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NCERT Solutions · Class 11 Chemistry Structure of Atom

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Exercises 2.61–2.67 (part 7 of 7)

  1. Exercise 2.61

    If the position of the electron is measured within an accuracy of ± 0.002\displaystyle 0.002 nm, calculate the uncertainty in the momentum of the electron. Suppose the momentum of the electron is h/4πm\displaystyle h/4\pi_{m} × 0.05\displaystyle 0.05 nm, is there any problem in defining this value.

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    NCERT’s answer
    Cannot be defined as the actual magnitude is smaller than uncertainity.
    Heisenberg's uncertainty principle says you cannot shrink the uncertainty in position and the uncertainty in momentum together below a fixed floor — pinning one down tighter only forces the other one up.The principle is written \[\Delta x \cdot \Delta p \geq \frac{h}{4\pi} \] where \(\displaystyle \Delta x \) is the uncertainty in position, \(\displaystyle \Delta p \) is the uncertainty in momentum, and \(\displaystyle h = 6.626 \times 10^{-34}\ \text{J s} \) is Planck's constant.Convert nm to m before touching the formula — leaving out the factor of \(\displaystyle 10^{-9}\) here throws the whole answer off by a billion. \[\Delta x = 0.002\ \text{nm} = 0.002 \times 10^{-9}\ \text{m} = 2 \times 10^{-12}\ \text{m} \]Rearranging for the minimum uncertainty in momentum, \[\Delta p \geq \frac{h}{4\pi\, \Delta x} = \frac{6.626 \times 10^{-34}\ \text{J s}}{4\pi \times 2 \times 10^{-12}\ \text{m}} \]Work the denominator first: \(\displaystyle 4\pi \times 2 \times 10^{-12} = 12.566 \times 2 \times 10^{-12} = 2.513 \times 10^{-11}\ \text{m} \). Then\[\Delta p \geq \frac{6.626 \times 10^{-34}}{2.513 \times 10^{-11}}\ \text{kg m s}^{-1} = 2.64 \times 10^{-23}\ \text{kg m s}^{-1} \](A joule is \(\displaystyle \text{kg m}^2\text{s}^{-2}\), so \(\displaystyle \text{J s}/\text{m} = \text{kg m s}^{-1}\) — a momentum unit, as it should be.)So fixing the electron's position to within $\displaystyle 0.002$ nm forces its momentum to be uncertain by at least \(\displaystyle 2.64 \times 10^{-23}\ \text{kg m s}^{-1} \).Now check whether a momentum built from a position spread of $\displaystyle 0.05$ nm — roughly the size of an atomic orbital — can even be called a definite number. Use the same expression, \(\displaystyle h/(4\pi \Delta x) \), but now with \(\displaystyle \Delta x = 0.05\ \text{nm} = 5 \times 10^{-11}\ \text{m} \): \[p = \frac{h}{4\pi \times 0.05\ \text{nm}} = \frac{6.626 \times 10^{-34}\ \text{J s}}{4\pi \times 5 \times 10^{-11}\ \text{m}} \]Denominator: \(\displaystyle 4\pi \times 5 \times 10^{-11} = 12.566 \times 5 \times 10^{-11} = 6.283 \times 10^{-10}\ \text{m} \). Then\[p = \frac{6.626 \times 10^{-34}}{6.283 \times 10^{-10}}\ \text{kg m s}^{-1} = 1.05 \times 10^{-24}\ \text{kg m s}^{-1} \]The comparison between this \(\displaystyle p\) and the \(\displaystyle \Delta p \) found above is the whole point of the question — not either number on its own. \[\frac{\Delta p}{p} = \frac{2.64 \times 10^{-23}}{1.05 \times 10^{-24}} \approx 25 \]The uncertainty in momentum, \(\displaystyle 2.64\times10^{-23}\ \text{kg m s}^{-1}\), is about $\displaystyle 25$ times bigger than the momentum value itself, \(\displaystyle 1.05\times10^{-24}\ \text{kg m s}^{-1}\). A quantity whose spread of possible values is $\displaystyle 25$ times its own size has not actually been pinned down to a number — zero, negative values, and values many times larger are all equally consistent with that spread. So yes, there is a problem: once the electron's position is known as precisely as $\displaystyle 0.05$ nm (atomic-orbital scale), its momentum cannot be assigned any definite value at all. This is exactly why an electron in an atom cannot be pictured as moving on a fixed orbit with a definite position and a definite momentum at every instant — the uncertainty principle rules that picture out.Answer: Δp ≥ $\displaystyle 2.64$ × $\displaystyle 10$⁻²³ kg m s⁻¹; the corresponding momentum h/($\displaystyle 4$π × $\displaystyle 0.05$ nm) = $\displaystyle 1.05$ × $\displaystyle 10$⁻²⁴ kg m s⁻¹ is about $\displaystyle 25$ times smaller than this uncertainty, so no definite value can be assigned to it — the uncertainty swamps the quantity itself.
