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EENS 2110 Mineralogy
Tulane University Prof. Stephen A. Nelson
Crystal Che mistry

This document last updated on 22-Sep-2014

As we have been discussing for the last several weeks, crystals, and thus minerals, are made up
of a 3-dimensional array of atoms arranged in an orderly fashion. Now we explore what these
atoms are and how they interact with one another to determine the physical and structural
properties of crystals. So, first we explore the properties of the atom.

Atoms

Atoms make up the chemical elements. Each chemical element has nearly identical atoms. An
atom is composed of three different particles:

Protons -- positively charged, reside in the center of the atom called the nucleus.

Electrons -- negatively charged, orbit in a cloud around nucleus.

Neutrons -- no charge, reside in the nucleus.

In a neutrally charged atom, each element has the same number of protons and the same
number of electrons.

Number of protons = Number of electrons.

Number of protons = atomic number.

Number of protons + Number of neutrons = atomic weight.

Isotopes are atoms of the same element with differing numbers of neutrons. i.e. the number of
neutrons may vary within atoms of the same element. Some isotopes are unstable which results
in radioactivity.

Example: K (potassium) has 19 protons. Every atom of K has 19 protons. The Atomic
number of K=19. Some atoms of K have 20 neutrons, others have 21, and others have 22.
Thus atomic weight of K can be 39, 40, or 41. 40K is radioactive and decays to 40Ar and
40Ca.

It is the electrons in the atoms that are responsible for the chemical properties of atoms. The
electronic configuration determines the types of atoms that can be bound to one another, the

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strength of the bonds, and the types of bonds. Thus, we need to look closely at the electrons
and the electronic configuration of atoms.
Bohr Atom

Electrons orbit around the nucleus in

different shells, labeled from the
innermost shell as K, L, M, N, etc. Each
shell can have a certain number of
electrons. The K-shell can have 2
Electrons, the L-shell, 8, the M-shell 18,
N-shell 32.

Each shell is associated with a principal

quantum number, n, where nK = 1, nL =
2, nM = 3, nN = 4, etc.

The number of electrons in each shell is

controlled by this principal quantum
number by the following relationship:

# electrons = 2n2

Thus, the K-shell can contain 2

electrons, the L-shell, 8 electrons, the
M-shell, 18 electrons, and the N-shell,
32 electrons.

Electrons in the outermost shells have higher energy than those in the inner shells. This is
because the electrons in the outermost shells would release more energy if they were to fall into
the inner shells. When such electronic transitions occur, the energy is released as photons, such
as X-rays, as we discussed previously.

Planck found that the energy released in the electronic transitions is only released in distinct
packets, which he called "quanta", and that these packets of energy are related to a constant
(now called Planck's constant, and the frequency or wavelength of the radiation released.

E = hν = hc/λ

where

E = energy
h = Planck's constant, 6.62517 x 10-27 erg.sec
ν = frequency
c = velocity of light = 2.99793 x 1010 cm/sec
λ = wavelength

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This led to the quantum mechanical view of the atom.

Quantum Mechanical View of the Atom

The quantum mechanical view of the atom suggests that the electrons are located within
specific regions of probability. These probability regions are described by the azimuthal
quantum number or orbital shape quantum number, l. A maximum of 2 electrons can be
found in each probability region, each electron have a spin quantum number with a value of
either +½ or -½. The orbital shape quantum number has the following values and designations
for the shape of the probability region in which the electrons are most probably to be found.

Value of l 1 2 3 4
Sub-shell designation s p d f

The sub-shell designations stand for sharp, principal, diffuse, and fundamental. The probability
regions described by these sub-shells are as follows:

s - orbitals - are spherical shaped

probability regions. The radius of these
spherical regions increases with
increasing principal quantum number, n.
Again, each of these orbitals can contain
a maximum of 2 electrons.

p - orbitals - these can only be

present if the principal quantum
number is 2 or greater. There are
3 different types of p orbitals,
designated px, py, and pz. These
are approximately peanut shaped
orbitals, with the axis oriented
vertically (pz ) and horizontally
(px & py).

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Since 2 electrons can occur in each of the different p orbitals, a maximum of 6 electrons
are associated with p-orbitals in each principal shell.

d - orbitals - These can only be present if the principal quantum number is 3 or greater.
There are 5 different probability regions of d orbitals. These are seen in the drawings
below, and are designated dz2, dx2 - y2, dxy, dyz, and dxz. Since 2 electrons can occur in
each of the different d orbitals, a maximum of 10 electrons can occur in d-orbitals for
each principal shell.

f - orbitals - these are more difficult to describe in a graphical sense, but it turns out
there are 7 possible f -orbitals, each being able to contain 2 electrons, for a maximum
total of 14 electrons. Only shells with principal quantum numbers of 5 or greater can
contain f -orbital electrons.

The Pauli Exclusion Principal states that no 2 electrons in an atom can have the same
quantum numbers, thus each of the sub-orbitals described above can have a maximum of 2
electrons, and each of these will have opposite values of the spin quantum number.
As the atomic number (number of protons) in an atom
increases, the shells and sub-shells with lower energy are filled
first. The drawing at the right illustrates qualitatively the
energy relationships between the various shells and sub-shells
of atoms. Thus 1s sub-shells with the lowest energy are filled
first. These are followed by 2s orbitals, then 2p orbitals. As
the principal quantum number increases to 3, the 3s, 3p, and 3d
orbitals are filled. But, beginning with n = 4, there is overlap
between the energies of s and d orbitals, and thus the 4s orbital
is filled before the 3d orbitals, and the 4p orbitals do not
contain electrons until the 3d orbitals are filled. This overlap
continues in a similar way for higher principle quantum
number shells.

