SEK. MEN. KEB. SULTAN ISMAIL, JOHOR BAHRU.

PHYSICAL CHEMISTRY/ UPPERSIX/ 2013 TOPIC : PERIODIC TABLE : PERIODICITY

ARRANGEMENT OF THE ELEMENTS 1. The Periodic Table is an arrangement of all the elements in order of their increasing proton number and also based on the electronic configuration of their atoms. 2. The position of an element in the Period Table is identified by the Period and Group it is in. 3. (a) The periods are the horizontal rows. There are are 7 periods in the Periodic Table. (b) The elements are arranged across a period in order of increasing proton number. (c) The valence orbits are being filled across a period. (d) The total number of main (principal) electron shells an atom has determines the period to which it belongs. 4. (a) The groups are the vertical column. There are 18 groups in the Periodic Table. (b) A Group contains elements with similar properties and similar valence electronic configuration. (c) The valence electronic configuration of elements of Groups 1,2 and 13 to 18 are shown below : Group 1 2 13 14 15 16 17 18 valence electronic configuration ns1 (1 valence electron) ns2 (2 valence electron) ns2np1 (3 valence electron) ns2np2 (4 valence electron) 2 3 ns np (5 valence electron) ns2np4 (6 valence electron) ns2np5 (7 valence electron) ns2np6 (8 valence electron)

5. (a) The periodic table is also divided into blocks. Group 1 and 2 are in the s-block as the atoms outermost electrons are in the valence electrons are in the s-orbitals; while Group 13 to 18 are in the p-block as the valence electrons are in the p-orbitals. (b) In each of the 4th, 5th, 6th and 7th Period, there is a set of 10 elements (located in Group 3 to 12) called d-block elements. The elements in the d-block have electrons filling up the dorbitals of their atoms. For example, the d-block elements in the 4th Period have their 3d orbitals filled up progressively after the 4s orbital is fully filled (according to Aufbau Principle). (c) In each of the 6th and 7th Period, there is a series of f-block elements elements which have their f orbitals containing electrons. They are called the lanthanides (4f orbitals are filled) and

the actinides (5f orbitals are filled). Blocks in the Periodic Table

4. Trends in atomic radius down a group of the Periodic Table The atomic radius increases down a group (a) Down a group, the nuclear charge increases, but the number of electrons and filled inner electrons shells also increases. Thus the screening effect of the inner electrons increases, offsetting the increase in nuclear charge. (b) The outermost electrons in the group are also further from the nucleus. Hence the attraction of the nucleus on the electrons in the outer shell is not as strong. Therefore, the atomic radius increases.

Nuclear charge increases. Inner filled shells increase Shielding increases Outer electrons further from nucleus Atomic radius increase

Ionic Radius

5. Neutral atoms or ions thatbhave the same number of electrons and the same electronic configuration are said to be isoelectronic. Table below shows the ionic radii of four species (O2- , F-, Na+ , and Mg2+) that are isoelectronic. They have the electronic configuration : 1s2 2s2 2p6

Species Ionic radius (nm) Nuclear charge No.of electrons

O20.140 +8 10

F0.136 +9 10

Na+
0.095 =11 10

Mg2+
0.065 +12 10

The ionic radii of four species that are isoelectronic

6. Table above shows that for a given number of electrons, the higher the nuclear charge, the higher the force of attraction and the smaller the ionic radius. 7. A positive ion (cation) is smaller than its neutral atom (refer table below) Neutral atom Atomic radius (nm) cation Ionic radius (nm) Na(11p, 11e-) 0.156 Na+ (11p, 10e-) 0.095 Mg (12p, 12e-) 0.136 Mg2+ (12p, 10e-) 0.065 Al (13p, 13e-) 0.125 Al3+ (13p, 10e-) 0.050

Comparing the size of an atom and its positive ion 8. Conversely, a negative ion (anion) is bigger than its neutral atom. (refer table below) Neutral atom Atomic radius (nm) cation Ionic radius (nm) P (15p, 15e-) 0.110 P3- (15p, 18e-) 0.212 S (16p, 16e-) 0.104 S2- (16p, 18e-) 0.184 Cl (17p, 17e-) 0.099 Cl- (17p, 18e-) 0.181

Comparing the size of an atom and its negative ion 9. The variations of ionic radii for Period 2 (Li + to F-) and Period 3 (Na+ to Cl-) are shown in figure below.

