Trends in some key periodic atomic properties Trends in Atomic size

The electron density in an atom extends far beyond the nucleus but we define the size of an atom in terms of its atomic radius one-half the distance between the two nuclei in two adjacent metal atoms. Definitions of atomic size
Metallic radius - one-half the distance between the nuclei of two adjacent atoms in a crystal of the element.

Covalent radius one-half the distance between bonded nuclei in a molecule of the element

For a covalent compound the bond length and known covalent radii is used.

Trends among the main group elements

The variation in atomic size are the result of two opposing influences:
Changes in n (principle quantum number): as n increases, the outer electrons spends more time farther from the nucleus, so the atoms are larger. Changes in Zeff: As Zeff increases, outer electrons are pulled closer to the nucleus the atoms are smaller. The net effect depends on the shielding of the increasing nuclear charge by inner electron. Down a group n dominates each member has 1 or more level of inner electrons; these shield the outer electrons very effectively.

Across a period - Zeff dominates from left to right (periodic table) electrons are added to same outer level, so the shielding by inner electrons does not change. Poor shielding the Zeff increase significantly outer electros are pulled closer.

Atomic radii of the main-group and transition elements.

Periodicity of atomic radius

Trends among the transition elements

Left to right size shrink through the first 2 or 3 elements Zeff increases
After that the size remains relatively constant because shielding by inner d electrons counteracts the increase in Zeff. Rank each set of main-group elements in order of decreasing atomic size:

a) Ca, Mg, Sr b) K, Ga, Ca c) Br, Rb, Kr d) Sr, Ca, Rb

a) Sr Ca Mg Group 2A size decrease up the group b) KCaGa - elements in Period 4 size decrease across a period c) RbBrKr Rb farthest to the left; K farthest to the right d) RbSrCa Ca has one fewer energy level, Rb farthest to the left

Ionic radii

Positive ions of elements in the same group increase in size down the group (Li+ to Rb+).
Also occurs with negative ions in the same group (F to I).

Radius Li: 152 pm; Li+: 76 pm

-when an electron is removed the nuclear charge remains the same (+3).
-BUT fewer electrons repelling each other.

-The positive charge can attract the two remaining electrons more strongly the electrons contract towards the nucleus.
-Decrease in ion size is greater when the electron removed comes from a higher energy level than the new outer electron. -For Li; the old outer electron was from a 2s orbital and the new outer electron is in a 1s orbital. -The shrinkage is great when 2 or more electrons are removed: -Mg atom: 160pm -Al atom: 143pm Mg2+ ion: 66pm Al3+ ion: 51pm

Sizes of ions and their neutral atoms (radii are given in picometers (1pm = 10-12m)

-From the figure above; anions are always larger than the atoms from which they are derived.
For anions, the nuclear charge is unchanged, but the added electron(s) introduces new repulsions and the electron clouds swell. F atom: 72 pm Fion: 133pm

increased electron-to-electron repulsion The oxide ion (O2-) & F- are isoelectronic have same electron configuration. BUT the oxide ion is larger than the fluoride ion because the O2- has only eight proton to attract ten 10 electrons. F- has nine protons to attract the same number of electrons.

Isoelectronic ion
Ionic radius (pm) Number of protons Number of electrons

O2-

F-

Na+

Mg2+

140

133

102

66

11

12

10

10

10

10

Sizes of isoelectronic ions

For each of these pairs, choose the smaller atom or ion:

a) Au atom or Au3+ ion

b) P atom or P3- ion c) Fe2+ ion or Fe3+ ion

a) Au3+ - cation smaller than its parent atom

b) P anions are larger than its parent atom

c) Fe3+ - both contain 26 protons; Fe3+ contains one electron fewer; radius smaller.

Trends in Ionization energy (IE) IE Energy required for the complete removal of 1 mol of electrons from 1 mol gaseous atoms or ions. Since energy flows into the system IE always positive IE1 first ionization energy removes outermost electron: Atom (g) ion+(g) + eion+(g) ion2+(g) + eE = IE1 > 0 IE2 second ionization energy removes a second electron E = IE2 (always > IE1)

Atoms with low IE1 form cations during reactions.

Atoms with high IE1 often form anions.

