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Lecture 8 Notes:

Thermodynamics
Physics 102.002
Prof. Michael Gold
September 24, 2007

Thermodynamics: Empirical laws


describing average properties of bulk
matter.

All matter is made up of atoms.


Atoms are very small (~0.1 nm) and
therefore bulk matter contains a very
very large number of atoms.
Avogadros number NA=6.02x1023
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physics 102.002 Lecture 8

Statistical Mechanics
Laws of thermodynamics can be understood (in fact
rigorously derived) from the average behavior of
molecules (atoms).
Thermodynamic laws are rigorously obeyed because the
typical number of molecules is so huge that typical
deviations from average are immeasurably small and the
probability of large deviations is infinitesimally small.

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physics 102.002 Lecture 8

Temperature
A measure of the mean kinetic energy of molecules
per degree of freedom.
Degree of freedom is the number of ways a
molecule can move.
Monatomic: f=3 displacement (vx,vy,vz)
Diatomic: f=5 displacement plus 2 rotational
modes at moderate temperatures.
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physics 102.002 Lecture 8

Heat
A form of energy (molecular kinetic energy)
that is transferred between materials as a
result of differences in temperature through
direct (thermal) contact.

Heat always flows from


hot to cold.
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physics 102.002 Lecture 8

Entropy
A measure of molecular disorder:
The arrow of time: disorder of universe always
increases with time.
Perpetual motion machines are impossible.
A thermodynamic limit to the efficiency of engines.
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How do we
know this?
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physics 102.002 Lecture 8

Law of definite
proportions
Whenever a given compound is formed from two
elements, the ratio of the combining masses of
the elements is observed to be constant. This
holds for every compound although the mass
ratio is different for each compound.
Dalton (1807)-- Atoms of each
element have a definite mass.
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physics 102.002 Lecture 8

Example
32g O + 12g C = CO2 carbon dioxide
16g O + 12g C = CO carbon monoxide

Ratio of oxygen in 2 compounds is 2:1

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Definition of a Mole
1 mole is an Avogadros number of things
(usually molecules).
Like 1 dozen.
Empirically defined as the number of carbon atoms in
12 g of carbon.

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physics 102.002 Lecture 8

Definition of amu
This also defines the atomic mass unit (amu).
12 amu is the mass of 1 carbon atom = mass of 1 mole
of carbon / Avogadros number= 12g/Avogadros
number. Obviously a very small number.
The 12 comes from the fact that the carbon-12 atom
Contains 6 protons + 6 neutrons (+6 electrons of
negligible mass). So 1amu is very nearly the mass of
a proton or neutron.

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Examples
1 mole of hydrogen has a mass of 1g.
the hydrogen atom has a mass of 1amu.

1 mole of oxygen has a mass of 16g. The oxygen


atom has mass of 16 amu.

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Density
Density = Mass/volume
Water density = 1g/cm3
Water is quite dense. We can measure
less-dense substances relative to water
via Archimedes principle

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Density of Ice
Unusual property that solid state is less
dense than liquid state.
density = 0.92 g/cm3
Think about the implications of this fact for life!

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Archimedes
FB

W=FB
g x (mass of object) = g
x (mass of displaced
water)

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Pressure
P = F/(area)

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States of matter
solid , liquid , gas
At very low temperatures
Super-fluid (zero viscosity fluid, liquid He-4
Super-conductor
High temperatures
plasma: ionized gas (e.g. inside fluorescent
lamps, stars)
Very high temperatures: quark-gluon plasma
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Measuring
Temperature
Most substances expand
when heated

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Measure of Heat
1 calorie = heat required to increase the
temperature of 1g water by 1 degree C
Note: food Calorie = 1 kilocalorie

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Ideal Gases
Important experiments with gases
leading to the ideal gas law. Ideal
means the limit of non-interacting
molecules. An excellent
approximation for many gases.

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Ideal Gas Law


P is pressure, V is volume
n is number of moles of the gas
T is the absolute temperature (Kelvin)
R is a universal constant 8.31 J/(mole K)

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Absolute Temperature (Kelvin scale)

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Microscopic View
A measure of the mean kinetic energy of molecules
per degree of freedom.

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Why is there no hydrogen in the


atmosphere?
At atmospheric temperatures, H atoms move very
fast on average, with a significant fraction
exceeding the earths escape velocity. Over time,
the H escapes earths gravity.
We can produce H by separating water which
requires energy.
Therefore, hydrogen is an energy storage device,
not a source of energy on earth.
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Microscopic view of pressure

Atomic collisions are perfectly elastic.


How can this be?
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Measuring Avogadros
Number
Einstein (1905) explained Brownian motion
(1828) -- the random motion of small particles
suspended in liquid-- an terms of motion of
molecules of which the liquid is composed.

R is displacement of particle of radius r in time t


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Perrins Experiment (1908)


Devised technique to produce small resin spheres of
Uniform size of about 10-6 m (micron)
Measured NA = 6 x 1023

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Weighing the Atom


Mass of atom =
(atomic mass units)/ Avogadros number

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Boltzmans Constant k

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