Uganda Advanced Certificate of
Education (UACE)
Inorganic Chemistry Study Notes (P525/2 & P525/3)
1. Periodic Trends & General Principles
Understanding periodic trends across Period 3 and down Groups is crucial for predicting
physical and chemical properties in Inorganic Chemistry.
1.1 Atomic and Ionic Radii
● Across a Period (e.g., Period 3: Na to Ar): Atomic radius decreases.
○ Reason: Nuclear charge increases (more protons are added to the nucleus) while
shielding effect remains relatively constant because electrons are added to the
same outermost energy level. The electrostatic force of attraction between the
nucleus and the outer electrons increases, pulling the electron cloud closer.
● Down a Group: Atomic radius increases.
○ Reason: The number of occupied energy levels (shells) increases down the group.
This increases the shielding effect, outweighing the increase in nuclear charge and
pushing the outermost electrons further from the nucleus.
1.2 Ionization Energy (IE)
First Ionization Energy is the energy required to remove one mole of electrons from one mole of
gaseous atoms to form one mole of gaseous singly charged cations.
● Across a Period: Generally increases due to increasing nuclear charge and decreasing
atomic radius, making it harder to remove an electron.
○ Anomalies in Period 3: * First IE of Aluminium (Al: 1s^2 2s^2 2p^6 3s^2 3p^1) is
lower than Magnesium (Mg: 1s^2 2s^2 2p^6 3s^2). The 3p electron in Al is in a
higher energy sub-shell and is better shielded by the inner 3s electrons, making it
easier to remove.
■ First IE of Sulfur (S: 3s^2 3p^4) is lower than Phosphorus (P: 3s^2 3p^3).
Phosphorus has a stable, half-filled 3p sub-shell. In Sulfur, spin-pair repulsion
between the two electrons in the same 3p orbital makes it easier to remove
one of them.
● Down a Group: Decreases down the group because of increasing atomic radius and
shielding effect, which weakens the attraction between the nucleus and the valence
electron.
1.3 Electronegativity
Electronegativity is the relative measure of the ability of an atom in a covalent bond to attract the
shared pair of electrons towards itself.
● Across a Period: Increases due to increasing nuclear charge and decreasing atomic
radius.
● Down a Group: Decreases because the valence electrons are further from the nucleus
and shielded by more inner shells.
2. Group II Elements: The Alkaline Earth Metals (Be,
Mg, Ca, Sr, Ba)
2.1 Trends in Physical Properties
● Reactivity with Water: Increases down the group.
○ Be does not react with water or steam even at red heat.
○ Mg reacts very slowly with cold water but rapidly with steam:
○ Ca, Sr, and Ba react with cold water with increasing vigor to form hydroxides and
hydrogen gas:
2.2 Solubility of Group II Compounds
The trends in solubility depend on the relative magnitudes of Lattice Energy (\Delta
H_{\text{latt}}) and Hydration Energy (\Delta H_{\text{hyd}}).
A. Solubility of Hydroxides (\text{M(OH)}_2)
● Trend: Increases down the group.
○ Explanation: Both lattice energy and hydration energy decrease down the group as
the cationic radius increases. However, the lattice energy decreases much faster
than the hydration energy of the hydroxide ion (which is relatively small). This
makes the overall enthalpy of solution (\Delta H_{\text{soln}}) more exothermic (or
less endothermic) down the group, increasing solubility.
B. Solubility of Sulfates (\text{MSO}_4)
● Trend: Decreases down the group.
○ Explanation: The sulfate ion (\text{SO}_4^{2-}) is very large. As the cation size
increases down the group, the change in lattice energy is relatively small. However,
the hydration energy of the cation decreases significantly. Since the decrease in
hydration energy outweighs the decrease in lattice energy, \Delta H_{\text{soln}}
becomes more endothermic down the group, making sulfates less soluble.
○ UACE Practical Note: \text{BaSO}_4 is highly insoluble and forms a dense white
precipitate, which is used as a qualitative test for sulfate ions (\text{SO}_4^{2-}).
2.3 Thermal Stability of Carbonates and Nitrates
● Trend: Thermal stability increases down the group.
