Lecture 2: The Arrangement of Electrons in Atoms

(Chemistry in Context ch. 6) Evidence for Electron Arrangements Atomic Spectra Successive Ionisation Energies Comparison of First Ionisation Energies Electron Arrangements Quantum Numbers Shapes of Orbitals Pauli Exclusion Principle Aufbau Principle

Electron Configurations Writing Electron configurations Electronic Configurations & the Periodic Table

The Spectrum of Atomic Hydrogen

-model (theory) of structure of atom based on negative electrons orbiting a compact, positive nucleus electrostatic attraction
-spectrum of atomic hydrogen: energy is lost by emission of light

problem why does spectrum of atomic hydrogen show

emissions at certain wavelengths only? Why not continuous range of wavelengths like a rainbow?

Wavelength, Energy and Frequency Reminder

long wavelength (l) low energy (E) low frequency (f) short wavelength (l) high energy (E) high frequency (f)

(continuous spectrum) e.g. light bulb, sunlight

(line spectrum e.g. sparks, excited gases)

neon signs use similar glowing electrified noble gas

-atomic spectra prove that electrons only adopt certain energy levels

E = hc = hn l
i.e. larger the energy drop, the higher the energy of the emitted photon energy (the higher its frequency and shorter its wavelength)

The Bohr Atom

Bohr: hydrogens electron only adopts certain orbits of particular energy (and distance from nucleus) electrons energy is quantised Niels Bohr

Quantisation only particular discrete energy levels are allowed. Like climbing stairs you cant stand between steps!

-photon of light emitted as excited hydrogen atom loses energy (when electron falls from higher energy state to lower)

high energy

low energy

convergence limit of Lyman Series

(Lyman series)

Lyman series (UV) electrons falling to ground state Balmer series (visible) electrons falling to n = 2 state
excited states

converging energy levels

n.b. electrons falling from: n = state to n = 1 state

emit radiation at the convergence limit (equals to atoms ionisation energy):
ground state

H+(g) + e H(g)

Ionisation Energies (6.3)

-ionisation energy is energy needed to remove an electron from an atom (to form a cation):

first ionisation

M+

second ionisation

M2+

all electrons attracted to positive nucleus ionisations are endothermic

relatively easy little energy required low value

more difficult (attraction to cation) more energy required higher value

Na reacts vigorously

Ionisation Energies (6.3)

-comparing succesive ionisation energies tells us that atoms electrons are arranged in shells: first I.E. second I.E.

with water

third I.E.

(kJ/mol)

Al (Gp III)
Mg (Gp II) Na (Gp I)

577
736 494

1820
1450 4560

2740
7740 6910

-electron removal from outer (valence) shell (easy)

-electron removal from inner (core) shell (difficult)

Na has a single outer electron, Mg has 2 and Al has 3

Plotting Successive Ionisation Energies (6.4)

-the electron shells are more obvious if we remove all the electrons of a large atom e.g. Na:
2 electrons in innermost shell (n=1)

1 electron in outer shell (n=3)

we can describe electron configuration of Na as 2-8-1

Plotting Successive Ionisation Energies (6.4)

-Q: What elements successive ionisation energies are plotted here?

Plotting Successive Ionisation Energies (6.4)

-Q: What elements successive ionisation energies are plotted here?

2 electrons in innermost shell (n=1)

4 electrons in outer shell (n=3)

we can describe electron configuration as 2-8-4 has 4 valence electrons (it is in Group IV) Si

Elements I.E. & Electron Subshells (6.5)

-evidence for shell structure also comes from comparing first I.E. of many elements -I.E. increases across a period (more protons added so electrons pulled in closer by greater nuclear charge) -I.E. is highest for stable noble gas electron configurations -little steps indicate sub-shells

1s
2s

2p
n = 2 shell period 2

3s 3p
n = 3 shell period 3

4s

Electron shells house atomic orbitals (6.5) Schrodingers Equation (1926) solutions are wavefunctions (y) called atomic orbitals

- there are n2 orbitals per shell i.e.

one orbital for n = 1

1s

Erwin Schrodinger

four orbitals for n = 2

2s 2p 2p 2p
3s 3p 3p 3p 3d 3 d 3d 3d 3d

nine orbitals for n = 3

The Hydrogen 1s orbital (6.6)

-dot plot shows electron density in 1s orbital (highest close to nucleus)

-small chance of finding electron far away from nucleus

to draw shape of orbital we can draw region within which there is 90% chance of finding electron

region is spherical: (all s orbitals are spherical)

2s orbital higher in energy than (further from nucleus)

1s

2s

2s orbital is also spherical but there is a nodal surface where electron cannot be found

p orbitals have two lobes:

an egg timer

-the three p orbitals within shells n = 2 are at right angles to each other i.e. 2px, 2py, 2pz

n l

ml

n l ml

but within each shell all are same energy (degenerate) in one electron atoms. name indicates the shell, shape of orbital and the orientation of its lobes. e.g.

2py
indicates radius of orbital. Determined by principal quantum number n

indicates shape (symmetry) of orbital. Determined by quantum number l indicates orientation of orbital. Determined by quantum number ml

Electron Spin and ms

Each orbital can hold two electrons. These must be of opposite spin (Pauli Exclusion Principle).

fourth quantum number electron spin ms = + or -

Pauli Exclusion Principle each electron in any atom has a unique set of four quantum numbers
-an electrons set of quantum numbers is like a unique address within the atom - tells us shell number, type of orbital, orientation of orbital, electron spin

Building Up Principle (6.7)

-to explain electron arrangement in all elements: -add successive electrons to hydrogen to form heavier elements -orbitals fill from lowest energies to highest: the Aufbau principle -in many-electron atoms, orbitals within each shell no longer degenerate e.g. 2p orbitals higher in energy than 2s orbitals

-for element of atomic no. Z, we add Z electrons to fill its orbitals -hydrogen has a half-full 1s orbital its electron configuration as 1s1

He has a full 1s orbital 1s2

Li is 1s2 2s1 or because of its He core we can write [He]2s1

Similarly, Be is [He]2s2

-only outermost shell contains valence electrons those available to take part in reactions -at boron (Z = 5) one 2p orbital is half occupied

-for C there is a choice sixth electron can either pair up with fifth or else go into a new p orbital

its more stable for carbons two 2p electrons have parallel spins and reside in two separate 2p orbitals of equal energy.

-similarly N has three unpaired electrons

at oxygen electrons begin to pair up so O has only two unpaired electrons:

At Ne, n = 2 shell is full (atom has 8 valence electrons - a stable octet)

Ne forms no compounds

-after Ne, period 3 elements (n = 3) starts to fill (same as 2nd period) -the 3s orbital starts to fill first at sodium:

He noble gas core

Ne noble gas core

The Building-up Principle has a surprise after Argon (Z = 40): 4s orbital is lower in energy than 3d so fills first. K has configuration [Ar]4s1 and NOT [Ar]3d1. fills after

fills first

The Building-up Principle has a surprise after Argon (Z = 40): 4s orbital is lower in energy than 3d so fills first. K has configuration [Ar]4s1 and NOT [Ar]3d1. fills after

fills first

order of filling

-potassium reacts more violently with water than does Na (WHY?) -the reaction produces which gas? (and which salt?)

2K(s) + H2O(l)

??? (aq) + ??? (g)