MODULE 2

Equilibrium Electrochemistry

C4740 Physical Chemistry III

 Module 2 – Overview & Learning Outcomes

• Section A: Thermodynamics of the Galvanic Cell & the Nernst Equation

• ΔG–EMF relationship; Nernst equation for non-ideal systems
• Section B: Standard Electrode Potentials
• Determination of E°; temperature dependence → ΔH° and ΔS°
• Section C: Classification of Cells
• Concentration cells (with/without transference); liquid junction potentials
• Section D: Ion-Selective Electrodes & Potentiometric Titrations
• ISE principles; Nikolsky–Eisenman equation; Gran plots
• By the end of this module, you will be able to:
• Derive and apply the Nernst equation to non-ideal electrochemical cells
• Determine standard electrode potentials and thermodynamic quantities from EMF data
• Distinguish cell types and evaluate junction potentials
• Describe ISE operating principles and interpret potentiometric titration data

C4740 · Module 2 – Equilibrium Electrochemistry

 SECTION A

Thermodynamics of the Galvanic Cell &

the Nernst Equation

C4740 · Module 2 – Equilibrium Electrochemistry

 Section A · Thermodynamics of the Galvanic Cell

• A galvanic cell converts the Gibbs energy of a spontaneous redox reaction into electrical work
• Fundamental relationship between cell EMF (E) and Gibbs energy:
• ΔG = −nFE (n = moles of electrons transferred; F = 96 485 C mol⁻¹)
• Spontaneous cell: ΔG < 0 → E > 0
• At standard conditions (all activities = 1):
• ΔG° = −nFE° (E° = standard cell potential)
• Link to equilibrium constant via ΔG° = −RT ln K:
• E° = (RT/nF) ln K or E° = (0.02569/n) ln K at 298 K
• Maximum electrical work extractable: w_elec = −nFE (at reversible conditions)
• Irreversibility (e.g. internal resistance) always reduces actual work below the maximum

C4740 · Module 2 – Equilibrium Electrochemistry

 Section A · Derivation of the Nernst Equation

Each term in Q is the activity of a species raised to its stoichiometric coefficient.

Starting point: ΔG = ΔG° + RT ln Q

−nFE = −nFE° + RT ln Q
Q = reaction quotient; rearranging gives the Nernst equation

Nernst Equation (general form)

E = E° − (RT/nF) ln Q
At 298 K: E = E° − (0.05916/n) log Q (using log₁₀)

Non-ideal form (using activities)

E = E° − (RT/nF) ln(∏ aᵢ^νᵢ)

aᵢ = γᵢ · cᵢ/c°; for ideal solutions γᵢ = 1 and aᵢ = cᵢ/c°

C4740 · Module 2 – Equilibrium Electrochemistry

 Section A · Applying the Nernst Equation – Worked Example

• Consider the cell: Zn(s) | ZnSO₄(aq, 0.010 mol/L) || CuSO₄(aq, 1.00 mol/L) | Cu(s)
• Half-reactions:
• Anode (oxidation): Zn → Zn²⁺ + 2e⁻ E°(Zn²⁺/Zn) = −0.763 V
• Cathode (reduction): Cu²⁺ + 2e⁻ → Cu E°(Cu²⁺/Cu) = +0.340 V
• Standard cell potential:
E° = E°(cathode) − E°(anode) = 0.340 − (−0.763) = +1.103 V
• Reaction quotient Q:
Q = a(Zn²⁺)/a(Cu²⁺) ≈ 0.010/1.00 = 0.010
• Nernst Expression:
E = E° -0.05916/2 log a(Zn²⁺)/a(Cu²⁺) ; n=2
• Ecell?
E = 1.103 − (0.05916/2) log(0.010)
= 1.162 V
• Non-ideal correction: replace concentrations with activities (aᵢ = γ±,i · cᵢ)

C4740 · Module 2 – Equilibrium Electrochemistry

 SECTION B

Standard Electrode Potentials

C4740 · Module 2 – Equilibrium Electrochemistry

 Section B · Standard Electrode Potentials (E°)

• E° is the electrode potential when all species are at unit activity, T = 298 K
• Measured relative to the Standard Hydrogen Electrode (SHE), defined as E° = 0 V
• SHE: Pt | H₂(g, 1 bar) | H⁺(aq, a = 1)
• Experimental determination via EMF measurements:
• Construct cell: SHE || electrode of interest
• Extrapolate EMF to zero ionic strength using Debye–Hückel correction
• Procedure: plot E + (2RT/F) ln m vs √m; extrapolate to m → 0
• Standard reduction potentials (selected, 25°C):
• F₂/F⁻: +2.87 V | MnO₄⁻/Mn²⁺: +1.51 V | Cl₂/Cl⁻: +1.36 V
• Ag⁺/Ag: +0.80 V | Cu²⁺/Cu: +0.34 V | H⁺/H₂: 0.00 V
• Zn²⁺/Zn: −0.76 V | Na⁺/Na: −2.71 V | Li⁺/Li: −3.04 V

C4740 · Module 2 – Equilibrium Electrochemistry

 Section B · Temperature Dependence of E° → ΔH° and ΔS°

Temperature coefficients are small but measurable with precision potentiometry. Important for battery design.

Gibbs–Helmholtz & EMF–entropy link

(∂E°/∂T)_P = ΔS°/(nF)
Measure dE°/dT experimentally to find ΔS° of the cell reaction

Entropy from temperature coefficient

ΔS° = nF (∂E°/∂T)_P
(∂E°/∂T) typically ≈ 10⁻⁴ V K⁻¹; can be + or − depending on reaction

Enthalpy from E° and ΔS°

ΔH° = −nFE° + TΔS° = −nF[E° − T(∂E°/∂T)]

Combines ΔG° = ΔH° − TΔS° with ΔG° = −nFE°

C4740 · Module 2 – Equilibrium Electrochemistry

 SECTION C

Classification of Cells

C4740 · Module 2 – Equilibrium Electrochemistry

 Section C · Concentration Cells – Without Transference

• A concentration cell generates EMF from a difference in activity between two half-cells of the same
electrode type
• Without transference: the two solutions are connected via a salt bridge (no direct ion transfer)
• Example: Ag | AgNO₃(a₁) || AgNO₃(a₂) | Ag
• EMF = (RT/F) ln(a₂/a₁) (for 1-electron process)
• If a₂ > a₁ then E > 0 (spontaneous)
• At 298 K: E = 0.05916 log(a₂/a₁) V
• Application: measurement of activity coefficients (Experiment 2)
• Measure E at known concentrations → calculate γ± via Nernst
• No chemical change occurs overall – only transport of concentration gradient is the driving force

C4740 · Module 2 – Equilibrium Electrochemistry

 Section C · Concentration Cells – With Transference & Junction Potentials

• With transference: solutions are in direct contact; ions physically cross the boundary
• The liquid junction potential (Ej) arises because cations and anions diffuse at different rates
• Fast ion creates a charge layer → potential difference opposes further diffusion
• Henderson equation for the junction potential:
• Ej = −(RT/F) Σ (uᵢzᵢΔcᵢ)/(Σ|zᵢ|uᵢΔcᵢ) · ln(c₂/c₁)
• KCl salt bridge minimises Ej because u(K⁺) ≈ u(Cl⁻) → near-equal diffusion rates
• Transference number tᵢ: measures how much current a given ion carries
• Cell EMF (with transference) = E(without transference) ± Ej

