- By the end of this chapter you should be able to describe the modern periodic table; deduce the type of an element and its properties from its position; explain why atomic radius decreases across a period; name and locate the blocks; relate the electronic configuration to the group number; define atomic radius, ionization energy, electron affinity and electronegativity and compare the last two; locate metals and non-metals; relate atomic radius to ionization energy and electron affinity; explain the variation of basic and acidic character with atomic number; calculate oxidation numbers; identify redox reactions; and write oxidation and reduction half-reactions.
- Lessons in this chapter:
- The modern periodic table and its blocks
- Atomic radius
- Ionization energy, electron affinity and electronegativity
- Metallic and non-metallic character; acidic and basic oxides
- Oxidation numbers
- Oxidation–reduction reactions and balancing ionic equations
🌳 Concept tree
- Chapter 3 — The Periodic Table and Classification of Elements
- ├── Lesson 1 The modern periodic table
│ ├── 1.1 The basis of arrangement
│ ├── 1.2 Description of the table
│ ├── 1.3 The four blocks of the periodic table
│ ├── 1.4 Types of elements
- │ └── 1.5 Using the configuration to find position
- Atomic radius
│ ├── 2.1 Definition
- │ ├── 2.2 Variation across a period (left to right)
│ ├── 2.3 Variation down a group
- │ └── 2.4 Ionic radius compared with atomic radius
- ├── Lesson 3 Ionization energy, electron affinity and electronegativity
- │ ├── 3.1 Ionization energy (ionization potential)
│ ├── 3.2 Electron affinity
│ ├── 3.3 Electronegativity
- │ ├── 3.4 Electron affinity versus electronegativity
- │ └── 3.5 Summary of the trends (representative elements)
- ├── Lesson 4 Metallic and non-metallic character; acidic and basic properties
│ ├── 4.1 Metals and non-metals
│ ├── 4.2 Trends of metallic character
- │ ├── 4.3 Oxides: acidic, basic, amphoteric and neutral
- │ └── 4.4 Acidic and basic character in the periodic table
- Oxidation numbers
│ ├── 5.1 Concept
│ ├── 5.2 Ionic compounds
│ ├── 5.3 Covalent compounds
│ ├── 5.4 Rules
│ └── 5.5 Worked examples
└── Lesson 6→Oxidation–reduction (redox) reactions
├── 6.1 Definitions
- ├── 6.2 Behaviour of an agent according to its oxidation number
- ├── 6.3 Identifying redox reactions by oxidation numbers
- ├── 6.4 Ionic equations, spectator ions and half-reactions
- ├── 6.5 Balancing ionic redox equations (half-reaction method)
├── 6.6 Special types of redox reactions
└── 6.7 Final summary
- As knowledge of the atom developed, the true energy levels and sublevels were discovered.
- By applying the Aufbau principle, the elements could be arranged so that each element has one electron more than the element before it.
- The modern periodic table is therefore built on two bases:
- the elements are arranged in ascending order of atomic number;
- the elements are arranged according to the Aufbau principle (the order of filling of sublevels).
- The order of filling sublevels coincides with the arrangement of the periods:
| Period |
Sublevels filled (in order of increasing energy) |
Number of elements |
| 1 |
1s |
2 |
| 2 |
2s < 2p |
8 |
| 3 |
3s < 3p |
8 |
| 4 |
4s < 3d < 4p |
18 |
| 5 |
5s < 4d < 5p |
18 |
| 6 |
6s < 4f < 5d < 6p |
32 |
| 7 |
7s < 5f < 6d < 7p |
32 (as far as discovered) |
- The table consists of 18 vertical groups and 7 horizontal periods.
- Elements are arranged in ascending atomic number; each element has one electron more than its predecessor in the period.
- Each period starts by filling a new energy level with one electron and then fills the sublevels in turn, ending with a noble gas.
- In a vertical group, the elements have similar electron configuration of the outer energy level, but different principal quantum number n.
- The period number equals the number of the outermost main level (n) of the element.
- Electronic distribution of the first 30 elements (number of electrons in each sublevel):
| Z |
Element |
Configuration |
| 1–2 |
H, He |
1s1, 1s2 |
| 3–10 |
Li … Ne |
[He] 2s1 … 2s2 2p6 |
| 11–18 |
Na … Ar |
[Ne] 3s1 … 3s2 3p6 |
| 19 |
K |
[Ar] 4s1 |
| 20 |
Ca |
[Ar] 4s2 |
| 21 |
Sc |
[Ar] 4s2 3d1 |
| 22 |
Ti |
[Ar] 4s2 3d2 |
| 23 |
V |
[Ar] 4s2 3d3 |
| 24 |
Cr |
[Ar] 4s1 3d5 |
| 25 |
Mn |
[Ar] 4s2 3d5 |
| 26 |
Fe |
[Ar] 4s2 3d6 |
| 27 |
Co |
[Ar] 4s2 3d7 |
| 28 |
Ni |
[Ar] 4s2 3d8 |
| 29 |
Cu |
[Ar] 4s1 3d10 |
| 30 |
Zn |
[Ar] 4s2 3d10 |
- (Chromium and copper are exceptions because half-filled (d5) and completely filled (d10) d sublevels are extra stable.)
- The table is divided into four main regions or blocks
- named after the sublevel which receives the last electron.
s-blockon the left.
The outermost electrons occupy the s sublevelgroup 1A (ns1) and group 2A (ns2), where n is the period number and the number of the last energy level.
| Comparison aspect | Main idea | Keywords |
|---|
| p-block | on the right | right |
| The outermost electrons occupy the p sublevel | - groups 3A (ns2 np1)
- 4A (np2)
- 5A (np3)
- 6A (np4)
- 7A (np5) and the zero group (noble gases
- np6)
- where p is saturated
| groupszerogroupnoble |
| • | (Helium is 1s2.) | Helium |
- in the middle.
