technical report proficiency study of menthol in ......thomas a. perfetti, 2013, the chemical...

Routine Analytical Chemistry Sub-Group

Technical Report

Proficiency Study of Menthol in

Cigarettes and Cut Filler

May 2018

Sub-Group Coordinator:

Linda A. Crumpler, Cerulean, U.S.A.

Author and Study Coordinator:

Hiromoto Yamazaki, Japan Tobacco Inc., Japan

Co-Author and Statistical Analysis:

Michael Morton, Ph.D., Altria Client Services LLC, U.S.A.

Table of Contents

1. Summary ........................................................................................................................... 3

2. Introduction ....................................................................................................................... 3

3. Organization ...................................................................................................................... 3

3.1 Participants .............................................................................................................. 3

3.2 Protocol ................................................................................................................... 4

4. Data – Blank Test ............................................................................................................. 5

5. Data – Descriptive Statistics ............................................................................................. 7

6. Data – Statistical Analysis ................................................................................................ 7

7. Results – Z-Scores ............................................................................................................ 7

8. Conclusions ....................................................................................................................... 9

APPENDIX A: Study Protocol ............................................................................................... 10

APPENDIX B: Data Tables .................................................................................................... 18

APPENDIX C: Data Graphs ................................................................................................... 21

RAC-116-0-CTR Proficiency Study of Menthol in Cigarettes and Cut Filler – May 2018 3/23

1. Summary

The CORESTA Routine Analytical Chemistry Sub-Group (RAC) conducted a proficiency

study of menthol in cigarettes and cut filler in the first quarter of 2017. This study included

four mentholated cigarettes with different levels of menthol and CORESTA Monitor Test Piece

No. 8 (CM8). Fifteen laboratories participated in this study. Based on these results, a method

has been proposed for evaluation and, if fit for purpose, will be proposed as a CORESTA

Recommended Method.

2. Introduction

The objective of this study was to evaluate in-house methods for determination of menthol in

cigarettes, cut filler, and non-tobacco material. Each laboratory received z-scores indicating

whether their results were in agreement with the other laboratories. The results were also

examined to determine if there were systematic differences associated with their analytical

methodology.

3. Organization

3.1 Participants

A list of the participating laboratories is provided in Table 1. The laboratories are listed in

alphabetical order; however the laboratory codes used in this report do not correspond to the

same order as provided in Table 1.

Table 1: List of participating laboratories

Participating Laboratories

Altria Client Services LLC, United States

BAT Brazil, Brazil

C.I.T.MONTEPAZ S.A., Uruguay

Global Laboratory Services, United States

ITC Life Sciences & Technology Centre, India

ITG Brands LLC, United States

Japan Tobacco Inc., Japan

JT International Germany GmbH, Germany

JTI Ökolab, Austria

KT&G, South Korea

Labstat International ULC, Canada

Landewyck Tobacco, Luxembourg

Philip Morris International, Switzerland

Reemtsma / Imperial Tobacco Central Lab Hamburg, Germany

RJ Reynolds Tobacco, United States


3.2 Protocol

Specific details from the protocol are described below and the full protocol is provided in

Appendix A. The mentholated cigarette samples in packs were produced by Japan Tobacco

Inc. in November 2016 and kept in a conditioned room (temperature: 22 °C, humidity: 60 %)

until shipping in February 2017. Participants were required to procure CM8 from Cerulean or

Borgwaldt KC GmbH to serve as a blank. Laboratories were requested to store all samples in

a conditioned room (temperature: 22 °C, humidity: 60 %) until analysis. The parameters to be

measured were menthol in cut filler, menthol in non-tobacco materials, menthol in whole

cigarette, and sample weight for each extraction. Two cigarettes from one pack were used for

an individual extraction. Three (3) independent replicate sample extractions and analyses were

required per sample and the data were to be reported in units of mg/cigarette. Laboratories

were requested to submit data and some chromatograms (the extractions of cut filler and whole

cigarette of Sample D and CM8, the lowest calibration standard) by March 15, 2017; however,

data were accepted until March 31, 2017. The samples are identified in Table 2.