C4740 · Module 2 – Equilibrium Electrochemistry

 Section C · Concentration Cells – Comparison

Without Transference With Transference

• Salt bridge separates half-cells • Direct contact between solutions

• No direct ion crossing the interface • Ions physically migrate across interface
• No liquid junction potential: Ej = 0 • Liquid junction potential Ej ≠ 0
• Simpler thermodynamic analysis • EMF = Nernst term ± Ej
• EMF = (RT/nF) ln(a₂/a₁) • Transference numbers appear in EMF equation
• Used in precise activity coefficient measurements • More common in practice (e.g., pH cells)
• Example: Ag|AgCl electrodes in separate • KCl bridge used to minimise Ej
compartments

C4740 · Module 2 – Equilibrium Electrochemistry

 SECTION D

Ion-Selective Electrodes & Potentiometric

Titrations

C4740 · Module 2 – Equilibrium Electrochemistry

 Section D · Principles of Ion-Selective Electrodes (ISE)

• An ISE develops a potential proportional to the activity of one specific ion in solution
• Key component: ion-selective membrane that is permeable (ideally) only to the target ion
• Types of ISE membranes:
• Glass membrane: H⁺-selective (pH electrode); also Na⁺ and Li⁺ variants
• Crystalline/solid-state: e.g. LaF₃ for F⁻; Ag₂S for S²⁻ and Ag⁺
• Liquid/polymer: doped PVC membranes for K⁺, Ca²⁺, NO₃⁻, etc.
• Gas-sensing: CO₂, NH₃ (internal ISE + diffusion membrane)
• The measured potential (cell EMF) follows the Nernst equation for the primary ion:
• E = const + (RT/zᵢF) ln aᵢ (Nernstian response: 59.16/zᵢ mV per decade at 25°C)
• Selectivity: real ISEs also respond to interfering ions (selectivity coefficient K_ij)

C4740 · Module 2 – Equilibrium Electrochemistry

 Section D · The Nikolsky–Eisenman Equation

Small Kᵢⱼ means high selectivity. The pH glass electrode has K(H,Na) ≈ 10⁻¹¹ — excellent H⁺ selectivity.

Nikolsky–Eisenman equation (ISE with interference)

E = const + (RT/zᵢF) ln [aᵢ + Σⱼ Kᵢⱼ · aⱼ^(zᵢ/zⱼ)]

Kᵢⱼ: potentiometric selectivity coefficient for ion j interfering with ion i

Ideal ISE (no interference)

E = const + (RT/zᵢF) ln aᵢ ≈ const + (S/zᵢ) log aᵢ

S = 59.16 mV/decade at 25°C (theoretical Nernstian slope)

ISE working range (selectivity condition)

aᵢ >> Kᵢⱼ · aⱼ^(zᵢ/zⱼ) for reliable measurement

When Kᵢⱼ is small, interference is negligible over a wide concentration range

C4740 · Module 2 – Equilibrium Electrochemistry

 Section D · Potentiometric Titrations & Gran Plots

• Potentiometric titration: monitor cell EMF as a function of titrant volume added

• Endpoint detected as a sharp inflection in the E vs. V curve
• Advantages over indicator-based titrations:
• Works in coloured or turbid solutions
• Objective: no colour-judgement required
• Can detect multiple equivalence points
• Gran plot (linearisation method):
• Before endpoint: plot 10^(E/S) × V_total vs V_titrant → linear, x-intercept = equivalence point
• After endpoint: similar plot using conjugate direction
• More precise than visual inflection; uses data away from the noisy equivalence point region
• Applications: acid-base, redox, precipitation, complexometric titrations
• ISE-based potentiometric titrations: used for ions not easily colour-indicated (F⁻, Cl⁻, Ca²⁺)

