Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
It
Monochromator Detector Amplifier
Atomiser
Atomization
Desolvation and vaporization of ions or atoms in a sample: high-temperature source such as flame or graphite furnace
Flame atomic absorption spectroscopy Graphite furnace atomic absorption spectroscopy
Solution MX
nebulisation
Salt mist of MX
Processes In Flame salt vapourised Molecules of MX Dissociation
M
M*
excited
*ATOMISED *
MX compound formed
M+
ionised
Source of radiation
Hollow cathode lamps or electrode less discharge lamps
Monochromator
Isolation of the absorption line from background light and from molecular emissions originating in the flame (tuned to a specific wavelength)
Detection
Calibration curve
Standards containing known concentrations of the analyte are introduced into the instrument Response is recorded Response is corrected for instrument output obtained with a blank
Blank contains all of the components of the original sample except for the analyte
Resulting data are then plotted to give a graph of corrected instrument response vs. analyte concentration An equation is developed for the calibration curve by a leastsquares technique so that sample concentrations can be computed directly
Detector
A photomultiplier measures the intensity of the incident light and generate an electrical signal proportional to the intensity
Interference
Lowers the signal
Chemical interference: formation of stable or refractory compounds (not atomized at certain T)
Use higher temperature Releasing agents, EDTA Chelating agents, LaCl3
Ionization interference
Alkali metals easily ionized (low ionization energy) Energy level of ion lower than parent Suppressed by adding elements that are easily analyzed, CsCl when using Na or K
Disadvantages:
only solutions can be analysed relatively large sample quantities required (1 2 mL) problems with refractory elements
Advantages:
inexpensive (equipment, day-to-day running) high sample throughput easy to use high precision
How it works?
A plasma source is used to dissociate the sample into its constituent atoms or ions, exciting them to a higher energy level. They return to their ground state by emitting photons of a characteristic wavelength depending on the element present. This light is recorded by an optical spectrometer.
Monochromator Detector
Interferences
two or more elements in the matrix emitting radiation at the same wavelength (e.g., Cu at 515.323 nm and Ar at 515.139 nm). These spectral interferences can be minimized by using a high resolution system by using several analytical lines for the detection of a single element interference involving the formation of undesired species (e.g., ions). It is important to note that an atom of a specific element (e.g., Fe) has a different emission spectra than one of its ions (e.g., Fe+, Fe+2, etc.)
How it works?
the gaseous atoms obtained by flame or electrothermal atomisation are excited to higher energy levels by absorption of the electromagnetic radiation and the fluorescence emission from these excited atoms is measured. This technique incorporates aspects of both absorption and emission. Measure the fluorescence emission resulting from the relaxation of the excited atoms. However, measurement is made 90o from source
Radiation source:
Continuous source: tungsten halide or deuterium lamp multi element detection, however low intensity due to stray radiations Line source: HCL high radiation however cannot do multi element Laser high radiant source
Atomization: Hydrogen diffusion Flame excellent detection limits (low b/ground), however suffers from matrix effect (only pure solutions can be used) Monochromator Detector: 90o to the radiation source
The intensity of the fluorescence radiation is measured at right angles to the direction of incident radiation and is correlated to the concentration of the element present, forming the basis of quantitative analysis. In quantitative atomic fluorescence spectrometric determinations the instrument is generally standardized by a calibration curve
Sample Preparation
The sample must be in the diluted form and filtered for particulates Type of sample: blood, urine, tissues, cerebral spinal fluid and other biological fluids by direct aspiration of the sample, usually dilution with water is required to prevent clogging of the burner In the preparation of standards, the matrix of the analyte must always be matched, Eg. Analysing Zn in waste water, standard solution is made up from ZnCl2
Case study: determination of heavy metals (Pb, Cr, As and K) in Selom plant
Raw Materials : Selom plant Chemicals: nitric acid and hydrochloric acid with ratio of 3:1 and distilled water Procedure: dry the fresh Selom in the oven before ashing process to avoid unnecessary explosion Burn the dry selom in the furnace at 500C for one hour About 5 g of Selom ash is required before acid digestion process The solution is then filtered and diluted to the required concentration for AAS and/or ICP-OES analysis Prepared the standard solution for each metal and obtained their calibration curve From the regresion equation the concentration of each element can be calculated
Ashing method
placingthe sample in an open inert vessel and destroying the combustible (organic) portion of the sample by thermal decomposition using a muffle furnace. Typical ashing temperatures are 450 to 550 C. Magnesium nitrate is commonly used as an ashing aid. Charring the sample prior to muffling is preferred. Charring is accomplished using an open flame.
Detection Limit (ppm): The conc required to give a signal equal to three times the standard deviation of base line (Blank) < 300 nm: AAS shows superior detectability because high thermal energy required to excite the atom for emission at these wavelength 300 < < 400 nm: either method exhibit comparable detectability
Differentiate
AAS-Flame Principle working method How it works Instrumentation advantages AES-ICP AFS