Adsorbed small charged molecules are known to give rise to a range of surface forces that affect the rheological characteristics of oxide dispersions. The behaviour of dicarboxylic acid bolaform compounds in alumina slurry was investigated to determine the macroscopic-microscopic effect of the compounds’ architecture on the interactions between spherical alumina particles. The surface forces in dispersions and between two macrobodies were characterized by yield stress and Atomic Force Microscopy (AFM) respectively. The surface chemistry was accessed via zeta potential while the adsorption behaviour was determined using total-carbon-content technique. Adsorbed trans and cis muconic acid resulted in a much higher yield stress and this is attributed to particle bridging. The trans-isomer has a better bridging ability due to its structure that enables further outreach to the neighbouring particles. The pull-off force from AFM measurement was used to quantify the strength of the bridging interactions and its dependence on the isomeric structure of the additives. The surface coverage of the adsorbed additives and its effects on bridging forces is obtained from the adsorption trend of trans and cis muconic acid. The yield stress under the influence of these adsorbed additives was compared with that obtained from non-ideal spherical alumina dispersions to evaluate the effect of surface roughness. In conclusion, surface roughness has little effect on yield stress enhancement and the architecture of muconic acid is ideal for particle bridging. The combination of rheology and AFM technique enable the definite determination of the underlying mechanism in bridging by small charged molecules.