  2. Exercise 2.62

    The quantum numbers of six electrons are given below. Arrange them in order of increasing energies. If any of these combination(s) has/have the same energy lists: 1. n = 4\displaystyle 4, l = 2\displaystyle 2, ml = –2\displaystyle 2 , ms = –1\displaystyle 1/2\displaystyle 2 2. n = 3\displaystyle 3, l = 2\displaystyle 2, ml = 1\displaystyle 1 , ms = +1\displaystyle 1/2\displaystyle 2 3. n = 4\displaystyle 4, l = 1\displaystyle 1, ml = 0\displaystyle 0 , ms = +1\displaystyle 1/2\displaystyle 2 4. n = 3\displaystyle 3, l = 2\displaystyle 2, ml = –2\displaystyle 2 , ms = –1\displaystyle 1/2\displaystyle 2 5. n = 3\displaystyle 3, l = 1\displaystyle 1, ml = –1\displaystyle 1 , ms = +1\displaystyle 1/2\displaystyle 2 6. n = 4\displaystyle 4, l = 1\displaystyle 1, ml = 0\displaystyle 0 , ms = +1\displaystyle 1/2\displaystyle 2

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    NCERT’s answer
    (v)
    < (ii) = (iv) < (vi) = (iii) < (i)
    Energy in a multi-electron atom depends on both \(\displaystyle n\) and \(\displaystyle l\) together, not on \(\displaystyle n\) alone — use the \(\displaystyle (n+l)\) rule, and \(\displaystyle m_l\), \(\displaystyle m_s\) never change the energy.The rule (Bohr–Bury / \(\displaystyle (n+l)\) rule) has two parts:
    Between two orbitals, the one with the lower value of \(\displaystyle (n+l)\) has the lower energy.
    If two orbitals have the same \(\displaystyle (n+l)\), the one with the lower \(\displaystyle n\) has the lower energy.
    Here \(\displaystyle n\) is the principal quantum number (shell) and \(\displaystyle l\) is the azimuthal quantum number (subshell shape: \(\displaystyle l=0,1,2,3\) for \(\displaystyle s,p,d,f\)). The magnetic quantum number \(\displaystyle m_l\) and spin quantum number \(\displaystyle m_s\) only distinguish orbitals within the same subshell — they do not shift the energy. This is the step people get wrong: two electrons with the same \(\displaystyle n\) and \(\displaystyle l\) but different \(\displaystyle m_l\)/\(\displaystyle m_s\) sit in the same subshell and so have identical energy, even though their quantum numbers look different on paper.Step $\displaystyle 1$ — read off \(\displaystyle n\) and \(\displaystyle l\) for each electron and form \(\displaystyle n+l\).\[\begin{array}{c|c|c|c} \text{Electron} & n & l & n+l \\ \hline 1 & 4 & 2\ (d) & 6 \\ 2 & 3 & 2\ (d) & 5 \\ 3 & 4 & 1\ (p) & 5 \\ 4 & 3 & 2\ (d) & 5 \\ 5 & 3 & 1\ (p) & 4 \\ 6 & 4 & 1\ (p) & 5 \\ \end{array} \]Step $\displaystyle 2$ — sort by \(\displaystyle n+l\), and inside a tie sort by \(\displaystyle n\).The smallest \(\displaystyle n+l\) is $\displaystyle 4$, belonging only to electron $\displaystyle 5$ (\(\displaystyle n=3,l=1\), a 3p electron) — this is the lowest-energy electron.The next group all share \(\displaystyle n+l=5\): electrons $\displaystyle 2$, $\displaystyle 3$, $\displaystyle 4$, 6. Within this group, apply the tie-breaker (lower \(\displaystyle n\) wins):
    \(\displaystyle n=3\): electrons $\displaystyle 2$ and $\displaystyle 4$ — both are \(\displaystyle n=3,\ l=2\), i.e. the same 3d subshell. Same \(\displaystyle n\) and same \(\displaystyle l\) means the same energy: electrons $\displaystyle 2$ and $\displaystyle 4$ are degenerate.
