PubMed · 13630847
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D G STUART, A HEMINGWAY. 1959. A modified gas analyzer for students.. https://doi.org/10.1152/jappl.1959.14.1.148
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The methyl migration between the protonated N,N-dimethylisopropylamine and other neutral aliphatic amines in the gas phase has been investigated by a hybrid external chemical ionization source ion trap mass spectrometer. Similar reactions have been found in the aqueous solution by Callahan and Wolfenden (J. Am. Chem. Soc. 2003; 125: 310). At the same time, density functional theory (DFT) calculations show that in contrast with the neutral N,N-dimethylisopropylamine, protonated N,N-dimethylisopropylamine is a better methyl donor. These results indicate that protonation promotes the methyl migration between aliphatic amines both in the gas phase and in the aqueous solution. In addition, methyl transfer also exists between the protonated N,N-dimethylisopropylamine and some other nitrogen-containing compounds.
Disconnected bubbles or ganglia of trapped gas may occur below the top of the capillary fringe through a number of mechanisms. In the presence of dense non-aqueous phase liquid (DNAPL), the disconnected gas phase experiences mass transfer of dissolved gases, including volatile components from the DNAPL. The properties of the gas phase interface can also change. This work shows for the first time that when seed gas bubbles exist spontaneous gas phase growth can be expected to occur and can significantly affect water-gas-DNAPL distributions, fluid flow, and mass transfer. Source zone behaviour was observed in three different experiments performed in a 2-dimensional flow cell. In each case, a DNAPL pool was created in a zone of larger glass beads over smaller glass beads, which served as a capillary barrier. In one experiment effluent water samples were analyzed to determine the vertical concentration profile of the plume above the pool. The experiments effectively demonstrated a) a cycle of spontaneous gas phase expansion and vertical advective mobilization of gas bubbles and ganglia above the DNAPL source zone, b) DNAPL redistribution caused by gas phase growth and mobilization, and c) that these processes can significantly affect mass transport from a NAPL source zone.
Nanobubbles at an interface between a hydrophobic solid and water have a wide range of implications, but the evidence for their existence is still being debated. Here we artificially induced nanobubbles on freshly cleaved HOPG substrates in water using the protocol developed previously and subjected the system to moderate levels of degassing (approximately 0.1 atm for 0.5 to 3 h). The AFM images after the partial degassing revealed that some nanobubbles had coalesced and detached from the substrate because of buoyancy, whereas others apparently remained unaffected. The size and spatial distributions of the nanobubbles after the partial degassing suggest that there is a critical size for a nanobubble above which it may grow. The contact angle of water next to nanobubbles (approximately 160 degrees) is much larger than the advancing contact angle of a macroscopic water droplet on the same substrate (approximately 80 degrees) both before and after the partial degassing and concomitant growth and shrinkage of the nanobubbles. The contact angle of a nanobubble also remained unchanged as the nanobubble was moved along the substrate by the AFM tip. The apparent lack of contact angle hysteresis in the nanobubble systems may suggest that the very large contact angle may correspond to a local minimum of the free-energy landscape.