Chem-805

Identification of organic and inorganic compounds by spectroscopy

Mass Spectrometry NMR Infrared

Mass Spectrometry
Simplest form of mass spectrometer performs 4 essential functions: (under vacuum 10-6 mm Hg)

It subjects vaporized molecules to bombardment by a stream of high-energy electrons, converting these molecules to ions These ions are then accelerated in an electric field The accelerated ions are then separated according to their mass-to-charge ratio in a magnetic or electric field The ions that have a particular mass-to-charge ratio are then detected by a device that counts the number of ions striking it

Mass Spectrometry: Introduction

MS is concerned with the separation of matter according to atomic and molecular mass. With recent development and improvement of instrumentation and techniques it can be used in the analysis of organic compounds of molecular mass up to as high as 200,000 Daltons.

MS uses magnetic and electric fields to exert forces on charged particles (ions) in a vacuum. Therefore, a compound must be charged or ionized to be analyzed by a mass spectrometer.

Mass Spectrometry
Atomic and molecular weight are expressed in Atomic Mass Unit (amu). The amu is based on a relative scale in which
12C

is assigned exactly 12 amu. Also called dalton

Each isotope has specific exact mass. MS is interested in exact mass up to 3-4 figures after decimal point (high resolution HR). Chemical atomic weight is the average weight taking into account the mass of each isotope and their natural abundance.

Components of a mass spectrometer

10-5 to 10-8 Torr System Inlet Ion Source Mass Analyzer Detector

Vacuum System

Signal processor

m/z

MS : Ionization
1. Gas Phase:
1. Electron ionization (EI) 2. Chemical ionization (CI) 3. Field Ionization (FI)

2. Desorption
1. 2. 3. 4. 5. 6. 7. 8. Field Desorption (FD) Fast Atom Bombardment (FAB) Secondary Ion Mass Spectrometry (SIMS) Laser Desorption (LD) Plasma Desorption (PD) Thermal Desorption Thermospray ionization (TS) Electrospray (ES)

Mass analyzers: Magnetic sector

In Magnetic Field (H) an ion of charge z and mass m experiences centripal force Hzv (where v is the velocity of the ion). At the same time, any particle moving on a circle of radius r experiences centrifugal force of mv2/r When these two forces are equal the ion travel on a circle and Hzv = mv2/r m/z = Hr/v We could measure v, the velocity of the ion to determine the mass but this is very difficult experimentally

Mass Spectrometer
If a molecule absorb an electron (creating a Negative Ion), It will be absorbed by the repeller plate The repeller plate (Positively charged) directs the ions through a series of accelerating plates Kinetic Energy : 1 mv2 = eV 2

In Magnetic Field (H) ions describe a curved Path (r -> curvature)

r = mv eH
Ions with reater m/e have larger curve Instruments has fixed curve => only particules with correct m/e can reach detector Magnetic field is varied to detect all ions

m = H2 r2 e 2v

Components of MS: Mass Analyzers

Mass Analyzer Dispersion of the ions is based on mass-to-charge ratio

There are several type of mass analyzers.

1. 2. 3. 4. 5. 6.

Magnetic sector Electrostatic and Magnetic sector Quadrupole MS filter Ion trap analyzers TOF Time-of-Flight FT-MS

Components of MS: Detector, Vacuum

Detector Convert the beam of ions in an electrical signal that can be processed, stored, displayed and recorded in many ways.

Electron Multiplier (most commonly used)

Other:

Faraday cup Photographic plates Scintillation type

MS require the high vacuum is maintained in all spectrometer components (except signal processing)

Vacuum System

Amplifying signal

Continuous Dynode electron multiplier Provide high gain and nanosecond response time.

