First Law of

Thermodynamics
„ The First Law of Thermodynamics tells
Chapter 12 us that the internal energy of a system
can be increased by
„ Adding energy to the system
„ Doing work on the system
The Laws of Thermodynamics
∆U = Q + W
(Part 2)
„ There are many processes through
which these could be accomplished
„ As long as energy is conserved

1 2

Work in a Gas Cylinder PV Diagrams

„ A force is applied to „ Used when the
slowly compress the pressure and volume
gas
„ The compression is
are known at each
slow enough for all step of the process
the system to remain
essentially in thermal
„ Work done on gas =
equilibrium Area under PV curve
„ W = - P ∆V „ This is true whether
„ This is the work done or not the pressure
on the gas stays constant

3 4

Types of Thermal PV diagram: Isothermal

Processes and Adiabatic processes
„ Isobaric
„ Pressure stays constant „ Adiabatic
„ Horizontal line on the PV diagram
Q=const
„ Isovolumetric „ Isothermal
T=const
„ Volume stays constant
„ Vertical line on the PV diagram „ Work can be
found from PV
„ Isothermal
diagram as an
Temperature stays the same
„
area under the
„ Adiabatic graph
„ No heat is exchanged with the surroundings
5 6

1
 First Law of
Thermodynamics
„ Energy conservation law
„ Relates changes in internal energy
to energy transfers due to heat
and work
„ Applicable to all types of processes
„ Provides a connection between
microscopic and macroscopic
worlds
7 8
∆U in Isovolumetric process
„ At V=const work W=0, therefore ∆U=Q
„ For ideal gas U=(3/2)nRT
„ Introduce molar specific heat at constant
volume for an ideal gas
„ Cv = 3/2 R
„ The change in internal energy can be
expressed as
∆U = nCv∆T
„ n is number of moles
9 10
Isolated System
„ An isolated system does not
interact with its surroundings
„ No energy transfer takes place and
no work is done
„ Therefore, the internal energy of
the isolated system remains
constant
11
Results of ∆U
„ First Law of thermodynamics provides a
connection between microscopic and
macroscopic worlds
„ Changes in the internal energy result in
changes in the measurable macroscopic
variables of the system
„ These include
Pressure
„
„ Temperature
„ Volume
Degrees of Freedom
„ Each way a gas can store energy is
called a degree of freedom
„ Each degree of freedom contributes
½ R to the molar specific heat
„ Cv = 3/2 R for mono-atomic gas (3
translational degrees of freedom)
„ In addition, gas can also have vibrational
and rotational degrees of freedom
Cyclic Processes
„ A cyclic process is one in
which the process
originates and ends at
the same state
„ Uf = Ui and Q = -W
„ The net work done per
cycle by the gas is equal
to the area enclosed by
the path representing the
process on a PV diagram
12
2
 Heat Engine Heat Engine, cont.
„ A heat engine takes in energy „ Since it is a cyclical
by heat and partially converts process, ∆U = 0
it to other forms „ Its initial and final internal
energies are the same
„ Energy is transferred from a „ Therefore, Qnet = Weng
source at a high temperature „ The work done by the
(Qh) engine equals the net
„ Work is done by the engine energy absorbed by the
(Weng) engine
„ Energy is expelled to a source „ The work is equal to the
at a lower temperature (Qc) area enclosed by the
curve of the PV diagram

13 14

Thermal Efficiency of a Heat Pumps and

Heat Engine
„ Thermal efficiency is defined as the
ratio of the work done by the engine to
the energy absorbed at the higher
temperature
Refrigerators
„ Heat engines can run in reverse
„ Energy is extracted from the cold reservoir
by work done on the heat pump
Energy is transferred to the hot reservoir
„

„ This process means the heat engine is

W Q − Qc Q running as a heat pump
e ≡ eng = h =1− c
Qh Qh Qh „ A refrigerator is a common type of heat
pump (coolant is compressed, increasing its
„ e = 1 (100% efficiency) only if Qc = 0 temperature)
„ No energy expelled to cold reservoir „ An air conditioner is another example of a
heat pump (energy is removed from cool air)
15 16

Heat Pump, cont Heat Pump, COP

Qc
„ The work is what „ In cooling mode, COP =
you pay for W
„ The Qc is the desired QH
benefit „ In heating mode, COP =
„ The coefficient of
W
performance (COP)
measures the „ The higher the number, the better
performance of the „ A good refrigerator or air
heat pump running conditioner typically has a COP of
in cooling mode
5 or 6
17 18

3
 Second Law of Summary of the First and
Thermodynamics Second Laws
„ No heat engine operating in a „ First Law
cycle can absorb energy from a „ We cannot get a greater amount of
reservoir and use it entirely for the energy out of a cyclic process than
performance of an equal amount we put in
of work
„ Second Law
„ Kelvin – Planck statement
„ Means that Qc cannot equal 0 „ We can’t break even
„ Some Qc must be expelled to the
environment
„ Means that e must be less than 100%
19 20

Reversible and Irreversible

Processes
„ A reversible process is one in which every
state along some path is an equilibrium
state
„ And one for which the system can be returned
to its initial state along the same path
„ An irreversible process does not meet
these requirements
„ Most natural processes are irreversible
„ Reversible process are an idealization, but
some real processes are good
approximations
21
Carnot Engine
„ A theoretical engine developed by French
engineer Sadi Carnot
„ A heat engine operating in an ideal,
reversible cycle (now called a Carnot
Cycle) between two reservoirs is the
most efficient engine possible
„ Carnot’s Theorem: No real engine
operating between two energy reservoirs
can be more efficient than a Carnot
engine operating between the same two
reservoirs
22

