Chapter 12 - Thermodynamics

A PowerPoint Presentation by
Paul E. Tippens, Professor of Physics
Southern Polytechnic State University
2007
Modified: D. Uhrich
THERMODYNAMICS
Thermodynamics is
the study of energy
relationships that
involve heat,
mechanical work,
and other aspects of
energy and heat
transfer.
Central Heating
Bellwork 12/10
Define Thermodynamics your best
guess (break it down)
Objectives: After finishing this
unit, you should be able to:
State and apply the first and
second laws of thermodynamics.
Demonstrate your understanding
of adiabatic, isochoric, isothermal,
and isobaric processes.
Write and apply a relationship for determining
the ideal efficiency of a heat engine.
Write and apply a relationship for determining
coefficient of performance for a refrigeratior.
A THERMODYNAMIC SYSTEM
A system is a closed environment in
which heat transfer can take place. (For
example, the gas, walls, and cylinder of
an automobile engine.)
Work done on
gas or work
done by gas
INTERNAL ENERGY OF SYSTEM
The internal energy U of a system is the
total of all kinds of energy possessed by
the particles that make up the system.
Usually the internal energy consists
of the sum of the potential and
kinetic energies of the working gas
molecules.
TWO WAYS TO INCREASE THE
INTERNAL ENERGY, AU.
HEAT PUT INTO
A SYSTEM
(Positive)
+AU
WORK DONE
ON A GAS
(Positive)
WORK DONE BY
EXPANDING GAS:
AW is positive
-AU
Decrease
TWO WAYS TO DECREASE THE
INTERNAL ENERGY, AU.
HEAT LEAVES A
SYSTEM
AQ is negative
Q
out

hot
W
out
hot
THERMODYNAMIC STATE
The STATE of a thermodynamic
system is determined by four
factors:
Absolute Pressure P in
Pascals
Temperature T in Kelvins
Volume V in cubic meters
Number of moles, n, of working gas
THERMODYNAMIC PROCESS
Increase in Internal Energy, AU.
Initial State:
P
1
V
1
T
1
n
1
Final State:
P
2
V
2
T
2
n
2
Heat input
Q
in

W
out

Work by gas
The Reverse Process
Decrease in Internal Energy, AU.
Initial State:
P
1
V
1
T
1
n
1
Final State:
P
2
V
2
T
2
n
2
Work on gas
Loss of heat
Q
out

W
in

THE FIRST LAW OF
THERMODYAMICS:
The net heat put into a system is equal to
the change in internal energy of the
system plus the work done BY the system.
AQ = AU + AW A = (final - initial)
Conversely, the work done ON a system is
equal to the change in internal energy plus
the heat lost in the process.
SIGN CONVENTIONS
FOR FIRST LAW
Heat Q input is positive
AQ = AU + AW A = (final - initial)
Heat OUT is negative
Work BY a gas is positive
Work ON a gas is negative
+Q
in

+W
out

+AU
-W
in

-Q
out

AU
APPLICATION OF FIRST
LAW OF THERMODYNAMICS
Example 1: In the figure, the
gas absorbs 400 J of heat and
at the same time does 120 J
of work on the piston. What
is the change in internal
energy of the system?
AQ = AU + AW
Apply First Law:
Q
in
400 J
W
out
=120 J
Example 1 (Cont.): Apply First Law

AU = +280 J
Q
in
400 J
W
out
=120 J
AU = AQ - AW
= (+400 J) - (+120 J)
= +280 J
AW is positive: +120 J (Work OUT)
AQ = AU + AW
AU = AQ - AW
AQ is positive: +400 J (Heat IN)
Example 1 (Cont.): Apply First Law

AU = +280 J
The 400 J of input thermal
energy is used to perform
120 J of external work,
increasing the internal
energy of the system by
280 J
Q
in
400 J
W
out
=120 J
The increase in
internal energy is:
Energy is conserved:
FOUR THERMODYNAMIC
PROCESSES:
IsovolumetricProcess: AV = 0, AW = 0
Isobaric Process: AP = 0
Isothermal Process: AT = 0, AU = 0
Adiabatic Process: AQ = 0
AQ = AU + AW
AQ = AU + AW so that AQ = AU
IsovolumetricPROCESS:
CONSTANT VOLUME, AV = 0, AW = 0
0
+AU -AU
Q
IN
Q
OUT
HEAT IN = INCREASE IN INTERNAL ENERGY

