12ChF321 Electron Arrangement

Electronic structure of atoms

Candidates should be able to: (a) Define the terms first ionisation energy and successive ionisation energy; (b) Explain that ionisation energies are influenced by nuclear charge, electron shielding and the distance of the outermost electron from the nucleus; (c) predict from successive ionisation energies of an element: (i) the number of electrons in each shell of an atom, (ii) the group of the element; (d) state the number of electrons that can fill the first four shells; (e) describe an orbital as a region that can hold up to two electrons, with opposite spins; (f) describe the shapes of s and p orbitals; (g) state the number of: (i) orbitals making up s-, p- and d-subshells, (ii) electrons that occupy s-, p- and d-subshells; (h) describe the relative energies of s-, p- and d- orbitals for the shells 1, 2, 3 and the 4s and 4p orbitals; (i) deduce the electron configurations of: (i) atoms, given the atomic number, up to Z = 36, (ii) ions, given the atomic number and ionic charge, limited to s and p blocks up to Z= 36; (j) classify the elements into s, p and d blocks.

Electron arrangements Only electrons are involved in chemical reactions (breaking and making bonds) we dont turn atoms into different atoms, so nuclei remain unchanged. It is therefore the electrons and their arrangement which give an atom its chemical properties. Our simple model was based on the ideas of Nils Bohr (1913) it isnt wrong, but it isnt sophisticated enough explain what we now need to understand. Bohr's model stated that electrons can only have fixed amounts of energy (called quanta) which means they are confined to specific energy levels, often called shells. They can move from one shell to another, but not exist anywhere outside a shell. Each shell has a number the principle quantum number, n. 2 electrons in the innermost shell well call that shell n=1 8 electrons in the second shell n=2 etc. Subsequent scientific principles, mainly Shroedingers wave equation, Heisenbergs uncertainty principle, and Paulis exclusion principle gave us the following more detailed and useful model: Electrons are actually found in defined regions of space called orbitals. Definition: An orbital is a region of space that can hold up to two electrons, each having opposite spins. Each type of orbital has a specific shape (they are actually fuzzy shapes but it is easier to draw the edge of the space where there is a 90% probability of finding the electron).

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12ChF321 Electron Arrangement

An s-orbital has the shape:

A p-orbital has the shape There are also d- and f-orbitals (the shapes get weirder !) Orbitals can only contain 0, 1 or 2 electrons, never more. (Paulis exclusion principle) Along with being negatively charged, electrons have a property called SPIN. We denote the spin of the first electron in an orbital as clockwise (shown as ) and a second electron in an orbital then has anticlockwise spin (). The opposite spins allow the electrons to share the same region of space, minimizing the repulsion between them due to their negative charges. Orbitals always come in sets - called subshells. A subshell is a set of orbitals of the same type: An s-subshell consists of one s-orbital (so it can contain up to 2 electrons) A p-subshell consists of three p-orbitals (can contain up to 6 electrons) These are arranged along the x,y and z axes (px, py and pz orbitals, so their orientation in space is at 90 to one another) A d-subshell consists of five d-orbitals (can contain up to 10 electrons) An f-subshell consists of seven f-orbitals (up to 14 electrons) The principle quantum shells n=1,2,3 etc. dont consist of a single energy level as Bohr thought, but in fact consist of a set of subshells. Each subshell has its own precise energy level. Shell n=1 is composed of just one s-subshell This is why n=1 can only contain up to 2 electrons. We call this subshell 1s Shell n=2 is composed of an s-subshell and a p-subshell This is why n=2 can contain up to 8 electrons We call these subshells 2s and 2p Shell n=3 is composed of an s-subshell, a p-subshell and a d-subshell This is why n=3 can actually contain up to 18 electrons We call these subshells 3s, 3p and 3d Page 2

12ChF321 Electron Arrangement

Shell n=4 is composed of an s-subshell, a p-, d- and f- subshell. n=4 can actually contain 32 electrons Filling Rules: When working out where the electrons go: RULE 1) An electron will go into the lowest available energy subshell. Within a shell, the ssubshell is lower in energy than the p-subshell, and p-subshells are lower in energy than the d-subshell etc. What determines the energy of a subshell is how far away from the nucleus (on average) the electrons are in that subshell the nearer to the nucleus, the lower the energy of the subshell. There are some surprises because of the shapes of the orbitals being different e.g. the electrons in the 4s subshell are on average nearer the nucleus than those in 3d. An energy level diagram helps show this, and gives us a way of deciding where to put electrons when we are filling them in to work out an electron arrangement. 4d 3d 3p 3s 2p 2s 1s n=1 n=2 n=3 n=4 n=5 This means the order of filling goes: 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, Remembering filling order: 4p 4s energy 5s

