School of Physics and Astronomy Junior Honours Thermodynamics

Lecture TOPIC 1
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GJA 2013-2014

(Finn : 1.1,1.3,1.5)

Synopsis: Preview, and introduction. Systems, surroundings and thermodynamic variables; work and equilibrium introduced.

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

Some denitions
Sample of interest = the system, interacts with surroundings, System and surroundings are separated by some kind of boundary wall. Closed system System cannot exchange matter with its surroundings, but may exchange energy eg. a xed mass of compressible uid in a cylinder closed by a moveable ideal piston (ideal = no leaks). Isolated system No exchange of anything whatsoever including any form of energy with surroundings. eg piston xed in position, and piston and cylinder insulated so there is no heat conduction. gas
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rest of universe surroundings system

Main postulate of thermodynamics Isolated systems settle into equilibrium states having uniform macroscopic properties (in the absence of potentials)*, 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, colour etc
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le topic01.pdf

Denition: 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 of homogeneous portions, with uniform properties in each portion. State functions and state variables The various properties that can be quantied 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. 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

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If the left-hand sample is unaected, 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 (eg 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 Dierent systems may have other key thermodynamic variables to those necessary to specify the state of a uid eg 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 ).

A short list of things you already know

The course assumes you are familiar with the following ... Phases of matter: solids, liquids and gasses 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 Flow and transport phenomena. Bernoullis equation; viscosity; Reynolds number; thermal and electrical conductivity. Elasticity and deformations. Youngs modulus; sound waves; bulk modulus; Compressibility
1 dV V dP

, heat capacity

dQ dT

, thermal expansivity

1 dV V dT

Appendix: Internal energy, U, of an ideal gas

Consider a monatomic gas in a large box with adiabatic walls or walls at the same temperature as the gas. Let n (vx )dvx be the density of atoms (atoms/m3 ) with an x component of velocity between vx and vx + dvx . They will strike the wall at a rate vx n (vx )dvx atoms per unit area per second. Since the wall does not change the distribution of velocities in the box (the gas is at equilibrium) the ux of atoms reected from the wall is the same as that incident. The pressure is the rate of momentum transfer to the wall per unit area which is twice the incident momentum:

P =
0

2 2mvx (vx n (vx )dvx ) = mnv x

with m the mass of an atom and n the total density of atoms,

n=

n (vx )dvx = 2
0

n (vx )dvx

n (vx ) 2 vx dvx n 2 = v 2 = v 2 and Given that the properties of a gas are isotropic v x y z 2 = v x 2 = v 2 + v 2 + v 2 = 3v 2 v x y z x 2 2 N mv nmv = (1) 3 3V with N the total number of atoms and V the volume. The equipartition theorem states that in the classical limit (kB T >>energy level spacing) a contribution of (1/2)kB T to the internal energy U arises from each independent quadratic term in the microscopic expression for the energy (Hamiltonian). Here kB is Boltzmanns constant. The translational kinetic energy therefore contributes 3 in2 2 ,z i }) per atom and i dependent quadratic terms (one for each spatial dimension {x 2 i,y 2 /2 = (3/2)kB T . Substituting this in EQN 1 gives mv P = P = N kB T Nmoles RT = V V (2) Therefore,

with R = kB NA and NA Avogadros number. Thus we have derived the Ideal gas equation. For both monatomic and molecular gases interactions between the atoms or molecules change the pressure from the simple expression derived above; this will be considered later in the course when we discuss the Van der Waals equation of state. Interactions also add further terms to the expression for the total energy U . A gas obeys the ideal gas equation when such interactions can be neglected. For non-interacting gases of rigid molecules the internal energy comprises only kinetic energy. For a monatomic gas U = (3/2)RT . For a diatomic gas there are twice as many velocity coordinates per molecule compared with the monatomic gas, but a constraint per molecule xes the component of the relative inter-particle velocity along the line joining its constituent atoms equal to zero. There are thus 5 independent velocity coordinates per molecule and the equipartition theorem gives U = (5/2)RT .