MODULE 1

Electrolyte Solutions

C4740 PHYSICAL CHEMISTRY III

 Overview & Learning Outcomes

• Section A: Introduction to Electrochemistry

• Scope, applications, and fundamental conventions
• Section B: Ideal and Non-Ideal Electrolyte Solutions
• Strong/weak electrolytes, ionic strength, activity, activity coefficients
• Section C: Theories of Electrolyte Solutions
• Debye–Hückel limiting law and extensions
• Ion pairing, conductivity, and transport properties
• By the end of this module, you will be able to:
• Explain electrolyte behavior using thermodynamic and electrostatic models
• Apply activity coefficient models to real electrolyte solutions
• Quantify ionic interactions using Debye–Hückel theory
• Calculate acid dissociation constant of weak acid

C4740 · Module 1 – Electrolyte Solutions

 SECTION A

Introduction to Electrochemistry

C4740 · Module 1 – Electrolyte Solutions

 Section A · Scope & Applications of Electrochemistry

• Electrochemistry studies the interconversion of chemical energy and electrical energy

• Central to a wide range of modern technologies:
• Energy storage and conversion: batteries, fuel cells, supercapacitors
• Corrosion science: understanding and prevention of metal oxidation
• Electrosynthesis: industrial chlorine/NaOH production (chlor-alkali process)
• Electroanalysis: pH electrodes, ion-selective electrodes, biosensors
• Electrocatalysis and water splitting (green hydrogen)
• Spans thermodynamics, kinetics, and transport phenomena at interfaces

C4740 · Module 1 – Electrolyte Solutions

 Section A · Electrochemical Systems & Conventions

• An electrochemical cell converts chemical reactions into electrical work (galvanic) or vice versa
(electrolytic)
• Key components: electrodes (anode/cathode), electrolyte solution, external circuit
• IUPAC sign convention:
• Anode: site of oxidation (negative terminal in galvanic cell)
• Cathode: site of reduction (positive terminal in galvanic cell)
• Cell notation (line notation):
• Anode || Cathode (e.g., Zn | ZnSO₄(aq) || CuSO₄(aq) | Cu)
• Phase boundaries denoted by | ; salt bridge denoted by ||
• Faraday's laws connect charge passed (Q = nF) to moles of substance converted
• F = 96 485 C mol⁻¹ (Faraday constant)

C4740 · Module 1 – Electrolyte Solutions

 SECTION B

Ideal and Non-Ideal Electrolyte

Solutions

C4740 · Module 1 – Electrolyte Solutions

 Section B · Strong vs Weak Electrolytes

• Strong electrolytes: completely dissociate in water

• Examples: NaCl, HCl, KNO₃, NaOH
• Conductivity is high and predictable at low concentrations
• Weak electrolytes: partially dissociate – governed by equilibrium constant Kₐ or Kb
• Examples: CH₃COOH, NH₃, H₂CO₃
• Degree of dissociation α depends on concentration
• Ostwald's Dilution Law for weak electrolytes: Kₐ = cα² / (1 – α)
• At infinite dilution (c → 0), all electrolytes approach full dissociation
• Kohlrausch's Law (strong electrolytes): Λm = Λm° − K√c
• Λm: molar conductivity; Λm°: limiting molar conductivity

C4740 · Module 1 – Electrolyte Solutions

 Section B · Ionic Strength & Electrostatic Interactions

• Real electrolyte solutions deviate from ideal behaviour due to long-range Coulombic interactions
• Ionic strength I captures the total electrostatic environment:
• I = ½ Σᵢ cᵢzᵢ² (cᵢ = molar concentration, zᵢ = charge number of ion i)
• Examples:
• 0.1 mol/L NaCl: I = ½[(0.1)(1)² + (0.1)(1)²] = 0.1 mol/L
• 0.1 mol/L MgCl₂: I = ½[(0.1)(2)² + (0.2)(1)²] = 0.3 mol/L
• Higher charge → much larger ionic strength → greater deviation from ideality
• Importance: ionic strength governs activity coefficients and thermodynamic properties
• Relevant for biological systems, ocean water, industrial brines

C4740 · Module 1 – Electrolyte Solutions

 Section B · Activity, Activity Coefficient & Chemical Potential

Activity accounts for non-ideal behaviour. For ideal solutions, γ± = 1 and a = c/c°.

