Free comparison

To construct the calibration curve, run 5-50 mL of the standard boron solution by means of a burette into 100 mL graduated flasks, add 30 mL of dilute sulphuric acid, and make up to volume. These solutions contain 1 — 10 /ig of B per 3 mL. Use 3 mL of each solution and of a boron-free comparison solution and proceed as above. Plot a calibration curve relating absorbance and boron content. 

The advantage of PHACIR over other tools is the alignment-free comparison of molecular structures. PHACIR depends on a translational- and rotation-free pattern comparison. 

Table 3 shows results obtained from a five-component, isothermal flash calculation. In this system there are two condensable components (acetone and benzene) and three noncondensable components (hydrogen, carbon monoxide, and methane). Henry s constants for each of the noncondensables were obtained from Equations (18-22) the simplifying assumption for dilute solutions [Equation (17)] was also used for each of the noncondensables. Activity coefficients for both condensable components were calculated with the UNIQUAC equation. For that calculation, all liquid-phase composition variables are on a solute-free basis the only required binary parameters are those for the acetone-benzene system. While no experimental data are available for comparison, the calculated results are probably reliable because all simplifying assumptions are reasonable the... 

Figure Bl.4.9. Top rotation-tunnelling hyperfine structure in one of the flipping inodes of (020)3 near 3 THz. The small splittings seen in the Q-branch transitions are induced by the bound-free hydrogen atom tiiimelling by the water monomers. Bottom the low-frequency torsional mode structure of the water duner spectrum, includmg a detailed comparison of theoretical calculations of the dynamics with those observed experimentally [ ]. The symbols next to the arrows depict the parallel (A k= 0) versus perpendicular (A = 1) nature of the selection rules in the pseudorotation manifold.

Light microscopy allows, in comparison to other microscopic methods, quick, contact-free and non-destmctive access to the stmctures of materials, their surfaces and to dimensions and details of objects in the lateral size range down to about 0.2 pm. A variety of microscopes with different imaging and illumination systems has been constmcted and is conunercially available in order to satisfy special requirements. These include stereo, darkfield, polarization, phase contrast and fluorescence microscopes. 

The sequence space of proteins is extremely dense. The number of possible protein sequences is 20. It is clear that even by the fastest combinatorial procedure only a very small fraction of such sequences could have been synthesized. Of course, not all of these sequences will encode protein stmctures which for functional purjDoses are constrained to have certain characteristics. A natural question that arises is how do viable protein stmctures emerge from the vast sea of sequence space The two physical features of folded stmctures are (l)in general native proteins are compact but not maximally so. (2) The dense interior of proteins is largely made up of hydrophobic residues and the hydrophilic residues are better accommodated on the surface. These characteristics give the folded stmctures a lower free energy in comparison to all other confonnations. 

Hayward, S., Kitao, A., Berendsen, H.J.C. Model-free methods to analyze domain motions in proteins from simulation A comparison of normal mode analysis and molecular dynamics simulation of lysozyme. Proteins 27 (1997) 425-437. 

Our discussion so far has considered the calculation of Helmholtz free energies, which a obtained by performing simulations at constant NVT. For proper comparison with expe inental values we usually require the Gibbs free energy, G. Gibbs free energies are obtaini trorn a simulation at constant NPT. 

Dewar and his co-workers, as mentioned above, investigated the reactivities of a number of polycyclic aromatic compounds because such compounds could provide data especially suitable for comparison with theoretical predictions ( 7.2.3). This work was extended to include some compounds related to biphenyl. The results were obtained by successively compounding pairs of results from competitive nitrations to obtain a scale of reactivities relative to that of benzene. Because the compounds studied were very reactive, the concentrations of nitric acid used were relatively small, being o-i8 mol 1 in the comparison of benzene with naphthalene, 5 x io mol 1 when naphthalene and anthanthrene were compared, and 3 x io mol 1 in the experiments with diphenylamine and carbazole. The observed partial rate factors are collected in table 5.3. Use of the competitive method in these experiments makes them of little value as sources of information about the mechanisms of the substitutions which occurred this shortcoming is important because in the experiments fuming nitric acid was used, rather than nitric acid free of nitrous acid, and with the most reactive compounds this leads to a... 

The applicability of the two-parameter equation and the constants devised by Brown to electrophilic aromatic substitutions was tested by plotting values of the partial rate factors for a reaction against the appropriate substituent constants. It was maintained that such comparisons yielded satisfactory linear correlations for the results of many electrophilic substitutions, the slopes of the correlations giving the values of the reaction constants. If the existence of linear free energy relationships in electrophilic aromatic substitutions were not in dispute, the above procedure would suffice, and the precision of the correlation would measure the usefulness of the p+cr+ equation. However, a point at issue was whether the effect of a substituent could be represented by a constant, or whether its nature depended on the specific reaction. To investigate the effect of a particular substituent in different reactions, the values for the various reactions of the logarithms of the partial rate factors for the substituent were plotted against the p+ values of the reactions. This procedure should show more readily whether the effect of a substituent depends on the reaction, in which case deviations from a hnear relationship would occur. It was concluded that any variation in substituent effects was random, and not a function of electron demand by the electrophile. ... 

