Carnot Cycle

In 1824 Sadi Carnot, a French engineer published a treatise in

which he abstracted the essential features of heat engines. We
will analyze a four step reversible Carnot cycle applied to an ideal
gas:
Reversible Carnot Cycle for an Ideal Gas

7.00
(P1, V1, TH)
6.00 Step 1: reversible isothermal
expansion at TH
5.00 Step 4:
reversible
Pressure (atm)

4.00 adiabatic (P2, V2, TH)

compression Step 2: reversible
3.00
from TL to TH adiabatic expansion
2.00 (P4, V4, TL) from TH to TL

1.00 Step 3: reversible isothermal (P3, V3, TL)

compression at TL
0.00
0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00
Volume (L)

Step 1: The ideal gas in thermal equilibrium with a high

temperature thermal reservoir at T H expands reversibly and
isothermally from V1 to V2. During this expansion qH of heat is
transferred from the high temperature reservoir to the gas to keep
the gas isothermal during the expansion. The reversible work done
by the ideal gas during this isothermal expansion is:
w1 = - n R TH ln (V2 / V1) = - qH
Why in this step is the reversible work the negative of the heat
transfered?
21.1
 Sadi Carnot was born in 1796 the son of
Lazare Carnot, a noted French
mathematician, engineer, and general. He
began his university studies at age 16 at the
Ecole Polytechnique in Paris. After two
years Sadi left the Ecole to work in the
Corps of Engineers. Unchallenged in the
Corps of Engineers he spent some time
analyzing heat engines, about which little
was known of their theory of operation. In
1824 he published his only work Reflexions sur la puissance motrice
du feu (Reflections on the Motive Power of Fire), which was mostly
ingnored by his contemporaries. This analysis set upper limits on the
efficiency of steam engines and paved the way for the development
of the 2nd Law of Thermodynamics. He died in 1832 at the age of
46, the victim of a cholera epidemic.
The figure is taken from a ChemTeam WEB page maintained by John
L. Park at dbhs.wvusd.k12.ca.us/Gallery/GalleryMenu.html

21.2
Step 2: The ideal gas expands reversibly and adiabatically from T H to TL.
The reversible work done by the ideal gas during this adiabatic expansion is:

w2 = n CV (TL - TH)
Could you derive this expression for the work done in the adiabatic
step?
Step 3: The ideal gas in thermal equilibrium with a low temperature thermal
reservoir at TL is compressed reversibly and isothermally from V 3 to V4.
During this expansion qL of heat is transferred from the ideal gas to the low
temperature reservoir to keep the gas isothermal during the compression. The
reversible work done by the ideal gas during the isothermal expansion is:

w3 = - n R TL ln (V4 / V3) = - qL
Step 4: The ideal gas is reversibly and adiabatically compressed back to its
initial state to complete the cycle. The reversible work done by the ideal gas
during this adiabatic compression is:

w4 = n CV (TH - TL)
The net work done in one complete cycle is the sum of the work
done in each of the cycle steps:
wnet = w1 + w2 + w3 + w4
= - n R TH ln (V2 / V1) + n CV (TL - TH)
- n R TL ln (V4 / V3) + n CV (TH - TL)
The work done in the adiabatic steps cancels to give:
wnet = - n R TH ln (V2 / V1) - n R TL ln (V4 / V3)

21.3
We can equate relations that we derived earlier for the adiabatic steps (see the
section on adiabatic processes):

CV ln (TH / TL) = R ln (V3 / V2) = R ln (V4 / V1)

to simplify the equation for the net work even more:

wnet = - n R TH ln (V2 / V1) - n R TL ln (V1 / V2)

