3766 © 1982 The Chemical Society of Japan Ball. Chem. Soc. Jin 58, 5766—5769 (1982) [Vol. 55, No. 12 The Mechanism of the Hydrolysis of Polyphosphates. VI.” The Effect of Cations on the Hydrolysis of cyclo-Tri- and cyelo-Tetraphosphates Makoto WATANABE Department of Industrial Chemisty, Chubu Institute of Technalogy, Motsamotocho, Kasugei, Aichi 487 (Recs red April 30, 1982) ‘The effect of cations on the rate of the hydrolysis of gelo-tri- and cyla-tetraphosphates was studied by adding ‘metal chlorides to aqueous solutions of the ring phosphates. The concentrations of the phosphates and metal chlorides were 0.025 mol dm-? and 0.1 mol dm-® respectively. ‘of both the elo-phosphates in acidic media and accelerated it in basic media. resulted: ‘Alkalimetal cations retarded the hydrolysis ‘The following sequence of efficiency Lit >Nat >K*. Magnesium, calcium, and nickel(II) cations retarded the hydrolysis of the gelo-phosphates in the pH range of 1.02.0 or 1.02.7, while they accelerated it inthe pH regions higher than 2.7 or 3.5. A copper(II) retarded, the hydrolysis at pH 1.0, and accelerated it in the pH ranges higher than 2.0. An aluminium ion highly accelerated the hydrolysis of both the ring phosphates at pH 1.0 and 2.0, ‘Though many papers concerning the hydrolysis of polyphosphates have been reported, there have been few reports about the effect of metal cations on the hydrolysis. Thilo and Wieker studied the catalytic efficiencies of cations on the hydrolysis of high polyphos- phates at pH 8 and obtained the following sequence of efficiency: ‘ABS Mgt Sats Sct DL DNat SK. Osterheld recently presented a review on the hydrolysis of condensed phosphates.® The present author has reported the reaction mechanism of the hydrolysis of chain and small-ring polyphosphates from the point of view of the interaction between a water molecule and a polyphosphate ion by using aqueous organic solvents.*-" Ina previous paper, the effect of metal cations on the hydrolysis of di- and triphosphates was reported. This paper describes the effect of metal cations on the hydrolysis of oyelo-tri- and elo-tetraphosphates. Ba SH Experimental Materials and Procedure. All the materials other than sodium gelo-tri- and gelo-tetraphosphates were commercial grade. Sodium oelo-tri- and gylo-tetraphosphates were produced by the method described in Refs. 10 and 11. The initial concentration of sodium gxlo-tri- and gela-tetrapho phates was 0.025 mol dm-%. ‘This concentration is suitable for analysis. oclo-Tri- and olo-tetraphosphate solutions free from sodium ions were prepared by passing the sodium clo- phosphate solutions mentioned above through cation-exchange resin in the H’ form. The olo-phosphate solutions without sodium ions were used to study the effect of alkali-metal cations on the rate of the hydrolysis of the elo-phosphates in ‘both acidic and basic media. These gylo-phosphate solutions ‘could not be used to investigate the effect of alkaline-carth, aluminium and some transition-metal cations over a wide pH range of the solution, because precipitates were formed. So the sodium gelo-phosphate solutions were used to test the effect of these cations on the rate of the hydrolysis ofthe cylo- phosphates. Metal chloride was added to the phosphate solutions to make it 0.1 moldm”*. ‘The metal chlorides used were LiCl, NaCl, KCl, MgGk, CaCh, AIC, NiGl, and CuCh, The pHs of the gelophosphate solutions containing cone of the cations mentioned above were controlled with hrydrochlorie seid. and/or aqueous. teramethylammonium hydroxide by using Hitachi-Horiba pH meter, F-7, at a given reaction temperature. The pH of the solution wat Periodically measured and if it was in need of adjustment, enough tetramethylammonium hydroxide or hydrochloric cid was added to bring it back to the proper pH. The pH Adjustment was made within 20.1 pH unit of the required Walue. At measured intervals of time, about a I-em* portion of the jlo-phosphate solution was withdrawn, About 50 mg of disodium dihydrogen ethylenediaminetetraacetate dihydrate (EDTA) was added to the phosphate solution containing a etal cation, and then the pH ofthe solution was adjusted to 17-9 with aqueous ammonia or hydrochloric acid and 8 mm of the solution wa spotted on Toyo No. SIA filter paper (2 by 50cm) for the separation of the phosphates in the solution, ‘When the gelo-phosphate solution did not contain any metal jon, the pH ofthe withdrawn I-cm? portion ofthe phosphate solution was adjusted to about 7 with aqueous ammonia or hhydrochlorie aid, ‘The separation ofthe phosphate species in the solution was made by spotting 8 mim ofthe solution on the filter paper mentioned above. The separation and determin tion ofthe phorphates in the sample solution were carried out by the method described in previous papers." When some precipitate was formed during the hydrolytic process ofthe gelo-phosphates, no further treatment was made, Results and Discussion The Effect of Cations. ‘The rate of the hydrolysis of gclo-tri- and gjlo-tetraphosphates obeyed first-order netics with respect to the concentration of the respec- tive gelo-phosphates under all the conditions studied. ‘The hydrolysis of sodium gelo-tri- and clo-tetraphos- phates is an acid- and base-catalyzed reaction.” As Tables 1 and 2 show, the hydrolysis of cylo-tri- and ‘elo-tetraphosphates in an aqueous solution containing alkali-metal cations or in a solution free from metal cations gave the result mentioned above. The rate of the hydrolysis of the gclo-phosphates in a solution containing Mgt, Cat, or Nit decreased with an increase in the pH of the solution from 1.0 to 2.7 or 3.5, while the rate of the hydrolysis of gclo-triphosphate containing Mg** and of gclo-tetraphosphate containingDecember, 1982] Tanue I. Rave consrants/min-! op rite LHYDROLYSWOF cyelo-TRIPHOSPHATE Sn Reaction temp Hydrolysis of Small-ting Phosphates 3767 ‘Taste 2. 