Chemical potential of ion i

μᵢ = μᵢ° + RT ln(aᵢ)
μᵢ°: standard chemical potential; aᵢ: activity of ion i

Activity of electrolyte (mean ionic activity)

a± = γ± · m± (m± = mean molal concentration)

γ±: mean activity coefficient; m±: (m₊^ν₊ · m₋^ν₋)^(1/ν)

Mean activity coefficient (empirical, dilute solutions)

log γ± = −A|z₊z₋|√I
A ≈ 0.509 in water at 25 °C (Debye–Hückel limiting law)

C4740 · Module 1 – Electrolyte Solutions

 SECTION C

Theories of Electrolyte Solutions

C4740 · Module 1 – Electrolyte Solutions

 Section C · Debye–Hückel Theory – Limiting Law

Debye–Hückel models the ionic atmosphere: each ion surrounded by a cloud of opposite charge that lowers its chemical
potential.
DH Limiting Law (DHLL)

log γ± = −A|z₊z₋| √I
A plot of log γ± vs √I……. A straight line
Valid only at very low I (< ~0.01 mol/L). A = 0.509 (water, 25°C), thus it is called a limiting law

Extended DH Law (EDHL)

log γ± = −A|z₊z₋| √I / (1 + Ba√I)

a: effective ionic diameter; B ≈ 3.281 × 10⁹ m⁻¹ (water, 25°C); extends to I ~ 0.1

C4740 · Module 1 – Electrolyte Solutions

 Section C · Ion Pairing & Short-Range Interactions

• At higher concentrations, ions of opposite charge come close enough to form ion pairs
• Bjerrum ion pairing: ions within distance q = |z₊z₋|e² / (8πε₀εrkT) are 'paired'
• Ion pairs are not chemically bonded – they reduce the effective number of free ions
• Reduces conductivity and osmotic pressure below DH predictions
• Types of ion pairs (Marcus & Hefter):
• Contact ion pair (CIP): ions directly touching, no intervening water
• Solvent-shared ion pair (SSIP): one water layer between ions
• Solvent-separated ion pair: two water layers between ions
• DH theory fails at I > ~0.1 mol/L partly because it ignores ion pairing
• Important in: seawater chemistry, biological electrolytes, ionic liquids

C4740 · Module 1 – Electrolyte Solutions

 Section C · Conductivity & Transport Properties

• Molar conductivity: Λm = κ/c (κ = specific conductance, S/m)

• Kohlrausch's law of independent migration of ions (infinite dilution):
• Λm° = ν₊λ₊° + ν₋λ₋° (λ°: limiting ionic conductivity)
• Debye–Hückel–Onsager equation (corrects for electrophoretic + relaxation effects):
• Λm = Λm° − (A + BΛm°)√c
• Relaxation effect: ion atmosphere lags behind moving ion, slowing it
• Electrophoretic effect: opposite-charge atmosphere moves against the ion
• Transport number tᵢ: fraction of total current carried by ion i
• tᵢ = |zᵢ|uᵢcᵢ / Σ|zⱼ|uⱼcⱼ (uᵢ = ionic mobility)
• Hittorf and moving boundary methods for measuring transport numbers (Experiment 1)

C4740 · Module 1 – Electrolyte Solutions

 MODULE 1 EXERCISES

Conceptual & Problem-Based Practice

C4740 · Module 1 – Electrolyte Solutions

 CONCEPTUAL EXERCISE C1

Question:

Explain why the primary hydration shell of the small, highly charged Al³⁺ ion is much more tightly held
and exchanges water molecules far more slowly than the primary hydration shell of the larger Cs⁺ ion.
In your answer, reference the Born model and charge density.

Hint: Think about how ion radius and charge affect the magnitude of ΔGsol in the Born equation.

C4740 · Module 1 – Exercises

 CONCEPTUAL EXERCISE C2

Question:

The Debye–Hückel Limiting Law (log γ± = −A|z₊z₋|√I) predicts that γ± always decreases as ionic
strength increases. However, for many electrolytes at moderate to high concentrations, γ± is
experimentally observed to increase above 1. Explain this failure and discuss what physical interactions
the DHLL neglects.

Hint: Consider ion pairing, short-range repulsions, and hydration shell effects at high concentrations.

C4740 · Module 1 – Exercises

 CONCEPTUAL EXERCISE C3

Question:

A student measures the molar conductivity of a 0.01 mol/L acetic acid (CH₃COOH) solution and finds it
is much lower than predicted by Kohlrausch's law based on Λm°(CH₃COO⁻) + Λm°(H⁺). However, the
molar conductivity of a 0.01 mol/L HCl solution matches the Kohlrausch prediction closely. Explain
these observations in terms of the nature of strong and weak electrolytes.

