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Chemical bonding and structure of matter · The periodic table

Electronic structure and interaction with electromagnetic radiation

Before you start, make sure you know: Electron configuration (Chemistry (high school))

When the light from a hydrogen lamp passes through a prism, you do not see a continuous rainbow, but just a few colored lines on a black background. It is the same reason fireworks on the Fourth of July glow in different colors. This fingerprint of lines, different for each element, is the experimental proof that the electrons in an atom cannot have just any energy: they can only occupy certain permitted levels. Understanding those levels, and the order in which they fill, is understanding why the periodic table has the shape it has.

Atomic spectra: the fingerprint of each element

When you look through a spectroscope at the white light of an incandescent bulb, a continuous band with all the colors appears, but when you focus on the hot gas in a sodium or neon tube you only see thin, isolated lines separated by dark regions: why don't gaseous atoms emit a continuous range of energy?

Comparison between the continuous spectrum of a light bulb, with all the colors without interruption, and the line spectrum of a hydrogen lamp, with only a few isolated violet, blue-green and red lines on a dark background light bulb (continuous spectrum) hydrogen lamp (line spectrum) violet blue-green red Dark regions: wavelengths not emitted

The fact that each element has its own pattern of lines, always the same, means that the electrons in that atom can only jump between certain fixed energy levels, characteristic of the element. It is, quite literally, an atomic fingerprint: this is how the composition of a star is identified without ever bringing back a sample of it, and how flame tests identify the metal salts in fireworks.

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Passing the light from a hydrogen discharge lamp through a prism produces a few colored lines on a black background, whereas light from a filament bulb breaks down into…

Passing the light from a hydrogen discharge lamp through a prism produces a few colored lines on a black background, whereas light from a filament bulb breaks down into a continuous rainbow. The figure compares the two spectra:

filament bulb hydrogen lamp
  1. a) What is the difference between a continuous spectrum and a line spectrum?
  2. b) Which of the two is an atomic emission spectrum? What information does it provide about the element producing it?
Solve
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Electrons in an atom can only occupy certain energy levels, which are different in each element, as illustrated in the figure: Explain, based on this idea: a) Why each…

Electrons in an atom can only occupy certain energy levels, which are different in each element, as illustrated in the figure:

element A n = 2 n = 1 element B n = 2 n = 1

Explain, based on this idea:

  1. a) Why each element emits light of characteristic colors and not others.
  2. b) Why the set of these lines serves to identify an element, just as a fingerprint identifies a person.
Solve
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Fireworks contain strontium salts (red light), barium salts (green light) and sodium salts (yellow light). a) What happens to the electrons in these atoms when the…

Fireworks contain strontium salts (red light), barium salts (green light) and sodium salts (yellow light).

  1. a) What happens to the electrons in these atoms when the combustion of gunpowder heats the salts?
  2. b) Where does the colored light we see come from? Explain the full process using the concept of transitions between energy levels.
Solve
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An electron in an atom is in level $n = 1$. a) What needs to happen for it to move to level $n = 3$? Does the atom absorb or release energy in this process? b) When the…

An electron in an atom is in level $n = 1$.

  1. a) What needs to happen for it to move to level $n = 3$? Does the atom absorb or release energy in this process?
  2. b) When the electron falls back to level $n = 1$, what does the atom emit? Draw the two processes in your notebook using arrows between the levels.

You can do it on paper and send a photo with your answer.

Solve
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In $1814$, Joseph Fraunhofer observed that the spectrum of the Sun is crossed by hundreds of dark lines: they appear at exactly the same wavelengths that elements emit…

In $1814$, Joseph Fraunhofer observed that the spectrum of the Sun is crossed by hundreds of dark lines: they appear at exactly the same wavelengths that elements emit in the lab, but in absorption, because the gases in the solar atmosphere absorb that light. The diagram compares the two spectra:

light from the Sun element in the lab
  1. a) Explain, using the concept of energy levels, why an element absorbs exactly the same wavelengths that it is capable of emitting.
  2. b) Two of the dark lines of the Sun coincide with the yellow doublet of sodium: what conclusion can be drawn about the solar atmosphere?
  3. c) Explain how it is possible to know the chemical composition of a distant star without ever retrieving a sample of it.
Solve

Energy of a photon: $E = h\nu$

Light behaves like a beam of particles, the photons, each with an energy that depends only on its frequency.