HEAT OUT = DECREASE IN INTERNAL ENERGY
No Work
Done
IsovolumetricEXAMPLE:
Heat input
increases P
with const. V
400 J heat input increases
internal energy by 400 J
and zero work is done.
B
A
P
2
V
1
= V
2
P
1
P
A
P
B
T
A
T
B
=
400 J
No Change in
volume:
AQ = AU + AW But AW = P AV
ISOBARIC PROCESS:
CONSTANT PRESSURE, AP = 0
+AU -AU
Q
IN
Q
OUT
HEAT IN = W
out
+ INCREASE IN INTERNAL ENERGY

Work Out
Work
In
HEAT OUT = W
out
+ DECREASE IN INTERNAL ENERGY
ISOBARIC EXAMPLE (Constant Pressure):
Heat input
increases V
with const. P
400 J heat does 120 J of
work, increasing the
internal energy by 280 J.
400 J
B
A
P
V
1
V
2

V
A
V
B

T
A
T
B

=
ISOBARIC WORK
400 J
Work = Area under PV curve
Work PV = A
B A
P
V
1
V
2
V
A
V
B
T
A
T
B
=
P
A
= P
B

ISOTHERMAL PROCESS:
CONST. TEMPERATURE, AT = 0, AU = 0
NET HEAT INPUT = WORK OUTPUT
AQ = AU + AW AND AQ = AW
AU = 0
AU = 0
Q
OUT
Work
In
Work Out
Q
IN
WORK INPUT = NET HEAT OUT
ISOTHERMAL EXAMPLE (Constant T):
P
A
V
A
=

P
B
V
B
Slow compression at
constant temperature:
----- No change in U.
AU = AT = 0
B
A
P
A
V
2
V
1
P
B
ISOTHERMAL EXPANSION (Constant T):
400 J of energy is absorbed
by gas as 400 J of work is
done on gas.
AT = AU = 0
AU = AT = 0
B
A
P
A
V
A
V
B
P
B
P
A
V
A
= P
B
V
B
T
A
= T
B
ln
B
A
V
W nRT
V
=
Isothermal Work
AQ = AU + AW ; AW = -AU or AU = -AW
ADIABATIC PROCESS:
NO HEAT EXCHANGE, AQ = 0
Work done at EXPENSE of internal energy
INPUT Work INCREASES internal energy
Work Out
Work
In
AU
+AU
AQ = 0
AW = -AU
AU = -AW
ADIABATIC EXAMPLE:
Insulated
Walls: AQ = 0
B
A
P
A

V
1
V
2

P
B

Expanding gas does
work with zero heat
loss. Work = -AU
ADIABATIC EXPANSION:
400 J of WORK is done,
DECREASING the internal
energy by 400 J: Net heat
exchange is ZERO. AQ = 0
AQ = 0
B
A
P
A
V
A
V
B
P
B
P
A
V
A
P
B
V
B
T
A
T
B
=
A A B B
PV PV

=
SPECIFIC HEAT CAPACITY
Remember the definition of specific heat
capacity as the heat per unit mass
required to change the temperature?
For example, copper: c = 390 J/kgK
Q
c
m t
=
A
MOLAR SPECIFIC HEAT CAPACITY
The mole is a better reference for gases
than is the kilogram. Thus the molar
specific heat capacity is defined by:
For example, a constant volume of oxygen
requires 21.1 J to raise the temperature of
one mole by one kelvin degree.
C =
Q
n AT
REMEMBER, FOR ANY PROCESS
INVOLVING AN IDEAL GAS:
PV = nRT
AU = nCv AT
AQ = AU + AW
P
A
V
A
P
B
V
B
T
A
T
B
=
Example Problem:
AB: Heated at constant V to 400 K.
A 2-L sample of Oxygen gas has an initial temp-
erature and pressure of 200 K and 1 atm. The
gas undergoes four processes:
BC: Heated at constant P to 800 K.
CD: Cooled at constant V back to 1 atm.
DA: Cooled at constant P back to 200 K.
PV-DIAGRAM FOR PROBLEM
B
A
P
B
2 L
1 atm
200 K
400 K 800 K
How many moles
of O2 are present?
Consider point A:
PV = nRT
3
(101, 300Pa)(0.002m )
0.122 mol
(8.314J/mol K)(200K)
PV
n
RT
= = =

