Electronic Structure and Periodic Properties
Light carries energy in small packets. An atom can take in or give off those packets only in fixed amounts. That one fact explains the red glow of a neon sign and the orange of a sodium streetlight. It also explains the shape of the periodic table. In this chapter you follow the electron. You will see where it can sit, how much energy each seat holds, and what happens when it moves. Then you will use that map to write the electron layout of any element. By the end the table will look less like a chart and more like a record of how electrons stack up.
By the end of this chapter you can
- Link wavelength, frequency and photon energy using c = λν and E = hν.
- Use the Bohr energy levels to predict the four visible lines of hydrogen.
- Name the four quantum numbers and say what each one fixes.
- Sketch an s, p, d or f orbital and count the nodes it carries.
- Write the electron configuration of any element, including the common exceptions.
- Draw an orbital diagram that obeys Pauli and Hund, then count unpaired electrons.
- Predict radius, ionization energy, electron affinity and electronegativity across the table.
Section 1Light and quantized energy
Light is a wave you can measure
Light is a moving pair of electric and magnetic fields. In empty space it always travels at one speed. That speed is c = 2.998 × 108 m/s. Every wave has a wavelength, written λ. Wavelength is the distance from one crest to the next crest. Every wave also has a frequency, written ν. Frequency counts how many crests pass a fixed point each second. Its unit is the hertz, which is just s-1.
The speed of light ties those two numbers together.
Because c never changes, λ and ν must trade off. A short wave has to come fast. A long wave has to come slowly. Blue light has a shorter wavelength than red light. So blue light must have the higher frequency. The amplitude is the height of the wave. Amplitude sets how bright the light looks. It does not set the color.
Visible light is a thin slice of the whole electromagnetic spectrum. Red light sits near 700 nm. Violet light sits near 400 nm. Radio waves can be meters long. X-rays are smaller than an atom. All of them are the same kind of wave at different sizes.
Energy comes in packets
For a long time light looked purely like a wave. Then two experiments broke that picture. Hot objects do not glow the way wave theory predicts. Light shining on a metal knocks electrons loose only above a threshold color. Max Planck and Albert Einstein fixed both problems with one idea. Light energy comes in countable pieces.
One piece of light energy is a photon. The energy of a photon depends only on frequency.
Here h is Planck's constant, 6.626 × 10-34 J·s. The number is tiny, so one photon carries very little energy. Still, the rule is strict. A photon of 400 nm light carries almost twice the energy of a 700 nm photon.
Energy that comes in fixed pieces is quantized. Think about coins. You can pay 25 cents or 50 cents. You cannot pay 25.3 cents, because no coin that size exists. Light works the same way. Brighter light means more photons, not bigger ones.
Worked example · the energy in green laser light
A green laser pointer puts out light at 532 nm. Find its frequency, the energy of one photon, and the energy of a mole of those photons.
Step 1 · put the wavelength in metersλ = 532 nm = 532 × 10-9 m = 5.32 × 10-7 m
Step 2 · use c = λν to get frequencyν = c / λ = (2.998 × 108 m/s) ÷ (5.32 × 10-7 m) = 5.635 × 1014 s-1
Step 3 · use E = hν for one photonE = (6.626 × 10-34 J·s)(5.635 × 1014 s-1) = 3.734 × 10-19 J
Step 4 · scale up to one mole(3.734 × 10-19 J)(6.022 × 1023 /mol) = 2.249 × 105 J/mol = 225 kJ/mol
Check the unitsJ·s times s-1 leaves J, so step 3 is set up right. And 225 kJ/mol is the right size. It sits close to the strength of a chemical bond, which is why light can drive reactions.
- Wavelength and frequency are locked together by c = λν.
- Short wavelength means high frequency and high photon energy.
- E = hν with h = 6.626 × 10-34 J·s gives the energy of one photon.
- Amplitude controls brightness. Frequency controls color and energy.
- Energy in packets is quantized. There is no half photon.
Section 2The Bohr model and line spectra
A glowing gas gives only certain colors
Put hydrogen gas in a glass tube and run current through it. The tube glows pink. Send that glow through a prism and the pink splits apart. You do not get a smooth rainbow. You get four sharp colored lines on a dark field. That pattern is a line spectrum.
Hydrogen's four visible lines sit at 656 nm, 486 nm, 434 nm and 410 nm. Every hydrogen sample in the universe gives the same four. Sodium gives a different set. Helium gives another. A line spectrum is a fingerprint for an element. That is how we know what stars are made of.
