Measure of wine alcoholic strength by volume by densimetry using hydrostatic balance
RESOLUTION OENO 24/2000
MEASURE OF WINE ALCOHOLIC STRENGTH BY VOLUME BY DENSIMETRY USING HYDROSTATIC BALANCE
THE GENERAL ASSEMBLY,
CONSIDERING Article 5 of the International Convention for the Unification of Methods of Analysis and Appraisal of Wine of 13 October 1954,
UPON THE PROPOSAL of the Sub-commission of Methods of Analysis and Appraisal of Wine,
DECIDES
To complete and substitute in Annex A of the Compendium of International Methods of Analysis of Wine and Musts, the method: “Determination of wine alcoholic strength by volume by densimetry using hydrostatic balance” by the following method:
1. METHOD OF MEASUREMENT
1.1. Strength and introduction
Measurement of alcoholic strength by volume should be determined before marketing notably to be in compliance with labelling rules.
Alcoholic strength by volume is equal to the number of litres of ethanol contained in 100 litres of wine measured at 20°C, referred to as “% vol.”.
1.2. Safety precaution
Respect safety measures concerning the use of distillation apparatuses, manipulation of hydro-alcoholic solutions and cleaning products.
1.3. Object and field of application
The method of measurement is densimetry using a hydrostatic balance.
In reference to regulatory provisions in force the trial temperature is set at 20°C.
1.4. Principle and definitions
The principle of this method involves firstly distilling wine volume by volume. The distilling method is described in the Compendium. Non volatile substances can be eliminated through distillation. Ethanol counterparts and ethanol found in esters are included in the alcoholic strength as they are found in the distillate.
Secondly, the volumetric weight of the distillate obtained is measured. The volumetric weight of a liquid at a given temperature is equal to the ratio of the weight over its volume: ρ=m/V, for wine, it is expressed in g/ml.
The alcoholic strength of wine can be measured by densimetry using a hydrostatic balance following the Archimedes principle by which any body plunged into a fluid undergoes a vertical push, from the bottom to the top, equal to the weight of the displaced fluid.
1.5. Reagents
Unless other wise indicated, only recognised analytical quality reagents should be used during the analysis with at least class 3 water corresponding to the definition of the standard ISO 3696:1987.
1.5.1. Solution for washing float device (sodium hydroxide , 30% m/v).
To prepare a 100 ml solution, weigh 30 g of sodium hydroxide and fill using 96% vol. ethanol.
1.6. Apparatus and material
current laboratory apparatus including:
1.6.1. Single-plate hydrostatic balance with 1 mg precision.
1.6.2. Floater with at least 20 ml volume, specifically adapted for the balance, suspended by a thread with a diameter less than or equal to 0.1 mm.
1.6.3. Cylindrical test tube with level indicator. The floater must entirely fill the test tube volume above the marker, only the slinging wire goes through the surface of the liquid. The cylindrical test tube should have an inside diameter at least above 6 mm of the floater.
1.6.4. Thermometer (or temperature measurement pipette) with degree and 10th of degree graduations, from 10°C to 40°C, calibrated to ± 0.05°C.
1.6.5. Calibrated weight by a recognized certification body.
1.7. Procedure
After each measurement, the floater and the test tube must be cleaned with distilled water, wiped with soft laboratory paper which doesn’t loose its fibres and rinsed with solution whose volumetric weight is to be determined. These measurements must be carried out once the apparatus has reached a stable level in order to limit alcohol loss through evaporation.
1.7.1. Balance calibration
While balances usually have internal calibration systems, hydrostatic balances must be calibrated with controlled weights by an official certification body.
1.7.2. Floater calibration
1.7.2.1. Fill cylindrical test tube up to marker with bidistilled water (or an equivalent purity, for example microfiltered water with a conductivity of 18.2 M/cm), whose temperature between 15°C to 25°C, but preferably at 20°C.
1.7.2.2. Plunge the floater and the thermometer into the liquid, shake, note down the volumetric weight on the apparatus and, if necessary, adjust the reading in order for it to be equal to the water measurement temperature.
1.7.3. Control using a hydroalcoholic solution
1.7.3.1. Fill the cylindrical test tube up to the marker with a known titre of hydroalcoholic solution at a temperature between 15°C to 25°C, preferably at 20°C.
