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Mussarat Jabeen
• Powerful analytical technique
• Smallest scale
• Destructive technique
• Useful for identification of species

According to the IUPAC

(International Union of Pure and
Applied Chemistry), it is the branch
of science dealing with all aspects of
mass spectroscopes and results
obtained with these instruments.
Contents Brief History of Mass Spectrometry

Nobel prize pioneers

Mass spectrometer

Structural analysis and Fragmentation Patterns

interpretation of mass spectrum

Applications of mass spectrometry

Brief History of Mass Spectrometry

1897 J.J. Thomson. Discovered electrons by cathode

rays experiment. Nobel prize in 1906.

1919 Francis Aston recognized 1st mass spectrometer

and measure z/m of ionic compounds.

1934 First double focusing magnetic analyzer was

invented by Johnson and Neil.

1966 Munson and Field described chemical

1968 Electrospray Ionization was invented by Dole,
Mack and friends.

1975 Atmospheric Pressure Chemical Ionization

(APCI) was developed by Carroll and others.

F. Hillenkamp, M.Karas and co-workers describe

1985 and coin the term matrix assisted laser
desorption ionization (MALDI).

1989 w. Paul discovered the ion trap technique.

Nobel prize pioneers

Joseph John Francis William Wolfgang Paul John Bennet Koichi Tanaka
Thomson Aston 1989 Nobel Prize for Fenn 2002 Nobel Prize
1906 Nobel Prize for 1922 Nobel Prize for Physics 2002 Nobel Prize for Chemistry
Physics Chemistry (for the development for Chemistry (mass
(theoretical and (mass spectrograph, of the ion trap (for the spectrometric
experimental of isotopes, in a technique) development of analyses of
investigations on the large number of non- Soft Desorption biological
conduction of radioactive ionization Method) macromolecules)
electricity by gases) elements)
Mass spectrometer
Understanding Mass Spectrometry

In a mass spectrometer, the same thing is

happening, except it's atoms and molecules that are
being deflected, and it's electric or magnetic fields
causing the deflection. It's also happening in a cabinet
that can be as small as a microwave or as large as a
chest freezer.
Mass spectrometer is similar to a prism.

In the prism, light is separated into its

component wavelengths which are then
detected with an optical receptor, such as
visualization. Similarly, in a mass
spectrometer the generated ions are
separated in the mass analyzer, digitized and
detected by an ion detector.
Basic Components of Mass Spectrometer

Four basic components

• Sample inlet
• Ionization source
• Mass analyzer
• Ion detector
Mass spectrometer

Sample Introduction Techniques

Initial pressure of sample is 760 mmHg or

~10-6 torr

Two techniques

•Direct Insertion (commonly used in MALDI)

•Direct infusion or injection (commonly used in ESI)

Mass spectrometer

Direct Insertion sample introduction technique

very simple technique

Sample is placed on a prob and inserted into ionization source and then
subjected to any number of desorption processes, such as laser
desorption or direct heating, to facilitate vaporization and ionization.
Direct infusion or injection sample introduction technique

Frequently used due to high efficiently

Used in coupling techniques like GC-MS and HPLC-MS
Ionization Methods used in Mass spectrometry

Commonly used

•Transfer of a charged molecule to the gas phase
•Electron ejection
•Electron capture

Formation of positive ions by the addition of a proton

Used for basic compounds like amines, peptides
Used in MALDI, APCI and ESI

Give net negative charge of 1- by removal of one proton

Used for acidic species like phenols, carboxylic acid, sulfonic acid etc.
Used in MALDI, APCI and ESI

produces a charged complex by non-covalently adding a

positively charged ion like alkali metal ion or ammonium ion
to a neutral molecule.
Used for Carbohydrates
Used in MALDI, APCI and ESI
Transfer of a charged molecule to the gas phase

Cation from solution to gas

Used in MALDI or ESI
Electron ejection

Electron is ejected to give positive ion

Usually for non-polar compounds with low
molecular weights like anthracene.
Electron capture

a net negative charge of 1- is achieved

with the absorption or capture of an
Used for halogenated compounds
Ionization Sources in mass spectrometer

•Electrospray Ionization (ESI)

