Gases

The perfect gas

1. Explain how the perfect gas equation of state arises by combination of Boyles law, Charless law and Avogadros Principle.

An equation of state is an equation that relates the variables that define the state of a system to each other. Boyle,
Charles, and Avogadro established these relations for gases at low pressures (perfect gases) by appropriate experiments.
1
Boyle determined how volume varies with pressure ( ), Charles how volume varies with temperature ( ), and
Avogadro how volume varies with amount of gas ( ). Combining all of these proportionalities into one we find

Inserting the constant of proportionality, R, yields the perfect gas equation

= =

2. Explain the term partial pressure and why Daltons law is a limiting law.

The partial pressure of a gas in a mixture of gases is the pressure the gas would exert if it alone occupied the same container
as the mixture at the same temperature. It is a limiting law because it holds exactly only under conditions where the gases
have no effect upon each other. This can only be true in the limit of zero pressure where molecules of the gas are separated
by many molecular diameters on the average. Hence. Dalton's law holds exactly only for a mixture of perfect gases; for real
gases, the law is only an approximation.

3. Use the kinetic model of gases to explain why light gases, such as H2 and He, are rare in the Earths atmosphere but heavier
gases, such as O2, CO2, and N2 are abundant.

The very light molecules of hydrogen (2.02 g mole-1) and helium (4.00 g mole-1) are rare in the Earth's atmosphere because
at atmospheric temperatures a significant fraction of these molecules travel at sufficiently high speeds to escape from the
planet's gravitational attraction. A very small fraction of the heavy molecules oxygen (32.0 g mol-1), carbon dioxide (44.0 g
mole-1) and nitrogen (28.0 g mole-1) have a speed sufficiently large to escape from the Earth's gravitational pull. This reflects
1
8 2
the basic kinetic theory relation = ( ) ; the mean speed decreases by a factor of M-1/2. Heavy molecules move more
slowly than light ones on the average.

Real gases
4. Explain how the compression factor varies with pressure and temperature and describe how it reveals information about
intermolecular interactions in gases.

Consider three temperature regions:

< . At very low pressures, all gases show a compression factor, 1. At high pressures, all gases have
> 1 signifying that they have a molar volume greater than a perfect gas, which implies that repulsive forces
are dominant. At intermediate pressures, most gases show < 1, indicating that attractive forces reducing the
molar volume below the perfect value are dominant
, 1 At low pressures, slightly greater than I at intermediate pressures, and significantly greater than 1
only at high pressures. There is a balance between the attractive and repulsive forces at low to intermediate
pressures, but the repulsive forces predominate at high pressures where the molecules are very close to each
other.
> , > 1 At all pressures because the frequency of collisions between mol-ecules increases with
temperature.

5. Describe the formulation of the van der Waals equation.

The van der Waals equation 'corrects' the perfect gas equation for both attractive and repulsive interactions between
the molecules in a real gas.
The repulsive interactions between molecules are taken into account by supposing that they cause the molecules
to behave as small but impenetrable spheres. The non-zero volume of the molecules implies that instead of moving in a
volume V they are restricted to a smaller volume V-nb, where nb is approximately the total volume taken up by the molecules

themselves. This argument suggests that the perfect gas law =
should be replaced by = when repulsions are
significant.
The pressure depends on both the frequency of collisions with the walls and the force of each collisions with the wall and the
force of each collision. Both the frequency of the collisions and their force are reduced by attractive interaction, which act
with a strength proportional to the molar concentration /, of the molecules in sample. Therefore, because both the
frequency and the force of collisions are reduced by attractive interactions, the pressure is reduced in proportion to the square
of this concentration.
2
If the reduction of pressure is written as () where a is a positive constant characteristic of each gas, the combined
effect of repulsive and attractive forces is the van der Waal equation
2
= ( )


In terms of molar volume =

= 2

The constants a and b are called the van der Waals coefficients. As can be understood from aboves discussion, a represents the
strength of attractive interactions and b that of the repulsive interactions of between the molecules. They are characteristic of
each gas but independent of the temperature.
6. What is the significance of the critical constants?

