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Chapter 8 Combining and choosing analytical techniques Mass Spectrometry The mass spectrometer can be used for: -Quantitative

analysis: as a sophisticated and very sensitive detector that can measure how much of a substance is present. -Qualitative analysis: to provide a unique fingerprint of substance; this can be used to identify the substance from an online database or to give information about the structure of a new or unknown compound. Instrumentation: The key principle of mass spectrometry is that a charged particle passing through a magnetic field is deflected along a circular path of radius proportional to the massto-charge ratio, m/e. Operation: -The sample, as a gas, enters the evacuated tube. -Positive ions are formed in the ionisation chamber when an electron beam dislodges electrons from the sample atoms or molecules. -The positive ions are accelerated by an electric field. -The ions enter a magnetic field perpendicular to their path. This causes the ions to move in a curved path with a radius that depends upon the mass-to-charge ratio(m/e) of the ions. - Only ions moving in a curved path of a particular radius, corresponding to a fixed m/e ratio, will reach the collector. - Particles of a different m/e ratio are able to reach the collector through adjustments to the accelerated voltage or the strength of the magnetic field. -The collector measures the current due to the ions reaching the detector and the data is recorded as a mass spectrum. Hoe the spectrum is formed: A molecular substance can give a range of peaks in the spectrum Factors causing the many peaks in the spectrum: -The fragmentation of the molecules into a large number of different positive ions. -The occurrence of different isotopes of the atoms that make up the molecules.

Fragmentation: The break-up of a molecule into a number of different smaller fragments in a mass spectrometer, the mass of which can be used to identify the molecule. FragmentationThe high energy electron beam can knock just one electron from the molecule, M, to form a positive ion M+: M + e- M+ + 2eBombarding electron M+ is called the molecular ion or parent molecular ion. Molecular ions: A molecule with either more or fewer electrons than it has protons so it carries an overall charge; in mass spectrometry, the ions formed when electrons are knocked out of a molecule or molecule fragment. Parent Molecular Ion: The ion formed when one electron is knocked out of a molecule in a mass spectrometer.

Isotope effects In the same spectrum additional peaks can be formed due to the occurrence of different isotopes of an element. The relative intensities of the ions depend on: - The energy of the bombarding electrons - The stability of the ion fragments formed - The ease with which ions can lose atoms. - A mass spectrometer measures the mass-to-charge ratio ( m/e) of atomic and molecular ions. - The peak with the highest m/e ratio is used to determine the molecular mass of a compound. - The fragmentation pattern of a molecule is used to determine its structure. - Each compound has a unique mass spectrum that can be used to identify the compound. 8.2 Combined techniques Many instruments combine two techniques to provide more detailed and rapid information about a sample. The most commonly used combined techniques are gas chromatographymass spectrometry (GC-MS) and high performance liquid chromatographymass spectrometry (HPLC-MS). The advantage of the techniques of gas chromatographymass spectrometry (GC-MS) and high performance (or high pressure ) liquid

chromatography mass spectrometry (HPLC-MS) is that the chromatography can separate a complex sample into any number of components and each one can be positively identified through mass spectrometry. GC-MS and HPLC-MS have become the essential techniques for forensic analysis. Synchrotron- the ultimate combined technique Is a giant collection of spectrometers linked via circular channels and covering an area equal to half a football field. A synchrotron accelerates and circulates electrons to close to the speed of light. The electrons are accelerated by magnets in a linear accelerator and in a booster ring and then transferred to an outer storage ring. As the electrons paths are bent through magnetic fields, the electrons generate electromagnetic radiation across the spectrum from infrared to X-ray. The radiation is channeled down beam lines where it is used as the source radiation for a range of chemical instruments. Synchrotrons have a number of advantages over conventional spectrometers: - The electromagnetic radiation is hundreds of thousands of times more intense. - A wide energy spectrum from infrared to X-rays is produced the radiation can be very finely tuned to select precise frequencies the radiation is highly polarized. - Short intense pulses of radiation lasting less than a nanosecond are produced. Most of the thirteen beamlines and spectroscopic techniques used in the synchrotron use X-ray radiation to perform a range of analyses. However, two of the beamlines use radiation in the region which we have considered in this book, infrared and ultraviolet radiation. A fantastic range of analyses can be carried out using a synchrotron: - The development of the anti-influenza drug Relenza depended on the identification of the structure of a crucial influenza enzyme by Australian scientists working on synchrotrons overseas. - Chocolate manufacturers used a synchrotron to investigate the optimum conditions of heating, cooling and stirring to form the best cocoa crystals for chocolate making. - Metal and ceramic surfaces used in jet aircraft engines are under investigation using the synchrotron to devise components that can run hotter and for longer. - Researchers in Chicago were able to take X-ray videos using a synchrotron and made new discoveries regarding the breathing patterns of beetles.

