28 INTERNAL ENERGY AND ENTROPY 2.2. Thermodynamic analysis For the more explicit examination of these thermoelastic phenomena it is necessary to develop relations between force, length, and temperature on the one hand and the thermodynamic quantities, internal energy and entropy, on the other. The required relations are obtainable directly from the first and second laws of thermodynamics. From the first law of thermodynamics the change in internal energy dU in any process is given by dU=do+aw, (2.4) where d@ and d W are respectively the heat absorbed by the system and the work done on it by the external forces. The second law defines the entropy change dS in a reversible process by the relation TdS=d0, (2.2) and hence from (2.1), we have for a reversible process dii=Tds+dw. (2.3) In discussing the equilibrium of a system which is subject to reversible changes (e.g. clastic deformations) it is convenient to introduce the Helmholtz free energy A, defined by the relation A=U-TS. (24) For a change taking place at constant temperature we have then dA=dU+Tds. (2.4) Combining this equation with (2.3) we obtain the standard ther- modynamic result dA=dW (constant T), (2.6) which signifies that in a reversible isothermal process the change in Heimholtz free energy is equal to the work done on the system by the applied forces. in most thermodynamic textbooks the subject is subsequently developed with particular reference to gases and liquids, for which the significant variables include pressure p and volume V. The work done on the system in a small displacement is then written as dW=—pdV.CHANGES ON NRFORMATION 29 In discussing problems related to the elasticity of solids, on the other hand, we are concerned primarily with the work done by the applied stress, corresponding, for example, to u tensile force f acting on a specimen of length 4, in which case the work done in a small displacement is dW=fdl (2.7) When in addition a hydrostatic pressure (e.g. atmospheric pressure) is also present the total work done by the applied forces becomes dW = fdi-pa¥, (2.7a) For strict accuracy it is necessary to take account of both terms on the right-hand side of (2.74). But in the case of rubbers, the volume change d ¥ is usually very small, and if p is the atmospheric pressure the term p dV is less than f df by a factor of 107 or 10°. Asa first approximation we may therefore neglect this term and use eqn (2.7), which is strictly accurate only at zero applied pressure or under constant-volume conditions, in place of the exact expression (2.7a) (the more accurate analysis, not involving this assumption, is referred to in § 2.4). By making use of eqns (2.6) and (2.7) the tension may then be expressed in the form y~(&) -(). 28) which shows thut the tensile force is equal to the change in Helmholtz free energy per unit increase in length of the specimen. ‘The significunce of the important relation (2.8) may be better appreciated by reference to Fig. 2.5, which represents diagrammati- cally the variation of Helmholtz free energy lor an clastic body as 2 function of its length | The unstressed state is such that the Helmholtz free energy is a minimum, sa that (04/00,=0 when ly Tf fis greater than f, (@A/al), is positive, corresponding to a tensile force, while if | is less than |, (@A/al), is negative, corresponding to a compressive force. (It should be noted, however, that the force-deformation relation will not in general be linear, except for very small strains.) The tension, like the free energy, may be expressed as the sum of two terms (from eqn (2.5), thus HQC), an30 INTERNAL ENERGY AND ENTROPY Fics, 2.5, Dependence of Helmholtz free energy A and force f on length | for specimen subjected Wo uniaxial extension or compression. = unstrained length. of which the first represents the change in internal energy and the second the change in entropy, per unit increase in Jength, The second term is related to the temperature coefficient af tension, as will now be shown. Writing qn (2.4) in differential form, we have for any change (i.e. not necessarily isothermal) dA=dU = FdS-S$ dT, whilst from (2.3) and (2.7) dij=fdl+Tds. Combination of these two equations gives dA fdl-SdT. Hence, by partial differentiation, aA aA rf ar By a well-known property of partial differentials Se a a). “aT vat ). and hence, from eqns (2.10), (8), --(%), es al, aT. =—5. (2.10)gn (2.11) gives the entropy change per unit extension in terms of the measurable quantity (df/d'T), the temperature coefficient of tension at constant length. Insertion of this relation in (2.9) gives for the corresponding internal energy change (a a r(2t). (2.12) The relations (2.11) and (2.12) are of fundamental importance in rubber elasticity, since they provide a direct means of determining experimentally both the internal energy and entropy changes accompanying a deformation. ‘Their application may be illustrated by reference to Fig. 2.6, in which the curve CC’ represents the Force at constant length 0 ‘Temperature (K) FIG. 2.6. Slope and intercept of force-temperature curve. variation with temperature of the force at constant length, which may or may not be linear. The slope of this curve at a point P is (af/aT),, which from eqn (2.11) gives the entropy change per unit extension (#S/01), for an isothermal extension at the temperature T. In a corresponding way, the intercept OA of the tangent to the curve al P on the vertical axis T= Ois f~ Tlaf/eT}, which by eqn (2.12) is equal to the change of internal energy per unit extension. ‘Thus the internal energy and entropy contributions to the force at any given value of the extension are directly obtainable from the experimental force-temperature plot. In particular, if the farce- temperature plot is linear (as in Fig, 2.1) beth internal energy anda2 INTERNAL ENERGY AND ENTROPY entropy terms are independent of temperature. [f in addition the force-temperature relation is represented by a straight line passing through the origin, the internal energy term is zera, i.¢. the clastic force arises solely from the change in entropy on extension.