7 Trends in periodic table, main group elements

a) Effective nuclear charge

b) Radii
c) Ionization energy
d) Electron affinity
e) Main group elements
7 Trends, a) effective nuclear charge
• for a specific electron, inner electrons shield nuclear charge
Zeff = Z – S, Z: nuclear charge, S: shielding
• Different methods exist for the calculation of S
• Simple model: S = number of inner electrons
• Slater-rules (simple variant used here, no d-electrons):

larger n 0
same n 0,35
electrons with n-1 contribute 0,85 per electron to S
< n-1 1,00

n: principal quantum number

7 Trends, a) effective nuclear charge
• Within a period (left to right):
increase of Zeff [Z increases, number of inner electrons constant]
• Within a group (top to bottom):
small increase of Zeff [Z increases strongly, more inner electrons]

• remark: smaller shielding for s electrons, because of probability at

nucleus
7 Trends in periodic table, b) radii
• definition:
nonbonding atomic radius: minimum nucleus-nucleus distance
during collisions
bonding atomic radius: from nucleus-nucleus distance in covalent
bonds between like elements (e. g. Cl₂)
• Period: decrease from left to right (increase Zeff)
• Group: increase top to bottom (n increases)
• Ionic radii: in general r(cation) < r(atom) < r(anion) (same element)
isoelectronic series: e. g. O²⁻ - F⁻ - Na⁺ - Mg²⁺ - Al³⁺
→ decreasing ionic radius
7 Trends in periodic table, b) radii
7 Trends in periodic table, c) ionization energy (IE)
• I₁ (1st IE): E → E⁺ + e⁻; I₂ (2nd IE): E⁺ → E²⁺ +e⁻ …
in general increase in IE in every step
large increase, if inner electrons are removed
7 Trends in periodic table, c) ionization energy (IE)
Considering only I₁
• Depending on Zeff and average distance of electron from nucleus
• Group: decrease top to bottom (radius)
• Period: increase left to right (Zeff, radius)
non-linear effects 2nd/3rd and 5th/6th group (electron configuration!)
small variations for transition metals: s- vs. d-electrons
7 Trends in periodic table, c) ionization energy
(IE)
7 Trends in periodic table, c) ionization energy (IE)
7 Trends in periodic table, d) Electron affinity (EA)
• EA: E + e⁻ → E⁻; E⁻ +e⁻ → E²⁻ …
usually negative energies (attraction)
• Group: similar values (radius vs. repulsion)
• Period: increase left to right
nonlinear effects 2nd/3rd and 5th/6th group (electron configuration!)
7 Trends in periodic table, d) electron affinity
(EA)
7 Trends in periodic table, general
• metals:
small ionization energies → cations
typically ionic compounds (or metal bonds)
metal oxides react in water basic
• nonmetals:
large electron affinities → anions
among nonmetals: covalent bonds
react in water acidic
• metalloids:
mixed properties
often semiconductors
7 Trends, e) main group elements
• 1A: Hydrogen + alkaline elements
• 2A: alkaline earth elements
• 3A: boron group
• 4A: carbon group
• 5A: pnictogenes
• 6A: chalkogenes
• 7A: halogens
• 8A: noble gases
7 Trends, e) main group elements
hydrogen
• synthesis:
• Steam Reforming CH₄ (g) + H₂O (g) → CO (g) + 3 H₂ (g) [Ni, 900° C]
CO (g) + H₂O (g) → CO₂ (g) + H₂ (g) [Co₃O₄, 450° C]
• CH₃OH + H₂O → 3 H₂ + CO₂ [Cu/ZnO/Al₂O₃, 270° C]
• Water gas H₂O (g) + C (s) → CO (g) + H₂ (g)
• typically H⁺
• also hydrides H⁻: metallic (e. g. NaH) and molecular (e. g. AsH₃)
7 Trends, e) main group elements
1A: alkaline elements Li – Na – K – Rb – Cs – (Fr); oxidation number: +1
• alkali – arabic for ashes
• Na/K: nerv system, K: fertilizer [Li: rechargable batteries]
• Elementary very reactive; small ionization energies
• 2 M + H₂ → 2 MH
• 2 M + 2H₂O → 2MOH + H₂
• oxides: Li₂O, peroxides: Na₂O₂,
superoxides: KO₂ – RbO₂ – CsO₂
• characteristic flame colors:
• Li – red
• Na – yellow
• K – purple
7 Trends, e) main group elements
2A: alkaline earth elements Be – Mg – Ca – Sr – Ba – (Ra); oxidation number: +2
• Mg: enzymes, Ca: bones (Ca₅[OH(PO₄)₃] hydroxy apatite)
• beryll Al₂Be₃[Si₆O₁₈]
• Be, Mg stable in air (passivation)
others M + 2H₂O → M(OH)₂ + H₂
• Water hardness: 1° dH = 10 mg/l CaO
• BaSO₄: contrast agent
• Characteristic flame colors:
• Ca – brick-red
• Sr – red
• Ba – green
7 Trends, e) main group elements
3A: boron group B – Al – Ga – In – Tl; oxidation number: +3 (heavier
elements: +1)
• Boron: special element, light, nonmetal, electron deficiency
• Elementary:
B₁₂ icosahedron
7 Trends, e) main group elements
3A: boron group B – Al – Ga – In – Tl; oxidation number: +3 (heavier
elements: +1)
• Boranes: boron-hydrogen compounds with
2 electrons – 3 center bonds
Diborane B₂H₆
B: sp³ hybridized
12 electrons for
8 bonds
• many structures: BₓHₓ₊₄ with x = 2, 5, 6, 8, 10, 12, 14, 16, 18
BₓHₓ₊₆ with x = 4, 5, 6, 8, 9, 10, 13, 14, 20
7 Trends, e) main group elements
4A: carbon group C – Si – Ge – Sn – Pb; oxidation number: +4
(heavier elements: +2)
• carbon: organic chemistry, C-C connections
• elementary: graphite – diamond – fullerenes – (graphen, nanotubes)
• carbides: acetylide ion C₂²⁻ covalent (e. g. SiC), interstitial (e. g. WC)
7 Trends, e) main group elements
graphite
7 Trends, e) main group elements
diamond
7 Trends, e) main group elements
fullerenes: C50 – C60 – C70
7 Trends, e) main group elements
carbon nanotubes
7 Trends, e) main group elements
4A: carbon group C – Si – Ge – Sn – Pb; oxidation number: +4
(heavier elements: +2)
• Silicon: sand, glass, elementary: semiconductor
• SiO₄-tetrahedron as basic module for multiple structures (connection
of tetrahedrons, varying bond angles and bond lengths)
• lead: car battery (later)
PbO, PbO₂ – minium Pb₃O₄ with PbO₄⁴⁻ plumbate ion
7 Trends, e) main group elements
5A: pnictogenes N – P – As – Sb – Bi; oxidation numbers: -3, (+5, +3)
• gr. pnigein – to stifle
• N: all oxidation numbers possible!
• N₂: low reactivity,
Haber process: N₂ + 3 H₂ → 2 NH₃ (later) fertilizer!
• Hydrazine N₂H₄ – rocket fuel
7 Trends, e) main group elements
5A: pnictogenes N – P – As – Sb – Bi; oxidation numbers: -3, (+5, +3)
• P: elementary: white (P₄) and red (amorphous) phosphorous
7 Trends, e) main group elements
5A: pnictogenes N – P – As – Sb – Bi; oxidation numbers: -3, (+5, +3)
• phosphate: P₄O₆, P₄O₁₀
fertilizer!
7 Trends, e) main group elements
5A: pnictogenes N – P – As – Sb – Bi; oxidation numbers: -3, (+5, +3)
• Energy storage in the body: ATP/ADP
adenosine triphosphate