•Nanoelectrospray Ionization (NanoESI)
•Atmospheric Pressure Chemical Ionization (APCI)
•Atmospheric pressure photoionization (APPI)
•Matrix-assisted laser desorption/ionization mass
spectrometry (MALDI-MS)
•Fast Atom Bombardment (FAB)
•Electron Ionization (EI)
•Chemical Ionization (CI)
•Thermal ionization (TI)
Ionization Sources

Hard ionization sources Soft ionization sources

leave excess Little excess

energy in energy in
molecule and molecule and
produced stable produced
fragments which unstable
is not further fragments
fragarmented which are
Electrospray Ionization (ESI)
The sample solution is sprayed from a region of the
strong electric field at the tip of a metal nozzle
maintained at a potential of anywhere from 700 V to
5000 V. The nozzle (or needle) to which the potential is
applied serves to disperse the solution into a fine spray
of charged droplets. Either dry gas, heat, or both are
applied to the droplets at atmospheric pressure thus
causing the solvent to evaporate from each droplet

For example peptides, proteins, carbohydrates,

small oligonucleotides, synthetic polymers, and
Nanoelectrospray Ionization (NanoESI)

where the spray needle has been made very small and
is positioned close to the entrance to the mass analyzer.
The end result of this rather simple adjustment is
increased efficiency, which includes a reduction in the
amount of sample needed.

•Very sensitive
•very low flow rates
•Very small droplet size (~5µ)
Atmospheric Pressure Chemical Ionization (APCI)

the liquid effluent of APCI is introduced directly into the ionization source.
However, the similarity stops there. The droplets are not charged and the
APCI source contains a heated vaporizer, which facilitates rapid
desolvation/vaporization of the droplets. Vaporized sample molecules are
carried through an ion-molecule reaction region at atmospheric pressure.
Atmospheric pressure photoionization (APPI)

it generates ions directly from

solution with relatively low
background and is capable of
analyzing relatively nonpolar

APPI vaporized sample passes through ultra-violet

APPI is much more sensitive than ESI or APCI.
Matrix-assisted laser desorption/ionization mass spectrometry

the analyte is first co-crystallized with a large molar excess of a matrix compound, usually a UV-
absorbing weak organic acid. Irradiation of this analyte-matrix mixture by a laser results in the
vaporization of the matrix, which carries the analyte with it. The matrix plays a key role in this
technique. The co-crystallized sample molecules also vaporize, but without having to directly
absorb energy from the laser. Molecules sensitive to the laser light are therefore protected from
direct UV laser excitation.
Fast Atom Bombardment (FAB)
Immobilized matrix is bombarded with a fast
beam of Argon or Xenon atoms. Charged
sample ions are ejected from the matrix and
extracted into the mass

Used for large compounds with low volatility (eg

peptides, proteins, carbohydrates)
Solid or liquid sample is mixed with a non-
volatile matrix (eg glycerol, crown
ethers, nitrobenzyl alcohol)
Electron Ionization (EI)

Energetic process a heated filament emits electrons which are

accelerated by a potential difference of usually 70eV into the sample
Ionization of the sample occurs by removal of an electron from the
molecule thus generating a positively charged ion with one unpaired

•Produces M+.radical cation giving molecular weight

•Produces abundant fragment ions
Chemical Ionization (CI)

process is initiated with a reagent gas such as

methane, isobutane, or ammonia, which is ionized by
electron impact.
High gas pressure in the ionization source is required
for the reaction between the reagent gas ions and
reagent gas neutrals.

possible mechanism
Reagent (R) + e- → R+ + 2 e-
R+ + RH → RH+ + R
RH+ + Analyte (A) → AH+ + R

biologically important molecules

(sugars, amino acids, lipids etc.).
Thermal ionization (TI)

Samples are deposited on rhenium or tantalum filament

and then carefully evaporated and sent to mass analyzer.

used to
•quantify toxic trace elements in foods.
•measurement of stable isotope ratio of
inorganic elements.
Mass Analyzer
Properties of mass Analyzer

Accuracy Mass Range Resolution Scan Speed

is a measure of The range over A measure of Analyzers

how close the value which a mass how well a are scanned
obtained is to the spectrometer mass with a
true value. The analyzer can spectrometer regular cycle
accuracy varies operate. separates time from
dramatically from ions of low to high
analyzer to different mass m/z or vice
analyzer depending versa.
on the analyzer
type and resolution.
Mass Analyzer