C4740 · Module 2 – Equilibrium Electrochemistry

 MODULE 2 EXERCISES

Conceptual & Problem-Based Practice

C4740 · Module 2 – Equilibrium Electrochemistry

 CONCEPTUAL EXERCISE C1

Question:
Explain why the standard hydrogen electrode (SHE) is assigned a potential of exactly zero volts by convention, rather than being
measured against some absolute reference. What practical difficulties would arise if we tried to measure 'absolute' electrode
potentials, and how does the SHE convention circumvent these?
Solution:
• Electrode potential arises from charge separation at a single metal–solution interface; this cannot be measured without
completing a circuit (i.e., connecting a second interface)
• Any measurement always records the potential difference between two electrodes — never the absolute potential of one
electrode alone
• Absolute single-electrode potentials therefore have no direct experimental meaning
• The SHE convention assigns E° = 0.000 V to H⁺(a=1)/H₂(1 bar)/Pt at 298 K as an arbitrary but universally agreed reference
• This allows all other electrode potentials to be tabulated as relative values on a consistent scale
• Theoretical absolute potentials can be estimated (≈ +4.44 V for SHE on an absolute vacuum scale) but are not directly
measurable and are not needed for practical electrochemistry

Hint: Think about what it means to measure potential at a single electrode interface. What is always measured in practice?

C4740 · Module 2 – Exercises

 CONCEPTUAL EXERCISE C2

Question:
A galvanic cell is constructed using two half-cells of the same redox couple but at different concentrations.
A student claims that such a cell must always have E° = 0 and therefore ΔG° = 0. Do you agree? Explain
how this cell can still generate a non-zero EMF and perform useful work, and identify the thermodynamic
driving force.
Solution:
• Agreed: E° = 0 and ΔG° = 0 — because both half-cells use the same redox couple at unit activity, so E°cell =
E°cathode − E°anode = 0
• However, ΔG and E are not zero when the concentrations differ from standard conditions
• The Nernst equation gives: E = E° − (RT/nF) ln Q = −(RT/nF) ln(a₁/a₂)
• If a₂ > a₁ (cathode side more concentrated), then E > 0 and the cell is spontaneous
• Thermodynamic driving force: the system lowers its Gibbs energy by equalising concentrations (like mixing)
• The cell does electrical work while progressing toward concentration equilibrium (a₁ = a₂ → E → 0)

Hint: Distinguish between ΔG° (standard conditions) and ΔG (actual conditions). Use the Nernst equation.

C4740 · Module 2 – Exercises

 CONCEPTUAL EXERCISE C3

Question:
In potentiometric measurements, a KCl salt bridge is almost universally used to connect two half-cells. (a) Explain the origin of
the liquid junction potential. (b) Why does KCl minimise—but not eliminate—this junction potential? (c) Under what conditions
might a KCl salt bridge introduce errors into your measurements?
Solution:
• (a) Junction potential origin: at the interface between two different electrolyte solutions, ions diffuse down their
concentration gradients. Cations and anions have different mobilities, so one species moves faster, creating a charge
imbalance and hence a potential difference (Ej)
• (b) KCl minimises Ej because u(K⁺) ≈ u(Cl⁻) (7.62 vs 7.91 × 10⁻⁸ m²V⁻¹s⁻¹) — so both ions migrate at nearly the same rate,
minimising charge separation. High KCl concentration also dominates the junction so that the ion mobilities in the junction
are largely those of K⁺/Cl⁻
• (c) KCl bridge introduces errors when:
• The sample contains significant Ag⁺ (AgCl precipitates in the bridge)
• K⁺ or Cl⁻ are the analyte ions — they contaminate the sample
• Very precise thermodynamic work is required — residual Ej is not perfectly zero

Hint: Compare the mobilities of K⁺ (u = 7.62×10⁻⁸ m²V⁻¹s⁻¹) and Cl⁻ (u = 7.91×10⁻⁸ m²V⁻¹s⁻¹).

