ME 7002 (522 EM1460) Advanced Thermodynamics

Fall, 2018
Topic 4. Reversible Processes and the Maximum Work Theorem
Instructor: Kuo-Long Pan

Contents
I. Possible and impossible processes
II. Quasi-static and reversible processes
III. Relaxation times and irreversibility
IV. The maximum work theorem
V. Coefficients of performance: engine, refrigerator, and heat pump
VI. The Carnot cycle
VII. Measurability of temperature and entropy
VIII. Power output and endoreversible engines

Reading
H. B. Callen, Thermodynamics and An Introduction to Thermostatistics, 2nd Ed., Chap. 4.

I. Possible and Impossible Processes

Criteria governing the occurrence of a specific process
․ Law of mechanics (conservation of energy)
․ Maximization of entropy

Example 4.1-1: maximum work extracted in a two-body system

Example 4.1-2: highest temperature obtained in a three-body system

II. Quasi-Static and Reversible Processes

Thermodynamic configuration space
․ The fundamental equation S = S(U, V, N1,…, Nr) defines a surface on the configuration
space whereby S/U  1/T is positive and U is a single valued function of S.
․ By definition, each point in the configuration space represents an equilibrium state.
Representation of a nonequilibrium state would require a space of immensely greater
dimension.
․ The fundamental equation of a composite system can be represented by a surface in a
configuration space with coordinate axes corresponding to the extensive parameters of all
of the subsystems.

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Quasi-static processes
․ A quasi-static process is defined in terms of a dense succession of equilibrium states, known
as a quasi-static locus on the hypersurface of configuration space.

․ A quasi-static process is an idealized concept, for a real process always involves

nonequilibrium intermediate states having no representation in the thermodynamic
configuration space.
․ A quasi-static process is an ordered succession of equilibrium states and does not involve
considerations of rates, velocities, or time, whereas a real process is a temporal succession
of equilibrium and nonequilibrium states.

Approximation of a quasi-static process

․ Although no real process is identical to a quasi-static process, one can simulate such a
process by leading a system through a succession of states that coincides at any desired
number of points with a given quasi-static locus.
․ As shown in Fig. 4.3 (Callen), this process can be approximated in terms of discrete
jumping between finite state points, by removing some constraints, through non-
representable nonequilibrium states. By spacing the points arbitrarily closely along the
quasi-static locus we approximate the process arbitrarily closely.
․ The identification of -PdV as the mechanical work and of TdS as the heat transfer is valid
only for quasi-static processes.

Reversible processes
․ The locus has unique directionality, proceeding from low entropy to high entropy. Such a
process is irreversible.
․ A quasi-static locus can be approximated by a real process in a closed system only if the

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 entropy is monotonically non-decreasing along the quasi-static locus.
․ The limiting case of a quasi-static process in which the increase in the entropy becomes
vanishingly small is called a reversible process. For such a process the final entropy is equal
to the initial entropy, and the process can be traversed in either direction, as shown in Fig.
4.4.
․ The difference of reversibility defined in different textbooks should be noticed (to be
discussed in the lecture).

III. Relaxation Times and Irreversibility

Relaxation time
․ The rate at which constraints can be relaxed as a system approximates a quasi-static locus
is characterized by the relaxation time  of the system.
․ Processes that occur in times shorter than  are not quasi-static, whereas processes that
occur in times longer than  can be approximately quasi-static.

An example of the adiabatic expansion of a gas in a cylinder fitted with a piston

․ Local rarefaction is homogenized by mechanical dissipation which involves diffusive
reflection and viscous damping.

Heat flow and irreversibility (more reading)

․ Quasi-static (in other books: reversible, quasi-equilibrium…) vs. reversible (isentropic,
reversible adiabatic…)

IV. The Maximum Work Theorem

Maximum work theorem
Consider a primary system associated with one auxiliary system into which work can be
transferred and another into which heat can be transferred:
․ For all processes leading from the specified initial state to the specified final state of the
primary system, the delivery of work is maximum (and the delivery of heat is minimum) for
a reversible process.
․ The delivery of work (and of heat) is identical for every reversible process.

Relevant diagram and terminologies

․ Reversible work sources: defined as systems enclosed by adiabatic impermeable walls and
characterized by relaxation times sufficiently short that all processes within them are
essentially quasi-static.

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․ Reversible heat sources: defined as systems enclosed by rigid impermeable walls and
characterized by relaxation times sufficiently short that all processes within them are
essentially quasi-static.

Proof
dU  dQRHS  dWRWS  0

dQRHS
dStot  dS  0
TRHS

dWRWS  TRHS dS  dU

T 
dWRWS maximum    RHS dQ  dU  1  TRHS / T  dQ    dW 
 T 
․ In an infinitesimal process, the maximum work that can be delivered to the reversible work
source is the sum of
(a) the work (-dW) directly extracted from the primary system
(b) a fraction (1  TRHS/T) of the heat (-dQ) directly extracted from the primary system.
․ The fraction (1  TRHS/T) of the extracted heat that can be converted to work in an
infinitesimal process is called the thermodynamic engine efficiency.