In the interactive, $\lambda$ and $\nu$ move independently; for light they are tied together, because $\lambda\nu = c$ is always the same. Halve the wavelength and you will see that, for the speed not to change, you have to double the frequency: the shorter the wavelength, the higher the frequency. An ultraviolet photon (short wavelength) is more energetic than a visible red-light photon (long wavelength). In general, infrared photons make molecules vibrate, while visible and UV photons can drive electronic transitions.

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Many old street lamps used sodium vapor lamps, which give a very intense yellow light. a) Why is their light practically monochromatic (single-colored), unlike the white…

Many old street lamps used sodium vapor lamps, which give a very intense yellow light.

  1. a) Why is their light practically monochromatic (single-colored), unlike the white light of a filament bulb?
  2. b) One of these street lamps illuminates a road and everything appears in shades of yellow and gray: explain, using the concept of a line spectrum, why car colors are harder to distinguish than under white light.
Solve
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The characteristic yellow line of sodium has a wavelength of $\lambda = 589\ \text{nm}$. Light travels in a vacuum at $c = 3\times10^{8}\ \text{m/s}$. a) Express the…

The characteristic yellow line of sodium has a wavelength of $\lambda = 589\ \text{nm}$. Light travels in a vacuum at $c = 3\times10^{8}\ \text{m/s}$.

  1. a) Express the wavelength in meters.
  2. b) Calculate the frequency of this light using $c = \lambda\times\nu$.
Solve
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The energy of a photon is $E = h\times\nu$, with Planck's constant $h = 6.63\times10^{-34}\ \text{J}\times\text{s}$. a) Calculate the energy of the sodium yellow photon,…

The energy of a photon is $E = h\times\nu$, with Planck's constant $h = 6.63\times10^{-34}\ \text{J}\times\text{s}$.

  1. a) Calculate the energy of the sodium yellow photon, of frequency $\nu = 5.1\times10^{14}\ \text{Hz}$.
  2. b) An ultraviolet photon has a higher frequency than visible light: is its energy greater or smaller? Justify your answer using the formula.
Solve
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Germicidal lamps in operating rooms emit ultraviolet light of $\lambda = 254\ \text{nm}$. Data: $h = 6.63\times10^{-34}\ \text{J}\times\text{s}$ and…

Germicidal lamps in operating rooms emit ultraviolet light of $\lambda = 254\ \text{nm}$. Data: $h = 6.63\times10^{-34}\ \text{J}\times\text{s}$ and $c = 3\times10^{8}\ \text{m/s}$.

  1. a) Calculate the energy of one of these photons using $E = \frac{h\times c}{\lambda}$.
  2. b) UV photons damage the DNA of microorganisms while visible light photons do not: relate this fact to the energy calculated in the previous part.
Solve
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A fireworks display simultaneously emits red ($\lambda \approx 700\ \text{nm}$), green ($\lambda \approx 530\ \text{nm}$) and blue ($\lambda \approx 450\ \text{nm}$)…

A fireworks display simultaneously emits red ($\lambda \approx 700\ \text{nm}$), green ($\lambda \approx 530\ \text{nm}$) and blue ($\lambda \approx 450\ \text{nm}$) light. The figure positions the three lines in the visible spectrum:

400 500 600 700 λ (nm) 450 nm 530 nm 700 nm
  1. a) Arrange the three colors in order of increasing frequency, reasoning from $c = \lambda\times\nu$.
  2. b) Then arrange them in order of increasing photon energy, using $E = h\times\nu$: which color corresponds to the most energetic electron transitions?
Solve
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The yellow light of sodium is actually a doublet: two very close lines of $\lambda_1 = 589.0\ \text{nm}$ and $\lambda_2 = 589.6\ \text{nm}$. Data:…

The yellow light of sodium is actually a doublet: two very close lines of $\lambda_1 = 589.0\ \text{nm}$ and $\lambda_2 = 589.6\ \text{nm}$. Data: $h = 6.63\times10^{-34}\ \text{J}\times\text{s}$ and $c = 3\times10^{8}\ \text{m/s}$.

