Thermodynamics II

The First Law of Thermodynamics

Heat and Work. First Law of Thermodynamics

Heat and Work on Quasi-Static Processes for a Gas.

The Second Law of Thermodynamics

Heat Engines and the Second Law of Thermodynamics

Refrigerators and the Second Law of Thermodynamics

The Carnot Engine

Heat Pumps

Irreversibility and disorder. Entropy

References: Tipler; wikipedia,

The First Law of Thermodynamics

Energy exists in many forms, such as mechanical energy, heat,
light, chemical energy, and electrical energy. Energy is the
ability to bring about change or to do work.
Thermodynamics is the study of energy.

Surroundings
System
The frontier of the system is
arbitrarily chosen

The system can interchange mass and energy

through the frontier with the environment.
An example of closed system - no mass flow- is
the gas confined in a cylinder. The frontier in this
case physical- is made by the cylinder and the
piston walls.

The First Law of Thermodynamics

First Law of Thermodynamics Conservation of Energy:
Energy can be changed from one form to another, but it cannot be created or
destroyed. The total amount of energy and matter in the Universe remains
constant, merely changing from one form to another.

The First Law of Thermodynamics (Conservation) states that energy is

always conserved, it cannot be created or destroyed. In essence,
energy can be converted from one form into another.
The energy balance of a system as a consequence of FLT- is a
powerful tool to analyze the interchanges of energy between the system
and its environment.
We need to define the concept of internal energy of the system, Eint as
an energy stored in the system.
Warning: It is no correct to say that a system has a large amount of
heat or a great amount of work
http://www.emc.maricopa.edu/faculty/farabee/BIOBK/BioBookEner1.html

The First Law of Thermodynamics. Heat, Work and Internal Energy

Joules Experiment and the First Law of Thermodynamics.
Equivalence between work and heat

1 calorie = 4.184 Joules

Work is done on water. The energy is transferred to
the water i. e. the system- . The energy transferred
appears as an increment of temperature.
We can replace the insulating walls by conducting
walls. We can transfer heat through the walls to the
system to produce the same increment of temperature.

Schematic diagram for Joules

experiment. Insulating walls to
prevent heat transfer enclose water.
As the weights fall at constant speed,
they turn a paddle wheel, which does
work on water.
If friction in mechanism is negligible,
the work done by the paddle wheel
on the water equal the change of
potential energy of the weights.

The increment of temperature of the system reflects the

increase of Internal Energy. Internal energy is a
function of state of the system

The sum of the heat transfer into the

system and the work done on the
system equals the change in the
internal energy of the system

Eint Qin Won

The First Law of Thermodynamics

Another method of
doing work.
Electrical work is
done on the
system by the
generator, which is
driven by the
falling weight.

The First Law of Thermodynamics. Application to a particular case:

A gas confined in a cylinder with a movable piston

The state of the gas will be
described by the Ideal Gas-Law.

PV n R T
How the confined gas
interchange energy (heat and
work) with the surroundings?.
What is the value of the internal
energy for the gas in the cylinder
First Law

Eint Qin Won

dEint Qin Won

How can we calculate the

energy heat and/or worktransferred, added of
subtracted, to the system?

Quasi static processes: a type of processes where the gas moves through a
series of equilibrium states. Then, we can apply the IGL. In practice, if we move
slowly the piston, will be possible to approximate quasi-static processes fairly well.

First Law of Thermodynamics. Fluxes of energy and mass on the earth

surface. Energy balance.
Rn = Rns + Rnl

ET

CO2

Energy fluxes:
Rn :

Net gain of heat energy from

radiation
ET
Latent heat, Energy associated to
the flux of water vapor leaving from
D
the system

Ph
Ph

Net fluxes of mass

Water
vapor

Ph: Net photosynthesis

H Sensible Heat.
Eint: Change
of the internal energy of the system
G Heat energy by conduction to the
D: Advection
soil
Energy balance (applying First Law):

Rn H ET G D - Ph = Eint

The First Law of Thermodynamics. Application to a particular case:

A gas confined in a cylinder with a movable piston. Internal Energy

Internal Energy for an Ideal Gas.

Only depends on the temperature of the
gas, and not of its volume or pressure
Experiment: Free expansion.
For a gas at low density an
ideal gas-, a free expansion does not
change the temperature of the gas.

