Periodic Properties of the Elements

Chapter 8

The Periodic Table

Based upon periodic law

Independently proposed in 1869 by L. Meyer and D. Mendeleev Similar properties recur periodically when elements are arranged according to increasing atomic number* Meyer used graphical methods of properties and atomic mass to find periodicity

Needed several different plots to confirm that there were recurrent themes

* From General Chemistry Petrucci et al. Prentice Hall, New Jersey, 2007, page342.

The Periodic Table

Mendeleev used table format

Left spaces for elements not yet found Predicted properties of proposed elements Noble gases had not been discovered Organization was based on the formation of the oxide or halide ratio and the atomic mass Atomic masses were converted to atomic number by H. G. J. Moseley using x-ray analysis

Other formats of the periodic table have been prepared since Mendeleevs version

Electron Configurations

e- configurations are linked to periodic table groups Valence e

Are part of the outermost or valence shells Usually have the highest principle quantum number Are involved in reactions Are completed energy levels, i.e. the e- from the previous noble gas Are not involved in reactions

Core e

Have rules for the orbital assignment of the e-

Non-H Elements

For multi-electron elements, e- may be counted and assigned to orbitals using spdf notation or orbital diagramming Orbitals have the same approximate shape as for hydrogen e- with the same are no longer degenerate Shielding or screening

inner e- act as a barrier to the p+ pull of the nucleus e- that are further away from the p+ are less tightly held (are loosely held) The amount of p+ charge that the shielded e- feels is reduced and known as Zeff or the effective nuclear charge

Non-H Elements

Effective Nuclear Charge

Zeff = Z - S p+ charge that the e- actually feels Is higher the closer the electron is to the nucleus The inner core/noble gas e- shield the outer/valence e- from the nuclear charge but do not shield each other Is an increased p+ pull/feeling of the nucleus on the e- when the e- is near to the nucleus Caused by overlap of the orbitals

Penetration

Electron Configurations

Rule 1 Aufbau Principle

The e- go into the ground state/lowest possible energy conformation in the order of increasing e- energy Start with filling the orbitals of lower energy first (inner shells), then the valence shells with eThe orbital filling order was determined by experiment No two e- in an atom can have the same set of four quantum numbers Results in 2e- per orbital and the 2e- have opposite spin Determined by the Stern-Gerlach experiment There should be as many unpaired e- as possible Orbitals are first filled with 1e-, and then doubled up due to e- erepulsions

Rule 2 Pauli Exclusion Principle

Rule 3 Hunds Rule

Electron Notation and Orbital Diagrams

Two ways to write the e- configurations (e.g. 16 O)

Spdf notation

Expanded version 16O: 1s2, 2s2, 2px2, 2py1, 2pz1 Condensed version 16O: 1s2, 2s2, 2p4 Inner electron version 16O: [He] 2s2, 2p4

Orbital diagrams

16

O:

1s

2s

2p

Electron Notation and Orbital Diagrams

Transition metal spdf notation may be written two ways:

[Noble gas] 3dx, 4sy [Noble gas] 4sy, 3dx common for larger transition metals, the lanthanides and the actinides Figure 8.7 has e- configurations for the elements Cr: [Ar] 3d5, 4s1 Cu: [Ar] 3d10, 4s1

Exceptions to the three rules are:

Electron Notation and Orbital Diagrams

The periodic table may be used to identify the orbital type that is being filled:

s block

Group 1A alkali metals Group 2A alkaline earth metals Groups 3A-8A Group 7A halogens Group 8A noble gases, have completely filled shells Groups 1B-8B transition metals Inner transition metals Lanthanides and actinides

p block

d block

f block

Periodic Properties and Trends

Atomic Size

Work with effective atomic radius distance at 90% of the e- charge density measured in terms of the internuclear distance (distance between 2 atoms) Measured originally in angstroms (), currently in pm
1 nm = 1000 pm = 1 x 10-9 m = 10

