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The Mixture measurements and the Gibbs-Duhem constraint article describes the inspected acetone–chloroform preparation, apparatus, paired readouts, controls and sampling limits.^[ref]

That existing apparatus account supplies the experimental controls and limitations. Its refractive index calibration yields mass fractions, which must be converted to mole fractions. For a measured component-A mass fraction $w_A$ and component molar masses $M_A,M_B$,Apply this conversion separately to the flask sample and to completely condensed vapor to obtain $x_A$ and $y_A$. Comparing $y_{i}P$ with $x_i{p}_i^{\ast }(T)$ tests Raoult's law at the measured temperature; using the changing temperature at each composition is essential. The chosen A/B values above are unrelated to the protocol's substances.

The more general diagnostic, retaining an ideal gas vapor and negligible pure-liquid pressure correction, isThis follows by replacing $\ln x_i$ with $\ln (x_i{\gamma }_i)$ in the chemical potential subtraction used for Raoult's law. A reproducible discrepancy from ${\gamma }_i=1$ can expose failure of the ideal solution approximation, but interpreting it requires checking measurement uncertainty, representative paired sampling and the ideal gas approximation. Apparent agreement within uncertainty supports an approximation over the tested conditions; it cannot establish exact ideality at every composition.

Positive or negative deviations of component partial pressures require activity coefficients different from one under these assumptions. An azeotrope is also absent from the chosen unequal-vapor pressure model: the explicit inequality in ideal binary vapor composition gives $y_A>x_A$ throughout $0<x_A<1$. An interior equality would require $p_A^{\ast }=p_B^{\ast }$; in that degenerate case every composition has $y_A=x_A$, rather than an isolated enrichment reversal. Neither an azeotrope nor liquid phase separation should be inferred from the ideal curves.

The Gibbs free energy of mixing compares the final mixture's Gibbs free energy with that of its initially separate components at the same temperature and pressure. For an ideal solution, subtract the pure-component reference from $G={\sum }_i{n}_i{\mu }_i$:For one mole of the chosen A/B ideal solution at $300\mathrm{K}$ and $x_A=0.4$,The individual chemical potential changes are $RT\ln 0.4\approx -2.28554\mathrm{kJ}\mathrm{mo}{\mathrm{l}}^{-1}$ for A and $RT\ln 0.6\approx -1.27417\mathrm{kJ}\mathrm{mo}{\mathrm{l}}^{-1}$ for B. Weighting these by $0.4\mathrm{mol}$ and $0.6\mathrm{mol}$ reproduces the total Gibbs free energy of mixing.

If ideality holds in a neighborhood of the specified temperature and pressure, differentiation at fixed component amounts givesThus the ideal mixing Gibbs free energy decrease comes entirely from the entropy increase; the mixing enthalpy and volume changes vanish. Ideality at a single isolated state alone does not determine temperature or pressure derivatives.^[ref]

The same formula rules out spontaneous separation into two liquid thermodynamic phases within this model. Per mole, the mixing Gibbs free energy $g_{\mathrm{mix}}=RT[x\ln x+(1-x)\ln (1-x)]$ hasAdding the pure-component reference contributions changes only a term linear in $x$. The total molar Gibbs free energy is therefore a strictly convex function: a separated pair of different compositions has a larger composition-weighted Gibbs free energy than the uniform sample with the same inventory. Such phase separation requires physics beyond this ideal solution model.

The entropy of mixing is the entropy change between initially separate components and their final mixture, with initial and final temperatures, pressures and component amount of substance values specified. For an ideal solution made from pure liquids at the same temperature and pressure, let $n={\sum }_i{n}_i$. ThenThe right-hand expression is the ideal solution result; the general definition does not require ideality. Each interior mole fraction has a negative logarithm, so mixing distinct components gives positive entropy of mixing. At a pure endpoint, use the limit $x\ln x\to 0$ as $x\to 0^{+}$.

