Proton Transfer Reactions

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Brønsted–Lowry Acids and Bases

  • A Brønsted–Lowry acid is a species that donates a proton (H⁺).
  • A Brønsted–Lowry base is a species that accepts a proton using a lone pair of electrons.
  • The theory applies to proton transfer in any solvent, including gas-phase reactions.
  • In HCl(g) + H₂O(l) → H₃O⁺(aq) + Cl⁻(aq), HCl acts as the acid and water as the base.
  • The formation of ions from a molecular acid or base is called dissociation or ionisation.

Proton transfer between an acid and a base

Proton transfer between an acid and a base

Conjugate Acids and Bases

  • A conjugate acid–base pair consists of two species that differ by a single H⁺ ion.
  • In CH₃COOH(aq) + H₂O(l) ⇌ CH₃COO⁻(aq) + H₃O⁺(aq), CH₃COOH/CH₃COO⁻ and H₂O/H₃O⁺ are conjugate pairs.
  • The acid and its conjugate base are related by the loss of one proton; the base and its conjugate acid by the gain of one proton.
  • Strong acids have weak conjugate bases; weak acids have strong conjugate bases.
  • Strong bases have weak conjugate acids.

Amphiprotic Species

  • An amphiprotic species can both donate and accept a proton (H⁺).
  • Water is amphiprotic: it donates a proton to NH₃ and accepts a proton from HCl.
  • An amphoteric substance can act as an acid or a base in a chemical reaction.
  • All amphiprotic substances are amphoteric, but not all amphoteric substances are amphiprotic.
  • Aluminium oxide, Al₂O₃, is amphoteric but not amphiprotic because it does not donate or accept protons.

The pH Scale

  • pH is defined as pH = –log[H⁺], where [H⁺] is the concentration of hydrogen ions in mol dm⁻³.
  • The hydrogen ion concentration can be found from pH using [H⁺] = 10^(–pH).
  • The pH scale is logarithmic: a change of 1 pH unit corresponds to a tenfold change in [H⁺].
  • Acidic solutions have pH < 7, basic solutions have pH > 7, and neutral solutions have pH = 7 at 298 K.
  • The lower the pH, the more acidic the solution; the higher the pH, the more alkaline the solution.
  • A pH meter gives the most accurate pH reading; universal indicator paper is less accurate.

The pH scale

The pH scale

The Ion Product of Water

  • Water undergoes self-ionisation: H₂O(l) ⇌ H⁺(aq) + OH⁻(aq).
  • The ion product of water, Kw, is defined as Kw = [H⁺][OH⁻].
  • At 298 K, Kw = 1.00 × 10⁻¹⁴ mol² dm⁻⁶.
  • In pure water at 298 K, [H⁺] = [OH⁻] = 1.00 × 10⁻⁷ mol dm⁻³, so pH = 7.
  • The ionisation of water is endothermic; increasing temperature increases Kw and decreases the pH of pure water.
  • Pure water remains neutral at any temperature because [H⁺] = [OH⁻].

Strong and Weak Acids and Bases

  • A strong acid dissociates almost completely in aqueous solution (e.g. HCl, HNO₃, H₂SO₄).
  • A weak acid dissociates only partially in aqueous solution (e.g. CH₃COOH, HCN, H₂CO₃).
  • A strong base dissociates almost completely (e.g. Group 1 metal hydroxides).
  • A weak base dissociates only partially (e.g. NH₃, amines).
  • Strong acids have a higher [H⁺], lower pH, greater electrical conductivity, and react more vigorously with metals than weak acids of the same concentration.
  • For hydrogen halides, acid strength increases down Group 17: HF < HCl < HBr < HI, because the H–X bond becomes longer and weaker.

Neutralisation Reactions

  • A neutralisation reaction is: acid + base → salt + water.
  • The essential reaction is H⁺(aq) + OH⁻(aq) → H₂O(l).
  • The salt is formed from the spectator ions not involved in water formation.
  • Acid + metal → salt + hydrogen; acid + metal oxide → salt + water; acid + metal hydroxide → salt + water.
  • Acid + metal carbonate → salt + water + carbon dioxide; acid + metal hydrogencarbonate → salt + water + carbon dioxide.
  • The salt produced depends on the acid used: hydrochloric acid forms chlorides, nitric acid forms nitrates, sulfuric acid forms sulfates.

