Thermodynamics Chapter 15
Dec 26, 2015
Thermodynamics
Chapter 15
Expectations
After this chapter, students will: Recognize and apply the four laws of
thermodynamics Understand what is meant by thermodynamic
terms Recognize and distinguish among four kinds of
thermal processes Distinguish between reversible and irreversible
processes
Expectations
After this chapter, students will: Analyze the properties and operations of heat
engines Calculate the changes in entropy associated with
thermal processes
Thermodynamics: Some Fundamentals
Thermodynamics is the study of the economy of heat energy and mechanical work, in the context of the ideal gas.
Understanding thermodynamic concepts and mathematical relationships depends on understanding some terms.
Systems and Their Boundaries
In mechanics, we introduced the idea of the system: a user-defined collection of objects.
In thermodynamics, “system” still means that. However, we add the notion that the system will usually include some definite amount of a fluid – typically, an ideal gas. It might also include other elements, such as the fluid’s container. It’s always important to be clear about what’s in the system, and what isn’t.
Systems and Their Boundaries
Once we have decided what the system is, we can say that the surroundings consists of everything that isn’t the system.
The system is separated from its surroundings by walls. If the walls do not allow heat to pass through them, they are adiabatic walls. If heat can pass freely through the walls, we call them diathermal walls.
The State of a System
The characteristics that tell us what we want to know about a system define its condition, or state.
If the system consists of some amount of an ideal gas, we’ll be interested in the temperature, pressure, volume, and mass of the gas. Those quantities are the state variables of the system.
Common Sense: 0th Law of ThermodynamicsSuppose we have three systems: A, B, and C.
Suppose that A is in thermal equilibrium with C. Suppose also that B is in thermal equilibrium with C.
Then: A is in thermal equilibrium with B, and no heat will flow between them if they are in contact.
(C is intended to be a thermometer.)
Energy Conservation: 1st Law of Thermodynamics
Mathematical statement:
What does this mean?
U is the change in the system’s internal energy
Uf is the system’s final internal energy
U0 is the system’s initial internal energy
Q is the heat added to the system
W is the work done by the system
WQUUU f 0
Energy Conservation: 1st Law of Thermodynamics
Think of U as being the system’s bank balance, and think of work and energy and heat as being forms of cash. What we’ve said is that the change in the system’s balance is its income (heat) minus its spending (work).
WQUUU f 0
Thermal Processes
A process is how the system, and its surroundings, change from one state to another.
We’re going to consider four special cases of thermal processes. These special cases help us to understand what the laws of thermodynamics tell us about systems and their properties.
Thermal Processes
In every case, we assume that the process occurs “slowly.” The technical term for “occurs slowly” is quasi-static.
What does “slowly” mean? It means that the system has time to mix during the process. At all times, we consider the temperature and the pressure of the system to be uniform (the same in all places throughout the system).
Isobaric Process
Isobaric: the pressure of the system is constant.
The result first:
Why should this be?
0VVPVPW f
Isobaric Process
Consider an ideal gas to which heat is added.
But A·S = V = Vf – Vi :
PASSFW
if VVPVPW
Isobaric Process
This process can be represented graphically, plotting pressure vs. volume. Notice that the work is the area under this plot (P times V).
Isochoric Process
Isochoric: the volume of the system is constant.
The result:
Why? If volume is constant, nothing moves. No motion, no work. Any heat added to the system only changes its internal energy.
QWQUW 0
Isochoric Process
Pressure-volume plot for an isochoric process:
No area under the plot means no work is done.
Isothermal Process
Isothermal: the temperature of the system is constant. Use the ideal gas equation to write P as a function of V:
Because P is not constant, V
nRTP
nRTPV
VPW
Isothermal Process
The work is still the area under the isotherm plot. To calculate it, we integrate:
i
f
V
V
V
VnRTW
dVV
nRTW
i
f
ln
(natural log)
Adiabatic Process
In an adiabatic process, no heat enters or leaves the system:
Q = 0. The First Law becomes:
But, as we learned in chapter 14,
(for a monatomic ideal gas).
WWQU
nRTU2
3
Adiabatic Process
If , then
and
so
WWQU
TnRU 2
3
fi TTnRTnRW 2
3
2
3
nRTU2
3
fi TTnRW 2
3
(monatomic ideal gas)
Adiabatic Process
Notice that the adiabatic curve is different from both isotherms (corresponding to the initial and final temperatures).
Its equation is:
where
ffii VPVP
V
P
c
c
specific heat capacity @ constant pressure
specific heat capacity @ constant volume
Specific Heat Capacities
Define a molar specific heat capacity, C, for an ideal gas: Q = C n T
First Law:
At constant pressure (isobaric):
WUQWQU
if VVPVPW
(SI units: J / mol·K)
Specific Heat Capacities
Substitute for Vi and Vf from the ideal gas equation:
For a monatomic ideal gas:
Substitute:
ifif TTnRVVPWP
nRTV
if TTnRU 2
3
ififif TTnRTTnRTTnRWUQ 2
5
2
3
Specific Heat Capacities
Equate this expression for Q to the one from our defining equation for molar heat capacity:
TnRTTnRQ if 2
5
2
5
RCTCnTnRQ P 2
5
2
5
Specific Heat Capacities
At constant volume (isochoric):
RC
TnRWUTCnQ
W
V 2
32
3
0
Specific Heat Capacities
A couple of things to note:
(for a monatomic ideal gas)
3
5
2
32
5
R
R
C
C
V
P
RRRCC VP 2
3
2
5
Second Law of Thermodynamics
Heat flows spontaneously from regions of higher temperature to regions of lower temperature. It does not flow spontaneously in the other direction.