A smooth rainbow would mean an electron can hold any energy at all. Sharp lines mean something else. The electron can only hold certain fixed energies. When it drops from a higher one to a lower one, the leftover energy leaves as a single photon. One jump gives one color.
Bohr's ladder of allowed energies
In 1913 Niels Bohr built a model that got hydrogen right. He let the electron circle the nucleus only in certain orbits. Each orbit carries a fixed energy set by a whole number n, called the principal quantum number.
The energies are negative because the electron is trapped. Zero energy means a free electron, far from the nucleus. The lowest rung, n = 1, is the ground state. Any higher rung is an excited state. Notice how fast the rungs crowd together. The gap from n = 1 to n = 2 is huge. The gap from n = 5 to n = 6 is small.
To find the photon, subtract the two energies.
A drop gives a negative ΔE. The atom lost that energy, so a photon of that size left. A climb gives a positive ΔE, which means the atom took a photon in. The four visible lines all end on n = 2. Jumps that end on n = 1 release far more energy, so they land in the ultraviolet.
Worked example · where the red line comes from
An excited hydrogen electron drops from n = 3 to n = 2. Find the photon's energy and wavelength.
Step 1 · find each energyE3 = −(2.179 × 10-18 J)/9 = −2.421 × 10-19 J
E2 = −(2.179 × 10-18 J)/4 = −5.448 × 10-19 J
Step 2 · subtract, final minus initialΔE = (−5.448 × 10-19) − (−2.421 × 10-19) = −3.026 × 10-19 J
The sign is negative, so the atom gave off a photon of 3.026 × 10-19 J.
Step 3 · turn energy into wavelengthhc = (6.626 × 10-34 J·s)(2.998 × 108 m/s) = 1.986 × 10-25 J·m
λ = hc/E = (1.986 × 10-25 J·m) ÷ (3.026 × 10-19 J) = 6.56 × 10-7 m = 656 nm
Check it656 nm is deep red, and red is the brightest hydrogen line by eye. The same steps with n = 4, 5 and 6 give 486, 434 and 410 nm.
- A line spectrum shows that electron energies are quantized.
- En = −(2.179 × 10-18 J)/n2 for hydrogen, and the sign means bound.
- ΔE = Efinal − Einitial. Negative means a photon came out.
- The visible lines at 656, 486, 434 and 410 nm all end on n = 2.
- Bohr's model nails hydrogen but fails for atoms with more electrons.
Section 3Quantum numbers and orbital shapes
From orbits to clouds
Bohr's neat circles cannot be right. An electron is small and fast, and the Heisenberg uncertainty principle says we cannot pin down both its place and its motion. So we stop asking where the electron is. We ask where it is likely to be. Erwin Schrödinger wrote an equation whose answers give exactly that. Each answer is an orbital.
An orbital is a region around the nucleus where one electron is likely to be found. Picture a swarm of gnats around a porch light. No single gnat has a path you can trace. Still, the swarm has a clear shape and a clear center. The darker part of the cloud means higher probability density.
Four numbers name every orbital
Each orbital is labeled by three quantum numbers. A fourth one describes the electron sitting in it.
- The principal quantum number n is 1, 2, 3 and up. It sets size and most of the energy. All orbitals with the same n form a shell.
- The angular momentum quantum number l runs from 0 up to n − 1. It sets shape. We write l = 0 as s, 1 as p, 2 as d and 3 as f. Orbitals that share n and l form a subshell.
- The magnetic quantum number ml runs from −l through 0 to +l. It sets direction in space. That gives 2l + 1 orbitals in a subshell.
- The spin quantum number ms is +½ or −½. It is the electron's own two-way property, drawn as an up or down arrow.
So s subshells hold 1 orbital, p hold 3, d hold 5 and f hold 7. Each orbital takes at most 2 electrons. A full shell therefore holds 2n2 electrons.
What the shapes look like
An s orbital is a ball centered on the nucleus. A p orbital is two lobes on opposite sides, like a long balloon pinched in the middle. The three p orbitals point along x, y and z. A d orbital usually has four lobes in a clover pattern, and the fifth d shape has two lobes with a ring around the middle. The seven f shapes are more involved still.
Most orbitals have places where the electron is never found. Those places are nodes. The count is fixed. Angular nodes equal l, so a p orbital has one flat nodal plane through the nucleus. Radial nodes equal n − l − 1, and those are thin shells of empty space. Add them and any orbital has n − 1 nodes in all. More nodes go with more energy.
Worked example · counting the fourth shell
How many subshells, orbitals and electrons fit in the shell with n = 4?