Hint: Think about the degree of dissociation α and how it affects the actual concentration of charge carriers.

C4740 · Module 1 – Exercises

 CONCEPTUAL EXERCISE C4

Question:

Describe, using diagrams if appropriate, the three types of ion pairs identified by Marcus and Hefter
(contact, solvent-shared, and solvent-separated). Explain how each type affects the measured molar
conductivity of an electrolyte solution relative to the Debye–Hückel–Onsager prediction.

Hint: Consider how each ion-pair type reduces the effective number of free ions that carry current.

C4740 · Module 1 – Exercises

 PROBLEM EXERCISE P1

Question:

Calculate the ionic strength of the following solutions: (a) 0.05 mol/L NaCl; (b) 0.05 mol/L CaCl₂; (c) a
mixture of 0.02 mol/L NaCl and 0.01 mol/L Na₂SO₄. For each, identify the ion with the greatest
contribution to I.

Hint: Use I = ½Σᵢcᵢzᵢ². Remember to account for stoichiometric dissociation of each salt.

C4740 · Module 1 – Exercises

 PROBLEM EXERCISE P2

Question:

Using the Debye–Hückel Limiting Law with A = 0.509 (water, 25°C), calculate the mean activity
coefficient γ± for: (a) 0.005 mol/L KCl; (b) 0.005 mol/L MgSO₄. Compare your values and explain the
difference. (Experimental values: γ±(KCl) ≈ 0.927; γ±(MgSO₄) ≈ 0.822 at 0.005 mol/L.)

Hint: Calculate I for each salt first. Note the role of |z₊z₋| in the DHLL formula.

C4740 · Module 1 – Exercises

 PROBLEM EXERCISE P3

Question:

The limiting molar conductivities at 25°C are: λ°(H⁺) = 349.8, λ°(CH₃COO⁻) = 40.9 S·cm²·mol⁻¹. A 0.01
mol/L acetic acid solution has a measured molar conductivity of 16.2 S·cm²·mol⁻¹.
(a) Calculate Λm° for acetic acid.
(b) Estimate the degree of dissociation α.
(c) Calculate Kₐ using Ostwald's Dilution Law.

Hint: For (b), use α = Λm/Λm°. For (c), Kₐ = cα²/(1 − α) where c = 0.01 mol/L.

C4740 · Module 1 – Exercises

 PROBLEM EXERCISE P4

Question:

The mean activity coefficient of HCl at 25°C in water is 0.796 at 0.1 mol/L and 0.758 at 0.2 mol/L.
(a) Calculate log γ± at each concentration and compare with the DHLL predictions (I = c for 1:1
electrolyte; A = 0.509).
(b) (b) At which concentration does the DHLL fail more significantly?

Hint: For (a), log(0.796) = ? and log(0.758) = ?. Compare with −0.509√I.

C4740 · Module 1 – Exercises

 PROBLEM EXERCISE P5

Question:

A conductivity cell (cell constant K* = 85.5 m⁻¹) is used to measure the conductance of a 0.01 mol/L KCl
solution. The measured resistance is 1240 Ω.
(a) Calculate the specific conductance κ.
(b) Calculate the molar conductivity Λm.
(c) The Debye–Hückel–Onsager equation gives Λm = Λm° − (A + BΛm°)√c with A = 60.2 and B =
0.2289, Λm°(KCl) = 149.9 S·cm²·mol⁻¹. Predict Λm at 0.01 mol/L and compare with your
experimental value.

Hint: κ = K*/R; Λm = 1000κ/c (c in mol/L gives Λm in S·cm²·mol⁻¹). Use c in mol/cm³ for consistency.

C4740 · Module 1 – Exercises

MODULE 1 SUMMARY

Key Takeaways
• Electrochemistry links thermodynamics, kinetics, and transport at interfaces.
• Strong vs. weak electrolytes differ in degree of dissociation (α); weak electrolytes obey Ostwald's Dilution
Law.
• Ionic strength I = ½Σcᵢzᵢ² governs deviations from ideal behaviour.
• Debye–Hückel theory quantifies non-ideality via ionic atmosphere.
• Next: Module 2 – Equilibrium Electrochemistry & the Nernst Equation.