Physical Properties

Fluid Properties and New Technologies:

Connecting Design with Reality
Allan H. Harvey and Arno Laesecke, National Institute of Standards and Technology

Addressing the challenges outlined here will help ensure that engineers of the future have the data they need.

ccurate thermophysical properties of uids are essential to design and operation in the chemical process industries (CPI). The necessity of having good thermo is widely recognized in this context, although it is often taken for granted that this will be provided by process simulation software. While traditional chemical manufacturing and hydrocarbon processing will continue to be important, developments such as miniaturization, decentralization, demand-controlled production, exible feedstocks and information technology, as well as new technologies that are emerging in such areas as waste minimization, biotechnology, advanced fuels and high-value chemicals, will catalyze dramatic changes in the uids-based industries. There is a growing emphasis on virtual tools for accelerating the development of new technologies. However, the dependence of many of these tools on robust property models, and the need for accurate data to validate these models, often go unrecognized. Research on uid properties cannot continue with business as usual if it is to meet the future needs of industry. Emerging technologies will require measurements and models for different uids, and improved ways of utilizing data. In principle, this should be an opportunity for the revitalization of property research. In reality, however, there is a fear that the current decline in support will continue, leaving the research community unable to supply essential data. This article reviews some of the areas where uid

property work can make a contribution, including molecular simulation, combinatorial methods and measurements, process miniaturization, environmental technology, unconventional mixtures and materials, and data standardization and exchange. It also discusses some of the challenges, many of them structural, that must be overcome if uid property researchers are to be successful in providing information that meets the needs of industry.

Opportunities in molecular simulation Molecular simulation can describe a variety of techniques, including quantum calculations of electronic structure and intermolecular forces, molecular dynamics (where forces are specied and the equations of motion are integrated), Monte Carlo simulation (the determination of equilibrium properties based on sampling of a statistical distribution), and methods such as Brownian dynamics where not all molecules are treated explicitly. Applications are discussed in Refs. 3 and 4. In the past, simulation has mainly been used to gain insight into molecular phenomena and to test theories. These uses will continue, but as computing power increases and as our ability to represent intermolecular forces improves, simulation will increasingly be used to calculate properties. This has already happened in thermochemistry, where heats of formation for many compounds can be calculated from quantum mechanics as accurately as they can be measured (and at lower cost). We foresee two ways in which molecular simulation

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Forum on fluid properties and new technologies

This article is based, in part, on Forum 2000 Fluid Properties for New Technologies: Connecting Virtual Design With Physical Reality, which was held in June 2000, in conjunction with the 14th Symposium on Thermophysical Properties in Boulder, CO. Here are some highlights of what panelists said about the role of fluid properties in developing technology and validating design tools. In the field of molecular simulation, increasing computer power is enabling simulation to produce thermophysical property results with much less labor than experiment or theory. However, there is a continuing need for experimental benchmarks and for theoretical advances. Miniaturized systems are opening up new avenues in chemical processing, and fluid property needs shift with process miniaturization and intensification. For example, fluid/wall interactions, surface tension and wettability play a more prominent role. Radioactive fluid waste at places such as the U.S. Dept. of Energy (DOE) Hanford site presents several challenges. For example, the models used to predict the behavior of complex multiphase slurries in holding tanks and pipelines during cleanup operations have been grossly inadequate and need to be improved. To improve the modeling of materials corrosion, environmental technology and crystallization, better data and models are needed for the transport properties of aqueous electrolytes, the equilibria among different species in solution, and the precipitation of solids from solution. The DOE Fossil Energy Offices Vision 21 program is developing highly efficient, environmentally benign electric power plants. The distinction between a power plant and a chemical plant will blur as fuels and other chemicals are produced in addition to electricity. Virtual tools for demonstration, design and optimization will be used throughout the program. Property data, particularly reference-quality data from institutions like the National Institute of Standards and Technology (NIST), are very valuable for process design and development. The use of design software needs to be accompanied by better uncertainty analysis and user education. In addition, there is a need for data on unconventional materials, such as electrolytes, solids, polymers and materials whose properties are a function of their synthesis history. There is potential in the study of soft solids, such as foods, soaps and partially molten metals, as well as in the study of heterogeneous and reacting mixtures. Although experimentation is costly, takes time and can be dangerous, there must be a proper balance between theory, simulation and experiment. A major issue in the discussion was the degree to which molecular simulation could replace experimentation. The consensus seemed to be that simulation is useful in initial screening, but that experimental data are still essential for final design. The need for continued theory and modeling work in cooperation with experimentation and simulation rather than in competition was emphasized. There was also discussion on the lack of efficient means for connecting fluid property research to the needs of industry, and on the (perhaps related) lack of funding for such research. More complete records of Forum 2000 can be found in Refs. 1 and 2.