For one mole of the chosen A/B ideal solution with $x_A=0.4$,For the same total amount of substance, equal mole fractions maximize this binary entropy of mixing: the composition function $s(x)=-x\ln x-(1-x)\ln (1-x)$ hasso its unique maximum is $s(1/2)=\ln 2$. This is a comparison between different prepared compositions, not a prediction that a closed sample changes its component inventory to become equimolar.

In the ideal solution and ideal gas vapor approximation, each component's partial pressure equals its liquid mole fraction times its pure-component vapor pressure at the same temperature:These pressure formulas neglect the change in the pure-liquid reference between its saturation pressure and $P$; appreciable real gas behavior also requires a more general treatment. The ideal solution definition in terms of chemical potentials does not require either approximation.^[ref]

A short derivation explains the reference choice. At vapor-liquid equilibrium, each component has the same chemical potential in the liquid and vapor. For an ideal gas mixture, chemical potential of an ideal gas giveswhere $p^{\circ }$ is a reference pressure. Approximate ${\mu }_i^{\ast }(T,P)$ by ${\mu }_i^{\ast }(T,p_i^{\ast })$ and subtract the pure-component equation from the mixture equation:Taking the exponential function gives Raoult's law. Summing partial pressures and normalizing gives $P$ and $y_i$; this last step uses the ideal gas vapor assumption separately from the liquid model.

The law is named after François-Marie Raoult, who measured vapor pressures and freezing behavior of chemical solutions.^[ref]

Hexane is an alkane with formula ${\mathrm{C}}_6{\mathrm{H}}_{14}$; the unqualified laboratory name often refers to the straight-chain isomer, n-hexane. Other constitutional isomers share the same formula.

Its mostly nonpolar molecular surface explains its use as a solvent for many hydrophobic substances. Commercial mixtures called hexanes need not be a chemically pure single isomer, so the material name and molecular identity should not be treated as interchangeable.

A partial correctness claim connecting a precondition $P$, a program $C$ and a postcondition $Q$: every terminating execution begun with $P$ ends with $Q$. State separately whether total correctness is intended.

The Practical Biology protocol uses cold sucrose in buffer solution, ground green leaves, muslin filtration, centrifugation and cold pellet resuspension. A $100\mathrm{W}$ lamp illuminates extract plus DCPIP from $12$–$15\mathrm{cm}$; a red-filter colorimeter monitors blue-color loss.^[ref]

Compare extract plus dye in darkness, illuminated dye without extract, extract without dye, and supernatant plus dye: controls for light, extract dependence, background color and incomplete separation. Green supernatant can remain active; a centrifugation pellet establishes neither purity nor intact chloroplasts.^[ref]

Here is an original logical check of the controls. Suppose only the illuminated extract-plus-dye condition loses blue color, while the dark mixture and illuminated dye-only mixture retain it. Removing light or removing extract each removes the effect in those comparisons. That supports a joint requirement under the tested conditions. If the dye-only mixture also loses blue color, the proposed attribution to extract has failed its control; a faster change in the extract mixture would require a quantitative comparison before attribution. These are conditional cases, not experimental results.

Even the favorable case leaves three distinct questions. Dye reduction demonstrates delivery of electrons to an artificial electron acceptor. An independently calibrated molecular oxygen readout is needed to measure molecular oxygen evolution. Demonstrating carbon fixation additionally requires evidence that carbon dioxide becomes incorporated into organic material. None of the latter quantities is supplied by a blue-color endpoint alone. An absorbance change also needs background and scattering controls before it can be treated as dye concentration; Beer-Lambert law states the relevant assumptions.

In particular, two hypothetical preparations can give the same dye endpoint while differing in whether their stromal Calvin cycle is functional. Observing only the dye discards that distinction. The counterexample establishes why dye decolorization cannot alone prove complete photosynthesis, carbon fixation, or an intact chloroplast. Temperature, extract loading and illumination must also be matched when comparing rates: a lamp can alter both light exposure and heating.