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Issue 2, 1995
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Phosphorus-31 NMR investigation of the heterogeneous hydrolytic decomposition of zinc(II) bis(O,O-dialkyl dithiophosphate) lubricant additives

Alan J. Burn,  Ian Gosney,  Chris P. Warrens  and  John P. Wastle 

Abstract

31 P NMR spectroscopy has been used to investigate the heterogeneous-phase hydrolysis of zinc(II) bis(O,O-dialkyl dithiophosphates)(ZnDTP), Zn[S2P(OR)2]21 where R = 2-propyl 1a, 2-butyl 1b, 4-methyl-2-pentyl 1c and 2-ethylhexyl 1d in a 1:1 mixture of heptane–p-xylene to which a tenfold excess of water (relative to ZnDTP) was added. In each case, the process leads to endproducts identical to those previously found for homogeneous-phase hydrolysis, viz. thiophosphoric acid 4, phosphoric acid 5 and alkyl dihydrogen phosphate 8. All hydrolyses are found to follow firstorder kinetics and the calculated relative rates of hydrolytic breakdown (kHET= 4.16–0.66 × 10–5 s–1) show a significant decrease as the size of alkyl group increases. This is attributed to the ratelimiting step for hydrolysis being the diffusion of the ZnDTP across the solvent–water interface.

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Article type: Paper
DOI: 10.1039/P29950000265
Citation: J. Chem. Soc., Perkin Trans. 2, 1995,0, 265-268
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    Phosphorus-31 NMR investigation of the heterogeneous hydrolytic decomposition of zinc(II) bis(O,O-dialkyl dithiophosphate) lubricant additives

    A. J. Burn, I. Gosney, C. P. Warrens and J. P. Wastle, J. Chem. Soc., Perkin Trans. 2, 1995, 0, 265
    DOI: 10.1039/P29950000265

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