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Chemistry 1811

Essay on a Manner of Determining the Relative Masses of the Elementary Molecules of Bodies

Amedeo Avogadro

Equal volumes of any gas, at the same heat and pressure, hold equal numbers of molecules.

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In depth · the introduction

Weigh two balloons of gas the same size, and — if you trust one daring idea — you have just compared the weights of their molecules.

One bold guess

Avogadro's guess is short: any two gases that fill the same volume, at the same warmth and pressure, hold the same number of molecules — no matter how heavy or light the gas.

If that is true, something wonderful follows. You can never see a single molecule, let alone weigh one. But if equal volumes hold equal numbers, then weighing two equal volumes of gas compares their molecules directly: the heavier volume has heavier molecules, in exactly the same ratio. Counting the uncountable becomes a matter of putting gases on a balance.

A count who worked alone

Amedeo Avogadro was an Italian nobleman, trained in law before he turned to physics, working quietly in Turin. He published the idea in 1811 — and almost no one listened, for fifty years. The giants of chemistry, Dalton and Berzelius among them, could not accept his second claim: that two identical atoms would pair into a molecule. Only in 1860, at a great congress in Karlsruhe, did Stanislao Cannizzaro show that Avogadro's idea untangled the whole knotted question of atomic weights — two years after Avogadro had died, never knowing he had been right.

Why it mattered

It gave chemistry a ruler. Before Avogadro, the same compound was written with different formulas by different chemists, because no one could agree how many atoms sat in a molecule. After him, the densities of gases pinned the molecular masses down, and the formulas fell into place. His hypothesis is the hidden hinge between “atoms exist” and “here is the formula for water.”

A car-park rule

Imagine a rule that says any car park of a given size always holds the same number of vehicles, whatever the model parked there. Now weigh the whole park. A heavy total means heavy cars; a light total means light cars — and the ratio of the two totals is exactly the ratio of the weights of single cars. Avogadro says gases obey just this rule, with molecules playing the part of the cars.

An interactive gas reaction: pick water, ammonia, or hydrogen chloride. Each reactant and product is a box of gas whose width is its combining volume, and a slider sets how many molecules sit in one unit of volume — the same number for every box. You can see one volume of oxygen having to split to make two volumes of water vapour.

Its place in the story

Avogadro's idea completes Dalton's atoms (see dalton-1808) and Gay-Lussac's volumes, and it is the argument Cannizzaro carried to Karlsruhe to finally settle the atomic weights. The number that bears Avogadro's name — about a 6 followed by twenty-three zeros — was only pinned down much later, when Jean Perrin watched tiny grains jitter under a microscope and counted his way to it.

The original document
Original source text
Amedeo Avogadro · Journal de Physique 73, 58–76 · 1811 · trans. Alembic Club Reprints No. 4
The starting point
Avogadro opens from Gay-Lussac's recent discovery that gases combine with one another in very simple ratios by volume — two volumes of hydrogen to one of oxygen, three of hydrogen to one of nitrogen — and asks what so clean a regularity must be telling us about the particles themselves.
The hypothesis
The first hypothesis to present itself in this connection, and apparently even the only admissible one, is the supposition that the number of integral molecules in any gases is always the same for equal volumes, or always proportional to the volumes.
He is careful with words. An “integral molecule” is the molecule of a compound; a “constituent molecule” the molecule of an element; an “elementary molecule” the atom — what he also calls the half-molecule. The distinction between atom and molecule, blurred in Dalton's chemistry, is the quiet hinge of the whole paper.
[ … ]
Why the molecules must divide
Two volumes of hydrogen and one of oxygen make two volumes of water vapour. If each particle were a single, indivisible atom, one volume of oxygen could yield at most one volume of product — yet two appear. The only escape is that the particle of an elementary gas is not one atom but a small molecule that splits when it combines.
Thus in all these cases there must be a division of the molecule into two; but it is possible that in other cases the division might be into four, eight, &c.
From here the prize falls out. At equal volume the gases hold equal numbers of molecules, so the ratio of their densities is the ratio of their molecular masses: weigh the gases and you have read their relative molecular weights directly, hydrogen taken as the unit.
[ … ]
The essay drew almost no following. For half a century chemists could not accept that two identical atoms would join into a molecule, and Avogadro, working far from the centres of chemistry, was largely unread until Cannizzaro revived the argument in 1858–1860.
Turin · 1811