•Quadrupole Ion Trap
•Linear Ion Trap
•Double-Focusing Magnetic Sector
•Quadrupole Time-of-Flight Tandem MS
•Quadrupole Time-of-Flight MS
-ions travel parallel to four rods
- opposite pairs of rods have
rapidly alternating potentials
- ions try to follow alternating
field in helical trajectories
- stable path only for one m/z
value for each field frequency

Smalll and low cost

Rmax ~ 500
Harder to push heavy molecule - m/zmax < 2000
Quadrupole Ion Trap

The quadrupole ion trap typically consists of a ring electrode and two hyperbolic endcap
electrodes. The motion of the ions induced by the electric field on these electrodes allows ions
to be trapped or ejected from the ion trap. In the normal mode, the radio frequency is scanned
to resonantly excite and therefore eject ions through small holes in the endcap to a detector. As
the RF is scanned to higher frequencies, higher m/z ions are excited, ejected, and detected.
Linear Ion Trap

The linear ion trap differs from the 3D ion trap as it confines ions along the axis of a
quadrupole mass analyzer using a two-dimensional (2D) radio frequency (RF) field
with potentials applied to end electrodes. The primary advantage to the linear trap
over the 3D trap is the larger analyzer volume lends itself to a greater dynamic ranges
and an improved range of quantitative analysis.
Double-Focusing Magnetic Sector
the ions are accelerated into a magnetic field using an electric field. A charged particle
traveling through a magnetic field will travel in a circular motion with a radius that depends on
the speed of the ion, the magnetic field strength, and the ion’s m/z. A mass spectrum is
obtained by scanning the magnetic field and monitoring ions as they strike a fixed point
Quadrupole Time-of-Flight Tandem MS

Time-of-flight analysis is based on accelerating a group of ions to a detector where

all of the ions are given the same amount of energy through an accelerating
potential. Because the ions have the same energy, but a different mass, the lighter
ions reach the detector first because of their greater velocity, while the heavier
ions take longer due to their heavier masses and lower velocity. Hence, the
analyzer is called time-of-flight because the mass is determined from the ions’ time
of arrival. Mass, charge, and kinetic energy of the ion all play a part in the arrival
time at the detector.
Quadrupole Time-of-Flight MS

Quadrupole-TOF mass analyzers are typically coupled to

electrospray ionization sources and more recently they have
been successfully coupled to MALDI. It has high
efficiency, sensitivity, and accuracy as compared to
Quadrupole and TOF analyzer.
Detectors used in mass spectrometer

Faraday Cup

Photomultiplier Conversion Dynode

Array Detector

Charge (or Inductive) Detector

Electron Multiplier
Faraday Cup
A Faraday cup involves an ion striking
the dynode (BeO, GaP, or CsSb)
surface which causes secondary
electrons to be ejected. This temporary
electron emission induces a positive
charge on the detector and therefore a
current of electrons flowing toward the

not particularly sensitive

offering limited amplification of signal
is tolerant of relatively high pressure.

– Ions are accelerated toward a grounded “collector electrode”

– As ions strike the surface, electrons flow to neutralize charge, producing a small
current that can be externally amplified.
– Size of this current is related to # of ions in
– No internal gain → less sensitive
Photomultiplier Conversion Dynode

the secondary electrons strike a phosphorus

screen instead of a dynode. The phosphorus
screen releases photons which are detected by
the photomultiplier. Photomultipliers also
operate like the electron multiplier where the
striking of the photon on scintillating surface
results in the release of electrons that are then
amplified using the cascading principle.

is not as commonly
Life limit is high as compared to others.
Array Detector
detects ions according to their different m/z, has
been typically used on magnetic sector mass

The primary advantage of this approach is that,

over a small mass range, scanning is not
necessary and therefore sensitivity is improved.
Charge (or Inductive) Detector

Charge detectors simply recognize a

moving charged particle (an ion) through
the induction of a current on the plate as
the ion moves past

Detection is independent of ion size.