Universal indicator across the pH scale

Universal indicator across the pH scale

pH Curves and Indicators

  • A pH curve shows how pH changes as acid or base is added during a titration.
  • All pH curves are S-shaped; the midpoint of the vertical section is the equivalence point.
  • Strong acid–strong base: equivalence point at pH 7.
  • Weak acid–strong base: equivalence point above pH 7; at half-equivalence, pH = pKa.
  • Weak base–strong acid: equivalence point below pH 7; at half-equivalence, pOH = pKb.
  • Weak acid–weak base: no sharp vertical section, so the equivalence point is difficult to determine and no suitable indicator exists.

The pOH Scale and Acid–Base Calculations (HL)

  • pOH is defined as pOH = –log[OH⁻].
  • The hydroxide concentration can be found from pOH using [OH⁻] = 10^(–pOH).
  • At 298 K, pH + pOH = 14.
  • The hydrogen ion concentration can be calculated from [OH⁻] using [H⁺] = Kw / [OH⁻].
  • For a strong acid, pH = –log[acid] (for monoprotic acids).
  • For a strong base, first find [OH⁻], then pOH, then pH = 14 – pOH.

Acid and Base Dissociation Constants (HL)

  • The acid dissociation constant, Ka, for HA(aq) ⇌ H⁺(aq) + A⁻(aq) is Ka = [H⁺][A⁻] / [HA].
  • The base dissociation constant, Kb, for B(aq) + H₂O(l) ⇌ BH⁺(aq) + OH⁻(aq) is Kb = [BH⁺][OH⁻] / [B].
  • pKa = –log Ka and pKb = –log Kb.
  • A larger Ka (smaller pKa) means a stronger acid; a larger Kb (smaller pKb) means a stronger base.
  • For conjugate acid–base pairs, Ka × Kb = Kw.
  • The range of pKa values for most weak acids is between 3 and 7.

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練習題

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  1. 1.Using your knowledge of the Brønsted-Lowry theory, which of the following correctly describes ammonia?

    Easy
    • Aneutral
    • Bacid
    • Cbase
    • Damphoteric
  2. 2.In the Brønsted–Lowry theory of acids and bases, the difference between a conjugate acid and its conjugate base is the presence of which of the following?

    Easy
    • Aa positive charge
    • Ba pair of electrons
    • Ca proton
    • Da hydrogen atom
  3. 3.Which of the following ions or compounds is amphiprotic?

    Medium
    • APO₄³⁻
    • BHCO₃⁻
    • CAl₂O₃
    • DP₄O₁₀
  4. 4.In the following reaction, identify which two species are acting as Brønsted–Lowry acids: H₃PO₄(aq) + OH⁻(aq) ⇋ H₂PO₄⁻(aq) + H₂O(l)

    Medium
    • AH₂PO₄⁻(aq) and OH⁻(aq)
    • BH₃PO₄(aq) and H₂PO₄⁻(aq)
    • CH₂PO₄⁻(aq) and H₂O(l)
    • DH₃PO₄(aq) and H₂O(l)
  5. 5.Potassium hydrogen carbonate reacts vigorously with dilute sulfuric acid. Identify the correct formulas of the substances produced in the reaction.

    Medium
    • AK₂SO₄ + H₂O + CO₂
    • BK₂SO₄ + CO₂
    • CKSO₄ + H₂O + CO₂
    • DKSO₄ + H₂CO₃
  6. 6.Copper(II) sulfate can be made by the reaction between dilute sulfuric acid and which of the following? I. Cu II. CuO III. CuCO₃

    Easy
    • AI and II only
    • BI and III only
    • CII and III only
    • DI, II and III
  7. 7.Which statement is correct for the following equation? HSO₄⁻(aq) + OH⁻(aq) ⇌ SO₄²⁻(aq) + H₂O(l)

    Medium
    • AOH⁻ and H₂O are an acid and conjugate base pair
    • BSO₄²⁻ is acting as Brønsted–Lowry acid
    • CHSO₄⁻ and SO₄²⁻ are a base and conjugate acid pair
    • DOH⁻ and H₂O are a base and conjugate acid pair
  8. 8.Which of the following statements about amphiprotic species are correct? (select all that apply)

    Medium
    • AThey can donate a proton.
    • BThey can accept a proton.
    • CAll amphiprotic species are also amphoteric.
    • DAll amphoteric species are also amphiprotic.
    • EThey must contain a metal ion.

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