Browning increase with

A420 increased with time in all solutions, except for the systems with eidier no acetate or no glucose. The absorbance-time plot showed that change in absorbance with time was not linear as the rate of browning increased with time (Figure 1). This is the typical shape of die reaction curve, and the induction period and shape of the curve have been explained as the initial absence of a reactant which is subsequently formed during heating (22). 

The rate of browning increases with increasing tanperature or time. Since these reactions have been shown to have a high temperature coefficient, lowering of the tanperature during the processing or the storage of food products can help to minimize these reactions. 

The suitability of the model reaction chosen by Brown has been criticised. There are many side-chain reactions in which, during reaction, electron deficiencies arise at the site of reaction. The values of the substituent constants obtainable from these reactions would not agree with the values chosen for cr+. At worst, if the solvolysis of substituted benzyl chlorides in 50% aq. acetone had been chosen as the model reaction, crJ-Me would have been —0-82 instead of the adopted value of —0-28. It is difficult to see how the choice of reaction was defended, save by pointing out that the variation in the values of the substituent constants, derivable from different reactions, were not systematically related to the values of the reaction constants such a relationship would have been expected if the importance of the stabilization of the transition-state by direct resonance increased with increasing values of the reaction constant. 

Example 5. Glycolysis of Polyurethanes with Propylene Oxide after Pretreatment with Ethanolamine.55 A rigid polyurethane foam (ca. 100 g) was dissolved in 30 g ethanolamine by heating. Excess ethanolamine was stripped, leaving a clear solution. Infrared and GPC analysis indicated that the clear solution obtained contained some residual polyurethane, aromatic polyurea, aliphatic polyols, aromatic amines, and N,N -bis(f -hydroxyethyljurea. Next the mixture was dissolved in 45 g propylene oxide and heated at 120°C in an autoclave for 2 h. The pressure increased to 40 psi and then fell to 30 psi at the end of the 2-h heating period. The product was a brown oil with a hydroxyl number of485. 

Brown and McDonald (1966) provided another type of kinetic evidence for these size relationships by determining secondary kinetic isotope effects in reactions of pyridine-4-pyridines with alkyl iodides. For example, the isotopic rate ratio in the reaction between 4-(methyl-d3)-pyridine and methyl iodide at 25-0 C in nitrobenzene solution was determined to be kjyfk = l-OOl, while that in the corresponding reaction with 2,6-(dimethyl-d6)-pyridine was 1-095. (Brown and McDonald (1966) estimate an uncertainty of 1% in the k jk values.) Furthermore, the isotopic rate ratio in the case of the 2-(methyl-d3)-compound increased from 1 030 to 1-073 as the alkyl group in the alkyl iodide was changed from methyl to isopropyl, i.e. the isotope effect increased with increasing steric requirements of the alkyl iodide. 

In 1868 two Scottish scientists, Crum Brown and Fraser [4] recognized that a relation exists between the physiological action of a substance and its chemical composition and constitution. That recognition was in effect the birth of the science that has come to be known as quantitative structure-activity relationship (QSAR) studies a QSAR is a mathematical equation that relates a biological or other property to structural and/or physicochemical properties of a series of (usually) related compounds. Shortly afterwards, Richardson [5] showed that the narcotic effect of primary aliphatic alcohols varied with their molecular weight, and in 1893 Richet [6] observed that the toxicities of a variety of simple polar chemicals such as alcohols, ethers, and ketones were inversely correlated with their aqueous solubilities. Probably the best known of the very early work in the field was that of Overton [7] and Meyer [8], who found that the narcotic effect of simple chemicals increased with their oil-water partition coefficient and postulated that this reflected the partitioning of a chemical between the aqueous exobiophase and a lipophilic receptor. This, as it turned out, was most prescient, for about 70% of published QSARs contain a term relating to partition coefficient [9]. 

Fig. 2 shows the effects of the intensity on the reaction rate of TCE. As shown, the TCE reaction rate increases with an increasing UV light intensity and it seems fliat more electron-hole pairs are produced by the UV li t. Thus, more photons can bring forth a greats degradation of the TCE. Obbe and Brown [4] reported that the dependency of the photoreaction rate on the ultraviolet li t intensity followed a power law. The reaction rate on the ultraviolet intensity follows a power law such as ... 

