Post on 17-Nov-2014
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PERIODICITY
The Periodic Table
• from left to right, in order of increasing proton number (atomic number)
1H
• horizontal rows or periods
2He
3Li 4Be 5B 6C 7N 8O 9F 10Ne
11Na 12Mg
1
2
3
4
5
6
7
13Al 14Si 15P 16S 17Cl 18Ar
The Periodic Table
1H 2He
3Li 4Be 5B 6C 7N 8O 9F 10Ne
11Na 12Mg
1
2
3
4
5
6
7
• vertical groups
13Al 14Si 15P 16S 17Cl 18Ar
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
• blocks: ss--blockblock, pp--blockblock, dd--blockblock and ff--blockblock
The Periodic Table
1H 2He
3Li 4Be 5B 6C 7N 8O 9F 10Ne
11Na 12Mg
1
2
3
4
5
6
7
• arrangement is such that elements show periodicity in physical and chemical properties
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
13Al 14Si 15P 16S 17Cl 18Ar
periodicity
the repeating pattern of physical and chemical properties
Atomic Radii
• Atomic radii describes the relative sizes of atoms.
• Atomic radii increase within a column going from the top to the bottom of the periodic table.
• Atomic radii decrease within a row going from left to right on the periodic table.– This last fact seems contrary to intuition.– How does nature make the elements smaller even though the electron number is increasing?
Periodic Trends in Atomic Radius
Li F
Cl
Br
I
Na
K
Rb
Mg Al Si P S
Cs
Ar
Atomic Radii
Atomic Radii
• The reason the atomic radii decrease across a period is due to shielding or screening effect.– Effective nuclear charge, Zeff, experienced by an electron is less than the actual nuclear charge, Z.
– The inner electrons block the nuclear charge’s effect on the outer electrons.
• Moving across a period, each element has an increased nuclear charge and the electrons are going into the same shell (2s and 2p or 3s and 3p, etc.).– Consequently, the outer electrons feel a stronger effective nuclear charge.
– For Li, Zeff ~ +1 For Be, Zeff ~ +2
Atomicradius/nm
Nuclearcharge
Atomic Radius Trend across Period 3
+12 +13 +14 +15 +16 +17 +18+11
Mg Al Si P S Cl ArNa
0.145 0.118 0.111 0.098 0.088 0.0790.190 0.071
decreases from left to right
Factors determining size
• Nuclear charge– the greater the nuclear charge, the
smaller the size
• Shielding effect by inner electrons– the greater the shielding effect, the
greater the size
• Number of shells– the greater the
number of shells, the greater the size
+11+17
Reasons for trend across the Period
• Nuclear charge increases across the Period
• Shielding effect is relatively constant
Hence, overall atomic radius decreases across the Period.
• Number of shells remains constant
Element
Li
Na
K
Rb
Cs
Atomic Radius/nm
0.123
0.157
0.203
0.216
0.235
Nuclear Charge
+3
+11
+19
+37
+55
ElectronicStructure
2.1
2.8.1
2.8.8.1
2.8.18.8.1
2.8.18.18.8.1
Atomic Radius Trend down Group 1
Atomic Radius vs Proton Number (Group 1)
0.05
0.1
0.15
0.2
0.25
3 11 19 37 55
AtomicRadius/nm
Proton Number
• The number of shells increases
• The increase in nuclear charge is nullified by the shielding effect of inner electrons
Reasons for trend down a Group
Atomic Radii
• Example 6-1: Arrange these elements based on their atomic radii.– Se, S, O, Te
You do it!You do it!
O < S < Se < Te
Atomic Radii
• Example 6-2: Arrange these elements based on their atomic radii.– P, Cl, S, Si
You do it!You do it!
Cl < S < P < Si
Atomic Radii
• Example 6-3: Arrange these elements based on their atomic radii.– Ga, F, S, As
You do it!You do it!
F < S < As < Ga
Ionic Radii
• Anions (negative ions) are always largerthan their neutral atoms.
1.191.261.71Ionic
Radius(Å
F1-O2-N3-Ion
0.720.730.75Atomic
Radius(Å)
FONElement
Ionic Radii
• Cations (positive ions) are always smallerthan their respective neutral atoms.
