Summary of Lecture-1

(refer to the discussion in the lecture for completeness)

Extensive parameters: Mathematically they are homogenous first order
function of the extensive parameters. For e.g. for internal energy an extensive
parameter
where, is the multiplicative constant. The above relation implies that if all
the extensive parameters are multiplied by , U is multiplied by the same
constant .
Similarly intensive parameters are homogenous zero order function of the
extensive parameters. For temperature T in can be written as:

Work (PV work) done is defined as

Pext can be taken as system pressure if equilibrium is established after the

step. Pext = Psystem in a reversible process as it takes place by infinitesimal
equilibrium states.

Shaded area work done.

Reversible

process

Work done in a complete reversible

cycle wcycle=0. [Exercise: Show this
from the above expression for w]

Irreversible process
If any intermediate step in the cyclic
process is irreversible then work done in
the complete (irreversible) cycle wcycle0.

Example 1
Take the example of a irreversible cyclic process involving two steps:
1) isothermal irreversible compression (P1, V1, T) (P2,V2,T) where V2<V1. It is accomplished as
discussed in the class. Work done is w1 = P2(V2 V1).
2) isothermal expansion: (P2, V2, T) (P1,V1,T). This can be done in 2 ways:
a) If done reversibly, then work done is w2 = RT ln (V2/V1). Hence wcycle = w1+w2>0.
b) If done irreversibly, then wcycle= P2(V2 V1) P1(V1 V2) = (P2 P1)(V1 V2) >0. By ideal
gas law P1<P2.
Exercise: Show the work done in the steps on the PV isotherm. Note: You can only show a
reversible path on the PV isotherm (i.e. only equilibrium intermediate steps are representable).
For an irreversible process only equilibrium intermediate states are representable on the
thermodynamic configuration space (here PV plane at constant T). Such equilibrium states for
step 1 and step 2b are the (P1, V1, T) and (P2,V2,T) . But nevertheless we can represent
irreversible work by shaded areas as discussed in the class and also shown above.
Exercise: Check to see that same amount of work as step 1 of Example 1 is done in a reversible
process containing two reversible steps i) (P1, V1, T) (P2,V1,T) ii) (P2,V1,T) (P2,V2,T) ;
where T=P2V1/R. Note: Here P2 and P1 are system pressures and this two step reversible path
can be represented in PV diagram. Sketch it? (hint: I already sketched it in the class but left off
the details).

It can reversed at any point by making an

infinitesimal change (which is pressure for
isothermal reversible expansion and
compression of ideal gas). It requires time
to equilibrate after each infinitesimal step.
(In other words, it involves all equilibrium
intermediate steps.

It cant be reversed at any point by making an

infinitesimal change as it does not involve all
infinitesimal reversible steps. Also it involves
many nonequilibrium intermediate states.
[Irreversibility of a process is ulmitately
decided by the corresponding entropy change
(dS) to be discussed in subsequent lectures]

 System and surroundings can be restored

to their initial conditions. [Exercise: Show
this]? Hint see the discussion for the
irreversible process below.

System and surroundings cant be

restored to their initial conditions. Its
illustrated below.

Take again the cyclic process in the Example 1. Note that system is restored to the original state by the
2nd step irrespective of the fact that its reversible or irreversible, but surroundings is never restored to
initial state. U since a state function, dU is constant for both the steps. (By virtue of Joules
experiment dU=0 as T is const, as will seen in the next lecture). w1 and w2 differs as one of them is
irreversible, hence q1 and q2 also differs. Hence in this example in the whole cycle a net amount of heat
is transferred to or from the surroundings (q2+q1= (w1+w2)<0). System is restored but with a mark on
the surroundings. Work was needed to be done to the system (by surroundings) and heat had to be
rejected to the surroundings (to maintain constant T). Note that system and surroundings forms an
isolated system and surroundings act as a thermal reservoir at constant temperature T.
Exercise: Consider the reverse of Example 1: Step1: Irreversible isothermal expansion, (P1,
V1, T) (P2,V2,T) where V2>V1. Step2: isothermal compression (P2, V2, T) (P1,V1,T) if done
a) reversibly b) irreversibly. Show that here too qcycle<0.

Some important formulas:

Basic knowledge of the fact expressed in Eq. (1) is needed to derive almost all equations in
this handout.
Heat capacity at constant volume

is defined as:

Exercise: Show that

Heat capacity at constant volume
Exercise: Show that

is defined as:

Lecture 2 (Summary)

2nd law of thermodynamics consists of 2 parts:

1.

(definition of entropy due to Clausius)

2. Change in entropy in any process is given by

where > applies
to irreversible process and the equality applies to reversible process.

Part 2 can be shown from the Clausius theorem (mathematical statement of second
law of thermodynamics):
(for cyclic processes)
Cyclic integral

This theorem is proved in the illustration of the 3rd point of the difference between
reversible and irreversible process. It is also discussed in the class.
Putting

in part 2 for isolated systems, for finite changes 0.

Entropy changes for:

a) Heating a substance at constant volume V, from temperature T1 to T2
(if CV is not a function of T)
b) Heating a substance at constant volume P, from temperature T1 to T2
(if CP is not a function of T)
c) Phase change at constant T and P:
d) Ideal gas changes at constant T:

e) For adiabatic processes: