Chapter 20 Thermodynamics

A PowerPoint Presentation by
Paul E. Tippens, Professor of
Physics
Southern Polytechnic State
2007
University

Thermodyna
mics is the
study
of
THERMODYNAMICS
energy
relationships
that involve
heat,
mechanical
work, and
other
Central Heating
aspects of

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, U.

+ U
WORK DONE
ON A GAS
(Positive)

HEAT PUT INTO

A SYSTEM
(Positive)

TWO WAYS TO DECREASE THE

INTERNAL ENERGY, U.
Wout
out

ho
t

Qout
-U
Decreas
e

WORK DONE
BY EXPANDING
GAS: W is
positive

ho
t

HEAT LEAVES A
SYSTEM
Q is
negative

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,
U.
Wout
Qin

Initial
State:
P1 V1 T1 n1

Heat input
Work by gas

Final State:
P2 V2 T2 n2

The Reverse Process

Decrease in Internal Energy,
U.
Win
Qout

Initial
State:
P1 V1 T1 n1

Work on gas
Loss of
heat

Final State:
P2 V2 T2 n2

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.

Q = U + W

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
Work BY a gas is
positive
Work ON a gas is
negative
Heat OUT is negative
Q = U + W

+Wout

+Qin

U
-Win

U
-Qout

final - initial)

APPLICATION OF FIRST
LAW OF
THERMODYNAMICS

Example 1: In the figure,

Wout =120
the gas absorbs 400 J of
J
heat and at the same time
does 120 J of work on the
piston. What is the
change in internal energy Qin
of the system?
400 J

Apply First Law:

Q = U + W

Example 1 (Cont.): Apply First

Law
Q is positive: +400 J (Heat IN)
W is positive: +120 J (Work
OUT)

Q = U + W
U = Q - W

U = Q - W
= (+400 J) - (+120 J)
= +280 J

Wout =120 J

Qin
400 J

U = +280 J

Example 1 (Cont.): Apply First

Law
Energy is
conserved:
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

The increase in
internal energy
is:

Wout =120 J
Qin
400 J

U = +280 J

FOUR THERMODYNAMIC
PROCESSES:
Isochoric
Isochoric Process:
Process:
00

V
V =
= 0,
0, W
W =
=

Isobaric
Isobaric Process:
Process:

P
P =
= 00

Isothermal
Isothermal Process:
Process: T
T =
= 0,
0, U
U =
=
00
Adiabatic
Q
Adiabatic Process:
Process:
Q =
= 00
Q = U + W

ISOCHORIC PROCESS:
CONSTANT VOLUME, V = 0, W =
0 0
Q = U + W

so that

Q = U

QIN
+U

QOUT

No Work
Done

-U

HEAT IN = INCREASE IN INTERNAL ENERGY

HEAT OUT = DECREASE IN INTERNAL ENERGY

ISOCHORIC EXAMPLE:
No Change in
volume:

P1

PA
TA

PB
TB

V1= V2
400 J
Heat input
increases P
with const.
V

400 J heat input

increases internal
energy by 400 J and
zero work is done.

ISOBARIC PROCESS:
CONSTANT PRESSURE, P = 0
Q = U + W

But

W = P V

QIN
+U

QOUT

Work
Out

-U

Work
In

HEAT IN = Wout + INCREASE IN INTERNAL ENERGY

HEAT OUT = Wout + DECREASE IN INTERNAL ENERGY

ISOBARIC EXAMPLE (Constant

Pressure):
P

VA
TA

400 J

Heat input
increases V
with const.
P

V1

VB
TB

V2

400 J heat does 120 J

of work, increasing
the internal energy by
280 J.

ISOBARIC WORK
P

VA
TA

400 J

V1

V2

TB

PA = P B

Work = Area under PV curve

Work P V

VB

ISOTHERMAL PROCESS:
CONST. TEMPERATURE, T = 0, U
=0
Q = U + W
W
QIN

U =
0

Work
Out

ANDQ =
QOUT
U = 0

Work
In

NET HEAT INPUT = WORK OUTPUT

WORK INPUT = NET HEAT OUT

ISOTHERMAL EXAMPLE (Constant

T):
PA

A
B

PB

U = T =
0
PAVA =
PBVB

V2

V1

Slow compression at
constant
temperature: ----No change in U.

