SPH 302/392: STRUCTURE AND PROPERTIES OF MATTER

Introduction
ο as the name suggests, this course looks at matter (solids, liquids, gases, plasma, etc) right
from the constituent particles (atoms, ions, molecule) to the bulk behavior we observe in
ordinary conditions. it lays the foundation for more advanced courses in Solid State
Physics, Materials Science, Thermodynamics, and Quantum Mechanics.
ο the knowledge gained (acquired) from this course unit can be applied in (manufacturing of
materials that can be utilized) in various fields as telecommunication, information
technology, security/defence/weaponry matters, transportation (automotive,
marine/maritime, aviation and space exploration), building/road/construction engineering,
in medicine and pharmaceutical areas, teaching/learning/research fields,
Cosmetic/fabric/textile/clothing industry, entertainment/leisure areas etc.

States of matter
ο there are five (5) known states of matter, i.e., solids, liquids, gases, plasma (extreme high
temperatures) and Bose-Einstein condensates (extreme low temperatures).
ο the first four are observable in everyday life.
ο the last exists in extreme situations – occur at extreme coldness (very low temperature).
ο historically, distinction is made based on qualitative differences in physical properties.
State of Matter
Solid Liquid Gas
• maintains both fixed • maintains fixed volume • maintains flexible
volume and shape, i.e., and variable (changing) volume and shape, i.e.,
are rigid and shape, i.e., are soft and are soft and
incompressible. compressible. compressible.
• constituent particles are • constituent particles are • constituent particles are
closed/tightly packed sparsely packed kept far apart.

plasma : flexible volume and shape, contains a significant number of ionized particles (+ve
or -ve) moving freely.

State/Phase transitions
A transformation from one state to another is called phase transition. Also, referred to as
phase change.

−1−
State transition involves either addition or subtraction of thermal energy.
It depends on temperature and pressure.
Affects - particles arrangement/aggregate
- energy of the particle
- distance between particles
A phase change can either be exothermic or endothermic.
# exothermic – heat energy is given out, i.e., removal of heat energy.
# endothermic – absorption of heat energy, i.e., input of heat energy.

Fig.1: Various forms of phase transitions

Solids
• Solids majorly exist in two kinds; viz, i) crystalline and ii) amorphous.
Crystalline solid
A crystal is a solid material in which the constituent particles are organized in a highly
ordered (periodic) fashion (pattern/manner), i.e., constituent particles have an ordered
arrangement, or, these are crystals with perfect periodicity, see Fig.2.
Crystalline solids are further classified into i) monocrystalline (see Fig.2(a)) and ii)
polycrystalline ((see Fig.2(b))

Fig.2: Schematic arrangement constitute particles in a crystalline, (a) monocrystal and (b)
polycrystal.

−2−
Are formed due to gradual cooling of liquids. Examples are sugar, salt, diamond, copper,
sulphates, etc.
Characteristics include
• definite geometrical shape
• basis arrangement of the constituent particles
• highly ordered 3D arrangement of constituent particles
• planes of crystal intersect at a particular angle.
• Particle arrangements/pattern are repeated throughout the solid.
Amorphous solid
Constituent particles are usually randomly ordered, i.e., the particles have disordered
arrangement (see Fig.3). They are formed due to the sudden/rapid cooling of liquids

Fig.3: Schematic arrangement of constituent particles in an amorphous solid

Examples are glass, plastic, rubber, paper, coal, wax, cotton, candy, thin film, lubricates,
foams, gels, etc. They lack definite shape.

Differences between crystalline and amorphous solids

Solid
Crystalline Amorphous
has an ordered arrangement (array) of has a disordered arrangement (array) of
constituent particles constituent particles
have long-range order of regular have short-range order of irregular
arrangement of constituent particles. arrangement of constituent particles.
known as true/perfect solids termed as supercooled liquids
cleavage (break) evenly along cleavage (break) into uneven parts with
particular points and directions. rugged edges
has a specific geometrical shape with Lacks specific geometrical shape
definite edges and faces

−3−
 are an-isotropic, i.e., have different are isotropic, i.e., have the same physical
physical properties in different space properties in all directions.
directions.
it has a sharp (well-defined) melting They melt over a range of temperatures.
points.
Have definite heat of fusion. Lacks definite heat of fusion.
it is symmetrical unsymmetrical
is more rigid it is soft
consist of metallic and non-metallic consist of non-metallic materials only
materials

Atomic bonding in crystals

• Bonding is the process responsible for the interaction between constituent particles.
• Supply of external energy is required to free/separate the bonded particles and get
them back to the ground state, as energy is consumed to breakdown the bond. This
energy is called binding (dissociation, cohesive, bond) energy.
• Bonding occurs between similar or dissimilar entities when an electrostatic interaction
between them produces a resultant state whose energy is lower than the sum of the
energies possessed by the individual particles in their ground states.

Types of bonding in crystals

Classified into two major categories, viz,: i) primary and ii) secondary
• primary bonding – are inter-atomic/ionic in nature, i.e., bonding between atoms/ions

• secondary bonding – are inter-molecular in nature, i.e., bonding between molecules.

Bonding
Primary Secondary
• interaction occurs only through the • interaction occurs through the
valence electron(s) molecules, i.e., molecular bonding due
• Further grouped into : fluctuating or permanent dipoles
ο ionic • further grouped into :
ο covalent ο hydrogen
ο metallic ο Van der Waals (VdW)

Ionic bonding/Crystal
Involves transfer of one/more valence electron(s) from an electropositive atom (element) to
an electronegative atom (element)

−4−
Ionic crystal structure consists of alternating positively-charged cations and negatively-
charged anions, i.e., ionic crystals are composed of alternating +ve and -ve ions. The ions
may either be monoatomic or polyatomic.

Generally, ionic crystals are from a combination of group 1 or 2 metals, and group 16 or 17
nonmetal or non-metallic polyatomic ions.
Ionic compound does not conduct electricity as solids, but do conduct when molten or in
aqueous solution/substance. The two types of atoms involved are dissimilar, for instance, Na
and Cl (metal and non-metal).
11Na → 1S22S2P63S1 17Cl → 1S22S2P63S2P5

Fig.4: Formation of sodium chloride crystal

In NaCl crystal, 11Na has only one electron in the outermost shell and Cl needs one more
electron to attain inert gas configuration. During the formation of NaCl molecule, one
electron from the Na atom is transferred to the Cl atom resulting to both Na and Cl ions
attaining a filled-shell configuration.
A strong electrostatic attraction is set up that bonds Na+ cation and the Cl- anion into a very
stable molecule NaCl (crystal) at the equilibrium spacing

Since NaCl exists as a molecule, the chemical reaction must be written as

2Na + Cl 2 → 2Na + + 2Cl − → NaCl

Other examples of are :

Mg + Cl 2 → Mg 2 + + 2Cl − → MgCl 2

2M g + O 2 → 2 M g 2 + + O 2 − → 2 M gO

Properties/characteristics of ionic crystal

• ionic bonds are strong
• hard and possess high MP and BP
• they are good ionic conductors, but poor conductor of both heat and electricity
• transparent over a wide range of electromagnetic (em) spectrum

−5−
 • they are bristle, i.e., possess neither ductility (ability to be made into sheet) nor
malleability (ability to be made into wires)
• soluble in polar liquids (such as water) but insoluble in non-polar liquids (such as ether,
acetone (alcohol) benzene etc)

Covalent bonding/crystal
Achieved by sharing of valence electrons between two atoms to form a molecule, i.e.,
covalent crystals are composed of atoms which are covalently bonded to one another.

Fig.5: Formation of hydrogen molecule through covalent bonding

For instance, in H2 molecule, the outermost shell of each atom possesses one electron. Each
H atom would like to gain an electron, and thus form a stable configuration.

This can be done by sharing the two electrons between pairs of H atoms, thereby producing
stable diatomic molecules

Also referred to as shared electron pair bonding

Other examples are diamond, water, carbon, etc.

Properties/characteristics of covalent crystal

• covalent bond/crystal is strong
• possess high MP and BP, but generally lower than for ionic crystals
• conductivity lie between insulator and semiconductors, e.g., Si and Ge are
semiconductors, while diamond is an insulator
• transparent to em wave in infrared region, but opaque at short wavelength
• they are bristle and hard
• insoluble in polar liquids but soluble in non-polar liquids
• bonding is highly directional

Metallic bonding/crystal
Valence electrons from all the atoms are free (mobile) to move throughout the metal.

−6−
The crystal (bonding) is considered as an array of positive metallic ions embedded in a sea
(cloud) of free and mobile electrons, see Fig.6, i.e., metallic crystals consist of metal cations
surrounded by a “sea” of mobile valence electrons.

In a solid, even a tiny of it comprises of billions of atoms. Thus, in a metallic crystal, the
number of electrons that moves freely will be so large that it is considered as though there is
an electron gas (cloud) contained in the metallic crystal.

The atoms embedded in this gas, but having lost the valence electrons, then become
positive ions

Fig.6: Metallic bonding

Properties/characteristics of metallic crystal

• compared to ionic and covalent, the metallic bonds are weaker
• lower MP and BP than either in ionic bonding or in covalent bonding
• excellent electrical and thermal conductors. This is attributed to easy movement their
valence electrons
• they are ductile and malleable
• good reflectors
• opaque to em radiation
• bonding is highly directional

Hydrogen bonding
Crystal solids that are held together by weak intermolecular forces.

Covalently bonded atom often produces an electric dipole configuration.

With hydrogen atom at the positive end of the dipole, bond arises as a result of electrostatic
attraction between atoms.

Characteristics of hydrogen bonding

• the bonding is always weak
• low MP
−7−
 • they are insulators
• transparent to visible and ultraviolet light
• bristle
• directional

Van der Waals (VdW) bonding

Is due to Van der Waals forces. Van der Waals are attractive/repulsive forces between
molecules including but not limited to dipole-dipole, dipole induced dipole, that doesn’t
include force due to covalent or ionic bonding or attraction between ions and molecules.

The Van der Waals force decreases as the fourth power of the constituent atoms/molecules
when the ambient temperature is sufficiently low.

These forces lead to condensation of gaseous to liquids and even from liquids to solids
though no other bonding mechanism exists (except in He).

Characteristics of VdW bonding

• bonding is weak, hence have low MP
• they are insulators
• they are short-ranged
• transparent to visible and ultraviolet light
• they are bristle
• they are non-directional

summary
Bonding (type) Description Typical cpds Typical properties
ionic electron(s) is(are) binary cpds made of • hard & very brittle
transferred from one constituents with very diff nt
• high melting temp
atom to another, & the electronegativity: e.g., I-VII • electrical insulator
resulting ions attract cpds such as NaCl. • water soluble.
each other.
covalent electron(s) is(are) shared cpds made of constituents • very hard (brittle)
equally between two with similar • high melting temp
atoms forming a bond. electronegativities, (III-V • electrical insulator or
energy lowered by cpds such as GaAs), solids semiconductors
delocalization of wave- made of one element only,
function. such as diamond
metallic electrons are delocalized metals in the Left & middle • ductile, malleable
throughout the solid, of periodic table (due to non-
forming a glue between directionality of bond.
positive ions can be hardened by

−8−
 preventing dislocation
motion with impurity)
• low melting temp
• good electrical &
thermal conductors
hydrogen involves H ions bound to essential in organic and • weak bond (stronger
one atom but still biological materials than VdW though)
attracted to another. • important for
special case because H is maintaining shape of
so small. DNA & proteins
Van der Waals no transfer of electrons. noble gas solids. • soft & weak
(VdW) dipole moments on solid made of non-polar (or • low melting temp
constituents align to slightly polar). • electrical insulators
cause attraction. Molecule binding to each • bonding strength
other (wax) increases with size of
molecule or polarity
of constituent.

Forces between atoms (bonding force)

In a solid crystal, forces responsible for bonding are of two kinds, i.e.,
i) attractive and ii) repulsive
These forces play an important role in keeping constituent particles (atoms, ions, molecules)
together (see Fig. Fig.7).

Fig.7: Variation of inter-atomic force F(r) with inter-atomic spacing r.

If the atoms are infinitely far apart, they do not interact with one another to form solid
crystal, and, the potential energy (p.e) would be absolutely zero, since p.e between two
atoms is inversely proportional to the separation distance.

