However, only a few years later Thomas Graham (1805-1869) proved that
the three phosphoric acids are not isomeric. He used the proportion of 2
P to 5 O in the oxide which Berzelius had thought justified at least
until "an example of the contrary could be sufficiently
established."[21] Refining the techniques of Gay-Lussac (1816) and
several other investigators, Graham characterized the three phosphoric
acids as "a terphosphate, a biphosphate, and phosphate of water."
Actually, this was the wrong terminology for what he meant and
formulated as trihydrate, bihydrate, and monohydrate of phosphorus
oxide. In his manner of writing the formulas, each dot over the symbol
for the element was to indicate an atom of oxygen; thus, he wrote:
... :: .. ... . .
H^{3} P H^{2} P and H P.[22]
[Illustration: Figure 5.--OVEN FOR THE CALCINATION OF BONES, about 1870.
"The operation is carried out in a rather high oven, such as shown....
The fresh bones are thrown in at the top of the oven, B. First, fuel in
chamber F is lighted, and a certain quantity of bones is burnt on the
grid D. When these bones are burning well, the oven is gradually filled
with bones, and the combustion maintains itself without addition of
other fuel. A circular gallery, C, surrounds the bottom of the oven and
carries the products of combustion into the chimney, H. The calcined
bones are taken out at the lower opening, G, by removing the bars of
grid B." (Translation of the description from FIGUIER, _Merveilles de
l'industrie_, volume 3, 1874, page 537.)]
[Illustration: Figure 6.--AN ADVERTISEMENT with view of plant for
manufacturing superphosphate about 1867. (From E. T. FREEDLEY,
_Philadelphia and its Manufacturers in 1867_, page 288.)]
Graham had come to this understanding of the phosphoric acids through
his previous studies of "Alcoates, definite compounds of Salts and
Alcohol analogous to the Hydrates" (1831). Liebig started from analogies
he saw with certain organic acids when he formulated the phosphoric
acids with a constant proportion of water (aq.) and varying proportions
of "phosphoric acid" (P) as follows:
2 P 3 aq. phosphoric acid
3 P 3 aq. pyrophosphoric acid
6 P 3 aq. metaphosphoric acid.
[Illustration: Figure 7.--FLORIDA HARD-ROCK PHOSPHATE MINING. (From
Carroll D. Wright, _The Phosphate Industry of the United States_, sixth
special report of the Commissioner of Labor, Government Printing Office,
Washington, 1893, plate facing page 43.)]
Salts are formed when a "basis," i.e., a metal oxide, replaces water.
When potassium-acid sulfate is neutralized by sodium base, the acid-salt
divides into Glauber's salt and potassium sulfate, which proves the
acid-salt to be a mixture of the neutral salt with its acid. Sodium-acid
phosphate behaves quite differently. After neutralization by a potassium
"base" (hydroxide), the salt does not split up; a uniform
sodium-potassium phosphate is obtained. Therefore, phosphoric acid is
truly three-basic![23]
Public-domain text, read in full here on John Shaqi.
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