Diffusion detectors

Figure 7.4—Light diffusion detector. Using nitrogen gas, the mobile phase is nebulised at the end of the column with a device of varying geometry. When a compound elutes from the column, the droplets under evaporation are transformed into fine particles that can diffuse light from a laser. This is called the Tyndall effect (it is similar to what is observed for a car when its lights are diffused by fog). The signal, detected by a photodiode, is proportional to the concentration of the compound. This detector can only be used for compounds that cannot be vaporised into the gas phase in the heated zone.

The eombination in a compact system of an infrared sensor and a laser as excitation source is called a photothermal camera. The surface heating is aehieved by the absorption of the focused beam of a laser. This localisation of the heating permits a three-dimensional heat diffusion in the sample to be examined. The infrared (IR) emission of the surface in the neighbourhood of the heating spot is measured by an infrared detector. A full surface inspection is possible through a video scanning of the excitation and detection spots on the piece to test (figure 1). 

McKillop and associates have examined the electrophoretic separation of alkylpyridines by CZE. Separations were carried out using either 50-pm or 75-pm inner diameter capillaries, with a total length of 57 cm and a length of 50 cm from the point of injection to the detector. The run buffer was a pH 2.5 lithium phosphate buffer. Separations were achieved using an applied voltage of 15 kV. The electroosmotic flow velocity, as measured using a neutral marker, was found to be 6.398 X 10 cm s k The diffusion coefficient,... 

The helium leak detector is a common laboratory device for locating minute leaks in vacuum systems and other gas-tight devices. It is attached to the vacuum system under test a helium stream is played on the suspected leak and any leakage gas is passed into a mass spectrometer focused for the helium-4 peak. The lack of nearby mass peaks simplifies the spectrometer design the low atmospheric background of helium yields high sensitivity helium s inertness ensures safety and its high diffusivity and low adsorption make for fast response. 

Information on ionization energies, solubiUties, diffusion coefficients, and soHd—Hquid distribution coefficients is available for many impurities from nearly all columns of the Periodic Table (86). Extrinsic Ge and Si have been used almost exclusively for infrared detector appHcations. Of the impurities,... 

Water Transport. Two methods of measuring water-vapor transmission rates (WVTR) ate commonly used. The newer method uses a Permatran-W (Modem Controls, Inc.). In this method a film sample is clamped over a saturated salt solution, which generates the desired humidity. Dry air sweeps past the other side of the film and past an infrared detector, which measures the water concentration in the gas. For a caUbrated flow rate of air, the rate of water addition can be calculated from the observed concentration in the sweep gas. From the steady-state rate, the WVTR can be calculated. In principle, the diffusion coefficient could be deterrnined by the method outlined in the previous section. However, only the steady-state region of the response is serviceable. Many different salt solutions can be used to make measurements at selected humidity differences however, in practice,... 

Carbon Dioxide Transport. Measuring the permeation of carbon dioxide occurs far less often than measuring the permeation of oxygen or water. A variety of methods ate used however, the simplest method uses the Permatran-C instmment (Modem Controls, Inc.). In this method, air is circulated past a test film in a loop that includes an infrared detector. Carbon dioxide is appHed to the other side of the film. AH the carbon dioxide that permeates through the film is captured in the loop. As the experiment progresses, the carbon dioxide concentration increases. First, there is a transient period before the steady-state rate is achieved. The steady-state rate is achieved when the concentration of carbon dioxide increases at a constant rate. This rate is used to calculate the permeabiUty. Figure 18 shows how the diffusion coefficient can be deterrnined in this type of experiment. The time lag is substituted into equation 21. The solubiUty coefficient can be calculated with equation 2. 

Various types of detector tubes have been devised. The NIOSH standard number S-311 employs a tube filled with 420—840 p.m (20/40 mesh) activated charcoal. A known volume of air is passed through the tube by either a handheld or vacuum pump. Carbon disulfide is used as the desorbing solvent and the solution is then analyzed by gc using a flame-ionization detector (88). Other adsorbents such as siUca gel and desorbents such as acetone have been employed. Passive (diffuse samplers) have also been developed. Passive samplers are useful for determining the time-weighted average (TWA) concentration of benzene vapor (89). Passive dosimeters allow permeation or diffusion-controlled mass transport across a membrane or adsorbent bed, ie, activated charcoal. The activated charcoal is removed, extracted with solvent, and analyzed by gc. Passive dosimeters with instant readout capabiUty have also been devised (85). 

Its main features are given by the use of a stream of inert carrier gas which percolates through a bed of an adsorbent covered with adsorbate and heated in a defined way. The desorbed gas is carried off to a detector under conditions of no appreciable back-diffusion. This means that the actual concentration of the desorbed species in the bed is reproduced in the detector after a time lag which depends on the flow velocity and the distance. The theory of this method has been developed for a linear heating schedule, first-order desorption kinetics, no adsorbable component in the entering carrier gas (Pa = 0), and the Langmuir concept, and has already been reviewed (48, 49) so that it will not be dealt with here. An analysis of how closely the actual experimental conditions meet the idealized model is not available. 

As previously stated, GPC is the method of choice for studying polymer degradation kinetics. The GPC trace, as given by the detector output, does not provide the true MWD due to various diffusion broadening processes inside the different parts of the equipment. The first step is to correct for instrument broadening if a precise evaluation of MWD is desired. Even with the best columns available, this correction may change the MWD significantly as can be visualized... 

Well-defined hydrodynamic conditions, with high rate of mass transport, are essential for successful use of electrochemical detectors. Based on the Nemst approximate approach, the thickness of the diffusion layer (<5) is empirically related to the solution flow rate (U) via... 

FIG. 33 X-Ray Diffraction Patterns of Ammonium Dodecane 1-Sulfonate. 2-D (a) and 3-D plots (b) of oriented samples. Both pictures show the presence of a nonordered smectic phase, since the diffuse, weak, wide-angle diffraction indicates only an average distance between the molecules and the sharp, intense small angle reflections a very well defined layer distance. The reflections are perpendicular to each other, so the structure should correspond to an orthogonal smectic A type. The pictures were obtained using an x-1000 area detector from Siemens. 

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