−9−
In all atoms, moving electric charges will be present, hence either attractive or repulsive
interaction takes place as the atom approach each other.
∗ the attractive forces between atoms bring them closer until a strong repulsive force arise
due to the overlap of electron shell. As they move closer, the atom attracts each other due
to the interatomic attractive force that is responsible for the bond formation ∗
Suppose two atoms 1 and 2 experience attractive and repulsive forces on each other, then
the inter-atomic or bonding force F(r) between them accordingly, maybe expressed as
A B
F (r) = − , {N > M} (1)
rM rN
where A, B, M, N are constants/integers.
On the RHS of (1), 1st and 2nd terms represent attractive and repulsive forces, respectively. At
large r, the attractive force predominates. The two atoms approach until they reach
equilibrium distance (spacing) r0. (i.e., bond length r0). If they continue to approach each
other further, the repulsive force predominates, tending to push back to their equilibrium
spacing r0.

Calculation of equilibrium spacing r0 (bond length)

The general expression for bonding forces between two atoms is denoted by (1).
At equilibrium spacing, r = r0 and force F(r) = 0, plugging these into (1)

A B B
= N r0 N − M =
r0 M
r0 A
1

r0 N B  B  N −M (2)
= r0 =  
r0 M A  A

Cohesive energy (CE), U(r)

This is the energy of the pair of constituent particles of the crystal at the equilibrium position
r = r0, i.e., at bond length. Also referred to as the “bonding/bond (also binding, dissociation)
energy”. Since energy is required to dissociate the atoms, CE is also dissociation energy.
The p.e (or the stored internal energy) U of a material is the sum of the individual energies of
the atoms plus their interaction energies.
Consider atoms in the ground state that are infinitely far apart ⇔ they do not interact with
each other to form solid crystal (i.e., r = ∞). The electric p.e (U) which is inversely
proportional to the separation distance r is nearly zero (see (3))
− ( zA e )( zBe ) R ( zA zB ) e2
U ( r ) = U AB = = ≅0 (3)
4πε 0 r r

−10−
NB: zA and zB are valence number of particle A and B, respectively, |e| is the electronic charge
(|e| = 1.60 × 10-19 C), R = 1/(4π ε0) = 9.0 × 109 N-m2/C2.

The U varies greatly with inter-atomic separation r. It is obtained by integrating (1) w.r.t to r


U ( r ) = − F ( r ) dr
−A − ( M −1 ) B − ( N −1 )
 A − B dr = −  Ar − M − Br − N dr  U (r ) = + −c
 ( ) 
U (r ) = −  r r
 M −1 N −1
 rM rN 
U ( r ) = − ar
−m −n
  A  − M +1  B  − N +1  + br −c
U ( r ) = −  r − r + c
 − M + 1   −N +1  a b (4)
U (r ) =− + −c
 A B  m n
U (r ) = −  r ( )−
− M −1
r ( ) + c
− N −1 r r
 −M + 1 N −1 

where, “a” = A/(M - 1), “m” = (M - 1), “b” = B/(N - 1), “n” = (N - 1), , and “c” is the constant of
integration. At r = ∞, U(r) = 0, then “c” = 0. Thus, (4) reduces to (5).
a b
U (r) = − + (5)
rm rn

The condition under which constituent particles form a stable lattice is that the function U(r)
exhibits a minimum value. For a finite value of r, i.e., at r = r0, this is known as the
equilibrium spacing of the system.

Fig.8: Variation of potential energy U with inter-atomic/ionic spacing r.

The minimum energy of U(r) at r = r0 is −ve and hence the energy needed to dissociate the
constituent particles is equals the +ve quantity of −ve Umin. , i.e., −Umin. The Umin occurs only
at r = r0 and if the parameters m and n satisfy the validity n > m. If the system is in
equilibrium, then r =r0, and U(r) = Umin
Differentiating (5) w.r.t. r, and setting the result to zero at r = r0, we have:

−11−
 am bn
− =0
[ dU / dr ]r = r 0
=0 r0m+1 r0n+1
d  a b am bn
=
− +  = 0 r0m+1 r0n+1
dr  r0m r0n 
d am bn
 −ar0− m + br0− n  = 0 m
= n
dr r0 r0 r0 r0
 amr0− m−1  − bnr0− n−1  = 0 am bn (6)
=
r0m r0n

Solving for r0 in (6),

 bn  m 1 1  am   bn 
r0n =   r0 (i) ⇔ = m  r0n−m =   (iii)
 am  r0  bn   am 
n
r0
1
r0n  bn   bn  n−m
=   (ii) r0 =   (iv) (7)
r0m  am   am 
Note that n > m, to prove this is so, proceed as follows.
Taking 2nd derivative of (5) w.r.t r, and setting the result to greater than 0, i.e.,
((d2U)/(dr2) > 0) at r = r0, we have:

 d 2U 
 dr 2  >0  bn  n−m
  r = r0 ( n + 1)   > ( m + 1) r0
 am 
 am(m + 1)   an (n + 1)   bn   bn 
− m+2 + n+2 >0 ( n + 1)   > ( m + 1)   {see eq.7(iii)}
 r0   r0   am   am 
 r0m + 2bn(n + 1)  −  r0n + 2 am(m + 1)  > 0 n +1 > m +1
n>m (8)
bn(n + 1)r0m > am(m + 1)r0n

Cohesive energy (CE)

• This is the energy between two constituent particles at equilibrium position, i.e., at bond
length (i.e., at r = r0). It is the energy needed to separate (or dislodge) the two
constituent particles, and equals
• CE is also referred to as the “dissociation energy” (DE), or “bonding energy” or “binding
energy” (BE).

Substituting “ r0 ” in (5), and consequently making use of 7(i),

n

a b a a m
U min ( r0 ) = − + n U min ( r0 ) = − + m 
r0m
r0 r0m
r0  n 
a b  am  a  m
U min ( r0 ) = − + m  {from 7(i)} U min ( r0 ) = − 1 − n  (9)
r0m
r0  bn  r0m
−12−
Thus, the min. value of energy U i.e., (Umin) is always -ve (see (9)). The +ve value, i.e., |Umin| is
the cohesive (dissociation) energy of the crystal lattice, i.e., the energy required to separate
the any pair of constituent particles.

CE of sodium chloride (NaCl) crystal

Let Na and Cl atoms be free at infinite separation distance r.
The energy required to remove valence electron from Na atom (i.e., its ionization energy),
leaving it as Na+ is 5.10 eV, this amount of energy is added to Na atom.

Na + 5.10 eV → Na+ + e− (10)

The electron affinity of Cl is 3.60 eV. This amount of energy is released out from Cl atom.
Thus, when the dislodged electron from the Na atom is added to Cl atom, 3.60 eV is
released and the Cl atom becomes negatively charged

Cl + e− → Cl − + 3.60 eV (11)

The net energy 5.10 – 3.60 = 1.50 eV is used in creating Na+ and Cl - ions at infinity.
Na + Cl + 1.50 eV → Na+ + Cl − (12)

At equilibrium spacing, r0 = 2.76 Å (for NaCl crystal), the U will be minimum and the energy
released in the formation of NaCl molecule (crystal) is called bond energy {i.e., potential
energy (p.e)} obtained as follows (from eq (3)):
2
− R ( z + z − ) e 2 −  9.0 × 10   ( + 1)( − 1)  1.60 × 10 
9 − 19

U min = = = 8.35 × 10 −19 J = 5.22 eV

r0  2.76 × 10 
− 10

Note z+ and z- for Na+ and Cl- ions are (+1) and (-1), respectively. Thus, energy released in
the formation of NaCl molecule is [5.10 – 3.60 – 5.22] = −3.72 eV. Therefore, to dissociate
NaCl molecule into Na+ and Cl- ions, it requires –[–3.72 eV] = 3.72 eV of energy.
Example
A common way to describe the bonding curve for secondary bonding is by using the
Lennard-Jones potential energy 𝑈(𝑟) expressed as :

𝑈(𝑟) = − + ,

where a = 10.37 × 10-78 J-m6 and b = 16.16 × 10-135 J-m12 are constants for attraction and
repulsion, respectively, for argon (Ar). Estimate the: i) bond length 𝑟 , and ii) bond energy of
the Ar.

solution
( )
i) at equilibrium 𝑟 = 𝑟 , and the derivative of energy w. “r” is minimum, i.e., =0

−13−
 𝑈(𝑟) = −𝑎𝑟 + 𝑏𝑟
( )
= −(−6𝑎𝑟 ) + (−12𝑏𝑟 ) = 6𝑎𝑟 − 12𝑏𝑟 = −
( )
at equilibrium spacing (min. energy) = 0, occurs at 𝑟 = 𝑟

− =0
× . × × .
𝑟 = = = × 10
= . × .

= (3.12 × 10 ) = 3.82 × 10 m = 3.82 Å

𝑎= ⇔𝑟 =

Alternatively: use (7(iv)), 𝑟 = ;

with parameters 𝑎 = 10.37 × 10 J-m6, 𝑏 = 16.16 × 10 J-m12, 𝑚 = 6, and 𝑛 = 12.

ii) for bond energy, 𝑈 = 𝑈(𝑟 )

𝑈 = 𝑈(𝑟 ) = − +

. × . ×
𝑈 = 𝑈(𝑟 ) = − +
. × . ×

𝑈 = 𝑈(𝑟 ) = −3.34 × 10 + 1.67 × 10

𝑈 = 𝑈(𝑟 ) = −3.34 + 1.67 × 10
𝑈 = 𝑈(𝑟 ) = −1.67 × 10 J
𝑈 = 𝑈(𝑟 ) = −10.4 meV
∴, the energy needed to separate a pair of argon gas particle is –[-10.4 meV] = 10.4 meV.
. ×
Alternatively: use (9), 𝑈(𝑟 ) = − 1− = −( )
1− = −10.4 meV
. ×

Can calculate F(r), as follows, by setting parameters:

𝑎 = 𝐴⁄(𝑀 − 1), 𝑚 = 𝑀 − 1, 𝑏 = 𝐵 ⁄(𝑁 − 1), 𝑛 = 𝑁 − 1

Leading to 𝑀 = 7, 𝐴 = 𝑚𝑎, 𝑁 = 13, 𝐵 = 𝑛𝑏, i.e.,

𝐴 = 6 × 10.37 × 10 = 62.22 × 10 N-m6.

𝐵 = 12 × 16.16 × 10 = 193.92 × 10 N-m12.

. . × . ×
∴ 𝐹(𝑟) = − = − N

. ×
𝑟 = = = (3.12 × 10 ) = 3.82 × 10 m = 3.82 Å
. ×

At equilibrium spacing r = r0
. . × . ×
𝐹(𝑟) = − =( )
−( )
N
. × . ×

−14−
 𝐹(𝑟) = (5.24 × 10 ) − (5.26 × 10 × 10 ) N

= (5.24 × 10 ) − (5.26 × 10 ) N

= (5.24 − 5.26) × 10 N

= 0.020 × 10 N

= 2.00 × 10 N

Questions
1. a) Calculate the electrostatic attractive force between pairs of Na+ and Cl− ions that
just touches each other. Ionic radii of Na+ and Cl− are 0.95 Å and 1.81 Å,
respectively. [+3.02 × 10-9 N]
b The equation below gives the bond energy U of NaCl crystal

𝑈(𝑟) = − +

i) using data from 1(a) above, estimate the value of parameter “b”.
[8.62 × 10-106 N-m10 ]
Hence or otherwise, calculate the;
ii) bond energy U (in eV) of the NaCl crystal [-7.40 × 10-19 J = -4.63 eV ]
iii) cohesive energy (in eV) in one mole of the NaCl crystal [2.79 × 1024 eV ]
2. a) The attractive force between a pair of magnesium ion Mg2+ and sulphur ion S2-
is 1.49 × 10-8 N. If the radius of S2- is 1.84 Å, determine the radius of the Mg2+.
[0.65 Å ]
b) Given ionization energy of magnesium atom as 7.66 eV and electron affinity of
sulphur as 2.07 eV, determine the cohesive energy in one mole (in eV) of MgS
crystal. [1.06 × 1025 eV ]
3. The below equation represents the total energy U(r) of a certain crystal
𝑈(𝑟) = − + ,

where the symbols have their usual meaning. Show that its bond length 𝑟 =

Lattice, Basis and Unit Cell

ο Lattice is the ordered/periodicity arrangement of constituents in a crystal.
ο A mono(single) crystal is distinguished by its regular shape, i.e., plane faces, sharp-straight
edges, symmetry ⇔ proportion to its components.
ο A naturally formed crystal has the shape of a polyhedron (a solid with many faces).
ο A crystal structure/scheme has a certain number of corners (c), faces (f ), and edges (ε)

−15−
 c+ f = ε +2 (13)

e.g., a cube with 8 corners, and 6 faces has: c = 8, f = 6, ∴ from eq (13)

c + f = ε + 2  8 + 6 = ε+2  ε = 12 edges

ο the first determination of crystal structure by x-ray diffraction analysis was reported by
W.L. Bragg and the first four crystals to be analyzed were KCl, NaCl, KBr and KI.
ο A crystal structure can be visualized based on the concept of crystal (space) lattice.
ο A crystal lattice is a 3D array of periodically located ideal points in space (note that in 2D, it
is called plane lattice).
ο the array can be defined by primitive basis vectors 𝚤̂, 𝚥̂ and 𝑘 which are three independently
shortest translational vectors connecting the sites.
ο Coordinates of all points belonging to a crystal is governed by:
𝑟⃗ = 𝑎𝚤̂ + 𝑏𝚥̂ + 𝑐𝑘, (14)
where i, j, k are integers, e.g., in 2-D (plane lattice) – different ways of selecting basis
vectors.