“PO₄³⁻“ + →

+ 33 kJ/mol
7 Trends, e) main group elements
5A: pnictogenes N – P – As – Sb – Bi; oxidation numbers: -3, (+5, +3)
• As/Sb:
• metalloid, GaAs: semiconductor material
• AsH₃ (also SbH₃) toxic gas

• Bi: metal
7 Trends, e) main group elements
6A: chalkogenes O – S – Se – Te – Po; oxidation numbers: -2, (+6, +4)
• gr: (copper) ore builder
• S: existing in elementary form (volkanoes) – S₈
on heating many intermediate structures, among them polymeric sulphur
vulkanization: S-S linkage of rubber

• SO₂, SO₃: ‚acid rain‘

• H₂S: danger
7 Trends, e) main group elements
7A: halogenes F – Cl – Br – I – (At);
oxidation number: -1, (+1, +3, +5, +7)
• gr: salt builder
• Interhalogen compounds: XX‘, XX‘₃, XX‘₅, XX‘₇
• I₃⁻: soluble iodine (I₂ insoluble in water, in KI-solution solvable)
verification of starch
7 Trends, e) main group elements
8A: noble gases He – Ne – Ar – Kr – Xe - (Rn)
• all unreactive, gases
• He: cooling agent
• Ne: illuminant
• Heavier elements exist also in compounds, formal oxidation numbers
+2, +4, +6, +8
e. g. XeF2, XeO3, …
KrF₂ (at low temperatures)