REPORT 

SANITIZED 

DETERMINATION OF THE WATER SOLUBILITY OF 

1,1,3,3-TETRAMETHYLBUTYL PEROXYPIVALATE 

.-.--____ 

NOTOX Projec

~ ) NOTOX Substan , - ·· 

· Page 1 of 13 · 
sponsor. 

• Page 2 -
The study described in this report has been correctly reported and was conducted in compliance with the most recent edition of: 

The OECD Principles of Good Laboratory Practice 

which are essentially in conformity with: 

The United States Food and Drug Administration. Title 21 Code of Federal 

Regulations Part 58. 

The United States Environmental Protection Agency (FIFRA). Title 40 Code of Federal Regulations Part 160. 

The United States Environmental Protection Agency (TSCA). Title 40 Code of Federal Regulations Part 792. 

Study Director 

Ir. M.J.C. Brekelmans 

(~·;;·~~, 

Management 

J.A.M.W. van Helvoirt 

(i'!ea!I"Of-Gil~y 

.. 

"""'\ 

Date: 

Page 3 
( 

This report was audited by the NOTOX Quality Assurance Unit to ensure that the methods and results accurately reflect the raw data. 

The dates of Quality Assurance inspections and audits are given below. During the on-site inspections procedures applicable to this type of study 

were inspected. 

DATES OF QAU INSPECTIONS/AUDITS 

on-site inspection (s) 

15 July 1997 

protocol inspection (s) 

22 May 1997 

report audit (s) 

26 August 1997 

Head of Quality Assurance 

C.J. Mitchell B.Sc. 

··-------

· Page 4 

REPORTING DATES 

15 July 1997 

22 May 1997 

26 August 1997 
Adopted July 27, 1995. 

EEC Directive 92/69 EEC, Part A, Methods for the determination of physico· chemical properties, A.6: "Water solubility'. EEC Publication no. L383, 

December 1992. 

Since 1,1,3,3-TETRAMETHYLBUTYL PEROXYPIVALATE is a liquid, the column elution method is not applicable, Therefore, the flask method was used for the determination of the water solubility of 1,1,3,3-TETRAMETHYLBUTYL PEROXYPIVALATE. 

The water solubility of 1,1,3,3-TETRAMETHYLBUTYL PEROXYPIVALATE at 19.5 ± 

l.O'C is < 0.6 mg/1. 

· Page 5 · 
Study Monitor 

Testing Facility 

Study Director 

Study plan 

TEST SUBSTANCE 

Identification 

Chemical name 

CAS No. 

Description 

Batch 

Purity 

Test substance storage 

Stability under storage 

conditions 

Expiry date 

~ 

(_ . ) ------'"'"""--------

NOTOX B.V. 

Hambakenwetering 3 

5231 DD 's-Hertogenbosch 

The Netherlands 

c 

____________ 

---_) 

Start: 01 July 1997 

Completed: 15 August 1997 

1,1,3,3-TETRAMETHYLBUTYL PEROXYPlVALATE 

Propaneperoxic acid, 2,2-dimethyl-,1,1,3,3-

tetramethylbutyl ester (9CI) 22288-41-4 

<nJourless liquid re-e-GepH·rtcafe of Analysis In freezer in the dark 

Stable 

Not indicated 

The sponsor is responsible for the completeness and GLP Compliance of all 

test substance data. 

PURPOSE AND PRINCIPLE 

The purpose of the study was to evaluate the solubility of the test substance in water. 

To determine the water solubility of the test substance, two different methods can be used : 

The column elution method for solubilities< 10·• g/1. 

- The flask method for solubilities~ 10- 2 g/1. 

Page 6 -
Organization for Economic Co

operation and Development (OECD}, OECD 

guideline for testing of chemicals no. 105: 'Water Solubility', Adopted 

July 27, 1995. 

European Economic Community (EEC), EEC-Directive 92/69 EEC, Part A, 

Methods for the determination of physico-chemical properties, A.6: 'Water 

solubility'. EEC Publication no. L383, December 1992. 