Carnot Cycle
Carnot Cycle, A to B
„ A to B is an isothermal
expansion at
temperature Th
„ The gas is placed in
contact with the high
temperature reservoir
„ The gas absorbs heat
Qh
„ The gas does work WAB
in raising the piston

23 24

4
 Carnot Cycle, B to C Carnot Cycle, C to D
„ B to C is an adiabatic „ The gas is placed in
expansion contact with the cold
„ The base of the temperature reservoir
cylinder is replaced at temperature Tc
by a thermally „ C to D is an isothermal
nonconducting wall
compression
„ No heat enters or
leaves the system „ The gas expels energy
QC
„ The temperature
falls from Th to Tc „ Work WCD is done on
„ The gas does work the gas
WBC
25 26

Carnot Cycle, D to A Carnot Cycle, PV Diagram

„ D to A is an adiabatic „ The work done by
compression
the engine is
„ The gas is again placed
against a thermally shown by the
nonconducting wall area enclosed by
„ So no heat is exchanged the curve
with the surroundings
„ The temperature of the „ The net work is
gas increases from TC to equal to Qh - Qc
Th
„ The work done on the
gas is WCD
27 28

Efficiency of a Carnot Notes About Carnot

Engine Efficiency
„ Carnot showed that the efficiency of the „ Efficiency is 0 if Th = Tc
engine depends on the temperatures of „ Efficiency is 100% only if Tc = 0 K
the reservoirs Such reservoirs are not available
TC „

ec = 1 − „ The efficiency increases as Tc is

Th
„ Temperatures must be in Kelvins
„ All Carnot engines operating between
the same two temperatures will have
the same efficiency
29
lowered and as Th is raised
„ In most practical cases, Tc is near
room temperature, 300 K
„ So generally Th is raised to increase
efficiency
30

5
Real Engines Compared to
Carnot Engines Example: Problem #32
„ All real engines are less efficient „ Tc = 80o C
than the Carnot engine „ Th = 350o C
„ Real engines are irreversible because „ Qh = 21000 J
of friction
„ Real engines are irreversible because
„ t=1s
they complete cycles in short
amounts of time Pout - ? Weng TC
„
ec = = 1−
„ Qc -? Qh Th
31 32

Entropy Entropy, cont.

Q
„ A state variable related to the Second „ Mathematically, ∆S = r
Law of Thermodynamics, the entropy T
„ This applies only to the reversible path,
„ Let Qr be the energy absorbed or even if the system actually follows an
expelled during a reversible, constant irreversible path
temperature process between two
To calculate the entropy for an irreversible
equilibrium states. Then the change in
„

process, model it as a reversible process

entropy during any constant
temperature process connecting the two „ When energy is absorbed, Q is positive
equilibrium states can be defined as the and entropy increases
ratio of the energy to the temperature „ When energy is expelled, Q is negative
and entropy decreases
33 34

More About Entropy Perpetual Motion Machines

„ Note, the equation defines the change „ A perpetual motion machine would operate
in entropy continuously without input of energy and
„ The entropy of the Universe increases without any net increase in entropy
in all natural processes „ Perpetual motion machines of the first type
„ This is another way of expressing the Second Law of would violate the First Law, giving out
Thermodynamics more energy than was put into the
„ There are processes in which the machine
entropy of a system decreases „ Perpetual motion machines of the second
„ If the entropy of one system, A, decreases it will be type would violate the Second Law,
accompanied by the increase of entropy of another possibly by no exhaust
system, B.
The change in entropy in system B will be greater
„ Perpetual motion machines will never be
invented
„
than that of system A. 35 36

6
 Entropy and Disorder Example: Problem#37
„ Entropy can be described in terms „ m = 70 kg
of disorder „ h = 25 m
„ A disorderly arrangement is much „ T = 300 K
more probable than an orderly one
if the laws of nature are allowed to Qr
act without interference „ ∆S -? ∆S =
T
„ This comes from a statistical
mechanics development

37 38

Entropy and Disorder, Heat Death of the

cont.
„ Isolated systems tend toward greater
disorder, and entropy is a measure of that
disorder
„ S = kB ln W
„ kB is Boltzmann’s constant
„ W is a number proportional to the probability that
the system has a particular configuration
„ This gives the Second Law as a statement of
what is most probable rather than what must
be
The Second Law also defines the direction of
„
time of all events as the direction in which the
entropy of the universe increases
39
Universe
„ The entropy of the Universe always
increases
„ The entropy of the Universe should
ultimately reach a maximum
„ At this time, the Universe will be at a state
of uniform temperature and density
„ This state of perfect disorder implies no
energy will be available for doing work
„ This state is called the heat death of the
Universe
40

The First Law and Human

Metabolism Measuring Metabolic Rate
„ The First Law can be applied to living „ The metabolic rate is related to
organisms oxygen consumption by
„ The internal energy stored in humans ∆U ∆Vo2
goes into other forms needed by the = 4.8
organs and into work and heat ∆t ∆t
„ The metabolic rate (∆U / ∆T) is directly „ About 80 W is the basal metabolic
proportional to the rate of oxygen rate, just to maintain and run
consumption by volume different body organs

41 42

7
Various Metabolic Rates Aerobic Fitness
„ One way to
measure a
person’s physical
fitness is their
maximum
capacity to use or
consume oxygen

43 44

Efficiency of the Human

Body

„ Efficiency is the ratio of the mechanical

power supplied to the metabolic rate or
total power input
45