    \(\displaystyle n=4\): electrons $\displaystyle 3$ and $\displaystyle 6$ — both are \(\displaystyle n=4,\ l=1\), i.e. the same 4p subshell. Again same \(\displaystyle n\) and same \(\displaystyle l\), so electrons $\displaystyle 3$ and $\displaystyle 6$ are degenerate.
    Since \(\displaystyle n=3 < n=4\), the 3d pair $\displaystyle (2, 4)$ sits below the 4p pair $\displaystyle (3, 6)$.
    The largest \(\displaystyle n+l\) is $\displaystyle 6$, belonging only to electron $\displaystyle 1$ (\(\displaystyle n=4,l=2\), a 4d electron) — this is the highest-energy electron.Step $\displaystyle 3$ — assemble the full order.\[5 \;<\; (2 = 4) \;<\; (3 = 6) \;<\; 1 \]In subshell language this is exactly the familiar filling order \(\displaystyle 3p < 3d < 4p < 4d\), and it confirms why \(\displaystyle m_l\) and \(\displaystyle m_s\) values (which differ within each pair) play no role in ranking energy — only \(\displaystyle n\) and \(\displaystyle l\) do.Answer: Increasing order of energy is \(\displaystyle 5 < 2 = 4 < 3 = 6 < 1\); electrons $\displaystyle 2$ and $\displaystyle 4$ (both 3d) have equal energy, and electrons $\displaystyle 3$ and $\displaystyle 6$ (both 4p) have equal energy.
  3. Exercise 2.63

    The bromine atom possesses 35\displaystyle 35 electrons. It contains 6\displaystyle 6 electrons in 2p orbital, 6\displaystyle 6 electrons in 3p orbital and 5\displaystyle 5 electron in 4p orbital. Which of these electron experiences the lowest effective nuclear charge ?
    NCERT’s answer
    4p
    Effective nuclear charge falls as more inner-shell electrons sit between an electron and the nucleus — and that number grows with the electron's distance from the nucleus (its principal quantum number \(\displaystyle n\)), not with how many electrons happen to share its own subshell.Bromine's ground-state configuration, matching the electrons given in the question, is\[1s^2\,2s^2\,2p^6\,3s^2\,3p^6\,3d^{10}\,4s^2\,4p^5 \qquad (2+2+6+2+6+10+2+5 = 35) \]So the 2p electrons sit in the \(\displaystyle n=2\) shell, the 3p electrons in the \(\displaystyle n=3\) shell, and the 4p electrons in the outermost \(\displaystyle n=4\) shell.The effective nuclear charge an electron feels is\[Z_{\text{eff}} = Z - S \]where \(\displaystyle Z\) is the actual nuclear charge ($\displaystyle 35$ for Br, in units of the elementary charge \(\displaystyle e\)) and \(\displaystyle S\) is the shielding (screening) constant contributed by the other electrons. Slater's rules give \(\displaystyle S\) precisely, by grouping orbitals as \(\displaystyle (1s)(2s,2p)(3s,3p)(3d)(4s,4p)\ldots\) and assigning each electron a contribution depending on where it sits relative to the electron of interest:
    an electron in the same group contributes \(\displaystyle 0.35\) (a common slip is to assume same-subshell electrons shield a lot — they don't, because they're at almost the same distance from the nucleus and mostly shield each other only weakly);
    an electron in the shell one inside (\(\displaystyle n-1\)) contributes \(\displaystyle 0.85\);
    an electron two or more shells inside (\(\displaystyle \le n-2\)) contributes the full \(\displaystyle 1.00\), since it sits almost entirely between the electron and the nucleus.
