### DISCLAIMER This report is the property of Clariant. Its content is confidential and not for general release. It is not allowed to cite and reveal the report or its content to a third party without prior written approval of Clariant. 

## REPORT
Leuco Sulfur Black 1 Determination of the Boiling Point /Boiling Range 

# harlanTM


# ...

Data Requirements I 

### Test Guidelines: EEC Directive 92/69, A.2, December 1992 OECD No. 103, July 1995



### Study Director:
Test Facility:

Sponsor:

Study Identification: Version: Study Completion Date: Council Regulation (EC) No. 440/2008, A.2

Dr Jens Franke 

### Harlan Laboratories Ltd. Zelgliweg 1 4452 Itingen 

### I Switzerland



### Clariant Products (Switzerland) Ltd. Rothausstrasse 61 4132 Muttenz I/ Switzerland
Harlan Laboratories Study 

### C30931
Final February 24, 2009 Page 1 of 18



## 188 ON SNIV1N08 

# p**~** 6J;)_7/ ).=<_Harlan Laboratories Study C30931 Leuco Sulfur Black 1


## CONTENTS Report Page2



### CONTENTS
.................................................................................................................................... 2 LIST OF TABLES
.......................................................................................................................... 2 LIST OF FIGURES
......................................................................................................................... 

### 2 GLP CERTIFICATE
....................................................................................................................... 3 SIGNATURES
................................................................................................................................ 

### 4 STATEMENT OF COMPLIANCE
................................................................................................ 

### 5 QUALITY ASSURANCE GLP STATEMENT
............................................................................. 6 PREFACE
....................................................................................................................................... 7 General Information
............................................................................................................... 7 Responsibilities
...................................................................................................................... 7 Schedule
................................................................................................................................. 7 Data Requirements 

### I Test Guidelines
.................................................................................... 8 

### Archiving
............................................................................................................................... 8 

### Summary of Study Plan Amendments
................................................................................... 8 

### 1 SUMMARY
........................................................................................................................... 9 2 PURPOSE
..... : ...................................................................................................................... 10 3 MATERIALS AND METHODS
......................................................................................... 11 3.1 Test Item
................................................................................................................ ll 3.2 Test System
............................................................................................................ 11 3.3 Principle of the Test
............................................................................................... 11 3.4 Performance of the Test
......................................................................................... 12 3.4.1 Test System
............................................................................................. 12 3.4.2 Preliminary Test
...................................................................................... 12 3.4.3 Main Test
................................................................................................. 12 3.5 Data Handling
........................................................................................................ 13 4 RESULTS AND DISCUSSION
.......................................................................................... 14 4.1 Preliminary Test
.................................................................................................... 14 4.2 Main Test
............................................................................................................... 14 5 CONCLUSION
.................................................................................................................... 15 6 TABLES
.............................................................................................................................. 16 7 FIGURES
............................................................................................................................. 17 

## LIST OF TABLES Table 1 Determination ofthe Boiling Point ofLeuco Sulfur Black 1 (Summary)
.................. 16 

## LIST OF FIGURES Figure 1 DSC-curve of Leuco Sulfur Black 1 (Preliminary Test)
............................................ 17 Figure 2 DSC-curve ofLeuco Sulfur Black 1 

### (1st Main Test)
.................................................. 

### 18

t. \ •. '•.\ Harlan Laboratories Study C30931 Leuco Sulfur Black I 

## GLP CERTIFICATE

..... 5chwelretisc:he EidgtftOssenschlft V Conf6diltatloo sul111 ConfedHIZIOnt Svii'Zifl Conftdernlun IYizra Swlu CDnftderatlon Report

fedt11l Deptrtment of Home Affairs DHA

- Ollbof

..... _POPII Fedtfll DoptrlmtM of tilt I<Mtonmenl. Tronspotl. Enerp and CommuniCitlorll OETEC 

# ---

.... 

