Entropy change systems

Figure 4.5-4 The system entropy change and the prestsure in cell 2 as a runction of the pressure in cell I.

Entropy Changes in the System. Entropy Changes in the Surroundings The Third Law of Thermodynamics and... 

Let us examine the time variation of the entropy of a composite system (entropy change for the composite system from time to i + dt), dS ... 

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. 

B2.4.2). The slope of the line gives AH, and the intercept at 1/J= 0 is related to A imimolecular reaction, such as many cases of exchange, might be expected to have a very small entropy change on gomg to the transition state. However, several systems have shown significant entropy contributions—entropy can make up more than 10% of the barrier. It is therefore important to measure the rates over as wide a range of temperatures as possible to obtain reliable thennodynamic data on the transition state. 

Second Law of Thermodynamics. The entropy change of any system together with its surroundings is positive for a real process, approaching zero as the process approaches reversibiUty ... 

The entropy change of any. system and its. surroundings, considered together, re.sulting from any real proce.s.s is positive, approaching zero when the proce.s.s approaches reversibility. 

Since heat transfer with respec t to the surroundings and with respect to the system are equal but of opposite sign, = —Q. Moreover, the second law requires for a reversible process that the entropy changes of system and surroundings be equalbut of opposite sign AS = —AS Equation (4-356) can therefore be written Q = TcAS In terms of rates this becomes... 

However, we have a problem in working out this integral unless we continuously monitor the movements of the car, we will not know just how much heat dQ will be put into the system in each temperature interval of T to T + dT over the range to Tj. The way out of the problem lies in seeing that, because Qextemai = 0 (see Fig. 5.2), there is no change in the entropy of the (system + environment) during the movement of the car. In other words, the increase of system entropy S2 - Si must be balanced by an equal deerease in the entropy of the environment. Since the environment is always at Tq we do not have to integrate, and can just write... 

As known, SEC separates molecules and particles according to their hydro-dynamic volume in solution. In an ideal case, the SEC separation is based solely on entropy changes and is not accompanied with any enthalpic processes. In real systems, however, enthalpic interactions among components of the chromatographic system often play a nonnegligible role and affect the corresponding retention volumes (Vr) of samples. This is clearly evident from the elution behavior of small molecules, which depends rather strongly on their chemical nature and on the properties of eluent used. This is the case even for... 

Entropy can be defined in several quantitative ways. If ITis the number of ways to arrange the components of a system without changing the internal... 

The second law of thermodynamics also consists of two parts. The first part is used to define a new thermodynamic variable called entropy, denoted by S. Entropy is the measure of a system s energy that is unavailable for work.The first part of the second law says that if a reversible process i f takes place in a system, then the entropy change of the system can be found by adding up the heat added to the system divided by the absolute temperature of the system when each small amount of heat is added ... 

The entropy change of a system during any process depends only upon its initial and final states and not upon the path of the process by which it proceeds from its initial to its final state. Thus one can devise a reversible idealized process to restore a system to its initial state following a change and thereby determine AS =... 

Entropy, like enthalpy (Chapter 8), is a state property. That is, tine entropy depends only on the state of a system, not on its history. The entropy change is determined by the entropies of the final and initial states, not on the path followed from one state to another. 

The relationship between entropy change and spontaneity can be expressed through a basic principle of nature known as the second law of thermodynamics. One way to state this law is to say that in a spontaneous process, there is a net increase in entropy, taking into account both system and surroundings. That is,... 

Notice that the second law refers to the total entropy change, involving both system and surroundings. For many spontaneous processes, the entropy change for the system is a negative quantity. Consider, for example, the rusting of iron, a spontaneous process ... 

AS° for this system at 25°C and 1 atm can be calculated from a table of standard entropies it is found to be —358.4 J/K. The negative sign of AS° is entirely consistent with the second law. All the law requires is that the entropy change of the surroundings be greater than 358.4 J/K, so that ASunIverse > 0. 

In principle, the second law can be used to determine whether a reaction is spontaneous. To do that, however, requires calculating the entropy change for the surroundings, which is not easy. We follow a conceptually simpler approach (Section 17.3), which deals only with the thermodynamic properties of chemical systems. 

In some cases, an alternative explanation is possible. It may be assumed that any very complex organic counterion can also interact with the CP matrix with the formation of weak non-ionic bonds, e.g., dipole-dipole bonds or other types of weak interactions. If the energy of these weak additional interactions is on the level of the energy of the thermal motion, a set of microstates appears for counterions and the surrounding CP matrix, which leads to an increase in the entropy of the system. The changes in Gibbs free energy of this interaction may be evaluated in a semiquantitative way [15]. 

E3.7 A block of copper weighing 50 g is placed in 100 g of HiO for a short time. The copper is then removed from the liquid, with no adhering drops of water, and separated from it adiabatically. Temperature equilibrium is then established in both the copper and water. The entire process is carried out adiabatically at constant pressure. The initial temperature of the copper was 373 K and that of the water was 298 K. The final temperature of the copper block was 323 K. Consider the water and the block of copper as an isolated system and assume that the only transfer of heat was between the copper and the water. The specific heat of copper at constant pressure is 0.389 JK. g l and that of water is 4.18 J-K 1-g 1. Calculate the entropy change in the isolated system. 

We will take this isolated system and displace it from equilibrium by an infinitesimal amount in some manner. The system will then return to equilibrium and an entropy change will occur in the system given by... 

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