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Electronic Structure of the Atom and the Periodic Table of the Elements

Based on the energy levels of the various sub-shells, we can begin filling in the electronic
structure of atoms as shown in the following table. Note that this table only goes up to atomic
number 36. A complete table can found in Klein and Dutrow on pages 44-46.

K L M N
At. # Elem.
1s 2s 2p 3s 3p 3d 4s 4p 4d 4f
1 H 1
2 He 2 <------- K-shell completely filled
3 Li 2 1
4 Be 2 2
5 B 2 2 1
6 C 2 2 2
7 N 2 2 3
8 O 2 2 4
9 F 2 2 5
10 Ne 2 2 6 <----L-shell completely filled
11 Na 2 2 6 1
12 Mg 2 2 6 2
13 Al 2 2 6 2 1
14 Si 2 2 6 2 2
15 P 2 2 6 2 3
16 S 2 2 6 2 4
17 Cl 2 2 6 2 5
18 Ar 2 2 6 2 6 <----3p-orbitals completely filled
19 K 2 2 6 2 6 1

20 Ca 2 2 6 2 6 2
21 Sc 2 2 6 2 6 1 2
22 Ti 2 2 6 2 6 2 2
23 V 2 2 6 2 6 3 2
24 Cr 2 2 6 2 6 5 1
25 Mn 2 2 6 2 6 5 2
26 Fe 2 2 6 2 6 6 2
27 Co 2 2 6 2 6 7 2
28 Ni 2 2 6 2 6 8 2
29 Cu 2 2 6 2 6 10 1

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30 Zn 2 2 6 2 6 10 2
31 Ga 2 2 6 2 6 10 2 1
32 Ge 2 2 6 2 6 10 2 2
33 As 2 2 6 2 6 10 2 3
34 Se 2 2 6 2 6 10 2 4
35 Br 2 2 6 2 6 10 2 5
36 Kr 2 2 6 2 6 10 2 6 <- 4p orbitals filled

This periodic filling of shells and sub-shells forms the basis of the periodic table of the
elements. Elements with similar configurations of outer shell electrons (called valence
electrons) have similar chemical properties. The rows in the table, labeled 1, 2, 3, 4, 5, 6, & 7,
correspond to the principal quantum number.

Column I is a groups of elements that have 1 electron on their outermost shell, which in
this case is an s - orbital. Group I elements are called the alkaline metals.

Elements in column II, called the alkaline - earth metals, all have 2 electrons in their
completely filled outer s-orbital shells.

Groups III, IV, V, VI, and VII all have the same number of outer shell electrons as the
group number. Group VII elements are known as the halogens.

Group VIII elements are all characterized by having completely filled p -orbital shells
with 8 electrons total in their outermost s - and p -shells. This group is known as the
Noble Gases or Inert Gases, inert because these elements do not combine with
themselves or any other element under normal conditions.

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The transition metals occur between the alkaline earths (Group II) and Group III. These
are elements with partially filled d - orbitals.

Note the discontinuity in the table at element 57. Beginning with Ce, 4f -orbitals begin
to be filled, and to keep the chart from becoming too wide, elements 58 to 71 (Ce to Lu)
are placed at the bottom of the chart. The series from La to Lu is known as the
Lanthanides and these elements are also commonly called the Rare Earth Elements.

Similarly, another discontinuity occurs at element 89, Ac where the 5f - orbitals begin to
be filled, starting with the element Th. elements 89 through 103 are referred to as the
Actinides.

The Ion

In a neutral atom, the number of protons and the number of electrons are equal, thus the
number of positive charges is the same as the number of negative charges and the atom has no
charge. However, some elements in the Periodic Table tend to loose electrons to become
positively charged and some elements tend to gain electrons to become negatively charged.
Atoms with an electrical charge are called ions.

Elements that tend to loose electrons are called metals, while those that tend to gain electrons
are non-metals.

Metals thus tend to form positively charged ions called cations, while non-metals tend to form
negatively charged ions called anions.

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Ionization Potential

When electrons are either removed or gained by an atom there is a transfer of energy. The
amount of energy required to remove an electron is called the ionization potential. The version
of the periodic table shown below gives value of the first ionization potential. Note that
elements with high ionization potential do not like to give up electrons, while those with low
ionization potential can give up electrons more readily and tend to become cations. We can
make the following observations:

The Noble gases all have very high first ionization potentials, indicating that their
electronic structure is stable. A glance at the periodic table showing filling shells (above)
indicates that the Noble Gases all have in common completely filled p - orbitals. It is
because these sub-orbital shells are full that these elements do not readily become ions
and do not easily combine with other elements to become compounds.