PROCESS AB: ISOCHORIC

What is the pressure
at point B?
P
A
P
B
T
A
T
B
=
1 atm

P
B
200 K

400 K
=
P
B
= 2 atm
or 203 kPa
B
A
P
B
2 L
1 atm
200 K
400 K 800 K
PROCESS AB: AQ = AU + AW
Analyze first law
for
Isovolumetricpr
ocess AB.
AW = 0
AQ = AU = nCv AT
AU = (0.122 mol)(21.1 J/mol K)(400 K - 200 K)
B
A
P
B
2 L
1 atm
200 K
400 K 800 K
AQ = +514 J AW = 0 AU = +514 J
PROCESS BC: ISOBARIC
What is the volume
at point C (& D)?
V
B
V
C
T
B
T
C
=
2 L

V
C
400 K

800 K
=
B
C
P
B
2 L
1 atm
200 K
400 K 800 K
D
4 L
V
C
= V
D
= 4 L
FINDING AU FOR PROCESS BC.
Process BC is
ISOBARIC.
AP = 0
AU = nCv AT
AU = (0.122 mol)(21.1 J/mol K)(800 K - 400 K)
AU = +1028 J
B
C
2 L
1 atm
200 K
400 K 800 K
4 L
2 atm
FINDING AW FOR PROCESS BC.
Work depends
on change in V.
AP = 0
Work = P AV
AW = (2 atm)(4 L - 2 L) = 4 atm L = 405 J
AW = +405 J
B
C
2 L
1 atm
200 K
400 K 800 K
4 L
2 atm
FINDING AQ FOR PROCESS BC.
Analyze first
law for BC.
AQ = AU + AW
AQ = +1028 J + 405 J
AQ = +1433 J
AQ = 1433 J AW = +405 J
B
C
2 L
1 atm
200 K
400 K 800 K
4 L
2 atm
AU = 1028 J
PROCESS CD: ISOCHORIC
What is temperature
at point D?
P
C
P
D
T
C
T
D
=
2 atm

1 atm
800 K

T
D
=
T
D
= 400 K
B
A
P
B
2 L
1 atm
200 K
400 K 800 K
C
D
PROCESS CD: AQ = AU + AW
Analyze first law
for
Isovolumetricpr
ocess CD.
AW = 0
AQ = AU = nCv AT
AU = (0.122 mol)(21.1 J/mol K)(400 K - 800 K)
AQ = -1028 J AW = 0 AU = -1028 J
C
D
P
B
2 L
1 atm
200 K
400 K
800 K
400 K
FINDING AU FOR PROCESS DA.
Process DA is
ISOBARIC.
AP = 0
AU = nCv AT
AU = (0.122 mol)(21.1 J/mol K)(400 K - 200 K)
AU = -514 J
A
D
2 L
1 atm
200 K
400 K 800 K
4 L
2 atm
400 K
FINDING AW FOR PROCESS DA.
Work depends
on change in V.
AP = 0
Work = P AV
AW = (1 atm)(2 L - 4 L) = -2 atm L = -203 J
AW = -203 J
A
D
2 L
1 atm
200 K
400 K 800 K
4 L
2 atm
400 K
FINDING AQ FOR PROCESS DA.
Analyze first
law for DA.
AQ = AU + AW
AQ = -514 J - 203 J
AQ = -717 J
AQ = -717 J AW = -203 J AU = -514 J
A
D
2 L
1 atm
200 K
400 K 800 K
4 L
2 atm
400 K
PROBLEM SUMMARY
AQ = AU + AW
For all
processes:
Process AQ AU AW
AB 514 J 514 J 0
BC 1433 J 1028 J 405 J
CD -1028 J -1028 J 0
DA -717 J -514 J -203 J
Totals 202 J 0 202 J