Mass Spectrum
Ionization: CH3OH + eCH3OH+ + 2em/z 32 Molecular ion Fragmentation: [CH3OH]+ [CH2OH] + + H

m/z 31
CH3+ + HO m/z 15 B Base Peak 100%

CHO+ + H2
m/z 29

Tabular presentation Bar graph presentation

B+

Benzamide: EI

M+

77

44 - NH2

C O

NH2

C6H5C=O + - CO m/z 105

C6H5+ m/z 77

105

3-methyl-6-i-PropylCyclohex-2-ene-1-one

MW = 152

Isotopic cluster M, M+1, M+2

Natural Abundance of a few elements

Isotope
1H 2H

Atomic weight 1.008

Mass 1.00783 2.01410

% Abundance 99.99 0.016

12C 13C 14N 15N 16O 17O 18O

12.011

12.0000 (std) 98.89 13.00336 1.11 14.0031 15.0001 15.9949 16.9991 17.9992 99.64 0.36 99.76 0.04 0.20

14.0067

15.9994

Natural Abundance of a few elements

Isotope
19F

Atomic weight 18.998 28.0855

Mass 18.9984 27.9769 28.9765 29.9738 31.9721 32.9715 33.9679 34.9689 36.9659

% Abundance 100.0 92.17 4.71 3.12 99.64 0.76 4.20 75.77 24.23

28Si 29Si 30Si 32S 33S 34S 35Cl 37Cl

32.066

35.4527

Natural Abundance of a few elements

Isotope
31P 79Br 81Br

Atomic weight 30.9738 79.9094

Mass 30.9738 78.9183 80.9163

% Abundance 100.0 50.52 49.48

126I

126.9045

126.9045

100.00

The Atomic weight:

Average atomic weight of all isotopes with their natural abundances

Atomic weight Br: [% 79Br x 78.9183] + [% 81Br x 80.9163] [50.52 x 78.9183] + [49.48 x 80.9163] = 79.9094

Natural Abundance of a few elements

Molecular formula
e.g C7H7NO :

M+ (molecular ion) m/z M mass of the most abundant isotope 7 x 12C = 84 7 x 1H = 7 1 x 14N = 14 1 x 16O = 16 m/z 121

Isotope peaks: (% respect to M)

M+1 due to (13C) or 15N (17O) or 2H are negligeable)

%(M+1) = (1.1 * #C) + (.38 * #N) = 8.08 % %(M+2) = (1.1 * #C)2/200 + (.2 * #O) = 0.5% For C, H, N,O, F, P composition

Molecular formula in general

Molecular ion: Even Mass : can contain C, H, O , halogen, even # N Odd Mass : can contain C, H, O , halogen, odd # N Fragmentation ions:

Even Mass : From even mass M+ comes from rearrangement or 2 bond breaking Odd Mass : From even mass M+ comes from single bond breaking
even Mass : from Odd Mass M+ comes from single bond breaking

Molecular formula: RULE of 13

Consider CH unit 13 amu

If we divide the mass by 13 we can establish easily possible formula:

Example: Molecular ion => 152 152 / 13 = # carbons = 11
Mass = 12 * 11 = 132 therefore H = 152 132 = 20

Basic formula C11 H20

If Oxygen is present : mass = 16 remove CH4 If Nitrogen is present : mass = 14 remove CH2 If one oxygen : If second oxygen : If third oxygen :

C11 H20 CH4 + O = C10 H16 O C10 H16 O CH4 + O = C9 H12 O2 C9 H12 O2 CH4 + O = C8 H8 O3

Molecular formula: RULE of 13

After establishing the basic formula with only Carbon/hydrogen, Other element can be introduced by substracting the proper hydrocarbon value 16O => CH4
14N 19F

=> =>

CH2 CH7

1H

28Si
31P 32S 35Cl 79Br 127I

=>
=> => => => =>

C2H4
C2H7 C2H8 C2H11 C6H7 C10H7

12

=>

Nitrogen rule

Molecular ion => 26 26 / 13 = # carbons = 2

Mass = 12 * 2 = 24 therefore H = 2

Molecular ion => 27 odd! 27 / 13 = # carbons = 2 Basic formula C2 H3 One Nitrogen C2 H3 - CH2 + N
H C N

Basic formula C2 H2
H C C H

Nitrogen rule
OH NH2

Molecular ion => 100 100 / 13 = # carbons = 7

Mass = 12 * 7 = 84 therefore H = 16

Molecular ion => 99 odd! Basic formula C7 H16

Basic formula C7 H16 1 Oxygen: C7 H16 - CH4 + O C6 H12 O

1 Nitrogen: C7 H16 CH2 + N

C6 H14 N

Calculating M+1 and M+2

Isotope peaks
Usually [M+2] peak is very small

Except for:
M Sulfur :
32S

M+1

M+2
34S

: 100

: 4.4

Silicon :
Chlorine : Bromine :

28Si:

100

29Si:

5.2

30Si

: 3.35
: 32.5 : 98

35Cl

: 100 : 100

37Cl

79Br

81Br

Isotope peaks : CH3Br

[12CH379Br]+ [12CH381Br]+

M-H
[12CH279Br]+

[13CH379Br]+

[12CH281Br]+ [13CH381Br]+

Bromine
79Br 81Br

79Br 81Br

2 intense peaks for the molecular ion, spaced by 2 daltons.