  1. a) Calculate the energy of each of the two photons using $E = \frac{h\times c}{\lambda}$.
  2. b) Calculate the energy difference between them.
  3. c) This difference corresponds to the energy gap between two subshells of the sodium atom: what does the existence of the doublet reveal about the structure of the atom's energy levels?
Solve
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Red LEDs ($\lambda = 660\ \text{nm}$) have existed since the 1960s, but the blue LED ($\lambda = 470\ \text{nm}$) was only achieved in the 1990s, an advance awarded the…

Red LEDs ($\lambda = 660\ \text{nm}$) have existed since the 1960s, but the blue LED ($\lambda = 470\ \text{nm}$) was only achieved in the 1990s, an advance awarded the Nobel Prize in Physics in $2014$. Data: $h = 6.63\times10^{-34}\ \text{J}\times\text{s}$ and $c = 3\times10^{8}\ \text{m/s}$.

  1. a) Calculate the energy of the red photon and that of the blue photon.
  2. b) How many times more energetic is the blue photon than the red one?
  3. c) An LED emits light when electrons jump a characteristic energy "step" of the semiconductor: using the previous results, explain why the blue LED was technologically much harder to manufacture than the red one.
Solve
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The first three energy levels of hydrogen are $E_1 = -13.6\ \text{eV}$, $E_2 = -3.4\ \text{eV}$ and $E_3 = -1.5\ \text{eV}$. When an electron drops from one level to a…

The first three energy levels of hydrogen are $E_1 = -13.6\ \text{eV}$, $E_2 = -3.4\ \text{eV}$ and $E_3 = -1.5\ \text{eV}$. When an electron drops from one level to a lower one, it emits a photon whose energy is exactly the difference between the two levels. The diagram shows the three levels and the two transitions:

E = 0 E₃ = −1.5 eV E₂ = −3.4 eV E₁ = −13.6 eV E = ? λ = ? E = ? λ = ?

Data: $1\ \text{eV} = 1.602\times10^{-19}\ \text{J}$, $h = 6.63\times10^{-34}\ \text{J}\times\text{s}$, $c = 3\times10^{8}\ \text{m/s}$.

  1. a) Calculate the energy emitted in transitions $E_3 \rightarrow E_2$ and $E_2 \rightarrow E_1$, in $\text{eV}$ and in joules.
  2. b) Calculate the wavelength of each photon in $\text{nm}$ and state which one falls in the visible range ($390$–$750\ \text{nm}$) and which one in the ultraviolet. Transition $E_3 \rightarrow E_2$ is the famous red H-alpha line of the Balmer series.
  3. c) Using your results, explain why the spectrum of hydrogen consists of discrete lines and is not continuous.
Solve
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A highlighter glows brightly under the ultraviolet light of a nightclub: its molecules absorb invisible UV photons and emit brightly colored visible light. a) Which…

A highlighter glows brightly under the ultraviolet light of a nightclub: its molecules absorb invisible UV photons and emit brightly colored visible light.

  1. a) Which photon is more energetic, the absorbed one (UV) or the emitted one (visible)? Justify your answer using $E = \frac{h\times c}{\lambda}$.
  2. b) Propose an explanation using the concept of transitions between energy levels: the electron goes up in a single transition, but comes down in two smaller transitions, losing energy along the way.
  3. c) Could a material emit blue light when illuminated with red light? Reason your answer in terms of energy.
Solve

From the Bohr atom to the quantum model: shells, subshells and orbitals

The Bohr model, with electrons in exact circular orbits, reasonably explains the energy jumps of hydrogen, but it cannot account for atoms with more electrons or for the real shape of the electron cloud. The quantum model replaces it with orbitals: regions where the probability of finding the electron is high. You only need the vocabulary here: electrons are grouped into shells ($n$), which contain subshells ($s$, $p$, $d$, $f$), which contain orbitals.

This atom with 17 protons is chlorine. Each electron in its cloud occupies an orbital; the Pauli exclusion principle says an orbital holds at most two electrons, and they must have opposite spins.

