Atomic Absorption Instrument Spectrophotometer

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Interferences in AA analysis Hg cold vapor and As hydride generation 1000 ppm AA standards

Atomic absorption spectroscopy (AAS)

Atomic absorption is the determination of the presence and concentrations of metals in liquid samples. Metals include Fe, Cu, Al, Pb, Ca, Zn, Cd and many more. Typical concentrations range in the low mg/L (ppm) range. In atomic absorption (AA) spectrometry, light of a specific wavelength is passed through the atomic vapor of an element of interest, and measurement is made of the attenuation of the intensity of the light as a result of absorption. Quantitative analysis by AA depends on: (1) Accurate measurement of the light intensity. (2) The radiation absorbed must be proportional to the atomic concentration. Metals will absorb ultraviolet light in their elemental form when they are excited by heat, either by flame or graphite furnace. Each metal has a characteristic wavelength that will be absorbed. The AAS instrument looks for a particular metal by focusing a beam of uv light at a specific wavelength through a flame and into a detector. The sample of interest is aspirated into the flame. If that metal is present in the sample, it will absorb some of the light, thus reducing its intensity. The instrument measures the change in intensity. A computer data system converts the change in intensity into an absorbance. The atomic absorption spectrophotometer. The following components make up the AA spectrometer : Hollow cathode lamp Source of the analytical light line for the element of interest Give a constant and intense beam of that analytical line Nebulizer Suck up liquid sample at a controlled rate Create a fine aerosol spray for introduction into the flame Mix the aerosol and fuel and oxidant thoroughly for introduction into the flame Flame Destroy any analyte ions and breakdown complexes o o o Create atoms of the element of interest, Fe , Cu , Zn , etc. Monochromator Isolate the analytical line photons passing through the flame Remove scattered light of other wavelengths from the flame In doing this, only a narrow spectral line impinges on the PMT. Photomultiplier tube (PMT) This is the detector. The PMT determines the intensity of photons of the analytical line exiting the monochromator. The PMT is the most commonly used detector for atomic absorption spectroscopy. However, solid state detectors are now replacing conventional vacuum-type photomultipliers. High tech electronics amplify, filter, and process the electrical signal, using a series of chips and microprocessors,

transmitting the result to an internal or external computer which handle all data-handling and display

Graphite Fufnace AA
The graphite furnace is an electrothermal atomiser system that can produce temperatures as high as 3,000C. The heated graphite furnace provides the thermal energy to break chemical bonds within the sample held in a graphite tube, and produce free ground state atoms. The ground-state atoms are capable of absorbing energy, in the form of light, and are elevated to an excited state. The amount of light energy absorbed increases as the concentration of the selected element increases. Flame AA can only analyse solutions, but graphite furnace can accept very small absolute quantities of solution, slurry or solid samples. New Instruments Fully automatic atomic absorption spectrometers are now available. All operations are controlled through the PC, with the AA-Win software based on a WINDOWS platform. The design with the flame burner and graphite furnace in one compact unit enables automatic interchanging of two analytical methods : Flame atomic absorption and Graphite Furnace Samples The samples and standards are often prepared with duplicate acid concentrations to replicate the analyte's chemical matrix as closely as possible. Acid contents of 1% to 10% are common. High acid concentrations help keep all dissolved ions in solution. Wastes Liquid sample not flowing into the flame collects on the bottom of the nebulizer chamber and flows by gravity through a waste tube to a glass waste container (highly acidic). Flames Atomic absorption instruments always use a nebulizer and a slot burner to increase the path length for sample absorption. Temperature of some flames Fuel H2 C2H2 H2 C2H2 oxidant Air Air O2 N2O Temperature (K) 2000-2100 2100-2400 2600-2700 2600-2800

For some elements that form refractory oxides (molecules hard to break down in the flame) nitrous oxide (N2O) needs to be used instead of air (78% N2 + 21% O2) for the oxidant. In that case, a slightly different burner head with a shorter burner slot length is used. Shutdown Most modern instruments control the ignition and shutdown procedures automatically.

Interference Effects in Atomic Absorption

ELEMENT

line nm

INTERFERENCES

Aluminium
13

Al

309.27
26.98

Enhanced effect caused by ionization. Add an ionization buffer such as 0.1%w/v potassium chloride to both sample and calibration standards

Antimony
15

Sb

121.75

206.83 217.58 231.15

High concentrations of Pb an Cu absorb at 217.58 line. Use line 206.83 or 231.15 if these elements are present. Acids cause depression of the response. Calibration solutions should be matched to the acid concentrations in the sample solutions. Can be determined by a hydride generation or Furnace method.

Arsenic
33

As

193.70

74.92

Flame interferences and scatter effects at arsenic wavelengths. Change to nitrous oxide/acetylene flame. Spike samples and add 1% nickel nitrate solution to digeststes prior to analysis. Can be determined by a hydride generation method.

Barium
56

Ba

137.34

553.55 455.40

Caused by presence of Ca or Ba ionization. Phosphate, silicon and aluminium cause depression in air/acetylene flame. Use nitrous oxide/acetylene flame and an ionisation buffer 0.1% w/v potassium as chloride. No ionization buffer is needed for determination at line 455.40 since this is the barium ion line.

Beryllium
4

Be

234.86

9.012

Acids enhances the response. Al, Si, Mg, depresses the response. Add 0.1% hydrofluoric acid to sample and calibration standards. Can use Furnace method.

