1. The electrochemical behavior ("activity") of collodion membranes depends upon acidic, dissociable groups located in the interstices of the membranes. The active groups can be determined by base exchange measurements. High base exchange capacity is always found with preparations of great "electrochemical activity;" medium and low base exchange capacities occur with electrochemically active as well as with inactive preparations. The observed base exchange capacity is determined by two factors: the inherent acidity of the collodion (its mean equivalent weight) and the submicroscopic micellar structure of the collodion. A comparison of the base exchange capacity of various collodion preparations and their inherent acidities therefore allows certain conclusions to be drawn concerning the relative availability of the micellar surfaces in the different preparations.
2. The inherent acidity of various collodion preparations, their "acid number," was determined by electrometric titration. Collodion in the acidic state, i.e. after exchange of all other cations for H+ ions, was titrated in an organic solvent mixture with alcoholic KOH using a quinhydrone electrode. Details of the experimental procedure are given in the paper. The acid numbers, expressed in milliliters of 0.01 N KOH per gram dry collodion, vary from 1.0 for a highly purified collodion preparation of very low electrochemical activity to 3.3 for a highly oxidized sample of very high activity. Acid numbers of about 1.5 (corresponding to an equivalent weight of about 67,000) are found both with inactive commercial and with fairly active oxidized preparations. The base exchange capacity of the same preparations in the fibrous state as measured after 48 hours of exchange time varies from 0.0013 ml. 0.01 N NaOH per gm. dry collodion for the most inactive preparation up to 0.26 ml. 0.01 N NaOH per gm. for the most active preparation. Thus the acid numbers over the whole range investigated differ only in the ratio of 1:3.3, whereas the base exchange values differ in the range of 1:200.
3. In the inactive preparation only one in 770 acid groups is available for base exchange, in the most active collodion one group in 13; values between these extremes are found with commercial and alcohol purified oxidized preparations.
4. The high base exchange capacity of the electrochemically active preparations is not so much due to their higher acid number as to their more open structure. This difference in structure is ascribed to the presence of a small fraction of low molecular weight material which inhibits normal formation and arrangement of the micelles.
5. Short time base exchange experiments with fibrous collodion indicate that the number of acid groups available for the typical electrochemical membrane functions may be estimated to be about 50 to 1000 times less numerous than those found in the 48 hour base exchange experiments. It is estimated that in membranes prepared even from the most active collodion not more than one in 500 acid groups may be available for the typical membrane functions; with the less active preparations this ratio is estimated to be as high as one in 1,000,000 or more.
Amine substitution into sulfuric acid – ammonia clusters
