Chapter three

Microscopic Theory and Macroscopic

Measurements
 Contents
❖ Determination o f the Absolute Temperature
❖ High and Low Absolute Temperatures
❖ Work, Internal Energy, and Heat
❖ Heat Capacity
❖ Entropy
❖ Intensive and Extensive Parameters
 Determination of the Absolute Temperature
The absolute temperature is a very important parameter since it appears explicitly in
most predictions of the theory.

❖ What procedure might be used for actually measuring the absolute

temperature of a system?
❖ In principle, the procedure can be based upon any theoretical relation which
involves β or T.
❖
➢ this theoretical relation showing how the susceptibilityΧ of a
paramagnetic substance depends on T.
❖ Measurements of the susceptibility of a suitable paramagnetic substance
provide a method for measuring the absolute temperature.
❖ Another theoretical relation involving T is the equation of state of an ideal
gas i.e.,
❖ In any gas, sufficiently dilute to be ideal, can be used to measure the
absolute temperature.
❖ In practice, this is indeed a very convenient method useful in many cases.
❖ To use the equation of state as a basis for measuring the absolute
temperature T, one can proceed as follows.
➢ A small amount of gas is put into a bulb and provisions are made for
keeping the volume V of this gas constant irrespective of its pressure.
❖ This constitutes a constant-volume gas
thermometer.
❖ Suppose that one has measured the fixed volume V
and the number of moles of gas in the bulb (so that
one knows the number N of gas molecules).
❖ A measurement of mean pressure yields, by virtue
of equation of state, the pertinent value of kT or β
of the gas (and hence also of any other system with
which the gas thermometer may be in thermal
equilibrium).
● Objectives: to make a comparison between two absolute temperatures than
to measure directly the value of β or kT.
● To achieve the goal, one chooses a standard system in a standard
macrostate and assigns to it, by definition, a certain value of the absolute
temperature T.
● By international convention one chooses as the standard system pure water,
and as its standard macrostate that where the solid, liquid, and gas forms of
water and this macrostate is called the triple point of water.
● Because there is only one definite value of pressure and temperature at
which all these three forms of water can coexist in equilibrium.
 ● The temperature of the system is unaffected by any changes in the relative
amounts of solid, liquid, and gas present under these circumstances.
● The triple point provides is a very reproducible standard of temperature.
● By international convention, adopted in 1954, one chooses to assign to the
absolute temperature Tt of water at its triple point the value

❖ The numerical value of the absolute temperature of any system can be obtained
by comparing it with the temperature Tt of water at its triple point.
❖ A determined numerical value can be expressed in terms of degrees Kelvin or
simply degrees K , commonly abbreviated as “ °K.”
❖ Some devices (gas thermometer device) to measure the value of β or kT at the
triple point of water where T = Tt, the value of k is immediately determined.
❖ Since the quantity β-1 = kT represents an energy which can be measured in
ergs, the constant k can then be expressed in units of ergs/degree.
❖ Let us illustrate how to measure absolute temperatures with a constant-volume
ideal gas thermometer.
❖ Using equation of state, the gas pressure measured on the thermometer is
directly proportional to the absolute temperature of the gas.
❖ The thermometer permits ready measurements of absolute temperature ratios in
terms of pressure ratios.
❖ Suppose that the thermometer is brought into thermal contact with some
system A; after it has reached equilibrium, its mean pressure will have some
definite value pA.
❖ Similarly, the thermometer is brought into thermal contact with some other
system B; after it has reached equilibrium, its mean pressure will have some
definite value pB.
❖ Using equation of state, the absolute temperatures TA and TB of A and B are
related by

❖ In particular cases the system B consists of water at its triple point and that the
thermometer in equilibrium with this system indicates a mean pressure pt.
❖ Then, the absolute temperature of A has the specific value