RULE 2) All the orbitals in a subshell will take one electron before any of them take a second electron (because electrons do repel, despite opposite spins)

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12ChF321 Electron Arrangement Writing electron arrangements You may be asked to write the electron arrangement in subshell notation, or using electronin-box diagrams. The method is the same: i) Find the number of electrons to fill in (same as the atomic number, for atoms) ii) Apply the filling rules
Atom electrons subshell notation 1s1 1s2 1s2 2s1 1s2 2s2 2p4 1s2 2s2 2p6 3s2 3p6 4s1 electrons-in-boxes

H He Li O K

1 2 3 8 19

1s

2s

2p

3s

3p

3d

4s

Its pretty time-consuming filling in all the notation, so sometimes we use the symbol for the Noble Gas at the end of the previous period to represent the inner shells e.g. K Ca Sc 1s2 2s2 2p6 3s2 3p6 4s1 = [Ar] 4s1 1s2 2s2 2p6 3s2 3p6 4s2 = [Ar] 4s2 1s2 2s2 2p6 3s2 3p6 3d1 4s2 = [Ar] 3d1 4s2

Electron arrangements for ions Work it out for the atom first, then either add electrons (for a negatively charged ion) or remove outermost electrons (for positively charged ions) to get the charge you need. Note: Putting electrons into 3d changes the relative energies of 3d and 4s, so electrons are removed from 4s before 3d. Check your understanding: Show electron arrangements i i) Kr ii) F+ iv) K v) S2-

iii) N3vi) Li+

Blocks Elements in the periodic table belong to either the s-block, d-block or p-block depending on which subshell the last electrons in (or the first to be removed) come from. Group 1 and Group 2 are the s-block elements* In between Group 2 and Group 3 are the d-block elements Groups 3-8 are the p-block elements* * Note: Helium is the exception, being an s-block element in Group 8

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12ChF321 Electron Arrangement Ionization Energies When an atom loses an electron to become a positive ion we say that it has been ionized. The first ionization energy of an element is defined as the energy needed to remove one electron from each atom in a mole of atoms of an element in the gaseous state. The energy needed to remove the electron is called the ionization energy. The symbol is Hi, and we add a subscript number to show which ionization we are describing: Hi1 = 1st ionization energy etc. We use an equation to show precisely what we mean: Ca(g) Ca+(g) + e- Hi1 = +590 kJ mol-1 Similarly, the second ionization energy of calcium (energy to remove not two electrons, but to remove one electron from a calcium ion having already had one removed) can be written as: Ca+(g) Ca2+(g) + eHi2 = +1150 kJ mol-1

(Note that these equations ALWAYS only have one electron in them) We could keep removing electrons until only the nucleus is left this would give us the successive ionization energies of the element, which are quite useful for understanding its electron arrangement. Check your understanding: vii) Write down an equation to show the third ionization energy of aluminium Successive Ionisation Energies For example, consider the successive ionization energies of sodium (ionization energies have been determined for most atoms, using emission spectra and electron bombardment of gaseous atoms). Get into the habit of working out the electron arrangement for the atom first, then writing under each ionization the identity of the electron which is removed:

Interpreting the data: The first electron is easy to remove, requiring least energy The next eight are fairly hard to remove, requiring progressively more energy The last two require much more energy to remove Page 5