Step 1 · list the allowed l valuesl goes from 0 to n − 1, so l = 0, 1, 2, 3. That is four subshells: 4s, 4p, 4d and 4f.
Step 2 · count orbitals with 2l + 14s gives 1, 4p gives 3, 4d gives 5 and 4f gives 7. Total = 1 + 3 + 5 + 7 = 16 orbitals.
Step 3 · two electrons per orbital2 × 16 = 32 electrons.
Check with the shortcut2n2 = 2(4)2 = 2(16) = 32. The two routes agree.
- An orbital is a probability cloud, not a path.
- n sets size, l sets shape, ml sets direction, ms sets spin.
- l must be less than n, and ml must lie between −l and +l.
- s, p, d and f subshells hold 1, 3, 5 and 7 orbitals.
- A shell holds 2n2 electrons, and every orbital carries n − 1 nodes.
Section 4Electron configurations
Fill the cheapest seats first
An atom at rest holds its electrons in the lowest energy arrangement it can. The Aufbau principle says to add electrons one at a time, always to the lowest open subshell. The written result is the electron configuration. Oxygen has 8 electrons, so oxygen is 1s2 2s2 2p4. The superscripts must add up to the atomic number.
The filling order is not simply 1s, 2s, 3s. Once several electrons crowd an atom, each one feels the pull of the nucleus plus the push of the others. That reshuffles the subshell energies. The useful order is this.
Look at 4s and 3d. The 4s subshell fills first, even though its n is larger. The diagonal chart below builds that order for you. Follow each gold arrow from its tail to its head, then start the next one.
Shorthand, core and valence
Long configurations get clumsy, so we use the last noble gas as a stand-in. Calcium is 1s2 2s2 2p6 3s2 3p6 4s2, which we shorten to [Ar] 4s2. The electrons hidden in the bracket are the core electrons. The ones written out are the valence electrons, and those are the ones that do chemistry. Elements in the same group share a valence pattern, which is exactly why they behave alike.
The exceptions worth knowing
In the first row of transition metals, 4s and 3d sit very close in energy. Two elements break the simple pattern because of that.
| Element | Pattern predicts | Measured | Why |
|---|---|---|---|
| Cr (24) | [Ar] 4s2 3d4 | [Ar] 4s1 3d5 | Half-filled d set, six unpaired spins |
| Cu (29) | [Ar] 4s2 3d9 | [Ar] 4s1 3d10 | Full d set of ten electrons |
| Mo (42) | [Kr] 5s2 4d4 | [Kr] 5s1 4d5 | Same half-filled gain, one row down |
| Ag (47) | [Kr] 5s2 4d9 | [Kr] 5s1 4d10 | Same full-set gain as copper |
Moving one s electron into the d set costs almost nothing here. Spreading the electrons out lowers repulsion, so the swapped version wins. Chromium ends with six unpaired electrons, which is more than any other element in its row.
Ions follow one more rule. When an atom loses electrons, the highest n goes first. Iron is [Ar] 4s2 3d6. Fe2+ is [Ar] 3d6, not [Ar] 4s2 3d4. Fe3+ is [Ar] 3d5. Anions just add electrons to the next open spot, so Cl- is [Ne] 3s2 3p6, the same as argon.
Worked example · arsenic, element 33
Write the full and short configurations for arsenic.
Step 1 · fill in order until you reach 331s2 (2) → 2s2 (4) → 2p6 (10) → 3s2 (12) → 3p6 (18) → 4s2 (20) → 3d10 (30) → 4p3 (33)
Step 2 · write it out1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p3
Step 3 · use the noble gas shorthandArgon is element 18, so arsenic is [Ar] 4s2 3d10 4p3.
Check the sum2 + 2 + 6 + 2 + 6 + 2 + 10 + 3 = 33. Arsenic has five valence electrons, which matches group 15.
- Add electrons to the lowest open subshell, and the superscripts must total the atomic number.
- The order 1s 2s 2p 3s 3p 4s 3d 4p 5s comes from the diagonal chart.
- [Noble gas] shorthand hides the core and shows the valence electrons.
- Cr is [Ar] 4s1 3d5 and Cu is [Ar] 4s1 3d10. Mo and Ag match them.
- Cations lose the highest n electrons first, so Fe3+ is [Ar] 3d5.
Section 5Orbital diagrams and Hund's rule
Boxes and arrows
A configuration like 2p4 tells you the count. It does not tell you how those four electrons are spread over the three 2p orbitals. An orbital diagram shows that. Draw one box for each orbital and one arrow for each electron. An up arrow is spin +½ and a down arrow is spin −½. Two rules decide where the arrows go.
