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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.

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]

Mass spectrometry separates and detects ions according to mass-to-charge ratio. It can distinguish isotopes which belong to the same chemical element but have different atomic masses. The instrument measures ions: interpreting the result as a neutral atomic mass requires accounting for Electron removal and its ionization energy. For a singly positive ion in its ground state, $m_{+}=m_{\mathrm{a}}-m_e+I/c^2$, where $m_e$ is the Electron rest mass, $I$ is the ionization energy, and $c$ is the speed of light.

For a simple illustrative analyzer, positive ions of mass $m$ and electric charge $q=ze$ gain kinetic energy $qV=m{v}^2/2$ across an electric potential difference $V$ before entering a transverse uniform magnetic field $B$. The Lorentz force supplies centripetal acceleration, soAt fixed $V$ and $B$, the measured bending radius $r$ separates mass-to-charge ratios, not masses independently of electric charge. This ideal model assumes negligible initial kinetic energy and speeds small compared with the speed of light; the historical focusing mass spectrograph used the geometry described below.

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.