When scientists apply Archie's first law they often include an extra parameter a, which was introduced about 10 years after the equation's first publication by Winsauer et al. (1952), and which is sometimes called the “tortuosity” or “lithology” parameter. This parameter is not, however, theoretically justified. Paradoxically, the Winsauer et al. (1952) form of Archie's law often performs better than the original, more theoretically correct version. The difference in the cementation exponent calculated from these two forms of Archie's law is important, and can lead to a misestimation of reserves by at least 20 % for typical reservoir parameter values. We have examined the apparent paradox, and conclude that while the theoretical form of the law is correct, the data that we have been analysing with Archie's law have been in error. There are at least three types of systematic error that are present in most measurements: (i) a porosity error, (ii) a pore fluid salinity error, and (iii) a temperature error. Each of these systematic errors is sufficient to ensure that a non-unity value of the parameter a is required in order to fit the electrical data well. Fortunately, the inclusion of this parameter in the fit has compensated for the presence of the systematic errors in the electrical and porosity data, leading to a value of cementation exponent that is correct. The exceptions are those cementation exponents that have been calculated for individual core plugs. We make a number of recommendations for reducing the systematic errors that contribute to the problem and suggest that the value of the parameter a may now be used as an indication of data quality.

This paper describes the extension of the concepts of connectedness and conservation of connectedness that underlie the generalized Archie's law for n phases to the interpretation of the saturation exponent. It is shown that the saturation exponent as defined originally by Archie arises naturally from the generalized Archie's law. In the generalized Archie's law the saturation exponent of any given phase can be thought of as formally the same as the phase (i.e. cementation) exponent, but with respect to a reference subset of phases in a larger n-phase medium. Furthermore, the connectedness of each of the phases occupying a reference subset of an n-phase medium can be related to the connectedness of the subset itself by G_i = G_refS_i^n_i. This leads naturally to the idea of the term S_i^n_i for each phase i being a fractional connectedness, where the fractional connectednesses of any given reference subset sum to unity in the same way that the connectednesses sum to unity for the whole medium. One of the implications of this theory is that the saturation exponent of any phase can be now be interpreted as the rate of change of the fractional connectedness with saturation and connectivity within the reference subset.

A large number (1253) of high-quality streaming potential coefficient (\(C_\mathrm{sp})\) measurements have been carried out on Berea, Boise, Fontainebleau, and Lochaline sandstones (the latter two including both detrital and authigenic overgrowth forms), as a function of pore fluid salinity (\(C_\mathrm{f})\) and rock microstructure. All samples were saturated with fully equilibrated aqueous solutions of NaCl (10\(^{-5}\) and 4.5 mol/dm\(^{3})\) upon which accurate measurements of their electrical conductivity and pH were taken. These \(C_\mathrm{sp}\) measurements represent about a fivefold increase in streaming potential data available in the literature, are consistent with the pre-existing 266 measurements, and have lower experimental uncertainties. The \(C_\mathrm{sp}\) measurements follow a pH-sensitive power law behaviour with respect to \(C_\mathrm{f}\) at medium salinities (\(C_\mathrm{sp} =-\,1.44\times 10^{-9} C_\mathrm{f}^{-\,1.127} \), units: V/Pa and mol/dm\(^{3})\) and show the effect of rock microstructure on the low salinity \(C_\mathrm{sp}\) clearly, producing a smaller decrease in \(C_\mathrm{sp}\) per decade reduction in \(C_\mathrm{f}\) for samples with (i) lower porosity, (ii) larger cementation exponents, (iii) smaller grain sizes (and hence pore and pore throat sizes), and (iv) larger surface conduction. The \(C_\mathrm{sp}\) measurements include 313 made at \(C_\mathrm{f} > 1\) mol/dm\(^{3}\), which confirm the limiting high salinity \(C_\mathrm{sp}\) behaviour noted by Vinogradov et al., which has been ascribed to the attainment of maximum charge density in the electrical double layer occurring when the Debye length approximates to the size of the hydrated metal ion. The zeta potential (\(\zeta \)) was calculated from each \(C_\mathrm{sp}\) measurement. It was found that \(\zeta \) is highly sensitive to pH but not sensitive to rock microstructure. It exhibits a pH-dependent logarithmic behaviour with respect to \(C_\mathrm{f}\) at low to medium salinities (\(\zeta =0.01133 \log _{10} \left( {C_\mathrm{f} } \right) +0.003505\), units: V and mol/dm\(^{3})\) and a limiting zeta potential (zeta potential offset) at high salinities of \({\zeta }_\mathrm{o} = -\,17.36\pm 5.11\) mV in the pH range 6–8, which is also pH dependent. The sensitivity of both \(C_\mathrm{sp}\) and \(\zeta \) to pH and of \(C_\mathrm{sp}\) to rock microstructure indicates that \(C_\mathrm{sp}\) and \(\zeta \) measurements can only be interpreted together with accurate and equilibrated measurements of pore fluid conductivity and pH and supporting microstructural and surface conduction measurements for each sample.

High‐quality streaming potential coupling coefficient measurements have been carried out using a newly designed cell with both a steady state methodology and a new pressure transient approach. The pressure transient approach has shown itself to be particularly good at providing high‐quality streaming potential coefficient measurements as each transient increase or decrease allows thousands of measurements to be made at different pressures to which a good linear regression can be fitted. Nevertheless, the transient method can be up to 5 times as fast as the conventional measurement approaches because data from all flow rates are taken in the same transient measurement rather than separately. Test measurements have been made on samples of Berea and Boise sandstone as a function of salinity (approximately 18 salinities between 10⁻⁵ mol/dm³ and 2 mol/dm³). The data have also been inverted to obtain the zeta potential. The streaming potential coefficient becomes greater (more negative) for fluids with lower salinities, which is consistent with existing measurements. Our measurements are also consistent with the high‐salinity streaming potential coefficient measurements made by Vinogradov et al. (2010). Both the streaming potential coefficient and the zeta potential have also been modeled using the theoretical approach of Glover (2012). This modeling allows the microstructural, electrochemical, and fluid properties of the saturated rock to be taken into account in order to provide a relationship that is unique to each particular rock sample. In all cases, we found that the experimental data were a good match to the theoretical model.