- The d sublevel is filled successively; as d holds up to 10 electrons, the block has ten vertical columns: seven belong to the B groups (3B to 7B, then 1B and 2B in the table’s numbering) and three columns together form the eighth group (Fe, Co, Ni and their analogues).
- placed separately at the bottom so the table does not become too long.
- The f sublevel (up to 14 electrons) is filled successively; it has two series:
Lanthanidesthe 4f sublevel is filled, 14 elements; the outer sublevel of all is 6s2.
Actinidesthe 5f sublevel is filled, 14 elements, all radioactive (unstable nuclei).
- The elements of the modern table are classified into four types:
| Comparison aspect | Main idea | Keywords |
|---|
| Noble (inert) gases | - last vertical column of the p-block (group zero/18). Configuration ends with np6 (helium 1s2). All sublevels of the period are filled
- so they are completely stable and form compounds with extreme difficulty
| lastverticalcolumnblock |
| Representative elements | - the s-block and the p-block except the zero group. All energy levels are full except the outermost
- and they tend to attain the configuration ns2 np6 by losing
- gaining or sharing electrons
| blockexceptzerogroup |
| Main (d-block) transition elements | the d sublevel is filled successively | sublevelfilledsuccessively |
| Inner transition elements | - the f-block
- where f is filled successively
| blockfilledsuccessively |
- The sixth period contains all four types (noble gas Rn is in the 6th period; Cs and Ba, representative; Hf to Hg, d-block; and the lanthanides), so it has four types.
| Comparison aspect | Main idea | Keywords |
|---|
| Period | = number of the outermost main level (largest n) | numberoutermostmainlevel |
| Group of s and p block elements | - (A groups) = number of electrons in the outermost level. Examples: 1A → ns1
- 2A → ns2
- 3A → ns2 np1 … 7A → ns2 np5. In every case the number of valence electrons equals the group number
| groupsnumberelectronsoutermost |
| Group of d block elements | - = number of electrons in (n−1)d plus ns: Sc (3) group 3B
- Ti 4B
- V 5B
- Cr 6B
- Mn 7B
- Ni (8
- 10) group VIII
- Cu (11) 1B
- Zn (12) 2B
| numberelectronsplusVIII |
| • | The block is the sublevel that receives the last electron | blocksublevelreceiveslast |
| Worked example 1.1. | - Locate ₁₇Cl: 1s2 2s2 2p6 3s2 3p5. Outer level n = 3 → period 3. Outer configuration ns2 np5 → group 7A (halogens)
- p-block
- representative non-metal
| Locate₁₇ClOuterlevel |
| Comparison aspect | Main idea | Keywords |
|---|
| Worked example 1.2. | - Locate ₂₀Ca: [Ar] 4s2 → period 4
- group 2A
- s-block
- representative element (an alkaline earth metal)
| Locate₂₀Caperiodgroup |
| Worked example 1.3. | - Locate ₂₆Fe: [Ar] 4s2 3d6 → period 4
- d-block (main transition element)
- group VIII (8 outer electrons: 2 + 6)
| Locate₂₆Feperiodblock |
| Worked example 1.4. | - An element has the configuration [Kr] 5s2 4d10 5p4. Period 5 (n = 5)
- p-block
- group 6A (ns2 np4)
- representative
- it is ₅₂Te (36 + 2 + 10 + 4 = 52)
| elementconfiguration4d10Period |
✍️ Worked examples
| Comparison aspect | Main idea | Keywords |
|---|
| Worked example 1.5. | - An element is in period 6
- group 1A. Its outer configuration is 6s1 and its atomic number is 55 (caesium)
- s-block
| elementperiodgroupouter |
| • | Worked example 1.6 — match elements to types (like the chapter exercises) | Workedexamplematchelements |
| ₈₆Rn | - [Xe] 4f14 5d10 6s2 6p6 — noble gas
- p-block
| 4f145d10nobleblock |
| ₅₅Cs | 6s1 — representative element in the s-block | representativeelementblock |
| ₂₃V | 4s2 3d3 — transition metal in the fourth period | transitionmetalfourthperiod |
| ₆₄Gd | - 4f7 5d1 6s2 — lanthanide
- inner transition
| lanthanideinnertransition |
| ₇₆Os | 4f14 5d6 6s2 — main transition metal in period 6 | 4f14maintransitionmetal |
- We study the trends of properties in the representative elements (s and p blocks).
- Because the wave theory shows it is impossible to fix the exact position of an electron, the atomic radius cannot be defined as "distance from the nucleus to the farthest electron".
- Instead:
- Atomic radius (covalent radius) is half the distance between the centres of the nuclei of two identical atoms bonded in a diatomic molecule.
- It is measured in picometres (pm); 1 pm = 10−12 m.
- In ionic crystals (such as NaCl) the size of each cation or anion is described by its ionic radius, which depends on the number of electrons lost or gained.
- Example in a Cl₂ molecule the distance between the two nuclei is 198 pm, so the atomic radius of chlorine = 198/2 = 99 pm.
| 1A |
2A |
3A |
4A |
5A |
6A |
7A |
| H 37 |
|
|
|
|
|
|
| Li 152 |
Be 113 |
B 88 |
C 77 |
N 70 |
O 66 |
F 64 |
| Na 186 |
Mg 160 |
Al 143 |
Si 117 |
P 110 |
S 104 |
Cl 99 |
| K 227 |
Ca 197 |
Ga 122 |
Ge 122 |
As 121 |
Se 117 |
Br 114 |
| Rb 247 |
Sr 215 |
In 163 |
Sn 140 |
Sb 141 |
Te 143 |
I 133 |
| Cs 265 |
Ba 217 |
Tl 170 |
Pb 175 |
Bi 155 |
Po 167 |
At 140 |
2.2 Variation across a period (left to right)
- The atomic radius decreases from group 1A to group 7A. Reason: the effective nuclear charge (Zeff) increases gradually.