Comparison of the Bohr model, with an electron in an exact circular orbit around the nucleus, and the quantum model, with a diffuse probability cloud around the nucleus Bohr model quantum model nucleus electron orbit with an exact trajectory nucleus probability cloud (orbital) denser = more likely
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The order of filling of subshells is $1s$, $2s$, $2p$, $3s$, $3p$, with maximum capacities of $2$ electrons in each s subshell and $6$ in each p subshell, as shown in…

The order of filling of subshells is $1s$, $2s$, $2p$, $3s$, $3p$, with maximum capacities of $2$ electrons in each s subshell and $6$ in each p subshell, as shown in the diagram:

1s 2s 2p 3s 3p max. 2 max. 2 max. 6 max. 2 max. 6 order of filling
  1. a) Write the electron configuration of nitrogen ($Z = 7$).
  2. b) Write the electron configuration of magnesium ($Z = 12$).
Solve

The filling order: the Aufbau principle and electron configuration

Electrons fill the lowest-energy subshells first (the Aufbau principle). Within a subshell, Hund's rule says electrons occupy separate orbitals with parallel spins before pairing up. Subshells do not fill in the naive order "$1s, 2s, 2p, 3s, 3p, 3d...$": from level $3$ onwards, the $4s$ sublevel has less energy than the $3d$, so it is filled first.

Aufbau diagram: the diagonals join the subshells in filling order, and the 4s, with less energy, fills before the 3d 1s 2s2p 3s3p3d 4s4p4d 5s5p 6s the 4s has less energy than the 3d (fills first)

Ions and isoelectronic species

Main-group atoms gain or lose electrons to reach a noble-gas configuration. Cations lose electrons from the highest shell first; anions add electrons to the same shell.

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The number of the highest energy level occupied by electrons corresponds to the period of the element in the periodic table. a) Which period is an atom in if its…

The number of the highest energy level occupied by electrons corresponds to the period of the element in the periodic table.

  1. a) Which period is an atom in if its configuration ends in $3s^1$? Which element is it?
  2. b) And which period is an atom in if its configuration ends in $2p^5$? Identify it using the periodic table.
Solve
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The electrons in the outermost level, called valence electrons, determine the group of the element. a) How many valence electrons does an atom whose configuration ends…

The electrons in the outermost level, called valence electrons, determine the group of the element.

  1. a) How many valence electrons does an atom whose configuration ends in $3s^2 3p^4$ have? Which group does it belong to?
  2. b) And one whose configuration ends in $3s^2 3p^3$? Name both elements.
Solve
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After the $3p$ subshell, $4s$ is filled before $3d$, as shown in the energy level diagram: Maximum capacities: s, $2$ electrons; p, $6$; d, $10$. a) Write the electron…

After the $3p$ subshell, $4s$ is filled before $3d$, as shown in the energy level diagram:

E 1s 2s 2p 3s 3p 4s 3d 4s before 3d

Maximum capacities: s, $2$ electrons; p, $6$; d, $10$.

  1. a) Write the electron configurations of potassium ($Z = 19$) and calcium ($Z = 20$).
  2. b) Write the electron configuration of iron ($Z = 26$), taking into account that after $4s$ is filled, $3d$ starts to fill.
Solve
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a) Write the electron configuration of the ions $\text{Na}^{+}$ ($Z = 11$) and $\text{Cl}^{-}$ ($Z = 17$) and verify that each matches that of a noble gas: which noble…
  1. a) Write the electron configuration of the ions $\text{Na}^{+}$ ($Z = 11$) and $\text{Cl}^{-}$ ($Z = 17$) and verify that each matches that of a noble gas: which noble gases are they?
  2. b) Argon, the ion $\text{K}^{+}$ ($Z = 19$) and the ion $\text{Ca}^{2+}$ ($Z = 20$) have the same number of electrons: how many? What are species that have the same number of electrons called?
Solve
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An element has the electron configuration $1s^2 2s^2 2p^6 3s^2 3p^6 4s^2 3d^{10} 4p^3$. a) What is its atomic number? Which element is it? b) In which period and in…

An element has the electron configuration $1s^2 2s^2 2p^6 3s^2 3p^6 4s^2 3d^{10} 4p^3$.