Elements in Group I (the alkalies), on the other hand have very low first ionization
potentials, and thus it is relatively easy to remove one electron. Since all of these
elements have in common an outermost shell containing 1 electron in the s - orbital,
these elements tend to become +1 ions (i.e. Li+1, Na+1, K+1, Rb+1, Cs+1, etc.) Note that
removal of this electron will leave the atoms with an electronic configuration of the
Noble gases, i.e. they will have completely filled outermost electron shells. Second
ionization potentials (the energy required to remove a second electron) is also very high
for these elements, again indicating that once they become +1 ions they have a stable
electronic configuration.

Elements in Group II (the alkaline earths) also have relatively low first ionization
potentials and have relatively low second ionization potentials. Thus, these elements
tend to lose 2 electrons to become +2 ions (i.e. Be+2, Mg+2, Ca+2, Sr+2, Ba+2, etc.) Once
they have lost these two electrons they also have an electronic configuration with
completely filled outer electron shells, similar to the Noble Gases.

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Elements in Group VII (the halogens) have very high first ionization potentials. They
don't like to give up electrons. But note that if they gain an electron to become a -1 ion,
they will also have completely filled outer electron shells similar to the Noble gases.
Thus these elements tend to gain electrons to become -1 ions (i.e. F-1, Cl-1, Br-1, etc.).

Based on similar reasoning, Group III elements tend to lose 3 electrons to become +3
ions (i.e. B+3, Al+3, Ga+3, etc.). Group IV elements tend to lose 4 electrons to become
+4 ions (i.e. C+4, Si+4, Ge+4). But Pb, usually only loses 2 electrons to become Pb+2.

Elements in Group V tend to lose 5 electrons to become +5 ions (i.e. N+5, P+5, As+5).

Group VI tend to gain electrons to become -2 ions (i.e. O-2, S-2, Se-2), but sulfur
sometimes loses 6 electrons to become S+6.

The transition elements all have d-orbital electrons in their outermost shells, and because
they have low to high first ionization potentials their behavior is somewhat variable. The
elements in the third column tend to become +3 ions (Sc+3, Y+3, La+3 ), those in the 4th
column tend to become +4 ions (Ti+4, Zr+4, Hf+4), and those in the 5th column tend to
become +5 ions (V+5, Nb+5, Ta+5). But the 5th through 11th column show variable
ions. For example, Cr is usually Cr+3, Mn can be usually Mn+2, Mn+3, or Mn+4, Fe can
be either Fe+2 (ferrous iron) or Fe+3 (ferric iron), Ni, Co, and Zn become +2 ions, and
Cu can be either Cu+1or Cu+2.

The rare earth elements tend to become +3 ions, with the exception of Eu, which can be
either Eu+2, or Eu+3. The actinides U and Th tend to become +4 ions.

To summarize, the common valence states of the common elements are listed in the table below
for quick reference.

Valence States of the Common Elements

H+1

Li+1 Be+2 B+3 C+4 N+5 O-2 F-1

Na+1 Mg+2 Al+3 Si+4 P+5 S-2 Cl-1

Transition Elements S+6

K+1 Ca+2 Sc+3 Ti+4 V+5 Cr+3 Mn+2 Fe+2 Co+2 Ni+2 Cu+2 Zn+2 Ga+3 Ge+4 As+3 Br-1
Mn+3 Fe+3 As+5
Mn+4
Th+4
REE +3, except Eu sometimes +2

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U+4

Electronegativity

Another way of looking at the tendency to gain or lose electrons is based on the
electronegativity. Electronegativity is defined as the ability of an atom in a crystal structure or
molecule to attract electrons into its outer shell. Elements with low values of electronegativity
are electron donors, and those with high values are electron acceptors. The Noble gases have
electronegativity values of zero, because they neither accept or donate electrons. As we will
see in our later discussion, electronegativity difference between atoms plays an important role
in determining they type of chemical bond that forms between elements.

Chemical Bonding

The chemical and physical properties of crystals depend almost entirely on the forces that bind
the atoms together in a crystal structure. These forces are known collectively as chemical
bonds. Chemical bonding depends on the electronic structure of the atoms involved, in
particular the valence electrons in the outermost shells, and on the size of the ion or atom.

In general we recognize 4 different types of chemical bonds, although as we will see, all bond
types are transitional from one type to another.
Ionic Bonds

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As we have seen, there is a tendency for atoms to lose or gain electrons and become ions in
order to achieve the stable electronic configuration with completely filled outer electron shells.
Positively charged ions are called cations and negatively charged ions are called anions. These
ions can achieve various values of electronic charge depending on the number of electrons
gained or lost.

+1 monovalent cations
+2 divalent cations
+3 trivalent cations
+4 tetravalent cations
+5 pentavalent cations
-1 monovalent anions
-2 divalent anions

When atoms become charged ions the force of attraction between oppositely charged ions
results in an ionic bond.

For example, Na has one

electron in its outermost shell.
It will tend to give up this
electron to become Na+1 ion.
Similarly, Cl has 7 electrons in
its outermost shell and would
like to gain an electron to
become Cl-1 ion. Once these
atoms become Na+1 and Cl-1,
the force of attraction between
the oppositely charged ions
results in an ionic bond.

Ionic bonds are non-directional in nature, that is the attractive forces occur form all directions.
Crystals made of ionically bonded atoms tend to have the following properties:
Dissolve easily in polar solvents like water (H2O is a polar solvent because the hydrogen
ions occur on one side the water molecule and give it a slight positive charge while the
other side of the water molecule has a slight negative charge).

