Electrocardiography is used to provide features for mental state monitoring systems. There is a need for quick mental state assessment in some applications such as attentive user interfaces. We analyzed how heart rate and heart rate variability features are influenced by working memory load (WKL) and time-on-task (TOT) on very short time segments (5s) with both statistical significance and classification performance results. It is shown that classification of such mental states can be performed on very short time segments and that heart rate is more predictive of TOT level than heart rate variability. However, both features are efficient for WKL level classification. What\'s more, interesting interaction effects are uncovered: TOT influences WKL level classification either favorably when based on HR, or adversely when based on HRV. Implications for mental state monitoring are discussed.