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In addition to what has already been said, you can think about the fact that NO2 has more bonds than NO. This means that for a given amount of energy that is applied toward breaking the bonds, the energy is absorbed by 4 bonds (in NO2) as opposed to just 2 bonds (in NO). So, it will take more energy to break a molecule of NO2, which means it has a higher heat capacity than that of NO.
If you think about it, the more atoms there are, the more heat is required to raise the substance by 1 degree celsius. Therefore, because NO2 has 3 atoms rather than only 2, it takes more heat because there are more atoms that can absorb the heat.
NO2 is more complex than NO considering it has one more atom in it. This makes the molecule more complex. Since there are more atoms present, there is room for more energy to be absorbed, hence a larger capacity for heat.
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