Ionic and Metallic Solids

Chapter 4A
Outlines
• Ionic solids
• Metallic solids
• Crystalline Solids and Unit Cell
• Coordination number
• Close Packing of metallic solids
• Close Packing of ionic solids
• Types of holes
• Born-Haber cycle
Ionic solids
What are ionic solids?
Ionic solids are material that are composed of positive and negative ions
and held together by electrostatic attractions.

What are the properties of ionic solids?

1-Very high melting points
2- Brittleness
3-Poor conductors in the solid state.
Example: NaCl
Metallic solids
What are metallic solids?
Metallic solids are composed of metal atoms that are held together by
metallic bonds.

What are the properties of metallic solids?

1-High melting points,
2-They range from soft and malleable to very hard.
3- Good conductors of electricity.
Example:
Crystalline Solids and Unit Cell
Crystalline solids can be regarded as solids where their atoms, ions, or molecules
exist in a regular (uniform), well-defined order. These solids takes up a three
dimensional aggregate of single atoms, ions, or whole molecules organized in
repeating patterns. (Fig.1)
Unit cell
Is the smallest, identical repeating pattern of the crystalline solids.
FF

Fig. 1
https://opentextbc.ca/chemistry/chapter/10-6-lattice-structures-in-crystalline-solids/
Close Packing
The atoms, ions, or molecules in the crystalline solids are called lattice points and
modeled as round spheres.
The two dimensional layers of a solid the “spheres” is represented by Close
Packing.
Assembling the two dimensional layers on top of each other results in a three
dimensional lattice point arrangement represented by a unit cell.
Stacking the two dimensional layers on top of each other creates a three
dimensional lattice point arrangement represented by a unit cell. (See Fig2)

Fig. 2 file:///C:/Users/CBE/Desktop/Chapter%204/Properties%20of%20solids.html
Metals Three Close Packing
Metals usually take one of the three structures types:
1)Cubic closest packed (cpp) (Fig.3)
2) Hexagonal closest packed (hcp) (Fig.4 )
3)Body centered cubic (bcc) (Fig.5 )

Fig. 3 Fig.4 Fig.5

Cubic Structure
1-Simple Cubic Structure
When placing a second “square” array layer (Fig. 6) directly over a first
“square” array layer a simple cubic structure is formed. This
arrangement is known as packing and refer to as AA…. Packing (Fig. 7).

Fig. 6 square arry

Fig. 7
Of spheres
1-Cubic Structure
The 3D arrangements of AA close packing results in the simple cubic
structure as in Fig. 8.

Fig. 8
2-Cubic closest packed (cpp)
In ccp the atoms are hexagonally arranged in three repeating arrays as
in Fig. 9.
The repeating pattern is of ABCABC….
The coordination number 12 (the atoms are in contact with 6 atoms in
their layer and 3 from above and 3 from below).

Fig. 9
3-Hexagonal Close Packing (hcp)
The repeating pattern is of ABAB….
The coordination number 12
Examples:
Metals that adopt ccp crystallizen arrangmets
Ag, Al, Ca, Cu, Ni, Pd and Pt.
Metals that adopt hcp crystallizen arrangmets
Cd, Co, Li, Mg, Na and Zn.

Fig. 1 Hexagonal close packing (ABAB ….)

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Close Packing
The Ionic Crystals Structures
• Anions which are larger in size compared to cationic metals.
• The anions arranged themselves in close-packed arrays. The smaller cations then
occupy the holes between the anions.
• Accordingly, there are two types of holes: tetrahedral and octahedral holes. (See
Fig. 1)

Fig. Tetrahedral hole Fig. Octahedral hole

 Tetrahedral and Octahedral holes

https://www.toppr.com/guides/chemistry/the-solid-state/tetrahedral-and-octahedral-voids/
II- Ionic Compounds
A- Cubic Structure (CS)
In cubic structure the anions and
cations are very close in size.
Example:
CsCl
Cs+ (174 pm) and Cl- (181 pm)
Cs+: Forms cubic unit cell.
Fig.
Cl- : occupy the center. https://opentextbc.ca/chemistry/chapter/10-6-lattice-structures-in-crystalline-solids/

Note: This is not bcc structure.

es/chemistry/the-solid-state/tetrahedral-and-octahedral-voids/
II- Ionic Compounds
B- FCC unit cell
anions and cations are different in size.
Example:
NaCl
Na+ (102 pm) and Cl- (181 pm)
Cl- forms an A-type lattice (ccp type).
Na+ occupy the octahedral holes in the lattice
Fig. NaCl unit cell
 II- Ionic Compounds

https://www.chem.wisc.edu/areas/clc/general/103/crystalLatti
ces/lattices.htm
Coordination Number
Coordination number
The number of other particles that each particle in a crystalline solid
contacts. (Fig. 1)

Fig. 1 The coordination number of this cubic lattice structure is six.

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Coordination Numbers
• Coordination numbers can be deduced from the type of the hole as
follow

Hole Coordination number

Cubic hole 8 CsCl
Octahedral hole 6 NaCl
Tetrahedral hole 4
Born-Harber Cycle
Born –Harber cycle is used for describing the formation of ionic
compounds from different elements.

Ionic solids are the product of the reaction of electropositive metals

with electronegative nonmetals kept in crystalline state by the lattice
energy.
Lattice energy can be defined as either energy released when gaseous
ions form one mole of a solid ionic compound or as the energy required
to convert one mole ionic solid into its gaseous ions.
Born-Harber Cycle
Hess law
The summation of enthalpy of all processes that are necessary for the
formation of the solid ionic compound from the elemental state of the
constituent atoms. This process is written as a cycle where that the total
energy on summation equals zero.
•  Enthalpy change of atomization enthalpy of ions
• Ionization enthalpy of cation
• Atomization enthalpy of anion
• Electron affinity of anion
• Lattice enthalpy
Born-Harber Cycle
Example
Born-Harber cycle of NaCl
• Calculate the lattice energy formation enthalpy of NaCl given that:
• ΔHa(Na) = + 109 kJ/mol; ΔHdiss(Cl2) = +242 kJ/mol;
ΔHf(NaCl)= -414 kJ/mol; ΔHEN(Cl)= -364 kJ/mol;
ΔHIE(Na)= +494
 Na (s)       -------------->   Na (g)                     ΔH1   =       108 kj

Born-Harber Cycle
• 1/2 Cl2(g)     ----------------> Cl (g)                ΔHdiss =           102 kj/mol
• Na (s)       -------------->   Na (g)                     ΔHsub =       108 kj/mol
• Na (g)         ----------------> Na+ (g) + e- (g)  ΔHIE =          496 kj/mol
• Cl (g) +  e- (g) ------------> Cl- (g)                ΔHEV =         -349 kj/mol
• Na+ (g) + Cl- (g) --------->  NaCl (s)           ΔHf =          - U
• ---------------------------------------------------------------------------------
• Na (s)  +  1/2 Cl2 (g)  --------------> NaCl         ΔH0f  = 375 kj/mol
375 kj/mol - U = - 411 kj/mol
U= 786 kj/mol
• ΔHsub:  Sublimation of sodium
•  IE: Ionization energy of the metal atom
•  EN: Electron affinity of non-metal atom
• ΔHdiss: Dissociation of chlorine Cl2 (g)---- 2Cl(g)
• Lattice energy (exothermic) U
• ΔHf : formation of NaCl from its ions.