Chapter 8 and 18– Acids and Bases

8.1 Theories of acids and bases

Arrhenius theory
• An acid is a substance which dissolves in water to produce H+ ions
• Acids which lose or gain only one hydrogen ion are called monoprotic e.g. HCl
• Acids which lose or gain only two hydrogen ions are called diprotic e.g. H2SO4
• Acids which lose or gain only three hydrogen ions are called triprotic e.g. H3PO4
• A hydrogen ion is a bare proton
• H+ ions have strong attraction for the lone pair in H2O – it forms the hydroxonium ion (H3O+)
• Unhydrated protons do not exist in solutions
• The acidic properties of the protons are not affected by the degree of hydration
• A base is a substance which reacts with acids to form salts
• e.g. CaO (s) + 2 HCl (aq) → CaCl2 (aq) + H2O (l)
• Soluble bases are known as alkalis and produce OH– ions in aqueous solution
• Neutralisation takes place when acids react with alkalis, producing salts and water
• HCl (aq) + NaOH (aq) → NaCl (aq) + H2O (l)
• Limitation of Arrhenius definition of acids and bases – only applicable to aqueous solutions
• NH3 (g) + HCl (g) → NH4Cl (s)

Brønsted-Lowry theory
• An acid is a proton donor
• A base is a proton acceptor
• Acid ⇌ Base + H+
• After the acid has donated its proton, the substance left is called a conjugate base
• After the base has accepted the proton, the substance left is called a conjugate acid
• Acid ⇌ Conjugate base + H+
• Base + H+ ⇌ Conjugate acid
• Members of a conjugate pair differ by the presence / absence of the hydrogen ion
• Water is described as amphiprotic – it can act as a base or acid
• Other amphiprotic species include HCO3–, HPO42– and H2PO4–
• Self ionisation of water: H2O + H2O → H3O+ + OH–

Lewis theory
• An acid is an electron pair acceptor leading to the formation of a dative covalent bond
• A base is an electron pair donor leading to the formation of a dative covalent bond
• Complex ions are formed through the bonding of a Lewis acid (metal) and base (ligand)

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 8.2 Properties of acids and bases
Uses of acids
• Industrial manufacture of fertilisers and detergents
• Removing rust from iron and steel
• Car batteries
• Preserving food
• Making fruit juice

Physical properties of acids

• Have a sour taste
• Turn moist blue litmus paper red
• Can conduct electricity

Chemical properties of acids

• Produce hydrogen gas with reactive metals (2 HCl + 2 Na → 2 NaCl + H2)
• Produce carbon dioxide with carbonates (2 HCl + Na2CO3 → 2 NaCl + CO2 + H2O )
• Produce salt and water with metal oxides (2 HCl + MgO → MgCl2 + H2O)
• Produce salt and water with metal hydroxides (HCl + NaOH → NaCl + H2O)

Uses of bases and alkalis

• Neutralise acid on teeth produced by bacteria when they feed on sugars in food (toothpaste
contains magnesium hydroxide)
• Remove excess acid in stomach
• Dissolve dirt and grease – floor cleaners contain NaOH and window cleaners contain NH3

Physical properties of bases and alkalis

• Have a bitter taste
• Feel soapy when in contact with skin
• Turn moist red litmus paper blue
• Can conduct electricity

Chemical properties of bases and alkalis

• Produce salt and water with acids (HCl + NaOH → NaCl + H2O)
• Produce salt, water and ammonia gases when heated with ammonium compounds
• (NH4Cl + NaOH → NaCl + NH3 + H2O
• Produce precipitate with solutions of some cations

8.3 The pH scale

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 • pH = – log10 [H+]
• pOH = – log10 [OH–]
• pKw = – log10 [Kw]
• pKa = – log10 [Ka]
• pKb = – log10 [Kb]
• pKw = pH + pOH = 14
• One pH unit represents a 10-fold change in acidity of basicity
• i.e. if pH = 1 then [H+] = 0.1 moldm–3 but if pH = 2 then [H+] = 0.01 moldm–3
• pH values depend on the concentration of the acid or base and the degree of dissociation
• Kc [H2O] = Kw = ionic product of water
• At 25 ºC, Kw = 10–14 mol2dm–6
• Kw is temperature-dependent
• The pH of a neutral solution varies with temperature
• Kw value rises with temperature
• For neutral solutions at 25 ºC, [H+] = [OH–] and pH = 7
• For acidic solutions at 25 ºC, [H+] > [OH–] and pH < 7
• For basic solutions at 25 ºC, [H+] < [OH–] and pH > 7
• When a weak acid dissociates in water, HA (aq) ⇌ H+ (aq) + A– (aq)
• When a weak base dissociates in water, BOH (aq) ⇌ B+ (aq) + OH– (aq)
• Ka = [H+] [A–] / [HA] = dissociation constant of acid
• Kb = [B+] [OH–] / [BOH] = dissociation constant of base
• Ka indicates the strength of the acid and is temperature-dependent
• A weak acid which has dissociated to a larger extent has a larger Ka value and a corresponding
smaller pKa value
• Ka x Kb = Kw if the Ka and Kb values belong to a conjugate acid-base pair
• pKa + pKb = pKw = 14