C4740 · Module 2 – Exercises

 CONCEPTUAL EXERCISE C4

Question:
The Nikolsky–Eisenman equation predicts that an ISE response becomes non-Nernstian at very low analyte activities. (a) Using
the equation E = const + (RT/zᵢF) ln[aᵢ + Kᵢⱼ aⱼ^(zᵢ/zⱼ)], explain why the response plateau at low aᵢ. (b) If a fluoride ISE has K(F,Cl) =
10⁻³ and [Cl⁻] = 0.01 mol/L, what is the lowest [F⁻] that can be reliably measured?
Solution:
• (a) At very low aᵢ, the Kᵢⱼ·aⱼ term dominates inside the logarithm. The equation becomes: E ≈ const + (RT/zᵢF)
ln(Kᵢⱼ·aⱼ) = constant (since aⱼ is fixed)
• Therefore E is independent of aᵢ — the electrode response is flat (non-Nernstian) below the detection limit
• (b) Calculation of detection limit for F⁻ ISE with K(F,Cl) = 10⁻³, [Cl⁻] = 0.01 mol/L:
• Detection limit: aᵢ = Kᵢⱼ · aⱼ^(zᵢ/zⱼ) = 10⁻³ × 0.01 = 1×10⁻⁵ mol/L
• So the lowest reliably measurable [F⁻] is approximately 1×10⁻⁵ mol/L (10 μmol/L)
• Practical remedy: add TISAB (total ionic strength adjustment buffer) to suppress Cl⁻ interference and fix ionic
strength

Hint: At the detection limit, the interference term equals the analyte term. Set Kᵢⱼ·aⱼ = aᵢ to find the limit.

C4740 · Module 2 – Exercises

 CONCEPTUAL EXERCISE C5

Question:
Explain, with reference to the Gibbs–Helmholtz equation and the relationship ΔG° = −nFE°, how a plot of
E°cell vs temperature can yield both ΔH° and ΔS° for a cell reaction. What assumptions must hold for this
analysis to be thermodynamically valid?
Solution:
• Starting from ΔG° = −nFE° and the Gibbs–Helmholtz equation: ΔS° = −(∂ΔG°/∂T)_P = nF(∂E°/∂T)_P
• Measuring E° at several temperatures and plotting E° vs T gives a slope = ΔS°/nF
• ΔS° = nF × (dE°/dT)
• ΔH° = ΔG° + TΔS° = −nFE° + TnF(dE°/dT) = nF[T(dE°/dT) − E°]
• Assumptions required:
• ΔH° and ΔS° are approximately constant over the temperature range studied (small ΔCp)
• Standard conditions are maintained (activities = 1) at each temperature — activity coefficients change with T
• The cell is measured reversibly (near-zero current, high-impedance voltmeter)

Hint: Use dE°/dT = ΔS°/nF and ΔH° = ΔG° + TΔS°. Think about what 'standard conditions' requires.

C4740 · Module 2 – Exercises

 PROBLEM EXERCISE P1

Question:
Calculate the EMF at 25°C of the cell: Zn(s) | ZnCl₂(0.0050 mol/L) || CuSO₄(0.100 mol/L) | Cu(s). Use γ±(ZnCl₂,
0.005) = 0.789 and γ±(CuSO₄, 0.1) = 0.150. E°(Cu²⁺/Cu) = +0.337 V; E°(Zn²⁺/Zn) = −0.763 V. (n = 2)
Solution
• E°cell = +0.337 − (−0.763) = +1.100 V
• Activity of Cu²⁺: For CuSO₄ (2:2 electrolyte), a(Cu²⁺) = γ±² · c = (0.150)² × 0.100 = 2.25×10⁻³
• Activity of Zn²⁺: For ZnCl₂ (1:2 electrolyte), mean activity a± = γ± · (4c³)^(1/3)... simplified: a(Zn²⁺) ≈ γ±² · c =
(0.789)² × 0.005 = 3.11×10⁻³
• Q = a(Zn²⁺)/a(Cu²⁺) = 3.11×10⁻³ / 2.25×10⁻³ = 1.38
E = 1.100 − (0.05916/2) log(1.38) = 1.100 − 0.00412 = +1.096 V
• Note: ideal assumption (γ± = 1) would give Q = 0.005/0.100 = 0.05 and E = 1.100 + 0.038 = 1.138 V — activity
correction is significant

Hint: Calculate a(Zn²⁺) and a(Cu²⁺) using a± = γ±·c. For ZnCl₂: a(Zn²⁺) = (γ±)²·c; use mean ion activity.

