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SCHOOL OF PURE AND APPLIED SCIENCES

DEPARTMENT OF
PHYSICAL SCIENCE

COURSE CODE: BPY 2201

COURSE TITLE: STRUCTURE AND PROPERTIES OF MATTER

Kimiti R. M

Kimiti2001@yahoo.com

copyright@2016-All rights reserved for MKU

MEANING OF SYMBOLS

Objectives

Activity

! Key note

Summary

Self Assessment Question (SAQs)

Further Reading
COURSE OUTLINE

Week Topic Lectures

1

10

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13

14
STRUCTURE AND PROPERTIES OF MATTER.
CHAPTER 1.

STATES OF MATTER.
1.1 INTRODUCTION.

The existence of three phases of matter is due to a struggle between inter-atomic (intermolecular)
forces and the motion which atoms (molecules) have because of their internal energy.

1.2 BROWNIAN MOTION.

The effect, on its own, does not offer conclusive proof for molecules but it clearly reveals that the
microscopic scale there is greater activity in matter; which macroscopically appears to be at rest.

The theory of the motion was worked out by Einstein and is found to correspond closely with
observation. His basic assumption was that the suspended particles have the same mean kinetic
energy as the molecules of the fluid and so behave just like very large molecules. Their motions
should therefore be similar to those of the fluid molecules.

1.3 THE UNIT CELL.

The unit is in general defined as that the volume of a solid from which the entire crystal can be
constructed by translational repetition in three dimensions.

1.4 ATOMIC BONDING IN SOLIDS.

1.4.1 Binding energy.

Materials consist of atoms held together by the attractive forces they exert on each other. These
forces are electrical in nature and create inter-atomic bonds of various types. The type formed in any

The nature of the bonds that hold the atoms together in molecules is explained by quantum mechanics
in terms of an atom consisting of a small nucleus, concentrating the mass and the positive charge,
surrounded by clouds or shells of electrons relatively far away. It is among the outermost, more loosely
bound electrons, the valence electrons, that chemical reactions and primary bond formation takes place.

case depends on the outer electrons in the electron clouds of the atoms involved.

1.4.2 Interaction energy (u).

Ions are all arranged in a crystal lattice. Coulombs attractive as well as quantum mechanical repulsive
energies are operative. According to Earns haw’s theory, a system cannot be in equilibrium under its
own electrostatic forces. The Born- Madelung theory hence assumed the existence of a quantum
mechanical repulsive force also.

Interaction energy ( )= (coulomb attraction energies + quantum mechanical repulsion)

Consider ions i and j in the lattice. Coulomb attraction force is given by;

…………………………………. (1)

Quantum mechanical repulsive force can be assumed to be given by;

⁄
………………………………….. (2)

Where A and p are constants. Interaction energy ( ) is then given by;

⁄
( ) ……………… (3)

Consider some ions in a crystal, having a distance of separation equal to R.

R
- + - + - + - + -
1 2 3 4 5 6

reference ion

Figure 3

Coulomb attraction energy =

= ⁄ ⁄ ⁄

= ⁄ ⁄ ⁄

= [ ,

Where

Suppose there are N ion pairs per unit volume. Interaction energy per unit volume (U) will be given
by;

Where M = number of nearest neighbors.

Since a perfect square is a minimum energy configuration;

( ) =0 ………………………………………………………………………………………………… (6a)

⁄
( ) ………………………………………………. (6b)

Hence,
 ⁄
……………………………………………………………………………….. (6c)

=- * +* + …………………………………………………………………………………. (6d)

For alkali halides, ⁄ Hence,

[ * + * + ………………………………………… (7a)

Per molecule,

……………………………………………………………………………………… (7b)

Per mole N=N0 (Avogadro’s number):

[ ……………………………………………………………………………… (7c)

The above consideration indicates that the main contribution to the binding energy of ionic crystals is
electrostatic and is called the Madelung energy.

1.4.3. Inter-atomic bonds (types of bonds)

1.4.3.1. Ionic bonds: The most stable electronic configuration for all but very light atoms is a
complete outer shell of eight electrons, called the octet, this structure may be obtained by the
donation of an electron by one atom to another. This results in electrostatic charges on the atoms,
creating the attractive forces of these ionic bonds.

1.4.3.2. Covalent bonds: Are formed when one or more pairs of valence electrons are shared
between two atoms, again resulting in stable electronic shells. Thus the atoms of carbon form
covalent bonds with other carbon atoms. Each carbon atom has four outer electrons and all can be
shared with four other carbon atoms to make four bonds, each consisting of two interlocking
electron clouds.

1.4.3.3. Metallic bond: In the metallic bond, the number of valence electrons is far too small to
provide complete shells for all atoms. The resulting bonds involve the concept of positively charged
atoms embedded in a permeating “gas” of electrons free to move about at will. The features of high
electrical conductivity, on-saturation of valence, and lack of direction in the bonding forces are
accounted for.

1.4.3.4. Van der Waals bond: They arise because, although the centers of negative and positive
charges in an atom coincide over a period of time, they do not coincide at any instant. There is a little
more of the electron cloud on one side of the nucleus than on the other. A weak electric ‘dipole’ is
produced giving rise to an attractive force between opposite ends of such dipoles neighboring atoms.

1.5 Crystalline and amorphous solids.

1.5.1 Nature of inter-atomic forces.

In the four types of the main inter-atomic forces just discussed, only attractions are considered but
there must also be inter-atomic repulsions, otherwise matter would collapse. Evidence, both
theoretical and experimental, suggests that at distances greater than one.

Atomic diameter the attractive force exceeds the repulsive force; whilst for small distances, i.e., less
than one atomic diameter, the reverse is true. In Fig.5 the dotted graphs show how the short-range
attractive force and the very short-range repulsive force between atoms vary with the separation of
the atoms; the total or resultant force is shown by the continuous graphs.