will be most useful. The rst is in screening candidate uids for a process. Simulations of moderate accuracy could narrow the list of candidates to the point where a few could be subjected to experiment. In this role, simulation may supplant the group-contribution estimation methods now used for compounds where data are lacking. Second, simulation can address experimentally inaccessible systems, such as those at extreme temperatures or pressures, unstable reaction intermediates, or hazardous compounds. An example is the investigation of the chainlength dependence of the critical density of n-alkanes (5,6). Simulations established that the critical density went through a maximum and declined, contrary to some correlations and the trend of one set of measurements (but in agreement with polymer theory). This has become a famous success story for simulation. However, the subsequent discovery (7) of a programming error (which affected the critical temperatures, but fortunately did not signicantly affect the critical densities) illustrates that simulations, like experiments, can have systematic errors.

Molecular simulation has a bright future. But will computer experiments totally replace real measurements? For several reasons, we believe that is probably not possible, and certainly not wise. First, for chemically stable systems, the best experiments still far surpass simulation in accuracy. Advances in computing power will help close that gap, but not as quickly as one might think. Typically, reducing the uncertainty in a property by an order of magnitude takes many orders of magnitude more computation. Barring major breakthroughs in methodology, it is safe to say that simulation will not catch up to experimentation for many decades, if at all. More fundamentally, the force fields used in simulations only approximate the true intermolecular forces, so even a perfect simulation cannot exactly represent reality. For example, multibody interactions are often neglected, and while this simplifies things, it is physically incorrect and introduces some error. Quantum calculations can improve potentials, but their cost goes up

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steeply with the level of theory and with molecular size. As increased computing power allows simulations with reduced statistical uncertainty, the force fields will become (and already are in many cases) the limiting factor in their accuracy. Because the development of force fields is dominated by the drug industry, much effort is expended to represent organic molecules in water at room (or body) temperature, while work for other applications lags behind. Since experimentation will be more accurate than simulation for most systems for the foreseeable future, measurements on benchmark systems will remain essential. Comparison to good data will be necessary to validate both simulation techniques and force elds. Finally, if molecular simulation of uid properties is to become widely useful, simulated data, just like measured data, should have uncertainty estimates so that those using them can know how much condence to place in them. Currently, these are often lacking.

of experimental work. Integration of sensors and actuators is required in order for microreaction technology to move beyond the laboratory into chemical production (11).

Opportunities in miniaturization The CPI will be transformed by miniaturization, much as the computer industry was by the microprocessor, except that the change in the CPI is likely to be faster. As microfabrication techniques improve, large-scale centralized production will give way to a spectrum of plants, ranging from large reneries to on-board gasoline processors in fuel-cell-powered vehicles to subcutaneous drug synthesis and delivery systems. The smaller scale will favor new approaches, such as electrochemical energy conversion (fuel cells) in preference to thermochemical conversion (combustion). Other examples include electrokinetically driven uid ow in lab-on-a-chip devices (8) and metastable (superheated) liquids as thermomechanical power converters of high energy density. We foresee two main trends. First, miniaturized systems will be fluid-based because fluid flow is the easiest way to transport material on the microscale. (Nature is the best example of this aqueous solutions are the main transport media in living organisms.) Second, electrochemistry and electrofluidics will become important because microfluidic and electronic systems can be coupled and integrated. Microscale technology will drive uid property research into relatively unexplored areas. It will be important to study the effects of small dimensions, connement and high surface-to-volume ratios (9,10). Additionally, the properties of polar uids and electrolytes in electric and magnetic elds will be important for the integration of uidics and electronics. Microscale thermophysical property sensors will allow investigation of new domains, such as metastable liquids for which small sample sizes are essential. Reducing sensor sizes will reduce thermal inertia so that measurements can be carried out much faster, overcoming a major stigma