10. Explanation for the variation of ionic size for Period 2 and 3 elements (a) The cation Li+ to B3+ are isoelectronic (containing 2 electrons). The ionic radii decrease from Li+ to B3+ because the number of electrons remains constant but the number of protons increases from 3 protons to 5 protons. The same basic explanation applies to cations Na+ to Al3+ which are isoelectronic to one another (containing 10 elecrons). Species Nuclear charge Number of electrons Ionic radius (pm) Li+ +3 2 60 Be2+ +4 2 31 B3+ +5 2 20

(b) The anions N3- to F- are isoelectronic (containing 10 electrons). The ionoc size decreases from N3- to F- because the number of electrons remains constant but the number of proton increases from 7 protons to 9 protons. This basic explanation is also true for the anions P 3- to Cl- which are isoelectronic to each other (containing 18 electrons). Species N3O2FNuclear charge +7 +8 +9 Number of 10 10 10 electrons Ionic radius (pm) 171 140 136 (c) The anions are larger than the cations because they have one extra quantum shell filled with electrons. Table below shows the cations and anions of period 2 and 3 Cations/Anion s Li+ , Be2+ , B3+ Electronic Configuration 1s2

N3- , O2- , FNa+ , Mg2+ , Al3+ P3- , S2- , Cl-

1s2 2s2 2p6 1s2 2s2 2p6 1s2 2s2 2p6 3s2 3p6

Melting Point, Boiling Point, and Enthalpy of Vaporisation 1. The melting point of an element is the temperature at which the element in the solid state changes into a liquid (i.e. the solid and liquid state are in equilibrium) at constant pressure. The melting point of an element depends on (a) The strength of the forces holding the particles together in the solid state; (b) The structure of the element in the solid state. 2. Types of structure and bonding in elements

Variation of Boiling Point, Melting Point And Enthalpy of Vaporisation Across The Second and Third Period 1. Boiling point is defined as the temperature at which the saturated vapour pressure of a liquid is equal to the external (usually 1 atm) 2. Boiling point is also defined as the temperature at which a liquid is in equilibrium with its vapour at 1 atm. 3. Melting point is the temperature where a solid is in equilibrium with its liquid at 1 atm. 4. Enthalpy of vaporisation is the heat energy required to change one mole of a substance from the liquid to the vapour state, at the boiling point of the

substance. 5. Boiling point, melting point and enthalpy of vaporisation are the measure of the strength of the attractive forces that holds the particles together in the solid or liquid state. 6. Generally, the stronger the attractive force the higher the boiling point, melting point and enthalpy of vaporisation. 7. The table below shows the variation of the melting point, boiling point and enthalpy of vaporisation of the Second period elements from lithium to neon. Element M.p./0C B.p./0C v/kJmol1

Li 181 1330 135

Be 1278 2480 294

B 2300 3930 539

C(diamo nd) 3022 4827 717 Giant covalent

N -210 -200 2.8

O -218 -183 3.4

F -220 -190 3.2

Ne -249 -245 1.8

Structure of the element 8.