Tend to form crystals with high symmetry.

Moderate hardness and density.

High melting temperatures.

Generally poor conductors of heat and electricity (they are good materials for thermal
and electrical insulation).

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Covalent Bonds

Covalent bonds can also be thought of as shared electron bonds. Covalent bonds develop when
atoms can achieve the a stable outer shell electron configuration by sharing electrons with
another atom. This results in each of the atoms having a stable electronic configuration part of
the time.

For example, Oxygen has six electrons in its

outer shell, 2 are in s-orbitals and 4 are in
p-orbitals. If it can gain two more electrons
to fill its p-orbital shells, it would have the
stable electronic configuration of a Noble
gas. A second Oxygen atom also needs 2
more electrons to achieve the stable
configuration. If the two Oxygens each share
2 electrons with each other, then each
Oxygen has the stable electronic
configuration part of the time. The covalent
bond thus formed is a very strong bond.
Thus we find oxygen gas is composed of O2
molecules. Similarly, F2 and Cl2 gases are
composed of covalently bonded F and Cl
pairs.

Covalent bonds are very strong directional bonds, that is they occur along the zone where they
electrons are shared. Covalently bonded crystals have the following properties:

Relatively insoluble in polar solvents like water.

High melting temperatures.

Generally form crystals structures of low symmetry.

Tend to have high hardness.

Generally poor conductors of heat and electricity.

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Elements near the right hand side of the periodic table tend to bond to each other by covalent
bonds to form molecules that are found in crystal structures. For example Si and O form an
SiO4-4 molecule that can bind to other atoms or molecules either covalently or ionically.
Carbon has four electrons in its outer shell and needs 4 more to achieve the stable electronic
configuration. So a Carbon atom can share electrons with 4 other Carbon atoms to form
covalent bonds. This results in compounds like diamond or graphite that are held together by
strong covalent bonds between Carbon atoms.

In reality, bonding between atoms usually does not take place as pure covalent or pure ionic
bonds, but rather as a mixture of bond types. The amount of each type is determined by the
electronegativity difference between the atoms involved.

For example, consultation of electronegativity chart

above shows Cl with a value of 3.16 and Na with a
value of 0.93. The electronegativity difference is 2.3,
suggesting that only 80% of the bonding in NaCl is
ionic. Even looking a larger electronegativity
difference like for NaF, the bonding would by only
about 90% ionic. Bonding between Oxygen atoms or
between Carbon atoms, where the electronegativity
difference is 0, would result in pure covalent bonds.

Metallic Bonds

None of the bond types discussed so far result in materials that can easily conduct electricity.
Pure metals however do conduct electricity easily and therefore must be bonded in a different
way.
This is the metallic bond, where positively charge atomic nuclei share
electrons in their electron clouds freely. In a sense, each atom is sharing
electrons freely with other atoms, and some of the electrons are free to move
from atom to atom. Since some of the electrons are free to move,
metallically bonded materials have high electrical conductivity.
Pure metals appear to bind in this way. When crystals are formed with metallic bonds they
have the following properties:

Low to Moderate hardness.

Usually very malleable and ductile.

Good thermal and electrical conductors.

Soluble only in acids.

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Crystals with high symmetry.

Residual Bonds

Residual bonds are weak bonds that involve the attraction of partially charged atoms or
molecules. These partial charges are created when electrons become concentrated on one side
of an atom or molecule to satisfy ionic or covalent bonds. This sometimes creates a polar atom
or molecule which has a concentration of negative charges on one side and a concentration of
positive charges on the other side. When residual bonds occur in a crystal structure, they
generally form planes or zones of easy cleavage because of the weakness of the residual bond.

Two special cases are discussed here.

Hydrogen Bonds - These occur in the special
case of hydrogen, because H has only one
electron. When Hydrogen gives up this electron
to become H+1 ion or shares its single electron
with another atom in a covalent bond, the
positively charged nucleus of the hydrogen
atom is exposed, giving that end of the H ion a
residual +1 charge. This is what causes the
H2O molecule to be a polar molecule seen here.
Similarly, an OH-1 molecule, common in sheet
silicate minerals like micas and clay minerals,
although possessing a -1 charge will have
exposed H nuclei that can bond to other
negative residual charges forming a weak
hydrogen bond. Layers of OH-1 molecules in
the sheet silicates result in the easy cleavage
along the {001} planes.

van der Waals Bonds are also residual bonds that result from polarization of atoms or
molecules. In the mineral graphite, the C atoms are held together by strong covalent
bonds, that result in concentrations of positive and negative charges at either end of the C
atoms. Bonding between sheets takes place as a result of the slight attraction between
these residual charges from one sheet to another.

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Mixture of Bonds in Crystals

Since most crystals are complex mixtures of atoms, there will likely be more than one bond
type in complex crystals. Thus, except in very simple compounds properties such as hardness,
cleavage, solution rate, and growth rate may be directional, as discussed in a previous lecture.

Examples of questions on this material that could be asked on an exam

1. Define the following : (a) atomic number, (b) atomic weight, (c) s-orbitals, (d)
p-orbitals, (e) d-orbitals, (f) ion, (g) cation, (h) anion.