79Br

and 81Br

Chlorine
35Cl

(P= .75) 37Cl (P= .25) Ratio 3:1

Probability : [M+] / [M + 2] = 0.75 / 0.25 = 3 / 1

100 : 33

Calculation of isotope pattern: 2 Cl

C2H235Cl2 1 Cl C2H235Cl 37Cl C2H237Cl 35Cl C2H2 37Cl2

2 Cl
P (2 35Cl) = (0.75 )2 = 0.563 P (35Cl 37Cl) + P (37Cl 35Cl ) = (0.75 ) (0.25 ) + (0.25 ) (0.75 ) = 0.375 P (2 37Cl) = (0.25 )2 = 0.063 [M+] / [M + 2] / [M + 4] = 100 / 66 / 11

Calculation of isotope pattern: ClBr

35Cl

=> .75 => 51%

37Cl

=> .25
81Br

79Br

=> 49%

[RClBr]+ can exist as 4 isotopic forms:

35Cl 79Br 35Cl 81Br
37Cl 79Br

0.75 x 0.51 = 38%

50%

M+2 0.75 x 0.49 = 37%

M+2 0.25 x 0.51 = 13%

37Cl 81Br

M+4 0.25 x 0.49 = 12%

At very high resolution, the 2 (M + 2) peaks can be distinguished (separated by 0.001 Dalton)

Chlorine and Bromine

The Molecular ion M+ is always the lowest mass peak in the ion cluster (regardless of its relative intensity)

Isotopic abundances for Carbon containing compounds

M+ => p(M) = p(n 12C) = (0.989)n The probability of finding 1 13C among n carbons is: [M+1]+ => p(M+1) = p(n -1) 12C + 1 13C = n p[n-1] 12C x p(13C) = n(0.989)n-1 (0.011) Relative ratio: [M+1]+ / [M+ ] = n(0.989)n-1 (0.011) / (0.989)n = n (0.011) / (0.989) = n (0.0111)

In percentage: n x 1.1 %

Isotopic abundances for Carbon containing compounds

When comparing calculated abundances with observed intensities: We see that the ratio is not identical: due to experimental error

The relative abundance of the larger peaks are reproducible to 10%

For smaller peaks, relative intensity is larger

Generally speaking, The size of the [M+1]+ ion can be used to figure out the number of carbons in a molecule
For example, if molecular ion is observed at m/z 118

and the ion at m/z 119 has an intensity of about 9%

There are probably 8 carbons (1.1% x 8 = 8.8% )

Isotopic abundances for Carbon containing compounds

Due to the relatively large error on peak intensity ( 10%) determination of the number of carbons is sometime ambiguous For example: [M+1]+ => intensity 22.5 2.3% Range covers 20.2 to 24.8 => 20 2 carbons

Isotopic abundances for other common nuclei

For 15N: [M+1]+ / [M]+ => n x 0.36%

For 33S: [M+1]+ / [M]+ => n x 0.80%

For 18O: [M+2]+ / [M]+ => n x 0.20%

For 34S: [M+2]+ / [M]+ => n x 4.42%

Calculating Peak Intensities from Isotopic abundances

Isotopic abundances for Silicon

Often observed is TMS compounds
M+2 larger than usual

Often observed either from GC column Or septum

Isotopic abundances for Sulfur

SO+ M+2 M+2

For 18O: [M+2]+ / [M]+ => n x 0.20%

For 34S: [M+2]+ / [M]+ => n x 4.42%

[M+2]+ = 4.42 + (2 x 0.20) = 4.82%

isotope pattern: 2 Cl (example)

When there are many carbons, isotopic pattern for 13C adds up to chlorine pattern

Steps in the Identification of Unknown

Identify Molecular ion M.+ Determine Molecular Formula (odd / even mass) Analyze heteroatom (M+1 and M+2 ) S, Si, Cl, Br, . Use rule of 13 to determine # Carbons (M+1 and M+2 ) Compare with 13C-NMR (# carbons) with APT experiment (JMOD) ( # protons) Compare with proton NMR ( # protons) Identify base peak (note if even / odd) One or two bond fragmentation Test your conclusions: in lab make derivatives (TMS or Na or K complexes mass shift)

Solving problems in MS
Try to identify the Molecular Ion or decide if it is present (most critical step in solving a structure)
Check if [M+1]+ ion is too large to accommodate reasonable number of carbons. (the [M+1]+ ion might be the very small M+ instead!) Determine the first loss from proposed molecular ion. Some loss are impossible (e.g 12, 14, 23 daltons) Does the spectrum appear dirty? (lots of small peaks even at high mass) If GC of the comopund Is available, compare retention time

Is the molecular weight even or odd?

An odd mass can be associated with an odd number of Nitrogen An even mass means no Nitrogen or an even number of Nitrogen This Rule is applicable only to Molecular ion and to odd-electron ions

Examine ion cluster for isotopic natural abundance (look for special heteroatom pattern). Try to calculate number of carbons

Solving problems in MS
From the overall appearance: is it a fragile compound? Is it likely to be aromatic or aliphatic? Look in the low mass ions. Do you see any clues of the family of compounds that you might be dealing with? Make a list of suggested losses from the molecular ion and try to make a pattellsrn from them. Look for intense odd-electron ions in the spectrum: this is almost impossible in compounds containing Nitrogen! These provides clues for rearrangements (retro Diels Alder, McLafferty) Speculate on the structure using all that information Index of Hydrogen deficiency

CxHyNzOn

Index = x y + z +1

Neutral losses and Ion series

M-1 H M-30 M-15 CH3 NO (Nitro compounds), H2 CO (anisoles)

M-16 M-17 M-18 M-19

O (rare) , NH2 OH , NH3 (rare) H2O F

M-31 CH3O
M-32 CH3OH M-35 Cl

M-20 HF (very rare) M-26 HCCH , CN

M-36 HCl
M-42 CH2=C=O, CH2=CH-CH3 M-43 CH3CO , C3H7 M-44 CO2 M-45 CH3CH2O , CO2H

M-27 HCN
M-28 H2C=CH2 , CO M-29 CH3CH2 , HCO

Neutral losses and Ion series

Figuring out which peak is molecular ion can be supported by identifying what fragment is lost. There can be sometimes 2 consecutive loss: In steroid, M-33 is often observed: comes from the loss of Me and H2O The ions loss are only useful from molecular ion There is no fragment in organic compounds between M-1 and M-15 Loss of M-14 is never observed! Other gaps in mass loss are: between 21-25, 33-34, 37-41 Ions in these areas should be viewed suspiciously: either compound is not pure or postulated molecular ion is wrong

Neutral losses and Ion series

Among the losses: most common are Loss of H, CH3 , H2O (from some oxygenated compounds),

HCCH (from aromatic compounds),

HCN (from aromatic compounds containing Nitrogen), CO and CH2=CH2 (both at 28! Difficult to tell which one is lost)

Ethyl radical (29)

Methoxy radical (31) Cl and HCl (35, 36) Acetyl (43) accompanied by m/z 43 prominent and propyl (43) radical

Resolution

Exact Masses of isotopes

Mass Defects
By definition the atomic weight of 12C is 12.0000 Daltons All other elements are determined relative to 12C Their difference to nearest integral is called Mass Defect Light element has small positive mass defect Vast majority of elements have substantial negative mass defect

Mass Defects
The Mass Defect of a C23H35O2Si is shown here on a low resolution MS (+/- 0.1)

Mass defect for H : 1.008-1.000 = .008

Mass defect for O : 15.995-16.000 = -.005 Mass defect for Si : 27.977 -28.000 = -.003 (35 x 0.008) + (2 x -.005) + (-.003) = .27 Mass defect for organic compounds is mainly due to Hydrogen due to their large number

Mass Defects
Mass defect brings the maximum of the C23H35O2Si peak not at 371 but at 371.25 If the Mass spectrometer measure the mass with a resolution of 1, the sensitivity is reduced.

