Physical properties Important data

T. Cairns and J. Sherma, eds.. Comprehensive Analytical Profiles of Important Pesticides, CRC Press, Boca Raton, Fla., 1992, 304 pp. From the series ModemMethods for Pesticide Analysis, provides detailed information on properties and analytical methodology for nine prominent pesticides, pyrethroids, and fumigants in food. Includes formulations and uses, chemical and physical properties, toxicity data, and tolerances on various foods and feeds. Analytical information may be given in enough detail for methods to be carried out without having to consult additional Hterature sources. 

Physical and Chemical Properties. More experimental and estimated data on the physical and chemical properties for 2,4-DNP are available than for other dinitrophenols (see Table 3-2). Even in the case of 2,4-DNP, reliable experimental or estimated values are not available for vapor pressure, Henry s law constant, and log K°<=. This is not surprising since dinitrophenols exist predominantly in the ionic forms at pH >6 with very low vapor pressure. If available, the physical constants are important in predicting the environmental transport of dinitrophenols. Therefore, it would be helpful to develop more reliable data on certain physical properties important in predicting the environmental fate of these compounds. 

On the basis of ext ensive exx>erimental work international co-operation within the European Federation of Chemical Engineering has resulted in the standardization of test mixtures. The booklet published byZuiderweg [195] contains the equilibrium data as well as all important physical properties and data concerning the chemical stability of the components for 11 systems. It is suggested to use mainly the test mixtures Usted in Table 29 so that it should be possible to compare the efficiency of packings and columns. 

Ethyleneimine (El) and its two most important derivatives, 2-methyla2iridine [75-55-8] (propyleneimine) (PI) and l-(2-hydroxyethyl)a2iridine [1072-52-2] (HEA) are colodess Hquids. They are miscible ia all proportions with water and the majority of organic solvents. Ethyleneimine is not miscible with concentrated aqueous NaOH solutions (>17% by weight) (24). Ethyleneimine has an odor similar to ammonia and is detectable only at concentrations >2 ppm. The physical properties of ethyleneimine and the derivatives mentioned are given ia Table 1. Thermodynamic data can be found ia the Hterature (32). 

DIPPR American Institute of Chemical Engineers and Design Institute for Physical Property Data numeric physical property data for commercially important chemicals and substances... 

Selected physical properties of various methacrylate esters, amides, and derivatives are given in Tables 1—4. Tables 3 and 4 describe more commercially available methacrylic acid derivatives. A2eotrope data for MMA are shown in Table 5 (8). The solubiUty of MMA in water at 25°C is 1.5%. Water solubiUty of longer alkyl methacrylates ranges from slight to insoluble. Some functionalized esters such as 2-dimethylaniinoethyl methacrylate are miscible and/or hydrolyze. The solubiUty of 2-hydroxypropyl methacrylate in water at 25°C is 13%. Vapor—Hquid equiUbrium (VLE) data have been pubHshed on methanol, methyl methacrylate, and methacrylic acid pairs (9), as have solubiUty data for this ternary system (10). VLE data are also available for methyl methacrylate, methacrylic acid, methyl a-hydroxyisobutyrate, methanol, and water, which are the critical components obtained in the commercially important acetone cyanohydrin route to methyl methacrylate (11). 

Propylene oxide is a colorless, low hoiling (34.2°C) liquid. Table 1 lists general physical properties Table 2 provides equations for temperature variation on some thermodynamic functions. Vapor—liquid equilibrium data for binary mixtures of propylene oxide and other chemicals of commercial importance ate available. References for binary mixtures include 1,2-propanediol (14), water (7,8,15), 1,2-dichloropropane [78-87-5] (16), 2-propanol [67-63-0] (17), 2-methyl-2-pentene [625-27-4] (18), methyl formate [107-31-3] (19), acetaldehyde [75-07-0] (17), methanol [67-56-1] (20), ptopanal [123-38-6] (16), 1-phenylethanol [60-12-8] (21), and / /f-butanol [75-65-0] (22,23). 

