (0,1) (1/2) (1/2) (0,1)

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Exercise. Give the fractional coordinates of the following unit cell.

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Counting Atoms in 3D Cells

Atoms in different positions in a cell are shared by differing numbers of unit cells

Vertex atom shared by 8 cells => 1/8 atom per cell Edge atom shared by 4 cells => 1/4 atom per cell Face atom shared by 2 cells => 1/2 atom per cell Body unique to 1 cell => 1 atom per cell

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B. Common unit cells

1. Unit cells from close packing of spheres

A single layer of spheres is closest-packed with a HEXAGONAL coordination of each sphere

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Two common types of close packing

A second layer of spheres is placed in the indentations left by the first layer. When a third layer of spheres is placed in the indentations of the second layer there are TWO choices.

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Two common types of close packing: another view

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Is the packing shown below also a close packing?

A B A C A

Cubic close packing (also called face centered close packing) abbreviation: ccp or fcc
Pattern: ABCABCABC. Contains a cuboctahedron

Coordination number of each sphere =

19

Choosing unit cell for cubic close packing (also called face centered close packing) Choice 1: corners and face-centered

Number of balls in a unit cell:

20

Examples

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Choice 2: edge and body centered

Number of balls in a unit cell:

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Hexagonal close packing: hcp Pattern: ABABAB

unit cell of hcp: choice 1

Contains an anti-cuboctahedron

Number of balls in a unit cell = ?

Coordination number of each sphere:

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Choice 2 Choice 1, another view

Number of balls in a unit cell:

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Structural characteristics of fcc and hcp Holes in close-packed structures

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Oh and Td Holes
View the structures of cuboctahedron or anti-cuboctahedron to obtain the following properties:

# balls : # Td holes = 1. Number of holes surrounding a ball: #Td =, #Oh = An octahedral hole is shared by __ balls. A tetrahedral hole is shared by __ balls.

# balls : # Oh holes =

No. of balls : no. of octahedral holes : no. of tetrahedral holes =

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Consider the unit cell for fcc (or ccp) again:

(a) Coordination number for each sphere (number of nearest balls): (b) Number of spheres in the unit cell: (c) Number of tetrahedron holes in the unit cell: (d) Number of tetrahedron holes in the unit cell: (e) Relationship between cell size (l) and radius of ball (r):

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Where are the holes?

Tetrahedral holes: under each corner

Octahedral holes: center + middle of the edges

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Consider the unit cell for hcp again: (a) Coordination number for each sphere (number of nearest balls): (b) Number of spheres in the unit cell: (c) Number of tetrahedron holes in the unit cell: (d) Number of tetrahedron holes in the unit cell:

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Relationship between cell size and radius of ball (r):

If the sphere radius is r,

a = ____

c = ___

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Relationship between cell size and radius of ball (r):

If the sphere radius is r,
c
a = 2r

c=2h c= 2h

2 8r 3

46 r 3

4 2r 3

4r(2/3)1/2

h =

8r 3

24r 3

26 r 3
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2. Body-centered cubic packing (bcc)

(a) Coordination number for each sphere:

(b) irregular holes only (c) number of spheres in the unit cell: (d) Relationship between cell size (l) and radius of ball (r):

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3. Primitive cubic packing (simple cubic)

(a) Coordination number for each sphere: (b) Type of holes: (c) Number of spheres in the unit cell: (d) Number of spheres in the unit cell: (e) Relationship between cell size (l) and radius of ball (r):
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4. Fraction of space occupied by spheres in different unit cells.

Fraction of space occupied by spheres. For FCC,

Vsphere Vunit cell

4 (4/3) r3 = = 74.05% 3 l l = 2(2)1/2 r

The fraction of space occupied by spheres for hcp is ________. (Both hcp and fcc are most close-packed structures.)

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5. CALCULATION OF DENSITY OF UNIT CELL

Density of Unit Cell

Mass of unit Cell = Volume of unit Cell

Mass of unit cell = Number of atoms in unit cell x Mass of each atom Mass of unit cell =

Z m

M Mass of each atom = m = N

Z = No of atoms in unit cell N is Avogadros Number M is the Molar mass of the Crystal a3 is the volume of the unit cell Where a is the edge length of a unit cell

ZM

a is the edge length of a cube usually expressed in pico metre or nano metre 1pm =10-12 m and 1nm = 10-9m, M is the molar mass of the element.

