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Atomic Mass Spectrometry


Atomic Mass Spectrometry is:

a versatile and widely used tool for identifying the elements present in samples of matter and for determining their concentrations

Advantages over atomic optical spectrometric methods:




Detection limits that are, for many elements, as great as three orders of magnitude better than optical methods Remarkably simple spectra that are usually unique and often easily interpretable The ability to measure atomic isotopic ratios

Disadvantages over atomic optical spectrometric methods:




Instrument costs two to three times that of optical atomic instruments Instrument drift that can be as high as 5% to 10% per hour Certain types of interference effects

Some General Features of Atomic Mass Spectrometry

Steps in AMS analysis:




Atomization Conversion of a fraction of the atoms formed in step 1 to a stream of ions (usually singly charged positive ions) Separating the ions formed in step 2 on the basis of their mass-to-charge ratio (m/z); where m = mass number of the ion in amu and z = number of fundamental charges that it bears Counting the number of ions of each type or measuring the ion current produced when the ions formed from the sample strike a suitable transducer

Atomic Masses in Mass Spectrometry

Mass Spectrometers discriminate among the masses of isotopes but other analytical instruments do not Atomic and molecular masses are generally expressed in atomic mass units (amu), or daltons (Da)

Thus, the atomic mass unit is then:

Relative atomic mass

Chlorine-35 has a mass that is 2.914071 times greater than the carbon isotope:

Nominal mass

a whole number precision in a mass measurement

Chemical atomic mass

Mass-to-charge ratio

The mass-to-charge ratio of an ion is the unitless ratio of its mass number to the number of fundamental charges z on the ion. 12C 1H + , m/z = 16.0313/1 = 16.0313 4 13C 1H 2+ , m/z = 17. 0346/2 = 8.5173 4
Most ions in mass spectrometry are singly charged; so the term mass-to-charge ratio is often shortened to mass

Types of Atomic Mass Spectrometry

Hyphenated methods - Combinations of two instrumental techniques that produce analytical results superior in some way to the results from either of the original individual methods - First mass spectrometric methods developed for qualitative and quantitative elemental analysis

Mass Spectrometers

An instrument that produces ions and separates them according to their massto-charge ratios, m/z

Three types used in atomic mass spectrometry:

quadrupole mass spectrometer time-of-flight mass spectrometer double-focusing mass spectrometer

Principal components of all types of mass spectrometer

The inlet system introduces a micro amount of sample into the ion source where the components of the sample are converted into gaseous ions by (a) bombardment with electrons, photons, ions, or molecules or (b) applying thermal or electrical energy.

The output of the ion source is a stream of positive (most common) or negative gaseous ions that are then accelerated into the mass analyzer whose function is analogous to the monochromator in an optical spectrometer. Dispersion depends on the mass-to-charge ratio rather than the wavelength of photons.

The transducer converts the beam of ions into an electrical signal that can be processed, stored in the memory of a computer, and displayed. Unlike most optical spectrometers, mass spectrometers require an elaborate vacuum system to maintain a low pressure in all of the components except the signal processor and readout.

Low pressure ensures infrequent collisions in the mass spectrometer to produce and maintain free ions and electrons.

Transducers for Mass Spectrometry

Electron multipliers 1. Discrete-dynode 2. Continuous-dynode The Faraday Cup Array Transducers

Discrete-dynode electron multiplier

Designed for collecting and converting positive ions into an electrical signal

Continuous-dynode electron multiplier

Cornucopia Glass doped with lead Voltage gradient

Continuous-dynode electron multiplier

The Faraday Cup

The transducer is aligned so that ions exiting the analyzer strike the collector electrode This electrode is surrounded by a cage that prevents the escape of reflected ions and ejected secondary electrons The collector electrode is inclined with respect to the path of the entering ions so that particles striking or leaving the electrode are reflected from the entrance of the cup The collector electrode and cage are connected to ground through a large resistor The charge of the positive ions striking the plate is neutralized by a flow of electrons from ground

The Faraday cup is:

inexpensive and simple mechanically and electrically speed at which a spectrum can be scanned is limited because of the need for high-impedance amplifier less sensitive because it has no internal amplification

Electrooptical ion detector

Array Transducers:

Microchannel plate

Quadruple Mass Analyzers

Most common type of mass spectrometer More compact, less expensive, more rugged than most types Has high scan rates; entire mass spectrum can be obtained in less than 100 ms Mass filter

A quadruple mass spectometer

The heart of a quadrupole instrument is the four parallel cylindrical rods that serve as electrodes At any given moment, all the ions except those having a certain m/z value strike the rods and are converted to neutral molecules Only ions having a limited range of

Time of Flight Mass Analyzers

An order of magnitude poorer in sensitivity and in detection limits than comparable quadrupole systems Simple, rugged, ease of accessibility to the ion source, virtually unlimited mass range, rapid data-acquisition rate

Double-Focusing Analyzers

Inductively Coupled Mass Spectrometry

Low detection limits for most elements High degree of sensitivity Reasonably good precision and accuracy

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