1.7.3.2. Plunge the floater and the thermometer into the liquid, shake, note down the volumetric weight on the apparatus (or the alcoholic strength if possible). The established alcoholic strength must be equal to the previously determined alcoholic strength.
Note 2: This alcoholic strength solution can be replaced by bidistilled water for floater calibration.
1.7.4. Measure volumetric weight of the distillate (or alcoholic strength if possible)
1.7.4.1. Pour the sample for the trial in the cylindrical test tube up to the marker level.
1.7.4.2. Plunge the floater and the thermometer into the liquid, shake, note down the volumetric weight on the apparatus (or the alcoholic strength if possible. Note the temperature if the volumetric mass is measured at t°C (t).
1.7.4.3. Correct t using a volumetric weight table t of hydroalcoholic mixtures [Table II of Annex II of the Compendium of methods of analysis of the OIV].
1.7.5. Clean the floater and cylindrical test tube.
1.7.5.1. Plunge the floater into the wash solution in the test tube.
1.7.5.2. Allow to soak 1 hour while turning the floater regularly.
1.7.5.3. Rinse with tap water, then with distilled water.
1.7.5.4. Wipe with soft laboratory paper which doesn’t loose its fibres.
Carry out these operations when the floater is used for the first time and then on a regular basis when necessary.
1.7.6. Result
Using 
, volumetric weight, calculate real alcoholic strength by using the table indicating volumetric alcoholic strength (% vol.) at 20°C according to volumetric weight at 20°C of hyrdoalcoholic mixtures. This is the international table adopted by the International Organisation of Legal Metrology in its recommendation number 22.
2. Comparison of measurements
Carried out using a hydrostatic balance with measurements obtained using an electronic density-meter (OIV Reference method, Annex A of the Compendium of International Methods of Analysis).
From samples whose alcoholic strength is between 4% vol. and 18% vol. the measurements of repeatability and reproducibility were performed after an inter-laboratory ring test. It is the comparison of the measurements of wine alcoholic strength of different samples using the hydrostatic balance and the electronic density-meter, including the repeatability and reproducibility values derived from pluri-annual intercomparison test trials performed on a large scale.
2.1. Samples:
Wines of different density and alcoholic strengths prepared monthly on an industrial scale, taken from a bottled stock stored under normal conditions, and supplied as anonymous products to laboratories.
2.2. Laboratories
laboratories participating into the monthly ring test organised by Unione Italiana Vini Verona, (Italy) according to ISO 5725 (UNI 9225) regulation and the 'International Protocol of Proficiency test for chemical analysis laboratories' established by AOAC, ISO and IUPAC (J. AOAC Intern., 1993, 74/4) and according to guidelines ISO 43 and ILAC G13. An annual report is supplied by the cited company to all participants.
2.3. Apparatus:
2.3.1. Electronic hydrostatic balance (whose precision allows to give the 5th decimal of density) eventually equipped with a data treatment device.
2.3.2. Electronic density-meter eventually equipped with an autosampler.
2.4. Analyses
According to method validation rules (resolution OENO 6/99), each sample is analysed twice consecutively to determine the alcoholic strength.
2.5. Results
Table 1 shows the results of the measurements obtained by the laboratories using the hydrostatic balance.
Table 2 shows the results obtained by the laboratories using an electronic densimeter.
2.6. Evaluations of the results
2.6.1. The trial results were examined for evidence of individual systematic error (p<0.025) using Cochran's and Grubbs' tests successively, by procedures described in the internationally agreed [“Protocol for the Design, Conduct and Interpretation of Method-Performance Studies" Ed W Horwitz, Pure and Applied Chemistry, 1995, 67, (2), 331 343.].
2.6.2. Repeatability (r) and reproducibility (R)
Calculations for repeatability (r) and reproducibility (R) as defined by the protocol were carried out on the results remaining after the removal of outliers. When assessing a new method there is often no validated reference or statutory method with which to compare precision criteria, hence it is useful to compare the precision data obtained from collaborative trials with “predicted” levels of precision. These “predicted” levels are calculated from the Horwitz formula. Comparison of the trial results and the predicted levels indicate as to whether the method is sufficiently precise for the level of analyte being measured.
The predicted Horwitz value is calculated from the Horwitz formula.
 |
where C = measured concentration of analyte expressed in decimals. (e.g. 1 g/100g = 0.01) [Horwitz, W., Analytical Chemistry, 1982, 54, 67A-76A.].