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Summary on fraction of space occupation

Name simple cubic body center ccp or fcc hcp coord. no. 6 sphere touching cell edge body diagonal face diagonal fraction of occupation 0.52 0.68 0.74 0.74

8 12 12

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C. The crystal structures of metals (or other elements)

They can be best described in terms of close-packed and non-close-packed structures. E.g.

simple cubic (sc) primitive cubic (cubic-P)

body-centered cubic (bcc)

fcc

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The crystal structures of metals

Table: The most stable crystal structures assumed by the elements in their solid phase
He hcp C N O F Ne d hcp sc - ccp Si P S Cl Are d sc or tet ccp Ge As Se Br Kr d rh hcp or ccp Sn Sb Te I Xe tet rh hcp or ccp Pb Bi Po At Rn ccp rh mono - ccp

Li bcc Na bcc K bcc Rb bcc Cs bcc

Be hcp Mg hcp Ca Sc Ti V Cr ccp hcp hcp bcc bcc Sr Y Zr Nb Mo ccp hcp hcp bcc bcc Ba La Hf Ta W bcc hcp hcp bcc bcc

Mn bcc Tc hcp Re hcp

Fe bcc Ru hcp Os hcp

Co Ni hcp ccp Rh Pd ccp ccp Ir Pt ccp ccp

Cu Zn ccp hcp Ag Cd ccp hcp Au Hg ccp rh

B rh Al ccp Ga sc In tet Tl hcp

Note: sc = simple cubic, tet = tetragonal, rh = rhombohedral, d = diamond or = orthorhombic, mono = monoclinic

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Polymorphism
e.g. Structure of Fe changes with Temperature
Many metals adopt different structures at different temperature or pressure. Polymorphism: A solid adopts different crystal forms In elemental solids, this is called Allotropy. -iron

-iron

-iron

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41

Structures of alloys a blend of metallic elements

(a)Substitutional solid solutions:
Replacement of one type of metal atoms in a structure by another.

(b) Interstitial solid solutions of nonmetals:

Additional small atoms (e.g. C, B, N) occupy holes within the lattice of original metal structure

Maybe formed, if -radii of the elements are similar. -structure of pure metals are the same. -electropositive character are similar.

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Structures of alloys
(c) Intermetallic compounds. Structure is different from the structures of either component metals

e.g. Cu, ccp, Zn, hcp, but alloy CuZn has the following structure

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Examples of alloys
Bronze is a substitutional alloy

Carbon Steel is an interstitial alloy

The Crystal Structures of Ionic solids

Many ionic solid structures can be regarded as derived from arrays in which the anions (sometimes the cations) stack together in fcc or hcp (or others) patterns and the counter ions occupy the octahedral and tetrahedral holes in the close packing.

e.g. Nail

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(a) MX structures
Rock salt structure

Close packing type of anion: Type of holes occupied by cation: Hole occupancy: Coordination no.of Na+ : Coordination no.of Cl- :
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Zinc blende (ZnS) structure

Close packing type of anion: Type of holes occupied by cation: Hole occupancy: Coordination no.of Zn2+ : Coordination no.of S2- :
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Cesium chloride structure

CsCl

NH4Cl

Close packing type of anion: Type of holes occupied by cation: Hole occupancy: Coordination no.of NH4+ : Coordination no.of Cl- :

49

Nickel-arsenide (NiAs) structure

Close packing type of As Type of holes occupied by Ni Hole occupancy: Coordination no.of As : Coordination no.of NI :
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Wurtzite (ZnS) structure

Close packing type of anion: Type of holes occupied by cation: Hole occupancy: Coordination no.of Zn2+ : Coordination no.of S2- :

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(b) MX2 structures

Fluoride (CaF2)

Close packing type of Ca2+: Type of holes occupied by F-: Hole occupancy: Coordination no.of Ca2+ : Coordination no.of F- :
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Rutile (TiO2)
Coordination number for Ti: Coordination number for O:

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(c) More complicated structures:

Perovskite structure ABO3 (CaTiO3) O Ca Ti

Ca and O form close packing. Ti's fill % of the holes. Coordination number of Ti: Coordination number of Ca: Coordination number of O:
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A[B2]O4 The Spinel structure ( ) MgAl2O4 A[B2]O4

O: fcc close-packing A: occupy 1/8 of T holes B: occupy of O holes Fe3O4 = Fe2+[Fe3+]2O4

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Relationship between some important structures

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4. Rationalizing Structures Based on Radius Ratio (r+/r-)

Why NaCl and CsCl adopt different structures?

Related to size of the cavity or r+/r-? Here, r+ and r- are ionic radii of cation and anion, respectively.

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Filling cavity with a particle

Just fitting Perfect packing occurs when anions touch and cations fit perfectly in the pocket. Then, anions touch anions and cations touch anions. If cations are too large (larger rM/rX), anions cannot touch (not ideal). If anions are too large (smaller rM/rX), cations rattle in pocket (worse). Conclusion: The listed rM/rX ratios are 58 the minima, not maxima.

Too big

Too small

For fcc structure MX

For fcc structure MX, X- is close-packed. If X- has its radius r-, how big in size is the octahedral hole? r+/r-=? (r++r-)/(r-+r-) = sin(45) r+/r- = 0.414

r- + r45
o

r- + r+

r+ + r+

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For simple cubic structure:

r +r
-

MM+

2r +2r

+
L2 +L2 = X2

Y= (L) Y = 2r-+2r+ = (3)1/2 (2r-) r+/r- = 0.732

(3)1/2

Y X L L

2 L2 = X2 X = 21/2L X2 + L2 = Y2 2 L2 + L2 = Y2 Y = 31/2L
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Summary:
r+/r0.155 to 3 trigonal 0.225 to 0.414 4 to 0.732 6 to 8 cubic 1 12 Close-packing

maximum coordination number type of holes

tetrahedral octahedral

The listed rM/rX ratios are the minima, not maxima.

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Some examples: Anions Crystal r+/rStructure C.N. NaCl 1.16/1.67=0.69 fcc 6 4 4 Structure all oct. holes half tet. holes hall tet. holes all cubic holes C.N. 6 4 4 8 Cations

ZnS 0.88/1.70=0.52 fcc (Zinc Blende) ZnS 0.88/1.70=0.52 hcp (Wurtzite) CsCl

1.81/1.67=1.08 simple 8 cubic

One can see that not all examples fit the table in the summary. This imply that one should be careful in using the pure ionic model.
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Radius ratios are only correct ca. 50% of the time, not very good for a family of archetypal ionic solids -random choice might be just as successful as radius ratio rules and saying that all adopt the NaCl structure more so!

Ionic radii change with coordination number r8 > r6 > r4 It is hard to determine Ionic radii

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D. The Energetic Aspect of Ionic Solids

An indication of stability for a solid: Lattice energy: Definition. The standard enthalpy change in the formation of gaseous ions from a solid. MX(s) M+(g) + X-(g)
HL > 0

(note: some books refer the Lattice energy to the reversed process!). Lattice disruption endothermic HL , Larger HL,

stability

How to obtain HL? (two methods)

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1. Thermodynamic Model: An Experimental Approach

M(g) + X(g) S D M(s) + X2(g) Hf0 IE-EA M+(g) + X-(g) HL MX(s)

Lattice enthalpy and the Born-Haber cycle

Hf0 + HL = S + D + IE - EA

IE: Ionization Energy; EA: Electron Affinity S: Sublimation Energy; D: Dissociation Energy Some thermo-chemical data (kJ/mol) at 298K for the alkali metal halides: Make comparison of data obtained by the two approaches and comment on their differences.

-Hf0 LiF 616.9 LiI 270.1

S 160.7 160.7

D 78.9 106.8

IE 520.5 520.5

EA 328.0 295.4

HL(exp) HL(theo) 1049.0 966 762.7 723

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2. Theoretical models for calculating lattice enthalpies (purely ionic model)

Consider electrostatic and repulsive interactions between the ions.

Electrostatic Repulsive forces (Born forces)

attractive + repulsive +

- electron-electron - nucleus-nucleus
electrostatic

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Equations proposed to estimate HL

The Born-Lande equation
2

HL =

NA|Z+Z-|e

40do

(1 -

1 )A n

HL =

NA|Z+Z-|e2

40do

1 (1 - ) A n
Born forces

electrostatic

The Born-Meyer equation

HL =

NA|Z+Z-|e2

40do

d (1 - ) A d0

d0
+ -

The Kapustinski equation

HL =

n|Z+Z-|

do

d (1 - ) K d0

HL

Z+ Z

Z+ Z

d0

r+ + r-

The Born-Lande equation

d0
+ B d0
n

HL =

NA|Z+Z-|e2

40do

1 (1 - ) A n

ER =

NA = Avogadro constant A = Madelung constant, relating to the geometry of the crystal. z+ = charge number of cation z = charge number of anion e = elementary charge, 1.6022 1019 C 0 = permittivity of free space d0 = distance to closest ion n = Born exponent, a number between 5 and 12, determined experimentally by measuring the compressibility of the solid, or derived theoretically

d0 U = EC + E R
Z+Z-e2

Ec = 4 d 0 o

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How is Born-Lande Equation derived?

d0
+ B d0
n

HL =
Consider

NA|Z+Z-|e2

40do

1 (1 - ) A n

ER =

d0 U =- HL = ?? U = EC + E R

Mz+(g) + Xz-(g) MX (s)

U = EC + E R

Ec = 4 d 0 o

Z+Z-e2

EC: from electrostatic interaction ER: from Born forces

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(1) Contribution from Electrostatic interactions between ions.