12ChF321 Electron Arrangement So, the successive ionization energies reflect the simple electron configuration [2,8,1] for sodium. In fact we always see big steps in ionization energy when we go from one principle quantum shell to another, whatever the atom. Factors which affect ionization energies: The nuclear charge the more protons in the nucleus, the more strongly they will attract the electron being ionized Distance from nucleus the further away the electron to be removed is from nucleus, the weaker the attraction of the nucleus will be Shielding complete filled inner shells of electrons shield the electron to be removed from the attraction of the nucleus We use these factors to discuss how and why ionization energies vary: The successive ionization energies of sodium show a large step between the 1st and 2nd ionization energies, and again between 9th and 10th ionization energies. This is because the 1st electron removed comes from the n=3 shell and is therefore significantly further from the nucleus than the 2nd electron to be removed. There are also two filled shells (n=1 and n=2) shielding it from the nuclear charge. Similarly the 9th comes from the n=2 and experiences shielding from the filled n=1 shell, while the 10th comes from n=1 and experiences no shielding. An electron which is further away, or is more heavily shielded from the nuclear charge, experiences a weaker attraction from the nucleus and hence takes less energy to ionize (remove completely, away from the atom). There is a generally increasing trend in successive ionization energies, even for electrons taken from the same principle quantum shell (and therefore a similar distance from the nucleus, with the same shielding). We see this in the 2nd 9th ionization energies of sodium. The nuclear charge is the same (same number of protons), so thats not the reason. With fewer electrons in the outer shell, the repulsion between them gets less. This means that the radius gets smaller (e.g. an O+ ion is smaller than an O atom). The outer shell electrons are now closer to the nucleus and experiencing a stronger nuclear attraction which would have to be overcome another electron could be removed. Successive ionization energies are used to confirm the electron arrangement of elements, thus confirming to which group elements belong. Comparing first ionization energies of different atoms We also compare first ionization energies of atoms across periods and down groups in order to gain an understanding of electron arrangements. Consider the first ionization energies of the first 40 elements. The peaks and dips are occupied by elements in the same groups in other words there is a repeating pattern from one period to the next this characteristic is called periodicity.

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12ChF321 Electron Arrangement Observations: Group 8 tend to have the highest Hi1, whereas Group 1 have the lowest. There is a general increasing trend in Hi1 across a period (but the trend is uneven we dont need to be able to explain the uneven-ness at Alevel, just the general trend) There is a decreasing trend in Hi1 down any group, (although the transition metals vary much less than the rest).

Knowing the factors which affect ionization energies, we can explain these observations: Across a period: - electrons are being removed from same principle quantum shell - and therefore experience same shielding from filled inner shells - but number of protons is increasing across a period, so nuclear charge increases - making atomic radius smaller as nucleus attracts electrons more strongly - hence more energy needed to remove an outer shell electron from the atom Down a group: - each atom down the group has one more shell of electrons - so the outer shell electrons experience more shielding from filled inner shells - and as shells are added the outer shell electron is further from the nucleus - this means the nucleus attracts the outer shell electrons less strongly - and hence the ionization energies decrease - despite the number of protons, and hence the nuclear charge is increasing From one period to the next: - nuclear charge increases by the addition of one proton - but this is outweighed by the addition of a further principal quantum shell - so the outer shell electron is further from the nucleus - and experiences more shielding from filled inner shells - making it less strongly attracted, requiring less energy to remove Check your understanding: viii) Why does Ne have a higher first ionization energy than Ar ? ix) Why do first ionisiation energies increase from Al to Si to P ? x) Why is the first ionization energy of Na much less than that of Ne ?

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12ChF321 Electron Arrangement

Answers to 'Check your understanding' questions

Show electron arrangements in: i) Kr 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 ii) F 1s2 2s2 2p6 iii) N31s2 2s2 2p6 + iv) K 1s2 2s2 2p6 3s2 3p6 v) S21s2 2s2 2p6 3s2 3p6 + vi) Li 1s2 Third ionization energy of aluminium vii) Al2+(g) Al3+(g) + e- this is denoted Hi3 viii) Why does Ne have a higher first ionization energy than Ar ? The electron removed on ionization of Ne is from the n=2 principle quantum shell, whereas in Ar the electron is removed from the n=3 shell. The n=2 shell is nearer to the nucleus and therefore the ionized electron in Ne experiences a stronger attraction to the protons in the nucleus, which requires more energy to overcome. There is also less shielding (only the n=1 shell shields this electron from the nucleus, whereas for Ar the n=2 shell also shields the ionized electron from the nuclear charge). These factors outweight the increasing nuclear charge going from Ne to Ar. ix) Why do first ionisiation energies increase from Al to Si to P ? In all three of these atoms the ionized electron is being removed from the n=3 principle quantum shell, so the approximate distance from the nucleus and the shielding from n=2 and n=1 shells is the same in each of these atoms. However, going from Al to Si to P there is one more proton in the nucleus each time so the attraction of the nucleus is stronger, and requires more energy to overcome. x) Why is the first ionization energy of Na much less than that of Ne ? The electron removed on ionization of Na is from the n=3 principle quantum shell, whereas in Ne the electron is removed from the n=2 shell. The n=3 shell is further from the nucleus and therefore the ionized electron in Na experiences a weaker attraction to the protons in the nucleus, which requires less energy to overcome. There are also two filled shells shielding the ionized electron in Na whereas only one filled inner shell shields the ionized electron in Ne. These factors outweight the increasing nuclear charge going from Ne to Na.

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