Opportunities in environmental technology Fluid thermophysical properties is only one of many areas where knowledge is needed for waste cleanup. Within this area, the prediction of phase equilibria and thermal effects is important. Waste tanks may contain water, electrolytes, solids, organics and gases. One cannot measure all the possible combinations, so reliable models encompassing these components are needed. Data on key subsystems will be necessary in order to develop and validate these models. An emerging environmental technology is supercritical water oxidation (SCWO), which is often complicated by the precipitation of solids. Good models for solid/uid equilibria (and reliable computation of complex phase diagrams) would be helpful in the design of SCWO processes. Models have been developed for a few systems, such as NaCl/H2O, but extension to other systems of interest is stymied by lack of experimental data. Transport properties of aqueous mixtures at these conditions are also important for SCWO, but data and models for these are also lacking. Even established technologies could use better uid properties. Air and steam stripping are widely used to clean contaminants from water. Hwang et al. (12) emphasized the dependence of these processes on the Henrys constant for the solute in water, and discussed the inadequacy of data at 25C for steam stripping conditions. Better measurements over a range of temperatures are needed, as are better predictions of Henrys constants and their temperature dependence. Regulatory agencies are starting to use databases of Henrys constants; the economic impacts of their decisions suggest that investment in standardization, validation and improvement of these databases would be worthwhile. A challenge is that many engineers working on environmental problems have a limited background in thermodynamics and physical properties. They may not be equipped to recognize where properties are crucial in a process, and may not know where to nd the necessary data or expertise. Fluid property experts need to be proactive in educating developers and users of environmental technology about the importance of property data. Opportunities in unconventional mixtures and materials Much uid property research over the years has been on hydrocarbons and commodity chemicals, and recently on non-ozone-depleting refrigerants. The future will require also studying different uids that are important in new technologies (and in some poorly understood old technologies). Some existing processes in need of reliable data and models include polymer systems, electrolytes, chemically reacting mixtures, and systems with precipitating

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solids. Transport properties are often poorly understood. In many cases, data exist near room temperature, but not at the conditions of importance in industry. Several of these complications may coexist, and it is a challenge to integrate independently developed knowledge, for example of electrolyte and polymer solutions. There are also areas where uid property information has not traditionally played an important role but that are ripe for integration of basic research. These include molten metals and products such as foods and soaps, as well as reacting mixtures such as combustion gases and gases used in semiconductor manufacture. New technologies will require research on uids that have been studied either not at all or not at the relevant conditions. For microtechnology, properties of uids near surfaces will be important. A knowledge gap exists with regard to the stability limits and properties of metastable uids (liquids cooled below the freezing point or heated above the boiling point, or subcooled vapors) (13). The growth of biotechnology will increase the need for solution properties of biomolecules and of larger structures such as cells. Properties of the uids and materials in fuel cells will be important. Room-temperature ionic liquids show promise as green solvents (14); data are lacking on their thermophysical properties and on the properties of solutions with ionic liquids as solvents. Many of the systems we have mentioned are messy, not only from an experimental standpoint, but also for theory and modeling. Fluid property researchers must move into more of these messy areas to remain relevant to industrial needs.

Opportunities in data standardization and exchange Individual companies can no longer afford to collect and maintain all the data they need for process modeling, so they are increasingly relying on third-party software and databases. This trend exacerbates problems of data exchange incompatible or inexible formats increase the overhead associated with transferring data among applications. Thus, uid property databases are becoming increasingly important. Engineers are more efficient if they can easily nd and use information in a trustworthy database rather than having to devote resources to searching literature, converting and formatting data, and so on. A trustworthy database must be much more than a collection of numbers. Users need numbers that represent the best judgment of experts, and also need realistic estimates of their uncertainty. There must also be standardized exchange protocols, so that data can ow easily among applications and across networks. AIChEs main data effort is the Design Institute for Physical Properties (DIPPR) program. DIPPR is funded by industrial sponsors. It supports some experimental work, but its most visible efforts are directed toward property

databases for the CPI. The best-known product of DIPPR is the database from its Project 801, which contains evaluated and correlated pure-component data for key properties. The database currently contains over 1,700 compounds, and about 50 new compounds are added each year. DIPPR 801 is widely used for pure-component properties in chemical process simulation. Another major source of evaluated uid property data is the National Institute of Standards and Technology (NIST), where the Standard Reference Data program is the focal point for data dissemination. Efforts range from referencequality correlations reecting expert consensus (and, in some cases, standards adopted by domestic or international bodies), to more predictive models for systems where data are scarce, to the NIST Chemistry Webbook (http://webbook.nist.gov/chemistry). The Thermodynamics Research Center (TRC) (recently returned to NIST from Texas A&M Univ.) issues a variety of data products and maintains an enormous database, with information on approximately 100 properties for 16,000 pure components and numerous mixtures. Other important efforts include the databases developed by DECHEMA in Germany and the Physical Properties Data Service (PPDS) based at the National Engineering Laboratory in Great Britain. These efforts require uid property experts to evaluate data, make judicious extrapolations and estimates, and produce reliable correlations. Experts also provide continuity, which is essential to data quality. For new technologies and processes, databases will have to add new compounds and mixtures and perhaps additional properties. A challenge for these efforts is to obtain steady funding both to maintain and expand the database and to employ property experts. In addition, the Internet, while providing new opportunities for both the use and dissemination of data, is forcing signicant structural changes on database providers. To be useful, these databases need to work smoothly with all the tools employed in process design, development and operation. This requires standardized protocols for data exchange. A major effort in that direction, aimed at all aspects of process modeling, is the Global CAPE-OPEN project (15). Project 991 of DIPPR has begun work specifically for the exchange of thermophysical property data, and database providers such as NIST TRC are working to improve and promote tools for data exchange.

The challenge of Garbage In, Gospel Out John Prausnitz cautioned (16) Never be impressed by calculated results merely because they come from a computer. The virtue of a computer is speed, not intelligence. As the development of technology comes to depend more on software, and as this software becomes easier to use, the temptation grows to use the results without giving any thought to whether the computer is doing the appropriate calculation for the problem at hand. We are not opposed to computation. Programs such as
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process simulators have greatly enhanced engineering productivity. New technologies will require more such tools, integrated throughout the development cycle. Virtual tools are considered key enabling technologies in many emerging areas, and rightly so. However, these virtual tools must be validated against physical reality. This is increasingly important as software becomes more complex. The dangers of using process simulation software without thinking about thermophysical properties have been discussed many times (1720). Without reliable properties, a process simulator is just an expensive random-number generator. However, todays accelerated product-development cycles often cannot wait for complete validation of uid properties. There are several ways to reduce the risks associated with incomplete knowledge. Developers of models should clearly state limitations with regard to not only temperature and pressure but also chemical composition and class of compound. Too often, correlations tted to hydrocarbon data get used for methanol or even sodium hydroxide. While formal analysis is often not possible or necessary, there should be some estimate of the uncertainty of the numbers produced. Developers should not oversell their models we particularly lament the use of the word predictive to describe correlations. Finally, modelers should recognize that, despite their caveats, some users will insist on employing models outside their intended range. Therefore, they should try to use functional forms that extrapolate in a realistic way, making use of physical boundary conditions such as the ideal-gas limit. Developers of software have a difficult job. On the one hand, they need to protect their users from getting bad answers. On the other hand, users with a deadline do not want to hear that getting no answer at all is preferable to getting a wrong answer. Vendors should make clear the limitations of their software, including limitations of underlying property models. Users should be warned when models are used outside their valid range, but actually incorporating such judgment into software (while avoiding boy who cried wolf effects from a multitude of warnings for unimportant matters) is far from trivial. A related problem is that modeling software typically produces a single answer with no indication of its uncertainty or its sensitivity to uncertain input variables. Unfortunately, estimating uncertainties for systems and processes of real-world complexity is a difficult problem. In the near term, users will have to rely on crude sensitivity estimates obtained by varying individual parameters. For the long term, modeling approaches that incorporate statistics show some promise (21). Users of software must pay attention to the limitations of their tools, preferably with enough understanding of the underlying models to judge how much trust to place in the results. It may be impractical for each user to have such understanding, but there must at least be access to an ex-

pert who can be consulted if the problem is of sufficient importance. Ultimately, there is no substitute for experienced engineering judgment.