2. What are ionic bonds and what physical properties are characteristic of compounds that
contain ionic bonds?

3. What are covalent bonds and what physical properties are characteristic of compounds
that contain ionic bonds?

4. What are metallic bonds and what physical properties are characteristic of compounds
that contain ionic bonds?

5. What are residual bonds and what physical properties are characteristic of compounds
that contain ionic bonds?

6. Name several elements in each of the following groups (a) Alkalies, (b) Alkaline Earths,
(c) halogens, (d) Nobel Gases, (e) Rare Earths, (f) Actinides

7. What is the common valence state of elements in each of the following groups (a)
Alkalies, (b) Alkaline Earths, (c) halogens

8. What is electronegativity and why is it mportant?

Return to EENS 2110 Page

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SOME BASIC FORMULAS

Distance formula
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Radius ratio
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Calculation of radius ratio

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Limiting radius ratio for 8-coordination (caesium chloride

structure)

The rotatable structure opposite shows the CsCl structure in which the Cs+ ion is
surrounded by 8 Cl- ions.

To get as close to the cation as possible, the anions must touch along the edge of the cube,
as shown in the figure below.

The side of the cube has a length, a, where:

a = 2r-

Along the body diagonal, the Cs+ is touching the two Cl- ions on either end so its length, d,
is:

d = r- + 2r+ + r- = 2r+ + 2r-

Figure 1 Two dimensional view of packing around Cs+ in CsCl showing two
opposite edges of the unit cell.
Using Pythagoras’ theorem, the length of the side and the body diagonal
of a cube are related:
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d2 = a2 + a2 + a2 = 3a2 = 3 × 4r-2 = 12r-2

d = 2(3)1/2r-

So,

2r- + 2r+ = 2r(3)1/2r-

r+ / r- = (3)1/2 – 1 = 0.732

Limiting radius ratio for 6-coordination (sodium chloride

structure)

The rotatable structure opposite shows the NaCl structure in which the
Na+ ion is surrounded by 6 Cl- ions.

As shown in the figure below, along the cube edge, the Na+ is touching
two Cl- ions so its length, a, is:
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a = (r-) + (2r+)+ (r-)= (2r+) + (2r-)

To get as close to the cation as possible, the anions must touch along
the diagonal of a face of the cube.

The diagonal has length, d, where:

d = r- + 2r- + r- = 4r-

Using Pythagoras’ theorem, the length of the side and face diagonal of
a cube are related:

d2 = a2 + a2 = 2a2

d = (2)1/2a

So,

4r- = (2)1/2(2r+ + 2r-)

r+ / r- = (2)1/2 – 1 = 0.414
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Limiting ratio for coordination No 3

Reference
For more detail of radius ratio calculation visit
https://www.youtube.com/watch?v=6vI_Cupxm9s&list=PLzpO
KLgp6dEWDzy0-s-CZRMMpAd8pPc3b&index=8
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Intext Questions
1.10 Give the significance of a ‘lattice point’.
1.11 Name the parameters that characterise a unit cell.
1.12 Distinguish between
(i) Hexagonal and monoclinic unit cells
(ii) Face-centred and end-centred unit cells.
1.13 Explain how much portion of an atom located at (i) corner and (ii) body-
centre of a cubic unit cell is part of its neighbouring unit cell.

1.6 Close Packed In solids, the constituent particles are close-packed, leaving the
Structures minimum vacant space. Let us consider the constituent particles as
identical hard spheres and build up the three dimensional structure in
three steps.
(a) Close Packing in One Dimension
There is only one way of arranging spheres in a one dimensional close
packed structure, that is to arrange them in a row and touching each
other (Fig. 1.13).
In this arrangement, each sphere is in contact
with two of its neighbours. The number of nearest
neighbours of a particle is called its coordination
Fig. 1.13: Close packing of spheres in number. Thus, in one dimensional close packed
one dimension arrangement, the coordination number is 2.
(b) Close Packing in Two Dimensions
Two dimensional close packed structure can be generated by stacking
(placing) the rows of close packed spheres. This can be done in two
different ways.
(i) The second row may be placed in contact with the first one such
that the spheres of the second row are exactly above those of the
first row. The spheres of the two rows are aligned horizontally as
well as vertically. If we call the first row as ‘A’ type row, the second
row being exactly the same as the first one, is also of ‘A’ type.
Similarly, we may place more rows to obtain AAA type of
arrangement as shown in Fig. 1.14 (a).

Fig. 1.14: (a) Square close packing (b) hexagonal close

packing of spheres in two dimensions

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In this arrangement, each sphere is in contact with four of its