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An aluminium ion extremely acceler- (20 g.02% 10" ated the rate of the hydrolysis of the crlo-phosphates at 'Nit+ increased with an increase in the pH of the solution from 3.5 to 5.0. The rate of the hydrolysis of the ‘gelo-phosphates in a solution containing Cu** decreased as the pH of the solution changed from 1.0 to 2.0. On the other hand, the rate increased as the pH of the solution increased from 2.0 to 27 and 3.5. In the ‘case of the hydrolysis of the ring phosphates in a solution containing Al", the rate of the hydrolysis of the cylo- phosphates increased with an increase in the pH of the solution from 1.0 to 2.0. For the hydrolysis of the short-chain polyphosphates, these cations used here all retarded the rate of the hydrolysis of the polyphosphates in acidic media and alkali-metal ions accelerated the rate in basic media. This tendency is the same as that of the hydrolysis of the ring phosphates in a solution containing alkali-metal ions. Magnesium, calcium, and nickel ions retarded the rate of the hydrolysis of the elo-phosphates in the pH region of 1.0—2.0 or 1.0— 2.7, while they seemed to accelerate the rate in the pH regions higher than 2.7 or 3.5. The rate was retarded by Gut at pH 1.0, while it was accelerated at a pH region pH 1.0 and 2.0. The acceleration of the rate of the hydrolysis by metal cations was not observed for the hydrolysis of di- and triphosphates in acidic media. Reaction Mechanism, ‘The activation parameters for the hydrolysis of yclo-tri- and cjlo-tetraphosphates were calculated by means of an Arrhenius plot and are listed in Tables 3 and 4 respectively. In the case of the hydrolysis of both the gelo-phosphates in a solution containing an alkali-metal ion or in a solution free from a metal ion, the activation energy increased with ‘an increase in the pH of the solution. ‘The activation ‘energy also seemed to increase by addition of an alkali- ‘metal ion into the phosphate solution. In previous papers,*- the author proposed the following hydrolysis mechanism for chain and small-ring phosphates and concluded that Reaction 2 is the rate-determining step:3768 Makoto Waravane [Wol. 55, No. 12 ‘Taaus 3, AcrIvATION PARAMETERS OF THE Tans 4, ACTIVATION PARAMETERS OF THE NYDROLYEI OF clo-rIPHORPHATE HYDROLYIE OF ofla-TETRAPHORPHATE Added ‘Activation __log (Feque ‘Raded “Katvation log (Requen Phosphate Qt PH item! faery” Phosphate Qn PH Shersy mol) factor) jie a 12.2 jie mo 13.1 — 20 m0 7 = fro 93 m4 ins 110.4 13.6 ins 118.3 13.3 jroo 27 Lo 992 83 Jue [po a ie Li {ze 100.3 22 ns u99 15.8 579 15.9 otro | jig Bo 23 ee Lo 98. 13.2 xe [20 0 ns Net {2 3 ei (ins 110.5 14.0 ns 125.4 15.1 pho ara 23 Lo 979 13.2 Gr Palo on 120 lx {20 100.2 22 Lins 109.9 13.9 1s 126.7 15.2 (to a8 m1 Lo 972 29 | 20 6 6 — feo toss 2.9 } 27 7 1 j27 15.9 4 [23 3 6 [35 07.6 119 15 8 7 fio 89.2 oe ° ° 1 MS 20 89.8 96 {xo 5 pio 13 [2 9 (NaPODAs yee | 2D 95.5 10.7 5 6 27 105.0 18 : ‘ eee { ‘0 7 to ‘nt ns 7 9 cu | 2! 973 22 ° 8 2:7 100.9 28 ee SU ome [27 (20 93.3 132 5 Asia media could be attributable to the exchange of a ite hydrogen ion with a catalytically les effective alkali a metal ion as follows: @ @ ® ‘As mentioned above, the effect of alkali-metal ions on the kinetics parameters and the order of the efficiency of alkali-metal ions for the hydrolysis of both the ring phosphates was the same as that of the hydrolysis of di- and triphosphates. So the same reaction mechanism described in a previous paper!’ may be applicable for the hydrolysis of the gelo-phosphates, and the reta tion of the hydrolysis rate by alkali-metal ions in acidic H M ° ° obob im — borobsm. 6) é é i " ‘The acceleration of the rate by alkali-metal ions in basic, media could be explained by the formation of the complex as follows: M 2 Re -obo-42m — obo. m Q w ‘As Tables 3 and 4 show, this acceleration is exclusively dependent on the entropy term. The retardaction of the rate of the hydrolysis of ojlo-tri- and oyelo-tetraphos- phates by Mg?*, Ca¥, Nit*, and Cu* in highly acidic media depended exclusively upon the entropy term. So, when the exchange of a hydrogen ion with a cataly- tically less effective Mg ion takes place according to Reaction 5, it could be concluded that there is a difference between the structures of the complexes of an alkali-metal ion and of an Mg’, Ca**, Nit*, or Cutt ion. The acceleration of the hydrolysis of the glo- phosphates by Cu** and Al** in acidic media depended