Dr.

Marei ke Zi nk /
Prof . Dr. Josef A. Ks
Experimental Physics II
Summer 2014
Laws of thermodynamics
Thermodynamics is a branch of physics concerned with
heat and temperature and their relation to energy and work
Thermodynamics was developed out of a desire to increase
the efficiency and power output of heat engines
Findings are common to all materials, not the peculiar
properties of particular materials
State variable
state variable is a property of a system that depends only
on the current state of the system, not on the way in which
the system acquired that state (independent of path)
a state variable describes the equilibrium state
internal energy, temperature, and pressure are state
variables
in contrast, mechanical work and heat are process quantities
because their values depend on the specific transition (or
path) between two equilibrium states
Mass (m)
Energy (E)
Enthalpy (H)
Internal energy (U)
Gibbs free energy (G)
Helmholtz free energy (F)
Entropy (S)
Pressure (P)
Temperature (T)
Volume (V)
Particle number (n
i
)
The following are considered to be state functions in
thermodynamics:
State variables of an ideal gas:
pressure p, temperature T, volume V
Work and ideal gas:
work done to the system > 0
work done by the system < 0
Changing state variables:
Isobar:
Volume change
Isochor:
Pressure change
Isotherm:
Change in compressibility
Volume change in general:
Isochor:
Laws of thermodynamics
Zeroth law of thermodynamics:
If two systems are in thermal equilibrium with a third system,
they must be in thermal equilibrium with each other. This law
helps define the notion of temperature.
First law of thermodynamics:
Because energy is conserved, the internal energy of a system
changes as heat flows in or out of it. Equivalently, machines
that violate the first law (perpetual motion machines) are
impossible. Heat is the flow of thermal energy from one object
to another.
Second law of thermodynamics:
The entropy of any isolated system cannot decrease. Such
systems spontaneously evolve towards thermodynamic
equilibrium the state of maximum entropy of the system.
Equivalently, machines that violate the second law (perpetual
motion machines) are impossible.
Third law of thermodynamics:
The entropy of any pure substance in thermodynamic
equilibrium approaches zero as the temperature approaches
zero. The entropy of a system at absolute zero is typically zero,
and in all cases is determined only by the number of different
ground states it has.
Zeroth law of thermodynamics
if two separate thermodynamic systems are each in thermal
equilibrium with a third, then all three are in thermal
equilibrium with each other
all heat is of the same kind
thermal equilibrium constitutes an equivalence relation on
pairs of thermodynamic systems
ideal gas: p
1
V
1
/N
1
= p
2
V
2
/N
2
= p
i
V
i
/N
i
=RT
First law of thermodynamics
version of the law of conservation of energy
energy can be transformed from one form to another, but
cannot be created or destroyed
the change in the internal energy of a closed system is equal
to the amount of heat supplied to the system, minus the
amount of work done by the system on its surroundings:
where and are quantities of heat supplied to the system by its
surroundings and of work done by the system on its
surroundings, respectively
perpetual motion machines of the first kind are impossible.
Adiabatic processes
there is transfer of energy as work but not as heat
the respective total quantities of energy transferred as work
are one and the same, determined just by the given initial
and final states
Reversible processes
heat transfer is reversible when it is driven by practically
negligibly small temperature gradients
work transfer is reversible when it occurs so slowly that
there are no frictional effects
when the heat and work transfers in the equations above are
infinitesimal in magnitude, they are often denoted by ,
rather than exact differentials denoted by "d:
Perpetual motion
perpetual motion machine of the first
kind produces work without the input of
energy (violates the first law of
thermodynamics)
perpetual motion machine of the second
kind is a machine which spontaneously
converts thermal energy into mechanical work
(violates second law of thermodynamics)
perpetual motion machine of the third
kind is defined as one that completely
eliminates friction and other dissipative forces,
to maintain motion forever
thought (or "gedanken") experiment appears to suggest that perpetual
motion may be possible: Maxwell's Demon, Brownian Ratchet
2 Gedankenexperimente
Maxwell's demon:
thought experiment created by the Scottish physicist James Clerk
Maxwell
to "show that the Second Law of Thermodynamics has only a statistical
certainty."
hypothetical demon opens the door to allow only the "hot" molecules of
gas to flow through to a favored side
Feynman-Smoluchowski ratchet
thought experiment about an apparent perpetual motion
machine
first analysed in 1912 by Polish physicist Marian
Smoluchowski
popularised by American Nobel laureate physicist Richard
Feynman in The Feynman Lectures on Physics
simple machine, consisting of a paddle wheel and a ratchet,
able to extract work from random fluctuations in violation of
the second law of thermodynamics
Feynman ratchet model led to the similar concept of
Brownian motors, which can extract useful work from
chemical potentials
First lawof thermodynamics:
Work done by expanding piston:
Ideal gas:
Isochore V=const:
Isobar p=const:
Enthalpy is a defined thermodynamic potential, designated
by the letter "H", that consists of the internal energy of the
system (U) plus the product of pressure (P) and volume (V)
of the system:
Isotherme (T=const):
Adiabatic (dQ=0):
Entropy
entropy (usual symbol S) is a measure of the number of
specific ways in which a thermodynamic system may be
arranged
taken to be a measure of disorder,
or a measure of progressing towards thermodynamic
equilibrium
define a state function S called entropy, which satisfies:
the change in entropy (S) for a thermodynamically
reversible process
,
Statistical mechanics
a microstate is a specific microscopic configuration of a
thermodynamic system that the system may occupy with a
certain probability in the course of its thermal fluctuations
the macrostate of a system refers to its macroscopic
properties, such as its temperature and pressure
macrostate is characterized by a probability distribution of
possible states across a certain statistical ensemble of all
microstates
for a given set of macroscopic variables, the entropy
measures the degree to which the probability of the system
is spread out over different possible microstates:
where k
B
is the Boltzmann constant.
The summation is over all the possible microstates of the
system, and p
i
is the probability that the system is in the ith
microstate.
Second law of thermodynamics
the entropy of an isolated system never decreases, because
isolated systems always evolve toward thermodynamic
equilibrium, a state with maximum entropy
second law is an empirically validated postulate
increases in entropy are due to dissipation of energy and due
to dispersion of matter
the efficiency of a quasi-static or reversible cycle depends
only on the temperatures of the two heat reservoirs, and is
the same, whatever the working substance (Carnot)
heat can never pass from a colder to a warmer body without
some other change, connected therewith, occurring at the
same time (Clausius)
Clausius equality for a reversible process:
reversible process combine it with irreversible process: