Velocity spectrometry

CSIRO Minerals has developed a particle size analyzer (UltraPS) based on ultrasonic attenuation and velocity spectrometry for particle size determination [269]. A gamma-ray transmission gauge corrects for variations in the density of the slurry. UltraPS is applicable to the measurement of particles in the size range 0.1 to 1000 pm in highly concentrated slurries without dilution. The method involves making measurements of the transit time (and hence velocity) and amplitude (attenuation) of pulsed multiple frequency ultrasonic waves that have passed through a concentrated slurry. From the measured ultrasonic velocity and attenuation particle size can be inferred either by using mathematical inversion techniques to provide a full size distribution or by correlation of the data with particle size cut points determined by laboratory analyses to provide a calibration equation. 

For stand-alone or hybrid TOF mass spectrometry, the ions examined must all start from some point at the same instant. From this zero time, the ions are accelerated through a short region by applying a short pulse of electric potential of several kilovolts. The acceleration gives the ions velocities that vary in proportion to the square root of their m/z values. 

There is no theoretical upper limit on m/z that can be examined, and TOF mass spectrometry is useful for substances having very high molecular mass. In practice, the current upper limit is about 350,000. Unfortunately, ions even of the same m/z value do have a spread of velocities after acceleration, so the resolution achievable with TOF is not very high because bunches of ions of one m/z value overlap those at the next m/z value. 

In TOP mass spectrometry, ions of different m/z values are detected as a function of their velocities along a flight tube (see Chapters 20 through 23). 

The catalytic experiments were performed at the stationnary state and at atmospheric pressure, in a gas flow microreactor. The gas composition (NO, CO, O2, C3H, CO2 and H2O diluted with He) is representative of the composition of exhaust gases. The analysis, performed by gas chromatography (TCD detector for CO2, N2O, O2, N2, CO and flame ionisation detector for C3H6) and by on line IR spectrometry (NO and NO2) has been previously described (1). A small amount of the sample (10 mg diluted with 40 mg of inactive a AI2O3 ) was used in order to prevent mass and heat transfer limitations, at least at low conversion. The hourly space velocity varied between 120 000 and 220 000 h T The reaction was studied at increasing and decreasing temperatures (2 K/min) between 423 and 773 K. The redox character of the feedstream is defined by the number "s" equal to 2[02]+[N0] / [C0]+9[C3H6]. ... 

In (3.3) the mass and velocity of the ions are m and v. Mass spectrometry data are usually plotted with ion abundance on the vertical axis and the mass-to-charge (m/z) ratio on the horizontal one. Solving for the mass-to-charge value (m/z), we obtain... 

Colby, S. M. King, T. B. Reilly, J. P. Improving the resolution of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry by exploiting the correlation between ion position and velocity. Rapid Comm. Mass Spectrom. 1994,8, 865-868. 

In electric-field driven separations an electric field causes ions to travel through a matrix, such as a gas, liquid, or gel. The movement is retarded by frictional forces from interaction with the matrix and the ions almost instantly reach a steady-state velocity. This velocity depends on properties of both the sample molecules and the surrounding matrix. The two main types of electric-field driven separations are ion mobility spectrometry where the matrix is a gas and electrophoresis where the matrix is a liquid or gel. 

In order to perform qualitative and quantitative analysis of the column effluent, a detector is required. Since the column effluent is often very low mass (ng) and is moving at high velocity (50-100 cm/s for capillary columns), the detector must be highly sensitive and have a fast response time. In the development of GC, these requirements meant that detectors were custom-built they are not generally used in other analytical instruments, except for spectroscopic detectors such as mass and infrared spectrometry. The most common detectors are flame ionization, which is sensitive to carbon-containing compounds and thermal conductivity which is universal. Among spectroscopic detectors, mass spectrometry is by far the most common. 

Ion mobility spectrometry (IMS) [3,12] is the most widely used instrument for drug detection. The sample is heated to vaporize the analyte, which is then ionized by atmospheric (ambient) pressure chemical ionization (APCI) [3]. The resulting gas-phase ions travel through a drift tube and are separated by their distinct velocities (mobilities) in a weak electrostatic field. IMS instruments use ambient air or nitrogen as the carrier gas, making it particularly adaptable to field applications. 

Time of Flight The principle of time-of-flight mass spectrometry (TOFMS) is very simple and makes use of the energy equation E = mv2/2 where m is mass and v is velocity. As illustrated in Figure 11.1, all ions are accelerated to constant energy E. The ions then enter a drift tube where they travel at velocity v. Because each ion mass m travels at a different velocity, the ions of different mass separate the lighter ones run ahead of the heavier ones. This separation means that each ion mass hits the detector at a different time. Ions of the same... 

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