Mass Spectrometry and Atomic Identification (4E)

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MCAT Chemical and Physical Foundations of Biological Systems › Mass Spectrometry and Atomic Identification (4E)

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1

An analytical lab uses a mass spectrometer to identify an unknown compound. The instrument detects ions, and neutral species are not observed. After a change in ion source settings, the total ion signal decreases substantially, but the $m/z$ positions of the remaining peaks are unchanged. The principle involved is that $m/z$ is determined by ion mass and charge, while signal intensity depends on the number of ions detected. Which conclusion about the ionization process is most consistent with these results? (Constants: $e=1.60\times10^{-19}\ \text{C}$.)

The molecular masses increased, but the instrument automatically corrected the $m/z$ axis to keep peaks fixed

The sample concentration increased, causing detector saturation that shifts peaks to lower $m/z$ values

The compound absorbed less infrared light after the settings change, reducing the apparent mass signal

Fewer ions were produced or transmitted, but the ions that were detected had the same mass-to-charge ratios as before

Explanation

This question tests understanding of the relationship between ion production and mass spectral features. In mass spectrometry, the m/z values of ions are intrinsic properties determined by their mass and charge, independent of how many ions are produced, while peak intensity reflects the number of ions detected. When ionization efficiency decreases, fewer ions are produced and detected, reducing signal intensity, but the m/z values of the ions that are formed remain unchanged because their mass-to-charge ratios are not affected by the ionization conditions. The correct answer A accurately describes this phenomenon: fewer ions but unchanged m/z values. Option C incorrectly suggests that detector saturation from increased concentration would shift m/z values, but detector response affects only intensity, not the measured m/z positions. When troubleshooting mass spectrometry experiments, remember that changes in ionization efficiency affect peak heights but not peak positions. A key diagnostic is that m/z shifts indicate calibration issues or instrumental problems, while intensity changes alone typically indicate ionization or transmission efficiency variations.

2

A lab analyzes a mixture containing chlorine using a mass spectrometer that produces mostly singly charged atomic ions. The spectrum shows two peaks at $m/z=35$ and $m/z=37$ with an intensity ratio of about 3:1. The principle involved is that isotopes of the same element have different masses but (here) the same charge, so their $m/z$ values differ by their mass difference. Which conclusion about the sample is most consistent with the data? (Constants: $e=1.60\times10^{-19}\ \text{C}$.)

The sample contains two isotopes of the same element with masses 35 u and 37 u in a ~3:1 abundance ratio

The peaks indicate two charge states of a 70 u ion: $z=+2$ at 35 and $z=+1$ at 37

The 37 peak must be instrument noise because true isotope peaks must have equal intensity

The sample contains two different elements whose atomic numbers differ by 2, producing peaks 2 units apart

Explanation

This question tests the ability to identify isotope patterns in mass spectrometry for atomic identification. Mass spectrometry separates ions by their mass-to-charge ratio, and isotopes of the same element appear at different m/z values corresponding to their different masses when they have the same charge. The observed peaks at m/z=35 and m/z=37 with a 3:1 intensity ratio perfectly match the natural isotopic distribution of chlorine, which has two stable isotopes: Cl-35 (75.8% abundance) and Cl-37 (24.2% abundance), giving approximately a 3:1 ratio. The correct answer A accurately identifies this as an isotopic pattern of chlorine. Option D incorrectly suggests these could be different charge states of a 70 u ion, but this would require z=+2 at m/z=35 (70/2=35) and an impossible non-integer charge at m/z=37. When analyzing atomic mass spectra, look for peaks separated by small integer mass differences with intensity ratios matching known isotopic abundances. Remember that isotopes of the same element will have the same charge state under identical ionization conditions.

3

A forensic lab uses electron ionization (EI) mass spectrometry to identify an unknown noble gas in a sealed ampule. The instrument forms predominantly singly charged ions ($z=+1$) and reports major peaks at $m/z=20$, $m/z=21$, and $m/z=22$ with relative abundances 90%, 0.3%, and 9.7%, respectively. (Principle: $m/z$ reflects isotope mass divided by charge.) Based on the spectrum, which atom is most likely present?