❖ The absolute temperature of any system can be readily determined by

measuring the pressure of a constant-volume gas thermometer.
❖ This particular method of measuring the absolute temperature is quite
convenient provided that the temperature is not so low or so high that the use
of gas thermometers becomes impractical.
❖ With the absolute temperature scale fixed by the particular convention, one can
use the equation of state of an ideal gas to determine the numerical value of the
constant.
❖ On the Kelvin temperature scale an energy of 1 electron volt corresponds to
an energy kT where T = 11,600°K.
❖ Also, room temperature is approximately 295°K; it corresponds to an energy
kT =1/40 electron volt, which represents roughly the mean kinetic energy of a
gas molecule at room temperature.
High and Low Absolute Temperatures
❖ This few representative temperature list used
to gain some intuitive appreciation of the
absolute temperature scale.
❖ Here the melting point of a substance is that
temperature where the solid and liquid forms
of the substance coexist in equilibrium (at a
pressure of 1 atmosphere).
❖ Above that temperature the substance is a
liquid.
❖ The boiling point of a substance is that temperature where the liquid and
gaseous forms of the substance coexist in equilibrium (at a pressure of 1
atmosphere).
❖ Above that temperature the substance at this pressure forms a gas. E.g., at the
melting point, water turns from ice to liquid water; at the boiling point, it
turns from liquid water into water vapor, i.e., into a gas.
❖ Let us consider any ordinary macroscopic system. Its absolute temperature T
is then positive and kT has a magnitude of the order of the mean energy
(above its ground state E0) per degree of freedom of the system; i.e.,
❖ Since every system has a lowest possible energy E0 of its ground state, it follows
that the absolute temperature has a minimum possible value T = 0 which the
system attains when its energy approaches that of its ground state.
❖ As the energy of the system increases above E0, its absolute temperature also
increases.
❖ There is no upper limit on how high the absolute temperature can be; this
corresponds to die fact that there is no upper limit on the possible magnitude of
the kinetic energy of the particles in any ordinary system.
❖ For example, temperatures of the order of 107 °K can occur in stars or in nuclear
fusion explosions on earth.
❖ The definition of the absolute temperature can be expressed in the behavior of
In Ω as a function of E.

❖ In the limiting case where E E0, i.e., where the energy of the system
approaches its lowest possible ground state value.
❖ The number Ω (E) of states accessible to the system in any small energy
interval between E and E + δE then approaches a value Ω0 which is very
small.
❖ A system has only one quantum state (or at most a relatively small number of
such states) corresponding to its lowest possible energy.
❖ Even if the number of states of the system in the energy interval δE near E0
were as large as f, InΩ0 would only be of the order of Inf; it would still be
utterly negligible compared to its value at higher energies which is of the
order of f .
❖ The entropy S = k InΩ of the system near its ground state energy E0 is thus
vanishingly small compared to its value at larger energies.
❖ Hence we are led to the following conclusion: As the energy of a system is
decreased toward its lowest possible value, the entropy of the system
tends to become negligibly small; or in symbols,
❖ The number of states increases very rapidly as the energy of the system is
increased above its ground state; one finds approximately

❖ As the energy E decreases to its lowest possible value E0, β becomes

exceedingly large and T β-1 .

❖ This limiting statement is called the third law of thermodynamics.

❖ In working at temperatures near absolute zero one must be careful that the
system under consideration is actually in equilibrium; this is particularly true
since the rate of attaining equilibrium may become quite slow at low
temperatures.
❖ The study of a system at low absolute temperatures is often of great interest
precisely because its entropy is then quite small.
❖ Correspondingly, the system is found distributed among a relatively small

number of states only.

 Work, Internal Energy, and Heat
❖ The basic relation

which connects the increase in the mean energy E of any system to the
macroscopic work W done on it and the heat Q absorbed by it.

