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CCEA GCE Chemistry (1110) · Unit A2 1: Further Physical and Organic Chemistry
Mini-Lesson

A2 1: Further Physical & Organic Chemistry

Unit A2 1 is the quantitative heart of the A2 year: rate equations, Kp, pH and Ka, buffers, Born–Haber cycles, entropy and Gibbs free energy.

The organic half goes deeper too — optical isomerism, carbonyl chemistry and aromatic chemistry, where you must explain mechanisms rather than recite products.

Work through each screen, answer the questions as you go (several are full A-level calculations) and collect ⭐ stars. Press Start when you're ready.

Kinetics

Rate equations, orders and the rate-determining step

rate = k[A]m[B]nthe orders m and n are found experimentally — never from the balanced equation
  • Zero order — changing [X] has no effect on the rate.
  • First order — rate ∝ [X]; the half-life is constant, whatever the starting concentration.
  • Second order — rate ∝ [X]²; doubling [X] gives the rate.

Units of k depend on the overall order: 1st → s⁻¹ · 2nd → mol⁻¹ dm³ s⁻¹ · 3rd → mol⁻² dm⁶ s⁻¹.

The rate equation is a window on the mechanism. Only species involved in or before the rate-determining (slowest) step appear in it, and the order in each equals the number of its molecules in that step. A species that is zero order is still consumed — just in a later, faster step.

Arrhenius: ln k = ln A − Ea/RT. Plot ln k against 1/T and the gradient is −Ea/R.

Calculate

Your turn — calculation 1

1For a reaction, rate = k[A]²[B]. When [A] = 0.200 mol dm⁻³ and [B] = 0.100 mol dm⁻³, the rate is 8.00 × 10⁻³ mol dm⁻³ s⁻¹. Calculate k, in mol⁻² dm⁶ s⁻¹.
mol⁻² dm⁶ s⁻¹
Hint: k = rate ÷ ([A]²[B]) = 8.00 × 10⁻³ ÷ (0.200² × 0.100).
Method

[A]² = 0.0400. [A]²[B] = 0.0400 × 0.100 = 4.00 × 10⁻³. k = 8.00 × 10⁻³ ÷ 4.00 × 10⁻³ = 2.00 mol⁻² dm⁶ s⁻¹.

Quick check

Think it through

?A reaction is found to be first order overall, and its half-life is measured as 40 s regardless of the starting concentration. What does the constant half-life confirm?
Equilibrium

Kp and partial pressures

partial pressure = mole fraction × total pressuremole fraction = moles of that gas ÷ total moles of gas

For aA(g) + bB(g) ⇌ cC(g) + dD(g):

Kp = (pCc × pDd) ÷ (pAa × pBb)

Only temperature changes K. Raising the pressure shifts the position of equilibrium so that Kp is restored — the constant itself does not change. For an exothermic forward reaction, raising the temperature decreases K.

Calculate

Your turn — calculation 2

2For N₂O₄(g) ⇌ 2NO₂(g), an equilibrium mixture at a total pressure of 100 kPa contains N₂O₄ and NO₂ with mole fractions 0.60 and 0.40. Calculate Kp in kPa, to 1 decimal place.
kPa
Hint: p(N₂O₄) = 0.60 × 100 = 60 kPa; p(NO₂) = 0.40 × 100 = 40 kPa. Kp = p(NO₂)² ÷ p(N₂O₄).
Method

Kp = 40² ÷ 60 = 1600 ÷ 60 = 26.7 kPa. (Units: kPa² ÷ kPa = kPa.)

Quick check

Think it through

?The forward reaction 2SO₂(g) + O₂(g) ⇌ 2SO₃(g) is exothermic. What happens to Kp when the temperature is raised?
Acids and bases

pH, Ka, Kw and buffers

pH = −log₁₀[H⁺]and [H⁺] = 10−pH

A strong acid dissociates fully, so [H⁺] = [acid]. A weak acid only partially dissociates:

Ka = [H⁺][A⁻] ÷ [HA]  →  [H⁺] = √(Ka × [HA])pKa = −log Ka — a smaller pKa means a stronger acid
Kw = [H⁺][OH⁻] = 1.00 × 10⁻¹⁴ at 298 K

A buffer is a weak acid plus its conjugate base. It resists pH change because each component mops up added base or acid:

  • Added H⁺: A⁻ + H⁺ → HA
  • Added OH⁻: HA + OH⁻ → A⁻ + H₂O
[H⁺] = Ka × ([HA] ÷ [A⁻])

A buffer does not stop pH changing — it limits the change. Because both reservoirs are large, the ratio [HA]/[A⁻] shifts only slightly, so the pH moves only slightly. Add enough acid to exhaust the conjugate base and the buffer collapses.

