SECOND LAW OF

THERMODYNAMICS
DIRECTIONS OF THERMODYNAMIC PROCESSES
▪ Irreversible process –processes that proceed
spontaneously in one direction but not the other.
▪ Thermodynamic processes that occur in nature are all irreversible
processes. (ex. flow of heat from hot body to a cooler body, free
expansion of gas).
▪ Non-equilibrium process
▪ Reversible process – one whose direction can be reversed
by an infinitesimal change in the conditions of the process,
and in which the system is always in or very close to
thermal equilibrium.
▪ Equilibrium process
▪ By making the temperature gradient and the pressure differences
in the substance very small, the system can be kept very close to
equilibrium states and make the process nearly reversible.
HEAT ENGINES
▪ any device that transforms heat partly into work or
mechanical energy

▪ Working substance – the matter inside the engine which

undergoes inflow and outflow of heat, expansion and
compression, and sometimes change of phase.
▪ Cyclic process – a sequence of processes that eventually
leaves the substance in the same state in which it started.
▪ Hot reservoir – heat source
▪ Cold reservoir – absorbs the
discarded heat from the engine.

▪ When a system is carried through

a cyclic process, it’s initial and
final internal energies are equal:

▪ The net heat Q absorbed per

cycle is

(1)
Thermal efficiency
▪ represents the fraction of QH that is converted to work.

(2)
SAMPLE PROBLEM 1
▪ A gasoline truck engine takes in 10,000 J of heat and
delivers 2000 J of mechanical work per cycle. The heat is
obtained by burning gasoline with heat of combustion
Lc = 5.0 x 104 J/g.
(a) What is the thermal efficiency of this engine?
(b) How much heat is discarded in each cycle?
(c) If the engine goes through 25 cycles per second, what is
its power output in watts? In horsepower?
(d) How much gasoline is burned in each cycle?
(e) How much gasoline is burned per second? Per hour?
INTERNAL-COMBUSTION ENGINE V – minimum volume
rV – maximum volume
▪ Gasoline engine (r = 8 to 10)
r – compression ratio
OTTO CYCLE
▪ A gasoline engine that has a
theoretical maximum thermal
efficiency e that depends on the
compression ratio r and the ratio
of heat capacities γ of the working
substance.

(3)

▪ For r = 8, and γ=1.4, e = 56%

▪ For real gasoline engines, e ≈ 35%
DIESEL CYCLE
▪ Similar to gasoline engine
▪ r = 15 to 20
▪ e = 65% to 70%
 REFRIGERATORS
▪ A heat engine operating in
reverse
▪ QC is positive
▪ QH and W are negative
▪ Coefficient of performance, K

(4)
 AIR CONDITIONER
▪ Works on the same principle
as a refrigerator
▪ Coefficient of performance, K

where
 THE SECOND LAW OF THERMODYNAMICS
▪ The “engine” statement (Kelvin-Planck statement)

▪ The “refrigerator” statement (Clausius statement)

 SAMPLE PROBLEM 2
▪A refrigerator has a coefficient of performance of
2.10. In each cycle it absorbs 3.40 x 104 J of heat
from the cold reservoir.
(a) How much mechanical energy is required each
cycle to operate the refrigerator?
(b) During each cycle, how much heat is discarded
to the high-temperature reservoir?
SEATWORK
▪A refrigerator has a coefficient of
performance of 2.25, runs on an input of 95 W
of electrical power, and keeps its inside
compartment at 5°C. If you put a dozen 1.0-L
plastic bottles of water at 31°C into this
refrigerator, how long will it take for them to
be cooled down to 5°C? (Ignore any heat that
leaves the plastic) cwater = 4190 J/Kg-K.
SAMPLE PROBLEM 3
▪A gasoline engine has a power output of 180
kW (about 241 hp). Its thermal efficiency is
28.0%.
(a) How much heat must be supplied to the
engine per second?
(b) How much heat is discarded by the engine
per second?
SEATWORK
▪ The Otto-cycle engine in a Mercedes-Benz SLK230
has a compression ratio of 8.8.
(a) What is the ideal efficiency of the engine?
Use γ = 1.40
(b) The engine in a Dodge Viper GT2 has a
slightly higher compression ratio of 9.6. How much
increase in the ideal efficiency results from this
increase in the compression ratio?
 THE SECOND LAW OF THERMODYNAMICS
▪ The “engine” statement (Kelvin-Planck statement)

▪ The “refrigerator” statement (Clausius statement)

According to the second law, no heat engine can have 100%
efficiency.