- Combined techniques such as gas chromatographymass spectrometry (GC-MS) and high performance liquid chromatographymass spectrometry (HPLC-MS) are used in analytical laboratories. A complex sample can be separated into a number of components and each one can be identified. - A variety of qualitative and quantitative analytical techniques are used to identify a particular substance. - The synchrotron is a sophisticated spectrometer that produces a wide spectrum of electromagnetic radiation from infrared to X-rays. 8.3 Assessing analytical techniques A summary of analytical techniques

Techniqu Typical Typical e analytes sample s Gravimet H2O; Foods; ric NaCl; water Analysis Ag

Advantages

Disadvantag es

Comments

Mass Any spectrom element etry s and compou nds that can be volatize d

Volumet

Acids/b

Limited analytes and samples; suitable for high concentratio ns only Huge Very low Expensive range detection limits; instrument; of unique trained elemen fingerprints technician ts and formed; huge needed to organic range of analytes; operate molecu readily les; automated must be able to be volatiz ed Cleanin Very cheap- only Suitable for

Very cheap- only basic laboratory equipment needed; easy to perform

Analyte must be easily separated from the other materials with which it is found (e.g. by heating or precipitation and separation) and the residue weighed. Used in quantitative analysis as a detector for AES, GC and LC; most useful for qualitative analysis to determine structure and identity of a compound

Suitable for routine quality

ric analysis

TLC

Drug prepara tions; dyes in foodstu ffs GC Low Water, molecul foods, ar mass drugs, organic biologi compou cal nds, e.g. sample acetone, s aspirin HPLC Medium Foods, to high drugs, molecul biologi ar mass cal organic sample compou s nds, e.g. pesticid es, enzyme s Atomic Many Genera emission metals, lly low spectrosc e.g. Ca, viscosit opy Na, Mg y solutio ns, e.g. waste water Atomic Most Genera

ases; oxidants /reducta nts, e.g. sodium hydroxi de, vitamin C Dyes, amino acids

g product s, soft drinks

basic laboratory equipment needed; easy to perform

relatively control of samples high concentratio ns only; relatively large sample size needed

Very cheap- only Poor Samples need to be colored basic laboratory precision or visible under UV light equipment and accuracy needed; easy to perform High sensitivity and precision; small sample size; readily automated Moderately Samples must be volatilized expensive without breaking down instrument; trained technician to operate

High sensitivity and precision; small sample size; readily automated

Moderately expensive instrument; trained technician needed to operate

Samples must be soluble in a suitable solvent

High sensitivity and precision; rapid, multielement analysis; readily automated

Moderately expensive instrument; trained technician needed to operate Moderately

ICP-AES can determine most elements; simpler machines are more limited

High sensitivity

Solid samples can be

absorptio metals, n e.g. Cu, spectrosc Fe, Zn opy

UVvisible

IR

NMR

Moderately Most useful for qualitative expensive; analysis- fingerprint or trained elucidation of structure technician needed to operate Organic Genera High sensitivity Very Technique mainly used to molecul lly and precision; expensive to determine structures rather es liquid small sample size buy and than routine chemical or solid operate analysis Chemical considerations Analyte Consider whether the analyte is a metal or non-metal. Is it coloured or transparent? What functional groups are present? Is the analyte volatile? Is it soluble in water or other solvents? Sample Consider the amount of sample available, the concentration of the analyte in the sample, the physical state of the sample, and possible interference from other compounds in the sample. Economic considerations Time The time taken for an analysis depends on whether a single analysis is to be performed per day or if hundreds of samples are required to be analysed per day, and if continuous monitoring, multi-element determination, or complex sample preparation are needed. Cost of equipment Many instruments cost tens or even hundreds of thousands of dollars.

Low molecul ar mass organic molecul es, e.g. aspirin, quinine Organic molecul es, e.g. ethanol

lly lowviscosit y solutio ns, e.g. waste water Liquid and gas sample s e.g. sunscre ens, soft drinks Solids, liquids or gases

and precision; readily automated

expensive instrument; trained technician needed to operate Not suitable for very low concentratio ns

analysed by graphite furnace AAS in which the viscous liquid or solid is atomized in a tiny carbon cup

Relatively simple to operate; readily automated

As a detector for GC and HPLC can readily determine ppm levels of analytes

Huge range of analytes and samples; small sample size

The cost of running analytical instruments and the cost of consumables also varies. Some NMR machines use expensive liquid helium as a coolant. Expertise Are specialist staff required to operate the instruments and interpret the data? Quality data Costs are generally greater for high quality data. - Various techniques are used in chemical analysis. - The technique selected depends upon the chemical and physical properties of the analyte, the nature of the sample and economic considerations such as time, costs of purchasing and operating equipment, salary costs of staff, and the level of accuracy and precision required.