UTEG COLLEGE

The Second Law

Brief review of last class (adiabatic processes)
The ideal gas and entropy
The second law
The Carnot cycle
A new function of state - entropy

Heat capacity
Using the first law, it is easily shown that:

Q
CV

Always true
V

For an ideal gas, U = f n( ) only. Therefore,

dU
CV
and U U U 0 CV d CV 0
0
d

Enthalpy, H = U + PV, therefore:

dH = dU + PdV + VdP = Q + VdP

Ideal gas:

dH
CP
dT

Q
CP

Always true
P

and H H H 0 C P d C P 0
0

Calculation of work for a reversible process

(1)

1. Isobaric (P = const)

(2)

2. Isothermal (PV = const)

3. Adiabatic (PV = const)

(3)

4. Isochoric (V = const)

(4)

V
For a given reversible path, there is some associated physics.

W PdV area under curve; U Q + W

Configuration Work on an ideal gas

W PdV 0

Isochoric

W P dV P V f Vi

Isobaric

V f
dV
W PdV nR
nR ln
Isothermal
Vi V
Vi
Note: for an ideal gas, U = U(), so W = Q for isothermal processes.
It is also always true that, for an ideal gas,
Vf

U CV f i

and

H C P f i

Adiabatic processes: Q = 0, so W = U, also PV = constant.

1
W CV f i
Pf V f PV

i i
1

3R
5R
cP 5
Monatomic:
c

;
c

V
P

2
2
cV 3

5R
7R
cP 7
Diatomic: cV
; cP
;

2
2
cV 5

Chapter 2

100% Conversion of Heat to Work

2
Q
M

W=Q

Heat in equals heat out; energy is conserved! However,

common sense tells us this will not work (or it will in a
while).

100% transfer of heat to from cold to hot body

2 > 1

Something is
clearlyMmissing
Q
from the first
law!
Q1

1 < 2
Heat in equals heat out; energy is conserved! But we know
this never happens in the real world.

The Second Law of Thermodynamics

Clausius statement: It is impossible to construct a device

that operates in a cycle and whose sole effect is to transfer
heat from a cooler body to a hotter body.
Kelvin-Planck statement: It is impossible to construct a
device that operates in a cycle and produces no other effect
than the performance of work and the exchange of heat
from a single reservoir.
Carnots theorem: No engine operating between two
reservoirs can be more efficient than a Carnot engine
operating between the same two reservoirs.

Conversion of Heat to Work (a heat engine)

Efficiency (*):

Heat reservoir at
temperature 2 > 1

W
W
output

Q2 Q2
input

Q2 Q1
Q1 *

1
Q2
Q2

Q1
Q2

Q2
Heat
Engine

Q heat
W work
both in Joules

W Q2 Q1 *

Q1

Cold reservoir at
temperature 1 < 2

Q2 Q1

*Be careful with the

signs for heat!

The Carnot Cycle

ab isothermal expansion
bc adiabatic expansion
cd isothermal compression
da adiabatic compression

1.
2.
3.
4.

2
1

1.
2.
3.
4.

W2 > 0, Q2 > 0 (in)

W' > 0, Q = 0
W1 < 0, Q1 < 0 (out)
W'' < 0, Q = 0

1
1
2

Stirlings engine is a good approximation to Carnots cycle.

The Carnot Cycle

1.
2.
3.
4.

ab isothermal expansion
bc adiabatic expansion
cd isothermal compression
da adiabatic compression
1.
2.
3.
4.

W2 > 0, Q2 > 0 (in)

W' > 0, Q = 0
W1 < 0, Q1 < 0 (out)
W'' < 0, Q = 0

T1
1
T2

Stirlings engine is a good approximation to Carnots cycle.

Pressure

The absolute temperature (Kelvin) scale

T(K) = T(oC) + 273.15
Triple point
of water:
273.16 K

Based on the
ideal gas law
0

100

200

300

400

Temperature (K)

The Second Law of Thermodynamics

Clausius statement: It is impossible to construct a device

that operates in a cycle and whose sole effect is to transfer
heat from a cooler body to a hotter body.
Kelvin-Planck statement: It is impossible to construct a
device that operates in a cycle and produces no other effect
than the performance of work and the exchange of heat
from a single reservoir.
Carnots theorem: No engine operating between two
reservoirs can be more efficient than a Carnot engine
operating between the same two reservoirs.