● Explanation (Polarizing Power): * Down the group, the ionic radius of the cation
(\text{M}^{2+}) increases while its charge (+2) remains constant. Consequently, the
charge density of the cation decreases.
○ A smaller cation with high charge density (like \text{Be}^{2+} or \text{Mg}^{2+}) has
a high polarizing power. It distorts the electron cloud of the large, polarizable
carbonate (\text{CO}_3^{2-}) or nitrate (\text{NO}_3^-) anion.
○ This polarization weakens the carbon-oxygen (or nitrogen-oxygen) bond within the
anion, making it easier to decompose upon heating.
○ Since polarizing power decreases down the group, more heat energy is required to
decompose the compounds.
● Equations of Decomposition: (Note: \text{NO}_2 is a brown gas, \text{O}_2 relights a
glowing splint)
3. Group IV Elements (C, Si, Ge, Sn, Pb)
3.1 Inert Pair Effect and Stability of Oxidation States
Group IV elements have a valence shell configuration of ns^2 np^2. They can exhibit oxidation
states of +2 and +4.
● Trend: The stability of the +4 oxidation state decreases down the group, while the
stability of the +2 oxidation state increases.
● Reason: The Inert Pair Effect. As we go down the group, the inner d and f orbitals
provide poor shielding. The outermost s electrons (ns^2) become increasingly held by the
nucleus and become reluctant to participate in bond formation. Thus, for heavier elements
like Lead (Pb), only the p electrons are lost/shared, making the +2 state the most stable.
○ Carbon and Silicon are stable in +4 (CO_2, SiO_2).
○ Lead is highly stable in +2 (Pb^{2+}). \text{Pb(IV)} compounds act as strong
oxidizing agents as they readily reduce to \text{Pb(II)}:
3.2 Tetrachlorides of Group IV
● Carbon Tetrachloride (\text{CCl}_4): Does not undergo hydrolysis with water.
○ Reason: Carbon has no available, low-energy d-orbitals in its valence shell (n=2) to
accept a lone pair of electrons from water molecules to initiate hydrolysis. It forms
an immiscible layer with water.
● Silicon Tetrachloride (\text{SiCl}_4): Hydrolyzes violently in water to give silicon dioxide
(silicic acid) and misty fumes of hydrogen chloride gas.
○ Reason: Silicon has vacant 3d orbitals in its valence shell which can accept lone
pairs of electrons from water molecules.
○ Equation:
● Lead(II) Chloride (\text{PbCl}_2): Is an ionic solid. It is insoluble in cold water but
dissolves in hot water to form a colorless solution.
3.3 Oxides of Group IV Elements
● \text{CO}_2: Acidic gas. Dissolves in water to form weak carbonic acid
(\text{H}_2\text{CO}_3).
● \text{SiO}_2: Weakly acidic giant covalent solid. It does not react with water but reacts
with hot concentrated alkalis:
● \text{PbO} (Litharge / Massicot): Amphoteric oxide.
○ Reaction with acid:
○ Reaction with alkali:
4. Group VII Elements: The Halogens (F, Cl, Br, I)
4.1 Oxidizing Power
● Trend: Oxidizing power decreases down the group: \text{F}_2 > \text{Cl}_2 > \text{Br}_2
> \text{I}_2.
● Explanation: Down the group, electronegativity and electron affinity decrease (due to
increasing atomic size and shielding), making it harder for the halogen atom to gain an
electron to form a halide ion (\text{X}^-).
● Displacement Reactions: A halogen higher in the group will displace a halide lower in
the group from its salt solution.
○ Example 1: Chlorine gas displaces bromide ions:
○ Example 2: Chlorine gas displaces iodide ions:
4.2 Reaction of Halogens with Sodium Hydroxide (\text{NaOH})
Halogens (except Fluorine) undergo disproportionation (simultaneous oxidation and reduction)
when reacted with sodium hydroxide. The reaction path depends on temperature.
A. With Cold, Dilute \text{NaOH} (15^\circ\text{C})
The halogen is reduced to a halide (\text{X}^-) and oxidized to a halate(I) (\text{XO}^-) ion.
For chlorine:
(Sodium chlorate(I) is used as a bleaching agent)
B. With Hot, Concentrated \text{NaOH} (70^\circ\text{C})
The halate(I) intermediate is thermally unstable and disproportionates further to halate(V)
(\text{XO}_3^-) and halide (\text{X}^-).