It can be seen that for one value of the separation R0 , the resultant inter-atomic force is zero. This is
the situation that normally exist in a solid, but if the atoms come close together-for example, when
the solid is compressed- they repel each other. They attract when they are pulled further apart. We
have only considered two atoms whereas in a solid each atom has interactions with many of its close
neighbors. The conclusion about the existence of an equilibrium separation, however will still hold
good.

In an ionic bond the short-range attractive part of the inter-atomic force arises from the attraction
between positive and negative ions which pulls them together until their electron clouds start to
overlap, thus creating a very short-range repulsive force. The attractive and repulsive forces in the
other types of bonds also arise from the electric charges in atoms.

1.5.2. Types of solids (formation of solids).

The formation of a solid would involve cooling the vapor of the material until it condenses into the
liquid state, and then further gradual cooling of the liquid until it solidifies. Results of such an
experiment, for a given quantity of the material, may be represented on a volume versus
temperature V (T) plot such as the one schematically shown in Fig 6. A sharp break or bend in V (T)
marks a change of phase occurring with decreasing temperature. When the temperature is brought
low enough, a liquid solid transition takes place (with the exception of liquid helium, which remains
liquid as T 0 in the absence of pressure) the solid persist to T=0.
A liquid may solidify in two ways: discontinuously to a crystalline solid, or continuously to an
amorphous solid (glass). The two solids resulting from these two quite different solidification
scenarios are labelled, correspondingly, 1 and 2 in Fig.6. Scenario 1 occurs at temperature Tf, the
freezing (or melting point). The liquid crystal transition is marked by a discontinuity in V (T), an
abrupt corruption to the volume of the crystalline solid. In a quenching experiment carried out at a
sufficiently low cooling rate, this is usually the route taken to arrive at the solid state. But at
sufficiently high cooling rates, it is found that most materials alter their behavior and follow route 2
to the solid phase. Tf is bypassed and the liquid phase persists until a lower temperature Tg is
reached. Here the second solidification scenario is realized.

The liquid glass transition occurs in a narrow temperature interval near Tg the glass transition
temperature. There is no volume discontinuity, instead V (T) bends over to acquire the small slope
(similar to that of the crystal) characteristic of the low thermal expansion of a solid.

Fig 7 presents, schematically and in a nut shell, the salient characteristics of the atomic arrangements
in glasses as opposed to crystals.

Both crystals and glasses are bona fide solids and share the essential attributes of the solid state.
Their fundamental difference is in the basic nature of their microscopic, atomic scale structure. For
an amorphous solid, the essential aspect with which its structure differs with respect to that of
crystalline solid is the absence of long-range order. There is no translational periodicity. On the other
hand, the atomic positions in the glass are not randomly distributed in space. Randomness is a trait
more properly associated with Fig 7c, at least in the low density limits in which the atoms comprising
the gas may be viewed as point particles.
For such a dilute gas (the ideal gas of the kinetic theory), the particle positions are totally
uncorrelated. Each atom may be located anywhere, independent of the positions of all other atoms.
But in Fig 7b, there is seen to be a high degree of local correlation. Each atom has (in the example
used here for illustration) three nearest neighbors at nearly the same distance from it. Bond angles
are also nearly equal. Thus, while the lack of long-range order in glasses implies randomness at large
separations, the atomic-scale structure is highly non-random for a few inter-atomic distances about
any given atom.

1.6 POLYMERS.

A polymer is a large molecule built by the repetition of small, simple chemical units. In some cases the
repetition is linear much as a chain is built up from its links. In other cases the chains are branched or
inter-connected to from three dimensional methods. The repeat unit of the polymer is usually
equivalent to the monomer or starting material from which the monomer is formed.

A polymeric solid consists of an assembly of very long molecules such that within the molecular chain
there are strong covalent bonds but between the chains only weak bonding occurs, usually the van
der Waals nature.

Conventionally solid- state physics deals with the properties of well-defined, regular arrays of atoms.
This certainly does not describe the usual situation in polymers. Many polymers have both crystalline
and amorphous regions. The proportion of crystalline to amorphous regions in a polymer depends on
its chemical composition, molecular arrangement and how it has been processed.

Polymeric materials are unique because of the range of structural forms that can be synthesized and
the way in which changes can be made in the structure in a local or general way. In contrast to many
materials, polymers do not have a unique molecular weight but are described in terms of weighted
average molecular weights representing the average and the distribution about the mean.

Thus in comparison to well ordered, covalent or ionically bonded inorganic materials, polymers are
weakly bonded, disordered materials. These differences are profound effect on most of the
properties of polymers. They are heat insulators and are usually soft and easily distorted. They are
electrically insulating and poor conductors of charge.
1.7 QUESTIONS.

1. Of what significance is the study of structure of materials?

2. Briefly describe the nature of inter atomic forces and how they act.
3. Why is the perfect symmetrical array the preferable arrangement of atoms in solids?
4. By considering a system of ions in a crystalline solid, determine an expression for the
Madelung energy for the system.
5. By considering a perfect crystal, which is upset in the simplest way possible, show that the
perfect crystal is a minimum energy configuration.
6. Consider a crystalline solid having N ion-pairs per unit volume and deduce an expression for
the interaction energy per unit volume (U).
7. Show that the lattice energy is equal to about 90% of the Madelung energy in the case of
ionic crystals.
8. How does the occurrence of three phases of matter arise?
9. For an amorphous solid, the essential aspect with which its structures differs with respect to
that of a crystalline solid is the absence of long-range order and translational periodicity.
Elaborate on this statement by explaining with the aid of a diagram the situation prevailing in
the gaseous state of a given material.
10. Both crystals and glasses are bonafide solids and share the essential attributes of the solid
state. What would you consider to constitute their fundamental difference?
CHAPTER 2

CRYSTAL STRUCTURES.
2.1 INTRODUCTION.
An approximation sufficiently accurate for the purpose of treatment of the geometrical
arrangements of the atoms in crystals is to suppose the atoms to be round, hard balls. These balls
rest against each other in various geometrical arrangements, each solid having its own mode of atom
placement. Solids in which atoms are arranged in some regular pattern in three dimensions are called
crystals. And the arrangement of atoms is termed the crystal structure. The internal regularity of
atom placement in solids often leads to a symmetry of their external shapes.