Consider two heat engines

Carnot

Hypothetical

T2 > T1

T2 > T1

Q2

Q2'
W = Q2 Q1

Q1

M'

W' = Q2' Q1'

Q1'

W' W

Q2' Q2

T1 < T2

T1 < T2

Efficiency =

Efficiency = ' >

Connect M' to M and run M in reverse

W = W'

T2 > T1
Q2'
M'
M

Q2
W'

Q1'

Q1
T1 < T2

Therefore, using:

W' W

,
Q2' Q2
Q2 Q2'
&
Q1 Q'1

M is a Carnot engine, so we are entitled to run it in reverse

This would be equivalent to:

T2 > T1
Q1
M

Q1
T1 < T2
This violates Clausius statement of the 2nd law!

Conversion of Heat to Work (a heat engine)

T2 > T1

T2 > T1

Q1

Q2 Q1

Q2

M'

Q1

Q1
T1 < T2

This violates Kelvin-Planck statement of the 2nd law!

The Clausius Inequality and the 2nd Law

Efficiency (*):

W
W
output

Q2 Q2
input

Q2 Q1

Q2
Q1
1
Q2

T1
1
T2

Heat reservoir at
temperature T2 > T1

or

T1 Q2Q1
Q1

T
Q2
Q2
Heat
2
Engine
Q Q
2

W Q2 Q1

T2 QT
11
Q2 Q1
orHeat reservoir
at 0
T2
T1

temperature T1 < T2

The Clausius Inequality and the 2nd Law

Divide any reversible cycle into a

series of thin Carnot cycles, where
the isotherms are infinitesimally
short:

Q2

Q1

We have proven that the entropy, S, is a state variable,

since the integral of the differential entropy (dS = dQ/T),
around a closed loop is equal to zero, i.e. the integration
of differential entropy is path independent!

The Clausius Inequality and the 2nd Law

Divide any reversible cycle into a

series of thin Carnot cycles, where
the isotherms are infinitesimally
short:

Q2

Q2 Q1

0
T2
T1

Q1

Qi
Qr
0
i T

T
i

There is one major caveat: the cycle must be reversible.

In other words, the above assumes only configuration
work (PdV) is performed.
If the cycle additionally includes dissipative work, it is
not clear how to include this in the above diagram.

Thermodynamic cycles for designing ideal engines

and heat pumps
http://auto.howstuffworks.com/engine1.htm
Engine process:

P (1.013 x 105) Pa

Pf

Work of engine :
B

Heat input to system : Q Qin Qout

Efficiency :

Pi

Vi

Vf

Weng W

Weng
Qin

Examples process by an ideal gas:

P (1.013 x 105) Pa

Pf

AB
Q
W

Pi

Eint

BC

Vf

DA

Vi ( Pf Pi )

Pf (V f Vi )

V f ( Pf Pi )

-Pi (V f Vi )

-1

-1

-1

-1

-Pf(Vf-Vi)

Pi(Vf-Vi)

Vi ( Pf Pi )

Pf (V f Vi )

V f ( Pf Pi )

-Pi (V f Vi )

-1

-1

-1

-1

Efficiency :
Vi

CD

Weng
Qin

Pi V f Vi

QAB QBC

Example from homework

Efficiency :

Weng
Qin

Pi V f Vi

QAB QBC

Also : W Weng Q Qin Qout

Qin Qout
Qout

1
Qin
Qin

QCD QDA
QAB QBC

Most efficient thermodynamic cycle -- Carnot

Sadi Carnot 1796-1832

Carnot cycle:
AB
BC
CD
DA

Isothermal at Th
Adiabatic
Isothermal at Tc
Adiabatic

Efficiency of Carnot cycle

Qin Qout
Qin
Tc
1
Th

Qout
Qin

iclicker exercise:
We discussed the efficiency of an engine as

Qin Qout
Qin

Qout
Qin

Is this result
A. Special to the Carnot cycle
B. General to all ideal thermodynamic cycles
iclicker exercise:
We discussed the efficiency of an engine running
with hot and cold reservoirs as
T
1 c
Th
Is this result
A. Special to the Carnot cycle
B. General to all ideal thermodynamic cycles

Note that for a Carnot cycle :

Qout
Qin

WAB
WCD

nRTc ln(VC / VD )

nRTh ln(VB / VA )

For adiabatic process

ThVB 1 TcVC 1
ThVA 1 TcVD 1
VC / VD VB / VA
Qout Tc

Qin
Th

iclicker exercise:
Why should we care about the Carnot
cycle?
A. We shouldnt
B. It approximately models some
heating and cooling technologies
C. It provides insight into another
thermodynamic variable -- entropy

The Otto cycle

Theoretical efficiency :
V2

1
V1

PHY 113 A Fall 2012 -- Lecture 32

11/19/2012

30

The Diesel cycle

Theoretical efficiency :
1 TD TA

1
TC TB

31

Engine vs heating/cooling designs