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Thermal Physics
1. Heat & Temperature
1. Temperature
2. Thermal Expansion
3. The Atomic Nature of Matter
4. Gas Laws
5. Kinetic-Molecular Theory
6. Phases
2. Calorimetry
1. Sensible Heat
2. Latent Heat
3. Chemical Potential Energy
3. Heat Transfer
1. Conduction
2. Convection
3. Radiation
4. Thermodynamics
THERMAL EXPANSION
Thermal expansion refers to a fractional change in size of a material in response to a change in
temperature.
This includes
changes in length compared to original length (/0) called linear expansion
changes in area compared to original area (A/A0) called areal expansion or superficial
expansion
changes in volume compared to original volume (V/V0) called volumetric expansion or
cubical expansion
For most materials, over small temperature ranges, these fractional changes
are directly proportional to temperature change (T) and
have the same sign (i.e., materials usually expand when heated and contract when
cooled)
are larger for liquids than solids
A coefficient of thermal expansion
is the ratio of the fractional change in size of a material to its change in temperature
is represented by the symbol (alpha) for solids and (beta) for liquids
uses the SI unit inverse kelvin (K1 or 1/K) or the equivalent acceptable
non SI unit inverse degree Celsius (1 or 1/).
Solids
tend to retain their shape when not constrained and so
are best described by a linear coefficient of thermal expansion, (alpha).
have an areal expansion that is very nearly twice their linear expansion, 2
Nearly all of the hydrogen and helium in the universe was created
in the first three minutes of the universe's existence (13.8 billion years
ago).
Nearly all of the elements heavier than helium found on the Earth
were created many millions of years before the solar system formed (4.5
billion years ago).
Stable atoms can be used over and over again (recycled) in different
combinations and will never "wear out".
can be "seen" only with great difficulty.
Since light is 10,000 times larger than atoms, atoms are too small to be
"seen" with light. (No optical device can ever be used to image atoms.)
x-ray diffraction
Avogadro's hypothesis
The number of molecules in a given volume of gas at a given temperature is the same for all
gases.
The ideal gas law (presented two ways)
functional thermodynamics
PV=nRT
statistical thermodynamics
PV=NkT
Thermodynamic changes with special names
An isobaric process is one that takes place without any change in pressure.
An isochoric process is one that takes place without any change in volume.
An isothermal process is one that takes place without any change in temperature.
Isothermal processes are often described as "slow".
The pressure of a gas is inversely proportional to its volume only if the change takes
place isothermally.
An adiabatic process is one that takes place without any exchange of heat.
Adiabatic processes are often described as "fast".
The pressure of a gas is not inversely proportional to its volume if the change takes place
adiabatically.
KINETIC-MOLECULAR THEORY
The kineticmolecular theory (kmt)
is a theory of ideal gases
can be used to deduce the properties of gases
can be applied to other systems such as free electrons in a metal
is sometimes called the molecularkinetic theory (mkt)
Postulates
All matter is composed of particles (molecules in general, but also atoms, ions, and free
electrons).
Molecules are very small relative to the distance between them.
Molecules are in constant random (chaotic) motion.
Collisions between molecules are perfectly elastic.
Equipartition of Energy
The time-averaged kinetic energy of the molecules in a gas
is divided equally among all the possible degrees of freedom
For a monatomic gas, there are 3 degrees of freedom, one for each spatial
direction (x, y, z)
For a monatomic gas, there are 5 degrees of freedom, one for each spatial
direction (x, y, z) plus one for each rotational axis (, ).
is equal for every kind of molecule in a mixture of gases
On average, heavier molecules move slower and lighter molecules move faster.
A proper discussion of kmt includes statistics.
gas, KT.
Molecular speeds are described by the Maxwell-Boltzmann distribution.
The curve of the Maxwell-Boltzmann distribution
resembles a bell curve
has no negative values
has a positive skew (most values are greater than the most probable value)
has a total area under the curve of 1
The probability of finding a molecule with a speed in a certain range is equal to the area under
the that section of the curve.
The most probable speed occurs at the maximum value of the distribution.
Higher temperature shifts the peak of the curve
"right" higher temperature increases the most probable speed
"down" higher temperature increases the statistical dispersion (the curve is flatter and
wider)
The measures of central tendency are not all the same (vp<v<vrms).
PHASES
solid
THERMODYNAMICS
Thermodynamics - the science that is concerned with energy, particularly energy-in-transit in the
forms of heat and work, and those properties of systems that are related to energy.
Energy the ability to do work. All energy is relative! Energy-in-transit is not relative.
Three kinds of energy:
(1) potential - energy due to relative position,
(2) kinetic - energy due to relative velocity,
(3) internal - the sum of all potential and kinetic energies of constituent parts [atoms, molecules,
etc.] of a system.
Two kinds of energy-in-transit:
(1) heat energy transferred between system and surroundings because of a temperature
difference, or gradient.
(2) work - energy transferred between system and surroundings because of a pressure
difference, or gradient.
