Physics

C 6 Courseno.6
Ch t II Chapter II
Thermodynamics and statistical physics
Thermodynamics
Thermodynamics studies the thermodynamic system from macroscopic
point of view.
Thermodynamic system a macroscopic system that has the property of
having a border area with the external medium where the exchange of heat,
work and substance (mass) transfer may occurs.
Thermodynamic system:
isolated there is no interaction with the environment isolated there is no interaction with the environment
sealed there is no substance transfer but there is energy exchange
opened there is both mass transfer and energy exchange with the
external medium
Thermodynamic quantities are specific physical quantities for which there are
dependency relations dependency relations.
All the physical quantities required for characterizing the thermodynamic
system are called status parameters.
Status parameters:
intensive do not depend on the mass or the size of the thermodynamic intensive do not depend on the mass or the size of the thermodynamic
system, its value is the same in all the system points.
example: temperature, pressure, concentration, specific heat
extensive there is a dependency of mass and size of the thermodynamic
system
example: volume, mass, number of moles, caloric capacity p , , , p y
Status function physical quantities that do not depend of the previous
status parameters but only on the status parameters at the present status parameters but only on the status parameters at the present
moment.
example: internal energy, entropy, the free energy
The thermodynamic equilibrium the status in which the properties of
the s stem do not ar in time the stat s parameters are constant the system do not vary in time the status parameters are constant.
The notion of temperature originates in the sensation the human senses
feel and it is a status parameter having the same value for bodies in feel and it is a status parameter having the same value for bodies in
equilibrium intensive parameter in case of an isolated system
consisting of n bodies in thermal contact, the condition for equilibrium is
that the temperature has the same value for all the bodies. This is the way that the temperature has the same value for all the bodies. This is the way
the empirical temperature is defined.
The function that depends only on the empirical temperature is called
absolute temperature or thermodynamic temperature and it is labeled with
T and it is measured in Kelvin (K).
The temperature scale previous defined is the so called thermodynamic
absolute scale of temperature and has the advantage of being independent absolute scale of temperature and has the advantage of being independent
on the properties of the thermometric substance.
Using this scale all the thermodynamic laws will have a simple form.
In many cases of practical importance, the heat exchange results in
thermal equilibrium between two systems, but the status of one system is t e a equ b u bet ee t o syste s, but t e status o o e syste s
barely affected. So the consequence of thermal contact is that one of the
bodies does not change its temperature.
The previous mentioned property might be used for determining the
temperature of the system that do not actually changes its temperature
after the thermal contact. The system that does changes his temperature
ft th th l t t i th ll d th t after the thermal contact is the so called thermometer.
A thermometer must be precise and easy to use, the readings should be
reproducible and very important is that the thermometer should not modify reproducible and very important is that the thermometer should not modify
the thermal properties of the system whose temperature one measures.
During the process of temperature measurement the thermometric
substance must undergo a reversible process substance must undergo a reversible process.
Since a classification based on the aggregation status (gas, liquid or solid)
of the thermometric substance does not provide a clear overview on all p
the thermal contact thermometers a short presentation of different
temperature measuring devices is given.
The volumetric thermometer
It works on the base of variation of the thermometric substance that can be in any
aggregation state at constant pressure The most common devices are the ones aggregation state at constant pressure. The most common devices are the ones
with liquid inside a glass capillary. The choice of thermometric liquid depends on
the temperature domain in which the thermometer is meant to be used; the domain
must be in between the boiling and solidification point of that substance and the
precision of the reading is also very important. Between the thermometric liquids
the usual choice is the Mercury (Hg) since can be use at high purity and the
reading on different Hg thermometers are comparable. Also the Hg is an excellent
heat conductor and the result of this characteristic is that the thermometer reaches heat conductor and the result of this characteristic is that the thermometer reaches
very fast the equilibrium state. Its specific heat is low so the thermometer do not
significantly change the temperature of the body of interest and it maintains the
liquid state over a large temperature domain.
Pressure thermometer
Those thermometers work on the base of pressure variation with
temperature in case a fluid (liquid or gas) kept at constant volume.
