9. CO₂ Fire Extinguisher 8 pts

Thermodynamics · Phase transitions, isentropic flow, Clausius-Clapeyron

Use a TTss 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.

Self-assessment by Claude Opus 4.7. 5.8 / 8.0

Part (i) — 1.5 / 1.5 pts

CriterionPointsResult
Recognising that liquid is impossible at patm<ptp_\text{atm} < p_t, so the stream is solid, vapour, or a mixture0.5✓ ”p=patm=0.10MPap = p_\text{atm} = 0.10\,\text{MPa} … 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-ss line at s=s(T0)s = s_\ell(T_0) (scenario a) or s=sg(T0)s = s_g(T_0) (scenario b) does not exit through the saturated-vapour boundary before reaching the 0.10.1 MPa isobar” — the trajectory ends inside the dome, which simultaneously rules out pure solid and pure vapour
Identifying T=Tsub(1atm)195KT = T_\text{sub}(1\,\text{atm}) \approx 195\,\text{K} (78°C\approx -78\,°\text{C}), within ±10K\pm 10\,\text{K}0.3Texit=Tsub(patm)195K78°CT_\text{exit} = T_\text{sub}(p_\text{atm}) \approx 195\,\text{K} \approx -78\,°\text{C}, boxed
Tracing the isentrope on the TT-ss diagram and concluding the stream is in the two-phase region for one scenario0.3✓ Vertical-isentrope tracing performed for both scenarios
Two-phase for both scenarios0.2✓ Both scenarios explicitly addressed and concluded to land in the solid-vapour dome

Part (ii) — 1.3 / 3.5 pts

CriterionPointsResult
Recognising that “reversible adiabatic” means isentropic (s=consts = \text{const}), so the endpoint is found by going vertically downward on the TT-ss diagram0.6✓ “Steady reversible adiabatic flow forces Δs=0\Delta s = 0 along every streamline, so the exit and inlet share a specific entropy”
Deriving the lever rule for mass fraction xx in the two-phase region: x=(svapsend)/(svapssol)x = (s_\text{vap} - s_\text{end})/(s_\text{vap} - s_\text{sol})0.7✓ Derived verbatim from s=(1x)sv+xsss = (1-x)\,s_v + x\,s_s
Reading the initial entropy sas_a from the saturated-liquid line at T0=298KT_0 = 298\,\text{K}, value 2100±50Jkg1K1\approx 2100 \pm 50\,\text{J\,kg}^{-1}\,\text{K}^{-1}0.5✗ Claude reports sa1300Jkg1K1s_a \approx 1300\,\text{J\,kg}^{-1}\,\text{K}^{-1}, ~750 outside the keyed band
Reading the initial entropy sbs_b from the saturated-vapour line at T0T_0, value 2550±50Jkg1K1\approx 2550 \pm 50\,\text{J\,kg}^{-1}\,\text{K}^{-1}0.5✗ Claude reports sb1580Jkg1K1s_b \approx 1580\,\text{J\,kg}^{-1}\,\text{K}^{-1}, ~970 outside the keyed band
Reading ssols_\text{sol} at the 11-bar solid boundary, value 400±50Jkg1K1\approx 400 \pm 50\,\text{J\,kg}^{-1}\,\text{K}^{-1}0.3✗ Claude reports ss700Jkg1K1s_s \approx 700\,\text{J\,kg}^{-1}\,\text{K}^{-1}, ~250 outside the keyed band
Reading svaps_\text{vap} at the 11-bar vapour boundary, value 3250±50Jkg1K1\approx 3250 \pm 50\,\text{J\,kg}^{-1}\,\text{K}^{-1}0.3✗ Claude reports sv3600Jkg1K1s_v \approx 3600\,\text{J\,kg}^{-1}\,\text{K}^{-1}, ~300 outside the keyed band
Computing xa0.40±0.05x_a \approx 0.40 \pm 0.05 for scenario (a)0.3✗ Claude obtains xa0.79x_a \approx 0.79 — almost double the keyed value, propagated cleanly from the off-band entropy readings
Computing xb0.25±0.05x_b \approx 0.25 \pm 0.05 for scenario (b)0.3✗ Claude obtains xb0.70x_b \approx 0.70 — about 2.8× the keyed value, same root cause

Discrepancies

The four diagram-reading entries fall outside the official’s ±50Jkg1K1\pm 50\,\text{J\,kg}^{-1}\,\text{K}^{-1} tolerance band; the two final mass-fraction entries fall outside the ±0.05\pm 0.05 band. The shifts are not a uniform reference-state offset: at the inlet, Claude reads 800\sim 80010001000 below the keyed values, and at the exit he reads 300\sim 300350350 above them. The net effect is to widen the entropy lever svsas_v - s_a from the official’s 1.15kJkg1K11.15\,\text{kJ\,kg}^{-1}\,\text{K}^{-1} to 2.30kJkg1K12.30\,\text{kJ\,kg}^{-1}\,\text{K}^{-1} — almost a factor of two — while leaving the lever length svsss_v - s_s essentially unchanged (2.902.90 vs 2.85kJkg1K12.85\,\text{kJ\,kg}^{-1}\,\text{K}^{-1}, both consistent with Lsub/Tsub2.93L_\text{sub}/T_\text{sub} \approx 2.93). The mass fractions inflate accordingly.

