The Laws of Thermodynamics

Chapter 12
Principles of Thermodynamics
Energy is conserved
o FIRST LAW OF THERMODYNAMICS
o Examples: Engines (Internal -> Mechanical)
Friction (Mechanical -> Internal)
All processes must increase entropy
o SECOND LAW OF THERMODYNAMICS
o Entropy is measure of disorder
o Engines can not be 100% efficient

Converting Internal Energy to
Mechanical
V P Q U A = A
Work done by expansion
A V x PA F x F W / , , A = A = A =
V P W A =
Example
A cylinder of radius 5 cm is kept at pressure with a piston
of mass 75 kg.

a) What is the pressure inside the
cylinder?
b) If the gas expands such that the
cylinder rises 12.0 cm, what work was
done by the gas?
c) What amount of the work went into
changing the gravitational PE of the
piston?
d) Where did the rest of the work go?
Solution
Given: M =75, A = t0.05
2
, Ax=0.12, P
atm
= 1.013x10
5
Pa
a) Find P
gas
atm gas
P
A
Mg
P + =
= 1.950x10
5
Pa
b) Find W
gas
V P W A =
x A P W A =
gas
= 183.8 J
c) Find W
gravity
mgh W =
= 88.3 J
d) Where did the other
work go?
Compressing the outside air
Quiz Review
A massive copper piston traps an ideal
gas as shown to the right. The piston is
allowed to freely slide up and down and
equilibrate with the outside air. Pick the
most correct statement?


A. The pressure is higher inside the
cylinder than outside.
B. The temperature inside the cylinder
is higher than outside the cylinder.
C. If the gas is heated by applying a
flame to cylinder, and the piston comes to a new
equilibrium, the inside pressure will have increased.
D. All of the above.
E. A and C.
Some Vocabulary
Isobaric
o P = constant


Isovolumetric
o V = constant


Isothermal
o T = constant


Adiabatic
o Q = 0
P
P
P
P
V
V
V
V
A massive piston traps an amount of
Helium gas as shown. The piston freely
slides up and down.
The system initially equilibrates at
room temperature (a)
Weight is slowly added to the piston,
isothermally compressing the gas to
half its original volume (b)

A. P
b
( > < = ) P
a
B. T
b
( > < = ) T
a
C. W
ab
( > < = ) 0

D. U
b
( > < = ) U
a
E. Q
ab
( > < = ) 0
Outside Air: Room T, Atm. P
Vocabulary: W
ab
is work done by gas between a and b
Q
ab
is heat added to gas between a and b
Example
V P W
V P Q U
A =
A = A
A massive piston traps an amount of
Helium gas as shown. The piston freely
slides up and down.
The system initially equilibrates at
room temperature (a)
Weight is slowly added to the piston,
adiabatically compressing the gas to
half its original volume (b)

A. P
b
( > < = ) P
a
B. W
ab
( > < = ) 0

C. Q
ab
( > < = ) 0
D. U
b
( > < = ) U
a
E. T
b
( > < = ) T
a

Outside Air: Room T, Atm. P
Vocabulary: W
ab
is work done by gas between a and b
Q
ab
is heat added to gas between a and b
Example
V P W
V P Q U
A =
A = A
A massive piston traps an amount of
Helium gas as shown. The piston freely
slides up and down.
The system initially equilibrates at
room temperature (a)
The gas is cooled, isobarically
compressing the gas to half its
original volume (b)

A. P
b
( > < = ) P
a
B. W
ab
( > < = ) 0

C. T
b
( > < = ) T
a

D. U
b
( > < = ) U
a
E. Q
ab
( > < = ) 0


Outside Air: Room T, Atm. P
Vocabulary: W
ab
is work done by gas between a and b
Q
ab
is heat added to gas between a and b
Example
V P W
V P Q U
A =
A = A
nRT PV =
Work from closed cycles
Consider cycle A -> B -> A
W
A->B

-W
B->A

Work from closed cycles
Consider cycle A -> B -> A
W
A->B->A
= Area
Work from closed cycles
Reverse the cycle, make it counter clockwise
-W
B->A

W
A->B

Example
a) What amount of work is
performed by the gas in the
cycle IAFI?



b) How much heat was
inserted into the gas in the
cycle IAFI?



c) What amount of work is
performed by the gas in the
cycle IBFI?
area enclosed = W
W
IAFI
= 3P
atm
= 3.04x10
5
J
W Q U = A
AU = 0

W = -3.04x10
5
J
Q = 3.04x10
5
J
V (m
3
)
One More Example
Consider a monotonic ideal
gas which expands according
to the PV diagram.