Bismuth
83

Bi

223.06
208.98

No serious interference effects with air/acetylene flame.

Boron
5

249.77

10.81

No serious interference effects using nitrous oxide/acetylene, fuel fich flame.

Cadmium
48

Cd

228.80
112.40

Adsorption and light scattering. Large excess of silicate depress response. Calibration solutions should be matched with conc.of sample solutions. Can use Furnace method with ammonim phosphate as a matrix modifier.

Caesium
55

Cs

852.11

132.91

Ionisation effects. Add 0.5% potassium as chloride to both sample and calibration solutions.

Calcium
20

Ca

422.67

40.08

Response is depressed by Al, Be,P, Si, Ti, and Zr in air acetylene flame. The addition of releasing agent 0.2% w/v lanthanum to both samples and calibration stds. reduces this effect. The N2O/acetylene flame eliminates many of these problems but an ionisation buffer 0.1% of potassium as chloride must be added to all solutions. Protein in biological samples depress response and 0.5% EDTA should be added to reduce this effect.

Chromium
24

Cr

357.87

52

Reduced sensitivity with air/acetylene flame. Ca, P, and chloride interference. Phosphate depresses response. Add a 0.25% w/v calcium to all solns. The N2O flame reduces interference effects with a x2 sensitivity

Cobalt
29

Co

240.73
26.98

Large amounts of transition elements affect the response. Calibration stds. should be matched to the concentrations of any of these elements present as major components in the sample soln. Use standard addition. Can use Furnace method.

Copper
29

Cu

324.75
63.55

Transition elements and mineral acids depress the response. Adsorption and scatter. Calibration stds.should be matched to the concentrations of any of these elements present as major components in the sample.

Gold
79

Au

242.80
196.97

Cyanide depresses the response and should be destroyed by fuming with a mix.of sulphuric and perchloric acids.Nitric and HCl give a slight depression, and sulphuric gives a severe depression. Calibration solns. should be matched to the concentrations of these acids in the sample solns. Use ionisation buffer 0.1% w/v of potassium as chloride.

Iron
26

Fe

248.33

55.85

Perchloric acid. Nitric acid, Ni and Si depress the response. Add 0.2% w/v calcium chloride to all solns. Citric acid depress response and this effect can be reduced by adding 0.5% v/v phosphoric acid to both sample and standards. Most of these interference effects can be solved by using the hotter N2O/acetylene flame.

Lithium
03

Li

670.78
6.941

Ionisation effects. Use ionisation buffer 0.1% w/v potassium as chloride to both samples and calibration stds. Strontium gives enhancement due to absorption by SrOH species. Standards should be matched to concentration of strontium in sample. Can be analysed by Flame photometry.

Lanthanum
57

La

550.13

138.91

Ionisation effects. Use ionisation buffer 0.1% w/v potassium as chloride to both samples and calibration stds. Use the N2O/acetyleny fuel rich flame.

Lead
82

Pb

217.00
207.20

The 283.31 line is preferred for routine analysis because of better S/N ratio and lower background interference effects.

Magnesium
12

Mg

24.31

285.21 279.55

Al and Si depress the response in the air/acetylene flame. Add 0.1% La or Sr as chloride to both sample and calibration stds. These effects are reduced in the hotter N2O/acetylene flame with addition of ionisation buffer 0.1% w/v potassium as chloride to all solns. Determination at the 279.55 line however, is the magnesium ion line and requires no KCl buffer with the hotter flame.

Manganese
25

Mn

279.48
54.94

Si depresses the response. Add 0.2% w/v calcium chloride to both samples and calibration stds. Mo and W depress response when -2 -2 acetylene pressure drops below 100 lb. (7Kg cm or 100 lb in ) Change to a full acetylene cylinder.

Mercury
80

Hg

253.65
200.59

Large amounts of Cobalt enhance response. Reducing agents (SnCl2) should be added in xs to all solutions. The cold vapour flameless method is recommended.

Molybdenum
42

Mo

313.26
95.94

Ca, Fe, Mn, Sulphate, and Sr depress response in air/acetylene flame. Add 0.5% w/v aluminium chloride or 2% w/v NH4Cl to both samples and calibration stds. or use the N2O/acetylene flame which gives a x2 increase in sensitivity. The presence of calcium and iron in the hotter flame may cause depressed response which can be reduced by adding 0.5% w/v aluminium or 1% w/v sodium sulphate to both sample and standards. Change acetylene cylinder when -2 -2 pressure falls below 100 lb (7Kg cm or 100 lb in )

Nickel

341.48

Nickel line interference. Use line at 341.48 for routine work. A large

28

Ni

232.00
58.71

excess of iron causes enhancement and calibration stds. should be matched to the concentration of this element in the sample solutions.

Potassium
19

766.49

39.10

Ionisation effects. Add 0.1% w/v sodium or caesium to both sample and calibration solns. High conc. of mineral acids depress response. Calibration stds. should contain the same conc. of acids. Usually analysed by Flame photometry.

Silicon
14

Si

251.61
28.09

Ionisation effects depress response. Use the N2O/acetylene fuel rich flame. Add ionisation buffer 0.1% w/v of an alkali metal as chloride.

Silver
47

Ag

328.07
107.87

Al, Zn, Th, KmnO4, iodate and tungstate depress the response. Do not use hydrochloric acid unless silver is in solution as a chloride complex. Calibration stds. should match the conc. of any of these present as major components in the sample.

