Chapter 4 Atomic Spectroscopy

Optical spectroscopic methods

In Optical spectrometry, elements in the sample are converted to gaseous atoms or elementary ions by a process called atomization. The absorption, emission, or fluorescence of the atomic species in the vapor is then measured. Determination of analytical sample concentration Linear relationship between absorbance and concentration

Optical spectroscopic methods

Atomic Absorption Spectroscopy Atomic Emission Spectroscopy Atomic Fluorescence Spectroscopy

Atomic Absorption Spectroscopy

I0
Light Source

It
Monochromator Detector Amplifier

E.g. Hollow cathode lamp

Atomiser

Fuel (e.g. acetylene) Air

Nebuliser, spray chamber, and burner Analyte solution

How does it work?

The solution is aspirated into the flame as a fine spray The solvent evaporates, leaving the dehydrated salt The salt is dissociated into free gaseous atoms in the ground state A certain fraction of these atoms absorbed energy from the flame (some of them are collided each other) and be raised to the excited electronic state The excited state have a short lifetime and returned to the ground hc E state by emitting photon with characteristic wavelength, The intensity of emission/absorption is directly proportional to the conc. of analyte in the solution, therefore a calibration curve of emission/absorption intensity vs conc. is prepared However, side reactions in the flame may decrease the population of free atom and hence reduced the emission/absorption signal

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

Flame atomic absorption spectroscopy

A flame provides a high-temperature source for desolvating and vaporizing a sample to obtain free atoms for spectroscopic analysis. In atomic absorption spectroscopy ground state atoms are desired. For atomic emission spectroscopy the flame must also excite the atoms to higher energy levels. The table lists temperatures that can be achieved in some commonly used flames.
Temperatures of some common flames

Fuel H2 C2H2 H2 C2H2

Oxidant Air Air O2 N2O

Temperature (K) 2000-2100 2100-2400 2600-2700 2600-2800

Solution MX
nebulisation

Liquid aerosol droplets

solvent evaporation

Salt mist of MX
Processes In Flame salt vapourised Molecules of MX Dissociation

M
M*
excited

Thermal and chemical

*ATOMISED *
MX compound formed

M+
ionised

Effect of temperature-boltzmann distribution

Source of radiation
Hollow cathode lamps or electrode less discharge lamps

Hollow cathode lamp

Sources: hollow-cathode lamp (HCL), used in atomic absorbtion Tube filled with inert gas (Ne or Ar) Hollow cathode (negative) made with metal we want to detect Run a high voltage between anode and cathode This makes Ne or Ar ionize Ne+ or Ar+ attracted to hollow metal cathode As these ions hit the metal, atoms of metal are ejected into the gas As metal atom interact with energetic electrons atoms are excited, so generate light at that metals wavelength since excitation is not by flame the linewidth is extra sharp

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

Atomic Absorption Spectroscopy

Widely used method for determination of single elements in analytical samples. Applications:
Water analysis Food analysis Analysis of additives in lubricating oils and greass Analysis of soil Clinical analysis

Atomic Emission Spectroscopy

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.

 Plasma: atomization and excitation source

A plasma is an electrically neutral, highly ionized gas that consists of ions, electrons, and atoms A high-frequency current of 27.120MHz is sent through a high-frequency coil, generating a magnetic field. Plasma is then formed from the gas (argon) flowing through the coil. In the plasma, there are the same number of Ar+ and electrons, maintaining an electrical balance. Temperature reaching 10000K Advantages over flame:
Lower inter-element interference (higher temperature With a single set of conditions signals for dozens of elements can be recorded simultaneously

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.)

Atomic Fluorescence Spectroscopy

Determination of single elements in analytical sample Determination of analytical sample concentration Monitor the fluorescence emission from the excited state Atomic fluorescence spectra:
Resonance fluorescence Radiationless transition + transition to ground state Transition to lower state + radiationless transition

Atomic Fluorescence Spectroscopy

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

Advantages and application

The main advantage of fluorescence detection compared to absorption measurements is the greater sensitivity achievable because the fluorescence signal has a much lower background as compared to the one observed in atomic absorption method Except for some favorable metals and metalloids (like Pb, Cd, Tl, Se, Te, As, Sb, etc.) there is no special advantage over more established AAS. Thus, not widespread use due to overwhelming success of AAS Applications: analysis of metals in lubricating oil, seawater, biological substance, agriculture samples

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.

Acid digestion/pressure digestion/microwave digestion

Acid digestion process are employed for the determination of elements in solid subsequent to sampling and mechanical sample preparation in order to completely transfer the analytes into solution so that it can be introduced to analysis instrument- ICPOES, AAS and ICP-MS Common acid used, mineral acids (HCl, HNO3, HF, H2SO4 etc)

Representatives Detectin Limit by AAS and Flame Emission Spectroscopy, FES/ICP

Element Ag Al Au Ca Cu Eu Hg K Mg Na Tl Zn Wavelength (nm) 328.1 309.3 396.2 242.8 267.7 422.7 324.8 459.4 253.6 766.5 285.2 589 276.8 535 213.9 Detection Limit (ppm) AAS FES (ICP) 0.001(A) 0.01 0.1 (N) 0.08 0.03 (N) 3 0.003 (A) 0.0003 0.006 (A) 0.01 0.06 (N) 0.0008 0.8 (A) 15 0.004 (A) 0.00008 0.004 (A) 0.1 0.001 (A) 0.0008 0.03 (A) 0.03 0.001(A) 15

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