Crystal chemistry at a glance The packing of spheres.

Metals and ionic compounds can be treated as 3-d arrays of hard spheres and in many cases satisfactory results for energy calculations can be obtained by completely neglecting the covalent character which is always present but often small. In simple cases it is possible to understand and even predict crystal structures based on the notion that the cations and anions pack together as would hard spheres with certain constraints, e.g. cations (often smaller) tend to be surrounded by anions. Unit Cells and the Description of Crystal Structures (Section 2.1) Not covered Fall 2001. Closest Packing (Close-packing) of Spheres (Section 2.2) The closest packing of identical spheres forms the basis for the structures of a number of metals, and the arrangement of the largest ions (often the anions) in a number of simple ionic structures There are two packing methods:

Hexagonal close-packed (hcp) Type ABABAB... (Figs. 2.2a and 2.3a) Cubic close-packed (ccp) or face-centred cubic (fcc) Type ABCABCABC... (Figs. 2.2b and 2.3b)

where A, B and C are hexagonally packed layers of spheres. Both fill 74% of the space in an extended structure. Simple Structures which are not Close-packed (Section 2.5) There are two other simple packing types which are found:

Body-centered cubic - 68% filled (Fig 2.6) Primitive (or simple) cubic - 52% filled(Fig 2.7)

(The body-centred cubic type is relatively common, but only -Po is know to adopt the primitive cubic structure.) Polymorphism of metals (Section 2.6) Many metals adopt one of the common packing types described above and many adopt more than one: Crystal Packing of Metals Cubic Close-Packed Hexagonal CloseWhere two or more symbols are used, the

(ccp) Body-Centred Cubic (bcc) H Li Na K Rb Cs Fr Be M g Ca Sr Ba Ra La Ce Pr Nd Sc Y La Ti Zr Hf V Nb Ta Cr M o W M n Tc Re

Packed Disordered ccp/hcp largest indicates the room temperature form. He B Al Fe Ru Os Co Rh Ir Ni Pd Pt Cu Zn Ga In Tl C Si Ge Sn Pb N P As Sb Bi O S Se Te Po F Cl Br I At Ne Ar Kr Xe Rn

Ag Cd Au Hg

P m

S m

Eu Gd

Tb

Dy Ho

Er

T m

Yb

Lu

The body-centred cubic structure is typically a higher temperature structure, though for some elements, e.g. sodium the phase transition occurs below room temperature. The closer packed structures also seem to be favoured by metals with larger numbers of valence electrons. Atomic Radii of Metals (Section 2.7) Not covered in detail in lectures, but read this section. Alloys (Section 2.8) Not covered Fall 2001. Ionic Solids Geometries of Crystal Lattices (Section 2.9) There are a few very common crystal structures adopted by large numbers of compounds. A few of them are shown below. For simple binary compounds which are predominantly ionic, the structure which is observed can often be predicted based on the stoichiometry (1:1, 1:2, etc.) and on the relative sizes of the ions. Anions tend to be larger than cations so, in an ideal structure, there is contact between adjacent anions, while the cations are in contact with the neighbouring anions, but there is no cation - cation contact.

Structures where the cations is large enough to push apart the anions can occur, but structures where the cation would be "loose" in their sites are undesirable. Therefore it is possible to calculate ranges over which a particular structure is likely based on the ratio of cation to anion radius. This illustrated below for three common 1:1 structures. (The pictures on the right are applets. You can change the viewing direction by dragging the mouse across them.) Zinc Blende (Cubic Zinc Sulphide) This strucure is based on cubic close-packed anions with cations in half the tetrahedral holes, that is, the cations are 4-coordinate.

The ideal radius ratio (either r+/r_ or r_/r+) is calculated by eliminating d from the following equations: 2r_ = 2d r+ + r_ = 3d/2 which gives: r+/r_ = 0.23 or r_/r+ = 4.44 Rock Salt (Sodium Chloride) This structure is based on cubic close-packed anions with cations in all the octahedral holes, that is, the cations a 6-coordinate.

The ideal radius ratio (either r+/r_ or r_/r+) is calculated by eliminating d from the following equations: 2r_ = 2d r+ + r_ = d which gives: r+/r_ = 0.41 or r_/r+ = 2.44 Cesium Chloride This structure is based on a primitive cubic packing of the ions. Each type (anion or cation) is 8-coordinate.