Sodium
11

Na

22.99

589.00 589.59

Ionisation effects. Add ionisation buffer 0.1% w/v potassium or caesium chloride to sample and calibration stds. Can be determined by Flame photometry.

Strontium
38

Sr

460.73

87.62

Phosphate, Al, Si, depress response. Add 0.5% w/v lanthanum or calcium chloride to all solutions or use the N2O/acetylene flame

Tin
50

Sn

224.61
118.69

The N2O / acetylene flame should be used for routine determinations in anything but aqueous solutions.

Uranium
92

238.01

358.49 356.66

CN in the flame gives a high noise level at 358.49nm. For this reason, the 356.66nm line is used for most determinatios. Use ionisation buffer 0.1% alkali metal as chloride.

Vanadium
23

318.54

50.94

Al and Ti enhances the response. Add 0.5% aluminium to all solutions. Ionisation effects can be eliminated by addition of 0.1% alkali metal as chloride to all solns.

Zinc
30

Zn

213.86
65.37

Response is depressed with large excess of silicon. The calibration solns. should be matched to the conc. of the element in the sample solns. Strontium removes Cu and phosphate contamination.

The response is enhanced in the presence of ammonium ions, chloride, fluoride and iron. Response is depressed by nickel (NiBr ), nitrate and sulphate. The addition of 0.2% m/v of ammonium fluoride to both sample and standard helps reduce interference effects.

Mercury Cold Vapor

Free mercury atoms can exist at room temperature can be analysed using atomic absorption without employing flame and graphite furnace techniques at high temperatures. Mercury is reduced in solution using stannous chloride or sodium borohydride in a closed system. The reaction quantitatively releases mercury (from the sample solution) and is carried by a stream of air or argon through a quartz sample sell placed in the light path of an AA instrument for analysis. The detection limit for mercury by this cold vapor technique is approximately 0.02 mg/L.
Zirconium
40

Hydride Generation
360.12

Zr

91.22

Hydride generation sampling systems are similar to cold vapor mercury systems, except that the hydrides generated must be heated in air/acetylene flame or electrically to create atoms in the free state. Samples are reacted in an external system with a reducing agent,usually sodium borohydride. Gaseous reaction products are then carried to a sampling cell in the light path of an AA spectrometer. The following metals can be analysed by HGAAS.
As Bi Ge Pb Sb Se Sn Te

The nebulizer required in AAS is not used in HGAAS. Continuous flow system or batch flow systems can be used. Acid contents of samples and standards of 10% to 50% are common; this is much much higher than in normal AAS. The reaction of many metalloid oxyanions with sodium borohydride and HCl produces a volatile hydride: H2Te,

H2Se, H3As, H3Sb, etc. The oxidation state of the metalloid is crucial and care must be taken to produce the specific metalloid oxidation state before the sample is introduced into the hydride generation system. For example, HGAAS analysis of selenium requires the Se(IV) oxidation state (selenite). Se(VI), the more highly oxidized state of the element (selenate), responds erratically and non reproducibly in the system. All selenium in Se calibration standards and samples must be in the Se(IV) form for analysis. Oxidize all Se in the sample to selenate using conc.nitric acid or hydrogen peroxide (decomposing the excess oxidant) and then reducing the contained selenate to selenite with boiling HCl. After that reduction step, the final acid content is made up to the required content and is immediately introduced into the hydride generation module. The sodium borohydride and hydrochloric acid reagents feed into the hydride generation reaction vessel must be optimized and may be different for different elements. Example concentrations are 0.35% NaBH4 and 50% HCl.

1000ppm ATOMIC ABSORPTION standards

This page provides a list of metals analysed by atomic absorption spectroscopy, and gives info on how to prepare a 1000 ppm AA standard solution from the pure element or from one of its salt. Use deionized water and store all solutions in stoppered polythene bottles.

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Preparation of 1000pm Stock AA Standards

Aluminium Dissolve 1.000 g of Aluminium metal in 25ml. of hydrochloric acid (S.G. 1.18) and a few drops of nitric acid (S.G. 1.42) Dilute to 1 litre in a volumetric flask with deionised water. Antimony

Dissolve 1.000g antimony in 10ml. conc. hydrochloric acid, a few drops of conc. nitric acid, and 10g of tartaric acid. Dilute to 1 litre with deionised water. Arsenic Dissolve 1.000g of arsenic powder in 50ml. conc. nitric acid. Dilute to 1 litre with deionised water or Dissolve 1.3200g arsenous oxide (As2O3) , dried to 110C, in 50ml. of conc. hydrochloric acid. Dilute to 1 litre with deionised water. Barium Dissolve 1.4380g.of barium carbonate (BaCO3) in 20ml. 1M hydrochloric acid. Dilute to 1litre in a volumetric flask with deionised water. Beryllium Dissolve 19.639g. of beryllium sulphate (BeSO4) in 250 deionised water. Dilute to 1 litre in a volumetric flask with deionised water. Bismuth Dissolve 1.000g. of bismuth metal in 50ml. conc. nitric acid Dilute to 1litre in a volumetric flask with deionised water. Dissolve 1.1148g. of bismuth trioxide (Bi2O3) in the minimum quantity of comc. hydrochloric acid. Dilute to 1litre in a volumetric flask with deionised water. Boron Dissolve 5.1744g. of boric acid (H3BO3) in 500ml. of deionised water. Dilute to 1litre in a volumetric flask with deionised water.. Cadmium Dissolve 1.000g. of cadmium metal in 20ml. of 5M.hydrochloric acid and 2 drops of conc. nitric acid. Dilute to 1litre with deionised water. Dissolve 2.0360g. of cadmium chloride in 250 ml deionised water.Dilute to 1 litre in a volumetric flask. Dissolve 2.1032g. of cadmium nitrate in 250ml.of deionised water. Diluteto1 litre in a volumetric flask. Caesium Dissolve 1.2670g. of caesium chloride (CsCl) in 100ml. of deionised water. Dilute to 1 litre in a volumetric flask with deionised water. Calcium

Dissolve 2.4973g. of calcium carbonate (CaCO3) in 25ml. of 1M hydrochloric acid. This should be added dropwise to avoid losses during the vigorous effervescence. Dilute to 1litre in a volumetric flask with deionised water. Dissolve 2.7693g. of calcium chloride (CaCl2) in 100ml. deionised water. Dilute to 1litre in a volumetric flask with deionised water. Chromium Dissolve 7.6960g. of chromium nitrate (Cr(NO3)3.9H2O) in 250ml.of deionised water. Dilute with more deionised water in 1 litre vol. Flask. Cobalt Dissolve 1.000g. of cobalt metal in 50ml. of 5M hydrochloric acid. Dilute to 1litre in a volumetric flask with deionised water.or Dissolve 4.9379g. of cobalt nitrate (Co(NO3)2.6H2O in 250 ml. deionised water. Dilute to 1litre in a volumetric flask with deionised water. Dissolve 4.0380g. of cobalt (11) chloride (CoCl2.6H2O) in 200ml. deionised water. Dilute to 1litre in a volumetric flask with deionised water. Copper Dissolve 1.000g. of copper metal in 50ml. of 5M nitric acid. Dilute to 1 litre in a volumetric flask with deionised water. or

Dissolve 3.7980g. of (Cu(NO3)2.3H2O in 250ml. of deionised water. Dilute to 1 litre in a volumetric flask with deionised water. Gold Dissolve 1.000g. of gold metal in 15ml. of conc. hydrochloric acid and 5ml. of conc. nitric acid. Dilute to 1 litre in a volumetric flask with deionised water.or Dissolve 1.8110g. of ammonium chloroaurate (NH4AuCl4) in 100ml.of deionised water. Dilute to 1 litre in a volumetric flask with deionised water. Iron Dissolve 1.000g. of iron wire or granules in 20ml. of 5M hydrochloric acid Dilute to 1 litre in a volumetric flask with deionised water.or Dissolve 4.8400g. of iron (111) chloride (FeCl3.6H2O) in 200ml. of deionised water. Dilute to 1 litre in a volumetric flask with deionised.water Lanthanum

Dissolve 1.1782g. of lanthanum oxide (La2O3) in 20ml. of 5M hydrochloric acid. Dilute to 1 litre in a volumetric flask with deionised water. Lead Dissolve 1.000g.of lead metal in 50ml. of 2M nitric acid. Dilute to 1 litre in a volumetric flask with deionised water. Dissolve1.5980g. of lead nitrate ( Pb(NO3)2 ) in 100ml. of deionised water. Dilute to 1 litre in a volumetric flask with deionised water. Magnesium Dissolve 1.000g. of magnesium metal in 50ml. of 5M hydrochloric acid. Dilute to 1 litre in a volumetric flask with deionised water.or Dissolve 3.9160g. of magnesium chloride (MgCl2.6H2O) in 200ml. of deionised water. Dilute to 1 litre in a volumetric flask with deionised water. Manganese Dissolve 1.000g. of manganese metal in50ml. of conc. hydrochloric acid. Dilute to 1 litre in a volumetric flask with deionised water. Dissolve 3.6077g. of manganesse chloride (MnCl2.4H20) in 50ml. conc. hydrochloric acid. Dilute to 1 litre in a volumetric flask with deionised water. Mercury Dissolve 1.000g. of mercury metal in20ml. of 5M nitric acid. Dilute to 1 litre in a volumetric flask with deionised water.or Dissolve 1.3520g. of mercury (11) chloride (HgCl2) in 250ml. of deionised water. Dilute to 1 litre in a volumetric flask with deionised water. or Dissolve 1 .0800g. of mercury (11) oxide (HgO) in 20ml. of 5M hydrochloric acid. Dilute to 1 litre in a volumetric flask with deionised water. Molybdenum Dissolve 1.000g. of molybdenum powder in 10 ml. of conc. hydrochloric acid and 10ml. of deionised water. Add 1ml. of conc.nitric acid. Use a magnetic stirrer to completely dissolve the molybdenum. Dilute to 1 litre in a volumetric flask with deionised water. or Dissolve 1.8403g. of ammonium molybdate (NH4)6MO7O22.4H2O in 500ml. of deionised water. Dilute to 1 litre in a volumetric flask with deionised water. or Dissolve 1.5000g. of molybdenum trioxide (MoO3) in 25ml. conc. hydrochloric acid. Dilute to 1 litre in a

volumetric flask with deionised water. Nickel Dissolve 1.000g. of nickel in 20ml. of conc. nitric acid. Dilute to 1 litre in a volumetric flask with deionised water.or Dissolve 4.9530g. of nickel nitrate (Ni(NO3)2.6H2O) in 1 litre volumetric flask with deionised water. Potassium Dissolve1 1.9070 g. of dry potassium chloride in 250 ml. of deionised water. Dilute to 1 litre in a volumetric flask with deionised water. Silica Dissolve about 7.6 g. of sodium metasilicate (Na2SiO3.5H2O in deionised water. Dilute to 1 litre in a volumetric flask with deionised water. Silver Dissolve 1.5750 of silver nitrate in 200ml. of deionised water. Dilute to 1 litre in a volumetric flask with deionised water. Sodium Dissolve 2.5420g. of sodium chloride (NaCl) in 200ml. of deionised water. Dilute with deionised water to 1 litre in a volumetric flask. Strontium Dissolve 2.4150g. of strontium nitrate (Sr(NO3)2 in 200ml. of deionised water. Dilute to 1 litre in a volumetric flask with water. Tin Dissolve 1.000g. of tin metal in 200ml. of conc. hydrochloric acid and 5ml. of conc.nitric acid. Dilute to 1 litre in a volumetric flask with deionised water. or Dissolve 2.9540 of tin (1V) chloride pentachloride (SnCl4.5H2O) in 500ml. deionised water.If precipitate forms, redissolve by adding 6M hydrochloric acid. Dilute to 1 litre in a volumetric flask with deionised water Uranium Dissolve 21.100g. of uranyl nitrate (UO2(NO3)26H2O) in 250ml. of deionised water. Dilute to 1 litre in a volumetric flask with deionised water.or Dissolve 14.329g. of uranyl chloride (UO2Cl2) in 250ml. of deionised water. Dilute to 1 litre in a volumetric

flask with deionised water. Vanadium Dissolve 1.000g. of vanadium metal in 25ml.conc.nitric acid. Dilute to 1 litre. Dissolve 2.2960g. of ammonium metavanadate (NH4VO3) in 20ml. of 100 volume hydrogen peroxide. Dilute to 1 litre in a volumetric flask with deionised water. Zinc Dissolve 1.000g. of zinc metal in 30ml. of 5M hydrochloric acid. Dilute to 1 litre in a volumetric flask with deionised water.or Dissolve 1.2450g. of zinc oxide (ZnO) in 5ml of deionised water followed by 25ml. of 5M hydrochloric acid. Dilute to 1 litre in a volumetric flask with deionised water Zirconium Dissolve 1.000g. of zirconium metal in 25ml. of hydrofluoric acid (40% w / v) in a P.T.F.E. beaker. Dilute to 1 litre in a polpropylene volumetric flask with deionised water, or Dissolve 3.7174g. of dry zirconium nitrate in 1 litre deionised water

Parts Per Million Conversions

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PPM conversion values and serial dilutions : How to dilute and calculate ppm concentrations and volumes, and how to convert ppm to molarity and percentage amounts.

ppm = parts per million PPM is a term used in chemistry to denote a very, very low concentration of a solution. One gram in 1000 ml is 1000 ppm and one thousandth of a gram (0.001g) in 1000 ml is one ppm. One thousanth of a gram is one milligram and 1000 ml is one liter, so that 1 ppm = 1 mg per liter = mg/Liter. PPM is derived from the fact that the density of water is taken as 1kg/L = 1,000,000 mg/L, and 1mg/L is 1mg/1,000,000mg or one part in one million. OBSERVE THE FOLLOWING UNITS 1 ppm = 1mg/l = 1ug /ml = 1000ug/L

ppm = ug/g =ug/ml = ng/mg = pg/ug = 10 ppm = mg/litres of water

-6

1 gram pure element disolved in 1000ml = 1000 ppm PPB = Parts per billion = ug/L = ng/g = ng/ml = pg/mg = 10
-9

Making up 1000 ppm solutions 1. From the pure metal : weigh out accurately 1.000g of metal, dissolve in 1 : 1 conc. nitric or hydrochloric acid, and make up to the mark in 1 liter volume deionised water. 2. From a salt of the metal : e.g. Make a 1000 ppm standard of Na using the salt NaCl. FW of salt = 58.44g. At. wt. of Na = 23 1g Na in relation to FW of salt = 58.44 / 23 = 2.542g. Hence, weigh out 2.542g NaCl and dissolve in 1 liter volume to make a 1000 ppm Na standard. 3. From an acidic radical of the salt : e.g. Make a 1000 ppm phosphate standard using the salt KH2PO4 FW of salt = 136.09 FW of radical PO4 = 95 1g PO4 in relation to FW of salt = 136.09 / 95 = 1.432g. Hence, weigh out 1.432g KH2PO4 and dissolve in 1 liter volume to make a 1000 ppm PO4 standard. Click this link for Atomic absorption standards

Dilution Formula = M1V1 = M2V2 req is the required value you want. req ppm x req vol -------------------------- = no of mls for req vol stock e.g. Make up 50 mls vol of 25 ppm from 100 ppm 25 x 50 / 100 = 12.5 mls. i.e. 12.5 mls of 100 ppm in 50 ml volume will give a 25 ppm solution

Serial dilutions

Making up 10 M to 10 M solutions from a 1M stock solution.

-1

-5

Pipette 10 ml of the 1M stock into a 100 ml volumetric flask and make up to the mark to give a 10 M soln. -1 -2 Now, pipette 10 ml of this 10 M soln. into another 100 ml flask and make up to the mark to give a 10 M soln. -2 -3 Pipette again, 10 ml of this 10 M soln. into yet another 100 ml flask and make up to mark to give a 10 M soln. -3 -4 Pipette a 10 ml of this 10 M soln. into another 100 ml flask and make up to mark to give a 10 M soln. -4 -5 And from this 10 M soln. pipette 10 ml into a 100 ml flask and make up to mark to give a final 10 M solution.