Greatest application of Mass Defect is surely very high resolution, which provide mass with .001 to .0001 accuracy

High resolution:
Exact Mass can provide Molecular Formula With sufficient accuracy, unique molecular formula can be determine

e.g. Distinguish CO, N2, CH2N and C2H4 (all having m/z 28)
CO
12C
16O

12.0000 15.9949 27.9949

N2

14N 14N

14.0031 14.0031 28.0062

CH2N

12C

12.0000 1H x2 2.0156 14N 14.0031 28.0187

C2H4

12C

x2 24.0000 1H x4 4.0312 28.0312

Exact Mass can provide Molecular Formula

Consider the following 2 formulas which have m/z 287: C15H10NO3Cl

C14H8N2O3Cl

Mass Defect of C15H10NO3Cl: (10 x .0078) + (.0031) + (3 x -.0051 ) + (-.0311 ) = .0347

Mass Defect of C14H8N2O3Cl: (8 x .0078) + (2 x .0031) + (3 x -.0051 ) + (-.0311 ) = .0202 With sufficiently high resolution MS, it is possible to propose a unique empirical formula for an ion.

Nitrogen rule M+ even even # of N 0, 2, 4, M+ odd odd # of N 1, 3, 5, Index of Hydrogen deficiency Index = C H/2 X/2 + N/2 + 1 e.g. C7H7NO Index = 7 - 3.5 + 1 = 5 Hydrogen deficiency can be unsaturation (multiple bonds) or cyclic structure R-CN

I=2
I=1 (1 DB + cycle) I=4 (3 DB + cycle)

Index of hydrogen deficiency : General Index = IV (I/2) + (III/2) +1 IV any tetravalent atom (e.g. C, Si..)

I any monovalent atom (e.g. H, D,Cl, Br, F )

III any trivalent atom (e.g. N, P, ) II any divalent atom (e.g. S, O,). These count for 0 in the formula Higher valences uses valence shells lewis octet rule

+ CH3-S-CH3
OI=0

+ CH3-N
I=1

O O-

CH3 + CH -P-CH
3

phosphine

OI=0

Fragmentation in different isomers

Molecular ion almost absent

Ionization Techniques
Electron Impact (EI) Under these conditions, very energetic Ions are produced => Fragmentation M.+ is often weak e.g. ROH often loose H2O

Intensity of M.+ Depends on the stability of the Ion Most Stable

Aromatic Conjugated Alkenes Cyclic compounds Sulfides Short Linear Alkanes Mercaptans Ketones Amines Ester Ether Acid ~ Amides ~ Aldehydes

Least Stable M.+ is often absent in:

Alcohols, Nitriles, Nitrates, Nitro, Nitriles

Other Ionization Techniques

Under EI (Electron Impact), the molecular ion may be weak or absent
In such case, the best solution is to run CI Chemical Ionization Which result in intense M+1 ion with little fragmentation CI Chemical Ionization Vaporized Sample is introduced with excess gas (usually methane) The gaz is ionized producing Primary ions that react with excess gaz to produce secondary ions CH .+ + CH CH + + CH . CH3+ + CH4 C2H5+ + H2 Secondary ions react with sample M:
4 4 5 3

CH5+ + M [M+H]+ + CH4 C2H5+ + M [M+H]+ + C2H4

Less energy than CI => less fragment

Chemical Ionization techniques

In Electron Impact (EI) and chemical ionization, vaporization of the Sample is a prerequisite. Therefore: the study of non-volatile or thermally fragile compound is not possible with these techniques. Several methods have been developed to go around these limitation (methods that enable ions to be obtained from liquid/solid)

1- Field Desorption: ions are desorbed by strong electric field

In this and other techniques,, the aim is to transfer energy to the Sample, causing transfer of molecules/ions to gas phase

2- SIMS : other source of energy is a beam of ions (Secondary Ion Mass Spectroscopy): Typically Argon (FAB)

Field Desorption methods give a high concentration of Molecular ion => Particularly useful for identification of unknown

Fast Atom Bombardment (FAB)

The sample is dissolved in a liquid matrix such as glycerol, thioglycerol, m-nitrobenzyl alcohol, or diethanolamine and a small amount (about 1 microliter) is placed on a target.

The target is bombarded with a fast atom beam (for example, 6 keV xenon atoms) that desorb molecular-like ions and fragments from the analyte.
Xe

e-

Xe+ + Xe

Xe+ Is accelerated to ~6-10 keV, and pass through Xe

Xe + Xe+

Xe

(Xenon with Kinetic energy) FAB

Cluster ions from the liquid matrix are also desorbed and produce a chemical background that varies with the matrix used.

