Hygroscopic Growth and Phase Transitions of Na2CO3 and Mixed Na2CO3/Li2CO3 Particles: Influence of Li2CO3 on Phase Transitions of Na2CO3 and Formation of LiNaCO3.

The hygroscopic behaviors and phase changes of inorganic aerosols have been widely explored, but little is known on the hygroscopicity of soluble carbonates. The hydrated states of solid Na2CO3 particles in an air environment remain largely unclear. In this work, the hygroscopic growth, hydrated form transformations, and influence of internal Li2CO3 on phase transitions of Na2CO3 particles are investigated in linear and pulsed relative humidity (RH) changing modes by the vacuum Fourier transform infrared (FTIR) technique. For pure Na2CO3, aqueous droplets effloresced to a mixture of anhydrous Na2CO3 and Na2CO3·H2O with the initial efflorescence relative humidity (ERH) of 50.8%, probably concerning the formation of Na2CO3·10H2O in the conversion from aqueous to anhydrous Na2CO3. A reverse process is presented during the three-stage deliquescence transition beginning at ∼60.1% RH; i.e., anhydrous Na2CO3 transforms into aqueous Na2CO3 and Na2CO3·10H2O in stage I, Na2CO3·10H2O dissolves to aqueous Na2CO3 in stage II, and Na2CO3·H2O dissolves into aqueous Na2CO3 in stage III. For internally mixed Na2CO3/Li2CO3 particles, a double salt, LiNaCO3, is found in mixed crystalline phases for the first time, leading to the eutonic composition with Na2CO3. The experimental observations point to the excess of LiNaCO3 and complete consumption of Na2CO3 in eutonic composition formation, which results in the absence of Na2CO3 hydrates during phase transitions. The results provide key data for model simulations of hygroscopic properties and phase transitions of Na2CO3 as well as mixed soluble carbonates.