ISOTHERMAL EXPANSION (Constant

T):
PA

PB

U = T = 0

VA
VB

400 J of energy is
absorbed by gas as 400
J of work is done on gas.
T = U = 0

PAVA = PBVB
TA = TB

Isothermal
Work

VB
W nRT ln
VA

ADIABATIC PROCESS:
NO HEAT EXCHANGE, Q = 0

Q = U + W ; W = -U or U = -W
U = -W

W = -U
U

Work
Out
Q =

+U

Work
In

Work done at EXPENSE of internal energy

INPUT Work INCREASES internal energy

ADIABATIC EXAMPLE:
PA

A
B

PB
V1

Insulated
Walls: Q =
0

Expanding gas
does work with
zero heat loss.
Work = -U

V2

ADIABATIC EXPANSION:
PA

PB

PAVA
TA

PBVB
TB

Q = 0

VA
VB
400 J of WORK is done,
DECREASING the
internal energy by 400
J: Net heat exchange is
ZERO. Q = 0

A A

B B

PV PV

MOLAR HEAT CAPACITY

OPTIONAL TREATMENT

The molar heat capacity C is defined

as the heat per unit mole per Celsius
degree.
Check
Check with
with your
your instructor
instructor
to
to see
see ifif this
this more
more
thorough
thorough treatment
treatment of
of
thermodynamic
thermodynamic processes
processes
is
is required.
required.

SPECIFIC HEAT CAPACITY

Remember the definition of specific
heat capacity as the heat per unit
mass required to change the
temperature?

Q
c
m t
For example, copper: c = 390 J/kgK

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:
Q
C=
n T
For example, a constant volume of
oxygen requires 21.1 J to raise the
temperature of one mole by one kelvin
degree.

SPECIFIC HEAT CAPACITY

CONSTANT VOLUME
How much heat is required
to raise the temperature of 2
moles of O2 from 0oC to
100oC?

Q = nCv T
Q = (2 mol)(21.1 J/mol K)(373 K - 273 K)
Q = +4220 J

SPECIFIC HEAT CAPACITY

CONSTANT VOLUME (Cont.)

Since the volume has not

changed, no work is done.
The entire 4220 J goes to
increase the internal energy,
U.

Q = U = nCv T = 4220 J
U = nCv T

Thus, U is determined by the

change of temperature and the

specific heat at constant volume.

SPECIFIC HEAT CAPACITY

CONSTANT PRESSURE
We have just seen that 4220 J
of heat were needed at
constant volume. Suppose we
want to also do 1000 J of work
at constant pressure?

Q = U + W
Q = 4220 J + J
Q = 5220 J

Same
Cp >
Cv

HEAT CAPACITY (Cont.)

Heat to raise
temperature of an ideal
gas, U, is the same
for any process.

U = nCvT
For constant pressure

Q = U + W
nCpT = nCvT + P V

Cp > Cv

Cp
Cv

REMEMBER, FOR ANY

PROCESS INVOLVING AN
IDEAL GAS:
PV = nRT

Q = U + W

PAVA
TA

PBVB
TB

U = nCv T

Example Problem:
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:
AB: Heated at constant V to 400 K.
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
How many
moles of O2 are
present?
Consider point
A: PV = nRT

PB
1 atm

400
K

800
K

200
K

A
2
L

PV (101, 300Pa)(0.002m 3 )
n

0.122 mol
RT (8.314J/mol K)(200K)

PROCESS AB: ISOCHORIC

What is the
pressure at point
B?
PA P B
=
TA T B
1 atm
PB
=
200 K 400 K

PB

400
K
200
K

1 atm

800
K

2
L

P B = 2 atm
or

203 kPa

PROCESS AB: Q = U + W
Analyze first
law for
ISOCHORIC
process
W = 0AB.

PB
1 atm

400
K
200
K

Q = U = nCv T

800
K

2
L

U = (0.122 mol)(21.1 J/mol K)(400 K - 200 K)

Q = +514 J

U = +514 J

W = 0

PROCESS BC: ISOBARIC

What is the
volume at point C
(& D)?
VB V C
=
TB T C
2L

VC

=
400 K 800 K

PB

400
K

800
K C

200
K

1 atm
2
L

D
4
L

VC = VD = 4 L

FINDING U FOR PROCESS

BC.
Process BC
is
ISOBARIC.

P = 0

2 atm

400
K
200
K

1 atm

U = nCv T

800
K C

2
L

4
L

U = (0.122 mol)(21.1 J/mol K)(800 K - 400 K)

U = +1028 J

FINDING W FOR PROCESS

BC.
Work
depends on
change in V.