The critical point of a substance is a single (, , ) point that is characterized by the critical constants( , , ). A liquid
being heated becomes indistinguishable from the gas or vapor phase at the critical point. At temperatures above the critical
temperature a gaseous substance cannot be liquefied by the application of pressure alone while at temperatures below the
critical temperature the vapor can be condensed by the application of pressure.
Liquids
I. Poiseuilles Equation for Viscous Flow in a Tube

This equation describes the rate of laminar flow of a liquid through a straight tube or pipe of length L and radius R.
We assume that the tube is parallel to the z axis and we assume that the velocity depends only on r, the perpendicular
distance from the center of the tube. Consider a portion of the fluid that is contained in an imaginary cylinder of radius r
that is concentric with the tube walls, as depicted in Figure 10.5.When a steady state has been reached there is no net
force on the fluid since it does not accelerate. The frictional force due to viscosity at the surface of the cylinder balances
the hydrostatic force pushing the liquid through the cylinder. From Newtons law of viscous flow,

=

where Ff is the magnitude of the frictional force on the liquid in the
imaginary cylinder and A is the area of its surface (excluding the area
of its ends). This area is the circumference times the length of the
cylinder.

= 2

The magnitude of the hydrostatic force on the liquid in the imaginary

cylinder is equal to the difference of the pressure at its ends times the
cross-sectional area of the cylinder:

= (2 1 ) 2

where P2 is the pressure at one end of the tube and P1 is the pressure at the other end. Equating the magnitudes of Fh/A and Ff /A
gives
(2 1 )
=| |=
2
We assume that is negative and conclude that / is positive since the magnitude of the flow velocity is larger in the center
of the tube. We multiply both sides of this equation by dr and integrate from = = where R is the radius of the tube and
is some value of r inside the tube.
( )
(2 1 )


= =
() 2

If the liquid does not slip on the tube walls uz(R) will vanish, and the integration yields

(2 1 ) 2
() = ( 2 )
4
where we replace r by r. This parabolic dependence of the flow velocity on position is represented
in the figure on the right. The length of each arrow in the figure is proportional to the flow velocity
at its location.
The total rate of flow of the liquid through the tube can be computed by considering cylindrical shell
of thickness dr and radius r concentric with the walls of the tube and then adding up the
contributions of all such shells. The volume of the fluid in this shell that flows out of the tube in 1 s
(the contribution of the shell to the volume rate of flow) is equal to the cross-sectional area of the
shell times a length equal to the distance traveled in 1 s. Since the circumference of a shell of
radius r is equal to 2r and since its thickness is dr,

( ) = 2 | ()|

The total volume rate of flow is the integral over all such shells:

(2 1 ) 2
= 2 | ()| = 2 ( 3 )
0 4 0
 (2 1 )4

= 8
Poiseuilles equation

This is Poiseuilles equation for the rate of flow of an incompressible liquid undergoing laminar flow in a tube of radius R. A different
version holds for the flow of a gas.
Points to remember:
Applies Newtons law of Viscous flow applicable when fluid is laminar and Newtonian
Involves a moving fluid through a circular tube of small internal diameter
Pressure difference across the ends of the tube is the driving force for the bulk flow.
Assumption: Flow rate is uniform and slow

II. Stokes Law in the Falling Sphere Method

The force Fd required to propel a small sphere of radius R through a quiescent, Fb

continuous medium of viscosity with a velocity v is

= 6v

The object experiences a viscous drag when it moves through the medium in order
to separate or push apart layers of intervening liquid.

Applying Newtons law of viscous flow and law of motion, we make an FBD of the
falling sphere, at equilibrium,

= = 0
+ = 0
=
Applying Archimedes principle

4 3 4 3
6v = s ( ) ( )
3 3
4 3
6v = ( ) (s l )
3

If the time t required for the sphere to fall a distance L is measured (v = L/t), the viscosity of the medium can be directly calculated

2 2 (s l )
=
9
Points to remember:
Limitations of Stokes Law as Used in the Falling-Sphere Method