-1

Molarity to ppm

conc. in mg/l Molarity = -----------------------gram mol solute x 1000 The FW of an ion species is equal to its concentration in ppm at 10 M. Fluoride has a FW of 19, hence a -3 -5 10 M concentration is equal to 19ppm, 1M is equal to 19,000 ppm and 1ppm is equal to 5.2 x 10 M. Go here for ISE molarity/ppm conversions shown in Table III.
-3

Ppm (parts per million) to % (parts per hundred)

Example:

1 ppm = 1/1,000,000 = 0.000001 = 0.0001% 10 ppm = 10/1,000,000 = 0.00001 = 0.001% 100 ppm = 100/1,000,000 = 0.0001 = 0.01% 200 ppn = 200/1,000,000 = 0.0002 = 0.02% 5000 ppm = 5000/1,000,000 = 0.005 = 0.5% 10,000 ppm = 10000/1,000,000 = 0.01 = 1.0% 20,000 ppm = 20000/1,000,000 = 0.02 = 2.0%

(Parts per hundred) % to ppm

Example:

0.01% = 0.0001 0.0001 x 1,000,000 = 100 ppm

Ppm (parts per million) to % (parts per hundred)

Example:

1 ppm = 1/1,000,000 = 0.000001 = 0.0001% 10 ppm = 10/1,000,000 = 0.00001 = 0.001% 100 ppm = 100/1,000,000 = 0.0001 = 0.01% 200 ppn = 200/1,000,000 = 0.0002 = 0.02% 5000 ppm = 5000/1,000,000 = 0.005 = 0.5% 10,000 ppm = 10000/1,000,000 = 0.01 = 1.0% 20,000 ppm = 20000/1,000,000 = 0.02 = 2.0%

Atomic Absorption Spectroscopy

Atomic Absorption Spectroscopy (AAS)

Atomic Absorption Spectroscopy in analytical chemistry is a technique for determining the concentration of a particular metal element within a sample. Atomic absorption spectroscopy can be used to analyze the concentration of over 62 different metals in a solution. Although atomic absorption spectroscopy dates to the nineteenth century, the modern form was largely developed during the 1950s by a team of Australian chemists, lead by Alan Walsh, working at the CSIRO (Commonwealth Science and Industry Research Organization) Division of Chemical Physics, in Melbourne Australia. Typically, the technique makes use of a flame to atomize the sample, but other atomizers such as a graphite furnace are also used. Three steps are involved in turning a liquid sample into an atomic gas:
1. 2. 3. Desolvation the liquid solvent is evaporated, and the dry sample remains Vaporizations the solid sample vaporizes to a gas Volatilization the compounds making up the sample are broken into free atoms.

The flame is arranged such that it is laterally long (usually 10cm) and not deep. The height of the flame must also be controlled by controlling the flow of the fuel mixture. A beam of light is focused through this flame at its longest axis (the lateral axis) onto a detector past the flame. The light that is focused into the flame is produced by a hollow cathode lamp. Inside the lamp is a cylindrical metal cathode containing the metal for excitation, and an anode. When a high voltage is applied across the anode and cathode, the metal atoms in the cathode are excited into producing light with a certain emission spectra. The type of hollow cathode tube depends on the metal being analyzed. For analyzing the concentration of copper in an ore, a copper cathode tube would be used, and likewise for any other metal being analyzed. The electrons of the atoms in the flame can be promoted to higher orbitals for an instant by absorbing a set quantity of energy (a quantum). This amount of energy is specific to a particular electron transition in a particular element. As the quantity of energy put into the flame is known, and the quantity remaining at the

other side (at the detector) can be measured, it is possible to calculate how many of these transitions took place, and thus get a signal that is proportional to the concentration of the element being measured.
[courtesy of http://en.wikipedia.org/wiki/Atomic_absorption_spectroscopy]

Cold Vapor Atomic Absorption (CVAA)

Since atoms for most AA elements cannot exist in the free, ground state at room temperature, heat must be applied to the sample to break the bonds combining atoms into molecules. The only notable exception to this is mercury. Free mercury atoms can exist at room temperature and, therefore, mercury can be measured by atomic absorption without a heated sample cell. In the cold vapor mercury technique, mercury is chemically reduced to the free atomic state by reacting the sample with a strong reducing agent like stannous chloride or sodium borohydride in a closed reaction system. The volatile free mercury is then driven from the reaction flask by bubbling air or argon through the solution. Mercury atoms are carried in the gas stream through tubing connected to an absorption cell, which is placed in the light path of the AA spectrometer. Sometimes the cell is heated slightly to avoid water condensation but otherwise the cell is completely unheated. As the mercury atoms pass into the sampling cell, measured absorbance rises indicating the increasing concentration of mercury atoms in the light path. Some systems allow the mercury vapor to pass from the absorption tube to waste, in which case the absorbance peaks and then falls as the mercury is depleted. The highest absorbance observed during the measurement will be taken as the analytical signal. In other systems, the mercury vapor is rerouted back through the solution and the sample cell in a closed loop. The absorbance will rise until an equilibrium concentration of mercury is attained in the system. The absorbance will then level off, and the equilibrium absorbance is used for quantitation. The entire cold vapor mercury process can be automated using flow injection techniques. Samples can be analyzed in duplicate at the rate of about 1 sample per minute with no operator intervention. Detection limits are comparable to those obtained using manual batch processes. The use of flow injection systems also minimizes the quantity of reagents required for the determinations, further reducing analysis costs. The sensitivity of the cold vapor technique is far greater than can be achieved by conventional flame AA. This improved sensitivity is achieved, first of all, through a 100% sampling efficiency. All of the mercury in the sample solution placed in the reaction flask is chemically atomized and transported to the sample cell for measurement. The sensitivity can be further increased by using very large sample volumes. Since all of the mercury contained in the sample is released for measurement, increasing the sample volume means that more mercury atoms are available to be transported to the sample cell and measured. The detection limit for mercury by this cold vapor technique is approximately 0.02 g/L. Although flow injection techniques use much smaller sample sizes. They provide similar