P = 0

Work = P V

2 atm

400
K

800
K C

200
K

1 atm
2
L

4
L

W = (2 atm)(4 L - 2 L) = 4 atm L = 405 J

W = +405 J

FINDING Q FOR PROCESS

BC.
Analyze
first law for
BC.

2 atm

Q = U + W

400
K

Q = +1433 J
U = 1028 J

800
K C

200
K

1 atm

Q = +1028 J + 405 J

Q = 1433 J

2
L

4
L

W = +405 J

PROCESS CD: ISOCHORIC

What is
temperature at
point D?
PC P D
=
TC T D
2 atm 1 atm
=
800 K
TD

PB
1 atm

400
K
200
K

A
2
L

T D = 400 K

800
K C
D

PROCESS CD: Q = U + W
Analyze first
law for
ISOCHORIC
process
W = 0CD.

PB

400
K
200
K

1 atm

Q = U = nCv T

800
K

C
400
DK

2
L

U = (0.122 mol)(21.1 J/mol K)(400 K - 800 K)

Q = -1028 J

U = -1028 J

W = 0

FINDING U FOR PROCESS

DA.
Process DA
is
ISOBARIC.

P = 0

U = nCv T

400
K

2 atm
1 atm

800
K

200
K

A
2
L

400
DK
4
L

U = (0.122 mol)(21.1 J/mol K)(400 K - 200 K)

U = -514 J

FINDING W FOR PROCESS

DA.
Work
depends on
change in V.

P = 0

400
K

2 atm
1 atm

200
K

Work = P V

800
K

2
L

400
DK
4
L

W = (1 atm)(2 L - 4 L) = -2 atm L = -203 J

W = -203 J

FINDING Q FOR PROCESS

DA.
Analyze
first law for
DA.

Q = U + W

2 atm
1 atm

Q = -514 J - 203 J
Q = -717 J
Q = -717 J

400
K

U = -514 J

800
K

200
K

A
2
L

400
DK
4
L

W = -203 J

PROBLEM SUMMARY
For all
Q
=
U
+
W
processes:
Process

AB

514 J

514 J

BC

1433 J

1028 J

405 J

CD

-1028 J -1028 J

DA

-717 J

-514 J

-203 J

Totals

202 J

202 J

NET WORK FOR

COMPLETE CYCLE IS
ENCLOSED
AREA
+404 J
B

2 atm

1 atm

2
atm
1
atm

2 atm

B -202 J C
Neg

1 atm

2
L

4
L

2
L

4
L

Area = (1 atm)(2 L)
Net Work = 2 atm L = 202 J

ADIABATIC EXAMPLE:
Example 2: A diatomic gas at 300 K and
1 atm is compressed adiabatically, decreasing
its volume by 1/12. (VA = 12VB). What is the
new pressure and temperature? ( = 1.4)
PB

Q = 0

VB

PAVA

PBVB

PAVA = PBVB
A

PA

VA

TA

TB

ADIABATIC (Cont.): FIND PB

B

PB

Q = 0

PAVA = PBVB
300 K

1
atm

12VB
PB PA

VB

A
VB 12VB

Solve for
PB:
VA
PB PA

V
B

1.4

PB (1 atm)(12)

1.4

PB = 32.4 atm
or 3284 kPa

ADIABATIC (Cont.): FIND TB

32.4
atm

Q = 0

1
atm

B TB=?
300 K

A
VB 12VB

PAVA PBVB

TA
TB

Solve for
TB

(1 atm)(12VB) (32.4 atm)(1 VB)

=
(300 K)
TB
TB = 810 K

ADIABATIC (Cont.): If VA= 96 cm3

and VA= 8 cm3, FIND W
32.4
atm

Q = 0

810 K
300 K

1
atm

A
8 cm3

96 cm3

W = - U = - nCV T &
K
Find n
from point
A

PV = nRT

Since Q =
0,
W = - U

CV= 21.1 j/mol

n=

PV
RT

ADIABATIC (Cont.): If VA= 96 cm3

and VA= 8 cm3, FIND W
PV (101,300 Pa)(8 x10-6 m3)
=
n=
RT
(8.314 J/mol K)(300 K)
n = 0.000325 mol &

T = 810 - 300 = 510 K

W = - U = - nCV T
W = - 3.50 J

CV= 21.1 j/mol K

32.4
atm

810 K
300 K

1
atm

A
8 cm3

96 cm3

HEAT ENGINES
Hot Res. TH

Qhot

Engin
e

Qcold

Cold Res.
TC

Wout

A heat engine is
any device which
through a cyclic
process:

Absorbs heat Qhot

Performs work
Wout
Rejects heat Qcold

THE SECOND LAW OF

THERMODYNAMICS
Hot Res.
TH

Qhot

Engine

Qcold

Wout

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.
TC
Not only can you not win (1st
law); you cant even break even
(2nd law)!