What is the value of the internal

energy for the gas in the cylinder?

If heat is added at constant volume, no work

is done, so the heat added equals the
increase of thermal energy

Eint Qin
Qin CV T
and

dEint CV dT n cV dT
Internal Energy is a state function, i.e. it is not dependent on the
process, only it depends of the initial and final temperature

The First Law of Thermodynamics. Application to a particular case:

A gas confined in a cylinder with a movable piston. Heat

Heat transferred to a system

If heat is added at constant

pressure the heat energy
transferred will be used to
expand the substance and to
increase the internal energy.

QP CP T
QP CP dT

If the substance expands, it

does work on its surroundings.
If heat is added at constant
volume, no work is done, so
the heat added equals the
increase of thermal energy

Qin ,V CV dT n cV dT
Qin ,V CV T n cV T

Applying the First Law of Thermodynamics

dEint QP Won CP dT PdV

PdV (CP CV ) dT
as d ( PV ) PdV dP V

and

P const dP 0

CP CV n R
The expansion is usually negligible for solids
and liquids, so for them CP ~ CV.

The First Law of Thermodynamics. Application to a particular case:

A gas confined in a cylinder with a movable piston

Heat transferred to a system. A summary

Heat energy can be added (or lost) to the system. The value of the heat
energy transferred depends of the process.

Ideal Gas

Typical processes are

- At constant volume

QV CV T ; QV CV dT

- At constant pressure

QP C P T ; QP C P dT

For the case of ideal gas

CP CV n R

From the Kinetic theory,

for
monoatomic gases
for biatomic gases

Relationship of Mayer

3
3
J
CV n R; cV R 12.47
2
2
mol K
5
5
J
CV n R cV R 20.79
2
2
mol K

For solids and liquids, as the expansion at constant pressure is usually

negligible CP ~ CV.

Adiabatic: A process in which no heat flows into or out of a system is

called an adiabatic process. Such a process can occur when the system is
extremely well insulated or when the process happens very quickly.

The First Law of Thermodynamics. Application to a particular case:

A gas confined in a cylinder with a movable piston. Work

Work done on the system, Won , is the energy transferred as work to the system.
When this energy is added to the system its value will be positive.
The work done on the gas in an
expansion is
V2

Won gas P dV
V1

Won gas Wby gas

P- V diagrams
Constant pressure
V2

Won gas P dV P (V1 V2 )

V1

If 5 L of an ideal gas at a pressure of 2 atm is cooled

so that it contracts at constant pressure until its
volume is 3 l, what is the work done on the gas?
[405.2 J]

The First Law of Thermodynamics. P-V diagrams

P- V diagrams

Conecting an initial state and a final state

by three paths
Constant pressure

Isothermal

V2

Won gas P dV P(V1 V2 )

V1

V2

Constant Volume

Won gas P dV 0
V1

V2

Constant Temperature

Won gas

V1

n RT
V2
dV n R T ln
V
V1

The First Law of Thermodynamics

A biatomic ideal gas undergoes a cycle starting at
point A (2 atm, 1L). Process from A to B is an
expansion at constant pressure until the volume is 2.5
L, after which is cooled at constant volume until its
pressure is 1 atm. It is then compressed at constant
pressure until the volume is again 1L, after which it is
heated at constant volume until it is back in its original
state. Find (a) the work, heat and change of internal
energy in each process (b) the total work done on the
gas and the total heat added to it during the cycle.
A system consisting of 0.32 mol of a monoatomic ideal gas
occupies a volume of 2.2 L, at a pressure of 2.4 atm.
The system is carried through a cycle consisting:
1. The gas is heated at constant pressure until its volume
is 4.4L.
2. The gas is cooled at constant volume until the pressure
decreased to 1.2 atm
3. The gas undergoes an isothermal compression back to
initial point.
(a) What is the temperature at points A, B and C
(b) Find W, Q and Eint for each process and for the entire
cycle

The First Law of Thermodynamics. Processes. P-V

Diagrams

Adiabatic Processes. No heat flows into or out of the system

The First Law of Thermodynamics. Processes. P-V

Diagrams

Adiabatic Processes. No heat flows into or out of the system

Qin 0
Adiabatic process
then Eint Won ,adiabatic n cV T
The equation of curve describing the adiabatic
process is