Have several types of radii and trends

Periodic Properties and Trends

Bonding atomic radius or covalent radius

measured as distance between 2 covalently bound or crystalline atoms (single bond) measured as distance between 2 nuclei in a solid as determined by the density of the solid, not bound atoms measured as distance between 2 ionically bound atoms taking into account the difference between anions and cations measured as distance between 2 metal atoms in the crystalline metallic solid Is an average bonding atomic radius determined using different bound elements Is smaller than the van der Waals radii

Non-bonding atomic radius or van der Waals radius

Ionic radius

Metallic radius

Atomic radius

Periodic Properties and Trends

Atomic Radii trend 1 The atomic radius increases as you go down a group Larger values of n give larger atoms Atomic Radii trend 2 The atomic radius decreases as you go across a row (left to right) e- are entering the same subshell (amount of shielding is the same) but the nucleus is growing (more p+ pull) Atomic Radii trend 3 Transition and inner transition radii change very little The e- are entering into inner subshells which have similar energy to the surrounding filled subshells Atomic Radii trend 4 Fully filled and filled orbital sets have decreased radii when compared to those around them - Related to shielding, Z eff and e e repulsions

Periodic Properties and Trends

Ion Radius

Isoelectronic the same number of eCations

Positively charged to obtain nearest noble gas or half filled orbital set Smaller than the starting atom due to increased Zeff Comparing 2 isoelectronic cations, the smaller one has more positive charge Negatively charged to obtain nearest noble gas or half filled orbital set Larger than the starting atom due to decreased Zeff Comparing 2 isoelectronic anions, the larger one has more negative charge

Anions

Periodic Properties and Trends

Ionization energy (IE) Is the amount of energy required for a gaseous atom to lose a loosely held e

Gives a positive energy value

The easier an element is to ionize, the more metallic the cation is The first e- is easy to remove, the second e- is difficult since it is more tightly held due to a cation having been formed Valence e- are relatively easily removed, whereas inner e- are very difficult as a set of filled orbitals must be opened/broken

Periodic Properties and Trends

Ionization Energy (cont.) Trends

Increases across rows (left to right, same n)

Related to Zeff Related to increased size and shielding

Decreases when going down groups (larger n)

Decreases with increasing atomic radii Al is smaller than Mg removal of e- from the p versus s subshell S is smaller than P filled orbitals require less energy to form than do other arrangements

Exceptions

Periodic Properties and Trends

Electron Affinity (EA)

Amount of energy lost upon gaining an e- in the gaseous state to form an anion

Stronger likelihood of gaining an e- high e- affinity low EA value large negative value (most negative number)

Need the new e- configuration to be more stable than the original (either filled or completely filled orbitals) First EA value commonly negative (spontaneous) Second EA value commonly positive (not spontaneousenergy is required to add the e-)

Periodic Properties and Trends

Magnetic properties

Based on ms Diamagnetic

All e- are paired Repelled or neutral to magnetic field Have at least 1 unpaired eAttracted to a magnetic field

Paramagnetic

Magnetism may be different for the atom and its ions

General Properties

Metals

Good conductors of heat and electricity Malleable and ductile solids Tend to lose e- to form cations (positively charged ions), some metals form more than one cation Require energy to lose the e- (not spontaneous) May be

Main group lose from the s orbital to obtain the nearest noble gas e- configuration Transition lose from the s subshell first, then the d subshell to form either filled or completely filled subshells (rarely form noble gas e- configuration)

General Properties

Non-metals

Groups 3A-8A Poor at conducting heat and electricity Brittle solids, liquids or gases Gain e- to make negatively charged ions (anions) with e- configurations of the nearest noble gas First e- gained spontaneously, second e- requires some energy for addition (not spontaneous)

General Properties

Noble gases

Group 8A Inert Complete e- configurations Other elements gain/lose e- to have the same econfiguration Tend to look like metals Have some metal properties and some non-metal properties Tend to gain e- to become the nearest noble gas, although some lose e-

Metalloids