# ·--**~** d" SWlSSme lC 

# Statement of GLP Compliance According to Article 14 paragraph 3 Ordinance on Good Laboratoly Practice (OGLP, SR 813.112.1] The notification authority for chemicals confirms that the foHowing test facility was inspected with respect to the compliance with the SWiss Ordinance on Good Laboratory PractiCe, adopted on 18th May 2005 (OGLP, SR 813.112.1). This Ordinance is baaed on the OECD Principles of Good Laboratory Practice, as revised In 1997 and adopted on 26th November 1997 by decision of the OECD Council [C(97)1861Finaq.
Unequivocal name and address of the test facility: Areas of expertise according to article 3 paragraph 1 letter d OGI..P: Harlan Laboratories Ltd. lelglweg 1**44521tingen,~erland.** 1 J Physical-chemical testing, 2J Toxicity studies, 4.1 Environmental toxicity studies on aquatic and terrestrial organisms, 5J Studies on behaviour In water, soil and air; bloaocumulation, 6.1 Residue studies, 1.1 Studies on etrects on mesocosms and natural ecosystems, 8J Analytical and clinical chemistry testing, 9.1 Other studies (safely pharmacology and anlmel melabollam). Inspection authority: Federal Office for the Environment (FOEN) I Federal Office of PubUc Health (FOPH) I Swiss Agency for Therapeutic Producls (SwissmecfiC) Date of inspection: 05th to D9th and 26th to 30th Novamber 2007 Date of decision: 30th Aprft 2008
Based on the above mentioned decision It can be confirmed that the above mentioned last facUlty Is able to conduct studies acc:ordlng to the aforementioned areas of expertise In compliance with the principles of GLP. The above mentioned test facility Is listed In the register and GLP 1st according to the Article 14 OGLP and is inspected on a regular basis according lo Article 6 paragraph 2 OGLP. Swiss Fed8f1!1.011ice of Public Health Consumer P.fO(ectlon directorate



## ,. __ .. __ .... _..,_....., .... _ _...,_,CIU'JIOr

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__ or ____ .., ___ _ •• .,.. • .,_ . ...,••mnoa.r.t...,(CI!1IZIICM Page 3Harlan Laboratories Study C30931 Leuco Sulfur Black 1 

## SIGNATURES

Study Director:

Management: Report Page4

Dr Jens Franke

### ~ Dr Jom Schreitmiiller

Date:**~7VotLf** Zf;-t( 

### lfl.O'\Harlan Laboratories Study C30931 Leuco Sulfur Black l


### GOOD LABORATORY PRACTICE Report



## STATEMENT OF COMPLIANCE Harlan Laboratories Study: Test Item: Study Director: C30931 Leuco Sulfur Black 1 Dr Jens Franke PageS

Study Title: Determination of the Boiling Point 

### I Boiling Range
This study has been performed in compliance with the: Swiss Ordinance relating to Good Laboratory Practice adopted May 18th, 2005 [RS 813.112.1]. This Ordinance is based on the OECD Principles of Good Laboratory Practice, as revised in 1997 and adopted on November 26th, 1997 by decision ofthe OECD Council [C (97)186/Final]. There were no circumstances that may have affected the quality or integrity of the data. Study Director: Dr Jens FrankeHarlan Laboratories Study C30931 Leuco Sulfur Black I Report Page 6 

## QUALITY ASSURANCE GLP STATEMENT Harlan Laboratories Ltd., Zelgliweg I, 4452 Itingen 

### I Switzerland
Harlan Laboratories Study: Test Item: Study Director: Study Title: C30931 Leuco Sulfur Black 1 Dr Jens Franke Detennination of the Boiling Point 

### I Boiling Range The general facilities and activities are inspected at least once a year and the results are reported to the responsible person and the management. Study procedures were periodically inspected. The study plan and this report were audited by the Quality Assurance. The dates are given below. 

### Dates of Reports to the Study Dates and Types ofQA Inspections Director and Test Facility Management December 16, 2008 Study plan December 16, 2008 January 06, 2009 Process based January 06, 2009 (Test perfonnance) February 18, 2009 Report February 18, 2009
This statement also confinns that this final report reflects the raw data. Quality Assurance: Mr Ulrich KofinkHarlan Laboratories Study C30931 Leuco Sulfur Black I


## PREFACE General Information Test Item: Study Title: Sponsor:
Study Monitor: Test Facility:
QA:



### Responsibilities Study Director: Deputy Study Director: Reporting: Technical Coordinator: HeadofQA:


### Schedule Experimental Starting Date: Experimental Completion Date: Study Completion Date: Report Page 7

Leuco Sulfur Black I Determination of the Boiling Point 

### I Boiling Range Clariant Products (Switzerland) Ltd. Rothausstrasse 6I 4132 Muttenz I 

### I Switzerland Dr Bruno 

### Kunz Harlan Laboratories Ltd. Zelgliweg 1 4452 Itingen 

### I Switzerland Harlan Laboratories Ltd. Quality Assurance GLP Zelgliweg 1 4452 Itingen 

### I Switzerland

Dr Jens Franke Ms Mirjam Weissenfeld Ms Sabine Affolter Mr Gregor Czichy Mr Tobias Fink

January 12, 2009 January 13,2009 February 24, 2009Harlan Laboratories Study C30931 Leuco Sulfur Black 1 Report



### Data Requirements I Test Guidelines Page 8



### This study followed the procedures indicated by the following internationally accepted guidelines and recommendations:

• EEC Directive 92/69, Part A, Methods for the determination of physico-chemical properties, A.2 "Boiling temperature", EEC Publication No. L383, December 1992. • OECD Guideline for Testing of Chemicals No. 103, "Boiling Point", adopted July 27, 1995. • Council Regulation (EC) No. 440/2008, 30 May 2008, Part A, Methods for the determination of physico-chemical properties, A.2 "Boiling temperature" 

### Archiving Harlan Laboratories Ltd., 4452 Itingen/Switzerland will retain the study plan, raw data, a sample of test item and the final report of the present study for at least ten years. No data will be discarded without the Sponsor's consent. 