= - n R ln (V2 / V1) (TH - TL)
= - n R TH ln (V2 / V1) (TH - TL) / TH
= + w1 (TH - TL) / TH
= - qH (TH - TL) / TH
Could you justify the steps in the above derivation?
Remembering the definition of efficiency of a heat engine we have for the
efficiency of our reversible cyclic Carnot engine:

efficiency = - wnet / qH = (TH - TL) / TH

Note that the efficiency of the reversible heat engine does not depend on the
nature of the working fluid, but only depends on the absolute temperatures
between which the engine is operating.
While we used an ideal gas as the working fluid to derive this result, the
result is general and applies to any reversible heat engine and in fact
represents the maximum efficiency possible for any engine.
Which is more efficient, your refrigerator or your freezer?
Which has the greater efficiency, an engine operating between 80 oC and 90
o
C or an engine operating between 90 oC and 100 oC?
Could you sketch how a single reversible Carnot cycle would appear on a TS
diagram, a plot of temperature versus entropy?
21.4
A temperature scale is defined by at a minimum two temperatures
and a interpolatable scale between the values of these two
temperatures. The temperatures that define the scale are known as
fixed points in temperature. They are associated with highly
reproducible systems and are determined by international
agreement. These fixed points in temperature are chosen by
international agreement. The latest agreement has been published
as The International Temperature Scale of 1990 (ITS-90) in
Metrologia, 27:3-10 (1990).
The efficiency of a heat engine will be a maximum, if the low
temperature reservoir is at 0 degrees on whatever absolute
temperature scale we choose. The results of the Carnot cycle
therefore define the thermodynamic scale of temperature in which
the lowest fixed point in temperature is absolute zero. All that
remains to complete the definition of the thermodynamic
temperature scale is to choose one other fixed point in temperature.
If we choose the other fixed point to be the triple point of water at
which air free ice, liquid water, and water vapor are all in
equilibrium at a temperature of 273.16 K,

then the thermodynamic and Kelvin scales of temperature agree

with each other. 21.5
The efficiency of a single reversible Carnot cycle can also be
written as:
efficiency = - wnet / qH = + qnet / qH = (qH + qL) / qH
Equating this expression for efficiency with the one we developed
previously:
(qH + qL) / qH = (TH - TL) / TH
gives after rearrangement:
q H / TH + qL / TL = 0

21.6
By extending this result for the single reversible Carnot cycle to any general
reversible cyclic process an analytic expression for entropy can be developed:

adiabats

isotherms

general
reversible
cycle

If we slice the general reversible cycle with a series of adiabats and

isotherms the general cyclic process can be represented as a sum of single
reversible Carnot cycles:

 ( qH / T H + qL / TL ) i = 0 Why is this sum equal to zero?

The sum is over all of the indvidual single reversible Carnot cycles that are
at least partly in the general reversible cycle. Notice that two adjacent single
reversible Carnot cycles will share an edge (see the colored arrows in the
above sketch) and that in the Carnot analysis of each of these adjacent cycles
that edge will be traversed in opposite directions and the corresponding
terms from the two Carnot cycles will cancel in the sum. The only terms
which will not cancel are for those edges that are outside the general cycle
(see the edge labeled with the green arrow).

21.7
As we let the number of adiabats and isotherms slicing the general
reversible cyclic process approach infinity:

1) the temperatures of the high, TH, and low, TL, thermal reservoirs
and the heats withdrawn, qH, and dumped, qL, into them, respectively,
approach each other for each individual single reversible Carnot cycle and
we can drop the subscripts distinguishing between them

and:
2) the sum over all the single reversible Carnot cycles is
replaced by an integral, which just represents an infinite sum over
differential quantities:

lim  (qH / TH + qL / TL ) -->  dqrev /T = 0

TH --> TL --> T

qH + qL --> dq

The rev subscript on dqrev is a reminder that these results apply to a

reversible process.
Why does qH + qL approach dqrev, the differential difference in heat transfer
for the single reversible Carnot cycle under consideration?
21.8
Remembering that if the cyclic integral of some function is equal
to zero, then that function is a state function, we define an
analytical expression for the differential change in the state
function entropy as:
dS  dqrev / T

21.9