Droplets desolvation

The flow rate accepted by the interface ranges between 100 and lOOOnL/min for most applications. The interfacing mechanism is based on the formation of the aerosol in high-vacuum conditions, followed by a quick droplet desolvation and the hnal vaporization of the solute on a target surface prior to ionization. The process is fast and requires less than 8 mm of path length. At the core of the interface there are a nano-nebulizer and a treated surface. The nebulizer tip... 

In ESI, the column effluent is passed through a small jet maintained at high voltage (kV range). Due to electronic charging, the liquid is broken into very small droplets. Desolvation of the droplets increases the electric field strength at the surface and leads to the ejection of charged compounds by ion evaporation (Fig. 2). 

Letter D in Figure 8.9 refers to the droplet desolvation process. Besides the competitive ionization process inherent to ESI and the effect of different solvent compositions on ionization efficiency, it is also feasible to conjecture that the shrinking droplet may impart a concentration gradient which could cause a shift in the equihbria of interest. However, prior hypotheses and recent evidence suggest that if the host-guest association is kinetically stable on the time scale of the ESI process (psec - msec), then a reliable snapshot of the solution phase equilibrium may be obtained [10,42]. Additional studies in this area may shed more light on the system dependence of this potentially deleterious effect. 

Droplet (Desolvation) Solid (Vaporization) Gas (Atomization) Atom (Ionization) Ion... 

Horner J. A., Lehn S. A. and Hieetje G. M. (2002) Computer simulation of aerosol-droplet desolvation in an inductively coupled plasma, Spectrochim. Acta, Part B 57 1025— 1042. 

The nebulization concept has been known for many years and is commonly used in hair and paint spays and similar devices. Greater control is needed to introduce a sample to an ICP instrument. For example, if the highest sensitivities of detection are to be maintained, most of the sample solution should enter the flame and not be lost beforehand. The range of droplet sizes should be as small as possible, preferably on the order of a few micrometers in diameter. Large droplets contain a lot of solvent that, if evaporated inside the plasma itself, leads to instability in the flame, with concomitant variations in instrument sensitivity. Sometimes the flame can even be snuffed out by the amount of solvent present because of interference with the basic mechanism of flame propagation. For these reasons, nebulizers for use in ICP mass spectrometry usually combine a means of desolvating the initial spray of droplets so that they shrink to a smaller, more uniform size or sometimes even into small particles of solid matter (particulates). 

These factors make it necessary to reduce the amount of solvent vapor entering the flame to as low a level as possible and to make any droplets or particulates entering the flame as small and of as uniform a droplet size as possible. Desolvation chambers are designed to optimize these factors so as to maintain a near-constant efficiency of ionization and to flatten out fluctuations in droplet size from the nebulizer. Droplets of less than 10 pm in diameter are preferred. For flow rates of less than about 10 pl/min issuing from micro- or nanobore liquid chromatography columns, a desolvation chamber is unlikely to be needed. 

The simplest desolvation chambers consist simply of a tube heated to about 150°C through which the spray of droplets passes. During passage through this heated region, solvent evaporates rapidly from the droplets and forms vapor. The mixed vapor and residual small droplets or particulates of sample matter are swept by argon through a second cooled tube, which allows vapor to... 

A second form of desolvation chamber relies on diffusion of small vapor molecules through pores in a Teflon membrane in preference to the much larger droplets (molecular agglomerations), which are held back. These devices have proved popular with thermospray and ultrasonic nebulizers, both of which produce large quantities of solvent and droplets in a short space of time. Bundles of heated hollow polyimide or Naflon fibers have been introduced as short, high-surface-area membranes for efficient desolvation. 

Solutions can be examined by ICP/MS by (a) removing the solvent (direct and electrothermal methods) and then vaporizing residual sample solute or (b) nebulizing the sample solution into a spray of droplets that is swept into the plasma flame after passing through a desolvation chamber, where excess solvent is removed. The direct and electrothermal methods are not as convenient as the nebulization inlets for multiple samples, but the former are generally much more efficient in transferring samples into the flame for analysis. 

An aerosol produced instrumentally has similar properties, except that the aerosol is usually produced from solutions and not from pure liquids. For solutions of analytes, the droplets consist of solute and solvent, from which the latter can evaporate to give smaller droplets of increasingly concentrated solution (Figure 19.1). If the solvent evaporates entirely from a droplet, the desolvated dry solute appears as small solid particles, often simply called particulate matter. 

The calculation shows how rapidly a droplet changes in diameter with time as it flows toward the plasma flame. At 40°C, a droplet loses 90% of its size within alxtut 1.5 sec, in which time the sweep gas has flowed only about 8 cm along the tube leading to the plasma flame. Typical desolvation chambers operate at 150°C and, at these temperatures, similar changes in diameter will be complete within a few milliseconds. The droplets of sample solution lose almost all of their solvent (dry out) to give only residual sample (solute) particulate matter before reaching the plasma flame. 

In a concentric-tube nebulizer, the sample solution is drawn through the inner capillary by the vacuum created when the argon gas stream flows over the end (nozzle) at high linear velocity. As the solution is drawn out, the edges of the liquid forming a film over the end of the inner capillary are blown away as a spray of droplets and solvent vapor. This aerosol may pass through spray and desolvation chambers before reaching the plasma flame. 

The thermospray device produces a wide dispersion of droplet sizes and transfers much of sample solution in unit time to the plasma flame. Therefore, it is essential to remove as great a proportion of the bigger droplets and solvent as possible to avoid compromising the flame performance. Consequently, the thermospray device usually requires both spray and desolvation chambers, especially for analyte solutions in organic solvents. 

Having removed the larger droplets, it may remain only to encourage natural evaporation of solvent from the remaining small droplets by use of a desolvation chamber. In this chamber, the droplets are heated to temperatures up to about 150 C, often through use of infrared heaters. The extra heat causes rapid desolvation of the droplets, which frequently dry out completely to leave the analyte as small particles that are swept by the argon flow into the flame. 

The large quantities of solvent vapor produced from the evaporating droplets must be removed before reaching the plasma flame, which is done by having cooling tubes sited after the heated desolvation chamber to condense the vapor into liquid. This condensed liquid is run to waste. 

After desolvation, the remaining fine particulate matter and residual droplets are swept by the argon carrier into the plasma flame, where fragmentation and ionization occur. 

To assist in the deposition of these larger droplets, nebulizer inlet systems frequently incorporate a spray chamber sited immediately after the nebulizer and before the desolvation chamber. Any liquid deposited in the spray chamber is wasted analyte solution, which can be run off to waste or recycled. A nebulizer inlet may consist of (a) only a nebulizer, (b) a nebulizer and a spray chamber, or (c) a nebulizer, a spray chamber, and a desolvation chamber. Whichever arrangement is used, the object is to transfer analyte to the plasma flame in as fine a particulate consistency as possible, with as high an efficiency as possible. 

The second step is to disperse the core material being encapsulated in the solution of shell material. The core material usually is a hydrophobic or water-knmiscible oil, although soHd powders have been encapsulated. A suitable emulsifier is used to aid formation of the dispersion or emulsion. In the case of oil core materials, the oil phase is typically reduced to a drop size of 1—3 p.m. Once a suitable dispersion or emulsion has been prepared, it is sprayed into a heated chamber. The small droplets produced have a high surface area and are rapidly converted by desolvation in the chamber to a fine powder. Residence time in the spray-drying chamber is 30 s or less. Inlet and outlet air temperatures are important process parameters as is relative humidity of the inlet air stream. 

---