Lecture #3 1

Lecture 3
Objectives: Students will be able to:
1. Describe the rst law in terms of heat and work interactions.
2. Describe the second law in terms of adiabatic and reversible processes.
3. Identify the dierence between internal and total energy.
4. Identify specialized thermodynamic equations and tell when they can be applied.
5. Describe ideal gas thermodynamic properties.
1. Heat, work and the rst law.
We observe that for a closed system the only way to change the energy of a system is by heat
and work interactions with the system. We write the dierential rst law as
dE = w +Q
where E is the total energy of the system. Note that dE is an exact dierential, whereas w
and Q are inexact. The integrated form is
E = w +Q
For an adiabatic process E = w
ad
and Q = 0, so w
ad
is path independent, but you could
also take a dierent path to get the same E, so w
ad
= w

+Q

.
Likewise, if the work interactions are zero then there must be some path independent heat
interaction,
dE = Q
rev
where Q
rev
is the reversible heat.
Now suppose that the whole system is translating and accelerating:
w = w
stationary
+mgy
. .
PE
+
m
2
(v
2
2
v
2
1
)
. .
KE
So,
E PE KE
. .
state function
= w
stationary
+Q
Dene the internal energy U = EPEKE so that U is also a state function, then,
U = w
stationary
+Q
Lecture #3 2
2. The second law.
Why does a basket ball bounce? If I drop a basket ball from a height of 1 m, will it return
to the same height when it bounces? Why not? Analyze the basket ball bounce in terms of
the rst law:
U + PE + KE = w +Q
We are converting potential and kinetic energy into internal energy of the gas molecules in the
ball, and the material of the ball, along with heat and work. The rst law does not preclude
the ball bouncing to the same height, and bouncing forever. However, we observe that this
never happens. Likewise, you can drop a weight into water and convert the potential energy of
the weight into internal energy of the water, however, we never observe the converse, although
the rst law says that it is possible. Hence the need for the second law of thermodynamics.
There is a directionality to spontaneous processes, this directionality gives rise to another
state function, which we call entropy.
We dene entropy as
dS =
Q
rev
T
the dierential entropy is the reversible heat divided by the absolute temperature. Note
that reversible heat requires that there be no temperature gradients, just as reversible work
required no force imbalances.
The second law can be written as
dS = dS
sys
+dS
surr
0
The Clausius statement of the second law: Heat cannot be converted into an equal amount
of work through a cyclical process.
Proof: For a cyclical process U = 0 and S = 0. Add heat to the system reversibly, then
extract work from the system reversibly and adiabatically.
U = 0 = Q
rev
+w
ad
w
ad
= Q
rev
OK, by 1st law. Now check second law
S = S
rev
+ S
ad
= 0
but S
ad
= 0 and S
rev
= Q
rev
/T = 0, so the second law is violated.
3. Generalized equations:
(a) Closed system, no translations
dU = Q+w
Lecture #3 3
(b) Open systems
dE = Q+W +

in
__

H
in
+gz
in
+
v
2
in
2
_
m
in
_

out
__

H
out
+gz
out
+
v
2
out
2
_
m
out
_
where
dE = d
_
U +mgz +
mv
2
2
_
(c) Steady state, d[ ]
cv
= 0

i
m
i
_

H
i
+
v
2
i
2
+gy
i
_
= Q+w
(d) Compressors & turbines (pressure change work)
H = Q+w
s
where w
s
is shaft work.
(e) Throttling devices (pressure drop)
H = Q
(f) Nozzles (KE P)

H =
1
2
(v
2
2
v
2
1
)
(g) Heat exchangers
H = Q
4. Ideal Gas State Properties

U =

U(T)
_

U
T
_
V
=

C
V

H =

H(T)
_

H
T
_
p
=

C
p

C
p
=

C
V
+R
=

C
p

C
V
Both

C
p
and

C
V
are only functions of temperature.
Lecture #3 4
5. Open system example: Filling a storage tank. A storage tank is pressurized by rapid lling
from a much larger storage reservoir. The tank is well-insulated. The tank volume is 2 m
3
and the gas in the tank is initially at 1 bar and 280 K. The air in the reservoir is at 100 bar
and 300 K. What is the temperature of the gas in the tank when the pressure reaches 5 bar?
Approach: This is an open system with negligible change in kinetic and potential energy.
There is one inlet stream and no outlet streams. Heat and work interactions are zero.
dE = dU =

H
in
n
in
,
with

H
in
a constant and n
in
= dn.
dU = nd

U +

Udn =

H
in
n.
We can rearrange this to
d

H
in

U
=
dn
n
.
We can integrate this between states 1 and 2:
ln
_

H
in

U
_

U
2

U
1
= lnn|
n
2
n
1
ln
_

H
in

U
1

H
in

U
2
_
= ln
_
n
2
n
1
_
.
Rearranging and assuming ideal gas behavior of the air,

H
in

U
1

H
in

U
2
=
n
2
n
1
=
P
2
V
2
RT
2
RT
1
P
1
V
1
=
P
2
T
1
P
1
T
2
.
Let us assume that the heat capacities are constant. The enthalpy and internal energy
can then be written as referenced to some temperature T
0
.

H =

H
0
+

C
P
(T T
0
) and

U =

U
0
+

C
V
(T T
0
). We can now write

H
in

U
1
=

H
0
+

C
P
(T
in
T
0
)
_

U
0
+

C
V
(T
1
T
0
)
_
=

H
0

U
0
+

C
P
T
in

C
V
T
1

_

C
P


C
V
_
T
0
But,

H
0

U
0
= P

V = RT
0
and

C
P

C
V
= R, for an ideal gas. Therefore,

H
0

U
0
RT
0
= 0,
and

H
in

U
1
=

C
P
T
in

C
V
T
1
Therefore,

C
P
T
in

C
V
T
1

C
P
T
in

C
V
T
2
=
P
2
T
1
P
1
T
2
.
Lecture #3 5
Solving for T
2
,
_

C
P
T
in

C
V
T
1
_
P
1
T
2
=
_

C
P
T
in

C
V
T
2
_
P
2
T
1
T
2
_
P
1
_

C
P
T
in

C
V
T
1
_
+P
2
T
1

C
V
_
= P
2
T
1

C
P
T
in
T
2
=
(P
2
/P
1
) T
1
T
in

T
in
T
1
+ (P
2
/P
1
) T
1
where =

C
P
/

C
V
. Using

C
V
= 5/2R and = 1.4 we get T
2
= 381.8 K. The number of
moles at this point is n =
P
2
V
RT
2
= 315 moles.