    For the 2p electron (group \(\displaystyle 2s,2p\), $\displaystyle 8$ electrons total):\[S_{2p} = \underbrace{(8-1)(0.35)}_{\text{other }2s,2p\text{ electrons}} + \underbrace{(2)(0.85)}_{1s\text{ electrons}} = 2.45 + 1.70 = 4.15 \] \[Z_{\text{eff}}(2p) = 35 - 4.15 = 30.85\ e \]For the 3p electron (group \(\displaystyle 3s,3p\), $\displaystyle 8$ electrons total):\[S_{3p} = \underbrace{(8-1)(0.35)}_{\text{other }3s,3p} + \underbrace{(8)(0.85)}_{2s,2p\text{ shell}} + \underbrace{(2)(1.00)}_{1s\text{ shell}} = 2.45 + 6.80 + 2.00 = 11.25 \] \[Z_{\text{eff}}(3p) = 35 - 11.25 = 23.75\ e \]For the 4p electron (group \(\displaystyle 4s,4p\), $\displaystyle 7$ electrons total): here is the step people usually miss — the \(\displaystyle n-1\) shell for a 4p electron is the whole \(\displaystyle n=3\) shell, which includes the $\displaystyle 10$ electrons of \(\displaystyle 3d\) as well as \(\displaystyle 3s,3p\), because all of them share \(\displaystyle n=3\). Those 3d electrons don't get treated as "same group" just because they're a different subshell; they get the full $\displaystyle 0.85$ as inner-shell shielders.\[S_{4p} = \underbrace{(7-1)(0.35)}_{\text{other }4s,4p} + \underbrace{(8+10)(0.85)}_{3s,3p,3d\text{ shell}} + \underbrace{(2+8)(1.00)}_{1s,\,2s,2p\text{ shells}} \] \[S_{4p} = 2.10 + 15.30 + 10.00 = 27.40 \] \[Z_{\text{eff}}(4p) = 35 - 27.40 = 7.60\ e \]Comparing the three:\[Z_{\text{eff}}(2p) = 30.85\ e \;>\; Z_{\text{eff}}(3p) = 23.75\ e \;>\; Z_{\text{eff}}(4p) = 7.60\ e \]Even though the 4p subshell has fewer electrons of its own ($\displaystyle 5$, versus $\displaystyle 6$ in each of 2p and 3p), it is shielded by every electron in the three shells inside it — including the full 3d¹⁰ set — so it ends up feeling by far the weakest pull from the nucleus. The 2p electron, being closest in and having only the two 1s electrons between it and the nucleus, feels almost the bare nuclear charge.Answer: The 4p electron experiences the lowest effective nuclear charge (\(\displaystyle Z_{\text{eff}} \approx 7.60\ e\), compared with \(\displaystyle \approx 23.75\ e\) for 3p and \(\displaystyle \approx 30.85\ e\) for 2p), because it is farthest from the nucleus and is shielded by all $\displaystyle 28$ electrons of the inner \(\displaystyle n=1\), \(\displaystyle n=2\), and \(\displaystyle n=3\) shells.
  4. Exercise 2.64

    Among the following pairs of orbitals which orbital will experience the larger effective nuclear charge?
    (i)
    2s and 3s,
    (ii)
    4d and 4f,
    (iii)
    3d and 3p.