The challenge of the missing bridge The topic of engineering judgment brings up what we refer to as the missing bridge. Clearly, there are industrial needs for uid property data, and there are researchers capable of meeting those needs. However, there must be a bridge between the industrial process and the researcher. Otherwise, researchers may work on problems that are not relevant to industrial needs, and process developers may miss advantages that could be realized from better data. In the CPI, this bridge, until recently, often took the form of corporate engineering groups. These groups, usually including a few property specialists, were repositories of expertise and experience and could discern where property information would meet a companys technical needs. Today, corporate restructuring has eliminated or greatly reduced many such groups. As a result, there is often nobody in a position to recognize uid property needs and to communicate those needs to researchers. It is not clear how to rectify this. It is unlikely that companies will once again employ a suite of property experts; at best they may realize that the optimum level of internal expertise is greater than zero. Perhaps industrial concerns can pool their resources to support research in useful directions. The Petroleum Research Fund of the American Chemical Society and the DIPPR program of AIChE are two existing efforts along these lines. As developers of technology rely more on external software such as process simulators, the providers of this software may help bridge the gap. If software vendors recognize the importance of uid properties in their product, they may employ property experts who can recognize needs, communicate them to researchers, and even develop models themselves. In order to ll this role, these companies must work with their customers to understand how the software is being used and where improvement is needed. It would also be helpful if the needs identied could be translated into research support, either directly or by making the needs known to funding agencies. Ultimately, developers of technology and uid property researchers need to take much of the initiative for bridgebuilding. Developers (in industry and in government technology efforts) must recognize that reliable models require reliable data as a foundation. They must look deeply enough at their processes to identify places where property data are inadequate, and they must be willing to support work to address those gaps. Researchers need to be proactive in interacting with developers and discerning their real needs. This may require understanding chemical reactions, rate processes, equipment design and other complications they might prefer to ignore. Fluid property researchers cannot afford to work in isolation and answer questions that nobody is asking.

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Table. First members of homologous series for which comprehensive measurements of thermophysical properties are lacking. Compound (Rank*) Styrene (21) Formaldehyde (24) Toluene (25) Ethylene oxide (27) 1,2-Ethanediol (29) Phenol (31) Acrylonitrile (36) Acetone (39) Aniline (45) Dimethyl ether Methylal Methyl formate Methylamine Formula C8H8 CH2O C7H8 C2H4O C2H6O2 C6H6O C3H3N (CH3)2CO C6H7N CH3-O-CH3 CH3-O-CH2-O-CH3 CH3-O-CHO CH3-NH2

I Figure 1. Three rst members of homologous series whose thermophysical properties should be characterized comprehensively.

* Numbers in parentheses indicate rank among the top 50 chemicals by production volume in the U.S. in 1997. Source: (24).

The role of measurements Fluid property research is undergoing a global shift. In the last decade, the amount of experimental research has declined in the U.S. and, to a lesser degree, in other industrialized countries such as Japan and Germany. In contrast, it has increased elsewhere, particularly in Asia and South America. This trend parallels the move of industrial production to low-cost labor regions. This may reect the stigma that measurements take too long and cost too much. Has experimental uid property research become just another commodity to be outsourced? Engineers should learn the value of thermophysical properties in college. However, it is in academia (at least in the U.S.) where measurements of uid properties are most in decline. In Birds critique (22) of priorities in academic chemical engineering, we see some possible reasons for this trend: The quest for funding is more important than the quest for knowledge Graduate students are trained as technicians in extremely narrow areas, so that their professors can churn out research publications. One can churn out more publications by avoiding painstaking experimental work. A viscometer cannot be downloaded from the Internet like simulation software. When students who have only been exposed to computation enter industry, they may continue to seek quick answers from the computer to all problems. The result is engineering as a video game, which may not describe reality. What, then, is the role of measurements? There is an important difference between knowledge acquisition through real experiments and through simulation. Simulations observe the behavior of a model system in a controlled state under rules given by the programmer. Measurements also conne a sample in a thermodynamic state, but the rules are those of nature, not the investigator, giving more potential for surprise and discovery.