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 8.4 Strong and weak acids and bases
• Strong acids and bases completely dissociate into their ions in aqueous solution
• HCl (aq) → H+ (aq) + Cl– (aq)
• Weak acids and bases partially dissociate into their ions in aqueous solution
• CH3COOH (aq) → H+ (aq) + CH3COO– (aq)
• Degree of dissociation (α) is the fraction or percentage of molecules that dissociates into ions
• Strong acids have a degree of dissociation value of 1
• Weak acids have a degree of dissociation value of less than 1
• Strong acids have a high concentration of ions and are good electrical conductors
• Weak acids have a low concentration of ions and are poor electrical conductors
• The strength of an acid is directly proportional to the concentration of hydrogen ions in the
solution
• Strong alkalis dissociate completely to produce OH– ions in aqueous solution
• KOH (aq) → K+ (aq) + OH– (aq)
• Weak alkalis dissociate partially to produce fewer OH– ions in aqueous solution
• NH3 (g) + H2O (l) ⇌ NH4+ (aq) + OH– (aq)
• Equimolar solution – two solutions with the same number of moles in the solution
• Difference in concentrations of H+ ions cannot be distinguished using acid-base titration
• Strong acids and bases in aqueous solution always release 57.3 kJmol–1 when mixed together
(enthalpy change of neutralisation)
• Weak acids and bases in aqueous solution will release a different amount of heat
• The degree of dissociation is controlled by the strength of the bond holding the H+ ion in the
molecule and the stability of the anion formed
• A strong acid will have a weak conjugate base
• A weak acid will have a stronger conjugate base
• Ka is a more satisfactory measure of the relative strength of weak acids
• Kb is a more satisfactory measure of the relative strength of weak bases

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 8.5 Acid deposition
• Acid deposition refers to any process in which acidic substances, including particles, gases
and precipitation, leave the atmosphere to be deposited on the surface of the Earth
• Wet deposition – acid rain, fog, snow
• Dry deposition – acidic gases, acidic particles
• Rainwater is naturally acidic with a pH of 5.6 as CO2 dissolves in it to form H2CO3
• Oxides of nitrogen
- Formed in the internal combustion engine of a car or jet engine
- N2 (g) + O2 (g) → 2 NO (g)
- 2 NO (g) + O2 (g) → 2 NO2 (g)
- Nitrogen (IV) oxide or NO2 causes the brown colour of smog
- NO2 forms nitric acid and nitrous acid
- 2 NO2 (g) + H2O (l) → HNO3 (aq) + HNO2 (aq)
- 2 HNO2 (aq) + O2 (g) → 2 HNO3 (aq)
• Sulfur dioxide
- Formed from the combustion of fossil fuels containing high level of sulfur impurities e.g. coal
- S (s) + O2 (g) → SO2 (g)
- SO2 (g) + H2O (l) ⇌ H2SO3 (aq)
- 2 SO2 (g) + O2 (g) ⇌ 2 SO3 (g)
- SO3 (g) + H2O (l) → H2SO4 (aq)
• Problems caused by acid deposition
- Plants cannot photosynthesise properly as H+ ions displace the metal ions needed in
chlorophyll
- H+ ions dissolve rocks, releasing aluminium ions which damage plant roots, leading to stunted
growth
- Fish cannot survive below pH 5.2
- No life can survive below pH 4
- Acid rain dissolves hazardous materials from rocks, which damage aquatic life
- Limestone and marble are dissolved by acid rain
- CaCO3 (s) + H2SO4 (aq) → CaSO4 (s) + H2O (l) + CO2 (g)
• Methods of dealing with acid deposition
- Pre-combustion method
- Hydrodesulfurisation: Crude oil is heated with hydrogen in the presence of a catalyst to
convert the sulfur present to H2S which is removed via bubbling through an alkaline solution
- Post-combustion method
- Exhaust gases are passed through a chamber containing bases for sulfur dioxide to react with
- CaCO3 (s) + SO2 (g) → CaSO3 (s) + CO2 (g)

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 8.6 Buffer solutions
• A buffer solution is a solution whose pH remains almost unchanged when a small amount of
acid or alkali is added to it – it has two parts: one to neutralise any acids and one to neutralise
any alkalis added
• There are two types of buffer solutions:
- Acidic buffer: a weak acid is mixed with the sodium salt of the weak acid
- e.g. ethanoic acid and sodium ethanoate
- Alkali buffer: a weak base is mixed with the salt of the weak base
- e.g. ammonia and ammonium chloride
• A buffer solution works by neutralising most of the extra acid or alkali added
• The two substances used must be a conjugate acid-base pair
• The weaker substance cannot be in excess
• e.g. a buffer solution containing CH3COOH and CH3COONa
- CH3COONa is completely ionised to CH3COO– and Na+
- CH3COOH is a weak acid and is only partially ionised to CH3COO– and H+
- Hence there is CH3COOH to neutralise bases and CH3COO– to neutralise acids
• Henderson-Hasselbach Equation:
- Acidic buffer: pH = pKa + lg [conjugate base] – lg [acid]
- Alkaline buffer: pOH = pKb + lg [conjugate acid] – lg [base]
• The pH of a buffer does not change on dilution
• The best buffer would be when pH of buffer = pKa of buffer (this is also the maximum buffering
capacity)
• A buffer should have a pKa ± 1 range (buffering zone) coinciding with the pH to be maintained
– out of this range, the buffer solution is not able to effectively maintain the pH range