    NCERT’s answer
    (i)
    2s (ii) 4d (iii) 3p
    Effective nuclear charge is what is left of the true nuclear pull after other electrons shield it away — and how much gets shielded away depends on how close an orbital sits to the nucleus (its \(\displaystyle n\)) and how deeply it dips in towards the nucleus (its \(\displaystyle l\)).The formula to name first: \(\displaystyle Z_{eff} = Z - S\), where \(\displaystyle Z\) is the actual nuclear charge (same for every orbital in a given atom), and \(\displaystyle S\) is the shielding (screening) constant contributed by the other electrons sitting between that orbital and the nucleus. A larger \(\displaystyle S\) means more of the nuclear charge is screened off, so \(\displaystyle Z_{eff}\) is smaller. Comparing two orbitals in the same atom is really comparing their \(\displaystyle S\) values.Two rules decide \(\displaystyle S\), and both come from how much an orbital's electron cloud penetrates close to the nucleus:
    Same \(\displaystyle l\), different \(\displaystyle n\): the orbital with the smaller \(\displaystyle n\) is intrinsically closer to the nucleus, with fewer inner shells of electrons sitting in between to screen it. Less screening, larger \(\displaystyle Z_{eff}\).
    Same \(\displaystyle n\), different \(\displaystyle l\): penetration towards the nucleus falls in the order \(\displaystyle s > p > d > f\) (lower \(\displaystyle l\) means the radial probability distribution has a bigger lobe close to the nucleus). An orbital that penetrates more spends more time in the region very near the nucleus, where the other electrons of that shell shield it less effectively. Lower \(\displaystyle l\), less screening, larger \(\displaystyle Z_{eff}\).
    The step people get wrong here: it is tempting to think a "higher-energy-looking" orbital (bigger \(\displaystyle n\) or \(\displaystyle l\)) always has the bigger \(\displaystyle Z_{eff}\) because it looks more "spread out." It is the opposite — being spread further out, or penetrating less, is exactly what lets other electrons get between that orbital and the nucleus and screen it, so \(\displaystyle Z_{eff}\) goes down, not up.(i) 2s and 3s. Both have \(\displaystyle l = 0\), so this is the same-\(\displaystyle l\), different-\(\displaystyle n\) case. The 2s orbital (\(\displaystyle n = 2\)) lies closer to the nucleus than 3s (\(\displaystyle n = 3\)), with one fewer full shell of electrons screening it. So 2s has the smaller shielding constant \(\displaystyle S\) and therefore the larger \(\displaystyle Z_{eff}\).(ii) 4d and 4f. Both have \(\displaystyle n = 4\), so this is the same-\(\displaystyle n\), different-\(\displaystyle l\) case, with \(\displaystyle l = 2\) for d and \(\displaystyle l = 3\) for f. Using the penetration order \(\displaystyle s > p > d > f\), the 4d orbital penetrates closer to the nucleus than 4f, so it is screened less by the other \(\displaystyle n = 4\) electrons. So 4d has the larger \(\displaystyle Z_{eff}\).(iii) 3d and 3p. Both have \(\displaystyle n = 3\), with \(\displaystyle l = 1\) for p and \(\displaystyle l = 2\) for d. Again by \(\displaystyle s > p > d > f\), 3p penetrates more than 3d, so 3p is screened less and has the larger \(\displaystyle Z_{eff}\).Answer: (i) 2s experiences the larger effective nuclear charge than 3s; (ii) 4d experiences the larger effective nuclear charge than 4f; (iii) 3p experiences the larger effective nuclear charge than 3d — in each pair, the orbital with the smaller \(\displaystyle n\), or (for equal \(\displaystyle n\)) the smaller \(\displaystyle l\), penetrates closer to the nucleus, is shielded less, and so feels the larger \(\displaystyle Z_{eff}\).
  5. Exercise 2.65

    The unpaired electrons in Al and Si are present in 3p orbital. Which electrons will experience more effective nuclear charge from the nucleus ?