Thermodynamic System just the thing that we are talking about! Everything else is called the
surroundings. The sum of the system and the surroundings is the universe.
Three kinds of systems:
(1) closed system a fixed quantity of material; energy can cross the system boundaries but
mass can not.
(2) open system a particular region of space; both mass and energy may cross the system
boundaries.
(3) isolated system (not an important concept) neither energy nor mass may cross the system
boundaries.
In elementary thermodynamics all systems consist only of atoms and molecules where the net electric
charge of the system is zero. In addition, all electrical and magnetic and surface forces are generally
neglected.
Thermodynamic Materials - Systems composed of atoms and molecules are called materials.
Two kinds of materials:
(1) pure materials - composed of only one molecular species, and
(2) mixtures - composed of two or more molecular species.
ideal mixtures - mixtures where the volume and enthalpy of the mixture are simply the sums of the
volumes and enthalpies of the pure components at the temperature and pressure of the mixture.
Elementary thermodynamics deals only with ideal mixtures. Advanced thermodynamics is concerned
with non-ideal mixtures, in phase equilibrium and reaction equilibrium.
Four basic concepts of materials:
(1) Quantity
(a) mass (or weight in a known gravitational field)
(b) number of objects (one gram mole = 6.025 x 10^23 objects)
mean-molar-mass (molecular weight or atomic weight) is the mass of one mole of a particular
collection of objects, and is the constant which allow conversion between these two measures of
quantity.
(2) Composition of a mixture
(a) fraction - quantity of a particular species per unit quantity of the mixture.
(b) concentration - quantity of a particular species per unit volume of the mixture.
(3) Phase - a homogeneous quantity of material, characterized throughout by a single set of
thermodynamic properties.
(a) solids - materials which are capable of resisting shear stresses.
(b) fluids - materials which exhibit continuous deformation under shear stress.
(c) liquids - fluids which can conform to their containers without occupying them completely.
(d) gases - fluids which conform to and completely occupy their containers.
(e) vapors - gases at temperatures less than their critical temperature.
quality - ratio of quantity of vapor to the total quantity of material [vapor & liquid] or [vapor & solid]
in a system
(4) State - defined by the properties of a material.
(a) subcooled liquid (or compressed liquid) - a liquid at a temperature below its saturation
temperature or at a pressure above its saturation pressure.
(b) superheated vapor - a vapor at a temperature above its saturation temperature or at a pressure
below its saturation pressure.
(c) saturated - if two or more phases exist within a system at equilibrium, the system is said to
be saturated and all phases present are saturated. In particular, if vapor and liquid phases are
both present within a system, the vapor is said to be saturated vapor and the liquid is said to be
saturated liquid
Thermodynamic Properties - any quantity that depends only on the state of a material and is
independent of the process by which a material arrives at a given state.
Properties of a System - the average or homogeneous properties of a system at equilibrium.
Two kinds of properties:
(1) intensive - independent of the quantity of material [T, P, Cp and Cv], and all specific and
molar properties.
(2) extensive - directly proportional to the quantity of material [V, S, U, H, etc.].
Pseudointensive properties - extensive properties expressed per unit quantity of material [v, s, u, h,
etc.].
Two kinds of pseudointensive properties:
(1) specific properties - expressed on a unit mass basis, and
[n = 0]
[n = 1]
[n = gamma,(Cp/Cv)]
[n = infinity]
passes during a reversible process may be considered to be equilibrium states. This is an idealized
situation that would require infinite time and/or equipment size to be realized. The concept of a
reversible process serves to set a maximum for the efficiency of a given process. Note that an
isentropic process is an adiabatic-reversible process, so that real isentropic processes are not possible.
thermodynamic cycle - a process for which the final and initial states are the same.
Four common idealized thermodynamic cycles:
(1) Carnot cycle - isothermal and isentropic compressions followed by isothermal and isentropic
expansions.
(2) Rankine cycle - isobaric and isentropic compressions followed by isobaric and isentropic
expansions.
(3) Otto cycle - isentropic and isochoric compressions followed by isentropic and isochoric
expansions.
(4) Diesel cycle - isentropic compression followed by isobaric, isentropic and isochoric
expansions
Thermodynamic Laws
A physical law is a simple statement of an observable physical phenomenon that has no
underlying, more-basic reason for being except that the most accurate observations have always proved
it to be true.
Zeroth law of thermodynamics If two thermodynamic systems are each in thermal equilibrium with a
third, then they are in thermal equilibrium with each other.
First law of thermodynamics Energy can neither be created nor destroyed. It can only change
forms. In any process, the total energy of the universe remains the same. For a thermodynamic
cycle the net heat supplied to the system equals the net work done by the system.
Second law of thermodynamics The entropy of an isolated system not in equilibrium will tend
to increase over time, approaching a maximum value at equilibrium.
Third law of thermodynamics As temperature approaches absolute zero, the entropy of a
system approaches a constant minimum.