Kudsen's automatic pipette, developed by the Danish physicist Martin Knudsen (1871-1949), allows quick and accurate transfer of a constant volume of liquid (sea water), usually around 15 mL. On the top of pipette is a double sided C vent that can establish flow between the body of the pipette and one of the branches (A or B), or isolate the body of the pipette from both of the branches. Sucking through the B branch the pipette is filled with liquid, it is closed with a twist of the C valve and the liquid is released by rotating the valve towards the A branch (so atmospheric air can enter the pipette). Emptying the pipette takes around 30 seconds. Before it's first use, the pipette must be calibrated with distilled water.
Knudsen's automatic bulb-burette, developed by the Danish physicist Martin Knudsen (1871-1949), is designed in a way that even routine field analysis in a boat laboratory would provide highly accurate measurements. The burette is filled with a mixture of silver nitrate from reservoir R, located above the burette, by opening the A valve. When the solution crosses the three-way C valve the A valve is closed preventing further solution flow in to the burette. Any extra solution is caught in the W bowl. Turn the C valve, which marks the zero on the scale, in order to allow atmospheric air to enter the burette. Since most open-ocean samples lie in a relatively small chlorinity range, the burette is designed so that much of its capacity is in the bulb (B). This allows the titration to be quick (by quickly releasing contents from the B area) and reduces the error that occurs from the slow drainage along the inner wall of the burette.
Each millimeter is divided in to twenty parts (double millimeter division of the Knudsen burette) which allows for highly accurate measurements (the scale is read up to a precision of 0.005 mL). From 0 to 16 the burette isn't divided, that usually starts from 16 and goes until 20.5 or 21.5. A single double millimeter on a Knudsen burette scale corresponds to one permille of chloride in the seawater sample. This burette can be used for titration of water from all of the oceans and seas, with the exemptions being areas with very low salinity (e.g. the Baltic Sea) and river estuaries which require the use of normal burettes.
For general reaction of some redox system
dependence of electrode potential of redox system upon activity of oxidised and reduced form in solution is described in Nernst’s equation for electrode potential:
where E = to electrode potential of redox system
E° = standard electrode potential of redox system
R = universal gas constant
T = thermodymical temperature
F = Faraday’s constant
z = number of electrons exchanged in redox reaction
aO = activity of oxidised form
aR = activity of reduced form
n = stechiometrical coefficient of oxidised form
m = stechiometrical coefficient of reduced form
Gas is under normal (or standard) conditions when: p0 = 105 Pa and T0 = 273.15 K (0 °C). IUPAC recommends that the former use of the pressure of 1 atm as standard pressure (equivalent to 101 325 Pa) should be discontinued. At these conditions, the molar volume of gas Vm0 is 0.022 711 m3 (22.711 L).
Potentiometric titration is a volumetric method in which the potential between two electrodes is measured (referent and indicator electrode) as a function of the added reagent volume. Types of potentiometric titrations for the determination of analytes in photoprocessing solutions include acid-base, redox, precipitation, and complexometric.
Potentiometric titrations are preferred to manual titrations, since they are more accurate and precise. They are also more easily adapted to automation, where automated titration systems can process larger volumes of samples with minimal analyst involvement.
A titration curve has a characteristic sigmoid curve. The part of the curve that has the maximum change marks the equivalence point of the titration. The first derivative, ΔE/ΔV, is the slope of the curve, and the endpoint occurs at the volume, V', where ΔE/ΔV has the maximum value.
Redox potential is the potential of a reversible oxidation-reduction electrode measured with respect to a reference electrode, corrected to the hydrogen electrode, in a given electrolyte.
Silver/silver-chloride electrode is by far the most common reference type used today because it is simple, inexpensive, very stable and non-toxic. It is mainly used with saturated potassium chloride electrolyte, but can be used with lower concentrations such as 3.5 mol dm-3 or 1 mol dm-3 potassium chloride. Silver/silver-chloride electrode is a referent electrode based on the following halfreaction
Potential vs. SHE / V | ||
---|---|---|
t / °C | 3.5 mol dm-3 | sat. solution |
15 | 0.212 | 0.209 |
20 | 0.208 | 0.204 |
25 | 0.205 | 0.199 |
30 | 0.201 | 0.194 |
35 | 0.197 | 0.189 |
Standards are materials containing a known concentration of an analyte. They provide a reference to determine unknown concentrations or to calibrate analytical instruments.
The accuracy of an analytical measurement is how close a result comes to the true value. Determining the accuracy of a measurement usually requires calibration of the analytical method with a known standard. This is often done with standards of several concentrations to make a calibration or working curve.
A primary standard is a reagent that is extremely pure, stable, has no waters of hydration, and has a high molecular weight.
A secondary standard is a standard that is prepared in the laboratory for a specific analysis. It is usually standardised against a primary standard.
Stratosphere is the part of the earth’s atmosphere extending from the top of the troposphere (typically 10 km to 15 km above the surface) to about 50 km. It is characterised by an increase in temperature with increasing altitude.
Generalic, Eni. "Standardna atmosfera." Croatian-English Chemistry Dictionary & Glossary. 29 June 2022. KTF-Split. {Date of access}. <https://glossary.periodni.com>.
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