FAB: Benefits
Sample introduction can be through direct insertion probe or LC/MS (continuous-flow FAB).

Benefits
rapid, simple relatively tolerant of variations in sampling

good for a large variety of compounds

Useful fragentation pattern strong ion currents -- good for high-resolution measurements

FAB: Limitations
Limitations high chemical background defines detection limits may be difficult to distinguish low-molecular-weight compounds from chemical background analyte must be soluble in the liquid matrix no good for multiply charged compounds with more than 2 charges requires a high concentration of the organic liquid matrix (typically 80 to 95% glycerol) which limits sensitivity Mass range Moderate Typically ~300 Da to about 6000 Da.

Comparing different techniques

Classification according to method of separating charged particule

1. Magnetic Field Deflection

1. 2. Magnetic Field only: Mass 12-500 in seconds Double Focussing: High resolution to 4 decimals r = 60,000

Quadrupole Mass Spectrometer

Quadrupole Mass Filter: Mass Scanning by varying RF & DC Frequencies Quadrupole Ion Storage (Ion Trap) - Compact -Inexpensive -Very Sensitive -GC/MS

Classification according to method of separating charged particule

3. Time of Flight

- Need Fast Electronic (10-7 s)

- Used With Sophisticated Ionization Methods (FAB, Laser Desorption .)

4. FT-ICR (Fourier Transform Ion Cyclotron Resonance)

- Very High Precision most expensive

5. MS/MS (Tandem Mass Spectro.) -Specific Ions are Separated in First MS - Pass one at a time in a collision chamber - Second MS produce Daughter Ions -used for large molecule and resolution of mixture

Time-of-Flight analyzer (TOF)

In TOF instruments, positive ions are produced periodically using brief pulses of electrons,

secondary ions or
laser generated photons

These pulses have typically a frequency of 10-50 kHz and lifetime 0.25ms The ions produced are then accelerated by electric field pulse (103-104 V) that has the same frequency as ionization pulse but lags behind. The accelerated ions then pass into a field-free drift tube (about 1 m long)

Time-of-Flight analyzer (TOF)

MALDI ionization, Time-of-flight Mass Spectrometer

Tandem-MS

Comparing Mass Spectrum of a compound in different type of mass spectrometers

Magnetic sector Quadrupole

Time of Flight

105

MW = 164

Organometallic compounds in MS
It is often possible to determine molecular weight of a compound by MS

For example: Manganese carbonyl => m/z 390

As Mn => 55 and C=O => 28 Mn2(CO)10

Another example: Iridium complex
NMR and IR can give a lot of information but without MS it is very difficult to show the presence of Cl With MS, It is easy to show that 4 Chlorine are present
Cl OC PEt3 Cl Cl Ir P Cl PEt3

Molecular ion is usually present with Laser desorption. However, ions produced That way comes from condensed phase (solid/liquid) and structure in these phase Might be very different from the one in gaz phase. With FAB most intense cation peak is the protonation ion (M+1) peak. Anion (M-1) can also be formed.

Isotope Abundance patterns for some atoms and group of atoms

Can be diagnostic for some isotopes

Calculation of isotope pattern

Abundances can be calculated by multiplying the abundances of the Constituent isotopes e.g. 185Re => 37%
79Br 187Re

=> 63% => 49%

=> 51%

81Br

[ReBr]+ can exist as 4 isotopic forms:

185Re79Br 185Re81Br 187Re79Br 187Re81Br

264 m/z 266 m/z 266 m/z

0.37 x 0.51 = 19% 0.37 x 0.49 = 18.1% 0.63 x 0.51 = 32.1% 0.63 x 0.49 = 30.9%

50.2%

268 m/z

Metastable ions
Some ions have so short lifetimes that they dissociate while moving through the spectrometer.

An ion of mass m1 is accelerated after initial ionization But a different ion m2 (daughter ion) passes the magnetic analyzer The resulting peak is neither m1 or m2 but appear at m* (metastable) m* = (m2)2/m1
These metastable ions are formed during 10-5 s (time spent between electrostatic and magnetic analyzer) are quite broad but provide direct information about ion reactions

Platinum

Tungsten

Index

MS-fragmentation