NET WORK FOR COMPLETE
CYCLE IS ENCLOSED AREA
B C
2 L
1 atm
4 L
2 atm
+404 J
B C
2 L
1 atm
4 L
2 atm
Neg
-202 J
Area = (1 atm)(2 L)
Net Work = 2 atm L = 202 J
2 L 4 L
B
C
1 atm
2 atm
ADIABATIC EXAMPLE:
AQ = 0
A
B
P
B
V
B
V
A
P
A
P
A
V
A
P
B
V
B
T
A
T
B
=
P
A
V
A
= P
B
V
B

Example 2: A diatomic gas at 300 K and
1 atm is compressed adiabatically, decreasing
its volume by 1/12. (V
A
= 12V
B
). What is the
new pressure and temperature? ( = 1.4)
ADIABATIC (Cont.): FIND P
B

AQ = 0
P
B
= 32.4 atm
or 3284 kPa
1.4
12
B
B A
B
V
P P
V
| |
=
|
\ .
1.4
(1atm)(12)
B
P=
P
A
V
A
= P
B
V
B

A
B
P
B
V
B
12V
B
1 atm
300 K Solve for P
B
:
A
B A
B
V
P P
V

| |
=
|
\ .
ADIABATIC (Cont.): FIND T
B

AQ = 0
T
B
= 810 K
(1 atm)(12V
B
)

(32.4 atm)(1 V
B
)
(300 K)

T
B
=
A
B
32.4 atm
V
B
12V
B
1 atm
300 K
Solve for T
B
T
B
=?
A A B B
A B
PV PV
T T
=
ADIABATIC (Cont.): If V
A
= 96 cm
3

and V
A
= 8 cm
3
, FIND AW
AQ = 0
AW = - AU = - nC
V
AT & C
V
= 21.1 j/mol K
A
B
32.4 atm
1 atm
300 K
810 K
Since AQ = 0,
AW = - AU
8 cm
3
96 cm
3
Find n from
point A
PV = nRT
PV
RT
n =
ADIABATIC (Cont.): If V
A
= 96 cm
3

and V
A
= 8 cm
3
, FIND AW
A
B
32.4 atm
1 atm
300 K
810 K
8 cm
3
96 cm
3
PV
RT
n =
=
(101,300 Pa)(8 x10
-6
m
3
)
(8.314 J/mol K)(300 K)
n = 0.000325 mol & C
V
= 21.1 j/mol K
AT = 810 - 300 = 510 K
AW = - AU = - nC
V
AT
AW = - 3.50 J
Absorbs heat Q
hot

Performs work W
out
Rejects heat Q
cold
A heat engine is any
device which through
a cyclic process:
Cold Res. T
C
Engine
Hot Res. T
H
Q
hot

W
out

Q
cold

HEAT ENGINES
THE SECOND LAW OF
THERMODYNAMICS
It is impossible to construct an
engine that, operating in a
cycle, produces no effect other
than the extraction of heat
from a reservoir and the
performance of an equivalent
amount of work.
Not only can you not win (1st law);
you cant even break even (2nd law)!
W
out

Cold Res. T
C
Engine
Hot Res. T
H
Q
hot

Q
cold

THE SECOND LAW OF
THERMODYNAMICS
Cold Res. T
C
Engine
Hot Res. T
H
400 J
300 J
100 J
A possible engine.
An IMPOSSIBLE
engine.
Cold Res. T
C
Engine
Hot Res. T
H
400 J
400 J
EFFICIENCY OF AN ENGINE
Cold Res. T
C
Engine
Hot Res. T
H
Q
H
W
Q
C
The efficiency of a heat engine
is the ratio of the net work
done W to the heat input Q
H
.
e = 1 -
Q
C
Q
H
e = =
W
Q
H
Q
H
- Q
C
Q
H
EFFICIENCY EXAMPLE
Cold Res. T
C
Engine
Hot Res. T
H
800 J
W
600 J
An engine absorbs 800 J and
wastes 600 J every cycle. What
is the efficiency?
e = 1 -
600 J
800 J
e = 1 -
Q
C
Q
H
e = 25%
Question: How many joules of work is done?
EFFICIENCY OF AN IDEAL
ENGINE (Carnot Engine)
For a perfect engine, the
quantities Q of heat gained
and lost are proportional to
the absolute temperatures T.
e = 1 -
T
C
T
H
e =
T
H
- T
C
T
H
Cold Res. T
C
Engine
Hot Res. T
H
Q
H