Pressure thermometers with liquid have a reservoir that is connected to a
capillary tube that has a spiral shape the end being equipped with a
indicator needle fixed on a leverage. The liquid has a initial pressure of
15-20 atmosphere in order to limit the influence of atmospheric pressure 15 20 atmosphere in order to limit the influence of atmospheric pressure
variations. When the thermometer is in contact with a higher temperature
body the thermometer liquid dilates and since the volume is constant the
extra pressure act on the spiral tube resulting a deformation.
Electric resistance pyrometer
Those thermometers work based on the variation of the electrical resistance with temperature
in case of conductor and semiconductor materials.
Generally the variation of the resistance for conductor materials has the form: y
But for the majority of conductors the variation is linear. Materials used for manufacturing the
thermometers must fulfill several conditions:
-the resistivity should be high enough, so there will be no need for a long wire and the
( )
3 2
0 t
ct bt at 1 R R + + + =
y g g , g
measurements should be sensitive and precise
-the thermal coefficient should be high
-stable chemical and physical properties
The best choice as materials are Platinum, Nichel and Copper. Due to its special properties , pp p p p
the platinum resistance thermometer was chosen as etalon for the international scale for the
temperature domain of 200
0
C to +600
0
C. The disadvantage of such device is the high price
of Platinum.
Seebeck thermometer (thermocouple)
Those thermometers work on the principle of direct thermoelectric effect (Seebeck effect) which
consist in producing thermoelectric voltages in a circuit consisting of different conductors (or
semiconductors) whose points of contact (welding) are maintained at different temperatures. ) p ( g) p
Each circuit is characterized by a certain thermoelectric voltage that depends on the size of the
T. A thermocouple is calibrated for measuring thermoelectric voltages at different known
values of temperature for example the cold welding is maintained at constant temperature (ice
T U
Seebeck
A o =
values of temperature for example the cold welding is maintained at constant temperature (ice
melting temperature).
The measuring range depend on the nature of the materials. For example the thermocouple
platinum/platinum-rhodium operate between 0 C and 1600 C.
Electro-mechanic thermometers
This type of thermometer works on the principle of resonance vibration frequency
dependence of quartz crystal temperature, due to its size changes that are
temperature dependent. In order to obtain a linear dependency of the resonant
frequency versus temperature the quartz crystal is cut at an angle. There are crystals
that change their frequency of 10
3
Hz per degree. Pulses provided by a quartz crystal
are compared with those provide by standard frequency If standard frequency scale p p y q y q y
correspond to zero temperature one can convert directly the frequency differences in
degrees. Resolution of such thermometer is very high of 10
-5 0
C, for a temperature
domain of 80
0
C to +250
0
C. The thermometer is use in calorimetry for both relative
and absolute measurements and absolute measurements.
Magnetic thermometers
These thermometers are used for measuring extremely low temperatures (below 2K),
in the domain of 0 002 2 K and work on the principle of adiabatic demagnetization of in the domain of 0.002 2 K and work on the principle of adiabatic demagnetization of
some magnetic substances. Those thermometers require very fine calibration the
temperature values being obtain from the magnetic susceptibility with the help the
exiting database for different magnetic substances.
Optical thermometers
These thermometers are used for the very high temperature domain above 1000
0
C.
The working principle is based on the laws of thermal radiation. The idea is to measure
the intensity of thermal radiation of the body of interest without a direct thermal contact
with the measuring device. The optical thermometers are visual or photoelectric and
the body of interest emits radiation in the domain of infrared, visible or ultraviolet.
The ideal gas model
th i t f l b f id ti l ti l ( t
Ideal gas
the gas consists of very large number of identical particles (atoms or
molecules)
the dimensions of particles are tiny relative to the inter-particle distances
so the atoms (or molecules) might be considered as material points so the atoms (or molecules) might be considered as material points.
the particles have a chaotic movement; the movement of a separate one
fallows the rules of the classical mechanics (Newton Laws)
the interatomic (intermolecular) forces are not considered; the particles the interatomic (intermolecular) forces are not considered; the particles
moves freely its trajectories are straight lines
the collisions particle-particle and particle-walls of the sealed vessel are
elastic
Between the ideal gas parameters there is a relation:
T R T R
m
V p v status equation of ideal gas T R T R V p v =

= status equation of ideal gas

K mol
J
314 , 8 R

=
constant of the ideal gas
This equation can be obtained directly on experimental basis or
theoretical with the help of the molecular-kinetic approach.