The structure adopted by a crystalline solid depends on various factors including the kind of bonds
formed and the size and the shape of the particles involved. For example, in metals where all the
positive ions attract all electrons, the bonding pulls equally in all directions, i.e. non-directional and
every ion tends to surround itself by as many other ions as is geometrically possible. A close-packed
structure results. On the other hand, in covalent solids the bonding is directional, i.e. every shared
electron is localized between only two atoms. This does not encourage close-packing since the
number of atoms immediately surrounding each atom is limited to the number of covalent bind it
forms. We shall begin our discussion with description of some common crystals structures, which will
then be analyzed by means of both theoretical and experimental techniques.

2.2 Some common crystal structures.

2.2.1 Hexagonal close-packing (hcp) structure.
The hexagonal close-packed structure is built up from layers of hexagons. Zinc and magnesium form
hcp crystals.

A small volume of the hcp structure (this volume contains the number of atoms in three unit cells) is
sketched in fig 1. This structure is termed a close-packed structure because it possess the maximum
density of packing hard spheres.

The maximum number of the nearest neighbors, which a typical a typical atom in this structure can
have, is 12. The typical atom is the one at the center of either the top or the bottom face of the
structure. The neighbors are then the 6 atoms in its plane, plus the 3 in the plane above and the 3 in
the plane below. The distance ‘a’ between the centers of adjacent atoms sites is called the atomic
diameter.

2.2.2. Face-centered cubic (fcc) or cubic close packed (ccp) structure.

A unit cell of this crystal structure is a cube. An atom occupies each corner of the cube and the center
of each face, hence the name face-centered cubic (fcc).

This structure is symmetrical with respect to rotation by 900 about any one of the cube edges. The
face centered cubic structure is close packed, each atom having 12 nearest neighbors. The atoms are
in contact along the diagonals of the faces. Copper and aluminum have this structures.
2.2.3. Body-centered cubic (bcc) structure.

Many elements possess structures, which are not formed of close packed planes. One of these is the
body centered cubic, which is sketched in fig 3. This unit cell is cubic with an atom at each corner and
an atom in the center of the cube. This structure is not close-packed, since each atom has eight
nearest neighbors. Atoms are in contact along body diagonals.

2.2.4 Tetrahedral structures.

These have particles at the center and at each of the four corners of a regular tetrahedron as shown
in fig 4. These more open arrangement is found in carbon (as diamond), silicon and germanium all
substances which form covalent bonds. The hardness of diamond is partly due to the fact that its
atoms are not in layers and so cannot slide over each other as they can in graphite, the other
crystalline form of carbon. Graphite forms layers of six-membered rings of carbon atoms that are
about two and a half times farther apart than are the carbon atoms in the layers, fig 4b. The forces
between the layers are weak, thus explaining why graphite flakes easily and is soft and suitable for
use in pencils and as a lubricant.

Graphite and diamond provide a good example of the importance of structure in determining
properties.

2.2.5. The simple cubic structure.

Another possible structure is the simple cubic arrangement of atoms. The unit cube of this structure
has atoms only at the corners of a cube, and the atoms therefore touch along cube edges (fig 5). This
structure is loosely packed, each atom has only six nearest neighbors. Only one element, P0 (in a
certain temperature region), exhibits this crystal structure.

2.3. DENSITY.
Density for crystal structures refers to the number of atoms per unit cell.

2.3.1. H.C.P.Structure.

Contribution to unit cell by atoms at the corners in the top and bottom layers= ⁄

Contribution from center atoms:

[ ⁄
[

Therefore, density = 2 + 1 + 3 = 6 atoms per unit cell.

3.3.2. F.C.C. structure.

Corner atoms: ⁄

Atoms on faces: ⁄

Density = 1+ 3 =4 atoms per unit cell.

From density considerations, it appears that the hexagonal close packing structure (HCP) is more
closely packed than the face centered cubic structure (FCC). However, available space should be
taken into account.

2.4. PACKING FRACTION-(relative density packing).

Density consideration do not take into account the available space in crystal structures. Hence
density alone cannot determine the more closely packed system. Consequently we resort to
calculating the packing fraction of the atoms in a unit cell.
2.4.1 H.C.P Structure
 Assumption – all atoms are contiguous.
a) Axial ratio ( ⁄ ):
For this structure it is even convenient to begin by calculating the ratio of the height of a unit cell to
the lattice parameter. For the purpose of determining the packing fraction we will define a unit cell
for the hcp structure as one that consists of six similar triangular blocks of height c and having an
inter atomic distance of a.

Consider one small isosceles triangle: from the sine rule, we can write,

⁄ ⁄

Applying the Pythagoras rule to right-angled triangle XYP:

=( ) ( )
√

= ( )

=( ) √

Axial ratio= √ .

b) Packing fraction.
Volume of a single triangular block=base area x height.

Area of one triangle.

Base = 2R;

[Altitude]2 =(2R)2 –R2 =3R2

⁄
Base area = ⁄ √
⁄ ⁄
⁄ [ ]
Height = c= ⁄ ⁄ [
√

Volume of one triangular block = base area x height.

⁄
= √ ( ⁄ )

= ⁄

Hence volume of the unit cell = ⁄

P.F. = (Volume of atoms per unit cell)(volume of the unit cell)

=
√

2.4.2 F.C.C. Structure.

Assumption – atoms touch one another along face diagonals. Let the radius of each atom be R and a
= lattice parameter. Consider a face of the unit cell:

Length of diagonal =4R=√ ⁄

⁄ ⁄

 Volume of atoms per unit cell = 4 x volume of an atom.

⁄ ⁄
 Volume of the unit cell =
⁄
P.F. =[ ⁄ [ ]

2.4.3. B.C.C.Structure.

Density =( ⁄ )

AB =body diagonal.