THE SECOND LAW OF

THERMODYNAMICS
Hot Res. TH

400 J

100 J

Engin
e

300 J
Cold Res. TC

A possible engine.

Hot Res. TH

400 J
Engin
e

400 J

Cold Res. TC

An IMPOSSIBLE
engine.

EFFICIENCY OF AN ENGINE
Hot Res. TH

QH

Engin
e

QC

Cold Res.
TC

The efficiency of a heat

engine is the ratio of the
net work done W to the
heat input QH.
QH- QC
W
e=
=
QH
QH
e=1-

QC
QH

EFFICIENCY EXAMPLE
Hot Res.
TH

800 J

Engin
e

600 J

Cold Res.
TC

An engine absorbs 800 J

and wastes 600 J every
cycle. What is the
efficiency?
QC
e=1QH
e=1-

600 J
800 J

e = 25%

Question: How many joules of work is done?

EFFICIENCY OF AN IDEAL
ENGINE (Carnot Engine)
Hot Res.
TH

QH
QC

Engin
e

Cold Res.
TC

For a perfect engine, the

quantities Q of heat
gained and lost are
proportional to the
absolute temperatures T.
T H- T C
e=
TH
e=1-

TC
TH

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=1e=1-

TC

Actual e = 0.5ei = 20%

TH

300 K
500 K

e = 40%

e=

QH

W = eQH = 0.20 (600 J)

Work = 120 J

REFRIGERATORS
Hot Res. TH

Qhot
Engin
e

Qcold

Cold Res.
TC

Win

A refrigerator is an
engine operating in
reverse: Work is done
on gas extracting heat
from cold reservoir and
depositing heat into
hot reservoir.

Win + Qcold = Qhot

WIN = Qhot - Qcold

THE SECOND LAW FOR

REFRIGERATORS
Hot Res.
TH

Qhot

Engin
e

Qcold

Cold Res.
TC

It is impossible to
construct a refrigerator
that absorbs heat from a
cold reservoir and
deposits equal heat to a
hot reservoir with W =
0.
If this were possible, we
could establish perpetual
motion!

COEFFICIENT OF
PERFORMANCE
Hot Res. TH

QH
QC

W
Engin
e

Cold Res.
TC

For an
IDEAL
refrigerator:

The COP (K) of a heat

engine is the ratio of
the HEAT Qc extracted
to the net WORK done
W.
QH
QC
K=
=
QH- QC
W
TH
K = THTC

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

400 K

C.O.P. (K) = 4.0

COP EXAMPLE (Cont.)

Next we will find QH by
500 K
assuming same K for
Hot Res.
actual refrigerator
TH
QH
W (Carnot).
QC
En
gin
K=
QH- QC
e
800 J
800
J
Cold Res.
4.0
=
TC
QH - 800 J
400 K
QH = 1000 J

COP EXAMPLE (Cont.)

500 K
Hot Res. TH

1000 J

Engin
e

Now, can you say how

much work is done in
each cycle?
Work = 1000 J - 800 J

800 J

Cold Res.
TC

400 K

Work = 200 J

Summary
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.
Q = U + W
final - initial)
Isochoric Process:
0

V = 0, W =

Isobaric Process:

P = 0

Isothermal Process: T = 0, U =
0

Summary (Cont.)
Units
The Molar
Q
are:Joules per c =
Specific
n T
mole per
Heat
capacity, C: Kelvin degree
The following are true for ANY process:

Q = U + W

PAVA PBVB

TA
TB

U = nCv T

PV = nRT

Summary (Cont.)
Hot Res.
TH

Qhot

Engin
e

Wout

Qcold

Cold Res.
TC

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.

Not only can you not win (1st

law); you cant even break even
(2nd law)!

Summary (Cont.)
The efficiency of a heat engine:
QC
e=1- Q
H

e=1-

TC
TH

The coefficient of performance of a

refrigerator:

QC
QC
K

Win QH QC

TC
K
TH TC

CONCLUSION: Chapter 20
Thermodynamics