W
Q
C

Example 3: A steam engine absorbs 600 J
of heat at 500 K and the exhaust
temperature is 300 K. If the actual
efficiency is only half of the ideal efficiency,
how much work is done during each cycle?
e = 1 -
T
C
T
H
e = 1 -
300 K
500 K
e = 40%
Actual e = 0.5e
i
= 20%
e =
W
Q
H
W = eQ
H
= 0.20 (600 J)
Work = 120 J
REFRIGERATORS
A refrigerator is an engine
operating in reverse:
Work is done on gas
extracting heat from cold
reservoir and depositing
heat into hot reservoir.
W
in
+ Q
cold
= Q
hot
W
IN
= Q
hot
- Q
cold
Cold Res. T
C
Engine
Hot Res. T
H
Q
hot
Q
cold
W
in
THE SECOND LAW FOR
REFRIGERATORS
It is impossible to construct a
refrigerator that absorbs heat
from a cold reservoir and
deposits equal heat to a hot
reservoir with AW = 0.
If this were possible, we could
establish perpetual motion!
Cold Res. T
C
Engine
Hot Res. T
H
Q
hot
Q
cold
COEFFICIENT OF PERFORMANCE
Cold Res. T
C
Engine
Hot Res. T
H
Q
H
W
Q
C
The COP (K) of a heat
engine is the ratio of the
HEAT Q
c
extracted to the
net WORK done W.
K =
T
H
T
H
- T
C
For an IDEAL
refrigerator:
Q
C

W
K = =
Q
H
Q
H
- Q
C
COP EXAMPLE
A Carnot refrigerator operates
between 500 K and 400 K. It
extracts 800 J from a cold
reservoir during each cycle.
What is C.O.P., W and Q
H
?
Cold Res. T
C
Eng
ine
Hot Res. T
H
800 J
W
Q
H
500 K
400 K
K =
400 K

500 K - 400 K
T
C
T
H
- T
C
=
C.O.P. (K) = 4.0
COP EXAMPLE (Cont.)
Next we will find Q
H
by
assuming same K for actual
refrigerator (Carnot).
Cold Res. T
C
Eng
ine
Hot Res. T
H
800 J
W
Q
H
500 K
400 K
K =
Q
C
Q
H
- Q
C
Q
H
= 1000 J
800 J

Q
H
- 800 J
= 4.0
COP EXAMPLE (Cont.)
Now, can you say how much
work is done in each cycle?
Cold Res. T
C
Engine
Hot Res. T
H
800 J
W
1000 J
500 K
400 K
Work = 1000 J - 800 J
Work = 200 J
Summary
AQ = AU + AW A = (final - initial)
The First Law of Thermodynamics: The net
heat taken in by a system is equal to the
sum of the change in internal energy and
the work done by the system.
IsovolumetricProcess: AV = 0, AW =
0
Isobaric Process: AP = 0
Isothermal Process: AT = 0, AU = 0
Adiabatic Process: AQ = 0
Summary (Cont.)
c =
Q
n AT
AU = nC
v
AT
The Molar
Specific Heat
capacity, C:
Units are:Joules
per mole per
Kelvin degree
The following are true for ANY process:
AQ = AU + AW
PV = nRT
Summary (Cont.)
The Second Law of Thermo: It is
impossible to construct an engine
that, operating in a cycle,
produces no effect other than the
extraction of heat from a reservoir
and the performance of an
equivalent amount of work.
Cold Res. T
C
Engine
Hot Res. T
H
Q
hot
Q
cold
W
out
Not only can you not win (1st law);
you cant even break even (2nd law)!
Summary (Cont.)
The efficiency of a heat engine:
e = 1 -
Q
C
Q
H
e = 1 -
T
C
T
H
The coefficient of performance of a refrigerator:
C C
in H C
Q Q
K
W Q Q
= =

C
H C
T
K
T T
=

CONCLUSION: Chapter 20
Thermodynamics