Giant metallic

Simple covalent

The table below shows the variation of the melting point, boiling point and enthalpy of vaporisation of the Third Period elements from sodium to argon. Element M.p./0C B.p./0C v/kJmol1

Na 98 890 89

Mg 650 1120 129

Al 660 2450 294

Si 1423 2680 377

P 44 280 12.4

S 120 445 9.7

Cl -101 -34 10.2

Ar -189 -186 6.5

Structure Giant metallic Giant Simple molecule of the covalent element 9. Consider the Third period: (a) The melting/ boiling points of sodium, magnesium and aluminium are high because the presence of strong metallic bonds in their giant metallic structures. (b) The melting/boiling point increases in the order Na<Mg<Al. This shows that the strength of the metallic bond increases in the same order. (c) The strength of metallic bonds depends on the number of electrons peratom that is contributed to form the bond. (d) Each sodium atom contributes one electron to the metallic bond, while magnesium contributes two and aluminium contributes three. (e) Silicon has a giant covalent structure with strong covalent bonds holding the atoms together in a three dimension array: melting involves the breaking of these strong covalent bonds. This accounts for the exceptional high melting/boiling of silicon. (f) Phosphorous, sulphur, chlorine and argon exist as a simple discrete molecules of P4, S8, Cl2 and Ar. (g) The intermolecular forces are the weak van der Waals forces. This accounts for their relatively low melting/boiling points. (h) The strength of the van der Waals forces depends on the size and total number of electrons in the respective molecules. (i) This diagrams below show the structure of the P4, S8, Cl2 and Ar molecules. P4 Cl2

Molecules No. of electrons (j)

P4 60

S8

S8 128

Cl2 34

Ar Ar 18

This causes the strength of the van der Waals forces and the melting/boiling point to increase in the order: Ar < Cl2 < P4 <S8 (k) The same general trend is also observed in their enthalpy of vaporisation. 10. Considering the Second Period: (a) Lithium and beryllium are metals with strong metallic bond in their giant metallic structure. This accounts for their high melting/boiling points. (b) Boron and carbon (diamond) have giant covalent structures with strong covalent bonds holding the atoms together. This accounts for their exceptionally high melting/boiling point. (c) Nitrogen (N2), oxygen (O2), fluorine (F2) and neon (Ne) exist as simple molecules or atoms. This accounts for their low melting/boiling points.

SEK. MEN. KEB. SULTAN ISMAIL, JOHOR BAHRU.

PHYSICAL CHEMISTRY/ UPPER SIX/ 2013 TOPIC : PERIODIC TABLE : PERIODICITY

Electronegativity 1. Electronegativity is a measure of the relative strength of atoms to attract electrons in a covalent bond to which they are bonded. Electronegativity is sometimes call electron-pulling ability. 2. Electronegativity depends on the size of the atom and the nuclear charge. Trend Of electronegativity Across a Period 1. The electronegativity (based on the Pauling scale) of the second and third period elements are given below. Second Period Element Li Be B C N O F Electronegati 1.0 1.5 2.0 2.5 3.0 3.5 4.0 vity Third Period Element Na Electronegati 0.9 vity Mg 1.2 Al 1.5 Si 1.8 P 2.1 S 2.5 Cl 3.0

The electronegativity increases across a period.

2. Going across a period from left to right, the atomic radius decreases but the nuclear charge increases. Hence, the attraction for bonding electrons increases. Trend Of Electronegativity Down A Group 1. The electronegativity of the Group 2 and Group 17 elements are given below. Group 1 Element Electronegati vity Group 17 Element Electronegati vity Be 1.5 Mg 1.2 Ca 1.0 Sr Be -

F 4.0

Cl 3.0

Br 2.8

I 2.5

2. Going down a group, the atomic radius increases while the effective nuclear charge remains almost constant. Hence, the attraction of the atoms for bonding electrons decreases causing the electronegativity to decrease. 3. Summary : Decreasing increasing

Trend Of Electrical Conductivity 1. The graph below shows the trend of electrical conductivity of the second and third period elements.