neighbours. Thus, the two dimensional coordination number is 4. Also,
if the centres of these 4 immediate neighbouring spheres are joined, a
square is formed. Hence this packing is called square close packing
in two dimensions.
(ii) The second row may be placed above the first one in a staggered
manner such that its spheres fit in the depressions of the first row.
If the arrangement of spheres in the first row is called ‘A’ type, the
one in the second row is different and may be called ‘B’ type. When
the third row is placed adjacent to the second in staggered manner,
its spheres are aligned with those of the first layer. Hence this layer
is also of ‘A’ type. The spheres of similarly placed fourth row will
be aligned with those of the second row (‘B’ type). Hence this
arrangement is of ABAB type. In this arrangement there is less free
space and this packing is more efficient than the square close
packing. Each sphere is in contact with six of its neighbours and
the two dimensional coordination number is 6. The centres of these
six spheres are at the corners of a regular hexagon (Fig. 1.14b)
hence this packing is called two dimensional hexagonal close-
packing. It can be seen in Figure 1.14 (b) that in this layer there
are some voids (empty spaces). These are triangular in shape. The
triangular voids are of two different types. In one row, the apex of
the triangles are pointing upwards and in the next layer downwards.
(c) Close Packing in Three Dimensions
All real structures are three dimensional structures. They can be
obtained by stacking two dimensional layers one above the other. In
the last Section, we discussed close packing in two dimensions which
can be of two types; square close-packed and hexagonal close-packed.
Let us see what types of three dimensional close packing can be obtained
from these.
(i) Three dimensional close packing from two dimensional square
close-packed layers: While placing the second square close-packed
layer above the first we follow the same rule that was
followed when one row was placed adjacent to the other.
The second layer is placed over the first layer such that
the spheres of the upper layer are exactly above those of
the first layer. In this arrangement spheres of both the
layers are perfectly aligned horizontally as well as
vertically as shown in Fig. 1.15. Similarly, we may place
more layers one above the other. If the arrangement of
spheres in the first layer is called ‘A’ type, all the layers
have the same arrangement. Thus this lattice has AAA....
type pattern. The lattice thus generated is the simple
cubic lattice, and its unit cell is the primitive cubic unit
cell (See Fig. 1.9).
(ii) Three dimensional close packing from two
dimensional hexagonal close packed layers: Three
Fig. 1.15: Simple cubic lattice formed dimensional close packed structure can be generated
by A A A .... arrangement by placing layers one over the other.

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(a) Placing second layer over the first layer

Let us take a two dimensional hexagonal close packed layer ‘A’ and
place a similar layer above it such that the spheres of the second layer
are placed in the depressions of the first layer. Since the spheres of the
two layers are aligned differently, let us call the second layer as B. It
can be observed from Fig. 1.16 that not all the triangular voids of the
first layer are covered by the spheres of the second layer. This gives rise
to different arrangements. Wherever a sphere of the second layer is
above the void of the first layer (or vice versa) a tetrahedral void is

Fig. 1.16: A stack of two layers of close packed spheres and voids
generated in them. T = Tetrahedral void; O = Octahedral void

formed. These voids are called tetrahedral voids because a tetrahedron

is formed when the centres of these four spheres are joined. They have
been marked as ‘T’ in Fig. 1.16. One such void has been shown
separately in Fig. 1.17.

Fig 1.17
Tetrahedral and
octahedral voids
(a) top view
(b) exploded side
view and
(c) geometrical shape
of the void.

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At other places, the triangular voids in the second layer are above
the triangular voids in the first layer, and the triangular shapes of these
do not overlap. One of them has the apex of the triangle pointing
upwards and the other downwards. These voids have been marked as
‘O’ in Fig. 1.16. Such voids are surrounded by six spheres and are
called octahedral voids. One such void has been shown separately in
Fig. 1.17. The number of these two types of voids depend upon the
number of close packed spheres.
Let the number of close packed spheres be N, then:
The number of octahedral voids generated = N
The number of tetrahedral voids generated = 2N
(b) Placing third layer over the second layer
When third layer is placed over the second, there are two possibilities.
(i) Covering Tetrahedral Voids: Tetrahedral voids of the second layer
may be covered by the spheres of the third layer. In this case, the
spheres of the third layer are exactly aligned with those of the first
layer. Thus, the pattern of spheres is repeated in alternate layers.
This pattern is often written as ABAB ....... pattern. This structure
is called hexagonal close packed (hcp) structure (Fig. 1.18). This
sort of arrangement of atoms is found in many metals like
magnesium and zinc.

Fig. 1.18
(a) Hexagonal cubic
close-packing
exploded view
showing stacking of
layers of spheres
(b) four layers
stacked in each case
and (c) geometry of
packing.

Fig. 1.19 A (ii) Covering Octahedral Voids: The

(a) ABCABC... third layer may be placed above
arrangement of the second layer in a manner such
C
layers when that its spheres cover the
octahedral void is octahedral voids. When placed in
covered (b) fragment (b) this manner, the spheres of the
of structure formed B
third layer are not aligned with
by this arrangement
those of either the first or the second
resulting in cubic
closed packed (ccp) A layer. This arrangement is called ‘C’
or face centred cubic type. Only when fourth layer is
(fcc) structure. (a) placed, its spheres are aligned with

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those of the first layer as shown in Figs. 1.18 and 1.19. This pattern
of layers is often written as ABCABC ........... This structure is called
cubic close packed (ccp) or face-centred cubic (fcc) structure. Metals
such as copper and silver crystallise in this structure.
Both these types of close packing are highly efficient and 74%
space in the crystal is filled. In either of them, each sphere is in contact
with twelve spheres. Thus, the coordination number is 12 in either of
these two structures.

1.6.1 Formula of a Earlier in the section, we have learnt that when particles are close-
Compound packed resulting in either ccp or hcp structure, two types of voids are
and Number generated. While the number of octahedral voids present in a lattice is
of Voids equal to the number of close packed particles, the number of tetrahedral
Filled voids generated is twice this number. In ionic solids, the bigger ions
(usually anions) form the close packed structure and the smaller ions
(usually cations) occupy the voids. If the latter ion is small enough
then tetrahedral voids are occupied, if bigger, then octahedral voids.
Not all octahedral or tetrahedral voids are occupied. In a given
compound, the fraction of octahedral or tetrahedral voids that are
occupied, depends upon the chemical formula of the compound, as
can be seen from the following examples.

