Mass supercritical

Several standard methods for the quantitative analysis of food samples are based on measuring the sample s mass following a selective solvent extraction. For example, the crude fat content in chocolate can be determined by extracting with ether for 16 h in a Soxhlet extractor. After the extraction is complete, the ether is allowed to evaporate, and the residue is weighed after drying at 100 °C. This analysis has also been accomplished indirectly by weighing a sample before and after extracting with supercritical GO2. 

SFC/MS. supercritical fluid chromatography and mass spectrometry used as a combined technique SID. surface-induced dissociation (or decomposition)... 

M. A. McHugh and V. J. Knikonis, Supercritical Fluid Extraction, Butterworth Pubhshers, Stoneham, Mass., 1986. 

The use of separation techniques, such as gel permeation and high pressure Hquid chromatography interfaced with sensitive, silicon-specific aas or ICP detectors, has been particularly advantageous for the analysis of siUcones in environmental extracts (469,483—486). Supercritical fluid chromatography coupled with various detection devices is effective for the separation of siUcone oligomers that have molecular weights less than 3000 Da. Time-of-flight secondary ion mass spectrometry (TOF-sims) is appHcable up to 10,000 Da (487). 

A. Garg, L. Gerhardt, and E. Gulari, Proceedings of the Second International Symposium on Supercritical Fluids Boston, Mass., 1991. 

K. Haitonen and M. L. Riekkola, Detection of /3-blockers in urine by solid-phase extraction-supercritical fluid exti action and gas cliromatogi aphy-mass spectrometi y , 7. Chromatogr. B 676 45-52 (1996). 

In order to reduce or eliminate off-line sample preparation, multidimensional chromatographic techniques have been employed in these difficult analyses. LC-GC has been employed in numerous applications that involve the analysis of poisonous compounds or metabolites from biological matrices such as fats and tissues, while GC-GC has been employed for complex samples, such as arson propellants and for samples in which special selectivity, such as chiral recognition, is required. Other techniques include on-line sample preparation methods, such as supercritical fluid extraction (SFE)-GC and LC-GC-GC. In many of these applications, the chromatographic method is coupled to mass spectrometry or another spectrometiic detector for final confirmation of the analyte identity, as required by many courts of law. 

The combination of ionic liquids with supercritical carbon dioxide is an attractive approach, as these solvents present complementary properties (volatility, polarity scale.). Compressed CO2 dissolves quite well in ionic liquid, but ionic liquids do not dissolve in CO2. It decreases the viscosity of ionic liquids, thus facilitating mass transfer during catalysis. The separation of the products in solvent-free form can be effective and the CO2 can be recycled by recompressing it back into the reactor. Continuous flow catalytic systems based on the combination of these two solvents have been reported [19]. This concept is developed in more detail in Section 5.4. 

A number of analytical techniques such as FTIR spectroscopy,65-66 13C NMR,67,68 solid-state 13 C NMR,69 GPC or size exclusion chromatography (SEC),67-72 HPLC,73 mass spectrometric analysis,74 differential scanning calorimetry (DSC),67 75 76 and dynamic mechanical analysis (DMA)77 78 have been utilized to characterize resole syntheses and crosslinking reactions. Packed-column supercritical fluid chromatography with a negative-ion atmospheric pressure chemical ionization mass spectrometric detector has also been used to separate and characterize resoles resins.79 This section provides some examples of how these techniques are used in practical applications. 

FIG. 17 Ion pair/supercritical fluid extraction (SFE) and derivatization gas chromatography-mass-spectrometry (GC-MS). 

Neutrons produced in a chain reaction are moving very fast, and most escape into the surroundings without colliding with another fissionable nucleus. However, if a large enough number of uranium nuclei are present in the sample, enough neutrons can be captured to sustain the chain reaction. In that case, there is a critical mass, a mass of fissionable material above which so few neutrons escape from the sample that the fission chain reaction is sustained. If a sample is supercritical,... 

In a nuclear weapon, the fissile material is initially subcritical. The challenge is to produce a supercritical mass so rapidly that the chain reaction takes place uniformly throughout the metal. Supercriticality can be achieved by shooting two subcritical blocks toward each other (as was done in the bomb that fell on Hiroshima) or by implosion of a single subcritical mass (the technique used in the bomb that destroyed Nagasaki). A strong neutron emitter, typically polonium, helps to initiate the chain reaction. 

CH3(CH2)3CH3 + CH3CH=CH2. critical mass The mass of fissionable material above which so few neutrons escape from a sample of nuclear fuel that the fission chain reaction is sustained a greater mass is supercritical and a smaller mass is subcritical. 

Fe(CN)6]3-(aq) + 6 H20(1). substrate The chemical species on which an enzyme acts, superconductor An electronic conductor that conducts electricity with zero resistance. See also high-temperature superconductor. supercooled Refers to a liquid cooled to below its freezing point but not yet frozen, supercritical fluid A fluid phase of a substance above its critical temperature and critical pressure. supercritical Having a mass greater than the critical mass. 

A supercritical fluid exhibits physical-chemical properties intermediate between those of liquids and gases. Mass transfer is rapid with supercritical fluids. Their dynamic viscosities are nearer to those in normal gaseous states. In the vicinity of the critical point the diffusion coefficient is more than 10 times that of a liquid. Carbon dioxide can be compressed readily to form a liquid. Under typical borehole conditions, carbon dioxide is a supercritical fluid. 

Nanoparticles of controllable size can be obtained in the supercritical antisolvent-enhanced mass-transfer (SAS-EM) process, which can... 

FIG. 20 22 Schematic of supercritical antisolvent with enhanced mass-transfer process to produce nanoparticles of controllable size. R, precipitation chamber SCF pump, supply of supercritical COg I, inline filter H, ultrasonic horn P, pump for drug solution G, pressure gauge. 

Pressurized Fluid Extraction followed by Gas Chromatography/Mass Spectrometry (PFE-GC/MS) On-line Supercritical Fluid Extraction - Gas Chromatography/Mass Spectrometry (SFE-GC/MS)... 

Interfaces for Supercritical Fluid Chromatography/Mass Spectrometry... 

Supercritical fluid chromatography Thin-layer chromatography Atomic absorption spectroscopy Nuclear magnetic resonance spectroscopy Mass spectrometry Fourier transform infrared spectrometry... 

Principles and Characteristics Supercritical fluid extraction uses the principles of traditional LSE. Recently SFE has become a much studied means of analytical sample preparation, particularly for the removal of analytes of interest from solid matrices prior to chromatography. SFE has also been evaluated for its potential for extraction of in-polymer additives. In SFE three interrelated factors, solubility, diffusion and matrix, influence recovery. For successful extraction, the solute must be sufficiently soluble in the SCF. The timescale for diffusion/transport depends on the shape and dimensions of the matrix particles. Mass transfer from the polymer surface to the SCF extractant is very fast because of the high diffusivity in SCFs and the layer of stagnant SCF around the solid particles is very thin. Therefore, the rate-limiting step in SFE is either... 

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