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    NCERT’s answer
    Si
    Effective nuclear charge is the net pull an electron actually feels once you subtract the shielding from every other electron in the atom — and Slater's rules let you put a number on it instead of guessing.Write out the two configurations first, since effective nuclear charge depends on exactly which shell each electron sits in.\[\text{Al } (Z=13):\ 1s^2\,2s^2\,2p^6\,3s^2\,3p^1 \] \[\text{Si } (Z=14):\ 1s^2\,2s^2\,2p^6\,3s^2\,3p^2 \]Al's single 3p electron is unpaired by default. Si's two 3p electrons go into two different p orbitals with parallel spins (Hund's rule), so both stay unpaired too — that is why the question can compare "the unpaired 3p electron" in each atom.Effective nuclear charge, \(\displaystyle Z_{eff} = Z - S \), is the nuclear charge \(\displaystyle Z \) reduced by a shielding constant \(\displaystyle S \) that accounts for the repulsion of the other electrons. Slater's rules build \(\displaystyle S \) by grouping electrons as \(\displaystyle (1s)(2s,2p)(3s,3p)(3d)\dots \) and adding up contributions for an electron being screened in the \(\displaystyle (3s,3p) \) group:
    every other electron in the same \(\displaystyle (3s,3p) \) group contributes \(\displaystyle 0.35 \)
    every electron one shell in (the \(\displaystyle n=2 \) group, \(\displaystyle 2s^22p^6 \)) contributes \(\displaystyle 0.85 \)
    every electron two shells in or deeper (the \(\displaystyle n=1 \) group, \(\displaystyle 1s^2 \)) contributes \(\displaystyle 1.00 \)
    This is the step people get wrong: it is tempting to assume the extra proton picked up going from Al to Si is fully cancelled by the extra electron that comes with it, since they're added together. They are not — an electron only screens another electron in its own outer group at the reduced rate of \(\displaystyle 0.35 \), not \(\displaystyle 1.00 \), because they occupy diffuse, overlapping orbitals rather than sitting cleanly inside one another.Aluminium's 3p electron. The \(\displaystyle (3s,3p) \) group holds \(\displaystyle 3s^2\,3p^1 \); excluding the electron itself, the other same-group electrons are just the \(\displaystyle 3s^2 \) pair (there is no second 3p electron to count):\[S_{Al} = (2)(0.35) + (8)(0.85) + (2)(1.00) = 0.70 + 6.80 + 2.00 = 9.50 \] \[Z_{eff}(Al) = 13 - 9.50 = 3.50 \]Silicon's 3p electron. The \(\displaystyle (3s,3p) \) group holds \(\displaystyle 3s^2\,3p^2 \); excluding the electron itself, the other same-group electrons are now \(\displaystyle 3s^2 \) plus the other 3p electron — three electrons in total:\[S_{Si} = (3)(0.35) + (8)(0.85) + (2)(1.00) = 1.05 + 6.80 + 2.00 = 9.85 \] \[Z_{eff}(Si) = 14 - 9.85 = 4.15 \]Comparing the two. Going from Al to Si, the nuclear charge rises by a full unit ($\displaystyle 13$ → $\displaystyle 14$), but the shielding constant rises by only \(\displaystyle 0.35 \) ($\displaystyle 9.50$ → $\displaystyle 9.85$), because the newly added electron sits in the same outer group and screens at the weak \(\displaystyle 0.35 \) rate rather than fully cancelling the extra proton. The net effect is that \(\displaystyle Z_{eff} \) goes up:\[Z_{eff}(Si) = 4.15 > Z_{eff}(Al) = 3.50 \]So the 3p electron in silicon feels a stronger net pull from the nucleus than the 3p electron in aluminium does — consistent with the general trend that effective nuclear charge increases left to right across a period, since electrons added to the same shell never shield one another as effectively as electrons already sitting in an inner shell.Answer: The 3p electron in Si experiences the greater effective nuclear charge — \(\displaystyle Z_{eff}(\text{Si}) \approx 4.15\) versus \(\displaystyle Z_{eff}(\text{Al}) \approx 3.50\) — because Si has one more proton than Al while its extra 3p electron shields only weakly (screening constant $\displaystyle 0.35$) rather than cancelling that extra charge.
