Redox Potential Electrodes

Platinum, Gold and Silver Electrodes

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Redox is an ideal solution for testing the oxidation/reduction in factory and industrial waste (chromium and cyanide concentration), fish farming and aquariums (water quality), and swimming pools (sanitation levels).

InLab ORP/Redox Electrodes

LE ORP/Redox Electrodes

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The BASi Oxygen Electrode.

Welcome to the dissolved oxygen (D.O.) theory Page. Basic principles of Polagrography cell (electrode) Polar gram EIDs dissolved oxygen electrode picture Electrode reactions Number of electrons involved Calibration Calibration in air saturated with water vapor Calibration in air saturated water Checking the sensor function Measurement and analytical quality assurance Cleaning of sensors Regeneration of sensors Polarization periods (startup periods) prior to measurement Approach flow Correction for salt content Influence of interfering gases Solubility functions Checking the oxygen meter and or logger Dissolved oxygen Applications Practical experiments

Dissolved Oxygen: The air we breathe contains about 20% oxygen. Fish and other aquatic organisms require oxygen as well. The term Dissolved Oxygen (DO or D.O.) refers to the amount of free oxygen dissolved in water which is readily available to respiring aquatic organisms. Water quality standards often express minimum concentrations of dissolved oxygen which must be maintained in order to support life as well as be of beneficial use. Levels of dissolved oxygen below 4-5 milligrams per liter affect fish health and levels below 2 milligrams per liter can be lethal to fish. Additionally, biochemical oxygen demand (BOD) is commonly used with reference to effluent discharges and is a common, environmental procedure for determining the extent to which oxygen within a sample can support microbial life. The test for BOD is especially important in waste water treatment, food manufacturing, and filtration facilities where the concentration is crucial to the overall process and end products. High concentrations of DO predict that oxygen uptake by microorganisms is low along with the required break down of nutrient sources in the medium. Basic principles of Polagrography cell: Liquid and Air state of equilibrium is reached when the partial pressure of oxygen, i.e. the part of the total pressure that is due to oxygen, is equal in air and in liquid. The liquid is then saturated with oxygen.

Figure 1.1 Air and liquid oxygen equilibrium

Polargram: When an electrode of noble metal such as platinum or gold is made 0.6 to 0.8 V negative with respect to a

suitable reference electrode such as AgAgCl or an calomel electrode in a neutral KCI solution (see Figure 1.2), the oxygen dissolved in the liquid is reduce at the surface of the noble metal.

Figure 1.2 Polarographhy diagram This above phenomenon can be observed from a current to voltage diagram called a polarogram of the electrode. As shown in Figure 1.3a, the negative voltage applied to the noble metal electrode (called the cathode) is increased, the current increases initially but soon it becomes saturated. In this plateau region of the polarogram, the reaction of oxygen at the cathode is so fast that the rate of reaction is limited by the diffusion of oxygen to the cathode surface. When the negative bias voltage is further increased, the current output of the electrode increases rapidly due to other reactions, mainly, the reduction of water to hydrogen. If a fixed voltage in the plateau region (for example, 0.6V) is applied to the cathode, the current output of the

electrode can be linearly calibrated to the dissolved oxygen (Figure 1.3b). It has to be noted that the current is proportional not to the actual concentration but to the activity or equivalent partial pressure of dissolved oxygen, which is often referred to as oxygen tension. A fixed voltage between -0.6 and -0.8 V is usually selected as the polarization voltage when using Ag/AgCl as the reference electrode or any other EID's dissolved oxygen electrodes. Additionally for physical and chemical correctness, partial pressure in a liquid actually refers to the fugacity. In the pressure range relevant to the measurements at hand, it is acceptable to equate the two values and this allows us to restrict the following considerations to the partial pressure. In dry, atmospheric air, the partial pressure of oxygen is 20.95% of the air pressure. This value is reduced over a water surface because water vapor has its own vapor pressure and a corresponding partial pressure.