performance capabilities, as the entire mercury signal generated is condensed into a much smaller time period relative to manual batch-type procedures.
[Courtesy of Concepts, Instrumentation and Techniques in Atomic Absorption Spectrophotomerty, Richard D. Beaty and Jack D. Kerber. PerkinElmer.]

Flame Atomic Absorption (FLAA)

Flame Atomic Absorption Spectroscopy is a fast and easy technique with an extremely high sensitivity (especially for elements like Pb, Cd, Cu and Cr), although problems can arise as a result of chemical (a much worse situation than with ICP-AES) and spectral interferences. The sample is atomized in the flame, through which radiation of a chosen wavelength (using a hollow cathode lamp) is sent. The amount of absorbed radiation is a quantitative measure for the concentration of the element to be analyzed. The most current gas mixtures used are air/acetylene and nitrous-oxide/acetylene. The latter resulting in higher atomization efficiencies and thus better detection limits for elements like Si, Al, Sc, Ti, V and Zr. The air/acetylene flame can be used for easy atomizable elements (e.g. As and Se). Background correction can be achieved with a deuterium lamp although several disadvantages subsequently occur. A disadvantage of the AAS technique is the non linearity of the calibration curves when absorbance becomes higher than 0.5 to 1. The relative standard deviations are between 0.3 and 1% for absorbances of 0.1 to 0.2. Detection limits for flame AAS vary enormously: from 1 - 5 ppb (e.g. Ca, Cd, Cr, Cu) to more than 1000 ppb (e.g. P). Some elements (e.g. B, C, Br) cannot be measured at all.
[Courtesy of http://www.mtm.kuleuven.ac.be/Research/Equipment/Chemical/FAAS.html]

Overview of Technique In flame atomic absorption spectroscopy a liquid sample is aspirated and mixed as an aerosol with combustible gasses (acetylene and air or acetylene and nitrous oxide.) The mixture is ignited in a flame of temperature ranging from 2100 to 2800 degrees C (depending on the fuel gas used.) During combustion, atoms of the element of interest in the sample are reduced to the atomic state. A light beam from a lamp whose cathode is made of the element being determined is passed through the flame into a monochronometer and detector. Free, unexcited ground state atoms of the element absorb light at characteristic wavelengths; this reduction of the light energy at the analytical wavelength is a measure of the amount of the element in the sample. Specific Sample Considerations Plant: solid samples must be in liquid form to be aspirated by the instrument. Therefore, solid material must be liquefied by means of some form of extract or digest protocol. Procedures have been devised that make the total amount of an element in the sample available for assay or that use some particular property to extract that portion of the element which exists in some chemical forms but not in others. The [plant dry ash/double acid] extraction method determines the total element content of the sample.

Soil: for ecological purposes there is more interest in measures of extractable or labile soil constituents than in total element content. Certain partitions of the total soil content of a given element are operationally defined by an extraction procedure, and arguments are usually offered that these partitions, so defined, correspond to different levels of biological availability or activity. The [HCl/H2SO4 double acid] extraction method, also referred to as North Carolina and Mehlich-1, is widely used to determine bioavailable Ca, K, Mg, Mn, P, and Zn in sandy acid soils characteristic of the eastern and southeastern United States. Water: aquatic samples of course need no liquefaction step, but researchers must still decide which analyte partition (dissolved, suspended, total) is of interest. Differing treatments of each sample partition are detailed in the U.S. EPA's discussion of [Content partitioning] of water samples.
[Courtesy of http://www.uga.edu/~sisbl/aaspec.html]

Graphite Furnace Atomic Absorption (GFAA)

Graphite furnace atomic absorption spectrometry is a highly sensitive spectroscopic technique that provides excellent detection limits for measuring concentrations of metals in aqueous and solid samples. GFAA has been used primarily in the field for the analysis of metals in water. GFAA could be used to determine metals in soil, but the sample preparation for metals in soil is extensive and is not practical for field applications. GFAA cannot be described as a truly field portable instrument. GFAA instruments are extremely sensitive and therefore, must be operated in a clean, climate controlled environment. This can be difficult but not impossible to achieve in a field environment. In addition, the 220-volt electrical power requirement often precludes remote operation. However, GFAA is an example of taking the laboratory to the field. Miniaturization of electronics has significantly reduced instrument size and weight, making it easier to use the instrument in a field laboratory. In atomic absorption (AA) spectrometry, light of a specific wavelength is passed through the atomic vapor of an element of interest, and measurement is made of the attenuation of the intensity of the light as a result of absorption. Quantitative analysis by AA depends on: (1) accurate measurement of the intensity of the light and (2) the assumption that the radiation absorbed is proportional to atomic concentration. Samples to be analyzed by AA must be vaporized or atomized, typically by using a flame or graphite furnace. The graphite furnace is an electrothermal atomizer system that can produce temperatures as high as 3,000C. The heated graphite furnace provides the thermal energy to break chemical bonds within the sample and produce free ground-state atoms. Ground-state atoms then are capable of absorbing energy, in the form of light, and are elevated to an excited state. The amount of light energy absorbed increases as the concentration of the selected element increases. GFAA has been used primarily for analysis of low concentrations of metals in samples of water. GFAA can be used to determine concentrations of metals in soil, but the sample preparation for