Mass spectrometer
Electron Multiplier
•Most important part
•made up of a series (12
to 24) of aluminum oxide
(Al2O3) dynodes
•Used for increasing

Ions strike the first dynode surface causing an

emission of electrons. These electrons are then
attracted to the next dynode held at a higher
potential and therefore more secondary
electrons are generated.
Mass spectrometer

Vacuum in the Mass Spectrometer

All mass spectrometers need a
vacuum to allow ions to reach
the detector without colliding
with other gaseous molecules
or atoms. If such collisions did
occur, the instrument would
suffer from reduced resolution
and sensitivity.
Mass spectrometer

Structural analysis and Fragmentation Patterns

Mass spectrum

Graph of ion intensity

(relative abundance)
along x-axis versus
mass-to-charge ratio
(m/z) (units
daltons, Da) along Y-

•Molecular ion (Parent ion)

•Fragmentation peaks
•Base peak
•Isotopic peaks
Mass spectrometer

Molecular ion (Parent ion)

the peak corresponding

to the mol wt of the

The peak of an ion

formed from the original
molecule by electron
ionization, by the loss of
an electron, or by
addition or removal of
an anion or cation and
also known as parent
peak, radical peak.
Mass spectrometer

Fragmentation peaks
The peaks observed by fragments of

The molecular ions are energetically

unstable, and some of them will break up
into smaller pieces. The simplest case is
that a molecular ion breaks into two
parts - one of which is another positive
ion, and the other is an uncharged free

The uncharged free radical won't produce a line on the mass

spectrum. Only charged particles will be accelerated, deflected and
detected by the mass spectrometer. These uncharged particles will
simply get lost in the machine - eventually, they get removed by the
vacuum pump.
Base peak
The most intense (tallest) peak in a mass spectrum, due to the
most abundant ion. Not to be confused with molecular ion: base
peaks are not always molecular ion and molecular ion are not
always base peaks.
Fragmentation Patterns

By using fragmentation pattern we can easily study the structure of

a compound.

Stevenson’s Rule
Homolytic bond cleavage
Heterolytic fragmentation
Alpha cleavage
Inductive cleavage
Retro Diels-Alder Cleavage
McLafferty rearrangement
Ortho effect
Onimum Reaction
CO Elimination
Stevenson’s Rule
The most probable fragmentation is the one that leaves
the positive charge on the fragment with the lowest
ionization energy
In other words, fragmentation processes that lead to the
formation of more stable ions are favored over
processes that lead to less-stable ions.

Cleavages that lead to the formation of more stable

carbocations are favored. When the loss of more than
one possible radical is possible, a corollary to
Stevenson’s Rule is that the largest alkyl radical to be
lost preferentially.
Homolytic bond cleavage

A type of ion fragmentation in which a bond is broken by

the transfer of one electron from the bond to the charged
atom, the other electron remaining on its starting atom.
The movement of one electron is signified by a fishhook
arrow. The fragmentation of a ketone is shown in the
Heterolytic bond cleavage

type of ion fragmentation in which a bond is broken by

the transfer of a pair of electrons from the bond to the
charged atom

The movement of 2 electrons is signified by a double-

barbed arrow and also referred to as charge-induced
Alpha cleavage
Alpha cleavage occurs on α-bonds adjacent to
heteroatoms (N, O, and S). Charge is stabilized by
heteroatom. Occurs only once in a fragmentation
(cation formed is too stable to fragment further)

For example in alcohols, aliphatic ethers, aromatic ethers, cyclic

compounds and aromatic ketones etc.
Fission of a bond two removed from a heteroatom or
functional group, producing a radical and an ion. Also
written as β-cleavage. For example allylic fragmentation.
Inductive cleavage

If an electron pair is completely

transferred towards a centre of
positive charge as a result of the
inductive effect, shown
schematically by the use of a
double-headed arrow, then the ion
will fragment by inductive
cleavage. The figure illustrates
this for a radical cation ether.
Retro Diels-Alder Cleavage

A multicentered ion fragmentation which is the

reverse of the classical Diels-Alder reaction
employed in organic synthesis that forms a cyclic
alkene by the cycloaddition of a substituted diene
and a conjugated diene. In the retro reaction, a
cyclic alkene radical cation fragments to form
either a diene and an alkene radical cation or a
diene radical cation and an alkene. Depending on
the substituents present in the original
molecule, the more stable radical cation will
McLafferty rearrangement
An ion fragmentation characterised by a
rearrangement within a six-membered ring
system. The most usual configuration is for a
radical cation formed by EI to undergo the
transfer of a γ- hydrogen atom to the ionisation
site through a ring system as shown here.

