Balancing spontaneity

The light emitted in the spontaneous recombination process can leave tire semiconductor, be absorbed or cause additional transitions by stimulating electrons in tire CB to make a transition to tire VB. In tliis stimulated recombination process anotlier photon is emitted. The rate of stimulated emission is governed by a detailed balance between absorjDtion, and spontaneous and stimulated emission rates. Stimulated emission occurs when tire probability of a photon causing a transition of an electron from tire CB to VB witli tire emission of anotlier photon is greater tlian that for tire upward transition of an electron from tire VB to tire CB upon absorjDtion of tire photon. These rates are commonly described in tenns of Einstein s H and 5 coefficients [8, 43]. For semiconductors, tliere is a simple condition describing tire carrier density necessary for stimulated emission, or lasing. This carrier density is known as... 

When a gas comes in contact with a solid surface, under suitable conditions of temperature and pressure, the concentration of the gas (the adsorbate) is always found to be greater near the surface (the adsorbent) than in the bulk of the gas phase. This process is known as adsorption. In all solids, the surface atoms are influenced by unbalanced attractive forces normal to the surface plane adsorption of gas molecules at the interface partially restores the balance of forces. Adsorption is spontaneous and is accompanied by a decrease in the free energy of the system. In the gas phase the adsorbate has three degrees of freedom in the adsorbed phase it has only two. This decrease in entropy means that the adsorption process is always exothermic. Adsorption may be either physical or chemical in nature. In the former, the process is dominated by molecular interaction forces, e.g., van der Waals and dispersion forces. The formation of the physically adsorbed layer is analogous to the condensation of a vapor into a liquid in fret, the heat of adsorption for this process is similar to that of liquefoction. 

Complete wetting, i.e. spontaneous spreading should always be sought to maximize adhesion. This condition occurs when, with reference to Fig. 4, it is not possible to satisfy the horizontal force balance, i.e. ys > Vl + Ysl- The thermodynamic driving force for the spreading process is the spreading coefficient. 

If AG is equal to 0, the process is at equilibrium, and there is no net flow either in the forward or reverse direction. When AG = 0, A.S = H/T, and the enthalpic and entropic changes are exactly balanced. Any process with a nonzero AG proceeds spontaneously to a final state of lower free energy. If AG is negative, the process proceeds spontaneously in the direction written. If AG is positive, the reaction or process proceeds spontaneously in the reverse direction. (The sign and value of AG do not allow us to determine how fast the process will go.) If the process has a negative AG, it is said to be exergonic, whereas processes with positive AG values are endergonic. 

Ethanol is classified for medical purposes as a central nervous system (CNS) depressant. Its effects—that is, being drunk—resemble the human response to anesthetics. There is an initial excitability and increase in sociable behavior, but this results from depression of inhibition rather than from stimulation. At a blood alcohol concentration of 0.1% to 0.3%, motor coordination is affected, accompanied by loss of balance, slurred speech, and amnesia. When blood alcohol concentration rises to 0.3% to 0.4%, nausea and loss of consciousness occur. Above 0.6%, spontaneous respiration and cardiovascular regulation are affected, ultimately leading to death. The LD50 of ethanol is 10.6 g/kg (Chapter 1 Focus On). 

For lithium metal in 1 Af HC1, the observed facts are that the metal dissolves spontaneously and a gas bubbles out of the solution. From Appendix 3 we select the two half-reactions (notice that the half-reactions are already balanced in both charge and number of atoms) ... 

Coagulation summarizes the mechanisms involved in stopping bleeding due to an injured or defective vessel wall. Coagulation is characterized by procoagulatory and anticoagulatory factors that are in balance under normal conditions. Vessel injuries are occluded by the coagulation system and spontaneous vessel occlusions dissolved by the fibrinolytic cascade. 

Write a balanced reaction for the spontaneous process when we allow a path for electron flow between the O2/H2O electrode and the H /H20 electrode as described in Section 5.3.3. 