The Horrat value gives a comparison of the actual precision measured with the precision predicted by the Horwitz formula for the method and at that particular level of concentration of the analyte. It is calculated as follows:
 |
2.6.1. Interlaboratory precision
A Horrat value of 1 usually indicates satisfactory inter-laboratory precision, whereas a value of more than 2 usually normally indicates unsatisfactory precision, i.e. one that is too variable for most analytical purposes or where the variation obtained is greater than that expected for the type of method employed. Hor is also calculated, and used to assess intra-laboratory precision, using the following approximation:
-
(Horwitz) = 0.66 
(Horwitz) (this assumes the approximation r = 0.66 R).
Table 3 shows the differences between the measurements obtained by laboratories using an electronic densimeter and those using a hydrostatic balance. Excluding the sample of 2000/3 with very low alcohol strength and for which both techniques show poor reproducibility, a very good concordance is generally observed for the other samples.
2.6.2. Fidelity parameters
Table 4 shows the averaged overall fidelity parameters computed from all monthly trials carried out from January 1999 until May 2001.
In particular:
- Repeatability (r)= 0.074 (% vol.) for the hydrostatic balance and 0.061 (% vol.) for electronic densitometry;
- Reproducibility (R)= 0.229 (% vol.) for the hydrostatic balance and 0.174 (% vol.) for electronic densimetry, this latter value is concordant to the value estimated for the electronic densimetry from the OIV Compendium of International Methods of Analysis;
2.7. Conclusion
The results concerning the determination of the alcoholic strength of a large range of wines show that the measurements carried out with the hydrostatic balance are concordant with those carried out by electronic densimetry using a flexion resonator and that the validation parameter values are similar for both methods.
Bibliography
- F.V. n. 1096; Cabanis Marie-Thérèse., Cassanas Geneviéve, Raffy Joëlle, Cabanis J.C., 1999: Validation de la mesure du titre alcoolometrique volumique;
- Cabanis Marie-Thérèse., Cassanas Geneviéve, Raffy Joëlle, Cabanis J.C., 1999: Intérêt de la balance hydrostatique “nouvelle génération” pour la détermination du titre alcoométrique des vins et des boissons spiritueuses. Rev. Franç. Œnol., 177/juillet-août, 28-31;
- Versini G., Larcher R., 2002: Comparison of wine density and alcoholic strenght measurement by hydrostatic balance and electronic density–meter. Communication at the OIV Sub-commission of analytical methods, Paris, 13-15 March 2002
- OIV, Recueil des méthodes internationales d’analyse des vins et des moûts, Office International de la Vigne et du Vin; Paris;
- 'International Protocol of Proficiency test for chemical analysis laboratories'., J. AOAC Intern., 1993, 74/4
- normes ISO 5725 et guides ISO 43;
- resolution OENO 6/99;
- Horwitz W., 1995. Protocol for the design, conduct and interpretation of method-performance studies, Pure and Applied Chemistry, 67/2, 331-343.
Legend:
mean: the mean of all the data used in the statistical analysis
n: total number of sets of data submitted
nc: number of results excluded from statistical analysis due to non-compliance
outliers: number of results excluded from statistical analysis due to determination as outliers by either Cochran’s or Grubbs’ tests
: number of results used in statistical analysis
r: repeatability limit
Sr: the standard deviation of the repeatability
the relative standard deviation of the repeatability (
x 100/MEAN).
: the HORRAT value for repeatability is the observed RSDr divided by the RSDr value estimated from the Horwitz formula using the approximation r = 0.66R
R: reproducibility limit
the standard deviation of the reproducibility
the HORRAT value for reproducibility is the observed RSDR value divided by the RSDR value calculated from HoR = RSDR(measured)/RSDR
Table 1: Hydrostatic Balance (HB)
MEAN |
n |
outliers |
n1 |
r |
sr |
RSDr |
Hor |
R |
sR |
RSDR |
HoR |
no. of replicates |
critical difference CrD95 |
|
1999/1 |
11.043 |
17 |
1 |
16 |
0.0571 |
0.0204 |
0.1846 |
0.1004 |
0.1579 |
0.0564 |
0.5107 |
0.18 |
2 |
0.1080 |
1999/2 |
11.247 |
14 |
1 |
13 |
0.0584 |
0.0208 |
0.1854 |
0.1011 |
0.1803 |
0.0644 |
0.5727 |
0.21 |
2 |
0.1241 |
1999/3 |
11.946 |
16 |
0 |
16 |
0.0405 |
0.0145 |
0.1211 |
0.0666 |
0.1593 |
0.0569 |
0.4764 |
0.17 |
2 |
0.1108 |
1999/4 |
7.653 |
17 |
1 |
16 |
0.0502 |
0.0179 |
0.2344 |
0.1206 |
0.1537 |
0.0549 |
0.7172 |
0.24 |
2 |
0.1057 |
1999/5 |
11.188 |
17 |
0 |
17 |
0.0871 |
0.0311 |
0.2780 |
0.1515 |
0.2701 |
0.0965 |
0.8622 |
0.31 |
2 |
0.1860 |
1999/6 |
11.276 |
19 |
0 |
19 |
0.0846 |
0.0302 |
0.2680 |
0.1462 |
0.2957 |
0.1056 |
0.9365 |
0.34 |
2 |
0.2047 |
1999/7 |
8.018 |
17 |
0 |
17 |
0.0890 |
0.0318 |
0.3964 |
0.2054 |
0.2573 |
0.0919 |
1.1462 |
0.39 |
2 |
0.1764 |
1999/9 |
11.226 |
17 |
0 |
17 |
0.0580 |
0.0207 |
0.1846 |
0.1423 |
0.2796 |
0.0999 |
0.8896 |
0.45 |
2 |
0.1956 |
1999/10 |
11.026 |
17 |
0 |
17 |
0.0606 |
0.0216 |
0.1961 |
0.1066 |
0.2651 |
0.0947 |
0.8588 |
0.31 |
2 |
0.1850 |
1999/11 |
7.701 |
16 |
1 |
15 |
0.0643 |
0.0229 |
0.2980 |
0.1535 |
0.2330 |
0.0832 |
1.0805 |
0.37 |
2 |
0.1616 |
1999/12 |
10.987 |
17 |
2 |
15 |
0.0655 |
0.0234 |
0.2128 |
0.1156 |
0.1258 |
0.0449 |
0.4089 |
0.15 |
2 |
0.0827 |
2000/1 |
11.313 |
16 |
0 |
16 |
0.0986 |
0.0352 |
0.3113 |
0.1699 |
0.2577 |
0.0920 |
0.8135 |
0.29 |
2 |
0.1754 |
2000/2 |
11.232 |
17 |
0 |
17 |
0.0859 |
0.0307 |
0.2731 |
0.1489 |
0.2535 |
0.0905 |
0.8060 |
0.29 |
2 |
0.1740 |
2000/3 |
0.679 |
10 |
0 |
10 |
0.0680 |
0.0243 |
3.5773 |
1.2783 |
0.6529 |
0.2332 |
34.3395 |
8.10 |
2 |
0.4604 |
2000/4 |
11.223 |
18 |
0 |
18 |
0.0709 |
0.0253 |
0.2257 |
0.1230 |
0.2184 |
0.0780 |
0.6951 |
0.25 |
2 |
0.1503 |
2000/5 |
7.439 |
19 |
1 |
18 |
0.0630 |
0.0225 |
0.3023 |
0.1549 |
0.1522 |
0.0544 |
0.7307 |
0.25 |
2 |
0.1029 |
2000/6 |
11.181 |
19 |
0 |
19 |
0.0536 |
0.0191 |
0.1710 |
0.0932 |
0.2783 |
0.0994 |
0.8890 |
0.32 |
2 |
0.1950 |
2000/7 |
10.858 |
16 |
0 |
16 |
0.0526 |
0.0188 |
0.1731 |
0.0939 |
0.1827 |
0.0653 |
0.6011 |
0.22 |
2 |
0.1265 |
2000/9 |
12.031 |
17 |
1 |
16 |
0.0602 |
0.0215 |
0.1787 |
0.0985 |
0.2447 |
0.0874 |
0.7263 |
0.26 |
2 |
0.1704 |
2000/10 |
11.374 |
18 |
0 |
18 |
0.0814 |
0.0291 |
0.2555 |
0.1395 |
0.2701 |
0.0965 |
0.8482 |
0.31 |
2 |
0.1866 |
2000/11 |
7.644 |
18 |
0 |
18 |
0.0827 |
0.0295 |
0.3863 |
0.1988 |
0.2289 |
0.0817 |
1.0694 |
0.36 |
2 |
0.1565 |
2000/12 |
11.314 |
19 |
1 |
18 |
0.0775 |
0.0277 |
0.2447 |
0.1336 |
0.2421 |
0.0864 |
0.7641 |
0.28 |
2 |
0.1667 |
2001/1 |
11.415 |
19 |
0 |
19 |
0.0950 |
0.0339 |
0.2971 |
0.1623 |
0.2410 |
0.0861 |
0.7539 |
0.27 |
2 |
0.1636 |
2001/2 |
11.347 |
19 |
0 |
19 |
0.0792 |
0.0283 |
0.2493 |
0.1361 |
0.1944 |
0.0694 |
0.6119 |
0.22 |
2 |
0.1316 |
2001/3 |
11.818 |
16 |
0 |
16 |
0.0659 |
0.0235 |
0.1990 |
0.1093 |
0.2636 |
0.0941 |
0.7965 |
0.29 |
2 |
0.1834 |
2001/4 |
11.331 |
17 |
0 |
17 |
0.1067 |
0.0381 |
0.3364 |
0.1836 |
0.1895 |
0.0677 |
0.5971 |
0.22 |
2 |
0.1229 |
2001/5 |
8.063 |
19 |
1 |
18 |
0.0782 |
0.0279 |
0.3465 |
0.1797 |
0.1906 |
0.0681 |
0.8442 |
0.29 |
2 |
0.1290 |
Table 2: Electronic Densimetry (ED)
MEAN n1 |
n |
outliers |
n1 |
r |
sr |
RSDr |
Hor |
R |
sR |
RSDR |
HoR |
no. of replicates |
critical difference CrD95 |
|
D1999/1 |
11.019 |
18 |
1 |
17 |
0.0677 |
0.0242 |
0.2196 |
0.1193 |
0.1996 |
0.0713 |
0.6470 |
0.23 |
2 |
0.1370 |
D1999/2 |
11.245 |
19 |
2 |
17 |
0.0448 |
0.0160 |
0.1423 |
0.0776 |
0.1311 |
0.0468 |
0.4165 |
0.15 |
2 |
0.0900 |
D1999/3 |
11.967 |
21 |
0 |
21 |
0.0701 |
0.0250 |
0.2091 |
0.1151 |
0.1552 |
0.0554 |
0.4631 |
0.17 |
2 |
0.1040 |
D1999/4 |
7.643 |
19 |
1 |
18 |
0.0610 |
0.0218 |
0.2852 |
0.1467 |
0.1340 |
0.0479 |
0.6262 |
0.21 |
2 |
0.0897 |
D1999/5 |
11.188 |
21 |
3 |
18 |
0.0260 |
0.0093 |
0.0829 |
0.0452 |
0.2047 |
0.0731 |
0.6536 |
0.24 |
2 |
0.1442 |
D1999/6 |
11.303 |
21 |
0 |
21 |
0.0652 |
0.0233 |
0.2061 |
0.1125 |
0.1466 |
0.0523 |
0.4631 |
0.17 |
2 |
0.0984 |
D1999/7 |
8.026 |
21 |
0 |
21 |
0.0884 |
0.0316 |
0.3935 |
0.2039 |
0.1708 |
0.0610 |
0.7600 |
0.26 |
2 |
0.1124 |
D1999/9 |
11.225 |
17 |
0 |
17 |
0.0372 |
0.0133 |
0.1183 |
0.0645 |
0.1686 |
0.0602 |
0.5366 |
0.19 |
2 |
0.1178 |
D1999/10 |
11.011 |
19 |
0 |
19 |
0.0915 |
0.0327 |
0.2969 |
0.1613 |
0.1723 |
0.0615 |
0.5588 |
0.20 |
2 |
0.1129 |
D1999/11 |
7.648 |
21 |
1 |
20 |
0.0615 |
0.0220 |
0.2872 |
0.1478 |
0.1538 |
0.0549 |
0.7183 |
0.24 |
2 |
0.1043 |
D1999/12 |
10.999 |
16 |
1 |
15 |
0.0428 |
0.0153 |
0.1389 |
0.0755 |
0.2015 |
0.0720 |
0.6541 |
0.23 |
2 |
0.1408 |
D2000/1 |
11.248 |
22 |
1 |
21 |
0.0697 |
0.0249 |
0.2212 |
0.1206 |
0.1422 |
0.0508 |
0.4516 |
0.16 |
2 |
0.0944 |
D2000/2 |
11.240 |
19 |
3 |
16 |
0.0448 |
0.0160 |
0.1424 |
0.0776 |
0.1619 |
0.0578 |
0.5145 |
0.19 |
2 |
0.1123 |
D2000/3 |
0.526 |
12 |
1 |
11 |
0.0327 |
0.0117 |
2.2185 |
0.7630 |
0.9344 |
0.3337 |
63.4009 |
14.39 |
2 |
0.6605 |
D2000/4 |
11.225 |
19 |
1 |
18 |
0.0476 |
0.0170 |
0.1514 |
0.0825 |
0.1350 |
0.0482 |
0.4295 |
0.15 |
2 |
0.0924 |
D2000/5 |
7.423 |
21 |
0 |
21 |
0.0628 |
0.0224 |
0.3019 |
0.1547 |
0.2635 |
0.0941 |
1.2677 |
0.43 |
2 |
0.1836 |
D2000/6 |
11.175 |
23 |
2 |
21 |
0.0606 |
0.0217 |
0.1938 |
0.1056 |
0.1697 |
0.0606 |
0.5424 |
0.20 |
2 |
0.1161 |
D2000/7 |
10.845 |
21 |
5 |
16 |
0.0440 |
0.0157 |
0.1449 |
0.0786 |
0.1447 |
0.0517 |
0.4766 |
0.17 |
2 |
0.0999 |
D2000/9 |
11.983 |
22 |
1 |
21 |
0.0841 |
0.0300 |
0.2507 |
0.1380 |
0.2410 |
0.0861 |
0.7183 |
0.26 |
2 |
0.1651 |
D2000/10 |
11.356 |
22 |
1 |
21 |
0.0635 |
0.0227 |
0.1997 |
0.1090 |
0.1865 |
0.0666 |
0.5866 |
0.21 |
2 |
0.1280 |
D2000/11 |
7.601 |
27 |
0 |
27 |
0.0521 |
0.0186 |
0.2448 |
0.1258 |
0.1685 |
0.0602 |
0.7916 |
0.27 |
2 |
0.1162 |
D2000/12 |
11.322 |
25 |
1 |
24 |
0.0476 |
0.0170 |
0.1503 |
0.0820 |
0.1594 |
0.0569 |
0.5028 |
0.18 |
2 |
0.1102 |
D2001/1 |
11.427 |
29 |
0 |
29 |
0.0706 |
0.0252 |
0.2207 |
0.1206 |
0.1526 |
0.0545 |
0.4771 |
0.17 |
2 |
0.1020 |
D2001/2 |
11.320 |
29 |
1 |
28 |
0.0675 |
0.0241 |
0.2128 |
0.1161 |
0.1570 |
0.0561 |
0.4952 |
0.18 |
2 |
0.1057 |
D2001/3 |
11.826 |
34 |
1 |
33 |
0.0489 |
0.0175 |
0.1476 |
0.0811 |
0.1762 |
0.0629 |
0.5322 |
0.19 |
2 |
0.1222 |
D2001/4 |
11.339 |
31 |
2 |
29 |
0.0639 |
0.0228 |
0.2012 |
0.1099 |
0.1520 |
0.0543 |
0.4788 |
0.17 |
2 |
0.1026 |
D2001/5 |
8.058 |
28 |
0 |
28 |
0.0473 |
0.0169 |
0.2098 |
0.1088 |
0.2025 |
0.0723 |
0.8976 |
0.31 |
2 |
0.1412 |
Table 3: Comparison of results between hydrostatic balance and electronic densimetry
MEAN (HB) |
n |
outliers |
n1 |
MEAN (ED) |
n |
outliers |
n1 |
TAV(HB-ED) |
|||||
1999/1 |
11.043 |
17 |
1 |
16 |
D1999/1 |
11.019 |
18 |
1 |
17 |
0.024 |
|||
1999/2 |
11.247 |
14 |
1 |
13 |
D1999/2 |
11.245 |
19 |
2 |
17 |
0.002 |
|||
1999/3 |
11.946 |
16 |
0 |
16 |
D1999/3 |
11.967 |
21 |
0 |
21 |
-0.021 |
|||
1999/4 |
7.653 |
17 |
1 |
16 |
D1999/4 |
7.643 |
19 |
1 |
18 |
0.010 |
|||
1999/5 |
11.188 |
17 |
0 |
17 |
D1999/5 |
11.188 |
21 |
3 |
18 |
0.000 |
|||
1999/6 |
11.276 |
19 |
0 |
19 |
D1999/6 |
11.303 |
21 |
0 |
21 |
-0.028 |
|||
1999/7 |
8.018 |
17 |
0 |
17 |
D1999/7 |
8.026 |
21 |
0 |
21 |
-0.008 |
|||
1999/9 |
11.226 |
17 |
0 |
17 |
D1999/9 |
11.225 |
17 |
0 |
17 |
0.002 |
|||
1999/10 |
11.026 |
17 |
0 |
17 |
D1999/10 |
11.011 |
19 |
0 |
19 |
0.015 |
|||
1999/11 |
7.701 |
16 |
1 |
15 |
D1999/11 |
7.648 |
21 |
1 |
20 |
0.052 |
|||
1999/12 |
10.987 |
17 |
2 |
15 |
D1999/12 |
10.999 |
16 |
1 |
15 |
-0.013 |
|||
2000/1 |
11.313 |
16 |
0 |
16 |
D2000/1 |
11.248 |
22 |
1 |
21 |
0.065 |
|||
2000/2 |
11.232 |
17 |
0 |
17 |
D2000/2 |
11.240 |
19 |
3 |
16 |
-0.008 |
|||
2000/3 |
0.679 |
10 |
|
0 |
10 |
D2000/3 |
0.526 |
12 |
|
1 |
11 |
* |
0.153 |
2000/4 |
11.223 |
18 |
0 |
18 |
D2000/4 |
11.225 |
19 |
1 |
18 |
-0.002 |
|||
2000/5 |
7.439 |
19 |
1 |
18 |
D2000/5 |
7.423 |
21 |
0 |
21 |
0.016 |
|||
2000/6 |
11.181 |
19 |
0 |
19 |
D2000/6 |
11.175 |
23 |
2 |
21 |
0.006 |
|||
2000/7 |
10.858 |
16 |
0 |
16 |
D2000/7 |
10.845 |
21 |
5 |
16 |
0.013 |
|||
2000/9 |
12.031 |
17 |
1 |
16 |
D2000/9 |
11.983 |
22 |
1 |
21 |
0.049 |
|||
2000/10 |
11.374 |
18 |
0 |
18 |
D2000/10 |
11.356 |
22 |
1 |
21 |
0.018 |
|||
2000/11 |
7.644 |
18 |
0 |
18 |
D2000/11 |
7.601 |
27 |
0 |
27 |
0.043 |
|||
2000/12 |
11.314 |
19 |
1 |
18 |
D2000/12 |
11.322 |
25 |
1 |
24 |
-0.008 |
|||
2001/1 |
11.415 |
19 |
0 |
19 |
D2001/1 |
11.427 |
29 |
0 |
29 |
-0.012 |
|||
2001/2 |
11.347 |
19 |
0 |
19 |
D2001/2 |
11.320 |
29 |
1 |
28 |
0.027 |
|||
2001/3 |
11.818 |
16 |
0 |
16 |
D2001/3 |
11.826 |
34 |
1 |
33 |
-0.008 |
|||
2001/4 |
11.331 |
17 |
0 |
17 |
D2001/4 |
11.339 |
31 |
2 |
29 |
-0.008 |
|||
2001/5 |
8.063 |
19 |
1 |
18 |
D2001/5 |
8.058 |
28 |
0 |
28 |
0.004 |
|||
Average difference/ TAV (HB-ED) |
0.014 |
||||||||||||
standard deviation on difference |
0.036 |
||||||||||||
* |
round 2000/3 is not taken into account (very low grade) |
||||||||||||
Table 4: Fidelity parameters
MEAN |
Hydrostatic balance |
Electronic densimeter |
|
n1 |
441 |
557 |
|
Weighted repeatability variance |
0.309 |
0.267 |
|
r |
0.074 |
0.061 |
|
sr |
0.026 |
0.022 |
|
Weighted reproducibility variance |
2.948 |
2.150 |
|
R |
0.229 |
0.174 |
|
sR |
0.082 |
0.062 |