The distonic radical cation so formed can break up by radical-

site-induced (α), or charged site-induced fragmentation as
shown in the figure. For example ketones, carboxylic acid and
Ortho effect

The interaction between substituents oriented ortho, as opposed to para

and meta, to each other on a ring system, can create specific
fragmentation pathways. This permits the distinction between these
isomeric species. The diagram shows a case in which only the ortho
isomer can undergo the rearrangement.
Onium Reaction
Onium Ion: A hypervalent species
containing a non-metallic element such
as the methonium ion CH5+. It includes
ions such as
oxonium, phosphonium, and nitronium
Mostly observed in cationic fragments containing
a heteroatom as charge carrier, e.g.
oxonium, ammonium, phosphonium and
sulphonium ions.

The onium reaction is not limited to alkyl

acyl groups can also undergo the
onium reaction
CO Elimination
Cyclic unsaturated carbonyl compounds and
cationic carbonyl fragments
which resulted from an a-cleavage tend to
eliminate CO .

If there is more than one CO group present

sequential elimination of all CO
groups is possible.
From carbonyl compounds CO elimination reaction
takes place like in aldehyde, ketones and phenols
Rules for interpretation of mass spectrum

•DBR Calculations
•Nitrogen Rule
•Isotopic effect
DBR Calculations

Double bond or ring calculations tell us about how many rings or double
bonds are present in a compound.
DBR= C-H/2+N/2+1
C= number of carbon atoms
H= number of hydrogen atoms
N= number of nitogen atoms
Nitrogen Rule
•If a compound contains an even number of nitrogen atoms (or no
nitrogen atoms), its molecular ion will appear at an even mass number.
• If, however, a compound contains an odd number of nitrogen
atoms, then its molecular ion will appear at an odd mass value.
• This rule is very useful for determining the nitrogen content of an
unknown compound.
Isotopic effect
Mass spectra (examples)

Strong M+ (but intensity decreases with an increase of branches.
Carbon-carbon bond cleavage
loss of CH units in series: M-14, M-28, M-42 etc
Strong M+, strong base peak at M-28 (loss of ethene)
A series of peaks: M-15, M-28, M-43 etc
Methyl, ethyl, propyl with an additional hydrogen give peaks
Alkenes Strong M+
Fragmentation ion has formula CnH2n+ and CnH2n-1
A series of peaks: M-15, M-29, M-43, M-57 etc
Strong M+
Strong base peak at M-1 peak due to the loss of terminal hydrogen
Alpha cleavage
Aromatic Hydrocarbons
Strong M+
Loss of hydrogen gives base peak
McLafferty rearrangement
Formation of benzyl cation or tropylium ion
M+ weak or absent
Loss of alkyl group via a-cleavage
Dehydration (loss of water) gives peak at M-18
Strong M+
M-1 due to hydrogen elimination
M-28 due to loss of CO
M-29 due to loss of HCO (formyl radical)
M+ weak but observable
Loss of alkyl radical due to a-cleavage
B-cleavage( formation of carbocation fragments through loss of alkoxy radicals)
C-O bond cleavage next to double bond
Peaks at M-31, M-45, M-59 etc
Aldehyde M+ weak, but observable (aliphatic)
Aliphatic : M-29, M-43 etc
McLafferty rearrangement is common gives the base peak
M+ strong (aromatic)
Aromatic: M-1 (loss of hydrogen)
M-29 (loss of HCO)
McLafferty rearrangement is common
Strong M+
A series of peaks M-15, M-29, M-43 etc
Loss of alkyl group attached to the carbonyl group by a-cleavage
Formation of acylium ion (RCO+)
McLafferty rearrangement
M+ weak but generally observable
Loss of alkyl group attached to the carbonyl group by a-cleavage
Formation of acylium ion (RCO+)
McLafferty rearrangement
Acyl portion of ester OR+
Methyl esters: M-31 due to loss of OCH3
Higher esters: M-32, M-45, M-46, M-59, M-60, M-73 etc
Carboxylic acids
Aliphatic carboxylic acids:
M+ weak but observable
A-cleavage on either side of C=O
M-17 due to loss of OH
M-45 due to loss of COOH
McLafferty rearrangement gives base peak
Aromatic carboxylic acids:
M+ Strong
A-cleavage on either side of C=O
M-17 due to loss of OH
M-18 due to loss of HOH
M-45 due to loss of COOH
McLafferty rearrangement gives base peak
M+ weak or absent
Nitrogen rule obey