For chlorine:
5. Transition Elements (d-Block)
A transition element is defined as a d-block element that forms at least one stable ion with a
partially filled d-subshell. (Note: Zinc is a d-block element but not a transition element because
its atom ([Ar] 3d^{10} 4s^2) and its only stable ion \text{Zn}^{2+} ([Ar] 3d^{10}) have fully filled
d-orbitals).
5.1 Characteristic Properties
1. Variable Oxidation States: Due to the small energy difference between the 3d and 4s
subshells, transition metals can use both 3d and 4s electrons for bonding. E.g., Iron
(\text{Fe}^{2+}, \text{Fe}^{3+}), Manganese (\text{Mn}^{2+} to \text{Mn}^{7+}).
2. Complex Ion Formation: Transition metal ions are small, highly charged, and have
empty, low-energy d-orbitals capable of accepting lone pairs of electrons from ligands.
3. Colored Compounds: d-orbital splitting occurs in the presence of ligands. Electrons
undergo d\text{-}d transitions by absorbing specific wavelengths of visible light; the
complementary color is transmitted/seen.
4. Catalytic Activity: They provide active surface areas for reactant adsorption or
participate in temporary redox pathways due to variable oxidation states (e.g., \text{Fe} in
the Haber Process, \text{V}_2\text{O}_5 in the Contact Process).
5. Magnetic Properties: Paramagnetism arises from the presence of unpaired d-electrons.
5.2 Common Complex Ions & Key Colors to Memorize
● [\text{Cu(H}_2\text{O)}_6]^{2+} : Pale Blue
● [\text{Cu(NH}_3)_4(\text{H}_2\text{O)}_2]^{2+} : Deep Blue / Royal Blue (Formed when
excess ammonia is added to \text{Cu}^{2+} solution)
● [\text{CuCl}_4]^{2-} : Yellow-Green (Formed when concentrated \text{HCl} is added to
\text{Cu}^{2+} solution)
● [\text{Fe(H}_2\text{O)}_6]^{2+} : Pale Green
● [\text{Fe(H}_2\text{O)}_6]^{3+} : Yellow / Pale Brown
● [\text{Fe(SCN)}(\text{H}_2\text{O)}_5]^{2+} : Blood-Red Solution (Confirmatory test for
\text{Fe}^{3+} using thiocyanate ions \text{SCN}^-)
6. Qualitative Analysis (UNEB Chemistry Paper 3 &
Theory Prep)
Qualitative analysis involves identifying unknown cations and anions in a sample.
6.1 Systematic Cation Testing using Aqueous Sodium Hydroxide
(\text{NaOH}(aq)) and Ammonia (\text{NH}_3(aq))
Cation Addition of dilute Addition of excess Addition of dilute Addition of excess
\text{NaOH}(aq) \text{NaOH}(aq) \text{NH}_3(aq) \text{NH}_3(aq)
dropwise dropwise
\text{Pb}^{2+} White precipitate: Precipitate White precipitate: Precipitate is
\text{Pb(OH)}_2(s) dissolves to form a \text{Pb(OH)}_2(s) insoluble
colorless solution:
[\text{Pb(OH)}_4]^{
2-}
\text{Al}^{3+} White precipitate: Precipitate White precipitate: Precipitate is
\text{Al(OH)}_3(s) dissolves to form a \text{Al(OH)}_3(s) insoluble
colorless solution:
[\text{Al(OH)}_4]^-
\text{Zn}^{2+} White precipitate: Precipitate White precipitate: Precipitate
\text{Zn(OH)}_2(s) dissolves to form a \text{Zn(OH)}_2(s) dissolves to form
colorless solution: a colorless
[\text{Zn(OH)}_4]^{ solution:
2-} [\text{Zn(NH}_3)_4
Cation Addition of dilute Addition of excess Addition of dilute Addition of excess
\text{NaOH}(aq) \text{NaOH}(aq) \text{NH}_3(aq) \text{NH}_3(aq)
dropwise dropwise
]^{2+}
\text{Cu}^{2+} Blue precipitate: Precipitate is Blue precipitate: Precipitate
\text{Cu(OH)}_2(s) insoluble \text{Cu(OH)}_2(s) dissolves to form
a deep blue
solution:
[\text{Cu(NH}_3)_4
(\text{H}_2\text{O)}
_2]^{2+}
\text{Fe}^{2+} Dirty green Precipitate is Dirty green Precipitate is
precipitate: insoluble (turns precipitate: insoluble
\text{Fe(OH)}_2(s) brown on standing \text{Fe(OH)}_2(s)
due to oxidation)
\text{Fe}^{3+} Reddish-brown Precipitate is Reddish-brown Precipitate is
precipitate: insoluble precipitate: insoluble
\text{Fe(OH)}_3(s) \text{Fe(OH)}_3(s)
\text{NH}_4^+ No precipitate. On N/A No reaction N/A
heating, a gas with
a pungent smell
(\text{NH}_3) that
turns damp red
litmus paper blue
is evolved.
