Lecture-2

Chapter 2: Heat and entropy

Dr. Mohammed Sultan

 The heat equations
By regarding the state functions (U) as continuous
differentiable functions of the variables P, V and T
Under infinitesimal increments of the variables, one can write:

, = +


, = +


, = +

Where (U/P)V is the derivative with respect to P at constant V
and so on
The partial derivatives are thermodynamic coefficients to be
taken from experiments.
 The heat absorbed by the system can be obtained from the first law, written in
the form dQ = dU + PdV

= + +


= + +


= + +

In the 2nd eq, V is a function of P and T, and rewrite:

= +

+
= + +

It is convenient to define a state function called the enthalpy:
+

= + +

The heat equations in terms of dQ are summarized below:

= + +



= + +




= + +

We can immediately read off the heat capacities at
constant V and P:

= , =

These are useful, because they express the heat capacities
as derivatives of state functions.
 Applications to ideal gas

- Free expansion of an ideal gas

- After a new equilibrium was established: the final temperature
was found to be the same as the initial temperature.
W = 0 since the gas pushes into a vacuum.
Q = 0 since the temperature was unchanged.
U = 0 by the first law.
 Choosing V and T as independent variables, we conclude that U(V 1, T) = U(V2, T),
that is, U is independent of V:
=
Of course, U is proportional to the total number of particles N, which has been
kept constant. The heat capacity at constant volume can now be written as a
total derivative:

= =

Assuming that CV is a constant, we can integrate the above to obtain

= =

where the constant of integration has been set to zero by defining U = 0 at T = 0.

It follows that:
+
= =


= +

= +
Thus, for an ideal gas
=
 We now work out the equation governing a reversible adiabatic
transformation. Setting dQ = 0, we have dU = -PdV, Since dU = CV dT we
obtain:
+ = 0
Using the equation of state PV = NkBT, we can write:

() +
= =

Thus
+ + = 0
+ + = 0

+ = 0 + = 0 where

Assuming that is a constant, an integration yields:
ln = ln + Constant = Constant
Using the equation of state, we can rewrite this in the equivalent form
1 = Constant
 Since > 1, the adiabatic path has a steeper slope
than an isotherm in a P-V diagram, as depicted in
Figure below.
 Definitions
A thermal reservoir (a heat bath) is defined as a
body which has such a huge heat capacity that its
temperature does not change when energy is added
to it. For example, a large block of copper can act as
a thermal reservoir for small additions of heat
energy.
An isothermal change is one in which the pressure
and volume are altered in such a way that the
temperature remains constant.
An adiabatic change is one in which no heat enters
the system when the volume and pressure change.
During an adiabatic process the temperature of the
system changes even though no heat enters the
system.
 Carnot cycle
In a cyclic transformation, the final state is the
same as the initial state and therefore, U = 0,
because U is a state function.
A reversible cyclic process can be represented by a
closed loop in the P-V diagram.
The area of the loop is the total work done by the
system in one cycle. Since U = 0, it is also equal to
the heat absorbed:

= = = Area enclosed
 It is composed of the following four reversible processes:
1 2: isothermal expansion
2 3: adiabatic reversible
expansion.
3 4: isothermal compression.
4 1: adiabatic reversible
compression.
 A Carnot cycle is a reversible cycle bounded by two
isotherms and two adiabatic lines as illustrated for an ideal
gas in Figure, where T2 > T1.
The system absorbs heat Q2 along the isothem T2, and
rejects heat Q1 along T1, with Q1 > 0 and Q2 > 0, By the first
law the net work output is
= 2 1
In one cycle of operation, the system receives an amount of
heat Q2 from a hot reservoir, performs work W, and rejects
"waste heat" Q1 to a cold reservoir. The efficiency of the
Carnot engine is defined as
1
= =1
2 2
which is 100% if there is no waste heat, i.e. Q1 = 0. But, as
we shall see, the second law of thermodynamics states that
this is impossible.
 Second law of thermodynamics
The second law of thermodynamics expresses the common
wisdom that "heat does not flow uphill".
It is stated more precisely by Clausius:
There does not exist a thermodynamic transformation whose
sole effect is to deliver heat from a reservoir of lower
temperature to a reservoir of higher temperature.
An equivalent statement is due to Kelvin:
There does not exist a thermodynamic transformation whose
sole effect is to extract heat from a reservoir and convert it
entirely into work.
The important word is "sole". The processes referred to may
be possible, but not without other effects. The logical
equivalence of the two statements can be demonstrated by
showing that the falsehood of one implies the falsehood of
the other.
 Consider two heat reservoirs at respective temperatures T2 and T1, with T2 > T1.