Pauli caps every box at two
The Pauli exclusion principle says no two electrons in one atom can share all four quantum numbers. An orbital already fixes n, l and ml. Only spin is left, and spin has two settings. So a box holds at most two electrons, and they must point opposite ways. Those two are a paired set. This single rule is why s holds 2, p holds 6, d holds 10 and f holds 14.
Hund spreads them out first
Orbitals in the same subshell have equal energy. We call them degenerate. Hund's rule says to put one electron in each degenerate box, all spinning the same way, before doubling up anywhere. Electrons repel each other, so two in one box cost extra energy. Keeping them in separate boxes with parallel spins keeps them farther apart and lowers the total energy.
Nitrogen shows the rule plainly. Its 2p3 electrons go one per box, all three arrows up. Oxygen has one more. That fourth electron must pair somewhere, so oxygen ends with two unpaired electrons.
Unpaired electrons are measurable. An atom or ion with unpaired electrons is paramagnetic, and a magnet pulls on it. With every electron paired it is diamagnetic, and a magnet pushes it away very weakly. Zinc, [Ar] 4s2 3d10, is diamagnetic. Iron, with four unpaired 3d electrons, is strongly drawn to a magnet.
Worked example · unpaired electrons in sulfur and iron
How many unpaired electrons does a sulfur atom have? What about an iron atom?
Step 1 · write sulfur's configurationSulfur is element 16, so it is [Ne] 3s2 3p4.
Step 2 · place the 3p electronsThree boxes, four electrons. One per box uses three. The fourth pairs with one of them.
Boxes read paired, single, single. That gives 2 unpaired electrons, so sulfur is paramagnetic.
Step 3 · do the same for ironIron is element 26, so it is [Ar] 4s2 3d6. The 4s pair is paired.
Five d boxes take one each, which uses five. The sixth pairs up.
Boxes read paired, single, single, single, single. That gives 4 unpaired electrons.
Why it mattersThose four unpaired spins are why iron sticks to a magnet. Zinc, with 3d10, has none and does not.
- An orbital diagram shows one box per orbital and one arrow per electron.
- Pauli: no two electrons share all four quantum numbers, so a box holds two at most.
- Paired electrons in one box must have opposite spins.
- Hund: fill degenerate boxes singly with parallel spins before pairing any.
- Unpaired electrons mean paramagnetic. All paired means diamagnetic.
Section 6Periodic trends
One idea runs all four trends
Every trend in this section comes from a tug of war. The nucleus pulls the outer electrons in. The inner electrons get in the way and push back. The net pull that an outer electron actually feels is the effective nuclear charge, written Zeff. The blocking by inner electrons is shielding.
Move right across a period and protons pile up fast. Shielding barely changes, because the new electrons go into the same shell. So Zeff climbs and the outer electrons get held tighter. Move down a group and the valence electrons start a brand new shell. They sit farther out, with a thick layer of core electrons in between. The grip loosens.
Atomic radius
The atomic radius shrinks left to right and grows top to bottom. Across period 2 it falls from 167 pm at lithium to 42 pm at fluorine. Down group 1 it rises from 167 pm at lithium to 298 pm at cesium. Adding a shell always wins over adding protons.
Ions break the pattern in a useful way. A cation lost electrons, so the remaining ones feel a stronger pull per electron. A sodium atom is near 190 pm, while Na+ is about 102 pm. An anion gained electrons, which adds repulsion. Cl- is about 181 pm, much wider than the chlorine atom it came from. In an isoelectronic set, every ion has the same electron count. Then the one with the most protons is smallest, so the order runs Na+ < Ne < F-.
Ionization energy
The ionization energy is the energy needed to pull the loosest electron off a gaseous atom. It rises left to right and falls top to bottom. Sodium needs 496 kJ/mol, while argon in the same period needs 1521 kJ/mol. Cesium, far down group 1, needs only 376 kJ/mol.
Two small dips break the rise, and both are worth knowing. Boron (801 kJ/mol) is lower than beryllium (899 kJ/mol), because boron's electron leaves a higher-energy 2p orbital. Oxygen (1314 kJ/mol) is lower than nitrogen (1402 kJ/mol), because oxygen already has a pair crowding one 2p orbital. Those dips are the orbital diagrams showing up in measured data.
