Ratio of Reactants

Both the ratios in the prepolymer production and the curing ratios will affect the final properties of the polyurethane. In the initial prepolymer production, the properties vary according to the molar ratios of the prepolymer. This is illustrated by the graphs compiled in Saunders and Frisch (Saunders, 1962). 

The effect of varying the mixing ratios of the chain extender has a number of different influences on some of the more common properties. The changes depend on the effect at the molecular level. 

The most commonly quoted property (hardness) remains relatively constant between 85 to 100% of the theoretical curative addition. This is due to the fact that the hard segments will provide the bulk of the stiffness to the product. Even when there is some hydrogen bonding, the hardness will stay approximately the same. Compression set needs a lower level of curative (85 to 95%) with some covalent cross-linking to develop the lowest set. 

Properties such as abrasion resistance, resilience, and heat buildup are normally the best at a lower level of curative. These properties rely on unhindered flexibility of the backbone chain. 

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If a reaction is reversible, there is a maximum conversion that can be achieved, the equilibrium conversion, which is less than 1.0. Fixing the mole ratio of reactants, temperature, and pressure fixes the equilibrium conversion. ... 

This experiment examines the effect of reaction time, temperature, and mole ratio of reactants on the synthetic yield of acetylferrocene by a Eriedel-Crafts acylation of ferrocene. A central composite experimental design is used to find the optimum conditions, but the experiment could be modified to use a factorial design. 

The ratio of reactants had to be controlled very closely to suppress these impurities. Recovery of the acrylamide product from the acid process was the most expensive and difficult part of the process. Large scale production depended on two different methods. If soHd crystalline monomer was desired, the acrylamide sulfate was neutralized with ammonia to yield ammonium sulfate. The acrylamide crystallized on cooling, leaving ammonium sulfate, which had to be disposed of in some way. The second method of purification involved ion exclusion (68), which utilized a sulfonic acid ion-exchange resin and produced a dilute solution of acrylamide in water. A dilute sulfuric acid waste stream was again produced, and, in either case, the waste stream represented a... 

The foam forming iagredients are carefully metered to obtain the proper ratio of reactants, thoroughly mixed by either mechanical or impingement means, then appHed as a Hquid, a spray, or a froth with subsequent expansion and cuiing. 

Precise coatrol of the course, speed, and extent of the reaction is essential for successful manufacture. Important factors are mole ratio of reactants catalyst (pH of reaction mixture) and reaction time and temperature. Amino resias are usually made by a batch process. The formaldehyde and other reactants are charged to a kettie, the pH adjusted, and the charge heated. Often the pH of the formaldehyde is adjusted before a dding the other reactants. Aqueous formaldehyde is most convenient to handle and lowest ia cost. 

Ratio and Multiplicative Feedforward Control. In many physical and chemical processes and portions thereof, it is important to maintain a desired ratio between certain input (independent) variables in order to control certain output (dependent) variables (1,3,6). For example, it is important to maintain the ratio of reactants in certain chemical reactors to control conversion and selectivity the ratio of energy input to material input in a distillation column to control separation the ratio of energy input to material flow in a process heater to control the outlet temperature the fuel—air ratio to ensure proper combustion in a furnace and the ratio of blending components in a blending process. Indeed, the value of maintaining the ratio of independent variables in order more easily to control an output variable occurs in virtually every class of unit operation. 

Trimethyl aluminum and propylene oxide form a mixture of 2-methyl-1-propanol and 2-butanol (105). Triethyl aluminum yields products of 2-methyl-1-butanol and 2-pentanol (106). The ratio of products is determined by the ratio of reactants. Hydrolysis of the products of methyl aluminum dichloride and propylene oxide results ia 2-methylpropeae and 2-butene, with elimination of methane (105). Numerous other nucleophilic (107) and electrophilic (108) reactions of propylene oxide have been described ia the Hterature. 

For the manufacturiag of potassium ethyl xanthate, 400% excess of alcohol and equimolar quantities of 50 wt % aqueous potassium hydroxide and carbon disulfide were used (77). After 30 min at 40°C, the mixture was vacuum dmm dried. The product was obtained ia near quantitative yield and assayed at 95%. It is claimed that potassium amyl xanthate can be made with almost the same ratio of reactants and 80 wt % caustic potash (78). 

Because PEA is such an important fragrance material this simple, essentially one-step process has been exhaustively studied to optimize reaction conditions and purification procedures. Because of the high reactivity of the iatermediates and the tendency toward polymer formation, critical factors such as throughput, temperature, molar ratios of reactants, addition rates, reactor materials and design, and agitation rate must be carefully balanced to provide an economical product with acceptable odor properties. 

Ammonium acetate and sodium methoxide are effective catalysts for the ammonolysis of soybean oil (49). Polyfunctional amines and amino alcohols such as ethylenediamine, ethanolamine, and diethanolamine react to give useful intermediates. Ethylenediamine can form either a monoamide or a diamide depending on the mole ratio of reactants. With an equimolar ratio of reactants and a temperature of >250° C, a cyclization reaction occurs to give imidazolines with ethylenediamine (48) ... 