How great an efficiency can an engine have, given two heat

reservoirs at temperatures T and T ?
H C
THE CARNOT CYCLE
▪ idealized heat engine that has the maximum possible efficiency
consistent with the second law.
▪ The Carnot cycle operates between two heat reservoirs at
temperatures TH and TC and uses only reversible processes.

▪ Its thermal efficiency depends only on TH and TC.

STEPS OF THE CARNOT CYCLE
1. The gas expands isothermally at temperature TH ,
absorbing heat QH (ab).
2. It expands adiabatically until its temperature drops to
TC (bc).
3. It is compressed isothermally at TC , rejecting heat
|QC|(cd).
4. It is compressed adiabatically back to its initial state
at temperature TH (da).
 SAMPLE PROBLEM 4
A Carnot engine takes 2000 J
of heat from a reservoir at 500
K, does some work, and
discards some heat to a
reservoir at 350 K. How much
work does it do, how much
heat is discarded, and what is
its efficiency?
SAMPLE PROBLEM 5
▪ Suppose 0.200 mol of an ideal diatomic gas γ = 1.40
undergoes a Carnot cycle between 227oC and 27oC,
starting at pa = 10.0 x 105 Pa at point a in the pV-diagram of
the Carnot cycle. The volume doubles during the
isothermal expansion step a→ b. (a) Find the pressure and
volume at points a, b, c, and d.
(b) Find Q, W, and U for each step and for the entire cycle.
(c) Find the efficiency directly from the results of part (b),
and compare with the value calculated using TH and TC.
THE CARNOT REFRIGERATOR
▪ Because each step in the Carnot cycle is reversible, the
entire cycle may be reversed,converting the engine into a
refrigerator.
▪ The coefficient of performance of the Carnot refrigerator is
SAMPLE PROBLEM 6
▪If the cycle described in Sample problem 5 is
run backward as a refrigerator, what is its
coefficient of performance?
THE CARNOT CYCLE AND THE SECOND LAW
▪ No engine can be more efficient than a Carnot
engine operating between the same two
temperatures.

▪ All Carnot engines operating between the same

two temperatures have the same efficiency,
irrespective of the nature of the working
substance.
ENTROPY
▪ provides a quantitative measure of randomness.

Consider an infinitesimal isothermal expansion of an ideal

gas. We add heat dQ and let the gas expand just enough to
keep the temperature constant.

The gas is more disordered after the expansion than before.

Thus the fractional volume change dV/V is a measure of the
increase in randomness
ENTROPY
▪ We introduce the symbol S for the entropy of the system,
and we define the infinitesimal entropy change dS during
an infinitesimal reversible process at absolute temperature
T as

▪ If a total amount of heat Q is added during a reversible

isothermal process at absolute temperature T, the total
entropy change ΔS = S2 - S1 is given by
SAMPLE PROBLEM 7
▪ What is the change of entropy of 1 kg of ice that is
melted reversibly at 0oC and converted to water at
0oC? The heat of fusion of water is Lf = 3.34 x 105
J/kg.

Ans: 1.22 x 103 J/K

ENTROPY IN REVERSIBLE PROCESS
▪ When a system proceeds from an initial state with entropy
S1 to a final state with entropy S2 , the change in entropy ΔS
= S2 - S1 does not depend on the path leading from the
initial to the final state but is the same for all possible
processes leading from state 1 to state 2.
SAMPLE PROBLEM 8
▪One kilogram of water at 0oC is heated to
100oC. Compute its change in entropy.
Assume that the specific heat of water is
constant at 4190 J/kg-K over this temperature
range.

Ans: 1.31 x 103 J/K

ENTROPY IN CYCLIC PROCESS
▪ the total entropy change during any reversible
cycle is zero
ENTROPY AND THE SECOND LAW
▪ An important statement of the second law of
thermodynamics is that the entropy of an isolated system
may increase but can never decrease.

▪ When a system interacts with its surroundings, the total

entropy change of system and surroundings can never
decrease.
▪ When the interaction involves only reversible processes, the
total entropy is constant and S = 0; when there is any
irreversible process, the total entropy increases and ΔS > 0.
SEATWORK
▪ (a) Calculate the change in entropy when 1.00 kg of water
at 100oC is vaporized and converted to steam (b) Compare
your answer to the change in entropy when 1.00 kg of ice is
melted at 0oC. Is the change in entropy greater for melting
or for vaporization? Interpret your answer using the idea
that entropy is a measure of the randomness of a system.