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Portlandite (Ca(OH)₂; also known as calcium hydroxide or hydrated lime), an archetypal alkaline solid, interacts with carbon dioxide (CO₂) via a classic acid–base “carbonation” reaction to produce a salt (calcium carbonate: CaCO₃) that functions as a low‐carbon cementation agent, and water. Herein, we revisit the effects of reaction temperature, relative humidity (RH), and CO₂concentration on the carbonation of portlandite in the form of finely divided particulates and compacted monoliths. Special focus is paid to uncover the influences of the moisture state (i.e., the presence of adsorbed and/or liquid water), moisture content and the surface area‐to‐volume ratio (s_a/v, mm⁻¹) of reactants on the extent of carbonation. In general, increasing RH more significantly impacts the rate and thermodynamics of carbonation reactions, leading to high(er) conversion regardless of prior exposure history. This mitigated the effects (if any) of allegedly denser, less porous carbonate surface layers formed at lower RH. In monolithic compacts, microstructural (i.e., mass‐transfer) constraints particularly hindered the progress of carbonation due to pore blocking by liquid water in compacts with limited surface area to volume ratios. These mechanistic insights into portlandite's carbonation inform processing routes for the production of cementation agents that seek to utilize CO₂borne in dilute (≤30 mol%) post‐combustion flue gas streams.

Synthetic hydrotalcites were produced by a co‐precipitation method. The hydrotalcites are represented by the general formula [M^II_(1‐x)M^III_(x)(OH)₂][Aⁿ⁻]_x/n·zH₂O, where M^IIis a divalent cation (eg, Mg²⁺or Ca²⁺), M^IIIis a trivalent cation (eg, Al³⁺) and Aⁿ⁻is the interlayer anion. Herein, M^II = Mg, and M^III = Al such that [Mg/Al] = [2, 3] (atomic units) and Aⁿ⁻, represents intercalant species including: OH⁻, SO₄²⁻and CO₃²⁻anions. The thermochemical data of each compound including their solubility constants (K_so), density and molar volume were quantified at T = 25 ± 0.5°C, andP = 1 bar. The solubilities of the synthetic hydrotalcites, irrespective of their divalent‐trivalent cation partitioning ratio, scaled as CO₃²⁻ < SO₄²⁻ < OH⁻; in order of decreasing solubility. The type of anion, very slightly, affected the solubility with less than ±1 log unit of variation for [Mg/Al] = 2, and ±2 log units of variation for [Mg/Al] = 3. The solubilities of these phases were strongly correlated with that of gibbsite (Al(OH)₃); such that activity of the [AlO₂⁻] species wassolubility determiningwith increasing pH. The tabulated thermodynamic data were used to construct solid‐solution models for phases encompassing both cation distribution ratios and to calculate stable phase equilibria relevant to alkali‐activated slag (AAS) systems for diverse activator compositions.