Chemistry of the p-Block Flashcards
What is the definition of ionisation energy?
The energy required to remove completely an electron from the gaseous atom or molecule in its ‘ground state’.
What is the equation for the first ionisation energy?
M(g) → M+(g) + e-
What is the equation for the third ionisation energy?
M2+(g) → M3+(g) + e-
What is a feature of the values for ionisation energies?
They are always positive as ionisation requires an input of energy.
What are the trends in ionisation energy in a group?
Ionisation energy decreases down a group. This is because the electron is further away from the nucleus.
However, there are deviations in period 4 and other lower periods.
Why is there a deviation in the ionisation energy trend in period 4?
Periods 3 and 4 and periods 5 and 6 have very similar ionisation energies due to the d and f blocks increasing the nuclear charge but not providing much shielding.
What are the trends in ionisation energy across a period?
Generally, ionisation energy increases from left to right. This is because the atoms have a greater nuclear charge and so attract the electron more tightly.
However, there are deviations from the trend in group 13 and group 16.
Why is there a drop in ionisation energy in group 13 and group 16?
In group 13, the electron is being removed from a p orbital rather than an s orbital. p orbitals are higher energy and so are further away from the nucleus.
In group 16, the electron is being removed from a p orbital with two electrons in it. This creates extra Coulombic repulsion.
What is the definition of electron affinity?
The energy released when a gaseous atom, molecule or ion in its ‘ground state’ gains an electron.
What is a generic equation for the first electron affinity?
X(g) + e- → X-(g)
What is a feature of the values for electron affinity?
The electron affinity is positive as this is a favourable process.
What is the general trend for the electron affinity across a period?
It generally increases. However there are many deviations in the trend.
How do the electron affinities compare in group 1 and group 13?
Group 1 have larger electron affinities compared with group 13. This is because group 1 atoms will get a full s orbital which is more stable.
How do the electron affinities compare in group 1 to group 2?
Group 1 electron affinities are positive whereas group 2 electron affinities are negative. This is because in group 2 the electron is being added to a higher energy p orbital.
What are the electron affinities like in group 15?
They are anomalously low. This is because there are already in an np3 sub-shell. The extra electron added will be paired which creates Coulombic repulsion
How do the electron affinities compare in periods 3 and 4 and periods 5 and 6?
They have very similar values due to the presence of a the d and f block. There is a large increase in nuclear charge but a small increase in shielding.
How do the electron affinities compare between the 2nd and 3rd period?
The 2nd period has lower electron affinities than the 3rd period. This is because 2nd period elements are very small and so have a high charge to radius ratio. This increases Coulombic and inter-electron repulsions.
What is the definition of electronegativity?
The ability of an atom to attract electron density towards itself in a molecule.
How is Pauling’s electronegativity calculated?
It is calculated by taking the change in bond energies between the measured bond energy and the expected bond energy and applying this into an equation. If the atoms had identical electronegativities, the difference would be zero.
How can electronegativity vary for the same element?
It depends on what is bonded to the element, the oxidation state and the hybridisation.
sp > sp2 > sp3 due to the greater s character and the electrons being held more tightly.
What are the features of a van Arkel Ketelaar triangle?
The y-axis is the ionicity parameter and is the difference in electronegativity between the two atoms.
The x-axis is the covalency parameter which is the average electronegativity of the two atoms.
What is the definition of atomic radius?
The distance from the centre of the nucleus to the outermost electron. However, the outermost electron does not have a well defined position.
What is the covalent atomic radius defined as?
Half the length of the symmetrical homonuclear bond.
What is the metallic atomic radius defined as?
The equivalent distance between ions in a metal lattice.
What is effective nuclear charge?
The outermost electrons feel a nuclear charge which is less than the actual nuclear charge because of shielding effects from other electrons.
What are the trends in effective nuclear charge?
Across a period, effective nuclear charge increases substantially.
Down a group, effective nuclear charge increases (to a smaller extent).
What is the most important factor for ionisation energy?
The distance between the nucleus and the electron.
Why can Slater’s rules not explain the reduction in ionisation energy down a group?
Slater’s rules do not take into account the distance from the nucleus or penetration.
What happens to atomic radius across a period?
Radii decrease from left to right.
This is because increasing nuclear charge means electrons are more tightly held which means the orbital size and energy decrease. This causes the radius to contract.
What happens to atomic radius down a group?
Populating orbitals of the next principal quantum shell so further away from the nucleus.
Slater’s rules do not explain this.
How do ionic radii compare to atomic radii?
