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 boundary of the system
is arbitrarily chosen

The system can exchange mass and energy

through the boundary with the environment.
An example of closed system - no mass flow- is
the gas confined in a cylinder. The boundary in this
case real wall- 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 exchanges 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 not 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 increase in temperature.
We can replace the insulating walls by conducting
walls. We can transfer heat through the walls to the
system to produce the same increase in temperature.
Schematic diagram for Joules
experiment. Insulating walls are
necessary to prevent heat transfer
from the enclosed water to the
surroundings.
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 equals the change of
potential energy of the weights.

The increase in temperature of the system is a

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

The sum of the heat transferred 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 does the confined gas
exchange 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 or
subtracted, to the system?

Quasi static processes: a type of process where the gas moves through a
series of equilibrium states. Then, we can apply the Ideal Gas Law. In practice, if
we move the piston slowly, it 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 for an Ideal Gas.

It only depends on the temperature
of the gas, and not on its volume nor its
pressure

What is the value of the internal

energy for the gas in the cylinder?

Experiment: Free expansion.

For a gas at low density an
ideal gas-, a free expansion does not
change the temperature of the gas.

If heat is added at constant volume, no work

is done, so the heat added equals to the
increase in 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, it only 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 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 in 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 to (or lost from) the system. The value of the heat
energy transferred depends on 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
CV n R
2
5
CV n R
2

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 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, it 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 to 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
decreases to 1.2 atm
3. The gas undergoes an isothermal compression back to
its 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.

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 heat added and the work done by
the gas during each part of the cycle. (c) Find the temperatures T1, T2, T3

The First Law of Thermodynamics.

Cyclic Processes. P-V

Diagrams

The First Law of Thermodynamics.

Cyclic Processes. P-V

Diagrams

At point D in the 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 at 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