Ionization energy

The amount of energy required to remove the highest-energy electron from an isolated neutral atom in the gaseous state is the atom's ionization energy.

Periodicity of first ionization energy (IE1)

Relationship:

1 IE1 atomic size

As size decreases, more energy needed to remove an electron. Down a group: atomic size increases distance between nucleus to outermost electron increases attraction lessens electron easy to remove. Exception: Group 3A IE1 B > Al, but not for the rest of the group. Filling the d sublevels in Periods 4, 5 & 6 causes greater than expected Zeff, which holds the outer electrons more tightly. Across a period: Zeff increases atomic size decreases. Attraction between outer electron and nucleus increase electron harder to remove IE1 increases across a period

Within a given energy level, more energy is required to remove an electron from an s orbital than is required to remove an electron from a p orbital.

Within a set of orbitals at the same energy level, more energy is required to remove an electron from a half-filled orbital than from a filled orbital.

Rank the elements in the order of decreasing IE1. a) Kr, He, Ar b) Sb, Te, Sn c) K, Ca, Rb d) I, Xe, Cs

a) He>Ar>Kr - going down a group, IE1 decreases

b) Te>Sb>Sn going across the periodic table, IE1 increases c) Ca >K>Rb K higher in Group 1A, Ca farther to the right-Period 4

d) Xe > I > Cs I farther to the right and in the previous period.

Variation in successive ionization energies

Successive IE IE2, IE3, IE4

Successive IE increases each electron is pulled away from an ion with a higher and higher positive charge.

The first IE energies of beryllium (MJ/mol).

After the outer electron removed high IE values recorded greater energy needed to remove an inner (core) electrons. Because of the significantly greater energy needed to remove core electron, they are not involved in chemical reaction.

Name the period 3 element with the following ionization energies (in kJ/mol) and write its electron configuration:

IE1 1012

IE2 1903

IE3 2910

IE4 4956

IE5 6278

IE6 22230

The largest increase occurs after IE5, that is, after the 5th valence electron has been removed. Five electrons would mean that the valence configuration is 3s23p3 and the element must be phosphorous, P (Z = 15). The complete electron configuration is 1s22s22p63s23p3.

Electron affinity (EA) EA energy change accompanying the addition of 1 mol of electrons to 1 mol of gaseous atoms or ions. EA1 formation of 1 mol of monovalent (-1) gaseous anions: Atom (g) + e- ion- (g) E = EA1 Energy released when the first electron is added the electron attracted to the atoms nuclear charge. EA1 usually negative EA2 always positive energy must be absorbed overcome electrostatic repulsions and add another electron to a negative ion. Other factors affect EA trends not as regular.

Electron affinities of the main-group elements

Negative values indicate energy is released when the anion forms. Positive values indicate energy absorbed to form anion.

For instance; We expect EA to decrease smoothly down a group because the nucleus is farther away from an electron being added. But only Group 1A exhibits this behavior. From left to right, increase in EA is observed but not a regular increase.

Why?? changes in sublevel energy and in electron-electron repulsion.

3 points when examining IE and EA

1) Reactive non-metals:
Elements in Group 6A and Group 7A (halogens) have high IE and negative EA (exothermic). These elements lose electrons with difficulty but attract them strongly. - form negative ions. 2) Reactive metals: Group 1A low IE & slightly negative EA.

Group 2A low IE1 & IE2; positive EA.

both groups lose electrons readily. Ionic form positive ions 3) Noble gas:

Group 8A high IE and slightly positive EA.

-do not tend to lose or gain electrons

Section summary

Connection between atomic structure and chemical reactivity

Trend in metallic behavior

Metals left and lower three-quarter of the periodic table. - shiny solid, moderate to high melting points, good thermal & electrical conductors, tend to lose electrons in reaction with non- metals. Non-metals: upper right of the periodic table, low melting points poor thermal & electrical conductors, gain electrons in reactions with metal. Metalloids located in the region between the other two classes & have properties between them. Metallic behavior decreases left to right and increases top to bottom in the periodic table.

Relative tendency to lose electrons Metal lose electron during chemical reaction because low IE compared to non-metal. The tendency to form cations increases down the group. Across the period more difficult to lose an electron (IE increases) & easier to gain one (EA more negative). Elements at the left form cations; elements on the right form anions