Fig.9: Visual representation of basis vectors.

ο the set of all points 𝑟⃗ specified by (14) defines the lattice.
ο the parallelopiped defined by vectors 𝚤̂, 𝚥̂ and 𝑘 is called a primitive cell, i.e., a =b = c=1
(3D parallelopiped) or a =b =1 (2D parallelogram).

−16−
 Fig.10: (a) Sketch showing the primitive cell. Note that 𝚤̂ and 𝚥̂ are primitive basis
vectors for various forms of phase transitions. (b) Representation of the unit
cell with six parameters.

ο the crystal structure is formed only when a basis of atoms is placed identically to each
(lattice point) (basis – identical group of atoms), i.e.,
Lattice + Basis = Crysta Structure (15)
ο the primitive cell is the smallest unit cell that made up a crystal. For instance, the unit cell
indicated in eq (14) becomes primitive cell if a =b = c = 1.
ο the length of vectors 𝑎, 𝑏 and 𝑐 are called lattice spacing (constant).
ο A unit cell in general case is an obliquely-angled parallelopiped with edges 𝑎, 𝑏, 𝑐 and
angle 𝛼(𝑎, 𝑏), 𝛽(𝑏, 𝑐) and 𝛾(𝑐, 𝑎), see Fig.10(b)
ο the six quantities fully describe the unit cell and are called parameters of the lattice.

Types of crystal structures and Bravais lattice

ο all crystals are classified into seven (7) systems on the basis of lattices (i.e., 𝑎, 𝑏, 𝑐) and axial
angles (i.e., 𝛼, 𝛽, 𝛾), and into 14 systems on the basis of unit cells.

Crystal Structure/Scheme Unit Cell (Bravais lattice)

Cubic
1 𝑎=𝑏=𝑐
∝= 𝛽 = 𝛾 = 90°

Tetragonal
2 𝑎=𝑏 𝑐
∝= 𝛽 = 𝛾 = 90°

Orthorhombic
3 𝑎 𝑏 𝑐
∝= 𝛽 = 𝛾 = 90°

Monoclinic
4 𝑎 𝑏 𝑐
∝= 𝛾 = 90° ; 𝛽 = 120°

−17−
 Triclinic
5 𝑎 𝑏 𝑐
∝ 𝛽 𝛾 90°

Rhombohedral/Trigonal
6 𝑎=𝑏=𝑐
∝= 𝛽 = 𝛾 90°

Hexagonal
7 𝑎=𝑏 𝑐
∝= 𝛽 = 90°, 𝛾 = 120°

There are 7 crystal structure schemes and 14 different unit cells (Bravais lattices)

Basis crystal structures

The important fundamental parameters that are used to study different arrangements of
atoms responsible for the formation of different crystal structures are:
§ Lattice constant (a) : it is the dimensional size (value) of a unit cell in a crystal
structure.
§ Atomic radius (r) : it is the radius of the spherical atom.
§ Nearest neighbor distance (nnd) : the distance between the centres of two adjacent
atoms. For similar atoms, each with radius r, nnd = 2r, i.e., nnd equals the atomic
diameter
§ Coordination number (CN) : is the number of the closest equidistant neighbor atoms
surrounding a lattice point (atom).
§ Atomic Packing Factor (APF) : is the ratio of the volume occupied by all atoms (vatoms)
to the volume of the unit cell (Vcube) itself.
.
𝐴𝑃𝐹 = = =
.

These unit crystal structures include:

• primitive cell
• simple-cubic cell (SCC) unit
• body-centred-cubic (BCC) cell unit
• face-centred-cubic (FCC) cell unit
• hexagonal-close-packed (HCP) cell unit

−18−
Simple-cubic cell (SCC) crystal structure

Fig.11: (a) Lattice points of a simple cubic configuration. (b) Relation between atomic
radius r and lattice constant “a” of SCC structure.

ο there is one lattice point at each of the eight (8) corners of the unit cell.
ο the atoms touch each other along the edges of the cube.
Atomic radius = r
Lattice constant = a = 2r  𝑟=

Nearest neighbour distance nnd = 2r = a

Coordination number = 6 (since each corner is surrounded by 6 equidistant nearest
neighbour atoms).
number of atoms in a unit cell = one-eighth of an atom at each of the eight corners,
i.e., {(1/8) × 8} = 1 Atom
.
𝐴𝑃𝐹 = = =
.

× × ×
𝐴𝑃𝐹 = = = = = π× = = 0.52 = 52%
ο the structure is loosely packed, i.e., 48% of it is empty.
ο examples of elements that exhibit SC structures are polonium, fluorine, oxygen, etc.
Body-centred-cubic (BCC) crystal structure

−19−
 Fig.12: (a) Lattice point positions of the body-centered cubic configuration. (b)
relation between atomic radius r and lattice constant a of BCC structure.

ο consists of one atom (lattice point) at each of the eight (8) corners plus one (1) atom at the
middle (centre) of the of the unit cell.
ο the atoms touch each other along cube diagonals, i.e., only the centre atom touches all the
8 corner atoms.
√
4𝑟 = 𝑎√3 ⸫ Atomic radius 𝑟 = 𝑎, and Lattice constant 𝑎 = 𝑟
√
√
nearest neighbour distance 2𝑟 = 𝑎

CN = 8 (since the central atom touches 8 corner atoms).

number of atoms per unit cell = ((1/8) × 8) + 1 = 2 Atoms
.
𝐴𝑃𝐹 = = =
.

√ √
× × ×
√ √
𝐴𝑃𝐹 = = = = = π× = π = 0.68 = 68%

ο the structure is 68% occupied, i.e., 32% of it is empty.

ο examples of substances that exhibit BCC structure are Tungsten, (W), Na, Fe, Cr, NaCl etc.
Face-centred-cubic (FCC) crystal structure

Fig.13: (a) Lattice point positions of face-centered cubic configuration. (b) relation
between atomic radius r and lattice constant “a” of FCC structure.

ο consists of one lattice point at each of the eight (8) corners plus one (1) centre atom on
each of six (6) faces of the cube of the unit cell.
ο atoms touch each other along face diagonals, i.e., only face atom in contact with
immediate 4 corner atoms.
√
Face diagonal 4𝑟 = 𝑎√2 ∴ Atomic radius 𝑟 = 𝑎, & lattice constant 𝑎 = 𝑟
√
√ √
NND = 2𝑟 = 2 𝑎 = 𝑎

−20−
 CN = 12 (centre of each face has one atom. This centre atom touches 4 corner atoms in
its plane, 4 faces centre atoms in each of the two planes on either side of its plane).
# of atoms in a unit cell = one-eighth of atom at each of the eight corners (1/8 × 8 = 1),
and one-half of an atom on each of the six faces (1/2 × 6 = 3 atoms)  total of 4
Atoms.
.
𝐴𝑃𝐹 = = =
.

√ √
× × × √ √
𝐴𝑃𝐹 = = = = = π× = π = 0.74 = 74%

ο FCC has the highest packing factor (density) (i.e., 74%).

ο examples of elements that exhibit FCC structures are Cu, Al, Pb, Ag, Au, Ni, Pt, etc.

Density ‘ρ’ of a Unit Cell

( ) ( )
𝐷𝑒𝑛𝑠𝑖𝑡𝑦 (𝜌) = ( )
= = 𝜌=
.

Assume M ≡ molar mass, NA ≡ 6.02 × 1023 number of particles in one-gram mole, i.e.,
Avogadro number.
mass of one atom = ∴ total mass = (no. of atoms)× (mass of 1 atom) = 𝑛 × =

volume of unit cell (cube) vcube = 𝑎

where n ≡ number of atoms / molecules / particles / in a unit cell,
M ≡ molecular wt. (molar mass), a ≡ lattice constant
NA = 6.02 × 1023 atoms per gram-mole ≡ Avogadro number (i.e., number of particles in
one gram of a mole) {or NA = 6.02 × 1026 atoms per kilogram}.
( )⁄
𝜌=  𝜌= ⇔ 𝑎=

Illustrations

Q1. Copper (Cu) has an FCC structure and atomic radius of 1.28 Å. Calculate the density (in
kg/m3) of Cu crystal given that the molar mass of Cu = 64 g, and NA = 6.02 × 1023.
A1. For an FCC structure, there are 4 atoms in the unit cell
×
mass of one atom = = g & mass of the unit cell = = g
. × . ×

Lattice constant “a” for FCC is

𝑎= 𝑟= × 1.28 × 10 = 3.62 × 10 m = 3.62 Å  3.62 × 10 cm.
√ √
×
∴ 𝜌= =( ) ( . )
= 8.96 g/cm3.
. × ×

To covert 8.96 g/cm3 into kg/m3  (8.96 × 1000) ≈ 8960 kg/m3.

−21−
 ( × )
Alternatively, 𝜌 = =( ) ( . )
= 8960 kg/m3
. × ×

How many atoms contained in 8.45 m3 volume of Cu?

Proceed as: get the total mass contained in the volume 8.45 m3 of Cu, then, divide by
the mass of one atom of Cu.
Mass m of Cu in 8.45 m3 𝑚 = 𝜌𝑉 = 8960 × 8.45 = 75712 kg
𝑀 64
Then, mass of one atom matom (in kg) of Cu 𝑚 = = kg
𝑁A 6.02 × 1026

∴ # of atoms in 8.45 m3 natoms is

𝑛 = = × 6.02 × 10 = 7.12 × 10 atoms

Alternatively, use 𝜌 = , by setting

𝑛 ≡ # of atoms contained in 8.45 m3 volume of Cu

𝑀 ≡ molar mass
𝑎 ≡ utilized the given volume, i.e., here use 8.45 m3
𝑁 ≡ Avogadro # {use 𝑁 = 6.02 × 10 if density 𝜌 is in g/cm3 or 𝑁 = 6.02 × 10 if
𝜌 is in kg/m3}
×
𝜌=  8960 =  𝑛 = 7.12 × 10 atoms
. × . ×

Q2. The density of α-iron (α-Fe) is 7.87 g/cm3 and its atomic mass is 56 g/mol. If α-Fe
crystallizes in BCC lattice, find the value of the lattice constant.
A2. molar mass = M = 56 g/mol ∴ mass of 1 atom = = g
. ×

note that BCC structure (lattice) has 2 atoms (molecules) per unit cell
×
∴ mass of the unit cell = = g  𝜌=  𝑎=
. ×

×
𝑎= = 2.87 × 10 cm  2.87 × 10 m  2.87 Å
. × . ×

How many atoms are there in 54.8 m3 volume of α-Fe ? {4.64 × 1030 atoms}
Q3. Calculate the lattice constant “a” of potassium bromide (KBr) whose density is 2.70
g/cm3 and belongs to FCC lattice. Molar mass of KBr is 120 g/mol and NA = 6.02 × 1023.
Also, calculate atomic radius r.
A3. molar mass. = M = 120 g/mol ∴ mass of an atom = = g
. ×

note that FCC lattice has 4 atoms (molecules) per unit cell
×
∴ mass of the unit cell = g thus, 𝜌=
. ×

×
𝑎= = = 6.66 × 10 cm = 6.66 × 10-10 m  6.66 Å
. × . ×

√ √
also note that in FCC, “r” and “a” relate as 𝑟 = 𝑎= × 6.66 Å = 2.35 Å
−22−
Exercise
a) Show that for an ideal HCP structure, the axial ratio c/a = 1.63.
b) The lattice constant and atomic mass of a diamond crystal are 3.57 Å and 12 g,
respectively. Calculate the density of the diamond.
c) Offer an explanation as to why covalently bonded materials are generally less dense
than either ionically or metallically bonded ones.
d) Ca crystallizes in an FCC form with lattice constant of 5.58 Å. Assuming a mass molar of
40 g and Avogadro number NA = 6.02 × 1023, Determine its: i) atomic radius r {1.97 Å}
and density ρ(in kg/m3) {1530 kg/m3}, ii) number of atoms in 10.52 m3 of Ca
{2.42 × 1029 atoms}.

e) Aluminium (Al) crystal whose density and atomic weight are 2700 kg/m3 and 27,
respectively, has an FCC crystal structure.
i) Determine the unit cell dimension and atomic diameter of Al
ii) Calculate the number of atoms contained in a 5.50 m3 volume of the Al crystal

f) The unit cell of Chromium (Cr) metal is cubic and contains 2 atoms, if the density of
Cr=7200 kg/m3, determine the dimension of Cr unit cell (molar mass of Cr = 52 g). What
is the number of atoms of Cr that contained in 0.865 m3 volume of Cr?