- Zeff is the actual nuclear charge felt by an electron in the atom. It is always less than the real nuclear charge (number of protons) because the inner (core) electrons shield part of the nuclear attraction from the outer electrons.
- Across a period the number of protons increases by one at each step while the electrons are added to the same main level, so the shielding by inner electrons does not change much. Zeff rises, the valence electrons are pulled closer, and the atom contracts.
- Hence the largest atom in a period is the alkali metal (1A) and the smallest is the halogen (7A).
- Example period 3: Na (186) > Mg (160) > Al (143) > Si (117) > P (110) > S (104) > Cl (99) pm.
2.3 Variation down a group
- The atomic radius increases with atomic number. Reasons:
- the number of energy levels increases;
- the filled inner levels shield the outer electrons from the nucleus;
- the repulsion between the electrons increases.
Example→group 1A: Li 152 < Na 186 < K 227 < Rb 247 < Cs 265 pm.
| Species |
Na |
Na+ |
Fe |
Fe2+ |
Fe3+ |
Cl |
Cl− |
| Radius (pm) |
186 |
102 |
126 |
78 |
64.5 |
99 |
181 |
| Protons |
11 |
11 |
26 |
26 |
26 |
17 |
17 |
| Electrons |
11 |
10 |
26 |
24 |
23 |
17 |
18 |
| Comparison aspect | Main idea | Keywords |
|---|
| Metal cation is smaller than its atom | - (Na+ < Na
- Fe2+ < Fe). Protons are the same but there are fewer electrons
- so the effective nuclear charge per electron increases and the outer level is lost (for Na the 3s electron is removed). The larger the positive charge the smaller the ion (Fe3+ < Fe2+ < Fe)
| Protonssamefewerelectrons |
| Non-metal anion is larger than its atom | - (Cl− > Cl). The protons are the same but there is one more electron
- so repulsion between electrons increases and the nuclear attraction per electron decreases (as in tug of war: the same pull shared by more electrons)
| protonssameelectronrepulsion |
✍️ Worked examples
- Worked example 2.1. Arrange in decreasing radius: Mg, Na, Cl, S. All in period 3: Na (186) > Mg (160) > S (104) > Cl (99).
- Worked example 2.2. Which is larger, Br or Br−? Br−, because it has one electron more than its (same) 35 protons.
- Worked example 2.3.
- Compare the ions S2−, Cl−, K+ and Ca2+ (all have 18 electrons) with 16, 17, 19 and 20 protons.
- More protons attract the same number of electrons more strongly, so the radius order is S2− > Cl− > K+ > Ca2+.
- Worked example 2.4 (periodic table figure type question).
- In the table element X is in period 2, group 1A; element A in period 3, group 1A; element B in period 3, group 7A.
- Radii A > X (extra shell); A > B (decrease across period).
- If an atom gains a moderate amount of energy its electrons are excited to higher levels.
- If the energy is large enough the weakest-bound electron is ejected and the atom becomes a positive ion.
- Ionization energy (potential) = the amount of energy required to remove one mole of electrons from one mole of isolated gaseous atoms.
- Because one, two or three electrons may be removed there are first, second, third … ionization energies:
M(g) → M+(g) + e− (first ionization energy, IE₁)
- M+(g) → M2+(g) + e− (second ionization energy, IE₂), and so on.
- Unit kJ/mol. All are endothermic (ΔH positive).
- First ionization energies (kJ/mol), selected H 1312; Li 520, Be 900, B 801, C 1086, N 1402, O 1314, F 1681, Ne 2081; Na 496, Mg 738, Al 578, Si 787, P 1012, S 1000, Cl 1251, Ar 1521; K 419; Cs 376.
- Trend in a period:
- generally increases from left to right because the effective nuclear charge increases and the atomic radius decreases, so the nucleus attracts the valence electrons more strongly and more energy is needed to remove one.
- Ionization energy is inversely related to atomic radius.
- (Small irregularities occur at 3A and 6A because of the stability of full and half-filled sublevels, e.g.
N > O.)
- Trend in a group decreases from top to bottom, because the number of shells increases, the atomic radius increases and the attraction of the nucleus for the valence electrons falls, so less energy is required to remove it.
- Noble gases have very high first ionization energies because of the stability of their saturated outer level.
- Successive ionization energies.
- IE₂ > IE₁ because the electron is removed from a positive ion in which the effective nuclear charge per electron is greater.
- For group 2A elements IE₃ is much bigger than IE₂, because the third electron must be taken from a saturated inner level.
- For magnesium:
Mg(g) → Mg+(g) + e− ΔH = +737 kJ/mol
Mg+(g) → Mg2+(g) + e− ΔH = +1450 kJ/mol
- Mg2+(g) → Mg3+(g) + e− ΔH = +7730 kJ/mol (a sudden large jump: the electron comes from the stable 2p6 level)
✍️ Worked examples
- Worked example 3.1.
- From IE values 496, 4562, 6910 kJ/mol for an element, find its group.
- A very big jump after the first value means one valence electron: group 1A (sodium).
- Worked example 3.2.
- Which has the larger first ionization energy Cl or Na?
- Cl, since it is at the right side of the same period (smaller radius and greater Zeff).
- Worked example 3.3. Which has the smaller IE: Rb or K? Rb, because it is lower in the group (larger radius).
- Worked example 3.4 — energy to ionise a sample (using the ΔH). The energy needed to remove one electron from every atom in 0.5 mol of gaseous magnesium atoms = 0.5 × 737 = 368.5 kJ.
- Removing an electron from a gaseous atom needs energy.