metals in soil is somewhat extensive and may require the use of a mobile laboratory. The more sophisticated GFAAs have a number of lamps and therefore are capable of simultaneous and automatic determinations for more than one element. Logistical needs include reagents for preparation and analysis of samples, matrix modifiers, a cooling system, and a 220-volt source of electricity. In addition, many analytical components of the GFAA system require significant space, which typically is provided by a mobile laboratory. The advantages of GFAA spectrometry include:
Greater sensitivity and detection limits than other methods Direct analysis of some types of liquid samples Low spectral interference Very small sample size
[Courtesy of http://www.clu-in.org/char/technologies/graphite.cfm]

Inductively Coupled Plasma Mass Spectroscopy (ICP-MS)

The Inductively Coupled Plasma coupled with a mass spectrograph give very high sensitivity for the determination of elements and even isotopes. This technique has the ability to detect very low levels (parts per billion) of most elements in a sample. The dynamic range is typically ten orders of magnitude and data reduction is relatively simple. Rapid data acquisition and data reduction enable the measurement of large numbers of samples in a short period of time. ICP-MS is the technique of choice for trace element analysis of natural waters, minerals, and rocks. High precision is achieved by using multiple internal standards.
[Courtesy of http://www.chemistry.nmsu.edu/Instrumentation/ICP_MS.html]

Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES)

Inductively coupled plasma optical emission spectroscopy is a major technique for elemental analysis. The sample to be analyzed, if solid, is normally first dissolved and then mixed with water before being fed into the plasma. Atoms in the plasma emit light (photons) with characteristic wavelengths for each element. This light is recorded by one or more optical spectrometers and when calibrated against standards the technique provides a quantitative analysis of the original sample. ICP instruments comprise various optical spectrometers, nebulizers (including glass concentric, parallel flow, JY pneumatic, cross flow, V groove, micro concentric, ultrasonic, CMA), spray chambers, ICP torch, and RF generators.
[Courtesy of http://icp-oes.net/]

Fourier Transform Infrared (FTIR)

FTIR spectrometers record the interaction of IR radiation with a sample, measuring the frequencies at which the sample absorbs the radiation and the intensities of the absorption. Determining these frequencies allows identification of the sample's chemical make-up, since chemical functional groups are known to absorb radiation at specific frequencies. The intensity of the absorption is related to the concentration of the component. Intensity and frequency of sample absorption are depicted in a two-dimensional plot called a spectrum. Intensity is generally reported in terms of percent transmittance, the amount of light that passes through it. In the interferometer the light passes through a beam splitter, which sends the light in two directions at right angles. One beam goes to a stationary mirror then back to the beam splitter. The other goes to a moving mirror. The motion of the mirror makes the total path length variable versus that taken by the stationary-mirror beam. When the two meet up again at the beam splitter, they recombine, but the difference in path lengths creates constructive and destructive interference pattern called an interferogram. The recombined beam passes through the sample. The sample absorbs all the different wavelengths characteristic of its spectrum, and this subtracts specific wavelengths from the interferogram. The detector now reports variation in energy versus time for all wavelengths simultaneously. A laser beam is superimposed to provide a reference for the instrument operation.
[Courtesy of http://www.chemistry.nmsu.edu/Instrumentation/PE_Spec1.html]

Description Infrared spectroscopy is an established analytical technique that identifies compounds by fingerprint light absorption spectra. A sample's molecular constituents are revealed through their characteristic frequency-dependent absorption bands. Click here for a typical IR spectrum. Laboratory infrared (IR) instruments have been used extensively for decades in fixed laboratory settings. Recently, manufacturers of the instruments have significantly reduced their overall size and power requirements to perform field analysis, while increasing their durability. Types of portable instrumentation include Multiple Internal Reflectance Infrared Spectrometers, Long Range Gas Monitors, Open Path Infrared Flammable Gas Detectors and Infrared Ambient Air Monitors, and Open Path Fourier Transform Infrared (FTIR) systems. Typical Uses In the environmental field, IR's primary use is air monitoring for volatile organic chemicals (VOCs) by FTIR. FTIR is the preferred method because interferometry (specific to FTIR) provides multiple, rapid scanning capability which allows near real-time analysis. Applications for which FTIR is suitable include fence-line or site perimeter monitoring, worker exposure monitoring, emission rate assessment, air impact measurement during emergency removals, air impact evaluation during remedial actions, vapor suppression technique evaluation, accidental release early warning systems, and industrial facility monitoring. Open-path FTIR was first employed at waste sites in 1990. Its use has grown as the technology has improved and matured. It has been employed at numerous sites over the last few years for applications in fugitive industrial emissions, industrial health and safety monitoring, and indoor air assessments. Recently, manufacturers of FTIR have reconfigured the systems into high-powered, durable

projectors and mirrors for use in field applications. In October 1996, EPA issued Toxic Compendium Method TO-16 recognizing open-path FTIR as an ambient air monitoring method.