School of Physics and Astronomy Junior Honours Thermodynamics GJA 2013-2014

Lecture TOPIC 2 1 (Finn: 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9) Synopsis: Temperature. The isotherm. Temperature and the Zeroth law of Thermodynamics. Temperature scales. Suppose two systems (A,B) which are thermally isolated from their surroundings (and from the rest of the universe) are put in thermal contact (connected by a diathermal wall) and allowed to reach thermal equilibrium: ie 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, fth, ... 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. Logical conclusion: If each is in thermal equilibrium with all the others, they must have the same value of some property that has a common value [see appendix]. This property is called 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 have to have a common temperature and (1) show no exchange of material (no diusion through wall of contact), (2) show no chemical reactions (chemical equilibrium), (3) be subject to no unbalanced force (mechanical equilibrium) (4) support no charge ow (electromagnetic equilibrium). For a simple uid, since only two state variables are required to specify an equilibrium state, T must be a function of P and V : T = f (P, V ). The function f depends on the material (it will be dierent for Ar, O2 , air, an Ideal gas, a Van der Waals gas etc). For notational convenience we use T (P, V ) to denote the function f (P, V ). Mathematically the relation T = f (P, V ) can also be expressed as F (P, V, T ) = 0 where the function F again depends on the material. Equivalently we can also write P = P (V, T ) and
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V = V (P, T ) where P (V, T ) and V (P, T ) are material dependent functions. The material dependent relationship between P, V and T is an example of an equation of state. For n moles (gram molecules) of an ideal gas occupying a volume V at pressure P and temperature T , the equation of state is P V = nRT , where R is the gas constant. Then T = T (P, V ) = P V /nR. Isotherms A system consisting of a xed mass of gas can exist in a number of equilibrium states corresponding to the same temperature T but with dierent values of its pressure and volume: P ,V , P ,V , P ,V , ..... .The line through plotted values (V ,P ), (V ,P ), (V ,P ), ..... is called an isotherm. An isotherm can be drawn for each value of the temperature (sketch). Temperature scales There are many possible practical temperature scales. For a xed amount of an ideal gas, kept in a vessel of constant volume, its pressure is directly proportional to a temperature dened to be TIG = P V /nR. Its value is stated in kelvin, denoted by the symbol K. In this context the variable P is called a thermometric property. Other systems have their own thermometric properties, eg XR , the electrical resistance of a sample of (a carefully chosen) metal; X , the length by which a liquid expands, when heated, into a narrow-bore tube (mercury-in-glass thermometer). Two point calibration - centigrade scale All practical thermometers have to be calibrated. For a liquid-in-glass thermometer, suppose the lengths of liquid are , steam and ice when the liquid sample is in equilibrium at, respectively, the unknown temperature , the temperature of the boiling point of water and the temperature of the freezing point of water. The centigrade temperature is dened by: ice = 100 steam ice This is an example of a two point callibration. Dierent thermometers calibrated at the same xed points (steam and ice points) agree at these points but, in general do not agree for other temperatures. One point calibration - Kelvin and Celsius scales For precision thermometry, the constant volume gas thermometer is used with temperature Tgasscale measured on the gas scale. In general the scale is specic to the density and type of gas used. The calibration equation uses ratios, and only one xed point is then needed. For example, the xed point can be taken to be the triple point of water where ice, water and water vapour coexist, which also imposes a xed pressure of water 2

vapour (Ptp (H2 O) 0.006 atmosphere). The temperature at this xed point is dened to have a numerical value eg. 273.16. The sample of gas used in the thermometer will exert a pressure Ptp (gas) at the xed point and a dierent pressure P (gas) at some other temperature. Temperature on the gas scale is then dened according to: Tgasscale = 273.16 (P (gas)/Ptp (gas)) For all gases, Tgasscale converges to the same limiting value (equal to that for an ideal gas) as the mass of gas in the xed volume is reduced to zero [reducing both P (gas) and Ptp (gas)]. This procedure and the choice of 273.16 for the value of the temperature at the triple point of water denes the ideal gas temperature scale, TIG : TIG = lim 273.16 (
Ptp0

P ) (in K, ie kelvin) Ptp

The temperatures of the ice point and the steam point on the ideal gas scale are approximately 273.15 K and 373.12 K. The convenient Celsius scale temperature, t, on which scale the ice point temperature is 0 C, is specied by: t( C) = T (K) 273.15 Ice melts (at atmospheric pressure) at 0 C and water boils at 99.97 C!

Statistical Redenition
From the observation that the ideal gas temperature is kinetic energy, it seems sensible to relate the denition of temperature to energy. We have the relationship mv 2 = 3kB T , equivalently the equipartioned energy of any degree of freedom is kB T /2. What is needed to relate Kelvins to Joules is an accurate measurement of kB . Speed of sound in ideal gas is c0 = P =
s

P =

NA kB T M
M c2

where is the density and M the molar mass. This implies kB = T N0A . This recently became measured more accurately than the critical point of water can be, using low desnity limit of speed of sound in argon, by resonance of copper sphere whose diameter is known to 11.7nm (500 atoms) (Michael de Podesta et al 2013 Metrologia 50 354 http://iopscience.iop.org/0026-1394/50/4/354)

Appendix: Zeroth Law Existence of T

Specically we show that there exist functions 1 (P1 , V1 ) and 2 (P2 , V2 ) describing systems 1 & 2 such that if 1 (PA , VA ) = 2 (PB , VB ) the state (VA , PA ) of system 1 and the state (VB , PB ) of system 2 are in thermal equilibrium Consider systems A, B, C each specied by two mechanical variables P, V . Systems A, B, C can be dierent masses of dierent gases obeying dierent equations of state. For A & C to be in thermal equilibrium some relationship between the dierent state variables must be satised. F1 (PA , VA , PC , VC ) = 0 where F1 is some function. Solving for PC PC = f1 (PA , VA , VC ) with f1 some other function. Similarly for B,C to be in thermal equilibrium F2 (PB , VB , PC , VC ) = 0 PC = f2 (PB , VB , VC ) (2) (1)

The condition for A and B to be separately in equilibrium with C from EQNs 1 and 2 is f1 (PA , VA , VC ) = f2 (PB , VB , VC ) (3)

The zeroth law gives that if A and B are separately in thermal equilibrium with C then A & B are also in thermal equilibrium with each other. Therefore, F3 (PA , VA , PB , VB ) = 0 (4)

For EQN 4, which does not depend on VC and EQN 3 to be equivalent VC must cancel from both sides of EQN 3. eg. f1 (PA , VA , VC ) = 1 (PA , VA ) (VC ) + (VC ) f2 (PB , VB , VC ) = 2 (PB , VB ) (VC ) + (VC ) Therefore there exist functions 1 (PA , VA ) and 2 (PB , VB ) that describe each system and EQN 3 implies that 1 (PA , VA ) = 2 (PB , VB ) when A and B are in thermal equilibrium.