Allotropism and Polymorphism

• Allotropism: Ability of an element to crystallize in more than one crystal structures under
different (conditions (pressures and temperatures), e.g., i) graphite and diamond are
allotropes of carbon, ii) O2 and O3 (ozone) are allotropes of oxygen
• Polymorphism: Ability of a compound to crystallize in more than one crystal structures
under different (conditions (pressures and temperatures), e.g., calcite and oragonites are
two forms of CaCO3.
NB: This leads only to the element (or compound) having the same chemical properties but
different physical properties
Q. Iron (Fe) crystallises into a BCC at 911 ℃ with a lattice constant 2.86 Å. At 913 ℃, Fe is a
FCC with a lattice constant 3.59 Å. What is the %age change in the volume of the Fe when
temperature changes from 911 ℃ to 913 ℃?
A. A BCC crystal structure has 2 atoms (i.e., its unit cell volume contains 2 atoms)
An FCC crystal structure has 4 atoms (i.e., its unit cell volume contains 4 atoms)
∴ VBCC = (2.86 Å)3 = 23.3937 Å3 & VFCC = (3.59 Å)3 = 46.2683 Å3
For comparison, we must consider two BCC unit cells (i.e., 4 atoms constitute 2 BCC unit
cells). This will be equal to one FCC unit cell (i.e., 4 atoms constitute 1 FCC unit cell)
Hence 2VBCC = 2 × VBCC = 2 × 23.3937 Å3 = 46.7874 Å3
−23−
 Change in volume ΔV = VFCC – 2VBCC = 46.2683 Å3 − 46.7874 Å3 = −0.5191 Å3
( . . )Å .
%age change in volume × 100 = × 100 = −1.12 %= %
. Å .

Directions and planes in a crystal

When dealing with the crystals, it is appropriate to refer to crystal geometrical planes and
directions of the straight lines joining the lattice points.
For this purpose, an indexing system devised by W.H. Miller, known as Miller Indices is widely
used.

Directions in a crystal
Crystallography is the study of crystal structures in relation to planes and directions.
Consider a cubic lattice in which a straight line passes through lattice points A, B, C, etc, and
one lattice point on the line such as point A is chosen as the origin (see Fig.14).

Fig.14: Representation of the directions of planes in a crystal.

# then, a position vector 𝑟⃗ that joins point A to any other point on the line, such as B, can be
represented by a vector as shown in (16) #
𝑟⃗ = 𝑋𝚤̂ + 𝑌𝚥̂ + 𝑍𝑘 , (16)
where X, Y, Z, are integers, and 𝚤̂, 𝚥̂, 𝑘 are basis (unit) vectors.
The direction of 𝑟⃗ depends on the integers X, Y, Z since 𝚤̂, 𝚥̂, 𝑘 are constants. The least
common multiple is removed and integers X, Y, Z are re-expressed as the smallest values x,
y, z, bearing the same relative ratio. The direction is then denoted as [xyz], i.e., with square
brackets.

𝑟⃗ = 𝚤̂ + 𝚥̂ + 𝑘 (17)
which provides the value of one (unity) for each of x, y, z. Therefore, the direction in Fig.14 is
denoted as [111].

−24−
NB: All lines in the space lattice parallel to ABC possess either same set of values for x, y, z,
as that of ABC or its common multiples.
Q1. Show that the direction [229] connects (0,0,0) and (3,3,2/3) points.
 1 1 3
A1. i.e.,  : :  , L.C.M of the denominators 3, 3, & 2 is 6
 3 3 2
 1 1 3
  : :  × 6 = ( 2: 2:9) → [ 229]
 3 3 2
Q2. Show that [211] is the direction that joins the origin and intercepts/coordinates (1,2,2).
   1 1 1
A2. i.e.,  1 : 1 : 1 , LCM of denominators = 2 ∴  : :  × 2 = ( 2:1:1) → [ 211]
 1 2 2  1 2 2

Miller indices (MI)

It is possible to define a system of parallel and equidistant planes which can be imagined to
pass through the atoms in a space lattice, such that they include all atoms in the crystal.
Such a system of planes is called crystallographic planes (directions). Many different systems
of planes could be identified for a given space lattice.
∗ the position of a crystallographic plane can be specified in terms of three whole integers
(number), called Miller indices ∗  (h:k:l) → [hkl] ∗
Consider a crystal plane intersecting the crystal axes, as shown in Fig.15.

Fig.15: Representation of crystal planes cutting crystallographic axes at points A, B, C.

Therefore, MI is defined as “a set of three whole integers (numbers) used to designate a plane
direction in a crystal”, i.e., A set of three numbers that specifies (identifies) crystal plane
direction.
It is represented using square brackets, i.e., (h:k:l) → [hkl]

−25−
Steps for finding MI
1. Determine the three intercepts/coordinates (i.e., lattice points) from the axes, let these
be (XYZ), i.e., pick up the coordinates of a given position, (XYZ).
2. Take the reciprocal (inverse) ratios of these numbers, i.e., (1/X:1/Y:1/Z)
3. Get LCM of the denominators, i.e., LCM of X, Y, Z.
4. Multiply all the reciprocal ratios with the LCM of the denominators to change them
into the smallest whole numbers (integers).
1 1 1   [YZ,ZX,XY]
 : :  × XYZ = (YZ : ZX : XY )
X Y Z 

5. This gives the MI as (YZ : ZX : XY ) ≡ (YZ , ZX , XY ) = [YZ , ZX , XY ]

Examples ( 3, 4 , 2 ) ( 3, 4,5 ) ( 1, 1, 2 )
1 1 1 1 1 1 1 1 1 
 : :  × 12 = ( 4:3:6 )  : :  × 60 = ( 20 :15 :12 )  : :  × 2 = ( 2:2 :1)
3 4 2 3 4 5 1 1 2 
∴ ( 4: 3 :6 ) → [ 4 3 6 ] ∴ ( 20 :15 :12 ) → [ 20,15,12] ∴ ( 2 : 2 :1) → [ 221]

Features (characteristics) of MI
I. If a plane is parallel to any axis, the intercept of the plane on that axis is infinity (∞) ⇔
hence, the MI for that axis is zero
II. If the intercept of a plane on any axis is negative, a bar is placed on the
corresponding MI e.g., ( 4, − 1, 3 ) ≡ ( 413 ) = [413] , i.e., ( h , − k , l ) ≡ ( h k l ) = [ h k l ] , implying

that integer “1” and “k” are negatives.

III. All equally spaced parallel planes have the same index number (hkl), e.g., the plane
(112), (224), (336), (448), and (5,5,10) are parallel to each other.
IV. Family of planes with the same MI are enclosed in curly brackets {hkl},
e.g.,{100} = (100), (010), (001), (100), (010), (001), etc.
V. Several directions in a crystal are equivalent because of the crystal symmetry.

Interplanar spacing / distance ‘d’

ο This is the separation distance between two successive (i.e., adjacent or neighboring)
crystal planes.
ο Let [hkl] be MI plane of the ABC

−26−
 Fig.16: Representation of inter-planar distance ’d ‘ of the crystal plane.
Let OP = dhkl passing through O, be the normal line to the plane ABC. Also let OP makes
angles α, β, γ, with x, y, z axes, respectively,

then Cos (α ) =
OP d
= =
d
=
hd since the convention MI
OA X ( a / h ) a
Xh = a, Yk = b, Zl = c
OP d d kd
Cos ( β ) = = = = a b c
OB Y ( b / k ) b X= , Y= , Y=
h k l
OP d d ld
Cos ( γ ) = = = = a b
h= , k = , l=
c
OC Z ( c / l ) c X Y Z

making use of the direction cosine concept:

1
now: Cos 2 (α ) + Cos 2 ( β ) + Cos 2 ( γ ) = 1 OP = d = d hk l =
h k2 2
l 2 
1/2

 h d  2  k d  2  ld  2  + +
hence:        2 2 
 a  + b  + c  =1
2
a b c 
     
1
hd2 2 2 2
k d l 2d 2 ∴ dh k l =
+ + =1  h 2 k 2 l 2  1/2
: a2 b2 c2  
 h2 k 2 l 2   a 2 + b 2 + c 2 
 
d 2  2 + 2 + 2  = 1
a b c  For cubic structure, a= b = c ≡ “a”
1 1
d2 = dh k l =
 h2 k 2 l 2   h 2 k 2 l 2  1/ 2
   
 2 + 2 + 2   2 + 2 + 2 
 a b c   a a a 
1 1
d= d hk l =
 h 2 k 2 l 2  1/2 1 2
 
( h + k2 + l2 )
1/2
 2 + 2 + 2 
 a b c  a
a
OP = d =dhkl ∴ d hk l =
h + k2 + l2
2

Let the next plane parallel to ABC be at a distance OQ from the origin O. Then, the intercepts
2a
are (X,Y,Z) → [2(a/h), 2(b/k), 2(c/l)]  ∴ OQ = 2dhk l =
h2 + k 2 + l 2

−27−
So, the spacing between adjacent planes OQ – OP = PQ, i.e.,
a
PQ = dhk l =
h + k2 + l2
2

Q1. Find the interplanar distance d for cubic crystals [011], [111], [222].
A1. For cubic crystal, a = b = c ≡ ”a”
a a a
dhk l = d011 = = = = d110 = d101
2
h +k +l 2 2 2
0 +1 +1 2 2
2
a a a
similarly, dhk l = d111 = = =
h2 + k 2 + l 2 12 + 12 + 12 3
a a a
dhk l = d222 = = = = 2d111
2
h +k +l 2 2 2
2 +2 +2 2 2
2 3

Q2. In SC lattice, find the ratio of intercepts of the three axes formed by (123) plane.

A2. If the plane cuts intercepts of length w1, w2, w3 on three crystal axes, then
p1, p2, p3 = qa : wb : sc
where a, b, c are primitive (basis) vectors. q, w, s are integers related to MI
by 1/q:1/w:1/s = h:k:l
 1 1 1
‫؞‬, (hkl) → (123)  q : w : r =  : :  × 6  ( p1, p2 , p3 ) = ( 6:3: 2)
 1 2 3
Q3. Find the ratio of inter-planar spacing of planes (100), (010), and (110) in a SC lattice.
Q4. In a tetragonal lattice, a= b = 2.5 Å, c = 1.8 Å, determine the lattice spacing between
(111).
A4. note that (h:k:l) → [hkl] → [111]
1 1 Å = 1.26 Å
dhk l = =
 h 2 k 2 l 2  1/ 2  12 12
12  1/ 2
   
 2 + 2 + 2   2
+ 2
+ 2 

 a b c   2.5 2.5 1.8 

Examples of cubic lattice crystallographic planes and their MI

−28−
 Fig.17: Representation of crystallographic plane orientation using Miller indices (a) [100],
(b) [110], (c) [122], (d) [362], (e) [362] and (f) [221].

x-rays diffraction (XRD) of crystal planes

ο Diffraction is the scattering of incident radiation by a regular array of lattice points whose
spacing is comparable to the wavelength of the radiation.
ο x-rays are EM wave, like ordinary light; hence, they exhibit interference and diffraction as
well, i.e., x-ray diffraction (XRD)
ο Diffraction occurs when waves pass through an object whose dimension are of the same
order of their own wavelength.
ο the wavelength of x-rays is of the same order of 1 Å (10-8 cm ≡ 10-10 m) so that ordinary
device such as ruled diffraction gratings do not produce observation effect with x-rays.
ο the German Physicist called Max von Laue suggested that a crystal which consists of a 3D
array of regularly spaced atoms could serve the purpose of a diffracting medium.
ο The crystal differs from ordinary diffraction grating in the sense that the diffracting centres
in the crystals are in one plane.
ο hence, the crystal acts as a space grating rather than a plane grating.
ο there are three (3) main XRD methods by which a crystal structure can be analyzed.
• Laue method – for single crystal
−29−
 • Rotating crystal method – for single crystal.

• Powder method – for finely crystalline/polycrystalline powder.

Bragg’s law
State that “ the x-rays reflected from different planes of a crystal interfere constructively if the
path difference is in integral multiple of the x-ray wavelength λ “
∗ consider a crystal made up of equidistant planes of atoms (lattice points) with the inter-
planar spacing “d”

Fig.18: Representation of XRD of crystal planes (Bragg’s law).