Given this signicant difference, measurements remain a primary method to study uid properties. However, experimenters cannot view their trade as the only path to knowledge. They must accept that many questions can be answered adequately by computer simulations, just as simulators must look to measurements to connect their work with reality. What is needed is cooperation among those engaged in simulation, experimentation and theory. For example, simulators can compare their results to experimental data where appropriate (as many theorists already do), and experimenters can make measurements chosen to validate simulation techniques and force elds and to discriminate among competing theories. Which uids should be measured? Comprehensive measurements (multiple properties over a wide range of conditions) of high accuracy are mainly needed for systems that are in some way unique, having a molecular interaction not covered in existing databases. For pure uids, rst members of homologous series are obvious targets. Surprisingly, many of these are poorly characterized. For example, a compilation of liquid viscosity data (23) has no data at all for dimethyl ether or formaldehyde. Molecular simulations for viscosities of such polar liquids have an uncertainty level of perhaps 30%, while simple experiments can achieve 0.3%. Some compounds in this category are shown in Figure 1, where isoelectron density surfaces and charge distributions highlight the polarity that makes them difficult to simulate or describe with theory. The table lists these and other rst members of homologous series that we believe need comprehensive, reference-quality measurements. Nine of these compounds ranked among the top 50 chemicals by production volume in the U.S. (24). Other candidates for measurements include representatives of industri-

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ally important multifunctional compound classes, such as ethanol amines or glycol ethers. Experience shows that long-term continuity is vital for fruitful experimental fluid property research. Such continuity is difficult to achieve in academia, and is increasingly rare in industry. On the other hand, long-term research is a trademark of national metrology laboratories like NIST in the U.S., the Federal Institution for Physics and Technology (PTB) in Germany, and the National Research Laboratory for Metrology (NRLM) in Japan. These labs often already have the instruments for such measurements; however, in many cases these are aging, custom-built apparatus that need to be automated and updated to efficiently perform comprehensive studies. New instruments and measurement methods have matured during the last two decades. These and other tools need to be employed in a systematic and coordinated manner to fill the gaps in our knowledge. Such a measurement agenda is daunting, especially if one considers combinatorial approaches that produce many candidate fluids for an application. Highly accurate comprehensive measurements will probably be limited to key fluids such as those listed in the table. For other systems, the need will be for high-speed study (sacrificing some accuracy) of a large number of fluids of varying molecular structure and mixture composition. Microtechnology and combinatorial methods can help address this need.

I Figure 2. An array platform has been developed at NIST for combinatorial

evaluations of sensing lms. Images courtesy of Dr. Michael Gaitan, NIST MEMS Project.

Combinatorial measurements Combinatorial chemistry can generate hundreds of thousands of new compounds (25). In this discovery process, identifying compounds and mixtures to perform a desired function will, in many cases, require characterizing both their chemical activities and their thermophysical properties. While high-throughput chemical screening can match the rates of compound synthesis, thermophysical properties cannot be measured at such rates with presently available instruments and techniques. However, the growing divergence between synthesis and characterization rates can be reversed by accelerated measurements with microsensors in a combinatorial approach. Traditionally, properties of fluids are measured on sample volumes ranging from 100 cm3 to 3 cm3 over wide ranges of pressures and temperatures. This is very timeconsuming measurement and data analysis of one property at one composition over a range of several hundred kelvins and several tens of megapascals might require several months. A different approach is needed for combinatorially synthesized compounds. They must be measured rapidly, usually at a single (often ambient) pressure and temperature, and in many different (often aqueous) mixtures. These composition-oriented measurements can be carried out much faster, because the mixture preparation can be highly