Table 2: Sample identification

Test Sample Target Menthol Level in Cut Filler

Sample A – commercial product Approx. 10 mg/g

Sample B – commercial product Approx. 7 mg/g

Sample C – commercial product Approx. 4 mg/g

Sample D – prototype product Approx. 2 mg/g

CORESTA Monitor Test Piece No.8 (CM8) No

Each laboratory used their own analytical method. A summary of the analytical methods are

given in Table 3 and Table 4.

Table 3: Extraction conditions

Lab Solvent Solvent

volume

Extraction

equipment

Extraction

time

Extraction

temperature 1 Methanol 100 ml Orbital shaker 60 minutes Room temp.

2 Methanol 50 ml Orbital shaker 30 minutes -

3 Isopropanol 40 ml Orbital shaker 60 minutes -

4 Methanol 40 ml Flat bed shaker 20 minutes x 2 22 °C

5 Methanol 40 ml INFORS shaker 120 minutes Room temp.

6 Isopropanol 20 ml Orbital shaker 60 minutes Ambient temp.

7 Isopropanol 50 ml Orbital shaker 54 hours Ambient temp.

8 Methanol 100 ml Orbital shaker 60 minutes Ambient temp.

9 Methanol 100 ml Ultrasonic 180 minutes Room temp.

10 Methanol 50 ml Orbital shaker 30 minutes Room temp.

11 Methanol 40 ml Flat bed shaker 30 minutes Room temp.

12 Methanol 20 ml / 15 ml Wrist action shaker / Orbital 20 minutes Room temp.

13 Methanol 25 ml Orbital shaker 60 minutes Room temp.

14 Methanol 50 ml Orbital shaker 60 minutes 55 °C

15 Ethanol 50 ml Heating mantle 30 minutes -

Note: - no information


Table 4: Analytical conditions

Lab Internal Standard Equipment Column Column Dimensions

1 Anethole GC/FID DB-Wax 30 m x 250 µm x 0.25 µm

2 Anethole GC/FID CP-WAX 52 25 m x 320 µm x 0.2 µm

3 Heptadecane GC/FID RTX-5 30 m x 250 µm x 0.25 µm

4 Heptadecane GC/FID DB-WAX 15 m x 530 µm x 1 µm

5 1,3-Butanediol GC/FID DB-WAX 30 m x 530 µm x 1 µm

6 Heptadecane GC/FID CP-WAX 30 m x 250 µm x 0.25 µm

7 Dodecane GC/FID HP-5 5 m x 200 µm x 0.11 µm

8 1-Octanol GC/FID DB-ALC1 15 m x 320 µm x 1.8 µm

9 Anethole GC/FID DB-WAX 15 m x 320 µm x 0.25µm

10 Decanol GC/FID Carbowax 30 m x 250 µm x 0.25 µm

11 Decanol GC/MS RTX-5 Amino 30 m x 250 µm x 1 µm

12 Anethole GC/FID RTX-5 15 m x 250 µm x 0.25µm

13 1,3-Butanediol GC/FID J&W DB-WAX 15 m x 530 µm x 1 µm

14 Anethole GC/FID BD-Waxetr 0.5 m x 250 µm x 0.4 µm

15 Anethole GC/FID DB-Wax 30 m x 320 µm x 0.25 µm

4. Data – Blank Test

CORESTA Monitor Test Piece No.8 (CM8) was produced according to ISO 16055 “Tobacco

and tobacco products - Monitor test piece - Requirements and use” and is non-mentholated.

Most laboratories reported that menthol in CM8 cut filler was not detected or below the

detection limit. However, one laboratory reported that a very small amount of menthol was

observed by GC-Flame Ionization Detector (FID) in the CM8 cut filler. The GC

chromatograms obtained by the laboratory for the extracted cut filler of Sample D and CM8

were provided in Figure 1 and 2 respectively.

Figure 1: GC-FID chromatogram on cut filler of Sample D


Figure 2: GC-FID chromatogram on cut filler of CM8

One laboratory used the Kentucky reference cigarette 1R6F for the blank test because CM8 was

not available at that time. This laboratory also reported a small amount of menthol - when using

GC-Mass spectrometry (MS) - in the 1R6F cut filler. GC-MS chromatograms obtained by the

laboratory for cut filler to extracts of Sample D and the 1R6F are provided in Figures 3 and 4,

respectively.