Also:

⁄
Volume of unit cell =
 * ( ) +
( )
P.F. = ⁄

2.4.4. Mixed structures.

The H.C.P, F.C.C, S.C., and B.C.C. fall into what is referred to as clean classifications of structures.
These are known as basic structures. A good number of elements and compounds crystallize into
mixed structures. Mixed structures are combinations or derivatives of basic structures. Examples of
mixed structures are the diamond, caesium chloride and sodium chloride structures.

Sodium chloride structure.

The unit cell of the sodium chloride structure consist of two face-centered cubic sub lattices, one of
Na ions having its origin at the point (0,0,0.), the other of the Cl ions having its origin midway along
the cube edge,say,at point (a/2,0,0).

This lattice is simple cubic if the difference between the Na and Cl ion positions is ignored.

If atoms touch one another,

Volume of the cell =

Atomic density:

 Na ions D= * + * +
 Cl ions D= * + [

P.F = (total volume of atoms per unit cell/ (volume of unit cell)
[
=

= [ ]
 = [

= [

= /3(0.38)
=2.38/3
=0.796

2.5. Miller indices.

We can imagine different sets or families of planes passing through lattice points. Planes parallel to
one another and equally spaced by a distance d, say, all belong to one set. The orientation of the
planes with respect to the axes of the unit cell is different for different sets. These orientations are
specified by three numbers called the miller indices. These numbers are defined in terms of the
intercepts of the plane on the coordinate axes.
Let one plane of the sets pass through the origin. Suppose that the adjacent plane has intercepts on
the axes of x1 , y1 and z1 in units of the cube edge (fig 7). There exists a number, say, s, such that the
product of s and the reciprocals of these intercepts gives the lowest set of integers having the same
ratio as 1/x1,1/y1and 1/z1.
Negative index numbers are used to specify planes with negative intercepts, a plane with negative x
intercepts is written( ̅ ). Planes of a form –i.e., planes which are equivalent in the crystal – are
enclosed in braces:{ } For example the planes { } embrace the group

Procedure:
i. Write down the intercepts.
ii. Take their reciprocals.
iii. If the reciprocals are the fractions then convert them to integers.
Example: intercepts, 4a, 3b, 2c
4a= x1, 3b=y1, 2c= z1.
Miller indices,

The miller index notation is especially useful for cubic systems. Among its desirable features;

 The distance d between adjacent planes of index numbers (hkl) is given in terms of the cube
edge ‘a’ by the expression

IN 2-DIMENSIONS.

Miller indices (hkl); intercepts on the x, y, z axes; ( )

2.6. X-ray crystallography.
The analysis of crystal structure by x-rays depends on the following facts;

i. X-rays, like light, have a wave like nature.

ii. When the rays fall on a crystal they are scattered beams reinforce (interfere constructively)
each other while in others they cancel each other (interfere destructively).
iii. The magnitude of their wavelength (10-10 -10-12m) is of the same order as the atomic spacings
in crystals-about 10,000 times less than those of light (10-6 -10-8m).

The simplest way of regarding what occurs when the x-rays fall on a crystal is to consider the crystal
is made up of regularly spaced layers of atoms (planes). Each of these layers produces a weak
‘reflected’ beam such that the angle of incidence equals to the angle of reflection, as for the
reflection of light by mirror (specular reflections). In fig 8a, reflection by a single layer of atoms is
shown; most of the beam passes through. Fig 8b shows a beam of x-rays falling on a set of parallel
layers of atoms. If all the reflected waves are to combine to produce a strong reflected beam (and
give an intense spot on a photographic plate) then they must all emerge in step. For this to happen
the path difference between successive layers must be a whole number of wavelengths of the x-rays
as they are in this case. Stated mathematically, the wave can be reflected only if it satisfies the
equation, (Bragg’s law)

Where:

d = distance between adjacent planes;

n = an integer.

If the Bragg’s law is not satisfied then crests of one wave may coincide with troughs from another
and the two tend to cancel out. The relation shows why radiation of wavelengths a
few angstrom units is most useful for crystal analysis. Strong reflections may be obtained from the
different sets of parallel planes, to give a pattern of spots characteristics of the particular structure.

The Braggs law requires that 0 and be matched. Monochromatic x-rays of

wavelength striking a three dimensional crystal at an arbitrary angle of incidence will not in general
be reflected. To satisfy the Braggs law requires an accident and to create an accident it is necessary
to scan in either wavelength or angle the standard method of diffraction used in the crystal
structure analysis are designed expressly to accomplish this: three simple, older methods, still used
by physicists are described here, but for professional crystallography these techniques have been
replaced by complicated precision camera methods.

QUESTIONS.

1. What is a crystal?
2. Calculate the packing fraction for the various crystal structures.
3. Describe the unit cell of sodium chloride structures.
4. Calculate the axial ratio for the ideal H.C.P. structure.
5. What is the basis of the crystallographic diffraction techniques?
6. What is the basis of x-ray crystallographic analysis?
7. The interatomic spacing of silicon is (diamond lattice) is 0.235 nm. Calculate the density
(atomic weight of silicon is 28)
8. Aluminum has a density of about 2,699 kg/m3. Its atomic weight is 26.97.
a. About how many gram moles of Al are contained in 1m3 of the solid?
b. About how many atoms are contained in 1m3?
c. Calculate the size of the unit cube for this fcc metal.
d. Calculate the atomic radius of Al.
e. What is the weight of a single atom of Al?

CHAPTER 3

FLUIDS AT REST.
3.1. Introduction.
The differences between the properties of a fluid and a solid depend on the forces that are exerted
between their molecules. We can picture a solid as a three dimensional array in which each molecule
is bound to all its close neighbors by strong, spring like forces. As a result, a solid is able to provide a
reaction force to oppose an applied force in any direction. In a liquid, the intermolecular forces are
relatively weak, and lack the long-range order that gives solids their stability. In gases, the
intermolecular forces are very weak, and the average spacing between the molecules is larger than in
liquids or solids. Both gases and liquids can be made to flow by applying relatively modest forces.
3.2 Surface energy and Surface tension.
Molecules within a liquid experience repulsive as well as attractive forces. At separations less than a
certain value, a repulsive force is dominant. At separations greater than a certain value, attractive
forces are dominant, but as the separation goes on increasing the attractive forces diminish and a
distance, r0 can be defined, at which the attractive forces are practically zero.

