Opposition effect

The observation that a system at equilibrium responds to a stress by reequilibrating in a manner that diminishes the stress, is formalized as Le Chatelier s principle. One of the most common stresses that we can apply to a reaction at equilibrium is to change the concentration of a reactant or product. We already have seen, in the case of sodium acetate and acetic acid, that adding a product to a reaction mixture at equilibrium converts a portion of the products to reactants. In this instance, we disturb the equilibrium by adding a product, and the stress is diminished by partially reacting the excess product. Adding acetic acid has the opposite effect, partially converting the excess acetic acid to acetate. 

All other things being equal, the strength of a weak acid increases if it is placed in a solvent that is more basic than water, whereas the strength of a weak base increases if it is placed in a solvent that is more acidic than water. In some cases, however, the opposite effect is observed. For example, the pKb for ammonia is 4.76 in water and 6.40 in the more acidic glacial acetic acid. In contradiction to our expectations, ammonia is a weaker base in the more acidic solvent. A full description of the solvent s effect on a weak acid s piQ or on the pKb of a weak base is beyond the scope of this text. You should be aware, however, that titrations that are not feasible in water may be feasible in a different solvent. 

Water, however, has the opposite effect. Actual equiUbtium constants at various temperatures are given in Table 7. A detailed study of the effect of pressure on urea conversion is given in Ref. 17. 

Activators enhance the adsorption of collectors, eg, Ca " in the fatty acid flotation of siUcates at high pH or Cu " in the flotation of sphalerite, ZnS, by sulfohydryl collectors. Depressants, on the other hand, have the opposite effect they hinder the flotation of certain minerals, thus improving selectivity. For example, high pH as well as high sulfide ion concentrations can hinder the flotation of sulfide minerals such as galena (PbS) in the presence of xanthates (ROCSS ). Hence, for a given fixed collector concentration there is a fixed critical pH that defines the transition between flotation and no flotation. This is the basis of the Barsky relationship which can be expressed as [X ]j[OH ] = constant, where [A ] is the xanthate ion concentration in the pulp and [Oi/ ] is the hydroxyl ion concentration indicated by the pH. Similar relationships can be written for sulfide ion, cyanide, or thiocyanate, which act as typical depressants in sulfide flotation systems. 

A substantial effort has been appHed to iacreaskig i by stmctural modification (114), eg, the phthalaziQe-l,4-diones (33) and (34) which have chemiluminescence quantum yields substantially higher than luminol (115,116). The fluorescence quantum yield of the dicarboxylate product from (34) is 14%, and the yield of singlet excited state is calculated to be 50% (116). Substitution of the 3-amino group of lumiaol reduces the CL efficiency > 10 — fold, whereas the opposite effect occurs with the 4-amino isomer (117). A series of pyridopyridaziae derivatives (35) have been synthesized and shown to be more efficient than luminol (118). 

Therefore, any perturbation acting on the crystal to increase or decrease the concentration of one species must have the opposite effect on the concentration of the other species (142). 

Other ingredients besides the elastomer and the cure system itself influence cure and scorch behavior. Usually the effect of a material on cure is pH-dependent. Ingredients which are basic in nature tend to accelerate the rate of both scorch and cure, whereas acidic materials exhibit the opposite effect. 

In contrast, antioxidants can have an opposite effect when peroxide curing. Because peroxide cross-linking involves a free-radical mechanism, and antioxidants are designed to scavenge free radicals, it is obvious that peroxide efficiency can be compromised by the addition of antioxidants. Thus the decomposition products of the ppds were acting as accelerators (29). 

Poly(vinyhdene chloride) also dissolves readily in certain solvent mixtures (82). One component must be a sulfoxide or A/,Al-diaIk5lamide. Effective cosolvents are less polar and have cycHc stmctures. They include aUphatic and aromatic hydrocarbons, ethers, sulfides, and ketones. Acidic or hydrogen-bonding solvents have an opposite effect, rendering the polar aprotic component less effective. Both hydrocarbons and strong hydrogen-bonding solvents are nonsolvents for PVDC. 

Equation 14 shows that an increase in acidity of the solution increases the concentration of uncomplexed metal, which must result from the displacement of from MA2, causing a simultaneous decrease in the ratio of complexed to free ligand [MA2]/[HA]. The opposite effects result upon decreasing the acidity. This behavior occurs in the pH range where appreciable amounts of both HA and A coexist. Outside this range the ligand is present almost entirely as either HA or MA2 and A , and the system is essentially independent of pH. 

Pollution can cause opposite effects in relahon to precipitation. Addition of a few particles that act as ice nuclei can cause ice particles to grow at the expense of supercooled water droplets, producing particles large enough to fall as precipitation. An example of this is commercial cloud seeding with silver iodide particles released from aircraft to induce rain. If too many particles are added, none of them grow sufficiently to cause precipitation. Therefore, the effects of pollution on precipitation are complex. 

Glycine and proUne have opposite effects on stability... 

The close structural similarities between polychloroprene and the natural rubber molecule will be noted. However, whilst the methyl group activates the double bond in the polyisoprene molecule the chlorine atom has the opposite effect in polychloroprene. Thus the polymer is less liable to oxygen and ozone attack. At the same time the a-methylene groups are also deactivated so that accelerated sulphur vulcanisation is not a feasible proposition and alternative curing systems, often involving the pendant vinyl groups arising from 1,2-polymerisation modes, are necessary. 

For cyclopentanone, cyclohexanone, and cycloheptanone, the K values for addition are 48, 1000, and 8 M , respectively. For aromatic aldehydes, the equilibria are affected by the electronic nature of the aryl substituent. Electron donors disfavor addition by stabilizing the aldehyde whereas electron-accepting substituents have the opposite effect. 

The existence of the nitronium ion in sulfuric-nitric acid mixtures was demonstrated both by cryoscopic measurements and by spectroscopy. An increase in the strong acid concentration increases the rate of reaction by shifting the equilibrium of step 1 to the right. Addition of a nitrate salt has the opposite effect by suppressing the preequilibrium dissociation of nitric acid. It is possible to prepare crystalline salts of nitronium ions, such as nitronium tetrafluoroborate. Solutions of these salts in organic solvents rapidly nitrate aromatic compounds. ... 

Generally there is a stiffening effect in compression compared to tension. As a first approximation one could assume that tension and compression behaviour are the same. Thomas has shown that typically for PVC, the compression modulus is about 10% greater than the tensile modulus. However, one needs to be careful when comparing the experimental data because normally no account is taken of the changes in cross-sectional area during testing. In tension, the area will decrease so that the true stress will increase whereas in compression the opposite effect will occur. 

Airway surfaces, like skin, are continually exposed to the ambient environment. In contrast to skin submucosal vessels, however, w hich shed excess heat by vasodilating when heated and conserve heat by vasoconstricting when chilled, it is unclear how the airway vasculature responds to temperature extremes. Inspiring cold air poses two challenges to conducting airway tissues the risk of tissue injury should inadequate heat reach the airway surface and excessive body heat loss due to increasing the radial temperature gradient. Vasodilation would protect airway tissue but increase heat loss, while vasoconstriction would produce the opposite effect. 

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