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Chemical Engineering
Thermodynamics
Yang, Yanhui
Content
• Reversibility
– Irreversible and reversible processes
• Entropy
– Joule’s experiment, ideal Carnot cycle, analysis of Carnot cycle,
efficiency, concept of entropy, entropy calculation
• 2 nd law of thermodynamics
– 2 nd law, entropy balance for open system, ideal work and lost
work.
• 3 rd law of thermodynamics
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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.
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Reversibility
• The work done is:
• However, during the expansion, we don’t 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
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Reversibility
• For simplicity, let’s take
and
. We conclude
and
.
• 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
.
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Reversibility
• Consider the same expansion in two steps (path 2):
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Reversibility
is greater than
. More work is done by the
gas in path 2 than in path 1.
.
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 1 st
step, it starts out at
expansion.
and expands.
for 2 nd
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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.
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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
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Entropy
• Consider Joule’s experiments:
• In Joule’s 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
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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:
, F is the property of
system, such as pressure (P).
,
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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:
P
• Assumption:
230 °C, 28 bar
• From Steam table:
• 100*( 2.6099-0.7037)=190.62kJ/K
50 °C, 1 bar
230 °C, 1 bar
T
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2 nd 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 2 nd law applies
only to isolated systems. Practically, we can always apply 2 nd 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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2 nd 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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2 nd 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 2 nd law. Assume that air is an ideal gas for which CP=7R/2 and
CV=5R/2.
Solutions:
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2 nd 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 1 st law:
• Entropy change of the gas (system)
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2 nd law of thermodynamics
• Entropy balance for open systems:
• Rate of entropy generation: based on 2 nd law of thermodynamics:
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2 nd law of thermodynamics
• Rate of total entropy change of the system:
• Rate of change of entropy of the surroundings:
• 2 nd 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.
• Rate of entropy accumulation:
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2 nd 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 (1 st law, neglecting kinetic energy
and potential energy):
fs
• Thermodynamics efficiency:
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2 nd law of thermodynamics
• Lost work: wasted work due to irreversibility in a process (steady-
state flow process, expressed in terms of rates):
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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3 rd 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
(1 st law of thermodynamics)
, cyclic process, S is state function
(2 nd law of thermodynamics)
,
(not all the heat can be converted to work)
(3 rd law of thermodynamics)
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