The zirconia sensor and the switch at λ = 1

Turn the engine mixture from lean to rich, record the voltage of a zirconia sensor and find the stoichiometric point; then change the sensor temperature and the yttria content and see what alters the reading.

Difficulty ●●○ ≈ 25 min

Aim Measure the sensor voltage as a function of λ, locate the jump, and explain why the voltage depends on temperature but not on the number of oxide vacancies.
Equilibrium exhaust from NIST-JANAF data · voltage from the Nernst equation

The oxygen sensor in a car exhaust

Cross-section of the sensor
exhaustλ = 1.050airp(O₂) = 0.2095 bar0.060 VY₂O₃–ZrO₂ solid electrolyteopen circuit: ions hop, but no net current
Sensor voltage
0.90.9511.051.1λ00.20.40.60.81E / V
CO, H₂ and O₂ in the equilibrium exhaust
0.90.9511.051.1λ10⁻²⁴10⁻¹⁸10⁻¹²10⁻⁶0.1mole fraction
  • CO
  • H₂
  • O₂

Equilibrium exhaust: CO₂ 11.91 %, H₂O 13.40 %, CO 1.7e-10 %, H₂ 4.4e-10 %, O₂ 0.9308 %; p(O₂) = 9.31e-3 bar.

E = (RT/4F) ln[0.2095/p(O₂)] = 0.060 V — lean: extra air, and free oxygen left over.

8 mol % Y₂O₃ leaves 3.70 % of the oxide sites empty (Zr₁₋ₓYₓO₂₋ₓ/₂, x = 0.148): O²⁻ moves by hopping into these vacancies.

The fuel is iso-octane, C₈H₁₈. The platinum electrodes are assumed to bring the exhaust to equilibrium at the sensor temperature through CO + ½O₂ ⇌ CO₂ and H₂ + ½O₂ ⇌ H₂O, with constants from the NIST-JANAF functions (Chase 1998); nitrogen oxides, unburnt fuel and response time are left out. The reference side is air with p(O₂) = 0.2095 bar. The lattice is a schematic projection of the fluorite structure with the number of vacancies computed from the composition; the hopping animation is illustrative only — at open circuit there is no net flow of ions.

Procedure

  1. At a sensor temperature of 900 K, start at λ = 1.05 and lower it by 0.01 at a time, recording the voltage down to λ = 0.95.
  2. Between 0.99 and 1.01 switch to steps of 0.001 and find where the voltage crosses 0.45 V.
  3. Repeat a few key points at 700 K and at 1000 K.
  4. Finally change the Y₂O₃ content from 3 to 10 mol% and watch what happens to the number of vacancies and to the voltage.

What to notice

  • At 900 K the lean side reads only 0.06–0.09 V (λ = 1.05–1.01) and the rich side 0.85–0.91 V (λ = 0.99–0.95); almost the whole jump happens within five parts per thousand of λ = 1.
  • The hotter the sensor, the lower the rich-side voltage (at λ = 0.95, 1.00 V at 700 K but 0.86 V at 1000 K): the combustion equilibrium constants fall with temperature, so the equilibrium oxygen pressure rises.
  • Changing the Y₂O₃ content changes the fraction of vacancies but leaves the voltage untouched: the Nernst voltage depends only on the oxygen activities on the two sides, as long as the electrolyte conducts oxide ions.

In a real lab

  • The sensor and exhaust pipe run at several hundred degrees, so let them cool before handling; an engine run indoors must vent its exhaust outside — carbon monoxide is odourless and deadly.
  • Leaded petrol poisons the sensor’s platinum electrodes and the catalytic converter — one reason cars with catalysts must run on unleaded fuel.
  • Real controllers take about 0.45 V as the boundary between rich and lean and keep the mixture swinging around the stoichiometric point; an ageing sensor responds more slowly, which the diagnostic system detects.

All experiments