❖ This relation provides the basis for the macroscopic measurement of all
the quantities appearing in it.
Work
❖ The macroscopic work done on a system is given by the increase in mean
energy of the system when the latter is thermally insulated (adiabatically
isolated) and some external parameter is changed.
❖ In practice, a measurement on a single system is sufficient for the deter
mination of a mean energy change and the corresponding work.
❖ The following examples illustrate some common procedures used for
measuring work.
1. Mechanical work
2. Electrical work
Mechanical work
A system consisting of a container filled
with water, a thermometer, and a paddle
wheel. Work can be done on this system by
the falling weight.
Electrical work
➔ A system A consisting of a container
filled with water, a thermometer, and
an electrical resistor.
➔ Work can be done on this system by
the battery.
❖ A process which is quasistatic, i.e., which is carried out sufficiently slowly so
that the system under consideration is at all times arbitrarily close to
equilibrium.
❖ Let us thus consider the important case of a fluid (i.e., of a substance which is
either a gas or a liquid) and derive an expression for the work done on this
fluid in a quasi-static process.
❖ Since the fluid is always essentially in equilibrium, the non uniformities of
density and other complications present in rapidly changing situations are
absent; instead, the fluid is always characterized by a well-defined mean
pressure p uniform throughout the fluid.
❖ Example : A fluid contained in a cylinder closed by a movable piston of area A .
The distance of the piston from the left wall is denoted by s.
➔ the mean force exerted by the fluid on the piston is
pA to the right;
➔ the mean force exerted by the piston on the fluid is
pA to the left.
 ❖ Suppose that the piston is moved very slowly to
the right by an amount ds (so that the volume of
the fluid is changed by an amount dv = A ds).

❖ The work done on the fluid is given by

where the minus sign occurs since the displacement ds and the force pA
acting on the gas have opposite directions.
❖ If the volume of the fluid is changed quasi-statically from some initial
volume Vi to some final volume Vf, its pressure p at any stage of this
process will be some function of its volume and temperature.
❖ The total work W done on the fluid in the
process is then simply obtained by adding
all the infinitesimal works :

➔ The work done on the fluid is positive if Vf < Dependence of the mean pressure p
Vi and negative if Vf > Vi. its magnitude is on the volume V of a particular
system.
equal to the shaded area contained below the The shaded area under the curve
represents the work done on the
curve. system when its volume is changed
quasi-statically from Vi to Vf.
 Internal energy
● Let us now turn our attention to the determination of the internal energy E
of a macroscopic system (i.e., the total energy of all its particles in the
frame of reference where the center of mass of the system is at rest).
● The value of E of the system in a given macrostate has significance only
when measured with respect to its value in some standard macrostate of
this system.
● Only differences in mean energy are relevant physically and such energy
differences can always be measured by the performance of work if the
system is kept adiabatically isolated.
 Heat
● The measurement of heat (commonly called calorimetry) is ultimately
reducible to the measurement of work.
● The heat Q absorbed by a system can be measured in two slightly
different ways: either by measuring it directly in terms of work, or by
comparing it with the known change of internal energy of some other
system which gives off the heat Q.
 Heat Capacity
❖ Consider a macroscopic system whose macrostate can be specified by its
absolute temperature T and by some other set of macroscopic parameters
denoted collectively by y
❖ Suppose that, starting with the system at a temperature T, an infinitesimal
amount of heat dQ is added to the system while all its other parameters y are
kept fixed.
❖ The temperature of the system will change by an infinitesimal amount dT which
depends on the nature of the system under consideration and which usually
depends also on the parameters T and y specifying the initial macrostate of this
system.
❖ The ratio

is called the heat capacity of the system and it is an easily measured property of
a system.

❖ Note that it depends ordinarily not only on the nature of the system, but also on
the parameters T and y specifying the macrostate of this system; i.e., in general,
Cy = Cv(T,y).
❖ The amount of heat dQ which must be added to a homogeneous system to
produce a given temperature change dT is expected to be proportional to the
total number of particles in this system.
❖ Hence it is convenient to define a related quantity, the specific heat, which
depends only on the nature of the substance under consideration, but not
on the amount present.
❖ This can be achieved by dividing the heat capacity Cy of v moles (or m
grams) of the substance by the corresponding number of moles (or of
grams).
❖ The heat capacity per mole or specific heat per mole is thus defined as
❖ The specific heat per gram is defined as

❖ The cgs units of the molar specific heat are ergs degree-1 mole-1.
❖ When all the external parameters of the system (such as its volume V) are
kept constant in the process of adding heat, no work is done on the system
so that dQ = dE ; i.e., the absorbed heat serves then merely to increase the
internal energy of the system.
❖ Denoting the external parameters collectively by the symbol x,
❖ The last expression is a derivative since dE is a genuine differential
quantity; we have written it as a partial derivative to indicate that all
the external parameters x are supposed to be kept constant.
❖ Note that the heat capacity must always be positive, i.e.,
❖ To indicate a typical order of magnitude, the specific heat of water at
room temperature is experimentally found to be 4.18 joules degree-1
gram-1 .
❖ The mean energy per mole of monatomic gas
where Na is Avogadro’s number and R = Nak is the gas constant.
❖ For a monatomic ideal gas, the molar specific heat Cv at constant
volume is given by
 Entropy
❖ The entropy S of a system determine by appropriate measurements of heat
and absolute temperature.
❖ The system is in equilibrium at the absolute temperature T and that an
infinitesimal amount of heat dQ is added to the system by bringing it into
contact with a heat reservoir at a temperature infinitesimally different
from T (so that the equilibrium is disturbed by a negligible amount and the
temperature T of the system remains well-defined).
❖ Then the resulting entropy change of the system is equal to
❖ Now, to compare the entropy of the system in two different macrostates
where the values of the external parameters of the system are the same.
❖ Assume that the absolute temperature is Ta in one macrostate and Tb in the
other.
❖ The system then has a well-defined entropy Sa = S(Ta) in the first
macrostate and a well-defined entropy Sb= S(Tb) in the second macrostate.
❖ It should be possible to calculate the entropy difference Sb-Sa by imagining
that the system is brought from the initial temperature Ta to the final tem
perature Tb in many successive infinitesimal steps.
❖ This can be done by placing the system in successive contacts with a series
of heat reservoirs of infinitesimally different temperatures.
❖ At all these stages the system would then be arbitrarily close to
equilibrium and thus would always have a well-defined temperature T.
❖ The entropy differences is given by
❖ This relation extremely interesting since it provides an explicit connection
between two very different types of information about the system under
consideration.
❖ On the one hand, involves the heat capacity which can be obtained from
purely macroscopic measurements of heat and temperature.
❖ On the other hand, it involves the entropy S = k InΩ which is a
quantity obtainable from a microscopic knowledge of the quantum
states of the system; i.e., either it can be calculated from first
principles, or it can be obtained by using spectroscopic data to
deduce the energy levels of the system.
❖ If the heat capacity Cx is independent of temperature in the
temperature range between Ta and Tb, entropy differences becomes

❖ The temperature dependence of the heat capacity of any substance

described
 Intensive and Extensive Parameters
❖ How the various macroscopic parameters are depend on the size of the
system under consideration.
❖ Parameters are of two types:
1. Intensive parameter which are independent of the size of the
system and
2. Extensive parameter which are proportional to the size of the system .
❖ These two types of parameters may be characterized by considering a
homogeneous macroscopic system in equilibrium and imagining the system
to be divided into two parts (e.g., by introducing a partition).
 Subdivision of a homogeneous macroscopic system
into two parts.

❖ Suppose that a macroscopic parameter y characterizing the entire system

assumes the values y1 and y2 for the two resulting subsystems. Then
I. the parameter y is said to be intensive if y = y1= y2
II. the parameter y is said to be extensive if y = y1+ y2
❖ For example, the mean pressure of a system is an intensive parameter, since
both parts of a system, after subdivision, will have the same mean pressure as
before.
❖ Similarly, the temperature of a system is an intensive parameter.
❖ On the other hand, the volume V of a system is an extensive parameter, as
is the total mass M of a system. The density p of a system, p = M/V, is then
an intensive parameter.
❖ Indeed, it is clear that the ratio of any two extensive parameters is an
intensive parameter.
❖ The internal energy E of a system is an extensive quantity.
❖ Indeed, no work is required to subdivide the system into two parts i f one
neglects the work involved in creating the two new surfaces.
❖ (This work is negligible for large systems for which the ratio of the
number of molecules near the boundary to the number of molecules in the
bulk of the system is very small.)