ARCHIVING 

NOTOX B.V. will archive the following data for at least 10 years: 

protocol, report, test substance reference sample and raw data. 

TEST SYSTEM AND RATIONALE 

Double distilled water. 

The test system is recognized by the international guidelines (EEC, OECD). 

VALIDATION OF THE TEST PROCEDURE 

The test method as outlined in this report is validated periodically, 

using 4-nitrophenol and 2,4-dichlorophenoxyacetic acid alternately. The results are in accordance with the criteria of OECD Guideline No.105 

"Water solubility' (1995). 

- Page 7 · 
Main study 

Since 1,1,3,3-TETRAMETHYLBUTYL PERDXYPIVALATE is a liquid, the column 

elution method is not applicable, Therefore, the flask method was used for 

the determination of the water solubility of 1,1,3,3-TETRAMETHYLBUTYL 

PEROXYPIVALATE. 

Approximately 440 mg (i.e approximately 0.5 ml) of the test substance was weighed into each of three Erlenmeyer flasks. To each flask, 100 ml double distilled water was added. The flasks were securely closed and placed on a 

magnetic stirring device. The content of each flask was stirred for 24, 48 

or 72 hours at 19.5 ± 1.0'C. 

Preparation of a blank: 

100 ml double distilled water was stirred for 72 hours at 19.5 ± 1.0'C. 

The blank solution was pretreated and analysed identically as the water 

samples from the main study. 

pH measurements: 

Each clear water sample from the main study was diluted in a 9:1 (v/v) 

ratio with a 0.1 M NaC1 solution, prior to pH measurement. 

- Page 8 
than water. Samples of the water phase were taken using a volume pipette. 

To avoid contamination, the outside part of the volume pipette which came 

in contact with the sample, was dried thoroughly before emptying the 

pipette in the centrifugation tube. 

Sample pretreatment preliminary test 

5 ml was taken from the water phase and centrifuged (5 min, 3500 g, 20°C). 

Then, 2.5 ml was taken from the centrifuged water phase and centrifuged a 

second time (same conditions). Thereafter 1.0 ml was taken and this water 

sample was centrifuged a third time (same conditions). The two and three 

times centrifuged water samples were analysed undiluted. 

Sample pretreatment main study 

From each Erlenmeyer flask, duplicate samples were taken and centrifuged 

five successive times at 41700 g and 20°C for 5 minutes. The five times 

centrifuged water samples were diluted by a factor 2 with acetonitrile prior to analysis. 

Analytical method 

Column 

Mobile phase 

Flow 

Detection 

Injection volume 

Calibration solutions 

LiChrospher 100 RP-8, 125 x 4 (I.D.) mm; 

d =5 ~m (Merck, Darmstadt, Germany) 

68/40 {v/v) acetonitrile (HPLC-grade, Labscan 

Limited Co., Dublin, Ireland)/Milli·Q water 

(Mi1lipore Corp., Bedford, MA, USA) 

1 ml/min 

UV at !..= 205 nm 

100 ~1 From two stock solutions with concentrations between 0.8 and 1.1 g/1 of 

1,1,3,3-TETRAMETHYLBUTYL PEROXYPIVALATE in acetonitrile, dilutions in 

mobile phase were prepared for calibration purposes. 

· Page 9 . 
n 1=1 

2. Maximum deviation: [(highest value - lowest value)/mean] x 100% 

3. Limit of detection: 

The limit of detection is defined as the absolute amount of 1,1,3,3· 

TETRAMETHYLBUTYL PEROXYPIVALATE at which the peak height is three 

times the noise level (ratio signal to noise is three (SIN=3)). Based 

on the noise and signal measurement, the limit of detection was 

calculated. 

Calibration 

1. In the chromatogram of the standard solution, one small peak and one large peak were observed. From information supplied by the sponsor, it 

was understood that the large peak derives from the major component of 1,1,3,3-TETRAMETHYLBUTYL PEROXYPIVALATE whereas the small peak derives 

from an impurity in the test substance. Quantitative analyses were 

based on the largest peak in the HPLC chromatogram of 1,1,3,3-

TETRAMETHYLBUTYL PEROXYPIVALATE. 

2. 

Response: R = Peak area test substance [units] 

Response factor: RF = 

R 

c 

[units • 1/mg] 

R response calibration solution [units] C concentration of test substance in calibration solution 

[mg/1] 

For the measurements of the preliminary test, the mean RF was 

calculated from 4 RF values. 

2. Calibration curve: 

The response was correlated with the concentration test substance, using linear regression analysis (least squares 

method). 

R = a • C + b 

R response calibration solution [units] C = concentration of test substance in calibration solution 

[mg/1] 

a slope [units'l/mg] 

b = intercept [units] 

For the measurements of the main study, a calibration curve was 

constructed from six data points. 

· Page 10 
or 

RF 

(R·b) • d 

c; ·········--·--· (mg/1] 

a 

R ; response sample (units] d ~ dilution factor 

Rf; mean response factor calibration solutions 

[units'l/mg] 

a ; slope [units'l/mg] 

b = intercept (units] 

2. The water solubility of a test substance is specified by the saturation mass concentration of the test substance in water at a given temperature and is expressed in g/1. 

3. Because the water solubility of 1,1,3,3-TETRAMETHYLBUTYL PEROXYPIVALATE was< 100 g/1, no correction for the mass fraction of the test substance in the water phase was made. 

Page 11 
was determined to be 8 mg/1. Because the test substance is a colourless 

liquid, there were some doubts if all undissolved test substance was 

separated from the water phase. Therefore, it was decided to regard the 

centrifugation steps critically during the main study. A higher relative 

centr1fuga1 field was chosen (S min, 41700 g) for each centrifugation 

step during the main study and centrifugation was repeated until the test 

substance concentration in the water samples had become stable. 

Main study 

Since 1,1,3,3·TETRAMETHYLBUTYL PEROXYPIVALATE is a liquid, the column 

elution method is not applicable, Therefore, the flask method was used for the determination of the water solubility of 1,1,3,3-TETRAMETHYLBUTYL 

PEROXYPIVALATE. 

The calibration curve (0.25 · 1.49 mg/1; six concentrations) had a 

correlation coefficient of 0.991 and a relative standard deviation in 

response of 8.5%. Each calibration solution was measured in duplicate. 

For calibration solutions 0.50 mg/1, the deviation between the two 

responses was between 6 and 18% while the deviation between the two responses was 48% for the 0.25 mg/1 calibration solution. Duplicate 

analyses of the pretreated water samples showed deviations in response between 24 and 200%. Based on all these results, it was concluded that 

the method of chemical analysis is not satisfactory at this low 

concentration level. 

Considering the responses of the pretreated water samples, it was found 

that these were all below the responses of the 0.25 mg/1 calibration solution. The signal to noise ratio was< 3 in the chromatograms of the 

0.25 mgll calibration solution, i.e below the limit of detection. 

Therefore it was concluded that the test substance concentrations in the 

pretreated water samples were all below the limit of detection. 

The limit of detection was determined from two chromatograms of the 

0.50 mg/1 calibration solution. The noise level (mean height) was determined to be 4 mm (attenuation of the integration unit:2). In the 

same chromatograms, the mean peak height of the test substance peak was 

21 mm. Therefore, the limit of detection was determined to be 0.3 mg/1 at 

an injection volume of 100 (i.e. 31 ng absolute). Because the water 

samples were diluted by a factor two, the water solubility was calculated 

to be< 0.6 mg/1. 

The pH of the water samples from the main study were determined to be 

· > 

In conclusion, 

---

the water solubility of 1,1,3,3-TETRAMETHYLBUTYL 

PEROXYPIVALATE at 19.5 ± 1.0"C is < 0.6 mg/1. 

Page 12 
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