---
title: "Mass spectrometry"
chunk: 3/8
source: "https://en.wikipedia.org/wiki/Mass_spectrometry"
category: "reference"
tags: "science, encyclopedia"
date_saved: "2026-05-05T03:13:45.652814+00:00"
instance: "kb-cron"
---

== Mass selection ==
Mass analyzers separate the ions according to their mass-to-charge ratio. The following two laws govern the dynamics of charged particles in electric and magnetic fields in vacuum:

  
    
      
        
          F
        
        =
        Q
        (
        
          E
        
        +
        
          v
        
        ×
        
          B
        
        )
      
    
    {\displaystyle \mathbf {F} =Q(\mathbf {E} +\mathbf {v} \times \mathbf {B} )}
  
 (Lorentz force law);

  
    
      
        
          F
        
        =
        m
        
          a
        
      
    
    {\displaystyle \mathbf {F} =m\mathbf {a} }
  
 (Newton's second law of motion in the non-relativistic case, i.e. valid only at ion velocity much lower than the speed of light).
Here F is the force applied to the ion, m is the mass of the ion, a is the acceleration, Q is the ion charge, E is the electric field, and v × B is the vector cross product of the ion velocity and the magnetic field
Equating the above expressions for the force applied to the ion yields:

  
    
      
        (
        m
        
          /
        
        Q
        )
        
          a
        
        =
        
          E
        
        +
        
          v
        
        ×
        
          B
        
        .
      
    
    {\displaystyle (m/Q)\mathbf {a} =\mathbf {E} +\mathbf {v} \times \mathbf {B} .}
  

This differential equation is the classic equation of motion for charged particles. Together with the particle's initial conditions, it completely determines the particle's motion in space and time in terms of m/Q. Thus mass spectrometers could be thought of as "mass-to-charge spectrometers". When presenting data, it is common to use the (officially) dimensionless m/z, where z is the number of elementary charges (e) on the ion (z=Q/e). This quantity, although it is informally called the mass-to-charge ratio, more accurately speaking represents the ratio of the mass number and the charge number, z.
There are many types of mass analyzers, using either static or dynamic fields, and magnetic or electric fields, but all operate according to the above differential equation. Each analyzer type has its strengths and weaknesses. Many mass spectrometers use two or more mass analyzers for tandem mass spectrometry (MS/MS). In addition to the more common mass analyzers listed below, there are others designed for special situations.
There are several important analyzer characteristics. The mass resolving power is the measure of the ability to distinguish two peaks of slightly different m/z. The mass accuracy is the ratio of the m/z measurement error to the true m/z. Mass accuracy is usually measured in ppm or milli mass units. The mass range is the range of m/z amenable to analysis by a given analyzer. The linear dynamic range is the range over which ion signal is linear with analyte concentration. Speed refers to the time frame of the experiment and ultimately is used to determine the number of spectra per unit time that can be generated.

=== Sector instruments ===

A sector field mass analyzer uses a static electric and/or magnetic field to affect the path and/or velocity of the charged particles in some way.
As shown above, sector instruments bend the trajectories of the ions as they pass through the mass analyzer, according to their mass-to-charge ratios, deflecting the more charged and faster-moving, lighter ions more. The analyzer can be used to select a narrow range of m/z or to scan through a range of m/z to catalog the ions present.

=== Time-of-flight ===

The time-of-flight (TOF) analyzer uses an electric field to accelerate the ions through the same potential, and then measures the time they take to reach the detector. If the particles all have the same charge, their kinetic energies will be identical, and their velocities will depend only on their masses. For example, ions with a lower mass will travel faster, reaching the detector first. Ions usually are moving prior to being accelerated by the electric field, this causes particles with the same m/z to arrive at different times at the detector. This difference in initial velocities is often not dependent on the mass of the ion, and will turn into a difference in the final velocity. This distribution in velocities broadens the peaks shown on the count vs m/z plot, but will generally not change the central location of the peaks, since the starting velocity of ions is generally centered at zero. To fix this problem, time-lag focusing/delayed extraction has been coupled with TOF-MS.

=== Quadrupole mass filter ===

Quadrupole mass analyzers use oscillating electrical fields to selectively stabilize or destabilize the paths of ions passing through a radio frequency (RF) quadrupole field created between four parallel rods. Only the ions in a certain range of mass/charge ratio are passed through the system at any time, but changes to the potentials on the rods allow a wide range of m/z values to be swept rapidly, either continuously or in a succession of discrete hops. A quadrupole mass analyzer acts as a mass-selective filter and is closely related to the quadrupole ion trap, particularly the linear quadrupole ion trap except that it is designed to pass the untrapped ions rather than collect the trapped ones, and is for that reason referred to as a transmission quadrupole.
A magnetically enhanced quadrupole mass analyzer includes the addition of a magnetic field, either applied axially or transversely. This novel type of instrument leads to an additional performance enhancement in terms of resolution and/or sensitivity depending upon the magnitude and orientation of the applied magnetic field.
A common variation of the transmission quadrupole is the triple quadrupole mass spectrometer. The "triple quad" has three consecutive quadrupole stages, the first acting as a mass filter to transmit a particular incoming ion to the second quadrupole, a collision chamber, wherein that ion can be broken into fragments. The third quadrupole also acts as a mass filter, to transmit a particular fragment ion to the detector. If a quadrupole is made to rapidly and repetitively cycle through a range of mass filter settings, full spectra can be reported.  Likewise, a triple quad can be made to perform various scan types characteristic of tandem mass spectrometry.

=== Ion traps ===

==== Three-dimensional quadrupole ion trap ====