Consider a liquid contained in a vessel. Consider a layer at the surface of thickness r0. The molecules
at the surface are acted upon by other molecules within the layer only consider a molecule situated
at O on the surface and imagine a sphere drawn with O as the center and distance r0 as the radius.
The molecules within the hemisphere, because of molecular symmetry, will exert a net downward
force on this molecule.

This force acts vertically downwards and it is normal to the surface of the liquid at O. there is no
upward force as there are no molecules in the upper part of the hemisphere. The whole liquid
surface is therefore under the influence of a downward force. To pull the molecules from the surface
or to extend the surface, some work has to be done, hence, molecules in the surface have potential
energy. In other words, the liquid surface is associated with a potential energy. This energy is
referred to as surface energy (S). S is the surface force per unit area.

For mathematical simplicity, the surface energy is replaced by a hypothetical tension acting parallel
to the surface and in all directions called surface tension ( . Surface tension is not really a
true tension, it simply replaces surface energy.

Equivalence of

Consider the surface of a liquid of sides L and x. consider a force F acting on the surface parallel to
the liquid surface and perpendicular to L. let the increase in length due to F be external work
done =F .In terms of S, work done =S(L X )=S x increase in area.

This implies that F x =SL and then, S (Surface energy in N/m2) =F/L (surface tension in N/m).
Therefore, we see that apart from units, surface tension is equivalent to surface energy.

3.3 Capillarity.
Capillarity is explained in terms of contact angle and the excess pressure across a curved
membrane.
3.3.1. Angle of contrast ( ).
When a liquid comes into contact with a solid, the angle which the surface of the liquid makes with
the solid surface, at the region of contact, is called a contact angle. Liquids with low value of surface
tension have small values of angle of contact. Liquids with large values of surface tension have higher
values of angle of contact. Angles of contact are always measured through the liquid.

When capillary tube is placed in a liquid, the liquid will rise in the tube if the angle of contact of the
liquid is acute and it will be depressed if its angle of contact is obtuse.

When water is placed on a clean glass, it wets the glass. This is the case due to the fact that water has
a low value of angle of contact, fig 4a. The force of cohesion between two water molecules is less
than the force of adhesion between a molecule of water and a molecule of glass. In the case of
mercury wetting does not occur since the forces of adhesion are less than the forces of cohesion
which leads to a greater value of angle of contact, fig 4b.

3.3.2. Excess pressure over a curved membrane.

Consider a curved membrane ABCD. Let the radius of curvature of CD be r1 and that of BC be r2.
 AB=DC=x, AD=BC=y

Let the surface energy be S and the excess pressure be P. because of the excess pressure, let the
membrane move by a distance to the new position A’B’C’D’. Let x change to (x + ) and y to (y
+ ). Change in area of the membrane is given by,

Work done by surface tension:

Multiplication by 2 due to the two surfaces on membrane.

P(xy) is the force in the membrane owing to which the membrane is shifted through . Work done
by this force is given by;

Therefore;

Compare triangles DCO and D’C’O’

Substituting for in equation 3;

* ( ) ( )+

( )

Equation 4 gives the excess pressure for angle of contact=0. In general, i.e. for angle of contact not
equal to zero,

( )
3.4 Capillary rise.
When a clean narrow tube of internal radius R is held vertically and lowered into water, the water
will rise to a height above the common level, inside the tube. The rise is called capillary rise. This rise
is due to the solid-liquid adhesion and is characteristic of any liquid whose angle of contact is acute.
The column of liquid above the common level is in equilibrium under two forces;

i. A downward force due to the weight of the liquid in the capillary tube above the
common level and
ii. Surface tension forces acting upwards above the periphery of the meniscus.

Weight of the liquid above the meniscus =[ ⁄ ]

= ⁄ ………………………………………………………….. (1)

Weight of the liquid above common level =[ ⁄ ]

= ( )

Length of periphery of meniscus =

Surface tension forces =

Therefore, ( )

( )

Or ( )

This is a correct expression if R <<h. in the case of tubes where R is not much different from h, the
expression gives inaccurate results.
3.5. Questions.
1. State the expression for the excess pressure over a curved membrane and hence show that
the excess pressure in the case of a soap bubble is given by; P=4S/R.
2. Explain what is meant by the terms surface tension and surface energy.
3. A soap bubble was slowly enlarged from a radius of 6 cm to one of 9 cm. the amount of work
necessary for enlargement was 20 x 10-4 joules. Calculate the surface tension of the soap
bubble.
4. Derive an expression for the surface tension ( of a liquid of density which rises to a
height h in a clean narrow tube of internal radius R If the angle of contact between the liquid
and the tube is .
5. If water rises in a capillary tube above the common surface, what will happen to
a mercury level in the same tube when it is placed in a dish of mercury ?illustrate this with
the aid of a diagram.
Calculate the differences in the level between the mercury surfaces inside the tube and outside.

Chapter 4

FLUIDS IN MOTION.
4.1. Introduction.
The motion of a fluid may be described by dividing the fluid into infinitesimal volume elements,
which we may call fluid particles, and to follow the motion of each particle. If we knew the forces
acting on each fluid particles, we could then solve for the positions and velocities of each particle as
functions of time. This procedure was first developed by Joseph Louis Lagrange (1736-1813).Because
the number of fluid particles is generally very large, using this method is a formidable task.

4.2. Viscous flow.

In the case of flowing fluids, there is an internal friction between the different layers. This internal
resistance (friction) is referred to as viscous drag or viscous force. When there is shearing or
tangential stress, fluids exhibit relative velocity among different layers and cannot remain in
equilibrium.