Valid only in the limit of a continuous medium (a medium that extends far in all directions from the sphere)
What will happen to the measured viscosity if the medium extends for only a few centimeters on all sides?
o Measured viscosity will be smaller due to compression of the liquid against the sides of the cylinder.
Solids
1. Explain how metallic conductors, semiconductors, and insulators are identified and explain their properties in terms of band
theory. Why is graphite an electronic conductor and diamond an insulator?
A metallic conductor is a substance with a conductivity that decreases as the temperature is raised. A semiconductor is a
substance with a conductivity that increases as the temperature is raised. A semiconductor generally has a lower conductivity
than that typical of metals, but the magnitude of the conductivity is not the criterion of the distinction. It is conventional to
classify semiconductors with very low electrical conductivities, such as most synthetic polymers and diamond, as insulators.
We shall use this term. But it should be appreciated that it is one of convenience rather than one of fundamental significance.
The conductivity of these three kinds of materials is explained by band theory. When each of N atoms of a metallic element
contributes one atomic orbital to the formation of molecular orbitals, the resulting N molecular orbitals form an almost
continuous band of levels. The orbital at the bottom of the band is fully bonding between all neighbors, and the orbital at the
top of the band is fully anti bonding between all immediate neighbors. If the atomic orbitals are s-orbitals, then the resulting
band is called an s-band; if the original orbitals are p-orbitals. Then they form a p band. In a typical case, there is so large an
energy difference between the s and p atomic orbitals that the resulting s and p bands are separated by a region of energy
in which there are no orbitals. This region is called the band gap, and its width is denoted Et. When electrons occupy the
orbitals in the bands, they do so in accord with the Pauli principle. If insufficient electrons arc present to fill the band, the
electrons close to the top of the band are mobile and the solid is a metallic conductor. An unfilled band is called a conduction
band and the energy of the highest occupied orbital at T= 0 K is called the Fermi level. Only the electrons close to the Fermi
level can contribute to conduction and to the heat capacity of a metal. If the band is full, then the electrons cannot transport
a current readily, and the solid is an insulator; more formally, it is a species of semiconductor with a large band gap. A full
band is called a valence band. The detailed population of the levels in a band taking into account the role of temperature is
expressed by the FermiDirac distribution.
The distinction between metallic conductors and semiconductors can be traced to their band structure: a metallic conductor
has an incomplete band, its conductance band, and a semiconductor has full bands, and hence lacks a conductance band.
The decreasing conductance of a metallic conductor with temperature stems from the scattering of electrons by the vibrating
atoms pop metal lattice. The increasing conductance of a semiconductor arises from the increasing population of an upper
empty band as the temperature is increased. Many substances, however, have such large band gaps that their ability to
conduct an electric current remains very low at all temperatures: it is conventional to refer to such solids as insulators. The
ability of a semiconductor to transport charge is enhanced by doping it, or adding substances in controlled quantities. If the
dopant provides additional electrons, then the semiconductor is classified as n-type. If it removes electrons from the valence
band and thereby increases the number of positive holes, it is classified as p-type. Diamond and graphite are covalent solids
in which covalent bonds in a definite spatial orientation link the atoms in a network extending through the crystal. In diamond
each sp3 hybridized carbon is covalently bonded tetrahedrally to its four neighbors. Each bond involves a low energy,
localized electron pair. This means that there is a large gap between the filled a band and the empty it band above it; it is
a large band gap semiconductor, an insulator. In graphite, bonds between sp2 hybridized carbon atoms form hexagonal
rings that repeat throughout each carbon contributes one p orbital and one electron. Neighboring p orbitals overlap to produce
a bond that extends throughout the graphene sheet and is half full; therefore, a conduction band that lies within graphene
sheet alone.

2. XRAY CRYSTALLOGRAPHY
A crystal lattice is considered to be made up of regular layers or planes of atoms equal distance apart. Since the wavelength
of X-rays is comparable to the interatomic distances, Laue (1912) suggested that crystal can act as grating to X-rays. Thus
when a beam of X-rays is allowed to fall on crystal, a large number of images of different intensities are formed. If the
diffracted waves are in the same phase, they reinforce each other and a series of bright spots are produced on a photographic
plate placed in their path. On the other hand, if
the diffracted waves are out of phase, dark
spots are caused on the photographic plate.
From the overall diffraction patterns produced
by a crystal, we can arrive at the detailed
information regarding the position of particles in
the crystal. The study of crystal structure with
the help of X-rays is called X-ray
crystallography.

Derivation of the Braggs Law

In 1913 the father-and-son, W.L. Bragg and W.H. Bragg worked out a mathematical relation to determine interatomic
distances from X-ray diffraction patterns. This relation is called the Bragg equation.
 They showed that:
(1) The X-ray diffracted from atoms in crystal planes obey the laws of reflection.
(2) The two rays reflected by successive planes will be in phase if the extra distance travelled by the second ray is an integral
number of wavelengths.