Figure 1.3 (a) Current to voltage diagram at different oxygen tension; (b) Calibration obtained at a fixed polarization voltage of 600 mV. When the cathode, the reference electrode, and the electrolyte are separated from the measurement medium by a polymer membrane, which is permeable to the dissolved gas but not to most of the ions and other species, and when most of the mass transfer resistance is confined in the membrane, EIDs electrode

system can measure oxygen tension in various liquids. This is the basic operating principle of the membrane covered polarographic Dissolve oxygen probe (Figure 1.4). The basic principle underlying the electrochemical determination of oxygen concentration is the use of membrane covered electrochemical sensors. The main components of the sensors are the oxygen permeable membrane, the working electrode, the electrolyte solution and a possible reference electrode. A voltage is applied between the gold (platinum or silver) cathode and the anode that consists of either lead or silver (AgAgCl), and causes the oxygen to react electrochemically. The higher the oxygen concentration the higher the resulting electric current. The current in the sensor is measured and, after calibration, converted into the concentration of dissolved oxygen. If the anode is made of silver, the meter applies the required voltage (polarographic sensor). If it is made of lead, the sensor is self-polarizing, i.e. the voltage is generated in the sensor by the electrodes themselves, comparable to the process in a battery (galvanic sensor). The meter merely evaluates the current.

Figure 1.4 Basic Polarographhy electrode

EIDs polaragraphoc dissolved oxygen electrode picture:

EIDs ELECTRODER - ABS body Dissolved Oxygen Sensor (ADO) EIDs dissolved oxygen, Probe, polaragraphic, ABS body, 12mm * 120mm, with 10K Negative Temperature Compensation Figure 1.5 Basic Polarographhy-electrode

Electrode reactions: For our polarographic electrodes, the reaction proceeds as follows: Cathodic reaction: 02 + 2H2 0 + 2e- H2O2 + 2OHH202 + 2e- -> 20H Anodic reaction: Ag + Cl- AgCl + e Overall reaction: 4Ag + 02 + 2 H2O + 4 Cl- 4 AgCl + 4 OHThe reaction tends to produce alkalinity in the medium together with a small amount of hydrogen peroxide.

Figure 1.4b Two-point calibration The rate at which oxygen enters a dissolved oxygen probe is a function of: the concentration of oxygen in the sample the diffusion coefficient/permeability of the membrane (function of temperature

Correction Altitude Pressure Calibration (ft) (mm Hg) Correction Factor -540 775 1.02 Sea 760 1 Level 500 746 0.98 1000 732 0.96 1500 720 0.95 2000 707 0.93 2500 694 0.91 3000 681 0.9 3500 668 0.88 4000 656 0.86

4500 5000 5500 6000

644 632 621 609

0.85 0.83 0.82 0.8

Table 1: Oxygen Value Corrected for Pressure (25 C) Relative Humidity and temperature effect and Temperature compensation %. DO (100% DO (0% Temperature R.H.) R.H.) (Celsius) (ppm, (ppm, mg/L) mg/L) 0 14.6 14.66 1 14.19 14.26 2 13.81 13.89 3 13.44 13.53 4 13.09 13.18 5 12.75 12.85 6 12.43 12.54 7 12.12 12.23 8 11.83 11.94 9 11.55 11.66 10 11.27 11.4 11 11.01 11.14 12 10.76 10.9 13 10.52 10.66 14 10.29 10.44 Table 2 above: Dissolved Oxygen Solubility vs. Temperature

Temperatur 790 e (Celsius) 15. 0 2 14. 1 8 14. 2 4 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

775 760 745 730 715 700 685 670 665 14. 6 14. 2 13. 8 13. 4 13. 1 12. 8 12. 4 12. 1 11. 8 11. 6 11. 3 11 10. 8 10. 5 10. 3 10. 1 9.8 5 9.6 5 9.4 5 14. 3 13. 9 13. 5 13. 2 12. 8 12. 5 12. 2 11. 9 11. 6 11. 3 11 10. 8 10. 5 10. 3 10. 1 9.8 7 9.6 5 9.4 6 9.2 6 13. 13. 13. 7 4 2 13. 13. 13. 12. 6 3 1 8 13. 12. 12. 13 3 7 4 12. 12. 12. 12. 9 6 4 1 12. 12. 12. 11. 6 3 1 8 12. 11. 11. 12 2 7 5 11. 11. 11. 11. 9 7 4 2 11. 11. 11. 10. 6 4 2 9 11. 11. 10. 10. 4 1 9 7 11. 10. 10. 10. 1 9 6 4 10. 10. 10. 10. 8 6 4 1 10. 10. 10. 9.9 6 4 1 1 10. 10. 9.6 9.9 3 1 8 10. 9.8 9.6 9.4 1 9 8 7 9.8 9.6 9.4 9.2 8 7 6 6 9.6 9.4 9.2 9.0 7 6 6 6 9.4 9.2 9.0 8.8 5 6 6 6 9.2 9.0 8.8 8.6 6 7 7 8 9.0 8.8 8.6 8.5 7 8 9 14 12. 9 12. 5 12. 2 11. 8 11. 5 11. 2 10. 9 10. 7 10. 4 10. 2 9.9 2 9.6 9 9.4 7 9.2 6 9.0 5 8.8 6 8.6 6 8.4 8 8.3 1 12. 6 12. 2 11. 9 11. 6 11. 3 11 10. 7 10. 4 10. 2 9.9 4 9.6 9 9.4 7 9.2 5 9.0 4 8.8 5 8.6 5 8.4 6 8.2 9 8.1 2