Neon, because its isotopes produce peaks at $m/z=20$, 21, and 22 for $z=+1$

Argon, because $m/z=20$ corresponds to a fragment of Ar formed in EI

Krypton, because heavier noble gases show multiple isotope peaks

Helium, because $m/z=20$ indicates a doubly charged ion of mass 40

Explanation

The skill being tested is identifying elements using isotope patterns in mass spectrometry. In mass spectrometry, atomic identification relies on the unique masses and relative abundances of isotopes for each element, where m/z corresponds to isotopic mass for singly charged ions. Here, the EI mass spectrum of a noble gas shows peaks at m/z=20, 21, and 22 with abundances 90%, 0.3%, and 9.7%, respectively. Choice A is correct because these match Neon's isotopes: ^20Ne (90.5%), ^21Ne (0.3%), ^22Ne (9.2%), consistent with the data for z=+1. Choice B fails because Helium's main isotope is ^4He, and m/z=20 would imply a mass 40 for z=+2, but Helium does not have an isotope at 40, reflecting a misconception about charge states. To verify similar patterns, compare observed abundances and m/z spacings to standard isotopic tables. Remember that noble gases often form singly charged ions in EI, so assume z=+1 unless evidence suggests otherwise.

4

A TOF mass spectrometer accelerates ions through the same potential difference. If the charge on an ion is doubled (from $+1$ to $+2$) while its mass stays constant, (Principle: $K=qV$; higher charge yields higher kinetic energy and thus higher velocity.) what change is most consistent with the measured flight time? Constants: $K=\tfrac{1}{2}mv^2$.

Flight time is unchanged because only mass affects TOF

Flight time increases because the ion experiences more repulsion in the flight tube

Flight time decreases because the ion gains more kinetic energy at the same voltage

Flight time becomes undefined because doubly charged ions cannot be detected

Explanation

This question tests understanding of charge effects on ion velocity in time-of-flight mass spectrometry. When an ion's charge doubles while mass remains constant, it gains twice the kinetic energy (K = qV) when accelerated through the same potential difference. Since K = ½mv², doubling the kinetic energy increases velocity by √2, thereby decreasing flight time. The correct answer B recognizes that higher charge leads to more kinetic energy, higher velocity, and shorter flight time. Answer A incorrectly suggests increased repulsion affects flight time, while C wrongly claims only mass matters in TOF. For TOF-MS calculations, remember that flight time is proportional to √(m/z), so doubling charge (halving m/z) reduces flight time by a factor of √2.

5

A sample contains a mixture of $\text{CO}$ and $\text{N}_2$, both of which have molecular mass 28 u. The MS is operated to detect singly charged molecular ions only, and both species produce a peak at $m/z=28$. (Principle: MS separates by $m/z$; isobars can be indistinguishable without additional information.) What is most consistent with the mass spectrometry result? Constants: none needed.

Both gases can contribute to the same $m/z=28$ peak, so MS alone may not differentiate them here

Only $\text{N}_2$ can appear at $m/z=28$ because $\text{CO}$ is neutral and cannot be ionized

The peak at $m/z=28$ must be a hydrogen fragment because small fragments dominate spectra

The instrument can distinguish $\text{CO}^+$ from $\text{N}_2^+$ at the same $m/z$ using only mass analysis

Explanation

This question tests understanding of mass spectrometry's limitations in distinguishing isobaric species. Isobars are different chemical species with the same mass, and when they carry the same charge, they appear at identical m/z values in standard mass spectrometry. CO and N₂ both have molecular mass 28 u (C=12, O=16, N=14), so their singly charged molecular ions both appear at m/z = 28. The correct answer B recognizes that MS alone cannot differentiate these isobaric species without additional techniques like high-resolution MS or tandem MS. Answer A incorrectly claims MS can distinguish them using only mass analysis, while C wrongly states CO cannot be ionized. When analyzing mixtures by MS, be aware that different molecules with identical masses produce overlapping peaks and require additional methods for differentiation.