Consider layers of a liquid moving with velocity u. newton found that viscous force per unit area ( is
proportional; to the velocity gradient (du/dz) perpendicular to the direction of flow:

Fig 7

Or

Where the coefficient of viscosity. Units of Kg/m/s

The relationship in equation 1 is known as newton’s law of viscosity and is true only for Newtonian
liquids, i.e. in the case of streamline flow. Streamline flow is continuous and steady. In contrast, we
have turbulent flow. When turbulence sets in, vertices are developed mainly on the solid boundaries.
Part of the energy is utilized for the development of the vertices. The factors responsible for the
development of vertices are;

i. Viscosity -
ii. Density –
iii. Lateral dimension of the channel in which the liquid is flowing-r.
The velocity at which turbulence sets in is called the critical velocity (Vc). Reynolds assumed that Vc is
a function of . An expression for Vc cam be obtained using dimensional analysis.

Vc =

Where k is known as Reynolds number.

[ [ [ [

Equating the indices;

T: -1 = -a

M: 0 = a + b b = -1

L: 1 = -a – 3b + c c = -1

Therefore,

Vc = k

As long as V<k , there will be streamline motion. Alternatively, if the value of k is less than 1000
we have streamline flow while for a value greater than 1500 turbulence sets in. in between the flow
is unstable.
 STREAMLINE (IDEAL) FLOW.
4.2.3. Continuity equation for one-dimensional flow.
For steady flow there cannot be an accumulation of mass inside the channel (tube). Consequently,
the mass entering the tube is equal to the mass leaving in unit time, i.e.

A1u1 = A2u2 or Au = m = constant

M=

Where m = mass rate flow

Mean velocity

A = cross-sectional area

4.4.1 Bernoulli’s Equation.

Bernoulli’s equation states the consequences of the principle that the work done on a fluid as it flows
from one place to another is equal to the change in its mechanical energy. Bernoulli’s equation can
be used under the following condition;

1. The fluid is incompressible; its density remains constant.

2. The fluid does not have appreciable frictional effects, it’s non-viscous. Consequently,
no mechanical energy is lost due to friction.
3. The flow is streamline, not turbulent.
4. The velocity of the fluid at any point does not change during the period of
observation. (This is called the steady-state assumption).

Equation: Any body that is accelerated does so due to the action of an applied force. The force is
given by newton’s second law: F =ma. If the velocity V of an elementary fluid particle is a function of
position and time, we may write the expression V=V(s, t). Thus

………………………………………………….. (3)
And since the velocity along a streamline is V = ds/dt, the acceleration in that direction is:

The term is the convective acceleration, or the variation of velocity at a point with respect to
time.

We will now apply newton’s second law to an element of a non-viscous fluid. From fig 9, writing

∑ along the streamline gives

F-F’-mg

( ) ( )

And since upon simplifying we get:

( ) ( )

Which is Euler’s equation of motion along a streamline for a non-viscous fluid. For steady flow
Hence, . Integration along a streamline for a constant-density fluid gives

Equation 7 states that the energy per unit mass of fluid id constant along a streamline for steady in-
compressible flow of a non-viscous flow. The pressure may vary with time, however, but it would
have no effect on the flow pattern.

4.4.2. Illustration of Bernoulli’s equation.

Bernoulli’s principle is widely applied in areas that include:

I. Flow of a liquid through a wide tank.

Consider a vessel with a liquid to a height h. we will apply the Bernoulli’s equation to calculate the
velocity of liquid flowing out of a hole at the bottom.
At point X, the pressure, velocity and position are respectively, P1 ,V1 ,and h1 while at Y the quantities
are P2 , V2 and h2 . Relative to v1,v2 is infinitely large so that v1 may be set equal to zero. Also, h1>>h2
such that we may safely approximate h2 to zero. Inserting these approximations in Bernoulli’s
equation yields the following results.

=√

The equation shows that the velocity of the liquid flowing out only depends on the height of the
liquid but not on the radius of the opening.

II. Discharge through a small orifice

A liquid under a static head h is allowed to flow through an orifice, whose diameter is small
compared with the head. Fig 11.

The velocity v of the issuing jet is then obtained by equating the pressure energy or head of the
liquid in the tank to its kinetic energy or velocity head at the jet. Thus, neglecting energy losses the
theoretical velocity of flow is given by-

√ .

Figure 11.

4.4.3 Flow of a liquid through a narrow tube *Poiseuille’s Formula+

Consider the flow of a liquid in a capillary tube of internal radius ‘a’ and of length L. Let P be the
pressure difference which maintains the flow.

Assumptions:

1. Streamlines are parallel to the axis of the tube.

2. The layer of the liquid in contact with the walls of the tube has a zero velocity.
 Consider a liquid cylinder of radius r coaxial with the capillary tube.

P main tube(pipe)
of radius a

r
a

wall of the liquid

cylinder ( of
L radius r).

figure 12
  Let u be the velocity of the liquid at the surface of the liquid cylinder. The velocity gradient at
the surface is du/dr. the viscous drag (force) per unit area is (du/dr). the viscous drag on
the surface of the liquid cylinder of radius r is given by

 The force due to pressure difference on the cylinder is given by

The viscous force on the cylinder and the force on it due to the excess pressure P, are together equal
to zero, since there is no acceleration of the liquid, i.e. we have orderly or laminar flow. Hence,

 Integrating this equation from wall of cylinder to wall of tube, gives

∫ ∫

 Consider a cylindrical shell of the liquid between radii r and (r +dr).the liquid in this shell has a
velocity u given by equation 3 and the quantity of liquid flowing per second at any cross-
section between tubes of radii r and (r +dr) is given by,
dv = (cross sectional area of shell) x (u).
Hence,

dV = (

 Integrating the above equation from the center of tube to the wall, gives V ,the total volume
of liquid issuing per second from the pipe (Poiseuille’s formula):
∫ ∫

4.4.4 Determination of viscosity of highly viscous liquids.

Stokes’ law: According to stokes’ law, a small sphere of radius ‘a’ falling through an infinite ocean of
viscous liquid, experiences a resistance due to viscosity and attains a constant velocity, .

