Professional Documents
Culture Documents
1.basic Thermodynamics
1.basic Thermodynamics
1. Introduction to thermodynamics
2. Relevance for atmosphere
3. Global perspectives
4. Heat machines & Geophysics
From Wikipedia, the free encyclopedia
Thermodynamics (from the Greek thermos meaning heat and dynamis meaning power)
is a branch of physics that studies the effects of changes in temperature, pressure, and
volume on physical systems at the macroscopic scale by analyzing the collective motion
of their particles using statistics. Roughly, heat means "energy in transit" and dynamics
relates to "movement"; thus, in essence thermodynamics studies the movement of energy
and how energy instills movement. Historically, thermodynamics developed out of the
need to increase the efficiency of early steam engines.
The starting point for most thermodynamic considerations are the laws of
thermodynamics, which postulate that energy can be exchanged between physical
systems as heat or work. They also postulate the existence of a quantity named entropy,
which can be defined for any system. In thermodynamics, interactions between large
ensembles of objects are studied and categorized. Central to this are the concepts of
system and surroundings. A system is composed of particles, whose average motions
define its properties, which in turn are related to one another through equations of state.
Properties can be combined to express internal energy and thermodynamic potentials are
useful for determining conditions for equilibrium and spontaneous processes.
With these tools, thermodynamics describes how systems respond to changes in their
surroundings. This can be applied to a wide variety of topics in science and engineering,
such as engines, phase transitions, chemical reactions, transport phenomena, and even
black holes. The results of thermodynamics are essential for other fields of physics and
for chemistry, chemical engineering, cell biology, biomedical engineering, and materials
science to name a few.
Quotes
these experimentalists do bungle things from time to time. But if your theory
is found to be against the Second Law of Thermodynamics I can give you no
hope; there is nothing for it but to collapse in deepest humiliation." Sir
Arthur Eddington
Isnt thermodynamics considered a fine intellectual structure, bequeathed by
past decades, whose every subtlety only experts in the art of handling
Hamiltonians would be able to appreciate? Pierre Perrot, author: A to Z
Dictionary of Thermodynamics
"Thermodynamics is a funny subject. The first time you go through it, you
don't understand it at all. The second time you go through it, you think you
understand it, except for one or two small points. The third time you go
through it, you know you don't understand it, but by that time you are so used
to it, it doesn't bother you any more." Arnold Sommerfeld
1.2
1.3
consists of nitrogen gas, N2, Oxygen, O2, Argon, Ar, etc. To a smaller extent there is also
carbon dioxide, CO2, Methane, CH4. These latter gases are strongly affected by biological
activity, and by burning of fossil fuels and organic material. Accordingly, the
concentration of these gases varies significantly with time. Notably, they also play an
important role for the radiation budget of the earth although they are not important
directly for the thermodynamical properties of the atmosphere which is the subject of
this course.
A material of special interest for this course is water, which exist in its all three phases
in the natural environment. Furthermore, the transition between water vapor and
water/ice is very important for many atmospheric processes and describing these
transition properties will be one of the main tasks in this course.
1.4
1.5
p=
F
.
A
1.7
T
V
nk Rk* =
k
n R*
T
n k k
V k n
Figure text: Mean molecular weight versus height for U.S. Standard Atmosphere.
1.8
0th law: Two systems that are in thermal equilibrium with a third are in
thermal equilibrium with each other.
d v2
dz
dv
v m
= mge z m
= mg
dt 2
dt
dt
,
d
( K + P ) = 0 K + P = const
dt
Energy is conserved in a mechanistic system, can change
between the kinetic energy of the point mass (energy of motion)
and the potential energy (energy of position).
For system with many particles, it can be shown that we also
consider changes in kinetic and potential energy in the way the
mass centre moves (the kinetic energy of a fictious body with
mass equal the entire system of point masses and moving with
its centre of mass velocity) and in the way the particles move
randomly or disorganized, this thus also represent a kinetic
energy but may represent internal kinetic energy (or
temperature)
Ordered mean motions are easily transferred to internal random
motions. Consider a balloon filled with water. If we drop it will
have a certain mean motion before it strikes the floor. However,
after hitting the floor the mean motion becomes zero and must
1.9
dU
= Q W ; Q is heating rate, W working rate. (these are
dt
equal zero for a closed system).
dU
d
=Q p
.
dt
dt
d
which implies that we
dt
dU = dQ + dW
The best way to understand energy and entropy indeed, all concepts, scientific or
otherwise is to use them in as many contexts as possible, proceeding from the familiar
to the unfamiliar.
From Wikipedia, the free encyclopedia
1.10
Thermodynamic processes
A thermodynamic process may be defined as the energetic evolution of a
thermodynamic system proceeding from an initial state to a final state. Typically, each
thermodynamic process is distinguished from other processes, in energetic character,
according to what parameters, as temperature, pressure, or volume, etc., are held fixed.
Furthermore, it is useful to group these processes into pairs, in which each variable held
constant is one member of a conjugate pair. The six most common thermodynamic
processes are shown below:
1.An isobaric process occurs at constant pressure.
2.An isochoric process, or isometric/isovolumetric process, occurs at constant
volume.
3.An isothermal process occurs at a constant temperature.
4.An isentropic process occurs at a constant entropy.
5.An isenthalpic process occurs at a constant enthalpy.
6.An adiabatic process occurs without loss or gain of heat.
