Law second

Two classically important statements have been provided. The first statement, due to Lord Kelvin, is that it is not possible by a cyclic process to take heat from a reservoir and convert it into work without at the same time transferring heat from a hot to a cold reservoir. This statement of the second law is related to equilibria when it is realized that work can be obtained from a system only when the system is not already at equilibrium. The statement recognizes that the spontaneous process is the flow of heat from a higher to a lower temperature and that only from such a spontaneous process can the work be acquired. The second important classic statement, due to Clausius, is that it is not possible to transfer heat from a cold to a hot reservoir without at the same time converting a certain amount of work into heat. The operation of a refrigerator readily illustrates this statement 

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Derive Eq. III-21 from the first and second laws of thermodynamics and related definitions. 

The treatments that are concerned in more detail with the nature of the adsorbed layer make use of the general thermodynamic framework of the derivation of the Gibbs equation (Section III-5B) but differ in the handling of the electrochemical potential and the surface excess of the ionic species [114-117]. The derivation given here is after that of Grahame and Whitney [117]. Equation III-76 gives the combined first- and second-law statements for the surface excess quantities... 

The adsorption of detergent-type molecules on fabrics and at the solid-solution interface in general shows a complexity that might be mentioned briefly. Some fairly characteristic data are shown in Fig. XlIl-15 [242]. There is a break at point A, marking a sudden increase in slope, followed by a maximum in the amount adsorbed. The problem is that if such data represent true equilibrium in a two-component system, it is possible to argue a second law violation (note Problem Xni-14) (although see Ref. 243). 

It was stated in Section XIII-6C that an adsorption maximum, as illustrated in Fig. Xin-15, implies a second law violation. Demonstrate this. Describe a specific set of operations or a machine that would put this violation into practice. 

In Section XVII-16C there is mention of S-shaped isotherms being obtained. That is, as pressure increased, the amount adsorbed increased, then decreased, then increased again. If this is equilibrium behavior, explain whether a violation of the second law of thermodynamics is implied. A sketch of such an isotherm is shown for nitrogen adsorbed on a microporous carbon (see Ref. 226). 

LID) see Ref. 139. In this last method, a small area, about 0.03 cm radius, is depleted by a laser beam, and the number of adatoms, N(t), that have diffused back is found as a function of time. From Pick s second law of diffusion ... 

As we shall see, because of the limitations that the second law of thennodynamics imposes, it may be impossible to find any adiabatic paths from a particular state A to another state B because In this... 

Obviously die first law is not all there is to the structure of themiodynamics, since some adiabatic changes occur spontaneously while the reverse process never occurs. An aspect of the second law is that a state fimction, the entropy S, is found that increases in a spontaneous adiabatic process and remains unchanged in a reversible adiabatic process it caimot decrease in any adiabatic process. 

The next few sections deal with the way these experimental results can be developed into a mathematical system. A reader prepared to accept the second law on faith, and who is interested primarily in applications, may skip section A2.1.4.2 and section A2.1.4.6 and perhaps even A2.1.4.7. and go to the final statement in section A2.1.4.8. 

The surfaces in which the paths satisfying the condition = 0 must lie are, thus, surfaces of constant entropy they do not intersect and can be arranged in an order of increasing or decreasmg numerical value of the constant. S. One half of the second law of thennodynamics, namely that for reversible changes, is now established. 

The total change d.S can be detennined, as has been seen, by driving the subsystem a back to its initial state, but the separation into dj.S and dj S is sometimes ambiguous. Any statistical mechanical interpretation of the second law requires that, at least for any volume element of macroscopic size, dj.S > 0. However, the total... 

Equation (A2.1.21) includes, as a special case, the statement dS > 0 for adiabatic processes (for which Dq = 0) and, a fortiori, the same statement about processes that may occur in an isolated system (Dq = T)w = 0). If the universe is an isolated system (an assumption that, however plausible, is not yet subject to experimental verification), the first and second laws lead to the famous statement of Clausius The energy of the universe is constant the entropy of the universe tends always toward a maximum. ... 

There are many equivalent statements of the second law, some of which involve statements about heat engines and perpetual motion machines of the second kind that appear superficially quite different from equation (A2.T21). They will not be dealt with here, but two variant fonns of equation (A2.T21) may be noted in... 

One may note, in concluding this discussion of the second law, that in a sense the zeroth law (thennal equilibrium) presupposes the second. Were there no irreversible processes, no tendency to move toward equilibrium rather than away from it, the concepts of thennal equilibrium and of temperature would be meaningless. 

In the Lewis and Gibson statement of the third law, the notion of a perfect crystalline substance , while understandable, strays far from the macroscopic logic of classical thennodynamics and some scientists have been reluctant to place this statement in the same category as the first and second laws of thennodynamics. Fowler and Guggenheim (1939), noting drat the first and second laws both state universal limitations on processes that are experunentally possible, have pointed out that the principle of the unattainability of absolute zero, first enunciated by Nemst (1912) expresses a similar universal limitation ... 

By the standard methods of statistical thermodynamics it is possible to derive for certain entropy changes general formulas that cannot be derived from the zeroth, first, and second laws of classical thermodynamics. In particular one can obtain formulae for entropy changes in highly di.sperse systems, for those in very cold systems, and for those associated, with the mixing ofvery similar substances. 

