Problem Set
NBPhO 2026
9. CO₂ Fire Extinguisher 8 pts
Use a – diagram of CO₂ to find the dry-ice fraction in the exhaust of a fire extinguisher for two cylinder orientations, then derive the condition under which adiabatic expansion of saturated vapour spontaneously condenses.
Part (i) — 1.5 / 1.5 pts
| Criterion | Points | Result |
|---|---|---|
| Recognising that liquid is impossible at , so the stream is solid, vapour, or a mixture | 0.5 | ✓ ” … lies entirely below this triple point … only the sublimation curve … two stable phases at most: solid and vapour, possibly in coexistence” |
| Excluding pure solid (cannot adiabatically expand through nozzle) | 0.2 | ✓ Reached via the alternative argument that “the constant- line at (scenario a) or (scenario b) does not exit through the saturated-vapour boundary before reaching the MPa isobar” — the trajectory ends inside the dome, which simultaneously rules out pure solid and pure vapour |
| Identifying (), within | 0.3 | ✓ , boxed |
| Tracing the isentrope on the - diagram and concluding the stream is in the two-phase region for one scenario | 0.3 | ✓ Vertical-isentrope tracing performed for both scenarios |
| Two-phase for both scenarios | 0.2 | ✓ Both scenarios explicitly addressed and concluded to land in the solid-vapour dome |
Part (ii) — 1.3 / 3.5 pts
| Criterion | Points | Result |
|---|---|---|
| Recognising that “reversible adiabatic” means isentropic (), so the endpoint is found by going vertically downward on the - diagram | 0.6 | ✓ “Steady reversible adiabatic flow forces along every streamline, so the exit and inlet share a specific entropy” |
| Deriving the lever rule for mass fraction in the two-phase region: | 0.7 | ✓ Derived verbatim from |
| Reading the initial entropy from the saturated-liquid line at , value | 0.5 | ✗ Claude reports , ~750 outside the keyed band |
| Reading the initial entropy from the saturated-vapour line at , value | 0.5 | ✗ Claude reports , ~970 outside the keyed band |
| Reading at the -bar solid boundary, value | 0.3 | ✗ Claude reports , ~250 outside the keyed band |
| Reading at the -bar vapour boundary, value | 0.3 | ✗ Claude reports , ~300 outside the keyed band |
| Computing for scenario (a) | 0.3 | ✗ Claude obtains — almost double the keyed value, propagated cleanly from the off-band entropy readings |
| Computing for scenario (b) | 0.3 | ✗ Claude obtains — about 2.8× the keyed value, same root cause |
Discrepancies
The four diagram-reading entries fall outside the official’s tolerance band; the two final mass-fraction entries fall outside the band. The shifts are not a uniform reference-state offset: at the inlet, Claude reads – below the keyed values, and at the exit he reads – above them. The net effect is to widen the entropy lever from the official’s to — almost a factor of two — while leaving the lever length essentially unchanged ( vs , both consistent with ). The mass fractions inflate accordingly.
A revealing internal symptom: Claude’s computed gap at the dome top corresponds via Clausius–Clapeyron to , while the official’s gap of implies . The NIST value for CO₂ at is , putting the official closer to truth. Claude’s self-consistency check across the sublimation curve (matching to ) verifies a difference, not the absolute positions, and so cannot catch the systematic stretch in his readings between dome and sublimation segment. A second cross-check at the vaporisation curve () would have flagged the issue.
Part (iii) — 3.0 / 3.0 pts
| Criterion | Points | Result |
|---|---|---|
| Setting up the comparison: condensation occurs iff the adiabat lies below the saturation curve in - space | 0.5 | ✓ Stated explicitly in the “complementary derivation”: “the isentropic cooling per unit pressure drop is greater than the saturation-curve cooling — i.e. the vapour cools below the saturation temperature corresponding to its current pressure and falls into the dome” |
| Deriving the saturation slope via Boltzmann (those who know and use Clausius–Clapeyron do not need to derive it) | 0.6 | ✓ Claude invokes Clausius–Clapeyron directly: — the scheme explicitly accepts this in lieu of the Boltzmann derivation |
| Obtaining the Clausius–Clapeyron form | 0.6 | ✓ Equivalent form used; with for the ideal-gas vapour this is identically |
| Adiabat slope from ideal-gas adiabatic law | 0.4 | ✓ "" combined with gives exactly |
| Comparing slopes to obtain the condition | 0.6 | ✓ Boxed result, derived twice: once from via Maxwell + Clausius–Clapeyron, once from the adiabat-vs-saturation slope comparison |
| Numerical check for water giving , hence condensation | 0.3 | ✓ , condensation does occur, plus the kettle-spout physical interpretation |
Overall score: 5.8 / 8.0 pts
Parts (i) and (iii) are clean, full-credit work. The 2.2-point dock all sits on Part (ii)‘s diagram-reading entries: Claude’s four entropy readings and both lever-rule mass fractions fall outside the keyed tolerance bands. The conceptual scaffolding of Part (ii) — recognising isentropic flow and deriving the lever rule — is intact (1.3 of 1.3 pts on those two items), but the numerical output is roughly a factor of two too high in solid fraction.
Numerical answers vs the official key: (exact match); vs official (out of band); vs official (out of band); condensation criterion (exact match); for water at (exact match).
Commentary
Where this solution goes beyond the grading scheme. The “Overview” front-loads the three structural ideas — reversible+adiabatic ⇒ isentropic, exit pressure below the triple point so liquid cannot exist, and the two starting states differ in entropy because the dome at has a finite width — and explicitly notes that pressures, velocities and Mach numbers along the channel never enter the bookkeeping. Part (i) supplements the answer with a “Physics remark — why a de Laval shape,” giving the area-velocity flip across that justifies the converging–diverging geometry, and adds the snow-maker framing that ties the abstract phase-fraction result to the everyday observable. Part (ii) carries an internal Clausius–Clapeyron consistency check ( vs ) and a closing “why scenario (a) gives more solid than (b)” paragraph that connects the lever rule back to the entropy gap across the dome. Part (iii) is unusually thorough: two independent derivations of the same boxed result (one via using Maxwell + Clausius–Clapeyron, one via adiabat-vs-saturation slope comparison), three consistency checks ( limit, critical-point breakdown, dimensional check), an explicit caveat about the ideal-gas premise failing near the critical point — and a closing remark contrasting fogging vapour with non-condensable expansion (refrigerator valve, bicycle pump) that makes the result feel physically populated.
Where the official solution is sharper. Two specific places. (1) The diagram-reading: the official’s four entropy values are internally consistent across both consistency checks — matches , and matches with , close to the NIST value . Claude’s readings only pass the first of these checks; the second would have caught his inflated lever and corrected the factor-of-two error in the mass fractions. The lesson is that one consistency check is not enough on a diagram with two saturation curves at very different temperatures — both gaps must be verified. (2) The official’s slope-comparison framing in Part (iii) is more direct than Claude’s route: comparing with in - space lets the criterion fall out from a single inequality between two well-known thermodynamic slopes, with no Maxwell relation required. Claude does present this route as his “complementary derivation,” but it sits below the longer Maxwell-relation path; reversing the order would put the cleaner derivation forward.