Let wavefront of monochromatic x-rays beam of wavelength λ be incident at angle θ on

atomic plane MN. Each atom scatters the x-rays in all directions
In certain directions, the scattered radiations are in-phase, i.e., they interfere constructively,
whereas in others, there is destructive inferences
Consider the x-rays QE and PC inclined at angle θ with the top of the crystal plane MN. They
are scattered along EQ’ and CP’, respectively, at angle θ with respect to plane MN
Let normal EB and ED be drawn to AC and CF, respectively. If EB and ED are incident and
reflected (diffracted) wavefronts, then path difference δ between them is given by (18)

δ = BC + CD , (18)

In Δ BEC; sinθ = (BC)/(EC) = (BC)/d  BC = dsinθ Thus,

Similarly, BC = CD = dsinθ
In Δ DEC; sinθ = (CD)/(EC) = (CD)/d  CD = dsinθ ∴ δ = 2dsinθ

δ = 2dsinθ , (19)

−30−
If the two consecutive planes scatter waves in-phase with each other, the δ must be an
integral multiple of wavelength λ, i.e., taking integer n
δ = nλ , where n = 0, 1, 2, 3, ···
Thus, the condition for in-phase scattering by the crystal planes is given by
nλ = δ
nλ = 2dsinθ (20)

• (20) is known as the Bragg’s law. This law describes diffraction condition, and it is a
consequence of the periodicity of the lattice structure

• the maximum possible value for sinθ ≤ 1 ; for n = 1

∴ λ ≤ 2d , ⇔ λ/(2d) ≤ 1

i.e., the wavelength λ should not exceed twice the inter-planar spacing d for
diffraction to occur  Bragg reflection can only occur for λ ≤ 2d. This is the
reason why visible light are unsuitable for the crystal diffraction.

Reflection rules of diffraction for common crystal metallic

structure
crystal structure diffraction does occur if: diffraction doesn’t occur if:

BCC h + k+ l = even number h + k+ l = odd number

FCC h, k, l unmixed, i.e., all h, k, l mixed, i.e., both even and odd
even or all odd numbers numbers
HCP all other cases (h + 2k) = 3n, l odd (n = odd integer)

Questions

Q1. In a certain diffractometer, x-rays with a wavelength λ = 1.32 Å were used to produce a
diffraction pattern for copper (Cu), the first-order diffraction (n=1) occurs at angle
θ=25.3°. Determine the spacing between the diffracting plane in the Cu.
× . ×
A1. 2𝑑 sin θ = 𝑛 (n=1)  𝑑= = ( . )
= 1.54 × 10 Å = 1.54 Å.
×

Q2. The spacing between subsequent lattice points of nickel crystal is 0.91 Å. In an XRD
experiment, the incident beam and diffracted beam make angle of 65° with the family of
1st order Bragg’s planes. Determine the: i) wavelength λ of the x-rays used, ii) energy (in
eV) of the x-rays used.

−31−
 × . × × ( . )
A2. i) 2𝑑 sin θ = 𝑛 (n=1, θ=57.5°)  𝜆= = = 1.53 Å
. ×
ii) 𝐸 = ℎ𝑓 = ℎ = (6.63 × 10 )
( . )
= 1.30 × 10 J = 8125 eV
×

Q3. The Bragg’s angle corresponding to the 1st order reflection [111] planes in a crystal is
30° when x-rays of λ=1.75 Å are used. Calculate the lattice spacing.
A3. 𝑑 = (a = b = c = ”a”, and h = k = l = 1)
√

𝑑 =
√
But from Bragg’s law
. √
2𝑑 sin θ = 𝑛 2 sin(30) = 1 × 1.75 × 10 𝑎= = 3.03 Å
√ ( )

Q4. Monochromatic x-rays of λ=1.40 Å are incident on a crystal having 1.5 Å inter-atomic
spacing. Find the various orders in which diffraction takes place.
× . × .
A4. 𝑛 = 2𝑑 sin θ  𝑛= = ( . )
×

𝑛 = 2.14 sin(θ)
 since sin(θ) should be always less than one, maximum number of orders of spectrum
is two ⇐
Q5. A sample of MgO crystal placed at 3 cm from the film, gives a [111] diffraction spot
located at 1 cm from the film centre.

Calculate the: i) diffraction angle and the

Bragg’s angle, ii) x-rays wavelength λ
that would produce first-, second-, and
third-order diffraction (take lattice
constant of MgO as 4.20 Å)

A5 𝑡𝑎𝑛(ϕ) = = 0.3333  ϕ = 18.4 ∴ diffraction angle (2θ) = 180 – 18.4 = 161.6°

 Bragg’s angle (θ) = (2θ)/2 = 80.8°

use Bragg’s law to get λ

Using 𝑛 = 2𝑑 sin θ, (“a” = 4.20 Å) = but 𝑑 =

√
. . Å
 𝑑 = Å= = 2.42 Å
√ √
× . ( . )
∴ n = 1,  𝜆 = = 4.78 Å
× . ( . )
n = 2,  𝜆 = = 2.39 Å

−32−
 × . ( . )
n = 3,  𝜆 = = 1.59 Å

Madelung constant ‘αm’

This is the formula used to determine the electric potential V of a single ion in a solid crystal.
In general, the electric potential Vi on an ion placed at position ri due to all other ions is
given by

e zj z
Vi = 
4πε 0 j ≠i rij
= ke j ,
j ≠i rij
(21)

where rij = |rj – ri| is the distance between the ith and jth ions, zj is the valence on the jth ion, |e|
= 1.60 × 10-19 C, and 𝑘 = × . × . ×
= 9.00 × 10 C2/N-m2 is the Coulomb constant.

If rij is normalized to the 1st nearest neighbor distance r0, the potential may be written as

1 zj ke
Vi = ke r = αm
(22)
r0 j ≠i ij  r0
 
 r0 
zj z j r0
with α m ≡  ≡ is the Madelung Constant (dimensionless) of the ith ion.
j ri j /r0 j ri j

The electric potential energy Ui of the ion at ri is then the product of its electric charge e with
potential acting at its site, i.e.,

k e2
U i = eVi = αm (23)
r0

Example

Consider a linear chain of ions of alternate signs shown (NaCl)

Fig.19: Linear chain of alternate Na+ and Cl− ions.

Let choose the Na+ in the middle (x = 0) as a reference and select r0 to be the shortest
distance between adjacent ions (the sum of their radii). The Coulomb energy of the other
ions in the 1D lattice on this Na atom can be decomposed by proximity (nearest neighbor)

• 1st nearest neighbors (i.e., 1st Coordination Number (CN) C1 )

−33−
 The reference Na+ has two Cl− as its neighbors on either side at ± 1r0 . Therefore, the
Coulomb attractive energy of these interactions is:

− k e 2 − ke 2 2 ke 2
C1 = + =− (24)
r0 r0 r0
• 2nd nearest neighbors (i.e., 2nd CN C2 )

Similarly, the Coulomb repulsive energy due to the next two Na+ at distance ± 2r0 is
+ ke 2 + ke 2 2 ke 2
C2 = + = (25)
2 r0 2 r0 2 r0
• 3rd nearest neighbors (i.e., 3rd CN C3 )

Attractive Coulomb energy due to the next two Cl− neighbors at distance ± 3r0 is
− ke 2 − ke 2 2 ke 2
C3 =
3r0
+
3r0
=−
3r0
(26)

• 4th nearest neighbors (i.e., 4th CN C4 )

Repulsive Coulomb energy due to the next two Na+ neighbors at distance ± 4r0 is

+ ke 2 + ke 2 2 ke 2
C4 = + = (27)
4 r0 4 r0 4 r0

• 5th nearest neighbors (i.e., 5th CN C5 )

Attractive Coulomb energy due to the next two Cl− neighbors at distance ± 5r0 is

−k e2 −k e2 2k e2
C5 = + =− (28)
5 r0 5r0 5 r0

and so on ·····

∴ total energy E due to all ions in a linear array is arrived at by adding eq (24) – (28).

2ke2 2ke2 2ke2 2ke2 2ke2

E=− + − + −
r0 2r0 3r0 4r0 5r0
2   
ke   1 1 1 1 1  
=− 2 − + − +  (29)
r0   1 2 3 4 5  
Use Maclaurin expansion

x1 x2 x3 x 4 x5
ln (1 + x ) = − + − + −⋅ ⋅ ⋅ (30)
1 2 3 4 5
Setting x = 1 , (30) convergences at ln ( 2) . Plugging this into (29)

11 12 13 14 15
ln (1 + 1) = − + − + − ⋅ ⋅ ⋅ = ln ( 2 ) (31)
1 2 3 4 5

−34−
Combining (29) and (31), the total potential energy becomes

ke2   ke2
E=−  2ln ( 2 ) = −
 αm
r0 r0 (32)
ke2
where is the Coulomb energy, αm = [2ln (2)] = 1.3863 is the Madelung Constant, for a
r0
single pair of Na+ and Cl−.

NB: the value NAαm = [NA 2ln (2)] is the Madelung constant per mole of ionic solid in linear
chain.

Question

Calculate the binding energy per mole for NaCl crystal, given that the nearest neighbor
distance r0 = 2.76 Å

Solution

 (1/8) × 8 = 1 Cl−
•1 Cl− at each face, shared by 2 unit-cells
(note, there are 6 faces)
 (1/2) × 6 = 3 Cl−
∴ total number of Cl− = 1 + 3 = 4
•1 Na+ at each edge, shared by 4 unit-cells
(note, there are 12 edges)
 (1/4) × 12 = 3 Na+
•1 Na+ at the centre of the unit cell
 1 × 1 = 1 Na+
•1 Cl− at each corner, shared by 8 unit-
∴ total number of Na+ = 1 + 3 = 4
cells (note, there are 8 corners)
⇔ number of Cl− = number of Na+

Let r0 be the distance between Na+ and Cl−.

• The 1st nearest neighbors (NN) of Na+ are 6 Cl− at distance 1 r0

• The 2nd NN are 12 Na+ ions at 2 r0

• The 3rd NN are 8 Cl− ions at 3 r0

• The 4th NN are 6 Na+ at 4 r0

• The 5th NN are 24 Cl− at 5 r0 ,………… and so on

Thus, the electrostatic potential U of a single ion in a crystal is arrived at by approximating

the ion as a point-charge of the surrounding ions

−35−
 k ( z +1e )( z −1e ) (z +1 −1
z )k e 2

U =− αm = − αm
r0 r0
 k e2   6 12 8 6 24 
=  
 
 − + − + − ⋅ ⋅ ⋅ 
 r0   1 2 3 4 5 

The series in the square bracket converges at a value that define the Madelung constant 𝛼
6 12 8 6 24
αm = − + − + − ⋅ ⋅ ⋅ ≈ 1.74756
1 2 3 4 5

For a mole of ions pair, NA using α m , the expression of NaCl-type lattice due to Coulombic
interactions;

N z 2ke2
U =− A αm = −
( 6.02 ×10 23
) (−1)(+1) ( 9 ×10 ) (1.60 ×10
9 −19 2
)
×1.74756 = 8.78 ×105 J
r0 ( 2.76 ×10 ) −10

Task: i) Given the ionic radii of Na+ and Cl− are 0.95 Å and 1.81 Å, respectively, estimate
APF of NaCl crystal. [68%]
ii) If the molar mass of NaCl crystal is 58 g/mol, determine its density based on the
data provided in (i) above. [2290 kg/m3]

Surface tension ‘β’ and surface energy ‘σ’

Surface tension is a fundamental property by which the gas-liquid interfaces are
characterized. The zones between liquid and gaseous states look like a surface of zero
thickness. The surface acts like a membrane under tension.

surface tension (β) is the force F exerted normally on the surface of a fluid per unit length L.
its SI unit is N/m.

= ( )
( )
 = (33)

It governs the shape that tiny masses of liquids can assume and the degree of contact a
liquid can make with another surface

surface energy (σ) is the work done W per unit surface area A, i.e., the amount of energy per
unit area A.

Its SI unit is J/m2.

• when the surface area of a given liquid is increased, work has to be performed against the
surface tension •.

Molecular force and surface tension β

ο surface of any liquid behaves as though is covered by a stretched membrane, i.e., β.
−36−
ο net force on a molecule at surface is directed into bulk of the liquid.

a. A molecule within the bulk liquid is surrounded on all sides by other molecules,
which attract it equally in all directions, leading to zero net force, i.e., ΣF = 0
b. A molecule at the surface experiences a net attractive force (i.e., ΣF ≠ 0) pointing
towards the liquid interior, because of there are no molecules of the liquids above
the surface.

Fig.20: Representation of molecular interactions (a) inside the surface of liquid and
(b) at the surface.

