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 number (Kn) is a dimensionless quantity used in fluid mechanics, defined by
where λ is mean free path and l is length.
Graduated pipettes (Mohr pipette) have a scale divided into units of one and of 1/10th of a millilitre. Because of their wide necks it is less accurate than the volumetric pipette. They are used when taking volume of solutions in which accuracy does not have to be very high. By sucking in (with mouth, propipette or a water pump) the liquid is pulled in a little bit above the mark and the opening of the pipet is closed with a forefingertip. Outer wall of pipet is wiped and, with a slight forefinger loosening, the liquid is released until it reaches the mark 0. A pipette is emptied out by lifting the forefinger off and letting the liquid flow out of the pipette freely.
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.
Pipettes are glass tubes which are tapers towards at both ends into narrow opened tubes. According to their design two types of pipettes can be distinguished:
Volumetric pipettes (transfer or belly pipette) are used in volumetric analysis, when there is a need for taking exact smaller volume of a sample solution or reagent. The upper tube of volumetric pipette has a ringlike marking (mark) which marks its calibrated volume. Pipettes calibrated to deliver (TD or Ex) the indicated volume. By sucking in (with mouth, propipette or a water pump) the liquid is pulled in a little bit above the mark and the opening of the pipet is closed with a forefingertip. Outer wall of pipet is wiped and, with a slight forefinger loosening, the liquid is released until it reaches the mark. Mark must figure as a tangent on a lower edge of the liquid meniscus. A pipette is emptied out by lifting the forefinger off and letting the liquid flow out of the pipette freely. After another 15 s and the tip of the pipette is pulled onto the inner wall of the vessel. It is absolutely forbidden to blow out the contents of the pipette
Graduated pipettes (Mohr pipette) have a scale divided into units of one and of 1/10th of a millilitre. Because of their wide necks it is less accurate than the volumetric pipette. They are used when taking volume of solutions in which accuracy does not have to be very high. They are filled in the same way as volumetric ones and liquid can be gradually released.
Volumetric pipettes (transfer or belly pipette) are used in volumetric analysis, when there is a need for taking exact smaller volume of a sample solution or reagent. The upper tube of volumetric pipette has a ringlike marking (mark) which marks its calibrated volume. Pipettes calibrated to deliver (TD or Ex) the indicated volume. By sucking in (with mouth, propipette or a water pump) the liquid is pulled in a little bit above the mark and the opening of the pipet is closed with a forefingertip. Outer wall of pipet is wiped and, with a slight forefinger loosening, the liquid is released until it reaches the mark. Mark must figure as a tangent on a lower edge of the liquid meniscus. A pipette is emptied out by lifting the forefinger off and letting the liquid flow out of the pipette freely. After another 15 s and the tip of the pipette is pulled onto the inner wall of the vessel. It is absolutely forbidden to blow out the contents of the pipette.
Originally chlorinity (symbol Cl) was defined as the weight of chlorine in grams per kilogram of seawater after the bromides and iodides had been replaced by chlorides. To make the definition independent of atomic weights, chlorinity is now defined as 0.3285233 times the weight of silver equivalent to all the halides.
The Mohr-Knudsen titration method served oceanographers for more than 60 years to determine salinity from chlorinity. This modification of the Mohr method uses special volumetric glassware calibrated directly in chlorinity units. The Mohr method uses potassium chromate (K2CrO4) as an indicator in the titration of chloride ions chloride (plus a small amount of bromide and iodide) with a silver nitrate (AgNO3) standard solution.
The other halides present are similarly precipitated.
A problem in the Mohr titration was that silver nitrate is not well suited for a primary standard. The Danish physicist Martin Knudsen (1871-1949) suggested that a standard seawater (Eau de mer Normale or Copenhagen Normal Water) be created and distributed to oceanographic laboratories throughout the world. This water was then used to standardize the silver nitrate solutions. In this way all chlorinity determinations were referred to one and the same standard which gave great internal consistency.
The relationship between chlorinity Cl and salinity S as set forth in Knudsen's tables is
In 1962, however, a better expression for the relationship between total dissolved salts and chlorinity was found to be
Generalic, Eni. "Knudsen pipette." Croatian-English Chemistry Dictionary & Glossary. 29 June 2022. KTF-Split. {Date of access}. <https://glossary.periodni.com>.
Glossary
Periodic Table