The ideal radius ratio (either r+/r_ or r_/r+) is calculated by eliminating d from the following equations: 2r_ = d r+ + r_ = 3d/2 which gives: r+/r_ = 0.72 or r_/r+ = 1.37 Other structures The other simple structures described in class are:

Wurtzite - another form of zinc sulphide based on hexagonally close packed sulphide ions with zinc ions in one half of the tetrahedral holes, just like the zinc blende structure. The same ideal radius ratio applies. Fluorite and Antifluorite - The fluorite typified by CaF2 structure is based on a facecentred cubic flouride arrangement with calcium ions in all the tetrahedral holes, and the anifluorite structure typified by K2O has the reverse arrangement. Rutile - The compound from which the name comes is TiO2. The ion Ti4+ cannot exist in a truly ionic compound: there will always be significant covalency because the ion would be very small and highly charged, strongly polarizing the counter anions. The structure is not based on cubic or hexagonal close packing. The cations are 6-coordinate and the anions are 3-coordinate. Perovskite - This is an example of a more complicated structure for compounds of the form ABX3. The named mineral is CaTiO3. It was used as an example of how to deduce the formula of an ionic compound from a picture of the unit cell.

Rationalization of Structures (Section 2.10) Ionic Radii and the Ideal Radius Ratios The basic premise for making predictions is that it is acceptable if the smaller ion (usually the cation) is too big for the hole in the close packed array of larger ions (usually the anions) so that the anions are forced apart. However, the smaller ion must not be a loose fit in its site. In this way, for 1:1 compounds we predict that:

Compounds with r+/r- from 0.22 to 0.41 will adopt the ZnS (blende or wurtzite) structures. Compounds with r+/r- from 0.41 to 0.72 will adopt the NaCl structure. Compounds with r+/r- greater than 0.72 will adopt the CsCl structure. I r+/r- is less than 0.22, the copounds are likely to be quite covalent.

When the actual structures are compared to what is predicted, the results are quite bad, especially for the ZnS structure, which persists in cases where r+/r- is much larger than the presumed limit of 0.41. Only a general trend can be detected. One difficulty is the difficulty in assigning reliable ratii to the ions. Structure Maps These are plots of the electronegativity difference between the elements of which the compound is formed, and the average principal quantum number of the elements. On such scatter diagrams (Figures 2.22 and 2.23) quite well defined zones of one structural type are revealed. This is not unexpected because there is a close link between ion size and the electronegativity and between size and the period in which the ion is found. The Born-Haber Cycle: Experimental Approaches to Lattice Energy Section 2.11 Born-Haber cycles represent, on paper, different routes for the formation of a ionic crystal structure from its elements. As an example, the cycle for the formation of Al2O3 from its elements, metallic aluminum and gaseous oxygen is given below. Usually such cycles are used to calculate a missing enthalpy, for example, Electron capture enthalpies which are difficult to measure directly by experiment. Apart from the lattice energy, the other quantities can be obtained reasonably precisely. The lattice energy can be obtained by calculation, as described in the next section.

The Lattice Energy of Sodium Chloride Section 4-2

The crystal lattice of the mineral rock salt (sodium chloride) is used as an example of the method of calculation. There are two significant terms which contribute to the energy: a. Coulombic (electrostatic) attractions and repulsions. b. Short range repulsions. In addition, there is a little vibrational energy and other minor sources which will not be considered. The diagram below shows a small part of the structure of the sodium chloride lattice.

The electrostatic potential energy (E) of any single ion is given by the sum of the series: Ecoul = 1/(4o)(- 6e2/d + 12e2/2d - 8e2/3d + 6e2/4d - 24e2/5d ...) The first term in the series corresponds to the 6 counter ions in the immediate coordination sphere of the chosen ion, and is negative because of the opposite charges. The second term goes with the 8 nearest similar ions, and so on. The coefficients in the series are not predictable in any straightforward way, and because of the alternation of signs, the series converges rather slowly. Nevertheless, the job has been done for a number of crystal structures. The general formula for a mole of ions is: Ecoul = NAzAzBe2/4od N is avagadro's number, and A is the Madlung constant. zA and zB are the charges on the ions. (For NaCl, zA = 1 and zB = -1 so E will be negative, as expected.) A selection of values of A is given below:

Structure NaCl CsCl ZnS (blende) ZnS (wurtzite) CaF2 TiO2 CdI2 Al2O3

A 1.74756 1.76267 1.63806 1.64132 5.03878 4.816 4.710 25.242

Notice how A is more or less constant for structures with the same stoichiometry, but increases rapidly with the number of ions in the formula unit. The other term contributing to the energy of the lattice comes from the short range repulsion between the cations and anion as their electron clouds start to overlap. The formula for this repulsion energy is: Erep = NB/dn B is a constant, and n varies with the nature of the ions, specifically their configuration: Ion Configuration He Ne Ar Kr Xe For mixed cases, an average can be used for n. The total lattice energy (U) is given by: U = Ecoul + Erep = NAzAzBe2/4od + NB/dn n 5 7 9 10 12