C4740 · Module 2 – Exercises

 PROBLEM EXERCISE P2

Question:
The cell Pt | H₂(g, 1 bar) | HCl(m) | AgCl(s) | Ag(s) has the following measured EMF values at 25°C: m = 0.005: E = 0.5096 V; m =
0.010: E = 0.4635 V; m = 0.020: E = 0.4174 V. (a) Write the cell reaction and derive the expression for E in terms of m and γ±. (b)
Use the DHLL to estimate γ± at each m (A = 0.509, z₊=z₋=1). (c) Extrapolate to find E°(AgCl/Ag).
Solution:
• (a) Cell reaction: ½H₂ + AgCl → Ag + H⁺ + Cl⁻; E = E° − (2RT/F)ln(m·γ±)
• Rearrange: E + (2RT/F)ln m = E° − (2RT/F)ln γ±
• (b) Using DHLL: log γ± = −0.509√I = −0.509√m (for 1:1 HCl)
• m = 0.005: log γ± = −0.036 → γ± = 0.921; m = 0.010: γ± = 0.894; m = 0.020: γ± = 0.866
• (c) Compute Y = E + 0.05916 ln m for each m, then plot Y vs √m:
• m=0.005: Y = 0.5096 + 0.05916×(−5.301) = 0.5096 − 0.3136 = 0.1960
• m=0.010: Y = 0.4635 − 0.2722 = 0.1913; m=0.020: Y = 0.4174 − 0.2307 = 0.1867
Extrapolation (linear fit to Y vs √m → √m=0): E°(AgCl/Ag) ≈ +0.222 V (literature: +0.2224 V) ✓

Hint: E = E° − (2RT/F) ln(m·γ±). Plot E + (2RT/F)ln(m) vs √m and extrapolate to m=0 to get E°.

C4740 · Module 2 – Exercises

 PROBLEM EXERCISE P3

Question:
A concentration cell (without transference) uses two silver–silver chloride electrodes in HCl solutions of molality m₁ = 0.100
mol/kg and m₂ = 0.010 mol/kg. (a) Write the cell notation and the Nernst expression. (b) Calculate E at 25°C assuming ideal
behaviour (γ± = 1). (c) Recalculate using γ±(0.100) = 0.796 and γ±(0.010) = 0.905.
Solution:
• (a) Cell: Ag|AgCl(s)|HCl(m₂)||HCl(m₁)|AgCl(s)|Ag; E = (2RT/F) ln[(m₂γ±₂)/(m₁γ±₁)]
• (b) Ideal (γ± = 1): E = (0.05916/1) log(m₁/m₂) = 0.05916 × log(0.100/0.010)
E (ideal) = 0.05916 × 1 = +0.05916 V ≈ 59.2 mV
• (c) Non-ideal: a₁ = m₁·γ±₁ = 0.100 × 0.796 = 0.0796; a₂ = m₂·γ±₂ = 0.010 × 0.905 = 0.00905
• E = (2RT/F) ln(a₁/a₂) = 0.05916 × log(0.0796/0.00905)
E (non-ideal) = 0.05916 × log(8.80) = 0.05916 × 0.944 = +0.0558 V ≈ 55.8 mV
• Activity correction reduces EMF by ~3.4 mV — significant for precision work

Hint: E = (RT/F) ln(a₂/a₁) = (2RT/F) ln[(m₂γ±₂)/(m₁γ±₁)]. Note n=1 for the Ag/AgCl electrode.