Thermodynamic potentials
As can be derived from the energy balance equation on a thermodynamic system there
exist energetic quantities called thermodynamic potentials, being the quantitative measure
of the stored energy in the system. The four most well known potentials are:
Internal energy
Helmholtz free energy
Enthalpy
Gibbs free energy
Potentials are used to measure energy changes in systems as they evolve from an initial
state to a final state. The potential used depends on the constraints of the system, such as
constant temperature or pressure. Internal energy is the internal energy of the system,
enthalpy is the internal energy of the system plus the energy related to pressure-volume
work, and Helmholtz and Gibbs free energy are the energies available in a system to do
useful work when the temperature and volume or the pressure and temperature are fixed,
respectively.
1.11
Q=
dU
d
+p
dt
dt
The internal energy U for a simple closed system such as a gas may be considered s
function of the two independent variables, temperature T and volume V, while the third
variable p is related to these two by the ideal gas law.
dU U dT U d
=
+
dt
T dt dt
Notably U has the dimension of pressure and
is sometimes called the internal pressure (for an ideal
gas U =0, Joules law and has been confirmed to
be small in experiments using real gases). Continuing
U = 0 for an ideal gas (pdV=0 for
dT U d
d
+
+p
dt dt
dt
dT U
d
+
+ p
dt
dt
U
T
U
=
T
Q=
above experiment)
The first partial derivative on the right hand side of this equation appears with
sufficient frequency that is has acquired a name, heat capacity (at constant volume)
Cv =
U
T
Its relevance is clear from the following equation appearing for constant volume.
Q = Cv
dT
, V=const.
dt
C v
U
U
=
=
0
V
V T T V
This relation holds for an ideal gas where interactions between molecules are negligible.
Cv depends on the total mass of the system and sometimes it is convenient to deal with
the specific heat capacity instead, thus
1.12
Cv =
cv
.
m
dU
d
+p
dt
dt
d
d T R dT RT dp
2
= R =
dt
dt p p dt
p dt
R dT RT dp dU
dU
dT RT dp
+ p
2
+R
=
dt
p dt dt
dt
p dt
p dt
dU dT
dT RT dp
=
+R
dT dt
dt
p dt
Q=
dT
dT
= Cp
dt
dt .
C p = Cv + R
We thus find that the heat capacity (or resistance to become warm when heated) is
larger under constant pressure than under constant volume. To show that cp greater than
cv makes physical sense, consider an ideal gas confined to a cylinder fitted with the usual
frictionless nut tightly fitted piston. Fix the piston in place and heat the gas for a certain
amount of time. The temperature of the gas rises in this constant volume process. Now let
the piston move freely so that gas pressure is constant. Heat the gas for the same amount
of time a before. Again the temperature increases, but in this process the piston rises; thus
work is done by the gas and consequently its internal energy doesnt increase as much as
before. This implies that the temperature increase isnt as great. Stated another way, cp is
greater than cv, which is consistent with what we derived.
1.13
For liquids and solid material the compressibility (implying that pd0) is essentially
zero and thus
C p Cv .
dU
d
+p
can now be written
dt
dt
dH
dp
dt
dt
We thus have
H
T
H
=
T
Q=
dT H dP
dP
+
dt P dt
dt
dT H
dp
+
dt V
dt
1.14
For constant pressure we have that the heat capacity (at constant volume) is
Cp =
H
T
Its relevance is clear from the following equation appearing for constant volume.
Q = CP
dT
, p=const.
dt
Using the definition of entalphy (and conidering the independent variables to be T and
p)
H = U + p
H (T , p ) = U (T , ) + p
H dT H dp U dT U d
dp
d
+
=
+
+
+p
T dt P dt T dt dt
dt
dt
d dp dT
+
= ( p, T )
=
dt
p dt T dt
dT H
U
d dp
H U U
p
+
V
p
=0
T dt P
p
dp dt
T T T
thus
U
+p
U
T
T
, ideal gas
= 0 (Joules law).
C p = Cv + p
= Cv + R
T
C p = Cv +
Note that the intermolecular forces are negligible in an ideal law. Joules law can be
showed in experiments where a chamber is split in two parts. The left part has a certain
pressure and the right volume has no pressure. If the wall is removed gas will go from left
to the right side. There is no exchange of heat, no work done and thus the internal energy
must remain constant.
+p
will be considered in later
T
T
sections. However, to pave the way forward we need to introduce the concept entropy,
which is done in section 3.
Joules law and the expression C p = Cv +
1.15
with work done by the system on the atmosphere which is the product of the pressure
times the volume. The term enthalpy is composed of the prefix en-, meaning to "put
into", plus the Greek suffix -thalpein, meaning "to heat".
Enthalpy is a quantifiable state function, and the total enthalpy of a system cannot be
measured directly; the enthalpy change of a system is measured instead. A possible
interpretation of enthalpy is as follows. Imagine we are to create the system out of
nothing, then, in addition to supplying the internal energy U for the system, we need to
do work to push the atmosphere away in order to make room for the system. Assuming
the environment is at some constant pressure P, this mechanical work required is just PV
where V is the volume of the system. Therefore, colloquially, enthalpy is the total amount
of energy one needs to provide to create the system and then place it in the atmosphere.
Conversely, if the system is annihilated, the energy extracted is not just U, but also the
work done by the atmosphere as it collapses to fill the space previously occupied by the
system, which is PV.
Enthalpy is a thermodynamic potential, and is useful particularly for nearly-constant
pressure processes, where any energy input to the system must go into internal energy or
the mechanical work of expanding the system. For systems at constant pressure, the
change in enthalpy is the heat received by the system plus the non-mechanical work that
has been done. In other words, when considering change in enthalpy, one can ignore the
compression/expansion mechanical work. Therefore, for a simple system, with a constant
number of particles, the difference in enthalpy is the maximum amount of thermal energy
derivable from a thermodynamic process in which the pressure is held constant.
1.16