Examples of surface tension β in everyday life

1. Insect walking on water
• several insects are able to on water surface
• their legs are formed to distribute their weight causing the surface of liquid to
become depressed minimizing potential energy to create balance of the force

• this enables insect(s) to move across the surface.

2. needle (paper clip) floating on water surface

• though the density of object is greater than water, surface tension along the
depression is enough to counteract the force of gravity pulling down the object
3. Drops of water

• when using a water dropper, the water does not flow in a continuous stream, but
rather in a series of drops
• the shape of the drop is determined by surface tension of water. The only reason
why the drop of water is not completely spherical is because the force of gravity
which is pulling it down

• in the absence of gravity, the drop could minimize tension which would results in a
perfectly spherical shape

−37−
 4. touching the tent

• common tent materials are somewhat rainproof in that the surface tension will
bridge pores in the finely woven material
• if you touch the tent with your hands, you break the surface tension and the rain
water will drip though

5. Soap and detergent

• helps the cleaning of garments by lowering the surface tension of water so that it
becomes more readily soaking into pores, soiled and stained areas
6. Washing with hot/warm water

• the major reason for using hot water for washing is that its surface tension is
lowered and is better wetting agent
• if the detergent lowers surface tension, then the heating may be unnecessary

# substance that reduces the surface tension of a liquid is called surfactant #, examples are
detergents, soap

Surface tension of common liquids

Liquid Temperature T (℃) Surface tension β (N/m)

Water 20 0.0728
Water 100 0.0589
Blood 37 0.0580
Mercury 20 0.4860
Benzene 20 0.0290
Glycerine 20 0.0690
Acetone 25 0.0230
ethanol 25 0.0220
Bromine 25 0.0410

Relationship between “β” and “σ”

Consider stretching a thin film of liquid on a horizontal plane ABDC, shown in Fig.21.

−38−
 Fig.21: Sketch of stretched thin film of a liquid.

Since the film has both upper and lower liquid-film surfaces, the force Fβ on BD due to
surface tension β is given by
Fβ = 2 β L (34)
If BD is displaced (moved) isothermally to B’D’ through distance x, then the work done Wβ
against force Fβ

work done = force × displacement W = ( 2 L β )( x ) = 2β Lx (35)

The increase in surface area = 2Lx (i.e., upper and lower surfaces).
Thus, the work done per unit area increment (surface energy σ) is given by
work done 2 β Lx
σ = = =β  σ =β (36)
area 2 Lx

 Eq (36) depicts the equivalence between surface tension β and surface energy σ ⇐
# oftentimes is more appropriate to explain surface phenomena in terms of energy
considerations rather than in force considerations #

Cohesive and adhesive forces

ο molecules in a liquid state experience strong inter-molecular attractive force, i.e., cohesive
and adhesive forces

ο cohesive ; - attraction between similar molecules/particles/entities, e.g., the molecules of

water droplets are themselves held together by the “cohesive forces”.
strong cohesive forces at the surface constitutes the surface tension.

ο adhesive ; - attraction between dissimilar molecules/particles/entities, e.g., the adhesive

forces between water molecules and the wall of a glass tube are stronger than cohesive
forces.

Contact angle (θ)

Surface of a liquid is usually curved either downward (concave) or upward (convex), where is
in contact with the wall of the solid container.

−39−
 +

Fig.22: (a) concave meniscus betweenn water and glass (b) convex meniscus
between mercury and glass. Note the angle θ is measured inside the liquid.
Such a concave or convex surface shape is known as meniscus The meniscus depends on the
relative strength of cohesive and adhesive forces.
If cohesive < adhesive, the liquid molecules tend to stick to the wall leading to concave
meniscus, e.g., water and glass, see Fig.22(a)

If cohesive > adhesive, the liquid entities themselves tend to stick together, and liquid
surface is pulled upwards from the wall, leading convex meniscus (e.g., between mercury and
glass, see Fig.22(b)).

 the contact angle θ is defined as the angle between the container’s surface and the
tangential line drawn to the liquid surface at the point of contact ⇐

# θ is measured through the liquid #

Capillarity action
This is the process by which a surface of liquid becomes elevated or depressed inside a tube
in relation to the surrounding liquid. This, too, is related to both contact angle θ and surface
tension α.

Suppose that a capillary tube is held vertically inside a liquid with a concave meniscus, see
Fig.23(a) and Fig.23(b).

Fig.23: Capillarity action (a) water-glass interface causes capillarity elevation/rise (b)
mercury-glass interface causes capillarity depression/fall

−40−
Surface tension exerts a downward-directed force on the walls of the tube. In accordance
with the Newton’s 3rd law of motion, the tube exerts an equal and opposite force on the
liquid which forces it to rise up within the tube.
At equilibrium, the weight of the liquid that has been lifted up equals to the vertical
component of the force exerted by the tube, see Fig.24.

Fig.24: Relationship between β and θ at equilibrium (a) height h of capillarity

elevation (b) resolved force component in term of β and θ
∗ consider a liquid of density, ρ, rises through vertical height, h, in a tube of radius r ∗
mass of liquid raised = density × volume ∴ wt. of liq. = m g
mass = ρ π r h 2
wt. = ρ π r 2 h g (37)

Length of the liquid surface in contact with the tube is equal to the circumference = 2πr
The vertical component of the force exerted by the tube is

force = length × surface tension F = ( 2πr ) ( β cos θ ) (38)

At equilibrium, (37) equals (38)

r ρ hg
∴ ρ πr 2 hg = 2πr β cosθ  β= (39)
2cos θ
For a perfect and clean glass, θ = 0°, i.e., Cos0° = 1, then
r ρ hg
 β= (40)
2

Factors affecting surface tension β :

• nature of the material(s)
• pressure (P)
• temperature (T) – increase in T lowers β.
• impurities, e.g., detergents, soap, salts, etc
• density of the liquid
• capillarity action
• contact angle

−41−
 • molecular (bond) forces, i.e., adhesive and cohesive forces
Illustrations

Q1. Calculate the radius of a capillarity tube if the water rises to a height of 12.5 cm within it,
assuming the angle of contact between the water and glass is 0° (take ρ = 1000 kg/m3,
β = 7.42 N/m and g = 10 m/s2).

A1. using (39), we have;

2 β cos θ 2 × 7.42 × cos 0 o
 r= = = 0.0121 m = 1.21 cm
ρhg 1000 × 0.125 × 10

Q2. Two glass capillarity tubes each 1.0 mm radius are put into two different liquids, one in
water and the other one in mercury. Compare the liquid level in the two tubes. Contact
angle between water and glass is 0° while contact angle between mercury and glass is
139°. Take 0.073 N/m and 0.473 N/m as the values of surface tension of water and
mercury, respectively, density of water = 1 g/cm3, density of mercury 13.6 g/cm3 and g
= 10 m/s2.

A2 using (39), we have

for water, for mercury,

2 β cos θ 2 × 0.073 × cos 0o 2 × 0.473× cos139o
 h= hw = hm =
rρ g 0.001×1000 ×10 0.001×1000 ×13.6 ×10
= 0.015 m = 1.5 cm = − 0.005 m = − 0.5 cm

NB: Liq water raises 1.5 cm up in the tube, and liq. mercury drops 0.5 cm down in the tube

Q3. The lower end of a glass capillarity tube is dipped in water, and the water initially rises to
a height of 9 cm. The tube is then broken at a height of 5 cm from the initial height.
What is the new height of the water column and the contact angle (take contact angle at
initial height h1 = 9 cm to be θ1 = θ°).

A3. Obviously, the new height h2 = 4 cm, and initial height h1 = 9 cm

ℎ= ⇔ =  = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

=  = cos 𝜃 = 𝜃 = cos = 63.6



Pressure difference (ΔP) across spherical interface

“Pressure difference” (ΔP) is also referred to as the “excess pressure “
Pressure Pi inside a soap bubble is greater than pressure Po outside

−42−
 Fig.25: Fluid interactions of surface tension, internal pressure and external
pressure on of liquid drop (or soap bubble).

To derive an expression for excess pressure ΔP inside an air-bubble

∗ consider force F acting on one-half of the bubble (hemisphere) ∗
- take r → radius of the bubble.
- take β → surface tension of the liquid.
∴ Force Fβ due to β (acting upwards, see Fig.25) is given as ;
Fβ = 2π rβ (41)

The net force Fo due to the outside pressure, Po (also directed upwards, see Fig.25) is acting
perpendicularly to area πr2, and is therefore
Fo = Poπr2
The net force Fi due to internal pressure Pi is downwards, see Fig.25, and has a magnitude

Fi = Piπr2
The hemisphere is at equilibrium, and therefore

Pi π r 2 = Po π r 2 + 2π r β 2β
 ΔP = (42)
 ( Pi − Po ) π r 2
= 2π r β r

• ΔP in (42) is the pressure difference (or the excess pressure)

• (42) is known as Young-Laplace equation that applies to all spherical liquid droplets
inside the liquid

Outside the liquid : -

A soap bubble (drop) has two surfaces and therefore, the excess ΔP is given by (43)

4β
ΔP = (43)
r

−43−
 • (43) is only applicable to all spherical liquid (soap) bubbles (droplets) outside the
liquid

Illustrations

Q A student using a circular loop of wire and soapy water (surface tension β of soapy water
is 0.025 N/m) produces a spherical droplet of bubble of radius 0.50 mm.
a) Find the pressure difference between inside and outside
The same soapy water is used to produce a soap bubble whose radius is double to that of
the spherical droplet.
b) Find the pressure difference between inside and outside
A a) for spherical liquid droplet (inside the liq.), we use (42),
2β 2 × 0.025
ΔP = = = 100 N/m2
r 0.0005
4β 4 × 0.025
b) using (43), we have; ΔP = = = 100 N/m2
r 0.001

Questions

Q Two similar soap bubbles (β = 0.025 N/m) have radii of 2.0 mm and 4.5 mm respectively.
For each bubble, determine the difference between the inside and outside pressures
Q A circular ring (r = 5.0 cm) is used to determine the surface tension of a liquid. The plane
of the ring is positioned so that it is parallel to the surface of the liquid. The ring is
immersed in the liquid and then pulled upward, so a thin film is formed between the ring
and the liquid. In addition to the rings weight, an upward force of 0.036 N is required to
lift the ring to the point where it just breaks free of the surface. What is the surface tension
of the liquid?
Q. A drop of oil (β = 0.032 N/m) has a radius of 0.010 mm. the drop is located at a distance
of 2.55 m below the surface of fresh water. The atmospheric pressure above the water is
1.01 × 105 Pa. a) What is the absolute pressure in the water at this depth?
b) Determine the absolute pressure inside the oil drop
Q. A soap bubble of diameter 6 cm floats in air. What is the excess pressure inside the
bubble when surface tension between soapy water and air is taken to be 0.15 N/m.
Q. A small bubble in water (β = 0.073 N/m) has a radius of 0.10 mm. Find the difference in
pressures between the inside and the outside of the bubbles.

Viscosity
When a liquid moves with steady speed (velocity) over a solid, it is observed that the layer of
the liquid in constant with the solid is more or less stationary.

−44−
Also, the velocity of any other layer of the liquid will be proportional to its distance from the
stationary layer, and it will be maximum for the most distant layer.

Fig.26: Layers of the incompressible liquid moving at different velocities.

𝑣 <𝑣 <𝑣 <𝑣 <𝑣 <𝑣 <𝑣

If specific layer is taken, then it is observed that a layer above it is moving faster than the
adjacent layer below it.
So, upper layer tries to increase the velocity of the lower layer while lower layer tries to
reduce motion of the upper layer. This creates internal frictional force between the layers.

∗ Viscosity is the property of a liquid (fluid) in which an internal frictional force acts between its
layers to oppose their relative motion ∗
These internal frictional forces are called viscous/resistive forces.

Viscous forces are intermolecular forces acting between the molecules of different layers of
liquid moving with different speeds / velocities.

Viscosity of a liquid decreases with increase in both temperature and pressure.

Coefficient of viscosity ‘η’

Consider a layer MN of a liquid moving with velocity υ w.r.t a parallel layer SQ, which is at
distance r away, see Fig.27 below.

Fig.27: Moving liquid (fluid) MN with force F relative to equal opposing F acting
in the opposite direction QS.

Consider force causing the motion be acting from M to N on a surface area Ω.

