Solubilities in aqueous nitrate solutions that appear to reverse the law of mass action
文献信息
Non-ideal aqueous electrolyte solutions have been studied since the start of the application of thermodynamics to chemistry in the late 19th century. The present study examines some of the most extreme non-ideal behavior ever observed: solubilities of alkali and NH4+ nitrate salts in water that appear to behave the opposite of how the Law of Mass Action would predict. A literature review discovered that the solubilities of NH4NO3 and many alkali nitrate salts increases when another nitrate-bearing electrolyte is added to solution. These occurrences were in concentrated solutions with insufficient water to provide all ions their preferred hydration number without sharing waters between ions. This water deficit results in the formation of contact ion-pairs as well as larger ion-clusters. These ion-clusters may be favored when there is more than one type of monovalent cation present.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.


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