6

A researcher increases the ionization energy in an EI source while analyzing the same compound. The molecular ion peak intensity decreases, and several lower-$m/z$ fragment peaks increase in intensity, while the molecular ion $m/z$ value stays the same. (Principle: fragmentation changes the distribution of ions but not the $m/z$ position of a given ion.) Which conclusion about the ionization process is most consistent with the data? Constants: none needed.

The observed changes are due to fluorescence quenching at higher energy

Higher ionization energy increased fragmentation, reducing molecular ion abundance without shifting its $m/z$

The analyzer recalibrated, shifting all peaks to lower $m/z$

The compound’s molecular mass decreased due to the higher ionization energy

Explanation

This question tests understanding of how ionization energy affects fragmentation without changing molecular ion m/z values. In electron ionization MS, increasing ionization energy deposits more internal energy into molecules, increasing fragmentation probability while the m/z value of any given ion (including the molecular ion) remains unchanged. The observation of decreased molecular ion intensity with increased fragment peaks at lower m/z values indicates enhanced fragmentation. The correct answer B recognizes that higher ionization energy increases fragmentation, redistributing signal from the molecular ion to fragments without shifting the molecular ion's m/z position. Answer A incorrectly suggests the mass changes with ionization energy, while C implies a calibration shift affecting all peaks. Remember that m/z values are determined by mass and charge, not by the ionization energy used to create the ions.

7

A chemist measures an unknown metal ion by mass spectrometry. The ion source can produce both $z=+1$ and $z=+2$ ions. Two peaks appear at $m/z=24$ and $m/z=12$ with similar isotopic patterning and no other major peaks. The principle used is that doubling the charge state halves $m/z$ for the same mass. Which conclusion is most consistent with the results?

Constants: $e = 1.60\times 10^{-19}\ \text{C}$; $1\ \text{amu} = 1.66\times 10^{-27}\ \text{kg}$.

The peaks indicate two different electronic transitions measured by atomic absorption spectroscopy

The $m/z=24$ peak is $M^{+}$ and the $m/z=12$ peak is $M^{2+}$ for the same metal

The $m/z=24$ peak is $M^{2+}$ and the $m/z=12$ peak is $M^{+}$ for the same metal

The two peaks must be two different elements because charge state does not affect $m/z$

Explanation

This question tests understanding of how charge states affect m/z values in mass spectrometry and the ability to deduce charge states from peak patterns. The fundamental principle is that m/z = M/z, so doubling the charge halves the m/z value for the same mass M. The observation of peaks at m/z = 24 and m/z = 12, where one is exactly half the other, strongly suggests the same metal ion in different charge states. Since 12 = 24/2, the m/z = 12 peak must have twice the charge of the m/z = 24 peak, meaning if m/z = 24 is M⁺ (z=+1), then m/z = 12 is M²⁺ (z=+2), both from a metal with mass M = 24 amu (likely magnesium). Choice C incorrectly claims charge state doesn't affect m/z, contradicting the fundamental m/z = M/z relationship that defines mass spectrometry. To identify charge state relationships, look for m/z values that are simple fractions of each other (1/2, 2/3, 3/4). When peaks show identical isotopic patterns at different m/z values with integer relationships, they likely represent the same species at different charge states.

8

A sample is analyzed by electron-impact ionization mass spectrometry. Two prominent peaks are observed: $m/z=28$ and $m/z=14$. The principle used is that fragmentation can produce smaller ions with lower mass-to-charge ratios, often with $z=+1$. Which interpretation is most consistent with these peaks?

Constants: $1\ \text{amu} = 1.66\times 10^{-27}\ \text{kg}$; $e = 1.60\times 10^{-19}\ \text{C}$.

The two peaks indicate two different retention times from gas chromatography rather than ion masses

The $m/z=28$ peak is an isotope peak of the $m/z=14$ ion caused by $^{14}$C labeling

The $m/z=14$ peak must represent the doubly charged form of the $m/z=28$ ion

The $m/z=14$ peak is most consistent with a fragment that has approximately half the mass of the $m/z=28$ parent ion

Explanation

This question tests understanding of fragmentation patterns in electron-impact ionization mass spectrometry, where high-energy electrons cause molecules to break into smaller pieces. In EI-MS, fragmentation produces ions with masses that are fractions of the parent ion mass, typically maintaining z=+1 charge, so fragment m/z values reflect actual fragment masses. The observation of peaks at m/z = 28 and m/z = 14, where one is exactly half the other, suggests that m/z = 14 is a fragment ion with approximately half the mass of the m/z = 28 parent ion. This pattern is consistent with molecules like N₂ (mass 28) fragmenting to N⁺ (mass 14) or CO (mass 28) fragmenting to C⁺ or O⁺, though the latter requires more energy. Choice B incorrectly interprets the m/z = 14 peak as a doubly charged form of m/z = 28, but EI typically produces singly charged ions, and fragmentation is the more common explanation for such patterns. To distinguish fragmentation from multiple charging, consider the ionization method: EI favors fragmentation and single charges, while ESI favors intact ions with multiple charges. When m/z values show simple integer relationships in EI-MS, fragmentation is usually the cause, not charge state differences.

9

A researcher uses mass spectrometry to distinguish between two isotopes of the same element. The instrument is set to detect only singly charged ions. Two peaks are observed at $m/z=63$ and $m/z=65$ with an intensity ratio of about 7:3. The principle used is that isotopes differ in mass but have the same chemical behavior, and for $z=+1$ the peak positions reflect isotopic masses. Based on the spectra, which atom is most likely present?

Constants: $1\ \text{amu} = 1.66\times 10^{-27}\ \text{kg}$; $e = 1.60\times 10^{-19}\ \text{C}$.

Zinc, because its dominant isotopes at 64 and 66 amu shift to 63 and 65 after ionization

Copper, due to isotopes near 63 and 65 amu with ~7:3 abundance

Nickel, because its multiple isotopes always produce exactly two peaks at 63 and 65

Gallium, because isotopes at 69 and 71 amu appear at 63 and 65 when singly charged

Explanation

This question tests atomic identification through isotopic abundance patterns in mass spectrometry, requiring recognition of characteristic isotope ratios. In mass spectrometry with singly charged ions, m/z values directly represent isotopic masses, and the intensity ratio reflects natural isotopic abundances unique to each element. The peaks at m/z = 63 and 65 with a 7:3 intensity ratio match copper's isotopic distribution: Cu-63 (~69.2%) and Cu-65 (~30.8%), giving approximately a 7:3 ratio. This specific combination of masses separated by 2 amu with this abundance ratio is diagnostic for copper, as it's the only common element with significant isotopes at exactly these masses with this ratio. Choice B incorrectly suggests zinc isotopes shift mass during ionization, but ionization only removes electrons without changing nuclear mass - Zn isotopes are at 64, 66, 67, 68, and 70, not 63 and 65. When identifying elements by isotope patterns, memorize key signatures: Cl (35/37, ratio 3:1), Br (79/81, ratio 1:1), and Cu (63/65, ratio 7:3). Always verify that both the m/z values AND intensity ratios match known isotopic data for conclusive identification.

10

In a TOF mass spectrometer, ions are accelerated from rest through a potential difference $V=2000\ \text{V}$. Two ions have the same mass but charges $+e$ and $+2e$. (Constants: $e=1.60\times10^{-19}\ \text{C}$.) (Principle: $qV$ sets kinetic energy after acceleration.) Which statement is most consistent with the expected TOF results?

Both ions have the same kinetic energy because they experience the same voltage

The $+2e$ ion has lower kinetic energy and arrives later

Arrival times depend only on ionization energy, not on charge

The $+2e$ ion has higher kinetic energy and arrives earlier

Explanation

The skill being tested is analyzing charge effects on time-of-flight in mass spectrometry. In TOF mass spectrometry, kinetic energy is qV, so higher charge leads to higher energy and velocity, thus shorter flight time. The ions have same mass but charges +e and +2e, accelerated through V=2000 V. Choice B is correct because +2e ion gains twice the energy, arriving earlier. Choice A fails by stating lower energy for +2e, misconstruing qV relationship. To verify, calculate KE = qV and v = sqrt(2KE/m) for arrival times. Remember charge multiplies energy in acceleration, affecting TOF.

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