### Summary of Study Plan Amendments There were no amendments to the study plan.Harlan Laboratories Study C30931 Leuco Sulfur Black 1


## 1 SUMMARY Report

The boiling point of Leuco Sulfur Black 1 was determined to be

which is equal to 99.9 

# oc ± 0.1 

# oc 373.1 K ± 0.1 

### K. Page 9

This result was obtained using Differential Scanning Calorimetry (Thermal Analysis) method. The atmospheric pressure during the measurements was 100.4 kPa (preliminary test) and 99.8 kPa (main tests). The boiling point of Leuco Sulfur Black 1 is influenced by its high water content. It can be assumed that the measured value corresponds to water only.Harlan Laboratories Study C30931 Leuco Sulfur Black 1 

## 2 PURPOSE Report

The purpose of the study was to evaluate the boiling point 

### I boiling range of the test item. Page 10Harlan Laboratories Study C30931 Leuco Sulfur Black I Report


## 3 MATERIALS AND METHODS 3.1 Test Item Data of test item as supplied by the Sponsor. Identification: Batch Number: Purity: Appearance: Expiry Date: Storage Conditions: 

### 3.2 Test System See detailed description in Section 3 .4.1. Leuco Sulfur Black 1 ESA0007595 45.5% Paste Liquid July 11,2011 At room temperature at about 20 

# oc Page 11



### Rationale: The test system(s) and test method(s) are recommended by international guidelines. 

### 3.3 Principle of the Test The above-mentioned guidelines contain several different methods for the determination of the boiling point 

### I boiling range. These methods include thermal analysis using a calorimeter and visual tests (e.g. capillary test). During the present study the thermal analysis was used. A phase transformation, e.g. melting or evaporation, or a reaction, e.g. dissociation, usually is associated with a heat effect. In the calorimeter, two identical aluminium sample containers, one filled with the test item and the other empty (used as a reference), are heated at a constant rate. During the experiment, the heat effect, i.e. the difference in heat flow, between the sample container and the reference container is registered.Harlan Laboratories Study C3093 I Leuco Sulfur Black I


### 3.4 Performance of the Test 3.4.1 Test System Report Page 12



### Differential Scanning Calorimeter (Preliminary Test and Main Tests) Instrument: Sample cups: Reference cup: Test conditions:


### 3.4.2 Preliminary Test Differential Scanning Calorimeter DSC 821, Mettler Toledo Aluminium cups. A lid with a defined perforation was used. Empty aluminium cup. The test was performed in an air atmosphere

A test item amount of 13.76 mg was heated up from 25 °C to 400 °C at a rate of20 °C/min. The quantities of heat absorbed or released were measured and recorded. Before and after the test, the weight and the appearance of the sample were determined.


### 3.4.3 Main Test As in the temperature range investigated, peaks were observed from which boiling of the sample could be deduced, the thermal analysis was repeated with 21.74 mg and 7.31 mg, respectively, in the immediate vicinity of the peak temperature (25 °C

- 215 °C). For the actual determination of the boiling point, the temperature rise was adjusted to 10 °C/min. Before and after the tests, the weight and the appearance of the sample were determined.Harlan Laboratories Study C30931 Leuco Sulfur Black 1


### 3.5 Data Handling Report Page 13

The standard boiling point is defined as the temperature at which the vapour pressure of a liquid is the same as the standard pressure (101.325 KPa). The measured boiling point depends on the atmospheric pressure. During thermal analysis the peak width of an endothermic reaction also depends on sample amount. Therefore, the onset point of the relevant endothermic peak will usually be stated as boiling point. For poorly defined endothermic peaks/effects the range will be stated in the result section. The temperature at the boiling point 

### I range is stated in degrees centigrade [ 0 C] and Kelvin [K] , with regard to the ambient pressure during the measurement. Results are given in degrees centigrade and in Kelvin. Conversion of units 

# ec to K): t 

### = T- 273.2 with t 

## = Celsius temperature, degrees Centigrade [ 0 C] T Thermodynamic temperature, Kelvin [K]
The boiling point depends on the atmospheric pressure. A correction to normalized pressure can be made. Because the correction factor for the boiling point is a specific parameter for each test item, the correction factor had to be determined. The determination of this correction factor is beyond the scope of this study, therefore no correction will be applied to the boiling point observed.Harlan Laboratories Study C30931 Leuco Sulfur Black 1 Report


## 4 RESULTS AND DISCUSSION Page 14



### The determination of the boiling point 

### I boiling range of the test item was performed according to the EEC Directive 92/69 and Council Regulation (EC) No. 440/2008, A.2 "Boiling temperature" and to the OECD Guideline No. 103: "Boiling point", adopted July 27, 1995. 

