Adjusting chemistry

An alternative way of portraying the pattern formation behaviour in systems of the sort under consideration here is to delineate the regions in chemical parameter space (the h k plane) over which the uniform state is unstable to non-uniform perturbations. We have already seen in chapter 4, and in Fig. 10.3, that we can locate the boundary of Hopf instability (where the uniform state is unstable to a uniform perturbation and at which spatially uniform time-dependent oscillations set in). We can use the equations derived in 10.3.2 to draw similar loci for instability to spatial pattern formation. For this, we can choose a value for the ratio of the diffusivities / and then find the conditions where eqn (10.48), regarded as a quadratic in either y or n, has two real positive solutions. The latter requires that 

For the roots to be real, the parameters must also satisfy the condition 

Recognizing that n and k can be related to the uniform stationary-state temperature excess 0SS = h/k, the condition for real positive solutions to eqn (10.48) to exist can be expressed as 

Changing / merely alters the size of the region of instability to pattern formation, as the values of n and k which form the locus are directly proportional to / in eqns (10.58) and (10.59). Thus, increasing / increases the range of n and k over which pattern formation is possible. Table 10.1 gives the general coordinates of the locus, which can be used for any / . 

The point at which the pattern instability and Hopf bifurcation loci cross, for a system with given / , is easily located by taking eqns (10.21) and (10.58). These give 

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Properties and Control. Early cupric chloride formations had slow etch rates and low copper capacity and were limited to batch operation. Regenerated continuous operation using modified formulations has brought useful improvements. Etch rates as high as 55 s for 1 oz copper are obtained from cupric chloride-sodium chloride-HCl systems operated at 130°F with conventional spray-etching equipment. Copper capacities are maintained at 20 oz/ gal and above. However, more recently, higher copper contents and adjusted chemistries at 125°F typically etch at 75 to 90 s for 1 oz copper. 

Surfaces are found to exliibit properties that are different from those of the bulk material. In the bulk, each atom is bonded to other atoms m all tliree dimensions. In fact, it is this infinite periodicity in tliree dimensions that gives rise to the power of condensed matter physics. At a surface, however, the tliree-dimensional periodicity is broken. This causes the surface atoms to respond to this change in their local enviromnent by adjusting tiieir geometric and electronic structures. The physics and chemistry of clean surfaces is discussed in section Al.7.2. 

The design and manufacture of adsorbents for specific appHcations involves manipulation of the stmcture and chemistry of the adsorbent to provide greater attractive forces for one molecule compared to another, or, by adjusting the size of the pores, to control access to the adsorbent surface on the basis of molecular size. Adsorbent manufacturers have developed many technologies for these manipulations, but they are considered proprietary and are not openly communicated. Nevertheless, the broad principles are weU known. 

Fluxes are usually added in the form of either limestone or dolomite. The fluxes provide the basic constituents (CaO and MgO) needed to balance the acid constituents (Si02 and AI2O2) from the coke and ore. These are the four primary oxides which form the slag, although minor amounts of other oxides such as MnO, Na20, K2O, P2 S Ti02, and sulfur are also present. Proper adjustment of the slag chemistry is necessary to obtain the desired... 

Control of chromium penetration, essential to permit tannage of the center of the hide, is accompHshed by pH adjustment. At a pH > 3.0 the reactivity of the hide to the chromium complex is greatiy increased. The pH is therefore raised gradually to the desired point by addition of a mild alkah, usually sodium bicarbonate. The chemistry of chrome tanning involves competing reactions that must be controlled for satisfactory results. 

An alternative to this process is low (<10 N/m (10 dynes /cm)) tension polymer flooding where lower concentrations of surfactant are used compared to micellar polymer flooding. Chemical adsorption is reduced compared to micellar polymer flooding. Increases in oil production compared to waterflooding have been observed in laboratory tests. The physical chemistry of this process has been reviewed (247). Among the surfactants used in this process are alcohol propoxyethoxy sulfonates, the stmcture of which can be adjusted to the salinity of the injection water (248). 

Fite refining adjusts the sulfur and oxygen levels in the bhster copper and removes impurities as slag or volatile products. The fire-refined copper is sold for fabrication into end products, provided that the chemistry permits product specifications to be met. Some impurities, such as selenium and nickel, are not sufficiently removed by fire refining. If these impurities are detrimental to fabrication or end use, the copper must be electrorefined. Other impurities, such as gold, silver, selenium, and tellurium, are only recovered via electrorefining. Virtually all copper is electrorefined. 

Alter the environment to render it less eorrosive. This approach may be as simple as maintaining clean metal surfaces. It is well known that the chemistry of the environment beneath deposits can become substantially different than that of the bulk environment. This difference can lead to localized, underdeposit corrosion (see Chap. 4, Underdeposit Corrosion ). The pit sites produced may then induce corrosion fatigue when cyclic stresses are present. The specific steps taken to reduce corrosivity vary with the metal under consideration. In general, appropriate adjustments to pH and reduction or elimination of aggressive ions should be considered. 

The role played by the various ingredients in the composition of sealant, and in particular on the durability of adhesion has been discussed recently [77]. Inert plasticizers, such as trimethylsilyl-endblocked-PDMS, are typically added to silicone sealant compositions in order to adjust the rheology of the uncured sealant. They result in a reduction of the modulus and hardness of the cured sealant. Differences in the durability of silicone sealants are found to be due to differences in their cure chemistry, and more specifically to the nature and... 

Chemical scaling is another form of fouling that occurs in NF and RO plants. The thermodynamic solubility of salts such as calcium carbonate and calcium and barium sulfate imposes an upper boundary on the system recovery. Thus, it is essential to operate systems at recoveries lower than this critical value to avoid chemical scaling, unless the water chemistry is adjusted to prevent precipitation. It is possible to increase system recovery by either adjusting the pH or adding an antisealant, or both. 

The aromatic portion of the molecules discussed in this chapter is frequently, if not always, an essential contributor to the intensity of their pharmacological action. It is, however, usually the aliphatic portion that determines the nature of that action. Thus it is a common observation in the practice Ilf medicinal chemistry that optimization of potency in these drug classes requires careful attention to the correct spatial orientation of the functional groups, their overall electronic densities, and the contribution that they make to the molecule s solubility in biological fluids. These factors are most conveniently adjusted by altering the substituents on the aromatic ring. 

NOTE Simple HW heating and LP steam boiler treatment apart, the term BW treatment is unfortunately often something of a misnomer. The practice is, in fact, generally recognized to be primarily concerned with adjustments to the boiler FW chemistry and the addition of polishing chemicals to compensate for deficiencies or potential problems associated with the FW rather than with the recirculating BW. 

Chemical relaxation techniques were conceived and implemented by M. Eigen, who received the 1967 Nobel Prize in Chemistry for his work. In a relaxation measurement, one perturbs a previously established chemical equilibrium by a sudden change in a physical variable, such as temperature, pressure, or electric field strength. The experiment is carried out so that the time for the change to be applied is much shorter than that for the chemical reaction to shift to its new equilibrium position. That is to say, the alteration in the physical variable changes the equilibrium constant of the reaction. The concentrations then adjust to their values under the new condition of temperature, pressure, or electric field strength. 

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