Chemical Engineering

Thermodynamics
Yang, Yanhui

Content

Reversibility
Irreversible and reversible processes
Entropy
Joules experiment, ideal Carnot cycle, analysis of Carnot cycle,
efficiency, concept of entropy, entropy calculation
2nd law of thermodynamics
2nd law, entropy balance for open system, ideal work and lost
work.
3rd law of thermodynamics

Reversibility

Irreversible processes: changes in the system which cannot be

reversed in their entirety without making changes elsewhere in the
universe.
Reversible processes: a process is reversible if a second process
can be performed such that surroundings and the system can be
restored to their initial state except for infinitesimal changes.
We will illustrate the characteristics of reversible processes by way
of an example:
Expansion of a piston-cylinder arrangement with mass m placed on
the piston and ideal gas in piston.
We choose the system as the gas.

Reversibility

The work done is:

However, during the expansion, we dont know how changed and

W cannot be calculated this way.
Work can be calculated by measuring the effect of this process on
the surroundings.
Do a force balance on the system (path 1):

Solving for

and substituting into

we get

Reversibility

For simplicity, lets take

and

and

. We conclude

The work required to bring the system and the surroundings back to
their initial state is
.
When m is moved onto the platform, the gas expands irreversibility
against . Both the system and surroundings cannot be brought
back to their original state without expenditure of work. An external
agent must lift m to .

Reversibility

Consider the same expansion in two steps (path 2):

Reversibility
is greater than
gas in path 2 than in path 1.

. More work is done by the

is less than

Note also that in each case, the difference between the external
force and gas pressure is finite during the expansion, e.g., during 1st
step, it starts out at
and expands.
for 2nd
expansion.

Reversibility

Is there a path for which we do not need to do work to put the

system and the surroundings into their original state? If yes, what
are the characteristics of such a path?
Yes, a reversible path (path 3). System traverses equilibrium states.
Consider dividing m into N with N platforms and dividing the
expansion process into N steps.

Reversibility
, work for isothermal reversible

expansion.
Work to reverse:
. As
. Both system and the surroundings can be brought
back to their initial state without expenditure of work

During the expansion at each step:

. As

Entropy

Consider Joules experiments:

In Joules experiments, mechanical work is converted to internal
energy and temperature of the system rises.
Note however that we never observe the paddles to start turning to
raise the weight with temperature of the water decreasing, even
though first law is valid for both processes.
There is a missing law. There is a natural order of the states of the
systems such that it is impossible for some states to proceed others
within an adiabatic enclosure. This is called adiabatic accessibility.

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Entropy
Ideal Carnot cycle: idealized reversible engine cycle operating in a
completely reversible manner in a 4-step cycle

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Entropy

Analysis of the ideal Carnot cycle

System: n kmol of an ideal gas in a cylinder-piston assembly.
Process: a 4-step cyclic processes (all reversible)
Step 1-2: isothermal and reversible heat absorption at T1 (T1=T2=TH)

Amount of heat absorbed by the system (the working fluid):

Step 2-3: adiabatic and reversible gas expansion from T2 to T3

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Entropy
Step 3-4: isothermal and reversible heat rejection at T3 (T3=T4=TC)

Amount of heat rejection by the system (the working fluid)

Step 4-1: adiabatic and reversible gas compression from T3 to T1

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Entropy

For a cyclic process:

Efficiency is defined as ratio of net work done over heat absorbed:

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Entropy

Carnot efficiency:

As QH is positive and QC is negative, a negative sign needs to be

inserted when absolute-value signs are removed.

There exists a property (Q/T) whose change in a cyclic process is

given by
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Entropy

We already have postulated the existence of a state function S(U, X)

that determines whether state B is adiabatically accessible from
state A. We postulate that S is monotonically increasing function of
U.
,
, thermodynamics temperature the scale of
this temperature turns out to be the same as the ideal gas
temperature scale.
Expanding S in its independent variables:
,

For a reversible process:

system, such as pressure (P).

, F is the property of
,
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Entropy

For an adiabatic reversible process, dS=0 and dQrev=0.