Couple this reaction with the ADP-ATP reaction, balance the net equation, and show that the coupled reaction is spontaneous. 

C14-0083. Although the ATP-ADP reaction is the principal energy shuttle in metabolic pathways, many other examples of coupled reactions exist. For example, the glutamic acid-glutamine reaction discussed in the text can couple with the acetyl phosphate reaction shown in Example 14-10. Write the balanced equation for the coupled reaction operating in the direction of overall spontaneity and calculate A G ° for the overall process. 

Although nuclides with mass numbers around 60 are the most stable, the balance of electrical repulsion and strong nuclear attraction makes many combinations of protons and neutrons stable for indefinite times. Nevertheless, many other combinations decompose spontaneously. For example, all hydrogen nuclides with j4 > 2 are so... 

In electrochemical cells we often find convective transport of reaction components toward (or away from) the electrode surface. In this case the balance equation describing the supply and escape of the components should be written in the general form (1.38). However, this equation needs further explanation. At any current density during current flow, the migration and diffusion fluxes (or field strength and concentration gradients) will spontaneously settle at values such that condition (4.14) is satisfied. The convective flux, on the other hand, depends on the arbitrary values selected for the flow velocity v and for the component concentrations (i.e., is determined by factors independent of the values selected for the current density). Hence, in the balance equation (1.38), it is not the total convective flux that should appear, only the part that corresponds to the true consumption of reactants from the flux or true product release into the flux. This fraction is defined as tfie difference between the fluxes away from and to the electrode ... 

When an aqueous phase (noted w) is brought in contact with a second immiscible phase (noted o), the different species dissolved in one or the two phases spontaneously distribute depending on their hydrophilic-lipophilic balance until the thermodynamic equilibrium is reached. The distribution of the charged species generates an interfacial region, in which the electrical field strength differs from zero, so that an electrical Galvani potential difference, is established across the interface ... 

The electrode processes that are reversible provide values for the equilibrium emfs of cells, which are related to the thermodynamic functions. The condition of reversibility is practically obtained by balancing cell emf against an external emf until only an unappreciable current passes through the cell, in order that the cell reactions proceed very slowly. It may, however, be pointed out that for many of the applications of electrometallurgy, it is clearly necessary to consider more rapid reaction rates. In that situation there is necessarily a departure from the equilibrium condition. Either the cell reactions occur spontaneously to produce electric energy, or an external source of electric energy is used to implement chemical reactions (electrolyses). 

The autonomic nervous system exerts the primary control on heart rate. Because the sympathetic and parasympathetic systems have antagonistic effects on the heart, heart rate at any given moment results from the balance or sum of their inputs. The SA node, which is the pacemaker of the heart that determines the rate of spontaneous depolarization, and the AV node are innervated by the sympathetic and parasympathetic systems. The specialized ventricular conduction pathway and ventricular muscle are innervated by the sympathetic system only. 

In a celebrated paper, Einstein (1917) analyzed the nature of atomic transitions in a radiation field and pointed out that, in order to satisfy the conditions of thermal equilibrium, one has to have not only a spontaneous transition probability per unit time A2i from an excited state 2 to a lower state 1 and an absorption probability BUJV from 1 to 2 , but also a stimulated emission probability B2iJv from state 2 to 1 . The latter can be more usefully thought of as negative absorption, which becomes dominant in masers and lasers.1 Relations between the coefficients are found by considering detailed balancing in thermal equilibrium... 

If, when a liquid drop is placed on a smooth surface, the forces of adhesion between the solid and the liquid are greater than the forces of cohesion of the liquid, then the liquid will spread and will perfectly wet the surface spontaneously. If the forces reach an intermediate balance determined by the interfacial energies ylv, ysj and ysv, then the liquid drop will form a definite contact angle (0) with the solid surface (Figure 4.12). 

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