Viscous forces result because the layer of fluid adjacent to an object is at rest with respect to the
object. When the object moves through the fluid, this layer experiences a frictional force from the
more rapidly moving layer next to it. Successive adjacent layers near the object produce frictional
forces on each other, and the net result is to retard the motion of the object through the fluid.

The resistance (viscous force) F is proportional to:

 (terminal velocity)
 a,(radius of the sphere)
 ,(viscosity of the liquid)
Dimensional analysis results give=A . Kutta and jakowski did show that A=6 . Hence

At terminal velocity: viscous drag force + upthrust due to liquid = weight of the object. Hence,

( ) ( )

Where a= radius of object,

= liquid density,

= density of material object.

Therefore,

4.5. Questions
1. Derive Bernoulli’s equation of motion for an ideal liquid.
2. What is the terminal velocity in air at of a spherical dust particle of radius
and density
a) What is the Reynolds number at terminal velocity?
b) Find the drag force at terminal velocity.
3. What is the significance of Reynolds number?
4. A hydraulic machine is driven by a jet from a nozzle of 25 mm diameter in a water main
under a gauge pressure of 700KN/m2. Neglecting any loss of energy, find the power supplied
to the machine.
5. Water flows from an orifice in the side of the tank. The head of water above the center line
of the orifice is 0.95 and the coefficient of discharge 0.6. Find the power of the jet.
6. A horizontal pipe (cross sectional area at one point=15cm2) carries water from one place to
one another. At the second point, the pressure difference is observed to be 200N/m2. How
many cubic meters of water flows out of the pipe per hour?

Chapter 5
KINETIC THEORY OF GASES.

5.1 INTRODUCTION.
Kinetic theory of matter regards all bodies as assemblies of particles in motion either vibrating or
flying about. Kinetic theory of gases seeks to explain the behavior of gases by considering the motion
of their molecules. The theory is based on the following basic assumptions:

1. A gas consists of identical particles known as molecules of each mass m.

2. The size of the molecules is extremely small, i.e. the volume of the molecules is
negligibly small fraction of the volume occupied by the gas.
3. The molecules exert no appreciable forces on one another except during collisions.
4. The molecules are in random motion and obey newton’s laws of motion.
5. Collisions with other molecules and wall of container are elastic and of negligible
duration
6. The total number of molecules is very large.

5.2. IDEAL GASES.

All gases approximate to ideal gases when they are dilute i.e. the intermolecular forces are negligible
when compared to thermal energy. They obey the ideal gas equation PV=RT.

5.2.1. Average kinetic energy per molecule of an ideal gas.

Consider a gas contained in a cubical vessel of side L. Gas molecules will have velocities ranging from
C to

Let x, y, z be the components of velocity

Consider a molecule moving along the x-component (direction)

 Momentum before collisions mx

 Momentum after collision is –mx
 Change in momentum =mx-(-mx)=2mx
 Time interval between two successive collisions
= i.e. time up to just before 2nd collision……….. (1)
Rate of change of momentum = 2mx

= = force (F)……………………………………………….. (2)

Pressure = ……………………………………………………………………………………………….. (3)

Suppose there are n molecules in the container, the x components of pressure for all molecules can
be expressed as follows;

Per mole (gm molecule):

 1gm molecule of any gas weighs where M is the molecular/atomic weight.

For 1 mole of any gas: Root mean square velocity of a molecule of any gas per mole-
depends on volume,

1. Hydrogen (molecule) –H2 √ √

𝑅 𝑗𝑘 𝑚𝑜𝑙𝑒

𝑥 𝑗𝑘 𝑚𝑜𝑙𝑒 𝑥 𝐾
√𝐶
𝑥 𝑘𝑔𝑚𝑜𝑙𝑒

√ 99 𝑥 𝑚 𝑠𝑒𝑐 𝑚𝑠𝑒𝑐
 5.2.2. Imperfect gases.
Many gases show marked deviations from the perfect gas equation, PV=RT, even at room
temperature.

5.3.1 What makes a gas real (deviate from perfect)?

i. Size of the molecules.

The perfect gas equation: , Assumes the size of the molecule to be zero, so that

But if provision is made for the size of the molecules, then is less
than . Van der Waal incorporated this change in V so that the corrected equation is

P (V-b) = RT……………………………………………………………………………. (1)

We shall now embark on modifying the ideal gas by obtaining an expression for the constant b.

The mean free path, i.e. the average distance travelled by a molecule between two collisions is given
by;

Where

If is not zero, the mean free path is reduced by and is then equal to ( This implies that
pressure should increase by a factor or . Then the equation PV=RT becomes,
( ⁄ )

PV =
( ⁄ )

( ⁄ )

( )

 Note =Volume of free space.

If n is the number of molecules per unit volume, for one mole,

Now, volume of one molecule is:

( )

Or

Hence b= and the perfect gas equation, PV=RT Becomes

 ii. Intermolecular forces.
In the case of imperfect gases, provision is made for intermolecular forces, i.e. it is not assumed that
intermolecular forces are negligible compared to thermal energy. In the bulk of the gas, because of
symmetry, the net force on a molecule is zero. But as the molecules approach the walls of their
container, they have to overcome the attractive forces due to neighboring molecules, hence the
pressure is reduced:

P= –

Or =P+

The correct equation P (V-b) = RT Becomes,

(P + (V-b) =RT……………………………………………………………… (7)

Van der Waal assumed that is proportional to:

i. The number of molecules striking the wall per unit area,

ii. The number of molecules that are attracting the colliding molecules,
iii.
Or

( )

This is the van der Waals simple equation which describes the behavior of ‘real’ gases, in terms of
two constants a and b.

Van der Waals equation.

The van der Waals equation is given by;

( )

Or

( )

The correction factors a/V2 and b are the parts, which accounts for non-ideal gas behavior. B
accounts for the volume of the container occupied by gas molecules, while a/V2 accounts for the
force of attraction between the molecules, which are neglected in the ideal gas equation. Values of
the constants a and b have to be obtained by experiment.