Total (non-infinitesimal) process

U  QRHS  WRWS  0

The reversibility condition: Stotal  S subsystem   dQRHS / TRHS  0

․ The integral can be evaluated in terms of known heat capacity: CRHS(T) = dQRHS/dTRHS of
the reversible heat source. This infers QRHS and WRWS.
․ The two equations provide the solution of all problems based on the maximum work
theorem.
․ For a thermal reservoir serving the reversible heat source, TRHS is fixed. Thus,
Q
Stotal  S subsystem  res  0
Tres

WRWS  Tres S subsystem  U subsystem

․ The theorem can also apply to the case of negative delivered work, but with the work that
must be supplied to the primary system being least.

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․ Example 4.5-1: maximum work extracted from a primary system
․ Example 4.5-2: minimum work needed for separation of chemical species

V. Coefficients of Performance
Thermodynamic engine

dQh  dWh   dQc  dWRWS  0

dQc
dS h  0
Tc

․ Thermodynamic engine
efficiency
dWRWS T
e   1 c
 dQh  Th

Refrigerator
․ Coefficient of refrigerator
performance
r 
 dQc   Tc
 dWRWS  Th  Tc

Heat pump
․ Coefficient of heat pump
performance
dQh Th
p  
 dWRWS  Th  Tc

VI. The Carnot Cycle

Specific processes to accomplish the delivery of maximum work
․ Auxiliary systems are employed to convey heat and work to the reversible heat and work
sources.
․ The auxiliary system must not enter into the overall energy or entropy accounting. Its state
should be recovered at the end of the process.

The Carnot cycle with finite heat and work transfers

․ The auxiliary system in contact with the primary system (hot reservoir) and with the
reversible work source: isothermal expansion.

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․ The auxiliary system in contact only with the reversible work source: adiabatic expansion.
․ The auxiliary system in contact with the cold reservoir and with the reversible work source:
isothermal compression.
․ The auxiliary system in contact only with the reversible work source: adiabatic
compression.

Heat transfer, net work, and thermodynamic (Carnot) efficiency

The Carnot cycle with changing Th and Tc

․ If the hot and cold systems are merely reversible heat sources, rather than reservoirs, the
Carnot cycle must be carried out in infinitesimal steps  ThdS …
․ There is no difference in the essential results, although Th and Tc are continually changing
variables and the net evaluation of the process requires an integration over the differential
steps.

Real efficiency
․ Real engines can never attain ideal thermodynamic efficiency because of mechanical
friction (also thermal/species diffusion …) and because they cannot be operated so slowly
as to be truly quasi-static. The efficiency seldom attains more than 30 or 40 %.

Example 4.7-1

VII. Measurability of Temperature and Entropy

Measurability of temperature

 e  1 Tc / Th

․ The ratio of two given temperatures must actually be determined in terms of the limiting
maximum efficiency of all real engines, but this is a difficulty of practice.
․ Arbitrary multiplicative constant and selection of fiducial systems

Measurability of entropy
T1, P1   S   S  
S1  S 0      dT    dP 
T0 , P0   T   P  T 
 P

T1, P1   S    P  
   
T0 , P0   P 
T 
 
 T 
S
 dT  dP 

T1, P1    P  

T0 , P0 
 V    dT  dP 
  T  S 

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VIII. Power Output and Endoreversible Engines
Endoreversible engine problem
․ In the Carnot engine the temperature difference is made “infinitely small,” resulting in an
infinitely slow process and an infinitesimal power output.
․ An endoreversible engine is defined as one in which the two processes of heat transfer are
the only irreversible processes in the cycle.

 Qh     T  T 
h h w
th

t  t h  tc 
1  Qh   1 Qc
 h Th  Tw  c Tt  Tc
1 1 Tw 1 1 Tt 
t  W
 h Th  Tw Tw  Tt  c Tt  Tc Tw  Tt 

Tw  cTh  Tt  cTc 
1/ 2 1/ 2

c
 T    cTc 
1/ 2 1/ 2

 
h h
 h   c1/ 2
1/ 2

2
W   Th1/ 2  Tc1/ 2 
power      h c  1/ 2 1/ 2 
 t  max  h   c 
 erp  1  Tc / Th 1/ 2

Homework #4
․ 4.1-1 (correction: interchange of v1 and v2)
․ 4.2-4 (correction: remove s0)
․ 4.5-2, 4.5-5
․ 4.6-8
․ 4.7-4
․ 4.8-1
․ 4.9-2