### 4.1 Preliminary Test The DSC-curve of the preliminary test (heating rate of 20 °C/min from 25 

## oc to 400 

## oq is shown in Figure 1. 

### An endothermic heat effect, the boiling, was observed at 99.8 °C. After the experiment, the sample had lost 55% of its mass and the colour ofthe sample was black. 

### 4.2 Main Test In 

### order to determine the boiling point more precisely, further DSC-runs were recorded between 25 

## oc and 215 °C with a heating rate of 10 °C/min. During these runs, the boiling point was determined to be 100.0 °C and 99.8 °C. The samples lost 51% and 50% of their mass, respectively. After the measurements the sample was a black powder. The DSC curve of the first main test is given in Figure 2. The results of the thermal analysis are summarized in Table 

### 1.Harlan Laboratories Study C30931 Leuco Sulfur Black I 

## 5 CONCLUSION Report



### The aim of this study was to determine the boiling point/range ofLeuco Sulfur Black I. 

### The boiling point of Leuco Sulfur Black 1 is determined to be

which is equal to 99.9 

# oc ± 

### 0.1 

# oc 373.1 K ± 

### 0.1 

### K. Page 15



### The atmospheric pressure during the measurements was 100.4 kPa (preliminary test) and 99.8 kPa (main tests). The boiling point of Leuco Sulfur Black 1 is influenced by its high water content. It can be assumed that the measured value corresponds to water only.Harlan Laboratories Study C30931 Leuco Sulfur Black 1


## 6 TABLES Report Page 16

Table 1 Determination of the Boiling Point of Leuco Sulfur Black 1 (Summary) Heating Range Heating Rate Boiling Point Boiling Point 

### [oC] [°C/min] 

### [OC] [K] Preliminary 25-400 20 99.8 373.0 Test 1st Main Test 25-215 10 100.0 373.2 2nd Main Test 25-215 10 99.8 373.0 Mean of boiling point: 99.9 373.1 Standard deviation(±): 0.1 0.1 The mean boiling point was calculated from the bold values (onset point of the endothermic reaction). The tabulated values represent rounded results obtained by calculation using the exact raw data.i-C:"'eXOmwExperiment:C30931/VT/LSB1/CZG/12.1.09,12.01.200914:21:53Methodenname:Vortest25-400/20°C/min/AirMethode:Vortest25-400/20°C/min/Air25.0-400.0°C20.00°C/min0-soIntegral-13.55e+03mJOnset99.75oc-100Peak122.14ocEndset146.14°CHeizrate20.00&C30931/VT/LSB1/CZG/12.1.09C30931/VT/LSBl/CZG/12.1.09,13.7600mgsol.OOl.SO200250300350ocHarlanLaboratoriesltd.:PhysChemMETTLERTOLEDOSTAReSystem'":l:j...........5§.0.....sit:lJoooolt:tli!l.c-oCZl!:!.(JI....CilnS'Q..'<(1)00.()0w....,0l'\0w(1)(:::n0CZl(:::IJjiirI:::0......g'ii30::s.[....3s·-l(1)E,'"'='....-.1-or$U-(')0zzenz0(').22-AexomWExperiment:C30931IHT1ILSB1ICZGI13.1.09,13.01.200912:01:110Methodenname:Maintest25-215°CI10°CIAir1\.....\1..-20-...,-40--60--80--100-Methode:Maintest25-215°CI10°CIAir25.0-215.0°C10.00°Cimin-120-Integral-20.84e+03mJOnset100.03°C&$C30931IHT1ILSB1ICZGI13.l.09Peakl.l.7.9l.°C-l.40-C30931IHTl.ILSBl.ICZG/13.l..09,21.7400mgEndsetl.38.2l.°CvHeizrate10.00°Cmin..-1II120IITII406080l.OOl.40l.60l.SO200oc-----HarlanLaboratoriesLtd.:PhysChemMETTLERTOLEDOSTAReSystem'T.!....8w0N0IJ:la-otZ.l"'...(')-·(jl>':'flI-CI.l['<0()0w.....,0t""'\0w0=n0tZ.ls::ttlI:::0-.g,-.,0-::1.3::$l)....::sCll-e."'d-00