The figure shows a beam of X-rays falling on the crystal surface. Two successive atomic planes of the crystal are shown
separated by a distance d. Let the X-rays of wavelength strike the first plane at an angle . Some of the rays will be reflected at the
same angle. Some of the rays will penetrate and get reflected from the second plane. These rays will reinforce those reflected from
the first plane if the extra distance travelled by them (CB + BD) is equal to integral number, n, of wavelengths. That is,
= + ()

Geometry shows that

= = ()
From (i) and (ii) it follows that
= 2
= 2
This is known as the Bragg equation. The reflection corresponding to n = 1 (for a given series of planes) is called the first order
reflection. The reflection corresponding to n = 2 is the second order reflection and so on. Bragg equation is used chiefly for
determination of the spacing between the crystal planes. For X-rays of specific wave length, the angle can be measured with the
help of Bragg X-ray spectrometer. The interplanar distance can then be calculated with the help of Bragg equation.
Simple Mixtures
The thermodynamic description of mixtures
1. Are there any circumstances under which two (real gases) will not mix spontaneously?

Perfect gases spontaneously mix in all proportions. There are, however, conceivable circumstances under which two real
gases might not mix spontaneously. Con-sider allowing two gases initially at the same pressure p to mix (so that mixing them
would not change the pressure). Consider carrying out this process at constant temperature as well. Then mixing would be
spontaneous if < 0. Consider entropic and enthalpic contributions:

Now > 0 would be positive, so mixing would always be favoured entropically. The only circumstances under which
mixing might not be spontaneous would be if > , that is if interactions between the species were so
energetically unfavorable as to outweigh the entropic term. We might consider such unfavorable interactions unlikely in
gases; after all = 0 for perfect gases. At the same time, we know that there are liquids for which such unfavorable
interactions prevent mixing at least in some proportions and at some temperatures (the proverbial oil and water). Consider
two such species at a temperature above the critical temperature of both and at a pressure high enough to make their
densities more typical of liquids than gases. Under such circumstances, the species are technically gases, although the term
supercritical fluid is more informative [Section 1C.I(c)]. One might find examples of immiscibility among such supercritical
fluids.

2. Explain the molecular origin of Raoults law and Henrys law.

Raoult's law defines the behaviour of ideal solutions. Like ideal gases, what makes the behaviour ideal can be expressed in
terms of intermolecular interactions. Unlike ideal gases, however, the interactions in an ideal solution cannot be neglected.
Instead, ideal behaviour amounts to having the same interactions among molecules of the mixture's different components as
molecules of each component have with other molecules of that same component. In shorthand, ideal behaviour consists of
A-B interactions being the same as A-A and B-B interactions. If that is the case, then the cohesive forces that would keep a
molecule in the liquid phase would be the same in the solution as in a pure liquid, and the vapor pressure of a component
will differ from that of a pure liquid only in proportion to its abundance (mole fraction). Thus, we expect Raoult's law to be
valid for mixtures of components that have very similar chemical structures. Similar structures imply both similar
intermolecular interactions (governed largely by polarity) and similar sizes (implying that the mole fraction is a good
approximation to the relative proportion of the surface area occupied by each componenta factor that is relevant to rates
of evaporation and condensation).

In an ideal dilute solution, on the other hand, Raoult's law holds for the solvent in the limit as x A approaches 1, not because
A-B interactions are like A-A interactions, but because there are so many more A-A interactions than A-B interactions that A-
A interactions dominate the behaviour of the solvent. For the solute, on the other hand, there are many more A-B interactions
than B-B interactions in the limit as xB approaches zero. Thus, only one kind of interaction (A-B) is important in determining
the affinity of the solute for the solution.
Properties of Solutions
3. Explain what is meant by a regular solution; what additional features distinguish a real solution from a regular solution?
A regular solution has excess entropy of zero, but an excess enthalpy that is non-zero and dependent on composition. We
can think of a regular solution as one in which the different molecules of the solution are distributed randomly, as in an ideal
solution, but have different energies of interaction with each other. Real solutions that are not regular may also have a non-
random distribution of molecules. This is particularly likely in the case of ionic solutions, in which ions of one charge are more
likely to be surrounded by ions on the opposite charge than of the same charge.
4. Explain the origin of the colligative properties.

All the colligative properties (properties that depend only on the number of solute particles present, not their chemical identity)
are a result of the lowering of the chemical potential of the solvent due to the presence of the solute. This reduction takes
the form = + ln , depending on whether or not the solution can be considered ideal. The lowering of the
chemical potential results in a freezing point depression and a boiling point elevation. Both of these effects can be explained
by the lowering of the vapor pressure of the solvent in solution due to the presence of the solute. The solute molecules get
in the way of the solvent molecules, reducing their escaping tendency.