- When one mole of gaseous atoms gains one mole of electrons the energy change may be release or absorption:
- Electron affinity = the amount of energy change (released or absorbed) when one mole of isolated gaseous atoms gains one mole of electrons.
- Example Br(g) + e− → Br−(g) ΔH = −325 kJ/mol (energy released, so the sign is negative).
- Electron affinity values (kJ/mol), s and p blocks:
| Li −59.6 |
Be >0 |
B −26.7 |
C −122 |
N +7 |
O −141 |
F −328 |
Ne +29 |
| Na −52.9 |
Mg >0 |
Al −42.5 |
Si −134 |
P −72.0 |
S −200 |
Cl −349 |
Ar +35 |
| K −48.4 |
Ca −2.4 |
Ga −28.9 |
Ge −119 |
As −78.2 |
Se −195 |
Br −325 |
Kr +39 |
| Rb −46.9 |
Sr −5.0 |
In −28.9 |
Sn −107 |
Sb −103 |
Te −190 |
I −295 |
Xe +41 |
| Cs −45.5 |
Ba −14 |
Tl −19.2 |
Pb −35.2 |
Bi −91.3 |
Po −183.3 |
At −270 |
Rn +41 |
| Comparison aspect | Main idea | Keywords |
|---|
| • | - The trend of electron affinity is irregular in periods and groups
- unlike atomic radius and ionization energy
| trendelectronaffinityirregular |
| • | - The most negative values (largest energy release) belong to the halogens (7A)
- because by gaining one electron they reach the configuration of the nearest noble gas
| mostnegativevalueslargest |
| Be and Mg | - have positive values (absorb energy) because the added electron must enter the higher-energy p sublevel
- while the s sublevel is complete
| positivevaluesabsorbenergy |
| Nitrogen | - has a positive value: its half-filled 2p3 is stable
- an added electron has to pair with one already present
- which causes repulsion and reduces stability
| positivevaluehalffilled |
| Noble gases | - have positive values because of the stability of their saturated configuration (the electron would have to enter a new
- higher level)
| positivevaluesbecausestability |
Electronegativity→is the ability of an atom to attract the electrons of the chemical bond towards itself.
It is expressed by a relative numberthe larger the number, the greater the ability to attract bonding electrons.
Examples (Pauling scale)F 4.0, O 3.5, N 3.0, Cl 3.2, C 2.5, H 2.1, Na 0.9, Cs 0.7.
| Comparison aspect | Main idea | Keywords |
|---|
| Trends | - increases across a period (increasing atomic number
- decreasing radius)
- decreases down a group
| increasesacrossperiodincreasing |
| Fluorine | is the most electronegative element | mostelectronegativeelement |
| • | The difference in electronegativity between two elements decides the type of bond between them (studied in Chapter 4 of the book) | differenceelectronegativitybetweenelements |
| Comparison aspect |
Electron affinity |
Electronegativity |
| Meaning |
Energy change when a free gaseous atom gains an electron |
Tendency of an atom in a bond to attract the bonding electrons |
| State of the atom |
Isolated atom in elementary state |
Atom combined with other atoms |
| Expressed by |
Energy (kJ/mol) |
Relative number without units |
| Regularity |
Irregular trend |
Regular trend |
| Comparison aspect | Main idea | Keywords |
|---|
| Across a period (left → right) | - atomic radius ↓
- ionization energy ↑
- electronegativity ↑
| atomicradiusionizationenergy |
| Down a group | - atomic radius ↑
- ionization energy ↓
- electronegativity ↓
| atomicradiusionizationenergy |
| • | - So the element with the largest ionization energy and electronegativity is at the top right (F
- with He having the highest IE)
- and the largest atoms are at the bottom left (Cs)
| elementlargestionizationenergy |
✍️ Worked examples
- Worked example 3.5. Arrange F, Cl, Br, I in increasing electronegativity: I < Br < Cl < F.
- Worked example 3.6.
- Why is the electron affinity of nitrogen positive while that of carbon is negative?
- C (2p2) can add an electron into an empty 2p orbital to reach the stable 2p3; N (2p3 half-filled) can only add by pairing electrons, which costs energy.
- Worked example 3.7 (figure-type question).
- In the first four periods an element D lies in group 1A period 3 and F in group 7A period 3, X in group 1A period 2.
- Ionization energy F > D, and X > D.
- The order of increasing IE D < X < F.
4.1 Metals and non-metals
- Berzelius (early 19th century) was the first to classify elements into metals and non-metals, before anything was known about the atom.
- The classification is still used, although there is no sharp boundary.
- Metals
- Their valence shell generally has less than half its capacity of electrons.
- They lose valence electrons to reach the noble-gas configuration, forming positive ions; hence they are electropositive.
- They conduct electricity because their few valence electrons move easily from place to place in the metal.
- They have large atomic radii and therefore small ionization energies.
- Their valence shell generally has more than half its capacity of electrons.
- They gain a few electrons to reach the noble-gas configuration, forming negative ions; they are electronegative.
- They are electrical insulators because the valence electrons are bound strongly to the nucleus and cannot move.
- They have small atomic radii and high ionization energies.
- (semimetals) B, Si, Ge, As, Sb, Te, At lie on a diagonal line between metals and non-metals.
- They have the appearance of metals but most properties of non-metals; their electronegativity is intermediate; their electrical conductivity is lower than that of metals but much higher than non-metals.
- They are used in transistors and semiconductors.