CP
P V const ;
CV
T V 1 const
T P1 const

A quantity of air is compressed adiabatically

and quasi-statically from an initial pressure of
1 atm and a volume of 4 L at temperature of
20C to half its original volume. Find (a) the
final pressure, (b) the final temperature and (c)
the work done on the gas.
cP = 29.19 J/(molK); cV = 20.85 J/
(molK). M=28.84 g

adiabatic coefficient

We can use the ideal gas to rewrite

the work done on the gas in an
adiabatic process in the form

Won gas ,adiab

Pf V f Pi Vi

The First Law of Thermodynamics. Processes. P-V

Diagrams

A polytropic process is a thermodynamic process that obeys the relation:

PVn = C,
where P is pressure, V is volume, n is any real number (the polytropic index), and C is a
constant. This equation can be used to accurately characterize processes of certain systems,
notably the compression or expansion of a gas, but in some cases, possibly liquids and solids.

For certain indices n, the process will be synonymous with other processes:
if n = 0, then PV0=P=const and it is an isobaric process (constant pressure)
if n = 1, then for an ideal gas PV= const and it is an isothermal process (constant
temperature)
if n = = cp/cV, then for an ideal gas it is an adiabatic process (no heat transferred)
if n = , then it is an isochoric process (constant volume)

The First Law of Thermodynamics.

Cyclic Processes. P-V

Diagrams

Two moles of an ideal monoatomic gas have an initial pressure P 1 = 2 atm and an initial
volume V1 = 2 L. The gas is taken through the following quasi-static cycle:
A.- It is expanded isothermally until it has a volume V2 = 4 L.
B.- It is then heated at constant volume until it has a pressure P 3= 2 atm
C.- It is then cooled at constant pressure until it is back to its initial state.
(a) Show this cycle on a PV diagram. (b) Calculate the head added and the work done by
the gas during each part of the cycle. (c) Find the temperatures T1, T2, T3

Solve the above problem considering the STEP A is an adiabatic

expansion. Determine the efficiency of the both cycles. Determine the
efficiency of a Carnot cycle operating between the temperature extremes
of the both cycles..

The First Law of Thermodynamics.

Cyclic Processes. P-V

Diagrams

The First Law of Thermodynamics.

Cyclic Processes. P-V

Diagrams

At point D in figure the pressure and temperature of

2 mol of an ideal monoatomic gas are 2 atm and
360 K. The volume of the gas at point B on the PV
diagram is three times that at point D and its
pressure is twice that a point C. Paths AB and DC
represent isothermal processes. The gas is carried
through a complete cycle along the path DABCD.
Determine the total work done by the gas and the
heat supplied to the gas along each portion of the
cycle

The First Law of Thermodynamics.

Cyclic Processes. P-V

Diagrams

The First Law of Thermodynamics.

Cyclic Processes. P-V

Diagrams

Second Law of Thermodynamics. Heat Engines

Heat Engines and the Second Law of
Thermodynamics
Refrigerators and the Second Law of
Thermodynamics
The Carnot Engine
Heat Pumps
Irreversibility and disorder. Entropy

A steamboat or steamship, sometimes

called a steamer, is a ship in which the
primary method of propulsion is
steam power

Second Law of Thermodynamics. Heat Engines

Zeroth Law Temperature
First Law of Thermodynamics Energy balance on the system.
(Conservation of Energy)
What are the rules to obtain useful energy (those that drives a machine,)?
Why the heat flows spontaneously from the hotter body to the colder one?

Second Law of Thermodynamics

No system can take energy as heat from a single source and
convert it completely into work without additional net changes in
the system or in the surroundings.
SECOND LAW, KELVIN STATEMENT
A process whose only net result is to transfer energy as heat from
a cooler object to a hotter one is impossible.
SECOND LAW, CLAUSIUS
STATEMENT

Second Law of Thermodynamics.

Heat Engines. Steam Engine

A heat engine is a cyclic device whose purpose is to convert as much heat

input into work as possible. Working substance (water in steam engine, air and
gasoline vapor in internal-combustion engine), that absorbs a quantity of heat,
Qh, does work on its surroundings, and gives an amount of heat, Qc, as it returns
to initial state.
Several hundreds atmospheres and
water vaporizes at about 500 C

Schematic drawing of a steam engine.

Heat Engines.
Internal-Combustion Engine

Second Law of Thermodynamics.