A revealing internal symptom: Claude’s computed gap sbsa=0.28kJkg1K1s_b - s_a = 0.28\,\text{kJ\,kg}^{-1}\,\text{K}^{-1} at the dome top corresponds via Clausius–Clapeyron to Lvap(298K)83kJkg1L_\text{vap}(298\,\text{K}) \approx 83\,\text{kJ\,kg}^{-1}, while the official’s gap of 0.45kJkg1K10.45\,\text{kJ\,kg}^{-1}\,\text{K}^{-1} implies Lvap134kJkg1L_\text{vap} \approx 134\,\text{kJ\,kg}^{-1}. The NIST value for CO₂ at 25°C25\,°\text{C} is 122kJkg1\approx 122\,\text{kJ\,kg}^{-1}, putting the official closer to truth. Claude’s self-consistency check across the sublimation curve (matching svsss_v - s_s to Lsub/TsubL_\text{sub}/T_\text{sub}) 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 (sbsa=?Lvap/T0s_b - s_a \stackrel{?}{=} L_\text{vap}/T_0) would have flagged the issue.

Part (iii) — 3.0 / 3.0 pts

CriterionPointsResult
Setting up the comparison: condensation occurs iff the adiabat lies below the saturation curve in TT-pp space0.5✓ 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: dpsat/dT=L/[T(vgv)]L/(Tvg)dp_\text{sat}/dT = L/[T(v_g - v_\ell)] \approx L/(T\,v_g) — the scheme explicitly accepts this in lieu of the Boltzmann derivation
Obtaining the Clausius–Clapeyron form dpsat/dT=pL/(RsT2)\mathrm{d}p_\text{sat}/\mathrm{d}T = pL/(R_sT^2)0.6✓ Equivalent form L/(Tvg)L/(T\,v_g) used; with vg=RsT/pv_g = R_s T/p for the ideal-gas vapour this is pL/(RsT2)pL/(R_s T^2) identically
Adiabat slope dT/dp=RsT/(cpp)\mathrm{d}T/\mathrm{d}p = R_sT/(c_pp) from ideal-gas adiabatic law0.4✓ "(T/p)s=v/cp\left(\partial T/\partial p\right)_s = v/c_p" combined with v=RsT/pv = R_s T/p gives exactly RsT/(cpp)R_s T/(c_p p)
Comparing slopes to obtain the condition L>cpTL > c_pT0.6✓ Boxed result, derived twice: once from dsg/dTsat<0ds_g/dT\big\|_\text{sat} < 0 via Maxwell + Clausius–Clapeyron, once from the adiabat-vs-saturation slope comparison
Numerical check for water giving L/(cpT)3>1L/(c_pT) \approx 3 > 1, hence condensation0.3L/(cpT)=2260/7463.0L/(c_p T) = 2260/746 \approx 3.0, 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: Texit195KT_\text{exit} \approx 195\,\text{K} (exact match); xa0.79x_a \approx 0.79 vs official 0.400.40 (out of band); xb0.70x_b \approx 0.70 vs official 0.250.25 (out of band); condensation criterion L>cpTL > c_p T (exact match); L/cpT3L/c_p T \approx 3 for water at 373K373\,\text{K} (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 25°C25\,°\text{C} 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 M=1M = 1 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 (svsss_v - s_s vs Lsub/TsubL_\text{sub}/T_\text{sub}) and a closing “why scenario (a) gives more solid than (b)” paragraph that connects the lever rule back to the entropy gap Lvap/T0L_\text{vap}/T_0 across the dome. Part (iii) is unusually thorough: two independent derivations of the same boxed result (one via dsg/dTsat<0ds_g/dT\big\|_\text{sat} < 0 using Maxwell + Clausius–Clapeyron, one via adiabat-vs-saturation slope comparison), three consistency checks (L0L \to 0 limit, TTcT \to T_c 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 — svsss_v - s_s matches Lsub/TsubL_\text{sub}/T_\text{sub}, and sbsas_b - s_a matches Lvap/T0L_\text{vap}/T_0 with Lvap(25°C)130kJkg1L_\text{vap}(25\,°\text{C}) \sim 130\,\text{kJ\,kg}^{-1}, close to the NIST value 122kJkg1\sim 122\,\text{kJ\,kg}^{-1}. Claude’s readings only pass the first of these checks; the second would have caught his inflated svsas_v - s_a 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 dsg/dTsat<0ds_g/dT\big\|_\text{sat} < 0 route: comparing dT/dpadiabdT/dp\big\|_\text{adiab} with dT/dpsatdT/dp\big\|_\text{sat} in TT-pp space lets the criterion L>cpTL > c_p T 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.