The ideal gas laws
Th l t bli h d i i i l ( i t l) h Those laws were established using an empirical (experimental) approach:
the isothermal compression law (Boyle Mariotte):
the constant pressure heating law (Gay Lussac):
. const T . const pV = =
p g ( y )
the constant volume heating law (Charles):
. const p . const
T
V
= =
the constant volume heating law (Charles):
the law of adiabatic compression:
. const V . const
T
p
= =
const TV const pV
1
= =

the law of adiabatic compression:
adiabatic coefficientandisequalwiththerationofmolarheat
. const TV . const pV = =
v
p
C
C
=
. const pV =
_
The law of polytrophic transformation:
polytrophiccoefficient
. co s pV
The molecular-kinetic theory of ideal gases
The molecular kinetic theory determine the laws for gases considering the
movement at atomic (or molecular) level. It assumes that the gas constituents
(atoms or molecules) moves freely with no other interaction then elastic
collisions. On the basis of a simple model the kinetic energy for a particle of a
mono-atomic gas is:
3
mv
2
T k
2
3
2
mv
B
= = c
K / J 10 38 1
R
k
23
= =
Boltzmann constant
K / J 10 38 , 1
N
k
a
B
= =
T is the absolute temperature of the considered gas
- Boltzmann constant
The previous relation allows a kinetic interpretation of temperature The The previous relation allows a kinetic interpretation of temperature. The
temperature is considered to be a measurement of the average kinetic
energy of gas particles, and has the same expression independent of the
gas particle nature gas particle nature.
The previous equation indicates that the zero kinetic energy (no movement)
corresponds to the zero of absolute temperature.
Physical phenomena in dilute gases
Dilute gases means those gases having a very low pressure so the
collisions of gas particles occurs only with the vessel walls. The distance
between two consecutive collisions is called free path. Since the fee
path varies after each collision the mean free path has to be
considered. The mean free path is labeled and is inversely to the gas
concentration (and pressure) and increases following a non linear
d d ith t t F th f th i t dependence with temperature. For rare gases the mean free path is at
least equal with the vessel dimensions or larger. If the mean free path is
larger then the vessel dimensions the dilute status is called vacuum.
Since the gas atoms (or molecules) collides only with vessel walls the Since the gas atoms (or molecules) collides only with vessel walls the
energy transfer is done only with the walls. Such heat exchange may
facilitate the heat transport if the walls are at different temperatures.
The heat transport is proportional with the dilute gas pressure thus the
number of gas particle collisions with the vessel walls.
On such principle the cryogenic vessels are built (see Dewar vessel).
Real gases
In order to describe the action of real gases one has to modify the status
equation for ideal gases considering the volume of the gas particles and
the interaction forces between the gas constituents.
The behavior of the real gas considering a pV=f(p) diagram one can
notice that the graph of the real gas has a minimum at low pressure while
th id l h th t i ll l ith th b i i the ideal gas has a curve that is parallel with the abscise axis.
The minimum position of the real gas curve is temperature dependent.
Considering the 1 and 2 states for which p
1
<p
2
and p
1
V
1
>p
2
V
2
:
1
3
4
pV pV
gaz real gaz ideal
2
3
Ideal gas Real gas
p p
a. b.
If the gas would be an ideal one at the p
2
, according to the isothermal
compression law, the corresponding volume is volume V
2
':
'
=
2 2 1 1
V p V p
The result is that so the corresponding volume of the real gas (at
p
2
pressure) is smaller then the one of the ideal gas at the same pressure
'
<
2 2
V V
(p
2
). The conclusion is that at low pressure the real gas is more
compressible then the ideal gas between the gas atoms (molecules) a
cohesive force is acting and the gas particles tend to come closer.