At the equilibrium distance (where d = do) dU/dd = 0: dU/dd = NAzAzBe2/4odo2 - NB/don+1 = 0 B = AzAzBe2don-1/4on U = (NAzAzBe2/4odo)(1-1/n) When all the constants are given their numerical values: U = 1389(zAzBM/do)(1 - 1/n) (kJ mol-1) Note that the calculated values of U are quite insensitive to the value of n. Generalization of the Lattice Enery Calculation Section 4-3 The derivation above produces an equation which requires precise knowledge of the crystal structure. Two other equations which are easier to use deserve mention: The Born-Meyer Equation U = (NAzAzBe2/4odo)(1-d*/do) In this equation the invariant n is replaced. The value d* = 34.5 pm works for most crystals. The Kapustinski Equation U = KnzAzBe2/4odo)(1-d*/do) Here K = 1.21 MJ mol-1 and n is the number of ions in the formula empirical formula of the compound, e.g. n = 5 for Al2O3. The value of d to be used is (r+ + r_) where these radii are the radii for 6-coordinate ions found in many tables. This equation works because it is found that (A/nd) is approximately constant from one structure to another.

Consequences of Lattice Enthalpies On the Existence or Non-existence of Simple Ionic Compounds Consider the thermodynamic data (in kJ) in the table below: Salt NaCl "NaCl2" "CaF" CaF2 Hf -412 +2529 -112 -1220 = U -787 -2180 -795 -2963 + HE
A

Hsu
b

Hdi
ss

+ HIP +495 +5057 +590 +1735

-349 -698 -164 -328

+108 +108 +178 +178

+121 +242 +79 +158

Note: The lattice energies for "NaCl2" is estimated assuming it would crystallize in the CaCl2 structure, and the lattice energy for "CaF" is estimated assuming it would crystallize in the NaF structure.

The hypothetical compound "NaCl2" is strongly endothermic due to the very large second ionization potential of Na+ Na2+ (4562 kJ mol-1) which is only partly compensated by the much larger lattice energy for a 1:2 stoichiometry. Any attempt to make this compound from Na and Cl2 would simply result in left-over Cl2. Both CaF2 and the hypothetical "CaF" are exothermic compounds, but CaF2 is far more stable. Once again the dominant terms are the lattice energies and the ionization potentials, but the second ionization potential: Ca+ Ca2+ (1145 kJ mol-1) is much smaller than for Na+. The compound "CaF", if it could be formed, would be very unstable with respect to CaF2 and excess Ca. The Thermal Decomposition of Carbonates of the Alkaline Earth Metals (Group II) (Section 2.12 (a) The reaction is: MCO3(s) MO(s) + CO2(g)

and is the temperature at which the equilibrium produces a pressure of 1 atm. Consider the thermodynamic data in the table below: MgC O3 Go kJ mol-1 Ho kJ mol-1 So J K-1 mol-1 +48.3 +100. 6 +175. CaC O3 +130. 4 +178. 3 +160. SrC O3 +183 .8 +234 .6 +171 BaCO
3

+218. 1 +269. 3 +172.

0 oC Note the following points:

6 840

.0 1100

1 1300

300

The temperature of decomposition rises from MgCO3 to BaCO3. The equilibriun constant will be unity (K = 1) when G = 0, and at this point: T = Ho/So (bcause G = H - T.S)

The entropy change, So, remains roughly constant, since it is mostly due to the evolution of the very disordered CO2 gas. Therefore the free energy change, Go, is largely determined by changes in the enthalpy, Ho. In turn the enthalpy is partly determined by the change in lattice energy going from the carbonate to the oxide. While total enthalpy change is positive, the lattice energy change makes a negative contribution to it, so the more more stable the oxide lattice relative to the carbonate the less positive the enthalpy will be. Since the stoichiometry of the compounds remains 1:1 and the charges remain the same (cation 2+, and anion 2-) the only other factor in the lattice energy calculation is the interionic separation. These are estimated in the Table below for the Mg and Ba compounds. % Compound Distance Compound Distance Change MgCO3 2.57 MgO 2.12 17.5 BaCO3 3.60 BaO 3.15 12.5
The (6-coordinate) radii of Mg2+ and Ba2+ are 0.72 and 1.75 respectively. The radius of O2- is 1.40 , and the effective ("thermodynamic") radius of CO32- is 1.85 .

Compound MgCO3 BaCO3

Lattice Energy 1630 1216

Compound MgO BaO

Lattice Energy 1911 1426

Lattice Energy Difference -281 -210

The lattice energies are calculated using the Kapustinski equation and the interionic distantances from the table above. Energies are in kJ mol-1

The percentage change in the cation - anion distance, and hence the change in lattice energy, is largest for MgCO3, and decreases to BaCO3, so the enthalpy change for MgCO3 will be smallest, and the decomposition temperature lowest.