EXAMPLE:

From the experiments on Tc, Vc and Pc for hydrogen molecules b was found to be
Find the molecular diameter of H2

( )

=
 =

Chapter 6.

THERMAL CONDUCTIVITY AND SPECIFIC HEATS OF SOLIDS, LIQUIDS

AND GASES.
6.2 Specific heat of solids.
Heat capacity and specific heat: we can change the state of a body by transferring energy to and
from it in the form of heat, or by doing work on the body. One property of a body that may change in
such a process is its temperature T. the change in temperatures that corresponds to the transfer
of a particular quantity of heat energy Q will depend on the circumstances under which the heat was
transferred. For example, in the case of a gas confined to a cylinder with a movable piston, we can
add heat and keep the piston fixed( thus keeping the volume constant),or we can add the heat and
allow the piston to move but keep the force on the piston constant ( thus keeping the gas under
constant pressure). We can even change the temperature by doing work on a system such as by
rubbing together two objects that exert frictional force on one another, in this case, no heat transfer
need occur.

it is convenient to define the heat capacity C of a body as the ratio of the amount of heat energy Q
transferred to a body in any process to its corresponding temperature change ( that is,

The specific heat capacity of any material is the heat capacity per unit mass. The values of this
quantity vary widely from one solid to another. If the specific heat capacity is multiplied by molar
mass M the molar heat capacity is obtained. Experimental evidence shows that with few exceptions,
the molar heat capacities of all solids have values close to 25 J/mol.K. This remarkable experimental
observation was pointed out in 1819 by French scientists P.L. Dulong (1785-1838). Samples with the
same number of moles have same number of atoms. Hence, we can conclude that the heat energy
required per atom to raise the temperature of a solid by a given amount seems with a few
exceptions, to be about the same for all solids. This is striking evidence for the atomic theory of
matter.

Molar heat capacities actually vary with temperatures approaching zero as T 0 and the Dulong- petit
value only at relative high temperatures. The Dulong-petit high temperatures variation of the molar
heat capacity requires an analysis based on quantum physics.

 Einstein: measurements of the molar heat capacities provide a sensitive probe of the manner
in which atoms absorb energy.
 Dulong and petit: according to Dulong and petite’s law, the specific heat of metals has a value
of 6 calories/mole. Further investigations were experimentally made on metals and non-
metals. The outcome of the investigations were as follows:
1. The specific heat is 6 calories per mole as predicted only at elevated
temperatures.
2. It decreases with temperature, 0 as T 0
3. At very low temperatures was found to be proportional to T3
6.2.1 classical theory
The atoms of solids have no translational or rotational energy but they vibrate, hence have
vibrational energy. The vibrations occur about their equilibrium position

Each atom has 6 degrees of freedom. Each degree of freedom has an energy ⁄ Therefore the
total energy is 3KT. Energy per mole is 3N0KT where N0 is the Avogadro number.

Molar heat capacity at constant volume.

A series of experiments was made and the specific heat of many metals were studied at different
temperatures.
Salient features.
The data plotted in fig 2 characterize materials that do not change their state in that temperature
range, i.e. they do not melt or change from one crystal structure to another. Measurements of heat
capacity are useful in studying such changes.

1. Molar heat capacity is a function of temperature.

2. only at high temperatures (very high in some cases)
3. as T

 Classical theory was inadequate in explaining these results.

6.2.2Einstein’s theory of specific heats.
Quantum mechanical approach:

i. To explain the variation of molar heat capacity with temperature, the following assumptions
were made:
1. A solid with N atoms is equivalent to 3N harmonic oscillators.
2. All the oscillators vibrate with the same frequency v.
3. Each made of vibration has an energy where = Planck’s constant, n=0,
1, 2…
4. The number of oscillators with energy is proportional to . The
⁄
exponential is known as Boltzmann factor. It gives the probability
that the energy state En is occupied.

Mode (n) Energy Number of oscillators.

0 0 ⁄

1 ⁄

2 2 ⁄

3 3 ⁄

ii. Total number of oscillators (N)

⁄ ⁄ ⁄

⁄
Where

iii. Total energy.(Et)

=
 iv. Average energy per oscillator.(EAV)

v. Energy per mole (u)

One mole contains N0 = Avogadro number. This is equivalent to 3 N0 harmonic oscillators.

U = number of oscillators x average energy per oscillator.

( )

( )

( )

Where:

vi. Analysis.
At high temperatures;

RECAP:

At low temperatures.

( )
( )
( )

vii. Conclusion.
⁄
At low temperatures, is proportional to

At high temperatures,

MERITS:
 1. Theory shows that is a function of temperatures.
2. At high temperatures,
3. As ,
DEMERITS:

At very low temperatures, experimental investigation shows that Law, but Einstein’s
⁄
theory shows that which is more rapid.

6.3 Specific heat of gases.

6.3.1 Difference of specific heats

The specific heat of a gas is the quantity of heat required to raise the temperature of one mole of gas
through unit temperature.

Two different conditions for the measurement of C can be specified.

( ) ( )

From the first law of thermodynamics we have the equilibrium condition given by;

………………………………………………………………………… (3)

Where the internal energy increase and the external work done.

( )

6.3.2 Ratio of specific heats (

=constant or PV = constant where ⁄

i. Monoatomic gases.
Examples – argon, neon, krypton. Each has 3 translational degrees of freedom. The internal energy
per atom is given by

( )

Energy per mole,

( ) ( )
 *( ) + ( )

Hence;

( )

*( ) +
⁄
*( ) +

ii. Diatomic gases.

Examples – oxygen, nitrogen, chlorine.

iii. Polyatomic gases.

Examples - Molecules have 3 translational +3 rotational degrees of freedom.

⁄ ⁄

6.6 QUESTIONS

A vessel contains 2.0 gm. of helium gas at 270 c. given that the relative atomic mass of helium is 4.0
and that for helium, determine.

i. The total translational kinetic energy of the gas.

ii. The specific heat capacity of the gas.