Retention time change

The column is not capable of separating any quantity of substances. If too much material is injected, then the retention factor and the peak width cease to be independent of sample size (see Figure 2.23). The peaks become wider and asymmetric and the retention time changes at the same time. Tailing is accompanied by decreased retention and fronting by an increase in k. 

In the search for the cause of retention time changes, we can make several distinctions ... 

Manual preparation of dilute hydroxide eluents caused retention time changes due to the inherent solubility of carbon dioxide in basic solutions. 

The acceleration of elution translates into a decrease of the compound retention times compared to those obtained in FID, for instance. Obviously, the shorter the column is, the more the phenomenon is pronounced. It is not problematic because the elution order of the compounds is conserved. One must nevertheless keep in mind that, when comparing two chromatograms (one in GC, the other in GC-MS), the analyte retention times change even though the chromatographic conditions are identical. 

Effect of a change in kg on resolution and retention time. The original value of kg is assumed to be 1. 

Any improvement in resolution obtained by increasing ki generally comes at the expense of a longer analysis time. This is also indicated in Figure 12.11, which shows the relative change in retention time as a function of the new capacity factor. Note that a minimum in the retention time curve occurs when b is equal to 2, and that retention time increases in either direction. Increasing b from 2 to 10, for example, approximately doubles solute B s retention time. 

Use of column selectivity to improve chromatographic resolution showing (a) the variation in retention time with mobile phase pH, and (b) the resulting change in alpha with mobile phase pH. 

The concentrations of benzoic acid, aspartame, caffeine, and saccharin in a variety of beverages are determined in this experiment. A Gig column and a mobile phase of 80% v/v acetic acid (pH = 4.2) and 20% v/v methanol are used to effect the separation. A UV detector set to 254 nm is used to measure the eluent s absorbance. The ability to adjust retention times by changing the mobile phase s pH is also explored. 

Two gas chromatograms showing the effect of polarity of the stationary phase on the separation efficiency for three substances of increasing polarity toluene, pyridine, and benzaldehyde. (a) Separation on silicone SE-30, a nonpolar phase, and (b) separation on elastomer OV-351, a more polar phase. Note the greatly changed absolute and relative retention times the more polar pyridine and benzaldehyde are affected most by the move to a more polar stationary phase. 

Chlorination can be carried out at 25°C or below. However, the reaction is exothermic and, as mills have used filtrate recycle, operating temperatures have unavoidably risen. Retention times are 30—60 minutes but decrease as temperature increases. In most mills the retention time cannot be changed because the tower is upflow in design. The normal pulp consistency is 3—4%, but the trend is toward higher (ca 10%) consistency or gas-phase chlorination. Target pH in the chlorination stage (also (7 ) is about 1.8. 

Retention and stereoselectivity on the BSA columns can be changed by the use of additives to the aqueous mobile phase (30). Hydrophobic compounds generally are highly retained on the BSA, and a mobile-phase modifier such as 1-propanol can be added to obtain reasonable retention times. The retention and optical resolution of charged solutes such as carboxyUc acids or amines can be controlled by pH and ionic strength of the mobile phase. 

It is seen that the viscosity of the gas will change significantly during a temperature program and, thus, at a constant gas mass flow rate, the inlet pressure will rise proportionally. This increase in inlet pressure will result in an increase in the inlet/outlet pressure ratio and, as a consequence, will extend the retention time and oppose the effect of any increase in temperature. It also follows that the effect of... 

To demonstrate the effect in more detail a series of experiments was carried out similar to that of volume overload, but in this case, the sample mass was increased in small increments. The retention distance of the front and the back of each peak was measured at the nominal points of inflection (0.6065 of the peak height) and the curves relating the retention data produced to the mass of sample added are shown in Figure 7. In Figure 7 the change in retention time with sample load is more obvious the maximum effect was to reduce the retention time of anthracene and the minimum effect was to the overloaded solute itself, benzene. Despite the reduction in retention time, the band width of anthracene is still little effected by the overloaded benzene. There is, however, a significant increase in the width of the naphthalene peak which... 

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