a) What work was done by
the gas from A to B?
b) What heat was added to
the gas between A and B?
c) What work was done by
the gas from B to C?
d) What heat was added to
the gas beween B and C?
e) What work was done by
the gas from C to A?
f) What heat was added to
the gas from C to A?
V (m
3
)
P (kPa)
25
50
75
0.2 0.4 0.6
A
B
C
Solution
a) Find W
AB




b) Find Q
AB

V (m
3
)
P (kPa)
25
50
75
0.2 0.4 0.6
A
B
C
W
AB
= Area

= 20,000 J
First find U
A
and U
B
PV U
nRT PV
nRT U
2
3
2
3
: Gas Monotonic
=
=
=
U
A
= 22,500 J, U
B
= 22,500 J, AU = 0
Finally, solve for Q
W Q U = A
Q = 20,000 J
Solution
c) Find W
BC




d) Find Q
BC

V (m
3
)
P (kPa)
25
50
75
0.2 0.4 0.6
A
B
C
W
AB
= -Area

= -10,000 J
First find U
B
and U
C
PV U
2
3
=
U
B
= 22,500 J, U
C
= 7,500 J, AU = -15,000
Finally, solve for Q
W Q U = A
Q = -25,000 J
Solution
e) Find W
CA




f) Find Q
CA

V (m
3
)
P (kPa)
25
50
75
0.2 0.4 0.6
A
B
C
W
AB
= Area

= 0 J
First find U
C
and U
A
PV U
2
3
=
U
C
= 7,500 J, U
A
= 22,500 J, AU = 15,000
Finally, solve for Q
W Q U = A
Q = 15,000 J
Continued Example
Take solutions from last problem and find:

a) Net work done by gas in the cycle
b) Amount of heat added to gas
W
AB
+ W
BC
+ W
CA
= 10,000 J
Q
AB
+ Q
BC
+ Q
CA
= 10,000 J
This does NOT mean that the engine is 100% efficient!
Give Quiz
Entropy
Measure of Disorder of the system
(randomness, ignorance)
S = k
B
log(N)
N = # of possible arrangements for fixed E and Q
p
x
p
y
Entropy
Total Entropy always rises!
(2nd Law of Thermodynamics)
Adding heat raises entropy
T Q S / = A
Defines temperature in Kelvin!
Why does Q flow from hot to cold?
Consider two systems, one with T
A
and one with T
B

Allow Q > 0 to flow from T
A
to T
B

Entropy changed by:

AS = Q/T
B
- Q/T
A


If T
A
> T
B
, then AS > 0

System will achieve more randomness by exchanging
heat until T
B
= T
A


Efficiencies of Engines
Consider a cycle described by:
W, work done by engine
Q
hot
, heat that flows into engine from
source at T
hot

Q
cold
, heat exhausted from engine at
lower temperature, T
cold

Efficiency is defined:

Q
hot
engine
Q
cold
W
hot
Q
W
e =
: engine
hot
cold hot
Q
Q Q
=
Since ,
hot
cold
Q
Q
=1
> >
hot
cold
hot
cold
hot
hot
cold
cold
T
T
Q
Q
T
Q
T
Q
0 / > = A T Q S
hot
cold
engines
T
T
e <1
:
Carnot Engines
Idealized engine
Most efficient possible
hot
cold
hot
T
T
Q
W
e = = 1
Carnot Cycle
Example
An ideal engine (Carnot) is rated at 50% efficiency when it is
able to exhaust heat at a temperature of 20 C. If the
exhaust temperature is lowered to -30 C, what is the new
efficiency.
Given, e=0.5 when T
cold
=293 K, Find e when T
cold
= 243 K

hot
cold
T
T
e =1
e
T T
cold hot

=
1
1
= 586 K
Solution
First, find T
hot

Now, find e given T
hot
=586 K and T
cold
=243 K
hot
cold
T
T
e =1
e = 0.585
Refrigerators
Q
hot
engine
Q
cold
W
Given: Refrigerated region is at T
cold

Heat exhausted to region with T
hot
Find: Efficiency
W
Q
e
cold
=
: or refrigerat
1 /
1

=
cold hot cold hot
cold
Q Q Q Q
Q
0 / > = A T Q S Since ,
> >
cold
hot
cold
hot
cold
cold
hot
hot
T
T
Q
Q
T
Q
T
Q
1 /
1
: or refrigerat

<
cold hot
T T
e
Note: Highest efficiency for small T differences
Heat Pumps
Q
hot
engine
Q
cold
W
Given: Inside is at T
hot

Outside is at T
cold
Find: Efficiency
W
Q
e
hot
=
: pump heat
hot cold cold hot
hot
Q Q Q Q
Q
/ 1
1

=
0 / > = A T Q S Since ,
> >
cold
hot
cold
hot
cold
cold
hot
hot
T
T
Q
Q
T
Q
T
Q
hot cold
T T
e
/ 1
1
: pump heat

<
Like Refrigerator: Highest efficiency for small AT
Example
A modern gas furnace can work at practically 100%
efficiency, i.e., 100% of the heat from burning the gas
is converted into heat for the home. Assume that a
heat pump works at 50% of the efficiency of an ideal
heat pump.

If electricity costs 3 times as much per kw-hr as gas,
for what range of outside temperatures is it
advantageous to use a heat pump?
Assume T
inside
= 295 K.
Solution
Find T for which e = 3 for heat pump.
Above this T: use a heat pump
Below this T: use gas
hot cold
T T
e
/ 1
1
: pump heat

<
295 / 1
1
5 . 0 3
T
e

= =
C 27 - K 8 . 245
6
5
295 = = = T
50% of ideal heat pump
Give Quiz