  1. a) What is its atomic number? Which element is it?
  2. b) In which period and in which group of the periodic table is it located? Justify both answers using its configuration.
Solve
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The shorthand electron configuration of an element is $[\text{Ar}]\ 4s^2 3d^{10} 4p^5$. a) Add up the electrons to find its atomic number and identify the element using…

The shorthand electron configuration of an element is $[\text{Ar}]\ 4s^2 3d^{10} 4p^5$.

  1. a) Add up the electrons to find its atomic number and identify the element using the periodic table.
  2. b) How many valence electrons does it have? What ion does it tend to form? Justify your answer by considering the configuration of the next noble gas.
Solve
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An element has atomic number $Z = 37$. a) Write its electron configuration (filling order: $1s$, $2s$, $2p$, $3s$, $3p$, $4s$, $3d$, $4p$, $5s$). b) Deduce its period…

An element has atomic number $Z = 37$.

  1. a) Write its electron configuration (filling order: $1s$, $2s$, $2p$, $3s$, $3p$, $4s$, $3d$, $4p$, $5s$).
  2. b) Deduce its period and group, and identify the element using the periodic table.
  3. c) Predict, justifying your answer from the configuration: how many valence electrons it has, which ion it forms most easily, and whether it will react violently with water.
Solve

Stable exceptions: half-filled and filled sublevels

The Aufbau order predicts most configurations, but not all of them. Some transition elements "cheat": an electron from the $4s$ jumps to the $3d$ so that this subshell is half-filled ($d^5$) or completely filled ($d^{10}$), configurations that are especially stable.

Orbital diagram of chromium: the expected configuration 4s² 3d⁴ versus the real one 4s¹ 3d⁵, with the 3d subshell half-filled and more stable 4s 3d Expected: 4s² 3d⁴ one electron moves from 4s to 3d Real (more stable): 4s¹ 3d⁵ 3d half-filled (d⁵)
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Iron ($Z = 26$) has the electron configuration $[\text{Ar}]\ 4s^2 3d^6$. a) Atoms lose the electrons from the highest shell first: write the electron configuration of…

Iron ($Z = 26$) has the electron configuration $[\text{Ar}]\ 4s^2 3d^6$.

  1. a) Atoms lose the electrons from the highest shell first: write the electron configuration of the $\text{Fe}^{2+}$ ion and that of the $\text{Fe}^{3+}$ ion.
  2. b) A half-filled subshell is particularly stable: what configuration does $\text{Fe}^{3+}$ reach in its $3d$ subshell? Use this fact to explain why $\text{Fe}^{3+}$ is so abundant in nature (rust and many iron minerals contain it).
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According to the usual filling order, chromium ($Z = 24$) should have the configuration $[\text{Ar}]\ 4s^2 3d^4$ and copper ($Z = 29$), $[\text{Ar}]\ 4s^2 3d^9$. In…

According to the usual filling order, chromium ($Z = 24$) should have the configuration $[\text{Ar}]\ 4s^2 3d^4$ and copper ($Z = 29$), $[\text{Ar}]\ 4s^2 3d^9$. In reality, their configurations are $[\text{Ar}]\ 4s^1 3d^5$ and $[\text{Ar}]\ 4s^1 3d^{10}$, respectively. The orbital box diagram shows the case of chromium:

4s 3d expected actual electron moves
  1. a) Compare the "expected" and "actual" configurations of each element: how many electrons are in the $3d$ subshell in each case?
  2. b) Half-filled ($d^5$) and fully filled ($d^{10}$) subshells are particularly stable: use this information to explain the two actual configurations.
  3. c) What does this example teach us about the difference between a simple filling rule and the actual electronic structure of atoms?
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Back to the beginning: The periodic table has blocks of $2$, $6$, $10$ and $14$ columns because they reflect exactly the maximum electron capacity of the $s$, $p$, $d$ and $f$ subshells as they fill according to energy order. And the red, green and yellow of those fireworks? They come from electrons in strontium, barium and sodium atoms dropping between energy levels and emitting photons.

Summary

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