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Conceptually, a lower molar entropy substance is just more ordered than another substance in comparison. For example H20 (s) has a lower molar entropy than say H20 (g). The particles in ice are more tightly and rigidly held together than in water vapor. You can also see this in the Boltzmann equation for entropy which is S=KblnW.
When one substance has a lower molar entropy than another, it means that substance is comparatively more ordered (less disorder). This further indicates that more heat is needed to make it more disordered than the other substance. For example, ice (solid H2O) has lower molar entropy than water (liquid H2O), so ice needs more heat than water to turn it into steam (gaseous H2O).
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