Concentration peak shapes

The scan rate, u = EIAt, plays a very important role in sweep voltannnetry as it defines the time scale of the experiment and is typically in the range 5 mV s to 100 V s for nonnal macroelectrodes, although sweep rates of 10 V s are possible with microelectrodes (see later). The short time scales in which the experiments are carried out are the cause for the prevalence of non-steady-state diflfiision and the peak-shaped response. Wlien the scan rate is slow enough to maintain steady-state diflfiision, the concentration profiles with time are linear within the Nemst diflfiision layer which is fixed by natural convection, and the current-potential response reaches a plateau steady-state current. On reducing the time scale, the diflfiision layer caimot relax to its equilibrium state, the diffusion layer is thiimer and hence the currents in the non-steady-state will be higher. 

The current during the stripping step is monitored as a function of potential, giving rise to peak-shaped voltammograms similar to that shown in Figure 11.37. The peak current is proportional to the analyte s concentration in the solution. 

For some nonionic, nonpolar polymers, such as polyethylene glycols, normal chromatograms can be obtained by using distilled water. Some more polar nonionic polymers exhibit abnormal peak shapes or minor peaks near the void volume when eluted with distilled water due to ionic interactions between the sample and the charged groups on the resin surface. To eliminate ionic interactions, a neutral salt, such as sodium nitrate or sodium sulfate, is added to the aqueous eluent. Generally, a salt concentration of 0.1-0.5 M is sufficient to overcome undesired ionic interactions. 

Cationic samples can be adsorbed on the resin by electrostatic interaction. If the polymer is strongly cationic, a fairly high salt concentration is required to prevent ionic interactions. Figure 4.18 demonstrates the effect of increasing sodium nitrate concentration on peak shapes for a cationic polymer, DEAE-dextran. A mobile phase of 0.5 M acetic acid with 0.3 M Na2S04 can also be used. 

In general, retention decreases as the modifier concentration increases because the modifier competes with the analytes for sites on the stationary phase. The effect on retention of changes in modifier concentration seems to be more pronounced for CSPs than for achiral stationary phases in SFC, and peak shapes are apt to degrade rapidly at low modifier concentrations [12]. Efficiency tends to decrease as the modifier concentration increases because analyte diffusion is slowed by the increased viscosity of the eluent [39]. 

The basic shape of LSV and CV, a peak-shaped voltammogram can be explained as follows. For a reduction reaction, 0+ne = R, when the voltage is made more negative the surface concentration of O starts to decrease and thus increases the concentration gradient and the reduction current starts to rise. Eventually, at more negative voltage the surface concentration reaches zero and diffusion cannot deliver O to the surface at the same rate. This results in decreasing current and a... 

This means that with increasing scan rate or lowering the solution concentration, the effect of lc will increase. Because a peak-shaped CV can only be obtained at a sufficiently high scan rate, the effect of electrode capacitance charging limits the CV application in low-concentration solutions. SWV has been developed to overcome this problem and to increase the quantitative accuracy of voltammetric techniques. The concentration for recording a SW voltammogram can be as low as a hundredth of that for recording a CV. 

The use of TFA as a mobile-phase additive in LC-MS can be problematical when using electrospray ionization. In negative ion detection, the high concentration of TFA anion can suppress analyte ionization. In positive ion detection, TFA forms such strong ion pairs with peptides that ejection of peptide pseudo-molecular ions into the gas phase is suppressed. This problem can be alleviated by postcolumn addition of a weaker, less volatile acid such as propionic acid.14 This TFA fix allows TFA to be used with electrospray sources interfaced with quadrupole MS systems. A more convenient solution to the TFA problem in LC-MS is to simply replace TFA with acetic or formic acid. Several reversed-phase columns are commercially available that have sufficient phase coverage and reduced levels of active silanols such that they provide satisfactory peptide peak shapes using the weaker organic acid additives.15... 

In packed column SFC, polar solutes such as amines and carboxylic acids often have too much retention or elute with poor peak shapes when neat carbon dioxide is used as a mobile phase [28, 92]. This is mainly due to the weak solvent strength of neat carbon dioxide compared to a liquid solvent. The use of modifiers is often necessary to enhance the solvating power of the mobile phase in SFC. Various alcohols such as methanol and isopropanol are commonly used modifiers in SFC, but other solvents such as acetonitrile was also utilized [92]. The concentrations of modifiers are usually less than 50%. The technique in which the concentrations of modifiers are greater than 50% is often called enhanced-fluidity liquid chromatography [93]. 

Figure 4.10 shows the effect of additive concentration on the separation of clen-buterol enantiomers on a polysaccharide-based chiral stationary phase [79]. The peak shapes were dramatically improved by adding an amine additive and the separation time was also reduced from 14 to 7 min when 1.0% amine was added to the mobile phase. Phinney and Sander [100] investigated the effect of amine additives using chiral stationary phases having either a macrocyclic glycopeptide or a... 

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