A selected ion flow tube study of the reactions of the PH+n ions (n=0 to 4) with several molecular gases at 300 K

Abstract

The reactions of ions in the series PH+n (n=0 to 4) have been studied at 300 K with CH3NH2, PH3, NH3, CH3CCH, H2S, C2H4, CH3OH, COS, C2H2, O2, H2O, CH4, HCN, CO2, CO, and H2 using a selected ion flow tube (SIFT) apparatus. The majority are fast binary reactions, the measured rate coefficients, k, being close to the respective collisional values, and for reactions involving polyatomic reactant molecules multiple product ions are observed. Most reaction mechanisms are represented in this large number of reactions including charge transfer, proton transfer, atom abstraction and especially evident is phosphorus atom insertion in which product ions such as HnPN+, HnPO+, HnPS+ and HnCmP+ are formed. The reactions of the PH+n ions (n=0 to 2) with CO2, CO, and H2 proceed by the process of ternary association except for the P+ reaction with CO2, in which PO+ is formed in a fast binary reaction. PH+4 reacts only with CH3NH2 and NH3 by fast proton transfer, a process which is always rapid when it is exothermic. Upper limits to the heats of formation of HPO+, H2PO+, PC2H2+ and HCP have also been deduced from their observation as products of some of the reactions.

Ions in the terrestrial atmosphere and in interstellar clouds

“…(Note that PC has been detected in circumstellar shells.) Following detailed laboratory studies of the reactions of PH: ions (n = 0-4) [57], some indications have been given as to the gas-phase reactions that may be involved in the synthesis of PN and other phosphorus-bearing molecules in interstellar clouds [57]. Only one chlorine-bearing molecule, HC1, has been detected, and proposed routes to its production (and to other possible interstellar chlorine-containing molecules) based on laboratory studies have been discussed [35].…”

Hydride abstraction of methylamine with Cu+(1S) in the gas phase: A density functional theory study

“…Because of its unique importance in the global nitrogen cycle, biology processes, and organic syntheses [1][2][3][4][5][6][7][8], over the past two decades, the gas-phase reactivity of amines with metal ions has been investigated by a great body of studies, wherein hydride abstraction leading to metal hydride and hydride-abstracted amine ions is always a substantial, if not a major, reaction channel [9][10][11][12][13][14][15][16]. For instance, Radecki and Allison have reported that Co + abstracts a hydride unit from amines to form CoH whenever there is an a-hydrogen available but not when there is no a-hydrogen [10].…”

The Chemistry of Phosphorus-bearing Molecules under Energetic Phenomena

“…We have also added the chemical reactions involving PH 3 from the chemical network of Charnley & Millar (1994), who took the rate coefficients of the neutral-neutral reactions H + PH n (n=1-3) from Kaye & Strobel (1983) following the experimental data of Lee et al (1976). Other ion-neutral reactions involving PH n products and species such as PS or HPS were also included in our network following Anicich (1993) and according to the experiments of Smith et al (1989). The two gas-phase reactions, N+CP→PN+C and P+CN→PN +C, proposed by Agúndez et al (2007) with reaction rates of 3×10 −10 cm 3 s −1 were also included in our network.…”

“…The gas-phase reactions were taken from the UMIST database (McElroy et al 2013), which includes the original network for phosphorus of Millar (1991). This network is based on the early experimental work of Thorne et al (1983Thorne et al ( , 1984 and Smith et al (1989), and only ∼30% of the reactions have rate coefficients measured in the laboratory. We have also added the chemical reactions involving PH 3 from the chemical network of Charnley & Millar (1994), who took the rate coefficients of the neutral-neutral reactions H + PH n (n=1-3) from Kaye & Strobel (1983) following the experimental data of Lee et al (1976).…”