Example 1.1 A compound is formed by two elements X and Y. Atoms of the element
Y (as anions) make ccp and those of the element X (as cations) occupy
all the octahedral voids. What is the formula of the compound?
Solution The ccp lattice is formed by the element Y. The number of octahedral
voids generated would be equal to the number of atoms of Y present in
it. Since all the octahedral voids are occupied by the atoms of X, their
number would also be equal to that of the element Y. Thus, the atoms
of elements X and Y are present in equal numbers or 1:1 ratio. Therefore,
the formula of the compound is XY.

Example 1.2 Atoms of element B form hcp lattice and those of the element A occupy
2/3rd of tetrahedral voids. What is the formula of the compound formed
by the elements A and B?
Solution The number of tetrahedral voids formed is equal to twice the number of
atoms of element B and only 2/3rd of these are occupied by the atoms
of element A. Hence the ratio of the number of atoms of A and B is 2
× (2/3):1 or 4:3 and the formula of the compound is A4B3.

Locating Tetrahedral and Octahedral Voids

We know that close packed structures have both tetrahedral and octahedral
voids. Let us take ccp (or fcc) structure and locate these voids in it.
(a) Locating Tetrahedral Voids
Let us consider a unit cell of ccp or fcc lattice [Fig. 1(a)]. The unit cell is divided
into eight small cubes.

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Each small cube has atoms at alternate corners [Fig. 1(a)]. In all, each small
cube has 4 atoms. When joined to each other, they make a regular tetrahedron.
Thus, there is one tetrahedral void in each small cube and eight tetrahedral
voids in total. Each of the eight small cubes have one void in one unit cell of ccp
structure. We know that ccp structure has 4 atoms per unit cell. Thus, the
number of tetrahedral voids is twice the number of atoms.

Fig. 1: (a) Eight tetrahedral voids per unit cell of ccp structure
(b) one tetrahedral void showing the geometry.

(b) Locating Octahedral Voids

Let us again consider a unit cell of ccp or fcc lattice [Fig. 2(a)]. The body centre
of the cube, C is not occupied but it is surrounded by six atoms on face centres.
If these face centres are joined, an octahedron is generated. Thus, this unit cell
has one octahedral void at the body centre of the cube.
Besides the body centre, there is one octahedral void at the centre of each
of the 12 edges. [Fig. 2(b)]. It is surrounded by six atoms, four belonging to the
same unit cell (2 on the corners and 2 on face centre) and two belonging to two
adjacent unit cells. Since each edge of the cube is shared between four adjacent
1 th
unit cells, so is the octahedral void located on it. Only of each void belongs
4
to a particular unit cell.

(a) (b)

Fig. 2: Location of octahedral voids per unit cell of ccp or fcc lattice (a) at the body centre
of the cube and (b) at the centre of each edge (only one such void is shown).

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Thus in cubic close packed structure:

Octahedral void at the body-centre of the cube = 1
12 octahedral voids located at each edge and shared between four unit cells
1
= 12  3
4
∴ Total number of octahedral voids = 4
We know that in ccp structure, each unit cell has 4 atoms. Thus, the number
of octahedral voids is equal to this number.

1.7 Packing In whatever way the constituent particles (atoms, molecules or ions)
Efficiency are packed, there is always some free space in the form of voids.
Packing efficiency is the percentage of total space filled by the
particles. Let us calculate the packing efficiency in different types of
structures.
1.7.1 Packing Both types of close packing (hcp and ccp) are equally efficient. Let us
Efficiency in calculate the efficiency of packing in ccp structure. In Fig. 1.20 let the
hcp and ccp unit cell edge length be ‘a’ and face diagonal AC = b.
Structures
In  ABC
AC2 = b2 = BC2 + AB2
= a2+a2 = 2a2 or
b= 2a
If r is the radius of the sphere, we find
b = 4r = 2a
4r
or a =  2 2r
2
a
(we can also write, r  )
2 2
We know, that each unit cell in ccp structure,
Fig. 1.20: Cubic close packing other has effectively 4 spheres. Total volume of four
sides are not provided with
spheres for sake of clarity. spheres is equal to 4   4 /3  r 3 and volume of the

 
3
cube is a 3 or 2 2r .
Therefore,
Volume occupied by four spheres in the unit cell 100
Packing efficiency = %
Total volumeof the unit cell

4   4 / 3  r 3  100
 %
2 
3
2r

16 / 3  r 3  100
 %  74%
16 2r 3
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1.7.2 Efficiency of From Fig. 1.21, it is clear that the