Set your cup of hot coffee down on the sidewalk tonight. Come back and get it in after a few minutes. It won’t be hotter.
Second Law and Heat Engines
As heat flows from a hotter region to a colder one, a device can be constructed that will use some of that heat to do mechanical work.
Such a device is called a heat engine.
Heat Engines
A familiar example: internal combustion (auto) engine.
Hot reservoir: burning fuel-air mixture
Cold reservoir: exhaust gases
Heat Engines: Energy Conservation
The principle of energy conservation requires:
CH QWQ
Heat Engines: Efficiency
Efficiency is defined as the ratio of the work done by the heat engine to the input heat it receives.
Efficiency is a dimensionless, unitless ratio.
H
C
H
CH
H Q
Q
Q
Q
We 1
Efficiency and Reversibility
A process is called reversible if both the system and its environment can be returned, after the process, to exactly the same states they were in before the process.
reversible
irreversible
Efficiency and Reversibility
No process involving friction is reversible.
Also, any process in which heat flows spontaneously from a hot to a cold reservoir is irreversible. The system can be restored to its original state, but the work required changes the environment further from its original state.
Carnot’s Principle
No irreversible heat engine operating between two reservoirs at constant temperatures can be more efficient than a reversible engine operating between the same temperatures. All reversible engines operating between the same two temperatures have the same efficiency.
Sadi Nicolas Leonard Carnot
1796 – 1832
French military engineer
Efficiency of a Carnot Engine
If a thermodynamic temperature scale is correctly defined, the ratio of the heat into the cold reservoir to the heat from the hot reservoir is equal to the ratio of the reservoir temperatures:
Lord Kelvin defined his thermodynamic temperature scale so that this is true. The temperatures in the above equation must be absolute (in Kelvins).
H
C
H
C
T
T
Q
Q
Efficiency of a Carnot Engine
Earlier, we said that the efficiency of a heat engine is
Substituting from the previous equation:
This is true for a Carnot engine. Notice that we are assuming that the reservoir temperaures are not changed by the operation of the engine.
H
CC T
Te 1
H
C
Q
Qe 1
A Different Kind of Reversibility
A heat engine diverts some of the heat flowing spontaneously from hot to cold, and uses it to generate output work.
If we are willing to input work, then we can cause heat to flow from cold to hot. (Heat pump, refrigerator.) Notice that this reverse operation is not the same thing as thermodynamic reversibility.
Heat Pumps and Refrigerators
Conservation of energy applies to heat pumps as well as to heat engines: QH = W + QC
For a thermodynamically-reversible heat pump or refrigerator:
Refrigerator: coefficient of performance
H
C
H
C
T
T
Q
Q
W
QCeperformanc of coeff.
Entropy
Entropy: the loss of our ability to use heat to perform work, because of the irreversible spontaneous flow of heat from higher to lower temperatures.
If heat flows into or out of a system reversibly, the system’s change in entropy is
T
QS SI units: J / K
Entropy and Reversible Engines
The change in entropy associated with the operation of a Carnot engine:
hot reservoir cold reservoir
total change:
H
HH T
QS
C
CC T
QS
H
H
C
C
H
H
C
Ctotal T
Q
T
Q
T
Q
T
QS
Entropy and Reversible EnginesBut Carnot’s principle said that
So, the total change in entropy associated with the operation of a Carnot engine is
So: the operation of a reversible engine does not change the total entropy of the universe. Irreversible processes increase the entropy of the universe.
0C
C
C
C
H
H
C
Ctotal T
Q
T
Q
T
Q
T
QS
H
H
C
C
H
C
H
C
T
Q
T
Q
T
T
Q
Q
Energy Unavailable for Doing Work
Consider a reversible engine working between reservoir temperatures of 650K and 150K.
Its efficiency:
If 1200 J of heat are drawn from
the hot reservoir, the work is
0.769 K 650
K 15011
H
CC T
Te
J 923J 1200769.0 HeQW
Energy Unavailable for Doing Work
Now we provide a path for our 1200 J of heat to flow irreversibly from the 650K reservoir to a cooler one, at 350K. Now our engine’s efficiency becomes:
0.571 K 350
K 15011
H
CC T
Te
Energy Unavailable for Doing Work
At this decreased efficiency, the work done by this 1200 J of heat is:
The work done by this heat in descending from 650 K to 150 K has decreased by 923 J – 685 J, or 238 J.
J 685J 1200571.0 HeQW
Energy Unavailable for Doing Work
We can also calculate this loss of work by calculating the increase in the entropy of the universe associated with the irreversible part of the heat flow:
J/K 1.582 K 650
J 1200
K 350
J 1200
K 650K 350650350
KKuniverse
QQS
Energy Unavailable for Doing Work
Then apply Eq. 15.19 from your textbook to calculate the energy unavailable for work:
The irreversible flow causes this.
J 237J/K 1.582K) (150
0
eunavailabl
universeeunavailabl
W
STW