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Avogadro's number means that 1 mole (mol) is equal to 6.0221 * 10^23 particles. Particles can refer to molecules/atoms/formula units. You usually use it when you need to convert moles to atoms/molecules. For example, the mass on the periodic table is molar mass so you would divide by avogadro's number to get the mass of a single atom.
On top of what everyone else has said, it was helpful for me to remember to use Avogadro's number when converting kJmol^-1 to J. Your last step in this conversion would be to divide by Avogadro's number to cancel the mol^-1 out and have your answer in just J. This came up for me when solving the Audio-Visual Modules, and I couldn't seem to get the answer right because I was forgetting this last step. Hope this helps!
Avogadro's number is approximated by 6.022*10^23 and it basically represents the number of atoms in a mole of any element which is different from the individual atomic mass. You can multiply the moles of something by Avogadro's number to get the atom amount of it. You can divide by Avogadro's number to get the mole value of something in atoms, photons, or formula units.
It tells us the number of photons, electrons, molecules, atoms, etc. Anything really small and it gives it to us per mol and it is 6.022x10^23. We use it when it asks how many photos per mole or how much mass a specific molecule has.
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