2. Li, Be, Na, Mg and Al are metals with delocalised electrons in their giant metallic structures. Hence, they are good conductors of electricity. 3. B, C(diamond), N, O, F, Ne, P, S, Cl and Ar are all non-metals. They do not have delocalised electrons in their solid structure. They are non-conductor of electricity. 4. Silicon is metalloid. It is essentially a non-metal but with a certain amount of metallic properties. Its conductivity is higher than the non-metals but lower than the metals. It is a semiconductor. Its conductivity can be increased by increasing temperature or by the addition of a measured of impurities. Ionisation Energy 1. The ionisation energy of an element is a measure of the tendency of the atom of the element to lose electrons to form positive ions. 2. The higher the ionisation energy, the more difficult it is for the atom to lose electrons. 3. The first ionisation is the minimum energy needed to remove one electron from every atom in one mole of gaseous atom to form one mole of gaseous unipositive ions under standard conditions. Mg(g) M+(g) + e H = 1st I.E. 4. The magnitude of the ionisation energy depends on: (a) atomic radius (b) nuclear charge (c) screening effect

Trend Of The First Ionisation Energy Across A Period 1. The tables and graphs below show the first ionisation energies of the second And third period elements. Second Period Element Li Be B C N O F Ne Proton 3 4 5 6 7 8 9 10 Number Atomic 0.152 0.111 0.088 0.077 0.070 0.066 0.064 0.06 Radius 2 st 1 I.E./KJ 520 900 801 1086 1402 1314 1681 2081 mol-1 Third period Element Proton Number Atomic Radius 1st I.E./KJ mol-1 Na 11 0.186 496 Mg 12 0.160 738 Al 13 0.143 578 Si 14 0.117 798 P 15 0.110 1012 S 16 0.104 1000 Cl 17 0.099 1251 Ar 18 0.09 4 1520

2. Going across a period, the atomic radius decreases while the nuclear charge increases. This causes a general increase in the first ionisation energy of the second and third period elements with increasing proton number. 3. However, the increase is not a smooth one. There is a reversal in trend between Be and B, and

between N and O in the second period. 4. The same reversal in trend is also evident in the third period between Mg and Al, and between P and S. 5. The first ionisation energies of Be and Mg are higher than expected because the first electron removed is from a stable s2 configuration. This make the removal of the electron more difficult than expected. Be : 1s2 2s2 Mg : 1s2 2s2 2p6 3s2 6. An alternative explanation is that the first ionisation energies of boron and aluminium are lower than expected. This arises because the first electron removed from the two atoms are from higher p orbitals. Take boron as example. 2p 2s 1s Be B

This electron in the 2p orbital in B is at a higher energy level and is also being shielded from the nucleus by two inner 2s electrons. This makes the electron in B easier to be removed than expected. This same applied to aluminium where the first electron removed is from a higher 3p orbital. 7. The first ionisation energies of nitrogen and phosphorous are higher than expected because the first electron removed is from a stable p3 configuration where all the three orbitals are singly filled. N : 1s2 2s2 2p3 P : 1s2 2s2 2p6 3s23p3 8. An alternative explanation is that the first ionisation energies of oxygen or sulphur are lower than expected. This arises because the first electron removed from the two atoms are formed a p orbital that is occupied by a pair of electrons. Take sulphur as example : 3p

3s P s The two electrons in the 3p orbital in sulphur experience mutual repulsion. This makes the electron easier to be removed than expected. 9. The first ionisation energies of the second period elements are higher than their corresponding third period elements. This is because, atoms of the second period elements are smaller and with higher nuclear charge than their counterparts in Period 3.

Trend Of First Ionisation Energy Down A Group 1. The first ionisation energies of the group 2 elements are as shown below. Element Proton Number Atomic Radius 1st I.E./KJ mol-1 Be 4 0.112 900 Mg 12 0.160 740 Ca 20 0.197 590 Sr 38 0.215 550 Ba 56 0.222 500

2. Going down Group 2 the atomic radius increases while the effective nuclear charge remains almost constant. The attraction between nucleus and electron gets weaker. 3. As a result, the first ionisation energy decreases when going down Group 2. 4. The same trend is also observed in other groups such as Group 17. Element 1st I.E./KJ mol-1 F 1680 Cl 1260 Br 1140 I 1010

SekolahMenengah Kebangsaan Sultan Ismail, Johor Bahru. Inorganic Chemistry/ Upper Six/ 2013 Topic : Period 3 Elements

Chemical properties Of The Period 3 Elements 1. Oxidising / reducing power of Period 3 elemets

Metal are usually reducing agents while non-metals are oxidizing agents. Going across the period (Na to Cl) the oxidizing power of the elements increases while the reducing power decreases.