Snch a generalization is consistent with the Second Law of Thennodynamics, since the //theorem and the generalized definition of entropy together lead to the conchision that the entropy of an isolated non-eqnilibrium system increases monotonically, as it approaches equilibrium. 

In 1872, Boltzmaim introduced the basic equation of transport theory for dilute gases. His equation detemiines the time-dependent position and velocity distribution fiinction for the molecules in a dilute gas, which we have denoted by /(r,v,0- Here we present his derivation and some of its major consequences, particularly the so-called //-tlieorem, which shows the consistency of the Boltzmann equation with the irreversible fomi of the second law of themiodynamics. We also briefly discuss some of the famous debates surrounding the mechanical foundations of this equation. 

This completes the heuristic derivation of the Boltzmann transport equation. Now we trim to Boltzmaim s argument that his equation implies the Clausius fonn of the second law of thennodynamics, namely, that the entropy of an isolated system will increase as the result of any irreversible process taking place in the system. This result is referred to as Boltzmann s H-theorem. 

We are going to carry out some spatial integrations here. We suppose that tire distribution function vanishes at the surface of the container and that there is no flow of energy or momentum into or out of the container. (We mention in passing that it is possible to relax this latter condition and thereby obtain a more general fonn of the second law than we discuss here. This requires a carefiil analysis of the wall-collision temi The interested reader is referred to the article by Dorfman and van Beijeren [14]. Here, we will drop the wall operator since for the purposes of this discussion it merely ensures tliat the distribution fiinction vanishes at the surface of the container.) The first temi can be written as... 

The are many ways to define the rate of a chemical reaction. The most general definition uses the rate of change of a themiodynamic state function. Following the second law of themiodynamics, for example, the change of entropy S with time t would be an appropriate definition under reaction conditions at constant energy U and volume V ... 

Pick s second law of difflision enables predictions of concentration changes of electroactive material close to the electrode surface and solutions, with initial and boundary conditions appropriate to a particular experiment, provide the basis of the theory of instrumental methods such as, for example, potential-step and cyclic voltanunetry. 

Figure Bl.28.2. Pick s laws of dififiision. (a) Pick s first law, (b) Pick s second law.

The diffusion of small molecules in polymers can be described using Pick s first and second laws. In a onedimensional situation, the flux J(c, x) as a function of the concentration c and the position x is given by... 

If tire diffusion coefficient is independent of tire concentration, equation (C2.1.22) reduces to tire usual fonn of Pick s second law. Analytical solutions to diffusion equations for several types of boundary conditions have been derived [M]- In tlie particular situation of a steady state, tire flux is constant. Using Henry s law (c = kp) to relate tire concentration on both sides of tire membrane to tire partial pressure, tire constant flux can be written as... 

In sorjDtion experiments, the weight of sorbed molecules scales as tire square root of tire time, K4 t) ai t if diffusion obeys Pick s second law. Such behaviour is called case I diffusion. For some polymer/penetrant systems, M(t) is proportional to t. This situation is named case II diffusion [, ]. In tliese systems, sorjDtion strongly changes tire mechanical properties of tire polymers and a sharjD front of penetrant advances in tire polymer at a constant speed (figure C2.1.18). Intennediate behaviours between case I and case II have also been found. The occurrence of one mode, or tire otlier, is related to tire time tire polymer matrix needs to accommodate tire stmctural changes induced by tire progression of tire penetrant. 

The pressure is usually calculated in a computer simulation via the virial theorem ol Clausius. The virial is defined as the expectation value of the sum of the products of the coordinates of the particles and the forces acting on them. This is usually written iV = X] Pxi where x, is a coordinate (e.g. the x ox y coordinate of an atom) and p. is the first derivative of the momentum along that coordinate pi is the force, by Newton s second law). The virial theorem states that the virial is equal to —3Nk T. 

The Boltzmann distribution is fundamental to statistical mechanics. The Boltzmann distribution is derived by maximising the entropy of the system (in accordance with the second law of thermodynamics) subject to the constraints on the system. Let us consider a system containing N particles (atoms or molecules) such that the energy levels of the... 

The trajectory is obtained by solving the differential equations embodied in Newton s second law (F = ma) ... 

The equation of motion is based on the law of conservation of momentum (Newton s second law of motion). This equation is written as... 

If the spring follows Hooke s law, the force it exerts on the mass is directly proportional and opposite to the excursion of the particle away from its equilibrium point Xe- The particle of mass m is accelerated by the force F = —kx of the spring. By Newton s second law, F = ma, where a is the acceleration of the mass... 

Write the rotational analog of Hooke s law for the torque x driving the oseillation in Problem 3. Write the rotational analog of Newton s second law. Combine the two laws to obtain the rotational analog of the Newton-Hooke equation, Eq. (4-1). 

From Newton s second law, noting that more than one force may influence each mass, where a is the acceleration a = =. For the coupled masses... 

The force on one nucleus due to sPetching or compressing the bond is equal to the force constant of the bond k times the distance between the nuclei x2 — xi). It is equal and opposite to the force acting on the other nucleus, and it is also equal to the mass times the acceleration x by Newton s second law (see section on the hamionic oscillator in Chapter 4). The equations of motion are... 

The classical-mechanical problem for the vibrational motion may now be solved using Newton s second law. The force on the x component of the i atom is... 

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