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Wikipedia says the Avogadro number was determined by Perrin in 1908. But Einstein used the value

$$N=6\times 10^{23}$$

as early as 1905 in order to estimate the size of the fluctuations of an molecule. How did he know it?

Addendum: Of course, the concept of a mole existed already. Proponents of the atomic theory of matter knew that a gram of an element contained a certain number of particles. According to this post, even the relative weights of atoms/molecules were known. However, I don't see there where the absolute scale for the mass of the atoms (and therefore the Avogadro number) was determined for the first time.

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Although the concept of the existence of the atoms originates from the ancient Greek, for them it was yet more a philosophical concept, they were very far from any experimental proof.1

Later, mainly the chemistry provided the first suggestion that it might be an experimental fact.

However, none of these results was strong enough at the time. In the late XIX. century, it was still a common concept of mainstream science to accept the "atomic theory", but just as a practical approximation to calculate the possible mass ratios of the elements in their compounds, but without a real meaning. It was so mainly because the lack of experimental proofs.

The acceptance of the "atom theory" happened surprisingly late, at the late XIX, early XX. century, which was also the start of Einstein's work.

The important thing is: Perrin's result alone was not enough for it, it was accepted because many, essentially different, experiments determined the same Avogadro number. Probably Perrin was the first, but also Einstein provided one, using Brownian motion.2

Einstein's method worked by the statistical analysis of the Brownian motion of oil particles suspended in water. He measured the average distance of the drops due to their random Brownian motion in a microscope. It depends on the size of the atoms: if the atoms would be smaller, then the Brownian motion would be slower due to the better statistical leveling of the water molecules around the oil drops.

The experimental challenge was big: he had to find oil drops whose size is big enough to become visible in the microscope, but they are not big enough to make their Brownian motion invisible.

1Actually, they didn't really have experimental results. They were good at axiomatizing their theories, but practice and experiments weren't their strong side. Furthermore, science, math and philosophy didn't differ conceptually in their world view: this separation happened millennia later.

2As per this paper, he doesn't mention Brownian motion in his paper, although he had probably heard about it. His work is a "new method to calculate the mass of the molecules" (my translation).

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  • $\begingroup$ Einstein used it to predict the size of the motions in Brownian motion. He used it as an assumption, not a result. $\endgroup$ Mar 31, 2019 at 14:37
  • $\begingroup$ @EricDavidKramer According this reference, Einstein doesn't mention the Brownian motion in his original paper, although he had probably heard from it. His work is an experimental proof to calculate the Avogadro number (and thus, the atomic theory). I think this is what I wrote (I insert the reference, too). $\endgroup$
    – peterh
    Mar 31, 2019 at 14:46
  • $\begingroup$ What I mean is that he calculated the size of the fluctuations/ $\endgroup$ Mar 31, 2019 at 15:08
  • $\begingroup$ @EricDavidKramer What depends on the Avogadro number. Then, measuring the actual size of the fluctuations, he could calculate the Avogadro number. And the result was the same than Perrins'. I think it is obvious in the post, or it isn't? $\endgroup$
    – peterh
    Mar 31, 2019 at 15:23
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    $\begingroup$ @EricDavidKramer The paper Einstein, Perrin, and Avagaro's Number - 1905 Revisited provides some additional reading. $\endgroup$
    – nwr
    Mar 31, 2019 at 17:51

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