- Position all metals lie to the left of the metalloids in the table; non-metals lie to the right.
| Comparison aspect | Main idea | Keywords |
|---|
| Across a period | - (left to right): the first group contains the strongest metals
- metallic character decreases gradually until the metalloids
- then non-metallic character increases and is highest in group 7A
| leftrightfirstgroup |
| Down a group | metallic character increases | metalliccharacterincreases |
| • | - So the strongest metals are at the bottom left (caesium is the most metallic) and the strongest non-metals at the top right (fluorine
- the strongest non-metal)
| strongestmetalsbottomleft |
| Worked example 4.1. | - Classify Si
- K. Metals: K
- non-metal: Cl
- metalloids: Si
| ClassifyMetalsmetalmetalloids |
| • | Worked example 4.2 | Workedexample |
- Why is Al a metal but Cl a non-metal?
- Al (3 valence electrons, large radius, low ionization energy) loses electrons; Cl (7 valence electrons, small radius, high electron affinity) gains one.
| Comparison aspect | Main idea | Keywords |
|---|
| Non-metal oxides | dissolve in water to give acids and are called acidic oxides. They react with alkalis to give a salt and water. CO₂(g) + H₂O(l) → H₂CO₃(aq) SO₃(g) + H₂O(l) → H₂SO₄(aq) CO₂(g) + 2NaOH(aq) → Na₂CO₃(aq) + H₂O(l) | dissolvewatergiveacids |
| Metal oxides | - are generally basic oxides. Some dissolve in water forming alkalis (alkaline oxides)
- they react with acids to give a salt and water. Na₂O(s) + H₂O(l) → 2NaOH(aq)
- K₂O(s) + H₂O(l) → 2KOH(aq) Na₂O(s) + 2HCl(aq) → 2NaCl(aq) + H₂O(l) MgO(s) + H₂SO₄(aq) → MgSO₄(aq) + H₂O(l)
| generallybasicSomedissolve |
| Amphoteric oxides | - (Al₂O₃
- ZnO
- Sb₂O₃
- SnO) react both with acids and with alkalis: Al₂O₃(s) + 6HCl(aq) → 2AlCl₃(aq) + 3H₂O(l) Al₂O₃(s) + 2NaOH(aq) → 2NaAlO₂(s) + H₂O(l) (sodium aluminate) ZnO(s) + H₂SO₄(aq) → ZnSO₄(aq) + H₂O(l) ZnO(s) + 2NaOH(aq) → Na₂ZnO₂(aq) + H₂O(l) (sodium zincate)
| Al₂O₃Sb₂O₃reactboth |
| Neutral oxides | - (CO
- N₂O) react neither with acids nor with alkalis and do not dissolve readily in water
| reactneitheracidsalkalis |
4.4 Acidic and basic character in the periodic table
| Comparison aspect | Main idea | Keywords |
|---|
| Across a period | - as atomic number increases the basic character of the oxide decreases and the acidic character increases. Period 3: Na₂O (strongly basic)
- MgO (basic)
- Al₂O₃ (amphoteric)
- SiO₂ (weakly acidic)
- P₄O₁₀ (acidic)
- SO₃ (strongly acidic)
- Cl₂O₇ (very strongly acidic). P₄O₁₀ + 6H₂O → 4H₃PO₄
- Cl₂O₇ + H₂O → 2HClO₄
| atomicnumberincreasesbasic |
| Down a group | (e.g. group 1): basic character of the hydroxides/oxides increases as atomic number increases (LiOH < NaOH < KOH < RbOH < CsOH) | basiccharacterhydroxidesoxides |
| • | - For the hydrides of group 7A the acidic strength increases down the group: HF < HCl < HBr < HI. As the radius of the halogen increases
- the attraction of the halogen to the hydrogen atom decreases
- so hydrogen is ionised more easily
| hydridesgroupacidicstrength |
| Comparison aspect | Main idea | Keywords |
|---|
| Worked example 4.3. | - Write balanced equations showing that sodium oxide is basic and sulphur trioxide is acidic. Na₂O + 2HCl → 2NaCl + H₂O
- SO₃ + 2NaOH → Na₂SO₄ + H₂O
| Writebalancedequationsshowing |
| Worked example 4.4. | - Show that tin(II) oxide is amphoteric. SnO + 2HCl → SnCl₂ + H₂O
- SnO + 2NaOH → Na₂SnO₂ + H₂O
| Showoxideamphoteric2HCl |
| Worked example 4.5. | - Classify the oxides CaO
- SO₂
- ZnO
- Li₂O. CaO basic
- SO₂ acidic
- ZnO amphoteric
- NO neutral
- Li₂O basic
| ClassifyoxidesLi₂Obasic |
| Worked example 4.6. | - Which is more acidic
- HI or HF in water? HI
- since the H–I bond is longer and weaker
| acidicwatersincebond |
5.1 Concept
- Before the nature of chemical bonding was understood, valency expressed an atom’s ability to combine with a number of other atoms.
- Today the concept of oxidation number is used instead.
- Oxidation number is a number that expresses the electric charge (positive or negative) that the atom or ion carries (or appears to carry) in the compound, whether ionic or covalent.
5.2 Ionic compounds
- The oxidation number of an ion or group equals its charge, with its sign: K+Br− (K +1, Br −1), Na+Cl−, Mg2+O2−, Ca2+CO₃2−, Cu2+SO₄2−.
5.3 Covalent compounds
- The atoms do not form ions, but the shared electrons are displaced towards the more electronegative atom; this atom is assigned a negative number and the less electronegative one a positive number.
- In molecules of an element (S₈, P₄, O₃, Cl₂, H₂, N₂, O₂) the electronegativities are equal, so there is no displacement and each atom has oxidation number zero.
- In molecules of two different atoms the bonding electrons are counted with the more electronegative atom. HCl: H +1, Cl −1. H₂O: H +1, O −2. CO₂: C +4, O −2.
- The sum of oxidation numbers of all atoms in a neutral compound is zero; in an ion it equals the charge of the ion.
- Group 1A elements are always +1; group 2A always +2; group 3A (Al) +3; fluorine is always −1. Start with these.
- is −2 in most compounds, except: peroxides (H₂O₂, Na₂O₂) −1; superoxides (KO₂) −½; oxygen difluoride (OF₂) +2.
- is +1 in most compounds, except metal hydrides (NaH, CaH₂, AlH₃) where it is −1.
- The oxidation number is calculated for one atom (or ion) at a time; some compounds contain atoms of the same element with different oxidation numbers (NH₄NO₂: N is −3 in NH₄+ and +3 in NO₂−).
- The highest oxidation state of a representative element does not exceed its group number (A groups).
- For a polyatomic group the oxidation number is the charge of the group: NO₃− (−1), CO₃2− (−2), SO₄2− (−2), NH₄+ (+1).
Illustrations→Na₂O: Na +1, O −2. Na₂O₂: O −1. KO₂: K +1, O −½. CaH₂: Ca +2, H −1. AlH₃: Al +3, H −1.
5.5 Worked examples
| Comparison aspect | Main idea | Keywords |
|---|
| Worked example 5.1. | Oxidation number of Cr in K₂Cr₂O₇: 2(+1) + 2x + 7(−2) = 0 → 2x = 12 → x = +6 | OxidationnumberK₂Cr₂O₇ |
| Worked example 5.2. | Mn in KMnO₄: +1 + x + 4(−2) = 0 → x = +7. Mn in MnO₂: x − 4 = 0 → +4. Mn in MnCl₂: x − 2 = 0 → +2 | KMnO₄MnO₂MnCl₂ |
| Worked example 5.3. | S in H₂SO₄: 2 + x − 8 = 0 → +6. S in Na₂S₂O₃: 2 + 2x − 6 = 0 → x = +2. S in SO₃2−: x − 6 = −2 → +4. S in H₂S: 2 + x = 0 → −2 | H₂SO₄Na₂S₂O₃SO₃2 |
| Worked example 5.4. | N in NH₄+: x + 4 = +1 → −3. N in NO₃−: x − 6 = −1 → +5. N in HNO₂: 1 + x − 4 = 0 → +3. N in N₂O: 2x − 2 = 0 → +1. N in NO₂: x − 4 = 0 → +4. N in N₂H₄: 2x + 4 = 0 → −2 | HNO₂N₂H₄ |
Worked example 5.5.Cl in NaClO: +1 + x − 2 = 0 → +1; in KClO₃: +1 + x − 6 = 0 → +5; in HClO₄: 1 + x − 8 = 0 → +7.
Worked example 5.6.C in CH₄: x + 4 = 0 → −4; in CH₃OH: x + 3 + (−2) + 1 = 0 → −2; in HCOOH: 2 + x − 4 = 0 → +2; in CO: +2; in CO₂: +4.
Worked example 5.7.O in H₂O₂: 2(+1) + 2x = 0 → −1; in OF₂: x + 2(−1) = 0 → +2; in KO₂: +1 + 2x = 0 → −½.
Worked example 5.8 — average number.Fe in Fe₃O₄: 3x − 8 = 0 → x = +8/3 (average of 2 Fe3+ and 1 Fe2+).
✍️ Worked examples
- Worked example 5.9 — from the group number.
- The highest oxidation number of chlorine (7A) is +7; of nitrogen (5A) is +5; of sulphur (6A) is +6.
- The lowest is (group number − 8) Cl −1, N −3, S −2.
- Oxidation the process in which an atom/ion loses electrons, resulting in an increase in its oxidation number (positive charge increases).
- Reduction the process in which an atom/ion gains electrons, resulting in a decrease in its oxidation number.
- The reducing agent is the reactant that loses electrons (it is oxidised); the oxidizing agent is the reactant that gains electrons (it is reduced).
- Oxidation and reduction always occur together; the number of electrons lost by the reducing agent equals the number gained by the oxidizing agent.
- A reaction in which no oxidation numbers change is not a redox reaction (e.g. neutralisation NaOH + HNO₃ → NaNO₃ + H₂O; precipitation AgNO₃ + NaCl → AgCl + NaNO₃; CaCO₃ + 2HCl → CaCl₂ + H₂O + CO₂).
- Central atom at its maximum oxidation number → oxidizing agent only: K₂Cr₂O₇ (Cr +6), HNO₃ (N +5), H₂SO₄ (S +6), KMnO₄ (Mn +7).
- Central atom at its minimum oxidation number → reducing agent only: NH₃ (N −3), CH₄ (C −4), H₂S (S −2), H₂.
- Central atom at an intermediate oxidation number → can be either, depending on the reaction: HNO₂ (N +3), SO₂ (S +4), H₂O₂ (O −1).
| Comparison aspect | Main idea | Keywords |
|---|
| Worked example 6.1. | - Zn + CuSO₄ → ZnSO₄ + Cu. Zn: 0 → +2 (oxidation
- Zn is the reducing agent). Cu: +2 → 0 (reduction
- CuSO₄/Cu2+ is the oxidizing agent)
| CuSO₄ZnSO₄oxidationreducing |
| Worked example 6.2. | - CuO + H₂ → Cu + H₂O. Cu +2 → 0 (reduced
- CuO is the oxidizing agent). H 0 → +1 (oxidised
- H₂ is the reducing agent)
| reducedoxidizingagentoxidised |
| Worked example 6.3. | - Fe₂O₃ + 3CO → 2Fe + 3CO₂. Fe +3 → 0 reduction (Fe₂O₃ oxidizing agent)
- C +2 → +4 oxidation (CO reducing agent)
| Fe₂O₃3CO₂reductionoxidizing |
| Worked example 6.4 — a non-redox reaction. | - CaCO₃ + 2HCl → CaCl₂ + H₂O + CO₂: Ca +2
- C +4
- O −2
- H +1
- Cl −1 on both sides. Nothing changes: not redox
| CaCO₃2HClCaCl₂both |
| Worked example 6.5 — oxidation or reduction? | - NO₂ → N₂O₄: N +4 → +4
- neither. Cr₂O₇2− → Cr₂O₃: Cr +6 → +3
- reduction. MnO₄− → MnO₂: Mn +7 → +4
- reduction. ClO₃− → ClO₄−: Cl +5 → +7
- oxidation. FeCl₂ → FeCl₃: Fe +2 → +3
- oxidation. O₂ → O₃: no change in oxidation number (not redox)
| N₂O₄neitherCr₂O₇2Cr₂O₃ |
6.4 Ionic equations, spectator ions and half-reactions
6.4 Ionic equations, spectator ions and half-reactions
- Consider the redox reaction 2NaI(aq) + Cl₂(g) → 2NaCl(aq) + I₂(s).