Calculate

Your turn — calculation 3

3Calculate the pH of 0.0200 mol dm⁻³ nitric acid, a strong monobasic acid, to 2 decimal places.
pH
Hint: Fully dissociated, so [H⁺] = 0.0200. pH = −log(0.0200).
Method

[H⁺] = 0.0200 mol dm⁻³ → pH = −log₁₀(0.0200) = 1.70.

Calculate

Your turn — calculation 4

4A 0.0500 mol dm⁻³ solution of a weak monobasic acid has a pH of exactly 3.00. Calculate its pKa, to 2 decimal places.
pK_a
Hint: [H⁺] = 10⁻³ = 1.00 × 10⁻³. Ka = [H⁺]² ÷ [HA] = (1.00 × 10⁻³)² ÷ 0.0500. Then pKa = −log Ka.
Method

[H⁺] = 1.00 × 10⁻³ mol dm⁻³. Ka = (1.00 × 10⁻³)² ÷ 0.0500 = 1.00 × 10⁻⁶ ÷ 0.0500 = 2.00 × 10⁻⁵ mol dm⁻³. pKa = −log(2.00 × 10⁻⁵) = 4.70.

Calculate

Your turn — calculation 5

5A buffer contains 0.100 mol dm⁻³ propanoic acid (Ka = 1.35 × 10⁻⁵ mol dm⁻³) and 0.150 mol dm⁻³ sodium propanoate. Calculate the pH, to 2 decimal places.
pH
Hint: [H⁺] = Ka × [HA] ÷ [A⁻] = 1.35 × 10⁻⁵ × (0.100 ÷ 0.150). Then pH = −log[H⁺].
Method

[H⁺] = 1.35 × 10⁻⁵ × 0.6667 = 9.00 × 10⁻⁶ mol dm⁻³. pH = −log(9.00 × 10⁻⁶) = 5.05. Note the pH is above pKa (4.87) because there is more conjugate base than acid.

Thermodynamics

Born–Haber cycles and lattice enthalpy

The lattice enthalpy of formation is the enthalpy change when one mole of an ionic solid forms from its gaseous ions. It is always exothermic and cannot be measured directly, so it is found indirectly with a Born–Haber cycle — an application of Hess's law.

ΔHf = ΔHat(metal) + IE + ΔHat(non-metal) + EA + ΔHLE

Rearranged: ΔHLE = ΔHf − (sum of all the other steps).

What makes a lattice enthalpy more exothermic: smaller ionic radius and higher ionic charge, because both increase the electrostatic attraction between the ions. That is why MgO (2+, 2−, small ions) has a lattice enthalpy several times more exothermic than NaCl.

Calculate

Your turn — calculation 6

6Use a Born–Haber cycle for KCl. ΔHf(KCl) = −437; ΔHat(K) = +89; 1st IE(K) = +419; ΔHat(½Cl₂) = +122; 1st EA(Cl) = −349, all in kJ mol⁻¹. Calculate the lattice enthalpy of formation of KCl (include the sign).
kJ mol⁻¹
Hint: ΔH_LE = ΔHf − (89 + 419 + 122 − 349).
Method

Sum of the other steps = 89 + 419 + 122 + (−349) = +281 kJ mol⁻¹. ΔHLE = −437 − 281 = −718 kJ mol⁻¹.

Thermodynamics

Entropy and Gibbs free energy

Entropy (S) measures the dispersal of energy and matter. Gases have far higher entropy than liquids, which have more than solids. An increase in the number of moles of gas raises entropy sharply.

ΔS = Σ S(products) − Σ S(reactants)S is in J K⁻¹ mol⁻¹
ΔG = ΔH − TΔSthe reaction is feasible when ΔG ≤ 0

The unit trap: ΔH is in kJ mol⁻¹ and ΔS is in J K⁻¹ mol⁻¹. Divide ΔS by 1000 before substituting, or your answer will be out by a factor of 1000.

Four cases: ΔH negative and ΔS positive → feasible at all temperatures. ΔH positive and ΔS positive → feasible only at high T. ΔH negative and ΔS negative → feasible only at low T. ΔH positive and ΔS negative → never feasible.