They follow similar trends but anions are larger due to greater inter-electron repulsion from more electrons.
Cations are smaller due to a greater Zeff.
What happens to radii when the oxidation state increases?
Radii will decrease due to a higher Zeff.
How does the radii change depending on coordination number?
More ligands around a metal centres means more electron density at the metal and an increased apparent size.
What happens to HOMO energies going down a group?
HOMO energies increase (less stable) and the s-p separation decreases.
This is because the electrons are in higher principal quantum shells so the electrons are further away from the nucleus.
Why are s electron energies lower than p electron energies?
S electrons are closer to the nucleus and more stabilised by the positive attractive force.
P electrons are less penetrating and so less stabilised by positive attractive force.
How does s and p orbital energy change across a period?
s and p orbital energies decrease across a period. This is more pronounced for s orbitals.
This is because Zeff is increased and s orbitals have a better penetration compared to p orbitals.
This also explains why the π and σ levels swap around from N2 to O2.
What are promotion energies?
The energy required to promote an electron from the ground state to the excited state.
This could be from an s orbital to a p orbital.
How do promotion energies change down a period?
Promotion energies generally increase down a group.
An exception is Ga and Ge.
How do forming oxides and fluorides affect the types of molecules formed?
Due to compounds containing fluorine having a higher covalency parameter, they are more likely to be discrete covalent molecules than in a covalent network structure.
What is the inert pair effect?
The tendency of the electrons in the outermost atomic s orbital to remain unionised or unshared in compounds of the group 13-16 elements.
It is also the observation that as a group is descended, the n-2 oxidation state becomes more favoured.
What are the causes of the inert pair effect?
Strength of covalent bonds decreases down a group due to poor orbital overlap. This means that bond enthalpy does not offset the hybridisation energy cost.
There are also relativistic effects which stabilise the 6s orbital for Tl and Pb.
What are relativistic effects?
The heavier the element, the faster the outer electrons move.
The theory of special relativity sates that objects moving near the speed of light gain mass.
How do relativistic effects cause stabilisation?
As the mass increases, the orbital contracts.
This is called direct relativistic orbital contraction.
This causes the s electrons of heavy elements to be more stable and less likely to be ionised or involved in bonding.
How are the different orbitals stabilised by relativistic effects?
S orbitals are stabilised the most as they have the best penetration.
P orbitals contact but not as much due to poorer penetration.
d and f orbitals experience indirect relativistic orbital expansion (destabilised). This is due to poor penetration and the contraction of s and p leaves them more shielded and less affected by Zeff.
What are trends in bond strength?
Generally, bonds become weaker and longer down a group. This is because there is a larger valence orbital volume but only two electrons per orbital so they are more diffuse. There is also less overlap and so sharing electron density is less effective.
Why do first row elements commonly form multiple bonds?
The 2pπ orbitals have a good overlap.
In second and later rows, they have poor overlap and so single bonds are favoured.
What are the features of pπ-dπ bonding?
A filled p orbital donates electrons to a vacant d orbital.
This happens in the P=O bond.
What is the valency of group 13 elements?
They only have three valence electrons so have a valence of 3. 3 bond pairs gives only 6 valence electrons so triel compounds are electron deficient (Lewis acids).
What is an exception in homonuclear bond strengths?
2nd period (from nitrogen to fluorine) are lower than expected due to greater electrostatic repulsions for smaller atoms which more charge-dense orbitals.
What are the trends for homonuclear bond energies going down a group?
Generally, bonds get weaker down the group due to larger valence orbitals and less effective overlap or sharing of electron density.
Why do group 1 and group 2 metals have low homonuclear bond energies?
The elements are more electropositive and so have adjacent partial positive charges. This causes electrostatic repulsion which destabilises the bonding interaction.
Hydrogen is an exception as it has a higher electronegativity along with small orbitals, good overlap, effective sharing of electron density. There are no electrostatic repulsions as there are only 2 electrons present. This is a very strong bond.
How do homonuclear bond energies change across a period?
Going from left to right (group 1 to 14), atoms get smaller and more electronegative. This leads to more effective orbital overlap and sharing of electron density causing stronger bonds.
From groups 15 to 17, lone pairs are present so the increased electrostatic repulsions weaken the bonds.
Why are B-F bonds very strong?
They have small orbitals with effective overlap and sharing of electron density. It is a polar covalent bond so there is additional electrostatic attraction. Pi donation from lone pairs on fluorine to empty p orbital on B is possible.
Why are Al-F bonds weaker than B-F bonds?
There are larger valence orbitals. This trend continues down the group.