| Comparison aspect | Main idea | Keywords |
|---|
| The overall ionic equation | 2Na+ + 2I− + Cl₂ → 2Na+ + 2Cl− + I₂ | |
| Na+ | is a spectator ion — its oxidation number does not change and it does not take part actively. Removing it gives the net ionic equation: 2I− + Cl₂ → 2Cl− + I₂ | spectatoroxidationnumberdoes |
| Iodide I− (−1) → I₂ (0) | oxidation. Chlorine Cl₂ (0) → Cl− (−1): reduction | oxidationChlorinereduction |
| • | - Writing each separately and adding electrons to keep the charge balanced: Oxidation half-reaction: 2I− → I₂ + 2e− Reduction half-reaction: Cl₂ + 2e− → 2Cl− Worked example 6.6 — metal with copper sulphate. Zn(s) + CuSO₄(aq) → ZnSO₄(aq) + Cu(s). Overall ionic: Zn + Cu2+ + SO₄2− → Zn2+ + SO₄2− + Cu. Spectator: SO₄2−. Net: Zn + Cu2+ → Zn2+ + Cu. Half-reactions: Zn → Zn2+ + 2e− (oxidation)
- Cu2+ + 2e− → Cu (reduction). Worked example 6.7 — sodium with water. 2Na + 2H₂O → 2NaOH + H₂. Ionic: 2Na + 2H₂O → 2Na+ + 2OH− + H₂. Oxidation: Na → Na+ + e− (×2). Reduction: 2H₂O + 2e− → H₂ + 2OH−. Na is the reducing agent
- water (H +1) is the oxidizing agent. OH− is not changed in oxidation number (it appears as product only). Worked example 6.8 — calcium with water. Ca + 2H₂O → Ca(OH)₂ + H₂. Net ionic: Ca + 2H₂O → Ca2+ + 2OH− + H₂. Oxidation: Ca → Ca2+ + 2e−. Reduction: 2H₂O + 2e− → H₂ + 2OH−
| Writingseparatelyaddingelectrons |
- Separate the oxidation and the reduction half-reactions.
- Balance atoms/ions in each half-reaction.
- Apply conservation of charge by adding electrons (lost on the right of the oxidation, gained on the left of the reduction).
- Multiply to make the electrons lost equal to the electrons gained.
- Add the two half-reactions (electrons cancel).
| Comparison aspect | Main idea | Keywords |
|---|
| Worked example 6.9 (pattern of the book). | Cr(s) + H+ → Cr3+ + H₂ | |
| Oxidation | - Cr → Cr3+ + 3e−. Reduction: 2H+ + 2e− → H₂. Multiply the first by 2 and the second by 3: 2Cr → 2Cr3+ + 6e−
- 6H+ + 6e− → 3H₂. Add: 2Cr + 6H+ → 2Cr3+ + 3H₂. Charge check: left +6
- right +6 ✓
| ReductionMultiplyfirstsecond |
| Worked example 6.10. | Al + Ni2+ → Al3+ + Ni | |
| Oxidation | Al → Al3+ + 3e− (×2). Reduction: Ni2+ + 2e− → Ni (×3). Add: 2Al + 3Ni2+ → 2Al3+ + 3Ni. Charge: +6 = +6 ✓ | Reduction3Ni22Al3Charge |
Worked example 6.11.Zn + Fe3+ → Zn2+ + Fe2+.
OxidationZn → Zn2+ + 2e−. Reduction: Fe3+ + e− → Fe2+ (×2). Add: Zn + 2Fe3+ → Zn2+ + 2Fe2+. Charge: +6 = +2 + 4 ✓.
Worked example 6.12.Br− + Cl₂ → Cl− + Br₂: 2Br− → Br₂ + 2e−; Cl₂ + 2e− → 2Cl−. Add: 2Br− + Cl₂ → Br₂ + 2Cl−.
Worked example 6.13 — balancing with oxidation numbers.Sn2+ + Fe3+ → Sn4+ + Fe2+. Sn rises by 2; Fe falls by 1. Two Fe3+ per Sn2+: Sn2+ + 2Fe3+ → Sn4+ + 2Fe2+. Total charge: +8 = +8 ✓.
