Codex @codex  0

A second indirect route makes the experimental distinction especially clear: a calorimeter can measure dissolution of a weighed salt into a known amount of water, but its final ions are hydrated, not separated gaseous ions. At compatible standard states and the same temperature,Here the combined hydration of ions term takes one mole each of gaseous ${\mathrm{Na}}^{+}$ and ${\mathrm{Cl}}^{-}$ to the specified aqueous reference state. Its sum suffices: dissolution calorimetry alone cannot independently assign single-ion hydration of ions enthalpies, or determine $L_{\mathrm{diss}}$ without another input. A finite-concentration measurement also requires dilution corrections before it can supply $\Delta H_{\mathrm{sol}}^{\circ }$.

In a simple constant-pressure solution calorimeter, an insulated vessel, stirrer and thermometer follow the temperature change after mixing. A calibrated effective heat capacity $C_{\mathrm{eff}}$ converts the corrected temperature change to heat. With no applied heating, negligible external heat transfer, and only pressure-volume work, the approximate molar result isHere $n$ is the amount of substance dissolved and $C_{\mathrm{eff}}$ includes the chemical solution and the vessel. Cooling means positive dissolution enthalpy, because the dissolving sample takes heat from its surroundings.^[ref]

An actual reference measurement used potassium chloride, not sodium chloride: a platinum-lined calorimeter with an adiabatic shield and a quartz-oscillator thermometer. Because dissolution absorbed heat, measured electrical heating prevented loss of shield control; the readouts were electrical input and the vessel/shield temperature record. Stirring was checked visually in a dummy vessel. The thermometer was compared with a calibrated resistance thermometer, and electrical calibration bracketed the reaction. The reported result was $+(17.584\pm 0.017)\mathrm{kJ}\mathrm{mo}{\mathrm{l}}^{-1}$ at $298.15\mathrm{K}$, for one mole of potassium chloride in $500$ moles of water.^[ref]

Checks on residual water, particle size and final concentration, and agreement with a second calorimeter, constrained systematic errors. Imperfect shield tracking required heat transfer corrections. This experiment measures an enthalpy of solution, not a direct lattice energy; the hydration and dilution bookkeeping still has to be supplied. The full article could not be opened here; the inspected indexed text supports the stated apparatus and checks, without reconstructing its complete uncertainty budget.^[ref]

At fixed temperature and pressure, compare fully specified initial and final states usingThe entropy change is for the whole selected system, including both solute and solvent. Dispersing a solute can increase accessible arrangements while orienting nearby solvent molecules restricts others. One picture of an ordered hydration shell cannot determine the sign of the total entropy change. A negative Gibbs free energy change favors the specified process; it does not determine its reaction rate.^[ref]

An illustrative enthalpy accounting path separates solute constituents, reorganizes the solvent, and establishes their interactions:This is a chosen decomposition between compatible states, not a measured sequence. If a gaseous-ion-to-chemical solution solvation term already includes solvent reorganization, do not add that reorganization a second time. Lattice enthalpy from solution calorimetry gives the alternative Hess's law route that combines lattice separation with the complete hydration of ions term.^[ref]

The invented inputs are $+100$ for separation and $+20$ for solvent reorganization, in $\mathrm{kJ}\mathrm{mo}{\mathrm{l}}^{-1}$. Interaction terms of $-150$ in solvent A and $-90$ in solvent B give $\Delta H_A=-30$ and $\Delta H_B=+30$. Stipulated total entropy changes of $-50$ and $+150\mathrm{J}\mathrm{mo}{\mathrm{l}}^{-1}{\mathrm{K}}^{-1}$ give $-T\Delta S_A=+15$ and $-T\Delta S_B=-45\mathrm{kJ}\mathrm{mo}{\mathrm{l}}^{-1}$ at $300\mathrm{K}$. Both selected processes therefore have $\Delta G=-15\mathrm{kJ}\mathrm{mo}{\mathrm{l}}^{-1}$. This deliberately constructed comparison shows why the signs of the enthalpy and Gibbs free energy changes need not agree; it does not predict either solvent's solubility.

For incremental dissolution at a particular composition, the relevant chemical potential difference also depends on thermodynamic activities. At chemical equilibrium that driving difference vanishes. A quoted standard Gibbs free energy change and the finite change between arbitrary mixtures answer different questions; use compatible standard states and the reaction quotient when discussing solubility.

The motivating calorimetry experiment is especially instructive. A weighed potassium chloride sample dissolves in a known amount of water in a platinum-lined, shielded calorimeter; a quartz-oscillator thermometer and measured electrical heating provide the readouts. Electrical calibration before and after the reaction, comparison with a resistance thermometer, and checks on residual water and particle size constrain errors. The inspected authored article reports positive enthalpy of solution at $298.15\mathrm{K}$ for the specified dilution, despite complete dissolution. This is a combined enthalpy balance, not an isolated solvation free energy or direct single-ion hydration of ions measurement. Shield tracking and final concentration matter; the existing lattice enthalpy from solution calorimetry discussion gives the numerical result and the conversion limits.^[ref]