If t t 3 d 4 id d f th d t l f th h If states 3 and 4 are considered for the ascendant slope of the graph one
can conclude that at high pressure domain the real gas compressibility is
smaller then the one of the ideal gas.
p
II
The isotherms of the real gases clearly
indicates the presence of a saturation curve
a characteristic of condensation phenomena
I
a characteristic of condensation phenomena
once the gases are compressed. The first
region below the saturation curve indicates
the coexistence of two phases (liquid and
O V
p ( q
saturated vapors) and the second region,
above the saturation curve, correspond to a
single phase, the gas one.
Status equation of real gases
The status equation of real gas is the empirical determined expression of
Van der Waals:
( ) T R b V
V
a
p
2
v =
|
.
|

\
|
+
2
V
a
- internal pressure
b co-volume
The Van der Waals equation offers a description that is consistent with
the isothermal behavior of real gases.
One has noticed that both a and b have a temperature dependant
characteristic.
Thermodynamics postulates
Between all the possible states of a thermodynamic system the
most important are the thermodynamic equilibrium states or the states very
close to equilibrium.
The first postulate of thermodynamics mentions that an isolated
system always achieves after a specific time interval the thermodynamic
equilibrium status and cannot leave itself that status (if the external equilibrium status and cannot leave itself that status (if the external
parameters are kept constant). This postulate indicates the direction of
thermodynamic evolution processes and also support the idea of process
irreversibility irreversibility.
There are some limitations regarding the first postulate: there is no
mention about the time frame require for achieving the thermal equilibrium q g q
or the phenomena involving spontaneous fluctuations in the vicinity of the
equilibrium status it means that only phenomena where fluctuations are
non essential can be considered. It is important to mention that the
equilibrium situation for an homogenous thermodynamic system is an
internal characteristic and does not change if the system is divided in
several sub-systems.
The second postulate express the transitivity of the thermodynamic
equilibrium: using an experimental approach one can notice that two
th d i t A i B th l t t (b t ith t thermodynamic systems A i B on thermal contact (but without mass
transfer in between), independent from the external parameters, remains on
the equilibrium status or the systems evolves towards a new equilibrium
status doe to energy exchange status doe to energy exchange.
This two component system now in contact with a third system C, in a This two component system now in contact with a third system C, in a
very similar way, follows the same path: A+B and C systems remains in
equilibrium or the systems evolves towards a new equilibrium status. If the
thermal contact is broken the equilibrium status is maintained and also in q
case of a new thermal contact between the systems the thermal equilibrium
is preserved. The temperature is a crucial parameter that allows us to
compare different equilibrium states.
The transitivity characteristic allows comparing the temperature values
for different thermod namic s stems itho t ha ing a thermal contact for different thermodynamic systems without having a thermal contact
between them only a third body is required and used as intermediate
system.
Problems
1. Inside a bottle there is molecular Nitrogen at T
1
=300 K and pressure p
1
=1,510
7
N/m
2
. From that bottle a quantity of Nitrogen was used for an experiment. At the
temperature of T
2
=280 K, the gas pressure is p
2
=0,610
7
N/m
2
and the mass of the
mass of the bottle dropped by m=3 2 kg One should determine: a) the number of mass of the bottle dropped by m=3,2 kg. One should determine: a) the number of
Nitrogen moles
1
in the initial state; b) the remaining m
2
Nitrogen mass.
2. Two sealed containers of V
1
=1 l and V
2
=2 l volumes are kept at constant t
1
=17C
and t
2
=23C temperatures and contain gases at p
1
=1 atm. and p
2
=2 atm.
pressures. The containers are connected through a tube of negligible volume that
has a closed valve. Calculate the final pressure p once the valve is opened.
3. a) A gas mass has a ciclical transformation
depicted in the figure Indicate the relation between depicted in the figure. Indicate the relation between
the volumes of the four states (1, 2, 3, 4)? Justify
the answer!
b) Represent the ciclical transformation in p-V
and V-T coordinates.