Triphenylphosphine (PPh3) was treated with concd. H2SO4 at 20degreesC and sulfonated 20 h/15degreesC with a 65% SO3 oleum under N-2. The resulting sulfonic acids were extd. into tributyl phosphate and hydrolyzed and neutralized with aq. 40% NaOH at 25degreesC. In 4 h, the sediment was filtered, washed with ice-water, dried 35degreesC, boiled in H2O, and cooled to ppt. and dry (100 Torr) di-Na salt of phenyidi(m-sulfophenyl)phosphine. The hydrolysis and neutralization filtrate evapd. to dryness (< 75degreesC), heated in EtOH to 80degreesC, and filtered, was evapd. and cooled to ppt. tri-Na salt of tri(m-sulfophenyl)phosphine. Optimum SO3/PPh3 mole ratios were 10 and 15, providing partition coeffs. 27.1 and 30, resp., and highest salt yields and purities; the best sulfonation time was 20 h. Salt structures were checked by FTIR and C-13 NMR.