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School of Physics and Astronomy Junior Honours Thermodynamics GJA 2016-2017

This document provides an overview of key concepts in thermodynamics, including: - Thermodynamics studies systems in equilibrium and how they exchange work, heat and matter with surroundings. - The zeroth law establishes temperature as a physical property allowing comparison of systems in thermal equilibrium. - Systems are defined by their state, characterized by state functions and variables like internal energy, pressure and volume, which are uniform throughout systems in equilibrium. - Thermodynamic processes like heating and cooling occur along paths called isotherms that maintain a constant temperature between states.

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70 views4 pages

School of Physics and Astronomy Junior Honours Thermodynamics GJA 2016-2017

This document provides an overview of key concepts in thermodynamics, including: - Thermodynamics studies systems in equilibrium and how they exchange work, heat and matter with surroundings. - The zeroth law establishes temperature as a physical property allowing comparison of systems in thermal equilibrium. - Systems are defined by their state, characterized by state functions and variables like internal energy, pressure and volume, which are uniform throughout systems in equilibrium. - Thermodynamic processes like heating and cooling occur along paths called isotherms that maintain a constant temperature between states.

Uploaded by

shfgakasg
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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School of Physics and Astronomy

Junior Honours Thermodynamics

GJA 2016-2017

Thermodynamics is the only physical theory of universal content which I am convinced,


within the areas of applicability of its basic concepts, will never be overthrown
A. Einstein 1949
Lecture TOPIC 1 (Finn : 1.1-1.9)
Synopsis: Preview, and introduction. Systems, surroundings and thermodynamic
variables; work and equilibrium introduced. Temperature and the Zeroth law of Thermodynamics.

Main postulate of thermodynamics


Isolated systems settle into equilibrium states having uniform macroscopic properties, eg uniform pressure P, uniform density = mass/V , uniform magnetisation etc. If
we disturb the system we will get the same response independent of where we carry out
the measurement, eg uniform thermal conductivity, compressibility, conductivity, etc
Definition: An equilibrium state is one in which all the bulk physical properties
do not change with time and are uniform throughout the system*.
* for the special case where there is phase separation the system comprises homogeneous
portions, with uniform properties in each portion.
State functions and state variables
The various properties that can be quantified without disturbing the system eg internal
energy U and V, P, T are called state functions or state properties. Properties whose
absolute values are easily measured eg. V,P,T are also called state variables.
An intensive property is a property of a system or of a material itself. It is independent
of how much of the material is present. e.g. density, temperature, pressure, specific
heat capacity
An extensive property is proportional to the amount of material. e.g. mass, energy,
volume, heat capacity
Often, these are distinguished these by using small letters for intensive properties, and
large for extensive ones. In doing calculations, it is very important to be careful with
units here: e.g. volume/mole, volume/kg and volume/atom are all intensive quantities.

Some definitions
Sample of interest = the system,
interacts with surroundings,

rest of universe

System and surroundings are separated by


some kind of boundary wall.

surroundings
system

Closed system
System cannot exchange matter with its surroundings, but may exchange energy
e.g. a fixed mass of compressible fluid in a
cylinder closed by a moveable ideal piston
(ideal = no leaks).
gas

Isolated system

 -

No exchange of anything whatsoever including any form of energy with surroundings.


e.g. piston fixed in position, and piston and
cylinder insulated so there is no heat conduction.
Adiabatic and diathermal boundary walls
Consider the arrangement opposite in which
two systems comprising gases are separated by a
rigid wall. If the right-hand gas sample is compressed (an external force pushes the piston in)
the values of its state variables will change. In
particular, its temperature will increase.

gas

more
gas

 -

If the left-hand sample is unaffected, the rigid wall between the two gas samples is
called adiabatic, implying there is no transfer of heat energy across it.
If the state of the left-hand gas sample changes (e.g. the property T of the gas increases)
the rigid wall is called diathermal. A thermal interaction (exchange of energy) will
have occurred, and the two samples are in thermal contact.
Adiabatic = No heat exchange = thermally insulating wall
Diathermal = Heat exchange = thermally conducting wall

Other Thermodynamic variables


Different systems may have other key thermodynamic variables to those necessary to
specify the state of a fluid, e.g. for an elastic band held under tension, the value of the
tension F and the length L of the band are also needed to describe its mechanical state
(and are much more relevant than P and V ).
2

A short list of things you already know


Phases of matter: solids, liquids and gases
Temperature. Thermometers, Kelvin and Celsius scales, absolute zero.
Ideal gases. Kinetic theory; Maxwell-Boltzmann velocity distributions; degrees of freedom and equipartition theorem.
Non-ideal gases. Lennard-Jones type interaction; van der Waals approach; instability
in PV isotherms; phase coexistence.
Liquid phase; vapour pressure; surface tension.
Properties of materials: compressibility, heat capacity, thermal expansivity, latent heat
Transport phenomena: Bernoulli equation; thermal and electrical conductivity.
Elasticity and deformations. Youngs modulus; sound waves; bulk modulus;
You should also have seen these definitions, shortly well see why they are incomplete.
dP
dV
; bulk modulus K = V dV
; heat capacity C = dQ
; thermal
Compressibility = 1
V dP
dT
1 dV
expansivity = V dT .

