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    The Karl Fischer Reaction: Stoichiometry

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    goparsuco
    teoria de karl fisher

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    The Karl Fischer Reaction: Stoichiometry

    Uploaded by

    goparsuco
    41 views3 pages
    teoria de karl fisher

    Original Title

    Karl Fisher Theory

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    © © All Rights Reserved

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    teoria de karl fisher

    Copyright:

    © All Rights Reserved
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    Download as pdf or txt
    41 views3 pages

    The Karl Fischer Reaction: Stoichiometry

    Uploaded by

    goparsuco
    teoria de karl fisher

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    of 3

    The Karl Fischer reaction

    Stoichiometry

    (1) CH3OH + SO2 + RN [RNH]SO3CH3


    (2) H2O + I2 + [RNH]SO3CH3 + 2 RN [RNH]SO4CH3 + 2 [RNH]I
    (RN = Base)

    Kinetics
    Reaction (1) reaches an equilibrium and produces as reaction intermediate methylsulfite.
    Reaction (2) is the oxidation-reduction step. It is very rapid. The rate of the reaction
    depends on the base chosen. Pyridine is not suitable for this purpose. Because of its
    weak basicity, the methyl sulphurous acid cannot be neutralized completely by pyridine.
    The equilibrium (1) is not completely shifted to the right. The reaction is therefore very
    slow and the end point is not stable. Because of this lack of stability, the repeatability of
    the results is often very poor.
    The investigation involved finding amines with a higher basicity and a better affinity for
    methyl sulfite. Dr. Scholz chose imidazole. This base shifts the equilibrium (1)
    completely to the right. The reaction proceeds at maximum speed and the end point is
    very stable. A much greater accuracy can be achieved.
    Imidazole seems to be the ideal KF base.

    Research at Riedel-de Haën

    1979 Beginning of research and development led by Dr. Eugen Scholz

    Purpose: To eliminate the unpleasant pyridine as the base.

    Results: Pyridine is not a reactant in the KF reaction. lt merely acts as a buffer.


    Pyridine can be replaced by bases which are superior for this application.

    Action: Determination of bases which optimize the reaction.


    Patent application for the use of these bases. Choice of base with the best
    buffer capacity: imidazole. Development of new KF reagents using
    imidazole as base in the HYDRANAL® reagents.
    Developments:
    Replacement of halogenated solvents to meet requirements of health care
    and environment. Replacement of the toxic methanol with ethanol: new
    HYDRANAL®-E Types

    New reagents
    As result of our research and development KF-Reagents with many advantages are
    produced.
    high titration speed
    stable end points
    accurate results
    no unpleasant odour
    increased safety
    Iong storage stability
    universal applicability

    Regular course of titration


    The diagram shows the regular course of the titration of 40 mg water with HYDRANAL®-
    Composite using methanol as the working medium. The efficiency of the reagent is
    demonstrated by the rapid titration of the free water, as seen from a portion of the curve.
    The gradient of this portion of the titration curve is dependent upon the rate of
    administration of reagent from the burette. After reaching the 20-second end-point, the
    point b (the excess of reagent), shows that the subsequent consumption of the reagent
    is virtually zero. This is an indication of the hermeticity of the cell and of the working
    technique of the titration.
    Vanishing end point
    The diagram depicts the titration of 40 mg water in the presence of 5 mL acetone.
    Portion b of the curve is no longer vertical and indicates a continual consumption of the
    excess reagent and is caused by the ketal formation. The "b" portion of the graph is in
    fact a straight line. The rate of this side reaction is indeed constant. The initial water
    content of the sample can therefore be evaluated by extrapolation of the b portion of the
    curve to t = 0. The origin of the curve, i.e. t = 0, should therefore be carefully deter-
    mined. The titration must be started as soon as the sample is added, or, even better,
    shortly beforehand (flying start).
    The graphical evaluation of the course of a titration enables the real water content of
    individual samples to be determined more accurately, in spite of a slow side reaction
    taking place. Such a method should always be used when the side reaction cannot be
    suppressed by suitable means.

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