14. 9 14. 5 14. 1 13. 14 7 13. 13. 6 4 13. 13 3 12. 12. 9 7 12. 12. 6 4 12. 12. 3 1 11. 12 8 11. 11. 7 5 11. 11. 5 2 11. 11 2 10. 10. 9 7 10. 10. 7 5 10. 10. 5 3 10. 10. 3 1 9.8 10 4 9.8 9.6 3 4

19 20 21 22 23
Temperature (Celsius) 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23

9.6 3 9.4 4 9.2 6 9.0 7 8.9 1

9.4 9.2 9.0 8.8 8.7 5 6 7 9 9.2 9.0 8.8 8.5 8.7 5 7 9 2 9.0 8.7 8.5 8.3 8.9 8 2 4 6 8.7 8.5 8.3 8.1 8.9 2 4 7 9 8.7 8.5 8.3 8.2 8.0 3 6 9 1 4

8.5 1 8.3 4 8.1 8 8.0 1 7.8 6

8.3 8.1 7.9 3 4 5 8.1 7.9 7.7 5 7 9 7.8 7.6 8 2 4 7.8 7.6 7.4 4 6 8 7.6 7.5 7.3 9 2 4

15.2 14.8 14.4 14 13.6 13.3 12.9 12.6 12.3 12 11.7 11.5 11.2 10.9 10.7 10.5 10.3 10 9.83 9.63 9.44 9.26 9.07 8.91

14.9 14.5 14.1 13.7 13.4 13 12.7 12.4 12.1 11.8 11.5 11.2 11 10.7 10.5 10.3 10.1 9.84 9.64 9.45 9.25 9.08 8.9 8.73

14.6 14.2 13.8 13.4 13.1 12.8 12.4 12.1 11.8 11.6 11.3 11 10.8 10.5 10.3 10.1 9.85 9.65 9.45 9.26 9.07 8.9 8.72 8.56

14.3 13.9 13.5 13.2 12.8 12.5 12.2 11.9 11.6 11.3 11 10.8 10.5 10.3 10.1 9.87 9.65 9.46 9.26 9.07 8.89 8.72 8.54 8.39

14 13.6 13.3 12.9 12.6 12.2 11.9 11.6 11.4 11.1 10.8 10.6 10.3 10.1 9.88 9.67 9.45 9.26 9.07 8.89 8.7 8.54 8.37 8.21

13.7 13.3 13 12.6 12.3 12 11.7 11.4 11.1 10.9 10.6 10.4 10.1 9.89 9.67 9.46 9.26 9.07 8.88 8.7 8.52 8.36 8.19 8.04

13.4 13.1 12.7 12.4 12.1 11.7 11.4 11.2 10.9 10.6 10.4 10.1 9.9 9.68 9.46 9.26 9.06 8.87 8.69 8.51 8.34 8.18 8.01 7.86

13.2 12.8 12.4 12.1 11.8 11.5 11.2 10.9 10.7 10.4 10.1 9.91 9.68 9.47 9.26 9.06 8.86 8.68 8.5 8.33 8.15 8 7.84 7.69

12.9 12.5 12.2 11.8 11.5 11.2 10.9 10.7 10.4 10.2 9.92 9.69 9.47 9.26 9.05 8.86 8.66 8.48 8.31 8.14 7.97 7.82 7.66 7.52

12.6 12.2 11.9 11.6 11.3 11 10.7 10.4 10.2 9.94 9.69 9.47 9.25 9.04 8.85 8.65 8.46 8.29 8.12 7.95 7.79 7.64 7.48 7.34

Table 3 above: Oxygen concentration (ppm) for varying pressures (mmHg) and temperatures (degrees Celsius) at 100% relative humidity