• Textile Coloration and Finishing
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• v.6 no.1
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• pp.33-43
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• 1994

In the present work, to clarify the mechanism of the neutral salt effect on the alkaline hydrolysis of PET, many salts with different cations like LiCl, NaCl, KCl, CsCl were added to the aqueous alkaline solutions. Then PET was hydrolyzed with aqueous solutions of many salts in alkali metal hydroxides under various conditions. Some conclusions obtained from the experimental results were summarized as follows. The reaction rate of the alkaline hydrolysis of PET was increased by the addition of neutral salts and In k was increased nearly linearly with the square root of ionic strength of reaction medium. This fact suggested that the ionic strength effect by Debye-Huckel and Bronsted theory was exerted on the reaction. The specific salt effect was also observed. The reaction rate was increased with the increase in the electrophilicity of cations of neutral salts, i. e., in the order of $Cs^+$/ < $K^+$/ $a^+$/ $i^$^+$. It was considered that the reaction rate was increased in the order of C $s^+$. < $K^+$. $a^+$. $i^+$. because the lowering effect of the cations on the negative charge of PET surface was increased with the electrophilicity of cations. It was thought that $E_{a}$ was increased because the cations of neutral salts decreased the negative charge of PET surface. It, however, was inferred from the increase in ${\Delta}$S＊ and the decrease in the ${\Delta}$G＊ that the cations of neutral salts associated with PET increased the collision frequency between carbonyl carbon and OH- ion and then accelerated the reaction rate.te.

• Textile Coloration and Finishing
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• v.7 no.4
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• pp.61-73
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• 1995

Inorganic salts have negative or positive effects on the rates of many chemical reactions and also the rates of acidic and alkaline hydrolysis of carboxylic esters. The direction of salt effects on the hydrolysis of ester depends on the charge of esters. It is expected that the rate of the alkaline hydrolysis of Poly(ethylene terephthalte)(PET), polymeric solid carboxytic polyester with carboxyl end group at the polymer end, is also influenced by inorganic salts. In the present work, to clarify the effect of divalent cations on the alkaline hydrolysis of PET, many salts with divalent cations like $MgCl_{2},CaCl_{2},SrCl_{2},BaCl_{2},$ were added to the aqueous alkaline solutions. Then PET was hydrolyzed with aqueous NaOH solution having many salts under various conditions. Some conclusions obtained from the experimental results were summarized as follows. Many salts with various divalent cations increased or decreased the reaction rate of alkaline hydrolysis of PET depending on their electrophilicity, hydration property, ability of ion pair formation, solubility, and the degree of interactions between divalent cations and anions, etc. The hydrolysis was interrupted in the order of $Ca^{+2} and was generally accelerated in the order of $Ba^{+2}. It was inferred from the increase in ΔS$^*$and the decrease in the ΔG$^*$that the divalent cations $Sr^{+2}$ and $Ba^{+2}$attracted by PET increased the collision frequency between carbonyl carbon and $OH^{-}$ion and then accelerated the reaction rate. $Mg^{+2}$and $Ca^{+2}$decreased the reaction rate because of their strong interaction with $OH^{-}$.

• Textile Coloration and Finishing
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• v.6 no.2
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• pp.10-16
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• 1994

Neutral salts have negative or positive effects on the rates of many chemical reactions and also on the rates of acidic and alkaline hydrolysis of carboxylic esters. The direction of neutral salt effects on the hydrolysis of ester depends on the charge of esters. Neutral salts accelerate alkaline hydrolysis of esters with negative charge, but decelerate alkaline hydrolysis of esters with positive charge, and have little effect on the alkaline hydrolysis of neutral esters. It is expected that the rate of the alkaline hydrolysis of Poly(ethylene terephthalte) (PET), polymeric solid carboxylic polyester with carboxyl end group at the polymer end, is also influenced positively by neutral salts. In the present work, to clarify the mechanism of the neutral salt effect on the alkaline hydrolysis of PET, many salts with different anions like NaF, NACl, NaBr, NaI were added to the aqueous alkaline solutions. Then PET was hydrolyzed with aqueous solutions of many salts in alkali metal hydroxides under various conditions. Some conclusions obtained from the experimental results were summarized as follows. The reaction rate of the alkaline hydrolysis of PET was increased by the addition of neutral salts and In k was increased nearly linearly with the square root of ionic strength of reaction medium. This fact suggested that the ionic strength effect by Debye-Huckel and Bronsted theory was exerted on the reaction. The specific salt effect was also observed. The reaction rate was increased with the decrease in the nucleophilicity of anions of neutral salts, i.e., in the order of $F^-$ <$Cl^-$<$Br^-$<$I^-$. It was thought that the reaction rate was increased in the order of $F^-$ <$Cl^-$<$Br^-$<$I^-$. because the completion of anions with $OH^-$ for carbonyl carbon became weaker with the decrease in the nucleophilicity and with the increase in the size of anions.