0.590.90Ionic
Radius (Å)
Be2+Li+Ion
1.121.52Atomic Radius (Å)
BeLiElement
0.680.851.16Ionic
Radius (Å)
Al3+Mg2+Na+Ion
1.431.601.86Atomic Radius (Å)
AlMgNaElement
A neutral atom is larger than its cation.
A neutral atom is smaller than its anion.
Li+ F-
Cl-
Br-
I-
Na+
K+
Rb+
Mg2+ Al3+ P3- S2-
Cs+
Ionic Radii
Ionic Radii
• Cation (positive ions) radii decrease from left to right across a period.– Increasing nuclear charge attracts the electrons and decreases the radius.
0.941.321.66Ionic
Radii(Å)
In3+Sr2+Rb+Ion
Ionic Radii
• Anion (negative ions) radii decrease from left to right across a period.– Increasing electron numbers in highly charged ions cause the electrons to repel and increase the ionic radius.
1.191.261.71Ionic
Radii(Å)
F1-O2-N3-Ion
Ionic Radii
• Cation (positive ions) radii decrease from left to right across a period.– Increasing nuclear charge attracts the electrons and decreases the radius.
0.941.321.66Ionic
Radii(Å)
In3+Sr2+Rb+Ion
Ionic Radii
• Anion (negative ions) radii decrease from left to right across a period.– Increasing electron numbers in highly charged ions cause the electrons to repel and increase the ionic radius.
1.191.261.71Ionic
Radii(Å)
F1-O2-N3-Ion
Na Na+
2.8.1Electronic Structure 2.8
NuclearCharge
+11 +11
• Nuclear charge attracting 1 less electron
• Loss of 1 shell
A neutral atom is larger than its cation.
2.8.7Electronic Structure
2.8.8
NuclearCharge
+17 +17
Nuclear charge attracting 1 more electron
A neutral atom is smaller than its anion.
Cl Cl−−−−
Ionic Radius vs Proton Number for Periods 2 and 3
0
0.05
0.1
0.15
0.2
0.25
3 4 5 6 7 8 9 11 12 13 14 15 16 17
Ionic radius/nm
Proton Number
Period 3 (Na+ Cl−)
Ionic radius decreases from Na+ to Si4+ because
2.8 2.8 2.8 2.8 2.8.8 2.8.8 2.8.8
Ion
Electronic
Structure
Nuclear
Charge
Na+ Mg2+ Al3+ Si4+ P3−−−− S2−−−− Cl−−−−
+11 +12 +13 +14 +15 +16 +17
Na+, Mg2+, Al3+, Si4+ are isoelectronic but the nuclear charge increases from +11 to +14.
Hence, the electrons are pulled closer to the nucleus.
Ionic radius decreases from P3− to Cl− because
P3−, S2−, Cl− are isoelectronic but the nuclear charge increases from +15 to +17
sharp rise in ionic radius from Si4+ to P3−
2.8 2.8 2.8 2.8 2.8.8 2.8.8 2.8.8
Ion
Electronic
Structure
Nuclear
Charge
Na+ Mg2+ Al3+ Si4+ P3−−−− S2−−−− Cl−−−−
+11 +12 +13 +14 +15 +16 +17
Electronegativity
Electronegativity is a measure of how strongly an atom of an element attracts valence electrons in a chemical bond.
Electronegativity
Periodic Trends in Electronegativity
Li F
Cl
Br
I
Na
K
Rb
Mg Al Si P S
Cs
Ar
0.93 1.31 1.61 1.90 2.19 2.58 3.16
0.83
0.98
0.82
0.79
2.66
2.96
3.98
Going down a Group, Electronegativity decreases because atomic radius increases.
Across a Period, Electronegativity increases because atomic radius decreases.
Electronegativity
• Example 6-11: Arrange these elements based on their electronegativity.– Se, Ge, Br, As
You do it!You do it!
Ge < As < Se < Br
Electronegativity
• Example 6-12: Arrange these elements based on their electronegativity.– Be, Mg, Ca, Ba
You do it!You do it!
Ba < Ca < Mg < Be
Ionisation Energy
The energy required to remove one mole of electrons from one mole of atoms of the element in the gaseous state to form one mole of positively charged gaseous ions.
e.g. H(g) → H+(g) + e- ∆H = +1310 kJ mol-1
Na(g) → Na+(g) + e- ∆H = +494 kJ mol-1
First Ionization Energies of Some Elements
Factors affecting ionisation energies
• Nuclear charge– the greater the nuclear charge, the
greater the I.E.