Quahty control testing of siUcones utilizes a combination of physical and chemical measurements to ensure satisfactory product performance and processibihty. Eor example, in addition to the usual physical properties of cured elastomers, the plasticity of heat-cured mbber and the extmsion rate of TVR elastomers under standard conditions are important to the customer. Where the siUcone appHcation involves surface activity, a use test is frequently the only rehable indicator of performance. Eor example, the performance of an antifoaming agent can be tested by measuring the foam reduction when the sihcone emulsion is added to an agitated standard detergent solution. The product data sheets and technical bulletins from commercial siUcone producers can be consulted for more information. 

Use of such a data system is easy, provided that the permanent system data bank has entries for the components of interest. Thus it is often important to the user that the data bank is extensive and not restricted to a small class of compounds. However, the number of chemical species is enormous and expanding at a rapid rate. Accordingly, for wide appHcation it is necessary that the physical property system embodies faciUties for the use of user-supphed data. 

Data compilations, the first recourse for an engineering calculation requiring physical property or parameter data, are often incomplete or do not contain data within the appropriate range of temperature or pressure (6—9). For this reason, correlation and estimation methods play an important role in apphed thermodynamics. 

It has been shown throughout this chapter that the properties of plastics are dependent on time. In Chapter 1 the dependence of properties on temperature was also highlighted. The latter is more important for plastics than it would be for metals because even modest temperature changes below 100°C can have a significant effect on properties. Clearly it is not reasonable to expect creep curves and other physical property data to be available at all temperatures. If information is available over an appropriate range of temperatures then it may be possible to attempt some type of interpolation. For example, if creep curves are available at 20°C and 60°C whereas the service temperature is 40°C then a linear interpolation would provide acceptable design data. 

A wide variety of physical properties are important in the evaluation of ionic liquids (ILs) for potential use in industrial processes. These include pure component properties such as density, isothermal compressibility, volume expansivity, viscosity, heat capacity, and thermal conductivity. However, a wide variety of mixture properties are also important, the most vital of these being the phase behavior of ionic liquids with other compounds. Knowledge of the phase behavior of ionic liquids with gases, liquids, and solids is necessary to assess the feasibility of their use for reactions, separations, and materials processing. Even from the limited data currently available, it is clear that the cation, the substituents on the cation, and the anion can be chosen to enhance or suppress the solubility of ionic liquids in other compounds and the solubility of other compounds in the ionic liquids. For instance, an increase in allcyl chain length decreases the mutual solubility with water, but some anions ([BFJ , for example) can increase mutual solubility with water (compared to [PFg] , for instance) [1-3]. While many mixture properties and many types of phase behavior are important, we focus here on the solubility of gases in room temperature IFs. 

An important but time-consuming factor in practically every design situation and in development of flowsheets is the collection and assembly of physical property data for the components of the. system in question. Often it is not sufficient tc obtain single data points from various tables, since many designs cover rather wide ranges of temperature and pressure and the effects of these on the properties must be taken into account. 

Therefore, when developing an estimate of process engineering time required, it is important to recognize the amount of effort that may be necessary to collect physical property data before any real work can commence. This same concern exists when evaluating K values and activity data for systems. 

Najjar, Bell, and Maddox studied the influence of physical property data on calculated heat transfer film coefficients and concluded that accurate fluid property data is extremely important when calculating heat transfer coefficients using the relationships offered by Dittus-Boelter, Sieder-Tate, and Petukhov. Therefore, the designer must strive to arrive at good consistent physical/thermal property data for these calculations. 

Pressure or density programming is the most popular of the gradient techniques in SFC. Density is the important parameter with respect to retention but pressure is the physical property which is directly monitored by SFC instruments. If enough experimental density-volume-temperature data are available for the mobile phase then a computer-based algorithm can be used to generate specific density programs. Such data are available for only a few mobile phases, such as carbon dioxide and the n-... 

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