Spectrometer linearity

A fluorescence spectrum shall be measured with a spectral resolution of 10 nm. The experimenter decides to use a crossed arrangement of grating spectrometer (linear dispersion 5 x 10 nm/mm) and an FPI with coatings of / = 0.98 and A = 0.3%. Estimate the optimum combination of spectrometer slit width and FPI plate separation. 

ISO 21270 2004 Surface chemical analysis - X-ray photoelectron and Auger electron spectrometers - Linearity of intensity scale... 

TPD is frequently used to detenuine (relative) surface coverages. The area below a TPD spectrum of a certain species is proportional to the total amount that desorbs. In this way one can detennine uptake curves that correlate gas exposure to surface coverage. If tire pumping rate of the UHV system is sufiBciently high, the mass spectrometer signal for a particular desorption product is linearly proportional to the desorption rate of the adsorbate [20, 21] ... 

Other instrumental advantages include its high sensitivity and a linear mass scale to m/z 10,000 at full sensitivity. The linearity of the mass scale means that it is necessary to calibrate the spectrometer using a single or sometimes two known mass standards. Some calibration is necessary because the start of the mass scale is subject to some instrumental zero offset. The digitized accumulation of spectra provides a better signal-to-noise ratio than can be obtained from one spectrum alone. 

The hnearity between M and makes the concept of absorbance so usehil that measurements made by sampling methods other than transmission are usually converted to a scale proportional to absorbance. The linearity between M and i is maintained only if the resolution of the spectrometer is adequate to eliminate contributions from wavelengths not absorbed by the species being measured. In addition, the apparent value of a is very dependent on resolution because a is 2l strong function of wavelength (30,31). 

An important parameter when considering GC resolution of the sample components is the carrier gas linear velocity (flow rate, F), which can be determined by injecting 5-50 /A of argon or butane and measuring the time from injection to detection by the mass spectrometer. An optimum linear velocity using helium as a carrier gas is approximately 30 cm/sec and... 

Striking support of this contention is found in recent data of Castro (16) shown in Figure 14. In this experiment, the polymerization (60-156) has been carried out in a cone-and-plate viscometer (Rheometrics Mechanical Spectrometer) and viscosity of the reaction medium monitored continuously as a function of reaction time. As can be seen, the viscosity appears to become infinite at a reaction time corresponding to about 60% conversion. This suggests network formation, but the chemistry precludes non-linear polymerization. Also observed in the same conversion range is very striking transition of the reaction medium from clear to opaque. 

There are two notable features of the quantitative performance of this type of interface. It has been found that non-linear responses are often obtained at low analyte concentrations. This has been attributed to the formation of smaller particles than at higher concentrations and their more easy removal by the jet separator. Signal enhancement has been observed due to the presence of (a) coeluting compounds (including any isotopically labelled internal standard that may be used), and (b) mobile-phase additives such as ammonium acetate. It has been suggested that ion-molecule aggregates are formed and these cause larger particles to be produced in the desolvation chamber. Such particles are transferred to the mass spectrometer more efficiently. It was found, however, that the particle size distribution after addition of ammonium acetate, when enhancement was observed, was little different to that in the absence of ammonium acetate when no enhancement was observed. 

The HPLC system used consisted of a 30 x 2 mm Luna CN column with linear gradient elution employing two mobile phases A and B (A, 90% H2O 10% acetonitrile B, 10% H2O 90% acetonittile) with both phases containing 5 mM ammonium acetate and 0.2% formic acid. The hnear gradient commenced with 50 50 A B increasing to 100% B after 1 min of the analysis this composition was maintained for 1 min before returning to 50 50 A B after 4 min. Positive-ion ionspray (pneumatically assisted electrospray) was used to obtain mass spectra, with the spectrometer operating at a resolution of 5000. 

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