Disproportionation→oxidation and reduction occur for the same element in one reactant, which is both oxidised and reduced.
| Comparison aspect | Main idea | Keywords |
|---|
| H₂O₂ → 2H₂O + O₂ | - O in H₂O₂ is −1
- it becomes −2 in H₂O (reduction) and 0 in O₂ (oxidation)
| becomesreductionoxidation |
| Cl₂ + 2NaOH → NaCl + NaClO + H₂O | Cl 0 → −1 and 0 → +1 | |
| Comproportionation | - (synproportionation) — two compounds or ions containing a common element in two different oxidation states react to give one product in
- the element has an intermediate state
| synproportionationcompoundsionscontaining |
| Comparison aspect | Main idea | Keywords |
|---|
| H₂S + SO₂ → 3S + 2H₂O | S −2 (oxidised) and S +4 (reduced) both give S0 | oxidisedreducedbothgive |
| I− + IO₃− + 6H+ → 3I₂ + 3H₂O | - I −1 and I +5 give I 0. (Check: atoms I 6
- O 3
- H 6
- charge 0 both sides ✓.)
| giveCheckatomscharge |
| Worked example 6.14. | - Identify the oxidation
- reduction
- oxidizing agent and reducing agent in MnO₂ + 4HCl → MnCl₂ + Cl₂ + 2H₂O (a pattern the book uses). Mn: +4 → +2 reduction
- MnO₂ oxidizing agent. Cl: −1 → 0 oxidation
- HCl reducing agent (only two of the four Cl− change)
| Identifyoxidationreductionoxidizing |
| Worked example 6.15. | - SO₂ + Cl₂ + 2H₂O → H₂SO₄ + 2HCl: S +4 → +6 oxidised (SO₂ reducing agent)
- Cl 0 → −1 reduced (Cl₂ oxidizing agent)
| 2H₂OH₂SO₄2HCloxidised |
| Worked example 6.16. | - Which of the following is not redox: (a) 2Mg + O₂ → 2MgO (redox)
- (b) NaOH + HCl → NaCl + H₂O (not redox)
- (c) H₂ + Cl₂ → 2HCl (redox)? (b)
| followingredox2MgONaOH |
- Oxidation number rises → oxidation (loss of electrons) → reducing agent.
- Oxidation number falls → reduction (gain of electrons) → oxidizing agent.
- Balance redox equations so that electrons lost = electrons gained and charge is conserved.
📌 Comprehensive Scientific Terminology & Definitions:
| Comparison aspect | Main idea | Keywords |
|---|
| Modern Periodic Table | - Systematic tabular arrangement of elements in increasing order of atomic numbers and the filling of subshells according to the Aufbau principle
- composed of 7 periods and 18 groups across four blocks: s
- and f
| Systematictabulararrangementelements |
| Atomic Radius | Half the distance between the nuclei of two identical covalently bonded atoms. Decreases across a period due to increased effective nuclear charge (Zeff) and increases down a group due to the addition of principal energy shells. | Halfdistancebetweennuclei |
| Ionization Energy (IE) | The minimum energy required to remove the most loosely bound electron from an isolated gaseous atom in its ground state: X(g) + IE → X+(g) + e− | minimumrequiredremovemost |
| Electronegativity | A relative measure of the tendency of an atom in a covalent bond to attract the shared pair of electrons toward itself. Fluorine is the most electronegative element (Pauling value = 4.0) | relativemeasuretendencyatom |
| Electron Affinity (EA) | The energy change associated with the addition of an electron to a gaseous atom in its ground state to form a univalent negative ion: X(g) + e− → X−(g) + EA | energychangeassociatedaddition |
⚖️ Governing Scientific Laws, Principles & Mathematical Formulas:
| Comparison aspect | Main idea | Keywords |
|---|
| Effective Nuclear Charge | Zeff = Zactual – Shielding (S) | ZeffZactualShielding |
| Periodic Trends Across a Period (Left to Right) | - Atomic Radius Decreases | IE
- Electronegativity
- EA Increase
| AtomicRadiusDecreasesElectronegativity |
| Periodic Trends Down a Group (Top to Bottom) | - Atomic Radius Increases | IE
- Electronegativity
- EA Decrease
| AtomicRadiusIncreasesElectronegativity |
| Basic Oxides (Metallic) | - React with acids to form salt + water (e.g
- Na₂O
- MgO
- CaO)
| Reactacidsformsalt |
| Acidic Oxides (Nonmetallic) | - Dissolve in water to form acids
- react with bases (e.g
- CO₂
- SO₃
- P₂O₅)
| Dissolvewaterformacids |
| Amphoteric Oxides | - Act as bases with acids and as acids with bases (e.g
- Al₂O₃
- ZnO
- SnO
- PbO)
| basesacidsAl₂O₃ |
🔍 In-Depth Explanations, Deductions & Core Concepts:
| Comparison aspect | Main idea | Keywords |
|---|
| Why does atomic radius decrease across a period? | - Because the nuclear charge increases by one proton with each consecutive element while electrons enter the same principal shell
- resulting in greater attractive pull on valence electrons without added shielding
| Becausenuclearchargeincreases |
| Why is the 2nd ionization energy of sodium exceptionally high? | - Because removing a second electron requires disrupting a stable
- filled noble-gas core (Ne octet
- 2p6)
- demanding an immense quantity of energy
| Becauseremovingsecondelectron |
| Why is Al₂O₃ classified as amphoteric? | - Because it reacts with strong acids (e.g
- HCl) forming aluminum chloride (basic behavior)
- and with strong bases (e.g
- NaOH) forming sodium meta-aluminate NaAlO₂ (acidic behavior)
| Becausereactsstrongacids |
| Periodic Property |
Across a Period (Left to Right) |
Down a Group (Top to Bottom) |
Fundamental Driving Cause |
| Atomic Radius |
Decreases |
Increases |
Increased Zeff across / Added electron shells down |
| Ionization Energy |
Increases |
Decreases |
Stronger electrostatic pull across / Increased shielding down |
| Electronegativity |
Increases |
Decreases |
Nucleus closer to bond pairs across / Shielded down |
| Metallic Character |
Decreases (Nonmetallic increases) |
Increases |
Valence electrons lost more easily down group |
💡 High-Yield Exam Traps & Key Takeaways:
- Most electronegative elements F (4.0) > O (3.5) > N (3.0) ≈ Cl (3.0).
- Largest atomic radius belongs to Cesium (Cs); smallest non-noble gas is Fluorine (F).