M+ weak but observable

M-1 visible peak due to loss of termiminal hydrogen
Nitro Compounds

M+ seldom observed
Loss of NO+ give visible peak
Loss of NO2+ give peak
Alkyl chloride and alkyl bromides
Strong M+2 peak
For Cl M/M+2 = 3:1
F or Br M/M+2 = 1:1
Loss of Cl or Br
Loss of HCl or HBr
Alkyl chloride
Applications of Mass Spectrometry
The technique has both quantitative and qualitative
uses. These include identifying unknown compounds,
determining the isotopic composition of elements in a
molecule, and determining the structure of a
compound by observing its fragmentation. Followings
are the main applications

Toxicity of Toothpastes
Measuring nanoparticle size
Protein characterization
Space exploration
Isotope dating and tracking
Molecular weight
Reaction mechanism
Toxicity of Toothpastes
DEG (diethylene glycol) which is a toxic chemical and usually present in
Chinese toothpastes.

Measuring nanoparticle size

Mass spectrometry is used to measure nanoparticle size like platinum
nanoparticles which is used as catalyst.
Once size of a sphere is measured, its density is also calculated.
Pharmacokinetics is often studied using mass spectrometry because of the
complex nature of the matrix (often blood or urine) and the need for high
sensitivity to observe low dose and long time point data.
Protein characterization
Mass spectrometry is an important emerging method for the
characterization of proteins. The two primary methods for ionization of
whole proteins are electrospray ionization (ESI) and (MALDI).

Space exploration
Mass spectrometers are also widely used in space missions to measure the
composition of plasmas. For example, the Cassini spacecraft carries the
Cassini Plasma Spectrometer (CAPS),[44] which measures the mass of ions
in Saturn's magnetosphere.

Isotope dating and tracking

Mass spectrometry is also used to determine the isotopic composition of
elements within a sample. Differences in mass among isotopes of an
element are very small, and the less abundant isotopes of an element are
typically very rare, so a very sensitive instrument is required. These
instruments, sometimes referred to as isotope ratio mass spectrometers
Molecular weight
Molecular weight can be determined by mass spectrometry.
Actual number of carbons, hydrogen, oxygen etc
By using relative intensities(peak hight), we can easily calculated the actual
numbers of C,H,O etc atoms.

Bonding can be studied by fragmentation patterns for example, beta
cleavage is possible only if double bonds or heteroatom present.

Reaction mechanism
Mass spectrometry is best technique to study reaction mechanism and
intermediates produced in reaction, for example, in carboxylic acid and
alcohols a peak at M-18 indicates that water is produced.
Determination of Elements

Bulk materials such as steel or refractory

Detection limits in ICPMS as in Table
metals, elements are determined by low-
resolution glow-discharge mass spectrometry.
High-resolution GDMS has been used to study
semiconductor materials. GDMS is considered
virtually free of matrix effects.
Species Analysis

Heavy metals in the environment are stored in complexes with

humic acids, can be converted by microbes in different
complexes, and can be transported in live animals and humans.
This applies to many elements such as
lead, mercury, arsenic, astatine, tin and platinum

For example, tin and lead alkylates established in

soil, water or muscle tissue by GC / MS after exhaustive
alkylation or thermal spray, and ICP-LC/MS API methods.
Environmental Chemistry

the analysis of trace elements and compounds

in environmental samples like air, water, soil etc
because of its detection power, specificity and
structural analysis functions
Generally, sample preparation is at least one
type of chromatography coupled with MS either
offline or online like GCMS

Dictionary of Mass Spectrometry, A.I. Mallet and S. Down, 2009

Introduction to spectroscopy, Donald L. Pavia
Hand book of spectroscopic data, B.D.Mistry.
Comprehensive analytical chemistry.
. Handbook of Spectroscopy, by G. Gauglitz and T. Vo-Dinh
Instant notes of Analytical chemistry, D.Kealey.
Modern Analytical Chemistry, David Harvey.
The Basics of Spectroscopy, David.W.Ball.
Encyclopedia of Analytical Chemistry Applications, Theory and
Instrumentation Edited by R.A.Meyers
Handbook of Analytical Techniques edited by Helmut Giinzler and Alex
Williams 1st Edition 2001
Encyclopedia of Spectroscopy and Spectrometry part 2(M-Z) Edited By
john C. lindon, George E. Tranter and John L. Holmes