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Environmental fate & pathways

Hydrolysis

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Description of key information

Hydrolysis: half-life <0.1 h at pH 4 and 20°C, 23 h at pH 7 and 25°C, 0.8 h at pH 9 and 25°C (OECD 111)

Key value for chemical safety assessment

Half-life for hydrolysis:
23 h
at the temperature of:
25 °C

Additional information

Measured half-life values of <0.1 h at pH 4 and 20°C, 23 h at pH 7 and 25°C, and 0.8 h at pH 9 and 25°C were determined for the substance in accordance with OECD 111. The study is considered to be reliable and has been assigned as key study.

As the hydrolysis reaction may be acid or base catalysed, the rate of reaction is expected to be slowest at pH 7 and increase as the pH is raised or lowered. For an acid-base catalysed reaction in buffered solution, the measured rate constant is a linear combination of terms describing contributions from the uncatalyzed reaction as well as catalysis by hydronium, hydroxide, and general acids or bases.

kobs= k0+ kH3O+[H3O+] + kOH-[OH-] + ka[acid] + kb[base]

 

At extremes of pH and under standard hydrolysis test conditions, it is reasonable to suggest that the rate of hydrolysis is dominated by either the hydronium or hydroxide catalysed mechanism. This is supported by studies for various organosilicon compounds in which calculation of kH3O+and kOH-from the experimental results at pH 4 and 9, respectively, resulted in reasonable estimates of the half-life at pH 7 (REFERENCES NEEDED).

 

Therefore, at low pH:

kobs≈kH3O+[H3O+]

 

At pH 4 [H3O+]=10-4mol dm-3 and at pH 2 [H3O+]=10-2mol dm-3; therefore, kobs at pH 2 should be approximately 100 times greater than kobs at pH 4.

 

The half-life of a substance at pH 2 is calculated based on:

t1/2(pH 2) = t1/2(pH 4) / 100

The calculated half-life of triethoxy(3-thiocyanatopropyl)silane at pH 2 is therefore 0.001 hours (3.6 seconds). However, it is likely that factors such as diffusion become rate-determining when the half-life is less than 5-10 seconds. As a worst-case it can therefore be considered that the half-life of the substance at pH 2 and 20-25°C is approximately 5 seconds. Reaction rate increases with temperature therefore hydrolysis will be faster at physiologically relevant temperatures compared to standard laboratory conditions. Under ideal conditions, hydrolysis rate can be recalculated according to the equation:

DT50(XºC) = DT50(T) x e(0.08.(T-X))

Where T = temperature for which data are available and X = target temperature.

Thus, for triethoxy(3-thiocyanatopropyl)silane the hydrolysis half-life at 37.5ºC and pH 7 (relevant for lungs and blood) is 8.5 hours. At 37.5ºC and pH 2 (relevant for conditions in the stomach following oral exposure), it is not appropriate to apply any further correction for temperature to the limit value and the hydrolysis half -life is therefore approximately 5 seconds.

The products of hydrolysis are (3-thiocyanatopropyl)silanetriol and ethanol.