An equal force will act on it in the opposite direction, say QS.
−45−
For viscous and incompressible liquids, the backward (viscous) force Fv depends on:

i) directly proportional to velocity υ (niu) of the liquid layer,

Fv ∝ -υ , i.e., Fv acts in the opposite direction to υ
ii) directly proportional to cross-section A of the cylinder (A = πr2), i.e., Fv ∝ A
iii) inversely proportional to radius r, i.e., Fv ∝ 1/r
Thus,
Aυ Aυ
Fv ∝ − Fv = −η (44)
r r
• the proportionality constant, η (eta), in (44) is referred to as the “coefficient of
viscosity “.
• S.I unit of η is (N/m2)-s, i.e., pascal-second.
• η depends on the nature of the liquid
• viscous fluids that obey (44) are called Newtonian fluids, e.g., water and most gases
• if the two layers are very close together, then we may write (44) as (45):
dυ dυ
Fv = − η( dA) Fv = − η A (45)
dr dr
• in (45), A = πr2 is the area , and dv/dr is the velocity-gradient, defined as the rate of
change of velocity υ with distance radius r.
 the value of viscosity (and compressibility) for ideal liquid is always zero, i.e., η = 0
 the viscosity of air (and some liquids) is utilized for damping moving parts of some
instrument.
 the knowledge of the coefficient of viscosity η of different oils, and its variation with
temperature helps us to: -

i. select suitable lubricate for a given machine.

ii. determine the molecular mass
iii. determine the crystal structure of huge molecules like protein and
cellulose.

Poiseuille’s equation
The Poiseuille’s equation is used to calculate / determine the flow-rates of a fluid (liq.).
Scientist Poiseuille did intensive investigation about the viscosity of a liquid through a
capillarity tube of length ’L’ and radius “a”, when the liquid is flowing under constant
pressure P
The following assumptions were made:
i. the liquid is incompressible

−46−
 ii. the liquid flow is parallel to the tube-axis, and, is streamlined, i.e., smoothly and
uninterrupted.
iii. the liquid flow is steady, i.e., no acceleration of the flow exists.
iv. the velocity υ of the layer in contact with the wall is zero, and, increases regularly
towards the inner side, being maximum along the axis.

Theory
Let MN be a capillarity tube of length “L” and radius “a” (see Fig.28(a))

Fig.28: Capillarity tube MN of length ”L“ with (a) maximum radius “r = a” and (b) radius
element dr to demonstrate the Poiseuille’s formulation.

Consider a cylindrical layer of the liquid co-axial with the tube of the inner radius “r” and the
outer radius “r + dr” (see Fig.28(b)).

Also, note the followings:

• the velocity of the liquid layer at distance radius r = υ

• the velocity of the liquid layer at distance radius r + dr = υ − dυ

ο for a cylinder with radius “r” and viscous force “Fv”, exerts “P” related as Fv = P(πr2). Thus,
using. (45), and, noting that curved surface area A = 2πrL (see Fig.28(a). Therefore, we first
derive the velocity υ by treating area A as the surface area of the cylinder (see Fig.28(a)),
i.e., circumference multiplied by the length L, i.e., AL = 2πrL

dυ Prdr = −2η Ldυ

Fv = −η A
dr P
dυ = − r dr
dυ 2ηL
Fv = −η(2π rL)
dr  −P 
dυ υ =   rdr
P π r 2 = −η(2π r ) L  2ηL 
dr −P 2
dυ υ= r +C (46)
P r = −2η L 4η L
dr

To get the value of integration constant C in (46), we use boundary conditions, i.e., the
velocity along sides of the tube is zero, i.e., υ = 0 at r = a , therefore ;

−47−
 −Pa 2 Pa 2 P 2 2 (47)
0= +C  C = ∴ υ= [a − r ]
4ηL 4ηL 4ηL

Now, we use cross-section area element dA of a cylinder of radius r, i.e., dA = 2πrdr, (see
Fig.28(b)). Now, to derive volume flow-rate of the liquid, we proceed as:
∴ infinitesimal volume (vol element) dV of liquid flowing in this area segment per second,
i.e., dV = υ(2πrdr). Therefore, the volume V of liquid flowing through the whole tube per
second is
a a
πP  ar 2 r 4  πP  a 4 a 4 
 dV =  2πυ rdr
0
V=
2ηL  2
− = −
4  0 2ηL  2 4 
a
πP πP  a 4 
 (a − r 2 ) rdr
2
V= V=
2ηL  
0 2ηL  4 
a
πP πPa 4
 ( a rdr − r dr )
2 3
V= V= (48)
2ηL 0 8ηL

Note that (48) gives the volume V of a liquid flowing per second, i.e., flow-rate per second.
Thus, coefficient of viscosity 𝜂 is expressable as 𝜂 =

Viscous Resistance Rv of the Flow-rate

Eq (48) can be re-expressed as;

πPa 4 P P
V= =  V= (49)
8ηL ( 8ηL ) ( πa 4 )  Rv
 
Thus, in (49), 𝑅 = ≡ liquid (fluid) resistance (in Nm-2-s/m3 ≡ Ns/m5), V ≡ flow-rate of
liquid, and, P ≡ pressure difference ΔP

When two dissimilar tubes of unequal When two dissimilar tubes of unequal
diameters are connected in series. diameters are connected in parallel.
• pressure difference P = P1 + P2 • pressure difference P is the same across
• liquid flow-rate V is the same across both tubes, i.e., P1 = P2 = P
both tubes, i.e., V1 = V2 = V • liquid flow-rate V = V1 + V2
• equivalent liquid resistance Req, • equivalent liquid resistance Req,
𝑅 =𝑅 +𝑅 1 1 1
= +
𝑅 𝑅 𝑅

−48−
Q. i) Estimate the mass of water flowing in 10 min through a tube of 0.1 cm in diameter and
40 cm long, if the there is a constant pressure head of 20 cm of water. The η of water =
8.89 × 10-4 Ns/m2 (g = 10 ms-2, density of water = 1000 kg/m3)
ii) What would the water’s viscous resistance Rv ?
A(i). Using (48), and, noting that pressure P in the column of a liquid P =ρhg

πPa 4 π ( ρ hg ) a 3.14 × (1000 × 0.2 × 10 ) × (0.0005) 4

4

V= = = = 1.37 × 10 −7 m 3 /s
8ηL 8ηL 8 × 0.000889 × 0.4

vol. of water in 10 min, V10min  V10 = 1.37 × 10-7 × (10 × 60) = 8.22 × 10-5 m3
mass m (in kg) in 10 min, M10min  M10 = ρ × V = 103 × 8.22 × 10-5 = 0.0822 kg (82 g)
8ηL 8 × 0.000889 × 0.4
A(ii). Using (49), Rv = = = 1.45 × 1010 Ns /m 5
πa 4 3.14 × (0.0005) 4

Stokes’s law (flow) and Terminal Velocity ‘υt’

If a small spherical body falling in a long column of liquid (fluid), it carries along with it the
layers of the liquid in contact with, and therefore it will produce some relative motion
between the layers of the liquid.

Relative motion is opposed by viscosity Fv and upthrust Fu forces, and if the body is
sufficiently small, the resultant opposing force equals the driving force Fg (weight) and the
effect moves at the constant velocity υ. This constant velocity is termed as the “terminal
velocity, υt “

∗ consider a small spherical solid object of radius r falling through viscous fluid of viscosity η
with terminal velocity υt ∗

Then, the opposing force (the Stoke’s force) Fs is directly proportional to:
i. coefficient of viscosity, η
ii. radius of the spherical object, r.
iii. terminal velocity, υt radius of the spherical object, r.
Fs ∝ η rυt  Fs = τ ηrυt ,

where τ (tau) is the proportionality constant.

Thus, Fs = τ η r υ t , proportionality constant, τ, was determined by Stokes and found to be 6π,

leading to the Stoke’s law (equation), see (50).
Fs = 6 πηr υ t (50)
ο if ρ is the density of the sphere, then downward force w = Fg = mg
4 4
ms = Vs ρ = πr 3ρ Fg = ms g = πr 3 ρ g (51)
3 3

−49−
 ο second force is the upthrust force, Fu, given as the weight of liquid (fluid) displaced,
let α be the density of fluid displaced
vol. of liquid (fluid) displaced by the spherical object = (4/3)πr3

 upthrust force Fu = mLg = (4/3)πr3αg

4 4
mL = VLα = πr 3α Fg = mL g = πr 3α g (52)
3 3
Net downward force Fn is arrived at by subtracting (52) from (51).

4 4 4 4
Fn = πr3ρ g − πr3α g = πr3 g ( ρ −α ) Fn = πr3 g ( ρ −α ) (53)
3 3 3 3
For the terminal velocity υt, (53) equals to upward force Fs given by the Stoke’s law, see (50)
4 3 2r 2 g
6πη rυ t = π r g ( ρ −α )  υt = (ρ −α ) (54)
3 9η

note that in (53) ρ and α are the densities of the spherical falling object, and of the liquid
(fluid), respectively. If:
• ρ > α , the sphere (body) falls freely downward
• ρ < α , the sphere (body) raises upward gradually
• ρ=α , i.e., νt = 0
2r 2 g
• ρ >> α , ρ −α ≅ ρ  υt = ρ ⇐
9η

Illustration

A spherical drop of water (density = 1000 kg/m3) of radius 0.01 cm is falling freely through a
medium whose density is 1.2 kg/m3 and coefficient of viscosity η = 0.018 Nm-2s. Taking
acceleration due to gravity g=10 m/s, calculate the terminal velocity υt of the drop.
(υt = 0.00121 m/s)

Applications of Stokes’s law

• determination of electric charge (e), e.g., in Millikan oil-drop experiment
• used in parachute, i.e., a person landing with the help of parachute
• cloud formations, i.e., account for the formation of clouds

Terminologies associated with the flow of liquid

Streamline: any path (straight, curved or zigzag) whose tangent at any point gives the
direction of the flow of liquid (fluid)
Line of flow: any path traced (followed) by a mass of moving liquid (fluid).
Streamline (steady) flow:
−50−
 • occurs when liquid moves in parallel layers with no disruption (mixing) between them
• velocity of the liquid (fluid) layers at any point remains constant, i.e., the velocity of any
molecule, at any point, coincides with that of the preceding one.
• any line of flow (streamline) does not cross each other.
Tube of flow: A bundle of streamlines having velocity of the liquid (fluid) elements over any
cross-section perpendicular to the direction of flow.
Laminar flow: it is special case of streamlined flow in which velocities of all molecules are in
straight line of flow (streamline) and are the same throughout the motion.
Turbulent flow:
• occurs whenever the velocity of a liquid layer is very high or it rushes past an obstacle so
that there is sudden change in its direction of motion.
• The motion of the liquid (fluid) becomes irregular forming eddies or whirlpools.

Critical velocity ‘υc’ and the Reynold’s number ‘R’

In a viscous fluid, the low-speed and uniform flow of liquid (fluid) can be described as
laminar, i.e., fluid flow in which speed varies regularly layer by layer. The fluid can be
imagined as layers. Bottom layer is stationary, with velocity layers above, increasing from
bottom to top, refer to Fig.26.

Thus, in laminar flow, the liquid is in a state of continually increasing shear strain. When the
speed is sufficiently large, the motion become disordered and irregular (turbulent flow).

Hence, there must exist a minimum velocity, called critical velocity, υc , below (or above)
which the flow is laminar (or turbulent)

From experimental observations, it is found that υc is

i. direct proportional to coefficient of viscosity, η

ii. inversely proportional to density of the liquid (fluid), α
iii. inversely proportional to diameter of the tube, d.

Thus,
η η
υc ∝  υc = R (55)
αd αd
• the proportionality constant, κ, in (55) is referred to as “ Reynold’s number ”
υ cα d
R=
η

• R is defined as the ratio of inertial force to the viscous force per unit area of flow

• R can be used to characterise any flow of liquid (fluid):

0 < 𝑅 < 2000 ⇔ streamline / laminar flow

−51−
 2000 < 𝑅 < 3000 ⇔ transition
𝑅 3000 ⇔ turbulent flow

Equation of continuity
Entails the flow of conservation of mass.

It states “ for any streamlined flow, the mass flow-rate is constant from one x-section of tube
of flow to another ”.

∗ a line of flow: - path followed by an element (mass) of moving liquid (fluid)

∗ streamline: - a curve whose tangent at any point is in the direction of liquid (fluid)
 in a steady flow, the streamlines coincide with the lines of flow ⇐

Assuming steady flow, we select a finite number of streamlines (see Fig.29(a)) to form a tube
of flow (see Fig.29(b)).

Fig.29: Sketches depicting an idealized (a) line of flow (b) tube of flow and (c)
streamlined flow.
As streamlines do not cross each other, liquid (fluid) that enters tube of flow must exist at
the other end.

