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the entropy increases because a higher heat capacity means that more energy will be needed to increase that substances temperature by 1 Celsius. That extra energy needed is transferred to the substances atoms and molecules and increase their energy. This increase in energy can result in an increase in translational, rotational, etc. energy which all result in an increase in the number of positions.
First, heat capacity is the heat required to raise the temperature of an object by 1 degree Celsius. In general, increasing molecular complexity tends to also lead to higher heat capacities, since larger molecules have more possible ways to vibrate, bend and rotate. The same is true of entropy. More complex molecules have higher entropies due to a greater number of available microstates. So, in this way, if entropy increases, then heat capacity also tends to increase.
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