Two ions:
+

d0
-

Ec =

(Z+)(Z-)e2

40do

In cryatals, e.g. 1 mol of NaCl, EC = ?

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e.g. NaCl type crystals

Ec = =

NA(Z+)(Z-)e2

40do

A = Madelung Constant

NA(Z+)(Z-)e2

40do

ANaCl
= 1.74756

ANaCl =

Ec =

NA(Z+)(Z-)e2

40do

A
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(2) Contribution from Born forces.

d0
+ -

ER =

NAB d0
n

n: born component, related to electronic configuration

ER =

B d0
n

d0

Ec = 4 d 0 o

Z+Z-e2

(3) Total energy

U = EC + E R
ER =
B d0
n

U=

NA(Z+)(Z-)e2

40do

A +

NAB d0
n
d0

It can be shown that

B=

NA(Z+)(Z-)e2 Ad0n-1

40don

Ec = 4 d 0 o

Z+Z-e2

U =

NAZ+Z-e2

40do

1 (1 - ) A n

HL =

NA|Z+Z-|e2

40do

1 (1 - ) A n

Born-Mayer Equation
+
Similar to Born-Lande equation. The term related to repusive force is modified.

d0
B e -d0/d

ER =

HL

NA|Z+Z-|e2 d = (1 ) A d0 40do NA|Z+Z-|e2 = 40( r+ + r-) (1 d )A r+ + r-

d0

U = EC + E R

Ec = 4 d 0 o

Z+Z-e2

d is a parameter that is approximately 34.5 pm if d0 is in pm.

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The Kapustinskii equation

d0
+ -

Kapustinkii noted that Madelung constant, d0 and empirical formula are interrelated. The Madelung constant divided by the number of ions in the chemical formula is almost constant for many crystal structures. He derived the following equation.

HL =

n|Z+Z-| do n|Z+Z-| r +r
+ -

d (1 )K d0 (1 d r +r
+ -

)K

K = 1.2025 104 Jmmol1 d = 3.45 1011 m n is the number of ions in the empirical formula z+ and z are the numbers of charge on the cation and anion, respectively r+ and r are the radii of the cation and anion, respectively.

Lattice energy can be estimated based only on the number ofions (n) in the empirical formula

Why different?

77

Consequences of lattice enthalpies (a) Thermal stabilities of ionic solids MCO3 MO + CO2

78

greater lattice energy MCO3 MO + CO2 smaller lattice energy

Lattice energy contribution favors the decomposition process because r(O-2) is less than r(CO32-) so that HL(MO) is larger than HL(MCO3). = HL(MO) - HL(MCO3) lattice energy change
M is smaller in% M O CO3 small % change in lattice scale M O M CO3 large % change in lattice scale is larger in%

A greatly exaggerated representation of the change in lattice parameter for cations of different sizes

disfavors decomposition

favors decomposition

Conclusion: Large cations stabilize large anions The lattice energy change is also proportional to the charge of cations. Therefore, MCO3 (M2+) are less stable than M2CO3 (M+).

79

(b) Solubility of ionic solids in water

Observations: (i) Salts of one small ion and one large counter-ion have higher solubility. (ii) Salts of anion and cation of similar size have low solubility.

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Explanation?
MX(s) HL M+(g) + X-(g)

Hs

H(M+) H(X-) M+(solv) + X-(solv)

Hs = HL + [H(M+) + H(X-)]

HL: positive, proportional to

1
(rM+ + rX-) rM+

H(M+) and H(X-) are all negative, proportional to 1 HL: disfavors the solution process [H(M+) + H(X-)]: favors the solution process

1 + r X-

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Size of M+ and XBoth are Large Both are Small One large One small

HL

[Hsol(M+) + Hsol(X-)]

solubility

Conclusion: salts having one small ion and one large counter-ion have higher solubility. Examples: CsF and LiI have the highest solubility when compared other alkali halides.
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End of Chapter 3

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