 Tie-line phase-fraction uncertainty

Tie-line phase-fraction uncertainty describes the uncertainty of the phase amount inferred from a tie-line phase-fraction fit. It depends on the uncertainties of the overall composition, the endpoint compositions and the model used to fit them. A conditional estimate treating endpoints as exact omits their contribution. All composition vectors below use two independent coordinates of a ternary liquid-liquid tie line; the third mole fraction is fixed by closure.

For fixed endpoints $\mathbf{a},\mathbf{b}$, let $\mathbf{d}=\mathbf{b}-\mathbf{a}$ and let the overall composition measurement $\mathbf{y}$ have covariance matrix ${\Sigma }_y$. With $W={\Sigma }_y^{-1}$ and an interior unconstrained fit,Here $u$ denotes standard uncertainty. The variance formula is exact for this linear estimator with fixed endpoints and known covariance; Gaussian errors are needed for a Gaussian sampling distribution, not for the variance identity itself. This is an instance of covariance-based uncertainty propagation.^[ref]

Endpoint errors enter through tie-line phase-fraction sensitivity. Near an exactly balanced composition $\mathbf{y}=(1-\lambda )\mathbf{a}+\lambda \mathbf{b}$, with the weight matrix held fixed, differentiating the fit givesIf overall and endpoint measurements are mutually independent, their combined first-order contribution isShared instruments or common reference data can correlate these measurements; then cross-covariances, including tie-line endpoint covariance, must also be propagated rather than discarded.^[ref]

For an original example, use endpoints $(0.60,0.30,0.10)$ and $(0.20,0.40,0.40)$ with overall composition $(0.44,0.34,0.22)$, so $\lambda =0.40$. Let the first two overall mole fractions have independent standard uncertainties $0.010$ and $0.005$. Then $\mathbf{g}=(-2,2)$ and $u^2=0.000500$, giving $u\approx 0.02236$ with exact endpoints. If each endpoint instead has independent coordinate uncertainties $0.005$, with all three measurements independent, the endpoint contribution isThe combined value becomes $u\approx \sqrt{0.000604}=0.02458$.

When the endpoints approach one another, their difference becomes less informative about phase fraction; at coincident endpoints this inference is undefined. Near the physical bounds, clipping an unconstrained fit to the interval from zero to one changes its sampling distribution, potentially creating a point mass at an endpoint. A symmetric Gaussian error summary can then be misleading. Propagating a joint input model through the actual bounded fit with a Monte Carlo method is one possible analysis; it must retain composition closure and the specified correlations. Neither a small uncertainty nor a small ternary tie-line consistency residual independently verifies chemical potential equality or phase stability.