  6. Exercise 2.66

    Indicate the number of unpaired electrons in :
    (a)
    P, (b) Si,
    (c)
    Cr,
    (d)
    Fe and
    (e)
    Kr.
    NCERT’s answer
    (a)
    $\displaystyle 3$ (b) $\displaystyle 2$ (c) $\displaystyle 6$ (d) $\displaystyle 4$ (e) zero
    Unpaired electrons are found by writing the ground-state electron configuration and then applying Hund's rule to whichever subshell is not completely full — degenerate orbitals get one electron each before any of them get a second.The two facts you need before counting:
    Hund's rule of maximum multiplicity: electrons entering a set of degenerate orbitals (same subshell — three \(\displaystyle p\), five \(\displaystyle d\), etc.) occupy them singly, with parallel spin, before any orbital receives a second electron. Pairing only starts once every orbital in that subshell already has one electron.
    Chromium and copper are Aufbau exceptions. For most atoms you can just fill \(\displaystyle 1s, 2s, 2p, \dots\) in order, but a half-filled or fully-filled \(\displaystyle d\) subshell is extra stable, so Cr and Cu "steal" one electron from the \(\displaystyle 4s\) orbital to complete \(\displaystyle 3d^5\) or \(\displaystyle 3d^{10}\). Missing this is the single most common slip in this question.
    (a) Phosphorus, P (\(\displaystyle Z = 15\))Aufbau filling gives \[1s^2\,2s^2\,2p^6\,3s^2\,3p^3 . \] The only partially filled subshell is \(\displaystyle 3p^3\): three electrons going into the three degenerate \(\displaystyle 3p\) orbitals (\(\displaystyle p_x, p_y, p_z\)). By Hund's rule they spread out one per orbital instead of pairing up: \[p_x\!\uparrow \quad p_y\!\uparrow \quad p_z\!\uparrow . \] That is $\displaystyle 3$ unpaired electrons.(b) Silicon, Si (\(\displaystyle Z = 14\))\[1s^2\,2s^2\,2p^6\,3s^2\,3p^2 . \] Now only two of the three \(\displaystyle 3p\) orbitals are occupied, and Hund's rule still puts them in separate orbitals rather than pairing them: \[p_x\!\uparrow \quad p_y\!\uparrow \quad p_z\,(\text{empty}) . \] That is $\displaystyle 2$ unpaired electrons.(c) Chromium, Cr (\(\displaystyle Z = 24\))Naive Aufbau filling would predict \(\displaystyle [\text{Ar}]\,4s^2\,3d^4\) — but this is exactly the exception flagged above. Emptying one \(\displaystyle 4s\) electron into the \(\displaystyle 3d\) subshell gives the more stable, experimentally observed configuration \[[\text{Ar}]\;4s^1\,3d^5 . \]
    \(\displaystyle 3d^5\): five electrons filling all five degenerate \(\displaystyle d\) orbitals singly (half-filled, maximally symmetric) → $\displaystyle 5$ unpaired electrons.
    \(\displaystyle 4s^1\): a single electron in an otherwise empty orbital → $\displaystyle 1$ unpaired electron.
    Total: \(\displaystyle 5 + 1 = \) $\displaystyle 6$ unpaired electrons. (If you had used the naive \(\displaystyle 4s^2 3d^4\) configuration you would have gotten $\displaystyle 4$ — the wrong count, because Cr is not a plain-Aufbau atom.)(d) Iron, Fe (\(\displaystyle Z = 26\))Iron is not an exception, so ordinary Aufbau filling applies: \[[\text{Ar}]\;4s^2\,3d^6 . \]
    \(\displaystyle 4s^2\): the single \(\displaystyle 4s\) orbital holds both electrons, paired → $\displaystyle 0$ unpaired electrons here.
