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Isotopes of a chemical element have the same atomic number $Z$, hence the same number of protons, but different neutron numbers $N$ and therefore different mass numbers $A=Z+N$. For example, every neon atomic nucleus contains ten protons: neon-20, neon-21, and neon-22 contain ten, eleven, and twelve neutrons, respectively. They occupy one chemical element box in the periodic table, rather than three boxes.

Three labels answer different questions. The chemical element fixes $Z$; the isotope specifies which neutron number accompanies that $Z$; the ion label specifies the net electric charge. Neutral ${}_{10}^{22}\mathrm{Ne}$ and the ion ${}_{10}^{22}{\mathrm{Ne}}^{+}$ both contain ten protons and twelve neutrons; they contain ten and nine electrons, respectively. Ordinary ionization changes the electron count, leaving the isotope unchanged. Changing the neutron number can change nuclear binding energy and the possibility of radioactive decay. Isotopic abundances can help distinguish material sources, while radioactive decay can additionally supply chronological information.

A mass spectrum makes the distinction experimentally visible: a single chemical element can give separate ion peaks at different mass-to-charge ratios. Its bulk atomic weight is a weighted mean governed by isotopic abundances, rather than the location of one compulsory peak. The historical mass spectrograph experiment and the synthetic neon mass spectrum below illustrate these complementary observations.

For a modern chosen example, the National Institute of Standards and Technology lists neutral magnesium atomic masses $23.985041697\mathrm{u}$, $24.985836976\mathrm{u}$, and $25.982592968\mathrm{u}$, with reference isotopic abundances $0.7899$, $0.1000$, and $0.1101$. They describe the isotopes with mass numbers 24, 25, and 26, respectively.^[ref] These modern inputs are not a reconstruction of historical observations.

Use the dimensionless mass-to-charge ratio coordinate $x=(m/\mathrm{u})/z$. For the illustration only, approximate ion masses by the neutral atomic masses. The singly charged positions are then near $23.98504$, $24.98584$, and $25.98259$; the doubly charged companions are near $11.99252$, $12.49292$, and $12.99130$. The neutral-to-ion correction already given above is essential at higher accuracy. A peak near $x=12$ alone need not identify a chemical element: another ion with a different electric charge can occupy the same mass-to-charge ratio interval.

For the narrow singly charged peak at $x\approx 24.98584$, the chosen full width at half maximum $\Delta x=0.12$ gives mass resolving power $R\approx 208.2$; widening to $\Delta x=1.20$ gives $R\approx 20.82$. Adjacent isotope spacings here are approximately one unit in $x$. Peaks are visibly separated in the first chosen profile and overlap strongly in the second. A small uncertainty in a fitted peak centre would not by itself make the overlapping components resolved.

Even integrated peak areas need a response model. For isotope fraction $f_i$, let ${\eta }_{i,z}$ collect the probability of ionization into electric charge state $z$, transmission through the analyzer, and the detection response. In a linear instrument with overall exposure factor $C$, the component area isEqual ${\eta }_{i,z}$ at a fixed $z$ makes normalized areas equal the fractions; otherwise it does not. In the chosen example, doubling only the mass-25 response changes the normalized areas to $0.71809$, $0.18182$, and $0.10009$, although the neutral sample is unchanged. Photographic darkening introduces another possible nonlinearity: neither line darkness nor peak height is a universal measure of neutral isotopic abundance. Calibration of position and calibration of intensity answer different questions. Matched standards, a known electric charge assignment, and a response correction make isotope analysis useful; a visually impressive set of peaks alone does not supply those controls.

Mass resolving power compares a peak coordinate $x$ with a stated width or separation criterion $\Delta x$. With $\Delta x$ taken as full width at half maximum, a Gaussian function of standard deviation $\sigma$ hasAt the neon-20 coordinate in the synthetic mass spectrum, $\sigma =0.04$ gives $\Delta x\approx 0.0942$ and $R\approx 212$, while $\sigma =0.70$ gives $\Delta x\approx 1.648$ and $R\approx 12.1$. The width criterion and relative peak areas both matter when judging whether a small neighboring isotope can be distinguished. Mass resolution also differs from the accuracy of a calibrated peak position.

A mass spectrometry instrument with a photographic readout. In the 1919 apparatus described in Chapter V: The Mass-Spectrograph, a gas discharge produced positive ions. Two narrow slits formed a ribbon beam in a vacuum; plates applied an electric field to spread it, an aperture selected part of it, and a magnetic field bent it oppositely. Focusing reduced the spread caused by differing ion speeds, concentrating a given mass-to-charge ratio into a line on a photographic plate.

The observed quantity was line displacement from a fiducial spot. Known reference lines calibrated displacement against mass-to-charge ratio; repeated exposures with changed magnetic field tested the calibration. Evacuation limited collisions. Comparing line shapes with narrow and wide apertures helped distinguish geometric broadening from photographic spreading. Finite slit widths, plate response, and overlapping molecular or multiply charged ions limited interpretation. See Chapter V: The Mass-Spectrograph (§§33–40: apparatus and photographic procedure; §§43 and 45–46: calibration, aperture comparisons, and accuracy).

In Mass spectra and isotopes by Francis William Aston (Nobel lecture, 12 December 1922), the reported neon lines at 20 and 22 have companions at 10 and 11 from doubly charged ions. That paired pattern and comparison with reference lines support different atomic masses within one chemical element, rather than an atomic mass concentrated at the bulk average. The lecture also describes an earlier failed separation by distillation and partial separation by diffusion, showing why the focused mass spectrum supplied stronger evidence. These numbers used a historical oxygen-based reference scale. The lecture's whole-number rule was an empirical approximation at its stated accuracy, not the modern exact definition $A=Z+N$.^[ref]

A mass spectrum displays detected signal against mass-to-charge ratio. Peak positions identify candidate ions; peak areas give isotopic abundances only after the response and overlapping contributions have been accounted for.

Broadening can hide a weak component without changing its area in this ideal model. An actual mass spectrum can also contain molecular ions, different electric charge states, background, and unequal detection responses. A missing visible peak therefore cannot by itself prove the absence of an isotope. Conversely, a fractional atomic weight is a property of a population: there is no requirement for an ion peak at the weighted mean.

The ratio of an ion's mass to its electric charge; in SI it has units $kg/C$. A convenient numerical mass spectrum coordinate is $x=(m/\mathrm{u})/z$, with $q=ze$ and positive integer $z$ here. This $x$ is dimensionless. Doubling $z$ at fixed mass halves $x$, so the electric charge state must be identified before assigning an isotope.

The Paul trap alternates focusing and defocusing electric forces. Their time average along a moving trajectory need not vanish, even when the electric field averages to zero at every fixed point. A spatial gradient makes the fast displacement correlate with the driving electric field; the RF-averaged trapping potential calculates the resulting restoring force.

Wolfgang Paul's lecture describes hyperbolic ring/endcap electrodes, loading by electron-impact ionization of low-pressure gas, and resonant ejection through an endcap hole into an electron multiplier. Sweeping RF voltage produces an air mass spectrum.^[ref]