Otto cycle representing

the internal-combustion
engine

Second Law of Thermodynamics.

Heat Engines.

No system can take energy as heat from a single source and

convert it completely into work without additional net changes in the
system or in the surroundings.
SECOND LAW, KELVIN STATEMENT
Efficiency of a heat engine

W Qh Qc
Qc

1
Qh
Qh
Qh
It is impossible to make a heat engine
with a efficiency of 100 per cent
It is impossible for a heat engine
working in a cycle to produce only the
effect of extracting heat from a single
reservoir and performing an equivalent
amount of work

Second Law of Thermodynamics.

Refrigerators. Heat Pumps

Schematic representation of a
refrigerator.

COP. Coefficient
of Performance
of a Refrigerator

Qc
COP
W

Second Law of Thermodynamics.

Refrigerators.
A process whose only net result is to
transfer energy as heat from a cooler object
to a hotter one is impossible.
SECOND LAW, CLAUSIUS STATEMENT

It is impossible for a refrigerator

working in a cycle to produce only the
effect of extracting heat from a cold
object and reject the same amount of
heat to a hot object

COP. Coefficient
of Performance
of a Refrigerator

Qc
COP
W

Second Law of Thermodynamics.

Refrigerators. Heat Pumps

The objective of a heat pump is to heat a
region of interest
Useful energy

Heat Pump

Qh
COPHP
W
COPHP. Coefficient of
Performance of a Heat
pump

Equivalence of the Heat Engine

and Refrigerator Statements

Second Law of Thermodynamics.

Maximum efficiency for a heat engine.

The Carnot Engine

What is the maximum possible
efficiency for a heat engine working
between two heat reservoirs?
Carnot Theorem
No engine working between two
given heat reservoirs can be more
efficient than a reversible engine
working between those two reservoirs

Carnot engine: A reversible engine

working in a cycle between two heat
reservoirs. The cycle is called a Carnot
cycle

Maximum efficiency for a heat engine.

Carnot cycle is a reversible cycle
between only two heat reservoirs

The Carnot Cycle

1.- A quasi-static isothermal absorption of
heat from a heat reservoir
2.- A quasi-static adiabatic expansion to a
lower temperature
3.- A quasi-static isothermal exhaustion of
heat to a cold reservoir
4.- A quasi-static adiabatic compression
back to the original state

W Qh Qc
Qc

1
Qh
Qh
Qh

Maximum efficiency for a heat engine.

The Carnot Cycle

Carnot cycle is a reversible cycle

between two heat reservoirs

W Qh Qc
Q

1 c
Qh
Qh
Qh

Isothermal processes

V2

Qh Wby gas

V1

V2
P dV n R Th ln
V1
V4

Qc Won gas P dV n R Tc ln
V3

Adiabatic processes
1
2
1
1

Th V
Th V
V2
Qc
V1 Tc

Qh T ln V3 Th
h
V4
Tc ln

1
3
1
4

Tc V
Tc V

V3
V4

V2 1 V3 1
V2 V3
1
1
V1
V4
V1 V4

W Qh Qc
Qc
Tc

1
1
Qh
Qh
Qh
Th

Second Law of Thermodynamics. Maximum efficiency for a Heat Engine;

Maximum COP for a Refrigerator and for a Heat Pump

W Th Tc
C

Qh
Th
Qc
Tc
COPmax

W Th Tc
Q
Th
COPHP max h
W Th Tc
A steam engine works between a hot reservoir at 100 C and a cold reservoir at 0C. (a)
What is the maximum possible efficiency of this engine? If the engine is run backwards
as refrigerator, what is its maximum coefficient of performance? If the engine is running
as heat pump, what is the maximum coefficient of performance?

Second Law of Thermodynamics.

Irreversibility, desorder:

Entropy
The free expansion of an idealgas: No work, no heat, no
change of internal energy,
But, is it the same state after
and before of the free
expansion?
Entropy, S: a physical magnitude whose net increment (system +
surroundings) indicates the irreversibility of a process:
In a irreversible process, the entropy of the universe increases
For any process, the entropy of the universe never decrease
A spontaneous heat transfer (from hotter body to a colder one) implies
an increment of entropy (It is a irreversible process)
Entropy: a thermodynamic function of disorder

Qrev
dS
T