Liquid-phase chlorination of butadiene in hydroxyhc or other polar solvents can be quite compHcated in kinetics and lead to extensive formation of by-products that involve the solvent. In nonpolar solvents the reaction can be either free radical or polar in nature (20). The free-radical process results in excessive losses to tetrachlorobutanes if near-stoichiometric ratios of reactants ate used or polymer if excess of butadiene is used. The "ionic" reaction, if a small amount of air is used to inhibit free radicals, can be quite slow in a highly purified system but is accelerated by small traces of practically any polar impurity. Pyridine, dipolar aptotic solvents, and oil-soluble ammonium chlorides have been used to improve the reaction (21). As a commercial process, the use of a solvent requites that the products must be separated from solvent as well as from each other and the excess butadiene which is used, but high yields of the desired products can be obtained without formation of polymer at higher butadiene to chlorine ratio. 

In a study of the kinetics of the reaction of 1-butanol with acetic acid at 0—120°C, an empirical equation was developed that permits estimation of the value of the rate constant with a deviation of 15.3% from the molar ratio of reactants, catalyst concentration, and temperature (30). This study was conducted usiag sulfuric acid as catalyst with a mole ratio of 1-butanol to acetic acid of 3 19.6, and a catalyst concentration of 0—0.14 wt %. 

Controlled hydrogenation over Ni or the electrochemical reduction of o -nitrobenzo itriles produced 3-amino-2,l-benzisoxazoles either as the major product or by-product, depending in part on the reaction media and ratio of reactants (72BSF2365, 65CB1562). Reduction of o-nitrobenzonitrile gave either 3-amino-2,l-benzisoxazole or 2-aminobenzonitrile. The benzisoxazole is presumed to arise via an intermediate hydroxylamine. The electrochemical reduction of o-nitrobenzonitrile at acid pH produced the hydroxylamine as the primary product. Reduction at neutral pH gave the amino-2,1-benzisoxazole and the hydroxylamine (72BSF2365). 

The ethoxyl content is controlled by the ratio of reactants and to a lesser degree by the reaction temperature. 

The strong influence of morphology and mixing is well illustrated with the composite particle investigation. These particles were composed of a nickel shell coated on spherical aluminum particles by hydrogen reduction in aqueous metal salt solution. The overall ratio of material in a particle was about 80 wt% Ni and 20 wt% aluminum. With these particles, the ratio of reactants was approximately the same as in the mixed powders, but the morphology of the reactants is radically different. 

When chloral was usedasthealdehyde2equivalents reacted with 1 equivalent of the enamine (98) regardless of the ratio of reactants or order of addition to give 2,6-bis(trichloromethyl)-5,5-dimethyl-4-morpholino-/ i-dioxane (183) in 83 % yield (126). Hydrolysis of 183 with hydrochloric acid at room temperature gave the hemiaeetal (184), but when heated with acid, the aldol product (185) was formed. 

Another class of complexes involves rj (N)-coordinated species of the Nl-unsubstituted pyrazoles. Chromium hexacarbcMiyl and pyrazole or 3,5-dimethyl-pyrazole form [(Hpz)Cr(CO)5] ot [(Hpz )Cr(CO)5] irrespective of the ratio of reactants. In similar circumstances, tungsten hexacarbonyl yields both [(Hpz)W(CO)5]... 

Product composition can be controlled to a considerable extent by the molar ratio of reactants alkylation tends to become more extensive as the molar ratio of carbonyl to amine increases. Product distribution is influenced also by the catalyst and by steric hindrance with the amount of higher alkylate formed being inversely proportional to the steric hindrance in the neighborhood of the function (60 2). Cyclic ketones tend to alkylate ammonia or amines to a further extent than do linear ketones of comparable carbon number 36). 

Fig. 6. Dependence of relative molar concentrations Wj/nA0 of reaction components on reciprocal space velocity W/F (hr kg mole-1) in the consecutive demethylation of m-xylene. Temperature 330°C, catalyst Ni-AljOs (55% wt. AljOs), initial molar ratio of reactants 0 = 5. The curves were calculated (1—xylene, 2—toluene, 3—benzene) the points are experimental values.

T. A. Ventrone, Ibid 38 CA 72, 113375 (1970) (a number of explosions during batch nitration are described. The effects of temp, rate of addition, and ratio of reactant on the explns are shown. It is suggested that safety standards be determined and enforced)... 

To simulate the process in the pilot reactor, the ratio of reactant flow rates should be the same as the ratio of total weight. With the feed rates in the correct proportion, the rate of heat release from the exothermic reaction, Q, should also be in the same proportion. However, R... 

Otsuka et al. (107) describe [Ni(CNBu )2], as a reddish brown microcrystalline substance, which is extremely air-sensitive. It can be recrystallized from ether at —78°C, and is soluble in benzene in the latter solution the infrared spectrum (2020s, br, 1603m, 1210m) and proton NMR (three peaks of equal intensity at t8.17, 8.81, and 8.94) were obtained. Neither analytical data nor molecular weight is available on this complex. The metal-ligand stoichiometry is presumably established by virtue of the molar ratio of reactants and by the stoichiometries of various reaction products. 

Figure 7 illustrates the use of HPGPC to aid a resin chemist in developing an in-house isocyanate crosslinker for a powder coating system. Isocyanate crosslinker X-02 gave desired properties and is considered the standard. At the early stage of the development, resin X-03 was initially made. By changing the types of reactants, molar ratio of reactants and reaction conditions, resin X-36 was the next iteration in the resin synthesis process. Finally, X-36 was fine-tuned to produce X-38 which matched X-02 in both its chemical reaction properties and its MWD. 

This reaction undergoes conversion in one sequence of consecutive elementary reaction steps and so only one propagating front is formed in a spatially distributed system [68]. Depending on the initial ratio of reactants, iodine as colored and iodide as uncolored product, or both, are formed [145]. 

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