Sodium, magnesium, aluminium (a) relatively low ionization energy radius and and large atomic radius. resulting in

Phosphorous, sulphur, chlorine (a) relatively small atomic high nuclear charge high electron affinity.

(b) form cations by losing electrons electrons. (c) good reducing agents P and S agents while

(b) form anions by gaining (c) function as oxidizing agents; are weak oxidizing chlorine is a

powerful oxidizing agent. P + 3e P3S + 2e S2Cl2 + 2e 2Cl-

2.

Reaction of the elements with water

(a) The metals become less reactive across the period.

(i) Sodium

reacts vigorously with cold water to form the strong alkali sodium hydroxide and hydrogen gas 2Na(s) + 2H2O(l) 2NaOH(aq) + H2(g)

(ii)

Magnesium very slow reaction with cold water (almost negligible) Mg(s) + 2H2O(l) Mg(OH)2(s) + H2(g) Reacts vigorously with steam to form magnesium oxide

and

hydrogen Mg(s) + H2O(g) MgO(s) + H2(g)

(iii) Aluminium with a

does not react with water or steam because it is covered layer of impermeable Al2O3 (**but will react with warm water if its layer of Al 2O3 is

removed, forming aluminium oxide and hydrogen : 2Al(s) + 3H2O(l) Al2O3(s) + 3H2(g)

(b)

Silicon, phosphorous, and sulphur do not react with water.

(c) Chlorine (I) acid.

dissolves in water to form hydrochloric acid and chloric

Cl2(g) + H2O(l) HCl(aq) + HOCl(aq)

3.

Reaction of the elements with oxygen

Generally the reactivity decreases across the Period.

(a) Sodium, magnesium and aluminium must be heated to react directly with oxygen to form ionic oxides.

(b) Silicon powder reacts vigorously to form a covalent giant molecular oxide.

(c) Dry phosphorous can ignite spontaneously in air to form acidic oxides. (that is why it is stored under water)

(d) Sulphur burns in air to form an acidic oxide.

(e) Chlorine does not react directly with oxygen.

Oxides Of Period 3 Elements

1.

Structure, bonding, and melting point of oxides of Period 3

The bonds between the element and oxygen change from ionic to covalent across the

period, as the difference in electronegativity between the element and oxygen decreases.

(a) Sodium, magnesium, and aluminium are metals, so they form ionic oxides. They have high melting and boiling due to strong electrovalent bonds between the oppositely charged ions.

2. Acid/ base nature of the oxides of Period 3 elements

Across the period the oxides change from basic oxides to amphoteric oxides to acidic oxide.

(a) Basic oxides

Na2O and MgO

Basic oxides are ionic metal oxides. Soluble basic oxides dissolve in water to form alkalis. All basic oxides will react with acids to form their respective salt and water.

(i) Sodium oxide dissolves in water to form sodium hydroxide, a strong alkali; Na2O(s) + H2O(l) 2NaOH(aq)

reacts readily with dilute acid to form salt and water. Na2O(s) + H2SO4(aq) Na2SO4(aq) + H2O(l)

(ii) Magnesium oxide

is only sparingly soluble in water (the magnesium hydroxide formed is also only slightly soluble in water forming a weak alkaline solution) MgO(s) + 2H2O(l) Mg(OH)2(aq)

reacts readily with dilute acid to form salt and water. MgO(s) + 2HCl(aq) MgCl2(aq) + H2O(l)

(b)

Amphoteric oxide

Al2O3

Amphoteric oxides are ionic metal oxides with covalent character. Amphoteric oxides have both acidic and basic properties. They react with both acid and base to form salts.