Removing a second electron always costs more. Sodium's first ionization energy is 496 kJ/mol. Its second is 4562 kJ/mol, roughly nine times as much. The second electron has to come out of the neon-like core. That huge jump is why sodium forms Na+ and never Na2+.
Worked example · from kJ per mole to joules per atom
Hydrogen's ionization energy is 1312 kJ/mol. How much energy is that for a single atom?
Step 1 · convert kilojoules to joules1312 kJ/mol = 1.312 × 106 J/mol
Step 2 · divide by Avogadro's number(1.312 × 106 J/mol) ÷ (6.022 × 1023 /mol) = 2.179 × 10-18 J per atom
Step 3 · compare with section 2That is exactly the Bohr ground-state energy, 2.179 × 10-18 J. Lifting the electron from n = 1 to n = ∞ costs the same energy as ionizing the atom, because those are the same event.
Electron affinity and electronegativity
The electron affinity is the energy change when a gaseous atom accepts an electron. A negative value means energy is released, so the atom wants the electron. Chlorine is the champion at −349 kJ/mol, with fluorine close behind at −328 kJ/mol. Beryllium and the noble gases have positive values, because their subshells are already full and a new electron has nowhere good to sit.
Finally, electronegativity measures how hard an atom pulls on electrons it is sharing inside a bond. The Pauling scale runs from 0.79 at cesium to 3.98 at fluorine. It rises toward the upper right, just like ionization energy. Oxygen is 3.44, nitrogen is 3.04, carbon is 2.55 and hydrogen is 2.20. You will use those four numbers constantly in the next chapter to decide whether a bond is polar.
- Zeff rises across a period and barely changes down a group.
- Radius falls across a period and rises down a group. Cations shrink, anions swell.
- Ionization energy rises across and falls down, with dips at group 13 and group 16.
- Electron affinity is most negative near chlorine and fluorine.
- Electronegativity runs from 0.79 at cesium to 3.98 at fluorine.
The chapter in one breath
- Light is a wave with c = λν, and it delivers energy in photons of size E = hν.
- Line spectra prove that an atom's electron energies are quantized, not continuous.
- Bohr's levels, En = −(2.179 × 10-18 J)/n2, give hydrogen's lines at 656, 486, 434 and 410 nm.
- Four quantum numbers name an orbital and the electron in it: n, l, ml and ms.
- Shapes follow l: s is a ball, p is two lobes, d is mostly four lobes, f is more complex.
- Configurations follow the diagonal order, with Cr and Cu taking 4s1 to gain a half or full d set.
- Pauli caps an orbital at two opposite spins, and Hund spreads electrons out before pairing them.
- Unpaired electrons make an atom paramagnetic, which is a property you can measure with a magnet.
- Zeff drives every periodic trend, so radius, ionization energy and electronegativity all follow one map.
ReferenceWords worth knowing
These are the terms this chapter leans on most. Come back to the list whenever a problem uses a word you want to pin down.
- amplitude
- The height of a wave. It controls brightness, not color or photon energy.
- Aufbau principle
- The rule that electrons fill the lowest open subshell first.
- core electrons
- The inner electrons hidden inside the noble gas bracket. They rarely take part in bonding.
- degenerate orbitals
- Orbitals in the same subshell, which all have equal energy.
- effective nuclear charge
- Written Zeff. The net pull an outer electron feels after inner electrons shield it.
- electron affinity
- The energy change when a gaseous atom gains one electron. Negative means energy is released.
- electron configuration
- The list of subshells with electron counts, such as 1s2 2s2 2p4.
- electronegativity
- How strongly an atom pulls on electrons it shares in a bond. Fluorine leads at 3.98.
- frequency
- Written ν. The number of wave crests passing a point each second, in s-1.
- ground state
- The lowest energy arrangement of an atom's electrons.
- Hund's rule
- Fill degenerate orbitals singly with parallel spins before any orbital gets a pair.
- ionization energy
- The energy needed to remove the loosest electron from a gaseous atom.
- isoelectronic
- Having the same number of electrons. Na+, Ne and F- are an isoelectronic set.
- node
- A place inside an orbital where the electron is never found.
- orbital
- A region around a nucleus where one electron is likely to be. It holds two electrons at most.
- paramagnetic
- Having one or more unpaired electrons, so a magnet attracts the sample.
- Pauli exclusion principle
- No two electrons in an atom may share all four quantum numbers.
- photon
- One packet of light energy, with E = hν.
- quantized
- Allowed only in fixed amounts, like coins rather than a smooth stream.
- wavelength
- Written λ. The distance from one wave crest to the next.