The interest attaching to the nitration of pyridine i-oxide and its derivatives has already been mentioned ( 8.2.5). Some data for these reactions are given in tables 8.1, 8.2 and 8.4. The 4-nitration of pyridine I-oxide is shown to occur through the free base by comparison with the case of i-methoxypyridinium cation ( 8.2.2), by the nature of the rate profile ( 8.2.1), and by consideration of the encounter rate ( 8.2.3). - Some of these criteria have been used to show that the same is true for... 

Comparison of the behaviour of cinnoline 2-oxide (vi, i = O) with that of 2-methoxycinnolinium (vi, R = OMe) suggests that at high acidities the former is nitrated as its conjugate acid (vi, R = OH), but that as the acidity is lowered the free base becomes active. At high acidities 5- and 8-nitration are dominant, but as the acidity is lowered 6-nitration becomes increasingly important. The 5- and 8-nitro compounds are probably formed mainly or wholly by nitration of the conjugate acid, and the 6-nitro compound wholly or mainly from the free base. ... 

D. Comparison of Free-Radical Reactivity with Theoretical Calculations... 

FIGURE 19 3 The free energies of ionization of ethanol and acetic acid in water The electrostatic po tential maps of ethoxide and acetate ion show the concentration of negative charge in ethoxide versus dispersal of charge in ac etate The color ranges are equal in both models to al low direct comparison... 

Nonfractionating continuous inlet. An inlet in which gas flows from a gas stream being analyzed to the mass spectrometer ion source without any change in the conditions of flow through the inlet or by the conditions of flow through the ion source. This flow is usually viscous flow, such that the mean free path is very small in comparison with the smallest dimension of a traverse section of the channel. The flow characteristics are determined mainly by collisions between gas molecules, i.e., the viscosity of the gas. The flow can be laminar or turbulent. 

Figure 6.11 Comparison of the number distribution of n-mers for polymers prepared from anionic and free-radical active centers, both with f = 50.

Even though the catalyst may be only partially converted to H B", the concentration of these ions may be on the order of 10 times greater than the concentration of free radicals in the corresponding stationary state of the radical mechanism. Likewise, kp for ionic polymerization is on the order of 100 times larger than the sum of the constants for all termination and transfer steps. By contrast, kp/kj which is pertinent for the radical mechanism, is typically on the order of 10. These comparisons illustrate that ionic polymerizations occur very fast even at low temperatures. 

A brief review has appeared covering the use of metal-free initiators in living anionic polymerizations of acrylates and a comparison with Du Font s group-transfer polymerization method (149). Tetrabutylammonium thiolates mn room temperature polymerizations to quantitative conversions yielding polymers of narrow molecular weight distributions in dipolar aprotic solvents. Block copolymers are accessible through sequential monomer additions (149—151) and interfacial polymerizations (152,153). 

Thermal Oxidative Stability. ABS undergoes autoxidation and the kinetic features of the oxygen consumption reaction are consistent with an autocatalytic free-radical chain mechanism. Comparisons of the rate of oxidation of ABS with that of polybutadiene and styrene—acrylonitrile copolymer indicate that the polybutadiene component is significantly more sensitive to oxidation than the thermoplastic component (31—33). Oxidation of polybutadiene under these conditions results in embrittlement of the mbber because of cross-linking such embrittlement of the elastomer in ABS results in the loss of impact resistance. Studies have also indicated that oxidation causes detachment of the grafted styrene—acrylonitrile copolymer from the elastomer which contributes to impact deterioration (34). 

Ultrasonic Microhardness. A new microhardness test using ultrasonic vibrations has been developed and offers some advantages over conventional microhardness tests that rely on physical measurement of the remaining indentation size (6). The ultrasonic method uses the DPH diamond indenter under a constant load of 7.8 N (800 gf) or less. The hardness number is derived from a comparison of the natural frequency of the diamond indenter when free or loaded. Knowledge of the modulus of elasticity of the material under test and a smooth surface finish is required. The technique is fast and direct-reading, making it useful for production testing of similarly shaped parts. 

Concern for personnel exposure to hydrazine has led to several innovations in packaging to minimize direct contact with hydrazine, eg, Olin s E-Z dmm systems. Carbohydrazide was introduced into this market for the same reason it is a soHd derivative of hydrazine, considered safer to handle because of its low vapor pressure. It hydrolyzes to release free hydrazine at elevated temperatures in the boiler. It is, however, fairly expensive and contributes to dissolved soHds (carbonates) in the water (193). In field tests, catalyzed hydrazine outperformed both hydrazine and carbohydrazide when the feedwater oxygen and iron levels were critical (194). A pubUshed comparison is available (195) of these and other proposed oxygen scavengers, eg, diethyUiydroxylarnine, ydroquinone, methyethylketoxime, and isoascorbic acid. 

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