The apparent rate constant kapp depends on the concentration of hydroxide ion as is shown in Fig. 1. The absorption maxima of TcCl2(acac) 2 in chloroform appear at 281,314(sh), 340(sh), 382 and 420 nm. On the other hand, the spectrum of the aqueous phase exhibits absorption maxima at 292,350 and 540 nm. The absorbances at 350 and 540 nm increase with time, but decrease after reaching maxima. This suggests that the chemical species which is formed by the back-extraction of TcCl2(acac)2 decomposes with time. In order to clarify the behavior of chloride ion liberated from the complex, an electrochemical method was introduced for the homogeneous system. In acetonitrile, no detectable change in the spectrum of TcCl2(acac)2 was observed. On the addition of an aqueous solution of hydroxide, however, the brown solution immediately turned red-violet, and exhibited absorption maxima at 292,350 and 540 nm. The red-violet... 

The aromaticity of the oils, as calculated from the ]H n.m.r. data using the Brown-Ladner equation (14), increase with temperature (see Figure 7) as does the /h atomic ratio as shown in Figure 7. 

The nitrogen atoms of the twisted amides discussed on pages 107-108 are to a greater or lesser extent pyramidal, and incipient lone pairs electron density is thus available for reactions with electrophiles. The classic example is the cage lactam [57] first prepared by Pracejus (1959), which has an amide nitrogen with near normal amine basicity. Brown and coworkers have measured rates of alkaline hydrolysis of a series of anilides [58] and [59] with related structures and find that the rate increases with increasing divergence... 

Brown and Chuah [84] and Oppermann el ol. [36] studied the spinning of partially oriented yam (POY) as a function of take-up speed from 500 to 5000m/min. Figures 11.18 and 11.19 show, respectively, development of the tenacity and elongation as a function of spinning speed. Tenacity increases with increasing... 

Table 9 gives the results of this calculation. In order to achieve a consistent formulation of the equilibrium we use the reciprocal of the dissociation constant given by Brown and Brady (1952) multiplied by ko- Since the measurements show that Henry s law is very well obeyed, the equilibrium mole fractions in Table 9 were given as above, computed with the aid of the Henry s law constants k and As may be seen from the equilibrium constants in the last column of the table, the stability of the complexes increases with the number of methyl groups in the benzene nucleus, which implies that the basicity of the aromatic substances also increases in the same sense. 

Because the rate of the ETC increases, with no ATP synthesis, energy is released as heat. Important uncouplers include 2,4-dinitrophenol (2,4-DNP) and aspirin (and other salicylates). Brown adipose tissue contains a natural uncoupling protein (UCP, formerly called thernio-genin), which allows energy loss as heat to maintain a basal temperature around the kidneys, neck, breastplate, and scapulae in newborns. 

Fusion of the llptlnlte macerals In bituminous coals commences at lower temperatures and reaches a much greater extent than that of the aromatic macerals (Figures 4 and 5). The greater thermal stability Indicated by the much higher fusion temperatures of the bituminous llptlnltes compared to brown coal llptlnltes can be explained In terms of these materials having a more highly crossllnked macromolecular structure than the llptlnltes In the brown coals. This Increase with coallflcatlon could be the consequence of In situ crosslinking of material or the selective loss of llptlnlte fractions that are less crossllnked and therefore less Inherently stable ... 

The nucleation rate increased from 65°C to 70°C and dropped from 70°C to 80°C. Thus 70°C seems to be the optimum temperature for maximum nucleation. Published work on alumina trihydrate by Misra and White (5) and Brown (9 10) revealed that the nucleation rate decreases with increasing temperature, at greater than 70 C by the former but from 50 to 75°C by the latter. This nucleation rate dependence on temperature differs with normal chemical reaction where the reaction rate increases with increase in temperature. It is not clear whether then-studies at different temperatures in the published work were conducted at constant initial absolute supersaturation (AC7C ) for all the temperatures studied or at constant initial concentration. The latter would account for the higher nucleation rates obtained at lower temperatures as the AC/C is higher at lower temperatures since C decreases with temperature. 

Information about the kinetics of dissolution reactions is provided by Delmon (1969) and by Brown et al. (1980). Dissolution may be either diffusion (i.e., transport) or surface controlled. If diffusion controlled, i. e., if the concentration of dissolved species immediately adjacent to the surface corresponds to the equilibrium solubility (Ce) of the solid phase, the concentration, c, of the dissolved species is diffusion controlled and increases with the square root of time, t, i. e.. 

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