Fractional changes and absolute values


Some thermodynamic quantities (e.g. Volume) have an obvious zero. Others (e.g. Temperature) have a less-obvious zero. For these quantities it makes sense to talk about
fractional changes.
Other quantities including internal energy, have no obvious choice of zero - consider
e.g. adding the rest mass energy to an ideal gas. It provides a big extra contribution, but
whether we include it or not, the measurable quantities of the ideal gas do not change.
We are free to choose the zero, but then should never use ratios.
ln V
ln V
; = d dT
.
Notice that some materials properties are log derivatives, e.g. = d dP
Log derivatives relate the fraction by which something has changed, rather than the
absolute amount, so only make sense when a reference state (e.g. zero) is well defined.

Zeroth Law
Suppose that two systems (A,B) which are
thermally isolated from their surroundings
are put in thermal contact (connected by
a diathermal wall) and allowed to reach
thermal equilibrium: i.e. their pressure
and volume reach equilibrium values.

diathermal
wall
A B

A C

B C

Experimental observation: if A and a third suitable system C are similarly brought


into thermal equilibrium, this results in no change in the values of the state variables of A,
then it is observed that B and C, if put in thermal contact are also in thermal equilibrium
with each other. This observation can be repeated for fourth, fifth, ... systems (D, E, ...).
and is summarised as the Zeroth Law of Thermodynamics:
Zeroth Law: If each of two systems is in thermal equilibrium with a third
system they are in thermal equilibrium with each other.
3

Existence of Temperature
If many systems are in thermal equilibrium with each other, they must have the same value
of some property (state variable). This property is called the thermodynamic temperature
T.
The temperature of a system is a property that determines whether or not
that system would be in thermal equilibrium with other systems.
For two systems to be in complete thermodynamic equilibrium, they must have a common temperature and show no net (1) exchange of material (no diffusion), (2) chemical
reaction (chemical equilibrium), (3) unbalanced force (mechanical equilibrium) (4) charge
flow (electromagnetic equilibrium).
For a simple fluid, only two state variables are required to specify an equilibrium
state, so temperature must be a function of P and V : T = T (P, V ). Mathematically
the relation T = T (P, V ) can also be expressed as F (P, V, T ) = 0 where the function F
depends on the material. Equivalently we can also write P = P (V, T ) and V = V (P, T )
where P (V, T ) and V (P, T ) are material dependent functions. The relationship between
P, V and T is an example of an equation of state, and depends on the material.
The equation of state for n moles of ideal gas can be written as T = T (P, V ) = P V /nR.
Isotherms
A system consisting of a fixed mass of gas can exist in a
number of equilibrium states corresponding to the same
temperature T but with different values of its pressure
and volume: (P 0 , V 0 ), (P 00 , V 00 ), (P 000 , V 000 ), ... . The line
through plotted values T (V, P ) = Ti , ... is called an
isotherm. An isotherm can be drawn for each value of
Ti . For given P, V a system has only one temperature, so
different isotherms cannot cross.
Three Temperatures are all the same
Remarkably, the Temperature related to the kinetic energy of an ideal gas, the Temperature which determines thermal equilibrium, and the Temperature which appear
in statistical distributions (Boltzmann, Fermi-Dirac and Bose-Einstein) are all the same.
Statistical Redefinition Kelvin = Joule/Boltzmann
If temperature is kinetic energy, we have the relationship mv 2 = 3kB T . Equivalently
the equipartioned energy of any degree of freedom is kB T /2. To relate Kelvins to Joules
requires an accurate measurement of kB , e.g. from the speed of sound in ideal gas:
s
s
r

P
P
NA kB T
M c20
c0 =
=
=
= kB =
s

M
T NA
where is the density and M the molar mass. This was recently measured more accurately
than the critical point of water can be, using low density limit of speed of sound in argon,
by resonance of copper sphere whose diameter is known to 11.7nm (500 atoms).
(de Podesta et al 2013 Metrologia 50 354 http://iopscience.iop.org/0026-1394/50/4/354)

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