Figure 3: GC-MS chromatogram on cut filler of Sample D


Figure 4: GC-MS chromatogram on cut filler of 1R6F

Menthol has been identified as a naturally occurring compound in tobacco (Alan Rodgman and

Thomas A. Perfetti, 2013, The Chemical Components of Tobacco and Tobacco Smoke, Second

Edition, CRC Press). This could be the reason that menthol was observed in non-mentholated

tobacco and in cut filler of non-mentholated cigarettes. Another possible reason could be

atmospheric or other contamination during analysis.

5. Data – Descriptive Statistics

The data tables, with descriptive statistics, for Samples A, B, C, and D are provided in

Appendix B. Graphs of the data are shown in Appendix C.

6. Data – Statistical Analysis

The analysis was carried out in basic conformance with ISO 13528. The assigned values and

the standard deviations for proficiency assessment were calculated using the robust procedure

given in Algorithm A of ISO 13528 and also found in ISO 5725-5. This algorithm mitigates

the effects of outlying observations and can be used in lieu of outlier detection and removal.

7. Results – Z-Scores

The primary output of a proficiency study is the z-scores. For each laboratory and each sample

and each analysis location, the z-score is defined by

𝑧 =𝑥 − 𝑥𝑎

𝜎𝑝

In the formula x is the laboratory value, xa is the assigned value, and 𝜎𝑝 is the standard deviation

for proficiency assessment. That is, each laboratory average is given a score depending on how

many standard deviation units it is from the assigned value and can take on positive or negative

values depending on whether it is above or below the assigned value.


As a general rule, the z-scores are regarded as reasonable if –2 < z < 2 and are thought to be

unacceptable if |z| > 3. Laboratories should consider |z| between 2 and 3 as a warning signal.

Laboratories should be particularly aware of the pattern of their results. For example a single

z-score signal should be looked into, but a pattern of problematic z-scores should be taken much

more seriously still. The z-scores are tabulated in Table 5 and shown graphically in Figure 5.

Table 5: Z-scores for each sample and each laboratory

Whole Cigarette Filler NTM

Lab A B C D A B C D A B C D

1 0.16 0.65 0.31 0.66 0.14 0.39 0.83 0.68 0.33 -0.20 -0.64 -0.86

2 0.21 0.43 0.33 0.19 0.80 0.25 0.41 0.38 0.20 0.81 -0.48 -0.44

3 -6.04 -5.71 -4.98 -2.98 -5.86 -6.20 -3.61 -3.01 -1.32 -2.65 -0.75 -0.46

4 0.37 0.65 1.00 0.63 0.47 0.80 0.87 0.62 0.00 0.70 -0.28 -0.45

5 0.23 0.21 0.22 0.98 0.27 0.58 0.66 1.04 0.21 0.45 1.35 2.17

6 -3.08 -3.42 -3.19 -2.70 -3.23 -3.47 -2.60 -3.08 -1.27 -1.68 -1.64 -2.03

7 -1.27 -1.22 -1.34 -1.20 -2.23 -2.15 -1.38 -1.63 0.43 0.58 -0.22 -0.20

8 0.15 0.02 0.20 0.42 0.32 0.45 0.32 0.50 -0.34 -0.38 0.35 0.54

9 2.34 1.08 1.09 0.90 1.32 1.10 1.13 1.16 2.27 0.75 -0.07 0.48

10 0.89 0.54 -0.40 -0.62 -0.02 0.21 -0.23 -0.27 -0.18 -1.12 -1.41 -1.30

11 0.27 -0.52 0.12 -0.06 -0.46 -0.34 -0.22 -0.01 1.15 1.34 0.78 1.23

12 0.98 1.25 1.03 0.96 0.92 1.12 0.82 0.60 1.12 0.74 0.29 0.03

13 -0.44 -0.24 0.19 0.36 -0.02 -0.30 -0.21 -0.01 -0.64 -0.06 0.35 -0.07

14 0.32 0.54 0.77 0.48 0.35 0.03 0.33 0.03 0.14 -0.02 0.87 1.03

15 -0.36 -0.41 -0.52 -0.70 0.42 0.20 -0.33 -0.23 -1.32 -0.60 1.35 0.46


Figure 5: Graphical representation of z-scores. For each laboratory, Sample A is the

leftmost point on the graph, followed in succession by Samples B, C, and D.

Laboratories 3, 6, and 7 used isopropanol as their extraction solvent. Focusing on the filler and

whole cigarette results, these laboratories had lower results than the other laboratories. Those

lower results suggest that isopropanol is a less effective solvent than methanol or ethanol. The

laboratory 7 results were closer to the other laboratories than were the results in laboratories 3

and 6, possibly due to the long extraction time employed by laboratory 7 as shown in Table 3.

8. Conclusions

The purpose of the study was to compare the results coming from each participating

laboratory’s in-house analytical method for menthol. In the study each laboratory measured

menthol in the tobacco filler, the whole cigarette, and the non-tobacco material of the cigarette.

Most of the laboratories used GC/FID, though with a wide range of columns. Extraction times

varied widely, though around one hour was the most common. The most common extraction

solvent was methanol. One laboratory used ethanol as the extraction solvent and the laboratory

performed similarly to the laboratories which used methanol. Three laboratories used

isopropanol as the extraction solvent, and it appeared to be a less effective solvent in tobacco

filler and in the whole cigarette. With that exception, however, the results were generally

comparable across the participating laboratories.

Based on these results, a method has been proposed for evaluation and, if fit for purpose, will

be proposed as a CORESTA Recommended Method.


APPENDIX A: Study Protocol

Routine Analytical Chemistry Sub-Group

Proficiency Trial

Determination of Menthol in Cigarettes and Cut Filler

Protocol

Hiromoto Yamazaki

Japan Tobacco Inc.

Japan

16 January 2017


Foreword

This CORESTA protocol describes the elements that the Standards Task Force has identified

as important for describing elements of an experimental protocol for a collaborative study or a

proficiency study as defined below (Horowitz 862):

• Collaborative study

“A collaborative study is an interlaboratory study in which each laboratory uses the

defined method of analysis to analyse identical portions of homogeneous materials to

assess the performance characteristics obtained for that method of analysis.”

CORESTA recognizes that collaborative studies require considerable effort and should

be conducted only on methods that have received adequate prior testing.

• Proficiency Study

“A proficiency study is an interlaboratory study consisting of one or more assays,

conducted by a group of laboratories on one or more identical materials, by whatever

method is in use in each laboratory, for the purpose of comparing the results of each

laboratory with those of other laboratories, with the objective of evaluating or improving

performance.”

Proficiency studies often serve as pre-work for selecting a method for a full

collaborative study.


1. Introduction

The overall objective of this project is to develop a CORESTA Recommended Method (CRM)

for the determination of menthol in cigarettes and cut filler (most likely by gas chromatography).

Other deliverables will be Technical reports and Sample Handling Guide for mentholated

cigarettes and cut filler.

2. Objective

The objective of this study is to evaluate in-house methods for determination of menthol in

cigarettes and cut filler by statistical analysis in order to assess similarities/differences between

methodologies.

3. Study Coordinator

Hiromoto Yamazaki

Senior Scientist

Japan Tobacco Inc.

Product Quality Research Center

1-17-7 Yokokawa Sumida-ku, Tokyo

Japan

E-mail: [email protected]

Tel: +81-3-6745-2134

4. Study Time Table

Date Activity

November, 2016 Sample production

Mid-February, 2017 Sample distribution by JT except CORESTA Monitor test piece (CM8)

Mid-February to March

15th, 2017 Analysis at participant laboratories

March 15th, 2017 Data submission by this date

March 15th to April, 2017 Statistical analysis by Dr. Morton

May 4th, 2017 Discuss results at RAC meeting

5. Samples

The test samples listed in Table 1 will be analysed.


Table 1: Test Samples

Test Sample Target Menthol Level

in Cut Filler

Sample

Distribution

Sample A – commercial product Approx. 10mg/g 1 carton

Sample B – commercial product Approx. 7 mg/g 1 carton

Sample C – commercial product Approx. 4 mg/g 1 carton

Sample D – prototype product Approx. 2 mg/g 1 carton

CORESTA Monitor 8 (CM8) test

piece No No

Test samples A, B, C and D were produced in November, 2016. They were kept in a conditioned

room (temperature: 22oC, humidity: 60%) until shipping.

CORESTA Monitor test piece (CM8) should be analysed as a blank.

CORESTA Monitor test piece (CM8) should be ordered from:

Cerulean

Rockingham Drive

Linford Wood East

Milton Keynes MK14 6LY

United Kingdom

Tel: +44 1908 23 38 33

Fax: +44 1908 23 53 33

e-mail: [email protected]

Borgwaldt KC GmbH

Spare Parts Department,

Schnackenburgallee 15,

D-22525 Hamburg

Germany,

Tel: +49 40 85 31 380

Fax: +49 40 850 56 00

e-mail: [email protected]

6. Analysis

6.1 Parameters to be measured

Laboratories should analyse the following all items:

- Menthol in cut filler

- Menthol in non-tobacco materials (NTMS; cigarette paper, filter and tipping paper)

- Menthol in whole cigarette

- Sample weight for each extraction

6.2 Sample preparation

All test samples should be kept in a conditioned room (temperature: 22 oC, humidity:

60 %) until analysis.

- Menthol in cut filler

Take out two (2) cigarettes from one pack. Slit them longitudinally and separate

them into cut filler and non-tobacco materials (NTMs; cigarette paper, filter and

tipping paper). Weigh all cut filler and record it. All cut filler should be used for an

individual extraction. Obtain three (3) individual extractions, one each from three

(3) packs of each test sample. They should be extracted as soon as possible after

opening a pack.

mailto:[email protected]

mailto:[email protected]


- Menthol in non-tobacco materials (NTM; cigarette paper, filter and tipping paper)

Take out two (2) cigarettes from one pack. Slit them longitudinally and separate

them into cut filler and non-tobacco materials (NTMs; cigarette paper, filter and

tipping paper). Weigh all NTMs and record it. All NTMs should be used for an

individual extraction. Obtain three (3) individual extractions, one each from three

(3) packs of each test sample. They should be extracted as soon as possible after

opening a pack.

- Menthol in whole cigarette

Take out two (2) cigarettes from one pack. Weigh total of two (2) cigarettes and

record it. Slit them longitudinally and separate them into cut filler and non-tobacco

materials (NTMs; cigarette paper, filter and tipping paper). All materials (cut filler

and NTMs) from two (2) cigarettes should be used for an individual extraction.

Obtain three (3) individual extractions, one each from three (3) packs of each test

sample. They should be extracted as soon as possible after opening a pack.

6.3 Extraction

Use in-house method except for above sample preparation.

6.4 Replicates

Analyse three (3) individual extractions to each test sample by in-house method.

Each extraction per test sample is from a separate pack.

6.5 Test units

- Menthol: mg/cigarette

- Sample weight: mg/cigarette

All results should be reported to second decimal places

7. Data Submission

Participating laboratories should use the embedded Excel document for data reporting.

Chromatograms (the extractions of cut filler and whole cigarette to Sample D and CM8, the

lowest calibration standard) obtained with your in-house method should be reported in the data

reporting sheet as well. Other requested methodological details should also be reported in the

data reporting sheet if not reported in advance to Project Leader.

The completed data sheet should be sent to the following by March 15th, 2017:

Hiromoto Yamazaki: Hiromoto.yamazaki(@)jt.com

Linda Crumpler: linda.crumpler(@)cerulean.com


Data Reporting Worksheet RAC-116-PRM

Report sheet of Proficiency study to the determination method of menthol in cigarettes and cut filler 170116.xlsx

8. Explanation of Statistics to be Applied for a Proficiency Study

The following text should be edited according to the suggestions from Dr. Morton (especially,

it should be “Horwitz” instead of “Horowitz”).

Select the appropriate description from the sections below and delete text that is not applicable.

For proficiency studies Z-scores are used to measure individual laboratory performance.

8.1 Z-Score Calculation

𝑧 =𝑥 − 𝑥𝑎

𝜎𝑝

where

𝑥 is the individual laboratory average

𝑥𝑎 is the assigned value

• It is ideal if the materials have an “assigned value” prior to the study. For example,

certified values or a consensus value from previous study. It is possible, however, to

develop a consensus value from the proficiency study itself.

𝜎𝑝 is the “standard deviation for proficiency assessment” and can be assigned/established in

several ways.

• It can be a “target“ established, for example, by a desired of “ fitness for purpose”

relative error.

• Through use something akin to the “Horwitz equation” which is a model fitted originally

by William Horwitz relating concentration and method variability.

• Based on variability seen among labs in the current or previuos studies. The Horwitz

Equation is used to estimate analytical method standard deviations as a function of the

analyte concentration alone. It is defined separately in three different intervals.

𝜎𝑝 = 0.01√𝑐, 13.8 % c

𝜎𝑝 = 0.02𝑐0.8495, 120𝑛𝑔

𝑔 c 13.8 %

𝜎𝑝 = 0.22𝑐, c < 120𝑛𝑔

𝑔


Appendix A : Système International (SI) Units and their Symbols

SI base units

Base Quantity Name Symbol

Length meter m

Mass kilogram kg

Time second s

Electric current ampere A

Temperature kelvin K

Amount of substance mole mol

Luminous intensity candela cd

SI derived units

Derived Quantity Name Symbol Equivalent

SI Units

Frequency hertz Hz s-1

Force newton N m·kg·s-2

Pressure pascal Pa N/m2

Energy joule J N·m

Power watt W J/s

Electric charge coulomb C s·A

Electric potential volt V W/A

Electric resistance ohm Ω V/A

Celsius temperature degree Celsius °C K*

*Unit degree Celsius is equal in magnititude to unit kelvin


SI prefixes

Factor Name Symbol Numerical Value

1012 tera T 1 000 000 000 000

109 giga G 1 000 000 000

106 mega M 1 000 000

103 kilo k 1 000

102 hecto h 100

101 deka da 10

10-1 deci d 0.1

10-2 centi c 0.01

10-3 milli m 0.001

10-6 micro µ 0.000 001

10-9 nano n 0.000 000 001

10-12 pico p 0.000 000 000 001


APPENDIX B: Data Tables

Whole Cigarette Menthol (mg/cig) Filler Menthol (mg/cig) NTM Menthol (mg/cig)

Lab Rep A B C D A B C D A B C D

1 1 14.536 9.025 3.350 2.017 5.815 4.316 2.040 1.065 8.914 4.511 1.403 0.850

2 14.739 9.264 3.475 2.020 5.781 4.356 2.027 1.051 8.926 4.552 1.374 0.863

3 14.785 8.812 3.346 2.020 5.620 4.108 2.023 1.101 8.838 4.487 1.405 0.865

2 1 14.600 9.000 3.430 1.980 6.110 4.240 1.880 1.010 8.840 4.510 1.410 0.870

2 14.740 8.820 3.320 1.930 6.050 4.300 1.960 1.060 8.760 4.850 1.440 0.880

3 14.820 8.970 3.430 1.860 6.150 4.080 1.900 1.010 8.890 4.770 1.390 0.930

3 1 10.608 6.075 1.920 1.255 2.488 1.776 0.784 0.492 8.118 3.644 1.361 0.921

2 10.590 5.978 1.977 1.279 2.522 1.757 0.758 0.498 8.170 4.330 1.376 0.840

3 10.494 6.090 2.002 1.305 2.383 1.877 0.785 0.538 8.089 4.165 1.408 0.913

4 10.600 – – – 2.414 – – – 7.997 – – –

4 1 14.882 9.029 3.603 2.039 5.934 4.496 1.988 1.086 8.788 4.815 1.415 0.920

2 14.735 9.018 3.546 1.929 5.968 4.387 1.991 1.007 8.637 4.647 1.463 0.883

3 14.862 9.058 3.575 2.069 5.859 4.355 2.151 1.098 8.774 4.603 1.434 0.874

5 1 14.710 8.920 3.280 2.130 5.860 4.350 2.040 1.120 8.810 4.560 1.650 1.040

2 14.790 8.840 3.310 2.080 5.560 4.050 1.950 1.110 8.970 4.610 1.660 1.100

3 14.700 8.720 3.500 2.040 6.010 4.590 1.960 1.150 8.720 4.750 1.580 1.180

6 1 12.398 7.014 2.494 1.368 4.002 2.766 1.068 0.484 8.100 4.076 1.294 0.780

2 12.656 7.194 2.408 1.274 3.846 2.824 1.052 0.504 8.096 4.358 1.256 0.718

3 12.558 7.162 2.442 1.368 3.834 2.880 1.062 0.504 8.164 4.264 1.276 0.792

7 1 13.913 8.027 2.873 1.651 4.391 3.346 1.441 0.711 8.931 4.663 1.503 0.948

2 13.648 8.303 2.895 1.660 4.304 3.268 1.368 0.741 8.961 4.659 1.419 0.901




3 13.658 8.134 3.070 1.613 4.626 3.328 1.406 0.707 8.932 4.672 1.412 0.890

8 1 14.669 8.764 3.260 1.978 5.930 4.389 1.945 1.079 8.646 4.635 1.577 0.972

2 14.809 8.664 3.372 1.922 5.769 4.339 1.838 0.993 8.447 4.306 1.467 0.985

3 14.562 8.785 3.442 2.014 5.814 4.115 1.877 1.064 8.612 4.502 1.491 0.962

9 1 16.081 9.385 3.705 2.097 6.605 4.560 2.170 1.152 10.039 4.609 1.492 0.960

2 16.373 9.016 3.595 2.081 6.242 4.597 2.036 1.118 9.673 4.678 1.456 0.980

3 15.961 9.306 3.493 2.024 6.320 4.422 2.145 1.165 9.788 4.807 1.439 0.967

10 1 15.090 8.800 3.330 1.770 5.920 3.980 1.710 0.940 8.670 4.180 1.370 0.810

2 14.720 9.000 3.130 1.680 5.560 4.410 1.730 0.920 8.770 4.500 1.330 0.820

3 15.710 9.150 3.130 1.830 5.470 4.190 1.750 0.920 8.500 4.340 1.210 0.840

11 1 15.000 8.950 3.440 1.740 5.490 4.100 1.720 0.950 9.430 4.960 1.550 1.050

2 14.670 8.560 3.300 1.840 5.490 3.900 1.770 0.940 9.130 4.830 1.540 0.980

3 14.620 7.940 3.270 2.040 5.260 3.970 1.710 1.010 9.310 4.640 1.600 1.060

12 1 15.530 9.500 3.690 2.080 6.070 4.480 2.020 1.080 9.401 4.698 1.533 0.918

2 15.020 9.420 3.540 2.090 6.230 4.510 2.080 1.050 9.043 4.716 1.503 0.902

3 15.160 9.030 3.520 2.070 6.200 4.610 1.980 1.050 9.380 4.674 1.479 0.976

13 1 14.281 8.486 3.386 2.009 5.660 4.020 1.730 0.940 8.597 4.494 1.529 0.906

2 14.137 8.731 3.335 1.966 5.650 3.950 1.740 0.980 8.543 4.564 1.491 0.929

3 14.461 8.628 3.350 1.900 5.640 4.040 1.740 0.980 8.130 4.570 1.517 0.936

14 1 14.480 8.800 3.500 1.980 5.930 4.200 1.800 0.950 8.850 4.780 1.560 0.980

2 14.930 8.850 3.500 1.990 6.130 4.150 1.900 1.010 8.810 4.430 1.570 1.050

3 14.980 9.300 3.540 1.980 5.500 4.030 1.970 0.960 8.750 4.440 1.590 1.010

15 1 14.200 8.420 3.220 1.690 5.740 4.030 1.650 0.920 8.140 4.440 1.630 0.960




2 14.500 8.580 3.220 1.810 5.720 4.310 1.730 0.970 7.870 4.400 1.640 0.990

3 14.330 8.610 3.060 1.730 6.220 4.230 1.730 0.910 8.270 4.480 1.620 0.950

Assigned Value

14.583 8.728 3.305 1.885 5.664 4.115 1.796 0.968 8.733 4.554 1.470 0.929

Std. Dev for Prof.

0.664 0.470 0.269 0.203 0.548 0.373 0.283 0.153 0.484 0.192 0.119 0.082


APPENDIX C: Data Graphs

technical report proficiency study of menthol in ......thomas a. perfetti, 2013, the chemical...

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