During the course of an investigation into the fundamental chemistry of the cyanide process, it became evident that the usual method of determining protective alkalinity was not completely satisfactory. T.he routine method for the determination of protective alkali by first removing free cyanide by the addition of silver nitrate, followed by titration of alkali with dilute acid using. phenolphthalein as indicator, can be shown to give correct results only when the alkali is a strong base. For other sUbstances, the alkali so determined is not the protective alkali. In view of the complications associated with the presence of zinc in cyanide solutions the discussion will be restricted in the first place to solutions free from zinc. Until the chemistry of simple cyanide solutions is placed on a quantitative basis it will be difficult to elucidate the behaviour of complex mill solutions.By the use of physico-chemical theory, it is possible to treat certain aspects of 'the chemistry of cyanide solutions in a manner which not only illustrates the important variables involved, but which also shows the need for care in interpretIng results obtained by conventional methods.In the following, comparatively simple systems are discussed; the principles established should be of use in interpreting the behaviour of more complex solutions. The methods described are not intended for routine work, but may be regarded as supplementary to the usual analysis carried out for the control of plant solutions, or as alternatives to be used when the latter do not appear to be satisfactory.