1. Anton Paar GmbH Anton-Paar-Str. 20, 8054 Graz, Austria-Europe Internet: http://www.anton-paar.com CarboQC Lab and at-line Beverage Carbonation Meter

2. Anton Paar GmbH Anton-Paar-Str. 20, 8054 Graz, Austria-Europe Internet: http://www.anton-paar.com Contents of this presentation Basics of CO 2 analysis Multiple Volume Expansion method CarboQC Lab and at-line beverage carbonation meter

3. Anton Paar GmbH Anton-Paar-Str. 20, 8054 Graz, Austria-Europe Internet: http://www.anton-paar.com Basics of CO 2 analysis What are the fundamental laws involved? How can the fundamental laws be applied to solve practical problems? How is the CO 2 solubility influenced and what are the consequences?

4. Anton Paar GmbH Anton-Paar-Str. 20, 8054 Graz, Austria-Europe Internet: http://www.anton-paar.com Fundamental gas laws in beverage CO 2 measurement c co 2 = ξco 2 * p co 2 Henrys law p tot = p co 2 + p Air + p H 2 O Daltons law c … concentrationξ … absorption / solubilityp … pressure m … massM … molar massV … volume R … gas constant Z … compression factor T … temp. m = p*M*V/R*T*Z Real gas law

5. Anton Paar GmbH Anton-Paar-Str. 20, 8054 Graz, Austria-Europe Internet: http://www.anton-paar.com CO 2 measurement units [g/l] Grams of CO 2 per liter of liquid Volumes [Vol.] Volumes of CO 2 at 0°C and 1 atm diss. per liquid volume 1 Vol. = 1.976 g/l Conversion

6. Anton Paar GmbH Anton-Paar-Str. 20, 8054 Graz, Austria-Europe Internet: http://www.anton-paar.com Combining the fundamental laws: #1 What happens in a bottle/can/chamber? p 2 *V 2L * ξ 2 gas mass dissolved in liquid volume V 2L p 2 *V 2G *M/(R*T 2 *Z 2 ) gas mass in gas volume V 2G p 1L *V 1L * ξ 1 gas mass dissolved in liquid volume V 1L p 1G *V 1G *M/(R*T 1G *Z 1 ) gas mass in gas volume V 1G Initial state (1): before volume / temperature / solubility change no equilibrium or equilibrium between phases Final state (2): after volume / temperature / solubility change equilibrium between phases

7. Anton Paar GmbH Anton-Paar-Str. 20, 8054 Graz, Austria-Europe Internet: http://www.anton-paar.com Combining the fundamental laws: #2 What happens in a bottle/can/chamber? p 2 = ? Gas solubility (Volumes of dissolved gas per volume of liquid at standard conditions) L = ξ / (M/(R*T 0 *Z 0 )) Equilibrium pressure in final state (2)

8. Anton Paar GmbH Anton-Paar-Str. 20, 8054 Graz, Austria-Europe Internet: http://www.anton-paar.com From:Rammert / Pahl, Brauwelt Nr. 12 Nürnberg 1991 CO 2 absorption coefficient / solubility is influenced by - temperature - sugar - acids & flavors - CO 2 pressure - dissolved air - etc. CO 2 absorption coefficient

9. Anton Paar GmbH Anton-Paar-Str. 20, 8054 Graz, Austria-Europe Internet: http://www.anton-paar.com Non-equilibrium state at bottle/can filling e.g. 10% headsp. 90% liquid volume At filling: Most CO 2 dissolved in beverage, little CO 2 in headspace if not actively enriched Equilibrium: CO 2 distributed approx. proportional to liquid to headspace ratio Headspace: Cans: 3...5% Bottles: 5...12% 0.33 Vol. 3.32 Vol. ~100% CO 2 e.g. 3.65 Vol. ~0% CO 2

10. Anton Paar GmbH Anton-Paar-Str. 20, 8054 Graz, Austria-Europe Internet: http://www.anton-paar.com Headspace related temperature effect 10% gas volume 90% liquid volume CO 2 dissolved in beverage at 40°F / 4°C in equilibrium state: CO 2 dissolved in same beverage at 70°F/ 21°C in equilibrium state: Beverage container: e.g. 10% headspace 0.40 Vol. 3.25 Vol. 3.40 Vol. 0.25 Vol.

11. Anton Paar GmbH Anton-Paar-Str. 20, 8054 Graz, Austria-Europe Internet: http://www.anton-paar.com Multiple Volume Expansion Method What happens to the gas partial pressures when the volume of the measuring chamber is expanded? How and why does the Multiple Volume Expansion Method work? What are the results?

12. Anton Paar GmbH Anton-Paar-Str. 20, 8054 Graz, Austria-Europe Internet: http://www.anton-paar.com CO 2 and air equilibrium pressures as a function of volume expansion The air pressure decreases excessively because the solubility of air is much lower than that of CO 2 !

13. Anton Paar GmbH Anton-Paar-Str. 20, 8054 Graz, Austria-Europe Internet: http://www.anton-paar.com CO 2 measurement w/o air compensation

14. Anton Paar GmbH Anton-Paar-Str. 20, 8054 Graz, Austria-Europe Internet: http://www.anton-paar.com CO 2 measurement w/o air compensation

15. Anton Paar GmbH Anton-Paar-Str. 20, 8054 Graz, Austria-Europe Internet: http://www.anton-paar.com CO 2 error due to dissolved air

16. Anton Paar GmbH Anton-Paar-Str. 20, 8054 Graz, Austria-Europe Internet: http://www.anton-paar.com How does the Multiple Volume Expansion Method work? A measuring chamber is completely filled with sample and sealed. The volume of the measuring chamber is expanded. Pressure and temperature equilibrium is generated. Equilibrium pressure and temperature are measured. The measuring chamber volume is further expanded, equilibrium is generated and pressure and temperature are again measured. The two pressures/temperatures are used for CO2 determination and dissolved air compensation.

17. Anton Paar GmbH Anton-Paar-Str. 20, 8054 Graz, Austria-Europe Internet: http://www.anton-paar.com CarboQC Multiple Volume Expansion Method 1. measurement deviation ? correction ! 2. measurement

18. Anton Paar GmbH Anton-Paar-Str. 20, 8054 Graz, Austria-Europe Internet: http://www.anton-paar.com Why does the Multiple Volume Expansion Method work? The Multiple Volume Expansion method makes use of the fact that the solubility of CO 2 is much higher than that of air. By expanding the volume of the measuring chamber the partial pressures of CO 2 and air change very differently. Therefore CO 2 and air partial pressures can be distinguished and the effect of dissolved air removed.

19. Anton Paar GmbH Anton-Paar-Str. 20, 8054 Graz, Austria-Europe Internet: http://www.anton-paar.com CarboQC Multiple Volume Expansion - Results

20. Anton Paar GmbH Anton-Paar-Str. 20, 8054 Graz, Austria-Europe Internet: http://www.anton-paar.com CarboQC Lab and at-line beverage carbonation meter New patented MVE Multiple Volume Expansion method No influence from dissolved air For accurate and traceable CO 2 measurements

21. Anton Paar GmbH Anton-Paar-Str. 20, 8054 Graz, Austria-Europe Internet: http://www.anton-paar.com CarboQC Measuring chamber Display Keypad

22. Anton Paar GmbH Anton-Paar-Str. 20, 8054 Graz, Austria-Europe Internet: http://www.anton-paar.com CarboQC Rear view

23. Anton Paar GmbH Anton-Paar-Str. 20, 8054 Graz, Austria-Europe Internet: http://www.anton-paar.com CarboQC ON / OFF switch Water-tight connection plug

24. Anton Paar GmbH Anton-Paar-Str. 20, 8054 Graz, Austria-Europe Internet: http://www.anton-paar.com CarboQC with semi-automatic filling device

25. Anton Paar GmbH Anton-Paar-Str. 20, 8054 Graz, Austria-Europe Internet: http://www.anton-paar.com Specifications of the CarboQC Measuring range 0 to 12 g/l (0 to 6 Vol.)at 30°C (86°F) 0 to 20 g/l (0 to 10 Vol.)< 15°C (59°F)

26. Anton Paar GmbH Anton-Paar-Str. 20, 8054 Graz, Austria-Europe Internet: http://www.anton-paar.com Specifications of the CarboQC Repeatability0.005 bar(0.07 psia) 0.05°C(0.1°F) 0.01 g/l(0.005 Vol.) Reproducibility0.015 bar(0.21 psia) 0.1°C(0.2 °F) 0.05 g/l(0.025 Vol.)

27. Anton Paar GmbH Anton-Paar-Str. 20, 8054 Graz, Austria-Europe Internet: http://www.anton-paar.com Benefits of the CarboQC No influence from dissolved air Highly accurate absolute pressure sensor no weather and sea level influence Very accurate temperature measurement due to impeller technique No calibration/adjustment with reference methods or CO 2 standards necessary Zero point calibration simply with (tap) water Small amounts of sample Fast and accurate results in a wide temperature range Versatile and easy to use with PFD filling device

28. Anton Paar GmbH Anton-Paar-Str. 20, 8054 Graz, Austria-Europe Internet: http://www.anton-paar.com Comparison to Zahm & Nagel results Zahm & Nagel requires snifting (venting) at bottles to decrease air influence leads to temperature & headspace volume dependent loss of CO 2 Zahm & Nagel is subject to full influence of air at cans due to no snifting being possible Zahm & Nagel pressure and temperature measurement provides only limited accuracy Headspace related temperature effect causes deviations The CarboQC provides more precise results than Zahm & Nagel CarboQC results are lower due to lack of air influence

29. Anton Paar GmbH Anton-Paar-Str. 20, 8054 Graz, Austria-Europe Internet: http://www.anton-paar.com Comparison to membrane-type instruments Drift due to change of membrane permeability Frequent recalibration necessary Influenced by sample pressure and flow rate Limited temperature range of calibration Large amount of sample required Reliable measurement, no drift Virtually no calibration necessary No influence of sample pressure and flow rate Accurate results on cold and warm samples Small amount of sample CarboQC Membrane-type

30. Anton Paar GmbH Anton-Paar-Str. 20, 8054 Graz, Austria-Europe Internet: http://www.anton-paar.com CarboQC summary Lab and at-line beverage carbonation meter Patented Multiple Volume Expansion method No influence from dissolved air Easy to use, fast and accurate Wide measurement temperature range Small amount of sample