Say, a liquid (fluid) layers enters a tube at point S where cross-section area is A1, and leaves
the tube at point Q where cross-section area is A2, as depicted in Fig.29(c).
Let υ1 and υ2 be velocities of the liquid (fluid) at points S and Q, respectively.
Vol. of liquid (fluid) that flows into the tube in time interval Δt across S will be ΔV1 = A1υ1Δt
and across Q will be ΔV2 = A2υ2Δt
If ρ1 and ρ2 are densities of liquid at points S and Q, respectively, then masses of liquid (fluid)
Δm1 and Δm2 at S and Q, respectively will be:
Δ m1 = ρ1 A1υ1 Δ t (a)
(56)
Δ m 2 = ρ 2 A2υ 2 Δ t (b)

Since no mass is lost (created), then Δm1 = Δm2

−52−
 Δ m1 = Δ m 2
ρ1 A1υ 1 = ρ 2 A2υ 2 (57)
or in a more general term
ρ Aυ = constant (58)
• (58) is called the “equation of continuity”, i.e., conservation of mass.
• for incompressible liquid (fluid), density ρ is constant, i.e., ρ1 = ρ2 =ρ, hence

Aυ = C (59)

• constant C in (59) gives volume flow-rate (or volume-flux density).

• from (59), the velocity of flow υ varies inversely with the cross-sectional area A.

Bernoulli’s principle (Equation/formulation)

It entails the law of conservation of energy. It gives the relationship between the velocity υ
of a liquid (fluid), and the pressure P it exerts
∗ it states that “ in any streamlined flow, the sum of pressure-energy, kinetic-energy and
potential-energy per unit mass of the liquid (fluid) remains constant at every cross-section of
the tube of flow ”
Alternatively, It states as “ fast (swift)-moving liquids (fluids) exert less pressure than slow-
moving (liquids) fluids “

Example of Bernoulli’s principle in everyday life;

• lifting of an aeroplane wing to enable the plane/aircraft to fly
• sailboat can sail into/through/against wind
• baseball can curve
• smoke drawn up through a chimney

Consider the tube of flow below, see Fig.30

Fig.30: Sketch demonstrating tube of flow for a given liquid (fluid).

Let P1 and P2 be pressures at S and Q, respectively.
Product of pressure P and volume V yields workdone
−53−
 P = F/A; and V = Ad (d ≡ distance)  PV = (F/A)(Ad) = Fd = work done W
Thus, the workdone on the liquid (fluid) entering at S, WS, is WS = P1A1υ1Δt ,
and workdone at Q, WQ is WQ = P2A2υ2Δt
Thus, net workdone WSQ is WSQ = P1A1υ1Δt - P2A2υ2Δt ,
This is equated to the energy of mass Δm of liquid (fluid) flowing from S to Q {see (56)}.
In other words,
P1 A1υ 1Δt − P2 A2 υ 2 Δt = −Δ m [ E1 − E2 ]
, (60)
P1 A1υ 1Δt − P2 A2 υ 2 Δt = Δ m [ E2 − E1 ]
where, 𝐸 and 𝐸 are energies per unit mass at points S and Q, respectively. The energy E
per unit mass of the Liquid (fluid) can as well be written as :
1
E = υ2 +U + φ , (61)
2
where : (1 2)υ 2 → kinetic-energy (k.e) per unit mass.
U → potential-energy (p.e) per unit mass.
φ → internal-energy per unit mass. Note that internal energy is the
thermal/chemical energy.
Thus,
P1 A1υ1 Δt
−
P2 A2υ 2 Δt
=
1 1 
υ 2 + U 2 + φ 2 −  υ1 + U 1 + φ 1 
2 2
P1 P2 1 1 
Δm Δm 2 2  − = υ 22 + U 2 + φ 2 −  υ12 + U 1 + φ1 
ρ1 ρ2 2 2 
but Δm = ρ Aυ Δt
P1 1 P 1
P1 A1υ1 Δt P2 A2υ 2 Δt 1 2  + υ12 + U 1 + φ1 = 2 + υ 22 + U 2 + φ 2 (62)
= υ 2 + U 2 + φ 2 −  υ1 + U 1 + φ 1 
2
− ρ1 2 ρ2 2
ρ1 A1υ1 Δt ρ 2 A2υ 2 Δt 2 
Eq (62) can be generalized as:
P 1
+ υ 2 + U + φ = constant , (63)
ρ 2
• (63) is called the Bernoulli’s equation with an additional term for thermal
(chemical) energy

• P/ρ is the pressure-energy per unit mass, 0.5ν2 is the kinetic-energy per unit mass,
U is the potential-energy per unit mass and φ is the thermal-energy per unit mass.

• for incompressible liquid (fluid), thermal energy φ is constant, i.e., φ1 = φ2 = φ, and

density of the fluid is constant as well, i.e., ρ1 = ρ2 = ρ; hence

−54−
 P1 1 P 1
+ υ12 + U1 + φ = 2 + υ22 + U 2 + φ
ρ 2 ρ 2
1 1
P1 + ρυ12 + ρ U1 + ρ φ = P2 + ρυ22 + ρU 2 + ρ φ
2 2
1 1
P1 + ρυ12 + ρ U1 = P2 + ρυ22 + ρ U 2
2 2
more generally,
1
P + ρυ 2 + ρ U = constant , (64)
2
• if the flow of the liquid (fluid) is due to gravity, and points S and Q lie at heights h1
and h2 respectively from a reference horizontal plane ZZ’, then,
p.e = U = Δ mg (h2 − h1) = Δ mgh

• p.e per unit mass U = hg , thus,

1
P + ρυ 2 + ρ hg = constant , (65)
2
Example 1

𝑃 + 𝜌𝜈 + 𝜌ℎ 𝑔 = 𝑃 + 𝜌𝜈 + 𝜌ℎ 𝑔

150000 + 12500 + 0 = 𝑃 + 50000 +

19600
∴ 𝑃 = 92900 Pa

Example 2
The speed of water in a hose increased from 19.6 m/s to 25.5 m/s going from the hose to
the nozzle. Assuming an horizontal and frictionless flow, calculate the pressure in the hose if
the pressure in the nozzle is 101000 N/m2 (take density of water as 1000 kg/m3 and
acceleration due to gravity as 10 m/s2)

Solution

p.e = 0, since the ground is level

∴ 𝑃 + 𝜌𝜈 + 𝜌ℎ 𝑔 = 𝑃 + 𝜌𝜈 + 𝜌ℎ 𝑔 , but ℎ = ℎ = ℎ , for horizontal ground

𝑃 + 𝜌𝜈 = 𝑃 + 𝜌𝜈
𝑃 + (0.5 × 1000 × 19.6 ) = (1.01 × 10 ) + (0.5 × 1000 × 25.5 )
𝑃 + (1.92 × 10 ) = (1.01 × 10 ) + (3.25 × 10 )
𝑃 = 2.34 × 10 N/m2

−55−
Applications of the Bernoulli’s principle
a) Torricelli’s theorem

Fig.31: Sketch demonstrating Torricelli’s theorem.

Assume the flow speed υout is much greater than the flow of speed near the top’s tank.
Assume the tank’s diameter is soo large that we can ignore the reduction in the water
level. Say at the top of the tank, pressure = Po same as at O (neglect both atmospheric
pressure, and pressure due to water column h)
At the top of the tank, υ = 0, U = 0
At the tap, υ = υout, and U = -hg ; U = p.e per unit mass
Assuming υ1 = υ2 =0, then the Bernoulli’s equation becomes:
1 1
P1 + ρ1υ12 + ρ1U 1 = P2 + ρ2υ22 + ρ2U 2
2 2
1 1
P1 + ρ1υ12 + ρ1h1 g = P2 + ρ2υ22 + ρ2 h2 g
2 2
Assume h1 = h2 = h, P1 = P2 = Po, υ1 = U1 = 0, υ2 = υout, U2 = −hg, ρ1 = ρ2 = ρ
1 2
Po = Po + ρυout − ρ hg
2
1
 ρυout
2
= ρ hg  υout = 2hg ms-1
2

Examples
1) Calculate the velocity with which a liquid emerges from a small hole in the side of a
tank of a large cross-sectional area if the hole is 0.20 m below the surface (take density
of water as 1000 kg/cm3, g = 10 m/s2)
Solution υout = 2hg = 2 × 0.20 × 10 = 2.00 ms -1
2) Water flows in a horizontal tube BD from point B to D. The water pressure changes by
600 N/m2 between B and D. If the cross-sectional areas are 30 cm2 and 15 cm2,
respectively, determine the flow-rate of the water in the tube (g = 10 m/s2)
Solution using (59), i.e., use the equation of continuity;
−56−
 AB υD 30
Aυ = Constant  ABυB = ADυD  =  = 2  υD = 2υB
AD υB 15
using the Bernoulli’s equation (see (62))
assume υ1 = υB, υ2 = υD, and since the tube is horizontal, UB = UD = U ; ρB = ρD = ρ , also φB
= φD = φ
PB 1 P 1 3
+ υB2 + U B + φB = D + υD2 + U D + φD  PB − PD = ρ υ B2
ρB 2 ρD 2 2
1 2 1 3
PB +ρυB = PD + ρυD2  600 = × 1000 × υ B2
2 2 2
1 2 × 600
 PB − PD = ρ υD2 − υ B2   υB =
2 3 × 1000
1  υ B = 0.63 ms −1
 PB − PD = ρ (2υB ) 2 − υB2 
2 ∴ υ D = 2 υ B = 1.26 ms −1

Therefore, flow rate  Aν = Constant

AB υ B = AD υ D   ( 30 × 10 −4 ) × 0.63  =  (15 × 10 −4 ) × 1.26  = 1.89 × 10 −3 m 3s −1
   
b) The venturi meter
Device / gauge used for measuring rate of flow of liquid (fluid) in a pipe

Fig.32: sketch of venturimeter measuring gauge.

A fluid of density ρ flows through a pipe of cross-section area B, then into reduced cross-
section area D, and a manometer is attached as shown in Fig.32. Let the mercury (liquid) in
the manometer gauge have a density α.
If υB and υD represent the velocities at B and D respectively, then according to the equation
of continuity (59) for an incompressible liquid (fluid) {ρ → constant}.
υB D υD B υB υD B D
Bυ B = Dυ D  =  =  =  υD = υB or υB = υD
υD B υB D D B D B (66)

According to the Bernoulli’s equation

−57−
  B2 
 2( PB − PD ) = ρυB 
2
− 1
D 
2

1 1
PB + ρυ = PD + ρυ
2
B
2
D υB
2

2 2  2( PB − PD ) = ρ
2
(B − D )
2
2
 2( PB − PD ) = ρ (υD2 − υB2 ) D
(67)
υD
2

 2( PB − PD ) = ρ
2 2
2
(B − D )
B

Recall; 𝜈 𝜈 ,𝐴 𝐵, 𝑃 𝑃
In other words, where the speed of water/liquid (fluid) is high, the pressure is low. Thus, can
be shown straightforwardly from (67) that:
2 ( PB − PD ) 2 ( PB − PD )
υB = D
ρ (B 2 − D 2 )
and υD = B
ρ (B 2 − D 2 )
(68)

Also, recall that PB − PD = ΔP = αhg (from the mercury manometer gauge)

2α hg 2α hg
∴ υB = D
ρ (B 2 − D 2 )
and ∴ υD = B
ρ (B 2 − D 2 )
(69)

If ρ = α, then eq. (69) reduces to eq. (70):

2 hg 2 hg
υB = D
(B 2 − D 2 )
and υD = B
(B 2 − D 2 )
(70)

Example
1) A powerful pump is placed at A and pumps water which flows smoothly and exit at B
with velocity 20 cm/s, as shown in Fig.33. The cross-section areas at B and C are 6.0 cm2
and 1.0 cm2, respectively. Find height h of mercury in the tube (take densities of water
and mercury as 1.0 g/cm3 and 13.6 g/cm3, g = 10 m/s2)

Fig.33: Sketch of the mercury manometer gauge.

Solution

By equation of continuity (59), υ C = Bυ B =

( 6 × 10 − 4 ) × 0.20 = 1.20 m /s
−4
C 1 × 10

Since the pipe is horizontal, υA = υB = 20 cm/s, (since A & B are of the same size).
Hence by Bernoulli’s principle, see (65):

−58−
 1 1
PB + ρυ B2 = PC + ρυ C2
2 2
1 1
PB − PC = ρ (υ C2 − υ B2 ) = × 1000 × (1.2 2 − 0.2 2 ) = 700 N/m 2
2 2

But PB – PC = ΔP = αhg, where α is the density of mercury (liquid)

PB − PC = Δ P = α hg
 700 = 13600 × h × 10  h = 5.15 × 10 − 3 m = 0.515 cm

c) The actions of carburettor, paint gun, insect sprayer, are based on the Bernoulli’s
principle
d) The actions of Bunsen burner, gas burner lie on the Bernoulli’s principle
e) Motion of the spinning ball

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