• Atomic/ ionic size
– the greater the atomic/ ionic size, the lower the I.E.
+9+3
• Shielding effect by inner electrons
– the greater the shielding effect, the lower the I.E.
Ionization Energy
• First, second, third, etc. ionization energies exhibit periodicity as well.
• Look at the following table of ionization energies versus third row elements.– Notice that the energy increases enormously when an electron is removed from a completed electron shell.
Ionization Energy
435611,58010,5509540IE4
(kJ/mol)
3232274577336912IE3
(kJ/mol)
1577181714514562IE2
(kJ/mol)
786578738496IE1
(kJ/mol)
IVA
Si
IIIA
Al
IIA
Mg
IA
Na
Group and
element
Ionization Energy
• The reason Na forms Na+ and not Na2+ is that the energy difference between IE1 and IE2 is so large.– Requires more than 9 times more energy to remove the second electron than the first one.
• The same trend is persistent throughout the series.– Thus Mg forms Mg2+ and not Mg3+.– Al forms Al3+.
Ionization Energy
• Example 6-7: What charge ion would be expected for an element that has these ionization energies?
You do it!You do it!
92040IE8 (kJ/mol)
17870IE7 (kJ/mol)
15160IE6 (kJ/mol)
11020IE5 (kJ/mol)
8410IE4 (kJ/mol)
6050IE3 (kJ/mol)
3370IE2 (kJ/mol)
1680IE1 (kJ/mol)
Notice that the largest increase in ionization energies occurs
between IE7 and IE8. Thus this element would form a 1- ion.
Periodic Trend in First Ionization Energy of Period 3
0
200
400
600
800
1000
1200
1400
1600
Na Mg Al Si P S Cl Ar
3rd period
Ionization Energy
• Example 6-4: Arrange these elements based on their first ionization energies.– Sr, Be, Ca, Mg
You do it!You do it!
Sr < Ca < Mg < Be
Ionization Energy
• Example 6-5: Arrange these elements based on their first ionization energies.– Al, Cl, Na, P
You do it!You do it!
Na < Al < P < Cl
Ionization Energy
• Example 6-6: Arrange these elements based on their first ionization energies.– B, O, Be, N
You do it!You do it!
B < Be < O < N
Periodic Trend in First Ionization Energy of Group 7
0
500
1000
1500
2000
F Cl Br I
Group 7
Periodic Trend in First Ionization Energy of Group 1
0
100
200
300
400
500
600
Li Na K Rb Cs
Group 1
Periodic Trend in Melting Points of Period 3
0
500
1000
1500
2000
Na Mg Al Si P S Cl Ar
3rd period
melting point depends both on the structure of the element and on the type of attractive forces holding the atoms together
302312336371454M.pt/K
CsRbKNaLiGroup 1
Melting point decreases down the group as the atoms become larger and the strength of the metallic bond decreases.
38726617253M.pt/K
I2Br2Cl2F2Group 17
The melting points increase as the van der Waals’
forces of attraction between the diatomic molecules
increases down the group.
CsRbKNaLiAlkali
metals
2,8,8,18,18,12,8,8,18,12,8,8,12,8,12,1Electronic
structure
increasing atomic and ionic radius
decreasing ionization energy
increasing reactivity
decreasing electronegativity
ALKALI METALS
increasing atomic and ionic radius
decreasing ionization energy
increasing reactivity
increasing electronegativity
HALOGENS
solidliquidgasgasState at r.t.p.
