Thermodynamic question answer

This discussion was initiated by Amit Katyal. I thought some of you may find it
useful.

Amit Katyal

Independent Researcher / Inventor - Hydrocarbons and Water Treatment

20h •

• Question
•
• Some questions about second law of thermodynamics and entropy 1. Can
we use equation “delta S = delta q/ T” for any process for which T is
constant? Can it be used for any isothermal process? Are all isothermal
processes reversible? Can an adiabatic process be reversible if it is carried
out infinitesimally slowly? Can we use equation “delta S = delta q/T” for
such an adiabatic change to get “delta S = 0”? 2. What is the meaning of
non PV work? How can it be extracted? I would welcome any comments on
these questions.

Discussions

Dr. Chaitanya Bapat

You can use the equation "delta S = delta q/ T " to calculate change in entropy
between two states of a system. Remember entropy is a state function. All
isothermal processes are not reversible. Yes adiabatic process can be reversible.
Such a process is called isentropic process. For a irreversible process net entropy
generation is always non zero. You have to use both first and second law of
thermodynamics to get the calculation right. Non pv work can mean work done
against frictional forces or flow work (like in a turbine).

Amit Katyal

Are isentropic processes infinitesimally slow processes? Flow through an

expansion valve in a refrigeration system is an isentropic process. Is it an
infinitesimally slow process?Can you give some examples of isothermal processes
which are not more or less reversible (no process is 100% reversible)?

Dr. Chaitanya Bapat yes, there is a confusion. In a refrigeration cycle, compression

of refrigerant vapour is isentropic. Is it an example of fast isentropic process? Is a
fast isentropic process, a reversible adiabatic process?

Dr. Chaitanya Bapat

Amit Katyal No there is no such rule. In fact a very fast process can also be
isentropic. Flow through a valve is a isenthalpic (constant enthalpy) process
almost never an isentropic process. I think you are getting confused a bit.

Amit Katyal

Dr. Chaitanya Bapat yes, there is a confusion. In a refrigeration cycle,

compression of refrigerant vapour is isentropic. Is it an example of fast isentropic
process? Is a fast isentropic process, a reversible adiabatic process? Is being
infinitesimally slow, a primary condition for reversibility?

Dr. Chaitanya Bapat

Amit Katyal Almost no real process in nature is truely isentropic. But it is a useful
approximation to analyze certain processes like compression, pumping etc. We
can then use factors like isentropic efficiency to get real life results.

Amit Katyal

Is compression an example of a fast isentropic process? I think compression is not

a reversible process. Is being infinitesimally slow, a primary condition for
reversibility?
Nikhilesh Mukherjee

I guess, condensation of vapor in a condenser though isothermal but not

reversible. In isothermal process system- surrounding ∆t =0, ∆U = 0. Vapor
condenses into liquid ( phase change), there is a gain in entropy as vapor
condenses. Phase change is a fast process. ∆t can't remain zero at phase change.
So process doesn't remain isothermal reversible. I guess you can't undo the
condensation by adding same heat to condenser and restore system-surrounding
back to their original state at phase change in a condenser.

Amit Katyal

Nikhilesh Mukherjee can we use “delta S = delta q/T” for condensation of vapour
in a condenser?

Nikhilesh Mukherjee

Amit Katyal Strictly no. ∆S = Qrev/T. delta Q has to be reversible that is you
should be able to restore system and surrounding to original position at any time.
T is constant. This eqn is only applicable when T is constant

If T is variable, you have to integrate between two end temperatures. In

condensation, at phase change Q is not reversible. It's a very fast heat transfer
when vapor condenses to liquid.

Nikhilesh Mukherjee

Amit Katyal Entropy is an extensive property. It's is sum of Q/T of all of molecules
in a gas mixture. dS = 0 when Entropy initial - Entropy final of system -
surrounding is zero. It doesn't depend on its path how they became same. Q is a
measure of internal energy. Internal energy is measure of internal molecular
(within molecule) arrangement. When at a given T all molecules have same
internal molecular state, the system is supposed to be in thermal equilibrium.
When all microstate of molelues are in equilibrium, system is reversible. It's an
ideal concept. Only it teaches when you can go near it to minimise entropy losses
and maximize useful application of energy.
Dr Bapat has explained your every point leaving no scope to add more.

Nikhilesh Mukherjee

Amit Katyal adiabatic process is assumed to be isentropic because delta Q is

considered = 0 which actually is not , even though the system is insulated and
process is very fast with little scope for radiation loss , delta Q is still not zero.
One reason we believe isothermal process as reversible or near reversible
because it is a very slow process. We assume system-surrounding stay in
equilibrium in very slow process.

As pointed out by Dr Bapat, all isothermal processes are not reversible,

particularly in condensation in condenser where there is phase change in
condenser , condensation is not reversible process. Phase change takes place in
split second, I have explained at phase change, ∆t is not zero. System -
Surrounding are not in reversible thermal equilibrium.

Dr. Chaitanya Bapat

Closed adiabatic process has no interaction with the surrounding. It only has to be
in equilibrium with itself. We assume that such equilibrium is attained
instantaneously. This of course doesn't happen in real life. That is why no real
process is truely isentropic. But it is good approximation for compression. This
assumption allows us to do calculations.

Amit Katyal

You mean that an infinitesimally slow isothermal process is reversible whereas an

extremely fast instantaneous adiabatic process is reversible.

Dr. Chaitanya Bapat

Amit Katyal The adiabatic process itself is not instantaneous. The substance is
assumed to attain equilibrium with itself instantaneously at all times during the
process. In isothermal process such equilibrium with surroundings cannot be
attained instantaneously in fact it takes long time so the process is slow.

Amit Katyal
Dr. Chaitanya Bapat will a closed adiabatic process always be more or less
reversible as it is always more or less always in quasi equilibrium with the
surroundings (as it is not interacting with the surroundings)?

Dr. Chaitanya Bapat

Amit Katyal As I said that is useful approximation. But it is NEVER exactly valid.
Which means that all adiabatic processes are not isentropic. The formula you are
using applies for reversible process. Irreversible process generates entropy. Never
just memorize formulas like this. Always draw a control volume. Write down the
first and second law expressions in first principles. Then simplify using your
assumptions. Otherwise you'll make mistakes. Compression can be approximated
as an isentropic process. Yes generally it is pretty fast. :)

Amit Katyal Reversible process has to be a quasi- equilibrium process. This means
that the substance has to be in equilibrium with the surroundings at all times
during the process. For an isothermal process this requires the process to be
infinitesimally slow. For a adiabatic process involving ideal gas such equilibrium
can be achieved quickly (assumed to be instantaneous in the ideal). So it depends
on the process

Amit Katyal

Dr. Chaitanya Bapat A closed adiabatic process is not exchanging heat or mass
with the surroundings. Do you mean that such a process is always in quasi
equilibrium with the surroundings so is more or less reversible ? do you mean
that a fast adiabatic process of compression is more or less reversible?