Temp, pressure and flow rate changes or irregular column bleed. Determines Types the limits of detector sensitivity and LOD. Solution: use detector time- General detector constant and data system sampling - Respond to bulk properties (e.g. rates, regularly flush the column with Refractive index) strong solvent, minimize temp fluctuations Specific detector Drift – baseline perturbation. Smaller - Respond to some properties of the than eluted peak. Source: (GC) change solute by the mobile phase (e.g. UV in temp, mobile phase flow rate and absorption) column bleed, (HPLC) change in Pressure temp and flow rate or vatriation of solvent ratios. Causes is Desired characteristics impurity in the mobile phases and incomplete colum equil. - Universal response Background noise – constant signal Responds to any component that above zero baseline. Sensitivity affected passes to the column by this. reduces sensitivity. Source – (GC) injection port compone3nts and - Linear dynamic range GC septa (low bleed septa) Linear response for calib cruve High stability – low background noise - Ease of operation High sensitivity – low background noise, - Reliablity fast response Could be used in a longer period of time without baseline drift - Fast response - Good Stability Results into a sharper peak Less electronic noise and less baseline drift
Arranged according the size: Limit of detection
Short term noise – base line Height of signal = (2)(largest noise
perturbations. Frequiency significantly signal) higher than the eluted peak. Solution: Noise filters. Source: electronic How to improve - Increasing peak sharpness Measure of the speed of response of a - Higher sample detector. More specifically time a - GC – optimum flow rate and high detector takes to resppnd to a sudden temp chang in a signal - HPLC signal - optimizing mobile phase ration and longer path T(constant)=V (peak volume)/flow rate lengths Increasing the time constant distorts the peak shapes. It shifts to a wider peak width as u increase the time Unit of LOD constant from the optimum
GC – g/sec or g/ml
HPLC – mM or mg/ml Linearity
Sensitivity Linearity = upper limit of linear
range/minimum detectability When linearity falls of is called the upper limit of dynamic range Linear range vs Dynamic range
Lowest point of concentration is called Linear Dynamic
the at a curve is called the minimum Part that is Lower limit of the detection linear range is the minimum detectability Upper limit is the Increases signal Decreases noise highest conc that will Detector Incease detector give a change in adjustment time constant detector signal, but Sensitive detector More data may not be linear system averaging Dynamic range Analyte Temp control usually has a bigger derivatization scope than linear Smaller k Higher reagent solvent purity Detector Classification Smaller column Better sample 1) Concentration versus Mass flow rate volume clean up Large plate number Constant flow A) concentration types Column switching Produces signal prop to concentration
B) Mass flow rate type
Time constant Produces signal prop to mass flow irrespective of the carrier gas volume 2) Bulk vs. Specific property
A) Bulk property
Measures a prop exhibited by both
mobile phase and the analyte. Adv. Could detect all solutes that could screen new samples of unknown competition. Disadv. Insensitive inherently
B) Specific property
Only exhibits signal when sample
present (aka analyte or solute proterty)
3) destructive vs. non destructive
Most HPLC detector are non destructive
4) digital vs analog
Analog – signal generated is digitalized
before they can be manipulated by digital computer