blackreddish-
brown
yellowish
green
pale yellowColour
2,8,8,18,72,8,8,72,8,72,7Electronic
structure
IBrClFHalogens
decreasing oxidising strength
No reactionNo reactionNo reactionNo reactionIodine
Solution turns
yellow, then
brown, then
black
precipitate
No reactionNo reactionNo reactionBromine
Solution turns
yellow, then
brown, then
black
precipitate
Solution turns
yellow, then
brown
No reactionNo reactionChlorine
Pale yellow
precipitate
Cream
precipitate
White
precipitate
(rapidly
darkens to
black in
sunlight)
No reactionAqueous
Ag+
I-Br-Cl-F-reagent
summary of reactions of the halide ions
Anomalous Behaviour
Bond Dissociation Energy of halogens
F2: 155
Cl2: 242
Br2: 193
I2: 151
0
50
100
150
200
250
300
Fluorine Chlorine Bromine Iodine
Anomalous Behaviour
Reduction Potentials of alkali metal ions
Li+: -3.05
Na+: -2.71
K+: -2.92
Rb+:-2.93
Cs+: -2.92
872387185532528274013801156Boiling
point /K
2,8,82,8,72,8,62,8,52,8,42,8,32,8,22,8,1Electronic
structure
ArClSPSiAlMgNaPeriod 3
decreasing atomic radius
increasing ionization energy
increasing electronegativity
decreasing metallic character
increasing hydrolysis of chlorides
increasingly acidic oxides
PERIOD 3
acidicweakly
acidic
neutralNature of
solution
dissolvefumes of HCl produceddissolve easilyReaction
with water
simple molecularionicionicStructure
nonenonenonenonepoorgoodgoodElectrical
conductivity
in
molten state
-351367658-14121413boiling pt/ oC
-101-80-112-70178 (sublimes)
714801Melting pt/ oC
gasliquidliquid(solid)
liquidsolidsolidsolidState at 25oC
Cl2S2Cl2PCl3(PCl5)
SiCl4Al2Cl6MgCl2NaClformula
Chlorides of Period 3
acidicacidicacidicacidicamphotericbasicbasicNatureof oxide
Cl2O7
forms HClO4 anacidic
solution
SO3 forms H2SO4 a
strong acid
P4O10
forms H3PO4 an acidic solution
Does notreact
Does not react
Forms Mg(OH)2(aq)
weakly alkaline
Forms NaOH(aq)
an alkaline solution
Reaction with water
simple moleculargiant covalent
ionicionicionicStructure
nonenonenonevery
poor
goodgoodgoodElectrical conductivity inmolten state
8045175223029803600-boiling pt/ oC
-9217241610202728521275Melting pt/ oC
liquid (gas)
liquid (gas)
solid (solid)
solidsolidsolidsolidState at 25oC
Cl2O7
(Cl2O)
SO3
(SO2)
P4O10
(P4O6)
SiO2Al2O3MgONa2Oformula
Oxides of Period 3
• exhibit variable oxidation states
• ability to form complex ions
• ability to form coloured compounds
• catalytic property
+2+1,+2+2+2+2,+3+2,+4,
+6,+7
+2,+3,
+6
+2,+3,
+4,+5
+2,+3,
+4
+3Common
oxidation
states
[Ar]3d104s2[Ar]3d104s1[Ar]3d84s2[Ar]3d74s2[Ar]3d64s2[Ar]3d54s2[Ar]3d54s1[Ar]3d34s2[Ar]3d24s2[Ar]3d14s2Electronic
structure
ZnCuNiCoFeMnCrVTiSc1st row of
d-block
decreasing stability of maximum oxidation state
increasing stability of +2 oxidation state
Variable oxidation states
Formation of Complex Ions
Low energy unfilled d-orbitals or p-orbitals can accept a lone pair of electrons from LIGANDS to form a dative bond.
Ligands : species that can donate a pair of non-bonding electrons to the central metal ion eg water, ammonia, chloride ion.
Result:complex ion
↑↓↑↓
↑↓
↑↓
↑
↑↑↓ ↑↓
↑↓ ↑↓
white light
Energy corresponds to particular frequency in visible spectrum
∆EEnergy is absorbed as electron is promoted.
Reflected light is complementary colour to
absorbed light.
Formation of Complex Ions
•Stabilises certain oxidation states
•Affects the solubility of compounds
•Major effect on the colour of the solution of a metal ion
Stereochemistry of Complex Ions
NH3
NH3
H3NNH3
Cu
2+
tetrahedral
H2O
H2O H2O
H2O
H2O
Cu
H2O2+
octahedral
Cl
ClCl
Cl
Cu
2-
Square planar
Complex ions are capable of exhibiting cis-trans & optical isomerism
Coordination Number: the number of particles around the central metal
Stereochemistry:cis-trans
Stereochemistry:cis-trans
Stereochemistry: Chirality
Stereochemistry: Chirality
Catalytic properties of Transition Elements