Calculate

Your turn — calculation 7

7For N₂(g) + 3H₂(g) → 2NH₃(g), ΔH = −92.2 kJ mol⁻¹ and ΔS = −198.7 J K⁻¹ mol⁻¹. Calculate ΔG at 298 K, in kJ mol⁻¹, to 1 decimal place (include the sign).
kJ mol⁻¹
Hint: Convert ΔS to kJ: −0.1987 kJ K⁻¹ mol⁻¹. ΔG = ΔH − TΔS = −92.2 − (298 × −0.1987).
Method

TΔS = 298 × (−0.1987) = −59.2 kJ mol⁻¹. ΔG = −92.2 − (−59.2) = −33.0 kJ mol⁻¹. Negative, so feasible at 298 K — but only just, and at the high temperatures used industrially ΔG becomes positive.

Sort it

When is the reaction feasible?

Using ΔG = ΔH − TΔS, tap a reaction, then tap when ΔG is negative.

♾️ At all temperatures

🔥 Only at high T

❄️ Only at low T

Further organic

Optical isomerism and carbonyl chemistry

A carbon bonded to four different groups is a chiral centre. The molecule then exists as two enantiomersnon-superimposable mirror images that rotate plane-polarised light by equal amounts in opposite directions. A 50 : 50 mixture is a racemic mixture and is optically inactive.

The carbonyl group, C=O, is polar (Cδ+=Oδ−), so it is attacked by nucleophilesnucleophilic addition.

  • NaBH₄ (the nucleophile is H⁻): aldehyde → primary alcohol; ketone → secondary alcohol.
  • HCN / KCN (the nucleophile is CN⁻) → a hydroxynitrile, lengthening the carbon chain by one.

Why HCN + propanone gives a racemate: the carbonyl carbon is trigonal planar, so CN⁻ can attack from either face with equal probability. Equal amounts of the two enantiomers form, and their optical rotations cancel exactly.

Distinguishing tests: 2,4-DNPH gives an orange precipitate with any carbonyl; Tollens' reagent gives a silver mirror only with an aldehyde.

Quick check

Think it through

?Propanone reacts with HCN to form a product containing a chiral centre, yet the product shows no optical activity. Why?
Further organic

Aromatic chemistry

Benzene is planar and regular hexagonal, with all six C–C bonds the same length — intermediate between a single and a double bond. Each carbon donates a p electron to a delocalised π system above and below the ring.

The evidence for delocalisation: hydrogenating cyclohexene releases −120 kJ mol⁻¹, so three isolated double bonds should release 3 × −120 = −360 kJ mol⁻¹. Benzene actually releases only about −208 kJ mol⁻¹ — it is roughly 152 kJ mol⁻¹ more stable than the Kekulé structure predicts.

Because the delocalised ring is so stable, benzene undergoes electrophilic substitution, which preserves the ring, rather than addition. It does not decolourise bromine water.

  • Nitration — conc. HNO₃ with conc. H₂SO₄ at 50–60 °C. The electrophile is the nitronium ion, NO₂⁺.
  • Halogenation — Br₂ with a halogen carrier (FeBr₃ or AlBr₃) to generate Br⁺.
Match it

Match the reaction to its mechanism

Tap a reaction on the left, then its mechanism on the right.

Reaction
Mechanism
Quick check

Think it through

?Why does benzene undergo substitution rather than addition?
Quick check

Think it through

?A buffer of ethanoic acid and sodium ethanoate has a small amount of NaOH added. Which species removes the added OH⁻?
Recap

The big ideas to know

Rates: rate = k[A]^m[B]^n — orders from experiment; only species in or before the RDS appear; constant half-life = first order

Kp: partial pressure = mole fraction × total pressure; only temperature changes K

Acids: pH = −log[H⁺] · [H⁺] = √(Ka[HA]) · Kw = 1.00 × 10⁻¹⁴ · buffer [H⁺] = Ka[HA]/[A⁻]

Thermodynamics: Born–Haber for lattice enthalpy · ΔG = ΔH − TΔS (convert ΔS to kJ)

Optical isomerism: four different groups → non-superimposable mirror images; a racemate is optically inactive

Carbonyls: nucleophilic addition; HCN gives a racemate because the C=O is planar

Aromatic: delocalisation makes benzene substitute, not add

That is Unit A2 1 — the toughest calculations in the course, plus the mechanisms to explain them. Press Finish to see your score.

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