C4740 · Module 2 – Exercises

 PROBLEM EXERCISE P4

Question:
The standard EMF of the cell Pt|H₂|HCl(aq)|AgCl|Ag is +0.2224 V at 25°C and +0.2262 V at 15°C. (a) Calculate ΔG°, ΔS°, and ΔH°
for the cell reaction at 25°C. (b) Predict E° at 35°C assuming dE°/dT is constant over this range. Take n = 1 and F = 96 485 C mol⁻¹.
Solution:
• dE°/dT = (E°₂₅ − E°₁₅)/(T₂₅ − T₁₅) = (0.2224 − 0.2262)/(298 − 288) = −3.8×10⁻⁴ V K⁻¹
• ΔG° = −nFE° = −1 × 96485 × 0.2224 = −21 458 J mol⁻¹ = −21.5 kJ mol⁻¹
• ΔS° = nF(dE°/dT) = 1 × 96485 × (−3.8×10⁻⁴) = −36.7 J mol⁻¹ K⁻¹
• ΔH° = ΔG° + TΔS° = −21 458 + 298×(−36.7) = −21 458 − 10 937 = −32 395 J mol⁻¹
ΔH° ≈ −32.4 kJ mol⁻¹ | ΔS° ≈ −36.7 J mol⁻¹ K⁻¹ | ΔG° ≈ −21.5 kJ mol⁻¹
• E° at 35°C: E°(308K) = E°(298K) + (dE°/dT)×ΔT = 0.2224 + (−3.8×10⁻⁴)(10) = 0.2224 − 0.0038
E°(35°C) ≈ 0.2186 V

Hint: dE°/dT = ΔE°/ΔT = (0.2224−0.2262)/(298−288). Then ΔS° = nF·(dE°/dT) and ΔH° = ΔG° + TΔS°.

C4740 · Module 2 – Exercises

 PROBLEM EXERCISE P5

Question:
A fluoride ISE is calibrated and gives the following data in NaF standards (TISAB used, so ionic strength = constant): [F⁻] / mol·L⁻¹:
1.00×10⁻⁴ → E = −85.0 mV; 1.00×10⁻³ → E = −114.5 mV; 1.00×10⁻² → E = −144.0 mV. (a) Determine the experimental Nernst
slope (mV/decade). (b) Compare with the theoretical value. (c) An unknown sample gives E = −128.0 mV. Calculate [F⁻] in the
unknown.
Solution:
• (a) Experimental Nernst slope:
• From 10⁻⁴ → 10⁻³: ΔE = −114.5 − (−85.0) = −29.5 mV per decade
• From 10⁻³ → 10⁻²: ΔE = −144.0 − (−114.5) = −29.5 mV per decade
Experimental slope = −29.5 mV/decade
• (b) Theoretical slope for F⁻ (z = −1): S = −59.16/1 = −59.16 mV/decade
• Experimental slope is about 50% of theoretical — sub-Nernstian response (common for anion ISEs)
• (c) Using calibration: log[F⁻] = (E − E_ref) / slope. At E = −128.0 mV:
• Using point (−114.5 mV at 1.00×10⁻³): Δlog = (−128.0 − (−114.5)) / (−29.5) = −13.5/(−29.5) = 0.458
log[F⁻] = −3 + 0.458 = −2.542 → [F⁻] = 10⁻²·⁵⁴² ≈ 2.87×10⁻³ mol/L

Hint: Slope = ΔE / Δ(log[F⁻]). Theoretical: −59.16/1 = −59.16 mV/decade for z = −1. Then interpolate for unknown.

C4740 · Module 2 – Exercises

 MODULE 2 SUMMARY

Key Takeaways
• ΔG = −nFE links thermodynamics to electrochemistry.
• The Nernst equation corrects for non-standard activities.
• E° is determined by extrapolation to zero ionic strength using DH corrections; temperature dependence yields
ΔH° and ΔS°.
• Concentration cells exploit activity differences; liquid junction potentials are minimised by KCl salt bridges.
• ISEs follow Nernstian response; the Nikolsky–Eisenman equation accounts for interfering ions.

• Next: Module 3 – Electrochemical Kinetics (Electrical Double Layer, Butler–Volmer equation, Tafel plots).

C4740