PERIODICITY

Dimitri Mendeleev was the first scientist to publish an organized periodic table of the known elements.

The Periodic Law states: When arranged by increasing atomic number, the chemical elements display a regular and repeating pattern of chemical and physical properties.

Besides the 4 blocks of the table, there is another way of classifying element: Metals Nonmetals Metalloids or Semi-metals. The following slide shows where each group is found.

Two Br atoms bonded together are 2.86 angstroms apart. So, the radius of each atom is 1.43 .

2.86
1.43 1.43

The trend for atomic radius in a group is to go from smaller at the top to larger at the bottom. With each step down the group, an entirely new shell added to the electron cloud, making the atoms larger with each step.

The trend across a horizontal period is less obvious. Each step adds a proton and an electron (and 1 or 2 neutrons). Electrons are added to existing shells or subshells.

The effect is that the more positive nucleus has a greater pull on the electron cloud because the shielding effect remains the same. As effective nuclear charge increases, the electron cloud is pulled in tighter. The ENC is the positive charge that an electron experiences from the nucleus.

Atoms become smaller as we move from left to right across a period. The closer an electron is to the nucleus, the more pull it feels. The smaller is the radius. The shielding effect is The attraction for electrons in the outermost shell by the nucleus is shielded by electrons in lower energy levels / inner shells.

Within group the atomic radii tend to increase. Atomic radii actually decrease across a row.

Atomic Radii for Main Group Elements

(s,p)

 Hvapour

= heat change when 1 mole element is converted frm liquid to vapour @ its bp Depends on 2 factors : 1. Bonding metallic, covalent & van der waals 2. Structure giant metallic, giant covalent & simple molecular

In P2, mp & bp increase from Li to giant molecule C Decrease abruptly to simple molecule N until monoatomic Ne The same trend is repeated for mp & bp across P3

mp & bp S > P since molecular size S8 > P4

Same trend also observed for enthalpies of vapourisation going across P2 & P3

Giant metallic structure

o Moving across metals in P2 & P3, gradual in valence e- & nuclear charge o Metallic bonds become stronger o Consequently mp, bp & Hvapour increases o Metals change frm liq to vap; ALL metallic bonds still exist have to be broken, bp >> mp o P2 > P3 ; atomic radii of metals smaller, stronger metallic bonds in P2

 Giant

covalent structure

oB, C (graphte/diamond) & Si ; giant covalent / network / giant crystal lattice structure oStrong covalent bonds must be broken before solid melts. omp, bp & Hvapour are very high omp (loosen the bond) < bp (break all bonds)

 Simple

molecular structure

o All non-metallic elements in P2 & P3 form small & discrete molecules o Covalent bonds within molecules are strong, but VdW forces between molecules are weak o mp, bp & Hvapour are low o VdW forces as molecular size o P4, S8, > N2, O2 o Cl2 > F2, Ar o Ar > Ne

Bonding, Structure and Properties

Structure Giant metallic Bonding Metallic Formula Type of Metallic force bond broken on melting/ boiling

Period Li 2

Be
Giant metallic Metallic
Metallic bond

B
Giant covalent Covalent
Covalent bond

C
Giant covalent Covalent
Covalent bond

N
Simple molecule Covalent N2 VdW

O
Simple molecule Covalent O2 VdW

F
Simple molecule Covalent F2 VdW

Ne
Monato mic
Ne VdW

Structure Bonding Formula Type of force broken on melting/ boiling

Period Na 3

Mg
Giant metallic Metallic Metallic bond

Al
Giant metallic Metallic Metallic bond

Si
Giant covalent Covalent Covalent bond

P
Simple molecule Covalent P4 VdW

S
Simple molecule Covalent S8 VdW

Cl
Simple molecule Covalent Cl2 VdW

Ar
Monato mic Ar VdW

Giant metallic Metallic Metallic bond

Structure and Properties

 Elements

in P2 & P3 can be classified into : Metals Metalloids Non-metals Across P2 & P3; EC decreases
Metal are good conductors in solid or molten state ; delocalised electrons present

Non-metals are non-conductors ; all valence e- used to form covalent bonds, no mobile electrons Noble gases stable octet arrangement ; no mobile eMetalloids are poor conductors EC of B, C(graphite) & Si higher than non-metals but lower than metals

If an electron is given enough energy (in the form of a photon) to overcome the effective nuclear charge holding the electron in the cloud, it can leave the atom completely. The atom has been ionized or charged. The number of protons and electrons is no longer equal. Lower IE, more easily its electrons can be removed

Def : The min energy required to remove 1 mol electron from substance in gaseous state (measured in kilojoules, kJ) Ionization energy is always endothermic, that is energy is added to the atom to remove the electron. Depends on : Distance between outer e- and nucleus Size of nuclear charge Shielding/screening effect

IE decreases as atomic radius increases

Distance btwn outer e- & nucleus , attraction of +ve charge nucleus for -ve charge e-

Nuclear charge , IE
Attraction on -ve charge outer e- by +vely charged nucleus stronger

screening effect, IE
Valence e- are shielded from attraction of nucleus by many inner shells electrons

a) as we go across P2 & P3, IE (1st) is larger ; ENC becomes higher as the number of protons in the nucleus of the atom becomes larger.
Exceptions : P2 ; Be, N > B, O : P3 ; Mg, P > Al, S

b) With an electron already in the orbital there is repulsion between the two in the same orbital and it comes out with less IE.