,

=0

But all these quantities are state functions, so this equality holds
even for non-adiabatic processes as well. it should be always zero.

Substituting definition of T,

we get:

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Entropy

Simplify the derivation

,

In the previous derivation: is generalized force, is the

generalized displacement. They are replaced by PdV (PV work)

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Entropy calculation

Entropy changes without phase change:

Isobaric heating:
Isothermal process:

Isometric heating:
Entropy changes involving phase change:
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Entropy calculation
Example: calculate the changes in entropy when 100 kg of liquid
water is heated from 50 C and 1 bar to 230 C and 28 bar.
System: 100 kg of liquid water originally at 50 C and 1 bar
Process: heating from 50 C and 1 bar to 230 C and 28 bar
Solution:

Assumption:

From Steam table:

100*( 2.6099-0.7037)=190.62kJ/K

230 C, 28 bar

50 C, 1 bar

230 C, 1 bar

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2nd law of thermodynamics

All processes proceed in a direction such that the total entropy

change is positive, approaching zero as the process approaches
reversibility
Isolated systems maximize their entropy. Note that 2nd law applies
only to isolated systems. Practically, we can always apply 2nd law to
the universe since universe is an isolated system.
The total entropy of the universe is ever increasing.

Inequality holds for all real processes. Equality is a limiting case of

idealized reversible processes.

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2nd law of thermodynamics

Carnot cycle:

Heat transfer between two reservoirs at TH and Tc insulated from

other parts of the universe:
System: cold reservoir
Process: heat transfer
Entropy change of cold reservoir:

Entropy change of hot reservoir:

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2nd law of thermodynamics

Example: An inventor has devised a complicated non-flow process
in which 1 kmol of air is the working fluid. The net effects of the
process are claimed to be as follows:

A change in state of the air from 500 K and 2 bar to 350 K and 1 bar
The production of 2,000 kJ of work
The transfer of an undisclosed amount of heat to a reservoir at 300 K
Determine whether the claimed performance of the process is consistent
with the 2nd law. Assume that air is an ideal gas for which CP=7R/2 and
CV=5R/2.
Solutions:
System: 1 kmol of air initially at 500 K and 2 bar
Process: gas expands to produce work

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2nd law of thermodynamics

Air changes from 2 bar and 500 K to 1 bar and 350 K

Heat transfer to the cold reservoir at 300 K, from 1st law:

Entropy change of the gas (system)

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2nd law of thermodynamics

Entropy balance for open systems:

Rate of entropy generation: based on 2nd law of thermodynamics:

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2nd law of thermodynamics

Rate of total entropy change of the system:

Rate of change of entropy of the surroundings:

2nd law:
When entropy generation is zero (
), process is internally
reversible within the CV
Heat transfer between the CV and its surroundings must also be
reversible.
Steady state entropy balance:
Rate of entropy accumulation:

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2nd law of thermodynamics

Ideal work: for a completely reversible process under steady-state
flow condition, rate of entropy generation:

With one entering and one leaving streams and one Q term:

From steady state energy balance (1st law, neglecting kinetic energy
and potential energy):

Thermodynamics efficiency:

fs

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2nd law of thermodynamics

Lost work: wasted work due to irreversibility in a process (steadystate flow process, expressed in terms of rates):

From steady-state energy balance:

fs

For a single surroundings temperature:

Divided by flow rate:

The greater the irreversibility of a process, the greater the rate of
entropy generation and the greater the amount of energy wasted

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3rd law of thermodynamics

The entropy of all perfect crystalline substances at 0 K is zero:

A more general form of the third law applies to systems such as

glasses that may have more than one minimum energy state: the
entropy of a system approaches a constant value as the
temperature approaches zero.
It is impossible by any procedure, no matter how idealized, to
reduce the temperature of any system to zero temperature in a finite
number of operations.

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Revisit Carnot cycle

(1st law of thermodynamics)

, cyclic process, S is state function

(2nd law of thermodynamics)

(not all the heat can be converted to work)

(3rd law of thermodynamics)

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