(a) If the Kelvin statement were false, we could extract heat from T1 and convert
it entirely into work. We could then convert the work back to heat entirely, and
deliver it to T2 (there being no law against this). Thus, the Clausius statement
would be negated.

(b) If the Clausius statement were false, we could let an amount of heat Q2 flow
uphill, from T1 to T2. We could then connect a Carnot engine between T2 and T1,
to extract Q2 from T2, and return an amount Q1 < Q2 back to T1. The net-work
output is Q2 Q1 > 0. Thus, an amount of heat Q2 Q1 is converted into work
entirely, without any other effect. This would contradict the Kelvin statement.

In the atomic view, heat transfer represents an exchange of energy residing in

the random motion of the atoms. In contrast, the performance of work requires
an organized action of the atoms. To convert heat entirely into work would mean
that chaos spontaneously reverts to order. This is extremely improbable, for in
the usual scheme of things, only one configuration corresponds to order, while
all others lead to chaos, The second law is the thermodynamic way of expressing
this idea.
- The principle that the entropy never decreases applies to the
"universe" consisting of a system and its environments. It does
not apply to a non-isolated system, whose entropy may increase
or decrease.
- Since the entropy is a state function, the entropy change of the
system in going from state A to state B is SB - SA, regardless of the
path, which may be reversible or irreversible. For an irreversible
path, the entropy of the environment changes, whereas for a
reversible path it does not.
- The entropy difference SB - SA is not necessarily equal to the
integral

/

- It is equal to the integral only if the path from A to B is
reversible. Otherwise, it is generally larger than the integral.
 Entropy of ideal gas
We can calculate the entropy of an ideal
gas as a function of V and T by integrating
dS = dQ/T. In Fig, we approach point A
along two alternative paths, with V kept
fixed along path 1, and T kept fixed along
path 2
Along path 1, we have

= /

and, hence,


, = , 0 + = , 0 + ln
0 0
In order to determine S(V, T0), we integrate dS = dQ/T along the isothermal path 2.
Since dU = 0, we have

= = =

Thus


, = 0 , + = 0 , + ln
0
 Comparing the two expressions for S(V, T), we
conclude that
, 0 = 0 + ln
where C0 is an arbitrary constant. Absorbing the
constant V0 into C0, we can write
, = 0 + ln + ln
3
For a monoatomic gas we have ( = ) and
2
hence
, = 0 + ln 3/2
 The limits of thermodynamics
Thermodynamics is an elegant theory and a very useful
practical tool. The self-consistency of the mathematical
structure has been demonstrated through axiomatic
formulation. However, confrontation with experiments indicates
that thermodynamics is valid only insofar as the atomic
structure of matter can be ignored.

In the atomic picture, thermodynamic quantities are subject to

small fluctuations. The second law of thermodynamics is true
only on the macroscopic scale, when such fluctuations can be
neglected. It is constantly being violated on the atomic scale.

Taking the second law as absolute would lead to the conclusion

that the entropy of the universe must forever increase, leading
towards an ultimate "heat death". Needless to say, this ceased
to be imperative in the atomic picture.
 Definitions of Entropy
1. is a state variable whose change is defined for
a reversible process at T where Q is the heat
absorbed.
2. a measure of the amount of energy which is
unavailable to do work.
3. a measure of the disorder of a system.
 Third Law
The entropy of a perfect crystal is zero when the
temperature of a the crystal is equal to absolute zero (0 K).
- At 0 K, there is no thermal motion, and if the crystal is
perfect, there will be no disorder.
- Once the temperature begins to rise above 0, the particles
begin to move and entropy gradually increases as the
average kinetic energy of the particles increases.
- When temperature reaches the melting point of the
substance (Tm), there is an abrupt increase in entropy as
the substance changes from a solid to a more disordered
liquid.
- Again the entropy increases gradually as the motion of the
particles increases until the temperature reaches the
boiling point of the substance (Tb). At this point, there is
another drastic increase in entropy as the substance
changes from a confined liquid particles to random motion
gas particles.