automated. In addition, measurement time and sample cost can be greatly lowered by reducing the sample volume to micro-, nano-, or even picoliters with micromachined thermophysical property sensors. Microsensors can be integrated into serial analyzers where several properties of the same sample can be measured rapidly. The microanalyzers can be operated in parallel to take advantage of the scalability of miniaturized systems. To fully exploit this scalability, it is necessary to expand the conventional mode of measurement (one uid at a time) to tens or even hundreds of different samples at once. Such cultural changes are difficult, but the potential of miniaturized systems demands that we embrace the new way of thinking. NIST has developed an array platform for performing combinatorial analyses of sensing lms (Figure 2). Each array element is a microhotplate with three functional layers: a heater that can reach 500C within milliseconds (inset), a thermometer/heat-distribution plate, and electrical contacts for monitoring a sample. Such microsensors and combinatorial methods open new horizons for experimentation on uids. Rapid composition-oriented measurements will generate much larger volumes of data. To derive the full benet from this combinatorial approach, these data must be effectively managed and integrated into databases. These data will also inuence the development of models. The capability to rapidly measure systems of many different molecular structures and compositions will promote the development of increasingly broad-based quantitative structureproperty relationships for the prediction of properties of new compounds.

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Literature Cited
1. Rainwater, J. C., et al., Forum 2000: Fluid Properties for New Technologies, Connecting Virtual Design with Physical Reality, J. Chem. Eng. Data, 46 (5), pp. 10021006 (Sept. 2001). 2. Rainwater, J. C., et al., Report on Forum 2000: Fluid Properties for New Technologies Connecting Virtual Design with Physical Reality, NIST Special Publication 975, U.S. Government Printing Office, Washington, DC (2001). Additional material on Forum 2000 is available at http://forum2000.boulder.nist.gov. 3. Deem, M. W., Recent Contributions of Statistical Mechanics in Chemical Engineering, AIChE J., 44 (12), pp. 25692596 (Dec. 1998). 4. Wilson, E. K., Bridging Chemistry and Engineering, Chem. & Eng. News, 77 (17), pp. 2432 (Apr. 26, 1999). 5. Siepmann, J. I., et al., Simulating the Critical Behavior of Complex Fluids, Nature, 365 (6444), pp. 330332 (Sept. 23, 1993). 6. Smit, B., et al., Computer Simulations of Vapor-Liquid Phase Equilibria of n-Alkanes, J. Chem. Phys., 102 (5), pp. 21262140 (Feb. 1, 1995). 7. Smit, B., et al., Erratum, J. Chem. Phys., 109 (1), p. 352 (July 1, 1998). 8. Kricka, L. J., Revolution on a Square Centimeter, Nature Biotech., 16 (6), pp. 513514 (June 1998). 9. Picraux, S. T., and P. J. McWorter, The Broad Sweep of Integrated Microsystems, IEEE Spectrum, 35 (12), pp. 2433 (Dec. 1998). 10. Jensen, K. F., Microchemical Systems: Status, Challenges, and Opportunities, AIChE J., 45 (10), pp. 20512054 (Oct. 1999). 11. Jensen, K. F., Microreaction Engineering Is Small Better?, Chem. Eng. Sci., 56 (2), pp. 293303 (Jan. 2001). 12. Hwang, Y.-L., et al., Steam Stripping for Removal of Organic Pollutants from Water. 2. Vapor-Liquid Equilibrium Data, Ind. Eng. Chem. Res., 31 (7), pp. 17591768 (July 1992). 13. Debenedetti, P. G., Metastable Liquids. Concepts and Principles, Princeton University Press, Princeton, NJ (1996). 14. Brennecke, J. F., and E. J. Maginn, Ionic Liquids: Innovative Fluids for Chemical Processing, AIChE J., 47 (11), pp. 23842389 (Nov. 2001). 15. Braunschweig, B. L., et al., Process Modeling: The Promise of Open Software Architectures, Chem. Eng. Prog., 96 (9), pp. 6576 (Sept. 2000). 16. Reid, R. C., et al., The Properties of Gases and Liquids, 4th ed., McGraw-Hill, New York, NY, Chapter 8 (1987). 17. Mathias, P. M., and H. C. Klotz, Take a Closer Look at Thermodynamic Property Models, Chem. Eng. Prog., 90 (6), pp. 6775 (June 1994). 18. Carlson, E. C., Dont Gamble With Physical Properties For Simulations, Chem. Eng. Prog., 92 (10), pp. 3546 (Oct. 1996). 19. Rhodes, C. L., The Process Simulation Revolution: Thermophysical Property Needs and Concerns, J. Chem. Eng. Data, 41 (5), pp. 947950 (Sept. 1996). 20. Linkson, P. B., Can You Trust Your Aqueous System Simulations?, Chem. Eng. Prog., 94 (5), pp. 6368 (May 1998). 21. Cipra, B., Revealing Uncertainties in Computer Models, Science, 287 (5455), pp. 960961 (Feb. 11, 2000). 22. Bird, R. B., Restore the Right Priorities, Chem. Eng. Prog., 92 (10), pp. 8083 (Oct. 1996). 23. Viswanath, D. S., and G. Natarajan, Data Book on the Viscosity of Liquids, Hemisphere Publishing, New York, NY (1989). 24. Chemical Manufacturers Association, U.S. Chemical Industry Statistical Handbook, CMA, Arlington, VA (1998). 25. Borman, S., Combinatorial Chemistry Redening the Scientic Method, Chem & Eng. News, 78 (20), pp. 5365 (May 15, 2000).