P2 ; Be : 1s22s2 B : 1s22s22p1 P3 ; Mg : 1s22s23s2 Al: 1s22s22p63s23p1 More energy is required to remove an electron from a fully filled s orbital than a singly occupied p orbital
P2 ; N : 1s22s22p3 O: 1s22s22p4 P3 ; P : 1s22s22p63s23p3 S: 1s22s22p63s23p4 More energy is required to remove an electron from a half filled p orbital than a partial filled p orbital

c) The trend going down a group shows a decrease in the IE1 which corresponds to an increase in the atomic radius. d) The 2nd, 3rd, and 4th ionization energies are those required to remove the 2nd, 3rd, and 4th electrons and so on.

Increase because ions produced become more +ve as more electrons are removed. The atom has been ionized or charged. The number of protons and electrons is no longer equal. Lower IE, more easily its electrons can be removed

Big jump shows how many valence electrons

Big jump

Frm SIE, 19 electrons contain in this element, thus it is K, with 3 shells & 1 valence electron e- confg : 1s22s22p6 3s23p64s1

Eg 1 : The graph of log IE of elements X is given above. Determine the electron configuration & position of X in the Periodic Table, hence its identity. Sol : element X consists of 3 shells with 7 valence electrons 1s22s22p63s23p5 P3, G17 ; Cl

Eg 2 :Partial SIE of an element Q is as follows.

Determine the valence shell configuration & position of Q in the Periodic Table.

Ans : ns2 ; G2 (Period unknown since SIE partially !!!)

Reaction with oxygen Reaction with water Hydrolysis of oxides Acidic & basic properties of oxides

Rx Oxygen

Sodium Sodium burns with an orange flame to produce the white solid.
Magnesium Magnesium burns with an intense white flame to give white solid.

Aluminium Aluminium will burn if powdered, otherwise the strong oxide layer inhibit the reaction. Sprinkle of aluminium powder into flame, white sparkles is produced. White aluminium oxide is formed. Silicon Silicon will burn if heated strongly. White solid silicon dioxide is produced.

Phosphorus White phosphorus catches fire spontaneously in air, with a white flame and producing clouds of white smoke - a mixture of phosphorus(III) oxide and phosphorus(V) oxide. In excess oxygen, the product is almost entirely phosphorus(V) oxide:

Sulphur Sulphur burns on gentle heating with a pale blue flame. It produces colourless sulphur dioxide gas.
In excess oxygen, some SO3 is also formed. Chlorine no effect ; Cl2O (yellowish gas) & Cl2O7 (colourless liquid) prepared by other means.

Ability as Ox Agt & Rd Agt

Good reducing agents (electron donors) @ Na, Mg, Al larger size & lower IE Eg : Al used in thermite rx to extract Cr by reducing Cr2O3 Good oxidising agent (electron acceptors) @ P, S & Cl2 smaller size & higher IE Eg : Cl2 oxidises Fe(II) to Fe(III)

Reactions with oxygen

Sodium

Magnesium

Which is which?

Sulphur

Rx Water
2Na + 2H2O 2NaOH + H2 (vigorously cold water) Mg + 2H2O Mg(OH) 2 + H2 (vigorously steam) 2Al + 3H2O Al2O3 + 3H2(vigorously out protective oxide layer)

Si + 2H2O SiO2 + 2H2 (slow steam @ red heat)

P & S do not react under any conditions Cl2 + H2O HCl + HClO(dissolves sparingly to form acids )

Chemical properties of the oxides

Reaction of oxides with water Na2O + H2O 2NaOH -dissolves readily in water, undergoes hydrolysis to produce OHMgO sparingly soluble in water, MgO + H2O Mg(OH)2 -undergoes hydrolysis to produce OHAl2O3 - insoluble in water, no hydrolysis occur

Reaction of oxides with water SiO2 - insoluble in water, no hydrolysis occur P4O10 + 6H2O 4H3PO4 (vigorously water) P4O6 + 6H2O 4H3PO3 - Hydrolysis occur to produce H+ SO2 + H2O H2SO3 (dissolves readily) SO3 + H2O H2SO4 (very exothermic) - Hydrolysis occur to produce H+,SO3 more acidic than SO2 Cl2O + H2O 2HClO (decompose to light to produce HCl & O2) Cl2O7 + H2O 2HClO4

Acid/base properties of oxides

Na2O dissolves in water to produce strong alkali Na2O + H2O 2NaOH MgO dissolves slowly in hot dilute acids MgO + H2SO4 MgSO4 + H2O

Al2O3 dissolves slowly in hot dilute mineral acids & hot, concentrated alkali (ionic compnd with covalent character) to show amphoteric nature BASE : ACID:
Al2O3+ 3H2SO4 Al2(SO4)3 + 3H2O
2NaAl(OH)4

Al2O3+ 2NaOH + 3H2O

SiO2 reacts as weak acid

SiO2 + 2NaOH Na2SiO3 + H2O

Oxides of P, S & Cl react with alkalis to produce salts

P4O10 + 12NaOH 4Na3PO4 + 6H2O P4O6 + 12NaOH 4Na3PO3 + 6H2O SO2 + 2NaOH Na2SO3 + H2O SO3 + 2NaOH Na2SO4 + H2O Cl2O + 2NaOH 2NaOCl + H2O Cl2O7 + 2NaOH 2NaClO4 + H2O

Use of SO2 in Food Preservative

-Widely used in food & beverage industries. -Preservatives & antioxidant => mild reducing & acidic properties. -Prevent growth of bacteria & avoid rancidity of f&b

END OF PERIODIC TABLE : PERIODICITY