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 8.7 Salt hydrolysis
• Salts are defined as the compound formed when an acid reacts with a base

Type of reactants Example pH level of salt solution

Strong base + Strong acid Sodium chloride Neutral pH = 7

Strong acid + Weak base Sodium ethanoate Acidic pH < 7

Weak acid + Strong base Ammonium chloride Alkaline pH > 7

Weak acid + Weak base Ammonium ethanoate Neutral pH = 7

•
• Salt hydrolysis is a reversible reaction
• It takes place for the following species
- An anion that is a strong conjugate base of a weak acid
- A cation that is a strong conjugate acid of a weak base
- A cation has a high charge density
• Strong acid + strong base
- e.g. K+ + Cl– → KCl
- K+ and Cl– do not undergo hydrolysis but are merely hydrated when dissolved in water
- Hence KCl is neutral
- K+ has a low charge density
- Cl– is a weak conjugate base of HCl
• Strong acid + weak base
- e.g. HCl + NH3 → NH4Cl
- Cl– is a weak conjugate base of HCl and does not undergo hydrolysis
- NH4+ is a strong conjugate of NH3
- NH4+ + H2O ⇌ NH3 + H3O+
- The excess H3O+ results in an overall acidic solution
• Weak acid + strong base
- e.g. CH3COOH + NaOH → CH3COONa + H2O
- Na+ does not undergo hydrolysis
- CH3COO– is a strong conjugate base of CH3COOH and undergoes hydrolysis
- CH3COO– behaves like a base
- CH3COO– + H2O ⇌ CH3COOH + OH–
- The excess OH results in an overall alkaline solution
• Weak acid + weak base
- e.g. CH3COOH + NH3 → CH3COONH4
- Both CH3COOH and NH3 undergo hydrolysis

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 - CH3COO– is a strong conjugate base of a weak acid
- NH4+ is a strong conjugate acid of a weak base
- Acidic hydrolysis: NH4+ + H2O ⇌ NH3 + H3O+
- Alkaline hydrolysis: CH3COO– + H2O ⇌ CH3COOH + OH–
- The pH of the salt solution depends on the strength of the conjugate acid and base involved
• If Ka > Kb then the salt is acidic
• If Ka < Kb then the salt is alkaline
• If Ka = Kb then the salt is neutral

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 8.8 Acid-base titrations
• Types of acid titrations:
1. Strong acid-strong base
2. Strong acid-weak base
3. Weak acid-strong base
4. Weak acid-weak base

5. Polyprotic acid-monoprotic base

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 • In polyprotic acids, the 1st dissociation proceeds more readily than the 2nd
• This is because the 1st dissociation produces H+ ions which suppresses the 2nd dissociation

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 8.9 Indicators
• Acid-base indicators are weak acids or bases
• An equilibrium is established between their molecular and ionic forms
• The molecular form has a different colour as compared to the ionic form
• e.g. HIn ⇌ H+ + In–
• Changes in pH cause a shift in the position of equilibrium – this favours a species over the other
• Dissociation constant of indicator (KIn) = [H3O+] [In–] / [HIn]
• Hence pH = pKIn + lg [H3O+] [In–] / [HIn]
• The end-point of a titration is the volume of reactant added until the indicator to changes colour
• The colour observed at the end will be a mixture of HIn and In–
• The end-point of a titration is detected when the indicator has a colour midway between its
extreme colours (when [HIn] = [In–])
• Different indicators change colour within pH ranges known as the ‘working range’The indicators
change colour over a range of 2 pH units (pKIn ± 1 unit)
• The equivalence point is defined as the point at which the solutions have been mixed in exactly
the right proportions specified by the stoichiometric equation

Types of indicators to use:

Type of titration Indicator Working range Acid colour Alkali colour

Methyl orange 3.1 – 4.4 Red Yellow

Strong acid- Screened

3.1 – 4.4 Violet Green
strong base methyl orange

Phenolphthalein 8.2 – 10.0 Colourless Pink

Strong acid-
Phenolphthalein 8.2 – 10.0 Colourless Pink
weak base

Methyl orange 3.1 – 4.4 Red Yellow

Weak acid-
strong base Screened
3.1 – 4.4 Violet Green
methyl orange

Weak acid-
– – – –
weak base

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