    \(\displaystyle 3d^6\): there are only five \(\displaystyle d\) orbitals. By Hund's rule the first five electrons go one to each orbital ($\displaystyle 5$ unpaired so far); the sixth electron has nowhere new to go, so it must pair up with one of the five:
    \[\uparrow\downarrow \quad \uparrow \quad \uparrow \quad \uparrow \quad \uparrow . \] That leaves four orbitals still singly occupied.Total: $\displaystyle 4$ unpaired electrons.(e) Krypton, Kr (\(\displaystyle Z = 36\))\[1s^2\,2s^2\,2p^6\,3s^2\,3p^6\,3d^{10}\,4s^2\,4p^6 . \] Krypton is a noble gas — every subshell (\(\displaystyle s\), \(\displaystyle p\), and \(\displaystyle d\)) is completely filled, so every orbital already contains two paired electrons and none is left half-empty for Hund's rule to act on.Total: $\displaystyle 0$ unpaired electrons.Answer: (a) P — $\displaystyle 3$ unpaired electrons; (b) Si — $\displaystyle 2$ unpaired electrons; (c) Cr — $\displaystyle 6$ unpaired electrons (from \(\displaystyle 4s^1 3d^5\)); (d) Fe — $\displaystyle 4$ unpaired electrons (from \(\displaystyle 4s^2 3d^6\)); (e) Kr — $\displaystyle 0$ unpaired electrons (all subshells filled).
  7. Exercise 2.67

    (a)
    How many subshells are associated with n = 4\displaystyle 4 ?
    (b)
    How many electrons will be present in the subshells having ms value of –1\displaystyle 1/2\displaystyle 2 for n = 4\displaystyle 4 ?
    NCERT’s answer
    $\displaystyle 16$
    The number of subshells in a shell equals the number of allowed values of the azimuthal quantum number \(\displaystyle l \), and every orbital — regardless of shell or subshell — holds exactly one electron with \(\displaystyle m_s = -\tfrac{1}{2} \) and one with \(\displaystyle m_s = +\tfrac{1}{2} \).(a) Subshells for \(\displaystyle n = 4 \)For a given principal quantum number \(\displaystyle n \), the azimuthal quantum number \(\displaystyle l \) (which labels the subshell) takes every integer value from \(\displaystyle 0 \) to \(\displaystyle n-1 \): \[l = 0, 1, 2, \ldots, (n-1) \]For \(\displaystyle n = 4 \): \[l = 0,\ 1,\ 2,\ 3 \quad \longrightarrow \quad 4s,\ 4p,\ 4d,\ 4f \]That is $\displaystyle 4$ values of \(\displaystyle l \), so there are $\displaystyle 4$ subshells associated with \(\displaystyle n = 4 \).(b) Electrons with \(\displaystyle m_s = -\tfrac{1}{2} \) in the \(\displaystyle n = 4 \) shellThe trap here is treating \(\displaystyle m_s \) as if it depended on which subshell or orbital the electron sits in — it does not. By the Pauli exclusion principle, every single orbital (no matter its \(\displaystyle l \) or \(\displaystyle m_l \)) can hold at most two electrons, and if it holds two, one must have \(\displaystyle m_s = +\tfrac{1}{2} \) and the other \(\displaystyle m_s = -\tfrac{1}{2} \). So exactly half of all electrons in a fully occupied shell carry \(\displaystyle m_s = -\tfrac{1}{2} \).First find the total number of electrons the \(\displaystyle n = 4 \) shell can hold, using the capacity formula \[\text{Maximum electrons in shell } n = 2n^2 \] where \(\displaystyle n \) is the principal quantum number and the factor $\displaystyle 2$ comes from the two spin states per orbital.For \(\displaystyle n = 4 \): \[2n^2 = 2(4)^2 = 2 \times 16 = 32 \]So the \(\displaystyle n = 4 \) shell holds $\displaystyle 32$ electrons in total when fully occupied. Since exactly half of these carry \(\displaystyle m_s = -\tfrac{1}{2} \): \[\frac{32}{2} = 16 \]Answer: (a) $\displaystyle 4$ subshells ( \(\displaystyle 4s, 4p, 4d, 4f\) ) are associated with \(\displaystyle n = 4 \). (b) $\displaystyle 16$ electrons in the \(\displaystyle n = 4 \) shell have \(\displaystyle m_s = -\tfrac{1}{2} \).