Closing thoughts Thermophysical properties of uids will be important for new technologies. But will the engineers of the future have the reliable data they need? Perhaps not, if uid properties are taken for granted and the challenges discussed here are not addressed. Molecular simulation offers promise, but more attention must be given to validating force elds and simulations with accurate data. High-quality measurements are needed, as are techniques to produce data more rapidly. Efforts must continue to produce reliable databases and to make their contents convenient to use and exchange. Simulators, theorists and experimenters must cooperate to leverage each others work. Perhaps most important, technology developers and researchers cannot operate in isolation, but must cultivate channels through which researchers can learn of needs and be supCEP ported in work to address those needs.

Acknowledgments
Several of our colleagues at NIST were instrumental in making Forum 2000 a reality and in the discussions that led to this article. We thank D. G. Friend, H. J. M. Hanley, W. M. Haynes, J. W. Magee, C. D. Muzny, J. C. Rainwater and especially C. D. Holcomb. We also thank all who contributed to the discussion, especially the panelists: Peter Cummings, Univ. of Tennessee and Oak Ridge National Laboratory; Ward TeGrotenhuis, Pacific Northwest National Laboratory; James Poppiti, U.S. Dept. of Energy; Andrzej Anderko, OLI Systems, Inc.; Thomas OBrien, U.S. Dept. of Energy; Paul Mathias, Aspen Technology, Inc.; and William Wakeham, Imperial College of Science, Technology and Medicine (currently at the Univ. of Southampton).

ALLAN H. HARVEY is a chemical engineer in the Theory and Modeling of Fluids Group of the Physical and Chemical Properties Div. at the National Institute of Standards and Technology (325 Broadway, Boulder, CO 80305; Phone: (303) 497-3555; Fax: (303) 497-5224; E-mail: aharvey@boulder.nist.gov). He has been with NIST since 1994, working in the areas of phaseequilibrium thermodynamics, thermodynamics of dilute solutions, and the properties of water and aqueous systems. Previously, he worked for Simulation Sciences Inc. He has a BS in chemical engineering from the Univ. of Missouri at Rolla and a PhD in chemical engineering from the Univ. of California at Berkeley. He is a member of AIChE and ASME. ARNO LAESECKE is with the Experimental Properties of Fluids Group of the Physical and Chemical Properties Div. at the National Institute of Standards and Technology (Phone: (303) 497-3197; E-mail: arno.laesecke@boulder.nist.gov). He joined NIST in 1988 as a visiting scientist with support from the German Science Foundation and the Joy L. Barton Charitable Trust and became a staff member in 1993. His interests include viscosity, thermal conductivity, and dielectric measurements of fluids, preferably metastable and/or polar, and the development of microscale thermophysical properties sensors for highthroughput and combinatorial studies. During 19911992, he was in the corporate research department of DaimlerChrysler AG, where he participated in the early development of the fuel-cell-powered NECAR. He earned his Dipl.-Ing. and Dr.-Ing. degrees in chemical engineering at the Univ. of Stuttgart (Germany). He is a member of AIChE.

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