(i) Aluminium oxide is ionic but the small ionic radius and high charge on the Al3+ ion causes it to polarize the O2- ion. Ad a result the ionic Al2O3 has some covalent character. Hence Al2O3 is amphoteric, i.e. having both acidic and basic properties. (ii) Aluminium oxide is insoluble in water, but reacts with both acid and alkali to form soluble salts. Al2O3(s) + 6H+(aq) 2Al3+(aq) + 3H2O(l) Al2O3(s) + 6HCl (aq) 2AlCl3(aq) + 3H2O(l) (basic property)

Al2O3(s) + 2OH-(aq) + 3H2O(l) 2Al(OH)4-(aq) Al2O3(s) + 2NaOH(aq) + 3H2O(l) 2Na[Al(OH)4](aq) (acidic

property) (c) Acidic oxides (oxides of Si, P, S and Cl) Acidic oxides are covalent oxides of non-metals. Soluble acidic oxides react with water to form acids, and with alkalis to form salts. Acidic oxides that are not soluble will react with alkalis to form salts.

Silicon (IV) oxide is not soluble in water but reacts with hot concentrated alkalis to form silicates (salts) : SiO2(s) + 2NaOH(aq) Na2SiO3(aq) + H2O(l) (sodium silicate)

Oxides of phosphorous, sulphur, and chlorine all dissolve in water to form acids. P4O6(l) + 6H2O(l) 4H3PO3(aq) P4O10(s) + 6H2O(l) 4H3PO4(aq) SO2(g) + H2O(l) H2SO3(aq) SO3(g) + H2O(l) H2SO4(aq) Cl2O(g) + H2O(l) 2HOCl(aq) Cl2O7(l) + H2O(l) 2HClO4(aq) (phosphoric (III) acid) (phosphoric (V) acid) (sulphuric (IV) acid) (sulphuric (VI) acid) (chloric (I) acid) (chloric (VII) acid)

3. Properties of oxides of Period 3 Summary Formula of oxide Oxidation number Structure Na2O MgO Al2O3 SiO2 P4O6 P4O10 +1 +2 +3 +4 +3 +5 Ionic lattice structure Giant covale nt SO2 SO3 +4 +6 Cl2O Cl2O7 +1 +7

simple covalent structure liquid solid gas gas liquid

Physical state (at room temp) Acid/base nature Solubility in water basic very sparingly pH 14 pH 9

solid

amphoter ic insoluble

acidic soluble form acid

Chlorides Of Period 3 1. Properties of chlorides of Period 3- summary Formula of chloride Oxidation number Structure (bond) Physical state (at room temp) Solubility in water soluble soluble NaCl MgCl2 AlCl3 Al2Cl6 +1 +2 +3 +4 SiCl4 PCl3 PCl5 +3/+5 -1 S2Cl2

giant ionic lattice (ionic) solid

simple molecular (covalent) liquid liquid solid Hydrolysed by water/white fumes of HCl/ liquid

(neutral) (slightly acidic)

forms acidic solution

2. Melting Point

NaCl, MgCl2 : Typical ionic compounds. Giant ionic lattice structure, and strong ionic bonds result in high melting points.

AlCl3 , SiCl4 , PCl5, S2Cl2 , Cl2 : simple covalent molecular structure. Weak intermolecular van der Waals forces give rise to low melting points

3. Solubility in water

Across the period- bonding changes from ionic to covalent which is more likely to be hydrolysed in water, i.e. react with water, changing from neutral to acidic solution

(i) NaCl(s) + aq Na+(aq) + Cl-(aq) hydrolysed

pH = 7 / ionic chloride, not

(ii) MgCl2(s) + aq Mg2+(aq) + 2Cl-(aq) pH = 6/ ionic with a little covalent character, slightly hydrolysed covalent chlorides, (iii) Al2Cl6(s) + 6H2O(l) 2Al(OH)3(s) + hydrolysed by water forming acidic solutions

6HCl(aq) SiCl4(l) + 2H2O(l) SiO2(s) + 4HCl(aq) PCl5(s) + 4H2O(l) H3PO4(aq) + 5HCl(aq) 2S2Cl2(l) + 2H2O(l) 3S(s) + SO2(g) + 4HCl(aq)