Packing in atom at the centre will be in touch
Body- with the other two atoms diagonally
Centred arranged.
Cubic In Δ EFD,
Structures b2 = a2 + a2 = 2a2
b = 2a
Now in Δ AFD
2 2 2 2 2 2
c = a + b = a + 2a = 3a
c = 3a
The length of the body diagonal
Fig. 1.21: Body-centred cubic unit
c is equal to 4r, where r is the radius
cell (sphere along the
of the sphere (atom), as all the three body diagonal are shown
spheres along the diagonal touch with solid boundaries).
each other.
Therefore, 3a = 4r
4r
a=
3
3
Also we can write, r = a
4
In this type of structure, total number of atoms is 2 and their volume

is 2 
4 r 3 .
3
3 3
 4   
Volume of the cube, a3 will be equal to  r  or a3   4 r  .
 3   3 
Therefore,
Volume occupied by two spheres in the unit cell  100
Packing efficiency = %
Total volume of the unit cell

2   4 /3  r 3  100
 %
 
3
 4/ 3 r
 

 8/ 3  r 3  100
 %  68%

64 / 3 3 r 3 
1.7.3 Packing In a simple cubic lattice the atoms are located only on the corners of the
Efficiency in cube. The particles touch each other along the edge (Fig. 1.22).
Simple Cubic Thus, the edge length or side of the cube ‘a’, and the radius of each particle,
Lattice r are related as
a = 2r
The volume of the cubic unit cell = a3 = (2r)3 = 8r3
Since a simple cubic unit cell contains only 1 atom
4 r 3
The volume of the occupied space =
3
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∴ Packing efficiency
Volume of one atom
= Volume of cubic unit cell  100%

4 3
r
= 3 
 100   100
Fig. 1.22 8r 3 6
Simple cubic unit cell. = 52.36% = 52.4 %
The spheres are in
contact with each Thus, we may conclude that ccp
other along the edge of and hcp structures have maximum
the cube. packing efficiency.

1.8 Calculations From the unit cell dimensions, it is possible to calculate the volume of
Involving the unit cell. Knowing the density of the metal, we can calculate the
mass of the atoms in the unit cell. The determination of the mass of a
Unit Cell single atom gives an accurate method of determination of Avogadro
Dimensions constant. Suppose, edge length of a unit cell of a cubic crystal determined
by X-ray diffraction is a, d the density of the solid substance and M the
molar mass. In case of cubic crystal:
3
Volume of a unit cell = a
Mass of the unit cell
= number of atoms in unit cell × mass of each atom = z × m
(Here z is the number of atoms present in one unit cell and m is the
mass of a single atom)
Mass of an atom present in the unit cell:
M
m = N (M is molar mass)
A

Therefore, density of the unit cell

mass of unit cell
=
volume of unit cell
z.m z.M zM
= = 3 or d = 3
a3 a .N A a NA
Remember, the density of the unit cell is the same as the density of
the substance. The density of the solid can always be determined by
other methods. Out of the five parameters (d, z M, a and NA), if any
four are known, we can determine the fifth.

Example 1.3 An element has a body-centred cubic (bcc) structure with a cell edge of
288 pm. The density of the element is 7.2 g/cm3. How many atoms are
present in 208 g of the element?
Solution Volume of the unit cell = (288 pm)3
= (288×10-12 m)3 = (288×10-10 cm)3
= 2.39×10-23 cm3

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Volume of 208 g of the element

mass 208 g
   28.88 cm 3
density 7.2 g cm 3
Number of unit cells in this volume
28.88cm 3
 = 12.08×1023 unit cells
2.39  1023 cm 3 / unit cell

Since each bcc cubic unit cell contains 2 atoms, therefore, the total number
of atoms in 208 g = 2 (atoms/unit cell) × 12.08 × 1023 unit cells
= 24.16×1023 atoms

X-ray diffraction studies show that copper crystallises in an fcc unit Example 1.4
cell with cell edge of 3.608×10-8 cm. In a separate experiment, copper is
determined to have a density of 8.92 g/cm3, calculate the atomic mass
of copper.
In case of fcc lattice, number of atoms per unit cell, z = 4 atoms Solution
3
dN A a
Therefore, M =
z
8.92 g cm –3  6.022  1023 atoms mol 1  (3.608  10 8 cm)3

4 atoms
= 63.1 g/mol
Atomic mass of copper = 63.1u

Silver forms ccp lattice and X-ray studies of its crystals show that the Example 1.5
edge length of its unit cell is 408.6 pm. Calculate the density of silver
(Atomic mass = 107.9 u).
Since the lattice is ccp, the number of silver atoms per unit cell = z = 4 Solution
–1 -3 –1
Molar mass of silver = 107.9 g mol = 107.9×10 kg mol
Edge length of unit cell = a = 408.6 pm = 408.6×10–12 m
z.M
Density, d = a 3 .N
A

=

4  107.9  103 kg mol 1  = 10.5×103 kg m–3
 408.6  10   6.022  10 
12 3 23 1
m mol
-3
= 10.5 g cm

Intext Questions
1.14 What is the two dimensional coordination number of a molecule in
square close-packed layer?
1.15 A compound forms hexagonal close-packed structure. What is the total
number of voids in 0.5 mol of it? How many of these are tetrahedral voids?

21 The Solid State

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Reference

For videos in HCP and CCP visit

https://www.youtube.com/watch?v=T8iHcvK0jiw&index=5&list=PLzpO
KLgp6dEWDzy0-s-CZRMMpAd8pPc3b

for types of voids visit

https://www.youtube.com/watch?v=QuXBoA_ax1Q&index=7&list=PLz
pOKLgp6dEWDzy0-s-CZRMMpAd8pPc3b