Key Confirmatory Test for \text{Pb}^{2+} vs \text{Al}^{3+}:
Add dilute potassium iodide (\text{KI}) solution:
● \text{Pb}^{2+} forms a bright yellow precipitate of Lead(II) iodide (\text{PbI}_2), which
dissolves on heating and recrystallizes as "golden spangles" upon cooling.
● \text{Al}^{3+} forms no precipitate (solution remains colorless).
6.2 Anion Identification Tests
1. Carbonate (\text{CO}_3^{2-}) and Hydrogen Carbonate (\text{HCO}_3^-)
● Initial Test: Add dilute hydrochloric acid (\text{HCl}) or nitric acid (\text{HNO}_3).
● Observation: Effervescence occurs; a colorless, odorless gas (\text{CO}_2) is evolved
which turns lime water (\text{Ca(OH)}_2(aq)) milky.
● Distinguishing Test (\text{CO}_3^{2-} vs \text{HCO}_3^-): Add aqueous Magnesium
sulfate (\text{MgSO}_4) or Magnesium chloride (\text{MgCl}_2) to the cold salt solution:
○ \text{CO}_3^{2-}: Forms an immediate white precipitate of \text{MgCO}_3(s) in
the cold.
○ \text{HCO}_3^-: No precipitate forms in the cold (since \text{Mg(HCO}_3)_2 is
soluble). A white precipitate forms only upon boiling / heating the mixture:
2. Sulfate (\text{SO}_4^{2-}) and Sulfite (\text{SO}_3^{2-})
● Test: Add dilute nitric acid (\text{HNO}_3) followed by Barium nitrate (\text{Ba(NO}_3)_2)
or Barium chloride (\text{BaCl}_2) solution.
○ \text{SO}_4^{2-}: Forms a white precipitate of \text{BaSO}_4 which is insoluble
in dilute nitric acid.
○ \text{SO}_3^{2-}: Forms a white precipitate of \text{BaSO}_3 which dissolves in
dilute nitric acid with effervescence of sulfur dioxide gas (\text{SO}_2). (The evolved
sulfur dioxide gas turns acidified potassium dichromate(VI) paper/solution from
orange to green).
3. Chloride (\text{Cl}^-)
● Test: Add dilute nitric acid (\text{HNO}_3) followed by Silver nitrate (\text{AgNO}_3)
solution.
● Observation: A white precipitate of Silver chloride (\text{AgCl}) is formed.
● Confirmatory Step: The white precipitate dissolves completely in dilute aqueous
ammonia (\text{NH}_3(aq)) to form a colorless complex:
4. Nitrate (\text{NO}_3^-) - The Brown Ring Test
● Test: To the salt solution, add a freshly prepared solution of Iron(II) sulfate
(\text{FeSO}_4). Tilt the test tube and carefully pour concentrated sulfuric acid
(\text{H}_2\text{SO}_4) down the side of the test tube so that it forms a layer at the
bottom.
● Observation: A brown ring forms at the junction of the two liquid layers.
● Explanation: The nitrate ion is reduced to nitrogen monoxide (\text{NO}) by \text{Fe}^{2+}
under acidic conditions. \text{NO} then coordinates with remaining hydrated Iron(II) ions to
form the brown nitroso complex: