Innovative Measurement Solutions www.cosaxentaur.com What is H2O and its Measurement Effects David Hailey, Ph.D. June 20th, 2013 Yes, I am “that” old 😆 www.cosaxentaur.com My late 1980’s Midwest Measurement Society badge, I am wearing it today ☺ www.cosaxentaur.com Moisture Basics Water exists in many forms… NOTE: Steam is typically regarded as a liquid, all gasses are invisible & if you can see it, then it's not a gas… 3 www.cosaxentaur.com What properties does water (H20) have? www.cosaxentaur.com Moisture Basics: Water Molecules Active molecules which can migrate 5 www.cosaxentaur.com Moisture Basics: Water Molecule A water molecule consists of one oxygen and two hydrogen atoms. QuickTime™ and a TIFF (Uncompressed) decompressor ar e needed to see this picture. Van der Waal radius of water: 2.82 Å to 3.2Å 6 www.cosaxentaur.com Moisture Basics: Water Molecules Size compared to: Molecular Weight Size Å Water H2O 18 1.3 - 1.77 Methane CH4 16 2.6 Benzene C6H6 78 5.68 Methanol CH3OH 32 2.9 Relatively a small molecule 7 www.cosaxentaur.com Moisture Basics: States of Water Vapor Van der Waal Forces Liquid Water Hydrogen bonding 8 www.cosaxentaur.com Moisture Basics: Saturated Vapor Pressure The process of evaporation in a closed container will proceed until there are as many molecules returning to the liquid as there are escaping. At this point the vapor is said to be saturated, and the pressure of that vapor (usually expressed in mmHg) is called the saturated vapor pressure. Since the molecular kinetic energy is greater at higher temperature, more molecules can escape the surface and the saturated vapor pressure is correspondingly higher. If the liquid is open to the air, then the vapor pressure is seen as a partial pressure along with the other constituents of the air. The temperature at which the vapor pressure is equal to the atmospheric pressure is called the boiling point. 9 Moisture Basics: A Simpler View: Equilibrium www.cosaxentaur.com Rates of evaporation and condensation are equal 10 Moisture Basics: Its about energy……. www.cosaxentaur.com q q A molecule evaporates when sufficient kinetic energy is gained through collisions with its neighbors for it to overcome the attractive forces between the liquid molecules. These forces include hydrogen bonds and Van der Waals force. As the molecule escapes it takes with it kinetic energy, leaving the water surface with a diminished total kinetic energy. A molecule condenses when it is moving slowly enough and is pulled back to the water surface by the attractive forces, i.e. its velocity is insufficient to resist the pull of the various forces of attraction. The molecule plunges into the water, transferring energy to the molecules near where it hit the surface and is once again liquid 11 Moisture Basics: Water Vapor q www.cosaxentaur.com q q Water vapor is water in pure gas phase It is not to be mistaken with steam, clouds, fog, mist, etc. where water is present in the form of droplets In gas form, behaves like an ideal gas: PV=nRT P ≡ Pressure V ≡ Volume n ≡ Number of moles of gas R ≡ Gas Constant T ≡ Absolute Temperature 12 www.cosaxentaur.com Moisture Basics: Water Vapor www.cosaxentaur.com Moisture Basics: Boyle’s Law . Animated graphics from NASA 2009, J. David Hailey Ph.D www.cosaxentaur.com Moisture Basics: Charle’s Law . Animated graphics from NASA 2009, J. David Hailey Ph.D Moisture Basics: Dalton’s Law John Dalton (1766 - 1844) www.cosaxentaur.com If there are n gases, the total pressure is the sum of the partial pressures of the n gases P(t) = P(1) + P(2) + ….. +P(n) All the n gases act independently from each other, as if the other gases did not exist! So in the atmosphere (14.7 psia) made up of primary nitrogen and oxygen P(atm) = P(nitrogen) + P(oxygen) + P(H2O) ….. +P(n) 16 www.cosaxentaur.com Moisture Basics: Practical Application of Daltons Law q q q Partial Water Vapor Pressure of Environment is higher than that of Pipeline. Pipeline absolute pressure is greater than the environment. Water will ingress the pipeline where ever it will find an opening. 17 www.cosaxentaur.com Moisture Basics: Absorption into materials Water is everywhere……. and is either part of or absorbed by almost all materials: • Plastics • Steel • Glass Any change in the energy level changes the equilibrium between evaporation and condensation. Taking this concept further, any change in energy (normally denoted by temperature) changes the amount of water absorbed in a material. www.cosaxentaur.com Moisture Basics: The Diurnal Effect As the atmosphere heats during the day, the moisture equilibrium in all materials changes as increased thermal energy increases evaporation rates. This occurs indoors as well as in external systems. The extent of the fluctuations depends on the wetted materials. Moisture Basics: Take Away • Moisture is everywhere. www.cosaxentaur.com • Water is a small mobile molecule. • Water behaves as a ideal gas; if you can see it, it is already liquid. • Water is absorbed in almost every material. • Any change in temperature shifts the condensation/evaporation equilibrium. • Gas phase water is typically higher in the ambient environment than in the process being measured. • Dalton’s Law applies being one of the least understood but most troublesome issues in moisture measurement. Moisture Measurement: Units of Measure www.cosaxentaur.com Moisture is measured in various different engineering units, that are suitable for particular applications: § Water Vapor Pressure (mbar, mm Hg, etc.) § Dewpoint (°C, °F) § Parts per million by volume (ppmv) § Parts per million by weight (ppmw) § Lbs of water per million standard cubic feet (at temp and pressure) § Grams per cubic meter (g/m3) § Relative humidity (% @ temperature) § Ug/ml (absolute measurement) These are not linear conversions; ppm to dew point is logarithmic, lbs H2O/ MMCF is a density measurement, dew point is pressure dependent etc. This means that the accuracy statements between units needs to be recalcualted based on dew point. 21 190 10.00 180 9.00 8.00 170 7.00 160 6.00 150 ppmv www.cosaxentaur.com Moisture Measurement: Units Comparison 5.00 140 4.00 130 3.00 120 110 100 ppmv is a concentration measurement whereas lbs H2O/MMCF is density 2.00 1.00 0.00 l b s / M M C F ppmV LBS MMCF Moisture Measurement: M-Calc training www.cosaxentaur.com Free conversion software from COSA Xentaur at www.cosaxentaur.com www.cosaxentaur.com Certified Moisture Dew Point Calibration Standard The calibration gas is supplied in specifically lined high pressure aluminum cylinders, which will discharge a constant water concentration from 1800 psi to 200 psi for nitrogen/water blends from 1 to 150 ppmv. NIST Traceable. Blending accuracy is ±10% and analytical accuracy is ±2%. The concentration is guaranteed for two years. NOTES: 1. Use N2 standards if under 70°F (21°FC), as CH4 standards will need a 4-stage regulator to keep Joule-Thomson effect from condensing out he H2O in the standard and you get a low (bad) calibration or reference measurement value. 2. TDLAS based measurement will read incorrectly (apx. -40% low) with N2 background in calibration standard. 3. HTF based will measure correctly regardless of background gas. Can Calibrate these units, and check others ESS: When things go bad….. www.cosaxentaur.com Joule Thomson effect in PA; 2012. Note insulation and the regulator still froze up. www.cosaxentaur.com ESS: When things go bad….. Same site, again: A brass regulator at the sample take off point. www.cosaxentaur.com ESS: When things go bad….. Brass regulators, Also consider the diurnal effects on the standards and the stream www.cosaxentaur.com Thank you for your attention, and your time!
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